bluuebunny/crossref_metadata_2025_split huggingface dataset:
Emerging Chemistry in Enhancing the Chemical and Photochemical Stabilities of Fused‐Ring Electron Acceptors in Organic Solar Cells
Authors: Liu Hongtao , Li Yibin , Xu Shaoheng , Zhou Yinhua , Li Zhong'an 
Published: September 2021

AbstractThe power conversion efficiency of organic solar cells (OSCs) has made exceptionally rapid progress in the past five years owing to the emergence of fused‐ring electron acceptors (FREAs). To achieve the commercialization, it is urgent to resolve the stability issues of OCSs from materials to devices. In particular, the state‐of‐the‐art FREAs, often synthesized by Knoevenagel condensation, generally contain two exocyclic vinyl groups (CC bond) as the conjugated bridges, which inevitably exhibit an obvious electron‐deficient characteristic due to the strong push‐pull electronic effect. As a result, these vinyl bridges are vulnerable to nucleophile attacking and/or photooxidation, leading to poor chemical and photochemical stabilities of FREAs that easily cause the degradation of device performance. In this perspective, an in‐depth understanding of the degradation mechanism of FREAs is provided, and then effective strategies reported recently are reviewed for improving the chemical and photochemical stabilities of FREAs from interfacial engineering to molecular engineering to additive engineering. Finally, a conclusion and outlook for the future design of highly efficient and stable FREAs are also presented.
Spin–Charge Interconversion in KTaO3 2D Electron Gases
Authors: Vicente‐Arche Luis M. , Bréhin Julien , Varotto Sara , Cosset‐Cheneau Maxen , Mallik Srijani , Salazar Raphaël , Noël Paul , Vaz Diogo C. , Trier Felix , Bhattacharya Suvam , Sander Anke , Le Fèvre Patrick , Bertran François , Saiz Guilhem , Ménard Gerbold , Bergeal Nicolas , Barthélémy Agnès , Li Hai , Lin Chia‐Ching , Nikonov Dmitri E. , Young Ian A. , Rault Julien E. , Vila Laurent , Attané Jean‐Philippe , Bibes Manuel 
Published: September 2021

AbstractOxide interfaces exhibit a broad range of physical effects stemming from broken inversion symmetry. In particular, they can display non‐reciprocal phenomena when time reversal symmetry is also broken, e.g., by the application of a magnetic field. Examples include the direct and inverse Edelstein effects (DEE, IEE) that allow the interconversion between spin currents and charge currents. The DEE and IEE have been investigated in interfaces based on the perovskite SrTiO3 (STO), albeit in separate studies focusing on one or the other. The demonstration of these effects remains mostly elusive in other oxide interface systems despite their blossoming in the last decade. Here, the observation of both the DEE and IEE in a new interfacial two‐dimensional electron gas (2DEG) based on the perovskite oxide KTaO3 is reported. 2DEGs are generated by the simple deposition of Al metal onto KTaO3 single crystals, characterized by angle‐resolved photoemission spectroscopy and magnetotransport, and shown to display the DEE through unidirectional magnetoresistance and the IEE by spin‐pumping experiments. Their spin–charge interconversion efficiency is then compared with that of STO‐based interfaces, related to the 2DEG electronic structure, and perspectives are given for the implementation of KTaO3 2DEGs into spin–orbitronic devices is compared.
Enabling Atomic‐Scale Imaging of Sensitive Potassium Metal and Related Solid Electrolyte Interphases Using Ultralow‐Dose Cryo‐TEM
Authors: Zhang Qing , Han Bing , Zou Yucheng , Shen Shaocheng , Li Menghao , Lu Xinzhen , Wang Man , Guo Zaiping , Yao Jianquan , Chang Zhi , Gu Meng 
Published: September 2021

