bluuebunny/crossref_metadata_2025_split huggingface dataset:
Synergistic Effect of Oxygen Vacancy and High Porosity of Nano MIL‐125(Ti) for Enhanced Photocatalytic Nitrogen Fixation
Authors: Sun Yangyang , Ji Houqiang , Sun Yanjun , Zhang Guangxun , Zhou Huijie , Cao Shuai , Liu Sixiao , Zhang Lei , Li Wenting , Zhu Xingwang , Pang Huan 
Published: December 2023

AbstractThis work reports that a low‐temperature thermal calcination strategy was adopted to modulate the electronic structure and attain an abundance of surface‐active sites while maintaining the crystal morphology. All the experiments demonstrate that the new photocatalyst nano MIL‐125(Ti)‐250 obtained by thermal calcination strategy has abundant Ti3+ induced by oxygen vacancies and high specific surface area. This facilitates the adsorption and activation of N2 molecules on the active sites in the photocatalytic nitrogen fixation. The photocatalytic NH3 yield over MIL‐125(Ti)‐250 is enhanced to 156.9 μmol g−1 h−1, over twice higher than that of the parent MIL‐125(Ti) (76.2 μmol g−1 h−1). Combined with density function theory (DFT), it shows that the N2 adsorption pattern on the active sites tends to be from “end‐on” to “side‐on” mode, which is thermodynamically favourable. Moreover, the electrochemical tests demonstrate that the high atomic ratio of Ti3+/Ti4+ can enhance carrier separation, which also promotes the efficiency of photocatalytic N2 fixation. This work may offer new insights into the design of innovative photocatalysts for various chemical reduction reactions.
Organocatalytic Lithium Chloride Oxidation by Covalent Organic Frameworks for Rechargeable Lithium‐Chlorine Batteries
Authors: Xu Yan , Wang Mingming , Sajid Muhammad , Meng Yahan , Xie Zehui , Sun Lidong , Jin Jian , Chen Wei , Zhang Shenxiang 
Published: December 2023

AbstractRechargeable Li−Cl2 battery is a promising high energy density battery system. However, reasonable cycle life could only be achieved under low specific capacities due to the sluggish oxidation of LiCl to Cl2. Herein, we propose an amine‐functionalized covalent organic framework (COF) with catalytic activity, namely COF−NH2, that significantly decreases the oxidation barrier of LiCl and accelerates the oxidation kinetics of LiCl in Li−Cl2 cell. The resulting Li−Cl2 cell using COF−NH2 (Li−Cl2@COF−NH2) simultaneously exhibits low overpotential, ultrahigh discharge capacity up to 3500 mAh/g and a promoted utilization ratio of deposited LiCl at the first cycle (UR−LiCl) of 81.4 %, which is one of the highest reported values to date. Furthermore, the Li−Cl2@COF−NH2 cell could be stably cycled for over 200 cycles when operating at a capacity of 2000 mAh/g at −20 °C with a Coulombic efficiency (CE) of ≈100 % and a discharge plateau of 3.5 V. Our superior Li−Cl2 batteries enabled by organocatalyst enlighten an arena towards high‐energy storage applications.
Influence of TiO2 nanofiller geometry on the rheological and optical properties of poly(acrylic acid)‐based nanocomposite hydrogels
Authors: Vera Myleidi , Mella Claudio , Palacio Daniel , Surabhi Srivathsava , Boury Bruno , Bouchmella Karim , Jeong Jong‐Ryul , Urbano Bruno F. 
Published: December 2023

