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NanoManufacturing

Michael De Volder, Engineering Department - IfM

Studying at Cambridge

Nanoscience News

Metal Halide Perovskite Nanorods: Shape Matters

By Chengxi Zhang, Jiayi Chen, Sheng Wang, Lingmei Kong, Simon W. Lewis, Xuyong Yang, Andrey L. Rogach, Guohua Jia from Wiley: Advanced Materials: Table of Contents. Published on Sep 28, 2020.

Metal halide perovskite nanorods show strong polarized emission, high optical gain, and improved charge transport, and thus hold promising applications in solar cells, light‐emitting diodes (LEDs), photodetectors, photodetectors/phototransistors, and lasers. Recent advances in the synthetic strategies, growth mechanism, and optical and electronic properties of these materials are discussed, and the emerging applications are highlighted. Abstract Quasi‐1D metal halide perovskite nanorods (NRs) are emerging as a type of materials with remarkable optical and electronic properties. Research into this field is rapidly expanding and growing in the past several years, with significant advances in both mechanistic studies of their growth and widespread possible applications. Here, the recent advances in 1D metal halide perovskite nanocrystals (NCs) are reviewed, with a particular emphasis on NRs. At first, the crystal structures of perovskites are elaborated, which is followed by a review of the major synthetic approaches toward perovskite NRs, such as wet‐chemical synthesis, substrate‐assisted growth, and anion exchange reactions, and discussion of the growth mechanisms associated with each synthetic method. Then, thermal and aqueous stability and the linear polarized luminescence of perovskite NRs are considered, followed by highlighting their applications in solar cells, light‐emitting diodes, photodetectors/phototransistors, and lasers. Finally, challenges and future opportunities in this rapidly developing research area are summarized.

Optimized Kinetics Match and Charge Balance Toward Potassium Ion Hybrid Capacitors with Ultrahigh Energy and Power Densities

By Yufan Peng, Rui Zhang, Binbin Fan, Weijian Li, Zhen Chen, Hui Liu, Peng Gao, Shibing Ni, Jilei Liu, Xiaohua Chen from Wiley: Small: Table of Contents. Published on Sep 28, 2020.

An integrated strategy consisting of charge/mass balance pursuance, electrolyte optimization, and tailored‐electrode design, is proposed to boost the electrochemical performance of potassium ion hybrid capacitors (PIHCs). The key parameters that determine the energy‐storage behavior are identified, and the general rules for high‐performance PIHCs design are proposed. This work provides a better fundamental understanding and invaluable guidance for high‐performance hybrid energy‐storage device design. Abstract Potassium ion hybrid capacitors (PIHCs) are of particular interest benefiting from high energy/power densities. However, challenges lie in the kinetic mismatch between battery‐type anode and capacitive‐type cathode, as well as the difficulty in achieving optimized charge/mass balance. These significantly sacrifice the electrochemical performance of PIHCs. Here, strategies including charge/mass balance pursuance, electrolyte optimization, and tailored electrode design, are employed, together, to address these challenges. The key parameters determining the energy storage properties of PIHCs are identified. Specifically, i) the good kinetic match between anode and cathode translates into the very small variation of cathode/anode mass ratio at various rates. This sets general rules for the pursuance of charge balance, and to maximize the electrochemical performance of hybrid devices. ii) A potassium bis(fluoroslufonyl)imide (KFSI)‐based electrolyte promotes better electrode kinetics and allows for the formation of more stable and intact solid electrolyte interphase layer, with respect to potassium hexafluorophosphate (KPF6)‐based electrolyte. And iii) hierarchically porous N/O codoped carbon nanosheets (NOCSs) with enlarged interlayer spacing, disordered structure, and abundant pyridinic‐N functional groups are advantageous in terms of high electronic/ionic transport dynamics and structural stability. All these together, contribute to the high energy/power density of the activated carbon//NOCSs PIHCs (113.4 Wh kg−1, at 17,000 W Kg−1).

Engineering Gadolinium‐Integrated Tellurium Nanorods for Theory‐Oriented Photonic Hyperthermia in the NIR‐II Biowindow

By Lile Dong, Kai Li, Ding Wen, Xuan Gao, Jing Feng, Hongjie Zhang from Wiley: Small: Table of Contents. Published on Sep 28, 2020.

The therapeutic evaluation of the biocompatible and multifunctional gadolinium‐integrated tellurium nanorods (Te–Gd) is evaluated at the cellular level as well as animal level, which all demonstrate that Te–Gd can be served as a multifunctional theranostic candidate for highly efficient theory‐oriented photonic hyperthermia of tumor in the near infrared II (NIR‐II) biowindow. Abstract Near‐infrared (NIR) light‐triggered hyperthermia has exhibited promising prospects in oncology therapy due to the unique merits including minimal invasiveness, monitorable, excellent therapeutic effect, and negligible side effects. Especially, the second NIR biowindow (NIR‐II, 1000–1700 nm) with less absorbance and scattering by skin tissue, and deep tissue penetration, has received extensive attention for photonic hyperthermia. Unfortunately, the dissatisfactory photothermal conversion efficiency (PCE) and cumbersome preparation process of photo‐driven heat conversion nanomaterials seriously hamper the future clinical application. To combat the aforementioned challenges, high imaging performance and desired therapeutic outcome 1D nanorods are constructed based on gadolinium‐integrated tellurium nanorods (Te–Gd). In this system, magnetic resonance (MR) imaging and X‐ray computed tomography (CT) imaging‐guided photonic hyperthermia can be easily implemented in cooperation with Te–Gd. Importantly, Te–Gd possesses high PCE (41%) in the NIR‐II biowindow because the transition of the excited electron can easily occur from the valence band (VB) to the conduction band (CB) on (1 0 1) and (1 0 2) crystal planes. Furthermore, the distinctive photostability, high tumor accumulation, as well as low systemic adverse effects of Te–Gd guarantee the potential in the clinic.

Rational Design of Sb@C@TiO2 Triple‐Shell Nanoboxes for High‐Performance Sodium‐Ion Batteries

By Ming Kong, Yan Liu, Bin Zhou, Kaixuan Yang, Jianfeng Tang, Ping Zhang, Wen‐Hua Zhang from Wiley: Small: Table of Contents. Published on Sep 28, 2020.

Sb@C@TiO2 triple‐shell nanoboxes (TSNBs) composed of an inner Sb hollow nanobox protected by a conductive carbon middle shell and a TiO2‐nanosheet‐constructed outer shell are synthesized through a template‐engaged galvanic replacement approach. Benefiting from the rational structural design,the Sb@C@TiO2 TSNBs exhibit enhanced sodium storage performance in terms of superior rate performance and outstanding long‐term cycling stability. Abstract Antimony is an attractive anode material for sodium‐ion batteries (SIBs) owing to its high theoretical capacity and appropriate sodiation potential. However, its practical application is severely impeded by its poor cycling stability caused by dramatic volumetric variations during sodium uptake and release processes. Here, to circumvent this obstacle, Sb@C@TiO2 triple‐shell nanoboxes (TSNBs) are synthesized through a template‐engaged galvanic replacement approach. The TSNB structure consists of an inner Sb hollow nanobox protected by a conductive carbon middle shell and a TiO2‐nanosheet‐constructed outer shell. This structure offers dual protection to the inner Sb and enough room to accommodate volume expansion, thus promoting the structural integrity of the electrode and the formation of a stable solid–electrolyte interface film. Benefiting from the rational structural design and synergistic effects of Sb, carbon, and TiO2, the Sb@C@TiO2 electrode exhibits superior rate performance (212 mAh g−1 at 10 A g−1) and outstanding long‐term cycling stability (193 mAh g−1 at 1 A g−1 after 4000 cycles). Moreover, a full cell assembled with a configuration of Sb@C@TiO2//Na3(VOPO4)2F displays a high output voltage of 2.8 V and a high energy density of 179 Wh kg−1, revealing the great promise of Sb@C@TiO2 TSNBs as the electrode in SIBs.

Modal Frustration and Periodicity Breaking in Artificial Spin Ice

By Robert Puttock, Alessandra Manzin, Volker Neu, Felipe Garcia‐Sanchez, Alexander Fernandez Scarioni, Hans W. Schumacher, Olga Kazakova from Wiley: Small: Table of Contents. Published on Sep 28, 2020.

Puttock and and co‐workers investigate how the inclusion of coupled nanomagnets in an artificial spin ice structure causes an energetically favorable disruption to the magnetic periodicity upon overcoming an energy barrier. A mix of Ising and chiral domains form under a controlled perturbation protocol, which alters the collective frustrated behavior across a correlated energy landscape. Abstract Here, an artificial spin ice lattice is introduced that exhibits unique Ising and non‐Ising behavior under specific field switching protocols because of the inclusion of coupled nanomagnets into the unit cell. In the Ising regime, a magnetic switching mechanism that generates a uni‐ or bimodal distribution of states dependent on the alignment of the field is demonstrated with respect to the lattice unit cell. In addition, a method for generating a plethora of randomly distributed energy states across the lattice, consisting of Ising and Landau states, is investigated through magnetic force microscopy and micromagnetic modeling. It is demonstrated that the dispersed energy distribution across the lattice is a result of the intrinsic design and can be finely tuned through control of the incident angle of a critical field. The present manuscript explores a complex frustrated environment beyond the 16‐vertex Ising model for the development of novel logic‐based technologies.

Understanding the Role of Metal–Organic Frameworks in Surface‐Enhanced Raman Scattering Application

By Chuanhui Huang, Ailin Li, Xiangyu Chen, Tie Wang from Wiley: Small: Table of Contents. Published on Sep 28, 2020.

Combining highly porous crystalline metal–organic frameworks (MOFs) with the surface‐enhanced Raman scattering (SERS) technique can achieve unprecedented advantages of high selectivity, high sensitivity, and expedience in analysis and detection. Herein, recent advances in research on the roles of MOFs in MOF‐SERS systems, particularly their structure‐to‐property correlation, are systematically highlighted. Abstract Metal–organic frameworks (MOFs), built from organic linkers and metal ions/clusters, have emerged as highly promising materials for wide applications. Combining highly porous crystalline MOFs with the surface‐enhanced Raman scattering (SERS) technique can achieve unprecedented advantages of high selectivity, high sensitivity, and expedience in analysis and detection. In this critical review, the aim is to present a comprehensive review of recent advances in understanding of the roles of MOFs in MOF‐SERS systems, particularly their structure‐to‐property correlation. Key examples are selected from representative literature to illustrate critical concepts and the MOF‐based property‐dependent applications are particularly emphasized. Finally, the barriers, future trends, and prospects for further advances in MOF‐SERS platforms are also discussed.

Cascade Reactions Catalyzed by Planar Metal–Organic Framework Hybrid Architecture for Combined Cancer Therapy

By Jing Mu, Liangcan He, Wenpei Fan, Wei Tang, Zhantong Wang, Chao Jiang, Dongyang Zhang, Yijing Liu, Hongzhang Deng, Jianhua Zou, Orit Jacobson, Junle Qu, Peng Huang, Xiaoyuan Chen from Wiley: Small: Table of Contents. Published on Sep 28, 2020.

A planar metal–organic framework (MOF)‐based composite is fabricated by in situ growth of ultrasmall gold nanoparticles and coloading of nitric oxide (NO) donor l‐Arginine into the MOF structure. Such engineered nanosheets proceed effective cascade reactions toward NO production in addition to combined photodynamic therapy, which offers a promising strategy for the development of advanced nanomedicine. Abstract Chemical transformation in cellular environment is critical for regulating biological processes and metabolic pathways. Harnessing biocatalytic cascades to produce chemicals of interest has become a research focus to benefit industrial and pharmaceutic areas. Nanoreactors, which can act as artificial cell‐like devices to organize cascade reactions, have been recently proposed for potential therapeutic applications for life‐threatening illnesses. Among various types of nanomaterials, there is a growing interest in 2D metal–organic frameworks (MOFs). By virtue of the ultralarge specific surface area, high porosity, and structural diversity, 2D MOF nanosheets hold great promise for a broad spectrum of biomedical use. Herein, a unique planar MOF‐based hybrid architecture (GMOF‐LA) is introduced by incorporating ultrasmall gold nanoparticles (Au NPs) as nanozyme and l‐Arginine (l‐Arg) as nitric oxide (NO) donor. The prepared Au NPs enable oxidation of glucose into hydrogen peroxide, which drives biocatalytic cascades to covert l‐Arg into NO. Interestingly, the well‐designed nanosheets not only possess excellent catalytical activity for NO generation, resulting in gas therapeutic effect, but also serve as a desired photosensitizer for photodynamic therapy. This study establishes a good example of exploring bioinspired nanoreactors for cooperative anticancer effect, which may pave the path for future “bench‐to‐bedside” design of nanomedicine.

Smart Bilayer Polyacrylamide/DNA Hybrid Hydrogel Film Actuators Exhibiting Programmable Responsive and Reversible Macroscopic Shape Deformations

By Yanhui Bi, Xiaoxue Du, Pingping He, Chunyan Wang, Chang Liu, Weiwei Guo from Wiley: Small: Table of Contents. Published on Sep 28, 2020.

Programmable stimuli‐responsive bilayer DNA hybrid hydrogel film actuators that can undergo reversible and macroscopic shape deformations at high speed are fabricated. By programming the sequences of incorporated DNA units, actuators that can respond to pH changes or the presence of metal ion/ligand stimuli are developed, which may have potential in future smart biosensing and biomedical applications. Abstract As a crucial instinct for the survival of organisms, adaptive smart deformation has been well shown via profusely astounding examples within biological morphogenesis in nature, which inspired the construction of biomimetic shape‐morphing materials with controlled actuating behaviors. Herein, the construction of nature‐inspired bilayer hydrogel film actuators, composed of a polyacrylamide hydrogel passive layer and a polyacrylamide‐DNA hybrid hydrogel active layer, which exhibited programmable stimuli‐responsive and reversible macroscopic shape deformations directed by the sequence of DNA crosslinking units in the active layer, is reported. As a proof‐of‐concept, the introduction of DNA i‐motif based crosslinking structures into the active layer, which can undergo pH‐stimulated formation and dissociation of crosslinking between polymers and therefore change the crosslinking density of the active layer, lead to the redistribution of the internal stresses within the bilayer structure, and result in the pH‐stimulated shape deformations. By programming the sequence of DNA units in the active layer, a Ag+/Cysteamine‐stimulated bilayer DNA hybrid hydrogel film actuator is further constructed and exhibits excellent actuation behaviors. Thanks to the micrometer‐scale thickness of the films, these actuators exhibit a high degree of macroscopic and reversible shape deformations at high speed, which may find use in future smart biosensing and biomedical applications.

Thu 19 Nov 15:00: On the Art of Wielding a Double-Edged Sword (or, Finessing Modern Networks)

From All Talks (aka the CURE list). Published on Sep 28, 2020.

On the Art of Wielding a Double-Edged Sword (or, Finessing Modern Networks)

Abstract Recent advances in networking technology have significantly increased network configurability, programmability, and flexibility. These advances have introduced programmability to all network components—from programmable switches and network cards to the deployment of configurable software switches on all nodes in an infrastructure.

This increase in network “softwarization” is a double-edged sword. On the one hand, network programmability facilitates the building of line-rate application-specific packet processing logic. This in turn enables building in-network system-specific optimizations, such as optimized distributed query processing, scheduling, and load balancing. In this talk, I will present FlairKV (NSDI ‘20), a key-value storage system that leverages programmable switches to significantly accelerate read operations.

On the other hand, increased network softwarization (perhaps not surprisingly) contributes to an increase in the frequency and complexity of network failures. Can modern systems tolerate these faults, and can we build a generic fault tolerance technique for them? In this talk, I will present NEAT (OSDI ‘18), a comprehensive study of the impact of network partitioning failures on modern systems. Moreover, we recently identified a peculiar type of network fault called partial partitioning. I will present NIFTY (OSDI ‘20), a generic fault tolerance technique for partial partitions.

Bio: Samer Al-Kiswany is an assistant professor at David Cheriton School of Computer Science at the University of Waterloo, Canada. His research interest is in distributed systems, networking, and data management and processing engines. In particular, his work focuses on reconsidering systems design in light of recent changes in cloud applications and platforms. Samer received his PhD from the University of British Columbia in 2013. After his PhD, he joined the University of Wisconsin–Madison as a postdoctoral fellow. Dr. Al-Kiswany is the recipient of ten national and international awards, including the Killam Doctoral Fellowship, the NSERC Postdoctoral Fellowship, and the IEEE George Michael HPC Fellowship.

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Fri 02 Oct 08:45: GRAND ROUNDS: "Becky...The case that kept on giving"

From All Talks (aka the CURE list). Published on Sep 28, 2020.

GRAND ROUNDS: "Becky...The case that kept on giving"

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Salt to Taste: The Critical Roles Played by Inorganic Salts in Organozinc Formation and in the Negishi Reaction

By Michael G Organ, Philip Eckert, Sepideh Sharif from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 28, 2020.

The first cross‐coupling of organozinc nucleophiles with aryl halides was reported in 1977 by Negishi. Unknown to all at the time was the importance of salt additives that were often present as a byproduct from the organozinc preparation. For decades, these salt additives were overlooked until 2006 when it was discovered that two different, yet effective methods for preparing organozinc solutions (i.e. one with salt and one without) provided drastically different results. Since this finding, the exact role of salt additives in cross‐coupling has been debated in the catalysis community. In this review we highlight all the major discoveries regarding the influence of salt additives on the formation of organozinc reagents and their use in the Negishi reaction. These effects include solubilizing key intermediates, the formation of higher order zincates, product inhibition, catalyst protection and solvent effects.

Thu 03 Dec 11:30: Title to be confirmed

From All Talks (aka the CURE list). Published on Sep 28, 2020.

Title to be confirmed

Abstract not available

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A Gold Nanoparticle Nanonuclease Relying on a Zn(II) Mononuclear Complex

By Paolo M Scrimin, Joanna Czescik, Susanna Zamolo, Tamis Darbre, Riccardo Rigo, Claudia Sissi, Adam Pecina, Laura Riccardi, Marco De Vivo, Fabrizio Mancin from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 28, 2020.

Similarly to enzymes, functionalized gold nanoparticles efficiently catalyze chemical reactions, hence the term nanozymes. Here we present our results showing how surface‐passivated gold nanoparticles behave as synthetic nanonucleases, able to cleave pBR322 plasmid DNA with the highest efficiency reported so far for catalysts based on a single metal ion mechanism. Experimental and computational data indicate that we have been successful in creating a catalytic site precisely mimicking that suggested for natural metallonucleases relying on a single metal ion for their activity. It comprises one Zn(II) ion to which a phosphate diester of DNA is coordinated. Importantly, as in nucleic acids‐processing enzymes, a positively charged arginine plays a key role by assisting with transition state stabilization and by reducing the pK a of the nucleophilic alcohol of a serine. Our results also show how designing a catalyst for a model substrate (bis‐ p ‐nitrophenylphosphate) may provide wrong indications as for its efficiency when it is tested against the real target (plasmid DNA).

Thu 26 Nov 11:30: Title to be confirmed

From All Talks (aka the CURE list). Published on Sep 28, 2020.

Title to be confirmed

Abstract not available

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Thu 19 Nov 11:30: Title to be confirmed

From All Talks (aka the CURE list). Published on Sep 28, 2020.

Title to be confirmed

Abstract not available

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Thu 12 Nov 11:30: Title to be confirmed

From All Talks (aka the CURE list). Published on Sep 28, 2020.

Title to be confirmed

Abstract not available

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Thu 05 Nov 11:30: Title to be confirmed

From All Talks (aka the CURE list). Published on Sep 28, 2020.

Title to be confirmed

Abstract not available

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Wed 02 Dec 16:00: Title to be confirmed

From All Talks (aka the CURE list). Published on Sep 28, 2020.

Title to be confirmed

Abstract not available

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Thu 29 Oct 11:30: TBC

From All Talks (aka the CURE list). Published on Sep 28, 2020.

TBC

Abstract not available

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Thu 22 Oct 11:30: TBC

From All Talks (aka the CURE list). Published on Sep 28, 2020.

TBC

Abstract not available

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Thu 15 Oct 11:30: The effects of planetary-scale volcanism on Io's interior structure and evolution

From All Talks (aka the CURE list). Published on Sep 28, 2020.

The effects of planetary-scale volcanism on Io's interior structure and evolution

Global volcanism has dominated the evolution of many worlds from the early Earth at the time when life emerged, to potentially habitable ocean worlds like Enceladus. By affecting large proportions of planetary interiors, far below the surface expressions that we observe, planetary volcanism leads to thermal, structural, and chemical evolution, and in the case of the Earth, has facilitated life. Io is an extreme ‘end-member’ that allows us to study planetary volcanism in relative isolation from other processes. A complete picture of planetary volcanism requires an investigation of volcanic systems in the crust together with magmatic processes in the underlying mantle that fuel them. This is a significant challenge because crustal volcanic systems evolve on much shorter timescales than planetary mantles, which has led previous works to focus on each domain separately. I develop a new parametrisation for the rapid, complex processes of volcanic systems that allow them to be investigated alongside much slower mantle processes. With this approach I propose: a) the formation of magmatic intrusions is a fundamental part of Io’s crustal heat balance, and controls the crustal thickness; b) magmatism and volcanism leads to a stratification in Io’s mantle, predicting the formation of ultra-high-temperature lava at depth; c) Io’s long-wavelength topography and crustal thickness variations can be used to infer the underlying tidal heating distribution.

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H2‐free Re‐based catalytic dehydroxylation of aldaric acid to muconic and adipic acid esters

By Brigita Hočevar, Anže Prašnikar, Matej Huš, Miha Grilc, Blaž Likozar from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 28, 2020.

Being one of the most demanded dicarboxylic acids, adipic acid can be directly produced from renewable sources. Hexoses from (hemi)cellulose are oxidized to aldaric acids and subsequently catalytically dehydroxylated. Hitherto performed homogeneously, we present the first heterogeneous catalytic process for converting an aldaric acid into muconic and adipic acid. The contribution of leached Re from the solid pre‐reduced catalyst was also investigated with hot‐filtration test and found to be inactive for dehydroxylation. Corrosive or hazardous (HBr/H 2 ) reagents are eschewed in lieu of simple alcohols and solid Re/C catalysts in an inert atmosphere. At 120 °C, the carboxylic groups are protected by esterification, which prevents lactonisation in the absence of water or acidic sites. Dehydroxylation and partial hydrogenation yield monohexenoates (93%). For complete hydrogenation to adipate, a 16% higher activation barrier necessitates higher temperatures. The mechanism of selective removal of adjacent OH* groups on Re(0001) and the role of methanol in hydrogen transfer are elucidated by DFT calculations as well as XPS, chemisorption and HR‐TEM experiments.

Thu 26 Nov 15:30: How to study animal minds HPS Virtual Conversation

From All Talks (aka the CURE list). Published on Sep 28, 2020.

How to study animal minds

A great deal of work in comparative psychology – the study of human and nonhuman animal minds – is dedicated to the question of how to avoid bias. How do we ensure researchers are not anthropomorphising (or oversimplifying) their subjects? In her new book, How to Study Animal Minds (2020), Kristin Andrews argues that comparative psychologists should aim to integrate a wide range of approaches for studying animal minds, rather than focus on avoiding bias. This Virtual Conversation brings together four scholars working at the intersection of HPS and comparative psychology to explore the question, ‘how should we study animal minds?’.

Speakers: Kristin Andrews (York University), Mike Dacey (Bates College), Ali Boyle (University of Cambridge), Marta Halina (University of Cambridge)

HPS Virtual Conversation

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Thu 05 Nov 15:30: A material history of 16th-century astronomy? Anita McConnell Lecture

From All Talks (aka the CURE list). Published on Sep 28, 2020.

A material history of 16th-century astronomy?

I first encountered the history of science in Cambridge in the later 1960s, when a prominent narrative in the curriculum at HPS was something called ‘the astronomical revolution’. The thread to be followed in this narrative was planetary theory and it led to an understanding of historical ‘cosmology’. This was terrific – intellectual and technical stimulation, sustained by a compelling storyline and offering a fresh start for my flagging engagement with science. I may have emerged ignorant of the astrolabe and knowing little more about even the armillary sphere, but I was switched on to the history of science. Might it have been different? Could we write an account of 16th-century astronomy based on objects? Probably not, but for an hour or so, it’s worth a try.

Anita McConnell Lecture

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Thu 29 Oct 15:30: The history of the electric charge c. 1897–1906 through the lenses of perspectival realism

From All Talks (aka the CURE list). Published on Sep 28, 2020.

The history of the electric charge c. 1897–1906 through the lenses of perspectival realism

Scientists often disagree both that something is and about what it is. This kind of scientific disagreement is of great interest to historians of science, who might want to establish who really discovered some entity – e.g. whether it was Joseph Priestley rather than Antoine Lavoisier who discovered what we now call ‘oxygen’; or, whether it was George J. Stoney or J.J. Thomson who really discovered the electron, given that in his Nobel Prize speech Thomson was still calling his entity a ‘corpuscle’. But, historiographical debates aside, disagreement that something is and about what it is also raises pressing questions for philosophers with realist leanings. How are we to spell out the realist commitment in cases where scientists disagree about the nature of the entity? What is it like to be a realist in the face of scientific disagreement? This paper takes some steps towards answering this question by looking at the case of the electric charge. As it happens, at the turn of the last century, there was a disagreement about the nature of the electron as the bearer of the electric charge. And there were also different views about the electric charge and the reasons why it is a ‘natural unit’. Digging (briefly for limits of space here) into the history of this scientific disagreement around 1897–1906 is instructive for two different reasons. First, it helps elucidate the nature of disagreement. This was rooted not in scientists accepting or denying pieces of evidence, but rather in the way in which pieces of evidence, or, better, data, were embedded in different scientific perspectives and used for inferring a variety of phenomena, from which the electric charge could in turn be inferred. Second, a brief foray into the history of the electric charge can help us understand the exact nature of the realist commitment that is compatible with what I call ‘perspectival disagreement’.

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En Route Towards the Control of Luminescent, Optically‐Active 3D Architectures

By Carlos Romero Nieto, Frank Rominger, Philip Hindenberg from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 28, 2020.

π‐Extended systems are key components for the development of future organic electronic technologies. While conceiving molecules with improved properties is fundamental for the evolution of materials science, keeping control over the 3D arrangement of molecules represents an ever‐expanding challenge. Herein, a synthetic protocol to replace carbon atoms of π‐systems by dissymmetric phosphorus atoms is reported; in particular, it allowed for conceiving new fused phosphapyrene derivatives with improved properties. The presence of dissymmetric phosphorus atoms precluded the formation of excimers. X‐ray diffraction revealed that, meanwhile, strong intermolecular interactions are taking place in the solid state. The phosphapyrenes photoluminesce in the visible region with high quantum yields; importantly, they are CD‐active. In addition, the unique non‐planar features of phosphorus atoms allowed for the control of the 3D arrangement of molecules, rendering lemniscate‐like structures. Based on our discoveries, we envisage the possibility to construct higher‐order, chiral 3D architectures from larger phosphorus‐containing π‐systems.

Thu 22 Oct 15:30: Linking the global and the local: the double burden of child malnutrition in Jamaica, c. 1960–2020

From All Talks (aka the CURE list). Published on Sep 28, 2020.

Linking the global and the local: the double burden of child malnutrition in Jamaica, c. 1960–2020

Following independence in 1962, successive governments in Jamaica tried to reduce the high rate of child malnutrition. Malnutrition was the result of a lack of protein and calories, also called PCM – Protein Calorie Malnutrition – and was a leading cause of death. Since the 1990s, however, the island has witnessed a nutrition transition with child malnutrition declining and child obesity increasing. Based on, amongst others, medical journals, newspaper reports, ministry papers, and reports of international agencies, this paper first of all explores how child malnutrition was measured and analysed; the various proposals put forward and implemented to reduce it; and the success rate of these policies. It will show that over time child malnutrition and the solutions proposed became increasingly localised; that is, greater attention was paid to the socio-economic and cultural context of pre-school children and their families and there was less reliance on outside agencies to reduce PCM . The paper will then move on to trace the rise in child obesity levels and show that contrary to the UK, US and many other western countries, child obesity in Jamaica is largely associated with higher income groups. Although child obesity has rapidly increased – in 2017 some 10.3% of children were obese – very few attempts have so far been made to localise the problem. The paper will explain why only recently campaigns – both government and NGO funded – have been started to address child obesity.

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Thu 19 Nov 15:30: The case for modelled democracy

From All Talks (aka the CURE list). Published on Sep 28, 2020.

The case for modelled democracy

The fact that most of us are ignorant on politically relevant matters presents a problem for democracy. In light of this, some have suggested that we impose epistemic constraints on democratic participation, and specifically that the franchise be restricted along competency lines – a suggestion that in turn runs the risk of violating a long-standing condition on political legitimacy to the effect that legitimate political arrangements cannot be open to reasonable objections. In this talk, I outline a way to solve the problem of public ignorance without restricting the franchise. The proposal involves filtering the electoral input of a universal franchise through a statistical model that simulates what the public’s political preferences would be, were it informed on politically relevant matters. The result is modelled democracy. I make the case that such democracy both solves the problem of public ignorance and satisfies the aforementioned condition on legitimacy.

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Thu 12 Nov 15:30: Africa, race and the most expensive vaccine yet: stakes of hepatitis B immunisation research in Senegal and the Gambia

From All Talks (aka the CURE list). Published on Sep 28, 2020.

Africa, race and the most expensive vaccine yet: stakes of hepatitis B immunisation research in Senegal and the Gambia

Among the earliest and most ambitious experiments of hepatitis B vaccine happened in West Africa from the mid 1970s to the mid 1980s. Yet both plasma and recombinant vaccines for this virus, which hit the market as the most expensive vaccines yet, were not widely provided in Africa until the 2000s. In this paper, I examine relations and disjunctions between the politics of experimentation and those of vaccine distribution across spaces (and times) of economic, epidemiological and racialised difference. My focus is on the planning of a research programme partially implemented in Senegal from the late 1970s, and another launched in 1986 as the Gambia Hepatitis Intervention Study. I show how the logics underpinning this research – to use vaccination as an experimental device for generating aetiological evidence of viral cancer causation – made it acceptable to test a technology that was expected to remain ‘too expensive for Africa’ in the foreseeable future, and discuss how not just patterns of accessibility but their modes of rendering acceptable were racialised.

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Fri 30 Oct 08:45: Where is the African meningitis belt now?

From All Talks (aka the CURE list). Published on Sep 28, 2020.

Where is the African meningitis belt now?

Abstract not available

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Fri 09 Oct 08:45: The role of infectious mammalian prions in disease phenotype

From All Talks (aka the CURE list). Published on Sep 28, 2020.

The role of infectious mammalian prions in disease phenotype

Abstract not available

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Fri 16 Oct 16:00: A study on coupled source-receiver interaction

From All Talks (aka the CURE list). Published on Sep 28, 2020.

A study on coupled source-receiver interaction

Abstract not available

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Fri 30 Oct 16:00: An ambient vibration-based bridge scour monitoring system

From All Talks (aka the CURE list). Published on Sep 28, 2020.

An ambient vibration-based bridge scour monitoring system

Abstract not available

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Fri 06 Nov 16:00: Title - tbc

From All Talks (aka the CURE list). Published on Sep 28, 2020.

Title - tbc

Abstract not available

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Fri 13 Nov 16:30: Title - tbc

From All Talks (aka the CURE list). Published on Sep 28, 2020.

Title - tbc

Abstract not available

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Fri 13 Nov 16:00: Wind dynamics of tall timber buildings

From All Talks (aka the CURE list). Published on Sep 28, 2020.

Wind dynamics of tall timber buildings

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Interaction of fibrinogen–magnetic nanoparticle bioconjugates with integrin reconstituted into artificial membranes

By Mihaela Delcea from RSC - Nanoscale latest articles. Published on Sep 28, 2020.

Nanoscale, 2020, Advance Article
DOI: 10.1039/D0NR04181E, Paper
Open Access Open Access
Creative Commons Licence  This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
Ulrike Martens, Una Janke, Sophie Möller, Delphine Talbot, Ali Abou-Hassan, Mihaela Delcea
Fibrinogen provides colloidal stability to maghemite NPs and fibrinogen–NP bioconjugates interact with integrin-containing artificial membranes as model system for platelets.
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CO2-gated anodic aluminum oxide based nanocomposite membrane for de-emulsification

By Patrick Theato from RSC - Nanoscale latest articles. Published on Sep 28, 2020.

Nanoscale, 2020, Accepted Manuscript
DOI: 10.1039/D0NR04248J, Paper
Open Access Open Access
Xia Huang, Hatice Mutlu, Patrick Theato
A carbon dioxide stimuli responsive organic-inorganic nanocomposite membrane was constructed on the basis of through-hole anodic aluminum oxide (AAO) template. The composite was prepared via surface-initiated reversible addition-fragmentation chain-transfer (SI-RAFT)...
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Iron nanoparticle templates for constructing 3D graphene framework with enhanced performance in sodium-ion batteries

By Yuta Nishina from RSC - Nanoscale latest articles. Published on Sep 28, 2020.

Nanoscale, 2020, Accepted Manuscript
DOI: 10.1039/D0NR05682K, Paper
Benoit Campeon, Wang Chen, Yuta Nishina
This study examines the synthesis and electrochemical performance of three-dimensional graphene for use as Li-ion batteries and Na-ion batteries. The in-situ formation of iron hydroxide nanoparticles (Fe(OH)x NPs) of various...
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TiS2/Celgard separator as efficient polysulfide shuttling inhibitor for high performance lithium-sulfur batteries

By Da Zhan from RSC - Nanoscale latest articles. Published on Sep 28, 2020.

Nanoscale, 2020, Accepted Manuscript
DOI: 10.1039/D0NR06429G, Paper
Guanfusheng Yan, Chuan Xu, Zhaohui Meng, Mingzhen Hou, Wen Yan, Naibo Lin, Linfei Lai, Da Zhan
The rapid capacity loss caused by the shuttling effect of polysulfide is one of the great challenges of Li-S batteries. In this work, we adopted a simple solid-phase sintering method...
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Smart strategies overcoming tumor hypoxia toward enhancement of cancer therapy

By Xiaolong Liang from RSC - Nanoscale latest articles. Published on Sep 28, 2020.

Nanoscale, 2020, Accepted Manuscript
DOI: 10.1039/D0NR05501H, Review Article
Menghong Xu, Ping Wang, Suhui Sun, Liquan Gao, LIhong Sun, Lulu Zhang, Jinxia Zhang, Shumin Wang, Xiaolong Liang
Hypoxia, as a typical factor composing tumor microenvironment, plays a vital role in tumor treatment resistance, tumor invasion and migration. Hypoxia inducible factor (HIF), as the vital response element of...
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Spatially pinned surface plasmon through short-circuiting electronic oscillation in waveguide-sustained SPPs

By Xinping Zhang from RSC - Nanoscale latest articles. Published on Sep 28, 2020.

Nanoscale, 2020, Accepted Manuscript
DOI: 10.1039/D0NR05991A, Paper
Yulan Fu, Xiaochen Zhang, Meng Wang, Xinping Zhang
A spatially pinned surface plasmon is constructed by connecting a gold nanoshell grating by a planar gold nanofilm, forming a periodical array of gold nanoloops. Dramatic electric field modulation and...
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Highly Aligned Carbon Nanotubes and their Sensor Applications

By Seung Hwan Chang from RSC - Nanoscale latest articles. Published on Sep 28, 2020.

Nanoscale, 2020, Accepted Manuscript
DOI: 10.1039/D0NR05951J, Paper
Imtisal Akhtar, Seung Hwan Chang
Flexible electronics are comprising carbon nanotube (CNT) membranes and polymer composites are used in diverse applications, including health monitoring. Devices prepared using such electronics need to exhibit acceptable sensitivity at...
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Controlling the non-linear emission of upconversion nanoparticles to enhance super-resolution imaging performance

By James Piper from RSC - Nanoscale latest articles. Published on Sep 28, 2020.

Nanoscale, 2020, Accepted Manuscript
DOI: 10.1039/D0NR04809G, Paper
Open Access Open Access
Creative Commons Licence  This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
Simone De Camillis, Peng Ren, Yueying Cao, Martin Ploschner, Denitza Denkova, Xianlin Zheng, Yiqing Lu, James Piper
Upconversion nanoparticles (UCNPs) exhibit unique optical properties such as photo-emission stability, large anti-Stokes shift, and long excited-state lifetimes, allowing significant advances in a broad range of applications from biomedical sensing...
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Memristors Based on 2D Materials as an Artificial Synapse for Neuromorphic Electronics

By Woong Huh, Donghun Lee, Chul‐Ho Lee from Wiley: Advanced Materials: Table of Contents. Published on Sep 27, 2020.

The recent progress regarding memristors based on 2D materials for neuromorphic electronics is reviewed. They are categorized by their various materials, structures, and mechanisms. Owing to their outstanding synaptic characteristics, neuromorphic devices based on 2D materials offer excellent performance, energy‐efficient operation, and modifiable synaptic functions applicable to complex learning. Abstract The memristor, a composite word of memory and resistor, has become one of the most important electronic components for brain‐inspired neuromorphic computing in recent years. This device has the ability to control resistance with multiple states by memorizing the history of previous electrical inputs, enabling it to mimic a biological synapse in the neural network of the human brain. Among many candidates for memristive materials, including metal oxides, organic materials, and low‐dimensional nanomaterials, 2D layered materials have been widely investigated owing to their outstanding physical properties and electrical tunability, low‐power‐switching capability, and hetero‐integration compatibility. Hence, a large number of experimental demonstrations on 2D material‐based memristors have been reported showing their unique memristive characteristics and novel synaptic functionalities, distinct from traditional bulk‐material‐based systems. Herein, an overview of the latest advances in the structures, mechanisms, and memristive characteristics of 2D material‐based memristors is presented. Additionally, novel strategies to modulate and enhance the synaptic functionalities of 2D‐memristor‐based artificial synapses are summarized. Finally, as a foreseeing perspective, the potentials and challenges of these emerging materials for future neuromorphic electronics are also discussed.

Recent Progress in Engineering the Atomic and Electronic Structure of Electrocatalysts via Cation Exchange Reactions

By Tao Ling, Mietek Jaroniec, Shi‐Zhang Qiao from Wiley: Advanced Materials: Table of Contents. Published on Sep 27, 2020.

Further development of electrocatalysts for renewable energy devices requires the design of catalytic materials at the atomic/electronic level, which is a grand challenge. The recent advances in the cation exchange strategy, a powerful tool for fine‐tuning atomic/electronic structure of electrocatalysts through surface faceting, heteroatom doping, defects formation, and strain modulation, are reviewed. Abstract In the past few decades, tremendous advances have been made in electrocatalysis due to the rational design of electrocatalysts at the nanoscale level. Further development requires engineering electrocatalysts at the atomic level, which is a grand challenge. Here, the recent advances in cation exchange strategy, which is a powerful tool for fine‐tuning atomic structure of electrocatalysts via surface faceting, heteroatom doping, defects formation, and strain modulation, are the main focus. Proper atomic structure engineering effectively adjusts the electronic structure, and thus enhances the electronic conductivity and facilitates the adsorption/desorption of reaction intermediates. By virtue, the cation exchange strategy greatly boosts the intrinsic and apparent activities of electrocatalysts and shows a great potential toward design of new energy conversion devices, such as water splitting devices and metal–air batteries. It is believed that cation exchange offers new insights and opportunities for the rational design of a new generation of electrocatalysts.

Fri 09 Oct 14:00: Title to be confirmed

From All Talks (aka the CURE list). Published on Sep 27, 2020.

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Air‐Stable Low‐Symmetry Narrow‐Bandgap 2D Sulfide Niobium for Polarization Photodetection

By Yang Wang, Peisong Wu, Zhen Wang, Man Luo, Fang Zhong, Xun Ge, Kun Zhang, Meng Peng, Yan Ye, Qing Li, Haonan Ge, Jiafu Ye, Ting He, Yunfeng Chen, Tengfei Xu, Chenhui Yu, Yueming Wang, Zhigao Hu, Xiaohao Zhou, Chongxin Shan, Mingsheng Long, Peng Wang, Peng Zhou, Weida Hu from Wiley: Advanced Materials: Table of Contents. Published on Sep 27, 2020.

Novel 2D anisotropic sulfide niobium (NbS3) is introduced into the material family by demonstrating its in‐plane structure, phonon vibrations, and electrical and optical anisotropies. Meaningfully, the NbS3 Schottky photodetectors exhibit broadband detection sensitivity (400–10 600 nm), excellent response time (as fast as 11 µs), photoelectrical dichroic ratio (1.84), and high‐quality polarization imaging. Abstract Low‐symmetry 2D materials with unique anisotropic optical and optoelectronic characteristics have attracted a lot of interest in fundamental research and manufacturing of novel optoelectronic devices. Exploring new and low‐symmetry narrow‐bandgap 2D materials will be rewarding for the development of nanoelectronics and nano‐optoelectronics. Herein, sulfide niobium (NbS3), a novel transition metal trichalcogenide semiconductor with low‐symmetry structure, is introduced into a narrowband 2D material with strong anisotropic physical properties both experimentally and theoretically. The indirect bandgap of NbS3 with highly anisotropic band structures slowly decreases from 0.42 eV (monolayer) to 0.26 eV (bulk). Moreover, NbS3 Schottky photodetectors have excellent photoelectric performance, which enables fast photoresponse (11.6 µs), low specific noise current (4.6 × 10−25 A2 Hz−1), photoelectrical dichroic ratio (1.84) and high‐quality reflective polarization imaging (637 nm and 830 nm). A room‐temperature specific detectivity exceeding 107 Jones can be obtained at the wavelength of 3 µm. These excellent unique characteristics will make low‐symmetry narrow‐bandgap 2D materials become highly competitive candidates for future anisotropic optical investigations and mid‐infrared optoelectronic applications.

Broad‐Spectral‐Range Sustainability and Controllable Excitation of Hyperbolic Phonon Polaritons in α‐MoO3

By Weikang Dong, Ruishi Qi, Tiansheng Liu, Yi Li, Ning Li, Ze Hua, Zirui Gao, Shuyuan Zhang, Kaihui Liu, Jiandong Guo, Peng Gao from Wiley: Advanced Materials: Table of Contents. Published on Sep 27, 2020.

Hyperbolic phonon polaritons in α‐MoO3 are measured in a broad spectral range using electron energy loss spectroscopy. Polaritons with different dispersion types can be sustained in multiple Reststrahlen bands covering both mid‐ and far‐infrared frequencies, and can be selectively excited by the electron beam. These findings provide new opportunities in nanophotonic applications such as directed light propagation and hyperlensing. Abstract Hyperbolic phonon polaritons (HPhPs) in orthorhombic‐phase molybdenum trioxide (α‐MoO3) show in‐plane hyperbolicity, great wavelength compression, and ultralong lifetime, therefore holding great potential in nanophotonic applications. However, its polaritonic response in the far‐infrared (FIR) range remains unexplored due to challenges in experimental characterization. Here, monochromated electron energy loss spectroscopy (EELS) in a scanning transmission electron microscope (STEM) is used to probe HPhPs in α‐MoO3 in both mid‐infrared (MIR) and FIR frequencies and correlate their behaviors with microstructures and orientations. It is found that low structural symmetry leads to various phonon modes and multiple Reststrahlen bands (RBs) over a broad spectral range (over 70 meV) and in different directions (55–63 meV and 119–125 meV along the b‐axis, 68–106 meV along the c‐axis, and 101–121 meV along the a‐axis). These HPhPs can be selectively excited by controlling the direction of swift electrons. These findings provide new opportunities in nanophotonic and optoelectronic applications, such as directed light propagation, hyperlenses, and heat transfer.

Elemental sulfur enabled divergent synthesis of disulfides, diselenides and polythiophenes from β‐CF3‐1,3‐enynes

By Shengnan Jin, Shi-Jun Li, Xingxing Ma, Jianke Su, Haohua Chen, Yu Lan, Qiuling Song from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 27, 2020.

Divergent synthesis for precise constructions of cyclic unsymmetrical diaryl disulfides or diselenides and polythiophenes from CF 3 ‐containing 1,3‐enynes and S 8 was developed when the ortho group is F, Cl, Br and NO 2 on aromatic rings. Meanwhile, disulfides (diselenides) were also quickly constructed when the ortho group is H. These transformations undergo cascade thiophene construction/selective C 3 ‐position thiolation process, featuring simple operations, divergent synthesis, broad substrate scope, readily available starting materials as well as valuable products. A novel plausible radical annulation process was proposed and validated by DFT calculations for the first time. A series of derivatizations about the thiophene (TBT) and disulfides were also well represented.

Synthesis and Properties of a Cyclohexa‐2,7‐Anthrylene Ethynylene Derivative

By Hironori Matsuki, Keisuke Okubo, Yuta Takaki, Yoshiki Niihori, Masaaki Mitsui, Eiichi Kayahara, Shigeru Yamago, Kenji Kobayashi from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 27, 2020.

The synthesis of a cyclohexa‐2,7‐(4,5‐diaryl)anthrylene ethynylene 1 was achieved for the first time by using 1,8‐diaryl‐3,6‐diborylanthracene and 1,8‐diaryl‐3,6‐diiodoanthracene as key synthetic intermediates. Macrocycle 1 possesses a planar conformation of approximately D6h symmetry, because of the triple bond linker between the anthracene units at the 2,7‐positions. It was confirmed that macrocycle 1, bearing bulky substituents at the outer peripheral positions, behaves as a monomeric form in solution without π‐stacking self‐association. Macrocycle 1 has an inner cavity size that allows specific inclusion of [9]cycloparaphenylene ([9]CPP), but not [8]CPP or [10]CPP, through aromatic edge‐to‐face CH‐π interaction.

[ASAP] Unraveling the Importance of Noncovalent Interactions in Asymmetric Hydroformylation Reactions

By Yuvraj Dangat, Sahil Popli, and Raghavan B. Sunoj from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Sep 27, 2020.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.0c06942

Fri 20 Nov 16:00: Title to be confirmed

From All Talks (aka the CURE list). Published on Sep 26, 2020.

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Discovery of Self‐Assembling Small Molecules as Vaccine Adjuvants

By Shuyu Jin, Hue Thi Vu, Kou Hioki, Naotaka Noda, Hiroki Yoshida, Toru Shimane, Shigenari Ishizuka, Ippei Takashima, Yoshiyuki Mizuhata, Kathleen Beverly Pe, Tetsuya Ogawa, Naoya Nishimura, Daniel Packwood, Norihiro Tokitoh, Hiroki Kurata, Sho Yamasaki, Ken J Ishii, Motonari Uesugi from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 26, 2020.

Immune potentiators, termed adjuvant, trigger early innate immune responses to ensure the generation of robust and long‐lasting adaptive immune responses of vaccines. Here we present study that takes advantage of a self‐assembling small molecule library for the development of a novel vaccine adjuvant. Cell‐based screening of the library and subsequent structural optimization led to the discovery of a simple, chemically tractable deoxycholate derivative (molecule 6 , also named cholicamide) whose well‐defined nano‐assembly potently elicits innate immune responses in macrophages and dendritic cells. Functional and mechanistic analyses indicate that the virus‐like assembly is engulfed inside cells and stimulates the innate immune response through toll‐like receptor 7 (TLR7), an endosomal TLR that detects single‐stranded viral RNA. As an influenza vaccine adjuvant in mice, molecule 6 was as potent as Alum, a clinically used adjuvant. The studies described here paves the way for a new approach to discovering and designing self‐assembling small‐molecule adjuvants against pathogens, including emerging viruses.

Decarboxylative Borylation of Stabilized and Activated Carbon Radicals

By Qiang Zhang, Xiaojuan Li, Weigang Zhang, Shengyang Ni, Yi Wang, Yi Pan from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 25, 2020.

A general decarboxylative borylation protocol of aliphatic and aromatic carboxylic acids has been developed. Both stabilized and activated aryl and alkyl radicals could be generated from the leaving‐group‐assisted N‐hydroxybenzimidoyl chloride esters, even trifluoroethyl substrates could be activated for further elaboration. Abstract Redox‐active esters (RAEs) as active radical precursors have been extensively studied for C−B bond formations. However, the analogous transformations of stabilized radicals from the corresponding acid precursors remain challenging owing to the strong preference towards single‐electron oxidation to the stable carbocations. This work describes a general strategy for rapid access to various aliphatic and aromatic boronic esters by mild photoinduced decarboxylative borylation. Both aryl and alkyl radicals could be generated from the leaving group‐assisted N‐hydroxybenzimidoyl chloride esters, even α‐CF3 substituted substrates could be activated for further elaboration.

Refolding of Cold‐Denatured Barstar Induced by Radio‐Frequency Heating: A New Method to Study Protein Folding by Real‐Time NMR Spectroscopy

By György Pintér, Harald Schwalbe from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 25, 2020.

A state‐of‐the‐art temperature‐jump probe head is used in combination with real‐time 2D NMR experiments to study the kinetics of folding of a cold‐denatured protein. Barstar contains two prolines that adopt a mix of cis and trans conformations in the cold‐denatured state. The high time resolution measurements reported here show evidence for multiple folding pathways related to proline isomerization. Abstract The C40A/C82A double mutant of barstar has been shown to undergo cold denaturation above the water freezing point. By rapidly applying radio‐frequency power to lossy aqueous samples, refolding of barstar from its cold‐denatured state can be followed by real‐time NMR spectroscopy. Since temperature‐induced unfolding and refolding is reversible for this double mutant, multiple cycling can be utilized to obtain 2D real‐time NMR data. Barstar contains two proline residues that adopt a mix of cis and trans conformations in the low‐temperature‐unfolded state, which can potentially induce multiple folding pathways. The high time resolution real‐time 2D‐NMR measurements reported here show evidence for multiple folding pathways related to proline isomerization, and stable intermediates are populated. By application of advanced heating cycles and state‐correlated spectroscopy, an alternative folding pathway circumventing the rate‐limiting cis‐trans isomerization could be observed. The kinetic data revealed intermediates on both, the slow and the fast folding pathway.

B‐Site Co‐Alloying with Germanium Improves the Efficiency and Stability of All‐Inorganic Tin‐Based Perovskite Nanocrystal Solar Cells

By Maning Liu, Hannu Pasanen, Harri Ali‐Löytty, Arto Hiltunen, Kimmo Lahtonen, Syeda Qudsia, Jan‐Henrik Smått, Mika Valden, Nikolai V. Tkachenko, Paola Vivo from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 25, 2020.

CsSn0.6Ge0.4I3 nanocrystals have been synthesized for the first time by a B‐site co‐alloying strategy. The introduction of Ge effectively decreases the high density of intrinsic Sn defects, resulting in an extended excitonic lifetime and enhanced solar cell performance. The stability of the new nanocrystals also improves owing to the effective protection of Sn2+ against oxidation. Abstract Colloidal lead‐free perovskite nanocrystals have recently received extensive attention because of their facile synthesis, the outstanding size‐tunable optoelectronic properties, and less or no toxicity in their commercial applications. Tin (Sn) has so far led to the most efficient lead‐free solar cells, yet showing highly unstable characteristics in ambient conditions. Here, we propose the synthesis of all‐inorganic mixture Sn‐Ge perovskite nanocrystals, demonstrating the role of Ge2+ in stabilizing Sn2+ cation while enhancing the optical and photophysical properties. The partial replacement of Sn atoms by Ge atoms in the nanostructures effectively fills the high density of Sn vacancies, reducing the surface traps and leading to a longer excitonic lifetime and increased photoluminescence quantum yield. The resultant Sn‐Ge nanocrystals‐based devices show the highest efficiency of 4.9 %, enhanced by nearly 60 % compared to that of pure Sn nanocrystals‐based devices.

Oral Insulin Delivery Platforms: Strategies To Address the Biological Barriers

By Yufen Xiao, Zhongmin Tang, Junqing Wang, Chuang Liu, Na Kong, Omid C. Farokhzad, Wei Tao from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 25, 2020.

Oral insulin delivery holds great promise as a convenient and economical means of diabetes treatment. This Minireview provides an overview of representative advances in facilitating oral insulin delivery by overcoming biological barriers, including strategies centered on moieties‐mediated transport, cell‐penetrating peptide assisted permeation, smart oral robotics transport, and microenvironment‐responsive release. Abstract Diabetes mellitus is a lifelong metabolic disease that requires frequent subcutaneous injections of insulin. However, this method of administration can be associated with patient discomfort and local tissue infection. Oral delivery of insulin has been pursued as a more convenient method for diabetes treatment, given its likely superior patient compliance and convenience as well as cost‐effectiveness. However, various biological barriers hinder the clinical translation of oral insulin. The rapid development of nanotechnology over the last decade offers great promise in improving the bioavailability of oral insulin. This Minireview provides an overview of biological barriers to oral insulin delivery, summarizes significant technological advances, and outlines future perspectives in oral insulin formulations as well as their hypoglycaemic effects.

N‐Bridged Acyclic Trimeric Poly‐Cyclodiphosphazanes: Highly Tuneable Cyclodiphosphazane Building Blocks

By Xiaoyan Shi, Felix León, Ying Sim, Shina Quek, Gavin Hum, Yi Xin Joycelyn Khoo, Zi Xuan Ng, Mian Yang Par, How Chee Ong, Varun K. Singh, Rakesh Ganguly, Jack K. Clegg, Jesús Díaz, Felipe García from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 25, 2020.

We have synthesized a completely new family of acyclic trimeric cyclodiphosphazane compounds comprising NH, NiPr, NtBu and NPh bridging groups. These species possess both a highly tuneable intra‐terminal N(H)R moiety distance that can be readily modulated by varying the steric bulk of the bridging groups, in addition to topological flexibility upon incorporation of weak non‐bonding interactions. Abstract We have synthesized a completely new family of acyclic trimeric cyclodiphosphazane compounds comprising NH, NiPr, NtBu and NPh bridging groups. In addition, the first NH‐bridged acyclic dimeric cyclophosphazane has been produced. The trimeric species display highly tuneable characteristics so that the distance between the terminal N(H)R moieties can be readily modulated by the steric bulk present in the bridging groups (ranging from ≈6 to ≈10 Å). Moreover, these species exhibit pronounced topological changes when a weak non‐bonding NH⋅⋅⋅π aryl interaction is introduced. Finally, the NH‐bridged chloride binding affinities have been calculated and benchmarked along with the existing experimental data available for monomeric cyclodiphosphazanes. Our results underscore these species as promising hydrogen bond donors for supramolecular host–guest applications.

Fragment‐Based Stabilizers of Protein–Protein Interactions through Imine‐Based Tethering

By Madita Wolter, Dario Valenti, Peter J. Cossar, Laura M. Levy, Stanimira Hristeva, Thorsten Genski, Torsten Hoffmann, Luc Brunsveld, Dimitrios Tzalis, Christian Ottmann from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 25, 2020.

A novel concept for optimizing orthosteric protein–protein interaction (PPI) stabilization is reported. Increasing interactions with the protein partner that contributes less to the composite binding pocket of the stabilizer (NF‐κB, red surface) results in increased stabilization, whereas further enhancing the interaction with the dominant partner protein (14‐3‐3, white surface) does not contribute to the stabilizing effect. Abstract Small‐molecule stabilization of protein–protein interactions (PPIs) is a promising concept in drug discovery, however the question how to identify or design chemical starting points in a “bottom‐up” approach is largely unanswered. We report a novel concept for identifying initial chemical matter for PPI stabilization based on imine‐forming fragments. The imine bond offers a covalent anchor for site‐directed fragment targeting, whereas its transient nature enables efficient analysis of structure–activity relationships. This bond enables fragment identification and optimisation using protein crystallography. We report novel fragments that bind specifically to a lysine at the PPI interface of the p65‐subunit‐derived peptide of NF‐κB with the adapter protein 14‐3‐3. Those fragments that subsequently establish contacts with the p65‐derived peptide, rather than with 14‐3‐3, efficiently stabilize the 14‐3‐3/p65 complex and offer novel starting points for molecular glues.

Direct Intermediate Regulation Enabled by Sulfur Containers in Working Lithium–Sulfur Batteries

By Jin Xie, Yun‐Wei Song, Bo‐Quan Li, Hong‐Jie Peng, Jia‐Qi Huang, Qiang Zhang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 25, 2020.

Lithium polysulfide intermediates are directly regulated by the sulfur container PESn in working lithium sulfur batteries. Through reversible storage and release of the sulfur species, the container molecule converts small PSs into large organosulfur species, endowing changed electrochemical behaviors to lithium–sulfur batteries. Abstract Polysulfide intermediates (PSs), the liquid‐phase species of active materials in lithium–sulfur (Li‐S) batteries, connect the electrochemical reactions between insulative solid sulfur and lithium sulfide and are key to full exertion of the high‐energy‐density Li‐S system. Herein, the concept of sulfur container additives is proposed for the direct modification on the PSs species. By reversible storage and release of the sulfur species, the container molecule converts small PSs into large organosulfur species. The prototype di(tri)sulfide‐polyethylene glycol sulfur container is highly efficient in the reversible PS transformation to multiply affect electrochemical behaviors of sulfur cathodes in terms of liquid‐species clustering, reaction kinetics, and solid deposition. The stability and capacity of Li‐S cells was thereby enhanced. The sulfur container is a strategy to directly modify PSs, enlightening the precise regulation on Li‐S batteries and multi‐phase electrochemical systems.

Suppressing Strong Exciton–Phonon Coupling in Blue Perovskite Nanoplatelet Solids by Binary Systems

By Shaomin Peng, Qi Wei, Bingzhe Wang, Zhipeng Zhang, Hongcheng Yang, Guotao Pang, Kai Wang, Guichuan Xing, Xiao Wei Sun, Zikang Tang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 25, 2020.

The effective suppression of exciton–phonon interactions of blue emissive CsPbBr3 nanoplatelets (NPLs) is realized by constructing binary NPL systems. The exciton–phonon coupling strength can be significantly reduced two times. Additionally, the energy transfer between binary NPLs originated from Förster resonance energy transfer (FRET) effect occurs within picoseconds, efficiently competing with the phonon interactions. Abstract Quasi‐two‐dimensional (2D) perovskites are promising candidates for light generation owing to their high radiative rates. However, strong exciton–phonon interactions caused by mechanical softening of the surface act as a bottleneck in improving their suitability for a wide range of lighting and display applications. Moreover, it is not easily available to tune the phonon interactions in bulk films. Here, we adopt bottom‐up fabricated blue emissive perovskite nanoplatelets (NPLs) as model systems to elucidate and as well as tune the phonon interactions via engineering of binary NPL solids. By optimizing component domains, the phonon coupling strength can be reduced by a factor of 2 driven by the delocalization of 2D excitons in out‐of‐plane orientations. It shows the picosecond energy transfer originated from the Förster resonance energy transfer (FRET) efficiently competes with the exciton–phonon interactions in the binary system.

A Mechanochemical Reaction Cascade for Controlling Load‐Strengthening of a Mechanochromic Polymer

By Yifei Pan, Huan Zhang, Piaoxue Xu, Yancong Tian, Chenxu Wang, Shishuai Xiang, Roman Boulatov, Wengui Weng from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 25, 2020.

A mechanochemical reaction cascade for controlling load‐strengthening of a mechanochromic polymer is realized by using two comb polymers, each containing either spirothiopyran or a Diels–Alder adduct in the proximity of the branch points. The threshold force to trigger crosslinking is increased by ca. 1 nN and the minimum concentration of mechanophores required for crosslinking is decreased by 100‐fold compared to previous examples. Abstract We demonstrate an intermolecular reaction cascade to control the force which triggers crosslinking of a mechanochromic polymer of spirothiopyran (STP). Mechanochromism arises from rapid reversible force‐sensitive isomerization of STP to a merocyanine, which reacts rapidly with activated C=C bonds. The concentration of such bonds, and hence the crosslinking rate, is controlled by force‐dependent dissociation of a Diels–Alder adduct of anthracene and maleimide. Because the adduct requires ca. 1 nN higher force to dissociate at the same rate as that of STP isomerization, the cascade limits crosslinking to overstressed regions of the material, which are at the highest rate of material damage. Using comb polymers decreased the minimum concentration of mechanophores required to crosslinking by about 100‐fold compared to previous examples of load‐strengthening materials. The approach described has potential for controlling a broad range of reaction sequences triggered by mechanical load.

Electrochemically Induced Metal–Organic‐Framework‐Derived Amorphous V2O5 for Superior Rate Aqueous Zinc‐Ion Batteries

By Shenzhen Deng, Zishun Yuan, Zhiwei Tie, Changda Wang, Li Song, Zhiqiang Niu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 25, 2020.

In situ electrochemical induction of crystalline V2O3‐containing MIL‐88B(V) and carbon material yields a composite termed a‐V2O5@C. The a‐V2O5@C composites displays appreciable electrochemical performance due to the unique amorphous structure of V2O5 and its composite state with carbon. Abstract The electrochemical performance of vanadium‐oxide‐based cathodes in aqueous zinc‐ion batteries (ZIBs) depends on their degree of crystallinity and composite state with carbon materials. An in situ electrochemical induction strategy was developed to fabricate a metal–organic‐framework‐derived composite of amorphous V2O5 and carbon materials (a‐V2O5@C) for the first time, where V2O5 is in an amorphous state and uniformly distributed in the carbon framework. The amorphous structure endows V2O5 with more isotropic Zn2+ diffusion routes and active sites, resulting in fast Zn2+ transport and high specific capacity. The porous carbon framework provides a continuous electron transport pathway and ion diffusion channels. As a result, the a‐V2O5@C composites display extraordinary electrochemical performance. This work will pave the way toward design of ZIB cathodes with superior rate performance.

Pb18O8Cl15I5: A Polar Lead Mixed Oxyhalide with Unprecedented Architecture and Excellent Infrared Nonlinear Optical Properties

By Xinglong Chen, Qun Jing, Kang Min Ok from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 25, 2020.

Noncentrosymmetric Pb18O8Cl15I5, the first mixed oxyhalide in the PbO–PbCl2–PbI2 system, was found to have an unprecedented structural architecture featuring two types of oxocentered Pb–O units with different dimensionality (see picture). Characterization based on the large single crystal revealed that Pb18O8Cl15I5 outperformed AgGaS2 in key properties for high‐performance infrared nonlinear optical materials (see picture). Abstract To develop high‐performance nonlinear optical (NLO) materials for infrared (IR) applications, we have applied a rational element‐composition design strategy and investigated the unexplored PbO–PbCl2–PbI2 system. By doing so, we discovered a new polar lead mixed oxyhalide, Pb18O8Cl15I5, the first synthetic metal oxyhalide combining both Cl− and I−. Pb18O8Cl15I5 reveals an unprecedented structural feature with two different dimensional types of oxocentered Pb–O units, namely, [O4Pb8]8+ clusters and [OPb2]2+ chains. Centimeter‐sized single crystals of Pb18O8Cl15I5 have been successfully grown under ambient conditions. Remarkably, Pb18O8Cl15I5 satisfies all fundamental yet rigorous criteria for high‐performance IR NLO materials, exhibiting the widest IR transparency (up to 16.0 μm) among oxide‐based crystals, strong second‐harmonic generation response (1.05×AgGaS2), superior birefringence (0.086 at 636 nm), and a high laser‐induced damage threshold (8.5×AgGaS2).

Fri 13 Nov 15:30: Title to be confirmed

From All Talks (aka the CURE list). Published on Sep 25, 2020.

Title to be confirmed

Abstract not available

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In‐cell NMR of functional riboswitch aptamers in eukaryotic cells

By P. Broft, S. Dzatko, M. Krafcikova, Robert Hansel-Hertsch, A. Wacker, Volker Doetsch, L. Trantirek, Harald Schwalbe from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 25, 2020.

We report here the in‐cell NMR‐spectroscopic observation of the binding of the cognate ligand 2’‐deoxyguanosine to the aptamer domain of the bacterial 2’‐deoxyguanosine‐sensing riboswitch in eukaryotic cells, namely Xenopus laevis oocytes and in human HeLa cells. The riboswitch is sufficiently stable in both cell types to allow for detection of binding of the ligand to the riboswitch. Most importantly, we show that the binding mode established by in vitro characterization of this prokaryotic riboswitch is maintained in eukaryotic cellular environment. Our data also bring important methodological insights: Thus far, in‐cell NMR studies on RNA in mammalian cells have been limited to investigations of short (

Design, Identification and Evolution of Surface Ruthenium (II/III) Single‐Site for CO Activation

By Liqun Kang, Bolun Wang, Adam Thetford, Ke Wu, Mohsen Danaie, Qian He, Emma Gibson, Ling-Dong Sun, Hiroyuki Asakura, Richard Catlow, Feng Ryan Wang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 25, 2020.

Ru(II) compounds are widely used in catalysis, photocatalysis and medical applications. They are usually obtained in reductive environment as molecular O 2 can oxidize Ru(II) to Ru(III) and Ru(IV). Here we report the design, identification and evolution of an air‐stable surface ‐[bipy‐Ru(II)(CO) 2 Cl 2 ] site that is covalently mounted onto a polyphenylene framework. Such Ru(II) site was obtained by reduction of ‐[bipy‐Ru(III)Cl 4 ] ‐ with simultaneous ligand exchange from Cl ‐ to CO. This structural evolution was witnessed by a combination of in situ X‐ray and infrared spectroscopy studies. The ‐[bipy‐Ru(II)(CO) 2 Cl 2 ] site enables oxidation of CO with a turnover frequency of 0.73 × 10 ‐2 s ‐1 at 462 K, while the Ru(III) site is completely inert. This work contributes to the studies of structure‐activity relationship by demonstrating a practical control over both geometric and electronic structures of single‐site catalysts at molecular level, which can be further applied in other single site catalyst researches.

Fri 13 Nov 15:00: Title to be confirmed

From All Talks (aka the CURE list). Published on Sep 25, 2020.

Title to be confirmed

Abstract not available

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Wed 18 Nov 15:00: Title to be confirmed

From All Talks (aka the CURE list). Published on Sep 25, 2020.

Title to be confirmed

Abstract not available

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Fri 06 Nov 14:00: Plato’s cube and the natural geometry of fragmentation

From All Talks (aka the CURE list). Published on Sep 25, 2020.

Plato’s cube and the natural geometry of fragmentation

Plato associated regular polyhedra with the classical Elements, in particular, he associated Earth with the cube. His views have been broadly regarded, at best, as metaphors.

However, if we approximate natural fragments by convex polyhedra and count the respective numbers for faces, vertices and edges then in most cases we find averages close to 6,8,12, the values corresponding to the cube.

I will explain this phenomenon by using the theory of convex mosaics, geometric computer simulations of such mosaics, discrete element simulations of fragmentation and, last but not least, field data from over 4000 fragments.

We found [1] that stress fields determine fragmentation patterns (albeit in an averaged sense) and a vast majority of naturally occurring stress fields produce patterns which yield fragments with cuboid averages.

Whether and to what extent these findings vindicate Plato’s views and how they are related to the Gömböc are interesting subjects which I am happy to discuss if time admits.

[1] https://www.pnas.org/content/117/31/18178.short

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Fri 30 Oct 15:30: Title to be confirmed

From All Talks (aka the CURE list). Published on Sep 25, 2020.

Title to be confirmed

Abstract not available

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Fri 30 Oct 15:00: Title to be confirmed

From All Talks (aka the CURE list). Published on Sep 25, 2020.

Title to be confirmed

Abstract not available

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Fri 16 Oct 15:30: Title to be confirmed

From All Talks (aka the CURE list). Published on Sep 25, 2020.

Title to be confirmed

Abstract not available

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Fri 16 Oct 15:00: Title to be confirmed

From All Talks (aka the CURE list). Published on Sep 25, 2020.

Title to be confirmed

Abstract not available

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Wed 07 Oct 15:00: EML webinar Liquid crystal elastomers

From All Talks (aka the CURE list). Published on Sep 25, 2020.

EML webinar Liquid crystal elastomers

Abstract not available

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Fri 23 Oct 14:00: New 1D models for localisation in slender structures

From All Talks (aka the CURE list). Published on Sep 25, 2020.

New 1D models for localisation in slender structures

Slender structures are subject to various localised instabilities: necking of bars under traction, bulging of cylindrical party balloons, beading in cylinders made up of soft gels, or folding of tape-springs. In all these examples, distinct states of deformation may coexist and classical one-dimensional (1D) models predict singular solutions. In particular, classical 1D models fail to describe interfaces or finite size effects. The most common remedy is to use full structural models based on 3D finite elasticity or nonlinear shell/membrane equations. However, this is computationally costly and often impracticable: simpler 1D regularised models depending on the strain and the strain gradient are therefore attractive. There is a recent effort to rigorously establish 1D higher-order models for the analysis of localisation in slender structures. I will introduce a systematic method to derive such models by a formal expansion, starting from a variety of full structural models for slender elastic structures. The expansion is performed near a finitely pre-strained state and therefore retains all sources of nonlinearity, coming from the geometry and the constitutive law. I will illustrate the method in the case of bulging and beading, and demonstrate its accuracy by comparing solutions of the 1D gradient model with solutions of the original structural model.

