bluuebunny/crossref_metadata_2025_split huggingface dataset:
Molecular Trapdoor in HEU Zeolite Enables Inverse CO2‐C2H2 Separation
Authors: Jia Jizhen , Yan Nana , Lian Xin , Liu Shanshan , Yue Bin , Chai Yuchao , Wu Guangjun , Xu Jian , Li Landong 
Published: November 2024

AbstractThe adsorptive separation of molecules with very similar physical properties is always a challenging task. Reported herein is the design and tailoring of zeolite adsorbent for the precise discrimination and separation of CO2‐C2H2 mixture through the pronounced trapdoor effect. Typically, Sr exchanged K‐type clinoptilolite, namely Sr/K‐HEU, is developed as a robust zeolite adsorbent for inverse CO2‐C2H2 separation, showing the‐state‐of‐the‐art dynamic CO2/C2H2 selectivity of 48.0 and sustainable CO2 dynamic uptake of 0.96 mmol/g at the same time. The perfect recyclability and the intrinsic low‐cost nature of Sr/K‐HEU make it a promising candidate for practical applications. Three‐dimensional electron diffraction determines the precise structure of Sr/K‐HEU and density functional theory calculations reveal the intricate interplay between guest molecules and the gate‐keeping extraframework cations. Briefly, extraframework Sr2+ cations from the ten‐membered rings of HEU zeolites act as the molecular trapdoor, allowing the entry of CO2 molecules while excluding C2H2. This work presents a new example of molecular trapdoor in zeolite and its successful application in the challenging inverse CO2‐C2H2 separation, which not only expands the scope of molecular trapdoor concept but also improves current understanding on the nature of molecular trapdoor.
Molecular‐level Modulation of N, S‐Co‐Doped Mesoporous Carbon Nanospheres for Selective Aqueous Catalytic Oxidation of Ethylbenzene
Authors: Liu Yumeng , Zhang Liangliang , Tan Zhengwen , Sun Wenyue , Zhang Ling , Qiao Zhen‐An 
Published: November 2024

AbstractSelective oxidation of aromatic alkanes into high value‐added products through benzylic C−H bond activation is one of the main reactions in chemical industry. On account of the constantly increasing demand for mass production, efficient, eco‐friendly and sustainable catalysts are urgently needed. Herein, we describe a facile and versatile emulsion‐assisted interface self‐assembly strategy towards molecular‐level fabrication of co‐doped mesoporous carbon nanospheres with controllable active N and S species. The method enables a high degree of control over nanoparticle sizes, mesoporous nanostructures, contents of heteroatoms and the chemical composition. The optimized catalyst exhibits high catalytic performance of 97 % ethylbenzene conversion and 98 % selectivity to acetophenone. Density functional theory simulations reveal that N, S‐co‐doping leads to the redistribution of charge and spin densities, introducing more active carbon atoms and realizing aerobic oxidation of ethylbenzene efficiently. This work presents a general strategy for molecular‐level design of carbon‐based catalysts, and also provides new insight into the influence of heteroatom‐doping on catalytic properties.
Cognitive Diversity for Creativity and Inclusive Growth
Authors: Thuo Martin , Jeffries‐EL Malika , Holly James , Martin Andrew , Blair Peter Q. 
Published: November 2024

AbstractCognitively diverse teams outperform high intelligence (IQ) teams in problem solving, while businesses with at least one woman in their board of directors financially outperform ones with all men boards. These well‐known facts are lost in most academic science enterprises. Herein, we make the case for looking at sources, approaches, and opportunities in expanding cognitive diversity of research teams for high productivity and efficiency.
Manipulating Aggregate Electrochemistry for High‐Performance Organic Redox Flow Batteries
Authors: Xiang Zhipeng , Ren Tianlu , Huang Mingbao , Li Wenjin , Wang Liwen , Wan Kai , Fu Zhiyong , Liang Zhenxing 
Published: November 2024

