bluuebunny/crossref_metadata_2025 huggingface dataset:
Programmable Shape‐Preserving Soft Robotics Arm via Multimodal Multistability
Authors: Shahryari Benyamin , Mofatteh Hossein , Sargazi Arian , Mirabolghasemi Armin , Meger David , Akbarzadeh Abdolhamid
Published: August 2024

Inflatable multistable materials have significantly advanced the design of shape‐preserving soft robotic arms, offering substantial benefits in terms of shape adaptability, energy efficiency, and safety, ensuring operational reliability even in the event of sudden power loss. However, existing strategies for realizing multistable arms often limit themselves to a single mode of multistability, commonly with rotationally symmetric designs favoring extension stability and asymmetric designs inducing bending stability. To address the limitation, this study introduces a pioneering platform termed multimodal multistability that utilizes geometrical frustration. A single cylindrical symmetric cell, designed for extension bistability, could achieve frustrated multistable states in bending by controlling the cell with multiple degrees of freedom incorporated pneumatic actuator. This platform extends the spectrum of attainable stable trajectories while preserving essential attributes of arms, such as load‐bearability, programmability, and reversibility of shape changes. Leveraging a pneumatic system with four degrees of freedom for pressure control, not only enables capturing previously unexplored stable configurations in mechanical metastructures but also allows for the control of their deformation modes. With applications spanning space exploration, medical instruments, and rescue missions, the multimodal multistability promises unparalleled flexibility and efficiency in the design and operation of soft robots.
Comprehensive Insight into Indium Oxide‐Based Catalysts for CO2 Hydrogenation: Thermal, Photo, and Photothermal Catalysis
Authors: Shi Zhisheng , Yang Liuqing , Lu Zhe , Han Qiutong , Wu Linlin , Wang Lu , Xiong Yujie , Ye Jinhua , Zou Zhigang , Zhou Yong
Published: August 2024

The conversion of carbon dioxide (CO2) into value‐added chemicals presents an innovative pathway for advancing the low‐carbon clean energy revolution, contributing significantly to CO2 emission reduction and resource utilization. Recently, In2O3‐based catalysts have emerged as a promising frontier in CO2 hydrogenation research. This review provides a comprehensive introduction of the latest advancements in the application of In2O3‐based catalysts across thermal, photocatalytic, and photothermal catalysis platforms. The review examines critical aspects such as structural properties, active sites, reaction mechanisms, performance enhancement, product impact, and the development of multi‐functional catalytic systems. Thermal Catalysis for CO2 hydrogenation involves the application of elevated temperatures to initiate and drive the hydrogenation reactions. Photocatalysis, on the other hand, harnesses light energy to facilitate these reactions. Among these approaches, photothermal catalysis has emerged as a particularly promising method for CO2 hydrogenation, offering several advantages over both thermal catalysis and photocatalysis. These advantages include more efficient energy utilization, a broader range of reaction conditions, enhanced synergistic effects, selective activation, and improved environmental sustainability. This review not only summarizes the current state of research in this field but also may provide critical insights and guidance for future studies aimed at advancing artificial carbon cycling processes.
Organic Surface Doping for High‐Performance Perovskite Transistors
Authors: Kim Ju‐Hyeon , Oh Chang‐Mok , Hwang In‐Wook , Park Kiyoung , Lee Kwanghee
Published: August 2024

Quasi‐2D perovskites have attracted significant attention because of their environmental robustness and superior long‐term stability compared with their 3D counterparts. However, they typically consist of a mixture of multiple quantum wells with different optoelectrical properties, which degrades the electronic properties and hinders further electronic applications. Here, to challenge this issue, a surface p‐doping strategy involving the introduction of a thiophene‐containing polymer onto the surface of quasi‐2D tin perovskites is reported. The tin ions in the perovskites effectively interact with the sulfur atoms in the thiophene moieties, thereby generating hole carriers and inducing p‐doping. The resulting doped quasi‐2D perovskites exhibit excellent surface crystallinity, lower trap density, and enhanced charge carrier transport capability along the perovskite semiconductor channels. Consequently, the doped quasi‐2D tin perovskite‐based transistors exhibit a high field‐effect mobility of 53 cm2V−1s−1 (7 cm2V−1s−1 for the control device) and an outstanding on/off ratio (>107), together with superior operational stability.
Skin Effect of Electromagnetic Flux in Anisotropic Zero‐Index Metamaterials
Authors: Mei Ran , Xu Yadong , Gao Lei , Xu He‐Xiu , Lai Yun , Luo Jie
Published: August 2024

Skin effect in electromagnetism describes the tendency of alternating current to predominantly flow near the surface rather than through the center of a conductor. Here, another skin effect of electromagnetic flux is reported to occur in non‐conductive materials, specifically within 3D anisotropic zero‐index metamaterials, as well as its potential application in subwavelength wave manipulation. It is found that when a medium of near‐zero longitudinal permittivity and permeability is embedded with inclusions whose transverse permittivity and/or permeability approach zero, the electromagnetic flux therein is directed and extremely compressed beneath the surfaces of inclusions within a skin depth less than λ0/150. This unusual effect empowers arbitrary control of electromagnetic flux at deep subwavelength scale. Customized subwavelength pathways for electromagnetic flux are demonstrated in full‐wave simulations via practical implementations. The study opens a new avenue for extreme confinement and flexible control of electromagnetic flux at deep‐subwavelength scale.
One‐Pot Reactions of Ynones with Isothiocyanates for Accessing 2‐Aminothiophenone and Indole‐Fused/Indole‐Substituted Thiophenone Derivatives
Authors: Jin Zefeng , Li Cuiying , Shen Guodong , Kang Honglan , Lv Xin
Published: August 2024