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Regulating Interfacial Chemistry in Lithium‐Ion Batteries by a Weakly‐Solvating Electrolyte

By Yu-Xing Yao, Xiang Chen, Chong Yan, Xue-Qiang Zhang, Wen-Long Cai, Jia-Qi Huang, Qiang Zhang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 25, 2020.

The performance of Li‐ion batteries (LIBs) is highly dependent on their interfacial chemistry, which is regulated by electrolytes. Conventional electrolyte typically contains polar solvents to dissociate Li salts. Herein we report a weakly‐solvating electrolyte (WSE) that consists of a pure non‐polar solvent, which leads to a peculiar solvation structure where ion pairs and aggregates prevail under a low salt concentration of 1.0 M. Importantly, WSE forms unique anion‐derived interphases on graphite electrodes that exhibit fast‐charging and long‐term cycling characteristics. First‐principles calculations unravel a general principle that the competitive coordination between anions and solvents to Li ions is the origin of different interfacial chemistries. By bridging the gap between solution thermodynamics and interfacial chemistry in batteries, this work opens a brand‐new way towards precise electrolyte engineering for energy storage devices with desired properties.

Self‐Degradable Supramolecular Photosensitizer with High Photodynamic Therapeutic Efficiency and Improved Safety

By Bin Yuan, Han Wu, Hua Wang, Bohan Tang, Jiang-Fei Xu, Xi Zhang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 25, 2020.

Concerning that the residues of photosensitizers (PS) may cause serious side effects under light, it is of great significant to timely ‘switch off’ PS after photodynamic therapy (PDT). Herein, we proposed a supramolecular strategy to regulate the activity of PS, fabricating a supramolecular PS with improved reactive oxygen species (ROS) generation efficiency and accelerated self‐degradation ability. During PDT treatment, the supramolecular PS exhibited good therapeutic efficiency as well as reduced dark toxicity. Moreover, the supramolecular PS could be degraded by ROS generated by itself and lose its PDT activities once PDT treatment finished. In this way, the side effects of PDT can be reduced without sacrificing the therapeutic efficiency. This work provides a novel strategy for smarter PDT beacon to further improve the safety of PDT treatment.

Photodriven Disproportionation of Nitrogen and Its Change to Reductive Nitrogen Photofixation

By Jianhua Yang, Haoyuan Bai, Yanzhen Guo, Han Zhang, Ruibin Jiang, Baocheng Yang, Jianfang Wang, Jimmy C. Yu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 25, 2020.

Nitrogen fixation is an essential process for sustaining life. Tremendous efforts have been made on the photodriven fixation of nitrogen into ammonia. However, the disproportionation of dinitrogen to ammonia and nitrate under ambient conditions has yet remained a grand challenge. In this work, the photodriven disproportionation of nitrogen is realized in water under visible light and ambient conditions using Fe‐doped TiO 2 microspheres. The oxygen vacancies associated with the Fe dopants activate chemisorbed N 2 molecules, which can then be fixed into NH 3 with H 2 O 2 as the oxidation product. The generated H 2 O 2 thereafter oxidizes NH 3 into nitrate. This disproportionation reaction can be turned to the reductive one by loading plasmonic Au nanoparticles in the doped TiO 2 microspheres. The generated H 2 O 2 can be effectively decomposed by the Au nanoparticles, resulting in the transformation of the disproportionation reaction to the completely reductive nitrogen photofixation.

A Novel Fabrication Strategy for MOFs Films/Aerogel Composite Catalysts via Substrate‐seeding Secondary‐growth

By Xiao-Jue Bai, Xing-Yu Lu, Ran Ju, Huan Chen, Lei Shao, Xu Zhai, Yu-Nong Li, Fu-Qiang Fan, Yu Fu, Wei Qi from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 25, 2020.

Substrate‐supported metal‐organic frameworks (MOFs) films are urgently desired for realizing their great potential in practical applications. Herein, a novel substrate‐seeding secondary‐growth strategy was developed to fabricate composite of uniform MOFs films on aerogel walls. Briefly, the organic ligand is “pre‐seeded” onto the aerogel walls, and then a small amount of metal ions solution is sprayed onto the prepared aerogel. The sprayed solution is diffused along the aerogel walls to form a continuous thin layer, which confines the nucleation reaction, promoting the formation of uniform MOFs films on the aerogel walls. The whole fabrication process is simple in operation, highly efficient and eco‐friendly. The resulted hierarchical MOFs/aerogel composites possess abundant accessible active sites and enables excellent mass transfer, which endows the composite outstanding catalytic activity and stability in both liquid phase CO2 cycloaddition and electrochemical OER process.

Tue 17 Nov 17:00: Gender and generation in premodern Europe

From All Talks (aka the CURE list). Published on Sep 25, 2020.

Gender and generation in premodern Europe

A discussion of Leah DeVun’s The Shape of Sex: Nonbinary Gender from Genesis to the Renaissance (2020) with the author.

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The key role of the interface in the highly sensitive mechanochromic luminescence properties of hybrid perovskites

By Nicolas Mercier, Maroua Ben Haj Salah, Jens Dittmer, Nabil Zouari, Chiara Botta from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 25, 2020.

Hybrid perovskite (HP) materials are of huge interest in both photovoltaics and lighting applications. Here we report that hybrid perovskite composites, as crystallized powders, can behave as intelligent materials showing highly sensitive and reversible mechanochromic luminescence (MCL). Composites consisting of monolayered 2D HP and 3D HP components exhibit reversible tunable colour emission upon mechanical strain. Spectroscopic investigations first reveal that the bluish‐whitish emission of the 2D HP turns into orange in the composite due to an energy transfer process. The bright green emission, observed as soon as the composite is slightly crushed, originates from the 3D HP after efficient energy funnelling from the multi‐layered 2D HP produced at the 2D/3D interface by the mechanical treatment. Besides highlighting the key role of the interfaces in light emission of HP, our findings pave the way for hybrid perovskites as highly sensitive MCL smart materials for mechanosensors, security papers or optical storage applications.

Tue 01 Dec 17:00: The shadow of slavery: measuring miscegenation in the early 20th century

From All Talks (aka the CURE list). Published on Sep 25, 2020.

The shadow of slavery: measuring miscegenation in the early 20th century

Commentary: Jenny Bangham

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Tue 10 Nov 17:00: Microbe smiths: engineering microbial control in 20th-century Japan

From All Talks (aka the CURE list). Published on Sep 25, 2020.

Microbe smiths: engineering microbial control in 20th-century Japan

Commentary: Mary Brazelton

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Tue 03 Nov 17:00: The body whole and quotidian: experiencing the body in 18th-century Britain

From All Talks (aka the CURE list). Published on Sep 25, 2020.

The body whole and quotidian: experiencing the body in 18th-century Britain

Abstract not available

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Modifiers VS. Channels: Creating Shape‐Selective Catalysis of Metal Nanoparticles/Porous‐Nanomaterials

By Chuanzhen Fang, Liwei Liu, Jiena Weng, Suoying Zhang, Xinglong Zhang, Zhen Ren, Yu Shen, Fanchen Meng, Bing Zheng, Sheng Li, Jiansheng Wu, Wenxiong Shi, Sungsik Lee, Weina Zhang, Fengwei Huo from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 25, 2020.

Shape‐selective catalysis is of great research interest for its key role in chemical synthesis. Porous nanomaterials with uniform pore structures, have been proven as ideal supports for metal nanoparticles (MNPs) to generate efficient shape‐selective catalysis. However, many widely used commercial irregular porous nanomaterials usually face the challenge to realize satisfactory shape selectivity due to the lack of molecular sieving structures. Herein, we report a concept of creating shape selectivity in MNPs/porous‐nanomaterials through intentionally poisoning certain MNPs using suitable modifiers. The remained MNPs within the porous nanomaterials can cooperate with the channels to generate selectivity. Such strategy not only applies to regular porous nanomaterials (metal‐organic frameworks, zeolites, etc.), but also can be extended to irregular porous nanomaterials (active carbon, P25, etc.). Potentially, the matching among different MNPs, corresponding modifiers and porous nanomaterials makes our strategy promising for wide applications in selective catalytic systems.

Diversification of unprotected alicyclic amines via C–H bond functionalization: Decarboxylative alkylation of transient imines

By Anirudra Paul, Jae Hyun Kim, Scott D. Daniel, Daniel Seidel from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 25, 2020.

Despite extensive efforts by many practitioners in the field, methods for the direct α‐C–H bond functionalization of unprotected alicyclic amines remain rare. A new advance in this area utilizes N‐lithiated alicyclic amines. These readily accessible intermediates are converted to transient imines through the action of a simple ketone oxidant, followed by alkylation with a β‐ketoacid under mild conditions to provide valuable β‐amino ketones with unprecedented ease. Regioselective α′‐alkylation is achieved for substrates with existing α‐substituents. The method is further applicable to the convenient one‐pot synthesis of polycyclic dihydroquinolones through the incorporation of a SNAr step.

Mon 02 Nov 16:00: How is electrical signal generated?

From All Talks (aka the CURE list). Published on Sep 25, 2020.

How is electrical signal generated?

The voltage-gated sodium (Nav) channels are responsible for the initiation and propagation of action potentials. Being associated with a variety of channelopathies, they are targeted by multiple pharmaceutical drugs and natural toxins. We determined the crystal structure of a bacterial Nav channel NavRh in a potentially inactivated state a few years ago, which is a homotetramer in primary sequence but exhibits structural asymmetry. Employing the modern methods of cryo-EM, we determined the near atomic resolution structures of a Nav channel from American cockroach (designated NavPaS) and from electric eel (designated EeNav1.4). Most recently, we have determined the cryo-EM structures of the human Nav channels, Nav1.2, Nav1.4, and Nav1.7 in complex with distinct auxiliary subunits and toxins.These structures reveal the folding principle and structural details of the single-chain eukaryotic Nav channels that are distinct from homotetrameric voltage-gated ion channels. Unexpectedly, the two structures were captured in drastically different states. Whereas the structure of NavPaS has a closed pore and the four VSDs in distinct conformations, that of EeNav1.4 and the human channels is open at the intracelluar gate with VSDs exhibiting similar “up”states. The most striking conformational differenc occurs to the III -IV linker, which is essential for fast inactivation. Based on the structural features, we suggest an allosteric blocking mechanism for fast inactivation of Nav channels by the IFM motif. Structural comparison of the conformationally distinct Nav channels provides important insights into the electromechanical coupling mechanism of Nav channels and offers the 3D template to map hundredes of disease mutations.

Join Zoom meeting https://zoom.us/j/99696631826?pwd=ckxaelB5d0ltMHE1bEN2dUVlbzZBZz09

Meeting ID: 996 9663 1826 Passcode: 744191

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Coumarins by Direct Annulation: β‐Borylacrylates as Ambiphilic C3‐Synthons

By Max Wienhold, John J. Molloy, Constantin G. Daniliuc, Ryan Gilmour from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 25, 2020.

Modular β‐borylacrylates have been validated as programmable, ambiphilic C 3 ‐synthons in the cascade annulation of 2‐halo‐phenol derivatives to generate structurally and electronically diverse coumarins. Key to this [3+3] disconnection is the BPin unit which serves a dual purpose as both a traceless linker for C(sp 2 )‐C(sp 2 ) coupling, and as a chromophore extension to enable inversion of the alkene geometry via selective energy transfer catalysis. Mild isomerisation is a pre‐condition to access 3‐substituted coumarins and provides a handle for divergence. The method is showcased in the synthesis of representative natural products that contain this venerable chemotype. Facile entry into π‐expanded estrone derivatives modified at the A‐ring is disclosed to demonstrate the potential of the method in bioassay development or in drug repurposing.

Thu 08 Oct 15:00: Bias in AI

From All Talks (aka the CURE list). Published on Sep 25, 2020.

Bias in AI

“Blame it on the algorithm” is a common refrain these days when systems that include algorithmic components deliver very clearly unacceptable results. Examples range from Amazon’s gender biased hiring (machine learning) algorithm that learned from biased examples, though racial bias in AI methods used for predictive policing, to the recent UK A -level grade “normalization” of 2020, which was biased by design. These scenarios are often succinctly referred to as “algorithmic bias”, and there are many more examples, some of which are not so obvious. Moreover, this phrasing often leads people to think that this purely a technology problem when in fact one must look at the complete system, including the human elements, in which the algorithm is created and operated, to understand how these systems make mistakes. The talk will highlight the ways in which “algorithmic bias” can arise, and how we can identify and mitigate the damage.

Bio:

Derek McAuley is a British academic who is Professor of Digital Economy in the School of Computer Science at the University of Nottingham and director of Horizon Digital Economy Research, an interdisciplinary research institute funded through the RCUK Digital Economy programme. He acted as a Specialist Advisor to the House of Lords European Union Committee into online platforms, and Chief Innovation Officer during the founding of the Digital Catapult. He is a Fellow of the British Computer Society and member of the UKCRC , a computing research expert panel of the Institution of Engineering and Technology and BCS .

https://en.wikipedia.org/wiki/Derek_McAuley

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Thu 22 Oct 13:00: Evolutionary legacies on ecosystem function and implications for global change: new insights from spectral biology

From All Talks (aka the CURE list). Published on Sep 25, 2020.

Evolutionary legacies on ecosystem function and implications for global change: new insights from spectral biology

An open question is whether the structure and function of relatively undisturbed ecosystems are inevitable consequences of climate and geology or whether the idiosyncracies of biogeographic and evolutionary processes, including the order and timing of lineage dispersal and diversification, have led to divergent outcomes in ecosystem function. The ecosystem composition and diversity of plant electromagnetic spectra—the patterns of reflected photons from plants—are emerging as important measures of biodiversity, alongside functional and phylogenetic components. Spectra contain abundant information about plant function and are tightly coupled to the tree of life. The evolutionary innovations and legacies of biogeographic history that have contributed to modern plant communities and ecosystems may be revealed from the spectral reflectance of plants and from increasingly available remote sensing data that provide environmental information across spatial and temporal scales. Understanding the context in which plants evolved and the role of evolutionary history in current ecosystem structure and function provides insight into how ecosystems will respond to future environmental changes. These insights combined with advancing methods for detecting and monitoring change in biodiversity and ecosystems can help prioritize conservation and inform strategies for maintaining a habitable planet in the face of global change.

Contact se389@cam.ac.uk for the Zoom link if you are not on our mailing list.

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[ASAP] Boosting Light Emission from Single Hydrogen Phthalocyanine Molecules by Charging

By Vibhuti Rai, Lukas Gerhard, Qing Sun, Christof Holzer, Taavi Repän, Marjan Krstić, Liang Yang, Martin Wegener, Carsten Rockstuhl, and Wulf Wulfhekel from Nano Letters: Latest Articles (ACS Publications). Published on Sep 25, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c03121

[ASAP] Optically Pumped Lasing in Microscale Light-Emitting Electrochemical Cell Arrays for Multicolor Displays

By Jie Liang, Manman Chu, Zhonghao Zhou, Yongli Yan, and Yong Sheng Zhao from Nano Letters: Latest Articles (ACS Publications). Published on Sep 25, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c02378

[ASAP] Photocurrent Imaging of Multi-Memristive Charge Density Wave Switching in Two-Dimensional 1T-TaS2

By Tarun Patel, Junichi Okamoto, Tina Dekker, Bowen Yang, Jingjing Gao, Xuan Luo, Wenjian Lu, Yuping Sun, and Adam W. Tsen from Nano Letters: Latest Articles (ACS Publications). Published on Sep 25, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c02537

[ASAP] Encapsulating Ultrafine Sb Nanoparticles in Na+ Pre-Intercalated 3D Porous Ti3C2Tx MXene Nanostructures for Enhanced Potassium Storage Performance

By Ruizheng Zhao, Haoxiang Di, Chengxiang Wang, Xiaobin Hui, Danyang Zhao, Rutao Wang, Luyuan Zhang, and Longwei Yin from ACS Nano: Latest Articles (ACS Publications). Published on Sep 25, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c06360

[ASAP] Polymer-Ligated Nanocrystals Enabled by Nonlinear Block Copolymer Nanoreactors: Synthesis, Properties, and Applications

By Yijiang Liu, Jialin Wang, Mingyue Zhang, Huaming Li, and Zhiqun Lin from ACS Nano: Latest Articles (ACS Publications). Published on Sep 25, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c06936

[ASAP] Insight into the Spin Properties in Undoped and Mn-Doped CdSe/CdS-Seeded Nanorods by Optically Detected Magnetic Resonance

By Joanna Dehnel, Yahel Barak, Itay Meir, Adam K. Budniak, Anjani P. Nagvenkar, Daniel R. Gamelin, and Efrat Lifshitz from ACS Nano: Latest Articles (ACS Publications). Published on Sep 25, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c05454

[ASAP] Engineering of Cascade-Responsive Nanoplatform to Inhibit Lactate Efflux for Enhanced Tumor Chemo-Immunotherapy

By Ke Li, Chuanchuan Lin, Ye He, Lu Lu, Kun Xu, Bailong Tao, Zengzilu Xia, Rui Zeng, Yulan Mao, Zhong Luo, and Kaiyong Cai from ACS Nano: Latest Articles (ACS Publications). Published on Sep 25, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c07071

[ASAP] Chirality-Dependent Second Harmonic Generation of MoS2 Nanoscroll with Enhanced Efficiency

By Qingkai Qian, Rui Zu, Qingqing Ji, Gang Seob Jung, Kunyan Zhang, Ye Zhang, Markus J. Buehler, Jing Kong, Venkatraman Gopalan■, and Shengxi Huang from ACS Nano: Latest Articles (ACS Publications). Published on Sep 25, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c05189

[ASAP] A Microorganism Bred TiO2/Au/TiO2 Heterostructure for Whispering Gallery Mode Resonance Assisted Plasmonic Photocatalysis

By Xin Yu, Xin Jin, Xuanyu Chen, Aizhu Wang, Jianming Zhang, Jian Zhang, Zhenhuan Zhao, Mingming Gao, Luca Razzari, and Hong Liu from ACS Nano: Latest Articles (ACS Publications). Published on Sep 25, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c06278

[ASAP] Mitigation of Carbon Nanotube Neurosensor Induced Transcriptomic and Morphological Changes in Mouse Microglia with Surface Passivation

By Darwin Yang, Sarah J. Yang, Jackson Travis Del Bonis-O’Donnell, Rebecca L. Pinals, and Markita P. Landry from ACS Nano: Latest Articles (ACS Publications). Published on Sep 25, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c06154

[ASAP] Localized and Programmable Chemical Vapor Deposition Using an Electrically Charged and Guided Molecular Flux

By Johannes Reiprich, Nishchay A. Isaac, Leslie Schlag, Thomas Kups, Marcus Hopfeld, Gernot Ecke, Thomas Stauden, Jörg Pezoldt, and Heiko O. Jacobs from ACS Nano: Latest Articles (ACS Publications). Published on Sep 25, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c03726

[ASAP] Liposomal Delivery of Mitoxantrone and a Cholesteryl Indoximod Prodrug Provides Effective Chemo-immunotherapy in Multiple Solid Tumors

By Kuo-Ching Mei, Yu-Pei Liao, Jinhong Jiang, Michelle Chiang, Mercedeh Khazaieli, Xiangsheng Liu, Xiang Wang, Qi Liu, Chong Hyun Chang, Xiao Zhang, Juan Li, Ying Ji, Brenda Melano, Donatello Telesca, Tian Xia, Huan Meng, and Andre E. Nel from ACS Nano: Latest Articles (ACS Publications). Published on Sep 25, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c05194

[ASAP] Synthetic Polymeric Antibacterial Hydrogel for Methicillin-Resistant Staphylococcus aureus-Infected Wound Healing: Nanoantimicrobial Self-Assembly, Drug- and Cytokine-Free Strategy

By Wenshuai Liu, Wenbin Ou-Yang, Chao Zhang, Qiangsong Wang, Xiangbin Pan, Pingsheng Huang, Chuangnian Zhang, Yuejie Li, Deling Kong, and Weiwei Wang from ACS Nano: Latest Articles (ACS Publications). Published on Sep 25, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c03855

[ASAP] Monitoring Intracranial Cerebral Hemorrhage Using Multicontrast Real-Time Magnetic Particle Imaging

By Patryk Szwargulski, Maximilian Wilmes, Ehsan Javidi, Florian Thieben, Matthias Graeser, Martin Koch, Cordula Gruettner, Gerhard Adam, Christian Gerloff, Tim Magnus, Tobias Knopp, and Peter Ludewig from ACS Nano: Latest Articles (ACS Publications). Published on Sep 25, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c06326

[ASAP] Exosome-Mediated Crosstalk between Keratinocytes and Macrophages in Cutaneous Wound Healing

By Xiaoju Zhou, Brooke A. Brown, Amanda P. Siegel, Mohamed S. El Masry, Xuyao Zeng, Woran Song, Amitava Das, Puneet Khandelwal, Andrew Clark, Kanhaiya Singh, Poornachander R. Guda, Mahadeo Gorain, Lava Timsina, Yi Xuan, Stephen C. Jacobson, Milos V. Novotny, Sashwati Roy, Mangilal Agarwal, Robert J. Lee, Chandan K. Sen, David E. Clemmer, and Subhadip Ghatak from ACS Nano: Latest Articles (ACS Publications). Published on Sep 25, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c03064

[ASAP] Perovskite Core–Shell Nanowire Transistors: Interfacial Transfer Doping and Surface Passivation

By You Meng, Zhengxun Lai, Fangzhou Li, Wei Wang, SenPo Yip, Quan Quan, Xiuming Bu, Fei Wang, Yan Bao, Takuro Hosomi, Tsunaki Takahashi, Kazuki Nagashima, Takeshi Yanagida, Jian Lu, and Johnny C. Ho from ACS Nano: Latest Articles (ACS Publications). Published on Sep 25, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c03101

[ASAP] All-Aqueous Liquid Crystal Nanocellulose Emulsions with Permeable Interfacial Assembly

By Long Bai, Siqi Huan, Bin Zhao, Ya Zhu, Jordi Esquena, Feng Chen, Guang Gao, Eyal Zussman, Guang Chu, and Orlando J. Rojas from ACS Nano: Latest Articles (ACS Publications). Published on Sep 25, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c05251

[ASAP] Genetically Encoded Quinone Methides Enabling Rapid, Site-Specific, and Photocontrolled Protein Modification with Amine Reagents

By Jun Liu, Rujin Cheng, Ned Van Eps, Nanxi Wang, Takefumi Morizumi, Wei-Lin Ou, Paul C. Klauser, Sharon Rozovsky, Oliver P. Ernst, and Lei Wang from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Sep 25, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c06820

[ASAP] Reticular Chemistry in the Construction of Porous Organic Cages

By Kongzhao Su, Wenjing Wang, Shunfu Du, Chunqing Ji, Mi Zhou, and Daqiang Yuan from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Sep 25, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c07367

[ASAP] Glycopeptide Self-Assembly Modulated by Glycan Stereochemistry through Glycan–Aromatic Interactions

By Changdong He, Shuang Wu, Dangliang Liu, Changbiao Chi, Weilin Zhang, Ming Ma, Luhua Lai, and Suwei Dong from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Sep 25, 2020.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.0c06360

[ASAP] An Internuclear J-Coupling of 3He Induced by Molecular Confinement

By George Razvan Bacanu, Jyrki Rantaharju, Gabriela Hoffman, Mark C. Walkey, Sally Bloodworth, Maria Concistrè, Richard J. Whitby, and Malcolm H. Levitt from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Sep 25, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c08586

Selectivity of Nitrate and Chloride Ions in Microporous Carbons: The Role of Anisotropic Hydration and Applied Potentials

By Patrick G. Campbell from RSC - Nanoscale latest articles. Published on Sep 25, 2020.

Nanoscale, 2020, Accepted Manuscript
DOI: 10.1039/D0NR04496B, Paper
Fikret Aydin, Maira R Ceron, Steven A Hawks, Diego Ignacio Oyarzun, Cheng Zhan, Tuan A Pham, Michael Stadermann, Patrick G. Campbell
Understanding ion transport in porous carbons is critical for a wide range of technologies, including supercapacitors and capacitive deionization for water desalination, yet many details remain poorly understood. For instance,...
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Membrane Poration, Wrinkling, and Compression: Deformations of Lipid Vesicles Induced by Amphiphilic Janus Nanoparticles

By Yan Yu from RSC - Nanoscale latest articles. Published on Sep 25, 2020.

Nanoscale, 2020, Accepted Manuscript
DOI: 10.1039/D0NR05355D, Paper
Jared Wiemann, Zhiqiang Shen, Huilin Ye, Ying Li, Yan Yu
Building upon our previous studies on interactions of amphiphilic Janus nanoparticles with glass-supported lipid bilayers, we study here how these Janus nanoparticles perturb the structural integrity and induce shape instabilities...
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A versatile UCST-type composite microsphere for image-guided chemoembolization and photothermal therapy against liver cancer

By Weiling He from RSC - Nanoscale latest articles. Published on Sep 25, 2020.

Nanoscale, 2020, Accepted Manuscript
DOI: 10.1039/D0NR04592F, Paper
Open Access Open Access
Dan Huang, Haitao Dai, Keyu Tang, Bin Chen, Hongzhang Zhu, Dubo Chen, Nan Li, Yingzhao Wang, Chuwei Liu, Yonghui Huang, Jianyong Yang, Chao Zhang, Run Lin, Weiling He
Development of novel chemoembolization agents to improve the treatment efficacy of transarterial chemoembolization (TACE) against liver cancer remains an urgent need in clinical practice. Herein, a versatile composite microsphere with...
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NanoSQUIDs from YBa2Cu3O7/SrTiO3 superlattices with bicrystal grain boundary Josephson junctions

By Dieter Koelle from RSC - Nanoscale latest articles. Published on Sep 25, 2020.

Nanoscale, 2020, Accepted Manuscript
DOI: 10.1039/D0NR05446A, Paper
Jianxin Lin, Julian Linek, R Kleiner, Dieter Koelle
We report on the fabrication and characterization of nanopatterned dc SQUIDs with grain boundary Josephson junctions based on heteroepitaxially grown YBa2Cu3O7 (YBCO)/ SiTrO3 (STO) superlattices on STO bicrystal substrates. Nanopatterning...
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Morphology-Controlled MoS2 by Low-Temperature Atomic Layer Deposition

By Nicola Pinna from RSC - Nanoscale latest articles. Published on Sep 25, 2020.

Nanoscale, 2020, Accepted Manuscript
DOI: 10.1039/D0NR03863F, Paper
Open Access Open Access
Chengxu Chen, Muhammad Hamid Raza, P Amsalem, Thorsten Schultz, Norbert Koch, Nicola Pinna
Two-dimensional (2D) transition metal dichalcogenides (TMDs) such as MoS2 are rising materials for multifarious applications such as sensing, catalysis, and energy storage. Due to their peculiar charge-transport properties, it is...
The content of this RSS Feed (c) The Royal Society of Chemistry

Arbitrary deformable and high-strength electroactive polymer/ MXene anti-exfoliative composite films assembled into high performance flexible all-solid-state supercapacitors

By Wenbin Zhong from RSC - Nanoscale latest articles. Published on Sep 25, 2020.

Nanoscale, 2020, Accepted Manuscript
DOI: 10.1039/D0NR04980H, Paper
Yang Zhou, Yubo Zou, Zhiyuan Peng, Chuying Yu, Wenbin Zhong
Flexible all-solid-state supercapacitors (ASSSs) are excellent energy storage devices for portable/wearable electronics. While the development of excellent comprehensive performance film electrode for extraordinary flexible ASSSs still faces a great challenge....
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Chemistry Evolves, Terms Evolve, but Phenomena Do Not Evolve: From Chalcogen–Chalcogen Interactions to Chalcogen Bonding

By Simon Kolb, Gwyndaf A. Oliver, Daniel B. Werz from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 24, 2020.

Chalcogen bonding describes the interaction of Lewis‐acidic chalcogen atoms with a variety of Lewis‐basic atoms. This Viewpoint assesses the development of this term from its predecessor “chalcogen–chalcogen interactions” through discussion of some of the varied and fascinating chemistry it has inspired. Abstract Chalcogen bonding is important in numerous aspects of chemistry, both in the solid state and in solution. Surveying the literature, it becomes clear that during its rebranding from chalcogen–chalcogen interactions, some parts of the community have somewhat neglected to recall its discovery and the initial studies referring to it in its previous guise. In this Viewpoint, we trace the path of research into this phenomenon, from its discovery, through its renaming, and to some of the varied and interesting chemistry it has led to so far, ranging from crystal engineering through supramolecular assembly to modern catalysis.

Amino‐Supported Solid Palladium Catalyst for Chemo‐ and Stereoselective Domino Reactions

By Jan-E. Bäckvall, Man-Bo Li, Jie Yang, Ying Yang, Guo-Yong Xu, Gen Luo, Jianping Yang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 24, 2020.

An amino‐supported solid palladium‐catalyzed oxidative domino reaction has been developed for the diastereoselective construction of alkyne‐substituted cyclopentenol compounds. This hetero­ge­neous catalyst exhibits high efficiency and excellent chemoselectivity, as well as good recyclability. The chemoselectivity of the domino reactions was readily controlled by switching the solvent and catalyst. Chiral syntheses and an oxidative carbocyclization‐borylation reaction have also been developed based on the heterogeneous Pd‐catalyzed domino strategy.

Advanced Materials and Systems for Biodegradable, Transient Electronics

By Won Bae Han, Joong Hoon Lee, Jeong‐Woong Shin, Suk‐Won Hwang from Wiley: Advanced Materials: Table of Contents. Published on Sep 24, 2020.

An advanced class of electronic system, transient electronics, that entirely dissolves in certain circumstances in controlled manners after fulfilling their functions is presented. Such unique properties enable comprehensive contributions in research fields of biomedicine and environment‐friendly and security system. This review describes the recent developments in materials and manufacturing processes, as well as various applications of transient technology. Abstract Transient electronics refers to an emerging class of advanced technology, defined by an ability to chemically or physically dissolve, disintegrate, and degrade in actively or passively controlled fashions to leave environmentally and physiologically harmless by‐products in environments, particularly in bio‐fluids or aqueous solutions. The unusual properties that are opposite to operational modes in conventional electronics for a nearly infinite time frame offer unprecedented opportunities in research areas of eco‐friendly electronics, temporary biomedical implants, data‐secure hardware systems, and others. This review highlights the developments of transient electronics, including materials, manufacturing strategies, electronic components, and transient kinetics, along with various potential applications.

Thu 22 Oct 09:30: Tumour structure and nomenclature These talks are aimed at Masters and first year PhD students but all are welcome to attend.

From All Talks (aka the CURE list). Published on Sep 24, 2020.

Tumour structure and nomenclature

Abstract not available

These talks are aimed at Masters and first year PhD students but all are welcome to attend.

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Thu 29 Oct 09:30: Overview of the core ideas in cancer research These talks are aimed at Masters and first year PhD students but all are welcome to attend.

From All Talks (aka the CURE list). Published on Sep 24, 2020.

Overview of the core ideas in cancer research

Abstract not available

These talks are aimed at Masters and first year PhD students but all are welcome to attend.

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Thu 05 Nov 09:30: The mutations that drive cancer These talks are aimed at Masters and first year PhD students but all are welcome to attend.

From All Talks (aka the CURE list). Published on Sep 24, 2020.

The mutations that drive cancer

Abstract not available

These talks are aimed at Masters and first year PhD students but all are welcome to attend.

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Thu 12 Nov 09:30: Introduction to the biology of metastasis These talks are aimed at Masters and first year PhD students but all are welcome to attend.

From All Talks (aka the CURE list). Published on Sep 24, 2020.

Introduction to the biology of metastasis

Abstract not available

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Thu 19 Nov 09:30: Cancer metabolism, a hallmark of cancer These talks are aimed at Masters and first year PhD students but all are welcome to attend.

From All Talks (aka the CURE list). Published on Sep 24, 2020.

Cancer metabolism, a hallmark of cancer

Abstract not available

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Thu 26 Nov 09:30: DNA repair: from mechanistic insights to therapeutic applications in cancer These talks are aimed at Masters and first year PhD students but all are welcome to attend.

From All Talks (aka the CURE list). Published on Sep 24, 2020.

DNA repair: from mechanistic insights to therapeutic applications in cancer

Abstract not available

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Thu 03 Dec 09:30: Cancer stem cells, evolution and heterogeneity These talks are aimed at Masters and first year PhD students but all are welcome to attend.

From All Talks (aka the CURE list). Published on Sep 24, 2020.

Cancer stem cells, evolution and heterogeneity

Abstract not available

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Thu 10 Dec 09:30: Exploring the role of the tumour microenvironment: what do the other cells do? These talks are aimed at Masters and first year PhD students but all are welcome to attend.

From All Talks (aka the CURE list). Published on Sep 24, 2020.

Exploring the role of the tumour microenvironment: what do the other cells do?

Abstract not available

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Thu 17 Dec 09:30: Systemic anti-cancer therapy These talks are aimed at Masters and first year PhD students but all are welcome to attend.

From All Talks (aka the CURE list). Published on Sep 24, 2020.

Systemic anti-cancer therapy

Abstract not available

These talks are aimed at Masters and first year PhD students but all are welcome to attend.

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LEAD‐m6A‐seq for Locus‐specific Detection of N6‐methyladenosine and Quantification of Differential Methylation

By Chuan He, Yuru Wang, Zijie Zhang, Caraline Sepich-Poore, Lisheng Zhang, Yu Xiao from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 24, 2020.

N 6 ‐methyladenosine (m 6 A) is a crucial RNA chemical mark which plays important roles in various biological processes. The development of highly multiplexed, cost‐effective, and easy‐to‐operate methodologies for locus‐specific analysis of m 6 A is critical for advancing our understanding of the roles of this modification. Here, we report a method which builds upon the principle of the previously reported SELECT approach by significantly improving its efficiency and coupling it to next generation sequencing technology for high‐throughput validation and detection of m 6 A modification at selected sites (LEAD‐m 6 A‐seq). Through probing cDNA extension mediated by Bst DNA polymerase at and near target cellular sites by sequencing, we evaluated m 6 A modification at these sites, and estimated differential methylation levels (0%‐84%) upon in vitro demethylation by FTO with high reproducibility. We envision that this strategy can be readily used for testing a greater number of sites with a broad dynamic range and modified to study other RNA modifications.

Cobalt‐Catalyzed Markovnikov‐Type Selective Hydroboration of Terminal Alkynes

By Jieping Chen, Xuzhong Shen, Zhan Lu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 24, 2020.

Here, we reported a cobalt‐catalyzed Markovnikov‐type hydroboration of terminal alkynes with HBpin to access α ‐alkenyl boronates with good regioselectivity and atom economy. A new ligand has been developed for cobalt hydride catalyst which has been used for a unique Markovnikov selective insertion of terminal alkynes into metal hydride bond. This operationally simple protocol exhibits excellent functional group tolerance to deliver valuable alkene derivatives.

Selective N‐terminal BRD4 bromodomain inhibitors by targeting non‐conserved residues and structured water displacement

By William Charles Krause Pomerantz, Huarui Cui, Anand Divakaran, Anil K. Pandey, Jorden A. Johnson, Huda Zahid, Zachariah J. Hoell, Mikael O. Ellingson, Ke Shi, Hideki Aihara, Daniel A. Harki from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 24, 2020.

Bromodomain and extra‐terminal (BET) family proteins, BRD2‐4 and T, are important drug targets; however, the biological functions of each bromodomain remain ill‐defined. Chemical probes that selectively inhibit a single BET bromodomain are lacking, although pan inhibitors of the first (D1), and second (D2), bromodomain are known. Here, we develop selective BET D1 inhibitors with preferred binding to of BRD4 D1. In competitive inhibition assays we show that our lead compound is 9‐33 fold selective for BRD4 D1 over the other BET bromodomains. X‐ray crystallography supports a role for the selectivity based on reorganization of a non‐conserved lysine and displacement of an additional structured water  in the BRD4 D1 binding site relative to our prior lead. Whereas pan‐D1 inhibitors displace BRD4 from MYC enhancers, BRD4 D1 inhibition in MM.1S cells is insufficient for stopping Myc expression and may lead to its upregulation. Future analysis of BRD4 D1 gene regulation may shed light on differential BET bromodomain functions.

Mon 19 Oct 16:30: Title to be confirmed

From All Talks (aka the CURE list). Published on Sep 24, 2020.

Title to be confirmed

Abstract not available

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Controllable Heterogeneous Nucleation for Patterning High‐Quality Vertical and Horizontal ZnO Microstructures toward Photodetectors

By Haohao Li, Meilin Liu, Jinjin Zhao, Hanfei Gao, Jiangang Feng, Lei Jiang, Yuchen Wu from Wiley: Small: Table of Contents. Published on Sep 24, 2020.

High‐quality ZnO crystal microrod and microbelt arrays with precise arrangement and pure crystallographic orientation are fabricated by the combination of the capillary‐bridge lithography method and hydrothermal method. The discussion of crystallization mechanism is performed through the competition between homogeneous and heterogeneous nucleation processes. Photodetectors based on microbelt arrays exhibit high optoelectronic performance owing to the smooth surface energy band. Abstract High‐quality crystalline micro‐ and nanostructures based on inorganic semiconductors including zinc oxide (ZnO) have attracted considerable interest in electronic and optoelectronic applications due to their outstanding properties. ZnO micro‐ and nanocrystals can be fabricated by the moderate and high throughput hydrothermal synthesis. Yet it is restricted by patterning large‐area ZnO crystals with high‐quality and programmable geometries through the hydrothermal process for the optoelectronic integration. Here, a capillary‐bridge manipulation approach is demonstrated to control the dewetting process of ZnO precursor solution for patterning precursor arrays. Based on precursor arrays, vertically aligned high‐quality ZnO microrod arrays with homogeneous morphology and pure crystallographic orientation are fabricated via a hydrothermal epitaxial method. Statistical results and crystallization theories guide the experimental optimization and discussion of the crystallization mechanism, dominated by the competition between homogeneous nucleation and heterogeneous nucleation. High‐quality ZnO microbelt arrays are achieved through a surfactant‐mediated hydrothermal method after ZnO microrod arrays are transferred to a polydimethylsiloxane substrate. Photodetectors based on ZnO microbelts exhibit a high responsivity of 2.3 × 104 A W−1, a light on–off ratio exceeding 105, and stable recyclability. It is anticipated that this work provides new insights into patterning inorganic high‐quality micro‐ and nanostructures for multi‐functional integrated devices.

Vacancies in Self‐Assembled Crystals: An Archetype for Clusters Statistics at the Nanoscale

By Jose Angel Pariente, Niccolò Caselli, Carlos Pecharromán, Alvaro Blanco, Cefe López from Wiley: Small: Table of Contents. Published on Sep 24, 2020.

Self‐assembly from a binary colloid and selective etching of one species creates vacancy‐doped crystals that serve as model systems for the study of vacancy cluster statistics. Hard sphere interaction precludes inter‐ or intra‐species affinities and secures random vacancy distribution. A cluster size tally from SEM in agreement with an analytical model of the crystal surface supports the hard sphere assumption. Abstract Complex systems involving networks have attracted strong multidisciplinary attention since they are predicted to sustain fascinating phase transitions in the proximity of the percolation threshold. Developing stable and compact archetypes that allow one to experimentally study physical properties around the percolation threshold remains a major challenge. In nanoscale systems, this achievement is rare since it is tied to the ability to control the intentional disorder and perform a vast statistical analysis of cluster configurations. Here, a self‐assembly method to fabricate perfectly ordered structures where random defects can be introduced is presented. Building binary crystals from two types of dielectric nanospheres and selectively removing one of them creates vacancies at random lattice positions that form a complex network of clusters. Vacancy content can be easily controlled and raised even beyond the percolation threshold. In these structures, the distribution of cluster sizes as a function of vacancy density is analyzed. For moderate concentrations, it is found to be homogeneous throughout the structure and in good agreement with the assumption of a random vacancy distribution.

Advances in the Design of 3D‐Structured Electrode Materials for Lithium–Metal Anodes

By Sunwoo Park, Hyoung‐Joon Jin, Young Soo Yun from Wiley: Advanced Materials: Table of Contents. Published on Sep 24, 2020.

This progress report reviews the design of 3D‐structured electrode materials for Li metal anode according to their categories, namely 1) metal‐based materials, 2) carbon‐based materials, and 3) their hybrids, and allows the results obtained under different experimental conditions to be seen at a single glance, thus being helpful for researchers working in related fields. Abstract Although the lithium–metal anode (LMA) can deliver a high theoretical capacity of ≈3860 mAh g−1 at a low redox potential of −3.040 V (vs the standard hydrogen electrode), its application in rechargeable batteries is hindered by the poor Coulombic efficiency and safety issues caused by dendritic metal growth. Consequently, careful electrode design, electrolyte engineering, solid–electrolyte interface control, protective layer introduction, and other strategies are suggested as possible solutions. In particular, one should note the great potential of 3D‐structured electrode materials, which feature high active specific surface areas and stereoscopic structures with multitudinous lithiophilic sites and can therefore facilitate rapid Li‐ion flux and metal nucleation as well as mitigate Li dendrite formation through the kinetic control of metal deposition even at high local current densities. This progress report reviews the design of 3D‐structured electrode materials for LMA according to their categories, namely 1) metal‐based materials, 2) carbon‐based materials, and 3) their hybrids, and allows the results obtained under different experimental conditions to be seen at a single glance, thus being helpful for researchers working in related fields.

Relative Thermodynamic Stability of Diamond and Graphite

By Mary Anne White, Samer Kahwaji, Vera L. S. Freitas, Riko Siewert, Joseph A. Weatherby, Maria D. M. C. Ribeiro da Silva, Sergey P. Verevkin, Erin R. Johnson, Josef W. Zwanziger from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 24, 2020.

Recent density‐functional theory (DFT) calculations raised the possibility that diamond could be degenerate with graphite at very low temperatures. Through high‐accuracy calorimetric experiments closing gaps in available data, we reinvestigate the relative thermodynamic stability of diamond and graphite. For T

Reductive Hexamerization of CO Involving Cooperativity Between Magnesium(I) Reductants and [Mo(CO)6]: Synthesis of Well‐Defined Magnesium Benzenehexolate Complexes

By Cameron Jones, Albert Paparo, K. Yuvaraj, Aidan J. R. Matthews, Iskander Douair, Laurent Maron from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 24, 2020.

Reactions of two magnesium(I) compounds, [{(ArNacnac)Mg}2] (ArNacnac = [HC(MeCNAr)2]‐Ar = mesityl (Mes) or o‐xylyl (Xyl)), with CO in the presence of [Mo(CO)6] lead to the reductive hexamerization of CO, and formation of magnesium benzenehexolate complexes, [{(ArNacnac)Mg}6(C6O6)]. [Mo(CO)6] is not consumed in these reactions, but is apparently required to initiate (or catalyze) the CO hexamerizations. A range of synthetic, spectroscopic and computational studies have been used to probe the mechanism of formation of the benzenehexolate complexes. The magnesium(I) reductive hexamerizations of CO are closely related to Liebig’s reduction of CO with molten potassium (to give K6C6O6, amongst other products), originally reported in 1834. As the mechanism of that reaction is still unknown, it seems reasonable that magnesium(I) reductions of CO could prove useful homogeneous models for its elucidation, and for the study of other C‐C bond forming reactions that use CO as a C1 feedstock (e.g. the Fischer‐Tropsch process).

Thu 14 Oct 13:00: Title to be confirmed

From All Talks (aka the CURE list). Published on Sep 24, 2020.

Title to be confirmed

Abstract not available

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Concise Total Synthesis of Tronocarpine

By Atsushi Nakayama, Tenta Nakamura, Toshihiro Zaima, Saho Fujimoto, Sangita Karanjit, Kosuke Namba from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 24, 2020.

A concise total synthesis of tronocarpine, a chippiine‐type indole alkaloid, was accomplished. The key feature of this total synthesis is one‐pot construction of the pentacyclic skeleton containing an azabicyclo[3.3.1]nonane core by tandem cyclization from an indole derivative having all carbon side chains and functional groups. This tandem cyclization consists of α,β‐unsaturated aldehyde formation, intramolecular aldol reaction, six‐membered lactamization, azide reduction, and seven‐membered lactamization. The stereochemical outcome in this tandem cyclization is controlled by the stereocenter at the C14 position. This strategy can be utilized to synthesize other chippiine‐type alkaloids with azabicyclo[3.3.1]nonane skeletons.

Mon 23 Nov 18:00: Professor Sadaf Farooqi - title to be confirmed

From All Talks (aka the CURE list). Published on Sep 24, 2020.

Professor Sadaf Farooqi - title to be confirmed

Abstract not available

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Mon 09 Nov 18:00: Dr Julia Wolf - title to be confirmed

From All Talks (aka the CURE list). Published on Sep 24, 2020.

Dr Julia Wolf - title to be confirmed

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Mon 12 Oct 18:00: Larmor Lecture - Climate change and cascading risks Online Lecture

From All Talks (aka the CURE list). Published on Sep 24, 2020.

Larmor Lecture - Climate change and cascading risks

Abstract not available

Online Lecture

  • Speaker: Professor Tim Benton Research Director – Emerging Risks, and Director – Energy, Environment and Resources Programme Royal Institute of International Affairs, Chatham House
  • Monday 12 October 2020, 18:00-19:00
  • Venue: Time and venue to be confirmed.
  • Series: Cambridge Philosophical Society; organiser: .

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Mon 26 Oct 18:00: A V Hill Lecture - Dr Andrew Muray - Title to be confirmed Online Lecture

From All Talks (aka the CURE list). Published on Sep 24, 2020.

A V Hill Lecture - Dr Andrew Muray - Title to be confirmed

Abstract not available

Online Lecture

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Thu 19 Nov 13:00: Title to be confirmed

From All Talks (aka the CURE list). Published on Sep 24, 2020.

Title to be confirmed

Abstract not available

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Thu 15 Oct 13:00: Title to be confirmed

From All Talks (aka the CURE list). Published on Sep 24, 2020.

Title to be confirmed

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Fragment Coupling Reactions in Total Synthesis That Form Carbon–Carbon Bonds via Carbanionic or Free Radical Intermediates

By Martin Tomanik, Ian Tingyung Hsu, Seth B. Herzon from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 24, 2020.

This review presents a survey of recent examples of fragment coupling reactions that form carbon–carbon bonds via carbanionic or free radical intermediates in total synthesis. The aim is to identify extensible lessons from each example that might be useful to students in the field. Powerful advances in the generation and application of carbanionic and free radical intermediates in complex settings are highlighted. Abstract Fragment coupling reactions that form carbon–carbon bonds are valuable transformations in synthetic design. Advances in metal‐catalyzed cross‐coupling reactions in the early 2000s brought a high level of predictability and reliability to carbon–carbon bond constructions involving the union of unsaturated fragments. By comparison, recent years have witnessed an increase in fragment couplings proceeding via carbanionic and open‐shell (free radical) intermediates. The latter has been driven by advances in methods to generate and utilize carbon‐centered radicals under mild conditions. In this Review, we survey a selection of recent syntheses that have implemented carbanion‐ or radical‐based fragment couplings to form carbon–carbon bonds. We aim to highlight the strategic value of these disconnections in their respective settings and to identify extensible lessons from each example that might be instructive to students.

The [(NHC)B(H)C6F5]+ Cations and Their [B](H)−CO Borane Carbonyls

By Chaohuang Chen, Jun Li, Constantin G. Daniliuc, Christian Mück‐Lichtenfeld, Gerald Kehr, Gerhard Erker from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 24, 2020.

The B−H containing [(NHC)B(H)C6F5]+ borenium cations were obtained by hydride abstraction from the heterocyclic carbene borane adducts (NHC)BH2C6F5. They cleanly add carbon monoxide to give the respective [(NHC)B(H)(C6F5)CO]+ boron carbonyl cations. The activated C≡O can be attacked by carbon nucleophiles and be reduced by an external hydride. Abstract Hydride abstraction from the heterocyclic carbene borane adducts (NHC)BH2C6F5 (NHC: IMes or IMe4) gave the B−H containing [(NHC)B(H)C6F5]+ borenium cations. They added carbon monoxide to give the respective [(NHC)B(H)(C6F5)CO]+ boron carbonyl cations. Carbon nucleophiles add to the boron carbonyl to give [B](H) acyls. Hydride reduced the [B]CO cation to hydroxymethylborane derivatives.

Organocatalytic Asymmetric C(sp2)−H Allylic Alkylation: Enantioselective Synthesis of Tetrasubstituted Allenoates

By Yimin Hu, Wangyu Shi, Bing Zheng, Jianning Liao, Wei Wang, Yongjun Wu, Hongchao Guo from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 24, 2020.

The first organocatalytic C(sp2)−H allylation of racemic trisubstituted allenoates with Morita–Baylis–Hillman (MBH) carbonates was achieved, providing highly functionalized tetrasubstituted allenoates with adjacent axial chirality and tertiary carbon stereocenters in high yields with good to excellent diastereoselectivities and enantioselectivities. Abstract Herein we describe the first organocatalytic asymmetric C(sp2)−H allylation of racemic trisubstituted allenoates with Morita–Baylis–Hillman (MBH) carbonates to access axially chiral tetrasubstituted allenoates. Various trisubstituted allenoates and MBH carbonates were well tolerated under mild reaction conditions, providing novel chiral tetrasubstituted allenoates with adjacent axial chirality and tertiary carbon stereocenters in high yields with good to excellent diastereoselectivities and enantioselectivities.

183W NMR Spectroscopy Guides the Search for Tungsten Alkylidyne Catalysts for Alkyne Metathesis

By Julius Hillenbrand, Markus Leutzsch, Christopher P. Gordon, Christophe Copéret, Alois Fürstner from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 24, 2020.

Silanolate ligands excel with molybdenum alkylidynes but are found to be inadequate for tungsten in that they impart undue Lewis acidity. This effect is manifested in the 183W NMR shifts, which are surprisingly easy to record by 1H,183W HMBC experiments. As a consequence, the ligand scaffold was redesigned and an unprecedented chelate alkoxide complex, which is a new lead in the quest for competent tungsten‐based alkyne metathesis catalysts, was developed. Abstract Triarylsilanolates are privileged ancillary ligands for molybdenum alkylidyne catalysts for alkyne metathesis but lead to disappointing results and poor stability in the tungsten series. 1H,183W heteronuclear multiple bond correlation spectroscopy, exploiting a favorable 5J‐coupling between the 183W center and the peripheral protons on the alkylidyne cap, revealed that these ligands upregulate the Lewis acidity to an extent that the tungstenacyclobutadiene formed in the initial [2+2] cycloaddition step is over‐stabilized and the catalytic turnover brought to a halt. Guided by the 183W NMR shifts as a proxy for the Lewis acidity of the central atom and by an accompanying chemical shift tensor analysis of the alkylidyne unit, the ligand design was revisited and a more strongly π‐donating all‐alkoxide ligand prepared. The new expanded chelate complex has a tempered Lewis acidity and outperforms the classical Schrock catalyst, carrying monodentate tert‐butoxy ligands, in terms of rate and functional‐group compatibility.

Versatile Nickel(II) Scaffolds as Coordination‐Induced Spin‐State Switches for 19F Magnetic Resonance‐Based Detection

By Da Xie, Meng Yu, Zhu‐Lin Xie, Rahul T. Kadakia, Chris Chung, Lauren E. Ohman, Kamyab Javanmardi, Emily L. Que from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 24, 2020.

Two proof‐of‐concept inorganic probes that exploit a novel mechanism for 19F magnetic resonance sensing based on converting from low‐spin (S=0) to high‐spin (S=1) Ni2+ are reported. Activation of diamagnetic NiL1 and NiL2 by light or β‐galactosidase, respectively, converts them into paramagnetic NiL0, which displays a single 19F NMR peak shifted by >35 ppm. This spin‐state switch is effective for sensing light or enzyme expression in live cells. Abstract 19F magnetic resonance (MR) based detection coupled with well‐designed inorganic systems shows promise in biological investigations. Two proof‐of‐concept inorganic probes that exploit a novel mechanism for 19F MR sensing based on converting from low‐spin (S=0) to high‐spin (S=1) Ni2+ are reported. Activation of diamagnetic NiL1 and NiL2 by light or β‐galactosidase, respectively, converts them into paramagnetic NiL0, which displays a single 19F NMR peak shifted by >35 ppm with accelerated relaxation rates. This spin‐state switch is effective for sensing light or enzyme expression in live cells using 19F MR spectroscopy and imaging that differentiate signals based on chemical shift and relaxation times. This general inorganic scaffold has potential for developing agents that can sense analytes ranging from ions to enzymes, opening up diverse possibilities for 19F MR based biosensing.

Intramolecular C(sp3)–H Bond Oxygenation by Transition‐Metal Acylnitrenoids

By Yuqi Tan, Shuming Chen, Zijun Zhou, Yubiao Hong, Sergei Ivlev, K. N. Houk, Eric Meggers from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 24, 2020.

Transition‐metal nitrenoids are well‐established for their C−H amination chemistry but this work demonstrates that N‐acylnitrenoids can surprisingly undergo C(sp3)–H oxygenations instead, even in an enantioselective fashion. Abstract This study demonstrates for the first time that easily accessible transition‐metal acylnitrenoids can be used for controlled direct C(sp3)‐H oxygenations. Specifically, a ruthenium catalyst activates N‐benzoyloxycarbamates as nitrene precursors towards regioselective intramolecular C−H oxygenations to provide cyclic carbonates, hydroxylated carbamates, or 1,2‐diols. The method can be applied to the chemoselective C−H oxygenation of benzylic, allylic, and propargylic C(sp3)−H bonds. The reaction can be performed in an enantioselective fashion and switched in a catalyst‐controlled fashion between C−H oxygenation and C−H amination. This work provides a new reaction mode for the regiocontrolled and stereocontrolled conversion of C(sp3)‐H into C(sp3)−O bonds.

Highly Selective Olefin Production from CO2 Hydrogenation on Iron Catalysts: A Subtle Synergy between Manganese and Sodium Additives

By Yao Xu, Peng Zhai, Yuchen Deng, Jinglin Xie, Xi Liu, Shuai Wang, Ding Ma from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 24, 2020.

A trace amount of Na additive not only promotes the CO2 hydrogenation rate and the olefin selectivity on Fe‐based catalysts, but also turns a Mn additive into a promoter by weakening the strong interaction between Fe and Mn species, leading to unprecedentedly high space‐time yields of olefins for CO2 hydrogenation. Abstract Mn and Na additives have been widely studied to improve the efficiency of CO2 hydrogenation to valuable olefins on Fe catalysts, but their effects on the catalytic properties and mechanism are still under vigorous debate. This study shows that Fe‐based catalysts with moderate Mn and Na contents are highly selective for CO2 hydrogenation to olefins, together with low selectivities for both CO and CH4 and much improved space‐time olefin yields compared to state‐of‐the‐art catalysts. Combined kinetic assessment and quasi in situ characterizations further unveil that the sole presence of Mn suppresses the activity of Fe catalysts because of the close contact between Fe and Mn, whereas the introduction of Na mediates the Fe–Mn interaction and provides strong basic sites. This subtle synergy between Na and Mn sheds light on the importance of the interplay of multiple additives that could bring an enabling strategy to improve catalytic activity and selectivity.

Autocatalytic Formation of High‐Entropy Alloy Nanoparticles

By Nils L. N. Broge, Martin Bondesgaard, Frederik Søndergaard‐Pedersen, Martin Roelsgaard, Bo Brummerstedt Iversen from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 24, 2020.

High‐entropy alloy (HEA) nanoparticles hold great promise as tunable catalysts, and surprisingly, Pt‐Ir‐Pd‐Rh‐Ru nanoparticles can be synthesized under benign low‐temperature solvothermal conditions. In situ X‐ray scattering and TEM reveal the solvothermal formation mechanism of Pt‐Ir‐Pd‐Rh‐Ru nanoparticles. The autocatalytic formation mechanism suggests that many types of HEA nanocatalysts should be accessible with scalable solvothermal reactions. Abstract High‐entropy alloy (HEA) nanoparticles hold great promise as tunable catalysts. Despite the fact that alloy formation is typically difficult in oxygen‐rich environments, we found that Pt‐Ir‐Pd‐Rh‐Ru nanoparticles can be synthesized under benign low‐temperature solvothermal conditions. In situ X‐ray scattering and transmission electron microscopy reveal the solvothermal formation mechanism of Pt‐Ir‐Pd‐Rh‐Ru nanoparticles. For the individual metal acetylacetonate precursors, formation of single metal nanoparticles takes place at temperatures spanning from ca. 150 °C for Pd to ca. 350 °C for Ir. However, for the mixture, homogenous Pt‐Ir‐Pd‐Rh‐Ru HEA nanoparticles can be obtained around 200 °C due to autocatalyzed metal reduction at the (111) facets of the forming crystallites. The autocatalytic formation mechanism suggests that many types of HEA nanocatalysts should accessible with scalable solvothermal reactions, thereby providing broad availability and tunability.

Conformation and Aromaticity Switching in a Curved Non‐Alternant sp2 Carbon Scaffold

By Chongwei Zhu, Kazutaka Shoyama, Frank Würthner from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 24, 2020.

A curved non‐alternant polycyclic aromatic hydrocarbon (PAH) containing fused heptagon and pentagon units is presented, as well as its conformational changes upon stepwise oxidation. Single‐crystal X‐ray analyses for neutral, cationic, dicationic, and a mixed valence species 1⋅(1.+)3 enabled the observed functional properties to be related to the molecular and supramolecular structures. Abstract A curved sp2 carbon scaffold containing fused pentagon and heptagon units (1) was synthesized by Pd‐catalyzed [5+2] annulation from a 3,9‐diboraperylene precursor and shows two reversible oxidation processes at low redox potential, accompanied by a butterfly‐like motion. Stepwise oxidation produced radical cation 1.+ and dication 12+. In the crystal structure, 1 exhibits a chiral cisoid conformation and partial π‐overlap between the enantiomers. For the radical cation 1.+, a less curved cisoid conformation is observed with a π‐dimer‐type arrangement. 12+ adopts a more planar structure with transoid conformation and slip‐stacked π‐overlap with closest neighbors. We also observed an intermolecular mixed‐valence complex of 1⋅(1.+)3 that has a huge trigonal unit cell [(1)72(SbF6)54⋅(hexane)101] and hexagonal columnar stacks. In addition to the conformational change, the aromaticity of 1 changes from localized to delocalized, as demonstrated by AICD and NICS(1)zz calculations.

Smart Design of Nanomaterials for Mitochondria‐Targeted Nanotherapeutics

By Si Si Liew, Xiaofei Qin, Jia Zhou, Lin Li, Wei Huang, Shao Q. Yao from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 24, 2020.

Smart design of nanotherapeutics: Mitochondria play pivotal roles in regulating cell survival and death. They have become important targets in organelle‐targeted therapy. This Review highlights a collection of the latest advances in the design strategies of multifunctional mitochondria‐targeted nanotherapeutics. Abstract Mitochondria are the powerhouse of cells. They are vital organelles that maintain cellular function and metabolism. Dysfunction of mitochondria results in various diseases with a great diversity of clinical appearances. In the past, strategies have been developed for fabricating subcellular‐targeting drug‐delivery nanocarriers, enabling cellular internalization and subsequent organelle localization. Of late, innovative strategies have emerged for the smart design of multifunctional nanocarriers. Hierarchical targeting enables nanocarriers to evade and overcome various barriers encountered upon in vivo administration to reach the organelle with good bioavailability. Stimuli‐responsive nanocarriers allow controlled release of therapeutics to occur at the desired target site. Synergistic therapy can be achieved using a combination of approaches such as chemotherapy, gene and phototherapy. In this Review, we survey the field for recent developments and strategies used in the smart design of nanocarriers for mitochondria‐targeted therapeutics. Existing challenges and unexplored therapeutic opportunities are also highlighted and discussed to inspire the next generation of mitochondrial‐targeting nanotherapeutics.

An Integrated Multi‐Function Heterogeneous Biochemical Circuit for High‐Resolution Electrochemistry‐Based Genetic Analysis

By Yifan Dai, Wei Xu, Rodrigo A. Somoza, Jean F. Welter, Arnold I. Caplan, Chung Chiun Liu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 24, 2020.

A heterogeneous multi‐function biochemical circuit that can identify, transform, translate, and amplify biological signals into physicochemical signals is constructed and integrated with an electrochemistry‐based sensing platform for genetic analysis. The platform is programmed to directly analyze the genome of SARS‐CoV‐2 in human cell lysate, demonstrating the capability and utility of this unique integrated system. Abstract Modular construction of an autonomous and programmable multi‐functional heterogeneous biochemical circuit that can identify, transform, translate, and amplify biological signals into physicochemical signals based on logic design principles can be a powerful means for the development of a variety of biotechnologies. To explore the conceptual validity, we design a CRISPR‐array‐mediated primer‐exchange‐reaction‐based biochemical circuit cascade, which probes a specific biomolecular input, transform the input into a structurally accessible form for circuit wiring, translate the input information into an arbitrary sequence, and finally amplify the prescribed sequence through autonomous formation of a signaling concatemer. This upstream biochemical circuit is further wired with a downstream electrochemical interface, delivering an integrated bioanalytical platform. We program this platform to directly analyze the genome of SARS‐CoV‐2 in human cell lysate, demonstrating the capability and the utility of this unique integrated system.

Redox‐Neutral TEMPO Catalysis: Direct Radical (Hetero)Aryl C−H Di‐ and Trifluoromethoxylation

By Johnny W. Lee, Sanghyun Lim, Daniel N. Maienshein, Peng Liu, Ming‐Yu Ngai from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 24, 2020.

A TEMPO‐catalyzed redox‐neutral di‐ and trifluoromethoxylation of arenes and heteroarenes is reported. The strategy exhibits high functional‐group tolerance and offers flexible late‐stage functionalization of druglike molecules. Mechanistic studies suggest an oxidative TEMPO./TEMPO+ redox catalytic cycle, and Li2CO3 plays an important role in preventing catalyst deactivation. Abstract Applications of TEMPO. catalysis for the development of redox‐neutral transformations are rare. Reported here is the first TEMPO.‐catalyzed, redox‐neutral C−H di‐ and trifluoromethoxylation of (hetero)arenes. The reaction exhibits a broad substrate scope, has high functional‐group tolerance, and can be employed for the late‐stage functionalization of complex druglike molecules. Kinetic measurements, isolation and resubjection of catalytic intermediates, UV/Vis studies, and DFT calculations support the proposed oxidative TEMPO./TEMPO+ redox catalytic cycle. Mechanistic studies also suggest that Li2CO3 plays an important role in preventing catalyst deactivation. These findings will provide new insights into the design and development of novel reactions through redox‐neutral TEMPO. catalysis.

Crystal Facet Induced Single‐Atom Pd/CoxOy on a Tunable Metal–Support Interface for Low Temperature Catalytic Oxidation

By Zehai Xu, Yufan Zhang, Lei Qin, Qin Meng, Zhen Xue, Liqin Qiu, Guoliang Zhang, Xinwen Guo, Qingbiao Li from Wiley: Small: Table of Contents. Published on Sep 24, 2020.

Single‐atom catalysts are achieved on tunable cobalt‐based nanoarrays through crystal facet induced atom trapping. By precisely controlling the metal–support interface, favorable surface chemistry can be provided to create configured heterogeneous Pd/CoxOy catalysts, which exhibit superior activity for low‐temperature oxidation (100% CO conversion at 90 °C) and prominent long‐term stability. Abstract Atomic dispersed metal sites in single‐atom catalysts are highly mobile and easily sintered to form large particles, which deteriorates the catalytic performance severely. Moreover, lack of criterion concerning the role of the metal–support interface prevents more efficient and wide application. Here, a general strategy is reported to synthesize stable single atom catalysts by crafting on a variety of cobalt‐based nanoarrays with precisely controlled architectures and compositions. The highly uniform, well‐aligned, and densely packed nanoarrays provide abundant oxygen vacancies (17.48%) for trapping Pd single atoms and lead to the creation of 3D configured catalysts, which exhibit very competitive activity toward low temperature CO oxidation (100% conversion at 90 °C) and prominent long‐term stability (continuous conversion at 60 °C for 118 h). Theoretical calculations show that O vacancies at high‐index {112} facet of CoxOy nanocrystallite are preferential sites for trapping single atoms, which guarantee strong interface adhesion of Pd species to cobalt‐based support and play a pivotal role in preventing the decrement of activity, even under moisture‐rich conditions (≈2% water vapor). The progress presents a promising opportunity for tailoring catalytic properties consistent with the specific demand on target process, beyond a facile design with a tunable metal–support interface.

Polyimide@Ketjenblack Composite: A Porous Organic Cathode for Fast Rechargeable Potassium‐Ion Batteries

By Chenglin Zhang, Yang Xu, Kaiming He, Yulian Dong, Huaping Zhao, Lukas Medenbach, Yuhan Wu, Andrea Balducci, Thomas Hannappel, Yong Lei from Wiley: Small: Table of Contents. Published on Sep 24, 2020.

An organic Polyimide@Ketjenblack composite is fabricated as potassium‐ion battery cathode through in situ polymerization. Benefiting from the porous structure and carbon skeleton for fast ion and electron transfer, the organic composite exhibits excellent electrochemical performance with large reversible capacity, high rate capability, and long cyclability. Abstract Potassium‐ion batteries (PIBs) configurated by organic electrodes have been identified as a promising alternative to lithium‐ion batteries. Here, a porous organic Polyimide@Ketjenblack is demonstrated in PIBs as a cathode, which exhibits excellent performance with a large reversible capacity (143 mAh g−1 at 100 mA g−1), high rate capability (125 and 105 mAh g−1 at 1000 and 5000 mA g−1), and long cycling stability (76% capacity retention at 2000 mA g−1 over 1000 cycles). The domination of fast capacitive‐like reaction kinetics is verified, which benefits from the porous structure synthesized using in situ polymerization. Moreover, a renewable and low‐cost full cell is demonstrated with superior rate behavior (106 mAh g−1 at 3200 mA g−1). This work proposes a strategy to design polymer electrodes for high‐performance organic PIBs.

Rapid Growth and Fusion of Protocells in Surface‐Adhered Membrane Networks

By Elif S. Köksal, Susanne Liese, Lin Xue, Ruslan Ryskulov, Lauri Viitala, Andreas Carlson, Irep Gözen from Wiley: Small: Table of Contents. Published on Sep 24, 2020.

The emergence and growth of model protocells on networks of lipid nanotubes is accelerated by a moderate increase in temperature. Compartments spontaneously encapsulate RNA fragments from the ambient aqueous solution while growing. With temperature increase, the fusion of adjacent compartments leads to redistribution of the RNA content. Abstract Elevated temperatures might have promoted the nucleation, growth, and replication of protocells on the early Earth. Recent reports have shown evidence that moderately high temperatures not only permit protocell assembly at the origin of life, but can have actively supported it. Here, the fast nucleation and growth of vesicular compartments from autonomously formed lipid networks on solid surfaces, induced by a moderate increase in temperature, are shown. Branches of the networks, initially consisting of self‐assembled interconnected nanotubes, rapidly swell into microcompartments which can spontaneously encapsulate RNA fragments. The increase in temperature further causes fusion of adjacent network‐connected compartments, resulting in the redistribution of the RNA. The experimental observations and the mathematical model indicate that the presence of nanotubular interconnections between protocells facilitates the fusion process.

Golden Bristlegrass‐Like Hierarchical Graphene Nanofibers Entangled with N‐Doped CNTs Containing CoSe2 Nanocrystals at Each Node as Anodes for High‐Rate Sodium‐Ion Batteries

By Min Su Jo, Jae Seob Lee, Sun Young Jeong, Jae Kwang Kim, Yun Chan Kang, Dong Won Kang, Sang Mun Jeong, Jung Sang Cho from Wiley: Small: Table of Contents. Published on Sep 24, 2020.

