bluuebunny/crossref_metadata_2025_split huggingface dataset:
Resilient finite‐time fault detection dissipative‐based filter for semi‐Markovian jump systems with incomplete measurements
Authors: Sakthivel Rathinasamy , Nithya Venkatesan , Suveetha Veeralpatti Thangavel 
Published: March 2022

SummaryIn this article, the problem of resilient finite‐time fault detection dissipative‐based filter design is investigated for a class discrete‐time semi‐Markovian jump systems with incomplete measurements, dynamic quantization and time‐varying delay. The considered system includes various network‐induced imperfections such as missing measurements, transmission delay and dynamic signal quantization. Specifically, all these imperfections are modeled using stochastic variables following Bernoulli random distribution. In addition, the transition probability of the semi‐Markov process is time‐varying along with the lower and upper bounds of the transition rate. Eventually, a set of sufficient conditions is derived in terms of linear matrix inequalities (LMIs) by assuming proper Lyapunov–Krasovskii functional and using S‐procedure lemma such that the augmented filtering error system is stochastically finite‐time bounded with prescribed dissipative performance. Finally, the applicability and usefulness of the proposed filter design is demonstrated through a pulse‐width‐modulation‐boost‐converter (PWM) model.
A Novel Biasing Scheme of Electrolyte‐Gated Organic Transistors for Safe In Vivo Amplification of Electrophysiological Signals
Authors: Di Lauro Michele , Zucchini Elena , De Salvo Anna , Delfino Emanuela , Bianchi Michele , Murgia Mauro , Carli Stefano , Biscarini Fabio , Fadiga Luciano 
Published: March 2022

AbstractSuccessful translation of organic transistors as sensors and transducers to clinical settings is hampered by safety and stability issues. The operation of such devices demands driving voltages across the biotic/abiotic interface, which may result in undesired electrochemical reactions that may harm both the patient and the device. In this study, a novel operational mode is presented for electrolyte‐gated organic transistors that avoid these drawbacks: the common‐drain/grounded‐source configuration. This approach reverts the standard common‐source/common‐ground configuration and achieves maximum signal amplification while applying null net bias across the electrolyte, with no parasitic currents. The viability of the proposed configuration is demonstrated by recording in vivo the somatosensory evoked activity from the barrel cortex of rats. The main inherent advantage of transistors with respect to passive electrodes is preserved in the proposed scheme: a superior signal‐to‐noise ratio is achieved which enables the detection of evoked activity at the single‐trial level. Then, common‐drain/grounded‐source organic transistors are proposed as ideal candidate devices for a harmless translational recording platform.
A Method for Deconvoluting and Quantifying the Real‐Time Species Fluxes and Ionic Currents Using In Situ Electrochemical Quartz Crystal Microbalance
Authors: Zheng Kai , Xian Yongqiu , Lin Zifeng 
Published: March 2022

AbstractElectrochemical quartz crystal microbalance (EQCM) is a powerful tool to screen the gravimetric response of electrochemically active electrodes. In this study, a method is proposed to deconvolute and quantify the real‐time fluxes and ionic currents of different species based on the EQCM measurement results. This work creatively conceptualizes the flux cyclic voltammograms (CVs) and ionic current CVs, and applys them to analyze the real‐time molecules and ion evolution. As a proof of concept, Ti3C2Tx MXene, the most studied 2D metal carbide, is investigated as a supercapacitor electrode in 1 m H2SO4 electrolyte. The real‐time H2O and H+ fluxes are obtained using the proposed approach and corresponding flux CVs are constructed. The potential‐dependent evolution of H2O and H+ fluxes suggest that the insertion of hydrated H+ contributes significantly to the double‐layer capacitance. The H+ CV calculated from the H+ flux overlaps with the experimental measured CV, confirming that H+ is the only interactive charge carrier for screening the Ti3C2Tx electrode charge.
A Chromic and Near‐Infrared Emissive Mechanophore Serving as a Versatile Force Meter in Micelle–Hydrogel Composites
Authors: Yang Fan , Li Xiaopei , Chen Yulan 
Published: March 2022

