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NanoManufacturing

Michael De Volder, Engineering Department - IfM

Studying at Cambridge

Nanoscience News

Giant Enhancement of Second Harmonic Generation Accompanied by the Structural Transformation of 7‐Fold to 8‐Fold Interpenetrated Metal–Organic Framework (MOF)

By Zhihui Chen, Gianpiero Gallo, Vaishali A. Sawant, Tianxiang Zhang, Menglong Zhu, Liangliang Liang, Anjana Chanthapally, Geetha Bolla, Hong Sheng Quah, Xiaogang Liu, Kian Ping Loh, Robert E. Dinnebier, Qing‐Hua Xu, Jagadese J. Vittal from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 06, 2019.

“A baby cheetah leaps several feet more than the cheetah mom” is an old saying in Tamil. In this case, an 8‐fold interpenetrated MOF shows a giant enhancement of the second harmonic generation (SHG) as compared to the parent 7‐fold interpenetrated MOF. As shown in the Research Article (DOI: 10.1002/anie.201911632) by R. E. Dinnebier, Q.‐H. Xu, J. J. Vittal et al., the 8‐fold interpenetrated MOF results from the removal of DMF from the channel in a single‐crystal‐to‐single‐crystal transformation.

Chameleon Metals: Autonomous Nano‐Texturing and Composition Inversion on Liquid Metals Surfaces

By Andrew Martin, Winnie Kiarie, Boyce Chang, Martin Thuo from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 06, 2019.

Chameleon metals: Metal passivating oxide layer is a complex pseudo‐equilibrium system with a plethora of undiscovered features. In their Research Article (DOI: 10.1002/anie.201912639), M. Thuo et al. exploit the complexity of this thin oxide layer to engineer surface design and structure, resulting in the formation of compositionally inverted surface features and nano‐scale fractal‐like designs.

Microporosity of a Guanidinium Organodisulfonate Hydrogen‐Bonded Framework

By Ivana Brekalo, David E. Deliz, Leonard J. Barbour, Michael D. Ward, Tomislav Friščić, K. Travis Holman from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 06, 2019.

Pores now found! The porous polymorph of guanidinium 1,4‐benzenedisulfonate, G2BDS, one of the simplest members of an archetypal class of hydrogen‐bonded frameworks, was prepared from its acetone solvate by single‐crystal‐to‐single‐crystal (SC‐SC) desolvation. The persistent porosity, phase behavior, and gas sorption characteristics are described. Abstract Guanidinium organosulfonates (GSs) are a large and well‐explored archetypal family of hydrogen‐bonded organic host frameworks that have, over the past 25 years, been regarded as nonporous. Reported here is the only example to date of a conventionally microporous GS host phase, namely guanidinium 1,4‐benzenedisulfonate (p‐G2BDS). p‐G2BDS is obtained from its acetone solvate, AcMe@G2BDS, by single‐crystal‐to‐single‐crystal (SC‐SC) desolvation, and exhibits a Type I low‐temperature/pressure N2 sorption isotherm (SABET=408.7(2) m2 g−1, 77 K). SC‐SC sorption of N2, CO2, Xe, and AcMe by p‐G2BDS is explored under various conditions and X‐ray diffraction provides a measurement of the high‐pressure, room temperature Xe and CO2 sorption isotherms. Though p‐G2BDS is formally metastable relative to the “collapsed”, nonporous polymorph, np‐G2BDS, a sample of p‐G2BDS survived for almost two decades under ambient conditions. np‐G2BDS reverts to zCO2@p‐G2BDS or yXe@p‐G2BDS (y,z=variable) when pressure of CO2 or Xe, respectively, is applied.

Theory and Ab Initio Calculation of Optically Excited States—Recent Advances in 2D Materials

By Kaichen Xie, Xiaosong Li, Ting Cao from Wiley: Advanced Materials: Table of Contents. Published on Dec 06, 2019.

2D materials exhibit unique physical phenomena and features that are absent in conventional bulk semiconductors. The theoretical and ab initio methods that yield the optically excited states in 2D materials are reviewed. Several analytical and numerical approaches are introduced and their results are compared with experiments. Abstract Recent studies of the optical properties of 2D materials have reported unique phenomena and features that are absent in conventional bulk semiconductors. Many of these interesting properties, such as enhanced light‐matter coupling, gate‐tunable photoluminescence, and unusual excitonic optical selection rules arise from the nature of the two‐ and multi‐particle excited states such as strongly bound Wannier excitons and charged excitons. The theory, modeling, and ab initio calculations of these optically excited states in 2D materials are reviewed. Several analytical and ab initio approaches are introduced. These methods are compared with each other, revealing their relative strength and limitations. Recent works that apply these methods to a variety of 2D materials and material‐defect systems are then highlighted. Understanding of the optically excited states in these systems is relevant not only for fundamental scientific research of electronic excitations and correlations, but also plays an important role in the future development of quantum information science and nano‐photonics.

“Design of Experiments” as a Method to Optimize Dynamic Disulfide Assemblies: Cages and Functionalizable Macrocycles

By Trevor A. Shear, Fuding Lin, Lev N. Zakharov, Darren W. Johnson from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 06, 2019.

Eight new macrocycles with reactive functional handles were synthesized through metalloid‐assisted self‐assembly. “Design of experiments” was utilized to optimize reaction conditions for multiple systems to significantly increase the yield of a single, targeted macrocycle. Abstract Cyclophanes are a venerable class of macrocyclic and cage compounds that often contain unusual conformations, high strain, and unusual properties. However, synthesis of complex, functional derivatives remains difficult due to low functional group tolerance, high dilution, extreme reaction conditions, and sometimes low yields using traditional stepwise synthetic methods. “Design of experiments” (DOE) is a method employed for the optimization of reaction conditions, and we showcase this approach to generate a dramatic increase in the yield of specific targets from two different self‐assembling systems. These examples demonstrate that DOE provides an additional tool in tuning self‐assembling, dynamic covalent systems.

A Novel Approach to Functionalization of Aryl Azides through the Generation and Reaction of Organolithium Species Bearing Masked Azides in Flow Microreactors

By Daisuke Ichinari, Yosuke Ashikari, Kyoko Mandai, Yoko Aizawa, Jun‐ichi Yoshida, Aiichiro Nagaki from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 06, 2019.

Beneath the mask: A novel and straightforward method for synthesizing aryl azides bearing a variety of functional groups by using flow microreactor system was achieved. This strategy is based on the generation and reaction of aryllithium species bearing a triazene as a masked azide group. Abstract A novel straightforward method for aryl azides having functional groups based on generation and reactions of aryllithiums bearing a triazene group from polybromoarenes using flow microreactor systems was achieved. The present approach will serve as a powerful method in organolithium chemistry and open a new possibility in the synthesis of polyfunctional organic azides.

Nitrenium Salts in Lewis Acid Catalysis

By Meera Mehta, Jose Manuel Goicoechea from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 06, 2019.

Molecular compounds featuring nitrogen atoms are typically regarded as Lewis bases and are extensively employed as donor ligands in coordination chemistry or as nucleophiles in organic chemistry. By contrast, electrophilic nitrogen‐containing compounds are much rarer. Nitrenium cations are a new family of nitrogen‐based Lewis acids, the reactivity of which remains largely unexplored. In this work, nitrenium ions are explored as catalysts in five organic transformations. These reactions are the first examples of Lewis acid catalysis employing nitrogen as the site of substrate activation. Moreover, these compounds are readily accessed from commercially available reagents and exhibit remarkable stability toward moisture, allowing for benchtop transformations without the need to pretreat solvents.

Facile Synthesis of Nanosized Single‐Crystalline Hierarchical Aluminophosphate Molecular Sieves from Highly Homogeneous and Concentrated Precursors

By Shuo Tao, Xiaolei Li, Xiaoge Wang, Ying Wei, Yunling Jia, Jing Ju, Yuanhui Cheng, Huaisheng Wang, Shuwen Gong, Xingjun Yao, Haixu Gao, Cunyin Zhang, Qiqi Zang, Zhi-Jian Tian from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 06, 2019.

The synthesis of nanosized hierarchical zeolite materials without growth modifiers and mesoporogens remains a substantial challenge. Herein, we report a general synthetic approach for nanosized single‐crystalline hierarchical aluminophosphate molecular sieves from preparing highly homogeneous and concentrated precursors and heating at elevated temperatures. Accordingly, aluminophosphate zeotypes of LTA (8‐rings), AEL (10‐rings), AFI (12‐rings), and –CLO (20‐rings) topologies, ranging from small to extra‐large pores, were synthesized. These materials show exceptional properties, including small crystallites (30‐150 nm), good monodispersity, abundant mesopores, and excellent thermal stability. The time‐dependent study reveals a nonclassical crystallization pathway by particle attachment. This work opens a new avenue for the development of nanosized hierarchical zeolite materials and understanding their crystallization mechanism.

Tue 03 Mar 14:30: Title to be confirmed

From All Talks (aka the CURE list). Published on Dec 06, 2019.

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Self‐amplified Photodynamic Therapy through 1O2‐mediated In Situ Internalization of Photosensitizers from a Ppa‐bearing Block Copolymer

By Zhiyong Liu, Tianye Cao, Yudong Xue, Mengting Li, Mengsi Wu, Jonathan W. Engle, Qianjun He, Weibo Cai, Minbo Lan, Weian Zhang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 06, 2019.

Nanocarriers are employed to deliver photosensitizers for photodynamic therapy (PDT) through the enhanced penetration and retention effect, but disadvantages including the premature leakage and non‐selective release of photosensitizers are still existing. Herein, we developed a 1 O 2 ‐responsive block copolymer (POEGMA‐ b ‐P(MAA‐ co ‐VSPpaMA) to enhance PDT via precisely controllable release of photosensitizers. Once nanoparticles formed by the block copolymer were accumulated in tumor and taken up by cancer cells, pyropheophorbide‐a (Ppa) could be controllably released via the trigger of singlet oxygen ( 1 O 2 ) generated by a short duration light irradiation, thus enhancing the photosensitization, which was demonstrated by confocal laser scanning microscopy and in vivo fluorescence imaging. Consequently, benefiting from the 1 O 2 ‐responsiveness of POEGMA‐ b ‐P(MAA‐ co ‐VSPpaMA) block copolymer, a self‐amplified photodynamic therapy could be well realized by regulating the release of Ppa with NIR illumination for enhancing the sensitization of Ppa, which may provide a new insight into the design of precise PDT.

Tue 10 Mar 14:30: Title to be confirmed

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Fri 13 Mar 16:30: Title to be confirmed

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Fri 06 Mar 16:30: Title to be confirmed

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Fri 28 Feb 16:30: Title to be confirmed

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Fri 21 Feb 16:30: Title to be confirmed

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Fri 14 Feb 16:30: Title to be confirmed

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Fri 07 Feb 16:30: Title to be confirmed

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Fri 31 Jan 16:30: Title to be confirmed

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Fri 24 Jan 16:30: Title to be confirmed

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Fri 17 Jan 16:30: Title to be confirmed

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Photoinduced Multiple Effects to Enhance Uranium Extraction from Natural Seawater by Black Phosphorus Nanosheets

By Yihui Yuan, Biye Niu, Qiuhan Yu, Xin Guo, Zhanhu Guo, Jun Wen, Tao Liu, Haiquan Zhang, Ning Wang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 06, 2019.

A BP‐PAO fiber enhanced by multiple photoinduced effects was fabricated by compositing black phosphorus (BP) nanosheet into the polyacrylamidoxime (PAO) fiber. The photocatalytic, photothermal, and photoelectric effects of the BP nanosheet endowed the BP‐PAO fiber with high antibiofouling activity and enhanced uranium extraction capacity from natural seawater. Abstract Based on the photoinduced photothermal, photoelectric, and photocatalytic effects of black phosphorus (BP) nanosheets, a BP‐PAO fiber with enhanced uranium extraction capacity and high antibiofouling activity is fabricated by compositing BP nanosheets into polyacrylamidoxime (PAO). The photothermal effect increases the coordination interaction between UO22+ and the functional amidoxime group, and the photoelectric effect produces the surface positive electric field that exhibits electrostatic attraction to the negative [UO2(CO3)3]4−, which all increase the capacity for uranium adsorption. The photocatalytic effect endows the adsorbent with high antibiofouling activity by producing biotoxic reactive oxygen species. Owing to these three photoinduced effects, the photoinduced BP‐PAO fiber shows a high uranium adsorption capacity of 11.76 mg g−1, which is 1.50 times of the PAO fiber, in bacteria‐containing natural seawater.

An Exceptionally Stable and Scalable Sugar–Polyolefin Frank–Kasper A15 Phase

By Kätchen K. Lachmayr, Charlotte M. Wentz, Lawrence R. Sita from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 06, 2019.

Supramolecular truffles: A readily accessible one‐component sugar–polyolefin conjugate is presented that quantitatively produces an exceptionally stable thermotropic soft matter Frank–Kasper A15 phase through a rapid and irreversible thermotropic order–order transition. Abstract “One‐component” soft material Frank–Kasper (FK) phases are an intriguing structural form of matter that possess periodically ordered structures arising from the self‐reconfiguration and close packing of an initial assembly of identical “deformable” spheres into two or more size‐ or shape‐distinct sets of particles. Significant challenges that must still be addressed to advance the field of soft matter FK phases further, however, include their rare and unpredictable occurrence, uncertain mechanisms of solid‐state assembly, and low thermodynamic stability. Here we show that a readily‐accessible sugar–polyolefin conjugate quantitatively produces an exceptionally stable solid‐state FK A15 phase through a rapid and irreversible thermotropic order–order transition, which contrary to other prevailing proposed mechanisms, does not require mass transfer between particles or large structural reorganization in the bulk to establish unit cell non‐equivalency. Our results provide the basis for a realistic strategy for obtaining practical and scalable quantities of a diverse range of sugar–polyolefin FK A15 phases with unique intrinsic physical properties and chemical reactivities not previously seen in such systems.

Imparting Superhydrophobicity with a Hierarchical Block Copolymer Coating

By Li‐Chen Cheng, John W. Simonaitis, Karim R. Gadelrab, Mukarram Tahir, Yi Ding, Alfredo Alexander‐Katz, Caroline A. Ross from Wiley: Small: Table of Contents. Published on Dec 06, 2019.

A robust and transparent silica‐like coating created through block copolymer self‐assembly imparts superhydrophobicity to a surface through its hierarchical multilevel structure. A model based on the hierarchical topography calculates the wetting angle and optimizes the superhydrophobicity, in agreement with the experimental trends, and explains how the superhydrophobicity arises through a combination of roughness at different lengthscales. Abstract A robust and transparent silica‐like coating that imparts superhydrophobicity to a surface through its hierarchical multilevel self‐assembled structure is demonstrated. This approach involves iterative steps of spin‐coating, annealing, and etching of polystyrene‐block‐polydimethylsiloxane block copolymer thin films to form a tailored multilayer nanoscale topographic pattern with a water contact angle up to 155°. A model based on the hierarchical topography is developed to calculate the wetting angle and optimize the superhydrophobicity, in agreement with the experimental trends, and explaining superhydrophobicity arising through the combination of roughness at different lengthscales. Additionally, the mechanical robustness and optically passive properties of the resulting hydrophobic surfaces are demonstrated.

An Interfacial Electron Transfer on Tetrahedral NiS2/NiSe2 Heterocages with Dual‐Phase Synergy for Efficiently Triggering the Oxygen Evolution Reaction

By Yang Yang, Yikun Kang, Huihui Zhao, Xiaoping Dai, Meilin Cui, Xuebin Luan, Xin Zhang, Fei Nie, Ziteng Ren, Weiyu Song from Wiley: Small: Table of Contents. Published on Dec 06, 2019.

Tetrahedral NiS2/NiSe2 heterocages with rich‐phase boundaries are constructed by a simultaneous sulfuration/selenylation process. The interfacial electron transfer induces electronic structure modulation, thus cooperating synergistically to change rate‐determining step of oxygen‐containing intermediates in the oxygen evolution reaction (OER), which efficiently triggers the OER process, and accelerate the OER kinetics. Abstract Tetrahedral NiS2/NiSe2 heterocages with rich‐phase boundaries are synthesized through a simultaneous sulfuration/selenylation process using Ni‐based acetate hydroxide prisms as precursor. Such a nanocage‐like NiS2/NiSe2 heterostructure can expose more active sites, accelerate the mass transport of the ions/gas, and optimize the interfacial electronic structure, which shows a significantly lower overpotential of 290 mV at 20 mA cm−2 than those of NiS/NiS2 and NiSe2 as counterparts. The experimental characterizations and theoretical density functional theory (DFT) calculations unveil that the interfacial electron transfer from NiSe2 to NiS2 at the heterointerface can modulate the electronic structure of NiS2/NiSe2, which further cooperates synergistically to change the Gibbs free energy of oxygen‐containing intermediates as the rate‐determining step (RDS) from 2.16 eV (NiSe2) and 2.10 eV (NiS2) to 1.86 eV (NiS2/NiSe2 heterostructures) during the oxygen evolution reaction (OER) process. And as a result, tetrahedral NiS2/NiSe2 heterocages with dual‐phase synergy efficiently trigger the OER process, and accelerate the OER kinetics. This work provides insights into the roles of the interfacial electron transfer in electrocatalysis, and can be an admirable strategy to modulate the electronic structure for developing highly active electrocatalysts.

Hierarchical Porous Organometallic Polymers Fabricated by Direct Knitting: Recyclable Single‐Site Catalysts with Enhanced Activity

By Yajing Shen, Qingshu Zheng, Haibo Zhu, Tao Tu from Wiley: Advanced Materials: Table of Contents. Published on Dec 06, 2019.

Robust porous organometallic polymers with atomically dispersed metal and hierarchical pores are fabricated via direct knitting of NHC‐M (M = Ir, Pd, Ru) complexes. These complexes function as highly efficient bifunctional single‐site and recyclable catalysts, and show dramatically enhanced catalytical activity and selectivity than corresponding NHC‐M complexes both for dehydrogenation and hydrogenation reactions. Abstract Porous organometallic polymers (POMPs) with hierarchical pore structures, high specific surface areas, and atomically dispersed metal (Ir, Pd, Ru) centers are successfully fabricated by a facile one‐pot method through direct knitting of diverse N‐heterocyclic carbene metal (NHC‐M) complexes. These polymers can function as recyclable solid single‐site catalysts and exhibit excellent catalytic activity and selectivity in both dehydrogenation and hydrogenation reactions even at ppm‐level catalyst loadings. Remarkably, a record turnover number (TON) of 1.01 × 106 is achieved in the hydrogenation of levulinic acid to γ‐valerolactone, which is 750 times higher than that attained with corresponding bis‐NHC‐Ir complex.

Low‐Iridium‐Content IrNiTa Metallic Glass Films as Intrinsically Active Catalysts for Hydrogen Evolution Reaction

By Zi‐Jian Wang, Ming‐Xing Li, Ji‐Hao Yu, Xing‐Bo Ge, Yan‐Hui Liu, Wei‐Hua Wang from Wiley: Advanced Materials: Table of Contents. Published on Dec 06, 2019.

An extremely flat low‐iridium‐content Ir25Ni33Ta42 metallic glass film with an ultralow Ir loading is presented as an intrinsically active and highly stable catalyst for the hydrogen evolution reaction (HER) in acids. This work provides a novel alloy system for HER in acids, and is helpful for the development of heterogeneous catalysts in multicomponent alloys. Abstract Although various catalytic materials have emerged for hydrogen evolution reaction (HER), it remains crucial to develop intrinsically effective catalysts with minimum uses of expensive and scarce precious metals. Metallic glasses (MGs) or amorphous alloys show up as attractive HER catalysts, but have so far limited to material forms and compositions that result in high precious‐metal loadings. Here, an Ir25Ni33Ta42 MG nanofilm exhibiting high intrinsic activity and superior stability at an ultralow Ir loading of 8.14 µg cm−2 for HER in 0.5 m H2SO4 is reported. With an overpotential of 99 mV for a current density of 10 mA cm−2, a small Tafel slope of 35 mV dec−1, and high turnover frequencies of 1.76 and 19.3 H2 s−1 at 50 and 100 mV overpotentials, the glassy film is among the most intrinsically active HER catalysts, outcompetes any reported MG, representative sulfides, and phosphides, and compares favorably with other precious‐metal‐containing catalysts. The outstanding HER performance of the Ir25Ni33Ta42 MG film is attributed to the synergistic effect of the novel alloy system and amorphous structure, which may inspire the development of multicomponent alloys for heterogeneous catalysis.

Dancing Brightly Under Light: Intriguing Photomechanical Luminescence in Constructing Through‐Space Conjugated AIEgens

By Jingjing Guo, Jianzhong Fan, Xinzhi Liu, Zujin Zhao, Ben Zhong Tang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 06, 2019.

Transforming molecular motions into macroscopic scale is a topic of great interest to nanoscience. Photomechanical effect is a promising strategy to realize this purpose but remains challenging to design molecular materials with superior photomechanical effect that can be visually monitored under UV light. Herein, we wish to report intriguing photomechanical luminescence driven by photodimerization of 2‐phenylbenzo[b]thiophene 1,1‐dioxide (P‐BTO) in molecular crystals, and elucidate working mechanism and substituent effect via crystallography analysis and theoretical calculation. Striking splitting, hopping and bending mechanical behaviors accompanied by significant blue fluorescence enhancement are observed for P‐BTO crystals under UV light, which is attributed to the formation of photodimer 2P‐BTO. Although 2P‐BTO is poorly π‐conjugated because of the central cyclobutane ring, it exhibits prominent through‐space conjugation and aggregation‐induced emission (AIE) characters, affording strong solid‐state blue fluorescence at 415 nm with an excellent quantum yield of up to 96.2%. This work not only provides novel molecular crystals with photomechanical luminescence but also explores a new kind of AIE luminogens (AIEgens) based on a tailored through‐space conjugated framework.

Green Metal‐Free Photochemical Hydroacylation of Unactivated Olefins

By Errika Voutyritsa, Christoforos G. Kokotos from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 06, 2019.

Photochemistry: A mild, metal‐free and easy‐to‐execute protocol for the direct photochemical hydroacylation of unactivated olefins was developed using phenylglyoxylic acid as the photoinitiator. Abstract Direct alkylation of C(sp2)−H bonds to convert an aldehyde into a ketone is a notorious transformation, due to the laborious challenge of the formation of ketyl or acyl radicals. Herein, we report a green, cheap, metal‐free and efficient method for the hydroacylation of olefins in water. This photochemical protocol utilizes phenylglyoxylic acid, a commercially available small organic molecule, as the photoinitiator, water as the solvent and household fluorescent lamps as the irradiation source, leading to a broad substrate scope of products in moderate to good yields. A wide range of aromatic and aliphatic aldehydes, terminal and non‐terminal alkenes and pharmaceutically relevant molecules can be employed, without the need of directing groups and additives or metal catalysts.

Structure and Properties of Violet Phosphorus and Its Phosphorene Exfoliation

By Lihui Zhang, Hongyang Huang, Bo Zhang, Mengyue Gu, Dan Zhao, Xuewen Zhao, Longren Li, Jun Zhou, Kai Wu, Yonghong Cheng, Jinying Zhang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 06, 2019.

Violet phosphorus single crystals and violet phosphorene have been synthesized. The structure was determined by single‐crystal X‐ray diffraction and observed by HRTEM. Violet phosphorus is more stable than black phosphorus. Violet phosphorene was obtained by mechanical and solvent exfoliation under ambient conditions. Abstract Black phosphorene has attracted much attention as a semiconducting two‐dimensional material. Violet phosphorus is another layered semiconducting phosphorus allotrope with unique electronic and optoelectronic properties. However, no confirmed violet crystals or reliable lattice structure of violet phosphorus had been obtained. Now, violet phosphorus single crystals were produced and the lattice structure has been obtained by single‐crystal x‐ray diffraction to be monoclinic with space group of P2/n (13) (a=9.210, b=9.128, c=21.893 Å, β=97.776°). The lattice structure obtained was confirmed to be reliable and stable. The optical band gap of violet phosphorus is around 1.7 eV, which is slightly larger than the calculated value. The thermal decomposition temperature was 52 °C higher than its black phosphorus counterpart, which was assumed to be the most stable form. Violet phosphorene was easily obtained by both mechanical and solution exfoliation under ambient conditions.

An Ultrasound Activated Vesicle of Janus Au‐MnO Nanoparticles for Promoted Tumor Penetration and Sono‐Chemodynamic Therapy of Orthotopic Liver Cancer

By Xiahui Lin, Shuya Liu, Xuan Zhang, Rong Zhu, Shan Chen, Xiaoyuan Chen, Jibin Song, Huanghao Yang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 06, 2019.

A smart self‐assembled US/GSH dual‐responsive nanovesicle was synthesized by self‐assembly of Janus Au‐MnO NP. It could be consecutively disassembled into the small Janus Au‐MnO NPs and smaller Au NPs and Mn2+ for dual MRI/PAI‐guided synergistic sono‐chemodynamic therapy. Abstract Sonodynamic therapy (SDT) has the advantages of high penetration, non‐invasiveness, and controllability, and it is suitable for deep‐seated tumors. However, there is still a lack of effective sonosensitizers with high sensitivity, safety, and penetration. Now, ultrasound (US) and glutathione (GSH) dual responsive vesicles of Janus Au‐MnO nanoparticles (JNPs) were coated with PEG and a ROS‐sensitive polymer. Upon US irradiation, the vesicles were disassembled into small Janus Au‐MnO nanoparticles (NPs) with promoted penetration ability. Subsequently, GSH‐triggered MnO degradation simultaneously released smaller Au NPs as numerous cavitation nucleation sites and Mn2+ for chemodynamic therapy (CDT), resulting in enhanced reactive oxygen species (ROS) generation. This also allowed dual‐modality photoacoustic imaging in the second near‐infrared (NIR) window and T1‐MR imaging due to the released Mn2+, and inhibited orthotopic liver tumor growth via synergistic SDT/CDT.

f‐Element Half‐Sandwich Complexes: A Tetrasilylcyclobutadienyl–Uranium(IV)–Tris(tetrahydroborate) Anion Pianostool Complex

By Josef T. Boronski, Laurence R. Doyle, John A. Seed, Ashley J. Wooles, Stephen T. Liddle from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 06, 2019.

Pianostool: The first example of an f‐element half‐sandwich cyclobutadienyl complex, which is only the second example of an actinide–cyclobutadienyl complex, is reported. Calculations suggest that U−C π‐bonding dominates, with no δ‐bonding component. Abstract Despite there being numerous examples of f‐element compounds supported by cyclopentadienyl, arene, cycloheptatrienyl, and cyclooctatetraenyl ligands (C5–8), cyclobutadienyl (C4) complexes remain exceedingly rare. Here, we report that reaction of [Li2{C4(SiMe3)4}(THF)2] (1) with [U(BH4)3(THF)2] (2) gives the pianostool complex [U{C4(SiMe3)4}(BH4)3][Li(THF)4] (3), where use of a borohydride and preformed C4‐unit circumvents difficulties in product isolation and closing a C4‐ring at uranium. Complex 3 is an unprecedented example of an f‐element half‐sandwich cyclobutadienyl complex, and it is only the second example of an actinide‐cyclobutadienyl complex, the other being an inverse‐sandwich. The U−C distances are short (av. 2.513 Å), reflecting the formal 2− charge of the C4‐unit, and the SiMe3 groups are displaced from the C4‐plane, which we propose maximises U−C4 orbital overlap. DFT calculations identify two quasi‐degenerate U−C4 π‐bonds utilising the ψ2 and ψ3 molecular orbitals of the C4‐unit, but the potential δ‐bond using the ψ4 orbital is vacant.

Photoactivated Fluorescence Enhancement in F,N‐Doped Carbon Dots with Piezochromic Behavior

By Lei Jiang, Haizhen Ding, Siyu Lu, Ting Geng, Guanjun Xiao, Bo Zou, Hong Bi from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 06, 2019.

Photoactivated fluorescence enhancement in F and N co‐doped carbon dots is presented. The F,N‐doped CDs exhibit fluorescence enhancement when exposed to UV and reversible piezochromic behavior while applying increasing pressure (1.0 atm to 9.98 GPa), with pressure‐triggered aggregation‐induced emission in the range 1.0 atm–0.65 GPa. Abstract Photoactivation in CdSe/ZnS quantum dots (QDs) on UV/Vis light exposure improves photoluminescence (PL) and photostability. However, it was not observed in fluorescent carbon quantum dots (CDs). Now, photoactivated fluorescence enhancement in fluorine and nitrogen co‐doped carbon dots (F,N‐doped CDs) is presented. At 1.0 atm, the fluorescence intensity of F,N‐doped CDs increases with UV light irradiation (5 s–30 min), accompanied with a blue‐shift of the fluorescence emission from 586 nm to 550 nm. F,N‐doped CDs exhibit photoactivated fluorescence enhancement when exposed to UV under high pressure (0.1 GPa). F,N‐doped CDs show reversible piezochromic behavior while applying increasing pressure (1.0 atm to 9.98 GPa), showing a pressure‐triggered aggregation‐induced emission in the range 1.0 atm–0.65 GPa. The photoactivated CDs with piezochromic fluorescence enhancement broadens the versatility of CDs from ambient to high‐pressure conditions and enhances their anti‐photobleaching.

Selective and Wash‐Resistant Fluorescent Dihydrocodeinone‐Derivatives Allow Single‐Molecule Imaging of mu‐Opioid Receptor Dimerisation

By Christian Gentzsch, Kerstin Seier, Antonios Drakopoulos, Marie-Lise Jobin, Yann Lanoiselée, Zsombor Koszegi, Damien Maurel, Remy Sounier, Harald Hübner, Peter Gmeiner, Sebastien Granier, Davide Calebiro, Michael Decker from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 06, 2019.

mu‐Opioid receptors (mu‐ORs) play a critical role in the modulation of pain and mediate the effects of the most powerful analgesic drugs. Despite extensive efforts, it remains insufficiently understood how mu‐ORs produce specific effects in living cells. We developed new fluorescent ligands based on the mu‐OR antagonist E‐p‐nitrocinnamoylamino‐dihydrocodeinone (CACO), that display high affinity, long residence time and pronounced selectivity. Using these ligands, we achieved single‐molecule imaging of m‐ORs on the surface of living cells at physiological expression levels. Our results reveal a high heterogeneity in the diffusion of mu‐ORs, with a relevant immobile fraction. Using a pair of fluorescent ligands of different color, we provide evidence that mu‐ORs interact with each other to form short‐lived homodimers on the plasma membrane. This approach provides a new strategy to investigate mu‐OR pharmacology at single‐molecule level.

Elucidating the Electrocatalytic CO2 Reduction Reaction over a Model Single‐Atom Nickel Catalyst

By Song Liu, Hong Bin Yang, Sung‐Fu Hung, Jie Ding, Weizheng Cai, Linghui Liu, Jiajian Gao, Xuning Li, Xinyi Ren, Zhichong Kuang, Yanqiang Huang, Tao Zhang, Bin Liu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 06, 2019.

“If I had a nickel!” A model nickel single‐atom catalyst bearing uniform and well‐defined Ni‐N4 moieties was prepared by coordinating molecular nickel phthalocyanine to carbon nanotubes through C−C covalent bonds. In their Research Article (DOI: 10.1002/anie.201911995), Y. Huang and B. Liu et al. describe a highly active catalyst for electrochemical CO2 to CO reduction with a high Faradaic efficiency and turnover frequency. The active site is an in‐situ‐generated Ni+ species.

Carl Duisberg Plaque for Reinhard Zellner / Karl Wamsler Award for Wolfgang A. Herrmann / Primo Levi Award for Vincenzo Balzani

By from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 06, 2019.

Nanographenes: Ultrastable, Switchable, and Bright Probes for Super‐Resolution Microscopy

By Xiaomin Liu, Shih‐Ya Chen, Qiang Chen, Xuelin Yao, Márton Gelléri, Sandra Ritz, Sachin Kumar, Christoph Cremer, Katharina Landfester, Klaus Müllen, Sapun Parekh, Akimitsu Narita, Mischa Bonn from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 06, 2019.

Super‐resolution fluorescence microscopy has enabled important breakthroughs in biology and materials science. In their Research Article (DOI: 10.1002/anie.201909220), X. Liu, M. Bonn, and co‐workers introduce nanographenes as a new class of fluorophores for super‐resolution fluorescence microscopy. Nanographenes exhibit outstanding photophysical properties of high brightness, intrinsic blinking even in air, excellent fluorescence recovery, and stability over several months.

Author Correction: Ultrasoft slip-mediated bending in few-layer graphene

By Arend M. van der Zande from Nature Materials - Issue - nature.com science feeds. Published on Dec 06, 2019.

Nature Materials, Published online: 06 December 2019; doi:10.1038/s41563-019-0578-y

Author Correction: Ultrasoft slip-mediated bending in few-layer graphene

Extraordinary Chiral Exchange-Bias Phenomenon: Engineering the Sign of the Bias Field in Orthogonal Bilayers by a Magnetically Switchable Response Mechanism

By Julio Camarero from RSC - Nanoscale latest articles. Published on Dec 06, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR08852K, Paper
Alberto Bollero, Volker Neu, V. Baltz, David Serantes, José Luis F. Cuñado, Javier F. Pedrosa, Ester M. Palmero, Marietta Seifert, Bernard Dieny, Rafael Perez del Real, Manuel vazquez, Oksana Chubykalo-Fesenko, Julio Camarero
Isothermal tuning of both the magnitude and the sign of the bias field has been achieved by exploiting a new phenomenon in a system consisting of two orthogonally coupled films:...
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Hierarchical nanotwins in single-crystal-like Nickel with high strength and corrosion resistance produced via a hybrid technique

By Xinghang Zhang from RSC - Nanoscale latest articles. Published on Dec 06, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR07472D, Communication
Qiang Li, Sichuang Xue, Patrick Price, Xing Sun, Jie Ding, Zhongxia Shang, Zhe Fan, Han Wang, Yifan Zhang, Youxing Chen, Haiyan Wang, Khalid Hattar, Xinghang Zhang
High-density growth nanotwins enable high-strength and good ductility in metallic materials. However, twinning propensity is greatly reduced in metals with high stacking fault energy. Here we adopted a hybrid technique...
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Quantum dots embedded N-doped functionalized multiwall carbon nanotubes boost short-circuit current of Ru(II) based dye-sensitized solar cells

By Qun Yang from RSC - Nanoscale latest articles. Published on Dec 06, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR09227G, Paper
Muhammad Wasim Khan, Xueqin Zuo, Huaibao Tang, Khalid Mehmood Ur Rehman, Mingzai Wu, Guang Li, Qun Yang
Here, we report a zinc sulfide quantum dots ZnS (QDs) moored N-doped functionalized multiwall carbon nanotubes wrapped with reduced graphene oxide (rGO). The multiwall carbon nanotubes (MWCNTs) have a tangled...
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Novel synthesis of platinum complexes and their intracellular delivery to tumor cells by means of magnetic nanoparticles

By Teresa Pellegrino from RSC - Nanoscale latest articles. Published on Dec 06, 2019.

Nanoscale, 2019, Advance Article
DOI: 10.1039/C9NR07015J, Paper
Open Access Open Access
Alessandra Quarta, Manuel Amorín, María José Aldegunde, Laura Blasi, Andrea Ragusa, Simone Nitti, Giammarino Pugliese, Giuseppe Gigli, Juan R. Granja, Teresa Pellegrino
Platinum-based drugs are popular in clinics as chemotherapeutic agents to treat solid tumors.
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One-pot “shielding-to-etching” strategy to synthesize amorphous MoS2 modified CoS/Co0.85Se heterostructured nanotube arrays for boosted energy-saving H2 generation

By Yijun Zhong from RSC - Nanoscale latest articles. Published on Dec 06, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR08812A, Paper
Yong Hu, Yulin Sun, Saijun Wang, Jiqiang Ning, Ziyang Zhang, Yijun Zhong
In this study, a facile one-pot “shielding-to-etching” strategy has been designed for the synthesis of amorphous MoS2 modified CoS/Co0.85Se heterostructured nanotube arrays (a-MoS2/CoS/Co0.85Se HNTs) as a highly efficient electrocatalyst for...
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Polyornithine-based polyplexes to boost effective gene silencing in CNS disorders

By Maria Vicent from RSC - Nanoscale latest articles. Published on Dec 06, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR06187H, Paper
Inmaculada Conejos-Sanchez, Elena Gallon, Amaya Niño-Pariente, Jayden Smith, Alerie Guzmán De la Fuente, Ludovica Di Canio, Stefano Pluchino, Robin Franklin, Maria Vicent
Gene silencing therapies have successfully suppressed the translation of target proteins, a strategy that holds great promise for the treatment of central nervous system (CNS) disorders. Advances in the current...
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Efficient Electrocatalytic Conversion of N2 to NH3 on NiWO4 Under Ambient Condition

By Jaephil Cho from RSC - Nanoscale latest articles. Published on Dec 06, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR08777J, Paper
Jia Wang, Haeseong Jang, Guangkai Li, Zexing Wu, Min Gyu Kim, Xien Liu, Jaephil Cho
Developing highly efficient and inexpensive catalyst is still a tremendous challenge for electrocatalytic nitrogen reduction reaction (NRR) which is a promising alternative to high-temperature and high-pressure industrials technology for the...
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Recent Progress of TMD Nanomaterials: Phase Transitions and Applications

By Wei Tao Zheng from RSC - Nanoscale latest articles. Published on Dec 06, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR08313H, Review Article
H. H. Huang, Xiaofeng Fan, David J. Singh, Wei Tao Zheng
Transition metal dichalcogenides (TMDs) show wide ranges in electronic properties ranging from the semiconducting, semi-metallic to metallic due to their ingenious structural differences. To obtain 2D TMDs with specific properties,...
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The visible nonlinear optical properties and passively Q-switched laser application of layered PtSe2 material

By Han Zhang from RSC - Nanoscale latest articles. Published on Dec 06, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR08980B, Paper
Na Cui, Feng Zhang, Yuqing Zhao, Yongping Yao, Qiangguo Wang, Lulu Dong, Huiyun Zhang, Shande Liu, Jinlong Xu, Han Zhang
Platinum diselenide (PtSe2) grouped as the type-II Dirac semi-metal materials is a potential saturable absorber (SA) to generate visible pulsed laser, attributing to its prominently optoelectronic properties. The high quality...
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1% defect enriches MoS2 quantum dot: catalysis and blue luminescence

By Ken-ichi Saitow from RSC - Nanoscale latest articles. Published on Dec 06, 2019.

Nanoscale, 2020, Advance Article
DOI: 10.1039/C9NR07612C, Paper
Jingmin Tang, Masanori Sakamoto, Haruhisa Ohta, Ken-ichi Saitow
MoS2 quantum dot, given by laser ablation, have 1% sulfur vacancies quantified by ESR as a functional defect. Very good catalyst, the shortest synthesis time, and room-temperature process are achieved against the top 10 papers of the HER of MoS2.
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Platinum (IV) Derivatives with Cinnamate Axial Ligands Are Potent Agents Against Both Differentiated and Tumorigenic Cancer Stem Rhabdomyosarcoma Cells

By Juraj Zajac, Vojtech Novohradsky, Lenka Markova, Viktor Brabec, Jana Kasparkova from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 05, 2019.

To design a new anticancer drug capable of inhibiting not only the proliferation of the differentiated tumor cells but also reducing the tumorigenic capability of cancer stem cells (CSCs), the new Pt(IV) prodrugs with axial cinnamate ligands were synthesized. We demonstrate their superior antiproliferative activity in monolayer and 3D spheroid antiproliferative activity tests using panel of cancer cell lines. Interestingly, an outstanding activity was found against rhabdomyosarcoma cells, one of the most problematic and poorly treatable pediatric tumors. The results also suggest that Pt(II) moiety and cinnamic acid are released from the molecules of the investigated Pt(IV) prodrugs in cancer cells and are reduced by intracellular reductants. Whereas the released Pt(II) compound inhibits antiproliferative activity of cancer cells by DNA‐damage mediated mechanism, the released cinnamic acid can trigger processes leading to differentiation, making the CSCs more sensitive to killing by the platinum part of the complex. To the best of our knowledge, Pt(IV) complex with axial cinnamate ligands is the first Pt(IV) prodrug capable of overcoming CSCs resistance and induce death in both CSCs and bulk cancer.

Analysis of Powders Containing Illicit Drugs Using Magnetic Levitation

By Christoffer K. Abrahamsson, Amit Nagarkar, Michael J. Fink, Daniel J. Preston, Shencheng Ge, Joseph S. Bozenko, George M. Whitesides from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 05, 2019.

Magneto‐Archimedes levitation (MagLev) separates mixtures of powdered illicit drugs and facilitates density‐based presumptive identification of dilute drugs (1.3 wt % fentanyl in a mixture with heroin and lactose; see picture). Combined use of MagLev and FTIR enables confirmatory identification of illicit drugs. Abstract Magneto‐Archimedes levitation (MagLev) enables the separation of powdered mixtures of illicit drugs (cocaine, methamphetamine, heroin, fentanyl, and its analogues), adulterants, and diluents based on density, and allows the presumptive identification of individual components. Small samples (mass

On crucial roles of two hydrated Mg2+ ions in reaction catalysis of the pistol ribozyme

By Marianna Teplova, Christoph Falschlunger, Olga Krasheninina, Michaela Egger, Aiming Ren, Dinshaw J Patel, Ronald Micura from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 05, 2019.

Pistol ribozymes constitute a new class of small self‐cleaving RNAs. We have solved crystal structures that provide three‐dimensional snapshots along the reaction coordinate of pistol phosphodiester cleavage, corresponding to the pre‐catalytic state, a vanadate mimic of the transition state, and the product. The resulting architectonic framework dictates the proposed underlying chemical mechanism, which is corroborated by functional assays that involve atomic mutagenesis of the ribozyme. Importantly, a hydrated Mg2+ ion remains innersphere–coordinated to N7–G33 in all three states. This is consistent with its likely role as acid in general acid base catalysis (δ and ß catalysis), supported further by the observation of a more than 1000‐fold rate reduction if its positioning is impaired by deletion of the N7 site. Strikingly, the new structures shed light on a second hydrated Mg2+ ion that approaches the scissile phosphate from its binding site in the pre‐cleavage state to reach out for water‐mediated H‐bonding in the cyclophosphate product. Because this second hydrated Mg2+ ion is also close to the 6‐oxygen atom of G40 (general base, γ catalysis), its potential impact on activation of G40 has been experimentally evaluated, however, the major role of the second Mg2+ ion appears to be the stabilization of product conformation. Together, our study delivers a mechanistic understanding of ribozyme–catalyzed backbone cleavage with unprecedented precision.

Synthetic Photoelectrochemistry

By Joshua Philip Barham, Burkhard König from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 05, 2019.

Photoredox Catalysis (PRC) and Synthetic Organic Electrochemistry (SOE) are often considered competing technologies in organic synthesis and their fusion has been largely overlooked. We review state‐of‐the‐art synthetic organic photoelectrochemistry, grouping examples into three categories: 1) electrochemically‐mediated PhotoRedox Catalysis (e‐PRC), 2) decoupled PhotoElectrochemistry (dPEC) and 3) interfacial PhotoElectrochemistry (iPEC). Such synergies prove beneficial not only for synthetic ‘greenness’ and chemical selectivity, but also in the accumulation of energy for accessing super‐oxidizing or reducing single‐electron‐transfer (SET) agents. Opportunities and challenges in this emerging and exciting field are discussed.

Exfoliated CrPS4 with Promising Photoconductivity

By Adam K. Budniak, Niall A. Killilea, Szymon J. Zelewski, Mykhailo Sytnyk, Yaron Kauffmann, Yaron Amouyal, Robert Kudrawiec, Wolfgang Heiss, Efrat Lifshitz from Wiley: Small: Table of Contents. Published on Dec 05, 2019.

Chromium thiophosphate (CrPS4) synthesis, characterization, exfoliation, and application are presented. Spectroscopy means describe bulk CrPS4 as a direct semiconductor with 1.30 eV bandgap at room temperature. A simple protocol for mechanical exfoliation directly onto electron microscopy grids is developed, then atomic resolution elemental maps are recorded. Liquid exfoliation of CrPS4 and converting suspension into an ink allows for the development of an all‐printed photodetector. Abstract Layered semiconductors have attracted significant attention due to their diverse physical properties controlled by composition and the number of stacked layers. Herein, large crystals of the ternary layered semiconductor chromium thiophosphate (CrPS4) are prepared by a vapor transport synthesis. Optical properties are determined using photoconduction, absorption, photoreflectance, and photoacoustic spectroscopy exposing the semiconducting properties of the material. A simple, one‐step protocol for mechanical exfoliation onto a transmission electron microscope grid is developed, and multiple layers are characterized by advanced electron microscopy methods, including atomic resolution elemental mapping confirming the structure by directly showing the positions of the columns of different elements' atoms. CrPS4 is also liquid exfoliated, and in combination with colloidal graphene, an ink‐jet‐printed photodetector is created. This all‐printed graphene/CrPS4/graphene heterostructure detector demonstrates a specific detectivity of 8.3 × 108 (D*). This study shows a potential application of both bulk crystal and individual flakes of CrPS4 as active components in light detection, when introduced as ink‐printable moieties with a large benefit for manufacturing.

Cellulose‐Based Microparticles for Magnetically Controlled Optical Modulation and Sensing

By Michael K. Hausmann, Alina Hauser, Gilberto Siqueira, Rafael Libanori, Signe Lin Vehusheia, Simone Schuerle, Tanja Zimmermann, André R. Studart from Wiley: Small: Table of Contents. Published on Dec 05, 2019.

Cellulose‐laden microparticles that enable light manipulation using an external magnetic field are generated in a microfluidic platform. Such a magneto‐optical coupling effect is achieved by combining superparamagnetic nanoparticles and oriented birefringent cellulose nanocrystals within the anisotropic microparticles. When suspended in a liquid medium, these functional microparticles can be exploited to locally probe the viscosity of fluids or to create color‐changing materials. Abstract Responsive materials with birefringent optical properties have been exploited for the manipulation of light in several modern electronic devices. While electrical fields are often utilized to achieve optical modulation, magnetic stimuli may offer an enticing complementary approach for controlling and manipulating light remotely. Here, the synthesis and characterization of magnetically responsive birefringent microparticles with unusual magneto‐optical properties are reported. These functional microparticles are prepared via a microfluidic emulsification process, in which water‐based droplets are generated in a flow‐focusing device and stretched into anisotropic shapes before conversion into particles via photopolymerization. Birefringence properties are achieved by aligning cellulose nanocrystals within the microparticles during droplet stretching, whereas magnetic responsiveness results from the addition of superparamagnetic nanoparticles to the initial droplet template. When suspended in a fluid, the microparticles can be controllably manipulated via an external magnetic field to result in unique magneto‐optical coupling effects. Using a remotely actuated magnetic field coupled to a polarized optical microscope, these microparticles can be employed to convert magnetic into optical signals or to estimate the viscosity of the suspending fluid through magnetically driven microrheology.

Light‐Powered Directional Nanofluidic Ion Transport in Kirigami‐Made Asymmetric Photonic‐Ionic Devices

By Meijuan Jia, Xian Kong, Lili Wang, Yanbing Zhang, Di Quan, Liping Ding, Diannan Lu, Lei Jiang, Wei Guo from Wiley: Small: Table of Contents. Published on Dec 05, 2019.

Kirigami‐made asymmetric 2D nanofluidic devices show directional ion transport properties upon full‐area light illumination. This transport phenomenon unveils a new driving mechanism that the enhanced carrier recombination rate at the membrane boundary breaks the symmetry in the transport direction, and thus drives the ion transport under symmetric light illumination. Abstract Nacre‐mimetic 2D nanofluidic materials with densely packed sub‐nanometer‐height lamellar channels find widespread applications in water‐, energy‐, and environment‐related aspects by virtue of their scalable fabrication methods and exceptional transport properties. Recently, light‐powered nanofluidic ion transport in synthetic materials gained considerable attention for its remote, noninvasive, and active control of the membrane transport property using the energy of light. Toward practical application, a critical challenge is to overcome the dependence on inhomogeneous or site‐specific light illumination. Here, asymmetric photonic‐ionic devices based on kirigami‐tailored graphene oxide paper are fabricated, and directional nanofluidic ion transport properties therein powered by full‐area light illumination are demonstrated. The in‐plane asymmetry of the graphene oxide paper is essential to the generation of photoelectric driving force under homogeneous illumination. This light‐powered ion transport phenomenon is explained based on a modified carrier diffusion model. In asymmetric nanofluidic structures, enhanced recombination of photoexcited charge carriers at the membrane boundary breaks the electric potential balance in the horizontal direction, and thus drives the ion transport in that direction under symmetric illumination. The kirigami‐based strategy provides a facile and scalable way to fabricate paper‐like photonic‐ionic devices with arbitrary shapes, working as fundamental elements for large‐scale light‐harvesting nanofluidic circuits.

Biodegradable Bi2O2Se Quantum Dots for Photoacoustic Imaging‐Guided Cancer Photothermal Therapy

By Hanhan Xie, Mingqiang Liu, Baihao You, Guanghong Luo, Yue Chen, Bilu Liu, Zhenyou Jiang, Paul K. Chu, Jundong Shao, Xue‐Feng Yu from Wiley: Small: Table of Contents. Published on Dec 05, 2019.

2D Bi2O2Se quantum dots (QDs) are synthesized by a facile top‐down approach. Boasting large photothermal conversion efficiency and excellent photoacoustic performance as well as suitable biodegradability, the Bi2O2Se QDs facilitate photoacoustic imaging of the entire tumors in photothermal cancer therapy. The semiconducting QDs are promising as a near‐infrared‐triggered theranostic agent in cancer therapy. Abstract As new 2D layered nanomaterials, Bi2O2Se nanoplates have unique semiconducting properties that can benefit biomedical applications. Herein, a facile top‐down approach for the synthesis of Bi2O2Se quantum dots (QDs) in a solution is described. The Bi2O2Se QDs with a size of 3.8 nm and thickness of 1.9 nm exhibit a high photothermal conversion coefficient of 35.7% and good photothermal stability. In vitro and in vivo assessments demonstrate that the Bi2O2Se QDs possess excellent photoacoustic (PA) performance and photothermal therapy (PTT) efficiency. After systemic administration, the Bi2O2Se QDs accumulate passively in tumors enabling efficient PA imaging of the entire tumors to facilitate imaging‐guided PTT without obvious toxicity. Furthermore, the Bi2O2Se QDs which exhibit degradability in aqueous media not only have sufficient stability during in vivo circulation to perform the designed therapeutic functions, but also can be discharged harmlessly from the body afterward. The results reveal the great potential of Bi2O2Se QDs as a biodegradable multifunctional agent in medical applications.

Deciphering an Abnormal Layered‐Tunnel Heterostructure Induced by Chemical Substitution for the Sodium Oxide Cathode

By Yao Xiao, Yan‐Fang Zhu, Wei Xiang, Zhen‐Guo Wu, Yong‐Chun Li, Jing Lai, Shi Li, Enhui Wang, Zu‐Guang Yang, Chun‐Liu Xu, Ben‐He Zhong, Xiao‐Dong Guo from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 05, 2019.

An abnormal layered‐tunnel heterostructure Na0.44Co0.1Mn0.9O2 cathode material induced by chemical element substitution is described. The crystal‐structure engineering strategy that was used gives an outlook into high‐performance sodium ion batteries. Abstract Demands for large‐scale energy storage systems have driven the development of layered transition‐metal oxide cathodes for room‐temperature rechargeable sodium ion batteries (SIBs). Now, an abnormal layered‐tunnel heterostructure Na0.44Co0.1Mn0.9O2 cathode material induced by chemical element substitution is reported. By virtue of beneficial synergistic effects, this layered‐tunnel electrode shows outstanding electrochemical performance in sodium half‐cell system and excellent compatibility with hard carbon anode in sodium full‐cell system. The underlying formation process, charge compensation mechanism, phase transition, and sodium‐ion storage electrochemistry are clearly articulated and confirmed through combined analyses of in situ high‐energy X‐ray diffraction and ex situ X‐ray absorption spectroscopy as well as operando X‐ray diffraction. This crystal structure engineering regulation strategy offers a future outlook into advanced cathode materials for SIBs.

Carbon Dots with Dual‐Emissive, Robust, and Aggregation‐Induced Room‐Temperature Phosphorescence Characteristics

By Kai Jiang, Xiaolu Gao, Xiangyu Feng, Yuhui Wang, Zhongjun Li, Hengwei Lin from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 05, 2019.

Carbon dots (CDs) with dual‐emissive, robust, and aggregation‐induced room‐temperature phosphorescence (RTP) characteristics are reported. Potential applications of the as‐prepared CDs in advanced anti‐counterfeit and information encryption are also demonstrated. Abstract Carbon dots (CDs) with dual‐emissive, robust, and aggregation‐induced RTP characteristics are reported for the first time. The TA‐CDs are prepared via hydrothermal treatment of trimellitic acid and exhibit unique white prompt and yellow RTP emissions in solid state under UV excitation (365 nm) on and off, respectively. The yellow RTP emission of TA‐CDs powder should be resulted from the formation of a new excited triplet state due to their aggregation, and the white prompt emission is due to their blue fluorescence and yellow RTP dual‐emissive nature. The RTP emission of TA‐CDs powder was highly stable under grinding, which is very rare amongst traditional pure organic RTP materials. To employ the unique characteristics of TA‐CDs, advanced anti‐counterfeiting and information encryption methodologies (water‐stimuli‐response producing RTP) were preliminarily investigated.

Radical Acylfluoroalkylation of Olefins through N‐Heterocyclic Carbene Organocatalysis

By Jun‐Long Li, Yan‐Qing Liu, Wen‐Lin Zou, Rong Zeng, Xiang Zhang, Yue Liu, Bo Han, Yu He, Hai‐Jun Leng, Qing‐Zhu Li from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 05, 2019.

Organocatalytic acylfluoroalkylation: A multicomponent radical acylfluoroalkylation of olefins through NHC organocatalysis was developed, and over 120 examples of fluoroketones were facilely accessed from simple materials. Moreover, a dearomative difunctionalization of indoles could be readily achieved in a highly diastereoselective manner. The generality and practicality were highlighted by the late‐stage modification of drug skeletons. Abstract Fluorinated ketones are widely prevalent in numerous biologically interesting molecules, and the development of novel transformations to access these structures is an important task in organic synthesis. Herein, we report the multicomponent radical acylfluoroalkylation of a variety of olefins in the presence of various commercially available aromatic aldehydes and fluoroalkyl reagents through N‐heterocyclic carbene organocatalysis. With this protocol, over 120 examples of functionalized ketones with diverse fluorine substituents have been synthesized in up to 99 % yield with complete regioselectivity. The generality of this catalytic strategy was further highlighted by its successful application in the late‐stage functionalization of pharmaceutical skeletons. Excellent diastereoselectivity could be achieved in the reactions forging multiple stereocenters. In addition, preliminary results have been achieved on the catalytic asymmetric variant of the olefin difunctionalization process.

Direct Catalytic Decarboxylative Amination of Aryl Acetic Acids

By Duanyang Kong, Patrick J. Moon, Odey Bsharat, Rylan J. Lundgren from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 05, 2019.

The direct, chemoselective amination of aryl acetic acids is reported. The process enables late‐stage alkylation of drug targets without interference from other protic groups or electrophiles. Mechanistic studies support the generation of a benzylic nucleophile which is aminated in a Chan–Lam‐type redox pathway. Abstract The decarboxylative coupling of a carboxylic acid with an amine nucleophile provides an alternative to the substitution of traditional organohalide coupling partners. Benzoic and alkynyl acids may be directly aminated by oxidative catalysis. In contrast, methods for intermolecular alkyl carboxylic acid to amine conversion, including amidate rearrangements and photoredox‐promoted approaches, require stoichiometric activation of the acid unit to generate isocyanate or radical intermediates. Reported here is a process for the direct chemoselective decarboxylative amination of electron‐poor arylacetates by oxidative Cu catalysis. The reaction proceeds at (or near) room temperature, uses native carboxylic acid starting materials, and is compatible with protic, electrophilic, and other potentially complicating functionality. Mechanistic studies support a pathway in which ionic decarboxylation of the acid generates a benzylic nucleophile which is aminated in a Chan–Evans–Lam‐type process.

Gold(III) π‐Allyl Complexes

By Jessica Rodriguez, György Szalóki, E. Daiann Sosa Carrizo, Nathalie Saffon‐Merceron, Karinne Miqueu, Didier Bourissou from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 05, 2019.

Go for gold: The π coordination of allyl moieties to (P,C) coordinated gold(III) has been authenticated and shown to promote nucleophilic addition. Spectroscopic and crystallographic analyses combined with detailed DFT calculations support tight quasi‐symmetric η3‐coordination of the allyl moiety. Abstract Gold(III) π‐complexes have been authenticated recently with alkenes, alkynes, and arenes. The key importance of PdII π‐allyl complexes in organometallic chemistry (Tsuji–Trost reaction) prompted us to explore gold(III) π‐allyl complexes, which have remained elusive so far. The (P,C)AuIII(allyl) and (methallyl) complexes 3 and 3′ were readily prepared and isolated as thermally and air‐stable solids. Spectroscopic and crystallographic analyses combined with detailed DFT calculations support tight quasi‐symmetric η3‐coordination of the allyl moiety. The π‐allyl gold(III) complexes are activated towards nucleophilic additions, as substantiated with β‐diketo enolates.

Fabrication and Mechanical Properties of Engineered Protein‐Based Adhesives and Fibers

By Jing Sun, Juanjuan Su, Chao Ma, Robert Göstl, Andreas Herrmann, Kai Liu, Hongjie Zhang from Wiley: Advanced Materials: Table of Contents. Published on Dec 05, 2019.

Recent progress on the design and mechanical investigation of engineered protein‐based biomaterials is reviewed. As the two representative examples, the main discussion is of proteinaceous adhesives and fibers. The hierarchical structures of proteins have a great influence on the mechanical properties of relevant biomaterials. Perspectives and challenges in the field of functional proteins are also presented. Abstract Protein‐based structural biomaterials are of great interest for various applications because the sequence flexibility within the proteins may result in their improved mechanical and structural integrity and tunability. As the two representative examples, protein‐based adhesives and fibers have attracted tremendous attention. The typical protein adhesives, which are secreted by mussels, sandcastle worms, barnacles, and caddisfly larvae, exhibit robust underwater adhesion performance. In order to mimic the adhesion performance of these marine organisms, two main biological adhesives are presented, including genetically engineered protein‐based adhesives and biomimetic chemically synthetized adhesives. Moreover, various protein‐based fibers inspired by spider and silkworm proteins, collagen, elastin, and resilin are studied extensively. The achievements in synthesis and fabrication of structural biomaterials by DNA recombinant technology and chemical regeneration certainly will accelerate the explorations and applications of protein‐based adhesives and fibers in wound healing, tissue regeneration, drug delivery, biosensors, and other high‐tech applications. However, the mechanical properties of the biological structural materials still do not match those of natural systems. More efforts need to be devoted to the study of the interplay of the protein structure, cohesion and adhesion effects, fiber processing, and mechanical performance.

Atomistic simulations of COSAN: amphiphiles without a Head‐and‐Tail design have a “head and tail” surfactant behavior

By David C Malaspina, Clara Viñas, Francesc Teixidor, Jordi Faraudo from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 05, 2019.

Cobaltabisdicarbollide  (COSAN) anions have an unexpectedly rich self‐assembly behavior, being able to lead to vesicles and micelles without having a classical surfactant molecular architecture. New terms such as theta‐shaped amphiphile, stealth amphiphile or intrinsic amphiphile have been coined to describe this molecule and new driving forces such as the “chaotropic effect” were invoked to understand its novel features. A key aspect in these interpretations of COSAN behavior is the assumption that the most stable form of these ions is the transoid rotamer which lacks a “hydrophilic head” and a “hydrophobic tail”. Using implicit solvent DFT calculations here we show that in water, the cisoid rotamer (which has a polar and an apolar region) is the most stable form of COSAN. Our MD simulations in water show that this cisoid rotamer has a well‐defined hydrophilic polar “head” and a hydrophobic apolar “tail”. In addition, our simulations show that the properties of this rotamer in water (interfacial affinity, micellization) match with those expected for a classical surfactant. Therefore, we conclude that the experimental results for the COSAN ions can be now understood in terms of its amphiphilic molecular architecture.

Diselenide‐Pemetrexed Assemblies for Combined Cancer Immuno‐, Radio‐, and Chemotherapies

By Tianyu Li, Shuojiong Pan, Shiqian Gao, Wentian Xiang, Chenxing Sun, Wei Cao, Huaping Xu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 05, 2019.

Immunotherapy has emerged as a promising new approach for cancer treatment. However, clinically available drugs have been limited until recently, and the antitumor efficacy of most cancer immunotherapies still needs to be improved. Herein, we develop diselenide‐pemetrexed assemblies that combine nature killer (NK) cell‐based cancer immunotherapy with radiotherapy and chemotherapy in a single system. The assemblies are prepared via co‐assembly between pemetrexed and cytosine‐containing diselenide through hydrogen bonds. Under γ‐radiation, the hydrogen bonds are cleaved, resulting in the release of pemetrexed. At the same time, diselenide can be oxidized to seleninic acid, which suppresses the expression of human leukocyte antigen E (HLA‐E) in cancer cells, thus activating the immune response of NK cells. In this way, cancer immunotherapy is combined with radiotherapy and chemotherapy, which reveals a new strategy for combination therapy in cancer treatment.

Structure‐Independent Conductance of Thiophene‐Based Single‐Stacking Junctions

By Wenjing Hong, Xiaohui Li, Qingqing Wu, Jie Bai, Songjun Hou, Wenlin Jiang, Chun Tang, Hang Song, Xiaojuan Huang, Jueting Zheng, Yang Yang, Junyang Liu, Yong Hu, Jia Shi, Zitong Liu, Colin J. Lambert, Deqing Zhang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 05, 2019.

Intermolecular charge transport is crucial in π‐conjugated materials but the experimental investigation remained challenging. Here, we show that charge transport through intermolecular and intramolecular paths in single‐molecule and single‐stacking thiophene junctions could be investigated using the mechanically controllable break junction (MCBJ) technique. We found that intermolecular charge transport ability through different single‐stacking junctions is approximately independent of molecular structures, which contrasts with the strong length dependence of conductance in single‐molecule junctions with the same building blocks, and the dominant charge transport path of molecules with two anchors transits from intramolecular to intermolecular paths when the conjugation pattern increased. The increase of conjugation further leads to higher binding probabilities due to the variation in binding energies supported by density functional theory (DFT) calculations. Our results demonstrate that intermolecular charge transport is not only the limiting step but also provides the efficient and dominate charge transport path at the single‐molecule scale.

A Case for Bond‐Network Analysis in Bridged Polycyclic Complex Molecule Synthesis: Hetidine and Hetisine Diterpenoid Alkaloids

By Nicolle A. Doering, Richmond Sarpong, Reinhard Walther Hoffmann from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 05, 2019.

A key challenge in the synthesis of diterpenoid alkaloids lies in identifying strategies that rapidly construct their multiply‐bridged polycyclic skeletons. Existing approaches to these structurally intricate secondary metabolites are discussed in the context of a ‘bond‐network analysis’ of molecular frameworks, which was originally devised by Corey some forty years ago. The retrosynthesis plans that emerge from a topological analysis of the highly bridged frameworks of the diterpenoid alkaloids are discussed in the context of eight recent syntheses of hetidine and hetisine natural products and their derivatives. This review highlights the extent to which network analyses of the type described here suffice for designing synthesis plans, as well as areas where they had to be amalgamated with functional group oriented synthetic planning considerations.

Ge=B π‐bonding: Synthesis and Reversible [2+2] Cycloaddition of Germaborenes

By Dominik Raiser, Christian Patrick Sindlinger, Hartmut Schubert, Lars Wesemann from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 05, 2019.

Phosphine stabilized germaborenes featuring an unprecedented Ge=B double bond with short B···Ge contacts of 1.886(2) (4) and 1.895(3) Å (5) were synthesized starting from an intramolecular germylene‐phosphine Lewis pair (1). After oxidative addition of borontrihalides BX3 (X = Cl, Br) the addition products were reduced with magnesium and catalytic amounts of anthracene to give the borylene derivatives in a yield of 78% (4) and 57% (5). These halide substituted germaborenes were characterized by single crystal structure analyses and the electronic structures were studied by quantum chemical calculations. Deduced from NBO NRT analysis the dominating Lewis‐structure contains a Ge=B double bond. The germaborenes exhibit at room temperature a reversible photochemically initiated [2+2] cycloaddition with a phenyl moiety of a terphenyl substituent, forming a complex heterocyclic structure with Ge(IV) in a strongly distorted coordination environment.

Stereoselective Syntheses, Structures and Properties of Extremely Distorted Chiral Nanographenes Embedding Hextuple Helicenes

By Myriam Roy, Veronika Berezhnaia, Marco Villa, Nicolas Vanthuyne, Michel Giorgi, Jean-Valère Naubron, Salomé Poyer, Valérie Monnier, Laurence Charles, Yannick Carissan, Denis Hagebaum-Reignier, Jean Rodriguez, Marc Gingras, Yoann Coquerel from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 05, 2019.

We report a molecular design and concept using pi‐system elongation and steric effects from helicenes surrounding a triphenylene core toward stable chiral polycyclic aromatic hydrocarbons (PAHs) with a maximal pi‐distortion to tackle their aromaticity, supramolecular and molecular properties. The selective syntheses, and the structural, conformational and chiroptical properties of two diastereomeric large multiple helicenes of formula C90H48 having a triphenylene core and embedding three [5]helicene units on their inner edges and three [7]helicene units at their periphery are reported based on diastereoselective and, when applicable, enantiospecific (!) Yamamoto‐type cyclotrimerizations of racemic or enantiopure 9,10‐dibromo[7]helicene. Both molecules have an extremely distorted triphenylene core, and one of them exhibits the largest torsion angle recorded so far for a benzene ring (twist = 36.9º). The analysis of aromaticity distribution in these model molecules using magnetic criteria revealed a non‐aromatic character of their triphenylene cores and provides a new look at aromaticity in three‐dimensional PAHs. One diastereomer can complex up to three silver(I) ions in the bay region (cavities) of its peripheral [7]helicene units, opening the door to chiral cationic metal‐nanographene hybrids.

Crystal‐to‐crystal synthesis of helically ordered polymers of trehalose via topochemical polymerization

By Kana M Sureshan, Kuntrapakam Hema, Rajesh G Gonnade from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 05, 2019.

We describe the synthesis of crystalline helical polymers of trehalose viatopochemical azide‐alkyne cycloaddition (TAAC) of a trehalose‐based monomer. An unsymmetrical trehalose derivative having azide and alkyne crystallizes in two different forms having almost similar packing; Form I, from ethyl acetate/n‐hexane and form II, from chloroform/n‐hexane. In form I, the alkyne group is disordered over two distant positions; Aand B. When the alkyne is at position B, molecules form a head‐to‐tail arrangement with an orientation suitable for their TAAC reaction to yield the polymer. However, in form II the chloroform molecules occupy the position B and thus block the reactive orientation. Upon heating, both the crystals undergo TAAC reaction to form crystalline polymers.Various studies revealed that form II releases the chloroform molecules upon heating, which makes the position Baccessible for the alkyne and thus to react. Powder X‐ray diffraction (PXRD) studies revealed that the monomers in both the crystals polymerize in a crystal‐to‐crystal fashion and Circular Dichroism (CD) studies of the product crystals revealed that the formed polymer is helically ordered. This solvent‐free, catalyst‐free polymerization method that eliminates the tedious purification of the polymeric product exemplifies the advantage of topochemical polymerization reaction over traditional solution‐phase polymerization.

Endogenous Nanoparticles Strain Perovskite Host Lattice Providing Oxygen Capacity and Driving Oxygen Exchange and CH4 Conversion to Syngas

By Kalliopi Kousi, Dragos Neagu, Leonidas Bekris, Evangelos Papaioannou, Ian Saxley Metcalfe from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 05, 2019.

Particles dispersed on the surface of oxide supports have enabled a wealth of applications in electro‐ photo‐ and heterogeneous catalysis. Dispersing nanoparticles within the bulk of oxides is, however, synthetically much more challenging and therefore less explored, but could open new dimensions to control material properties analogous to substitutional doping of ions in crystal lattices. Here we demonstrate such a concept allowing extensive, controlled growth of metallic nanoparticles, at nanoscale proximity, within a perovskite oxide lattice as well as on its surface. By employing operando techniques, we show that in the emergent nanostructure, the endogenous nanoparticles and the perovskite lattice become reciprocally strained and seamlessly connected, enabling enhanced oxygen exchange. Additionally, even deeply embedded nanoparticles can reversibly exchange oxygen with a methane stream, driving its redox conversion to syngas with remarkable selectivity and long term cyclability while surface particles are present. These results not only exemplify the means to create extensive, self‐strained nanoarchitectures with enhanced oxygen transport and storage capabilities, but also demonstrate that deeply submerged, redox‐active nanoparticles could be entirely accessible to reaction environments, driving redox transformations and thus offering intriguing new alternatives to design materials underpinning several energy conversion technologies.

Synthesis of Cu‐Substituted CoS2@CuxS Double‐Shelled Nanoboxes via Sequential Ion Exchange for Efficient Sodium Storage

By Xiong-Wen (David) Lou from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 05, 2019.

Construction of hybrid architectures for electrode materials has been demonstrated as an efficient strategy to boost the sodium storage properties because of the synergetic effect from each component. However, the fabrication of hybrid nanostructures with rational structure and desired composition for decent sodium storage is still challenging. Herein, an integrated nanostructure composed of Cu‐substituted CoS 2 @Cu x S double‐shelled nanoboxes (denoted as Cu‐CoS 2 @Cu x S DSNBs) is synthesized through a rational metal‐organic framework (MOF)‐based templating strategy. The unique shell configuration and complex composition endow the Cu‐CoS 2 @Cu x S DSNBs electrode with enhanced electrochemical performance in terms of superior rate capability and stable cyclability.

Thu 23 Jan 14:00: How epithelial cells polarise and why this goes wrong in cancer Host: Hansong Ma

From All Talks (aka the CURE list). Published on Dec 05, 2019.

How epithelial cells polarise and why this goes wrong in cancer

Abstract not available

Host: Hansong Ma

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Thu 10 Dec 13:00: Title to be confirmed

From All Talks (aka the CURE list). Published on Dec 05, 2019.

Title to be confirmed

Abstract not available

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3D‐Printed Scanning‐Probe Microscopes with Integrated Optical Actuation and Read‐Out

By Philipp‐Immanuel Dietrich, Gerald Göring, Mareike Trappen, Matthias Blaicher, Wolfgang Freude, Thomas Schimmel, Hendrik Hölscher, Christian Koos from Wiley: Small: Table of Contents. Published on Dec 05, 2019.

3D‐printed scanning‐probe microscopy (SPM) engines offer a tremendous freedom of design allowing the integration of several measurement principles in one monolithic structure, which includes excitation and read‐out already. Atomic force microscopy with atomic‐scale step‐height resolution as well as scanning near‐field optical microscopy characterizing active and passive optical elements is demonstrated. Wafer‐level fabrication of massively SPM arrays is possible. Abstract Scanning‐probe microscopy (SPM) is the method of choice for high‐resolution imaging of surfaces in science and industry. However, SPM systems are still considered as rather complex and costly scientific instruments, realized by delicate combinations of microscopic cantilevers, nanoscopic tips, and macroscopic read‐out units that require high‐precision alignment prior to use. This study introduces a concept of ultra‐compact SPM engines that combine cantilevers, tips, and a wide variety of actuator and read‐out elements into one single monolithic structure. The devices are fabricated by multiphoton laser lithography as it is a particularly flexible and accurate additive nanofabrication technique. The resulting SPM engines are operated by optical actuation and read‐out without manual alignment of individual components. The viability of the concept is demonstrated in a series of experiments that range from atomic‐force microscopy engines offering atomic step height resolution, their operation in fluids, and to 3D printed scanning near‐field optical microscopy. The presented approach is amenable to wafer‐scale mass fabrication of SPM arrays and capable to unlock a wide range of novel applications that are inaccessible by current approaches to build SPMs.

