bluuebunny/crossref_metadata_2025_split huggingface dataset:
Hydrophilic‐Zincophobic Separator Enabling by Crystal Structure Regulation toward Stabilized Zn Metal Anode
Authors: Lv Shujun , Su Mingyu , Li Zhuo , Mao Yiyang , Yin Jinling , cao Dianxue , Wang Guiling , Yi Jin , Ning Fanghua , Zhu Kai 
Published: March 2024

AbstractAqueous zinc‐ion batteries (ZIBs) hold significant promise for large‐scale energy storage. While considerable strides have been made in modifying separators, the challenge of developing dendrite‐free, corrosion‐resistant, and cost‐effective separators for achieving extended cycling performance of Zn anodes persists. In light of this, a TiO2 coating separator to mitigate interfacial corrosion and passivation reactions, thereby facilitating high‐performance ZIBs is designed. This study delves into the influence of the loading amount and crystal phase of the TiO2 coating layers on separator modification. Zn symmetric cells employing the anatase TiO2‐modified glass fiber (A‐TiO2@GF) separator demonstrate superior Zn2+ ion transport kinetics in a mild ZnSO4 electrolyte, ensuring sustained long‐term stability and uniform Zn deposition. Furthermore, the reduced hydrogen evolution reaction (HER) activity of A‐TiO2 coatings curbs H+ ion migration, minimizing interfacial corrosion and HER. Consequently, the assembled Zn||CaV8O20 zinc‐ion full cells demonstrate outstanding long‐term durability and impressive specific capacity, boasting a discharge capacity of 142 mAh g−1 after 1000 cycles. This work introduces a straightforward interface engineering strategy for creating efficient separators in zinc‐ion batteries, promoting uniform Zn deposition.
Time‐Dependent Information Encryption in Liquid Crystalline Polymer with Programmable Glass Transition Temperature
Authors: Zhang Jianying , Song Chenjie , Zhang Shuoning , Qin Shengyu , Ren Yunxiao , Zhang Lanying , Xiao Jiumei , Li Kexuan , Hu Wei , Yang Huai 
Published: March 2024

AbstractTime‐dependent dynamic information encryption technology is a promising approach to enhancing the security and complexity of information transmission. Herein, a time‐dependent information encryption model from a liquid crystalline polymer (LCP) film with a programmable glass transition temperature (Tg) and gradually adjustable fluorescence is demonstrated. The programmable Tg is achieved by adjusting the degree of order of the LC molecules via a configuration interconversion of spiropyran‐based materials (SPBMs), which can convert between a V‐shaped colorless spiro (SP) and a rodlike dark‐colored merocyanine (MC) form. An LCP film obtained by visible light polymerization exhibits a lower Tg than UV light, because the SPBM molecules keep different configurations in the two films. By adjusting the ratio of two isomerization forms of SPBM molecules during the polymerization process, the Tg values of LCP films can change from 11.6 °C to 31.1 °C. Based on the isomerization rate of SPBM in the LCP films with different Tg, time‐dependent information encryption is successfully achieved.
Copper(I)‐Arsine Clusters with a Near‐Unity Phosphorescence Quantum Yield for X‐Ray Scintillation and LED Applications
Authors: Demyanov Yan V. , Ma Zihao , Jia Zhenglin , Rakhmanova Marianna I. , Carignan Gia M. , Bagryanskaya Irina Yu. , Sulyaeva Veronika S. , Globa Anastasiya A. , Brel Valery K. , Meng Lingqiang , Meng Hong , Lin Qianqian , Li Jing , Artemev Alexander V. 
Published: March 2024

