bluuebunny/crossref_metadata_2025_split huggingface dataset:
Universal Copolymerization of Crosslinked Polyether Electrolytes for All‐Solid‐State Lithium‐Metal Batteries
Authors: Lei Chengjun , Zhou Tiankun , Zhang Mingjie , Liu Tingting , Xu Chen , Wang Rui , He Xin , Liang Xiao 
Published: July 2024

AbstractSolid polymer electrolytes (SPEs) are pivotal in advancing the practical implementation of all‐solid‐state batteries. Poly(1,3‐dioxane) (PDOL)‐based electrolytes have attracted significant attention due to the pseudo‐high conductivity achieved through sophisticated in situ polymerization methods; however, such PDOL‐based electrolytes present challenges of crystallization over time and monomers residual during processing. In this study, integrating LiTFSI and LiDFOB as a universal copolymerization strategy for developing high‐performance PDOL electrolytes with a wide range of epoxy crosslinkers is proposed. It is discovered that this approach leverages the protective effects of TFSI anions on the boron active center and catalyzes polymer chain growth via crosslinking. The homogenously crosslinked (benzene‐centered) PDOL electrolyte exhibits remarkable thermo‐mechanical stability (up to 100 °C), high ion migration number (tLi+ = 0.42), a wide electrochemical window (≈5.0 V vs Li+/Li), and high ionic conductivity (4.5×10−4 S cm−1). Notably, the crosslinked PDOL electrolyte is in the all‐solid‐state with minimal monomer/oligomer residual, exhibiting no crystallization during relaxation, delivering a robust performance in all‐solid‐state lithium metal batteries.
Constructing Gradient Separator to Stabilize Bi‐electrodes Toward High‐Performance Zn Metal Batteries
Authors: Tian Penghui , Gao Yuliang , Huang Shifeng , Cao Yanjiao , Liu Zihan , Huo Yaodong , Li Mengjing , Gu Xiaojun , Wu Limin 
Published: July 2024

AbstractAqueous zinc (Zn) metal batteries have considerable potential as large‐scale energy storage systems. However, cathodic metal ions dissolution and anodic dendrite growth constrain their further development. Here, an ion gradient separator is proposed to stabilize the bi‐electrodes of Zn metal batteries. The results show that the constructed low Zn2+ concentration region in the separator helps the NH4V4O10 (NVO) model cathode to maintain good electrolyte wettability and form a N/ZnS/ZnF2‐rich cathode‐electrolyte interphase (CEI), exhibiting a low vanadium (V) dissolution behavior. Meanwhile, the high Zn2+ concentration region in the separator and the flexible solid electrolyte interphase (SEI) inhibit the dendrite growth and parasitic reactions of the Zn metal anode and further prevent the diffusion of V ions. As a proof‐of‐concept, the NVO||Zn battery with gradient separator can achieve 88.1% capacity retention even after cycling over 800 cycles at 1 A g−1, while the ordinary separator only maintains 14.8%. This work presents an innovative gradient separator strategy for achieving high‐performance Zn metal batteries and sheds light on other rechargeable batteries.
Promises of MOF‐Based and MOF‐Derived Materials for Electrocatalytic CO2 Reduction
Authors: Mamaghani Alireza Haghighat , Liu Jingwei , Zhang Zhen , Gao Rui , Wu Yuxuan , Li Haibo , Feng Ming , Chen Zhongwei 
Published: July 2024

