bluuebunny/crossref_metadata_2025_split huggingface dataset:
Modulating the Macroscopic Helicity of Poly(m‐phenylenediamine) by Achiral Monomer Copolymerization
Authors: Zha Xinlin , Xu Guilin , Xiong Yi , Yan Zhong , Liu Ke , Li Mufang , Chen Yuanli , Lu Jing , Wang Dong 
Published: November 2022

AbstractDesigning artificial systems to mimic chiral superstructures and exploring how achiral molecules precisely modulate their chirality is crucial to understand the origin of homochirality in nature. Herein, the tunability nature of supramolecular chirality is subtly applied to fabricate robust chiral covalent polymers with controlled macroscopic helicity. When using conventional supramolecular transcription methods to prepare chiral poly(m‐phenylenediamine), simply introducing various small amounts of achiral diaminopyridines (DAPs) to copolymerize with m‐phenylenediamine (MPD) enables the resulting chiral copolymers with adjustable helical configurations and chiroptical activities in an enantiopure template system. The strong hydrogen bonds between DAPs and the template molecules ((S)/(R)‐PhgC16) proved to be the driving force for guiding the chiral polymerization mode of MPD. Impressively, the exquisite self‐sorting phenomenon is observed by tuning the stoichiometric ratio of DAP and (R)‐PhgC16, where the as‐prepared copolymers with opposite helicity can exist simultaneously to form a double network structure and their chiroptical activity can be well regulated. In addition, based on such a copolymerization strategy, a conceptual library of helical functional copolymers is built with editable polymer types including conducting polymers and designable amine‐aldehyde condensation‐based polymers. This copolymerization‐mediated synthetic strategy may facilitate the development of chiral polymers with controlled morphologies and dynamic compositions.
Rapid Melt‐Quenching Enables General Synthesis of High‐Loading Single‐Atom Catalysts with Bicontinuous Nanoporous Structure
Authors: Jiang Kang , Liu Zhixiao , Lu Ying‐Rui , Wang Mengjia , Chen Dechao , Cai Lebin , Chan Ting‐Shan , Liu Pan , Pan Anlian , Tan Yongwen 
Published: November 2022

AbstractSingle‐atom catalysts have attracted extensive attention due to their unique atomic structures and extraordinary activities in catalyzing chemical reactions. However, the lack of general and efficient approaches for producing high‐density single atoms on suitably tailored supporting matrixes hinders their industrial applications. Here, a rapid melt‐quenching strategy with high throughput to synthesize single atoms with high metal‐atom loadings of up to 9.7 wt% or 2.6 at% on nanoporous metal compounds is reported, representing several‐fold improvements compared to benchmarks in the literature. Mechanism characterizations reveal that the high‐temperature melting provides the essential liquid environment and activation energy to achieve the atomization of metals, while the following rapid‐quenching pins the isolated metal atoms and stabilizes the coordination environment. In comparison with carbon‐supported single‐atom catalysts, various collaboration combinations of single atoms and nanoporous metal compounds can be synthesized using the strategy, thus achieving efficient hydrazine oxidation‐assisted H2 production. This synthesis protocol is highly compatible with automatic operation, which provides a feasible and general route to design and manufacture specific single‐atom catalysts with tunable atomic metal components and supporting matrixes, thus promoting the deployment of single‐atom catalysts for various energy technology applications.
Visible‐Light‐Induced Radical Type Ring‐Opening of Sulfonium Salts with Heteroarenes by Copper Photocatalyst
Authors: Zhu Xiaolong , Song Xiuyan , Li Xuan , Wang Fengxiao , Lv Jian , Jiang Min , Yang Daoshan 
Published: November 2022