An Artificial Somatic Reflex Arc

By Ke He, Yaqing Liu, Ming Wang, Geng Chen, Ying Jiang, Jiancan Yu, Changjin Wan, Dianpeng Qi, Meng Xiao, Wan Ru Leow, Hui Yang, Markus Antonietti, Xiaodong Chen from Wiley: Advanced Materials: Table of Contents. Published on Dec 05, 2019.

An artificial somatic reflex arc that enables the actuation of electrochemical actuators in response to tactile stimulations is presented. The pressure sensor perceives the pressure only if the sensed pressure is above the threshold, and the threshold controlling unit can be activated and triggers the actuators to complete the reflex actions, which mimics the all‐or‐none response. Abstract The emulation of human sensation, perception, and action processes has become a major challenge for bioinspired intelligent robotics, interactive human–machine interfacing, and advanced prosthetics. Reflex actions, enabled through reflex arcs, are important for human and higher animals to respond to stimuli from environment without the brain processing and survive the risks of nature. An artificial reflex arc system that emulates the functions of the reflex arc simplifies the complex circuit design needed for “central‐control‐only” processes and becomes a basic electronic component in an intelligent soft robotics system. An artificial somatic reflex arc that enables the actuation of electrochemical actuators in response to the stimulation of tactile pressures is reported. Only if the detected pressure by the pressure sensor is above the stimulus threshold, the metal–organic‐framework‐based threshold controlling unit (TCU) can be activated and triggers the electrochemical actuators to complete the motion. Such responding mechanism mimics the all‐or‐none law in the human nervous system. As a proof of concept, the artificial somatic reflex arc is successfully integrated into a robot to mimic the infant grasp reflex. This work provides a unique and simplifying strategy for developing intelligent soft robotics, next‐generation human–machine interfaces, and neuroprosthetics.

BowtieArene: A Dual Macrocycle Exhibiting Stimuli‐Responsive Fluorescence

By Sheng-Nan Lei, Hongyan Xiao, Yi Zeng, Chen-Ho Tung, Li-Zhu Wu, Huan Cong from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 05, 2019.

Although being highly useful in supramolecular chemistry, pillararenes lack fluorophore in their skeleton. Here we present BowtieArene, a novel fluorescent dual macrocycle, structurally featuring a central tetraphenylethylene‐derived fluorophore and double pillar‐like, pentagon‐shaped cavities which are comparable to pillar[5]arene. This concisely‐prepared, figure‐of‐eight molecule exhibits vapor absorption and host‐guest capabilities, as well as intriguing switchable fluorescence. The fluorochromism of BowtieArene can be triggered by multiple external stimuli including solvent, vapor, and mechanic force, with excellent reversibility and stability. Experimental and theoretical evidences support that the fluorochromism should be closely related to molecular packing.

Multilamellar LipoCEST Agents Obtained from Osmotic Shrinkage of Paramagnetically Loaded Giant Unilamellar Vescicles (GUVs)

By Martina Tripepi, Giuseppe Ferrauto, Paolo Oronzo Bennardi, Silvio Aime, Daniela Delli Castelli from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 05, 2019.

Moving from nano‐ to micro‐systems may not just be a matter of scale, but it might imply changes in the properties of the systems that can open new routes for the development of efficient MRI contrast agents. This is the case reported in the present paper, where giant liposomes (Giant Unilamellar Vesicles, GUVs) loaded with Ln(III) complexes have been studied as MRI CEST contrast agents. The comparison between nanosized liposomes (Small Unilamellar Vesicles, SUVs) and GUVs sharing the same formulation led to differences that could not be accounted only in term of the mere increase in size (from 100‐150 nm to 1‐2 µm). Upon osmotic shrinkage GUVs yielded a Saturation Transfer effect of three order of magnitude higher than SUVs consistent with the increase in vesicles volume. Confocal microscopy showed that the shrinkage of GUVs resulted in multilamellar particles whereas SUVs are known to yield asymmetrical, discoidal shape.

Mon 09 Dec 11:30: Growing Biosensors from Cambridge

From All Talks (aka the CURE list). Published on Dec 05, 2019.

Growing Biosensors from Cambridge

Over the past 20 years, Abcam has established itself as a global leader in high-quality biological reagents – the key bio-sensensors enabling life scientists worldwide in research, drug discovery and diagnostics.

Learn about how a local Cambridge start-up successfully expanded into a thriving publicly-listed global business, with 1,100 employees at 11 sites working at the forefront of life sciences innovation.

This talk will review Abcam’s technologies, and describe how its partnering & collaboration model with both established and novel instrumentation and clinical platforms is supporting the advance of ground-breaking analytical approaches that are accelerating the development of tomorrow’s medicines.

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[ASAP] Pseudoneutrophil Cytokine Sponges Disrupt Myeloid Expansion and Tumor Trafficking to Improve Cancer Immunotherapy

By Shuya Li†, Qin Wang†, Yanqiong Shen†, Muhammad Hassan†, Jizhou Shen†, Wei Jiang†, Yitan Su†, Jing Chen†, Li Bai†, Wenchao Zhou‡, and Yucai Wang*†§ from Nano Letters: Latest Articles (ACS Publications). Published on Dec 05, 2019.

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Nano Letters
DOI: 10.1021/acs.nanolett.9b03753

[ASAP] Fe3O4@TiO2-Laden Neutrophils Activate Innate Immunity via Photosensitive Reactive Oxygen Species Release

By Peng Zhang†?, Qin Zhao†?, Miusi Shi†, Chengcheng Yin†, Zifan Zhao†, Kailun Shen†, Yun Qiu†, Yin Xiao‡, Yanbing Zhao§, Xiangliang Yang§, and Yufeng Zhang*†? from Nano Letters: Latest Articles (ACS Publications). Published on Dec 05, 2019.

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Nano Letters
DOI: 10.1021/acs.nanolett.9b03777

[ASAP] Controlling the Magnetic Anisotropy of the van der Waals Ferromagnet Fe3GeTe2 through Hole Doping

By Se Young Park†‡§, Dong Seob Kim§?, Yu Liu?, Jinwoong Hwang#?, Younghak Kim?, Wondong Kim?, Jae-Young Kim?, Cedomir Petrovic?, Choongyu Hwang?, Sung-Kwan Mo#, Hyung-jun Kim?, Byoung-Chul Min?, Hyun Cheol Koo?, Joonyeon Chang?, Chaun Jang*?, Jun Woo Choi*?, and Hyejin Ryu*? from Nano Letters: Latest Articles (ACS Publications). Published on Dec 05, 2019.

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Nano Letters
DOI: 10.1021/acs.nanolett.9b03316

[ASAP] Integrating Rh Species with NiFe-Layered Double Hydroxide for Overall Water Splitting

By Bowei Zhang†§‡?, Chongqin Zhu¶?, Zishan Wu§‡?, Eli Stavitski?, Yu Hui Lui†, Tae-Hoon Kim#, Huan Liu§‡, Ling Huang§‡, Xuechen Luan?, Lin Zhou#, Kun Jiang???, Wenyu Huang?, Shan Hu*†, Hailiang Wang*§‡, and Joseph S. Francisco*¶ from Nano Letters: Latest Articles (ACS Publications). Published on Dec 05, 2019.

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Nano Letters
DOI: 10.1021/acs.nanolett.9b03460

[ASAP] Engineering Chirally Blind Protein Pseudocapsids into Antibacterial Persisters

By Ibolya E. Kepiro†?, Irene Marzuoli†‡?, Katharine Hammond†§?, Xiaoliang Ba?, Helen Lewis†, Michael Shaw†#, Smita B. Gunnoo†, Emiliana De Santis†, Urszula Lapin´ska¶, Stefano Pagliara¶, Mark A. Holmes?, Christian D. Lorenz?, Bart W. Hoogenboom§?, Franca Fraternali‡, and Maxim G. Ryadnov*†? from ACS Nano: Latest Articles (ACS Publications). Published on Dec 05, 2019.

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ACS Nano
DOI: 10.1021/acsnano.9b06814

[ASAP] Correction to Wedge Dyakonov Waves and Dyakonov Plasmons in Topological Insulator Bi2Se3 Probed by Electron Beams

By Nahid Talebi*, Cigdem Ozsoy-Keskinbora, Hadj M. Benia, Klaus Kern, Christoph T. Koch, and Peter A. van Aken from ACS Nano: Latest Articles (ACS Publications). Published on Dec 05, 2019.

ACS Nano
DOI: 10.1021/acsnano.9b09363

[ASAP] Underlying Promotion Mechanism of High Concentration of Silver Nanoparticles on Anammox Process

By Meng-Wen Peng†, Xiu-Ling Yu‡, Yong Guan*§, Peng Liu?, Peng Yan†, Fang Fang†, Jinsong Guo†, and You-Peng Chen*† from ACS Nano: Latest Articles (ACS Publications). Published on Dec 05, 2019.

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ACS Nano
DOI: 10.1021/acsnano.9b08263

[ASAP] Tuning the Porosity of Supraparticles

By Wendong Liu, Michael Kappl*, and Hans-Ju¨rgen Butt from ACS Nano: Latest Articles (ACS Publications). Published on Dec 05, 2019.

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ACS Nano
DOI: 10.1021/acsnano.9b05673

[ASAP] Synthesis of PdM (M = Zn, Cd, ZnCd) Nanosheets with an Unconventional Face-Centered Tetragonal Phase as Highly Efficient Electrocatalysts for Ethanol Oxidation

By Qinbai Yun‡§?, Qipeng Lu‡??, Cuiling Li‡??, Bo Chen‡, Qinghua Zhang#, Qiyuan He‡, Zhaoning Hu‡, Zhicheng Zhang‡, Yiyao Ge‡, Nailiang Yang‡?, Jingjie Ge‡, Yan-Bing He?, Lin Gu#%^, and Hua Zhang*†‡ from ACS Nano: Latest Articles (ACS Publications). Published on Dec 05, 2019.

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ACS Nano
DOI: 10.1021/acsnano.9b07775

[ASAP] Polyfunctional Nanofibril Appendages Mediate Attachment, Filamentation, and Filament Adaptability in Leptothrix cholodnii

By Tatsuki Kunoh*‡?, Kana Morinaga†?, Shinya Sugimoto?, Shun Miyazaki†, Masanori Toyofuku‡§, Kenji Iwasaki?, Nobuhiko Nomura*‡§, and Andrew S. Utada*‡§ from ACS Nano: Latest Articles (ACS Publications). Published on Dec 05, 2019.

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ACS Nano
DOI: 10.1021/acsnano.9b04663

[ASAP] Single-Phase Borophene on Ir(111): Formation, Structure, and Decoupling from the Support

By Nikolay A. Vinogradov†, Andrey Lyalin‡?, Tetsuya Taketsugu‡?, Alexander S. Vinogradov§, and Alexei Preobrajenski*† from ACS Nano: Latest Articles (ACS Publications). Published on Dec 05, 2019.

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ACS Nano
DOI: 10.1021/acsnano.9b08296

[ASAP] Gapless van der Waals Heterostructures for Infrared Optoelectronic Devices

By Yao Wen‡†, Peng He§†, Qisheng Wang§†, Yuyu Yao§, Yu Zhang‡, Sabir Hussain§, Zhenxing Wang§, Ruiqing Cheng§, Lei Yin§, Marshet Getaye Sendeku§, Feng Wang§, Chao Jiang§, and Jun He*‡ from ACS Nano: Latest Articles (ACS Publications). Published on Dec 05, 2019.

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ACS Nano
DOI: 10.1021/acsnano.9b08375

[ASAP] Hierarchical Porous Wood Cellulose Scaffold with Atomically Dispersed Pt Catalysts for Low-Temperature Ethylene Decomposition

By Huizhang Guo*†‡, Peter Warnicke§, Michele Griffa?, Ulrich Mu¨ller?, Zupeng Chen#, Robin Schaeublin?, Zhidong Zhang?, and Mirko Lukovic´*†‡ from ACS Nano: Latest Articles (ACS Publications). Published on Dec 05, 2019.

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ACS Nano
DOI: 10.1021/acsnano.9b07801

[ASAP] Transcription of Chirality from Metal–Organic Framework to Polythiophene

By Takashi Kitao†‡, Yujiro Nagasaka‡, Masanobu Karasawa?, Toshiki Eguchi#, Nobuo Kimizuka#, Kazuyuki Ishii?, Teppei Yamada#, and Takashi Uemura*†‡§ from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Dec 05, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b10880

[ASAP] Isolation and Study of Ruthenium–Cobalt Oxo Cubanes Bearing a High-Valent, Terminal RuV–Oxo with Significant Oxyl Radical Character

By Jaruwan Amtawong†, David Balcells‡, Jarett Wilcoxen§, Rex C. Handford†, Naomi Biggins†, Andy I. Nguyen†?, R. David Britt§, and T. Don Tilley*†? from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Dec 05, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b10320

[ASAP] Electrochemical Resistive-Pulse Sensing

By Rongrong Pan†§, Keke Hu†‡, Dechen Jiang*§, Uri Samuni†‡, and Michael V. Mirkin*†‡ from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Dec 05, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b10329

[ASAP] The Aza-hexadehydro-Diels–Alder Reaction

By Severin K. Thompson and Thomas R. Hoye* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Dec 05, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b11243

[ASAP] Oriented Two-Dimensional Covalent Organic Framework Films for Near-Infrared Electrochromic Application

By Qing Hao†§, Zhi-Juan Li‡§, Cheng Lu†§, Bing Sun†?, Yu-Wu Zhong*‡§, Li-Jun Wan†§, and Dong Wang*†§ from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Dec 05, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b09956

[ASAP] Correlation between Structure and Energetic Properties of Three Nitroaromatic Compounds: Bis(2,4-dinitrophenyl) Ether, Bis(2,4,6-trinitrophenyl) Ether, and Bis(2,4,6-trinitrophenyl) Thioether

By Marco Reichel†, Dominik Dosch†, Thomas Klapo¨tke*, and Konstantin Karaghiosoff from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Dec 05, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b11086

[ASAP] Understanding Structure–Property Relationships of MoO3-Promoted Rh Catalysts for Syngas Conversion to Alcohols

By Arun S. Asundi†, Adam S. Hoffman‡, Pallavi Bothra†§, Alexey Boubnov‡?, Fernando D. Vila#, Nuoya Yang?, Joseph A. Singh?, Li Zeng†, James A. Raiford†, Frank Abild-Pedersen†§, Simon R. Bare‡, and Stacey F. Bent*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Dec 05, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b07460

[ASAP] 1D to 2D Self Assembly of Cyclic Peptides

By Ignacio Insua and Javier Montenegro* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Dec 05, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b10582

[ASAP] a-C–H Functionalization of p-Bonds Using Iron Complexes: Catalytic Hydroxyalkylation of Alkynes and Alkenes

By Yidong Wang, Jin Zhu, Austin C. Durham, Haley Lindberg, and Yi-Ming Wang* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Dec 05, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b11716

[ASAP] Carboxylation of Benzylic and Aliphatic C–H Bonds with CO2 Induced by Light/Ketone/Nickel

By Naoki Ishida*, Yusuke Masuda, Yuuya Imamura, Katsushi Yamazaki, and Masahiro Murakami* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Dec 05, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b12529

[ASAP] Bis-Monophospholyl Dysprosium Cation Showing Magnetic Hysteresis at 48 K

By Peter Evans, Daniel Reta, George F.S. Whitehead, Nicholas F. Chilton*, and David P. Mills* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Dec 05, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b11515

[ASAP] Fungal Highly Reducing Polyketide Synthases Biosynthesize Salicylaldehydes That Are Precursors to Epoxycyclohexenol Natural Products

By Ling Liu†‡, Man-Cheng Tang*†?, and Yi Tang*†§ from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Dec 05, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b09669

[ASAP] Large Chiral Nanotubes Self-Assembled by DNA Bricks

By Sha Sun*†, Yuxuan Yang‡, Dongmin Li†, and Jin Zhu§ from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Dec 05, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b08737

[ASAP] Emissive Single-Crystalline Boroxine-Linked Colloidal Covalent Organic Frameworks

By Austin M. Evans†, Ioannina Castano†, Alexandra Brumberg†, Lucas R. Parent†‡§, Amanda R. Corcos†?, Rebecca L. Li†, Nathan C. Flanders†, David J. Gosztola?, Nathan C. Gianneschi†‡§?#?, Richard D. Schaller†?, and William R. Dichtel*†? from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Dec 05, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b08815

[ASAP] Interstitial Boron Atoms in the Palladium Lattice of an Industrial Type of Nanocatalyst: Properties and Structural Modifications

By Tianyi Chen†§, Ieuan Ellis†?, Thomas J. N. Hooper‡, Emanuela Liberti§, Lin Ye†, Benedict T. W. Lo†, Colum O’Leary§, Alexandra A. Sheader§, Gerardo T. Martinez§, Lewys Jones§, Ping-Luen Ho†§, Pu Zhao†, James Cookson?, Peter T. Bishop?, Philip Chater?, John V. Hanna*‡, Peter Nellist*§, and Shik Chi Edman Tsang*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Dec 05, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b06120

[ASAP] Inserting Nitrogen: An Effective Concept To Create Nonplanar and Stimuli-Responsive Perylene Bisimide Analogues

By Sakiho Hayakawa†, Ayumi Kawasaki‡§, Yongseok Hong?, Daisuke Uraguchi†, Takashi Ooi†?, Dongho Kim*?, Tomoyuki Akutagawa*‡§, Norihito Fukui*†, and Hiroshi Shinokubo*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Dec 05, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b09556

[ASAP] A Highly Luminescent Chiral Tetrahedral Eu4L4(L')4 Cage: Chirality Induction, Chirality Memory, and Circularly Polarized Luminescence

By Yanyan Zhou, Hongfeng Li*, Tianyu Zhu, Ting Gao, and Pengfei Yan* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Dec 05, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b07178

[ASAP] Atomically Defined Nanopropeller Fe3Co6Se8(Ph2PNTol)6: Functional Model for the Electronic Metal–Support Interaction Effect and High Catalytic Activity for Carbodiimide Formation

By Jonathan A. Kephart†, Benjamin S. Mitchell†, Andrei Chirila†, Kevin J. Anderton‡, Dylan Rogers†, Werner Kaminsky†, and Alexandra Velian*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Dec 05, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b12473

Composition-induced type I and direct bandgap transition metal dichalcogenides alloy vertical heterojunctions

By David J. Srolovitz from RSC - Nanoscale latest articles. Published on Dec 05, 2019.

Nanoscale, 2020, Advance Article
DOI: 10.1039/C9NR08345F, Paper
Songsong Zhou, Jinliang Ning, Jianwei Sun, David J. Srolovitz
Using alloying and/or twisting between layers to achieve the type I direct bandgaps vertical heterojunction in transition metal dichalcogenide family of MX2 (M = {Mo, W}, X = {S, Se}).
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Membrane Lipids Destabilize Short Interfering Ribonucleic Acid (siRNA)/Polyethylenimine Nanoparticles

By Hasan Uludag from RSC - Nanoscale latest articles. Published on Dec 05, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR08128C, Paper
Yousef Nademi, Tian Tang, Hasan Uludag
Cell entry of polymeric nanoparticles (NPs) bearing polynucleotides is an important stage for successful gene delivery. In this work, we addressed the influence of cell membrane lipids on the integrity...
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Photo-assisted Rechargeable Battery: Synergy, Compatibility and Stability of TiO2/dye/Cu2S Bifunctional Composite Electrode

By Wei Lu from RSC - Nanoscale latest articles. Published on Dec 05, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR09224B, Communication
Chong Xu, Xu Zhang, Lianfeng Duan, Xueyu Zhang, Xuesong Li, Wei Lu
Herein we present a simple and novel approach to fabricate the bifunctional compatible electrode, which have functionalities of photoelectric conversion and energy storage. The integrated photo-assisted rechargeable battery of two-electrode...
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Support Interactions Dictated Active Edge Sites over MoS2-Carbon Composites for Hydrogen Evolution

By Xiuqiang Xie from RSC - Nanoscale latest articles. Published on Dec 05, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR09023A, Paper
Xiaobin Qiu, Yewei Huang, Zhenzhen Nie, Beibei Ma, Yongwen Tan, Zhenjun Wu, Nan Zhang, Xiuqiang Xie
The rational design and synthesis of MoS2-based electrocatalysts with desirable active sites for hydrogen evolution reaction have been actively pursued. Herein, we demonstrate a microwave-assisted steam heating method for the...
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SPION decorated exosome delivery of TNF-α to cancer cell membranes through magnetism

By Lei Rao from RSC - Nanoscale latest articles. Published on Dec 05, 2019.

Nanoscale, 2020, Advance Article
DOI: 10.1039/C9NR05865F, Paper
Manjiao Zhuang, Xuelian Chen, Dan Du, Jiamei Shi, Mian Deng, Qian Long, Xiaofei Yin, Yayu Wang, Lei Rao
The construction and therapy strategy of a CTNF-α-exosome-SPION and the preparation of the CTNF-α-exosome-SPION by gene engineering and dehydration synthesis are described here. The CTNF-α-exosome-SPION displays membrane targeting anticancer activity with the help of magnetic force.
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Amphiphilic anthanthrene trimers that exfoliate graphite and individualize single wall carbon nanotubes

By Dirk M. Guldi from RSC - Nanoscale latest articles. Published on Dec 05, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR08062G, Paper
Open Access Open Access
Peter Münich, Matthias Pfäffli, Michel Volland, Shi-Xia Liu, Robert Haener, Dirk M. Guldi
A phosphodiester-linked dialkynyl substituted anthanthrene trimer (1) has been designed and synthesized. Its graphene ribbon like structure is expected to facilitate interactions with nanographene (NG) and single wall carbon nanotubes...
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Large Amplitude Charge Noise and Random Telegraph Fluctuations in Room-Temperature Graphene Single-Electron Transistors

By Jan Andries Mol from RSC - Nanoscale latest articles. Published on Dec 05, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR08574B, Paper
Jasper Paul Fried, Xinya Bian, Jacob Swett, Ivan Kravchenko, Andrew Davidson Briggs, Jan Andries Mol
We analyze the noise in liquid-gated, room temperature, graphene quantum dots. These devices display extremely large noise amplitudes. The observed noise is explained in term of a charge noise model...
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Synthesis of Ternary Metal Oxide as a Positive Electrode for Mg-Li Hybrid Ion Batteries

By Iftikhar Ahmed from RSC - Nanoscale latest articles. Published on Dec 05, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR08758C, Paper
Muhammad Asif, Muhammad Rashad, Zeeshan Ali, Iftikhar Ahmed
Rechargeable magnesium-ion battery (MIB) has emerged as an exciting energy storage system owing to highly stable magnesiation and de-magnesiation process and high theoratical energy density. However, MIB technology is restricted...
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Loading FeOOH on Ni(OH)2 hollow nanorods to obtain a three-dimensional sandwich catalyst with strong electron interactions for efficient oxygen-evolution reaction

By Qiang Zhao from RSC - Nanoscale latest articles. Published on Dec 05, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR08297B, Paper
Wenjun Guo, Dandan Li, Dazhong Zhong, Shuai Chen, Genyan Hao, Guang Liu, Jinping Li, Qiang Zhao
The sustainable production of hydrogen by water splitting requires the exploration of highly efficient electrocatalysts from abundant non-precious metals on earth. Ni(OH)2 hollow nanorod arrays were obtained on Ni foam...
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Electrosynthesis of defective indium selenide with 3D structure on substrate for tunable CO2 electroreduction to syngas

By Dexin Yang, Qinggong Zhu, Xiaofu Sun, Chunjun Chen, Weiwei Guo, Guanying Yang, Buxing Han from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 04, 2019.

Syngas (CO/H2) is feedstock for producing a variety of valuable chemicals and liquid fuel, and CO2 electrochemical reduction to syngas is very promising. However, producing syngas with high efficiency is difficult. Herein, we discovered that defective indium selenide synthesized by electrosynthesis method on carbon paper (γ‐In2Se3/CP) was an extremely efficient electrocatalyst for this reaction. CO and H2 were the only product and CO/H2 ratio could be tuned in a wide range by changing applied potential or the composition of electrolyte. Especially, using nanoflower‐like γ‐In2Se3/CP (F‐γ‐In2Se3/CP) as electrode, the current density could be as high as 90.1 mA cm‐2 at CO/H2 ratio of 1/1. In addition, the Faradaic efficiency of CO could reach 96.5% with the current density of 55.3 mA cm‐2 at very low overpotential of 220 mV. The outstanding electrocatalytic performance of the F‐γ‐In2Se3/CP can be attributed to its defect‐rich, 3D structure, and good contact with CP substrate.

Helical Pore Alignment on Cylindrical Carbon

By Jun Maruyama, Tsutomu Shinagawa, Mitsuru Watanabe, Yukiyasu Kashiwagi, Shohei Maruyama, Toru Nagaoka, Wakana Matsuda, Yusuke Tsutsui, Shu Seki, Hiroshi Uyama from Wiley: Small: Table of Contents. Published on Dec 04, 2019.

Polystyrene nanoparticles cylindrically self‐assemble with fructose in the presence of both carbon nanofibers and sodium alginate. Carbonization generates fructose‐derived honeycomb‐like carbon walls with helically aligned nanopores left after the polystyrene decomposition. The diffuse reflectance circular dichroism measurement shows the chirality of the cylindrical carbon. Abstract Interest in chiral substances has mainly focused on the substances themselves, but not on the accompanying space, especially regarding the pore alignment. As a method to form both the chiral substance and the accompanying space, cylindrical self‐assembly of uniform polystyrene nanoparticles with fructose is carried out in the presence of both carbon and sodium alginate, which is followed by heat treatment in an inert atmosphere. The carbonization generates fructose‐derived honeycomb‐like carbon walls with helically aligned nanopores left after the polystyrene decomposition. The diffuse reflectance circular dichroism measurements give peaks with opposite signs for the d‐ and l‐fructose‐derived cylindrical carbons. Circularly polarized light sensitivity in transient photoconductivity is confirmed apparently in the carbon‐based helical structures. This sensitivity as well as straightforward formation of composites with another component to give helicity shows potential applications of the helically aligned pores.

Importance of Volume Ratio in Photonic Effects of Lanthanide‐Doped LaPO4 Nanocrystals

By Yuxia Luo, Liyi Li, Hon Tung Wong, Ka‐Leung Wong, Peter A. Tanner from Wiley: Small: Table of Contents. Published on Dec 04, 2019.

The variation of luminescence decay rate with filling factor of nanoparticles dispersed in solvents, and with medium refractive index (nmed), is fitted by the model of Pukhov, enabling an estimation of quantum yields. The local field effects upon energy transfer (ET) between Tb3+ and Eu3+ are studied in a wide range of nmed. The ET rate is independent on nmed and the energy transfer efficiency decreases with an increase in nmed. Abstract Experimental variation of the volume ratio (filling factor: i.e., volume of nanoparticles (NPs) compared with that of medium) of nanocomposite materials with doped lanthanide ions demonstrates that it has a significant affect upon local field effects. Lanthanum orthophosphate NPs are doped with Eu3+ and/or Tb3+ and immersed in organic solvents and lead borate glasses for Tb3+ 5D4 lifetime measurements. For media with a refractive index (nmed) less than that of LaPO4 (nnp = 1.79), the 5D4 emission decay rate increases with increasing volume ratio of the NPs, whereas for nmed > 1.79, the decay rate decreases with increasing volume ratio. Fitting with the model of Pukhov provides an estimation of the radiative lifetime of 5D4 and the quantum yield. Energy transfer (ET) from Tb3+ to Eu3+ occurs in co‐doped LaPO4 NPs with excitation into a Tb3+ absorption band. The ET rate is independent on nmed and the energy transfer efficiency decreases with an increase in nmed. The behavior of ET rate with regard to the local field is consistent with the Dexter, but not Förster, equation for ET rate involving the electric dipole–electric dipole mechanism. This has consequences when using the spectroscopic ruler approach to measure distances between donor–acceptor chromophores.

Crystal Engineering of Room Temperature Phosphorescence in Organic Solids

By Ehsan Hamzehpoor, Dmitrii F. Perepichka from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 04, 2019.

Solid state packing in a series of azatriangulenetrione (TANGO) derivatives controls their luminescence properties. Co‐alignment of transition dipoles in π‐stacks leads to efficient room temperature phosphorescence while their 60° rotation caused by sterically hindering tert‐butyl groups results in an almost pure fluorescence. The phosphorescence quantum yield of 42 % is achieved for pure HTANGO crystals without heavy atoms. Abstract We report a series of highly emissive azatriangulenetrione (TANGO) solids in which the luminescent properties are controlled by engineering the molecular packing by adjusting the steric size of substituents. The co‐alignment of “phosphorogenic” carbonyl groups within the π‐stacks results in an almost pure triplet emission in HTANGO, TCTANGO, TBTANGO and TITANGO, while their rotation by ≈60° in the sterically hindered tBuTANGO leads to an almost pure singlet emission. Despite strong π‐interactions, aggregation‐induced quenching and triplet–triplet annihilation are avoided in HTANGO and TCTANGO which display efficient phosphorescence in the solid state. To our knowledge, HTANGO with the solid‐state phosphorescence quantum yield of 42 % at room temperature is the most efficient phosphor composed of the 1st/2nd raw elements only.

Enantioselective Total Synthesis of Cymoside through a Bioinspired Oxidative Cyclization of a Strictosidine Derivative

By Yingchao Dou, Cyrille Kouklovsky, Vincent Gandon, Guillaume Vincent from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 04, 2019.

A bioinspired oxidative cascade cyclization allows to accomplish the first total synthesis of cymoside, a monoterpene indole alkaloid which possesses a unique furo[3,2‐b]indoline‐containing hexacyclic‐fused skeleton. Abstract The first total synthesis of the caged monoterpene indole alkaloid cymoside is reported. This natural product displays a unique hexacyclic‐fused skeleton whose biosynthesis implies an early oxidative cyclization of strictosidine. Our approach to the furo[3,2‐b]indoline framework relied on an unprecedented biomimetic sequence which started by the diastereoselective oxidation of the indole ring into a hydroxyindolenine which triggered the addition of an enol ether and was followed by the trapping of an oxocarbenium intermediate.

Wenjun Tang

By from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 04, 2019.

“My greatest achievement has been the development of a series of chiral phosphorus ligands that are useful in asymmetric catalysis. The most exciting thing about my research is the unexpected reactivity and selectivity observed with a newly designed catalyst …” Find out more about Wenjun Tang in his Author Profile.

Atypical Hybrid Metal–Organic Frameworks (MOFs): A Combinative Process for MOF‐on‐MOF Growth, Etching, and Structure Transformation

By Sujeong Lee, Sojin Oh, Moonhyun Oh from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 04, 2019.

Well‐designed atypical hybrid metal–organic frameworks (MOFs) with unique morphologies and complicated components are constructed with regulated combinations of three distinctive processes: MOF‐on‐MOF growth, etching, and structural transformation. The resulting hybrid MOFs are utilized as precursor materials for the generation of active oxygen reduction reaction (ORR) catalysts. Abstract The structural, compositional, and morphological features of metal–organic frameworks (MOFs) govern their properties and applications. Construction of hybrid MOFs with complicated structures, components, or morphologies is significant for the development of well‐organized MOFs. An advanced route is reported for construction of atypical hybrid MOFs with unique morphologies and complicated components: 1) MOF‐on‐MOF growth of a 3D zeolitic imidazolate framework (ZIF) on a ZIF‐L template, 2) etching of a part of the 2D ZIF‐L template, and 3) structural transformation of 2D ZIF‐L into 3D ZIF. The formation of core–shell‐type MOF rings and plates is controlled by regulating the three processes. The formation route for the core–shell‐type MOF rings and plates was monitored by tracking changes in morphology, structure, and composition. Carbon materials prepared from the pyrolysis of the core–shell‐type hybrid MOFs displayed enhanced oxygen reduction reaction activities compared to their monomeric counterparts.

Dual Enhancement of Gold Nanocluster Electrochemiluminescence: Electrocatalytic Excitation and Aggregation‐Induced Emission

By Huaping Peng, Zhongnan Huang, Haohua Deng, Weihua Wu, Kaiyuan Huang, Zhenglian Li, Wei Chen, Juewen Liu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 04, 2019.

Drying enabled the electrocatalytic excitation and aggregation‐induced emission of ligand‐capped gold nanoclusters (AuNCs), allowing a record high solid‐phase electrochemiluminescence (ECL) yield of 78 % and visual ECL. This work supports the in‐depth design and study of ECL in AuNCs and other materials in aqueous solutions. Abstract Ligand‐protected gold nanoclusters (AuNCs) have emerged as a new class of electrochemiluminescence (ECL) luminophores for their interesting catalytic and emission properties, although their quantum yield (ΦECL) in aqueous medium is low with a poor mechanistic understanding of the ECL process. Now it is shown that drying AuNCs on electrodes enabled both enhanced electrochemical excitation by an electrocatalytic effect, and enhanced emission by aggregation‐induced ECL (AIECL) for 6‐aza‐2‐thiothymine (ATT) protected AuNCs with triethylamine (TEA) as a coreactant. The dried ATT‐AuNCs/TEA system resulted in highly stable visual ECL with a ΦECL of 78 %, and a similar enhancement was also achieved with methionine‐capped AuNCs. The drying enabled dual‐enhancement mechanism has solved a challenging mechanistic problem for AuNC ECL probes, and can guide further rational design of ECL emitters.

Nanoaggregate Probe for Breast Cancer Metastasis through Multispectral Optoacoustic Tomography and Aggregation‐Induced NIR‐I/II Fluorescence Imaging

By Juan Ouyang, Lihe Sun, Zhuo Zeng, Cheng Zeng, Fang Zeng, Shuizhu Wu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 04, 2019.

An activatable nanoprobe with AIE feature has been developed as the dual‐mode probe for monitoring breast cancer metastasis optoacoustically and fluorescently. The focus of orthotopic breast tumors can be located through 3D multispectral optoacoustic tomography (MSOT) imaging, and the sequential metastases of primary tumors to lymph nodes and lung can be mapped spatiotemporally. Abstract An activatable nanoprobe for imaging breast cancer metastases through near infrared‐I (NIR‐I)/NIR‐II fluorescence imaging and multispectral optoacoustic tomography (MSOT) imaging was designed. With a dihydroxanthene moiety serving as the electron donor, quinolinium as the electron acceptor and nitrobenzyloxydiphenylamino as the recognition element, the probe can specifically respond to nitroreductase and transform into an activated D‐π‐A structure with a NIR emission band extending beyond 900 nm. The activated nanoprobe exhibits NIR emission enhanced by aggregation‐induced emission (AIE) and produces strong optoacoustic signal. The nanoprobe was used to detect and image metastases from the orthotopic breast tumors to lymph nodes and then to lung in two breast cancer mouse models. Moreover, the nanoprobe can monitor the treatment efficacy during chemotherapeutic course through fluorescence and MSOT imaging.

Calcium Hydride Reduction of Polycyclic Aromatic Hydrocarbons

By Andrew S. S. Wilson, Chiara Dinoi, Michael S. Hill, Mary F. Mahon, Laurent Maron, Emma Richards from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 04, 2019.

A fragrant reduction: A molecular calcium hydride effects the two electron reduction of polyaromatic hydrocarbons, including naphthalene (E0=−3.1 V). Abstract A molecular calcium hydride effects the two electron reduction of polyaromatic hydrocarbons, including naphthalene (E0=−3.1 V).

Pd/Cu‐Catalyzed Enantioselective Sequential Heck/Sonogashira Coupling: Asymmetric Synthesis of Oxindoles Containing Trifluoromethylated Quaternary Stereogenic Centers

By Xingfeng Bai, Caizhi Wu, Shaozhong Ge, Yixin Lu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 04, 2019.

Pd and Cu work together: A highly enantioselective Pd/Cu‐catalyzed Heck/Sonogashira coupling reaction was developed to prepare chiral oxindoles containing quaternary stereogenic centers, particularly trifluoromethylated ones. The synthetic utilities of this enantioselective protocol were exemplified through several stereospecific derivatizations and the synthesis of EGIS‐12,233, a potent and selective antagonist for 5‐HT6/7 receptors. Abstract An asymmetric palladium and copper co‐catalyzed Heck/Sonogashira reaction between o‐iodoacrylanilides and terminal alkynes to synthesize chiral oxindoles was developed. In particular, a wide range of CF3‐substituted o‐iodoacrylanilides reacted with terminal alkynes, affording the corresponding chiral oxindoles containing trifluoromethylated quaternary stereogenic centers in high yields with excellent enantioselectivities (94–98 % ee). This asymmetric Heck/Sonogashira reaction provides a general approach to access oxindole derivatives containing quaternary stereogenic centers including CF3‐substituted ones.

Total Synthesis and Structural Revision of a Harziane Diterpenoid

By Moritz Hönig, Erick M. Carreira from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 04, 2019.

Reassignment: The first total synthesis of nominal harziane diterpenoid 1 is disclosed, whose spectral characteristics do not match those of the reported natural product. Stereochemical analysis and subsequent synthesis of the epimeric tertiary alcohol lead to reassignment of configuration of the natural product as shown for 2. Abstract The first total synthesis of nominal harziane diterpenoid 1 is disclosed, whose spectral characteristics did not match those of the reported natural product. Stereochemical analysis and subsequent synthesis of the epimeric tertiary alcohol led to reassignment of configuration of the natural product as shown for 2. At the heart of the synthesis is an enyne cycloisomerization that sets a key quaternary stereocenter within a cyclobutane with high diastereocontrol. The route features strategies for the synthesis of the highly congested 6‐5‐7‐4 carbon skeleton characteristic of the caged harziane diterpenoids.

Stereospecific and Chemoselective Copper‐Catalyzed Deaminative Silylation of Benzylic Ammonium Triflates

By Jonas Scharfbier, Benjamin M. Gross, Martin Oestreich from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 04, 2019.

SiR, the NMe has surrendered: Benzylic ammonium salts can be transformed into the corresponding silanes by a copper‐catalyzed SN2‐type displacement. The enantioenrichment of the precursors is completely retained in the α‐chiral silanes. A cyclopropyl group at the benzylic carbon atom remains intact, thereby supporting an ionic reaction mechanism. Abstract A method for the synthesis of benzylsilanes starting from the corresponding ammonium triflates is reported. Silyl boronic esters are employed as silicon pronucleophiles, and the reaction is catalyzed by copper(I) salts. Enantioenriched benzylic ammonium salts react stereospecifically through an SN2‐type displacement of the ammonium group to afford α‐chiral silanes with inversion of the configuration. A cyclopropyl‐substituted substrate does not undergo ring opening, thus suggesting an ionic reaction mechanism with no benzyl radical intermediate.

Improved Stability and Tunable Functionalization of Parallel β‐Sheets via Multicomponent N‐Alkylation of the Turn Moiety

By Manuel G. Ricardo, Celia G. Moya, Carlos S. Pérez, Andrea Porzel, Ludger A. Wessjohann, Daniel G. Rivera from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 04, 2019.

Keep it folded: An Ugi‐derived N‐alkylation suitably positioned at the turn moiety of a non‐cyclic parallel β‐sheet peptide enhances the folding propensity and thermal stability in aqueous solution. It also enables the installation of various functionalities, for example an extra cationic group to abolish aggregation, or a thiol for conjugation to a fluorescent label. Abstract In contrast to the myriad of methods available to produce α‐helices and antiparallel β‐sheets in synthetic peptides, just a few are known for the construction of stable, non‐cyclic parallel β‐sheets. Herein, we report an efficient on‐resin approach for the assembly of parallel β‐sheet peptides in which the N‐alkylated turn moiety enhances the stability and gives access to a variety of functionalizations without modifying the parallel strands. The key synthetic step of this strategy is the multicomponent construction of an N‐alkylated turn using the Ugi reaction on varied isocyano‐resins. This four‐component process assembles the orthogonally protected turn fragment and incorporates handles serving for labeling/conjugation purposes or for reducing peptide aggregation. NMR and circular dichroism analyses confirm the better‐structured and more stable parallel β‐sheets in the N‐alkylated peptides compared to the non‐functionalized variants.

Nanoparticle Size‐Fractionation through Self‐Standing Porous Covalent Organic Framework Films

By Kaushik Dey, Shebeeb Kunjattu H., Anurag M. Chahande, Rahul Banerjee from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 04, 2019.

Panning for (nano)gold: A strategic approach to design self‐standing, covalent organic framework (COF) films with high permeability is reported for the size‐selective fractionation of gold nanoparticles. The vertical nanochannels of the COF pores allow selective passage of the nanoparticles. Abstract Covalent organic frameworks (COFs) have attracted attention due to their ordered pores leading to important industrial applications like storage and separation. Combined with their modular synthesis and pore engineering, COFs could become ideal candidates for nanoseparations. However, the fabrication of these microcrystalline powders as continuous, crack‐free, robust films remains a challenge. Herein, we report a simple, slow annealing strategy to construct centimeter‐scale COF films (Tp‐Azo and Tp‐TTA) with micrometer thickness. The as‐synthesized films are porous (SABET=2033 m2 g−1 for Tp‐Azo) and chemically stable. These COFs have distinct size cut‐offs (ca. 2.7 and ca. 1.6 nm for Tp‐Azo and Tp‐TTA, respectively), which allow the size‐selective separation of gold nanoparticles. Unlike, other conventional membranes, the durable structure of the COF films allow for excellent recyclability (up to 4 consecutive cycles) and easy recovery of the gold nanoparticles from the solution.

Enantioenriched Methylene‐Bridged Benzazocanes Synthesis by Organocatalytic and Superacid Activations

By Rodolphe Beaud, Bastien Michelet, Yasmin Reviriot, Agnès Martin‐Mingot, Jean Rodriguez, Damien Bonne, Sébastien Thibaudeau from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 04, 2019.

Organocatalysis meets superacid: An original synthetic strategy based on the sequential association of organocatalytic and superacid activations has been developed that allows the efficient preparation of optically‐enriched methylene‐bridged benzazocanes closely related to bioactive morphinan and benzomorphan scaffolds from simple achiral linear precursors. Abstract Achieving in a straightforward way the synthesis of enantioenriched elaborated three‐dimensional molecules related to bioactive natural products remains a long‐standing quest in organic synthesis. Enantioselective organocatalysis potentially offers a unique opportunity to solve this problem, especially when combined with complementary modes of activation. Here, we report the sequential association of organocatalytic and superacid activations of simple linear achiral readily available precursors to promote the formation of unique highly elaborated chiral methylene‐bridged benzazocanes exhibiting three to five fully‐controlled stereocenters. This peculiar backbone, difficult to assemble by standard synthetic approaches, is closely related to bioactive natural and synthetic morphinans and benzomorphans. The formation of a highly reactive chiral 7‐membered ring N‐acyl iminium superelectrophilic ion, evidenced by low‐temperature in situ NMR experiments, triggers a challenging stereoselective Friedel–Crafts‐type cyclization.

Cellulose Nanocrystal Elastomers with Reversible Visible Color

By Charlotte E. Boott, Andy Tran, Wadood Y. Hamad, Mark J. MacLachlan from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 04, 2019.

Mechanical stress sensors were prepared from cellulose nanocrystal‐elastomer composites, which provide a reversible visible color readout. Abstract Responsive photonic crystals have potential applications in mechanical sensors and soft displays; however, new materials are constantly desired to provide new innovations and improve on existing technologies. To address this, we report stretchable chiral nematic cellulose nanocrystal (CNC) elastomer composites that exhibit reversible visible color upon the application of mechanical stress. When stretched (or compressed) the colorless materials maintain their chiral nematic structure but the helical pitch is reduced into the visible region, resulting in coloration of the CNC‐elastomer composite. By increasing the percentage elongation of the material (ca. 50–300 %), the structural color can be tuned from red to blue. The color of the materials was characterized by reflectance optical microscopy and reflectance circular dichroism to confirm the wavelength and polarization of the reflected light. We also probed the mechanism of the structural color using 2D‐X‐ray diffraction. Finally, by either water‐patterning the starting CNC film, or by forming a CNC film with gradient color, through masked evaporation, we were able to prepare encoded stretchable chiral nematic CNC‐elastomers.

Synthetic Humic Acids Solubilize Otherwise Insoluble Phosphates to Improve Soil Fertility

By Fan Yang, Shuaishuai Zhang, Jingpeng Song, Qing Du, Guixiang Li, Nadezda V. Tarakina, Markus Antonietti from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 04, 2019.

Making the P: Artificial humic acids made from biomass in a hydrothermal process are a practical route to solubilize otherwise insoluble phosphorous species which contributes to the fertility of soils. Agricultural chemical tests indicate that the content of total P and directly plant‐available P improved. Abstract Artificial humic acids (A‐HA) made from biomass in a hydrothermal process turn otherwise highly insoluble phosphates (e.g. iron phosphate as a model) into highly available phosphorus, which contributes to the fertility of soils and the coupled plant growth. A detailed electron microscopy study revealed etching of the primary iron phosphate crystals by the ‐COOH and phenolic groups of humic acids, but also illustrated the importance of the redox properties of humic matter on the nanoscale. The combined effects result in the formation of then bioavailable phosphate nanoparticles stabilized by humic matter. Typical agricultural chemical tests indicate that the content of total P and directly plant‐available P improved largely. Comparative pot planting experiments before and after treatment of phosphates with A‐HA demonstrate significantly enhanced plant growth, as quantified in higher aboveground and belowground plant biomass.

Steric Mixed‐Cation 2D Perovskite as a Methylammonium Locker to Stabilize MAPbI3

By Xingtao Wang, Yong Wang, Taiyang Zhang, Xiaomin Liu, Yixin Zhao from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 04, 2019.

Locked up: The steric PTA‐MA mixed‐cation 2D perovskite of PTAMAPbI4 is demonstrated as an effective methylammonium (MA) cation locker to stabilize MAPbI3 by steric effect of the phenyltrimethylammonium (PTA) cation. This MA cation locked MAPbI3 based perovskite exhibited significantly enhanced stability and photovoltaic performance. Abstract The reduced dimension perovskite including 2D perovskites are one of the most promising strategies to stabilize lead halide perovskite. A mixed‐cation 2D perovskite based on a steric phenyltrimethylammonium (PTA) cation is presented. The PTA‐MA mixed‐cation 2D perovskite of PTAMAPbI4 can be formed on the surface of MAPbI3 (PTAI‐MAPbI3) by controllable PTAI intercalation by either spin coating or soaking. The PTAMAPbI4 capping layer can not only passivate PTAI‐MAPbI3 perovskite but also act as MA+ locker to inhibit MAI extraction and significantly enhance the stability. The highly stable PTAI‐MAPbI3 based perovskite solar cells exhibit a reproducible photovoltaic performance with a champion PCE of 21.16 %. Such unencapsulated devices retain 93 % of initial efficiency after 500 h continuous illumination. This steric mixed‐cation 2D perovskite as MA+ locker to stabilize the MAPbI3 is a promising strategy to design stable and high‐performance hybrid lead halide perovskites.

Blocking the Hype‐Hypocrisy‐Falsification‐Fakery Pathway is Needed to Safeguard Science

By Henning Hopf, Stephen A. Matlin, Goverdhan Mehta, Alain Krief from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 04, 2019.

Hype in science is commonplace, compounded by the hypocrisy of those who engage in or tolerate it while disapproving of the consequences. These are first steps along a slippery slope of hype, hypocrisy, data falsification, and dissemination of fake science, encouraged by systemic drivers in the contemporary structure of the science establishment. Collective, concerted intervention is required to discourage entry to this dangerous pathway; chemists must play and active role. Abstract In chemistry and other sciences, hype has become commonplace, compounded by the hypocrisy of those who tolerate or encourage it while disapproving of the consequences. This reduces the credibility and trust upon which all science depends for support. Hype and hypocrisy are but first steps down a slippery slope towards falsification of results and dissemination of fake science. Systemic drivers in the contemporary structure of the science establishment encourage exaggeration and may lure the individual into further steps along the hype‐hypocrisy‐falsification‐fakery continuum. Collective, concerted intervention is required to effectively discourage entry to this dangerous pathway and to restore and protect the probity and reputation of the science system. Chemists must play and active role in this effort.

Beating Thermal Coarsening in Nanoporous Materials via High‐Entropy Design

By Soo‐Hyun Joo, Jae Wung Bae, Won‐Young Park, Yusuke Shimada, Takeshi Wada, Hyoung Seop Kim, Akira Takeuchi, Toyohiko J. Konno, Hidemi Kato, Ilya V. Okulov from Wiley: Advanced Materials: Table of Contents. Published on Dec 04, 2019.

A novel high‐entropy design strategy for the synthesis of solid‐solution nanoporous materials with exceptional thermal stability at elevated temperatures is pioneered. Multiprincipal element alloying overcomes the universial relationship of coarsening via suppressed surface diffusion, and the preservation of size‐related physical properties is the key benefit of high‐entropy design. Abstract Controlling the feature sizes of 3D bicontinuous nanoporous (3DNP) materials is essential for their advanced applications in catalysis, sensing, energy systems, etc., requiring high specific surface area. However, the intrinsic coarsening of nanoporous materials naturally reduces their surface energy leading to the deterioration of physical properties over time, even at ambient temperatures. A novel 3DNP material beating the universal relationship of thermal coarsening is reported via high‐entropy alloy (HEA) design. In newly developed TiVNbMoTa 3DNP HEAs, the nanoporous structure is constructed by very fine nanoscale ligaments of a solid‐solution phase due to enhanced phase stability by maximizing the configuration entropy and suppressed surface diffusion. The smallest size of 3DNP HEA synthesized at 873 K is about 10 nm, which is one order of magnitude smaller than that of conventional porous materials. More importantly, the yield strength of ligament in 3DNP HEA approaches its theoretical strength of G/2π of the corresponding HEA alloy even after thermal exposure. This finding signifies the key benefit of high‐entropy design in nanoporous materials—exceptional stability of size‐related physical properties. This high‐entropy strategy should thus open new opportunities for developing ultrastable nanomaterials against its environment.

Expanding the Toolbox of Metal–Phenolic Networks via Enzyme‐Mediated Assembly

By Qi‐Zhi Zhong, Joseph J. Richardson, Shiyao Li, Wenjie Zhang, Yi Ju, Jianhua Li, Shuaijun Pan, Jingqu Chen, Frank Caruso from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 04, 2019.

The toolbox of metal–phenolic networks is expanded by enzyme‐mediated assembly, where a range of monophenols are converted into catechol‐containing molecules and cross‐linked by metal ions. This strategy preserves functionality of the monophenol precursors, while conferring benefits of catechol‐containing molecules (e.g., universal adhesion) to the networks. Abstract Functional coatings are of considerable interest because of their fundamental implications for interfacial assembly and promise for numerous applications. Universally adherent materials have recently emerged as versatile functional coatings; however, such coatings are generally limited to catechol, (ortho‐diphenol)‐containing molecules, as building blocks. Here, we report a facile, biofriendly enzyme‐mediated strategy for assembling a wide range of molecules (e.g., 14 representative molecules in this study) that do not natively have catechol moieties, including small molecules, peptides, and proteins, on various surfaces, while preserving the molecule's inherent function, such as catalysis (≈80 % retention of enzymatic activity for trypsin). Assembly is achieved by in situ conversion of monophenols into catechols via tyrosinase, where films form on surfaces via covalent and coordination cross‐linking. The resulting coatings are robust, functional (e.g., in protective coatings, biological imaging, and enzymatic catalysis), and versatile for diverse secondary surface‐confined reactions (e.g., biomineralization, metal ion chelation, and N‐hydroxysuccinimide conjugation).

Halide Anion Triggered Reactions of Michael Acceptors with Tropylium Ion

By Mohanad A. Hussein, Uyen P. N. Tran, Vien T. Huynh, Junming Ho, Mohan Bhadbhade, Herbert Mayr, Thanh V. Nguyen from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 04, 2019.

The tropylium ion adds to electron‐deficient olefins in a new reaction triggered by halide ions. Tropylium bromide undergoes noncatalyzed, regioselective additions to a large variety of Michael acceptors, converting acrylic esters into β‐bromo‐α‐cycloheptatrienylpropionic esters. Quantum chemical calculations elucidated the analogy to the amine‐ or phosphine‐catalyzed Morita–Baylis–Hillman and Rauhut–Currier reactions. Abstract Tropylium bromide undergoes noncatalyzed, regioselective additions to a large variety of Michael acceptors. In this way, acrylic esters are converted into β‐bromo‐α‐cycloheptatrienylpropionic esters. The reactions are interpreted as nucleophilic attack of bromide ions at the electron‐deficient olefins and the approach of the tropylium ion to the incipient carbanion. Quantum chemical calculations were performed to elucidate the analogy to the amine‐ or phosphine‐catalyzed Rauhut–Currier reactions. Subsequent synthetic transformations of the bromo‐cycloheptatrienylated adducts are reported.

Acyclic Branched α‐Fluoroketones for the Direct Asymmetric Mannich Reaction; Access to β‐Fluoro Amines Bearing Tetrasubstituted Fluorine Stereocenters.

By Barry M. Trost, Jacob S. Tracy, Tas Yusoontorn, Chao-I Hung from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 04, 2019.

The preparation of acyclic β‐fluoro amines bearing tetrasubstituted fluorine stereocenters is described via a direct Zn/ProPhenol‐catalyzed Mannich reaction. The reaction utilizes branched vinyl or alkynyl α‐fluoroketones that can be coupled with a range of aryl, heteroaryl, vinyl or cyclopropyl aldimines in high yield and with excellent diastereo‐ (up to >20:1) and enantioselectivity (up to 99%). The use of readily cleaved tert‐butoxycarbonyl (Boc) or carboxy benzyl (Cbz) imine protecting groups adds utility to the reaction by allowing for easy access to the free amine products under mild and chemoselective reaction conditions.

The Mutation of the “Nobel Prize in Chemistry” into the “Nobel Prize in Chemistry or Life Sciences”:  Several Decades of Transparent and Opaque Evidence of Change within the Nobel Prize Program

By Jeffrey Ira Seeman, Guillermo Restrepo from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 04, 2019.

Over the past several decades, the Nobel Prize program has slowly but steadily been modified in both transparent and opaque ways.  A transparent change has been the creation of the Nobel Prize in Economic Sciences, more officially known as the Sveriges Riksbank Prize in Economic Sciences in Memory of Alfred Nobel.  An opaque change has been the mutation of the Nobel Prize in Chemistry into what is effectively the “Nobel Prize in Chemistry or Life Sciences.”  This paper presents a detailed study of this opaque change, including evidence that the disciplines of chemistry and biochemistry cover, today, intellectually quite distinct and generally scientifically unrelated intellectual territory.  This paper supports the evolution of the Nobel Prizes, and encourages the Nobel Prize program to move from opaque to transparent change processes for the next generations of achievement in the sciences.

Formation of Short Zn‐Zn Bonds Stabilized by Simple Cyanide and Isocyanide Ligands

By Lester Andrews, Han-Gook Cho from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 04, 2019.

: Cyanogen diluted in argon was reacted with laser ablated Zn atoms to produce the ZnCN, NCZnCN and NCZnZnCN cyanides and their higher energy isocyanide counterparts ZnNC, CNZnNC and CNZnZnNC, which were isolated in excess argon at 4 K. These reaction products, identified from the matrix infrared spectra of their –CN and –NC chromophore ligand stretching modes, were confirmed by 13C and 15N isotopic substitution and comparison with frequencies calculated by the B3LYP and CCSD(T) methods using the all electron aug‐cc‐pVTZ basis sets. The cyanide and isocyanide products were increased markedly by mercury arc UV photolysis, which matches the zinc atomic absorption. The observed cyanide and dicyanide product frequencies were separated by 87.8, 103.5 and 101.3 cm‐1, respectively. The above electronic structure calculations that produce appropriate ligand frequencies for these dizinc products also provide their Zn‐Zn bond lengths: formed through annealing and characterized by CCSD(T) calculations find a short 2.367 Å Zn‐Zn bond in the NCZnZnCN cyanide, a short 2.347 Å Zn‐Zn bond in the 37.4 kJ/mol higher energy isocyanide CNZnZnNC, and a longer 4.024 Å bond in the dizinc van der Waals dimer. Thus the diatomic cyanide (‐CN) and isocyanide (‐NC) ligands are as capable of stabilizing the Zn‐Zn bond as many much larger ligands based on their measured and our calculated Zn‐Zn bond lengths. This is the first example of dizinc complexes stabilized by different ligand isomers. Additional weaker bands in this region can be assigned to the analogous trizinc molecules NCZnZnZnCN and CNZnZnZnNC.

Yttrium‐86 Is a Positron Emitting Surrogate of Gadolinium for Noninvasive Quantification of Whole‐Body Distribution of Gadolinium‐Based Contrast Agents

By Mariane Le Fur, Nicholas J. Rotile, Carlos Correcher, Veronica Clavijo Jordan, Alana W. Ross, Ciprian Catana, Peter Caravan from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 04, 2019.

Yttrium‐86 PET imaging can inform on the clearance and biodistribution of the gadolinium‐based contrast agents used in MRI. Trace amounts of contrast agent can be detected in kidney 48 h post injection in rodents. Abstract Gadolinium‐based contrast agents (GBCAs) are used to provide diagnostic information in clinical magnetic resonance (MR) examinations. Gadolinium (Gd) has been detected in the brain, bone and skin of patients, months and years following GBCA administration, raising concerns about long term toxicity. Despite increased scrutiny, the concentration, chemical form and fate of the retained gadolinium species remain unknown. Importantly, the whole body biodistribution and organ clearance of GBCAs is poorly understood in humans. Gadolinium lacks suitable isotopes for nuclear imaging. We demonstrate that the yttrium‐86 isotope can be used as a gadolinium surrogate. We show that Gd and their analogous Y complexes have similar properties both in solution and in vivo, and that yttrium‐86 PET can be used to track the biodistribution of GBCAs over a two‐day period.

Online Monitoring of Electrochemical Carbon Corrosion in Alkaline Electrolytes by Differential Electrochemical Mass Spectrometry

By Sandra Möller, Stefan Barwe, Justus Masa, Daniela Wintrich, Sabine Seisel, Helmut Baltruschat, Wolfgang Schuhmann from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 04, 2019.

Caught in the act: Direct detection of CO2 as a marker for carbon oxidation in alkaline electrolytes is now possible using a novel DEMS cell (DEMS=differential electrochemical mass spectrometry) and a specially designed experimental procedure. A high oxygen evolution reaction (OER) catalyst loading on carbon suppresses carbon corrosion in alkaline media. Abstract Carbon corrosion at high anodic potentials is a major source of instability, especially in acidic electrolytes and impairs the long‐term functionality of electrodes. In‐depth investigation of carbon corrosion in alkaline environment by means of differential electrochemical mass spectrometry (DEMS) is prevented by the conversion of CO2 into CO32−. We report the adaptation of a DEMS system for online CO2 detection as the product of carbon corrosion in alkaline electrolytes. A new cell design allows for in situ acidification of the electrolyte to release initially dissolved CO32− as CO2 in front of the DEMS membrane and its subsequent detection by mass spectrometry. DEMS studies of a carbon‐supported nickel boride (NixB/C) catalyst and Vulcan XC 72 at high anodic potentials suggest protection of carbon in the presence of highly active oxygen evolution electrocatalysts. Most importantly, carbon corrosion is decreased in alkaline solution.

Selective Synthesis of Conjugated Chiral Macrocycles: Sidewall Segments of (−)/(+)‐(12,4) Carbon Nanotubes with Strong Circularly Polarized Luminescence

By Jinyi Wang, Guilin Zhuang, Muqing Chen, Dapeng Lu, Zhe Li, Qiang Huang, Hongxing Jia, Shengsheng Cui, Xiang Shao, Shangfeng Yang, Pingwu Du from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 04, 2019.

Segments: For the first time, two chiral conjugated macrocycles ([4]CAn2,6), as (−)/(+)‐(12,4) carbon nanotube segments, are synthesized and the physical properties studied. The hoop‐shaped molecules can be directly viewed by an STM technique. Chiral enantiomers with (−)/(+) helicity of the [4]CAn2,6 were successfully isolated. These new tubular chiral carbon nanotube segments exhibit strong circularly polarized luminescence (glum≈0.1). Abstract Carbon nanotubes (CNTs) have unusual physical properties that are valuable for nanotechnology and electronics, but the chemical synthesis of chirality‐ and diameter‐specific CNTs and π‐conjugated CNT segments is still a great challenge. Reported here are the selective syntheses, isolations, characterizations, and photophysical properties of two novel chiral conjugated macrocycles ([4]cyclo‐2,6‐anthracene; [4]CAn2,6), as (−)/(+)‐(12,4) carbon nanotube segments. These conjugated macrocyclic molecules were obtained using a bottom‐up assembly approach and subsequent reductive elimination reaction. The hoop‐shaped molecules can be directly viewed by a STM technique. In addition, chiral enantiomers with (−)/(+) helicity of the [4]CAn2,6 were successfully isolated by HPLC. The new tubular CNT segments exhibit large absorption and photoluminescence redshifts compared to the monomer unit. The carbon enantiomers are also observed to show strong circularly polarized luminescence (glum≈0.1). The results reported here expand the scope of materials design for bottom‐up synthesis of chiral macrocycles and enrich existing knowledge of their optoelectronic properties.

Difunctionalization of Alkenes Involving Metal Migration

By Yuqiang Li, Dong Wu, Hong-Gang Cheng, Guoyin Yin from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 04, 2019.

The direct difunctionalization of alkenes, a cheap and abundant feedstock, represents one of the most attractive strategies to greatly increase the molecular complexity in synthetic organic chemistry. In contrast with the 1,2‐difunctionalization of alkenes, recent advances showcase that alkene 1,n‐difunctionalizations (n ≠ 2) involving metal migration is an emerging and rapidly growing area of research. This promising strategy not only opens a novel avenue for future development of alkene transformations, but also significantly renovates the bond disconnections available in modern organic synthesis. In this Minireview, we summarize the recent progress in the migratory difunctionalization of alkenes, with an emphasis on the driving force for metal migration.The direct difunctionalization of alkenes, a cheap and abundant feedstock, represents one of the most attractive strategies to greatly increase molecular complexity in synthetic organic chemistry. In contrast with 1,2‐difunctionalization of alkenes, recent advances showcase that alkene 1,n‐difunctionalizations (n ≠ 2) involving metal migration is an emerging and rapidly growing area of research. This promising strategy not only opens a novel avenue for future development of alkene transformations, but also significantly renovates the bond disconnections available in modern organic synthesis. In this Minireview, we summarize recent progress in the migratory difunctionalization of alkenes, with an emphasis on the driving force for metal migration.

Injury‐Triggered Blueing Reactions of Psilocybe “Magic” Mushrooms

By Claudius Lenz, Jonas Wick, Daniel Braga, María García‐Altares, Gerald Lackner, Christian Hertweck, Markus Gressler, Dirk Hoffmeister from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 04, 2019.

Magic mushroom blues: Hallucinogenic Psilocybe mushrooms turn blue when injured. We report that the phosphatase PsiP and the laccase PsiL degrade psilocybin and initiate blueing. MALDI‐MS and in situ NMR spectroscopy show that the blue color is due to a mixture of quinoid psilocyl oligomers, primarily coupled via carbon 5. Abstract Upon injury, psychotropic psilocybin‐producing mushrooms instantly develop an intense blue color, the chemical basis and mode of formation of which has remained elusive. We report two enzymes from Psilocybe cubensis that carry out a two‐step cascade to prepare psilocybin for oxidative oligomerization that leads to blue products. The phosphatase PsiP removes the 4‐O‐phosphate group to yield psilocin, while PsiL oxidizes its 4‐hydroxy group. The PsiL reaction was monitored by in situ 13C NMR spectroscopy, which indicated that oxidative coupling of psilocyl residues occurs primarily via C‐5. MS and IR spectroscopy indicated the formation of a heterogeneous mixture of preferentially psilocyl 3‐ to 13‐mers and suggest multiple oligomerization routes, depending on oxidative power and substrate concentration. The results also imply that phosphate ester of psilocybin serves a reversible protective function.

Tunable Thermoelastic Anisotropy in Hybrid Bragg Stacks with Extreme Polymer Confinement

By Zuyuan Wang, Konrad Rolle, Theresa Schilling, Patrick Hummel, Alexandra Philipp, Bernd A. F. Kopera, Anna M. Lechner, Markus Retsch, Josef Breu, George Fytas from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 04, 2019.

Hybrid Bragg stacks, consisting of alternating hectorite and polyvinylpyrrolidone layers, are fabricated with angstrom precision. By controlling the sample composition, tunable mechanical and thermal anisotropy ratios, up to 7 and 38 respectively, are achieved. Abstract Controlling thermomechanical anisotropy is important for emerging heat management applications such as thermal interface and electronic packaging materials. Whereas many studies report on thermal transport in anisotropic nanocomposite materials, a fundamental understanding of the interplay between mechanical and thermal properties is missing, due to the lack of measurements of direction‐dependent mechanical properties. In this work, exceptionally coherent and transparent hybrid Bragg stacks made of strictly alternating mica‐type nanosheets (synthetic hectorite) and polymer layers (polyvinylpyrrolidone) were fabricated at large scale. Distinct from ordinary nanocomposites, these stacks display long‐range periodicity, which is tunable down to angstrom precision. A large thermal transport anisotropy (up to 38) is consequently observed, with the high in‐plane thermal conductivity (up to 5.7 W m−1 K−1) exhibiting an effective medium behavior. The unique hybrid material combined with advanced characterization techniques allows correlating the full elastic tensors to the direction‐dependent thermal conductivities. We, therefore, provide a first analysis on how the direction‐dependent Young's and shear moduli influence the flow of heat.

Structure Selectivity of Alkaline Periodate Oxidation on Lignocellulose for Facile Isolation of Cellulose Nanocrystals

By Peiwen Liu, Bo Pang, Sebastian Dechert, Xizhou Cecily Zhang, Loren B Andreas, Steffen Fischer, Franc Meyer, Kai Zhang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 04, 2019.

Structure based: A novel method based on a recyclable and newly selective alkaline periodate oxidation at pH 10 provides a sustainable strategy for the efficient isolation of cellulose nanocrystals (CNCs) from various lignocellulosic materials. The isolation the CNCs results from the structural differences between the ordered and non‐ordered regions of the lignocellulose. Abstract Reported here for the first time is the alkaline periodate oxidation of lignocelluloses for the selective isolation of cellulose nanocrystals (CNCs). With the high concentrations as a potassium salt at pH 10, periodate ions predominantly exist as dimeric orthoperiodate ions (H2I2O104−). With reduced oxidizing activity in alkaline solutions, dimeric orthoperiodate ions preferentially oxidized non‐ordered cellulose regions. The alkaline surroundings promoted the degradation of these oxidized cellulose chains by β‐alkoxy fragmentation and generated CNCs. The obtained CNCs were uniform in size and generally contained carboxy groups. Furthermore, the reaction solution could be reused after regeneration of the periodate with ozone gas. This method allows direct production of CNCs from diverse sources, in particular lignocellulosic raw materials including sawdust (European beech and Scots pine), flax, and kenaf, in addition to microcrystalline cellulose and pulp.

N‐Confused Phlorin‐Prodigiosin Chimera: meso‐Aryl Oxidation and π‐Extension Triggered by Peripheral Coordination

By Guangxian Su, Qizhao Li, Masatoshi Ishida, Chengjie Li, Feng Sha, Xin‐Yan Wu, Lu Wang, Glib Baryshnikov, Dawei Li, Hans Ågren, Hiroyuki Furuta, Yongshu Xie from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 04, 2019.

On the periphery: Peripheral coordination of PdII and BF2 with N‐confused phlorin‐prodigiosin chimera triggered unique reactions in the presence of triethylamine (TEA). In the case of PdII, the meso‐phenyl group undergoes oxidation and in the case of BF2, there is π extension through a N,N‐diethylaminovinyl group. Abstract An N‐confused phlorin isomer bearing a dipyrrin moiety at the α‐position of the confused pyrrole ring (1) was synthesized. PdII and BIII coordination at the peripheral prodigiosin‐like moiety of 1 afforded the corresponding complexes 2 and 3. Reflux of 2 in triethylamine (TEA) converted the meso‐phenyl into the PdII‐coordinating phenoxy group to afford 4. Under the same reaction conditions, TEA was linked to the α‐position of the dipyrrin unit in 3 as an N,N‐diethylaminovinyl group to afford 5. Furthermore, peripheral coordination of BIII in 3 and 5 improved the planarity of the phlorin macrocycle and thus facilitated the coordination of AgIII at the inner cavity to afford 3‐Ag and 5‐Ag, respectively. These results provide an effective approach for developing unique porphyrinoids through peripheral coordination.

Understanding the Role of Internal Diffusion Barriers in Pt/Beta Zeolite Catalyzed Isomerization of n‐Heptane

By Zhongyuan Guo, Xin Li, Shen Hu, Guanghua Ye, Xinggui Zhou, Marc‐Olivier Coppens from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 04, 2019.

Diffusion barriers on interfaces: There exist very strong internal diffusion barriers in Beta zeolites, which subsequently reduce their activity and selectivity in catalysing the isomerization of n‐heptane. The Beta zeolite with no observable internal interfaces (see picture) can be 180 % higher in activity and 22 % higher in selectivity. Abstract Applications of zeolites in catalysis are plagued by strong diffusion resistance, which results from limitations to molecular transport in micropores, across external crystal surfaces, but also across internal interfaces. The first type of diffusion resistance is well understood, the second is receiving increasing attention, while the diffusion barriers at internal interfaces remain largely unclear. We take Pt/Beta catalyzed isomerization of n‐heptane as the model system to explore the role of internal diffusion barriers in zeolite catalysis. The two as‐synthesized Pt/Beta catalysts have an identical Pt loading, similar Beta particle size and acidity, but different internal structures. A Pt/Beta crystal with no observable internal interfaces can be 180 % higher in activity and 22 % higher in selectivity than its counterpart with numerous internal interfaces. This can only be attributed to the strong transport barriers across internal interfaces, as supported by directly comparing the apparent diffusivities of the two Beta samples.

Flexible Total Synthesis of 11‐Deoxylandomycins and Their Non‐Natural Analogues by Way of Asymmetric Metal Catalysis

By Juyeol Lee, Jihun Kang, Sukhyun Lee, Young Ho Rhee from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 04, 2019.

A collective total synthesis of 11‐ deoxylandomycins is reported using Pd‐catalyzed asymmetric hydroalkoxylation of alkoxyallene as the key strategy. This de novo approach allowed for an access to various natural and non‐natural congeners of 11‐deoxylandomycins. Abstract A de novo first collective total synthesis of 11‐deoxylandomycins is reported. A signature step is featured by the Pd‐catalyzed asymmetric addition of alcohol to ene‐alkoxyallenes that assembles oligomeric 2,3,6‐trideoxyoligosaccharides. The unique feature of the protocol is illustrated by a flexible access to various natural 11‐deoxylandomycins as well as non‐natural analogues.

On‐Surface Synthesis and Characterization of Triply Fused Porphyrin–Graphene Nanoribbon Hybrids

By Luis M. Mateo, Qiang Sun, Shi‐Xia Liu, Jesse J. Bergkamp, Kristjan Eimre, Carlo A. Pignedoli, Pascal Ruffieux, Silvio Decurtins, Giovanni Bottari, Roman Fasel, Tomas Torres from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 04, 2019.

Made on the surface: A porphyrin–graphene nanoribbon hybrid is prepared by selective on‐surface synthesis. The atomically precise structure of the hybrid is characterized by bond‐resolved scanning tunneling microscopy and noncontact atomic force microscopy. Scanning tunneling spectroscopy (STS), in combination with DFT calculations, reveals a low electronic gap of 0.4 eV. Abstract On‐surface synthesis offers a versatile approach to prepare novel carbon‐based nanostructures that cannot be obtained by conventional solution chemistry. Graphene nanoribbons (GNRs) have potential for a variety of applications. A key issue for their application in molecular electronics is in the fine‐tuning of their electronic properties through structural modifications, such as heteroatom doping or the incorporation of non‐benzenoid rings. In this context, the covalent fusion of GNRs and porphyrins (Pors) is a highly appealing strategy. Herein we present the selective on‐surface synthesis of a Por–GNR hybrid, which consists of two Pors connected by a short GNR segment. The atomically precise structure of the Por–GNR hybrid has been characterized by bond‐resolved scanning tunneling microscopy (STM) and noncontact atomic force microscopy (nc‐AFM). The electronic properties have been investigated by scanning tunneling spectroscopy (STS), in combination with DFT calculations, which reveals a low electronic gap of 0.4 eV.