A copper or silver‐catalyzed cascade addition/5‐exo‐dig cyclization/isomerization reaction of isothiocyanate with ynone has been developed. This strategy enables the synthesis of a variety of (Z)‐2‐ylidene‐5‐aminothiophen‐3‐one derivatives with diverse substitutions in a single vessel. The method is featured with pot‐economy as well as regio‐ and Z‐selectivity. Several biologically active molecules could be modified using this strategy. Moreover, the relevant indole‐fused and indole‐substituted thiophenone derivatives were also assembled in one pot by merging this strategy with other bond formation methods. Based on the experiments and the related reports, a cascade pathway triggered by the addition of ynone‐derived radical towards the C(sp)‐atom of isothiocyanate was proposed to elucidate the probable process of the transformation.
Visible Light Mediated Difluoroalkylation of Alkenes Using Mercaptobenzothiazole‐Derived Sulfide Reagent
Authors: Sorokin Artem O. , Levin Vitalij V. , Dilman Alexander D.
Published: August 2024

A method for the reductive difluoromethylation of alkenes with 2‐difluoromethylthio(benzothiazole) under photocatalytic conditions is described. The reaction involves the generation of the difluoromethyl radical by means of trimethyltriazinane, which serves as a precursor for the strongly reducing cyclic diaminoalkyl radical.
Real‐Time Radiation Beam Monitoring by Flexible Perovskite Thin Film Arrays
Authors: Fratelli Ilaria , Basiricò Laura , Ciavatti Andrea , Margotti Lorenzo , Cepić Sara , Chiari Massimo , Fraboni Beatrice
Published: August 2024

Real‐time and in‐line transversal monitoring of ionizing radiation beams is a crucial task for several applications which span from medical treatments to particle accelerators in high energy physics. Here a flexible and large area device based on 2D hybrid perovskite thin films (phenylethylammonium lead bromide), fabricated onto a thin flexible polyimide substrate, able to map the transversal beam profile of high energy radiation beams is reported. The performance of this novel tool is here compared with the one offered by standard commercial large‐area technology, namely radiochromic sheets. The great potential of this class of devices is demonstrated by successfully mapping in real‐time a 5 MeV proton beam at fluxes between 108 and 1010 H+ s−1 cm−2, confirming the capability to operate in a radiation‐harsh environment without output signal saturation issues. The versatility and scalability of here proposed detecting system are demonstrated by the development of a multipixel array able to map in real‐time a 40 kVp X‐ray beam spot (dose rate 8 mGy s−1). Perovskite thin film‐based detectors are thus assessed as a very promising class of thin, flexible devices for real‐time, in‐line, large‐area, conformable, reusable, transparent, and low‐cost transversal beam monitoring of different ionizing radiation.
Rational Designing Microenvironment of Gas‐Diffusion Electrodes via Microgel‐Augmented CO2 Availability for High‐Rate and Selective CO2 Electroreduction to Ethylene
Authors: Rabiee Hesamoddin , Li Mengran , Yan Penghui , Wu Yuming , Zhang Xueqin , Dorosti Fatereh , Zhang Xi , Ma Beibei , Hu Shihu , Wang Hao , Zhu Zhonghua , Ge Lei
Published: August 2024

Efficient electrochemical CO2 reduction reaction (CO2RR) requires advanced gas‐diffusion electrodes (GDEs) with tunned microenvironment to overcome low CO2 availability in the vicinity of catalyst layer. Herein, for the first time, pyridine‐containing microgels‐augmented CO2 availability is presented in Cu2O‐based GDE for high‐rate CO2 reduction to ethylene, owing to the presence of CO2‐phil microgels with amine moieties. Microgels as three‐dimensional polymer networks act as CO2 micro‐reservoirs to engineer the GDE microenvironment and boost local CO2 availability. The superior ethylene production performance of the GDE modified by 4‐vinyl pyridine microgels, as compared with the GDE with diethylaminoethyl methacrylate microgels, indicates the bifunctional effect of pyridine‐based microgels to enhance CO2 availability, and electrocatalytic CO2 reduction. While the Faradaic efficiency (FE) of ethylene without microgels was capped at 43% at 300 mA cm−2, GDE with the pyridine microgels showed 56% FE of ethylene at 700 mA cm−2. A similar trend was observed in zero‐gap design, and GDEs showed 58% FE of ethylene at −4.0 cell voltage (>350 mA cm−2 current density), resulting in over 2‐fold improvement in ethylene production. This study showcases the use of CO2‐phil microgels for a higher rate of CO2RR‐to‐C2+, opening an avenue for several other microgels for more selective and efficient CO2 electrolysis.
Adherence to adult clinical practice guidelines for Down syndrome
Authors: Wood Jordan C. , Gochyyev Perman , Santoro Stephanie L.
Published: August 2024

