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NanoManufacturing

Michael De Volder, Engineering Department - IfM

Studying at Cambridge

Nanoscience News

Tue 30 Apr 14:30: Title to be confirmed

From All Talks (aka the CURE list). Published on Apr 19, 2019.

Title to be confirmed

Abstract not available

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C‐Terminal Bioconjugation of Peptides through Photoredox Catalyzed Decarboxylative Alkynylation

By Marion Garreau, Franck Le Vaillant, Jerome Waser from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 18, 2019.

We report the first decarboxylative alkynylation of the C‐terminus of peptides starting from free carboxylic acids. The reaction is fast, metal‐free and proceeds cleanly to afford alkynylated peptides with a broad tolerance for the C‐terminal amino acid. Through the use of hypervalent iodine reagents, the introduction of a broad range of functional groups was successful. C‐terminal selectivity was achieved by differentiation of the oxidation potentials of the carboxylic acids based on the use of fine‐tuned organic dyes.

Evidence of Spin Frustration in a Vanadium Diselenide Monolayer Magnet

By Ping Kwan Johnny Wong, Wen Zhang, Fabio Bussolotti, Xinmao Yin, Tun Seng Herng, Lei Zhang, Yu Li Huang, Giovanni Vinai, Sridevi Krishnamurthi, Danil W. Bukhvalov, Yu Jie Zheng, Rebekah Chua, Alpha T. N'Diaye, Simon A. Morton, Chao‐Yao Yang, Kui‐Hon Ou Yang, Piero Torelli, Wei Chen, Kuan Eng Johnson Goh, Jun Ding, Minn‐Tsong Lin, Geert Brocks, Michel P. de Jong, Antonio H. Castro Neto, Andrew Thye Shen Wee from Wiley: Advanced Materials: Table of Contents. Published on Apr 18, 2019.

Monolayer VSe2 represents a unique system for exploring the interplay between charge density wave and magnetism phenomena. Evidence of spin frustration is obtained in monolayer VSe2, which is significant toward the search for exotic low‐dimensional quantum phases and further theoretical and experimental studies of van der Waals monolayer magnets. Abstract Monolayer VSe2, featuring both charge density wave and magnetism phenomena, represents a unique van der Waals magnet in the family of metallic 2D transition‐metal dichalcogenides (2D‐TMDs). Herein, by means of in situ microscopy and spectroscopic techniques, including scanning tunneling microscopy/spectroscopy, synchrotron X‐ray and angle‐resolved photoemission, and X‐ray absorption, direct spectroscopic signatures are established, that identify the metallic 1T‐phase and vanadium 3d1 electronic configuration in monolayer VSe2 grown on graphite by molecular‐beam epitaxy. Element‐specific X‐ray magnetic circular dichroism, complemented with magnetic susceptibility measurements, further reveals monolayer VSe2 as a frustrated magnet, with its spins exhibiting subtle correlations, albeit in the absence of a long‐range magnetic order down to 2 K and up to a 7 T magnetic field. This observation is attributed to the relative stability of the ferromagnetic and antiferromagnetic ground states, arising from its atomic‐scale structural features, such as rotational disorders and edges. The results of this study extend the current understanding of metallic 2D‐TMDs in the search for exotic low‐dimensional quantum phenomena, and stimulate further theoretical and experimental studies on van der Waals monolayer magnets.

Single‐Stimulus‐Induced Modulation of Multiple Optical Properties

By Hai Li, Chaoran Li, Wei Sun, Yuzhu Wang, Wenqiang Hua, Jingjing Liu, Shumin Zhang, Zhijie Chen, Shenghua Wang, Zhiyi Wu, Qishan Zhu, Rujun Tang, Jia Yu, Le He, Geoffrey A. Ozin, Xiaohong Zhang from Wiley: Advanced Materials: Table of Contents. Published on Apr 18, 2019.

A new type of smart optical materials based on the nanorod crystalline colloidal array (CCA) is developed, which enables the modulation of two optical properties by the same stimulus. An unusual monoclinic crystal structure is formed in the CCA. This work will provide a new smart optical platform with interesting implications for a variety of purposes. Abstract Stimuli‐responsive smart optical materials hold great promise for applications in active optics, display, sensing, energy conversion, military camouflage, and artificial intelligence. However, their applications are greatly restricted by the difficulty of tuning different optical properties within the same material, especially by a single stimulus. Here, magnetic modulations of multiple optical properties are demonstrated in a crystalline colloidal array (CCA) of magnetic nanorods. Small‐angle X‐ray scattering studies reveal that these nanorods form an unusual monoclinic crystal in concentrated suspensions. The CCA exhibits optical anisotropy in the form of a photonic bandgap and birefringence, thus enabling magnetic tuning of the structural color and transmittance at a rate of 50 Hz. As a proof‐of‐concept, it is further demonstrated that the fabrication of a multifunctional device for display, anticounterfeiting, and smart‐window applications based on this multiple magneto‐optical effect. The study not only provides a new model system for understanding colloidal assembly, but also opens up opportunities for new applications of smart optical materials for various purposes.

A Liquid‐Metal–Elastomer Nanocomposite for Stretchable Dielectric Materials

By Chengfeng Pan, Eric J. Markvicka, Mohammad H. Malakooti, Jiajun Yan, Leiming Hu, Krzysztof Matyjaszewski, Carmel Majidi from Wiley: Advanced Materials: Table of Contents. Published on Apr 18, 2019.

A liquid‐metal (LM)–elastomer nanocomposite is presented as a stretchable dielectric material. This material's architecture shows a unique combination of enhanced electric permittivity, controlled dielectric breakdown strength, and rubber‐like mechanical properties. These properties enable LM–elastomer nanocomposites to have potentially transformative impact on soft materials actuation, energy storage, and energy harvesting. Abstract Stretchable high‐dielectric‐constant materials are crucial for electronic applications in emerging domains such as wearable computing and soft robotics. While previous efforts have shown promising materials architectures in the form of dielectric nano‐/microinclusions embedded in stretchable matrices, the limited mechanical compliance of these materials significantly limits their practical application as soft energy‐harvesting/storage transducers and actuators. Here, a class of liquid metal (LM)–elastomer nanocomposites is presented with elastic and dielectric properties that make them uniquely suited for applications in soft‐matter engineering. In particular, the role of droplet size is examined and it is found that embedding an elastomer with a polydisperse distribution of nanoscale LM inclusions can enhance its electrical permittivity without significantly degrading its elastic compliance, stretchability, or dielectric breakdown strength. In contrast, elastomers embedded with microscale droplets exhibit similar improvements in permittivity but a dramatic reduction in breakdown strength. The unique enabling properties and practicality of LM–elastomer nanocomposites for use in soft machines and electronics is demonstrated through enhancements in performance of a dielectric elastomer actuator and energy‐harvesting transducer.

Graphitic Carbon Nitride (g‐C3N4)‐Derived N‐Rich Graphene with Tuneable Interlayer Distance as a High‐Rate Anode for Sodium‐Ion Batteries

By Jinlong Liu, Yaqian Zhang, Lei Zhang, Fangxi Xie, Anthony Vasileff, Shi‐Zhang Qiao from Wiley: Advanced Materials: Table of Contents. Published on Apr 18, 2019.

Well‐controlled N‐doped few‐layer graphene (N‐FLG) with tunable interlayer structure, nitrogen content, and nitrogen configuration, is realized through the pyrolysis of g‐C3N4 under zinc catalysis and appropriate temperature. The optimal N‐FLG‐800 features significantly enlarged interplanar spacing and high nitrogen content with pyridinic and pyrrolic configurations, resulting in superior Na+ storage performance and ultrahigh rate capability. Abstract Heteroatom‐doped carbon materials with expanded interlayer distance have been widely studied as anodes for sodium‐ion batteries (SIBs). However, it remains unexplored to further enlarge the interlayer spacing and reveal the influence of heteroatom doping on carbon nanostructures for developing more efficient SIB anode materials. Here, a series of N‐rich few‐layer graphene (N‐FLG) with tuneable interlayer distance ranging from 0.45 to 0.51 nm is successfully synthesized by annealing graphitic carbon nitride (g‐C3N4) under zinc catalysis and selected temperature (T = 700, 800, and 900 °C). More significantly, the correlation between N dopants and interlayer distance of resultant N‐FLG‐T highlights the effect of pyrrolic N on the enlargement of graphene interlayer spacing, due to its stronger electrostatic repulsion. As a consequence, N‐FLG‐800 achieves the optimal properties in terms of interlayer spacing, nitrogen configuration and electronic conductivity. When used as an anode for SIBs, N‐FLG‐800 shows remarkable Na+ storage performance with ultrahigh rate capability (56.6 mAh g−1 at 40 A g−1) and excellent long‐term stability (211.3 mAh g−1 at 0.5 A g−1 after 2000 cycles), demonstrating the effectiveness of material design.

Biocompatible SuFEx Click Chemistry: Thionyl Tetrafluoride (SOF4) Derived Connective Hubs For Bioconjugation to DNA and Proteins

By Feng Liu, Hua Wang, Suhua Li, Grant A. L. Bare, Xuemin Chen, Chu Wang, John E Moses, Peng Wu, K. Barry Sharpless from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 18, 2019.

We report here the development of a suite of biocompatible SuFEx transformations from the SOF4‐derived iminosulfur oxydifluoride‐hub in aqueous buffer conditions. Thes biocompatible SuFEx reactions of iminosulfur oxydifluorides (R‐N=SOF2) with primary amines give sulfamides (8 examples, up to 98%), while the reaction with secondary amines furnish sulfuramidimidoyl fluoride products (8 examples, up to 97%). Likewise, under mild buffered conditions, phenols react with the iminosulfur oxydifluorides (Ar‐N=SOF2) to produce sulfurofluoridoimidates (13 examples, up to 99%), which can themselves be further modified by nucleophiles. These transformations open the potential for asymmetric and trisubstituted linkages projecting from the sulfur(VI) center, including versatile S‐N and S‐O connectivity (9 examples, up to 94%). Finally, the SuFEx bioconjugation of iminosulfur oxydifluorides to amine‐tagged single‐stranded DNA and to BSA protein demonstrate the potential of SOF4 derived SuFEx click chemistry in biological applications.

Transition‐Metal Free Deconstructive Lactamization of Piperidines

By Fernando Sartillo-Piscil, Julio Romero-Ibañez, Silvano Cruz.Gregorio, Jacinto Sandoval-Lira, Julio M Hernández-Pérez, Leticia Quintero from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 18, 2019.

One of the major synthetic challenges in organic synthesis is the activation or deconstructive functionalization of unreactive C(sp3)−C(sp3) bonds. This requires using transition or precious metal catalysts. However, we present here a deconstructive lactamization of piperidines without using transition metal catalysts. To this end, we use 3‐alkoxyamino‐2‐piperidones, which were prepared from piperidines through a dual C(sp3)−H oxidation, as transitory substrates. Experimental and theoretical studies confirm that this unprecedent lactamization occurs in a tandem manner involving an oxidative deamination of 3‐alkoxyamino‐2‐piperidones to 3‐keto‐2‐piperidones, followed by a regioselective Baeyer‐Villiger oxidation to N‐carboxyanhydride intermediates, which finally undergo a spontaneous and concerted decarboxylative intramolecular translactamization.

Cobalt‐Catalyzed Allylic Alkylation Enabled by Organophotoredox Catalysis

By Koji Takizawa, Tomoyuki Sekino, Shunta Sato, Tatsuhiko Yoshino, Masahiro Kojima, Shigeki Matsunaga from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 18, 2019.

Co‐catalyzed allylic substitution reactions have long received little attention arguably because no characteristic advantage of Co catalysis over Rh or Ir catalysis was ever known. Here we describe a general and regioselective Co‐catalyzed allylic alkylation using an in situ catalyst activation by organophotoredox catalysis. This noble‐metal‐free catalytic system exhibited unprecedentedly high reactivity and regioselectivity for the allylation with an allyl sulfone, for the first time representing a unique synthetic utility of a Co‐catalyzed method compared to the related Rh‐ or Ir‐catalyzed reactions.

Interfacial Coordinational Coupled Defect Engineering Boosted Portable Zinc‐Air Battery with Broad Work Temperature

By Li An, Bolong Huang, Yu Zhang, Rui Wang, Nan Zhang, Tengyuan Dai, Pinxian Xi, Chun-Hua Yan from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 18, 2019.

Atomic‐thick interfacial dominated bifunctional catalyst NiO/CoO transition interfacial nanowires (TINWs) with abundant coordinational defective sites display high electroactivities and durabilities in the oxygen evolution reaction (OER) and the oxygen reduction reaction (ORR). Density functional theory (DFT) calculations unravel that the excellent OER/ORR performance arises from the electron‐rich interfacial region coupled with coordinational defective sites, thus endows the fast‐redox rate with lower activation barrier for fast electron transfer. When assembled as air‐electrode, NiO/CoO TINWs delivered the high specific capacity of 842.58 mAh gZn‐1, the large energy density of 996.44 Wh kgZn‐1 with long‐time stability of more than 33 h (25 oC), and also the superior performance at low (‐10 oC) and high temperature (80 oC). Transitional interface engineering open perspectives for rational design advanced oxygen‐involved catalysts for wide temperature compatible metal‐air batteries.

Dehydrogenative Synthesis of 2,2′‐Bipyridyls through Regioselective Pyridine Dimerization

By Shuya Yamada, Takeshi Kaneda, Philip Steib, Kei Murakami, Kenichiro Itami from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 18, 2019.

Two become one: A palladium‐catalyzed dehydrogenative C2‐selective dimerization of pyridine is described. A variety of 2,2′‐bipyridyls can be prepared directly from unfunctionalized pyridine without additional pre‐halogenation or pre‐metalation steps. The reaction is applicable to a series of sterically hindered 3‐substituted pyridine derivatives and enables the concise synthesis of twisted 3,3′‐disubstituted‐2,2′‐bipyridyls, an underdeveloped class of ligands. Abstract 2,2′‐Bipyridyls have been utilized as indispensable ligands in metal‐catalyzed reactions. The most streamlined approach for the synthesis of 2,2′‐bipyridyls is the dehydrogenative dimerization of unfunctionalized pyridine. Herein, we report on the palladium‐catalyzed dehydrogenative synthesis of 2,2′‐bipyridyl derivatives. The Pd catalysis effectively works with an AgI salt as the oxidant in the presence of pivalic acid. A variety of pyridines regioselectively react at the C2‐positions. This dimerization method is applicable for challenging substrates such as sterically hindered 3‐substituted pyridines, where the pyridines regioselectively react at the C2‐position. This reaction enables the concise synthesis of twisted 3,3′‐disubstituted‐2,2′‐bipyridyls as an underdeveloped class of ligands.

Efficient and Stable CsPbI3 Solar Cells via Regulating Lattice Distortion with Surface Organic Terminal Groups

By Tianhao Wu, Yanbo Wang, Zhensheng Dai, Danyu Cui, Tao Wang, Xiangyue Meng, Enbing Bi, Xudong Yang, Liyuan Han from Wiley: Advanced Materials: Table of Contents. Published on Apr 18, 2019.

A novel strategy for achieving efficient and stable CsPbI3 solar cells via regulating lattice distortion with a surface organic terminal group (OTG) is proposed. As the steric hindrance of the OTG increases, the CsPbI3 perovskite will be more stable under ambient conditions. Consequently, the optimized CsPbI3 device shows negligible degradation of efficiency after 30 day aging in ambient air. Abstract All‐inorganic cesium lead iodide perovskites (CsPbI3) are promising wide‐bandgap materials for use in the perovskite/silicon tandem solar cells, but they easily undergo a phase transition from a cubic black phase to an orthorhombic yellow phase under ambient conditions. It is shown that this phase transition is triggered by moisture that causes distortion of the corner‐sharing octahedral framework ([PbI6]4−). Here, a novel strategy to suppress the octahedral tilting of [PbI6]4− units in cubic CsPbI3 by systematically controlling the steric hindrance of surface organic terminal groups is provided. This steric hindrance effectively prevents the lattice distortion and thus increases the energy barrier for phase transition. This mechanism is verified by X‐ray diffraction measurements and density functional theory calculations. Meanwhile, the formation of an organic capping layer can also passivate the surface electronic trap states of perovskite absorber. These modifications contribute to a stable power conversion efficiency (PCE) of 13.2% for the inverted planar perovskite solar cells (PSCs), which is the highest efficiency achieved by the inverted‐structure inorganic PSCs. More importantly, the optimized devices retained 85% of their initial PCE after aging under ambient conditions for 30 days.

Intermolecular Radical C(sp3)−H Amination under Iodine Catalysis

By Alexandra E. Bosnidou, Kilian Muñiz from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 18, 2019.

Radically new: A process for the intermolecular C−H amination of aliphatic positions is based on the combination of a catalytic amount of iodine, an iodine(III) oxidant, visible light, and sulfonamides. Under these conditions, amidyl radicals are generated that promote the selective functionalization of C−H bonds. Abstract The direct amination of aliphatic C−H bonds has remained one of the most tantalizing transformations in organic chemistry. Herein, we report on a unique catalyst system, which enables the elusive intermolecular C(sp3)−H amination. This practical synthetic strategy provides access to aminated building blocks and fosters innovative multiple C−H amination within a new approach to aminated heterocycles. The synthetic utility is demonstrated by the synthesis of four relevant pharmaceuticals.

Phenothiazine‐Based Organic Catholyte for High‐Capacity and Long‐Life Aqueous Redox Flow Batteries

By Changkun Zhang, Zhihui Niu, Sangshan Peng, Yu Ding, Leyuan Zhang, Xuelin Guo, Yu Zhao, Guihua Yu from Wiley: Advanced Materials: Table of Contents. Published on Apr 18, 2019.

A class of heteroaromatic phenothiazine derivatives is explored as catholytes for aqueous organic RFBs. The selected phenothiazine derivative possesses extremely fast redox kinetics with electron‐transfer rate constant of 0.32 cm s−1, excellent stability, and high solubility, leading to a high reversible capacity of ≈71 Ah L−1. The flow battery demonstrates a remarkable stability with no capacity decay over hundreds of cycles. Abstract Redox‐active organic materials have been considered as one of the most promising “green” candidates for aqueous redox flow batteries (RFBs) due to the natural abundance, structural diversity, and high tailorability. However, many reported organic molecules are employed in the anode, and molecules with highly reversible capacity for the cathode are limited. Here, a class of heteroaromatic phenothiazine derivatives is reported as promising positive materials for aqueous RFBs. Among these derivatives, methylene blue (MB) possesses high reversibility with extremely fast redox kinetics (electron‐transfer rate constant of 0.32 cm s−1), excellent stability in both neutral and reduced states, and high solubility in an acetic‐acid–water solvent, leading to a high reversible capacity of ≈71 Ah L−1. Symmetric RFBs based on MB electrolyte demonstrate remarkable stability with no capacity decay over 1200 cycles. Even concentrated MB catholyte (1.5 m) is still able to deliver stable capacity over hundreds of cycles in a full cell system. The impressive cell performance validates the practicability of MB for large‐scale electrical energy storage.

Inorganic Salts Induce Thermally Reversible and Anti‐Freezing Cellulose Hydrogels

By Xiong‐Fei Zhang, Xiaofeng Ma, Ting Hou, Kechun Guo, Jiayu Yin, Zhongguo Wang, Lian Shu, Ming He, Jianfeng Yao from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 18, 2019.

“Hotspot” in materials science: Anti‐freezing and thermally reversible cellulose hydrogels were fabricated in an aqueous ZnCl2/CaCl2 solution, whereby the Zn2+ ions contribute to the cellulose dissolution and the Ca2+ ions act as a gelling agent. These new cellulose‐based hydrogels may find application in flexible and wearable devices for use at temperatures as low as −70 °C. Abstract Inspired by the anti‐freezing mechanisms found in nature, ionic compounds (ZnCl2/CaCl2) are integrated into cellulose hydrogel networks to enhance the freezing resistance. In this work, cotton cellulose is dissolved by a specially designed ZnCl2/CaCl2 system, which endows the cellulose hydrogels specific properties such as excellent freeze‐tolerance, good ion conductivity, and superior thermal reversibility. Interestingly, the rate of cellulose coagulation could be promoted by the addition of extra water or glycerol. This new type of cellulose‐based hydrogel may be suitable for the construction of flexible devices used at temperature as low as −70 °C.

Design of Bistable Gold@Spin‐Crossover Core–Shell Nanoparticles Showing Large Electrical Responses for the Spin Switching

By Ramón Torres‐Cavanillas, Roger Sanchis‐Gual, Julien Dugay, Marc Coronado‐Puchau, Mónica Giménez‐Marqués, Eugenio Coronado from Wiley: Advanced Materials: Table of Contents. Published on Apr 18, 2019.

A simple protocol to prepare core–shell nanoparticles with a metallic core (gold) and an ultrathin (≈4 nm) molecular spin‐crossover (SCO) shell is presented. An electrical device based on assemblies of these gold@SCO nanoparticles displays a large change in conductance, which is associated with the spin switching near room temperature. Abstract A simple chemical protocol to prepare core–shell gold@spin‐crossover (Au@SCO) nanoparticles (NPs) based on the 1D spin‐crossover [Fe(Htrz)2(trz)](BF4) coordination polymer is reported. The synthesis relies on a two‐step approach consisting of a partial surface ligand substitution of the citrate‐stabilized Au NPs followed by the controlled growth of a very thin layer of the SCO polymer. As a result, colloidally stable core@shell spherical NPs with a Au core of ca. 12 nm and a thin SCO shell 4 nm thick, are obtained, exhibiting a narrow distribution in sizes. Differential scanning calorimetry proves that a cooperative spin transition in the range 340–360 K is maintained in these Au@SCO NPs, in full agreement with the values reported for pristine 4 nm SCO NPs. Temperature‐dependent charge‐transport measurements of an electrical device based on assemblies of these Au@SCO NPs also support this spin transition. Thus, a large change in conductance upon spin state switching, as compared with other memory devices based on the pristine SCO NPs, is detected. This results in a large improvement in the sensitivity of the device to the spin transition, with values for the ON/OFF ratio which are an order of magnitude better than the best ones obtained in previous SCO devices.

Anti‐Ambipolar Transport with Large Electrical Modulation in 2D Heterostructured Devices

By Ruiqing Cheng, Lei Yin, Feng Wang, Zhenxing Wang, Junjun Wang, Yao Wen, Wenhao Huang, Marshet Getaye Sendeku, Liping Feng, Yufang Liu, Jun He from Wiley: Advanced Materials: Table of Contents. Published on Apr 18, 2019.

A novel van der Waals heterostructured device with very large electrical modulation and nonvolatile properties is demonstrated. The corresponding anti‐ambipolar transport and negative transconductance feature can be well controlled and be applied in logic circuit including Schmitt triggers and multivalue output, providing a new direction for designing future electronics devices. Abstract Van der Waals materials and their heterostructures provide a versatile platform to explore new device architectures and functionalities beyond conventional semiconductors. Of particular interest is anti‐ambipolar behavior, which holds potentials for various digital electronic applications. However, most of the previously conducted studies are focused on hetero‐ or homo‐ p–n junctions, which suffer from a weak electrical modulation. Here, the anti‐ambipolar transport behavior and negative transconductance of MoTe2 transistors are reported using a graphene/h‐BN floating‐gate structure to dynamically modulate the conduction polarity. Due to the asymmetric electrical field regulating effect on the recombination and diffusion currents, the anti‐ambipolar transport and negative transconductance feature can be systematically controlled. Consequently, the device shows an unprecedented peak resistance modulation factor (≈5 × 103), and effective photoexcitation modulation with distinct threshold voltage shift and large photo on/off ratio (≈104). Utilizing this large modulation effect, the voltage‐transfer characteristics of an inverter circuit variant are further studied and its applications in Schmitt triggers and multivalue output are further explored. These properties, in addition to their proven nonvolatile storage, suggest that such 2D heterostructured devices display promising perspectives toward future logic applications.

From Alkyl Halides to Ketones: Nickel‐Catalyzed Reductive Carbonylation Utilizing Ethyl Chloroformate as the Carbonyl Source

By Renyi Shi, Xile Hu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 18, 2019.

Inside source: A nickel‐catalyzed three‐component coupling of alkyl halides and ethyl chloroformate can be used to prepare a wide range of unsymmetrical and symmetrical dialkyl ketones under mild reaction conditions. Ethyl chloroformate serves as a safe CO source relative to either toxic CO or metal carbonyl reagents used by other methods. Abstract Ketones are an important class of molecules in synthetic and medicinal chemistry. Rapid and modular synthesis of ketones remains in high demand. Described here is a nickel‐catalyzed three‐component reductive carbonylation method for the synthesis of dialkyl ketones. A wide range of both symmetric and asymmetric dialkyl ketones can be accessed from alkyl halides and a safe CO source, ethyl chloroformate. The approach offers complementary substrate scope to existing carbonylation methods while avoiding the use of either toxic CO or metal carbonyl reagents.

Enhanced Photoelectrochemical Water Splitting through Bismuth Vanadate with a Photon Upconversion Luminescent Reflector

By Dongho Choi, Seong Kyung Nam, Kiwon Kim, Jun Hyuk Moon from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 18, 2019.

A luminescent back reflector (LBR) capable of photon upconversion (UC) is used to improve the light harvesting of Mo:BiVO4 photoelectrodes. The LBR converts the wavelengths of 600–650 nm and 350–450 nm to a wavelength that can be absorbed by a Mo:BiVO4 photoelectrode. Mo:BiVO4/LBR exhibits a photocurrent density of 5.25 mA cm−2 at 1.23 V versus the reversible hydrogen electrode. Abstract As the performance of photoanodes for solar water splitting steadily improves, the extension of the absorption wavelength in the photoanodes is highly necessary to substantially improve the water splitting. We use a luminescent back reflector (LBR) capable of photon upconversion (UC) to improve the light harvesting capabilities of Mo:BiVO4 photoelectrodes. The LBR is prepared by dispersing the organic dye pair meso‐tetraphenyltetrabenzoporphine palladium and perylene capable of triplet–triplet annhilation‐based UC in a polymer film. The LBR converts the wavelengths of 600–650 nm corresponding to the sub‐band gap of Mo:BiVO4 and the wavelengths of 350–450 nm that are not sufficiently absorbed in Mo:BiVO4 to a wavelength that can be absorbed by a Mo:BiVO4 photoelectrode. The LBR improves the water splitting reaction of Mo:BiVO4 photoelectrodes by 17 %, and consequently, the Mo:BiVO4/LBR exhibits a photocurrent density of 5.25 mA cm−2 at 1.23 V versus the reversible hydrogen electrode. The Mo:BiVO4/LBR exhibits hydrogen/oxygen evolution corresponding to the increased photocurrent density and long‐term operational stability for the water splitting reaction.

Enantioselective Synthesis of Biaryl Atropisomers by Palladium‐Catalyzed C−H Olefination using Chiral Spiro Phosphoric Acid Ligands

By Jun Luo, Tao Zhang, Lei Wang, Gang Liao, Qi‐Jun Yao, Yong‐Jie Wu, Bei‐Bei Zhan, Yu Lan, Xu‐Feng Lin, Bing‐Feng Shi from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 18, 2019.

Axially chiral biaryl derivatives can be prepared by Pd(II)‐catalyzed atroposelective C−H activation with the aid of a new chiral spiro phosphoric acid ligand. In their Communication (DOI: 10.1002/anie.201902126) Y. Lan, X.‐F. Lin, B.‐F. Shi, and co‐workers show that using the new ligand allows a broad range of axially chiral quinoline derivatives to be synthesized in good yields with excellent enantioselectivities (up to 98 % ee).

An Auto‐Switchable Dual‐Mode Seawater Energy Extraction System Enabled by Metal–Organic Frameworks

By Wei Zhang, Wenqian Chen, Xiaoli Zhao, Qi Dang, Yucen Li, Tianyu Shen, Fengchang Wu, Liang Tang, Hu Jiang, Ming Hu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 18, 2019.

Switching for sea energy: An auto‐switchable dual‐mode seawater energy extraction system is presented that could provide both high energy density and power density by choosing different solutes in seawater as electron acceptors. This device had a theoretical energy density of 3960 Wh kg−1, and a high practical power density of 100±4 mW cm−2. Abstract Harvesting energy directly in oceans by electrochemical devices is essential for driving underwater appliances such as underwater vehicles or detectors. Owing to the extreme undersea environment, it is important but difficult to use the devices with both a high energy density and power density simultaneously. Inspired by marine organisms that have switchable energy extraction modes (aerobic respiration for long‐term living or anaerobic respiration to provide instantaneously high output power for fast movement), an auto‐switchable dual‐mode seawater energy extraction system is presented to provide high energy density and power density both by initiatively choosing different solutes in seawater as electron acceptors. With assistance from metal–organic frameworks, this device had a theoretical energy density of 3960 Wh kg−1, and a high practical power density of 100±4 mW cm−2 with exceptional stability and low cost, making practical applications in seawater to be possible.

Generation and EPR Spectroscopy of the First Silenyl Radicals, R2C=Si.−R: Experiment and Theory

By Daniel Pinchuk, Yosi Kratish, Jomon Mathew, Lieby Zborovsky, Dmitry Bravo‐Zhivotovskii, Boris Tumanskii, Yitzhak Apeloig from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 18, 2019.

Two persistent silenyl radicals (R2C=Si.−R; t1/2≈30 min) were generated from lithium‐ and mercury‐substituted silenes and characterized by EPR spectroscopy and density functional theory (DFT) calculations. According to the hyperfine coupling constants and the calculations, silenyl radicals have a strongly bent structure (∡Si−Si=C=140.7°) whereas R2C=C.−R is nearly linear. The spin is mostly located in a Si(sp) orbital. Abstract The first two persistent silenyl radicals (R2C=Si.−R), with a half‐life (t1/2) of about 30 min, were generated and characterized by electron paramagnetic resonance (EPR) spectroscopy. The large hyperfine coupling constants (hfccs) (a(29Siα)=137.5–148.0 G) indicate that the unpaired electron has substantial s character. DFT calculations, which are in good agreement with the experimentally observed hfccs, predict a strongly bent structure (∡C=Si−R=134.7–140.7°). In contrast, the analogous vinyl radical, R2C=C.−R (t1/2≈3 h), exhibits a small hfcc (a(13Cα)=26.6 G) and has a nearly linear geometry (∡C=C−R=168.7°).

Iridium‐Based Cubic Nanocages with 1.1‐nm‐Thick Walls: A Highly Efficient and Durable Electrocatalyst for Water Oxidation in an Acidic Medium

By Jiawei Zhu, Zitao Chen, Minghao Xie, Zhiheng Lyu, Miaofang Chi, Manos Mavrikakis, Wanqin Jin, Younan Xia from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 18, 2019.

Iridium‐based cubic nanocages are fabricated with a composition of Ir44Pd10, together with well‐defined {100} facets, and porous walls of only 1.1 nm in thickness, as reported by Y. Xia and co‐workers in their Communication (DOI: 10.1002/anie.201901732). When applied as a catalyst toward water oxidation, the nanocages show substantially enhanced activity and durability, outperforming most of the electrocatalysts reported for use in acidic media.

Screening Therapeutic Agents Specific to Breast Cancer Stem Cells Using a Microfluidic Single‐Cell Clone‐Forming Inhibition Assay

By Dongguo Lin, Peiwen Li, Jin Feng, Zhun Lin, Xiao Chen, Na Yang, Lihui Wang, Dayu Liu from Wiley: Small: Table of Contents. Published on Apr 18, 2019.

A microfluidic single‐cell assay for screening therapeutic agents specific to cancer stem cells provides new tools for individualized cancer therapy. Abstract Screens of cancer stem cells (CSCs)‐specific agents present significant challenges to conventional cell assays due to the difficulty in preparing CSCs ready for drug testing. To overcome this limitation, developed is a microfluidic single‐cell assay for screening breast cancer stem cell–specific agents. This assay takes advantage of the single‐cell clone‐forming capability of CSCs, which can be specifically inhibited by CSC‐targeting agents. The single‐cell assay is performed on a microfluidic chip with an array of 3840 cell‐capturing units; the single‐cell arrays are easily formed by flowing a cell suspension into the microchip. Achieved is a single cell‐capture rate of ≈60% thus allowing more than 2000 single cells to be analyzed in a single test. Over long‐term suspension culture, only a minority of cells survive and form tumorspheres. The clone‐formation rate of MCF‐7, MDA‐MB‐231, and T47D cells is 1.67%, 5.78%, and 5.24%, respectively. The clone‐forming inhibition assay is conducted by exposing the single‐cell arrays to a set of anticancer agents. The CSC‐targeting agents show complete inhibition of single‐cell clone formation while the nontargeting ones show incomplete inhibition effects. The resulting microfluidic single‐cell assay with the potential to screen CSC‐specific agents with high efficiency provides new tools for individualized tumor therapy.

How Many Phosphoric Acid Units Are Required to Ensure Uniform Occlusion of Sterically‐Stabilized Nanoparticles within Calcite?

By Marcel Douverne, Yin Ning, Aikaterini Tatani, Fiona C. Meldrum, Steven P. Armes from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 18, 2019.

Polymerization‐induced self‐assembly (PISA) mediated by reversible addition‐fragmentation chain transfer (RAFT) polymerization offers a platform technology for the efficient and versatile synthesis of well‐defined sterically‐stabilized block copolymer nanoparticles. Herein we synthesize a series of such nanoparticles with tunable anionic charge density within the stabilizer chains, which are prepared via statistical copolymerization of anionic 2‐(phosphonooxy)ethyl methacrylate (P) with non‐ionic glycerol monomethacrylate (G). Systematic variation of the P/G molar ratio enables elucidation of the minimum number of phosphate groups per copolymer chain required to promote nanoparticle occlusion within a model inorganic crystal (calcite). Moreover, the extent of nanoparticle occlusion correlates strongly with the phosphate content of the steric stabilizer chains. This study is the first to examine the effect of systemically varying the anionic charge density of nanoparticles on their occlusion efficiency and sheds new light on maximizing guest nanoparticles loading within calcite host crystals.

Activity of Atomically Precise Titania Nanoparticles in CO Oxidation

By Yan-Xia Zhao, Meng-Meng Wang, Yan Zhang, Xun-Lei Ding, Sheng-Gui He from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 18, 2019.

Understanding the property evolution of atomically precise nanoparticles along the continuous change of size atom by atom is critical for selecting potential candidates to assemble nanomaterials with desirable functionality, but it is very experimentally challenging especially for the systems having mixtures of elements such as metal oxides. In this work, the capability to oxidize carbon monoxide has been experimentally measured for titania nanocluster anions of (TiO2)nOm− (−3 ≤ m ≤ 3) across a rather broad size range in gas phase. The stoichiometric (TiO2)nO− exhibits superior oxidative activity over other clusters of (TiO2)nOm− (m ≠ 1) even when the cluster dimensions upsize to n = 60, indicating that each atom still counts in the chemical behaviour of titania nanoparticles composed of ~180 atoms. The fasnating result not only offers a promising building block of TinO2n+1 for devising new nanoscale titania materials with desirable oxidative activity, but also provides a compelling molecular‐level evidence for Mars‐van Krevelen mechanism of CO oxidation over titania supports.

Fri 10 May 16:00: On the Consistency of Supervised Learning with Missing Values

From All Talks (aka the CURE list). Published on Apr 18, 2019.

On the Consistency of Supervised Learning with Missing Values

In many application settings, the data have missing features which make data analysis challenging. An abundant literature addresses missing data in an inferential framework: estimating parameters and their variance from incomplete tables. Here, we consider supervised-learning settings: predicting a target when missing values appear in both training and testing data. We show the consistency of two approaches in prediction. A striking result is that the widely-used method of imputing with the mean prior to learning is consistent when missing values are not informative. This contrasts with inferential settings where mean imputation is pointed at for distorting the distribution of the data. That such a simple approach can be consistent is important in practice. We analyze further decision trees. These can naturally tackle empirical risk minimization with missing values, due to their ability to handle the half-discrete nature of incomplete variables. After comparing theoretically and empirically different missing values strategies in trees, we recommend using the “missing incorporated in attribute” method as it can handle both non-informative and informative missing values.

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Gold Difluorocarbenoid Complexes: Spectroscopic and Chemical Profiling

By Alois Fürstner, Alexander G Tskhovrebov, Julia B. Lingnau from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 18, 2019.

Gold carbenes of the general type [LAu=CR2]+ are sufficiently long‐lived for spectroscopic inspection only if the substituents R compensate for the largely missing stabilization of the carbene center by the [LAu]+ fragment. pi‐Donation by two fluorine substituents (R = F) is insufficient; rather, difluorocarbene complexes are so deprived in electron density that they sequester even weakly coordinating anions such as triflate or triflimide. This particular bonding situation translates into unmistakable carbenium ion chemistry upon reaction with stilbene as a model substrate.

Fri 17 May 13:00: Toward General Relativistic Cosmological N-body Simulations

From All Talks (aka the CURE list). Published on Apr 18, 2019.

Toward General Relativistic Cosmological N-body Simulations

Abstract not available

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A Photochemical Route towards Metal Sulfide Nanosheets from Layered Metal Thiolate Complexes

By Jiahao Guo, Yitao Cao, Run Shi, Geoffrey I.N. Waterhouse, Li-Zhu Wu, Chen-Ho Tung, Tierui Zhang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 18, 2019.

Synthesizing nanomaterials with anisotropic architectures, especially two‐dimensional (2D) nanosheets (NSs), is a key focus of materials science research. Metal sulfide nanosheets (MSNSs) are typically obtained involving exfoliation of bulk metal sulfides with layered structures. The synthesis of NSs of intrinsically non‐layered metal sulfides has received relatively less attention. Herein, we demonstrate that metal alkanethiolates with lamellar structures can serve as effective scaffolds for constructing NSs. A novel photochemical step was employed to transform 2D metal thiolates into MSNSs. By this strategy the 2D nature of metal thiolate precursors were preserved in the final products, resulting in the successful synthesis of NSs of binary PbS, CdS and Cu9S5, as well as ternary wurtzite CuInS2, Cu2SnS3. Results encourage the wider utilization of photochemical strategies in the synthesis of anisotropic MSNSs.

Wed 12 Jun 16:00: The parallelism of evolution of multi-drug resistant clones

From All Talks (aka the CURE list). Published on Apr 18, 2019.

The parallelism of evolution of multi-drug resistant clones

Escherichia coli is an extremely diverse bacterial species composed of thousands of distinct lineages. Despite many of these lineages (presumably) inhabiting identical niches, and therefore undergoing identical selection pressures, only a handful of lineages have emerged as dominant, globally disseminated MDR clones. Large scale genomic analysis of these MDR clones, and contextual comparison against the background population from which they emerge, has allowed us to identify a number of key evolutionary steps in the emergence of these MDR clones, and their parallelism across a number of the most globally dominant MDR clones. Combining genomics with experimental evolution and classical molecular microbiology is allowing us to confirm these key mechanisms that underpin the evolution of successful MDR clones of E. coli

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Wed 22 May 16:00: Sickle cell anaemia: the first molecular disease

From All Talks (aka the CURE list). Published on Apr 18, 2019.

Sickle cell anaemia: the first molecular disease

Abstract not available

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Tue 07 May 13:00: Title to be confirmed

From All Talks (aka the CURE list). Published on Apr 18, 2019.

Title to be confirmed

Abstract not available

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Fri 26 Apr 16:00: Nuisance parameters

From All Talks (aka the CURE list). Published on Apr 18, 2019.

Nuisance parameters

The role of models for the purpose of developing understanding of physical, biological or sociological processes is emphasized. Realistic models for such systems are often high-dimensional, although interest typically lies in a low-dimensional parameter such as a treatment or exposure effect. There are settings in which it seems sensible to model explicitly only those aspects of direct concern, retaining a level of agnosticism over the rest of the data generating mechanism. This rather vague idea and its implications will be illustrated with specific examples.

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Cross‐peaks in simple 2D NMR experiments from chemical exchange of transverse magnetization

By Christopher Andrew Waudby, Tom Frenkiel, John Christodoulou from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 18, 2019.

Two‐dimensional correlation measurements such as COSY, NOESY, HMQC and HSQC experiments are central to small molecule and biomolecular NMR spectroscopy, and commonly form the basis of more complex experiments designed to study chemical exchange occurring during additional mixing periods. However, exchange occurring during chemical shift evolution periods can also influence the appearance of such spectra. While this is often exploited through one‐dimensional lineshape analysis (‘dynamic NMR’), the analysis of exchange across multiple chemical shift evolution periods has received less attention. Here we report that chemical exchange‐induced cross‐peaks can arise in even the simplest two‐dimensional NMR experiments. These cross‐peaks can have highly distorted phases that contain rich information about the underlying exchange process. The quantitative analysis of such peaks, from a single 2D spectrum, can provide a highly accurate characterization of underlying exchange processes.

An Integrated Approach Toward Renewable Energy Storage Using Rechargeable Ag@Ni0.67Co0.33S‐Based Hybrid Supercapacitors

By Goli Nagaraju, S. Chandra Sekhar, Bhimanaboina Ramulu, Jae Su Yu from Wiley: Small: Table of Contents. Published on Apr 18, 2019.

Hierarchical nano‐Ag@Ni0.67Co0.33S forest‐like architectures as an effective battery‐type electrode are facilely prepared and employed for hybrid supercapacitors. With the wind/solar energies, a self‐powered renewable energy system is proposed to store eco‐benign energy into hybrid supercapacitors. Abstract Self‐powered charging systems in conjunction with renewable energy conversion and storage devices have attracted promising attention in recent years. In this work, a prolific approach to design a wind/solar‐powered rechargeable high‐energy density pouch‐type hybrid supercapacitor (HSC) is proposed. The pouch‐type HSC is fabricated by engineering nature‐inspired nanosliver (nano‐Ag) decorated Ni0.67Co0.33S forest‐like nanostructures on Ni foam (nano‐Ag@NCS FNs/Ni foam) as a battery‐type electrode and porous activated carbon as a capacitive‐type electrode. Initially, the core–shell‐like NCS FNs/Ni foam is prepared via a single‐step wet‐chemical method, followed by a light‐induced growth of nano‐Ag onto it for enhancing the conductivity of the composite. Utilizing the synergistic effects of forest‐like nano‐Ag@NCS FNs/Ni foam as a composite electrode, the fabricated device shows a maximum capacitance of 1104.14 mF cm−2 at a current density of 5 mA cm−2 and it stores superior energy and power densities of 0.36 mWh cm−2 and 27.22 mW cm−2, respectively along with good cycling stability, which are higher than most of previous reports. The high‐energy storage capability of HSCs is further connected to wind fans and solar cells to harvest renewable energy. The wind/solar charged HSCs can effectively operate various electronic devices for a long time, enlightening its potency for the development of sustainable energy systems.

Real‐Time Mapping of Ultratrace Singlet Oxygen in Rat during Acute and Chronic Inflammations via a Chemiluminescent Nanosensor

By Shenghai Zhang, Hongbo Cui, Min Gu, Na Zhao, Mengqi Cheng, Jiagen Lv from Wiley: Small: Table of Contents. Published on Apr 18, 2019.

A singlet oxygen responsive chemiluminescent nanosensor is developed. This nanosensor is demonstrated specific to singlet oxygen among common reactive oxygen species with the nm level quantification capacity. Ultratrace singlet oxygen in Dark Agouti rat during acute and chronic rheumatic arthritis is first imaged, revealing the potential for investigating singlet oxygen relevant bioevents at whole‐animal level. Abstract Sensing nonradiation‐induced singlet oxygen (1O2) in whole‐animal is deemed as one of the most challenging tasks in noninvasive techniques due to the µs level lifetime of 1O2 and quenching by numerous reductants in tissues. Here a distinct chemiluminescent (CL) nanosensor (NTPE‐PH) that boasts ultrahigh concentrated CL units in one nanoparticle is reported. Taking advantage of the intramolecular energy transfer mechanism that promises high energy transfer efficiency and the aggregation‐induced emission behavior that guarantees high CL amplification, the NTPE‐PH sensor is sensitive to a nm level 1O2. Experiments demonstrate that the NTPE‐PH yields a highly selective CL response toward 1O2 among common reactive oxygen species. With proved low cytotoxicity and good animal compatibility, real‐time mapping of ultratrace 1O2 in whole‐animal during acute and chronic inflammations is first achieved. It is anticipated that the NTPE‐PH sensor can be a useful tool for monitoring 1O2 variation during immune response and pathological processes corresponding to different stimuli, even with drug treatment included.

Biomimetic Design of Hollow Flower‐Like g‐C3N4@PDA Organic Framework Nanospheres for Realizing an Efficient Photoreactivity

By Haihui Wang, Qianying Lin, Litian Yin, Yuling Yang, Yuan Qiu, Chunhua Lu, Huanghao Yang from Wiley: Small: Table of Contents. Published on Apr 18, 2019.

Bioinspired hollow flower‐like g‐C3N4@PDA organic framework nanospheres are successfully synthesized via a mild and green method. This strategy opens up a new avenue for exploiting more potential hollow organic framework nanospheres. Significantly, the g‐C3N4@PDA provides a paradigm of a highly efficient photo‐catalyst that can be used as nano‐medicine toward cancer therapy. Abstract Organic framework polymers have attracted much interest due to the enormous potential design space offered by the atomically precise spatial assembly of organic molecular building blocks. The morphology control of organic frameworks is a complex issue that hinders the development of organic frameworks for practical applications. Biomimetic self‐assembly is a promising approach for designing and fabricating multiple‐functional nanoarchitectures. A bioinspired hollow flower‐like organic framework nanosphere heterostructure comprised of carbon nitride and polydopamine (g‐C3N4@PDA) is successfully synthesized via a mild and green method. This heterostructure can effectively avoid the agglomeration of nanosheets to better access the hollow nanospheres with high open‐up specific surface area. The electron delocalization of g‐C3N4 and PDA under visible light can largely promote photoelectron transfer and enhance the photocatalytic activity of the g‐C3N4@PDA. Furthermore, the g‐C3N4@PDA can effectively enhance the generation of reactive oxygen species under irradiation, which can lead to cell apoptosis and enhance the performance for cancer therapy. Therefore, the as‐prepared g‐C3N4@PDA provides a paradigm of highly efficient photocatalyst that can be used as nanomedicine toward cancer therapy. This study could open up a new avenue for exploiting more other potential hollow nanosphere organic frameworks.

A Double‐Buffering Strategy to Boost the Lithium Storage of Botryoid MnOx/C Anodes

By Cheng Yang, Yu Yao, Yuebin Lian, Yujie Chen, Rahim Shah, Xiaohui Zhao, Muzi Chen, Yang Peng, Zhao Deng from Wiley: Small: Table of Contents. Published on Apr 18, 2019.

Botryoid binder‐free lithium ion battery anodes composed of yolk–shell MnOx nanoparticles confined in nitrogen‐doped carbonized nanofibers are fabricated by electrospinning manganese‐based metal organic frameworks. This hierarchical architecture provides double buffering for cyclic volume fluctuation during charge/discharge, ensuring the structural stability and integrity of the composite electrode toward prolonged lithium storage performance. Abstract Transition metal oxides (TMOs) are regarded as promising candidates for anodes of lithium ion batteries, but their applications have been severely hindered by poor material conductivity and lithiated volume expansion. As a potential solution, herein is presented a facile approach, by electrospinning a manganese‐based metal organic framework (Mn‐MOF), to fabricate yolk–shell MnOx nanostructures within carbon nanofibers in a botryoid morphology. While the yolk–shell structure accomodates the lithiated volume expansion of MnOx, the fiber confinement ensures the structural integrity during charge/discharge, achieving a so‐called double‐buffering for cyclic volume fluctuation. The formation mechanism of the yolk–shell structure is well elucidated through comprehensive instrumental characterizations and cogitative control experiments, following a combined Oswald ripening and Kirkendall process. Outstanding electrochemical performances are demonstrated with prolonged stability over 1000 cycles, boosted by the double‐buffering design, as well as the “breathing” effect of lithiation/delithiation witnessed by ex situ imaging. Both the fabrication methodology and electrochemical understandings gained here for nanostructured MnOx can also be extended to other TMOs toward their ultimate implementation in high‐performance lithium ion batteries (LIBs).

Non‐Magnetic Injectable Implant for Magnetic Field‐Driven Thermochemotherapy and Dual Stimuli‐Responsive Drug Delivery: Transformable Liquid Metal Hybrid Platform for Cancer Theranostics

By Dan Wang, Wensheng Xie, Qin Gao, Hao Yan, Junxin Zhang, Jingsong Lu, BorShuang Liaw, Zhenhu Guo, Fei Gao, Lan Yin, Guifeng Zhang, Lingyun Zhao from Wiley: Small: Table of Contents. Published on Apr 18, 2019.

A magnetic field‐driven transformable liquid metal (LM) hybrid platform incorporating doxorubicin (DOX)‐loaded mesoporous silica within PEGylated LM is fabricated. The as‐prepared LM hybrid capable of pH/AFM dual stimuli‐responsive drug release and magnetic thermochemotherapy can be promising as smart theranostic agents for non‐magnetic cancer multimodality treatment and CT scan. Abstract Transformable liquid metal (LM)‐based materials have attracted considerable research interest in biomedicine. However, the potential biomedical applications of LMs have not yet been fully explored. Herein, for the first trial, the inductive heating property of gallium–indium eutectic alloy (EGaIn) under alterative magnetic field is systematically investigated. By virtue of its inherent metallic nature, LM possesses excellent magnetic heating property as compared to the conventional magnetite nanoparticles, therefore enabling its unique application as non‐magnetic agents in magnetic hyperthermia. Moreover, the extremely high surface tension of LM could be dramatically lowered by a rather facile PEGylation approach, making LM an ideal carrier for other theranostic cargos. By incorporating doxorubicin (DOX)‐loaded mesoporous silica (DOX‐MS) within PEGylated LM, a magnetic field‐driven transformable LM hybrid platform capable of pH/AFM dual stimuli‐responsive drug release and magnetic thermochemotherapy are successfully fabricated. The potential application for breast cancer treatment is demonstrated. Furthermore, the large X‐ray attenuation ability of LM endows the hybrid with the promising ability for CT imaging. This work explores a new biomedical use of LM and a promising cancer treatment protocol based on LM hybrid for magnetic hyperthermia combined with dual stimuli‐responsive chemotherapy and CT imaging.

Environmentally‐Friendly Exfoliate and Active Site Self‐Assembly: Thin 2D/2D Heterostructure Amorphous Nickel–Iron Alloy on 2D Materials for Efficient Oxygen Evolution Reaction

By Yuanzhe Wang, Yanyan Zhou, Minze Han, Yaokai Xi, Huanhuan You, Xianfeng Hao, Zhiping Li, Junshuang Zhou, Dandan Song, Dong Wang, Faming Gao from Wiley: Small: Table of Contents. Published on Apr 18, 2019.

This study emphasizes a viable idea to probe efficient electrocatalysts by means of the synergistic effect environmentally‐friendly exfoliate in aqueous solution and active site self‐assembly on the inert base of two‐dimensional (2D) materials, which forms a unique thin 2D/2D heterostructure in‐suit (NiFe/MoS2, NiFe/Graphene, NiFe/Ti3C2 Mxene). Abstract A class of 2D layered materials exhibits substantial potential for high‐performance electrocatalysts due to high specific surface area, tunable electronic properties, and open 2D channels for fast ion transport. However, liquid‐phase exfoliation always utilizes organic solvents that are harmful to the environment, and the active sites are limited to edge sites. Here, an environmentally friendly exfoliator in aqueous solution is presented without utilizing any toxic or hazardous substance and active site self‐assembly on the inert base of 2D materials. Benefiting from thin 2D/2D heterostructure and strong interfacial coupling, the resultant highly disordered amorphous NiFe/2D materials (Ti3C2 MXene, graphene and MoS2) thin nanosheets exhibit extraordinary electrocatalytic performance toward oxygen evolution reaction (OER) in alkaline media. DFT results further verify the experimental results. The study emphasizes a viable idea to probe efficient electrocatalysts by means of the synergistic effect of environmentally friendly exfoliator in aqueous solution and active site self‐assembly on the inert base of 2D materials which forms the unique thin 2D/2D heterostructure in‐suit. This new type of heterostructure opens up a novel avenue for the rational design of highly efficient 2D materials for electrocatalysis.

3D Fabrication of Fully Iron Magnetic Microrobots

By Carlos C. J. Alcântara, Sangwon Kim, Sunkey Lee, Bumjin Jang, Prakash Thakolkaran, Jin‐Young Kim, Hongsoo Choi, Bradley J. Nelson, Salvador Pané from Wiley: Small: Table of Contents. Published on Apr 18, 2019.

Biocompatible and degradable Fe microrobots with enhanced magnetic volume are fabricated by 3D template‐assisted deposition. Microhelices are able to execute 3D motion in viscous fluids and outperform metal‐coated polymer structures in upstream motion measurements inside microfluidic channels. Furthermore, microrollers are able to move at 500 µm s−1, about 20 body lengths per second, under low intensity magnetic fields. Abstract Biocompatibility and high responsiveness to magnetic fields are fundamental requisites to translate magnetic small‐scale robots into clinical applications. The magnetic element iron exhibits the highest saturation magnetization and magnetic susceptibility while exhibiting excellent biocompatibility characteristics. Here, a process to reliably fabricate iron microrobots by means of template‐assisted electrodeposition in 3D‐printed micromolds is presented. The 3D molds are fabricated using a modified two‐photon absorption configuration, which overcomes previous limitations such as the use of transparent substrates, low writing speeds, and limited depth of field. By optimizing the geometrical parameters of the 3D molds, metallic structures with complex features can be fabricated. Fe microrollers and microswimmers are realized that demonstrate motion at ≈20 body lengths per second, perform 3D motion in viscous environments, and overcome higher flow velocities than those of “conventional 3D printed helical microswimmers.” The cytotoxicity of these microrobots is assessed by culturing them with human colorectal cancer (HCT116) cells for four days, demonstrating their good biocompatibility characteristics. Finally, preliminary results regarding the degradation of iron structures in simulated gastric acid liquid are provided.

Uncovering the Mechanism Behind the Improved Stability of 2D Organic–Inorganic Hybrid Perovskites

By Zhiming Shi, Zhen Cao, Xiaojuan Sun, Yuping Jia, Dabing Li, Luigi Cavallo, Udo Schwingenschlögl from Wiley: Small: Table of Contents. Published on Apr 18, 2019.

2D organic–inorganic hybrid perovskites (OIHPs) may resolve the stability problem of bulk OIHPs. Two processes are identified to play a critical role: First, the 2D structure supports additional distortions that enhance the intrinsic structural stability. Second, the surface terminations of 2D OIHPs suppress degradation effects due to humidity. Building on this, 2D OIHPs are designed with optimal stability and favorable electronic properties. Abstract 2D organic–inorganic hybrid perovskites (OIHPs) may resolve the stability problem of bulk OIHPs. First‐principles calculations are employed to investigate the mechanism behind their favorable material properties. Two processes are identified to play a critical role: First, the 2D structure supports additional distortions that enhance the intrinsic structural stability. Second, the surface terminations of 2D OIHPs suppress degradation effects due to humidity. Having uncovered the stabilization mechanism, 2D OIHPs are designed with optimal stability and favorable electronic properties.

Bifacial Contact Junction Engineering for High‐Performance Perovskite Solar Cells with Efficiency Exceeding 21%

By Wu‐Qiang Wu, Jin‐Feng Liao, Yong Jiang, Lianzhou Wang, Dai‐Bin Kuang from Wiley: Small: Table of Contents. Published on Apr 18, 2019.

A 1D closely packed and high aspect ratio metal oxide nanowire‐based thin film is demonstrated to achieve favorable bifacial contact junction engineering for large‐area perovskite solar cells with efficiency exceeding 21% owing to the facilitated electron extraction, effective hole blocking, and suppressed charge recombination. Abstract Ordered 1D metal oxide structure is desirable in thin film solar cells owing to its excellent charge collection capability. However, the electron transfer in 1D electron transporting layer (ETL)‐based devices is still limited to a submicrometer‐long pathway that is vertical to the substrate. Here, an innovative closely packed rutile TiO2 nanowire (CRTNW) network parallel to the facet of fluorine‐doped tin oxide (FTO) substrate is reported, which can serve as a 1D nanoscale electron transport pathway for efficient perovskite solar cells (PSCs). The PSC constructed using newly prepared CRTNW ETL achieves an impressive power conversion efficiency of 21.10%, which can be attributed to the facilitated electron extraction induced by the favorable junctions formed at FTO/ETL and ETL/perovskite interfaces and also the suppressed charge recombination originating from improved perovskite morphology with large grains, flat surface, and good surface coverage. The bifacial contact junctions engineering also enables large‐area device fabrication. The PSC with 1 cm2 aperture yields an efficiency of 19.50% under one sun illumination. This work highlights the significance of controlling the orientation and packing density of the ordered 1D oxide nanostructured thin films for highly efficient optoelectronic devices in a large‐scale manner.

Functionalized Carbon Dots on Graphene as Outstanding Non‐Metal Bifunctional Oxygen Electrocatalyst

By Juhun Shin, Jian Guo, Tingting Zhao, Zhengxiao Guo from Wiley: Small: Table of Contents. Published on Apr 18, 2019.

Heteroatom‐doped carbon dots embedded on porous graphene provide enriched active sites for bifunctional oxygen electrocatalysis. Controlling the size and functional groups of carbon, performances are comparable to noble‐metal‐containing species with good stability. This appoints the utilization of a new class of non‐metal electrocatalysts. Abstract Carbon‐based bifunctional electrocatalysts for both oxygen reduction and evolution reactions are potentially cost‐effective to replace noble metals in energy devices such as fuel cells, metal–air batteries, and photoelectrochemical converters, but enrichment of active sites holds the key to efficiency. Here, graphene frameworks with heteroatom‐doped carbon dots (CDs) are developed via a hydrothermal route followed by pyrolysis. The CDs are rationally prepared with careful selection of heteroatoms, embedded on the substrate to provide enriched active sites. Structural characterizations (e.g., transmission electron microscopy and X‐ray photoelectron spectroscopy) reveal the successful addition of CDs with nitrogen and sulfur species. Especially, a heat‐treated N,S codoped sample, NS‐CD@gf_a900, exhibits the optimum oxygen electrocatalysis, even closer to noble‐metal counterparts, as a result of the effect of active sites of the CDs and the synergistic behavior of N and S. Considering the importance of size and dopants of the material, this approach not only suggests a straightforward preparation route of nanocarbons, but also appoints the utilization of a new class of non‐metal species as efficient oxygen electrocatalysts.

Pyrrolic‐Type Nitrogen‐Doped Hierarchical Macro/Mesoporous Carbon as a Bifunctional Host for High‐Performance Thick Cathodes for Lithium‐Sulfur Batteries

By Pauline Han, Sheng‐Heng Chung, Arumugam Manthiram from Wiley: Small: Table of Contents. Published on Apr 18, 2019.

Hierarchical macro/mesoporous carbons with an interconnected network are synthesized via a SiO2 template method and utilized to obtain high‐loading, high‐thickness sulfur cathodes. The carbons are then doped with pyrrolic‐type nitrogens to further impede the diffusing LiPS species. The cathodes display improved redox ability with high electrochemical utilization of sulfur. Abstract Lithium‐sulfur (Li‐S) batteries are highly considered as a next‐generation energy storage device due to their high theoretical energy density. For practical viability, reasonable active‐material loading of >4.0 mg cm−2 must be employed, at a cost to the intrinsic instability of sulfur cathodes. The incursion of lithium polysulfides (LiPS) at higher sulfur loadings results in low active material utilization and poor cell cycling capability. The use of high‐surface‐area hierarchical macro/mesoporous inverse opal (IOP) carbons to investigate the effects of pore volume and surface area on the electrochemical stability of high‐loading, high‐thickness cathodes for Li‐S batteries is presented here. The IOP carbons are additionally doped with pyrrolic‐type nitrogen groups (N‐IOP) to act as a polar polysulfide mediator and enhance the active‐material reutilization. With a high sulfur loading of 6.0 mg cm−2, the Li‐S cells assembled with IOP and N‐IOP carbons are able to attain a high specific capacity of, respectively, 1242 and 1162 mA h g−1. The N‐IOP enables the Li‐S cells to demonstrate good electrochemical performance over 300 cycles.

Gadolinium Metallofullerene‐Based Activatable Contrast Agent for Tumor Signal Amplification and Monitoring of Drug Release

By Sheng Wang, Zijian Zhou, Zhantong Wang, Yijing Liu, Orit Jacobson, Zheyu Shen, Xiao Fu, Zhi‐Yi Chen, Xiaoyuan Chen from Wiley: Small: Table of Contents. Published on Apr 18, 2019.

An activatable magnetic resonance imaging contrast agent, which is based on gadolinium metallofullerene and pH‐responsive polymer, is developed for tumor detection and drug delivery. Once the agent reaches the tumor area, the pH‐responsive polymer allows activation of magnetic resonance contrast and drug release (ON state). Therefore, the agent can be used for tumor signal‐amplification and monitoring of drug release. Abstract Activatable imaging probes are promising to achieve increased signal‐to‐noise ratio for accurate tumor diagnosis and treatment monitoring. Magnetic resonance imaging (MRI) is a noninvasive imaging technique with excellent anatomic spatial resolution and unlimited tissue penetration depth. However, most of the activatable MRI contrast agents suffer from metal ion‐associated potential long‐term toxicity, which may limit their bioapplications and clinical translation. Herein, an activatable MRI agent with efficient MRI performance and high safety is developed for drug (doxorubicin) loading and tumor signal amplification. The agent is based on pH‐responsive polymer and gadolinium metallofullerene (GMF). This GMF‐based contrast agent shows high relaxivity and low risk of gadolinium ion release. At physiological pH, both GMF and drug molecules are encapsulated into the hydrophobic core of nanoparticles formed by the pH‐responsive polymer and shielded from the aqueous environment, resulting in relatively low longitudinal relativity and slow drug release. However, in acidic tumor microenvironment, the hydrophobic‐to‐hydrophilic conversion of the pH‐responsive polymer leads to amplified MR signal and rapid drug release simultaneously. These results suggest that the prepared activatable MRI contrast agent holds great promise for tumor detection and monitoring of drug release.

Additive‐Assisted Novel Dual‐Salt Electrolyte Addresses Wide Temperature Operation of Lithium–Metal Batteries

By Xuehui Shangguan, Gaojie Xu, Zili Cui, Qinglei Wang, Xiaofan Du, Kai Chen, Suqi Huang, Guofeng Jia, Faqiang Li, Xiao Wang, Di Lu, Shanmu Dong, Guanglei Cui from Wiley: Small: Table of Contents. Published on Apr 18, 2019.

The addition of lithium difluorophosphate (LiPO2F2) additive into a novel dual‐salt electrolyte dramatically improves cycleability and rate capability of a LiNi0.5Mn0.3Co0.2O2/Li (NMC/Li) battery, ranging from −40 to 90 °C. In this novel dual‐salt electrolyte, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and self‐synthesized lithium trifluoro(perfluoro‐tert‐butyloxyl)borate (LiTFPFB) are dissolved in dominant carbonate solvents with low melting point and high boiling point. Abstract In this study, self‐synthesized lithium trifluoro(perfluoro‐tert‐butyloxyl)borate (LiTFPFB) is combined with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) to formulate a novel 1 m dual‐salt electrolyte, which contains lithium difluorophosphate (LiPO2F2) additive and dominant carbonate solvents with low melting point and high boiling point. The addition of LiPO2F2 into this novel dual‐salt electrolyte dramatically improves cycleability and rate capability of a LiNi0.5Mn0.3Co0.2O2/Li (NMC/Li) battery, ranging from −40 to 90 °C. The NMC/Li batteries adopt a Li–metal anode with low thickness of 100 µm (even 50 µm) and a moderately high cathode mass loading level of 10 mg cm−2. For the first time, this paper provides valuable perspectives for developing practical lithium–metal batteries over a wide temperature range.

A Cut‐and‐Weld Process to 3D Architectures from Multiresponsive Crosslinked Liquid Crystalline Polymers

By Xiaoxiong Zheng, Song Guan, Chen Zhang, Ting Qu, Wei Wen, Yongbin Zhao, Aihua Chen from Wiley: Small: Table of Contents. Published on Apr 18, 2019.

A cut‐and‐weld process based on crosslinked liquid crystalline polymer films is demonstrated to prepare complex 2D or 3D architectures with photo‐ and humidity‐responsiveness. This process provides a practical route to integrate smart complex 3D architectures into soft robots especially for operating small objects via remote manipulation. Abstract Crosslinked liquid crystalline polymers (CLCPs) have garnered extensive attention in recent years for their significant values in the design of light‐driven soft actuators. However, poor processabilities due to the insoluble and infusible crosslinked networks prevent their practical applications severely. In this study, a weldable azobenzene‐containing CLCP is designed with photo‐ and humidity‐responsive actuations, which enables a cut‐and‐weld process to 3D CLCP architectures. The tensile properties and stability are almost unchanged after welding, much better than those of the films pasted by common adhesive tapes. Meanwhile, the mechanisms of the welding process are clarified on the base of surface hydrogen bonding and further crosslinking. By taking advantage of the cut‐and‐weld process, a 3D “claw” integrated into a robotic arm is realized for grabbing millimeter‐scale objects by remote control. This work enhances significantly not only the processability of CLCP films but also the utilization of leftover pieces, which provides an efficient approach to create functional 3D structures from film precursors for the potential application in the smart materials.

Inkjet‐Printed High‐Efficiency Multilayer QLEDs Based on a Novel Crosslinkable Small‐Molecule Hole Transport Material

By Liming Xie, Xueying Xiong, Qiaowen Chang, Xiaolian Chen, Changting Wei, Xia Li, Meng Zhang, Wenming Su, Zheng Cui from Wiley: Small: Table of Contents. Published on Apr 18, 2019.

A novel crosslinkable hole transport material, 4,4′‐bis(3‐vinyl‐9H‐carbazol‐9‐yl)‐1, 1′‐biphenyl (CBP‐V), is synthesized and investigated for inkjet printing of quantum dots light‐emitting diodes (QLEDs). The resulting CBP‐V film after crosslinking exhibits excellent solvent resistance properties. Impressively, red QLED is successfully fabricated by inkjet printing CBP‐V and quantum dots bilayer. Maximum external quantum efficiency of 11.6% is achieved, which is 92% of a reference spin‐coated QLED (12.6%). Abstract Quantum dots light‐emitting diodes (QLEDs) have attracted much interest owing to their compatibility with low‐cost inkjet printing technology and potential for use in large‐area full‐color pixelated display. However, it is challenging to fabricate high efficiency inkjet‐printed QLEDs because of the coffee ring effects and inferior resistance to solvents from the underlying polymer film during the inkjet printing process. In this study, a novel crosslinkable hole transport material, 4,4′‐bis(3‐vinyl‐9H‐carbazol‐9‐yl)‐1,1′‐biphenyl (CBP‐V) which is small‐molecule based, is synthesized and investigated for inkjet printing of QLEDs. The resulting CBP‐V film after thermal curing exhibits excellent solvent resistance properties without any initiators. An added advantage is that the crosslinked CBP‐V film has a sufficiently low highest occupied molecular orbital energy level (≈−6.2 eV), high film compactness, and high hole mobility, which can thus promote the hole injection into quantum dots (QDs) and improve the charge carrier balance within the QD emitting layers. A red QLED is successfully fabricated by inkjet printing a CBP‐V and QDs bilayer. Maximum external quantum efficiency of 11.6% is achieved, which is 92% of a reference spin‐coated QLED (12.6%). This is the first report of such high‐efficiency inkjet‐printed multilayer QLEDs and demonstrates a unique and effective approach to inkjet printing fabrication of high‐performance QLEDs.