AbstractThe properties of macroscopic polymer nanocomposites are highly dependent on the nanoparticle–polymer interfacial region, which varies with the morphology of the nanoparticles. Herein, we used TiO2 nanofillers with very low aspect ratio, the same chemical composition, and surface functions, but different geometries (nanospheres and nanoplates) dispersed in a poly(acrylic acid) matrix to analyze the influence of the nanoparticle geometry on the properties of nanocomposite hydrogels. The geometry was found to affect the swelling and rheological properties of the nanocomposite polymers. Particularly, the yield strain (from 25% to 130%), modulus (from 17,500 to 25,000 Pa), and brittleness of nanoplates based nanocomposite increased more significantly. Finite‐difference time‐domain simulations demonstrated that nanoplates increased the wavelength of the absorption maxima (224 nm for NS to 240 nm for NP) and charge distribution. The results obtained in this research indicate that the nanofiller shape markedly influences the rheological properties of the nanocomposite polymers, opening the door to further research focused on polymer–nanofiller interactions, and their effect on the macroscopic properties of the nanocomposites.
How “international” is international research collaboration?
Authors: Gök Abdullah , Karaulova Maria 
Published: December 2023

AbstractIn the context of the increasing global connectivity in science, this article investigates the internal heterogeneity of international research collaborations (IRCs). We focus on the prevalence of shared heritage collaborations and the rise of multiple institutional affiliations as a collaboration mechanism. An analytical typology of IRCs based on the characteristics of collaborating researchers' location and heritage is developed and empirically tested on the dataset of Russia's publications in 2015. We found that shared heritage IRC and IRC via multiple affiliations are the cornerstones of internationalization. Significant structural differences are revealed between conventional IRC and these nonconventional IRCs across fields of science, locations, visibility of international partners, and the sources of funding. These results contribute towards a better understanding of IRC as a complex, heterogeneous phenomenon, which encompasses a variety of arrangements for knowledge creation across borders. A more nuanced understanding of IRC is needed for smarter university strategy, metric development, and policymaking.
Modern Organometallic C−H Functionalizations with Earth‐Abundant Iron Catalysts: An Update
Authors: Cattani Silvia , Cera Gianpiero 
Published: December 2023

AbstractIron‐catalyzed C−H activation has recently emerged as an increasingly powerful synthetic method for the step‐ and atom‐ economical direct C−H functionalizations of otherwise inert C−H bonds. Iron's low‐cost and toxicity along with its catalytic versatility have encouraged the scientific community to elect this metal for the development of new C−H activation methodologies. Within this review, we aim to present a collection of the most recent examples of iron‐catalyzed C−H functionalizations with a particular emphasis on modern synthetic strategies and mechanistic aspects.
Enzymatic Strategies for the Biosynthesis of N‐Acyl Amino Acid Amides
Authors: Kua Glen Kai Bin , Nguyen Giang Kien Truc , Li Zhi 
Published: December 2023

AbstractAmide bond‐containing biomolecules are functionally significant and useful compounds with diverse applications. For example, N‐acyl amino acids (NAAAs) are an important class of lipoamino acid amides with extensive use in food, cosmetic and pharmaceutical industries. Their conventional chemical synthesis involves the use of toxic chlorinating agents for carboxylic acid activation. Enzyme‐catalyzed biotransformation for the green synthesis of these amides is therefore highly desirable. Here, we review a range of enzymes suitable for the synthesis of NAAA amides and their strategies adopted in carboxylic acid activation. Generally, ATP‐dependent enzymes for NAAA biosynthesis are acyl‐adenylating enzymes that couple the hydrolysis of phosphoanhydride bond in ATP with the formation of an acyl‐adenylate intermediate. In contrast, ATP‐independent enzymes involve hydrolases such as lipases or aminoacylases, which rely on the transient activation of the carboxylic acid. This occurs either through an acyl‐enzyme intermediate or by favorable interactions with surrounding residues to anchor the acyl donor in a suitable orientation for the incoming amine nucleophile. Recently, the development of an alternative pathway involving ester‐amide interconversion has unraveled another possible strategy for amide formation through esterification‐aminolysis cascade reactions, potentially expanding the substrate scope for enzymes to catalyze the synthesis of a diverse range of NAAA amides.
Highly Selective Thioether Oxidation with H2O2 Catalyzed by Zr‐Substituted Keggin Phosphotungstate: Mechanistic Insights
Authors: Zalomaeva Olga V. , Maksimchuk Nataliya V. , Marikovskaya Sofia M. , Antonov Artem A. , Kholdeeva Oxana A. 
Published: December 2023

