bluuebunny/crossref_metadata_2025_split huggingface dataset:
Uncharacteristic Adsorption Breakthrough Behavior of a Core–Shell Copper Hydroxysulfate Metal–Organic Framework Against Gaseous Formaldehyde
Authors: Yen Tran Thi , Vikrant Kumar , Szulejko Jan E. , Kim Ki‐Hyun 
Published: December 2023

AbstractCore–Shell structured microspheres with a packed nano‐platelet copper hydroxysulfate (CHS) core and an octahedral crystalized metal–organic framework‐199 (CHS@M199) shell are synthesized and tested as adsorbent for gaseous formaldehyde (FA). CHS@M199 outperforms reference materials (e.g., activated carbon (AC), CHS, and M199) with adsorption capacity (Q) of 8.13 mg g−1 and partition coefficient (PC) of 0.263 mol kg−1 Pa−1 against 10 Pa FA at 10% breakthrough (BT) level with the aid of large surface area and copper sites for coordinating with carbonyl group. Contrary to general expectations, CHS@M199 exhibits a unique adsorption behavior in that BT volume increases systematically with the rise in FA inlet partial pressure (e.g., 5–10 Pa). The 10% BT capacity of CHS@M199 decreases noticeably (8.13 to 2.08 mg g−1) with increasing relative humidity (0.016 to 10%), reflecting water‐FA competition for hydrophilic adsorption sites. Although FA adsorption on CHS@M199 diminishes with elevated RH levels, such reduction intensifies when simulating ambient conditions (through stepwise addition of competing components: O2, CO2, and H2O). The FA adsorption on CHS@M199 is well described by both pseudo‐first‐order (PFO) and pseudo‐second‐order (PSO) kinetics. Polymerization may play a pivotal role in the adsorption of FA on CHS@M199, as Qi‐LeVan isotherm best fits the experimental data.
Enhanced Oxygen Reduction Reaction Activity of Manganese Oxide via p−d Hybridization with Aluminum Group Element Dopants
Authors: Qin Guoqing , Hao Yixin , Ma Haoliang , Tian Mengmeng , Yu Xiaofei , Li Lanlan , Zhang Xinghua , Lu Zunming , Ren Jianwei , Hu Feng , Yang Xiaojing , Peng Shengjie 
Published: December 2023

AbstractDoping engineering is an effective strategy to improve the electrocatalytic activity of manganese oxides by enhancing their poor electrical conductivity and oxygen adsorption capacity. Herein, p‐block aluminum group metal ions (Al3+, Ga3+, and In3+) are introduced into cryptomelane‐type manganese oxide octahedral molecular sieves (OMS‐2), leading to p−d orbital hybridization between the p‐orbitals of the aluminum group metals and d‐orbitals of Mn, facilitating the oxygen reduction reaction. The aluminum group metal‐doped OMS‐2 exhibits excellent catalytic activity, rapid reaction kinetics, and favorable stability compared to commercial Pt/C. Among the three prepared catalysts, Ga‐doped OMS‐2 (Ga‐OMS‐2) has stronger oxygen reduction activity. Experimental and theoretical calculations show that the superiority of Ga‐OMS‐2 is attributed to p−d hybridization, which enriches the reaction sites and enhances the binding strength of the catalyst to the O2 reaction intermediates. As a proof of concept, Zinc−air batteries assembled with Ga‐OMS‐2 as a catalyst exhibit superior power density and cycle life to commercial Pt/C. This p−d hybridization strategy gives insight into the p‐block metal doping of catalysts prepared with other transition metals with excellent electrocatalytic activity and durability for energy storage and conversion.
Designing of Hexagonal Nanosheets with Edge‐Sharing [IrO6] Octahedral Crystals for Efficient and Stable Acidic Water Splitting
Authors: Zhu Lin , Ma Chenglong , Li Danni , Shao Xiang , Cao Limei , Yang Ji 
Published: December 2023