AbstractMechanofluorochromic polymers, which can indicate damage or excessive stress in highly polarized environments with a clearly perceptible optical signal, are potentially useful in a variety of exciting applications. However, most reported fluorochromic mechanophores exhibit poor color contrast and fluorescence penetration, or are irreversible in polarized phase after mechanical activation. Here, this challenge is tackled by designing and engineering a novel near‐infrared (NIR) emissive, rhodanmin derived mechanophore (Rh‐Co) in a kind of hydrogel composites. The ring‐opened Rh‐Co is unique in high molar extinction coefficient and bright NIR emission with such optical transition under force directly corresponding to covalent bond scission and reversibly switchable in an aqueous environment. The hydrogel composites thus can sensitively change their color from yellow to green and emit highly penetrated NIR fluorescence when different types of forces (tension, compression, and friction force) are applied, highlighting the potential applications of Rh‐Co in biocompatible environments as a “force meter.”
Zero‐Dimensional Luminescent Metal Halide Hybrids Enabling Bulk Transparent Medium as Large‐Area X‐Ray Scintillators
Authors: Li Bohan , Xu Yan , Zhang Xinlei , Han Kai , Jin Jiance , Xia Zhiguo 
Published: March 2022

AbstractScintillators are critical in medical imaging, non‐destructive security screening, and space exploration applications. However, it still remains a challenge to achieve large‐area and high‐transparency scintillators by a low‐cost and easy‐to‐implement way. Herein, a large transparent medium with a diameter over 10 cm is prepared via a facile melt‐quenching strategy using a stoichiometric mixture of ethyltriphenylphosphonium bromide (ETPBr) and MnBr2 as raw materials. Benefiting from the crystallization behavior of high‐efficiency green‐emitting (ETP)2MnBr4 nanocrystals hybridized with amorphous phase in the transparent wafer, the (ETP)2MnBr4‐based transparent medium as a scintillator evidences a high transparency (over 80%, ranging from 500 to 800 nm), a high light yield of ≈35 000 ± 2000 photon per MeV, a low detection limit of 103 nGy S–1, and a competitive spatial resolution of 13.4 lp mm–1 for X‐ray imaging. This work offers a distinctive simple and fast melt‐quenching methodology to fabricate (ETP)2MnBr4 metal halide X‐ray scintillator wafer with large‐area and shape flexibility, excellent transparency, and high scintillation performance for the medical or industrial X‐ray imaging application.
A Review on the Bioinspired Photocatalysts and Photocatalytic Systems
Authors: Yang Liuqing , Fan Deqi , Li Zhaolin , Cheng Yelan , Yang Xiaofei , Zhang Tierui 
Published: March 2022

AbstractAfter long‐term evolution, organisms in nature have achieved optimal structure, organization, and function to adapt to the environment. Some ingenious biological structures have highly efficient solar light absorption, matter transmission, and natural photocatalytic properties, such as leaves, sunflowers, seaweeds, algae, bacteria. Artificial photocatalysis, which involves CO2 reduction and water splitting to obtain green renewable energy or oxygen, is of great significance for solving the problem of energy shortages, achieving carbon neutrality, and building a sustainable society. In order to improve the efficiency of artificial photocatalysis, it is necessary to develop highly efficient photocatalysts by expanding ideas and drawing innovative inspiration from nature. Artificially constructed photocatalysts with bionic structures achieved by simulating natural organisms have gradually become an exciting research field with great potential in recent years. This article reviews bioinspired photocatalysts and photocatalytic systems from the aspects of principle, composition, construction method, and the achieved performance. It is expected that this review will help researchers develop a systematic and in‐depth understanding for the biomimetic design of photocatalysts and photocatalytic systems.
Symmetrically Ion‐Gated In‐Plane Metal‐Oxide Transistors for Highly Sensitive and Low‐Voltage Driven Bioelectronics
Authors: Kang Jingu , Jang Young‐Woo , Moon Sang Hee , Kang Youngjin , Kim Jaehyun , Kim Yong‐Hoon , Park Sung Kyu 
Published: March 2022

AbstractTo provide a unique opportunity for on‐chip scaled bioelectronics, a symmetrically gated metal‐oxide electric double layer transistor (EDLT) with ion‐gel (IG) gate dielectric and simple in‐plane Corbino electrode architecture is proposed. Using amorphous indium‐gallium‐zinc oxide (a‐IGZO) semiconductor and IG dielectric layers, low‐voltage driven EDLTs with high ionotronic effects can be realized. More importantly, in contrast to the conventional asymmetric rectangular EDLTs which can cause non‐uniform potential variation in the active channel layer and eventually degrade the sensing performance, the new symmetrical in‐plane type EDLTs achieve high and spatially uniform ion responsive behaviors. The symmetrically gated a‐IGZO EDLTs exhibited a responsivity of 129.4% to 5 ppm mercury (Hg2+) ions which are approximately three times higher than that with conventional electrode structure (responsivity of 38.5%). To confirm the viability of the new device architectures and the findings, the detailed mechanism of the symmetric gating effects in the in‐plane EDLTs with a variety of electrical characterization and 3D fine element analysis simulations is also discussed.
Deconvolution of Light‐Induced Ion Migration Phenomena by Statistical Analysis of Cathodoluminescence in Lead Halide‐Based Perovskites
Authors: Shirzadi Erfan , Tappy Nicolas , Ansari Fatemeh , Nazeeruddin Mohammad Khaja , Hagfeldt Anders , Dyson Paul J. 
Published: March 2022