Masthead: (Small 16/2019)

By from Wiley: Small: Table of Contents. Published on Apr 18, 2019.

Lithium–Metal Batteries: Additive‐Assisted Novel Dual‐Salt Electrolyte Addresses Wide Temperature Operation of Lithium–Metal Batteries (Small 16/2019)

By Xuehui Shangguan, Gaojie Xu, Zili Cui, Qinglei Wang, Xiaofan Du, Kai Chen, Suqi Huang, Guofeng Jia, Faqiang Li, Xiao Wang, Di Lu, Shanmu Dong, Guanglei Cui from Wiley: Small: Table of Contents. Published on Apr 18, 2019.

In article number 1900269, Guofeng Jia, Guanglei Cui, and co‐workers combine self‐synthesized lithium trifluoro(perfluoro‐tert‐butyloxyl)borate (LiTFPFB) with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) to formulate a 1 m dual‐salt electrolyte, which contains lithium difluorophosphate (LiPO2F2) additive and dominant carbonate solvents with low melting point and high boiling point. This addition dramatically improves cyclability and rate capability of a LiNi0.5Mn0.3Co0.2O2/Li (NMC/Li) battery, unprecedentedly ranging from −40 °C to 90 °C.

Quantum Dots: Inkjet‐Printed High‐Efficiency Multilayer QLEDs Based on a Novel Crosslinkable Small‐Molecule Hole Transport Material (Small 16/2019)

By Liming Xie, Xueying Xiong, Qiaowen Chang, Xiaolian Chen, Changting Wei, Xia Li, Meng Zhang, Wenming Su, Zheng Cui from Wiley: Small: Table of Contents. Published on Apr 18, 2019.

In article number 1900111, Wenming Su and co‐workers synthesize a crosslinkable hole transport material, 4,4′‐bis(3‐vinyl‐9H‐carbazol‐9‐yl)‐1,1′‐biphenyl (CBP‐V) for inkjet printing of quantum dots light‐emitting diodes (QLEDs). The inkjet‐printed CBP‐V film is smooth and flat. After thermal curing, an extremely dense and crosslinked solvent resistant film is formed. The function of this film for QLED is hole transport and to help hole injection at the hole transport layer (CBP‐V)/QD. Finally, the hole and electron are recombined in the quantum dot layer and emit red light, achieving high efficiency.

Water Purification: Metal–Organic Frameworks and Their Derived Materials: Emerging Catalysts for a Sulfate Radicals‐Based Advanced Oxidation Process in Water Purification (Small 16/2019)

By Chaohai Wang, Jeonghun Kim, Victor Malgras, Jongbeom Na, Jianjian Lin, Jungmok You, Ming Zhang, Jiansheng Li, Yusuke Yamauchi from Wiley: Small: Table of Contents. Published on Apr 18, 2019.

In article number 1900744, Jeonghun Kim, Jiansheng Li, Yusuke Yamauchi, and co‐workers review the progress of metal–organic framework (MOF) related materials for sulfate radical (SO4•−)‐based advanced oxidation processes (SR‐AOPs) for application in water purification, which will significantly promote the development of MOFs‐based materials toward environmental remediation.

Microrobotics: 3D Fabrication of Fully Iron Magnetic Microrobots (Small 16/2019)

By Carlos C. J. Alcântara, Sangwon Kim, Sunkey Lee, Bumjin Jang, Prakash Thakolkaran, Jin‐Young Kim, Hongsoo Choi, Bradley J. Nelson, Salvador Pané from Wiley: Small: Table of Contents. Published on Apr 18, 2019.

Theories suggest that ancient Egyptians believed that the bones of gods were made of iron. Indeed, iron has been suggested as a key material in implantable biodegradable medical devices. In article number 1805006, Sangwon Kim, Bradley J. Nelson, Salvador Pané, and co‐workers describe how to manufacture three‐dimensional fully iron magnetic microrobots for biomedical applications using two‐photon polymerization and electrodeposition.

Development of “CLAN” Nanomedicine for Nucleic Acid Therapeutics

By Cong‐Fei Xu, Shoaib Iqbal, Song Shen, Ying‐Li Luo, Xianzhu Yang, Jun Wang from Wiley: Small: Table of Contents. Published on Apr 18, 2019.

A cationic lipid assisted PEG‐b‐PLA nanoparticle (CLAN) has been developed via encapsulation of nucleic acids inside the aqueous core for disease treatment. In this Review, the development and working mechanisms of CLANs, the ways to improve its delivery efficacy, and their application are summarized. Finally, the prospective for further development of CLAN is also discussed. Abstract Nucleic acid‐based macromolecules have paved new avenues for the development of therapeutic interventions against a spectrum of diseases; however, their clinical translation is limited by successful delivery to the target site and cells. Therefore, numerous systems have been developed to overcome delivery challenges to nucleic acids. From the viewpoint of clinical translation, it is highly desirable to develop systems with clinically validated materials and controllability in synthesis. With this in mind, a cationic lipid assisted PEG‐b‐PLA nanoparticle (CLAN) is designed that is capable of protecting nucleic acids via encapsulation inside the aqueous core, and delivers them to target cells, while maintaining or improving nucleic acid function. The system is formulated from clinically validated components (PEG‐b‐PLA and its derivatives) and can be scaled‐up for large scale manufacturing, offering potential for its future use in clinical applications. Here, the development and working mechanisms of CLANs, the ways to improve its delivery efficacy, and its application in various disease treatments are summarized. Finally, a prospective for the further development of CLAN is also discussed.

Metal–Organic Frameworks and Their Derived Materials: Emerging Catalysts for a Sulfate Radicals‐Based Advanced Oxidation Process in Water Purification

By Chaohai Wang, Jeonghun Kim, Victor Malgras, Jongbeom Na, Jianjian Lin, Jungmok You, Ming Zhang, Jiansheng Li, Yusuke Yamauchi from Wiley: Small: Table of Contents. Published on Apr 18, 2019.

Metal–organic frameworks (MOFs) related materials as catalysts for sulfate radical (SO4•−)‐based advanced oxidation processes (SR‐AOPs) have been attracting extensive attention in water purification. This work reviews the progress of pristine MOFs, MOFs composites, and their derivatives for SR‐AOPs application. The mechanisms, current challenges, and future research directions are also provided in detail. Abstract With the ever‐growing environmental issues, sulfate radical (SO4•−)‐based advanced oxidation processes (SR‐AOPs) have been attracting widespread attention due to their high selectivity and oxidative potential in water purification. Among various methods generating SO4•−, employing heterogeneous catalysts for activation of peroxymonosulfate or persulfate has been demonstrated as an effective strategy. Therefore, the future advances of SR‐AOPs depend on the development of adequate catalysts with high activity and stability. Metal–organic frameworks (MOFs) with large surface area, ultrahigh porosity, and diversity of material design have been extensively used in heterogeneous catalysts, and more recently, enormous effort has been made to utilize MOFs‐based materials for SR‐AOPs applications. In this work, the state‐of‐the‐art research on pristine MOFs, MOFs composites, and their derivatives, such as oxides, metal/carbon hybrids, and carbon materials for SR‐AOPs, is summarized. The mechanisms, including radical and nonradical pathways, are also detailed in the discussion. This work will hopefully promote the future development of MOFs‐based materials toward SR‐AOPs applications.

Wed 08 May 16:00: Title to be confirmed

From All Talks (aka the CURE list). Published on Apr 18, 2019.

Title to be confirmed

Abstract not available

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Copper‐Catalyzed N‐F Bond Activation for Uniform Intramolecular C‐H Amination to Pyrrolidines and Piperidines

By Pedro J. Pérez, Feliu Maseras, Kilian Muñiz, Tomas Belderrain, Daniel Bafaluy, Jose Maria Muñoz-Molina, Ignacio Funes-Ardoiz, Sebastian Herold, Adiran J de Aguirre, Hongwei Zhang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 18, 2019.

The dual function of the N‐F bond as an effective oxidant and subsequent nitrogen source in intramolecular aliphatic C‐H functionalization reactions is explored. Copper catalysis is demonstrated to exercise full regio‐ and chemoselectivity control, which opens new synthetic venues to nitrogenated heterocycles with predictable ring size. For the first time, a uniform catalysis manifold has been identified for the construction of both pyrrolidine and piperidine cores. The individual steps of this new copper oxidation catalysis are elucidated by control experiments and computational studies, clarifying the singularity of the N‐F function and characterizing the catalytic cycle to be based on a copper(I/II) manifold.

Thu 16 May 11:30: Transposable elements as catalysts of cellular innovation Hosted by: Eric Miska & Azim Surani

From All Talks (aka the CURE list). Published on Apr 18, 2019.

Transposable elements as catalysts of cellular innovation

Abstract not available

Hosted by: Eric Miska & Azim Surani

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Fri 17 May 14:00: Title to be confirmed

From All Talks (aka the CURE list). Published on Apr 18, 2019.

Title to be confirmed

Abstract not available

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Wed 15 May 16:30: Affinoid Duflo theorem for primitive ideals with trivial central character

From All Talks (aka the CURE list). Published on Apr 18, 2019.

Affinoid Duflo theorem for primitive ideals with trivial central character

Let R be a mixed characteristic DVR with field of fractions K. Let G be a connected, simply-connected, split semisimple affine algebraic group scheme over R with Lie algebra L(G). Ardakov and Wadsley (2013) asked whether we can characterise the primitive ideals in the affinoid enveloping algebra of L(G) with K-rational central character. 

I will begin by reviewing Duflo’s theorem characterizing the primitive spectrum of the classical enveloping algebra of L(G).I will then characterise the primitive ideals in the affinoid enveloping algebra with trivial central character using an affinoid version of Beilinson-Bernstein localisation.

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High‐Stability MnOx Nanowires@C@MnOx Nanosheet Core–Shell Heterostructure Pseudocapacitance Electrode Based on Reversible Phase Transition Mechanism

By Zhipeng Ma, Fengyang Jing, Yuqian Fan, Liyin Hou, Li Su, Lukai Fan, Guangjie Shao from Wiley: Small: Table of Contents. Published on Apr 18, 2019.

A stable MnOx@C@MnOx core–shell heterostructure consisting of vertical MnOx nanosheets grown evenly on the surface of the MnOx@carbon nanowires are obtained by simple liquid phase method combined with thermal treatment. The MnOx undergoes a reversible phase transformation reaction of Mn3O4↔α‐phase MnO2. Hence, the hierarchical MnOx@C@MnOx heterostructure electrode exhibits a superior cyclic performance. Abstract A stable MnOx@C@MnOx core–shell heterostructure consisting of vertical MnOx nanosheets grown evenly on the surface of the MnOx@carbon nanowires are obtained by simple liquid phase method combined with thermal treatment. The hierarchical MnOx@C@MnOx heterostructure electrode possesses a high specific capacitance of 350 F g−1 and an excellent cycle performance owing to the existence of the pore structure among the ultrasmall MnOx nanoparticles and the rapid transmission of electrons between the active material and carbon coating layer. Particularly, according to the in situ Raman spectra analysis, no characteristic peaks corresponding to MnOOH are found during charging/discharging, indicating that pseudocapacitive behavior of the MnOx electrode have no relevance to the intercalation/deintercalation of protons (H+) in the electrolyte. Further combining in situ X‐ray powder diffraction analysis, the diffraction peak of α‐MnO2 can be detected in the process of charging, while Mn3O4 phase is found in discharge products. Therefore, these results demonstrate that the MnOx undergoes a reversible phase transformation reaction of Mn3O4↔α‐MnO2. Moreover, the assembled all‐solid‐state asymmetric supercapacitor with a MnOx@C@MnOx electrode delivers a high energy density of 23 Wh kg−1, an acceptable power density of 2500 W kg−1, and an excellent cyclic stability performance of 94% after 2000 cycles, showing the potential for practical application.

Wed 12 Jun 14:15: TBC

From All Talks (aka the CURE list). Published on Apr 18, 2019.

TBC

Abstract not available

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Wed 05 Jun 14:15: TBC

From All Talks (aka the CURE list). Published on Apr 18, 2019.

TBC

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Wed 29 May 14:15: TBC

From All Talks (aka the CURE list). Published on Apr 18, 2019.

TBC

Abstract not available

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Wed 22 May 14:15: TBC

From All Talks (aka the CURE list). Published on Apr 18, 2019.

TBC

Abstract not available

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Wed 15 May 14:15: TBC

From All Talks (aka the CURE list). Published on Apr 18, 2019.

TBC

Abstract not available

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Wed 08 May 16:30: Title to be confirmed

From All Talks (aka the CURE list). Published on Apr 18, 2019.

Title to be confirmed

Abstract not available

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Wed 08 May 14:15: TBC

From All Talks (aka the CURE list). Published on Apr 18, 2019.

TBC

Abstract not available

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Wed 01 May 16:30: Title to be confirmed

From All Talks (aka the CURE list). Published on Apr 18, 2019.

Title to be confirmed

Abstract not available

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Wed 01 May 14:15: Life, the universe and everything . . . with Anne

From All Talks (aka the CURE list). Published on Apr 18, 2019.

Life, the universe and everything . . . with Anne

Abstract not available

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Wed 24 Apr 14:15: Analytic results for two-loop five-particle amplitudes

From All Talks (aka the CURE list). Published on Apr 18, 2019.

Analytic results for two-loop five-particle amplitudes

In this talk I will review recent advances that lead to the first complete calculation of five-particle scattering amplitudes at two loops, for amplitudes in N=4 super Yang-Mills and N=8 supergravity. In particular, I will review the space of pentagon functions, which covers all functions needed for two-loop five-particle amplitudes in any gauge theory, including QCD .

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A general treatment to study molecular complexes stabilized by hydrogen, halogen and carbon bond networks: Experiment and theory of (CH2F2)n···(H2O)m

By Camilla Calabrese, Weixing Li, Giacomo Prampolini, Luca Evangelisti, Iciar Uriarte, Ivo Cacelli, Sonia Melandri, Emilio J Cocinero from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 18, 2019.

Rotational spectra of several difluomethane water adducts have been observed using two broadband chirped pulse Fourier transform microwave (CP FTMW) spectrometers. The experimental structures of (CH2F2)···(H2O)2, (CH2F2)2···(H2O), (CH2F2)···(H2O)3 and (CH2F2)2···(H2O)2 were unambiguously identified with the aid of 18 isotopic substituted species. A subtle competition between hydrogen, halogen and carbon bonds is observed and a detailed analysis was performed on the complex network of non‐covalent interactions, which stabilize each cluster. The study shows that the combination of stabilizing contacts networks is able to reinforce the interaction strength through a cooperative effect, which can lead to large stable oligomers.

Tue 28 May 14:30: Title to be confirmed

From All Talks (aka the CURE list). Published on Apr 18, 2019.

Title to be confirmed

Abstract not available

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Tue 21 May 14:30: Title to be confirmed

From All Talks (aka the CURE list). Published on Apr 18, 2019.

Title to be confirmed

Abstract not available

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Fri 03 May 13:00: Surveillance, detection and response to emerging International Health Emergencies: the role of the WHO

From All Talks (aka the CURE list). Published on Apr 18, 2019.

Surveillance, detection and response to emerging International Health Emergencies: the role of the WHO

Dr Oliver Morgan is Director Health Emergency Information and Risk Assessment, Health Emergencies Programme,at the World Health Organisation.

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Selenium‐Modified Microgels as Bio‐Inspired Oxidation Catalysts

By Kok Hui Tan, Wenjing Xu, Simon Stefka, Dan Demco, Tetiana Kahrandiuk, Volodymyr Ivasiv, Roman Nebesnyi, Vladislav Petrovskii, Igor Potemkin, Andrij Pich from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 18, 2019.

Active colloidal catalysts inspired by the glutathione peroxidase (GPx) were synthesized by integration of catalytically active selenium (Se) moieties into aqueous microgels. Diselenide crosslinker (Se X‐linker) was successfully synthesized and incorporated into microgels through precipitation polymerization, along with conventional crosslinker N,N´‐Methylenebis(acrylamide) (BIS). Diselenide bonds inside the microgels were cleaved through oxidation by H2O2 and converted to seleninic acid whilst maintaining the microgel microstructure intact. Using this approach catalytically active microgels with variable amounts of seleninic acid were synthesized. Remarkably, the microgels exhibited higher catalytic activity and selectivity at low reaction temperatures compared with the molecular Se catalyst in a model oxidation reaction of acrolein to acrylic acid and methyl acrylate.

[ASAP] Graphene Oxide Flakes Tune Excitatory Neurotransmission in Vivo by Targeting Hippocampal Synapses

By Rossana Rauti, Manuela Medelin, Leon Newman, Sandra Vranic, Giacomo Reina, Alberto Bianco, Maurizio Prato, Kostas Kostarelos, Laura Ballerini from Nano Letters: Latest Articles (ACS Publications). Published on Apr 18, 2019.

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Nano Letters
DOI: 10.1021/acs.nanolett.8b04903

[ASAP] Nanovoid Membranes Embedded with Hollow Zwitterionic Nanocapsules for a Superior Desalination Performance

By Zhijuan Sun, Qian Wu, Changhuai Ye, Wei Wang, Liuchun Zheng, Fengkai Dong, Zhuan Yi, Lixin Xue, Congjie Gao from Nano Letters: Latest Articles (ACS Publications). Published on Apr 18, 2019.

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Nano Letters
DOI: 10.1021/acs.nanolett.9b00060

[ASAP] Tracking Sub-Nanometer Shift in the Scattering Centroid of Single Gold Nanorods during Electrochemical Charging

By Tao Liu, Shasha Liu, Wenxuan Jiang, Wei Wang from ACS Nano: Latest Articles (ACS Publications). Published on Apr 18, 2019.

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ACS Nano
DOI: 10.1021/acsnano.8b09636

[ASAP] Link between Low-Fouling and Stealth: A Whole Blood Biomolecular Corona and Cellular Association Analysis on Nanoengineered Particles

By Alessia C. G. Weiss, Hannah G. Kelly, Matthew Faria, Quinn A. Besford, Adam K. Wheatley, Ching-Seng Ang, Edmund J. Crampin, Frank Caruso, Stephen J. Kent from ACS Nano: Latest Articles (ACS Publications). Published on Apr 18, 2019.

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ACS Nano
DOI: 10.1021/acsnano.9b00552

[ASAP] Atomic-Scale Chemical Conversion of Single-Layer Transition Metal Dichalcogenides

By Peng Chen, Yun-Ting Chen, Ro-Ya Liu, Han-De Chen, Dengsung Lin, Alexei V. Fedorov, Tai-Chang Chiang from ACS Nano: Latest Articles (ACS Publications). Published on Apr 18, 2019.

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ACS Nano
DOI: 10.1021/acsnano.9b00756

[ASAP] Solution Conditions Tune and Optimize Loading of Therapeutic Polyelectrolytes into Layer-by-Layer Functionalized Liposomes

By Santiago Correa, Natalie Boehnke, Elad Deiss-Yehiely, Paula T. Hammond from ACS Nano: Latest Articles (ACS Publications). Published on Apr 18, 2019.

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ACS Nano
DOI: 10.1021/acsnano.9b00792

[ASAP] The Route to Supercurrent Transparent Ferromagnetic Barriers in Superconducting Matrix

By Yurii P. Ivanov, Soltan Soltan, Joachim Albrecht, Eberhard Goering, Gisela Schütz, Zaoli Zhang, Andrey Chuvilin from ACS Nano: Latest Articles (ACS Publications). Published on Apr 18, 2019.

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ACS Nano
DOI: 10.1021/acsnano.9b00888

[ASAP] Copper Sulfide Facilitates Hepatobiliary Clearance of Gold Nanoparticles through the Copper-Transporting ATPase ATP7B

By Xiaodong Wang, Liangran Guo, Sihang Zhang, Yuan Chen, Yi-Tzai Chen, Binbin Zheng, Jingwen Sun, Yuyi Qian, Yixin Chen, Bingfang Yan, Wei Lu from ACS Nano: Latest Articles (ACS Publications). Published on Apr 18, 2019.

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ACS Nano
DOI: 10.1021/acsnano.9b01154

[ASAP] Self-Assembly of Short Chain Poly-N-isopropylacrylamid Induced by Superchaotropic Keggin Polyoxometalates: From Globules to Sheets

By Thomas Buchecker, Philipp Schmid, Isabelle Grillo, Sylvain Prévost, Markus Drechsler, Olivier Diat, Arno Pfitzner, Pierre Bauduin from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Apr 18, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.8b12181

[ASAP] Initial Steps in Forming the Electrode–Electrolyte Interface: H2O Adsorption and Complex Formation on the Ag(111) Surface from Combining Quantum Mechanics Calculations and Ambient Pressure X-ray Photoelectron Spectroscopy

By Jin Qian, Yifan Ye, Hao Yang, Junko Yano, Ethan J. Crumlin, William A. Goddard III from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Apr 18, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.8b13672

[ASAP] Automated Stoichiometry Analysis of Single-Molecule Fluorescence Imaging Traces via Deep Learning

By Jiachao Xu, Gege Qin, Fang Luo, Lina Wang, Rong Zhao, Nan Li, Jinghe Yuan, Xiaohong Fang from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Apr 18, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b00688

[ASAP] Controllable Covalent-Bound Nanoarchitectures from DNA Frames

By Zhiwei Lin, Yan Xiong, Shuting Xiang, Oleg Gang from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Apr 18, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b01510

[ASAP] Molecular-Level Understanding of Continuous Growth from Iron-Oxo Clusters to Iron Oxide Nanoparticles

By Hogeun Chang, Byung Hyo Kim, Hu Young Jeong, Jeong Hee Moon, Minwoo Park, Kwangsoo Shin, Sue In Chae, Jisoo Lee, Taegyu Kang, Back Kyu Choi, Jiwoong Yang, Megalamane S. Bootharaju, Hyoin Song, Seong Hee An, Kyung Man Park, Joo Yeon Oh, Hoonkyung Lee, Myung Soo Kim, Jungwon Park, Taeghwan Hyeon from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Apr 18, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b01670

[ASAP] Iridium-Catalyzed Asymmetric Borylation of Unactivated Methylene C(sp3)–H Bonds

By Ronald L. Reyes, Tomohiro Iwai, Satoshi Maeda, Masaya Sawamura from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Apr 18, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b01952

[ASAP] Rh(III)-Catalyzed C–H Activation-Initiated Directed Cyclopropanation of Allylic Alcohols

By Erik J. T. Phipps, Tomislav Rovis from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Apr 18, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b02156

[ASAP] Molecular Glue that Spatiotemporally Turns on Protein–Protein Interactions

By Rina Mogaki, Kou Okuro, Ryosuke Ueki, Shinsuke Sando, Takuzo Aida from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Apr 18, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b02427

[ASAP] Direct Functionalization of White Phosphorus to Cyclotetraphosphanes: Selective Formation of Four P–C Bonds

By Shanshan Du, Jimin Yang, Jingyuan Hu, Zhengqi Chai, Gen Luo, Yi Luo, Wen-Xiong Zhang, Zhenfeng Xi from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Apr 18, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b02628

[ASAP] Taming Ambident Triazole Anions: Regioselective Ion Pairing Catalyzes Direct N-Alkylation with Atypical Regioselectivity

By Harvey J. A. Dale, George R. Hodges, Guy C. Lloyd-Jones from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Apr 18, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b02786

[ASAP] Copper-Catalyzed Trifluoromethylation of Alkyl Bromides

By David J. P. Kornfilt, David W. C. MacMillan from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Apr 18, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b03024

[ASAP] Conversion of Aldehydes to Branched or Linear Ketones via Regiodivergent Rhodium-Catalyzed Vinyl Bromide Reductive Coupling–Redox Isomerization Mediated by Formate

By Robert A. Swyka, William G. Shuler, Brian J. Spinello, Wandi Zhang, Chunling Lan, Michael J. Krische from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Apr 18, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b03113

[ASAP] Ketone Synthesis by a Nickel-Catalyzed Dehydrogenative Cross-Coupling of Primary Alcohols

By Thomas Verheyen, Lars van Turnhout, Jaya Kishore Vandavasi, Eric S. Isbrandt, Wim M. De Borggraeve, Stephen G. Newman from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Apr 18, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b03280

How all sizes fit together

By Philip Ball from Nature Materials - Issue - nature.com science feeds. Published on Apr 18, 2019.

How all sizes fit together

How all sizes fit together, Published online: 18 April 2019; doi:10.1038/s41563-019-0362-z

How all sizes fit together

Fast movement in a crowd

By Stephen Shevlin from Nature Materials - Issue - nature.com science feeds. Published on Apr 18, 2019.

Fast movement in a crowd

Fast movement in a crowd, Published online: 18 April 2019; doi:10.1038/s41563-019-0353-0

Fast movement in a crowd

Leveraging machine vision in cell-based diagnostics to do more with less

By Anne E. Carpenter from Nature Materials - Issue - nature.com science feeds. Published on Apr 18, 2019.

Leveraging machine vision in cell-based diagnostics to do more with less

Leveraging machine vision in cell-based diagnostics to do more with less, Published online: 18 April 2019; doi:10.1038/s41563-019-0339-y

Highly quantitative, robust, single-cell analyses can help to unravel disease heterogeneity and lead to clinical insights, particularly for complex and chronic diseases. Advances in computer vision and machine learning can empower label-free cell-based diagnostics to capture subtle disease states.

Ascent of machine learning in medicine

From Nature Materials - Issue - nature.com science feeds. Published on Apr 18, 2019.

Ascent of machine learning in medicine

Ascent of machine learning in medicine, Published online: 18 April 2019; doi:10.1038/s41563-019-0360-1

Machine learning is swiftly infiltrating many areas within the healthcare industry, from diagnosis and prognosis to drug development and epidemiology, with significant potential to transform the medical landscape.

Opportunities and challenges using artificial intelligence in ADME/Tox

By Sean Ekins from Nature Materials - Issue - nature.com science feeds. Published on Apr 18, 2019.

Opportunities and challenges using artificial intelligence in ADME/Tox

Opportunities and challenges using artificial intelligence in ADME/Tox, Published online: 18 April 2019; doi:10.1038/s41563-019-0332-5

At the recent Artificial Intelligence Applications in Biopharma Summit in Boston, USA, a panel of scientists from industry who work at the interface of machine learning and pharma discussed the diverging opinions on the past, present and future role of AI for ADME/Tox in drug discovery and development.

Lighting up Weyl semimetals

By Hongming Weng from Nature Materials - Issue - nature.com science feeds. Published on Apr 18, 2019.

Lighting up Weyl semimetals

Lighting up Weyl semimetals, Published online: 18 April 2019; doi:10.1038/s41563-019-0330-7

By measuring the photocurrent from illuminated Weyl semimetals, an optical signature of topological properties arising from Weyl fermions has been revealed, highlighting nonlinear optical effects and applications of Weyl semimetals.

How to develop machine learning models for healthcare

By Lily Peng from Nature Materials - Issue - nature.com science feeds. Published on Apr 18, 2019.

How to develop machine learning models for healthcare

How to develop machine learning models for healthcare, Published online: 18 April 2019; doi:10.1038/s41563-019-0345-0

Rapid progress in machine learning is enabling opportunities for improved clinical decision support. Importantly, however, developing, validating and implementing machine learning models for healthcare entail some particular considerations to increase the chances of eventually improving patient care.

Exploiting machine learning for end-to-end drug discovery and development

By Alex M. Clark from Nature Materials - Issue - nature.com science feeds. Published on Apr 18, 2019.

Exploiting machine learning for end-to-end drug discovery and development

Exploiting machine learning for end-to-end drug discovery and development, Published online: 18 April 2019; doi:10.1038/s41563-019-0338-z

This Perspective describes the application of machine learning models in the design, synthesis and characterisation of molecules at different stages in the drug discovery and development process.

Light-facilitated Drug Delivery System from Pseudo-protein/Hyaluronic Acid Nanocomplex with Improved Anti-Tumor Effect

By Chih-Chang Chu from RSC - Nanoscale latest articles. Published on Apr 18, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR01909J, Paper
YING JI, Juan Li, Jihui Zhao, Shuo Shan, Chih-Chang Chu
Reduction-sensitive nanomedicine is a promising strategy to achieve controlled release of payloads in response to intracellular reductive milieu. However, endolysosomal sequestration of internalized carriers and insufficient redox potential in endolysosomes...
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Valence mediated tunable magnetism and electronic properties by ferroelectric polarization switching in 2D FeI2/In2Se3 van der Waals heterostructures

By Yuanxu Wang from RSC - Nanoscale latest articles. Published on Apr 18, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR01510H, Paper
Wei Sun, Wang Wenxuan, Dong chen, Z. X. Cheng, Yuanxu Wang
Exploring two-dimensional (2D) materials with both ferromagnetic and ferroelectric properties are scientifically interesting and of great technical importance to numerous functionalities in nanoscale devices. In this work, we have demonstrated...
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Wearable solid-state capacitors based on two-dimensional material all-textile heterostructures

By Felice Torrisi from RSC - Nanoscale latest articles. Published on Apr 18, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR00463G, Paper
Siyu Qiang, Tian Carey, Adrees Arbab, Weihua Song, Chaoxia Wang, Felice Torrisi
Two dimensional (2D) materials are a rapidly growing area of interest for wearable electronics, due to their flexible and unique electrical properties. All-textile based wearable electronic components are key to...
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Nanocarbon Materials in Water Disinfection: State-of-the-Art and Future Directions

By Yuan Chen from RSC - Nanoscale latest articles. Published on Apr 18, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR02007A, Minireview
Liang Wang, Ziwen Yuan, H. Enis Karahan, Yilei Wang, Xiao Sui, Fei Liu, Yuan Chen
Water disinfection practices are critical for supplying safe drinking water. Existing water disinfection methods come with various drawbacks, calling for alternative or complementary solutions. Nanocarbon materials (NCMs) offer unique advantages...
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Alternatives to Cryogenic Distillation: Advanced Porous Materials in Adsorptive Light Olefin/Paraffin Separations

By Yuxiang Wang, Shing Bo Peh, Dan Zhao from Wiley: Small: Table of Contents. Published on Apr 17, 2019.

Adsorptive light olefin/paraffin separations facilitated by advanced porous materials such as zeolites and metal–organic frameworks are reviewed. Different separation mechanisms realized in these materials are highlighted, and constructive perspectives on future directions of the field are provided. Abstract As primary feedstocks in the petrochemical industry, light olefins such as ethylene and propylene are mainly obtained from steam cracking of naphtha and short chain alkanes (ethane and propane). Due to their similar physical properties, the separations of olefins and paraffins—pivotal processes to meet the olefin purity requirement of downstream processing—are typically performed by highly energy‐intensive cryogenic distillation at low temperatures and high pressures. To reduce the energy input and save costs, adsorptive olefin/paraffin separations have been proposed as promising techniques to complement or even replace cryogenic distillation, and growing efforts have been devoted to developing advanced adsorbents to fulfill this challenging task. In this Review, a holistic view of olefin/paraffin separations is first provided by summarizing how different processes have been established to leverage the differences between olefins and paraffins for effective separations. Subsequently, recent advances in the development of porous materials for adsorptive olefin/paraffin separations are highlighted with an emphasis on different separation mechanisms. Last, a perspective on possible directions to push the limit of the research in this field is presented.

A Low‐Spin Three‐Coordinate Cobalt(I) Complex and Its Reactivity toward H2 and Silane

By Jonghoon Choi, Yunho Lee from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 17, 2019.

Fits to a T: A three‐coordinate low‐spin cobalt(I) complex with an acridane‐based pincer ligand was synthesized. It reacts with H2 and PhSiH3 by σ‐complexation at the cobalt center, which has an empty orbital. In this example, the homolysis of a σ‐bond via bimolecular hydrogen atom transfer (HAT) occurs rather than oxidative addition. Abstract A three‐coordinate low‐spin cobalt(I) complex generated using a pincer ligand is presented. Since an empty orbital is sterically exposed at the site trans to the N donor of an acridane moiety, the cobalt(I) center accepts the coordination of various donors such as H2 and PhSiH3 revealing σ‐complex formation. At this low‐spin cobalt(I) site, homolysis of H–H and Si−H bonds preferentially occurs via bimolecular hydrogen atom transfer instead of two‐electron oxidative addition. When the resulting CoII–H species was exposed to N2, H2 evolution readily occurs at ambient conditions. These results suggest single‐electron processes are favored at the structurally rigidified cobalt center.

A Universal Strategy for Activating the Multi‐Color Room‐Temperature Afterglow of Carbon Dots in a Boric Acid Matrix

By Wei Li, Wan Zhou, Zhishan Zhou, Haoran Zhang, Xuejie Zhang, Jianle Zhuang, Yingliang Liu, Bingfu Lei, Chaofan Hu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 17, 2019.

The room‐temperature phosphorescence (RTP) of CDs was activated by one‐step heat treatment of CDs and boric acid (BA). Heteroatom‐free CDs (a‐CDs) possess favorable RTP in BA matrix with a lifetime as high as 1.6 s. Blue, green, yellow‐green, and orange RTP CD‐based materials were obtained. These CD‐based RTP materials were successfully applied in information encryption owing to their distinctive RTP performance. Abstract Carbon dots (CDs) have attracted attention in metal‐free afterglow materials, but most CDs were heteroatom‐containing and the afterglow emissions are still limited to the short‐wavelength region. A universal approach to activate the room‐temperature phosphorescence (RTP) of both heteroatom‐free and heteroatom‐containing CDs was developed by one‐step heat treatment of CDs and boric acid (BA). The introduction of an electron‐withdrawing boron atom in composites can greatly reduce the energy gap between the singlet and triplet state; the formed glassy state can effectively protect the excited triplet states of CDs from nonradiative deactivation. A universal host for embedding CDs to achieve long‐lifetime and multi‐color (blue, green, green‐yellow and orange) RTP via a low cost, quick and facile process was developed. Based on their distinctive RTP performances, the applications of these CD‐based RTP materials in information encryption and decryption are also proposed and demonstrated.

Assembled Vitamin B2 Nanocrystals with Optical Waveguiding and Photosensitizing Properties for Potential Biomedical Application

By Jinbo Fei, Luru Dai, Fuping Gao, Jie Zhao, Junbai Li from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 17, 2019.

Guiding light: Self‐assembled monocrystalline vitamin B2 nanorods were produced that exhibit optical waveguiding and photosensitizing properties. They can be applied to optically waveguided single‐cell photodynamic therapy with high efficiency. Abstract Great success has been achieved in recent years in the development of synthetic or assembled nanobiomaterials. Among these, biomolecule‐based nanoarchitectures with special optical property are of particular interest. Here, we demonstrate that vitamin B2 nanocrystals assembled as nanorods can be obtained with precise control. Excitingly, such one‐dimensional nanostructures not only exhibit intrinsic optical waveguiding properties but also the ability to sensitize oxygen to produce reactive oxygen species. With these properties, we applied the obtained vitamin B2 nanorods under remotely localized light illumination into single tumour cells in vitro for anticancer photodynamic therapy. Further, vitamin B2 nanorods were explored for in vivo photodynamic therapy by using a tumour model. With such bionanostructures, new features and functions of vitamin B2 and its derivatives have been developed.

Intermolecular, Branch‐Selective, and Redox‐Neutral Cp*IrIII‐Catalyzed Allylic C−H Amidation

By Tobias Knecht, Shobhan Mondal, Jian‐Heng Ye, Mowpriya Das, Frank Glorius from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 17, 2019.

A new branch! A novel strategy for the mild, highly branch‐selective and redox‐neutral allylic C−H amidation is described. Naturally occurring and abundant carboxylic acids were converted into the corresponding dioxazolones and reliably coupled with terminal and internal olefins. The synthetic value of this transformation was demonstrated in the coupling of complex and bioactive scaffolds. Abstract Herein, we report the redox‐neutral, intermolecular, and highly branch‐selective amidation of allylic C−H bonds enabled by Cp*IrIII catalysis. A variety of readily available carboxylic acids were converted into the corresponding dioxazolones and efficiently coupled with terminal and internal olefins in high yields and selectivities. Mechanistic investigations support the formation of a nucleophilic IrIII–allyl intermediate rather than the direct insertion of an Ir–nitrenoid species into the allylic C−H bond.

Efficient and Monochromatic Electrochemiluminescence of Aqueous‐Soluble Au Nanoclusters via Host–Guest Recognition

By Liqiong Yang, Bin Zhang, Li Fu, Kena Fu, Guizheng Zou from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 17, 2019.

On the same wavelength: A promising strategy to screen environmentally friendly, biocompatible, and efficient electrochemiluminophores is proposed via rigidification of the shell of Au nanoclusters by host–guest recognition. Abstract Inspired by the enhanced photoluminescence of Au nanoclusters (AuNCs) with a rigid shell, the formation of rigid host–guest assemblies on AuNC surfaces was employed to screen novel electrochemiluminophores with 6‐aza‐2‐thiothymine(ATT)‐protected AuNCs (ATT‐AuNCs) and l‐arginine (ARG) as models for the first time. The rigid host–guest assemblies formed between ARG and ATT on the ATT‐AuNC surface enabled aqueous‐soluble ARG/ATT‐AuNCs with a dramatically enhanced electrochemiluminescence (ECL) compared to ATT‐AuNCs. This includes one cathodic ECL process (−1.30 V) and three anodic ECL processes (+0.78, 0.90, and 1.05 V) in a so‐called half‐scan experiment without a co‐reactant, as well as a 70‐fold enhanced oxidative‐reduction ECL at +0.78 V with tri‐n‐propylamine as a co‐reactant. Importantly, the ECL of the ARG/ATT‐AuNCs is highly monochromatic with an emission maximum around 532 nm and a full width at half‐maximum of 36 nm, which is of great interest for color‐selective ECL assays.

Reversible Oxygen Redox Chemistry in Aqueous Zinc‐Ion Batteries

By Fang Wan, Yan Zhang, Linlin Zhang, Daobin Liu, Changda Wang, Li Song, Zhiqiang Niu, Jun Chen from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 17, 2019.

Rezinking zinc batteries: Aqueous zinc‐ion batteries based on VOPO4 cathodes and a water‐in‐salt electrolyte displayed highly reversible oxygen redox chemistry at high voltages (see graph). The oxygen redox process not only led to increased capacity and a higher average operating voltage of the Zn/VOPO4 batteries, but also improved rate capability and cycling performance. Abstract Rechargeable aqueous zinc‐ion batteries (ZIBs) are promising energy‐storage devices owing to their low cost and high safety. However, their energy‐storage mechanisms are complex and not well established. Recent energy‐storage mechanisms of ZIBs usually depend on cationic redox processes. Anionic redox processes have not been observed owing to the limitations of cathodes and electrolytes. Herein, we describe highly reversible aqueous ZIBs based on layered VOPO4 cathodes and a water‐in‐salt electrolyte. Such batteries display reversible oxygen redox chemistry in a high‐voltage region. The oxygen redox process not only provides about 27 % additional capacity, but also increases the average operating voltage to around 1.56 V, thus increasing the energy density by approximately 36 %. Furthermore, the oxygen redox process promotes the reversible crystal‐structure evolution of VOPO4 during charge/discharge processes, thus resulting in enhanced rate capability and cycling performance.

Tailored Peptide Phenyl Esters Block ClpXP Proteolysis by an Unusual Breakdown into a Heptamer–Hexamer Assembly

By Markus Lakemeyer, Eva Bertosin, Friederike Möller, Dóra Balogh, Ralf Strasser, Hendrik Dietz, Stephan A. Sieber from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 17, 2019.

Tight and loose: Covalent (R)‐amino acid modifiers are novel tools for probing the activity and oligomerization of the bacterial ClpXP protease. Substoichiometric binding strengthens the ClpX–ClpP interaction. Depending on the substitution of the compound, proteolysis is either stimulated or efficiently inhibited by formation of an unprecedented complex assembly. Abstract The proteolytic complex ClpXP is fundamental to bacterial homeostasis and pathogenesis. Because of its conformational flexibility, the development of potent ClpXP inhibitors is challenging, and novel tools to decipher its intricate regulation are urgently needed. Herein, we present amino acid based phenyl esters as molecular probes to study the activity and oligomerization of the ClpXP complex of S. aureus. Systematic screening of (R)‐ and (S)‐amino acids led to compounds showing potent inhibition, as well as stimulation of ClpXP‐mediated proteolysis. Substoichiometric binding of probes arrested ClpXP in an unprecedented heptamer–hexamer assembly, in which the two heptameric ClpP rings are dissociated from each other. At the same time, the affinity between ClpX and ClpP increased, leading to inhibition of both enzymes. This conformational arrest is beneficial for the consolidated shutdown of ClpXP, as well as for the study of the oligomeric state during its catalytic cycle.

Organic Photodynamic Nanoinhibitor for Synergistic Cancer Therapy

By Yuyan Jiang, Jingchao Li, Ziling Zeng, Chen Xie, Yan Lyu, Kanyi Pu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 17, 2019.

Despite its great potential in cancer treatment, photodynamic therapy (PDT) often exacerbates hypoxia and subsequently compromises its therapeutic efficacy. To overcome this issue, an organic photodynamic nanoinhibitor (OPNi) is synthesized to have additional ability to counteract carbonic anhydrase IX (CA‐IX), a molecular target in hypoxia‐mediated signalling cascade. OPNi is composed of a metabolizable semiconducting polymer as the photosensitizer and a CA‐IX antagonist‐conjugated amphiphilic polymer as the matrix. Such a molecular structure allows OPNi not only to selectively bind CA‐IX positive cancer cells to facilitate its tumor accumulation but also to regulate CA‐IX‐related pathway. The integration of CA‐IX inhibition into targeted PDT process eventually has a synergistic effect, leading to the superior anti‐tumor efficacy over sole PDT as well as the reduced probability of hypoxia‐induced cancer metastasis. This study thus proposes a molecular strategy to devise simple yet amplified photosensitizers to conquer the pitfalls of traditional PDT.

Large‐Scale, Bottom‐Up Synthesis of Binary Metal–Organic Framework Nanosheets for Efficient Water Oxidation

By Fei‐Long Li, Pengtang Wang, Xiaoqing Huang, David James Young, Hui‐Fang Wang, Pierre Braunstein, Jian‐Ping Lang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 17, 2019.

Ultrathin, binary MOF nanosheets (NSs) have been successfully prepared for the first time and directly used as efficient oxygen evolution reaction (OER) catalysts. The binary MOF NSs exhibit a highly composition‐dependent OER activity. The optimized Ni–Fe–MOF NSs are highly active and stable towards the OER. Abstract Ultrathin metal–organic framework (MOF) nanosheets (NSs) offer potential for many applications, but the synthetic strategies are largely limited to top‐down, low‐yield exfoliation methods. Herein, Ni–M–MOF (M=Fe, Al, Co, Mn, Zn, and Cd) NSs are reported with a thickness of only several atomic layers, prepared by a large‐scale, bottom‐up solvothermal method. The solvent mixture of N,N‐dimethylacetamide and water plays key role in controlling the formation of these two‐dimensional MOF NSs. The MOF NSs can be directly used as efficient electrocatalysts for the oxygen evolution reaction, in which the Ni–Fe–MOF NSs deliver a current density of 10 mA cm−2 at a low overpotential of 221 mV with a small Tafel slope of 56.0 mV dec−1, and exhibit excellent stability for at least 20 h without obvious activity decay. Density functional theory calculations on the energy barriers for OER occurring at different metal sites confirm that Fe is the active site for OER at Ni–Fe–MOF NSs.

The Furan Shuffling Hypothesis: A Biogenetic Proposal for Eremophilane Sesquiterpenoids

By Nicolas Lardon, Raphael Liffert, Anthony Linden, Karl Gademann from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 17, 2019.

Shuffle the rings: An unusual furan rearrangement biogenetically connecting the eremophilane natural product microsphaeropsisin B and its regioisomer periconianone C is postulated. Strong experimental support for this intriguing mechanistic pattern is provided by total synthesis comprising an α‐ketol rearrangement. Abstract Based on the structural similarities of the recently isolated eremophilane‐type sesquiterpenoids microsphaeropsisin B and C and the iso‐eremophilane periconianone C, a revised biogenetic hypothesis for C8–C11‐connected iso‐eremophilanes is presented and corroborated by strong experimental evidence. The first enantioselective total syntheses of microsphaeropsisin B and C were achieved starting from a known intermediate, whose synthesis was elaborated previously in the total synthesis of periconianone A, and in a total of 15 steps starting from γ‐hydroxy carvone. Mild reaction conditions for the subsequent α‐ketol rearrangement not only resulted in the herein proposed conversion of microsphaeropsisin B into periconianone C, but also in the conversion of microsphaeropsisin C into 4‐epi‐periconianone C.

Circularly‐Polarized Electrochemiluminescence from a Chiral Bispyrene Organic Macrocycle

By Francesco Zinna, Silvia Voci, Lorenzo Arrico, Elodie Brun, Alexandre Homberg, Laurent Bouffier, Tiziana Funaioli, Jérôme Lacour, Neso Sojic, Lorenzo Di Bari from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 17, 2019.

A polarizing pair: Circularly polarized electrochemiluminescence from a chiral organic molecule is observed. The macrocyclic scaffold leads to an efficient excimer formation between two pyrene moieties that are covalently attached. As a result, highly polarized emission is obtained upon electrochemical excitation. Abstract The first observation of circular polarization of electrochemiluminescence (ECL) from a purely organic derivative is reported. A bispyrene scaffold mounted on a constrained polyether macrocycle displaying intense excimer fluorescence and highly circularly‐polarized (CP) photoluminescence has been selected for this purpose. The compound displays an ECL dissymmetry factor of about |8×10−3|, which is in good agreement with the corresponding photoluminescence value. This observation is the first step towards the molecular engineering of tailored dyes that can act as both ECL and CP‐ECL reporters for (bio)analysis by bringing a new level of information when dealing with chiral environments. Additionally, it provides an extra dimension to the ECL phenomenon and opens the way to chiral detection and discrimination.

Evolving the Promiscuity of Elizabethkingia meningoseptica Oleate Hydratase for the Regio‐ and Stereoselective Hydration of Oleic Acid Derivatives

By Matthias Engleder, Gernot A. Strohmeier, Hansjörg Weber, Georg Steinkellner, Erich Leitner, Monika Müller, Daniel Mink, Martin Schürmann, Karl Gruber, Harald Pichler from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 17, 2019.

Redefining the substrate spectrum: The highly regio‐ and stereoselective hydration of oleic acid derivatives by an oleate hydratase is possible. The carboxylate of a free fatty acid—previously considered essential—is not mandatory for the conversion, which thus expands hydration biocatalysis beyond inferred restrictions. Abstract The addition of water to non‐activated carbon–carbon double bonds catalyzed by fatty acid hydratases (FAHYs) allows for highly regio‐ and stereoselective oxyfunctionalization of renewable oil feedstock. So far, the applicability of FAHYs has been limited to free fatty acids, mainly owing to the requirement of a carboxylate function for substrate recognition and binding. Herein, we describe for the first time the hydration of oleic acid (OA) derivatives lacking this free carboxylate by the oleate hydratase from Elizabethkingia meningoseptica (OhyA). Molecular docking of OA to the OhyA 3D‐structure and a sequence alignment uncovered conserved amino acid residues at the entrance of the substrate channel as target positions for enzyme engineering. Exchange of selected amino acids gave rise to OhyA variants which showed up to an 18‐fold improved conversion of OA derivatives, while retaining the excellent regio‐ and stereoselectivity in the olefin hydration reaction.

Biredox Eutectic Electrolytes Derived from Organic Redox‐Active Molecules: High‐Energy Storage Systems

By Changkun Zhang, Yumin Qian, Yu Ding, Leyuan Zhang, Xuelin Guo, Yu Zhao, Guihua Yu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 17, 2019.

Busy BEE: A biredox eutectic electrolyte (BEE) is derived from the intermolecular interactions between the redox‐active molecules N‐butylphthalimide and 1,1‐dimethylferrocene. Given the high concentration of active materials, the flow cell based on the BEE delivers stable cycling performance, and high volumetric capacity and power density. The facile and effective strategy has potential for high‐performance nonaqueous redox flow batteries for high‐energy storage systems. Abstract One promising candidate for high‐energy storage systems is the nonaqueous redox flow battery (NARFB). However, their application is limited by low solubility of redox‐active materials and poor performance at high current density. Reported here is a new strategy, a biredox eutectic, as the sole electrolyte for NARFB to achieve a significantly higher concentration of redox‐active materials and enhance the cell performance. Without other auxiliary solvents, the biredox eutectic electrolyte is formed directly by the molecular interactions between two different redox‐active molecules. Such a unique electrolyte possesses high concentration with low viscosity (3.5 m, for N‐butylphthalimide and 1,1‐dimethylferrocene system) and a relatively high working voltage of 1.8 V, enabling high capacity and energy density of NARFB. The resulting high‐performance NARFB demonstrates that the biredox eutectic based strategy is potentially promising for low‐cost and high‐energy storage systems.

MOF‐on‐MOF: Oriented Growth of Multiple Layered Thin Films of Metal–Organic Frameworks

By Ken Ikigaki, Kenji Okada, Yasuaki Tokudome, Takashi Toyao, Paolo Falcaro, Christian J. Doonan, Masahide Takahashi from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 17, 2019.

The precise alignment of multiple layers of metal–organic framework (MOF) thin films, or MOF‐on‐MOF films, over macroscopic length scales is presented. The MOF‐on‐MOF films are fabricated by epitaxially matching the interface. This strategy allows for the synthesis of aligned MOF films that cannot be grown on a Cu(OH)2 surface. Abstract The precise alignment of multiple layers of metal–organic framework (MOF) thin films, or MOF‐on‐MOF films, over macroscopic length scales is presented. The MOF‐on‐MOF films are fabricated by epitaxially matching the interface. The first MOF layer (Cu2(BPDC)2, BPDC=biphenyl‐4,4′‐dicarboxylate) is grown on an oriented Cu(OH)2 film by a “one‐pot” approach. Aligned second (Cu2(BDC)2, BDC=benzene 1,4‐dicarboxylate, or Cu2(BPYDC)2, BPYDC=2,2′‐bipyridine‐5,5′‐dicarboxylate) MOF layers can be deposited using liquid‐phase epitaxy. The co‐orientation of the MOF films is confirmed by X‐ray diffraction. Importantly, our strategy allows for the synthesis of aligned MOF films, for example, Cu2(BPYDC)2, that cannot be grown on a Cu(OH)2 surface. We show that aligned MOF films furnished with Ag nanoparticles show a unique anisotropic plasmon resonance. Our MOF‐on‐MOF approach expands the chemistry of heteroepitaxially oriented MOF films and provides a new toolbox for multifunctional porous coatings.

Cyclohexanehexone with Ultrahigh Capacity as Cathode Materials for Lithium‐Ion Batteries

By Yong Lu, Xuesen Hou, Licheng Miao, Lin Li, Ruijuan Shi, Luojia Liu, Jun Chen from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 17, 2019.

Six pack: Cyclohexanehexone (C6O6) is synthesized and applied as a cathode material in lithium‐ion batteries, exhibiting an ultrahigh capacity of 902 mA h g−1 (1533 Wh kg−1). As a result of its limited dissolution, C6O6 shows relatively good cycling stability (a capacity retention of 82 % after 100 cycles at 50 mA g−1) in ionic liquid electrolyte. Abstract Organic carbonyl compounds show potential as cathode materials for lithium‐ion batteries (LIBs) but the limited capacities (

Direct Non‐oxidative Methane Conversion in a Millisecond Catalytic Wall Reactor

By Su Cheun Oh, Emily Schulman, Junyan Zhang, Jiufeng Fan, Ying Pan, Jianqiang Meng, Dongxia Liu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 17, 2019.

Wall to wall: The upgrade of CH4 by direct non‐oxidative methane conversion is facilitated by a Fe/SiO2 millisecond catalytic wall reactor. The reactor design results in stable methane conversion, C2+ selectivity, coke yield, and long‐term durability. Abstract Direct non‐oxidative methane conversion (DNMC) has been recognized as a single‐step technology that directly converts methane into olefins and higher hydrocarbons. High reaction temperature and low catalyst durability, resulting from the endothermic reaction and coke deposition, are two main challenges. We show that a millisecond catalytic wall reactor enables stable methane conversion, C2+ selectivity, coke yield, and long‐term durability. These effects originate from initiation of the DNMC on a reactor wall and maintenance of the reaction by gas‐phase chemistry within the reactor compartment. The results obtained under various temperatures and gas flow rates form a basis for optimizing the process towards lighter C2 or heavier aromatic products. A process simulation was done by Aspen Plus to understand the practical implications of this reactor in DNMC. High carbon and thermal efficiencies and low cost of the reactor materials are realized, indicating the technoeconomic viability of this DNMC technology.

High Accuracy Protein Structures from Minimal Sparse Paramagnetic Solid‐State NMR Restraints

By Alberto Perez, Kari Gaalswyk, Christopher P. Jaroniec, Justin L. MacCallum from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 17, 2019.

Within a single day: Combining the Modeling Employing Limited Data (MELD) framework with sparse solid‐state NMR experiments exploiting the paramagnetic resonance enhancement effect can produce accurate protein structures from sparse datasets. Abstract There is a pressing need for new computational tools to integrate data from diverse experimental approaches in structural biology. We present a strategy that combines sparse paramagnetic solid‐state NMR restraints with physics‐based atomistic simulations. Our approach explicitly accounts for uncertainty in the interpretation of experimental data through the use of a semi‐quantitative mapping between the data and the restraint energy that is calibrated by extensive simulations. We apply our approach to solid‐state NMR data for the model protein GB1 labeled with Cu2+‐EDTA at six different sites. We are able to determine the structure to 0.9 Å accuracy within a single day of computation on a GPU cluster. We further show that in some cases, the data from only a single paramagnetic tag are sufficient for accurate folding.

Isolated Diatomic Ni‐Fe Metal–Nitrogen Sites for Synergistic Electroreduction of CO2

By Wenhao Ren, Xin Tan, Wanfeng Yang, Chen Jia, Shumao Xu, Kaixue Wang, Sean C. Smith, Chuan Zhao from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 17, 2019.

The collaborative coordination of CO at diatomic Ni‐Fe sites anchored on nitrogenated carbon is the key to a new nickel–iron catalyst developed for the electroreduction of CO2. The catalyst achieves a high Faradaic efficiency of 98 % at −0.7 V, outstanding turnover frequency, and robust electrode durability. Abstract Polynary single‐atom structures can combine the advantages of homogeneous and heterogeneous catalysts while providing synergistic functions based on different molecules and their interfaces. However, the fabrication and identification of such an active‐site prototype remain elusive. Here we report isolated diatomic Ni‐Fe sites anchored on nitrogenated carbon as an efficient electrocatalyst for CO2 reduction. The catalyst exhibits high selectivity with CO Faradaic efficiency above 90 % over a wide potential range from −0.5 to −0.9 V (98 % at −0.7 V), and robust durability, retaining 99 % of its initial selectivity after 30 hours of electrolysis. Density functional theory studies reveal that the neighboring Ni‐Fe centers not only function in synergy to decrease the reaction barrier for the formation of COOH* and desorption of CO, but also undergo distinct structural evolution into a CO‐adsorbed moiety upon CO2 uptake.

Quantifying Chemical Structure and Machine‐Learned Atomic Energies in Amorphous and Liquid Silicon

By Noam Bernstein, Bishal Bhattarai, Gábor Csányi, David A. Drabold, Stephen R. Elliott, Volker L. Deringer from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 17, 2019.

In silico(n): Machine learning makes it possible to quantify the local structure in amorphous solids and the local atomically‐resolved energy at the same time, as demonstrated here for an ensemble of amorphous and liquid Si structures. Abstract Amorphous materials are being described by increasingly powerful computer simulations, but new approaches are still needed to fully understand their intricate atomic structures. Here, we show how machine‐learning‐based techniques can give new, quantitative chemical insight into the atomic‐scale structure of amorphous silicon (a‐Si). We combine a quantitative description of the nearest‐ and next‐nearest‐neighbor structure with a quantitative description of local stability. The analysis is applied to an ensemble of a‐Si networks in which we tailor the degree of ordering by varying the quench rates down to 1010 K s−1. Our approach associates coordination defects in a‐Si with distinct stability regions and it has also been applied to liquid Si, where it traces a clear‐cut transition in local energies during vitrification. The method is straightforward and inexpensive to apply, and therefore expected to have more general significance for developing a quantitative understanding of liquid and amorphous states of matter.

Phase‐Controlled Synthesis of Monolayer Ternary Telluride with a Random Local Displacement of Tellurium Atoms

By Bijun Tang, Jiadong Zhou, Pingping Sun, Xiaowei Wang, Lichun Bai, Jiadong Dan, Jiefu Yang, Kun Zhou, Xiaoxu Zhao, Stephen J. Pennycook, Zheng Liu from Wiley: Advanced Materials: Table of Contents. Published on Apr 17, 2019.

2D ternary transitional metal dichalcogenides have been spotlighted recently. A one‐step chemical vapor deposition (CVD) method to synthesize monolayer WTe2xS2(1−x) alloys is reported. By tuning the ratio of chalcogen precursors and H2 flow rate, both semiconducting 1H and metallic 1T´ structures can be obtained. Local displacement of Te atoms from the original 1H lattice sites is also observed and studied. Abstract Alloying 2D transition metal dichalcogenides has opened up new opportunities for bandgap engineering and phase control. Developing a simple and scalable synthetic route is therefore essential to explore the full potential of these alloys with tunable optical and electrical properties. Here, the direct synthesis of monolayer WTe2xS2(1−x) alloys via one‐step chemical vapor deposition (CVD) is demonstrated. The WTe2xS2(1−x) alloys exhibit two distinct phases (1H semiconducting and 1T ´ metallic) under different chemical compositions, which can be controlled by the ratio of chalcogen precursors as well as the H2 flow rate. Atomic‐resolution scanning transmission electron microscopy–annular dark field (STEM‐ADF) imaging reveals the atomic structure of as‐formed 1H and 1T ´ alloys. Unlike the commonly observed displacement of metal atoms in the 1T ´ phase, local displacement of Te atoms from original 1H lattice sites is discovered by combined STEM‐ADF imaging and ab initio molecular dynamics calculations. The structure distortion provides new insights into the structure formation of alloys. This generic synthetic approach is also demonstrated for other telluride‐based ternary monolayers such as WTe2xSe2(1−x) single crystals.

Quasicrystal Photonic Metasurfaces for Radiation Controlling of Second Harmonic Generation

By Yutao Tang, Junhong Deng, King Fai Li, Mingke Jin, Jack Ng, Guixin Li from Wiley: Advanced Materials: Table of Contents. Published on Apr 17, 2019.

Nonlinear optical quasicrystal metasurfaces are designed based on the geometric‐phase‐controlled plasmonic meta‐atoms. The far‐field radiation behavior of second harmonic generation waves are determined by both the tiling schemes of quasicrystal metasurfaces and the local symmetry of meta‐atoms they consist of. The proposed concept may open new avenues for designing nonlinear optical sources with metasurface crystals. Abstract Photonic metasurfaces, a kind of 2D structured medium, represent a novel platform to manipulate the propagation of light at subwavelength scale. In linear optical regime, many interesting topics such as planar meta‐lenses, metasurface optical holography, and so on have been widely investigated. Recently, metasurfaces have gone into the nonlinear optical regime. While it is recognized that the local symmetry of the meta‐atoms plays a vital role in determining the polarization, phase, and intensity of the nonlinear waves, much less attention has been paid to the global symmetry of the nonlinear metasurfaces. According to the Penrose tiling and the newly proposed hexagonal quasicrystalline tiling, nonlinear optical quasicrystal metasurfaces are designed and fabricated based on the geometric‐phase‐controlled plasmonic meta‐atoms with local rotational symmetry. It is found that the far‐field radiation behavior of second harmonic generation waves are determined by both the tiling schemes of quasicrystal metasurfaces and the local symmetry of meta‐atoms they consist of. The proposed concept may open new avenues for designing nonlinear optical sources with metasurface crystals.

Thu 23 May 16:00: Colloids in confinement: From two-dimensional melting to membrane transport

From All Talks (aka the CURE list). Published on Apr 17, 2019.

Colloids in confinement: From two-dimensional melting to membrane transport

Colloidal suspensions have long been regarded as an excellent source of experimental model systems, due to their large size, slow timescales and inherent tunability. In this talk, I will discuss two examples of how complex natural phenomena can be studied by building systems in which colloids are confined to one- and two-dimensional geometries. In particular, in 2D, we have established the full phase behaviour of the simplest two-dimensional system, hard disks, by studying the structure and dynamics of colloidal monolayers. In 1D, we can gain an insight into transport through porous membranes by studying colloidal dynamics in microscale channels with tuneable potential landscapes.

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Precise Surface Engineering of Cathode Materials for Improved Stability of Lithium‐Ion Batteries

By Yuan Liu, Xi‐Jie Lin, Yong‐Gang Sun, Yan‐Song Xu, Bao‐Bao Chang, Chun‐Tai Liu, An‐Min Cao, Li‐Jun Wan from Wiley: Small: Table of Contents. Published on Apr 17, 2019.

Surface modification of cathode materials is indispensable to stabilize the cathode–electrolyte interface. The synthesis strategies suited for the creation of a uniform shell with thickness controlled at nanometer accuracy are introduced, with the corresponding formation mechanisms discussed in detail, in order to present the synthesis–structure–performance relationship to facilitate understanding of the stability of high‐energy electrode materials. Abstract As lithium‐ion batteries continue to climb to even higher energy density, they meanwhile cause serious concerns on their stability and reliability during operation. To make sure the electrode materials, particularly cathode materials, are stable upon extended cycles, surface modification becomes indispensable to minimize the undesirable side reaction at the electrolyte–cathode interface, which is known as a critical factor to jeopardizing the electrode performance. This Review is targeted at a precise surface control of cathode materials with focus on the synthetic strategies suitable for a maximized surface protection ensured by a uniform and conformal surface coating. Detailed discussions are taken on the formation mechanism of the designated surface species achieved by either wet‐chemistry routes or instrumental ones, with attention to the optimized electrochemical performance as a result of the surface control, accordingly drawing a clear image to describe the synthesis–structure–performance relationship to facilitate further understanding of functional electrode materials. Finally, perspectives regarding the most promising and/or most urgent developments for the surface control of high‐energy cathode materials are provided.

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 Apr 17, 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.

Smart Microcapsules with Molecular Polarity‐ and Temperature‐Dependent Permeability

By Ji‐Won Kim, Sang Seok Lee, Jinho Park, Minhee Ku, Jaemoon Yang, Shin‐Hyun Kim from Wiley: Small: Table of Contents. Published on Apr 17, 2019.

Smart microcapsules are designed to have molecular polarity‐ and temperature‐dependent permeability using microfluidic technology. The shell is composed of a polymeric framework whose void is filled with phase change material (PCM). This enables the selective permeation of molecules that are soluble in the molten PCM and the rate of permeation is adjustable with partition coefficient and temperature. Abstract Microcapsules with molecule‐selective permeation are appealing as microreactors, capsule‐type sensors, drug and cell carriers, and artificial cells. To accomplish molecular size‐ and charge‐selective permeation, regular size of pores and surface charges have been formed in the membranes. However, it remains an important challenge to provide advanced regulation of transmembrane transport. Here, smart microcapsules are designed that provide molecular polarity‐ and temperature‐dependent permeability. With capillary microfluidic devices, water‐in‐oil‐in‐water (W/O/W) double‐emulsion drops are prepared, which serve as templates to produce microcapsules. The oil shell is composed of two monomers and dodecanol, which turns to a polymeric framework whose continuous voids are filled with dodecanol upon photopolymerization. One of the monomers provides mechanical stability of the framework, whereas the other serves as a compatibilizer between growing polymer and dodecanol, preventing macrophase separation. Above melting point of dodecanol, molecules that are soluble in the molten dodecanol are selectively allowed to diffuse across the shell, where the rate of transmembrane transport is strongly influenced by partition coefficient. The rate is drastically lowered for temperatures below the melting point. This molecular polarity‐ and temperature‐dependent permeability renders the microcapsules potentially useful as drug carriers for triggered release and contamination‐free microreactors and microsensors.

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 Apr 17, 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.

Responsive Porous Microcarriers With Controllable Oxygen Delivery for Wound Healing

By Yuxiao Liu, Xin Zhao, Cheng Zhao, Hui Zhang, Yuanjin Zhao from Wiley: Small: Table of Contents. Published on Apr 17, 2019.

Responsive porous microcarriers are derived from GelMa inverse opal particles integrated with oxygen‐carrying protein hemoglobin and molybdenum disulfide quantum dots. These designed microcarriers can deliver oxygen photo‐controllably through near‐infrared radiation, and they are demonstrated to be able to maintain cell survival in a hypoxic environment and promote wound healing successfully. Abstract Microcarriers with oxygen‐delivering capacity have attracted increasing interest in the field of tissue regeneration. Here, a kind of molybdenum disulfide quantum dots (MoS2 QDs) integrated responsive porous microcarriers with controllable oxygen‐delivering ability for wound healing is presented. The specific gelatin methacryloyl (GelMa) porous microcarriers are derived from inverse opal microparticles which can be decorated with the oxygen‐carrying protein hemoglobin. Because of their characteristic porous structure, interconnected nanochannels, and excellent biocompatibility, the resultant microcarriers could carry oxygen extensively and provide support for tissue repair physically and biologically. Besides, since the typical photothermal effect of 2D materials and their derived 2D QDs, the inverse opal particles integrated with MoS2 QDs are imparted with photo‐responsive capacity, which makes them able to release oxygen photo‐controllably. It is demonstrated that the designed microcarriers can promote the repair of abdominal wall defects effectively with their multifunctional features. These remarkable properties point to the potential value of the microcarriers in wound healing and tissue engineering.

Peptide‐Directed DNA‐Templated Protein Labelling for The Assembly of a Pseudo‐IgM

By Thorbjørn B Nielsen, Rasmus P Thomsen, Michael R Mortensen, Jørgen Kjems, Per F Nielsen, Thomas E Nielsen, Anne Louise Bank Kodal, Emiliano Clo, Kurt Vesterager Gothelf from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 17, 2019.

