bluuebunny/crossref_metadata_2025_split huggingface dataset:
Bridging the Catalytic Turnover Gap Between Single‐Atom Iron Nanozymes and Natural Enzymes by Engineering the First and Second Shell Coordination
Authors: Choi Daeeun , Jung Hyeonjung , Im Jihye , Yi Seung Yeop , Kim Seongbeen , Lee Donghyun , Park Seonhye , Lee Changha , Kim Jaeyun , Han Jeong Woo , Lee Jinwoo 
Published: December 2023

AbstractSingle‐atom nanozymes (SAzymes) constitute a promising category of enzyme‐mimicking materials with outstanding catalytic performance. The performance of SAzymes improves through modification of the coordination environments around the metal center. However, the catalytic turnover rates of SAzymes, which are key measures of the effectiveness of active site modifications, remain lower than those of natural enzymes, especially in peroxidase‐reactions. Here, the first and second shell coordination tuning strategy that yields SAzymes with structures and activities analogous to those of natural enzymes is reported. The optimized SAzyme exhibits a turnover rate of 52.7 s−1 and a catalytic efficiency of 6.97 × 105 M−1 s−1. A computational study reveals that axial S‐ligands induce an alternative reaction mechanism, and SO2− functional groups provide hydrogen bonds to reduce the activation energy. In addition, SAzyme shows superior anti‐tumor ability in vitro and in vivo. These results demonstrate the validity of coordination engineering strategies and the carcinostatic potential of SAzymes.
Longevous Cycling of Rechargeable Zn‐Air Battery Enabled by “Raisin‐Bread” Cobalt Oxynitride/Porous Carbon Hybrid Electrocatalysts
Authors: Park Moon Gyu , Hwang Jeemin , Deng Ya‐Ping , Lee Dong Un , Fu Jing , Hu Yongfeng , Jang Myeong Je , Choi Sung Mook , Feng Renfei , Jiang Gaopeng , Qian Lanting , Ma Qianyi , Yang Lin , Jun Yun Seok , Seo Min Ho , Bai Zhengyu , Chen Zhongwei 
Published: December 2023

AbstractDeveloping commercially viable electrocatalyst lies at the research hotspot of rechargeable Zn‐air batteries, but it is still challenging to meet the requirements of energy efficiency and durability in realistic applications. Strategic material design is critical to addressing its drawbacks in terms of sluggish kinetics of oxygen reactions and limited battery lifespan. Herein, a “raisin‐bread” architecture is designed for a hybrid catalyst constituting cobalt nitride as the core nanoparticle with thin oxidized coverings, which is further deposited within porous carbon aerogel. Based on synchrotron‐based characterizations, this hybrid provides oxygen vacancies and Co‐Nx‐C sites as the active sites, resulting from a strong coupling between CoOxNy nanoparticles and 3D conductive carbon scaffolds. Compared to the oxide reference, it performs enhanced stability in harsh electrocatalytic environments, highlighting the benefits of the oxynitride. Furthermore, the 3D conductive scaffolds improve charge/mass transportation and boost durability of these active sites. Density functional theory calculations reveal that the introduced N species into hybrid can synergistically tune the d‐band center of cobalt and improve its bifunctional activity. As a result, the obtained air cathode exhibits bifunctional overpotential of 0.65 V and a battery lifetime exceeding 1350 h, which sets a new record for rechargeable Zn‐air battery reported so far.
Strong Substrate Influence on Atomic Structure and Properties of Epitaxial VO2 Thin Films
Authors: Atul Atul , Ahmadi Majid , Koutsogiannis Panagiotis , Zhang Heng , Kooi Bart J. 
Published: December 2023

