bluuebunny/crossref_metadata_2025_split huggingface dataset:
Selective Interface Engineering with Large π‐Conjugated Molecules Enables Durable Zn Anodes
Authors: Zhang Feng , Meng Qiangqiang , Qian Jia‐Wei , Chen Jingwei , Dong Wei‐Xu , Chen Kai , Cui Yang‐Feng , Dou Shi Xue , Chen Li‐Feng 
Published: January 2025

AbstractUndesirable dendrite growth and side reactions at the electrical double layer (EDL) of Zn/electrolyte interface are critical challenges limiting the performance of aqueous zinc ion batteries. Through density functional theory calculations, we demonstrate that grafting large π‐conjugated molecules (e.g. bilirubin, biliverdin, lumirubin, and hemoglobin) onto Zn surface induces preferential adsorption on non‐(002) facets, leading to interfacial charge redistribution, upshifted Zn d‐band center, and enhanced H+ fixation capability. Among these, bilirubin (BR) is identified as the most effective, preferentially adsorbing onto non‐Zn(002) facets to inhibit hydrogen evolution reaction and promote Zn(002) planar growth during plating. This approach results in average Coulombic efficiency of 99.86 % over 4000 cycles in Zn||BR‐1@Cu cells and prolonged lifespan exceeding 1600 h in BR‐1@Zn||BR‐1@Zn cells at 10 mA cm−2 and 1 mAh cm−2. Even under harsh conditions of 25 mA cm−2 and 10 mAh cm−2, BR‐1@Zn||BR‐1@Zn cell maintains a lifespan of over 400 h. Furthermore, BR‐1@Zn||MnO2 and BR‐1@Zn||NVO full cells achieve 76.4 % and 86.1 % capacity retention after 800 and 1400 cycles at 1.0 A g−1, respectively. This study underscores the importance of grafting large π‐conjugated molecules to allow selective Zn(002) exposure, Zn d‐band center upshift, and EDL structure regulation, paving the way towards durable Zn anodes.
Cyclometalated Half‐Sandwich Ruthenium(II) Complexes: Synthesis, Structure, and Catalytic Activity in Imine Synthesis
Authors: Ye Lin‐Wu , Liu Yong , Yao Zi‐Jian 
Published: January 2025

ABSTRACTFour kinds of cyclometalated half‐sandwich ruthenium(II) complexes 1–4 with air stability were synthesized, which were supported by C,N‐donor Schiff base ligands as raw materials by C‐H activation. These newly synthesized ruthenium(II) complexes were characterized and studied by infrared (IR), ultraviolet (UV), nuclear magnetic resonance (NMR), and other analytical or spectroscopic techniques, and their exact structures of ruthenium(II) complexes were confirmed by single‐crystal X‐ray analysis. Cyclometalated half‐sandwich ruthenium(II) complexes 1–4 exhibited good catalytic activity in catalyzing the oxidative homo‐coupling of primary amines, dehydrogenation of secondary amines, and cross‐coupling reaction of amines with alcohols to synthesize imines, all of which were conducted in an open flask with air as oxidant. There was little effect of different substituents on ruthenium complexes ligands on catalytic efficiency. Ruthenium catalysts had the characteristics of mild reaction conditions, strong universality of substrate, good stability, and high catalytic efficiency, which had potential application in industrial production.
Development of natural deep eutectic solvent‐assisted liquid–liquid extraction method for soap removal from biodiesel: Optimization and kinetics
Authors: Abed Khalid M. , Hayyan Adeeb , Hizaddin Hanee F. , Hashim Mohd Ali , Basirun Wan Jefrey , Alanazi Yousef Mohammed , Saleh Jehad , Gupta Bhaskar Sen , M. Salleh M. Zulhaziman 
Published: January 2025

AbstractThe soap content in biodiesel is an important challenge during the production and purification processing of biodiesel. Natural deep eutectic solvents (NADES) have recently attracted considerable interest as an environmentally suitable substitute for traditional solvents in the biodiesel industry. This work investigates the soap removal from the contaminated biodiesel using NADES. Eight choline chloride‐based deep eutectic solvents (DESs) were screened using the conductor‐like screening model for real solvents (COSMO‐RS) to identify the most suitable solvent for soap removal and were validated experimentally. The effect of NADES molar ratio, NADES:biodiesel ratio, mixing speed and extraction time on the extraction efficiency were investigated. COSMO‐RS screening revealed that the malonic acid‐based NADES possess higher soap elimination, and this is compatible with the experimental screening. The higher extraction efficiency of 99.18% was achieved under the optimum conditions of 1:3 of NADES molar ratio, 1:1 DES:biodiesel, 150 rpm and 15 min of extraction time. The soap removal followed the first‐order kinetic equation with a rate constant of 0.183 min−1. This technique offers innovative and environmentally friendly routes for downstream processing of contaminated biodiesel.
Electrooxidation of Ethylene Glycol to Glycolic Acid with Pt‐Ni(OH)2 Catalysts: High Efficiency and Selectivity for PET Plastics Upgrading
Authors: Li Zijian , Wang Shao , Yin Yijun , Qin Rui , Wei Chenyang , Luo Hongxia , Mu Tiancheng 
Published: January 2025