AbstractThe oxygen evolution reaction (OER) is a critical factor for advancing the industrial application of proton exchange membrane (PEM) electrolyzers. However, the low mass activity of iridium‐based catalysts has become a critical obstacle in improving the efficiency of the OER. To address this problem, a hexagonal system nanosheet structure with lattice distortion and edge‐connected [IrO6] octahedron is designed to enhance both mass activity and durability. This material exhibits a high mass activity of 217 mA mgIr−1 at 1.55 V relative to the reversible hydrogen electrode (RHE), which is 13 times greater than that of Rutile IrO2. Furthermore, the voltage of T‐CsIr exhibits no significant increase after 400 h of continuous operation at a current density of 10 mA cm−2. Integrating X‐ray experimental analysis with theoretical calculations reveals that the shortening of the Ir─Ir bond and the reduction of Ir3+ proportion effectively modulate the adsorption energy of the rate‐determining step, thereby significantly promoting the kinetics of the OOH* deprotonation process. These results demonstrate that regulation of lattice distortion is a feasible approach to effectively improve the OER catalytic performance.
Subnanometer Nanowire‐Reinforced Construction of COF‐Based Membranes with Engineering Biomimetic Texture for Efficient and Stable Proton Conduction
Authors: Zhu Liyu , Zhang Limei , Ren Yuting , Lei Jiandu , Wang Luying , Liu Jing 
Published: December 2023

AbstractAchieving rapid ion transport through nanochannels is essential for both biological and artificial membrane systems. Covalent organic frameworks (COFs) with well‐defined nanostructures hold great promise for addressing the above challenge. However, due to the limited processability and inadequate interlamellar interaction of COF materials, it is extremely difficult to integrate them to prepare high‐performance proton conductors. Herein, inspired by the ingenious bio‐adhesion strategy in nature, ultrafast proton conduction is achieved by taking advantage of COF membranes where TP‐COF nanosheets are linked by subnanometer nanowires/lignocellulosic nanofibrils composites (SNWs/LCNFs) through electrostatic and π‐π interactions to form an ordered and robust structure. Notably, the synthesized SNWs exhibited impressive proton conductivity and adhesion capacity due to their inbuilt phosphotungstic acid (HPW) molecules and multidimensional interactions. Therefore, attributed to the synergistic contribution of TP‐COFs and SNWs, the composite membrane achieves ultrahigh proton conductivity (0.395 S cm−1 at 80 °C and 100% RH), superior mechanical property (109.8 MPa), exceptional fuel cell performance (71.6 mW cm−2), and superior operational stability (OCV decay rate is about 1.5 mV h−1), demonstrating outstanding competitiveness. More importantly, the proposed design concept has the potential to be applied in membranes for various electrochemical devices and molecular separations.
Noninvasive Needle‐Free Cancer Vaccine Cream Patch Based on Fluorinated Chitosan
Authors: Xiao Zhisheng , Li Guangzhi , Deng Dashi , Wei Ting , Chen Guoping , Tao Huiquan , Chao Yu , Liu Bo , Li Qiaofeng , Yang Yifan , Liu Zhuang , Chen Qian 
Published: December 2023