AbstractRare‐earth element‐free materials that exhibit strong room temperature phosphorescence (RTP) and X‐ray scintillation properties are gaining global interest incessantly in the recent years. This work reports a series of easily synthesizable cubane Cu4I4‐triarsenic clusters [Cu4I4(R3As)3L] (L = none or nitrile), that exhibit a strong yellow‐green RTP with quantum efficiencies up to 100% and short decay times (4.4–4.9 µs). The title cluster complexes display X‐ray scintillation properties with a record ultralow detection limit (18.1 nGy s−1) and a perfectly linear dose rate response within a remarkably wide dose rate window (0–640 µGyair s−1). The cluster [Cu4I4(Ph3As)3] is highlighted as an efficient phosphor for UV‐pumped white and yellow LED devices, demonstrating an excellent white spectrum with a CIE index of (0.32,0.33) and bright yellow emission, respectively. These results may stimulate the future efforts in designing highly efficient arsenic‐based RTP materials and enriching the Cu4I4 cluster family.
Review on high‐performance polymeric bipolar membrane design and novel electrochemical applications
Authors: Yan Junying , Yu Weisheng , Wang Zihao , Wu Liang , Wang Yaoming , Xu Tongwen 
Published: March 2024

AbstractElectrochemical devices allow the conversion and storage of renewable energy into high‐value chemicals to mitigate carbon emissions, such as hydrogen production by water electrolysis, carbon dioxide reduction, and the electrochemical synthesis of ammonia. Independent regulation of the electrode pH environment is essential for optimizing the electrode reaction kinetics and enriching the catalyst species. The in situ water dissociation (WD, ) in bipolar membranes (BPMs) offers the possibility of realizing this pH adjustment. Here, the design principles of high‐performance polymeric BPMs in electrochemical device applications are presented by analyzing and connecting WD principles and current–voltage curves. The structure–transport property relationships and membrane durability, including the chemical and mechanical stability of the anion‐ and cation‐exchange layers as well as the integrality of the interfacial junction, are systematically discussed. The advantages of BPMs in new electrochemical devices and major challenges to break through are also highlighted. The improved ion and water transport in the membrane layer and the minimized WD overpotential and ohmic loss at high current densities are expected to facilitate the promotion of BPMs from conventional chemical production to novel electrochemical applications.
From small to large—The application of in situ polymerization within tumor cells
Authors: Jia Mingjie , Liu Yonghang , Wei Peng , Yi Tao 
Published: March 2024

AbstractThe “laboratory” of cells has the capacity to polymerize monosaccharides, amino acids, and nucleotides. Tumor cells, characterized by the overexpression of multiple enzymes and existing in a slightly acidic and highly redox‐potent environment, have attracted the attention of chemists aiming to transfer chemical reactions from the traditional laboratory flask to this “cellular laboratory”. Polymers, resulting from the repetitive linkage of monomers, have garnered extensive utility in the biomedical field due to their diverse structural and physicochemical properties. When the polymerization reaction proceeds in situ within the tumor cells, this in situ transformation from small‐to‐large combines the rapid uptake of monomeric molecules with the strong retention ability of polymers, exerting a profound impact on drug delivery within tumors. Moreover, it shows promising applications in the regulation of cell behavior, imaging, therapy, and theranostics. Given the diverse functions of in situ polymerization in relation to tumor cells, this review focuses on a comprehensive examination of various strategies for in situ polymerization within tumor cells, categorizing these strategies based on the formation mechanisms of polymers. The applications in this domain concerning in situ polymerization within tumor cells are also explored. Moreover, a discussion of specific limitations in current research and insights into potential future directions from the authors' perspective are provided.
Unraveling a history of overlap: A phenotypic comparison of RBCK1‐related disease and glycogen storage disease type IV
Authors: Crane Haley M. , Asher Stephanie , Conway Laura , Drivas Theodore G. , Kallish Staci 
Published: March 2024