AbstractElectrocatalytic CO2 reduction (ECR) powered by renewable electricity is a promising technology to mitigate carbon emissions and lessen the dependence on fossil fuels toward a carbon‐neutral energy cycle. Metal–organic frameworks (MOFs) and their derivatives, due to their excellent intrinsic activity, have emerged as promising materials for the ECR to high‐demand products. However, challenges such as unsatisfactory energy efficiency, selectivity, and relatively low production rates hinder their industrial scalability. Here, a comprehensive and critical review is presented that summarizes the state‐of‐the‐art progress in MOF‐based and MOF‐derived CO2 electroreduction catalysts from design and functionality perspectives. The fundamentals of CO2 reduction reaction (CO2RR) over heterogeneous catalysts, reaction mechanisms, and key challenges faced by ECR are described first to establish a solid foundation for forthcoming in‐depth analyses. MOF's building blocks, properties, and shortcomings pertinent to ECR including low conductivity and stability, are systematically discussed. Moreover, comprehensive discussions are provided on MOF‐based and MOF‐derived catalysts design, fabrication, characterization, and CO2RR activity to pinpoint the intricate structure‐property‐performance relationship. Finally, promising recommendations are put forward for enhancing MOF electrocatalysts activity, selectivity, and durability. This work may serve as a guideline for developing high‐performance MOF‐related catalysts for CO2RR, benefiting researchers working in this growing and potentially game‐changing area.
Gastrointestinal manifestations in Williams syndrome: A prospective analysis of an adult and pediatric cohort
Authors: Boechler Michael , Fu Yi‐Ping , Raja Neelam , Ruiz‐Escobar Emily , Nimmagadda Likitha , Osgood Sharon , Levin Mark D. , Hadigan Colleen , Kozel Beth A. 
Published: July 2024

AbstractWilliams syndrome (WS) is a multi‐system condition caused by the deletion of 25–27 coding genes on human chromosome 7. Irritability, gastrointestinal (GI) reflux and slow growth are commonly reported in infants with WS, but less data exist regarding GI concerns in older children and adults with the condition. This study evaluates 62 individuals with WS (31 children aged 3–17, and 31 adults aged 18–62) as well as 36 pediatric and adult controls to assess current and historical rates of common GI symptoms. Data were evaluated using a regression model including age, sex, self‐reported race, and diagnosis. Symptoms including food intolerance, reflux, dysphagia, choking/gagging, vomiting, constipation, bloating, diarrhea, hematochezia, rectal prolapse, abdominal pain, and weight loss are more common in those with WS relative to controls. In addition, people with WS utilize more GI medications, specialty care, procedures, and supplemental feeds. Among those with WS, symptoms were present at similar rates in children and adults, except for diverticular disease, which was not noted until adulthood. GI symptoms are frequent in people with WS and serve as a significant source of morbidity.
Structure–function coupling reveals the brain hierarchical structure dysfunction in Alzheimer's disease: A multicenter study
Authors: Sun Yibao , Wang Pan , Zhao Kun , Chen Pindong , Qu Yida , Li Zhuangzhuang , Zhong Suyu , Zhou Bo , Lu Jie , Zhang Xi , Wang Dawei , Han Ying , Yao Hongxiang , Liu Yong 
Published: July 2024

AbstractBACKGROUNDAlzheimer's disease (AD) is a neurodegenerative condition characterized by cognitive decline. To date, the specific dysfunction in the brain's hierarchical structure in AD remains unclear.METHODSWe introduced the structural decoupling index (SDI), based on a multi‐site data set comprising functional and diffusion‐weighted magnetic resonance imaging data from 793 subjects, to assess their brain hierarchy.RESULTSCompared to normal controls (NCs), individuals with AD exhibited increased SDI within the posterior superior temporal sulcus, insular gyrus, precuneus, hippocampus, amygdala, postcentral gyrus, and cingulate gyrus; meanwhile, the patients with AD demonstrated decreased SDI in the frontal lobe. The SDI in those regions also showed a significant correlation with cognitive ability. Moreover, the SDI was a robust AD neuroimaging biomarker capable of accurately distinguishing diagnostic status (area under the curve [AUC] = 0.86).DISCUSSIONOur findings revealed the dysfunction of the brain's hierarchical structure in AD. Furthermore, the SDI could serve as a promising neuroimaging biomarker for AD.Highlights
This study utilized multi‐center, multi‐modal data from East Asian populations.
We found an increased spatial gradient of the structure decoupling index (SDI) from sensory–motor to higher‐order cognitive regions.
Changes in SDI are associated with energy metabolism and mitochondria.
SDI can identify Alzheimer's disease (AD) and further uncover the disease mechanisms of AD.
Foreclosure, memory decline, and dementia probability: A longitudinal cohort study
Authors: Kim Min Hee , Schwartz Gabriel L. 
Published: July 2024