AbstractIn recent years, cancer vaccines that intend to specifically initiate host immune responses against cancer have achieved some clinical success. Delivery of vaccines with traditional needles is usually associated with the risk of infection and poor patient compliance. The development of needle‐free vaccines may overcome these limitations. In this work, a needle‐free patch is designed for effective cancer vaccination using a fluorine chain‐modified cationic polymer, fluorinated chitosan (FCS), which is able to transdermatically deliver the antigen to antigen‐presenting cells in the skin. Specifically, a transdermal carrier, FCS, and model antigen ovalbumin (OVA) can self‐assemble into nanoparticles, which can reversibly open the tight junction‐associated proteins of epithelial cells and penetrate across the epidermis. The needle‐free cancer vaccine patch is fabricated by mixing FCS‐OVA nanoparticles with the US Food and Drug Administration‐approved immune adjuvant imiquimod (R837) in blank cream. Such a needle‐free cancer vaccine can generate robust immune responses to protect mice against ovalbumin‐expressing melanoma (B16‐OVA). Compared to traditional intradermal injection, needle‐free cancer vaccines achieved an even more efficient protection effect against B16‐OVA cancer cells. This work indicated that the novel needle‐free cancer vaccine may provide a compelling technology for simple and safe vaccination, which may help to increase vaccination coverage.
Sieve Tube‐Inspired Polysulfide Cathode with Long‐Range Ordered Channels and Localized Capture‐Catalysis Microenvironments for Efficient Li–S Batteries
Authors: Zhu Ran , Zhao Zhenyang , Yan Rui , Wu Min , Zheng Weiqion , Wang Mao , Cheng Chong , Li Shuang , Zhao Changsheng 
Published: December 2023

AbstractAccelerating the conversion of soluble lithium polysulfides (LiPSs) to solid Li2S2/Li2S through single‐atom cathodes has emerged as a promising strategy for realizing high‐performance lithium–sulfur batteries. However, rationally optimizing the conversion effects and spatial capture abilities of LiPSs intermediates on the atomic catalytic sites is extremely required but still faces enormous challenges. Here, inspired by the delicate structure of sieve tubes in plants, Fe single‐atom cathode (channel‐FeSAC) equipped with long‐range ordered channels and localized capture‐catalysis microenvironments towards efficient LiPSs conversion is reported on designing. Benefiting from the individual and stable catalytic areal for localized capture and migration inhibition abilities on LiPSs and fully confined triple‐phase boundaries between atomic catalytic centers, conductive carbon, and electrolytes, the channel‐FeSAC can effectively convert polysulfides, thus eliminating the shuttle effects and generation of inactive LiPSs. It is also elucidated that the channel‐FeSAC exhibits superior migration inhibition of polysulfide and accelerates Li2S deposition/conversion kinetics compared with bowl‐FeSAC and flat‐FeSAC. The outstanding areal capacity and cycling stability under high sulfur loading and low electrolyte/sulfur ratio verify that the channel‐FeSAC holds great potential as cathodes for high‐performance cathodes. This work offers vital insights into the essential roles of bioinspired fully confined channels and catalytic microenvironments in polysulfide catalysis for efficient lithium–sulfur batteries.
Undercoordination Chemistry of Sulfur Electrocatalyst in Lithium–Sulfur Batteries
Authors: Wang Jiayi , Li Gaoran , Zhang Xiaomin , Zong Kai , Yang Yi , Zhang Xiaoyu , Wang Xin , Chen Zhongwei 
Published: December 2023

AbstractUndercoordination chemistry is an effective strategy to modulate the geometry‐governed electronic structure and thereby regulate the activity of sulfur electrocatalysts. Efficient sulfur electrocatalysis is requisite to overcome the sluggish kinetics in lithium–sulfur (Li–S) batteries aroused by multi‐electron transfer and multi‐phase conversions. Recent advances unveil the great promise of undercoordination chemistry in facilitating and stabilizing sulfur electrochemistry, yet a related review with systematicness and perspectives is still missing. Herein, it is carefully combed through the recent progress of undercoordination chemistry in sulfur electrocatalysis. The typical material structures and operational strategies are elaborated, while the underlying working mechanism is also detailly introduced and generalized into polysulfide adsorption behaviors, polysulfide conversion kinetics, electron/ion transport, and dynamic reconstruction. Moreover, perspectives on the future development of undercoordination chemistry are further proposed.
Multi‐Length Scale Communication Effects in Catalysis: Thinking Big and Acting Small
Authors: Moyano Albert , Crusats Joaquim 
Published: December 2023