AbstractRBCK1‐related disease is a rare, multisystemic disorder for which our current understanding of the natural history is limited. A number of individuals initially carried clinical diagnoses of glycogen storage disease IV (GSD IV), but were later found to harbor RBCK1 pathogenic variants, demonstrating challenges of correctly diagnosing RBCK1‐related disease. This study carried out a phenotypic comparison between RBCK1‐related disease and GSD IV to identify features that clinically differentiate these diagnoses. Literature review and retrospective chart review identified 25 individuals with RBCK1‐related disease and 36 with the neuromuscular subtype of GSD IV. Clinical features were evaluated to assess for statistically significant differences between the conditions. At a system level, any cardiac, autoinflammation, immunodeficiency, growth, or dermatologic involvement were suggestive of RBCK1, whereas any respiratory involvement suggested GSD IV. Several features warrant further exploration as predictors of RBCK1, such as generalized weakness, heart transplant, and recurrent infections, among others. Distinguishing RBCK1‐related disease will facilitate correct diagnoses and pave the way for accurately identifying affected individuals, as well as for developing management recommendations, treatment, and an enhanced understanding of the natural history. This knowledge may also inform which individuals thought to have GSD IV should undergo reevaluation for RBCK1.
Linear enamel hypoplasia inHomonaledireappraised in light of new Retzius periodicities
Authors: Skinner Mark Fretson , Delezene Lucas Kyle , Skinner Matthew M. , Mahoney Patrick 
Published: March 2024

AbstractObjectivesAmong low‐latitude apes, developmental defects of enamel often recur twice yearly, linkable to environmental cycles. Surprisingly, teeth ofHomonaledifrom Rising Star in South Africa (241–335 kya), a higher latitude site with today a single rainy season, also exhibit bimodally distributed hypoplastic enamel defects, but with uncertain timing and etiology. Newly determined Retzius periodicities for enamel formation in this taxon enable a reconstruction of the temporal patterning of childhood stress.MethodsUsing high resolution casts of 31 isolated anterior teeth fromH.naledi, 82 enamel defects (linear enamel hypoplasia [LEH]) were identified. Seventeen teeth are assigned to three individuals. Perikymata in the occlusal wall of enamel furrows and between the onsets of successive LEH were visualized with scanning electron microscopy and counted. Defects were measured with an optical scanner. Conversion of perikymata counts to estimates of LEH duration and inter‐LEH interval draws upon Retzius periodicities of 9 and 11 days.ResultsAnterior teeth record more than a year of developmental distress, expressed as two asymmetric intervals centered on 4.5 and 7.5 months bounded by three LEH. Durations, also, show bimodal distributions, lasting 3 or 12 weeks. Short duration LEH are more severe than long duration. Relative incisor/canine rates of formation are indistinguishable from modern humans.DiscussionWe invoke a disease and dearth model, with short episodes of distress reflecting onset of disease in young infants, lasting about 3 weeks, followed by a season of undernutrition, possibly intensified by secondary plant compounds, spanning about 12 weeks, inferably coincident with austral winter.
Fairness perceptions of income‐based educational inequality: The impact of social class and ideological orientations
Authors: Lee Jung‐Sook , Stacey Meghan 
Published: March 2024

AbstractIncome‐based educational inequality is a global issue. In Australia, schools in the relatively large private sector charge a range of fees, with public schools also exhibiting considerable income differences. Using a nationally representative sample in the Australian Survey of Social Attitudes, we examined the public's fairness perceptions of income‐based educational inequality and how their fairness perceptions are related to self‐interest (particularly regarding social class) and ideological orientations. We found that people hold diverse views about the fairness of income‐based educational inequality and that the number of people who perceived it as unfair was almost double the number of those who perceived it as fair. Respondents categorised as upper/upper‐middle‐class were, however, more likely to perceive income‐based educational inequality as fair, while agreement with government responsibility for economic well‐being was associated with a negative view of income‐based educational inequality. Implications of these findings for the promotion of socially just and equitable education are discussed.
Chloride and Hydride Transfer as Keys to Catalytic Upcycling of Polyethylene into Liquid Alkanes
Authors: Zhang Wei , Yao Hai , Khare Rachit , Zhang Peiran , Yang Boda , Hu Wenda , Ray Debmalya , Hu Jianzhi , Camaioni Donald M. , Wang Huamin , Kim Sungmin , Lee Mal‐Soon , Sarazen Michele L. , Chen Jingguang G. , Lercher Johannes A. 
Published: March 2024