AbstractThe metal–insulator transition (MIT) observed in vanadium dioxide has been a topic of great research interest for past decades, with the underlying physics yet not fully understood due to the complex electron interactions and structures involved. The ability to understand and tune the MIT behavior is of vital importance from the perspective of both underlying fundamental science as well as potential applications. In this work, scanning transmission electron microscopy (STEM) is used to investigate cross‐section lamella of the VO2 films deposited using pulsed laser deposition on three substrates: c‐cut sapphire, TiO2(101) and TiO2(001). Advanced STEM imaging is performed in which also the oxygen atom columns are resolved. The overall film quality and structures on atomic and nanoscale are linked to the electrical transition characteristics. Relatively poor MIT characteristics are observed on c‐sapphire due to the presence of very small domains with six orientation variants, and on TiO2 (001) due to the presence of cracks induced by stress relaxation. However, the MIT on TiO2 (101) behaves favorably, despite similar stress relaxation which, however, only leads to domain boundaries but no cracks.
Integration of Metal Meshes as Transparent Conducting Electrodes into Perovskite Solar Cells
Authors: Ongaro Chiara , Roose Bart , Fleury Jeremy , Schneider René , Frohna Kyle , Ooi Zher Ying , Heier Jakob , Stranks Samuel D. , Schüler Andreas 
Published: December 2023

AbstractAs the demand for photovoltaic technologies continues to grow, the quest for efficient and sustainable transparent conducting electrodes (TCEs) rapidly rises. Traditional solutions, such as indium tin oxide (ITO), face challenges related to indium scarcity and environmental impact. To tackle these issues, a novel metal mesh rear TCE consisting of gold micro‐meshes is developed as ITO replacement in perovskite solar cells (PSCs). This study reveals that optimized Au meshes can guarantee 75% of the extracted photocurrent compared to reference devices with ITO and a promising power conversion efficiency (PCE) of 8.65%. By utilizing hybrid mesh structures with a 10‐nm ITO layer, the PCE further improves to 12.1%, with the extracted current exceeding 80% of the reference. Metal meshes can even serve to replace the opaque metal contact of PSCs, amplifying their functionality and efficiency through bifacial and multi‐junction applications. Here, aerosol jet‐printed silver meshes serve as front electrodes, combined with either 5–10 nm of Au, achieving efficient semi‐transparent devices (PCE 16.8%), or with 5–10 nm of ITO, providing enhanced bifacial properties while maintaining competitive efficiency. Overall, this work highlights remarkable features of metal meshes, making them promising alternatives to commonly used TCEs in optoelectronic applications.
Constructing 1D/2D NiCo‐LDH Nanowire/MXene Composites for Efficient And Stable Lithium Storage
Authors: Yang Tao , Zhang Zehao , Ma Pin , Li Haibo 
Published: December 2023

AbstractBimetallic layered double hydroxide (LDH) delivers competitive performance in lithium‐ion battery (LIB) because of the unique layered structure. However, the electrochemical performance of LDH is hindered by the low conductivity and the huge structure change upon cycling. To face this challenge, the 1D/2D NiCo‐LDH nanowire/MXene composites (NiCo‐LDH/MXene) are dedicatedly constructed via a simple one‐step hydrothermal method. Owing to the robust conductive skeleton is enabled by MXene nanosheets and abundant electroactive sites provided by NiCo‐LDH nanowires, the NiCo‐LDH/MXene anode exhibits rapid ion diffusion, exceptional redox reaction, and superior structural stability. Consequently, it offers a high specific capacitance of 1081 mAh g−1 after 100 cycles at the current density of 100 mA g−1 and impressive rate performance, i.e., 439 mAh g−1 at the current density of 1000 mA g−1. These results will motivate the exploration of advanced electrode materials for application in energy storage devices.
Contractible Plasmonic Nanospheres Array with Dynamically Tailorable Gap Size for Molecule Trapping and Sensitive SERS Detection
Authors: Yan Sisi , Tang Haibin , Sun Jiacheng , Zhu Chuhong , Pan Qijun , Chen Bin , Meng Guowen 
Published: December 2023