AbstractThe use of hierarchically structured materials as catalysts has been finding increasing application in the past years. For these catalytic systems, not only the nano‐scale matters: a high degree of order across multiple length scales, along with its control and analytical assessment, is of paramount importance to obtain innovative properties that can find application in catalysis. Most reviews dealing with hierarchically structured materials are concerned with the “bottom‐up” transfer of structural information along the different length scales, with special emphasis on the transmission of chirality. Due to their mesoscale size together with their complex behaviour, these systems are often susceptible to feel the effects of macroscopic forces, that can exert a “top‐down” control of their catalytic properties, so that an external stimulus, acting at the level of the supramolecular architecture of the catalyst, can ultimately determine the outcome of the catalyzed reaction at the molecular level. We review in this paper some recent reports that deal with the experimental implementation of this concept, either by using a mechanical force in a full range direct transmission to the reaction coordinate, or by means of a stepwise relay transmission from the macroscopic level (purely supramolecular chirality) to the nanoscopic one. We focus in this review on these multi‐length scale communication control effects, identifying the different mechanisms that are affecting the catalytic activity.
Organo‐Catalyzed Intermolecular Dehydrative Coupling Reaction to Prepare Arylacetic Acid Derivatives
Authors: Chen Fei , Geng Huidan , Zhao Yonglong , Li Chun , Guo Bing , Tang Lei , Yang Yuanyong 
Published: December 2023

AbstractHerein, the use of triphenylmethylium tetrakis(pentafluorophenyl)borate as an efficient catalyst for the intermolecular dehydrative coupling of p‐hydroxymandelic acid hydrate with substituted aromatic amines and (thio)phenols was developed, which allows for the preparation of arylacetic acid derivatives in a convenient manner. Notably, this method offers several advantages, including being prefunctionalization free, high atom efficiency, and high regioselectivity. Additionally, it exhibits a broad substrate scope, enabling the synthesis of a range of arylacetic acid derivatives. Furthermore, this method can also be applied to the etherification of arylthiol derivatives, facilitating the preparation of various thiolated products, which would enhance the applicability and potential utility of this method in organic synthesis.
Emerging Additive Manufacturing Methods for Wearable Sensors: Opportunities to Expand Access to Personalized Health Monitoring
Authors: Yin Ziyu , Clark Kaylee M. , Ray Tyler R. 
Published: December 2023

AbstractPersistent disparities exist in access to state‐of‐the‐art healthcare disproportionately affecting underserved and vulnerable populations. Advances in wearable sensors enabled by additive manufacturing (AM) offer new opportunities to address such disparities and enhance equitable access advanced diagnostic technologies. Additive manufacturing provides a pathway to rapidly prototype bespoke, multifunctional wearable sensors thereby circumventing existing barriers to innovation for resource‐limited settings imposed by the need for specialized facilities, technical expertise, and capital‐intensive processes. This review examines recent progress in the additive manufacture of wearable platforms for physiological health monitoring. Supported by an initial overview of relevant techniques, representative examples of 3D printed wearable sensors highlight the potential for measuring clinically‐relevant biophysical and biochemical signals of interest. The review concludes with a discussion of the promise and utility of additive manufacturing for wearable sensors, emphasizing opportunities for expanding access to vital healthcare technology and addressing critical health disparities.
Theoretical Study on Functionalizing A–D–A Type Non‐Fullerene Acceptor by Fused Rings and Side Chains for Organic Solar Cells
Authors: Ma Li , Zhang Cai‐Rong , Zhang Mei‐Ling , Liu Xiao‐Meng , Gong Ji‐Jun , Chen Yu‐Hong , Liu Zi‐Jiang , Wu You‐Zhi , Chen Hong‐Shan 
Published: December 2023