The development of methods for conjugation of DNA to proteins is of high relevance for integration of protein function and DNA structures. Here, we demonstrate that protein binding peptides can direct a DNA‐templated reaction, furnishing DNA‐protein conjugates selectively with one DNA label. Quantitative conversion of oligonucleotides is achieved at low stoichiometries and the reaction can be performed in complex biological matrixes such as cell lysates. Further, we have applied a star‐like pentameric DNA nanostructure to assemble five DNA‐Rituximab conjugates, made by our reported method, into a pseudo‐IgM antibody structure that was subsequently characterized by negative stain transmission electron microscopy (nsTEM) analysis.

Scalable biosynthesis of the seaweed neurochemical kainic acid

By Jonathan R. Chekan, Shaun M. K. McKinnie, Malia L. Moore, Shane G. Poplawski, Todd P. Michael, Bradley S. Moore from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 17, 2019.

Kainic acid, the flagship member of the kainoid family of natural neurochemicals, is a widely used neuropharmacological agent that helped unravel the key role of ionotropic glutamate receptors, including the kainate receptor, in the central nervous system. Worldwide shortages of this seaweed natural product in 2000 prompted numerous chemical syntheses that now number in excess of 70, including scalable preparations with as few as six‐steps. Herein we report the discovery and characterization of the concise two‐enzyme biosynthetic pathway to kainic acid from L‐glutamic acid and dimethylallyl pyrophosphate in red macroalgae and show that the biosynthetic genes are co‐clustered in genomes of Digenea simplex and the edible Palmaria palmata. Moreover, we applied a key biosynthetic α‐ketoglutarate‐dependent dioxygenase enzyme in a biotransformation methodology to efficiently construct kainic acid on the gram scale. This study establishes both the feasibility of mining seaweed genomes for their biotechnological prowess and the applicability of the genes as biocatalysts in the synthesis of fine chemicals.

Asymmetric Synthesis of Alkyl Fluorides: Hydrogenation of Fluorinated Olefins

By Sudipta Ponra, Jianping Yang, Sutthichat Kerdphon, Pher G. Andersson from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 17, 2019.

The development of new general methods for the synthesis of chiral fluorine‐containing molecules is important for several scientific disciplines. By the Ir‐catalyzed asymmetric hydrogenation of tri‐substituted vinyl‐fluorides, a straightforward preparation of chiral organofluorine molecules is disclosed. The developed method represents a catalytic asymmetric process that enables the synthesis of chiral fluorine molecules with or without carbonyl framework. Owing to the tunable steric and electronic properties of azabicyclo iridium‐thiazole‐phosphine catalyst, this stereoselective reaction could be optimized and found compatible with various aromatic, aliphatic and heterocyclic systems with a variety of functional groups providing the highly desirable product in excellent yield and enantioselectivities.

Valence‐to‐Core X‐ray Emission Spectroscopy as a Probe of O‐O Bond Activation in Cu2O2 complexes

By George Cutsail, Nicole Gagnon, Andrew Spaeth, William Tolman, Serena DeBeer from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 17, 2019.

Valence‐to‐Core (VtC) X‐ray emission spectroscopy (XES) was used to directly detect the presence of an O‐O bond in a complex comprising the [Cu2(II)(µ‐η2:η2‐O2)]2+ core relative to its isomer with a cleaved O‐O bond having a [Cu(III)2(µ‐O)2]2+ unit. The experimental studies are complemented by DFT calculations, which show that the unique VtC XES feature of the [Cu2(II)(µ‐η2:η2‐O2)]2+core corresponds to the copper stabilized in‐plane 2p π peroxo molecular orbital. These calculations illustrate the sensitivity of VtC XES for probing the extent of O‐O bond activation in µ‐η2:η2‐O2 species and highlight the potential of this method for time‐resolved studies of reaction mechanisms.

Optical multiplexed bioassays improve biomedical diagnostics

By Fan Zhang, Yong Fan, Shangfeng Wang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 17, 2019.

Conventional analytical methods based on single detection to determine one disease marker are usually not sufficient and accurate because the progression of disease generally involves multiple chemicals and biomolecules. The drive for simultaneous analysis of multiple targets, which plays a key role in both basic biomedical research and clinical applications, demands the development of multiplexed bioassays with high‐throughput. In this minireview, we systematically summarize the recent progress of optical multiplexed analytical techniques to improve biomedical diagnostics, in which fluorescence and surface enhanced Raman scattering (SERS) with distinctive optical features are chosen as the main readout signals. Taking advantage of the multiplexed strategies in the biomedical field, a selection of recent contributions from biosensing of multiple chemicals and multicolor cellular tracking to in vivo multiplexed bioimaging are highlighted. Finally, we frame the future outlook of challenges and opportunities of multiplexed bioanalysis.

Sequential C−H Borylation and N‐Demethylation of 1,1′‐Biphenylamines: Alternative Route to Polycyclic BN‐Heteroarenes

By Jianbo Zhang, Hoimin Jung, Dongwook Kim, Sehoon Park, Sukbok Chang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 17, 2019.

A two‐step borane‐mediated C−H borylation and N‐demethylation of biphenylamines has been developed to provide a range of new BN‐heteroarenes with distinct photophysical and structural properties. The unprecedented intramolecular N‐demethylation of borane‐amine intermediates was enabled by a B(C6F5)3 catalyst, albeit at high temperature. The procedure features transition metal free conditions to liberate environmentally benign byproducts (H2 and CH4) by a mechanistically intriguing ionic pathway. Abstract Described herein is an unprecedented access to BN‐polyaromatic compounds from 1,1′‐biphenylamines by sequential borane‐mediated C(sp2)−H borylation and intramolecular N‐demethylation. The conveniently in situ generated Piers’ borane from a borinic acid reacts with a series of N,N‐dimethyl‐1,1′‐biphenyl‐2‐amines in the presence of PhSiH3 to afford six‐membered amine‐borane adducts bearing a C(sp2)−B bond at the C2′‐position. These species undergo an intramolecular N‐demethylation with a B(C6F5)3 catalyst to provide BN‐isosteres of polyaromatics. According to computational studies, a stepwise ionic pathway is suggested. Photophysical characters of the resultant BN‐heteroarenes shown them to be distinctive from those of all‐carbon analogues.

β‐Selective Aroylation of Activated Alkenes by Photoredox Catalysis

By Zhen Lei, Arghya Banerjee, Elena Kusevska, Eric Rizzo, Peng Liu, Ming‐Yu Ngai from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 17, 2019.

Compatible: A photocatalytic β‐selective alkene aroylation, using readily available aroyl chlorides and activated alkenes, was developed. The synthetic utility of the reaction is highlighted by its broad functional‐group compatibility and high levels of chemo‐ and regioselectivity. The reaction is amenable to late‐stage functionalization of complex molecules including derivatives of sugars, peptides, natural products, nucleosides, and commercially available drugs. Abstract Late‐stage synthesis of α,β‐unsaturated aryl ketones remains an unmet challenge in organic synthesis. Reported herein is a photocatalytic non‐chain‐radical aroyl chlorination of alkenes by a 1,3‐chlorine atom shift to form β‐chloroketones as masked enones that liberate the desired enones upon workup. This strategy suppresses side reactions of the enone products. The reaction tolerates a wide array of functional groups and complex molecules including derivatives of peptides, sugars, natural products, nucleosides, and marketed drugs. Notably, addition of 2,6‐di‐tert‐butyl‐4‐methyl‐pyridine enhances the quantum yield and efficiency of the cross‐coupling reaction. Experimental and computational studies suggest a mechanism involving PCET, formation and reaction of an α‐chloro‐α‐hydroxy benzyl radical, and 1,3‐chlorine atom shift.

Spontaneous Resolution by Crystallization of an Octanuclear Iron(III) Complex Using Only Racemic Reagents

By Konstantinos A. Lazarou, Karilys González‐Nieves, Indranil Chakraborty, Raphael G. Raptis from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 17, 2019.

Pair off: Only racemic reagents are used to achieve the spontaneous resolution, by crystallization, of the P and M enantiomers of an [Fe8] complex having T symmetry. During crystallization the (S)‐ and (R)‐phenolates coordinate selectively to the M and P complexes, respectively. Abstract The P and M enantiomers of the octanuclear [Fe8(μ4‐O)4(μ‐4‐Cl‐pz)12Cl4] complex, having T symmetry, were resolved by temporary substitution of chloride ligands by racemic 4‐sBu‐phenolates and subsequent crystallization, where the (S)‐ and (R)‐phenolates coordinate selectively to the M and P complexes, respectively. The complexes were characterized by circular dichroism analysis and X‐ray structure determination. This work constitutes a rare example of enantiomeric recognition resulting in spontaneous resolution upon crystallization.

Globular Polymer Grafts Require a Critical Size for Efficient Molecular Sieving of Enzyme Substrates

By Stuart A. McNelles, Victoria M. Marando, Alex Adronov from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 17, 2019.

Size matters: High‐generation bis‐MPA dendrons functionalized with a strained cyclooctyne at the core were prepared and conjugated to α‐chymotrypsin through SPAAC. Upon reaching a critical generation of dendron, the resulting conjugates were nearly inactive against macromolecular substrates while retaining full activity against small molecules. Abstract A series of 2,2‐bis(hydroxymethyl)propionic acid dendrons of generation 2 through 8 having a strained cyclooctyne at the core and hydroxy groups at the periphery were prepared by a divergent method and used to functionalize azide‐decorated α‐chymotrypsin. The ability of the appended dendrons to selectively block enzyme activity (through a molecular sieving effect) was investigated using a small molecule substrate (benzoyl‐l‐tyrosine p‐nitroanilide), as well as two proteins of different size (casein and bovine serum albumin). Additionally, the ability of dendrons to block complexation with a chymotrypsin antagonist, α‐antichymotrypsin, was investigated, and it was found that the dendron coating effectively prevented inhibition by this antagonist. We found that a critical generation is required to achieve efficient sieving with bis‐MPA dendrons, which illustrates the importance of macromolecular architecture and size in the shielding of proteins.

Bioactive Patchy Nanoparticles with Compartmentalized Cargoes for Simultaneous and Trackable Delivery

By Chin Ken Wong, Fan Chen, Andreas Walther, Martina H. Stenzel from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 17, 2019.

Easy as ABC: There is increasing interest in ABC triblock terpolymers to assemble multicompartment patchy nanoparticles (NPs) bottom‐up. Now, two chemically distinct molecules are segregated in either the patches or core compartment of patchy NPs that bear a sugar corona. Bioactive patchy NPs containing compartmentalized cargoes are promising for drug delivery with real‐time release monitoring. Abstract Recent years have seen an increased interest in the use of ABC triblock terpolymers to bottom‐up assemble multicompartment patchy nanoparticles. Despite these experimental and theoretical efforts, the applications of polymer‐based patchy nanoparticles remain rather limited. One of the major challenges that eclipses their potential is the lack of knowledge to selectively encapsulate cargoes within different compartments that are separated in the nanometer length scale. Here, strategies are reported to segregate two chemically distinct molecules in either the patches or core compartment of patchy nanoparticles that bear a (bioactive) sugar corona. The potential use of these bioactive patchy nanoparticles containing compartmentalized cargoes for simultaneous drug delivery with real‐time release monitoring capabilities is further demonstrated.

DECHEMA Prize for Dörthe Rother/DECHEMA Early‐Career Researcher Prize for Pierre Stallforth/NCK Prize for David Margulies

By from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 17, 2019.

Chemistry of Layered Pnictogens: Phosphorus, Arsenic, Antimony, and Bismuth

By Jiri Sturala, Zdenek Sofer, Martin Pumera from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 17, 2019.

2D pnictogens: Recent advances in exfoliation and modification of layered materials from Group 15 elements are discussed in this Minireview. Abstract Materials with few layers have been subjected to extensive research for the last few decades owing to their remarkable properties as for example catalysts, optical and electrical devices, or sensors. The properties and electronic structure of these materials can be tailored by the introduction of substituents. In the case of more reactive species, the modification also can improve stability, which is also an important factor with respect to device fabrication. This review focuses on monoelemental layered materials of Group 15 elements (pnictogens) and in particular their modification, leading to better ambient stability and/or different properties by covalent and non‐covalent modifications. The future modification and application of pnictogens are outlined.

Promoting Frustrated Lewis Pairs for Heterogeneous Chemoselective Hydrogenation via the Tailored Pore Environment within Metal–Organic Frameworks

By Zheng Niu, Weijie Zhang, Pui Ching Lan, Briana Aguila, Shengqian Ma from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 17, 2019.

FLP in MOFs: Frustrated Lewis pairs (FLPs) anchored in a metal–organic framework (MOF) that features activation groups including open metal sites and hydroxy groups can serve as a highly efficient heterogeneous catalyst to selectively reduce the imine bond in α,β‐unsaturated imine substrates to afford unsaturated amine compounds by directly using hydrogen gas under moderate pressure. Abstract Frustrated Lewis pairs (FLPs) have recently been advanced as efficient metal‐free catalysts for catalytic hydrogenation, but their performance in chemoselective hydrogenation, particularly in heterogeneous systems, has not yet been achieved. Herein, we demonstrate that, via tailoring the pore environment within metal–organic frameworks (MOFs), FLPs not only can be stabilized but also can develop interesting performance in the chemoselective hydrogenation of α,β‐unsaturated organic compounds, which cannot be achieved with FLPs in a homogeneous system. Using hydrogen gas under moderate pressure, the FLP anchored within a MOF that features open metal sites and hydroxy groups on the pore walls can serve as a highly efficient heterogeneous catalyst to selectively reduce the imine bond in α,β‐unsaturated imine substrates to afford unsaturated amine compounds.

Isolation of a Diylide‐Stabilized Stannylene and Germylene: Enhanced Donor Strength through Coplanar Lone Pair Alignment

By Chandrajeet Mohapatra, Lennart T. Scharf, Thorsten Scherpf, Bert Mallick, Kai‐Stephan Feichtner, Christopher Schwarz, Viktoria H. Gessner from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 17, 2019.

Boost me up! The first diylide‐substituted germylene and stannylene Y2Ge and Y2Sn were prepared by salt metathesis using a metalated ylide. The tetrylenes exhibit unusual structures in which the three lone pairs at the adjacent C‐E‐C atoms are coplanarly arranged. This bonding situation results in a remarkable increase of the HOMO energy and the donor strength, thus making these tetrylenes donors as strong as cyclic alkyl(amino)carbenes. Abstract The preparation of the first stable diylide‐substituted stannylene and germylene (Y2E, with E=Ge, Sn and Y=[PPh3‐C‐SO2Tol]−) is reported. The synthesis is easily accomplished in one step from the sulfonyl‐substituted metalated ylide YNa and the corresponding ECl2 precursors. Y2Ge and Y2Sn exhibit unusual structures in the solid state and in solution, in which the three adjacent lone pairs in the C‐E‐C linkage are arranged coplanar to each other. As shown by DFT studies, this bonding situation is preferred over the typical π‐donation from the ligands into the empty p‐orbital at the metal due to the strong anion‐stabilizing ability of the sulfonyl groups in the ylide backbone and their additional coordination to the metal. The alignment of the three lone pairs leads to a remarkable boost of the HOMO energy and thus of the donor strengths of the tetrylenes. Hence, Y2Ge and Y2Sn become stronger donors than their diamino or diaryl congeners and comparable to cyclic alkyl(amino)carbenes. First reactivity studies confirm the high reactivity of Y2Ge and Y2Sn, which for example undergo an intramolecular C−H activation reaction via metal–ligand cooperation.

Nanohoop Rotaxanes from Active Metal Template Syntheses and Their Potential in Sensing Applications

By Jeff M. Van Raden, Brittany M. White, Lev N. Zakharov, Ramesh Jasti from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 17, 2019.

Two high‐yielding strategies are used to prepare nanohoop [2]rotaxanes, which owing to the π‐rich macrocycle are highly emissive. Metal coordination leads to molecular shuttling and modulates fluorescence in both organic and aqueous conditions. A self‐immolative [2]rotaxane was designed that self‐destructs in the presence of an analyte, eliciting a strong fluorescent turn‐on response, serving as proof‐of‐concept for a molecular sensor. Abstract The unique optoelectronic properties and smooth, rigid pores of macrocycles with radially oriented π systems render them fascinating candidates for the design of novel mechanically interlocked molecules with new properties. Two high‐yielding strategies are used to prepare nanohoop [2]rotaxanes, which owing to the π‐rich macrocycle are highly emissive. Then, metal coordination, an intrinsic property afforded by the resulting mechanical bond, can lead to molecular shuttling as well as modulate the observed fluorescence in both organic and aqueous conditions. Inspired by these findings, a self‐immolative [2]rotaxane was then designed that self‐destructs in the presence of an analyte, eliciting a strong fluorescent turn‐on response, serving as proof‐of‐concept for a new type of molecular sensing material. More broadly, this work highlights the conceptual advantages of combining compact π‐rich macrocyclic frameworks with mechanical bonds formed via active‐template syntheses.

A Peptide‐Induced Self‐Cleavage Reaction Initiates the Activation of Tyrosinase

By Ioannis Kampatsikas, Aleksandar Bijelic, Matthias Pretzler, Annette Rompel from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 17, 2019.

Activation through self‐cleavage: The structural and biochemical characterization of polyphenol oxidase 1 (PPO1) from Malus domestica (MdPPO1) reveals self‐cleavage as an activation route for plant PPOs. A self‐cleavage‐inducing peptide was identified that controls the proteolytic activation process and also works as an activator for other PPOs. Abstract The conversion of inactive pro‐polyphenol oxidases (pro‐PPOs) into the active enzyme results from the proteolytic cleavage of its C‐terminal domain. Herein, a peptide‐mediated cleavage process that activates pro‐MdPPO1 (Malus domestica) is reported. Mass spectrometry, mutagenesis studies, and X‐ray crystal‐structure analysis of pro‐MdPPO1 (1.35 Å) and two separated C‐terminal domains, one obtained upon self‐cleavage of pro‐MdPPO1 and the other one produced independently, were applied to study the observed self‐cleavage. The sequence Lys 355–Val 370 located in the linker between the active and the C‐terminal domain is indispensable for the self‐cleavage. Partial introduction (Lys 352–Ala 360) of this peptide into the sequence of two other PPOs, MdPPO2 and aurone synthase (CgAUS1), triggered self‐cleavage in the resulting mutants. This is the first experimental proof of a self‐cleavage‐inducing peptide in PPOs, unveiling a new mode of activation for this enzyme class that is independent of any external protease.

High Electron Mobility of Amorphous Red Phosphorus Thin Films

By Pedro E. M. Amaral, Glen P. Nieman, Gregory R. Schwenk, Hao Jing, Raymond Zhang, Elizabeth B. Cerkez, Daniel Strongin, Hai‐Feng Ji from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 17, 2019.

One alternative to black phosphorus (BP) is red phosphorus (RP), which is much more affordable and easier to process. Through field‐effect transistors (FET) measurements it is demonstrated that amorphous red phosphorus (a‐RP) films are semiconductive with a high mobility of 387 cm2 V−1 s−1 and a current switching ratio of circa 103, which is comparable to the electronic characteristics previously reported for BP. Abstract Black phosphorus (BP) has been gathering great attention for its electronic and optoelectronic applications due to its high electron mobility and high ION/OFF current switching ratio. The limitations of this material include its low synthetic yield and high cost. One alternative to BP is another type of phosphorus allotrope, red phosphorus (RP), which is much more affordable and easier to process. Although RP has been widely used in industry for hundreds of years and considered as an insulating material, in this study, we demonstrate through field‐effect transistors (FET) measurements that amorphous red phosphorus (a‐RP) films are semiconductive with a high mobility of 387 cm2 V−1 s−1 and a current switching ratio of ≈103, which is comparable to the electronic characteristics previously reported for BP. The films were produced via a thermal evaporation method or a facile drop‐casting approach onto Si/SiO2 substrates. We also report a study of the oxidation process of the films over time and a method to stabilize the films via doping a‐RP with metal oxides. The doped films retain stability for one thousand I–V cycles, with no signs of degradation.

Metal Phosphorous Trichalcogenides (MPCh3): From Synthesis to Contemporary Energy Challenges

By Rui Gusmão, Zdenek Sofer, Martin Pumera from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 17, 2019.

MPCh3 player: A new era for metal phosphorous trichalcogenides (MPCh3), a distinctive class of 2D layered materials, first synthesized in the late 1800s, is beginning. With an unusual intercalation behavior, MPCh3 were intensively studied in the 1970s for lithium batteries. Presently rediscovered as 2D nanomaterial for water splitting catalysis and energy storage applications. Abstract Owing to their unique physical and chemical properties, layered two‐dimensional (2D) materials have been established as the most significant topic in materials science for the current decade. This includes layers comprising mono‐element (graphene, phosphorene), di‐element (metal dichalcogenides), and even multi‐element. A distinctive class of 2D layered materials is the metal phosphorous trichalcogenides (MPCh3, Ch=S, Se), first synthesized in the late 1800s. Having an unusual intercalation behavior, MPCh3 were intensively studied in the 1970s for their magnetic properties and as secondary electrodes in lithium batteries, but fell from scrutiny until very recently, being 2D nanomaterials. Based on their synthesis and most significant properties, the present surge of reports related to water‐splitting catalysis and energy storage are discussed in detail. This Minireview is intended as a baseline for the anticipated new wave of researchers who aim to explore these 2D layered materials for their electrochemical energy applications.

Minimizing the Entropy Penalty for Ligand Binding: Lessons from the Molecular Recognition of the Histo Blood‐Group Antigens by Human Galectin‐3

By Ana Gimeno, Sandra Delgado, Pablo Valverde, Sara Bertuzzi, Manuel Alvaro Berbís, Javier Echavarren, Alessandra Lacetera, Sonsoles Martín‐Santamaría, Avadhesha Surolia, Francisco Javier Cañada, Jesus Jiménez‐Barbero, Ana Ardá from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 17, 2019.

Conformational preorganization of the natural A/B blood‐group antigens is the origin of the high‐affinity interaction with human galectin‐3, a lectin of increasing biomedical interest. A combination of structural techniques shows that the fucose residue does not participates in direct contacts with the protein, however it modulates the kinetics and thermodynamics of the molecular recognition process. Abstract Ligand conformational entropy plays an important role in carbohydrate recognition events. Glycans are characterized by intrinsic flexibility around the glycosidic linkages, thus in most cases, loss of conformational entropy of the sugar upon complex formation strongly affects the entropy of the binding process. By employing a multidisciplinary approach combining structural, conformational, binding energy, and kinetic information, we investigated the role of conformational entropy in the recognition of the histo blood‐group antigens A and B by human galectin‐3, a lectin of biomedical interest. We show that these rigid natural antigens are pre‐organized ligands for hGal‐3, and that restriction of the conformational flexibility by the branched fucose (Fuc) residue modulates the thermodynamics and kinetics of the binding process. These results highlight the importance of glycan flexibility and provide inspiration for the design of high‐affinity ligands as antagonists for lectins.

Interplay of H‐Bonds with Aromatics in Isolated Complexes Identifies Isomeric Carbohydrates

By Erik Saparbaev, Vladimir Kopysov, Ruslan Yamaletdinov, Aleksandr Y. Pereverzev, Oleg V. Boyarkin from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 17, 2019.

Clearly identified: The formation of intermolecular hydrogen bonds in isolated non‐covalent complexes of carbohydrates and aromatic molecules leads to distinct signatures in UV‐MS spectra. This allows the identification of any type of carbohydrate isomers, even in the case of oligosaccharides. Abstract The tremendous isomeric diversity of carbohydrates enables a wide range of their biological functions but makes the identification and study of these molecules difficult. We investigated the ability of intermolecular interactions to communicate structural specificity of carbohydrates to protonated aromatic molecules in non‐covalent complexes, isolated and cooled in the gas phase. Our study revealed that small structural differences between carbohydrate isomers of any type, including enantiomers, are accurately communicated by these interactions to aromatic molecules as detectable changes in their electronic excitation spectra. The specific response of the aromatics to the isomers of carbohydrates is fine‐tuned by the interplay of the various involved non‐covalent bonds. These findings enable the gas‐phase identification and relative quantification of any isomers of oligosaccharides in their solution mixtures using the 2D UV‐MS fingerprinting technique.

Activation of a nonheme Fe(III)–OOH by a second Fe(III) to hydroxylate strong C–H bonds: possible implications for sMMO

By Subhasree Kal, Lawrence Que from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 17, 2019.

Nonheme iron oxygenases contain either mono‐iron or di‐iron active sites, and the role of the second iron in the latter enzymes is a topic of particular interest, especially for soluble methane monooxygenase (sMMO). Herein we report the activation of a nonheme FeIII–OOH intermediate in a synthetic mono‐iron system using FeIII(OTf)3 to form a high‐valent oxidant capable of effecting cyclohexane and benzene hydroxylation within seconds at ‐40 °C. Our results show that the second iron acts as a Lewis acid to activate the iron‐hydroperoxo intermediate, leading to the formation of a powerful FeV=O oxidant ‐ a possible role for the second iron in sMMO.

Wed 01 May 16:15: How to design a programming language

From All Talks (aka the CURE list). Published on Apr 17, 2019.

How to design a programming language

Now that interactive digital systems are ubiquitous, principled design has become essential – understanding user needs in order to build systems that are fit for purpose. Are programming languages also user interfaces, and do they need similar design processes? This talk asks whether programming languages are purely “internal” components of a system, derived from engineering and mathematical considerations, or whether human factors are also a core consideration in programming language research. A key question is who gets to write programs – will programming in future be an activity just for technical specialists, or is it a tool for everyone? The tools of AI research are a key concern, many reflecting the resources of the large companies that sponsor their development. Could new languages enable AI research in a greater diversity of contexts, including low-income countries?

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Ionophore‐based biphasic chemical sensing in droplet microfluidics

By Xuewei Wang, Meng Sun, Stephen Ferguson, J. Damon Hoff, Yu Qin, Ryan Bailey, Mark Meyerhoff from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 17, 2019.

Droplet microfluidics is an enabling platform for high‐throughput screens, single cell studies, low‐volume chemical diagnostics, and microscale material syntheses. Analytical methods for real‐time and in situ detection of chemicals in the droplets will greatly benefit these applications, but they remain limited. Herein, we report a novel heterogeneous chemical sensing strategy based on functionalization of the oil phase with rationally combined sensing reagents. Sub‐nanoliter oil segments containing pH‐sensitive fluorophores, ionophores, and ion‐exchangers enable highly selective and rapid fluorescence detection of physiologically important electrolytes (K+, Na+, and Cl‐) and polyions (protamine) in sub‐nanoliter aqueous droplets. Electrolyte analysis in whole blood is demonstrated without suffering from optical interference from the sample matrix. Moreover, an oil phase doped with a boronic acid‐appended aza‐BODIPY dye allows indication of H2O2 in the aqueous droplets, exemplifying sensing of targets beyond ionic species.

Wed 24 Apr 16:15: Hand Tracking on HoloLens 2

From All Talks (aka the CURE list). Published on Apr 17, 2019.

Hand Tracking on HoloLens 2

Hands are the primary and most direct way we interact with the world. We use tools all the time, but our hands are always with us. With HoloLens 2, we introduced a new way for users to interact with virtual objects in mixed reality – simply reaching out and touching them. Direct Manipulation lets users grab, move, and adjust digital content in the same ways as they do with real, physical objects. To enable this kind of interaction, we must first track the user’s hands.

In this talk, I will describe how we at Microsoft turned research into product to bring Fully Articulated Hand Tracking to HoloLens. This story starts nine years ago with an internship project about fitting smooth 3D models to pictures of dolphins, and ends today with a hand tracker that can accurately and robustly track the surface and joints of a user’s hands at 45Hz, while also being performant enough to fit within the power and computation constraints of a head-mounted device.

I will present the technical highlights of our journey from research to product, focusing on several key engineering efforts and algorithmic innovations. This includes making our code over 500 times faster through careful low-level optimization, collecting a massive dataset of 3D hand data to understand how human hands look and move, and developing a photo-realistic synthetic data pipeline for preparing vast amounts of noise-free training data for machine learning.

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A Single Atom Change Facilitates the Membrane Transport of Green Fluorescent Proteins in Mammalian Cells

By Govindasamy Mugesh, Surendar R. Jakka, Vijayakumar Govindaraj from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 17, 2019.

Direct delivery of proteins into mammalian cells is a challenging problem in biological and biomedical applications. The most common strategies for the delivery of proteins into the cells include the use of cell‐penetrating peptides or supercharged proteins. Herein, we show for the first time that a single atom change, hydrogen to halogen, at one of the tyrosine residues can increase the cellular entry of 28 kDa green fluorescent protein (GFP) in mammalian cells. The protein uptake is facilitated by a receptor‐mediated endocytosis and the cargo can be released effectively into cytosol by co‐treatment with the endosomolytic peptide ppTG21.

Wed 27 Nov 15:00: Title to be confirmed

From All Talks (aka the CURE list). Published on Apr 17, 2019.

Title to be confirmed

Abstract not available

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Wed 13 Nov 15:00: Title to be confirmed

From All Talks (aka the CURE list). Published on Apr 17, 2019.

Title to be confirmed

Abstract not available

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Wed 16 Oct 15:00: Title to be confirmed

From All Talks (aka the CURE list). Published on Apr 17, 2019.

Title to be confirmed

Abstract not available

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Wed 02 Oct 15:00: Title to be confirmed

From All Talks (aka the CURE list). Published on Apr 17, 2019.

Title to be confirmed

Abstract not available

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Wed 25 Sep 15:00: Title to be confirmed

From All Talks (aka the CURE list). Published on Apr 17, 2019.

Title to be confirmed

Abstract not available

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Mitochondria‐Targeting Intracellular Delivery of Native Proteins by Using Biodegradable Silica Nanoparticles

By Peiyan Yuan, Xin Mao, Xiaofeng Wu, Si Si Liew, Lin Li, Shao Q. Yao from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 17, 2019.

Mitochondria are key organelles in mammalian cells whose dysfunctions are linked to various diseases. Drugs targeting mitochondrial proteins thus provide a highly promising strategy for potential therapeutics. Current methods of mitochondria‐targeting delivery of small molecule drugs are available, but not suitable for macromolecules such as proteins (including antibodies). Herein, we report the first example of mitochondria‐targeting intracellular delivery of native proteins (and antibodies) by using biodegradable silica nanoparticles (BS‐NPs). Endowed with surface‐modified triphenylphosphonium (TPP) and cell‐penetrating poly(disulfide)s (CPD), these protein‐loaded nanocapsules were capable of rapid intracellular uptake with minimal endolysosomal trapping, thus providing sufficient time for effective mitochondrial localization followed by glutathione‐triggered biodegradation and mitochondrial release of native functional proteins to take part in further biological processes.

Wed 11 Sep 15:00: Title to be confirmed

From All Talks (aka the CURE list). Published on Apr 17, 2019.

Title to be confirmed

Abstract not available

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Wed 03 Jul 15:00: Title to be confirmed

From All Talks (aka the CURE list). Published on Apr 17, 2019.

Title to be confirmed

Abstract not available

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Wed 19 Jun 15:00: A 'proton ratchet' couples the membrane potential to protein secretion (and perhaps also mitochondrial protein import)

From All Talks (aka the CURE list). Published on Apr 17, 2019.

A 'proton ratchet' couples the membrane potential to protein secretion (and perhaps also mitochondrial protein import)

The proton-motive force (PMF) – the electrochemical gradient of protons across energy-conserving membranes – powers protein transport in bacteria, mitochondria and chloroplasts. Here, we propose a ‘proton ratchet’ mechanism for this process. In the Sec system of bacteria, protons are stripped from lysine side chains of the pre-protein at the cytosolic face of the plasma membrane, then replaced on the exterior, aided by the pH component of the PMF (∆pH; acidic outside). This gives the translocating region of pre-protein a net negative charge, allowing it to diffuse down the electrical component (∆ψ; positive outside). For mitochondrial import (through the TIM23 complex) the proton ratchet acts in the opposite direction, with negatively charged residues protonated for passage across the inner membrane into the negative matrix. The proton ratchet is an elegant solution for coupling the PMF to membrane transport, likely to be used by a range of other transporters of charged molecules.

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Wed 29 May 15:00: Title to be confirmed

From All Talks (aka the CURE list). Published on Apr 17, 2019.

Title to be confirmed

Abstract not available

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Wed 22 May 15:00: Mitochondria and Hypoxia Signalling

From All Talks (aka the CURE list). Published on Apr 17, 2019.

Mitochondria and Hypoxia Signalling

Metabolic reprogramming and mitochondrial metabolism is a hallmark of cancer. Tumour cells rely on glycolysis and mitochondrial oxidative phosphorylation (OXPHOS) to survive and thus mitochondrial OXPHOS has become an increasingly attractive area for therapeutic exploitation in cancer. However, given the importance of mitochondrial function for normal physiological processes, delineating how mitochondrial OXPHOS underlies tumorigenesis is crucial for understanding the potential therapeutic benefit of exploiting mitochondrial metabolism in cancer.

When considering the metabolic landscape of tumours, while tumour origin, genetic background and heterogeneity contribute to a diverse metabolic environment across tumours, the central unifying metabolic stimulus in tumours is hypoxia (low oxygenation). Hypoxia is a key feature of the tumour microenvironment, and presents a major clinical and therapeutic challenge as it enables tumours to survive, metastasize and resist killing by front-line treatments. My group has long-standing expertise in hypoxia signalling, and important advances to our understanding of the key transcriptional drivers involved in hypoxia signalling such as hypoxia inducible factor (HIF), have enabled us to identify and develop novel small molecule HIF signalling inhibitors.

Hypoxia and HIF activation, as well as oncogenic and proliferative signals are known to drive metabolic adaptive responses primarily through transcriptional (and epigenetic) re-programming that in part promote a shift in fuel utilization, resulting in dynamic changes in glycolysis and OXPHOS . Alterations in mitochondrial metabolism are not only a downstream consequence of HIF activation, but mitochondria as the cellular sites for oxygen consumption, regulate hypoxia (and HIF ) signalling through multiple means, including basal oxygen consumption rate (OCR), metabolic intermediates and reactive oxygen species (ROS) generation. But how do tumours dial up their mitochondria to fuel their metabolic demands when oxygen is limiting? Other than HIF itself, the key molecular mechanisms controlling intracellular oxygenation and hypoxia signalling that contribute to tumorigenesis through control of tumour metabolic adaptive responses and tumour cell survival/growth are not understood.

Thus, we have been investigating the cross-talk between mitochondria and hypoxia (and HIF ) signalling. Previously, we discovered the redox-sensitive mitochondrial import protein, coiled-coil helix coiled-coil helix domain-containing protein 4 (CHCHD4) is critical for controlling intracellular oxygenation, hypoxia signalling and metabolism in tumour cells. We have shown that CHCHD4 (also known as MIA40 ) is required for tumour growth in vivo, and is an essential gene in cancer irrespective of aetiology. CHCHD4 provides an import and oxidoreductase-mediated protein folding function along with the sulfhydryl oxidase GFER (ALR/Erv1) as a key component of the mitochondrial disulfide relay system (DRS) within the intermembrane space (IMS). In this way, CHCHD4 participates in electron transfer to complex IV (CIV), the molecular oxygen acceptor of the respiratory chain. Overexpression of CHCHD4 in a range of human cancers correlates with increased tumour progression, disease recurrence and poor patient survival, and provides a proliferative and metabolic advantage to tumour cells in both normoxia and hypoxia. Using our novel small molecule HIF inhibitors, genome-wide CRISPR /Cas9 deletion screening, global proteomic and SILAC analyses, as well as a range of unique cell and model systems that we have generated, we have been investigating how the CHCHD4 -HIF axis works, and how the CHCHD4 -HIF axis contributes to tumorigenesis.

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Wed 22 May 15:00: Is the child the father of the political man?

From All Talks (aka the CURE list). Published on Apr 17, 2019.

Is the child the father of the political man?

Some of the enduring questions in the social sciences concern the origins of our political sentiments. For example, why do some support generous welfare provisions, whereas others favour minimal government-level intervention? And why are some advocates for tighter border controls, whereas other embrace immigration as a cultural good? Although the origins of such attitudes almost certainly reflect multiple factors, individual differences in specific personality traits and general intelligence have often been posited as an important driving influence. However the vast majority of this work has been cross-sectional and thus limits our causal understandings of these putative links; that is, reverse causation (or some other causal path) might be at play.

Some of my recent research work has sought to address this gap in knowledge. In this talk I will present results from studies of two large UK longitudinal cohorts of individuals for whom measures of childhood temperament and general intelligence, as well as adult socio-political attitudes, were available. The findings strongly indicated that political attitudes are (in part) grounded in early childhood psychological characteristics; however, the results also deviated notably from previous findings in the literature suggesting that new perspectives concerning the origins of political attitudes need to be considered.

Dr Gary Lewis is a senior lecturer in psychology at Royal Holloway, University of London. His research is broadly concerned with the study of human individual differences and he has specific interests in personality, social attitudes, and social perception. He uses a range of methods to answer questions in these areas, including neuroimaging, quantitative genetics, and behavioural experiments.

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Wed 15 May 13:00: Adaptive immunity in wild songbirds Host: Professor Jim Kaufman (jfk31@cam.ac.uk)

From All Talks (aka the CURE list). Published on Apr 17, 2019.

Adaptive immunity in wild songbirds

Abstract not available

Host: Professor Jim Kaufman (jfk31@cam.ac.uk)

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Mon 27 May 15:00: Title to be confirmed

From All Talks (aka the CURE list). Published on Apr 17, 2019.

Title to be confirmed

Abstract not available

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Thu 02 May 15:00: Title to be confirmed

From All Talks (aka the CURE list). Published on Apr 17, 2019.

Title to be confirmed

Abstract not available

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Wed 05 Jun 14:15: Understanding the Dynamics of Unentangled Associating Polymers by Means of Molecular Simulations

From All Talks (aka the CURE list). Published on Apr 17, 2019.

Understanding the Dynamics of Unentangled Associating Polymers by Means of Molecular Simulations

Associating polymers are a family of macromolecules that have sticky groups that can create intermolecular reversible bonds with energies on the order of a few tens of kT. These bonds can associate and dissociate easily at room temperature and, above the percolation threshold, associating polymers form transient solid soft materials. These materials have many applications as sacrificial components in tough physical double networks, synthetic matrices for tissue engineering, injectable biomaterials for minimally invasive surgery or self-healing soft materials. In all cases, it is very important to understand and predict both the dynamical response of the material (i.e. its mechanical properties or the diffusion of the network forming constituents). Recent experiments have revealed that a variety of unentangled associative polymers with different architectures and different nature of the associating interactions exhibit an unexpected diffusion behavior, with a phenomenological superdiffusive scaling at length-scales and time-scales much longer than the molecular size and relaxation time. In this talk, I will discuss a new coarse-grained molecular model of unentangled associating polymers that successfully explains the observed anomalous behavior and reveals three basic mechanisms of molecular diffusion: caging dynamics, walking diffusion and molecular hopping, all of which depend very strongly on polymer concentration, length of the segments between stickers and the association/dissociation kinetics. The apparent superdiffusive scaling results primarily from molecular hopping, which dominates the dynamics at long times if the kinetics of attachment are much slower than the relaxation time of polymer strands between stickers and the formation of loops is favourable. Finally, I will discuss how the molecular parameters affect the diffusivity and relaxation modulus, as well as the non-linear flow behaviour, and how to confirm other predictions of the model experimentally and by means of Molecular Dynamics simulations.

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Wed 29 May 14:15: Using the Energy Landscape to Elucidate Protein-Ligand Interactions First Year PhD Report

From All Talks (aka the CURE list). Published on Apr 17, 2019.

Using the Energy Landscape to Elucidate Protein-Ligand Interactions

Due to polymorphism and the long timescales involved, it is difficult to characterise the precise nature of protein-ligand interactions experimentally. Many biological systems exhibit broken ergodicity, thus limiting the usefulness of standard molecular dynamics and Monte Carlo procedures. Basin-hopping and discrete path sampling provide alternative techniques that can effectively explore configuration space and provide data to construct kinetic transition networks, respectively. These methods have been applied to the enzyme HemS, which experiment suggests can regulate haem and NADH interactions to control a novel oxygen-independent haem-breakdown process. Specifically, the results presented provide new insight into the conformation of a double-phenylalanine gate – thought to be essential to the regulatory nature of the protein – and its response to the approach of NADH towards haem.

First Year PhD Report

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Induced Fit of C2H2 in a Flexible MOF through Cooperative Action of Open Metal Sites

By Heng Zeng, Mo Xie, Yong-Liang Huang, Yifang Zhao, Xiao-Jing Xie, Jian-Ping Bai, Meng-Yan Wan, Rajamani Krishna, Weigang Lu, Dan Li from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 17, 2019.

Porous materials that can undergo pore structure adjustment to better accommodate specific molecules are ideal for separation and purification. Here we report a stable microporous metal‐organic framework, JNU‐1, featuring one‐dimensional diamond‐shaped channels with high‐density of open metal sites arranged on the surface for cooperative binding of acetylene. Together with its framework flexibility and appropriate pore geometry, JNU‐1 exhibits an induced‐fit behavior for acetylene. The specific binding sites and continuous framework adaptation upon increased acetylene pressure are validated by molecular modeling and in situ X‐ray diffraction study. This unique induced‐fit behavior endows JNU‐1 with an unprecedented increase in acetylene binding‐affinity (adsorption enthalpy value can reach up to 47.6 kJ mol‐1 at ca. 2.0 mmol g‐1 of loading).

Thu 06 Jun 12:00: Studying viruses in people using mathematics

From All Talks (aka the CURE list). Published on Apr 17, 2019.

Studying viruses in people using mathematics

Abstract not available

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Wed 24 Apr 14:15: Simulating the Quantum Behavior of Matter: Algorithms and Applications

From All Talks (aka the CURE list). Published on Apr 17, 2019.

Simulating the Quantum Behavior of Matter: Algorithms and Applications

Both electrons and nuclei follow the laws of quantum mechanics, and even though classical approximations and/or empirical models can be quite successful in many cases, a full quantum description is needed to achieve predictive simulations of matter. Traditionally, simulations that treat both electrons and nuclei as quantum particles have been prohibitively demanding. In this talk I will present several recent algorithmic advances that have increased dramatically the range of systems that are amenable to quantum modelling: on one hand, by using accelerated path integral schemes to treat the nuclear degrees of freedom, and on the other by using machine-learning potentials to reproduce inexpensively high-end electronic-structure calculations. I will give examples of both approaches, and discuss how the two can be used in synergy to make fully quantum modelling affordable.

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Functional Polyion Complex Vesicles enabled by Supramolecular Reversible Coordination Polyelectrolytes

By Wenjuan Zhou, Jiahua Wang, Peng Ding, Xuhong Guo, Martien A. Cohen Stuart, Junyou Wang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 17, 2019.

PICsomes (vesicles formed by polyelectrolyte complexation) have attracted attention as delivery systems for bio‐cargo because they have walls consisting of hydrophilic yet insoluble polymer material, which may endow them with unique properties regarding permeability. So far, controlled formation of PICsomes seemed to require pairs of diblock copolymers with carefully length‐matched anionic and cationic blocks, which is synthetically rather demanding. Here, we report a new class of PICsomes in which the anionic/neutral diblock copolymer is replaced by an anionic, reversible, supramolecular polyelectrolyte based on metal‐ligand coordination. This supramolecular polyelectrolyte tends to form exclusively inside the wall of the assembly, and therefore is possibly capable to self‐adjust its length to that of the cationic block provided. Moreover, the supramolecular coordination polyelectrolyte introduces new and tunable properties and functions associated with the metal, which can be chosen from a large variety. As a proof‐of‐concept we prepare Mn‐based PICsomes and show that these display high magnetic relaxivity as well as enhanced contrast in in vitro MR imaging tests. The generic applicability of our approach, together with the new functions derived from the metal ions, demonstrates a robust strategy for the preparation of a variety of PICsomes with well‐defined and tunable structures and properties.

[ASAP] Terahertz Detection with Perfectly-Absorbing Photoconductive Metasurface

By Thomas Siday, Polina P. Vabishchevich, Lucy Hale, Charles Thomas Harris, Ting Shan Luk, John L. Reno, Igal Brener, Oleg Mitrofanov from Nano Letters: Latest Articles (ACS Publications). Published on Apr 17, 2019.

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Nano Letters
DOI: 10.1021/acs.nanolett.8b05118

[ASAP] Unprecedented New Crystalline Forms of SnSe in Narrow to Medium Diameter Carbon Nanotubes

By Charlotte A. Slade, Ana M. Sanchez, Jeremy Sloan from Nano Letters: Latest Articles (ACS Publications). Published on Apr 17, 2019.

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Nano Letters
DOI: 10.1021/acs.nanolett.9b00133

[ASAP] High Affinity to Skeleton Rare Earth Doped Nanoparticles for Near-Infrared II Imaging

By Shuqing He, Si Chen, Daifeng Li, Yifan Wu, Xiao Zhang, Jianfeng Liu, Jun Song, Liwei Liu, Junle Qu, Zhen Cheng from Nano Letters: Latest Articles (ACS Publications). Published on Apr 17, 2019.

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Nano Letters
DOI: 10.1021/acs.nanolett.9b00140

[ASAP] Three-Dimensional, High-Resolution Printing of Carbon Nanotube/Liquid Metal Composites with Mechanical and Electrical Reinforcement

By Young-Geun Park, Hyegi Min, Hyobeom Kim, Anar Zhexembekova, Chang Young Lee, Jang-Ung Park from Nano Letters: Latest Articles (ACS Publications). Published on Apr 17, 2019.

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Nano Letters
DOI: 10.1021/acs.nanolett.9b00150

[ASAP] Direct Synthesis of Water-Dispersible Magnetic/Plasmonic Heteronanostructures for Multimodality Biomedical Imaging

By Jingbin Zeng, Mingfu Gong, Dawei Wang, Mengmeng Li, Wenjing Xu, Zhiwei Li, Shichuan Li, Dong Zhang, Zifeng Yan, Yadong Yin from Nano Letters: Latest Articles (ACS Publications). Published on Apr 17, 2019.

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Nano Letters
DOI: 10.1021/acs.nanolett.9b00171

[ASAP] Tip-Enhanced Infrared Difference-Nanospectroscopy of the Proton Pump Activity of Bacteriorhodopsin in Single Purple Membrane Patches

By Valeria Giliberti, Raffaella Polito, Eglof Ritter, Matthias Broser, Peter Hegemann, Ljiljana Puskar, Ulrich Schade, Laura Zanetti-Polzi, Isabella Daidone, Stefano Corni, Francesco Rusconi, Paolo Biagioni, Leonetta Baldassarre, Michele Ortolani from Nano Letters: Latest Articles (ACS Publications). Published on Apr 17, 2019.

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Nano Letters
DOI: 10.1021/acs.nanolett.9b00512

[ASAP] Aqueous Zinc-Ion Storage in MoS2 by Tuning the Intercalation Energy

By Hanfeng Liang, Zhen Cao, Fangwang Ming, Wenli Zhang, Dalaver H. Anjum, Yi Cui, Luigi Cavallo, Husam N. Alshareef from Nano Letters: Latest Articles (ACS Publications). Published on Apr 17, 2019.

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Nano Letters
DOI: 10.1021/acs.nanolett.9b00697

[ASAP] Exciton–Plasmon Energy Exchange Drives the Transition to a Strong Coupling Regime

By Tigran V. Shahbazyan from Nano Letters: Latest Articles (ACS Publications). Published on Apr 17, 2019.

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Nano Letters
DOI: 10.1021/acs.nanolett.9b00827

[ASAP] Stable Efficiency Exceeding 20.6% for Inverted Perovskite Solar Cells through Polymer-Optimized PCBM Electron-Transport Layers

By Dong Yang, Xiaorong Zhang, Kai Wang, Congcong Wu, Ruixia Yang, Yuchen Hou, Yuanyuan Jiang, Shengzhong Liu, Shashank Priya from Nano Letters: Latest Articles (ACS Publications). Published on Apr 17, 2019.

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Nano Letters
DOI: 10.1021/acs.nanolett.9b00936

[ASAP] Formation and Healing of Defects in Atomically Thin GaSe and InSe

By David G. Hopkinson, Viktor Zólyomi, Aidan P. Rooney, Nick Clark, Daniel J. Terry, Matthew Hamer, David J. Lewis, Christopher S. Allen, Angus I. Kirkland, Yuri Andreev, Zakhar Kudrynskyi, Zakhar Kovalyuk, Amalia Patanè, Vladimir I. Fal’ko, Roman Gorbachev, Sarah J. Haigh from ACS Nano: Latest Articles (ACS Publications). Published on Apr 17, 2019.

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ACS Nano
DOI: 10.1021/acsnano.8b08253

[ASAP] Halide Ligands To Release Strain in Cadmium Chalcogenide Nanoplatelets and Achieve High Brightness

By Marion Dufour, Junling Qu, Charlie Greboval, Christophe Méthivier, Emmanuel Lhuillier, Sandrine Ithurria from ACS Nano: Latest Articles (ACS Publications). Published on Apr 17, 2019.

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ACS Nano
DOI: 10.1021/acsnano.8b09794

[ASAP] Plasmon Excitations in Mixed Metallic Nanoarrays

By Kevin M. Conley, Neha Nayyar, Tuomas P. Rossi, Mikael Kuisma, Volodymyr Turkowski, Martti J. Puska, Talat S. Rahman from ACS Nano: Latest Articles (ACS Publications). Published on Apr 17, 2019.

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ACS Nano
DOI: 10.1021/acsnano.8b09826

[ASAP] Fabricating CsPbX3-Based Type I and Type II Heterostructures by Tuning the Halide Composition of Janus CsPbX3/ZrO2 Nanocrystals

By Haiyu Liu, Yeshu Tan, Muhan Cao, Huicheng Hu, Linzhong Wu, Xiaoya Yu, Lu Wang, Baoquan Sun, Qiao Zhang from ACS Nano: Latest Articles (ACS Publications). Published on Apr 17, 2019.

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ACS Nano
DOI: 10.1021/acsnano.9b00001

[ASAP] Altering the Properties of Graphene on Cu(111) by Intercalation of Potassium Bromide

By Mathias Schulzendorf, Antoine Hinaut, Marcin Kisiel, Res Jöhr, Rémy Pawlak, Paolo Restuccia, Ernst Meyer, Maria Clelia Righi, Thilo Glatzel from ACS Nano: Latest Articles (ACS Publications). Published on Apr 17, 2019.

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ACS Nano
DOI: 10.1021/acsnano.9b00278

[ASAP] Revealing the Surface Effect of the Soluble Catalyst on Oxygen Reduction/Evolution in Li–O2 Batteries

By Zhen-Zhen Shen, Shuang-Yan Lang, Yang Shi, Jian-Min Ma, Rui Wen, Li-Jun Wan from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Apr 17, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.8b12183

[ASAP] Chirality-Selected Chemical Modulation of Amyloid Aggregation

By Nan Gao, Zhi Du, Yijia Guan, Kai Dong, Jinsong Ren, Xiaogang Qu from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Apr 17, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.8b12537

[ASAP] Two-in-One Chemogene Assembled from Drug-Integrated Antisense Oligonucleotides To Reverse Chemoresistance

By Quanbing Mou, Yuan Ma, Fei Ding, Xihui Gao, Deyue Yan, Xinyuan Zhu, Chuan Zhang from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Apr 17, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.8b13875

[ASAP] Branched Copper Oxide Nanoparticles Induce Highly Selective Ethylene Production by Electrochemical Carbon Dioxide Reduction

By Jinmo Kim, Woong Choi, Joon Woo Park, Cheonghee Kim, Minjun Kim, Hyunjoon Song from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Apr 17, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b00911

[ASAP] A Mononuclear, Nonheme FeII–Piloty’s Acid (PhSO2NHOH) Adduct: An Intermediate in the Production of {FeNO}7/8 Complexes from Piloty’s Acid

By Alex M. Confer, Avery C. Vilbert, Aniruddha Dey, Kyle M. Lancaster, David P. Goldberg from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Apr 17, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b01700

[ASAP] Versatile Nanoemulsion Assembly Approach to Synthesize Functional Mesoporous Carbon Nanospheres with Tunable Pore Sizes and Architectures

By Liang Peng, Chin-Te Hung, Shuwen Wang, Xingmiao Zhang, Xiaohang Zhu, Zaiwang Zhao, Changyao Wang, Yun Tang, Wei Li, Dongyuan Zhao from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Apr 17, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b02091

[ASAP] Pd-Mediated Synthesis of Ag33 Chiral Nanocluster with Core–Shell Structure in T Point Group

By Fan Tian, Rong Chen from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Apr 17, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b02162

[ASAP] Ru-Based Catechothiolate Complexes Bearing an Unsaturated NHC Ligand: Effective Cross-Metathesis Catalysts for Synthesis of (Z)-a,ß-Unsaturated Esters, Carboxylic Acids, and Primary, Secondary, and Weinreb Amides

By Zhenxing Liu, Chaofan Xu, Juan del Pozo, Sebastian Torker, Amir H. Hoveyda from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Apr 17, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b02318

[ASAP] Enantioselective Total Synthesis of (+)-Arboridinine

By Zhen Zhang, Sujun Xie, Bin Cheng, Hongbin Zhai, Yun Li from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Apr 17, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b02362

Scalable fabrication of metal-phenolic nanoparticle by coordination-driven flash nanocomplexation for cancer theranostics

By Yongming Chen from RSC - Nanoscale latest articles. Published on Apr 17, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR02185J, Paper
Zhijia Liu, Zhicheng Le, Liejing Lu, Ying Zhu, Chengbiao Yang, Pengfei Zhao, Zhiyong Wang, Jun Shen, Lixin Liu, Yongming Chen
Although various nanomaterials have been developed for cancer theranostics, it remains a key challenge for effective integration of therapeutic drugs and diagnostic agents into a single multicomponent nanoparticle via a...
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Enhancing water permeation through alumina membranes by changing from cylindrical to conical nanopores

By Jianwen Jiang from RSC - Nanoscale latest articles. Published on Apr 17, 2019.

Nanoscale, 2019, Advance Article
DOI: 10.1039/C8NR09602C, Paper
Anjaiah Nalaparaju, John Wang, Jianwen Jiang
Water permeation through highly hydrophilic alumina membranes can be enhanced by conical nanopores.
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High-efficient elimination of intracellular bacteria via a metal organic frameworks (MOFs) based three-in-one delivery system

By Jianlong Wang from RSC - Nanoscale latest articles. Published on Apr 17, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR01284B, Paper
Xu Zhang, Lizhi Liu, Lunjie Huang, Wentao Zhang, Rong Wang, Tianli Yue, Jing Sun, Guoliang Li, Jianlong Wang
Plenty of infectious diseases that cause clinical failures and relapses after antibiotic therapy have been confirmed related to pathogenic intracellular bacteria. The existing therapeutic strategies fail to eliminate intracellular bacteria...
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Packaging of DNA origami in viral capsids

By Stanislav Kler from RSC - Nanoscale latest articles. Published on Apr 17, 2019.

Nanoscale, 2019, Advance Article
DOI: 10.1039/C8NR10113B, Communication
Idit Kopatz, Ran Zalk, Yael Levi-Kalisman, Efrat Zlotkin-Rivkin, Gabriel A. Frank, Stanislav Kler
DNA origami in self-assembled SV40 capsid, a new type of encapsulation substrate for medical applications.
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Spontaneous MXenes monolayer assembly at liquid-air interface

By Andrey A. Eliseev from RSC - Nanoscale latest articles. Published on Apr 17, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR00525K, Paper
Dmitrii I. Petukhov, Andrey Chumakov, Alena S Kan, Vasily A. Lebedev, Artem A. Eliseev, Oleg Konovalov, Andrey A. Eliseev
Here we report on spontaneous assembly of Ti3C2Tx MXene flakes into monolayer films at liquid-air interface. According to X-ray reflectivity and grazing incidence X-ray fluorescence both the structure of the...
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Valley polarization of exciton-polaritons in monolayer WSe2 in a tunable microcavity

By Barbara Piętka from RSC - Nanoscale latest articles. Published on Apr 17, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR02038A, Paper
Mateusz Król, Katarzyna Lekenta, Rafał Mirek, Karolina Łempicka, Daniel Stephan, Karol Nogajewski, Maciej R. Molas, Adam Babiński, Marek Potemski, Jacek Szczytko, Barbara Piętka
Monolayer transition metal dichalcogenides, known for exhibiting strong excitonic resonances, constitute a very interesting and versatile platform for investigation of light–matter interactions. In this work we report on a strong...
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Translocation intermediates of Ubiquitin through an α-Hemolysin nanopore: implications for detection of post-translational modifications

By Mauro Chinappi from RSC - Nanoscale latest articles. Published on Apr 17, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C8NR10492A, Paper
Emma Letizia Bonome, Fabio Cecconi, Mauro Chinappi
Nanopore based sensors constitute a promising approach to single molecule protein characterization being able, in principle, to detect sequences, structural elements and folding states of proteins and polypeptide chains. In...
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Plastic Recovery and Self-healing in Longitudinally Twinned SiGe Nanowires

By Arunkumar Subramanian from RSC - Nanoscale latest articles. Published on Apr 17, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR02073J, Paper
Md Ruhul Amin Shikder, Ajaykrishna Ramasubramanian, Mahjabin Maksud, Vitaliy Yurkiv, J. Yoo, Charles Thomas Harris, Gokul Vasudevamurthy, Farzad Mashayek, Arunkumar Subramanian
This paper reports on plastic recovery and self-healing behavior in longitudinally-twinned and [112] orientated SiGe nanowire (NW) beams when they are subjected to large bending strains. The NW alloys are...
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Superior Li-ion storage of VS4 nanowire anchored on reduced graphene

By Y. Z. Huang from RSC - Nanoscale latest articles. Published on Apr 17, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR01953G, Paper
Guang Yang, Huanhuan Wang, Bowei Zhang, Shini Foo, Mingbo Ma, Xun Cao, Jilei Liu, Shibing Ni, Madhavi Srinivasan, Y. Z. Huang
Research in VS4 is lagging due to its difficulty in tailored synthesis. Herein, unique architecture design of one-dimensional VS4 nanowires anchored on reduced graphene oxide are demonstrated via a facile...
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Single Phase of Spinel Co2RhO4 Nanotubes with Remarkably Enhanced Catalytic Performance for Oxygen Evolution Reaction

By Myung Hwa Kim from RSC - Nanoscale latest articles. Published on Apr 17, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR02197C, Communication
So Yeon Kim, Areum Yu, Yejung Lee, Ha Yeon Kim, Yeon Jae Kim, Nam-Suk Lee, Chongmok Lee, Youngmi Lee, Myung Hwa Kim
We report the effective crystal growth for a unique single phase of spinel cobalt rhodium oxide (Co2RhO4) nanotubes via the electrospinning process combined with the thermal annealing process. In the...
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Controllable Acidophilic Dual-Emission Fluorescent Carbonized Polymer Dots for Selectively Bacteria-Imaging

By Bai Yang from RSC - Nanoscale latest articles. Published on Apr 17, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR01118H, Paper
Xiaohuan Zhao, Qiu ling Tang, Shoujun Zhu, Wenhuan Bu, Mingxi Yang, Xinchan Liu, Yang Meng, Weixian Yu, Hongchen Sun, Bai Yang
Fluorescent materials are powerful contrast agents that are critical modules in the field of photoelectric devices and bioimaging. As emerging fluorescent materials, carbonized polymer dots (CPDs) with high quantum yield...
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In-situ Etching Assisted Synthesis of Pt-Fe-Mn Ternary Alloys with High-index Facets as Efficient Catalysts for Electro-oxidation Reactions

By Shi-Gang Sun from RSC - Nanoscale latest articles. Published on Apr 17, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C8NR10231G, Paper
Congli Qin, Aixin Fan, Xin Zhang, Xiaoping Dai, Hui Sun, Danhua Ren, Zhun Dong, Yao Wang, Chenglong Luan, Jinyu Ye, Shi-Gang Sun
Pt-based alloys enclosed with high-index facets (HIFs) generally showed much higher specific catalytic activities than those of the counterparts with low-index facets for electric catalytic reactions. However, the exposure of...
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Enhancing the photocatalytic activity of ZnSn(OH)6 achieved by a gradual sulfur doping tactics

By Xiaodong Yi from RSC - Nanoscale latest articles. Published on Apr 17, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR01103J, Paper
XInyi LIan, Zhou Chen, Xiang Yu, Tingting Fan, dong yun yun, Hesheng Zhai, Weiping Fang, Xiaodong Yi
To solve the intrinsic deficiency inherited from the large band gap of ZnSn(OH)6 (ZSH), a gradual sulfur doping strategy was firstly proposed here to expand the optical absorption range, improve...
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Enhanced CO2 reduction and valuable C2+ chemical production by a CdS-Photosynthetic hybrid system

By Po Keung Wong from RSC - Nanoscale latest articles. Published on Apr 17, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR02896J, Communication
Bo Wang, Zhifeng Jiang, Jimmy Chai-mei Yu, Jianfang Wang, Po Keung Wong
Semi-artificial photosynthesis is an emerging technique in recent years. Here, we presented an inorganic-biological hybrid system composed of a photosynthetic Rhodopseudomonas palustris and CdS nanoparticles coated on the bacterial surface....
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Recent Progress in Molecular Design of Fused Ring Electron Acceptors for Organic Solar Cells

By Somnath Dey from Wiley: Small: Table of Contents. Published on Apr 16, 2019.

Remarkable advancement has been made in the efficiency of organic solar cells (OSCs) in recent times, mostly due to novel fused ring electron acceptors (FREAs). Here, structural evolution of FREAs to enhance efficiency is comprehensively discussed. Moreover, recent progress in polymer design, semi‐transparent OSCs, ternary, and tandem OSCs is provided. The challenges and future development of FREAs are briefly addressed. Abstract The quest for sustainable energy sources has led to accelerated growth in research of organic solar cells (OSCs). A solution‐processed bulk‐heterojunction (BHJ) OSC generally contains a donor and expensive fullerene acceptors (FAs). The last 20 years have been devoted by the OSC community to developing donor materials, specifically low bandgap polymers, to complement FAs in BHJs. The current improvement from ≈2.5% in 2013 to 17.3% in 2018 in OSC performance is primarily credited to novel nonfullerene acceptors (NFA), especially fused ring electron acceptors (FREAs). FREAs offer unique advantages over FAs, like broad absorption of solar radiation, and they can be extensively chemically manipulated to tune optoelectronic and morphological properties. Herein, the current status in FREA‐based OSCs is summarized, such as design strategies for both wide and narrow bandgap FREAs for BHJ, all‐small‐molecule OSCs, semi‐transparent OSC, ternary, and tandem solar cells. The photovoltaics parameters for FREAs are summarized and discussed. The focus is on the various FREA structures and their role in optical and morphological tuning. Besides, the advantages and drawbacks of both FAs and NFAs are discussed. Finally, an outlook in the field of FREA‐OSCs for future material design and challenges ahead is provided.

Unidirectional presentation of membrane proteins in nanoparticle‐supported liposomes

By Wen Chen, Junling Guo, Yongfei Cai, Qingshan Fu, Bing Chen, James Jeiwen Chou from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 16, 2019.

Presentation of membrane proteins to host immune systems has been a challenging problem due to complexity arising from the poor in vivo stability of the membrane‐mimetic media often used for solubilizing the membrane proteins. We report the use of functionalized, biocompatible nanoparticles as substrates to guide the formation of proteoliposomes that can present many copies of membrane proteins in a unidirectional manner. The approach was demonstrated to present the membrane‐proximal region of the HIV‐1 envelope glycoprotein. These nanoparticle‐supported liposomes are broadly applicable as membrane antigen vehicles for inducing host immune responses.

Artificial Neuron and Synapse Realized in an Antiferromagnet/Ferromagnet Heterostructure Using Dynamics of Spin–Orbit Torque Switching

By Aleksandr Kurenkov, Samik DuttaGupta, Chaoliang Zhang, Shunsuke Fukami, Yoshihiko Horio, Hideo Ohno from Wiley: Advanced Materials: Table of Contents. Published on Apr 16, 2019.

Control of spintronics‐based binary and analog devices by pulses down to 1 ns and its applications are studied. It is found that the response of the binary device reproduces the behavior of a biological neuron while the analog device responds like a synapse. This is the first implementation of both elements based on the same material and working principle. Abstract Efficient information processing in the human brain is achieved by dynamics of neurons and synapses, motivating effective implementation of artificial spiking neural networks. Here, the dynamics of spin–orbit torque switching in antiferromagnet/ferromagnet heterostructures is studied to show the capability of the material system to form artificial neurons and synapses for asynchronous spiking neural networks. The magnetization switching, driven by a single current pulse or trains of pulses, is examined as a function of the pulse width (1 s to 1 ns), amplitude, number, and pulse‐to‐pulse interval. Based on this dynamics and the unique ability of the system to exhibit binary or analog behavior depending on the device size, key functionalities of a synapse (spike‐timing‐dependent plasticity) and a neuron (leaky integrate‐and‐fire) are reproduced in the same material and on the basis of the same working principle. These results open a way toward spintronics‐based neuromorphic hardware that executes cognitive tasks with the efficiency of the human brain.

Concerted Nucleophilic Aromatic Substitution Reactions

By John Murphy, Simon Rohrbach, Andrew J. Smith, Jia Hao Pang, Darren L. Poole, Tell Tuttle, Shunsuke Chiba from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 16, 2019.

Recent developments in experimental and computational chemistry have identified a rapidly growing class of nucleophilic aromatic substitutions that proceed by concerted (cSNAr),1,2 rather than classical two‐step, SNAr mechanisms. Whereas traditional SNAr reactions require substantial activation of the aromatic ring by electron‐withdrawing substituents, such activating groups are not mandatory in the concerted pathways. At this crucial stage of growth in understanding of these reactions, our aim is to review the current state of knowledge on CSNAr reactions. [The review includes many types of substrates and nucleophiles; it specifically excludes transition metal‐related processes that might involve concerted substitutions on arenes].

Cell Encapsulation in Soft, Anisometric Poly(ethylene) Glycol Microgels Using a Novel Radical‐Free Microfluidic System

By Luis P. B. Guerzoni, Jonas C. Rose, David B. Gehlen, Alexander Jans, Tamàs Haraszti, Matthias Wessling, Alexander J. C. Kuehne, Laura De Laporte from Wiley: Small: Table of Contents. Published on Apr 16, 2019.