AbstractIn this manuscript, we report a radical type ring‐opening of sulfonium salts with heteroarenes under visible light conditions. This developed method does not require noble metal photocatalysts, or stoichiometric amount of external oxidants, and has a application prospect in the synthesis of organosulfur compounds and bioactive molecules. This radical type ring‐opening photocatalytic system could inspire further applications of sulfonium salts in C(sp3)−C(sp2) bond forming reactions.magnified image
Investigation of the temporal and spatial flow features within the high‐shear mixer by modal decomposition techniques
Authors: Zhao Shuchun , Li Wei , Zhang Jinli 
Published: November 2022

AbstractAn insightful comprehension of hydrodynamics in the high‐shear mixer (HSM) is crucial for its design and optimization. Therefore, the energetical and dynamical dominant features of inline HSM's velocity fields are extracted by proper orthogonal decomposition (POD) and dynamic mode decomposition (DMD), of which the sampling spaces are generated through Large‐Eddy Simulation. POD results reveal that the significant flow structures located in the shear gap and the adjacent regions of rotor/stator slot inlets comprise various energy levels. The strip‐shaped structures at the rotor/stator leading edges, wake and large‐scale vortices within the outflow region, and circulation inside the rotor slot are also visualized. DMD results emphasize the importance of flow patterns oscillating lower than rotor teeth passage frequency and reveal that the coherent structures shift and expand as their frequencies decrease. The POD and DMD analyses provide an insightful perspective of the spatial and temporal behaviors of the flow in HSM.
Heat transfer within dynamically structured bubbling fluidized beds subject to vibration: A two‐fluid modeling study
Authors: Guo Qiang , Chiu Shawn , Da Wei , Boyce Christopher M. 
Published: November 2022

AbstractBubbling fluidized beds are often used to achieve a uniform particle temperature distribution in industrial processes involving gas and particles. However, the chaotic bubble dynamics pose significant challenges in scale‐up. Recent work (Guo et al., 2021, PNAS 118, e2108647118) has shown that using vibration can structure the bubbling pattern to a highly predictable manner with the characteristic bubble properties independent of system width, opening opportunities to address key issues associated with conventional bubbling fluidized beds. Herein, using two‐fluid modeling simulations, we studied heat transfer characteristics within the dynamically structured bubbling fluidized bed and compared to unstructured bubbling fluidized beds and packed beds. Simulations show that the structured bubbling fluidized bed can achieve the most uniform particle temperature distribution because it can achieve the best particle mixing while maintaining a global heat transfer coefficient similar to that of a freely bubbling fluidized bed.
Bio‐Inspired Deaminative Hydroxylation of Aminoheterocycles and Electron‐Deficient Anilines
Authors: Ghiazza Clément , Wagner Lucas , Fernández Sergio , Leutzsch Markus , Cornella Josep 
Published: November 2022

AbstractAmong the tools available to chemists for drug design of bioactive compounds, the bioisosteric replacement of atoms or groups of atoms is the cornerstone of modern strategies. Despite the undeniable interest in amino‐to‐hydroxyl interchange, enzymatic deaminative hydroxylation remains unmatched. Herein, we report a user friendly and safe procedure to selectively convert aminoheterocycles to their hydroxylated analogues by means of a simple pyrylium tetrafluoroborate salt. The hydroxylation step relies on a Lossen‐type rearrangement under mild conditions thus avoiding the use of strong hydroxide bases. In addition to biorelevant heterocycles, the deaminative hydroxylation of electron‐deficient anilines was also demonstrated. Finally, mechanistic experiments allowed the identification of the key intermediates, thus unveiling a rather unusual mechanism for this formal aromatic substitution.
Modelling Development in Radical (Co)Polymerization of Multivinyl Monomers
Authors: Lyu Jing , Li Yinghao , Li Zishan , Polanowski Piotr , Jeszka Jeremiasz K. , Matyjaszewski Krzysztof , Wang Wenxin 
Published: November 2022