AbstractOrganic molecule in solutions is the energy storage unit in the organic redox flow batteries (ORFBs), of which the aggregation is acknowledged pivotal but has been rarely investigated. By establishing a pyridinium library, the manipulation over the aggregation in solutions is investigated at the molecular level. Both theoretical calculations and physiochemical methods are used to characterize the aggregate's structure, and salient findings are as follows. First, the singly‐reduced monoradicals simultaneously aggregate in a concentrated solution, which is driven by the solvation effect, orbital overlap and dispersion interaction. Second, the aggregation can be manipulated by the molecular engineering strategy and counteracted by introducing either electrostatic repulsive force or twisted geometry. Third, the monoradical's aggregation yields a decrease in the molecular singly occupied molecular orbital energy level and a linear scaling relationship with its thermodynamic potential. As a result, the increase in the concentration lowers the battery's voltage, which counteracts its effort to increase the battery's energy density. The anti‐aggregation is proven effective in breaking the scaling relationship and accordingly, a molecular strategy to manipulate aggregate electrochemistry is developed. This work provides physical insights into the electrolytic solution and chemical strategy for optimizing the flow battery.
Self‐Organized Integrated Electrocatalyst on Oxygen Conversion for Highly Durable Zinc‐Air Batteries
Authors: Chang Qian , He Feng , Zhang Zhihui , Fu Xinlong , Wang Yi , Huang Changshui , Li Yuliang 
Published: November 2024

AbstractEfficient bifunctional electrocatalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are key for clean energy applications such as rechargeable metal‐air batteries. Highly efficient bifunctional electrocatalysts have been the focus of great attention by scientists. Here, an innovative and continuous growth method is established to fabricate integrated Janus structure Co3O4/CoNGDY catalyst, which can work for bifunctional oxygen catalytic conversion, achieving highly durable zinc‐air batteries. Embedded in the hydrangea‐shaped N‐doped graphdiyne (NGDY), the Co3O4/CoNGDY is self‐organized by CoNGDY at the NGDY contact sites and Co3O4 at the upper part, in which Co3O4 works as OER catalyst and CoNGDY acts as ORR catalyst. Due to the incomplete charge transfer within integrated structure, NGDY reduces the d‐band center of the Co sites, so the adsorption strength of intermediates is balanced, and the catalytic activity for ORR/OER is increased. The Co3O4/CoNGDY can serve as an efficient air electrode of rechargeable zinc‐air batteries. The rechargeable Co3O4/CoNGDY‐based aqueous zinc‐air batteries demonstrate excellent performance with a high specific capacity of 746.8 mAh g−1 and an extremely long lifetime of more than 5000 hours. The recoverable modularized cylindrical Co3O4/CoNGDY‐based solid‐state zinc‐air batteries with a power density of up to 167.6 mW cm−2 can be achieved.
Chemoenzymatic Synthesis of the Cyclopiane Family of Diterpenoid Natural Products
Authors: Wang Tao , Zou Jiasheng , Wang Kaibiao , Liu Yuanning , Zhang Shouqi , Kong Yao , Xu Zhengren 
Published: November 2024

AbstractA three‐stage chemoenzymatic synthesis of the cyclopiane family and related diterpenes is reported. Deoxyconidiogenol with a 6/5/5/5‐fused tetracyclic cyclopiane skeleton was first produced by an engineered E. coli host harboring the corresponding terpene cyclase PchDS. Ten cyclopiane diterpenes were synthesized by late‐stage functionalization of rings A, B and D of the cyclopiane skeleton through direct redox operations, directed C−H activation, and enzymatic hydroxylation, respectively. Skeletal diversification was achieved by taking advantage of the selective 1,2‐alkyl migration of a cyclopiane cation generated chemically or enzymatically. Three cyclopiane‐related skeletons, including the spiro 5/5/5/5‐tetracyclic skeleton of spiroviolene, the angular 5/6/5/5‐fused ring system of phomopsene, and the new linear 5/6/5/5‐fused tetracyclic ring system of amycolatene, were produced either by chemical skeletal transformation from the cyclopiane skeleton, or by terpene cyclases discovered by genome mining.
General and Fast Gas–Solid Synthesis of Functional MXenes and Derivatives on the Scale of Tens of Grams
Authors: Liu Yang , Liu Sen , Zhao Guoqiang , Shen Maoqiang , Gao Xinyue , Zhao Yanhao , Liu Xuesen , Hou Linrui , Yuan Changzhou 
Published: November 2024