A Unified Total Synthesis of the Actinoallolides, a Family of Potent Anti‐Trypanosomal Macrolides

By Matthew J. Anketell, Theodore M. Sharrock, Ian Paterson from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 04, 2019.

The first total synthesis of the potent anti‐trypanosomal macrolides (+)‐actinoallolides A–E has been achieved using the stereocontrolled aldol reactions of three chiral ketone building blocks. Trypanosoma parasites cause two key neglected tropical diseases, currently affecting over 8 million people. This convergent strategy features a challenging “do or die” ring‐closing metathesis to form the trisubstituted macrocyclic (8E)‐alkene. Abstract Trypanosoma protozoan parasites are the causative agents of Chagas disease and sleeping sickness, two neglected tropical diseases where there is an urgent need for improved treatments and the evaluation of promising drug leads like the actinoallolides. Enabled by the highly stereocontrolled aldol reactions of three chiral ketone building blocks, an efficient first total synthesis of the potent anti‐trypanosomal macrolide (+)‐actinoallolide A has been achieved in 17 steps and 8 % overall yield. Our convergent route features an adventurous ring‐closing metathesis to form the requisite trisubstituted (8E)‐alkene in the 12‐membered macrolactone, followed by the controlled installation of the labile transannular hemiacetal. Late‐stage diversification then provides ready access to the congeneric (+)‐actinoallolides B–E.

Tue 18 Feb 14:00: Title to be confirmed

From All Talks (aka the CURE list). Published on Dec 04, 2019.

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Synthesis of 2D ultralarge protein supramolecular nanofilm by chemoselective thiol‐disulfide exchange and emergent functions

By Yan Xu, Yongchun Liu, Xinyi Hu, Rongrong Qin, Hao Su, Juling Li, Peng Yang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 04, 2019.

The design and scalable synthesis of robust 2D biological ultrathin films with a tunable structure and function and the ability to be easily transferred to a virtually arbitrary substrate remain key challenges in chemistry and materials science. Here, we implicate the potential of the thiol‐disulfide exchange reaction in the synthesis of a macroscopic 2D ultrathin proteinaceous film with the potential for scaled‐up fabrication and on‐demand encapsulation/release of functional molecules. The synthesis success is determined by the chemoselectivity and site‐specificity of the reaction between the Cys6‐Cys127 disulfide bond of native lysozyme and cysteine, as supported by the superior redox potential of the Cys6‐Cys127 disulfide bond over that of other disulfide bonds in native lysozyme and other unreactive proteins. The partially unfolded lysozyme‐cysteine conjugate monomers are formed by this strategy, which then further aggregate at the air/water or solid/liquid interface to form an ultralarge 2D nanofilm (e.g., 900 cm 2 ) with ~100% optical transparency. On the basis of amyloid‐like aggregation inside the nanofilm, this material presents robust adhesion onto a virtually arbitrary substrate and on‐demand controllability to mediate the encapsulation and release of small, mid‐sized and large molecules without significant activity loss upon the surface immobilization of active proteins. Our approach provides an important application for the thiol‐disulfide exchange reaction in the biocompatible large‐scale preparation of 2D proteinaceous nanofilms and coatings with the capability of tunable functional molecular block encapsulation and release.

Visible Light‐Driven Halogen Bond Donor Based Molecular Switches: From Reversible Unwinding to Handedness Inversion in Self‐Organized Soft Helical Superstructures

By Hao Wang, Hari Krishna Bisoyi, Bing-Xiang Li, Michael McConney, Timothy Bunning, Quan Li from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 04, 2019.

Visible light‐driven molecular switches endowing reversible modulation of the functionalities of self‐organized soft materials are currently highly sought after for fundamental scientific studies and technological applications. Herein, we report the design and synthesis of two novel halogen bond donor chiral molecular switches that are able to exhibit reversible photoisomerization upon exposure to visible light of different wavelengths. These halogen bond donor based chiral molecular switches induce photoresponsive helical superstructures, i.e., cholesteric liquid crystals, when doped into the commercially available room temperature achiral liquid crystal host 5CB which also acts as a halogen bond acceptor. The induced helical superstructure containing the molecular switch with terminal iodo atoms exhibits visible light‐driven reversible unwinding, i.e., a cholesteric‐nematic phase transition. Interestingly, the molecular switch with terminal bromo atoms confers reversible handedness inversion to the helical superstructure upon irradiation with visible light of different wavelengths. This visible light‐driven reversible handedness inversion, enabled by halogen bond donor molecular switch, is unprecedented. These halogen bond donor chiral molecular switches would inspire the development of visible light‐driven advanced photonic materials based on specific molecular interactions and beyond.

Synthesis of Biaryl‐Bridged Cyclic Peptides via Catalytic Oxidative Cross‐Coupling Reactions

By Mor Ben-Lulu, Eden Gaster, Anna Libman, Doron Pappo from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 04, 2019.

Biaryl‐bridged cyclic peptides comprise an intriguing class of structurally diverse natural products with significant biological activity. Especially noteworthy are the antibiotics arylomycin and its synthetic analog G0775, which exhibits potent activity against Gram‐negative bacteria. Here, we present a simple, flexible, and reliable strategy based on activating group‐assisted catalytic oxidative coupling for assembling biaryl‐bridged cyclic peptides from natural amino acids. The synthetic approach was utilized for preparing a number of natural and unnatural biaryl‐bridged cyclic peptides, including arylomycin/G0775 and RP 66453 cyclic cores.

Aqueous Phase Visible‐Light‐Excited Organic Room‐Temperature Phosphorescence via Cucurbit[8]uril‐Mediated Supramolecular Assembling

By Jie Wang, Zizhao Huang, Xiang Ma, He Tian from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 04, 2019.

Solid state materials with efficient room‐temperature phosphorescence (RTP) emissions have found widespread applications in material science, while liquid or solution‐phase pure organic RTP emission system has been rarely reported due to the non‐radiative decay and quenchers from the liquid medium. Herein we propose the first example of visible‐light excited pure organic RTP in aqueous solution via a supramolecular host‐guest assembling strategy. The unique cucurbit[8]uril‐mediated quaternary stacking structure allows tunable photoluminescence and visible‐light excitation, enabling the fabrication of multi‐color hydrogels and cell imaging. The present “assembling‐induced emission” approach, as a proof of concept, contributes to the construction of novel metal‐free RTP system with tunable photoluminescence in aqueous solution, providing broad opportunities for further applications in biological imaging, detection, optical sensors and so forth.

On the Influence of Oxygen On the Degradation of Fe‐N‐C Catalysts

By Kavita Kumar, Laetitia Dubau, Michel Mermoux, Jingkun Li, Andrea Zitolo, Jaysen Nelayah, Frederic Jaouen, Frederic Maillard from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 04, 2019.

Precious metal‐free catalysts for oxygen reduction reaction (ORR) in proton exchange membrane fuel cells are gaining momentum, with Fe‐N‐C catalysts comprising atomic FeN x sites the most promising candidate. Research and development is shifting from activity targets to improved durability in fuel cells of Fe‐N‐C catalysts. Their durability has been extensively studied using accelerated stress tests (AST) performed at room temperature and in inert‐gas saturated acidic pH electrolyte. Here, we reveal stronger degradation of the Fe‐N‐C structure and four times higher ORR activity loss when performing load cycling AST in O 2 ‐ vs. Ar‐saturated pH 1 electrolyte. Raman spectroscopy results point towards strong carbon corrosion after AST in O 2 , even when cycling at low potentials of 0.3‐0.7 V vs. the reversible hydrogen electrode, while no corrosion occurred after any load cycling AST in Ar. The load cycling AST in O 2 leads to the loss of a significant fraction of FeN x sites, as shown by energy dispersive X‐ray spectroscopy analyses, and to the formation of Fe‐oxides. The results support that the unexpected carbon corrosion occurring at such low potential in the presence of O 2 is due to reactive oxygen species produced between H 2 O 2 and Fe sites via Fenton reactions.

Rhodium‐Catalyzed Remote C(sp3)−H Borylation of Silyl Enol Ethers Jie Li, Shuanglin Qu, and Wanxiang Zhao*

By Jie Li, Shuanglin Qu, Wanxiang Zhao from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 04, 2019.

A rhodium‐catalyzed remote C(sp3)−H borylation of silyl enol ethers (SEEs, E/Z mixtures) via alkene isomerization and hydroboration is reported. The reaction exhibits mild reaction conditions and excellent functional group tolerance. This method is compatible with an array of SEEs, including linear and branched SEEs derived from aldehyde and ketone, and provide direct access to a broad range of structurally diverse 1,n‐borylethers in excellent regioselectivity and good yields, which are precursors to various valuable chemicals, such as 1,n‐diols and aminoalcohols.

Unravelling the Synergy between Oxygen Vacancy and Oxygen Substitution in BiO2‐x for Efficient Molecular Oxygen Activation

By Yueshuang Mao, Pengfei Wang, Lina Li, Zongwei Chen, Haitao Wang, Yi Li, Sihui Zhan from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 04, 2019.

Defects are ubiquitous in nanomaterials, which often bring new properties that are absent in their pristine counterparts. To date, most studies have focused on the effect of single defect while ignoring the synergy (electronic or other effect) of multifold defects. Herein, a model of photocatalytic molecular oxygen (O2 ) activation is selected to unravel the role of dual defects by decorating bismuth oxide with surface O vacancy and bulk O substitution simultaneously. Results show that introducing dual defects plays a spatial and electronic synergistic process: (i) the O substitution can induce a local electric field in the bulk of BiO2‐x , which can promote bulk separation of electrons and holes immediately after their generation; (ii) the O vacancy can efficiently lower the conduction band, serve as the capture center for electrons, thus facilitate the adsorption and activation of O2 . Notably, this effect is greatly promoted by the co‐existence of bulk O substitution, and DFT calculations show that only O substitution nearby O vacancy can play this role. This work is expected to inspire more brilliant studies on the versatility of defects engineering in various fields.

Thu 26 Mar 14:00: TBD

From All Talks (aka the CURE list). Published on Dec 04, 2019.

TBD

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Thu 02 Apr 14:00: TBD

From All Talks (aka the CURE list). Published on Dec 04, 2019.

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Thu 05 Mar 12:30: Title to be confirmed

From All Talks (aka the CURE list). Published on Dec 04, 2019.

Title to be confirmed

Abstract not available

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Thu 20 Feb 12:30: Title to be confirmed

From All Talks (aka the CURE list). Published on Dec 04, 2019.

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Thu 06 Feb 13:00: Title to be confirmed

From All Talks (aka the CURE list). Published on Dec 04, 2019.

Title to be confirmed

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Thu 23 Jan 13:00: Bank Intermediation and Consumer Bankruptcy

From All Talks (aka the CURE list). Published on Dec 04, 2019.

Bank Intermediation and Consumer Bankruptcy

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A General Route to Fabricate Low‐ruthenium‐based Bimetals Electrocatalysts for pH‐universal Hydrogen Evolution Reaction via Carbon Quantum Dots

By Yuan Liu, Xue Li, Qinghua Zhang, Weidong Li, Yu Xie, Hanyu Liu, Lu Shang, Zhongyi Liu, Zhimin Chen, Lin Gu, Zhiyong Tang, Tierui Zhang, Siyu Lu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 04, 2019.

It is a challenging but pressing task to design and synthesize novel, efficient, and robust pH‐universal hydrogen evolution reaction (HER) electrocatalysts for scalable and sustainable hydrogen production through electrochemical water splitting. Here, we report a facile method to prepare an efficient and robust Ru–M (M=Ni, Mn, Cu) bimetal nanoparticle and carbon quantum dot hybrid (RuM/CQDs) for pH‐universal HER. As exemplified by RuNi/CQDs, the catalysts exhibit outstanding HER performance at all pH levels. The unexpected low overpotentials of 13, 58 and 18 mV shown by RuNi/CQDs allow a current density of 10 mA cm‐2 in 1 M KOH, 0.5 M H2SO4 and 1 M PBS, respectively, for Ru loading at 5.93 μgRu cm‐2. This performance is among the best catalytic activities reported for any platinum‐free electrocatalyst. RuMn/CQDs and RuCu/CQDs electrocatalysts also exhibit ideal performance. Theoretical calculations reveal the underlying mechanism, whereby Ni doping results in a moderate weakening of the hydrogen bonding energy of nearby surface Ru atoms, which plays a critical role in improving the HER intrinsic activity. It also improves the interconnective metal skeleton, facilitating electron transfer and leading to the superior HER performance. Thus, this study proposes a promising approach to the development of highly efficient bimetal/carbon hybrid compounds with advanced HER performance.

Red‐Carbon‐Quantum‐Dot‐Doped SnO2 Composite with Enhanced Electron Mobility for Efficient and Stable Perovskite Solar Cells

By Wei Hui, Yingguo Yang, Quan Xu, Hao Gu, Shanglei Feng, Zhenhuang Su, Miaoran Zhang, Jiaou Wang, Xiaodong Li, Junfeng Fang, Fei Xia, Yingdong Xia, Yonghua Chen, Xingyu Gao, Wei Huang from Wiley: Advanced Materials: Table of Contents. Published on Dec 04, 2019.

An effective composite electron transport layer (ETL) is fabricated using carboxylic‐acid‐ and hydroxyl‐rich red‐carbon quantum dots to dope low‐temperature solution‐processed SnO2. The electron mobility of SnO2 is dramatically increased by ≈20 times from 9.32 × 10−4 to 1.73 × 10−2 cm2 V−1 s−1. A planar perovskite solar cell based on this novel SnO2 ETL demonstrates an outstanding improvement in efficiency up to 22.77%. Abstract An efficient electron transport layer (ETL) plays a key role in promoting carrier separation and electron extraction in planar perovskite solar cells (PSCs). An effective composite ETL is fabricated using carboxylic‐acid‐ and hydroxyl‐rich red‐carbon quantum dots (RCQs) to dope low‐temperature solution‐processed SnO2, which dramatically increases its electron mobility by ≈20 times from 9.32 × 10−4 to 1.73 × 10−2 cm2 V−1 s−1. The mobility achieved is one of the highest reported electron mobilities for modified SnO2. Fabricated planar PSCs based on this novel SnO2 ETL demonstrate an outstanding improvement in efficiency from 19.15% for PSCs without RCQs up to 22.77% and have enhanced long‐term stability against humidity, preserving over 95% of the initial efficiency after 1000 h under 40–60% humidity at 25 °C. These significant achievements are solely attributed to the excellent electron mobility of the novel ETL, which is also proven to help the passivation of traps/defects at the ETL/perovskite interface and to promote the formation of highly crystallized perovskite, with an enhanced phase purity and uniformity over a large area. These results demonstrate that inexpensive RCQs are simple but excellent additives for producing efficient ETLs in stable high‐performance PSCs as well as other perovskite‐based optoelectronics.

Carbon Nanotubes Enabling Highly Efficient Cell Apoptosis by Low‐Intensity Nanosecond Electric Pulses via Perturbing Calcium Handling

By Zheng Mao, Youyu Zhang, Nan Lu, Shun Cheng, Ronghan Hong, Qing Huo Liu from Wiley: Small: Table of Contents. Published on Dec 04, 2019.

A physical method that combines carbon nanotubes with low intensity nanosecond electric pulses (nsEPs) is proposed for highly efficient cancer cell apoptosis induction. Mechanism research suggests that carbon nanotubes are able to amplify the electric field, enhancing the membrane permeabilization and intracellular effects induced by nsEPs, ultimately triggering mitochondrial signaling pathway‐mediated cell apoptosis by perturbing calcium handling. Abstract Effective induction of targeted cancer cells apoptosis with minimum side effects has always been the primary objective for anti‐tumor therapy. In this study, carbon nanotubes (CNTs) are employed for their unique ability to target tumors and amplify the localized electric field due to the high aspect ratio. Highly efficient and cancer cell specific apoptosis is finally achieved by combining carbon nanotubes with low intensity nanosecond electric pulses (nsEPs). The underlying mechanism may be as follows: the electric field produced by nsEPs is amplified by CNTs, causing an enhanced plasma membrane permeabilization and Ca2+ influx, simultaneously triggering Ca2+ release from intracellular storages to cytoplasm in a direct/indirect manner. All the changes above lead to excessive mitochondrial Ca2+ uptake. Substructural damage and obvious mitochondria membrane potential depolarization are caused subsequently with the combined action of numerously reactive oxygen species production, ultimately initiating the apoptotic process through the translocation of cytochrome c to the cytoplasm and activating apoptotic markers including caspase‐9 and ‐3. Thus, the combination of nanosecond electric field with carbon nanotubes can actually promote HCT116 cell death via mitochondrial signaling pathway‐mediated cell apoptosis. These results may provide a new and highly efficient strategy for cancer therapy.

A Bioinspired Nanoprobe with Multilevel Responsive T1‐Weighted MR Signal‐Amplification Illuminates Ultrasmall Metastases

By Yao Li, Xiao Zhao, Xiaoli Liu, Keman Cheng, Xuexiang Han, Yinlong Zhang, Huan Min, Guangna Liu, Junchao Xu, Jian Shi, Hao Qin, Haiming Fan, Lei Ren, Guangjun Nie from Wiley: Advanced Materials: Table of Contents. Published on Dec 04, 2019.

An ultrasensitive T1‐weighted magnetic resonance imaging contrast agent, UMFNP‐CREKA, is presented to accurately detect ultrasmall breast cancer metastases. UMFNP‐CREKA exhibits multilevel responsive T1 magnetic resonance (MR) signal‐amplification capacity in response to overall features of the metastasis microenvironment (mild acidity and elevated H2O2). As a result, UMFNP‐CREKA can detect metastases at an unprecedented minimum detection limit of 0.39 mm. Abstract Metastasis remains the major cause of death in cancer patients. Thus, there is a need to sensitively detect tumor metastasis, especially ultrasmall metastasis, for early diagnosis and precise treatment of cancer. Herein, an ultrasensitive T1‐weighted magnetic resonance imaging (MRI) contrast agent, UMFNP‐CREKA is reported. By conjugating the ultrasmall manganese ferrite nanoparticles (UMFNPs) with a tumor‐targeting penta‐peptide CREKA (Cys‐Arg‐Glu‐Lys‐Ala), ultrasmall breast cancer metastases are accurately detected. With a behavior similar to neutrophils' immunosurveillance process for eliminating foreign pathogens, UMFNP‐CREKA exhibits a chemotactic “targeting‐activation” capacity. UMFNP‐CREKA is recruited to the margin of tumor metastases by the binding of CREKA with fibrin‐fibronectin complexes, which are abundant around tumors, and then release of manganese ions (Mn2+) to the metastasis in response to pathological parameters (mild acidity and elevated H2O2). The localized release of Mn2+ and its interaction with proteins affects a marked amplification of T1‐weighted magnetic resonance (MR) signals. In vivo T1‐weighted MRI experiments reveal that UMFNP‐CREKA can detect metastases at an unprecedented minimum detection limit of 0.39 mm, which has significantly extended the detection limit of previously reported MRI probe.

Mon 09 Dec 18:30: Blood is thicker than water

From All Talks (aka the CURE list). Published on Dec 04, 2019.

Blood is thicker than water

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Thu 16 Jan 15:30: Talk title tbc

From All Talks (aka the CURE list). Published on Dec 04, 2019.

Talk title tbc

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Thu 30 Jan 15:30: Non invasive deep brain stimulation via temporally interfering electric fields

From All Talks (aka the CURE list). Published on Dec 04, 2019.

Non invasive deep brain stimulation via temporally interfering electric fields

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Thu 19 Mar 15:30: How do our brains form maps of the world?

From All Talks (aka the CURE list). Published on Dec 04, 2019.

How do our brains form maps of the world?

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Thu 12 Mar 15:30: Broca’s region: cytoarchitecture, transmitter receptors and brain mapping

From All Talks (aka the CURE list). Published on Dec 04, 2019.

Broca’s region: cytoarchitecture, transmitter receptors and brain mapping

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Thu 05 Mar 15:30: The interpersonal function of emotional expressions

From All Talks (aka the CURE list). Published on Dec 04, 2019.

The interpersonal function of emotional expressions

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Thu 27 Feb 15:30: The neural basis of flexible semantic retrieval

From All Talks (aka the CURE list). Published on Dec 04, 2019.

The neural basis of flexible semantic retrieval

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Thu 06 Feb 15:30: Attention, perception, and neural response: testing the limits

From All Talks (aka the CURE list). Published on Dec 04, 2019.

Attention, perception, and neural response: testing the limits

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Thu 23 Jan 15:30: Combining brain mapping with machine-learning on individual differences

From All Talks (aka the CURE list). Published on Dec 04, 2019.

Combining brain mapping with machine-learning on individual differences

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[ASAP] Metal/LiF/Li2O Nanocomposite for Battery Cathode Prelithiation: Trade-off between Capacity and Stability

By Junmou Du†, Wenyu Wang†, Alex Yong Sheng Eng‡, Xiaoxiao Liu†, Mintao Wan†, Zhi Wei Seh‡, and Yongming Sun*† from Nano Letters: Latest Articles (ACS Publications). Published on Dec 04, 2019.

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Nano Letters
DOI: 10.1021/acs.nanolett.9b04278

[ASAP] Near-Field Electrospinning for Three-Dimensional Stacked Nanoarchitectures with High Aspect Ratios

By Yang-Seok Park†‡?, Junyoung Kim†‡?, Jung Min Oh†‡?, Seungyoung Park§, Seungse Cho§, Hyunhyub Ko§, and Yoon-Kyoung Cho*†‡§ from Nano Letters: Latest Articles (ACS Publications). Published on Dec 04, 2019.

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Nano Letters
DOI: 10.1021/acs.nanolett.9b04162

[ASAP] Strongly Confined Excitons in GaN/AlN Nanostructures with Atomically Thin GaN Layers for Efficient Light Emission in Deep-Ultraviolet

By A. A. Toropov*†, E. A. Evropeitsev†, M. O. Nestoklon†, D. S. Smirnov†, T. V. Shubina†, V. Kh. Kaibyshev†, G. V. Budkin†, V. N. Jmerik†, D. V. Nechaev†, S. Rouvimov‡, S. V. Ivanov†, and B. Gil†§ from Nano Letters: Latest Articles (ACS Publications). Published on Dec 04, 2019.

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Nano Letters
DOI: 10.1021/acs.nanolett.9b03517

[ASAP] Fabrication and Imaging of Monolayer Phosphorene with Preferred Edge Configurations via Graphene-Assisted Layer-by-Layer Thinning

By Yangjin Lee†‡, Sol Lee†‡, Jun-Yeong Yoon†‡, Jinwoo Cheon‡§?, Hu Young Jeong*?, and Kwanpyo Kim*‡† from Nano Letters: Latest Articles (ACS Publications). Published on Dec 04, 2019.

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Nano Letters
DOI: 10.1021/acs.nanolett.9b04292

[ASAP] A Reconfigurable Remotely Epitaxial VO2 Electrical Heterostructure

By Yuwei Guo†?, Xin Sun‡?, Jie Jiang†§, Baiwei Wang†, Xinchun Chen?*, Xuan Yin?, Wei Qi?, Lei Gao?*, Lifu Zhang†, Zonghuan Lu‡, Ru Jia†, Saloni Pendse†, Yang Hu†‡, Zhizhong Chen†, Esther Wertz‡, Daniel Gall†, Jing Feng§, Toh-Ming Lu‡, and Jian Shi†#* from Nano Letters: Latest Articles (ACS Publications). Published on Dec 04, 2019.

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Nano Letters
DOI: 10.1021/acs.nanolett.9b02696

[ASAP] Reactive Oxygen Correlated Chemiluminescent Imaging of a Semiconducting Polymer Nanoplatform for Monitoring Chemodynamic Therapy

By Youjuan Wang†, Linan Shi†, Zhifei Ye†, Kesong Guan†, Lili Teng†, Jianghong Wu‡, Xia Yin†, Guosheng Song*†, and Xiao-Bing Zhang† from Nano Letters: Latest Articles (ACS Publications). Published on Dec 04, 2019.

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Nano Letters
DOI: 10.1021/acs.nanolett.9b03556

[ASAP] Nanophotonic Cell Lysis and Polymerase Chain Reaction with Gravity-Driven Cell Enrichment for Rapid Detection of Pathogens

By Byungrae Cho†‡§, Sang Hun Lee†§, Jihwan Song†¦, Saptati Bhattacharjee†, Jeffrey Feng†, SoonGweon Hong†§, Minsun Song†‡§, Wonseok Kim†§, Jonghwan Lee†§, Doyeon Bang†§, Bowen Wang†, Lee W. Riley?, and Luke P. Lee*†‡§?#¶ from ACS Nano: Latest Articles (ACS Publications). Published on Dec 04, 2019.

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ACS Nano
DOI: 10.1021/acsnano.9b04685

[ASAP] MoS2 Memtransistors Fabricated by Localized Helium Ion Beam Irradiation

By Jakub Jadwiszczak*†‡§?, Darragh Keane†?, Pierce Maguire†‡, Conor P. Cullen†?, Yangbo Zhou*?, Huading Song§, Clive Downing†?, Daniel Fox†‡, Niall McEvoy†?, Rui Zhu¶, Jun Xu¶, Georg S. Duesberg†?#, Zhi-Min Liao§?, John J. Boland†?, and Hongzhou Zhang*†‡ from ACS Nano: Latest Articles (ACS Publications). Published on Dec 04, 2019.

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ACS Nano
DOI: 10.1021/acsnano.9b07421

[ASAP] Rotation-Selective Moiré Magnification of Structural Color Pattern Arrays

By John You En Chan†, Qifeng Ruan*†, Ray Jia Hong Ng†, Cheng-Wei Qiu‡, and Joel K. W. Yang*†§ from ACS Nano: Latest Articles (ACS Publications). Published on Dec 04, 2019.

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ACS Nano
DOI: 10.1021/acsnano.9b06772

[ASAP] Dendrimer Ligand Directed Nanoplate Assembly

By Katherine C. Elbert†#, Thi Vo‡#, Nadia M. Krook§, William Zygmunt‡, Jungmi Park†, Kevin G. Yager||, Russell J. Composto§, Sharon C. Glotzer*‡?¶, and Christopher B. Murray*†§ from ACS Nano: Latest Articles (ACS Publications). Published on Dec 04, 2019.

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ACS Nano
DOI: 10.1021/acsnano.9b07348

[ASAP] Programmable Ultralight Magnets via Orientational Arrangement of Ferromagnetic Nanoparticles within Aerogel Hosts

By Yuanyuan Li†, Qingkun Liu‡, Andrew J. Hess‡, Shu Mi†, Xiaoduo Liu†, Ziyu Chen†, Yong Xie*†‡, and Ivan I. Smalyukh*‡§? from ACS Nano: Latest Articles (ACS Publications). Published on Dec 04, 2019.

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ACS Nano
DOI: 10.1021/acsnano.9b04818

[ASAP] Lanthanide-Boosted Singlet Oxygen from Diverse Photosensitizers along with Potent Photocatalytic Oxidation

By Jinyi Zhang†, Shihong Wu‡, Xiaomei Lu‡, Peng Wu*‡, and Juewen Liu*† from ACS Nano: Latest Articles (ACS Publications). Published on Dec 04, 2019.

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ACS Nano
DOI: 10.1021/acsnano.9b06840

[ASAP] Stepwise Electrocatalysis as a Strategy against Polysulfide Shuttling in Li–S Batteries

By Hualin Ye†, Jianguo Sun‡, Shengliang Zhang†, Haibin Lin†, Tianran Zhang†, Qiaofeng Yao†, and Jim Yang Lee*† from ACS Nano: Latest Articles (ACS Publications). Published on Dec 04, 2019.

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ACS Nano
DOI: 10.1021/acsnano.9b07121

[ASAP] Nanomedicines Lost in Translation

By Keegan Guidolin†‡? and Gang Zheng*‡§? from ACS Nano: Latest Articles (ACS Publications). Published on Dec 04, 2019.

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ACS Nano
DOI: 10.1021/acsnano.9b08659

[ASAP] Unlocking Acyclic p-Bond Rich Structure Space with Tetraethynylethylene–Tetravinylethylene Hybrids

By Kelsey L. Horvath†, Nicholas L. Magann†, Madison J. Sowden†, Michael G. Gardiner, and Michael S. Sherburn* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Dec 04, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b08885

[ASAP] Fullerene-Based Switching Molecular Diodes Controlled by Oriented External Electric Fields

By Adam Jaros?#†‡, Esmaeil Farajpour Bonab#§?, Michal Straka*†, and Cina Foroutan-Nejad*§?? from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Dec 04, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b07215

[ASAP] Direct in Vitro Selection of Trans-Acting Ribozymes for Posttranscriptional, Site-Specific, and Covalent Fluorescent Labeling of RNA

By Mohammad Ghaem Maghami†‡, Carolin P. M. Scheitl†, and Claudia Ho¨bartner*†‡ from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Dec 04, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b10531

[ASAP] Polymeric, Cost-Effective, Dopant-Free Hole Transport Materials for Efficient and Stable Perovskite Solar Cells

By Fuguo Zhang†?, Zhaoyang Yao†?, Yaxiao Guo†, Yuanyuan Li‡, Jan Bergstrand?, Calvin J. Brett‡?#, Bin Cai?, Alireza Hajian‡, Yu Guo§, Xichuan Yang?, James M Gardner§, Jerker Widengren?, Stephan V. Roth#?, Lars Kloo§, and Licheng Sun*†? from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Dec 04, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b08424

[ASAP] Rhodium-Catalyzed Regiodivergent and Enantioselective Hydroboration of Enamides

By Xiao-Yan Bai†, Wei Zhao†, Xin Sun, and Bi-Jie Li* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Dec 04, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b10578

The phase diagram of 2D antiferromagnets

By Stephan Roche from Nature Nanotechnology - Issue - nature.com science feeds. Published on Dec 04, 2019.

Nature Nanotechnology, Published online: 04 December 2019; doi:10.1038/s41565-019-0592-x

The magnetic phase diagram of thin-layered antiferromagnets is revealed experimentally by investigating the tunnelling conductance as a function of magnetic field. A rich magnetic behaviour in CrCl3 is uncovered, from which relevant magnetic information is extracted that is not easily available with other approaches.

Nanotechnology intervention of the microbiome for cancer therapy

By Leaf Huang from Nature Nanotechnology - Issue - nature.com science feeds. Published on Dec 04, 2019.

Nature Nanotechnology, Published online: 04 December 2019; doi:10.1038/s41565-019-0589-5

This review highlights key opportunistic areas for applying nanotechnologies towards the manipulation of the microbiome for the treatment of cancer, gives an overview of seminal work and discusses future challenges and our perspective on this emerging area.

The two directions of cancer nanomedicine

From Nature Nanotechnology - Issue - nature.com science feeds. Published on Dec 04, 2019.

Nature Nanotechnology, Published online: 04 December 2019; doi:10.1038/s41565-019-0597-5

The cancer nanomedicine field is heading in two directions — debating whether the clinical translation of nanomaterials should be accelerated or whether some of the long-standing drug delivery paradigms have to be challenged first.

The Onpattro story and the clinical translation of nanomedicines containing nucleic acid-based drugs

By Pieter R. Cullis from Nature Nanotechnology - Issue - nature.com science feeds. Published on Dec 04, 2019.

Nature Nanotechnology, Published online: 04 December 2019; doi:10.1038/s41565-019-0591-y

The regulatory approval of Onpattro, a lipid nanoparticle-based short interfering RNA drug for the treatment of polyneuropathies induced by hereditary transthyretin amyloidosis, paves the way for clinical development of many nucleic acid-based therapies enabled by nanoparticle delivery.

Nanoparticle-based photothermal heating to drive chemical reactions within a solid: using inhomogeneous polymer degradation to manipulate mechanical properties and segregate carbonaceous by-products

By Laura I Clarke from RSC - Nanoscale latest articles. Published on Dec 04, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR07401E, Paper
Honglu Huang, Gabriel Firestone, Daniela Fontecha, Russell Gorga, Jason Bochinski, Laura I Clarke
Photothermal heating via metal nanoparticles is utilized to degrade polyethylcyanoacrylate (PECA), which undergoes a thermally-driven depolymerization process, resulting in (i) monomer loss from the sample, (ii) repolymerization to form shorter...
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Degradation of ZnGa2O4:Cr3+ luminescent nanoparticles in lysosomal-like medium

By Thomas Lecuyer from RSC - Nanoscale latest articles. Published on Dec 04, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR06867H, Paper
Cyrille Richard, Florence Gazeau, Nathalie Mignet, Daniel Scherman, Damien Alloyeau, Guillaume Wang, Johanne Seguin, Yohann Corvis, rene lai-kuen, Morgane Desmau, Jeanne Volatron, marc antoine durand, Thomas Lecuyer
The ultimate goal of in vivo imaging is to provide safe tools to probe the inside of a body in order to obtain pathological information, monitor activities, and examine disease...
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Effects of high-k gate dielectrics on the electrical performance and reliability of an amorphous indium–tin–zinc–oxide thin film transistor (a-ITZO TFT): an analytical survey

By Amjad Meftah from RSC - Nanoscale latest articles. Published on Dec 04, 2019.

Nanoscale, 2019, Advance Article
DOI: 10.1039/C9NR03395E, Paper
Taki Eddine Taouririt, Afak Meftah, Nouredine Sengouga, Marwa Adaika, Slimane Chala, Amjad Meftah
This study is a numerical simulation obtained by using Silvaco Atlas software to investigate the effect of different types of dielectric layers, inserted between the channel and the gate, on the performance and reliability of an a-ITZO TFT.
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Thick grain boundary induced strengthening in nanocrystalline Ni alloy

By X. Zhang from RSC - Nanoscale latest articles. Published on Dec 04, 2019.

Nanoscale, 2019, Advance Article
DOI: 10.1039/C9NR06843K, Paper
Jie Ding, D. Neffati, Qiang Li, R. Su, Jin Li, S. Xue, Z. Shang, Y. Zhang, H. Wang, Y. Kulkarni, X. Zhang
Mo enriched thick GBs in nanocrystalline Ni alloy are stronger barriers than conventional GBs to the transmission of dislocations.
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Correction: Dopamine-melanin nanoparticles scavenge reactive oxygen and nitrogen species and activate autophagy for osteoarthritis therapy

By Jinmin Zhao from RSC - Nanoscale latest articles. Published on Dec 04, 2019.

Nanoscale, 2019, Advance Article
DOI: 10.1039/C9NR90272D, Correction
Open Access Open Access
Creative Commons Licence  This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
Gang Zhong, Xueyuan Yang, Xianfang Jiang, Anil Kumar, Huiping Long, Jin Xie, Li Zheng, Jinmin Zhao
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Plasmonic Nanosponges Filled by Silicon for Enhanced White Light Emission

By Dmitry Zuev from RSC - Nanoscale latest articles. Published on Dec 04, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR08952G, Paper
Artem Larin, Alexandre Nomine, Eduard Ageev, Jaafar Ghanbaja, Lada Kolotova, Sergey Starikov, Stéphanie Bruyère, Thierry Belmonte, Sergey Makarov, Dmitry Zuev
Plasmonic nanosponges is a powerful platform for various nanophotonic applications owing to extremely high local field enhancement in the metallic nanopores. The filling of the nanopores by the high-refractive index...
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Multiple modes integrated biosensor based on higher order Fano metamaterials

By Jianquan Yao from RSC - Nanoscale latest articles. Published on Dec 04, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR07777D, Paper
Xin Yan, Zhang Zhang, Lanju Liang, Maosheng Yang, Dequan Wei, Xiaoxian Song, Haiting Zhang, Yuying Lu, Longhai Liu, Mengjin Zhang, Tao Wang, Jianquan Yao
A multiple modes integrated biosensor based on higher order Fano metamaterials (FRMMs) is proposed. The frequency shift (Δf ) of x-polarized quadrupolar (Qx), octupolar (Ox), hexadecapolar (Hx), y-polarized quadrupolar (Qy)...
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Metallo-responsive self-assembly of lipophilic guanines in hydrocarbon solvents: a systematic SAXS structural characterization

By Paolo Mariani from RSC - Nanoscale latest articles. Published on Dec 04, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR08556D, Paper
Adriano Gonnelli, Silvia Pieraccini, Enrico Junior Baldassarri, Sergio S. Funari, Stefano Masiero, Maria Grazia Ortore, Paolo Mariani
Lipophilic guanines (LipoGs) in aprotic solvents undergo different self-assembly processes based on different H-bonded motifs. Cylindrical nanotubes made by π-π stacked guanine tetramers (G-quadruplexes) and flat, tape-like aggregates (G-ribbons) have...
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Predictive theoretical screening of phase stability for chemical order and disorder in quaternary 312 and 413 MAX phases

By Johanna Rosen from RSC - Nanoscale latest articles. Published on Dec 04, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR08675G, Paper
Open Access Open Access
Martin Dahlqvist, Johanna Rosen
In this work we systematically explore a class of atomically laminated materials, Mn+1AXn (MAX) phases upon alloying between two transition metals, M´ and M´´, from Group III to VI (Sc,...
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An RNase H-powered DNA walking machine for sensitive detection of RNase H and the screening of related inhibitors

By Xia Chu from RSC - Nanoscale latest articles. Published on Dec 04, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR07550J, Paper
Yafang Wang, Namin Hu, Chang Liu, Cunpeng Nie, Manman He, Juan Zhang, Qiaoqin Yu, Chuan Zhao, Ting-ting Chen, Xia Chu
Ribonuclease H (RNase H), an intracellular ribonuclease, plays a crucial role in cellular processes, and especially relates with many diseases processes. Here, we report a novel signal amplification strategy based...
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Unexpected Surfactant Role of Immiscible Nitrogen in the Structural Development of Silver Nanoparticles: An Experimental and Numerical Investigation

By Eun-Ae Choi from RSC - Nanoscale latest articles. Published on Dec 04, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR08076G, Paper
Jungheum Yun, Hee-Suk Chung, Sang-Geul Lee, Jong Seong Bae, Tae Eun Hong, Kazutoshi Takahashi, Seung Min Yu, Jucheol Park, Qixin Guo, Gun-Hwan Lee, Seung Zeon Han, Yoshifumi Ikoma, Eun-Ae Choi
Artificially designing the crystal orientation and face of noble metal nanoparticles is important to realizing unique chemical and physical features that are very different from those of noble metals in...
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Nickel‐Catalyzed Electrochemical Reductive Relay Cross‐Coupling of Alkyl Halides to Aryl Halides

By Ke-Jin Jiao, Dong Liu, Hong-Xing Ma, Hui Qiu, Ping Fang, Tian-Sheng Mei from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 03, 2019.

A Highly regioselective Ni‐catalyzed electrochemical reductive relay cross‐coupling between an aryl halide and an alkyl halide has been developed in an undivided cell. Various functional groups are tolerated under this mild reaction conditions, which provides an alternative approach for the synthesis of 1,1‐diarylalkanes

Masthead: (Adv. Mater. 49/2019)

By from Wiley: Advanced Materials: Table of Contents. Published on Dec 03, 2019.

Low Dose of X‐Ray‐Excited Long‐Lasting Luminescent Concave Nanocubes in Highly Passive Targeting Deep‐Seated Hepatic Tumors

By Zheng‐Zhe Chen, Liu‐Chun Wang, Divinah Manoharan, Chin‐Lai Lee, Lai‐Chin Wu, Wan‐Ting Huang, Eng‐Yen Huang, Chia‐Hao Su, Hwo‐Shuenn Sheu, Chen‐Sheng Yeh from Wiley: Advanced Materials: Table of Contents. Published on Dec 03, 2019.

Dispersed and well‐defined ZnGa2O4:Cr3+ (ZGC) concave nanocubes are reported as providing highly passive targeting of deep‐seated hepatic tumors. They also exhibit much stronger long‐lasting luminescence in UV and X‐ray excitation for the dispersed cubic ZGC compared with the agglomerative form that cannot be charged using X‐rays with a low dose of 0.5 Gy. Abstract Chromium‐doped zinc gallate, ZnGa2O4:Cr3+ (ZGC), is viewed as a long‐lasting luminescence (LLL) phosphor that can avoid tissue autofluorescence interference for in vivo imaging detection. ZGC is a cubic spinel structure, a typical agglomerative or clustered morphology lacking a defined cubic shape, but a sphere‐like feature is commonly obtained for the nanometric ZGC. The substantial challenge remains achieving a well‐defined cubic feature in nanoscale. The process by which dispersed and well‐defined concave cubic ZGC is obtained is described, exhibiting much stronger LLL in UV and X‐ray excitation for the dispersed cubic ZGC compared with the agglomerative form that cannot be excited using X‐rays with a low dose of 0.5 Gy. The cubic ZGC reveals a specific accumulation in liver and 0.5 Gy used at the end of X‐ray excitation is sufficient for imaging of deep‐seated hepatic tumors. The ZGC nanocubes show highly passive targeting of orthotopic hepatic tumors.

Intelligent Metamaterials Based on Nonlinearity for Magnetic Resonance Imaging

By Xiaoguang Zhao, Guangwu Duan, Ke Wu, Stephan W. Anderson, Xin Zhang from Wiley: Advanced Materials: Table of Contents. Published on Dec 03, 2019.

Coupled nonlinear metamaterials, featuring a self‐adaptive, or intelligent, response that selectively amplifies the magnetic field, are harnessed to enhance the magnetic field for lower radio‐frequency energy excitation and suppress its resonance for higher energy excitation. These intelligent metamaterials serve to enhance the signal‐to‐noise ratio of magnetic resonance imaging by more than tenfold. Abstract Metamaterials provide a powerful platform to probe and enhance nonlinear responses in physical systems toward myriad applications. Herein, the development of a coupled nonlinear metamaterial (NLMM) featuring a self‐adaptive response that selectively amplifies the magnetic field is reported. The resonance of the NLMM is suppressed in response to higher degrees of radio‐frequency excitation strength and recovers during a subsequent low excitation strength phase, thereby exhibiting an intelligent, or nonlinear, behavior by passively sensing excitation signal strength and responding accordingly. The nonlinear response of the NLMM enables us to boost the signal‐to‐noise ratio during magnetic resonance imaging to an unprecedented degree. These results provide insights into a new paradigm to construct NLMMs consisting of coupled resonators and pave the way toward the utilization of NLMMs to address a host of practical technological applications.

Two‐Photon Up‐Conversion Photoluminescence Realized through Spatially Extended Gap States in Quasi‐2D Perovskite Films

By Xixiang Zhu, Hengxing Xu, Yongtao Liu, Jia Zhang, Miaosheng Wang, Ilia N. Ivanov, Olga S. Ovchinnikova, Bin Hu from Wiley: Advanced Materials: Table of Contents. Published on Dec 03, 2019.

Gap states present a new approach to develop multi‐photon upconversion light emission in quasi‐2D perovskite films under continuous‐wave infrared excitation. Magneto‐photoluminescence (PL) and polarization‐dependent PL reveal that the gap states are essentially spatially extended states involved in orbit–orbit interaction toward generating multi‐photon excitation in quasi‐2D perovskite films. Abstract A new approach to generate a two‐photon up‐conversion photoluminescence (PL) by directly exciting the gap states with continuous‐wave (CW) infrared photoexcitation in solution‐processing quasi‐2D perovskite films [(PEA)2(MA)4Pb5Br16 with n = 5] is reported. Specifically, a visible PL peaked at 520 nm is observed with the quadratic power dependence by exciting the gap states with CW 980 nm laser excitation, indicating a two‐photon up‐conversion PL occurring in quasi‐2D perovskite films. Decreasing the gap states by reducing the n value leads to a dramatic decrease in the two‐photon up‐conversion PL signal. This confirms that the gap states are indeed responsible for generating the two‐photon up‐conversion PL in quasi‐2D perovskites. Furthermore, mechanical scratching indicates that the different‐n‐value nanoplates are essentially uniformly formed in the quasi‐2D perovskite films toward generating multi‐photon up‐conversion light emission. More importantly, the two‐photon up‐conversion PL is found to be sensitive to an external magnetic field, indicating that the gap states are essentially formed as spatially extended states ready for multi‐photon excitation. Polarization‐dependent up‐conversion PL studies reveal that the gap states experience the orbit–orbit interaction through Coulomb polarization to form spatially extended states toward developing multi‐photon up‐conversion light emission in quasi‐2D perovskites.

Are Cu2Te‐Based Compounds Excellent Thermoelectric Materials?

By Kunpeng Zhao, Ke Liu, Zhongmou Yue, Yancheng Wang, Qingfeng Song, Jian Li, Mengjia Guan, Qing Xu, Pengfei Qiu, Hong Zhu, Lidong Chen, Xun Shi from Wiley: Advanced Materials: Table of Contents. Published on Dec 03, 2019.

By introducing Ag2Te into Cu2Te, the phase‐transition features are well tuned and the high carrier concentration is substantially reduced, leading to a record‐high zT of 1.8. It is demonstrated that Cu2Te, Cu2S, and Cu2Se are all excellent thermoelectric (TE) materials that are beyond all other state‐of‐the‐art TE materials. Abstract Most of the state‐of‐the‐art thermoelectric (TE) materials exhibit high crystal symmetry, multiple valleys near the Fermi level, heavy constituent elements with small electronegativity differences, or complex crystal structure. Typically, such general features have been well observed in those well‐known TE materials such as Bi2X3‐, SnX‐, and PbX‐based compounds (X = S, Se, and Te). The performance is usually high in the materials with heavy constituent elements such as Te and Se, but it is low for light constituent elements such as S. However, there is a great abnormality in Cu2X‐based compounds in which Cu2Te has much lower TE figure of merit (zT) than Cu2S and Cu2Se. It is demonstrated that the Cu2Te‐based compounds are also excellent TE materials if Cu deficiency is sufficiently suppressed. By introducing Ag2Te into Cu2Te, the carrier concentration is substantially reduced to significantly improve the zT with a record‐high value of 1.8, 323% improvement over Cu2Te and outperforms any other Cu2Te‐based materials. The single parabolic band model is used to further prove that all Cu2X‐based compounds are excellent TE materials. Such finding makes Cu2X‐based compounds the only type of material composed of three sequent main group elements that all possess very high zT  s above 1.5.

Nanoscale Topotactic Phase Transformation in SrFeOx Epitaxial Thin Films for High‐Density Resistive Switching Memory

By Junjiang Tian, Haijun Wu, Zhen Fan, Yang Zhang, Stephen J. Pennycook, Dongfeng Zheng, Zhengwei Tan, Haizhong Guo, Pu Yu, Xubing Lu, Guofu Zhou, Xingsen Gao, Jun‐Ming Liu from Wiley: Advanced Materials: Table of Contents. Published on Dec 03, 2019.

The resistive‐switching (RS) mechanism in SrFeOx epitaxial thin films is revealed to be the formation/rupture of perovskite SrFeO3 nanofilaments in the brownmillerite SrFeO2.5 matrix, mediated by the electric‐field‐induced local topotactic phase transformation. With this mechanism, SrFeOx‐based RS devices can be downscaled to the 100 nm range and exhibit excellent performance. Abstract Resistive switching (RS) memory has stayed at the forefront of next‐generation nonvolatile memory technologies. Recently, a novel class of transition metal oxides (TMOs), which exhibit reversible topotactic phase transformation between insulating brownmillerite (BM) phase and conducting perovskite (PV) phase, has emerged as promising candidate materials for RS memories. Nevertheless, the microscopic mechanism of RS in these TMOs is still unclear. Furthermore, RS devices with simultaneously high density and superior memory performance are yet to be reported. Here, using SrFeOx as a model system, it is directly observed that PV SrFeO3 nanofilaments are formed and extend almost through the BM SrFeO2.5 matrix in the ON state and are ruptured in the OFF state, unambiguously revealing a filamentary RS mechanism. The nanofilaments are ≈10 nm in diameter, enabling to downscale Au/SrFeOx/SrRuO3 RS devices to the 100 nm range for the first time. These nanodevices exhibit good performance including ON/OFF ratio as high as ≈104, retention time over 105 s, and endurance up to 107 cycles. This study significantly advances the understanding of the RS mechanism in TMOs exhibiting topotactic phase transformation, and it also demonstrates the potential of these materials for use in high‐density RS memories.

Atomically Dispersed Binary Co‐Ni Sites in Nitrogen‐Doped Hollow Carbon Nanocubes for Reversible Oxygen Reduction and Evolution

By Xiaopeng Han, Xiaofei Ling, Deshuang Yu, Dengyu Xie, Linlin Li, Shengjie Peng, Cheng Zhong, Naiqin Zhao, Yida Deng, Wenbin Hu from Wiley: Advanced Materials: Table of Contents. Published on Dec 03, 2019.

Atomically dispersed Co‐Ni sites embedded in N‐doped hollow carbon nanocubes are synthesized, promoting oxygen reduction/evolution and zinc–air batteries with reduced overpotentials, increased energy efficiency, and enhanced reversibility. The single atomic sites and synergistic effect of the dual metal centers can decrease the energetic barrier and accelerate the reaction kinetics, contributing to superior electrochemical properties of resultant hybrid catalysts. Abstract With the inspiration of developing bifunctional electrode materials for reversible oxygen electrocatalysis, one strategy of heteroatom doping is proposed to fabricate dual metal single‐atom catalysts. However, the identification and mechanism functions of polynary single‐atom structures remain elusive. Atomically dispersed binary Co‐Ni sites embedded in N‐doped hollow carbon nanocubes (denoted as CoNi‐SAs/NC) are synthesized via proposed pyrolysis of dopamine‐coated metal‐organic frameworks. The atomically isolated bimetallic configuration in CoNi‐SAs/NC is identified by combining microscopic and spectroscopic techniques. When employing as oxygen electrocatalysts in alkaline medium, the resultant CoNi‐SAs/NC hybrid manifests outstanding catalytic performance for bifunctional oxygen reduction/evolution reactions, boosting the realistic rechargeable zinc–air batteries with high efficiency, low overpotential, and robust reversibility, superior to other counterparts and state‐of‐the‐art precious‐metal catalysts. Theoretical computations based on density functional theory demonstrate that the homogenously dispersed single atoms and the synergistic effect of neighboring Co‐Ni dual metal center can optimize the adsorption/desorption features and decrease the overall reaction barriers, eventually promoting the reversible oxygen electrocatalysis. This work not only sheds light on the controlled synthesis of atomically isolated advanced materials, but also provides deeper understanding on the structure–performance relationships of nanocatalysts with multiple active sites for various catalytic applications.

Quantum Topological Boundary States in Quasi‐Crystals

By Yao Wang, Yong‐Heng Lu, Jun Gao, Ke Sun, Zhi‐Qiang Jiao, Hao Tang, Xian‐Min Jin from Wiley: Advanced Materials: Table of Contents. Published on Dec 03, 2019.

The quantum features of single photons can be well preserved in quasi‐crystals via topological boundary states, particularly, in the appearance of diffusion‐induced decoherence and environmental noise decoherence. The confirmed compatibility between topological states and single photons leads to a new an avenue to “quantum topological photonics” and provides more possibilities for quantum materials and quantum technologies. Abstract Topological phases play a novel and fundamental role in matter and display extraordinary robustness to smooth changes in material parameters or disorder. A crossover between topological material and quantum information may lead to inherent fault‐tolerant quantum simulations and quantum computing. Quantum features may be preserved by being encoded among topological structures of physical evolution systems. This requires stimulation, manipulation, and observation of topological phenomena at the single quantum particle level, which has not, however, yet been realized. It is asked whether the quantum features of single photons can be preserved in topological structures. The boundary states are experimentally observed at the genuine single‐photon level and the performance of the topological phase is demonstrated to protect the quantum features against diffusion‐induced decoherence in coupled waveguides and noise decoherence from the ambient environment. Compatibility between macroscopic topological states and microscopic single photons in the ambient environment is thus confirmed, leading to a new avenue to “quantum topological photonics” and providing more new possibilities for quantum materials and quantum technologies.

Extending the Photovoltaic Response of Perovskite Solar Cells into the Near‐Infrared with a Narrow‐Bandgap Organic Semiconductor

By Xiaoming Zhao, Chao Yao, Tianran Liu, J. Clay Hamill, Guy Olivier Ngongang Ndjawa, Guangming Cheng, Nan Yao, Hong Meng, Yueh‐Lin Loo from Wiley: Advanced Materials: Table of Contents. Published on Dec 03, 2019.

A near‐infrared (NIR)‐harvesting perovskite solar cell with a power‐conversion efficiency of 21.6% and an operational half‐life of 1900 h is achieved by directly incorporating a multifunctional organic semiconductor that both extends light absorption and passivates defects in the perovskite active layer. Abstract Typical lead‐based perovskites solar cells show an onset of photogeneration around 800 nm, leaving plenty of spectral loss in the near‐infrared (NIR). Extending light absorption beyond 800 nm into the NIR should increase photocurrent generation and further improve photovoltaic efficiency of perovskite solar cells (PSCs). Here, a simple and facile approach is reported to incorporate a NIR‐chromophore that is also a Lewis‐base into perovskite absorbers to broaden their photoresponse and increase their photovoltaic efficiency. Compared with pristine PSCs without such an organic chromophore, these solar cells generate photocurrent in the NIR beyond the band edge of the perovskite active layer alone. Given the Lewis‐basic nature of the organic semiconductor, its addition to the photoactive layer also effectively passivates perovskite defects. These films thus exhibit significantly reduced trap densities, enhanced hole and electron mobilities, and suppressed illumination‐induced ion migration. As a consequence, perovskite solar cells with organic chromophore exhibit an enhanced efficiency of 21.6%, and substantively improved operational stability under continuous one‐sun illumination. The results demonstrate the potential generalizability of directly incorporating a multifunctional organic semiconductor that both extends light absorption and passivates surface traps in perovskite active layers to yield highly efficient and stable NIR‐harvesting PSCs.

Deep‐Subwavelength Holey Acoustic Second‐Order Topological Insulators

By Zhiwang Zhang, Houyou Long, Chen Liu, Chen Shao, Ying Cheng, Xiaojun Liu, Johan Christensen from Wiley: Advanced Materials: Table of Contents. Published on Dec 03, 2019.

Higher‐order topological insulators belong to a new class of materials with unusual topological phases supporting lower‐dimensional boundary states. Along this frontier, a deep‐subwavelength acoustic second‐order topological insulator is proposed to explore corner states in three different frequency ranges. Besides the topological robustness against fabrication imperfections, a programmable device is designed to achieve acoustic imaging beyond the diffraction limit. Abstract Higher‐order topological insulators (HOTIs) belong to a new class of materials with unusual topological phases. They have garnered considerable attention due to their capabilities in confining energy at the hinges and corners, which is entirely protected by the topology, and have thus become attractive structures for acoustic wave studies and control. However, for most practical applications at audible and low frequencies, compact and subwavelength implementations are desirable in addition to providing robust guiding of sound beyond a single‐frequency operation. Here, a holey HOTI capable of sustaining deeply confined corner states 50 times smaller than the wavelength is proposed. A remarkable resilience of these surface‐confined acoustic states against defects is experimentally observed, and topologically protected sound is demonstrated in three different frequency regimes. Concerning this matter, the findings will thus have the capability to push forward exciting applications for robust acoustic imaging way beyond the diffraction limit.

Room‐Temperature Active Modulation of Valley Dynamics in a Monolayer Semiconductor through Chiral Purcell Effects

By Zilong Wu, Jingang Li, Xiaotian Zhang, Joan M. Redwing, Yuebing Zheng from Wiley: Advanced Materials: Table of Contents. Published on Dec 03, 2019.

Monolayer semiconductors with spin‐dependent contrasting phenomena at K and K′ valleys feature addressable valley degree of freedom for valleytronic applications. Chiral Purcell effects in plasmonic chiral metamaterials are demonstrated to be able to control the relaxation of targeted valley excitons at a monolayer WSe2 in a versatile way, allowing the actively tunable modulation of valley dynamics at room temperature. Abstract Spin‐dependent contrasting phenomena at K and K′ valleys in monolayer semiconductors have led to addressable valley degree of freedom, which is the cornerstone for emerging valleytronic applications in information storage and processing. Tunable and active modulation of valley dynamics in a monolayer WSe2 is demonstrated at room temperature through controllable chiral Purcell effects in plasmonic chiral metamaterials. The strong spin‐dependent modulation on the spontaneous decay of valley excitons leads to tunable handedness and spectral shift of valley‐polarized emission, which is analyzed and predicted by an advanced theoretical model and further confirmed by experimental measurements. Moreover, large active spectral tuning (≈24 nm) and reversible ON/OFF switching of circular polarization of emission are achieved by the solvent‐controllable thickness of the dielectric spacer in the metamaterials. With the on‐demand and active tunability in valley‐polarized emission, chiral Purcell effects can provide new strategies to harness valley excitons for applications in ultrathin valleytronic devices.

Freeform, Reconfigurable Embedded Printing of All‐Aqueous 3D Architectures

By Guanyi Luo, Yafeng Yu, Yuxue Yuan, Xue Chen, Zhou Liu, Tiantian Kong from Wiley: Advanced Materials: Table of Contents. Published on Dec 03, 2019.

Freeform, reconfigurable all‐aqueous three‐dimensional (3D) architectures are fabricated by embedded‐bioprinting using aqueous two‐phase systems (ATPSs). The reconfigurable aqueous‐in‐aqueous 3D microstructures can be stabilized for weeks by interfacial membranes via hydrogen bonds. By incorporating living cells in compartmentalized ink, this approach can be used in engineering tissue‐like constructs for applications in drug screening, in vitro tissue models and regenerative medicine. Abstract Aqueous microstructures are challenging to create, handle, and preserve since their surfaces tend to shrink into spherical shapes with minimum surface areas. The creation of freeform aqueous architectures will significantly advance the bioprinting of complex tissue‐like constructs, such as arteries, urinary catheters, and tracheae. The generation of complex, freeform, three‐dimensional (3D) all‐liquid architectures using formulated aqueous two‐phase systems (ATPSs) is demonstrated. These all‐liquid microconstructs are formed by printing aqueous bioinks in an immiscible aqueous environment, which functions as a biocompatible support and pregel solution. By exploiting the hydrogen bonding interaction between polymers in ATPS, the printed aqueous‐in‐aqueous reconfigurable 3D architectures can be stabilized for weeks by the noncovalent membrane at the interface. Different cells can be separately combined with compartmentalized bioinks and matrices to obtain tailor‐designed microconstructs with perfusable vascular networks. The freeform, reconfigurable embedded printing of all‐liquid architectures by ATPSs offers unique opportunities and powerful tools since limitless formulations can be designed from among a breadth of natural and synthetic hydrophilic polymers to mimic tissues. This printing approach may be useful to engineer biomimetic, dynamic tissue‐like constructs for potential applications in drug screening, in vitro tissue models, and regenerative medicine.

Boosting the Performance of Environmentally Friendly Quantum Dot‐Sensitized Solar Cells over 13% Efficiency by Dual Sensitizers with Cascade Energy Structure

By Zhenxiao Pan, Liang Yue, Huashang Rao, Jie Zhang, Xinhua Zhong, Zonglong Zhu, Alex K.‐Y. Jen from Wiley: Advanced Materials: Table of Contents. Published on Dec 03, 2019.

A cosensitization strategy with use of dual heavy‐metal‐free NIR absorption Zn–Cu–In–Se and Zn–Cu–In–S quantum dots (QDs) as cosensitizers is applied to control the light‐absorption, electron‐injection, and charge‐recombination processes simultaneously in QD‐sensitized solar cells (QDSCs). An average power conversion efficiency of 13.18% and a new certified efficiency record of 12.98% are obtained for environmentally friendly QDSCs under AM 1.5G 1 sun irradiation. Abstract Generally, high light‐harvesting efficiency, electron‐injection efficiency, and charge‐collection efficiency are the prerequisites for high‐efficiency quantum‐dot‐sensitized solar cells (QDSCs). However, it is fairly difficult for a single QD sensitizer to meet these three requirements simultaneously. It is demonstrated that these parameters can be felicitously balanced by a cosensitization strategy through the adoption of environmental‐friendly Zn–Cu–In–Se and Zn–Cu–In–S dual QD sensitizers with cascade energy structure. Experimental results indicate that: i) the combination of the dual QDs can improve the light‐harvesting capability of the cells, especially in the visible light window; ii) the cosensitization approach can facilitate electron injection, benefitting from the cascade energy structure of the two QD sensitizers employed; iii) the charge‐collection efficiency can be remarkably enhanced by the suppressed charge‐recombination process due to the improved QD coverage on TiO2. Consequently, this cosensitization strategy delivers a new certified efficiency record of 12.98% for liquid‐junction QDSCs under AM 1.5G 1 sun irradiation. Moreover, the constructed cells exhibit good stability in a high‐humidity environment.

Cesium Lead Inorganic Solar Cell with Efficiency beyond 18% via Reduced Charge Recombination

By Qiufeng Ye, Yang Zhao, Shaiqiang Mu, Fei Ma, Feng Gao, Zema Chu, Zhigang Yin, Pingqi Gao, Xingwang Zhang, Jingbi You from Wiley: Advanced Materials: Table of Contents. Published on Dec 03, 2019.

The power conversion efficiency of inorganic perovskite solar cells (PSCs) is still low compared with hybrid PSCs. The use of lithium fluoride on SnO2 and PbCl2 additive in perovskite is reported for reducing the charge recombination; 18.64% efficiency of CsPbI3–xBrx solar cells is demonstrated; and the devices show over than 1000 h light soaking stability. Abstract Cesium‐based inorganic perovskite solar cells (PSCs) are promising due to their potential for improving device stability. However, the power conversion efficiency of the inorganic PSCs is still low compared with the hybrid PSCs due to the large open‐circuit voltage (VOC) loss possibly caused by charge recombination. The use of an insulated shunt‐blocking layer lithium fluoride on electron transport layer SnO2 for better energy level alignment with the conduction band minimum of the CsPbI3‐xBrx and also for interface defect passivation is reported. In addition, by incorporating lead chloride in CsPbI3‐xBrx precursor, the perovskite film crystallinity is significantly enhanced and the charge recombination in perovksite is suppressed. As a result, optimized CsPbI3‐xBrx PSCs with a band gap of 1.77 eV exhibit excellent performance with the best VOC as high as 1.25 V and an efficiency of 18.64%. Meanwhile, a high photostability with a less than 6% efficiency drop is achieved for CsPbI3‐xBrx PSCs under continuous 1 sun equivalent illumination over 1000 h.

Water‐Triggered Hyperbranched Polymer Universal Adhesives: From Strong Underwater Adhesion to Rapid Sealing Hemostasis

By Chunyan Cui, Chuanchuan Fan, Yuanhao Wu, Meng Xiao, Tengling Wu, Dongfei Zhang, Xinyu Chen, Bo Liu, Ziyang Xu, Bo Qu, Wenguang Liu from Wiley: Advanced Materials: Table of Contents. Published on Dec 03, 2019.

A hyperbranched polymer adhesive fabricated using a ternary Michael addition reaction of hydrophobic multi‐vinyl monomers with dopamine demonstrates strong underwater adhesion to diverse materials without any oxidant. This is due to water‐triggered fast coacervation and increased outward exposure of catechols. Introducing long‐chain alkylamine contributes to the formation of an injectable hemostatic sealant that can rapidly stop visceral bleeding, especially hemorrhage from deep wound. Abstract Despite recent advance in bioinspired adhesives, achieving strong adhesion and sealing hemostasis in aqueous and blood environments is challenging. A hyperbranched polymer (HBP) with a hydrophobic backbone and hydrophilic adhesive catechol side branches is designed and synthesized based on Michael addition reaction of multi‐vinyl monomers with dopamine. It is demonstrated that upon contacting water, the hydrophobic chains self‐aggregate to form coacervates quickly, displacing water molecules on the adherent surface to trigger increased exposure of catechol groups and thus rapidly strong adhesion to diverse materials from low surface energy to high energy in various environments, such as deionized water, sea water, PBS, and a wide range of pH solutions (pH = 3 to 11) without use of any oxidant. Also, this HBP adhesive (HBPA) exhibits a robust adhesion to fractured bone, precluding the problem of mismatched surface energy and mechanical properties. The HBPA's adhesion is repeatable in a wet condition. Intriguingly, the HBPA is capable of gluing dissimilar materials with distinct properties. Importantly, introducing long alkylamine into this modular hyperbranched architecture contributes to formation of an injectable hemostatic sealant that can rapidly stop visceral bleeding, especially hemorrhage from deep wound.

Skin‐Friendly Electronics for Acquiring Human Physiological Signatures

By Yujia Zhang, Tiger H. Tao from Wiley: Advanced Materials: Table of Contents. Published on Dec 03, 2019.

A set of degradable epidermal electronics consisting of both physical and biochemical sensors is presented as skin‐friendly electronics. Featuring stable operation and on‐demand decomposition, strong adhesion and easy detachment are achieved concurrently through a genetically engineered plasticized copolymer. Human experiments show that multidimensional physiological signals can be measured using these devices and analyzed for important states using a machine learning algorithm. Abstract Epidermal sensing devices offer great potential for real‐time health and fitness monitoring via continuous characterization of the skin for vital morphological, physiological, and metabolic parameters. However, peeling them off can be difficult and sometimes painful especially when these skin‐mounted devices are applied on sensitive or wounded regions of skin due to their strong adhesion. A set of biocompatible and water‐decomposable “skin‐friendly” epidermal electronic devices fabricated on flexible, stretchable, and degradable protein‐based substrates are reported. Strong adhesion and easy detachment are achieved concurrently through an environmentally benign, plasticized protein platform offering engineered mechanical properties and water‐triggered, on‐demand decomposition lifetime (transiency). Human experiments show that multidimensional physiological signals can be measured using these innovative epidermal devices consisting of electro‐ and biochemical sensing modules and analyzed for important physiological signatures using an artificial neural network. The advances provide unique, versatile capabilities and broader applications for user‐ and environmentally friendly epidermal devices.

SnSe/MoS2 van der Waals Heterostructure Junction Field‐Effect Transistors with Nearly Ideal Subthreshold Slope

By Jian Guo, Laiyuan Wang, Yiwei Yu, Peiqi Wang, Yu Huang, Xiangfeng Duan from Wiley: Advanced Materials: Table of Contents. Published on Dec 03, 2019.

A 2D SnSe/MoS2 van der Waals heterostructure‐based junction field‐effect transistor (JFET) is constructed and systematically studied. It exhibits well‐behaviored n‐channel JFET characteristics with a nearly ideal subthreshold swing SS of 60.3 mV dec−1, a small pinch‐off voltage VP of −0.25 V, and high ON/OFF ratio over 106, demonstrating excellent electronic performance especially in the subthreshold regime. Abstract The minimization of the subthreshold swing (SS) in transistors is essential for low‐voltage operation and lower power consumption, both critical for mobile devices and internet of things (IoT) devices. The conventional metal‐oxide‐semiconductor field‐effect transistor requires sophisticated dielectric engineering to achieve nearly ideal SS (60 mV dec−1 at room temperature). However, another type of transistor, the junction field‐effect transistor (JFET) is free of dielectric layer and can reach the theoretical SS limit without complicated dielectric engineering. The construction of a 2D SnSe/MoS2 van der Waals (vdW) heterostructure‐based JFET with nearly ideal SS is reported. It is shown that the SnSe/MoS2 vdW heterostructure exhibits excellent p–n diode rectifying characteristics with low saturate current. Using the SnSe as the gate and MoS2 as the channel, the SnSe/MoS2 vdW heterostructure exhibit well‐behavioured n‐channel JFET characteristics with a small pinch‐off voltage VP of −0.25 V, nearly ideal subthreshold swing SS of 60.3 mV dec−1 and high ON/OFF ratio over 106, demonstrating excellent electronic performance especially in the subthreshold regime.

Biomimetic Nanosilica–Collagen Scaffolds for In Situ Bone Regeneration: Toward a Cell‐Free, One‐Step Surgery

By Shao‐Jie Wang, Dong Jiang, Zheng‐Zheng Zhang, You‐Rong Chen, Zheng‐Dong Yang, Ji‐Ying Zhang, Jinjun Shi, Xing Wang, Jia‐Kuo Yu from Wiley: Advanced Materials: Table of Contents. Published on Dec 03, 2019.

A biosilicification strategy is developed to provide a uniform and robust osteoinductive surface on porous natural collagen scaffolds. The resultant nanosilica–collagen (nSC) scaffolds possess topographical and chemical cues for superior in situ bone defect repair, without the use of exogenous cells or growth factors. This novel preparation of biomimetic bone scaffolds shows promising clinical applications in the treatment of bone defects. Abstract Current approaches to fabrication of nSC composites for bone tissue engineering (BTE) have limited capacity to achieve uniform surface functionalization while replicating the complex architecture and bioactivity of native bone, compromising application of these nanocomposites for in situ bone regeneration. A robust biosilicification strategy is reported to impart a uniform and stable osteoinductive surface to porous collagen scaffolds. The resultant nSC composites possess a native‐bone‐like porous structure and a nanosilica coating. The osteoinductivity of the nSC scaffolds is strongly dependent on the surface roughness and silicon content in the silica coating. Notably, without the use of exogenous cells and growth factors (GFs), the nSC scaffolds induce successful repair of a critical‐sized calvarium defect in a rabbit model. It is revealed that topographic and chemical cues presented by nSC scaffolds could synergistically activate multiple signaling pathways related to mesenchymal stem cell recruitment and bone regeneration. Thus, this facile surface biosilicification approach could be valuable by enabling production of BTE scaffolds with large sizes, complex porous structures, and varied osteoinductivity. The nanosilica‐functionalized scaffolds can be implanted via a cell/GF‐free, one‐step surgery for in situ bone regeneration, thus demonstrating high potential for clinical translation in treatment of massive bone defects.

Compartmentalized Jet Polymerization as a High‐Resolution Process to Continuously Produce Anisometric Microgel Rods with Adjustable Size and Stiffness

By Andreas J. D. Krüger, Onur Bakirman, Luis. P. B. Guerzoni, Alexander Jans, David B. Gehlen, Dirk Rommel, Tamás Haraszti, Alexander J. C. Kuehne, Laura De Laporte from Wiley: Advanced Materials: Table of Contents. Published on Dec 03, 2019.

Compartmentalized microfluidic jet gelation allows for the continuous high‐throughput fabrication of anisometric microgel rods with adjustable aspect ratio and stiffness. High‐frequency laser pulses initiate local ultrafast photopolymerization in the jet leading to microgels with rod diameter significantly smaller than the channel diameter to overcome the size limits of established microfluidic plug flow gelation. Abstract In the past decade, anisometric rod‐shaped microgels have attracted growing interest in the materials‐design and tissue‐engineering communities. Rod‐shaped microgels exhibit outstanding potential as versatile building blocks for 3D hydrogels, where they introduce macroscopic anisometry, porosity, or functionality for structural guidance in biomaterials. Various fabrication methods have been established to produce such shape‐controlled elements. However, continuous high‐throughput production of rod‐shaped microgels with simultaneous control over stiffness, size, and aspect ratio still presents a major challenge. A novel microfluidic setup is presented for the continuous production of rod‐shaped microgels from microfluidic plug flow and jets. This system overcomes the current limitations of established production methods for rod‐shaped microgels. Here, an on‐chip gelation setup enables fabrication of soft microgel rods with high aspect ratios, tunable stiffness, and diameters significantly smaller than the channel diameter. This is realized by exposing jets of a microgel precursor to a high intensity light source, operated at specific pulse sequences and frequencies to induce ultra‐fast photopolymerization, while a change in flow rates or pulse duration enables variation of the aspect ratio. The microgels can assemble into 3D structures and function as support for cell culture and tissue engineering.

High‐Performance Thermally Conductive Phase Change Composites by Large‐Size Oriented Graphite Sheets for Scalable Thermal Energy Harvesting

By Si Wu, Tingxian Li, Zhen Tong, Jingwei Chao, Tianyao Zhai, Jiaxing Xu, Taisen Yan, Minqiang Wu, Zhenyuan Xu, Hua Bao, Tao Deng, Ruzhu Wang from Wiley: Advanced Materials: Table of Contents. Published on Dec 03, 2019.