AbstractPotassium‐based solid electrolyte interphases (SEIs) have a much smaller damage threshold than their lithium counterpart; thus, they are significantly more beam sensitive. Here, an ultralow‐dose cryogenic transmission electron microscopy (cryo‐TEM) technique (≈8 e Å−2 s−1 × 10 s), which enables the atomic‐scale chemical imaging of the electron‐beam‐sensitive potassium metal and SEI in its native state, is adapted. The potassium‐based SEI consists of large brackets of diverse inorganic phases (≈hundreds of nanometers) interspersed with amorphous phases, which are different from the tiny nanocrystalline inorganic phases (≈a few nanometers) formed in a lithium‐based SEI. Organic phosphate‐based electrolyte solvents induce the formation of a thin and stable SEI layer for enhanced cycling performance, while the carbonate ester‐based electrolytes result in large quantities of metastable KHCO3, and K4CO4 products in the SEI, depleting the potassium reserves in the battery. The findings provide deep insights and guidance in the selection of optimum electrolytes that should be used for potassium batteries.
PEDOT:PSS‐Coated Stimulation Electrodes Attenuate Irreversible Electrochemical Events and Reduce Cell Electropermeabilization
Authors: Dijk Gerwin , Ruigrok Hermanus J. , O'Connor Rodney P. 
Published: September 2021

AbstractElectroporation or electropermeabilization occurs when cells are exposed to sufficiently high‐pulsed electric fields. This phenomenon is now an important technique to facilitate the transmembrane transport of molecules, however, the role of the electrode material and associated electrochemical events remain unclear. Here, it is shown that electrical stimulation with PEDOT:PSS‐coated electrodes strongly reduces irreversible electrochemical reactions that otherwise lead to changes in pH and the generation of reactive oxygen species. Coated electrodes exhibit a slightly higher threshold for cell stimulation, however, little electropermeabilization is observed at voltages that greatly exceed the threshold for uncoated electrodes. The findings indicate that electrically induced, extracellular chemical changes represent an important mechanism in the cellular electropermeabilization response. Moreover, PEDOT:PSS‐coated electrodes separate the delivery of electric pulses from chemical changes, which paves the way for future experiments that could lead to a better understanding of underlying mechanisms.
Facile Amidogen Bio‐Activation Method Can Boost the Soft Tissue Integration on 3D Printed Poly–Ether–Ether–Ketone Interface
Authors: Liu Xi , Huang Lijun , Zhang Hao , Liu Yujian , Wu Chunyan , Luo Qixing , Yin Feiyang , Yan Xiaolong , Zhao Jinbo , Su Yanwen , He Jiankang , Li Weimiao , Li Dichen , Shi Changquan , Yang Pinyi , Zhao Zhenhuan , Du Tao , Wu Weiwei , Li Xiaofei , Wang Lei 
Published: September 2021

AbstractPoly‐ether‐ether‐ketone (PEEK) implants with good mechanical properties and chemical inertia, meet the urgent needs of bone substitute. However, its inert interface leads to poor soft tissue integration, which prolongs healing time of surgical incision with many complications. Herein, (3‐aminopropyl) triethoxysilane is connected to 3D printed (3DP) PEEK interface by chemical modification. The homogeneous amino groups on amidogen interface enhance PEEK's hydrophilicity and proteinophilia significantly. Fibroblasts cultured on the amidogen PEEK interface show much stronger potential of cell adhesion and migration. Furthermore, soft tissue ingrowth into 3DP PEEK scaffold occurs more and faster in the amidogen interface in vivo. The observation of the microstructure shows tighter implant–tissue bonding interfaces on the amidogen PEEK. To mimic real surgery, 3DP PEEK implants of the same proportions in clinical practice are used to reconstruct the chest wall defects of rabbits. A significant reduction in healing time and incision complications are observed in the amidogen PEEK groups. In addition, 19 related proteins are found in the fibroblasts cultured on the amidogen PEEK interface, which can be used to trace the biological mechanisms. In all, the facile amidogen bio‐activation method can significantly boost the soft tissue integration on 3DP PEEK interface with less surgical complications.
Photoinduced Electron and Energy Transfer Pathways and Photocatalytic Mechanisms in Hybrid Plasmonic Photocatalysis
Authors: Ramakrishnan Sundaram Bhardwaj , Mohammadparast Farshid , Dadgar Andishaeh P. , Mou Tong , Le Tien , Wang Bin , Jain Prashant K. , Andiappan Marimuthu 
Published: September 2021