Adults with Down syndrome (DS) have unique health care needs with evidence‐based care guidelines to address these. Yet, the 2020 adult guidelines were unstudied; we aimed to assess adherence to these guidelines. We reviewed clinical and demographic data from medical charts of 327 adults with DS who were seen in the MGH DSP. We calculated adherence to care guidelines and analyzed correlations between both demographic traits and clinical results. Mean adherence rate to each of the nine adult guidelines was 67.3%. Adherence rates that were below our mean adherence rate included colonoscopy (42.9%), iron (41.9%), audiology specialist (35.8%), and audiogram (35.2%). We found four significant correlations: assigned females at birth had a significantly higher body mass index (BMI) than assigned males at birth (p < 0.001), Hispanic patients had a significantly higher BMI than other patients (p = 0.015), Hispanic patients had a significantly higher rate of diabetes than other patients (p = 0.036), and Black patients had a significantly lower rate of hypothyroidism than other patients (p = 0.004). We assessed the adherence rates to adult DS guidelines and highlighted disparities in healthcare for patients with DS to inform clinicians on how to improve care for patients with DS.
Discovery, Characterization and Synthetic Application of a Promiscuous Nonheme Iron Biocatalyst with Dual Hydroxylase/Desaturase Activity
Authors: Xu Hao , Zhao Jidong , Renata Hans
Published: August 2024

Alpha‐ketoglutarate‐dependent dioxygenases (αKGDs) have recently emerged as useful biocatalysts for C−H oxidation and functionalization. In this work, we characterized a new αKGD from aculene biosynthesis, AneA, which displays broad promiscuity toward a number of substrates with different ring systems. Unexpectedly, AneA was found to be capable of both desaturation and hydroxylation and require an amino ester motif on its substrate for productive catalysis. Insights gathered from the functional characterization and substrate‐activity profiling of AneA enabled the development of a chemoenzymatic strategy toward several complex sesquiterpenoids.
Long‐Term Autotrophic Growth and Solar‐to‐Chemical Conversion in Shewanella Oneidensis MR‐1 through Light‐Driven Electron Transfer
Authors: Shi Yan , Zhang Kejing , Chen Jianxin , Zhang Bingtian , Guan Xun , Wang Xin , Zhang Tong , Song Han , Zou Long , Duan Xiangfeng , Gao Haichun , Lin Zhang
Published: August 2024

Members of the genus Shewanella are known for their versatile electron accepting routes, which allow them to couple decomposition of organic matter to reduction of various terminal electron acceptors for heterotrophic growth in diverse environments. Here, we report autotrophic growth of Shewanella oneidensis MR‐1 with photoelectrons provided by illuminated biogenic CdS nanoparticles. This hybrid system enables photosynthetic oscillatory acetate production from CO2 for over five months, far exceeding other inorganic‐biological hybrid system that can only sustain for hours or days. Biochemical, electrochemical and transcriptomic analyses reveal that the efficient electron uptake of S. oneidensis MR‐1 from illuminated CdS nanoparticles supplies sufficient energy to stimulate the previously overlooked reductive glycine pathway for CO2 fixation. The continuous solar‐to‐chemical conversion is achieved by photon induced electric recycling in sulfur species. Overall, our findings demonstrate that this mineral‐assisted photosynthesis, as a widely existing and unique model of light energy conversion, could support the sustained photoautotrophic growth of non‐photosynthetic microorganisms in nutrient‐lean environments and mediate the reversal of coupled carbon and sulfur cycling, consequently resulting in previously unknown environmental effects. In addition, the hybrid system provides a sustainable and flexible platform to develop a variety of solar products for carbon neutrality.
Long‐term Durability of Seawater Electrolysis for Hydrogen: From Catalysts to Systems
Authors: Liu Yu , Wang Yong , Fornasiero Paolo , Tian Ge , Strasser Peter , Yang Xiao‐Yu
Published: August 2024

Direct electrochemical seawater splitting is a renewable, scalable, and potentially economic approach for green hydrogen production in environments where ultra‐pure water is not readily available. However, issues related to low durability caused by complex ions in seawater pose great challenges for its industrialization. In this review, a mechanistic analysis of durability issues of electrolytic seawater splitting is discussed. We critically analyze the development of seawater electrolysis and identify the durability challenges at both the anode and cathode. Particular emphasis is given to elucidating rational strategies for designing electrocatalysts/electrodes/interfaces with long lifetimes in realistic seawater including inducing passivating anion layers, preferential OH−adsorption, employing anti‐corrosion materials, fabricating protective layers, immobilizing Cl− on the surface of electrocatalysts, tailoring Cl− adsorption sites, inhibition of OH− binding to Mg2+ and Ca2+, inhibition of Mg and Ca hydroxide precipitation adherence, and co‐electrosynthesis of nano‐sized Mg hydroxides. Synthesis methods of electrocatalysts/electrodes and innovations in electrolyzer are also discussed. Furthermore, the prospects for developing seawater splitting technologies for clean hydrogen generation are summarized. We found that researchers have rethought the role of Cl− ions, as well as more attention to cathodic reaction and electrolyzers, which is conducive to accelerate the commercialization of seawater electrolysis.
Stable Dendrite‐Free Room Temperature Sodium‐Sulfur Batteries Enabled by a Novel Sodium Thiotellurate Interface
Authors: Gao Wanjie , Su Laisuo , Yu Yueheng , Lu Yuhan , Liu Xi , Peng Yi , Xiong Xiaosong , He Jiarui , Chen Yuanfu , Wu Yuping
Published: August 2024