A method for synthesizing high‐performance thermally conductive phase‐ change composites is demonstrated. Large aligned graphite sheets inside the composite are generated from worm‐like expanded graphite. The aligned and interconnected graphite framework enhances KPCM up to 4.4–35.0 W m−1 K−1 at graphite loadings below 40.0 wt%, which may accelerate the high‐power‐density, low‐cost, and large‐scale applications of phase‐change materials. Abstract Efficient thermal energy harvesting using phase‐change materials (PCMs) has great potential for cost‐effective thermal management and energy storage applications. However, the low thermal conductivity of PCMs (KPCM) is a long‐standing bottleneck for high‐power‐density energy harvesting. Although PCM‐based nanocomposites with an enhanced thermal conductivity can address this issue, achieving a higher K (>10 W m−1 K−1) at filler loadings below 50 wt% remains challenging. A strategy for synthesizing highly thermally conductive phase‐change composites (PCCs) by compression‐induced construction of large aligned graphite sheets inside PCCs is demonstrated. The millimeter‐sized graphite sheet consists of lateral van‐der‐Waals‐bonded and oriented graphite nanoplatelets at the micro/nanoscale, which together with a thin PCM layer between the sheets synergistically enhance KPCM in the range of 4.4–35.0 W m−1 K−1 at graphite loadings below 40.0 wt%. The resulting PCCs also demonstrate homogeneity, no leakage, and superior phase change behavior, which can be easily engineered into devices for efficient thermal energy harvesting by coordinating the sheet orientation with the thermal transport direction. This method offers a promising route to high‐power‐density and low‐cost applications of PCMs in large‐scale thermal energy storage, thermal management of electronics, etc.

Colloidal Single‐Layer Photocatalysts for Methanol‐Storable Solar H2 Fuel

By Yingping Pang, Md Nasir Uddin, Wei Chen, Shaghraf Javaid, Emily Barker, Yunguo Li, Alexandra Suvorova, Martin Saunders, Zongyou Yin, Guohua Jia from Wiley: Advanced Materials: Table of Contents. Published on Dec 03, 2019.

A scalable stacking‐hinderable strategy is developed to enable exclusive single‐layer growth mode for transition metal dichalcogenides selectively sandwiched by surfactant molecules. These can act as efficient solar‐driven photocatalysts for solar H2 fuel production from hydrogen‐stored liquid carrier—methanol. Abstract Molecular surfactants are widely used to control low‐dimensional morphologies, including 2D nanomaterials in colloidal chemical synthesis, but it is still highly challenging to accurately control single‐layer growth for 2D materials. A scalable stacking‐hinderable strategy to not only enable exclusive single‐layer growth mode for transition metal dichalcogenides (TMDs) selectively sandwiched by surfactant molecules but also retain sandwiched single‐layer TMDs' photoredox activities is developed. The single‐layer growth mechanism is well explained by theoretical calculation. Three types of single‐layer TMDs, including MoS2, WS2, and ReS2, are successfully synthesized and demonstrated in solar H2 fuel production from hydrogen‐stored liquid carrier—methanol. Such H2 fuel production from single‐layer MoS2 nanosheets is COx‐free and reliably workable under room temperature and normal pressure with the generation rate reaching ≈617 µmole g−1 h−1 and excellent photoredox endurability. This strategy opens up the feasible avenue to develop methanol‐storable solar H2 fuel with facile chemical rebonding actualized by 2D single‐layer photocatalysts.

Flexible Honeycombed Nanoporous/Glassy Hybrid for Efficient Electrocatalytic Hydrogen Generation

By Rui Li, Xiongjun Liu, Ruoyu Wu, Jing Wang, Zhibin Li, K. C. Chan, Hui Wang, Yuan Wu, Zhaoping Lu from Wiley: Advanced Materials: Table of Contents. Published on Dec 03, 2019.

A free‐standing honeycombed nanoporous/glassy sandwich hybrid is developed through dealloying metallic glass (MG) precursor. The honeycombed Pt‐rich nanoporous structure providing fertile active sites and large contact areas combined with the introduced compressive lattice‐strain on the surface gives rise to better hydrogen evolution activity. Furthermore, the ductility of the intermediate MG matrix contributes to the excellent flexibility of the hybrid. Abstract Hydrogen evolution reaction (HER) in alkaline media urgently requires electrocatalysts concurrently possessing excellent activity, flexible free‐standing capability, and low cost. A honeycombed nanoporous/glassy sandwich structure fabricated through dealloying metallic glass (MG) is reported. This free‐standing hybrid shows outstanding HER performance with a very small overpotential of 37 mV at 10 mA cm−2 and a low Tafel slope of 30 mV dec−1 in alkaline media, outperforming commercial Pt/C. By alloying 3 at% Pt into the MG precursor, a honeycombed Pt75Ni25 solid solution nanoporous structure, with fertile active sites and large contact areas for efficient HER, is created on the dealloyed MG surface. Meanwhile, the surface compressive lattice‐strain effect is also introduced by substituting the Pt lattice sites with the smaller Ni atoms, which can effectively reduce the hydrogen adsorption energy and thus improve the hydrogen evolution. Moreover, the outstanding stability and flexibility stemming from the ductile MG matrix also make the hybrid suitable for practical electrode application. This work not only offers a reliable strategy to develop cost‐effective and flexible multicomponent catalysts with low Pt usage for efficient HER, but also sheds light on understanding the alloying effects of the catalytic process.

Liberating N‐CNTs Confined Highly Dispersed CoNx Sites for Selective Hydrogenation of Quinolines

By Wanbing Gong, Qinglin Yuan, Chun Chen, Yang Lv, Yue Lin, Changhao Liang, Guozhong Wang, Haimin Zhang, Huijun Zhao from Wiley: Advanced Materials: Table of Contents. Published on Dec 03, 2019.

A “laser irradiation in liquid” technique is innovatively utilized to liberate the abundant highly dispersed single‐atom CoNx sites confined inside carbon nanotubes. They can be used as a high‐performance selective hydrogenation catalyst to convert quinoline and its derivatives into value‐added fine chemicals. Abstract Selective hydrogenation of quinoline and its derivatives is an important means to produce corresponding 1,2,3,4‐tetrahydroquinolines for a wide spectrum of applications. A facile and efficient “laser irradiation in liquid” technique to liberate the inaccessible highly dispersed CoNx active sites confined inside N‐doped carbon nanotubes is demonstrated. The liberated CoNx sites possess generic catalytic activities toward selective hydrogenation of quinoline and its hydroxyl, methyl, and halogen substituted derivatives into corresponding 1,2,3,4‐tetrahydroquinolines with almost 100% conversion efficiency and selectivity. This laser irradiation treatment approach should be widely applicable to unlock the catalytic powers of inaccessible catalytic active sites confined by other materials.

Validating a Predictive Structure–Property Relationship by Discovery of Novel Polymers which Reduce Bacterial Biofilm Formation

By Adam A. Dundas, Olutoba Sanni, Jean‐Frédéric Dubern, Georgios Dimitrakis, Andrew L. Hook, Derek J. Irvine, Paul Williams, Morgan R. Alexander from Wiley: Advanced Materials: Table of Contents. Published on Dec 03, 2019.

A quantitative structure–activity relationship is extrapolated to develop a biomaterial capable of reducing biofilm formation, outperforming previously identified hit biomaterials. A high efficacy for reducing the biofilm formation of six clinically relevant bacterial species to catheter‐associated urinary tract infections is observed with an average 55‐fold reduction compared to clinically used silicone catheters. Abstract Synthetic materials are an everyday component of modern healthcare yet often fail routinely as a consequence of medical‐device‐centered infections. The incidence rate for catheter‐associated urinary tract infections is between 3% and 7% for each day of use, which means that infection is inevitable when resident for sufficient time. The O'Neill Review on antimicrobial resistance estimates that, left unchecked, ten million people will die annually from drug‐resistant infections by 2050. Development of biomaterials resistant to bacterial colonization can play an important role in reducing device‐associated infections. However, rational design of new biomaterials is hindered by the lack of quantitative structure–activity relationships (QSARs). Here, the development of a predictive QSAR is reported for bacterial biofilm formation on a range of polymers, using calculated molecular descriptors of monomer units to discover and exemplify novel, biofilm‐resistant (meth‐)acrylate‐based polymers. These predictions are validated successfully by the synthesis of new monomers which are polymerized to create coatings found to be resistant to biofilm formation by six different bacterial pathogens: Pseudomonas aeruginosa, Proteus mirabilis, Enterococcus faecalis, Klebsiella pneumoniae, Escherichia coli, and Staphylococcus aureus.

Contents: (Adv. Mater. 49/2019)

By from Wiley: Advanced Materials: Table of Contents. Published on Dec 03, 2019.

Nonlinear Metamaterials: Intelligent Metamaterials Based on Nonlinearity for Magnetic Resonance Imaging (Adv. Mater. 49/2019)

By Xiaoguang Zhao, Guangwu Duan, Ke Wu, Stephan W. Anderson, Xin Zhang from Wiley: Advanced Materials: Table of Contents. Published on Dec 03, 2019.

In article number 1905461, Stephan W. Anderson, Xin Zhang, and co‐workers present a coupled nonlinear metamaterial featuring a self‐adaptive response that selectively amplifies the magnetic field depending on the radio‐frequency excitation energy. The nonlinearity in metamaterials is harnessed to achieve in excess of a 10‐fold enhancement in the signal‐to‐noise ratio in magnetic resonance imaging.

Topological Insulators: Deep‐Subwavelength Holey Acoustic Second‐Order Topological Insulators (Adv. Mater. 49/2019)

By Zhiwang Zhang, Houyou Long, Chen Liu, Chen Shao, Ying Cheng, Xiaojun Liu, Johan Christensen from Wiley: Advanced Materials: Table of Contents. Published on Dec 03, 2019.

In article number 1904682, Ying Cheng, Xiaojun Liu, Johan Christensen, and co‐workers propose the marriage of spoof surface acoustic waves and second‐order topological insulators supporting extremely confined corner states 50 times smaller than the wavelength. Besides the topological robustness against fabrication imperfections, a programmable device is designed to achieve acoustic imaging far beyond the diffraction limit.

Chiral Metamaterials: Room‐Temperature Active Modulation of Valley Dynamics in a Monolayer Semiconductor through Chiral Purcell Effects (Adv. Mater. 49/2019)

By Zilong Wu, Jingang Li, Xiaotian Zhang, Joan M. Redwing, Yuebing Zheng from Wiley: Advanced Materials: Table of Contents. Published on Dec 03, 2019.

In article number 1904132, Yuebing Zheng and co‐workers achieve room‐temperature valley modulation by embedding monolayer WSe2 in Moiré chiral metamaterials. The spin‐dependent interactions between valley excitons and plasmon‐enhanced chiral electromagnetic near‐fields enable asymmetric Purcell effects on the spontaneous decay of excitons at the K and K' valleys of the monolayer WSe2, leading to facilely tunable valley‐polarized emission at room temperature.

Photocatalysts: Colloidal Single‐Layer Photocatalysts for Methanol‐Storable Solar H2 Fuel (Adv. Mater. 49/2019)

By Yingping Pang, Md Nasir Uddin, Wei Chen, Shaghraf Javaid, Emily Barker, Yunguo Li, Alexandra Suvorova, Martin Saunders, Zongyou Yin, Guohua Jia from Wiley: Advanced Materials: Table of Contents. Published on Dec 03, 2019.

Hydrogen production from methanol using nanocatalysts generally requires hash conditions, including high pressure, elevated temperature, and ultraviolet light irradiation. In article number 1905540, Yunguo Li, Zongyou Yin, Guohua Jia, and co‐workers develop a general scalable stacking‐hinderable strategy to exclusively produce single‐layer transition metal dichalcogenide nanosheets (MoS2, WS2, and ReS2) that can be directly used as remarkable photocatalysts for methanol‐storable solar H2 fuel production.

Perovskite Solar Cells: Extending the Photovoltaic Response of Perovskite Solar Cells into the Near‐Infrared with a Narrow‐Bandgap Organic Semiconductor (Adv. Mater. 49/2019)

By Xiaoming Zhao, Chao Yao, Tianran Liu, J. Clay Hamill, Guy Olivier Ngongang Ndjawa, Guangming Cheng, Nan Yao, Hong Meng, Yueh‐Lin Loo from Wiley: Advanced Materials: Table of Contents. Published on Dec 03, 2019.

In article number 1904494, Yueh‐Lin Loo and co‐workers demonstrate a near‐infrared‐harvesting perovskite solar cell with enhanced power‐conversion efficiency as high as 21.6% and improved stability, with an operational half‐life of 1900 h, by directly incorporating a multifunctional organic semiconductor that both extends light absorption and passivates defects in the perovskite active layers. This work provides a promising approach to prepare highly efficient and stable perovskites solar cells and opens a new application field for the rational design of narrow‐bandgap organic semiconductors.

Nanomedicine‐Based Immunotherapy for the Treatment of Cancer Metastasis

By Pengcheng Zhang, Yihui Zhai, Ying Cai, Yuliang Zhao, Yaping Li from Wiley: Advanced Materials: Table of Contents. Published on Dec 03, 2019.

Recent advances in nanomedicine‐based immunotherapy for the treatment of cancer metastasis are reviewed, starting with a brief introduction of metastasis cascade and nanomedicine‐based cancer immunotherapy. Recent strategies that can modulate key immune cells participating in metastasis cascade including cell intravasation and extravasation, blood circulation, and micrometastatic colony formation and proliferation are summarized. Abstract Metastasis is the leading cause of cancer‐associated death, with poor prognosis even after extensive treatment. The dormancy of metastatic cancer cells during dissemination or after colony formation is one major reason for treatment failure, as most drugs target cells of active proliferation. Immunotherapy has shown great potential in cancer therapy because the activity of effector cells is less affected by the metabolic status of cancer cells. In addition, metastatic cells out of immunosuppressive tumor microenvironment (TME) are more susceptible to immune clearance, although these cells can achieve immune surveillance evasion via strategies such as platelet and macrophage recruitment. Since nanomaterials themselves or their carried drugs have the capability to modulate the immune system, a great amount of focus has been placed on nanomedicine strategies that leverage immune cells participating the metastatic cascade. These nanomedicines successfully inhibit the tumor metastasis and prolong the survival of model animals. Immune cells that are involved in the metastasis cascade are first summarized and then recent and inspiring strategies and nanomaterials in this growing field are highlighted.

Rekindling RNAi Therapy: Materials Design Requirements for In Vivo siRNA Delivery

By Byungji Kim, Ji‐Ho Park, Michael J. Sailor from Wiley: Advanced Materials: Table of Contents. Published on Dec 03, 2019.

RNA interference‐mediated therapy has been researched for the past 20 years, but has suffered from a lack of effective oligonucleotide‐delivery systems. With advancements in nanoparticle design, the first siRNA‐based formulation was FDA‐approved in 2018. The challenges in in vivo RNAi and materials design requirements to overcome them are reviewed. Recent trends in research and clinical translation are also discussed. Abstract With the recent FDA approval of the first siRNA‐derived therapeutic, RNA interference (RNAi)‐mediated gene therapy is undergoing a transition from research to the clinical space. The primary obstacle to realization of RNAi therapy has been the delivery of oligonucleotide payloads. Therefore, the main aims is to identify and describe key design features needed for nanoscale vehicles to achieve effective delivery of siRNA‐mediated gene silencing agents in vivo. The problem is broken into three elements: 1) protection of siRNA from degradation and clearance; 2) selective homing to target cell types; and 3) cytoplasmic release of the siRNA payload by escaping or bypassing endocytic uptake. The in vitro and in vivo gene silencing efficiency values that have been reported in publications over the past decade are quantitatively summarized by material type (lipid, polymer, metal, mesoporous silica, and porous silicon), and the overall trends in research publication and in clinical translation are discussed to reflect on the direction of the RNAi therapeutics field.

Bridging Biological and Artificial Neural Networks with Emerging Neuromorphic Devices: Fundamentals, Progress, and Challenges

By Jianshi Tang, Fang Yuan, Xinke Shen, Zhongrui Wang, Mingyi Rao, Yuanyuan He, Yuhao Sun, Xinyi Li, Wenbin Zhang, Yijun Li, Bin Gao, He Qian, Guoqiang Bi, Sen Song, J. Joshua Yang, Huaqiang Wu from Wiley: Advanced Materials: Table of Contents. Published on Dec 03, 2019.

A comprehensive overview of biological and artificial neural networks is presented, including their key computing elements and related important functions, such as synapses, neurons, plasticity, learning, and memory, along with their electronic demonstrations using emerging devices. As a perspective, the connections and gaps between them and the challenges for building more bio‐plausible artificial neural networks are discussed. Abstract As the research on artificial intelligence booms, there is broad interest in brain‐inspired computing using novel neuromorphic devices. The potential of various emerging materials and devices for neuromorphic computing has attracted extensive research efforts, leading to a large number of publications. Going forward, in order to better emulate the brain's functions, its relevant fundamentals, working mechanisms, and resultant behaviors need to be re‐visited, better understood, and connected to electronics. A systematic overview of biological and artificial neural systems is given, along with their related critical mechanisms. Recent progress in neuromorphic devices is reviewed and, more importantly, the existing challenges are highlighted to hopefully shed light on future research directions.

Advanced Nanotechnology Leading the Way to Multimodal Imaging‐Guided Precision Surgical Therapy

By Cong Wang, Wenpei Fan, Zijian Zhang, Yu Wen, Li Xiong, Xiaoyuan Chen from Wiley: Advanced Materials: Table of Contents. Published on Dec 03, 2019.

State‐of‐the‐art advances in advanced nanotechnology for precision surgery are presented, with emphasis on multimodal imaging‐guided precision surgery for intraoperative visualization and synergistic surgical therapy for the elimination of residual lesions. These are of great value to push forward the development of nanomaterials in oncological surgery and clinical translation. Abstract Surgical resection is the primary and most effective treatment for most patients with solid tumors. However, patients suffer from postoperative recurrence and metastasis. In the past years, emerging nanotechnology has led the way to minimally invasive, precision and intelligent oncological surgery after the rapid development of minimally invasive surgical technology. Advanced nanotechnology in the construction of nanomaterials (NMs) for precision imaging‐guided surgery (IGS) as well as surgery‐assisted synergistic therapy is summarized, thereby unlocking the advantages of nanotechnology in multimodal IGS‐assisted precision synergistic cancer therapy. First, mechanisms and principles of NMs to surgical targets are briefly introduced. Multimodal imaging based on molecular imaging technologies provides a practical method to achieve intraoperative visualization with high resolution and deep tissue penetration. Moreover, multifunctional NMs synergize surgery with adjuvant therapy (e.g., chemotherapy, immunotherapy, phototherapy) to eliminate residual lesions. Finally, key issues in the development of ideal theranostic NMs associated with surgical applications and challenges of clinical transformation are discussed to push forward further development of NMs for multimodal IGS‐assisted precision synergistic cancer therapy.

Graphene/Half‐Metallic Heusler Alloy: A Novel Heterostructure toward High‐Performance Graphene Spintronic Devices

By Songtian Li, Konstantin V. Larionov, Zakhar I. Popov, Takahiro Watanabe, Kenta Amemiya, Shiro Entani, Pavel V. Avramov, Yuya Sakuraba, Hiroshi Naramoto, Pavel B. Sorokin, Seiji Sakai from Wiley: Advanced Materials: Table of Contents. Published on Dec 03, 2019.

A novel heterostructure consisting of high‐quality single‐layer graphene (SLG) and a half‐metallic Heusler alloy Co2Fe(Ge0.5Ga0.5) (CFGG) is developed. This new heterostructure shows unusual weak interfacial interaction, which leads to distinctive features such as preservation of the robust magnetism and half‐metallic characteristic of CFGG near the interface, and the quasi‐free‐standing nature of SLG, providing a new platform for future development of advanced graphene spintronic devices. Abstract Graphene‐based vertical spin valves (SVs) are expected to offer a large magnetoresistance effect without impairing the electrical conductivity, which can pave the way for the next generation of high‐speed and low‐power‐consumption storage and memory technologies. However, the graphene‐based vertical SV has failed to prove its competence due to the lack of a graphene/ferromagnet heterostructure, which can provide highly efficient spin transport. Herein, the synthesis and spin‐dependent electronic properties of a novel heterostructure consisting of single‐layer graphene (SLG) and a half‐metallic Co2Fe(Ge0.5Ga0.5) (CFGG) Heusler alloy ferromagnet are reported. The growth of high‐quality SLG with complete coverage by ultrahigh‐vacuum chemical vapor deposition on a magnetron‐sputtered single‐crystalline CFGG thin film is demonstrated. The quasi‐free‐standing nature of SLG and robust magnetism of CFGG at the SLG/CFGG interface are revealed through depth‐resolved X‐ray magnetic circular dichroism spectroscopy. Density functional theory (DFT) calculation results indicate that the inherent electronic properties of SLG and CFGG such as the linear Dirac band and half‐metallic band structure are preserved in the vicinity of the interface. These exciting findings suggest that the SLG/CFGG heterostructure possesses distinctive advantages over other reported graphene/ferromagnet heterostructures, for realizing effective transport of highly spin‐polarized electrons in graphene‐based vertical SV and other advanced spintronic devices.

Asymmetric Redox‐Polymer Interfaces for Electrochemical Reactive Separations: Synergistic Capture and Conversion of Arsenic

By Kwiyong Kim, Stephen Cotty, Johannes Elbert, Raylin Chen, Chia‐Hung Hou, Xiao Su from Wiley: Advanced Materials: Table of Contents. Published on Dec 03, 2019.

Redox‐active polymer materials are exploited for the reactive separation of arsenic oxyanions. The molecular selectivity of a metallopolymer is combined with the electrocatalytic properties of a radical‐based organic electrode to achieve exceptional separation factors and redox‐mediated transformation. This work paves the way for advanced redox‐materials to be used in synergistic electrochemical processes for water purification, chemical and environmental process intensification, and electrocatalysis. Abstract Advanced redox‐polymer materials offer a powerful platform for integrating electroseparations and electrocatalysis, especially for water purification and environmental remediation applications. The selective capture and remediation of trivalent arsenic (As(III)) is a central challenge for water purification due to its high toxicity and difficulty to remove at ultra‐dilute concentrations. Current methods present low ion selectivity, and require multistep processes to transform arsenic to the less harmful As(V) state. The tandem selective capture and conversion of As(III) to As(V) is achieved using an asymmetric design of two redox‐active polymers, poly(vinyl)ferrocene (PVF) and poly‐TEMPO‐methacrylate (PTMA). During capture, PVF selectively removes As(III) with exceptional uptake (>100 mg As/g adsorbent), and during release, synergistic electrocatalytic oxidation of As(III) to As(V) with >90% efficiency can be achieved by PTMA, a radical‐based redox polymer. The system demonstrates >90% removal efficiencies with real wastewater and concentrations of arsenic as low as 10 ppb. By integrating electron‐transfer through the judicious design of asymmetric redox‐materials, an order‐of‐magnitude energy efficiency increase can be achieved compared to non‐faradaic, carbon‐based materials. The study demonstrates for the first time the effectiveness of asymmetric redox‐active polymers for integrated reactive separations and electrochemically mediated process intensification for environmental remediation.

Catalysis of a Single Transition Metal Site for Water Oxidation: From Mononuclear Molecules to Single Atoms

By Huayang Zhang, Wenjie Tian, Xiaoguang Duan, Hongqi Sun, Shaomin Liu, Shaobin Wang from Wiley: Advanced Materials: Table of Contents. Published on Dec 03, 2019.

Focusing on single transition metal (TM) site catalysis, a clear roadmap with the correlations between the catalytic performances in water oxidation and the single‐TM‐site‐based structures including coordination and geometric structure, TM species, and support is provided. Bridging remarks between single metallic molecular complexes and single‐atom catalysts are also given. Abstract Low‐cost, nonprecious transition metal (TM) catalysts toward efficient water oxidation are of critical importance to future sustainable energy technologies. The advances in structure engineering of water oxidation catalysts (WOCs) with single TM centers as active sites, for example, single metallic molecular complexes (SMMCs), supported SMMCs, and single‐atom catalysts (SACs) in recent reports are examined. The efforts made on these configurations in terms of design principle, advanced characterization, performances and theoretical studies, are critically reviewed. A clear roadmap with the correlations between the single‐TM‐site‐based structures (coordination and geometric structure, TM species, support), and the catalytic performances in water oxidation is provided. The insights bridging SMMCs with SACs are also given. Finally, the challenges and opportunities in the single‐TM‐site catalysis are proposed.

Antibiotic‐Free Antibacterial Strategies Enabled by Nanomaterials: Progress and Perspectives

By Yue Wang, Yannan Yang, Yiru Shi, Hao Song, Chengzhong Yu from Wiley: Advanced Materials: Table of Contents. Published on Dec 03, 2019.

Antibiotic‐free strategies are promising candidates to revolutionize approaches to control bacterial infection. Recent progress in antibiotic‐free antibacterial approaches driven by innovations in advanced nanomaterials is highlighted. Their antibacterial mechanisms, structure–performance relationship, and current translation into practical antibacterial applications are summarized. Insights into a future without antibiotics are presented. Abstract Bacterial infection is one of the top ten leading causes of death globally and the worst killer in low‐income countries. The overuse of antibiotics leads to ever‐increasing antibiotic resistance, posing a severe threat to human health. Recent advances in nanotechnology provide new opportunities to address the challenges in bacterial infection by killing germs without using antibiotics. Antibiotic‐free antibacterial strategies enabled by advanced nanomaterials are presented. Nanomaterials are classified on the basis of their mode of action: nanomaterials with intrinsic or light‐mediated bactericidal properties and others that serve as vehicles for the delivery of natural antibacterial compounds. Specific attention is given to antibacterial mechanisms and the structure–performance relationship. Practical antibacterial applications employing these antibiotic‐free strategies are also introduced. Current challenges in this field and future perspectives are presented to stimulate new technologies and their translation to fight against bacterial infection.

Developments of Diketopyrrolopyrrole‐Dye‐Based Organic Semiconductors for a Wide Range of Applications in Electronics

By Qian Liu, Steven E. Bottle, Prashant Sonar from Wiley: Advanced Materials: Table of Contents. Published on Dec 03, 2019.

Diketopyrrolopyrrole (DPP) is one of the most promising building blocks for the construction of semiconductors for organic electronics. Inspired by their success in organic field‐effect transistors and organic solar cells, DPP‐based semiconductors have been introduced into more devices. The DPP‐based semiconductors used for wide range of electronic devices are summarized. Abstract In recent times, fused aromatic diketopyrrolopyrrole (DPP)‐based functional semiconductors have attracted considerable attention in the developing field of organic electronics. Over the past few years, DPP‐based semiconductors have demonstrated remarkable improvements in the performance of both organic field‐effect transistor (OFET) and organic photovoltaic (OPV) devices due to the favorable features of the DPP unit, such as excellent planarity and better electron‐withdrawing ability. Driven by this success, DPP‐based materials are now being exploited in various other electronic devices including complementary circuits, memory devices, chemical sensors, photodetectors, perovskite solar cells, organic light‐emitting diodes, and more. Recent developments in the use of DPP‐based materials for a wide range of electronic devices are summarized, focusing on OFET, OPV, and newly developed devices with a discussion of device performance in terms of molecular engineering. Useful guidance for the design of future DPP‐based materials and the exploration of more advanced applications is provided.

Blue Light Emitting Defective Nanocrystals Composed of Earth‐Abundant Elements

By Eric C. Hansen, Yun Liu, Hendrik Utzat, Sophie N. Bertram, Jeffrey C. Grossman, Moungi G. Bawendi from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 03, 2019.

Cu‐Al‐S/ZnS nanocrystals give rise to bright blue photoluminescence arising from highly localized, optically‐active defect states. Abstract Copper‐based ternary (I–III–VI) chalcogenide nanocrystals (NCs) are compositionally‐flexible semiconductors that do not contain lead (Pb) or cadmium (Cd). Cu‐In‐S NCs are the dominantly studied member of this important materials class and have been reported to contain optically‐active defect states. However, there are minimal reports of In‐free compositions that exhibit efficient photoluminescence (PL). Here, we report a novel solution‐phase synthesis of ≈4 nm defective nanocrystals (DNCs) composed of copper, aluminum, zinc, and sulfur with ≈20 % quantum yield and an attractive PL maximum of 450 nm. Extensive spectroscopic characterization suggests the presence of highly localized electronic states resulting in reasonably fast PL decays (≈1 ns), large vibrational energy spacing, small Stokes shift, and temperature‐independent PL linewidth and PL lifetime (between room temperature and ≈5 K). Furthermore, density functional theory (DFT) calculations suggest PL transitions arise from defects within a CuAl5S8 crystal lattice, which supports the experimental observation of highly‐localized states. The results reported here provide a new material with unique optoelectronic characteristics that is an important analog to well‐explored Cu‐In‐S NCs.

Detecting Counterion Dynamics in DNA–Protein Association

By Channing C. Pletka, Ridvan Nepravishta, Junji Iwahara from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 03, 2019.

Ion atmosphere: The condensation of cations around DNA and their release upon DNA–protein association have been proposed to contribute to binding thermodynamics and kinetics. In this work, NMR spectroscopy has been used to characterize the ion atmosphere around DNA and directly detect the release of cations upon DNA–protein association. This release is observed as an increase in the apparent diffusion coefficient Dapp of cations. Abstract Due to a high density of negative charges on its surface, DNA condenses cations as counterions, forming the so‐called “ion atmosphere”. Although the release of counterions upon DNA–protein association has been postulated to have a major contribution to the binding thermodynamics, this release remains to be confirmed through a direct observation of the ions. Herein, we report the characterization of the ion atmosphere around DNA using NMR spectroscopy and directly detect the release of counterions upon DNA–protein association. NMR‐based diffusion data reveal the highly dynamic nature of counterions within the ion atmosphere around DNA. Counterion release is observed as an increase in the apparent ionic diffusion coefficient, which directly provides the number of counterions released upon DNA–protein association.

Photosensitized intermolecular carboimination of alkenes through persistent radical effect

By Tuhin Patra, Peter Bellotti, Frank Glorius from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 03, 2019.

An intermolecular, two‐component vicinal carboimination of alkenes has been accomplished via energy transfer catalysis. Oxime esters of alkyl carboxylic acids are used as bifunctional reagents to generate both alkyl and iminyl radicals. Subsequently, the addition of alkyl radical to alkenes generates a transient radical for selective radical‐radical cross coupling with persistent iminyl radical. Furthermore, this protocol readily allows for direct access to aliphatic primary amines and α ‐amino acids through simple hydrolysis.

Synthetic Applications of Oxidative Aromatic Coupling—From Biphenols to Nanographenes

By Marek Grzybowski, Bartłomiej Sadowski, Holger Butenschön, Daniel T. Gryko from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 03, 2019.

Coupling up: The dehydrogenative coupling of arenes is an ultimate example of C−H activation. This Review highlights the most exciting examples of the Scholl reaction, ranging from the synthesis of biphenols through natural products to nanographenes and on‐surface dehydrogenation reported since 2013. Abstract Oxidative aromatic coupling occupies a fundamental place in the modern chemistry of aromatic compounds. It is a method of choice for the assembly of large and bewildering architectures. Considerable effort was also devoted to applications of the Scholl reaction for the synthesis of chiral biphenols and natural products. The ability to form biaryl linkages without any prefunctionalization provides an efficient pathway to many complex structures. Although the chemistry of this process is only now becoming fully understood, this reaction continues to both fascinate and challenge researchers. This is especially true for heterocoupling, that is, oxidative aromatic coupling with the chemoselective formation of a C−C bond between two different arenes. Analysis of the progress achieved in this field since 2013 reveals that many groups have contributed by pushing the boundary of structural possibilities, expanding into surface‐assisted (cyclo)dehydrogenation, and developing new reagents.

Highly Selective Production of Ethylene by the Electroreduction of Carbon Monoxide

By Ruixue Chen, Hai‐Yan Su, Deyu Liu, Rui Huang, Xianguang Meng, Xiaoju Cui, Zhong‐Qun Tian, Dong H. Zhang, Dehui Deng from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 03, 2019.

CORTE in the act: A direct electrocatalytic process allows a highly selective CO reduction to ethylene (CORTE) with water over Cu catalysts at room temperature and ambient pressure. An unprecedented 52.7 % Faradaic efficiency of ethylene formation results from optimization of the cathode structure to facilitate CO diffusion. Abstract Conversion of carbon monoxide to high value‐added ethylene with high selectivity by traditional syngas conversion process is challenging because of the limitation of Anderson‐Schulz–Flory distribution. Herein we report a direct electrocatalytic process for highly selective ethylene production from CO reduction with water over Cu catalysts at room temperature and ambient pressure. An unprecedented 52.7 % Faradaic efficiency of ethylene formation is achieved through optimization of cathode structure to facilitate CO diffusion at the surface of the electrode and Cu catalysts to enhance the C−C bond coupling. The highly selective ethylene production is almost without other carbon‐based byproducts (e.g. C1–C4 hydrocarbons and CO2) and avoids the drawbacks of the traditional Fischer–Tropsch process that always delivers undesired products. This study provides a new and promising strategy for highly selective production of ethylene from the abundant industrial CO.

Asymmetric Hydrogenation of Unfunctionalized, Tetrasubstituted, Acyclic Olefins

By Raphael Bigler, Kyle A. Mack, Jeff Shen, Paolo Tosatti, Chong Han, Haiming Zhang, Michelangelo Scalone, Andreas Pfaltz, Scott E. Denmark, Stefan Hildbrand, Francis Gosselin from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 03, 2019.

Asymmetric hydrogenation has evolved as one of the most powerful tools to construct stereocenters. However, the asymmetric hydrogenation of unfunctionalized, tetrasubstituted, acyclic olefins remains the pinnacle of asymmetric synthesis and an unsolved challenge. We report herein the discovery of an iridium catalyst for the first, generally‐applicable, highly enantio‐ and diastereoselective hydrogenation of such olefins and the mechanistic insights of the reaction. The power of this chemistry is demonstrated by the successful hydrogenation of a wide variety of electronically and sterically diverse olefins in excellent yield, enantio‐ and diastereoselectivity.

An Integrated Plasmo‐Photoelectronic Nanostructure Biosensor Detects an Infection Biomarker Accompanying Cell Death in Neutrophils

By Younggeun Park, Byunghoon Ryu, Qiufang Deng, Baihong Pan, Yujing Song, Yuzi Tian, Hasan B. Alam, Yongqing Li, Xiaogan Liang, Katsuo Kurabayashi from Wiley: Small: Table of Contents. Published on Dec 03, 2019.

The lack of an appropriate biosensing technology to detect the early onset of bacterial infections has prohibited timely clinical treatment of sepitc shock. This article presents a highly miniaturized plasmo‐photoelectronic device incorporating high‐affinity antibody‐conjugated hemispherical gold nanoparticles and a few‐layer molybdenum disulfide (MoS2) photoconductive channel to detect a blood biomarker released by neutrophils with high speed and sensitivity. Abstract Bacterial infections leading to sepsis are a major cause of deaths in the intensive care unit. Unfortunately, no effective methods are available to capture the early onset of infectious sepsis near the patient with both speed and sensitivity required for timely clinical treatment. To fill the gap, the authors develop a highly miniaturized (2.5 × 2.5 µm2) plasmo‐photoelectronic nanostructure device that detected citrullinated histone H3 (CitH3), a biomarker released to the blood circulatory system by neutrophils. Rapidly detecting CitH3 with high sensitivity has the great potential to prevent infections from developing life‐threatening septic shock. To this end, the author's device incorporates structurally engineered arrayed hemispherical gold nanoparticles that are functionalized with high‐affinity antibodies. A nanoplasmonic resonance shift induces a photoconduction increase in a few‐layer molybdenum disulfide (MoS2) channel, and it provides the sensor signal. The device achieves label‐free detection of serum CitH3 with a 5‐log dynamic range from 10−4 to 101 ng mL and a sample‐to‐answer time

Electron‐Beam‐Driven III‐Nitride Plasmonic Nanolasers in the Deep‐UV and Visible Region

By Tao Tao, Ting Zhi, Bin Liu, Peng Chen, Zili Xie, Hong Zhao, Fangfang Ren, Dunjun Chen, Youdou Zheng, Rong Zhang from Wiley: Small: Table of Contents. Published on Dec 03, 2019.

Ultralow‐threshold III‐nitride‐based plasmonic nanolasers emitting from the green to the deep‐ultraviolet region are demonstrated by energetic electron beam injection. Spatial and temporal coherences are observed for the first time, proving exciton‐plasmon coupled polariton lasing. This finding provides innovative insight that will contribute to the practical applications for computing systems and on‐chip optical communication. Abstract Plasmonic nanolasers based on wide bandgap semiconductors are presently attracting immense research interests due to the breaking in light diffraction limit and subwavelength mode operation with fast dynamics. However, these plasmonic nanolasers have so far been mostly realized in the visible light ranges, or most are still under optical excitation pumping. In this work, III‐nitride‐based plasmonic nanolasers emitting from the green to the deep‐ultraviolet (UV) region by energetic electron beam injection are reported, and a threshold as low as 8 kW cm−2 is achieved. A fast decay time as short as 123 ps is collected, indicating a strong coupling between excitons and surface plasmon. Both the spatial and temporal coherences are observed, which provide a solid evidence for exciton‐plasmon coupled polariton lasing. Consequently, the achievements in III‐nitride‐based plasmonic nanolaser devices represent a significant step toward practical applications for biological technology, computing systems, and on‐chip optical communication.

Inner Surface Design of Functional Microchannels for Microscale Flow Control

By Shuli Wang, Xian Yang, Feng Wu, Lingli Min, Xinyu Chen, Xu Hou from Wiley: Small: Table of Contents. Published on Dec 03, 2019.

Microscale flow behaviors in microfluidics are dominated by the interfaces between the fluids and the inner surfaces of microchannels. Here, the microchannel inner surface designs are systematically reviewed, including the solid surface and liquid surface designs, and their applications in microscale flow control. The prospective opportunities for the development of surface designs of microchannels are also highlighted. Abstract Fluidic flow behaviors in microfluidics are dominated by the interfaces created between the fluids and the inner surface walls of microchannels. Microchannel inner surface designs, including the surface chemical modification, and the construction of micro‐/nanostructures, are good examples of manipulating those interfaces between liquids and surfaces through tuning the chemical and physical properties of the inner walls of the microchannel. Therefore, the microchannel inner surface design plays critical roles in regulating microflows to enhance the capabilities of microfluidic systems for various applications. Most recently, the rapid progresses in micro‐/nanofabrication technologies and fundamental materials have also made it possible to integrate increasingly complex chemical and physical surface modification strategies with the preparation of microchannels in microfluidics. Besides, a wave of researches focusing on the ideas of using liquids as dynamic surface materials is identified, and the unique characteristics endowed with liquid–liquid interfaces have revealed that the interesting phenomena can extend the scope of interfacial interactions determining microflow behaviors. This review extensively discusses the microchannel inner surface designs for microflow control, especially evaluates them from the perspectives of the interfaces resulting from the inner surface designs. In addition, prospective opportunities for the development of surface designs of microchannels, and their applications are provided with the potential to attract scientific interest in areas related to the rapid development and applications of various microchannel systems.

Advanced Actuator Materials Powered by Biomimetic Helical Fiber Topologies

By Geoffrey M. Spinks from Wiley: Advanced Materials: Table of Contents. Published on Dec 03, 2019.

Mechanical actuation systems in plants and animals almost always involve helical structures and studies show that a helical arrangement of fibers in a compliant matrix generates a great diversity of movements and mechanical amplifications. Opportunities are identified to develop advanced artificial muscles since only a limited number of nature's mechanisms have been recreated in biomimetic systems to date. Abstract Helical constructs are ubiquitous in nature at all size domains, from molecular to macroscopic. The helical topology confers unique mechanical functions that activate certain phenomena, such as twining vines and vital cellular functions like the folding and packing of DNA into chromosomes. The understanding of active mechanical processes in plants, certain musculature in animals, and some biochemical processes in cells provides insight into the versatility of the helix. Most of these natural systems consist of helically oriented filaments embedded in a compliant matrix. In some cases, the matrix can change volume and in others the filaments can contract and the matrix is passive. In both cases, the helically arranged fibers determine the overall shape change with a great variety of responses involving length contraction/elongation, twisting, bending, and coiling. Synthetic actuator materials and systems that employ helical topologies have been described recently and demonstrate many fascinating and complex shape changes. However, significant new opportunities exist to mimic some of the most remarkable actions in nature, including the Vorticella's coiling stalk and DNA's supercoils, in the quest for superior artificial muscles.

Engineering Smart Nanofluidic Systems for Artificial Ion Channels and Ion Pumps: From Single‐Pore to Multichannel Membranes

By Zhen Zhang, Xiaodong Huang, Yongchao Qian, Weipeng Chen, Liping Wen, Lei Jiang from Wiley: Advanced Materials: Table of Contents. Published on Dec 03, 2019.

Inspired by the working mechanism of the biological ion channels and ion pumps in electric eels, a generic strategy for engineering smart nanofluidic systems for artificial ion channels and ion pumps is proposed and put into context with recent advances. These artificial systems show great promise in single‐molecule analysis, smart mass delivery, and energy conversion. Abstract Biological ion channels and ion pumps with intricate ion transport functions widely exist in living organisms and play irreplaceable roles in almost all physiological functions. Nanofluidics provides exciting opportunities to mimic these working processes, which not only helps understand ion transport in biological systems but also paves the way for the applications of artificial devices in many valuable areas. Recent progress in the engineering of smart nanofluidic systems for artificial ion channels and ion pumps is summarized. The artificial systems range from chemically and structurally diverse lipid‐membrane‐based nanopores to robust and scalable solid‐state nanopores. A generic strategy of gate location design is proposed. The single‐pore‐based platform concept can be rationally extended into multichannel membrane systems and shows unprecedented potential in many application areas, such as single‐molecule analysis, smart mass delivery, and energy conversion. Finally, some present underpinning issues that need to be addressed are discussed.

Metastable Chiral Azobenzenes Stabilized in a Double Racemate

By Amalu Mohan, Devika Sasikumar, Vinayak Bhat, Mahesh Hariharan from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 03, 2019.

Self‐assembly of chiral organic chromophores garners huge significance owing to the abundance of supramolecular chirality found in natural systems. We report an interdigitated molecular organization involving axially chiral twisted octabrominated perylenediimide (OBPDI) transferring chiral sense to achiral aromatic moieties. The two‐component crystalline architectures of OBPDI and electron rich aromatic units were facilitated through π‐hole•••π based donor‐acceptor interactions and the charge transfer characteristics in the ground and excited states of OBPDI cocrystals were established through spectroscopic and theoretical techniques. The OBPDI cocrystals entailed a remarkable homochiral segregation of P and M enantiomers of both the molecular entities in the same crystal system to render twisted double racemic architectures. Synergistically engendered cavities with stored chiral information of twisted OBPDI stabilized higher energy P/M enantiomers of trans‐azobenzene through non‐covalent interactions.

Dual Light and Temperature Responsive Micrometer‐Sized Structural Color Actuators

By Alberto Belmonte, Yera Ye Ussembayev, Tom Bus, Inge Nys, Kristiaan Neyts, Albertus P. H. J. Schenning from Wiley: Small: Table of Contents. Published on Dec 03, 2019.

Light and temperature responsive micrometer‐sized structural color actuators based on photonic polymer particles are fabricated. The particles exhibit anisotropic visible reflection ranging from red to blue. Upon light exposure, the particles show reversible asymmetric shape deformations combined with structural color changes. On increasing the temperature, the deformation is followed by a reduction or disappearance of the reflection. Abstract Externally induced color‐ and shape‐changes in micrometer‐sized objects are of great interest in novel application fields such as optofluidics and microrobotics. In this work, light and temperature responsive micrometer‐sized structural color actuators based on cholesteric liquid‐crystalline (CLC) polymer particles are presented. The particles are synthesized by suspension polymerization using a reactive CLC monomer mixture having a light responsive azobenzene dye. The particles exhibit anisotropic spot‐like and arc‐like reflective colored domains ranging from red to blue. Electron microscopy reveals a multidirectional asymmetric arrangement of the cholesteric layers in the particles and numerical simulations elucidate the anisotropic optical properties. Upon light exposure, the particles show reversible asymmetric shape deformations combined with structural color changes. When the temperature is increased above the liquid crystal‐isotropic phase transition temperature of the particles, the deformation is followed by a reduction or disappearance of the reflection. Such dual light and temperature responsive structural color actuators are interesting for a variety of micrometer‐sized devices.

Thickness‐Dependent In‐Plane Polarization and Structural Phase Transition in van der Waals Ferroelectric CuInP2S6

By Jianming Deng, Yanyu Liu, Mingqiang Li, Sheng Xu, Yingzhuo Lun, Peng Lv, Tianlong Xia, Peng Gao, Xueyun Wang, Jiawang Hong from Wiley: Small: Table of Contents. Published on Dec 03, 2019.

First observations of intrinsic in‐plane polarization in van der Waals ferroelectrics CuInP2S6 single crystals, and more interestingly, such in‐plane polarization is thickness dependent, which rotates perpendicular to the layer below 90 nm thickness. A structural phase transition from monoclinic to trigonal structure is responsible for the disappearance of in‐plane ferroelectricity and the abrupt change of elastic properties at the critical thickness. Abstract van der Waals (vdW) layered materials have rather weaker interlayer bonding than the intralayer bonding, therefore the exfoliation along the stacking direction enables the achievement of monolayer or few layers vdW materials with emerging novel physical properties and functionalities. The ferroelectricity in vdW materials recently attracts renewed interest for the potential use in high‐density storage devices. With the thickness becoming thinner, the competition between the surface energy, depolarization field, and interfacial chemical bonds may give rise to the modification of ferroelectricity and crystalline structure, which has limited investigations. In this work, combining the piezoresponse force microscope scanning, contact resonance imaging, the existence of the intrinsic in‐plane polarization in vdW ferroelectrics CuInP2S6 single crystals is reported, whereas below a critical thickness between 90 and 100 nm, the in‐plane polarization disappears. The Young's modulus also shows an abrupt stiffness at the critical thickness. Based on the density functional theory calculations, these behaviors are ascribed to a structural phase transition from monoclinic to trigonal structure, which is further verified by transmission electron microscope technique. These findings demonstrate the foundational importance of structural phase transition for enhancing the rich functionality and broad utility of vdW ferroelectrics.

Biodegradable Nanoprodrugs: “Delivering” ROS to Cancer Cells for Molecular Dynamic Therapy

By Zhong‐min Tang, Yan‐yan Liu, Da‐long Ni, Jia‐jia Zhou, Meng Zhang, Pei‐ran Zhao, Bin Lv, Han Wang, Da‐yong Jin, Wen‐bo Bu from Wiley: Advanced Materials: Table of Contents. Published on Dec 03, 2019.

Biodegradable nanoprodrugs of transferrin‐modified MgO2 nanosheets are developed to selectively deliver reactive oxygen species to cancer cells for molecular dynamic therapy strategy. The nanosheets favor acidic conditions and low catalase activity in the tumor microenvironment to react with protons and release nontoxic Mg2+. This reaction simultaneously produces abundant H2O2 and highly toxic ·OH, which destroys tumor cells. Abstract Biodegradable nanoprodrugs, inheriting the antitumor effects of chemotherapy drugs and overcoming the inevitable drawback of side effects on normal tissues, hold promise as next‐generation cancer therapy candidates. Biodegradable nanoprodrugs of transferrin‐modified MgO2 nanosheets are developed to selectively deliver reactive oxygen species to cancer cells for molecular dynamic therapy strategy. The nanosheets favor the acidic and low catalase activity tumor microenvironment to react with proton and release nontoxic Mg2+. This reaction simultaneously produces abundant H2O2 to induce cell death and damage the structure of transferrin to release Fe3+, which will react with H2O2 to produce highly toxic ·OH to kill tumor cells.

A Factorial Design Approach for Hydrothermal Synthesis of Phase Pure AgInO2 – A Parametric Optimization Study

By Beatriceveena T. V., Sree Rama Murthy A., Murugesan S., Prabhu E., K.I. Gnanasekar from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 03, 2019.

Owing to a wide range of industrial applications and fundamental importance, delafossite compounds have gathered tremendous interest in research community. In this study, the formation of hexagonal nanoplates of AgInO 2 mainly dominated by (00l) facets with no metallic Ag impurity, reported using a facile hydrothermal route at 180 o C using KOH as mineralizer by adopting a factorial design approach. Rietveld analysis of the powder XRD pattern and SAED confirms the rhombohedral system of AgInO 2 . FE‐SEM image shows a uniform hexagonal plate‐like morphology with an average width of about 300 nm and thickness of 70 nm. XPS and EDX analysis confirm K + ion free AgInO 2 . A specific surface area of about 48.5 m 2 /g is arrived from N 2 adsorption studies. Temperature‐dependent AC impedance measurements revealed an activation energy of 0.24 eV/f.u. Further, TG‐DTA studies found that the compound is stable in air up to 595 °C.

Polyketide Cyclizations for the Synthesis of Polyaromatics

By Vincent C. Fäseke, Felix C. Raps, Christof Sparr from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 03, 2019.

The folding and cyclization of poly‐β‐carbonyl chains controlled by the intricate enzymatic polyketide synthase machinery results in a remarkable diversity of aromatic natural products. Synthetic methods that allow for the preparation of highly reactive polyketide chains and control over their folding in ensuing cyclizations likewise lead to versatile divergent preparations of aromatic scaffolds valuable for numerous applications. Although biomimetic polyketide cyclizations have repeatedly been applied in the total synthesis of polyphenol natural products, their prospects for the preparation of the broad range of polyaromatic architectures has yet to reach its full potential. This review highlights some of the virtues of applying polyketide logic for the retrosynthetic analysis of polycyclic aromatic scaffolds, the increasing accessibility of precursors and the potential of small‐molecule catalysts for controlling polyketide cyclizations to provide polyaromatic scaffolds.

Gold and Carbene Relay Catalytic Enantioselective Cycloisomerization/Cyclization Reactions of Ynamides and Enals

By Liejin Zhou, Xingxing Wu, Xing Yang, Chengli Mou, Runjiang Song, Shuyan Yu, Huifang Chai, Lutai Pan, Zhichao Jin, Yonggui Robin Chi from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 03, 2019.

The combination of gold catalyst and N‐heterocyclic carbene (NHC) in the same solution for relay reactions was disclosed. The ynamide substrate was activated by gold catalyst to form an intermediate that subsequently reacted with the enals to form bicyclic δ‐lactam products with excellent diastereo‐ and enantio‐selectivities. Abstract The combined use of gold as transition metal catalyst and N‐heterocyclic carbene (NHC) as organic catalyst in the same solution for relay catalytic reactions was disclosed. The ynamide substrate was activated by gold catalyst to form unsaturated ketimine intermediate that subsequently reacted with the enals (via azolium enolate intermediate generated with NHC) effectively to form bicyclic lactam products with excellent diastereo‐ and enantio‐selectivities. The gold and NHC coordination and dissociation can be dynamic and tunable events, and thus allow the co‐existence of both active metal and carbene organic catalysts in appreciable concentrations, for the dual catalytic reaction to proceed.

Wed 15 Jan 14:00: The Golden Road: Synthesis and Surface Chemistry of Gold Nanocrystals BP Sustainability Lecture

From All Talks (aka the CURE list). Published on Dec 03, 2019.

The Golden Road: Synthesis and Surface Chemistry of Gold Nanocrystals

That “finely-divided metals” have unusual optical properties has been known since ancient times. Gold, for instance, can appear red, green, blue or brown on the nanoscale. In this talk I will describe synthetic methods to create colloidal gold nanocrystals of tunable size, shape, and therefore tunable optical properties. The structure-directing agents in the synthesis are thought to bind to different crystal facets of the growing nanocrystals and therefore dictate nanocrystal shape: new, improved imaging methods are beginning to allow us to see if this is true. The surface is where the nanocrystals meet and greet the rest of the world; strategies to coat them isotropically and anisotropically with hard and soft shells will be discussed.

BP Sustainability Lecture

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[ASAP] Exploring the Potential of c-Plane Indium Gallium Nitride Quantum Dots for Twin-Photon Emission

By Saroj Kanta Patra†‡ and Stefan Schulz*† from Nano Letters: Latest Articles (ACS Publications). Published on Dec 03, 2019.

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Nano Letters
DOI: 10.1021/acs.nanolett.9b03740

[ASAP] Reversible Tuning of the Plasmoelectric Effect in Noble Metal Nanostructures Through Manipulation of Organic Ligand Energy Levels

By Thakshila Liyanage†, Malpuri Nagaraju†, Merrell Johnson‡, Barry B. Muhoberac†, and Rajesh Sardar*†§ from Nano Letters: Latest Articles (ACS Publications). Published on Dec 03, 2019.

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Nano Letters
DOI: 10.1021/acs.nanolett.9b03588

[ASAP] Coexistence of Magnetic Orders in Two-Dimensional Magnet CrI3

By Ben Niu†‡?, Tang Su§‡?, Brian A. Francisco‡, Subhajit Ghosh?, Fariborz Kargar?, Xiong Huang?, Mark Lohmann‡, Junxue Li‡, Yadong Xu‡, Takashi Taniguchi#, Kenji Watanabe#, Di Wu†, Alexander Balandin?, Jing Shi*‡, and Yong-Tao Cui*‡ from Nano Letters: Latest Articles (ACS Publications). Published on Dec 03, 2019.

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Nano Letters
DOI: 10.1021/acs.nanolett.9b04282

[ASAP] Visualizing in Vivo Dynamics of Designer Nanoscaffolds

By Eric J. Young†‡, Jonathan K. Sakkos†‡, Jingcheng Huang†‡, Jacob K. Wright†‡, Benjamin Kachel§, Miguel Fuentes-Cabrera??, Cheryl A. Kerfeld†‡#, and Daniel C. Ducat*†‡ from Nano Letters: Latest Articles (ACS Publications). Published on Dec 03, 2019.

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Nano Letters
DOI: 10.1021/acs.nanolett.9b03651

[ASAP] Semiconductor–Ferromagnetic Insulator–Superconductor Nanowires: Stray Field and Exchange Field

By Yu Liu†‡, Saulius Vaitieke?nas‡§, Sara Marti´-Sa´nchez?, Christian Koch?, Sean Hart?#, Zheng Cui??, Thomas Kanne‡, Sabbir A. Khan†‡, Rawa Tanta†‡, Shivendra Upadhyay‡§, Martin Espin~eira Cachaza†‡, Charles M. Marcus‡§, Jordi Arbiol??, Kathryn A. Moler?#?, and Peter Krogstrup*†‡ from Nano Letters: Latest Articles (ACS Publications). Published on Dec 03, 2019.

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Nano Letters
DOI: 10.1021/acs.nanolett.9b04187

[ASAP] Ultralow Dissipation Patterned Silicon Nanowire Arrays for Scanning Probe Microscopy

By Pardis Sahafi†‡, William Rose§, Andrew Jordan†‡, Ben Yager†‡, Miche`le Piscitelli†‡, and Raffi Budakian*†‡? from Nano Letters: Latest Articles (ACS Publications). Published on Dec 03, 2019.

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Nano Letters
DOI: 10.1021/acs.nanolett.9b03668

[ASAP] Diels–Alder Reactions in Water Are Determined by Microsolvation

By Luis Ruiz Pestana†‡§, Hongxia Hao†‡, and Teresa Head-Gordon*†‡ from Nano Letters: Latest Articles (ACS Publications). Published on Dec 03, 2019.

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Nano Letters
DOI: 10.1021/acs.nanolett.9b04369

[ASAP] Control of Ionic Mobility via Charge Size Asymmetry in Random Ionomers

By Boran Ma†, Trung Dac Nguyen‡, and Monica Olvera de la Cruz*†‡§? from Nano Letters: Latest Articles (ACS Publications). Published on Dec 03, 2019.

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Nano Letters
DOI: 10.1021/acs.nanolett.9b02743

[ASAP] Sheddable Prodrug Vesicles Combating Adaptive Immune Resistance for Improved Photodynamic Immunotherapy of Cancer

By Ang Gao†, Binfan Chen†, Jing Gao†, Fengqi Zhou†, Madiha Saeed†, Bo Hou†, Yaping Li*†‡, and Haijun Yu*†‡ from Nano Letters: Latest Articles (ACS Publications). Published on Dec 03, 2019.

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Nano Letters
DOI: 10.1021/acs.nanolett.9b04012

[ASAP] Conducting and Lithiophilic MXene/Graphene Framework for High-Capacity, Dendrite-Free Lithium–Metal Anodes

By Haodong Shi†‡?, Chuanfang John Zhang#?, Pengfei Lu†, Yanfeng Dong†§, Pengchao Wen†, and Zhong-Shuai Wu*† from ACS Nano: Latest Articles (ACS Publications). Published on Dec 03, 2019.

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ACS Nano
DOI: 10.1021/acsnano.9b07710

[ASAP] Highly Efficient Metal-Free Nitrogen-Doped Nanocarbons with Unexpected Active Sites for Aerobic Catalytic Reactions

By Yangming Lin*†‡, Zigeng Liu‡, Yiming Niu†, Bingsen Zhang†, Qing Lu‡, Shuchang Wu†, Gabriele Centi§, Siglinda Perathoner§, Saskia Heumann‡, Linhui Yu*‡?, and Dang Sheng Su†? from ACS Nano: Latest Articles (ACS Publications). Published on Dec 03, 2019.

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ACS Nano
DOI: 10.1021/acsnano.9b05856

[ASAP] Spatially Controlled Fabrication and Mechanisms of Atomically Thin Nanowell Patterns in Bilayer WS2 Using in Situ High Temperature Electron Microscopy

By Jun Chen, Gyeong Hee Ryu, Qianyang Zhang, Yi Wen, Kuo-Lun Tai, Yang Lu, and Jamie H. Warner* from ACS Nano: Latest Articles (ACS Publications). Published on Dec 03, 2019.

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ACS Nano
DOI: 10.1021/acsnano.9b08220

[ASAP] A Dual Wavelength Polymerization and Bioconjugation Strategy for High Throughput Synthesis of Multivalent Ligands

By Zihao Li†#, Shashank Kosuri‡#, Henry Foster†, Jarrod Cohen§, Coline Jumeaux??, Molly M. Stevens??, Robert Chapman*†, and Adam J. Gormley*‡ from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Dec 03, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b09899

[ASAP] Site-Selective and Stereoselective O-Alkylation of Glycosides by Rh(II)-Catalyzed Carbenoid Insertion

By Jicheng Wu†#, Xiaolei Li†#, Xiaotian Qi‡, Xiyan Duan†?, Weston L. Cracraft§, Ilia A. Guzei§, Peng Liu*‡?, and Weiping Tang*†§ from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Dec 03, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b11262

[ASAP] Spotlights on Recent JACS Publications

By ACS Contributing Correspondents from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Dec 03, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b12985

[ASAP] Measuring and Modulating Substrate Confinement during Nitrogen-Atom Transfer in a Ru2-Based Metal-Organic Framework

By Chen-Hao Wang, Wen-Yang Gao, and David C. Powers* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Dec 03, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b09620

[ASAP] Correction to “Z-Selective Alkene Isomerization by High-Spin Cobalt(II) Complexes”

By Chi Chen, Thomas R. Dugan, William W. Brennessel, Daniel J. Weix*, and Patrick L. Holland* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Dec 03, 2019.

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b12184

[ASAP] Advancing Chelation Chemistry for Actinium and Other +3 f-Elements, Am, Cm, and La

By Benjamin W. Stein*†, Amanda Morgenstern†§, Enrique R. Batista*†, Eva R. Birnbaum†, Sharon E. Bone†, Samantha K. Cary, Maryline G. Ferrier†, Kevin D. John†, Juan Lezama Pacheco‡, Stosh A. Kozimor*†, Veronika Mocko†, Brian L. Scott†, and Ping Yang*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Dec 03, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b10354

[ASAP] Energy Transfer to Ni-Amine Complexes in Dual Catalytic, Light-Driven C–N Cross-Coupling Reactions

By Max Kudisch†, Chern-Hooi Lim†‡, Pall Thordarson*§, and Garret M. Miyake*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Dec 03, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b11049

[ASAP] Dynamic-Reversible Photoacoustic Probe for Continuous Ratiometric Sensing and Imaging of Redox Status in Vivo

By Judun Zheng, Qin Zeng, Ruijing Zhang, Da Xing*, and Tao Zhang* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Dec 03, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b10353

[ASAP] Synthesis of (-)-Mitrephorone A via a Bioinspired Late Stage C–H Oxidation of (-)-Mitrephorone B

By Lukas Anton Wein†, Klaus Wurst‡, Peter Angyal§, Lara Weisheit†, and Thomas Magauer*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Dec 03, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b11646

[ASAP] Bis(3-nitro-1-(trinitromethyl)-1H-1,2,4-triazol-5-yl)methanone: An Applicable and Very Dense Green Oxidizer

By Gang Zhao‡, Ping Yin§, Dheeraj Kumar†, Gregory H. Imler?, Damon A. Parrish?, and Jean’ne M. Shreeve*‡ from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Dec 03, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b11326

[ASAP] General Way To Construct Micro- and Mesoporous Metal–Organic Framework-Based Porous Liquids

By Sanfeng He, Lihan Chen, Jing Cui, Biao Yuan, Hongliang Wang, Fang Wang, Yi Yu, Yongjin Lee*, and Tao Li* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Dec 03, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b08458

Optical Properties of Symmetry-breaking Tetrahedral Nanoparticle

By Ishan Barman from RSC - Nanoscale latest articles. Published on Dec 03, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR08515G, Paper
Peng Zheng, Debadrita Paria, Haitao Wang, Ming Li, Ishan Barman
Spectrally rich but geometrically simple plasmonic metallic nanoparticles are highly favored in nanophotonics. Yet, they remain elusive owing to the symmetry-induced mode degeneracy and interband transitions-induced plasmonic damping. Hence, most...
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Ultra stable superatomic structure of doubly magic Ga13 and Ga13Li electrolyte

By Nicola Gaston from RSC - Nanoscale latest articles. Published on Dec 03, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR06959C, Paper
Krista Grace Steenbergen, Nicola Gaston
We report the extreme thermal stability of the superatomic electronic structure for 13-atom gallium clusters and the Ga13Li electrolyte. Using previously-validated first-principles simulations,[K. G. Steenbergen and N. Gaston, Phys. Rev....
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Room temperature single electron transistor based on a size-selected aluminium cluster

By Joris Van de Vondel from RSC - Nanoscale latest articles. Published on Dec 03, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR09467A, Paper
Vyacheslav S. Zharinov, Thomas Picot, Jeroen E. Scheerder, Ewald Janssens, Joris Van de Vondel
Single electron transistors (SET) are powerful devices to study the properties of nanoscale objects. However, the capabilities to place a nano-object between electrical contacts under pristine conditions are lacking. Here,...
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Hierarchical Heterostructure of SnO2 Confined on CuS Nanosheets for Efficient Electrocatalytic CO2 Reduction

By Tao Wu from RSC - Nanoscale latest articles. Published on Dec 03, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR08726E, Paper
Xiang Wang, Jing Lv, Jiaxu Zhang, Xiao-Li Wang, Chaozhuang Xue, Guo-Qing Bian, Dong-Sheng Li, Ying Wang, Tao Wu
CO2 direct electroreduction to ratio-tunable syngas (CO+H2) is an appealing solution to provide important feedstocks for many industrial processes. However, low-cost, earth-abundant yet efficient and stable electrocatalysts for composition-adjustable syngas...
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Synthesis of Switch-off Fluorescent Water-Stable Copper Nanoclusters Hg2+ Sensors in Simple One-Pot Approach by In-Situ Metal Reduction Strategy in the Presence of Thiolated Polymer Ligand Template

By Olga García from RSC - Nanoscale latest articles. Published on Dec 03, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR08439H, Paper
Jesús Benavides, Isabel Quijada-Garrido, Olga García
The fabrication of stable fluorescent copper nanoclusters (CuNCs) in aqueous media is still challenging despite their low price and potential biomedical applications. Herein, we report a facile and efficient strategy...
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Negative capacitance switching in size-modulated Fe3O4 nanoparticles with spontaneous non-stoichiometry: confronting its generalized origin in non-ferroelectric materials

By Kalyan Kumar Chattopadhyay from RSC - Nanoscale latest articles. Published on Dec 03, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR07902E, Paper
Souvik Bhattacharjee, Anibrata Banerjee, Nilesh Mazumder, Kausik Chanda, Saikat Sarkar, Kalyan Kumar Chattopadhyay
A persistent low-frequency negative capacitance (NC) dispersion has been detected in half-metallic polycrystalline magnetite (Fe3O4) nanoparticles having a size-variation: 13 – 236 nm, under the application of moderate dc bias....
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Thermal conductivity of V2O5 nanowires and their contact thermal conductance

By Xiangfan XU from RSC - Nanoscale latest articles. Published on Dec 03, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR08803B, Paper
Qilang Wang, Xin Liang, Bohai Liu, Yihui Song, Guohua Gao, Xiangfan XU
Vanadium pentoxide (V2O5) based composites show outstanding performance as the cathode materials in Lithium ion batteries. Yet the inferior thermal conductivity restricted the heat dissipation through the cathode electrode. In...
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Memristive Synapse with High Reproducibility for Flexible Neuromorphic Networks Based on Biological Nanocomposites

By Shusheng Pan from RSC - Nanoscale latest articles. Published on Dec 03, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR08001E, Paper
Jun Ge, Dongyuan Li, Changqiao Huang, Xuanbo Zhao, Jieli Qin, Huanyu Liu, Weiyong Ye, Wenchao Xu, Zhiyu Liu, Shusheng Pan
Memristive synapses from biomaterials are promising for building flexible and implantable artificial neuromorphic systems due to their remarkable mechanical and biological properties. However, these biological devices are limited to relatively...
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Correction: Compliments of confinements: substitution and dimension induced magnetic origin and band-bending mediated photocatalytic enhancements in Bi1−xDyxFeO3 particulate and fiber nanostructures

By S. Bharathkumar from RSC - Nanoscale latest articles. Published on Dec 03, 2019.

Nanoscale, 2019, Advance Article
DOI: 10.1039/C9NR90271F, Correction
Open Access Open Access
Creative Commons Licence  This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
M. Sakar, S. Balakumar, P. Saravanan, S. Bharathkumar
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Plant defensin PvD1 modulates the membrane composition of breast tumour-derived exosomes

By Diana Gaspar from RSC - Nanoscale latest articles. Published on Dec 03, 2019.

Nanoscale, 2019, Advance Article
DOI: 10.1039/C9NR07843F, Paper
Open Access Open Access
Creative Commons Licence  This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
Julia Skalska, Filipa D. Oliveira, Tiago N. Figueira, Érica O. Mello, Valdirene M. Gomes, Grant McNaughton-Smith, Miguel A. R. B. Castanho, Diana Gaspar
Plant defensin PvD1 attenuates recruitment of CD63 and CD9 to emerging exosomes of breast cancer MCF-7 cells, and binds to mature exosomes, which uncovers the nutraceutical potential of the natural source of PvD1, the bean Phaseolus vulgaris.
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Atomic-scale oxidation mechanisms of single-crystal magnesium

By Qiuming Peng from RSC - Nanoscale latest articles. Published on Dec 03, 2019.

Nanoscale, 2019, Advance Article
DOI: 10.1039/C9NR07265A, Paper
Yong Sun, Jinming Wang, Jianxin Guo, Qun Zu, Jianyu Huang, Qiuming Peng
Understanding the oxidation process of active metals plays a crucial role in improving their mechanical/oxidation properties.
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Ultra-Tough and Highly Ordered Macroscopic Fibers Assembly from 2D Functional Metal Oxides Nanosheets Liquid Crystals and Strong Ionic Interlayer Bridging

By Yao Li from RSC - Nanoscale latest articles. Published on Dec 03, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR08918G, Communication
Yalei Wang, Yuanchuan Zheng, Sheng Li, Jiupeng Zhao, Yao Li
Macroscopic assembly of 2D nanomaterials, especially for the one-dimensional macroscopic ordered fibers assembly from 2D liquid crystals (LCs), is rising to an unprecedented height and will continue to be an...
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Tue 10 Dec 13:00: Title to be confirmed

From All Talks (aka the CURE list). Published on Dec 02, 2019.

Amorphous Metal‐Organic Framework‐Dominated Nanocomposites with Both Compositional and Structural Heterogeneity for Oxygen Evolution

By Chao Liu, Jing Wang, Jingjing Wan, Yan Cheng, Rong Huang, Chaoqi Zhang, Wenli Hu, Guangfeng Wei, Chengzhong Yu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Amorphous metal‐organic frameworks ( a MOFs) are an emerging family of attractive materials with great application potential, however a MOFs are usually prepared under harsh conditions and a MOFs with complex compositions and structures are rarely reported. In this work, an a MOF‐dominated nanocomposite ( a MOF‐NC) with both structural and compositional complexity has been synthesized using a facile approach. A ligand‐competition amorphization mechanism is proposed based on experimental and density functional theory calculation results. The a MOF‐NC possesses a core‐shell‐nanorod@nanosheet architecture, including a Fe‐rich Fe‐Co‐ a MOF core and a Co‐rich Fe‐Co‐ a MOF shell in the core‐shell structured nanorod, and amorphous Co(OH) 2 nanosheets as the outer layer. Benefiting from the structural and compositional heterogeneity, the a MOF‐NC demonstrates an excellent oxygen evolution reaction activity with a low overpotential of 249 mV at 10.0 mA cm ‐2 and Tafel slope of 39.5 mV/dec. This study has provided an efficient strategy for the synthesis of a MOF‐based composites with improved performance.

Multi‐wall Sn/SnO2@Carbon Hollow Nanofibers Anode Material for High‐Rate and Long‐Life Lithium‐Ion Batteries

By Songwei Gao, Nü Wang, Shuai Li, Dianming Li, Zhimin Cui, Guichu Yue, Jingchong Liu, Xiaoxian Zhao, Lei Jiang, Yong Zhao from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

The rational design of hierarchical hollow nanomaterials is of great importance to the high‐rate and long‐cycle anode materials in lithium‐ion batteries. In this paper, multi‐wall Sn/SnO2@carbon hollow nanofibers evolve from SnO2 nanofibers are designed and pro‐gramable synthesized by electrospinning, polypyrrole coating and annealing reduction method. The synthesized hollow nanofibers have a special wire‐in‐double‐wall‐tube structure with larger specific surface area and abundant inner spaces, which can provide effective contacting area of electrolyte with electrode materials and more active sites for redox reaction. Furthermore, it shows excellent cycling stability by virtue of effectively alleviate the volume expansion caused pulverization of tin‐based electrode materials. Even after 2000 cycles, the wire‐in‐double‐wall‐tube Sn/SnO2@carbon nanofibers exhibit a high specific capacity of 986.3 mAh g‐1 (1 A·g‐1) and still maintains 508.2 mAh g‐1 at high current density of 5 A·g‐1. This outstanding electrochemical performance suggests the multi‐wall Sn/SnO2@ carbon hollow nanofibers are great promising for high performance energy storage systems.

The Application of Carbon Nanotube/Graphene‐Based Nanomaterials in Wastewater Treatment

By Zefang Yin, Chaojie Cui, Hang Chen, Duoni, Xiang Yu, Weizhong Qian from Wiley: Small: Table of Contents. Published on Dec 02, 2019.