Biocompatible cell‐loaded poly(ethylene) glycol rod‐shaped micogels are continuously produced via microfluidics. The microgels are very soft and their aspect ratio and stiffness are tuned by varying flow parameters and precursors concentrations. A rapid, radical‐free crosslinking mechanism is combined with cell‐adhesive and enzymatically degradable peptides. Encapsulated primary fibroblasts are viable, and grow and spread across the microgel's anisometric structure. Abstract Complex 3D artificial tissue constructs are extensively investigated for tissue regeneration. Frequently, materials and cells are delivered separately without benefitting from the synergistic effect of combined administration. Cell delivery inside a material construct provides the cells with a supportive environment by presenting biochemical, mechanical, and structural signals to direct cell behavior. Conversely, the cell/material interaction is poorly understood at the micron scale and new systems are required to investigate the effect of micron‐scale features on cell functionality. Consequently, cells are encapsulated in microgels to avoid diffusion limitations of nutrients and waste and facilitate analysis techniques of single or collective cells. However, up to now, the production of soft cell‐loaded microgels by microfluidics is limited to spherical microgels. Here, a novel method is presented to produce monodisperse, anisometric poly(ethylene) glycol microgels to study cells inside an anisometric architecture. These microgels can potentially direct cell growth and can be injected as rod‐shaped mini‐tissues that further assemble into organized macroscopic and macroporous structures post‐injection. Their aspect ratios are adjusted with flow parameters, while mechanical and biochemical properties are altered by modifying the precursors. Encapsulated primary fibroblasts are viable and spread and migrate across the 3D microgel structure.

Iridium‐Catalyzed Distal Hydroboration of Aliphatic Internal Alkenes

By Guangzhu Wang, xinyi Liang, Lili Chen, Qian Gao, Jian-Guo Wang, Panke Zhang, Qian Peng, Senmiao Xu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 16, 2019.

Regioselective hydroboration of aliphatic internal alkenes remains a great challenge. Reported here is an iridium‐catalyzed hydroboration of aliphatic internal alkenes, providing distal borylated products in good to excellent yields with high regioselectivity (up to 99:1). We also demonstrated that the C‐B bond of the distal borylated product could be converted facilely to other functionalities. DFT calculation indicated that reaction undergoes an unexpected Ir(III/V) cycle.

Temperature Gradients Drive Bulk Flow Within Microchannel Lined by Fluid–Fluid Interfaces

By Guillermo J. Amador, Ziyu Ren, Ahmet F. Tabak, Yunus Alapan, Oncay Yasa, Metin Sitti from Wiley: Small: Table of Contents. Published on Apr 16, 2019.

A micropump that exploits surface tension gradients induced by temperature changes is developed. The micropump is demonstrated in a lab‐on‐a‐chip device for blood diagnosis. Due to its low energy consumption, it can operate with absorption of solar irradiation. The device has the potential to replace bulky syringe pumps and be implemented in low‐resource settings with limited electricity. Abstract Surface tension gradients induce Marangoni flow, which may be exploited for fluid transport. At the micrometer scale, these surface‐driven flows can be quite significant. By introducing fluid–fluid interfaces along the walls of microfluidic channels, bulk fluid flows driven by temperature gradients are observed. The temperature dependence of the fluid–fluid interfacial tension appears responsible for these flows. In this report, the design concept for a biocompatible microchannel capable of being powered by solar irradiation is provided. Using microscale particle image velocimetry, a bulk flow generated by apparent surface tension gradients along the walls is observed. The direction of flow relative to the imposed temperature gradient agrees with the expected surface tension gradient. The phenomenon's ability to replace bulky peripherals, like traditional syringe pumps, on a diagnostic microfluidic device that captures and detects leukocyte subpopulations within blood is demonstrated. Such microfluidic devices may be implemented for clinical assays at the point of care without the use of electricity.

Improved Epitaxy of AlN Film for Deep‐Ultraviolet Light‐Emitting Diodes Enabled by Graphene

By Zhaolong Chen, Zhiqiang Liu, Tongbo Wei, Shenyuan Yang, Zhipeng Dou, Yunyu Wang, Haina Ci, Hongliang Chang, Yue Qi, Jianchang Yan, Junxi Wang, Yanfeng Zhang, Peng Gao, Jinmin Li, Zhongfan Liu from Wiley: Advanced Materials: Table of Contents. Published on Apr 16, 2019.

Guided by density functional theory (DFT) calculations, a N2‐plasma‐treated graphene buffer layer is developed to grow high‐quality AlN for deep‐ultraviolet light‐emitting diode (DUV‐LED) applications. The plasma treatment of graphene can facilitate AlN nucleation, thus increasing the growth rate of the AlN film and improving the film quality. The as‐fabricated LED shows a low turn‐on voltage, good reliability, and high output power. Abstract The growth of single‐crystal III‐nitride films with a low stress and dislocation density is crucial for the semiconductor industry. In particular, AlN‐derived deep‐ultraviolet light‐emitting diodes (DUV‐LEDs) have important applications in microelectronic technologies and environmental sciences but are still limited by large lattice and thermal mismatches between the epilayer and substrate. Here, the quasi‐van der Waals epitaxial (QvdWE) growth of high‐quality AlN films on graphene/sapphire substrates is reported and their application in high‐performance DUV‐LEDs is demonstrated. Guided by density functional theory calculations, it is found that pyrrolic nitrogen in graphene introduced by a plasma treatment greatly facilitates the AlN nucleation and enables fast growth of a mirror‐smooth single‐crystal film in a very short time of ≈0.5 h (≈50% decrease compared with the conventional process), thus leading to a largely reduced cost. Additionally, graphene effectively releases the biaxial stress (0.11 GPa) and reduces the dislocation density in the epilayer. The as‐fabricated DUV‐LED shows a low turn‐on voltage, good reliability, and high output power. This study may provide a revolutionary technology for the epitaxial growth of AlN films and provide opportunities for scalable applications of graphene films.

α‐Fe2O3 Nanoparticles Decorated C@MoS2 Nanosheet Arrays with Expanded Spacing of (002) Plane for Ultrafast and High Li/Na‐Ion Storage

By Jing Zhan, Kuan Wu, Xue Yu, Mengjia Yang, Xu Cao, Bo Lei, Dengyu Pan, Hu Jiang, Minghong Wu from Wiley: Small: Table of Contents. Published on Apr 16, 2019.

The design of vertically grown MoS2 nanosheet arrays with expanded spacing of (002) plane, decorated with graphite carbon and Fe2O3 nanoparticles, on flexible carbon fiber cloth is reported. Due to the unique 3D ordered Fe2O3@C@MoS2 array‐type nanostructures, these electrodes manifest an outstanding electrochemical performance for lithium‐ion and sodium‐ion batteries. Abstract MoS2 nanosheets as a promising 2D nanomaterial have extensive applications in energy storage and conversion, but their electrochemical performance is still unsatisfactory as an anode for efficient Li+/Na+ storage. In this work, the design and synthesis of vertically grown MoS2 nanosheet arrays, decorated with graphite carbon and Fe2O3 nanoparticles, on flexible carbon fiber cloth (denoted as Fe2O3@C@MoS2/CFC) is reported. When evaluated as an anode for lithium‐ion batteries, the Fe2O3@C@MoS2/CFC electrode manifests an outstanding electrochemical performance with a high discharge capacity of 1541.2 mAh g−1 at 0.1 A g−1 and a good capacity retention of 80.1% at 1.0 A g−1 after 500 cycles. As for sodium‐ion batteries, it retains a high reversible capacity of 889.4 mAh g−1 at 0.5 A g−1 over 200 cycles. The superior electrochemical performance mainly results from the unique 3D ordered Fe2O3@C@MoS2 array‐type nanostructures and the synergistic effect between the C@MoS2 nanosheet arrays and Fe2O3 nanoparticles. The Fe2O3 nanoparticles act as spacers to steady the structure, and the graphite carbon could be incorporated into MoS2 nanosheets to improve the conductivity of the whole electrode and strengthen the integration of MoS2 nanosheets and CFC by the adhesive role, together ensuring high conductivity and mechanical stability.

Anion‐Modulated HER and OER Activities of 3D Ni–V‐Based Interstitial Compound Heterojunctions for High‐Efficiency and Stable Overall Water Splitting

By Haijing Yan, Ying Xie, Aiping Wu, Zhicheng Cai, Lei Wang, Chungui Tian, Xiaomeng Zhang, Honggang Fu from Wiley: Advanced Materials: Table of Contents. Published on Apr 16, 2019.

An anion‐modulation strategy is presented to create 3D Ni‐V interstitial compound heterojunctions (Ni3N‐VN/nickel foam (NF) and Ni2P‐VP2/NF). The excellent hydrogen evolution reaction (HER) activity of Ni3N‐VN/NF and oxygen evolution reaction (OER) activity of Ni2P‐VP2/NF and minimal mutual influence make them easy to couple to achieve overall water splitting with a low driving voltage and remarkable stability. Abstract Overall water splitting driven by a low voltage is crucial for practical H2 evolution, but it is challenging. Herein, anion‐modulation of 3D Ni–V‐based transition metal interstitial compound (TMIC) heterojunctions supported on nickel foam (Ni3N‐VN/NF and Ni2P‐VP2/NF) as coupled hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) catalysts for efficient overall water splitting is demonstrated. The heterointerface in Ni3N‐VN has a suitable H* absorption energy, being favorable for enhancing HER activity with onset overpotential (ηonset) of zero and Tafel slope of 37 mV dec−1 in 1 m KOH (close to that of Pt/C/NF). For the OER, the synergy of Ni2P‐VP2 with oxide species can give enhanced activity with ηonset of 220 mV and Tafel slope of 49 mV dec−1. The good activity is ascribed to heterointerface for activating the intermediates, good conductivity of TMICs for electron‐transfer, and porous structure facilitation of mass‐transport. Additionally, the minimal mutual influence of Ni3N‐VN/NF and Ni2P‐VP2/NF allows easy coupling for efficient overall water splitting with a low driving voltage (≥1.43 V), a voltage of 1.51 V at 10 mA cm−2, and remarkable durability for 100 h. It can be driven by a solar cell (1.5 V), indicating its potential to store intermittent energy.

Artificial Microbial Arenas: Materials for Observing and Manipulating Microbial Consortia

By Lothar Wondraczek, Georg Pohnert, Felix H. Schacher, Angela Köhler, Michael Gottschaldt, Ulrich S. Schubert, Kirsten Küsel, Axel A. Brakhage from Wiley: Advanced Materials: Table of Contents. Published on Apr 16, 2019.

The study of microbial consortia offers exciting challenges for materials research. Advanced materials allow for the fabrication of adaptive microbial arenas as a new class of habitats for multispecies communities. Simulating complex environmental conditions, such habitats will facilitate the elucidation of functional interdependencies within the microbiome toward stable cocultivation, community training and directed evolution. Abstract From the smallest ecological niche to global scale, communities of microbial life present a major factor in system regulation and stability. As long as laboratory studies remain restricted to single or few species assemblies, however, very little is known about the interaction patterns and exogenous factors controlling the dynamics of natural microbial communities. In combination with microfluidic technologies, progress in the manufacture of functional and stimuli‐responsive materials makes artificial microbial arenas accessible. As habitats for natural or multispecies synthetic consortia, they are expected to not only enable detailed investigations, but also the training and the directed evolution of microbial communities in states of balance and disturbance, or under the effects of modulated stimuli and spontaneous response triggers. Here, a perspective on how materials research will play an essential role in generating answers to the most pertinent questions of microbial engineering is presented, and the concept of adaptive microbial arenas and possibilities for their construction from particulate microniches to 3D habitats is introduced. Materials as active and tunable components at the interface of living and nonliving matter offer exciting opportunities in this field. Beyond forming the physical horizon for microbial cultivates, they will enable dedicated intervention, training, and observation of microbial consortia.

Recent Advances on Electrochemical Biosensing Strategies toward Universal Point of Care Systems

By Yifan Dai, Chung Chiun Liu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 16, 2019.

A number of very recently developed electrochemical biosensing strategies are promoting electrochemical biosensing systems into practical point‐of‐care applications. Focus of research endeavors in biosensing community has transferred from detection of a specific analyte to the development of general biosensing strategies that can be applied for a single category of analytes, such as nucleic acid, protein and cell. In this review, we describe most recent cutting‐edge researches on electrochemical biosensing strategies. These described developments resolved critical challenges on application of electrochemical biosensors to the practical point‐of‐care systems, such as rapid readout, simple biosensor fabrication method, ultra‐high detection sensitivity, direct analysis in complex biological matrix and multiplexed targets analysis. This review provides general guidelines both for scientists in the biosensing research community and for the biosensor industry on development of point‐of‐care system, benefiting global healthcare.

Synthesis, Properties and Application of Tetrakis(pentafluoroethyl)gallate, [Ga(C2F5)4]−

By Mark Niemann, Beate Neumann, Hans-Georg Stammler, Berthold Hoge from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 16, 2019.

Weakly coordinating anions (WCA) are important for academic reasons as well as for technical applications. Tetrakis(pentafluoroethyl)gallate, [Ga(C2F5)4]−, a new WCA, is accessible by treatment of [GaCl3(dmap)] (dmap = 4‐dimethylaminopyridine) with LiC2F5. The anion [Ga(C2F5)4]− proved to be reluctant towards deterioration by aqueous hydrochloric acid or lithium hydroxide. Various salts of [Ga(C2F5)4]− were synthesized with cations such as [PPh4]+, [CPh3]+, [(O2H5)2(OH2)2]2+ and [Li(dec)2]+ (dec = diethyl carbonate). Thermolysis of [(O2H5)2(OH2)2][Ga(C2F5)4]2 gives rise to a dihydrate of tris(pentafluoroethyl)gallane, [Ga(C2F5)3(OH2)2]. All products were characterized by NMR and IR spectroscopy, mass spectrometry, X‐ray diffraction and elemental analysis. Furthermore an outlook for the application of [Li(dec)2][Ga(C2F5)4] as a conducting salt in lithium‐ion batteries is presented.

Regio‐ and Enantioselective Formal Hydroamination of Enamines for the Synthesis of 1,2‐Diamines

By Lu Yu, Peter Somfai from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 16, 2019.

The asymmetric formal hydroamination of enamines using Cu‐H catalyst is reported. The method provides a straightforward and efficient approach for the synthesis of chiral 1,2‐dialkyl amines in good yields with high level of enantioselectivities for a broad range of substrates, and should have significant value for the preparation of molecules bearing a 1,2‐diamine motif.

Direct Writing of a 90 wt% Particle Loading Nanothermite

By Haiyang Wang, Jinpeng Shen, Dylan J. Kline, Noah Eckman, Niti R. Agrawal, Tao Wu, Peng Wang, Michael R. Zachariah from Wiley: Advanced Materials: Table of Contents. Published on Apr 16, 2019.

Particle loading is a critical parameter that is routinely used for benchmarking the energy density and energy release rate of nanoenergetic materials, including propellants, explosives, and pyrotechnics. An ink formulation is developed with only 10 wt% of polymers, which can bind a 90 wt% nanothermite using a simple direct‐writing approach. Abstract The additive manufacturing of energetic materials has received worldwide attention. Here, an ink formulation is developed with only 10 wt% of polymers, which can bind a 90 wt% nanothermite using a simple direct‐writing approach. The key additive in the ink is a hybrid polymer of poly(vinylidene fluoride) (PVDF) and hydroxy propyl methyl cellulose (HPMC) in which the former serves as an energetic initiator and a binder, and the latter is a thickening agent and the other binder, which can form a gel. The rheological shear‐thinning properties of the ink are critical to making the formulation at such high loadings printable. The Young's modulus of the printed stick is found to compare favorably with that of poly(tetrafluoroethylene) (PTFE), with a particle packing density at the theoretical maximum. The linear burn rate, mass burn rate, flame temperature, and heat flux are found to be easily adjusted by varying the fuel/oxidizer ratio. The average flame temperatures are as high as ≈2800 K with near‐complete combustion being evident upon examination of the postcombustion products.

Multiphotoluminescence from a Triphenylamine Derivative and Its Application in White Organic Light‐Emitting Diodes Based on a Single Emissive Layer

By Xiaomeng Li, Jieshun Cui, Qiankai Ba, Zhe Zhang, Shaoqing Chen, Guoxin Yin, Yu Wang, Bobo Li, Guohong Xiang, Kwang Soo Kim, Hu Xu, Zhaoyu Zhang, Hsing‐Lin Wang from Wiley: Advanced Materials: Table of Contents. Published on Apr 16, 2019.

Single‐emissive‐layer white organic light‐emitting diodes (WOLEDs) are demonstrated by using a small molecule, tris(4‐(phenylethynyl)phenyl)amine, without additional doping. By adjusting the annealing temperature, multiphotoluminescence is observed and various energy states are formed due to the change in the molecular configuration and packing with smaller spacing from heat‐induced rotation of the benzene rings. Abstract White organic light‐emitting diode (WOLED) technology has attracted considerable attention because of its potential use as a next‐generation solid‐state lighting source. However, most of the reported WOLEDs that employ the combination of multi‐emissive materials to generate white emission may suffer from color instability, high material cost, and a complex fabrication procedure which can be diminished by the single‐emitter‐based WOLED. Herein, a color‐tunable material, tris(4‐(phenylethynyl)phenyl)amine (TPEPA), is reported, whose photoluminescence (PL) spectrum is altered by adjusting the thermal annealing temperature nearly encompassing the entire visible spectra. Density functional theory calculations and transmission electron microscopy results offer mechanistic understanding of the PL redshift resulting from thermally activated rotation of benzene rings and rotation of 4‐(phenylethynyl) phenyl)amine connected to the central nitrogen atom that lead to formation of ordered molecular packing which improves the π–π stacking degree and increases electronic coupling. Further, by precisely controlling the annealing time and temperature, a white‐light OLED is fabricated with the maximum external quantum efficiency of 3.4% with TPEPA as the only emissive molecule. As far as it is known, thus far, this is the best performance achieved for single small organic molecule based WOLED devices.

Monitoring Nanocrystal Self‐Assembly in Real Time Using In Situ Small‐Angle X‐Ray Scattering

By Irina Lokteva, Michael Koof, Michael Walther, Gerhard Grübel, Felix Lehmkühler from Wiley: Small: Table of Contents. Published on Apr 16, 2019.

Time‐resolved self‐assembly of colloidal PbS nanocrystals upon controlled solvent evaporation is studied using in situ synchrotron small‐angle X‐ray scattering and X‐ray cross correlation analysis. PbS nanocrystals first form a highly ordered hexagonal closed‐packed superlattice in a solvent vapor saturated atmosphere, followed by a transition into the final body‐centered cubic superlattice upon complete evaporation of the solvent. Abstract Self‐assembled nanocrystal superlattices have attracted large scientific attention due to their potential technological applications. However, the nucleation and growth mechanisms of superlattice assemblies remain largely unresolved due to experimental difficulties to monitor intermediate states. Here, the self‐assembly of colloidal PbS nanocrystals is studied in real time by a combination of controlled solvent evaporation from the bulk solution and in situ small‐angle X‐ray scattering (SAXS) in transmission geometry. For the first time for the investigated system a hexagonal closed‐packed (hcp) superlattice formed in a solvent vapor saturated atmosphere is observed during slow solvent evaporation from a colloidal suspension. The highly ordered hcp superlattice is followed by a transition into the final body‐centered cubic superlattice upon complete drying. Additionally, X‐ray cross‐correlation analysis of Bragg reflections is applied to access information on precursor structures in the assembly process, which is not evident from conventional SAXS analysis. The detailed evolution of the crystal structure with time provides key results for understanding the assembly mechanism and the role of ligand–solvent interactions, which is important both for fundamental research and for fabrication of superlattices with desired properties.

Self‐Healing, Adhesive, and Highly Stretchable Ionogel as a Strain Sensor for Extremely Large Deformation

By Li Mei Zhang, Yuan He, Sibo Cheng, Hao Sheng, Keren Dai, Wen Jiang Zheng, Mei Xiang Wang, Zhen Shan Chen, Yong Mei Chen, Zhigang Suo from Wiley: Small: Table of Contents. Published on Apr 16, 2019.

An ionogel nanocomposite with the combined features of excellent autonomous self‐healing, strong adhesion, high stretchability, and strain sensitivity is fabricated. A conformal strain sensor based on the nanocomposite is demonstrated by changing electrical resistance with special distortion, like arbitrary curved and moving surfaces of a balloon with large inflation. The proof‐of‐concept strain sensor holds great potential for exploring various conformal mechanical sensor systems. Abstract Fabricating a strain sensor that can detect large deformation over a curved object with a high sensitivity is crucial in wearable electronics, human/machine interfaces, and soft robotics. Herein, an ionogel nanocomposite is presented for this purpose. Tuning the composition of the ionogel nanocomposites allows the attainment of the best features, such as excellent self‐healing (>95% healing efficiency), strong adhesion (347.3 N m−1), high stretchability (2000%), and more than ten times change in resistance under stretching. Furthermore, the ionogel nanocomposite–based sensor exhibits good reliability and excellent durability after 500 cycles, as well as a large gauge factor of 20 when it is stretched under a strain of 800–1400%. Moreover, the nanocomposite can self‐heal under arduous conditions, such as a temperature as low as −20 °C and a temperature as high as 60 °C. All these merits are achieved mainly due to the integration of dynamic metal coordination bonds inside a loosely cross‐linked network of ionogel nanocomposite doped with Fe3O4 nanoparticles.

Precise Patterning of Organic Semiconductor Crystals for Integrated Device Applications

By Xiujuan Zhang, Wei Deng, Ruofei Jia, Xiaohong Zhang, Jiansheng Jie from Wiley: Small: Table of Contents. Published on Apr 16, 2019.

Precise patterning of high‐mobility organic semiconductor crystals (OSCCs) is a prerequisite for practical applications. In this Review, recent fantastic progress in the development of patterning technologies of OSCCs and their corresponding device/circuit applications are systematically summarized. Abstract Development of high‐performance organic electronic and optoelectronic devices relies on high‐quality semiconducting crystals that have outstanding charge transport properties and long exciton diffusion length and lifetime. To achieve integrated device applications, it is a prerequisite to precisely locate the organic semiconductor crystals (OSCCs) to form a specifically patterned structure. Well‐patterned OSCCs can not only reduce leakage current and cross‐talk between neighboring devices, but also facilely integrate with other device elements and their corresponding interconnects. In this Review, general strategies for the patterning of OSCCs are summarized, and the advantages and limitations of different patterning methods are discussed. Discussion is focused on an advanced strategy for the high‐resolution and wafer‐scale patterning of OSCC by a surface microstructure‐assisted patterning method. Furthermore, the recent progress on OSCC pattern‐based integrated circuities is highlighted. Finally, the research challenges and directions of this young field are also presented.

pH‐Regulated Heterostructure Porous Particles Enable Similarly Sized Protein Separation

By Yongyang Song, Jun‐Bing Fan, Xiuling Li, Xinmiao Liang, Shutao Wang from Wiley: Advanced Materials: Table of Contents. Published on Apr 16, 2019.

Heterostructure porous particles synthesized by double emulsion interfacial polymerization can successfully separate proteins with similar size. Double emulsion interfacial polymerization endows the particles with a nanoscale carboxylic layer outside the particles and inside the pores, allowing pH‐regulated adsorption of proteins. Optimizing the environmental pH can enable the effective separation of proteins with similar size in a short time. Abstract Porous particles are frequently used for various healthcare applications that involve protein separation processes. However, conventional porous particles, either homogeneous particles or those subjected to surface modification with a layer of specific molecules, often encounter bottlenecks in separating proteins with similar size. Here, it is reported that heterostructure‐enabled separation particles (HESP), synthesized by a double emulsion interfacial polymerization process, can effectively and rapidly separate similarly sized proteins. Double emulsion interfacial polymerization endows the HESP with a nanoscale carboxylic layer outside the particles and inside the pores, allowing pH‐regulated selective adsorption of proteins. Thus, by optimizing the environmental pH, proteins with similar size can be effectively and rapidly separated. These HESP are expected to show potential in widespread applications ranging from biomolecule adsorption, encapsulation, and separation to controlled release and other biomedical fields.

Chirality Controls Mesenchymal Stem Cell Lineage Diversification through Mechanoresponses

By Yan Wei, Shengjie Jiang, Mengting Si, Xuehui Zhang, Jinying Liu, Zheng Wang, Cen Cao, Jianyong Huang, Houbing Huang, Lili Chen, Shutao Wang, Chuanliang Feng, Xuliang Deng, Lei Jiang from Wiley: Advanced Materials: Table of Contents. Published on Apr 16, 2019.

The chirality of a constructed 3D extracellular matrix is capable of controlling mesenchymal stem cell (MSC) lineage diversification in vitro and in vivo. The chirality provides primary heterogeneity to initiate biphasic fibronectin tethering, which induces significant alterations in mechanosensing and mechanotransduction to specify stem cell lineages of osteogenesis or adipogenesis. The findings present potential strategies for the biogenesis and regeneration. Abstract Biogenesis and tissue development are based on the heterogenesis of multipotent stem cells. However, the underlying mechanisms of stem cell fate specification are unclear. Chirality is one of the most crucial factors that affects stem cell development and is implicated in asymmetrical cell morphology formation; however, its function in heterogeneous cell fate determination remains elusive. In this study, it is reported that the chirality of a constructed 3D extracellular matrix (ECM) differentiates mesenchymal stem cells to diverse lineages of osteogenic and adipogenic cells by providing primary heterogeneity. Molecular analysis shows that left‐handed chirality of the ECM enhances the clustering of the mechanosensor Itgα5, while right‐handed chirality decreases this effect. These differential adhesion patterns further activate distinct mechanotransduction events involving the contractile state, focal adhesion kinase/extracellular signal‐regulated kinase 1/2 cascades, and yes‐associated protein/runt‐related transcription factor 2 nuclear translocation, which direct heterogeneous differentiation. Moreover, theoretical modeling demonstrates that diverse chirality mechanosensing is initiated by biphasic modes of fibronectin tethering. The findings of chirality‐dependent lineage specification of stem cells provide potential strategies for the biogenesis of organisms and regenerative therapies.

Hierarchically Porous Carbon Plates Derived from Wood as Bifunctional ORR/OER Electrodes

By Xinwen Peng, Lei Zhang, Zhongxin Chen, Linxin Zhong, Dengke Zhao, Xiao Chi, Xiaoxu Zhao, Ligui Li, Xihong Lu, Kai Leng, Cuibo Liu, Wei Liu, Wei Tang, Kian Ping Loh from Wiley: Advanced Materials: Table of Contents. Published on Apr 16, 2019.

The use of enzymes allows precise fabrication of wood‐based architectures, generating a large number of nanopores by selective hydrolysis of cellulose or hemicellulose, while retaining the mechanically strong, crosslinked structure intact. Such hierarchically porous, N‐doped wood plates exhibit a superb oxygen reduction reaction and oxygen evolution reaction activity in alkaline electrolyte for self‐supporting electrodes in high‐performance Zn–air batteries. Abstract Porous carbon electrodes have emerged as important cathode materials for metal–air battery systems. However, most approaches for fabricating porous carbon electrodes from biomass are highly energy inefficient as they require the breaking down of the biomass and its subsequent reconstitution into powder‐like carbon. Here, enzymes are explored to effectively hydrolyze the partial cellulose in bulk raw wood to form a large number of nanopores, which helps to maximally expose the inner parts of the raw wood to sufficiently dope nitrogen onto the carbon skeletons during the subsequent pyrolysis process. The resulting carbons exhibit excellent catalytic activity with respect to the oxygen reduction and oxygen evolution reactions. As‐fabricated cellulose‐digested, carbonized wood plates are mechanically strong, have high conductivity, and contain a crosslinked network and natural ion‐transport channels and can be employed directly as metal‐free electrodes without carbon paper, polymer binders, or carbon black. When used as metal‐free cathodes in zinc–air batteries, they result in a specific capacity of 801 mA h g−1 and an energy density of 955 W h kg−1 with the long‐term stability of the batteries being as high as 110 h. This work paves the way for the ready conversion of abundant biomass into high‐value engineering products for energy‐related applications.

All‐in‐One Porous Polymer Adsorbents with Excellent Environmental Chemosensory Responsivity, Visual Detectivity, Superfast Adsorption, and Easy Regeneration

By Yiming Xie, Wen Huang, Bingna Zheng, Shimei Li, Qiantong Liu, Zirun Chen, Weicong Mai, Ruowen Fu, Dingcai Wu from Wiley: Advanced Materials: Table of Contents. Published on Apr 16, 2019.

An advanced adsorbent with superadsorption, environmental stimuli response, and real‐time detection capability is designed and fabricated to efficiently treat polluted water. The adsorbent presents a hairy microporous nanospherical morphology, emits pH‐dependent blue/a white fluorescence, enables visible detection and superfast removal of micropollutants, exhibits excellent flow‐through adsorption performance, and demonstrates high regeneration efficiency. Abstract It remains a formidable challenge to construct advanced adsorbents with superb adsorption, environmental stimuli response, and real‐time detection capability for efficiently treating contaminants from complex environmental systems. A novel class of an all‐in‐one microporous adsorbent that simultaneously has excellent environmental chemosensory responsivity, visual detectivity, superfast micropollutant adsorption, as well as easy regeneration is reported herein. The advanced microporous adsorbent discussed in this study presents a hairy nanospherical morphology composed of a hairy stimuli‐responsive polymeric shell and a shell‐assisted superadsorptive microporous core. The adsorbent not only exhibits a valuable capability of pollutant detection by visible fluorescence quenching, but can also remove organic micropollutants from polluted water with super‐rapid speed (79%, 98%, and 100% of its equilibrium uptake in 7 s, 10 s, and 2 min, respectively) and excellent recyclability (>96%). More importantly, the adsorbent still shows unimpeded adsorption performance in the flow‐through adsorption tests (15 mL min−1), indicating a very appealing application prospect.

Low‐Temperature Conversion of Alcohols into Bulky Nanoporous Graphene and Pure Hydrogen with Robust Selectivity on CaO

By Gao‐Feng Han, Zhi‐Wen Chen, Jong‐Pil Jeon, Seok‐Jin Kim, Hyuk‐Jun Noh, Xiang‐Mei Shi, Feng Li, Qing Jiang, Jong‐Beom Baek from Wiley: Advanced Materials: Table of Contents. Published on Apr 16, 2019.

The cheaply available CaO can simultaneously transform renewable alcohols into pure hydrogen (≈99%) and high‐value graphene at a temperature as low as 500 °C. The concept on the comprehensive utilization of biomass with a carbon‐negative cycle offers a new way to mitigate global warming and the world's energy demands. Abstract The direct conversion of biorenewable alcohols into value‐added graphene and pure hydrogen (H2) at benign conditions is an important challenge, especially, considering the open carbon‐reduced cycle. In this study, it is demonstrated that inexpensive calcium oxide (CaO, from eggshells) can transform alcohols into bulky nanoporous graphene and pure hydrogen (≈99%) with robust selectivity at the temperature as low as 500 °C. Consequently, the growth of graphene can follow the direction of alcohol flow and uniformly penetrate into bulky nanoporous CaO platelets longer than 1 m without clogging. The experimental results and density functional theory calculations demonstrate that alcohol molecules can be catalytically carbonized on the surface of CaO at low temperature. The concept of the comprehensive utilization of biomass‐derived alcohols offers a carbon‐negative cycle for mitigating global warming and the energy demand.

Implanting Niobium Carbide into Trichoderma Spore Carbon: a New Advanced Host for Sulfur Cathodes

By Shenghui Shen, Xinhui Xia, Yu Zhong, Shengjue Deng, Dong Xie, Bo Liu, Yan Zhang, Guoxiang Pan, Xiuli Wang, Jiangping Tu from Wiley: Advanced Materials: Table of Contents. Published on Apr 16, 2019.

A novel hybrid host consisting of a N,P‐codoped trichoderma spore carbon (TSC) matrix and a conductive NbC adsorbent for sulfur cathodes is proposed. The designed TSC/NbC‐S electrode displays extraordinary performance with superior rate capability (810 mAh g−1 at 5 C) and ultrastable cycling life (937.9 mAh g−1 at 0.1 C after 500 cycles). Abstract Tailored construction of advanced carbon hosts is playing a great role in the development of high‐performance lithium–sulfur batteries (LSBs). Herein, a novel N,P‐codoped trichoderma spore carbon (TSC) with a bowl structure, prepared by a “trichoderma bioreactor” and annealing process is reported. Moreover, TSC shows excellent compatibility with conductive niobium carbide (NbC), which is in situ implanted into the TSC matrix in the form of nanoparticles forming a highly porous TSC/NbC host. Importantly, NbC plays a dual role in TSC for not only pore formation but also enhancement of conductivity. Excitingly, the sulfur can be well accommodated in the TSC/NbC host forming a high‐performance TSC/NbC‐S cathode, which exhibits greatly enhanced rate performance (810 mAh g−1 at 5 C) and long cycling life (937.9 mAh g−1 at 0.1 C after 500 cycles), superior to TSC‐S and other carbon/S counterparts due to the larger porosity, higher conductivity, and better synergetic trapping effect for the soluble polysulfide intermediate. The synergetic work of porous the conductive architecture, heterodoped N&P polar sites in TSC and polar conductive NbC provides new opportunities for enhancing physisorption and chemisorption of polysulfides leading to higher capacity and better rate capability.

The First 2D Homochiral Lead Iodide Perovskite Ferroelectrics: [R‐ and S‐1‐(4‐Chlorophenyl)ethylammonium]2PbI4

By Chen‐Kai Yang, Wang‐Nan Chen, Yan‐Ting Ding, Jing Wang, Yin Rao, Wei‐Qiang Liao, Yuan‐Yuan Tang, Peng‐Fei Li, Zhong‐Xia Wang, Ren‐Gen Xiong from Wiley: Advanced Materials: Table of Contents. Published on Apr 16, 2019.

2D homochiral lead iodide perovskite ferroelectrics, [R‐ and S‐1‐(4‐chlorophenyl)ethylammonium]2PbI4, crystallize in a polar space group P1 at room temperature, and undergo a 422F1 type ferroelectric phase transition at 483 and 473.2 K, respectively, showing a multiaxial ferroelectric nature. However, their racemic counterpart adopts a centrosymmetric space group P21/c, exhibiting no high‐temperature phase transition. Abstract 2D organic–inorganic lead iodide perovskites have recently received tremendous attention as promising light absorbers for solar cells, due to their excellent optoelectronic properties, structural tunability, and environmental stability. However, although great efforts have been made, no 2D lead iodide perovskites have been discovered as ferroelectrics, in which the ferroelectricity may improve the photovoltaic performance. Here, by incorporating homochiral cations, 2D lead iodide perovskite ferroelectrics [R‐1‐(4‐chlorophenyl)ethylammonium]2PbI4 and [S‐1‐(4‐chlorophenyl)ethylammonium]2PbI4 are successfully obtained. The vibrational circular dichroism spectra and crystal structural analysis reveal their homochirality. They both crystalize in a polar space group P1 at room temperature, and undergo a 422F1 type ferroelectric phase transition with transition temperature as high as 483 and 473.2 K, respectively, showing a multiaxial ferroelectric nature. They also possess semiconductor characteristics with a direct bandgap of 2.34 eV. Nevertheless, their racemic analogue adopts a centrosymmetric space group P21/c at room temperature, exhibiting no high‐temperature phase transition. The homochirality in 2D lead iodide perovskites facilitates crystallization in polar space groups. This finding indicates an effective way to design high‐performance 2D lead iodide perovskite ferroelectrics with great application prospects.

Engineered Bacterial Bioreactor for Tumor Therapy via Fenton‐Like Reaction with Localized H2O2 Generation

By Jin‐Xuan Fan, Meng‐Yun Peng, He Wang, Hao‐Ran Zheng, Zong‐Lin Liu, Chu‐Xin Li, Xia‐Nan Wang, Xin‐Hua Liu, Si‐Xue Cheng, Xian‐Zheng Zhang from Wiley: Advanced Materials: Table of Contents. Published on Apr 16, 2019.

A Fenton‐like bioreactor based on bacteria is reported for tumor therapy without exogenous H2O2 provision. It is found that this bioreactor can achieve effective tumor colonization, and realize a self‐supplied therapeutic Fenton‐like reaction without additional H2O2 provision. Abstract Synthetic biology based on bacteria has been displayed in antitumor therapy and shown good performance. In this study, an engineered bacterium Escherichia coli MG1655 is designed with NDH‐2 enzyme (respiratory chain enzyme II) overexpression (Ec‐pE), which can colonize in tumor regions and increase localized H2O2 generation. Following from this, magnetic Fe3O4 nanoparticles are covalently linked to bacteria to act as a catalyst for a Fenton‐like reaction, which converts H2O2 to toxic hydroxyl radicals (•OH) for tumor therapy. In this constructed bioreactor, the Fenton‐like reaction occurs with sustainably synthesized H2O2 produced by engineered bacteria, and severe tumor apoptosis is induced via the produced toxic •OH. These results show that this bioreactor can achieve effective tumor colonization, and realize a self‐supplied therapeutic Fenton‐like reaction without additional H2O2 provision.

Revealing the Cluster‐Cloud and Its Role in Nanocrystallization

By Biao Jin, Yanming Wang, Zhaoming Liu, Arthur France‐Lanord, Jeffrey C. Grossman, Chuanhong Jin, Ruikang Tang from Wiley: Advanced Materials: Table of Contents. Published on Apr 16, 2019.

Liquid cell transmission electron microscopy reveals a new nanocrystallization pathway. The nanoparticle crystallization is mediated by an important intermediate phase of condensed atomic cluster aggregates, which is defined as a cluster‐cloud. Specifically, it follows three fundamental steps: formation of the cluster‐cloud through the aggregation of clusters; condensation of the cluster‐cloud to a poorly crystallized nanoparticle; and multiple out‐and‐in relaxations toward a single crystal via order–disorder phase separation. Abstract Elucidating the early stages of crystallization from supersaturated solutions is of critical importance, but remains a great challenge. An in situ liquid cell transmission electron microscopy study reveals an intermediate state of condensed atomic clusters during Pd and Au crystallizations, which is named a “cluster‐cloud.” It is found that nucleation is initiated by the collapse of a cluster‐cloud, first forming a nanoparticle. The subsequent particle maturation proceeds via multiple out‐and‐in relaxations of the cluster‐cloud to improve crystallinity: from a poorly crystallized phase, the particle evolves into a well‐defined single‐crystal phase. Both experimental investigations and atomistic simulations suggest that the cluster‐cloud‐mediated nanocrystallization involves an order–disorder phase separation and reconstruction, which is energetically favored compared to local rearrangements within the particle. This finding grants new insights into nanocrystallization mechanisms, and provides useful information for the improvement of synthesis pathways of nanocrystals.

Epitaxial Growth of CsPbX3 (X = Cl, Br, I) Perovskite Quantum Dots via Surface Chemical Conversion of Cs2GeF6 Double Perovskites: A Novel Strategy for the Formation of Leadless Hybrid Perovskite Phosphors with Enhanced Stability

By Yi Wei, Kai Li, Ziyong Cheng, Manman Liu, Hui Xiao, Peipei Dang, Sisi Liang, Zhijian Wu, Hongzhou Lian, Jun Lin from Wiley: Advanced Materials: Table of Contents. Published on Apr 16, 2019.

Leadless hybrid perovskites are obtained by the epitaxial synthesis of CsPbX3 (X = Cl, Br, I) perovskite quantum dots through surface chemical conversion of Cs2GeF6 double perovskites with PbX2 (X = Cl, Br, I). The obtained CsPbBr3/Cs2GeF6 products show high color purity and enhanced stability, indicating their potential application in lighting devices. Abstract Lead halide perovskites (LHPs) have received increased attention owing to their intriguing optoelectronic and photonic properties. However, the toxicity of lead and the lack of long‐term stability are potential obstacles for the application of LHPs. Herein, the epitaxial synthesis of CsPbX3 (X = Cl, Br, I) perovskite quantum dots (QDs) by surface chemical conversion of Cs2GeF6 double perovskites with PbX2 (X = Cl, Br, I) is reported. The experimental results show that the surface of the Cs2GeF6 double perovskites is partially converted into CsPbX3 perovskite QDs and forms a CsPbX3/Cs2GeF6 hybrid structure. The theoretical calculations reveal that the CsPbBr3 conversion proceeds at the Cs2GeF6 edge through sequential growth of multiple PbBr6 4− layers. Through the conversion strategy, luminescent and color‐tunable CsPbX3 QDs can be obtained, and these products present high stability against decomposition due to anchoring effects. Moreover, by partially converting red emissive Cs2GeF6:Mn4+ to green emissive CsPbBr3, the CsPbBr3/Cs2GeF6:Mn4+ hybrid can be employed as a low‐lead hybrid perovskite phosphor on blue LED chips to produce white light. The leadless CsPbX3/Cs2GeF6 hybrid structure with stable photoluminescence opens new paths for the rational design of efficient emission phosphors and may stimulate the design of other functional CsPbX3/Cs‐containing hybrid structures.

Boosting Water Dissociation Kinetics on Pt–Ni Nanowires by N‐Induced Orbital Tuning

By Yufang Xie, Jinyan Cai, Yishang Wu, Yipeng Zang, Xusheng Zheng, Jian Ye, Peixin Cui, Shuwen Niu, Yun Liu, Junfa Zhu, Xiaojing Liu, Gongming Wang, Yitai Qian from Wiley: Advanced Materials: Table of Contents. Published on Apr 16, 2019.

The water dissociation kinetics of Pt–Ni nanowires are significantly boosted via N‐induced orbital tuning. N can specifically bind to the Ni sites and subsequently enable the Ni sites to provide empty dz2 orbitals for water adsorption and activation. These N‐modified Pt–Ni nanowires display an unprecedented alkaline hydrogen evolution catalysis. Abstract Although it is commonly believed that the water‐dissociation‐related Volmer process is the rate‐limiting step for alkaline hydrogen evolution reaction (HER) on Pt‐based catalysts, the underlying essence, particularly on the atomic scale, still remains unclear. Herein, it is revealed that the sluggish water‐dissociation behavior probably stems from unfavorable orbital orientation and the kinetic issue is successfully resolved via N‐induced orbital tuning. Impressively, N modified Pt–Ni nanowires deliver an ultralow overpotential of 13 mV at 10 mA cm−2, which represents a new benchmark for alkaline HER catalysis. Fine‐structural characterization and density functional theory analysis illustrate that the introduced nitrogen can uniquely modulate the electron densities around the Ni sites, and further create empty dz2 orbitals with superior orientation for water adsorption and activation. More importantly, it is demonstrated that N‐induced orbital modulation can generally boost the alkaline HER activities of Pt–Co, Pt–Ni, and Pt–Cu, offering a new perspective for the design of HER catalysts and beyond.

Scalable Fabrication of Highly Crystalline Organic Semiconductor Thin Film by Channel‐Restricted Screen Printing toward the Low‐Cost Fabrication of High‐Performance Transistor Arrays

By Shuming Duan, Xiong Gao, Yu Wang, Fangxu Yang, Mingxi Chen, Xiaotao Zhang, Xiaochen Ren, Wenping Hu from Wiley: Advanced Materials: Table of Contents. Published on Apr 16, 2019.

A highly crystalline organic semiconductor thin‐film array is fabricated by screen printing using a simple and efficient method. The as‐prepared organic 8 × 8 field‐effect‐transistor array exhibits excellent performance characteristics and a maximum mobility of 12.10 cm2 V−1 s−1. The method can also be carried out using a flexible substrate, with good performance. Abstract Control over the morphology and crystallinity of small‐molecule organic semiconductor (OSC) films is of key importance to enable high‐performance organic optoelectronic devices. However, such control remains particularly challenging for solution‐processed OSC devices because of the complex crystallization kinetics of small‐molecule OSC materials in the dynamic flow of inks. Here, a simple yet effective channel‐restricted screen‐printing method is reported, which uses small‐molecule OSCs/insulating polymer to yield large‐grained small‐molecule OSC thin‐film arrays with good crystallization and preferred orientation. The use of cross‐linked organic polymer banks produces a confinement effect to trigger the outward convective flow at two sides of the channel by the fast solvent evaporation, which imparts the transport of small‐molecule OSC solutes and promotes the growth of small‐molecule OSC crystals parallel to the channel. The small‐molecule OSC thin‐film array produced by screen printing exhibits excellent performance characteristics with an average mobility of 7.94 cm2 V−1 s−1 and a maximum mobility of 12.10 cm2 V−1 s−1, which are on par with its single crystal. Finally, screen printing can be carried out using a flexible substrate, with good performance. These demonstrations bring this robust screen‐printing method closer to industrial application and expand its applicability to various flexible electronics.

A Dynamic Graphene Oxide Network Enables Spray Printing of Colloidal Gels for High‐Performance Micro‐Supercapacitors

By Zhiyuan Xiong, Xiawei Yun, Ling Qiu, Youyi Sun, Bo Tang, Zijun He, Jing Xiao, Dwayne Chung, Tuck Wah Ng, Hao Yan, Ranran Zhang, Xiaogong Wang, Dan Li from Wiley: Advanced Materials: Table of Contents. Published on Apr 16, 2019.

Spray printing of graphene oxide (GO)‐containing colloidal gels is achieved with high throughput and high fidelity by exploiting their ultrafast elastic‐like recovery, which is endowed by the GO network. Wearable high‐performance micro‐supercapacitors are fabricated through spray printing of GO/polyaniline gels. This work highlights the hidden potential of two‐dimensional materials as functional yet highly efficient rheological enhancers for industrial processing of nanomaterials. Abstract Properly controlling the rheological properties of nanoparticle inks is crucial to their printability. Here, it is reported that colloidal gels containing a dynamic network of graphene oxide (GO) sheets can display unusual rheological properties after high‐rate shearing. When mixed with polyaniline nanofiber dispersions, the GO network not only facilitates the gelation process but also serves as an effective energy‐transmission network to allow fast structural recovery after the gel is deformed by high‐rate shearing. This extraordinary fast recovery phenomenon has made it possible to use the conventional air‐brush spray technique to print the gel with high‐throughput and high fidelity on nonplanar flexible surfaces. The as‐printed micro‐supercapacitors exhibit an areal capacitance 4–6 times higher than traditionally spray‐printed ones. This work highlights the hidden potential of 2D materials as functional yet highly efficient rheological enhancers to facilitate industrial processing of nanomaterial‐based devices.

A Novel Hybrid‐Layered Organic Phototransistor Enables Efficient Intermolecular Charge Transfer and Carrier Transport for Ultrasensitive Photodetection

By Yuanhong Gao, Ya Yi, Xinwei Wang, Hong Meng, Dangyuan Lei, Xue‐Feng Yu, Paul K. Chu, Jia Li from Wiley: Advanced Materials: Table of Contents. Published on Apr 16, 2019.

A novel hybrid‐layered organic phototransistor, (HL‐OPT) architecture consisting of an organic semiconductor channel layer for fast carrier transport, a photoactive organic bulk‐heterojunction layer, and an ultrathin inorganic interlayer sandwiched in between is proposed. By combining the virtues of the charge‐trapping effect and efficient carrier transport simultaneously, significant enhancement in the photodetection performance is achieved from the fabricated HL‐OPT. Abstract The interfacial charge effect is crucial for high‐sensitivity organic phototransistors (OPTs), but conventional layered and hybrid OPTs have a trade‐off in balancing the separation, transport, and recombination of photogenerated charges, consequently impacting the device performance. Herein, a novel hybrid‐layered phototransistor (HL‐OPT) is reported with significantly improved photodetection performance, which takes advantages of both the charge‐trapping effect (CTE) and efficient carrier transport. The HL‐OPT consisting of 2,7‐dioctyl[1]benzothieno[3,2‐b][1]benzothiophene (C8‐BTBT) as conduction channel, C8‐BTBT:[6,6]‐phenyl‐C61‐butyric acid methyl ester (PC61BM) bulk heterojunction as photoactive layer, and sandwiched MoO3 interlayer as a charge‐transport interlayer exhibits outstanding photodetection characteristics such as a photosensitivity (Ilight/Idark) of 2.9 × 106, photoresponsivity (R) of 8.6 × 103 A W−1, detectivity (D*) of 3.4 × 1014 Jones, and external quantum efficiency of 3 × 106% under weak light illumination of 32 µW cm−2. The mechanism and strategy described here provide new insights into the design and optimization of high‐performance OPTs spanning the ultraviolet and near infrared (NIR) range as well as fundamental issues pertaining to the electronic and photonic properties of the devices.

Manipulate the Electronic and Magnetic States in NiCo2O4 Films through Electric‐Field‐Induced Protonation at Elevated Temperature

By Meng Wang, Xuelei Sui, Yujia Wang, Yung‐Hsiang Juan, Yingjie Lyu, Huining Peng, Tongtong Huang, Shengchun Shen, Chenguang Guo, Jianbing Zhang, Zhuolu Li, Hao‐Bo Li, Nianpeng Lu, Alpha T. N'Diaye, Elke Arenholz, Shuyun Zhou, Qing He, Ying‐Hao Chu, Wenhui Duan, Pu Yu from Wiley: Advanced Materials: Table of Contents. Published on Apr 16, 2019.

Ionic‐liquid‐gating‐induced protonation is realized in the inverse spinel NiCo2O4 with an elevated environmental temperature, and has a major impact on the electronic and magnetic states. This study takes the understanding of the ionic‐liquid‐gating‐induced protonation process a step further and provides a generic strategy to boost this effect in extended material systems. Abstract Ionic‐liquid‐gating‐ (ILG‐) induced proton evolution has emerged as a novel strategy to realize electron doping and manipulate the electronic and magnetic ground states in complex oxides. While the study of a wide range of systems (e.g., SrCoO2.5, VO2, WO3, etc.) has demonstrated important opportunities to incorporate protons through ILG, protonation remains a big challenge for many others. Furthermore, the mechanism of proton intercalation from the ionic liquid/solid interface to whole film has not yet been revealed. Here, with a model system of inverse spinel NiCo2O4, an increase in system temperature during ILG forms a single but effective method to efficiently achieve protonation. Moreover, the ILG induces a novel phase transformation in NiCo2O4 from ferrimagnetic metallic into antiferromagnetic insulating with protonation at elevated temperatures. This study shows that environmental temperature is an efficient tuning knob to manipulate ILG‐induced ionic evolution.

Tuning Oxygen Vacancies in Ultrathin TiO2 Nanosheets to Boost Photocatalytic Nitrogen Fixation up to 700 nm

By Yunxuan Zhao, Yufei Zhao, Run Shi, Bin Wang, Geoffrey I. N. Waterhouse, Li‐Zhu Wu, Chen‐Ho Tung, Tierui Zhang from Wiley: Advanced Materials: Table of Contents. Published on Apr 16, 2019.

Ultrathin TiO2 nanosheets with abundant oxygen vacancies (VO) are synthesized through a facile copper‐doping strategy, exhibiting remarkable and stable performance for the photofixation of N2 to NH3 at a rate of 78.9 µmol g−1 h−1 under ambient conditions (especially up to 700 nm). The outstanding activity can be attributed to the existence of VO and compressive strain in the nanosheets. Abstract Dinitrogen reduction to ammonia using transition metal catalysts is central to both the chemical industry and the Earth's nitrogen cycle. In the Haber–Bosch process, a metallic iron catalyst and high temperatures (400 °C) and pressures (200 atm) are necessary to activate and cleave NN bonds, motivating the search for alternative catalysts that can transform N2 to NH3 under far milder reaction conditions. Here, the successful hydrothermal synthesis of ultrathin TiO2 nanosheets with an abundance of oxygen vacancies and intrinsic compressive strain, achieved through a facile copper‐doping strategy, is reported. These defect‐rich ultrathin anatase nanosheets exhibit remarkable and stable performance for photocatalytic reduction of N2 to NH3 in water, exhibiting photoactivity up to 700 nm. The oxygen vacancies and strain effect allow strong chemisorption and activation of molecular N2 and water, resulting in unusually high rates of NH3 evolution under visible‐light irradiation. Therefore, this study offers a promising and sustainable route for the fixation of atmospheric N2 using solar energy.

Field and Current Control of the Electrical Conductivity of an Artificial 2D Honeycomb Lattice

By Yiyao Chen, Brock Summers, Ashutosh Dahal, Valeria Lauter, Giovanni Vignale, Deepak K. Singh from Wiley: Advanced Materials: Table of Contents. Published on Apr 16, 2019.

Magnetic charge movement can profoundly impact the electrical properties of a magnetic material, essentially manifesting the spintronic model of electrical conduction. An artificial magnetic honeycomb provides a facile platform to realize it. It is shown that the rearrangement of magnetic charges to a Wigner‐crystal‐type novel state gives rise to a colossal change in electrical conductivity in a neodymium honeycomb lattice. Abstract The conductivity of a neodymium‐based artificial honeycomb lattice undergoes dramatic changes upon application of magnetic fields and currents. These changes are attributed to a redistribution of magnetic charges that are formed at the vertices of the honeycomb due to the nonvanishing net flux of magnetization from adjacent magnetic elements. It is suggested that the application of a large magnetic field or a current causes a transition from a disordered state, in which magnetic charges are distributed at random, to an ordered state, in which they are regularly arranged on the sites of two interpenetrating triangular Wigner crystals. The field and current tuning of electrical properties are highly desirable functionalities for spintronics applications. Consequently, a new spintronics research platform can be envisaged using artificial magnetic honeycomb lattices.

Stable Na Plating and Stripping Electrochemistry Promoted by In Situ Construction of an Alloy‐Based Sodiophilic Interphase

By Shuai Tang, Yi‐Yang Zhang, Xia‐Guang Zhang, Jun‐Tao Li, Xue‐Yin Wang, Jia‐Wei Yan, De‐Yin Wu, Ming‐Sen Zheng, Quan‐Feng Dong, Bing‐Wei Mao from Wiley: Advanced Materials: Table of Contents. Published on Apr 16, 2019.

Stable Na plating/stripping electrochemical behaviors are achieved by using the in situ formed sodiophilic sodium‐metal (metal = Au, Sn, Sb) alloy interphase. By simultaneous control over the stripping cut‐off potential and employment of anchored metal particles, Na plating/stripping cycling is extended to 2000 times at 2 mA cm−2 with an average Coulombic efficiency of 99.9% on the sodium‐metal alloy‐based interphase. Abstract Sodium metal anodes are poor due to the reversibility of Na plating/stripping, which hinders their practical applications. A strategy to form a sodiophilic Au–Na alloy interphase on a Cu current collector, involving a sputtered Au thin layer, is shown to enable efficient Na plating/stripping for a certain period of time. Herein, electrochemical behaviors of Na plating on different substrates are explored, and it is revealed that the sodiophilic interphase can be achieved universally by in situ formation of M–Na (M = Au, Sn, and Sb) alloys during Na plating prior to Na bulk deposition in the initial cycle. Moreover, it is found that repetitive alloying–dealloying leads to falling‐off of thin film sodiophilic materials and thus limits the lifespan of efficient Na cycling. Therefore, an approach is further developed by employing particles of sodiophilic materials combined with the control over the cutoff potential, which significantly improves the stability of Na plating/stripping process. Especially, the low‐cost Cu@Sn‐NPs and Cu@Sb‐MPs composite current collectors allow Na plating and stripping to cycle for 2000 and 1700 times with the average efficiency of 99.9% at 2 mA cm−2.

Space‐Confined Polymerization: Controlled Fabrication of Nitrogen‐Doped Polymer and Carbon Microspheres with Refined Hierarchical Architectures

By Tao Wang, Yan Sun, Liangliang Zhang, Kaiqian Li, Yikun Yi, Shuyan Song, Mingtao Li, Zhen‐An Qiao, Sheng Dai from Wiley: Advanced Materials: Table of Contents. Published on Apr 16, 2019.

A space‐confined polymerization strategy is designed to synthesize a new kind of 2,6‐diaminopyridine‐based multichamber polymer microsphere (MCP) and N‐doped multichamber carbon microsphere (MCC). The morphology and sizes of the MCP are controlled by a dual‐surfactant system. The chambers in the MCC are fully penetrated with abundant micropores by CO2 activation. Abstract The construction of refined architectures plays a crucial role in performance improvement and application expansion of advanced materials. The synthesis of carbon microspheres with a refined hierarchical structure is still a problem in synthetic methodology, because it is difficult to achieve the necessary delicate control of the interior structure and outer shell across the microscale to nanoscale. Nitrogen‐doped multichamber carbon (MCC) microspheres with a refined hierarchical structure are realized here via a surfactant‐directed space‐confined polymerization strategy. The MCC precursor is not the traditional phenolic resol but a new kind of 2,6‐diaminopyridine‐based multichamber polymer (MCP) with a high nitrogen content up to 20 wt%. The morphology and sizes of MCP microspheres can be easily controlled by a dual‐surfactant system. The as‐synthesized MCC with a highly microporous shell, a multichamber inner core, and beneficial N‐doping can serve as a promising supercapacitor material.

Healing of Planar Defects in 2D Materials via Grain Boundary Sliding

By Xiaoxu Zhao, Yujin Ji, Jianyi Chen, Wei Fu, Jiadong Dan, Yuanyue Liu, Stephen J. Pennycook, Wu Zhou, Kian Ping Loh from Wiley: Advanced Materials: Table of Contents. Published on Apr 16, 2019.

It is found that 2D planar defects in multilayered 2D crystals can be healed by grain boundary (GB) sliding, which works like a “wiper blade” to correct all metastable phases into thermodynamically stable phases along its trace. The driving force for GB sliding is the gain in interlayer binding energy. The study highlights the role of the often‐neglected interlayer interactions for defect repair, which have significant potential for obtaining large‐scale defect‐free 2D films. Abstract Understanding the mechanisms and kinetics of defect annihilations, particularly at the atomic scale, is important for the preparation of high‐quality crystals for realizing the full potential of 2D transition metal dichalcogenides (TMDCs) in electronics and quantum photonics. Herein, by performing in situ annealing experiments in an atomic resolution scanning transmission electron microscope, it is found that stacking faults and rotational disorders in multilayered 2D crystals can be healed by grain boundary (GB) sliding, which works like a “wiper blade” to correct all metastable phases into thermodynamically stable phases along its trace. The driving force for GB sliding is the gain in interlayer binding energy as the more stable phase grows at the expanse of the metastable ones. Density functional theory calculations show that the correction of 2D stacking faults is triggered by the ejection of Mo atoms in mirror twin boundaries, followed by the collective migrations of 1D GB. The study highlights the role of the often‐neglected interlayer interactions for defect repair in 2D materials and shows that exploiting these interactions has significant potential for obtaining large‐scale defect‐free 2D films.

Atomically Transition Metals on Self‐Supported Porous Carbon Flake Arrays as Binder‐Free Air Cathode for Wearable Zinc−Air Batteries

By Dongxiao Ji, Li Fan, Linlin Li, Shengjie Peng, Deshuang Yu, Junnan Song, Seeram Ramakrishna, Shaojun Guo from Wiley: Advanced Materials: Table of Contents. Published on Apr 16, 2019.

A class of single‐atom‐anchored hierarchically porous monoliths for flexible energy storage is prepared by a facile and easily scalable “impregnation–carbonization–acidification” strategy. It exhibits excellent bifunctional electrocatalytic activity for oxygen reduction/evolution reactions. Wearable zinc–air batteries based on this binder‐free monolith show low overpotential and high mechanical stability. Abstract Metal single‐atom materials with their high atom utilization efficiency and unique electronic structures usually show remarkable catalytic performances in many crucial chemical reactions. Herein, a facile and easily scalable “impregnation‐carbonization‐acidification” strategy for fabricating a class of single‐atom‐anchored (including cobalt and nickel single atoms) monolith as superior binder‐free electrocatalysts for developing high‐performance wearable Zn–air batteries is reported. The as‐prepared single atoms, supported by N‐doped carbon flake arrays grown on carbon nanofibers assembly (M SA@NCF/CNF), demonstrate the dual characteristics of excellent catalytic activity (reversible oxygen overpotential of 0.75 V) and high stability, owing to the greatly improved active sites' accessibility and optimized single‐sites/pore‐structures correlations. Furthermore, wearable Zn–air battery based on Co SA@NCF/CNF air electrode displays superior stability under deformation, satisfactory energy storage capacity, and good practicality to be utilized as an integrated battery system. Theoretical calculations reveal a mechanism for the promotion of the catalytic performances on single atomic sites by lowering the overall oxygen reduction/evolution reaction barriers comparing to metal cluster co‐existing configuration. These findings provide a facile strategy for constructing free‐standing single‐atom materials as well as the engineering of high‐performance binder‐free catalytic electrodes.

Monodisperse and Uniform Mesoporous Silicate Nanosensitizers Achieve Low‐Dose X‐Ray‐Induced Deep‐Penetrating Photodynamic Therapy

By Wenjing Sun, Tianhang Shi, Li Luo, Xiaomei Chen, Peng Lv, Ying Lv, Yixi Zhuang, Jinjie Zhu, Gang Liu, Xiaoyuan Chen, Hongmin Chen from Wiley: Advanced Materials: Table of Contents. Published on Apr 16, 2019.

A metal‐incorporated mesoporous silica nanosensitizer is synthesized, which achieves low‐dose X‐ray‐induced deep‐penetrating photodynamic therapy. This efficient killing of cancer cells is attributed to the synergy of radiotherapy and photodynamic therapy. The present research is of great value to the development of silicate‐based X‐ray‐induced photodynamic therapy for cancer management. Abstract X‐ray‐induced photodynamic therapy (X‐PDT) combines both the advantages of radiotherapy (RT) and PDT, and has considerable potential applications in clinical deep‐penetrating cancer therapy. However, it is still a major challenge to prepare monodisperse nanoscintillators with uniform size and high light yield. In this study, a general and rapid synthesis method is presented that can achieve large‐scale preparation of monodisperse and uniform silicate nanoscintillators. By simply adjusting the metal dopants, silicate nanoscintillators with controllable size and X‐ray‐excited optical luminescence (450–900 nm) are synthesized by employing a general ion‐incorporated silica‐templating method. To make full use of external radiation, the silicate nanoscintillators are conjugated with photosensitizer rose bengal and arginylglycylaspartic acid (RGD) peptide, making them intrinsically dual‐modal targeted imaging probes. Both in vitro and in vivo experiments demonstrate that the silicate nanosensitizers can accumulate effectively in tumors and achieve significant inhibitory effect on tumor progression under low‐dose X‐ray irradiation, while minimally affecting normal tissues. The insights gained in this study may provide an attractive route to synthesize nanosensitizers to overcome some of the limitations of RT and PDT in cancer treatment.

Electro‐Optic Modulation in Hybrid Metal Halide Perovskites

By Yuan Gao, Grant Walters, Ying Qin, Bin Chen, Yimeng Min, Ali Seifitokaldani, Bin Sun, Petar Todorovic, Makhsud I. Saidaminov, Alan Lough, Sefaattin Tongay, Sjoerd Hoogland, Edward H. Sargent from Wiley: Advanced Materials: Table of Contents. Published on Apr 16, 2019.

Optical anisotropy in hybrid metal halide perovskites is demonstrated and the first account of the linear electro‐optic effect in these materials reported. These findings, along with the flexibility and solution‐processability of these materials, may suggest new applications for hybrid metal halide perovskites in polarizing optics and electro‐optic modulators. Abstract Rapid and efficient conversion of electrical signals to optical signals is needed in telecommunications and data network interconnection. The linear electro‐optic (EO) effect in noncentrosymmetric materials offers a pathway to such conversion. Conventional inorganic EO materials make on‐chip integration challenging, while organic nonlinear molecules suffer from thermodynamic molecular disordering that decreases the EO coefficient of the material. It has been posited that hybrid metal halide perovskites could potentially combine the advantages of inorganic materials (stable crystal orientation) with those of organic materials (solution processing). Here, layered metal halide perovskites are reported and investigated for in‐plane birefringence and linear electro‐optic response. Phenylmethylammonium lead chloride (PMA2PbCl4) crystals are grown that exhibit a noncentrosymmetric space group. Birefringence measurements and Raman spectroscopy confirm optical and structural anisotropy in the material. By applying an electric field on the crystal surface, the linear EO effect in PMA2PbCl4 is reported and its EO coefficient is determined to be 1.40 pm V−1. This is the first demonstration of this effect in hybrid metal halide perovskites, materials that feature both highly ordered crystalline structures and solution processability. The in‐plane birefringence and electro‐optic response reveal that layered perovskite crystals could be further explored for potential applications in polarizing optics and EO modulation.

Well‐Dispersed Nickel‐ and Zinc‐Tailored Electronic Structure of a Transition Metal Oxide for Highly Active Alkaline Hydrogen Evolution Reaction

By Tao Ling, Tong Zhang, Binghui Ge, Lili Han, Lirong Zheng, Feng Lin, Zhengrui Xu, Wen‐Bin Hu, Xi‐Wen Du, Kenneth Davey, Shi‐Zhang Qiao from Wiley: Advanced Materials: Table of Contents. Published on Apr 16, 2019.

A controlled tailoring of electronic structure of an oxide for the hydrogen evolution reaction (HER) is reported. Dual Ni and Zn doping is shown to be responsible for a significant increase in the HER activity of the host oxide, which was previously considered as catalytically inactive. The engineered oxide nanorods exhibit significantly high HER activity and are amongst the most active reported. Abstract The practical scale‐up of renewable energy technologies will require catalysts that are more efficient and durable than present ones. This is, however, a formidable challenge that will demand a new capability to tailor the electronic structure. Here, an original electronic structure tailoring of CoO by Ni and Zn dual doping is reported. This changes it from an inert material into one that is highly active for the hydrogen evolution reaction (HER). Based on combined density functional theory calculations and cutting‐edge characterizations, it is shown that dual Ni and Zn doping is responsible for a highly significant increase in HER activity of the host oxide. That is, the Ni dopants cluster around surface oxygen vacancy of the host oxide and provide an ideal electronic surface structure for hydrogen intermediate binding, while the Zn dopants distribute inside the host oxide and modulate the bulk electronic structure to boost electrical conduction. As a result, the dual‐doped Ni, Zn CoO nanorods achieve current densities of 10 and 20 mA cm−2 at overpotentials of, respectively, 53 and 79 mV. This outperforms reported state‐of‐the‐art metal oxide, metal oxide/metal, metal sulfide, and metal phosphide catalysts.

Stressing the Role of DNA as a Drug Carrier: Synthesis of DNA–Drug Conjugates through Grafting Chemotherapeutics onto Phosphorothioate Oligonucleotides

By Yuanyuan Guo, Jiao Zhang, Fei Ding, Gaifang Pan, Jing Li, Jing Feng, Xinyuan Zhu, Chuan Zhang from Wiley: Advanced Materials: Table of Contents. Published on Apr 16, 2019.

