bluuebunny/crossref_metadata_2025_split huggingface dataset:
Redox‐Bipolar Covalent Organic Framework Cathode for Advanced Sodium‐Organic Batteries
Authors: Cheng Linqi , Yan Xiaoli , Yu Jie , Zhang Xupeng , Wang Heng‐Guo , Cui Fengchao , Wang Yinghui 
Published: November 2024

AbstractRedox‐active covalent organic frameworks (COFs) are promising candidates for sodium‐ion batteries (SIBs). However, the construction of redox‐bipolar COFs with the anions and cations co‐storage feature for SIBs is rarely reported. Herein, redox‐bipolar COF constructed from aniline‐fused quinonoid units (TPAD‐COF) is developed as the cathode material in SIBs for the first time. The unique integration of conductive aniline skeletons and quinone redox centers endows TPAD‐COF with high ionic/electrical conductivity, abundant redox‐active sites, and fascinating bipolar features. Consequently, the elaborately tailored TPAD‐COF cathode exhibits higher specific capacity (186.4 mAh g−1 at 0.05 A g−1) and superior cycling performance (over 2000 cycles at 1.0 A g−1 with 0.015% decay rate per cycle). Impressively, TPAD‐COF also displays a high specific capacity of 101 mAh g−1 even at −20 °C. As a proof of concept, all‐organic SIBs (AOSIBs) are assembled using TPAD‐COF cathode and disodium terephthalate anode, which also show impressive electrochemical properties, indicating the potential application of TPAD‐COF cathode in AOSIBs. The work will pave the avenue toward advanced COFs cathode for rechargeable batteries through rational molecular design.
Engineered Biomimetic Cancer Cell Membrane Nanosystems Trigger Gas‐Immunometabolic Therapy for Spinal‐Metastasized Tumors
Authors: Lu Hongwei , Liang Bing , Hu Annan , Zhou Hao , Jia Chao , Aji Abudula , Chen Qing , Ma Yiqun , Cui Wenguo , Jiang Libo , Dong Jian 
Published: November 2024

AbstractDespite great progress in enhancing tumor immunogenicity, conventional gas therapy cannot effectively reverse the tumor immunosuppressive microenvironment (TIME), limiting immunotherapy. The development of therapeutic gases that are tumor microenvironment responsive and efficiently reverse the TIME for precisely targeted tumor gas‐immunometabolic therapy remains a great challenge. In this study, a novel cancer cell membrane‐encapsulated pH‐responsive nitric oxide (NO)‐releasing biomimetic nanosystem (MP@AL) is prepared. Lactate oxidase (Lox) in MP@AL consumed oxygen to promote the decomposition of lactate, a metabolic by‐product of tumor glycolysis, and the generation of H2O2, while L‐arginine (L‐Arg) in MP@AL is oxidized by H2O2 to generate nitric oxide (NO). For one thing, NO led to mitochondrial dysfunction in tumor cells to reduce oxygen consumption and promote the efficiency of Lox in lactate decomposition, thus reversing lactate‐induced TIME; for another, NO effectively triggered immunogenic cell death, activated anti‐tumor immune response and long‐term immune memory, and ensured a favorable effect in the synergistic interaction with PD‐L1 antibody for inhibiting tumor growth and recurrence. Therefore, a novel gas‐immunometabolic therapy dual closed‐loop nanosystem for enhancing tumor immunogenicity and remodeling lactate‐induced TIME is established. Overall, this work will provide new ideas for gas therapy to effectively remodel the TIME to enhance cancer immunotherapy.
Entropic Design of Anionic Site to Improve Anionic Redox Stability in Lithium‐Rich Cathode
Authors: Zheng Chaoliang , Zhang Juan , Mao Huican , Wang Yaqing , Yang Xiaoxu , Li Jie , Zhang Di , Feng Ting , Wang Xindong , Kang Feiyu , Li Jianling 
Published: November 2024