AbstractThe Zr‐monosubstituted phosphotungstate (Bu4N)8[{PW11O39Zr(μ‐OH)(H2O)}2] (1) is a highly active and selective catalyst for thioether sulfoxidation with aqueous H2O2 in acetonitrile or acetonitrile/ethanol. The reaction proceeds unprecedentedly fast and completes within seconds at room temperature. Various sulfides produce corresponding sulfoxides with selectivity of 98–99 % and oxidant utilization efficiency of 92–99 %. The reaction mechanism was investigated using test substrates, kinetic, isotopic labeling, and spectroscopic tools. The oxidation of thianthrene‐5‐oxide and competitive sulfide‐sulfoxide oxidation point to an electrophilic oxidation mechanism, but a V‐shaped Hammett plot found for oxidation of p‐substituted thioanisoles may suggest a biphilic nature of active species. Kinetic studies revealed that the rate‐limiting step of the reaction is the interaction of a peroxo zirconium intermediate with organic substrates. ATR‐FT‐IR and 31P NMR spectroscopic studies coupled with stoichiometric experiments indicated that peroxo species capable of transferring an oxygen atom to thioethers are dimeric side‐on mono‐ and diperoxo complexes, [Zr2(μ‐η2 : η2‐O2){PW11O39}2(H2O)x]]8− (I) and [{Zr(μ‐η2‐O2)}2(PW11O39)2(H2O)y]10− (II), and monomeric Zr‐hydroperoxo [Zr(η2‐OOH)PW11O39]4− (III) and peroxo [Zr(η2‐O2)PW11O39]5− (IV) species, which dominate at high excess of H2O2. While I and III are endowed with electrophilic oxygen, which can be transferred to electron‐rich sulfides, more negatively charged II and IV preferably react with thioethers comprising electron‐withdrawing substituents.
Enhancing multifunctional photocatalysis with acetate‐assisted cesium doping and unlocking the potential of Z‐scheme solar water splitting
Authors: Ma Mengmeng , Li Jingzhen , Zhu Xiaogang , Liu Kong , Huang Kaige , Yuan Guodong , Yue Shizhong , Wang Zhijie , Qu Shengchun 
Published: December 2023

AbstractGraphitic carbon nitride (g‐C3N4) has been extensively doped with alkali metals to enlarge photocatalytic output, in which cesium (Cs) doping is predicted to be the most efficient. Nevertheless, the sluggish diffusion and doping kinetics of precursors with high melting points, along with imprecise regulation, have raised the debate on whether Cs doping could make sense. For this matter, we attempt to confirm the positive effects of Cs doping on multifunctional photocatalysis by first using cesium acetate with the character of easy manipulation. The optimized Cs‐doped g‐C3N4 (CCN) shows a 41.6‐fold increase in visible‐light‐driven hydrogen evolution reaction (HER) compared to pure g‐C3N4 and impressive degradation capability, especially with 77% refractory tetracycline and almost 100% rhodamine B degraded within an hour. The penetration of Cs+ is demonstrated to be a mode of interlayer doping, and Cs–N bonds (especially with sp2 pyridine N in C═N–C), along with robust chemical interaction and electron exchange, are fabricated. This atomic configuration triggers the broadened spectral response, the improved charge migration, and the activated photocatalytic capacity. Furthermore, we evaluate the CCN/cadmium sulfide hybrid as a Z‐scheme configuration, promoting the visible HER yield to 9.02 mmol g−1 h−1, which is the highest ever reported among all CCN systems. This work adds to the rapidly expanding field of manipulation strategies and supports further development of mediating served for photocatalysis.
Capturing Sialyl‐glycan on Live Cancer Cells by Tailored Boronopeptide**
Authors: Chatterjee Saurav , Chowdhury Arnab , Saproo Sheetanshu , Mani Tripathi Nitesh , Naidu Srivatsava , Bandyopadhyay Anupam 
Published: December 2023