AbstractSurface‐enhanced Raman spectroscopy (SERS) is a powerful analysis technique, and the SERS sensitivity is strongly dependent on metallic nanogaps with a greatly enhanced local electromagnetic field (i.e., hot spots). Once the analytes are located in the hot spot region, their Raman signals are enormously amplified. However, delivering analytes into such tiny hot spots remains a great challenge, particularly for molecules with small Raman scattering cross‐sections and no metal affinity. Here, by employing the isotropic contraction characteristics of polyvinyl chloride (PVC) when heated, a molecule trapping and SERS sensing strategy is demonstrated based on a large‐area ordered gold‐coated polystyrene nanospheres (PS@Au NSs) array with well‐controlled gap size assembled on PVC sheet. Compared with the traditional contraction‐adsorption mode, the developed adsorption‐contraction mode enables efficient delivery of analytes with or without metal affinity into the hot spots between the PS@Au NSs, leading to a significantly improved SERS performance with a large SERS enhancement factor of ≈3.57 × 107. The contractible SERS substrate exhibits a high sensitivity of 10−12 m for rhodamine 6G (R6G), 10−10 m for thiram, and 5 × 10−6 m for 2,3,4‐trichlorobiphenyl, as well as good signal reproducibility with relative standard deviations of 2.81% and 4.25% for R6G and thiram, respectively.
G3BP1 and SLU7 Jointly Promote Immune Evasion by Downregulating MHC‐I via PI3K/Akt Activation in Bladder Cancer
Authors: Zheng Xianchong , Chen Jiawei , Deng Minhua , Ning Kang , Peng Yulu , Liu Zhenhua , Li Xiangdong , Zhou Zhaohui , Tang Huancheng , Li Yaoying , Kang Tiebang , Liu Zhuowei 
Published: December 2023

AbstractImmune checkpoint inhibitors (ICIs) show promise as second‐line treatment for advanced bladder cancer (BLCA); however, their responsiveness is limited by the immune evasion mechanisms in tumor cells. This study conduct a Cox regression analysis to screen mRNA‐binding proteins and reveals an association between Ras GTPase‐activating protein‐binding protein 1 (G3BP1) and diminished effectiveness of ICI therapy in patients with advanced BLCA. Subsequent investigation demonstrates that G3BP1 enhances immune evasion in BLCA cells by downregulating major histocompatibility complex class I (MHC‐I) through phosphoinositide 3‐kinase (PI3K)/Akt signaling activation. Mechanistically, G3BP1 interacts with splicing factor synergistic lethal with U5 snRNA 7 (SLU7) to form a complex with poly(A)‐binding protein cytoplasmic 1 and eukaryotic translation initiation factor 4 gamma 1. This complex stabilizes the closed‐loop structure of the mRNAs of class IA PI3Ks and consequently facilitates their translation and stabilization, thereby activating PI3K/Akt signaling to downregulate MHC‐I. Consistently, targeting G3BP1 with epigallocatechin gallate (EGCG) impedes immune evasion and sensitizes BLCA cells to anti‐programmed cell death (PD)‐1 antibodies in mice. Thus, G3BP1 and SLU7 collaboratively contribute to immune evasion in BLCA, indicating that EGCG is a precision therapeutic agent to enhance the effectiveness of anti‐PD‐1 therapy.
A Novel Cargo Delivery System‐AnCar‐ExoLaIMTS Ameliorates Arthritis via Specifically Targeting Pro‐Inflammatory Macrophages
Authors: Li Song , Wu Ya‐ran , Peng Xiu‐qin , Chen Han‐gang , Zhang Tong‐yi , Chen Hua , Yang Jing , Xie Yang‐li , Qi Hua‐bing , Xiang Wei , Huang Bo , Zhou Si‐ru , Hu Yan , Tan Qiao‐yan , Du Xiao‐lan , Huang Jun‐lan , Zhang Ruo‐bin , Li Xiao‐hong , Luo Feng‐tao , Jin Min , Su Nan , Luo Xiao‐qing , Huang Shuo , Yang Peng , Yan Xiao‐Jing , Lian Ji‐qin , Zhu Ying , Xiong Yan , Xiao Gong‐yi , Liu Ying‐ying , Shen Chen , Kuang Liang , Ni Zhen‐hong , Chen Lin 
Published: December 2023