As high‐performance anodes for sodium‐ion batteries, golden bristlegrass‐like graphene nanofibers entangled with N‐doped CNTs containing CoSe2 nanocrystals are designed and synthesized. The synthesized unique nanostructure exhibits high cycling and rate performances even at extremely high current densities. The synergistic effect of the golden bristlegrass‐like unique structure and the N‐doped CNTs/graphene composite results in efficient anode materials for sodium‐ion batteries. Abstract Golden bristlegrass‐like unique nanostructures comprising reduced graphene oxide (rGO) matrixed nanofibers entangled with bamboo‐like N‐doped carbon nanotubes (CNTs) containing CoSe2 nanocrystals at each node (denoted as N‐CNT/rGO/CoSe2 NF) are designed as anodes for high‐rate sodium‐ion batteries (SIBs). Bamboo‐like N‐doped CNTs (N‐CNTs) are successfully generated on the rGO matrixed nanofiber surface, between rGO sheets and mesopores, and interconnected chemically with homogeneously distributed rGO sheets. The defects in the N‐CNTs formed by a simple etching process allow the complete phase conversion of Co into CoSe2 through the efficient penetration of H2Se gas inside the CNT walls. The N‐CNTs bridge the vertical defects for electron transfer in the rGO sheet layers and increase the distance between the rGO sheets during cycles. The discharge capacity of N‐CNT/rGO/CoSe2 NF after the 10 000th cycle at an extremely high current density of 10 A g−1 is 264 mA h g−1, and the capacity retention measured at the 100th cycle is 89%. N‐CNT/rGO/CoSe2 NF has final discharge capacities of 395, 363, 328, 304, 283, 263, 246, 223, 197, 171, and 151 mA h g−1 at current densities of 1, 2, 4, 6, 8, 10, 12, 14, 16, 18, and 20 A g−1, respectively.

Enhanced Photothermal Therapy through the In Situ Activation of a Temperature and Redox Dual‐Sensitive Nanoreservoir of Triptolide

By Hai‐Jun Liu, Mingming Wang, Xiangxiang Hu, Shanshan Shi, Peisheng Xu from Wiley: Small: Table of Contents. Published on Sep 24, 2020.

A triptolide nanoreservoir, which can be in situ activated by near‐infrared light (NIR) laser irradiation and intracellular high redox potential, is developed to overcome the thermoresistance of cancer cells. Thanks to the inhibited photothermal therapy (PTT) induced heat shock response, the photothermal therapy efficacy of the gold nanorod/mesoporous nanocomplex is greatly improved. Abstract Photothermal therapy (PTT) has attracted tremendous attention due to its noninvasiveness and localized treatment advantages. However, heat shock proteins (HSPs) associated self‐preservation mechanisms bestow cancer cells thermoresistance to protect them from the damage of PTT. To minimize the thermoresistance of cancer cells and improve the efficacy of PTT, an integrated on‐demand nanoplatform composed of a photothermal conversion core (gold nanorod, GNR), a cargo of a HSPs inhibitor (triptolide, TPL), a mesoporous silica based nanoreservoir, and a photothermal and redox di‐responsive polymer shell is developed. The nanoplatform can be enriched in the tumor site, and internalized into cancer cells, releasing the encapsulated TPL under the trigger of intracellular elevated glutathione and near‐infrared laser irradiation. Ultimately, the liberated TPL could diminish thermoresistance of cancer cells by antagonizing the PTT induced heat shock response via multiple mechanisms to maximize the PTT effect for cancer treatment.

Fundamental Understanding of the Formation Mechanism for Graphene Quantum Dots Fabricated by Pulsed Laser Fragmentation in Liquid: Experimental and Theoretical Insight

By Sukhyun Kang, Kyung Hwan Jung, Sungwook Mhin, Yong Son, Kangpyo Lee, Won Rae Kim, Heechae Choi, Jeong Ho Ryu, Hyuksu Han, Kang Min Kim from Wiley: Small: Table of Contents. Published on Sep 24, 2020.

The pulsed laser fragmentation in liquid (PLFL) process is a promising technique for the synthesis of carbon‐based functional materials. A mechanism for the formation of graphene quantum dots from carbon precursor by the PLFL process is reported, through the combination of experimental and theoretical studies. Abstract The pulsed laser fragmentation in liquid (PLFL) process is a promising technique for the synthesis of carbon‐based functional materials. In particular, there has been considerable attention on graphene quantum dots (GQDs) derived from multiwalled carbon nanotubes (MWCNTs) by the PLFL process, owing to the low cost and rapid processing time involved. However, a fundamental deep understanding of the formation of GQDs from MWCNTs by PLFL has still not been achieved despite the high demand. In this work, a mechanism for the formation of GQDs from MWCNTs by the PLFL process is reported, through the combination of experimental and theoretical studies. Both the experimental and computational results demonstrate that the formation of GQDs strongly depends on the pulse laser energy. Both methods demonstrate that the critical energy point, where a plasma plume is generated on the surface of the MWCNTs, should be precisely maintained to produce GQDs; otherwise, an amorphous carbon structure is favorably formed from the scattered carbons.

Combined Tumor Environment Triggered Self‐Assembling Peptide Nanofibers and Inducible Multivalent Ligand Display for Cancer Cell Targeting with Enhanced Sensitivity and Specificity

By Weike Chen, Shuxin Li, John C. Lang, Yan Chang, Zui Pan, Peter Kroll, Xiankai Sun, Liping Tang, He Dong from Wiley: Small: Table of Contents. Published on Sep 24, 2020.

A new family of self‐assembling peptide monomer precursors can undergo tumor microenvironment triggered chemical transformation and subsequent supramolecular assembly with induced multivalent ligand presentation for enhanced tumor cell targeting sensitivity and specificity. The structure–activity relationship suggests that the ligand‐receptor binding is dependent on the supramolecular morphology with elongated nanofibers being more effective than shorter nanofibers and spherical aggregates. Abstract Many new technologies, such as cancer microenvironment‐induced nanoparticle targeting and multivalent ligand approach for cell surface receptors, are developed for active targeting in cancer therapy. While the principle of each technology is well illustrated, most systems suffer from low targeting specificity and sensitivity. To fill the gap, this work demonstrates a successful attempt to combine both technologies to simultaneously improve cancer cell targeting sensitivity and specificity. Specifically, the main component is a targeting ligand conjugated self‐assembling monomer precursor (SAM‐P), which, at the tumor site, undergoes tumor‐triggered cleavage to release the active form of self‐assembling monomer capable of forming supramolecular nanostructures. Biophysical characterization confirms the chemical and physical transformation of SAM‐P from unimers or oligomers with low ligand valency to supramolecular assemblies with high ligand valency under a tumor‐mimicking reductive microenvironment. The in vitro fluorescence assay shows the importance of supramolecular morphology in mediating ligand–receptor interactions and targeting sensitivity. Enhanced targeting specificity and sensitivity can be achieved via tumor‐triggered supramolecular assembly and induces multivalent ligand presentation toward cell surface receptors, respectively. The results support this combined tumor microenvironment‐induced cell targeting and multivalent ligand display approach, and have great potential for use as cell‐specific molecular imaging and therapeutic agents with high sensitivity and specificity.

High Performance Lithium‐Ion Batteries Using Layered 2H‐MoTe2 as Anode

By Manas Ranjan Panda, Rashmi Gangwar, Divyamahalakshmi Muthuraj, Supriya Sau, Dhanshree Pandey, Arup Banerjee, Aparna Chakrabarti, Archna Sagdeo, Matthew Weyland, Mainak Majumder, Qiaoliang Bao, Sagar Mitra from Wiley: Small: Table of Contents. Published on Sep 24, 2020.

Semiconducting 2H‐phase of MoTe2 synthesized by a solid‐state route is used as anode material in lithium‐ion batteries. In situ X‐ray absorption near‐edge structures reveal the unique lithium reaction pathway and storage mechanism, which is further complemented by density functional theory calculations. The full cell exhibits a high energy density of 454 Wh kg−1 with outstanding cycling stability, implying its potential for practical applications. Abstract The major challenges faced by candidate electrode materials in lithium‐ion batteries (LIBs) include their low electronic and ionic conductivities. 2D van der Waals materials with good electronic conductivity and weak interlayer interaction have been intensively studied in the electrochemical processes involving ion migrations. In particular, molybdenum ditelluride (MoTe2) has emerged as a new material for energy storage applications. Though 2H‐MoTe2 with hexagonal semiconducting phase is expected to facilitate more efficient ion insertion/deinsertion than the monoclinic semi‐metallic phase, its application as an anode in LIB has been elusive. Here, 2H‐MoTe2, prepared by a solid‐state synthesis route, has been employed as an efficient anode with remarkable Li+ storage capacity. The as‐prepared 2H‐MoTe2 electrodes exhibit an initial specific capacity of 432 mAh g−1 and retain a high reversible specific capacity of 291 mAh g−1 after 260 cycles at 1.0 A g−1. Further, a full‐cell prototype is demonstrated by using 2H‐MoTe2 anode with lithium cobalt oxide cathode, showing a high energy density of 454 Wh kg−1 (based on the MoTe2 mass) and capacity retention of 80% over 100 cycles. Synchrotron‐based in situ X‐ray absorption near‐edge structures have revealed the unique lithium reaction pathway and storage mechanism, which is supported by density functional theory based calculations.

Co‐Induced Electronic Optimization of Hierarchical NiFe LDH for Oxygen Evolution

By Yanping Lin, Hao Wang, Chun‐Kuo Peng, Liangmin Bu, Chao‐Lung Chiang, Kai Tian, Yue Zhao, Jianqing Zhao, Yan‐Gu Lin, Jong‐Min Lee, Lijun Gao from Wiley: Small: Table of Contents. Published on Sep 24, 2020.

Hierarchical nanostructures fabricated from edge‐rich nickel–iron–cobalt layered double hydroxides (NiFeCo‐LDH) nanosheets and carbon fiber are synthesized by solvent‐thermal treatment of ZIF‐67/CF. Owing to the synergistic interaction between the three metal ions, largely exposed active surface sites and tunable electronic structure in LDH materials, NiFeCo‐LDH/CF displays superior oxygen evolution reaction performance and robust stability. Abstract Developing efficient and stable non‐noble electrocatalysts for the oxygen evolution reaction (OER) remains challenging for practical applications. While nickel–iron layered double hydroxides (NiFe‐LDH) are emerging as prominent candidates with promising OER activity, their catalytic performance is still restricted by the limited active sites, poor conductivity and durability. Herein, hierarchical nickel–iron–cobalt LDH nanosheets/carbon fibers (NiFeCo‐LDH/CF) are synthesized through solvent‐thermal treatment of ZIF‐67/CF. Extended X‐ray adsorption fine structure analyses reveal that the Co substitution can stabilize the Fe local coordination environment and facilitate the π‐symmetry bonding orbital in NiFeCo‐LDH/CF, thus modifying the electronic structures. Coupling with the structural advantages, including the largely exposed active surface sites and facilitated charge transfer pathway ensured by CF, the resultant NiFeCo‐LDH/CF exhibits excellent OER activity with an overpotential of 249 mV at 10 mA cm−1 as well as robust stability over 20 h.

Enhancement of Magneto‐Mechanical Actuation of Micropillar Arrays by Anisotropic Stress Distribution

By Jeong Eun Park, Jisoo Jeon, Sei Jin Park, Sukyoung Won, Zahyun Ku, Jeong Jae Wie from Wiley: Small: Table of Contents. Published on Sep 24, 2020.

When a magnetic field is applied at an offset angle with respect to the magnetic particle alignment, a magnetic torque is generated within the micropillars. The direction of magnetic actuation is determined by the offset angle between the main axis of pillars and the magnetic field axis. Anisotropic micropillar cross sections drastically enhance their magneto‐mechanical actuation. Abstract Magnetically active shape‐reconfigurable microarrays undergo programmed actuation according to the arrangement of magnetic dipoles within the structures, achieving complex twisting and bending deformations. Cylindrical micropillars have been widely used to date, whose circular cross‐sections lead to identical actuation regardless of the actuating direction. In this study, micropillars with triangular or rectangular cross‐sections are designed and fabricated to introduce preferential actuation directions and explore the limits of their actuation. Using such structures, controlled liquid wetting is demonstrated on micropillar surfaces. Liquid droplets pinned on magnetic micropillar arrays undergo directional spreading when the pillars are actuated as depinning of the droplets is enabled only in certain directions. The enhanced deformation due to direction dependent magneto‐mechanical actuation suggests that micropillar arrays can be fundamentally tailored to possess application specific responses and opens up opportunities to exploit more complex designs such as micropillars with polygonal cross sections. Such tunable wetting of liquids on microarray surfaces has potential to improve printing technologies via contactless reconfiguration of stamp geometry by magnetic field manipulation.

Ultrafast Growth and Locomotion of Dandelion‐Like Microswarms with Tubular Micromotors

By Xiaolong Lu, Hui Shen, Ying Wei, Hongbin Ge, Joseph Wang, Hanmin Peng, Wenjuan Liu from Wiley: Small: Table of Contents. Published on Sep 24, 2020.

Dandelion‐like microswarms assembled from tubular micromotors are capable of performing ultrafast growth and locomotion in surfactant‐free low concentrated H2O2 solutions. With the ultrasound oscillation of self‐generated bubbles, such microswarms could overcome the tremendous and chaotic drag force from extensive and disordered bubble generation in single units, offering a new rapid methodology for constructing distinctive dynamic assembly for microrobots. Abstract Dynamic assembly and cooperation represent future frontiers for next generations of advanced micro/nano robots, but the required local interaction and communication cannot be directly translated from macroscale robots through the minimization because of tremendous technological challenges. Here, an ultrafast growth and locomotion methodology is presented for dandelion‐like microswarms assembled from catalytic tubular micromotors. With ultrasound oscillation of self‐generated bubbles, such microswarms could overcome the tremendous and chaotic drag force from extensive and disordered bubble generation in single units. Tubular MnO2 micromotor individuals headed by self‐generated oxygen bubbles are ultrasonically driven to swim rapidly in surfactant‐free H2O2 solutions. A large bubble core fused from multiple microbubbles is excited to oscillate and the resultant local intensified acoustic field attracts the individual micromotors to school around it, leading to a simultaneous growth of dandelion‐like microswarms. The bubble‐carried micromotor groups driven by ultrasound could swarm at a zigzag pattern with an average speed of up to 50 mm s−1, which is validated in low H2O2 concentrations. Additionally, such superfast locomotion could be ultrasonically modulated on demand. The ultrafast microswarm growth and locomotion strategy offers a new paradigm for constructing distinct dynamic assemblies and rapid transmission of artificial microrobots, paving the way to a myriad of promising applications.

Tin Nanodots Derived From Sn2+/Graphene Quantum Dot Complex as Pillars into Graphene Blocks for Ultrafast and Ultrastable Sodium‐Ion Storage

By Zheng Liu, Su Zhang, Zhipeng Qiu, Chao Huangfu, Lin Wang, Tong Wei, Zhuangjun Fan from Wiley: Small: Table of Contents. Published on Sep 24, 2020.

Graphene quantum dot edge‐anchored tin nanodots pillared graphene blocks (NGQD/Sn‐NG) as sodium‐ion battery anodes exhibit excellent rate performance (555 mAh g−1 at 0.1 A g−1 and 198 mAh g−1 at 10 A g−1), and ultra‐long cycling stability (184 mAh g−1 remaining even after 2000 cycles at 5 A g−1). Abstract Tin (Sn) is considered to be an ideal candidate for the anode of sodium ion batteries. However, the design of Sn‐based electrodes with maintained long‐term stability still remains challenging due to their huge volume expansion (≈420%) and easy pulverization during cycling. Herein, a facile and versatile strategy for the synthesis of nitrogen‐doped graphene quantum dot (GQD) edge‐anchored Sn nanodots as the pillars into reduced graphene oxide blocks (NGQD/Sn‐NG) for ultrafast and ultrastable sodium‐ion storage is reported. Sn nanodots (2–5 nm) anchored at the edges of “octopus‐like” GQDs via covalent SnOC/SnNC bonds function as the pillars that ensure fast Na‐ion/electron transport across the graphene blocks. Moreover, the chemical and spatial (layered structure) confinements not only suppress Sn aggregation, but also function as physical barriers for buffering volume change upon sodiation/desodiation. Consequently, the NGQD/Sn‐NG with high structural stability exhibits excellent rate performance (555 mAh g−1 at 0.1 A g−1 and 198 mAh g−1 at 10 A g−1) and ultra‐long cycling stability (184 mAh g−1 remaining even after 2000 cycles at 5 A g−1). The confinement‐induced synthesis together with remarkable electrochemical performances should shed light on the practical application of highly attractive tin‐based anodes for next generation rechargeable sodium batteries.

Engineering Solvation Complex–Membrane Interaction to Suppress Cation Crossover in 3 V Cu‐Al Battery

By Huimin Wang, Yang Sun, Matthew Li, Gaoran Li, Kaiming Xue, Zhongwei Chen, Denis Y. W. Yu from Wiley: Small: Table of Contents. Published on Sep 24, 2020.

A 3 V Cu‐Al battery with earth‐abundant Cu and Al foils and inexpensive polypropylene membrane in 3 m LiTFSI fluoroethylene carbonate (FEC) electrolyte is demonstrated. The repulsive interactions between Cu‐solvation structure and polypropylene suppress Cu crossover and self‐discharge. The Cu‐Al battery exhibits excellent cycle stability in 3 m LiTFSI FEC electrolyte due to the high binding energy between Cu ions and FEC solvent. Abstract Metal–metal batteries such as the 3 V Cu‐Al system are highly desirable for large‐scale energy storage owing to their low cost and excellent scalability of Cu and Al foils. However, the dissolved Cu cations will crossover from the cathode to the anode leading to poor electrochemical performance. In this work, it is demonstrated that the reversibility of the Cu‐Al battery depends strongly on the interaction of the Cu ions with the electrolyte solvent and subsequently the affinity of the solvated Cu ion with the membrane separator. Specifically, a series of common carbonate‐based electrolyte solvents are investigated via molecular dynamics and contact angle measurements to understand the interaction between the solvents and a polypropylene (PP) membrane, as well as that between cations and solvent. Among different solvents, fluoroethylene carbonate (FEC) is shown to drastically enhance the coulombic efficiency to 97%, compared to that of 27% with dimethyl carbonate. Remarkable cyclability of a 3 V Cu‐Al battery with 3 m LiTFSI FEC and PP membrane up to 1000 cycles is further demonstrated. This finding opens new opportunities for the development of low‐cost, high performance Cu‐Al systems for stationary applications.

Binary Nanoparticle Superlattices for Plasmonically Modulating Upconversion Luminescence

By Kerong Deng, Lili Xu, Xin Guo, Xiaotong Wu, Yulian Liu, Zhimin Zhu, Qian Li, Qiuqiang Zhan, Chunxia Li, Zewei Quan from Wiley: Small: Table of Contents. Published on Sep 24, 2020.

Homogeneous, well‐defined, and distinct two‐dimensional binary nanoparticle superlattices (BNSLs) are self‐assembled from spherical upconversion (NaREF4:Yb/Er UCNPs) and gold nanoparticles, aiming to plasmonically modulate the upconversion luminescence (UCL). The ordered arrangement of BNSLs can achieve modified UCL with a dominant red emission, reduced lifetime, and even fine‐structured lineshape containing more sharp peaks, due to the collective plasmon resonance. Abstract Engineering a facile and controllable approach to modulate the spectral properties of lanthanide‐doped upconversion nanoparticles (UCNPs) is always an ongoing challenge. Herein, long‐range ordered, distinct two‐dimensional (2D) binary nanoparticle superlattices (BNSLs) composed of NaREF4:Yb/Er (RE = Y and Gd) UCNPs and plasmonic metallic nanoparticles (Au NPs), including AB, AB3, and AB13 lattices, are fabricated via a slow evaporation‐driven self‐assembly to achieve plasmonic modulation of upconversion luminescence (UCL). Optical measurements reveal that typical red–green UCL from UCNPs can be effectively modulated into reddish output in BNSLs, with a drastically shortened lifetime. Notably, for AB3‐ and AB13‐type BNSLs with more proximal Au NPs around each UCNP, modified UCL with fine‐structured spectral lineshape is observed. These differences could be interpreted by the interplay of collective plasmon resonance introduced by 2D periodic Au arrays and spectrally selective energy transfer between UCNPs and Au. Thus, fabricating UCNP‐Au BNSLs with desired lattice parameters and NP configurations could be a promising way to tailor the UCL through controlled plasmonic modulation.

An Activatable Nano‐Prodrug for Treating Tyrosine‐Kinase‐Inhibitor‐Resistant Non‐Small Cell Lung Cancer and for Optoacoustic and Fluorescent Imaging

By Xin Xie, Chenyue Zhan, Jie Wang, Fang Zeng, Shuizhu Wu from Wiley: Small: Table of Contents. Published on Sep 24, 2020.

A nano‐prodrug for treating tyrosine‐kinase‐inhibitor‐resistant non‐small cell lung cancer is fabricated. It accumulates in lung tumor and releases two active drugs to effectively inhibit both the upstream and downstream proteins of the epidermal growth factor receptor (EGFR) signaling pathway to achieve high therapeutic efficacy. A near‐infrared (NIR) dye is generated in this process for fluorescence and optoacoustic imaging of drug release. Abstract Non‐small cell lung cancer (NSCLC) is the most common type of lung cancer and the cause of high rate of mortality. The epidermal growth factor receptor (EGFR)‐targeted tyrosine kinase inhibitors are used to treat NSCLC, yet their curative effects are usually compromised by drug resistance. This study demonstrates a nanodrug for treating tyrosine‐kinase‐inhibitor‐resistant NSCLC through inhibiting upstream and downstream EGFR signaling pathways. The main molecule of the nanodrug is synthesized by linking a tyrosine kinase inhibitor gefitinib and a near‐infrared dye (NIR) on each side of a disulfide via carbonate bonds, and the nanodrug is then obtained through nanoparticle formation of the main molecule in aqueous medium and concomitant encapsulation of a serine threonine protein kinase (Akt) inhibitor celastrol. Upon administration, the nanodrug accumulates at the tumor region of NSCLC‐bearing mice and releases the drugs for tumor inhibition, and the dye for fluorescence and optoacoustic imaging. Through suppressing the phosphorylation of upstream EGFR and downstream Akt in the EGFR pathway by gefitinib and celastrol, respectively, the nanodrug exhibits high inhibition efficacy against orthotopic NSCLC in mouse models.

DNA Nanostructures as Pt(IV) Prodrug Delivery Systems to Combat Chemoresistance

By Yi‐Fang Zhong, Jin Cheng, Yan Liu, Tao Luo, Yuqi Wang, Kai Jiang, Fangli Mo, Jie Song from Wiley: Small: Table of Contents. Published on Sep 24, 2020.

Three DNA nanostructures with varied sizes and shapes are constructed and their efficiency as Pt(IV) prodrug delivery systems to combat chemoresistance are investigated. This study has revealed that 6x6x64nt‐Pt(IV), which markedly enhances the cellular internalization of platinum drugs and shows high tumor passive targeting ability, is the optimal design for Pt(IV) prodrug delivery in vitro and in vivo. Abstract Cisplatin is a first‐line drug in clinical cancer treatment but its efficacy is often hindered by chemoresistance in cancer cells. Reduced intracellular drug accumulation is revealed to be a major mechanism of cisplatin resistance. Nanoscale drug delivery systems could help to overcome this problem because of their more active cellular uptake and more accurate tumor localization. DNA nanostructures have emerged as promising drug delivery systems because of their intrinsic biocompatibility and structural programmability. Herein, three diverse DNA nanostructures are constructed and their potential for cisplatin prodrug delivery is investigated. Results found that these DNA nanostructures could remarkably enhance the cellular internalization of platinum drugs and thus increase the anticancer activity, not only to regular lung cancer cells (A549), but more importantly to cisplatin‐resistant cancer cells (A549cisR). Further, in vivo studies also demonstrate that cisplatin prodrug loaded DNA nanostructures could effectively suppress tumor growth in both regular and cisplatin‐resistant tumor models. This study suggests that DNA nanostructures are effective carriers for platinum prodrug delivery to combat chemoresistance.

A Biomimetic Polymer Magnetic Nanocarrier Polarizing Tumor‐Associated Macrophages for Potentiating Immunotherapy

By Lingqiao Liu, Yi Wang, Xing Guo, Jingya Zhao, Shaobing Zhou from Wiley: Small: Table of Contents. Published on Sep 24, 2020.

A biomimetic polymer magnetic nanocarrier is developed, which possesses a great capacity of potentiating immunotherapy of breast cancer through selectively targeting and polarizing tumor‐associated macrophages. The polarization is ascribed to the fact that Fe3O4 nanoparticles mainly activate the IRF5 signaling pathway via iron ions instead of the previously reported reactive oxygen species‐induced NF‐κB signaling pathway. Abstract The progress of antitumor immunotherapy is usually limited by tumor‐associated macrophages (TAMs) that account for the highest proportion of immunosuppressive cells in the tumor microenvironment, and the TAMs can also be reversed by modulating the M2‐like phenotype. Herein, a biomimetic polymer magnetic nanocarrier is developed with selectively targeting and polarizing TAMs for potentiating immunotherapy of breast cancer. This nanocarrier PLGA‐ION‐R837 @ M (PIR @ M) is achieved, first, by the fabrication of magnetic polymer nanoparticles (NPs) encapsulating Fe3O4 NPs and Toll‐like receptor 7 (TLR7) agonist imiquimod (R837) and, second, by the coating of the lipopolysaccharide (LPS)‐ treated macrophage membranes on the surface of the NPs for targeting TAMs. The intracellular uptake of the PIR @ M can greatly polarize TAMs from M2 to antitumor M1 phenotype with the synergy of Fe3O4 NPs and R837. The relevant mechanism of the polarization is deeply studied through analyzing the mRNA expression of the signaling pathways. Different from previous reports, the polarization is ascribed to the fact that Fe3O4 NPs mainly activate the IRF5 signaling pathway via iron ions instead of the reactive oxygen species‐induced NF‐κB signaling pathway. The anticancer effect can be effectively enhanced through potentiating immunotherapy by the polarization of the TAMs in the combination of Fe3O4 NPs and R837.

Targeted Theranostic Nano Vehicle Endorsed with Self‐Destruction and Immunostimulatory Features to Circumvent Drug Resistance and Wipe‐Out Tumor Reinitiating Cancer Stem Cells

By Manu M. Joseph, Adukkadan N. Ramya, Vineeth M. Vijayan, Jyothi B. Nair, Blossom T. Bastian, Raveendran K. Pillai, Sreelekha T. Therakathinal, Kaustabh K. Maiti from Wiley: Small: Table of Contents. Published on Sep 24, 2020.

Here, the precise elimination of drug‐sensitive and resistant cancer cells along with cancer stem cells with the intelligent fabrication of a targeted theranostic nano vehicle (TTNV) is demonstrated. A tumor‐targeted biodistribution followed by a striking pattern of bioelimination of this TTNV contributes to the wipe‐out of tumor mass on both folate receptor‐positive and CD44‐positive tumor‐bearing mice. Abstract The downsides of conventional cancer monotherapies are profound and enormously consequential, as drug‐resistant cancer cells and cancer stem cells (CSC) are typically not eliminated. Here, a targeted theranostic nano vehicle (TTNV) is designed using manganese‐doped mesoporous silica nanoparticle with an ideal surface area and pore volume for co‐loading an optimized ratio of antineoplastic doxorubicin and a drug efflux inhibitor tariquidar. This strategically framed TTNV is chemically conjugated with folic acid and hyaluronic acid as a dual‐targeting entity to promote folate receptor (FR) mediated cancer cells and CD44 mediated CSC uptake, respectively. Interestingly, surface‐enhanced Raman spectroscopy is exploited to evaluate the molecular changes associated with therapeutic progression. Tumor microenvironment selective biodegradation and immunostimulatory potential of the MSN‐Mn core are safeguarded with a chitosan coating which modulates the premature cargo release and accords biocompatibility. The superior antitumor response in FR‐positive syngeneic and CSC‐rich human xenograft murine models is associated with a tumor‐targeted biodistribution, favorable pharmacokinetics, and an appealing bioelimination pattern of the TTNV with no palpable signs of toxicity. This dual drug‐loaded nano vehicle offers a feasible approach for efficient cancer therapy by on demand cargo release in order to execute complete wipe‐out of tumor reinitiating cancer stem cells.

Multiphase Assembly of Small Molecule Microcrystalline Peptide Hydrogel Allows Immunomodulatory Combination Therapy for Long‐Term Heart Transplant Survival

By Poulami Majumder, Yichuan Zhang, Marcos Iglesias, Lixin Fan, James A. Kelley, Caroline Andrews, Nimit Patel, Jason R. Stagno, Byoung Chol Oh, Georg J. Furtmüller, Christopher C. Lai, Yun‐Xing Wang, Gerald Brandacher, Giorgio Raimondi, Joel P. Schneider from Wiley: Small: Table of Contents. Published on Sep 24, 2020.

Combination therapies targeting pathways in immune rejection of transplants hold promise for restorative surgery patients. Microcrystalline tofacitinib hydrogel (MTH) can be syringe‐injected directly to the grafting site to locally deliver tofacitinib, a potent JAK1/3 inhibitor. A single application of MTH, in combination with systemic CTLA4‐Ig, a co‐stimulation inhibitor, affords significant graft survival in mice receiving heterotopic heart transplants. Abstract Combination therapies that target multiple pathways involved in immune rejection of transplants hold promise for patients in need of restorative surgery. Herein, a noninteracting multiphase molecular assembly approach is developed to crystallize tofacitinib, a potent JAK1/3 inhibitor, within a shear‐thinning self‐assembled fibrillar peptide hydrogel network. The resulting microcrystalline tofacitinib hydrogel (MTH) can be syringe‐injected directly to the grafting site during surgery to locally deliver the small molecule. The rate of drug delivered from MTH is largely controlled by the dissolution of the encapsulated microcrystals. A single application of MTH, in combination with systemically delivered CTLA4‐Ig, a co‐stimulation inhibitor, affords significant graft survival in mice receiving heterotopic heart transplants. Locoregional studies indicate that the local delivery of tofacitinib at the graft site enabled by MTH is required for the observed enhanced graft survival.

Rational Design of FeNi Bimetal Modified Covalent Organic Frameworks for Photoconversion of Anthropogenic CO2 into Widely Tunable Syngas

By Bin Han, Xinwen Ou, Zuqi Zhong, Shujie Liang, Hong Deng, Zhang Lin from Wiley: Small: Table of Contents. Published on Sep 24, 2020.

Photocatalytic conversion of low‐concentration CO2 into syngas with a widely tunable CO/H2 ratio is achieved on Fe/Ni‐covalent organic frameworks. The differences of adsorption affinities for CO2 and H2O on metal sites are the determining factors for tuning the CO/H2 ratio, providing a modular catalyst design strategy. Abstract Direct photoconversion of low‐concentration CO2 into a widely tunable syngas (i.e., CO/H2 mixture) provides a feasible outlet for the high value‐added utilization of anthropogenic CO2. However, in the low‐concentration CO2 photoreduction system, it remains a huge challenge to screen appropriate catalysts for efficient CO and H2 production, respectively, and provide a facile parameter to tune the CO/H2 ratio in a wide range. Herein, by engineering the metal sites on the covalent organic frameworks matrix, low‐concentration CO2 can be efficiently photoconverted into tunable syngas, whose CO/H2 ratio (1:19–9:1) is obviously wider than reported systems. Experiments and density functional theory calculations indicate that Fe sites serve as the H2 evolution sites due to the much stronger binding affinity to H2O, while Ni sites act as the CO production sites for the higher affinity to CO2. Notably, the widely tunable syngas can also be produced over other Fe/Ni‐based bimetal catalysts, regardless of their structures and supporting materials, confirming the significant role of the metal sites in regulating the selectivity of CO2 photoreduction and providing a modular design strategy for syngas production.

Zeolite Nanosheets Stabilize Catalyst Particles to Promote the Growth of Thermodynamically Unfavorable, Small‐Diameter Carbon Nanotubes

By Jennifer Carpena‐Núñez, Rahul Rao, Donghun Kim, Ksenia V. Bets, Dmitri N. Zakharov, J. Anibal Boscoboinik, Eric A. Stach, Boris I. Yakobson, Michael Tsapatsis, Dario Stacchiola, Benji Maruyama from Wiley: Small: Table of Contents. Published on Sep 24, 2020.

Cobalt‐nanoparticle stabilization on the external surface of Mobil‐five (MFI) nanosheets leads to a catalyst/support registry, to the suppression of particle coarsening during high‐temperature annealing, and to the growth of small‐diameter single‐wall carbon nanotubes (CNTs) of nearly all chiralities, including the thermodynamically unfavorable zig‐zag and near‐zig‐zag CNTs. Abstract A challenge in the synthesis of single‐wall carbon nanotubes (SWCNTs) is the lack of control over the formation and evolution of catalyst nanoparticles and the lack of control over their size or chirality. Here, zeolite MFI nanosheets (MFI‐Ns) are used to keep cobalt (Co) nanoparticles stable during prolonged annealing conditions. Environmental transmission electron microscopy (ETEM) shows that the MFI‐Ns can influence the size and shape of nanoparticles via particle/support registry, which leads to the preferential docking of nanoparticles to four or fewer pores and to the regulation of the SWCNT synthesis products. The resulting SWCNT population exhibits a narrow diameter distribution and SWCNTs of nearly all chiral angles, including sub‐nm zigzag (ZZ) and near‐ZZ tubes. Theoretical simulations reveal that the growth of these unfavorable tubes from unsupported catalysts leads to the rapid encapsulation of catalyst nanoparticles bearing them; their presence in the growth products suggests that the MFI‐Ns prevent nanoparticle encapsulation and prologue ZZ and near‐ZZ SWCNT growth. These results thus present a path forward for controlling nanoparticle formation and evolution, for achieving size‐ and shape‐selectivity at high temperature, and for controlling SWCNT synthesis.

Probing the Irregular Lattice Strain‐Induced Electronic Structure Variations on Late Transition Metals for Boosting the Electrocatalyst Activity

By Tong Wu, Mingzi Sun, Bolong Huang from Wiley: Small: Table of Contents. Published on Sep 24, 2020.

The simplified strain effect in electroactivity is extended based on theoretical calculations for typical transition metals. By probing the irregular electronic structure with consideration of facet, an insightful understanding of typical strain effect on the modulation of electroactivity in transition metal catalysts is obtained. This work supplies pivotal theoretical reference for future catalyst design. Abstract Owing to the simplicity in practice and continuous fine‐tuning ability toward the binding strengths of adsorbates, the strain effect is intensively explored, especially focused on the modulation of catalytic activity in transition metal (TM) based electrocatalysts. Recently, more and more abnormal cases have been found that cannot be explained by the conventional simplified models. In this work, the strain effects in five late TMs, Fe, Co, Ni, Pd, and Pt are studied in‐depth regarding the facet engineering, the surface atom density, and the d‐band center. Interestingly, the irregular response of Fe lattice to the applied strain is identified, indicating the untapped potential of achieving the phase change by precise strain modulation. For the complicated high‐index facets, the surface atom density has become the pivotal factor in determining the surface stability and electroactivity, which identifies the potential of high entropy alloys (HEA) in electrocatalysis. The work supplies insightful understanding and significant references for future research in subtle modulation of electroactivity based on the precise facet engineering in the more complex facets and morphologies.

ZnO/Nanocarbons‐Modified Fibrous Scaffolds for Stem Cell‐Based Osteogenic Differentiation

By Yi Xia, Xin Fan, Hua Yang, Ling Li, Chao He, Chong Cheng, Rainer Haag from Wiley: Small: Table of Contents. Published on Sep 24, 2020.

ZnO/nanocarbons‐modified fibrous scaffolds are fabricated for mesenchymal stem cells‐based osteogenic differentiation. The scaffolds show enhanced expression of alkaline phosphatase, bone sialoprotein, vinculin, and larger cell‐spreading area. The combined benefits of unique nanostructures and Zn2+ ions releasing not only endow the scaffolds with simultaneously enhanced osteogenic and anti‐infective capabilities but also provide new insights for designing stem cells‐regeneration scaffolds. Abstract Currently, mesenchymal stem cells (MSCs)‐based therapies for bone regeneration and treatments have gained significant attention in clinical research. Though many chemical and physical cues which influence the osteogenic differentiation of MSCs have been explored, scaffolds combining the benefits of Zn2+ ions and unique nanostructures may become an ideal interface to enhance osteogenic and anti‐infective capabilities simultaneously. In this work, motivated by the enormous advantages of Zn‐based metal–organic framework‐derived nanocarbons, C‐ZnO nanocarbons‐modified fibrous scaffolds for stem cell‐based osteogenic differentiation are constructed. The modified scaffolds show enhanced expression of alkaline phosphatase, bone sialoprotein, vinculin, and a larger cell spreading area. Meanwhile, the caging of ZnO nanoparticles can allow the slow release of Zn2+ ions, which not only activate various signaling pathways to guide osteogenic differentiation but also prevent the potential bacterial infection of implantable scaffolds. Overall, this study may provide new insight for designing stem cell‐based nanostructured fibrous scaffolds with simultaneously enhanced osteogenic and anti‐infective capabilities.

Highly Stable Vanadium Redox‐Flow Battery Assisted by Redox‐Mediated Catalysis

By Lu Xia, Ting Long, Wenyue Li, Fangfang Zhong, Mei Ding, Yong Long, Zhizhao Xu, Yanqiang Lei, Yong Guan, Du Yuan, Yiqiong Zhang, Chuankun Jia, Lidong Sun, Qijun Sun from Wiley: Small: Table of Contents. Published on Sep 24, 2020.

A highly stable vanadium redox‐flow battery assisted by Prussian blue catalyst is demonstrated, which offers a redox‐mediated catalysis process to facilitate the interfacial charge transfer and enhance the energy efficiency. The battery shows a maximum power density of 1215 mW cm−2, the best average voltage efficiency of ≈90% and energy efficiency of ≈88% at 100 mA cm−2. Abstract With good operation flexibility and scalability, vanadium redox‐flow batteries (VRBs) stand out from various electrochemical energy storage (EES) technologies. However, traditional electrodes in VRBs, such as carbon and graphite felt with low electrochemical activities, impede the interfacial charge transfer processes and generate considerable overpotential loss, which significantly decrease the energy and voltage efficiencies of VRBs. Herein, by using a facile electrodeposition technique, Prussian blue/carbon felt (PB/CF) composite electrodes with high electrochemical activity for VRBs are successfully fabricated. The PB/CF electrode exhibits excellent electrochemical activity toward VO2+/VO2+ redox couple in VRB with an average cell voltage efficiency (VE) of 90% and an energy efficiency (EE) of 88% at 100 mA cm−2. In addition, due to the uniformly distributed PB particles that are strongly bound to the surface of carbon fibers in CF, VRBs with the PB/CF electrodes show much better long‐term stabilities compared with the pristine CF‐based battery due to the redox‐mediated catalysis. A VRB stack consisting of three single cells (16 cm2) is also constructed to assess the reliability of the redox‐mediated PB/CF electrodes for large‐scale application. The facile technique for the high‐performance electrode with redox‐mediated reaction is expected to shed new light on commercial electrode design for VRBs.

Masthead: (Small 38/2020)

By from Wiley: Small: Table of Contents. Published on Sep 24, 2020.

Micropillar Arrays: Enhancement of Magneto‐Mechanical Actuation of Micropillar Arrays by Anisotropic Stress Distribution (Small 38/2020)

By Jeong Eun Park, Jisoo Jeon, Sei Jin Park, Sukyoung Won, Zahyun Ku, Jeong Jae Wie from Wiley: Small: Table of Contents. Published on Sep 24, 2020.

In the article number 2003179, Jeong Jae Wie and co‐workers report enhanced twisting or bending actuation of rectangular micropillars containing pre‐programmed horizontal or vertical magnetic particle alignment. Anisotropic stress distributions of rectangular pillars drastically enhance magneto‐mechanical actuation of micropillars in comparison to square micropillars. Magnetically deformed micropillars are selectively shape‐fixed by local evaporative assembly of polymeric solution even after removal of the magnetic field.

Sodium‐Ion Batteries: Golden Bristlegrass‐Like Hierarchical Graphene Nanofibers Entangled with N‐Doped CNTs Containing CoSe2 Nanocrystals at Each Node as Anodes for High‐Rate Sodium‐Ion Batteries (Small 38/2020)

By Min Su Jo, Jae Seob Lee, Sun Young Jeong, Jae Kwang Kim, Yun Chan Kang, Dong Won Kang, Sang Mun Jeong, Jung Sang Cho from Wiley: Small: Table of Contents. Published on Sep 24, 2020.

As anodes for high‐rate sodium‐ion batteries, golden bristlegrass‐like graphene nanofibers entangled with bamboo‐like N‐doped carbon nanotubes (CNTs) containing CoSe2 nanocrystals at each node are designed and synthesized in article number 2003391 by Yun Chan Kang, Sang Mun Jeong, Jung Sang Cho, and co‐workers.

Protocells: Rapid Growth and Fusion of Protocells in Surface‐Adhered Membrane Networks (Small 38/2020)

By Elif S. Köksal, Susanne Liese, Lin Xue, Ruslan Ryskulov, Lauri Viitala, Andreas Carlson, Irep Gözen from Wiley: Small: Table of Contents. Published on Sep 24, 2020.

In article number 2002529, Irep Gozen and co‐workers present experimental evidence that nucleation and growth of protocell‐like membrane compartments from surface‐adhered lipid nanotube networks are significantly enhanced at temperatures between 40 and 70 °C, and fusion can be initiated at ≈90 °C. They show that the microcontainers (5–15 μm) formed in this manner encapsulate and redistribute RNA, and corroborate that lipid nanotube–interconnected neighboring vesicles join and fuse more rapidly than in bulk suspensions.

Graphene Quantum Dots: Fundamental Understanding of the Formation Mechanism for Graphene Quantum Dots Fabricated by Pulsed Laser Fragmentation in Liquid: Experimental and Theoretical Insight (Small 38/2020)

By Sukhyun Kang, Kyung Hwan Jung, Sungwook Mhin, Yong Son, Kangpyo Lee, Won Rae Kim, Heechae Choi, Jeong Ho Ryu, Hyuksu Han, Kang Min Kim from Wiley: Small: Table of Contents. Published on Sep 24, 2020.

The pulsed laser fragmentation in liquid (PLFL) process is a promising technique for the synthesis of carbon‐based functional materials. However, a fundamental deep understanding of the formation of graphene quantum dots (GQDs) from multiwalled carbon nanotubes (MWCNTs) by PLFL has still not been achieved despite the high demand. In article number 2003538, Jeong Ho Ryu, Hyuksu Han, Kang Min Kim, and co‐workers report a mechanism for the formation of GQDs from MWCNTs by the PLFL process, through the combination of experimental and theoretical studies.

Dandelion‐Like Microswarms: Ultrafast Growth and Locomotion of Dandelion‐Like Microswarms with Tubular Micromotors (Small 38/2020)

By Xiaolong Lu, Hui Shen, Ying Wei, Hongbin Ge, Joseph Wang, Hanmin Peng, Wenjuan Liu from Wiley: Small: Table of Contents. Published on Sep 24, 2020.

In article number 2003678, Xiaolong Lu, Wenjuan Liu, and co‐workers report dandelion‐like microswarms assembled from tubular micromotors, which are capable of performing ultrafast growth and locomotion. With the ultrasound oscillation of self‐generated bubbles, such microswarms could move at an average speed of up to 50 mm s−1 and exhibit an instant and wireless response to ultrasound stimuli.

Layered Oxide Cathode for Potassium‐Ion Battery: Recent Progress and Prospective

By Xinyuan Zhang, Zhixuan Wei, Khang Ngoc Dinh, Nan Chen, Gang Chen, Fei Du, Qingyu Yan from Wiley: Small: Table of Contents. Published on Sep 24, 2020.

Layered oxides are regarded as promising cathode materials for potassium‐ion batteries. This work presents the recent advancements in KxMO2 cathodes, in terms of fundamental chemistry and structural evolution. Additionally, the existing issues and optimization strategies for material design are discussed, aiming at providing valuable insights for future research and development of advanced energy storage systems. Abstract Rechargeable potassium‐ion batteries (KIBs) have demonstrated great potential as alternative technologies to the currently used lithium‐ion batteries on account of the competitive price and low redox potential of potassium which is advantageous to applications in the smart grid. As the critical component determining the energy density, appropriate cathode materials are of vital need for the realization of KIBs. Layered oxide cathodes are promising candidates for KIBs due to high reversible capacity, appropriate operating potential, and most importantly, facile and easily scalable synthesis. In light of this trend, the recent advancements and progress in layered oxides research for KIBs cathodes, covering material design, structural evolution, and electrochemical performance are comprehensively reviewed. The structure–performance correlation and some effective optimization strategies are also discussed. Furthermore, challenges and prospects of these layered cathodes are included, with the purpose of providing fresh impetus for future development of these materials for advanced energy storage systems.

Plasmonic Metallic Heteromeric Nanostructures

By Guangchao Zheng, Stefanos Mourdikoudis, Zhicheng Zhang from Wiley: Small: Table of Contents. Published on Sep 24, 2020.

Plasmonic heteromers possess unique physicochemical properties and wide applications. In this work, the challenges for the synthetic approaches are discussed with respect to tuning the thermodynamics and kinetic properties. Then, plasmonic heteromers with their structure advantages displaying unique properties and applications compared to other hybrid nanostructures are strengthened. Finally, perspectives for further exploitation of plasmonic heteromers are demonstrated. Abstract Binary, ternary, and other high‐order plasmonic heteromers possess remarkable physical and chemical properties, enabling them to be used in numerous applications. The seed‐mediated approach is one of the most promising and versatile routes to produce plasmonic heteromers. Selective growth of one or multiple domains on desired sites of noble metal, semiconductor, or magnetic seeds would form desired heteromeric nanostructures with multiple functionalities and synergistic effects. In this work, the challenges for the synthetic approaches are discussed with respect to tuning the thermodynamics, as well as the kinetic properties (e.g., pH, temperature, injection rate, among others). Then, plasmonic heteromers with their structure advantages displaying unique activities compared to other hybrid nanostructures (e.g., core–shell, alloy) are highlighted. Some of the main most recent applications of plasmonic heteromers are also presented. Finally, perspectives for further exploitation of plasmonic heteromers are demonstrated. The goal of this work is to provide the current know‐how on the synthesis routes of plasmonic heteromers in a summarized manner, so as to achieve a better understanding of the resulting properties and to gain an improved control of their performances and extend their breadth of applications.

Wed 11 Nov 14:30: First-principles simulation of electronic processes due to ionic projectiles traversing matter

From All Talks (aka the CURE list). Published on Sep 24, 2020.

First-principles simulation of electronic processes due to ionic projectiles traversing matter

Ions shooting through matter transfer energy to the electrons along its trajectory at rates of up to keV per Angstrom. This rate depends on the projectile velocity, peaking when it is similar to average electron velocities in the system, typically around two to five percent of the speed of light. Because of its interest to radiation damage in various contexts (mostly nuclear, aerospace, and medical), the problem has been studied for over a century, but surprisingly little is known about the microscopic processes taking place beyond what obtained from perturbative approaches. The problem is strongly non-adiabatic and very strongly far from equilibrium. It is also nanoscopic (around the projectile) and of quantum nature. I will present our efforts in advancing our understanding of such processes by means of simulations based on time-dependent density-functional theory in real time, with special emphasis on the dependence on the chemistry of the irradiated matter, but also some notes on methodological advances prompted by the problem, in particular on quantum evolution in an evolving Hilbert space.

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[ASAP] Realization of the Square-Root Higher-Order Topological Insulator in Electric Circuits

By Lingling Song, Huanhuan Yang, Yunshan Cao, and Peng Yan from Nano Letters: Latest Articles (ACS Publications). Published on Sep 24, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c03049

[ASAP] Novel Bionic Topography with MiR-21 Coating for Improving Bone-Implant Integration through Regulating Cell Adhesion and Angiogenesis

By Zhen Geng, Zhaoyang Li, Zhenduo Cui, Jing Wang, Xianjin Yang, and Changsheng Liu from Nano Letters: Latest Articles (ACS Publications). Published on Sep 24, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c03240

[ASAP] Inert Shell Effect on the Quantum Yield of Neodymium-Doped Near-Infrared Nanoparticles: The Necessary Shield in an Aqueous Dispersion

By Artiom Skripka, Antonio Benayas, Carlos D. S. Brites, Inocencio R. Martín, Luís D. Carlos, and Fiorenzo Vetrone from Nano Letters: Latest Articles (ACS Publications). Published on Sep 24, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c03187

[ASAP] Controllable Thermal Conductivity in Twisted Homogeneous Interfaces of Graphene and Hexagonal Boron Nitride

By Wengen Ouyang, Huasong Qin, Michael Urbakh, and Oded Hod from Nano Letters: Latest Articles (ACS Publications). Published on Sep 24, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c02983

[ASAP] Transient Lattice Response upon Photoexcitation in CuInSe2 Nanocrystals with Organic or Inorganic Surface Passivation

By Samantha M. Harvey, Daniel W. Houck, Matthew S. Kirschner, Nathan C. Flanders, Alexandra Brumberg, Ariel A. Leonard, Nicolas E. Watkins, Lin X. Chen, William R. Dichtel, Xiaoyi Zhang, Brian A. Korgel, Michael R. Wasielewski, and Richard D. Schaller from ACS Nano: Latest Articles (ACS Publications). Published on Sep 24, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c05553

[ASAP] Nanotopography Enhances Dynamic Remodeling of Tight Junction Proteins through Cytosolic Liquid Complexes

By Xiao Huang, Xiaoyu Shi, Mollie Eva Hansen, Initha Setiady, Cameron L. Nemeth, Anna Celli, Bo Huang, Theodora Mauro, Michael Koval, and Tejal A. Desai from ACS Nano: Latest Articles (ACS Publications). Published on Sep 24, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c04866

[ASAP] Enhancing the Rapid Na+-Storage Performance via Electron/Ion Bridges through GeS2/Graphene Heterojunction

By Xing Ou, Zhiming Xiao, Jia-feng Zhang, Chunhui Wang, Dong Wang, Bao Zhang, and Yingpeng Wu from ACS Nano: Latest Articles (ACS Publications). Published on Sep 24, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c06371

[ASAP] Correction to 3D Crumpled Ultrathin 1T MoS2 for Inkjet Printing of Mg-Ion Asymmetric Micro-supercapacitors

By Yuanlong Shao, Jui-Han Fu, Zhen Cao, Kepeng Song, Ruofan Sun, Yi Wan, Atif Shamim, Luigi Cavallo, Yu Han, Richard B. Kaner, and Vincent C. Tung from ACS Nano: Latest Articles (ACS Publications). Published on Sep 24, 2020.

ACS Nano
DOI: 10.1021/acsnano.0c07499

[ASAP] Sustainable Personal Protective Clothing for Healthcare Applications: A Review

By Nazmul Karim, Shaila Afroj, Kate Lloyd, Laura Clarke Oaten, Daria V. Andreeva, Chris Carr, Andrew D. Farmery, Il-Doo Kim, and Kostya S. Novoselov from ACS Nano: Latest Articles (ACS Publications). Published on Sep 24, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c05537

[ASAP] Influence of Defects and H2O on the Hydrogenation of CO2 to Methanol over Pt Nanoparticles in UiO-67 Metal–Organic Framework

By Emil Sebastian Gutterd, Sri Harsha Pulumati, Gurpreet Kaur, Andrea Lazzarini, Bjrn Gading Solemsli, Anette Eleonora Gunnæs, Christian Ahoba-Sam, Maria Evangelou Kalyva, Johnny Andreas Sannes, Stian Svelle, Egill Skúlason, Ainara Nova, and Unni Olsbye from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Sep 24, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c07153

[ASAP] Mechanistic Insight into Concerted Proton–Electron Transfer of a Ru(IV)-Oxo Complex: A Possible Oxidative Asynchronicity

By Hiroaki Kotani, Hinatsu Shimomura, Kei Ikeda, Tomoya Ishizuka, Yoshihito Shiota, Kazunari Yoshizawa, and Takahiko Kojima from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Sep 24, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c05738

[ASAP] Pillar[5]arene-Containing Metallacycles and Host–Guest Interaction Caused Aggregation-Induced Emission Enhancement Platforms

By Wei Tuo, Yan Sun, Shuai Lu, Xiaopeng Li, Yao Sun, and Peter J. Stang from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Sep 24, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c08697

[ASAP] Glycoside Hydrolases Restrict the Side Chain Conformation of Their Substrates To Gain Additional Transition State Stabilization

By Jonathan C. K. Quirke and David Crich from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Sep 24, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c05592

[ASAP] In Situ Identification of Reaction Intermediates and Mechanistic Understandings of Methane Oxidation over Hematite: A Combined Experimental and Theoretical Study

By Yulian He, Facheng Guo, Ke R. Yang, Jake A. Heinlein, Scott M. Bamonte, Jared J. Fee, Shu Hu, Steven L. Suib, Gary L. Haller, Victor S. Batista, and Lisa D. Pfefferle from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Sep 24, 2020.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.0c07179

[ASAP] All-Carboxylate-Protected Superatomic Silver Nanocluster with an Unprecedented Rhombohedral Ag8 Core

By Kuan-Guan Liu, Xue-Mei Gao, Tongyu Liu, Mao-Lin Hu, and De-en Jiang from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Sep 24, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c06682

Minimizing Two-Dimensional Ti3C2Tx MXene Nanosheet Loading in Carbon-free Silicon Anodes

By Jodie Lutkenhaus from RSC - Nanoscale latest articles. Published on Sep 24, 2020.

Nanoscale, 2020, Accepted Manuscript
DOI: 10.1039/D0NR06086K, Paper
Kasturi Sarang, Xiaofei Zhao, Dustin Holta, Miladin Radovic, Micah Green, Eun-Suok Oh, Jodie Lutkenhaus
Silicon anodes are promising for high energy batteries because of their excellent theoretical gravimetric capacity (3579 mAh/g). However, silicon’s large volume expansion and poor conductivity hinder its practical application; thus,...
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Carbon supported noble metal nanoparticles as efficient catalysts for electrochemical water splitting

By Alain Penicaud from RSC - Nanoscale latest articles. Published on Sep 24, 2020.

Nanoscale, 2020, Accepted Manuscript
DOI: 10.1039/D0NR05659F, Communication
Open Access Open Access
Meng Liu, Ferdinand Hof, Miriam Moro, Giovanni Valenti, Francesco Paolucci, Alain Penicaud
Due to an increasing requirement of clean and sustainable hydrogen energy economy, it is significant to develop new highly effective catalysts for electrochemical water splitting. In alkaline electrolyte, Platinum (Pt)...
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Supramolecular Antibiotics: A Strategy for Conversion of Broad-Spectrum to Narrow-Spectrum Antibiotics for Staphylococcus aureus

By Sankaran Thayumanavan from RSC - Nanoscale latest articles. Published on Sep 24, 2020.

Nanoscale, 2020, Accepted Manuscript
DOI: 10.1039/D0NR04886K, Paper
Thameez M. Koyasseril-Yehiya, Alam García-Heredia, Francesca Anson, Poornima Rangadurai, M. Sloan Siegrist, Sankaran Thayumanavan
The propensity of broad-spectrum antibiotics to indiscriminately kill both pathogenic and beneficial bacteria has a profound impact on the spread of resistance across multiple bacterial species. Alternative approaches that narrow...
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Low Loss Slow Light Waveguiding in Coupled Subwavelength Silicon Mie Resonators

By Arseniy I Kuznetsov from RSC - Nanoscale latest articles. Published on Sep 24, 2020.

Nanoscale, 2020, Accepted Manuscript
DOI: 10.1039/D0NR05248E, Paper
Ding Lu, Ye Feng Yu, Dmitry Morits, Mingbin Yu, Ang Y. L. Thomas, Hong-Son Chu, Lim Soon Thor, Eng Ping Ching, Ramon Paniagua-Dominguez, Arseniy I Kuznetsov
Subwavelength light-guiding optical devices have gained great attention in the photonics community because they provide unique opportunities for miniaturization and functionality of the optical interconnect technology. On the other hand,...
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Highly purified extracellular vesicles from human cardiomyocytes demonstrate preferential uptake by human endothelial cells

By Molly M. Stevens from RSC - Nanoscale latest articles. Published on Sep 24, 2020.

Nanoscale, 2020, Advance Article
DOI: 10.1039/D0NR04278A, Paper
Open Access Open Access
Creative Commons Licence  This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
Limor Zwi-Dantsis, Charles W. Winter, Ulrike Kauscher, Arianna Ferrini, Brian Wang, Thomas E. Whittaker, Steve R. Hood, Cesare M. Terracciano, Molly M. Stevens
Highly purified EVs isolated from human cardiomyocytes show differential uptake in cardiac cell types.
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Enhancing LiAlOX synaptic performance by reducing Schottky barrier height for deep neural network application

By Xiangshui Miao from RSC - Nanoscale latest articles. Published on Sep 24, 2020.

Nanoscale, 2020, Accepted Manuscript
DOI: 10.1039/D0NR04782A, Paper
Yaoyao Fu, Boyi Dong, Wan-Ching Su, Zhi-Yang Lin, Kuan-Ju Zhou, Ting-Chang Chang, Fuwei Zhuge, Yi Li, Yuhui He, Bin Gao, Xiangshui Miao
Although good performance has been reported in shallow neural network, the application of memristor synapses towards realistic deep neural network has met more stringent requirements on the synapse properties, especially...
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In-situ growth of CeO2 onto g-C3N4 nanosheets toward spherical g-C3N4/CeO2 nanozyme with enhanced peroxidase-like catalysis: A selective colorimetric analysis strategy for mercury (II)

By Hua Wang from RSC - Nanoscale latest articles. Published on Sep 24, 2020.

Nanoscale, 2020, Accepted Manuscript
DOI: 10.1039/D0NR05315E, Paper
Xiaoting Zhao, Shuai Li, Xiaoxue Yu, Ruotong Gang, Hua Wang
Cerium dioxide (CeO2) nanocatalysts were initially grown in situ onto 2D graphitic carbon nitride (g-C3N4) nanosheets to yield the nanocomposites of g-C3N4/CeO2 with spherical structure for the catalysis-based colorimetric analysis...
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The Role of Carbon Dots – Derived Underlayer in Hematite Photoanodes

By A Belen Jorge from RSC - Nanoscale latest articles. Published on Sep 24, 2020.

Nanoscale, 2020, Accepted Manuscript
DOI: 10.1039/D0NR06139E, Paper
Open Access Open Access
Creative Commons Licence  This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
Qian Guo, Hui Luo, Jifang Zhang, Qiushi Ruan, Arun Prakash, Yuanxing Fang, Zailai Xie, Xuanhua Li, Xinchen Wang, Junwang Tang, Joe Briscoe, Magdalena Titirici, A Belen Jorge
Hematite is a promising candidate as photoanode for solar-driven water splitting, with a theoretically predicted maximum solar-to-hydrogen conversion efficiency of ~ 16%. However, the interfacial charge transfer and recombination greatly...
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Ørsted and Bunsen: Voltaic Batteries, Electric Arcs, Electromagnetism, and Electrolysis

By Curt Wentrup from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 23, 2020.

200 years ago Ørsted in Copenhagen discovered electromagnetism. He also studied galvanism and the construction of voltaic batteries and electromagnets. In Marburg, Bunsen, 34 years his junior, had similar interests. He constructed a coal‐zinc battery surpassing anything known at that time. In 1841 he visited Scandinavia, where Berzelius, Palmstedt, and Ørsted soon used his battery to power electrical apparatus. Abstract 200 years ago Ørsted laid the foundation of electromagnetism in his famous experiment in which a magnetic needle is deflected in the electrical field of a platinum wire. For this he used his own Cu‐Zn trough battery, which was among the best then available, but 21 years later it was surpassed by the coal‐zinc battery invented by Bunsen, which became highly successful and acclaimed. That year, 1841, Bunsen made his first direct contact with Scandinavia when he visited Berzelius in Stockholm, Palmstedt in Gothenburg, and Ørsted, Scharling, and Zeise in Copenhagen. Like almost everybody in continental Europe, they adopted Bunsen's battery, and Ørsted used it for his experiments with a very large electromagnet. The paths of Ørsted's and Bunsen's research crossed again much later through the synthesis of elemental aluminum, which was first achieved by Ørsted in 1825 (although it was probably not obtained as the pure metal) and performed quite differently by Bunsen, by electrolysis using his coal‐zinc battery, in 1854.

Carbide Dihydrides: Carbonaceous Species Identified in Ta4+‐Mediated Methane Dehydrogenation

By Jozef Lengyel, Nikita Levin, Frank J. Wensink, Olga V. Lushchikova, Robert N. Barnett, Uzi Landman, Ueli Heiz, Joost M. Bakker, Martin Tschurl from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 23, 2020.

The products of methane dehydrogenation by gas‐phase Ta 4 + clusters are structurally characterized using infrared multiple photon dissociation (IRMPD) spectroscopy in conjunction with quantum chemical calculations. The obtained spectra of [4Ta,C,2H] + reveal a dominance of vibrational bands of a H 2 Ta 4 C + carbide dihydride structure over those of indicative for a HTa 4 CH + carbyne hydride one, as is unambiguously verified by studies employing various methane isotopologues. Because methane dehydrogenation by metal cations M + typically leads to the formation of either MCH 2 + carbene or HMCH + carbyne hydride structures, the observation of a H 2 MC + carbide dihydride structure implies that it is imperative to consider this often‐neglected class of carbonaceous intermediates in the reaction of metals with hydrocarbons.

Needles from haystacks: single‐scan selective excitation of individual NMR signals in overlapping multiplets

By Peter Kiraly, Nicolas Kern, Mateusz P. Plesniak, Mathias Nilsson, David J. Procter, Gareth A. Morris, Ralph William Adams from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 23, 2020.

2D NMR is an immensely powerful structural tool, but time‐consuming. Targeting individual chemical groups by selective excitation in a 1D experiment can give the information required far more quickly. A major problem, however, is that proton NMR spectra are often extensively overlapped, so that in practice only a minority of sites can be selectively excited. Here we overcome that problem using a fast, single‐scan method that allows selective excitation of the signals of a single proton multiplet even where it is severely overlapped by other multiplets. The advantages of the method are illustrated in a selective 1D NOESY experiment, the most efficient way to determine relative configuration unambiguously by NMR. The new approach presented here has the potential to broaden significantly the applicability of selective excitation, and unlock its real potential for many other experiments.

High Ammonia Uptake of a Metal‐Organic Framework Adsorbent in a Wide Pressure Range

By Dae Won Kim, Dong Won Kang, Minjung Kang, Jung-Hoon Lee, Jong Hyeak Choe, Yun Seok Chae, Doo San Choi, Hongryeol Yun, Chang Seop Hong from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 23, 2020.

Although numerous porous adsorbents have been investigated for NH 3  capture applications, these materials often exhibit insufficient NH 3 uptake, low NH 3 affinity at the ppm level, and poor chemical stability against wet NH 3 conditions. Herein, we report the NH 3 capture properties of M 2 (dobpdc) complexes (M = Mg 2+ , Mn 2+ , Co 2+ , Ni 2+ , and Zn 2+ ; dobpdc 4− = 4,4‐dioxidobiphenyl‐3,3‐dicarboxylate) that contain open metal sites. The NH 3 uptake of Mg 2 (dobpdc) at 298 K was 23.9 mmol g −1 at 1 bar and 8.25 mmol g −1 at 570 ppm, which are record high capacities at both pressures among existing porous adsorbents. The strength of the interactions between the Lewis acid open metal sites and NH 3 followed the trend of Ni > Mg > Co > Mn, which was determined by NH 3 ‐temperature programmed desorption curves. The structural stability of Mg 2 (dobpdc) upon exposure to wet NH 3 was superior to that of the other M 2 (dobpdc) and the frameworks tested. Our van der Waals‐corrected density functional theory calculations predicted that this may be associated with the higher stability of MgO 6 coordination compared to that of Mg(NH 3 ) 6 . Overall, these results demonstrate that Mg 2 (dobpdc) is a recyclable compound that exhibits significant NH 3 affinity and capacity, making it a promising candidate for real‐world NH 3 ‐capture applications.

A Review of Shape Memory Polymers and Composites: Mechanisms, Materials, and Applications

By Yuliang Xia, Yang He, Fenghua Zhang, Yanju Liu, Jinsong Leng from Wiley: Advanced Materials: Table of Contents. Published on Sep 23, 2020.

Shape memory polymers are promising stimuli‐responsive materials that have provoked the interest of scientists over the past several decades. Progress in the mechanisms and applications of shape memory polymers is summarized, with a focus on the design and regulation of the shape memory effect. Future prospects and challenges in this exciting field are also proposed. Abstract Over the past decades, interest in shape memory polymers (SMPs) has persisted, and immense efforts have been dedicated to developing SMPs and their multifunctional composites. As a class of stimuli‐responsive polymers, SMPs can return to their initial shape from a programmed temporary shape under external stimuli, such as light, heat, magnetism, and electricity. The introduction of functional materials and nanostructures results in shape memory polymer composites (SMPCs) with large recoverable deformation, enhanced mechanical properties, and controllable remote actuation. Because of these unique features, SMPCs have a broad application prospect in many fields covering aerospace engineering, biomedical devices, flexible electronics, soft robotics, shape memory arrays, and 4D printing. Herein, a comprehensive analysis of the shape recovery mechanisms, multifunctionality, applications, and recent advances in SMPs and SMPCs is presented. Specifically, the combination of functional, reversible, multiple, and controllable shape recovery processes is discussed. Further, established products from such materials are highlighted. Finally, potential directions for the future advancement of SMPs are proposed.

State of the Art and Perspectives of Hierarchical Zeolites: Practical Overview of Synthesis Methods and Use in Catalysis

By Dorien Kerstens, Brent Smeyers, Jonathan Van Waeyenberg, Qiang Zhang, Jihong Yu, Bert F. Sels from Wiley: Advanced Materials: Table of Contents. Published on Sep 23, 2020.

A practical overview of the most recent literature on synthesis of hierarchical zeolites for most relevant zeolite topologies is presented. Several fine‐tuning efforts of established and novel synthesis methods are discussed. Remaining challenges and points of attention and a personal view for future synthesis research to obtain the most sustainable and catalytically active hierarchical zeolites are also presented. Abstract Microporous zeolites have proven to be of great importance in many chemical processes. Yet, they often suffer from diffusion limitations causing inefficient use of the available catalytically active sites. To address this problem, hierarchical zeolites have been developed, which extensively improve the catalytic performance. There is a multitude of recent literature describing synthesis of and catalysis with these hierarchical zeolites. This review attempts to organize and overview this literature (of the last 5 years), with emphasis on the most important advances with regard to synthesis and application of such zeolites. Special attention is paid to the most common and important 10‐ and 12‐membered ring zeolites (MTT, TON, FER, MFI, MOR, FAU, and *BEA). In contrast to previous reviews, the research per zeolite topology is brought together and discussed here. This allows the reader to instantly find the best synthesis method in accordance to the desired zeolite properties. A summarizing graph is made available to enable the reader to select suitable synthesis procedures based on zeolite acidity and mesoporosity, the two most important tunable properties.

A Self‐Healing Amalgam Interface in Metal Batteries

By Ye Fan, Tao Tao, Yuxuan Gao, Chao Deng, Baozhi Yu, Ying (Ian) Chen, Shengguo Lu, Shaoming Huang from Wiley: Advanced Materials: Table of Contents. Published on Sep 23, 2020.

An effective, universal strategy, introducing an amalgam interface, to resolve the interfacial issues of metal anodes/electrolytes toward high‐performance metal batteries is presented. Such amalgam interface in all‐solid‐state symmetric cells, which shows a high electron/ion dual‐conductivity, can undergo a reversible isothermal phase transition from solid (Li‐rich amalgam) to liquid (Li‐deficient amalgam) during cycling process at room temperature. Abstract Poor cyclability and safety concerns caused by the uncontrollable dendrite growth and large interfacial resistance severely restrict the practical applications of metal batteries. Herein, a facile, universal strategy to fabricate ceramic and glass phase compatible, and self‐healing metal anodes is proposed. Various amalgam‐metal anodes (Li, Na, Zn, Al, and Mg) show a long cycle life in symmetric cells. It has been found that liquid Li amalgam shows a complete wetting with the surface of lanthanum lithium titanate electrolyte and a glass‐phase solid‐state electrolyte. The interfacial compatibility between the lithium metal anode and solid‐state electrolyte is dramatically improved by using an in situ regenerated amalgam interface with high electron/ion dual‐conductivity, obviously decreasing the anode/electrolyte interfacial impedance. The lithium‐amalgam interface between the metal anode and electrolyte undergoes a reversible isothermal phase transition between solid and liquid during the cycling process at room temperature, resulting in a self‐healing surface of metal anodes.

Bio‐Photonic Waveguide of a DNA‐Hybrid Semiconductor Prismatic Hexagon

By Seokho Kim, Chunzhi Cui, Jingyuan Huang, Heeso Noh, Dong Hyuk Park, Dong June Ahn from Wiley: Advanced Materials: Table of Contents. Published on Sep 23, 2020.