AbstractThe modification of fused rings in the central backbone, side chains, and end groups of the non‐fullerene acceptor (NFA) for organic solar cells (OSCs) can modulate properties and photovoltaic performance. In order to investigate the effect of fused rings and side chains on photovoltaic performance, PBDB‐T is selected as electron donor and IDTIC, IDIC, IDIC‐PhC6, IDIC‐C4Ph, 4TIC, ITIC‐OE, IDTTIC, ITC6‐IC, ITIC, and C8‐ITIC are selected as NFAs. Based on quantum chemistry calculations, the geometries, electronic structures, excitation properties, excited‐state lifetimes, and electrostatic potentials (ESPs) of the monomer and the PBDB‐T:NFA complexes are studied, and the rate constants of charge transfer (CT), exciton dissociation (ED) and charge recombination (CR) processes are analyzed. The results show that the increase of fused‐ring in NFA's backbone by substituting phenyl or thienyl with bithiophene can elevate the highest occupied molecular orbital energies, reduce the gap of frontier molecular orbital energies, induce red‐shift of absorption spectrum, increase CT energy, improve CT and ED rates. This work provides a detailed understanding of tuning optoelectronic properties and photovoltaic performance by modifying NFA's side chains and extending backbones.
TD‐YOLO: A Lightweight Detection Algorithm for Tiny Defects in High‐Resolution PCBs
Authors: Ling Qin , Isa Nor Ashidi Mat 
Published: December 2023

AbstractPrinting circuit board (PCB) defect inspection precisely and efficiently is an essential and challenging issue. Therefore, based on several improvements upon YOLOv5‐nano, a novel lightweight detector named TD‐YOLO is proposed to inspect tiny defects in PCBs. First, the lightweight ShuffleNet block is implemented into the backbone to effectively reduce the model weight. Second, novel anchors are designed using modified k‐means clustering to accelerate the model convergence and yield superior detection precision. Then, data augmentation strategy is recomposed by rejecting mosaic augmentation to suppress the emergence of extremely tiny targets. Finally, a mighty feature pyramid network namely MPANet, is newly proposed to boost the feature fusion capability of the model. The experiment results denote TD‐YOLO achieves the highest 99.5% mean average precision on our dataset, outperforming other state of the arts. Specially, the detection metrics for the smallest two defects, such as spur and mouse bite, are increased by 2.1% and 1.2%, respectively, compared with YOLOv5‐nano. Besides, TD‐YOLO has only 1.33 million parameters, decreased by 25% than the baseline. Using a mediocre processor, the detection speed is boosted by 20%, reaching 37 frames per second for the input size of 22402240 pixels.
Advanced Cooling Textiles: Mechanisms, Applications, and Perspectives
Authors: Zhang Xueping , Wang Fei , Guo Hanyu , Sun Fengqiang , Li Xiangshun , Zhang Chentian , Yu Chongwen , Qin Xiaohong 
Published: December 2023

AbstractHigh‐temperature environments pose significant risks to human health and safety. The body's natural ability to regulate temperature becomes overwhelmed under extreme heat, leading to heat stroke, dehydration, and even death. Therefore, the development of effective personal thermal‐moisture management systems is crucial for maintaining human well‐being. In recent years, significant advancements have been witnessed in the field of textile‐based cooling systems, which utilize innovative materials and strategies to achieve effective cooling under different environments. This review aims to provide an overview of the current progress in textile‐based personal cooling systems, mainly focusing on the classification, mechanisms, and fabrication techniques. Furthermore, the challenges and potential application scenarios are highlighted, providing valuable insights for further advancements and the eventual industrialization of personal cooling textiles.
Thioester‐Based Coupled Fluorogenic Assays in Microdevice for the Detection of Single‐Molecule Enzyme Activities of Esterases with Specified Substrate Recognition
Authors: Ukegawa Tatsuya , Komatsu Toru , Minoda Mayano , Matsumoto Takuya , Iwasaka Takumi , Mizuno Tadahaya , Tachibana Ryo , Sakamoto Shingo , Hanaoka Kenjiro , Kusuhara Hiroyuki , Honda Kazufumi , Watanabe Rikiya , Urano Yasuteru 
Published: December 2023