AbstractINTRODUCTIONHousing insecurity is rising among older adults; health researchers know little about how this may impact their cognitive health. We investigated links between foreclosure and older adults’ memory and probability of dementia.METHODSUsing the Health and Retirement Study (2008 to 2018), we fit mixed models comparing the memory and dementia probability scores of 249 older adults who experienced foreclosure (treated) with 15,645 who did not. Baseline covariates included sociodemographics and health. Models were stratified by age group.RESULTSForeclosure was associated with faster memory decline among middle‐aged (50 to 64) older adults (−0.007 standard deviations/year, 95% confidence interval: −0.13, −0.001). Compared to average memory decline among middle‐aged older adults who were stably housed, foreclosure equated to 3.7 additional years of aging over 10 years. Among those 65+, differences between those who were and were not foreclosed upon were short‐lived and less clear, potentially driven by depletion‐of‐susceptibles bias.DISCUSSIONForeclosure may endanger older adults’ memory.Highlights
Housing instability is a key determinant of cognitive aging.
We examined foreclosure and levels and changes in memory and dementia probability scores in the US older adult population.
Foreclosure was associated with faster memory decline among middle‐aged (50 to 64) older adults, equivalent to 3.7 additional years of cognitive aging over 10 years.
Foreclosure yielded sharp memory declines and increases in dementia probability among older adults 65 and above.
Foreclosure imposes a greater risk for older adults’ cognitive decline.
Eine Photocrosslinker Sonde zur Erfassung der Substrate der caseinolytischen Protease P
Authors: Gronauer Thomas F. , Eck Laura K. , Ludwig Christina , Sieber Stephan A. 
Published: July 2024

AbstractProteinhomöostase in Bakterien wird durch Proteasen wie der tetradekameren caseinolytischen Protease P (ClpP) reguliert. Obwohl Substrate von ClpP in genetisch veränderten Zellen bereits erfolgreich erfasst wurden, fehlen bislang Methoden, um diese in nativen Zellen zu identifizieren. In dieser Publikation beschreiben wir eine in situ Trapping‐Methode, die trifunktionale Sonden nutzt, die an das aktive Zentrum von ClpP binden und benachbarte Substrate mit Hilfe eines Photocrosslinkers binden. Nach Anreicherung des Komplexes durch das Alkin erfolgt die Substratanalyse durch Massenspektrometrie (MS). Wir zeigen, dass unsere beiden Traps substoichiometrisch an ClpP binden, die Proteaseaktivität von ClpP nicht inhibieren, Selektivität für ClpP in Staphylococcus aureus Zellen aufweisen und zahlreiche bekannte und neue Substrate identifizieren konnten. Die exemplarische Validierung dieser Substrate mittels eines gezielten Proteomik‐Ansatzes bestätigte die Zuverlässigkeit dieser Methode. Zusammenfassend bieten wir eine neuartige chemische Plattform zur Identifizierung von Serinprotease‐Substraten in nativen Zellen.
Programmable Chemical Evolution with Natural/Non‐Natural Building Blocks
Authors: Liu Ping , Jannatul Refeya , Chen Juan , Hou Lihua , Gao Mingjuan , Wang Pengjie , Wang Lulu , Jin Dekui , Chen Hao , Liu Rong , Wang Ran , Zhu Yinhua , Fang Bing , Jia Lirong , Sun Yanan , Zhang Yixin , Ren Fazheng , Lin Weilin 
Published: July 2024