The practical application of room‐temperature sodium‐sulfur (RT Na−S) batteries is severely hindered by inhomogeneous sodium deposition and notorious sodium polysulfides (NaPSs) shuttling. Herein, novel sodium thiotellurate (Na2TeS3) interfaces are constructed both on the cathode and anode for Na−S batteries to simultaneously address the Na dendritic growth and polysulfides shuttling. On the cathode side, a heterostructural sodium sulfide/sodium telluride embedded in a carbon matrix (Na2S/Na2Te@C) is rationally designed through a facile carbothermal reaction, where the Na2TeS3 interface will be in situ chemically obtained. Such an interface provides abundant electron/ion diffusion channels and ensures rich catalytic surfaces toward Na−S redox, which could significantly improve the utilization of active material and alleviate polysulfides shuttling in the cathode. On the anode side, the inevitable formation of soluble polytellurosulfides species will migrate on Na anode surface, finally constructing a compact and smooth solid‐electrolyte Na2TeS3 interphase (SEI) layer. Such electrochemical formed Na2TeS3 interface can significantly enhance ionic transport and stabilize Na deposition, thus realizing dendrite‐free Na‐metal plating/stripping. Benefitting from these advantages, an anode‐free cell fabricated with the Na2S/Na2Te@C cathode exhibits an ultrahigh initial discharge capacity of 634 mAh g−1 at 0.1 C, which could pave a new path to design high‐performance cathodes for anode‐free RT Na−S batteries.
A Dynamically Ion‐Sieved Electrolyte towards Ultralong‐Lifespan Zn‐Ion Batteries
Authors: Ji Yuyao , Hu Qiang , Zhao Jingxin , Han Cuiping , Cheng Hui‐Ming
Published: August 2024

The practical deployment of Zn‐ion batteries faces challenges such as dendrite growth, side reactions and cathode dissolution in traditional electrolytes. Here, we develop a highly conductive and dynamically ion‐sieved electrolyte to simultaneously enhance the Zn metal reversibility and suppress the cathode dissolution. The dynamic ion screen at the electrode/electrolyte interface is achieved by numerous pyrane rings with a radius of 3.69 Å, which can selectively facilitate the plating/stripping and insertion/extraction process of [Zn(H2O)6]2+ and Zn2+ on the anode and cathode surfaces. As a proof of concept, Zn//Zn symmetric cells deliver exceptional cyclic stability for over 6,800 h and ultrahigh cumulative plated capacity of 1.95 Ah cm−2. Zn//Na2Mn3O7 cells exhibit satisfactory cycling performance with capacity retention of 82.7 % after 4,000 cycles, and the assembled pouch cells achieve excellent stability and durability. This work provides valuable insights into the development of electrolytes aimed at enhancing the interface stability of aqueous batteries.
Designing Cooperative Ion Transport Pathway in Ultra‐Thin Solid‐State Electrolytes toward Practical Lithium Metal Batteries
Authors: Feng Guo , Ma Qianyi , Luo Dan , Yang Tingzhou , Nie Yihang , Zheng Zhuoyi , Yang Leixin , Li Shibin , Li Qingying , Jin MingLiang , Wang Xin , Chen Zhongwei
Published: August 2024

Solid polymer electrolytes (SPEs) are promising for high‐energy‐density solid‐state Li metal batteries due to their decent flexibility, safety, and interfacial stability. However, their development was seriously hindered by the interfacial instability and limited conductivity, leading to inferior electrochemical performance. Herein, we proposed to design ultra‐thin solid‐state electrolyte with long‐range cooperative ion transport pathway to effectively increase the ionic conductivity and stability. The impregnation of PVDF−HFP inside pores of fluorinated covalent organic framework (CF3−COF) can disrupt its symmetry, rendering rapid ion transportation and inhibited anion immigration. The functional groups of CF3−COF can interact with PVDF−HFP to form fast Li+ transport channels, which enables the uniform and confined Li+ conduction within the electrolyte. The introduction of CF3−COF also enhances the mechanical strength and flexibility of SPEs, as well as ensures homogeneous Li deposition and inhibited dendrite growth. Hence, a remarkably high conductivity of 1.21×10−3 S cm−1 can be achieved. Finally, the ultra‐thin SPEs with an extremely long cycle life exceed 9000 h can be obtained while the NCM523/Li pouch cell demonstrates a high capacity of 760 mAh and 96 % capacity retention after cycling, holding great promises to be utilized for practical solid‐state Li metal batteries.
Selective Activation of Peptide‐Thioester Precursors for Templated Native Chemical Ligations
Authors: Spaltenstein Paul , Giesler Riley J. , Scherer Samuel R. , Erickson Patrick W. , Kay Michael S.
Published: August 2024

Chemical protein synthesis enables access to proteins that would otherwise be difficult or impossible to obtain with traditional means such as recombinant expression. Chemoselective ligations provide the ability to join peptide segments prepared by solid‐phase peptide synthesis. While native chemical ligation (NCL) is widely used, it is limited by the need for C‐terminal thioesters with suitable reaction kinetics, properly placed native Cys or thiolated derivatives, and peptide segment solubility at low mM concentrations. Moreover, repetitive purifications to isolate ligated products are often yield‐sapping, hampering efficiency and progress. In this work, we demonstrate the use of Controlled Activation of Peptides for Templated NCL (CAPTN). This traceless multi‐segment templated NCL approach permits the one‐pot synthesis of proteins by harnessing selective thioester activation and orthogonal conjugation chemistries to favor formation of the full‐length ligated product while minimizing side reactions. Importantly, CAPTN provides kinetic enhancements allowing ligations at sterically hindered junctions and low peptide concentrations. Additionally, this one‐pot approach removes the need for intermediate purification. We report the synthesis of two E. coli ribosomal subunits S16 and S17 enabled by the chemical tools described herein. We anticipate that CAPTN will expedite the synthesis of valuable proteins and expand on templated approaches for chemical protein synthesis.
Aza‐Diarylethenes Undergoing Both Photochemically and Thermally Reversible Electrocyclic Reactions
Authors: Hamatani Shota , Kitagawa Daichi , Kobatake Seiya
Published: August 2024