A DNA–drug conjugate (DDC) is constructed by an effective conjugation method based on the reaction between the phosphorothioate groups in the deoxyribonucleic acid (DNA) backbone and benzyl‐bromide‐modified chemotherapeutics. After grafting a multitude of paclitaxel molecules on DNA, the resulting amphiphilic DDC self‐assembles into SNA‐like micellar nanoparticles, which are further engineered into a new drug delivery system with multifunctionalities for a comprehensive antitumor therapy. Abstract To stress the role of deoxyribonucleic acid (DNA) as a drug carrier, an efficient conjugation strategy in which chemotherapeutics can be grafted onto a phosphorothiolated DNA backbone through the reaction between the phosphorothioate group (PS) and a benzyl bromide group is proposed. As a proof of concept, benzyl‐bromide‐modified paclitaxel (PTX) is employed to graft onto the DNA backbone at the PS modification sites. Due to the easy preparation of phosphorothiolated DNA at any desired position during its solid‐phase synthesis, diblock DNA strands containing both normal phosphodiester segment (PODNA) and phosphorothiolate segment (PSDNA) are directly grafted with a multitude of PTXs without using complicated and exogenous linkers. Then, the resulting amphiphilic PODNA‐blocked‐(PSDNA‐grafted PTX) conjugates (PODNA‐b‐(PSDNA‐g‐PTX)) assemble into PTX‐loaded spherical nucleic acid (SNA)‐like micellar nanoparticles (PTX‐SNAs) with a high drug loading ratio up to ≈53%. Importantly, the PODNA segment maintains its molecular recognition property and biological functions, which allows the as‐prepared PTX‐SNAs to be further functionalized with tumor‐targeting aptamers, fluorescent probe strands, or antisense sequences. These multifunctional PTX‐SNAs demonstrate active tumor‐targeting delivery, efficient inhibition of tumor growth, and the reversal of drug resistance both in vitro and in vivo for comprehensive antitumor therapy.

Do Images of Biskyrmions Show Type‐II Bubbles?

By James C. Loudon, Alison C. Twitchett‐Harrison, David Cortés‐Ortuño, Max T. Birch, Luke A. Turnbull, Aleš Štefančič, Feodor Y. Ogrin, Erick O. Burgos‐Parra, Nicholas Bukin, Angus Laurenson, Horia Popescu, Marijan Beg, Ondrej Hovorka, Hans Fangohr, Paul A. Midgley, Geetha Balakrishnan, Peter D. Hatton from Wiley: Advanced Materials: Table of Contents. Published on Apr 16, 2019.

Research on skyrmions has yielded reports of biskyrmions: bound pairs of counter‐rotating vortices of magnetization. This study combines electron microscopy, X‐ray holography, and simulations to investigate biskyrmions in MnNiGa. It demonstrates that images of biskyrmions can be explained as type‐II magnetic bubbles. It is not the magnetization but the magnetic flux density from this object that forms the counter‐rotating vortices. Abstract The intense research effort investigating magnetic skyrmions and their applications for spintronics has yielded reports of more exotic objects including the biskyrmion, which consists of a bound pair of counter‐rotating vortices of magnetization. Biskyrmions have been identified only from transmission electron microscopy images and have not been observed by other techniques, nor seen in simulations carried out under realistic conditions. Here, quantitative Lorentz transmission electron microscopy, X‐ray holography, and micromagnetic simulations are combined to search for biskyrmions in MnNiGa, a material in which they have been reported. Only type‐I and type‐II magnetic bubbles are found and images purported to show biskyrmions can be explained as type‐II bubbles viewed at an angle to their axes. It is not the magnetization but the magnetic flux density resulting from this object that forms the counter‐rotating vortices.

Freely Suspended, van der Waals Bound Organic Nanometer‐Thin Functional Films: Mechanical and Electronic Characterization

By Lilian S. Schaffroth, Jakob Lenz, Veit Giegold, Maximilian Kögl, Achim Hartschuh, R. Thomas Weitz from Wiley: Advanced Materials: Table of Contents. Published on Apr 16, 2019.

Freestanding membranes composed of an electron‐conductive organic small‐molecular semiconductor are realized via a solution‐crystallization approach. Despite the comparably weak van der Waals force holding the small molecules together, the suspended films can be as thin as only 6 nm. The films show promising mechanical and semiconducting properties and optical planar chirality. Abstract Determining the electronic properties of nanoscopic, low‐dimensional materials free of external influences is key to the discovery and understanding of new physical phenomena. An example is the suspension of graphene, which has allowed access to their intrinsic charge transport properties. Furthermore, suspending thin films enables their application as membranes, sensors, or resonators, as has been explored extensively. While the suspension of covalently bound, electronically active thin films is well established, semiconducting thin films composed of functional molecules only held together by van der Waals interactions could only be studied supported by a substrate. In the present work, it is shown that by utilizing a surface‐crystallization method, electron conductive films with thicknesses of down to 6 nm and planar chiral optical activity can be freely suspended across several hundreds of nanometers. The suspended membranes exhibit a Young's modulus of 2–13 GPa and are electronically decoupled from the environment, as established by temperature‐dependent field‐effect transistor measurements.

Self‐Assembling Endogenous Biliverdin as a Versatile Near‐Infrared Photothermal Nanoagent for Cancer Theranostics

By Ruirui Xing, Qianli Zou, Chengqian Yuan, Luyang Zhao, Rui Chang, Xuehai Yan from Wiley: Advanced Materials: Table of Contents. Published on Apr 16, 2019.

An endogenic near‐infrared‐absorbing photothermal nanoagent is developed based on self‐assembling biliveridin in cooperation with short peptides and metal ions. The nanoagent integrates multimodal imaging and therapeutic functions and provides promising opportunities for noninvasive, targeted, controllable precision tumor photothermal therapy. Abstract Photothermal nanomaterials that integrate multimodal imaging and therapeutic functions provide promising opportunities for noninvasive and targeted diagnosis and treatment in precision medicine. However, the clinical translation of existing photothermal nanoagents is severely hindered by their unclear physiological metabolism, which makes them a strong concern for biosafety. Here, the utilization of biliverdin (BV), an endogenic near‐infrared (NIR)‐absorbing pigment with well‐studied metabolic pathways, to develop photothermal nanoagents with the aim of providing efficient and metabolizable candidates for tumor diagnosis and therapy, is demonstrated. It is shown that BV nanoagents with intense NIR absorption, long‐term photostability and colloidal stability, and high photothermal conversion efficiency can be readily constructed by the supramolecular multicomponent self‐assembly of BV, metal‐binding short peptides, and metal ions through the reciprocity and synergy of coordination and multiple noncovalent interactions. In vivo data reveal that the BV nanoagents selectively accumulate in tumors, locally elevate tumor temperature under mild NIR irradiation, and consequently induce efficient photothermal tumor ablation with promising biocompatibility. Furthermore, the BV nanoagents can serve as a multimodal contrast for tumor visualization through both photoacoustic and magnetic resonance imaging. BV has no biosafety concerns, and thereby offers a great potential in precision medicine by integrating multiple theranostic functions.

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By from Wiley: Advanced Materials: Table of Contents. Published on Apr 16, 2019.

Contents: (Adv. Mater. 16/2019)

By from Wiley: Advanced Materials: Table of Contents. Published on Apr 16, 2019.

Organic Semiconducting Membranes: Freely Suspended, van der Waals Bound Organic Nanometer‐Thin Functional Films: Mechanical and Electronic Characterization (Adv. Mater. 16/2019)

By Lilian S. Schaffroth, Jakob Lenz, Veit Giegold, Maximilian Kögl, Achim Hartschuh, R. Thomas Weitz from Wiley: Advanced Materials: Table of Contents. Published on Apr 16, 2019.

Purely van der Waals bound films composed of organic small molecules can be suspended across gaps several hundreds of nanometers long, as shown by R. Thomas Weitz and co‐workers in article number 1808309. These solution‐crystallized freestanding films are used in fieldeffect transistors and are characterized with respect to their mechanical stability via local nanoindentation. Cover Image by Christoph Hohmann, Nanosystems Initiative Munich (NIM).

Electrocatalysis: Well‐Dispersed Nickel‐ and Zinc‐Tailored Electronic Structure of a Transition Metal Oxide for Highly Active Alkaline Hydrogen Evolution Reaction (Adv. Mater. 16/2019)

By Tao Ling, Tong Zhang, Binghui Ge, Lili Han, Lirong Zheng, Feng Lin, Zhengrui Xu, Wen‐Bin Hu, Xi‐Wen Du, Kenneth Davey, Shi‐Zhang Qiao from Wiley: Advanced Materials: Table of Contents. Published on Apr 16, 2019.

Transition‐metal oxides were previously considered inactive toward hydrogen evolution. In article 1807771, Tao Ling, Shi‐Zhang Qiao, and co‐workers demonstrate that tailored control of an oxide via dual‐elemental doping can turn it into a superactive material for hydrogen evolution. This strategy of electronic structure engineering potentially revolutionizes the design of catalytic oxide materials.

Water Splitting: Boosting Water Dissociation Kinetics on Pt–Ni Nanowires by N‐Induced Orbital Tuning (Adv. Mater. 16/2019)

By Yufang Xie, Jinyan Cai, Yishang Wu, Yipeng Zang, Xusheng Zheng, Jian Ye, Peixin Cui, Shuwen Niu, Yun Liu, Junfa Zhu, Xiaojing Liu, Gongming Wang, Yitai Qian from Wiley: Advanced Materials: Table of Contents. Published on Apr 16, 2019.

Pt–Ni(N) nanowires are presented by Xiaojing Liu, Gongming Wang, and co‐workers in article number 1807780. The introduced nitrogen can enable the Ni sites to create empty dz2 orbitals with superior orientation for water adsorption and dissociation, and thus resolve the kinetic issue of Pt–Ni nanowires for alkaline hydrogen evolution.

Spintronics: Field and Current Control of the Electrical Conductivity of an Artificial 2D Honeycomb Lattice (Adv. Mater. 16/2019)

By Yiyao Chen, Brock Summers, Ashutosh Dahal, Valeria Lauter, Giovanni Vignale, Deepak K. Singh from Wiley: Advanced Materials: Table of Contents. Published on Apr 16, 2019.

In article number 1808298, Giovanni Vignale, Deepak K. Singh, and co‐workers demonstrate a one‐to‐one correspondence between the colossal enhancement in electrical conductivity in applied magnetic field and magnetic charge crystallization of a two‐dimensional magnetic material in the form of a triangular Wigner crystal state (blue triangular structure) in a Nd‐honeycomb lattice. The neutron reflectometry measurement (green‐yellow pattern) on BL‐4A beamline at ORNL constitutes key evidence of this novel effect. Image credit: Oak Ridge National Laboratory/Jill Hemman.

Metasurfaces: From Single‐Dimensional to Multidimensional Manipulation of Optical Waves with Metasurfaces (Adv. Mater. 16/2019)

By Shuqi Chen, Zhancheng Li, Wenwei Liu, Hua Cheng, Jianguo Tian from Wiley: Advanced Materials: Table of Contents. Published on Apr 16, 2019.

Realizing optical wave manipulation in an arbitrary dimension with metasurfaces will greatly advance the realization of optical computation and biological sensing, for example. In article number 1802458, Shuqi Chen and co‐workers briefly review and classify the recent advances in metasurfaces from the viewpoint of different dimensional manipulations of optical waves, showing the development trend of metasurfaces for effective dimensional manipulation of optical waves.

Biomedical Materials: Engineered Bacterial Bioreactor for Tumor Therapy via Fenton‐Like Reaction with Localized H2O2 Generation (Adv. Mater. 16/2019)

By Jin‐Xuan Fan, Meng‐Yun Peng, He Wang, Hao‐Ran Zheng, Zong‐Lin Liu, Chu‐Xin Li, Xia‐Nan Wang, Xin‐Hua Liu, Si‐Xue Cheng, Xian‐Zheng Zhang from Wiley: Advanced Materials: Table of Contents. Published on Apr 16, 2019.

In article number 1808278, Xian‐Zheng Zhang and co‐workers develop an integrative bioreactor based on engineered bacteria for tumor therapy. This bioreactor displays bacterial tumor tropism and spontaneously supplies localized H2O2 for a therapeutic Fenton‐like reaction, achieving precise and long‐term tumor therapy.

Paving the Path toward Reliable Cathode Materials for Aluminum‐Ion Batteries

By Feng Wu, Haoyi Yang, Ying Bai, Chuan Wu from Wiley: Advanced Materials: Table of Contents. Published on Apr 16, 2019.

Aluminum‐ion batteries are promising low‐cost energy storage and conversion devices. The progress of key cathode materials is summarized and challenges for cathode reactions are proposed, followed by the approaches to enhance the reactions. Additionally, the issues of anode and electrolyte (interface) are addressed for a comprehensive understanding of AIBs. Abstract Aluminum metal is a high‐energy‐density carrier with low cost, and thus endows rechargeable aluminum batteries (RABs) with the potential to act as an inexpensive and efficient electrochemical device, so as to supplement the increasing demand for energy storage and conversion. Despite the enticing aspects regarding cost and energy density, the poor reversibility of electrodes has limited the pursuit of RABs for a long time. Fortunately, ionic‐liquid electrolytes enable reversible aluminum plating/stripping at room temperature, and they lay the very foundation of RABs. In order to integrate with the aluminum‐metal anode, the selection of the cathode is pivotal, but is limited at present. The scant option of a reliable cathode can be accounted for by the intrinsic high charge density of Al3+ ions, which results in sluggish diffusion. Hence, reliable cathode materials are a key challenge of burgeoning RABs. Herein, the main focus is on the insertion cathodes for RABs also termed aluminum‐ion batteries, and the recent progress and optimization methods are summarized. Finally, an outlook is presented to navigate the possible future work.

From Single‐Dimensional to Multidimensional Manipulation of Optical Waves with Metasurfaces

By Shuqi Chen, Zhancheng Li, Wenwei Liu, Hua Cheng, Jianguo Tian from Wiley: Advanced Materials: Table of Contents. Published on Apr 16, 2019.

Realizing optical wave manipulation in arbitrary dimension with metasurfaces indicates a bright future for the real application of artificial nanostructures. A classification of metasurfaces is provided from the viewpoint of the different dimensional manipulations of optical waves. Furthermore, the development trend of metasurfaces for effective dimensional manipulation of optical waves is shown. Abstract Metasurfaces, 2D artificial arrays of subwavelength elements, have attracted great interest from the optical scientific community in recent years because they provide versatile possibilities for the manipulation of optical waves and promise an effective way for miniaturization and integration of optical devices. In the past decade, the main efforts were focused on the realization of single‐dimensional (amplitude, frequency, polarization, or phase) manipulation of optical waves. Compared to the metasurfaces with single‐dimensional manipulation, metasurfaces with multidimensional manipulation of optical waves show significant advantages in many practical application areas, such as optical holograms, sub‐diffraction imaging, and the design of integrated multifunctional optical devices. Nowadays, with the rapid development of nanofabrication techniques, the research of metasurfaces has been inevitably developed from single‐dimensional manipulation toward multidimensional manipulation of optical waves, which greatly boosts the application of metasurfaces and further paves the way for arbitrary design of optical devices. Herein, the recent advances in metasurfaces are briefly reviewed and classified from the viewpoint of different dimensional manipulations of optical waves. Single‐dimensional manipulation and 2D manipulation of optical waves with metasurfaces are discussed systematically. In conclusion, an outlook and perspectives on the challenges and future prospects in these rapidly growing research areas are provided.

Progress and Perspectives of Thin Film Kesterite Photovoltaic Technology: A Critical Review

By Sergio Giraldo, Zacharie Jehl, Marcel Placidi, Victor Izquierdo‐Roca, Alejandro Pérez‐Rodríguez, Edgardo Saucedo from Wiley: Advanced Materials: Table of Contents. Published on Apr 16, 2019.

The latest achievements and future perspectives of thin film photovoltaic kesterite technology are presented. Through a critical review of the available literature, the VOC deficit is confirmed as the major challenge for the future of this technology. The main possible origins are clearly identified, and some technological solutions based on doping and alloying strategies are proposed. Abstract The latest progress and future perspectives of thin film photovoltaic kesterite technology are reviewed herein. Kesterite is currently the most promising emerging fully inorganic thin film photovoltaic technology based on critical raw‐material‐free and sustainable solutions. The positioning of kesterites in the frame of the emerging inorganic solar cells is first addressed, and the recent history of this family of materials briefly described. A review of the fast progress achieved earlier this decade is presented, toward the relative slowdown in the recent years partly explained by the large open‐circuit voltage (VOC) deficit recurrently observed even in the best solar cell devices in the literature. Then, through a comparison with the close cousin Cu(In,Ga)Se2 technology, doping and alloying strategies are proposed as critical for enhancing the conversion efficiency of kesterite. In the second section herein, intrinsic and extrinsic doping, as well as alloying strategies are reviewed, presenting the most relevant and recent results, and proposing possible pathways for future implementation. In the last section, a review on technological applications of kesterite is presented, going beyond conventional photovoltaic devices, and demonstrating their suitability as potential candidates in advanced tandem concepts, photocatalysis, thermoelectric, gas sensing, etc.

Fri 10 May 14:30: Challenges and Opportunities in Designing Quantum Materials

From All Talks (aka the CURE list). Published on Apr 16, 2019.

Challenges and Opportunities in Designing Quantum Materials

Unconventional superconductivity with high critical temperatures, nematicity, frustrated magnetism, spin-liquid phases or the recently discussed Kitaev model-based phases are a few examples of exotic states in correlated materials. One of the big challenges in solid state physics is the microscopic description of such systems. Moreover, being able to understand these materials implies the possibility of designing compounds with desirable properties.

In this talk I will review the world of some families of correlated materials ranging from unconventional superconductors to frustrated magnets and present some strategies on how to model them microscopically.

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Fri 26 Apr 14:30: Crystal and Magnetic Structures of a Family of Quantum Kagome Antiferromagnets

From All Talks (aka the CURE list). Published on Apr 16, 2019.

Crystal and Magnetic Structures of a Family of Quantum Kagome Antiferromagnets

Materials constructed from kagome layers of antiferromagnetically coupled S = ½ moments are highly prized as they offer a unique opportunity to explore the elusive quantum spin liquid state (QSL) [1]. The mineral herbertsmithite, ZnCu3(OH)6Cl2, for instance, contains such an array of Cu2+ S = ½ ions and consequently, has garnered considerable attention as a QSL candidate [2]. However, the substantial Cu2+/Zn2+ disorder within the crystal structure of herbertsmithite continues to call into question our ability to rationalise its magnetic ground state [3]. More recently, an alternative Cu2+-based mineral known as Zn-doped barlowite, ZnCu3(OH)6FBr, has shown promise as a new materialisation of the QSL state [4], with first-principles studies indicating that the extent of the anti-site disorder is reduced in comparison to herbertsmithite owing to the different stacking of the kagome planes in Zn-barlowite [5]. Despite this interest, the crystal and magnetic structures of the parent material barlowite, Cu4(OH)6FBr, were poorly understood with several conflicting reports in the literature [6-8]. Here, I will introduce these developments in the field of highly frustrated magnetism before presenting our comprehensive powder neutron diffraction study of barlowite. In doing so, I will discuss the intriguing structural phase transition we observe in this material at T = 250 K, and clarify the nature of its magnetic ground below TN = 15 K [9]. Furthermore, I will show that we can tune the magnetic ground state of barlowite from antiferromagnetic order to quantum disorder upon Zn-doping though our magnetometry and muon spectroscopy measurements. Finally, I will discuss our efforts to control the nature of the structural phase transition within a new family compounds through exchange of the halide ions in barlowite. [1] L. Savary and L. Balents, Rep. Prog. Phys. 80, 016502 (2017). [2] M. P. Shores et al., JACS 127 , 13462-13463 (2005). [3] M. Fu et al., Science 350, 655-658 (2015). [4] T.-H. Han, J. Singleton and J. A. Schlueter, Phys. Rev. Lett. 113, 227203 (2014). [5] Z. Lui et al., Phys. Rev. B 92 , 220102® (2015). [6] Z. Feng et al., Phys. Rev. B 98 , 155127 (2018). [7] C. M. Pasco et al., Phys. Rev. Mater. 2, 0444061 (2018). [8] R. W. Smaha et al., J. Solid State Chem. 268, 123-129 (2018). [9] K. Tustain et al., Phys. Rev. Mater. 2, 111405® (2018)

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Tue 07 May 11:00: An Introduction to Beko R&D and how Sensors are Integral to the Smart Home To register to attend: https://beko-rd-industry-lecture.eventbrite.co.uk

From All Talks (aka the CURE list). Published on Apr 16, 2019.

An Introduction to Beko R&D and how Sensors are Integral to the Smart Home

The lecture will begin with an introduction from Dr Ronan Daly (IfM). We will then continue with the talk being split into three parts:
  1. Dr Conway will introduce the Beko R&D Centre and its parent company Arçelik. This will include their current research interests and how they aim to engage with universities and the opportunities that can arise from this.
  2. Dr Anderson will describe his career path from university to industry with an aim of showing the exciting possibilities for cutting edge research away from academia.
  3. Finally presentations on some of the research at Beko R&D into novel sensors and how they offer many diverse advantages and opportunities for the smart home. Beko R&D is aiming to be at the forefront of this by collaborating with companies and universities to research areas that can enhance user comfort and safety in the home. This can be from low cost sensors with built-in energy harvesting, to HMI sensors allowing new ways of user interaction.

To register to attend: https://beko-rd-industry-lecture.eventbrite.co.uk

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Oxygen evolution electrocatalysis of a single MOF‐derived composite nanoparticle on the tip of a nanoelectrode

By Harshitha Barike Aiyappa, Patrick Wilde, Thomas Quast, Justus Masa, Corina Andronescu, Yen-Ting Chen, Martin Muhler, Roland A. Fischer, Wolfgang Schuhmann from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 16, 2019.

Determination of the intrinsic electrocatalytic activity of nanomaterials by means of conventional macroelectrode techniques is compromised by ensemble and film effects. Here, a unique ‘particle at the stick’ approach is used to grow a single metal‐organic frame­work (MOF) nanoparticle (ZIF‐67) on a nanoelectrode surface which is subsequently pyrolyzed to generate a cobalt/nitrogen‐doped carbon (CoN/C) composite nanoparticle that exhibits extremely high catalytic activity towards the oxygen evolution reaction (OER) with a current density of up to 230 mA cm‐2 at 1.77 V (vs. RHE), and a remarkably high turn‐over frequency (TOF) of 29.7 s‐1 at 540 mV overpotential. Identical location transmission electron microscopy (IL‐TEM) analysis substantiates the ‘self‐sacrificial’ template nature of the MOF, while post‐electrocatalysis studies reveal agglomeration of Co centers with­in the Co‐N/C composite during the OER. Thus, ‘single‐entity’ electro­chemical analysis provides measures for deriving the intrinsic electro­catalytic activity apart from furnishing insights into the transient beha­vior of the electrocatalyst under reaction conditions.

A Peanut‐Shaped Polyaromatic Capsule: Solvent‐Dependent Transformation and Electronic Properties of a Non‐Contacted Fullerene Dimer

By Kyosuke Matsumoto, Shunsuke Kusaba, Yuya Tanaka, Yoshihisa Sei, Munetaka Akita, Kazushi Aritani, Masa-aki Haga, Michito Yoshizawa from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 16, 2019.

Synthesis of molecular containers capable of incorporating multiple fullerenes, for the study of the nanocluster properties, remains challenging. Here we report that room‐temperature mixing of metal ions with W‐shaped bispyridine ligands featuring polyaromatic panels results in the quantitative formation of a peanut‐shaped M2L4 capsule. The polyaromatic capsule reversibly converts into two molecules of an ML2 double tube in response to changes in the solvent. Notably, the capsule allows for the incorporation of two fullerene molecules into the connected, two spherical cavities at room temperature. The close proximity yet non‐contact of the encapsulated C60 molecules, with a separation of 6.4 Å, was revealed by X‐ray crystallographic analysis. The resultant, unusual fullerene dimer undergoes sequential reduction within the capsule to generate (C60•–)2, C60•–•C602–, and (C602–)2 species. Furthermore, temperature‐controlled stepwise incorporation of two C60 molecules into the capsule is demonstrated.

Thu 13 Jun 12:30: Union Debt Management

From All Talks (aka the CURE list). Published on Apr 16, 2019.

Union Debt Management

We study the role of government debt maturity in currency unions to identify whether debt management can help governments hedge their budgets against spending shocks. We first use a novel and detailed dataset of debt portfolios of five Euro Area countries to run a battery of VARs, estimating the responses of holding period returns to fiscal shocks. We find that government portfolios, which in our sample comprise mainly of nominal assets, have not been effective in absorbing idiosyncratic fiscal risks, whereas they have been very effective in absorbing aggregate risks. To shed light on this finding, as well as to investigate what types of debt are optimal in a currency area in the presence of both aggregate and idiosyncratic shocks, we setup a formal model of optimal debt management with two countries, benevolent governments and distortionary taxes. Our key finding is that governments should focus on issuing inflation indexed long term debt since this allows them to take full advantage of fiscal hedging.

When we look at the data we find a stark increase in the issuance of real long term debt since the beginning of the Euro in many of the countries in our sample, which our model explains as an optimal response of governments to the introduction of the common currency.

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Thu 09 May 13:45: An Overview of the Flix Programming Language

From All Talks (aka the CURE list). Published on Apr 16, 2019.

An Overview of the Flix Programming Language

In this talk I will present Flix, a functional programming language with aspects of logic programming. I will present the original motivation for Flix and how Flix has evolved since then. The talk will cover some of the recent research on Flix, including (a) how to generalize Datalog from constraints on relations to constraints on lattices, (b) how to verify components of abstract interpreters written in Flix, (c) a design of implicit parameters for logic languages, and (d) programming with first-class Datalog constraints.

Biography:

Magnus Madsen is an assistant professor at the Department of Computer Science at Aarhus University in Denmark. He was previously a postdoctoral researcher at the University of Waterloo in Canada. He has done research internships at Microsoft Research (USA) and Samsung Research America (USA).

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Lipase‐powered mesoporous silica nanomotors for triglyceride degradation

By Lei Wang, Ana Cândida Hortelão, Xin Huang, Samuel Sanchez from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 16, 2019.

We report lipase‐based nanomotors, capable of enhanced Brownian motion over long periods in triglyceride solution and of degrading triglyceride droplets that mimic ‘blood lipids’. We achieved about 40 minutes of enhanced diffusion of lipase modified mesoporous silica nanoparticles (MSNPs) through a biocatalytic reaction between lipase and its corresponding water‐soluble oil substrate (triacetin) as fuel, which resulted in an enhanced diffusion coefficient (i.e., ~50% increase) at low triacetin concentration (e.g.,

Mon 20 May 13:30: The opportunities for sensors in physiologically relevant organ on a chip devices To register to attend: https://kirkstall-industry-lecture.eventbrite.co.uk

From All Talks (aka the CURE list). Published on Apr 16, 2019.

The opportunities for sensors in physiologically relevant organ on a chip devices

Organ on a chip technology is creating a lot of interest in the academic and industrial community – but what actually is an ‘organ on a chip’?

There are few standards and a divergence of opinions about what is the most important factor to ensure that the technology actually moves from lab curiosity to mainstream application. This presentation aims to explain the origins of the technology and clarify the requirements of several of the leading applications.

Many applications need long term cell culture rather than a quick go/no go toxicity assay. Live cell monitoring provides many opportunities for novel biosensors and imaging technologies.

The presentation will close with a review on the status of several leading commercial approaches to organ on a chip.

To register to attend: https://kirkstall-industry-lecture.eventbrite.co.uk

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Wed 08 May 14:15: Reviving an old idea of Boys and Handy: the transcorrelated method in the context of FCIQMC

From All Talks (aka the CURE list). Published on Apr 16, 2019.

Reviving an old idea of Boys and Handy: the transcorrelated method in the context of FCIQMC

Over fifty years ago, Boys and Handy (of this department) proposed a non-unitary similarity transformation of the Schrodinger Hamiltonian, as a means to tackle the electron correlation problem. The resulting Hamiltonian is non-Hermitian, and their idea ran into severe technical difficulties due to optimisations problems within a Slater-Jastrow framework. We re-visit their idea, using FCIQMC to solve the resulting effective Hamiltonian. We show that this approach obviates the difficulties they encountered, as well as resulting in increased accuracy due to the FCI nature of the method. The resulting methodology results in dramatically improved basis set convergence for ab initio Hamiltonians, as well as being applicable to strongly correlated electronic systems.

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Thu 25 Apr 14:00: Complex materials: A journey from disappearing ice phases and ‘pink’ phosphorus to stacking disordered silver iodide

From Materials Chemistry Research Interest Group. Published on Apr 16, 2019.

Complex materials: A journey from disappearing ice phases and ‘pink’ phosphorus to stacking disordered silver iodide

The research activities of our group focus on the structural characterisation of complex materials including disordered crystals, amorphous, glassy and nanomaterials as well as liquids. Our keen ambition is to establish links between the atomic structure of materials, and their chemical and physical properties and performances. Building on this, we also investigate complex phase transitions, crystallisation phenomena, chemical reactions in confinements as well as the chemical functionalisation of nanomaterials including carbon nanotubes and graphene. In this talk, I will present an overview over our most recent work including the following topics: (1) Doping-induced disappearance of ice II from the phase diagram. Ammonium fluoride acts as a ‘magic ingredient’ that enables us to let ice II disappear from the phase diagram in a highly selective fashion.[1] A detailed understanding of the underlying mechanisms and thermodynamics is presented, and we argue that our new finding has wider implications that enables us to understand some of the anomalies of water’s phase diagram including the anomalous properties of liquid water. The selective disappearance of a particular phase with the aid of a dopant highlights the exciting possibility of potentially discovering new phases of ice but also other materials in the future using specific impurities. (2) New 1D allotropes of phosphorus and arsenic. The pnictogen nanomaterials, including phosphorene and arsenene, display remarkable electronic and chemical properties. Yet, the structural diversity that these main group elements are capable of is still poorly explored. We filled single-wall carbon nanotubes with elemental phosphorus and arsenic from the vapour phase.[2,3] Using electron microscopy, chains of highly reactive P4 and As4 molecules were found as well as new one-dimensional allotropes: a single-stranded zig-zag chain and a double-stranded zig-zag ladder. These linear structures represent important intermediates between the gas-phase clusters of the pnictogens and the extended 2D sheets of phosphorene and arsenene. Remarkably, band-gap calculations predict that the insulating P4 and As4 chains become semiconducting, once converted to the zig-zag ladder, and form fully metallic allotropes in the form of the zig-zag chain. (3) Stacking disorder everywhere! Stacking-disordered materials consist of structurally well-defined layers that are stacked on top of one another in a disordered fashion. Naturally, stacking disorder is found for a wide range of layered materials such as graphite or molybdenum sulphide. Using our MCDIF FaX program, we can model the diffuse diffraction features that arise from stacking disorder and obtain quantitative insights into the extents of different types of stacking as well as memory effects within the stacking sequences. Following extensive work on stacking disorder in ice and diamond, we have now identified a first system, silver iodide, where the stacking disorder can be controlled in a quantitative fashion.[4] This now offers the fascinating prospect of being able to fine-tuning the physical and chemical properties of a material between the extreme polytypic endmembers.

[1] J.J. Shephard, B. Slater, P. Harvey, M. Hart, C.L. Bull, S.T. Bramwell, C.G. Salzmann, Nat. Phys., 14 (2018) 569–572 [2] M. Hart, E.R. White, J. Chen, C.M. McGilvery, C.J. Pickard, A. Michaelides, A. Sella, M.S.P. Shaffer, C.G. Salzmann, Angew. Chem. Int. Ed. 56 (2017) 8144-8148 [3] M. Hart, J. Chen, A. Michaelides, A. Sella, M.S.P. Shaffer, C.G. Salzmann, Angew. Chem. Int. Ed. 57 (2018) 11649-11653 [4] R.L. Smith, M. Vickers, M. Rosillo-Lopez, C.G. Salzmann, Cryst. Growth Des. 19 (2019) 2131-2138

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Thu 25 Apr 14:00: Complex materials: A journey from disappearing ice phases and ‘pink’ phosphorus to stacking disordered silver iodide

From All Talks (aka the CURE list). Published on Apr 16, 2019.

Complex materials: A journey from disappearing ice phases and ‘pink’ phosphorus to stacking disordered silver iodide

The research activities of our group focus on the structural characterisation of complex materials including disordered crystals, amorphous, glassy and nanomaterials as well as liquids. Our keen ambition is to establish links between the atomic structure of materials, and their chemical and physical properties and performances. Building on this, we also investigate complex phase transitions, crystallisation phenomena, chemical reactions in confinements as well as the chemical functionalisation of nanomaterials including carbon nanotubes and graphene. In this talk, I will present an overview over our most recent work including the following topics: (1) Doping-induced disappearance of ice II from the phase diagram. Ammonium fluoride acts as a ‘magic ingredient’ that enables us to let ice II disappear from the phase diagram in a highly selective fashion.[1] A detailed understanding of the underlying mechanisms and thermodynamics is presented, and we argue that our new finding has wider implications that enables us to understand some of the anomalies of water’s phase diagram including the anomalous properties of liquid water. The selective disappearance of a particular phase with the aid of a dopant highlights the exciting possibility of potentially discovering new phases of ice but also other materials in the future using specific impurities. (2) New 1D allotropes of phosphorus and arsenic. The pnictogen nanomaterials, including phosphorene and arsenene, display remarkable electronic and chemical properties. Yet, the structural diversity that these main group elements are capable of is still poorly explored. We filled single-wall carbon nanotubes with elemental phosphorus and arsenic from the vapour phase.[2,3] Using electron microscopy, chains of highly reactive P4 and As4 molecules were found as well as new one-dimensional allotropes: a single-stranded zig-zag chain and a double-stranded zig-zag ladder. These linear structures represent important intermediates between the gas-phase clusters of the pnictogens and the extended 2D sheets of phosphorene and arsenene. Remarkably, band-gap calculations predict that the insulating P4 and As4 chains become semiconducting, once converted to the zig-zag ladder, and form fully metallic allotropes in the form of the zig-zag chain. (3) Stacking disorder everywhere! Stacking-disordered materials consist of structurally well-defined layers that are stacked on top of one another in a disordered fashion. Naturally, stacking disorder is found for a wide range of layered materials such as graphite or molybdenum sulphide. Using our MCDIF FaX program, we can model the diffuse diffraction features that arise from stacking disorder and obtain quantitative insights into the extents of different types of stacking as well as memory effects within the stacking sequences. Following extensive work on stacking disorder in ice and diamond, we have now identified a first system, silver iodide, where the stacking disorder can be controlled in a quantitative fashion.[4] This now offers the fascinating prospect of being able to fine-tuning the physical and chemical properties of a material between the extreme polytypic endmembers.

[1] J.J. Shephard, B. Slater, P. Harvey, M. Hart, C.L. Bull, S.T. Bramwell, C.G. Salzmann, Nat. Phys., 14 (2018) 569–572 [2] M. Hart, E.R. White, J. Chen, C.M. McGilvery, C.J. Pickard, A. Michaelides, A. Sella, M.S.P. Shaffer, C.G. Salzmann, Angew. Chem. Int. Ed. 56 (2017) 8144-8148 [3] M. Hart, J. Chen, A. Michaelides, A. Sella, M.S.P. Shaffer, C.G. Salzmann, Angew. Chem. Int. Ed. 57 (2018) 11649-11653 [4] R.L. Smith, M. Vickers, M. Rosillo-Lopez, C.G. Salzmann, Cryst. Growth Des. 19 (2019) 2131-2138

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Wed 29 May 17:00: Intersubjectivity, Place and Embodied Cognition in Children’s Literature Translation Studies

From All Talks (aka the CURE list). Published on Apr 16, 2019.

Intersubjectivity, Place and Embodied Cognition in Children’s Literature Translation Studies

Within children’s literature translation studies emphasis has usually been placed on comparing the source text and the target text in terms of lexis, semantics, cultural elements, etc. What might be a little bit surprising is that scarcely any attention has been given to the reader’s embodied experience of the scene in translation. We will address this issue during the seminar. Through a close reading of two initial passages – the first from Anne of Green Gables by Lucy Maud Montgomery and the second from Alice’s Adventures in Wonderland by Lewis Carroll and their first pre-war translations into Polish, we will verify whether the passages in the target language might offer their readers at least similar embodied experience of certain places to the experience of place which might be evoked by the original.

Beata Piecychna is a visiting scholar from the University of Bialystok, Poland. Her research interests include: children’s literature translation studies, translation theory, translation criticism, translational hermeneutics, cognitive linguistics, cognitive translatology. Laureate of the Kosciuszko Foundation grant to conduct a study on mental simulation in the translation process at the University of California in San Diego.

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Wed 01 May 14:15: Stabilization of AgI’s polar surfaces by the aqueous environment, and its implications for ice formation

From All Talks (aka the CURE list). Published on Apr 16, 2019.

Stabilization of AgI’s polar surfaces by the aqueous environment, and its implications for ice formation

Silver iodide is probably the best inorganic ice nucleating particle known, a feature generally attributed to the excellent lattice match between its basal crystal faces and ice. However, the polar nature of this crystal termination means the surface energy diverges with crystal size unless a polarity compensation mechanism prevails. In this simulation study, the extent to which the surrounding aqueous environment is able to provide such polarity compensation is investigated. On its own, it is found that pure water is unable to stabilize the AgI crystal in a physically reasonable manner, and that mobile charge carriers such as dissolved ions, are essential. In other words, proximate dissolved ions must be considered an integral part of the heterogeneous ice formation mechanism.

This work relies on recent advances in simulation methodology in which appropriate electric and electric displacement fields are imposed (“finite field methods”). A useful by-product of this study is the direct comparison to the commonly used Yeh-Berkowitz method that this enables. Here it is found that naive application of the latter leads to physically unreasonable results, and greatly influences the structure of water in the contact layer. This work should therefore be of general importance to those studying polar/charged surfaces in aqueous environments. I will also highlight recent work that uses the finite field methods to understand the response of bulk electrolyte solutions to imposed electric and electric displacement fields.

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Wed 01 May 13:00: Modality-general and modality-specific processes in hallucinations PLEASE NOTE, WEDNESDAY, 1ST MAY. THIS IS AN EXTRA ZANGWILL TALK AND WILL TAKE PLACE AT 1.00PM. PLEASE ALSO NOTE, THERE WILL BE NO ZANGWILL TEA TODAY

From All Talks (aka the CURE list). Published on Apr 16, 2019.

Modality-general and modality-specific processes in hallucinations

There is a growing recognition in psychosis research of the importance of hallucinations in modalities other than the auditory. This has focused attention on cognitive and neural processes that might be shared by, and which might contribute distinctly to, hallucinations in different modalities. In this talk I address some issues around the modality-generality of cognitive and neural processes in hallucinations, including the role of perceptual and reality-monitoring systems, top-down and bottom-up processes in relation to the psychological and neural substrates of hallucinations, and the phenomenon of simultaneous multimodal hallucinations of the same entity. I suggest that a functional systems approach, inspired by some neglected aspects of the writings of A. R. Luria, can help us to understand patterns of hallucinatory experience across modalities and across clinical and non-clinical groups. Understanding the interplay between modality-general and modality-specific processes may bear fruit for improved diagnosis and therapeutic approaches to dealing with distressing hallucinations.

Charles Fernyhough is a psychologist and writer. The focus of his recent scientific work has been in applying ideas from mainstream developmental psychology to the study of psychosis, particularly the phenomenon of voice-hearing (in which individuals hear voices in the absence of any speaker). He is PI on the interdisciplinary Hearing the Voice project, supported by the Wellcome Trust. He is a Professor of Psychology at Durham University, and is active in outreach and public engagement work on themes relating to his research, with regular contributions to mainstream media. His latest non-fiction book is The Voices Within: The history and science of how we talk to ourselves, published by Profile Books/Wellcome Collection. His other non-fiction books include The Baby in the Mirror: A child’s world from birth to three (Granta, 2008) and Pieces of Light: Memory and its stories (Profile, 2012; shortlisted for the 2013 Royal Society Winton Prize for Science Books). He is the author of two novels: The Auctioneer (Fourth Estate, 1999) and A Box of Birds (Unbound, 2013). He is the editor of Others (Unbound, 2019), an anthology exploring how books and literature can show us other points of view, with net profits supporting refugee and anti-hate charities.

PLEASE NOTE, WEDNESDAY, 1ST MAY. THIS IS AN EXTRA ZANGWILL TALK AND WILL TAKE PLACE AT 1.00PM. PLEASE ALSO NOTE, THERE WILL BE NO ZANGWILL TEA TODAY

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Tue 14 May 13:10: Rare Diseases, equity and social justice in contemporary UK healthcare

From All Talks (aka the CURE list). Published on Apr 16, 2019.

Rare Diseases, equity and social justice in contemporary UK healthcare

In 2013, the four UK health departments launched a collaborative UK Strategy for Rare Diseases, which included outlining a shared vision ‘to ensure no one gets left behind just because they have a rare disease’ (Department of Health, 2013). At the time, this formal recognition of concerns about equity and social justice in UK healthcare for patients with rare diseases was heralded as a ‘landmark’ by campaigners. Since then, whilst some changes have been welcomed as improvements, the persistence of problems, such as delays in diagnosis, restricted funding of medicines, and patchy local provision, remain on the agenda. This talk will explore the formation and impact of campaigning on rare diseases in contemporary UK healthcare. Questions considered will include: How are ‘rare diseases’ defined and constituted? And what forms of systematic disadvantage are they associated with? Rare diseases, as an emergent site of activism, may illuminate new and pressing factors effecting the distribution of healthcare in the UK today.

Alev Sen is a PhD candidate at the Department of Sociology, University of Cambridge.

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Tue 07 May 13:10: The Future of Coal in the Global Energy Transition: Geopolitical, Economic, and Technological Perspectives

From All Talks (aka the CURE list). Published on Apr 16, 2019.

The Future of Coal in the Global Energy Transition: Geopolitical, Economic, and Technological Perspectives

World energy demand is rising year by year as populations increase and emerging economies continue their rapid expansion. Coal, historically a major source of energy, has continued to remain a major player in the power mix despite concerns about its greenhouse emissions and effects on global climate change. While western countries have begun to move away from coal, developing countries such as China and India are driving demand on international coal markets and increasing their use of coal for electricity generation. Balancing the often competing interests of sustainability and economic development is a difficult policy question, with political, economic, and technological factors to consider.

Stephanie is pursuing an MPhil in Public Policy. Her independent research focuses on energy and technology policy, especially in developing countries.

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Tue 23 Apr 13:10: Decolonising African politics: Where is there evidence of change?

From All Talks (aka the CURE list). Published on Apr 16, 2019.

Decolonising African politics: Where is there evidence of change?

Decolonising the university is a growing concern in the social sciences. It is no longer acceptable to assume that Western theories and histories are sufficient for making sense of the world –all the more clear as western democracies are being destabilised by forms of populism, fake news, even Brexit. This paper examines the evidence for recent change in the use of Western-centred epistemological concepts and practices with regards to published scholarship on the politics of Africa. Political scholars recognise that a constrained higher education sector and scholarly conventions limit theory generation from Africa, but little is known about efforts to navigate and generate new ideas and theoretical approaches from the continent. This paper aims to build an evidence base for moves to decolonising knowledge production through a systematic review of theoretical conventions in published scholarship. It poses and addresses the questions: How is theory being engaged in the study of the politics of Africa? To what extent does the study of the politics of Africa inform theory generation?

Dr Stephanie Diepeveen is a Research Associate and Deputy Director in Cambridge’s Centre of Governance and Human Rights, and a Postdoctoral Research Associate at Darwin College. Stephanie’s research explores the intersections of forms of power and digital technology, beginning from an empirical lens in East Africa.

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Tue 30 Apr 13:10: The making of the ‘climate migrant’: how a label emerges and circulates

From All Talks (aka the CURE list). Published on Apr 16, 2019.

The making of the ‘climate migrant’: how a label emerges and circulates

How we categorise migrants matters. The different implications of labelling for ‘political refugees’, ‘asylum seekers’, ‘economic migrant’ or ‘illegal alien’ are important because each label conditions the rights and conditions of the people designated. Since the mid-1980s, the ‘climate migrant’ label has gained traction among experts in academia, the press and policy-making circles. I begin by presenting the debate between ‘maximalism’ – which seeks to quantify climate-induced migratory flows and identify ‘climate migrants’ – and ‘minimalism’, which disputes the usefulness of the ‘climate migrant’ label on analytical and practical grounds. This leaves us with a tension. On the one hand, minimalism has made a convincing case for a nuanced understanding of the environment as one driver of mobility among many. On the other, the ‘climate migrant’ label retains significant appeal, and we must still contend with the inevitability of labelling, which is inherently reductive. As a potential way out of this bind, I argue that a critical study of ‘climate migrants’ should focus both on how the label is made – that is the discursive practices used to conceptualise, contest and deploy it for policy purposes – but also on how the label circulates, asking questions such as: how does it spread? How does it evolve in the process? What facilitates or hinders its movement? Why and how does the label ‘stick’ to certain people and not to others? I end with some suggestions for how we may begin to answer these questions, drawing in particular on multi-sited ethnography.

David Durand-Delacre is a 1st year PhD student in the Geography Department.

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A High‐Performance Self‐Regenerating Solar Evaporator for Continuous Water Desalination

By Yudi Kuang, Chaoji Chen, Shuaiming He, Emily M. Hitz, Yilin Wang, Wentao Gan, Ruiyu Mi, Liangbing Hu from Wiley: Advanced Materials: Table of Contents. Published on Apr 16, 2019.

A wood‐based evaporator with a rationally designed artificial channel‐array is reported for long‐term solar desalination. The unique channel‐array design endows the evaporator with a real‐time self‐regenerating property, which allows a stable and highly efficient steam generation (≈75% efficiency) of the evaporator in a wide range of salt concentrations, from pure water to 20 wt% NaCl solution. Abstract Emerging solar desalination by interfacial evaporation shows great potential in response to global water scarcity because of its high solar‐to‐vapor efficiency, low environmental impact, and off‐grid capability. However, solute accumulation at the heating interface has severely impacted the performance and long‐term stability of current solar evaporation systems. Here, a self‐regenerating solar evaporator featuring excellent antifouling properties using a rationally designed artificial channel‐array in a natural wood substrate is reported. Upon solar evaporation, salt concentration gradients are formed between the millimeter‐sized drilled channels (with a low salt concentration) and the microsized natural wood channels (with a high salt concentration) due to their different hydraulic conductivities. The concentration gradients allow spontaneous interchannel salt exchange through the 1–2 µm pits, leading to the dilution of salt in the microsized wood channels. The drilled channels with high hydraulic conductivities thus function as salt‐rejection pathways, which can rapidly exchange the salt with the bulk solution, enabling the real‐time self‐regeneration of the evaporator. Compared to other salt‐rejection designs, the solar evaporator exhibits the highest efficiency (≈75%) in a highly concentrated salt solution (20 wt% NaCl) under 1 sun irradiation, as well as long‐term stability (over 100 h of continuous operation).

Fri 07 Jun 14:00: Title to be confirmed

From All Talks (aka the CURE list). Published on Apr 16, 2019.

Title to be confirmed

Abstract not available

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Fri 10 May 14:00: Title to be confirmed

From All Talks (aka the CURE list). Published on Apr 16, 2019.

Title to be confirmed

Abstract not available

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Fri 26 Apr 14:00: Bio-electromechanical interfaces and sensors based on functional nanomaterials

From All Talks (aka the CURE list). Published on Apr 16, 2019.

Bio-electromechanical interfaces and sensors based on functional nanomaterials

Abstract not available

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[ASAP] Asymmetric Multimetallic Mesoporous Nanospheres

By Hao Lv, Dongdong Xu, Lizhi Sun, Joel Henzie, Aaron Lopes, Qingyu Gu, Yusuke Yamauchi, Ben Liu from Nano Letters: Latest Articles (ACS Publications). Published on Apr 16, 2019.

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Nano Letters
DOI: 10.1021/acs.nanolett.9b01223

[ASAP] Experiments and Simulations of Complex Sugar-Based Coil-Brush Block Polymer Nanoassemblies in Aqueous Solution

By Mei Dong, Michiel G. Wessels, Jee Young Lee, Lu Su, Hai Wang, Rachel A. Letteri, Yue Song, Yen-Nan Lin, Yingchao Chen, Richen Li, Darrin J. Pochan, Arthi Jayaraman, Karen L. Wooley from ACS Nano: Latest Articles (ACS Publications). Published on Apr 16, 2019.

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ACS Nano
DOI: 10.1021/acsnano.8b08811

[ASAP] Nanocrystals in Molten Salts and Ionic Liquids: Experimental Observation of Ionic Correlations Extending beyond the Debye Length

By Vladislav Kamysbayev, Vishwas Srivastava, Nicholas B. Ludwig, Olaf J. Borkiewicz, Hao Zhang, Jan Ilavsky, Byeongdu Lee, Karena W. Chapman, Suriyanarayanan Vaikuntanathan, Dmitri V. Talapin from ACS Nano: Latest Articles (ACS Publications). Published on Apr 16, 2019.

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ACS Nano
DOI: 10.1021/acsnano.9b01292

[ASAP] DNA Logic Operations in Living Cells Utilizing Lysosome-Recognizing Framework Nucleic Acid Nanodevices for Subcellular Imaging

By Yi Du, Pai Peng, Tao Li from ACS Nano: Latest Articles (ACS Publications). Published on Apr 16, 2019.

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ACS Nano
DOI: 10.1021/acsnano.9b01324

[ASAP] Assessing Lysine and Cysteine Reactivities for Designing Targeted Covalent Kinase Inhibitors

By Ruibin Liu, Zhi Yue, Cheng-Chieh Tsai, Jana Shen from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Apr 16, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.8b13248

[ASAP] Artificial Signal Feedback Network Mimicking Cellular Adaptivity

By Hui Liu, Qiuxia Yang, Ruizi Peng, Hailan Kuai, Yifan Lyu, Xiaoshu Pan, Qiaoling Liu, Weihong Tan from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Apr 16, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.8b13816

[ASAP] Durable Solar-Powered Systems with Ni-Catalysts for Conversion of CO2 or CO to CH4

By Hunter Shirley, Xiaojun Su, Harshin Sanjanwala, Kallol Talukdar, Jonah W. Jurss, Jared H. Delcamp from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Apr 16, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b00937

[ASAP] Heterologous Prime-Boost Enhances the Antitumor Immune Response Elicited by Plant-Virus-Based Cancer Vaccine

By Hui Cai, Sourabh Shukla, Chao Wang, Hema Masarapu, Nicole F. Steinmetz from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Apr 16, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b01523

[ASAP] Benzoladderene Mechanophores: Synthesis, Polymerization, and Mechanochemical Transformation

By Jinghui Yang, Matias Horst, Joseph A. H. Romaniuk, Zexin Jin, Lynette Cegelski, Yan Xia from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Apr 16, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b01736

[ASAP] Quinoline Triradicals: A Reactivity Study

By Raghavendhar R. Kotha, Ravikiran Yerabolu, Mohammad Sabir Aqueel, James S. Riedeman, Lucas Szalwinski, Duanchen Ding, John J. Nash, Hilkka I. Kenttämaa from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Apr 16, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b01740

[ASAP] Lithium-Doping Stabilized High-Performance P2–Na0.66Li0.18Fe0.12Mn0.7O2 Cathode for Sodium Ion Batteries

By Lufeng Yang, Xiang Li, Jue Liu, Shan Xiong, Xuetian Ma, Pan Liu, Jianming Bai, Wenqian Xu, Yuanzhi Tang, Yan-Yan Hu, Meilin Liu, Hailong Chen from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Apr 16, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b01855

[ASAP] Coordinative Reduction of Metal Nodes Enhances the Hydrolytic Stability of a Paddlewheel Metal–Organic Framework

By Dahae Song, Jinhee Bae, Hoon Ji, Min-Bum Kim, Youn-Sang Bae, Kyo Sung Park, Dohyun Moon, Nak Cheon Jeong from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Apr 16, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b02114

[ASAP] Oriented External Electric Fields: Tweezers and Catalysts for Reactivity in Halogen-Bond Complexes

By Chao Wang, David Danovich, Hui Chen, Sason Shaik from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Apr 16, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b02174

[ASAP] A Radical Approach to Anionic Chemistry: Synthesis of Ketones, Alcohols, and Amines

By Shengyang Ni, Natalia M. Padial, Cian Kingston, Julien C. Vantourout, Daniel C. Schmitt, Jacob T. Edwards, Monika M. Kruszyk, Rohan R. Merchant, Pavel K. Mykhailiuk, Brittany B. Sanchez, Shouliang Yang, Matthew A. Perry, Gary M. Gallego, James J. Mousseau, Michael R. Collins, Robert J. Cherney, Pavlo S. Lebed, Jason S. Chen, Tian Qin, Phil S. Baran from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Apr 16, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b02238

[ASAP] Diaryl-?3-chloranes: Versatile Synthesis and Unique Reactivity as Aryl Cation Equivalent

By Misuzu Nakajima, Kazunori Miyamoto, Keiichi Hirano, Masanobu Uchiyama from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Apr 16, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b02436

[ASAP] Sterically Controlled Self-Assembly of a Robust Multinuclear Palladium Catalyst for Ethylene Polymerization

By Qian Liu, Richard F. Jordan from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Apr 16, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b02465

[ASAP] Spotlights on Recent JACS Publications

By from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Apr 16, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b04067

Structure-property correlations in a phase-pure high-temperature superconductor with a record BCS Tc = 55 K

By Jagdish Narayan from RSC - Nanoscale latest articles. Published on Apr 16, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR00562E, Paper
Anagh Bhaumik, Jagdish Narayan
Here, we report the detailed structure-property correlations in the phase-pure robust B-doped Q-carbon high-temperature superconductor having a record Bardeen-Cooper-Schrieffer (BCS) superconducting transition temperature (Tc) of 55 K. This superconducting phase...
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O2, NO2 and NH3 coordination to Co-porphyrin studied with scanning tunneling microscopy on Au(111)

By Se-Jong Kahng from RSC - Nanoscale latest articles. Published on Apr 16, 2019.

Nanoscale, 2019, Advance Article
DOI: 10.1039/C9NR00843H, Paper
Min Hui Chang, Na-Young Kim, Yun Hee Chang, Yeunhee Lee, Un Seung Jeon, Howon Kim, Yong-Hyun Kim, Se-Jong Kahng
We observed a square ring structure in O2, a rectangular ring structure in NO2, and a bright-center structure in NH3 coordinated to Co-porphyrin.
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Stabilizing electrochemical Li−O2 batteries with a metal-based cathode of PdNi on Ni nonwoven fabric

By Ji-Jing Xu from RSC - Nanoscale latest articles. Published on Apr 16, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR02390A, Paper
Huanfeng Wang, Junfeng Li, Xuexi Sun, Ji-Jing Xu
The design of a nanoporous cathode for Li−O2 battery that achieves the high chemical stability as well as the superior electrochemical performance remains an enormous challenge. A novel approach for...
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Study on Water Splitting Characteristics for CdS Nanosheets Driven by the Coupling Effect between Photocatalysis and Piezoelectricity

By Ping Liu from RSC - Nanoscale latest articles. Published on Apr 16, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR01676G, Paper
Yan Zhao, Xueyan Huang, Fan Gao, Lulu Zhang, Qinfen Tian, Zhi-Bin Fang, Ping Liu
Ultrathin semiconductors have been proposed as an excellent platform to promote solar conversion due to their ultra-large specific surface area and unique surface structures. So far the researchers designed and...
The content of this RSS Feed (c) The Royal Society of Chemistry

Wed 15 May 10:30: Title to be Confirmed

From All Talks (aka the CURE list). Published on Apr 15, 2019.

Title to be Confirmed

Abstract not available

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Synthesis, Structures, and Near‐IR Absorption of Heterole‐fused Earring Porphyrins

By Licheng Wu, Feilong Li, Yutao Rao, Bin Wen, Ling Xu, Mingbo Zhou, Takayuki Tanaka, Atsuhiro Osuka, Jianxin Song from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 15, 2019.

Abstract: A reaction sequence of regioselective peripheral bromination, Suzuki‐Miyaura coupling with 2‐borylated thiophene or pyrrole, and oxidative ring‐closure with FeCl3 allowed the synthesis of heterole‐fused earring porphyrins 4Pd and 9Pd from the parent earring porphyrin 1. Differently pyrrole‐fused porphyrins 5H and 6H and their PdII complexes 5Pd and 6Pd were also synthesized. The structures of 4Pd, 5H, 6Pd, and 8Pd have been revealed by X‐ray analysis to be roughly coplanar but considerably twisted due to constraints imposed by heterole‐fused structures. 5Pd exhibits an intensified band at 1505 nm, while 4Pd and 9Pd display small but remarkably red‐shifted absorption bands reaching around 2200 nm.

The rise of fiber electronics

By Xiaojie Xu, Songlin Xie, Ye Zhang, Huisheng Peng from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 15, 2019.

As a new direction of applied chemistry, fiber electronics allow configuration changes from three to two dimensions and then to one dimension in electronic devices. The resulting fiber devices have unique properties, such as ultraflexibility, tissue adaptability and weavability, enabling their use in a variety of applications, particularly in various emerging fields related to implantable devices and wearable systems. Here, we summarize the different types of fiber electrode materials based on the one‐dimensional configuration and their distinctive interfaces, various devices and promising applications and highlight the remaining challenges and future directions.

Geochemical Sources and Availability of Amidophosphates on the Early Earth

By Clémentine Gibard, Eddy I Jiménez, Terence Kee, Ramanarayanan Krishnamurthy, Matthew Pasek from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 15, 2019.

Phosphorylation of (pre)biotically relevant molecules in aqueous medium leading to sugar‐phosphates, (oligo)nucleotides, (oligo)peptides and lipids/vesicles has recently been demonstrated by the use of water‐soluble diamidophosphate (DAP). Naturally, questions arise relating to the prebiotic plausibility and availability of DAP and other amidophosphosphorus species on the early earth. Herein, we demonstrate that DAP and other amino‐derivatives of phosphates/phosphite are generated when Fe3P (surrogate of mineral schreibersite), condensed phosphates and reduced oxidation state phosphorus compounds that could be available on early earth are exposed to aqueous ammonia solutions. Additionally, DAP is shown to remain in aqueous solution under conditions where phosphate is precipitated out by divalent metals. These results show, for the first time, that nitrogenated analogs of phosphate and reduced phosphite species can be produced (alongside the usual oxygenated versions) and remain in solution, which increase the potential for abiotic phosphorylation reactions by overcoming the thermodynamic barrier in water.

Cobalt‐Catalyzed Enantioselective Hydroboration/Cyclization of 1,7‐Enynes: Asymmetric Synthesis of Chiral Quinolinones Containing Quaternary Stereogenic Centers

By Caizhi Wu, Jiayu Liao, Shaozhong Ge from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 15, 2019.

An asymmetric cobalt‐catalyzed hydroboration/cyclization of 1,7‐enynes to synthesize chiral six‐membered N‐heterocyclic compounds was developed. A variety of aniline‐tethered 1,7‐enynes react with pinacolborane to afford the corresponding chiral boryl‐functionalized quinoline derivatives in high yields with high enantioselectivity. This cobalt‐catalyzed asymmetric cyclization of 1,7‐enyens provides a general approach to access a series of chiral quinoline derivatives containing quaternary stereocenters.

Oxygen Evolution Reaction at Carbon Edge Sites: Activity Evolution and Structure‐Function Relationships Clarified by Polycyclic Aromatic Hydrocarbons

By Yangming Lin, Qing Lu, Feihong Song, Linhui Yu, Anna K Mechler, Robert Schlögl, Saskia Heumann from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 15, 2019.

The abundant surface chemical information and edge structures of carbon materials have attracted tremendous interest in catalysis. For the oxygen evolution reaction (OER), edge effects of carbon materials have been rarely studied in detail due to the complexity of various coexisting edge configurations and the controversy between carbon corrosion and carbon catalysis. In the present work, the exact roles of common carbon active edge sites in OER using polycyclic aromatic hydrocarbons (PAHs) with designated configurations (zigzag and armchair) as model probe molecules were interrogated with the focus on structure‐function relationships. Zigzag configurations of PAHs were determined to show high activity for OER while also showing a remarkable stability at a reasonable potential. It performs with a TOF value of 0.276 s‐1 in 0.1 M KOH. The catalytic activity of carbon edge sites could be further effectively regulated by extending their π conjugation structure at a molecular level.

Facile Preparation of Spirolactones by an Alkoxycarbonyl Radical Cyclization Cross‐Coupling Cascade

By Larry E. Overman, Nicholas A. Weires, Yuriy Slutskyy from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 15, 2019.

An alkoxycarbonyl radical 5‐exo cyclization cross‐coupling cascade has been developed that allows functionalized γ‐butyrolactones to be prepared in one step from simple tertiary alcohol‐derived homoallylic oxalate precursors. The reaction succeeds with aryl and vinyl electrophiles and is compatible with heterocyclic fragments in both coupling partners. This chemistry allows for the rapid construction of spirolactones, which are of interest in drug discovery endeavors.

Heterodiatomic Multiple Bonding in Group 13: A Complex with a B‐Al π Bond Reduces CO2

By Alexander Hofmann, Marc-André Légaré, Leonie Wüst, Holger Braunschweig from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 15, 2019.

Heterodiatomic multiple bonds have never been observed within group 13. In this contribution, we disclose a method that generates [(CAAC)PhB=AlCp3t] (1), a complex featuring π bonding between boron and aluminum through the association of singlet fragments. We present the properties of this multiple bond as well as the reactivity of the complex with carbon dioxide, which yields a boron CO complex via an unusual metathesis reaction.

Charge Transport through Self‐assembled Monolayers of Monoterpenoids

By Brian Joseph Cafferty, Yuan Li, Mostafa Baghbanzadeh, Dmitrij Rappoport, M. Hassan Beyzavi, George M. Whitesides from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 15, 2019.

The nature of the processes at the origin of life that selected specific classes of molecules for broad incorporation into cells is controversial. Among those classes selected were polyisoprenoids and their derivatives. This paper tests the hypothesis that polyisoprenoids were early contributors to membranes in part because they (or their derivatives) could facilitate charge transport by quantum tunneling. It measures charge transport across self‐assembled monolayers (SAMs) of carboxyl‐terminated monoterpenoids (O2C(C9HX)) and alkanoates (O2C (C7HX)) with different degrees of unsaturation, supported on silver (AgTS) bottom electrodes, with Ga2O3/EGaIn top electrodes. Measurements of current density of SAMs of linear length‐matched hydrocarbons—both saturated and unsaturated—show that completely unsaturated molecules transport charge faster than those that are completely saturated by approximately a factor of ten. This increase in relative rates of charge transport correlates with the number of carbon‐carbon double bonds, but not with the extent of conjugation. These results suggest that polyisoprenoids—even fully unsaturated—are not sufficiently good tunneling conductors for their conductivity to have favored them as building blocks in the prebiotic world.

Corrigendum: Efficient Homogeneous Electrocatalytic Water Oxidation by a Manganese Cluster with an Overpotential of Only 74 mV

By Totan Ghosh, Galia Maayan from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 15, 2019.

Biomimetic chiral photonic crystals

By Jiawei Lv, Defang Ding, Xuekang Yang, Ke Hou, Xiang Miao, Dawei Wang, Baichuan Kou, Ling Huang, Zhiyong Tang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 15, 2019.

Although it is well known that the amazing iridescent colors from the cuticle of beetles reflect intricate nanoscale organization of bio‐fibers, artificial inorganic materials with comparable optical response have not yet been synthesized with abiotic nano‐building blocks. Such materials have broad applications including circular polarizers, circularly polarized luminescence, lasers, etc. Here, we describe a general method to fabricate biomimetic chiral photonic crystals via Langmuir‐Schaefer assembly of colloidal inorganic nanowires. We not only reproduce the intricate helical structure and circularly polarized color reflection in beetles, but also acquire the highest chiroptical activity with a dissymmetry factor of ‐1.6 among the chiral inorganic nanostructures. More importantly, beyond nature, programmable structural control based on the precise interlayer arrangement endows us an unprecedented freedom to manipulate the optical activity of as‐fabricated chiral photonic crystals.

Vibrational Signatures of Chirality Recognition Between alpha‐Pinene and Alcohols for Theory Benchmarking

By Robert Medel, Caroline Stelbrink, Martin A. Suhm from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 15, 2019.

Chirality recognition between largely rigid molecules can be applied as a benchmark for the description of intermolecular forces by theoretical methods because one constituent is merely mirrored so that other deficits of the methods, such as neglect of anharmonicity, should mostly cancel. To test this approach, mixed OH···pi bridged dimers between the enantiomers of the bicyclic monoterpene alpha‐pinene and the chiral secondary alcohols borneol, alpha‐fenchol, isopinocampheol and 1‐phenylethanol were formed in a supersonic jet and probed by linear FTIR spectroscopy. With borneol and alpha‐fenchol, pronounced shifts in the hydroxyl stretching frequencies upon exchange of the handedness are observed. From three tested density functionals only B3LYP‐D3(BJ) is able to predict these diastereomeric shifts in a satisfactory manner, while M06‐2X and omegaB97X‐D fall short.

Wed 29 May 13:00: Uterine immunity one cell at a time Host: Dr Bidesh Mahata (bm11@sanger.ac.uk)

From All Talks (aka the CURE list). Published on Apr 15, 2019.

Uterine immunity one cell at a time

Abstract not available

Host: Dr Bidesh Mahata (bm11@sanger.ac.uk)

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Wed 22 May 13:00: Title to be confirmed Host: Dr Bidesh Mahata (bm11@sanger.ac.uk)

From All Talks (aka the CURE list). Published on Apr 15, 2019.

Title to be confirmed

Abstract not available

Host: Dr Bidesh Mahata (bm11@sanger.ac.uk)

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Gold(I)‐Catalyzed Cascade Cyclization Reactions of Allenynes for the Synthesis of Fused Cyclopropanes and Acenaphthenes

By Takaya Ikeuchi, Shinsuke Inuki, Shinya Oishi, Hiroaki Ohno from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 15, 2019.

Gold‐catalyzed reaction of phenylene‐tethered allenynes with a benzofuran gave 1‐(naphth‐1‐yl)cyclopropa[b]benzofuran derivatives, whereas the reaction of 1‐allenyl‐2‐ethynyl‐3‐methylbenzene derivatives in the absence of benzofuran gave acenaphthenes in good yields. These results can be rationalized by nucleophilic attack of the alkyne moiety to an activated allene to form a vinyl cation intermediate..

Wed 08 May 13:00: Antigen receptor repertoires and specificities at single-cell resolution Host: Dr Bidesh Mahata (bm11@sanger.ac.uk)

From All Talks (aka the CURE list). Published on Apr 15, 2019.

Antigen receptor repertoires and specificities at single-cell resolution

Abstract not available

Host: Dr Bidesh Mahata (bm11@sanger.ac.uk)

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A gas phase CanMn4‐nO4+ cluster model for the oxygen evolving complex of photosystem II

By Silvia Mauthe, Irene Fleischer, Thorsten Marco Bernhardt, Sandra Marianne Lang, Robert N. Barnett, Uzi Landman from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 15, 2019.