AbstractThe rising of MXenes not only enriches the two‐dimensional material family but also brings more opportunities for diverse functional applications. However, the controllable synthesis of MXenes is still unsatisfied via the common liquid‐solid etching route, considering the unsolved problems like safety risk, time cost and easy oxidation. Herein, a facile yet efficient gas‐solid (G‐S) reaction methodology is devised by using hydrogen fluoride gas derived from fluorinated organics as the MAX etchant toward high‐efficiency fabrication of multiple MXenes and their derivatives. The innovative G‐S reaction strategy exhibits superb versatility to achieve different gram‐level MXenes (V2C, Ti3C2, Nb2C, Ti2N, Ti3CN, (Mo2/3Y1/3)2C) in a very short time, and even realizes in situ heteroatom doping or synchronous phase conversion of MXenes directly from MAX phases. The obtained MXenes and their derivatives exhibit excellent structure stability and high electron/ion conductivity, making them promising materials for electrochemical applications. In particular, the N‐doped V2C MXene shows superior adsorption and catalytic activity toward lithium polysulfides for advanced lithium sulfur batteries.
Thiosulfate‐Mediated Polysulfide Redox for Energetic Aqueous Battery
Authors: Feng Yutong , Yu Xiaoyu , Wang Boya , Zhang Tengsheng , Zhou Wanhai , Wang Yifeng , Li Xinran , Zhao Jian , Zhao Jingwen , Li Wei , Ma Chenyan , Zhao Dongyuan , Chao Dongliang 
Published: November 2024

AbstractSulfur‐based aqueous batteries (SABs) are regarded as promising candidates for safe, low‐cost, and high‐energy storage. However, the sluggish redox kinetics of polysulfides pose a significant challenge to the practical performance of SABs. Herein, we report a unique redox regulation strategy that leverages thiosulfate‐mediated ligand‐chain interaction to accelerate the polysulfide redox process (S0/S2−). The S2O32− species in the electrolyte can induce the rapid reduction of polysulfide through a spontaneous chemical reaction with sulfur species, while facilitating the reversible oxidation of short‐chain sulfides. Moreover, the thiosulfate redox pair (S2O32−/S4O62−) within the K2S2O3 electrolyte contributes additional capacity at higher potential (E0 >0 V vs SHE). Consequently, the elaborate SAB delivers an unprecedented K+ storage capacity of 2470 mAh gs−1, coupled with a long cycling life exceeding 1000 cycles. Remarkably, thiosulfate‐mediated SAB achieves an energy density of 616 Wh kgS+Zn−1, surpassing both organic K–S batteries and conventional aqueous battery systems. This work elucidates the mechanism underlying the thiosulfate‐mediated polysulfide redox process, thereby opening a pathway for the development of high‐energy aqueous batteries.
Visible Light‐Mediated [4+2] Annulation of Silylimines with Olefins to 1‐Aminotetralins Enabled by Diradical Hydrogen Atom Transfer of C−H Bonds
Authors: Liu Qian , Huang Yao , Zhou Xiang , Fernández Israel , Xiong Yang 
Published: November 2024

AbstractA facile photochemical, one‐pot synthesis of highly functionalized 1‐aminotetralins derivatives (>70 examples) from readily accessible o‐alkyl and o‐formyl aryl silylimines with olefins is described. A diradical‐mediated hydrogen atom transfer (DHAT) of primary, secondary, and tertiary C(sp3)−H bonds of o‐alkyl arylsilylimines and C(sp2)−H bonds of o‐formyl arylsilylimines enabled a [4+2] annulation with olefins in excellent diastereoselectivity. This was accomplished upon irradiation at λ = 420 nm in the presence of thioxanthen‐9‐one (10 mol %) as the sensitizer via energy transfer. Moreover, sulfur‐substituted o‐alkyl silylimines can undergo such photochemical process in the absence of an external photosensitizer. This effective protocol is compatible with a variety of functional groups and can be applied to the modification of bioactive molecules. Based on mechanistic evidences and computational studies, it is suggested that the silyl substituent enables an efficient energy transfer leading to the formation of a key C,N‐diradical and subsequent [4+2]‐cyclization was supported by a better molecular orbital matching between the HSOMO of the 1,4‐diradical intermediate and the LUMO of the olefins. Thus, upon irradiation, the excited silylimine unlocks a carbon‐to‐nitrogen DHAT and subsequent [4+2] cyclization that allows the divergent functionalization of benzylic C(sp3)−H bonds and C(sp2)−H bonds.
Repulsive Vector Couplings and Massive Strange Stars
Authors: Köpp Fábio , Horvath Jorge , Hadjimichef Dimiter , Zen Vasconcellos César A. 
Published: November 2024