AbstractMacrophages are heterogenic phagocytic cells that play distinct roles in physiological and pathological processes. Targeting different types of macrophages has shown potent therapeutic effects in many diseases. Although many approaches are developed to target anti‐inflammatory macrophages, there are few researches on targeting pro‐inflammatory macrophages, which is partially attributed to their non‐s pecificity phagocytosis of extracellular substances. In this study, a novel recombinant protein is constructed that can be anchored on an exosome membrane with the purpose of targeting pro‐inflammatory macrophages via antigen recognition, which is named AnCar‐ExoLaIMTS. The data indicate that the phagocytosis efficiencies of pro‐inflammatory macrophages for different AnCar‐ExoLaIMTS show obvious differences. The AnCar‐ExoLaIMTS3 has the best targeting ability for pro‐inflammatory macrophages in vitro and in vivo. Mechanically, AnCar‐ExoLaIMTS3 can specifically recognize the leucine‐rich repeat domain of the TLR4 receptor, and then enter into pro‐inflammatory macrophages via the TLR4‐mediated receptor endocytosis pathway. Moreover, AnCar‐ExoLaIMTS3 can efficiently deliver therapeutic cargo to pro‐inflammatory macrophages and inhibit the synovial inflammatory response via downregulation of HIF‐1α level, thus ameliorating the severity of arthritis in vivo. Collectively, the work established a novel gene/drug delivery system that can specifically target pro‐inflammatory macrophages, which may be beneficial for the treatments of arthritis and other inflammatory diseases.
Polydopamine‐Modified 2D Iron (II) Immobilized MnPS3 Nanosheets for Multimodal Imaging‐Guided Cancer Synergistic Photothermal‐Chemodynamic Therapy
Authors: Xie Hanhan , Yang Ming , He Xiaoli , Zhan Zhen , Jiang Huaide , Ma Yanmei , Hu Chengzhi 
Published: December 2023

AbstractManganese phosphosulphide (MnPS3), a newly emerged and promising member of the 2D metal phosphorus trichalcogenides (MPX3) family, has aroused abundant interest due to its unique physicochemical properties and applications in energy storage and conversion. However, its potential in the field of biomedicine, particularly as a nanotherapeutic platform for cancer therapy, has remained largely unexplored. Herein, a 2D “all‐in‐one” theranostic nanoplatform based on MnPS3 is designed and applied for imaging‐guided synergistic photothermal‐chemodynamic therapy. (Iron) Fe (II) ions are immobilized on the surface of MnPS3 nanosheets to facilitate effective chemodynamic therapy (CDT). Upon surface modification with polydopamine (PDA) and polyethylene glycol (PEG), the obtained Fe‐MnPS3/PDA‐PEG nanosheets exhibit exceptional photothermal conversion efficiency (η = 40.7%) and proficient pH/NIR‐responsive Fenton catalytic activity, enabling efficient photothermal therapy (PTT) and CDT. Importantly, such nanoplatform can also serve as an efficient theranostic agent for multimodal imaging, facilitating real‐time monitoring and guidance of the therapeutic process. After fulfilling the therapeutic functions, the Fe‐MnPS3/PDA‐PEG nanosheets can be efficiently excreted from the body, alleviating the concerns of long‐term retention and potential toxicity. This work presents an effective, precise, and safe 2D “all‐in‐one” theranostic nanoplatform based on MnPS3 for high‐efficiency tumor‐specific theranostics.
RNA m6A Methylation Suppresses Insect Juvenile Hormone Degradation to Minimize Fitness Costs in Response to A Pathogenic Attack
Authors: Guo Zhaojiang , Bai Yang , Zhang Xinyi , Guo Le , Zhu Liuhong , Sun Dan , Sun Kaiyue , Xu Xudan , Yang Xin , Xie Wen , Wang Shaoli , Wu Qingjun , Crickmore Neil , Zhou Xuguo , Zhang Youjun 
Published: December 2023