AbstractThe electroconversion of polyethylene terephthalate (PET) into C2 fine chemicals and hydrogen (H2) presents a promising solution for advancing the circular plastics economy. In this study, we report the electrooxidation of ethylene glycol (EG) to glycolic acid (GA) using a Pt−Ni(OH)2 catalyst, achieving a high Faraday efficiency (>90 %) even at high current densities (250 mA cm−2 at 0.8 V vs. RHE). Notably, this catalyst outperforms most existing Pt‐based catalysts in terms of catalytic activity. Experimental analyses reveal that: 1) Ni(OH)2 enhances the adsorption of OH− ions and promotes the rapid generation of *OH active species, which are essential for the efficient oxidation of EG to GA; 2) the oxygenophilic nature of Pt improves EG adsorption, and in synergy with Ni, accelerates the oxidation process. Furthermore, Pt lowers the electrolysis potential, preventing excessive oxidation and ensuring high selectivity for GA. This work offers a promising pathway for the electrooxidation‐based upgrading of PET plastics and provides valuable insights for future research in this area.
Elliptical Silicon Nanowire Covered by the SEI in a 2D Chemo‐Mechanical Simulation
Authors: Schoof Raphael , Köbbing Lukas , Latz Arnulf , Horstmann Birger , Dörfler Willy 
Published: January 2025

AbstractUnderstanding the mechanical interplay between silicon anodes and their surrounding solid‐electrolyte interphase (SEI) is essential to improve the next generation of lithium‐ion batteries. We model and simulate a 2D elliptical silicon nanowire with SEI via a thermodynamically consistent chemo‐mechanical continuum ansatz using a higher order finite element method in combination with a variable‐step, variable‐order time integration scheme. Considering a soft viscoplastic SEI for three half cycles, we see at the minor half‐axis the largest stress magnitude at the silicon nanowire surface, leading to a concentration anomaly. This anomaly is caused by the shape of the nanowire itself and not by the SEI. Also for the tangential stress of the SEI, the largest stress magnitudes are at this point, which can lead to SEI fracture. However, for a stiff SEI, the largest stress magnitude inside the nanowire occurs at the major half‐axis, causing a reduced concentration distribution in this area. The largest tangential stress of the SEI is still at the minor half‐axis. In total, we demonstrate the importance of considering the mechanics of the anode and SEI in silicon anode simulations and encourage further numerical and model improvements.
Mechanical Properties of Cycled Single Crystal LiNi0.8Mn0.1Co0.1O2 (NMC811) Particles
Authors: Jangde Ashutosh , Kumar Mirtunjay , Tuğrul Gülenç İdris , Wheatcroft Laura , Inkson Beverley J. 
Published: January 2025

AbstractSingle crystal (SC) particle morphologies are attracting significant attention as an alternative to polycrystalline (PC) secondary particles within battery cathodes, to circumvent the degradation paths associated with weak grain boundaries. In the pristine state, the key cathode material LiNi0.8Mn0.1Co0.1O2 (NMC811) exhibits anisotropic mechanical behaviour due to its trigonal
crystal lattice. Here the mechanical properties of cycled SC NMC811 particles are evaluated in real time using in situ compression in a scanning electron microscope (SEM), as a function of both particle orientation, and electrochemical charge‐discharge rate. After 100 cycles, the SC NMC811 particles retain their external morphology, however their non‐basal and basal plane fracture strengths systematically decrease as a function of increasing charge rate C/10→2 C, consistent with accelerated lattice degradation. For all charge rates, the cycled and discharged NMC811 single crystal particles retain the
crystallographic dependence of their strength and deformation mechanisms, with cycled SC particles strongest for compression normal to the (0001) layered structure. The accelerated mechanical softening of cycled NMC811 SC particles at higher C‐rates occurs in parallel with degradation of the electrochemical performance of the NMC811 single crystals, and indicates a higher risk of fracture‐related degradation processes with fast‐charging regimes.
Discovery of Severe Acute Respiratory Syndrome Coronavirus 2 Main Protease Inhibitors through Rational Design of Novel Fluorinated 1,3,4‐oxadiazole Amide Derivatives: An In‐Silico Study
Authors: Jiang Huiying , Xia Heping , Wang Zhonghua , Xiong Fei 
Published: January 2025