ABSTRACTWe describe in this work the hypothetical nuclear matter QCD phase composed of up, down and strange quarks, introducing repulsive vector interactions, which yield an enhanced MIT bag model (vMIT). Repulsive interactions seem a crucial ingredient to describe stable (and massive hybrid) compact star configurations, to comply with recent observations of pulsars with masses above . The motivation of our study, based on a known and widespread theoretical approach, is to review some of its foundations in view of recent observational advances on pulsar properties with a higher precision measurements. We address in this contribution the stability of compact stars with vector interactions, highlighting also the role of the bag constant and its impact on the stellar incompressibility. Therefore we reassess the proposal formulated by Bodmer, Terazawa, Witten, Farhi, and Jaffe, which suggests that strange quark matter may actually be more stable than ordinary hadronic matter. On this line of investigation, we analyze the dimensionless tidal deformability constraints of the intriguing central compact object (CCO) within the supernova remnant HESS J1731‐347 and the GW170817 event as strange matter candidates.
The Art of Chilling Out: How Neurons Regulate Torpor
Authors: Ohba Akinobu , Yamaguchi Hiroshi 
Published: November 2024

ABSTRACTEndothermic animals expend significant energy to maintain high body temperatures, which offers adaptability to varying environmental conditions. However, this high metabolic rate requires increased food intake. In conditions of low environmental temperature and scarce food resources, some endothermic animals enter a hypometabolic state known as torpor to conserve energy. Torpor involves a marked reduction in body temperature, heart rate, respiratory rate, and locomotor activity, enabling energy conservation. Despite their biological significance and potential medical applications, the neuronal mechanisms regulating torpor still need to be fully understood. Recent studies have focused on fasting‐induced daily torpor in mice due to their suitability for advanced neuroscientific techniques. In this review, we highlight recent advances that extend our understanding of neuronal mechanisms regulating torpor. We also discuss unresolved issues in this research field and future directions.
Queuosine tRNA Modification: Connecting the Microbiome to the Translatome
Authors: Rashad Sherif 
Published: November 2024

ABSTRACTTransfer RNA (tRNA) modifications play an important role in regulating mRNA translation at the codon level. tRNA modifications can influence codon selection and optimality, thus shifting translation toward specific sets of mRNAs in a dynamic manner. Queuosine (Q) is a tRNA modification occurring at the wobble position. In eukaryotes, queuosine is synthesized by the tRNA‐guanine trans‐glycosylase (TGT) complex, which incorporates the nucleobase queuine (or Qbase) into guanine of the GUN anticodons. Queuine is sourced from gut bacteria and dietary intake. Q was recently shown to be critical for cellular responses to oxidative and mitochondrial stresses, as well as its potential role in neurodegenerative diseases and brain health. These unique features of Q provide an interesting insight into the regulation of mRNA translation by gut bacteria, and the potential health implications. In this review, Q biology is examined in the light of recent literature and nearly 4 decades of research. Q's role in neuropsychiatric diseases and cancer is highlighted and discussed. Given the recent interest in Q, and the new findings, more research is needed to fully comprehend its biological function and disease relevance, especially in neurobiology.
Ubiquitin and Ubiquitin‐Like Modifications in Organelle Stress Signaling: Ub, Ub, Ub, Ub, Stayin’ Alive, Stayin’ Alive
Authors: Lafont Elodie , Chevet Eric 
Published: November 2024

ABSTRACTDue to various intracellular and external cues, cellular organelles are frequently stressed in both physiological and pathological conditions. Sensing these stresses initiates various signaling pathways which may lead to adaptation of the stressed cells or trigger its their death. At the unicellular level, this stress signaling involves a crosstalk between different organelles. At the multicellular level, such pathways can contribute to indicate the presence of a stressed cell to its neighboring cells. Here, we highlight the crucial and diverse roles played by Ubiquitin and Ubiquitin‐like modification in organelle stress signaling.
Dose‐dependent effects of anthocyanin‐rich extracts on obesity‐induced inflammation and gut microbiota modulation
Authors: Vannuchi Nicholas , Jamar Giovana , de Rosso Veridiana Vera , Pisani Luciana Pellegrini 
Published: November 2024