AbstractStudying the compositional instability of mixed ion perovskites under light illumination is important to understand the mechanisms underlying their efficiency and stability. However, current techniques are limited in resolution and are unable to deconvolute minor ion migration phenomena. Here, a method that enables ion migration to be studied allowing different segregation mechanisms to be elucidated is described. Statistical analysis is applied to cathodoluminescence data to generate compositional distribution histograms. Using these histograms, two different ion migration phenomena, horizontal ion migration (HIM) and vertical ion migration (VIM), are identified in different perovskite films. It is found that most passivating agents inhibit HIM, but not VIM. However, VIM can be reduced by deposition of imidazolium iodide on the perovskite surface. This method can be used to study perovskite‐based devices efficiency and stability by providing molecular level mechanistic understanding of passivation approaches leading to performance improvement of perovskite solar cells via rational design.
Pharmacological Perturbation of Mechanical Contractility Enables Robust Transdifferentiation of Human Fibroblasts into Neurons
Authors: He Zheng‐Quan , Li Yu‐Huan , Feng Gui‐Hai , Yuan Xue‐Wei , Lu Zong‐Bao , Dai Min , Hu Yan‐Ping , Zhang Ying , Zhou Qi , Li Wei 
Published: March 2022

AbstractDirect cell reprogramming, also called transdifferentiation, is valuable for cell fate studies and regenerative medicine. Current approaches to transdifferentiation are usually achieved by directly targeting the nuclear functions, such as manipulating the lineage‐specific transcriptional factors, microRNAs, and epigenetic modifications. Here, a robust method to convert fibroblasts to neurons through targeting the cytoskeleton followed by exposure to lineage‐specification surroundings is reported. Treatment of human foreskin fibroblasts with a single molecule inhibitor of the actomyosin contraction, can disrupt the cytoskeleton, promote cell softening and nuclear export of YAP/TAZ, and induce a neuron‐like state. These neuron‐like cells can be further converted into mature neurons, while single‐cell RNA‐seq shows the homogeneity of these cells during the induction process. Finally, transcriptomic analysis shows that cytoskeletal disruption collapses the original lineage expression profile and evokes an intermediate state. These findings shed a light on the underestimated role of the cytoskeleton in maintaining cell identity and provide a paradigm for lineage conversion through the regulation of mechanical properties.
Size‐Controllable Nickel Sulfide Nanoparticles Embedded in Carbon Nanofibers as High‐Rate Conversion Cathodes for Hybrid Mg‐Based Battery
Authors: Zhu Guilei , Xia Guanglin , Pan Hongge , Yu Xuebin 
Published: March 2022

AbstractThe integration of highly‐safe Mg anode and fast Li+ kinetics endows hybrid Mg2+/Li+ batteries (MLIBs) a promising future, but the practical application is circumvented by the lack of appropriate cathodes that enable the realization of an enough participation of Mg2+ in the reactions, resulting in a high dependence on Li+. Herein, the authors develop a series of size‐controllable nickel sulfide nanoparticles embedded in carbon nanofibers (NiS@C) with synergistic effect of particle diameter and carbon content as the cathode material for MLIBs. The optimized particle size is designed to maximize the utilization of the active material and remit internal stress, and appropriate carbon encapsulation efficiently inhibiting the pulverization of particles and accelerates the ability of conducting ions and electrons. In consequence, the representative NiS@C delivers superior electrochemical performance with a highest discharge capacity of 435 mAh g−1 at 50 mA g−1. Such conversion cathode also exhibits excellent rate performance and remarkable cycle life. Significantly, the conversion mechanism of NiS in MLIBs is unambiguously demonstrated for the first time, affirming the corporate involvement of both Mg2+ and Li+ at the cathodic side. This work underlines a guide for developing conversion‐type materials with high rate capability and cyclic performance for energy storage applications.
Versatile boron‐based thermally activated delayed fluorescence materials for organic light‐emitting diodes
Authors: Han Jianmei , Chen Yanying , Li Nengquan , Huang Zhongyan , Yang Chuluo 
Published: March 2022