AbstractRadical polymerization (RP) of multivinyl monomers (MVMs) provides a facile solution for manipulating polymer topology and has received increasing attention due to their industrial and academic significance. Continuous efforts have been made to understand their mechanism, which is the key to regulating materials structure. Modelling techniques have become a powerful tool that can provide detailed information on polymerization kinetics which is inaccessible by experiments. Many publications have reported the combination of experiments and modelling for free radical polymerization (FRP) and reversible‐deactivation radical polymerizations (RDRP) of MVMs. Herein, a minireview is presented for the most important modelling techniques and their applications in FRP/RDRP of MVMs. This review hopes to illustrate that the combination of modelling and wet experiments can be a great asset to polymer researchers and inspire new thinking for the future MVMs experiment optimization and product design.
Stereoselective Construction of Tertiary Homoallyl Alcohols and Ethers by Nucleophilic Substitution at Quaternary Carbon Stereocenters
Authors: Chen Xu , Patel Kaushalendra , Marek Ilan 
Published: November 2022

AbstractAn efficient method for the stereoselective construction of tertiary C−O bonds via a stereoinvertive nucleophilic substitution at the quaternary carbon stereocenter of cyclopropyl carbinol derivatives using water, alcohols and phenols as nucleophiles has been developed. This substitution reaction proceeds under mild conditions and tolerates several functional groups, providing a new access to the stereoselective formation of highly congested tertiary homoallyl alcohols and ethers.
Unravelling the Complex LiOH‐Based Cathode Chemistry in Lithium–Oxygen Batteries**
Authors: Zhang Xiahui , Dong Panpan , Noh Seunghyo , Zhang Xianghui , Cha Younghwan , Ha Su , Jang Ji‐Hoon , Song Min‐Kyu 
Published: November 2022

AbstractThe LiOH‐based cathode chemistry has demonstrated potential for high‐energy Li−O2batteries. However, the understanding of such complex chemistry remains incomplete. Herein, we use the combined experimental methods with ab initio calculations to study LiOH chemistry. We provide a unified reaction mechanism for LiOH formation during discharge via net 4 e−oxygen reduction, in which Li2O2acts as intermediate in low water‐content electrolyte but LiHO2as intermediate in high water‐content electrolyte. Besides, LiOH decomposes via 1 e−oxidation during charge, generating surface‐reactive hydroxyl species that degrade organic electrolytes and generate protons. These protons lead to early removal of LiOH, followed by a new high‐potential charge plateau (1 e−water oxidation). At following cycles, these accumulated protons lead to a new high‐potential discharge plateau, corresponding to water formation. Our findings shed light on understanding of 4 e−cathode chemistries in metal–air batteries.
Bioinspired Total Synthesis of Complex Nucleoside Antibiotics A201A, A201D and A201E
Authors: Wang Jiaxiang , Gao Jiahui , Guo Tianyun , Huo Xing , Zhang Wenhua , Liu Jian , Wang Xiaolei 
Published: November 2022

AbstractHerein, bioinspired total syntheses of A201A, A201D, and A201E based on a previously reported biosynthetic pathway are presented. The challenging 1,2‐cis‐furanoside, a core structure of the A201 family, was obtained by remote 2‐quinolinecarbonyl‐assisted glycosylation. We accomplished the total synthesis of A201A and A201E based on the critical 1,2‐cis‐furanoside moiety through late‐stage glycosylation without any interference from basic dimethyl adenosine. We also confirmed the absolute configuration of A201E by total synthesis. This modular synthesis strategy enables efficient preparation of A201 family antibiotics, allowing the study of their structure–activity relationships and mode of action. This study satisfies the increasing demand for developing novel antibiotics inspired by the A201 family.
Dendritic Quaternary‐Encoded Oligourethanes for Data Encryption
Authors: Shi Qiangqiang , Zhou Xin , Xu Jie , Zhang Jialin , Wang Ning , Zhang Guoying , Hu Jinming , Liu Shiyong 
Published: November 2022