AbstractCobalt‐free manganese‐rich layered oxide is considered one of the most promising cathode materials for next‐generation lithium‐ion batteries due to its high capacity and low cost. However, irreversible anionic redox (OAR) leads to serious failure problems and hinders its wide application. To solve the above problems, the entropy design strategy of anionic sites is proposed, which is more direct and relevant to the regulation of the OAR process compared to the traditional entropy design of TM sites. The entropic design improves the structural diversity and long‐range disorder of the material, which effectively inhibits oxygen release and drastic structural strain, and alleviates structural degradation. After 400 cycles at 1C, the capacity and voltage decay per cycle are only 0.092 mAh g−1 and 1.36 mV, respectively. The long cycle test (10C and 1000 cycles) at high current shows that the voltage and capacity decay are only 0.04 mAh g−1 and 0.66 mV per cycle, respectively. Meanwhile, the rate performance at 10C reaches 175 mAh g−1. The charge compensation regulation and performance enhancement mechanism are investigated by systematic in‐situ/ex‐situ characterization and theoretical calculation. This research provides new ideas for the design of lithium‐rich cathodes with stable OAR and high structural adaptability.
Neuro‐Actuating Photonic Skin Enabled by Ion‐Gel Transistor with Thermo‐Adaptive Block Copolymer
Authors: Kim Gwanho , Lee Seokyeong , Yoon Jungwon , Lee Kyuho , Kim Woojoong , Kim Jiwon , Jang Jihye , Ha Jebong , Kim Taebin , Zhao Kaiying , Kim HoYeon , Lee Seonju , Oh Ji Hye , Kim Junsu , Hassan Tufail , Cho Soo Yeong , Ryu Du Yeol , Koo Chong Min , Park Chanho , Park Cheolmin 
Published: November 2024

AbstractDespite significant progress in developing artificial synapses to emulate the human nervous system for bio‐signal transmission, synapses with thermo‐adaptive coloration and soft actuators driven by temperature change have seldom been reported. Herein, a photonic neuro‐actuating synaptic skin is presented enabling thermoresponsive synaptic signal transmission, color variation, and actuation. First, a thermoresponsive display synapse is developed based on a 3‐terminal ion‐gel transistor with a poly (3,4‐ethylene dioxythiophene):poly (styrene sulfonate) (PEDOT:PSS) semiconducting channel mixed with 2D titanium carbide (Ti3C2Tx) MXene and a thermo‐adaptive 1D block copolymer (BCP) photonic crystal (PC) gate insulator. Temperature‐dependent synaptic behavior is successfully observed in the ion‐gel transistor with the corresponding structural colors, leading to a thermo‐adaptive display synapse. The 3 × 3 arrays of thermo‐adaptive display synapses with Joule heaters show that each pixel is controlled by the thermoresponsive structural color and synaptic output. The synaptic output current from the MXene ion‐gel transistor can be converted and amplified to a voltage signal, which powers a soft actuator connected to the ion‐gel display synapse and triggers temperature‐dependent actuation related to the thermoresponsive synaptic performance. This study showcases a thermo‐adaptive photonic neuro‐actuating artificial skin that emulates muscle‐combined neuronal human skin with visualization capability.
Chemodivergent Phototransformations of Green Fluorescent Protein Related Chromophores: Wavelength‐Dependent Photodimerization and Spirocyclization
Authors: Opryshko Victoria E. , Ivanov Dmitrii S. , Danshina Anastasia A. , Krasnova Svetlana A. , Eshtukov‐Shcheglov Artur V. , Mikhaylov Andrey A. , Smirnov Alexander Yu. , Baranov Mikhail S. 
Published: November 2024