AbstractBoronic acid‐containing molecules are substantially popularized in chemical biology and medicinal chemistry due to the broad spectrum of covalent conjugations as well as interaction modules offered by the versatile boron atom. Apparently, the WGA peptide (wheat germ agglutinin, 62–73), which shows a considerably low binding affinity to sialic acid, turned into a selective and >5 folds potent binder with the aid of a suitable boronic acid probe installed chemoselectively. In silico studies prompted us to install BA probes on the cysteine residue, supposedly located in close proximity to the bound sialic acid. In vitro studies revealed that the tailored boronopeptides show enhanced binding ability due to the synergistic recognition governed by selective non‐covalent interactions and cis‐diol boronic acid conjugation. The intense binding is observed even in 10 % serum, thus enabling profiling of sialyl‐glycan on cancer cells, as compared with the widely used lectin, Sambucus nigra. The synergistic binding mode between the best boronopeptide (P3) binder and sialic acid was analyzed via 1H and 11B NMR.
Separator Design Strategies to Advance Rechargeable Aqueous Zinc Ion Batteries
Authors: Du He , Yi Zhihui , Li Huiling , Lv Wensong , Hu Nan , Zhang Xiaoyan , Chen Wenjian , Wei Zongwu , Shen Fang , He Huibing 
Published: December 2023

AbstractWith the increasing demand for low‐cost and high‐safety portable batteries, aqueous zinc‐ion batteries (ZIBs) have been regarded as a potential alternative to the lithium‐ion batteries, bringing about extensive research dedicated in the exploration of high‐performance and highly reversible ZIBs. Although separators are generally considered as non‐active components in conventional research on ZIBs, advanced separators designs seem to offer effective solutions to the majority of issues within ZIBs system. These issues encompass concerns related to the zinc anode, cathode, and electrolyte. Initially, we delve into the origins and implications of various inherent problems within the ZIBs system. Subsequently, we present the latest research advancements in addressing these challenges through separators engineering. This includes a comprehensive, detailed exploration of various strategies, coupled with instances of advanced characterizations to provide a more profound insight into the mechanisms that influence the separators. Finally, we undertake a multi‐criteria evaluation, based on application standards for diverse substrate separators, while proposing guiding principles for the optimal design of separators in zinc batteries. This review aims to furnish valuable guidance for the future development of advanced separators, thereby nurturing progress in the field of ZIBs.
Ferrocenyl Dinuclear Gold(I) Complexes. Study of their Structural Features and the Influence of Bridging and Phosphane Ligands in a Catalytic Cyclization Reaction
Authors: Pérez‐Sánchez Juan Carlos , Herrera Raquel P. , Concepción Gimeno M. 
Published: December 2023

AbstractThe combination of the ferrocene moiety with gold(I) catalysis remains a relatively unexplored field. In this article, we delve into the synthesis, characterization, and potential catalytic activity of four complexes utilizing both monodentate and bidentate ferrocenyl diphenylphosphane ligands (ppf and dppf), coordinated with two gold(I) metal centers, linked by either chloride or pentafluorophenylthiolate bridging ligands. This leads to the formation of cationic “self‐activated” precatalysts capable of initiating the catalytic cycle without the need for external additives. The catalytic activity of these complexes was assessed through a model reaction in gold(I) catalysis, specifically the cyclization of a N‐propargylbenzamide to produce an oxazole. In addition, we studied and compared the influence exerted by both the phosphane and the bridging ligand on the performance of these catalysts.
Gele aus materialchemischer Sicht
Authors: Schubert Ulrich 
Published: December 2023

ZusammenfassungGele bestehen aus einer festen und einer flüssigen Phase, die sich gegenseitig durchdringen. Die Flüssigkeit wird dadurch immobilisiert. Bei Hydrogelen ist die flüssige Phase Wasser, bei Organogelen eine andere Flüssigkeit. Zur Bildung der festen Phase müssen natürliche oder synthetische Polymere, Moleküle oder kolloidale Partikel durch kovalente Bindungen oder nicht‐kovalente Wechselwirkungen quervernetzt werden. Anhand ausgewählter Anwendungsbeispiele werden in diesem Artikel unterschiedliche Arten von Gelen und Netzwerkstrukturen vorgestellt.
SMSE: A serverless platform for multimedia cloud systems
Authors: Denninnart Chavit , Amini Salehi Mohsen 
Published: December 2023