One of the fundamental processes in nature, the oxidation of water, is catalyzed by a small CaMn3O4·MnO cluster located in photosystem II (PSII). Herein, we report the first successful preparation of a series of isolated ligand‐free tetrameric CanMn4‐nO4+ (n = 0 ‐ 4) cluster ions which are employed as structural models for the catalytically active site of PSII. Gas phase reactivity experiments with D2O and H218O in an ion trap reveal the facile deprotonation of multiple water molecules via hydroxylation of the cluster oxo‐bridges for all investigated clusters. However, only the mono‐calcium cluster CaMn3O4+ is observed to oxidize water via elimination of hydrogen peroxide. Concurrent first‐principles density functional theory (DFT) calculations elucidate mechanistic details of the deprotonation and oxidation reactions mediated by CaMn3O4+ as well as the role of calcium.

Generating New Cross Relaxation Pathways by Coating Prussian Blue on NaNdF4 for Enhanced Photothermal Agents

By Zhongzheng Yu, Wenbo Hu, Hui Zhao, Xiaofei Miao, Yan Guan, Weizheng Cai, Zhiping Zeng, Quli Fan, Timothy T. Y. Tan from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 15, 2019.

Cross relaxation among sensitizers is commonly regarded as deleterious in fluorescent materials, while it is favorable in photothermal agents. In this work, we coated Prussian blue (PB) on NaNdF4 nanoparticles for the first time to fabricate core‐shell nanocomplex to generate new cross relaxation pathways between the ladder‐like energy levels of Nd3+ ions and continuous energy band of PB. The photothermal conversion efficiency was exceptionally improved and the mechanism of enhanced photothermal effect was investigated. In vivo photoacoustic imaging and photothermal therapy demonstrated the potential of the enhanced photothermal agents. Moreover, the concept of generating new cross relaxation pathways between different materials is proposed to contribute to the design of all kind of enhanced photothermal agents.

Wed 01 May 13:00: Regulators of chicken B cell development – basic research and application Host: Professor Jim Kaufman (jfk31@cam.ac.uk)

From All Talks (aka the CURE list). Published on Apr 15, 2019.

Regulators of chicken B cell development – basic research and application

Abstract not available

Host: Professor Jim Kaufman (jfk31@cam.ac.uk)

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Wed 24 Apr 13:00: Fish 'n' HIFs: Hypoxia signalling in zebrafish models of infection and inflammation Host: Dr Naomi McGovern (nm390@cam.ac.uk)

From All Talks (aka the CURE list). Published on Apr 15, 2019.

Fish 'n' HIFs: Hypoxia signalling in zebrafish models of infection and inflammation

Abstract not available

Host: Dr Naomi McGovern (nm390@cam.ac.uk)

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Developing Through‐Space Charge Transfer Polymers as A General Approach to Realize Full‐Color and White Emission with Thermally Activated Delayed Fluorescence

By Jun Hu, Qiang Li, Xingdong Wang, Shiyang Shao, Lixiang Wang, Xiabin Jing, Fosong Wang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 15, 2019.

Different from through‐bond charge transfer polymers with conjugated donor‐acceptor architectures, here we report the development of through‐space charge transfer polymers (TSCT‐polymers) containing non‐conjugated polystyrene backbone and spatially separated donor and acceptor units for solution‐processed OLEDs with full‐color and white emission. By tuning the charge transfer strength between donor and acceptors with different electron‐accepting ability, emission color spanning from deep blue (455 nm) to red (616 nm) region can be achieved. Meanwhile, by incorporating two kinds of donor/acceptor pairs in one polymer to create duple through‐space charge transfer channels, blue and yellow emission can be simultaneously obtained to realize white electroluminescence from a single polymer. The TSCT‐polymers exhibit thermally activated delayed fluorescence effect with delayed‐component lifetimes in range of 0.36–1.98 μs, and unexpected aggregation‐induced emission effect with emission intensity enhanced by up to 117 folds from solution to aggregation state, giving promising electroluminescent performance with maximum external quantum efficiency of 7.1%, 16.2%, 1.0% and 14.1% for deep blue, green, red and white emission, respectively.

Thu 02 May 16:00: Studying charge density wave systems and THz collective excitations with a meV atomic beam

From All Talks (aka the CURE list). Published on Apr 15, 2019.

Studying charge density wave systems and THz collective excitations with a meV atomic beam

Helium atom scattering (HAS) provides access to the low-energy meV region of surface vibrational modes and allows to study subtle effects such as the influence of van der Waals bonding. The ability of HAS to observe charge density waves (CDWs) – periodic modulations of the electron density – will be discussed. Examples include multivalley CDWs in Sb(111) and a CDW phase-transition in the one-dimensional topological metal Bi(114). Moreover, the experimental dispersion curves of the topological insulator Bi2Se3 reveal two additional branches, suggesting the presence of surface plasmons in the THz region.

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A Colorimetric Multifunctional Sensing Method for Structural‐Durability‐Health Monitoring Systems

By Healin Im, Seongin Hong, Yunsu Lee, Hanseung Lee, Sunkook Kim from Wiley: Advanced Materials: Table of Contents. Published on Apr 15, 2019.

A colorimetric multifunctional sensing method is demonstrated for durability‐health monitoring systems. The system consists of an array with four indium gallium zinc oxide (IGZO)‐based phototransistors, a light source at a wavelength of 405 nm through a side‐emitting optical fiber, and pH‐ and Cl‐selective color‐variable membranes. This system can detect multiple parameters regarding durability in concrete. Abstract A colorimetric multifunctional phototransmittance‐based structural durability monitoring system is developed. The system consists of an array with four indium gallium zinc oxide (IGZO)‐based phototransistors, a light source at a wavelength of 405 nm through a side‐emitting optical fiber, and pH‐ and Cl‐selective color‐variable membranes. Under illumination at the wavelength of 405 nm at corrosion status, the pH‐ and Cl‐responsive membrane, showing a change in their color, generates a change in the intensity of the transmitted light, which is received by the phototransistor array in the form of an electrical current. Ids and R (Ids/IpH 12) are inversely proportional to the pH, which ranges from 10 to 12. When the pH drops from 12 to 10, the magnitude of Ids and R increases to ≈103. In the case of Cl detection, Ids and R (Ids/ICl 0 wt%) increase nearly 50 times with an increase in Cl concentration of 0.05 wt%, and when the Cl concentration reaches 0.30 wt%, Ids and R increase to ≈103 times greater. This multifunctional colorimetric durability sensing system demonstrates considerable potential as a novel smart‐diagnostic tool of structural durability with high stability, high sensitivity, and multifunction.

Giant Barocaloric Effect at the Spin Crossover Transition of a Molecular Crystal

By Steven P. Vallone, Anthony N. Tantillo, António M. dos Santos, Jamie J. Molaison, Rafal Kulmaczewski, Antonin Chapoy, Pezhman Ahmadi, Malcolm A. Halcrow, Karl G. Sandeman from Wiley: Advanced Materials: Table of Contents. Published on Apr 15, 2019.

A giant barocaloric effect is found at low pressures in a near‐room‐temperature spin‐crossover molecular crystal. Structural data obtained by neutron diffraction are correlated with magnetic data and heat‐capacity studies under hydrostatic pressure. This first experimental study of the barocaloric potential of spin‐crossover compounds provides motivation for a wider examination of the material class. Abstract The first experimental evidence for a giant, conventional barocaloric effect (BCE) associated with a pressure‐driven spin crossover transition near room temperature is provided. Magnetometry, neutron scattering, and calorimetry are used to explore the pressure dependence of the SCO phase transition in polycrystalline samples of protonated and partially deuterated [FeL2][BF4]2 [L = 2,6‐di(pyrazol‐1‐yl)pyridine] at applied pressures of up to 120 MPa (1200 bar). The data indicate that, for a pressure change of only 0–300 bar (0–30 MPa), an adiabatic temperature change of 3 K is observed at 262 K or 257 K in the protonated and deuterated materials, respectively. This BCE is equivalent to the magnetocaloric effect (MCE) observed in gadolinium in a magnetic field change of 0–1 Tesla. The work confirms recent predictions that giant, conventional BCEs will be found in a wide range of SCO compounds.

Superelastic Hard Carbon Nanofiber Aerogels

By Zhi‐Long Yu, Bing Qin, Zhi‐Yuan Ma, Jin Huang, Si‐Cheng Li, Hao‐Yu Zhao, Han Li, Yin‐Bo Zhu, Heng‐An Wu, Shu‐Hong Yu from Wiley: Advanced Materials: Table of Contents. Published on Apr 15, 2019.

A family of hard carbon aerogels with nanofibrous structure templated by various nanofibers are fabricated, which display robust and stable mechanical performances, including high strength, extremely fast recovery speed (860 mm s−1), and ultralow energy loss coefficient (

Sr₆Cd₂Sb₆O₇S₁₀: Strong SHG Response Activated by Highly Polarizable Sb/O/S Groups

By Ruiqi Wang, Fei Liang, Fakun Wang, Yangwu Guo, Xian Zhang, Yi Xiao, Kejun Bu, Zheshuai Lin, Jiyong Yao, Tianyou Zhai, Fu-Qiang Huang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 15, 2019.

A new nonlinear optical (NLO) oxysulfide Sr₆Cd₂Sb₆O₇S₁₀ containing functional 5s²‐electron [SbOxS5‐x]7− (x = 0, 1) groups is synthesized by solid state reaction. This compound displays a four‐times stronger phase‐matchable second harmonic generation (SHG) response than AgGaS₂ (AGS) under the laser radiation of 2.09 μm. Single‐crystal‐based optical measurements reveal temperature‐tuning SHG intensity and novel photoluminescence properties. Theoretical analyses demonstrate that [SbOS₄]7− and [SbS₅]7− tetragonal pyramids make predominate contribution to the enhanced SHG effect, in which mixed anionic [SbOS₄]7− units hold more dedication than [SbS₅]7−. This work proposes that ns²‐electron oxysulfide groups can serve as new functional building units in NLO materials and opens new avenue for other optoelectronic material design.

Dynamic Nanostructures from DNA‐Coupled Molecules, Polymers, and Nanoparticles

By Shine K. Albert, Xiaole Hu, So‐Jung Park from Wiley: Small: Table of Contents. Published on Apr 15, 2019.

The programmability and responsive nature of DNA's molecular recognition properties provides a powerful tool for the fabrication of smart nanomaterials and devices. Here, recent advances in the assembly of dynamic DNA nanostructures that are capable of on‐demand structure and property changes in response to various external stimuli are presented. Abstract Dynamic and reconfigurable systems that can sense and react to physical and chemical signals are ubiquitous in nature and are of great interest in diverse areas of science and technology. DNA is a powerful tool for fabricating such smart materials and devices due to its programmable and responsive molecular recognition properties. For the past couple of decades, DNA‐based self‐assembly is actively explored to fabricate various DNA–organic and DNA–inorganic hybrid nanostructures with high‐precision structural control. Building upon past development, researchers have recently begun to design and assemble dynamic nanostructures that can undergo an on‐demand transformation in the structure, properties, and motion in response to various external stimuli. In this Review, recent advances in dynamic DNA nanostructures, focusing on hybrid structures fabricated from DNA‐conjugated molecules, polymers, and nanoparticles, are introduced, and their potential applications and future perspectives are discussed.

Wed 24 Apr 13:00: Visual selection in the mouse: behavioural and cortical mechanisms

From All Talks (aka the CURE list). Published on Apr 15, 2019.

Visual selection in the mouse: behavioural and cortical mechanisms

A fundamental function of our brain is to selectively process sensory input that is most relevant for decision-making. I will describe our approach to understand this process by studying behavioural changes and neuronal circuit changes in visual cortex in mice learning to perform visual decision-making tasks.

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Impact of Locally Administered Carboxydextran‐Coated Super‐Paramagnetic Iron Nanoparticles on Cellular Immune Function

By Luisa Pedro, Quentin Harmer, Eric Mayes, Jacqueline D. Shields from Wiley: Small: Table of Contents. Published on Apr 15, 2019.

The mechanisms of transit of super‐paramagnetic iron nanoparticles (SPIO) used for identification of lymph nodes (LNs) in cancer, and the impact of accumulation on macrophage function remain unclear. This study shows that SPIO nanoparticles use noncellular mechanisms to rapidly reach draining LNs via lymphatics. SPIOs induce only transient changes in macrophages with no long‐term alterations in phenotype or functional capacity. Abstract Interstitially administered iron oxide particles are currently used for interoperative localization of sentinel lymph nodes (LNs) in cancer staging. Several studies have described concerns regarding the cellular accumulation of iron oxide nanoparticles relating them to phenotype and function deregulation of macrophages, impairing their ability to mount an appropriate immune response once an insult is present. This study aims to address what phenotypic and functional changes occur during lymphatic transit and accumulation of these particles. Data show that 60 nm carboxydextran‐coated iron nanoparticles use a noncellular mechanism to reach the draining LNs and that their accumulation in macrophages induces transient phenotypic and functional changes. Nevertheless, macrophages recover their baseline levels of response within 7 days, and are still able to mount an appropriate response to bacterially induced inflammation.

Broadband High‐Efficiency Chiral Splitters and Holograms from Dielectric Nanoarc Metasurfaces

By Dapeng Wang, Yongsop Hwang, Yanmeng Dai, Guangyuan Si, Shibiao Wei, Duk‐Yong Choi, Daniel E. Gómez, Arnan Mitchell, Jiao Lin, Xiaocong Yuan from Wiley: Small: Table of Contents. Published on Apr 15, 2019.

Nanoarc metasurfaces hold promise for simultaneous broadband and high efficiency applications. A few compelling functionalities, such as chiral beamsplitting, broadband holography, and helicity‐selective holography, can be achieved by dielectric nanoarcs. The continuous nanoarc metasurfaces prevail over plasmonic or dielectric discretized building block strategies and they can lead to novel designs of spin‐controllable metadevices. Abstract Simultaneous broadband and high efficiency merits of designer metasurfaces are currently attracting widespread attention in the field of nanophotonics. However, contemporary metasurfaces rarely achieve both advantages simultaneously. For the category of transmissive metadevices, plasmonic or conventional dielectric metasurfaces are viable for either broadband operation with relatively low efficiency or high efficiency at only a selection of wavelengths. To overcome this limitation, dielectric nanoarcs are proposed as a means to accomplish two advantages. Continuous nanoarcs support different electromagnetic resonant modes at localized areas for generating phase retardation. Meanwhile, the geometric nature of nanoarc curvature endows the nanoarcs with full phase coverage of 0–2π due to the Pancharatnam–Berry phase principle. Experimentally incorporated with the chiral‐detour phase principle, a few compelling functionalities are demonstrated, such as chiral beamsplitting, broadband holography, and helicity‐selective holography. The continuous nanoarc metasurfaces prevail over plasmonic or dielectric discretized building block strategies and the findings lead to novel designs of spin‐controllable metadevices.

Biopebble Containers: DNA‐Directed Surface Assembly of Mesoporous Silica Nanoparticles for Cell Studies

By Pengchao Sun, Arnold Leidner, Simone Weigel, Peter G. Weidler, Stefan Heissler, Tim Scharnweber, Christof M. Niemeyer from Wiley: Small: Table of Contents. Published on Apr 15, 2019.

DNA‐directed self‐assembly of mesoporous silica nanoparticles (MSN) on patterned surfaces can be used for efficient self‐assembly of microstructured surface architectures. The patterns promote the adhesion and guidance of cells and they are capable of affecting the fate of adhered cells through triggered release of MSN cargo. Abstract The development of methods for colloidal self‐assembly on solid surfaces is important for many applications in biomedical sciences. Toward this goal, described is a versatile class of mesoporous silica nanoparticles (MSN) that contain on their surface various types of DNA molecules to enable their self‐assembly into micropatterned surface architectures useful for cell studies. Monodisperse dye‐doped MSN are synthesized by biphase stratification and functionalized with an aptamer oligonucleotide that serves as gatekeeper for the triggered release of encapsulated molecular cargo, such as fluorescent dye rhodamine B or the anticancer drug doxorubicin. One or two additional types of oligonucleotides are installed on the MSN surface to enable DNA‐directed immobilization on solid substrates bearing patterns of complementary capture oligonucleotides. It is demonstrated that this strategy can be used for efficient self‐assembly of microstructured surface architectures, which not only promote the adhesion and guidance of cells but also are capable of affecting the fate of adhered cells through triggered release of their cargo. It is believed that this approach is useful for diverse applications in tissue engineering and nanobio sciences.

A Molecular Hero Suit for In Vitro and In Vivo DNA Nanostructures

By Megan E. Kizer, Robert J. Linhardt, Arun Richard Chandrasekaran, Xing Wang from Wiley: Small: Table of Contents. Published on Apr 15, 2019.

DNA nanostructures perform a wide array of functions from drug delivery to molecular circuits. Their applications in in vitro and in vivo circumstances require special thought in developing a molecular hero suit. This suit equips specialized DNA nanostructures with cell targeting agents, encapsulating therapeutic cargo, and a body armor to protect them from degradation. Abstract Precise control of DNA base pairing has rapidly developed into a field full of diverse nanoscale structures and devices that are capable of automation, performing molecular analyses, mimicking enzymatic cascades, biosensing, and delivering drugs. This DNA‐based platform has shown the potential of offering novel therapeutics and biomolecular analysis but will ultimately require clever modification to enrich or achieve the needed “properties” and make it whole. These modifications total what are categorized as the molecular hero suit of DNA nanotechnology. Like a hero, DNA nanostructures have the ability to put on a suit equipped with honing mechanisms, molecular flares, encapsulated cargoes, a protective body armor, and an evasive stealth mode.

Thu 16 May 13:00: Thinking/researching/teaching race, genetics and intelligence in HPS and STS

From All Talks (aka the CURE list). Published on Apr 15, 2019.

Thinking/researching/teaching race, genetics and intelligence in HPS and STS

This presentation will feature an open discussion exploring strategies and approaches towards thinking, researching and teaching these controversial topics of long-standing interest, with specialists in the history of genetics and anthropology, philosophy of intelligence, and the ethnography of biomedicine, forensics and citizen science.

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Thu 09 May 13:00: How wide and how tall? Genome Wide Association Studies in debate, from height to educational attainment and back

From All Talks (aka the CURE list). Published on Apr 15, 2019.

How wide and how tall? Genome Wide Association Studies in debate, from height to educational attainment and back

In April 2018 a study was published that claimed to have found evolutionary differences between human populations on different continents, with a larger selection in some populations for genes which could be linked to educational attainment (Racimo et al, Genetics, 208, 1565–1584). A few months later the same research group presented new results calling to question the very foundations of their own methodology (Jeremy Berg et al, BioRxiv, 23 June 2018).

In this paper based on a chapter in progress I trace how claims about evolutionary differences between human populations in the selection of complex traits were constructed from 2010 to 2018, starting with the publication of GWAS -data linked to height by the so-called GIANT -consortium in 2010 (Nature, 467, 832–838). This article was considered a breakthrough in GWA -studies of complex human traits, finding hundreds of genetic markers correlating to height differences between individuals. Although the authors carefully noted that these genetic markers could not be used for predictive purposes, but should rather be regarded as indicators of genetic loci suitable for further exploration of functional genetic links to height, this set of markers was subsequently used in a study investigating evolutionary explanations to height differences between different European populations (Nature Genetics, 44, 1015–1019). The article published in 2012 was hence one of the first to claim to have found active selection for a complex human trait which differed between populations.

After these two initial articles were published, several years of similar research followed on ever larger datasets, as the GIANT consortium grew. With the increasing power of new datasets, including genetic data from hundreds of thousands of individuals, the number of genetic markers that could be statistically linked to height differences between individuals also grew. These results were in their turn used as starting points for new studies of the evolutionary background to differences in height between different populations, notably between southern and northern Europeans. Simultaneously, the success of the 2010-study had sparked a whole new field of research applying GWAS to an increasing number of human traits, including one as complex and highly culturally dependent as ‘educational attainment’. In 2018 the field hence culminated in a study claiming to have found an evolutionary background to differences between human populations in the frequency of genetic markers that could be linked to educational attainment. The political implications of this claim sparked a controversy within the population genetics community (Novembre et al, Genetics, 208, 1351–1355) which led to a reconsideration of earlier results. Comparing the GWAS -results from one data set (GIANT) to another (UK Biobank) researchers found that the statistical link between certain genetic markers and height all but disappeared. The explanation given was that the GIANT -dataset suffered from unknown population stratification. This finding brought to question the methodology as such, since it uncovered a hitherto underestimated sensitivity to confounding factors.

Interestingly, the seminal article of the field, published in 2010, included a clear warning of using GWAS -results for prediction. Instead it stated that the genetic markers found should only be used as a starting point for further investigations of genetic functionality. This story hence unfolds as a case study of how scientific results take on new meanings as they leave their original setting and are interpreted by other researchers and implemented as starting points for new studies.

Another aspect of this case study is that the original datasets used had a very heavy bias of northern European genetic data. Recent studies have shown that genetic markers found by GWAS in one population cannot necessarily be transferred in a meaningful way to another population. This story hence also serves as a very concrete illustration of how a Eurocentric approach may skew scientific results.

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Enhanced Circularly Polarized Luminescence in Emissive Charge‐Transfer Complexes

By Jianlei Han, Dong Yang, Xue Jin, Yuqian Jiang, Minghua Liu, Pengfei Duan from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 15, 2019.

Circularly polarized luminescence of charge‐transfer complexes was demonstrated for the first time. The complexes feature a large glum value owing to charge‐transfer interactions. Benefiting from the large magnetic dipole transition moment in the charge‐transfer state, the CPL activity of mixed‐stack CT complexes exhibited large circular polarization. Abstract Achieving a large dissymmetry factor (glum) is a challenge in the field of circularly polarized luminescence (CPL). A chiral charge‐transfer (CT) system consisting of chiral electron donor and achiral electron acceptor shows bright circularly polarized emission with large glum value. The chiral emissive CT complexes could be fabricated through various approaches, such as grinding, crystallization, spin coating, and gelatinization, by simply blending chiral donor and achiral acceptor. The structural synergy originating from π–π stacking and strong CT interactions resulted in the long‐range ordered self‐assembly, enabling the formation of supramolecular gels. Benefiting from the large magnetic dipole transition moment in the CT state, the CPL activity of CT complexes exhibited large circular polarization. Our design strategy of the chiral emissive CT complexes is expected to help the development of new molecular engineering strategies for designing highly efficient CPL‐active materials.

Wed 24 Apr 10:00: Canopus and RCanopus: Scalable Consensus for Permissioned Blockchains  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 Apr 15, 2019.

Canopus and RCanopus: Scalable Consensus for Permissioned Blockchains

A critical problem with the consensus protocols underlying blockchains is that they do not scale well. As the number of transactions needing linearization increases, network traffic from topology-oblivious broadcasts can quickly overwhelm the network or a central coordinator. Thus, achieving strong linearizabiilty is typically restricted to a handful of participants, or systems must resort to weaker forms of consensus, such as those using proof of work. To address this problem, we propose Canopus, a highly-parallel consensus protocol that exploits modern data center network topology, parallelism, and consensus semantics to achieve scalability. Our key insight is to make network communication patterns topology-aware. In our prototype implementation, Canopus achieves rates as high as 5m linearizable transactions/second over 21 nodes distributed across 7 datacenters. I will also outline an extension, Resilient Canopus, that makes Canopus Byzantine Fault Tolerant as well as network partition tolerant.

 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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Wed 24 Apr 10:00: Canopus and RCanopus: Scalable Consensus for Permissioned Blockchains  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 Apr 15, 2019.

Canopus and RCanopus: Scalable Consensus for Permissioned Blockchains

A critical problem with the consensus protocols underlying blockchains is that they do not scale well. As the number of transactions needing linearization increases, network traffic from topology-oblivious broadcasts can quickly overwhelm the network or a central coordinator. Thus, achieving strong linearizabiilty is typically restricted to a handful of participants, or systems must resort to weaker forms of consensus, such as those using proof of work. To address this problem, we propose Canopus, a highly-parallel consensus protocol that exploits modern data center network topology, parallelism, and consensus semantics to achieve scalability. Our key insight is to make network communication patterns topology-aware. In our prototype implementation, Canopus achieves rates as high as 5m linearizable transactions/second over 21 nodes distributed across 7 datacenters. I will also outline an extension, Resilient Canopus, that makes Canopus Byzantine Fault Tolerant as well as network partition tolerant.

 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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Ultra‐Tough Inverse Artificial Nacre Based on Epoxy‐Graphene by Freeze‐Casting

By Chuanjin Huang, Jingsong Peng, Sijie Wan, Yi Du, Shixue Dou, Hanoch Daniel Wagner, Antoni P. Tomsia, Lei Jiang, Qunfeng Cheng from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 15, 2019.

Layer upon layer: Inspired by the structure of nacre, inverse artificial nacres based on epoxy graphene with different epoxy layer thicknesses were fabricated by a freeze‐casting technique. The optimized nanocomposite shows exceptional fracture toughness and temperature‐sensing. Abstract Epoxy nanocomposites combining high toughness with advantageous functional properties are needed in many fields. However, fabricating high‐performance homogeneous epoxy nanocomposites with traditional methods remains a great challenge. Nacre with outstanding fracture toughness presents an ideal blueprint for the development of future epoxy nanocomposites. Now, high‐performance epoxy‐graphene layered nanocomposites were demonstrated with ultrahigh toughness and temperature‐sensing properties. These nanocomposites are composed of ca. 99 wt % organic epoxy, which is in contrast to the composition of natural nacre (ca. 96 wt % inorganic aragonite). These nanocomposites are named an inverse artificial nacre. The fracture toughness reaches about 4.2 times higher than that of pure epoxy. The electrical resistance is temperature‐sensitive and stable under various humidity conditions. This strategy opens an avenue for fabricating high‐performance epoxy nanocomposites with functional properties.

Template‐Free Synthesis and Selective Filling of Janus Nanocups

By Xiaolian Qiang, Andrea Steinhaus, Chen Chen, Ramzi Chakroun, André H. Gröschel from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 15, 2019.

Janus nanocups with attoliter volume and strictly different chemistry on the inside and the outside allow selective storage of molecular components as well as the capture of nanoparticles. In their Communication (DOI: 10.1002/anie.201814014), A. H. Gröschel and co‐workers present a synthetic route to Janus nanocups from ABC triblock terpolymers and investigate their properties.

Identification of Chemokine Ligands by Biochemical Fragmentation and Simulated Peptide Evolution

By Jens‐Alexander Fuchs, Cyrill Brunner, Philipp Schineis, Jan A. Hiss, Gisbert Schneider from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 15, 2019.

Fragmentation of the chemokine‐receptor CCL19/CCR7 binding domain led to a hexapeptide as a template for de novo peptide design. Computer‐generated peptides were characterized in terms of their binding to CCl19. Potent ligands were identified as starting points for developing innovative protein–protein interaction modulators. Abstract Short linear peptides can overcome certain limitations of small molecules for targeting protein–protein interactions (PPIs). Herein, the interaction between the human chemokine CCL19 with chemokine receptor CCR7 was investigated to obtain receptor‐derived CCL19‐binding peptides. After identifying a linear binding site of CCR7, five hexapeptides binding to CCL19 in the low micromolar to nanomolar range were designed, guided by pharmacophore and lipophilicity screening of computationally generated peptide libraries. The results corroborate the applicability of the computational approach and the chosen selection criteria to obtain short linear peptides mimicking a protein–protein interaction site.

Hydrogen Peroxide Assisted Synthesis of Highly Luminescent Sulfur Quantum Dots

By Henggang Wang, Zhenguang Wang, Yuan Xiong, Stephen V. Kershaw, Tianzi Li, Yue Wang, Yongqing Zhai, Andrey L. Rogach from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 15, 2019.

An H2O2‐assisted top‐down approach was proposed to synthesize brightly luminescent sulfur quantum dots (SQDs), which allows us to simultaneously control the final size, to tune their emission color, and to improve their emission quantum yield (up to 23 %) by eliminating surface traps. White light emitting diodes using blue emissive SQDs and orange emissive copper nanoclusters are also demonstrated. Abstract An H2O2‐assisted top‐down approach is used to synthesize brightly luminescent, color‐tunable sulfur quantum dots (SQDs), with a photoluminescence quantum yield of up to 23 %. The formation of SQDs involves dissolution of bulk sulfur powder into small particles in an alkaline environment in the presence of polyethylene glycol, followed by H2O2‐assisted etching of polysulfide species, which has the advantage of the passivation of surface states. This synthetic strategy allows us to simultaneously control the final size of SQDs, to tune their emission color, and to improve their emission quantum yield by eliminating surface traps. Down‐conversion white light emitting diodes were also fabricated using blue emissive SQDs and orange emissive copper nanoclusters, with CIE color coordinates of (0.33, 0.32) and a high color rendering index of 91. The water‐soluble, highly luminescent SQDs are promising luminescent materials that can be produced from abundant precursor materials.

Thu 25 Apr 15:00: A Decade of Ubiquitous Computing Research in Mental Health

From All Talks (aka the CURE list). Published on Apr 15, 2019.

A Decade of Ubiquitous Computing Research in Mental Health

Abstract: This year it is ten years since smartphones became widely available as an open platform and have since then been used for creating novel personalised health applications. From the very beginning, there has been an interest in exploiting the advantages of mobile and wearable technologies in mental health to unobtrusively sense and analyse human behaviour, assess and predict mental health status, and to deliver feedback and intervention when needed.

In this talk, I look back on the last decade of Ubicomp research in mental health and use this as an stepping stone for discussing current and future research opportunities. The historical review is based on two recent surveys that I’ve been part of. The first survey presents a review of 45 systems presented over the years and investigate which mental health disease they are designed for, as well as their technical features in terms of sensing, prediction, intervention, and clinical assessment [1]. The second survey investigate whether changes in depressive symptoms can be detected by monitoring the patient’s behaviour using mobile and wearable technology – a core research goal in early research. We reviewed 46 studies, collection more than 17 different features and investigated whether these many studies agree on the relationship between depressive symptoms and patient behaviour collected from mobile and wearable devices. The review shows agreement across studies that some behaviour is strongly correlated to changes in depressive symptoms, while others show no or conflicting correlation [2].

Based on these two surveys, I will discuss current opportunities for research in ubicomp and mental health. In particular I will provide an example of moving from sensing to intervention technology and will present our current technological work in supporting this.

1. Bardram JE, Matic A. A Decade of Ubiquitous Computing Research in Mental Health. Unpublished manuscript. 2019.

2. Rohani DA, Faurholt-Jepsen M, Kessing LV, Bardram JE. Correlations Between Objective Behavioral Features Collected From Mobile and Wearable Devices and Depressive Mood Symptoms in Patients With Affective Disorders: Systematic Review. JMIR Mhealth Uhealth 2018;6(8):e165. DOI : 10.2196/mhealth.9691. PMID : 30104184

Bio: Jakob E. Bardram, PhD, is a professor in computer science at the Technical University of Denmark [www.dtu.dk], adjunct professor in public health at the Faculty of Health and Medical Sciences at the University of Copenhagen [www.sund.ku.dk], and the director of the Copehagen Center for Health Technology [www.cachet.dk]. He is the co-founder of Cetrea and Monsenso [monsenso.com], where he is serving as board member and chief scientific officer. His main research areas are software architecture, mobile & ubiquitous computing, and user interface software technology with a focus on healthcare, ranging from activity-based software architectures for electronic medical records, to interactive displays for clinical logistics in hospitals, and to personal health technology for mental health. Read more on his home page [www.bardram.net] and google scholar [scholar.google.dk/citations?user=pRriaUQAAAAJ].

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[ASAP] Holey Graphene Metal Nanoparticle Composites via Crystalline Polymer Templated Etching

By David L. White, Seth C. Burkert, Sean I. Hwang, Alexander Star from Nano Letters: Latest Articles (ACS Publications). Published on Apr 15, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.8b04755

[ASAP] Thermoelectric Conversion at 30 K in InAs/InP Nanowire Quantum Dots

By Domenic Prete, Paolo Andrea Erdman, Valeria Demontis, Valentina Zannier, Daniele Ercolani, Lucia Sorba, Fabio Beltram, Francesco Rossella, Fabio Taddei, Stefano Roddaro from Nano Letters: Latest Articles (ACS Publications). Published on Apr 15, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b00276

[ASAP] Transport Studies of Epi-Al/InAs Two-Dimensional Electron Gas Systems for Required Building-Blocks in Topological Superconductor Networks

By Joon Sue Lee, Borzoyeh Shojaei, Mihir Pendharkar, Anthony P. McFadden, Younghyun Kim, Henri J. Suominen, Morten Kjaergaard, Fabrizio Nichele, Hao Zhang, Charles M. Marcus, Chris J. Palmstrøm from Nano Letters: Latest Articles (ACS Publications). Published on Apr 15, 2019.

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Nano Letters
DOI: 10.1021/acs.nanolett.9b00494

[ASAP] Pursuing Specific Chemotherapy of Orthotopic Breast Cancer with Lung Metastasis from Docking Nanoparticles Driven by Bioinspired Exosomes

By Fei Xiong, Xiang Ling, Xing Chen, Jing Chen, Jiaxing Tan, Wuji Cao, Liang Ge, Minglin Ma, Jun Wu from Nano Letters: Latest Articles (ACS Publications). Published on Apr 15, 2019.

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Nano Letters
DOI: 10.1021/acs.nanolett.9b00824

[ASAP] Spontaneous Formation of 1D Pattern in Monolayer VSe2 with Dispersive Adsorption of Pt Atoms for HER Catalysis

By Zhong-Liu Liu, Bao Lei, Zhi-Li Zhu, Lei Tao, Jing Qi, De-Liang Bao, Xu Wu, Li Huang, Yu-Yang Zhang, Xiao Lin, Ye-Liang Wang, Shixuan Du, Sokrates T. Pantelides, Hong-Jun Gao from Nano Letters: Latest Articles (ACS Publications). Published on Apr 15, 2019.

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Nano Letters
DOI: 10.1021/acs.nanolett.9b00889

[ASAP] A General Approach to Free-Standing Nanoassemblies via Acoustic Levitation Self-Assembly

By Qianqian Shi, Wenli Di, Dashen Dong, Lim Wei Yap, Lin Li, Duyang Zang, Wenlong Cheng from ACS Nano: Latest Articles (ACS Publications). Published on Apr 15, 2019.

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ACS Nano
DOI: 10.1021/acsnano.8b09628

[ASAP] Photoinduced Doping To Enable Tunable and High-Performance Anti-Ambipolar MoTe2/MoS2 Heterotransistors

By Enxiu Wu, Yuan Xie, Qingzhou Liu, Xiaodong Hu, Jing Liu, Daihua Zhang, Chongwu Zhou from ACS Nano: Latest Articles (ACS Publications). Published on Apr 15, 2019.

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ACS Nano
DOI: 10.1021/acsnano.9b00201

[ASAP] Lasing in Ni Nanodisk Arrays

By Sara Pourjamal, Tommi K. Hakala, Marek Necada, Francisco Freire-Fernández, Mikko Kataja, Heikki Rekola, Jani-Petri Martikainen, Päivi Törmä, Sebastiaan van Dijken from ACS Nano: Latest Articles (ACS Publications). Published on Apr 15, 2019.

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ACS Nano
DOI: 10.1021/acsnano.9b01006

[ASAP] Substrate Metabolism-Driven Assembly of High-Quality CdSxSe1–x Quantum Dots in Escherichia coli: Molecular Mechanisms and Bioimaging Application

By Li-Jiao Tian, Yuan Min, Wen-Wei Li, Jie-Jie Chen, Nan-Qing Zhou, Ting-Ting Zhu, Dao-Bo Li, Jing-Yuan Ma, Peng-Fei An, Li-Rong Zheng, Hai Huang, Yang-Zhong Liu, Han-Qing Yu from ACS Nano: Latest Articles (ACS Publications). Published on Apr 15, 2019.

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ACS Nano
DOI: 10.1021/acsnano.9b01581

[ASAP] Nanobuffering of pH-Responsive Polymers: A Known but Sometimes Overlooked Phenomenon and Its Biological Applications

By Wei Tao, Junqing Wang, Wolfgang J. Parak, Omid C. Farokhzad, Jinjun Shi from ACS Nano: Latest Articles (ACS Publications). Published on Apr 15, 2019.

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ACS Nano
DOI: 10.1021/acsnano.9b01696

[ASAP] Enhanced Generation of Non-Oxygen Dependent Free Radicals by Schottky-type Heterostructures of Au–Bi2S3 Nanoparticles via X-ray-Induced Catalytic Reaction for Radiosensitization

By Xin Wang, Chenyang Zhang, Jiangfeng Du, Xinghua Dong, Shan Jian, Liang Yan, Zhanjun Gu, Yuliang Zhao from ACS Nano: Latest Articles (ACS Publications). Published on Apr 15, 2019.

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ACS Nano
DOI: 10.1021/acsnano.9b01818

[ASAP] In Situ Photoconversion of Multicolor Luminescence and Pure White Light Emission Based on Carbon Dot-Supported Supramolecular Assembly

By Huang Wu, Yong Chen, Xianyin Dai, Peiyu Li, J. Fraser Stoddart, Yu Liu from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Apr 15, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.8b13675

[ASAP] Arsenoplatin-1 Is a Dual Pharmacophore Anticancer Agent

By Ðenana Miodragovic, Antonello Merlino, Elden P. Swindell, Abraham Bogachkov, Richard W. Ahn, Sara Abuhadba, Giarita Ferraro, Tiziano Marzo, Andrew P. Mazar, Luigi Messori, Thomas V. O’Halloran from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Apr 15, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.8b13681

[ASAP] Topology Exploration in Highly Connected Rare-Earth Metal–Organic Frameworks via Continuous Hindrance Control

By Yutong Wang, Liang Feng, Weidong Fan, Kun-Yu Wang, Xia Wang, Xiaokang Wang, Kai Zhang, Xiurong Zhang, Fangna Dai, Daofeng Sun, Hong-Cai Zhou from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Apr 15, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b00122

[ASAP] Growth Kinetics of Individual Co Particles Ex-solved on SrTi0.75Co0.25O3-d Polycrystalline Perovskite Thin Films

By Yong-Ryun Jo, Bonjae Koo, Min-Ji Seo, Jun Kyu Kim, Siwon Lee, Kyeounghak Kim, Jeong Woo Han, WooChul Jung, Bong-Joong Kim from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Apr 15, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b01882

[ASAP] A NIR Light Gated DNA Nanodevice for Spatiotemporally Controlled Imaging of MicroRNA in Cells and Animals

By Jian Zhao, Hongqian Chu, Ya Zhao, Yi Lu, Lele Li from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Apr 15, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b01931

[ASAP] Synthesis of Sialidase-Resistant Oligosaccharide and Antibody Glycoform Containing a2,6-Linked 3Fax-Neu5Ac

By Hong-Jay Lo, Larissa Krasnova, Supriya Dey, Ting Cheng, Haitian Liu, Tsung-I Tsai, Kevin Binchia Wu, Chung-Yi Wu, Chi-Huey Wong from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Apr 15, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b01991

[ASAP] Photodriven Oxidation of Water by Plastoquinone Analogs with a Nonheme Iron Catalyst

By Young Hyun Hong, Jieun Jung, Tatsuo Nakagawa, Namita Sharma, Yong-Min Lee, Wonwoo Nam, Shunichi Fukuzumi from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Apr 15, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b02517

[ASAP] A Self-Assembled Organic/Metal Junction for Water Photo-Oxidation

By Astrid J. Olaya, Terumasa Omatsu, Jonnathan C. Hidalgo-Acosta, Julieta S. Riva, Victor Costa Bassetto, Natalia Gasilova, Hubert H. Girault from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Apr 15, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b02693

Quantum non-demolition measurement of an electron spin qubit

By Seigo Tarucha from Nature Nanotechnology - Issue - nature.com science feeds. Published on Apr 15, 2019.

Quantum non-demolition measurement of an electron spin qubit

Quantum non-demolition measurement of an electron spin qubit, Published online: 15 April 2019; doi:10.1038/s41565-019-0426-x

While measurement of an electron spin commonly destroys it, the quantum non-demolition measurement implemented here for an electron spin qubit in a semiconductor quantum dot preserves the measured spin and allows for exponential suppression of readout errors by repeated measurements.

Boron-Titanate Monolayer Nanosheets for Highly Selective Adsorption of Immunoglobulin G

By Jian-Hua Wang from RSC - Nanoscale latest articles. Published on Apr 15, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR01111K, Paper
Peng-Fei Guo, Xi-Ming Wang, Mengmeng Wang, Ting Yang, Ming-Li Chen, Jian-Hua Wang
Boron-titanate monolayer nanosheets are prepared through a scalable step by step intercalation approach for anchoring 3-mercaptopropyltriethoxysilane (MPTS) on the surface. MPTS provides clickable sites with 4-vinylphenylboronic acid (VPBA) via a...
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Dehydration impeding ionic conductance through two-dimensional angstrom-scale slits

By FengChao Wang from RSC - Nanoscale latest articles. Published on Apr 15, 2019.

Nanoscale, 2019, Advance Article
DOI: 10.1039/C9NR00317G, Paper
YanZi Yu, JingCun Fan, Jun Xia, YinBo Zhu, HengAn Wu, FengChao Wang
Energy barriers which impede ionic conductance through 2D angstrom-scale slits can be theoretically connected to the partial dehydration process.
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Highly-efficient solar steam generation of supported metal-organic framework membranes by a photo-induced electron transfer process

By Chunying Duan from RSC - Nanoscale latest articles. Published on Apr 15, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C8NR09080G, Paper
Liyong Chen, Dezhi Li, Yanxin Wang, Chunying Duan
Porphyrin-based molecules possess excellent photo-physical properties, and are widely applied to solar-to-energy-related research fields. Nonetheless, these molecules featuring small cross section of optical absorption and high radiative recombination rate give...
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Laser printing of optically resonant hollow crystalline carbon nanostructures from 1D and 2D metal-organic frameworks

By Thierry Belmonte from RSC - Nanoscale latest articles. Published on Apr 15, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR02167A, Communication
Valentin Milichko, Leila Mingabudinova, Anastasiia S. Zalogina, Andrei Krasilin, Margarita I. Petrova, Pavel Trofimov, Yuri A. Mezenov, Evgenii Ubyivovk, Peter Lönnecke, Alexandre Nomine, Jaafar Ghanbaja, Thierry Belmonte
Using a hybrid approach involving a slow diffusion method to synthesize 1D and 2D MOFs followed by their treatment with femtosecond infrared laser radiation, we generated 100-600 nm well-defined hollow...
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The role of excitons within the hole transporting layer in quantum dot light emitting device degradation

By Hany Aziz from RSC - Nanoscale latest articles. Published on Apr 15, 2019.

Nanoscale, 2019, Advance Article
DOI: 10.1039/C8NR09560D, Paper
Open Access Open Access
Creative Commons Licence  This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
Tyler Davidson-Hall, Hany Aziz
Electroluminescence and photoluminescence stability of QDLEDs is found to depend on the hole transporting layer and materials that are highly susceptible to exciton-induced degradation can negatively impact QDLED stability.
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Optical Response of Magnetically Actuated Biocompatible Membranes

By Bernard Dieny from RSC - Nanoscale latest articles. Published on Apr 15, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR00585D, Paper
Hélène Joisten, Alain Truong, Svetlana Ponomareva, Cécile Naud, Robert Morel, Yanxia HOU, Isabelle Joumard, Stephane Auffret, Philippe Sabon, Bernard Dieny
Biocompatible suspended magneto-elastic membranes were prepared. They consist of PDMS (Polydimethylsiloxane) films, with embedded arrays of micrometric magnetic pillars made by lithography techniques. For visible light wavelengths, our membranes constitute...
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Cauliflower-like CeO2-TiO2 Hybrid Nanostructures with Extreme Photocatalytic and Self-Cleaning Properties

By Oral Cenk Aktas from RSC - Nanoscale latest articles. Published on Apr 15, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR01208G, Communication
Salih Veziroglu, Katharina Röder, Ole Gronenberg, Alexander Vahl , Oleksandr Polonskyi, Thomas Strunskus, Horst-Gunter Rubahn, Lorenz Kienle, Jost Adam, Jacek Fiutowski, Franz Faupel, Oral Cenk Aktas
In recent years, heterogenous photocatalysis gained an enormous interest due to continuously increasing environmental pollution. Here we propose a facile approach to synthesize cauliflower-like CeO2-TiO2 hybrid structures by magnetron reactive...
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Nanostructured electrically conductive hydrogels via ultrafast laser processing and self-assembly

By Wei Xiong from RSC - Nanoscale latest articles. Published on Apr 15, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR01230C, Paper
Yufeng Tao, Chengyiran Wei, Jingwei Liu, Chunsan Deng, Song Cai, Wei Xiong
Electrically conductive polymers have emerged as functional materials for future electronics due to their high electrical conductivity, real-time responsiveness, easy film-formation ability and desirable stretchability. However, the previously-developed conductive polymer...
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Combining dielectrophoresis and concentration polarization-based preconcentration to enhance bead-based immunoassay sensitivity

By Gilad Yossifon from RSC - Nanoscale latest articles. Published on Apr 15, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR02506E, Paper
Sinwook Park, Gilad Yossifon
Ionic concentration-polarization (CP)-based biomolecule preconcentration is an established method for enhancing the detection sensitivity of target biomolecules immunoassay. However, its main drawback lies in its inability to directly control the...
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Single-excitation, dual-emission biomass quantum dots: preparation and application for ratiometric fluorescence imaging of coenzyme A in living cells

By Shulin Zhao from RSC - Nanoscale latest articles. Published on Apr 15, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR01809C, Communication
Yong Cui, Rongjun Liu, Fanggui Ye, Shulin Zhao
Ratiometric fluorescence imaging can decrease or even eliminate the influences of the microenvironment, localized probe distribution, and instrumental parameters, thereby permitting more accurate monitoring of intracellular molecular events. Therefore, developing...
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Molecular swings as extremely active ion transporters

By Huaqiang Zeng, Changliang Ren, Feng Chen, Ruijuan Ye, Yong Siang Ong, Hongfang Lu, Su Seong Lee, Jackie Ying from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 14, 2019.

Ions get transported across membrane mostly via carrier or channel mechanisms. We report herein a unique class of molecular machine‐inspired membrane transporters, termed molecular swings that utilize a previously unexplored swing mechanism for promoting ion transport in a highly efficient manner. In particular, the molecular swing, which carries a 15‐crown‐5 unit as the ion‐binding and transporting unit, exhibits extremely high ion transport activities with EC50 values of 46 nM (a channel:lipid molar ratio of 1:4800 or 0.021 mol% relative to lipid) and 110 nM for K+ and Na+ ions, respectively. Remarkably, such ion transport activities remain high in cholesterol‐rich environment, with EC50 values of 130 (0.045 mol% relative to lipid/cholesterol) and 326 nM, respectively, for K+ and Na+ ions.

Mechanochromism, Twisted/Folded Structures Determination, and Derivatization of N‐Phenyl Fluorenylidene‐Acridane

By Yutaka Matsuo, Ya Wang, Hiroshi Ueno, Takafumi Nakagawa, Hiroshi Okada from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 14, 2019.

N‐phenyl fluorenylidene‐acridane (Ph‐FA) compounds with electron‐withdrawing and ‐donating substituents (H, MeO, Ph, NO2, Br, F) at the para position of the phenyl group were successfully synthesized by the Barton‐Kellogg reaction of N‐aryl thioacridones and diazofluorene. By using the substituent on nitrogen to alter electronic properties, both the folded and twisted conformers of p‐NO2‐C6H4‐FA were crystallographically characterized to understand charge transfer from the electron‐donating acridane moiety to the electron‐accepting fluorenylidene moiety. Ground state mechanochromism, thermochromism, vapochromism, and proton‐induced chromism were demonstrated by utilizing folded/twisted conformational change between the conformers. Protonation and chemical oxidation of Ph‐FA gave two stable acridiniums, namely, fluorenyl acridinium and acridinium radical cation. The present studies will contribute to development of functional dyes and organic semiconductors.

Collective Total Synthesis of the Prostaglandins Family via Stereocontrolled Organocatalytic Baeyer‐Villiger Oxidation

By Kejie Zhu, Sha Hu, Minjie Liu, Haihui Peng, Fener Chen from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 14, 2019.

A new protocol for the synthesis of prostaglandins using a stereocontrolled organocatalytic Baeyer‐Villiger (B‐V) oxidation was described for the first time. The key B‐V oxidation of racemic cyclobutanone with aqueous hydrogen peroxide has enabled an early stage construction of bicyclic lactone skeleton in high enantiomeric excess (up to 99%). The generated bicyclic lactone is fully primed with two desired stereocenters and enabled the assembly of the entire family of prostaglandins. Furthermore, reactivity and enantioselectivity of B‐V oxidation of racemic bicyclic cyclobutanones were evaluated and 90‐99% ee was obtained, representing one of the most efficient ways for chiral lactones synthesis. This study further facilitates the synthesis of prostaglandins and chiral lactone‐containing natural products to promote new drug discoveries.

Metalloradicals Supported by a meta‐Carborane Ligand

By Guo-Xin Jin, Peng-Fei Cui, Yang Gao, Guo Shu-Ting, Yue-Jian Lin, Zhen-Hua Li from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 14, 2019.

In this work, a pincer type complex [Cp*Ir‐(SNPh)(SNHPh)(C2B10H9)] (2) has been synthesized and its reactivity has been studied in detail. Interestingly, molecular hydrogen can induce the transformation between the metalloradical [Cp*Ir‐(SNPh)2(C2B10H9)] (5•) and the complex 2. A mixed‐valence complex [(Cp*Ir)2‐(SNPh)2(C2B10H8)] (7•+) is also synthesized by one‐electron oxidation. Studies show that the complex 7•+ is fully delocalized, possessing a 4c‐1e (S‐Ir‐Ir‐S) bonding interaction. DFT calculations also provided good agreement with the experimental results.

Thu 02 May 13:10: From molecules to materials: new catalysts for artificial photosynthesis

From All Talks (aka the CURE list). Published on Apr 13, 2019.

From molecules to materials: new catalysts for artificial photosynthesis

Molecular hydrogen is the ultimate clean fuel due to its extremely high energy density and its clean combustion to water. However, the challenge lies to produce it sustainably from water, which requires catalysts to lower the kinetic energy barrier. Molecular catalysts based on non-precious metals fascinates synthetic chemists the most due to their tunability which allows us to tailor the structure and control their properties. However, molecular catalysts are somewhat disadvantaged by practical consideration because they often function in homogeneous solution and display limited long-term stability. Having an effective scaffold to mount the catalyst on, representing ‘heterogenisation’ of the molecule, is a key part of building a practical system that brings together the benefits of homogeneous and heterogeneous catalysis. Metal-organic framework, a type of crystalline material composed of metal clusters connected by organic linkers, offers a step further by allowing us to build tunable three-dimensional architecture by using molecules as the building blocks. In this talk, I will explore how the metal-organic framework enables us to transfer the chemistry of molecular catalysts into a solid material while still enjoying the benefits of heterogenous catalysis.

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Fri 10 May 11:00: Modelling and Assessing the Impacts of Intercropping, as a Sustainable Farming Practice, on Food Security, Air Quality, and Public Health

From All Talks (aka the CURE list). Published on Apr 13, 2019.

Modelling and Assessing the Impacts of Intercropping, as a Sustainable Farming Practice, on Food Security, Air Quality, and Public Health

Agriculture is the major emitter of atmospheric ammonia (NH3) in Europe, China, and the US (85 – 95%). This NH3 is also attributable to approximately 20% of the fine particulate matter (PM2.5) formed, which harms human health in the neighbourhood areas. The fast-growing food production, due to the rising world population and their more meat-inclined dietary habits, could thus worsen the pollution problem. Previous field studies have shown that soybean intercropping can exploit the mutualistic interactions between crops to promote legume nitrogen fixation for enhancing crop yield, reducing fertiliser use, and thus diminishing NH3 emission. In this study, we aim to investigate the potential benefit of large-scale intercropping on crop productivity, air quality, and public health. To quantify crop yield and NH3 emission under intercropping, we implement into a soil biogeochemical model, DeNitrification-DeComposition (DNDC), a new scheme to parametrize the belowground interactions of intercropped crops. With the DNDC -simulated NH3 emission, we predict the formation of downwind PM2 .5 using a global 3-D chemical transport model, GEOS -Chem. We find that, if all Chinese farms are adopting maize-soybean intercropping, the same croplands which were initially for only maize or soybean can now produce both crops with comparable yields (90-100%) as their monoculture counterparts. The fertiliser use for intercropping is 42% lower, leading to a reduction in NH3 emission by 45% and a drop in PM2 .5 concentration by up to 2.3% (equivalent to 1.5 μg m-3). This improvement can spare the Chinese government US$13 billion per year in air pollution-related health damage costs. Toward a better understanding on how regional conversion to sustainable farming alternatives may affect global climate and air quality, we are developing a process-based NH3 volatilisation scheme and the parametrisation of crop-crop belowground interactions into the Community Earth System Model (CESM). We hope that our study can help policymakers to evaluate the costs and benefits of adopting sustainable alternatives and derive a science-based long-term strategy for food security and air pollution mitigation.

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Thu 09 May 15:00: Particles in Membranes

From All Talks (aka the CURE list). Published on Apr 13, 2019.

Particles in Membranes

The interplay of curvature and particles diffusing in biological membranes is responsible for organizing and shaping the membrane and gives rise to a variety of cellular functions. Hybrid models combining a continuum representation of the membrane with discrete, highly coarse grained descriptions of particles have a long history in physics, while mathematical analysis is still in its infancy. We present a hierarchy of variational formulations of existing hybrid models, where the coupling of particles and membrane is formulated in terms of linear constraints to the minimization of the Canham–Helfrich energy of the membrane. Utilizing concepts from shape calculus, we derive a numerically feasible representation of the derivative of the minimal Canham–Helfrich energy for given particle positions with respect to the particle positions. This representation is applied in numerical investigations of the clustering behaviour of BAR domains and paves the way to Langevin dynamics of particles in membranes.

This is joint work with C.M. Elliott, C. Gräser and T. Kies

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New Mechanistic Insight into the Reaction of Organic Acids with SO3 at the Air‐Water Interface

By Jie Zhong, Hao Li, Manoj Kumar, Jiarong Liu, Ling Liu, Xiuhui Zhang, Xiao Cheng Zeng, Joseph S. Francisco from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 13, 2019.

The gas‐phase reaction of organic acids with SO3 has been recognized as essential in promoting aerosol particle formation. However, this reaction at the air‐water interface is poorly understood. Herein, we performed systematic Born‐Oppenheimer molecular dynamics (BOMD) simulations to study the reaction of various organic acids with SO3 on the surface of a water droplet. The results show that at the air‐water interface, the organic acid‐SO3 reaction follows a distinctly different mechanism than that in the gas phase. At the interface, the reaction occurs on the picosecond scale, within which the ion pairs of sulphuric‐carboxylic anhydride and hydronium form. This distinct reaction mechanism at the aqueous surface has important atmospheric implications, e.g., promoting water condensation, uptaking atmospheric condesation species, and incorporating “SO42‐” into organic species in aerosol particles. Therefore, the reaction acts as another path towards aerosol formation under humid conditions.

Mon 13 May 14:15: Flexoelectricity from first principles

From All Talks (aka the CURE list). Published on Apr 13, 2019.

Flexoelectricity from first principles

The flexoelectric (FxE) effect, where polarization is induced by a strain gradient, is universal in all insulators. As devices shrink to the micro and nano scale, large strain gradients can occur, and therefore the FxE effect can play a significant role in their electrical and mechanical properties. Also, the FxE effect can be exploited for novel device design paradigms such as piezoelectric ``meta-materials’’ constructed from nonpiezoelectric constituents, or mechanical switching of ferroelectric polarization. One of the crucial limitations to understanding and exploiting the FxE effect has been the lack of an efficient first-principles methodology to calculate all of the components of the bulk FxE tensor; the clamped-ion transverse and shear components in particular are problematic. We have developed such a methodology based on density functional perturbation theory to calculate the full bulk, clamped-ion FxE tensor with unprecedented accuracy and efficiency. In this talk I will review the microscopic aspects of the FxE effect, describe our computational methodology, and provide results for some simple systems including cubic perovskite oxides.

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High-speed scanning ion conductance microscopy for sub-second topography imaging of live cells

By Tilman E. Schäffer from RSC - Nanoscale latest articles. Published on Apr 13, 2019.

Nanoscale, 2019, Advance Article
DOI: 10.1039/C8NR10162K, Paper
Stefan Simeonov, Tilman E. Schäffer
High-speed scanning ion conductance microscopy (HS-SICM) reveals ultra-fast morphodynamics of live cells at a rate of 0.6 s per frame.
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Ultrahigh‐Loading Zinc Single‐Atom Catalyst for Highly Efficient Oxygen Reduction in Both Acidic and Alkaline Media

By Jia Li, Siguo Chen, Na Yang, Mingming Deng, Shumaila Ibraheem, Jianghai Deng, Jing Li, Li Li, Zidong Wei from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 12, 2019.

Slow and steady wins the race: An atomically dispersed Zn–N–C catalyst with an ultrahigh loading of single Zn atoms of 9.33 wt % (see HAADF‐STEM image) was successfully prepared by decreasing the annealing rate to 1° min−1. The Zn–N–C catalyst exhibited comparable ORR activity to that of the corresponding Fe–N–C catalyst, and greater ORR stability in both acidic and alkaline media. Abstract Atomically dispersed Zn–N–C nanomaterials are promising platinum‐free catalysts for the oxygen reduction reaction (ORR). However, the fabrication of Zn–N–C catalysts with a high Zn loading remains a formidable challenge owing to the high volatility of the Zn precursor during high‐temperature annealing. Herein, we report that an atomically dispersed Zn–N–C catalyst with an ultrahigh Zn loading of 9.33 wt % could be successfully prepared by simply adopting a very low annealing rate of 1° min−1. The Zn–N–C catalyst exhibited comparable ORR activity to that of Fe–N–C catalysts, and significantly better ORR stability than Fe–N–C catalysts in both acidic and alkaline media. Further experiments and DFT calculations demonstrated that the Zn–N–C catalyst was less susceptible to protonation than the corresponding Fe–N–C catalyst in an acidic medium. DFT calculations revealed that the Zn–N4 structure is more electrochemically stable than the Fe–N4 structure during the ORR process.

Electrochemical Real‐Time Mass Spectrometry (EC‐RTMS): Monitoring Electrochemical Reaction Products in Real Time

By Peyman Khanipour, Mario Löffler, Andreas M. Reichert, Felix T. Haase, Karl J. J. Mayrhofer, Ioannis Katsounaros from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 12, 2019.

A revolutionary method has been developed that allows the detection of electrochemical reaction products at the time they are formed. This enables highly sensitive, time‐ and potential‐resolved investigations of electrocatalyst selectivity for electrosynthesis reactions. The formation of a wide range of CO2 reduction products is followed during potential step and sweep experiments, for pristine and anodized copper. Abstract Methods that provide real‐time information are essential to resolve transients occurring at dynamic interfaces. Now a powerful method is presented that enables the time‐ and potential‐resolved characterization of liquid and gaseous products of electrochemical reactions shortly after their formation. To demonstrate its extraordinary potential, the electrochemical real time mass spectrometry (EC‐RTMS) approach is used to determine the products of the CO2 reduction reaction (CO2RR) during potential step or sweep experiments on pristine and in situ anodized copper. The enhanced formation of several C2+ products over C1 products is tracked directly after copper anodization, with unprecedented temporal resolution. This new technique creates exciting new opportunities for resolving processes that occur at short timescales and eventually for guiding the design of new, robust catalysts for selective electrosynthesis under dynamic operation.

Enantioselective Synthesis of Biaryl Atropisomers by Pd‐Catalyzed C−H Olefination using Chiral Spiro Phosphoric Acid Ligands

By Jun Luo, Tao Zhang, Lei Wang, Gang Liao, Qi‐Jun Yao, Yong‐Jie Wu, Bei‐Bei Zhan, Yu Lan, Xu‐Feng Lin, Bing‐Feng Shi from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 12, 2019.

The discovery of proper ligands to simultaneously modulate the reactivity and effectively control the stereoselectivity is a central topic in the field of enantioselective C−H activation. Herein, the synthesis of axially chiral biaryls by Pd‐catalyzed atroposelective C−H olefination is reported. A broad range of axially chiral quinoline derivatives were synthesized in good yields with excellent enantioselectivities (up to 98 % ee). Abstract The discovery of proper ligands to simultaneously modulate the reactivity and effectively control the stereoselectivity is a central topic in the field of enantioselective C−H activation. Herein, we reported the synthesis of axially chiral biaryls by Pd‐catalyzed atroposelective C−H olefination. A novel chiral spiro phosphoric acid, STRIP, was identified as a superior ligand for this transformation. A broad range of axially chiral quinoline derivatives were synthesized in good yields with excellent enantioselectivities (up to 98 % ee). Density functional theory was used to gain a theoretical understanding of the enantioselectivities in this reaction.

Polymeric Carbon Nitride/Reduced Graphene Oxide/Fe2O3: All‐Solid‐State Z‐Scheme System for Photocatalytic Overall Water Splitting

By Zhiming Pan, Guigang Zhang, Xinchen Wang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 12, 2019.

Improving charge transfer: A ternary heterojunction was designed, in which polymeric carbon nitride (PCN) and Fe2O3 served as the hydrogen evolution photocatalyst and the oxygen evolution photocatalyst, respectively, while reduced graphene oxide (RGO) acted as an electron transfer “freeway”. This all‐solid‐state Z‐scheme system showed promising activity for photocatalytic stoichiometric water splitting under simulated sunlight irradiation. Abstract The charge transfer between hydrogen evolution photocatalysts (HEPs) and oxygen evolution photocatalysts (OEPs) is the rate‐determining step that controls the overall performance of a Z‐scheme water‐splitting system. Here, we carefully design reduced graphene oxide (RGO) nanosheets for use as solid‐state mediators to accelerate the charge carrier transfer between HEPs (e.g., polymeric carbon nitride (PCN)) and OEPs (e.g., Fe2O3), thus achieving efficient overall water splitting. The important role of RGO could also be further proven in other PCN‐based Z‐systems (BiVO4/RGO/PCN and WO3/RGO/PCN), illustrating the universality of this strategy.

Scalable Polymer Nanocomposites with Record High‐Temperature Capacitive Performance Enabled by Rationally Designed Nanostructured Inorganic Fillers

By He Li, Ding Ai, Lulu Ren, Bin Yao, Zhubing Han, Zhonghui Shen, Jianjun Wang, Long‐Qing Chen, Qing Wang from Wiley: Advanced Materials: Table of Contents. Published on Apr 12, 2019.

High‐temperature dielectric polymer nanocomposites with facilely prepared nanostructured Al2O3 fillers exhibit remarkable electrical energy storage and discharging capabilities at elevated temperatures and high electric fields, outperforming the state‐of‐the‐art polymer dielectrics. The significant impact of the filler morphology on conduction behavior and capacitive performance of the composites is revealed. Abstract Next‐generation microelectronics and electrical power systems call for high‐energy‐density dielectric polymeric materials that can operate efficiently under elevated temperatures. However, the currently available polymer dielectrics are limited to relatively low working temperatures. Here, the solution‐processable polymer nanocomposites consisting of readily prepared Al2O3 fillers with systematically varied morphologies including nanoparticles, nanowires, and nanoplates are reported. The field‐dependent electrical conduction of the polymer nanocomposites at elevated temperatures is investigated. A strong dependence of the conduction behavior and breakdown strength of the polymer composites on the filler morphology is revealed experimentally and is further rationalized via computations. The polymer composites containing Al2O3 nanoplates display a record capacitive performance, e.g., a discharged energy density of 3.31 J cm−3 and a charge–discharge efficiency of >90% measured at 450 MV m−1 and 150 °C, significantly outperforming the state‐of‐the‐art dielectric polymers and nanocomposites that are typically prepared via tedious, low‐yield approaches.

Intrinsically Optimizing Charge Transfer via Tuning Charge/Discharge Mode for Lithium–Oxygen Batteries

By Wei Liu, Yue Shen, Yao Yu, Xia Lu, Wang Zhang, Zhaoming Huang, Jintao Meng, Yunhui Huang, Zaiping Guo from Wiley: Small: Table of Contents. Published on Apr 12, 2019.

A simple and effective strategy is presented via tuning charge/discharge mode to systematically investigate the Li2O2 bridged relationship between the discharge current and the charge overpotential. The effects of the discharge current density on the morphology, lithium vacancies, ionic conductivity, and electronic conductivity of Li2O2 have been extensively studied via theoretic calculation and advanced characterization techniques. Abstract Lithium–oxygen batteries have an ultrahigh theoretical energy density, almost ten times higher than lithium‐ion batteries. The poor conductivity of the discharge product Li2O2, however, severely raises the charge overpotential and pulls down the cyclability. Here, a simple and effective strategy is presented for regular formation of lithium vacancies in the discharge product via tuning charge/discharge mode, and their effects on the charge transfer behavior. The effects of the discharge current density on the lithium vacancies, ionic conductivity, and electronic conductivity of the discharge product Li2O2 are systematically investigated via electron spin resonance, spin‐alignment echo nuclear magnetic resonance, and tungsten nanomanipulators, respectively. The study by density functional theory indicates that the lithium vacancies in Li2O2 generated during the discharge process are highly dependent on the current density. High current can induce a high vacancy density, which enhances the electronic conductivity and reduces the overpotential. Meanwhile, with increasing discharge current, the morphology of the Li2O2 changes from microtoroids to thin nanoplatelets, effectively shortening the charge transfer distance and improving the cycling performance. The Li2O2 grown in fast discharge mode is more easily decomposed in the following charging process. The lithium–oxygen battery cycling in fast‐discharge/slow‐charge mode exhibits low overpotential and long cycle life.

Highly Reproducible Physiological Asymmetric Membrane with Freely Diffusing Embedded Proteins in a 3D‐Printed Microfluidic Setup

By Paul Heo, Sathish Ramakrishnan, Jeff Coleman, James E. Rothman, Jean‐Baptiste Fleury, Frederic Pincet from Wiley: Small: Table of Contents. Published on Apr 12, 2019.