AbstractTransforming polyolefin waste into liquid alkanes through tandem cracking‐alkylation reactions catalyzed by Lewis‐acid chlorides offers an efficient route for single‐step plastic upcycling. Lewis acids in dichloromethane establish a polar environment that stabilizes carbenium ion intermediates and catalyzes hydride transfer, enabling breaking of polyethylene C−C bonds and forming C−C bonds in alkylation. Here, we show that efficient and selective deconstruction of low‐density polyethylene (LDPE) to liquid alkanes is achieved with anhydrous aluminum chloride (AlCl3) and gallium chloride (GaCl3). Already at 60 °C, complete LDPE conversion was achieved, while maintaining the selectivity for gasoline‐range liquid alkanes over 70 %. AlCl3 showed an exceptional conversion rate of 5000
, surpassing other Lewis acid catalysts by two orders of magnitude. Through kinetic and mechanistic studies, we show that the rates of LDPE conversion do not correlate directly with the intrinsic strength of the Lewis acids or steric constraints that may limit the polymer to access the Lewis acid sites. Instead, the rates for the tandem processes of cracking and alkylation are primarily governed by the rates of initiation of carbenium ions and the subsequent intermolecular hydride transfer. Both jointly control the relative rates of cracking and alkylation, thereby determining the overall conversion and selectivity.
Water‐Doped Brønsted Acidic Protic Ionic Liquids for Enhanced Tributyl Citrate Synthesis in a Two‐Phase Esterification System
Authors: Więcławik Justyna , Brzęczek‐Szafran Alina , Barteczko Natalia , Chrobok Anna 
Published: March 2024

AbstractTributyl citrate (TBC) plays a crucial role as a plasticizer, enhancing the flexibility of polymers such as polyvinyl chloride. Its biodegradability and non‐toxic nature contribute to eco‐friendly appeal, making it a preferred additive in diverse industries, including food packaging, medical devices, toys, and consumer goods. Herein, a method for the synthesis of TBC using inexpensive Brønsted acidic protic ionic liquids (ILs) in a two‐phase reaction system is presented. The esterification process is carried out with high yield (>99 %), selectivity (up to 98 %) and short reaction time of 2 h. The catalyst in the form of IL shows excellent performance and stability, desirable for industrial applications.
Recent Advances of Aminopeptidases‐Responsive Small‐Molecular Probes for Bioimaging
Authors: Xu Chengyan , Cui Kaixi , Ye Zhifei , Feng Yurong , Wang Huabin , Liu Hong‐wen 
Published: March 2024

AbstractAminopeptidases, enzymes with critical roles in human body, are emerging as vital biomarkers for metabolic processes and diseases. Aberrant aminopeptidase levels are often associated with diseases, particularly cancer. Small‐molecule probes, such as fluorescent, fluorescent/photoacoustics, bioluminescent, and chemiluminescent probes, are essential tools in the study of aminopeptidases‐related diseases. The fluorescent probes provide real‐time insights into protein activities, offering high sensitivity in specific locations, and precise spatiotemporal results. Additionally, photoacoustic probes offer signals that are able to penetrate deeper tissues. Bioluminescent and chemiluminescent probes can enhance in vivo imaging abilities by reducing the background. This comprehensive review is focused on small‐molecule probes that respond to four key aminopeptidases: aminopeptidase N, leucine aminopeptidase, Pyroglutamate aminopeptidase 1, and Prolyl Aminopeptidase, and their utilization in imaging tumors and afflicted regions. In this review, the design strategy of small‐molecule probes, the variety of designs from previous studies, and the opportunities of future bioimaging applications are discussed, serving as a roadmap for future research, sparking innovations in aminopeptidase‐responsive probe development, and enhancing our understanding of these enzymes in disease diagnostics and treatment.
Sanierung von Bruchsteinmauerwerk an Staumauern des Ruhrverbands
Authors: Klahn Stefan 
Published: March 2024