ABSTRACTAs severe acute respiratory syndrome coronavirus 2 (SARS‑CoV‑2) variants continue to emerge, there is an urgent need to develop more effective antiviral drugs capable of combating the COVID‐19 pandemic. The main protease (Mpro) of SARS‐CoV‐2 is an evolutionarily conserved drug discovery target. The present study mainly focused on chemoinformatics computational methods to investigate the efficacy of our newly designed trifluoromethyl‐1,3,4‐oxadiazole amide derivatives as SARS‐CoV‐2 Mpro inhibitors. Drug‐likeness absorption, distribution, metabolism, excretion, and toxicity analysis, molecular docking simulation, density functional theory (DFT), and molecular dynamics simulation methods were included. A comprehensive drug‐likeness analysis was performed on the 14 newly designed compounds (1a–1n), and this series of small molecule inhibitors showed potential anti‐SARS‐CoV‐2 activity. In order to reveal the mechanism of drug interaction, these novel compounds were classified by structure, and molecular docking simulations were performed. The results showed good interactions and identified the key amino acid residue GLY‐143. Further DFT analysis using B3LYP‐D3BJ functional and 6‐311 + + G (d, p) basis set was performed to optimize the optimal configuration of the Mpro inhibitors, and the infrared spectrum of the vibration frequency was analyzed to clearly understand the structure and stability of the drug. The electrostatic potential map was analyzed to predict the reactivity of functional groups and protein‐substrate interactions. The frontier molecular orbital analysis and density of states map showed the reactivity level and stability of the drug itself, among which 1i had the smallest energy gap difference (ΔEgap = 3.64 ev), showing good reactivity. The analysis of global reactivity descriptors such as electrophilic index (ω) and chemical potential (μ) also showed that our newly designed Mpro inhibitors had stronger interactions. Molecular dynamics simulation further revealed the stable binding of the Mpro inhibitors in a solvent environment. The binding free energy results calculated by Molecular Mechanics / Poisson Boltzmann Surface Area (MM/PBSA) all exceeded the Food and Drug Administration‐approved standard reference drug (Nirmatrelvir), and the free energy landscape and principal component analysis also further described the energy sites formed during the binding process between the drug molecule and the ligand‐protein and the changes in conformation. These new series of small molecule inhibitors studied in this work will provide the necessary theoretical basis for the synthesis and activity evaluation of novel SARS‐CoV‐2 Mpro inhibitors.
Amphibian‐Derived Peptides as Natural Inhibitors of SARS‐CoV‐2 Main Protease (Mpro): A Combined In Vitro and In Silico Approach
Authors: Spinelli Roque , Sanchis Iván , Rietmann Álvaro , Húmpola María Verónica , Siano Álvaro 
Published: January 2025

ABSTRACTThe COVID‐19 pandemic, caused by the SARS‐CoV‐2 virus, has highlighted the urgent need for novel therapeutic agents targeting viral enzymes such as the main protease (Mpro), which plays a crucial role in viral replication. In this study, we investigate the inhibitory potential of 23 peptides isolated from the skin of amphibians belonging to the Hylidae and Leptodactylidae families against SARS‐CoV‐2 Mpro. Five peptides demonstrated significant inhibition using a colorimetric Mpro inhibition assay, with IC50 values ranging from 41 to 203 µM. Among these, peptides Hp‐1081 and Hp‐1971, derived from Boana pulchella, exhibited the strongest activity, comparable to the natural Mpro inhibitor quercetin. The binding mechanism of the most potent peptide, Hp‐1081, was further investigated through docking and molecular dynamics (MDs) simulations and energetic analysis, which revealed key Mpro residues involved in the binding process. Moreover, because SARS‐CoV‐2 infection can induce ROS overproduction, the antioxidant activity of Hp‐1081 was assessed, reaching 48% of DPPH radical scavenging activity at 100 µM. The most potent peptides also showed no toxicity against human erythrocytes and Artemia salina. This study provides insight into the antiviral potential of amphibian‐derived peptides and highlights their applicability as natural templates for drug development targeting coronaviruses.
Review on the o‐Aminoaniline Moiety in Peptide and Protein Chemistry
Authors: Hong Ziyong Z. 
Published: January 2025