AbstractBenzylidene imidazolones with an ortho‐sec‐amino group undergo chemodivergent photochemical transformations, based on the wavelength of irradiation. Irradiation at 525 nm causes dimerization and the formation of cyclobutanes with two spiroatoms, related to dictazoles in 87–98% yield. In turn, irradiation at 365 nm provides access to spirocyclic indolines in 67–92% yield. Each of the processes proceeds with exclusive atom economy and chemoselectivity.
Asymmetric Transfer Hydrogenation of 3‐Substituted 2H‐1,4‐Benzoxazines under Tethered Cp*Rh(III)‐Diamine Catalysis with Unexpected Reversal of Enantioselectivity
Authors: Li Xiaohan , Yang Ji , He Zhenni , Huang Wei , Yang Jianbo , Li Huanrong , Xu Lijin , Shi Qian 
Published: November 2024

AbstractThe asymmetric transfer hydrogenation of 3‐substituted 2H‐1,4‐benzoxazines with an azeotropic mixture of HCO2H/NEt3 (5/2) using tethered Cp*Rh(III)‐diamine catalysis has been realized. This process allows access to a broad range of chiral 3,4‐dihydro‐2H‐1,4‐benzoxazines in high yields with up to 99% ee, and tolerates a variety of functional groups. The enantiocontrol is achieved by the judicious choice of catalyst and hydrogen source. This reaction proceeds with unexpected reversal of enantioselectivity, which is attributed to the acidic reaction conditions and the hydrogen bond between the N−H of the rhodium species and the O atom in the substrate.
Stereoconvergent Access to Z‐Allylborons from E/Z‐Mixed 1,3‐Dienes via Cu‐Guanidine Catalysis
Authors: Zhang Ai , Zhang Huangfeng , Jin Tao , Ge Lin , Ma Xiaoyan , Tang Jinghua , Liu Jinyu , Tan Choon‐Hong , Lee Richmond , Ge Yicen 
Published: November 2024

AbstractMerging the stereoisomeric mixture of substrate into a single product through stereospecific transformation is a challenging but higher‐order synthetic strategy, which perfectly meets the demand of cost control in the precise chemical production. In this work, the stereoconvergent synthesis of Z‐allylic boronates was realized with protoborylation of E/Z‐mixed 1,3‐dienes catalyzed by a novel copper‐guanidine complex. The reaction could proceed smoothly under very mild conditions with good functional group tolerance, and convert diverse aryl‐substituted 1,3‐dienes into the desired Z‐1,4‐addition products with excellent chemo‐, regio‐, and stereoselectivities in minutes. Detailed mechanistic studies also helped to disclose the origin of stereoconvergency. Both E‐ and Z‐diene were found directly undergoing a rapid borylation without E/Z isomerization of C=C bond, followed by a convergent formation of the same thermodynamically stable allylcopper intermediate before the slow protonation step occurred.
Activation of Hidden Catalytic Sites in 2D Basal Plane via p–n Heterojunction Interface Engineering Toward Efficient Oxygen Evolution Reaction
Authors: Kim Eugene , Kim Sungsoon , Kim Yongchul , Hamkins Kiran , Baek Jihyun , Kim MinJoong , Liu Tae‐Kyung , Choi Young Moon , Lee Jung Hwan , Jang Gyu Yong , Lee Kug‐Seung , Lee Geunsik , Zheng Xiaolin , Park Jong Hyeok 
Published: November 2024

AbstractNonprecious metal‐based 2D materials have shown promising electrocatalytic activity toward the oxygen evolution reaction (OER). However, the catalytically active sites of 2D materials are mainly presented at the edge, and most of their basal planes are still catalytically inactive, which turns into a significant drawback on the catalytic efficiency. Here, a novel p–n heterojunction strategy is suggested that generates active sites on the basal plane of 2D NiFe‐layered double hydroxide (NiFe‐LDH). The n‐type NiFe‐LDH is first grown on a nickel foam (NF) substrate, and p‐type Co3O4 nanocubes are deposited through a simple dip‐coating method to fabricate a Co3O4/NiFe‐LDH@NF p–n heterojunction electrode. As a result, electron transfer is induced at the interface of p‐type Co3O4 and n‐type NiFe‐LDH, which consequently promotes oxidation of the inert Ni2+ state to a more catalytically active Ni3+ state on the inert basal plane of NiFe‐LDH. As‐prepared Co3O4/NiFe‐LDH@NF electrodes obtained enhanced OER performance showing a high current density of 100 mA cm−2 at 1.48 V (vs RHE) which outperforms that of pristine NiFe‐LDH@NF. The utilization of the p–n junction concept will disclose a new strategy for modifying the electronic structure of the catalytically inactive basal plane and stimulating its electrocatalytic activity.
Updated risk prediction model for pancreaticoduodenectomy using data from the National Clinical Database in Japan
Authors: Mizuma Masamichi , Endo Hideki , Yamamoto Hiroyuki , Shimura Mitsuhiro , Iseki Masahiro , Unno Michiaki , Oshikiri Taro , Kakeji Yoshihiro , Shirabe Ken 
Published: November 2024