The carbon nanotube (CNT)/graphene‐based nanomaterials have great potential as absorbent materials for organic wastewater treatment. The combination of new adsorption materials and traditional adsorption and desorption equipment and technologies will greatly shorten the industrialization process of new materials. Promoting the practical application of new materials will bring new vitality to the field of wastewater treatment. Abstract The treatment of organic wastewater is of great significance. Carbon nanotube (CNT)/graphene‐based nanomaterials have great potential as absorbent materials for organic wastewater treatment owing to their high specific surface area, mesoporous structure, tunable surface properties, and high chemical stability; these attributes allow them to endure harsh wastewater conditions, such as acidic, basic, and salty conditions at high concentrations or at high temperatures. Although a substantial amount of work has been reported on the performance of CNT/graphene‐based nanomaterials in organic wastewater systems, engineering challenges still exist for their practical application. Herein, the adsorption mechanism of CNT‐ and graphene‐based nanomaterials is summarized, including the adsorption mechanism of CNTs and graphene at the atomic and molecular levels, their hydrophilic and hydrophobic surface properties, and the structure–property relationship required for adsorption to occur. Second, the structural modification and recombination methods of CNT‐ and graphene‐based adsorbents for various organic wastewater systems are introduced. Third, the engineering challenges, including the molding of macroscopically stable adsorbents, adsorption isotherm models and adsorption kinetic behaviors, and reversible adsorption performance compared to that of activated carbon (AC) are discussed. Finally, cost issues are discussed in light of scalable and practical application of these materials.

Dynamic Complex‐to‐Complex Transformations of Heterobimetallic Systems Influence the Cage Structure or Spin State of Iron(II) Ions

By Matthias Hardy, Niklas Struch, Julian J. Holstein, Gregor Schnakenburg, Norbert Wagner, Marianne Engeser, Johannes Beck, Guido H. Clever, Arne Lützen from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Two new heterobimetallic cages, a trigonal bipyramidal and a cubic one, were assembled from the same mononuclear metalloligand adopting the molecular library approach, using iron(II) and palladium(II) building blocks. The ligand system was designed to readily assemble through subcomponent self‐assembly. It allowed the introduction of steric strain at the iron(II) centres, which stabilizes its paramagnetic high‐spin state. This steric strain was utilized to perform dynamic complex‐to‐complex transformations with both, the metalloligand and heterobimetallic cages. Addition of sterically less crowded subcomponents as a chemical stimulus transformed all complexes to their previously reported low‐spin analogues. The metalloligand and bipyramid incorporated the new building block more readily than the cubic cage, probably because the geometric structure of the sterically crowded metalloligand favours the cube formation. Furthermore it was possible to provoke structural transformations upon addition of more favourable chelating ligands, converting the cubic structures into bipyramidal ones.

Chiral Phosphoric Acid‐Catalyzed Kinetic Resolution of 2‐Amido Benzyl Alcohols: Asymmetric Synthesis of 4H‐3,1‐Benzoxazines

By Subramani Rajkumar, Mengyao Tang, Xiaoyu Yang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

An efficient method for asymmetric synthesis of 4 H ‐3,1‐benzoxazines was developed via kinetic resolution of 2‐amido benzyl alcohols through chiral phosphoric acid catalyzed intramolecular cyclizations. A broad range of benzyl alcohols (both secondary and tertiary alcohols) could be kinetically resolved with high selectivities, with s factor up to 94. Mechanistic studies were performed to elucidate the mechanism of these reactions, in which the amide moieties reacted as the electrophiles. Gram‐scale reaction and facile transformations of the chiral products well demonstrate the potential of this method in asymmetric synthesis of biologically active chiral heterocycles.

Construction of ultrathin V3S4@C nanosheets assembled hierarchical nanotubes towards alkali‐ion batteries with ion‐dependent electrochemical mechanisms

By Yang Liu, Zehang Sun, Xuan Sun, Yue Lin, Ke Tan, Jinfeng Sun, Longwei Liang, Linrui Hou, Changzhou Yuan from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Rational design of universal alkali metal ions (Li + , Na + and K + ) host materials are still enormously challengeable for rechargeable batteries. Herein, the ultrathin core‐shell V 3 S 4 @C nanosheets assembled hierarchical nanotubes (V 3 S 4 @C NS‐HNTs) are firstly synthesized via a self‐template strategy, and evaluated as general anodes for alkali‐ion batteries. Systematical in‐situ/ex‐situ structural/physicochemical characterizations and density functional theory calculations bring insights into intrinsic relationship between crystal structures and electrochemical mechanisms of the V 3 S 4 @C NS‐HNTs electrode. The unique V 3 S 4 @C NS‐HNTs are endowed with strong structural rigidness due to the layered VS 2 subunits and interlayer occupied V atoms, and efficient alkali‐ion adsorption/diffusion thanks to the electroactive V 3 S 4 ‐C interfaces. More impressively, the resulted V 3 S 4 @C NS‐HNTs anode exhibit distinct alkali‐ion dependent charge storage mechanisms, and particularly exceptional long‐durability cyclic performance in storage of K + , benefiting from synergistic contributions of pseudocapacitive and reversible intercalation/de‐intercaltion behaviors, superior to those of the conversion reaction involved Li + ‐/Na + ‐storage counterparts.

First Observation of Photoinduced Mo‐CN Bond Breakage Leading to Spin Triplet Trapping in Octacyanomolybdate

By Corine Mathonière, Xinghui Qi, Sébastien Pillet, Coen de Graaf, El-Eulmi Bendeif, Philippe Guionneau, Mathieu Rouzières, Valérie Marvaud, Olaf Stefanczyk, Michał Magott, Dawid Pinkowicz from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

The photo‐induced properties of the octacoordinated complex, K4MoIV(CN)8·2H2O, are studied by theoretical calculations, crystallographic, optical and magnetic measurements. After blue light irradiation, the crystal structure collected at 10 K reveals an heptacoordinated Mo(CN)7species originating from the light‐induced breaking of one Mo‐CN bond, concomitant with the photo‐induced formation of a paramagnetic signal. When it is heated to 70 K, the compound recovers its original diamagnetic ground state demonstrating the full reversibility. The photomagnetic properties show a partial conversion to a triplet state possessing a significant magnetic anisotropy in agreementwith the theoretical studies. Inspired by our results, we have isolated a new compound [K(crypt‐222)]3[MoIV(CN)7]·3CH3CN using a photochemical pathway confirming that the photo‐dissociation is also activatedin solution.

Catalytic Selective Dihydrosilylation of Internal Alkynes Enabled by Rare‐Earth Ate Complex

By Wufeng Chen, Haibin Song, Jianfeng Li, Chunming Cui from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Hydrosilylation of alkynes generally yielded vinylsilanes, which are generally inert to the further hydrosilylation because of the steric effects. We report here the first successful dihydrosilylation of aryl‐ and silyl‐substituted internal alkynes enabled by a rare‐earth ate complex to yield geminal bis and tris(silanes), respectively. The lanthanum bis(amido) ate complex supported by an ene‐diamido ligand proved to be the ideal catalyst for this unprecedented transformation, while the same series of yttrium and samarium alkyl and samarium bis(amido) ate complexes exhibited poor activity and selectivity, indicating the significant effects of the ionic size and ate structure of the rare‐earth catalysts.

Stable Heterometallic Cluster‐Based Organic Frameworks Catalysts for Artificial Photosynthesis

By Ya-Qian Lan, Long-Zhang Dong, Lei Zhang, Qing Huang, Meng Lu, Wen-Xin Ji, Jiang Liu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Coupling CO 2 reduction with H 2 O oxidation reactions on one photocatalyst has always been a challenging task in artificial photosynthesis. Herein, we first report a series of stable heterometallic Fe 2 M cluster‐based MOFs ( NNU‐31‐M , M = Co, Ni, Zn) photocatalysts, which can achieve the overall conversion of CO 2 and H 2 O to HCOOH and O 2 without the assistance of additional sacrificial agent and photosensitizer. The heterometallic cluster units and photosensitive ligands excited by visible light generate separated electrons and holes. Then, low‐valent metal M accepts electrons to reduce CO 2 , and high‐valent Fe uses holes to oxidize H 2 O. This is the first MOF photocatalyst system to finish artificial photosynthetic full reaction. It is noted that NNU‐31‐Zn exhibits the highest HCOOH yield of 26.3 μmol g ‐1 h ‐1 (selectivity of ca . 100%). Furthermore, the DFT calculations based on crystal structures demonstrate the photocatalytic reaction mechanism. This work proposes a new strategy for how to design crystalline photocatalyst to realize artificial photosynthetic overall reaction.

Corrigendum: Dynamics of Synthetic Membraneless Organelles in Microfluidic Droplets

By Miriam Linsenmeier, Marie R. G. Kopp, Fulvio Grigolato, Leonidas Emmanouilidis, Dany Liu, Dominik Zürcher, Maria Hondele, Karsten Weis, Umberto Capasso Palmiero, Paolo Arosio from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Imidazotetrazines as Weighable Diazomethane Surrogates for Esterifications and Cyclopropanations

By Riley Svec, Paul J. Hergenrother from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Diazomethane is one of the most versatile reagents in organic synthesis, but its utility is limited by its hazardous nature. Although alternative methods exist to perform the unique chemistry of diazomethane, these suffer from diminished reactivity and/or correspondingly harsher conditions. Here we describe the repurposing of imidazotetrazines (such as temozolomide, TMZ, the standard of care for glioblastoma) for use as synthetic precursors of alkyl diazoniums.  TMZ is employed to conduct esterifications and metal‐catalyzed cyclopropanations, and results show that methyl ester formation from a wide variety of substrates is especially efficient and operationally simple. TMZ is a commercially available solid that is non‐explosive and non‐toxic, and should find broad utility as a replacement for diazomethane.

Metabolic Labeling of Peptidoglycan with NIR‐II Dye Enables in vivo Imaging of Gut Microbiota

By Chaoyong James Yang, Wei Wang, Qinglai Yang, Yahui Du, Xiaobo Zhou, Xiaochen Du, Qiuyue Wu, Liyuan Lin, Yanling Song, Fuyou Li, Weihong Tan from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Deepening our understanding of mammalian gut microbiota has been greatly hampered by the lack of a facile, real‐time and in vivo bacterial imaging method. To address this unmet need in microbial visualization, we herein report the development of a second near‐infrared (NIR‐II)‐based method for in vivo imaging of gut bacteria. Using D‐propargylglycine in gavage and then click reaction with an azide‐containing NIR‐II dye, gut microbiota of a donor mouse was strongly labeled with NIR‐II fluorescence on their peptidoglycan. The bacteria could be readily visualized in recipient mouse gut with high spatial resolution and deep tissue penetration under NIR irradiation. We then adopted this chemical strategy to image different bacterial species, which expanded its applicability in microbiology. Moreover, by employing this method, we found that the biogeography of gut microbiota was dramatically affected by host’s gastrointestinal motilities. The NIR‐II‐based metabolic labeling strategy reported here, to our knowledge, provides the first protocol for facile in vivo visualization of gut microbiota within deep tissues, and offers an instrumental tool for deciphering the complex biology of these gut “dark matters”.

Heterobifunctional rotaxanes for asymmetric catalysis

By Noel Pairault, Hui Zhu, Dennis Jansen, Alexander Huber, Constantin Daniliuc, Stefan Grimme, Jochen Niemeyer from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Heterobifunctional rotaxanes serve as efficient catalysts for the addition of malonates to Michael‐acceptors. We report a series of four different heterobifunctional rotaxanes, featuring an amine‐based thread and a chiral 1,1´‐binaphthyl‐phosphoric acid based macrocycle. High‐level DFT calculations provided mechanistic insights and enabled rational catalyst improvements, leading to interlocked catalysts that surpass their non‐interlocked counterparts in terms of reaction rates and stereoselectivities.

Explore the Unknown—The Value of Basic Research

By Katharina Kohse‐Höinghaus, Harald Fuchs, Tao Zhang, Yueliang Wu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

The Beijing Declaration on basic research was recently signed by Presidents of the Chinese Academy of Sciences (CAS) and the German National Academy of Sciences, Leopoldina. With this undertaking both academies underlined their joint efforts to “promote the scientific spirit”, strive for excellence, encourage collaborative, inclusive and responsible scientific research, and foster a favorable environment for scientific development.

Welch Award in Chemistry:A. P. Alivisatos and C. M. Lieber / Wilhelm Exner Medal:J. M. DeSimone / Ernst Schering Prize:P. Cramer

By from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Hybrid Halide Perovskites: Discussions on Terminology and Materials

By Nicolas Mercier from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

What′s my name? In this Viewpoint, a critical discussion about the use of the word “perovskite” and some acronyms (DJ, RP, ACI, d‐HP, hollow perovskites) is proposed, and a description of perovskite networks through an elimination/substitution process from the ABX3 structure is compared to the known dimensional reduction concept. Abstract Hybrid halide perovskites (HP) have emerged in the last decade as a new class of semiconductors with superior performances in photovoltaic and electronic devices. The literature about these halide semiconductors is abundant and a lot of names/expressions are used to define networks, structures, or materials. In this context, there is a need to offer some discussions about the relevance of using the word “perovskite” and the associated expressions (“RP” (Ruddlesden–Popper), “DJ” (Dion–Jacobson), “ACI” (alternating cations in the interlayer space), “hexagonal perovskites”, “hollow perovskites”, “d‐HP” (deficient 3D HP),…). Moreover, the description of perovskite networks through elimination/substitution processes from the ABX3 structure will be compared to the known dimensional reduction concept.

Corrigendum: Molecularly Mixed Composite Membranes for Advanced Separation Processes

By Guanghui Zhu, Fengyi Zhang, Matthew P. Rivera, Xunxiang Hu, Guoyan Zhang, Christopher W. Jones, Ryan P. Lively from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Graphical Abstract: Angew. Chem. Int. Ed. 50/2019

By from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Frontispiece: A Versatile 3D and 4D Printing System through Photocontrolled RAFT Polymerization

By Zhiheng Zhang, Nathaniel Corrigan, Ali Bagheri, Jianyong Jin, Cyrille Boyer from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Photopolymerization RAFT 3D and 4D printing is achieved using an eco‐friendly resin under mild conditions as shown by N. Corrigan, C. Boyer et al. in their Research Article on page 17954. The resulting materials show RAFT‐dependent mechanical properties and can be post‐functionalized.

Back Cover: Catalytic Enantioselective Cyclopropenation of Internal Alkynes: Access to Difluoromethylated Three‐Membered Carbocycles (Angew. Chem. Int. Ed. 50/2019)

By Zhi‐Qi Zhang, Meng‐Meng Zheng, Xiao‐Song Xue, Ilan Marek, Fa‐Guang Zhang, Jun‐An Ma from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

An answer to the long‐standing challenge of catalytic enantioselective cyclopropenation of internal alkynes with acceptor‐carbene precursors is presented by I. Marek, F.‐G. Zhang, J.‐A. Ma, and co‐workers in their Communication on page 18191 ff. This Rh‐catalyzed transformation utilizes a fluorinated diazo reagent to react with internal alkynes, providing facile access to enantioenriched three‐membered carbocycles. The picture shows the cyclical world with major elements of the reaction.

Inside Back Cover: Nucleation and Growth of Amino Acid and Peptide Supramolecular Polymers through Liquid–Liquid Phase Separation (Angew. Chem. Int. Ed. 50/2019)

By Chengqian Yuan, Aviad Levin, Wei Chen, Ruirui Xing, Qianli Zou, Therese W. Herling, Pavan Kumar Challa, Tuomas P. J. Knowles, Xuehai Yan from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

The separation of the liquid phase into solute‐rich and solute‐poor phases is an elementary step leading to the nucleation of supramolecular nanofibrils from amphiphilic amino acids and peptides. As X. Yan, T. P. J. Knowles et al. show in their Research Article on page 18116 ff., the solute‐rich liquid droplets with low enthalpy act as nucleation sites, significantly decrease the nucleation barrier towards solid phase, and eventually form thermodynamically more favorable nanofibrils.

Inside Cover: Selective Autonomous Molecular Transport and Collection by Hydrogel‐Embedded Supramolecular Chemical Gradients (Angew. Chem. Int. Ed. 50/2019)

By Shiyan Zhang, Chunjie Zhang, Hao Chen, Spencer J. Kieffer, Frank Neubrech, Harald Giessen, Andrew G. Alleyne, Paul V. Braun from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Chemical‐gradient‐driven concentration enhances the sensitivity and selectivity of chemical sensors. In their Communication on page 18165, P. V. Braun et al. show how hydrogel‐embedded radially symmetric cyclodextrin gradients direct transport of molecules including the nerve agent simulant 4‐methylumbelliferyl phosphate. To provide near real‐time read‐out of the analyte concentration an array of IR‐resonant metallic nanoantennas was used to enhance the IR signal generated by the analyte.

Cover Picture: Luminescence and Light‐Driven Energy and Electron Transfer from an Exceptionally Long‐Lived Excited State of a Non‐Innocent Chromium(III) Complex (Angew. Chem. Int. Ed. 50/2019)

By Steffen Treiling, Cui Wang, Christoph Förster, Florian Reichenauer, Jens Kalmbach, Pit Boden, Joe P. Harris, Luca M. Carrella, Eva Rentschler, Ute Resch‐Genger, Christian Reber, Michael Seitz, Markus Gerhards, Katja Heinze from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Inversion symmetry increases the excited‐state lifetime of a molecular ruby at room temperature in fluid solution to 4.5 ms while the photoluminescence quantum yield remains as high as 8.2 %, as shown by K. Heinze and co‐workers in their Research Article on page 18075. The chromium(III) complex [Cr(tpe)2]3+ is furthermore competent in light‐induced electron and energy transfer processes, and thus resembles classical noble metal complexes.

Intermolecular Stereospecific Substitution of Underivatized Enantioenriched Secondary Alcohols by Organocatalysis

By Sunisa Akkarasamiyo, Joseph S. M. Samec from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Mitsunobu revisited: The use of (2‐hydroxybenzyl)diphenylphosphine oxide as an efficient catalyst has recently enabled the development of a catalytic redox‐neutral Mitsunobu reaction. This reaction constitutes the first intermolecular stereospecific substitution of non‐allylic alcohols where only water is formed as a by‐product. Abstract The stereospecific substitution of non‐derivatized and non‐allylic enantioenriched alcohols with only water as a by‐product would enable the use of readily available alcohols as substrates for green and sustainable transformations. However, the poor leaving group ability of the OH group has hampered the development of such a process. Denton and co‐workers recently described the use of (2‐hydroxybenzyl)diphenylphosphine oxide as a catalyst of a redox‐neutral and zero‐waste‐generating Mitsunobu reaction. This innovative process constitutes the first intermolecular stereospecific substitution of non‐allylic alcohols, and might find industrial applications.

Chemical Functionalization of Nanodiamonds: Opportunities and Challenges Ahead

By Giacomo Reina, Li Zhao, Alberto Bianco, Naoki Komatsu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Nanodiamonds are forever: Nanodiamonds (NDs) are used in a variety of fields spanning from electronics and optics to biomedicine. Controlled surface functionalization can make NDs high‐performant nanomaterials. In this Minireview, different methodologies of synthesis, purification, and surface functionalization as well as biomedical applications are critically discussed. Abstract Nanodiamond(ND)‐based technologies are flourishing in a wide variety of fields spanning from electronics and optics to biomedicine. NDs are considered a family of nanomaterials with an sp3 carbon core and a variety of sizes, shapes, and surfaces. They show interesting physicochemical properties such as hardness, stiffness, and chemical stability. Additionally, they can undergo ad‐hoc core and surface functionalization, which tailors them for the desired applications. Noteworthy, the properties of NDs and their surface chemistry are highly dependent on the synthetic method used to prepare them. In this Minireview, we describe the preparation of NDs from the materials‐chemistry viewpoint. The different methodologies of synthesis, purification, and surface functionalization as well as biomedical applications are critically discussed. New synthetic approaches as well as limits and obstacles of NDs are presented and analyzed.

Site‐Specific Encoding of Photoactivity in Antibodies Enables Light‐Mediated Antibody–Antigen Binding on Live Cells

By Thomas Bridge, Saher A. Shaikh, Paul Thomas, Joaquin Botta, Peter J. McCormick, Amit Sachdeva from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Site‐specific installation of a single photoactive amino acid in an antibody enables development of photoactive antibodies allowing light‐controlled, cell‐specific delivery of small molecules on live cancer cells. Abstract Antibodies have found applications in several fields, including, medicine, diagnostics, and nanotechnology, yet methods to modulate antibody–antigen binding using an external agent remain limited. Here, we have developed photoactive antibody fragments by genetic site‐specific replacement of single tyrosine residues with photocaged tyrosine, in an antibody fragment, 7D12. A simple and robust assay is adopted to evaluate the light‐mediated binding of 7D12 mutants to its target, epidermal growth factor receptor (EGFR), on the surface of cancer cells. Presence of photocaged tyrosine reduces 7D12‐EGFR binding affinity by over 20‐fold in two out of three 7D12 mutants studied, and binding is restored upon exposure to 365 nm light. Molecular dynamics simulations explain the difference in effect of photocaging on 7D12‐EGFR interaction among the mutants. Finally, we demonstrate the application of photoactive antibodies in delivering fluorophores to EGFR‐positive live cancer cells in a light‐dependent manner.

Electronic Tuning of Mixed Quinoidal‐Aromatic Conjugated Polyelectrolytes: Direct Ionic Substitution on Polymer Main‐Chains

By Christopher L. Anderson, Nan Dai, Simon J. Teat, Bo He, Shu Wang, Yi Liu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

All in the mix: Conjugated polyelectrolytes are a class of conjugated polymers with ionic substituents. The direct ionic substitution of mixed quinoidal‐aromatic polymers is shown to be an efficient strategy for forming low band gap conjugated polyelectrolytes. These materials display high activity in photothermal therapy applications. Abstract The synthesis of conjugated polymers with ionic substituents directly bound to their main chain repeat units is a strategy for generating strongly electron‐accepting conjugated polyelectrolytes, as demonstrated through the synthesis of a series of ionic azaquinodimethane (iAQM) compounds. The introduction of cationic substituents onto the quinoidal para‐azaquinodimethane (AQM) core gives rise to a strongly electron‐accepting building block, which can be employed in the synthesis of ionic small molecules and conjugated polyelectrolytes (CPEs). Electrochemical measurements alongside theoretical calculations indicate notably low‐lying LUMO values for the iAQMs. The optical band gaps measured for these compounds are highly tunable based on structure, ranging from 2.30 eV in small molecules down to 1.22 eV in polymers. The iAQM small molecules and CPEs showcase the band gap reduction effects of combining the donor‐acceptor strategy with the bond‐length alternation reduction strategy. As a demonstration of their utility, the iAQM CPEs so generated were used as active agents in photothermal therapy.

Nucleation and Growth of Amino Acid and Peptide Supramolecular Polymers through Liquid–Liquid Phase Separation

By Chengqian Yuan, Aviad Levin, Wei Chen, Ruirui Xing, Qianli Zou, Therese W. Herling, Pavan Kumar Challa, Tuomas P. J. Knowles, Xuehai Yan from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Separation into rich and poor: The formation of supramolecular nanofibrils from amphiphilic amino acids and short peptides follows a nucleation–elongation mechanism mediated by liquid–liquid phase separation. The initial formation of solute‐poor and solute‐rich liquid droplets is entropy driven, while the transition of liquid droplets to nanofibrils is dominated by enthalpic interactions. Abstract The transition of peptides and proteins from the solution phase into fibrillar structures is a general phenomenon encountered in functional and aberrant biology and is increasingly exploited in soft materials science. However, the fundamental molecular events underpinning the early stages of their assembly and subsequent growth have remained challenging to elucidate. Here, we show that liquid–liquid phase separation into solute‐rich and solute‐poor phases is a fundamental step leading to the nucleation of supramolecular nanofibrils from molecular building blocks, including peptides and even amphiphilic amino acids. The solute‐rich liquid droplets act as nucleation sites, allowing the formation of thermodynamically favorable nanofibrils following Ostwald's step rule. The transition from solution to liquid droplets is entropy driven while the transition from liquid droplets to nanofibrils is mediated by enthalpic interactions and characterized by structural reorganization. These findings shed light on how the nucleation barrier toward the formation of solid phases can be lowered through a kinetic mechanism which proceeds through a metastable liquid phase.

Anisotropic Thermal Expansion as the Source of Macroscopic and Molecular Scale Motion in Phosphorescent Amphidynamic Crystals

By Mingoo Jin, Sho Yamamoto, Tomohiro Seki, Hajime Ito, Miguel A. Garcia‐Garibay from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Jumping crystals: Multifunctional amphidynamic crystalline materials based on dumbbell shape gold(I) complexes are characterized by motion at the molecular and macroscopic scales. Macroscopic motion occurs in the form thermosalient crystal moving and/or jumping as the result of anisotropic thermal expansion. Phosphorescence of the crystals is correlated to the molecular rotation. Abstract Herein we report a crystalline molecular rotor with rotationally modulated triplet emission that displays macroscopic dynamics in the form of crystal moving and/or jumping, also known as salient effects. Molecular rotor 2 with a central 1,4‐diethynyl‐2,3‐difluorophenylene rotator linked to two gold(I) nodes, crystalizes as infinite 1D chains through intermolecular gold(I)–gold(I) interactions. The rotational motion changes the orientation of the central phenylene, changing the electronic communication between adjacent chromophores, and thus the emission intensities. Crystals of 2 showed the large and reversible thermal expansion/compression anisotropy, which accounts for 1) a nonlinear Arrhenius behavior in molecular‐level rotational dynamics, which correlates with 2) changes in emission, and determines 3) the macroscopic crystal motion. A molecular rotor analogue 3 has properties similar to those of 2, suggesting a generalized way to control mechanical properties at molecular and macroscopic scales.

Visible‐Light‐Driven Janus Microvehicles in Biological Media

By Marta Pacheco, Beatriz Jurado‐Sánchez, Alberto Escarpa from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

A light‐driven multifunctional Janus micromotor was assembled from CdTe or CdSe@ZnS quantum dots (QDs), a polycaprolactone shell, and an asymmetric Fe3O4 patch for propulsion. Efficient propulsion was observed in complex samples such as human blood serum. The micromotors were used for efficient endotoxin removal and for mercury removal by cationic exchange with the CdSe@ZnS core–shell QDs. Abstract A light‐driven multifunctional Janus micromotor for the removal of bacterial endotoxins and heavy metals is described. The micromotor was assembled by using the biocompatible polymer polycaprolactone for the encapsulation of CdTe or CdSe@ZnS quantum dots (QDs) as photoactive materials and an asymmetric Fe3O4 patch for propulsion. The micromotors can be activated with visible light (470–490 nm) to propel in peroxide or glucose media by a diffusiophoretic mechanism. Efficient propulsion was observed for the first time in complex samples such as human blood serum. These properties were exploited for efficient endotoxin removal using lipopolysaccharides from Escherichia coli O111:B4 as a model toxin. The micromotors were also used for mercury removal by cationic exchange with the CdSe@ZnS core–shell QDs. Cytotoxicity assays in HeLa cell lines demonstrated the high biocompatibility of the micromotors for future detoxification applications.

Insight into Three‐Coordinate Aluminum Species on Ethanol‐to‐Olefin Conversion over ZSM‐5 Zeolites

By Zichun Wang, Luke A. O'Dell, Xin Zeng, Can Liu, Shufang Zhao, Wenwen Zhang, Marianne Gaborieau, Yijiao Jiang, Jun Huang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Three's company: Three‐coordinate Al3+ species working with Brønsted acid sites can accelerate bioethanol dehydration from >9 h to 1–2 h at the much lower reaction temperature and a short unsteady‐state period. Abstract Commercial bioethanol can be readily converted into ethylene by a dehydration process using solid acids, such as Brønsted acidic H‐ZSM‐5 zeolites, and thus, it is an ideal candidate to replace petroleum and coal for the sustainable production of ethylene. Now, strong Lewis acidic extra‐framework three‐coordinate Al3+ species were introduced into H‐ZSM‐5 zeolites to improve their catalytic activity. Remarkably, Al3+ species working with Brønsted acid sites can accelerate ethanol dehydration at a much lower reaction temperature and shorten the unsteady‐state period within 1–2 h, compared to >9 h for those without Al3+ species, which can significantly enhance the ethanol dehydration efficiency and reduce the cost. The reaction mechanism, studied by solid‐state NMR, shows that strong Lewis acidic EFAl‐Al3+ species can collaborate with Brønsted acid sites and promote ethanol dehydration either directly or indirectly via an aromatics‐based cycle to produce ethylene.

Visible‐Light‐Driven N‐Heterocyclic Carbene Catalyzed γ‐ and ϵ‐Alkylation with Alkyl Radicals

By Lei Dai, Zi‐Hao Xia, Yuan‐Yuan Gao, Zhong‐Hua Gao, Song Ye from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

A merger: The merging of photoredox catalysis and N‐heterocyclic carbene (NHC) catalysis for γ‐ and ϵ‐alkylation of enals with alkyl halides was developed, giving the corresponding γ‐substituted α,β‐unsaturated esters and ϵ‐substituted α,β‐γ,δ‐diunsaturated esters exclusively in good yields. Abstract The merging of photoredox catalysis and N‐heterocyclic carbene (NHC) catalysis for γ‐ and ϵ‐alkylation of enals with alkyl radicals was developed. The alkylation reaction of γ‐oxidized enals with alkyl halides worked well for the synthesis γ‐multisubstituted‐α,β‐unsaturated esters, including those with challenging vicinal all‐carbon quaternary centers. The synthesis of ϵ‐multisubstituted‐α,β‐γ,δ‐diunsaturated esters by an unprecedented NHC‐catalyzed ϵ‐functionalization was also established.

Luminescence and Light‐Driven Energy and Electron Transfer from an Exceptionally Long‐Lived Excited State of a Non‐Innocent Chromium(III) Complex

By Steffen Treiling, Cui Wang, Christoph Förster, Florian Reichenauer, Jens Kalmbach, Pit Boden, Joe P. Harris, Luca M. Carrella, Eva Rentschler, Ute Resch‐Genger, Christian Reber, Michael Seitz, Markus Gerhards, Katja Heinze from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Super‐long luminescence lifetime (4500 μs) at room temperature, high quantum yield (8.2 %) and reversible redox chemistry in the complex [Cr(tpe)2]3+ containing an Earth‐abundant first row transition metal ion is enabled by ligand bite angle, inversion symmetry and ligand non‐innocence (tpe=1,1,1‐tris (pyrid‐2‐yl)ethane). [Cr(tpe)2]3+ is competent in light‐induced energy and electron transfer processes similar to classical noble metal ion complexes. Abstract Photoactive metal complexes employing Earth‐abundant metal ions are a key to sustainable photophysical and photochemical applications. We exploit the effects of an inversion center and ligand non‐innocence to tune the luminescence and photochemistry of the excited state of the [CrN6] chromophore [Cr(tpe)2]3+ with close to octahedral symmetry (tpe=1,1,1‐tris(pyrid‐2‐yl)ethane). [Cr(tpe)2]3+ exhibits the longest luminescence lifetime (τ=4500 μs) reported up to date for a molecular polypyridyl chromium(III) complex together with a very high luminescence quantum yield of Φ=8.2 % at room temperature in fluid solution. Furthermore, the tpe ligands in [Cr(tpe)2]3+ are redox non‐innocent, leading to reversible reductive chemistry. The excited state redox potential and lifetime of [Cr(tpe)2]3+ surpass those of the classical photosensitizer [Ru(bpy)3]2+ (bpy=2,2′‐bipyridine) enabling energy transfer (to oxygen) and photoredox processes (with azulene and tri(n‐butyl)amine).

Activation and Characterization of Cryptic Gene Cluster: Two Series of Aromatic Polyketides Biosynthesized by Divergent Pathways

By Zhen‐Yu Ji, Qiu‐Yue Nie, Yue Yin, Mei Zhang, Hai‐Xue Pan, Xian‐Feng Hou, Gong‐Li Tang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Breaking the silence: A silent gene cluster was engaged by the expression of a positive regulator gene in tandem mode, directing the biosynthesis of eight aromatic polyketides. These polyketides comprise two different frameworks, two pentacyclic isomers (1 and 2) and six glycosylated tetracyclines (3–8), which are proposed to arise from divergent pathways originating from a common intermediate. Abstract One biosynthetic gene cluster (BGC) usually governs the biosynthesis of a series of compounds exhibiting either the same or similar molecular scaffolds. Reported here is a multiplex activation strategy to awaken a cryptic BGC associated with tetracycline polyketides, resulting in the discovery of compounds having different core structures. By constitutively expressing a positive regulator gene in tandem mode, a single BGC directed the biosynthesis of eight aromatic polyketides with two types of frameworks, two pentacyclic isomers and six glycosylated tetracyclines. The proposed biosynthetic pathway, based on systematic gene inactivation and identification of intermediates, employs two sets of tailoring enzymes with a branching point from the same intermediate. These findings not only provide new insights into the role of tailoring enzymes in the diversification of polyketides, but also highlight a reliable strategy for genome mining of natural products.

Trismaleimide Dendrimers: Helix‐to‐Superhelix Supramolecular Transition Accompanied by White‐Light Emission

By Fen Li, Xiaohui Li, Ying Wang, Xin Zhang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

White‐light superhelix: Trismaleimide dendrimers grow through the generations in an alternating OFF/ON fluorescence fashion. A peripherally alkyl‐modified dendrimer forms fluorescent, hierarchical superhelical structures where the primary and higher‐order helical directions are opposing. During superhelix formation, white‐light emission is observed. Abstract Reported here are unprecedented fluorescent superhelices composed of primary, supramolecular polymers of the opposite helical twist. A new class of functional dendrimers was synthesized by amino‐ene click reactions, and they demonstrate an alternating OFF/ON fluorescence with generation growth. A peripherally alkyl‐modified dendrimer displays helix‐sense‐selective supramolecular polymerization, which predominantly forms right‐handed (or left‐handed) helical supramolecular polymers in the solution containing chiral solvents. With increasing the concentration, these primary helical supramolecular polymers spontaneously twist around themselves in the opposite direction to form superhelical structures. Atomic force microscopy and circular dichroism measurements were used to directly observe the helix‐to‐superhelix transition occurring with a reversal in the helical direction. Exceptional white‐light emission was observed during superhelix formation.

Hydrostibination

By Katherine M. Marczenko, Joseph A. Zurakowski, Karlee L. Bamford, Joshua W. M. MacMillan, Saurabh S. Chitnis from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Sb is the new B: A new family of Lewis acidic and hydridic diaminostibines were prepared and used in the catalyst‐ and initiator‐free hydrostibination of robust multiple bonds. The results further the concept of a diagonal relationship between boron and the heaviest Group 15 elements. Abstract A rigid naphthalenediamine framework has been used to prepare antimony hydrides that feature LUMO shapes and energies similar to those found in secondary boranes. By exploiting this feature, we introduce the first examples of uncatalyzed hydrostibination reactions of robust C≡C, C=C, C=O, and N=N bonds as new elementary hydrometalation reactions analogous to hydroboration. These results endorse the notion of a diagonal relationship between the lightest p‐block element and the heaviest Group 15 elements and may lead to the conception of novel reaction chemistry.

Quantification of the Charge Consuming Phenomena under High‐Voltage Hold of Carbon/Carbon Supercapacitors by Coupling Operando and Post‐Mortem Analyses

By Patryk Przygocki, Paula Ratajczak, François Béguin from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

The degradation mechanisms occurring during high‐voltage hold of supercapacitors are revealed through a self‐consistent approach combining operando analyses of evolving gases by electrochemical mass spectrometry (EMS) and post‐mortem analyses of electrodes by temperature programmed desorption–TPD. Abstract Enhancing the operating voltage of supercapacitors (SCs), hence their specific energy, is important. However, long‐term hold at high voltage entails loss of capacitance, increase of resistance and internal pressure. Such detrimental effects could be reduced by obtaining quantitative information on the relative impact of the various mechanisms leading to the worsening of the SCs performance. Now, for a carbon/carbon supercapacitor in aqueous Li2SO4, a self‐consistent approach is used to assign leaking charge during high voltage hold to the charge: 1) distributed throughout the electrochemical cell (steady‐state leakage current measurements), 2) spent at each electrode for gases production (operando electrochemical mass spectrometry (EMS) analysis and pressure records), 3) utilized to oxidize the electrodes surface (from post‐mortem surface functionality determination by temperature programmed desorption (TPD)), and 4) used for other parasitic reactions.

A Divergent Synthetic Route to the Vallesamidine and Schizozygine Alkaloids: Total Synthesis of (+)‐Vallesamidine and (+)‐14,15‐Dehydrostrempeliopine

By Xiangyu Zhang, James C. Anderson from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Necessity is the mother of invention and never more so than in target synthesis. The total synthesis of (+)‐vallesamidine and (+)‐14,15‐dehydrostrempeliopine was possible from a common intermediate that is related to other alkaloids and necessitated the development of a [1,4] hydride transfer/Mannich cyclisation to build ring E (see scheme). Abstract The total synthesis of representative members of the schizozygine alkaloids, (+)‐vallesamidine and (+)‐14,15‐dehydrostrempeliopine, were completed from a late‐stage divergent intermediate. The synthesis took advantage of efficient nitro‐group reactions with the A/B/C ring skeleton constructed concisely on a gram scale through an asymmetric Michael addition, nitro‐Mannich/lactamisation, Tsuji–Trost allylation, and intramolecular C−N coupling reaction. Other key features of the synthesis are a novel [1,4] hydride transfer/Mannich‐type cyclisation to build ring E and a diastereoselective ring‐closing metathesis reaction to construct ring D. This approach gave access to a late‐stage C14,C15 alkene divergent intermediate that could be simply transformed into (+)‐vallesamidine, (+)‐14,15‐dehydrostrempeliopine, and potentially other schizozygine alkaloids and unnatural derivatives.

Water‐Induced Growth of a Highly Oriented Mesoporous Graphitic Carbon Nanospring for Fast Potassium‐Ion Adsorption/Intercalation Storage

By Yong Qian, Song Jiang, Yang Li, Zheng Yi, Jie Zhou, Jie Tian, Ning Lin, Yitai Qian from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Spring loaded: A spring‐like highly oriented mesoporous graphitic carbon anode (OGCS) undergoes K‐adsorption in mesopores then K‐intercalation in the graphite layer to form KC8 with a low discharge voltage. It provides a large number of active edge‐plane sites and expands one‐dimensionally along the long axis, resulting in ultra‐high capacity and long‐term stability over 10 000 cycles. Abstract A highly oriented mesoporous graphitic carbon nanospring (OGCS) with graphitic layers that are perpendicular to the axis is prepared by hydrothermal treatment of epoxy resin at 500 °C and annealing at 1400 °C. Water plays an important role in not only forming the graphitic carbon nanospring with a high [002] orientation and a large amount of active edge‐plane sites, but also in the generation of the mesoporous structure, which facilitate fast K‐ion adsorption and diffusion. In situ and ex situ measurements confirm that OGCS undergoes K‐adsorption in mesopores and then K‐intercalation in the graphite layer to form KC8 with a low discharge voltage. The spring‐like nanostructure can expand one‐dimensionally along the axial direction to accommodate the volume variation. The OGCS electrode thus shows a much better K‐storage performance than that of unoriented graphitic carbon.

Multifunctional Tubular Organic Cage‐Supported Ultrafine Palladium Nanoparticles for Sequential Catalysis

By Nana Sun, Chiming Wang, Hailong Wang, Le Yang, Peng Jin, Wei Zhang, Jianzhuang Jiang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

What a team! The excellent photocatalytic activity of porous organic cages, together with cage‐supported ultrafine palladium nanoparticles, enables sequential reactions, including‐visible light‐induced aerobic hydroxylation and hydrogenation. Abstract The imine condensation reaction of 5,5′‐(benzo[c][1,2,5]thiadiazole‐4,7‐diyl)diisophthalaldehyde with cyclohexanediamine resulted in a shape‐persistent multifunctional tubular organic cage (MTC1). It exhibits selective fluorescence sensing towards divalent Pd ions with a very low detection limit (38 ppb), suggesting effective complexation between these two species. Subsequent reduction of MTC1 and Pd(OAc)2 with NaBH4 afforded a cage‐supported catalyst with well‐dispersed ultrafine Pd nanoparticles (NPs) in a narrow size distribution (1.9±0.4 nm), denoted as Pd@MTC1‐1/5. Such ultrafine Pd NPs in Pd@MTC1‐1/5, in cooperation with photocatalytically active MTC1, enable efficient sequential reactions involving visible light‐induced aerobic hydroxylation of 4‐nitrophenylboronic acid to 4‐nitrophenol and the following hydride reduction with NaBH4. This is the first example of a multifunctional organic cage capable of sensing, directing nanoparticle growth, and catalyzing sequential reactions.

P2‐Na0.67AlxMn1−xO2: Cost‐Effective, Stable and High‐Rate Sodium Electrodes by Suppressing Phase Transitions and Enhancing Sodium Cation Mobility

By Xiangsi Liu, Wenhua Zuo, Bizhu Zheng, Yuxuan Xiang, Ke Zhou, Zhumei Xiao, Peizhao Shan, Jingwen Shi, Qi Li, Guiming Zhong, Riqiang Fu, Yong Yang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Al the better: Sodium layered P2‐stacking Na0.67MnO2 materials have shown great promise for sodium‐ion batteries. Undesired Jahn–Teller effect of the Mn4+/Mn3+ redox couple lead to cracks, amorphization and rapid capacity decay. These problems are overcome by introducing Al to decrease the number of Mn3+ Jahn–Teller centers, giving pure P2‐type Na0.67AlxMn1−xO2 materials. Abstract Sodium layered P2‐stacking Na0.67MnO2 materials have shown great promise for sodium‐ion batteries. However, the undesired Jahn–Teller effect of the Mn4+/Mn3+ redox couple and multiple biphasic structural transitions during charge/discharge of the materials lead to anisotropic structure expansion and rapid capacity decay. Herein, by introducing abundant Al into the transition‐metal layers to decrease the number of Mn3+, we obtain the low cost pure P2‐type Na0.67AlxMn1−xO2 (x=0.05, 0.1 and 0.2) materials with high structural stability and promising performance. The Al‐doping effect on the long/short range structural evolutions and electrochemical performances is further investigated by combining in situ synchrotron XRD and solid‐state NMR techniques. Our results reveal that Al‐doping alleviates the phase transformations thus giving rise to better cycling life, and leads to a larger spacing of Na+ layer thus producing a remarkable rate capability of 96 mAh g‐1 at 1200 mA g‐1.

Asymmetric Dearomatization of Indole Derivatives with N‐Hydroxycarbamates Enabled by Photoredox Catalysis

By Yuan‐Zheng Cheng, Qing‐Ru Zhao, Xiao Zhang, Shu‐Li You from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Unlocked: Dearomatization of indoles and their derivatives provides efficient synthetic routes for substituted indolines. For this asymmetric dearomatization reaction the indoles function as electrophiles. The combined utilization of a photocatalyst and chiral phosphoric acid (CPA) open to air unlocks the umpolung reactivity of indoles, enabling enantioselective dearomatization of indoles with N‐hydroxycarbamates as nucleophiles. Abstract Dearomatization of indoles provides efficient synthetic routes for substituted indolines. In most cases, indoles serve as nucleophiles. Reported here is an asymmetric dearomatization reaction of indole derivatives that function as electrophiles. The combination of a photocatalyst and chiral phosphoric acid open to air unlocks the umpolung reactivity of indoles, enabling their dearomatization with N‐hydroxycarbamates as nucleophiles. A variety of fused indolines bearing intriguing oxy‐amines were constructed in excellent yields with moderate to high enantioselectivities. Mechanistic studies show that the realization of two sequential single‐electron transfer oxidations of the indole derivatives is key, generating the configurationally biased carbocation species while providing the source of stereochemical induction. These results not only provide an efficient synthesis of enantioenriched indoline derivatives, but also offer a novel strategy for further designing asymmetric dearomatization reactions.

Sequential Oxidation and C−H Bond Activation at a Gallium(I) Center

By Aishabibi Kassymbek, Sergei F. Vyboishchikov, Bulat M. Gabidullin, Denis Spasyuk, Melanie Pilkington, Georgii I. Nikonov from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

NacNac! Who′s there? In situ oxidation of the GaI compound 1 results in the transient monomeric oxo derivative NacNacGa=O, which adds to C−H bonds of a variety of substrates featuring hard donor sites. Density‐functional calculations are also presented. Abstract In situ oxidation of the GaI compound NacNacGa by either N2O or pyridine oxide results in the generation of a labile monomeric oxide, NacNacGa(O), which can easily cleave the C−H bonds of aliphatic and aromatic substrates featuring good donor sites. The products of this reaction are gallium organyl hydroxides. DFT calculations show that these reactions start with the formation of NacNac‐Ga(O)(L) adducts, the oxo ligand of which can easily abstract protons from nearby C−H bonds, even for sp2‐hybridized carbon centers. Aliphatic amines do not enter this reaction for kinetic reasons, presumably because of the unfavorable sterics.

Copernicium: A Relativistic Noble Liquid

By Jan‐Michael Mewes, Odile R. Smits, Georg Kresse, Peter Schwerdtfeger from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

The physicochemical properties of copernicium (Cn) were explored by means of first‐principles free‐energy calculations. The resulting melting and boiling points of 283±11 K and 340±10 K classify Cn as a volatile liquid, for which a density very similar to that of mercury is calculated. However, in contrast to metallic mercury, bulk Cn exhibits a large band gap of 6.4 eV and is dominated by dispersion interactions, which is consistent with a noble‐gas‐like character. Abstract The chemical nature and aggregate state of superheavy copernicium (Cn) have been subject of speculation for many years. While strong relativistic effects render Cn chemically inert, which led Pitzer to suggest a noble‐gas‐like behavior in 1975, Eichler and co‐workers in 2008 reported substantial interactions with a gold surface in atom‐at‐a‐time experiments, suggesting a metallic character and a solid aggregate state. Herein, we explore the physicochemical properties of Cn by means of first‐principles free‐energy calculations, which confirm Pitzer's original hypothesis: With predicted melting and boiling points of 283±11 K and 340±10 K, Cn is indeed a volatile liquid and exhibits a density very similar to that of mercury. However, in stark contrast to mercury and the lighter Group 12 metals, we find bulk Cn to be bound by dispersion and to exhibit a large band gap of 6.4 eV, which is consistent with a noble‐gas‐like character. This non‐group‐conforming behavior is eventually traced back to strong scalar‐relativistic effects, and in the non‐relativistic limit, Cn appears as a common Group 12 metal.

Loading Photochromic Molecules into a Luminescent Metal–Organic Framework for Information Anticounterfeiting

By Zhiqiang Li, Guannan Wang, Yingxiang Ye, Bin Li, Huanrong Li, Banglin Chen from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Secret agent MOF: Reversible confidential information protection is realized by loading photoswitchable molecules into lanthanide MOFs. The light‐triggered open‐ and closed‐form isomerization of the diarylethene unit regulates the luminescence on–off switching of the lanthanide emitting center, allowing for reversible multiple information anticounterfeiting by simply alternating the exposure to UV and visible light. Abstract Stimuli‐responsive photoluminescent materials have attracted considerable attention owing to their potential applications in security protection because the information recorded directly in materials with static luminescent outputs are usually visible under either ambient or UV light. Herein, we realize reversible information anticounterfeiting by loading a photoswitchable diarylethene derivative into a lanthanide metal–organic framework (MOF). Light triggers the open‐ and closed‐form isomerization of the diarylethene unit, which respectively regulates the inactivation and activation of the photochromic FRET process between the diarylethene acceptor and lanthanide donor, resulting in reversible luminescence on–off switching of the lanthanide emitting center in the MOF host. This photoresponsive host–guest system allows for reversible multiple information pattern visible/invisible transformation by simply alternating the exposure to UV and visible light.

Asymmetric Desymmetrization of Oxetanes for the Synthesis of Chiral Tetrahydrothiophenes and Tetrahydroselenophenes

By Renwei Zhang, Wengang Guo, Meng Duan, K. N. Houk, Jianwei Sun from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Tamed: A new catalytic asymmetric approach for the synthesis of chiral tetrahydrothiophenes and tetrahydroselenophenes bearing all‐carbon quaternary stereocenters is disclosed. This reaction employs a chiral acid to promote efficient desymmetrization of the oxetanes by either a well‐positioned internal sulfur or selenium nucleophile with excellent enantioselectivities. Key to success is the taming of the sulfur and selenium reactivities in the form of a thioester and selenoester, respectively. Abstract Chiral tetrahydrothiophenes and tetrahydroselenophenes are highly useful structural units. Described here is a new catalytic asymmetric approach for their synthesis. With a suitable chiral Brønsted acid catalyst, an oxetane desymmetrization by a well‐positioned internal sulfur or selenium nucleophile proceeded efficiently to generate all‐carbon quaternary stereocenters with excellent enantioselectivities. Taming the sulfur and selenium nucleophile in the form of a thioester and selenoester, respectively, is crucial to the success of this work. This approach also allows the facile synthesis of chiral tetrahydrothiopyrans. Mechanistic studies, including DFT calculations, suggested an intramolecular acyl‐transfer pathway. Utilities of the chiral products are also demonstrated.

A Versatile 3D and 4D Printing System through Photocontrolled RAFT Polymerization

By Zhiheng Zhang, Nathaniel Corrigan, Ali Bagheri, Jianyong Jin, Cyrille Boyer from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

RAFT 3D and 4D printing is achieved using an eco‐friendly resin under mild conditions. The resulting materials show RAFT‐dependent mechanical properties and can be post‐functionalized after fabrication. Solvation induced actuation of photocontrolled 3D printed hydrogels demonstrates a 4D printing system. Abstract Reversible addition‐fragmentation chain‐transfer (RAFT) polymerization is a valuable tool for synthesizing macromolecules with controlled topologies and diverse chemical functionalities. However, the application of RAFT polymerization to additive‐manufacturing processes has been prevented due to the slow polymerization rates of typical systems. In this work, we developed and optimized a rapid visible (green) light mediated RAFT polymerization process and applied it to an open‐air 3D printing system. The reaction components are non‐toxic, metal free and environmentally friendly, which tailors these systems toward biomaterial fabrication. The inclusion of RAFT agent in the photosensitive resin provided control over the mechanical properties of 3D printed materials and allowed these materials to be post‐functionalized after 3D printing. Additionally, photoinduced spatiotemporal control of the network structure provided a one‐pass approach to 4D printed materials. This RAFT‐mediated 3D and 4D printing process should provide access to a range of new functional and stimuli‐responsive materials.

Organoplatinum‐Substituted Polyoxometalate Inhibits β‐amyloid Aggregation for Alzheimer's Therapy

By Jing Zhao, Kexin Li, Kaiwei Wan, Tiedong Sun, Nannan Zheng, Fanjiao Zhu, Jichao Ma, Jia Jiao, Tianchan Li, Jinyuan Ni, Xinghua Shi, Hui Wang, Qiang Peng, Jing Ai, Wanhai Xu, Shaoqin Liu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

An organic platinum‐substituted polyoxometalate, (Me4N)3[PW11O40(SiC3H6NH2)2PtCl2] (abbreviated as PtII‐PW11) was designed and prepared. It can effectively inhibit Aβ42 aggregation in vitro, reduce Aβ deposition and rescue memory loss in vivo without noticeable cytotoxicity. PtII‐PW11 demonstrates its potential as therapeutic drug for AD treatment. Abstract Aggregated β‐amyloid (Aβ) is widely considered as a key factor in triggering progressive loss of neuronal function in Alzheimer's disease (AD), so targeting and inhibiting Aβ aggregation has been broadly recognized as an efficient therapeutic strategy for curing AD. Herein, we designed and prepared an organic platinum‐substituted polyoxometalate, (Me4N)3[PW11O40(SiC3H6NH2)2PtCl2] (abbreviated as PtII‐PW11) for inhibiting Aβ42 aggregation. The mechanism of inhibition on Aβ42 aggregation by PtII‐PW11 was attributed to the multiple interactions of PtII‐PW11 with Aβ42 including coordination interaction of Pt2+ in PtII‐PW11 with amino group in Aβ42, electrostatic attraction, hydrogen bonding and van der Waals force. In cell‐based assay, PtII‐PW11 displayed remarkable neuroprotective effect for Aβ42 aggregation‐induced cytotoxicity, leading to increase of cell viability from 49 % to 67 % at a dosage of 8 μm. More importantly, the PtII‐PW11 greatly reduced Aβ deposition and rescued memory loss in APP/PS1 transgenic AD model mice without noticeable cytotoxicity, demonstrating its potential as drugs for AD treatment.

Chemical Epigenetics: The Impact of Chemical and Chemical Biology Techniques on Bromodomain Target Validation

By Matthias Schiedel, Mustafa Moroglu, David M. H. Ascough, Anna E. R. Chamberlain, Jos J. A. G. Kamps, Angelina R. Sekirnik, Stuart J. Conway from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Progress in the study of bromodomains, and the development of their ligands, has been underpinned by many disciplines, but chemistry and chemical biology have undoubtedly played a very significant role. Here we review the key chemistry and chemical biology techniques that have furthered our study of bromodomains, enabled the development of bromodomain ligands, and played a critical role in the validation of bromodomains as therapeutic targets. Abstract Epigenetics is currently the focus of intense research interest across a broad range of disciplines due to its importance in a multitude of biological processes and disease states. Epigenetic functions result partly from modification of the nucleobases in DNA and RNA, and/or post‐translational modifications of histone proteins. These modifications are dynamic, with cellular machinery identified to modulate and interpret the marks. Our focus is on bromodomains, which bind to acetylated lysine residues. Progress in the study of bromodomains, and the development of bromodomain ligands, has been rapid. These advances have been underpinned by many disciplines, but chemistry and chemical biology have undoubtedly played a significant role. Herein, we review the key chemistry and chemical biology approaches that have furthered our study of bromodomains, enabled the development of bromodomain ligands, and played a critical role in the validation of bromodomains as therapeutic targets.

Hot π‐Electron Tunneling of Metal–Insulator–COF Nanostructures for Efficient Hydrogen Production

By Jintao Ming, Ai Liu, Jiwu Zhao, Pu Zhang, Haowei Huang, Huan Lin, Ziting Xu, Xuming Zhang, Xuxu Wang, Johan Hofkens, Maarten B. J. Roeffaers, Jinlin Long from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

COFing hydrogen: A MIS (metal–insulator–semiconductor) photosystem can efficiently extract hot π‐electrons of n‐type organic COF semiconductors for hydrogen production and gain a 32‐fold‐enhanced carrier efficiency and an impressive turnover frequency of 789.5 h−1 under visible light excitation. Abstract A metal–insulator–semiconductor (MIS) photosystem based on covalent organic framework (COF) semiconductors was designed for robust and efficient hydrogen evolution under visible‐light irradiation. A maximal H2 evolution rate of 8.42 mmol h−1 g−1 and a turnover frequency of 789.5 h−1 were achieved by using a MIS photosystem prepared by electrostatic self‐assembly of polyvinylpyrrolidone (PVP) insulator‐capped Pt nanoparticles (NPs) with the hydrophilic imine‐linked TP‐COFs having =C=O−H−N= hydrogen‐bonding groups. The hot π‐electrons in the photoexcited n‐type TP‐COF semiconductors can be efficiently extracted and tunneled to Pt NPs across an ultrathin PVP insulating layer to reduce protons to H2. Compared to the Schottky‐type counterparts, the COF‐based MIS photosystems give a 32‐fold‐enhanced carrier efficiency, attributed to the combined enhancement of photoexcitation rate, charge separation, and oxidation rate of holes accumulated in the valence band of the TP‐COF semiconductor.

Convergent Total Syntheses of (−)‐Rubriflordilactone B and (−)‐pseudo‐Rubriflordilactone B

By Mujahid Mohammad, Venkaiah Chintalapudi, Jeffrey M. Carney, Steven J. Mansfield, Pollyanna Sanderson, Kirsten E. Christensen, Edward A. Anderson from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Rubri B or not Rubri B? A convergent late‐stage fragment coupling and rhodium‐catalyzed [2+2+2] alkyne cyclotrimerization strategy provides access to the natural product (−)‐rubriflordilactone B, and the proposed structure of (−)‐pseudo‐rubriflordilactone B. Thus, the uncertainty surrounding the identity of pseudo‐rubriflordilactone B is resolved, and a synthetic platform that offers broad scope for the exploration of this natural product family is established. Abstract A highly convergent strategy for the synthesis of the natural product (−)‐rubriflordilactone B, and the proposed structure of (−)‐pseudo‐rubriflordilactone B, is described. Late stage coupling of diynes containing the respective natural product FG rings with a common AB ring aldehyde precedes rhodium‐catalyzed [2+2+2] alkyne cyclotrimerization to form the natural product skeleton, with the syntheses completed in just one further operation. This work resolves the uncertainty surrounding the identity of pseudo‐rubriflordilactone B and provides a robust platform for further synthetic and biological investigations.

Stabilized Carbenium Ions as Latent, Z‐type Ligands

By Lewis C. Wilkins, Youngmin Kim, Elishua D. Litle, François P. Gabbaï from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Like in a capacitor about to arc, the positive face of the xanthylium cation installed in a new ambiphilic ligand architecture stands set to engage the adjacent gold center in a Au→Ccarbenium interaction. This interaction shows that stabilized carbenium ions may act as latent Z‐type ligands, which, in the present case, enhance the carbophilic reactivity of the adjacent gold center. Abstract Controlling the reactivity of transition metals using secondary, σ‐accepting ligands is an active area of investigation that is impacting molecular catalysis. Herein we describe the phosphine gold complexes [(o‐Ph2P(C6H4)Acr)AuCl]+ ([3]+; Acr=9‐N‐methylacridinium) and [(o‐Ph2P(C6H4)Xan)AuCl]+ ([4]+; Xan=9‐xanthylium) where the electrophilic carbenium moiety is juxtaposed with the metal atom. While only weak interactions occur between the gold atom and the carbenium moiety of these complexes, the more Lewis acidic complex [4]+ readily reacts with chloride to afford a trivalent phosphine gold dichloride derivative (7) in which the metal atom is covalently bound to the former carbocationic center. This anion‐induced AuI/AuIII oxidation is accompanied by a conversion of the Lewis acidic carbocationic center in [4]+ into an X‐type ligand in 7. We conclude that the carbenium moiety of this complex acts as a latent Z‐type ligand poised to increase the Lewis acidity of the gold center, a notion supported by the carbophilic reactivity of these complexes.

Asymmetric Alkenyl C−H Functionalization by CpxRhIII forms 2H‐Pyrrol‐2‐ones through [4+1]‐Annulation of Acryl Amides and Allenes

By Shou‐Guo Wang, Yang Liu, Nicolai Cramer from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Two become one: An efficient CpxRhIII‐catalyzed enantioselective alkenyl C−H functionalization/[4+1] annulation of acryl amides and allenes gives access to synthetically relevant 2H‐pyrrol‐2‐ones with a quaternary stereocenter in excellent selectivity of up to 97:3 er. The reaction operates under mild conditions and displays a broad functional‐group tolerance. The allene serves as a one‐carbon unit in the [4+1]‐annulation. Abstract An efficient CpxRhIII‐catalyzed enantioselective alkenyl C−H functionalization/[4+1] annulation of acryl amides and allenes is reported. The described transformation provides straightforward access to enantioenriched α,β‐unsaturated‐γ‐lactams bearing a quaternary stereocenter. The reaction operates under mild conditions, displays a broad functional‐group tolerance, and provides 2H‐pyrrol‐2‐ones with excellent selectivity of up to 97:3 er. Such scaffolds are frequently found in natural products and synthetic bioactive compounds and are of significant synthetic value. It is noteworthy that the allene serves as a one‐carbon unit in the [4+1]‐annulation.

Tuning the Gate‐Opening Pressure in a Switching pcu Coordination Network, X‐pcu‐5‐Zn, by Pillar‐Ligand Substitution

By Ai‐Xin Zhu, Qing‐Yuan Yang, Soumya Mukherjee, Amrit Kumar, Cheng‐Hua Deng, Andrey A. Bezrukov, Mohana Shivanna, Michael J. Zaworotko from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Pillars of adsorption: Pillar substitution enables the fine‐tuning of the gate‐opening/gate‐closing pressures for a family of flexible coordination networks. The fact that linker flexibility favors lower gate‐opening pressure has broad implications for controlling a key parameter of switching adsorbent materials. Abstract Coordination networks that reversibly switch between closed and open phases are of topical interest since their stepped isotherms can offer higher working capacities for gas‐storage applications than the related rigid porous coordination networks. To be of practical utility, the pressures at which switching occurs, the gate‐opening and gate‐closing pressures, must lie between the storage and delivery pressures. Here we study the effect of linker substitution to fine‐tune gate‐opening and gate‐closing pressure. Specifically, three variants of a previously reported pcu‐topology MOF, X‐pcu‐5‐Zn, have been prepared: X‐pcu‐6‐Zn, 6=1,2‐bis(4‐pyridyl)ethane (bpe), X‐pcu‐7‐Zn, 7=1,2‐bis(4‐pyridyl)acetylene (bpa), and X‐pcu‐8‐Zn, 8=4,4′‐azopyridine (apy). Each exhibited switching isotherms but at different gate‐opening pressures. The N2, CO2, C2H2, and C2H4 adsorption isotherms consistently indicated that the most flexible dipyridyl organic linker, 6, afforded lower gate‐opening and gate‐closing pressures. This simple design principle enables a rational control of the switching behavior in adsorbent materials.

The Fundamentals of Real‐Time Surface Plasmon Resonance/Electrogenerated Chemiluminescence

By Marie‐Pier Dinel, Stefano Tartaggia, Gregory Q. Wallace, Denis Boudreau, Jean‐Francois Masson, Federico Polo from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

3 signals, 1 instrument: The integration of surface plasmon resonance (SPR), cyclic voltammetry, and electrochemiluminescence (ECL) techniques is reported. The combined responses were used to survey the interfacial adsorption and energy transfer processes involved in ECL on a plasmonic substrate. Abstract We report the integration of surface plasmon resonance (SPR), cyclic voltammetry and electrochemiluminescence (ECL) responses to survey the interfacial adsorption and energy transfer processes involved in ECL on a plasmonic substrate. It was observed that a Tween 80/tripropylamine nonionic layer formed on the gold electrode of the SPR sensor, while enhancing the ECL emission process, affects the electron transfer process to the luminophore, Ru(bpy)32+, which in turn has an impact on the plasmon resonance. Concomitantly, the surface plasmon modulated the ECL intensity, which decreased by about 40 %, due to an interaction between the excited state of Ru(bpy)32+ and the plasmon. This occurred only when the plasmon was excited, demonstrating that the optically excited surface plasmon leads to lower plasmon‐mediated luminescence and that the plasmon interacts with the excited state of Ru(bpy)32+ within a very thin layer.

A Cyclic (Alkyl)(boryl)germylene Derived from a Cyclic (Alkyl)(amino)germylene

By Bin Rao, Rei Kinjo from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Ring expansion of a five‐membered cyclic (alkyl)(amino)germylene with a dihaloborane followed by reduction in the presence of Lewis base affords six‐membered cyclic (alkyl)(boryl)germylene–Lewis base adducts. Upon heating, the latter not only undergo dimeric skeletal isomerization to give a cyclic (alkyl)(germyl)germylene featuring η3‐coordination, but also react with H2. Abstract A cyclic (alkyl)(amino)germylene undergoes a ring expansion reaction with dibromomesitylborane (MesBBr2) to afford a six‐membered dibromogermane derivative. In the presence of Lewis bases (PMe3 or MeNHC), reduction of the latter with two equivalents of potassium graphite (KC8) gives rise to cyclic (alkyl)(boryl)germylene–Lewis base adducts. Upon heating, the germylene—PMe3 adduct reacts with H2 to yield a germane, probably via a base‐free germylene featuring a small HOMO–LUMO gap.

Base‐Stabilized [PO]+/[PO2]+ Cations

By Jiliang Zhou, Liu Leo Liu, Levy L. Cao, Douglas W. Stephan from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

PO+ and PO2+ cations stabilized by cyclopropenylidene have been prepared by an atomically precise delivery of P+ and O atoms. The former species exhibits ambiphilic reactivity, while both species acts as electrophiles in reactions with fluoride. Abstract The salts [(BAC)2PO][BF4] (5) and [(BAC)2PO2][BF4] (4) (BAC=bis(diisopropylamino) cyclopropenylidene), consisting of the PO+ and PO2+ cations, respectively, coordinated to the singlet carbenes, have been prepared. Computational investigations reveal that the electronic structure of the PO+ cation is a hybrid between the charge‐localized and charge‐delocalized resonance forms, resulting in ambiphilic reactivity. Compound 5 reacts as a donor with the transition‐metal complex K2PtCl4 to furnish [[(BAC)2PO]2PtCl2][BF4]2 (6) and KCl. Remarkably, both 5 and 4 have shown to act as electrophiles undergoing reactions with fluoride anion, leading to [OPF2]− and (BAC)PO2F, respectively.

Nickel‐Catalyzed Domino Heck‐Type Reactions Using Methyl Esters as Cross‐Coupling Electrophiles

By Yan‐Long Zheng, Stephen G. Newman from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Partner up: Methyl esters are shown to be viable cross‐coupling partners in intramolecular cyclization reactions with a tethered olefin. Both a boronic acid and mild hydride donors can be used in this nickel‐catalyzed reaction, providing differentially substituted indanone products. Abstract While esters are frequently used as traditional electrophiles in substitution chemistry, their application in cross‐coupling chemistry is still in its infancy. This work demonstrates that methyl esters can be used as coupling electrophiles in Ni‐catalyzed Heck‐type reactions through the challenging cleavage of the C(acyl)−O bond under relatively mild reaction conditions at either 80 or 100 °C. With the σ‐NiII intermediate generated from the insertion of acyl NiII species into the tethered C=C bond, carbonyl‐retentive products were formed by domino Heck/Suzuki–Miyaura coupling and Heck/reduction pathways when organoboron and mild hydride nucleophiles are used.

Rb4Li2TiOGe4O12: A Titanyl Nonlinear Optical Material with the Widest Transparency Range

By Mingjun Xia, Chuan Tang, Rukang Li from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Crystal clear: A germanate Rb4Li2TiOGe4O12 mid‐infrared (MIR) nonlinear optical (NLO) crystal, containing well‐aligned compressed TiO5 groups and distorted GeO4 tetrahedra, shows a strong second‐harmonic generation (SHG) response. It exhibits concurrently short ultraviolet and long IR cutoffs, fully covering the atmospheric window spectral range of 3–5 μm. Abstract Practical mid‐infrared (MIR) coherent light beams generated by frequency conversion in nonlinear optical (NLO) crystals are indispensable in time‐resolved infrared vibrational spectroscopy, remote light detection and ranging, and free‐space communications. Herein, a new titanyl germanate Rb4Li2TiOGe4O12 (RLTG) MIR NLO crystal was obtained by heavier element substitution. It features a complicated structure network composed of compressed TiO5 square pyramids and distorted GeO4 tetrahedra, separated by Rb+ and Li+ cations. More importantly, RLTG exhibits concurrently short ultraviolet (0.28 μm) and long IR (5.58 μm) transmittance cutoffs, fully covering the atmospheric transparent window of 3–5 μm. Related to the short UV cutoff, it shows a higher laser‐induced damage threshold in comparison to commercial MIR NLO crystals, about twice that of KTiOPO4 (KTP) and 50 times that of AgGaS2 (AGS).

Catalytic Enantioselective Cyclopropenation of Internal Alkynes: Access to Difluoromethylated Three‐Membered Carbocycles

By Zhi‐Qi Zhang, Meng‐Meng Zheng, Xiao‐Song Xue, Ilan Marek, Fa‐Guang Zhang, Jun‐An Ma from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Three's a crowd: A highly enantioselective RhII‐catalyzed cyclopropenation reaction of difluorodiazoethane (PhSO2CF2CHN2) with challenging internal alkynes is reported (up to 99 % yield, 97 % ee). Versatile stereoselective transformations of these unique strained cyclopropenes are also demonstrated. Abstract Herein we described an efficient RhII‐catalyzed enantioselective cyclopropenation reaction of internal alkynes with a masked difluorodiazoethane reagent (PhSO2CF2CHN2, Ps‐DFA). This asymmetric transformation offers efficient access to a broad range of enantioenriched difluoromethylated cyclopropenes (40 examples, up to 99 % yield, 97 % ee). The synthetic utility of obtained strained carbocycles is demonstrated by subsequent stereodefined processes, including cross‐couplings, hydrogenation, Diels–Alder reaction, and Pauson–Khand reaction.

A DNA–Azobenzene Nanopump Fueled by Upconversion Luminescence for Controllable Intracellular Drug Release

By Yue Zhang, Yue Zhang, Guobin Song, Yuling He, Xiaobo Zhang, Ying Liu, Huangxian Ju from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

A DNA nanopump is produced with azobenzene‐functionalized DNA strands for efficient and controllable drug release through the photoisomerization of azobenzene fueled by the simultaneous UV and visible‐light emissions of upconversion nanoparticles (UCNPs) under NIR irradiation. This triggers the release of an anticancer drug and enhances anticancer therapy. Abstract Stimulus‐responsive drug release possesses considerable significance in cancer therapy. This work reports an upconversion‐luminescence‐fueled DNA–azobenzene nanopump for rapid and efficient drug release. The nanopump is constructed by assembling the azobenzene‐functionalized DNA strands on upconversion nanoparticles (UCNPs). Doxorubicin (DOX) is loaded in the nanopump by intercalation in the DNA helix. Under NIR light, the UCNPs emit both UV and visible photons to fuel the continuous photoisomerization of azo, which acts as an impeller pump to trigger cyclic DNA hybridization and dehybridization for controllable DOX release. In a relatively short period, this system demonstrates 86.7 % DOX release. By assembling HIV‐1 TAT peptide and hyaluronic acid on the system, targeting of the cancer‐cell nucleus is achieved for perinuclear aggregation of DOX and enhanced anticancer therapy. This highly effective drug delivery nanopump could contribute to chemotherapy development.

Detection and Chiral Recognition of α‐Hydroxyl Acid through 1H and CEST NMR Spectroscopy Using a Ytterbium Macrocyclic Complex

By Haonan He, Kelu Zhao, Long Xiao, Yi Zhang, Yi Cheng, Sikang Wan, Shizhen Chen, Lei Zhang, Xin Zhou, Kai Liu, Hongjie Zhang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Chiral and CEST: Three YbDO3A(ala)3 derivatives display the ability to act as a chiral recognition reagent for alpha hydroxyl acids based on proton and chemical exchange saturation transfer (CEST) NMR spectroscopy in an aqueous environment. The sensitivity ranged from 15 to 40 ppm. Abstract Chiral α‐hydroxyl acids are of great importance in chemical synthesis. Current methods for recognizing their chirality by 1H NMR are limited by their small chemical shift differences and intrinsic solubility problem in organic solvents. Herein, we developed three YbDO3A(ala)3 derivatives to recognize four different commercially available chiral α‐hydroxyl acids in aqueous solution through 1H NMR and chemical exchange saturation transfer (CEST) spectroscopy. The shift difference between chiral α‐hydroxyl acid observed by proton and CEST NMR ranged from 15–40 and 20–40 ppm, respectively. Our work demonstrates for first time, that even one chiral center on the side‐arm chain of cyclen could set the stage for rotation of the other two non‐chiral side chains into a preferred position. This is ascribed to the lower energy state of the structure. The results show that chiral YbDO3A‐like complexes can be used to discriminate chiral α‐hydroxyl acids with a distinct signal difference.

Hypervalent Iodine Based Reversible Covalent Bond in Rotaxane Synthesis

By Markéta Kandrnálová, Zoran Kokan, Václav Havel, Marek Nečas, Vladimír Šindelář from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

The interlocked bambusuril: Reactive hypervalent iodine species possessing dynamic covalent bonds are utilized in a constitutive sense for the near quantitative synthesis of rotaxanes via the stabilization by the bambusuril anion receptor. A mechanism for the (dis)assembly of the rotaxanes is proposed to involve the breaking and forming of the labile O−I bond within the bambusuril. Abstract Reversible covalent bonds play a significant role in achieving the high‐yielding synthesis of mechanically interlocked molecules. Still, only a handful of such bonds have been successfully employed in synthetic procedures. Herein, we introduce a novel approach for the fast and simple preparation of interlocked molecules, combining the dynamic bond character of bis(acyloxy)iodate(I) anions with macrocyclic bambusuril anion receptors. The proof of principle was demonstrated on rotaxane synthesis, with near‐quantitative yields observed in both the classical and “in situ” approach. The rotaxane formation was confirmed in the solid‐state and solution by the X‐ray and NMR studies. Our novel approach could be utilized in the fields of dynamic combinatorial chemistry, supramolecular polymers, or molecular machines, as well inspire further research on molecules that exhibit dynamic behavior, but owing to their high reactivity, have not been considered as constituents of more elaborate supramolecular structures.

