bluuebunny/crossref_metadata_2025_split huggingface dataset:
Surface modification of spherical silica micro‐powder using silane coupling agents and their application in epoxy resin‐based composite materials
Authors: Wang Daobei , Yu Mingdong , Wang Yining , Yao Zhiqiang , Xia Anqi , Li Lin , Wang Dongzhi 
Published: March 2024

AbstractIn recent years, the packaging industry has utilized electronic packaging materials with epoxy resin (EP) and high‐performance fillers, exhibiting superior mechanical properties and thermal conductivity. Spherical silica micro‐powder (SSP) is a critical thermal conductive filler but faces challenges due to its inorganic nature. Surface modification is essential to improve SSP's compatibility and dispersion in organic matrices for effective use in EP‐based composites. In this paper, the effects of the following four modification methods on SSP/EP composites were studied: (1) the processes include co‐modification with dimethyldimethoxysilane (DMDMS) and trimethylethoxysilane (MTES), (2) modification with NaOH, (3) co‐modification with DMDMS and MTES in an alkaline environment after NaOH modification, and (4) co‐modification with methyltrimethoxysilane (MTMS) and propyltrimethoxysilane (PTMOS). Through comprehensive characterization and evaluation, it is evident that modification schemes 1, 3, and 4 significantly enhance SSP's hydrophobicity, dispersibility, and compatibility with EP. This led to the improvement of thermal conductivity and stability of the composite, and modification scheme 4 showed the highest enhancement, with a 42.6% increase in thermal conductivity. Moreover, the mechanical properties of modified composite materials, such as bending strength, impact resistance, and tensile strength, surpass those of unmodified SSP/EP composite materials. The study provides valuable insights for reducing manufacturing costs and enhancing productivity in the electronic packaging sector.
A climatological analysis of northward‐moving typhoon in environments of the Northeast China cold vortex
Authors: Zhao Dajun , Yu Yubin , Wei Na , Song Jinjie , Chen Lianshou 
Published: March 2024

AbstractThis study investigates the influence of the Northeast China cold vortex (NCCV) on the northward‐moving typhoons (NTCs) over the western North Pacific (WNP). There is a significant inverse relationship between the NCCV during June–September and simultaneous NTCs during 1981–2021. Fewer (more) NTCs are observed during NCCV active (inactive) year a combination of less (more) NTC genesis, particularly over the central Pacific region of 10°–30° N and 130°–150° E, and fewer (more) NTCs moving northwestward and making landfall in coastal regions of the Yellow Sea and Bohai Sea. These regions are characterized by significantly decreased low‐level vorticity and mid‐level humidity, which impedes NTC genesis and notably enhances the deep‐layer subtropical straight westerly steering flow, thus blocking the northward movement of NTCs. These remarkable environmental changes during different NCCV years are clearly linked with the changes of an anomalous anticyclone in the subtropics (20°–30° N, 120°–160° E). In short, more (less) NCCV activity strengthens (weakens) the anomalous anticyclone, resulting in fewer (more) NTCs.
Identifying the Role of Electrolyte Additives for Lithium Plating on Graphite Electrode by Operando X‐ray Tomography
Authors: Klein Antoine , Sadd Matthew , Mozhzhukhina Nataliia , Olsson Martina , Broche Ludovic , Xiong Shizhao , Matic Aleksandar 
Published: March 2024

AbstractThe plating of lithium metal on the graphite electrode is a major degradation mechanism in lithium‐ion batteries (LIBs). It brings a significant risk of internal shortcircuit by penetration of dendritic lithium through the separator, leading to short cycle life and safety issues. Understanding how and when plating occurs is crucial for the development of mitigation strategies, e. g. tuning the electrolyte composition. Here we present an operando X‐ray tomographic microscopy (XTM) study to directly monitor the plating of lithium metal in a lithium/graphite cell. XTM enables a non‐destructive and quantitative characterization at operando conditions of lithium deposition on a graphite electrode at relevant conditions. In this work it allows us to probe the role of the electrolyte additives vinylene carbonate (VC) and lithium bis(fluorosulfonyl)imide (LiFSI) in the standard LIB electrolyte LP57 (base electrolyte without additives). The additives show overall better performances in terms of delayed onset of lithium plating which is important for the utilisation of the full capacity of graphite intercallaiton. We show that there is a transition during lithiation of the dominating mechanism, once lithium plating is initiated this rapidly becomes dominating and hinders further intercalation. For the base electrolyte a homogeneous and dense morphology of plated lithium is found, whereas a more dendritic morphology is observed in the presence of additives. During delithiation, there is a rapid stripping of some of the plated lithium followed by deintercalation. In addition, our work provides a general methodology to track the morphology of plated lithium, which is crucial for fundamental research about battery safety.
The T‐locus – inspiration and distraction?
Authors: Erickson Robert P. 
Published: March 2024