AbstractHybrid plasmonic nanostructures are built on plasmonic metalnanostructures surrounded by catalytic metals or metal oxides. Recent studies have shown that hybrid plasmonic nanocatalysts can concurrently utilize thermal energy and photon stimuli and exhibit high catalytic activity, selectivity, and stability that are not attainable in conventional purely thermally activated catalytic processes. The hybrid plasmonic photocatalytic approach has recently emerged as an attractive concept for the conversion of solar energy into chemical energy, the distributed synthesis of valuable chemicals such as ammonia with little to no requirement of external heating, and the development of coke‐resistant and selective catalytic processes. The field of hybrid plasmonic photocatalysis has grown tremendously in the last decade. In this review article, the advantages of visible‐light‐augmented hybrid plasmonic photocatalysis over conventional pure thermally activated heterogeneous catalysis are discussed. Fundamental insights are provided into photocatalytic mechanisms by which the photoexcited charge carriers (electrons and holes) are formed and transferred to adsorbates triggering chemical transformations on the surface of hybrid plasmonic nanocatalysts. Computational modeling used for predicting and understanding the photocatalytic activity and selectivity on hybrid plasmonic nanostructures is also reviewed. The review closes with a discussion of the current challenges, new opportunities, and future outlook for hybrid plasmonic photocatalysis.
High‐QChiroptical Resonances by Quasi‐Bound States in the Continuum in Dielectric Metasurfaces with Simultaneously Broken In‐Plane Inversion and Mirror Symmetries
Authors: Kim Kwang‐Hyon , Kim Ju‐Ryong 
Published: September 2021

AbstractBound states in the continuum (BIC) have recently attracted great attention in photonics. Metasurfaces with broken inversion symmetry exhibit high‐Qresonances via quasi‐BIC, enabling low threshold lasing, sensing, and efficient nonlinear generation. Recently, chiral BICs have been investigated by using double layer structure or out‐of‐plane perturbation, requiring complicated fabrication processes. This work presents chiral quasi‐BIC by simultaneously breaking the in‐plane inversion and mirror symmetries in dielectric metasurfaces. For such a simultaneous symmetry breaking, the metasurfaces exhibit quasi‐BIC with strong chirality, resulting in near‐unity circular dichroism with high quality factor of several orders‐of‐magnitude. As the chiral quasi‐BIC appears only by in‐plane structural perturbation, it is much more feasible for practical fabrications compared with preceding results. Due to the symmetry‐protected nature of its original BIC, the proposed approach does not require fine tuning of structural parameters for observing the desired effects unlike the accidental BIC. The results presented in this work pave the way for chiral sensing with high spectral resolution, nonlinear chiroptics with high efficiency, low‐threshold circular polarized lasing, and security applications.
One‐Pot Enzyme Cascade Catalyzed Asymmetrization of Primary Alcohols: Synthesis of Enantiocomplementary Chiral β‐Nitroalcohols
Authors: Chatterjee Ayon , Rao D. H. Sreenivasa , Kumar Padhi Santosh 
Published: September 2021

AbstractBiocatalytic asymmetrization of inexpensive and stable primary alcohols to prepare enantioenriched β‐nitroalcohols is an important development in green chemistry for the production of chiral pharmaceutical intermediates. Herein, we report a one‐pot, two‐step cascade reaction sequence in which first benzylic alcohols were oxidized to produce corresponding benzaldehydes using horse liver alcohol dehydrogenase (HLADH). The in situ generated aldehydes were then reacted in a biphasic medium with nitromethane by Arabidopsis thaliana hydroxynitrile lyase (AtHNL) or Baliospermum montanum HNL (BmHNL) catalyzed Henry reaction to produce stereoselective β‐nitroalcohols with (R) or (S) configuration, respectively. Using HLADH‐AtHNL, (R)‐β‐nitroalcohols were obtained in up to 64% conversion, and HLADH‐BmHNL, (S)‐β‐nitroalcohols in up to 70% conversion, while in both cases excellent stereoselectivity (up to >99% ee) was achieved. The concept was proven by functionalization of sp3 C−H bond of ten simple achiral benzylic alcohols to enantiocomplementary chiral β‐nitroalcohols.magnified image
Organic Matrix Assisted Low‐temperature Crystallization of Black Phase Inorganic Perovskites
Authors: Chen Yuetian , Liu Xiaomin , Zhao Yixin 
Published: September 2021

