bluuebunny/crossref_metadata_2025_split huggingface dataset:
Laser‐Printed All‐Carbon Responsive Material and Soft Robot
Authors: Yu Wenjie , Zhao Weiwei , Zhu Xinbei , Li Mingyue , Yi Xiaosu , Liu Xiaoqing 
Published: July 2024

AbstractResponsive materials and actuators are the basis for the development of various leading‐edge technologies but have so far mostly been designed based on polymers, incurring key limitations related to sensitivity and environmental tolerance. This work reports a new responsive material, laser‐printed carbon film (LPCF), produced via direct laser transformation of a liquid organic precursor and consists of graphitic and amorphous carbons. The high activity of amorphous carbon combined with the dual‐gradient structure enables the LPCF to have a actuation speed of 9400° s−1 in response to the stimulus of organic vapor. LPCF exhibits a conductivity of 950 S m−1 and excellent resistance to various extreme environmental conditions, which are unachievable for polymer‐based materials. Additionally, an LPCF‐based all‐carbon soft robot that can mimic the complex continuous backward somersaulting motions without manual intervention is constructed. The locomotion velocity of the robot reaches a value of 1.19 BL s−1, which is almost one to two orders of magnitude faster than that of reported soft robots. This work not only offers a new paradigm for highly responsive materials but also provides a great design and engineering example for the next generation of biomimetic robots with life‐like performance.
Atomic‐Level Observation of Potential‐Dependent Variations at the Surface of an Oxide Catalyst during Oxygen Evolution Reaction
Authors: Park Chang Hyun , Lee Hyungdoh , Choi Jin‐Seok , Yun Tae Gyu , Lim Younghwan , Bae Hyung Bin , Chung Sung‐Yoon 
Published: July 2024

AbstractUnderstanding the intricate details of the surface atomic structure and composition of catalysts during the oxygen evolution reaction (OER) is crucial for developing catalysts with high stability in water electrolyzers. While many notable studies highlight surface amorphization and reconstruction, systematic analytical tracing of the catalyst surface as a function of overpotential remains elusive. Heteroepitaxial (001) films of chemically stable and lattice‐oxygen‐inactive LaCoO3 are thus utilized as a model catalyst to demonstrate a series of atomic‐resolution observations of the film surface at different anodic potentials. The first key finding is that atoms at the surface are fairly dynamic even at lower overpotentials. Angstrom‐scale atomic displacements within the perovskite framework are identified below a certain potential level. Another noteworthy feature is that amorphization (or paracrystallization) with no long‐range order is finally induced at higher overpotentials. In particular, surface analyses consistently support that the oxidation of lattice oxygen is coupled with amorphous phase formation at the high potentials. Theoretical calculations also reveal an upward shift of oxygen 2p states toward the Fermi level, indicating enhanced lattice oxygen activation when atom displacement occurs more extensively. This study emphasizes that the degradation behavior of OER catalysts can distinctively vary depending on the overpotential level.
Biometabolically Derived Selenium Nanoparticles Armed with Protein Protective Suit toward High‐Performance Li‐Se Batteries
Authors: Xia Yang , Lu Chengwei , Fan Wenluxi , Fang Ruyi , Xu Lusheng , Huang Haichan , Xiao Zhen , Zhang Jun , Huang Hui , Gan Yongping , He Xinping , Tao Xinyong , Xia Xinhui , Zhang Wenkui 
Published: July 2024

AbstractSelenium (Se) serves as a burgeoning high‐energy‐density cathode material in lithium‐ion batteries. However, the development of Se cathode is strictly limited by low Se utilization and inferior cycling stability arising from intrinsic volume expansion and notorious shuttle effect. Herein, a microbial metabolism strategy is developed to prepare “functional vesicle‐like” Se globules via Bacillus subtilis subsp. from selenite in sewage, in which Se nanoparticles are armed with a natural biological protein membrane with rich nitrogen and phosphorus, achieving the eco‐efficient conversion of trash into treasure (selenite, SeO32− → Selenium, Se). The appealing‐design “functional vesicle‐like” Se globules are beneficial to accommodate volume changes of Se in electrochemical reactions, confining polyselenides via chemisorption, and enhancing mechanical strength of electrode by associated bacteria debris, realizing comprehensive utilization of microorganism. By conceptualizing “functional vesicle‐like” Se globules, rather than artificial Se‐host composites, as cathode for lithium–selenium batteries, it exhibits outstanding cycling stability and improved rate performance. This strategy opens the door to design smart electrode materials with unattainable structure that cannot be achieved by traditional approaches, achieving eco‐efficient conversion of pollutants into energy‐storage nanomaterials, which will be a promising research field for interdisciplinary of energy, biology, and environment.
Integration of Wallach's Rule into Intermolecular Charge Transfer: A Visual Strategy for Chiral Purification
Authors: Wang Wei , Gong Jianye , Zhao Jiaqiang , Zhang Hao , Wen Wei , Zhao Zujin , Li Yan Jie , Wang Jianguo , Huang Cheng Zhi , Gao Peng Fei 
Published: July 2024