AbstractNon‐natural building blocks (BBs) present a vast reservoir of chemical diversity for molecular recognition and drug discovery. However, leveraging evolutionary principles to efficiently generate bioactive molecules with a larger number of diverse BBs poses challenges within current laboratory evolution systems. Here, we introduce programmable chemical evolution (PCEvo) by integrating chemoinformatic classification and high‐throughput array synthesis/screening. PCEvo initiates evolution by constructing a diversely combinatorial library to create ancestral molecules, streamlines the molecular evolution process and identifies high‐affinity binders within 2–4 cycles. By employing PCEvo with 108 BBs and exploring >1017 chemical space, we identify bicyclic peptidomimetic binders against targets SAR‐CoV‐2 RBD and Claudin18.2, achieving nanomolar affinity. Remarkably, Claudin18.2 binders selectively stain gastric adenocarcinoma cell lines and patient samples. PCEvo achieves expedited evolution in a few rounds, marking a significant advance in utilizing non‐natural building blocks for rapid chemical evolution applicable to targets with or without prior structural information and ligand preference.
Heteroatoms‐Stabilized Single Palladium Atoms on Amorphous Zeolites: Breaking the Tradeoff between Catalytic Activity and Selectivity for Alkyne Semihydrogenation
Authors: Bai Risheng , He Guangyuan , Li Junyan , Li Lin , Zhang Tianjun , Wang Xingxing , Zhang Wei , Zou Yongcun , Zhang Jichao , Mei Donghai , Corma Avelino , Yu Jihong 
Published: July 2024

AbstractAs a fundamental industrial catalytic process, the semihydrogenation of alkynes presents a challenge in striking a balance between activity and selectivity due to the issue of over‐hydrogenation. Herein, we develop an efficient catalytic system based on single‐atom Pd catalysts supported on boron‐containing amorphous zeolites (Pd/AZ−B), achieving the tradeoff breaking between the activity and selectivity for the selective hydrogenation of alkynes. Advanced characterizations and theoretical density functional theory calculations confirm that the incorporated B atoms in the Pd/AZ−B can not only alter the geometric and electronic properties of Pd atoms by controlling the electron migration from Pd but also mitigate the interaction between alkene and the catalyst supports. This boosts the exceptional catalytic efficacy in the semihydrogenation of phenylacetylene to styrene under mild conditions (298 K, 2 bar H2), achieving a recorded turnover frequency (TOF) value of 24198 h−1 and demonstrating 95 % selectivity to styrene at full conversion of phenylacetylene. By comparison, the heteroatom‐free amorphous zeolite‐anchored Pd nanoparticles and the commercial Lindlar catalyst have styrene selectivities of 73 % and 15 %, respectively, under identical reaction conditions. This work establishes a solid foundation for developing highly active and selective hydrogenation catalysts by controllably optimizing their electronic and steric properties.
Recyclable Polythioesters and Poly(thioester‐co‐peptoid)s via Ring‐Opening Cascade Polymerization of Amino Acid N‐Carboxyanhydrides
Authors: Wang Shuo , Tian Zi‐You , Lu Hua 
Published: July 2024