Selective Autonomous Molecular Transport and Collection by Hydrogel‐Embedded Supramolecular Chemical Gradients

By Shiyan Zhang, Chunjie Zhang, Hao Chen, Spencer J. Kieffer, Frank Neubrech, Harald Giessen, Andrew G. Alleyne, Paul V. Braun from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Selective molecular transport is driven by a hydrogel film containing a built‐in radially symmetric cyclodextrin gradient. The transport performance, including the selectivity, rate, and concentration enhancement limit, is found to be strongly dependent on the host–guest interaction strength. Using an array of IR resonant nanosensors the concentration of an analyte could be quantified. Abstract Selective transport and concentration of molecules to specified regions on a substrate both enhances the potential to detect such molecules and provides a path to spatially localize such molecules prior to initiation of subsequent chemical reactions. Here, we first embed radially symmetric α‐, β‐, and γ‐cyclodextrin gradients in a hydrogel matrix. Driven by host‐guest interactions between the cyclodextrins and the target molecule, we observe these gradients can serve to direct 2D molecular transport. Using xanthene dyes and organophosphates as target molecules, we found the transport metrics, e.g., selectivity, rate, and concentration limits, are strongly dependent on the specific cyclodextrin forming the gradient. In all cases, as the concentrating power of the gradient increased, the rate of target concentration slowed, which we hypothesize is because stronger interactions between the target and the cyclodextrin decrease the rate of target diffusion. The concentration enhancement for the nerve agent simulant 4‐methylumbelliferyl phosphate (15.8) is the greatest when the gradient is formed using β‐cyclodextrin while directed concentration of cyanomethyl phosphonate, a smaller non‐aromatic organophosphate, is observed only for the smaller α‐CD. To provide a near real‐time read‐out of the concentration of the analyte, we used an array of IR resonant metallic nanoantennas tuned to a specific IR absorption band of the analyte to enhance the IR signal generated by the analyte.

Self‐Assembly of MXene‐Surfactants at Liquid–Liquid Interfaces: From Structured Liquids to 3D Aerogels

By Shaowei Shi, Bingqing Qian, Xinyu Wu, Huilou Sun, Haiqiao Wang, Hao‐Bin Zhang, Zhong‐Zhen Yu, Thomas P. Russell from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

We're jammin’: The formation, assembly, and jamming of a new type MXene‐based Janus‐like nanoparticle surfactants, termed MXene‐surfactants (MXSs), is reported through the cooperative assembly of MXene and amine‐functionalized polyhedral oligomeric silsesquioxane at the oil–water interface. The MXSs can significantly enhance the interfacial activity of MXene nanosheets. Abstract 2D transition metal carbides and nitrides (MXenes), a class of emerging nanomaterials with intriguing properties, have attracted significant attention in recent years. However, owing to the highly hydrophilic nature of MXene nanosheets, assembly strategies of MXene at liquid–liquid interfaces have been very limited and challenging. Herein, through the cooperative assembly of MXene and amine‐functionalized polyhedral oligomeric silsesquioxane at the oil–water interface, we report the formation, assembly, and jamming of a new type MXene‐based Janus‐like nanoparticle surfactants, termed MXene‐surfactants (MXSs), which can significantly enhance the interfacial activity of MXene nanosheets. More importantly, this simple assembly strategy opens a new platform for the fabrication of functional MXene assemblies from mesoscale (e.g., structured liquids) to macroscale (e.g., aerogels), that can be used for a range of applications, including nanocomposites, electronic devices, and all‐liquid microfluidic devices.

Protecting the Lithium Metal Anode for a Safe Flexible Lithium‐Air Battery in Ambient Air

By Tong Liu, Xi‐lan Feng, Xin Jin, Ming‐zhe Shao, Yu‐tong Su, Yu Zhang, Xin‐bo Zhang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Hold up an umbrella! A stable hydrophobic composite polymer electrolyte inspired by umbrellas was designed and fabricated on a lithium anode for a flexible Li‐air battery that can safely operate in the ambient air. Based on the in situ fabricated multifunctional electrolyte, the pouch‐type flexible Li‐air battery showed stable electrochemical performance and safety even under extreme conditions. Abstract The flexible Li‐air battery (FLAB) with ultrahigh energy density is a hopeful candidate for flexible energy storage devices. However, most current FLAB operate in a pure oxygen atmosphere, which is limited by safety and corrosion issues from the metallic lithium anode and has thus greatly impeded the application of FLAB. Now, inspired by the protection effect of the umbrella, a stable hydrophobic composite polymer electrolyte (SHCPE) film with high flexibility, hydrophobicity, and stability was fabricated to protect the lithium anode. The SHCPE mitigated lithium corrosion and improved the capacity, rate performance, and cycle life (from 24 cycles to 95 cycles) of a battery in the ambient air. Based on the protection of SHCPE and the catalysis of MnOOH, the prepared pouch‐type FLAB displayed high flexibility, stable performances, long cycling life (180 cycles), and excellent safety; the battery can bear soaking in water, high temperature, and nail penetration.

Self‐Healable Solid Polymeric Electrolytes for Stable and Flexible Lithium Metal Batteries

By Na Wu, Ya‐Ru Shi, Shuang‐Yan Lang, Jin‐Ming Zhou, Jia‐Yan Liang, Wei Wang, Shuang‐Jie Tan, Ya‐Xia Yin, Rui Wen, Yu‐Guo Guo from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Solid but flexible: A self‐healing solid polymer electrolyte (featuring fast self‐healing within 60 s after a deep cut with a blade) endows solid Li metal full batteries with freely bending flexibility and superior cycling stability as demonstrated by the small capacity decay of 0.1 % per cycle over 100 cycles. Abstract The key issue holding back the application of solid polymeric electrolytes in high‐energy density lithium metal batteries is the contradictory requirements of high ion conductivity and mechanical stability. In this work, self‐healable solid polymeric electrolytes (SHSPEs) with rigid‐flexible backbones and high ion conductivity are synthesized by a facile condensation polymerization approach. The all‐solid Li metal full batteries based on the SHSPEs possess freely bending flexibility and stable cycling performance as a result of the more disciplined metal Li plating/stripping, which have great implications as long‐lifespan energy sources compatible with other wearable devices.

Logic‐Gate‐Actuated DNA‐Controlled Receptor Assembly for the Programmable Modulation of Cellular Signal Transduction

By Shan Chen, Zhifei Xu, Wen Yang, Xiahui Lin, Jingying Li, Juan Li, Huanghao Yang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Logical, oh responsible, practical: An aptamer‐based nongenetic approach was designed for logic actuation of endogenous receptor assembly and modulation of the corresponding signal transduction. Logic gates were created that respond to multiple inputs, leading to modulation of c‐Met/HGF signal pathways and cell behavior, providing a robust chemical tool for biomedical applications. Abstract Programming cells to sense multiple inputs and activate cellular signal transduction cascades is of great interest. Although this goal has been achieved through the engineering of genetic circuits using synthetic biology tools, a nongenetic and generic approach remains highly demanded. Herein, we present an aptamer‐controlled logic receptor assembly for modulating cellular signal transduction. Aptamers were engineered as “robotic arms” to capture target receptors (c‐Met and CD71) and a DNA logic assembly functioned as a computer processor to handle multiple inputs. As a result, the DNA assembly brings c‐Met and CD71 into close proximity, thus interfering with the ligand–receptor interactions of c‐Met and inhibiting its functions. Using this principle, a set of logic gates was created that respond to DNA strands or light irradiation, modulating the c‐Met/HGF signal pathways. This simple modular design provides a robust chemical tool for modulating cellular signal transduction.

Asymmetric Hybrid Polyoxometalates: A Platform for Multifunctional Redox‐Active Nanomaterials

By Elizabeth Hampson, Jamie M. Cameron, Sharad Amin, Joungman Kyo, Julie A. Watts, Hiroki Oshio, Graham N. Newton from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

A one‐pot approach to the isolation of an asymmetrically functionalized organic–inorganic hybrid Wells–Dawson polyoxometalate is presented. The cluster bears two organophosphonate moieties with contrasting physical properties: a chelating metal‐binding group and a long aliphatic chain unit that facilitates solvent‐dependent self‐assembly into soft redox‐active nanostructures. Abstract Access to asymmetrically functionalized polyoxometalates is a grand challenge as it could lead to new molecular nanomaterials with multiple or modular functionality. Now, a simple one‐pot synthetic approach to the isolation of an asymmetrically functionalized organic–inorganic hybrid Wells–Dawson polyoxometalate in good yield is presented. The cluster bears two organophosphonate moieties with contrasting physical properties: a chelating metal‐binding group, and a long aliphatic chain that facilitates solvent‐dependent self‐assembly into soft nanostructures. The orthogonal properties of the modular system are effectively demonstrated by controlled assembly of POM‐based redox‐active nanoparticles. This simple, high‐yielding synthetic method is a promising new approach to the preparation of multi‐functional hybrid metal oxide clusters, supermolecular systems, and soft‐nanomaterials.

Genetically Encoded Ratiometric RNA‐Based Sensors for Quantitative Imaging of Small Molecules in Living Cells

By Rigumula Wu, Aruni P. K. K. Karunanayake Mudiyanselage, Fatemeh Shafiei, Bin Zhao, Yousef Bagheri, Qikun Yu, Kathleen McAuliffe, Kewei Ren, Mingxu You from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Ratiometric fluorogenic RNA‐based sensors were developed to quantify metabolites and signaling molecules in living cells. Novel red‐colored RNA‐based sensors were engineered. These RNA‐based sensors can be genetically encoded and engineered into versatile probes for a wide range of cellular targets. Abstract Precisely determining the intracellular concentrations of metabolites and signaling molecules is critical in studying cell biology. Fluorogenic RNA‐based sensors have emerged to detect various targets in living cells. However, it is still challenging to apply these genetically encoded sensors to quantify the cellular concentrations and distributions of targets. Herein, using a pair of orthogonal fluorogenic RNA aptamers, DNB and Broccoli, we engineered a modular sensor system to apply the DNB‐to‐Broccoli fluorescence ratio to quantify the cell‐to‐cell variations of target concentrations. These ratiometric sensors can be broadly applied for live‐cell imaging and quantification of metabolites, signaling molecules, and other synthetic compounds.

Aluminium‐Mediated Carbon Dioxide Reduction by an Isolated Monoalumoxane Anion

By Mathew D. Anker, Martyn P. Coles from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Suck it up! An isolated monoalumoxane anion reacts with the greenhouse gases CO2 and N2O to generate potentially useful chemical compounds. Abstract The deoxygenative conversion of carbon dioxide to carbon monoxide is promoted by the aluminyl anion [Al(NONAr)]− (NONAr=[O(SiMe2NAr)2]2−, Ar=2,6‐iPr2C6H3). The reaction proceeds via the isolable monoalumoxane anion [Al(NONAr)(O)]−, containing a terminal aluminum‐oxygen bond. This species reacts with a second equivalent of carbon dioxide to afford the carbonate [Al(NONAr)(CO3)]−, and with nitrous oxide to generate the hyponitrite anion, [Al(NONAr)(κ2O,O′‐N2O2)]−.

Loss of Single‐Domain Function in a Modular Assembly Line Alters the Size and Shape of a Complex Polyketide

By Huiyun Peng, Keishi Ishida, Christian Hertweck from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Biosynthetic switch: Genetic and chemical analyses revealed a remarkable case where polyketide chain length and scaffold depend on the function of a single β‐keto processing domain of a multimodular polyketide synthase. A ketoreductase domain functions as a molecular switch between diverging pathways, leading either to the antifungal aureothin or to the nematicidal luteoreticulin. Abstract The structural wealth of complex polyketide metabolites produced by bacteria results from intricate, highly evolved biosynthetic programs of modular assembly lines, in which the number of modules defines the size of the backbone, and the domain composition controls the degree of functionalization. We report a remarkable case where polyketide chain length and scaffold depend on the function of a single β‐keto processing domain: A ketoreductase domain represents a switch between diverging biosynthetic pathways leading either to the antifungal aureothin or to the nematicidal luteoreticulin. By a combination of heterologous expression, mutagenesis, metabolite analyses, and in vitro biotransformation we elucidate the factors governing non‐colinear polyketide assembly involving module skipping and demonstrate that a simple point mutation in type I polyketide synthase (PKS) can have a dramatic effect on the metabolic profile. This finding sheds new light on possible evolutionary scenarios and may inspire future synthetic biology approaches.

Expanding the Arsenal of PtIV Anticancer Agents: Multi‐action PtIV Anticancer Agents with Bioactive Ligands Possessing a Hydroxy Functional Group

By Thirumal Yempala, Tomer Babu, Subhendu Karmakar, Alina Nemirovski, Maisaloon Ishan, Valentina Gandin, Dan Gibson from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

The conjugation of an anticancer agent to the axial position of PtIV in a cisplatin prodrug enables the release of the active drug upon reduction of PtIV inside cancer cells. A carbonate was used to bridge the hydroxido axial ligand of PtIV and the hydroxy group of the anticancer agent. The gemcitabine–cisplatin conjugate was more potent and less toxic than gemcitabine alone or co‐administered gemcitabine and cisplatin. Abstract Most multi‐action PtIV prodrugs have bioactive ligands containing carboxylates. This is probably due to the ease of carboxylating the OH axial ligands and because following reduction, the active drug is released. A major challenge is to expand the arsenal of bioactive ligands to include those without carboxylates. We describe a general approach for synthesis of PtIV prodrugs that release drugs with OH groups. We linked the OH groups of gemcitabine (Gem), paclitaxel (Tax), and estramustine (EM) to the PtIV derivative of cisplatin by a carbonate bridge. Following reduction, the axial ligands lost CO2, rapidly generating the active drugs. In contrast, succinate‐linked drugs did not readily release the free drugs. The carbonate‐bridged ctc‐[Pt(NH3)2(PhB)(Gem‐Carb)Cl2] was significantly more cytotoxic than the succinate‐bridged ctc‐[Pt(NH3)2(PhB)(Gem‐Suc)Cl2], and more potent and less toxic than gemcitabine, cisplatin, and co‐administration of cisplatin and gemcitabine.

Copper‐Catalyzed Enantioselective Allylboration of Alkynes: Synthesis of Highly Versatile Multifunctional Building Blocks

By Eva Rivera‐Chao, Maider Mitxelena, Jesús A. Varela, Martín Fañanás‐Mastral from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Complexity from simplicity: A copper‐catalyzed enantioselective alkyne allylboration provides access to non‐racemic densely functionalized molecules from simple starting materials with remarkable chemo‐, regio‐, and enantioselectivity. These multifunctional products are easily converted into a variety of important molecular scaffolds. Abstract The first copper‐catalyzed enantioselective allylboration of alkynes is reported. The method employs a multitasking chiral NHC‐Cu catalyst and provides access to densely functionalized molecules from simple starting materials with excellent levels of chemo‐, regio‐, and enantioselectivity. These multifunctional products display highly versatile reactivity as shown by the synthesis of a variety of non‐racemic molecular scaffolds. DFT calculations were conducted to gain insight into the high selectivity levels of this catalytic process.

Normalized Lithium Growth from the Nucleation Stage for Dendrite‐Free Lithium Metal Anodes

By Nan Li, Qian Ye, Kun Zhang, Huibo Yan, Chao Shen, Bingqing Wei, Keyu Xie from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Homogenization of Li nucleation from the nucleation stage and normalization of Li growth can be achieved on PNIPAM polymer brushes with lithiophilic functional groups modified Cu substrates. The obtained planar columnar Li anode exhibits excellent cycle stability at an ultra‐high current density of 20 mA cm−2. Abstract Inducing uniform deposition of lithium from the stage of metal crystallization nucleation is of vital importance to achieve dendrite‐free lithium anodes. Herein, using experiments and simulation, homogenization of Li nucleation and normalization of Li growth can be achieved on PNIPAM polymer brushes with lithiophilic functional groups modified Cu substrates. The lithiophilic functional groups of amide O can homogenize ion mass transfer and induce the uniform distribution of Li nucleation sites. What is more, the ultra‐small space between each brush can act as the channels for Li transportation and normalization growth. Owing to the synergistic effect of homogenization and normalization of electrodeposited Li, the obtained planar columnar Li anode exhibits excellent cycle stability at an ultra‐high current density of 20 mA cm−2.

Catalytic Enantioselective Methylene C(sp3)−H Amidation of 8‐Alkylquinolines Using a Cp*RhIII/Chiral Carboxylic Acid System

By Seiya Fukagawa, Masahiro Kojima, Tatsuhiko Yoshino, Shigeki Matsunaga from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Enantioselective cleavage of methylene C(sp3)−H bonds was achieved by using an achiral Cp*RhIII catalyst combined with a binaphthyl‐based chiral carboxylic acid. Directing‐group‐assisted C−H amidation reactions of 8‐alkylquinolines with dioxazolones proceed with high enantioselectivity under mild conditions in the presence of various functional groups. Abstract Catalytic enantioselective directed methylene C(sp3)−H amidation reactions of 8‐alkylquinolines using a Cp*RhIII/chiral carboxylic acid (CCA) hybrid catalytic system are described. A binaphthyl‐based chiral carboxylic acid efficiently differentiates between the enantiotopic methylene C−H bonds, which leads to the formation of C−N bonds with good enantioselectivity.

A Photolabile Semiconducting Polymer Nanotransducer for Near‐Infrared Regulation of CRISPR/Cas9 Gene Editing

By Yan Lyu, Shasha He, Jingchao Li, Yuyan Jiang, He Sun, Yansong Miao, Kanyi Pu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Gene genie: A photolabile semiconducting polymer nanotransducer (pSPN) is synthesized not only to act as the gene vector to deliver plasmids into cells but also to behave as the photoregulator to remotely and noninvasively activate CRISPR/Cas9 gene editing. Abstract Noninvasive regulation of CRISPR/Cas9 gene editing is conducive to understanding of gene function and development of gene therapy; however, it remains challenging. Herein, a photolabile semiconducting polymer nanotransducer (pSPN) is synthesized to act as the gene vector to deliver CRISPR/Cas9 plasmids into cells and also as the photoregulator to remotely activate gene editing. pSPN comprises a 1O2‐generating backbone grafted with polyethylenimine brushes through 1O2‐cleavable linkers. NIR photoirradiation spontaneously triggers the cleavage of gene vectors from pSPN, resulting in the release of CRISPR/Cas9 plasmids and subsequently initiating gene editing. This system affords 15‐ and 1.8‐fold enhancement in repaired gene expression relative to the nonirradiated controls in living cells and mice, respectively. As this approach does not require any specific modifications on biomolecular components, pSPN represents the first generic nanotransducer for in vivo regulation of CRISPR/Cas9 gene editing.

Catalytic Asymmetric Conjugate Addition of a Borylalkyl Copper Complex for Chiral Organoboronate Synthesis

By Won Jun Jang, Jaesook Yun from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Neat as a new Bpin: Asymmetric catalytic conjugate addition of a borylalkyl copper nucleophile generated in situ from a 1,1‐diborylmethane to α,β‐unsaturated diesters enabled the enantioselective incorporation of a CH2Bpin moiety at the β‐position of the diesters. The resulting β‐chiral alkylboronates were obtained in up to 86 % yield with high enantioselectivity (see scheme). Abstract We report the catalytic enantioselective conjugate addition of a borylalkyl copper nucleophile generated in situ from a 1,1‐diborylmethane derivative to α,β‐unsaturated diesters. In the presence of a chiral N‐heterocyclic carbene (NHC)–copper catalyst, this method facilitated the enantioselective incorporation of a CH2Bpin moiety at the β‐position of the diesters to yield β‐chiral alkyl boronates in up to 86 % yield with high enantioselectivity. The alkylboron moiety in the resulting chiral diester products was converted into various functional groups by organic transformation of the C−B bond.

Cu‐Mediated Amination of (Hetero)Aryl C−H bonds with NH Azaheterocycles

By Jin‐Feng Yu, Jian‐Jun Li, Peng Wang, Jin‐Quan Yu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

N‐(hetero)arylated heteroarenes were synthesized through Cu‐mediated C−H amination with NH azaheterocycles. This directing‐group (DG)‐mediated reaction proceeds with air as the sole oxidant, and its outstanding compatibility with heterocycles enables late‐stage diversification of a wide range of drug compounds containing multiple heterocycles. Abstract Direct synthesis of N‐(hetero)arylated heteroarenes has been realized through Cu‐mediated C−N coupling of NH azaheterocycles with aryl C−H bonds under aerobic conditions. This method features a broad scope of both heterocyclic arenes (pyridine, quinoline, pyrazole, imidazole, furan, thiophene, benzofuran, and indole) and NH azaheterocycles (imidazole, pyrazole, indole, azindole, purine, indazole, benzimidazole, pyridone, carbazole), providing a versatile method for the synthesis of pharmaceutically important N‐(hetero)arylated heteroarenes. The versatility of this reaction was further demonstrated through late‐stage modification of marketed drugs and the synthesis of a key intermediate for accessing a class of angiotensin II receptor 1 antagonists.

Tunable Reduction of 2,4,6‐Tri(4‐pyridyl)‐1,3,5‐Triazine: From Radical Anion to Diradical Dianion to Radical Metal–Organic Framework

By Shuxuan Tang, Huapeng Ruan, Rui Feng, Yue Zhao, Gengwen Tan, Li Zhang, Xinping Wang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Within the framework: By controlling of the reductants and reaction conditions, reduction of 2,4,6‐tri(4‐pyridyl)‐1,3,5‐triazine (TPT) resulted in four radical anion salts and a diradical dianion salt. One of the radical anion salts forms one‐dimensional (1D) magnetic chain of TPT.−, and two of the others form radical metal‐organic frameworks (RMOFs). TPT..2− in the diradical dianion salt features an open‐shell singlet ground state. Abstract The reduction of 2,4,6‐tri(4‐pyridyl)‐1,3,5‐triazine (TPT) with alkali metals resulted in four radical anion salts (1, 2, 4 and 5) and one diradical dianion salt (3). Single‐crystal X‐ray diffraction and electron paramagnetic resonance (EPR) spectroscopy reveal that 1 contains the monoradical anion TPT.− stacked in one‐dimensional (1D) with K+(18c6) and 2 can be viewed as a 1D magnetic chain of TPT.−, while 4 and 5 form radical metal‐organic frameworks (RMOFs). 1D pore passages, with a diameter of 6.0 Å, containing solvent molecules were observed in 5. Variable‐temperature EPR measurements show that 3 has an open‐shell singlet ground state that can be excited to a triplet state, consistent with theoretical calculation. The work suggests that the direct reduction approach could lead to the formation of RMOFs.

Selective Late‐Stage Sulfonyl Chloride Formation from Sulfonamides Enabled by Pyry‐BF4

By Alejandro Gómez‐Palomino, Josep Cornella from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

It's never too late: The conversion of primary sulfonamides into sulfonyl chlorides has been achieved by capitalizing on the use of Pyry‐BF4 as activating reagent. The mild reaction conditions and high selectivity of the protocol permit the presence of a preponderance of functional groups and the conversion of poorly nucleophilic and unreactive sulfonamides for late‐stage functionalizations. Abstract Reported here is a simple and practical functionalization of primary sulfonamides, by means of a pyrylium salt (Pyry‐BF4), with nucleophiles. This simple reagent activates the poorly nucleophilic NH2 group in a sulfonamide, enabling the formation of one of the best electrophiles in organic synthesis: a sulfonyl chloride. Because of the variety of primary sulfonamides in pharmaceutical contexts, special attention has been focused on the direct conversion of densely functionalized primary sulfonamides by a late‐stage formation of the corresponding sulfonyl chloride. A variety of nucleophiles could be engaged in this transformation, thus permitting the synthesis of complex sulfonamides, sulfonates, sulfides, sulfonyl fluorides, and sulfonic acids. The mild reaction conditions and the high selectivity of Pyry‐BF4 towards NH2 groups permit the formation of sulfonyl chlorides in a late‐stage fashion, tolerating a preponderance of sensitive functionalities.

M. Kevin Brown

By from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

“The best advice I have ever been given is ‘Don't listen to everyone else's advice!' My favorite quote is ‘Simplicity is the ultimate sophistication' …” Find out more about M. Kevin Brown in his Author Profile.

Electrolytes for Rechargeable Lithium–Air Batteries

By Jingning Lai, Yi Xing, Nan Chen, Li Li, Feng Wu, Renjie Chen from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Performance enhancers: Electrolytes for Li–air batteries include non‐aqueous liquid electrolytes, solid‐state electrolytes, aqueous electrolytes, and hybrid electrolytes. This Review shows the importance of electrolytes to the mechanisms and performance of lithium–air batteries and provides a basis for selecting suitable electrolytes. The existing challenges, solutions, as well as guidance for the future direction of this field are also considered. Abstract Lithium–air batteries are promising devices for electrochemical energy storage because of their ultrahigh energy density. However, it is still challenging to achieve practical Li–air batteries because of their severe capacity fading and poor rate capability. Electrolytes are the prime suspects for cell failure. In this Review, we focus on the opportunities and challenges of electrolytes for rechargeable Li–air batteries. A detailed summary of the reaction mechanisms, internal compositions, instability factors, selection criteria, and design ideas of the considered electrolytes is provided to obtain appropriate strategies to meet the battery requirements. In particular, ionic liquid (IL) electrolytes and solid‐state electrolytes show exciting opportunities to control both the high energy density and safety.

Single Chromium Atoms Supported on Titanium Dioxide Nanoparticles for Synergic Catalytic Methane Conversion under Mild Conditions

By Qikai Shen, Changyan Cao, Runkun Huang, Lei Zhu, Xin Zhou, Qinghua Zhang, Lin Gu, Weiguo Song from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Single chromium atoms supported on titanium dioxide nanoparticles are an efficient synergistic heterogeneous catalyst. This system was used for direct methane oxidation to C1 oxygenated products with H2O2 as oxidant under mild conditions. Abstract Direct conversion of methane to value‐added chemicals with high selectivity under mild conditions remains a great challenge in catalysis. Now, single chromium atoms supported on titanium dioxide nanoparticles are reported as an efficient heterogeneous catalyst for direct methane oxidation to C1 oxygenated products with H2O2 as oxidant under mild conditions. The highest yield for C1 oxygenated products can be reached as 57.9 mol molCr−1 with selectivity of around 93 % at 50 °C for 20 h, which is significantly higher than those of most reported catalysts. The superior catalytic performance can be attributed to the synergistic effect between single Cr atoms and TiO2 support. Combining catalytic kinetics, electron paramagnetic resonance, and control experiment results, the methane conversion mechanism was proposed as a methyl radical pathway to form CH3OH and CH3OOH first, and then the generated CH3OH is further oxidized to HOCH2OOH and HCOOH.

Searching for Small Molecules with an Atomic Sort

By Brendan M. Duggan, Reiko Cullum, William Fenical, Luis A. Amador, Abimael D. Rodríguez, James J. La Clair from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

The discovery of biologically active small molecules requires sifting through large amounts of data to identify unique or unusual arrangements of atoms. Here, an atom‐based sort is developed, tested and evaluated to identify novel features of secondary metabolites, outlining an important step towards the translation of autonomous systems to identify atomic novelty within a complex mixture of small molecules. Abstract The discovery of biologically active small molecules requires sifting through large amounts of data to identify unique or unusual arrangements of atoms. Here, we develop, test and evaluate an atom‐based sort to identify novel features of secondary metabolites and demonstrate its use to evaluate novelty in marine microbial and sponge extracts. This study outlines an important ongoing advance towards the translation of autonomous systems to identify, and ultimately elucidate, atomic novelty within a complex mixture of small molecules.

Enantioselective Alkynylation of Trifluoromethyl Ketones Catalyzed by Cation‐Binding Salen Nickel Complexes

By Dongseong Park, Carina I. Jette, Jiyun Kim, Woo‐Ok Jung, Yongmin Lee, Jongwoo Park, Seungyoon Kang, Min Su Han, Brian M. Stoltz, Sukwon Hong from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Cation‐binding salen nickel catalysts were developed for the enantioselective alkynylation of trifluoromethyl ketones in high yield (up to 99 %) and high enantioselectivity (up to 97 % ee). The reaction proceeds with substoichiometric quantities of base (10–20 mol % KOt‐Bu) and open to air. UV‐vis analysis revealed the pendant oligo‐ether group of the catalyst strongly binds to the potassium cation with 1:1 binding stoichiometry (Ka=6.6×105 m−1). Abstract Cation‐binding salen nickel catalysts were developed for the enantioselective alkynylation of trifluoromethyl ketones in high yield (up to 99 %) and high enantioselectivity (up to 97 % ee). The reaction proceeds with substoichiometric quantities of base (10–20 mol % KOt‐Bu) and open to air. In the case of trifluoromethyl vinyl ketones, excellent chemo‐selectivity was observed, generating 1,2‐addition products exclusively over 1,4‐addition products. UV‐vis analysis revealed the pendant oligo‐ether group of the catalyst strongly binds to the potassium cation (K+) with 1:1 binding stoichiometry (Ka=6.6×105 m−1).

On the Products of Cholesterol Autoxidation in Phospholipid Bilayers and the Formation of Secosterols Derived Therefrom

By Emily Schaefer, Nadia Zopyrus, Zosia Zielinski, Glenn Facey, Derek Andrew Pratt from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

In homogenous organic solution, cholesterol autoxidation leads to a mixture of epimers of 5 primary products, whose concentrations vary in the presence/absence of antioxidants, such as Vitamin E. Two of the products (5 a ‐OOH and 6 b ‐OOH) undergo Hock fragmentation to yield electrophilic secosterols implicated in disease. Herein, we show that the product distribution is similar in phospholipid bilayers, in that the 7‐OOHs are the major products, but the presence of Vitamin E has no effect on the product distribution. Cholesterol 7 a ‐OOH, but not 7 b ‐OOH, undergoes Hock fragmentation to yield a mixture of unprecedented A‐ring cleavage products and 6,7‐epoxides. When subjected to typical derivatization conditions, 7 a ‐OOH yields products with essentially indistinguishable chromatographic and spectroscopic features from the previously identified secosterols, casting further doubt on their controversial origin from endogenous O 3 .

Peptide‐Catalyzed Atroposelective Fragment Couplings that Form Axially Chiral Non‐C2‐Symmetric Biaryls

By Gavin Coombs, Marcus Hao-Yi Sak, Scott J. Miller from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

We have demonstrated that small, modular, tetrameric peptides featuring a Lewis‐basic residue, β ‐dimethylaminoalanine (Dmaa), are capable of atroposelectively coupling naphthols and ester‐bearing quinones, yielding non‐ C 2 ‐symmetric BINOL‐type scaffolds with good yields and enantioselectivities. The study culminates in the asymmetric synthesis of backbone‐substituted scaffolds similar to 3,3ʹ‐disubstituted BINOLs, such as ( R )‐TRIP, with good (94:6 e.r.) to excellent (>99.9:0.1 e.r.) enantioselectivity after recrystallization, and a diastereoselective net arylation of a minimally modified, nonsteroidal anti‐inflammatory drug (NSAID), naproxen.

Mon 16 Dec 14:15: PM2.5/NOx modelling for health exposure research

From All Talks (aka the CURE list). Published on Dec 02, 2019.

Reduction of activated alkenes by P(III)/P(V) redox cycling catalysis

By Lars Longwitz, Thomas Werner from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

In this work, the carbon‐carbon double bond of unsaturated carbonyl compounds is readily reduced by a phosphetane oxide catalyst in the presence of a simple organosilane as terminal reductant and water as the hydrogen source. A catalyst screening was conducted and quantitative hydrogenation was observed when 1.0 mol% of a methyl substituted phosphetane oxides was employed as the catalyst. The procedure is highly selective towards activated double bonds tolerating a variety of functional groups which are usually prone to reduction. In total, 25 alkenes and two alkynes were hydrogenated to the corresponding alkanes in excellent yields up to 99%. Notably, less active poly(methylhydrosiloxane) could also be utilized as the terminal reductant. Mechanistic investigation revealed the phosphane as the catalyst resting state and a protonation/deprotonation sequence as the crucial step in the catalytic cycle.

Wed 12 Feb 14:15: Title to be confirmed

From All Talks (aka the CURE list). Published on Dec 02, 2019.

Title to be confirmed

Abstract not available

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Electrochemical Access to Aza‐Polycyclic Aromatic Hydrocarbons: Rhodaelectro‐Catalyzed Domino Annulations

By Wei-Jun Kong, Zhigao Shen, Lars H. Finger, Lutz Ackermann from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 02, 2019.

Nitrogen‐doped polycyclic aromatic hydrocarbons (aza‐PAHs) have found broad applications in material science. Herein, a modular electrochemical synthesis of aza‐PAHs was developed via a rhodium‐catalyzed cascade C−H activation and alkyne annulations. A multifunctional N‐methoxylimidamide ensured high chemo‐ and regioselectivities. The isolation of two key rhodacyclic intermediates allowed to delineate the exact order of three C−H activation events. In addition, the metalaelectro‐catalyzed multiple C−H transformation was characterized by an outstanding functional group tolerance, including highly reactive iodo and azido groups.

Tue 28 Jan 14:30: Cell competition during development and disease Hosted by: Gurdon Institute PhD Society (GPS)

From All Talks (aka the CURE list). Published on Dec 02, 2019.

Cell competition during development and disease

Abstract not available

Hosted by: Gurdon Institute PhD Society (GPS)

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Thu 12 Dec 15:00: Dynamic Compilation and Optimization of Software Network Functions

From All Talks (aka the CURE list). Published on Dec 02, 2019.

Dynamic Compilation and Optimization of Software Network Functions

Abstract: Software Network Functions (NFs) promise increased flexibility and easy development process of network services by moving functionality away from dedicated hardware devices to standard general-purpose servers. Traditional approaches to design and develop those NFs are based on a static compilation, where the input of the compiler is a fixed description of the forwarding plane semantics and the output is the code that can accommodate any packet processing behaviour set by the controller at run-time. Ideally, the compiler should automatically optimize the generated code depending on the declarative description of the data plane semantic that is available in the original NF code. However, it is also true that the actual packet processing behaviour of the data plane program is available only at runtime. In this talk, I will propose a dynamic approach to the data plane compilation, where not only the static features but also the run-time data are exploited to further optimize the output program. This would make it possible to generate a custom version of the original NF that is optimal to the data plane semantic and the packet processing behavior at the same time, hence being able to considerably improve the performance of the original application even by a 40-50% factor.

Bio: Sebastiano Miano is a third-year Ph.D. student at the Polytechnique University of Turin in Italy whose research interest range from networked-systems architectures, programmable hardware, Network Function Virtualization (NFV) and Sofware Defined Networks (SDN). During his Ph.D., he studied new models of network functions that can be used to improve the programmability and performance of the end-host networking, using technologies such as eBPF and XDP together with specialized hardware devices (e.g., SmartNICs).

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[ASAP] Concentrically Integrative Bioassembly of a Three-Dimensional Black Phosphorus Nanoscaffold for Restoring Neurogenesis, Angiogenesis, and Immune Homeostasis

By Yun Qian†?, Wei-En Yuan*‡?, Yuan Cheng‡, Yunqi Yang‡§, Xinhua Qu*?, and Cunyi Fan*† from Nano Letters: Latest Articles (ACS Publications). Published on Dec 02, 2019.

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Nano Letters
DOI: 10.1021/acs.nanolett.9b03980

[ASAP] Smart, Elastic, and Nanofiber-Based 3D Scaffolds with Self-Deploying Capability for Osteoporotic Bone Regeneration

By Lihuan Wang†, Yuyou Qiu‡, Yuxia Guo?, Yang Si§, Lifang Liu†, Jianping Cao‡, Jianyong Yu†§, Xiaoran Li*§, Qi Zhang*‡, and Bin Ding*†§ from Nano Letters: Latest Articles (ACS Publications). Published on Dec 02, 2019.

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Nano Letters
DOI: 10.1021/acs.nanolett.9b04313

[ASAP] Sparked Reduced Graphene Oxide for Low-Temperature Sodium-Beta Alumina Batteries

By Dana Jin†‡?, Hae Gon Lee§?, Sangjin Choi†‡, Sungsoon Kim†‡, Younki Lee?, Sori Son?, Yoon-Cheol Park?, Joon Sang Lee*§, Keeyoung Jung*?, and Wooyoung Shim*†‡#? from Nano Letters: Latest Articles (ACS Publications). Published on Dec 02, 2019.

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Nano Letters
DOI: 10.1021/acs.nanolett.9b03646

[ASAP] Chemical Reactions Impede Thermal Transport Across Metal/ß-Ga2O3 Interfaces

By Henry T. Aller†, Xiaoxiao Yu‡, Adam Wise§, Robert S. Howell?, Andrew J. Gellman‡?, Alan J. H. McGaughey†§, and Jonathan A. Malen*†§ from Nano Letters: Latest Articles (ACS Publications). Published on Dec 02, 2019.

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Nano Letters
DOI: 10.1021/acs.nanolett.9b03017

[ASAP] Correlated Topological States in Graphene Nanoribbon Heterostructures

By Jan-Philip Joost†, Antti-Pekka Jauho‡, and Michael Bonitz*† from Nano Letters: Latest Articles (ACS Publications). Published on Dec 02, 2019.

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Nano Letters
DOI: 10.1021/acs.nanolett.9b04075

[ASAP] Narrow Optical Line Widths in Erbium Implanted in TiO2

By Christopher M. Phenicie†§, Paul Stevenson†§, Sacha Welinski†§, Brendon C. Rose†, Abraham T. Asfaw†, Robert J. Cava‡, Stephen A. Lyon†, Nathalie P. de Leon†, and Jeff D. Thompson*† from Nano Letters: Latest Articles (ACS Publications). Published on Dec 02, 2019.

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Nano Letters
DOI: 10.1021/acs.nanolett.9b03831

[ASAP] Two-Dimensional Cationic Networks and Their Spherical Curvature with Tunable Opening–Closing

By Lingling Zhang†?, Liping Huang†?, Shanshan Wu†?, Xin Xu†, Junhui Bao†, Bowen Shen‡, Liwei Zhang†, Yu Hou†, Longyi Jin§, Tie Chen§, Zujin Yang?, Myongsoo Lee‡, Hongbing Ji*†, and Zhegang Huang*† from Nano Letters: Latest Articles (ACS Publications). Published on Dec 02, 2019.

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Nano Letters
DOI: 10.1021/acs.nanolett.9b04421

[ASAP] Circular Dichroism Measurement of Single Metal Nanoparticles Using Photothermal Imaging

By Patrick Spaeth†, Subhasis Adhikari†, Laurent Le†, Thomas Jollans†, Sergii Pud†, Wiebke Albrecht†‡, Thomas Bauer§, Marti´n Caldarola*§?, L. Kuipers§, and Michel Orrit*† from Nano Letters: Latest Articles (ACS Publications). Published on Dec 02, 2019.

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Nano Letters
DOI: 10.1021/acs.nanolett.9b03853

[ASAP] A MnO2 Nanoparticle-Dotted Hydrogel Promotes Spinal Cord Repair via Regulating Reactive Oxygen Species Microenvironment and Synergizing with Mesenchymal Stem Cells

By Liming Li†‡#, Bing Xiao†§#, Jiafu Mu†, Yu Zhang†, Chenyang Zhang†, Hongcui Cao?, Rongjun Chen?, Hirak Kumar Patra?, Bo Yang†, Shiqing Feng¶¦, Yasuhiko Tabata?, Nigel K. H. Slater?, Jianbin Tang*§, Youqing Shen§, and Jianqing Gao*†‡ from ACS Nano: Latest Articles (ACS Publications). Published on Dec 02, 2019.

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ACS Nano
DOI: 10.1021/acsnano.9b07598

[ASAP] Highly Adhesive Li-BN Nanosheet Composite Anode with Excellent Interfacial Compatibility for Solid-State Li Metal Batteries

By Jiayun Wen†?, Ying Huang†?, Jian Duan†?, Yongmin Wu§, Wei Luo*†, Lihui Zhou?, Chenchen Hu†, Liqiang Huang†, Xueying Zheng†, Wenjuan Yang†, Zhaoyin Wen*‡, and Yunhui Huang*† from ACS Nano: Latest Articles (ACS Publications). Published on Dec 02, 2019.

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ACS Nano
DOI: 10.1021/acsnano.9b08803

[ASAP] Discovery of Stable and Selective Antibody Mimetics from Combinatorial Libraries of Polyvalent, Loop-Functionalized Peptoid Nanosheets

By Jae Hong Kim†#, Samuel C. Kim‡#, Mark A. Kline†, Elissa M. Grzincic†, Blakely W. Tresca†, Joshua Cardiel‡, Mohsen Karbaschi‡, Dilani C. Dehigaspitiya§, Yulin Chen?, Venkatareddy Udumula?, Tengyue Jian?, Daniel J. Murray†, Lisa Yun†, Michael D. Connolly†, Jianfang Liu†, Gang Ren†, Chun-Long Chen?, Kent Kirshenbaum§, Adam R. Abate*‡?, and Ronald N. Zuckermann*† from ACS Nano: Latest Articles (ACS Publications). Published on Dec 02, 2019.

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ACS Nano
DOI: 10.1021/acsnano.9b07498

[ASAP] Dendritic Cell-Activating Magnetic Nanoparticles Enable Early Prediction of Antitumor Response with Magnetic Resonance Imaging

By Adam J. Grippin†‡, Brandon Wummer†, Tyler Wildes†, Kyle Dyson†, Vrunda Trivedi†, Changlin Yang†, Mathew Sebastian†, Hector R. Mendez-Gomez†, Suraj Padala†, Mackenzie Grubb‡, Matthew Fillingim†, Adam Monsalve‡, Elias J. Sayour*†, Jon Dobson*‡§, and Duane A. Mitchell*† from ACS Nano: Latest Articles (ACS Publications). Published on Dec 02, 2019.

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ACS Nano
DOI: 10.1021/acsnano.9b05037

[ASAP] Colloidal CdSe Quantum Wells with Graded Shell Composition for Low-Threshold Amplified Spontaneous Emission and Highly Efficient Electroluminescence

By Yusuf Kelestemur†‡, Yevhen Shynkarenko†‡, Marco Anni§, Sergii Yakunin†‡, Maria Luisa De Giorgi§, and Maksym V. Kovalenko*†‡ from ACS Nano: Latest Articles (ACS Publications). Published on Dec 02, 2019.

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ACS Nano
DOI: 10.1021/acsnano.9b05313

[ASAP] Bifunctional NbS2-Based Asymmetric Heterostructure for Lateral and Vertical Electronic Devices

By Bolun Wang†, Hao Luo†, Xuewen Wang†, Enze Wang†, Yufei Sun†, Yu-Chien Tsai‡, Hui Zhu§, Peng Liu‡, Kaili Jiang‡, and Kai Liu*† from ACS Nano: Latest Articles (ACS Publications). Published on Dec 02, 2019.

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ACS Nano
DOI: 10.1021/acsnano.9b06627

[ASAP] Neutron Activated 153Sm Sealed in Carbon Nanocapsules for in Vivo Imaging and Tumor Radiotherapy

By Julie T.-W. Wang†, Rebecca Klippstein†, Markus Martincic‡, Elzbieta Pach§, Robert Feldman?, Martin S?efl?#, Yves Michel?, Daniel Asker†, Jane K. Sosabowski?, Martin Kalbac?, Tatiana Da Ros?, Ce´cilia Me´nard-Moyon¶, Alberto Bianco¶, Ioanna Kyriakou?, Dimitris Emfietzoglou?, Jean-Claude Saccavini?, Bele´n Ballesteros*§, Khuloud T. Al-Jamal*†, and Gerard Tobias*‡ from ACS Nano: Latest Articles (ACS Publications). Published on Dec 02, 2019.

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ACS Nano
DOI: 10.1021/acsnano.9b04898

[ASAP] Chemoenzymatic Synthesis of O-Mannose Glycans Containing Sulfated or Nonsulfated HNK-1 Epitope

By Tian Gao†‡?, Jingyu Yan§?, Chang-Cheng Liu†‡, Angelina S. Palma?, Zhimou Guo§, Min Xiao†, Xi Chen?, Xinmiao Liang§, Wengang Chai#, and Hongzhi Cao*†‡ from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Dec 02, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b08964

[ASAP] Pd-Catalyzed Enantioselective Heck Reaction of Aryl Triflates and Alkynes

By Chenghao Zhu†, Haoke Chu‡, Gen Li‡, Shengming Ma*‡, and Junliang Zhang*†‡ from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Dec 02, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b10883

[ASAP] De Novo Carborane-Containing Macrocyclic Peptides Targeting Human Epidermal Growth Factor Receptor

By Yizhen Yin†#, Nobuaki Ochi‡, Timothy W. Craven§, David Baker§, Nagio Takigawa‡, and Hiroaki Suga*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Dec 02, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b09106

[ASAP] Multiresponsive Luminescent Cationic Cyclometalated Gold(III) Amphiphiles and Their Supramolecular Assembly

By Ming-Yi Leung, Sammual Yu-Lut Leung, King-Chin Yim, Alan Kwun-Wa Chan, Maggie Ng, and Vivian Wing-Wah Yam* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Dec 02, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b10607

[ASAP] Enzymatic Synthesis of Cu(II)-Responsive Deoxyribozymes through Polymerase Incorporation of Artificial Ligand-Type Nucleotides

By Yusuke Takezawa, Takahiro Nakama, and Mitsuhiko Shionoya* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Dec 02, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b08955

[ASAP] Origin of the Breakthrough Productivity of Ruthenium–Cyclic Alkyl Amino Carbene Catalysts in Olefin Metathesis

By Daniel L. Nascimento and Deryn E. Fogg* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Dec 02, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b10750

[ASAP] Efficient Photocatalytic CO2 Reduction by a Ni(II) Complex Having Pyridine Pendants through Capturing a Mg2+ Ion as a Lewis-Acid Cocatalyst

By Dachao Hong†, Takuya Kawanishi†‡, Yuto Tsukakoshi‡, Hiroaki Kotani‡, Tomoya Ishizuka‡, and Takahiko Kojima*‡ from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Dec 02, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b10597

[ASAP] Realization of Both n- and p-Type GeTe Thermoelectrics: Electronic Structure Modulation by AgBiSe2 Alloying

By Manisha Samanta†, Tanmoy Ghosh†, Raagya Arora‡, Umesh V. Waghmare‡§?, and Kanishka Biswas*†§? from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Dec 02, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b11405

[ASAP] Fluorescence Monitoring of Peptide Transport Pathways into Large and Giant Vesicles by Supramolecular Host–Dye Reporter Pairs

By Andrea Barba-Bon†, Yu-Chen Pan§, Frank Biedermann‡, Dong-Sheng Guo§, Werner M. Nau*†, and Andreas Hennig*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Dec 02, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b09563

[ASAP] Unusual Electronic Effects of Ancillary Ligands on the Perfluoroalkylation of Aryl Iodides and Bromides Mediated by Copper(I) Pentafluoroethyl Complexes of Substituted Bipyridines

By Eric D. Kalkman, Michael G. Mormino, and John F. Hartwig* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Dec 02, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b10540

[ASAP] Lewis Acid Dominant Windmill-Shaped V8 Clusters: A Bifunctional Heterogeneous Catalyst for CO2 Cycloaddition and Oxidation of Sulfides

By Jia-Peng Cao†, Yun-Shan Xue†, Ning-Fang Li, Jun-Jie Gong, Run-Kun Kang, and Yan Xu* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Dec 02, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b11146

[ASAP] Enhanced Negative Thermal Expansion Induced by Simultaneous Charge Transfer and Polar–Nonpolar Transitions

By Takumi Nishikubo*†, Yuki Sakai‡†, Kengo Oka§, Tetsu Watanuki?, Akihiko Machida?, Masaichiro Mizumaki?, Koki Maebayashi†, Takashi Imai†, Takahiro Ogata†, Keisuke Yokoyama¶, Yoichi Okimoto¶, Shin-ya Koshihara¶, Hajime Hojo?, Takashi Mizokawa#, and Masaki Azuma*†‡ from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Dec 02, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b10336

Hydrophilic microporous membranes for selective ion separation and flow-battery energy storage

By Qilei Song from Nature Materials - Issue - nature.com science feeds. Published on Dec 02, 2019.

Nature Materials, Published online: 02 December 2019; doi:10.1038/s41563-019-0536-8

Ion-selective membranes are widely used for water purification and electrochemical energy devices but designing their pore architectures is challenging. Membranes with narrow channels and hydrophilic functionality are shown to exhibit salt ions transport and selectivity towards small organic molecules.

Synthesis of orthogonally assembled 3D cross-stacked metal oxide semiconducting nanowires

By Yonghui Deng from Nature Materials - Issue - nature.com science feeds. Published on Dec 02, 2019.

Nature Materials, Published online: 02 December 2019; doi:10.1038/s41563-019-0542-x

Orthogonal self-assembly of amphiphilic diblock copolymers and polyoxometallates followed by calcination allows the formation of cross-stacked multilayer 3D arrays of tungsten oxide nanowires.

A CO2‐Tolerant Perovskite Oxide with High Oxide Ion and Electronic Conductivity

By Ming Li, Hongjun Niu, John Druce, Helena Téllez, Tatsumi Ishihara, John A. Kilner, Hripsime Gasparyan, Michael J. Pitcher, Wen Xu, J. Felix Shin, Luke M. Daniels, Leanne A. H. Jones, Vin R. Dhanak, Dingyue Hu, Marco Zanella, John B. Claridge, Matthew J. Rosseinsky from Wiley: Advanced Materials: Table of Contents. Published on Dec 01, 2019.

A single‐phase mixed ionic–electronic conductor (MIEC) based on the perovskite oxide Bi0.15Sr0.85Co0.8Fe0.2O3−δ (BiSCF) combines exceptional bulk transport properties, displaying an oxide ion conductivity among the highest for known MIECs, with high CO2 tolerance, which gives BiSCF a significant advantage over existing MIECs such as the well‐known Ba0.5Sr0.5Co0.8Fe0.2O3−δ for practical applications. Abstract Mixed ionic–electronic conductors (MIECs) that display high oxide ion conductivity (σo) and electronic conductivity (σe) constitute an important family of electrocatalysts for a variety of applications including fuel cells and oxygen separation membranes. Often MIECs exhibit sufficient σe but inadequate σo. It has been a long‐standing challenge to develop MIECs with both high σo and stability under device operation conditions. For example, the well‐known perovskite oxide Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCF) exhibits exceptional σo and electrocatalytic activity. The reactivity of BSCF with CO2, however, limits its use in practical applications. Here, the perovskite oxide Bi0.15Sr0.85Co0.8Fe0.2O3−δ (BiSCF) is shown to exhibit not only exceptional bulk transport properties, with a σo among the highest for known MIECs, but also high CO2 tolerance. When used as an oxygen separation membrane, BiSCF displays high oxygen permeability comparable to that of BSCF and much higher stability under CO2. The combination of high oxide transport properties and CO2 tolerance in a single‐phase MIEC gives BiSCF a significant advantage over existing MIECs for practical applications.

The Quest for Zero Loss: Unconventional Materials for Plasmonics

By Michael B. Cortie, Matthew D. Arnold, Vicki J. Keast from Wiley: Advanced Materials: Table of Contents. Published on Dec 01, 2019.

The quest for superior plasmonic materials is discussed and the evolution of the field from the elements, through to alloys and intermetallic compounds, semiconductors, conducting oxides and, most recently, topological insulators, considered. Although both gold and silver remain very attractive choices for plasmonic devices, it is shown that there are instances where alternative materials may be a better choice. Abstract There has been an ongoing quest to optimize the materials used to build plasmonic devices: first the elements were investigated, then alloys and intermetallic compounds, later semiconductors were considered, and, most recently, there has been interest in using more exotic materials such as topological insulators and conducting oxides. The quality of the plasmon resonances in these materials is closely correlated with their structure and properties. In general gold and silver are the most commonly specified materials for these applications but they do have weaknesses. Here, it is shown how, in specific circumstances, the selection of certain other materials might be more useful. Candidate alternatives include TixN, VO2, Al, Cu, Al‐doped ZnO, and Cu–Al alloys. The relative merits of these choices and the many pitfalls and subtle problems that arise are discussed, and a frank perspective on the field is provided.

Designing with Light: Advanced 2D, 3D, and 4D Materials

By Kenward Jung, Nathaniel Corrigan, Mustafa Ciftci, Jiangtao Xu, Soyoung E. Seo, Craig J. Hawker, Cyrille Boyer from Wiley: Advanced Materials: Table of Contents. Published on Dec 01, 2019.

Light is a powerful stimulus, providing easy access to spatiotemporal control, and has been widely employed for material design. As such, photochemical methods empower the fabrication of sophisticated 2D, 3D, and 4D materials at lengths ranging from nano‐ to macroscale. Abstract Recent achievements and future opportunities for the design of 2D, 3D, and 4D materials using photochemical reactions are summarized. Light is an attractive stimulus for material design due to its outstanding spatiotemporal control, and its ability to mediate rapid polymerization under moderate reaction temperatures. These features have been significantly enhanced by major advances in light generation/manipulation with light‐emitting diodes and optical fiber technologies which now allows for a broad range of cost‐effective fabrication protocols. This combination is driving the preparation of sophisticated 2D, 3D, and 4D materials at the nano‐, micro‐, and macrosize scales. Looking ahead, future challenges and opportunities that will significantly impact the field and help shape the future of light as a versatile and tunable design tool are highlighted.

Defective Porous Carbon Polyhedra Decorated with Copper Nanoparticles for Enhanced NIR‐Driven Photothermal Cancer Therapy

By Yangziwan Weng, Shanyue Guan, Li Wang, Heng Lu, Xiangmin Meng, Geoffrey I. N. Waterhouse, Shuyun Zhou from Wiley: Small: Table of Contents. Published on Dec 01, 2019.

The copper nanoparticles supported on defective porous carbon polyhedra are successfully prepared by heating a Cu‐BTC metal organic framework (MOF) precursor at different temperatures under an argon atmosphere. The copper nanoparticle size and carbon defect concentration in the obtained products increase with synthesis temperature, thus imparting the samples with distinct NIR absorption properties and photothermal heating reponses. Abstract Currently, there is tremendous interest in the discovery of new and improved photothermal agents for near‐infrared (NIR)‐driven cancer therapy. Herein, a series of novel photothermal agents, comprising copper nanoparticles supported on defective porous carbon polyhedra are successfully prepared by heating a Cu‐BTC metal–organic framework (MOF) precursor at different temperatures (t) in the range 400–900 °C under an argon atmosphere. The copper nanoparticle size and carbon defect concentration in the obtained products (denoted herein as Cu@CPP‐t) increase with synthesis temperature, thus imparting the Cu@CPP‐t samples with distinct NIR absorption properties and photothermal heating responses. The Cu@CPP‐800 sample shows a remarkable photothermal conversion efficiency of 48.5% under 808 nm laser irradiation, representing one of the highest photothermal efficiencies yet reported for a carbon‐based photothermal agent. In vivo experiments conducted with tumor bearing nude Balb/c mice confirm the efficacy of Cu@CPP‐800 as a very promising NIR‐driven phototherapy agent for cancer treatment. Results encourage the wider use of MOFs as low cost precursors for the synthesis of carbon‐supported metal nanoparticle composites for photothermal therapy.

Additional Lithium Storage on Dynamic Electrode Surface by Charge Redistribution in Inactive Ru Metal

By Yunok Kim, Ji Hyun Um, Hyunjoon Lee, Woosung Choi, Woon Ih Choi, Hyo Sug Lee, Ok‐Hee Kim, Ji Man Kim, Yong‐Hun Cho, Won‐Sub Yoon from Wiley: Small: Table of Contents. Published on Dec 01, 2019.

Pure ruthenium metal composed of ≈5 nm primary particles is designed as an anode material for lithium‐ion battery. Additional lithium storage by charge redistribution on the inactive but environmentally sensitive nanoparticles is identified beyond traditional view that metal nanoparticles are inactive against lithium. This work shed light on inactive nanostructured materials in developing high‐capacity electrode for next generation batteries. Abstract Beyond a traditional view that metal nanoparticles formed upon electrochemical reaction are inactive against lithium, recently their electrochemical participations are manifested and elucidated as catalytic and interfacial effects. Here, ruthenium metal composed of ≈5 nm nanoparticles is prepared and the pure ruthenium as a lithium‐ion battery anode for complete understanding on anomalous lithium storage reaction mechanism is designed. In particular, the pure metal electrode is intended for eliminating the electrochemical reaction‐derived Li2O phase accompanied by catalytic Li2O decomposition and the interfacial lithium storage at Ru/Li2O phase boundary, and thereby focusing on the ruthenium itself in exploring its electrochemical reactivity. Intriguingly, unusual lithium storage not involving redox reactions with electron transfer but leading to lattice expansion is identified in the ruthenium electrode. Size‐dependent charge redistribution at surface enables additional lithium adsorption to occur on the inactive but more environmentally sensitive nanoparticles, providing innovative insight into dynamic electrode environments in rechargeable lithium chemistry.

Soft Hybrid Scaffold (SHS) Strategy for Realization of Ultrahigh Energy Density of Wearable Aqueous Supercapacitors

By Jian Shang, Qiyao Huang, Lei Wang, Yu Yang, Peng Li, Zijian Zheng from Wiley: Advanced Materials: Table of Contents. Published on Dec 01, 2019.

Soft hybrid scaffold (SHS) strategy is a scalable fabrication technique that allows the formation of flexible, high‐mass‐loading, and highly conductive hybrid electrodes comprising of homogeneously interconnected nanosized carbon and pseudomaterials. Wearable aqueous supercapacitors using SHS electrodes (SHS@SCs) show higher energy density than both commercial SCs and state‐of‐the‐art aqueous SCs, with good cycle life, mechanical flexibility, and remarkable wearable attributes. Abstract Future wearable electronics requires safe and high‐energy‐density supercapacitors (SCs). Commercial SCs making use of organic electrolytes show high energy density, but the flammability of the electrolyte raises serious safety concerns. Aqueous SCs, on the other hand, are very safe, but the energy density is low due to the much narrower voltage window and the difficulty of fabricating thick electrodes. A new materials strategy named soft hybrid scaffold (SHS), which allows easy buildup of ultrathick electrodes made of 3D porous pseudo‐material‐modified carbon networks, is reported. The carbon network provides excellent mechanical stability and electric conductivity, the hierarchically porous structures ensure rapid ionic transport, and the pseudomaterials enlarge the electrochemical window. Asymmetric aqueous SCs using SHS electrodes show higher energy density than both commercial organic SCs and literature‐reported aqueous SCs, with good cycle life and mechanical flexibility. The aqueous SC device is tailorable, waterproof, and fire‐retardant, representing a high safety toward practical applications.

Engineered Nanoplatelets for Targeted Delivery of Plasminogen Activators to Reverse Thrombus in Multiple Mouse Thrombosis Models

By Junchao Xu, Yinlong Zhang, Jiaqi Xu, Guangna Liu, Chunzhi Di, Xiao Zhao, Xiang Li, Yao Li, Ningbo Pang, Chengzhi Yang, Yanyi Li, Bozhao Li, Zefang Lu, Meifang Wang, Kesheng Dai, Rong Yan, Suping Li, Guangjun Nie from Wiley: Advanced Materials: Table of Contents. Published on Dec 01, 2019.

Tailor‐designed platelet membrane‐camouflaged polymeric nanoparticles (designated as nanoplatelet) for targeting delivery of the thrombolytic drug (rt‐PA) are developed to navigate multiple acute thrombosis diseases. This nanoplatform can efficiently target to clot site and dissolve thrombus, simultaneously overcoming the main disadvantages of existing thrombolysis therapy (i.e., life‐threatening bleeding risk, a narrow therapeutic time window, and extremely low drug circulation time). Abstract Rapid cut‐off of blood supply in diseases involving thrombosis is a major cause of morbidity and mortality worldwide. However, the current thrombolysis strategies offer limited results due to the therapeutics' short half‐lives, low targeting ability, and unexpected bleeding complications. Inspired by the innate roles of platelets in hemostasis and pathological thrombus, platelet membrane‐camouflaged polymeric nanoparticles (nanoplatelets) are developed for targeting delivery of the thrombolytic drug, recombinant tissue plasminogen activator (rt‐PA), to local thrombus sites. The tailor‐designed nanoplatelets efficiently accumulate at the thrombi in pulmonary embolism and mesenteric arterial thrombosis model mice, eliciting a significantly enhanced thrombolysis activity compared to free rt‐PA. In addition, the nanoplatelets exhibit improved therapeutic efficacy over free rt‐PA in an ischemic stroke model. Analysis of in vivo coagulation indicators suggests the nanoplatelets might possess a low risk of bleeding complications. The hybrid biomimetic nanoplatelets described offer a promising solution to improve the efficacy and reduce the bleeding risk of thrombolytic therapy in a broad spectrum of thrombosis diseases.

A High‐Voltage, Dendrite‐Free, and Durable Zn–Graphite Battery

By Gang Wang, Benjamin Kohn, Ulrich Scheler, Faxing Wang, Steffen Oswald, Markus Löffler, Deming Tan, Panpan Zhang, Jian Zhang, Xinliang Feng from Wiley: Advanced Materials: Table of Contents. Published on Dec 01, 2019.

A high‐voltage and durable Zn–graphite battery is reported, which is enabled by a LiPF6‐containing hybrid electrolyte. The battery can perform at a high voltage of 2.8 V and output a record midpoint discharge voltage of 2.2 V. High rate capability (charge within 3 min) and long‐term cycling stability (>97% capacity retention after 2000 cycles) are also achieved. Abstract The intrinsic advantages of metallic Zn, like high theoretical capacity (820 mAh g−1), high abundance, low toxicity, and high safety have driven the recent booming development of rechargeable Zn batteries. However, the lack of high‐voltage electrolyte and cathode materials restricts the cell voltage mostly to below 2 V. Moreover, dendrite formation and the poor rechargeability of the Zn anode hinder the long‐term operation of Zn batteries. Here a high‐voltage and durable Zn–graphite battery, which is enabled by a LiPF6‐containing hybrid electrolyte, is reported. The presence of LiPF6 efficiently suppresses the anodic oxidation of Zn electrolyte and leads to a super‐wide electrochemical stability window of 4 V (vs Zn/Zn2+). Both dendrite‐free Zn plating/stripping and reversible dual‐anion intercalation into the graphite cathode are realized in the hybrid electrolyte. The resultant Zn–graphite battery performs stably at a high voltage of 2.8 V with a record midpoint discharge voltage of 2.2 V. After 2000 cycles at a high charge–discharge rate, high capacity retention of 97.5% is achieved with ≈100% Coulombic efficiency.

3D Printing of Textiles: Potential Roadmap to Printing with Fibers

By Kony Chatterjee, Tushar K. Ghosh from Wiley: Advanced Materials: Table of Contents. Published on Dec 01, 2019.

The feasibility of current 3D printing techniques for textile manufacturing is explored. Current 3D printing techniques using soft materials are examined, with a focus on printing heterogeneous/anisotropic structures. The properties required as polymers transition from fibers, to yarns, to fabrics are presented. Limitations and opportunities in 3D printing of textiles are discussed. Abstract 3D printing (3DP) has transformed engineering, manufacturing, and the use of advanced materials due to its ability to produce objects from a variety of materials, ranging from soft polymers to rigid ceramics. 3DP offers the advantage of being able to print at a variety of lengths scales; from a few micrometers to many meters. 3DP has the unique ability to produce customized small lots, efficiently. Yet, one crucial industry that has not been able to adequately explore its potential is textile manufacturing. The research in 3DP of textiles has lagged behind other areas primarily due to the difficulty in obtaining some of the unique characteristics of strength, flexibility, etc., of textiles, utilizing a fundamentally different manufacturing technology. Textiles are their own class of materials due to the specific structural developments that occur during the various stages of textile manufacturing: from fiber extrusion to assembly of the fibers to fabrics. Here, the current 3DP technologies are reviewed with emphasis on soft and anisotropic structures, as well as the efforts toward 3DP of textiles. Finally, a potential pathway to 3DP of textiles, dubbed as printing with fibers to create textile structures is proposed for further exploration.

Extending the Colloidal Transition Metal Dichalcogenide Library to ReS2 Nanosheets for Application in Gas Sensing and Electrocatalysis

By Beatriz Martín‐García, Davide Spirito, Sebastiano Bellani, Mirko Prato, Valentino Romano, Anatolii Polovitsyn, Rosaria Brescia, Reinier Oropesa‐Nuñez, Leyla Najafi, Alberto Ansaldo, Giovanna D'Angelo, Vittorio Pellegrini, Roman Krahne, Iwan Moreels, Francesco Bonaccorso from Wiley: Small: Table of Contents. Published on Dec 01, 2019.

Colloidal synthesis of rhenium disulfide nanosheets enables a simple and cost‐effective exploitation of its peculiar layer‐independent properties for gas‐sensing and electrochemical H2 production. The surface functionalization of the nanosheets leads to sensitive and fast response gas sensors, while their assembly with carbon nanotubes enhances its electrocatalytic activity, making both device performances competitive with chemical vapor deposition rhenium disulfide. Abstract Among the large family of transition metal dichalcogenides, recently ReS2 has stood out due to its nearly layer‐independent optoelectronic and physicochemical properties related to its 1T distorted octahedral structure. This structure leads to strong in‐plane anisotropy, and the presence of active sites at its surface makes ReS2 interesting for gas sensing and catalysts applications. However, current fabrication methods use chemical or physical vapor deposition (CVD or PVD) processes that are costly, time‐consuming and complex, therefore limiting its large‐scale production and exploitation. To address this issue, a colloidal synthesis approach is developed, which allows the production of ReS2 at temperatures below 360 °C and with reaction times shorter than 2h. By combining the solution‐based synthesis with surface functionalization strategies, the feasibility of colloidal ReS2 nanosheet films for sensing different gases is demonstrated with highly competitive performance in comparison with devices built with CVD‐grown ReS2 and MoS2. In addition, the integration of the ReS2 nanosheet films in assemblies together with carbon nanotubes allows to fabricate electrodes for electrocatalysis for H2 production in both acid and alkaline conditions. Results from proof‐of‐principle devices show an electrocatalytic overpotential competitive with devices based on ReS2 produced by CVD, and even with MoS2, WS2, and MoSe2 electrocatalysts.

Engineering the Structure of Mesoporous Bioactive Glass Microspheres by the Surface Effect of Inverse Opal Templates and Temperature

By Lijun Ji, Mindong Gong, Tong Xu, Jun Gu, Xu Jiang, Taotao Liang, Yu Chen, Qingren Liu from Wiley: Small: Table of Contents. Published on Dec 01, 2019.

The surface properties of inverse opals can strongly affect ion and block copolymer distribution in their pores. This surface effect principle can be used for the controlled synthesis of colloids with complex composition. Mesoporous magnetic bioactive glass colloids with ordered mesopores, core–shell structure, open surface pores, and disordered mesopores are prepared by using polystyrene and carbon inverse opal templates. Abstract The interactions of ions and molecules with material surface are highly dependent on the surface properties of the material. Therefore, the distribution of ions or molecules near the material surface may be affected by the surface properties. This phenomenon can be significant enough for controlling the structure of a material synthesized in the sub‐micrometer scale confinement space of a template. This work confirms that inverse opals are perfect templates for offering confinement space, while their different surface properties can strongly affect ion and block copolymer distribution in the confinement space. This surface effect principle can be used for the controlled synthesis of colloids with complex composition. As an example, four kinds of mesoporous magnetic bioactive glass colloids with ordered mesopores, core–shell structure, open surface pores, or disordered mesopores are prepared by using polystyrene and carbon inverse opal templates. This work reveals that inverse opal templates possess great advantage in controlled synthesizing colloidal structures due to their surface effect on ions and molecules and confinement space.

Activating Low Acidic Pronucleophiles: Chiral Organosuperbases Take Action

By Yu-Hui Wang, Zhong-Yan Cao, Qing-Hua Li, Guo-Qiang Lin, Jian Zhou, Ping Tian from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 01, 2019.

Direct deprotonation represents an extremely simple, straightforward, and atom‐economic strategy to activate the pronucleophiles bearing an acidic proton. However, the difficulty often arises while activating pronucleophiles with a low acidic proton by using conventional chiral tertiary amines. To overcome this great challenge, a handful of novel chiral Brønsted superbases, including amidines, guanidines, cyclopropenimines, and iminophosphoranes, have been discovered in recent years. This minireview mainly focuses on the application of these organosuperbases in the catalytic asymmetric reactions of low acidic pronucleophiles, and especially highlights their comparisons to the conventional tertiary amines, to demonstrate their highly efficient deprotonation processes and further stereoselectivity‐controlled conversions. The advantage of these new superbases brings a great opportunity for developing more asymmetric transformations of low acidic pronucleophiles.

Bioinspired Synthesis of (‐)‐PF‐1018

By Hugo Quintela-Varela, Cooper Jamieson, Qianzhen Shao, Kendall Houk, Dirk Trauner from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 01, 2019.

The combination of electrocyclizations and cycloadditions accounts for the formation of a range of fascinating natural products. Cascades consisting of 8pelectrocyclizations, followed by 6p electrocyclization, and a cycloaddition are relatively common. We now report the synthesis of the tetramic acid PF‐1018 through an 8p electrocyclization, the product of which is immediately intercepted by a Diels–Alder cycloaddition. The success of this pericyclic cascade was critically dependent on the substitution pattern of the starting polyene and could be rationalized through DFD calculations. The completion of the synthesis required the instalment of a trisubstituted double bond via radical deoxygenation. An unexpected byproduct formed through 4‐exo‐trig radical cyclization could be recycled through an unprecedented triflation/fragmentation.

Electrochemical Difunctionalization of Alkenes via Four‐component Reactions Cascade Mumm Rearrangement: Rapid Access to Functionalized Imides

By Peipei Sun, Xiaofeng Zhang, Ting Cui, Xin Zhao, Ping Liu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Dec 01, 2019.

An electrochemical four‐component reaction cascade Mumm rearrangement was developed, representing a rare example of in situ generation of O‐acyl isoamides for 1,3‐(O®N) acyl transfer. Inexpensive, commercially available arylethylenes, aryl or heterocyclic acids, acetonitrile, and alcohols were used as substrates. A wide range of aryl acids and alcohols were found to be tolerated and provided imides in satisfactory yields. Subsequent hydrolysis of imides could be utilized to synthesize valuable amides and β‐amino alcohol derivatives.

Preferential formation of mono‐metallofullerenes governed by the encapsulation energy of the metal elements: A case study on Eu@C2n (2n = 74‐84) revealing a general rule

By Lipiao Bao, Ying Li, Pengyuan Yu, Wangqiang Shen, Peng Jin, Xing Lu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Nov 30, 2019.

Entrapping one to three metal atom(s) or a metallic cluster inside fullerene cages affords endohedral metallofullerenes (EMFs) classified as mono‐EMFs, di‐EMFs, tri‐EMFs and cluster‐EMFs, respectively. Although the coexistence of diverse EMF‐species in the soot is common for rare earth metals, we herein report for the first time that europium tends to induce the preferential formation of mono‐EMFs instead. Mass spectroscopy reveals that mono‐EMFs (EuC 2n ) prevail in the Eu‐containing soot. Theoretical calculations demonstrate that the encapsulation energy of the endohedral metal element accounts for the selective formation of the mono‐EMFs and rationalize similar observations for EMFs containing other metals like Ca, Sr, Ba or Yb. Consistently, all the isolated Eu‐EMFs are actually mono‐EMFs including Eu@ D 3 h (1)‐C 74 , Eu@ C 2 v (19138)‐C 76 , Eu@ C 2 v (3)‐C 78 , Eu@ C 2 v (3)‐C 80 and Eu@ D 3 d (19)‐C 84 which are identified by crystallography in this work. Remarkably, Eu@ C 2 v (19138)‐C 76 represents as the first Eu‐containing EMF with a cage that violates the isolated‐pentagon‐rule and Eu@ C 2 v (3)‐C 78 is the first C 78 ‐based EMF stabilized by merely one metal atom.

Thu 06 Feb 13:00: TBC Lunch provided

From All Talks (aka the CURE list). Published on Nov 30, 2019.