AbstractExploring the molecular packing and interaction between chiral molecules, no matter single enantiomer or racemates, is important for recognition and resolution of chiral drugs. However, sensitive and non‐destructive analysis methods are lacking. Herein, an intermolecular‐charge transfer (ICT) based spectroscopy is reported to reveal the differences in interaction between the achiral acceptor 1,2,4,5‐tetracyanobenzene (TCNB) and the chiral donors, including S, R, and racemic naproxen (S/R/rac‐NAP). In this process, S‐NAP+TCNB and R‐NAP+TCNB display a narrower band gap attributed to the newly formed ICT state. In contrast, the mixed rac‐NAP and TCNB exhibit almost no significant change due to the strong affinity between the stereoisomers according to the Wallach's rule. Thus, S/R‐NAP can be easily distinguished from rac‐NAP based on significantly different optical behavior. The single crystal analysis, infrared spectroscopy, fluorescence spectroscopy, and theoretical calculation of naproxen confirm the importance of carboxyl for this differentiation in molecular packing and interaction. In addition, the esterification derivatization of naproxen achieves the manipulation of the intermolecular interaction model of racemates from the absolute Wallach's rule to a coexisting form of Wallach's rule and ICT. Further, visualized chiral purification of naproxen by the simple cocrystallization method is achieved through the collaboration of ICT and Wallach's rule.
Amplifying High‐Performance Organic Solar Cells Through Differencing Interactions of Solid Additive with Donor/Acceptor Materials Processed from Non‐Halogenated Solvent
Authors: Haris Muhammad , Ullah Zakir , Lee Seungjin , Ryu Du Hyeon , Ryu Seung Un , Kang Bong Joo , Jeon Nam Joong , Kim Bumjoon J. , Park Taiho , Shin Won Suk , Song Chang Eun 
Published: July 2024

AbstractDeveloping non‐halogenated solvent‐processed organic solar cells (OSCs) demands precise control over the bulk‐heterojunction (BHJ) morphology of the photoactive layer. However, the limited solubility of halogen‐free solvents to photoactive materials hinders microstructure morphology fine‐tuning for boosting photovoltaic performance. This study not only examines the debated intermolecular interactions between the DBrDIB solid additive and photoactive materials but also analyzes the substantial influence of volatile solid additive on the BHJ morphological properties. The DBrDIB effectively restricts the excessive aggregation of Y6‐BO and regulates the phase separation, which is attributed to strong intermolecular interactions with Y6‐BO and rapid quenching during morphology formation. It then achieves a well‐mixed D/A phase with favorable domain size, resulting in a balanced aggregation and dispersion of D/A, ultimately leading to markedly enhanced charge transfer and transport as well as suppressed charge recombination. The transformative use of the o‐xylene/DBrDIB solvent system propels PM6:Y6‐BO and PM6:Y6‐HU OSCs to impressive efficiencies of 17.9% and 19.1%, respectively, outperforming those of the control devices. These findings provide crucial insights into theoretical and experimental areas, offering actionable guidelines for designing high‐performance OSCs processed from halogen‐free solvent.
Cretaceous and Paleocene fossils reveal an extinct higher clade within Cornales, the dogwood order
Authors: Nguyen Austin T. , Atkinson Brian A. 
Published: July 2024