AbstractPolythioesters (PTEs) are emerging sustainable polymers for their degradability and recyclability. However, low polymerizability of monomers and extensive side reactions often hampered the polymerization process. Moreover, copolymers containing both thioester and other types of functional groups in the backbone are highly desirable but rarely accomplished owing to several synthetic challenges. Here, we report the ring‐opening cascade polymerization (ROCAP) of N‐(2‐(acetylthio)ethyl)‐glycine N‐carboxyanhydrides (TE‐NCA) to afford recyclable PTEs and unprecedented poly(thioester‐co‐peptoid)s (P(TE‐co‐PP)s) in a controlled manner. By developing appropriated carboxylic acid‐tertiary amine dual catalysts, intramolecular S‐to‐N acyl shift is coupled into the ROCAP process of TE‐NCA to yield products with dispersity below 1.10, molecular weight (Mn) up to 84.5 kDa, and precisely controlled ratio of thioester to peptoids. Random copolymerization of sarcosine NCA (Sar‐NCA) and TE‐NCA gives thioester‐embedded polysarcosine with facile backbone degradation while maintaining the water solubility. This work represents a paradigm shift for the ROP of NCAs, enriches the realm of cascade polymerizations, and provides a powerful synthetic approach to functional PTEs and P(TE‐co‐PP)s that are otherwise difficult or impossible to make.
Confinement Synthesis of Atomic Copper‐Anchored Polymeric Carbon Nitride in Crystalline UiO‐66‐NH2 for High‐Performance CO2‐to‐CH3OH Photocatalysis
Authors: Liu Xingbing , Zhu Changyan , Li Mengying , Xing Hongzhu , Zhu Siyang , Liu Xin , Zhu Guangshan 
Published: July 2024

AbstractPhotocatalytic CO2 reduction to value‐added fuels displays an attractive scenario to enhance energy supply and reduce global warming. We report herein the confinement synthesis of polymeric carbon nitride (PCN) incorporating with Cu single atoms (CuSAs) inside the crystalline UiO‐66‐NH2, which combines the merits of heterojunction photocatalysis and single‐atom catalysis (SAC) to achieve high‐performance CO2‐to‐CH3OH conversion. A series of spectral studies displays the formation of CuSAs@PCN inside the crystalline UiO‐66‐NH2. Remarkably, the ternary composite shows an excellent photocatalytic turnover frequency of 4.15 mmol ⋅ h−1 ⋅ g−1 for CO2‐to‐CH3OH conversion. Theoretical and experimental studies demonstrate the doping of CuSAs, as well as the formation of type‐II heterojunction, are causal factors to achieve CH3OH generation. The study provides new insights designing high‐performance photocatalyst for CO2 conversion to fuels at atomic scale.
Copper Intercalation Induces Amorphization of 2D Cu/WO3 for Room‐Temperature Ferromagnetism
Authors: Zhao Duanduan , Gao Bo , An Guangyu , Xu Song , Tian Qingyong , Xu Qun 
Published: July 2024

AbstractFerromagnetism in the two‐dimensional limit has become an intriguing topic for exploring new physical phenomena and potential applications. To induce ferromagnetism in 2D materials, intercalation has been proposed to be an effective strategy, which could introduce lattice distortion and unpaired spin into the material to modulate the magnetocrystalline anisotropy and magnetic exchange interactions. To strengthen the understanding of the magnetic origin of 2D material, Cu was introduced into a 2D WO3 through chemical intercalation in this work (2D Cu/WO3). In contrast to the diamagnetic nature of Cu and WO3, room‐temperature ferromagnetism was characterized for 2D Cu/WO3. Experimental and theoretical results attribute the ferromagnetism to the bound magnetic polaron in 2D Cu/WO3, which is consist of unpaired spins from W5+/W4+ with localized carriers from oxygen vacancies. Overall, this work provides a novel approach to introduce ferromagnetism into diamagnetic WO3, which could be applied for a wider scope of 2D materials.
Mechanistic Insights into Curvature Formation in Synthetic Vesicles
Authors: Cook Alexander B. 
Published: July 2024