AbstractThe use of sequence‐defined digital polymers for data storage and encryption has received increasing attention due to their precision structures similar to natural biomacromolecules (e.g., DNA) but increased stability. However, the rapid development of sequencing techniques raises the concern of information leakage. Herein, dendritic quaternary‐encoded oligourethanes bearing a photoresponsive trigger, self‐immolative backbones, and a mass spectrometry tag of PEG dendron have been developed for data encryption. Although the sequence information in linear analogs can be readily deciphered by mass spectrometry, sequencing of dendritic oligourethanes cannot be achieved by either primary MS or tandem MS/MS owing to the unique spatial conformation. Intriguingly, the fragmentation pathways of a quaternary dendrimer under MS/MS conditions can be converted to 2772‐bit 2D matrices with ≈1.98×1087permutations, serving as high‐strength encryption keys for highly reliable data encryption.
Kinetic Resolution of Azaarylethynyl Tertiary Alcohols by Chiral Brønsted Acid Catalysed Phosphine‐Mediated Deoxygenation
Authors: Wang Guanghui , Li Lulu , Jiang Yifeng , Zhao Xiaowei , Ban Xu , Shao Tianju , Yin Yanli , Jiang Zhiyong 
Published: November 2022

AbstractA chiral Brønsted acid catalysed phosphine‐mediated deoxygenation protocol is reported. This metal‐free method provides a precise kinetic resolution platform for azaarylethynyl tertiary alcohols, which are a broad category of biologically and synthetically important azaarene derivatives. In addition to providing an efficient method for the first asymmetric preparation of these tertiary alcohols, the strategy facilitates the construction of azaaryl‐functionalized allenes with good to excellent enantioselectivities. The high selectivity factors (sup to 235), broad substrate scope, and ability to convert azaaryl compounds into both chiral tertiary alcohols and allenes robustly underscore the efficiency and promising utility of this method. The practicability is further validated by the successful synthesis of deuterated allenes with high ee values and substantial incorporation of deuterium using inexpensive D2O as the deuterium source.
Diboraanthracene‐Doped Polymer Systems for Colour‐Tuneable Room‐Temperature Organic Afterglow
Authors: Jovaišaitė Justina , Kirschner Sven , Raišys Steponas , Kreiza Gediminas , Baronas Paulius , Juršėnas Saulius , Wagner Matthias 
Published: November 2022

AbstractOrganic ultralong room temperature phosphorescence (RTP), or organic afterglow, is a unique phenomenon, gaining widespread attention due to its far‐reaching application potential and fundamental interest. Here, two laterally expanded 9,10‐dimesityl‐dihydro‐9,10‐diboraanthracene (DBA) derivatives are demonstrated as excellent afterglow materials for red and blue‐green light emission, which is traced back to persistent thermally activated delayed fluorescence and RTP. The lateral substitution of polycyclic DBA scaffold, together with weak transversal electron‐donating mesityl groups, ensures the optimal molecular properties for (reverse) intersystem crossing and long‐lived triplet states in a rigid poly(methyl methacrylate) matrix. The achieved afterglow emission quantum yields of up to 3 % and 15 %, afterglow lifetimes up to 0.8 s and 3.2 s and afterglow durations up to 5 s and 25 s (for red and blue‐green emitters, respectively) are attributed to the properties of single molecules.
A Semi‐solid Zinc Powder‐based Slurry Anode for Advanced Aqueous Zinc‐ion Batteries
Authors: Yang Zefang , Zhang Qi , Li Wenbin , Xie Chunlin , Wu Tingqing , Hu Chao , Tang Yougen , Wang Haiyan 
Published: November 2022