AbstractPremiseCharacterization and phylogenetic integration of fossil angiosperms with uncertain affinities is relatively limited, which may obscure the diversity of extinct higher taxa in the flowering plant tree of life. The order Cornales contains a diversity of extinct taxa with uncertain familial affinities that make it an ideal group for studying turnover in angiosperms. Here, we describe a new extinct genus of Cornales unassignable to an extant family and conduct a series of phylogenetic analyses to reconstruct relationships of fossils across the order.MethodsTwo permineralized endocarps were collected from the Cedar District Formation (Campanian, 82–80 Ma) of Sucia Island, State of Washington, United States. Fossils were sectioned with the cellulose acetate peel technique and incorporated into a morphological dataset. To assess the utility of this dataset to accurately place taxa in their respective clades, we used a series of phylogenetic pseudofossilization analyses. We then conducted a total‐evidence analysis and a scaffold‐based approach to determine relationships of fossils.ResultsBased on their unique combination of characters, the fossils represent a new genus, Fenestracarpa washingtonensis gen. nov. et sp. nov. Pseudofossilization analyses indicate that our morphological dataset can be used to accurately recover taxa at the major clade to family level, generally with moderate to high support. The total‐evidence and scaffold‐based analyses recovered Fenestracarpa and other fossil genera in an entirely extinct clade within Cornales.ConclusionsOur findings increase the reported diversity of extinct Cornales and indicate that the order's initial radiation likely included the divergence of an extinct higher clade that endured the end‐Cretaceous Mass extinction but perished during the Cenozoic.
V‐Y advancement flap for the repair of localized cutaneous defects following nasal closure in severe hereditary hemorrhagic telangiectasia
Authors: Jama Guled M. , Gane Simon 
Published: July 2024

Key points
In patients with severe refractory epistaxis due to hereditary hemorrhagic telangiectasia, the most effective results are achieved by surgical closure of the nares to permanently prevent nasal airflow.
Flap failure and dehiscence can occur and result in fistula formation and clinical relapse.
We describe the utility of a V‐Y advancement flap in repairing localized cutaneous defects in patients who have previously undergone nasal closure for severe HHT.
Prospects and challenges in using neuronal extracellular vesicles in biomarker research
Authors: Rocha Debora A. S. , Santos Luis E. , Da Fonseca Pedro B. , De Felice Fernanda G. 
Published: July 2024

AbstractExtracellular vesicles (EVs) hold promise as a source of disease biomarkers. The diverse molecular cargo of EVs can potentially indicate the status of their tissue of origin, even against the complex background of whole plasma. The main tools currently available for assessing biomarkers of brain health include brain imaging and analysis of the cerebrospinal fluid of patients. Given the costs and difficulties associated with these methods, isolation of EVs of neuronal origin (NEVs) from the blood is an attractive approach to identify brain‐specific biomarkers. This perspective describes current key challenges in EV‐ and NEV‐based biomarker research. These include the relative low abundance of EVs, the lack of validated isolation methods, and the difficult search for an adequate target for immunocapturing NEVs. We discuss that these challenges must be addressed before NEVs can fulfill their potential for biomarker research.Highlights
NEVs are promising sources of biomarkers for brain disorders.
Immunocapturing NEVs from complex biofluids presents several challenges.
The choice of surface target for capture will determine NEV yield.
Contamination by non‐EV sources is relevant for biomarkers at low concentrations.
A Chemoselective Enrichment Strategy for In‐Depth Coverage of the Methyllysine Proteome
Authors: Yan Lufeng , Zheng Manqian , Fan Mingzhu , Yao Rui , Zou Kun , Feng Shan , Wu Mingxuan 
Published: July 2024

AbstractProteomics is a powerful method to comprehensively understand cellular posttranslational modifications (PTMs). Owing to low abundance, tryptic peptides with PTMs are usually enriched for enhanced coverage by liquid chromatography‐mass spectrometry/mass spectrometry (LC–MS/MS). Affinity chromatography for phosphoproteomes by metal‐oxide and pan‐specific antibodies for lysine acetylome allow identification of tens of thousands of modification sites. Lysine methylation is a significant PTM; however, only hundreds of methylation sites were identified by available approaches. Herein we report an aryl diazonium based chemoselective strategy that enables enrichment of monomethyllysine (Kme1) peptides through covalent bonds with extraordinary sensitivity. We identified more than 10000 Kme1 peptides from diverse cell lines and mouse tissues, which implied a wide lysine methylation impact on cellular processes. Furthermore, we found a significant amount of methyl marks that were not S‐adenosyl methionine (SAM)‐dependent by isotope labeling experiments.
Light‐Activated Nanocatalyst for Precise In‐Situ Antimicrobial Synthesis via Photoredox‐Catalytic Click Reaction
Authors: Zhao Minyang , Cao Lei , Bai Qingqing , Lu Yaru , Li Bowen , Wu Wenbo , Ye Jinzhou , Chen Xinhan , Wang Zhihong , Liu Bin , Mao Duo 
Published: July 2024