AbstractDuring the last few years, organoboron‐based thermally activated delayed fluorescence (TADF) materials have received extensive attention in optoelectronic area, owing to the unique electronegativity of boron atom. Herein, many research progress of organoboron‐based TADF materials for organic optoelectronic devices is summarized. This review comprehensively documents the organoboron‐based TADF materials according to the emission colors from blue to red‐near‐infrared (red‐NIR), covering the molecular design strategies, photophysical properties, and optoelectronic performance in organic light‐emitting diodes (OLEDs). The current progress and future challenges in this fast‐growing fields are reviewed systematically, providing instructive guidance for the future research on high‐performance TADF‐OLEDs.
Guided Synthesis of a Mo/Zn Dual Single‐Atom Nanozyme with Synergistic Effect and Peroxidase‐like Activity
Authors: Ma Chong‐Bo , Xu Yaping , Wu Lixin , Wang Quan , Zheng Jia‐Jia , Ren Guoxi , Wang Xiaoyu , Gao Xingfa , Zhou Ming , Wang Ming , Wei Hui 
Published: March 2022

AbstractWe present a facile route towards a dual single‐atom nanozyme composed of Zn and Mo, which utilizes the non‐covalent nano‐assembly of polyoxometalates, supramolecular coordination complexes as the metal‐atom precursor, and a macroscopic amphiphilic aerogel as the supporting substrate. The dual single‐atoms of Zn and Mo have a high content (1.5 and 7.3 wt%, respectively) and exhibit a synergistic effect and a peroxidase‐like activity. The Zn/Mo site was identified as the main active center by X‐ray absorption fine structure spectroscopy and density functional theory calculation. The detection of versatile analytes, including intracellular H2O2, glucose in serum, cholesterol, and ascorbic acid in commercial beverages was achieved. The nanozyme has an outstanding stability and maintained its performance after one year's storage. This study develops a new peroxidase‐like nanozyme and provides a robust synthetic strategy for single‐atom catalysts by utilizing an aerogel as a facile substrate that is capable of stabilizing various metal atoms.
Monoazadichalcogenasumanenes: Synthesis, Structures, and Ring Reconstruction via Atom Transfer under Acidic Conditions
Authors: Shang Jihai , Wang Renjie , Yuan Chengshan , Liu Zitong , Zhang Hao‐Li , Shao Xiangfeng 
Published: March 2022

AbstractBuckybowls have unique properties that can be tailored by embedding main‐group elements into their π‐scaffolds. Herein, a synthetic approach is developed for producing monoazadichalcogenasumanenes (4 a/4 b, 6 a/6 b, 7 a/7 b) derived from sumanene by replacing its three benzylic carbons with one nitrogen and two chalcogen atoms (S for 4 a/4 b, Se for 6 a/6 b, Te for 7 a/7 b). Monoazadichalcogenasumanenes are deeper π‐bowls than trichalcogensumanenes as the C−N bond is much shorter than C−X (X=S, Se, Te). The bowl‐depth of 4 b (0.95 Å) is greater than that of corannulene (0.85 Å). The nitrogen atom donates electron density to the entire π‐system that makes monoazadichalcogenasumanenes electron‐rich. They undergo ring reconstruction of chalcogenophene ring via transferring a chalcogen atom from one molecule to another under acidic conditions. The nitrogen and chalcogen atoms play crucial role on this reaction.
Formation of Breslow Intermediates from N‐Heterocyclic Carbenes and Aldehydes Involves Autocatalysis by the Breslow Intermediate, and a Hemiacetal
Authors: Wessels Alina , Klussmann Martin , Breugst Martin , Schlörer Nils E. , Berkessel Albrecht 
Published: March 2022

AbstractUnder aprotic conditions, the stoichiometric reaction of N‐heterocyclic carbenes (NHCs) such as imidazolidin‐2‐ylidenes with aldehydes affords Breslow Intermediates (BIs), involving a formal 1,2‐C‐to‐O proton shift. We herein report kinetic studies (NMR), complemented by DFT calculations, on the mechanism of this kinetically disfavored H‐translocation. Variable time normalization analysis (VTNA) revealed that the kinetic orders of the reactants vary for different NHC‐to‐aldehyde ratios, indicating different and ratio‐dependent mechanistic regimes. We propose that for high NHC‐to‐aldehyde ratios, the H‐shift takes place in the primary, zwitterionic NHC‐aldehyde adduct. With excess aldehyde, the zwitterion is in equilibrium with a hemiacetal, in which the H‐shift occurs. In both regimes, the critical H‐shift is auto‐catalyzed by the BI. Kinetic isotope effects observed for R‐CDO are in line with our proposal. Furthermore, we detected an H‐bonded complex of the BI with excess NHC (NMR).
Iridium‐Catalyzed Asymmetric Allylic Substitution of Methyl Azaarenes
Authors: Liu Xi‐Jia , Zhang Wen‐Yun , Zheng Chao , You Shu‐Li 
Published: March 2022