AbstractThe T/t locus was a major focus of study by mouse geneticists during the 20th century. In the 70s, as the study of cell surface antigens controlling transplantation antigens was taking off, several laboratories hypothesized that alleles of this locus would control cell surface antigens important for embryonic development. One such antigen, the embryonal carcinoma F9 antigen was said to be an example. Other antigens were described on sperm and embryos that were said to be controlled by alleles at the T/t complex. These findings were later found to be false. The history of the findings and their refutation is described.
A Review on the Traditional Applications, Phytochemistry, and Pharmacology of the Genus Physochlaina G. Don
Authors: Rasheed Tantray Younas , Jan Ishrat , Mohiuddin Irshad , Gorla Preeti , Anand Charul , Chandra Arya Jagdish , Ahmad Bhat Shahnawaz , Kumar Vijay , Narasimhaji Ch. Venkata , Nagayya Shiddamallayya , Acharya Rabinarayan 
Published: March 2024

AbstractPhysochlaina is a genus of flowering plants belonging to the family Solanaceae and consists of 10 species distributed in various Asian countries. The species of the genus have been traditionally used to cure a variety of illnesses due to their highly valuable medicinal properties, including cancer, asthma, cough, weakness, stomachache, diarrhea, swelling, spasms, toothache, boils, ulcers, rheumatic pain, chronic bronchitis, gastric problems, abdominal pain, palpitation, and insomnia. The species have gained significant attention due to their remarkable ethnopharmacological and ethnomedicinal significance. The researchers have isolated so far 71 biologically active secondary metabolites from different Physochlaina species, which include flavonoids, alkaloids, coumarins, phenolic acids, iridoids, and sterols. These compounds exhibit diverse biological activities, such as antibacterial, anti‐oxidant, anti‐inflammatory, cytotoxic, and anticancer properties. The present review has been compiled with the intention of providing a comprehensive overview of the botany, distribution, traditional uses, phytochemical profile, and biological activities of the genus Physochlaina for future exploration of plant‐based drugs and therapeutic approaches. The present review contributes to understanding the significant pharmacological potential of Physochlaina species and unraveling their chemical composition, highlighting their relevance in developing therapeutic agents. Till date, numerous pharmacological properties and isolated phytochemicals of Physochlaina species that support the species traditional and ethnobotanical history have been documented in a number of scientific publications. However, greater emphasis should be paid to in vivo investigations on various extracts and their phytoconstituents as well as mechanistic analysis to help drug developers better understand how to use Physochlaina species as significant therapeutic resources for herbal formulations using various techniques.
Advancements in Addressing Microcrack Formation in Ni–Rich Layered Oxide Cathodes for Lithium–Ion Batteries
Authors: Xu Tianmei , Wu Jingjing , Ding Juan , Huang Yingde , Huang Yudai , Zhao Wengao 
Published: March 2024

AbstractNickel–rich layered oxides of LiNi1–x–yCoxMn(Al)yO2 (where 1–x–y>0.6) are considered promising cathode active materials for lithium‐ion batteries (LIBs) due to their high reversible capacity and energy density. However, the widespread application of NCM(A) is limited by microstructural degradation caused by the anisotropic shrinkage and expansion of primary particles during the H2→H3 phase transition. In this mini–review, we comprehensively discuss the formation of microcracks, subsequent material degradation, and related alleviation strategies in nickel–rich layered NCM(A). Firstly, theories on microcracks′ formation and evolution mechanisms are presented and critically analyzed. Secondly, recent advancements in mitigation strategies to prevent degradation in Ni–rich NCM/NCA are highlighted. These strategies include doping, surface coating, structural optimization, and morphology engineering. Finally, we provide an outlook and perspective to identify promising strategies that may enable the practical application of Ni–rich NCM/NCA in commercial settings.
Anodic Oxidation of Aliphatic and Aromatic Amides, Bisamides and Related Derivatives
Authors: Becker James Y. 
Published: March 2024