AbstractAll‐inorganic perovskites have attracted increasing attention for applications in perovskite solar cells (PSCs) and optoelectronics, including light‐emitting devices (LEDs). Cesium lead halide perovskites with tunable I/Br ratios and a band gap aligning with the sunlight region are promising candidates for PSCs. Although impressive progress has been made to improve device efficiency from the initial 2.9 % with low phase stability to over 20 % with high stability, there are still questions regarding the perovskite crystal growth mechanism, especially at low temperatures. In this Minireview, we summarize recent developments in using an organic matrix, including the addition and use of organic ions, polymers, and solvent molecules, for the crystallization of black phase inorganic perovskites at temperatures lower than the phase transition point. We also discuss possible mechanisms for this low‐temperature crystallization and their effect on the stability of black phase perovskites. We conclude with an outlook and perspective for further fabrication of large‐scale inorganic perovskites for optoelectronic applications.
Stable Interface Chemistry and Multiple Ion Transport of Composite Electrolyte Contribute to Ultra‐long Cycling Solid‐State LiNi0.8Co0.1Mn0.1O2/Lithium Metal Batteries
Authors: Yang Ke , Chen Likun , Ma Jiabin , Lai Chen , Huang Yanfei , Mi Jinshuo , Biao Jie , Zhang Danfeng , Shi Peiran , Xia Heyi , Zhong Guiming , Kang Feiyu , He Yan‐Bing 
Published: September 2021

AbstractSevere interfacial side reactions of polymer electrolyte with LiNi0.8Co0.1Mn0.1O2 (NCM811) cathode and Li metal anode restrict the cycling performance of solid‐state NCM811/Li batteries. Herein, we propose a chemically stable ceramic‐polymer‐anchored solvent composite electrolyte with high ionic conductivity of 6.0×10−4 S cm−1, which enables the solid‐state NCM811/Li batteries to cycle 1500 times. The Li1.4Al0.4Ti1.6(PO4)3 nanowires (LNs) can tightly anchor the essential N, N‐dimethylformamide (DMF) in poly(vinylidene fluoride) (PVDF), greatly enhancing its electrochemical stability and suppressing the side reactions. We identify the ceramic‐polymer‐liquid multiple ion transport mechanism of the LNs‐PVDF‐DMF composite electrolyte by tracking the 6Li and 7Li substitution behavior via solid‐state NMR. The stable interface chemistry and efficient ion transport of LNs‐PVDF‐DMF contribute to superior performances of the solid‐state batteries at wide temperature range of −20–60 °C.
Overcoming the Low Driving Force in Forming Depolymerizable Polymers through Monomer Isomerization
Authors: Chen Hanlin , Shi Zhen , Hsu Tze‐Gang , Wang Junpeng 
Published: September 2021