AbstractThe excessive and prolonged use of antibiotics contributes to the emergence of drug‐resistant S. aureus strains and potential dysbacteriosis‐related diseases, necessitating the exploration of alternative therapeutic approaches. Herein, we present a light‐activated nanocatalyst for synthesizing in situ antimicrobials through photoredox‐catalytic click reaction, achieving precise, site‐directed elimination of S. aureus skin infections. Methylene blue (MB), a commercially available photosensitizer, was encapsulated within the CuII‐based metal–organic framework, MOF‐199, and further enveloped with Pluronic F‐127 to create the light‐responsive nanocatalyst MB@PMOF. Upon exposure to red light, MB participates in a photoredox‐catalytic cycle, driven by the 1,3,5‐benzenetricarboxylic carboxylate salts (BTC−) ligand presented in the structure of MOF‐199. This light‐activated MB then catalyzes the reduction of CuII to CuI through a single‐electron transfer (SET) process, efficiently initiating the click reaction to form active antimicrobial agents under physiological conditions. Both in vitro and in vivo results demonstrated the effectiveness of MB@PMOF‐catalyzed drug synthesis in inhibiting S. aureus, including their methicillin‐resistant strains, thereby accelerating skin healing in severe bacterial infections. This study introduces a novel design paradigm for controlled, on‐site drug synthesis, offering a promising alternative to realize precise treatment of bacterial infections without undesirable side effects.
Temperature‐Responsive Formation Cycling Enabling LiF‐Rich Cathode‐Electrolyte Interphase
Authors: Hong Luxi , Zhang Yi , Mei Pan , Ai Bing , Zhang Yuan , Zhou Chenhuan , Bao Xiaoguang , Zhang Wei 
Published: July 2024

AbstractFormation of LiF‐rich cathode‐electrolyte interphase is highly desirable for wide‐temperature battery, but its application is hindered by the unwanted side reactions associated with conventional method of introducing fluorinated additives. Here, we developed an additive‐free strategy to produce LiF‐rich cathode electrolyte interphase (CEI) by low‐temperature formation cycling. Using LiNi0.33Mn0.33Co0.33O2 as a model cathode, the atomic ratio of LiF in the CEI formed at −5 °C is about 17.7 %, enhanced by ~550 % compared to CEI formed at 25 °C (2.7 %). The underlying mechanism is uncovered by both experiments and theoretic simulation, indicating that the decomposition of LiPF6 to LiF is transformed into spontaneous and exothermic on positively charged cathode surface and lowering the temperature shift chemical equilibrium towards the formation of LiF‐rich CEI. Superior to conventional fluorinated additives, this approach is free from unwanted side reactions, imparting batteries with both high‐temperature (60 °C) cyclability and low‐temperature rate performance (capacity enhanced by 100 % at 3 C at −20 °C). This low‐temperature formation cycling to construct LiF‐rich CEI is extended to various cathode systems, such as LiNi0.8Mn0.1Co0.1O2, LiCoO2, LiMn2O4, demonstrating the versatility and potential impact of our strategy in advancing the performance and stability of wide‐temperature batteries and beyond.
Structural Basis of Cucurbituril‐Containing Self‐Assembled Supramolecular Chiral Materials
Authors: Xu Yunying , Hao Aiyou , Xing Pengyao 
Published: July 2024

AbstractMacrocycle‐based host–guest complexation offers an intriguing protocol in producing chiroptical materials, while the bulky size and dynamic exchange between hosts and guests hinders the ordered aggregation to afford the long‐range chiral arrangement. It remains great challenges in assembling cucurbit[n]urils (CB[n]s) included complexes to induce supramolecular chirality ascribed to the excellent water solubility and flexible packing. Herein, we unveiled the structural basis on the formation of chiroptical coassemblies from CB[n] (n=6, 7) complexes. Perylene diimides (PDIs) with cationic chiral pendants formed complexes in the aqueous media, which selectively showed chiroptical properties. Chlorination at the bay position, increasing alkyl length of cationic chiral pendants or reducing the number of polyaromatic rings would hinder the chiral aggregation. In a comprehensive manner, CB[6] favors ordered aggregation into one‐dimensional fibrous nanoarchitectures that greatly facilitates the supramolecular chirality. In contrast, CB[7] with larger cavity and water solubility shrinks the ordered arrangement of complexes, reducing the formation possibility of supramolecular chiral nanoarchitectures. This work suggests the great potential of CB[6] in the preparation and manipulation of supramolecular chiral assemblies, shedding light on the macrocycle‐based functional chiroptical materials.
Se‐dopant Modulated Selective Co‐Insertion of H+ and Zn2+ in MnO2 for High‐Capacity and Durable Aqueous Zn‐Ion Batteries
Authors: Ye Jia‐Jia , Li Pei‐Hua , Hou Zhiguo , Zhang Wei , Zhu Wenhui , Jin Song , Ji Hengxing 
Published: July 2024