DNA–DNA recognition is achieved based on the waveguide effect of a 1D hybrid prismatic hexagon crystal. This 1D hybrid‐crystal can simultaneously discern one base mismatch of a sequence through waveguide performance. Abstract A successful identification of DNA–DNA recognition, based on the waveguide effect of a 1D hybrid prismatic hexagon crystal interfacing of DNA with an organic semiconductor is achieved. This bio‐hybrid 1D crystal simultaneously discerns the complementary case at its one end against a 1‐mer mismatch in 27‐mer nucleic acid sequence at the other end. The loss coefficient value of this waveguide is estimated to be 0.159 µm−1 for the perfect match, which is a stark discrepancy compared to 0.244 µm−1 for the 1‐mer mismatch, implying waveguide performance with a higher efficiency. These results demonstrate successfully that multiple biological interactions can be realized by the optical waveguide of the single 1D bio‐hybrid‐crystal and will push this class of materials into bio‐related applications.

Discovery and Biosynthesis of Bolagladins: Unusual Lipodepsipeptides from Burkholderia gladioli Clinical Isolates

By Yousef Dashti, Ioanna T. Nakou, Alex J. Mullins, Gordon Webster, Xinyun Jian, Eshwar Mahenthiralingam, Gregory L. Challis from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 23, 2020.

Bolagladins A and B were discovered as products of a cryptic nonribosomal peptide synthetase in two Burkholderia gladioli strains isolated from the lungs of cystic fibrosis patients. These metabolites contain a unique citrate‐primed fatty acid and a rare dehydro‐β‐alanine residue. A combination of bioinformatics analysis and genetic and biochemical experiments illuminated the mechanisms for the installation of these unusual structural features. Abstract Two Burkholderia gladioli strains isolated from the lungs of cystic fibrosis patients were found to produce unusual lipodepsipeptides containing a unique citrate‐derived fatty acid and a rare dehydro‐β‐alanine residue. The gene cluster responsible for their biosynthesis was identified by bioinformatics and insertional mutagenesis. In‐frame deletions and enzyme activity assays were used to investigate the functions of several proteins encoded by the biosynthetic gene cluster, which was found in the genomes of about 45 % of B. gladioli isolates, suggesting that its metabolic products play an important role in the growth and/or survival of the species. The Chrome Azurol S assay indicated that these metabolites bind ferric iron, which suppresses their production when added to the growth medium. Moreover, a gene encoding a TonB‐dependent ferric‐siderophore receptor is adjacent to the biosynthetic genes, suggesting that these metabolites may function as siderophores in B. gladioli.

A Tandem 0D/2D/2D NbS2 Quantum Dot/Nb2O5 Nanosheet/g‐C3N4 Flake System with Spatial Charge–Transfer Cascades for Boosting Photocatalytic Hydrogen Evolution

By Bo Lin, Zihao Chen, Pin Song, Haishi Liu, Lixing Kang, Jun Di, Xiao Luo, Longqing Chen, Chao Xue, Bowen Ma, Guidong Yang, Jun Tang, Jiadong Zhou, Zheng Liu, Fucai Liu from Wiley: Small: Table of Contents. Published on Sep 23, 2020.

A tandem 0D/2D/2D NbS2 quantum dot/Nb2O5 nanosheet/g‐C3N4 flake (NSNOCN) system is developed. The unique spatial arrangement and morphology of NbS2, Nb2O5, and g‐C3N4 in the newly designed NSNOCN can introduce plenty of spatial charge–transfer cascades from g‐C3N4 to NbS2 via Nb2O5 to accelerate the charge transfer and boost the photocatalytic H2 evolution activity. Abstract The relatively high recombination rate of charges remains the most critical limiting factor for solar‐driven water splitting for hydrogen generation. Herein, a tandem 0D/2D/2D NbS2 quantum dot/Nb2O5 nanosheet/g‐C3N4 flake (NSNOCN) system is designed. Owing to the unique spatial‐arrangement and elaborate morphology of 0D NbS2, 2D Nb2O5, and 2D g‐C3N4 in the newly designed NSNOCN, plenty of spatial charge–transfer cascades from g‐C3N4 to NbS2 via Nb2O5 are formed to accelerate separation and transfer of charges significantly, thus contributing to a high photocatalytic H2 generation rate of 13.99 mmol h−1 g−1 (an apparent quantum efficiency of 10.8% at 420 nm), up to 107.6 and 43.7 times by contrast with that of g‐C3N4 and Nb2O5, respectively. This work can provide a new platform in the design of artificial photocatalytic systems with high charge–transfer efficiency.

Bright and Stable NIR‐II J‐aggregated AIE Dibodipy for Dynamic in vivo Bioimaging

By Fan Zhang, Qisong Zhang, Peng Yu, Yong Fan, Caixia Sun, Haisheng He, Xuan Liu, Lingfei Lu, Mengyao Zhao, Hongxin Zhang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 23, 2020.

Organic dyes, emitting in the second near‐infrared (NIR‐II, 900‐1700 nm) window, with high molar extinction coefficient (MEC) and quantum yield (QY) in aqueous is essential for in vivo bioimaging and biosensing. In this work, we developed a dibodipy based J‐aggregated aggregation induced emission (AIE) molecule THPP to meet this aim. THPP exhibits a high MEC of dibodipy structure and has intensified absorption and emission in J‐aggregated state, which significantly enhanced the fluorescence intensity (~55 folds) and extends the maximal absorption/emission wavelengths to 970/1010 nm in NIR‐II region. Based on the bright THPP , imaging with high frame rate (34 frames per second) in a deep ‘valid penetration depth’ up to 6 mm can be achieved. This enabled simultaneously and dynamically imaging of vasculatures and deeply located visceral. Besides, we succeeded in monitoring the respiratory rate of acute‐lung‐injury mice and tracing the collateral circulation process with a high frame rate.

A surface strained and geometry tailored nanoreactor promotes the ammonia electrosynthesis

By Panpan Li, Zhaoyu Jin, Zhiwei Fang, Guihua Yu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 23, 2020.

A surface strained and geometry optimized TiO 2 nanoreactor was reported to enhance the performance of the electrocatalytic nitrogen fixation. The nanotubular confinement allows to spatially regulate the mass transport of nitrogen during the NRR process and offers an enlarged surface area, thus boosting the ammonia production with high selectivity. Besides, both experimental and theoretical evidence support strained Ti 3+ sites demonstrate a more favorable pathway for the N 2 activation and selective NH 3 production with a faster kinetic rate than the pristine TiO 2 . Therefore, TiO 2 ‐based nanoreactor with surface and bulk structure tailoring delivered the NH 3 yield rate up to 5.50 μg h ‐1 cm ‐2 (16.67 μg h ‐1 mg ‐1 ) and the high faradaic efficiency of 26% under ambient aqueous conditions. Our findings highlight the concept of lattice strain and geometry modified nanoreactors, which will have broad implications in the renewable energy catalysis and electrosynthesis of valuable products.

Toward flexible zinc‐ion hybrid capacitors with superhigh energy density and ultralong cycling life: the pivotal role of ZnCl2 salt‐based electrolytes

By Cheng Wang, Zengxia Pei, Qiangqiang Meng, Chunmei Zhang, Xiao Sui, Ziwen Yuan, Sijie Wang, Yuan Chen from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 23, 2020.

Zinc (Zn) ion hybrid capacitors (ZIHCs) are promising energy storage devices for emerging flexible electronics, but they still suffer from trade‐off in energy density and cycling life. Herein, we prove that such a dilemma can be well‐addressed by deploying ZnCl 2 based electrolytes. Combining experimental studies and density functional theory (DFT) calculations, for the first time, we demonstrate an intriguing chloride ion (Cl ‐ ) facilitated desolvation mechanism in hydrated [ZnCl] + (H 2 O) n‐1 (with n=1‐6) clusters. Based on this mechanism, a “water‐in‐salt” type hydrogel electrolyte filled with ZnCl 2 was developed to concurrently improve the energy storage capacity of porous carbon materials and the reversibility of Zn metal electrode. The resulting ZIHCs deliver a battery‐level energy density up to 217 Wh kg ‐1 at a power density of 450 W kg ‐1 , an unprecedented cycling life of 100,000 cycles, together with excellent low‐temperature adaptability and mechanical flexibility.

Synthesis and Multiplexed Activity Profiling of Synthetic Acylphloroglucinol Scaffolds

By John Porco, Brian Bachmann, Jonathan Boyce, Benjamin Reisman from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 23, 2020.

Herein, we report novel formic acid‐mediated rearrangements of dearomatized acylphloroglucinols to access a structurally diverse group of synthetic acylphloroglucinol scaffolds (SASs). Density functional theory (DFT)‐optimized orbital and stereochemical analyses shed light on the mechanism of these rearrangements. Products were evaluated by multiplexed activity profiling (MAP), an unbiased platform which determines multiple biological readouts simultaneously at single‐cell resolution for markers of cell signaling and can aid in distinguishing genuine activity from assay interference. Using MAP, we identified a number of SASs that suppressed pS6 (Ser235/236), a marker for activation of the mTOR and ERK signaling pathways. These results illustrate how biomimetic synthesis and multiplexed activity profiling can reveal the pharmacological potential of novel chemotypes via diversity‐oriented synthesis.

Effects of anion carriers on capacitance and self‐discharge behaviors of zinc ion capacitor

By Zhaodong Huang, Tairan Wang, Hao Song, Xinliang Li, Guojin Liang, Donghong Wang, Qi Yang, Ze Chen, Longtao Ma, Zhuoxin Liu, Biao Gao, Jun Fan, Chunyi Zhi from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 23, 2020.

Introducing pseudocapacitive behavior and ion hybrid capacitor technique were deemed effective to improve the energy density of supercapacitors. However, the current research about ion hybrid capacitor only considered the reaction of cations during the electrochemical process, leading to a flawed mechanism understanding. Here, the effects of various anions carriers on the electrochemical behaviors of titanium nitride‐based zinc ion capacitor (Zn‐TiN capacitor) have been carefully explored. Density functional theory (DFT) calculation results revealed the stable structure of TiN‐SO 4 after adsorbed process, enabling SO 4 2‐ participate in the electrochemical process and construct a two‐step adsorption and intercalation energy storage mechanism, which greatly improved the capacitance and anti‐self‐discharge ability of Zn‐TiN capacitor. Zn‐TiN capacitor delivered an ultrahigh capacitance of 489.8 F g ‐1 and remained 83.92% of capacitance even after 500 h resting time. It is believed that designing an appropriate energy storage system to involve anions in the electrochemical process can significantly improve the capacitance and anti‐self‐discharge ability of ion hybrid capacitors.

Mn‐O Covalency Governs the Intrinsic Activity of Co‐Mn Spinel Oxides for Boosted Peroxymonosulfate Activation

By Zhi-Yan Guo, Chen-Xuan Li, Miao Gao, Xiao Han, Ying-Jie Zhang, Wen-Jun Zhang, Wen-Wei Li from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 23, 2020.

Transition metal (TM)‐based bimetallic spinel oxides can efficiently activate peroxymonosulfate (PMS) presumably attributed to enhanced electron transfer between TMs, but the existing model cannot fully explain the efficient TM redox cycling. Here, we discover a critical role of TM‐O covalency in governing the intrinsic catalytic activity of Co 3‐x Mn x O 4 spinel oxides. Experimental and theoretical analysis reveal that the Co sites significantly raises the Mn valence and enlarges Mn‐O covalency in octahedral configuration, thereby lowering the charge transfer energy to favor Mn Oh ‐PMS interaction. With appropriate Mn IV /Mn III ratio to balance PMS adsorption and Mn IV reduction, the Co 1.1 Mn 1.9 O 4 exhibits remarkable catalytic activities for PMS activation and pollutant degradation, outperforming all the reported TM spinel oxides. The improved understandings on the origins of spinel oxides activity for PMS activation may inspire the development of more active and robust metal oxide catalysts.

The active site of a prototypical “rigid” drug target is marked by extensive conformational dynamics

By Himanshu Singh, Chandan K. Das, Suresh K. Vasa, Kristof Grohe, Lars V. Schäfer, Rasmus Linser from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 23, 2020.

Drug discovery, in particular optimization of candidates via medicinal chemistry, is generally guided by structural biology. For optimizing binding kinetics, however, relevant for efficacy and off‐target effects, information on protein motion is important. Here, we demonstrate for the prototypical textbook example of an allegedly “rigid protein” that substantial active‐site dynamics have generally remained unrecognized despite thousands of medicinal‐chemistry studies on this model over decades. Comparing cryogenic X‐ray structures, solid‐state NMR on micro‐crystalline protein at room temperature, and solution NMR structure and dynamics, supported by MD simulations, we show that under physiologically relevant conditions the pocket is in fact shaped by pronounced open/close conformational‐exchange dynamics. In accordance, the conventional workflow even seems to suggest a conformational distribution of the active site incongruent with the solution case. The study, which is of general significance for pharmacological research, evinces a generic pitfall in drug discovery routines.

Thu 17 Jun 13:00: Title to be confirmed

From All Talks (aka the CURE list). Published on Sep 23, 2020.

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Thu 16 Dec 13:00: Title to be confirmed

From All Talks (aka the CURE list). Published on Sep 23, 2020.

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Thu 16 Sep 13:00: Title to be confirmed

From All Talks (aka the CURE list). Published on Sep 23, 2020.

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Thu 20 May 13:00: Title to be confirmed

From All Talks (aka the CURE list). Published on Sep 23, 2020.

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Fri 23 Apr 13:00: Title to be confirmed Please note this seminar is on a Friday

From All Talks (aka the CURE list). Published on Sep 23, 2020.

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Thu 18 Mar 13:00: Title to be confirmed

From All Talks (aka the CURE list). Published on Sep 23, 2020.

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Thu 25 Feb 13:00: Title to be confirmed

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Thu 21 Jan 13:00: Title to be confirmed

From All Talks (aka the CURE list). Published on Sep 23, 2020.

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Miscibility‐Controlled Phase Separation in Double‐Cable Conjugated Polymers for Single‐Component Organic Solar Cells with Efficiencies over 8 %

By Xudong Jiang, Jinjin Yang, Safakath Karuthedath, Junyu Li, Wenbin Lai, Cheng Li, Chengyi Xiao, Long Ye, Zaifei Ma, Zheng Tang, Frédéric Laquai, Weiwei Li from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 23, 2020.

A naphthalene diimide based double‐cable conjugated polymer provided a record efficiency of 8.4 % in single‐component organic solar cells. It simultaneously facilitates exciton separation and charge transport via miscibility control. Abstract A record power conversion efficiency of 8.40 % was obtained in single‐component organic solar cells (SCOSCs) based on double‐cable conjugated polymers. This is realized based on exciton separation playing the same role as charge transport in SCOSCs. Two double‐cable conjugated polymers were designed with almost identical conjugated backbones and electron‐withdrawing side units, but extra Cl atoms had different positions on the conjugated backbones. When Cl atoms were positioned at the main chains, the polymer formed the twist backbones, enabling better miscibility with the naphthalene diimide side units. This improves the interface contact between conjugated backbones and side units, resulting in efficient conversion of excitons into free charges. These findings reveal the importance of charge generation process in SCOSCs and suggest a strategy to improve this process: controlling miscibility between conjugated backbones and aromatic side units in double‐cable conjugated polymers.

Catalytic Enantioselective [2+2] Cycloaddition of α‐Halo Acroleins: Construction of Cyclobutanes Containing Two Tetrasubstituted Stereocenters

By Lei Zeng, Jingjing Xu, Dongsheng Zhang, Zhongliang Yan, Guolin Cheng, Weidong Rao, Lizhu Gao from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 23, 2020.

A [2+2] cycloaddition reaction of electronically diverse arylalkenes with α‐bromo acroleins provided highly functionalized cyclobutanes bearing two adjacent tetrasubstituted stereocenters. Mechanistic studies revealed cis‐cyclobutane could be enantioselectively transformed into the trans isomer in reaction system. Abstract A catalytic enantioselective formal [2+2] cycloaddition between α‐halo acroleins and electronically diverse arylalkenes is described. In the presence of (S)‐oxazaborolidinium cation as the catalyst, densely functionalized cyclobutanes containing two vicinal tetrasubstituted stereocenters were produced in high yields and high diastereoselectivities with excellent enantioselectivities. Mechanistic studies revealed that the cis isomer could be transformed into the trans isomer via an enantiocontrolled process. A gram‐scale reaction of this catalytic method was used to demonstrate its synthetic potential.

General Principles for the Design of Visible‐Light‐Responsive Photoswitches: Tetra‐ortho‐Chloro‐Azobenzenes

By Lucien N. Lameijer, Simon Budzak, Nadja A. Simeth, Mickel J. Hansen, Ben L. Feringa, Denis Jacquemin, Wiktor Szymanski from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 23, 2020.

Molecular photoswitches that respond to visible light irradiation enable external, non‐invasive control over biological systems, materials, and molecular machines. Here we present a systematic spectroscopic and theoretical investigation into the photochemistry of tetra‐ortho‐chloro‐azobenzenes and outline the design principles that allow the optimization of those emerging photochromes on a molecular level. Abstract Molecular photoswitches enable reversible external control of biological systems, nanomachines, and smart materials. Their development is driven by the need for low energy (green‐red‐NIR) light switching, to allow non‐invasive operation with deep tissue penetration. The lack of clear design principles for the adaptation and optimization of such systems limits further applications. Here we provide a design rulebook for tetra‐ortho‐chloroazobenzenes, an emerging class of visible‐light‐responsive photochromes, by elucidating the role that substituents play in defining their key characteristics: absorption spectra, band overlap, photoswitching efficiencies, and half‐lives of the unstable cis isomers. This is achieved through joint photochemical and theoretical analyses of a representative library of molecules featuring substituents of varying electronic nature. A set of guidelines is presented that enables tuning of properties to the desired application through informed photochrome engineering.

General Synthesis of Single‐Atom Catalysts for Hydrogen Evolution Reactions and Room‐Temperature Na‐S Batteries

By Wei‐Hong Lai, Heng Wang, Lirong Zheng, Quan Jiang, Zi‐Chao Yan, Lei Wang, Hirofumi Yoshikawa, Daiju Matsumura, Qiao Sun, Yun‐Xiao Wang, Qinfen Gu, Jia‐Zhao Wang, Hua‐Kun Liu, Shu‐Lei Chou, Shi‐Xue Dou from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 23, 2020.

Universality in preparing samples with atomic metal dopants is vital to expand the diversity of single‐atom materials and their widespread applications. We provide a comprehensive library of single atoms for systematically investigating their different electrocatalytic behaviors in HER and RT Na‐S batteries. In particular, the tune of single‐atom local structures can achieve unexpected performance in general electrochemistry. Abstract Herein, we report a comprehensive strategy to synthesize a full range of single‐atom metals on carbon matrix, including V, Mn, Fe, Co, Ni, Cu, Ge, Mo, Ru, Rh, Pd, Ag, In, Sn, W, Ir, Pt, Pb, and Bi. The extensive applications of various SACs are manifested via their ability to electro‐catalyze typical hydrogen evolution reactions (HER) and conversion reactions in novel room‐temperature sodium sulfur batteries (RT‐Na‐S). The enhanced performances for these electrochemical reactions arisen from the ability of different single active atoms on local structures to tune their electronic configuration. Significantly, the electrocatalytic behaviors of diverse SACs, assisted by density functional theory calculations, are systematically revealed by in situ synchrotron X‐ray diffraction and in situ transmission electronic microscopy, providing a strategic library for the general synthesis and extensive applications of SACs in energy conversion and storage.

Experimentally Observed Reverse Intersystem Crossing‐Boosted Lasing

By Zhonghao Zhou, Chan Qiao, Kang Wang, Lu Wang, Jie Liang, Qian Peng, Zhiyou Wei, Haiyun Dong, Chuang Zhang, Zhigang Shuai, Yongli Yan, Yong Sheng Zhao from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 23, 2020.

Reverse intersystem crossing‐boosted lasing was experimentally demonstrated in self‐assembled microspheres with uniformly dispersed organic thermally activated delayed‐fluorescence molecules. The lasing intensity increases with increasing temperature due to the involvement of regenerated singlets in population inversion, which provides a way to overcome triplet‐related losses for high‐performance organic lasers. Abstract Thermally activated delayed‐fluorescent (TADF) materials are anticipated to overcome triplet‐related losses towards electrically driven organic lasers. Thus far, contributions from triplets to lasing have not yet been experimentally demonstrated owing to the limited knowledge about the excited‐state processes. Herein, we experimentally achieve reverse intersystem crossing (RISC)‐boosted lasing in organic microspheres with uniformly dispersed TADF emitters. In these materials, triplets are continuously converted to radiative singlets through RISC, giving rise to reduced losses in stimulated emission. The involvement of regenerated singlets in population inversion results in a thermally activated lasing; that is, the lasing intensity increases with increasing temperature, accompanied by accelerated depletion of the excited‐state population. Benefiting from the suppression of triplet accumulations by RISC processes, a high‐repetition‐rate microlaser was achieved.

Serial Femtosecond Zero Dose Crystallography Captures a Water‐Free Distal Heme Site in a Dye‐Decolorising Peroxidase to Reveal a Catalytic Role for an Arginine in FeIV=O Formation

By Marina Lučić, Dimitri A. Svistunenko, Michael T. Wilson, Amanda K. Chaplin, Bradley Davy, Ali Ebrahim, Danny Axford, Takehiko Tosha, Hiroshi Sugimoto, Shigeki Owada, Florian S. N. Dworkowski, Ivo Tews, Robin L. Owen, Michael A. Hough, Jonathan A. R. Worrall from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 23, 2020.

Femtosecond X‐ray crystallography reveals the pristine structures of the FeIII and FeIV=O redox states of a B‐type dye‐decolorising heme peroxidase. These structures reveal a water‐free distal heme site, which together with the presence of an asparagine, imply the operation of the distal arginine as a catalytic base in the heterolysis of peroxide. Abstract Obtaining structures of intact redox states of metal centers derived from zero dose X‐ray crystallography can advance our mechanistic understanding of metalloenzymes. In dye‐decolorising heme peroxidases (DyPs), controversy exists regarding the mechanistic role of the distal heme residues aspartate and arginine in the heterolysis of peroxide to form the catalytic intermediate compound I (FeIV=O and a porphyrin cation radical). Using serial femtosecond X‐ray crystallography (SFX), we have determined the pristine structures of the FeIII and FeIV=O redox states of a B‐type DyP. These structures reveal a water‐free distal heme site that, together with the presence of an asparagine, imply the use of the distal arginine as a catalytic base. A combination of mutagenesis and kinetic studies corroborate such a role. Our SFX approach thus provides unique insight into how the distal heme site of DyPs can be tuned to select aspartate or arginine for the rate enhancement of peroxide heterolysis.

A Voltage‐Responsive Synthetic Cl−‐Channel Regulated by pH

By Shao‐Ping Zheng, Ji‐Jun Jiang, Arie Lee, Mihail Barboiu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 23, 2020.

Voltage‐controlled translocation through chloride channels in bilayer membranes simultaneously regulated by pH is demonstrated. This voltage/pH regulated channel system represents an unexplored alternative for ion‐pumping along artificial ion‐channels. Abstract Transmembrane protein channels are an important inspiration for the design of artificial ion channels. Their dipolar structure helps overcome the high energy barrier to selectively translocate water and ions sharing one pathway, across the cell membrane. Herein, we report that the amino‐imidazole (Imu) amphiphiles self‐assemble via multiple H‐bonding to form stable artificial Cl−‐channels within lipid bilayers. The alignment of water/Cl− wires influences the conduction of ions, envisioned to diffuse along the hydrophilic pathways; at acidic pH, Cl−/H+ symport conducts along a partly protonated channel, while at basic pH, higher Cl−/OH− antiport translocate through a neutral channel configuration, which can be greatly activated by applying strong electric field. This voltage/pH regulated channel system represents an unexplored alternative for ion‐pumping along artificial ion‐channels, parallel to that of biology.

A Non‐aqueous H3PO4 Electrolyte Enables Stable Cycling of Proton Electrodes

By Yunkai Xu, Xianyong Wu, Heng Jiang, Longteng Tang, Kenneth Y. Koga, Chong Fang, Jun Lu, Xiulei Ji from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 23, 2020.

The proton as a charge carrier offers a vast potential for battery systems with characteristics of high power and long longevity. A non‐aqueous proton electrolyte of anhydrous H3PO4 solvated in acetonitrile for proton batteries is presented. It facilitates stable cycle performance of electrode materials that otherwise lose capacity rapidly in aqueous electrolytes. Abstract A non‐aqueous proton electrolyte is devised by dissolving H3PO4 into acetonitrile. The electrolyte exhibits unique vibrational signatures from stimulated Raman spectroscopy. Such an electrolyte exhibits unique characteristics compared to aqueous acidic electrolytes: 1) higher (de)protonation potential for a lower desolvation energy of protons, 2) better cycling stability by dissolution suppression, and 3) higher Coulombic efficiency owing to the lack of oxygen evolution reaction. Two non‐aqueous proton full cells exhibit better cycling stability, higher Coulombic efficiency, and less self‐discharge compared to the aqueous counterpart.

Chemical Vapor Deposition for Atomically Dispersed and Nitrogen Coordinated Single Metal Site Catalysts

By Shengwen Liu, Maoyu Wang, Xiaoxuan Yang, Qiurong Shi, Zhi Qiao, Marcos Lucero, Qing Ma, Karren L. More, David A. Cullen, Zhenxing Feng, Gang Wu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 23, 2020.

Atomically dispersed and nitrogen coordinated iron (Fe‐N‐C) catalysts are prepared by using chemical vapor deposition. The catalysts exhibit outstanding oxygen‐reduction activity in acidic electrolytes, which can further transfer into membrane electrode assemblies (MEAs) for fuel cell applications. The MEAs are capable of generating current densities of 27 mA cm−2 at 0.9 V (1.0 bar O2) and 117 mA cm−2 at 0.8 V (1.0 bar air). Abstract Atomically dispersed and nitrogen coordinated single metal sites (M‐N‐C, M=Fe, Co, Ni, Mn) are the popular platinum group‐metal (PGM)‐free catalysts for many electrochemical reactions. Traditional wet‐chemistry catalyst synthesis often requires complex procedures with unsatisfied reproducibility and scalability. Here, we report a facile chemical vapor deposition (CVD) strategy to synthesize the promising M‐N‐C catalysts. The deposition of gaseous 2‐methylimidazole onto M‐doped ZnO substrates, followed by an in situ thermal activation, effectively generated single metal sites well dispersed into porous carbon. In particular, an optimal CVD‐derived Fe‐N‐C catalyst exclusively contains atomically dispersed FeN4 sites with increased Fe loading relative to other catalysts from wet‐chemistry synthesis. The catalyst exhibited outstanding oxygen‐reduction activity in acidic electrolytes, which was further studied in proton‐exchange membrane fuel cells with encouraging performance.

Direct Observation of Defect‐Aided Structural Evolution in a Nickel‐Rich Layered Cathode

By Shuang Li, Zhenpeng Yao, Jianming Zheng, Maosen Fu, Jiajie Cen, Sooyeon Hwang, Huile Jin, Alexander Orlov, Lin Gu, Shun Wang, Zhongwei Chen, Dong Su from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 23, 2020.

The structural evolution of a Ni‐rich NMC cathode in a solid‐state cell was investigated by in situ transmission electron microscopy. Antiphase boundary (APB) and twin boundary (TB) separating layered phases played an important role in the phase change. Upon Li depletion, the APB extended across the layered structure, while Li/transition metal (TM) ion mixing in the layered phases induced rock‐salt phase formation along the coherent TB. Abstract Ni‐rich LiNi1−x−yMnxCoyO2 (NMC) layered compounds are the dominant cathode for lithium ion batteries. The role of crystallographic defects on structure evolution and performance degradation during electrochemical cycling is not yet fully understood. Here, we investigated the structural evolution of a Ni‐rich NMC cathode in a solid‐state cell by in situ transmission electron microscopy. Antiphase boundary (APB) and twin boundary (TB) separating layered phases played an important role on phase change. Upon Li depletion, the APB extended across the layered structure, while Li/transition metal (TM) ion mixing in the layered phases was detected to induce the rock‐salt phase formation along the coherent TB. According to DFT calculations, Li/TM mixing and phase transition were aided by the low diffusion barriers of TM ions at planar defects. This work reveals the dynamical scenario of secondary phase evolution, helping unveil the origin of performance fading in Ni‐rich NMC.

A Two‐Dimensional Metal–Organic Polymer Enabled by Robust Nickel–Nitrogen and Hydrogen Bonds for Exceptional Sodium‐Ion Storage

By Liubin Wang, Youxuan Ni, Xuesen Hou, Li Chen, Fujun Li, Jun Chen from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 23, 2020.

A metal–organic polymer is synthesized via d–π hybridization. It features a two‐dimensional layered structure by nickel–nitrogen and hydrogen bonds and promises good electrochemical performance with abundant redox centers of conjugated benzoid carbonyls and imines. Abstract Organic electrode materials suffer from low electronic conductivity and poor structure stability. Herein, a metal–organic polymer, Ni‐coordinated tetramino‐benzoquinone (Ni‐TABQ), is synthesized via d–π hybridization. The polymer chains are stitched by hydrogen bonds to feature as a robust two‐dimensional (2D) layered structure. It offers both electron conduction and Na+ diffusion pathways along the directions of the polymer chains and the hydrogen bonds. With both the conjugated benzoid carbonyls and imines as the redox centers for the insertion and extraction of Na+, the Ni‐TABQ delivers high capacities of about 469.5 mAh g−1 at 100 mA g−1 and 345.4 mAh g−1 at 8 A g−1. The large capacities are sustained for 100 cycles with almost 100 % coulombic efficiencies. The exceptional electrochemical performance is attributed to the unique 2D electron conduction and Na+ diffusion pathways enabled by the robust Ni–N and hydrogen bonds.

Structures and Structural Evolution of Sublayer Surfaces of Metal–Organic Frameworks

By Xiaocang Han, Pan Liu, Fang Lin, Wenqian Chen, Ruichun Luo, Qi Han, Zhuo Jiang, Xiaodong Wang, Shuangxi Song, Kolan Madhav Reddy, Hexiang Deng, Mingwei Chen from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 23, 2020.

The atomic‐scaled configurations of sublayer surfaces and their evolution of MIL‐101 crystals were directly imaged from their charge density projections by low‐dose spherical aberration corrected high‐resolution transmission electron microscopy. The surface transformation from a sublayer to a stable surface is fulfilled by the successive addition of hybrid Cr3(μ3‐O)‐(benzenedicarboxylate)x complexes, which is regulated by inorganic Cr3(μ3‐O) trimers. Abstract The structural characterization of sublayer surfaces of MIL‐101 is reported by low‐dose spherical aberration‐corrected high‐resolution transmission electron microscopy (HRTEM). The state‐of‐the‐art microscopy directly images atomic/molecular configurations in thin crystals from charge density projections, and uncovers the structures of sublayer surfaces and their evolution to stable surfaces regulated by inorganic Cr3(μ3‐O) trimers. This study provides compelling evidence of metal–organic frameworks (MOFs) crystal growth via the assembly of sublayer surfaces and has important implications in understanding the crystal growth and surface‐related properties of MOFs.

Quantification of High‐Temperature Transition Al2O3 and Their Phase Transformations

By Libor Kovarik, Mark Bowden, Amity Andersen, Nicholas R. Jaegers, Nancy Washton, János Szanyi from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 23, 2020.

Quantification of the microstructure of transition aluminas represents a formidable challenge due to high degree of structural disorder. In this work, an XRD recursive‐stacking formalism is developed and used for the quantification of high‐temperature transition aluminas. Abstract High‐temperature treatment of γ‐Al2O3 can lead to a series of polymorphic transformations, including the formation of δ‐Al2O3 and θ‐Al2O3. Quantification of the microstructure in the range where δ‐ and θ‐Al2O3 are formed represents a formidable challenge, as both phases accommodate a high degree of structural disorder. In this work, we explore the use of an XRD recursive‐stacking formalism for the quantification of high‐temperature transition aluminas. We formulate the recursive‐stacking methodology for modelling of disorder in δ‐Al2O3 and twinning in θ‐Al2O3 and show that explicitly accounting for the disorder is necessary to reliably model the XRD patterns of high‐temperature transition alumina. We also use the recursive stacking approach to study phase transformation during high‐temperature (1050 °C) treatment. We show that the two different intergrowth modes of δ‐Al2O3 have different transformation characteristics and that a significant portion of δ‐Al2O3 is stabilized with θ‐Al2O3 even after prolonged high‐temperature exposures.

Bright Infrared‐to‐Ultraviolet/Visible Upconversion in Small Alkaline Earth‐Based Nanoparticles with Biocompatible CaF2 Shells

By Stefan Fischer, Chris Siefe, Dayne F. Swearer, Claire A. McLellan, A. Paul Alivisatos, Jennifer A. Dionne from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 23, 2020.

Near‐infrared (NIR)‐to‐ultraviolet (UV) upconverting nanoparticles (UCNPs) exhibit great potential ranging from phototherapy to photocatalysis. Herein, we investigate the upconversion emission and efficiency of sub‐15 nm alkaline‐earth rare‐earth fluoride nanoparticles (M1−xLnxF2+x, MLnF) with a CaF2 shell. By varying the alloying of the host, lanthanide doping concentration, and nanoparticle size, we synthesize bright and efficient sub‐15 nm UCNPs. Abstract Upconverting nanoparticles (UCNPs) are promising candidates for photon‐driven reactions, including light‐triggered drug delivery, photodynamic therapy, and photocatalysis. Herein, we investigate the NIR‐to‐UV/visible emission of sub‐15 nm alkaline‐earth rare‐earth fluoride UCNPs (M1−xLnxF2+x, MLnF) with a CaF2 shell. We synthesize 8 alkaline‐earth host materials doped with Yb3+ and Tm3+, with alkaline‐earth (M) spanning Ca, Sr, and Ba, MgSr, CaSr, CaBa, SrBa, and CaSrBa. We explore UCNP composition, size, and lanthanide doping‐dependent emission, focusing on upconversion quantum yield (UCQY) and UV emission. UCQY values of 2.46 % at 250 W cm−2 are achieved with 14.5 nm SrLuF@CaF2 particles, with 7.3 % of total emission in the UV. In 10.9 nm SrYbF:1 %Tm3+@CaF2 particles, UV emission increased to 9.9 % with UCQY at 1.14 %. We demonstrate dye degradation under NIR illumination using SrYbF:1 %Tm3+@CaF2, highlighting the efficiency of these UCNPs and their ability to trigger photoprocesses.

Large‐Area Single‐Crystal Graphene via Self‐Organization at the Macroscale

By Huy Quang Ta, Alicja Bachmatiuk, Rafael Gregorio Mendes, David J. Perello, Liang Zhao, Barbara Trzebicka, Thomas Gemming, Slava V. Rotkin, Mark H. Rümmeli from Wiley: Advanced Materials: Table of Contents. Published on Sep 23, 2020.

Graphene flakes, nucleated over a polycrystalline graphene film, are shown to synchronize during growth, so as to ultimately yield a common crystal orientation at the macroscale, namely, large‐area single‐crystal growth. The work also demonstrates that graphene synthesis can be advanced to control the nucleated crystal shape, registry, and relative alignment between graphene crystals for wafer‐scale areas. Abstract In 1665 Christiaan Huygens first noticed how two pendulums, regardless of their initial state, would synchronize.  It is now known that the universe is full of complex self‐organizing systems, from neural networks to correlated materials. Here, graphene flakes, nucleated over a polycrystalline graphene film, synchronize during growth so as to ultimately yield a common crystal orientation at the macroscale. Strain and diffusion gradients are argued as the probable causes for the long‐range cross‐talk between flakes and the formation of a single‐grain graphene layer. The work demonstrates that graphene synthesis can be advanced to control the nucleated crystal shape, registry, and relative alignment between graphene crystals for large area, that is, a single‐crystal bilayer, and (AB‐stacked) few‐layer graphene can been grown at the wafer scale.

Fri 30 Oct 08:45: Equine induced pluripotent stem cells (iPSCs) as an alternative source of obtaining chondrocytes

From All Talks (aka the CURE list). Published on Sep 23, 2020.

Equine induced pluripotent stem cells (iPSCs) as an alternative source of obtaining chondrocytes

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Nanoscale hyperspectral imaging of amyloid secondary structures in liquid

By Ewelina Lipiec, Janina Kaderli, Jan Kobierski, Roland Riek, Katarzyna Skirlińska-Nosek, Kamila Sofińska, Marek Szymoński, Renato Zenobi from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 23, 2020.

Abnormal aggregation of amyloid‐β is a very complex and heterogeneous process. Due to methodological limitations, the aggregation pathway is still not fully understood. In this communication a new approach is presented in which the secondary structure of single amyloid‐β aggregates is investigated with tip‐enhanced Raman spectroscopy (TERS) in a liquid environment. Clearly resolved TERS signatures of the amide I and amide III bands enabled a detailed analysis of the molecular structure of single aggregates at each phase of the primary aggregation of amyloid‐β and also of small species on the surface of fibrils attributed to secondary nucleation. Notably, a β‐sheet rearrangement from antiparallel in protofibrils to parallel in fibrils is observed. This study allows better understanding of Alzheimer’s disease etiology and the methodology can be applied in studies of other neurodegenerative disorders.

Direct writing large‐area multi‐layer ultrasmooth films by an all‐solution process: toward high‐performance QLEDs

By Huan Liu, Min Zhang, Huanhuan Deng, Lili Meng, Hongqin Wang, Yunjun Wang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 23, 2020.

With increasing the film area/layer, deteriorating in both smoothness and uniformity of thin‐films frequently happen, which remains a barrier for making large‐area quantum dot light‐emitting diodes (QLEDs) by solution processes. Here, we demonstrated a facile all‐solution process guided by the conical fiber array to write multi‐layer ultrasmooth thin‐films directly in centimeter scale. The side‐by‐side fibrous array helps to align surface tensions at the tri‐phase contact line to facilitate large‐area homogeneous deposition, which was verified by theoretical simulation. The Laplace pressure along individual conical fiber contributes to the steady liquid transfer. Thin‐films with small roughness (

Thu 15 Oct 09:00: Shaping tissues: the role of mechanics across different scales. Host: Ben Steventon

From All Talks (aka the CURE list). Published on Sep 23, 2020.

Shaping tissues: the role of mechanics across different scales.

Understanding how complex organ shape emerges during development remains a major challenge. Here, we use high spatio-temporal live imaging with biophysical modelling to explore at cellular and tissue scales the underlying biophysical processes driving morphogenesis of zebrafish skeletal muscle and the Drosophila heart.

The skeletal muscle of swimming vertebrates forms a distinctive chevron morphology, which is believed to aid swimming. This shape can be altered by perturbing muscle cell differentiation or the interaction between muscle segments (myotomes) and surrounding tissues. We find that, soon after segmentation from the presomitic mesoderm, the future myotome spreads across the underlying tissues. The mechanical coupling between the future myotome and the surrounding tissues appears to spatially vary, effectively resulting in spatially heterogeneous friction. Using a vertex model combined with experimental validation, we show that the interplay of tissue spreading and friction is sufficient to drive the initial phase of chevron shape formation. However, local anisotropic stresses, generated during muscle cell differentiation, combined with tissue plasticity, are necessary to reach the acute angle of the wild-type chevron. This work reveals how a sequence of local cellular events can have a nonlocal and irreversible mechanical impact at the tissue scale.

How cells integrate different mechanical stimuli to accomplish complicated tasks in vivo remains unclear. We explore this problem in the context of heart formation during Drosophila embryogenesis, where individual cells form precise inter-cellular connections between partner cells. We find that non-muscle Myosin II clusters periodically oscillate within cardioblasts with ~4-min intervals. We observe that filopodia dynamics – including protrusions, retraction, binding stabilization, and binding separation – are correlated with the periodic localisation of Myosin II clusters at the cell leading edge. Perturbing the Myosin II activity and oscillatory pattern alters the filopodia properties and binding dynamics and results in mismatched cardioblasts. By simultaneously changing the activity of Myosin II and filopodia adhesion levels, we further demonstrate that levels of Myosin II and adhesion are balanced to ensure precise connectivity between cardioblasts. Combined, we propose a mechanical proofreading machinery of robust cell matching, whereby oscillations of Myosin II within cardioblasts periodically probe filopodia adhesion strength and ensure correct cell-cell connection formation.

Host: Ben Steventon

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An Active‐Site Sulfonate Group Creates a Fast Water Oxidation Electrocatalyst That Exhibits High Activity in Acid

By Aaron G. Nash, Colton J. Breyer, Brett D. Vincenzini, Gregory I. Elliott, Jens Niklas, Oleg G. Poluektov, Arnold L. Rheingold, Diane K. Smith, Djamaladdin G. Musaev, Douglas Grotjahn from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 23, 2020.

The storage of solar energy in chemical bonds will depend on pH‐universal catalysts that are not only impervious to acid, but actually thrive in it. Whereas other homogeneous water oxidation catalysts are less active in acid, here we report a catalyst that maintains high electrocatalytic turnover frequency at pH values as low as 1.1 and 0.43 (kcat = 1501 ± 608 s‐1 and 831 ± 254 s‐1, respectively). Moreover, current densities, related to catalytic reaction rates, ranged from 15 to 50 mA cm‐2 mM‐1 comparable to those reported for state‐of‐the‐art heterogeneous catalysts and 30 to 100 times greater than those measured here for two prominent literature homogeneous catalysts at pH 1.1 and 0.43. The catalyst also exhibits excellent durability when a chemical oxidant is used (CeIV, 7400 turnovers, TOF 0.88 s‐1). Preliminary computational studies suggest that the unusual active‐site sulfonate group acts a proton relay even in strong acid, as intended.

Tue 29 Sep 18:00: Coding and Decoding of Calcium Signals in Plants

From All Talks (aka the CURE list). Published on Sep 23, 2020.

Coding and Decoding of Calcium Signals in Plants

Registration: https://forms.gle/4HBJUEth66ubUAWR8

This talk is open to all including non-members, subjected to availability. Please register by Monday 28 September to receive the link for the online lecture.

Abstract: Although plants do not have a nerve system, they are capable of detecting and responding to environmental changes. In fact, many of such signaling mechanisms are highly conserved at the molecular level in plants and animals. One good example is that both plants and animals utilize calcium ion (Ca2+) as a universal signal in response to myriad of stimuli. A fundamental question is how Ca2+, a simple cation, encodes complex information with high specificity. Extensive research has established a two-step process (coding and decoding) that governs the specificity of Ca2+ signals. While the coding mechanism entails a complex array of channels and transporters, the decoding process features a number of Ca2+ sensors and effectors that convert Ca2+ signals into cellular effects. Along this general paradigm, some signaling components may be highly conserved, but others divergent among different organisms. In plant cells, Ca2+ participates in numerous signaling processes and here I focus on the latest discoveries we have made on Ca2+-encoding mechanisms in development and defense. In particular, we use examples such as polarized cell growth of pollen tube and root hair in which tip-focused Ca2+ oscillations specify the signaling events for rapid cell elongation (just like in animal axon guidance and fungal hyphae growth). In plant-microbe interaction, like human immune response, Ca2+ spiking and oscillations hold the key to signaling specificity. Herbivore attack or mechanical wounding can trigger Ca2+ waves traveling a long distance to transmit and convert the local signal to a systemic defense program in the whole plant (reminiscent to animal synaptic transmission). The future work will further expand the toolkit for Ca2+ encoding mechanisms and place the Ca2+ signaling steps into the larger signaling networks.

Speaker profile: Professor Sheng Luan is Associate Chair of the Department of Plant and Microbial Biology at the University of California Berkeley. Prof Luan received his PhD in Cell and Developmental Biology at Harvard University, and continued his postdoctoral training there. He joined UC Berkeley in 1995 and became a full professor in 2004. His current research looks at calcium signalling mechanisms in plants. He has published more than 150 research and review articles in premier journals including Annual Review of Plant Biology, Trends in Plant Sciences, PNAS , Nature and Science Signaling, among many others. Prof Luan received numerous awards including the Charles Albert Shull Award and the Alexander von Humboldt Prize. He is a Fellow of AAAS and a Fellow of the American Society of Plant Biologists. He was selected as Web of Science “Highly Cited Researcher” in 2014, 2015, 2016 and 2018. Prof Luan is the founding Editor-in-Chief of Molecular Plant, a leading plant biology journal published by Cell Press.

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DOI: 10.1039/D0NR06382G, Paper
Open Access Open Access
Creative Commons Licence  This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
Ijaz Rashid, Muhammad U. Hassan, Muhammad Nazim, Mohamed Elsherif, Qian Dou, Debo Hu, kamran khattak, Qing Dai, Haider Butt
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Assembly‐Induced Strong Circularly Polarized Luminescence of Spirocyclic Chiral Silver(I) Clusters

By Han Wu, Xin He, Biao Yang, Cui-Cui Li, Liang Zhao from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 22, 2020.

Supramolecular assembly of molecular chiral compounds is crucial for the comprehension of chirality propagation and achieving superior chirality‐related properties. In this work, spirocyclic Ag 9 clusters as a new form of intrinsically chiral metal clusters have been constructed through vertex‐sharing of two in situ generated heteroaryl diide‐centered metal rings. Such core‐peripheral type clusters exhibit versatile photoluminescent and chiroptical behaviours under different aggregation conditions. In contrast to a ligand‐based fluorescence emission in a diluted solution of the clusters, a solvent polarity‐caused assembly gives rise to new cluster‐based phosphorous luminescence due to radiative mode switching and aggregation‐induced emission. Furthermore, the assembly of cluster enantiomers engenders micrometer‐long helical nanofibers, whose handedness is determined by absolute configuration of individual spirocyclic clusters. Benefiting from exciton couplings of helical arrangements of chelating ligands at both molecular and microscopic levels, the assembled film of cluster enantiomers exhibits circularly polarized luminescence with a remarkably high anisotropy factor of 0.16.

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By Rüdiger Maria Exner, Fernando Cortezon-Tamarit, Sofia Ioana Pascu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 22, 2020.

Polymethine cyanine dyes have been widely recognized as promising chemical tools for a range of life sciences and biomedical applications, such as fluorescent staining of DNA and proteins in gel electrophoresis, fluorescence guided surgery or as ratiometric probes for probing biochemical pathways. The photophysical properties of such dyes can be tuned through the synthetic modification of the conjugated backbone, e.g. by altering aromatic cores or by varying the length of the conjugated polymethine chain. Alternative routes to shaping the absorption, emission and photostability of dyes of this family are centered around the chemical modifications on the polymethine chain. This minireview aims to discuss strategies for the introduction of substituents in the meso ‐position, their effect on the photophysical properties of these dyes and some structure‐activity correlations which could help overcome common limitations in the state of the art in the synthesis.

NIR‐Sensitized Cationic and Hybrid Radical/Cationic Polymerization and Crosslinking

By Yulian Pang, Atsushi Shiraishi, Dietmar Keil, Sergey Popov, Veronika Strehmel, Hongjun Jao, Jochen S. Gutmann, Yinquan Zou, Bernd Strehmel from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 22, 2020.

NIR sensitized cationic polymerization proceeded with good efficiency as studied with epoxides, vinyl ether, and oxetanes.  A heptacyanine functioned as sensitizer while iodonium salts served as coinitiator.  The anion uptakes a special function as concluded by a series selected from fluorinated phosphates (a: [PF6]‐, b: [PF3(C2F5)3]‐, c: [PF3(n‐C4F9)3]), aluminates (d: [Al(O‐t‐C4F9)4]‐, e: [Al(O(C3F6)CH3)4]‐ , and methide [C(O‐SO2CF3)3]‐ (f).  Vinyl ether showed the best cationic polymerization efficiency followed by oxetanes and oxiranes.  Density functional theory calculations provided a rough pattern regarding the electrostatic potential of each anion where d exhibited a rather better performance compared to e.  The more efficient shielding of all CF3‐groups can explain these findings.  Anion d also better performed as b, which was introduced as alternative to a.  In addition, formation of interpenetrating polymer networks (IPNs) using trimethylpropane triacrylate and either oxetane or epoxide‐based monomer successfully proceeded in the case of NIR sensitized polymerization were anion d served as anion for the sensitizer and the iodonium salt.  No successful IPN formation occurred in the case of UV‐LED initiation using the same monomers but the photoinitiating system comprised of thioxanthone/iodonium salt.  Exposure was carried out with new NIR‐LED devices emitting at either 805 nm or 870 nm.

Unusual Magnetic Field Responsive Circularly Polarized Luminescence Probes with Highly Emissive Chiral Eu(III) Complexes

By Junhui Zhang, Lixiong Dai, Alexandra M. Webster, Wesley Ting Kwok Chan, Steven L. Cobb, Ga-Lai Law from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 22, 2020.

Chirality is ubiquitous within biological systems where many of the roles and functions are still undetermined. Given this, there is a clear need to design and develop sensitive chiral optical probes that can function within a biological setting. Here we report the design and synthesis of magnetically responsive Circularly Polarized Luminescence (CPL) complexes displaying exceptional photophysical properties (quantum yield up to 31% and |g lum | up to 0.240) by introducing chiral substituents onto the macrocyclic scaffolds. Magnetic CPL responses are observed in these chiral Eu(III) complexes, promoting an exciting development to the field of magneto‐optics. The |g lum | of the 5 D 0 à 7 F 1 transition increases by 20% from 0.222 (0 T) to 0.266 (1.4 T) displaying a linear relationship between the Δg lum and the magnetic field strength. These Eu(III) complexes with magnetic CPL responses, provides potential development to be used in CPL imaging applications due to improved sensitivity and resolution.

Shear stress‐responsive polymersome nanoreactors inspired by the marine bioluminescence of dinoflagellates

By Omar Rifaie-Graham, Nikolas F.B. Galensowske, Charlie Dean, Jonas Pollard, Sandor Balog, Micael G. Gouveia, Mohamed Chami, Antoine Vian, Esther Amstad, Marco Lattuada, Nico Bruns from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 22, 2020.

Some marine plankton called dinoflagellates emit light in response to the movement of surrounding water, resulting in a phenomenon called milky seas or sea sparkle. The underlying concept, a shear‐stress induced permeabilisation of biocatalytic reaction compartments, is transferred to polymer‐based nanoreactors. Amphiphilic block copolymers that carry nucleobases in their hydrophobic block are self‐assembled into polymersomes. The membrane of the vesicles can be transiently switched between an impermeable to a semipermeble state by shear forces occurring in flow or during turbulent mixing of polymersome dispersions. Nucleobase pairs in the hydrophobic leaflet separate when mechanical force is applied, exposing their hydrogen bonding motifs and therefore making the membrane less hydrophobic and more permeable for water soluble compounds. This polarity switch is used to release payload of the polymersomes on demand, and to activate biocatalytic reactions in the interior of the polymersomes, such as luminescence reactions or radical polymerizations catalysed by the enzyme horseradish peroxidase. Such bio‐inspired shear stress‑responsive nanoreactors have potential for applications ranging from gel‐formation on demand, to three‐dimensional inkjet printing, and shear‐stress triggered drug delivery.

Synthesis of Vinylene‐Linked Two‐Dimensional Conjugated Polymers via the Horner‐Wadsworth‐Emmons Reaction

By Dominik L. Pastoetter, Shunqi Xu, Mino Borrelli, Matthew Addicoat, Bishnu P. Biswal, Silvia Paasch, Arezoo Dianat, Heidi Thomas, Reinhard Berger, Sebastian Reineke, Eike Brunner, Gianaurelio Cuniberti, Marcus Richter, Xinliang Feng from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 22, 2020.

Interest in linear conjugated polymers has significantly increased in recent decades due to their semiconducting properties and promising applications in organic optoelectronics. To date, the extension of linear conjugated polymers into two‐dimensional conjugated polymers (2D CPs), which can also be regarded as 2D π‐conjugated covalent organic frameworks (COFs), remains largely unexplored due to limited synthetic methodologies. In this work, we demonstrate the first synthesis of vinylene‐linked 2D CPs, namely, 2D poly(phenylenequinoxalinevinylene)s 2D‐PPQV1 and 2D‐PPQV2 , via the Horner‐Wadsworth‐Emmons (HWE) reaction of C 2 ‐symmetric 1,4‐bis(diethylphosphonomethyl)benzene or 4,4'‐bis(diethylphosphonomethyl)biphenyl with C 3 ‐symmetric 2,3,8,9,14,15‐hexa(4‐formylphenyl)diquinoxalino[2,3‐ a :2',3'‐ c ]phenazine as monomers. Density functional theory (DFT) simulations unveil the crucial role of the initial reversible C‐C single bond formation for the synthesis of crystalline 2D CPs. Powder X‐ray diffraction (PXRD) studies and nitrogen adsorption‐desorption measurements demonstrate the formation of proclaimed crystalline, dual‐pore structures with surface areas of up to 440 m 2 /g. More importantly, the optoelectronic properties of the obtained 2D‐PPQV1 (E g =2.2 eV) and 2D‐PPQV2 (E g =2.2 eV) are compared with those of cyano‐vinylene‐linked 2D‐CN‐PPQV1 (E g =2.4 eV) produced by the Knoevenagel reaction and imine‐linked 2D COF analog ( 2D‐C=N‐PPQV1 , E g =2.3 eV), unambiguously proving the superior conjugation of the vinylene‐linked 2D CPs using the HWE reaction.

Precise alkoxyamine‐design enables automated tandem mass spectrometry sequencing of digital poly(phosphodiester)s

By Kévin Launay, Jean-Arthur Amalian, Eline Laurent, Laurence Oswald, Abdelaziz Al Ouahabi, Alexandre Burel, Florent Dufour, Christine Carapito, Jean-Louis Clément, Jean-François Lutz, Laurence Charles, Didier Gigmes from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 22, 2020.

Increasing data storage density is one of the major challenges of the information industry. To be widely applicable, writing and reading information have to be dense, convenient and fast. A major step towards reliable reading of information coded in the sequence of long poly(phosphodiester)s was previously achieved by introducing an alkoxyamine spacer between information sub‐segments. However, MS/MS decoding had to be performed manually to safely identify useful fragments of low abundance compared to side‐products induced by the amide‐based alkoxyamine used. Here, alternative alkoxyamines were designed to prevent these side‐reactions and enable automated MS/MS sequencing. Different styryl‐TEMPO spacers were prepared to increase radical delocalization and stiffness of the structure. Their dissociation behavior was investigated by EPR and best MS/MS data were recorded for polymers with alkoxyamines containing in‐chain benzyl ring, avoiding all side‐reactions during synthesis or sequencing. As a result, automated decoding of these polymers can be achieved using the MS‐DECODER software, which performs interpretation of fragmentation data recorded for each sub‐segment prior to align the so‐obtained digital sequences in their original order based on the mass tag defining the initial location of each sub‐segment.

Chelation Crosslinking of Biodegradable Elastomers

By Ying Chen, Paula G. Miller, Xiaochu Ding, Chelsea E. T. Stowell, Katie M. Kelly, Yadong Wang from Wiley: Advanced Materials: Table of Contents. Published on Sep 22, 2020.

A versatile metal chelation crosslink in biodegradable elastomers is reported. The types of metal ions, ligand density, and metal–ligand ratio offer fine control of the polymers’ properties. A subcutaneous implantation in mice reveals higher biocompatibility than the widely use biomaterial, polycaprolactone. Abstract Widely present in nature and in manufactured goods, elastomers are network polymers typically crosslinked by strong covalent bonds. Elastomers crosslinked by weak bonds usually exhibit more plastic deformation. Here, chelation as a mechanism to produce biodegradable elastomers is reported. Polycondensation of sebacic acid, 1,3‐propanediol, and a Schiff‐base (2‐[[(2‐hydroxyphenyl) methylene]amino]‐1,3‐propanediol) forms a block copolymer that binds several biologically relevant metal ions. Chelation offers a unique advantage unseen in conventional elastomer design because one ligand binds multiple metal ions, yielding bonds of different strengths. Therefore, one polymeric ligand coordinated with different metal ions produces elastomers with vastly different characteristics. Mixing different metal ions in one polymer offers another degree of control on material properties. The density of the ligands in the block copolymer further regulates the mechanical properties. Moreover, a murine model reveals that Fe3+ crosslinked foam displays higher compatibility with subcutaneous tissues than the widely used biomaterial—polycaprolactone. The implantation sites restore to their normal architecture with little fibrosis upon degradation of the implants. The versatility of chelation‐based design has already shown promise in hydrogels and highly stretchy nondegradable polymers. The biodegradable elastomers reported here would enable new materials and new possibilities in biomedicine and beyond.

Chemically Stable Black Phase CsPbI3 Inorganic Perovskites for High‐Efficiency Photovoltaics

By Yong Wang, Yuetian Chen, Taiyang Zhang, Xingtao Wang, Yixin Zhao from Wiley: Advanced Materials: Table of Contents. Published on Sep 22, 2020.

The recent progress of CsPbI3 perovskite for highly efficient and stable photovoltaics are summarized. Furthermore, those important phase stabilization strategies for the black phase CsPbI3 are also discussed. With the advancing of fundamental study on CsPbI3 perovskite material properties, the CsPbI3 perovskite and other inorganic perovskite will become more and more promising for high‐efficiency and stable perovskites solar cells. Abstract Research on chemically stable inorganic perovskites has achieved rapid progress in terms of high efficiency exceeding 19% and high thermal stabilities, making it one of the most promising candidates for thermodynamically stable and high‐efficiency perovskite solar cells. Among those inorganic perovskites, CsPbI3 with good chemical components stability possesses the suitable bandgap (≈1.7 eV) for single‐junction and tandem solar cells. Comparing to the anisotropic organic cations, the isotropic cesium cation without hydrogen bond and cation orientation renders CsPbI3 exhibit unique optoelectronic properties. However, the unideal tolerance factor of CsPbI3 induces the challenges of different crystal phase competition and room temperature phase stability. Herein, the latest important developments regarding understanding of the crystal structure and phase of CsPbI3 perovskite are presented. The development of various solution chemistry approaches for depositing high‐quality phase‐pure CsPbI3 perovskite is summarized. Furthermore, some important phase stabilization strategies for black phase CsPbI3 are discussed. The latest experimental and theoretical studies on the fundamental physical properties of photoactive phase CsPbI3 have deepened the understanding of inorganic perovskites. The future development and research directions toward achieving highly stable CsPbI3 materials will further advance inorganic perovskite for highly stable and efficient photovoltaics.

Mesoporous Nanoarchitectures for Electrochemical Energy Conversion and Storage

By Yuxing Yan, Guangrui Chen, Peihong She, Guiyuan Zhong, Wenfu Yan, Bu Yuan Guan, Yusuke Yamauchi from Wiley: Advanced Materials: Table of Contents. Published on Sep 22, 2020.

Mesoporous nanomaterials have attracted significant attention in various important fields, especially as electrode materials or catalysts for energy storage and conversion devices. A comprehensive overview on the synthetic strategies and recent developments of mesoporous nanostructures, their electrochemical properties in energy storage and conversion systems, and future directions for design and synthesis of advanced mesoporous nanostructures is provided. Abstract Mesoporous materials have attracted considerable attention because of their distinctive properties, including high surface areas, large pore sizes, tunable pore structures, controllable chemical compositions, and abundant forms of composite materials. During the last decade, there has been increasing research interest in constructing advanced mesoporous nanomaterials possessing short and open channels with efficient mass diffusion capability and rich accessible active sites for electrochemical energy conversion and storage. Here, the synthesis, structures, and energy‐related applications of mesoporous nanomaterials are the main focus. After a brief summary of synthetic methods of mesoporous nanostructures, the delicate design and construction of mesoporous nanomaterials are described in detail through precise tailoring of the particle sizes, pore sizes, and nanostructures. Afterward, their applications as electrode materials for lithium‐ion batteries, supercapacitors, water‐splitting electrolyzers, and fuel cells are discussed. Finally, the possible development directions and challenges of mesoporous nanomaterials for electrochemical energy conversion and storage are proposed.

Filament‐Free Bulk Resistive Memory Enables Deterministic Analogue Switching

By Yiyang Li, Elliot J. Fuller, Joshua D. Sugar, Sangmin Yoo, David S. Ashby, Christopher H. Bennett, Robert D. Horton, Michael S. Bartsch, Matthew J. Marinella, Wei D. Lu, A. Alec Talin from Wiley: Advanced Materials: Table of Contents. Published on Sep 22, 2020.

A resistive memory cell based on the electrochemical migration of oxygen vacancies for in‐memory neuromorphic computing is presented. By using the average statistical behavior of all oxygen vacancies to store analogue information states, this cell overcomes the stochastic and unpredictable switching plaguing filament‐forming memristors, and instead achieves linear, predictable, and deterministic switching. Abstract Digital computing is nearing its physical limits as computing needs and energy consumption rapidly increase. Analogue‐memory‐based neuromorphic computing can be orders of magnitude more energy efficient at data‐intensive tasks like deep neural networks, but has been limited by the inaccurate and unpredictable switching of analogue resistive memory. Filamentary resistive random access memory (RRAM) suffers from stochastic switching due to the random kinetic motion of discrete defects in the nanometer‐sized filament. In this work, this stochasticity is overcome by incorporating a solid electrolyte interlayer, in this case, yttria‐stabilized zirconia (YSZ), toward eliminating filaments. Filament‐free, bulk‐RRAM cells instead store analogue states using the bulk point defect concentration, yielding predictable switching because the statistical ensemble behavior of oxygen vacancy defects is deterministic even when individual defects are stochastic. Both experiments and modeling show bulk‐RRAM devices using TiO2‐X switching layers and YSZ electrolytes yield deterministic and linear analogue switching for efficient inference and training. Bulk‐RRAM solves many outstanding issues with memristor unpredictability that have inhibited commercialization, and can, therefore, enable unprecedented new applications for energy‐efficient neuromorphic computing. Beyond RRAM, this work shows how harnessing bulk point defects in ionic materials can be used to engineer deterministic nanoelectronic materials and devices.

Near‐Infrared AIE Dots with Chemiluminescence for Deep‐Tissue Imaging

By Chenchen Liu, Xiuxia Wang, Junkai Liu, Qiang Yue, Sijie Chen, Jacky W. Y. Lam, Liang Luo, Ben Zhong Tang from Wiley: Advanced Materials: Table of Contents. Published on Sep 22, 2020.

Near‐infrared chemiluminescence (NIR CL): A novel aggregation‐induced emission (AIE) luminogen named TBL is designed and the NIR CL emission of TBL dots can penetrate through 3 cm‐thick pork ham, which is much better than NIR fluorescence and blue CL emission. Moreover, the successful differentiation of tumor and normal tissue makes this system promising for CL‐guided tumor diagnosis and surgery. Abstract Near‐infrared (NIR) chemiluminescence (CL) emission is highly favorable for deep‐tissue imaging, but chemically conjugated NIR CL emitters with the aggregation‐induced emission (AIE) property for biotechnology are seldom reported. Herein, an AIE‐active NIR CL emitter, TBL, is synthesized by conjugating luminol unit with electron‐accepting benzothiadiazole and an electron‐donating triphenylamine, and subsequently TBL dots are prepared by using F127 as the surfactant. The CL emission of TBL dots can last continuously for over 60 min and can be employed for quantitative (in vitro) and qualitative (in vivo) detection of 1O2. Strikingly, the NIR CL emission can penetrate through tissues with a total thickness of over 3 cm, exhibiting significantly better performance than NIR fluorescence emission and blue CL emission. Moreover, the successful differentiation of tumor and normal tissues by TBL‐based CL imaging in vivo also paves the way for CL‐guided cancer diagnosis and surgery.

Regio‐ and Enantioselective Ni‐Catalyzed Formal Hydroalkylation, Hydrobenzylation and Hydropropargylation of Acrylamides to α‐Tertiary Amides

By Wei Shu, Lou Shi from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 22, 2020.

To develop enantioselective alkyl‐alkyl cross‐couplings with coinstantaneous formation of a stereogenic center without the use of sensitive organometallic species is attractive yet challenging. Herein, we report the intermolecular regio‐ and enantioselective formal hydrofunctionalizations of acrylamides, forging a stereogenic center α ‐position to the newly formed C sp3 ‐C sp3 bond for the first time. The use of a new developed chiral ligand enables the electronically‐reversed formal hydrofunctionalizations, including hydroalkylation, hydrobenzylation, and hydropropargylation, offering an efficient way to access diverse enantioenriched amides with a tertiary α ‐stereogenic carbon center which is facile to racemize. This operationally simple protocol allows for the anti‐Markovnikov enantioselective hydroalkylation, and unprecedented hydrobenzylation, hydropropargylation under mild conditions with excellent functional group compatibility, delivering a wide range of amides with excellent levels of enantioselectivity.

Phase‐junction Electrocatalysts towards Enhanced Hydrogen Evolution Reaction in Alkaline Media

By Qiang Fu, Xianjie Wang, Jiecai Han, Jun Zhong, Zhang Tongrui, Tai Yao, Chengyan Xu, Tangling Gao, Shibo Xi, Ce Liang, Lingling Xu, Ping Xu, Bo Song from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 22, 2020.

To ensure the sustainable hydrogen production via water electrolysis technique, robust, earth‐abundant and high‐efficient electrocatalyst is highly required. Nowadays, to overcome the limitation of conventional single‐phase component , constructing hybrid system could lead to further improvement in electrocatalytic activity. Interface engineering in composite catalysts is thus critical to determine the performance, and phase‐junction interface is supposed to obviously improve the catalytic activity. Here, as a proof‐of‐concept, we presented a combination of theoretical and experimental investigation to certify that nickel diphosphide phase‐junction (c‐NiP 2 /m‐NiP2 ) is an effective electrocatalyst for hydrogen production in alkaline media. The overpotential (at 10 mA cm ‐2 ) for NiP2‐650 (c/m ) in alkaline media could be significantly reduced by 26% and 96% compared with c‐NiP2 and m‐NiP2 , respectively. The enhancement of catalytic activity should be attributed to the strong water dissociation ability and the rearrangement of electrons around the phase‐junction, which markedly improved the Volmer step and benefited the reduction process of adsorbed protons.

Fighting against Drug‐Resistant Tumors using a Dual‐Responsive Pt(IV)/Ru(II) Bimetallic Polymer

By Xiaolong Zeng, Yufei Wang, Jianxiong Han, Wen Sun, Hans‐Jürgen Butt, Xing‐Jie Liang, Si Wu from Wiley: Advanced Materials: Table of Contents. Published on Sep 22, 2020.

A dual‐responsive Pt(IV)/Ru(II) bimetallic polymer is designed to treat drug‐resistant tumors in a patient‐derived‐xenograft (PDX) model. The polymer self‐assembles into nanoparticles, which circulate in bloodstream, accumulate at tumor sites, and are taken up by drug‐resistant cancer cells. The released cisplatin and Ru(II) complexes via intracellular reduction and light irradiation as well as photogenerated 1O2 inhibit the growth of drug‐resistant tumors. Abstract Drug resistance is a major problem in cancer treatment. Herein, the design of a dual‐responsive Pt(IV)/Ru(II) bimetallic polymer (PolyPt/Ru) to treat cisplatin‐resistant tumors in a patient‐derived xenograft (PDX) model is reported. PolyPt/Ru is an amphiphilic ABA‐type triblock copolymer. The hydrophilic A blocks consist of biocompatible poly(ethylene glycol) (PEG). The hydrophobic B block contains reduction‐responsive Pt(IV) and red‐light‐responsive Ru(II) moieties. PolyPt/Ru self‐assembles into nanoparticles that are efficiently taken up by cisplatin‐resistant cancer cells. Irradiation of cancer cells containing PolyPt/Ru nanoparticles with red light generates 1O2, induces polymer degradation, and triggers the release of the Ru(II) anticancer agent. Meanwhile, the anticancer drug, cisplatin, is released in the intracellular environment via reduction of the Pt(IV) moieties. The released Ru(II) anticancer agent, cisplatin, and the generated 1O2 have different anticancer mechanisms; their synergistic effects inhibit the growth of drug‐resistant cancer cells. Furthermore, PolyPt/Ru nanoparticles inhibit tumor growth in a PDX mouse model because they circulate in the bloodstream, accumulate at tumor sites, exhibit good biocompatibility, and do not cause side effects. The results demonstrate that the development of stimuli‐responsive multi‐metallic polymers provides a new strategy to overcome drug resistance.

Beyond Substrates: Strain Engineering of Ferroelectric Membranes

By David Pesquera, Eric Parsonnet, Alexander Qualls, Ruijuan Xu, Andrew J. Gubser, Jieun Kim, Yizhe Jiang, Gabriel Velarde, Yen‐Lin Huang, Harold Y. Hwang, Ramamoorthy Ramesh, Lane W. Martin from Wiley: Advanced Materials: Table of Contents. Published on Sep 22, 2020.