TBC

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MXene‐Based Dendrite‐Free Potassium Metal Batteries

By Xiao Tang, Dong Zhou, Peng Li, Xin Guo, Bing Sun, Hao Liu, Kang Yan, Yury Gogotsi, Guoxiu Wang from Wiley: Advanced Materials: Table of Contents. Published on Nov 29, 2019.

A high‐performance potassium metal anode is developed by confining potassium metal into a titanium‐deficient and nitrogen‐containing MXene/carbon nanotube freestanding scaffold. These potassium metal anodes exhibit a dendrite‐free morphology with high Coulombic efficiency and long cycle life during plating/stripping processes. Abstract Potassium metal batteries are considered as attractive alternatives beyond lithium‐ion batteries. However, uncontrollable dendrite growth on the potassium metal anode has restrained their practical applications. A high‐performance potassium anode achieved by confining potassium metal into a titanium‐deficient nitrogen‐containing MXene/carbon nanotube freestanding scaffold is reported. The high electronic transport and fast potassium diffusion in this scaffold enable reduced local current density and homogeneous ionic flux during plating/stripping processes. Furthermore, as verified by theoretical calculations and experimental investigations, such “potassium‐philic” MXene sheets can induce the nucleation of potassium, and guide potassium to uniformly distribute in the scaffold upon cycling. Consequently, the as‐developed potassium metal anodes exhibit a dendrite‐free morphology with high Coulombic efficiency and long cycle life during plating/stripping processes. Such anodes also deliver significantly improved electrochemical performances in potassium–sulfur batteries compared with bare potassium metal anodes. This work can provide a new avenue for developing potassium metal‐based batteries.

Toward Efficient Carbon and Water Cycles: Emerging Opportunities with Single‐Site Catalysts Made of 3d Transition Metals

By Gang Wan, Guanghui Zhang, Xiao‐Min Lin from Wiley: Advanced Materials: Table of Contents. Published on Nov 29, 2019.

A critical review is provided on the progress of integrating 3d transition‐metal single‐site catalysts into carbon using support‐assisted pyrolysis, with applications toward key chemical and electrochemical reactions in carbon and water cycles. The latest material chemistry developments that enable the identification of catalytic reaction centers, key performance descriptors that influence catalyst activity and stability, are highlighted. Abstract Advances in the chemical and electrochemical transformation of carbon and water are vital for delivering affordable and environmentally friendly energy sources and chemicals. Central to this challenge is the performance of materials. Traditionally, noble metal particles or metal complexes have been used as catalysts for many reactions. Recently, 3d transition‐metal single‐site catalysts (3dTM‐SSCs) have emerged as potentially transformational candidates for the next‐generation high‐performance noble‐metal‐free catalysts. Designing catalysts at the molecular level can lead to a more efficient utilization of metal atoms and at the same time enhance catalytic performance under harsh reaction conditions. Despite this promise, several fundamental issues remain, in particular the structural evolution of 3dTM‐SSCs during the synthesis, the molecular‐level insights into the structure of the active sites, catalytic mechanisms, and the long‐term cycling stability. Here, the material chemistries that facilitate the 3dTM‐SSCs generation through a controlled pyrolytic synthesis are discussed, with focus on elucidating the underlying performance descriptors that can tune the catalytic properties in various critical reactions in carbon and water cycles. The current challenges and possible solutions for improving these novel catalytic materials are also highlighted.

Wireless Monitoring Using a Stretchable and Transparent Sensor Sheet Containing Metal Nanowires

By Teppei Araki, Takafumi Uemura, Shusuke Yoshimoto, Ashuya Takemoto, Yuki Noda, Shintaro Izumi, Tsuyoshi Sekitani from Wiley: Advanced Materials: Table of Contents. Published on Nov 29, 2019.

Optically and mechanically imperceptible sensor sheets that allow the wireless monitoring of biological signals to obtain low‐noise measurements are discussed. This includes effective improvement methods for an Ag nanowire based track in terms of transparency, stretchability, reliability, and miniaturization with treatments, such as nanolevel Au plating. In addition, an organic amplifier is explored toward a high signal‐to‐noise ratio. Abstract Mechanically and visually imperceptible sensor sheets integrated with lightweight wireless loggers are employed in ultimate flexible hybrid electronics (FHE) to reduce vital stress/nervousness and monitor natural biosignal responses. The key technologies and applications for conceptual sensor system fabrication are reported, as exemplified by the use of a stretchable sensor sheet completely conforming to an individual's body surface to realize a low‐noise wireless monitoring system (

In Pursuit of Zero 2.0: Recent Developments in Nonfouling Polymer Brushes for Immunoassays

By Jacob T. Heggestad, Cassio M. Fontes, Daniel Y. Joh, Angus M. Hucknall, Ashutosh Chilkoti from Wiley: Advanced Materials: Table of Contents. Published on Nov 29, 2019.

The development of nonfouling polymer brush surfaces has ushered in a new wave of in vitro diagnostic (IVD) tests. Polymer brushes eliminate nonspecific protein adsorption to the surface and thus enable ultrasensitive detection of proteins directly from complex biological milieu. Diagnostic platforms capable of point‐of‐care testing are highlighted. Abstract “Nonfouling” polymer brush surfaces can greatly improve the performance of in vitro diagnostic (IVD) assays due to the reduction of nonspecific protein adsorption and consequent improvement of signal‐to‐noise ratios. The development of synthetic polymer brush architectures that suppress adventitious protein adsorption is reviewed, and their integration into surface plasmon resonance and fluorescent sandwich immunoassay formats is discussed. Also, highlighted is a novel, self‐contained immunoassay platform (the D4 assay) that transforms time‐consuming laboratory‐based assays into a user‐friendly and point‐of‐care format with a sensitivity and specificity comparable or better than standard enzyme‐linked immunosorbent assay (ELISA) directly from unprocessed samples. These advancements clearly demonstrate the utility of nonfouling polymer brushes as a substrate for ultrasensitive and robust diagnostic assays that may be suitable for clinical testing, in field and laboratory settings.

Biomaterials as Tools to Decode Immunity

By Haleigh B. Eppler, Christopher M. Jewell from Wiley: Advanced Materials: Table of Contents. Published on Nov 29, 2019.

The selectivity and memory of the immune system have positioned vaccines and immunotherapies as important clinical advances. New tools to study the interactions of immune signals with immune cells and tissues will help drive the next generation of these technologies. Emerging methods in which tunable properties of biomaterials are creating new tools to decode and control immunity are highlighted. Abstract The immune system has remarkable capabilities to combat disease with exquisite selectivity. This feature has enabled vaccines that provide protection for decades and, more recently, advances in immunotherapies that can cure some cancers. Greater control over how immune signals are presented, delivered, and processed will help drive even more powerful options that are also safe. Such advances will be underpinned by new tools that probe how immune signals are integrated by immune cells and tissues. Biomaterials are valuable resources to support this goal, offering robust, tunable properties. The growing role of biomaterials as tools to dissect immune function in fundamental and translational contexts is highlighted. These technologies can serve as tools to understand the immune system across molecular, cellular, and tissue length scales. A common theme is exploiting biomaterial features to rationally direct how specific immune cells or organs encounter a signal. This precision strategy, enabled by distinct material properties, allows isolation of immunological parameters or processes in a way that is challenging with conventional approaches. The utility of these capabilities is demonstrated through examples in vaccines for infectious disease and cancer immunotherapy, as well as settings of immune regulation that include autoimmunity and transplantation.

Cell Mechanical and Physiological Behavior in the Regime of Rapid Mechanical Compressions that Lead to Cell Volume Change

By Anna Liu, Tong Yu, Katherine Young, Nicholas Stone, Srinivas Hanasoge, Tyler J. Kirby, Vikram Varadarajan, Nicholas Colonna, Janet Liu, Abhishek Raj, Jan Lammerding, Alexander Alexeev, Todd Sulchek from Wiley: Small: Table of Contents. Published on Nov 29, 2019.

Studies of rapid cell deformation have discovered the phenomenon of cell volume exchange for efficient, convective intracellular macromolecule delivery. This paper characterizes a controlled cell volume exchange mechanism dependent on strain rate and cell viscoelastic properties that can predict volume change for multiple human cell types. This process maintains cell viability and function for invaluable downstream cell engineering applications. Abstract Cells respond to mechanical forces by deforming in accordance with viscoelastic solid behavior. Studies of microscale cell deformation observed by high speed video microscopy have elucidated a new cell behavior in which sufficiently rapid mechanical compression of cells can lead to transient cell volume loss and then recovery. This work has discovered that the resulting volume exchange between the cell interior and the surrounding fluid can be utilized for efficient, convective delivery of large macromolecules (2000 kDa) to the cell interior. However, many fundamental questions remain about this cell behavior, including the range of deformation time scales that result in cell volume loss and the physiological effects experienced by the cell. In this study, a relationship is established between cell viscoelastic properties and the inertial forces imposed on the cell that serves as a predictor of cell volume loss across human cell types. It is determined that cells maintain nuclear envelope integrity and demonstrate low protein loss after the volume exchange process. These results define a highly controlled cell volume exchange mechanism for intracellular delivery of large macromolecules that maintains cell viability and function for invaluable downstream research and clinical applications.

Thermodynamically Stable Mesoporous C3N7 and C3N6 with Ordered Structure and Their Excellent Performance for Oxygen Reduction Reaction

By In Young Kim, Sungho Kim, Selvarajan Premkumar, Jae‐Hun Yang, Siva Umapathy, Ajayan Vinu from Wiley: Small: Table of Contents. Published on Nov 29, 2019.

Thermodynamically stable C3N7 and C3N6 are discovered for the first time via stabilization of NN bonds in tetrazine and/or triazole moieties through a low‐temperature pyrolysis process of 5‐amino‐1H‐tetrazole. Triazole‐based mesoporous C3N7 exhibits better oxygen reduction reaction activity than s‐heptazine‐based carbon nitrides due to its inordinate core structure. Abstract Carbon nitrides with a high N/C atomic ratio (>2) are expected to offer superior basicity and unique electronic properties. However, the synthesis of these nanostructures is highly challenging since many parts of the CN frameworks in the carbon nitride should be replaced with thermodynamically less stable NN frameworks as the nitrogen content increases. Thermodynamically stable C3N7 and C3N6 with an ordered mesoporous structure are synthesized at 250 and 300 °C respectively via a pyrolysis process of 5‐amino‐1H‐tetrazole (5‐ATTZ). Polymerization of the precursor to the ordered mesoporous C3N7 and C3N6 is clearly proved by X‐ray and electron diffraction analyses. A combined analysis including diverse spectroscopy and FDMNES and density functional theory (DFT) calculations demonstrates that the NN bonds are stabilized in the form of tetrazine and/or triazole moieties in the C3N7 and C3N6. The ordered mesoporous C3N7 represents the better oxygen reduction reaction (ORR) performances (onset potential: 0.81 V vs reversible hydrogen electrode (RHE), electron transfer number: 3.9 at 0.5 V vs RHE) than graphitic carbon nitride (g‐C3N4) and the ordered mesoporous C3N6. The study on the mechanism of ORR suggests that nitrogen atoms in the tetrazine moiety of the ordered mesoporous C3N7 act as active sites for its improved ORR activity.

Regio‐ and Stereoselective Thianthrenation of Olefins to Access Versatile Alkenyl Electrophiles

By Tobias Ritter, Junting Chen, Jiakun Li, Matthew Plutschack, Florian Berger from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Nov 29, 2019.

Here we report a regioselective alkenyl electrophile synthesis from unactivated olefins via a direct and regioselective C–H thianthrenation reaction. The selectivity is proposed to arise from an unusual inverse electron demand hetero Diels‐Alder reaction. The alkenyl sulfonium salts can serve as electrophiles for palladium and ruthenium catalyzed cross‐coupling reactions to make alkenyl C–C, C–Cl, C–Br and C–SCF3 bonds stereo‐retentively.

New Chiral Brønsted Acid from Chiral Phosphoric Acid Boron Complex and Water: Asymmetric Reduction of Indoles

By Kai Yang, Yixian Lou, Chenglan Wang, Liang-Wen Qi, Tongchang Fang, Feng Zhang, Hetao Xu, Lu Zhou, Wangyang Li, Guan Zhang, Peiyuan Yu, Qiuling Song from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Nov 29, 2019.

A new chiral Brønsted acid, generated in situ from chiral phosphoric acid boron (CPAB) complex and water, was successfully applied to asymmetric indole reduction. This “designer acid catalyst”, being more acidic than TsOH as suggested by DFT calculations, allows for the unprecedented direct asymmetric reduction of C2‐aryl substituted N‐unprotected indoles and features good to excellent enantioselectivities with broad functional group tolerance. DFT calculations and mechanistic experiments indicates that this reaction undergoes C3‐protonation and hydride transfer processes. Besides, bulky C2‐alkyl substituted N‐unprotected indoles are also suitable for this system.

Enantiomeric Control of Intrinsically Chiral Nanocrystals

By Uri Hananel, Assaf Ben‐Moshe, Daniel Tal, Gil Markovich from Wiley: Advanced Materials: Table of Contents. Published on Nov 29, 2019.

Chiral nanocrystals can be prepared with high enantioselectivity by utilizing chiral biomolecules. The several chiral nanocrystal systems that are studied so far are reviewed with insights on the role of the chiral molecules and the possible mechanisms that may lead to chiral shape formation. The imprinting of the chiral shape to achiral functional materials is discussed. Abstract The chiral aspect of inorganic crystals that crystallize in chiral space groups has been largely ignored until recently, partly due to difficulties in characterizing the chiroptical properties of bulk crystals, and also due to the difficulty in separating (sub)micrometer‐scale chiral crystal enantiomers. In recent years, the colloidal synthesis of intrinsically chiral nanocrystals (NCs) of several chiral inorganic compounds with significant enantiomeric excess has been demonstrated. This is achieved through the use of chiral molecular ligands, which bind to the atomic/ionic components of the crystals, preferentially forming one crystal enantiomorph. Here, recent progress on several aspects of these NCs is described, including the connection between ligand structure and its ability to direct NC handedness, chiral amplification in the synthesis leading to enantiopure NC samples, spontaneous symmetry breaking, the formation of NCs with chiral shapes, the connection between lattice and shape chirality and mixed contributions of atomic‐scale and shape chirality to the chiroptical properties.

Cobalt Chalcogenides/Cobalt Phosphides/Cobaltates with Hierarchical Nanostructures for Anode Materials of Lithium‐Ion Batteries: Improving the Lithiation Environment

By Liping Liang, Jiancheng Li, Mingyuan Zhu, Ying Li, Shulei Chou, Wenxian Li from Wiley: Small: Table of Contents. Published on Nov 29, 2019.

The research progress on the synthesis methods, structural characteristics, and electrochemical performances of cobalt chalcogenides/cobalt phosphides/cobaltates with hierarchical nanostructures for lithium‐ion batteries (LIBs) is presented here. The concluding remarks highlight the research challenges and possible development directions of cobalt chalcogenides/cobalt phosphides/cobaltates with tailored hierarchical nanostructures for LIBs. Abstract Lithium‐ion batteries (LIBs) are widely used in electric vehicles and portable electronic devices due to their high energy density, long cycle life, environmental friendliness, and negligible memory effect, though they also suffer from low power density, safety issues, and an aging effect. Cobalt chalcogenides/phosphides as promising anode materials have attracted intensive interests due to their high theoretical capacity based on the conversion mechanism. Cobaltates (XCo2O4, X = the other metal) have attracted attention because the X element can partially replace the high cost and toxic cobalt element. The serious volume variation during the cycling process has an impact, however, on the lithiation environment of above materials. Hierarchical construction can provide more active sites and shorten the diffusion pathways of Li ions as well as accommodating the volume expansion during lithiation processes. Herein, the research progress on the synthesis methods, structural characteristics, and electrochemical performances of cobalt chalcogenides/cobalt phosphides/cobaltates with hierarchical nanostructures for LIBs is presented. The concluding remarks highlight the research challenges and possible development directions of cobalt chalcogenides/cobalt phosphides/cobaltates with tailored hierarchical nanostructures for LIBs.

High‐Voltage Aqueous Na‐Ion Battery Enabled by Inert‐Cation‐Assisted Water‐in‐Salt Electrolyte

By Liwei Jiang, Lilu Liu, Jinming Yue, Qiangqiang Zhang, Anxing Zhou, Oleg Borodin, Liumin Suo, Hong Li, Liquan Chen, Kang Xu, Yong‐Sheng Hu from Wiley: Advanced Materials: Table of Contents. Published on Nov 29, 2019.

The Na IC‐WiS electrolyte exhibits many advantages for aqueous Na‐ion batteries, including a wide electrochemical window, low viscosity, favorable solid elecrtolyte interphase (SEI) containing NaF on the surface of anode, and also for mitigating dissolution of the electrodes and the inertness of TEA+ cation intercalation to electrodes. Abstract Water‐in‐salt (WiS) electrolytes provide a new pathway to widen the electrochemical window of aqueous electrolytes. However, their formulation strongly depends on the solubility of the chosen salts, imposing a stringent restriction on the number of possible WiS systems. This issue becomes more severe for aqueous Na‐ion batteries (ANIBs) owing to the relatively lower solubility of sodium salts compared to its alkaline cousins (Li, K, and Cs). A new class of the inert‐cation‐assisted WiS (IC‐WiS) electrolytes containing the tetraethylammonium (TEA+) inert cation is reported. The Na IC‐WiS electrolyte at a superhigh concentration of 31 mol kg–1 exhibits a wide electrochemical window of 3.3 V, suppresses transition metal dissolution from the cathode, and ensures singular intercalation of Na into both cathode and anode electrodes during cycling, which is often problematic in mixed alkali cation systems such as K–Na and Li–Na. Owing to these unique advantages of the IC‐WiS electrolyte, the NaTiOPO4 anode and Prussian blue analog Na1.88Mn[Fe(CN)6]0.97·1.35H2O cathode can be coupled to construct a full ANIB, delivering an average voltage of 1.74 V and a high energy density of 71 Wh kg−1 with a capacity retention of 90% after 200 cycles at 0.25C and of 76% over 800 cycles at 1C.

Neodymium‐Sensitized Nanoconstructs for Near‐Infrared Enabled Photomedicine

By Zhongzheng Yu, Wen Kiat Chan, Timothy Thatt Yang Tan from Wiley: Small: Table of Contents. Published on Nov 29, 2019.

This review article summarizes three energy transfer pathways of all kinds of Nd3+‐sensitized nanoconstructs focusing on the properties of Nd3+ ions and discusses their recent potential applications as near‐infrared enabled photomedicine. It will contribute to the fabrication of novel Nd3+‐sensitized nanoconstructs for near‐infrared enabled photomedicine, aiming for potentially safer and more efficient designs closer to clinical usage. Abstract Neodymium (Nd3+)‐sensitized nanoconstructs have gained increasing attention in recent decades due to their unique properties, especially optical properties. The design of various Nd3+‐sensitized nanosystems is expected to contribute to medical and health applications, due to their advantageous properties such as high penetration depth, excellent photostability, non‐photobleaching, low cytotoxicity, etc. However, the low conversion efficiency and potential long‐term toxicity of Nd3+‐sensitized nanoconstructs are huge obstacles to their clinical translations. This review article summarizes three energy transfer pathways of all kinds of Nd3+‐sensitized nanoconstructs focusing on the properties of Nd3+ ions and discusses their recent potential applications as near‐infrared (NIR) enabled photomedicine. This review article will contribute to the design and fabrication of novel Nd3+‐sensitized nanoconstructs for NIR‐enabled photomedicine, aiming for potentially safer and more efficient designs to get closer to clinical usage.

Strategies for Constructing Upconversion Luminescence Nanoprobes to Improve Signal Contrast

By Zhen Li, Tao Liang, Qirong Wang, Zhihong Liu from Wiley: Small: Table of Contents. Published on Nov 29, 2019.

UCNPs‐based nanoprobes have been established as promising tools for biosensing in complex bio‐samples, such as serum, saliva, living cells, tissues, and even living animals. However, the low signal contrast is the bottleneck of UC‐nanoprobes and restricts their further applications in biological and medical research. Recent efforts on circumventing this difficulty are presented. Abstract Lanthanide‐doped upconversion nanoparticles (UCNPs) can convert two or more lower‐energy near‐infrared photons to a single photon with higher energy, which makes them particularly suitable for constructing nanoprobes with large imaging depth and minimal interference of autofluorescence and light scattering from biosamples. Furthermore, they feature excellent photostability, sharp and narrow emissions, and large anti‐Stokes shift, which confer them the capability of long‐period bioimaging and real‐time tracking. In recent years, UCNPs‐based nanoprobes (UC‐nanoprobes) have been attracting increasing interest in biological and medical research. Signal contrast, the ratio of signal intensity after and before the reaction of the probe and target, is the determinant factor of the sensitivity of all reaction‐based probes. This progress report presents the methods of constructing UC‐nanoprobes, with a focus fixed on recent strategies to improve the signal contrast, which have kept on promoting the bioapplication of this type of probe.

Magnetically Powered Shape‐Transformable Liquid Metal Micromotors

By Min Liu, Yongxin Wang, Yanbing Kuai, Jiawei Cong, Yunli Xu, Hong‐Guang Piao, Liqing Pan, Yiman Liu from Wiley: Small: Table of Contents. Published on Nov 29, 2019.

Magnetically powered shape‐transformable liquid metal (LM) micromotors are fabricated by a simple, versatile ice‐assisted transfer printing method. The LM micromotors display efficient propulsion under magnetic fields, and can undergo dramatic morphological transformation when exposed to an alternating magnetic field, holding great promise for controlled drug delivery, cargo transport, chemical sensing that are not possible with rigid‐bodies microrobots. Abstract Shape‐transformable liquid metal (LM) micromachines have attracted the attention of the scientific community over the past 5 years, but the inconvenience of transfer routes and the use of corrosive fuels have limited their potential applications. In this work, a shape‐transformable LM micromotor that is fabricated by a simple, versatile ice‐assisted transfer printing method is demonstrated, in which an ice layer is employed as a “sacrificial” substrate that can enable the direct transfer of LM micromotors to arbitrary target substrates conveniently. The resulting LM microswimmers display efficient propulsion of over 60 µm s−1 (≈3 bodylength s−1) under elliptically polarized magnetic fields, comparable to that of the common magnetic micro/nanomotors with rigid bodies. Moreover, these LM micromotors can undergo dramatic morphological transformation in an aqueous environment under the irradiation of an alternating magnetic field. The ability to transform the shape and efficiently propel LM microswimmers holds great promise for chemical sensing, controlled cargo transport, materials science, and even artificial intelligence in ways that are not possible with rigid‐bodies microrobots.

Enhancement of Fluorescence Emission for Tricolor Quantum Dots Assembled in Polysiloxane toward Solar Spectrum‐Simulated White Light‐Emitting Devices

By Guangqi Hu, Yuqiong Sun, Jianle Zhuang, Xuejie Zhang, Haoran Zhang, Mingtao Zheng, Yong Xiao, Yeru Liang, Hanwu Dong, Hang Hu, Bingfu Lei, Chaofan Hu, Yingliang Liu from Wiley: Small: Table of Contents. Published on Nov 29, 2019.

This work prepares the tricolor quantum‐dot‐based hybrid composites that present significant enhancement of fluorescence emission and outstanding photothermal stability. Using the as‐prepared hybrid fluorescent material, the fabricated light‐emitting diodes exhibit solar spectrum‐simulated emission and the recorded color rendering index (CRI) of 97, indicating an application perspective in the eye protecting and required high‐CRI fields. Abstract Commercial white light‐emitting diodes (LEDs) have the undesirable characteristics of blue‐rich emission and low color rendering index (CRI), while the constituent quantum dots (QDs) suffer from aggregation‐induced fluorescence quenching and poor stability. Herein, a strategy is developed to assemble tricolor QDs into a polysiloxane matrix using a polymer‐mediated hybrid approach whereby the hybrid composite exhibits a significant enhancement of aggregation‐dispersed emission, outstanding photostability, high thermal stability, and outstanding fluorescence recovery. Using the as‐prepared hybrid fluorescent materials, the fabricated LEDs exhibit solar spectrum‐simulated emission with adjustable Commission Internationale de L'Eclairage coordinates, correlated color temperature, and a recorded CRI of 97. Furthermore, they present no ultraviolet emission and weak blue emission, thus indicating an ideal healthy and high‐CRI white LED lighting source.

An Organic‐Inorganic Hybrid Exhibiting Electrical Conduction and Single‐Ion‐Magnetism

By Yongbing Shen, Goulven Cosquer, Hiroshi Ito, David Chukwuma Izuogu, Alex J.W. Thom, Toshiaki Ina, Tomoya Uruga, Takefumi Yoshida, Shinya Takaishi, Brian K. Breedlove, Zhao-Yang Li, Masahiro Yamashita from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Nov 29, 2019.

The first three–dimensional (3D) conductive single‐ion magnet (SIM), (TTF)2[Co(pdms)2] (TTF = tetrathiafulvalene and H2pdms = 1,2‐bis(methanesulfonamido)benzene), was electrochemically synthesized and investigated structurally, physically and theoretically. The quite close oxidation potential between neutral TTF and the coordination precursor, (HNEt3)2[M(pdms)2] (M = Co, Zn) causes multiple charge transfers (CTs) between SIM donor [M(pdms)2]n– and the TTF●+ acceptor as well as an intra‐donor CT from the pdms ligand to Co ion upon electrocrystallization. Usually TTF works as a donor, whereas in our system, TTF works as both a donor and an accepter due to the close oxidation potentials. Furthermore, the [M(pdms)2]n–  donor and TTF●+ acceptor are not segregated but strongly interact with each other, contrary to reported layered donor‐acceptor electrical conductors. The strong intermolecular and intramolecular interactions, combined with the CT, cause relatively high electrical conductivity to very low temperature. Furthermore, SIM behaviour with slow magnetic relaxation and opening of hysteresis loops were observed. (TTF)2[Co(pdms)2] (2‐Co) is an excellent building block for preparing new conductive SIM.

Mon 27 Jan 13:00: IMC

From All Talks (aka the CURE list). Published on Nov 29, 2019.

IMC

Abstract not available

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Probing Contact‐Electrification‐Induced Electron and Ion Transfers at a Liquid–Solid Interface

By Jinhui Nie, Zewei Ren, Liang Xu, Shiquan Lin, Fei Zhan, Xiangyu Chen, Zhong Lin Wang from Wiley: Advanced Materials: Table of Contents. Published on Nov 29, 2019.

The mechanism behind the contact electrification between liquid and solid remains controversial. According to experimental results and theoretical calculations, the contact electrification of ionic liquids and solids is caused by both electron transfer and ion transfer. Furthermore, the contact electrification between nonionic liquids and solids is mainly due to electron transfer. Abstract As a well‐known phenomenon, contact electrification (CE) has been studied for decades. Although recent studies have proven that CE between two solids is primarily due to electron transfer, the mechanism for CE between liquid and solid remains controversial. The CE process between different liquids and polytetrafluoroethylene (PTFE) film is systematically studied to clarify the electrification mechanism of the solid–liquid interface. The CE between deionized water and PTFE can produce a surface charges density in the scale of 1 nC cm−2, which is ten times higher than the calculation based on the pure ion‐transfer model. Hence, electron transfer is likely the dominating effect for this liquid–solid electrification process. Meanwhile, as ion concentration increases, the ion adsorption on the PTFE hinders electron transfer and results in the suppression of the transferred charge amount. Furthermore, there is an obvious charge transfer between oil and PTFE, which further confirms the presence of electron transfer between liquid and solid, simply because there are no ions in oil droplets. It is demonstrated that electron transfer plays the dominant role during CE between liquids and solids, which directly impacts the traditional understanding of the formation of an electric double layer (EDL) at a liquid–solid interface in physical chemistry.

Atomic Spatial and Temporal Imaging of Local Structures and Light Elements inside Zeolite Frameworks

By Boyuan Shen, Xiao Chen, Dali Cai, Hao Xiong, Xin Liu, Changgong Meng, Yu Han, Fei Wei from Wiley: Advanced Materials: Table of Contents. Published on Nov 29, 2019.

Atomic imaging of a ZSM‐5 framework by integrated differential phase contrast (iDPC)‐scanning transmission electron microscopy (STEM) is reported. The ZSM‐5 lattices are atomically resolved to reveal 3D frameworks and local structures of ZSM‐5 nanocrystals with a high resolution and signal‐to‐noise ratio. Light‐element aromatics adsorbed in ZSM‐5 and the structural changes of channels during the in situ heating process are also imaged. Abstract Identifying the atomic structures of porous materials in spatial and temporal dimensions by (scanning) transmission electron microscope ((S)TEM) is significant for their wide applications in catalysis, separation and energy storage. However, the sensitivity of materials to electron beams made it difficult to reduce the electron damage to specimens while maintaining the resolution and signal‐to‐noise ratio. It is therefore still challenging to capture multiple images of the same area in one crystal to image the temporal changes of lattices. Usings integrated differential phase contrast (iDPC) STEM, atomic‐resolution imaging of beam‐sensitive zeolite frameworks is achieved with an ultralow dose of 40 e− Å−2, 2–3 orders of magnitude lower than that of conventional STEM. Based on the iDPC technique, not only the atomic 3D architecture of ZSM‐5 crystals but also the changes of frameworks are observed during in situ experiments. Local structures and light‐element aromatics in ZSM‐5 crystals can also be revealed directly under iDPC‐STEM. These results provided not only an efficient tool to image beam‐sensitive materials with ultralow beam current but also a new strategy to observe and investigate the hydrocarbon pools in zeolite catalysts at the single‐molecule scale.

Color‐Based Optical Detection of Glass Transitions on Microsecond Timescales Enabled by Exciplex Dynamics

By Stefano Canossa, Georgy A. Filonenko from Wiley: Advanced Materials: Table of Contents. Published on Nov 29, 2019.

Photoluminescence (PL) is a powerful tool for sensing and imaging. PL sensors are given one more advantage—defined sensing timescale. Sensitivity of probe excited state to changes in polymer dynamics allows the performance of fast measurements on emission timescales. Abstract Every measurement technique operates on a given timescale and measurements using emissive small molecule sensors are no exception. A family of luminescent sensors providing first optical characterization of dynamic phenomena in polymers at a timescale of several microseconds is described. This performance originates from the dynamics manifested in the excited state of the sensor molecules where diffusioncontrolled events select the emission color while radiative phenomena define the global operation timescale. Since the mechanism responsible for signal generation is confined to the short lived excited state of emissive probe, it is possible observe an unprecedented link between the timescale of sensory action and that of photoluminescence. An application of this new methodology is demonstrated by performing general, short timescale detection of glass transitions in a temperature ranges precluding the informative range of conventional techniques by tens of degrees.

Relieving the Photosensitivity of Organic Field‐Effect Transistors

By Jie Liu, Longfeng Jiang, Jia Shi, Chunlei Li, Yanjun Shi, Jiahui Tan, Haiyang Li, Hui Jiang, Yuanyuan Hu, Xinfeng Liu, Junsheng Yu, Zhongming Wei, Lang Jiang, Wenping Hu from Wiley: Advanced Materials: Table of Contents. Published on Nov 29, 2019.

The correlation of photosensitivity of organic field‐effect transistors (OFETs) to organic semiconductor bulk traps and semiconductor/dielectric interface traps is established and verified by systematical experimental studies. Highly ordered single crystals in combination with polymer dielectrics having low surface trap densities can ensure constant brightness output for series‐connected OFET‐driven organic light‐emitting diodes. Abstract It is generally believed that the photoresponse behavior of organic field‐effect transistors (OFETs) reflects the intrinsic property of organic semiconductors. However, this photoresponse hinders the application of OFETs in transparent displays as driven circuits due to the current instability resulting from the threshold voltage shift under light illumination. It is necessary to relieve the photosensitivity of OFETs to keep the devices stable. 2,6‐diphenyl anthracene thin‐film and single‐crystal OFETs are fabricated on different substrates, and it is found that the degree of molecular order in the conducting channels and the defects at the dielectric/semiconductor interface play important roles in determining the phototransistor performance. When highly ordered single‐crystal OFETs are fabricated on polymeric substrates with low defects, the photosensitivity (P) decreases by more than 105 times and the threshold voltage shift (ΔVT) is almost eliminated compared with the corresponding thin‐film OFETs. This phenomenon is further verified by using another three organic semiconductors for similar characterizations. The decreased P and ΔVT of OFETs ensure a good current stability for OFETs to drive organic light‐emitting diodes efficiently, which is essential to the application of OFETs in flexible and transparent displays.

Tape‐Casting Li0.34La0.56TiO3 Ceramic Electrolyte Films Permit High Energy Density of Lithium–Metal Batteries

By Zhouyang Jiang, Suqing Wang, Xinzhi Chen, Wenlong Yang, Xiang Yao, Xinchao Hu, Qingyue Han, Haihui Wang from Wiley: Advanced Materials: Table of Contents. Published on Nov 29, 2019.

The energy density of all‐solid‐state lithium–metal batteries based on oxide electrolytes is depend on the thickness of the electrolytes. The production and application of freestanding Li0.34La0.56TiO3 ceramic film with a thickness below 41 µm prepared by tape‐casting demonstrate the feasibility and challenges of the commercial application of ceramic oxide electrolytes. Abstract Ceramic oxide electrolytes are outstanding due to their excellent thermostability, wide electrochemical stable windows, superior Li‐ion conductivity, and high elastic modulus compared to other electrolytes. To achieve high energy density, all‐solid‐state batteries require thin solid‐state electrolytes that are dozens of micrometers thick due to the high density of ceramic electrolytes. Perovskite‐type Li0.34La0.56TiO3 (LLTO) freestanding ceramic electrolyte film with a thickness of 25 µm is prepared by tape‐casting. Compared to a thick electrolyte (>200 µm) obtained by cold‐pressing, the total Li ionic conductivity of this LLTO film improves from 9.6 × 10−6 to 2.0 × 10−5 S cm−1. In addition, the LLTO film with a thickness of 25 µm exhibits a flexural strength of 264 MPa. An all‐solid‐state Li–metal battery assembled with a 41 µm thick LLTO exhibits an initial discharge capacity of 145 mAh g−1 and a high capacity retention ratio of 86.2% after 50 cycles. Reducing the thickness of oxide ceramic electrolytes is crucial to reduce the resistance of electrolytes and improve the energy density of Li–metal batteries.

Acoustic Holographic Cell Patterning in a Biocompatible Hydrogel

By Zhichao Ma, Andrew W. Holle, Kai Melde, Tian Qiu, Korbinian Poeppel, Vincent Mauricio Kadiri, Peer Fischer from Wiley: Advanced Materials: Table of Contents. Published on Nov 29, 2019.

Acoustic holographic cell manipulation enables complex‐shape cellular pattern formation in a biocompatible hydrogel. Hydrogel encapsulation enables the custom‐designed cell assemblies to be transferred and incubated with good cell viability. This technology holds promise for noncontact, long‐range, long‐term cellular pattern formation, with a wide variety of potential applications in tissue engineering and mechanobiology. Abstract Acoustophoresis is promising as a rapid, biocompatible, noncontact cell manipulation method, where cells are arranged along the nodes or antinodes of the acoustic field. Typically, the acoustic field is formed in a resonator, which results in highly symmetric regular patterns. However, arbitrary, nonsymmetrically shaped cell assemblies are necessary to obtain the irregular cellular arrangements found in biological tissues. It is shown that arbitrarily shaped cell patterns can be obtained from the complex acoustic field distribution defined by an acoustic hologram. Attenuation of the sound field induces localized acoustic streaming and the resultant convection flow gently delivers the suspended cells to the image plane where they form the designed pattern. It is shown that the process can be implemented in a biocompatible collagen solution, which can then undergo gelation to immobilize the cell pattern inside the viscoelastic matrix. The patterned cells exhibit F‐actin‐based protrusions, which indicate that the cells grow and thrive within the matrix. Cell viability assays and brightfield imaging after one week confirm cell survival and that the patterns persist. Acoustophoretic cell manipulation by holographic fields thus holds promise for noncontact, long‐range, long‐term cellular pattern formation, with a wide variety of potential applications in tissue engineering and mechanobiology.

Acetylene and Diacetylene Functionalized Covalent Triazine Frameworks as Metal‐Free Photocatalysts for Hydrogen Peroxide Production: A New Two‐Electron Water Oxidation Pathway

By Liang Chen, Lei Wang, Yangyang Wan, Ying Zhang, Zeming Qi, Xiaojun Wu, Hangxun Xu from Wiley: Advanced Materials: Table of Contents. Published on Nov 29, 2019.

Covalent triazine frameworks incorporated with acetylene and diacetylene moieties exhibit a unique two‐electron water oxidation pathway toward H2O2 production in addition to the two‐electron oxygen reduction pathway. Both experimental and theoretical investigations reveal that carbon–carbon triple bonds are critical to modulate the electronic structures and provide active sites for photocatalytic H2O2 production. Abstract Metal‐free polymer photocatalysts have shown great promise for photocatalytic H2O2 production via two‐electron reduction of molecular O2. The other half‐reaction, which is the two‐electron oxidation of water, still remains elusive toward H2O2 production. However, enabling this water oxidation pathway is critically important to improve the yield and maximize atom utilization efficiency. It is shown that introducing acetylene (CC) or diacetylene (CCCC) moieties into covalent triazine frameworks (CTFs) can remarkably promote photocatalytic H2O2 production. This enhancement is inherent to the incorporated carbon–carbon triple bonds which are essential in modulating the electronic structures of CTFs and suppressing charge recombinations. Furthermore, the acetylene and diacetylene moieties can significantly reduce the energy associated with OH* formation and thus enable a new two‐electron oxidation pathway toward H2O2 production. The study unveils an important reaction pathway toward photocatalytic H2O2 production, reflecting that precise control over the chemical structures of polymer photocatalysts is vital to achieve efficient solar‐to‐chemical energy conversion.

Ultrahigh‐Sensitivity Sandwiched Plasmon Ruler for Label‐Free Clinical Diagnosis

By Jingjie Nan, Shoujun Zhu, Shunsheng Ye, Weihong Sun, Ying Yue, Xiaoduo Tang, Jingwei Shi, Xuesong Xu, Junhu Zhang, Bai Yang from Wiley: Advanced Materials: Table of Contents. Published on Nov 29, 2019.

Significantly high sensitivity and a broad dynamic range of biomolecular detection are obtained using a novel sandwiched plasmon ruler (SW‐PR). Unprecedented performance in clinical diagnosis is achieved in a highly precise manner without using extra antibodies or a chemical immobilization technique. Furthermore, the facile operation and low‐cost instrumentation of the SW‐PR platform accelerate the clinical translation of point‐of‐care plasmonic sensors. Abstract Optical biosensors, especially those based on plasmonic structures, have emerged recently as a potential tool for disease diagnostics. Plasmonic biosensors have demonstrated impressive benefits for the label‐free detection of trace biomarkers in human serum. However, widespread applications of these technologies are hindered because of their insufficient sensitivity, their relatively complex chemical immobilization processes, and the use of prism couplers. Accordingly, a sandwiched plasmon ruler (SW‐PR) based on a Au nanohole array with ultrahigh sensitivity arising from the plasmonic coupling effect is developed. Highly confined surface charges caused by Bloch wave surface plasmon polarizations substantially increase the coupling efficiency. This platform exhibits thickness sensitivity as high as 61 nm nm−1 and can detect at least 200 000‐fold lower analyte concentrations than a nanowell sensing platform with the same wavelength shift. Additionally, the sandwiched plasmonic biosensor allows precise and label‐free testing of clinical biomarkers, namely C‐reactive protein and procalcitonin, in patient serum samples without requiring a sophisticated prism coupler, extra antibodies, or a chemical immobilization technique. This study yields new insight into the structural design of plasmon rulers and will open exciting avenues for disease diagnosis and therapy follow‐up at the point‐of‐care.

Nacre‐Inspired Composite Electrolytes for Load‐Bearing Solid‐State Lithium‐Metal Batteries

By Aijun Li, Xiangbiao Liao, Hanrui Zhang, Lei Shi, Peiyu Wang, Qian Cheng, James Borovilas, Zeyuan Li, Wenlong Huang, Zhenxuan Fu, Martin Dontigny, Karim Zaghib, Kristin Myers, Xiuyun Chuan, Xi Chen, Yuan Yang from Wiley: Advanced Materials: Table of Contents. Published on Nov 29, 2019.

A versatile bottom‐up approach to fabricate large‐scale nacre‐like ceramic/polymer electrolytes (NCPEs) to enhance the mechanical robustness of solid‐state lithium‐metal batteries is described. Lithium‐metal batteries with such NCPE maintain stable cycling performance even under harsh mechanical loads, while cells with pure ceramic or pure polymer electrolytes fail under the same load. Abstract Solid‐state lithium‐metal batteries with solid electrolytes are promising for next‐generation energy‐storage devices. However, it remains challenging to develop solid electrolytes that are both mechanically robust and strong against external mechanical load, due to the brittleness of ceramic electrolytes and the softness of polymer electrolytes. Herein, a nacre‐inspired design of ceramic/polymer solid composite electrolytes with a “brick‐and‐mortar” microstructure is proposed. The nacre‐like ceramic/polymer electrolyte (NCPE) simultaneously possesses a much higher fracture strain (1.1%) than pure ceramic electrolytes (0.13%) and a much larger ultimate flexural modulus (7.8 GPa) than pure polymer electrolytes (20 MPa). The electrochemical performance of NCPE is also much better than pure ceramic or polymer electrolytes, especially under mechanical load. A 5 × 5 cm2 pouch cell with LAGP/poly(ether‐acrylate) NCPE exhibits stable cycling with a capacity retention of 95.6% over 100 cycles at room temperature, even undergoes a large point load of 10 N. In contrast, cells based on pure ceramic and pure polymer electrolyte show poor cycle life. The NCPE provides a new design for solid composite electrolyte and opens up new possibilities for future solid‐state lithium‐metal batteries and structural energy storage.

Fri 31 Jan 12:00: Doubt thy models: rethinking hypothesis testing in NLP Rescheduled

From All Talks (aka the CURE list). Published on Nov 29, 2019.

Doubt thy models: rethinking hypothesis testing in NLP

Recent years have seen the rise of machine learning models in NLP research, which are applied inter alia, to research on questions motivated by linguistic theory. Indeed, it has now become relatively easy to model and to test research problems. The ease with which models can be deployed comes at the risk of careless use, which may potentially lead to unreliable findings and ultimately even hinder our ability to extend our knowledge. Such misuse may stem, for example, from unfamiliarity with the assumptions and hypotheses that are implicit to the models, or inherent confounds that demand experimental controls. In this talk, I will focus on problems that are specific to linguistically-motivated questions (e.g., semantic change), but also to classical NLP research more generally, (e.g., polysemy resolution and representation), where word embeddings are the prominent ML models. Major problems include biases induced by word frequency, similarity estimation of noisy word vector representations, and the evaluation of models’ performance in the absence of properly validated evaluation tasks in general. I will suggest ways to mitigate some of these problems, and share some ideas about performing valid scientific research in the age of all-to-easy modeling.

Rescheduled

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Thu 16 Jan 16:15: A small RNA-based innate immune system guards the integrity of germ cell genomes Host: Anne Ferguson-Smith

From All Talks (aka the CURE list). Published on Nov 29, 2019.

A small RNA-based innate immune system guards the integrity of germ cell genomes

PIWI -family proteins and their associated small RNAs (piRNAs) act in an evolutionarily conserved innate immune mechanism that provides an essential protection for germ cell genomes against the activity of mobile genetic elements. piRNA populations comprise a molecular definition of transposons that permits them to be distinguished from host genes and selectively silenced. piRNAs can be generated in two distinct ways. Primary piRNAs emanate from discrete genomic loci, termed piRNA clusters, and appear to be derived from long, single-stranded precursors. The biogenesis of primary piRNAs involves at least two nucleolytic steps. Zucchini cleaves piRNA cluster transcripts to generate monophosphorylated piRNA 5’ ends. piRNA 3’ ends are likely formed by exonucleolytic trimming, after a piRNA precursor is loaded into its PIWI partner. Secondary piRNAs arise during the adaptive ping-pong cycle, with their 5’ termini being formed by the activity of PIW Is themselves. At least in Drosophila, piRNAs are maternally deposited and transmit an epigenetic signal essential for the effective control of at least some transposable elements. Our continuing efforts combine genetics, biochemistry, structural biology, and evolutionary and computational approaches to understand how the piRNA pathway effectively discriminates self from non-self at the genomic level.

Host: Anne Ferguson-Smith

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Thu 02 Apr 09:30: The microenvironment in the myeloid malignancies These talks are aimed at Masters and first year PhD students but all are welcome to attend.

From All Talks (aka the CURE list). Published on Nov 29, 2019.

The microenvironment in the myeloid malignancies

Abstract not available

These talks are aimed at Masters and first year PhD students but all are welcome to attend.

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Thu 26 Mar 09:30: Breast cancer: demographics, presentation, diagnosis & patient pathway These talks are aimed at Masters and first year PhD students but all are welcome to attend.

From All Talks (aka the CURE list). Published on Nov 29, 2019.

Breast cancer: demographics, presentation, diagnosis & patient pathway

Abstract not available

These talks are aimed at Masters and first year PhD students but all are welcome to attend.

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Thu 20 Feb 09:30: The challenges in therapeutic targeting of the RAF-MEK-ERK signalling pathway

From All Talks (aka the CURE list). Published on Nov 29, 2019.

The challenges in therapeutic targeting of the RAF-MEK-ERK signalling pathway

Abstract not available

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Thu 13 Feb 09:30: The AKT inhibitor Capivasertib (AZD5363): From Discovery to Clinical Proof of Concept These talks are aimed at first year MRes/PhD students but all are welcome to attend.

From All Talks (aka the CURE list). Published on Nov 29, 2019.

The AKT inhibitor Capivasertib (AZD5363): From Discovery to Clinical Proof of Concept

Abstract not available

These talks are aimed at first year MRes/PhD students but all are welcome to attend.

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Wed 11 Dec 14:30: Solution-Processed Organic Semiconductors for Applications in Opto-electronic

From All Talks (aka the CURE list). Published on Nov 29, 2019.

Solution-Processed Organic Semiconductors for Applications in Opto-electronic

Organic semiconductors have potential applications in various low cost, large area, flexible, light-weight devices ranging from sensors, light-emitting diodes (LEDs), displays, transistors, solar cells, photodetectors, and ratchets. In this talk, I will discuss doping organic semiconductors and designing of organic semiconductors for applications in organic solar cells, photodetectors, and electrochemical transistors.

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Coupling Topological Insulator SnSb2Te4 Nanodots with Highly Doped Graphene for High‐Rate Energy Storage

By Zhibin Wu, Gemeng Liang, Wei Kong Pang, Tengfei Zhou, Zhenxiang Cheng, Wenchao Zhang, Ye Liu, Bernt Johannessen, Zaiping Guo from Wiley: Advanced Materials: Table of Contents. Published on Nov 28, 2019.

Topological insulator SnSb2Te4 nanodots coupled with few‐layered graphene show excellent rate capability and durable cycling performance for pseudocapacitive Li‐ion and K‐ion storage. They achieve this through boosting the conductive topological surfaces, atomic doping, and interface interaction, benefitting from the rapid ion transport accelerated by the PN heterojunction, virtual electron highways provided by the conductive topological surface state, and extraordinary pseudocapacitive contribution. Abstract Topological insulators have spurred worldwide interest, but their advantageous properties have scarcely been explored in terms of electrochemical energy storage, and their high‐rate capability and long‐term cycling stability still remain a significant challenge to harvest. p‐Type topological insulator SnSb2Te4 nanodots anchoring on few‐layered graphene (SnSb2Te4/G) are synthesized as a stable anode for high‐rate lithium‐ion batteries and potassium‐ion batteries through a ball‐milling method. These SnSb2Te4/G composite electrodes show ultralong cycle lifespan (478 mAh g−1 at 1 A g−1 after 1000 cycles) and excellent rate capability (remaining 373 mAh g−1 even at 10 A g−1) in Li‐ion storage owing to the rapid ion transport accelerated by the PN heterojunction, virtual electron highways provided by the conductive topological surface state, and extraordinary pseudocapacitive contribution, whose excellent phase reversibility is confirmed by synchrotron in situ X‐ray powder diffraction. Surprisingly, durable lifespan even at practical levels of mass loading (>10 mg cm−2) for Li‐ion storage and excellent K‐ion storage performance are also observed. This work provides new insights for designing high‐rate electrode materials by boosting conductive topological surfaces, atomic doping, and the interface interaction.

Wed 11 Mar 16:00: Dogs, Cats, Disease, and the Galapagos Islands

From All Talks (aka the CURE list). Published on Nov 28, 2019.

Dogs, Cats, Disease, and the Galapagos Islands

After working on the Islands for most of 2019, Ben is in the process of developing a new Veterinary programme for 2020 to attend to the growing need for veterinary healthcare in this archipelago. When you think of the Galapagos Islands, you think of their unique and endemic wildlife, its pioneering research into conservation, and the source of Charles Darwin’s Theory of Evolution. However, Ben hopes to bring recognition to the areas not often talked about on Documentaries; the growing conflict between domesticated animals and wildlife.

This talk will provide an incredible insight into the veterinary world of invasive species, the problems they are causing, but also the problems that are affecting them.

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Mixed Organic Ligand Shells: Controlling the Nanoparticle Surface Morphology toward Tuning the Optoelectronic Properties

By Christian Henkel, Judith E. Wittmann, Johannes Träg, Johannes Will, Lisa M. S. Stiegler, Peter Strohriegl, Andreas Hirsch, Tobias Unruh, Dirk Zahn, Marcus Halik, Dirk M. Guldi from Wiley: Small: Table of Contents. Published on Nov 28, 2019.

The optical properties of perylene bisimides (PBI) are strongly aggregation dependent. Thus, PBIs are perfect candidates for probing interdye interactions on top of nanoparticle surfaces. The synergetic interplay of different spectroscopy techniques and molecular dynamics simulations gives deep insights into the formed H‐aggregates. This knowledge is used to fine‐tune the surface morphology of the attached dye molecules. Abstract Precise control over the ratio of perylene bisimide (PBI) monomers and aggregates, immobilized on alumina nanoparticle (NP) surfaces, is demonstrated. Towards this goal, phosphonic acid functionalized PBI derivatives (PA‐PBI) are shown to self‐assemble into stoichiometrically mixed monolayers featuring aliphatic, glycolic, or fluorinated phosphonic acid ligands, serving as imbedding matrix (PA‐M) to afford core–shell NPs. Different but, nevertheless, defined PBI monomer/aggregate composition is achieved by either the variation in the PA‐PBI to PA‐M ratios, or the utilization of different PA‐Ms. Various steady‐state as well as time‐resolved spectroscopy techniques are applied to probe the core–shell NPs with respect to changes in their optical properties upon variations in the shell composition. To this end, the ratio between monomer and excimer‐like emission assists in deriving information on the self‐assembled monolayer composition, local ordering, and corresponding aggregate content. With the help of X‐ray reflectivity measurements, accompanied by molecular dynamics simulations, the built‐up of the particle shells, in general, and the PBI aggregation behavior, in particular, are explored in depth.

Fast‐Acting Black‐Phosphorus‐Assisted Depression Therapy with Low Toxicity

By Liguo Jin, Ping Hu, Yinyin Wang, Luojia Wu, Kang Qin, Haoxin Cheng, Shuhua Wang, Bingxing Pan, Hongbo Xin, Wenhua Zhang, Xiaolei Wang from Wiley: Advanced Materials: Table of Contents. Published on Nov 28, 2019.

A black phosphorus (BP)‐nanosheet‐based drug delivery system is developed for synergistic photothermal/chemotherapy of depression. BP nanosheets can improve the biocompatibility of the antidepressant drug Fluoxetine. More importantly, BP‐Fluoxetine, under near‐infrared irradiation, greatly shortens the therapy time of depression with no obvious side effects, which has great potential for clinical application in the future. Abstract A black phosphorus (BP)‐nanosheet‐based drug‐delivery system containing a therapeutic drug (Fluoxetine, Flu) is synthesized. According to subsequent behavioral, biochemical, and electrophysiological analysis, BP‐Flu, after irradiated with near‐infrared light (808 nm), can significantly reduce the therapy time of depression. Meanwhile, the inherent biotoxicity of Flu is also alleviated.

A New Opportunity for 2D van der Waals Heterostructures: Making Steep‐Slope Transistors

By Juan Lyu, Jing Pei, Yuzheng Guo, Jian Gong, Huanglong Li from Wiley: Advanced Materials: Table of Contents. Published on Nov 28, 2019.

2D materials are predicted to be a rich library of cold‐source (CS) materials. Transistors based on 2D metallic CS material:2D semiconducting channel material van der Waals (vdW) heterostructures can have steep subthreshold‐slopes below 60 mV dec−1 because of the multiple inherent advantages of the 2D vdW heterostructures, namely desired density of states–energy relations and gate‐tunable barrier heights. Abstract The use of a foreign metallic cold source (CS) has recently been proposed as a promising approach toward the steep‐slope field‐effect‐transistor (FET). In addition to the selection of source material with desired density of states–energy relation (D(E)), engineering the source:channel interface for gate‐tunable channel‐barrier is crucial to CS‐FETs. However, conventional metal:semiconductor (MS) interfaces generally suffer from strong Fermi‐level pinning due to the inevitable chemical disorder and defect‐induced gap states, precluding the gate tunability of the barriers. By comprehensive materials and device modeling at the atomic scale, it is reported that 2D van der Waals (vdW) MS interfaces, with their atomic sharpness and cleanness, can be considered as general ingredients for CS‐FETs. As test cases, InSe‐based n‐type FETs are studied. It is found that graphene can be spontaneously p‐type doped along with slightly opened bandgap around the Dirac‐point by interfacing with InSe, resulting in superexponentially decaying hot carrier density with increasing n‐type channel‐barrier. Moreover, the D(E) relations suggest that 2D transition‐metal dichalcogenides and 2D transition‐metal carbides are a rich library of CS materials. Graphene, Cd3C2, T‐VTe2, H‐VTe2, and H‐TaTe2 CSs lead to subthreshold swing below 60 mV dec−1. This work broadens the application potentials of 2D vdW MS heterostructures and serves as a springboard for more studies on low‐power electronics based on 2D materials.

Microfluidic Designing Microgels Containing Highly Concentrated Gold Nanoparticles for SERS Analysis of Complex Fluids

By Yeong Hwa Kim, Dong Jae Kim, Sangmin Lee, Dong‐Ho Kim, Sung‐Gyu Park, Shin‐Hyun Kim from Wiley: Small: Table of Contents. Published on Nov 28, 2019.

Surface‐enhanced Raman scattering (SERS)‐active microgels are designed by uniformly loading highly concentrated gold nanoparticles in microgel using microfluidic technology. High density and uniform distribution of gold nanoparticles enhance SERS activity and secure signal reproducibility. Moreover, the hydrogel matrix enables the direct detection of small target molecules without interruption from large adhesives. This class of SERS substrates is promising for point‐of‐care analysis of complex samples. Abstract Surface‐enhanced Raman scattering (SERS) is one of the most promising methods to detect small molecules for point‐of‐care analysis as it is rapid, nondestructive, label‐free, and applicable for aqueous samples. Here, microgels containing highly concentrated yet evenly dispersed gold nanoparticles are designed to provide SERS substrates that simultaneously achieve contamination‐free metal surfaces and high signal enhancement and reproducibility. With capillary microfluidic devices, water‐in‐oil‐in‐water (W/O/W) double‐emulsion drops are prepared to contain gold nanoparticles and hydrogel precursors in innermost drop. Under hypertonic condition, water is selectively pumped out from the innermost drops. Therefore, gold nanoparticles are gently concentrated without forming aggregates, which are then captured by hydrogel matrix. The resulting microgels have a concentration of gold nanoparticles ≈30 times higher and show Raman intensity two orders of magnitude higher than those with no enrichment. In addition, even distribution of gold nanoparticles results in uniform Raman intensity, providing high signal reproducibility. Moreover, as the matrix of the microgel serves as a molecular filter, large adhesive proteins are rejected, which enables the direct detection of small molecules dissolved in the protein solution. It is believed that this advanced SERS platform is useful for in situ detection of toxic molecules in complex mixtures such as biological fluids, foods, and cosmetics.

Controllable Design of MoS2 Nanosheets Grown on Nitrogen‐Doped Branched TiO2/C Nanofibers: Toward Enhanced Sodium Storage Performance Induced by Pseudocapacitance Behavior

By Ling Wang, Guorui Yang, Jianan Wang, Shengjie Peng, Wei Yan, Seeram Ramakrishna from Wiley: Small: Table of Contents. Published on Nov 28, 2019.

A novel architecture of MoS2 nanosheets grown on nitrogen‐doped branched TiO2/C nanofibers are prepared via electrospinning and hydrothermal treatment method as anode materials for sodium‐ion batteries. The rational designed architecture and components can enhance the electronic conductivity and cycling stability of the electrode. The kinetic analysis demonstrates that pseudocapacitive contribution is the major factor to achieve excellent rate performance. Abstract In this work, expanded MoS2 nanosheets grown on nitrogen‐doped branched TiO2/C nanofibers (NBT/C@MoS2 NFs) are prepared through electrospinning and hydrothermal treatment method as anode materials for sodium‐ion batteries (SIBs). The continuous 1D branched TiO2/C nanofibers provide a large surface area to grow expanded MoS2 nanosheets and enhance the electronic conductivity and cycling stability of the electrode. The large surface area and doping of nitrogen can facilitate the transfer of both Na+ ions and electrons. With the merits of these unique design and extrinsic pseudocapacitance behavior, the NBT/C@MoS2 NFs can deliver ultralong cycle stability of 448.2 mA h g−1 at 200 mA g−1 after 600 cycles. Even at a high rate of 2000 mA g−1, a reversible capacity of 258.3 mA h g−1 can still be achieved. The kinetic analysis demonstrates that pseudocapacitive contribution is the major factor to achieve excellent rate performance. The rational design and excellent electrochemical performance endow the NBT/C@MoS2 NFs with potentials as promising anode materials for SIBs.

Ti‐Based Oxide Anode Materials for Advanced Electrochemical Energy Storage: Lithium/Sodium Ion Batteries and Hybrid Pseudocapacitors

By Shuaifeng Lou, Yang Zhao, Jiajun Wang, Geping Yin, Chunyu Du, Xueliang Sun from Wiley: Small: Table of Contents. Published on Nov 28, 2019.

Titanium‐based oxides including TiO2 and M‐Ti‐O compounds (M = Li, Nb, Na, etc.) family, exhibit advantageous structural dynamics for practical applications in energy storage fields. In this review, the essentials, issues, and advances of Ti‐based oxides for electrochemical energy storage from lithium‐ion batteries to sodium‐ion batteries, and then the hybrid pseudocapacitors are summarized. Abstract Titanium‐based oxides including TiO2 and M‐Ti‐O compounds (M = Li, Nb, Na, etc.) family, exhibit advantageous structural dynamics (2D ion diffusion path, open and stable structure for ion accommodations) for practical applications in energy storage systems, such as lithium‐ion batteries, sodium‐ion batteries, and hybrid pseudocapacitors. Further, Ti‐based oxides show high operating voltage relative to the deposition of alkali metal, ensuring full safety by avoiding the formation of lithium and sodium dendrites. On the other hand, high working potential prevents the decomposition of electrolyte, delivering excellent rate capability through the unique pseudocapacitive kinetics. Nevertheless, the intrinsic poor electrical conductivity and reaction dynamics limit further applications in energy storage devices. Recently, various work and in‐depth understanding on the morphologies control, surface engineering, bulk‐phase doping of Ti‐based oxides, have been promoted to overcome these issues. Inspired by that, in this review, the authors summarize the fundamental issues, challenges and advances of Ti‐based oxides in the applications of advanced electrochemical energy storage. Particularly, the authors focus on the progresses on the working mechanism and device applications from lithium‐ion batteries to sodium‐ion batteries, and then the hybrid pseudocapacitors. In addition, future perspectives for fundamental research and practical applications are discussed.

The Confinement Effect of Angstrom‐Sized Pores in Asymmetrical Membrane Constructed by Zeolitic Imidazolate Frameworks: Partially Dehydrated Ion Transport Performance

By Ruirui Li, Bingxin Lu, Zhiqiang Xie, Jin Zhai from Wiley: Small: Table of Contents. Published on Nov 28, 2019.

Asymmetrical membrane with angstrom‐sized pores is constructed by growth of ZIF‐90 membrane on the porous anodic aluminum oxide film. Novel ion transport behavior can be observed in the asymmetrical membrane with angstrom‐sized pores. Molecular dynamics simulations imply that the ions transporting across the membrane are partly dehydrated. And this asymmetrical membrane exhibits excellent alkali metal ion separation performance. Abstract The confinement effect in asymmetrical biological ion channels makes the state of molecules and ions differs from that in the external environment, and the mass transfer confined in the biological ion channels is in a single strand form. Herein, an asymmetrical membrane with angstrom‐sized pores is constructed by growth of ZIF‐90 membrane on the porous anodic aluminum oxide film. Due to the confinement effect of angstrom‐sized pores of ZIF‐90, ions transport through the pores of ZIF‐90 suffer from multiple dehydration‐hydration‐dehydration process in the form of a single ionic chain. Molecular dynamics simulations imply that ions inside the pores of ZIF‐90 are partially dehydrated. In alkaline condition, high rectification ratios of 237, 295, and 357 can be achieved in 10 × 10−3 m KCl, NaCl, and LiCl electrolyte, respectively. Besides, the strong electrostatic interaction between ions and the confined ZIF‐90 pores makes the ions transport through the asymmetrical membrane suffer from an energy barrier, and the energy barrier is different with different ion species. This work helps to understand the ions transfer mechanism through angstrom‐sized pores, which can provide guidance for the design of asymmetrical membrane and boost their applications.

Wed 05 Feb 14:15: Title to be confirmed

From All Talks (aka the CURE list). Published on Nov 28, 2019.

Title to be confirmed

Abstract not available

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Thu 05 Mar 13:00: Mixing mitosis and meiosis in Drosophila Host: Helene Rangone-Briatte

From All Talks (aka the CURE list). Published on Nov 28, 2019.

Mixing mitosis and meiosis in Drosophila

Abstract not available

Host: Helene Rangone-Briatte

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Thu 20 Feb 14:00: Rapid microbial evolution across the parasite-mutualist continuum Host: Frank Jiggins

From All Talks (aka the CURE list). Published on Nov 28, 2019.

Rapid microbial evolution across the parasite-mutualist continuum

Abstract not available

Host: Frank Jiggins

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Tue 03 Nov 11:30: Title to be confirmed Hosted by: Gurdon Institute Postdoc Association (GIPA)

From All Talks (aka the CURE list). Published on Nov 28, 2019.

Title to be confirmed

Abstract not available

Hosted by: Gurdon Institute Postdoc Association (GIPA)

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Thu 06 Feb 13:00: Decoding Transcriptional Regulation and Kinetics Using Single-Cell Transcriptomics. Host: Eric Miska

From All Talks (aka the CURE list). Published on Nov 28, 2019.

Decoding Transcriptional Regulation and Kinetics Using Single-Cell Transcriptomics.

Abstract not available

Host: Eric Miska

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Wed 15 Jan 14:15: Small Things Make Big Differences Athena SWAN Talk

From All Talks (aka the CURE list). Published on Nov 28, 2019.

Small Things Make Big Differences

Abstract not available

Athena SWAN Talk

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Cobalt Single‐Atom‐Intercalated Molybdenum Disulfide for Sulfide Oxidation with Exceptional Chemoselectivity

By Zhongxin Chen, Cuibo Liu, Jia Liu, Jing Li, Shibo Xi, Xiao Chi, Haisen Xu, In‐Hyeok Park, Xinwen Peng, Xing Li, Wei Yu, Xiaowang Liu, Linxin Zhong, Kai Leng, Wei Huang, Ming Joo Koh, Kian Ping Loh from Wiley: Advanced Materials: Table of Contents. Published on Nov 28, 2019.

A vertically structured, cobalt single‐atom‐intercalated MoS2 catalyst (Co1‐in‐MoS2) is developed for the chemoselective oxidation of sulfides to produce 34 high‐value, multifunctional sulfone derivatives and late‐stage functionalization of pharmaceuticals (Tamiflu). Abstract The identification of chemoselective oxidation process en route to fine chemicals and specialty chemicals is a long‐standing pursuit in chemical synthesis. A vertically structured, cobalt single atom‐intercalated molybdenum disulfide catalyst (Co1‐in‐MoS2) is developed for the chemoselective transformation of sulfides to sulfone derivatives. The single‐atom encapsulation alters the electron structure of catalyst owing to confinement effect and strong metal–substrate interaction, thus enhancing adsorption of sulfides and chemoselective oxidation at the edge sites of MoS2 to achieve excellent yields of up to 99% for 34 examples. The synthetic scopes can be extended to sulfide‐bearing alkenes, alkynes, aldehydes, ketones, boronic esters, and amines derivatives as a toolbox for the synthesis of high‐value, multifunctional sulfones and late‐stage functionalization of pharmaceuticals, e.g., Tamiflu. The synthetic utility of cobalt single atom‐intercalated MoS2, together with its reusability, scalability, and simplified purification process, renders it promising for industrial productions.

Novel Organophosphate‐Derived Dual‐Layered Interface Enabling Air‐Stable and Dendrite‐Free Lithium Metal Anode

By Xuejun Liu, Jie Liu, Tao Qian, Hongli Chen, Chenglin Yan from Wiley: Advanced Materials: Table of Contents. Published on Nov 28, 2019.

A dual‐layered film, generated through a facile surface chemistry, functions as a stable interface to guarantee the dendrite‐free deposition of Li metal in a working air‐stable battery. The characteristic dual‐layered structure consists of the organic components on the top layer and the inorganic substances in the bottom layer. Abstract Lithium (Li) metal, as a promising candidate for next‐generation energy storage systems, suffers from an extremely unstable interface that is prone to crack, causing serious corrosion of Li metal and dendrite growth. To address this, a novel dual‐layered interface on the Li metal anode is reported, which is featured with organics (COPO3, (CO)2PO2, and (CO)3PO) on the top and inorganics (Li3PO4) at the bottom. The flexible organic layer with reduced Young's modulus (≈550 MPa) contributes to maintain structural integrity, while the rigid inorganic layer with improved Young's modulus of ≈12 GPa is beneficial to suppress the Li dendrite growth. Accordingly, the protected Li is stabilized to maintain successive electrodeposition over 800 cycles of plating/stripping process at a current density of 2 mA cm−2. Furthermore, the uniform dual‐layered interface tends to prevent the corrosion of air to Li metal, exhibiting almost the same performance as the Li metal treated in the inert atmosphere.

Folding of single-stranded circular DNA into rigid rectangular DNA accelerates its cellular uptake

By Makiya Nishikawa from RSC - Nanoscale latest articles. Published on Nov 28, 2019.

Nanoscale, 2019, Advance Article
DOI: 10.1039/C9NR08695A, Paper
Open Access Open Access
Shozo Ohtsuki, Yukako Shiba, Tatsuoki Maezawa, Kumi Hidaka, Hiroshi Sugiyama, Masayuki Endo, Yuki Takahashi, Yoshinobu Takakura, Makiya Nishikawa
Rectangular DNA with many staples, a more rigid structure than the others, efficiently interacted with immune cells.
To cite this article before page numbers are assigned, use the DOI form of citation above.
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Lubricant‐Infused PET Grafts with Built‐In Biofunctional Nanoprobes Attenuate Thrombin Generation and Promote Targeted Binding of Cells

By Maryam Badv, Jeffrey I. Weitz, Tohid F. Didar from Wiley: Small: Table of Contents. Published on Nov 27, 2019.

The biofunctional lubricant‐infused poly(ethylene terephthalate) vascular grafts created in this study prevent nonspecific adhesion and promote targeted binding of endothelial cells. These surfaces significantly attenuate thrombin generation and blood clot formation compared to unmodified vascular grafts and can capture endothelial cells from whole blood. Abstract New surface coatings that enhance hemocompatibility and biofunctionality of synthetic vascular grafts such as expanded poly(tetrafluoroethylene) (ePTFE) and poly(ethylene terephthalate) (PET) are urgently needed. Lubricant‐infused surfaces prevent nontargeted adhesion and enhance the biocompatibility of blood‐contacting surfaces. However, limited success has been made in incorporating biofunctionality onto these surfaces and generating biofunctional lubricant‐infused coatings that both prevent nonspecific adhesion and enhance targeted binding of biomolecules remains a challenge. Here, a new generation of fluorosilanized lubricant‐infused PET surfaces with built‐in biofunctional nanoprobes is reported. These surfaces are synthesized by starting with a self‐assembled monolayer of fluorosilane that is partially etched using plasma modification technique, thereby creating a hydroxyl‐terminated fluorosilanized PET surface. Simultaneously, silanized nanoprobes are produced by amino‐silanizing anti‐CD34 antibody in solution and directly coupling the anti‐CD34‐aminosilane nanoprobes onto the hydroxyl terminated, fluorosilanized PET surface. The PET surfaces are then lubricated, creating fluorosilanized biofunctional lubricant‐infused PET substrates. Compared with unmodified PET surfaces, the designed biofunctional lubricant‐infused PET surfaces significantly attenuate thrombin generation and blood clot formation and promote targeted binding of endothelial cells from human whole blood.

Soft Ring‐Shaped Cellu‐Robots with Simultaneous Locomotion in Batches

By Tanchen Ren, Pu Chen, Longjun Gu, Mehmet Giray Ogut, Utkan Demirci from Wiley: Advanced Materials: Table of Contents. Published on Nov 27, 2019.

Scaffold‐free cell based ring‐shape mini‐robots are fabricated through a simple but efficient and robust method. Multiple cellu‐robots can be actuated en masse to assemble under a single uniform external acoustic signal to form more complex structures. To explore the application of the cellu‐robots, a two‐layer brain surrogate is assembled concentrically with an outer neuron‐rich cellu‐robot and an inner astrocyte‐rich cellu‐robot. Abstract Untethered mini‐robots can move single cells or aggregates to build complex constructs in confined spaces and may enable various biomedical applications such as regenerative repair in medicine and biosensing in bioengineering. However, a significant challenge is the ability to control multiple microrobots simultaneously in the same space to operate toward a common goal in a distributed operation. A locomotion strategy that can simultaneously guide the formation and operation of multiple robots in response to a common acoustic stimulus is developed. The scaffold‐free cellu‐robots comprise only highly packed cells and eliminate the influence of supportive materials, making them less cumbersome during locomotion. The ring shape of the cellu‐robot contributes to anisotropic cellular interactions which induce radial cellular orientation. Under a single stimulus, several cellu‐robots form predetermined complex structures such as bracelet‐like ring‐chains which transform into a single new living entity through cell–cell interactions, migration or cellular extensions between cellu‐robots.

Fri 14 Feb 13:00: TBC Lunch provided

From All Talks (aka the CURE list). Published on Nov 27, 2019.

TBC

Abstract not available

Lunch provided

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Thu 12 Dec 11:00: Moonshot Thinking to Unleash Innovation, Dr Pablo Rodriguez - Telefonica Alpha: MSR Cambridge, Lecture Series Please note, this event may be recorded. Microsoft will own the copyright of any recording and reserves the right to distribute it as required.

From All Talks (aka the CURE list). Published on Nov 27, 2019.

Moonshot Thinking to Unleash Innovation, Dr Pablo Rodriguez - Telefonica Alpha: MSR Cambridge, Lecture Series

Innovation in most large companies these days is fairly incremental. There is nothing inherently wrong in this, as much of our progress as a society has resulted from such innovation. Over recent years, however, we are seeing a radical departure from incremental innovation. Instead, we look at organisations who intentionally set extremely ambitious innovation objectives, where incremental innovation cannot get the job done.

The focus of this talk is to discuss the ways in which organisations mobilise resources to go after bold objectives which can move the needle: Moonshots. These are not incremental innovation activities, but instead multi-year missions that mobilise extensive scientific and technological resources to expand the horizons for both organizations and societies, and transform both in the process.