AbstractMnO2 is commonly used as the cathode material for aqueous zinc‐ion batteries (AZIBs). The strong Coulombic interaction between Zn ions and the MnO2 lattice causes significant lattice distortion and, combined with the Jahn–Teller effect, results in Mn2+ dissolution and structural collapse. While proton intercalation can reduce lattice distortion, it changes the electrolyte pH, producing chemically inert byproducts. These issues greatly affect the reversibility of Zn2+ intercalation/extraction, leading to significant capacity degradation of MnO2. Herein, we propose a novel method to enhance the cycling stability of δ‐MnO2 through selenium doping (Se−MnO2). Our work indicates that varying the selenium doping content can regulate the intercalation ratio of H+ in MnO2, thereby suppressing the formation of ZnMn2O4 by‐products. Se doping mitigates the lattice strain of MnO2 during Zn2+ intercalation/deintercalation by reducing Mn−O octahedral distortion, modifying Mn−O bond length upon Zn2+ insertion, and alleviating Mn dissolution caused by the Jahn–Teller effect. The optimized Se−MnO2 (Se concentration of 0.8 at.%) deposited on carbon nanotube demonstrates a notable capacity of 386 mAh g−1 at 0.1 A g−1, with exceptional long‐term cycle stability, retaining 102 mAh g−1 capacity after 5000 cycles at 3.0 A g−1.
Enhancing Reversibility and Kinetics of Anionic Redox in O3‐NaLi1/3Mn2/3O2 through Controlled P2 Intergrowth
Authors: Yang Yihang , Wang Qing , Hou Jingrong , Liu Jie , Sun Tianyi , Tang Mingxue , Chen Chien‐Te , Kuo Chang‐Yang , Hu Zhiwei , Zheng Tingting , Yan Guochun , Ma Jiwei 
Published: July 2024

AbstractAnionic redox chemistry can surpass theoretical limits of conventional layered oxide cathodes in energy density. A recent model system of sodium‐ion batteries, O3‐NaLi1/3Mn2/3O2, demonstrated full anionic redox capacity but is limited in reversibility and kinetics due to irreversible structural rearrangement and oxygen loss. Solutions to these issues are missing due to the challenging synthesis. Here, we harness the unique structural richness of sodium layered oxides and realize a controlled ratio of P2 structural intergrowth in this model compound with the overall composition maintained. The resulted O3 with 27 % P2 intergrowth structure delivers an excellent initial Coulombic efficiency of 87 %, comparable to the state‐of‐the‐art Li‐rich NMCs. This improvement is attributed to the effective suppression of irreversible oxygen release and structural changes, evidenced by operando Differential Electrochemical Mass Spectroscopy and X‐ray Diffraction. The as‐prepared intergrowth material, based on the environmentally benign Mn, exhibits a reversible capacity of 226 mAh g−1 at C/20 rate with excellent cycling stability stemming from the redox reactions of oxygen and manganese. Our work isolates the role of P2 structural intergrowth and thereby introduces a novel strategy to enhance the reversibility and kinetics of anionic redox reactions in sodium layered cathodes without compromising capacity.
Sterically Controlled Lewis Acid−Base Interaction Toward para‐Selective Borylation of Aromatic Aldimines and Benzylamines
Authors: Guria Saikat , Hassan Mirja Md Mahamudul , Dey Sayan , Singh Krishna Nand , Chattopadhyay Buddhadeb 
Published: July 2024

AbstractSite‐selective C−H bond functionalization of arenes at the para position remains extremely challenging primarily due to its relative inaccessibility from the catalytic site. As a consequence, it is significantly restricted to limited molecular scaffolds. Herein, we report a method for the para‐C−H borylation of aromatic aldimines and benzylamines using commercially available ligands under iridium catalysis. The established method displays excellent para selectivity for variously substituted aromatic aldimines, benzylamines and bioactive molecules. Based on several control experiments, it is proposed that a Lewis acid−base interaction between the nitrogen and boron functionality guides the para selectivity via a steric shield for the aromatic aldimines, where Bpin acts as a transient directing group. However, the steric shield of the in situ generated N−Bpin moiety controlled the overall selectivity for the para borylation of benzylamines.