AbstractPeptides and proteins are important functional biomolecules both inside and outside of living organisms. The ability to prepare various types of functionalized peptides and proteins is essential for understanding fundamental biological processes, such as protein folding and post‐translational modifications (PTMs), and for developing new therapeutics for many diseases, such as cancers and neurodegenerative diseases. The o‐aminoaniline moiety was first proposed for activation to a thioester precursor and used for native chemical ligation to prepare large peptides and proteins. In the past decade, the function of o‐aminoaniline has been greatly expanded to facilitate the preparation of homogeneously modified peptide and protein samples, where the modifications can include cyclization, C‐terminus diversification, etc. Many o‐aminoaniline derivatives have also been developed to overcome the inherent limitations of previous versions. In this review, we attempt to summarize the recent developments of different o‐aminoaniline derivatives, focusing on their application to the preparation of functional peptide and protein molecules.
Reactions of Tertiary Aliphatic Cations with Silylated Alkynes: Substitution, Cyclization and Unexpected C−H Activation Products
Authors: Charki Paul , Cordier Marie , Ylijoki Kai E. O. , Müller Daniel S. 
Published: January 2025

AbstractCapozzi's groundbreaking work in 1982 introduced a fascinating reaction involving highly reactive tertiary aliphatic cations and silylated alkynes. This reaction provided an innovative solution to the challenge of coupling a fully substituted tertiary aliphatic fragment with an alkyne moiety. Building upon Capozzi's pioneering efforts, we started an extensive exploration of reaction conditions to expand the initial scope of this reaction. Through meticulous control of the reaction parameters, we uncovered conditions capable of accommodating various functional groups, thereby enhancing the reaction‘s applicability. Intriguingly, our study revealed remarkably high diastereoselectivities for substrates with substitution in the α‐position. Additionally, we made an unexpected discovery: an intriguing C−H activation of a cyclooctane ring furnishing a cyclooctane‐fused cyclobutene. These findings not only extend the utility of Capozzi's original concept but also underscore the potential of highly reactive cations in modern organic C−H activation reactions.
Enhanced K‐Storage Kinetics for N‐Doped Carbon via Controllable Dedoping Strategy
Authors: Zhang Wanying , Chen Hong , Pang Yinshuang , Chen Ningning , Liu Zhi , Xia Haobo , Chen Ran , Zheng Jing , Lin Zixia , Lai Qingxue 
Published: January 2025

AbstractAs a potential alternative to next‐generation LIBs, carbonaceous materials have garnered significant attention as anode materials for potassium‐ion batteries due to their low cost and environmental friendliness. However, carbonaceous materials cannot fulfill the demand of anode for PIBs, due to volume expansion and poor stability during charging/discharging process. It is well‐known that N doping can provide active sites for K‐storage, and expand the layer distance between graphite layers. Therefore, a simple one‐step pyrolysis strategy was proposed to synthesize different nitrogen‐doped carbon to investigate the effects of N‐doping and dedoping on K‐storage performance. Through the synergistic effect of N‐doping and the carbon vacancy defects formed during the de‐doping process, alleviating volume expansion and promoted K+ transport rate. As a result, the PNC demonstrate excellent electrochemical performance, showing good long‐term cycling stability (with a capacity of 195 mAh/g after 300 cycles at a current density of 200 mA/g) and outstanding rate performance. These findings provide valuable insights for the design and development of advanced anode materials with efficient potassium ion storage capabilities.
Recent Progress of Mechanofluorochromism and Mechanoluminescence for Phenothiazine Derivatives and Analogues
Authors: Zhao He , Fan Baiyang , Hu Siwen , Liu Xing liang , Xue Pengchong 
Published: January 2025

AbstractMechanofluorochromism (MFC) and mechanoluminescence (ML) materials have garnered significant attention from researchers due to their potential applications in anti‐counterfeiting, optical recording, photodynamic therapy, bioimaging, stress sensing, display technology, and ink‐free printing paper. Among the various building blocks utilized in these materials, phenothiazine (PTZ) has emerged as a widely employed fundamental component owing to its distinctive electronic and optical properties as well as its facile modification capabilities. Summarizing the recent progress of PTZ derivatives and analogues in this field holds practical significance. In this review article, we classify over one hundred compounds into a few classes based on the positions of substituents and provide detailed descriptions of their contributions to MFC and ML research respectively. This comprehensive review aims to offer theoretical insights and practical examples for researchers engaged in designing and developing new phenothiazine functional materials while serving as a bridge for further exploration of MFC or ML studies.
Fluorinated Macrocycle for Adsorptive Separation and Chromatographic Separation of Toluene and Methylcyclohexane
Authors: Wang Bin , Li Zhao‐Xian , Wu Hai‐Ning , Ning Zi‐Yue , Ju Peng‐Fei , Liu Yue , Zhang Zhi‐Yuan , Li Chunju 
Published: January 2025