From the original IBM 360 mainframe computer, NASA , DARPA, Google X, or Telefonica´s skunkworks facility — Alpha, more and more organisations are trying to inductively develop a coherent approach to creating and executing organisational moonshots.

Doing so requires orchestrating diverse teams of data scientists, developers, programmers, technologists, and business strategists, to work together on audacious projects with the right culture and purpose. Moonshots will affect hundreds of millions of people, create a positive societal impact, and have the potential to grow into billion Euro businesses. Moonshot efforts at Alpha include areas of mental health, learning tutors, AI economies, or distributed energy, some of which will be discussed during the talk.

Please note, this event may be recorded. Microsoft will own the copyright of any recording and reserves the right to distribute it as required.

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Oxygen Doping Induced by Nitrogen Vacancies in Nb4N5 Enables Highly Selective CO2 Reduction

By Jiantao Fu, Haihong Bao, Yifan Liu, Yuying Mi, Yuan Qiu, Longchao Zhuo, Xijun Liu, Jun Luo from Wiley: Small: Table of Contents. Published on Nov 27, 2019.

Nitrogen‐vacancy is constructed in Nb4N5 lattice by a hydrogen annealing method, which is then refilled by the oxygen in air. The incorporation of oxygen atoms into Nb4N5 promotes the CO2 reduction reaction, which shows a high Faradaic efficiency (91%) and superior structural electrochemical stability (up to 30 h). Abstract Surface vacancy engineering holds great promise for boosting the electrocatalytic activity for CO2 reduction reaction; however, the vacancies are generally unstable and may degrade into the inactive phase during electrolysis. Stabilizing the vacancy‐enriched structure by heteroatoms can be an effective strategy to get a robust and active catalyst. Herein, a nitrogen‐vacancy enriched Nb4N5 on N‐doped carbons is constructed, which is thereafter stabilized by a self‐enhanced oxygen doping process. This oxygen‐doped complex is used as an effective CO2 catalyst, which exhibits a maximum CO Faradaic efficiency of 91% at −0.8 V (vs reversible hydrogen electrode, RHE) and long‐term stability throughout 30 h of electrocatalysis. Density function theory calculations suggest that the incorporation of oxygen in Nb4N5 facilitates the formation of *COOH and thus promotes the CO2 reduction.

SPION‐Decorated Exosome Delivered BAY55‐9837 Targeting the Pancreas through Magnetism to Improve the Blood GLC Response

By Manjiao Zhuang, Dan Du, Lingling Pu, Haixing Song, Mian Deng, Qian Long, Xiaofei Yin, Yayu Wang, Lei Rao from Wiley: Small: Table of Contents. Published on Nov 27, 2019.

A nano‐delivery system (BAY‐exosome‐SPION (superparamagnetic iron oxide nanoparticle)) with enhanced blood glucose response capacity is constructed. Exosomes provide BAY55‐9837 with longer plasma half‐life and SIPON enables BAY‐exosome to gain a favorable targeting property. With the help of magnetic force, BAY‐exosome‐SPION can respond properly to the increase of blood glucose, thus accumulates in the pancreas islet and promotes the insulin secretion. Abstract BAY55‐9837, a potential therapeutic peptide in the treatment of type 2 diabetes mellitus (T2DM), is capable of inducing glucose (GLC)‐dependent insulin secretion. However, the therapeutic benefit of BAY55‐9837 is limited by its short half‐life, lack of targeting ability, and poor blood GLC response. How to improve the blood GLC response of BAY55‐9837 is an existing problem that needs to be solved. In this study, a method for preparing BAY55‐9837‐loaded exosomes coupled with superparamagnetic iron oxide nanoparticle (SPIONs) with pancreas islet targeting activity and an enhanced blood GLC response with the help of an external magnetic force (MF) is demonstrated. The plasma half‐life of BAY55‐9837 loaded in exosome‐SPION is 27‐fold longer than that of BAY55‐9837. The active targeting property of SIPONs enables BAY‐exosomes to gain a favorable targeting property, which improves the BAY55‐9837 blood GLC response capacity with the help of an external MF. In vivo studies show that BAY‐loaded exosome‐based vehicle delivery enhances pancreas islet targeting under an external MF and markedly increases insulin secretion, thereby leading to the alleviation of hyperglycemia. The chronic administration of BAY‐exosome‐SPION/MF significantly improves glycosylated hemoglobin and lipid profiles. BAY‐exosome‐SPION/MF maybe a promising candidate for a peptide drug carrier for T2DM with a better blood GLC response.

Wed 19 Feb 13:00: Green Custard Ltd

From All Talks (aka the CURE list). Published on Nov 27, 2019.

Green Custard Ltd

Abstract not available

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Wed 12 Feb 13:00: Ourpath

From All Talks (aka the CURE list). Published on Nov 27, 2019.

Ourpath

Abstract not available

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Thu 12 Dec 16:00: Leptoquark Pair Production at Future Hadron Colliders Unusual Location

From All Talks (aka the CURE list). Published on Nov 27, 2019.

Leptoquark Pair Production at Future Hadron Colliders

As new physics continues to evade detection at the LHC , proposals have been made for future colliders with the aim of extending the mass reach and improving sensitivity to physics beyond the standard model. The scalar leptoquark provides a particularly interesting new physics candidate. At tree-level, leptoquark-mediated transitions may account for the hints at lepton flavour universality violation observed by experiments such as Belle and LHCb. I will present estimates of the sensitivity of the high luminosity and high energy modes of the LHC and of a 100 TeV future circular collider to these leptoquarks, focusing on their pair production and decay into the dimuon dijet channel.

Unusual Location

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Direct Visualization of Exciton Transport in Defective Few‐Layer WS2 by Ultrafast Microscopy

By Huan Liu, Chong Wang, Zhengguang Zuo, Dameng Liu, Jianbin Luo from Wiley: Advanced Materials: Table of Contents. Published on Nov 27, 2019.

Defect‐limited exciton transport in defective few‐layer WS2 is directly visualized by ultrafast microscopy. Neutral excitons can be captured by defects to form bound excitons in 7.75–17.88 ps, leading to decreased exciton lifetime and diffusion coefficient. Compared with the pristine sample, the exciton transport length of the defective sample is dramatically reduced from 349.44 to 107.40 nm. Abstract As defects usually limit the exciton diffusion in 2D transition metal dichalcogenides (TMDCs), the interaction knowledge of defects and exciton transport is crucial for achieving efficient TMDC‐based devices. A direct visualization of defect‐modulated exciton transport is developed in few‐layer WS2 by ultrafast transient absorption microscopy. Atomic‐scale defects are introduced by argon plasma treatment and identified by aberration‐corrected scanning transmission electron microscopy. Neutral excitons can be captured by defects to form bound excitons in 7.75–17.88 ps, which provide a nonradiative relaxation channel, leading to decreased exciton lifetime and diffusion coefficient. The exciton diffusion length of defective sample has a drastic reduction from 349.44 to 107.40 nm. These spatially and temporally resolved measurements reveal the interaction mechanism between defects and exciton transport dynamics in 2D TMDCs, giving a guideline for designing high‐performance TMDC‐based devices.

Supramolecular Nanodiscs Self‐Assembled from Non‐Ionic Heptamethine Cyanine for Imaging‐Guided Cancer Photothermal Therapy

By Xueluer Mu, Yingxi Lu, Fapu Wu, Yuhan Wei, Huihui Ma, Yingjie Zhao, Jing Sun, Shaofeng Liu, Xianfeng Zhou, Zhibo Li from Wiley: Advanced Materials: Table of Contents. Published on Nov 27, 2019.

A two‐dimensional nanodisc‐based supramolecular structure is formed by using a nonionic heptamethine cyanine dye. The nanodiscs exhibit unique photothermal and photoacoustic properties to make imaging‐guided tumor therapy a reality. This strategy represents a new paradigm in drug delivery; single‐component supramolecular nanomedicines that are self‐delivering and self‐formulating, providing a technology platform for synergistic clinical cancer imaging and therapy. Abstract Supramolecular nanomedicines, which use supramolecular design to improve the precision and effectiveness of pharmaceutical practice and optimize pharmacokinetic profiles, have gathered momentum to battle cancer and other incurable diseases, for which traditional small‐molecular and macromolecular drugs are less effective. However, the lack of clinical approval of supramolecular assembly‐based medicine underscores the challenges facing this field. A 2D nanodisc‐based supramolecular structure is formed by a non‐ionic heptamethine cyanine (Cy7) dye, which generates fluorescence self‐quenching but unique photothermal and photoacoustic properties. These Cy7‐based supramolecular nanodiscs exhibit passive tumor‐targeting properties to not only visualize the tumor by near‐infrared fluorescence imaging and photoacoustic tomography but also induce photothermal tumor ablation under irradiation. Due to the nature of organic small molecule, they induce undetectable acute toxicity in mice and can be eliminated by the liver without extrahepatic metabolism. These findings suggest that the self‐assembling cyanine discs represent a new paradigm in drug delivery as single‐component supramolecular nanomedicines that are self‐delivering and self‐formulating, and provide a platform technology for synergistic clinical cancer imaging and therapy.

Van der Waals Integrated Hybrid POM‐Zirconia Flexible Belt‐Like Superstructures

By Bilal Akram, Bing Ni, Xun Wang from Wiley: Advanced Materials: Table of Contents. Published on Nov 27, 2019.

Heteromaterials developed from two distinct inorganic materials possess unique catalytic properties. Polyoxometalate clusters not only act as catalytically active building blocks of heteromaterial but also strengthen the structure via various interactions due to their concise atomic connectivity. Such materials are endowed with new properties resulting from interfacial interactions between the different materials. Abstract A facile one‐step solvothermal approach to engineer a van der Waals integrated heteromaterial self‐assembled superstructure composed of two structurally distinct species that is polyoxomolybdate and zirconia (POM‐ZrO2) is reported. Nonclassical aggregation‐based self‐assembly process grows the superstructure. The introduced POM not only behaves as a catalytically active component of the hybrid structure but also imparts flexibility to the developed POM‐ZrO2 superstructures. The material shows high performance toward oxygenation of thioethers as a result of its morphology, composition, and structure. This growing strategy may introduce a viable pathway to the rational design of Van der Waals integrated complex hybrid, catalytically active assemblies with potential applications in different fields.

Ball‐Mill‐Exfoliated Graphene: Tunable Electrochemistry and Phenol Sensing

By Xiaoyu Li, Jian Shen, Can Wu, Kangbing Wu from Wiley: Small: Table of Contents. Published on Nov 27, 2019.

Ball‐mill‐exfoliated graphene is prepared by a simple ball‐milling method with the aid of cetyltrimethyl ammonium bromide (CTAB), and the influence mechanisms of ball‐milling time on the structure and electrochemistry properties are further explored. Finally, a sensing platform for simultaneous measurement of three phenols with high sensitivity and promising applications is successfully developed. Abstract A simple wet ball‐milling method for exfoliating pristine graphite to graphene nanosheets is proposed. The surfactant of cetyltrimethyl ammonium bromide is utilized to greatly improve the exfoliation efficiency of graphene nanosheets. Variation of the ball‐milling time is an efficient way to control the size and thickness of graphene nanosheets, as well as the level of edge defects. With an increase of ball‐milling time, superior electrochemical reactivity is imparted owing to enlarged active area and increased catalytic ability. The obtained graphene nanosheets are sensitive for electrochemical oxidation of phenols (e.g., hydroquinone, p‐chlorophenol, and p‐nitrophenol), and thus qualified for the simultaneous sensing of trace level of phenols. The detection limits of simultaneous monitoring of hydroquinone, p‐chlorophenol, and p‐nitrophenol are as low as 0.017, 0.024, and 0.42 mg L−1, respectively. The proposed strategy thus opens up a new way to tune electrochemistry of graphene materials as well as to design their new applications.

Electrochemical Monitoring of Paclitaxel‐Induced ROS Release from Mitochondria inside Single Cells

By Hong Jiang, Xin‐Wei Zhang, Quan‐Lan Liao, Wen‐Tao Wu, Yan‐Ling Liu, Wei‐Hua Huang from Wiley: Small: Table of Contents. Published on Nov 27, 2019.

A platinized SiC@C nanowire electrode with excellent electrochemical and mechanical performance is fabricated and inserted into single cells to monitor reactive oxygen species (ROS) generation from intracellular mitochondria. This allows in situ quantification of paclitaxel‐induced ROS production in real time and identification of the site of which paclitaxel induces mitochondrial ROS generation inside single living cells. Abstract Mitochondria are believed to be the major source of intracellular reactive oxygen species (ROS). However, in situ, real‐time and quantitative monitoring of ROS release from mitochondria that are present in their cytosolic environment remains a great challenge. In this work, a platinized SiC@C nanowire electrode is placed into a single cell for in situ detection of ROS signals from intracellular mitochondria, and antineoplastic agent (paclitaxel) induced ROS production is successfully recorded. Further investigations indicate that complex IV (cytochrome c oxidase, COX) is the principal site for ROS generation, and significantly more ROS are generated from mitochondria in cancer cells than that from normal cells. This work provides an effective approach to directly monitor intracellular mitochondria by nanowire electrodes, and consequently obtains important physiological evidence on antineoplastic agent‐induced ROS generation, which will be of great benefit for better understanding of chemotherapy at subcellular levels.

Retrosynthesis of Tunable Fluorescent Carbon Dots for Precise Long‐Term Mitochondrial Tracking

By Xin Geng, Yuanqiang Sun, Zhaohui Li, Ran Yang, Yanmin Zhao, Yifei Guo, Jinjin Xu, Fengting Li, Ying Wang, Siyu Lu, Lingbo Qu from Wiley: Small: Table of Contents. Published on Nov 27, 2019.

Mitochondria tracking carbon dots with intrinsic mitochondrial imaging capability and tunable long‐wavelength fluorescence from green to red are precisely synthesized via a retrosynthesis method using citric acid and m‐aminophenol as the starting molecules. Due to the high photostability and good biocompatibility, these carbon dots are suitable for long‐term imaging of mitochondria in living cells. Abstract Mitochondria play a significant role in many cellular processes. Precise long‐term tracking of mitochondrial status and behavior is very important for regulating cell fate and treating mitochondrial diseases. However, developing probes with photostability, long‐term tracking capability, and tunable long‐wavelength fluorescence has been a challenge in mitochondrial targeting. Carbon dots (CDs) as new fluorescent nanomaterials with low toxicity and high stability show increasing advantages in bioimaging. Herein, the mitochondria tracking CDs (MitoTCD) with intrinsic mitochondrial imaging capability and tunable long‐wavelength fluorescence from green to red are synthesized where the lipophilic cation of rhodamine is served as the luminescent center of CDs. Due to the excellent photostability, superior fluorescence properties and favorable biocompatibility, these MitoTCD are successfully used for mitochondrial targeting imaging of HeLa cells in vitro and can be tracked as long as six passages, which is suitable for long‐term cell imaging. Moreover, these MitoTCD can also be used for zebrafish imaging in vivo.

Freestanding Lamellar Porous Carbon Stacks for Low‐Temperature‐Foldable Supercapacitors

By Yu Yang, Sze‐Wing Ng, Dongdong Chen, Jian Chang, Dongrui Wang, Jian Shang, Qiyao Huang, Yonghong Deng, Zijian Zheng from Wiley: Small: Table of Contents. Published on Nov 27, 2019.

Low‐temperature‐foldable freestanding lamellar porous carbon stacks are obtained by filtration of holey reduced graphene oxides, carbon nanotubes, and carbon microfibers. By simply using ionic liquid as the electrolyte and combining the advanced porous multilayer structure, the obtained supercapacitor exhibits an ultrahigh areal energy density of 2.1 mWh cm−2, excellent cycling stability, and outstanding low‐temperature foldability. Abstract High‐performance supercapacitors (SCs) are important energy storage components for emerging wearable electronics. Rendering low‐temperature foldability to SCs is critically important when wearable devices are used in a cold environment. However, currently reported foldable SCs do not have a stable electrochemical performance at subzero temperatures, while those that are performing are not foldable. Herein, a freestanding pure‐carbon‐based porous electrode, namely, lamellar porous carbon stack (LPCS), is reported, which enables stable low‐temperature‐foldable SCs. The LPCS, which is fabricated with a simple vacuum filtration of a mixture of carbon fibers (CFs), holey reduced graphene oxides (HRGOs), and carbon nanotubes (CNTs), possesses a lamellar stacking of porous carbon thin sheets, in which the CFs act as the skeleton and the HRGOs and CNTs act as binders. The unique structure leads to excellent compression resilience, high foldability, and high electronic and ionic conductivity. SCs made with the LPCS electrodes and ionic liquid electrolyte show a high energy density (2.1 mWh cm−2 at 2 mA cm−2), low‐temperature long lifetime (95% capacity after 10 000 cycles at −30 °C), and excellent low‐temperature foldability (86% capacity after 1000 folding cycles at −30 °C).

Multifunctional Boron‐Doped Diamond Colloidal AFM Probes

By Sven Daboss, Peter Knittel, Christoph E. Nebel, Christine Kranz from Wiley: Small: Table of Contents. Published on Nov 27, 2019.

Novel conductive colloidal atomic force microscopy (AFM) probes are presented, taking advantage of the superior physical and electrochemical properties of boron‐doped diamond (BDD). These spherical BDD–AFM–scanning electrochemical probe microscopy (SECM) probes with relatively low force constants are highly suitable for multifunctional scanning probe microscopy (SPM) experiments using the same probe in different SPM techniques ranging from electrochemical force spectroscopy to conductive AFM imaging. Abstract Scanning probe microscopy techniques providing information on conductivity, chemical fluxes, and interfacial reactivity synchronized with topographical information have gained importance within the last decades. Herein, a novel colloidal atomic force microscopy (AFM) probe is presented using a spherical boron‐doped diamond (BDD) electrode attached and electrically connected to a modified silicon nitride cantilever. These conductive spherical BDD–AFM probes allow for electrochemical force spectroscopy. The physical robustness of these bifunctional probes, and the excellent electrochemical properties of BDD renders this concept a unique multifunctional tool for a wide variety of scanning probe studies including conductive AFM, hybrid atomic force–scanning electrochemical microscopy, and tip‐integrated chem/bio sensing.

A Red Emissive Two‐Photon Fluorescence Probe Based on Carbon Dots for Intracellular pH Detection

By Xiaoxue Ye, Yunhui Xiang, Qirong Wang, Zhen Li, Zhihong Liu from Wiley: Small: Table of Contents. Published on Nov 27, 2019.

A pH‐responsive probe based on carbon dots is fabricated for two‐photon fluorescence imaging in living systems. The aggregation causes quenching switched by pH‐induced protonation, which is utilized to modulate the fluorescence emission intensity, achieving intracellular pH monitoring. Considering the “turn‐on” signals of acidic conditions, the as‐prepared pH‐CDs can be applied for acidic environment imaging in vivo. Abstract Intracellular pH is closely related with many biological processes, including cellular proliferation, apoptosis, endocytic processes, signal transduction, and enzymatic activity. The use of fluorescent probes has become an essential method for intracellular pH detection, but existing fluorescent probes have substantial limitations, such as requiring tedious synthetic preparation, suffering from an inappropriate response range and insufficiently long emission wavelength. In this work, a red emissive two‐photon fluorescence probe based on carbon dots (pH‐CDs) is fabricated using a facile one‐pot hydrothermal method for the monitoring of intracellular pH. pH‐CDs possess a variety of superior properties, including high selectivity, excellent photostability, and low cytotoxicity. Furthermore, they exhibit a pH‐sensitive response in the range of 1.0–9.0 and a linear range of 3.5–6.5, which is desirable for tracking the pH value in living cells. It is demonstrated that the pH‐dependent fluorescence signal is regulated via switching between aggregation and disaggregation of CDs. More importantly, pH‐CDs can be successfully applied to sense and visualize pH fluctuation in cells, tissue, and zebrafish. These findings suggest that the as‐prepared pH‐CDs probe has significant potential for practical application in living systems.

Controlled Electrodeposition of Gold on Graphene: Maximization of the Defect‐Enhanced Raman Scattering Response

By Balakrishna Ananthoju, Ravi K. Biroju, Wolfgang Theis, Robert A. W. Dryfe from Wiley: Small: Table of Contents. Published on Nov 27, 2019.

Defect‐engineered chemical vapour deposition graphene/Au hybrids are used to study the surface‐enhanced Raman spectroscopic response of a solution phase dye. In‐plane defects of graphene are created using H2/Ar plasma treatment to control gold nanoparticle (Au NP) density via electrodeposition. Localized surface plasmon coupling is responsible for the enhancement, which is augmented by defect‐enhanced functionalization of graphene with Au NPs. Abstract A reliable method to prepare a surface‐enhanced Raman scattering (SERS) active substrate is developed herein, by electrodeposition of gold nanoparticles (Au NPs) on defect‐engineered, large area chemical vapour deposition graphene (GR). A plasma treatment strategy is used in order to engineer the structural defects on the basal plane of large area single‐layer graphene. This defect‐engineered Au functionalized GR, offers reproducible SERS signals over the large area GR surface. The Raman data, along with X‐ray photoelectron spectroscopy and analysis of the water contact angle are used to rationalize the functionalization of the graphene layer. It is found that Au NPs functionalization of the “defect‐engineered” graphene substrates permits detection of concentrations as low as 10−16 m for the probe molecule Rhodamine B, which offers an outstanding molecular sensing ability. Interestingly, a Raman signal enhancement of up to ≈108 is achieved. Moreover, it is observed that GR effectively quenches the fluorescence background from the Au NPs and molecules due to the strong resonance energy transfer between Au NPs and GR. The results presented offer significant direction for the design and fabrication of ultra‐sensitive SERS platforms, and also open up possibilities for novel applications of defect engineered graphene in biosensors, catalysis, and optoelectronic devices.

Preferential Tumor Accumulation of Polyglycerol Functionalized Nanodiamond Conjugated with Cyanine Dye Leading to Near‐Infrared Fluorescence In Vivo Tumor Imaging

By Fumi Yoshino, Tsukuru Amano, Yajuan Zou, Jian Xu, Fuminori Kimura, Yoshio Furusho, Tokuhiro Chano, Takashi Murakami, Li Zhao, Naoki Komatsu from Wiley: Small: Table of Contents. Published on Nov 27, 2019.

Nanodiamonds (ND) functionalized with polyglycerol (PG) and further conjugated with cyanine7 (Cy7) near‐infrared dye (ND‐PG‐Cy7) show preferential accumulation in tumor lesions in vivo thanks to the stealth property of PG. The prolonged in vivo circulation of ND‐PG‐Cy7 enables fluorescence tumor imaging based only on the enhanced permeation and retention effect, or passive targeting, without any active targeting. Abstract Preferential accumulation of nanoparticles in a tumor is realized commonly by combined effects of active and passive targeting. However, passive targeting based on an enhanced permeation and retention (EPR) effect is not sufficient to observe clear tumor fluorescence images in most of the in vivo experiments using tumor‐bearing mice. Herein, polyglycerol‐functionalized nanodiamonds (ND‐PG) conjugated with cyanine dye (Cy7) are synthesized and it is found that the resulting ND‐PG‐Cy7 is preferentially accumulated in the tumor, giving clear fluorescence in in vivo and ex vivo fluorescence images. One of the plausible reasons is the longer in vivo blood circulation time of ND‐PG‐Cy7 (half‐life: 58 h determined by the pharmacokinetic analysis) than that of other nanoparticles (half‐life:

Correlation between the Carbon Nanotube Growth Rate and Byproducts in Antenna‐Type Remote Plasma Chemical Vapor Deposition Observed by Vacuum Ultraviolet Absorption Spectroscopy

By Masafumi Inaba, Takumi Ochiai, Kazuyoshi Ohara, Ryogo Kato, Tasuku Maki, Toshiyuki Ohashi, Hiroshi Kawarada from Wiley: Small: Table of Contents. Published on Nov 27, 2019.

The density of C2H4 just before reaching the carbon nanotube (CNT) growth region is investigated by vacuum ultraviolet absorption spectroscopy for an antenna‐type remote plasma chemical vapor deposition with a CH4/H2 system. The plasma discharge forms C2Hx species, which reversibly reform to C2H4 in the plasma‐off state. The density of formed C2H4 is correlated to the CNT growth rate. Abstract For sp2 or sp3 carbon material growth, it is important to investigate the precursors or intermediates just before growth. In this study, the density of ethylene (C2H4) outside the plasma discharge space and just before reaching the carbon nanotube (CNT) growth region is investigated by vacuum ultraviolet absorption spectroscopy for plasma discharge in an antenna‐type remote plasma chemical vapor deposition with a CH4/H2 system, with which the growth of very long (≈0.5 cm) CNT forests is achieved. Single‐wall CNT forests have the potential for application as electrodes in battery cells, vertical wiring for high current applications, and thermal interface materials. It is observed that the plasma discharge decomposes the CH4 source gas and forms C2Hx species, which reversibly reform to C2H4 in the plasma‐off state. In addition, the density of the formed C2H4 has a strong correlation to the CNT growth rate. Therefore, the C2H4 density is a good indicator of the density of C2Hx species for CNT growth in the CH4/H2 plasma system.

Graphene Oxide‐Assisted and DNA‐Modulated SERS of AuCu Alloy for the Fabrication of Apurinic/Apyrimidinic Endonuclease 1 Biosensor

By Junyao Li, Hang Heng, Jianlin Lv, Tingting Jiang, Zhaoyin Wang, Zhihui Dai from Wiley: Small: Table of Contents. Published on Nov 27, 2019.

Anisotropic AuCu alloy is combined with graphene oxide (GO) to form a high SERS active substrate. Intrinsic effect of DNA on SERS activity of AuCu/GO is investigated and employed in fabricating an apurinic/apyrimidinic endonuclease 1 (APE1) biosensor. Benefitting from SERS substrate and sensing strategy, the SERS biosensor reveals superior analytical performance than standard methods in quantifying APE1 in human serum. Abstract Fabrication of high‐performance surface‐enhanced Raman scattering (SERS) biosensors relies on the coordination of SERS substrates and sensing strategies. Herein, a SERS active AuCu alloy with a starfish‐like structure is prepared using a surfactant‐free method. By covering the anisotropic AuCu alloy with graphene oxide (GO), enhanced SERS activity is obtained owing to graphene‐enhanced Raman scattering and assembly of Raman reporters. Besides, stability of SERS is promoted based on the protection of GO to the AuCu alloy. Meanwhile, it is found that SERS activity of AuCu/GO can be regulated by DNA. The regulation is sequence and length dual‐dependent, and short polyT reveals the strongest ability of enhancing the SERS activity. Relying on this phenomenon, a SERS biosensor is designed to quantify apurinic/apyrimidinic endonuclease 1 (APE1). Because of the APE1‐induced cycling amplification, the biosensor is able to detect APE1 sensitively and selectively. In addition, APE1 in human serum is analyzed by the SERS biosensor and enzyme‐linked immunosorbent assay (ELISA). The data from the SERS method are superior to that from ELISA, indicating great potential of this biosensor in clinical applications.

Rational Construction of 3D‐Networked Carbon Nanowalls/Diamond Supporting CuO Architecture for High‐Performance Electrochemical Biosensors

By Zhaofeng Zhai, Bing Leng, Nianjun Yang, Bing Yang, Lusheng Liu, Nan Huang, Xin Jiang from Wiley: Small: Table of Contents. Published on Nov 27, 2019.

The 3D‐networked CuO@carbon nanowalls/diamond (C/D) architecture is rationally designed, and it demonstrates excellent performance in the electrochemical biosensing of glucose, due to the synergistic effect coming from high‐electrocatalytic‐activity CuO and the C/D transducer with large surface area, accessible open surfaces, and high electrical conduction. Besides, the robust diamond nanoplatelet scaffolds improve structural stability of the designed electrode. Abstract Tremendous demands for highly sensitive and selective nonenzymatic electrochemical biosensors have motivated intensive research on advanced electrode materials with high electrocatalytic activity. Herein, the 3D‐networked CuO@carbon nanowalls/diamond (C/D) architecture is rationally designed, and it demonstrates wide linear range (0.5 × 10−6–4 × 10−3 m), high sensitivity (1650 µA cm−2 mm−1), and low detection limit (0.5 × 10−6 m), together with high selectivity, great long‐term stability, and good reproducibility in glucose determination. The outstanding performance of the CuO@C/D electrode can be ascribed to the synergistic effect coming from high‐electrocatalytic‐activity CuO nanoparticles and 3D‐networked conductive C/D film. The C/D film is composed of carbon nanowalls and diamond nanoplatelets; and owing to the large surface area, accessible open surfaces, and high electrical conduction, it works as an excellent transducer, greatly accelerating the mass‐ and charge‐transport kinetics of electrocatalytic reaction on the CuO biorecognition element. Besides, the vertical aligned diamond nanoplatelet scaffolds could improve structural and mechanical stability of the designed electrode in long‐term performance. The excellent CuO@C/D electrode promises potential application in practical glucose detection, and the strategy proposed here can also be extended to construct other biorecognition elements on the 3D‐networked conductive C/D transducer for various high‐performance nonenzymatic electrochemical biosensors.

Janus Graphene Liquid Crystalline Fiber with Tunable Properties Enabled by Ultrafast Flash Reduction

By In Ho Kim, Tae Hong Im, Han Eol Lee, Ji‐Soo Jang, Hee Seung Wang, Gil Yong Lee, Il‐Doo Kim, Keon Jae Lee, Sang Ouk Kim from Wiley: Small: Table of Contents. Published on Nov 27, 2019.

Ultrafast photothermal treatment by flash light can effectively reduce graphene oxide liquid crystalline fibers. Resultant flash induced graphene fibers with different reduction conditions enable delicate controllability of the mechanical properties and electrical conductivity along with spatial control of reduction level. Humidity sensors are fabricated from flash reduced graphene fibers and reveal superior sensing performance over conventional thermally reduced counterparts. Abstract Flash photothermal treatment via Xenon lamp with a broad wavelength spectrum can effectively remove oxygen functionalities and restore sp2 domains at graphitic carbon materials. The chemical composition and relevant structure formation of flash reduced graphene oxide liquid crystal (GOLC) fibers are investigated in accordance with flash irradiation conditions. Owing to the spatial controllability of reduction level via anisotropic flash irradiation, the mechanical properties and electrical conductivity of graphene fibers can be delicately counterbalanced to attain desired properties. High sensitivity humidity sensors can be fabricated from the flash reduced fibers demonstrating notably higher sensitivity over the thermally reduced counterparts. This ultrafast flash reduction holds great promise for multidimensional macroscopic GO based structures, enabling a wide range of potential applications, including textile electronics and wearable sensors.

Boron‐Doped Diamond for Hydroxyl Radical and Sulfate Radical Anion Electrogeneration, Transformation, and Voltage‐Free Sustainable Oxidation

By Junzhuo Cai, Tiezheng Niu, Penghui Shi, Guohua Zhao from Wiley: Small: Table of Contents. Published on Nov 27, 2019.

Novel insight concerning the radical mechanism at a boron‐doped diamond (BDD) anode is obtained, given by a series of advanced methods including in situ electrochemical electron paramagnetic resonance (EPR) spectroscopy. An important strategy for sustainable oxidation, in particular for in situ water remediation, is revealed. This strategy provides new theoretic evidence and will expand environmental applications of boron‐doped diamond materials. Boron‐doped diamond‐based electrochemical advanced oxidation processes (BDD‐EAOPs) have attracted much attention. However, few systematic studies concerning the radical mechanism in BDD‐EAOPs have been published. In situ electron paramagnetic resonance spectrometry is used to confirm that SO4•− is directly electrogenerated from SO42−. Then, excess SO4•− dimerizes to form S2O82− and accumulates in the BDD‐EAOP system. But no S2O82− accumulates at pH = 10 owing to the rapid transformation of SO4•− and S2O82−. Above the overpotential of water oxidation, •OH is electrogenerated and cooperated with SO4•−. In the power‐off phase, the accumulated S2O82− can be reactivated to SO4•− via specific degradation intermediates to achieve sustainable degradation. Di‐n‐butyl phthalate (DnBP), a typical endocrine disruptor, is selected as a model contaminant. Surprisingly, 99.8% of DnBP (initial concentration of 1 mg L−1) is removed, using an intermittent power supply strategy with a periodic 10 min power‐on phase at a duty ratio of 1:2, reducing the electrical energy consumption (1.8 kWh m−3) by more than 30% compared with continuous power supply consumption. These radical electrogeneration transformation mechanisms reveal an important new strategy for sustainable oxidation, especially for in situ water restoration, and are expected to provide a theoretical basis for BDD applications.

Untangling Cooperative Effects of Pyridinic and Graphitic Nitrogen Sites at Metal‐Free N‐Doped Carbon Electrocatalysts for the Oxygen Reduction Reaction

By James A. Behan, Eric Mates‐Torres, Serban N. Stamatin, Carlota Domínguez, Alessandro Iannaci, Karsten Fleischer, Md. Khairul Hoque, Tatiana S. Perova, Max García‐Melchor, Paula E. Colavita from Wiley: Small: Table of Contents. Published on Nov 27, 2019.

Co‐presence of pyridinic and graphitic N‐sites in metal‐free carbon electrodes modulates the binding energy of hydroperoxide/hydroperoxyl intermediates and promotes selectivity toward 4e‐reduction in the oxygen reduction reaction. Abstract Metal‐free carbon electrodes with well‐defined composition and smooth topography are prepared via sputter deposition followed by thermal treatment with inert and reactive gases. X‐ray photoelectron spectroscopy (XPS) and Raman spectroscopy show that three carbons of similar N/C content that differ in N‐site composition are thus prepared: an electrode consisting of almost exclusively graphitic‐N (NG), an electrode with predominantly pyridinic‐N (NP), and one with ≈1:1 NG:NP composition. These materials are used as model systems to investigate the activity of N‐doped carbons in the oxygen reduction reaction (ORR) using voltammetry. Results show that selectivity toward 4e‐reduction of O2 is strongly influenced by the NG/NP site composition, with the material possessing nearly uniform NG/NP composition being the only one yielding a 4e‐reduction. Computational studies on model graphene clusters are carried out to elucidate the effect of N‐site homogeneity on the reaction pathway. Calculations show that for pure NG‐doping or NP‐doping of model graphene clusters, adsorption of hydroperoxide and hydroperoxyl radical intermediates, respectively, is weak, thus favoring desorption prior to complete 4e‐reduction to hydroxide. Clusters with mixed NG/NP sites display synergistic effects, suggesting that co‐presence of these sites improves activity and selectivity by achieving high theoretical reduction potentials while facilitating retention of intermediates.

ZnS/C/MoS2 Nanocomposite Derived from Metal–Organic Framework for High‐Performance Photo‐Electrochemical Immunosensing of Carcinoembryonic Antigen

By Qiuxi Wei, Chen Wang, Ping Li, Tsunghsueh Wu, Nianjun Yang, Xing Wang, Yanying Wang, Chunya Li from Wiley: Small: Table of Contents. Published on Nov 27, 2019.

A metal‐organic framework based on ionic liquid is used as a template to synthesize MoS2 nanoparticles and is further carbonized to yield light‐responsive ZnS/C/MoS2 nanocomposites. Carcinoembryonic antigen (CEA) is selected as a model to construct a sandwich‐type photo‐electrochemical immunosensor. The excellent photoelectrochemical performance of ZnS/C/MoS2 nanocomposites, and the immunosensing CAE, are demonstrated and practically used in a clinical serum sample assay. Abstract A hexafluorophosphate ionic liquid is used as a functional monomer to prepare a metal–organic framework (Zn‐MOF). Zn‐MOF is used as a template for MoS2 nanosheets synthesis and further carbonized to yield light‐responsive ZnS/C/MoS2 nanocomposites. Zn‐MOF, carbonized‐Zn‐MOF, and ZnS/C/MoS2 nanocomposites are characterized by Fourier transform infrared spectroscopy, transmission electron microscopy, X‐ray diffraction pattern, scanning electron microscopy (SEM), element mapping, Raman spectroscopy, X‐ray photoelectron spectroscopy, fluorescence, and nitrogen‐adsorption analysis. Carcinoembryonic antigen (CEA) is selected as a model to construct an immunosensing platform to evaluate the photo‐electrochemical (PEC) performances of ZnS/C/MoS2 nanocomposites. A sandwich‐type PEC immunosensor is fabricated by immobilizing CEA antibody (Ab1) onto the ZnS/C/MoS2/GCE surface, subsequently binding CEA and the alkaline phosphatase‐gold nanoparticle labeled CEA antibody (ALP‐Au‐Ab2). The catalytic conversion of vitamin C magnesium phosphate produces ascorbic acid (AA). Upon being illuminated, AA can react with photogenerated holes from ZnS/C/MoS2 nanocomposites to generate a photocurrent for quantitative assay. Under optimized experimental conditions, the PEC immunosensor exhibits excellent analytical characteristics with a linear range from 2.0 pg mL−1 to 10.0 ng mL−1 and a detection limit of 1.30 pg mL−1 (S/N = 3). The outstanding practicability of this PEC immunosensor is demonstrated by accurate assaying of CEA in clinical serum samples.

Nitrogen‐Doped Graphene‐Encapsulated Nickel–Copper Alloy Nanoflower for Highly Efficient Electrochemical Hydrogen Evolution Reaction

By Bin Liu, Hui‐Qing Peng, Junye Cheng, Kui Zhang, Da Chen, Dong Shen, Shuilin Wu, Tianpeng Jiao, Xin Kong, Qili Gao, Shuyu Bu, Chun‐Sing Lee, Wenjun Zhang from Wiley: Small: Table of Contents. Published on Nov 27, 2019.

A novel nanoflower‐like electrocatalyst comprising few‐layer nitrogen‐doped graphene‐encapsulated nickel–copper alloy on a porous nitrogen‐doped graphic carbon framework is synthesized by a facile and scalable method, and exhibits high activity and excellent stability for hydrogen evolution due to the collective effects, including unique porous flowered architecture and the synergetic effect between the bimetallic alloy core and the graphene shell. Abstract Development of high‐performance and low‐cost nonprecious metal electrocatalysts is critical for eco‐friendly hydrogen production through electrolysis. Herein, a novel nanoflower‐like electrocatalyst comprising few‐layer nitrogen‐doped graphene‐encapsulated nickel–copper alloy directly on a porous nitrogen‐doped graphic carbon framework (denoted as Nix Cuy @ NG‐NC) is successfully synthesized using a facile and scalable method through calcinating the carbon, copper, and nickel hydroxy carbonate composite under inert atmosphere. The introduction of Cu can effectively modulate the morphologies and hydrogen evolution reaction (HER) performance. Moreover, the calcination temperature is an important factor to tune the thickness of graphene layers of the Nix Cuy @ NG‐NC composites and the associated electrocatalytic performance. Due to the collective effects including unique porous flowered architecture and the synergetic effect between the bimetallic alloy core and graphene shell, the Ni3Cu1@ NG‐NC electrocatalyst obtained under optimized conditions exhibits highly efficient and ultrastable activity toward HER in harsh environments, i.e., a low overpotential of 122 mV to achieve a current density of 10 mA cm−2 with a low Tafel slope of 84.2 mV dec−1 in alkaline media, and a low overpotential of 95 mV to achieve a current density of 10 mA cm−2 with a low Tafel slope of 77.1 mV dec−1 in acidic electrolyte.

Charge Transfer Salt and Graphene Heterostructure‐Based Micro‐Supercapacitors with Alternating Current Line‐Filtering Performance

By Doudou Zhao, Wei Chang, Chenbao Lu, Chongqing Yang, Kaiyue Jiang, Xing Chang, Hualin Lin, Fan Zhang, Sheng Han, Zhongsheng Hou, Xiaodong Zhuang from Wiley: Small: Table of Contents. Published on Nov 27, 2019.

In‐plane micro‐supercapacitors (MSCs) based on charge transfer salt (TTF‐TCNQ) and graphene heterostructures are fabricated and exhibit typical alternating current line‐filtering performance. Such MSCs can reach a phase angle of 73.2° at 120 Hz and a specific capacitance of 151 µF cm2, and are regarded as a new option for miniaturized electronics. Abstract The rapid development of lightweight and wearable devices requires electronic circuits possessing compact, high‐efficiency, and long lifetime in very limited space. Alternating current (AC) line filters are usually tools for manipulating the surplus AC ripples for the operation of most common electronic devices. So far, only aluminum electrolytic capacitors (AECs) can be utilized for this target. However, the bulky volume in the electronic circuits and limited capacitances have long hindered the development of miniaturized and flexible electronics. In this work, a facile laser‐assisted fabrication approach toward an in‐plane micro‐supercapacitor for AC line filtering based on graphene and conventional charge transfer salt heterostructure is reported. Specifically, the devices reach a phase angle of 73.2° at 120 Hz, a specific capacitance of 151 µF cm−2, and relaxation time constant of 0.32 ms at the characteristic frequency of 3056 Hz. Furthermore, the scan rate can reach up to 1000 V s−1. Moreover, the flexibility and stability of the micro‐supercapacitors are tested in gel electrolyte H2SO4/PVA, and the capacitance of micro‐supercapacitors retain a stability over 98% after 10 000 cycles. Thus, such micro‐supercapacitors with excellent electrochemical performance can be almost compared with the AECs and will be the next‐generation capacitors for AC line filters.

Maltase Decorated by Chiral Carbon Dots with Inhibited Enzyme Activity for Glucose Level Control

By Mengling Zhang, Huibo Wang, Bo Wang, Yurong Ma, Hui Huang, Yang Liu, Mingwang Shao, Bowen Yao, Zhenhui Kang from Wiley: Small: Table of Contents. Published on Nov 27, 2019.

Chiral carbon dots (CDs) with opposite optical rotation to the raw materials are synthesized by electrochemical polymerization from l‐ or d‐Glu in aqueous alkali and their optical activity can be tuned facilely by adjusting the reaction time. In addition, DCDs could act as an effective α‐glucosidase inhibitor for regulating blood glucose level. Abstract Carbon dots (CDs) have attracted increasing attention in disease therapy owing to their low toxicity and good biocompatibility. Their therapeutic effect strongly depends on the CDs structure (e.g., size or functional groups). However, the impact of CDs chirality on maltase and blood glucose level has not yet been fully emphasized and studied. Moreover, in previous reports, chiral CDs with targeted optical activity have to be synthesized from precursors of corresponding optical rotation, severely limiting chiral CDs design. Here, chiral CDs with optical rotation opposite to that of the precursor are facilely prepared through electrochemical polymerization. Interestingly, their chirality can be regulated by simply adjusting reaction time. At last, the resultant (+)‐DCDs (700 µg mL−1) are employed to modify maltase in an effort to regulate the hydrolytic rate of maltose, showing an excellent inhibition ratio to maltase of 54.7%, significantly higher than that of (−)‐LCDs (15.5%) in the same reaction conditions. The superior performance may be attributed to the preferable combination of DCDs with maltase. This study provides an electrochemical method to facilely regulate CDs chirality, and explore new applications of chiral CDs as antihyperglycemic therapy for controlling blood glucose levels.

Nickel Nitride Particles Supported on 2D Activated Graphene–Black Phosphorus Heterostructure: An Efficient Electrocatalyst for the Oxygen Evolution Reaction

By Xiao Wang, Qiaoxia Li, Penghui Shi, Jinchen Fan, Yulin Min, Qunjie Xu from Wiley: Small: Table of Contents. Published on Nov 27, 2019.

A black phosphorus (BP)–activated graphene (AG) heterostructure is designed for supporting nickel nitride (Ni3N) to enhance the performance of oxygen evolution reaction (OER). The Ni3N/BP‐AG exhibits excellent electrocatalytic performance toward OER with low overpotential and small Tafel slope. It also shows remarkable stability with a retention rate of ≈86.4% OER activity after 10 000 s. Abstract Hydrogen is regarded as the most promising green clean energy in the 21st century. Developing the highly efficient and low‐cost electrocatalysts for oxygen evolution reaction (OER) is of great concern for the hydrogen industry. In the water electrolyzed reaction, the overpotential and the kinetics are the main hurdles for OER. Therefore, an efficient and durable oxygen evolution reaction electrocatalyst is required. In this study, an activated graphene (AG)–black phosphorus (BP) nanosheets hybrid is fabricated for supporting Ni3N particles (Ni3N/BP‐AG) in the application of OER. The Ni3N particles are combined with the BP‐AG heterostructure via facile mechanical ball milling under argon protection. The synthesized Ni3N/BP‐AG shows excellent catalytic performance toward the OER, demanding the overpotential of 233 mV for a current density of 10 mA cm−2 with a Tafel slope of 42 mV dec−1. The Ni3N/BP‐AG catalysts also show remarkable stability with a retention rate of the current density of about 86.4% after measuring for 10 000 s in potentiostatic mode.

Single‐Atom Nanozyme Based on Nanoengineered Fe–N–C Catalyst with Superior Peroxidase‐Like Activity for Ultrasensitive Bioassays

By Nan Cheng, Jin‐Cheng Li, Dong Liu, Yuehe Lin, Dan Du from Wiley: Small: Table of Contents. Published on Nov 27, 2019.

A new single atom nanozyme (SAN), carbon nanotube supported single Fe atoms anchored on N‐doped carbon (CNT/FeNC), was developed for bioanalytical applications. The CNT/FeNC with robust atomic Fe–Nx moieties showed superior peroxidase‐like activity. A series of paper based bioassays were developed using SAN as the signal element. Abstract Single‐atom catalysts are becoming a hot research topic owing to their unique characteristics of maximum specific activity and atomic utilization. Herein, a new single‐atom nanozyme (SAN) based on single Fe atoms anchored on N‐doped carbons supported on carbon nanotube (CNT/FeNC) is proposed. The CNT/FeNC with robust atomic Fe–Nx moieties is synthesised, showing superior peroxidase‐like activity. Furthermore, the CNT/FeNC is used as the signal element in a series of paper‐based bioassays for ultrasensitive detection of H2O2, glucose, and ascorbic acid. The SAN provides a new type of signal element for developing various biosensing techniques.

Strong Electrochemiluminescence Emission from Oxidized Multiwalled Carbon Nanotubes

By Ruina Wang, Haishan Wu, Rui Chen, Yuwu Chi from Wiley: Small: Table of Contents. Published on Nov 27, 2019.

For the first time, strong electrochemiluminescence (ECL) with a broad emission spectrum and long maximum emission wavelength (685 nm) is observed from HNO3‐oxidized multiwalled carbon nanotubes (MWCNTs). The ECL emission results from the immobilized GQDs (IGQDs) on MWCNTs, which may have more abundant surface states and lower surface state energy than other carbon‐based quantum dots. Abstract Carbon nanotubes (CNTs) as well‐known nanomaterials are extensively studied and widely applied in various fields. Nitric acid (HNO3) is often used to treat CNTs for purification purposes and preparing oxidized CNTs for various applications. However, too little attention is paid to investigating the effect of HNO3 treatment on the optical properties of CNTs. In this work, it is observed for the first time that HNO3‐oxidized multiwalled carbon nanotubes (ox‐MWCNTs) have strong electrochemiluminescence (ECL) activity, which enables ox‐MWCNTs to become new and good ECL carbon nanomaterials after carbon quantum dots (CQDs) and graphene quantum dots (GQDs). Various characterization technologies, such as transmission electron microscope (TEM), X‐ray photoelectron spectroscopy (XPS), and Raman spectroscopy, are used to reveal the relationship between ECL activity and surface states. The ECL behaviors of ox‐MWCNTs are investigated in detail and a possible ECL mechanism is proposed. Finally, the new ECL nanomaterials of ox‐MWCNTs are envisioned to have promising applications in sensitive ECL sensing and in the study of CNT‐based catalysts.

Zwitterion‐Functionalized Detonation Nanodiamond with Superior Protein Repulsion and Colloidal Stability in Physiological Media

By Viktor Merz, Julian Lenhart, Yvonne Vonhausen, Maria E. Ortiz‐Soto, Jürgen Seibel, Anke Krueger from Wiley: Small: Table of Contents. Published on Nov 27, 2019.

The covalent functionalization of nanodiamond particles with a combination of a triglycol linker and zwitterionic headgroups ensures the colloidal stability of the nanoparticles in physiological media such as fetal bovine serum and Dulbecco's modified Eagle medium. It simultaneously prevents nonspecific adsorption of serum proteins and thus the formation of a hard protein corona—an essential prerequisite for biomedical applications. Abstract Nanodiamond (ND) is a versatile and promising material for bioapplications. Despite many efforts, agglomeration of nanodiamond and the nonspecific adsorption of proteins on the ND surface when exposed to biofluids remains a major obstacle for biomedical applications. Here, the functionalization of detonation nanodiamond with zwitterionic moieties in combination with tetraethylene glycol (TEG) moieties immobilized by click chemistry to improve the colloidal dispersion in physiological media with strong ion background and for the simultaneous prevention of nonspecific interactions with proteins is reported. Based on five building blocks, a series of ND conjugates is synthesized and their performance is compared in biofluids, such as fetal bovine serum (FBS) and Dulbecco's modified Eagle medium (DMEM). The adsorption of proteins is investigated via dynamic light scattering (DLS) and thermogravimetric analysis. The colloidal stability is tested with DLS monitoring over prolonged periods of time in various ratios of water/FBS/DMEM and at different pH values. The results show that zwitterions efficiently promote the anti‐fouling properties, whereas the TEG linker is essential for the enhanced colloidal stability of the particles.

Building Carbon‐Based Versatile Scaffolds on the Electrode Surface to Boost Capacitive Performance for Fiber Pseudocapacitors

By Jiachen Liang, Huifang Li, Huan Li, Ximan Dong, Xiaoyu Zheng, Ying Tao, Zhe Weng, Zheng‐Hong Huang, Quan‐Hong Yang from Wiley: Small: Table of Contents. Published on Nov 27, 2019.

A versatile carbon‐based scaffold for loading pseudocapacitive materials on carbonaceous fibers is built by conformally coating conductive pen ink on the surface of activated carbon fibers, which enhances the loading mass and utilization efficiency of pseudocapacitive materials simultaneously. The fibrous supercapacitors display a capacitance of up to 649 mF cm−2 and stable cycling performance. Abstract In order to fabricate high performance fiber pseudocapacitors, the trade‐off between high mass loading and high utilization efficiency of pseudocapacitive materials should be carefully addressed. Here, a solution that is to construct a carbon‐based versatile scaffold is reported for loading pseudocapacitive materials on carbonaceous fibers. The scaffold can be easily built by conformally coating commercial pen ink on the fibers without any destruction to the fiber skeleton. Due to the high electrical conductivity and abundant macropore structure, it can provide sufficient loading room and a high ion/electron conductive network for pseudocapacitive materials. Therefore, their loading mass and utilization efficiency can be increased simultaneously, and thus the as‐designed fibrous electrode displays a high areal capacitance of 649 mF cm−2 (or 122 mF cm−1 based on length), which is higher than most of the reported fiber pseudocapacitors. The simple and low‐cost strategy opens up a new way to prepare high performance portable/wearable energy storage devices.

Nanocarbon Chemistry

By Nianjun Yang, Hua Zhang from Wiley: Small: Table of Contents. Published on Nov 27, 2019.

Masthead: (Small 48/2019)

By from Wiley: Small: Table of Contents. Published on Nov 27, 2019.

Strong Electrochemiluminescence Emission from Oxidized Multiwalled Carbon Nanotubes

By Ruina Wang, Haishan Wu, Rui Chen, Yuwu Chi from Wiley: Small: Table of Contents. Published on Nov 27, 2019.

Hydrogen Evolution Reaction: Nitrogen‐Doped Graphene‐Encapsulated Nickel–Copper Alloy Nanoflower for Highly Efficient Electrochemical Hydrogen Evolution Reaction (Small 48/2019)

By Bin Liu, Hui‐Qing Peng, Junye Cheng, Kui Zhang, Da Chen, Dong Shen, Shuilin Wu, Tianpeng Jiao, Xin Kong, Qili Gao, Shuyu Bu, Chun‐Sing Lee, Wenjun Zhang from Wiley: Small: Table of Contents. Published on Nov 27, 2019.

In article number 1901545, Wenjun Zhang and co‐workers synthesize a novel nanoflower‐like electrocatalyst comprising of few‐layer nitrogen‐doped graphene encapsulated nickel copper alloy on porous graphic carbon framework by a facile and scalable method, and it exhibits high activity and excellent stability for hydrogen evolution.

Boron‐Doped Diamond: Boron‐Doped Diamond for Hydroxyl Radical and Sulfate Radical Anion Electrogeneration, Transformation, and Voltage‐Free Sustainable Oxidation (Small 48/2019)

By Junzhuo Cai, Tiezheng Niu, Penghui Shi, Guohua Zhao from Wiley: Small: Table of Contents. Published on Nov 27, 2019.

Boron‐doped diamond is perfect for efficient and sustainable oxidation of pollutants with aid of electrochemically generated radicals. In article number 1900153, Penghui Shi, Guohua Zhao, and co‐workers provide theoretical and experimental evidence of in‐situ generation of SO4•− radicals as well as their oxidation mechanism of pollutants on boron‐doped diamond surfaces.

Functional Metallofullerenes: Functional Metallofullerene Materials and Their Applications in Nanomedicine, Magnetics, and Electronics (Small 48/2019)

By Taishan Wang, Chunru Wang from Wiley: Small: Table of Contents. Published on Nov 27, 2019.

In article number 1901522, Taishan Wang and Chunru Wang review endohedral metallofullerene materials and their new functions and applications in cancer nanomedicine, antioxidative agents, spin probes, single‐molecule magnets, spin qubits, and electronic devices.

Tumor Imaging: Preferential Tumor Accumulation of Polyglycerol Functionalized Nanodiamond Conjugated with Cyanine Dye Leading to Near‐Infrared Fluorescence In Vivo Tumor Imaging (Small 48/2019)

By Fumi Yoshino, Tsukuru Amano, Yajuan Zou, Jian Xu, Fuminori Kimura, Yoshio Furusho, Tokuhiro Chano, Takashi Murakami, Li Zhao, Naoki Komatsu from Wiley: Small: Table of Contents. Published on Nov 27, 2019.

In article number 1901930, Li Zhao, Naoki Komatsu, and co‐workers functionalize nanodiamonds with polyglycerol and cyanine dye, effectively shielding protein adsorption in the blood stream, and prolonging in vivo circulation significantly. As a result, only the tumor is clearly imaged by near‐infrared fluorescence from the nanodiamonds due to their preferential accumulation in tumor rather than the organs such as the liver and spleen.

Oxygen Reduction Reaction: Untangling Cooperative Effects of Pyridinic and Graphitic Nitrogen Sites at Metal‐Free N‐Doped Carbon Electrocatalysts for the Oxygen Reduction Reaction (Small 48/2019)

By James A. Behan, Eric Mates‐Torres, Serban N. Stamatin, Carlota Domínguez, Alessandro Iannaci, Karsten Fleischer, Md. Khairul Hoque, Tatiana S. Perova, Max García‐Melchor, Paula E. Colavita from Wiley: Small: Table of Contents. Published on Nov 27, 2019.

In article number 1902081, Max García‐Melchor, Paula E. Colavita, and co‐workers show the cooperative effects induced by the co‐presence of pyridinic and graphitic N‐sites in metal‐free carbon electrodes modulate the binding energy of hydroperoxide/hydroperoxyl intermediates, promoting the selectivity towards 4e‐reduction in the oxygen reduction reaction.

MOF Photochemistry: ZnS/C/MoS2 Nanocomposite Derived from Metal–Organic Framework for High‐Performance Photo‐Electrochemical Immunosensing of Carcinoembryonic Antigen (Small 48/2019)

By Qiuxi Wei, Chen Wang, Ping Li, Tsunghsueh Wu, Nianjun Yang, Xing Wang, Yanying Wang, Chunya Li from Wiley: Small: Table of Contents. Published on Nov 27, 2019.

In article number 1902086, Yanying Wang, Chunya Li, and co‐workers use ionic liquid–based Zn‐ metal–organic framework (MOF) as template for MoS2 nanoparticles synthesis, which are then carbonized to yield light‐responsive ZnS/C/MoS2 nanocomposites. ZnS/C/MoS2 nanocomposites can produce good photocurrent response under the excitation of visible light and are used as a photoactive element to construct a sandwich‐type immunosensing platform for carcinoembryonic antigen. Excellent photoelectrochemical sensing performances of the immunosensor are successfully demonstrated.

Carbon Dots: Retrosynthesis of Tunable Fluorescent Carbon Dots for Precise Long‐Term Mitochondrial Tracking (Small 48/2019)

By Xin Geng, Yuanqiang Sun, Zhaohui Li, Ran Yang, Yanmin Zhao, Yifei Guo, Jinjin Xu, Fengting Li, Ying Wang, Siyu Lu, Lingbo Qu from Wiley: Small: Table of Contents. Published on Nov 27, 2019.

In article number 1901517, Zhaohui Li, Ying Wang, and co‐workers report a kind of mitochondria tracking carbon dots with intrinsic mitochondrial imaging capability and tunable long‐wavelength fluorescence from green to red. These carbon dots are precisely synthesized via a retrosynthesis method and are suitable for long‐term imaging of mitochondria in living cells.

1D Carbon‐Based Nanocomposites for Electrochemical Energy Storage

By Changwei Shi, Kwadwo Asare Owusu, Xiaoming Xu, Ting Zhu, Guobin Zhang, Wei Yang, Liqiang Mai from Wiley: Small: Table of Contents. Published on Nov 27, 2019.

1D carbon‐based nanocomposites are categorized into four configurations, including 1D carbon‐embedded, carbon‐coated, carbon‐encapsulated, and carbon‐supported nanostructures. The important advances in the synthesis and applications of 1D carbon‐based nanocomposites for different energy storage systems, and in situ characterization techniques for understanding the fundamental mechanism and predicting their optimization, are discussed. Abstract Electrochemical energy storage (EES) devices have attracted immense research interests as an effective technology for utilizing renewable energy. 1D carbon‐based nanostructures are recognized as highly promising materials for EES application, combining the advantages of functional 1D nanostructures and carbon nanomaterials. Here, the recent advances of 1D carbon‐based nanomaterials for electrochemical storage devices are considered. First, the different categories of 1D carbon‐based nanocomposites, namely, 1D carbon‐embedded, carbon‐coated, carbon‐encapsulated, and carbon‐supported nanostructures, and the different synthesis methods are described. Next, the practical applications and optimization effects in electrochemical energy storage devices including Li‐ion batteries, Na‐ion batteries, Li–S batteries, and supercapacitors are presented. After that, the advanced in situ detection techniques that can be used to investigate the fundamental mechanisms and predict optimization of 1D carbon‐based nanocomposites are discussed. Finally, an outlook for the development trend of 1D carbon‐based nanocomposites for EES is provided.

Carbon Dots, Unconventional Preparation Strategies, and Applications Beyond Photoluminescence

By Xue‐Tao Tian, Xue‐Bo Yin from Wiley: Small: Table of Contents. Published on Nov 27, 2019.

Carbon dots are reviewed in terms of their unconventional preparation strategies and applications beyond photoluminescence, including electrochemiluminescence, solar photovoltaics, photocatalysis, and theranostics. With the discussions, the dualities of carbon dots are revealed. Abstract Carbon dots (C‐dots) are generally separated into graphene quantum dots (GQDs) and carbon nanodots (CNDs) based on their respective top‐down and bottom‐up preparation processes. However, GQDs can be prepared by carbonization of small‐molecule precursors as revealed with unconventional preparation strategies. Thus, it is their structures rather than their precursors and preparation strategy that govern whether C‐dots are GQDs or CNDs. Here, the composites, structure, and electronic properties of C‐dots are discussed. C‐dots generally consist of a graphite‐like core and amorphous oxygen‐containing shell. When graphite becomes C‐dots, its conduction and valence bands are separated, and the quantum confinement effect appears. Combined with the light‐harvesting ability inherited from graphite, electrons in the core of C‐dots are transferred from conduction to valence bands, leading to electron–hole pair formation upon light excitation. The photoexcitation activities, such as photovoltaic conversion, photocatalysis, and photodynamic therapy, are influenced by the electronic properties of the core. Different to the semiconductor properties of core, the C‐dot shell is electrochemically active, leading to electrochemiluminescence (ECL). The oxygen‐containing groups in shell can conjugate to functional species for use in imaging and therapy. The applications of C‐dots beyond photoluminescence, including ECL, solar photovoltaics, photocatalysis, and theranostics, are reviewed.

Recent Advances of Porous Graphene: Synthesis, Functionalization, and Electrochemical Applications

By Yuanyuan Zhang, Qijin Wan, Nianjun Yang from Wiley: Small: Table of Contents. Published on Nov 27, 2019.

Synthesis of 2D and 3D porous graphene is reviewed together with their functionalization with hetero‐atoms and other functional materials. Electrochemical applications of these porous graphene are highlighted in the fields of electrochemical sensing, electrocatalysis, and electrochemical energy storage and conversion. The future research directions and challenges on porous graphene are also discussed and outlined. Abstract Graphene is a 2D sheet of sp2 bonded carbon atoms and tends to aggregate together, due to the strong π–π stacking and van der Waals attraction between different layers. Its unique properties such as a high specific surface area and a fast mass transport rate are severely blocked. To address these issues, various kinds of 2D holey graphene and 3D porous graphene are either self‐assembled from graphene layers or fabricated using graphene related materials such as graphene oxide and reduced graphene oxide. Porous graphene not only possesses unique pore structures, but also introduces abundant exposed edges and accelerates mass transfer. The properties and applications of these porous graphenes and their composites/hybrids have been extensively studied in recent years. Herein, recent progress and achievements in synthesis and functionalization of various 2D holey graphene and 3D porous graphene are reviewed. Of special interest, electrochemical applications of porous graphene and its hybrids in the fields of electrochemical sensing, electrocatalysis, and electrochemical energy storage, are highlighted. As the closing remarks, the challenges and opportunities for the future research of porous graphene and its composites are discussed and outlined.

Far‐Red to Near‐Infrared Carbon Dots: Preparation and Applications in Biotechnology

By Xinxin Shi, Hongmin Meng, Yuanqiang Sun, Lingbo Qu, Yuehe Lin, Zhaohui Li, Dan Du from Wiley: Small: Table of Contents. Published on Nov 27, 2019.

Far‐red to near‐infrared emitting carbon dots (CDs) are promising nanomaterials in the biomedical field. In this Review, far‐red to near‐infrared CDs are systematically summarized from their precursors and synthesis strategies, including top‐down and bottom‐up, to their applications in biosensing, bioimaging, and therapy. Finally, this Review discusses current challenges and opportunities of far‐red to near‐infrared CDs. Abstract As novel fluorescent nanomaterials, carbon dots (CDs) exhibit excellent photostability, good biocompatibility, and high quantum yield (QY). Their superior properties make them promising candidates for biomedical assays and therapy. Among them, the red‐emission (>600 nm) CDs have attracted increasing attention in the past years due to their little damage to the biological matrix, deep tissue penetration, and minimum autofluorescence background of biosamples. This Review, summarizes the recent progress of far‐red to near‐infrared (NIR) CDs from the preparation and their biological applications. The challenges in designing far‐red and NIR CDs and their further applications in biomedical fields are also discussed.

A Perspective on Fluorescent Nanodiamond Bioimaging

By Marco D. Torelli, Nicholas A. Nunn, Olga A. Shenderova from Wiley: Small: Table of Contents. Published on Nov 27, 2019.

The field of fluorescent nanodiamonds (FNDs) has advanced greatly over the past few years. This Review summarizes the advances made in the synthesis, functionalization, and application of FNDs to bioimaging. Highlights range from super‐resolution microscopy, through cellular and whole animal imaging, up to constantly emerging fields including sensing and hyperpolarized magnetic resonance imaging. Abstract The field of fluorescent nanodiamonds (FNDs) has advanced greatly over the past few years. Though historically limited primarily to red fluorescence, the wavelengths available for nanodiamonds have increased due to continuous technical advancement. This Review summarizes the strides made in the synthesis, functionalization, and application of FNDs to bioimaging. Highlights range from super‐resolution microscopy, through cellular and whole animal imaging, up to constantly emerging fields including sensing and hyperpolarized magnetic resonance imaging.

Functional Metallofullerene Materials and Their Applications in Nanomedicine, Magnetics, and Electronics

By Taishan Wang, Chunru Wang from Wiley: Small: Table of Contents. Published on Nov 27, 2019.

Endohedral metallofullerenes exhibit combined properties from carbon cages as well as internal metal moieties and have great potential in wide application as molecule materials. This Review provides a summary of above metallofullerene studies reported recently, including in the field of tumor inhibition, tumor vascular‐targeting therapies, antioxidative activity, spin probes, single‐molecule magnets, spin qubits, and electronic devices. Abstract Endohedral metallofullerenes exhibit combined properties from carbon cages as well as internal metal moieties and have great potential in a wide range of applications as molecule materials. Along with the breakthrough of mass production of metallofullerenes, their applied research has been greatly developed with more and more new functions and practical applications. For gadolinium metallofullerenes, their water‐soluble derivatives have been demonstrated with antitumor activity and unprecedented tumor vascular‐targeting therapy. Metallofullerene water‐soluble derivatives also can be applied to treat reactive oxygen species (ROS)‐induced diseases due to their high antioxidative activity. For magnetic metallofullerenes, the internal electron spin and metal species bring about spin sensitivity, molecular magnets, and spin quantum qubits, which have many promising applications. Metallofullerenes are significant candidates for fabricating useful electronic devices because of their various electronic structures. This Review provides a summary of the metallofullerene studies reported recently, in the fields of tumor inhibition, tumor vascular‐targeting therapies, antioxidative activity, spin probes, single‐molecule magnets, spin qubits, and electronic devices. This is not an exhaustive summary and there are many other important study results regarding metallofullerenes. All of this research has revealed the irreplaceable role of metallofullerene materials.

Nanodiamond‐Based Theranostic Platform for Drug Delivery and Bioimaging

By Guanyue Gao, Qingyue Guo, Jinfang Zhi from Wiley: Small: Table of Contents. Published on Nov 27, 2019.

Theranostic nanodiamonds (NDs) are promising candidates in cancer therapy. In this Concept paper, recent progresses in ND‐based target drug delivery systems and bioimaging probes are briefly introduced, and the future perspectives for theranostic NDs in biomedical application are discussed. Abstract Nanodiamonds (NDs) are promising candidates for biomedical application due to their excellent biocompatibility and innate physicochemical properties. In this Concept article, nanodiamond‐based theranostic platforms, which combine both drug delivery features and bioimaging functions, are discussed. The latest developments of therapeutic strategies are introduced and future perspectives for theranostic NDs are addressed.

Temperature‐Invariant Superelastic and Fatigue Resistant Carbon Nanofiber Aerogels

By Chao Li, Yan‐Wei Ding, Bi‐Cheng Hu, Zhen‐Yu Wu, Huai‐Ling Gao, Hai‐Wei Liang, Jia‐Fu Chen, Shu‐Hong Yu from Wiley: Advanced Materials: Table of Contents. Published on Nov 27, 2019.

A graphitic carbon nanofiber aerogel (CNFA) is fabricated from structural biological material (i.e., bacterial cellulose) by engineering pyrolysis chemistry, which perfectly inherits the hierarchical structures from macroscopic to microscopic scales. This CNFA maintains superelasticity without plastic deformation after 2 × 106 compressive cycles, and exhibits temperature‐invariant superelasticity and fatigue resistance over a wide temperature range from −100 to 500 °C. Abstract Superelastic and fatigue‐resistant materials that can work over a wide temperature range are highly desired for diverse applications. A morphology‐retained and scalable carbonization method is reported to thermally convert a structural biological material (i.e., bacterial cellulose) into graphitic carbon nanofiber aerogel by engineering the pyrolysis chemistry. The prepared carbon aerogel perfectly inherits the hierarchical structures of bacterial cellulose from macroscopic to microscopic scales, resulting in remarkable thermomechanical properties. In particular, it maintains superelasticity without plastic deformation even after 2 × 106 compressive cycles and exhibits exceptional temperature‐invariant superelasticity and fatigue resistance over a wide temperature range at least from −100 to 500 °C. This aerogel shows unique advantages over polymeric foams, metallic foams, and ceramic foams in terms of thermomechanical stability and fatigue resistance, with the realization of scalable synthesis and the economic advantage of biological materials.

2D Perovskite Sr2Nb3O10 for High‐Performance UV Photodetectors

By Siyuan Li, Yong Zhang, Wei Yang, Hui Liu, Xiaosheng Fang from Wiley: Advanced Materials: Table of Contents. Published on Nov 27, 2019.

Liquid‐exfoliated 2D wide‐bandgap perovskite Sr2Nb3O10 (SNO) nanosheets are explored for high‐performance UV photodetection. Phototransistors based on individual few‐layer SNO nanosheets exhibit outstanding, narrowband, and thickness‐dependent photoresponsivity as high as 1214 A W−1 and fast response speed. Flexible, transparent photodetectors with high mechanical stability are easily fabricated based on SNO nanosheet film. Abstract 2D perovskites, due to their unique properties and reduced dimension, are promising candidates for future optoelectronic devices. However, the development of stable and nontoxic 2D wide‐bandgap perovskites remains a challenge. 2D all‐inorganic perovskite Sr2Nb3O10 (SNO) nanosheets with thicknesses down to 1.8 nm are synthesized by liquid exfoliation, and for the first time, UV photodetectors (PDs) based on individual few‐layer SNO sheets are investigated. The SNO sheet‐based PDs exhibit excellent UV detecting performance (narrowband responsivity = 1214 A W−1, external quantum efficiency = 5.6 × 105%, detectivity = 1.4 × 1014 Jones @270 nm, 1 V bias), and fast response speed (trise ≈ 0.4 ms, tdecay ≈ 40 ms), outperforming most reported individual 2D sheet‐based UV PDs. Furthermore, the carrier transport properties of SNO and the performance of SNO‐based phototransistors are successfully controlled by gate voltage. More intriguingly, the photodetecting performance and carrier transport properties of SNO sheets are dependent on their thickness. In addition, flexible and transparent PDs with high mechanical stability are easily fabricated based on SNO nanosheet film. This work sheds light on the development of high‐performance optoelectronics based on low‐dimensional wide‐bandgap perovskites in the future.

Integration of Optical Surface Structures with Chiral Nanocellulose for Enhanced Chiroptical Properties

By Rui Xiong, Shengtao Yu, Saewon Kang, Katarina M. Adstedt, Dhriti Nepal, Timothy J. Bunning, Vladimir V. Tsukruk from Wiley: Advanced Materials: Table of Contents. Published on Nov 27, 2019.

Hierarchical chiroptical systems are constructed by combining imprinted surface optical structures, including optical gratings and microlenses, with the natural chiral organization of cellulose nanocrystals. The resulting biofilms with embedded optical elements exhibit vivid, controllable structural coloration combined with highly asymmetric broadband circular dichroism and a microfocusing capability not typically found in traditional photonic bioderived materials. Abstract The integration of chiral organization with photonic structures found in many living creatures enables unique chiral photonic structures with a combination of selective light reflection, light propagation, and circular dichroism. Inspired by these natural integrated nanostructures, hierarchical chiroptical systems that combine imprinted surface optical structures with the natural chiral organization of cellulose nanocrystals are fabricated. Different periodic photonic surface structures with rich diffraction phenomena, including various optical gratings and microlenses, are replicated into nanocellulose film surfaces over large areas. The resulting films with embedded optical elements exhibit vivid, controllable structural coloration combined with highly asymmetric broadband circular dichroism and a microfocusing capability not typically found in traditional photonic bioderived materials without compromising their mechanical strength. The strategy of imprinting surface optical structures onto chiral biomaterials facilitates a range of prospective photonic applications, including stereoscopic displays, polarization encoding, chiral polarizers, and colorimetric chiral biosensing.

[ASAP] Correction to Unraveling the Enzymatic Activity of Oxygenated Carbon Nanotubes and Their Application in the Treatment of Bacterial Infections

By Huan Wang, Penghui Li, Dongqin Yu, Yan Zhang, Zhenzhen Wang, Chaoqun Liu, Hao Qiu, Zhen Liu*, Jinsong Ren*, and Xiaogang Qu* from Nano Letters: Latest Articles (ACS Publications). Published on Nov 27, 2019.

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Nano Letters
DOI: 10.1021/acs.nanolett.9b04830