Horizontal free‐standing membrane having a physiological lipid composition is reconstituted in a 3D‐printing‐based microfluidic chip. Simultaneous monitoring of the membrane processes with a microscope and patch‐clamp amplifier reveals that the membrane is free‐standing, horizontal, fully fluid, stable, flat, and large enough. Dual open‐channels adjacent to the bilayer are freely used to alter each lipid monolayer composition and oriented protein insertion. Abstract Experimental setups to produce and to monitor model membranes have been successfully used for decades and brought invaluable insights into many areas of biology. However, they all have limitations that prevent the full in vitro mimicking and monitoring of most biological processes. Here, a suspended physiological bilayer‐forming chip is designed from 3D‐printing techniques. This chip can be simultaneously integrated to a confocal microscope and a path‐clamp amplifier. It is composed of poly(dimethylsiloxane) and consists of a ≈100 µm hole, where the horizontal planar bilayer is formed, connecting two open crossed‐channels, which allows for altering of each lipid monolayer separately. The bilayer, formed by the zipping of two lipid leaflets, is free‐standing, horizontal, stable, fluid, solvent‐free, and flat with the 14 types of physiologically relevant lipids, and the bilayer formation process is highly reproducible. Because of the two channels, asymmetric bilayers can be formed by making the two lipid leaflets of different composition. Furthermore, proteins, such as transmembrane, peripheral, and pore‐forming proteins, can be added to the bilayer in controlled orientation and keep their native mobility and activity. These features allow in vitro recapitulation of membrane process close to physiological conditions.

Chemical Properties, Structural Properties, and Energy Storage Applications of Prussian Blue Analogues

By Wei‐Jie Li, Chao Han, Gang Cheng, Shu‐Lei Chou, Hua‐Kun Liu, Shi‐Xue Dou from Wiley: Small: Table of Contents. Published on Apr 12, 2019.

This Review provides a comprehensive overview of the latest research progress on Prussian blue analogues (PBAs), including the synthesis methods, structural and chemical properties of PBAs, various applications for these PBAs, and the effects of their structural and chemical properties on material synthesis and applications. Finally, some personal viewpoints on the challenges and outlook for PBAs application are included. Abstract Prussian blue analogues (PBAs, A2T[M(CN)6], A = Li, K, Na; T = Fe, Co, Ni, Mn, Cu, etc.; M = Fe, Mn, Co, etc.) are a large family of materials with an open framework structure. In recent years, they have been intensively investigated as active materials in the field of energy conversion and storage, such as for alkaline‐ion batteries (lithium‐ion, LIBs; sodium‐ion, NIB; and potassium‐ion, KIBs), and as electrochemical catalysts. Nevertheless, few review papers have focused on the intrinsic chemical and structural properties of Prussian blue (PB) and its analogues. In this Review, a comprehensive insight into the PBAs in terms of their structural and chemical properties, and the effects of these properties on their materials synthesis and corresponding performance is provided.

meta‐ and para‐Phenylenediamine‐fused Porphyrin Dimers: Synthesis and Magnetic Interactions in Their Dication Diradicals

By Atsuhiro Osuka, Kenichi Kato from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 12, 2019.

meta‐ and para‐Phenylenediamine‐fused NiII‐porphyrin dimers were synthesized by SNAr reaction of meso,β,β‐trichloro NiII‐porphyrin with meta‐ and para‐phenylenediamines and subsequent Pd‐catalyzed intramolecular C–H arylation. Their tetrachlorinated dication diradicals were very stable, allowing SQUID magnetometry that revealed clear open‐shell characters for both meta‐ and para‐isomers with ferro‐ and anti‐ferromagnetic interactions, respectively. Nitrogen analogue of Thiele’s hydrocarbon usually displays predominant closed‐shell nature but its hidden diradical characters increase in a twisted conformation or upon insertion of an additional phenylene spacer. The observed distinct diradical nature of the para‐congener indicates that diradical properties can be enhanced also by efficient spin delocalization.

NIR Light Activated Combination Therapy with Precisely Integrated Photosensitizer and Prodrug by a Host‐Guest Strategy

By Yanli Zhao, Hongzhong Chen, Xiaowei Zeng, Huijun Phoebe Tham, Soo Zeng Fiona Phua, Wei Cheng, Wenfeng Zeng, Haoran Shi, Lin Mei from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 12, 2019.

Co‐delivery of photosensitizers with reactive oxygen species (ROS) sensitive prodrugs for light triggered ROS generation and cascaded prodrug activation has drawn tremendous attention. However, the absence of a feasible method to deliver the two components with a precise ratio has impaired the application potential. Herein, we report an efficient method to fabricate a nanosized delivery platform with an optimized ratio of the two components by the means of host‐guest strategy for maximizing the combination therapy efficacy in the cancer treatment. The key features of this host‐guest strategy for the combination therapy lie in (i) the ratio between photosensitizer and ROS sensitive prodrug could be tuned easily, (ii) NIR irradiation as single external stimulus could sensitize the photosensitizer and activate paclitaxel prodrug for its release, and (iii) the accumulation process could be tracked by NIR imaging for maximizing the efficacy of photodynamic and chemotherapy.

Negative Charging of Au Nanoparticles during Methanol Synthesis from CO₂/H₂ on a Au/ZnO Catalyst: Insights from Operando Infrared and Near‐ambient Pressure XPS and XAS

By R. Juergen Behm, Ali M. Abdel-Mageed, Alexander Klyushin, Azita Rezvani, Axel Knop-Gericke, Robert Schlögl from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 12, 2019.

Kinetic measurements in combination with time resolved operando infrared (DRIFTS), in situ near ambient pressure X‐ray photoelectron spectroscopy (NAP‐XPS) and X‐ray absorption near edge spectroscopy (XANES) measurements at the O K‐edge together with high resolution electron microscopy were applied to evaluate the electronic and structural properties of Au/ZnO under industrial and idealized methanol synthesis conditions. CO adsorption during the reaction revealed the presence of negatively charged Au nanoparticles / Au sites under reaction conditions, which are formed during the initial phase of the reaction. Near ambient pressure XPS and XANES demonstrate the build‐up of O‐vacancies during the reaction, which goes along with a substantial increase in the methanol formation rate. The results are discussed in comparison with previous findings for Cu/ZnO and Au/ZnO catalysts.

Transformation of Metal‐Organic Frameworks into Stable Organic Frameworks with Inherited Skeletons and Catalytic Properties

By Chuan-De Wu, Kai Chen from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 12, 2019.

Metal‐organic frameworks (MOFs) are an emerging class of porous materials with attractive properties; however, their practical applications are heavily hindered by the fragile nature. We report herein an effective strategy to transform fragile coordination bonds in MOFs into stable covalent organic bonds under mild annealing decarboxylative coupling reaction conditions, which results in highly stable organic framework materials. This strategy endows successfully inherit the intrinsic framework skeletons, porosity and properties of the parent MOFs in the daughter organic framework materials which exhibit excellent chemical stability under harsh catalytic conditions. Therefore, this work opens a new avenue to synthesize stable organic framework materials derived from MOFs for applications in different fields.

Mixed‐Metal MOFs: Unique Opportunities in Metal‐organic Framework Functionality and Design

By Mohammad Yaser Masoomi, Ali Morsali, Amarajothi Dhakshinamoorthy, Hermenegildo García from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 12, 2019.

Mixed‐metal metal organic frameworks (MM‐MOFs) can be considered those MOFs having two metals anywhere in the structure. The present review summarizes the various strategies reported for preparation of MM‐MOFs and some of their applications in adsorption, gas separation and catalysis. It is shown that compared to homometallic MOFs, MM‐MOFs bring about the opportunity to take advantage of the complexity and the synergism derived from the presence of different metal ions in the structure of MOFs. This is reflected in a superior performance and even stability of MM‐MOFs respect to related single metal MOFs. Emphasis is made on the use of MM‐MOFs as catalysts for tandem reaction.

Covalent Inter‐Carbon‐Allotrope Architectures Consisting of the Endohedral Fullerene Sc3N@C80 and Single Walled Carbon Nanotubes

By Andreas Hirsch, Tao Wei, Oliver Martin, Muqing Chen, Shangfeng Yang, Frank Hauke from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 12, 2019.

Using a reductive sidewall functionalization concept we prepared for the first time a covalent inter‐carbon‐allotrope hybrid consisting of single walled carbon nanotubes (SWCNTs) and the endohedral fullerene Sc3N@C80. The characterization of this new compound type was accomplished by a variety of techniques including absorption spectroscopy, Raman spectroscopy, TG‐MS, TG‐GC‐MS and MALDI‐TOF mass spectroscopy. HRTEM investigations were carried out to visualize this highly integrated architecture.

Development of Dip‐Pen Nanolithography (DPN) and Its Derivatives

By Guoqiang Liu, Michael Hirtz, Harald Fuchs, Zijian Zheng from Wiley: Small: Table of Contents. Published on Apr 12, 2019.

Dip‐pen nanolithography (DPN) is a unique nanofabrication tool that can directly write a variety of molecular patterns on a surface with high resolution and excellent registration using a scanning tip. DPN has experienced a tremendous evolution since its invention in 1999. This work reviews the technical development of DPN and its derivative technologies over the past 20 years. Abstract Dip‐pen nanolithography (DPN) is a unique nanofabrication tool that can directly write a variety of molecular patterns on a surface with high resolution and excellent registration. Over the past 20 years, DPN has experienced a tremendous evolution in terms of applicable inks, a remarkable improvement in fabrication throughput, and the development of various derivative technologies. Among these developments, polymer pen lithography (PPL) is the most prominent one that provides a large‐scale, high‐throughput, low‐cost tool for nanofabrication, which significantly extends DPN and beyond. These developments not only expand the scope of the wide field of scanning probe lithography, but also enable DPN and PPL as general approaches for the fabrication or study of nanostructures and nanomaterials. In this review, a focused summary and historical perspective of the technological development of DPN and its derivatives, with a focus on PPL, in one timeline, are provided and future opportunities for technological exploration in this field are proposed.

Flexible Micropillar Electrode Arrays for In Vivo Neural Activity Recordings

By Mingde Du, Shouliang Guan, Lei Gao, Suye Lv, Siting Yang, Jidong Shi, Jinfen Wang, Hongbian Li, Ying Fang from Wiley: Small: Table of Contents. Published on Apr 12, 2019.

Flexible micropillar electrode arrays with multiscale hierarchical surface structure are prepared by a biotemplate method. The recording sites with protruding micropillars can form a tight interface with the soft cerebral cortex of the rat brain, which allows for the in vivo multichannel recordings of epileptiform activity with high signal‐to‐noise ratio. Abstract Flexible electronics that can form tight interfaces with neural tissues hold great promise for improving the diagnosis and treatment of neurological disorders and advancing brain/machine interfaces. Here, the facile fabrication of a novel flexible micropillar electrode array (µPEA) is described based on a biotemplate method. The flexible and compliant µPEA can readily integrate with the soft surface of a rat cerebral cortex. Moreover, the recording sites of the µPEA consist of protruding micropillars with nanoscale surface roughness that ensure tight interfacing and efficient electrical coupling with the nervous system. As a result, the flexible µPEA allows for in vivo multichannel recordings of epileptiform activity with a high signal‐to‐noise ratio of 252 ± 35. The ease of preparation, high flexibility, and biocompatibility make the µPEA an attractive tool for in vivo spatiotemporal mapping of neural activity.

Artificial Photosynthesis with Polymeric Carbon Nitride: When Meeting Metal Nanoparticles, Single Atoms, and Molecular Complexes

By Yanrui Li, Tingting Kong, Shaohua Shen from Wiley: Small: Table of Contents. Published on Apr 12, 2019.

Modifying polymeric carbon nitride (PCN) with metal nanoparticles, metal complexes, and single metal atoms is effective to extend the absorption spectrum range, improve charge separation, and accelerate surface reaction kinetics for great improvement in artificial photosynthesis. The recent progresses in metal/PCN photocatalyst systems for water splitting and CO2 reduction are reviewed. Abstract Artificial photosynthesis for solar water splitting and CO2 reduction to produce hydrogen and hydrocarbon fuels has been considered as one of the most promising ways to solve increasingly serious energy and environmental problems. As a well‐documented metal‐free semiconductor, polymeric carbon nitride (PCN) has been widely used and intensively investigated for photocatalytic water splitting and CO2 reduction, owing to its physicochemical stability, visible‐light response, and facile synthesis. However, PCN as a photocatalyst still suffers from the fast recombination of electron‐hole pairs and poor water redox reaction kinetics, greatly restricting its activity for artificial photosynthesis. Among the various modification approaches developed so far, decorating PCN with metals in different existences of nanoparticles, single atoms and molecular complexes, has been evidently very effective to overcome these limitations to improve photocatalytic performances. In this Review article, a systematic introduction to the state‐of‐the‐art metal/PCN photocatalyst systems is given, with metals in versatility of nanoparticles, single atoms, and molecular complexes. Then, the recent processes of the metal/PCN photocatalyst systems in the applications of artificial photosynthesis, e.g., water splitting and CO2 reduction, are reviewed. Finally, the remaining challenges and opportunities for the development of high efficiency metal/PCN photocatalyst systems are presented and prospected.

Specific K+ Binding Sites as CO2 Traps in a Porous MOF for Enhanced CO2 Selective Sorption

By Na Li, Ze Chang, Hongliang Huang, Rui Feng, Wei‐Wei He, Ming Zhong, David G. Madden, Michael J. Zaworotko, Xian‐He Bu from Wiley: Small: Table of Contents. Published on Apr 12, 2019.

K+ cations in effect serve as CO2 traps and enhance the CO2 selective sorption in an embedded K+ MOF. Abstract Metal‐organic frameworks (MOFs) can be fine‐tuned to boost sorbent‐sorbate interactions in order to improve gas sorption and separation performance, but the design of MOFs with ideal structural features for gas separation applications remains a challenge. Herein it is reported that unsaturated alkali metal sites can be immobilized in MOFs through a tetrazole based motif and that gas affinity can thereby be boosted. In the prototypal MOF of this type‐NKU‐521 (NKU denotes Nankai University), K+ cations are effectively embedded in a trinuclear Co2+‐tetrazole coordination motif. The embedded K+ sites are exposed to the pores of NKU‐521 through water removal, and the isosteric heat (Qst) for CO2 is boosted to 41 kJ mol‐1. The nature of the binding site is validated by molecular simulations and structural characterization. The K+ cations in effect serve as gas traps and boost the CO2‐framework affinity, as measured by the Qst, by 24%. In addition, the impact of unsaturated alkali metal sites upon the separation of hydrocarbons is evaluated for the first time in MOFs using ideal adsorbed solution theory (IAST) calculations and column breakthrough experiments. The results reveal that the presence of exposed K+ sites benefits gas sorption and hydrocarbon separation performances of this MOF.

Amorphous Mn3O4 Nanocages with High‐Efficiency Charge Transfer for Enhancing Electro‐Optic Properties of Liquid Crystals

By Guanshui Ma, Binbin Jia, Dongyu Zhao, Zhao Yang, Jian Yu, Juzhe Liu, Lin Guo from Wiley: Small: Table of Contents. Published on Apr 12, 2019.

Amorphous materials with dangling bonds and band tails could lead the energy of the system to a metastable state and thus facilitate surface electron escape and transfer. The as‐synthesized amorphous Mn3O4 octahedral nanocages are dispersed in a nematic liquid crystal matrix E7, and a markedly decreased threshold voltage and saturation voltage, a higher contrast, and a faster response time are achieved. Abstract Improving electro‐optic properties is essential for fabricating high‐quality liquid crystal displays. Herein, by doping amorphous Mn3O4 octahedral nanocages (a‐Mn3O4 ONCs) into a nematic liquid crystal (NLC) matrix E7, outstanding electro‐optic properties of the blend are successfully obtained. At a doping concentration of 0.03 wt%, the maximum decreases of threshold voltage (Vth) and saturation voltage (Vsat) are 34% and 31%, respectively, and the increase of contrast (Con) is 160%. This remarkable electro‐optic activity can be attributed to high‐efficiency charge transfer within the a‐Mn3O4 ONCs NLC system, caused by metastable electronic states of a‐Mn3O4 ONCs. To the best of our knowledge, such remarkable decreased electro‐optic activity is observed for the first time from doping amorphous semiconductors, which could provide a new pathway to develop excellent energy‐saving amorphous materials and improve their potential applications in electro‐optical devices.

Magnesium‐Catalyzed Hydroboration of Terminal and Internal Alkynes

By Marc Magre, Bholanath Maity, Alban Falconnet, Luigi Cavallo, Magnus Rueping from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 12, 2019.

MgBu2 proved to be an efficient catalyst for the hydroboration of terminal and internal alkynes, achieving good yields and selectivities. The compatibility with many functional groups makes the Mg‐catalyzed hydroboration of alkynes very attractive as a late stage functionalization protocol. Moreover, experimental investigations together with DFT calculations provide insight into the reaction mechanism. Abstract A magnesium‐catalyzed hydroboration of alkynes providing good yields and selectivities for a wide range of terminal and symmetrical and unsymmetrical internal alkynes has been developed. The compatibility with many functional groups makes this magnesium catalyzed procedure attractive for late stage functionalization. Experimental mechanistic investigations and DFT calculations reveal insights into the reaction mechanism of the magnesium catalyzed protocol.

Validating the Biphilic Hypothesis of Nontrigonal Phosphorus(III) Compounds

By Kyounghoon Lee, Anastasia V. Blake, Akira Tanushi, Sean M. McCarthy, Daniel Kim, Sydney M. Loria, Courtney M. Donahue, Kyle D. Spielvogel, Jason M. Keith, Scott R. Daly, Alexander T. Radosevich from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 12, 2019.

Double agent: P K‐edge XANES and TDDFT calculations were used to quantify how nontrigonal structural deformations affect the electronic structure and reactivity of a series of P(NNN) compounds. The results suggest that biphilic PIII reactivity reported previously with and without a transition‐metal host stems from a common low‐lying phosphorus‐based acceptor orbital that becomes energetically accessible in response to nontrigonal PIII distortions. Abstract Constraining σ3‐P compounds in nontrigonal, entatic geometries has proven to be an effective strategy for promoting biphilic oxidative addition reactions more typical of transition metals. Although qualitative descriptions of the impact of structure and symmetry on σ3‐P complexes have been proposed, electronic structure variations responsible for biphilic reactivity have yet to be elucidated experimentally. Reported here are P K‐edge XANES data and complementary TDDFT calculations for a series of structurally modified P(N)3 complexes that both validate and quantify electronic structure variations proposed to give rise to biphilic reactions at phosphorus. These data are presented alongside experimentally referenced electronic structure calculations that reveal nontrigonal structures predicted to further enhance biphilic reactivity in σ3‐P ligands and catalysts.

Polymerization of rac‐Lactide Using Achiral Iron Complexes: Access to Thermally Stable Stereocomplexes

By Paul Marin, Mathieu J.‐L. Tschan, Florence Isnard, Carine Robert, Pierre Haquette, Xavier Trivelli, Lise‐Marie Chamoreau, Vincent Guérineau, Iker del Rosal, Laurent Maron, Vincenzo Venditto, Christophe M. Thomas from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 12, 2019.

Chainlinks: Enantiopure poly(lactic acid) (PLA) forms stereocomplexes when enantiomeric PLA chains are mixed in equivalent amounts. The reported achiral iron complexes are highly active, productive, and stereoselective under mild reaction conditions for the ring‐opening polymerization of lactide. The corresponding catalytic systems enable the production of stereoblock polymers with high molecular weights. Abstract Enantiopure poly(lactic acid) (PLA) can form stereocomplexes when enantiomeric PLA chains are mixed in equivalent amounts. Such materials provide interesting features that might be suitable for numerous applications. Despite several advantages, the main drawback of PLA is its narrow window of processing, thus limiting its use for industrial applications. Reported herein are achiral iron complexes, that are highly active, productive, and stereoselective under mild reaction conditions for the ring‐opening polymerization of lactide. The corresponding catalytic systems enable the production of stereoblock polymers with high molecular weights, allowing the formation of thermally stable and industrially relevant stereocomplexes.

A Photo‐responsive Small‐Molecule Approach for the Opto‐epigenetic Modulation of DNA Methylation

By Ha Phuong Nguyen, Sabrina Stewart, Mikiembo N. Kukwikila, Sioned Fôn Jones, Daniel Offenbartl‐Stiegert, Shiqing Mao, Shankar Balasubramanian, Stephan Beck, Stefan Howorka from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 12, 2019.

A small‐molecule approach for the modulation of DNA methylation with light is presented. The strategy uses a photo‐tunable version of a clinically used drug (5‐aza‐2′‐deoxycytidine) to alter the catalytic activity of DNA methyltransferases. After uptake by cells, the photo‐regulated molecule can be light‐controlled to reduce genome‐wide DNA methylation levels in proliferating cells. Abstract Controlling the functional dynamics of DNA within living cells is essential in biomedical research. Epigenetic modifications such as DNA methylation play a key role in this endeavour. DNA methylation can be controlled by genetic means. Yet there are few chemical tools available for the spatial and temporal modulation of this modification. Herein, we present a small‐molecule approach to modulate DNA methylation with light. The strategy uses a photo‐tuneable version of a clinically used drug (5‐aza‐2′‐deoxycytidine) to alter the catalytic activity of DNA methyltransferases, the enzymes that methylate DNA. After uptake by cells, the photo‐regulated molecule can be light‐controlled to reduce genome‐wide DNA methylation levels in proliferating cells. The chemical tool complements genetic, biochemical, and pharmacological approaches to study the role of DNA methylation in biology and medicine.

Nonlinear Optical Switching in Regioregular Porphyrin Covalent Organic Frameworks

By Bishnu P. Biswal, Sreeramulu Valligatla, Mingchao Wang, Tanmay Banerjee, Nabil A. Saad, Bala Murali Krishna Mariserla, Naisa Chandrasekhar, Daniel Becker, Matthew Addicoat, Irena Senkovska, Reinhard Berger, D. Narayana Rao, Stefan Kaskel, Xinliang Feng from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 12, 2019.

COF it up! Three regioregular porphyrin‐based porous covalent organic frameworks (COFs) with excellent nonlinear optical (NLO) properties are presented. Por‐COF‐HH and its metalated congeners, Por‐COF‐ZnCu and Por‐COF‐ZnNi, were prepared by Schiff base condensation of tetrasubstituted porphyrin aldehydes and amines. The NLO switching and high‐parameter values obtained for these Por‐COFs are promising for optical switching and optical limiting devices. Abstract Covalent organic frameworks (COFs) have garnered immense scientific interest among porous materials because of their structural tunability and diverse properties. However, the response of such materials toward laser‐induced nonlinear optical (NLO) applications is hardly understood and demands prompt attention. Three novel regioregular porphyrin (Por)‐based porous COFs—Por‐COF‐HH and its dual metalated congeners Por‐COF‐ZnCu and Por‐COF‐ZnNi—have been prepared and present excellent NLO properties. Notably, intensity‐dependent NLO switching behavior was observed for these Por‐COFs, which is highly desirable for optical switching and optical limiting devices. Moreover, the efficient π‐conjugation and charge‐transfer transition in ZnCu‐Por‐COF enabled a high nonlinear absorption coefficient (β=4470 cm/GW) and figure of merit (FOM=σ1/σo, 3565) value compared to other state‐of‐the‐art materials, including molecular porphyrins (β≈100–400 cm/GW), metal–organic frameworks (MOFs; β≈0.3–0.5 cm/GW), and graphene (β=900 cm/GW).

Thu 02 May 12:30: Off-Market Block Trades, Transparency and Information Efficiency: New Evidence from Futures Markets

From All Talks (aka the CURE list). Published on Apr 12, 2019.

Off-Market Block Trades, Transparency and Information Efficiency: New Evidence from Futures Markets

Alex Frino University of Wollongong

Off market trades are transactions in securities markets which are executed away from the main market and later reported to the market. Off market trades are a recent phenomenon in futures markets and while there is a rich body of literature analysing off market trading in equities markets, this is the first study to analyse off market trading in futures markets. This issue is particularly topical, as the Chicago Mercantile Exchange introduced off-market trading for commodity futures in January 2018 which generated significant debate about the impact of the lack of transparency they create (Parking, April 8 2018, Wall Street Journal). In this paper, we examine the price impact of off market trades at the time they are executed and the time they are later reported to market. We find a statistically significant price reaction both around the time they are executed and the time they are later reported. We conclude that the market learns from trading around the off-market trade and impounds some of the information conveyed by the trade at the time they are executed. Given that the market reacts significantly at the time the trades are reported, suggesting that the reporting of the trades conveys information to the market, we conclude that delaying reporting of trades has an impact on market price efficiency. These findings contrast to findings for equities markets which conclude that the withholding of trade information has no impact on the speed of adjustment of the market to the information conveyed by the off-market trade (Gemmill, 1997, Journal of Finance).

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A BODIPY‐Based Donor/Donor–Acceptor System: Towards Highly Efficient Long‐Wavelength‐Excitable Near‐IR Polymer Dots with Narrow and Strong Absorption Features

By Lei Chen, Dandan Chen, Yifei Jiang, Jicheng Zhang, Jiangbo Yu, Christopher C. DuFort, Sunil R. Hingorani, Xuanjun Zhang, Changfeng Wu, Daniel T. Chiu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 12, 2019.

Bright lights, small dots: Achieving long‐wavelength‐excitable near‐infrared semiconducting polymer dots with simultaneously high fluorescence quantum yield, strong absorption cross‐section, narrow absorption‐emission bandwiths, and large Stokes shift by employing a BODIPY‐based donor/donor‐acceptor system. Abstract Bright long‐wavelength‐excitable semiconducting polymer dots (LWE‐Pdots) are highly desirable for in vivo imaging and multiplexed in vitro bioassays. LWE‐Pdots have been obtained by incorporating a near‐infrared (NIR) emitter into the backbone of a polymer host to develop a binary donor–acceptor (D–A) system. However, they usually suffer from severe concentration quenching and a trade‐off between fluorescence quantum yield (Φf) and absorption cross‐section (σ). Herein, we describe a ternary component (D1/D2–A) strategy to achieve ultrabright, green laser‐excitable Pdots with narrow‐band NIR emission by introducing a BODIPY‐based assistant polymer donor as D1. The D1/D2–A Pdots possess improved Φf and σ compared to corresponding binary D2–A Pdots. Their Φf is as high as 40.2 %, one of the most efficient NIR Pdots reported. The D1/D2–A Pdots show ultrahigh single‐particle brightness, 83‐fold brighter than Qdot 705 when excited by a 532 nm laser. When injected into mice, higher contrast in vivo tumor imaging was achieved using the ternary Pdots versus the binary D–A Pdots.

Unveiling the Layer‐Dependent Catalytic Activity of PtSe2 Atomic Crystals for the Hydrogen Evolution Reaction

By Dake Hu, Tianqi Zhao, Xiaofan Ping, Husong Zheng, Lei Xing, Xiaozhi Liu, Jingying Zheng, Lifei Sun, Lin Gu, Chenggang Tao, Dong Wang, Liying Jiao from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 12, 2019.

Through thick and thin: Since the thickness of two‐dimensional (2D) PtSe2 flakes can be controlled by adjusting synthesis conditions, their layer‐dependent catalytic activity for the hydrogen evolution reaction could be investigated from both theoretical and experimental perspectives. Structure–activity correlations were drawn, providing new insights for the design and synthesis of ultrathin catalysts. Abstract Two‐dimensional (2D) PtSe2 shows the most prominent layer‐dependent electrical properties among various 2D materials and high catalytic activity for hydrogen evolution reaction (HER), and therefore, it is an ideal material for exploring the structure–activity correlations in 2D systems. Here, starting with the synthesis of single‐crystalline 2D PtSe2 with a controlled number of layers and probing the HER catalytic activity of individual flakes in micro electrochemical cells, we investigated the layer‐dependent HER catalytic activity of 2D PtSe2 from both theoretical and experimental perspectives. We clearly demonstrated how the number of layers affects the number of active sites, the electronic structures, and electrical properties of 2D PtSe2 flakes and thus alters their catalytic performance for HER. Our results also highlight the importance of efficient electron transfer in achieving optimum activity for ultrathin electrocatalysts. Our studies greatly enrich our understanding of the structure–activity correlations for 2D catalysts and provide new insight for the design and synthesis of ultrathin catalysts with high activity.

A Microfabricated Sandwiching Assay for Nanoliter and High‐Throughput Biomarker Screening

By Praveen Bandaru, Dafeng Chu, Wujin Sun, Soufian Lasli, Chuanzhen Zhao, Shuang Hou, Shiming Zhang, Jiahua Ni, Giorgia Cefaloni, Samad Ahadian, Mehmet Remzi Dokmeci, Shiladitya Sengupta, Junmin Lee, Ali Khademhosseini from Wiley: Small: Table of Contents. Published on Apr 12, 2019.

In this work, a simple and low‐cost but sensitive, low‐volume, and scalable bioassay for monitoring of biomarkers with orders of magnitude less cells and sample volume is developed. The combination of microwell arrays as a cell culture substrate and micropillar arrays for drug delivery or biomolecular detection in response to drugs enables drug screening in one platform. Abstract Cells secrete substances that are essential to the understanding of numerous immunological phenomena and are extensively used in clinical diagnoses. Countless techniques for screening of biomarker secretion in living cells have generated valuable information on cell function and physiology, but low volume and real‐time analysis is a bottleneck for a range of approaches. Here, a simple, highly sensitive assay using a high‐throughput micropillar and microwell array chip (MIMIC) platform is presented for monitoring of biomarkers secreted by cancer cells. The sensing element is a micropillar array that uses the enzyme‐linked immunosorbent assay (ELISA) mechanism to detect captured biomolecules. When integrated with a microwell array where few cells are localized, interleukin 8 (IL‐8) secretion can be monitored with nanoliter volume using multiple micropillar arrays. The trend of cell secretions measured using MIMICs matches the results from conventional ELISA well while it requires orders of magnitude less cells and volumes. Moreover, the proposed MIMIC is examined to be used as a drug screening platform by delivering drugs using micropillar arrays in combination with a microfluidic system and then detecting biomolecules from cells as exposed to drugs.

Silica‐Mediated Formation of Nickel Sulfide Nanosheets on CNT Films for Versatile Energy Storage

By Pengyi Lu, Xiaowei Wang, Lei Wen, Xiaotong Jiang, Wenlei Guo, Lei Wang, Xiao Yan, Feng Hou, Ji Liang, Hui‐Ming Cheng, Shi Xue Dou from Wiley: Small: Table of Contents. Published on Apr 12, 2019.

Flexible, freestanding, and continuous nickel sulfide nanosheet/CNT (NS/CNT) films are fabricated through a silica‐mediated conversion process. The NS nanosheets with controllable phases and compositions are homogeneously and intimately attached on highly graphitized and few‐walled CNTs. The NS/CNT can be directly used as a multifunctional electrode and achieves extraordinary performance for both supercapacitor application and Li/Na ion storage. Abstract An effective, nondestructive, and universal strategy to homogeneously modify freestanding carbon nanotube (CNT) films with various active species is essential to achieve functional electrodes for flexible electrochemical energy storage, which is challenging and has attracted considerable research interest. In this work, a generalizable concept, to utilize silicon oxide as the intermediate to uniformly decorate various metal sulfide nanostructures throughout CNT films is reported. Taking nickel sulfide nanosheet/CNT (NS/CNT) films, in which the NS nanosheets are homogeneously attached on the intact few‐walled CNTs, as an example, the sheet‐like NS provides sufficient active sites for redox reactions and the CNT network acts as an efficient electron highway, maintaining the structural integrity of the composite and also buffering volume changes. These merits enable NS/CNT films to meet the requirements of versatile energy storage applications. When used for supercapacitors, a high specific capacitance (2699.7 F g−1/10 A g−1), outstanding rate performance at extremely high rates (1527 F g−1/250 A g−1), remarkable cycling stability, and excellent flexibility can be achieved, among the best performance so far. Moreover, it also delivers excellent performance in the storage of Li and Na ions, meaning it is also potentially suitable for Li/Na ion batteries.

On‐Surface Synthesis of 8‐ and 10‐Armchair Graphene Nanoribbons

By Kewei Sun, Penghui Ji, Junjie Zhang, Jinxi Wang, Xuechao Li, Xin Xu, Haiming Zhang, Lifeng Chi from Wiley: Small: Table of Contents. Published on Apr 12, 2019.

Currently unavailable armchair graphene nanoribbons (8‐ and 10‐AGNRs) are synthesized on Au (111) surfaces by using pre‐synthesized 3‐AGNRs as a ladder ribbon to laterally fuse with heterogeneous AGNRs of 5‐AGNRs and 7‐AGNRs. Both high resolution scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS) are utilized to characterize the geometric and electronic structures of 8‐ and 10‐AGNRs on Au (111). Abstract Armchair graphene nanoribbons (AGNRs) with 8 and 10 carbon atoms in width (8‐ and 10‐AGNRs) are synthesized on Au (111) surfaces via lateral fusion of nanoribbons that belong to different subfamilies. Poly‐para‐phenylene (3‐AGNR) chains are pre‐synthesized as ladder ribbons on Au (111). Subsequently, synthesized 5‐ and 7‐AGNRs can laterally fuse with 3‐AGNRs upon annealing at higher temperature, producing 8‐ and 10‐AGNRs, respectively. The synthetic process, and their geometric and electronic structures are characterized by scanning tunneling microscopy/spectroscopy (STM/STS). STS investigations reveal the band gap of 10‐AGNR (2.0 ± 0.1 eV) and a large apparent band gap of 8‐AGNRs (2.3 ± 0.1 eV) on Au (111) surface.

Interfacial Assembly of Signal Amplified Multienzymes and Biorecognized Antibody into Proteinosome for an Ultrasensitive Immunoassay

By Xu Yan, Tingting Wang, Dong Yao, Jiayun Xu, Quan Luo, Junqiu Liu from Wiley: Small: Table of Contents. Published on Apr 12, 2019.

A multifunctional self‐assembled proteinosome based on the integration of signal amplification elements (enzyme) and biorecognition unit (antibody) is designed for developing an immunoassay. Using imidacloprid as a model target, the proteinosome‐based immunoassay reaches a limit of detection down to the picogram mL−1 level, which is over 150‐fold lower than that of the conventional enzyme‐linked immunosorbent assay. Abstract Enzyme as signal tag has been widely employed in colorimetric immunoassays for decades. Nevertheless, it remains a great challenge to substantially improve the detection sensitivity of enzyme‐based immunoassays, which inhibits further critical applications. To circumvent this confinement, a multifunctional self‐assembled proteinosome based on the integration of signal amplification elements (enzyme) and biorecognition unit (antibody) is proposed for fabricating an immunoassay strategy with significantly enhanced sensitivity. Owing to the self‐assembly technique, this proteinosome not only efficiently loads abundant enzymes to possess high catalytic activity, but also enhances enzymatic stability and maintains recognition ability of antibody. Using imidacloprid as a model target, the proteinosome‐based immunoassay reaches a limit of detection down to the picogram mL−1 level, which is 150‐fold lower than that of conventional enzyme‐linked immunosorbent assay. This method provides a versatile approach for constructing spherical proteinosome as a recognizer and amplifier for profiling a broad range of target antigen.

Hierarchical Porous SWCNT Stringed Carbon Polyhedrons and PSS Threaded MOF Bilayer Membrane for Efficient Solar Vapor Generation

By Xu Ma, Wenzhang Fang, Yi Guo, Zhuoyi Li, Danke Chen, Wen Ying, Zhen Xu, Chao Gao, Xinsheng Peng from Wiley: Small: Table of Contents. Published on Apr 12, 2019.

A metal–organic framework (MOF)‐based single‐walled carbon nanotube stringed carbon polyhedron and polystyrene sulfonate threaded Cu3(BTC)3•3H2O (HKUST‐1) bilayer membrane shows hierarchical pores, high in‐plane thermal conductivity but thermal insulate along vertical direction, high solar adsorption, robust structures, and a hydrophilic surface. Based on these advantages, it presents 90.8% efficiency and long‐term durability for solar vapor generation. Abstract Interfacial solar vapor generation is considered to be an efficient and eco‐friendly technology for harvesting solar energy and providing freshwater. However, the efficient and long‐term steady evaporation of seawater under 1 sun becomes a critical issue when it comes to practical applications. Based on this issue, a special double‐layer structure, which contains a metal–organic‐framework‐derived hierarchical porous carbon membrane (HPCM) for solar absorption and a polystyrene sulfonate (PSS)@Cu3(BTC)3•3H2O (HKUST‐1)/single‐walled carbon nanotube (SWCNT) (PHS) membrane for water supply and salt blocking, is designed in this work. The converted heat is utilized efficiently in situ to drive the evaporation of water‐trapped HPCM. The PHS membrane with PSS modified channels successfully prevents the deposition of salt. Due to the synergistic combination of the HPCM and PHS membranes, the device exhibits a remarkably high water evaporation rate of 1.38 kg m−2 h−1 and solar‐vapor generation efficiency of 90.8% under 1 sun.

Nanoparticle‐Regulated Semiartificial Magnetotactic Bacteria with Tunable Magnetic Moment and Magnetic Sensitivity

By Qilong Li, Haitao Chen, Xueyan Feng, Chanchan Yu, Feng Feng, Yahong Chai, Pan Lu, Tao Song, Xiuyu Wang, Li Yao from Wiley: Small: Table of Contents. Published on Apr 12, 2019.

Semiartificial magnetotactic bacteria (SAMTB) are successfully obtained via a facile but beneficial strategy by depositing one layer or a multilayer of synthetic magnetic nanoparticles on the surface of MTB by electrostatic interaction. SAMTB retain the advantages of strong mobility and magnetotaxis of natural MTB while realizing tunable magnetic properties and magnetotactic motion. Abstract Micro‐/nanomotors are widely used in micro‐/nanoprocessing, cargo transportation, and other microscale tasks because of their ability to move independently. Many biological hybrid motors based on bacteria have been developed. Magnetotactic bacteria (MTB) have been employed as motors in biological systems because of their good biocompatibility and magnetotactic motion in magnetic fields. However, the magnetotaxis of MTB is difficult to control due to the lack of effective methods. Herein, a strategy that enables control over the motion of MTB is presented. By depositing synthetic Fe3O4 magnetic nanoparticles on the surface of MTB, semiartificial magnetotactic bacteria (SAMTB) are produced. The overall magnetic properties of SAMTB, including saturation magnetization, residual magnetization, and blocking temperature, are regulated in a multivariate and multilevel fashion, thus regulating the magnetic sensitivity of SAMTB. This strategy provides a feasible method to manoeuvre MTB for applications in complex fluid environments, such as magnetic drug release systems and real‐time tracking systems. Furthermore, this concept and methodology provide a paradigm for controlling the mobility of micro‐/nanomotors based on natural small organisms.

Dynamically Programmed Switchable DNA Hydrogels Based on a DNA Circuit Mechanism

By Motoi Oishi, Kazuki Nakatani from Wiley: Small: Table of Contents. Published on Apr 12, 2019.

A new class of switchable DNA hydrogels with a dynamically programmed DNA system is devised based on a DNA circuit system through cascading toehold‐mediated DNA displacement reactions. The DNA hydrogels exhibit a significant sharp phase transition due to synchronization of the catalytic cleavage of cross‐linking points and the main chains in response to an appropriate input. Abstract Biological stimuli‐responsive DNA hydrogels have attracted much attention in the field of medical engineering owing to their unique phase transitions from gel to sol through cleavage of DNA cross‐linking points in response to specific biomolecular inputs. In this paper, a new class of biological stimuli‐responsive DNA hydrogels with a dynamically programmed DNA system that relies on a DNA circuit system through cascading toehold‐mediated DNA displacement reactions is constructed, allowing the catalytic cleavage of cross‐linking points and main chains in response to an appropriate DNA input. The dynamically programmed DNA hydrogels exhibit a significant sharp phase transition from gel to sol in comparison to another DNA hydrogel showing noncatalytic cleavage of cross‐linking points due to synchronization of the catalytic cleavage of cross‐linking points and the main chains. Further, the sol–gel phase transitions of the DNA hydrogels in response to the DNA input are easily tunable by changing the cross‐linking density. Additionally, with a structure‐switching aptamer, DNA hydrogels encapsulating PEGylated gold nanoparticles can be used as enzyme‐free signal amplifiers for the colorimetric detection of adenosine 5′‐triphosphate (ATP); this detection system provides simplicity and higher sensitivity (limit of detection: 5.6 × 10−6 m at 30 min) compared to other DNA hydrogel‐based ATP detection systems.

Insights into the Crystallinity of Layer‐Structured Transition Metal Dichalcogenides on Potassium Ion Battery Performance: A Case Study of Molybdenum Disulfide

By Yulian Dong, Yang Xu, Wei Li, Qun Fu, Minghong Wu, Eberhard Manske, Jörg Kröger, Yong Lei from Wiley: Small: Table of Contents. Published on Apr 12, 2019.

Crystallinity of layer‐structured transition metal dichalcogenides is studied to reveal its effect on potassium ion battery performance, by taking molybdenum disulfide as a demonstrator. The effect is dependent on the K‐ion storage mechanism. Lower crystallinity benefits ion intercalation, while higher crystallinity promotes surface ion storage when conversion reaction mainly contributes to the capacity. Abstract Layer‐structured transition metal dichalcogenides (LS‐TMDs) are being heavily studied in K‐ion batteries (KIBs) owing to their structural uniqueness and interesting electrochemical mechanisms. Synthetic methods are designed primarily focusing on high capacities. The achieved performance is often the collective results of several contributing factors. It is important to decouple the factors and understand their functions individually. This work presents a study focusing on an individual factor, crystallinity, by taking MoS2 as a demonstrator. The performance of low and high‐crystallized MoS2 is compared to show the function of crystallinity is dependent on the electrochemical mechanism. Lower crystallinity can alleviate diffusional limitation in 0.5–3.0 V, where intercalation reaction takes charge in storing K‐ions. Higher crystallinity can ensure the structural stability of the MoS2 layers and promote surface charge storage in 0.01–3.0 V, where conversion reaction mainly contributes. The low‐crystallized MoS2 exhibits an intercalation capacity (118 mAh g−1), good cyclability (85% over 100 cycles), and great rate capability (41 mAh g−1 at 2 A g−1), and the high‐crystallized MoS2 delivers a high capacity of 330 mAh g−1 at 1 A g−1 and retains 161 mAh g−1 at 20 A g−1, being one of the best among the reported LS‐TMDs in KIBs.

NixMnyCozO Nanowire/CNT Composite Microspheres with 3D Interconnected Conductive Network Structure via Spray‐Drying Method: A High‐Capacity and Long‐Cycle‐Life Anode Material for Lithium‐Ion Batteries

By Qing Li, Guozhen Zhu, Yunhao Zhao, Ke Pei, Renchao Che from Wiley: Small: Table of Contents. Published on Apr 12, 2019.

A NixMnyCozO (x + y + z = 1) nanowire/carbon nanotube (CNT) composite with microspherical morphology and a 3D interconnected conductive network structure is synthesized via a spray‐drying method, and demonstrates excellent electrochemical performance. After 1000 cycles at 5 A g−1, its discharge capacity is maintained at 790 mAh g−1. This work demonstrates a universal method to construct a 3D conductive network for anode materials. Abstract The combination of high‐capacity and long‐term cycling stability is an important factor for practical application of anode materials for lithium‐ion batteries. Herein, NixMnyCozO nanowire (x + y + z = 1)/carbon nanotube (CNT) composite microspheres with a 3D interconnected conductive network structure (3DICN‐NCS) are prepared via a spray‐drying method. The 3D interconnected conductive network structure can facilitate the penetration of electrolyte into the microspheres and provide excellent connectivity for rapid Li+ ion/electron transfer in the microspheres, thus greatly reducing the concentration polarization in the electrode. Additionally, the empty spaces among the nanowires in the network accommodate microsphere volume expansion associated with Li+ intercalation during the cycling process, which improves the cycling stability of the electrode. The CNTs distribute uniformly in the microspheres, which act as conductive frameworks to greatly improve the electrical conductivity of the microspheres. As expected, the prepared 3DICN‐NCS demonstrates excellent electrochemical performance, showing a high capacity of 1277 mAh g−1 at 1 A g−1 after 2000 cycles and 790 mAh g−1 at 5 A g−1 after 1000 cycles. This work demonstrates a universal method to construct a 3D interconnected conductive network structure for anode materials

Mesh‐Like Carbon Nanosheets with High‐Level Nitrogen Doping for High‐Energy Dual‐Carbon Lithium‐Ion Capacitors

By Zhao Li, Liujun Cao, Wei Chen, Zechuan Huang, Hao Liu from Wiley: Small: Table of Contents. Published on Apr 12, 2019.

To circumvent the mismatched electrode kinetics between anode and cathode and alleviate cycle degradation problem in current Li‐ion capacitors (LICs). Herein, a dual‐carbon symmetric configuration is designed by using a mesh‐like nitrogen (N)‐doped carbon nanosheets with multiscale pore structure as both cathodic and anodic electrodes in LICs device. With this rational design, the optimal LICs device achieves a superior electrochemical performance. Abstract Li‐ion capacitors (LICs) have demonstrated great potential for bridging the gap between lithium‐ion batteries and supercapacitors in electrochemical energy storage area. The main challenge for current LICs (contain a battery‐type anode as well as a capacitor‐type cathode) lies in circumventing the mismatched electrode kinetics and cycle degradation. Herein, a mesh‐like nitrogen (N)‐doped carbon nanosheets with multiscale pore structure is adopted as both cathode and anode for a dual‐carbon type of symmetric LICs to alleviate the above mentioned problems via a facile and green synthesis approach. With rational design, this dual‐carbon LICs exhibits a broad high working voltage window (0–4.5 V), an ultrahigh energy density of 218.4 Wh kg–1electrodes (229.8 Wh L–1electrodes), the highest power density of 22.5 kW kg–1electrodes (23.7 kW L–1electrodes) even under an ultrahigh energy density of 97.5 Wh kg–1electrodes (102.6 Wh L–1electrodes), as well as reasonably good cycling stability with capacity retention of 84.5% (only 0.0016% capacity loss per cycle) within 10 000 cycles under a high current density of 5 A g−1. This study provides an efficient method and option for the development of high performance LIC devices.

Topography‐Induced Cell Self‐Organization from Simple to Complex Aggregates

By Jing Luo, Jingxin Meng, Zhen Gu, Luying Wang, Feilong Zhang, Shutao Wang from Wiley: Small: Table of Contents. Published on Apr 12, 2019.

Three‐dimensional cellular aggregates with complex architectures are control‐lably self‐organized through the use of nona‐dhesive hydrogel templates with defined geometries. The self‐organization of the cellular aggregates can be affected by the induction of multiscale topography through confined templates at the macroscale and cell interactions at the nanoscale, demonstrated by the variation of cellular pseudopodia and corresponding E‐cadherin from adjacent frontier cells. Abstract Self‐organization is a fundamental and indispensable process in a living system. To understand cell behavior in vivo such as tumorigenesis, 3D cellular aggregates, instead of 2D cellular sheets, have been employed as a vivid in vitro model for self‐organization. However, most focus on the macroscale wetting and fusion of cellular aggregates. In this study, it is reported that self‐organization of cells from simple to complex aggregates can be induced by multiscale topography through confined templates at the macroscale and cell interactions at the nanoscale. On the one hand, macroscale templates are beneficial for the organization of individual cells into simple and complex cellular aggregates with various shapes. On the other hand, the realization of these macro‐organizations also depends on cell interactions at the nanoscale, as demonstrated by the intimate contact between nanoscale pseudopodia stretched by adjacent frontier cells, much like holding hands and by the variation in the intermolecular interactions based on E‐cadherin. Therefore, these findings may be very meaningful for clarifying the organizational mechanism of tumor development, tissue engineering and regenerative medicine.

Contactless Electrical and Structural Characterization of Semiconductor Nanowires with Axially Modulated Doping Profiles

By Wuhan Yuan, Gozde Tutuncuoglu, Amar Mohabir, Liping Liu, Leonard C. Feldman, Michael A. Filler, Jerry W. Shan from Wiley: Small: Table of Contents. Published on Apr 12, 2019.

A high‐throughput technique for electrical and structural characterization of individual Si nanowires (NWs) is required to achieve large‐scale applications. Electro‐orientation spectroscopy is demonstrated to fulfill this requirement by noncontact characterization of NWs with axially programmed dopant profiles. This work serves as a first step toward efficient measurement of complete nanowire device ensembles with complex dopant structures. Abstract Efficient characterization of semiconductor nanowires having complex dopant profiles or heterostructures is critical to fully understand these materials and the devices built from them. Existing electrical characterization techniques are slow and laborious, particularly for multisegment nanowires, and impede the statistical understanding of highly variable samples. Here, it is shown that electro‐orientation spectroscopy (EOS)—a high‐throughput, noncontact method for statistically characterizing the electrical properties of entire nanowire ensembles—can determine the conductivity and dimensions of two distinct segments in individual Si nanowires with axially encoded dopant profiles. This analysis combines experimental measurements and computational simulations to determine the electrical conductivity of the nominally undoped segment of two‐segment Si nanowires, as well as the ratio of the segment lengths. The efficacy of this approach is demonstrated by comparing results generated by EOS with conventional four‐point‐probe measurements. This work provides new insights into the control and variability of semiconductor nanowires for electronic applications and is a critical first step toward the high‐throughput interrogation of complete nanowire‐based devices.

Reversible Image Contrast Manipulation with Thermally Tunable Dielectric Metasurfaces

By Khosro Zangeneh Kamali, Lei Xu, Jonathan Ward, Kai Wang, Guixin Li, Andrey E. Miroshnichenko, Dragomir Neshev, Mohsen Rahmani from Wiley: Small: Table of Contents. Published on Apr 12, 2019.

The first thermal contrast tuning of an image made of metasurfaces is demonstrated. The heat increases the refractive index of the silicon nanoparticles and subsequently shifts the resonance of the metasurface. This resonance shift leads to variation of the transmission intensity of the interrogating light wavelength. Using this concept, a Yin‐Yang image with tunable contrast is made. Abstract Increasing demand for higher resolution of miniaturized displays requires techniques achieving high contrast tunability of the images. Employing metasurfaces for image contrast manipulation is a new and rapidly growing field of research aiming to address this need. Here, a new technique to achieve image tuning in a reversible fashion is demonstrated by dielectric metasurfaces composed of subwavelength resonators. It is demonstrated that by controlling the temperature of a metasurface the encoded transmission pattern can be tuned. To this end, two sets of nanoresonators composed of nonconcentric silicon disks with a hole that exhibit spectrally sharp Fano resonances and forming a Yin‐Yang pattern are designed and fabricated. Through exploitation of the thermo‐optical properties of silicon, full control of the contrast of the Yin‐Yang image is demonstrated by altering the metasurface temperature by ΔT ≈ 100 °C. This is the first demonstrated technique to control an image contrast by temperature. Importantly, the turning technique does not require manipulating the external stimulus, such as polarization or angle of the illumination and/or the refractive index of this environment. These results open many opportunities for transparent displays, optical switches, and tunable illumination systems.

Highly Dynamic Nanocomposite Hydrogels Self‐Assembled by Metal Ion‐Ligand Coordination

By Kunyu Zhang, Weihao Yuan, Kongchang Wei, Boguang Yang, Xiaoyu Chen, Zhuo Li, Zhiyong Zhang, Liming Bian from Wiley: Small: Table of Contents. Published on Apr 12, 2019.

A generalized approach for the ultrafast fabrication of self‐assembled metal‐ion‐containing nanocomposite hydrogels is established by bisphosphonate‐metal ions coordination. This strategy is highly versatile and generalizable for a wide array of metal ions, including the cations of alkaline earth metals and transition metals. The obtained nanocomposite hydrogels exhibit tunable mechanical properties, excellent injectability, fast stress relaxation, and efficient ion diffusion. Abstract Hydrogels are emerging biomaterials with desirable physicochemical characteristics. Doping of metal ions such as Ca2+, Mg2+, and Fe2+ provides the hydrogels with unique attributes, including bioactivity, conductivity, and tunability. Traditionally, this doping is achieved by the interaction between metal ions and corresponding ligands or the direct incorporation of as‐prepared metal‐based nanoparticles (NPs). However, these approaches rely on a complex and laborious preparation and are typically restricted to few selected ion species. Herein, by mixing aqueous solutions of ligands (bisphosphonates, BPs), polymer grafted with ligands, and metal ions, a series of self‐assembled metallic‐ion nanocomposite hydrogels that are stabilized by the in situ formed ligand‐metal ion (BP‐M) NPs are prepared. Owing to the universal coordination between BPs and multivalent metal ions, the strategy is highly versatile and can be generalized for a wide array of metal ions. Such hydrogels exhibit a wide spectrum of mechanical properties and remarkable dynamic properties, such as excellent injectability, rapid stress relaxation, efficient ion diffusion, and triggered disassembly for harvesting encapsulated cells. Meanwhile, the hydrogels can be conveniently coated or patterned onto the surface of metals via electrophoresis. This work presents a universal strategy to prepare designer nanocomposite materials with highly tunable and dynamic behaviors.

Conductive Polymer Hydrogel Microfibers from Multiflow Microfluidics

By Jiahui Guo, Yunru Yu, Huan Wang, Han Zhang, Xiaoxuan Zhang, Yuanjin Zhao from Wiley: Small: Table of Contents. Published on Apr 12, 2019.

Conductive hydrogel microfibers with alginate shells and poly (3, 4‐ethylenedioxythiophene): poly (4‐styrenesulfonate) cores are fabricated using a multiflow capillary microfluidic spinning approach. The practical values of microfibers in stretch sensitivity and bending stability are also explored based on various electrical characterizations. The microfibers show good conductivity and do not interfere with each other during electron conduction with outer alginate shells. Abstract Conductive hydrogels are receiving increasing attention for their utility in electronic area applications requiring flexible conductors. Here, it is presented novel conductive hydrogel microfibers with alginate shells and poly (3, 4‐ethylenedioxythiophene): poly (4‐styrenesulfonate) (PEDOT: PSS) cores fabricated using a multiflow capillary microfluidic spinning approach. Based on multiflow microfluidics, alginate shells are formed immediately from the fast gelation reaction between sodium alginate (Na‐Alg) and sheath laminar calcium chloride flows, while PEDOT: PSS cores are solidified slowly in the hollow alginate hydrogel shell microreactors after their precursor solutions are injected in situ as the center fluids. The resultant PEDOT: PSS‐containing microfibers are with features of designed morphology and highly controllable package, because material compositions or the sizes of their shell hydrogels can be tailored by using different concentrations or flow rates of pregel solutions. Moreover, the practical values of these microfibers in stretch sensitivity and bending stability are explored based on various electrical characterizations of the compound materials. Thus, it is believed that these microfluidic spinning PEDOT: PSS conductive microfibers will find important utility in electronic applications requiring flexible electronic systems.

An Increase in Membrane Cholesterol by Graphene Oxide Disrupts Calcium Homeostasis in Primary Astrocytes

By Mattia Bramini, Martina Chiacchiaretta, Andrea Armirotti, Anna Rocchi, Deepali D. Kale, Cristina Martin, Ester Vázquez, Tiziano Bandiera, Stefano Ferroni, Fabrizia Cesca, Fabio Benfenati from Wiley: Small: Table of Contents. Published on Apr 12, 2019.

Alterations in several cellular processes in cortical astrocytes exposed to graphene oxide (GO), including intracellular Ca2+ ([Ca2+]i) homeostasis and cholesterol metabolism, are found and investigated. GO exposure impairs spontaneous and evoked astrocyte [Ca2+]i signals and induces a marked increase in membrane cholesterol levels. Importantly, cholesterol depletion fully rescues [Ca2+]i dynamics in GO‐treated cells, indicating a causal relationship between these GO‐mediated effects. Abstract The use of graphene nanomaterials (GNMs) for biomedical applications targeted to the central nervous system is exponentially increasing, although precise information on their effects on brain cells is lacking. In this work, the molecular changes induced in cortical astrocytes by few‐layer graphene (FLG) and graphene oxide (GO) flakes are addressed. The results show that exposure to FLG/GO does not affect cell viability or proliferation. However, proteomic and lipidomic analyses unveil alterations in several cellular processes, including intracellular Ca2+ ([Ca2+]i) homeostasis and cholesterol metabolism, which are particularly intense in cells exposed to GO. Indeed, GO exposure impairs spontaneous and evoked astrocyte [Ca2+]i signals and induces a marked increase in membrane cholesterol levels. Importantly, cholesterol depletion fully rescues [Ca2+]i dynamics in GO‐treated cells, indicating a causal relationship between these GO‐mediated effects. The results indicate that exposure to GNMs alters intracellular signaling in astrocytes and may impact astrocyte–neuron interactions.

Comment on “Topical Delivery of Avastin to the Posterior Segment of the Eye In Vivo Using Annexin A5‐Associated Liposomes”: Topical Liposomal Bevacizumab Results in Negligible Retinal Concentrations

By Arto Urtti from Wiley: Small: Table of Contents. Published on Apr 12, 2019.

This Comment includes critical discussion on previously published research on retinal delivery of bevacizumab with topically applied liposomes. The Comment indicates that the retinal bevacizumab levels after topical delivery are in fact several orders of magnitude below clinically relevant concentrations. Abstract The previously published report suggests that liposomes, functionalized with annexin‐5, can deliver bevacizumab to the retina after topical administration as eyedrops. Topical delivery of bevacizumab would be an attractive alternative to the current treatment that involves monthly intravitreal injections to the eye. In this Comment, the retinal concentrations of topically applied liposomal bevacizumab are compared to the levels reached after intravitreal injections. The comparison reveals that the topical liposomal delivery results in retinal bevacizumab concentrations that are about 3–5 orders of magnitude below the lowest bevacizumab concentrations during clinical treatment with intravitreal injections. Major improvement is needed before topical bevacizumab delivery can be considered clinically feasible.

Masthead: (Small 15/2019)

By from Wiley: Small: Table of Contents. Published on Apr 12, 2019.

Self‐Organization: Topography‐Induced Cell Self‐Organization from Simple to Complex Aggregates (Small 15/2019)

By Jing Luo, Jingxin Meng, Zhen Gu, Luying Wang, Feilong Zhang, Shutao Wang from Wiley: Small: Table of Contents. Published on Apr 12, 2019.

In article number 1900030, Jingxin Meng, Shutao Wang, and co‐workers prepare non‐adhesive templates with defined geometries by laser etching, which can be used to controllably organize 3D cellular aggregates in vitro. The self‐organization of cells from simple to complex aggregates reveals the synergistic effect of multiscale topography from confined templates at the macroscale and cell interactions at the nanoscale.

Supercapacitors: Silica‐Mediated Formation of Nickel Sulfide Nanosheets on CNT Films for Versatile Energy Storage (Small 15/2019)

By Pengyi Lu, Xiaowei Wang, Lei Wen, Xiaotong Jiang, Wenlei Guo, Lei Wang, Xiao Yan, Feng Hou, Ji Liang, Hui‐Ming Cheng, Shi Xue Dou from Wiley: Small: Table of Contents. Published on Apr 12, 2019.

In article number 1805064, Feng Hou, Ji Liang, and co‐workers fabricate flexible, free‐standing, and continuous nickel sulfide nanosheet/carbon nanotube (NS/CNT) films through a silicamediated conversion process. The nickel sulfide nanosheets with controllable phases and compositions are homogeneously and intimately attached on highly graphitized and fewwalled CNTs. The NS/CNT can be directly used as a multi‐functional electrode and achieves extraordinary performance for both supercapacitor application and Li/Na ion storage.

Semiartificial Magnetotactic Bacteria: Nanoparticle‐Regulated Semiartificial Magnetotactic Bacteria with Tunable Magnetic Moment and Magnetic Sensitivity (Small 15/2019)

By Qilong Li, Haitao Chen, Xueyan Feng, Chanchan Yu, Feng Feng, Yahong Chai, Pan Lu, Tao Song, Xiuyu Wang, Li Yao from Wiley: Small: Table of Contents. Published on Apr 12, 2019.

In article number 1900427, Xiuyu Wang, Li Yao, and co‐workers produce semi‐artificial magnetotactic bacteria (SAMTB) with synthetic magnetic nanoparticles on the surface of MTB. The SAMTB retain the advantages of strong mobility and magnetotaxis of natural MTB while realizing tunable magnetic properties and magnetotactic motion.

High‐Throughput Drug Screening: A Microfabricated Sandwiching Assay for Nanoliter and High‐Throughput Biomarker Screening (Small 15/2019)

By Praveen Bandaru, Dafeng Chu, Wujin Sun, Soufian Lasli, Chuanzhen Zhao, Shuang Hou, Shiming Zhang, Jiahua Ni, Giorgia Cefaloni, Samad Ahadian, Mehmet Remzi Dokmeci, Shiladitya Sengupta, Junmin Lee, Ali Khademhosseini from Wiley: Small: Table of Contents. Published on Apr 12, 2019.

In article number 1900300, Junmin Lee, Ali Khademhosseini, and co‐workers develop a nanoliter and high‐throughput drug screening platform based on the combination of microwell arrays as a cell culture substrate, and micropillar arrays for drug delivery and biomolecular detection in response to drugs. The developed platform requires only a small amount of sample volume from a few cells and demonstrates increasing control and throughput while allowing direct and real‐time on‐chip measurements. It is expected to aid in improving drug screening on patient biopsies from solid tumors to realize personalized cancer therapy.

Fast Charging Lithium Batteries: Recent Progress and Future Prospects

By Gao‐Long Zhu, Chen‐Zi Zhao, Jia‐Qi Huang, Chuanxin He, Jian Zhang, Shaohai Chen, Lei Xu, Hong Yuan, Qiang Zhang from Wiley: Small: Table of Contents. Published on Apr 12, 2019.

The fast charging of rechargeable batteries is reviewed and the critical values of ionic and electrical conductivity of electrodes that are employed in fast charging are also proposed. The requirements of electrode, solid electrolytes, and their interfaces are also presented to meet the practical application in fast charging batteries. Abstract Fast charging enables electronic devices to be charged in a very short time, which is essential for next‐generation energy storage systems. However, the increase of safety risks and low coulombic efficiency resulting from fast charging severely hamper the practical applications of this technology. This Review summarizes the challenges and recent progress of lithium batteries for fast charging. First, it describes the definition of fast charging and proposes a critical value of ionic and electrical conductivity of electrodes for fast charging in a working battery. Then based on this definition, the requirements and optimization strategies of the electrode, electrolyte, and electrode/electrolyte interface for fast charging are proposed. Finally, a general conclusion and perspectives on the better understanding of lithium batteries with fast charging capability are presented.

Recent Progress in Multivalent Metal (Mg, Zn, Ca, and Al) and Metal‐Ion Rechargeable Batteries with Organic Materials as Promising Electrodes

By Jian Xie, Qichun Zhang from Wiley: Small: Table of Contents. Published on Apr 12, 2019.

Organic multivalent metal and metal‐ion rechargeable batteries are reviewed. Fundamentals including organic structures, cell configurations, and key relevant electrochemical parameters are presented. This Review provides a fundamental guidance for future development of organic multivalent metal‐ion rechargeable batteries. Abstract The emerging demand for electronic and transportation technologies has driven the development of rechargeable batteries with enhanced capacity storage. Especially, multivalent metal (Mg, Zn, Ca, and Al) and metal‐ion batteries have recently attracted considerable interests as promising substitutes for future large‐scale energy storage devices, due to their natural abundance and multielectron redox capability. These metals are compatible with nonflammable aqueous electrolytes and are less reactive when exposed in ambient atmosphere as compared with Li metals, hence enabling potential safer battery systems. Luckily, green and sustainable organic compounds could be designed and tailored as universal host materials to accommodate multivalent metal ions. Considering these advantages, effective approaches toward achieving organic multivalent metal and metal‐ion rechargeable batteries are highlighted in this Review. Moreover, organic structures, cell configurations, and key relevant electrochemical parameters are presented. Hopefully, this Review will provide a fundamental guidance for future development of organic‐based multivalent metal and metal‐ion rechargeable batteries.

Wed 29 May 15:00: Inside-out: How emotions are perceived in the face

From All Talks (aka the CURE list). Published on Apr 12, 2019.

Inside-out: How emotions are perceived in the face

The vast majority of research into the nonverbal communication of emotions focuses on prototypical expressive patterns, often deliberately posed by actors upon instructions by the researcher. In terms of the displayed emotions, the criterion for usage typically is clearly and easily recognizable expressions. In this talk, I would like to argue that the emotional clarity and prototypicality of facial displays is not sufficient to capture the complexities and subtleties of human emotion perception. Based on a number of studies I show that perceivers go beyond what is directly observable and make inferences about the underlying states, intentions, and qualities of others. These concern attributes of the stimulus target, i.e. the type of facial expression and the presence of situational cues. As such, the same facial expression is interpreted differently depending on its temporal or contextual shaping. Furthermore, attributes of the perceiver such as experiential and motivational factors impact the meaning of facial expressions. This can be seen in situations when facial mimicry is experimentally inhibited, thereby leading to stronger reliance on conceptual and often stereotypical knowledge in emotion interpretation. The findings will be discussed building on a range of techniques (i.e., facial EMG , eye tracking, binocular rivalry), with the goal to elucidate the social and emotional meaning of facial expressions.

Dr Eva Krumhuber is an assistant professor in the Department of Experimental Psychology at University College London. Her research investigates the social psychological aspects of face perception and various factors that moderate people’s judgments. Eva obtained her PhD degree in social psychology at Cardiff University for which she won the Hadyn Ellis Prize for Outstanding Dissertation. Subsequent postdoctoral work in Switzerland and Germany led to the development of new animation software for an award-winning market research project, as well as technological applications to aid cultural understanding and empathy in children and young adults. Besides her contributions to psychology, her research has proven relevant in industry for the successful modelling of emotions in virtual characters, also being commercially used by the film and video games industry. Eva has published widely within the field of psychology and computer science, and currently serves as an Associate Editor of the Journal of Nonverbal Behavior, and Frontiers in Psychology: Personality and Social Psychology.

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Fri 21 Feb 17:30: The Enigmatic Premodern Book

From All Talks (aka the CURE list). Published on Apr 12, 2019.

The Enigmatic Premodern Book

Abstract not available

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Fri 10 May 14:00: [Special Statslab Seminar] Scalable methods for machine learning optimisation

From All Talks (aka the CURE list). Published on Apr 12, 2019.

[Special Statslab Seminar] Scalable methods for machine learning optimisation

Optimisation methods play one of the most important roles in machine learning area. High-dimensionality of machine learning models and large volume of training data introduce a variety of challenges, both from the fundamental optimisation methodology perspective and distributed computation perspective. In this talk, I will present techniques that allow us to accelerate training of machine learning models in distributed computing systems, and approximately solve certain classes of submodular optimisation problems by using simple surrogate functions. In both these problems, we leverage combining lossy data compression with optimisation. Time permitting, I will also briefly discuss some recent results and open questions that arise in online decision making under uncertainty, statistical relational learning, and inverse problems for stochastic processes on graphs.

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A Highly Efficient Self‐Healing Elastomer with Unprecedented Mechanical Properties

By Luzhi Zhang, Zenghe Liu, Xueli Wu, Qingbao Guan, Shuo Chen, Lijie Sun, Yifan Guo, Shuliang Wang, Jianchun Song, Eric Meade Jeffries, Chuanglong He, Feng‐Ling Qing, Xiaoguang Bao, Zhengwei You from Wiley: Advanced Materials: Table of Contents. Published on Apr 12, 2019.