Exploring novel molecular photoswitches plays a crucial role in the field of photo‐functional materials chemistry. In this study, we synthesized aza‐diarylethenes with benzothiophene‐S,S‐dioxide as a part of the hexatriene structure and investigated their photochromic properties. Unlike previously reported aza‐diarylethenes, which exhibit fast thermally reversible photochromism, the compounds synthesized here exhibited pseudo‐photochemically reversible photochromism. Due to their thermal stability, we successfully isolated the colored isomer. X‐ray crystallographic analysis revealed for the first time that the colored isomer adopts a closed‐ring structure with a bond between carbon and nitrogen atoms. Remarkably, these aza‐diarylethenes exhibited not only photochemical ring‐closing and ring‐opening reactions but also thermal ring‐closing and ring‐opening reactions, driven by a thermal equilibrium between the open‐ and closed‐ring isomers. This behavior, unprecedented for common diarylethenes, was elucidated through kinetic analysis, revealing an energy‐level diagram for the thermal equilibrium between these isomers. Furthermore, 1H NMR spectroscopy revealed that both photochemically and thermally generated closed‐ring isomers adopt the same molecular structure, which was well explained based on the reaction mechanism of photochemical and thermal ring‐closing reactions. These findings not only advance the field of aza‐diarylethenes but also inspire future research in the development of new photoswitches.
Bidirectional Molecular Motors by Controlling Threading and Dethreading Pathways of a Linked Rotaxane
Authors: Miyagishi Hiromichi V. , Masai Hiroshi , Terao Jun
Published: August 2024

Artificial molecular motors have been presented as models for biological molecular motors. In contrast to the conventional artificial molecular motors that rely on covalent bond rotation, molecular motors with mechanically interlocked molecules (MIMs) have attracted considerable attention owing to their ability to generate significant rotational motion by dynamically shuttling macrocyclic components. The topology of MIM‐type rotational molecular motors is currently limited to catenane structures, which require intricate synthetic procedures that typically produce a low synthetic yield. In this study, we develop a novel class of MIM‐type molecular motors with a rotaxane‐type topology. The switching of the threading/dethreading pathways of the linked rotaxane by protecting/deprotecting the bulky stopper group and changing the solvent polarity enables a net unidirectional rotation of the molecular motor. The threading/dethreading reaction rates were quantitatively evaluated through detailed spectroscopic investigations. Repeated net unidirectional rotation and switching of the direction of rotation were also achieved. Our findings demonstrate that linked rotaxanes can serve as MIM‐type molecular motors with reversible rotational direction controlled by threading/dethreading reactions. These motors hold potential as components of molecular machinery.
High‐Stable All‐Iron Redox Flow Battery with Innovative Anolyte based on Steric Hindrance Regulation
Authors: Yang Jiahui , Wei Wei , Zhou Chengxi , Yan Hui , Che Hangxin , Hao Leiduan , Tan Xinyi , Robertson Alex W. , Wu Tai‐Sing , Soo Yun‐Liang , Tang Ao , Sun Zhenyu
Published: August 2024

All‐soluble all‐iron redox flow batteries (AIRFBs) are an innovative energy storage technology that offer significant financial benefits. Stable and affordable redox‐active materials are essential for the commercialization of AIRFBs, yet the battery stability must be significantly improved to achieve practical value. Herein, ferrous complexes combined with the triisopropanolamine (TIPA) ligand are identified as promising anolytes to extend battery life by reducing cross‐contamination due to a pronounced steric hindrance effect. The coordination structure and failure mechanism of our Fe‐TIPA complexes were determined by molecular dynamics simulation and spectroscopic experiments. By coupling with [Fe(CN)6]4−/3−, Fe‐TIPA/Fe‐CN AIRFBs retained excellent stability exceeding 1831 cycles at 80 mA ⋅ cm−2, yielding an energy efficiency of ~80 % and maintaining a steady discharge capacity. Moreover, the all‐soluble electrolyte was tested in an industrial‐scale Fe‐TIPA/Fe‐CN AIRFB prototype energy storage system, where an energy efficiency of 81.3 % was attained. Given the abundance of iron resources, we model the TIPA AIRFB electrolyte cost to be as low as 32.37 $/kWh, which is significantly cheaper than the current commercial level. This work demonstrates that steric hindrance is an effective measure to extended battery life, facilitating the commercial development of affordable flow batteries.
Robust Sandwich‐Structured Thermally Activated Delayed Fluorescence Molecules Utilizing 11,12‐Dihydroindolo[2,3‐a]carbazole as Bridge
Authors: Lan Xia , Zeng Jiajie , Chen Jinke , Yang Tao , Dong Xiaobin , Tang Ben Zhong , Zhao Zujin
Published: August 2024