Upon release from their growth substrates, the properties of single‐crystal ferroelectric BaTiO3 membranes integrated on silicon are tuned via the interlayer stress from epitaxially coupled electrode layers where the removal of substrate clamping improves the polarization switching speed. Using this strategy, highly sensitive mechanical control of the dielectric properties in membranes integrated on polymers is also demonstrated. Abstract Strain engineering in perovskite oxides provides for dramatic control over material structure, phase, and properties, but is restricted by the discrete strain states produced by available high‐quality substrates. Here, using the ferroelectric BaTiO3, production of precisely strain‐engineered, substrate‐released nanoscale membranes is demonstrated via an epitaxial lift‐off process that allows the high crystalline quality of films grown on substrates to be replicated. In turn, fine structural tuning is achieved using interlayer stress in symmetric trilayer oxide‐metal/ferroelectric/oxide‐metal structures fabricated from the released membranes. In devices integrated on silicon, the interlayer stress provides deterministic control of ordering temperature (from 75 to 425 °C) and releasing the substrate clamping is shown to dramatically impact ferroelectric switching and domain dynamics (including reducing coercive fields to

Antioxidative Stannous Oxalate Derived Lead‐Free Stable CsSnX3 (X = Cl, Br, and I) Perovskite Nanocrystals

By Cuiting Kang, Huashang Rao, Yueping Fang, Jiejun Zeng, Zhenxiao Pan, Xinhua Zhong from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 22, 2020.

The current research on all‐inorganic perovskite NCs is mainly focused on Pb‐based materials (CsPbX3, X = Cl, Br, and I). However, the toxicity of Pb has become a major obstacle to its application. Correspondingly, lead‐free CsSnX3 perovskite NCs are becoming a promising alternative, but suffer from extremely poor stability. Herein, we highlight the significant effect of Sn(II) precursors used in the synthesis on the stability of the resultant CsSnX3 NCs. A new method is proposed for synthesizing CsSnX3 NCs using Cs2CO3, SnC2O4, and NH4X as corresponding constituent precursors, wherein the ratio of reactants can be facilely adjusted. Stable CsSnX3 NCs can be obtained with the use of antioxidative SnC2O4 as the Sn(II) precursor. Experimental results show that the improvement of NCs stability is mainly ascribed to the role of oxalate in the SnC2O4 precursor. Oxalate ion has a strong antioxidative ability and can effectively inhibit the oxidation of Sn(II) during the synthesis. Besides, oxalate as a bidentate capping ligand is demonstrated to be coordinated on the surface of formed NCs. This can not only passivate the uncoordinated Sn on the surface but also prevent the oxidation of the NCs.

Bipolar Membranes to Promote Formation of Tight Ice‐Like Water for Efficient and Sustainable Water Splitting

By Byung Su Kim, Seul Chan Park, Do‐Hyeong Kim, Gi Hyeon Moon, Jong Gyu Oh, Jaeyoung Jang, Moon‐Sung Kang, Kyung Byung Yoon, Yong Soo Kang from Wiley: Small: Table of Contents. Published on Sep 22, 2020.

Tight ice‐like water improves water dissociation and ion transport kinetics, significantly reducing the overpotential of a bipolar membrane for efficient water splitting. The interaction between water molecules and hematite nanoparticles grown on a graphene oxide catalyst effectively rearranges the network of water molecules to form tight ice‐like water having stronger intermolecular hydrogen bonds. Abstract Bipolar membranes (BPMs) have recently received much attention for their potential to improve the water dissociation reaction (WDR) at their junction by utilizing catalysts. Herein, composite catalysts (Fe2O3@GO) comprising hematite nanoparticles (α‐Fe2O3) grown on 2D graphene oxide (GO) nanosheets are reported, which show unprecedentedly high water dissociation performance in the BPM. Furthermore, new catalytic roles in facilitating WDR at the catalyst–water interface are mechanistically elucidated. It is demonstrated that the partially dissociated bound water, formed by the strongly Lewis‐acidic Fe atoms of the Fe2O3@GO catalyst, helps the “ice‐like water” to become tighter, consequently resulting in weaker intramolecular OH bonds, which reduces activation barriers and thus significantly improves the WDR rate. Notably, Fe2O3@GO‐incorporated BPM shows an extremely low water dissociation potential (0.89 V), compared to commercially available BPM (BP‐1E, 1.13 V) at 100 mA cm−2, and it is quite close to the theoretical potential required for WDR (0.83 V). This performance reduces the required electrical energy consumption for water splitting by ≈40%, as compared to monopolar (Nafion 212 and Selemion AMV) membranes. These results can provide a new approach for the development of water dissociation catalysts and BPMs for realizing highly efficient water splitting systems.

SeC Bonding Promoting Fast and Durable Na+ Storage in Yolk–Shell SnSe2@SeC

By Shuhao Xiao, Zhenzhe Li, Jintao Liu, Yushan Song, Tingshuai Li, Yong Xiang, Jun Song Chen, Qingyu Yan from Wiley: Small: Table of Contents. Published on Sep 22, 2020.

Yolk–shell SnSe2@C nanospheres with SeC bonds in the carbon shell are synthesized by selenization of the SnO2@C precursor. Density functional theory calculation results reveal that the SeC bonding can enhance the charge transfer properties and the binding energy between the SnSe2 core and the carbon shell, leading to greatly improved high‐rate performance and cycling stability for a sodium‐ion battery. Abstract Tin‐based compounds have received much attention as anode materials for lithium/sodium ion batteries owing to their high theoretical capacity. However, the huge volume change usually leads to the pulverization of electrode, giving rise to a poor cycle performance, which have severely hampered their practical application. Herein, highly durable yolk–shell SnSe2 nanospheres (SnSe2@SeC) are prepared by a multistep templating method, with an in situ gas‐phase selenization of the SnO2@C hollow nanospheres. During this process, Se can be doped into the carbon shell with a tunable amount and form SeC bonds. Density functional theory calculation results reveal that the SeC bonding can enhance the charge transfer properties as well as the binding interaction between the SnSe2 core and the carbon shell, favoring an improved rate performance and a superior cyclability. As expected, the sample delivers reversible capacities of 441 and 406 mAh g−1 after 2000 cycles at 2 and 5 A g−1, respectively, as the anode material for a sodium‐ion battery. Such performances are significantly better than the control sample without the SeC bonding and also other metal selenide‐based anodes, evidently showing the advantage of Se doping in the carbon shell.

Interface Engineering of Partially Phosphidated Co@Co–P@NPCNTs for Highly Enhanced Electrochemical Overall Water Splitting

By Jiqing Jiao, Wenjuan Yang, Yuan Pan, Chao Zhang, Shoujie Liu, Chen Chen, Dingsheng Wang from Wiley: Small: Table of Contents. Published on Sep 22, 2020.

A composite catalyst comprising partially phosphidated core@shell Co@Co–P nanoparticles encapsulated in bamboo‐like N, P co‐doped carbon nanotubes is prepared through a pyrolysis–oxidation–phosphidation strategy. As a bifunctional catalyst for both the hydrogen evolution reaction and oxygen evolution reaction, it exhibits an excellent activity and stability for water splitting. A special route for the interface engineering of heterostructures is provided. Abstract Interface engineering is promising but still challenging for developing highly efficient and stable non‐noble‐metal‐based electrocatalysts for water splitting. Herein, partially phosphidated core@shell Co@Co–P nanoparticles encapsulated in bamboo‐like N, P co‐doped carbon nanotubes (denoted as Part‐Ph Co@Co–P@NPCNTs) are prepared through a pyrolysis–oxidation–phosphidation strategy. In this structure, each Co nanoparticle is covered with a thin Co–P layer to form a special core@shell heterojunction interface, and the core@shell structure is further encapsulated by N, P co‐doped CNTs that not only protect the Co from corrosion but also guarantee an effective and fast electron transfer on cobalt phosphide. As a bifunctional catalyst for both the hydrogen evolution reaction and oxygen evolution reaction, it exhibits an excellent activity for overall water splitting, and enables long‐term operation without significant degradation. Density functional theory calculations demonstrate that the interface of the Co/Co2P heterojunction could lower the values of ΔGH* (hydrogen adsorption) and ΔGB (water dissociation), which are negatively correlated to the j10, because of the electronic structures of up‐shifted d‐band center. This study not only presents an efficient and stable electrocatalyst for overall water splitting but also provides a special route for the interface engineering of heterostructures.

Alkali‐Etched Ni(II)‐Based Metal–Organic Framework Nanosheet Arrays for Electrocatalytic Overall Water Splitting

By Jian Zhou, Yibo Dou, Xue‐Qian Wu, Awu Zhou, Lun Shu, Jian‐Rong Li from Wiley: Small: Table of Contents. Published on Sep 22, 2020.

The introduction of defects into metal–organic framework (MOF) by alkali‐etching treatment to create rich active sites and tailor electrical conductivity is proposed. The resultant defect‐rich Ni(II)‐MOF nanosheet array exhibits excellent electrocatalytic overall water splitting performance, comparable to the noble metal‐based benchmark catalysts. Abstract The exploration of efficient electrocatalysts is the central issue for boosting the overall efficiency of water splitting. Herein, pertinently creating active sites and improving conductivity for metal–organic frameworks (MOFs) is proposed to tailor electrocatalytic properties for overall water splitting. An Ni(II)‐MOF nanosheet array is presented as an ideal material model and a facile alkali‐etched strategy is developed to break its NiO bonds accompanied with the introduction of extra‐framework K cations, which contribute to creating highly active open metal sites and largely improving the electrical conductivity. As a result, the assembled defect‐Ni‐MOF||defect‐Ni‐MOF electrolyte cell delivers a lower and stable voltage of 1.50 V at 10 mA cm−2 in alkaline medium for overall water splitting, comparable to the combination of iridium and platinum as benchmark catalysts.

Electrochemical Insights, Developing Strategies, and Perspectives toward Advanced Potassium–Sulfur Batteries

By Xiaomin Yuan, Bo Zhu, Jinkui Feng, Chengguo Wang, Xun Cai, Kun Qiao, Rongman Qin from Wiley: Small: Table of Contents. Published on Sep 22, 2020.

As a brand‐new, efficient, and low‐cost battery system, potassium–sulfur (K–S) batteries offer a great playground for chemists to underpin investigations on large‐scale power applications. This article addresses the electrochemical kinetic concept and discusses rational strategies on rational physical regulation and chemical engineering of K–S batteries, providing prospective outlooks in materials optimization, structure innovations, as well as relevant electrochemistry. Abstract The boosting demand for high‐capacity energy storage systems requires innovative battery technologies with low‐cost and sustainability. The advancement of potassium–sulfur (K–S) batteries have been triggered recently due to abundant resource and cost effectiveness. However, the functional performance of K–S batteries is fundamentally restricted by the vague understanding of K–S electrochemistry and the imperfect cell components or architectures, facing the issues of low cathode conductivity, intermediate shuttle loss, poor anode stability, electrode volume fluctuation, etc. Inspired by considerable research efforts on rechargeable metal–sulfur batteries, the holistic K–S system can be stabilized and promoted through various strategies on rational physical regulation and chemical engineering. In this review, first an attempt is made to address the electrochemical kinetic concept of K–S system on the basis of the emerging studies. Then, the classification of performance‐improving strategies is thoroughly discussed in terms of specific battery component and prospective outlooks in materials optimization, structure innovations, as well as relevant electrochemistry are provided. Finally, the critical perspectives and challenges are discussed to demonstrate the forward‐looking developmental directions of K–S batteries. This review not only endeavors to provide a deep understanding of the electrochemistry mechanism and rational designs for high‐energy K–S batteries, but also encourages more efforts in their large‐scale practical realization.

Establishing Multifunctional Interface Layer of Perovskite Ligand Modified Lead Sulfide Quantum Dots for Improving the Performance and Stability of Perovskite Solar Cells

By Ruiman Ma, Zhenwei Ren, Can Li, Yong Wang, Zhanfeng Huang, Yong Zhao, Tingbin Yang, Yongye Liang, Xiao Wei Sun, Wallace C. H. Choy from Wiley: Small: Table of Contents. Published on Sep 22, 2020.

A multifunctional interface layer is formed on perovskite film through establishing perovskite as the ligand on PbS quantum dots (QDs). The multifunctions are strong interactions of PbS QDs with perovskites particularly at the grain boundaries, an inhibition of iodide ions mobilization, and the reduction of the dangling bonds of Pb2+. Finally, the perovskite device efficiency and stability are highly improved. Abstract While organic–inorganic halide perovskite solar cells (PSCs) show great potential for realizing low‐cost and easily fabricated photovoltaics, the unexpected defects and long‐term stability against moisture are the main issues hindering their practical applications. Herein, a strategy is demonstrated to address the main issues by introducing lead sulfide quantum dots (QDs) on the perovskite surface as the multifunctional interface layer on perovskite film through establishing perovskite as the ligand on PbS QDs. Meanwhile, the multifunctions are featured in three aspects including the strong interactions of PbS QDs with perovskites particularly at the grain boundaries favoring good QDs coverage on perovskites for ultimate smooth morphology; an inhibition of iodide ions mobilization by the strong interaction between iodide and the incorporated QDs; and the reduction of the dangling bonds of Pb2+ by the sulfur atoms of PbS QDs. Finally, the device performances are highly improved due to the reduced defects and non‐radiative recombination. The results show that both open‐circuit voltage and fill factor are significantly improved to the high values of 1.13 V and 80%, respectively in CH3NH3PbI3‐based PSCs, offering a high efficiency of 20.64%. The QDs incorporation also enhances PSCs’ stability benefitting from the induced hydrophobic surface and suppressed iodide mobilization.

Nanoengineered Organic Electrodes for Highly Durable and Ultrafast Cycling of Organic Sodium‐Ion Batteries

By Ranjith Thangavel, Megala Moorthy, Bala Krishnan Ganesan, Wontae Lee, Won‐Sub Yoon, Yun‐Sung Lee from Wiley: Small: Table of Contents. Published on Sep 22, 2020.

A series of uniform and ultrathin (Å‐level) metal oxide coatings employing atomic layer deposition are used to stabilize the electrode–electrolyte interface, and to reduce solubility of the organic electrode (perylene‐3,4,9,10‐tetracarboxylicacid dianhydride) in organic sodium‐ion batteries. The chemical stability of the metal oxide coating layer plays a critical role in influencing the redox behavior, and improving kinetics of organic electrodes. Abstract Sodium‐ion batteries (SIBs) have become increasingly important as next‐generation energy storage systems for application in large‐scale energy storage. It is very crucial to develop an eco‐friendly and green SIB technique with superior performance for sustainable future use. Replacing the conventional inorganic electrode materials with green and safe organic electrodes will be a promising approach. However, the poor electrochemical kinetics, unstable electrode–electrolyte interface, high solubility of the electrodes in the electrolyte, and large amount of conductive carbon present great challenges for organic SIBs. In this study, the issues of organic electrodes are addressed through atomic‐level manipulation of these organic molecules using a series of ultrathin (Å‐level) metal oxide coatings (Al2O3, ZnO, and TiO2). Uniform and precise coatings on the perylene‐3,4,9,10‐tetracarboxylicacid dianhydride by gas‐phase atomic layer deposition technique shows a stable interphase, enhanced electrochemical kinetics (71C, 10 A g−1), and excellent stability (89%–500 cycles) compared to conventional organic electrode (70%–200 cycles). Further studies reveal that the chemical stability of the metal oxide coating layer plays a critical role in influencing the redox behavior, and improving kinetics of organic electrodes. This study opens a new avenue for developing high‐energy organic SIBs with performance equivalent to inorganic counterparts.

Fusiform‐Shaped g‐C3N4 Capsules with Superior Photocatalytic Activity

By Zhixiang Jiang, Xiao Zhang, Hsueh‐Shih Chen, Ping Yang, San Ping Jiang from Wiley: Small: Table of Contents. Published on Sep 22, 2020.

Fusiform‐shaped g‐C3N4 capsules are synthesized by nucleation kinetics of supramolecular assemblies and high temperature thermal polycondensation. These capsules reveal excellent properties in the photocatalytic H2 evolution and photocatalytic reduction of CO2. Besides that, the special selective reduction of CO2 to CO or CH4 is observed with the variation of nanostructure. Abstract Carbon nitride (g‐C3N4) nanostructure rebuilding is an effective means to modify its photocatalytic properties, especially the hollow micron‐nanostructure. The increased scattering in the body effectively improves the light utilization efficiency and improves catalytic properties. In this work, fusiform‐shaped g‐C3N4 capsules are created by controlling the nucleation kinetics of supramolecular assemblies. The fusiform‐shaped capsule micron‐nanostructure is synthesized with ultrathin wall thickness and adjusted carbon/nitride ratios which decrease the recombination rate of photo‐generated carriers. The hollow nanostructure and relatively higher specific surface area of the fusiform‐shaped capsule effectively enhance light scattering inside body and lead to an enhanced carrier utilization efficiency. Moreover, the decrease of bandgap and relatively negative conduction band position affect the response of hollow fusiform‐shaped g‐C3N4 capsules (Hf‐g‐C3N4) in visible light region and improve the photo‐reducing performance. In term of H2 evolution property, Hf‐g‐C3N4 has been improved to 7052 µmol g−1 h−1, which is 10.9 times higher compared with bulk structure. More importantly, Hf‐g‐C3N4 can produce CH4 at the rate of 1.63 µmol g−1 h−1 without help of co‐catalyst and hole sacrificial agent in the photocatalytic reduction reaction of CO2 to CH4. At same time, the selective photocatalytic reduction of CO2 is another advantage of Hf‐g‐C3N4.

Modulation of Disordered Coordination Degree Based on Surface Defective Metal–Organic Framework Derivatives toward Boosting Oxygen Evolution Electrocatalysis

By Xinyue Zheng, Gan Jia, Guozheng Fan, Wenjun Luo, Zhaosheng Li, Zhigang Zou from Wiley: Small: Table of Contents. Published on Sep 22, 2020.

A squarate‐based metal–organic framework ([Co3(C4O4)2(OH)2]⋅3H2O) with complete coordination environment is employed to explore the effect of defect‐induced disordered coordination degree for electrochemical activity. Proper modulation of defect concentration leads to electronic reconfiguration near metal active centers, resulting in optimized electrocatalytic performance. Abstract Seeking potential electrocatalysts with both large‐scale application and robust activity for the oxygen evolution reaction allows for no delay. Herein, a squarate‐based metal–organic framework (MOF) ([Co3(C4O4)2(OH)2]⋅3H2O) is reported for electrocatalytic water oxidation. A facile, green, and low‐cost strategy is proposed to introduce defects by not only rationally breaking CoO bonds to form defective coordination environment and electronic reconfiguration, but also systematically modulates defect concentration to optimize electrochemical performance. As a result, the post‐treated surface defective MOF derivative (Co‐MOF‐3h) achieves a current density of 50 mA cm−2 at an overpotential of 380 mV, owing to larger active surface area, more opened active sites, and favorable conducting channels. Finally, density functional theory calculations have further validated the effect of defective coordination in regard to electronic structure for electrocatalysts. This study delivers inspirations in defect engineering and is in favor of developing high‐efficiency electrocatalysts.

Highly Ordered Nanochannels in a Nanosheet‐Directed Thin Zeolite Nanofilm for Precise and Fast CO2 Separation

By Bin Wang, Tangyin Wu, Miao Yu, Shiguang Li, Rongfei Zhou, Weihong Xing from Wiley: Small: Table of Contents. Published on Sep 22, 2020.

Ordered and perpendicular nanochannels are assembled in a preferentially oriented zeolite nanofilm as a CO2 fast path. A “gel nuclei‐less” route is developed to tune the orientation and thickness of crystalline nanofilms. This nanofilm displays milestone CO2 permeance in the order of 10−5 mol (m2 s Pa)−1 and selectivity more than 100 for the CO2/CH4 mixture. Abstract Precise molecular and ion separations depend largely on the size and uniformity of the nanochannels in a defect‐free microporous nanofilm. Ordered and perpendicular nanochannels with uniform pore size are assembled into a continuous and defect‐free film by a “gel nuclei‐less” route. The ultrathin (

Aqueous Rechargeable Li+/Na+ Hybrid Ion Battery with High Energy Density and Long Cycle Life

By Xueqian Zhang, Mengfei Dong, Yali Xiong, Zhiguo Hou, Huaisheng Ao, Mengke Liu, Yongchun Zhu, Yitai Qian from Wiley: Small: Table of Contents. Published on Sep 22, 2020.

A low‐cost light‐weight cathode current collector is developed with corrosion resistance and high adhesion, contributing to the long cycle of the battery. By adding urea into electrolyte, the electrochemical stability window is expanded to 3.2 V. The electrochemical reaction production of urea deposited on electrode surfaces forms a solid‐electrolyte interphase layer, which helps maintain cathode structural stability and extend battery circulating life. Abstract The practical application of aqueous rechargeable batteries is hampered by the low energy density and poor cycle stability, which mostly arises from the corrosion of cathode current collector, exfoliation of active material, and narrow electrochemical stability window of aqueous electrolyte. A light‐weight and low‐cost cathode current collector composed of graphite and carbon nanotube coated on nylon membrane exhibiting corrosion resistance and strong adhesion is developed. Also, a modified aqueous electrolyte with the addition of urea whose window is expanded to ≈3.2 V is developed that contributes to the formation of solid‐electrolyte interphase on surfaces of electrodes. LiMn2O4/NaTi2(PO4)3 Li+/Na+ hybrid ion battery using such aqueous electrolyte and current collector is demonstrated to cycle up to 10 000 times with low cost (60 dollars per kWh) and high energy density (100 Wh kg−1) for stationary energy storage and electronic vehicles applications.

Electrochemical Charging Effect on the Optical Properties of InP/ZnSe/ZnS Quantum Dots

By Jumi Park, Yu‐Ho Won, Taehyung Kim, Eunjoo Jang, Dongho Kim from Wiley: Small: Table of Contents. Published on Sep 22, 2020.

The photoluminescence properties of quantum dots (QDs) are vulnerable to electrochemical charging due to Auger recombination between the additional charge and photo‐induced charge carriers. However, the QDs passivated by thicker mid‐shell are relatively stable about the charging owing to small phonon effects and large spatial distribution of charge carriers in the large volume. Abstract Semiconductor quantum dots (QDs) are spotlighted as a key type of emissive material for the next generation of light‐emitting diodes (LEDs). This work presents the investigation of the electrochemical charging effect on the absorption and emission of the InP/ZnSe/ZnS QDs with different mid‐shell thicknesses. The excitonic peak is gradually bleached during electrochemical charging, which is caused by 1Se (or 1Sh) state filling when the electron (or hole) is injected into the InP core. Additional charges also lead to photoluminescence (PL) intensity reduction, however, it is greatly mitigated as the mid‐shell thickness increases. Various PL measurements reveal that the PL reduction under electrochemical charging is attributed to the acoustic phonon‐assisted Auger recombination. Here, the Auger recombination in QDs with a thick mid‐shell is reduced under the electrochemically charged condition, indicating that QDs with larger volume are more stable emitters in charge‐injecting devices such as LEDs. Furthermore, the negative and positive trion Auger recombination rate constants are estimated, respectively, via electrochemical charging. The negative trion Auger rate constants decrease with an increase in the mid‐shell thickness increases, whereas the positive trion Auger rate constants are not heavily reliant on the mid‐shell thickness.

Thu 03 Dec 16:00: TBA

From All Talks (aka the CURE list). Published on Sep 22, 2020.

TBA

TBA

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Thu 05 Nov 16:00: Seismic behaviour of structures with basements in liquefiable soil

From All Talks (aka the CURE list). Published on Sep 22, 2020.

Seismic behaviour of structures with basements in liquefiable soil

TBA

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Tue 20 Oct 17:00: The first Egyptian society

From All Talks (aka the CURE list). Published on Sep 22, 2020.

The first Egyptian society

Abstract not available

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Frustrated Lewis Pair Chelation as a Vehicle for Low Temperature Semiconductor Element and Polymer Deposition

By Alvaro Omaña, Rachel Green, Ryo Kobayashi, Yingjie He, Evan Antoniuk, Michael Ferguson, Yuqiao Zhou, Jonathan Veinot, Takeaki Iwamoto, Alex Brown, Eric Rivard from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 22, 2020.

The stabilization of silicon(II) and germanium(II) dihydrides by an intramolecular Frustrated Lewis Pair (FLP) ligand, PB, i Pr­2P(C6H4)BCy2 (Cy = cyclohexyl) is reported. The resulting hydride complexes [PB{SiH2}] and [PB{GeH2}] are indefinitely stable at room temperature, yet can deposit films of silicon and germanium, respectively, upon mild thermolysis in solution. Hallmarks of this work include: (1) the ability to recycle the FLP phosphine‐borane ligand (PB) after element deposition, and (2) the single‐source precursor [PB{SiH2}] deposits Si films at a record low temperature from solution (110 °C). The dialkylsilicon(II) adduct [PB{SiMe2}] was also prepared, and shown to release poly(dimethylsilane) [SiMe2]n upon heating. Overall, this study introduces a “closed loop” deposition strategy for semiconductors that steers materials science away from the use of harsh reagents or high temperatures.

Liquid‐Metal Synthesized Ultrathin SnS Layers for High‐Performance Broadband Photodetectors

By Vaishnavi Krishnamurthi, Hareem Khan, Taimur Ahmed, Ali Zavabeti, Sherif Abdulkader Tawfik, Shubhendra Kumar Jain, Michelle J. S. Spencer, Sivacarendran Balendhran, Kenneth B Crozier, Ziyuan Li, Lan Fu, Md Mohiuddin, Mei Xian Low, Babar Shabbir, Andreas Boes, Arnan Mitchell, Christopher F. McConville, Yongxiang Li, Kourosh Kalantar‐Zadeh, Nasir Mahmood, Sumeet Walia from Wiley: Advanced Materials: Table of Contents. Published on Sep 22, 2020.

Miniaturized photodetectors are key for the next generation of sensing, communication, and imaging technologies. Single‐atom‐thick SnS layers are printed on a millimeter scale to showcase application in high‐performance photodetectors. These SnS‐based ultrafast photodetectors show a broadband spectral response ranging from deep ultraviolet to near infrared wavelengths (i.e., 280 to 850 nm) with excellent figures of merit. Abstract Atomically thin materials face an ongoing challenge of scalability, hampering practical deployment despite their fascinating properties. Tin monosulfide (SnS), a low‐cost, naturally abundant layered material with a tunable bandgap, displays properties of superior carrier mobility and large absorption coefficient at atomic thicknesses, making it attractive for electronics and optoelectronics. However, the lack of successful synthesis techniques to prepare large‐area and stoichiometric atomically thin SnS layers (mainly due to the strong interlayer interactions) has prevented exploration of these properties for versatile applications. Here, SnS layers are printed with thicknesses varying from a single unit cell (0.8 nm) to multiple stacked unit cells (≈1.8 nm) synthesized from metallic liquid tin, with lateral dimensions on the millimeter scale. It is reveal that these large‐area SnS layers exhibit a broadband spectral response ranging from deep‐ultraviolet (UV) to near‐infrared (NIR) wavelengths (i.e., 280–850 nm) with fast photodetection capabilities. For single‐unit‐cell‐thick layered SnS, the photodetectors show upto three orders of magnitude higher responsivity (927 A W−1) than commercial photodetectors at a room‐temperature operating wavelength of 660 nm. This study opens a new pathway to synthesize reproduceable nanosheets of large lateral sizes for broadband, high‐performance photodetectors. It also provides important technological implications for scalable applications in integrated optoelectronic circuits, sensing, and biomedical imaging.

Mon 28 Sep 10:30: Characterizing and forecasting tumour evolution Please email anna.toporska@cruk.cam.ac.uk by Friday 25 September to receive a ZOOM registration link

From All Talks (aka the CURE list). Published on Sep 22, 2020.

Characterizing and forecasting tumour evolution

Characterizing the mode – the way, manner, or pattern – of evolution in tumours is important for clinical forecasting and optimizing cancer treatment. DNA sequencing studies have inferred various modes, including branching, punctuated and neutral evolution, but it is unclear why a particular pattern predominates in any given tumour. Dr Robert Noble will argue that differences in tumour architecture can explain the variety of observed genetic patterns. He will present results of spatially explicit population genetic models showing that, within biologically relevant parameter ranges, human tumours are expected to exhibit four distinct onco-evolutionary modes (oncoevotypes), governed by the mode of cell dispersal and the range of cell-cell interaction. New quantitative indices will be introduced for describing and classifying these oncoevotypes. Dr Noble will further present an investigation of when, why and how intratumour heterogeneity can be used to forecast tumour growth rate and progression-free survival. He will thus provide explanations – grounded in evolutionary theory – for empirical findings in various cancers. This work informs the search for new prognostic biomarkers and contributes to the development of predictive oncology.

Please email anna.toporska@cruk.cam.ac.uk by Friday 25 September to receive a ZOOM registration link

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Tue 17 Nov 13:00: Mechanistic basis of epigenetic switching and memory Hosted by: Ben Simons & Emma Rawlins

From All Talks (aka the CURE list). Published on Sep 22, 2020.

Mechanistic basis of epigenetic switching and memory

Abstract not available

Hosted by: Ben Simons & Emma Rawlins

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Simultaneous Enantiospecific Detection of Multiple Compounds in Mixtures using NMR Spectroscopy

By Lars T. Kuhn, Kumar Motiram-Corral, Toby J. Athersuch, Teodor Parella, Míriam Pérez-Trujillo from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 22, 2020.

Chirality plays a fundamental role in nature, but its detection and quantification still face many limitations. To date, the enantiospecific analysis of mixtures necessarily requires prior separation of the individual components. The simultaneous enantiospecific detection of multiple chiral molecules in a mixture represents a major challenge, which would lead to a significantly better understanding of the underlying biological processes; e.g. via enantiospecifically analysing metabolites in their native environment. Here, we report on the first in situ enantiospecific detection of a thirty‐nine‐component mixture. As a proof of concept, eighteen essential amino acids at physiological concentrations were simultaneously enantiospecifically detected using NMR spectroscopy and a chiral solvating agent. This work represents a first step towards the simultaneous multicomponent enantiospecific analysis of complex mixtures, a capability that will have substantial impact on metabolism studies, metabolic phenotyping, chemical reaction monitoring, and many other fields where complex mixtures containing chiral molecules require efficient characterisation.

Oganesson − A noble gas element that is neither noble nor a gas

By Peter Schwerdtfeger, O. R. Smits, J.-M. Mewes, Paul Jerabek, Peter Schwerdtfeger from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 22, 2020.

Oganesson (Og) is the last entry into the Periodic Table completing the seventh period of elements and group 18 of the noble gases. Only three atoms of Og have been successfully produced in nuclear collision experiments, with an estimate half‐life for [[EQUATION]] of [[EQUATION]] ms. [1] With such a short lifetime, chemical and physical properties inevitably have to come from accurate relativistic quantum theory. Here, we employ two complementary computational approaches, namely parallel tempering Monte‐Carlo (PTMC) simulations and first‐principles thermodynamic integration (TI), both calibrated against a highly accurate coupled‐cluster reference to pin‐down the melting and boiling points of this super‐heavy element. In excellent agreement, these approaches show Og to be a solid at ambient conditions with a melting point of ~325 K. In contrast, calculations in the nonrelativistic limit reveal a melting point for Og of 220 K, suggesting a gaseous state as expected for a typical noble gas element. Accordingly, relativistic effects shift the solid‐to‐liquid phase transition by about 100 K.

Revealing isolated M‐N3C1 active sites for efficient collaborative oxygen reduction catalysis

By Feng Li, Gao-Feng Han, Yunfei Bu, Hyuk-Jun Noh, Jong-Pil Jeon, Tae Joo Shin, Seok-Jin Kim, Yuen Wu, Hu Young Jeong, Zhengping Fu, Yalin Lu, Jong-Beom Baek from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 22, 2020.

Single atom catalysts (SACs) are of great importance for oxygen reduction, a critical process in renewable energy technologies such as fuel cells and metal‐air batteries. The catalytic performance of SACs largely depends on the structure of their active sites, but explorations of highly active structures for SAC active sites are still limited. Herein, we demonstrate a combined experimental and theoretical study of oxygen reduction catalysis on SACs, which incorporate M‐N 3 C 1 site structure, composed of atomically dispersed transition metals (e.g., Fe, Co, and Cu) in nitrogen doped carbon nanosheets. The resulting SACs with M‐N 3 C 1 sites exhibited prominent oxygen reduction catalytic activities in both acidic and alkaline media, following the trend Fe‐N 3 C 1 > Co‐N 3 C 1 > Cu‐N 3 C 1 . Theoretical calculations suggest the C atoms in these structures behave as collaborative adsorption sites to M atoms, thanks to interactions between the d / p orbitals of the M/C atoms in the M‐N 3 C 1 sites, enabling dual site oxygen reduction. Compared with the common single site mechanism, the proposed dual site mechanism was determined to be more favorable for oxygen reduction catalysis, in good agreement with the experimental findings.

A General and Highly Selective Palladium‐Catalyzed Hydroamidation of 1,3‐Diynes

By Jiawang Liu, Carolin Schneider, Ji Yang, Zhihong Wei, Haijun Jiao, Robert Franke, Ralf Jackstell, Matthias Beller from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 22, 2020.

A chemo‐, regio‐ and stereoselective mono‐hydroamidation of (un)symmetrical 1,3‐diynes is described. Key for the success of this novel transformation is the utilization of an advanced palladium catalyst system with the specific ligand L6 (Neolephos). The synthetic value of this general approach to synthetically useful α‐alkynyl‐α, β‐unsaturated amides is showcased by diversification of several structurally complex molecules and marketed drugs. Control experiments and density functional theory (M06L‐SMD) computations also suggest the crucial role of the substrate in controlling the regioselectivity of unsymmetrical 1,3‐diynes.

[ASAP] Dual-Mode Infrared Absorption by Segregating Dopants within Plasmonic Semiconductor Nanocrystals

By Stephen L. Gibbs, Christopher Dean, Joey Saad, Bharat Tandon, Corey M. Staller, Ankit Agrawal, and Delia J. Milliron from Nano Letters: Latest Articles (ACS Publications). Published on Sep 22, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c02992

[ASAP] Magnetic Vortex States in Toroidal Iron Oxide Nanoparticles: Combining Micromagnetics with Tomography

By George R. Lewis, James C. Loudon, Robert Tovey, Yen-Hua Chen, Andrew P. Roberts, Richard J. Harrison, Paul A. Midgley, and Emilie Ringe from Nano Letters: Latest Articles (ACS Publications). Published on Sep 22, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c02795

[ASAP] Bismuth Oxyhydroxide-Pt Inverse Interface for Enhanced Methanol Electrooxidation Performance

By Xuchun Wang, Miao Xie, Fenglei Lyu, Yun-Mui Yiu, Zhiqiang Wang, Jiatang Chen, Lo-Yueh Chang, Yujian Xia, Qixuan Zhong, Mingyu Chu, Hao Yang, Tao Cheng, Tsun-Kong Sham, and Qiao Zhang from Nano Letters: Latest Articles (ACS Publications). Published on Sep 22, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c03340

[ASAP] Engineering Complex Synaptic Behaviors in a Single Device: Emulating Consolidation of Short-term Memory to Long-term Memory in Artificial Synapses via Dielectric Band Engineering

By Jun Tao, Debarghya Sarkar, Salil Kale, Prakhar Kumar Singh, and Rehan Kapadia from Nano Letters: Latest Articles (ACS Publications). Published on Sep 22, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c03548

[ASAP] Intermetallic PtCu Nanoframes as Efficient Oxygen Reduction Electrocatalysts

By Ho Young Kim, Taehyun Kwon, Yoonhoo Ha, Minki Jun, Hionsuck Baik, Hu Young Jeong, Hyungjun Kim, Kwangyeol Lee, and Sang Hoon Joo from Nano Letters: Latest Articles (ACS Publications). Published on Sep 22, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c02812

[ASAP] Solar Freckles: Long-Term Photochromic Tattoos for Intradermal Ultraviolet Radiometry

By Jesse L. Butterfield, Sean P. Keyser, Karan V. Dikshit, Hyejin Kwon, Maranke I. Koster⊗, and Carson J. Bruns from ACS Nano: Latest Articles (ACS Publications). Published on Sep 22, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c05723

[ASAP] Grain Boundary Motion in Two-Dimensional Hexagonal Boron Nitride

By Xibiao Ren and Chuanhong Jin from ACS Nano: Latest Articles (ACS Publications). Published on Sep 22, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c05501

[ASAP] Electron and X-ray Focused Beam-Induced Cross-Linking in Liquids: Toward Rapid Continuous 3D Nanoprinting and Interfacing using Soft Materials

By Tanya Gupta, Evgheni Strelcov, Glenn Holland, Joshua Schumacher, Yang Yang, Mandy B. Esch, Vladimir Aksyuk, Patrick Zeller, Matteo Amati, Luca Gregoratti, and Andrei Kolmakov from ACS Nano: Latest Articles (ACS Publications). Published on Sep 22, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c04266

[ASAP] Ambipolar Deep-Subthreshold Printed-Carbon-Nanotube Transistors for Ultralow-Voltage and Ultralow-Power Electronics

By Luis Portilla, Jianwen Zhao, Yan Wang, Liping Sun, Fengzhu Li, Malo Robin, Miaomiao Wei, Zheng Cui, Luigi G. Occhipinti, Thomas D. Anthopoulos, and Vincenzo Pecunia from ACS Nano: Latest Articles (ACS Publications). Published on Sep 22, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c06619

[ASAP] Synergistic Bimetallic Metallic Organic Framework-Derived Pt–Co Oxygen Reduction Electrocatalysts

By Yin Xiong, Yao Yang, Francis J. DiSalvo, and Héctor D. Abruña from ACS Nano: Latest Articles (ACS Publications). Published on Sep 22, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c04559

[ASAP] Space-Selective Chemodynamic Therapy of CuFe5O8 Nanocubes for Implant-Related Infections

By Geyong Guo, Huilin Zhang, Hao Shen, Chongzun Zhu, Renke He, Jin Tang, Ya Wang, Xingwu Jiang, Jiaxing Wang, Wenbo Bu, and Xianlong Zhang from ACS Nano: Latest Articles (ACS Publications). Published on Sep 22, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c05255

[ASAP] Catalytic Asymmetric Synthesis of Chiral Covalent Organic Frameworks from Prochiral Monomers for Heterogeneous Asymmetric Catalysis

By Jian-Cheng Wang, Xuan Kan, Jin-Yan Shang, Hua Qiao, and Yu-Bin Dong from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Sep 22, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c07461

[ASAP] Spotlights on Recent JACS Publications

By ACS Contributing Correspondents from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Sep 22, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c10087

[ASAP] Mechanistic Insight into the Photoredox-Nickel-HAT Triple Catalyzed Arylation and Alkylation of α-Amino Csp3–H Bonds

By Bholanath Maity, Chen Zhu, Huifeng Yue, Long Huang, Moussab Harb, Yury Minenkov, Magnus Rueping, and Luigi Cavallo from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Sep 22, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c05010

[ASAP] Methane Borylation Catalyzed by Ru, Rh, and Ir Complexes in Comparison with Cyclohexane Borylation: Theoretical Understanding and Prediction

By Rong-Lin Zhong and Shigeyoshi Sakaki from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Sep 22, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c07239

[ASAP] Facile H/D Exchange at (Hetero)Aromatic Hydrocarbons Catalyzed by a Stable Trans-Dihydride N-Heterocyclic Carbene (NHC) Iron Complex

By Subhash Garhwal, Alexander Kaushansky, Natalia Fridman, Linda J. W. Shimon, and Graham de Ruiter from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Sep 22, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c07689

[ASAP] Correction to “Inorganic Halide Double Perovskites with Optoelectronic Properties Modulated by Sublattice Mixing”

By Christopher J. Bartel, Jacob M. Clary, Christopher Sutton, Derek Vigil-Fowler, Bryan R. Goldsmith, Aaron M. Holder, and Charles B. Musgrave from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Sep 22, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c08740

Publisher Correction: Predictive modelling of structure formation in semiconductor films produced by meniscus-guided coating

By Tomasz Marszalek from Nature Materials - Issue - nature.com science feeds. Published on Sep 22, 2020.

Nature Materials, Published online: 22 September 2020; doi:10.1038/s41563-020-00832-0

Publisher Correction: Predictive modelling of structure formation in semiconductor films produced by meniscus-guided coating

Nanoparticle‐Based Electrodes with High Charge Transfer Efficiency through Ligand Exchange Layer‐by‐Layer Assembly

By Yongmin Ko, Cheong Hoon Kwon, Seung Woo Lee, Jinhan Cho from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

Various energy electrodes using high‐energy nanoparticles (NPs) have great difficulty in enhancing their performance due to poor charge transfer between neighboring NPs, which mainly originates from the presence of bulky organic ligands onto the NPs. Recent progress on the control over organic ligands of energy NPs and adsorption approaches for the preparation of high‐performance energy electrodes is introduced. Abstract Organic‐ligand‐based solution processes of metal and transition metal oxide (TMO) nanoparticles (NPs) have been widely studied for the preparation of electrode materials with desired electrical and electrochemical properties for various energy devices. However, the ligands adsorbed on NPs have a significant effect on the intrinsic properties of materials, thus influencing the performance of bulk electrodes assembled by NPs for energy devices. To resolve these critical drawbacks, numerous approaches have focused on developing unique surface chemistry that can exchange bulky ligands with small ligands or remove bulky ligands from NPs after NP deposition. In particular, recent studies have reported that the ligand‐exchange‐induced layer‐by‐layer (LE‐LbL) assembly of NPs enables controlled assembly of NPs with the desired interparticle distance, and interfaces, dramatically improving the electrical/electrochemical performance of electrodes. This emerging approach also demonstrates that efficient surface ligand engineering can exploit the unique electrochemical properties of individual NPs and maximize the electrochemical performance of the resultant NP‐assembled electrodes through improved charge transfer efficiency. This report focuses on how LE‐LbL assembly can be effectively applied to NP‐based energy storage/conversion electrodes. First, the basic principles of the LE‐LbL approach are introduced and then recent progress on NP‐based energy electrodes prepared via the LE‐LbL approach is reviewed.

High Throughput Methods in the Synthesis, Characterization, and Optimization of Porous Materials

By Ivan G. Clayson, Daniel Hewitt, Martin Hutereau, Tom Pope, Ben Slater from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

High throughput synthetic, computational, and analytic/machine learning approaches applied to porous materials are reviewed. The benefits of a virtuous circle, where there is feedback between each strand of research, are highlighted. Abstract Porous materials are widely employed in a large range of applications, in particular, for storage, separation, and catalysis of fine chemicals. Synthesis, characterization, and pre‐ and post‐synthetic computer simulations are mostly carried out in a piecemeal and ad hoc manner. Whilst high throughput approaches have been used for more than 30 years in the porous material fields, routine integration of experimental and computational processes is only now becoming more established. Herein, important developments are highlighted and emerging challenges for the community identified, including the need to work toward more integrated workflows.

Shape Changing Robots: Bioinspiration, Simulation, and Physical Realization

By Dylan Shah, Bilige Yang, Sam Kriegman, Michael Levin, Josh Bongard, Rebecca Kramer‐Bottiglio from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

Biological tissues exhibit incredible dynamic plasticity, enabling organisms to grow and thrive in challenging environments. Inspired by such feats, engineers have begun to design robots capable of actively editing their own structure and behaviors. An overview of the literature on shape changing robots is provided, and how multifunctional materials will help solve grand challenges to enable next‐generation robots is elucidated. Abstract One of the key differentiators between biological and artificial systems is the dynamic plasticity of living tissues, enabling adaptation to different environmental conditions, tasks, or damage by reconfiguring physical structure and behavioral control policies. Lack of dynamic plasticity is a significant limitation for artificial systems that must robustly operate in the natural world. Recently, researchers have begun to leverage insights from regenerating and metamorphosing organisms, designing robots capable of editing their own structure to more efficiently perform tasks under changing demands and creating new algorithms to control these changing anatomies. Here, an overview of the literature related to robots that change shape to enhance and expand their functionality is presented. Related grand challenges, including shape sensing, finding, and changing, which rely on innovations in multifunctional materials, distributed actuation and sensing, and somatic control to enable next‐generation shape changing robots are also discussed.

Transparent Zinc‐Mesh Electrodes for Solar‐Charging Electrochromic Windows

By Haizeng Li, Wu Zhang, Abdulhakem Y. Elezzabi from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

The first example of flexible transparent zinc‐mesh electrodes are demonstrated to assemble large‐scale Zn‐anode‐based electrochromic windows, and solar‐charging smart windows with sunlight‐intermittency issues perfectly addressed are presented. These findings facilitate new opportunities for the development of next‐generation transparent electrochemical devices. Abstract Newly born zinc‐anode‐based electrochromic devices (ZECDs), incorporating electrochromic and energy storage functions in a single transparent platform, represent the most promising technology for next‐generation transparent electronics. As the existing ZECDs are limited by opaque zinc anodes, the key focus should be on the development of transparent zinc anodes. Here, the first demonstration of a flexible transparent zinc‐mesh electrode is reported for a ZECD window that yields a remarkable electrochromic performance in an 80 cm2 device, including rapid switching times (3.6 and 2.5 s for the coloration and bleaching processes, respectively), a high optical contrast (67.2%), and an excellent coloration efficiency (131.5 cm2 C−1). It is also demonstrated that such ZECDs are perfectly suited for solar‐charging smart windows as they inherently address the solar intermittency issue. These windows can be colored via solar charging during the day, and they can be bleached during the night by supplying electrical energy to electronic devices. The ZECD smart window platform can be scaled to a large area while retaining its excellent electrochromic characteristics. These findings represent a new technology for solar‐charging windows and open new opportunities for the development of next‐generation transparent batteries.

A Narrow‐Bandgap n‐Type Polymer with an Acceptor–Acceptor Backbone Enabling Efficient All‐Polymer Solar Cells

By Huiliang Sun, Han Yu, Yongqiang Shi, Jianwei Yu, Zhongxiang Peng, Xianhe Zhang, Bin Liu, Junwei Wang, Ranbir Singh, Jaewon Lee, Yongchun Li, Zixiang Wei, Qiaogan Liao, Zhipeng Kan, Long Ye, He Yan, Feng Gao, Xugang Guo from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

A narrow‐bandgap polymer acceptor L14 with an acceptor–acceptor (A–A) backbone is synthesized, showing lower‐lying frontier molecular orbitals, higher electron mobility, and larger absorption coefficient without sacrificing photovoltage compared to its donor–acceptor (D–A) analog polymer, L11. When applied in all‐polymer solar cells, L14 yields an outstanding efficiency of 14.3%. Abstract Narrow‐bandgap polymer semiconductors are essential for advancing the development of organic solar cells. Here, a new narrow‐bandgap polymer acceptor L14, featuring an acceptor–acceptor (A–A) type backbone, is synthesized by copolymerizing a dibrominated fused‐ring electron acceptor (FREA) with distannylated bithiophene imide. Combining the advantages of both the FREA and the A–A polymer, L14 not only shows a narrow bandgap and high absorption coefficient, but also low‐lying frontier molecular orbital (FMO) levels. Such FMO levels yield improved electron transfer character, but unexpectedly, without sacrificing open‐circuit voltage (Voc), which is attributed to a small nonradiative recombination loss (Eloss,nr) of 0.22 eV. Benefiting from the improved photocurrent along with the high fill factor and Voc, an excellent efficiency of 14.3% is achieved, which is among the highest values for all‐polymer solar cells (all‐PSCs). The results demonstrate the superiority of narrow‐bandgap A–A type polymers for improving all‐PSC performance and pave a way toward developing high‐performance polymer acceptors for all‐PSCs.

Interface Engineering in Multiphase Systems toward Synthetic Cells and Organelles: From Soft Mater Fundamentals to Biomedical Applications

By Zhou Liu, Wen Zhou, Cheng Qi, Tiantian Kong from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

Engineered liquid–liquid interfaces of multiphase systems are effective for constructing compartmentalized cell‐mimicking systems. Key features and examples of synthetic cells including lipid vesicles, polymer vesicles, hybrid systems and coacervate droplets are outlined, and their imitative biological behaviors such as growth, fusion, and energy conversion are summarized. Progress and challenges associated with state‐of‐art applications of cell‐inspired synthetic compartments are highlighted. Abstract Synthetic cells have a major role in gaining insight into the complex biological processes of living cells; they also give rise to a range of emerging applications from gene delivery to enzymatic nanoreactors. Living cells rely on compartmentalization to orchestrate reaction networks for specialized and coordinated functions. Principally, the compartmentalization has been an essential engineering theme in constructing cell‐mimicking systems. Here, efforts to engineer liquid–liquid interfaces of multiphase systems into membrane‐bounded and membraneless compartments, which include lipid vesicles, polymer vesicles, colloidosomes, hybrids, and coacervate droplets, are summarized. Examples are provided of how these compartments are designed to imitate biological behaviors or machinery, including molecule trafficking, growth, fusion, energy conversion, intercellular communication, and adaptivity. Subsequently, the state‐of‐art applications of these cell‐inspired synthetic compartments are discussed. Apart from being simplified and cell models for bridging the gap between nonliving matter and cellular life, synthetic compartments also are utilized as intracellular delivery vehicles for nuclei acids and nanoreactors for biochemical synthesis. Finally, key challenges and future directions for achieving the full potential of synthetic cells are highlighted.

Tunable Piezoelectricity of Multifunctional Boron Nitride Nanotube/Poly(dimethylsiloxane) Stretchable Composites

By Peter Snapp, Chullhee Cho, Dongwon Lee, Md Farhadul Haque, SungWoo Nam, Cheol Park from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

Boron nitride nanotube/poly(dimethylsiloxane) (BNNT/PDMS) stretchable composites are prepared via co‐solvent blending with tetrahydrofuran. The composites demonstrate augmented Young's modulus and thermal conductivity without losing stretchability while developing a piezoelectric response comparable to widely used piezoelectric polymers. Uniquely, application of strain reversibly aligns BNNTs, further enhancing piezoelectric response and permitting applications as low‐frequency‐vibration detectors. Abstract Boron nitride nanotubes (BNNT) uniformly dispersed in stretchable materials, such as poly(dimethylsiloxane) (PDMS), could create the next generation of composites with augmented mechanical, thermal, and piezoelectric characteristics. This work reports tunable piezoelectricity of multifunctional BNNT/PDMS stretchable composites prepared via co‐solvent blending with tetrahydrofuran (THF) to disperse BNNTs in PDMS while avoiding sonication or functionalization. The resultant stretchable BNNT/PDMS composites demonstrate augmented Young's modulus (200% increase at 9 wt% BNNT) and thermal conductivity (120% increase at 9 wt% BNNT) without losing stretchability. Furthermore, BNNT/PDMS composites demonstrate piezoelectric responses that are linearly proportional to BNNT wt%, achieving a piezoelectric constant (|d33|) of 18 pmV−1 at 9 wt% BNNT without poling, which is competitive with commercial piezoelectric polymers. Uniquely, BNNT/PDMS accommodates tensile strains up to 60% without plastic deformation by aligning BNNTs, which enhances the composites’ piezoelectric response approximately five times. Finally, the combined stretchable and piezoelectric nature of the composite was exploited to produce a vibration sensor sensitive to low‐frequency (≈1 kHz) excitation. This is the first demonstration of multifunctional, stretchable BNNT/PDMS composites with enhanced mechanical strength and thermal conductivity and furthermore tunable piezoelectric response by varying BNNT wt% and applied strain, permitting applications in soft actuators and vibration sensors.

Plasmonic Oxygen‐Deficient TiO2‐x Nanocrystals for Dual‐Band Electrochromic Smart Windows with Efficient Energy Recycling

By Shengliang Zhang, Sheng Cao, Tianran Zhang, Jim Yang Lee from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

A dual‐band electrochromic smart window assembled using a plasmonic oxygen‐deficient TiO2‐x nanocrystal electrode not only successfully overcomes the issues of aliovalent substitutional doping in dual‐band electrochromic applications, but also delivers the independent control of visible light and near‐infrared with impressive electrochromic performance and efficient energy recycling, which can significantly reduce the energy consumption of buildings and electrochromic devices. Abstract Dual‐band electrochromic smart windows capable of the spectrally selective modulation of visible (VIS) light and near‐infrared (NIR) can regulate solar light and solar heat transmittance to reduce the building energy consumption. The development of these windows is however limited by the number of available dual‐band electrochromic materials. Here, plasmonic oxygen‐deficient TiO2‐x nanocrystals (NCs) are discovered to be an effective single‐component dual‐band electrochromic material, and that oxygen‐vacancy creation is more effective than aliovalent substitutional doping to introduce dual‐band properties to TiO2 NCs. Oxygen vacancies not only confer good near‐infrared (NIR)‐selective modulation, but also improve the Li+ diffusion in the TiO2‐x host, circumventing the disadvantage of aliovalent substitutional doping with ion diffusion. Consequently optimized TiO2‐x NC films are able to modulate the NIR and visible light transmittance independently and effectively in three distinct modes with high optical modulation (95.5% at 633 nm and 90.5% at 1200 nm), fast switching speed, high bistability, and long cycle life. An impressive dual‐band electrochromic performance is also demonstrated in prototype devices. The use of TiO2‐x NCs enables the assembled windows to recycle a large fraction of energy consumed in the coloration process (“energy recycling”) to reduce the energy consumption in a round‐trip electrochromic operation.

The Experimentalist's Guide to the Cycloid, or Noncollinear Antiferromagnetism in Epitaxial BiFeO3

By Stuart R. Burns, Oliver Paull, Jean Juraszek, Valanoor Nagarajan, Daniel Sando from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

A thorough, critical review of the literature concerning the room‐temperature multiferroic BiFeO3 is presented. Specifically, research exploring the structure and behavior of the incommensurate spin cycloid is addressed. After elucidating the importance of this magnetic oxide for functional devices and nanotechnologies, possible techniques for probing the spin cycloid, alongside perturbations and behavior under various external stimuli, are discussed. Abstract Bismuth ferrite (BiFeO3) is one of the most widely studied multiferroics. The coexistence of ferroelectricity and antiferromagnetism in this compound has driven an intense search for electric‐field control of the magnetic order. Such efforts require a complete understanding of the various exchange interactions that underpin the magnetic behavior. An important characteristic of BiFeO3 is its noncollinear magnetic order; namely, a long‐period incommensurate spin cycloid. Here, the progress in understanding this fascinating aspect of BiFeO3 is reviewed, with a focus on epitaxial films. The advances made in developing the theory used to capture the complexities of the cycloid are first chronicled, followed by a description of the various experimental techniques employed to probe the magnetic order. To help the reader fully grasp the nuances associated with thin films, a detailed description of the spin cycloid in the bulk is provided. The effects of various perturbations on the cycloid are then described: magnetic and electric fields, doping, epitaxial strain, finite size effects, and temperature. To conclude, an outlook on possible device applications exploiting noncollinear magnetism in BiFeO3 films is presented. It is hoped that this work will act as a comprehensive experimentalist's guide to the spin cycloid in BiFeO3 thin films.

Liquid Metal Initiator of Ring‐Opening Polymerization: Self‐Capsulation into Thermal/Photomoldable Powder for Multifunctional Composites

By Xiankai Li, Mingjie Li, Qinghui Shou, Li Zhou, Anle Ge, Danfeng Pei, Chaoxu Li from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

Ring‐opening polymerization initiated by sonicating EGaIn in fluidic lactones enables self‐capsulation of EGaIn droplets into polylactone shells with tunable thickness. With thermal/photomoldability, biocompatibility, biodegradability, and high photothermal efficiency, powder of EGaIn capsules is ideal for multifunctional composites (e.g., with sintering ability, notch‐insensitive tearing property, electric conductivity, and photothermal effect), applicable in stretchable electronics, biomedicines, and smart materials. Abstract Liquid metal nanodroplets not only share similar metallic properties and nanoscale effect with solid metal nanoparticles, but also possess the additional uniqueness in nonvolatile fluidity and ambient sintering ability into continuous conductors. In most cases, liquid metal nanodroplets are encapsulated into ultrathin and fragile shells of oxides and amphiphile monolayers, and may be hindered from incorporating homogeneously into various composites through conventional processing methods. In this study, ring‐opening polymerization is found to be initiated by sonicating the liquid metal EGaIn in fluidic lactones. By this in situ polymerization, EGaIn nanodroplets are encapsulated into polylactone shells with tunable thickness, which can further be dried into a solid powder. Besides high chemical stability and dispersibility in organic solvents, the powder of the EGaIn capsules combines the exceptional properties of the EGaIn droplets (e.g., photothermal effect) and the polylactone shells (e.g., biocompatibility, biodegradability, and compatibility with different polymer matrixes), being capable of being introduced into thermoplastic composites through liquid casting and thermal‐ or photomolding for the notch‐insensitive tearing property, sintering‐induced electric conductivity, and photothermal effect. Thus, the EGaIn initiator of ring‐opening polymerization may start a pathway to produce stable andthermal/photomoldable powders of EGaIn capsules and their multifunctionalcomposites, applicable in biomedicines, soft electronics, and smart robots.

Synergistic Interface‐Assisted Electrode–Electrolyte Coupling Toward Advanced Charge Storage

By Shuo Sun, Dewei Rao, Teng Zhai, Qi Liu, Hao Huang, Bo Liu, Hongshen Zhang, Liang Xue, Hui Xia from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

A “smart” Co3O4–redox electrolyte (RE) interface that not only significantly increases the electrochemical activity of Co3O4 but also effectively confines the redox species is created, thus simultaneously achieving remarkable enhancement of faradaic charge storage capability and suppressed self‐discharge. With such a synergistic interface, the energy density of RE‐enhanced aqueous rechargeable batteries can be effectively increased without compromising the low self‐discharge. Abstract Owing to the limited charge storage capability of transitional metal oxides in aqueous electrolytes, the use of redox electrolytes (RE) represents a promising strategy to further increase the energy density of aqueous batteries or pseudocapacitors. The usual coupling of an electrode and an RE possesses weak electrode/RE interaction and weak adsorption of redox moieties on the electrode, resulting in a low capacity contribution and fast self‐discharge. In this work, Fe(CN)64− groups are grafted on the surface of Co3O4 electrode via formation of CoN bonds, creating a synergistic interface between the electrode and the RE. With such an interface, the coupled Co3O4–RE system exhibits greatly enhanced charge storage from both Co3O4 and RE, delivering a large reversible capacity of ≈1000 mC cm−2 together with greatly reduced self‐discharge. The significantly improved electrochemical activity of Co3O4 can be attributed to the tuned work function via charge injection from Fe(CN)64−, while the greatly enhanced adsorption of K3Fe(CN)6 molecules is achieved by the interface induced dipole–dipole interaction on the liquid side. Furthermore, this enhanced electrode–electrolyte coupling is also applicable in the NiO–RE system, demonstrating that the synergistic interface design can be a general strategy to integrate electrode and electrolyte for high‐performance energy storage devices.

Multifunctional Polymer‐Regulated SnO2 Nanocrystals Enhance Interface Contact for Efficient and Stable Planar Perovskite Solar Cells

By Shuai You, Haipeng Zeng, Zhiliang Ku, Xiaoze Wang, Zhen Wang, Yaoguang Rong, Yang Zhao, Xin Zheng, Long Luo, Lin Li, Shujing Zhang, Min Li, Xingyu Gao, Xiong Li from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

A biological polymer is employed to regulate the arrangement of SnO2 nanocrystals on a substrate and induce vertical crystal growth of a perovskite layer on top. The enhanced interface contact between the electron transport layer and the perovskite layer significantly contributes to the improvement of efficiency and stability of derived planar perovskite solar cells. Abstract Perovskite solar cells (PSCs) have rapidly developed and achieved power conversion efficiencies of over 20% with diverse technical routes. Particularly, planar‐structured PSCs can be fabricated with low‐temperature (≤150 °C) solution‐based processes, which is energy efficient and compatible with flexible substrates. Here, the efficiency and stability of planar PSCs are enhanced by improving the interface contact between the SnO2 electron‐transport layer (ETL) and the perovskite layer. A biological polymer (heparin potassium, HP) is introduced to regulate the arrangement of SnO2 nanocrystals, and induce vertically aligned crystal growth of perovskites on top. Correspondingly, SnO2–HP‐based devices can demonstrate an average efficiency of 23.03% on rigid substrates with enhanced open‐circuit voltage (VOC) of 1.162 V and high reproducibility. Attributed to the strengthened interface binding, the devices obtain high operational stability, retaining 97% of their initial performance (power conversion efficiency, PCE > 22%) after 1000 h operation at their maximum power point under 1 sun illumination. Besides, the HP‐modified SnO2 ETL exhibits promising potential for application in flexible and large‐area devices.

Enantioselective Syntheses of Strychnos and Chelidonium Alkaloids through Regio‐ and Stereocontrolled Cooperative Catalysis

By Luke S. Hutchings‐Goetz, Chao Yang, James W. B. Fyfe, Thomas N. Snaddon from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

Enantioselective syntheses of strychnos and chelidonium alkaloids were achieved via the regio‐ and stereocontrolled synthesis of homoallylic amines through isothiourea/transition‐metal cooperative catalysis. Indole acetic acid esters were established as remarkably effective nucleophiles, enabling syntheses of akuammicine, strychnine, and an SIRT‐1 inhibitor. Structure‐based reactivity challenges were overcome to synthesize three chelidonium alkaloids. Abstract We describe enantioselective syntheses of strychnos and chelidonium alkaloids. In the first case, indole acetic acid esters were established as excellent partner nucleophiles for enantioselective cooperative isothiourea/Pd catalyzed α‐alkylation. This provides products containing indole‐bearing stereocenters in high yield and with excellent levels of enantioinduction in a manner that is notably independent of the N‐substituent. This led to concise syntheses of (−)‐akuammicine and (−)‐strychnine. In the second case, the poor performance of ortho‐substituted cinnamyl electrophiles in the enantioselective cooperative isothiourea/Ir catalyzed α‐alkylation was overcome by appropriate substituent choice, leading to enantioselective syntheses of (+)‐chelidonine, (+)‐norchelidonine, and (+)‐chelamine.

Beyond the Polysulfide Shuttle and Lithium Dendrite Formation: Addressing the Sluggish Sulfur Redox Kinetics for Practical High‐Energy Li‐S Batteries

By Chen Zhao, Gui‐Liang Xu, Tianshou Zhao, Khalil Amine from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

A rational combination of selenium‐doped sulfur cathode design with electrolyte modulation enables robust shuttle‐ and dendrite‐free cathode and anode chemistries. This strategy is demonstrated to be effective in achieving ultrastable Li‐S batteries even under high cathode loading and low electrolyte conditions with a pouch cell configuration. Abstract Electrolyte modulation simultaneously suppresses polysulfide the shuttle effect and lithium dendrite formation of lithium–sulfur (Li‐S) batteries. However, the sluggish S redox kinetics, especially under high S loading and lean electrolyte operation, has been ignored, which dramatically limits the cycle life and energy density of practical Li‐S pouch cells. Herein, we demonstrate that a rational combination of selenium doping, core–shell hollow host structure, and fluorinated ether electrolytes enables ultrastable Li stripping/plating and essentially no polysulfide shuttle as well as fast redox kinetics. Thus, high areal capacity (>4 mAh cm−2) with excellent cycle stability and Coulombic efficiency were both demonstrated in Li metal anode and thick S cathode (4.5 mg cm−2) with a low electrolyte/sulfur ratio (10 μL mg−1). This research further demonstrates a durable Li‐Se/S pouch cell with high specific capacity, validating the potential practical applications.

An Intelligent DNA Nanorobot for Autonomous Anticoagulation

By Linlin Yang, Yumeng Zhao, Xuemei Xu, Kangli Xu, Mingzhi Zhang, Kui Huang, Huaizhi Kang, Hsiao‐chu Lin, Yang Yang, Da Han from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

A DNA nanorobot is presented that can intelligently regulate thrombin functions when it senses an over‐boosted coagulation environment. Under normal coagulation conditions it does not perform. The trigger concentrations of nanorobot can be tuned arbitrarily, which makes the nanorobot useful for autonomous anticoagulation in various medical scenarios and inspires a more efficient and safer strategy for personalized medicine. Abstract Artificial nanorobots that can recognize molecular triggers and respond with programable operations provide an inspiring proof‐of‐principle for personalized theragnostic applications. We have constructed an intelligent DNA nanorobot for autonomous blood anticoagulation in human plasma. The DNA nanorobot comprises a barrel‐shaped DNA nanostructure as the framework and molecular reaction cascades embedded as the computing core. This nanorobot can intelligently sense the concentration of thrombin in the local environment and trigger an autonomous anticoagulation when excess thrombin is present. The triggering concentration of thrombin at which the nanorobot responds can be tuned arbitrarily to avoid possible side effects induced by excess thrombin. This makes the nanorobot useful for autonomous anticoagulation in various medical scenarios and inspires a more efficient and safer strategy for future personalized medicine.

Periodically Ordered, Nuclease‐Resistant DNA Nanowires Decorated with Cell‐Specific Aptamers as Selective Theranostic Agents

By Chang Xue, Songbai Zhang, Xin Yu, Shuyao Hu, Yi Lu, Zai‐Sheng Wu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

A periodically ordered nick‐hidden DNA nanowire composed of six distinct oligonucleotide components was developed as a powerful drug‐delivery vehicle for the accurate diagnosis and targeted therapy of cancers (see picture). Owing to the high serum stability and active targeting functionality of the construct, NWs loaded with doxorubicin exhibited a long blood‐circulation time and high specificity in inducing cancer‐cell apoptosis. Abstract DNA nanostructures have shown potential in cancer therapy. However, their clinical application is hampered by the difficulty to deliver them into cancer cells and susceptibility to nuclease degradation. To overcome these limitations, we report herein a periodically ordered nick‐hidden DNA nanowire (NW) with high serum stability and active targeting functionality. The inner core is made of multiple connected DNA double helices, and the outer shell is composed of regularly arranged standing‐up hairpin aptamers. All termini of the components are hidden from nuclease attack, whereas the target‐binding sites are exposed to allow delivery to the cancer target. The DNA NW remained intact during incubation for 24 h in serum solution. Animal imaging and cell apoptosis showed that NWs loaded with an anticancer drug displayed long blood‐circulation time and high specificity in inducing cancer‐cell apoptosis, thus validating this approach for the targeted imaging and therapy of cancers.

Nickel Nanoparticle Catalyzed Mono‐ and Di‐Reductions of gem‐Dibromocyclopropanes Under Mild, Aqueous Micellar Conditions

By Alex B. Wood, Margery Cortes‐Clerget, Joseph R. A. Kincaid, Bhornrawin Akkachairin, Vani Singhania, Fabrice Gallou, Bruce H. Lipshutz from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

Double reduction of gem‐dibromocyclopropanes, done in one pot in recyclable water and with a base metal, Ni, leads to the corresponding cyclopropanes. This new technology is tolerant of several functional groups and can be modified to allow mono‐reduction, including mono‐ or di‐deuteration. Residual levels of Ni in the products tend to be less than 2 ppm. Abstract Mild mono‐ and di‐hydrodehalogenative reductions of gem‐dibromocyclopropanes are described, providing an easy and green approach towards the synthesis of cyclopropanes. The methodology utilizes 0.5–5 mol % TMPhen‐nickel as the catalyst, which, when activated with a hydride source such as sodium borohydride, cleanly and selectively dehalogenates dibromocyclopropanes. Double reduction proceeds in a single operation at temperatures between 20–45 °C and at atmospheric pressure in an aqueous designer surfactant medium. At lower loading and either in the absence of ligand or in the presence of 2,2′‐bipyridine, this new technology can also be used to gain access to not only monobrominated cyclopropanes, interesting building blocks for further use in synthesis, but also mono‐ or di‐deuterated analogues. Taken together, this base‐metal‐catalyzed process provides access to cyclopropyl‐containing products and is achieved under environmentally responsible conditions.

Coordination of Actinide Single Ions to Deformed Graphdiyne: Strategy on Essential Separation Processes in Nuclear Fuel Cycle

By Tianyu Yuan, Shijie Xiong, Xinghai Shen from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

Graphdiyne provides a new platform for the separation of actinides and lanthanides, that is, Th4+ and UO22+, and Cs+ and Sr2+. The actinides or Cs+ adsorbed on graphdiyne were determined to be present in the single‐ion state. Abstract The coordination of actinides and lanthanides, as well as strontium and cesium with graphdiyne (GDY) was studied experimentally and theoretically. On the basis of experimental results and/or theoretical calculations, it was suggested that Th4+, Pu4+, Am3+, Cm3+, and Cs+ exist in single‐ion states on the special triangular structure of GDY with various coordination patterns, wherein GDY itself is deformed in different ways. Both experiment and theoretical calculations strongly indicate that UO22+, La3+, Eu3+, Tm3+ and Sr2+ are not adsorbed by GDY at all. The distinguished adsorption behaviors of GDY afford an important strategy for highly selective separation of actinides and lanthanides, Th4+ and UO22+, and Cs+ and Sr2+, in the nuclear fuel cycle. Also, the present work sheds light on an approach to explore the unique functions and physicochemical properties of actinides in single‐ion states.