A dimethylglyoxime–urethane (DOU)‐based polyurethane elastomer self‐heals immediately at room temperature and shows world‐record strength and toughness. Cu(II)DOU coordination bonds greatly strengthen the materials while enhancing the dynamics of the DOU bonds to facilitate self‐healing. This material design reconciles the contradictory properties of mechanical robustness and self‐healing efficiency that provides a powerful new strategy to create high‐performance self‐healing materials. Abstract It is highly desirable, although very challenging, to develop self‐healable materials exhibiting both high efficiency in self‐healing and excellent mechanical properties at ambient conditions. Herein, a novel Cu(II)–dimethylglyoxime–urethane‐complex‐based polyurethane elastomer (Cu–DOU–CPU) with synergetic triple dynamic bonds is developed. Cu–DOU–CPU demonstrates the highest reported mechanical performance for self‐healing elastomers at room temperature, with a tensile strength and toughness up to 14.8 MPa and 87.0 MJ m−3, respectively. Meanwhile, the Cu–DOU–CPU spontaneously self‐heals at room temperature with an instant recovered tensile strength of 1.84 MPa and a continuously increased strength up to 13.8 MPa, surpassing the original strength of all other counterparts. Density functional theory calculations reveal that the coordination of Cu(II) plays a critical role in accelerating the reversible dissociation of dimethylglyoxime–urethane, which is important to the excellent performance of the self‐healing elastomer. Application of this technology is demonstrated by a self‐healable and stretchable circuit constructed from Cu–DOU–CPU.

A New Architecture for Fibrous Organic Transistors Based on a Double‐Stranded Assembly of Electrode Microfibers for Electronic Textile Applications

By Soo Jin Kim, Hyoungjun Kim, Jongtae Ahn, Do Kyung Hwang, Hyunsu Ju, Min‐Chul Park, Hoichang Yang, Se Hyun Kim, Ho Won Jang, Jung Ah Lim from Wiley: Advanced Materials: Table of Contents. Published on Apr 12, 2019.

Fibrous organic transistors with a double‐stranded assembly of electrode microfibers are successfully demonstrated. This architecture not only allows the channel dimension of the device to be readily controlled by varying the thickness of the semiconductor layer and the twisted length of the two electrode microfibers, but also passivates the device without affecting interconnections with other electrical components. Abstract Herein, a unique device architecture is proposed for fibrous organic transistors based on a double‐stranded assembly of electrode microfibers for electronic textile applications. A key feature of this work is that the semiconductor channel of the fiber transistor comprises a twist assembly of the source and drain electrode microfibers that are coated by an organic semiconductor. This architecture not only allows the channel dimension of the device to be readily controlled by varying the thickness of the semiconductor layer and the twisted length of the two electrode microfibers, but also passivates the device without affecting interconnections with other electrical components. It is found that the control of crystalline nanostructure of the semiconductor layer is critical for improving both the production yield of the device and the charge‐carrier transport in the device. The resulting fibrous organic transistors show a high output current of over −5 mA at a low operation voltage of −1.3 V and a good on/off current ratio of 105. The device performance is maintained after repeated bending deformation and washing with a strong detergent solution. Application of the fibrous organic transistors to switch current‐driven LED devices and detection of electrocardiography signals from a human body are demonstrated.

Ultrasmall Oxygen‐Deficient Bimetallic Oxide MnWOX Nanoparticles for Depletion of Endogenous GSH and Enhanced Sonodynamic Cancer Therapy

By Fei Gong, Liang Cheng, Nailin Yang, Oshra Betzer, Liangzhu Feng, Qiang Zhou, Yonggang Li, Ruihua Chen, Rachela Popovtzer, Zhuang Liu from Wiley: Advanced Materials: Table of Contents. Published on Apr 12, 2019.

A new type of sonodynamic therapy (SDT) agent based on ultrasmall oxygen‐deficient bimetallic oxide MnWOX nanoparticles, which exhibit much higher sono‐sensitization efficiency compared with conventional SDT agents, as well as glutathione depletion capability to further favor SDT. Furthermore, their multimodal imaging functions and rapid renal clearance make them promising theranostic agents for imaging‐guided SDT. Abstract Sonodynamic therapy (SDT) triggered by ultrasound (US) has attracted increasing attention owing to its abilities to overcome critical limitations including low tissue‐penetration depth and phototoxicity in photodynamic therapy. Herein, the design of a new type of sonosensitizer is revealed, namely, ultrasmall oxygen‐deficient bimetallic oxide MnWOX nanoparticles, for multimodal imaging‐guided enhanced SDT against cancer. As‐made MnWOX nanoparticles with poly(ethylene glycol) (PEG) modification show high physiological stability and biocompatibility. Interestingly, such MnWOX‐PEG nanoparticles exhibit highly efficient US‐triggered production of 1O2 and •OH, higher than that of previously reported sonosensitizers (e.g., protoporphyrin IX and titanium dioxide), because the oxygen‐deficient structure of MnWOX serves as an electron trap site to prevent electron–hole recombination. The glutathione depletion capability of MnWOX‐PEG can also further favor SDT‐triggered cancer cell killing. With efficient tumor homing as illustrated by computer tomography and magnetic resonance imaging, MnWOX‐PEG enables effective destruction of mouse tumors under US stimulation. After accomplishing its therapeutic functions, MnWOX‐PEG can be metabolized by the mouse body without any long‐term toxicity. Herein, a new type of sono‐sensitizing agent with high SDT efficacy, multimodal imaging functions, and rapid clearance is presented, an agent which is promising for noninvasive SDT cancer treatment.

Precise Self‐Assembly of Nanoparticles into Ordered Nanoarchitectures Directed by Tobacco Mosaic Virus Coat Protein

By Jianting Zhang, Kun Zhou, Yejun Zhang, Mingming Du, Qiangbin Wang from Wiley: Advanced Materials: Table of Contents. Published on Apr 12, 2019.

Biomolecules‐guided self‐assembly has become one of the most promising approaches of fabricating designed nanostructures and functional materials. A facile and effective strategy is demonstrated for the hierarchical assembly of functional nanoparticles into diverse structures from discrete nanostructures to 2D periodic lattices based on the functionalized cylinder‐shaped tobacco mosaic virus coat protein. Abstract Self‐assembly guided by biological molecules is a promising approach for fabricating predesigned nanostructures. Protein is one such biomolecule possessing deterministic 3D crystal structure and peptide information, which acts as a good candidate for templating functional nanoparticles (fNPs). However, inadequate coordination efficacy during the establishment of interfacial interactions with fNPs makes it highly challenging to precisely fabricate designed nanostructures and functional materials. Here, a facile and robust strategy is reported for the hierarchical assembly of fNPs into ordered architectures, with unprecedentedly large sizes up to tens of micrometers, using a hollow cylinder‐shaped tobacco mosaic virus coat protein (TMV disk). The rational design of the site‐specific functional groups on the TMV disk not only demonstrates the powerful capability of directing various discrete fNP assemblies with high controllability but also assists in precise assembly of a TMV monolayer sheet structure for further organizing homogeneous and heterogeneous fNP periodic lattices by varying the types of fNPs. The high precision and adjustability of the pattern fashions of different fNPs unambiguously corroborate the validity of this innovative strategy, which provides a convenient route to design and assemble protein‐based hierarchical ordered architectures for use in nanophotonics and nanodevices.

Fri 24 May 16:30: Neuroscience & Creativity: Insights from Unnatural Bedfellows PLEASE NOTE: THIS ZANGWILL TALK IS TAKING PLACE AT THE USUAL TIME OF 4.30PM. THE ZANGWILL TEA WILL BE AT 4.00PM

From All Talks (aka the CURE list). Published on Apr 12, 2019.

Neuroscience & Creativity: Insights from Unnatural Bedfellows

For psychologists and neuroscientists of creativity, the first step towards uncovering the neurocognitive basis of this incredible ability is to settle on which empirical approach to adopt. The choices are vast. The dominant approach views creativity as a unitary and domain-general construct. Alternative approaches vary in their focus. Some take on a multidimensional view of creativity in evaluating diverse creative mental operations. This talk explores how the chosen path of investigation necessarily impacts wider conceptualizations of the creative brain and why we need to be cognizant of the same. Also discussed are the unique challenges of adopting the neuroscientific perspective in examining creativity as well as the unusual insights this union affords.

Bio: Anna Abraham is a Professor of Psychology in Leeds Beckett University. She investigates the neurocognitive basis of creativity and other aspects of the human imagination including the reality-fiction distinction, mental time travel, self-referential thinking and mental state reasoning. Her educational background is in the disciplines of psychology and neuroscience, and she has studied and worked in several academic institutions across the world. She is the author of the 2018 book, The Neuroscience of Creativity, with Cambridge University Press. For more information, please visit her website: http://www.anna-abraham.com/

PLEASE NOTE: THIS ZANGWILL TALK IS TAKING PLACE AT THE USUAL TIME OF 4.30PM. THE ZANGWILL TEA WILL BE AT 4.00PM

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Polyproline Tri‐Helix Macrocycles as Nanosized Scaffolds to Control Ligand Patterns for Selective Protein Oligomer Interactions

By Cin‐Hao Lin, Hsin‐Chuan Wen, Cheng‐Chin Chiang, Jen‐Sheng Huang, Yunching Chen, Sheng‐Kai Wang from Wiley: Small: Table of Contents. Published on Apr 12, 2019.

Polyproline tri‐helix macrocycles form scaffolds for ligands to be adjustably conjugated at the desired locations to create desired ligand patterns. With efficient modular synthetic strategies, the generated ligand patterns selectively interact with isolable protein oligomers and receptor oligomers on the cell surface. This universal tool can be employed to probe and manipulate receptor arrangements, and as potential nanomedicine. Abstract Multivalent ligand–receptor interactions play essential roles in biological recognition and signaling. As the receptor arrangement on the cell surface can alter the outcome of cell signaling and also provide spatial specificity for ligand binding, controlling the presentation of ligands has become a promising strategy to manipulate or selectively target protein receptors. The lack of adjustable universal tools to control ligand positions at the size of a few nanometers has prompted the development of polyproline tri‐helix macrocycles as scaffolds to present ligands in designated patterns. Model lectin Helix pomatia agglutinin has shown selectivity toward the matching GalNAc ligand pattern matching its binding sites arrangement. The GalNAc pattern selectivity is also observed on intact asialoglycoprotein receptor oligomer on human hepatoma cells showing the pattern‐selective interaction can be achieved not only on isolated protein oligomers but also the receptors arranged on the cell surface. As the scaffold design allows convenient creation of versatile ligand patterns, it can be expected as a promising tool to probe the arrangement of receptors on the cell surface and as nanomedicine to manipulate signaling or cell recognition.

Long‐Distance Rate Acceleration by Bulk Gold

By Alexander Schlimm, Roland Löw, Talina Rusch, Fynn Röhricht, Thomas Strunskus, Tobias Tellkamp, Frank Sönnichsen, Uwe Manthe, Olaf Magnussen, Felix Tuczek, Rainer Herges from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 12, 2019.

Remote control: Azobenzenes standing upright on a gold surface isomerize from cis to trans faster than in solution by several orders of magnitude. A coupling unit allows to tune between those extremes. Experimental and theoretical investigations show that the 1300‐fold rate acceleration is due to a singlet–triplet–singlet spin change, which is forbidden in solution but mediated by bulk gold over 11 bonds and a distance of 14 Å. Abstract We report on a very unusual case of surface catalysis involving azobenzenes in contact with a Au(111) surface. A rate acceleration of the cis–trans isomerization on gold up to a factor of 1300 compared to solution is observed. By using carefully designed molecular frameworks, the electronic coupling to the surface can be systematically tuned. The isomerization kinetics of molecules with very weak coupling to the metal is similar to that found in solution. For their counterparts with strong coupling, the relaxation rate is shown to depend on the spin‐density distribution in the triplet states of the molecules. This suggests that an intersystem crossing is involved in the relaxation process. Aside from their impact on catalytic processes, these effects could be used to trigger reactions over long distances.

[ASAP] InGaN Platelets: Synthesis and Applications toward Green and Red Light-Emitting Diodes

By Zhaoxia Bi, Filip Lenrick, Jovana Colvin, Anders Gustafsson, Olof Hultin, Ali Nowzari, Taiping Lu, Reine Wallenberg, Rainer Timm, Anders Mikkelsen, B. Jonas Ohlsson, Kristian Storm, Bo Monemar, Lars Samuelson from Nano Letters: Latest Articles (ACS Publications). Published on Apr 12, 2019.

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Nano Letters
DOI: 10.1021/acs.nanolett.8b04781

[ASAP] Efficient Ultrathin Liquid Junction Photovoltaics Based on Transition Metal Dichalcogenides

By Li Wang, Justin B. Sambur from Nano Letters: Latest Articles (ACS Publications). Published on Apr 12, 2019.

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Nano Letters
DOI: 10.1021/acs.nanolett.9b00070

[ASAP] Genetically Engineered Cell Membrane Nanovesicles for Oncolytic Adenovirus Delivery: A Versatile Platform for Cancer Virotherapy

By Peng Lv, Xuan Liu, Xiaomei Chen, Chao Liu, Yang Zhang, Chengchao Chu, Junqing Wang, Xiaoyong Wang, Xiaoyuan Chen, Gang Liu from Nano Letters: Latest Articles (ACS Publications). Published on Apr 12, 2019.

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Nano Letters
DOI: 10.1021/acs.nanolett.9b00145

[ASAP] Direct Photoluminescence Probing of Ferromagnetism in Monolayer Two-Dimensional CrBr3

By Zhaowei Zhang, Jingzhi Shang, Chongyun Jiang, Abdullah Rasmita, Weibo Gao, Ting Yu from Nano Letters: Latest Articles (ACS Publications). Published on Apr 12, 2019.

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Nano Letters
DOI: 10.1021/acs.nanolett.9b00553

[ASAP] Manganese as a Catalytic Mediator for Photo-oxidation and Breaking the pH Limitation of Nanozymes

By Jinyi Zhang, Shihong Wu, Xiaomei Lu, Peng Wu, Juewen Liu from Nano Letters: Latest Articles (ACS Publications). Published on Apr 12, 2019.

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Nano Letters
DOI: 10.1021/acs.nanolett.9b00725

[ASAP] Adhesion Stabilized en Masse Intracellular Electrical Recordings from Multicellular Assemblies

By Oskar Staufer, Sebastian Weber, C. Peter Bengtson, Hilmar Bading, Amin Rustom, Joachim P. Spatz from Nano Letters: Latest Articles (ACS Publications). Published on Apr 12, 2019.

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Nano Letters
DOI: 10.1021/acs.nanolett.9b00784

[ASAP] Enhancing Microcirculation on Multitriggering Manner Facilitates Angiogenesis and Collagen Deposition on Wound Healing by Photoreleased NO from Hemin-Derivatized Colloids

By Chia-Hao Su, Wei-Peng Li, Ling-Chuan Tsao, Liu-Chun Wang, Ya-Ping Hsu, Wen-Jyun Wang, Min-Chiao Liao, Chin-Lai Lee, Chen-Sheng Yeh from ACS Nano: Latest Articles (ACS Publications). Published on Apr 12, 2019.

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ACS Nano
DOI: 10.1021/acsnano.8b09417

[ASAP] Hydrophilic/Hydrophobic Interphase-Mediated Bubble-like Stretchable Janus Ultrathin Films toward Self-Adaptive and Pneumatic Multifunctional Electronics

By Peng Xiao, Yun Liang, Jiang He, Lei Zhang, Shuai Wang, Jincui Gu, Jiawei Zhang, Youju Huang, Shiao-Wei Kuo, Tao Chen from ACS Nano: Latest Articles (ACS Publications). Published on Apr 12, 2019.

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ACS Nano
DOI: 10.1021/acsnano.8b09600

[ASAP] Catalase-Integrated Hyaluronic Acid as Nanocarriers for Enhanced Photodynamic Therapy in Solid Tumor

By Soo Zeng Fiona Phua, Guangbao Yang, Wei Qi Lim, Apoorva Verma, Hongzhong Chen, Thirumaran Thanabalu, Yanli Zhao from ACS Nano: Latest Articles (ACS Publications). Published on Apr 12, 2019.

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ACS Nano
DOI: 10.1021/acsnano.9b01087

[ASAP] Use of Polymeric Nanoparticle Platform Targeting the Liver To Induce Treg-Mediated Antigen-Specific Immune Tolerance in a Pulmonary Allergen Sensitization Model

By Qi Liu, Xiang Wang, Xiangsheng Liu, Sanjan Kumar, Grant Gochman, Ying Ji, Yu-Pei Liao, Chong Hyun Chang, Wesley Situ, Jianqin Lu, Jinhong Jiang, Kuo-Ching Mei, Huan Meng, Tian Xia, Andre E. Nel from ACS Nano: Latest Articles (ACS Publications). Published on Apr 12, 2019.

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ACS Nano
DOI: 10.1021/acsnano.9b01444

[ASAP] Spatially Resolved Chemical Analysis of Geobacter sulfurreducens Cell Surface

By Nikolai Lebedev, Rhonda M. Stroud, Matthew D. Yates, Leonard Martin Tender from ACS Nano: Latest Articles (ACS Publications). Published on Apr 12, 2019.

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ACS Nano
DOI: 10.1021/acsnano.9b02032

[ASAP] Correction to Molecular Orbital Gating Surface-Enhanced Raman Scattering

By Chenyang Guo, Xing Chen, Song-Yuan Ding, Dirk Mayer, Qingling Wang, Zhikai Zhao, Lifa Ni, Haitao Liu, Takhee Lee, Bingqian Xu, Dong Xiang from ACS Nano: Latest Articles (ACS Publications). Published on Apr 12, 2019.

ACS Nano
DOI: 10.1021/acsnano.9b02533

[ASAP] Computational Estimation of Microsecond to Second Atomistic Folding Times

By Upendra Adhikari, Barmak Mostofian, Jeremy Copperman, Sundar Raman Subramanian, Andrew A. Petersen, Daniel M. Zuckerman from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Apr 12, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.8b10735

[ASAP] Strategy to Lengthen the On-Time of Photochromic Rhodamine Spirolactam for Super-resolution Photoactivated Localization Microscopy

By Zhiwei Ye, Haibo Yu, Wei Yang, Ying Zheng, Ning Li, Hui Bian, Zechen Wang, Qiang Liu, Youtao Song, Mingyan Zhang, Yi Xiao from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Apr 12, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.8b11369

[ASAP] The Oxidation of Platinum under Wet Conditions Observed by Electrochemical X-ray Photoelectron Spectroscopy

By Rik Mom, Lorenz Frevel, Juan-Jesús Velasco-Vélez, Milivoj Plodinec, Axel Knop-Gericke, Robert Schlögl from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Apr 12, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.8b12284

[ASAP] Stoichiometry-Controlled InP-Based Quantum Dots: Synthesis, Photoluminescence, and Electroluminescence

By Yang Li, Xiaoqi Hou, Xingliang Dai, Zhenlei Yao, Liulin Lv, Yizheng Jin, Xiaogang Peng from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Apr 12, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.8b12908

[ASAP] Double-Circularly Connected Saloph-Belt Macrocycles Generated from a Bis-Armed Bifunctional Monomer

By Takashi Nakamura, Shinnosuke Tsukuda, Tatsuya Nabeshima from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Apr 12, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b00171

[ASAP] Nonadditive Ion Effects Drive Both Collapse and Swelling of Thermoresponsive Polymers in Water

By Ellen E. Bruce, Pho T. Bui, Bradley A. Rogers, Paul S. Cremer, Nico F. A. van der Vegt from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Apr 12, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b00295

[ASAP] Azobenzene-Bridged Expanded “Texas-sized” Box: A Dual-Responsive Receptor for Aryl Dianion Encapsulation

By Xiaodong Chi, Wanglai Cen, Jack A. Queenan, Lingliang Long, Vincent M. Lynch, Niveen M. Khashab, Jonathan L. Sessler from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Apr 12, 2019.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b01241

Artificial muscle with reversible and controllable deformation based on stiffness-variable carbon nanotube spring-like nanocomposite yarn

By Xiaodong He from RSC - Nanoscale latest articles. Published on Apr 12, 2019.

Nanoscale, 2019, Advance Article
DOI: 10.1039/C9NR00611G, Communication
Liangliang Xu, Qingyu Peng, Yue Zhu, Xu Zhao, Minglong Yang, Shasha Wang, Fuhua Xue, Ye Yuan, Zaishan Lin, Fan Xu, Xianxian Sun, Jianjun Li, Weilong Yin, Yibin Li, Xiaodong He
An artificial muscle based on a stiffness-variable CNT spring-like nanocomposite yarn shows controllable and reversible deformation, and potential application.
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Direct Laser Writing of Flexible Planar Supercapacitors Based on GO and Black Phosphorus Quantum Dots Nanocomposites

By Hong-Bo Sun from RSC - Nanoscale latest articles. Published on Apr 12, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR02530H, Paper
Xiu-Yan Fu, Zhao-Di Chen, Yong-lai Zhang, Dong-Dong Han, Jia-Nan Ma, Wei Wang, Zi-Rui Zhang, Hong Xia, Hong-Bo Sun
The research interests in wearable electronics has continuously stimulated the development of flexible energy storage systems with high performance and robustness. However, open problems with respect to energy storage efficiency...
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Permanently Hydrophilic, Piezoelectric PVDF Nanofibrous Scaffolds Promoting Unaided Electromechanical Stimulation on Osteoblasts

By Leonardo Barrios from RSC - Nanoscale latest articles. Published on Apr 12, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C8NR10384D, Paper
Maria Kitsara, Andreu Blanquer, Gonzalo Murillo, vincent humblot, Sara De Bragança Vieira, Carme Nogues, Elena Ibañez, Jaume Esteve, Leonardo Barrios
Biomimetic functional scaffolds for tissue engineering should fulfil specific requirements concerning structural, bio-chemical and electro-mechanical characteristics, depending on the tissue that they are designed to resemble. In bone tissue engineering,...
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A ratiometric theranostic nanoprobe for pH imaging-guided photodynamic therapy

By Shiying Li from RSC - Nanoscale latest articles. Published on Apr 12, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR00093C, Paper
Hong Cheng, Guiling Fan, Jinghao Fan, Linping Zhao, Rongrong Zheng, Xiyong Xu, Shiying Li
Abnormal pH microenvironment goes along with the development of tumor, which also affects the therapeutic efficiency of anti-tumor drugs. In this work, a Fӧrster resonance energy transfer (FRET)-based theranostic fluorescent...
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Hollow Black TiAlOx Nanocomposites for Solar Thermal Desalination

By Zhenhai Wen from RSC - Nanoscale latest articles. Published on Apr 12, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C8NR10117E, Paper
Luocai Yi, Dianpeng Qi, Ping Shao, Chaojun Lei, Yang Hou, Pingwei Cai, Genxiang Wang, Xiaodong Chen, Zhenhai Wen
Although solar-thermal conversion technique shows great potential for seawater desalination, there remains a grand challenge in exploring low-cost and high-efficiency photothermal materials. We here report a molten salt assisted galvanic...
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Nanozyme-based cascade colorimetric aptasensor for amplified detection of ochratoxin A

By Yue He from RSC - Nanoscale latest articles. Published on Apr 12, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR02872B, Paper
Fengyu Tian, Jing Zhou, Bining Jiao, Yue He
Colorimetric assays have been widely developed for the detection of toxin ochratoxin A (OTA), but most of them suffer from moderate sensitivity when they are adopted for the detection of...
The content of this RSS Feed (c) The Royal Society of Chemistry

Construction of Sandwich-like Porous Structure of Graphene-Coated Foam Composites for Ultrasensitive and Flexible Pressure Sensor

By Long-Cheng Tang from RSC - Nanoscale latest articles. Published on Apr 12, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR02672J, Paper
Li ZHAO, Fei Qiang, Shouwei Dai, Shichang Shen, Yunzhuo Huang, Neng-Jian Huang, Guodong Zhang, Li-Zhi Guan, Jiefeng Gao, Yihu Song, Long-Cheng Tang
Ultrasensitive and flexible pressure sensors that can perceive and respond to environmental stimuli have attracted considerable attention due to their potential applications in wearable electronics and electronic skin devices. Here,...
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Wed 08 May 14:15: Prym varieties and Brill-Noether theory

From All Talks (aka the CURE list). Published on Apr 11, 2019.

Prym varieties and Brill-Noether theory

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Ambient Fast Synthesis and Active Sites Deciphering of Hierarchical Foam‐Like Trimetal–Organic Framework Nanostructures as a Platform for Highly Efficient Oxygen Evolution Electrocatalysis

By Qizhu Qian, Yapeng Li, Yi Liu, Lai Yu, Genqiang Zhang from Wiley: Advanced Materials: Table of Contents. Published on Apr 11, 2019.

Hierarchical trimetallic NiCoFe‐based metal–organic framework (MOF) nanofoam with modulated molar ratios is successfully synthesized through the developed mild one‐pot ambient‐temperature solution‐phase method, which can be directly utilized as efficient oxygen evolution reaction (OER) catalysts with extraordinary activity and excellent durability. The metal hydroxide and oxyhydroxide evolved from the pristine MOF structure are demonstrated as the active species for high OER activity. Abstract Metal–organic frameworks (MOFs) have attracted tremendous interest due to their promising applications including electrocatalysis originating from their unique structural features. However, it remains a challenge to directly use MOFs for oxygen electrocatalysis because it is quite difficult to manipulate their dimension, composition, and morphology of the MOFs with abundant active sites. Here, a facile ambient temperature synthesis of unique NiCoFe‐based trimetallic MOF nanostructures with foam‐like architecture is reported, which exhibit extraordinary oxygen evolution reaction (OER) activity as directly used catalyst in alkaline condition. Specifically, the (Ni2Co1)0.925Fe0.075‐MOF‐NF delivers a minimum overpotential of 257 mV to reach the current density of 10 mA cm−2 with a small Tafel slope of 41.3 mV dec−1 and exhibits high durability after long‐term testing. More importantly, the deciphering of the possible origination of the high activity is performed through the characterization of the intermediates during the OER process, where the electrochemically transformed metal hydroxides and oxyhydroxides are confirmed as the active species.

A Highly Stretchable Liquid Metal Polymer as Reversible Transitional Insulator and Conductor

By Hongzhang Wang, Youyou Yao, Zhizhu He, Wei Rao, Liang Hu, Sen Chen, Ju Lin, Jianye Gao, Pengju Zhang, Xuyang Sun, Xiangjiang Wang, Yuntao Cui, Qian Wang, Shijin Dong, Guozhen Chen, Jing Liu from Wiley: Advanced Materials: Table of Contents. Published on Apr 11, 2019.

A highly stretchable (680% strain) liquid metal polymer as a temperature‐controlled reversible transitional insulator and conductor is demonstrated. After freezing, the liquid metal droplets solidify and expand in volume, whereas the insulating polymer shrinks and becomes rigid, leading to the connection of liquid metal (conductive). It would recover to the initial state (insulative) after heating. Abstract Materials with a temperature‐controlled reversible electrical transition between insulator and conductor are attracting huge attention due to their promising applications in many fields. However, most of them are intrinsically rigid and require complicated fabrication processes. Here, a highly stretchable (680% strain) liquid metal polymer composite as a reversible transitional insulator and conductor (TIC), which is accompanied with huge resistivity changes (more than 4 × 109 times) reversibly through a tuning temperature in a few seconds is introduced. When frozen, the insulated TIC becomes conductive and recovers after warming. Both the phase change of the liquid metal droplets and the rigidity change of the polymer contribute directly to transition between insulator and conductor. A simplified model is established to predict the expansion and connection of liquid metal droplets. Along with high stretchability, straightforward fabrication methods, rapid triggering time, large switching ratio, good repeatability, the TIC offers tremendous possibilities for numerous applications, like stretchable switches, semiconductors, temperature sensors, and resistive random‐access memory. Accordingly, a system that can display numbers and letters via converting alternative TIC temperature to a binary signal on a computer is conceived and demonstrated. The present discovery suggests a general strategy for fabricating and stimulating a stretchable transitional insulator and conductor based on liquid metal and allied polymers.

In Operando Probing of Lithium‐Ion Storage on Single‐Layer Graphene

By Kun Ni, Xiangyang Wang, Zhuchen Tao, Jing Yang, Na Shu, Jianglin Ye, Fei Pan, Jian Xie, Ziqi Tan, Xuemei Sun, Jie Liu, Zhikai Qi, Yanxia Chen, Xiaojun Wu, Yanwu Zhu from Wiley: Advanced Materials: Table of Contents. Published on Apr 11, 2019.

A single‐layer graphene film is electrochemically cycled as an anode in a half cell to probe the evolution of the electrode/electrolyte interface and lithium‐storage mechanism, which are followed by in operando Raman spectroscopy and Fourier transform infrared spectroscopy. The understanding may provide new insight on the Li deposition on carbon and the role of high‐specific surface area carbons as anodes for Li‐ion batteries. Abstract Despite high‐surface area carbons, e.g., graphene‐based materials, being investigated as anodes for lithium (Li)‐ion batteries, the fundamental mechanism of Li‐ion storage on such carbons is insufficiently understood. In this work, the evolution of the electrode/electrolyte interface is probed on a single‐layer graphene (SLG) film by performing Raman spectroscopy and Fourier transform infrared spectroscopy when the SLG film is electrochemically cycled as the anode in a half cell. The utilization of SLG eliminates the inevitable intercalation of Li ions in graphite or few‐layer graphene, which may have complicated the discussion in previous work. Combining the in situ studies with ex situ observations and ab initio simulations, the formation of solid electrolyte interphase and the structural evolution of SLG are discussed when the SLG is biased in an electrolyte. This study provides new insights into the understanding of Li‐ion storage on SLG and suggests how high‐surface‐area carbons could play proper roles in anodes for Li‐ion batteries.

Dual Interfacial Design for Efficient CsPbI2Br Perovskite Solar Cells with Improved Photostability

By Jingjing Tian, Qifan Xue, Xiaofeng Tang, Yuxuan Chen, Ning Li, Zhicheng Hu, Tingting Shi, Xin Wang, Fei Huang, Christoph J. Brabec, Hin‐Lap Yip, Yong Cao from Wiley: Advanced Materials: Table of Contents. Published on Apr 11, 2019.

The efficiency and photostability of all‐inorganic mixed‐halide perovskite solar cells (PVSCs) can be simultaneously enhanced by introducing an amino‐functionalized polymer PN4N as a novel cathode interlayer and dopant‐free PDCBT hole‐transporting layer. The favorable interaction between perovskite crystal and PN4N/PDCBT can effectively improve CsPbI2Br film quality, with power conversion efficiency over 16%. Abstract A synergic interface design is demonstrated for photostable inorganic mixed‐halide perovskite solar cells (PVSCs) by applying an amino‐functionalized polymer (PN4N) as cathode interlayer and a dopant‐free hole‐transporting polymer poly[5,5′‐bis(2‐butyloctyl)‐(2,2′‐bithiophene)‐4,4′‐dicarboxylate‐alt‐5,5′‐2,2′‐bithiophene] (PDCBT) as anode interlayer. First, the interfacial dipole formed at the cathode interface reduces the workfunction of SnO2, while PDCBT with deeper‐lying highest occupied molecular orbital (HOMO) level provides a better energy‐level matching at the anode, leading to a significant enhancement in open‐circuit voltage (Voc) of the PVSCs. Second, the PN4N layer can also tune the surface wetting property to promote the growth of high‐quality all‐inorganic perovskite films with larger grain size and higher crystallinity. Most importantly, both theoretical and experimental results reveal that PN4N and PDCBT can interact strongly with the perovskite crystal, which effectively passivates the electronic surface trap states and suppresses the photoinduced halide segregation of CsPbI2Br films. Therefore, the optimized CsPbI2Br PVSCs exhibit reduced interfacial recombination with efficiency over 16%, which is one of the highest efficiencies reported for all‐inorganic PVSCs. A high photostability with a less than 10% efficiency drop is demonstrated for the CsPbI2Br PVSCs with dual interfacial modifications under continuous 1 sun equivalent illumination for 400 h.

Key Aspects of Lithium Metal Anodes for Lithium Metal Batteries

By Zahid Ali Ghazi, Zhenhua Sun, Chengguo Sun, Fulai Qi, Baigang An, Feng Li, Hui‐Ming Cheng from Wiley: Small: Table of Contents. Published on Apr 11, 2019.

Lithium (Li) metal anode is broadly recognized as an excellent candidate for nextgeneration energy storage devices owing to its high specific energy density. In this Review, a conceptual understanding about the key aspects of Li metal anode is provided, the most recent advancements in Li metal battery technology are outlined and suggestions for future research on Li anodes are presented. Abstract Rechargeable batteries are considered promising replacements for environmentally hazardous fossil fuel‐based energy technologies. High‐energy lithium‐metal batteries have received tremendous attention for use in portable electronic devices and electric vehicles. However, the low Coulombic efficiency, short life cycle, huge volume expansion, uncontrolled dendrite growth, and endless interfacial reactions of the metallic lithium anode are major obstacles in their commercialization. Extensive research efforts have been devoted to address these issues and significant progress has been made by tuning electrolyte chemistry, designing electrode frameworks, discovering nanotechnology‐based solutions, etc. This Review aims to provide a conceptual understanding of the current issues involved in using a lithium metal anode and to unveil its electrochemistry. The most recent advancements in lithium metal battery technology are outlined and suggestions for future research to develop a safe and stable lithium anode are presented.

Recent Progress in Three‐Terminal Artificial Synapses: From Device to System

By Hong Han, Haiyang Yu, Huanhuan Wei, Jiangdong Gong, Wentao Xu from Wiley: Small: Table of Contents. Published on Apr 11, 2019.

Recently, various artificial devices have been made to emulate synaptic plastic for neuromorphic computing, and to build artificial sensory and motor systems. This Review summarizes recent progress in three‐terminal artificial synapses from device to system. Abstract Synapses are essential to the transmission of nervous signals. Synaptic plasticity allows changes in synaptic strength that make a brain capable of learning from experience. During development of neuromorphic electronics, great efforts have been made to design and fabricate electronic devices that emulate synapses. Three‐terminal artificial synapses have the merits of concurrently transmitting signals and learning. Inorganic and organic electronic synapses have mimicked plasticity and learning. Optoelectronic synapses and photonic synapses have the prospective benefits of low electrical energy loss, high bandwidth, and mechanical robustness. These artificial synapses provide new opportunities for the development of neuromorphic systems that can use parallel processing to manipulate datasets in real time. Synaptic devices have also been used to build artificial sensory systems. Here, recent progress in the development and application of three‐terminal artificial synapses and artificial sensory systems is reviewed.

Nucleic Acid–Based Functional Nanomaterials as Advanced Cancer Therapeutics

By Ye Yuan, Zi Gu, Chi Yao, Dan Luo, Dayong Yang from Wiley: Small: Table of Contents. Published on Apr 11, 2019.

Nucleic acid–based functional nanomaterials (NAFN) have been widely used as emerging drug delivery nanocarriers. In this Review, the recent progress on NAFN as advanced cancer therapeutics is highlighted. Examples are presented to show how NAFN are rationally designed to address the problems in cancer therapy. The challenges and future development of NAFN toward biomedical applications are also discussed. Abstract Nucleic acid–based functional nanomaterials (NAFN) have been widely used as emerging drug delivery nanocarriers for cancer therapeutics. Considerable works have demonstrated that NAFN can effectively load and protect therapeutic agents, and particularly enable targeting delivery to the tumor site and stimuli‐responsive release. These outstanding performances are due to NAFN's unique properties including inherent biological functions and sequence programmability as well as biocompatibility and biodegradability. In this Review, the recent progress on NAFN as advanced cancer therapeutics is highlighted. Three main cancer therapy approaches are categorized including chemo‐, immuno‐, and gene‐therapy. Examples are presented to show how NAFN are rationally and exquisitely designed to address problems in cancer therapy. The challenges and future development of NAFN are also discussed toward future more practical biomedical applications.

Spotlights on our sister journals: Angew. Chem. Int. Ed. 18/2019

By from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 11, 2019.

CSC and CIC Awards 2019

By from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 11, 2019.

Teruaki Mukaiyama (1927–2018)

By Dieter Seebach from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 11, 2019.

Teruaki Mukaiyama, formerly Professor at Tokyo Institute of Technology, Tokyo University, and Tokyo University of Science passed away on November 17, 2018. As one of the most productive organic chemists he has enriched the field of synthetic organic chemistry in 60 years of research. His most important contributions are reviewed herein by a close friend.

Graphical Abstract: Angew. Chem. Int. Ed. 18/2019

By from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 11, 2019.

Inside Back Cover: Four Boron Atoms, Four Positive Charges, and Four Skeletal Electrons: A Fluorescent σ‐Aromatic Tetraborane(4) (Angew. Chem. Int. Ed. 18/2019)

By Anna Widera, Hubert Wadepohl, Hans‐Jörg Himmel from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 11, 2019.

Overcoming the “Coulomb explosion”: The electron‐donating capability of the bicyclic guanidinate hpp enables the synthesis of an extremely electron‐deficient fourfold base‐stabilized analogue of the hypothetical [B4H4]4+. In their Communication on page 5897 ff., H.‐J. Himmel and co‐workers show that the σ‐aromatic tetracationic compound displays fluorescence and is stabilized in the solid state by the lattice energy.

Inside Cover: Highly Selective Synthesis of Iridium(III) Metalla[2]catenanes through Component Pre‐Orientation by π⋅⋅⋅π Stacking (Angew. Chem. Int. Ed. 18/2019)

By Wei‐Long Shan, Yue‐Jian Lin, F. Ekkehardt Hahn, Guo‐Xin Jin from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 11, 2019.

The topology of interlinked metallacycles can be controlled through their substitution pattern. In their Communication on page 5882 ff., F. E. Hahn, G.‐X. Lin, and co‐workers describe the synthesis of metalla[2]catenanes from dinuclear iridium complexes and anthracene‐bridged dipyridyl ligands. Noncovalent π–π‐stacking interactions play a crucial role in the formation of these catenanes.

Frontispiece: The Dominant Role of Oxygen in Modulating the Chemical Evolution Pathways of Tyrosine in Peptides: Dityrosine or Melanin

By Xiaokang Ren, Qianli Zou, Chengqian Yuan, Rui Chang, Ruirui Xing, Xuehai Yan from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 11, 2019.

Peptides In their Communication on page 5872 ff., X. Yan and co‐workers reveal that oxygen concentration determines whether dityrosine or melanin is formed from tyrosine in the chemical evolution of tyrosine‐containing peptides and proteins.

Cover Picture: Halogen‐Dependent Surface Confinement Governs Selective Alkane Functionalization to Olefins (Angew. Chem. Int. Ed. 18/2019)

By Guido Zichittella, Matthias Scharfe, Begoña Puértolas, Vladimir Paunović, Patrick Hemberger, Andras Bodi, László Szentmiklósi, Núria López, Javier Pérez‐Ramírez from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 11, 2019.

Heaven can wait. Operando spectroscopy techniques can distinguish surface and gas‐phase processes in alkane oxyhalogenation. In their Communication on page 5877, J. Pérez‐Ramírez et al. unravel the mechanistic origin of the halogen effect steering catalysis. Selective alkane conversion into olefins is driven by surface‐confined chlorine. A colony of bats depicts the unselective gas‐phase radical‐chain mechanism with bromine. An angel views the selectivity control on earth.

Back Cover: General Cyclopropane Assembly by Enantioselective Transfer of a Redox‐Active Carbene to Aliphatic Olefins (Angew. Chem. Int. Ed. 18/2019)

By Marc Montesinos‐Magraner, Matteo Costantini, Rodrigo Ramírez‐Contreras, Michael E. Muratore, Magnus J. Johansson, Abraham Mendoza from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 11, 2019.

The construction of a carbon stereocenter in a future “carbon city” is shown in which these moieties are assembled in a unified and programmable way. This approach is well‐established in conventional construction in which a few general tools can build unrelated structures. As shown by A. Mendoza et al. in their Communication on page 5930 ff., one strategy can serve the assembly of cyclopropane stereocenters with different functionality (colored atoms in the illustration).

High Thermal Conductivity in Boron Arsenide: From Prediction to Reality

By Fei Tian, Zhifeng Ren from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 11, 2019.

Boron arsenide has been recently predicted to be a new thermal conductor. In this Minireview, developments of boron arsenide growth techniques resulting in bigger and better crystals are discussed, and measurements of related properties, including thermal conductivity, are summarized. Abstract Modern first‐principles calculations predict that the thermal conductivity of boron arsenide is second only to that of diamond, the best thermal conductor, which may be of benefit for waste heat management in electronic devices. With the optimization of single‐crystal growth methods, large‐size and high‐quality boron arsenide single crystals have been grown and thermal conductivity measurements have verified the related predictions. Benefiting from the increased size and improved qualities, additional properties have been characterized. Important factors related to boron arsenide, remaining challenges, and the future outlook are addressed in this minireview.

Proof of Concept for Hydrogen Bonding to Gold, Au⋅⋅⋅H−X

By Hubert Schmidbaur from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 11, 2019.

Convincing and consistent evidence for the existence of hydrogen bonding to gold has been obtained. An ammonium or pyridinium group has been shown to be an efficient hydrogen bond donor unit for gold(I) coordination centers, and the assembly leads to the structural pattern typical for standard hydrogen bonds. This constitutes the first rigorous, scrutinizing, and comprehensive study of hydrogen bonds to a metal atom, with gold being an ideal model element because of relativistic effects.

Strange Case of Signor Volta and Mister Nicholson: How Electrochemistry Developed as a Consequence of an Editorial Misconduct

By Luigi Fabbrizzi from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 11, 2019.

Electrochemistry under political constraints: The invention of the pile by Alessandro Volta and the subsequent discovery by William Nicholson of the electrolysis of water (1800) took place under uncomfortable conditions, owing to the political and military troubles in Europe at the time. In spite of this, the astounding news spread quickly and stimulated hundreds of practitioners, thus giving rise to the flowering of a new discipline: electrochemistry. Abstract This Essay tells the colourful history of the invention of the pile by Alessandro Volta and of the subsequent discovery by William Nicholson of the electrolysis of water, carried out with the Voltaic pile (1800). Indeed, as a result of the dissemination of Volta's paper among London scientists, favoured by an incorrect behaviour of the President of the Royal Society, the article by Nicholson was published months before the publication of Volta's letter. The outstanding news that electricity could be generated by a simple and easy to build instrument (the pile) was printed also by daily newspapers, which favoured its spreading all over Europe and stimulated a multitude of enthusiast practitioners and amateurs to construct their own pile and to carry out the electrical decomposition of a variety of aqueous electrolytes. The correct chemical interpretation of the pile and of electrolysis had to wait for nearly one century, but in 1800 electrochemistry was born.

Palladium(II)‐Initiated Catellani‐Type Reactions

By Hong‐Gang Cheng, Shuqing Chen, Ruiming Chen, Qianghui Zhou from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 11, 2019.

Cooperative solutions: Palladium(II)‐initiated norbornene (NBE)‐mediated cooperative catalysis has enabled significant developments of the Catellani reaction. These advances and their application in the synthesis of bioactive molecules are summarized in this Minireview. Abstract The Catellani reaction is known as a powerful strategy for the expeditious synthesis of highly substituted arenes and benzo‐fused rings, which are usually difficult to access through traditional cross‐coupling strategies. It utilizes the synergistic interplay of palladium and norbornene catalysis to facilitate sequential ortho C−H functionalization and ipso termination of aryl halides in a single operation. In classical Catellani‐type reactions, aryl halides are mainly used as the substrates, and a Pd0 catalyst is required to initiate the reaction. Nevertheless, recent advances showcase that Catellani‐type reactions can also be initiated by a PdII catalyst with different starting materials instead of aryl halides via different reaction mechanisms and under different conditions. This emerging concept of PdII/norbornene cooperative catalysis has significantly advanced Catellani‐type reactions, thus enabling future developments of this field. In this Minireview, PdII‐initiated Catellani‐type reactions and their application in the synthesis of bioactive molecules are summarized.

Functional Polymeric Materials Based on Main‐Group Elements

By Fernando Vidal, Frieder Jäkle from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 11, 2019.

Polymers go main group! This Review shows how the incorporation of the full range of available main‐group elements into polymers leads to new functional hybrid materials with potential use in diverse application fields ranging from advanced elastomers, responsive gels, biodegradable materials, to organic electronics, imaging agents, sensors, and supported catalysts. Abstract The past decade has witnessed tremendous advances in the synthesis of polymers that contain elements from the main groups beyond those found in typical organic polymers. Unique properties that arise from dramatic differences in bonding and molecular geometry, electronic structure, and chemical reactivity, are exploited in diverse application fields. Herein we highlight recent advances in inorganic backbone polymers, discuss how Lewis acid/base functionalization of polymers results in unprecedented reactivity, and survey conjugated hybrids with unique electronic structures for sensor and device applications.

Synthesis of Bisheteroarylalkanes by Heteroarylboration: Development and Application of a Pyridylidene–Copper Complex

By Yuan Huang, M. Kevin Brown from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 11, 2019.

Pyridylidene–copper complexes for Cu/Pd‐catalyzed heteroarylboration of alkenylheteroarenes is presented. The significance of 1,1′‐heteroarylalkanes as building blocks for drug discovery and the availability of the pyridylidene‐Cu complexes makes this method attractive. Chiral variants of the pyridylidene‐Cu complexes were prepared and utilized in the enantioselective arylboration of E‐alkenes. Abstract The development of pyridylidene‐Cu‐complexes and their application in Cu/Pd‐catalyzed heteroarylboration of alkenylheteroarenes is reported. The significance of 1,1′‐heteroarylalkanes as building blocks for drug discovery, as well as the straightforward and modular sequence to prepare the pyridylidene‐Cu‐complexes, makes this catalyst and it applications attractive for chemical synthesis. Furthermore, chiral variants of the pyridylidene‐Cu‐complexes have been prepared and utilized in the enantioselective arylboration of E‐alkenes, further demonstrating the value and potential of this class of catalysts.

Shifting Oxygen Charge Towards Octahedral Metal: A Way to Promote Water Oxidation on Cobalt Spinel Oxides

By Shengnan Sun, Yuanmiao Sun, Ye Zhou, Shibo Xi, Xiao Ren, Bicheng Huang, Hanbin Liao, Luyuan Paul Wang, Yonghua Du, Zhichuan J. Xu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 11, 2019.

The oxygen evolution activity of Co‐based spinel oxides is dominated by the catalytically critical TMO6 octahedra. Pushing more active Co into octahedral sites and shifting the oxygen charge to octahedral Co significantly enhance the activity. Abstract Cobalt spinel oxides are a class of promising transition metal (TM) oxides for catalyzing oxygen evolution reaction (OER). Their catalytic activity depends on the electronic structure. In a spinel oxide lattice, each oxygen anion is shared amongst its four nearest transition metal cations, of which one is located within the tetrahedral interstices and the remaining three cations are in the octahedral interstices. This work uncovered the influence of oxygen anion charge distribution on the electronic structure of the redox‐active building block Co−O. The charge of oxygen anion tends to shift toward the octahedral‐occupied Co instead of tetrahedral‐occupied Co, which hence produces strong orbital interaction between octahedral Co and O. Thus, the OER activity can be promoted by pushing more Co into the octahedral site or shifting the oxygen charge towards the redox‐active metal center in CoO6 octahedra.

A Main‐Group Element Radical Based One‐Dimensional Magnetic Chain

By Rui Feng, Li Zhang, Huapeng Ruan, Yue Zhao, Gengwen Tan, Xinping Wang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 11, 2019.

The reduction of a pyridinyl functionalized borane 1 with potassium in THF afforded the first main‐group element radical based one‐dimensional magnetic chain (1K)n, which was formed through the self‐assembly of the borane radical anions by coordination to the potassium cations. The magnetic measurements and theoretical calculations reveal that the spin centers in (1K)n feature an antiferromagnetic interaction. Abstract The first main‐group element radical based one‐dimensional magnetic chain (1K)n was realized by one‐electron reduction of the pyridinyl functionalized borane 1 with elemental potassium in THF in the absence of 18‐crown‐6 (18‐c‐6). The electron spin density of (1K)n mainly resides at the boron centers with a considerable contribution from central benzene and pyridine moieties. The spin centers exhibit an antiferromagnetic interaction as demonstrated by magnetic measurements and theoretical calculations. In contrast, the reduction in the presence of 18‐c‐6 afforded the separated radical anion salt 1K(Crown), in which the potassium cation was trapped by THF and 18‐c‐6 molecules. Further one‐electron reduction of 1K(Crown) and (1K)n led to the diamagnetic monomer and polymer, respectively.

Plasmonic Nickel–TiO2 Heterostructures for Visible‐Light‐Driven Photochemical Reactions

By Shuai He, Jiawei Huang, Justin L. Goodsell, Alexander Angerhofer, Wei David Wei from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 11, 2019.

Some electrons like it hot: Plasmon‐mediated charge transfer in Ni–TiO2 heterostructures was used to harvest visible‐light energy for photochemical reactions. The plasmon‐generated hot electrons were transferred from Ni to TiO2 to either occupy oxygen vacancies or produce Ti3+, while the plasmon‐generated hot holes were transferred to surface oxygens at TiO2. Furthermore, the transferred hot electrons play a primary role in driving methylene blue degradation. Abstract Plasmon‐mediated carrier transfer (PMCT) at metal–semiconductor heterojunctions has been extensively exploited to drive photochemical reactions, offering intriguing opportunities for solar photocatalysis. However, to date, most studies have been conducted using noble metals. Inexpensive materials capable of generating and transferring hot carriers for photocatalysis via PMCT have been rarely explored. Here, we demonstrate that the plasmon excitation of nickel induces the transfer of both hot electrons and holes from Ni to TiO2 in a rationally designed Ni–TiO2 heterostructure. Furthermore, it is discovered that the transferred hot electrons either occupy oxygen vacancies (VO) or produce Ti3+ on TiO2, while the transferred hot holes are located on surface oxygens at TiO2. Moreover, the transferred hot electrons are identified to play a primary role in driving the degradation of methylene blue (MB). Taken together, our results validate Ni as a promising low‐cost plasmonic material for prompting visible‐light photochemical reactions.

Synthesis and Reactivity of Paramagnetic Nickel Polypyridyl Complexes Relevant to C(sp2)–C(sp3)Coupling Reactions

By Megan Mohadjer Beromi, Gary W. Brudvig, Nilay Hazari, Hannah M. C. Lant, Brandon Q. Mercado from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 11, 2019.

The synthesis and both the stoichiometric and catalytic reactivity of polypyridyl supported NiI halide and aryl species relevant to modern C(sp2)–C(sp3) couplings is reported. The complexes can be generated through elementary reactions which are relevant to contemporary coupling reactions, and their nuclearity is dependent on the ancillary ligand. Abstract A number of new transition metal catalyzed methods for the formation of C(sp2)–C(sp3) bonds have recently been described. These reactions often utilize bidentate polypyridyl‐ligated Ni catalysts, and paramagnetic NiI halide or aryl species are proposed in the catalytic cycles. However, there is little knowledge about complexes of this type. Here, we report the synthesis of paramagnetic bidentate polypyridyl‐ligated Ni halide and aryl complexes through elementary reactions proposed in catalytic cycles for C(sp2)–C(sp3) bond formation. We investigate the ability of these complexes to undergo organometallic reactions that are relevant to C(sp2)–C(sp3) coupling through stoichiometric studies and also explore their catalytic activity.

The Dominant Role of Oxygen in Modulating the Chemical Evolution Pathways of Tyrosine in Peptides: Dityrosine or Melanin

By Xiaokang Ren, Qianli Zou, Chengqian Yuan, Rui Chang, Ruirui Xing, Xuehai Yan from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 11, 2019.

One way or another: The selective generation of dityrosine or melanin from tyrosine has been revealed to greatly depend on oxygen concentration in the chemical evolution of tyrosine‐containing peptides and proteins. This study paves the way for precisely designing biomaterials with controlled photoluminescence and photothermal properties reminiscent of the natural counterparts. Abstract In diverse biological systems, the oxidation of tyrosine to melanin or dityrosine is crucial for the formation of crosslinked proteins and thus for the realization of their structural, biological, and photoactive functionalities; however, the predominant factor in determining the pathways of this chemical evolution has not been revealed. Herein, we demonstrate for tyrosine‐containing amino acid derivatives, peptides, and proteins that the selective oxidation of tyrosine to produce melanin or dityrosine can be readily realized by manipulating the oxygen concentration in the reaction system. This oxygen‐dependent pathway selection reflects the selective chemical evolution of tyrosine to dityrosine and melanin in anaerobic and aerobic microorganisms, respectively. The resulting melanin‐ and dityrosine‐containing nanomaterials reproduce key functions of their natural counterparts with respect to their photothermal and photoluminescent characteristics, respectively. This work reveals the plausible role of oxygen in the chemical evolution of tyrosine derivatives and provides a versatile strategy for the rational design of tyrosine‐based multifunctional biomaterials.

Skeletal Rearrangement of Twisted Thia‐Norhexaphyrin: Multiply Annulated Polypyrrolic Aromatic Macrocycles

By Qizhao Li, Masatoshi Ishida, Hiroto Kai, Tingting Gu, Chengjie Li, Xin Li, Glib Baryshnikov, Xu Liang, Weihua Zhu, Hans Ågren, Hiroyuki Furuta, Yongshu Xie from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 11, 2019.

Oxidation of a nonaromatic thia‐modified norhexaphyrin with directly linked N‐confused pyrrole and thiophene rings triggered cleavage of a C−S bond to afford three multiply annulated polypyrrolic aromatic macrocycles with global or local aromaticity. This approach is a path to porphyrinoids with tunable structures and aromaticity based on thiophene cleavage and desulfurization. Abstract A hybrid thia‐norhexaphyrin comprising a directly linked N‐confused pyrrole and thiophene unit (1) revealed unique macrocycle transformations to afford multiply inner‐annulated aromatic macrocycles. Oxidation with 2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone triggered a cleavage of the C−S bond of the thiophene unit, accompanied with skeletal rearrangement to afford unique π‐conjugated products: a thiopyrrolo‐pentaphyrin embedded with a pyrrolo[1,2]isothiazole (2), a sulfur‐free pentaphyrin incorporating an indolizine moiety (3), and a thiopyranyltriphyrinoid containing a 2H‐thiopyran unit (4). Furthermore, 2 underwent desulfurization reactions to afford a fused pentaphyrin containing a pyrrolizine moiety (5) under mild conditions. Using expanded porphyrin scaffolds, oxidative thiophene cleavage and desulfurization of the hitherto unknown N‐confused core‐modified macrocycles would be a practical approach for developing unique polypyrrolic aromatic macrocycles.

A Polymer Coating Transfer Enrichment Method for Direct Mass Spectrometry Analysis of Lipids in Biofluid Samples

By Wenpeng Zhang, Spencer Chiang, Zishuai Li, Qinhua Chen, Yu Xia, Zheng Ouyang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 11, 2019.

A porous polymer coating transfer enrichment method was developed for the fast and direct mass spectrometry analysis of lipids in raw biofluid samples, enabling fast and reliable lipid profiling, detailed structure identification, and quantitation. Abstract A porous polymer coating transfer enrichment method is developed for the direct mass spectrometry (MS) analysis of lipids. The enrichment is fast (ca. 1 min) and enables the profiling and quantitation of lipids in small‐volume biofluid samples. Coupled with a photochemical Paternò–Büchi reaction, this method enables the fast determination of lipid structure at the C=C location level and point‐of‐care lipid biomarker analysis.

High Blocking Temperature of Magnetization and Giant Coercivity in the Azafullerene Tb2@C79N with a Single‐Electron Terbium–Terbium Bond

By Georgios Velkos, Denis S. Krylov, Kyle Kirkpatrick, Lukas Spree, Vasilii Dubrovin, Bernd Büchner, Stanislav M. Avdoshenko, Valeriy Bezmelnitsyn, Sean Davis, Paul Faust, James Duchamp, Harry C. Dorn, Alexey A. Popov from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 11, 2019.

New kids on the blocking: The azafullerene Tb2@C79N featuring a single‐electron Tb−Tb bond is found to be an air‐stable single‐molecule magnet with a high 100‐s blocking temperature of magnetization of 24 K and large coercivity. Tb magnetic moments with an easy‐axis single‐ion magnetic anisotropy are strongly coupled by the unpaired spin of the single‐electron Tb−Tb bond. Abstract The azafullerene Tb2@C79N is found to be a single‐molecule magnet with a high 100‐s blocking temperature of magnetization of 24 K and large coercivity. Tb magnetic moments with an easy‐axis single‐ion magnetic anisotropy are strongly coupled by the unpaired spin of the single‐electron Tb−Tb bond. Relaxation of magnetization in Tb2@C79N below 15 K proceeds via quantum tunneling of magnetization with the characteristic time τQTM=16 462±1230 s. At higher temperature, relaxation follows the Orbach mechanism with a barrier of 757±4 K, corresponding to the excited states, in which one of the Tb spins is flipped.

NiFe Alloy Nanoparticles with hcp Crystal Structure Stimulate Superior Oxygen Evolution Reaction Electrocatalytic Activity

By Changhong Wang, Hongchao Yang, Yejun Zhang, Qiangbin Wang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 11, 2019.

Hcp‐NiFe alloy nanoparticles encapsulated in N‐doped carbon shells (hcp‐NiFe@NC) were successfully synthesized through a facile MOF‐annealing strategy. Benefiting from the crystal structure and electronic property, the hcp‐NiFe@NC exhibits outstanding OER performance over the conventional fcc‐NiFe@NC catalyst. Abstract Tuning the crystal phase of metal alloy nanomaterials has been proved a significant way to alter their catalytic properties based on crystal structure and electronic property. Herein, we successfully developed a simple strategy to controllably synthesize a rare crystal structure of hexagonal close‐packed (hcp) NiFe nanoparticle (NP) encapsulated in a N‐doped carbon (NC) shell (hcp‐NiFe@NC). Then, we systemically investigated the oxygen evolution reaction (OER) performance of the samples under alkaline conditions, in which the hcp‐NiFe@NC exhibits superior OER activity compared to the conventional face‐centered cubic (fcc) NiFe encapsulated in a N‐doped carbon shell (fcc‐NiFe@NC). At the current densities of 10 and 100 mA cm−2, the hcp‐NiFe@NC with Fe/Ni ratio of ≈5.4 % only needs ultralow overpotentials of 226 mV and 263 mV versus reversible hydrogen electrode in 1.0 m KOH electrolyte, respectively, which were extremely lower than those of fcc‐NiFe@NC and most of other reported NiFe‐based electrocatalysts. We proposed that hcp‐NiFe possesses favorable electronic property to expedite the reaction on the NC surface, resulting higher catalytic activity for OER. This research provides a new insight to design more efficient electrocatalysts by considering the crystal phase correlated electronic property.

Asymmetric Total Syntheses of the Akuammiline Alkaloids (−)‐Strictamine and (−)‐Rhazinoline

By Wenfei Li, Zhitao Chen, Di Yu, Xin Peng, Guohua Wen, Siqi Wang, Fei Xue, Xiao‐Yu Liu, Yong Qin from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 11, 2019.

Unified syntheses of the challenging methanoquinolizidine‐containing akuammiline alkaloids (−)‐strictamine and (−)‐rhazinoline have been achieved in an enantioselective fashion employing photocatalytic cascade and transition‐metal‐mediated cyclization reactions as key steps. Abstract Strictamine and rhazinoline are representative methanoquinolizidine‐containing akuammiline alkaloids that possess different stereochemistry at the C16 position. A unified approach to the enantioselective total syntheses of these two molecules is described. The key steps in this synthesis include a photocatalytic intra/intermolecular type II radical cascade reaction, a Tsuji–Trost allylation, a palladium‐ or nickel‐mediated cyclization, and a late‐stage intramolecular N‐alkylation reaction.

Efficient Room‐Temperature Phosphorescence of a Solid‐State Supramolecule Enhanced by Cucurbit[6]uril

By Zhi‐Yuan Zhang, Yong Chen, Yu Liu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 11, 2019.

An uncommon phosphorescent effect of an organic single molecule enhanced by supramolecular assembly of host–guest complexation is reported. The chromophore bromophenyl‐methyl‐pyridinium (PY) gives an enhanced phosphorescent efficiency of 81.2 % under ambient conditions after complexation with cucurbit[6]uril. The strict encapsulation of cucurbit[6]uril suppresses the nonradiative relaxation and promotes intersystem crossing. Abstract Efficient emission of purely organic room‐temperature phosphorescence (RTP) is of great significant for potential application in optoelectronics and photobiology. Herein, we report an uncommon phosphorescent effect of organic single molecule enhanced by resulting supramolecular assembly of host–guest complexation. The chromophore bromophenyl‐methyl‐pyridinium (PY) with different counterions as guests display various phosphorescence quantum yields from 0.4 % to 24.1 %. Single crystal X‐ray diffraction results indicate that the chromophore with iodide counterion (PYI) exhibits the highest efficiency maybe due to the halogen‐bond interactions. Significantly, the nanosupramolecular assembly of PY chloride complexation with the cucurbit[6]uril gives a greatly enhanced phosphorescent quantum yield up to 81.2 % in ambient. Such great enhancement is because of the strict encapsulation of cucurbit[6]uril, which prevents the nonradiative relaxation and promotes intersystem crossing (ISC). This supramolecular assembly concept with counterions effect provides a novel approach for the improvement of RTP.

A Borocarbonitride Ceramic Aerogel for Photoredox Catalysis

By Zhishan Luo, Yuanxing Fang, Min Zhou, Xinchen Wang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 11, 2019.

A 3D borocarbonitride ceramic aerogel was successfully synthesized by biohydrogel templates for photoredox catalysis. The unique structures show good crystallinity and a tunable band gap, which promotes exciton dissociation and charge separation for an improved photocatalytic performance. This work affords a sustainable green method for fabricating BCN aerogels based on biotemplates and provides new opportunities in photocatalysis. Abstract Borocarbonitride (BCN) is a new type of photocatalyst, but bulk BCN shows a large band gap, and low surface area, and moderate activity for photocatalysis. Here, a three‐dimensional (3D) porous ceramic BCN aerogel was developed as an effective photocatalyst for relevant reactions. The unique structures endow the aerogel with an adjustable band gap and a high surface area, excellent stability, and improved crystallinity, which accelerates the separation and transfer of electron‐hole pairs and promotes catalytic kinetics, thus enhancing the performance of photocatalytic reactions for hydrogen generation and carbon dioxide reduction. This work supplies a low‐cost, convenient and green synthesis method for building ceramic aerogels, and it provides a simple colloid chemistry strategy combined with boron‐containing compounds to facilitate further innovative breakthroughs in the novel ceramic aerogel materials design and development in the field of catalysis.

A Nucleophilicity Scale for the Reactivity of Diazaphospholenium Hydrides: Structural Insights and Synthetic Applications

By Jingjing Zhang, Jin‐Dong Yang, Jin‐Pei Cheng from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 11, 2019.

P−H superhydrides: The unexpected philicity of P−H bonds in diazaphospholenes has made their applications to catalytic reductions a burgeoning field. A three‐parameter kinetic equation was used to evaluate their nucleophilicity parameters (N), which cover over ten N units. Kinetic studies imply their much superior hydricity over commonly used hydrides, with 2‐H‐1,3,2‐diazaphospholene being the strongest nucleophilic donor ever quantified by the Mayr equation. Abstract Nucleophilicity parameters (N, sN) of a group of representative diazaphospholenium hydrides were derived by kinetic investigations of their hydride transfer to a series of reference electrophiles with known electrophilicity (E) values, using the Mayr equation log k2=sN(N+E). The N scale covers over ten N units, ranging from the most reactive hydride donor (N=25.5) to the least of the scale (N=13.5). This discloses the highest N value ever quantified in terms of Mayr's nucleophilicity scales reported for neutral transition‐metal‐free hydride donors and implies an exceptional reactivity of this reagent. Even the least reactive hydride donor of this series is still a better hydride donor than those of many other nucleophiles such as the C−H, B−H, Si−H and transition‐metal M−H hydride donors. Structure–reactivity analysis reveals that the outstanding hydricity of 2‐H‐1,3,2‐diazaphospholene benefits from the unsaturated skeleton.

Reactive Amphiphilic Conjugated Polymers for Inhibiting Amyloid β Assembly

By Han Sun, Jing Liu, Shengliang Li, Lingyun Zhou, Jianwu Wang, Libing Liu, Fengting Lv, Qi Gu, Baoyang Hu, Yuguo Ma, Shu Wang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 11, 2019.

Disassembly: A poly(p‐phenylene vinylene) derivative functionalized with p‐nitrophenyl esters (PPV‐NP) inhibits the assembly of amyloid proteins, degrades preformed fibrils, and reduces the cytotoxicity of amyloid aggregations in living cells. PPV‐NP is attached to the proteins through hydrophobic interactions and irreversible covalent linkages. This innovative approach offers new insights into the development of therapeutic strategies for amyloidosis. Abstract Protein misfolding and aberrant aggregations are associated with multiple prevalent and intractable diseases. Inhibition of amyloid assembly is a promising strategy for the treatment of amyloidosis. Reported here is the design and synthesis of a reactive conjugated polymer, a poly(p‐phenylene vinylene) derivative, functionalized with p‐nitrophenyl esters (PPV‐NP) and it inhibits the assembly of amyloid proteins, degrades preformed fibrils, and reduces the cytotoxicity of amyloid aggregations in living cells. PPV‐NP is attached to the proteins through hydrophobic interactions and irreversible covalent linkage. PPV‐NP also exhibited the capacity to eliminate Aβ plaques in brain slices in ex vivo assays. This work represents an innovative attempt to inhibit protein pathogenic aggregates, and may offer insights into the development of therapeutic strategies for amyloidosis.

Photoacoustic Imaging of Nanoparticle Transport in the Kidneys at High Temporal Resolution

By Xingya Jiang, Bujie Du, Shaoheng Tang, Jer‐Tsong Hsieh, Jie Zheng from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Apr 11, 2019.

Photoacoustic imaging was used to visualize the transport of Au25(SG)18 nanoclusters through the aorta to the renal parenchyma and its subsequent filtration into the renal pelvis at a temporal resolution of 1 s, allowing the accurate quantification of the glomerular filtration rate of individual kidneys in normal and pathological conditions. This broadens the biomedical applications of engineered nanoparticles in preclinical kidney research. Abstract Noninvasive monitoring of kidney elimination of engineered nanoparticles at high temporal and spatial resolution will not only significantly advance our fundamental understandings of nephrology on the nanoscale, but also aid in the early detection of kidney disease, which affects more than 10 % of the worldwide population. Taking advantage of strong NIR absorption of the well‐defined Au25(SG)18 nanocluster, photoacoustic (PA) imaging was used to visualize its transport in situ through the aorta to the renal parenchyma and its subsequent filtrat