Constructing folded molecular structures is emerging as a promising strategy to develop efficient thermally activated delayed fluorescence (TADF) materials. Most folded TADF materials have V‐shaped configurations formed by donors and acceptors linked on carbazole or fluorene bridges. In this work, a facile molecular design strategy is proposed for exploring sandwich‐structured molecules, and a series of novel and robust TADF materials with regular U‐shaped sandwich conformations are constructed by using 11,12‐dihydroindolo[2,3‐a]carbazole as bridge, xanthone as acceptor, and dibenzothiophene, dibenzofuran, 9‐phenylcarbazole and indolo[3,2,1‐JK]carbazole as donors. They hold outstanding thermal stability with ultrahigh decomposition temperatures (556–563 °C), and exhibit fast delayed fluorescence and excellent photoluminescence quantum efficiencies (86 %–97 %). The regular and close stacking of acceptor and donors results in rigidified molecular structures with efficient through‐space interaction, which are conducive to suppressing intramolecular motion and reducing reorganized excited‐state energy. The organic light‐emitting diodes (OLEDs) using them as emitters exhibit excellent electroluminescence performances, with maximum external quantum efficiencies of up to 30.6 %, which is a leading value for the OLEDs based on folded TADF emitters. These results demonstrate the proposed strategy of employing 11,12‐dihydroindolo[2,3‐a]carbazole as bridge for planar donors and acceptors to construct efficient folded TADF materials is applicable.
Asymmetric Coupled Binuclear‐Site Catalysts for Low‐Temperature Selective Acetylene Semi‐Hydrogenation
Authors: Lu Fei , Wang Jingnan , Chai Shanshan , Wang Yan , Yao Yongbin , Wang Xi
Published: August 2024

Heterogeneous metal catalysts with bifunctional active sites are widely used in chemical industries. Although their improvement process is typically based on trial‐and‐error, it is hindered by the lack of model catalysts. Herein, we report an effective vacancy‐pair capturing strategy to fabricate 12 heterogeneous binuclear‐site catalysts (HBSCs) comprising combinations of transition metals on titania. During the synthesis of these HBSCs, proton‐passivation treatment and step‐by‐step electrostatic anchorage enabled the suppression of single‐atom formation and the successive capture of two target metal cations on the titanium–oxygen vacancy‐pair site. Additionally, during acetylene hydrogenation at 20 °C, the HBSCs (e.g., Pt1Pd1−TiO2) consistently generated more than two times the ethylene produced by their single‐atom counterparts (e.g., Pd1−TiO2). Furthermore, the Pt1Pd1 binuclear sites in Pt1Pd1−TiO2 were demonstrated to catalyze C2H2 hydrogenation via a bifunctional active‐site mechanism: initially C2H2 chemisorb on the Pt1 site, then H2 dissociates and migrates from Pd1 to Pt1, and finally hydrogenation occurs at the Pt1−Pd1 interface.
Non‐Fluorinated Cyclic Ether‐Based Electrolyte with Quasi‐Conjugate Effect for High‐Performance Lithium Metal Batteries
Authors: Zhu Xiao , Chen Jiawei , Liu Gaopan , Mo Yanbing , Xie Yihua , Zhou Kang , Wang Yonggang , Dong Xiaoli
Published: August 2024

Fluorinated ether‐based electrolytes are commonly employed in lithium metal batteries (LMBs) to attenuate the coordination ability of ether solvents with Li+ and induce inorganic‐rich interphase, whereas fluorination inevitably introduces exorbitant production expenses and environmental anxieties. Herein, a non‐fluorinated molecular design strategy has been conceptualized by incorporating methoxy as an electron‐donating group to generate a quasi‐conjugate effect for tuning the affinity of Li+‐solvent, thereby enabling the cyclic ether solvent 2‐methoxy‐1,3‐dioxolane with weak solvation ability and exceptional Li metal‐compatibility. Accordingly, the optimized electrolyte exhibits anion‐dominant solvation structure for inorganic‐rich interphase and fulfills an impressive Li plating/stripping Coulombic efficiency of 99.6 %. As‐fabricated Li||LiFePO4 full cells with limited Li (N/P=2.5) showcase a high capacity retention of 83 % after 150 cycles, indicating excellent cycling stability. Moreover, the full LMBs demonstrate exceptional tolerance towards a wide temperature range from −20 °C to 60 °C, displaying a remarkable capacity retention of 90 % after 110 cycles at −20 °C. Such a molecular design strategy offers a promising avenue for electrolyte engineering beyond fluorination in order to cultivate high‐performance LMBs.
Constructing Targeted Strong Nb4d−O2p−Li2s Configurations to Obtain Excellent Energy Density and Long Life for Li‐Rich Cathodes
Authors: Hu Kanghui , Tang Huoqiang , Zheng Baoping , Yu Lei , Xiong Feng , Li Haoyu , Qiu Lang , Wan Fang , Song Yang , Zhong Benhe , Wu Zhenguo , Guo Xiaodong
Published: August 2024

The Li‐rich Mn‐based cathode materials (LMRs) deliver excellent energy density and exhibit low cost, which are considered as the most promising cathode materials for the next generation lithium‐ion batteries. However, the irreversible redox reaction of the oxygen atoms directly leads to release oxygen and intensifies phase transformation. Besides, the local stress and strain will be generated due to the unit‐cell volume difference between R‐3m and C2/m phases, which continuously aggravates the collapse of secondary particles. Herein, the strong Nb4d−O2p−Li2s configurations at the Li1 sites of the TM‐layer in the C2/m phase and secondary particles with the radial arrangement of refined primary particles are designed to inhibit oxygen release and relieve lattice stress by Nb2O5 treatment. Meanwhile, the preferential growth of the active {010} planes is presented to obtain an excellent transmission rate of Li+. As a result, the designed LMR delivers remarkable electrochemical properties with high discharge capacity and initial coulomb efficiency of 276 mAh g−1 and 85 % at 0.1 C, outstanding cycling retention rate of 81 % after 300 cycles. This novel crystal structure combining oxygen coordination regulation and micro‐nano scale design provides inspiration for the design of high‐performance LMRs.
Spiral‐Concave Prussian Blue Crystals with Rich Steps: Growth Mechanism and Coordination Regulation
Authors: Zhang Guangxun , Li Yong , Du Guangyu , Lu Jingqi , Wang Qiujing , Wu Ke , Zhang Songtao , Chen Han‐Yi , Zhang Yizhou , Xue Huai‐Guo , Shakouri Mohsen , Liu Zheng , Pang Huan
Published: August 2024