AbstractThe booming of aqueous zinc‐ion batteries (AZIBs) draws the researchers’ attention to issues of zinc metal anodes, such as uncontrollable dendrite growth, corrosion, and volume effects. Zinc powder anode is more suitable for the industrial application of AZIBs than the widely used zinc foil anode due to its low cost, tunability and processability. However, the related solutions are rarely studied because the above issues of zinc metal anode are more serious in zinc powder anode. Herein, for the first time, we design a semi‐solid zinc slurry anode consisting of zinc powder and zincophilic tin additive dispersed in a conductive elastic rheological network. Zinc can be deposited homogeneously on the dispersed tin particles, which avoids agglomerative zinc deposition and alleviates volume change during repeated zinc stripping/plating. Moreover, the practical application of the full cell with slurry is very promising since its operating life can be easily extended by facile slurry renewal.
Ein Helikales Zweischichtiges Nichtbenzoides Nanographen als [10]Helicen mit Zwei Eingebetteten Heptagonalen Ringen
Authors: Yang Lin , Ju Yang‐Yang , Medel Miguel A. , Fu Yubin , Komber Hartmut , Dmitrieva Evgenia , Zhang Jin‐Jiang , Obermann Sebastian , Campaña Araceli G. , Ma Ji , Feng Xinliang 
Published: November 2022

AbstractDie atomgenaue Synthese von helikalen mehrschichtigen Nanographenen (NG) neuer Topologie ist aufgrund ihrer exotischen physikochemischen Eigenschaften von substanziellem Interesse. Allerdings ist die Synthese dieser Nanographene, speziell mit nicht benzoiden Ringen, äußerst herausfordernd. Wir präsentieren in diesem Artikel die effiziente Synthese des ersten helikalen zweischichtigen nichtbenzoiden Nanographens (HBNG1) ausgehend von einem maßgeschneiderten Azulen‐Vorläufer, welcher bereits das neuartige Strukturelement zweier in [10]Helicen eingebetteter heptagonaler Ringe enthält. Die Einkristalldiffraktometrie gibt Einblick in die sterisch stark gespannte Doppelschichtstruktur mit einem Rekordwert für den kleinsten Interschichtabstand von nur 3.2 Å, in der Substanzklasse der doppelschichtigen Nanographene. Bemerkenswerterweise kommt es im Raum zwischen den Schichten zu π–π Wechselwirkungen. Wir untersuchten diesen Effekt durch in situ Spektroelektrochemie und Simulationen mittels Dichtefunktionaltheorie (DFT). Des Weiteren wurden die chiroptischen Eigenschaften derP/M‐Enantiomere vonHBNG1durch Zirkulardichroismus und zirkular polarisierter Fluoreszenz charakterisiert.
Small Fluorogenic Amino Acids for Peptide‐Guided Background‐Free Imaging
Authors: de Moliner Fabio , Konieczna Zuzanna , Mendive‐Tapia Lorena , Saleeb Rebecca S. , Morris Katie , Gonzalez‐Vera Juan Antonio , Kaizuka Takeshi , Grant Seth G. N. , Horrocks Mathew H. , Vendrell Marc 
Published: November 2022

AbstractThe multiple applications of super‐resolution microscopy have prompted the need for minimally invasive labeling strategies for peptide‐guided fluorescence imaging. Many fluorescent reporters display limitations (e.g., large and charged scaffolds, non‐specific binding) as building blocks for the construction of fluorogenic peptides. Herein we have built a library of benzodiazole amino acids and systematically examined them as reporters for background‐free fluorescence microscopy. We have identified amine‐derivatized benzoselenadiazoles as scalable and photostable amino acids for the straightforward solid‐phase synthesis of fluorescent peptides. Benzodiazole amino acids retain the binding capabilities of bioactive peptides and display excellent signal‐to‐background ratios. Furthermore, we have demonstrated their application in peptide‐PAINT imaging of postsynaptic density protein‐95 nanoclusters in the synaptosomes from mouse brain tissues.
Interfaces with Fluorinated Amphiphiles: Superstructures and Microfluidics
Authors: Junge Florian , Lee Pin‐Wei , Kumar Singh Abhishek , Wasternack Janos , Pachnicz Michał P. , Haag Rainer , Schalley Christoph A. 
Published: November 2022