AbstractDie Staumauern des Ruhrverbands, hergestellt aus örtlichem Bruchstein des Sauerlands, sind über 100 Jahre alt und bedürfen einer ständigen Pflege und Instandhaltung, um die Standsicherheit und Gebrauchstauglichkeit zukunftsorientiert sicherzustellen. Hierzu sind Schäden durch Bewuchs und Frostwechselreaktionen zu beseitigen und neue Schäden möglichst lange zu verhindern. Der vorliegende Beitrag beschreibt den Ablauf solcher Sanierungsmaßnahmen, angefangen von der Bestandsaufnahme über Instandsetzungsmaßnahmen bis hin zur Pflege. Außerdem gibt er einen Überblick über die notwendigen Randbedingungen.
Bending a Cumulene with Electrons: Stepwise Chemical Reduction and Structural Study of a Tetraaryl[4]Cumulene
Authors: Zhou Zheng , Johnson Matthew A. , Wei Zheng , Bühringer Martina U. , Garner Marc H. , Tykwinski Rik , Petrukhina Marina A. 
Published: March 2024

AbstractChemical reduction of a [4]cumulene with cesium metal was explored, and the structural changes stemming from electron acquisition are detailed using X‐ray crystallography. It is found that the [4]cumulene undergoes dramatic geometric changes upon stepwise reduction, including bending of the cumulenic core and twisting of the endgroups from orthogonal to planar. The structural deformation is consistent with early theoretical reports that suggest that the twisting should occur upon reduction of both even and odd [n]cumulenes. The current results, on the other hand, are inconsistent with a previous experimental study of a [3]cumulene in which the predicted twisting is not observed upon reduction. DFT calculations reveal that the barrier to deformation is an order of magnitude lower in a [3]cumulene than a [4]cumulene, allowing the barrier to be overcome in the solid‐state.
Three‐Dimensional Self‐Supported Ge Anode for Advanced Lithium‐Ion Batteries
Authors: Fang Xiang Xiang , Jiang Chaoyan , Yue Chuang , Hu Fang 
Published: March 2024

AbstractThree‐dimensional (3D) self‐supported Ge anode is one of the promising candidates to replace the traditional graphite anode material for high‐performance binder‐free lithium‐ion batteries (LIBs). The enlarged surface area and the shortened ions/electrons transporting distance of the 3D electrode would greatly facilitate the rapid transfer of abundant lithium ions during cycling, thus achieve enhanced energy and power density during cycling. Cycle stability of the 3D self‐supported Ge electrode would be improved due to the obtained enough space could effectively accommodate the large volume expansion of the Ge anode. In this review, we first describe the electrochemical properties and Li ions storage mechanism of Ge anode. Moreover, the recent advances in the 3D self‐supported Ge anode architectures design are majorly illustrated and discussed. Challenges and prospects of the 3D self‐supported Ge electrode are finally provided, which shed light on ways to design more reliable 3D Ge‐based electrodes in energy storage systems.
A Study on Auto‐Catalysis and Product Inhibition: A Nucleophilic Aromatic Substitution Reaction Catalysed within the Cavity of an Octanuclear Coordination Cage
Authors: Dorrat Jack C. , Taylor Christopher G. P. , Young Rosemary J. , Solea Atena B. , Turner David R. , Dennison Genevieve H. , Ward Michael D. , Tuck Kellie L. 
Published: March 2024