Investigating the formation and transformation mechanisms of spiral‐concave crystals holds significant potential for advancing innovative material design and comprehension. We examined the kinetics‐controlled nucleation and growth mechanisms of Prussian Blue crystals with spiral concave structures, and constructed a detailed crystal growth phase diagram. The spiral‐concave hexacyanoferrate (SC‐HCF) crystals, characterized by high‐density surface steps and a low stress‐strain architecture, exhibit enhanced activity due to their facile interaction with reactants. Notably, the coordination environment of SC‐HCF can be precisely modulated by the introduction of diverse metals. Utilizing X‐ray absorption fine structure spectroscopy and in situ ultraviolet‐visible spectroscopy, we elucidated the formation mechanism of SC‐HCF to Co‐HCF facilitated by oriented adsorption‐ion exchange (OA‐IE) process. Both experimental data, and density functional theory confirm that Co‐HCF possesses an optimized energy band structure, capable of adjusting the local electronic environment and enhancing the performance of the oxygen evolution reaction. This work not only elucidates the formation mechanism and coordination regulation for rich steps HCF, but also offers a novel perspective for constructing nanocrystals with intricate spiral‐concave structures.
A simple subtropical high‐pressure system index over the South Atlantic
Authors: Quagraine Kwesi A. , Hewitson Bruce , Nkrumah Francis , Quagraine Kwesi T. , Egbebiyi Temitope S.
Published: August 2024

This research introduces a novel index for the South Atlantic High Pressure (SAHP) system to enhance understanding of regional climate variability and change. Subtropical highs significantly influence regional climates, yet comprehensive indices to measure their behaviours are lacking. Utilizing ERA5 reanalysis data from 1940 to 2023, the proposed index estimates a weighted centroid of the area surrounding the maximum sea level pressure within a 3 hPa range. This method ensures robustness and flexibility in contiguous area estimation specific to subtropical high events. Results showed the index effectively reflects the position and intensity of the SAHP. The study reveals that latitudinal variability of the SAHP has a strong unimodal structure, whereas longitudinal variability exhibits a bimodal structure. Seasonal patterns of the index show noticeable changes, with winter (JJA) and spring (SON) months having relatively high index values compared to summer (DJF) and autumn (MAM) months, underscoring the intra‐annual variability of the SAHP index. During ENSO events, the mean centroid position of the SAHP shifts significantly, moving westwards and polewards during El Niño and showing greater stability during La Niña. The index, with minimal computation requirements and flexibility, can be applied across diverse datasets, aiding in the assessment of future subtropical high changes.
Educating for living diversity: ‘Migrant’ identities, belonging and community‐centred pedagogies for social justice
Authors: Gholami Reza , Costantini Giada
Published: August 2024

This paper addresses the continued conundrums of racial and religious diversity in education. While social diversity is steadily increasing in Global North countries, there is little evidence of meaningful conviviality. Conversely, despite decades of dedicated multiculturalist policymaking, there is ample evidence of persisting educational disparities affecting pupils from minority backgrounds, as well as de facto segregation inside classrooms. This paper examines two reasons for the ongoing situation. Firstly, we explore the history of ‘intercultural’ approaches to education and demonstrate that they are too detached from the unequal dynamics of social and political life in diverse contexts. Secondly, we employ the concept of ‘museumification’ to show that diversity is often performed and curated, which ultimately keeps dominant structures intact. We conducted multi‐stakeholder participatory research in Birmingham, UK. The research involved several stages and outcomes, including collecting stories from Birmingham denizens with a refugee/immigrant background, working with a celebrated photographer to produce portraits of participants and using these materials to co‐produce educational resources for primary and secondary schools. Our findings suggest that ‘diversity’ must be approached, taught and learned as a lived/living reality, which will account for its highly complex, iterative and dis/located dynamics at the level of individual and communal identities. We articulate this through the concept of ‘living diversity’.
Training, assessment and competence in Counselling for Depression: Experiences of trainees, trainers and supervisors
Authors: O'Brien Reginald Thomas , Burr Vivien , Dale Heather
Published: August 2024

Background

Since the inception of Counselling for Depression (CfD) in the UK as a competence‐based training course for experienced therapists, there has been remarkably little empirical work exploring the experiences and views of trainees and those involved in course delivery.

Aims

This qualitative study aimed to explore trainees', trainers' and supervisors' experiences of CfD training and their perceptions and understanding of competence in the context of CfD training and assessment.

Methods

Semi‐structured interviews were carried out with 19 participants recruited from two UK training courses and the BACP Practice Network. The interviews were analysed using Template Analysis.

Findings

Two key themes are reported here: tensions in the CfD competence model and tensions in CfD methods of training and assessment. Participants reported challenges in adapting to the CfD model. They felt that its use drew them away from core values in their practice so that they felt their identity as a therapist was threatened. In particular, they questioned the possibility of integrating person‐centred and emotion‐focussed approaches and felt that the directivity of emotion‐focussed therapy was out of keeping with their core practice values. They also identified a number of difficulties with the CfD training and assessment; the training period was seen as an inadequate preparation for workplace practice, and the assessment process was criticised for being too narrow and was regarded as having little connection to the competence framework.