AbstractThis Minireview discusses recent developments in research on the interfacial phenomena of fluorinated amphiphiles, with a focus on applications that exploit the unique and manifold interfacial properties associated with these amphiphiles. Most notably, fluorinated amphiphiles form stable aggregates with often distinctly different morphologies compared to their nonfluorinated counterparts. Consequently, fluorinated surfactants have found wide use in high‐performance applications such as microfluidic‐assisted screening. Additionally, their fluorine‐specific behaviour at solid/liquid interfaces, such as the formation of superhydrophobic coatings after deposition on surfaces, will be discussed. As fluorinated surfactants and perfluorinated materials in general pose potential environmental threats, recent developments in their remediation based on their adsorption onto fluorinated surfaces will be evaluated.
Boosting Benzene Oxidation with a Spin‐State‐Controlled Nuclearity Effect on Iron Sub‐Nanocatalysts
Authors: Bu Fanle , Chen Chaoqiu , Yu Yu , Hao Wentao , Zhao Shichao , Hu Yongfeng , Qin Yong 
Published: November 2022

AbstractA fundamental understanding of the nature of nuclearity effects is important for the rational design of superior sub‐nanocatalysts with low nuclearity, but remains a long‐standing challenge. Using atomic layer deposition, we precisely synthesized Fe sub‐nanocatalysts with tunable nuclearity (Fe1–Fe4) anchored on N,O‐co‐doped carbon nanorods (NOC). The electronic properties and spin configuration of the Fe sub‐nanocatalysts were nuclearity dependent and dominated the H2O2activation modes and adsorption strength of active O species on Fe sites toward C−H oxidation. The Fe1‐NOC single atom catalyst exhibits state‐of‐the‐art activity for benzene oxidation to phenol, which is ascribed to its unique coordination environment (Fe1N2O3) and medium spin state (t2g4eg1); turnover frequencies of 407 h−1at 25 °C and 1869 h−1at 60 °C were obtained, which is 3.4, 5.7, and 13.6 times higher than those of Fe dimer, trimer, and tetramer catalysts, respectively.
Preparation of a salt‐responsive Gemini viscoelastic surfactant for application to solids‐free drilling fluids
Authors: Deng Yilin , Sun Jinsheng , Wang Ren , Yang Jie , Qu Yuanzhi , Wang Jiao , Huang Hongjun , Cheng Rongchao , Gao Shifeng , Ren Han 
Published: November 2022

AbstractIn order to solve the problem of poor rheological properties of solid‐free drilling fluids in salt‐bearing formations and prevent drilling accidents such as lost circulation, formation collapse, and wellbore instability, it is crucial to develop a new type of viscosifier. In this study, a salt‐responsive Gemini viscoelastic surfactant (NT‐1) was synthesized by using erucamide as a hydrophobic chain and introducing a benzene ring and a carboxyl group into the linker. In addition, it is used as a viscosifier for solid‐free drilling fluids. The structure of the surfactant was characterized by 1H nuclear magnetic resonance (NMR), 13C NMR, Fourier transform infrared spectroscopy, and electrospray ionization tandem mass spectrometry (ESI‐MS), and its physicochemical properties were determined by surface tensiometer, thermogravimetric‐differential scanning calorimetry, dynamic lighting scattering and rheometer. Its performance in solid‐free drilling fluids was evaluated according to the American Petroleum Institute (API) standard. The results show that the surfactant has a low critical micelle concentration (31.74 μmol/L), excellent thermal stability and water solubility. In particular, NT‐1 can self‐assemble into worm‐like micelles under the action of salt, and the spatial network structure formed by the interweaving of these micelles can endow the drilling fluid with good rheology and viscoelasticity. NT‐1 is compatible with conventional drilling fluid polymer additives, which can effectively improve solid‐free drilling fluids' rheological properties and fluid loss properties in salt layers. The temperature resistance in drilling fluid systems can reach 120°C. This work verifies the feasibility of using viscoelastic surfactants as viscosifiers in solid‐free drilling fluids and provides new ideas for developing salt‐responsive smart drilling fluids.