Engineering Platinum–Oxygen Dual Catalytic Sites via Charge Transfer towards Highly Efficient Hydrogen Evolution

By Fei Lu, Ding Yi, Shoujie Liu, Fei Zhan, Bo Zhou, Lin Gu, Dmitri Golberg, Xi Wang, Jiannian Yao from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

Atomically dispersed Pt embedded in Ti1−xO2 (Pt1O1/Ti1−xO2) was engineered via a cation‐deficient electrostatic anchorage route. The inherent charge transfer within the Pt−O realm thus evolved the catalytic matrix into the dual Pt−OPt catalytic sites towards high‐efficient and durable hydrogen evolution. Abstract A dual‐site catalyst allows for a synergetic reaction in the close proximity to enhance catalysis. It is highly desirable to create dual‐site interfaces in single‐atom system to maximize the effect. Herein, we report a cation‐deficient electrostatic anchorage route to fabricate an atomically dispersed platinum–titania catalyst (Pt1O1/Ti1−xO2), which shows greatly enhanced hydrogen evolution activity, surpassing that of the commercial Pt/C catalyst in mass by a factor of 53.2. Operando techniques and density functional calculations reveal that Pt1O1/Ti1−xO2 experiences a Pt−O dual‐site catalytic pathway, where the inherent charge transfer within the dual sites encourages the jointly coupling protons and plays the key role during the Volmer–Tafel process. There is almost no decay in the activity of Pt1O1/Ti1−xO2 over 300 000 cycles, meaning 30 times of enhancement in stability compared to the commercial Pt/C catalysts (10 000 cycles).

Targeted Degradation of Transcription Coactivator SRC‐1 through the N‐Degron Pathway

By Yeongju Lee, Jiwon Heo, Hoibin Jeong, Kyung Tae Hong, Do Hoon Kwon, Min Hyeon Shin, Misook Oh, Ganesh A. Sable, G‐One Ahn, Jun‐Seok Lee, Hyun Kyu Song, Hyun‐Suk Lim from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

A PROTAC composed of a selective stapled peptide for transcription coactivator SRC‐1 linked to a specific ligand for UBR E3 ligase induces the selective degradation of SRC‐1. This first‐in‐class SRC‐1 degrader efficiently impairs SRC‐1‐mediated transcription and suppresses cancer cell invasion and migration in vitro and in vivo and holds promise as an invaluable tool to probe SRC‐1 functions. Abstract Aberrantly elevated steroid receptor coactivator‐1 (SRC‐1) expression and activity are strongly correlated with cancer progression and metastasis. Here we report, for the first time, the development of a proteolysis targeting chimera (PROTAC) that is composed of a selective SRC‐1 binder linked to a specific ligand for UBR box, a unique class of E3 ligases recognizing N‐degrons. We showed that the bifunctional molecule efficiently and selectively induced the degradation of SRC‐1 in cells through the N‐degron pathway. Importantly, given the ubiquitous expression of the UBR protein in most cells, PROTACs targeting the UBR box could degrade a protein of interest regardless of cell types. We also showed that the SRC‐1 degrader significantly suppressed cancer cell invasion and migration in vitro and in vivo. Together, these results demonstrate that the SRC‐1 degrader can be an invaluable chemical tool in the studies of SRC‐1 functions. Moreover, our findings suggest PROTACs based on the N‐degron pathway as a widely useful strategy to degrade disease‐relevant proteins.

Rational Control of Charge Transfer Excitons Toward High‐Contrast Reversible Mechanoresponsive Luminescent Switching

By Zongrui Wang, Fei Yu, Wangqiao Chen, Jianfeng Wang, Jinyu Liu, Changjiang Yao, Jianfeng Zhao, Huanli Dong, Wenping Hu, Qichun Zhang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

A simple and practicable strategy is established to obtain high‐contrast reversible mechanoresponsive PL switching by introducing a volatile third party into the lattice of mixed‐stacking CT cocrystal. This has the purpose of constructing the loosely packing mode to realize a facile control of molecular assemblies and CT excitons in the solid state. Abstract A practicable strategy to rationally obtain the reversible mechanochromic luminescent (MCL) material with high‐contrast ratio (green versus red) has been established. By introducing a volatile third party (small‐sized solvent molecules) into the lattice of charge transfer (CT) cocrystal of mixed‐stacking 1:1 coronene (Cor.) and napthalenetetracarboxylic diimide (NDI), a noteworthy reconfigurable molecular assembly is ingeniously achieved owing to the loosely packing arrangement as well as weakened intermolecular interactions. Accordingly, the CT excited state, strongly corresponding to the molecular stacking modes, can be intentionally tailored through external stimulus (heating, grinding, or solvent), accompanying distinct changes in photophysical properties. Subsequently, a high‐contrast reversible MCL with highly sensitive and good reproducibility is realized and the underlying mechanism is thoroughly revealed.

Spatial and Kinetic Regulation of Sulfur Electrochemistry on Semi‐Immobilized Redox Mediators in Working Batteries

By Jin Xie, Hong‐Jie Peng, Yun‐Wei Song, Bo‐Quan Li, Ye Xiao, Meng Zhao, Hong Yuan, Jia‐Qi Huang, Qiang Zhang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

A semi‐immobilization strategy is proposed for redox mediator (RM) design to effectively regulate the sulfur electrochemistry whilst circumventing the inherent shuttle issue in a working lithium sulfur battery. Small imide molecules as the model RMs were co‐polymerized with a polyether of moderate chain length, rendering a semi‐immobilized RM (PIPE) that is spatially restrained in the cathode yet kinetically active. Abstract Use of redox mediators (RMs) is an effective strategy to enhance reaction kinetics of multi‐electron sulfur electrochemistry. However, the soluble small‐molecule RMs usually aggravate the internal shuttle and thus further reduce the battery efficiency and cyclability. A semi‐immobilization strategy is now proposed for RM design to effectively regulate the sulfur electrochemistry while circumvent the inherent shuttle issue in a working battery. Small imide molecules as the model RMs were co‐polymerized with moderate‐chained polyether, rendering a semi‐immobilized RM (PIPE) that is spatially restrained yet kinetically active. A small amount of PIPE (5 % in cathode) extended the cyclability of sulfur cathode from 37 to 190 cycles with 80 % capacity retention at 0.5 C. The semi‐immobilization strategy helps to understand RM‐assisted sulfur electrochemistry in alkali metal batteries and enlightens the chemical design of active additives for advanced electrochemical energy storage devices.

Intracellular Ruthenium‐Promoted (2+2+2) Cycloadditions

By Joan Miguel‐Ávila, María Tomás‐Gamasa, José L. Mascareñas from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

Ruthenium‐mediated cycloaromatization reactions engaging three alkyne units can be performed in intracellular settings in a biocompatible way. This synthetically powerful reaction allows access to a variety of relatively complex, functional cyclic products inside cells, therefore providing an artificial metabolic route to these interesting species. Abstract Metal‐mediated intracellular reactions are becoming invaluable tools in chemical and cell biology, and hold promise for strongly impacting the field of biomedicine. Most of the reactions reported so far involve either uncaging or redox processes. Demonstrated here for the first time is the viability of performing multicomponent alkyne cycloaromatizations inside live mammalian cells using ruthenium catalysts. Both fully intramolecular and intermolecular cycloadditions of diynes with alkynes are feasible, the latter providing an intracellular synthesis of appealing anthraquinones. The power of the approach is further demonstrated by generating anthraquinone AIEgens (AIE=aggregation induced emission) that otherwise do not go inside cells, and by modifying the intracellular distribution of the products by simply varying the type of ruthenium complex.

Single‐Molecule 3D Orientation Imaging Reveals Nanoscale Compositional Heterogeneity in Lipid Membranes

By Jin Lu, Hesam Mazidi, Tianben Ding, Oumeng Zhang, Matthew D. Lew from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

A fluorescent molecule within soft matter itself acts as a nanoscale sensor, where intermolecular forces influence its orientation in 3D space. Imaging the position, orientation, and wobble of single molecules reveals a high‐dimensional “fingerprint” of the chemical environment within lipid nanodomains and enzyme‐induced compositional transformations within membranes. Abstract In soft matter, thermal energy causes molecules to continuously translate and rotate, even in crowded environments, thereby impacting the spatial organization and function of most molecular assemblies, such as lipid membranes. Directly measuring the orientation and spatial organization of large collections (>3000 molecules μm−2) of single molecules with nanoscale resolution remains elusive. In this paper, we utilize SMOLM, single‐molecule orientation localization microscopy, to directly measure the orientation spectra (3D orientation plus “wobble”) of lipophilic probes transiently bound to lipid membranes, revealing that Nile red's (NR) orientation spectra are extremely sensitive to membrane chemical composition. SMOLM images resolve nanodomains and enzyme‐induced compositional heterogeneity within membranes, where NR within liquid‐ordered vs. liquid‐disordered domains shows a ≈4° difference in polar angle and a ≈0.3π sr difference in wobble angle. As a new type of imaging spectroscopy, SMOLM exposes the organizational and functional dynamics of lipid‐lipid, lipid‐protein, and lipid‐dye interactions with single‐molecule, nanoscale resolution.

Dealkenylative Alkenylation: Formal σ‐Bond Metathesis of Olefins

By Manisha Swain, Gusein Sadykhov, Ruoxi Wang, Ohyun Kwon from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

The dealkenylative alkenylation of alkene C(sp3)−C(sp2) bonds has been an unexplored area for C−C bond formation. Reported herein are β‐alkylated styrene derivatives synthesized through the reactions of readily accessible feedstock olefins with β‐nitrostyrenes by ozone/FeII‐mediated radical substitutions. The strategy was applied to the syntheses of the natural product iso‐moracin and the drug (E)‐metanicotine. Abstract The dealkenylative alkenylation of alkene C(sp3)−C(sp2) bonds has been an unexplored area for C−C bond formation. Herein 64 examples of β‐alkylated styrene derivatives, synthesized through the reactions of readily accessible feedstock olefins with β‐nitrostyrenes by ozone/FeII‐mediated radical substitutions, are reported. These reactions proceed with good efficiencies and high stereoselectivities under mild reaction conditions and tolerate an array of functional groups. Also demonstrated is the applicability of the strategy through several synthetic transformations of the products, as well as the syntheses of the natural product iso‐moracin and the drug (E)‐metanicotine.

N‐Annulated Perylene Bisimides to Bias the Differentiation of Metastable Supramolecular Assemblies into J‐ and H‐Aggregates

By Elisa E. Greciano, Joaquín Calbo, Enrique Ortí, Luis Sánchez from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

The distinctive self‐assembling features of N‐annulated perylene bisimides 1 and 2 are reported. Diester 1, with no H‐bonding interaction operating, affords stable cooperative J‐type supramolecular polymers. The incorporation of amide functional groups in 2 results in a stimulating differentiation with several pathways to achieve up to three J‐type aggregates and a fourth H‐type aggregate depending on the experimental conditions utilized. Key: methylcyclohexane (MCH), toluene (Tol). Abstract The unique self‐assembling features of N‐annulated perylene bisimides (PBIs) 1 and 2 are reported. The stability of the aggregates of diester 1, in which no H‐bonding interactions are operative, corroborates the significance of long‐range van der Waals and dipole–dipole electrostatic interactions in the construction of stable supramolecular assemblies. The incorporation of amide functional groups within the N‐annulated PBI in 2 stimulates pathway differentiation to achieve up to three J‐type aggregates and a fourth H‐type aggregate depending on the experimental conditions. The results presented demonstrate unprecedented levels of control over synthetic supramolecular self‐assembly and the rich differentiation that N‐annulated PBIs exhibit, opening the door to new, complex, functional supramolecular materials.

In Situ Dispersion of Palladium on TiO2 During Reverse Water–Gas Shift Reaction: Formation of Atomically Dispersed Palladium

By Nicholas C. Nelson, Linxiao Chen, Debora Meira, Libor Kovarik, János Szanyi from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

Dilution of Pd/TiO2 with neat TiO2 results in the formation of atomically dispersed Pd under reverse water–gas shift (rWGS) reaction conditions at 400 °C and a several fold increase in activity. Abstract The application of single‐atom catalysts (SACs) to high‐temperature hydrogenation requires materials that thermodynamically favor metal atom isolation over cluster formation. We demonstrate that Pd can be predominantly dispersed as isolated atoms onto TiO2 during the reverse water–gas shift (rWGS) reaction at 400 °C. Achieving atomic dispersion requires an artificial increase of the absolute TiO2 surface area by an order of magnitude and can be accomplished by physically mixing a precatalyst (Pd/TiO2) with neat TiO2 prior to the rWGS reaction. The in situ dispersion of Pd was reflected through a continuous increase of rWGS activity over 92 h and supported by kinetic analysis, infrared and X‐ray absorption spectroscopies and scanning transmission electron microscopy. The thermodynamic stability of Pd under high‐temperature rWGS conditions is associated with Pd‐Ti coordination, which manifests upon O‐vacancy formation, and the artificial increase in TiO2 surface area.

Enantio‐ and Site‐Selective α‐Fluorination of N‐Acyl 3,5‐Dimethylpyrazoles Catalyzed by Chiral π–CuII Complexes

By Kazuaki Ishihara, Kazuki Nishimura, Katsuya Yamakawa from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

N‐Acyl 3,5‐dimethylpyrazoles underwent enantioselective α‐fluorination catalyzed by a chiral π–copper(II) complex. The fast and scalable reaction, which was developed on the basis of the finding that α‐hydrogen atoms in the pseudo‐Z conformation of N‐acyl pyrazoles have higher acidity, shows wide substrate scope, and the α‐fluorinated products can be converted into esters, amides, ketones, and alcohols without epimerization (see scheme). Abstract Catalytic enantioselective α‐fluorination reactions of carbonyl compounds are among the most powerful and efficient synthetic methods for constructing optically active α‐fluorinated carbonyl compounds. Nevertheless, α‐fluorination of α‐nonbranched carboxylic acid derivatives is still a big challenge because of relatively high pKa values of their α‐hydrogen atoms and difficulty of subsequent synthetic transformation without epimerization. Herein we show that chiral copper(II) complexes of 3‐(2‐naphthyl)‐l‐alanine‐derived amides are highly effective catalysts for the enantio‐ and site‐selective α‐fluorination of N‐(α‐arylacetyl) and N‐(α‐alkylacetyl) 3,5‐dimethylpyrazoles. The substrate scope of the transformation is very broad (25 examples including a quaternary α‐fluorinated α‐amino acid derivative). α‐Fluorinated products were converted into the corresponding esters, secondary amides, tertiary amides, ketones, and alcohols with almost no epimerization in high yield.

Diradical Organic One‐Dimensional Polymers Synthesized on a Metallic Surface

By Ana Sánchez‐Grande, José I. Urgel, Aleš Cahlík, José Santos, Shayan Edalatmanesh, Eider Rodríguez‐Sánchez, Koen Lauwaet, Pingo Mutombo, Dana Nachtigallová, Reed Nieman, Hans Lischka, Bruno Torre, Rodolfo Miranda, Oliver Gröning, Nazario Martín, Pavel Jelínek, David Écija from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

The synthesis and characterization of atomically precise one‐dimensional diradical peripentacene polymers on a Au(111) surface is reported. By means of high‐resolution scanning probe microscopy complemented by theoretical simulations, evidence of their magnetic properties is provided, which arise from the presence of two unpaired spins at their termini. Abstract We report on the synthesis and characterization of atomically precise one‐dimensional diradical peripentacene polymers on a Au(111) surface. By means of high‐resolution scanning probe microscopy complemented by theoretical simulations, we provide evidence of their magnetic properties, which arise from the presence of two unpaired spins at their termini. Additionally, we probe a transition of their magnetic properties related to the length of the polymer. Peripentacene dimers exhibit an antiferromagnetic (S=0) singlet ground state. They are characterized by singlet–triplet spin‐flip inelastic excitations with an effective exchange coupling (Jeff) of 2.5 meV, whereas trimers and longer peripentacene polymers reveal a paramagnetic nature and feature Kondo fingerprints at each terminus due to the unpaired spin. Our work provides access to the precise fabrication of polymers featuring diradical character which are potentially useful in carbon‐based optoelectronics and spintronics.

Templated‐Assembly of CsPbBr3 Perovskite Nanocrystals into 2D Photonic Supercrystals with Amplified Spontaneous Emission

By David Vila‐Liarte, Maximilian W. Feil, Aurora Manzi, Juan Luis Garcia‐Pomar, He Huang, Markus Döblinger, Luis M Liz‐Marzán, Jochen Feldmann, Lakshminarayana Polavarapu, Agustín Mihi from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

Perovskite nanocrystals (NCs) are self‐assembled into 2D photonic supercrystals using pre‐patterned polydimethylsiloxane (PDMS) templates and their optical spectra are tunable by varying the lattice spacing. These photonic crystals show amplified spontaneous emission (ASE) under lower optical excitation fluences in the near‐IR region due to enhanced multi‐photon absorption caused by light trapping in the photonic crystal. Abstract Perovskite nanocrystals (NCs) have revolutionized optoelectronic devices because of their versatile optical properties. However, controlling and extending these functionalities often requires a light‐management strategy involving additional processing steps. Herein, we introduce a simple approach to shape perovskite nanocrystals (NC) into photonic architectures that provide light management by directly shaping the active material. Pre‐patterned polydimethylsiloxane (PDMS) templates are used for the template‐induced self‐assembly of 10 nm CsPbBr3 perovskite NC colloids into large area (1 cm2) 2D photonic crystals with tunable lattice spacing, ranging from 400 nm up to several microns. The photonic crystal arrangement facilitates efficient light coupling to the nanocrystal layer, thereby increasing the electric field intensity within the perovskite film. As a result, CsPbBr3 2D photonic crystals show amplified spontaneous emission (ASE) under lower optical excitation fluences in the near‐IR, in contrast to equivalent flat NC films prepared using the same colloidal ink. This improvement is attributed to the enhanced multi‐photon absorption caused by light trapping in the photonic crystal.

Stable Ti3+ Defects in Oriented Mesoporous Titania Frameworks for Efficient Photocatalysis

By Kun Lan, Ruicong Wang, Qiulong Wei, Yanxiang Wang, Anh Hong, Pingyun Feng, Dongyuan Zhao from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

By introducing a compatible reducing agent into a mono‐micelle assembly process, ordered mesoporous TiO2 microspheres that combine a radially aligned mesostructure with Ti3+ defects in mesoporous frameworks are formed. The reductant acts as a building block of mesostructured frameworks and reduces Ti4+ in situ to generate defects during calcination, giving rise to the coexistence of bulk Ti3+ defects and an ordered mesostructure. Abstract By introducing a compatible reducing agent (2‐ethylimidazole) into a mono‐micelle assembly process, we present a type of ordered mesoporous TiO2 microspheres that combines radially aligned mesostructure with Ti3+ defects in mesoporous frameworks. Such reductant acts as a building block of mesostructured frameworks and reduces Ti4+ in situ to generate defects during calcination, giving rise to the coexistence of bulk Ti3+ defects and an ordered mesostructure. The mesoporous TiO2 has both excellent mesoporosity (a high surface area of 106 m2 g−1, a mean pore size of 18.4 nm) and stable defects with an extended photoresponse. Such integration of unique mesoscopic architecture and atomic vacancies provide both effective mass transportation and enhanced light utilization, leading to a remarkable increase in H2 generation rate. A maximum H2 evolution rate of 19.8 mmol g−1 h−1 can be achieved, along with outstanding stability under solar light.

PST‐24: A Zeolite with Varying Intracrystalline Channel Dimensionality

By Donghui Jo, Jingjing Zhao, Jung Cho, Jeong Hwan Lee, Yang Liu, Chang‐jun Liu, Xiaodong Zou, Suk Bong Hong from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

PST‐24, a medium‐pore zeolite with a disordered arrangement of double 5‐ring (d5r) units, has been synthesized under excess fluoride conditions. Its three ordered polytypes have different channel dimensionalities, depending on the d5r arrangement order. Abstract Herein we report the synthesis, structure solution, and catalytic properties of PST‐24, a novel channel‐based medium‐pore zeolite. This zeolite was synthesized via the excess fluoride approach. Electron diffraction shows that its structure is built by composite cas‐zigzag (cas‐zz) building chains, which are connected by double 5‐ring (d5r) columns. While the cas‐zz building chains are ordered in the PST‐24 framework, the d5r columns adopt one of two possible arrangements; the two adjacent d5r columns are either at the same height or at different heights, denoted arrangements S and D, which can be regarded as open and closed valves that connect the channels, respectively. A framework with arrangement D only has a 2D 10‐ring channel system, whereas that with arrangement S only contains 3D channels. In actual PST‐24 crystals, the open and closed valves are almost randomly dispersed to yield a zeolite framework where the channel dimensionality varies locally from 2D to 3D.

Pressure‐Suppressed Carrier Trapping Leads to Enhanced Emission in Two‐Dimensional Perovskite (HA)2(GA)Pb2I7

By Songhao Guo, Yongsheng Zhao, Kejun Bu, Yongping Fu, Hui Luo, Mengting Chen, Matthew P. Hautzinger, Yingqi Wang, Song Jin, Wenge Yang, Xujie Lü from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

A remarkably enhanced emission (by 12‐fold) is achieved using pressure to modulate the structure of a highly distorted 2D halide perovskite (HA)2(GA)Pb2I7. In situ structural, spectroscopic, and theoretical analyses reveal that lattice compression under a mild pressure within 1.6 GPa considerably suppresses the carrier trapping, leading to the significantly improved performance. Abstract A remarkable PL enhancement by 12 fold is achieved using pressure to modulate the structure of a recently developed 2D perovskite (HA)2(GA)Pb2I7 (HA=n‐hexylammonium, GA=guanidinium). This structure features a previously unattainable, extremely large cage. In situ structural, spectroscopic, and theoretical analyses reveal that lattice compression under a mild pressure within 1.6 GPa considerably suppresses the carrier trapping, leading to significantly enhanced emission. Further pressurization induces a non‐luminescent amorphous yellow phase, which is retained and exhibits a continuously increasing band gap during decompression. When the pressure is released to 1.5 GPa, emission can be triggered by above‐band gap laser irradiation, accompanied by a color change from yellow to orange. The obtained orange phase could be retained at ambient conditions and exhibits two‐fold higher PL emission compared with the pristine (HA)2(GA)Pb2I7.

Identification of Histone deacetylase (HDAC)‐Associated Proteins with DNA‐Programmed Affinity Labeling

By Jianfu Zhang, Jianzhao Peng, Yiran Huang, Ling Meng, Qingrong Li, Feng Xiong, Xiaoyu Li from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

DNA‐based affinity labeling probes enabled the capture and characterization of HDAC‐associated proteins, including direct and indirect binders in HDAC complexes. This method provides a simple and broadly applicable chemical tool to study protein–protein interactions. Abstract Histone deacetylase (HDAC) is a major class of deacetylation enzymes. Many HDACs exist in large protein complexes in cells and their functions strongly depend on the complex composition. The identification of HDAC‐associated proteins is highly important in understanding their molecular mechanisms. Although affinity probes have been developed to study HDACs, they were mostly targeting the direct binder HDAC, while other proteins in the complex remain underexplored. We report a DNA‐based affinity labeling method capable of presenting different probe configurations without the need for preparing multiple probes. Using one binding probe, 9 probe configurations were created to profile HDAC complexes. Notably, this method identified indirect HDAC binders that may be inaccessible to traditional affinity probes, and it also revealed new biological implications for HDAC‐associated proteins. This study provided a simple and broadly applicable method for characterizing protein‐protein interactions.

Structural Elucidation of the Mechanism of Molecular Recognition in Chiral Crystalline Sponges

By Shi‐Yuan Zhang, David Fairen‐Jimenez, Michael J. Zaworotko from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

The chiral recognition mechanism of a family of chiral metal–organic materials was investigated towards the resolution of three racemic mixtures of phenylpropanol. X‐ray single‐crystal analysis of host–guest interactions revealed the specific binding sites with shape complementarity between the guest molecules and the adaptable chiral cavity. Abstract To gain insight into chiral recognition in porous materials we have prepared a family of fourth generation chiral metal–organic frameworks (MOFs) that have rigid frameworks and adaptable (flexible) pores. The previously reported parent material, [Co2(S‐mandelate)2(4,4′‐bipyridine)3](NO3)2, CMOM‐1S, is a modular MOF; five new variants in which counterions (BF4−, CMOM‐2S) or mandelate ligands are substituted (2‐Cl, CMOM‐11R; 3‐Cl, CMOM‐21R; 4‐Cl, CMOM‐31R; 4‐CH3, CMOM‐41R) and the existing CF3SO3− variant CMOM‐3S are studied herein. Fine‐tuning of pore size, shape, and chemistry afforded a series of distinct host–guest binding sites with variable chiral separation properties with respect to three structural isomers of phenylpropanol. Structural analysis of the resulting crystalline sponge phases revealed that host–guest interactions, guest–guest interactions, and pore adaptability collectively determine chiral discrimination.

Immunological Evaluation of Co‐Assembling a Lipidated Peptide Antigen and Lipophilic Adjuvants: Self‐Adjuvanting Anti‐Breast‐Cancer Vaccine Candidates

By Taku Aiga, Yoshiyuki Manabe, Keita Ito, Tsung‐Che Chang, Kazuya Kabayama, Shino Ohshima, Yoshie Kametani, Ayane Miura, Hiroto Furukawa, Hiroshi Inaba, Kazunori Matsuura, Koichi Fukase from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

A co‐assembled vaccine, composed of lipidated antigens and lipophilic adjuvants, is reported. This vaccine design possesses both antigen multivalency and antigen‐specific immunostimulation properties, and induces a robust immune response. This simple vaccine initiated a potent immune response without requiring complex synthesis, allowing efficient and practical development of self‐adjuvanting vaccines. Abstract Co‐assembling vaccines composed of a lipidated HER2‐derived antigenic CH401 peptide and either a lipophilic adjuvant, Pam3CSK4, α‐GalCer, or lipid A 506, were evaluated as breast cancer vaccine candidates. This vaccine design was aimed to inherit both antigen multivalency and antigen‐specific immunostimulation properties, observed in reported self‐adjuvanting vaccine candidates, by using self‐assembly and adjuvant‐conjugated antigens. Under vaccination concentrations, respective lipophilic adjuvants underwent co‐assembly with lipidated CH401, which boosted the anti‐CH401 IgG and IgM production. In particular, α‐GalCer was responsible for the most significant immune activation. Therefore, the newly developed vaccine design enabled the optimization of adjuvants against the antigenic CH401 peptide in a simple preparatory manner. Overall, the co‐assembling vaccine design opens the door for efficient and practical self‐adjuvanting vaccine development.

Engineering Sensitized Photon Upconversion Efficiency via Nanocrystal Wavefunction and Molecular Geometry

By Shan He, Runchen Lai, Qike Jiang, Yaoyao Han, Xiao Luo, Yuyang Tian, Xue Liu, Kaifeng Wu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

By simultaneously engineering molecular geometry and nanocrystal wavefunction, energy transfer and photon upconversion efficiencies of a perovskite nanocrystal/molecule system can be improved by orders of magnitude. Abstract Triplet energy transfer from inorganic nanocrystals to molecular acceptors has attracted strong attention for high‐efficiency photon upconversion. Here we study this problem using CsPbBr3 and CdSe nanocrystals as triplet donors and carboxylated anthracene isomers as acceptors. We find that the position of the carboxyl anchoring group on the molecule dictates the donor‐acceptor coupling to be either through‐bond or through‐space, while the relative strength of the two coupling pathways is controlled by the wavefunction leakage of nanocrystals that can be quantitatively tuned by nanocrystal sizes or shell thicknesses. By simultaneously engineering molecular geometry and nanocrystal wavefunction, energy transfer and photon upconversion efficiencies of a nanocrystal/molecule system can be improved by orders of magnitude.

Heavy‐Atom Tunneling Through Crossing Potential Energy Surfaces: Cyclization of a Triplet 2‐Formylarylnitrene to a Singlet 2,1‐Benzisoxazole

By Cláudio M. Nunes, Luís P. Viegas, Samuel A. Wood, José P. L. Roque, Robert J. McMahon, Rui Fausto from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

Heavy‐atom tunneling: The discovery of a new and distinct heavy‐atom quantum mechanical tunneling (QMT) reaction is presented. Triplet syn‐2‐formyl‐3‐fluorophenylnitrene spontaneously cyclizes to singlet 4‐fluoro‐2,1‐benzisoxazole under cryogenic conditions. Computational and experimental rate constants are in fair agreement and provide evidence for a mechanism involving heavy‐atom QMT through crossing triplet to singlet potential energy surfaces. Abstract Not long ago, the occurrence of quantum mechanical tunneling (QMT) chemistry involving atoms heavier than hydrogen was considered unreasonable. Contributing to the shift of this paradigm, we present here the discovery of a new and distinct heavy‐atom QMT reaction. Triplet syn‐2‐formyl‐3‐fluorophenylnitrene, generated in argon matrices by UV‐irradiation of an azide precursor, was found to spontaneously cyclize to singlet 4‐fluoro‐2,1‐benzisoxazole. Monitoring the transformation by IR spectroscopy, temperature‐independent rate constants (k≈1.4×10−3 s−1; half‐life of ≈8 min) were measured from 10 to 20 K. Computational estimated rate constants are in fair agreement with experimental values, providing evidence for a mechanism involving heavy‐atom QMT through crossing triplet to singlet potential energy surfaces. Moreover, the heavy‐atom QMT takes place with considerable displacement of the oxygen atom, which establishes a new limit for the heavier atom involved in a QMT reaction in cryogenic matrices.

Regenerable Covalent Organic Frameworks for Photo‐enhanced Uranium Adsorption from Seawater

By Wei‐Rong Cui, Fang‐Fang Li, Rui‐Han Xu, Cheng‐Rong Zhang, Xiao‐Rong Chen, Run‐Han Yan, Ru‐Ping Liang, Jian‐Ding Qiu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

Photoelectric and photocatalytic effects endow the covalent organic framework NDA‐TN‐AO with good anti‐biofouling activity. This occurs by generating biotoxic reactive oxygen species and promoting photoelectrons to reduce the adsorbed UVI to insoluble UIV, thereby improving the uranium adsorption capacity. Abstract Uranium is a key resource for the development of the nuclear industry, and extracting uranium from the natural seawater is one of the most promising ways to address the shortage of uranium resources. Herein, a semiconducting covalent organic framework (named NDA‐TN‐AO) with excellent photocatalytic and photoelectric activities was synthesized. The excellent photocatalytic effect endowed NDA‐TN‐AO with a high anti‐biofouling activity by generating biotoxic reactive oxygen species and promoting photoelectrons to reduce the adsorbed UVI to insoluble UIV, thereby increasing the uranium extraction capacity. Owing to the photoinduced effect, the adsorption capacity of NDA‐TN‐AO to uranium in seawater reaches 6.07 mg g−1, which is 1.33 times of that in dark. The NDA‐TN‐AO with enhanced adsorption capacity is a promising material for extracting uranium from the natural seawater.

Stimuli‐Responsive Cycloaurated “OFF‐ON” Switchable Anion Transporters

By Mohamed Fares, Xin Wu, Deepthi Ramesh, William Lewis, Paul A. Keller, Ethan N. W. Howe, Ricardo Pérez‐Tomás, Philip A. Gale from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

Bis‐imidazole‐based anion transporters have been complexed to AuIII to switch off their anion transport properties. In the presence of reducing agents such as GSH the gold is sequestered from the transporter and transport is switched on. This provides a method of targeting anion transporters to tissue with higher concentrations of GSH including tumors. Abstract Anion transporters have shown potential application as anti‐cancer agents that function by disrupting homeostasis and triggering cell death. In this research article we report switchable anion transport by gold complexes of anion transporters that are “switched on” in situ in the presence of the reducing agent GSH by decomplexation of gold. GSH is found in higher concentrations in tumors than in healthy tissue and hence this approach offers a strategy to target these systems to tumors.

Irreversible Amide‐Linked Covalent Organic Framework for Selective and Ultrafast Gold Recovery

By Hai‐Long Qian, Fan‐Lin Meng, Cheng‐Xiong Yang, Xiu‐Ping Yan from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

Going for gold: A building‐block exchange strategy gave an irreversible amide‐linked covalent organic framework (COF). The irreversible‐amide linked COF gave good stability, unprecedented fast adsorption kinetics, excellent selectivity and outstanding adsorption capacity for gold recovery. Abstract Design of stable adsorbents for selective gold recovery with large capacity and fast adsorption kinetics is of great challenge, but significant for the economy and the environment. Herein, we show the design and preparation of an irreversible amide‐linked covalent organic framework (COF) JNU‐1 via a building block exchange strategy for efficient recovery of gold. JNU‐1 was synthesized through the exchange of 4,4′‐biphenyldicarboxaldehyde (BA) in mother COF TzBA consisting of 4,4′,4′′‐(1,3,5‐triazine‐2,4,6‐triyl)trianiline (Tz) and BA with terephthaloyl chloride. The irreversible amide linked JNU‐1 gave good stability, unprecedented fast kinetics, excellent selectivity and outstanding adsorption capacity for gold recovery. X‐ray photoelectron spectroscopy along with thermodynamic study and quantum mechanics calculation reveals that the excellent performance of JNU‐1 for gold recovery results from the formation of hydrogen bonds C(N)−H⋅⋅⋅Cl and coordinate interaction of O and Au. The rational design of irreversible bonds as both inherent linkage and functional groups in COFs is a promising way to prepare stable COFs for diverse applications.

Cyclopropenylmethyl Cation: A Concealed Intermediate in Gold(I)‐Catalyzed Reactions

By Mathis Kreuzahler, Gebhard Haberhauer from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

A more thorough investigation of the gold(I)‐catalyzed haloalkynylation of arylalkynes was conducted. 13C‐Labeling experiments and quantum chemical calculations reveal a hitherto overlooked intermediate, namely the cyclopropenylmethyl cation. Consideration of this intermediate should facilitate the development of new synthetic methods for the construction of larger cyclic conjugated enyne systems. Abstract The last years have witnessed many gold‐catalyzed reactions of alkynes. One of the most prominent species in the reaction of two alkyne units is the vinyl‐substituted gold vinylidene intermediate. Here, we were able to show that the reaction of a haloacetylene and an alkyne proceeds via a hitherto overlooked intermediate, namely the cyclopropenylmethyl cation. The existence and relative stability of this concealed intermediate is verified by quantum chemical calculations and 13C‐labeling experiments. A comparison between the cyclopropenylmethyl cation and the well‐known vinylidene intermediate reveals that the latter is more stable only for smaller cycles. However, this stability reverses in larger cycles. In the case of the smallest representative of both species, the vinylidene cation is the transition state en route to the cyclopropenylmethyl cation. The discovery of this intermediate should help to get a deeper understanding for gold‐catalyzed carbon–carbon bond‐forming reactions of alkynes. Furthermore, since enynes can be formed from the cyclopropenylmethyl cation, the inclusion of this intermediate should enable the development of new synthetic methods for the construction of larger cyclic halogenated and non‐halogenated conjugated enyne systems.

Quantum Defects as a Toolbox for the Covalent Functionalization of Carbon Nanotubes with Peptides and Proteins

By Florian A. Mann, Niklas Herrmann, Felipe Opazo, Sebastian Kruss from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

Two new quantum defects were incorporated into single‐walled carbon nanotubes (SWCNT) carrying anchor groups for functionalization with biomolecules. The potential and versatility of this approach was demonstrated by the conjugation of a GFP‐binding nanobody as well as the growth of (fluorescent) peptide chains directly on the nanotube's carbon lattice. Abstract Single‐walled carbon nanotubes (SWCNTs) are a 1D nanomaterial that shows fluorescence in the near‐infrared (NIR, >800 nm). In the past, covalent chemistry was less explored to functionalize SWCNTs as it impairs NIR emission. However, certain sp3 defects (quantum defects) in the carbon lattice have emerged that preserve NIR fluorescence and even introduce a new, red‐shifted emission peak. Here, we report on quantum defects, introduced using light‐driven diazonium chemistry, that serve as anchor points for peptides and proteins. We show that maleimide anchors allow conjugation of cysteine‐containing proteins such as a GFP‐binding nanobody. In addition, an Fmoc‐protected phenylalanine defect serves as a starting point for conjugation of visible fluorophores to create multicolor SWCNTs and in situ peptide synthesis directly on the nanotube. Therefore, these quantum defects are a versatile platform to tailor both the nanotube's photophysical properties as well as their surface chemistry.

Two Pyrophosphates with Large Birefringences and Second‐Harmonic Responses as Ultraviolet Nonlinear Optical Materials

By Xuefang Lu, Zhaohui Chen, Xuerui Shi, Qun Jing, Ming‐Hsien Lee from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

An ideal balance has been achieved among nonlinear optical (NLO) effect, birefringence and cut‐off edge for Rb3PbBi(P2O7)2 pyrophosphate. Promising UV NLO materials, Rb3PbBi(P2O7)2 and Cs3PbBi(P2O7)2, were obtained in which [PbPO]∞ layers and BiO6 polyhedra containing two types of lone‐pair cations are present. Abstract Two new pyrophosphates nonlinear optical (NLO) materials, Rb3PbBi(P2O7)2 (I) and Cs3PbBi(P2O7)2 (II), were successfully designed and synthesized. Both compounds exhibit large NLO effects and birefringences. Material I presents the scarce case of possessing the coexistence of large birefringence (0.031 at 1064 nm and 0.037 at 532 nm) and second harmonic generation (SHG) response (2.8× potassium dihydrogen phosphate (KDP)) in ultraviolet NLO phosphates and its SHG is the largest in the phase‐matching (PM) pyrophosphates. Both I and II have three‐dimensional (3D) crystal structures composed of corner‐shared RbO12 (CsO11), RbO10 (CsO10), BiO6, PbO7 (PbO6) and P2O7 groups, in which P2O7 and PbO7 (PbO6) units form an alveolate [PbPO]∞ skeleton frame. Theoretical calculations reveal that the P−O, Bi−O and Pb−O units are mainly responsible for the moderate birefringence and large SHG efficiency of I.

Rational Design of Microporous MOFs with Anionic Boron Cluster Functionality and Cooperative Dihydrogen Binding Sites for Highly Selective Capture of Acetylene

By Yuanbin Zhang, Jianbo Hu, Rajamani Krishna, Lingyao Wang, Lifeng Yang, Xili Cui, Simon Duttwyler, Huabin Xing from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

Two isostructural boron‐cluster‐functionalized supramolecular MOFs were rationally designed. They feature suitable pore size and cooperative dihydrogen bonding sites for highly selective capture of acetylene from carbon dioxide and ethylene. Abstract Separation of acetylene (C2H2) from carbon dioxide (CO2) or ethylene (C2H4) is important in industry but limited by the low capacity and selectivity owing to their similar molecular sizes and physical properties. Herein, we report two novel dodecaborate‐hybrid metal–organic frameworks, MB12H12(dpb)2 (termed as BSF‐3 and BSF‐3‐Co for M=Cu and Co), for highly selective capture of C2H2. The high C2H2 capacity and remarkable C2H2/CO2 selectivity resulted from the unique anionic boron cluster functionality as well as the suitable pore size with cooperative proton‐hydride dihydrogen bonding sites (B−Hδ−⋅⋅⋅Hδ+−C≡C−Hδ+⋅⋅⋅Hδ−−B). This new type of C2H2‐specific functional sites represents a fresh paradigm distinct from those in previous leading materials based on open metal sites, strong electrostatics, or hydrogen bonding.

Corrigendum: An Excimer Clamp for Measuring Damaged‐Base Excision by the DNA Repair Enzyme NTH1

By Yong Woong Jun, David L. Wilson, Anna M. Kietrys, Elizabeth R. Lotsof, Savannah G. Conlon, Sheila S. David, Eric T. Kool from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

Corrigendum: Vancomycin Resistance is Overcome by Conjugation of Polycationic Peptides

By Florian Umstätter, Cornelius Domhan, Tobias Hertlein, Knut Ohlsen, Eric Mühlberg, Christian Kleist, Stefan Zimmermann, Barbro Beijer, Karel D. Klika, Uwe Haberkorn, Walter Mier, Philipp Uhl from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

Graphical Abstract: Angew. Chem. Int. Ed. 40/2020

By from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

Inside Back Cover: N‐Annulated Perylene Bisimides to Bias the Differentiation of Metastable Supramolecular Assemblies into J‐ and H‐Aggregates (Angew. Chem. Int. Ed. 40/2020)

By Elisa E. Greciano, Joaquín Calbo, Enrique Ortí, Luis Sánchez from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

The self‐assembling features of N‐annulated perylene bisimides (PBIs) 1 and 2 are discussed by E. Ortí, L. Sánchez, and co‐workers in their Research Article on page 17517. The stability of the aggregates of diester 1 substantiates the significance of van der Waals and dipole–dipole electrostatic interactions in the construction of stable supramolecular assemblies. The incorporation of amide functional groups in 2 results in a stimulating pathway differentiation to achieve up to three J‐type aggregates and a fourth H‐type aggregate depending on the experimental conditions.

Frontispiece: How Far Does Energy Migrate in DNA and Cause Damage? Evidence for Long‐Range Photodamage to DNA

By Arthur Kuhlmann, Larissa Bihr, Hans‐Achim Wagenknecht from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

DNA Lesions In their Communication on page 17378, H.‐A. Wagenknecht et al. report a new DNA architecture to address the question how far energy migrates in DNA and forms cyclobutane pyrimidine dimers as photodamages causing skin cancer.

Inside Cover: Quantum Defects as a Toolbox for the Covalent Functionalization of Carbon Nanotubes with Peptides and Proteins (Angew. Chem. Int. Ed. 40/2020)

By Florian A. Mann, Niklas Herrmann, Felipe Opazo, Sebastian Kruss from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

sp3 quantum defects can be used for covalent functionalization of single‐walled carbon nanotubes (SWCNTs) under preservation of their near‐infrared (NIR) fluorescence. In their Research Article on page 17732, S. Kruss and co‐workers describe how peptide chains are directly grown on the SWCNT sidewall by using an Fmoc‐protected phenylalanine defect. A second maleimide defect enables attachment of proteins via thiol groups. This chemistry provides access to NIR‐fluorescent SWCNT bioconjugates and applications in photonics, biosensing, and medicine.

Back Cover: Single‐Molecule 3D Orientation Imaging Reveals Nanoscale Compositional Heterogeneity in Lipid Membranes (Angew. Chem. Int. Ed. 40/2020)

By Jin Lu, Hesam Mazidi, Tianben Ding, Oumeng Zhang, Matthew D. Lew from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

The rotational dynamics of single fluorescent dyes are influenced by their surrounding nano‐environment within lipid membranes. In their Research Article on page 17572, M. D. Lew and co‐workers show that super‐resolved imaging of molecular orientation and wobble in 3D resolves lipid composition, liquid‐ordered and ‐disordered phases, and enzyme activity in membranes.

Cover Picture: Templated‐Assembly of CsPbBr3 Perovskite Nanocrystals into 2D Photonic Supercrystals with Amplified Spontaneous Emission (Angew. Chem. Int. Ed. 40/2020)

By David Vila‐Liarte, Maximilian W. Feil, Aurora Manzi, Juan Luis Garcia‐Pomar, He Huang, Markus Döblinger, Luis M Liz‐Marzán, Jochen Feldmann, Lakshminarayana Polavarapu, Agustín Mihi from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

CsPbBr3 perovskite nanocrystals are readily shaped into large‐area 2D photonic crystals by means of nanoimprinting lithography, as shown by L. Polavarapu, A. Mihi et al. in their Research Article on page 17750. The periodic patterning provides efficient light coupling to the nanocrystal layer, increasing the electric field intensity within the perovskite film and resulting in amplified spontaneous emission (ASE) under lower optical excitation fluences in the near‐IR. The cover image illustrates the nanocrystal assembly process and the resulting photonic architecture after the mold has been removed.

Synthetic Organic Design for Solar Fuel Systems

By Julien Warnan, Erwin Reisner from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

Organic and hybrid systems have emerged to challenge the classical inorganic structures through their enormous chemical diversity and modularity. Recent advances in the design of synthetic architectures and promising strategies toward (solar) fuel synthesis are discussed, highlighting progress on materials from dyes and catalysts to polymers and covalent organic frameworks. Abstract From the understanding of biological processes and metalloenzymes to the development of inorganic catalysts, electro‐ and photocatalytic systems for fuel generation have evolved considerably during the last decades. Recently, organic and hybrid organic systems have emerged to challenge the classical inorganic structures through their enormous chemical diversity and modularity that led earlier to their success in organic (opto)electronics. This Minireview describes recent advances in the design of synthetic organic architectures and promising strategies toward (solar) fuel synthesis, highlighting progress on materials from organic ligands and chromophores to conjugated polymers and covalent organic frameworks.

Production of Hydrogen Peroxide by Photocatalytic Processes

By Huilin Hou, Xiangkang Zeng, Xiwang Zhang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

Peroxide from sunlight: The production of H2O2 by photocatalysis is a sustainable process, since it uses water and oxygen as the source materials and solar light as the energy. Encouraging processes have been developed in the last decade for the photocatalytic production of H2O2, and these are discussed in this Review. Abstract Hydrogen peroxide (H2O2) has received increasing attention because it is not only a mild and environmentally friendly oxidant for organic synthesis and environmental remediation but also a promising new liquid fuel. The production of H2O2 by photocatalysis is a sustainable process, since it uses water and oxygen as the source materials and solar light as the energy. Encouraging processes have been developed in the last decade for the photocatalytic production of H2O2. In this Review we summarize research progress in the development of processes for the photocatalytic production of H2O2. After a brief introduction emphasizing the superiorities of the photocatalytic generation of H2O2, the basic principles of establishing an efficient photocatalytic system for generating H2O2 are discussed, highlighting the advanced photocatalysts used. This Review is concluded by a brief summary and outlook for future advances in this emerging research field.

Improving Cancer Immunotherapy Outcomes Using Biomaterials

By Shuangqian Yan, Zichao Luo, Zhenglin Li, Yu Wang, Jun Tao, Changyang Gong, Xiaogang Liu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

Immunotherapy is a promising strategy to treat tumors, but its low response rate and side effects are major challenges in clinical applications. This Minireview highlights a range of biomaterials with the potential to alter the tumor microenvironment to improve effectiveness and outcomes of cancer immunotherapy. Abstract Immunotherapy has made great strides in improving clinical outcomes in cancer treatment. However, few patients exhibit adequate response rates for key outcome measures and desired long‐term responses, and they often suffer systemic side effects due to the dynamic nature of the immune system. This has motivated a search for alternative strategies to improve unsatisfactory immunotherapeutic outcomes. In recent years, biomaterial‐assisted immunotherapy has shown promise in cancer treatment with improved therapeutic efficacy and reduced side effects. These biomaterials have illuminated fundamental mechanisms underlying the immunoediting process, while greatly improving the efficacy of chimeric antigen receptor (CAR) T‐cell therapy, cancer vaccine therapy, and immune checkpoint blockade therapy. This Minireview discusses recent advances in engineered biomaterials that address limitations associated with conventional cancer immunotherapies.

Natural Soft/Rigid Superlattices as Anodes for High‐Performance Lithium‐Ion Batteries

By Wei Bai, Jingyu Gao, Kun Li, Gongrui Wang, Tengfei Zhou, Pengju Li, Shengyong Qin, Genqiang Zhang, Zaiping Guo, Chong Xiao, Yi Xie from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

A misfit compound, PbNbS3, has a soft/rigid superlattice structure. Soft PbS sublayers contribute the capacity, and the rigid NbS2 sublayers maintain the stability and dominate the conductivity, thus promoting the migration of electrons and lithium ions, leading to competitive lithium‐ion anode performance. Abstract Volume expansion and poor conductivity are two major obstacles that hinder the pursuit of the lithium‐ion batteries with long cycling life and high power density. Herein, we highlight a misfit compound PbNbS3 with a soft/rigid superlattice structure, confirmed by scanning tunneling microscopy and electrochemical characterization, as a promising anode material for high performance lithium‐ion batteries with optimized capacity, stability, and conductivity. The soft PbS sublayers primarily react with lithium, endowing capacity and preventing decomposition of the superlattice structure, while the rigid NbS2 sublayers support the skeleton and enhance the migration of electrons and lithium ions, as a result leading to a specific capacity of 710 mAh g−1 at 100 mA g−1, which is 1.6 times of NbS2 and 3.9 times of PbS. Our finding reveals the competitive strategy of soft/rigid structure in lithium‐ion batteries and broadens the horizons of single‐phase anode material design.

Achieving Pure Green Electroluminescence with CIEy of 0.69 and EQE of 28.2% from an Aza‐Fused Multi‐Resonance Emitter

By Yuewei Zhang, Dongdong Zhang, Jinbei Wei, Xiangchen Hong, Yang Lu, Deping Hu, Guomeng Li, Ziyang Liu, Yang Chen, Lian Duan from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

By fusing aza‐aromatics onto a B−N skeleton, a hybridized multi‐resonance charge‐transfer molecule AZA‐BN was synthesized. The AZA‐BN device exhibits narrow‐band green electroluminescence with a maximum external quantum efficiency/CIE coordinate y of 28.2 %/0.69, representing the purest green bottom‐emitting organic light‐emitting diode. Abstract Pure green emitters are essential for realizing an ultrawide color gamut in next‐generation displays. Herein, by fusing the difficult‐to‐access aza‐aromatics onto B (boron)–N (nitrogen) skeleton, a hybridized multi‐resonance and charge transfer (HMCT) molecule AZA‐BN was successfully synthesized through an effective one‐shot multiple cyclization method. AZA‐BN shows pure green fluorescence with photoluminance quantum yield of 99.7 %. The corresponding green device exhibits a maximum external quantum efficiency and power efficiency of 28.2 % and 121.7 lm W−1, respectively, with a full width half maximum (FWHM) of merely 30 nm and Commission Internationale de l'Eclairage (CIE) coordinate y of 0.69, representing the purest green bottom‐emitting organic light‐emitting diode.

Revealing Crystallization‐Induced Blue‐Shift Emission of a Di‐Boron Complex by Enhanced Photoluminescence and Electrochemiluminescence

By Jonathan M. Wong, Ruizhong Zhang, Peidong Xie, Liuqing Yang, Minlin Zhang, Ruixue Zhou, Ruiyao Wang, Yue Shen, Bing Yang, Hong‐Bo Wang, Zhifeng Ding from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

Crystallization‐induced emission of a di‐boron complex luminophore, which gives blue‐shifted and enhanced photoluminescence and electrochemiluminescence (ECL) in the annihilation pathway, is reported. ECL at crystalline film/solution interfaces was further enhanced by means of both co‐reactant route and restriction of intramolecular rotation. Abstract Elucidating the effects of crystallization‐induced blue‐shift emission of a newly synthesized di‐boron complex (DBC) by enhanced photoluminescence (PL) and electrochemiluminescence (ECL) in the annihilation pathway was realized for the first time. The 57 nm blue‐shift and great enhancement in the crystalline lattice relative to the DBC solution were attributed to the restriction of intramolecular rotation (RIR) and confirmed by PL imaging, X‐ray diffraction, as well as DFT calculations. It was discovered that ECL at crystalline film/solution interfaces can be further enhanced by means of both co‐reactant route and RIR. The RIR contributions with co‐reactant increased ECL up to 5 times more. Very interestingly, the co‐reactant system was found to give off a red‐shifted light emission. Mechanistic studies reveal that a difference between location of the ECL in the co‐reactant route and that in the annihilation pathway leads to an alternative emission wavelength.

Ordered Solid‐State Microstructures of Conjugated Polymers Arising from Solution‐State Aggregation

By Ze‐Fan Yao, Zi‐Yuan Wang, Hao‐Tian Wu, Yang Lu, Qi‐Yi Li, Lin Zou, Jie‐Yu Wang, Jian Pei from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

Using temperature‐controlled polymer aggregation, the solid‐state microstructures of conjugated polymers are finely tuned. The temperature‐controlled strategy enhances the molecular ordering in thin films and leads to efficient charge transport. A polymer transistor with tuned molecular ordering exhibited improved electron mobilities of up to 3.71 cm2 V−1 s−1, which is two orders of magnitude higher than the disordered samples. Abstract Controlling the solution‐state aggregation of conjugated polymers for producing specific microstructures remains challenging. Herein, a practical approach is developed to finely tune the solid‐state microstructures through temperature‐controlled solution‐state aggregation and polymer crystallization. High temperature generates significant conformation fluctuation of conjugated backbones in solution, which facilitates the polymer crystallization from solvated aggregates to orderly packed structures. The polymer films deposited at high temperatures exhibit less structural disorders and higher electron mobilities (up to two orders of magnitude) in field‐effect transistors, compared to those deposited at low temperatures. This work provides an effective strategy to tune the solution‐state aggregation to reveal the relationship between solution‐state aggregation and solid‐state microstructures of conjugated polymers.

Boosting the Quantum Efficiency of Ultralong Organic Phosphorescence up to 52 % via Intramolecular Halogen Bonding

By Zhan Yang, Chao Xu, Wenlang Li, Zhu Mao, Xiangyu Ge, Qiuyi Huang, Huangjun Deng, Juan Zhao, Feng Long Gu, Yi Zhang, Zhenguo Chi from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

Intramolecular halogen bonding promotes the intersystem crossing rate in organic molecules and enhances the afterglow efficiency up to 52.1 %. This is the highest value achieved in molecular crystals reported so far. Abstract Ultralong organic phosphorescence (UOP) has attracted increasing attention due to its potential applications in optoelectronics, bioelectronics, and security protection. However, achieving UOP with high quantum efficiency (QE) over 20 % is still full of challenges due to intersystem crossing (ISC) and fast non‐radiative transitions in organic molecules. Here, we present a novel strategy to enhance the QE of UOP materials by modulating intramolecular halogen bonding via structural isomerism. The QE of CzS2Br reaches up to 52.10 %, which is the highest afterglow efficiency reported so far. The crucial reason for the extraordinary QE is intramolecular halogen bonding, which can not only effectively enhance ISC by promoting spin–orbit coupling, but also greatly confine motions of excited molecules to restrict non‐radiative pathways. This work provides a reasonable strategy to develop highly efficient UOP materials for practical applications.

An Adduct of Sulfur Monoxide to a Frustrated Sn/P Lewis Pair

By Philipp Holtkamp, Timo Glodde, Dario Poier, Beate Neumann, Hans‐Georg Stammler, Norbert W. Mitzel from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

The first adduct of SO to a main group metal system was found by reacting PhNSO with an intramolecular Sn/P frustrated Lewis pair; the exceptional stability of the adduct is attributed to the polarity of the incorporated SO unit. Abstract The geminal frustrated Lewis pair (F5C2)3SnCH2P(tBu)2 (1) reacted with N‐sulfinylaniline PhNSO to afford the first sulfur monoxide adduct of a main group metal, (F5C2)3SnCH2P(tBu)2⋅SO (2), which contains a SnCPSO ring. The second product is a phenylnitrene adduct of 1. The surprising stability of 2 was compared with the stabilities of the so far inaccessible O2 and S2 adducts of 1. Attempts to prepare these from 1 and the elemental chalcogens (O2, S8, Se∞, Te∞) led to four‐membered SnCPE ring systems. Quantum‐chemical investigations of 2 demonstrate the bond polarity of the SO unit to stabilize 2.

Fluorogenic Probe Using a Mislow–Evans Rearrangement for Real‐Time Imaging of Hydrogen Peroxide

By Dianne Pham, Upamanyu Basu, Ivanna Pohorilets, Claudette M. St Croix, Simon C. Watkins, Kazunori Koide from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

A fluorogenic probe that selectively undergoes a [2,3]‐sigmatropic rearrangement (seleno Mislow–Evans rearrangement) with H2O2, followed by acetal hydrolysis, is reported to produce a green fluorescent molecule in seconds. Unlike other electrophilic probes, the current probe acts as a nucleophile. The fast kinetics enabled real‐time imaging of H2O2 produced in endothelial cells in 8 seconds and in a zebrafish wound healing model. Abstract Hydrogen peroxide (H2O2) mediates the biology of wound healing, apoptosis, inflammation, etc. H2O2 has been fluorometrically imaged with protein‐ or small‐molecule‐based probes. However, only protein‐based probes have afforded temporal insights within seconds. Small‐molecule‐based electrophilic probes for H2O2 require many minutes for a sufficient response in biological systems. Here, we report a fluorogenic probe that selectively undergoes a [2,3]‐sigmatropic rearrangement (seleno‐Mislow‐Evans rearrangement) with H2O2, followed by acetal hydrolysis, to produce a green fluorescent molecule in seconds. Unlike other electrophilic probes, the current probe acts as a nucleophile. The fast kinetics enabled real‐time imaging of H2O2 produced in endothelial cells in 8 seconds (much earlier than previously shown) and H2O2 in a zebrafish wound healing model. This work may provide a platform for endogenous H2O2 detection in real time with chemical probes.

Materials Design Principles for Air‐Stable Lithium/Sodium Solid Electrolytes

By Yizhou Zhu, Yifei Mo from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

Sulfide solid electrolytes are promising for all‐solid‐state batteries, but many of them exhibit poor air stability. Thermodynamic analyses are performed to investigate stability trends and identify promising material systems with desirable moisture and electrochemical stability and also to provide design principles for the development of air‐stable solid electrolytes. Abstract Sulfide solid electrolytes are promising inorganic solid electrolytes for all‐solid‐state batteries. Despite their high ionic conductivity and desirable mechanical properties, many known sulfide solid electrolytes exhibit poor air stability. The spontaneous hydrolysis reactions of sulfides with moisture in air lead to the release of toxic hydrogen sulfide and materials degradation, hindering large‐scale manufacturing and applications of sulfide‐based solid‐state batteries. In this work, we systematically investigate the hydrolysis and reduction reactions in Li‐ and Na‐containing sulfides and chlorides by applying thermodynamic analyses based on a first principles computation database. We reveal the stability trends among different chemistries and identify the effect of cations, anions, and Li/Na content on moisture stability. Our results identify promising materials systems to simultaneously achieve desirable moisture stability and electrochemical stability, and provide the design principles for the development of air‐stable solid electrolytes.

Morphometric Cell Classification for Single‐Cell MALDI‐Mass Spectrometry Imaging

By Klára Ščupáková, Frédéric Dewez, Axel K. Walch, Ron M. A. Heeren, Benjamin Balluff from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

Understanding how cells regulate their bioenergetic demands, adjust to the microenvironment, or respond to stimuli is the aim of molecular biology. Yet, methods able to describe the molecular content, histological identity, and spatial context of a single cell do not exist. The presented method integrates morphometric image analysis to delineate and classify individual cells with their cell‐specific molecular profiles obtained by MALDI‐MSI. Abstract The large‐scale and label‐free molecular characterization of single cells in their natural tissue habitat remains a major challenge in molecular biology. We present a method that integrates morphometric image analysis to delineate and classify individual cells with their single‐cell‐specific molecular profiles. This approach provides a new means to study spatial biological processes such as cancer field effects and the relationship between morphometric and molecular features.

Tailoring A Poly(ether sulfone) Bipolar Membrane: Osmotic‐Energy Generator with High Power Density

By Yue Sun, Tiandu Dong, Chunxin Lu, Weiwen Xin, Linsen Yang, Pei Liu, Yongchao Qian, Yuanyuan Zhao, Xiang‐Yu Kong, Liping Wen, Lei Jiang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

Herein, a new bipolar membrane, with different functional groups in the poly(ether sulfone) chain, is fabricated by a nonsolvent‐induced phase separation (NIPS) and spin‐coating (SC) method. The asymmetric structure helps to form distinct ion rectification and results in good power generation performance. Abstract Osmotic energy, obtained through different concentrations of salt solutions, is recognized as a form of a sustainable energy source. In the past years, membranes derived from asymmetric aromatic compounds have attracted attention because of their low cost and high performance in osmotic energy conversion. The membrane formation process, charging state, functional groups, membrane thickness, and the ion‐exchange capacity of the membrane could affect the power generation performance. Among asymmetric membranes, a bipolar membrane could largely promote the ion transport. Here, two polymers with the same poly(ether sulfone) main chain but opposite charges were synthesized to prepare bipolar membranes by a nonsolvent‐induced phase separation (NIPS) and spin‐coating (SC) method. The maximum power density of the bipolar membrane reaches about 6.2 W m−2 under a 50‐fold salinity gradient, and this result can serve as a reference for the design of bipolar membranes for osmotic energy conversion systems.

Non‐Diazo C−H Insertion Approach to Cyclobutanones through Oxidative Gold Catalysis

By Zhitong Zheng, Youliang Wang, Xu Ma, Yuxue Li, Liming Zhang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

Insertion into unactivated C(sp3)−H bonds by metal carbenes/carbenoids is a reaction of significant synthetic value. In this study, easily accessible alkynone substrates are converted into strained cyclobutanones through such an insertion by an oxidatively generated β‐diketone‐α‐gold carbene. This reaction serves as a benign and more synthetically expedient alternative to diazo‐based approaches. Abstract Cyclobutanones are synthetically versatile compounds that often require extensive effort to access. Herein, we report a facile synthesis of cyclobutanones based on the C(sp3)−H insertion chemistry of oxidatively generated gold carbenes. Various cyclobutanones were obtained in synthetically useful yields from substrates with minimal structural prefunctionalization. This discovery reveals new synthetic utilities of gold‐catalyzed oxidative transformations of alkynones.

Composition‐Tunable Antiperovskite CuxIn1−xNNi3 as Superior Electrocatalysts for the Hydrogen Evolution Reaction

By Jiaxi Zhang, Longhai Zhang, Li Du, Huolin L. Xin, John B. Goodenough, Zhiming Cui from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

A composition tuning strategy is employed to develop a group of ANNi3 antiperovskite nitrides (A=In or Cu). By partial substitution of the A site in the pristine antiperovskite nitride, a remarkable enhancement of the hydrogen evolution reaction (HER) performance is achieved on the derived CuxIn1−xNNi3 electrocatalysts. This is ascribed to the lowered kinetic barrier and optimal hydrogen adsorption free energy by the compositional adjustment. Abstract A group of newly reported antiperovskite nitrides CuxIn1−xNNi3 (0≤x≤1) with tunable composition are employed as electrocatalysts for the hydrogen evolution reaction (HER). Cu0.4In0.6NNi3 shows the highest intrinsic performance among all developed catalysts with an overpotential of merely 42 mV at 10 mA cmgeo−2. Stability tests at a high current density of 100 mA cmgeo−2 show its super‐stable performance with only 7 mV increase in overpotential after more than 60 hours of measurement, surpassing commercial Pt/C (increase of 170 mV). By partial substitution, the derived antiperovskite nitride achieves a smaller kinetic barrier of water dissociation compared to the unsubstituted InNNi3 and CuNNi3, revealed by first‐principle calculations. It is found that the partially substituted CuxIn1−xNNi3 possesses a thermal neutral and desirable Gibbs free energy of hydrogen for HER, ascribed to the tailoring of the energy of d‐band center arose by the A‐site (A=Cu or In) substitution and a resulting optimization of adsorbate interactions.

Porphyrin/Ionic‐Liquid Co‐assembly Polymorphism Controlled by Liquid–Liquid Phase Separation

By Chengqian Yuan, Mengyao Yang, Xiaokang Ren, Qianli Zou, Xuehai Yan from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

Droplets controlled, polymorphism achieved: Ion‐cluster‐rich droplets formed through liquid–liquid phase separation trigger the nucleation and growth of multicomponent co‐assembly. Manipulating the intermolecular interactions within the droplets can yield co‐assembly polymorphism and tunable phase‐transition behaviors. Abstract Understanding and controlling multicomponent co‐assembly is of primary importance in different fields, such as materials fabrication, pharmaceutical polymorphism, and supramolecular polymerization, but these aspects have been a long‐standing challenge. Herein, we discover that liquid–liquid phase separation (LLPS) into ion‐cluster‐rich and ion‐cluster‐poor liquid phases is the first step prior to co‐assembly nucleation based on a model system of water‐soluble porphyrin and ionic liquids. The LLPS‐formed droplets serve as the nucleation precursors, which determine the resulting structures and properties of co‐assemblies. Co‐assembly polymorphism and tunable supramolecular phase transition behaviors can be achieved by regulating the intermolecular interactions at the LLPS stage. These findings elucidate the key role of LLPS in multicomponent co‐assembly evolution and enable it to be an effective strategy to control co‐assembly polymorphism as well as supramolecular phase transitions.

An RCM‐Based Total Synthesis of the Antibiotic Disciformycin B

By Philipp Waser, Karl‐Heinz Altmann from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

Large or small (ring), that was the question. The antibiotic disciformycin B has been synthesized in 18 linear steps from simple starting materials. The key step was the macrocyclization of the tetraene 7 by ring‐closing olefin metathesis (RCM). Abstract The total synthesis of the potent new antibiotic disciformycin B (2) is described, which shows significant activity against methicillin‐ and vancomycin‐resistant Staphylococcus aureus (MRSA/VRSA) strains. The synthetic route is based on macrocyclization of a tetraene substrate to the 12‐membered macrolactone core by ring‐closing olefin metathesis (RCM). Although macrocyclization was accompanied by concomitant cyclopentene formation by an alternative RCM pathway, conditions were established to give the macrocycle as the major product. Key steps in the construction of the RCM substrate include a highly efficient Evans syn‐aldol reaction, the asymmetric Brown allylation of angelic aldehyde, and the stereoselective Zn(BH4)2‐mediated 1,2‐reduction of an enone. The synthesis was completed by late‐stage dehydrative glycosylation to introduce the d‐arabinofuranosyl moiety and final chemoselective allylic alcohol oxidation.

How Far Does Energy Migrate in DNA and Cause Damage? Evidence for Long‐Range Photodamage to DNA

By Arthur Kuhlmann, Larissa Bihr, Hans‐Achim Wagenknecht from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

Hop as far as possible: Long‐range energy migration in DNA cause damages 105 Å away from the site of light absorption. The evidence of long‐range formation of cyclobutane pyrimidine dimers is fundamental for our understanding of DNA photodamaging. Abstract A new DNA architecture addresses the question, how far energy migrates in DNA and forms cyclobutane pyrimidine dimers (CPDs) as photodamages causing skin cancer. The 3‐methoxyxanthone nucleoside allows site‐selective photoenergy injection into DNA. The designated CPD site lacks the phosphodiester bond and can be placed in defined distances. The CPD formation links two oligonucleotides together and allows probing by gel electrophoresis. We obtained a sigmoidal distance dependence with R0 of 25±3 Å. Below R0, short‐range energy migration occurs with high CPD yields and shallow distance dependence, characteristic for a coherent process. 5‐methyl‐C as epigenetic modification on the 3′‐side facilitates CPD formation. Above R0, long‐range incoherent energy migration occurs over 30 A‐T pairs (105.4 Å). The evidence of long‐range CPD formation is fundamental for our understanding of DNA photodamaging. Open access funding enabled and organized by Projekt DEAL.

Stereoselective On‐Surface Cyclodehydrofluorization of a Tetraphenylporphyrin and Homochiral Self‐Assembly

By Hui Chen, Lei Tao, Dongfei Wang, Zhuo‐Yan Wu, Jun‐Long Zhang, Song Gao, Wende Xiao, Shixuan Du, Karl‐Heinz Ernst, Hong‐Jun Gao from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

Thermally induced cyclodehydrofluorization of a tetraphenylporphyrin proceeded with high stereoselectivity on a gold surface in an ultrahigh vacuum to give the prochiral windmill product (see scheme), which aggregated into a two‐dimensional conglomerate. Such surface topochemistry enabled by alignment and dense packing may offer new possibilities for stereoselective synthesis in other systems. Abstract The thermally induced cyclodehydrofluorization of iron tetrakis(pentafluorophenyl)porphyrin proceeded highly stereoselectively to give a prochiral product on a gold surface in an ultrahigh vacuum, whereas dehydrocyclization of the respective iron tetrakisphenylporphyrin did not show such selectivity. Stereoselectivity was predominantly observed for closely packed layers, which is an indication of intermolecular cooperativity and steric constraints induced by adjacent species. Density functional theory identified intermolecular packing constraints as the origin of such selectivity during the reaction. Scanning tunneling microscopy revealed the formation of an enantiomerically pure two‐dimensional self‐assembly as a conglomerate of mirror domains. On‐surface two‐dimensional topochemistry, as reported herein, may open new routes for stereoselective synthesis.