AbstractThe mimicking of natural lipid bilayers with synthetic amphiphilic systems is of great interest to researchers, as insights could lead to better understanding of the complexities of cell membranes, as well as new materials and healthcare technologies. Recapitulating natural lipid asymmetry across bilayer membranes has important implications for curvature in cell, vesicle, and organelle morphologies, but has been challenging to achieve with synthetic lipid combinations or standard amphiphilic block copolymers. In a recent article, Elizebath et al. report the synthesis of a new type of synthetic amphiphile able to induce asymmetry in an artificial bilayer membrane dynamically. The molecules were designed around an extended π‐conjugated hydrophobic core with tertiary amine‐terminated oxyalkylene side chains. Protonation of the tertiary amines on the bilayer exterior leads to curvature induction, bilayer fission, and vesicle formation as monitored by time‐resolved spectroscopy techniques and microscopy. The results were further validated with density functional theory (DFT) calculations. The delicate balance between different molecular scale interactions in the supramolecular structures led to the dynamic transformation of the bilayer membranes. Insights described could be used to advance the assembly of hierarchical life‐like materials.
The effects of seasonal climate change on the safflower genotypes productivity under Central Anatolian conditions
Authors: Koç Hasan 
Published: July 2024

AbstractThis study aimed to investigate the effect of seasonal climate change on safflower genotypes productivity in Central Anatolian conditions during 2021 and 2022. The research focused on seed yield, oil content, and oil yield, considering variations in growing degree days (GDD) at different growth stages. In both years, seed yield was significantly affected by lack of rainfall. In 2021, safflower genotypes had an average seed yield of 1540 kg ha−1, while in 2022, it increased to 2390 kg ha−1 due to higher rainfall during critical growth stages. Different genotypes showed different performances in seed yield each year, highlighting the importance of selecting drought‐tolerant genotypes for breeding programmes. Oil content also showed significant variations between genotypes and years. Drought stress during flowering and seed filling periods generally led to a decrease in safflower oil content. However, in 2021, despite drought during the seedling stage, there was an increase in average oil content, possibly due to compensatory mechanisms related to reduced seed yield and dry matter content. In addition, the study looked at GDD values at different growth stages and found considerable variation among genotypes in GDD accumulation. Genotypes with higher GDD accumulation tended to have higher seed and oil yields, indicating better stress tolerance. Conversely, early maturing genotypes with lower GDD levels were better suited for regions with lower average temperatures. The results highlight the importance of considering both rainfall and temperature factors when selecting safflower genotypes for specific regions. In conclusion, the study highlights the impact of seasonal climate change on safflower productivity and the need to develop new safflower varieties capable of adapting to the predicted hotter and drier conditions due to climate change.
Characterization of maltose‐binding protein–fused heparinases with enhanced thermostability by application of rigid and flexible linkers
Authors: Wu Xi , Yun Zhenyu , Su Nan , Zhao Lin , Zhang Hui , Zhang Mengyan , Wu Qi , Zhang Chong , Xing Xin‐Hui 
Published: July 2024

AbstractHeparinases, including heparinases I–III (HepI, HepII, and HepIII, respectively), are important tools for producing low‐molecular‐weight heparin, an improved anticoagulant. The poor thermostability of heparinases significantly hinders their industrial and laboratory applications. To improve the thermostability of heparinases, we applied a rigid linker (EAAAK)5 (R) and a flexible linker (GGGGS)5 (F) to fuse maltose‐binding protein (MBP) and HepI, HepII, and HepIII from Pedobacter heparinus, replacing the original linker from the plasmid pMAL‐c2X. Compared with their parental fusion protein, MBP‐fused HepIs, HepIIs, and HepIIIs with linkers (EAAAK)5 or (GGGGS)5 all displayed enhanced thermostability (half‐lives at 30°C: 242%–464%). MBP‐fused HepIs and HepIIs exhibited higher specific activity (127%–324%), whereas MBP‐fused HepIIIs displayed activity similar to that of their parental fusion protein. Kinetics analysis revealed that MBP‐fused HepIIs showed a significantly decreased affinity toward heparin with increased Km values (397%–480%) after the linker replacement, whereas the substrate affinity did not change significantly for MBP‐fused HepIs and HepIIIs. Furthermore, it preliminarily appeared that the depolymerization mechanism of these fusion proteins may not change after linker replacement. These findings suggest the superior enzymatic properties of MBP‐fused heparinases with suitable linker designs and their potential for the bioproduction of low‐molecular‐weight heparin.