AbstractAimRisk prediction models for mortality, severe postoperative complications, and postoperative pancreatic fistula in patients undergoing pancreaticoduodenectomy were established using data from the National Clinical Database more than a decade ago, and the surgical outcomes of pancreaticoduodenectomy have improved over the years. The aim of this study is to update the risk prediction model for pancreaticoduodenectomy using National Clinical Database data.MethodsBetween 2019 and 2021, the data of 35 365 patients who underwent pancreaticoduodenectomy and who were registered in the National Clinical Database were retrospectively analyzed. According to the registration year, the patients were divided into two cohorts: the development cohort (2019–2020; n = 23 654) and the validation cohort (2021; n = 11 711). Logistic regression analyses were performed to create risk models for surgical mortality, severe postoperative complications, and grade C postoperative pancreatic fistula.ResultsOverall, the rates of surgical mortality, severe postoperative complications, and grade C postoperative pancreatic fistula were 1.8%, 2.2%, and 1.3%, respectively. Logistic regression analyses revealed 28, 28, and 14 risk factors for surgical mortality, severe postoperative complications, and grade C postoperative pancreatic fistula, respectively. The area under the receiver operating characteristic curve of the risk model in the development cohort was 0.759 for surgical mortality, 0.712 for severe complications, and 0.699 for postoperative pancreatic fistula, comparable to the validation cohort. The calibration plots were favorable in both cohorts.ConclusionThe updated risk model for pancreaticoduodenectomy will be useful to predict surgical mortality, severe postoperative complications, and grade C postoperative pancreatic fistula.
Is Alcohol Consumption Pattern Dependent on Prenatal Sex‐Steroids? A Digit Ratio (2D:4D) Study Among University Students
Authors: Ślawski Barbara , Kasielska‐Trojan Anna , Manning John T. , Antoszewski Bogusław 
Published: November 2024

ABSTRACTIntroductionThere is evidence that alcohol consumption is influenced by prenatal sex steroids (as measured by digit ratio [2D:4D]). Here, we clarify the effect size of the relationship in a student (rather than a patient) population.MethodsThere were 258 (169 women) participants. Digit length was measured directly with calipers. Alcohol use was evaluated by the Polish version of Alcohol Use Disorders Identification Test (AUDIT) and operationalized as total AUDIT scores and grams of alcohol/week.ResultsDigit ratios were sexually dimorphic (males < females). There were negative correlations between right 2D:4D and Dr‐l (right 2D:4D minus left 2D:4D) and AUDIT scores and grams of alcohol/week in both sexes. Relationships varied from small (r = −0.29) to large (r = −0.69) and they were stronger in males in comparison to females and for right 2D:4D in comparison to Dr‐l. In males only, there were small (r = 0.21) to moderate (r = 0.31) positive associations with body size (height, weight, and mean right digit length) and alcohol consumption. Multiple regression analyses showed relationships between digit ratios remained significant but those for body size did not.ConclusionAlcohol consumption was negatively related to 2D:4D, suggesting high prenatal testosterone and low prenatal estrogen are linked to its consumption. Correlations varied in strength from small to large with the strongest found for right 2D:4D and for males. Positive relationships between body size and alcohol were small to moderate, confined to males, and were not independent of digit ratios. Prenatal androgenization may influence alcohol drinking patterns in non‐clinical individuals.
Stable Isotopes Analysis of Black Lion Tamarins Reveals Increasing Arthropod Consumption When Fruit Productivity Decreases in Forest Fragments
Authors: Raskin Amazone , Kaisin Olivier , Michel Loïc N. , Lejeune Benjamin , Lepoint Gilles , Amaral Rodrigo Gonçalves , Bufalo Felipe , Sabino Gabriel Pavan , Araújo Márcio Silva , Rezende Gabriela Cabral , Brotcorne Fany , Culot Laurence 
Published: November 2024