Phosphorothioate Modification of mRNA Accelerates the Rate of Translation Initiation to Provide More Efficient Protein Synthesis

By Daisuke Kawaguchi, Ayumi Kodama, Naoko Abe, Kei Takebuchi, Fumitaka Hashiya, Fumiaki Tomoike, Kosuke Nakamoto, Yasuaki Kimura, Yoshihiro Shimizu, Hiroshi Abe from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

Phosphorothioate (PS) modification of mRNA leads to enhanced protein expression in a reconstituted E. coli translation system. Single‐turnover analysis of PS‐mRNA translation showed that phosphorothioate modification increases the number of translating ribosomes, thus suggesting that translation initiation is more efficient on the modified mRNA. Abstract Messenger RNAs (mRNAs) with phosphorothioate modification (PS‐mRNA) to the phosphate site of A, G, C, and U with all 16 possible combinations were prepared, and the translation reaction was evaluated using an E. coli cell‐free translation system. Protein synthesis from PS‐mRNA increased in 12 of 15 patterns when compared with that of unmodified mRNA. The protein yield increased 22‐fold when the phosphorothioate modification at A/C sites was introduced into the region from the 5′‐end to the initiation codon. Single‐turnover analysis of PS‐mRNA translation showed that phosphorothioate modification increases the number of translating ribosomes, thus suggesting that the rate of translation initiation (rate of ribosome complex formation) is positively affected by the modification. The method provides a new strategy for improving translation by using non‐natural mRNA.

A General Catalyst Based on Cobalt Core–Shell Nanoparticles for the Hydrogenation of N‐Heteroarenes Including Pyridines

By Kathiravan Murugesan, Vishwas G. Chandrashekhar, Carsten Kreyenschulte, Matthias Beller, Rajenahally V. Jagadeesh from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

One fits all: Co/Co3O4 core–shell nanoparticles prepared by pyrolysis of a Co‐pyromellitic acid template on silica served as stable and reusable catalysts for the selective hydrogenation of pyridines, quinolines, and other heteroarenes. Abstract Herein, we report the synthesis of specific silica‐supported Co/Co3O4 core–shell based nanoparticles prepared by template synthesis of cobalt‐pyromellitic acid on silica and subsequent pyrolysis. The optimal catalyst material allows for general and selective hydrogenation of pyridines, quinolines, and other heteroarenes including acridine, phenanthroline, naphthyridine, quinoxaline, imidazo[1,2‐a]pyridine, and indole under comparably mild reaction conditions. In addition, recycling of these Co nanoparticles and their ability for dehydrogenation catalysis are showcased.

Photocatalytic Vicinal Aminopyridylation of Methyl Ketones by a Double Umpolung Strategy

By Honggu Im, Wonjun Choi, Sungwoo Hong from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

A photocatalytic strategy for the vicinal aminopyridylation of ketones was developed using pyridinium N−N ylides as bifunctional reagents. Intriguingly, the synthetic advances of this approach were highlighted by the selective installation of amino and pyridyl groups into the nucleophilic α‐position and electrophilic carbonyl carbon, respectively. Abstract A photocatalytic double umpolung strategy for the vicinal aminopyridylation of ketones was developed using pyridinium N−N ylides. The inversion of the polarity of the pyridinium N−N ylides by single‐electron oxidation successfully enables radical‐mediated 1,3‐dipolar cycloadditions with enolsilanes formed in situ from ketones, followed by homolytic cleavage of the N−N bond. Intriguingly, the nucleophilic amino and electrophilic pyridyl groups in the ylides can be installed at the nucleophilic α‐position and electrophilic carbonyl carbon, respectively, which are typically inaccessible by their innate polarity‐driven reactivity. This method accommodates a broad scope, and the utility was further demonstrated by the late‐stage functionalization of complex biorelevant molecules. Moreover, the strategy can be successfully applied to enamides.

A Yolk–Shell‐Structured FePO4 Cathode for High‐Rate and Long‐Cycling Sodium‐Ion Batteries

By Zhuangzhuang Zhang, Yichen Du, Qin‐Chao Wang, Jingyi Xu, Yong‐Ning Zhou, Jianchun Bao, Jian Shen, Xiaosi Zhou from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

FePO4 nanospheres consisting of mesoporous nanoyolks supported inside robust porous nanoshells are synthesized by a judicious multi‐step templating strategy using carbon nanospheres as the starting material. Their architecture and composition allow these hierarchical FePO4 yolk–shell nanospheres to manifest excellent sodium storage performance as a cathode material for sodium‐ion batteries. Abstract Amorphous iron phosphate (FePO4) has attracted enormous attention as a promising cathode material for sodium‐ion batteries (SIBs) because of its high theoretical specific capacity and superior electrochemical reversibility. Nevertheless, the low rate performance and rapid capacity decline seriously hamper its implementation in SIBs. Herein, we demonstrate a sagacious multi‐step templating approach to skillfully craft amorphous FePO4 yolk–shell nanospheres with mesoporous nanoyolks supported inside the robust porous outer nanoshells. Their unique architecture and large surface area enable these amorphous FePO4 yolk–shell nanospheres to manifest remarkable sodium storage properties with high reversible capacity, outstanding rate performance, and ultralong cycle life.

Spodium Bonds: Noncovalent Interactions Involving Group 12 Elements

By Antonio Bauzá, Ibon Alkorta, José Elguero, Tiddo J. Mooibroek, Antonio Frontera from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

A spodium bond (SpB) is defined as the net attractive interaction between a Group 12 element acting as a Lewis acid and electron‐rich atoms (Lewis bases or anions). These noncovalent interactions involve antibonding Sp–ligand orbitals and are markedly different from coordination bonds. Evidence for SpBs is provided by ab initio calculations and examining solid‐state structures. Abstract The term spodium (Sp) bond is proposed to refer to a net attractive interaction between any element of Group 12 and electron‐rich atoms (Lewis bases or anions). These noncovalent interactions are markedly different from coordination bonds (antibonding Sp–ligand orbital involved). Evidence is provided for the existence of this interaction by calculations at the RI‐MP2/aug‐cc‐pVTZ level of theory, atoms‐in‐molecules, and natural bond orbital analyses and by examining solid‐state structures in the Cambridge Structure Database.

BIMP‐Catalyzed 1,3‐Prototropic Shift for the Highly Enantioselective Synthesis of Conjugated Cyclohexenones

By Jonathan C. Golec, Eve M. Carter, John W. Ward, William G. Whittingham, Luis Simón, Robert S. Paton, Darren J. Dixon from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

Get a shift on: An enantioselective bifunctional iminophosphorane (BIMP)‐catalysed 1,3‐prototropic shift of structurally diverse β,γ‐unsaturated cyclohexenones is reported. The reaction is high yielding (up to 99 %) in a short time span and proceeds with a high level of selectivity (up to 99 % ee) on a wide range of substrates. To complement the experimental data, in‐depth computational studies were undertaken, including multivariate linear regression of TS energy. Abstract A bifunctional iminophosphorane (BIMP)‐catalysed enantioselective synthesis of α,β‐unsaturated cyclohexenones through a facially selective 1,3‐prototropic shift of β,γ‐unsaturated prochiral isomers, under mild reaction conditions and in short reaction times, on a range of structurally diverse substrates, is reported. α,β‐Unsaturated cyclohexenone products primed for downstream derivatisation were obtained in high yields (up to 99 %) and consistently high enantioselectivity (up to 99 % ee). Computational studies into the reaction mechanism and origins of enantioselectivity, including multivariate linear regression of TS energy, were carried out and the obtained data were found to be in good agreement with experimental findings.

Constructing Charge‐Transfer Excited States Based on Frontier Molecular Orbital Engineering: Narrowband Green Electroluminescence with High Color Purity and Efficiency

By Yincai Xu, Chenglong Li, Zhiqiang Li, Qingyang Wang, Xinliang Cai, Jinbei Wei, Yue Wang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

A molecular design strategy based on frontier molecular orbital engineering (FMOE) has been developed for constructing narrowband green emitters. Combining the advantages of a twisted donor–acceptor structure and multiple resonance skeleton has led to an OLED that exhibits a strong narrowband green emission with CIE of (0.23, 0.69) and a maximum external quantum efficiency of 27.0 %. Abstract The design and synthesis of organic materials with a narrow emission band in the longer wavelength region beyond 510 nm remain a great challenge. For constructing narrowband green emitters, we propose a unique molecular design strategy based on frontier molecular orbital engineering (FMOE), which can integrate the advantages of a twisted donor–acceptor (D‐A) structure and a multiple resonance (MR) delayed fluorescence skeleton. Attaching an auxiliary donor to a MR skeleton leads to a novel molecule with twisted D‐A and MR structure characteristics. Importantly, a remarkable red‐shift of the emission maximum and a narrowband spectrum are achieved simultaneously. The target molecule has been employed as an emitter to fabricate green organic light‐emitting diodes (OLEDs) with Commission Internationale de L'Eclairage (CIE) coordinates of (0.23, 0.69) and a maximum external quantum efficiency (EQE) of 27.0 %.

High‐Tc Enantiomeric Ferroelectrics Based on Homochiral Dabco‐derivatives (Dabco=1,4‐Diazabicyclo[2.2.2]octane)

By Da‐Wei Fu, Ji‐Xing Gao, Wen‐Hui He, Xue‐Qin Huang, Yu‐Hua Liu, Yong Ai from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

The first examples of homochiral dabco‐based (dabco=1,4‐diazabicyclo[2.2.2]octane) ferroelectrics, [R‐ and S‐2‐Me‐H2dabco][TFSA]2 (TFSA=bis(trifluoromethylsulfonyl)ammonium), were designed from the non‐ferroelectric [H2dabco][TFSA]2. They show two phase transitions with a transition temperature (Tc) up to 405.8 K and 415.8 K, higher than the Tc of most dabco‐based or homochiral ferroelectrics. Abstract 1,4‐Diazabicyclo[2.2.2]octane (dabco) and its derivatives have been extensively utilized as building units of excellent molecular ferroelectrics for decades. However, the homochiral dabco‐based ferroelectric remains a blank. Herein, by adding a methyl (Me) group accompanied by the introduction of homochirality to the [H2dabco]2+ in the non‐ferroelectric [H2dabco][TFSA]2 (TFSA=bis(trifluoromethylsulfonyl)ammonium), we successfully designed enantiomeric ferroelectrics [R and S‐2‐Me‐H2dabco][TFSA]2. The two enantiomers show two sequential phase transitions with transition temperature (Tc) as high as 405.8 K and 415.8 K, which is outstanding in both dabco‐based ferroelectrics and homochiral ferroelectrics. To our knowledge, [R and S‐2‐Me‐H2dabco][TFSA]2 are the first examples of dabco‐based homochiral ferroelectrics. This finding opens an avenue to construct dabco‐based homochiral ferroelectrics and will inspire the exploration of more eminent enantiomeric molecular ferroelectrics.

Utilizing Vinylcyclopropane Reactivity: Palladium‐Catalyzed Asymmetric [5+2] Dipolar Cycloadditions

By Miao‐Miao Li, Qin Xiong, Bao‐Le Qu, Yu‐Qing Xiao, Yu Lan, Liang‐Qiu Lu, Wen‐Jing Xiao from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

By switching the reactivity of Pd‐containing dipolar intermediates from all‐carbon 1,3‐dipoles to oxo‐1,5‐dipoles, Pd‐catalyzed asymmetric [5+2] cycloadditions of vinylcyclopropanes (VCPs) with photogenerated ketenes are achieved. A variety of chiral seven‐membered lactone‐fused polycyclic molecules are produced with good reaction efficiency and selectivity. Abstract Vinylcyclopropanes (VCPs) are commonly used in transition‐metal‐catalyzed cycloadditions, and the utilization of their recently realized reactivities to construct new cyclic architectures is of great significance in modern synthetic chemistry. Herein, a palladium‐catalyzed, visible‐light‐driven, asymmetric [5+2] cycloaddition of VCPs with α‐diazoketones is accomplished by switching the reactivity of the Pd‐containing dipolar intermediate from an all‐carbon 1,3‐dipole to an oxo‐1,5‐dipole. Enantioenriched seven‐membered lactones were produced with good reaction efficiencies and selectivities (23 examples, 52–92 % yields with up to 99:1 er and 12.5:1 dr). In addition, computational investigations were performed to rationalize the observed high chemo‐ and periselectivities.

The Sphingosine and Acyl Chains of Ceramide [NS] Show Very Different Structure and Dynamics That Challenge Our Understanding of the Skin Barrier

By Oskar Engberg, Andrej Kováčik, Petra Pullmannová, Martin Juhaščik, Lukáš Opálka, Daniel Huster, Kateřina Vávrová from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

Dynamic chains in a rigid matrix: While the sphingosine chains of ceramide molecules in the outermost human skin layer were originally assumed to be fully rigid, spectroscopic data reveals that they display a complex dynamic behavior. These new insights will help fine‐tune the molecular model of the skin lipid barrier. Abstract The lipid phase of the uppermost human skin layer is thought to comprise highly rigid lipids in an orthorhombic phase state to protect the body against the environment. By synthesizing sphingosine‐d28 deuterated N‐lignoceroyl‐d‐erythro‐sphingosine (ceramide [NS]), we compare the structure and dynamics of both chains of that lipid in biologically relevant mixtures using X‐ray diffraction, 2H NMR analysis, and infrared spectroscopy. Our results reveal a substantial fraction of sphingosine chains in a fluid and dynamic phase state at physiological temperature. These findings prompt revision of our current understanding of the skin lipid barrier, where an extended ceramide [NS] conformation is preferred and a possible domain structure is proposed. Mobile lipid chains may be crucial for skin elasticity and the translocation of physiologically important molecules.

Darren Johnson

By from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

“The best advice I have ever been given is in two parts: 1) while it is important in life to learn how to connect dots, you have to collect dots first, and 2) don't forget to give yourself time to think …” Find out more about Darren Johnson in his Author Profile

Pentacyclic Nano‐Trefoil

By Huiyeong Ju, Yumiko Tsuruoka, Miho Hyano, Eunji Lee, Ki-Min Park, Mari Ikeda, Jun-ichi Ishii, Shunsuke Kuwahara, Yoichi Habata from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

Tetra‐armed cyclen ( 1 ) bearing two 4‐(4’‐pyridyl)benzyl and two 3,5‐difluorobenzyl groups and its Ag + complexes were prepared and structurally characterized. The complex formed between 1 and Ag + undergoes a reversible structural transformation between a 2:2 dimeric complex and a 3:5 pentacyclic trefoil complex with changes in the Ag + / 1 molar ratio. It was also revealed that the 3:5 trefoil complex could encapsulate benzene and benzene‐ d 6 selectively in solid‐state. The benzene‐included structures are stabilized by C‐H···F‐C interactions between the benzene molecule and the ligand molecule.

Elucidating Zeolite Channel Geometry–Reaction Intermediate Relationships for the Methanol‐to‐Hydrocarbon Process

By Donglong Fu, Alessandra Lucini Paioni, Cheng Lian, Onno Heijden, Marc Baldus, Bert M. Weckhuysen from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

Zeolite channel geometry–reaction intermediate relationships during the methanol‐to‐hydrocarbon process were identified using advanced solid‐state NMR spectroscopy. As described by M. Baldus, B. M. Weckhuysen, and co‐workers in their Research Article (DOI: 10.1002/anie.202009139), the more extended straight zeolite channels promote the aromatic cycle, while the more constrained sinusoidal zeolite channels favor the olefin cycle.

Oxidative Addition of Water, Alcohols, and Amines in Palladium Catalysis

By Annette Grünwald, Frank W. Heinemann, Dominik Munz from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

The oxidative addition of OH, NH, and weak CH bonds to a palladium(0) complex is facile, allows for additive‐free catalysis, and suggests the non‐innocence of water in palladium catalysis. The oxidative addition of protic solvents or adventitious water switches the chemoselectivity in catalysis with alkynes through activation of the terminal C−H bond. Abstract The homolytic cleavage of O−H and N−H or weak C−H bonds is a key elementary step in redox catalysis, but is thought to be unfeasible for palladium. In stark contrast, reported here is the room temperature and reversible oxidative addition of water, isopropanol, hexafluoroisopropanol, phenol, and aniline to a palladium(0) complex with a cyclic (alkyl)(amino)carbene (CAAC) and a labile pyridino ligand, as is also the case in popular N‐heterocyclic carbene (NHC) palladium(II) precatalysts. The oxidative addition of protic solvents or adventitious water switches the chemoselectivity in catalysis with alkynes through activation of the terminal C−H bond. Most salient, the homolytic activation of alcohols and amines allows atom‐efficient, additive‐free cross‐coupling and transfer hydrogenation under mild reaction conditions with usually unreactive, yet desirable reagents, including esters and bis(pinacolato)diboron.

Food‐Poisoning Bacteria Employ a Citrate Synthase and a Type II NRPS To Synthesize Bolaamphiphilic Lipopeptide Antibiotics

By Benjamin Dose, Claudia Ross, Sarah P. Niehs, Kirstin Scherlach, Johanna P. Bauer, Christian Hertweck from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

When life gives you citrate… Genome mining of food‐spoiling bacteria revealed unprecedented lipocyclopeptides (bolagladins) with antimycobacterial activity. A specialized citrate synthase and nonribosomal peptide synthetases (NRPSs) play key roles in the formation and loading of their unusual tricarboxylic fatty acid tail, thus generating a bolaamphiphilic natural product (see scheme). Abstract Mining the genome of the food‐spoiling bacterium Burkholderia gladioli pv. cocovenenans revealed five nonribosomal peptide synthetase (NRPS) gene clusters, including an orphan gene locus (bol). Gene inactivation and metabolic profiling linked the bol gene cluster to novel bolaamphiphilic lipopeptides with antimycobacterial activity. A combination of chemical analysis and bioinformatics elucidated the structures of bolagladin A and B, lipocyclopeptides featuring an unusual dehydro‐β‐alanine enamide linker fused to an unprecedented tricarboxylic fatty acid tail. Through a series of targeted gene deletions, we proved the involvement of a designated citrate synthase (CS), priming ketosynthases III (KS III), a type II NRPS, including a novel desaturase for enamide formation, and a multimodular NRPS in generating the cyclopeptide. Network analyses revealed the evolutionary origin of the CS and identified cryptic CS/NRPS gene loci in various bacterial genomes.

Enantio‐ and Regioselective NiH‐Catalyzed Reductive Hydroarylation of Vinylarenes with Aryl Iodides

By Yuli He, Chuang Liu, Lei Yu, Shaolin Zhu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

A mild NiH‐catalyzed enantioselective hydroarylation process enabled by a new chiral bis imidazoline ligand is reported. A wide variety of enantioenriched 1,1‐diarylalkanes, a structure found in a number of biologically active molecules, were obtained in high yields with excellent enantioselectivities. Abstract A highly enantio‐ and regioselective hydroarylation process of vinylarenes with aryl halides has been developed using a NiH catalyst and a new chiral bis imidazoline ligand. A broad range of structurally diverse, enantioenriched 1,1‐diarylalkanes, a structure found in a number of biologically active molecules, have been obtained with excellent yields and enantioselectivities under extremely mild conditions.

α‐Selective Ring‐Opening Reactions of Bicyclo[1.1.0]butyl Boronic Ester with Nucleophiles

By Varinder Kumar Aggarwal, Lin Guo, Adam Noble from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

The reaction of bicyclo[1.1.0]butyl pinacol boronic ester (BCB‐Bpin) with nucleophiles has been studied. Unlike BCBs bearing electron‐withdrawing groups, which react with nucleophiles at the β‐position, BCB‐Bpin reacts with a diverse set of heteroatom (O, S, N)‐centred nucleophiles exclusively at the α‐position. Aliphatic alcohols, phenols, carboxylic acids, thiols and sulfonamides were found to be competent nucleophiles, providing ready access to α‐heteroatom‐substituted cyclobutyl boronic esters. In contrast, sterically hindered bis‐sulfonamides and related nucleophiles reacted with BCB‐Bpin at the β’‐position leading to cyclopropanes with high trans‐selectivity. The origin of selectivity is discussed.

A Robust Mixed‐Lanthanide PolyMOF Membrane for Ratiometric Temperature Sensing

By Tongtong Feng, Yingxiang Ye, Xiao Liu, Hui Cui, Zhiqiang Li, Ying Zhang, Bin Liang, Huanrong Li, Banglin Chen from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

A polyMOF membranous luminescent thermometer is realized through the copolymerizion of mixed‐lanthanide MOF with butyl methacrylate monomers. The membrane material not only exhibits ratiometric temperature sensing behavior in a flexible form but also shows remarkable stability under harsh conditions, making it a promising candidate for commercial applications. Abstract Temperature sensors play a significant role in biology, chemistry, and engineering, especially those that can work accurately in a noninvasive manner. We adopted a photoinduced post‐synthetic copolymerization strategy to realize a membranous ratiometric luminescent thermometer based on the emissions of two lanthanide ions. This novel mixed‐lanthanide polyMOF membrane exhibits not only the integrity and temperature sensing behaviour of the Ln‐MOF powder but also excellent mechanical properties, such as flexibility, elasticity, and processability. Moreover, the polyMOF membrane shows remarkable stability under harsh conditions, including high humidity, strong acid and alkali (pH 0–14), which allowed the mapping of temperature distributions in extreme circumstances. This work highlights a simple strategy for polyMOF membrane formation and pushes forward the further practical application of Ln‐MOF‐based luminescent thermometers in various fields and conditions.

Anion Solvation Reconfiguration Enables High‐Voltage Carbonate Electrolytes for Stable Zn/Graphite Cells

By Zheng Chen, Yue Tang, Xiaofan Du, Bingbing Chen, Guoli Lu, Xiaoqi Han, Yaojian Zhang, Wuhai Yang, Pengxian Han, Jingwen Zhao, Guanglei Cui from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

Through the strategy of anion solvation regulation, a reconfigurated anion solvation network is formed which significantly reduces the oxidative‐vulnerable anion‐carbonate affinities. This leads to an enhanced oxidation stability of carbonate electrolytes which enables highly stable Zn/graphite cells. Abstract Conventional carbonate solvents with low HOMO levels are theoretically compatible with the low‐cost, high‐voltage chemistry of Zn/graphite batteries. However, the nucleophilic attack of the anion on carbonates induces an oxidative breakdown at high potentials. Here, we restore the inherent anodic stability of carbonate electrolytes by designing a micro‐heterogeneous anion solvation network. Based on the addition of a strongly electron‐donating solvent, trimethyl phosphate (TMP), the oxidation‐vulnerable anion‐carbonate affinities are decoupled because of the preferential sequestration of anions into solvating TMP domains around the metal cations. The hybridized electrolytes elevate the electrochemical window of carbonate electrolytes by 0.45 V and enable the operation of Zn/graphite dual‐ion cells at 2.80 V with a long cycle life (92 % capacity retention after 1000 cycles). By inheriting the non‐flammability from TMP and the high ion‐transport kinetics from the carbonate systems, this facile strategy provides cells with the additional benefits of fire retardancy and high‐power capability.

A Smart Theranostic Nanocapsule for Spatiotemporally Programmable Photo‐Gene therapy

By Xue Gong, Ruomeng Li, Jing Wang, Jie Wei, Kang Ma, Xiaoqing Liu, Fuan Wang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

A self‐sufficient therapeutic photo‐gene therapy nanosystem was realized through the delicate design of DNAzyme prodrugs and MnO2 adjuvant into nanocapsule with tumor‐specific recognition/activation features. Abstract The therapeutic performance of DNAzyme‐involved gene silencing is significantly constrained by inefficient conditional activation and insufficient cofactor supply. Herein, a self‐sufficient therapeutic nanosystem was realized through the delicate design of DNAzyme prodrugs and MnO2 into a biocompatible nanocapsule with tumor‐specific recognition/activation features. The indocyanine green (ICG)‐modified DNA prodrugs are designed by splitting the DNAzyme and then reconstituted into the exquisite catalyzed hairpin assembly (CHA) amplification circuit. Based on the photothermal activation of ICG, the nanocapsule was disassembled to expose the MnO2 ingredient which was immediately decomposed into Mn2+ ions to supplement an indispensable DNAzyme cofactor on‐demand with a concomitant O2 generation for enhancing the auxiliary phototherapy. The endogenous microRNA catalyzes the amplified assembly of DNA prodrugs via an exquisite CHA principle, leading to the DNAzyme‐mediated simultaneous silencing of two key tumor‐involved mRNAs. This self‐activated theranostic nanocapsule could substantially expand the toolbox for accurate diagnosis and programmable therapeutics.

Aptamers with Tunable Affinity Enable Single‐Molecule Tracking and Localization of Membrane Receptors on Living Cancer Cells

By Pietro Delcanale, David Porciani, Silvia Pujals, Alexander Jurkevich, Andrian Chetrusca, Kwaku D. Tawiah, Donald H. Burke, Lorenzo Albertazzi from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

Rational engineering of low‐affinity aptamers expands the toolkit of affinity probes for super‐resolution microscopy. In their Research Article (DOI: 10.1002/anie.202004764), D. H. Burke, L. Albertazzi, and co‐workers demonstrate that a low‐affinity aptamer targeting cell‐surface EGFR allows for simultaneous single‐molecule tracking and single‐molecule localization microscopy of individual receptors at high labeling density to define spatiotemporal dynamics on living and unperturbed cancer cells. Cover picture: Bri Ebenroth.

Electrochemical Reduction of CO2 to Ethane through Stabilization of an Ethoxy Intermediate

By Anthony Vasileff, Yanping Zhu, Xing Zhi, Yongqiang Zhao, Lei Ge, Hao Ming Chen, Yao Zheng, Shi‐Zhang Qiao from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

Iodide‐derived copper shows higher selectivity and faster kinetics towards ethane production from CO2 than other catalyst systems. In their Communication (DOI: 10.1002/anie.202004846), H. M. Chen, Y. Zheng, S. Z. Qiao, and co‐workers use in situ X‐ray absorption fine structure and in situ Raman techniques to show that trace iodine and positively charged copper species better stabilize the ethoxy intermediate, which was found to be the selectivity‐determining intermediate towards ethane production.

Covalent Triazine Framework Nanoparticles via Size‐Controllable Confinement Synthesis for Enhanced Visible‐Light Photoredox Catalysis

By Wei Huang, Niklas Huber, Shuai Jiang, Katharina Landfester, Kai A. I. Zhang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

Size‐controllable covalent triazine framework nanoparticles were synthesized through a confined polymerization strategy within silica capsules. They show a manifold increase in photocatalytic activity compared to the bulk system. Abstract For metal‐free, organic conjugated polymer‐based photocatalysts, synthesis of defined nanostructures is still highly challenging. Here, we report the formation of covalent triazine framework (CTF) nanoparticles via a size‐controllable confined polymerization strategy. The uniform CTF nanoparticles exhibited significantly enhanced activity in the photocatalytic formation of dibenzofurans compared to the irregular bulk material. The optoelectronic properties of the nanometer‐sized CTFs could be easily tuned by copolymerizing small amounts of benzothiadiazole into the conjugated molecular network. This optimization of electronic properties led to a further increase in observed photocatalytic efficiency, resulting in total an 18‐fold enhancement compared to the bulk material. Full recyclability of the heterogeneous photocatalysts as well as catalytic activity in dehalogenation, hydroxylation and benzoimidazole formation reactions demonstrated the utility of the designed materials.

Complex Cascade Reaction Networks via Cross β Amyloid Nanotubes

By Chiranjit Mahato, Ayan Chatterjee, Dibyendu Das from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

Biocatalytic reaction networks integrate complex cascade transformations via spatial localization of multiple enzymes confined within the cellular milieu. Inspired by Nature’s ingenuity, we demonstrate that short peptide based cross‐β amyloid nanotubular hybrids can promote different kinds of cascade reactions, from simple two‐step, multistep to complex convergent cascades. The compartmentalizing ability of paracrystalline cross‐β phases was utilized to colocalize sarcosine oxidase (SOX) and hemin as artificial peroxidase. Further, the catalytic potential of the amyloid nanotubes with ordered arrays of imidazoles were used as hydrolase mimic. The designed SOX‐hemin amyloid nanohybrids featuring a single extant enzyme could integrate different logic networks to access complex digital designs with the help of three concatenated AND gates and biologically relevant stimuli as inputs.

Photoinduced Aerobic Iodoarene‐Catalyzed Spirocyclization of N‐Oxy‐Amides to N‐Fused Spirolactams

By Kevin Cariou, Loïc Habert from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

Iodoarene catalysis is a powerful methodology that usually requires an excess of oxidant, or of redox mediator if the terminal oxidant is dioxygen, to generate the key hypervalent iodine intermediate to proceed efficiently. We report that, using the spiro‐cyclization of amides as a benchmark reaction, aerobic iodoarene catalysis can be enabled by relying on a pyrylium photocatalyst under blue light irradiation. This unprecedented dual organocatalytic system allows the use of low catalytic loading of both catalysts under very mild operating conditions.

Dual Intramolecular Electron Transfer for In Situ Coreactant‐Embedded Electrochemiluminescence Microimaging of Membrane Protein

By Huangxian Ju, Ningning Wang, Hang Gao, Yunzhi Li, Guangming Li, Weiwei Chen, Zhongchao Jin, Jianping Lei, Qin Wei from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

The demand for transporting coreactant to emitter and short lifetime of the radicals in electrochemiluminescence (ECL) emission inhibit greatly its application in cytosensing and microscopic imaging. Herein we designed a dual intramolecular electron transfer strategy and tertiary amine conjugated polymer dots (TEA‐Pdots) to develop a coreactant‐embedded ECL mechanism and microimaging system. The TEA‐Pdots could produce ECL emission at +1.2 V without need of coreactant in test solution. The superstructure and intramolecular electron transfer led to unprecedented ECL strength, which was 132 and 45 times stronger than those from the mixture of Pdots with TEA at equiv alent and 62.5 times higher amounts, respectively. The ECL efficiency was even higher than that of typical [Ru(bpy) 3 ] 2+ system. Therefore, this strategy and coreactant‐embedded ECL system could be used for in situ ECL microimaging of membrane protein on single living cells without additional permeable treatment for transporting coreactant. The feasibility and validity were demonstrated by evaluating the specific protein expression on cell surface. This work opens new avenues for ECL applications in single cell analysis and dynamic study of biological events.

Hexafluoroisopropanol‐Promoted Haloamidation and Halolactonization of Unactivated Alkenes

By Chenxiao Qi, Guillaume Force, Vincent Gandon, David Leboeuf from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

Pyrrolidine and piperidine derivatives bearing halide functional groups are prevalent building blocks in drug discovery as halides can serve as an anchor for post‐modifications. In principle, one of the simplest ways to build these frameworks is the haloamination of alkenes. While several progresses have been made in this field, notably the development of enantioselective versions, this reaction is still fraught with limitations in terms of reactivity. Besides, a major question remaining is to understand the mechanism at work. The formation of a haliranium intermediate is typically mentioned, but limited mechanistic evidence supports it. Herein, we report an efficient metal‐ and oxidant‐free protocol to achieve the haloamidation of olefins, which is promoted by hexafluoroisopropanol, along with a DFT investigation of the mechanism. We anticipate that these findings should guide the future development of more complex transformations in the field of halofunctionalization.

Directional bonding in {Nb10} inorganic frameworks

By May Nyman, Nicolas P. Martin from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

Metal‐oxo clusters offer opportunity to assemble inorganic and metal‐organic frameworks by a controlled building‐block approach, which led to the revolutionary discoveries of zeolites and MOFs. Polyoxometalate clusters are soluble in water, but more challenging to link into frameworks—the inert oxo‐caps that provide solubility are resistant to replacement or further connectivity. Here we demonstrate how the unique directional bonding and varying basicity of the decaniobate ([Nb10]) oxo‐caps can be exploited to build 1D, 2D, and 3D inorganic frameworks. In nine structures, A+ (A=Li, Na, K, Rb and Cs), AE2+ (AE=Ca, Sr, Ba) and Mn2+ demonstrate that the dimensionality of the obtained material is controlled by cation charge and size. Increased cation charge decreases selectivity for oxo‐site bonding, leading to higher‐dimensional linking. Larger cation radii also decreases bonding selectivity, yielding higher dimensional materials. Ion‐exchange studies of the A+‐Nb10 family shows exclusive selectivity for Cs+ over other alkalis, important for radioactive‐Cs removal and sequestration.

Desolvation‐Triggered Versatile Transfer‐Printing of Pure BN Films with Thermal–Optical Dual Functionality

By Yujin Han, Hyeuk Jin Han, Yoonhyuk Rah, Cheolgyu Kim, Moohyum Kim, Hunhee Lim, Kwang Ho Ahn, Hanhwi Jang, Kyoungsik Yu, Taek‐Soo Kim, Eugene N. Cho, Yeon Sik Jung from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

A facile approach to print a pure boron nitride (BN) film with both high thermal conductivity (≈167 W m−1 K−1) and optical transparency (≈90%) on various substrates is developed based on desolvation‐induced adhesion switching. This approach allows near‐perfect transfer yield (≈100%) while ensuring good interfacial contact, realizing the full potential of the thermal and optical properties of BN for practical devices. Abstract Although hexagonal boron nitride (BN) nanostructures have recently received significant attention due to their unique physical and chemical properties, their applications have been limited by a lack of processability and poor film quality. In this study, a versatile method to transfer‐print high‐quality BN films composed of densely stacked BN nanosheets based on a desolvation‐induced adhesion switching (DIAS) mechanism is developed. It is shown that edge functionalization of BN sheets and rational selection of membrane surface energy combined with systematic control of solvation and desolvation status enable extensive tunability of interfacial interactions at BN–BN, BN–membrane, and BN–substrate boundaries. Therefore, without incorporating any additives in the BN film and applying any surface treatment on target substrates, DIAS achieves a near 100% transfer yield of pure BN films on diverse substrates, including substrates containing significant surface irregularities. The printed BNs demonstrate high optical transparency (>90%) and excellent thermal conductivity (>167 W m−1 K−1) for few‐micrometer‐thick films due to their dense and well‐ordered microstructures. In addition to outstanding heat dissipation capability, substantial optical enhancement effects are confirmed for light‐emitting, photoluminescent, and photovoltaic devices, demonstrating their remarkable promise for next‐generation optoelectronic device platforms.

Long‐Range Ordered Amorphous Atomic Chains as Building Blocks of a Superconducting Quasi‐One‐Dimensional Crystal

By Chao An, Yonghui Zhou, Chunhua Chen, Fucong Fei, Fengqi Song, Changyong Park, Jianhui Zhou, Horst‐Günter Rubahn, Victor V. Moshchalkov, Xuliang Chen, Gufei Zhang, Zhaorong Yang from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

Combination of long‐range ordered and short‐range disordered structures at the atomic level is demonstrated for a quasi‐1D linear chain compound. Under compression, the constituent atomic chains of the material are amorphized without breaking the orientational and periodic translation symmetries of the chain lattice. This lattice of amorphous atomic chains hosts a quantum condensate of Cooper pairs. Abstract Crystalline and amorphous structures are two of the most common solid‐state phases. Crystals having orientational and periodic translation symmetries are usually both short‐range and long‐range ordered, while amorphous materials have no long‐range order. Short‐range ordered but long‐range disordered materials are generally categorized into amorphous phases. In contrast to the extensively studied crystalline and amorphous phases, the combination of short‐range disordered and long‐range ordered structures at the atomic level is extremely rare and so far has only been reported for solvated fullerenes under compression. Here, a report on the creation and investigation of a superconducting quasi‐1D material with long‐range ordered amorphous building blocks is presented. Using a diamond anvil cell, monocrystalline (TaSe4)2I is compressed and a system is created where the TaSe4 atomic chains are in amorphous state without breaking the orientational and periodic translation symmetries of the chain lattice. Strikingly, along with the amorphization of the atomic chains, the insulating (TaSe4)2I becomes a superconductor. The data provide critical insight into a new phase of solid‐state materials. The findings demonstrate a first ever case where superconductivity is hosted by a lattice with periodic but amorphous constituent atomic chains.

A Cost‐Effective, Aqueous‐Solution‐Processed Cathode Interlayer Based on Organosilica Nanodots for Highly Efficient and Stable Organic Solar Cells

By Mengqi Cui, Dan Li, Xiaoyan Du, Na Li, Qikun Rong, Ning Li, Lingling Shui, Guofu Zhou, Xinghua Wang, Christoph J. Brabec, Li Nian from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

An aqueous‐solution‐processed cathode interlayer based on cost‐effective organosilica nanodots (OSiNDs) is demonstrated for organic solar cells (OSCs) with power conversion efficiency over 17% and excellent operational stability. The high photostability of OSiNDs‐based OSCs is attributed to the avoidance of photoinduced shunts and the photocatalytic effect, which are ineluctable shortcomings in inverted OSCs based on ZnO cathode interlayers. Abstract The performance and industrial viability of organic photovoltaics are strongly influenced by the functionality and stability of interface layers. Many of the interface materials most commonly used in the lab are limited in their operational stability or their materials cost and are frequently not transferred toward large‐scale production and industrial applications. In this work, an advanced aqueous‐solution‐processed cathode interface layer is demonstrated based on cost‐effective organosilica nanodots (OSiNDs) synthesized via a simple one‐step hydrothermal reaction. Compared to the interface layers optimized for inverted organic solar cells (i‐OSCs), the OSiNDs cathode interlayer shows improved charge carrier extraction and excellent operational stability for various model photoactive systems, achieving a remarkably high power conversion efficiency up to 17.15%. More importantly, the OSiNDs’ interlayer is extremely stable under thermal stress or photoillumination (UV and AM 1.5G) and undergoes no photochemical reaction with the photoactive materials used. As a result, the operational stability of inverted OSCs under continuous 1 sun illumination (AM 1.5G, 100 mW cm−2) is significantly improved by replacing the commonly used ZnO interlayer with OSiND‐based interfaces.

Facile Morphological Qualification of Transferred Graphene by Phase‐Shifting Interferometry

By Ukjae Lee, Yun Sung Woo, Yoojoong Han, Humberto R. Gutiérrez, Un Jeong Kim, Hyungbin Son from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

Phase‐shifting interferometry (PSI) is successfully demonstrated as a non‐destructive, fast, accurate, and reproducible imaging tool to measure the morphological quality of transferred graphene, compared to conventional imaging tools. Very fine structures, such as graphene wrinkles, various polymer residues on graphene, and tearíng/opening of graphene can be successfully visualized using PSI in a one‐shot measurement within few seconds. Abstract Post‐growth graphene transfer to a variety of host substrates for circuitry fabrication has been among the most popular subjects since its successful development via chemical vapor deposition in the past decade. Fast and reliable evaluation tools for its morphological characteristics are essential for the development of defect‐free transfer protocols. The implementation of conventional techniques, such as Raman spectroscopy, atomic force microscopy (AFM), and transmission electron microscopy in production quality control at an industrial scale is difficult because they are limited to local areas, are time consuming, and their operation is complex. However, through a one‐shot measurement within a few seconds, phase‐shifting interferometry (PSI) successfully scans ≈1 mm2 of transferred graphene with a vertical resolution of ≈0.1 nm. This provides crucial morphological information, such as the surface roughness derived from polymer residues, the thickness of the graphene, and its adhesive strength with respect to the target substrates. Graphene samples transferred via four different methods are evaluated using PSI, Raman spectroscopy, and AFM. Although the thickness of the nanomaterials measured by PSI can be highly sensitive to their refractive indices, PSI is successfully demonstrated to be a powerful tool for investigating the morphological characteristics of the transferred graphene for industrial and research purposes.

Better, Faster, and Less Biased Machine Learning: Electromechanical Switching in Ferroelectric Thin Films

By Lee A. Griffin, Iaroslav Gaponenko, Nazanin Bassiri‐Gharb from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

A fast, easily implementable approach to improve the interpretability of machine‐learning analyses in materials science is demonstrated. Systematic application of techniques and parameter selection curtails the influence of overinterpretation, reduces user bias, and ultimately improves the quality of such studies. Previously identified exotic phenomena in ferroelectric films can be thus well described by classic ferroelectric and non‐ferroelectric phenomena. Abstract Machine‐learning techniques are more and more often applied to the analysis of complex behaviors in materials research. Frequently used to identify fundamental behaviors within large and multidimensional datasets, these techniques are strictly based on mathematical models. Thus, without inherent physical or chemical meaning or constraints, they are prone to biased interpretation. The interpretability of machine‐learning results in materials science, specifically materials’ functionalities, can be vastly improved through physical insights and careful data handling. The use of techniques such as dimensional stacking can provide the much needed physical and chemical constraints, while proper understanding of the assumptions imposed by model parameters can help avoid overinterpretation. These concepts are illustrated by application to recently reported ferroelectric switching experiments in PbZr0.2Ti0.8O3 thin films. Through systematic analysis and introduction of physical constraints, it is argued that the behaviors present are not necessarily due to exotic mechanisms previously suggested, but rather well described by classical ferroelectric switching superimposed by non‐ferroelectric phenomena, such as electrochemical deformation, electrostatic interactions, and/or charge injection.

Graphene‐Quantum‐Dots‐Induced Centimeter‐Sized Growth of Monolayer Organic Crystals for High‐Performance Transistors

By Jinwen Wang, Xiaofeng Wu, Jing Pan, Tanglue Feng, Di Wu, Xiujuan Zhang, Bai Yang, Xiaohong Zhang, Jiansheng Jie from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

A facile graphene quantum dots (GQDs)‐induced self‐assembly method is developed to achieve centimeter‐sized growth of monolayer organic crystals on a solution interface. The spreading area of organic solvent is greatly enhanced by tuning the pH value of the GQDs solution. The strong π–π stacking interactions between the GQDs and the organic molecules also effectively reduce the nucleation energy and afford a cohesive force to bond the precipitated crystals together, enabling large‐area growth of monolayer organic crystals. Organic field‐effect transistors based on the monolayer 2,7‐didecyl benzothienobenzothiopene crystals exhibit a high mobility up to 2.6 cm2 V−1 s−1. Abstract Monolayer organic crystals have attracted considerable attention due to their extraordinary optoelectronic properties. Solution self‐assembly on the surface of water is an effective approach to fabricate monolayer organic crystals. However, due to the difficulties in controlling the spreading of organic solution on the water surface and the weak intermolecular interaction between the organic molecules, large‐area growth of monolayer organic crystals remains a great challenge. Here, a graphene quantum dots (GQDs)‐induced self‐assembly method for centimeter‐sized growth of monolayer organic crystals on a GQDs solution surface is reported. The spreading area of the organic solution can be readily controlled by tuning the pH value of the GQDs solution. Meanwhile, the π–π stacking interaction between the GQDs and the organic molecules can effectively reduce the nucleation energy of the organic molecules and afford a cohesive force to bond the crystals, enabling large‐area growth of monolayer organic crystals. Using 2,7‐didecyl benzothienobenzothiopene (C10‐BTBT) as an examples, centimeter‐sized monolayer C10‐BTBT crystal with uniform molecular packing and crystal orientation is attained. Organic field‐effect transistors based on the monolayer C10‐BTBT crystals exhibit a high mobility up to 2.6 cm2 V−1 s−1, representing the highest mobility value for solution‐assembled monolayer organic crystals. This work provides a feasible route for large‐scale fabrication of monolayer organic crystals toward high‐performance organic devices.

3D Microstructures of Liquid Crystal Networks with Programmed Voxelated Director Fields

By Yubing Guo, Hamed Shahsavan, Metin Sitti from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

3D liquid crystal network microstructures, such as micrometer‐scale suspended films, helical coils, and circular rings, with programmable 3D director fields, are demonstrated with direct laser writing. High‐resolution (around 5 µm) programmed fields are enabled by pixelated microchannels. Various shape morphing modes are obtained by varying the programmed 3D director fields inside the same liquid crystal network microstructures. Abstract The shape‐shifting behavior of liquid crystal networks (LCNs) and elastomers (LCEs) is a result of an interplay between their initial geometrical shape and their molecular alignment. For years, reliance on either one‐step in situ or two‐step film processing techniques has limited the shape‐change transformations from 2D to 3D geometries. The combination of various fabrication techniques, alignment methods, and chemical formulations developed in recent years has introduced new opportunities to achieve 3D‐to‐3D shape‐transformations in large scales, albeit the precise control of local molecular alignment in microscale 3D constructs remains a challenge. Here, the voxel‐by‐voxel encoding of nematic alignment in 3D microstructures of LCNs produced by two‐photon polymerization using high‐resolution topographical features is demonstrated. 3D LCN microstructures (suspended films, coils, and rings) with designable 2D and 3D director fields with a resolution of 5 µm are achieved. Different shape transformations of LCN microstructures with the same geometry but dissimilar molecular alignments upon actuation are elicited. This strategy offers higher freedom in the shape‐change programming of 3D LCN microstructures and expands their applicability in emerging technologies, such as small‐scale soft robots and devices and responsive surfaces.

Cellulose‐Based Fully Green Triboelectric Nanogenerators with Output Power Density of 300 W m−2

By Renyun Zhang, Christina Dahlström, Haiyang Zou, Julia Jonzon, Magnus Hummelgård, Jonas Örtegren, Nicklas Blomquist, Ya Yang, Henrik Andersson, Martin Olsen, Magnus Norgren, Håkan Olin, Zhong Lin Wang from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

Fully green triboelectric nanogenerators (FG‐TENGs) are made with cellulose materials and graphite electrodes that have output power density of up to 300 W m−2. The mechanism behind the high output is the high density of the regenerated cellulose that eliminates the influence of moisture. Such a high output density is on the same order of magnitude as that obtained with fluoropolymers. Abstract Triboelectric nanogenerators (TENGs) have attracted increasing attention because of their excellent energy conversion efficiency, the diverse choice of materials, and their broad applications in energy harvesting devices and self‐powered sensors. New materials have been explored, including green materials, but their performances have not yet reached the level of that for fluoropolymers. Here, a high‐performance, fully green TENG (FG‐TENG) using cellulose‐based tribolayers is reported. It is shown that the FG‐TENG has an output power density of above 300 W m−2, which is a new record for green‐material‐based TENGs. The high performance of the FG‐TENG is due to the high positive charge density of the regenerated cellulose. The FG‐TENG is stable after more than 30 000 cycles of operations in humidity of 30%–84%. This work demonstrates that high‐performance TENGs can be made using natural green materials for a broad range of applications.

Superhigh Uniform Magnetic Cr Substitution in a 2D Mo2C Superconductor for a Macroscopic‐Scale Kondo Effect

By Chuan Xu, Zhen Liu, Zongyuan Zhang, Zhibo Liu, Jingyin Li, Minghu Pan, Ning Kang, Hui‐Ming Cheng, Wencai Ren from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

Controlled uniform lattice substitution of a 2D Mo2C superconductor by magnetic Cr atoms is performed through chemical vapor deposition, with the Cr concentration up to ≈46.9 at%. The controlled substitutional doping enables the tuning of the competition of the 2D superconductor and the Kondo effect across the whole sample, and the Kondo effect with a high Kondo temperature is achieved at high Cr concentration. Abstract Substitutional doping provides an effective strategy to tailor the properties of 2D materials, but it remains an open challenge to achieve tunable uniform doping, especially at high doping level. Here, uniform lattice substitution of a 2D Mo2C superconductor by magnetic Cr atoms with controlled concentration up to ≈46.9 at% by chemical vapor deposition and a specifically designed Cu/Cr/Mo trilayer growth substrate is reported. The concentration of Cr atoms can be easily tuned by simply changing the thickness of the Cr layer, and the samples retain the original structure of 2D Mo2C even at a very high Cr concentration. The controlled uniform Cr doping enables the tuning of the competition of the 2D superconductor and the Kondo effect across the whole sample. Transport measurements show that with increasing Cr concentration, the superconductivity of the 2D Cr‐doped Mo2C crystals disappears along with the emergence of the Kondo effect, and the Kondo temperature increases monotonously. Using scanning tunneling microscopy/spectroscopy, the mechanism of the doping level effect on the interplay and evolution between superconductivity and the Kondo effect is revealed. This work paves a new way for the synthesis of 2D materials with widely tunable doping levels, and provides new understandings on the interplay between superconductivity and magnetism in the 2D limit.

Magnetic Skyrmions in a Hall Balance with Interfacial Canted Magnetizations

By Jingyan Zhang, Ying Zhang, Yang Gao, Guoping Zhao, Lei Qiu, Kaiyou Wang, Pengwei Dou, Wenlin Peng, Yuan Zhuang, Yanfei Wu, Guoqiang Yu, Zhaozhao Zhu, Yunchi Zhao, Yaqin Guo, Tao Zhu, Jianwang Cai, Baogen Shen, Shouguo Wang from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

Néel‐type skyrmions at zero field and room temperature are experimentally observed using Lorentz‐TEM in a Hall balance with core structure of [Co/Pt]n/NiO/[Co/Pt]n. Interfacial canted magnetizations across NiO spacer give rise to the nucleation of high‐density skyrmions under pulsed current, which shows a strong dependence on interlayer exchange coupling. The physical mechanism of the skyrmions in synthetic antiferromagnets is presented. Abstract Magnetic skyrmions are attracting interest as efficient information‐storage devices with low energy consumption, and have been experimentally and theoretically investigated in multilayers including ferromagnets, ferrimagnets, and antiferromagnets. The 3D spin texture of skyrmions demonstrated in ferromagnetic multilayers provides a powerful pathway for understanding the stabilization of ferromagnetic skyrmions. However, the manipulation mechanism of skyrmions in antiferromagnets is still lacking. A Hall balance with a ferromagnet/insulating spacer/ferromagnet structure is considered to be a promising candidate to study skyrmions in synthetic antiferromagnets. Here, high‐density Néel‐type skyrmions are experimentally observed at zero field and room temperature by Lorentz transmission electron microscopy in a Hall balance (core structure [Co/Pt]n/NiO/[Co/Pt]n) with interfacial canted magnetizations because of interlayer ferromagnetic/antiferromagnetic coupling between top and bottom [Co/Pt]n multilayers, where the Co layers in [Co/Pt]n are always ferromagnetically coupled. Micromagnetic simulations show that the generation and density of skyrmions are strongly dependent on interlayer exchange coupling (IEC) and easy‐axis orientation. Direct experimental evidence of skyrmions in synthetic antiferromagnets is provided, suggesting that the proposed approach offers a promising alternative mechanism for room‐temperature spintronics.

A Non‐Invasive Nanoprobe for In Vivo Photoacoustic Imaging of Vulnerable Atherosclerotic Plaque

By Xiaoxiao Ge, Hongtu Cui, Jian Kong, Shi‐Yu Lu, Rui Zhan, Jianing Gao, Yangkai Xu, Shuangyan Lin, Kaixin Meng, Lingyun Zu, Shaojun Guo, Lemin Zheng from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

Direct identification of vulnerable atherosclerotic plaque at the molecular level is critical to prevent cardiovascular death. Osteopontin antibody (OPN Ab)/Ti3C2/indocyanine green nanoprobes with excellent photoacoustic performance well realize the non‐invasive in vivo imaging of vulnerable plaque through the targeted recognition of OPN‐overexpressed foam cells that are the main ingredients of vulnerable plaque, significantly advancing the innovation of cardiovascular disease diagnosis technology. Abstract Vulnerable atherosclerotic (AS) plaque is the major cause of cardiovascular death. However, clinical methods cannot directly identify the vulnerable AS plaque at molecule level. Herein, osteopontin antibody (OPN Ab) and NIR fluorescence molecules of ICG co‐assembled Ti3C2 nanosheets are reported as an advanced nanoprobe (OPN Ab/Ti3C2/ICG) with enhanced photoacoustic (PA) performance for direct and non‐invasive in vivo visual imaging of vulnerable AS plaque. The designed OPN Ab/Ti3C2/ICG nanoprobes successfully realize obvious NIR fluorescence imaging toward foam cells as well as the vulnerable AS plaque slices. After intravenous injection of OPN Ab/Ti3C2/ICG nanoprobes into AS model mice, in vivo imaging results show a significantly enhanced PA signal in the aortic arch accumulated with vulnerable plaque, well indicating the remarkable feasibility of OPN Ab/Ti3C2/ICG nanoprobes to distinguish the vulnerable AS plaque. The proposed OPN Ab/Ti3C2/ICG nanoprobes not only overcome the clinical difficulty to differentiate vulnerable plaque, but also achieve the non‐invasively specific in vivo imaging of vulnerable AS plaque at molecule level, greatly promoting the innovation of cardiovascular diagnosis technology.

Proximity‐Coupling‐Induced Significant Enhancement of Coercive Field and Curie Temperature in 2D van der Waals Heterostructures

By Luman Zhang, Xinyu Huang, Hongwei Dai, Mingshan Wang, Hui Cheng, Lei Tong, Zheng Li, Xiaotao Han, Xia Wang, Lei Ye, Junbo Han from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

Significant enhancements of Curie temperature (TC) and coercive field (HC) are achieved in ultrathin Fe3GeTe2 (FGT) flakes by using the proximity effect between FGT and FePS3 (FPS). The TC is improved by more than 30 K and the HC is increased by ≈100%, which makes 2D FPS/FGT heterostructures promising candidates for applications in magnetic sensors and storage devices. Abstract Magnetism in 2D has long been the focus of condensed matter physics due to its important applications in spintronic devices. A particularly promising aspect of 2D magnetism is the ability to fabricate 2D heterostructures with engineered optical, electrical, and quantum properties. Recently, the discovery of intrinsic ferromagnetisms in atomic thick materials has provided a new platform for investigations of fundamental magnetic physics. In contrast to 2D CrI3 and Cr2Ge2Te6 insulators, itinerant ferromagnetic Fe3GeTe2 (FGT), which has a larger intrinsic perpendicular anisotropy, higher Curie temperature (TC), and relatively better stability, is a promising candidate for achieving permanent room‐temperature ferromagnetism through interface or component engineering. Here, it is shown that the ferromagnetic properties of FGT thin flakes can be modulated through coupling with a FePS3. The magneto‐optical Kerr effect results show that the TC of FGT is improved by more than 30 K and that the coercive field is increased by ≈100% due to the proximity coupling effect, which changes the spin textures of FGT at the interface. This work reveals that antiferromagnet/ferromagnet coupling is a promising way to engineer the magnetic properties of itinerant 2D ferromagnets, which paves the way for applications in advanced magnetic spintronic and memory devices.

Enantiomeric MOF Crystals Using Helical Channels as Palettes with Bright White Circularly Polarized Luminescence

By Chong Zhang, Zhi‐Ping Yan, Xi‐Yan Dong, Zhen Han, Si Li, Ting Fu, Yan‐Yan Zhu, You‐Xuan Zheng, Yun‐Yin Niu, Shuang‐Quan Zang from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

Achiral‐aggregation‐caused quenching fluorophores are helically arranged in the chiral channels of enantiomeric metal–organic frameworks (MOFs) for color‐tunable and bright white circularly polarized luminescence (photoluminescence quantum yield (PLQY), ≈33%). The experimental results indicate that the helical arrangement is superior to the ET process in the amplification of the luminescence dissymmetry factor. Also, the MOF‐based composites are assembled into a bright white circularly polarized light‐emitting diode (PLQY, ≈30%). Abstract The host–guest chemistry of metal–organic frameworks (MOFs) has enabled the derivation of numerous new functionalities. However, intrinsically chiral MOFs (CMOFs) with helical channels have not been used to realize crystalline circularly polarized luminescence (CPL) materials. Herein, enantiomeric pairs of MOF crystals are reported, where achiral fluorophores adhere to the inner surface of helical channels via biology‐like H‐bonds and hence inherit the helicity of the host MOFs, eventually amplifying the luminescence dissymmetry factor (glum) of the host l/d‐CMOF (±1.50 × 10−3) to a maximum of ±0.0115 for the composite l/d‐CMOF⊃fluorophores. l/d‐CMOF⊃fluorophores in pairs generate bright color‐tunable CPL and almost ideal white CPL (0.33, 0.32) with a record‐high photoluminescence quantum yield of ≈30%, which are further assembled into a white circularly polarized light‐emitting diode. The present strategy opens a new avenue for propagating the chirality of MOFs to realize universal chiroptical materials.

In Situ Designing a Gradient Li+ Capture and Quasi‐Spontaneous Diffusion Anode Protection Layer toward Long‐Life Li−O2 Batteries

By Yue Yu, Gang Huang, Jia‐Zhi Wang, Kai Li, Jin‐Ling Ma, Xin‐Bo Zhang from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

A gradient LiF/F‐doped carbon protection layer with synergistic functions of homogenizing Li+ flux, fast Li+ diffusion ability, and low Li+ diffusion barrier is prepared by a one‐step in situ reaction to solve the challenges relating to unstable lithium anode in Li–O2 batteries, and, as a result, significantly boost the cycling stability of the Li–O2 batteries. Abstract Lithium metal is the only anode material that can enable the Li−O2 battery to realize its high theoretical energy density (≈3500 Wh kg−1). However, the inherent uncontrolled dendrite growth and serious corrosion limitations of lithium metal anodes make it experience fast degradation and impede the practical application of Li−O2 batteries. Herein, a multifunctional complementary LiF/F‐doped carbon gradient protection layer on a lithium metal anode by one‐step in situ reaction of molten Li with poly(tetrafluoroethylene) (PTFE) is developed. The abundant strong polar C‐F bonds in the upper carbon can not only act as Li+ capture site to pre‐uniform Li+ flux but also regulate the electron configuration of LiF to make Li+ quasi‐spontaneously diffuse from carbon to LiF surface, avoiding the strong Li+‐adhesion‐induced Li aggregation. For LiF, it can behave as fast Li+ conductor and homogenize the nucleation sites on lithium, as well as ensure firm connection with lithium. As a result, this well‐designed protection layer endows the Li metal anode with dendrite‐free plating/stripping and anticorrosion behavior both in ether‐based and carbonate ester‐based electrolytes. Even applied protected Li anodes in Li−O2 batteries, its superiority can still be maintained, making the cell achieve stable cycling performance (180 cycles).

Perovskite Films with Reduced Interfacial Strains via a Molecular‐Level Flexible Interlayer for Photovoltaic Application

By Cong‐Cong Zhang, Shuai Yuan, Yan‐Hui Lou, Qing‐Wei Liu, Meng Li, Hiroyuki Okada, Zhao‐Kui Wang from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

A protonated amino silane coupling agent as an interlayer is exploited on rigid and flexible substrates, which not only sets up well‐matched growth underlay but also serves as a structural component of the lattice units, leading to less‐distorted perovskite films, resulting in an obvious advance in device performance, stability, and mechanical tolerance in the corresponding flexible device. Abstract Interface strains and lattice distortion are inevitable issues during perovskite crystallization. Silane as a coupling agent is a popular connector to enhance the compatibility between inorganic and organic materials in semiconductor devices. Herein, a protonated amine silane coupling agent (PASCA‐Br) interlayer between TiO2 and perovskite layers is adopted to directionally grasp both of them by forming the structural component of a lattice unit. The pillowy alkyl ammonium bromide terminals at the upper side of the interlayer provide well‐matched growth sites for the perovskite, leading to mitigated interface strain and ensuing lattice distortion; meanwhile, its superior chemical compatibility presents an ideal effect on healing the under‐coordinated Pb atoms and halogen vacancies of bare perovskite crystals. The PASCA‐Br interlayer also serves as a mechanical buffer layer, inducing less cracked perovskite film when bending. The developed molecular‐level flexible interlayer provides a promising interfacial engineering for perovskite solar cells and their flexible application.

Embedded Nickel‐Mesh Transparent Electrodes for Highly Efficient and Mechanically Stable Flexible Perovskite Photovoltaics: Toward a Portable Mobile Energy Source

By Meng Li, Wei‐Wei Zuo, Antonio Gaetano Ricciardulli, Ying‐Guo Yang, Yan‐Hua Liu, Qiong Wang, Kai‐Li Wang, Gui‐Xiang Li, Michael Saliba, Diego Di Girolamo, Antonio Abate, Zhao‐Kui Wang from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

Research on flexible mobile energy‐supply devices will promote the development of the Internet of Things. An embedded metal nickel (Ni)‐mesh transparent conductive electrode is used as a flexible substrate for perovskite solar cells (PSCs). These Ni‐mesh‐based PSCs exhibit excellent electric properties and remarkable environmental and mechanical stability. Abstract The rapid development of Internet of Things mobile terminals has accelerated the market's demand for portable mobile power supplies and flexible wearable devices. Here, an embedded metal‐mesh transparent conductive electrode (TCE) is prepared on poly(ethylene terephthalate) (PET) using a novel selective electrodeposition process combined with inverted film‐processing methods. This embedded nickel (Ni)‐mesh flexible TCE shows excellent photoelectric performance (sheet resistance of ≈0.2–0.5 Ω sq−1 at high transmittance of ≈85–87%) and mechanical durability. The PET/Ni‐mesh/polymer poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS PH1000) hybrid electrode is used as a transparent electrode for perovskite solar cells (PSCs), which exhibit excellent electric properties and remarkable environmental and mechanical stability. A power conversion efficiency of 17.3% is obtained, which is the highest efficiency for a PSC based on flexible transparent metal electrodes to date. For perovskite crystals that require harsh growth conditions, their mechanical stability and environmental stability on flexible transparent embedded metal substrates are studied and improved. The resulting flexible device retains 76% of the original efficiency after 2000 bending cycles. The results of this work provide a step improvement in flexible PSCs.

Redistributing Li‐Ion Flux by Parallelly Aligned Holey Nanosheets for Dendrite‐Free Li Metal Anodes

By Yangen Zhou, Xiao Zhang, Yu Ding, Jiwoong Bae, Xuelin Guo, Yu Zhao, Guihua Yu from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

Parallelly aligned holey 2D materials on a lithium metal anode are designed to redistribute the nonuniform Li‐ion flux both in the electrolyte and in the solid‐electrolyte interphase, as well as to provide fast Li‐ion transport. The protected Li anode achieves ultralong lifetime with low overpotential at a high rate with high capacity. Abstract Li metal is the most ideal anode material to assemble rechargeable batteries with high energy density. However, nonuniform Li‐ion flux during repeated Li plating and stripping leads to continuous Li dendrite growth and dead Li formation, which causes safety risks and short lifetime and thus impedes the commercialization of Li metal batteries. Here, parallelly aligned holey nanosheets on a Li metal anode are reported to simultaneously redistribute the Li‐ion flux in the electrolyte and in the solid‐electrolyte interphase, which allows uniform Li‐ion distribution as well as fast Li‐ion diffusion for reversible Li plating and stripping. With holey MgO nanosheets as an example, the protected Li anodes achieve Coulombic efficiency of ≈99% and ultralong‐term reversible Li plating/stripping over 2500 h at a high current density of 10 mA cm−2. A full‐cell battery, using the protected anode, a 4 V Li‐ion cathode, and a commercial carbonate electrolyte, shows capacity retention of 90.9% after 500 cycles.

Unconventional Charge–Spin Conversion in Weyl‐Semimetal WTe2

By Bing Zhao, Bogdan Karpiak, Dmitrii Khokhriakov, Annika Johansson, Anamul Md. Hoque, Xiaoguang Xu, Yong Jiang, Ingrid Mertig, Saroj P. Dash from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

An outstanding feature of the topological Weyl semimetal WTe2 is its novel spin topologies in the electronic band structure. An unconventional charge–spin conversion in WTe2 due to its lower crystal symmetry combined with large Berry curvature and spin‐texture of the Fermi states is demonstrated. These findings have great potential for utilizing WTe2 for spintronic circuits and quantum technologies. Abstract An outstanding feature of topological quantum materials is their novel spin topology in the electronic band structures with an expected large charge‐to‐spin conversion efficiency. Here, a charge‐current‐induced spin polarization in the type‐II Weyl semimetal candidate WTe2 and efficient spin injection and detection in a graphene channel up to room temperature are reported. Contrary to the conventional spin Hall and Rashba–Edelstein effects, the measurements indicate an unconventional charge‐to‐spin conversion in WTe2, which is primarily forbidden by the crystal symmetry of the system. Such a large spin polarization can be possible in WTe2 due to a reduced crystal symmetry combined with its large spin Berry curvature, spin–orbit interaction with a novel spin‐texture of the Fermi states. A robust and practical method is demonstrated for electrical creation and detection of such a spin polarization using both charge‐to‐spin conversion and its inverse phenomenon and utilized it for efficient spin injection and detection in the graphene channel up to room temperature. These findings open opportunities for utilizing topological Weyl materials as nonmagnetic spin sources in all‐electrical van der Waals spintronic circuits and for low‐power and high‐performance nonvolatile spintronic technologies.

Enabling High‐Performance Tandem Organic Photovoltaic Cells by Balancing the Front and Rear Subcells

By Pei Cheng, Hao‐Cheng Wang, Ran Zheng, Yuan Zhu, Shuixing Dai, Zeyuan Li, Chung‐Hao Chen, Yepin Zhao, Rui Wang, Dong Meng, Chenhui Zhu, Kung‐Hwa Wei, Xiaowei Zhan, Yang Yang from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

In tandem organic photovoltaics, most ultraviolet–visible photons are absorbed by the front sub‐cell, so in the rear sub‐cell, excitons generated on large‐bandgap donors will be reduced significantly. This reduces the conductivity and limits the hole‐transporting property of the rear sub‐cell. An infrared‐absorbing polymer donor is introduced, which provides a second hole‐generation/transporting mechanism to minimize the aforementioned detrimental effects. Abstract In tandem organic photovoltaics, the front subcell is based on large‐bandgap materials, whereas the case of the rear subcell is more complicated. The rear subcell is generally composed of a narrow‐bandgap acceptor for infrared absorption but a large‐bandgap donor to realize a high open‐circuit voltage. Unfortunately, most of the ultraviolet–visible part of the photons are absorbed by the front subcell; as a result, in the rear subcell, the number of excitons generated on large‐bandgap donors will be reduced significantly. This reduces the (photo) conductivity and finally limits the hole‐transporting property of the rear subcell. In this work, a simple and effective way is proposed to resolve this critical issue. To ensure sufficient photogenerated holes in the rear subcell, a small amount of an infrared‐absorbing polymer donor as a third component is introduced, which provides a second hole‐generation and transporting mechanism to minimize the aforementioned detrimental effects. Finally, the short‐circuit current density of the two‐terminal tandem organic photovoltaic is significantly enhanced from 10.3 to 11.7 mA cm−2 (while retaining the open‐circuit voltage and fill factor) to result in an enhanced power conversion efficiency of 15.1%.

A Metal–Organic Framework as a Multifunctional Ionic Sieve Membrane for Long‐Life Aqueous Zinc–Iodide Batteries

By Huijun Yang, Yu Qiao, Zhi Chang, Han Deng, Ping He, Haoshen Zhou from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

Space‐resolution Raman and micro‐IR spectroscopies originally revealed the negative influence of water and iodine species to zinc anode. A metal–organic framework (MOF) membrane is adopted to concurrently suppress shuttling of triiodide and regulate electrolyte solvation. Benefiting from the MOF membrane, an aqueous zinc–iodide battery achieves long life (>6000 cycles), high capacity retention (84.6%), and high reversibility (Coulombic efficiency: 99.65%). Abstract The introduction of the redox couple of triiodide/iodide (I3−/I−) into aqueous rechargeable zinc batteries is a promising energy‐storage resource owing to its safety and cost‐effectiveness. Nevertheless, the limited lifespan of zinc–iodine (Zn–I2) batteries is currently far from satisfactory owing to the uncontrolled shuttling of triiodide and unfavorable side‐reactions on the Zn anode. Herein, space‐resolution Raman and micro‐IR spectroscopies reveal that the Zn anode suffers from corrosion induced by both water and iodine species. Then, a metal–organic framework (MOF) is exploited as an ionic sieve membrane to simultaneously resolve these problems for Zn–I2 batteries. The multifunctional MOF membrane, first, suppresses the shuttling of I3− and restrains related parasitic side‐reaction on the Zn anode. Furthermore, by regulating the electrolyte solvation structure, the MOF channels construct a unique electrolyte structure (more aggregative ion associations than in saturated electrolyte). With the concurrent improvement on both the iodine cathode and the Zn anode, Zn–I2 batteries achieve an ultralong lifespan (>6000 cycles), high capacity retention (84.6%), and high reversibility (Coulombic efficiency: 99.65%). This work not only systematically reveals the parasitic influence of free water and iodine species to the Zn anode, but also provides an efficient strategy to develop long‐life aqueous Zn–I2 batteries.