AbstractThe ability of an octanuclear cubic coordination cage to catalyse a nucleophilic aromatic substitution reaction on a cavity‐bound guest was studied with 2,4‐dinitrofluorobenzene (DNFB) as the guest/substrate. It was found that DNFB undergoes a catalysed reaction with hydroxide ions within the cavity of the cubic cage (in aqueous buffer solution, pH 8.6). The rate enhancement of kcat/kuncat was determined to be 22, with cavity binding of the guest being required for catalysis to occur. The product, 2,4‐dinitrophenolate (DNP), remained bound within the cavity due to electrostatic stabilisation and exerts two apparently contradictory effects: it initially auto‐catalyses the reaction when present at low concentrations, but at higher concentrations inhibits catalysis when a pair of DNP guests block the cavity. When encapsulated, the UV/Vis absorption spectrum of DNP is red‐shifted when compared to the spectrum of free DNP in aqueous solution. Further investigations using other aromatic guests determined that a similar red‐shift on cavity binding also occurred for 4‐nitrophenolate (4NP) at pH 8.6. The red‐shift was used to determine the stoichiometry of guest binding of DNP and 4NP within the cage cavity, which was confirmed by structural analysis with X‐ray crystallography; and was also used to perform catalytic kinetic studies in the solution‐state.
Cavity Catalysis of an Enantioselective Reaction under Vibrational Strong Coupling
Authors: Singh Jaibir , Garg Pallavi , Anand Ramasamy Vijaya , George Jino 
Published: March 2024

AbstractStrong light‐matter interaction is emerging as an exciting tool for controlling chemical reactions. Here, we demonstrate an L‐proline‐catalyzed direct asymmetric Aldol reaction under vibrational strong coupling. Both the reactants (4‐nitrobenzaldehyde and acetone) carbonyl bands are coupled to an infrared photon and react in the presence of L‐proline. The reaction mixture is eluted from the cavity, and the conversion yields and enantiomeric excess are quantified using NMR and chiral HPLC. The conversion yields increase by up to 90 % in ON‐resonance conditions. Interestingly, a large increase in the conversion yield does not affect the enantiomeric excess. Further control experiments were carried out by varying the temperature, and we propose that the rate‐limiting step may not be the deciding factor in enantioselectivity. Whereas the formation of the enamine intermediate is modified by cavity coupling experiments. For this class of enantioselective reactions, strong coupling does not change the enantiomeric excess, possibly due to the large energy difference in chiral transition states. Strong coupling can boost the formation of enamine intermediate, thereby favouring the product yield. This gives more hope to test polaritonic chemistry based on enantioselective reactions in which the branching ratios can be controlled.
N‐Heterocyclic Carbene Analogues of Wittig Hydrocarbon
Authors: Steffenfauseweh Henric , Vishnevskiy Yury V. , Neumann Beate , Stammler Hans‐Georg , de Bruin Bas , Ghadwal Rajendra S. 
Published: March 2024

AbstractN‐Heterocyclic carbene (NHC) analogues of Wittig hydrocarbon, [(NHC)(Stil)(NHC)] (3a‐c) (NHC = SIPr (1a) = C[N(Dipp)CH2]2, Dipp = 2,6‐iPr2C6H3; IPr (1b) = C[N(Dipp)CH]2; Me‐IPr (1c) = C[N(Dipp)CMe]2 and Stil = C6H4CHCHC6H4) have been reported as crystalline solids. 3a‐c are prepared by two‐electron reductions of the corresponding bis‐1,3‐imidazoli(ni)um bromides [(NHC)(Stil)NHC)](Br)2 (2a‐c) with KC8 in >94 % yields. 2a‐c are accessible by the nickel catalyzed direct C−C coupling of NHCs (1a‐c) with (E)‐4,4'‐dibromostilbene. One‐electron oxidation of 3a,b yields the corresponding radical cations [(NHC)(Stil)NHC)]B(C6F5)4 4a,b. All compounds have been characterized by UV‐Vis/NMR/EPR spectroscopy as well as 2a, 3a, and 3b by single crystal X‐ray diffraction. The electronic structures of representative systems have been analyzed by quantum chemical calculations.