AbstractSingle‐molecule enzyme activity assay is a platform that enables the analysis of enzyme activities at single proteoform level. The limitation of the targetable enzymes is the major drawback of the assay, but the general assay platform is reported to study single‐molecule enzyme activities of esterases based on the coupled assay using thioesters as substrate analogues. The coupled assay is realized by developing highly water‐soluble thiol‐reacting probes based on phosphonate‐substituted boron dipyrromethene (BODIPY). The system enables the detection of cholinesterase activities in blood samples at single‐molecule level, and it is shown that the dissecting alterations of single‐molecule esterase activities can serve as an informative platform for activity‐based diagnosis.
Rechargeable Zinc–Air versus Lithium–Air Battery: from Fundamental Promises Toward Technological Potentials
Authors: Bi Xuanxuan , Jiang Yi , Chen Ruiting , Du Yuncheng , Zheng Yun , Yang Rong , Wang Rongyue , Wang Jiantao , Wang Xin , Chen Zhongwei 
Published: December 2023

AbstractAs battery technologies that can potentially increase the energy density and expand application scenarios of the lithium‐ion batteries, rechargeable metal‒air batteries have attracted extensive research interests. Among a variety types of metal anodes investigated, zinc (Zn)‒air and lithium (Li)‒air batteries hold best prospects for real‐world applications and attract the most scientific community interests. It has been more than 10 years since Cho et al. first compared Li–air and Zn–air batteries, during which great progress has been made. In this review, these two representative metal‒air battery technologies are compared in view of the most recent progresses and improvements in the last decade, especially efforts that push these technologies toward real world applications. It starts with the fundamentals of Zn–air and Li–air batteries, and discusses the progress made in electrolyte design, anode protection, and cathode catalysts development. It ends with an evaluation of the current research state along with an overall future perspective. Such a comprehensive comparison of typical non‐aqueous and aqueous battery systems with a focus on practical application criteria would be a timely review of metal‒air battery development in the last decade, which shed light for fundamental and applied research, eventually leading to real‐world application.
Interfacial Design Contributing to High Conversion Efficiency in Mg3(Sb, Bi)2/Bi2Te3 Thermoelectric Module with Superior Stability
Authors: Qu Nuo , Sun Yuxin , Liu Zihang , Xie Liangjun , Zhu Yuke , Wu Hao , Chai Ronghao , Cheng Jinxuan , Guo Fengkai , Zhang Qian , Wang Ruiqi , Li Bangming , Wei Zhiguo , Cai Wei , Sui Jiehe 
Published: December 2023

AbstractMg3(Sb, Bi)2‐based materials possess excellent room‐temperature thermoelectric performance, while poor interfacial behaviors occur when connected with metal electrodes due to the strong chemical activity and volatility of Mg element. In this study, a high efficiency of 7.1% under a temperature difference of 230 K is achieved in n‐Mg3(Sb, Bi)2/p‐Bi2Te3 thermoelectric module. When changing the interfacial layer from Fe powder to Fe foil, it effectively prevents a significant diffusion of both Mg and Bi elements from the material matrix to the interfacial layer, resulting in an extremely low contact resistivity ≈3.4 µΩ cm2 that is almost one order lower than of that of Fe powder/Mg3(Sb, Bi)2 junction ≈30 µΩ cm2. Particularly, a thin diffusion layer with a width of ≈2 µm is initially observed in the unannealed Fe foil/Mg3(Sb, Bi)2 junction. Even after thermal aging at 573 K for 28 days, the diffusion‐layer width is basically unchanged and its corresponding contact resistivity maintained as low as ≈5.8 µΩ cm2. Overall, this work provides deep insights into interfacial design and paves the way for high‐performance and sustainable low‐grade waste heat recovery.