Conclusion

The findings suggest a need for changes in policy and practice, specifically in regard to training and assessment.
Deciphering the cellular landscape and potential targets of nasopharyngeal and oral cancers using single‐cell RNA sequencing
Authors: Zhang Yanfei , Qin Xiaoyu , Lou Weihua , Wang Liang , Lu Wuhao , Gao Changhui , Hu Shousen
Published: August 2024

Cellular heterogeneity in nasopharyngeal cancer (NPC) and oral cancer remains unclear. In the current study, using single‐cell RNA sequencing techniques, we investigated the cellular landscape in NPC and oral cancers. We identified a diverse range of cell types within the tumor microenvironment (TME) and variations in cell infiltration between NPC and oral cancer. In oral cancer, we observed a predominant infiltration of epithelial cells, fibroblasts, and endothelial cells (ECs), while T cells were the main infiltrating cell population in NPCs. We further classified these infiltrating cells into subclusters. Additionally, we observed complex interactions among cells that led to distinct trajectories. In particular, a unique epithelial subcluster with high expression of major histocompatibility complex class II (MHC‐II) molecules was correlated with a favorable outcome and infiltration of CD4+ T cells. In addition, MHC‐II+ epithelial cells inhibited mouse tumor growth and promoted T‐cell infiltration. Consequently, our findings provide a deep understanding of the TME showing a significant prognostic value and therapeutic potential.
Effects of different timing and rate of glyphosate application on the residue level, grain quality, and processing performance of two Canadian malting barley varieties
Authors: Izydorczyk Marta S. , McMillan T. , Tittlemier S. A. , O'Donovan J. , Tidemann B. D.
Published: August 2024

Background and Objectives

A preharvest application of glyphosate on malting barley can assist in the management of perennial weed growth before harvest and serves as a harvest aid by drying down the crop. The main objective of this study was to assess the effects of preharvest glyphosate application at two glyphosate rates (900 or 1125 g ae/ha) and three application timings based on the maturity and seed moisture level (soft dough, hard dough, or mature).

Findings

The levels of glyphosate residue in barley grain were highly variable among locations and years ranging from 0 to 95 mg/kg. Glyphosate application at both rates at the soft dough stage significantly decreased the kernel weight of barley grain. Barley grain with up to 40 mg/kg of glyphosate residue exhibited adequate germination energy required for malting purposes; however, the residue negatively affected the growth of roots during the malting process. The levels of α‐amylase in malt decreased with increasing levels of glyphosate residue in barley. Other malt and wort parameters were generally not affected by the glyphosate application on barley.

Conclusions

Too early application of glyphosate at the soft dough stage of barley grain development reduced the kernel weight and size, interfered with roots production, affected synthesis of α‐amylase, and reduced the malt extract in several cases.

Significance and Novelty

Results indicated that in the majority of environments, when glyphosate was applied at the recommended stage and rate, neither the maximum residue limit was exceeded nor were the germination and malting quality of barley impaired. In real farming conditions, it might be hard to achieve similar results despite adherence to the recommended timing of glyphosate application because of the nonuniform level of crop maturity in the field and/or uncontrollable environmental effects.
Fatal case of meningococcal meningitis in a child from rural Bhutan: A case report
Authors: Bhandari Purushotam , Dorji Thinley , Sharma Tulsi Ram , Mynak Mimi Lhamu
Published: August 2024

Key Clinical Message

N meningiditis remains an important cause of central nervous system infection. A high index of suspicion is required especially in infants. While empirical antibiotics may be initiated, diagnostic measures must be adopted for guided therapy. Notification of such cases contributes to surveillance data and deciding on providing vaccines to the population.
Anti‐PL‐12 anti‐synthetase syndrome manifesting with multiple digital ischemia: Case report & review of the literature
Authors: Doumeth Sarah Abi , Petrinec Emily , Chaudhary Haseeb , Mattar Maya
Published: August 2024

Key Clinical Message

Acute digital ischemia is a rare manifestation of anti‐synthetase syndrome in the absence of Raynaud's phenomenon. A high index of suspicion may result in early diagnosis and better clinical outcomes.

A 61‐year‐old male patient was admitted to the hospital for worsening arthralgias with morning stiffness lasting hours, as well as left sided headaches, and jaw pain while eating. He had significant weight loss and subjective fever at home. Multiple fingers and toes were noted to be ischemic. His laboratory workup was pertinent for significantly elevated inflammatory markers, and mild Creatinine kinase elevation. Chest imaging and later lung biopsy were notable for organizing pneumonia. Conventional angiogram showed evidence of significant digital disease without collaterals. Subsequent autoimmune screening tests with extended myositis‐specific and myositis‐associated panels revealed a strongly positive anti‐PL‐12 antibody and moderately positive anti‐ SSA‐52KD IgG ab. After ruling out infectious etiologies and malignancy, anti‐synthetase syndrome (ASyS) diagnosis was considered in the presence of ischemic digits, organizing pneumonia, polyarthralgia, constitutional symptoms, increased inflammatory markers and positive antibodies. The patient was treated with high dose prednisone and mycophenolate mofetil along with amlodipine and sildenafil for digital vasodilation. Acute digital ischemia may be the first manifestation of ASyS with ILD. A high index of suspicion is warranted for early diagnosis and better outcomes.