AbstractHerein, an Ir‐catalyzed asymmetric allylic substitution reaction of methyl azaarenes is described. Azaarenes such as (benzo)thiazole, oxazole, benzoimidazole, pyridine, and (iso)quinoline are all tolerated. The corresponding chiral azaarene derivatives are obtained in good yields with high enantioselectivity (up to 96 % yield and 99 % ee). The utilization of the Knochel reagent TMPZnBr⋅LiBr warrants the in situ formation of benzylic nucleophiles without additional activating reagents. 1H NMR studies suggested a two‐fold function of the Knochel reagent in this reaction. The synthetic utility of this method has been showcased by a concise enantioselective synthesis of an allosteric protein kinase modulator.
Atomic‐Layered Cu5 Nanoclusters on FeS2 with Dual Catalytic Sites for Efficient and Selective H2O2 Activation
Authors: Ling Cancan , Liu Xiufan , Li Hao , Wang Xiaobing , Gu Huayu , Wei Kai , Li Meiqi , Shi Yanbiao , Ben Haijie , Zhan Guangming , Liang Chuan , Shen Wenjuan , Li Yaling , Zhao Jincai , Zhang Lizhi 
Published: March 2022

AbstractRegulating the distribution of reactive oxygen species generated from H2O2 activation is the prerequisite to ensuring the efficient and safe use of H2O2 in the chemistry and life science fields. Herein, we demonstrate that constructing a dual Cu−Fe site through the self‐assembly of single‐atomic‐layered Cu5 nanoclusters onto a FeS2 surface achieves selective H2O2 activation with high efficiency. Unlike its unitary Cu or Fe counterpart, the dual Cu−Fe sites residing at the perimeter zone of the Cu5/FeS2 interface facilitate H2O2 adsorption and barrierless decomposition into ⋅OH via forming a bridging Cu‐O‐O‐Fe complex. The robust in situ formation of ⋅OH governed by this atomic‐layered catalyst enables the effective oxidation of several refractory toxic pollutants across a broad pH range, including alachlor, sulfadimidine, p‐nitrobenzoic acid, p‐chlorophenol, p‐chloronitrobenzene. This work highlights the concept of building a dual catalytic site in manipulating selective H2O2 activation on the surface molecular level towards efficient environmental control and beyond.
A Symmetry‐Based Kinematic Theory for Nanocrystal Morphology Design
Authors: Ni Bing , González‐Rubio Guillermo , Kirner Felizitas , Zhang Siyuan , Cölfen Helmut 
Published: March 2022

AbstractThe growth of crystalline nanoparticles (NPs) generally involves three processes: nucleation, growth, and shape evolution. Among them, the shape evolution is less understood, despite the importance of morphology for NP properties. Here, we propose a symmetry‐based kinematic theory (SBKT) based on classical growth theories to illustrate the process. Based on the crystal lattice, nucleus (or seed) symmetry, and the preferential growth directions under the experimental conditions, the SBKT can illustrate the growth trajectories. The theory accommodates the conventional criteria of the major existing theories for crystal growth and provides tools to better understand the symmetry‐breaking process during the growth of anisotropic structures. Furthermore, complex dendritic growth is theoretically and experimentally demonstrated. Thus, it provides a framework to explain the shape evolution, and extends the morphogenesis prediction to cases, which cannot be treated by other theories.
Manganese‐Catalyzed Asymmetric Hydrogenation of 3H‐Indoles
Authors: Liu Chenguang , Wang Mingyang , Xu Yihan , Li Yibiao , Liu Qiang 
Published: March 2022

AbstractThe asymmetric hydrogenation (AH) of 3H‐indoles represents an ideal approach to the synthesis of useful chiral indoline scaffolds. However, very few catalytic systems based on precious metals have been developed to realize this challenging reaction. Herein, we report a Mn‐catalyzed AH of 3H‐indoles with excellent yields and enantioselectivities. The kinetic resolution of racemic 3H‐indoles by AH was also achieved with high s‐factors to construct quaternary stereocenters. Many acid‐sensitive functional groups, which cannot be tolerated when using a state‐of‐the‐art ruthenium catalyst, were compatible with manganese catalysis. This new process expands the scope of this transformation and highlights the uniqueness of earth‐abundant metal catalysis. The reaction could proceed with catalyst loadings at the parts per million (ppm) level with an exceptional turnover number of 72 350. This is the highest value yet reported for an earth‐abundant metal‐catalyzed AH reaction.