AbstractBioinsecticides and transgenic crops based on the bacterial pathogen Bacillus thuringiensis (Bt) can effectively control diverse agricultural insect pests, nevertheless, the evolution of resistance without obvious fitness costs has seriously eroded the sustainable use of these Bt products. Recently, it has been discovered that an increased titer of juvenile hormone (JH) favors an insect host (Plutella xylostella) to enhance fitness whilst resisting the Bt pathogen, however, the underlying regulatory mechanisms of the increased JH titer are obscure. Here, the involvement of N6‐methyladenosine (m6A) RNA modification in modulating the availability of JH in this process is defined. Specifically, it is found that two m6A methyltransferase subunit genes, PxMettl3 and PxMettl14, repress the expression of a key JH‐degrading enzyme JH esterase (JHE) to induce an increased JH titer, mitigating the fitness costs associated with a robust defense against the Bt pathogen. This study identifies an as‐yet uncharacterized m6A‐mediated epigenetic regulator of insect hormones for maintaining fitness during pathogen defense and unveils an emerging Bt resistance‐related m6A methylation atlas in insects, which further expands the functional landscape of m6A modification and showcases the pivotal role of epigenetic regulation in host‐pathogen interactions.
Electron Modulated and Phosphate Radical Stabilized 1T‐Rich MoS2 for Ultra‐Fast‐Charged Sodium Ion Storage
Authors: Zhang Yuxiang , Wang Jing , Shan Lina , Han Bo , Gao Qiang , Cai Zhao , Zhou Chenggang , Tian Xike , Sun Ruimin , Mai Liqiang 
Published: December 2023

AbstractMetallic phase molybdenum sulfide (1T‐MoS2) is considered as an attractive electrode material for sodium‐ion batteries (SIBs) owing to its abundant active sites, metallic conductivity and high theoretical capacity. Unfortunately, the thermodynamic unstable characteristic under natural conditions makes 1T‐MoS2 difficult to synthesize directly, which greatly hinders its further applications. Herein, an electron modulated and phosphate radical stabilized strategy is employed to construct stable 1T‐rich MoS2 (1T‐P‐MoS2). The PO43− groups are intercalated into MoS2 via a simple one‐step synthesis process, which enlarges the interlayer spacings and improves the insertion/extraction kinetics of Na+. Density functional theory (DFT) calculations and experiments demonstrate that the PO43− can give partial electrons to Mo upon PO43− intercalation, which triggers the reorganization of Mo 4d orbitals, resulting in a spontaneous phase transition of MoS2 from 2H to 1T phase, thereby enhancing the electrical conductivity of MoS2. The obtained 1T‐P‐MoS2 exhibits ultra‐fast charged properties (up to 277.1 mAh g−1 at 40 A g−1, discharged/charged within 25 s) and excellent cycling performance (up to 498.9 mAh g−1 after 300 cycles at 1 A g−1). This work provides a feasible technical solution and analyses the deep mechanisms on tuning of metal sulfide electrodes for advanced SIBs.
Persistence and disadoption of sustainable agricultural practices in the Mississippi Delta region
Authors: Pathak Santosh , Wang Hua , Tran Dat Q. , Adusumilli Naveen C. 
Published: December 2023

AbstractThe working lands programs in the United States are specifically tailored to support farmers in initiating or enhancing conservation practices. The expectation is that farmers receiving financial assistance will continue implementing these practices even after their initial contracts end, thereby increasing the programs’ cost‐effectiveness and promoting natural resources conservation. However, little is known about the likelihood of persistence and disadoption of conservation practices once the initial cost‐share contracts expire. Using the first‐order Markov chain framework on state‐level conservation practices acreage data from the Mississippi Delta region (2005–2022), this study provides quantitative estimates of changing (dis)adoption patterns of four conservation practices: cover crops (CCs), conservation tillage (CT), nutrient and irrigation management (NIM), and conservation crop rotation (CCR). The findings reveal a higher probability of persistence of NIM practices. In contrast, acres devoted to CCs and CT tend to transition into other alternative practices, indicating a greater likelihood of disadoption. Importantly, the likelihood of acres that initially adopt conservation practices with funding shifting to a condition of no conservation activity is minimal. The transition probability estimates facilitate the prediction of future adoption rates of conservation practices and aid funding agencies in prioritizing their conservation efforts.
One‐Carbon Ring Expansion of Indoles and Pyrroles: A Straightforward Access to 3‐Fluorinated Quinolines and Pyridines
Authors: Guo Huaixuan , Qiu Shiqin , Xu Peng 
Published: December 2023