ABSTRACTGiven the cryptic and elusive nature of prey consumption, quantifying its contribution to the diet of free‐ranging primates using behavioral methods is challenging. In this context, the use of carbon and nitrogen‐stable isotopes represents a promising alternative approach. Here, we used stable isotope analysis to estimate the proportion of arthropods and fruits in the diet of black lion tamarins (Leontopithecus chrysopygus), an endangered primate endemic to the Brazilian Atlantic Forest. To do so, we ran stable isotope mixing models using isotopic data from hair samples of black lion tamarins living in six forest fragments showing different levels of habitat quality. Furthermore, we ran linear mixed models to assess the influence of habitat quality—fruit productivity (estimated by tree total basal area) and arthropod biomass – and individual characteristics (sex and body mass) on tamarins' δ15N values (a proxy for trophic position). Our results revealed that arthropods contributed more to black lion tamarins' diet than reported in previous behavioral studies, suggesting that behavioral observations may considerably underestimate the importance of arthropodivory in the diet of arboreal primates. The degree of arthropodivory and frugivory was similar within groups, in line with the strong group cohesion and synchronization of feeding behaviors of this species and supporting the role of site‐specific habitat characteristics on dietary choice. Arthropod consumption was higher in areas with lower fruit productivity and did not increase when arthropod biomass increased, suggesting that fruits represent a limiting but preferred resource for this species. These results demonstrate the dietary plasticity of black lion tamarins in areas of lower forest quality, where they manage to compensate low fruit productivity by shifting to a diet richer in arthropods. Considering that this species occurs within a highly fragmented landscape, preserving and protecting small forest patches remains crucial for the conservation of this species.
Geregelter Ladungstransfer in metallorganischen Donor‐Akzeptor‐Gerüstverbindungen für hochempfindliche Photodetektoren
Authors: Xu Zhiyun , Chandresh Abhinav , Mauri Anna , Esmaeilpour Meysam , Monnier Vincent , Odobel Fabrice , Heinke Lars , Wenzel Wolfgang , Kozlowska Mariana , Diring Stéphane , Haldar Ritesh , Wöll Christof 
Published: November 2024