AbstractWhile depolymerizable polymers have been intensely pursued as a potential solution to address the challenges in polymer sustainability, most depolymerization systems are characterized by a low driving force in polymerization, which poses difficulties for accessing diverse functionalities and architectures of polymers. Here, we address this challenge by using a cyclooctene‐based depolymerization system, in which the cis‐to‐trans alkene isomerization significantly increases the ring strain energy to enable living ring‐opening metathesis polymerization at monomer concentrations ≥0.025 M. An additional trans‐cyclobutane fused at the 5,6‐position of the cyclooctene reduces the ring strain energy of cyclooctene, enabling the corresponding polymers to depolymerize into the cis‐cyclooctene monomers. The use of excess triphenylphosphine was found to be essential to suppress secondary metathesis and depolymerization. The high‐driving‐force living polymerization of the trans‐cyclobutane fused trans‐cyclooctene system holds promise for developing chemically recyclable polymers of a wide variety of polymer architectures.
Cycloadditions of Donor–Acceptor Cyclopropanes and ‐butanes using S=N‐Containing Reagents: Access to Cyclic Sulfinamides, Sulfonamides, and Sulfinamidines
Authors: Oliver Gwyndaf A. , Loch Maximilian N. , Augustin André U. , Steinbach Pit , Sharique Mohammed , Tambar Uttam K. , Jones Peter G. , Bannwarth Christoph , Werz Daniel B. 
Published: September 2021

AbstractWe present (3+2)‐ and (4+2)‐cycloadditions of donor–acceptor (D–A) cyclopropanes and cyclobutanes with N‐sulfinylamines and a sulfur diimide, along with a one‐pot, two‐step strategy for the formal insertion of HNSO2 into D–A cyclopropanes. These are rare examples of cycloadditions with D–A cyclopropanes and cyclobutanes whereby the 2π component consists of two different heteroatoms, thus leading to five‐ and six‐membered rings containing adjacent heteroatoms.
Biosynthesis of Chuangxinmycin Featuring a Deubiquitinase‐like Sulfurtransferase
Authors: Zhang Xingwang , Xu Xiaokun , You Cai , Yang Chaofan , Guo Jiawei , Sang Moli , Geng Ce , Cheng Fangyuan , Du Lei , Shen Yuemao , Wang Sheng , Lan Haidong , Yang Fan , Li Yuezhong , Tang Ya‐Jie , Zhang Youming , Bian Xiaoying , Li Shengying , Zhang Wei 
Published: September 2021

AbstractThe knowledge on sulfur incorporation mechanism involved in sulfur‐containing molecule biosynthesis remains limited. Chuangxinmycin is a sulfur‐containing antibiotic with a unique thiopyrano[4,3,2‐cd]indole (TPI) skeleton and selective inhibitory activity against bacterial tryptophanyl‐tRNA synthetase. Despite the previously reported biosynthetic gene clusters and the recent functional characterization of a P450 enzyme responsible for C−S bond formation, the enzymatic mechanism for sulfur incorporation remains unknown. Here, we resolve this central biosynthetic problem by in vitro biochemical characterization of the key enzymes and reconstitute the TPI skeleton in a one‐pot enzymatic reaction. We reveal that the JAMM/MPN+ protein Cxm3 functions as a deubiquitinase‐like sulfurtransferase to catalyze a non‐classical sulfur‐transfer reaction by interacting with the ubiquitin‐like sulfur carrier protein Cxm4GG. This finding adds a new mechanism for sulfurtransferase in nature.
Organic Long Persistent Luminescence Through In Situ Generation of Cuprous(I) Ion Pairs in Ionic Solids
Authors: Liang Xiao , Luo Xu‐Feng , Yan Zhi‐Ping , Zheng You‐Xuan , Zuo Jing‐Lin 
Published: September 2021

AbstractRecent development of most organic long persistent luminescence (OLPL) systems employed binary or tertiary doping. However, the design strategies towards OLPL materials with hour‐long afterglow duration are still quite limited. Here, we propose a novel OLPL system through melt‐casting method with 0.1 mol % of CuI complexes: 2,2′‐bis(diphenylphosphino)‐1,1′‐binaphthyl BINAP‐CuX (X=Cl, Br and I) doped into the triphenylphosphine (TPP) host. The charge separation was initiated prior to excitation through host coordination with CuI complexes, resulting in semi‐free halogen ions and in situ generated CuI cations, which forms TPP + BINAP‐CuX ionic pairs and subsequently ionic solids. The OLPL lifetime can be readily modulated by different halogen atoms and the afterglow can last up to more than 3 hours perceivable to human eyes. This is a rare example of OLPL initiated through host‐guest coordination that could potentially expand the definition of OLPL systems and design strategies.
Precatalyst‐Enabled Selectivity: Enantioselective NiH‐Catalyzed anti‐Hydrometalative Cyclization of Alkynones to Endo‐ and Heterocyclic Allylic Alcohols
Authors: Zhang Xiao‐Wen , Zhu Ming‐Hui , Zeng Hai‐Xiang , Li Qi‐Yang , Liu Wen‐Bo 
Published: September 2021