AbstractAchieving the adsorptive separation and chromatographic separation of industrially the important chemicals toluene and methylcyclohexane using the same material is a highly desirable goal. We have successfully accomplished this using a fluorinated macrocycle tetrafluoroterphen[3]arene (4FTP3), which was synthesized and used for gas chromatographic separation in our previous work. The macrocycle 4FTP3 permitted the adsorptive separation of toluene from a toluene/methylcyclohexane mixture (1 : 1, v/v) with a purity of 99.3 % in a single adsorption cycle. Additionally, the use of 4FTP3 as a gas chromatographic stationary phase permitted the high‐resolution separation of a toluene/methylcyclohexane mixture, with a retention capacity decreasing in the order of: toluene>methylcyclohexane. Single‐crystal structural analysis revealed that the C−H⋅⋅⋅F interactions between 4FTP3 and toluene resulted in an enhanced binding affinity, association enthalpy, and longer retention time for toluene. This macrocycle is of particular interest for use as a separation material due to its simultaneous adsorptive separation and gas chromatographic separation of toluene/methylcyclohexane. The present fluorinated macrocycle may therefore have roles to play in both analytical science and the chemical industry.
Deep Learning‐Based Hydrological Drought Prediction in the Wardha River Basin, India
Authors: Janardhana Mangala , Kikon Ayilobeni 
Published: January 2025

ABSTRACTDrought is an abnormal condition characterized by dry weather which can continue for days, months, and years. Drought often has major effects on the ecosystems and agriculture of vulnerable regions leading to catastrophe on the local economies. Deep learning was employed in this study to forecast hydrological drought in the Wardha River basin in Maharashtra, Vidarbha region, India. Monthly streamflow data from 1971 to 2020 for the Wardha River serve as the basis for analysis. The study calculates the standardized streamflow index (SSI) at several timescales (3, 6, 9, 12, and 24 months). Deep learning models, specifically the long short‐term memory (LSTM) model and the multilayer perceptron (MLP) model, are employed for drought prediction within the study region. The models are trained with data spanning from 1971 to 2005 and tested against data from 2006 to 2020. Predictions are made for lead time scales of 6 and 12 months by considering lagged SSI values. Drought event lead time scale forecasts will serve as an early warning strategy. The 6‐ and 12‐month lead times of the SSI forecast could be used as a warning for anticipated drought conditions. The study assesses model efficiency by comparing the root mean square error (RMSE) and mean absolute error (MAE) between the LSTM and MLP models. The results indicate that the LSTM model performs better for higher time scales in predicting hydrological drought, whereas the MLP model demonstrates superior predictive capabilities for lower time scales of drought index.
National Horizon Scanning for Future Crops Under a Changing UK Climate
Authors: Redhead John W. , Brown Matt , Price Jeff , Robinson Emma , Nicholls Robert J. , Warren Rachel , Pywell Richard F. 
Published: January 2025

ABSTRACTMost national assessments of climate change‐related risks to agriculture focus on the productivity of existing crops. However, one adaptation option is to switch to alternative crops better suited to changing local climates. Spatially explicit projections of relative climatic suitability across a wide range of crops can identify which ones might be viable alternatives. Parametrising process‐based models for multiple crops is complex, so there is value in using simpler approaches to ‘horizon scan’ to identify high‐level issues and target further research. We present a horizon scan approach based on EcoCrop data, producing mapped changes in suitability under +2°C and +4°C warming scenarios (above pre‐industrial), for over 160 crops across the United Kingdom. For the United Kingdom, climate change is likely to bring opportunities to diversify cropping systems. Many current and potential new crops show widespread increases in suitability under a +2°C warming scenario. However, under a +4°C scenario, several current crops (e.g. onions, strawberries, oats, wheat) begin to show declines in suitability in the region of the United Kingdom where most arable crops are currently grown. Whilst some new crops with increasing suitability may offer viable alternatives (e.g. soy, chickpea, grapes), the greatest average increases in suitability across crops occur outside the UK's current areas of greatest agricultural production. Realising these opportunities would thus be likely to require substantial changes to current farming systems and supply chains. By highlighting these opportunities and challenges, our approach provides potentially valuable information to farmers and national assessments.