AbstractBei der photoinduzierten Ladungstrennung sind organische Dünnschichten mit Donor‐ und Akzeptor‐Chromophoren für Anwendungen wie künstliche Photosynthese und Photodetektion von entscheidender Bedeutung. Eine der größten Herausforderungen ist die Optimierung der Ladungstrennungseffizienz und die Bestimmung des optimalen Akzeptor/Donor‐Verhältnisses. Dies ist aufgrund der Variabilität der molekularen Packung in diesen typischerweise amorphen organischen Aggregaten nur schwer zu erreichen. Metallorganische Gerüstverbindungen (MOFs) bieten einen rationalen Ansatz, indem sie die systematische Herstellung von Donor/Akzeptor‐Mischungen mit einstellbaren Verhältnissen innerhalb eines kristallinen Gitters ermöglichen. Wir demonstrieren diesen Ansatz, indem wir Naphthalindiimid (NDI)‐Donor‐ und Akzeptor‐Chromophore als Linker in eine hoch orientierte, monolithische MOF‐Dünnschicht einbauen. Durch die Anpassung der NDI‐Akzeptor‐Linkerkonzentration während der Schicht‐für‐Schicht‐Synthese der oberflächenmontierten MOF‐Dünnschichten (SURMOFs) konnten wir die Effizienz der Ladungstrennung erheblich steigern. Überraschenderweise lag die optimale Akzeptorkonzentration bei nur 3 %, womit eine vierzigfache Steigerung in der Effizienz der Photodetektion im Vergleich zu rein NDI‐Donor‐basierten SURMOFs erreicht wurde. Dieses unerwartete Verhalten wurde durch eine theoretische Analyse erklärt, die durch die gut definierte kristalline Struktur der SURMOFs ermöglicht wurde. Mit Hilfe der Dichtefunktionaltheorie und kinetischer Monte‐Carlo‐Simulationen konnten wir zwei gegensätzliche durch Akzeptoren bewirkte Effekte feststellen: Dem positive Effekt der Unterdrückung einer unerwünschten Rekombination von Ladungsträgern wirkt bei hohen Konzentrationen eine Verringerung der Ladungsträgermobilität entgegen.
Upcycling Iron Oxide Scale Slag into a High‐Performance, Sustainable Ozone Catalyst
Authors: Du Qing , Fang Yanfen , Lan Xing , Gu Cheng , Huang Di , Shen Zhou , Zhu Zhi , Chen Chuncheng , Yan Yan 
Published: November 2024

AbstractUpcycling iron slag into a monolithic catalyst has led to low‐cost heterogeneous catalytic ozonation (HCO) strategies for water treatment. The primary industrial challenges are the low chemical oxygen demand (COD) reduction rate in treating authentic wastewater and difficulties sustaining close‐loop reaction cycles. In this study, we present a monolithic catalyst transformed from low‐cost iron oxide scale slag (IOSM) for highly efficient, sustainable ozone catalysis. The IOSM, constituted of 59.70 % Fe2O3 and 40.30 % Fe3O4, effectively decomposes ozone into superoxide radicals (⋅O2−) through a close‐loop cyclic reaction facilitated by interfacial charge transfer. This mechanism enables super‐fast degradation of 100 mg L−1 tetracycline at ozone concentrations below 1.00 mg L−1 in just four minutes, with the iron leaching merely at 59 μg L−1 after 10 cycles. In tests with authentic antibiotic wastewater, the IOSM‐based HCO system achieves a record‐breaking 81.70 % COD reduction within two hours. This research underscores the potential of upcycling industrial waste into highly effective ozone catalysts for sustainable practices in wastewater treatment.
Interfacial Proton Precompensation: Suppressing Deprotonation‐Driven Lattice Collapse for Enhanced Efficiency and Stability in Perovskite Solar Cells
Authors: Xu Bingying , Liu Guozhen , Wang Pengfei , Li Wenzhe , Ying Zhehan , Liu Jing , Shi Yantao 
Published: November 2024

AbstractThe chemical property of the buried interface plays a crucial role in improving the performance and stability of perovskite solar cells (PSCs). The SnO2/perovskite interface prepared from SnO2 alkaline hydrogel with high proton affinity triggers directional migration and irreversible reactions of protons, exacerbating the disintegration of perovskite crystal. In this study, we proposed proton precompensation strategy to suppress the deprotonation effect of the buried interface and improve the durability of the devices. By modulating the chemical environment and surface energy state of the buried interface, the domain‐limiting and spontaneous compensation of protons in formamidinium (FA+) under coulomb force were achieved, thereby stabilizing the perovskite crystal structure. The stability of target perovskite films under UV illumination and heating at 85 °C was significantly enhanced. As a result, the devices can retain around 90 % of their initial power conversion efficiency (PCE) after 1000 h of continuous irradiation at the maximum power point (MPP). Moreover, due to the reduction of defect content at the buried interface and the improvement of conductivity and carrier mobility by the precompensation treatment, the interfacial energy loss and non‐radiative recombination were substantially diminished. The target PSC devices exhibited much higher PCE of 25.55 % than the control devices (23.03 %).