AbstractA highly enantioselective NiH‐catalyzed hydrocyclization of alkynones with unparalleled anti‐ and endocyclic selectivities is described. The choice of the precatalysts has significant influence in tuning the regio‐ and enantioselectivity. Using Ni(OTs)2/Phox as a precatalyst and (EtO)2MeSiH as a hydride source, an array of enantioenriched O‐, N‐, and S‐containing heterocyclic tertiary allylic alcohols are obtained in 24–81 % yields with 80:20–99:1 er. Mechanistic investigations and synthetic application are also carried out. This study represents an efficient access to a set of allylic alcohols that are unable to access by the state‐of‐the‐art coupling reactions.
A Solvent‐Polarity‐Induced Interface Self‐Assembly Strategy towards Mesoporous Triazine‐Based Carbon Materials
Authors: Zhang Rui , Liu Zhilin , Gao Tu‐Nan , Zhang Liangliang , Zheng Yuenan , Zhang Jianan , Zhang Ling , Qiao Zhen‐An 
Published: September 2021

AbstractTriazine‐based materials with porous structure have recently received numerous attentions as a fascinating new class because of their superior potential for various applications. However, it is still a formidable challenge to obtain triazine‐based materials with precise adjustable meso‐scaled pore sizes and controllable pore structures by reported synthesis approaches. Herein, we develop a solvent polarity induced interface self‐assembly strategy to construct mesoporous triazine‐based carbon materials. In this method, we employ a mixed solvent system within a suitable range of polarity (0.223≤Lippert–Mataga parameter (Δf) ≤0.295) to induce valid self‐assembly of skeleton precursor and surfactant. The as‐prepared mesoporous triazine‐based carbon materials possess uniform tunable pore sizes (8.2–14.0 nm), high surface areas and ultrahigh nitrogen content (up to 18 %). Owing to these intriguing advantages, the fabricated mesoporous triazine‐based carbon materials as functionalized porous solid absorbents exhibit predominant CO2 adsorption performance and exceptional selectivity for the capture of CO2 over N2.
Preparation of bimetal modified HMS molecular sieve and its desulfurization performance mechanism
Authors: Song Xiaoli , Pang Yaming , Gao Liguo 
Published: September 2021

AbstractIn this paper, dodecylamine (DDA) is used as the template, and ethyl orthosilicate (TEOS) is used as the silicon source. The HMS molecular sieve is prepared by in situ synthesis and modified by Cu, Ce, and Cu/Ce. The Cu/Ce‐HMS molecular sieve catalyst was synthesized for the first time. Scanning electron microscopy (SEM), energy dispersive spectrometer (EDS), and Fourier transform infrared spectrometer (FTIR) were used to characterize the synthesized composite molecular sieve. The results showed that the metal was loaded on the HMS intact and did not change the morphology of the HMS. A mixture of n‐hexane and dibenzothiophene (DBT) was used as the model oil, and the oxidation removal of DBT in the model oil was used as a probe reaction to study the photocatalytic oxidative desulfurization performance of the composite catalyst. The results show that the desulfurization rate after modification is Cu/Ce‐HMS molecular sieve > Cu‐HMS molecular sieve > Ce‐HMS. Finally, we explored the reaction mechanism of catalyst desulfurization. The results of ultraviolet diffuse reflectance showed that the modified molecular sieve Cu/Ce‐HMS had a smaller band gap, greater reaction activity, and stronger photocatalytic performance, which is benefit to improve the desulfurization efficiency. We report a simple and effective preparation method of composite molecular sieve catalyst, which provides a certain reference for future desulfurization research.