AbstractThe current comprehensive review covers four main parts, of which some are presented in the form of a personal account. 1. Anodic oxidation of a) N‐alkyl and N,N‐diallyl carbonyl moieties, b) Azacycloalkyl amides and the effect of ring‐size on the outcome, c) Lactams, d) Sulfonamides, and e) The effect of a substituent R attached to carbonyl (N−CO−R) or sulfonamides (N−SO2R) on their oxidation potentials. 2. Anodic oxidation of aromatic amides, in particular of type Ph2CHCONHAr, lacking hydrogen(s) at the α‐position to nitrogen. They undergo three types of bond‐cleavage, yielding a variety of fragmentation products. 3. a) Anodic oxidation of symmetrical bisamides of type ZCONH(CH2)nNHCOZ (Z=Me, Ph, Ar; n=2–4) under constant current electrolysis, in methanol. For n=3, 4 they afford mostly mono‐ and dimethoxylation products. For n=2 they undergo ′CH2−CH2′ bond cleavage to yield fragmentation products. b) Anodic oxidation of symmetrical bisamides of type ArCONH(CH2)2NHCOAr under controlled potential electrolysis, in acetonitrile, leads togem‐unsymmetrical bisamides of type ArCONHCH2NHCOMe as the major product, in fair yields. 4. Utilization of the anodic process in organic synthesis to form C−C bonds by bothintra‐andinetrmolecular processes; as well as C−O and C−N bonds for generating heterocycles.
Functional Plasticity of a Viral Terpene Synthase, OILTS, that Shows Non–Specific Metal Cofactor Binding and Metal–Dependent Biosynthesis
Authors: Jung Youngcheol , Mitsuhashi Takaaki , Kikuchi Takashi , Fujita Makoto 
Published: March 2024

AbstractOILTS is a viral class I terpene synthase found from the giant virus Orpheovirus IHUMI–LCC2. It exhibits a unique structure and demonstrates high plasticity to metal cofactors, allowing it to biosynthesize different cyclic terpene frameworks. Notably, while OILTS produces only (+)‐germacrene D–4–ol with the most common cofactor, Mg2+, it also biosynthesizes a different cyclic terpene, (+)‐cubebol, with Mn2+, Co2+, or Ni2+, presenting a rare instance of cofactor‐dependent enzyme catalysis. This is the first report of (+)‐cubebol biosynthesis, to our knowledge. In addition, OILTS can uptake Zn2+ as a cofactor, which is uncommon among ordinary terpene synthases. These findings suggest that OILTS′s functional plasticity may benefit the virus in diverse host environments, highlighting potential evolutionary implications.
Enhancing Intramolecular Ferromagnetic Coupling in Tetrathiafulvalene–Nitronyl Nitroxide‐Based Compounds through Spin Polarization Mechanism
Authors: Franquesa‐Viñas Pau , Ribas‐Ariño Jordi , Santiago Raul , Deumal Mercè 
Published: March 2024

AbstractSpin‐polarized donor radicals based on tetrathiafulvalene (TTF) derivatives and nitronyl nitroxide (NN) radicals in which one‐electron oxidation involves the HOMO instead of the SOMO are well known for exhibiting magnetoresistance. In particular, BTBN consists of one dibromo‐TTF and one NN radical, which are linked by a phenyl coupler group. One of the key factors driving magnetoresistance is the presence of intramolecular ferromagnetic (FM) coupling between the oxidized π‐donor (TTF+⋅, D unit) and NN (R unit). Here, a theoretical study is carried out to assess suitable candidates with enhanced FM coupling with respect BTBN, which is thus used as a reference. The study is conducted via in silico chemical modification of the substituents of the BTBN basic functional units (D and R radicals, C coupler) to benefit from the spin polarization mechanism to boost the intramolecular FM coupling, aiming to distort the BTBN radical arrangement within the molecular crystal as little as possible, in the event the material can be synthesized. NICSiso(1) and Wiberg's Bond Order are analyzed to further assist in identifying promising potential candidates, since the decrease in aromaticity is expected to enhance the diradical character and give rise to a larger magnetic coupling value. The most favorable diradical building block to replace the BTBN moiety results from using a hydroxyl‐ethylene (−(H)C=C(OH)−) as a coupler preserving BTBN original radicals, namely, NN and TTF+⋅ units. This study aims at illustrating the feasibility of improving the intramolecular FM interaction between radical moieties, which is fully realized, as a first step towards the synthesis of new materials with (possibly) enhanced magnetoresistance properties.
Mono‐Ortho‐Beryllated Carbodiphosphoranes: Synthesis, Structure, Bonding and Reactivity
Authors: Buchner Magnus R. , Kreuzer Lukas K. , Thomas‐Hargreaves Lewis R. , Müller Matthias , Ivlev Sergei I. , Frenking Gernot , Pan Sudip 
Published: March 2024