Evaporated SexTe1‐x Thin Films with Tunable Bandgaps for Short‐Wave Infrared Photodetectors

By Chaoliang Tan, Matin Amani, Chunsong Zhao, Mark Hettick, Xiaohui Song, Der‐Hsien Lien, Hao Li, Matthew Yeh, Vivek Raj Shrestha, Kenneth B. Crozier, Mary C. Scott, Ali Javey from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

Thermally evaporated SexTe1‐x alloy thin films with tunable bandgaps (from 0.31 eV to 1.87 eV) are prepared for the fabrication of high‐performance short‐wave infrared photodetectors. The Se0.32Te0.68‐film‐based photoconductor fabricated on an optical cavity substrate exhibits a cut‐off wavelength at ≈1.7 μm and gives a responsivity of 1.5 AW−1 and implied detectivity of 6.5 × 1010 cm Hz1/2 W−1 at 1.55 μm at room temperature. Abstract Semiconducting absorbers in high‐performance short‐wave infrared (SWIR) photodetectors and imaging sensor arrays are dominated by single‐crystalline germanium and III–V semiconductors. However, these materials require complex growth and device fabrication procedures. Here, thermally evaporated SexTe1‐x alloy thin films with tunable bandgaps for the fabrication of high‐performance SWIR photodetectors are reported. From absorption measurements, it is shown that the bandgaps of SexTe1‐x films can be tuned continuously from 0.31 eV (Te) to 1.87 eV (Se). Owing to their tunable bandgaps, the peak responsivity position and photoresponse edge of SexTe1‐x film‐based photoconductors can be tuned in the SWIR regime. By using an optical cavity substrate consisting of Au/Al2O3 to enhance its absorption near the bandgap edge, the Se0.32Te0.68 film (an optical bandgap of ≈0.8 eV)‐based photoconductor exhibits a cut‐off wavelength at ≈1.7 μm and gives a responsivity of 1.5 AW−1 and implied detectivity of 6.5 × 1010 cm Hz1/2 W−1 at 1.55 μm at room temperature. Importantly, the nature of the thermal evaporation process enables the fabrication of Se0.32Te0.68‐based 42 × 42 focal plane arrays with good pixel uniformity, demonstrating the potential of this unique material system used for infrared imaging sensor systems.

Tumor‐Activated Size‐Enlargeable Bioinspired Lipoproteins Access Cancer Cells in Tumor to Elicit Anti‐Tumor Immune Responses

By Jie Li, Hong Wang, Yuqi Wang, Xiang Gong, Xiaoxuan Xu, Xianyi Sha, Ao Zhang, Zhiwen Zhang, Yaping Li from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

The use of immunogenic cell death (ICD)‐inducing agents has potential to potentiate antitumor immune responses and remodel the immunosuppression in tumor, but is tremendously hampered by the poor delivery efficiency. A tumor‐activated size‐enlargeable bioinspired lipoprotein of oxaliplatin prodrug (TA‐OBL) with efficient cancer cell accessibility is designed to boost the ICD‐induced antitumor immunity for synergizing immune‐checkpoint‐blockades‐mediated cancer immunotherapy. Abstract The limited lymphocytes infiltration and immunosuppression in tumor are the major challenges of cancer immunotherapy. The use of immunogenic cell death (ICD)‐inducing agents has potential to potentiate antitumor immune responses, but is tremendously hampered by the poor delivery efficiency. Herein, a tumor‐activated size‐enlargeable bioinspired lipoprotein of oxaliplatin (TA‐OBL) is designed to access cancer cells and boost the ICD‐induced antitumor immunity for synergizing immune‐checkpoint blockades (ICBs)‐mediated immunotherapy. TA‐OBL is constructed by integrating a legumain‐sensitive melittin conjugate for improving intratumoral permeation and cancer cell accessibility, a pH‐sensitive phospholipid for triggering size‐enlargement and drug release in intracellular acidic environments, a nitroreductase‐sensitive hydrophobic oxaliplatin prodrug (N‐OXP) for eliciting antitumor immunity into the bioinspired nano‐sized lipoprotein system. TA‐OBL treatment produced robust antitumor immune responses and its combination with ICBs demonstrates strong therapeutic benefits with delayed tumor growth and extended survival rate, making it a promising delivery nanoplatform to elicit antitumor immunity for cancer immunotherapy.

3D Ordering at the Liquid–Solid Polar Interface of Nanowires

By Mahdi Zamani, Giulio Imbalzano, Nicolas Tappy, Duncan T. L. Alexander, Sara Martí‐Sánchez, Lea Ghisalberti, Quentin M. Ramasse, Martin Friedl, Gözde Tütüncüoglu, Luca Francaviglia, Sebastien Bienvenue, Cécile Hébert, Jordi Arbiol, Michele Ceriotti, Anna Fontcuberta i Morral from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

Experimental observations and molecular dynamics simulations highlight the 3D nature of atomic‐scale ordering of liquid Ga in contact with solid GaAs in a nanowire growth configuration, elucidating the role played by the liquid ordering in controlling the growth. Abstract The nature of the liquid–solid interface determines the characteristics of a variety of physical phenomena, including catalysis, electrochemistry, lubrication, and crystal growth. Most of the established models for crystal growth are based on macroscopic thermodynamics, neglecting the atomistic nature of the liquid–solid interface. Here, experimental observations and molecular dynamics simulations are employed to identify the 3D nature of an atomic‐scale ordering of liquid Ga in contact with solid GaAs in a nanowire growth configuration. An interplay between the liquid ordering and the formation of a new bilayer is revealed, which, contrary to the established theories, suggests that the preference for a certain polarity and polytypism is influenced by the atomic structure of the interface. The conclusions of this work open new avenues for the understanding of crystal growth, as well as other processes and systems involving a liquid–solid interface.

A High‐Energy Aqueous Manganese–Metal Hydride Hybrid Battery

By Meng Yang, Ru Chen, Yinlin Shen, Xiangyu Zhao, Xiaodong Shen from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

A high‐energy aqueous manganese–metal hydride battery is developed based on Mn2+/MnO2 two‐electron reactions at the cathode and on hydrogen absorption/desorption reactions at the anode. This new aqueous hybrid battery can achieve a high operating voltage of about 2.2 V and an impressive energy density of about 240 Wh kg−1. Abstract Aqueous rechargeable batteries show great application prospects in large‐scale energy storage because of their reliable safety and low cost. However, a key challenge in developing this battery system lies in its low energy density. Herein, a high‐energy manganese–metal hydride (Mn–MH) hybrid battery is reported in which a Mn‐based cathode operated by the Mn2+/MnO2 deposition–dissolution reactions, a hydrogen‐storage alloy anode that absorbs and desorbs hydrogen in an alkaline solution, and a proton‐exchange membrane separator are employed. Given the benefit derived from the high solubility and high specific capacity of the Lewis acidic MnCl2 in the cathode and the low electrode potential of the MH anode, this aqueous Mn–MH hybrid battery exhibits impressive electrochemical properties with admirable discharge voltage plateaus up to 2.2 V, a competitive energy density of about 240 Wh kg−1 (based on the total mass of the 5.5 m MnCl2 solution and the hydrogen storage alloy electrode system), good cycling stability over 130 cycles, and a desirable rate capability. This work demonstrates a new strategy for achieving high‐performance and low‐cost aqueous rechargeable batteries.

A Machine‐Fabricated 3D Honeycomb‐Structured Flame‐Retardant Triboelectric Fabric for Fire Escape and Rescue

By Liyun Ma, Ronghui Wu, Sai Liu, Aniruddha Patil, Hao Gong, Jia Yi, Feifan Sheng, Yuzei Zhang, Jiang Wang, Jun Wang, Wenxi Guo, Zhong Lin Wang from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

A multifunctional 3D honeycomb‐structure fabric triboelectric nanogenerator (3D F‐TENG) is fabricated from yarn to fabric by scalable and continuous textile fabrication technology. The 3D F‐TENG can be used as a smart indoor carpet, which has functions of flame retardancy, noise reduction, precise rescue location, and real‐time route guidance under fire conditions. Abstract Fire disaster is one of the most common hazards that threaten public safety and social development: how to improve the fire escape and rescue capacity remains a huge challenge. Here, a 3D honeycomb‐structured woven fabric triboelectric nanogenerator (F‐TENG) based on a flame‐retardant wrapping yarn is developed. The wrapping yarn is fabricated through a continuous hollow spindle fancy twister technology, which is compatible with traditional textile production processes. The resulting 3D F‐TENG can be used in smart carpets as a self‐powered escape and rescue system that can precisely locate the survivor position and point out the escape route to timely assist victim search and rescuing. As interior decoration, the unique design of the honeycomb weaving structure endows the F‐TENG fabric with an excellent noise‐reduction ability. In addition, combining with its good machine washability, air permeability, flame‐retardency, durability, and repeatability features, the 3D F‐TENG may have great potential applications in fire rescue and wearable sensors as well as smart home decoration.

Laser Generation of Sub‐Micrometer Wrinkles in a Chalcogenide Glass Film as Physical Unclonable Functions

By Paloma Martinez, Irene Papagiannouli, Dominique Descamps, Stéphane Petit, Joël Marthelot, Anna Lévy, Baptiste Fabre, Jean‐Baptiste Dory, Nicolas Bernier, Jean‐Yves Raty, Pierre Noé, Jérôme Gaudin from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

The formation of random patterns induced by a laser pulse focused on amorphous Ge‐based chalcogenide thin film capped with a very thin SiN layer is demonstrated. These non‐deterministic surface patterns are wrinkles of sub‐100 nm height with a sub‐micrometer periodicity that depends on the impinging laser fluence. Application as physical unclonable functions is demonstrated using a dedicated fast recognition algorithm. Abstract Laser interaction with solids is routinely used for functionalizing materials' surfaces. In most cases, the generation of patterns/structures is the key feature to endow materials with specific properties like hardening, superhydrophobicity, plasmonic color‐enhancement, or dedicated functions like anti‐counterfeiting tags. A way to generate random patterns, by means of generation of wrinkles on surfaces resulting from laser melting of amorphous Ge‐based chalcogenide thin films, is presented. These patterns, similar to fingerprints, are modulations of the surface height by a few tens of nanometers with a sub‐micrometer periodicity. It is shown that the patterns' spatial frequency depends on the melted layer thickness, which can be tuned by varying the impinging laser fluence. The randomness of these patterns makes them an excellent candidate for the generation of physical unclonable function tags (PUF‐tags) for anti‐counterfeiting applications. Two specific ways are tested to identify the obtained PUF‐tag: cross‐correlation procedure or using a neural network. In both cases, it is demonstrated that the PUF‐tag can be compared to a reference image (PUF‐key) and identified with a high recognition ratio on most real application conditions. This paves the way to straightforward non‐deterministic PUF‐tag generation dedicated to small sensitive parts such as, for example, electronic devices/components, jewelry, or watchmak.

Suppressing Defects‐Induced Nonradiative Recombination for Efficient Perovskite Solar Cells through Green Antisolvent Engineering

By Wenzhan Xu, Yu Gao, Wenjie Ming, Fang He, Jingzhou Li, Xu‐Hui Zhu, Feiyu Kang, Jiangyu Li, Guodan Wei from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

Antisolvent engineering is employed to tune the crystal nucleation and grain growth of perovskite for achieving efficient perovskite solar cells. The engineering of perovskites treated with the green antisolvent MABr‐Eth, suppressing defects‐induced nonradiative recombination in perovskite solar cells, is developed. As expected, the device delivers over 21% power conversion efficiency and a better storage and light‐soaking stability. Abstract Organic–inorganic hybrid perovskites have attracted considerable attention due to their superior optoelectronic properties. Traditional one‐step solution‐processed perovskites often suffer from defects‐induced nonradiative recombination, which significantly hinders the improvement of device performance. Herein, treatment with green antisolvents for achieving high‐quality perovskite films is reported. Compared to defects‐filled ones, perovskite films by antisolvent treatment using methylamine bromide (MABr) in ethanol (MABr‐Eth) not only enhances the resultant perovskite crystallinity with large grain size, but also passivates the surface defects. In this case, the engineering of MABr‐Eth‐treated perovskites suppressing defects‐induced nonradiative recombination in perovskite solar cells (PSCs) is demonstrated. As a result, the fabricated inverted planar heterojunction device of ITO/PTAA/Cs0.15FA0.85PbI3/PC61BM/Phen‐NADPO/Ag exhibits the best power conversion efficiency of 21.53%. Furthermore, the corresponding PSCs possess a better storage and light‐soaking stability.

A Compliant Ionic Adhesive Electrode with Ultralow Bioelectronic Impedance

By Liang Pan, Pingqiang Cai, Le Mei, Yuan Cheng, Yi Zeng, Ming Wang, Ting Wang, Ying Jiang, Baohua Ji, Dechang Li, Xiaodong Chen from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

A compliant ionic adhesive electrode, based on an alginate–polyacrylamide (Alg‐PAAm) hydrogel, with ultralow interfacial impedance on the skin is created to record dynamically weak surface electromyography signals with high signal‐to‐noise ratio and low crosstalk. Due to excellent properties, a prosthetic hand is successfully driven to precisely grasp a needle based on the Alg‐PAAm compliant electrodes. Abstract Simultaneous implementation of high signal‐to‐noise ratio (SNR) but low crosstalk is of great importance for weak surface electromyography (sEMG) signals when precisely driving a prosthesis to perform sophisticated activities. However, due to gaps with the curved skin during muscle contraction, many electrodes have poor compliance with skin and suffer from high bioelectrical impedance. This causes serious noise and error in the signals, especially the signals from low‐level muscle contractions. Here, the design of a compliant electrode based on an adhesive hydrogel, alginate–polyacrylamide (Alg‐PAAm) is reported, which eliminates those large gaps through the strong electrostatic interaction and abundant hydrogen bond with the skin. The obtained compliant electrode, having an ultralow bioelectrical impedance of ≈20 kΩ, can monitor even 2.1% maximal voluntary contraction (MVC) of muscle. Furthermore, benefiting from the high SNR of >5:1 at low‐level MVC, the crosstalk from irrelevant muscle is minimized through reducing the electrode size. Finally, a prosthesis is successfully demonstrated to precisely grasp a needle based on a 9 mm2 Alg‐PAAm compliant electrode. The strategy to design such compliant electrodes provides the potential for improving the quality of dynamically weak sEMG signals to precisely control prosthesis in performing purposefully dexterous activity.

Masthead: (Adv. Mater. 38/2020)

By from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

Superconductivity of Topological Surface States and Strong Proximity Effect in Sn1–xPbxTe‐Pb Heterostructures

By Hao Yang, Yao‐Yi Li, Teng‐Teng Liu, Huan‐Yi Xue, Dan‐Dan Guan, Shi‐Yong Wang, Hao Zheng, Can‐Hua Liu, Liang Fu, Jin‐Feng Jia from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

Enhanced Charge Injection Properties of Organic Field Effect Transistor by Molecular Implantation Doping

By Youngrok Kim, Seungjun Chung, Kyungjune Cho, David Harkin, Wang‐Taek Hwang, Daekyoung Yoo, Jae‐Keun Kim, Woocheol Lee, Younggul Song, Heebeom Ahn, Yongtaek Hong, Henning Sirringhaus, Keehoon Kang, Takhee Lee from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

Contents: (Adv. Mater. 38/2020)

By from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

Boron Nitride FIlms: Desolvation‐Triggered Versatile Transfer‐Printing of Pure BN Films with Thermal–Optical Dual Functionality (Adv. Mater. 38/2020)

By Yujin Han, Hyeuk Jin Han, Yoonhyuk Rah, Cheolgyu Kim, Moohyum Kim, Hunhee Lim, Kwang Ho Ahn, Hanhwi Jang, Kyoungsik Yu, Taek‐Soo Kim, Eugene N. Cho, Yeon Sik Jung from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

In article number 2002099, Eugene N. Cho, Yeon Sik Jung, and co‐workers develop a new approach to printing pure BN films with highly compact and aligned architectures based on desolvation‐induced interfacial adhesion switching. The binder‐free BN films achieve both high thermal conductivity and optical transparency, demonstrating the multifunctionality of thermal management and optical enhancement for a variety of optoelectronic devices.

Organic Photovoltaics: A Cost‐Effective, Aqueous‐Solution‐Processed Cathode Interlayer Based on Organosilica Nanodots for Highly Efficient and Stable Organic Solar Cells (Adv. Mater. 38/2020)

By Mengqi Cui, Dan Li, Xiaoyan Du, Na Li, Qikun Rong, Ning Li, Lingling Shui, Guofu Zhou, Xinghua Wang, Christoph J. Brabec, Li Nian from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

The performance and industrial viability of organic photovoltaics are strongly influenced by the functionality and stability of the interface layers. In article number 2002973, Na Li, Ning Li, Xinghua Wang, Li Nian, and co‐workers present an advanced aqueous solution‐processed cathode interface layer based on cost‐effective organosilica nanodots (OSiNDs). Devices based on the OSiNDs interlayer show improved efficiency and highly enhanced operational stability compared to devices based on the commonly used ZnO interlayer.

Chalcogenide Films: Laser Generation of Sub‐Micrometer Wrinkles in a Chalcogenide Glass Film as Physical Unclonable Functions (Adv. Mater. 38/2020)

By Paloma Martinez, Irene Papagiannouli, Dominique Descamps, Stéphane Petit, Joël Marthelot, Anna Lévy, Baptiste Fabre, Jean‐Baptiste Dory, Nicolas Bernier, Jean‐Yves Raty, Pierre Noé, Jérôme Gaudin from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

“Pop‐art” like patterns resulting from the interaction of a single laser pulse focused on a‐Ge based chalcogenide thin film capped with a SiN layer are presented by Jérôme Gaudin and co‐workers. These nondeterministic surface patterns, described in article number 2003032, are wrinkles with a height of less than 100 nm and sub‐micrometer periodicity, which depends on the impinging laser fluence. Application as physical unclonable functions is demonstrated using a fast recognition algorithm.

Graphene: Facile Morphological Qualification of Transferred Graphene by Phase‐Shifting Interferometry (Adv. Mater. 38/2020)

By Ukjae Lee, Yun Sung Woo, Yoojoong Han, Humberto R. Gutiérrez, Un Jeong Kim, Hyungbin Son from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

In article number 2002854, Un Jeong Kim, Hyungbin Son, and co‐workers use phase‐shifting interferometry to quickly obtain morphological information of atomic‐scale structures on transferred graphene over a large area. The obtained morphological information includes wrinkles, various polymer residues, and tearing/opening of the transferred graphene, and it can be used to evaluate the quality of the transferred graphene, such as the physical integrity, thickness, and adhesive strength to the target substrate.

Superconductivity: Long‐Range Ordered Amorphous Atomic Chains as Building Blocks of a Superconducting Quasi‐One‐Dimensional Crystal (Adv. Mater. 38/2020)

By Chao An, Yonghui Zhou, Chunhua Chen, Fucong Fei, Fengqi Song, Changyong Park, Jianhui Zhou, Horst‐Günter Rubahn, Victor V. Moshchalkov, Xuliang Chen, Gufei Zhang, Zhaorong Yang from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

Crystalline and amorphous structures are two of the most common solid‐state phases. The combination of short‐range disordered and long‐range ordered structures at the atomic level is extremely rare. In article number 2002352, Xuliang Chen, Gufei Zhang, Zhaorong Yang, and co‐workers develop a system with long‐range ordered but short‐range disordered building blocks by compressing a linear chain compound under high pressure. Thus a first case where superconductivity is hosted by a lattice with periodic but amorphous constituent atomic chains is demonstrated.

The Bulk Heterojunction in Organic Photovoltaic, Photodetector, and Photocatalytic Applications

By Andrew Wadsworth, Zeinab Hamid, Jan Kosco, Nicola Gasparini, Iain McCulloch from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

The development of the bulk heterojunction, in terms of materials design, device engineering, and the underpinning physical understanding, has led to significant improvements in organic photovoltaics. Looking forward, the bulk heterojunction concept is likely to allow even greater solar cell efficiencies and interestingly, can be applied to other organic electronic applications, such as organic photodetectors and photocatalysts. Abstract Organic semiconductors require an energetic offset in order to photogenerate free charge carriers efficiently, owing to their inability to effectively screen charges. This is vitally important in order to achieve high power conversion efficiencies in organic solar cells. Early heterojunction‐based solar cells were limited to relatively modest efficiencies (

Mechanotribological Aspects of MXene‐Reinforced Nanocomposites

By Massoud Malaki, Rajender S. Varma from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

Comprehensive insights into the material, mechanical, and tribological properties of MXene nanolayers are provided. Potential applications and the recent advancements attained in MXene‐reinforced nanocomposites are discussed, starting with the synthesis, fabrication techniques, intricacies of the underlying physics and mechanisms, and finally focusing on the progress in experimental and computational studies. Abstract MXenes are recently discovered 2D nanomaterial with superior mechanical, thermal, and tribological properties, being commonly employed in a wide variety of critical research areas, ranging from cancer therapy to energy and environmental applications. Due to their special properties, such as mechanoceramic nature with excellent mechanical performance, thermal stability and rich surface properties, MXenes have tremendous potential as advanced composite structures, especially those based on polymers due to a great affinity between macromolecules and the terminating groups of 2D MXenes. MXenes have been extensively explored in metal matrix nanocomposites as well as in solid‐ or liquid‐based lubrication systems owing to the 2D structure and antifriction characteristics. The purpose of the this paper is to provide a comprehensive insight into the material, mechanical, and tribological properties of the MXene nanolayers with discussions on the recent advancements attained from MXene‐reinforced nanocomposites starting with the synthesis, fabrication techniques, intricacies of the underlying physics and mechanisms, and finally focusing on the progress in computational studies. This analysis of MXene‐based composites will stimulate an emerging field with innumerable opportunities and ample potentials to produce newfangled materials and structures with targeted properties.

Tue 27 Oct 16:00: TBC

From All Talks (aka the CURE list). Published on Sep 21, 2020.

TBC

Abstract not available

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Thu 12 Nov 13:00: Translation research in plant breeding, can we finish the job!

From All Talks (aka the CURE list). Published on Sep 21, 2020.

Translation research in plant breeding, can we finish the job!

In the post-genomic era, contribution to crop genetic improvement may requires fine characterization of agronomic traits, identification of the genes involved and engineering leader alleles and subsequent pyramiding to produce highly performing plant prototypes. At FloCAD team we established a workflow to enhance translational research. General strategy and case studies will be presented. Identified bottlenecks will be discussed.

Contact se389@cam.ac.uk for the Zoom link if you are not on our mailing list.

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Vinylene‐Linked Covalent Organic Frameworks with Symmetry‐Tuned Polarity and Photocatalytic Activity

By Junsong Xu, Can Yang, Shuai Bi, Wenyan Wang, Yafei He, Dongqing Wu, Qifeng Liang, Xinchen Wang, Fan Zhang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 21, 2020.

The polarity of a semiconducting molecule dominantly affects its intrinsic photophysical properties, which can be tuned by varying the molecular geometry. Herein, we developed a D3h‐symmetric tricyanomesitylene as a new monomer which could be reticulated into a vinylene‐linked covalent organic framework (g‐C54N6‐COF) via Knoevenagel condensation with another D3h‐symmetric monomer 2,4,6‐tris(4′‐formyl‐biphenyl‐4‐yl)‐1,3,5‐triazine. Meanwhile, replacing tricyanomesitylene with a C2v‐symmetric 3,5‐dicyano‐2,4,6‐trimethylpyridine gave birth to a less‐symmetric vinylene‐linked COF (g‐C52N6‐COF). The octupolar conjugated characters of g‐C54N6‐COF were reflected in its scarce solvatochromic effects either in ground or excited states, and endowed it with more promising semiconducting behaviors as compared with g‐C52N6‐COF, such as enhanced light‐harvesting and excellent photo‐induced charge generation and separation. Along with the matched energy level, g‐C54N6‐COF enabled the two‐half reactions of photocatalytic water splitting with average O2 evolution rate of 51.0 μmol h‐1 g‐1 and H2 evolution rate of 2518.9 μmol h‐1 g‐1. Such values are among the highest of state‐of‐the‐art COF photocatalysts.

Scalable Fabrication of Molybdenum Disulfide Nanostructures and their Assembly

By Yun Huang, Kang Yu, Huaizhi Li, Kai Xu, Zexi Liang, Debora Walker, Paulo Ferreira, Peer Fischer, Donglei (Emma) Fan from Wiley: Advanced Materials: Table of Contents. Published on Sep 21, 2020.

Molybdenum disulfide nanoribbons and their oxide hybrids with tunable dimensions from several to tens of micrometers are fabricated in a scalable and reproducible fashion. They disperse in suspension, transport along prescribed trajectories with electric manipulation, and instantly assemble upon UV‐click chemical reaction at the “press of a light button.” The nanoribbons demonstrate rapid optoelectric response and effectively remove mercury from solution. Abstract Molybdenum disulfide (MoS2) is a multifunctional material that can be used for various applications. In the single‐crystalline form, MoS2 shows superior electronic properties. It is also an exceptionally useful nanomaterial in its polycrystalline form with applications in catalysis, energy storage, water treatment, and gas sensing. Here, the scalable fabrication of longitudinal MoS2 nanostructures, i.e., nanoribbons, and their oxide hybrids with tunable dimensions in a rational and well‐reproducible fashion, is reported. The nanoribbons, obtained at different reaction stages, that is, MoO3, MoS2/MoO2 hybrid, and MoS2, are fully characterized. The growth method presented herein has a high yield and is particularly robust. The MoS2 nanoribbons can readily be removed from its substrate and dispersed in solution. It is shown that functionalized MoS2 nanoribbons can be manipulated in solution and assembled in controlled patterns and directly on microelectrodes with UV‐click‐chemistry. Owing to the high chemical purity and polycrystalline nature, the MoS2 nanostructures demonstrate rapid optoelectronic response to wavelengths from 450 to 750 nm, and successfully remove mercury contaminants from water. The scalable fabrication and manipulation followed by light‐directed assembly of MoS2 nanoribbons, and their unique properties, will be inspiring for device fabrication and applications of the transition metal dichalcogenides.

[ASAP] Gate-Tunable Surface States in Topological Insulator β-Ag2Te with High Mobility

By Pengliang Leng, Fangting Chen, Xiangyu Cao, Yuxiang Wang, Ce Huang, Xuandong Sun, Yaozhi Yang, Junchen Zhou, Xiaoyi Xie, Zihan Li, Enze Zhang, Linfeng Ai, Yunkun Yang, and Faxian Xiu from Nano Letters: Latest Articles (ACS Publications). Published on Sep 21, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c01676

[ASAP] Controlled Nutrient Delivery to Pancreatic Islets Using Polydopamine-Coated Mesoporous Silica Nanoparticles

By Mehdi Razavi, Rosita Primavera, Bhavesh D Kevadiya, Jing Wang, Mujib Ullah, Peter Buchwald, and Avnesh S Thakor from Nano Letters: Latest Articles (ACS Publications). Published on Sep 21, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c02576

[ASAP] Two-Stage Assembly of Mesocrystal Fibers with Tunable Diameters in Weak Magnetic Fields

By Martin Kapuscinski, Pierre Munier, Mo Segad, and Lennart Bergström from Nano Letters: Latest Articles (ACS Publications). Published on Sep 21, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c02770

[ASAP] Glutathione-S-transferase Fusion Protein Nanosensor

By Ryan M. Williams, Jackson D. Harvey, Januka Budhathoki-Uprety, and Daniel A. Heller from Nano Letters: Latest Articles (ACS Publications). Published on Sep 21, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c02691

[ASAP] Vertically Aligned and Ordered Arrays of 2D MCo2S4@Metal with Ultrafast Ion/Electron Transport for Thickness-Independent Pseudocapacitive Energy Storage

By Zongbin Hao, Xingchen He, Hongdou Li, Denis Trefilov, Yangyang Song, Yang Li, Xinxin Fu, Yushuang Cui, Shaochun Tang, Haixiong Ge, and Yanfeng Chen from ACS Nano: Latest Articles (ACS Publications). Published on Sep 21, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c02973

[ASAP] Atomic-Level Electronic Properties of Carbon Nitride Monolayers

By Dingguan Wang, Zishen Wang, Wei Liu, Arramel, Jun Zhou, Yuan Ping Feng, Kian Ping Loh, Jishan Wu, and Andrew T. S. Wee from ACS Nano: Latest Articles (ACS Publications). Published on Sep 21, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c06535

[ASAP] Supramolecular Chirality Synchronization in Thin Films of Plasmonic Nanocomposites

By Piotr Szustakiewicz, Natalia Kowalska, Dorota Grzelak, Tetsuya Narushima, Monika Góra, Maciej Bagiński, Damian Pociecha, Hiromi Okamoto, Luis M. Liz-Marzán, and Wiktor Lewandowski from ACS Nano: Latest Articles (ACS Publications). Published on Sep 21, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c03964

[ASAP] Design of Core–Shell Quantum Dots–3D WS2 Nanowall Hybrid Nanostructures with High-Performance Bifunctional Sensing Applications

By Shin-Yi Tang, Chun-Chuan Yang, Teng-Yu Su, Tzu-Yi Yang, Shu-Chi Wu, Yu-Chieh Hsu, Yu-Ze Chen, Tzu-Neng Lin, Ji-Lin Shen, Heh-Nan Lin, Po-Wen Chiu, Hao-Chung Kuo, and Yu-Lun Chueh from ACS Nano: Latest Articles (ACS Publications). Published on Sep 21, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c01264

[ASAP] Pulsing Liquid Alloys for Nanomaterials Synthesis

By Mohannad Mayyas, Maedehsadat Mousavi, Mohammad B. Ghasemian, Roozbeh Abbasi, Hongzhe Li, Michael J. Christoe, Jialuo Han, Yifang Wang, Chengchen Zhang, Md. Arifur Rahim, Jianbo Tang, Jiong Yang, Dorna Esrafilzadeh, Rouhollah Jalili, Francois-Marie Allioux, Anthony P. O’Mullane, and Kourosh Kalantar-Zadeh from ACS Nano: Latest Articles (ACS Publications). Published on Sep 21, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c06724

[ASAP] Sustainable and Biodegradable Wood Sponge Piezoelectric Nanogenerator for Sensing and Energy Harvesting Applications

By Jianguo Sun, Hengyu Guo, Javier Ribera, Changsheng Wu, Kunkun Tu, Marco Binelli, Guido Panzarasa, Francis W. M. R. Schwarze, Zhong Lin Wang, and Ingo Burgert from ACS Nano: Latest Articles (ACS Publications). Published on Sep 21, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c05493

[ASAP] Quasi-metal Microwave Route to MoN and Mo2C Ultrafine Nanocrystalline Hollow Spheres as Surface-Enhanced Raman Scattering Substrates

By Ruifeng Du, Wencai Yi, Wentao Li, Haifeng Yang, Hua Bai, Junfang Li, and Guangcheng Xi from ACS Nano: Latest Articles (ACS Publications). Published on Sep 21, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c05935

[ASAP] Engineering Organization of DNA Nano-Chambers through Dimensionally Controlled and Multi-Sequence Encoded Differentiated Bonds

By Zhiwei Lin, Hamed Emamy, Brian Minevich, Yan Xiong, Shuting Xiang, Sanat Kumar, Yonggang Ke, and Oleg Gang from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Sep 21, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c07263

[ASAP] Single-Atom Co–N4 Electrocatalyst Enabling Four-Electron Oxygen Reduction with Enhanced Hydrogen Peroxide Tolerance for Selective Sensing

By Fei Wu, Cong Pan, Chun-Ting He, Yunhu Han, Wenjie Ma, Huan Wei, Wenliang Ji, Wenxing Chen, Junjie Mao, Ping Yu, Dingsheng Wang, Lanqun Mao, and Yadong Li from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Sep 21, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c07790

[ASAP] All-Photochemical Rotation of Molecular Motors with a Phosphorus Stereoelement

By Gregory B. Boursalian, Eise R. Nijboer, Ruth Dorel, Lukas Pfeifer, Omer Markovitch, Alex Blokhuis, and Ben L. Feringa from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Sep 21, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c08249

[ASAP] Actinide Separation Inspired by Self-Assembled Metal–Polyphenolic Nanocages

By Lei Mei, Peng Ren, Qun-yan Wu, Yu-bin Ke, Jun-shan Geng, Kang Liu, Xue-qing Xing, Zhi-wei Huang, Kong-qiu Hu, Ya-lan Liu, Li-yong Yuan, Guang Mo, Zhong-hua Wu, John K. Gibson, Zhi-fang Chai, and Wei-qun Shi from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Sep 21, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c08048

[ASAP] High-Temperature Pulse Method for Nanoparticle Redispersion

By Hua Xie, Min Hong, Emily M. Hitz, Xizheng Wang, Mingjin Cui, Dylan J. Kline, Michael R. Zachariah, and Liangbing Hu from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Sep 21, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c04887

[ASAP] Insights into the Mechanism of n-Hexane Reforming over a Single-Site Platinum Catalyst

By Shuchen Zhang, Luning Chen, Zhiyuan Qi, Lei Zhuo, Jeng-Lung Chen, Chih-Wen Pao, Ji Su, and Gabor A. Somorjai from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Sep 21, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c07911

[ASAP] 3D Cage COFs: A Dynamic Three-Dimensional Covalent Organic Framework with High-Connectivity Organic Cage Nodes

By Qiang Zhu, Xue Wang, Rob Clowes, Peng Cui, Linjiang Chen, Marc A. Little, and Andrew I. Cooper from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Sep 21, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c07732

2D metal–organic framework for stable perovskite solar cells with minimized lead leakage

By Alex K.-Y. Jen from Nature Nanotechnology - Issue - nature.com science feeds. Published on Sep 21, 2020.

Nature Nanotechnology, Published online: 21 September 2020; doi:10.1038/s41565-020-0765-7

Two-dimensional conjugated metal–organic frameworks used as an electron-extraction layer enable the realization of highly stable perovskite solar cells with minimized lead ion leakage.

Complex-amplitude metasurface-based orbital angular momentum holography in momentum space

By Stefan A. Maier from Nature Nanotechnology - Issue - nature.com science feeds. Published on Sep 21, 2020.

Nature Nanotechnology, Published online: 21 September 2020; doi:10.1038/s41565-020-0768-4

A complex-amplitude metasurface hologram is conceptually designed and three-dimensionally printed. The device allows for high-bandwidth orbital angular momentum multiplexing holography and holographic video displays.

Relation between microscopic interactions and macroscopic properties in ferroics

By Manfred Fiebig from Nature Nanotechnology - Issue - nature.com science feeds. Published on Sep 21, 2020.

Nature Nanotechnology, Published online: 21 September 2020; doi:10.1038/s41565-020-0763-9

Both extrinsic and intrinsic factors determine the properties of ferroic materials and are difficult to disentangle. This study on artificial crystals of planar nanomagnets with well-defined, tuneable magnetic interactions unveils the intrinsic correlations between microscopic interactions and macroscopic properties such as the domain size and morphology or the domain-wall mobility.

Optical fibres with embedded two-dimensional materials for ultrahigh nonlinearity

By Zhongfan Liu from Nature Nanotechnology - Issue - nature.com science feeds. Published on Sep 21, 2020.

Nature Nanotechnology, Published online: 21 September 2020; doi:10.1038/s41565-020-0770-x

The internal surface of an optical fibre can be covered by uniform two-dimensional-material layers for highly nonlinear and low-loss light propagation.

The looks of a million-year-old polymer glass

By Juan J. de Pablo from Nature Materials - Issue - nature.com science feeds. Published on Sep 21, 2020.

Nature Materials, Published online: 21 September 2020; doi:10.1038/s41563-020-00812-4

Polymeric glasses with significant thermodynamic and kinetic stability have been fabricated using physical vapour deposition, providing a mean to gather insight into the properties of glasses aged for millions of years.

Quantum registers hit the right wavelength

By John J. L. Morton from Nature Materials - Issue - nature.com science feeds. Published on Sep 21, 2020.

Nature Materials, Published online: 21 September 2020; doi:10.1038/s41563-020-00808-0

Controlling nuclear spins coupled to an electron spin in silicon carbide has enabled development of a ‘quantum register’ interfaced with telecom photons, leading to the possibility of distant transport of quantum information.

Look beneath the surface

By German Sastre from Nature Materials - Issue - nature.com science feeds. Published on Sep 21, 2020.

Nature Materials, Published online: 21 September 2020; doi:10.1038/s41563-020-0771-z

Zeolitic catalyst particles are grown with nanosized fins that improve mass transport into the interior of the particle. This delays catalyst deactivation in the methanol-to-hydrocarbons process.

Recapitulating macro-scale tissue self-organization through organoid bioprinting

By Matthias P. Lutolf from Nature Materials - Issue - nature.com science feeds. Published on Sep 21, 2020.

Nature Materials, Published online: 21 September 2020; doi:10.1038/s41563-020-00803-5

A 3D bioprinting approach has been developed to facilitate tissue morphogenesis by directly depositing organoid-forming stem cells in an extracellular matrix, with the ability to generate intestinal epithelia and branched vascular tissue constructs.

Looking deeper into zeolites

By Stephen Shevlin from Nature Materials - Issue - nature.com science feeds. Published on Sep 21, 2020.

Nature Materials, Published online: 21 September 2020; doi:10.1038/s41563-020-0787-4

Avelino Corma, professor at the Institute of Chemical Technology (ITQ-CSIC-Polytechnical University of Valencia), talks to Nature Materials about challenges facing zeolites, and issues faced in commercializing research.

Towards chirality control of graphene nanoribbons embedded in hexagonal boron nitride

By Xiaoming Xie from Nature Materials - Issue - nature.com science feeds. Published on Sep 21, 2020.

Nature Materials, Published online: 21 September 2020; doi:10.1038/s41563-020-00806-2

Oriented trenches are created in h-BN using different catalysts, and used as templates to grow seamlessly integrated armchair and zigzag graphene nanoribbons with chirality-dependent electrical and magnetic conductance properties.

Carbazole isomers induce ultralong organic phosphorescence

By Bin Liu from Nature Materials - Issue - nature.com science feeds. Published on Sep 21, 2020.

Nature Materials, Published online: 21 September 2020; doi:10.1038/s41563-020-0797-2

A carbazole isomer, typically present as an impurity in commercially produced carbazole batches, is shown to be responsible for the ultralong phosphorescence observed in these compounds and their derivatives.

Micro- to nano-scale chemical and mechanical mapping of antimicrobial-resistant fungal biofilms

By Aaron Elbourne from RSC - Nanoscale latest articles. Published on Sep 21, 2020.

Nanoscale, 2020, Advance Article
DOI: 10.1039/D0NR05617K, Paper
Duy Quang Pham, Saffron J. Bryant, Samuel Cheeseman, Louisa Z. Y. Huang, Gary Bryant, Madeleine F. Dupont, James Chapman, Christopher C. Berndt, Jitraporn (Pimm) Vongsvivut, Russell J. Crawford, Vi Khanh Truong, Andrew S. M. Ang, Aaron Elbourne
The heterogeneity of fungal biofilms are spatially characterized using a combination of AFM, nanoindentation, and ATR-FTIR.
To cite this article before page numbers are assigned, use the DOI form of citation above.
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Achieving High‐Performance Perovskite Photovoltaic by Morphology Engineering of Low‐Temperature Processed Zn‐Doped TiO2 Electron Transport Layer

By Ming‐Chung Wu, Yen‐Tung Lin, Shih‐Hsuan Chen, Meng‐Huan Jao, Yin‐Hsuan Chang, Kun‐Mu Lee, Chao‐Sung Lai, Yang‐Fang Chen, Wei‐Fang Su from Wiley: Small: Table of Contents. Published on Sep 20, 2020.

This work introduces a morphology engineering method to prepare low‐temperature processed TiO2 layer for perovskite devices. The morphology of TiO2 layer can be controlled using a spray coating strategy, which can manipulate the growth of perovskite layer. Combining the spray coating technique and a metal ion doping strategy, a perovskite photovoltaic with efficiency over 21% can be obtained. Abstract Perovskite solar cells (PSCs) have become one of the most promising renewable energy converting devices. However, in order to reach a sufficiently high power conversion efficiency (PCE), the PSCs typically require a high‐temperature sintering process to prepare mesostructured TiO2 as an efficient electron transport layer (ETL), which prohibits the PSCs from commercialization in the future. This work investigates a low‐temperature synthesis of TiO2 nanocrystals and introduces a two‐fluid spray coating process to produce a nanostructured ETL for the following deposition of perovskite layer. The temperature during the whole deposition process can be maintained under 150 °C. Compared to the typical planar TiO2 layer, the perovskite layer fabricated on a nanostructured TiO2 layer shows uniform compactness, preferred orientation, and high crystallinity, leading to reproducible and promising device performance. The detail mechanisms are revealed by the contact angle test, morphology characterization, grazing incident wide angle X‐Ray scattering measurement, and space charge limited currents analysis. Finally, optimized device performance can be achieved through adequate Zn doping in the TiO2 layer, demonstrating an average PCE of 19.87% with champion PCE of 21.36%. The efficiency can maintain over 80% of its original value after 3000 h storage in ambient atmosphere. This study suggests a promising approach to offer high‐efficiency PSCs using the low‐temperature process.

Development of Magnet‐Driven and Image‐Guided Degradable Microrobots for the Precise Delivery of Engineered Stem Cells for Cancer Therapy

By Tanyong Wei, Jiang Liu, Dongfang Li, Shuxun Chen, Yachao Zhang, Junyang Li, Lei Fan, Zhangyan Guan, Chung‐Mau Lo, Lidai Wang, Kwan Man, Dong Sun from Wiley: Small: Table of Contents. Published on Sep 20, 2020.

A magnet‐driven and image‐guided degradable microrobot is developed to achieve precise delivery of engineered stem cells in vivo. The microrobot meets the requirements of degradability, mechanical strength, and magnetic drive. Guided by photoacoustic imaging, microrobots successfully deliver cells to a targeted site for tumor treatment in mice. This study verifies the feasibility of magnetic microrobots in wireless and minimally invasive surgery. Abstract Precise delivery of therapeutic cells to the desired site in vivo is an emerging and promising cellular therapy in precision medicine. This paper presents the development of a magnet‐driven and image‐guided degradable microrobot that can precisely deliver engineered stem cells for orthotopic liver tumor treatment. The microrobot employs a burr‐like porous sphere structure and is made with a synthesized composite to fulfill degradability, mechanical strength, and magnetic actuation capability simultaneously. The cells can be spontaneously released from the microrobots on the basis of the optimized microrobot structure. The microrobot is actuated by a gradient magnetic field and guided by a unique photoacoustic imaging technology. In preclinical experiments on nude mice, microrobots carrying cells are injected via the portal vein and the released cells from the microrobots can inhibit the tumor growth greatly. This paper reveals for the first time of using degradable microrobots for precise delivery of therapeutic cells in vascular tissue and demonstrates its therapeutic effect in preclinical test.

Understanding the Early Stages of Nickel Sulfide Nanocluster Growth: Isolation of Ni3, Ni4, Ni5, and Ni8 Intermediates

By Alexander J. Touchton, Guang Wu, Trevor W. Hayton from Wiley: Small: Table of Contents. Published on Sep 20, 2020.

In situ spectroscopic monitoring of nickel sulfide nanocluster formation allows for the identification of the fundamental reaction steps, such as metal atom addition, CS oxidative addition, and CC reductive elimination, that occur during cluster growth. This unprecedented level of detail will enable the targeted synthesis of larger Ni sulfide clusters. Abstract Addition of sub‐stoichiometric quantities of PEt3 and diphenyl disulfide to a solution of [Ni(1,5‐cod)2] generates a mixture of [Ni3(SPh)4(PEt3)3] (1), unreacted [Ni(1,5‐cod)2], and [(1,5‐cod)Ni(PEt3)2], according to 1H and 31P{1H} NMR spectroscopic monitoring of the in situ reaction mixture. On standing, complex 1 converts into [Ni4(S)(Ph)(SPh)3(PEt3)3] (2), via formal addition of a “Ni(0)” equivalent, coupled with a CS oxidative addition step, which simultaneously generates the Ni‐bound phenyl ligand and the μ3‐sulfide ligand. Upon gentle heating, complex 2 converts into a mixture of [Ni5(S)2(SPh)2(PEt3)5] (3) and [Ni8(S)5(PEt3)7] (4), via further addition of “Ni(0)” equivalents, in combination with a series of C–S oxidative addition and CC reductive elimination steps, which serve to convert thiophenolate ligands into sulfide ligands and biphenyl. The presence of 1–4 in the reaction mixture is confirmed by their independent syntheses and subsequent spectroscopic characterization. Overall, this work provides an unprecedented level of detail of the early stages of Ni nanocluster growth and highlights the fundamental reaction steps (i.e., metal atom addition, CS oxidative addition, and CC reductive elimination) that are required to grow an individual cluster.

Tunable Surface Selenization on MoO2‐Based Carbon Substrate for Notably Enhanced Sodium‐Ion Storage Properties

By Fanyan Zeng, Maohui Yu, Wanting Cheng, Wenxiu He, Yang Pan, Yaohui Qu, Cailei Yuan from Wiley: Small: Table of Contents. Published on Sep 20, 2020.

A rational strategy of tunable surface selenization on high‐crystalline substrate is demonstrated for constructing robust MoO2@MoSe2 heterostructures. The induced self‐built electric fields and strong chemical couplings can signally improve reaction kinetics, create extra active sites, and alleviate electrode pulverization for sodium‐ion storage. As expected, the selenization product exhibits satisfying reversible capacity and ultralong cycling life (6000 cycles). Abstract Transition metal chalcogenides with high theoretical capacity are promising conversion‐type anode materials for sodium ion batteries (SIBs), but often suffer from unsatisfied cycling stability (hundreds of cycles) caused by structural collapse and agglomerate. Herein, a rational strategy of tunable surface selenization on highly crystalline MoO2‐based carbon substrate is designed, where the sheet‐like MoSe2 can be coated on the surface of bundle‐like N‐doped carbon/granular MoO2 substrate, realizing partial transformation from MoO2 to MoSe2, and creating b‐NC/g‐MoO2@s‐MoSe2‐10 with robust hierarchical MoO2@MoSe2 heterostructures and strong chemical couplings (MoC and MoN). Such well‐designed architecture can provide signally improved reaction kinetics and reinforced structural integrity for fast and stable sodium‐ion storage, as confirmed by the ex situ results and kinetic analyses as well as the density functional theory calculations. As expected, the b‐NC/g‐MoO2@s‐MoSe2‐10 delivers splendid rate capability and ultralong cycling stability (254.2 mAh g−1 reversible capacity at 5.0 A g−1 after 6000 cycles with ≈89.0% capacity retention). Therefore, the tunable surface strategy can provide new insights for designing and constructing heterostructures of transition metal chalcogenides toward high‐performance SIBs.

A Hybrid Organo‐Nanotheranostic Platform of Superlative Biocompatibility for Near‐Infrared‐Triggered Fluorescence Imaging and Synergistically Enhanced Ablation of Tumors

By Ozioma Udochukwu Akakuru, Chuang Liu, M. Zubair Iqbal, Gohar Ijaz Dar, Gao Yang, Kun Qian, Elvis Ikechukwu Nosike, Jie Xing, Zhoujing Zhang, Yanying Li, Juan Li, Aiguo Wu from Wiley: Small: Table of Contents. Published on Sep 20, 2020.

The well‐known individual biocompatibility track records of the tri‐organo‐components of indocyanine green (ICG)‐embedded glycol chitosan (GC)‐polypyrrole (PP) nanoparticles (NPs), endow the hybrid ICG@GC‐PP NPs with the highly sought‐aftersuperlative biocompatibility for effectual biomedical application. Advantageously, plethora ICG is transported to the tumor site, where one‐time near‐infrared irradiation results in prolonged tumor fluorescence imaging, and total tumor regression within 14 days by the synergistic heating effects of ICG and PP. Abstract The quest for an all‐organic nanosystem with negligible cytotoxicity and remarkable in vivo tumor theranostic capability is inescapably unending. Hitherto, the landscape of available photothermal agents is dominated by metal‐based nanoparticles (NPs) with attendant in vivo negatives. Here, an all‐organic‐composed theranostic nanosystem with outstanding biocompatibility for fluorescence image‐guided tumor photothermal therapy, and as a potential alternative to metal‐based photothermal agents is developed. This is rationally achieved by compartmentalizing indocyanine green (ICG) in glycol chitosan (GC)‐polypyrrole (PP) nanocarrier to form hybrid ICG@GC‐PP NPs (≈65 nm). The compartmentalization strategy, alongside the high photothermal conversion ability of PP jointly enhances the low photostability of free ICG. Advantageously, ICG@GC‐PP is endowed with an impeccable in vivo performance by the well‐known biocompatibility track records of its individual tri organo‐components (GC, PP, and ICG). As a proof of concept, ICG@GC‐PP NPs enables a sufficiently prolonged tumor diagnosis by fluorescence imaging up to 20 h post‐injection. Furthermore, owing to the complementary heating performances of PP and ICG, ICG@GC‐PP NPs‐treated mice by one‐time near‐infrared irradiation exhibit total tumor regression within 14 days post‐treatment. Therefore, leveraging the underlying benefits of this study will help to guide the development of new all‐organic biocompatible systems in synergism, for safer tumor theranostics.

A Spheroid‐Forming Hybrid Gold Nanostructure Platform That Electrochemically Detects Anticancer Effects of Curcumin in a Multicellular Brain Cancer Model

By Intan Rosalina Suhito, Novi Angeline, Kwang‐Ho Lee, Huijung Kim, Chun Gwon Park, Zhengtang Luo, Tae‐Hyung Kim from Wiley: Small: Table of Contents. Published on Sep 20, 2020.

A multifunctional conductive platform that allows for highly efficient multicellular cancer spheroid formation and real‐time non‐destructive electrochemical monitoring of spheroid viability under various drug treatment conditions. The platform is useful for high throughput drug screening based on 3D multicellular culture models. Abstract In this study, a multifunctional platform that enables the highly efficient formation of 3D multicellular cancer spheroids and precise real‐time assessments of the anticancer effects of curcumin in a brain tumor coculture model is reported. A highly conductive gold nanostructure (HCGN) is fabricated to facilitate cancer spheroid formation without using anti‐cell adhesion molecules. A neuroblastoma (SH‐SY5Y) and glioblastoma (U‐87MG) coculture model is generated on HCGN with a specific cell‐to‐cell ratio (SH‐SY5Y: U‐87MG = 1:1), and their redox behaviors are successfully measured without destroying the distinct 3D structure of the multicellular spheroids. Using electrochemical signals as an indicator of spheroid viability, the effects of potential anticancer compounds on cocultured spheroids are further assessed. Remarkably, decreased cell viability in 3D spheroids caused by a low concentration of curcumin (30 µM) is detectable using the electrochemical method (29.4%) but not with a conventional colorimetric assay (CCK‐8). The detection is repeated more than ten times for both short‐ (63 h) and long‐term cultivation (144 h) without damaging the spheroids, enabling real‐time, non‐destructive pharmacokinetic analysis of various drug candidates. Therefore, it can be concluded that the hybrid platform is a highly promising, precise, and high‐throughput drug screening tool based on 3D cell cultivation.

Rational Design of a Replication‐Competent and Inheritable Magnetic Viruses for Targeting Biomedical Applications

By Yan‐Peng Xu, Hang‐Yu Zhou, Guang‐Chuan Wang, Ying Zhang, Tianxu Yang, Yueqi Zhao, Rui‐Ting Li, Rong‐Rong Zhang, Yan Guo, Xiaoyu Wang, Xiao‐Feng Li, Cheng‐Feng Qin, Ruikang Tang from Wiley: Small: Table of Contents. Published on Sep 20, 2020.

Infection with live‐attenuated vaccines always inevitably induces side effects that reduce their safety. Here, a rationally designed magnetic virus is suggested with inheritable magnetism, which retains its original biological infectivity while its tropism can be precisely controlled by magnetism. This study provides a proof of concept in virus vaccine improvement by a combination of gene modification and material incorporation. Abstract Infection with live‐attenuated vaccines always inevitably induces side effects that reduce their safety. This study suggests a concept of magnetic virus produced by genetically modifying viral surfaces with Fe3O4 nanoparticles (NPs) to control their tropisms. An iron‐affinity peptide is designed to be displayed on the viral surface protein (VP1) of human enterovirus type 71 (EV71), a typical nonenveloped picornavirus, as the model. The modified EV71 can self‐bind with Fe3O4 NPs under physiological conditions, resulting in novel EV71‐Fe3O4 hybrid materials. This rationally engineered EV71 with Fe3O4 retains its original biological infectivity, but its tropism can be precisely controlled by magnetism. Both in vitro and in vivo experiments demonstrate that EV71‐Fe3O4 can infect only a desired area within the limit of the applied magnetic field, which effectively reduces its pathological damage. More importantly, this characteristic of EV71 can be inherited due to the gene‐induced coassembly of viruses and NPs. This achievement provides a proof of concept in virus vaccine improvement by a combination of gene modification and material incorporation, leading to great potential for biomedical developments.

[ASAP] Picometer Resolution Structure of the Coordination Sphere in the Metal-Binding Site in a Metalloprotein by NMR

By Andrea Bertarello, Ladislav Benda, Kevin J. Sanders, Andrew J. Pell, Michael J. Knight, Vladimir Pelmenschikov, Leonardo Gonnelli, Isabella C. Felli, Martin Kaupp, Lyndon Emsley, Roberta Pierattelli, and Guido Pintacuda from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Sep 19, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c07339

Converting 2D Nanofiber Membranes to 3D Hierarchical Assemblies with Structural and Compositional Gradients Regulates Cell Behavior

By Shixuan Chen, Alec McCarthy, Johnson V. John, Yajuan Su, Jingwei Xie from Wiley: Advanced Materials: Table of Contents. Published on Sep 18, 2020.

A new class of 3D nanofiber assemblies with structural and compositional gradients is developed based on electrospinning, gas‐foaming expansion, coating, diffusion, encapsulation, and crosslinking. Such assemblies with gradients in pore sizes, fiber organizations, and contents of signaling molecules can be used to engineer tissue constructs for tissue repair and build biomimetic disease models for studying disease biology and screening drugs. Abstract New methods are described for converting 2D electrospun nanofiber membranes to 3D hierarchical assemblies with structural and compositional gradients. Pore‐size gradients are generated by tuning the expansion of 2D membranes in different layers with incorporation of various amounts of a surfactant during the gas‐foaming process. The gradient in fiber organizations is formed by expanding 2D nanofiber membranes composed of multiple regions collected by varying rotating speeds of mandrel. A compositional gradient on 3D assemblies consisting of radially aligned nanofibers is prepared by dripping, diffusion, and crosslinking. Bone mesenchymal stem cells (BMSCs) on the 3D nanofiber assemblies with smaller pore size show significantly higher expression of hypoxia‐related markers and enhanced chondrogenic differentiation compared to BMSCs cultured on the assemblies with larger pore size. The basic fibroblast growth factor gradient can accelerate fibroblast migration from the surrounding area to the center in an in vitro wound healing model. Taken together, 3D nanofiber assemblies with gradients in pore sizes, fiber organizations, and contents of signaling molecules can be used to engineer tissue constructs for tissue repair and build biomimetic disease models for studying disease biology and screening drugs, in particular, for interface tissue engineering and modeling.

Graphene Nanoribbons: On‐Surface Synthesis and Integration into Electronic Devices

By Zongping Chen, Akimitsu Narita, Klaus Müllen from Wiley: Advanced Materials: Table of Contents. Published on Sep 18, 2020.

Precision synthesis of graphene nanoribbons (GNRs) with chemically defined structures is crucial for their fundamental studies as well as device applications. The recent progress in the surface‐assisted synthesis of GNRs under ultrahigh vacuum and chemical vapor deposition conditions is summarized, and the updates in the applications of on‐surface synthesized GNRs, especially directing toward transistor devices, are subsequently addressed. Abstract Graphene nanoribbons (GNRs) are quasi‐1D graphene strips, which have attracted attention as a novel class of semiconducting materials for various applications in electronics and optoelectronics. GNRs exhibit unique electronic and optical properties, which sensitively depend on their chemical structures, especially the width and edge configuration. Therefore, precision synthesis of GNRs with chemically defined structures is crucial for their fundamental studies as well as device applications. In contrast to top‐down methods, bottom‐up chemical synthesis using tailor‐made molecular precursors can achieve atomically precise GNRs. Here, the synthesis of GNRs on metal surfaces under ultrahigh vacuum (UHV) and chemical vapor deposition (CVD) conditions is the main focus, and the recent progress in the field is summarized. The UHV method leads to successful unambiguous visualization of atomically precise structures of various GNRs with different edge configurations. The CVD protocol, in contrast, achieves simpler and industry‐viable fabrication of GNRs, allowing for the scale up and efficient integration of the as‐grown GNRs into devices. The recent updates in device studies are also addressed using GNRs synthesized by both the UHV method and CVD, mainly for transistor applications. Furthermore, views on the next steps and challenges in the field of on‐surface synthesized GNRs are provided.

Understanding Plant Biomass via Computational Modeling

By Shengfei Zhou, Kai Jin, Markus J. Buehler from Wiley: Advanced Materials: Table of Contents. Published on Sep 18, 2020.

The hierarchical structures and properties of plant biomass (especially wood) and relevant computational modeling are reviewed, which may inspire the bottom‐up design of new bio‐based materials and the manufacturing of nanomaterials from plant biomass. Both modeling and relevant experimental studies of wood cell wall, cellulose, lignin, and their molecular units are summarized. Common hierarchical structures in nature are also compared with wood. Abstract Plant biomass, especially wood, has been used for structural materials since ancient times. It is also showing great potential for new structural materials and it is the major feedstock for the emerging biorefineries for building a sustainable society. The plant cell wall is a hierarchical matrix of mainly cellulose, hemicellulose, and lignin. Herein, the structure, properties, and reactions of cellulose, lignin, and wood cell walls, studied using density functional theory (DFT) and molecular dynamics (MD), which are the widely used computational modeling approaches, are reviewed. Computational modeling, which has played a crucial role in understanding the structure and properties of plant biomass and its nanomaterials, may serve a leading role on developing new hierarchical materials from biomass in the future.

Transcription Factor Based Small‐Molecule Sensing with a Rapid Cell Phone Enabled Fluorescent Bead Assay

By Margaret Chern, Padric M. Garden, R C. Baer, James E. Galagan, Allison M. Dennis from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 18, 2020.

The allosteric transcription factor TetR acts as a sensor and actuator in this quantum dot enabled fluorescent bead assay for the small molecule anhydrotetracycline. This rapid, antibody‐free biosensor produces a visible change in fluorescent color, which can be detected by eye or with an inexpensive digital camera, based on dose‐dependent analyte‐responsive protein‐DNA binding. The adaptable sensor uses easily accessible biomolecular components. Abstract Recently, allosteric transcription factors (TFs) were identified as a novel class of biorecognition elements for in vitro sensing, whereby an indicator of the differential binding affinity between a TF and its cognate DNA exhibits dose‐dependent responsivity to an analyte. Described is a modular bead‐based biosensor design that can be applied to such TF‐DNA‐analyte systems. DNA‐functionalized beads enable efficient mixing and spatial separation, while TF‐labeled semiconductor quantum dots serve as bright fluorescent indicators of the TF‐DNA bound (on bead) and unbound states. The prototype sensor for derivatives of the antibiotic tetracycline exhibits nanomolar sensitivity with visual detection of bead fluorescence. Facile changes to the sensor enable sensor response tuning without necessitating changes to the biomolecular affinities. Assay components self‐assemble, and readout by eye or digital camera is possible within 5 minutes of analyte addition, making sensor use facile, rapid, and instrument‐free.

Co‐crystal Prediction by Artificial Neural Networks

By Jan‐Joris Devogelaer, Hugo Meekes, Paul Tinnemans, Elias Vlieg, René Gelder from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 18, 2020.

An artificial neural network calculates whether two molecules are likely to form a co‐crystal. The approach shows excellent performance on the proposed co‐crystal training and validation sets, and has an estimated accuracy of 80 % for molecules for which previous co‐crystallization data is unavailable. The figure illustrates the prediction of the newly discovered drug–drug co‐crystal containing ketoprofen and carbamazepine. Abstract A significant amount of attention has been given to the design and synthesis of co‐crystals by both industry and academia because of its potential to change a molecule's physicochemical properties. Yet, difficulties arise when searching for adequate combinations of molecules (or coformers) to form co‐crystals, hampering the efficient exploration of the target's solid‐state landscape. This paper reports on the application of a data‐driven co‐crystal prediction method based on two types of artificial neural network models and co‐crystal data present in the Cambridge Structural Database. The models accept pairs of coformers and predict whether a co‐crystal is likely to form. By combining the output of multiple models of both types, our approach shows to have excellent performance on the proposed co‐crystal training and validation sets, and has an estimated accuracy of 80 % for molecules for which previous co‐crystallization data is unavailable.

Anisotropic Protein Organofibers Encoded With Extraordinary Mechanical Behavior for Cellular Mechanobiology Applications

By Chao Ma, Bo Li, Baiqi Shao, Baiheng Wu, Dong Chen, Juanjuan Su, Hongjie Zhang, Kai Liu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 18, 2020.

By combining synthetic biology and protein engineering, anisotropic protein organofibers with extraordinary mechanical properties for cellular mechanobiology applications are assembled. This approach can be used to fabricate novel protein‐based fiber devices that are suitable for various translations such as mechano‐patch engraftments as well as organ‐regeneration matrix scaffolds in the near future. Abstract Hydrogels enable a variety of applications due to their dynamic networks, structural flexibility, and tailorable functionality. However, their mechanical performances are limited, specifically in the context of cellular mechanobiology. It is also difficult to fabricate robust gel networks with a long‐term durability. Thus, a new generation of soft materials showing outstanding mechanical behavior for mechanobiology applications is highly desirable. We combined synthetic biology and supramolecular assembly to prepare elastin‐like protein (ELP) organogel fibers with extraordinary mechanical properties. The mechanical performance and stability of the assembled anisotropic proteins are superior to other organo‐/hydrogel systems. Bone‐derived mesenchymal cells were introduced into the organofiber system for stem‐cell lineage differentiation. This approach demonstrates the feasibility of mechanically strong and anisotropic organonetworks for mechanobiology applications and holds great potential for tissue‐regeneration translations.

Hydrogen‐Bonding‐Promoted Cascade Rearrangement Involving the Enlargement of Two Rings: Efficient Access to Polycyclic Quinoline Derivatives

By Wen‐Bin Cao, Shijun Li, Meng‐Meng Xu, Haiyan Li, Xiao‐Ping Xu, Yu Lan, Shun‐Jun Ji from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 18, 2020.

Natural‐product‐like polycyclic pyrrolo[2,3‐c]quinoline derivatives have been easily constructed in one‐step process from easily available starting materials. This reaction involves two ring enlargements and four heterocyclic ring formations via cascade rearrangement process. DFT studies reveal the crucial hydrogen‐bonding interaction in the detailed mechanistic investigation. Abstract An efficient cascade reaction of tryptamine‐derived isocyanides with C,N‐cyclic azomethine imines is described. The polycyclic pyrrolo[2,3‐c]quinoline derivatives, which benefited from rearrangement process driven by hydrogen bonding, could be directly assembled in moderate to good yields (40–87 %) under metal‐free and mild conditions. This transformation involved four new heterocyclic rings formations and uniquely, ring opening of indole as well as ring expansion of C,N‐cyclic azomethine imine. Both experimental and DFT studies provided guidance on the in‐depth insight into the reaction pathways and hydrogen bonding was identified to lower the free energy barrier in transition states. This work constitutes a rare example of tryptamine‐derived isocyanide‐based cascade reactions, and potentially could be a powerful synthetic strategy for accessing polycyclic analogues involved in natural products.

A Near‐Infrared Photo‐Switched MicroRNA Amplifier for Precise Photodynamic Therapy of Early‐Stage Cancers

By Yue Zhang, Weiwei Chen, Yue Zhang, Xiaobo Zhang, Ying Liu, Huangxian Ju from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 18, 2020.

A NIR photo‐switched miRNA amplifier is proposed for precise photodynamic therapy of early‐stage cancers. The designed photozipper avoids off‐target damage during in vivo delivery and can be controllably cleaved to trigger miRNA‐responsive cascade activation of photosensitizers under UV and blue emissions of UCNPs, which amplifies ROS generation for highly efficient cancer treatment. Abstract Stimuli‐responsive photodynamic therapy (PDT) is a hot topic in precise medicine, but the low abundance of responsive trigger molecules in early‐stage disease limits application. Here we designed an amplifier with multiple upconversion luminances to achieve a near‐infrared photo‐switched cascade reaction triggered by specific microRNA and precise PDT of early‐stage cancers. This amplifier was composed of photo‐caged DNA nanocombs and an upconversion nanoparticle (UCNP) sensitized with IRDye 800CW. The nanocomb was prepared by assembling a photozipper‐protected hairpin and two kinds of hybridizable hairpin probes on a DNA skeleton. Upon 808‐nm light irradiation, the produced UV light cleaved off the photozipper to induce microRNA‐responsive cascade hybridization reaction, activating the photosensitizers linked to different hairpins to generate reactive oxygen species (ROS) under the simultaneously emitted blue light for efficient PDT.

A Prelude to Biogermylene Chemistry

By Pritam Mahawar, Mishi Kaushal Wasson, Mahendra Kumar Sharma, Chandan Kumar Jha, Goutam Mukherjee, Perumal Vivekanandan, Selvarajan Nagendran from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 18, 2020.

The biological application of an air‐, water‐, and culture‐medium‐stable germylene is demonstrated. The compound DPMGeOH (DPM=dipyrromethene ligand) shows strong antiproliferative effects on human cancer cell lines but is only minimally toxic to normal epithelial cells. Abstract The biological applications of germylenes remain unrealised owing to their unstable nature. We report the isolation of air‐, water‐, and culture‐medium‐stable germylene DPMGeOH (3; DPM=dipyrromethene ligand) and its potential biological application. Compound 3 exhibits antiproliferative effects comparable to that of cisplatin in human cancer cells. The cytotoxicity of compound 3 on normal epithelial cells is minimal and is similar to that of the currently used anticancer drugs. These findings provide a framework for a plethora of biological studies using germylenes and have important implications for low‐valent main‐group chemistry.

In Vitro Reconstitution Reveals a Central Role for the N‐Oxygenase PvfB in (Dihydro)pyrazine‐N‐oxide and Valdiazen Biosynthesis

By Gina L. Morgan, Bo Li from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Sep 18, 2020.

Novel activity is reported for the diiron N‐oxygenase PvfB from the Pseudomonas virulence factor pathway. Instead of modifying anilines like other N‐oxygenases, PvfB oxygenates the α‐amine of valine tethered to a carrier protein, first to a hydroxylamine then a nitroso, as characterized by protein NMR spectroscopy. The activity of PvfB is key to the biosynthesis of two different types of N−O bond‐containing natural products. Abstract The Pseudomonas virulence factor (pvf) operon is essential for the biosynthesis of two very different natural product scaffolds: the (dihydro)pyrazine‐N‐oxides and the diazeniumdiolate, valdiazen. PvfB is a member of the non‐heme diiron N‐oxygenase enzyme family that commonly convert anilines to their nitroaromatic counterparts. In contrast, we show that PvfB catalyzes N‐oxygenation of the α‐amine of valine, first to the hydroxylamine and then the nitroso, while linked to the carrier protein of PvfC. PvfB modification of PvfC‐tethered valine was observed directly by protein NMR spectroscopy, establishing the intermediacy of the hydroxylamine. This work reveals a central role for PvfB in the biosynthesis of (dihydro)pyrazine‐N‐oxides and valdiazen.

Exploration and Investigation of Periodic Elements for Electrocatalytic Nitrogen Reduction

By Shivaraj B. Patil, Di‐Yan Wang from Wiley: Small: Table of Contents. Published on Sep 18, 2020.

This review focuses on electrocatalytic properties of periodic elements toward the nitrogen reduction reaction. Recent advancements and working mechanisms of various elements are illustrated with appropriate tables and graphs. Overall, this review intends to open different directions for the fabrication of high efficiency electrocatalysts. Abstract High demand for green ecosystems has urged the human community to reconsider and revamp the traditional way of synthesis of several compounds. Ammonia (NH3) is one such compound whose applications have been extended from fertilizers to explosives and is still being synthesized using the high energy inhaling Haber‐Bosch process. Carbon free electrocatalytic nitrogen reduction reaction (NRR) is considered as a potential replacement for the Haber‐Bosch method. However, it has few limitations such as low N2 adsorption, selectivity (competitive HER reactions), low yield rate etc. Since it is at the early stage, tremendous efforts have been devoted in understanding the reaction mechanism and screening of the electrocatalysts and electrolytes. In this review, the electrocatalysts are classified based on the periodic table with heat maps of Faraday efficiency and yield rate of NH3 in NRR and their electrocatalytic properties toward NRR are discussed. Also, the activity of each element is discussed and short tables and concise graphs are provided to enable the researchers to understand recent progress on each element. At the end, a perspective is provided on countering the current challenges in NRR. This review may act as handbook for basic NRR understandings, recent progress in NRR, and the design and development of advanced electrocatalysts and systems.

Lead‐Free Dual‐Phase Halide Perovskites for Preconditioned Conducting‐Bridge Memory

By Ji Su Han, Quyet Van Le, Hyojung Kim, Yoon Jung Lee, Da Eun Lee, In Hyuk Im, Min Kyung Lee, Seung Ju Kim, Jaehyun Kim, Kyung Ju Kwak, Min‐Ju Choi, Sol A Lee, Kootak Hong, Soo Young Kim, Ho Won Jang from Wiley: Small: Table of Contents.