AbstractObesity and its associated inflammatory state pose a significant health burden. Anthocyanins, bioactive compounds found in fruits and vegetables, have garnered interest in their potential to attenuate these conditions. Understanding the dose‐dependent response of anthocyanins is essential for optimizing their therapeutic potential in preventing and managing obesity. This comprehensive review explores the current knowledge on the dose‐dependent effects of anthocyanins on obesity in both human and animal models, analyzing the structure and mechanism of absorption of these compounds. The article also highlights the diverse mechanisms underlying anthocyanin action, the symbiosis between anthocyanins and gut microbiota impacting metabolite production, influencing diverse health outcomes, modulating cytokines, and activating anti‐inflammatory pathways. Additionally, their impact on energy metabolism and lipid regulation is discussed, highlighting potential contributions to weight management through AMPK and PPARγ pathways. Despite promising results, dose‐dependent effects are fundamental considerations, with some studies indicating less favorable outcomes at higher doses. Future research should focus on optimizing dosages, accounting for individual responses, and translating findings into effective clinical applications for obesity management.
‘I'm a tough cookie’: An IPA study of the experience of burnout in trainee counselling psychologists
Authors: Archer Angelina 
Published: November 2024

AbstractObjectiveCounselling psychology training consists of several professional, academic and personal demands. Poor management of these demands could lead to trainees experiencing burnout and potentially dropping out from training. The existing literature primarily focuses on the stressors of counselling psychology training or the effects of burnout in general, but the research is sparse on burnout being a potentially useful learning experience for trainees. The aim of this paper was to present the experiences of eight third‐year trainee counselling psychologists, with a specific focus on how burnout influenced their development as they approached the end of their training. This paper was written from a larger doctoral research thesis.MethodIn‐depth, semi‐structured interviews were analysed using interpretative phenomenological analysis (IPA).Results and ConclusionsFour themes emerged from the analysis: A perfect storm: The demands of counselling psychology training, Treading on shaky foundations, Ripple effect of the training and Rebuilding from the ashes: Learning from burnout. The overall findings suggested burnout was characterised as perseverance through unaddressed difficulties, shame and significant personal upheaval from the training process. However, most trainees learned from their experience of burnout and reported developing greater resilience and self‐awareness. Recommendations and areas for future research are also discussed in this paper.
Spigelian Hernia Unveiled: A Case Report of Unexpectedly Extended Hernial Sac and Successful Surgical Intervention
Authors: Mansour Marah , Saiouf Yaman , Gharib Karim , Deeb Dani , Almokdad Mohammad Yaman 
Published: November 2024

ABSTRACTSpigelian hernia is a rare type of abdominal hernia; diagnosis is primarily through computed tomography, which is crucial for accurate diagnosis and planning early surgical intervention to preserve the herniated sac's contents.
α‐D Nucleoside Based Self‐Healing Supramolecular Hydrogels Derived from the α‐D Anomers of 2’‐Deoxyguanosine and Fluorescent 8‐Azapurine 2’‐Deoxyribofuranosides
Authors: Deshmukh Sushma , Budow‐Busse Simone , Kondhare Dasharath , Schäfer Andreas H. , Leonard Peter , Seela Frank 
Published: November 2024

AbstractSelf‐assembly of α‐D nucleosides to supramolecular hydrogels is described in detail. Hydrogel formation is studied on α‐D 2’‐deoxyguanosine (α‐dG), and the fluorescent 8‐azapurine α‐D nucleosides 2‐amino‐8‐aza‐2’‐deoxyadenosine (α‐2‐NH2‐z8Ad) and 8‐aza‐2’‐deoxyisoguanosine (α‐z8iGd). These compounds were prepared from α‐D 8‐aza‐2’‐deoxyguanosine by an activation/amination protocol followed by deamination. Protonation and deprotonation pKa values of monomeric nucleosides were determined. Fluorescence measurements displayed the pH‐dependent fluorescence intensity of α‐D 8‐azapurine nucleosides. α‐dG and α‐z8iGd self‐assemble to gels that are selective for K+‐ions. The α‐dG gel is transparent and the α‐z8iGd gel shows fluorescence. α‐2‐NH2‐z8Ad forms fluorescent gels in the presence of alkali metal ions of different size. SEM images expose a large condensed and flat structure for the α‐dG gel, whereas the α‐2‐NH2‐z8Ad gel consists of flakes that are connected to bundles. A porous structure generated by helical cylindric fibers was found for the α‐z8iGd gel. All α‐D hydrogels show long‐term lifetime stability. The α‐z8iGd hydrogel in KCl solution has the highest Tgel value. The minimum gelation concentration of the hydrogels is 0.3‐0.5 mg nucleoside/100 μL alkali ion solution. In periodical step‐strain experiments, the hydrogels of α‐dG, α‐2‐NH2‐z8Ad and α‐z8iGd displayed thixotropy. Based on their self‐healing and shear‐thinning properties the hydrogels are injectable.