AbstractThe reaction of organoberyllium compounds with hexaphenylcarbodiphosphorane yields mono‐ortho‐beryllated complexes, which feature a double dative Be=C bond. The bonding situation in these compounds together with a simple carbodiphosphorane and an N‐heterocyclic carbene adduct was analysed with energy decomposition analysis in combination with natural orbital for chemical valence as well as with quantum theory of atoms‐in‐molecules. Furthermore, the driving forces accountable for mono‐ortho‐beryllation were elucidated along with the reactivity of the Be=C bond.
Recovery of valuable metals from cathode materials of spent ternary lithium‐ion battery using natural product as reducing reagent
Authors: Dong Liping , Li Yongjian , Shi Pei , Tian Shichao , Ren Zhongqi , Zhou Zhiyong 
Published: March 2024

AbstractIn recent years, ternary lithium‐ion batteries (LIBs) have been vigorously promoted in the field of new energy vehicles for their excellent overall performance, and the rapid growth of battery production and sales has brought about a proliferation of spent LIBs. The recycling of cathode materials of spent ternary LIBs, which are rich in many valuable metal elements, will bring multiple environmental and economic benefits. In this paper, a systematic study of the key influencing factors in the wet leaching and recycling process was carried out. A natural product tea polyphenol was innovatively used as the reducing reagent, and a sulphuric acid–tea polyphenol leaching system was constructed for the reductive acid leaching of cathode materials of spent ternary LIBs. Under the optimum leaching conditions, the leaching efficiencies of lithium, nickel, cobalt, and manganese were 99.54%, 98.88%, 99.37%, and 98.45%, respectively. After leaching, a stepwise precipitation method was used to separate and recover the valuable metal ions from the leachate. In summary, an innovatively complete recycling process route for cathode materials of spent ternary LIBs was constructed, which provides a solid theoretical basis and technical support for the efficient and clean recycling of spent LIBs.
Pressure Induces Six‐fold Coordination for the Lighter Pnictides Phosphorus and Arsenic Triiodide
Authors: Gain Pranab , Mondal Soumya , Datta Ayan 
Published: March 2024

AbstractIn this study, we employ an evolutionary algorithm in conjunction with first‐principles density functional theory (DFT) calculations to comprehensively investigate the structural transitions, electronic properties, and chemical bonding behaviors of XI3 compounds, where X denotes phosphorus (P) and arsenic (As), across a range of elevated pressures. Our computational analyses reveal a distinctive phenomenon occurring under compression, wherein the initially trigonal structures of PI3 (P 63) and AsI3 (R‐3) undergo an intriguing transformation, leading to the emergence of six‐coordinated monoclinic phases (C2/m) at 6 GPa and 2 GPa for PI3 and AsI3, respectively. These high‐pressure phases exhibit their stability up to 10 GPa for PI3 and 12 GPa for AsI3. Notably, the resulting structures at elevated pressures bear striking resemblance to the widely recognized six‐coordinated octahedral BiI3 crystal configuration observed at ambient conditions. Our investigation further underscores the pivotal role of pressure‐induced reactivity of the lone‐pair electrons in PI3 and AsI3, facilitating their enhanced stereochemical reactivity and thereby enabling higher six‐fold coordination. Complementary analyses employing electron localization function (ELF) and density of states (DOS) effectively delineate the progression towards augmented coordination in PI3 and AsI3 with increasing pressure. While the phenomenon of heightened coordination is conventionally associated with heavier pnictide iodides such as SbI3 and BiI3 under ambient conditions due to heightened ionic character and relativistic effects in bismuth (Bi) and antimony (Sb), our findings accentuate that analogous structural transformations can also be induced in lighter elements like phosphorus (P) and arsenic (As) under the influence of pressure.
Possibilities and Limitations of Kinetic Studies in On‐Surface Synthesis by Real Time X‐ray Photoelectron Spectroscopy
Authors: Lackinger Markus 
Published: March 2024