Abstract3‐Fluorinated quinolines and pyridines are prevalent pharmacophores, yet their synthesis is often challenging. Herein, we demonstrate that dibromofluoromethane as bromofluorocarbene source enables the one‐carbon ring expansion of readily available indoles and pyrroles to structurally diverse 3‐fluorinated quinolines and pyridines. This straightforward protocol requires only a short reaction time of ten minutes and can be performed under air atmosphere. Preliminary investigations reveal that this strategy can also be applied to the synthesis of other valuable azines by using different 1,1‐dibromoalkanes as bromocarbene sources.
Pauling‐Type Adsorption of O2Induced by Heteroatom Doped ZnIn2S4for Boosted Solar‐Driven H2O2Production
Authors: Zhang Kailian , Tian Lei , Yang Jingfei , Wu Fengxiu , Wang Leigang , Tang Hua , Liu Zhao‐Qing 
Published: December 2023

AbstractBreaking the trade‐off between activity and selectivity has perennially been a formidable endeavor in the field of hydrogen peroxide (H2O2) photosynthesis, especially the side‐on configuration of oxygen (O2) on the catalyst surface will cause the cleavage of O−O bonds, which drastically hinders the H2O2production performance. Herein, we present an atomically heteroatom P doped ZnIn2S4catalyst with tunable oxygen adsorption configuration to accelerate the ORR kinetics essential for solar‐driven H2O2production. Indeed, the spectroscopy characterizations (such as EXAFS and in situ FTIR) and DFT calculations reveal that heteroatom P doped ZnIn2S4at substitutional and interstitial sites, which not only optimizes the coordination environment of Zn active sites, but also facilitates electron transfer to the Zn sites and improves charge density, avoiding the breakage of O−O bonds and reducing the energy barriers to H2O2production. As a result, the oxygen adsorption configuration is regulated from side‐on (Yeager‐type) to end‐on (Pauling‐type), resulting in the accelerated ORR kinetics from 874.94 to 2107.66 μmol g−1 h−1. This finding offers a new avenue toward strategic tailoring oxygen adsorption configuration by the rational design of doped photocatalyst.
Tuning Active Site Flexibility by Defect Engineering of Graphene Ribbon Edge‐hosted Fe−N3 Sites
Authors: Yang Piaoping , Li Jiang , Vlachos Dionisios G. , Caratzoulas Stavros 
Published: December 2023

AbstractNitrogen‐doped, carbon‐supported transition metal catalysts are excellent for several reactions. Structural engineering of M−Nx sites to boost catalytic activity is rarely studied. Here, we demonstrate that the structural flexibility of Fe−N3 site is vital for tuning the electronic structure of Fe atoms and regulating the catalytic transfer hydrogenation (CTH) activity. By introducing carbon defects, we construct Fe−N3 sites with varying Fe−N bond lengths distinguishable by X‐ray absorption spectroscopy. We investigate the CTH activity by density‐functional theory and microkinetic calculations and reveal that the vertical displacement of the Fe atom out of the plane of the support, induced by the Fe−N3 distortion, raises the Fe
orbital and strengthens binding. We propose that the activity is controlled by the relaxation of the reconstructed site, which is further affected by Fe−N bond length, an excellent activity descriptor. We elucidate the origin of the CTH activity and principles for high‐performing Fe−N−C catalysts by defect engineering.