AbstractThe kinetics of coupling reactions on surfaces can be quantitatively studied in real time by X‐ray Photoelectron Spectroscopy (XPS). From fitting experimental data, kinetic reaction parameters such as the rate constant's pre‐exponential and activation energy can be deduced and compared to quantum chemical simulations. To elucidate the possibilities and limitations of this approach, we propose studies in which experimental data are first simulated and subsequently fitted. Knowing the exact kinetic parameters used in the simulation allows one to evaluate the accuracy of the fit result. Here, several experimental influences, such as the data point density and the addition of noise, are explored for a model reaction with first‐order kinetics. The proposed procedure sheds light on the accuracy with which kinetic parameters can be derived and may also help in the design of future experiments.
Coarsening of Quasi Two‐Dimensional Emulsions Formed by Islands in Free‐Standing Smectic Films
Authors: Klopp Christoph , Trittel Torsten , Stannarius Ralf 
Published: March 2024

AbstractWe study the coarsening behavior of assemblies of islands on smectic A freely suspended films in ISS microgravity experiments. The islands can be regarded as liquid inclusions in a two‐dimensional fluid in analogy to liquid droplets of the discontinuous phase of an emulsion. The coarsening is effectuated by two processes, predominantly by island coalescence, but to some extend also by Ostwald ripening, whereby large islands grow at the expense of surrounding smaller ones. A peculiarity of this system is that the continuous and the discontinuous phases consist of the same material. We determine the dynamics, analyze the self‐similar aging of the island size distribution and discuss characteristic exponents of the mean island growth.
Tetrel Bonding of the Carbenium Ion Forms a Pentacoordinate Carbon Atom
Authors: Scheiner Steve 
Published: March 2024

AbstractAs a flat trigonal species, the CR3+ carbenium ion contains a pair of deep π‐holes above and below its molecular plane. In the case of CH3+ a first base will form a covalent bond with the central C, making the combined species tetrahedral. Approach of a second base to the opposite side results in a longer but rather strong noncovalent tetrel bond (TB). While CMe3+ can also form a similar asymmetric complex with a pair of bases, it also has the capacity to form a pair of nearly equivalent TBs, such that the resulting symmetric trigonal bipyramid configuration is only slightly higher in energy. When the three substituents on the central C are phenyl rings, the symmetric configuration with two TBs predominates. These tetrel bonds are quite strong, reaching up to 20 kcal/mol. Adding OPH2 or OCH substituents to the phenyl rings permits the formation of intramolecular C⋅⋅O TBs to the central C, very similar in many respects to the case where these TBs are intermolecular.
New Perspectives on Delocalization Pathways in Aromatic Molecular Chameleons
Authors: Leyva‐Parra Luis , Casademont‐Reig Irene , Pino‐Rios Ricardo , Ruiz Lina , Alonso Mercedes , Tiznado William 
Published: March 2024

AbstractThis study comprehensively analyzes the magnetically induced current density of polycyclic compounds labeled as “aromatic chameleons” since they can arrange their π‐electrons to exhibit aromaticity in both the ground and the lowest triplet state. These compounds comprise benzenoid moieties fused to a central skeleton with 4n π‐electrons and traditional magnetic descriptors are biased due to the superposition of local magnetic responses. In the S0 state, our analysis reveals that the molecular constituent fragments preserve their (anti)aromatic features in agreement with two types of resonant structures: one associated with aromatic benzenoids and the other with a central antiaromatic ring. Regarding the T1 state, a global and diatropic ring current is revealed. Our aromaticity study is complemented with advanced electronic and geometric descriptors to consider different aspects of aromaticity, particularly important in the evaluation of excited state aromaticity. Remarkably, these descriptors consistently align with the general features on the main delocalization pathways in polycyclic hydrocarbons consisting of fused 4n π‐electron rings. Moreover, our study demonstrates an inverse correlation between the singlet‐triplet energy difference and the antiaromatic character of the central ring in S0.