SummaryAlong with the rise of domain‐specific computing (ASICs hardware) and domain‐specific programming languages, we envision that the next step is the emergence of domain‐specific cloud platforms. Considering multimedia streaming as one of the most trendy applications in the IT industry, the goal of this study is to develop serverless multimedia streaming engine (SMSE), the first domain‐specific serverless platform for multimedia streaming. SMSE democratizes multimedia service development via enabling content providers (or even end‐users) to rapidly develop their desired functionalities on their multimedia contents. Upon developing SMSE, the next goal of this study is to deal with its efficiency challenges and develop a function container provisioning method that can efficiently utilize cloud resources and improve the users' quality of service. In particular, we develop a dynamic method that provisions durable or ephemeral containers depending on the spatiotemporal and data‐dependency characteristics of the functions. Evaluating the prototype implementation of SMSE under real‐world settings demonstrates its capability to reduce both the containerization overhead, and the makespan time of serving multimedia processing functions (by up to 30%) in compare to the function provision methods that are being used in the general‐purpose serverless cloud systems.
Soybean planting date and seeding rate effect on germinability and vigor of harvested seed
Authors: Colet Fabiano , Lindsey Alexander J. , Lindsey Laura E. 
Published: December 2023

AbstractSeed is one of the most crucial inputs for soybean [Glycine max (L.) Merr.] production due to its influence on plant population, uniformity, and yield, as well as its cost as an input. Seeds of good quality have high germinability and vigor, providing an adequate stand with uniformly good growth and development even under adverse conditions. This study aimed to measure the effect of soybean planting date and seeding rate on harvested seed mass, seed germinability, and seed vigor. Seeds were collected from a field experiment during the 2020 and 2021 growing seasons at two locations in Ohio: Western Agricultural Research Station and Northwest Agricultural Research Station. The study was conducted using a split‐plot randomized complete block design (planting date–whole plot; seeding rate–subplot) with four replications. Standard germination and accelerated aging tests were conducted in the laboratory using seeds harvested from the field study. All four site‐years demonstrated that planting soybean very late (June 16–July 1) produced lower weight seeds than the other planting dates. Across planting date and seeding rate treatments, the harvested seed germinability was ≥94%. However, soybean planted in early June (June 1–June 15) had the lowest seed vigor results (64%–81%) compared to other planting dates (80%–89%). Rainfall at R7–R8 development stages is negatively correlated with the seed vigor. The results will help seed producers optimize seed production and quality and suggest avoiding planting in June to increase harvested seed vigor.
Variation in seed protein, selected minerals, phytic acid, and potential mineral bioavailability of cowpea [Vigna unguiculata (L.) Walp] mutants and accessions
Authors: Ntswane Moshieng , Labuschagne Maryke , Shandu Siphiwokuhle F. , Mbuma Ntombokulunga W. 
Published: December 2023

AbstractCowpea [Vigna unguiculata (L.) Walp] has the potential to contribute to the eradication of hunger and malnutrition. The study objectives were to evaluate the variability of cowpea mutants; International Institute of Tropical Agriculture (IITA) and South African genotypes for protein content, selected minerals, phytic acid, and the bioavailability of iron (Fe) and zinc (Zn); to identify superior cowpea mutants, IITA, and South African genotypes; and to determine the correlation between measured characteristics. A total of 31 cowpea genotypes were planted at five different environments in South Africa. Significant (p ≤ 0.05) genotype and genotype by environment interaction effects were observed for protein, minerals, and phytic acid concentration. High broad‐sense heritability (>50%) was observed for almost all the characteristics. Thirteen Namibian mutants, five IITA genotypes, and six South African genotypes that combined high protein, Fe, and Zn were identified. The IITA genotype IT93K‐452‐1 and South African genotypes Oloyin and Orelu had good Fe bioavailability. Nine Namibian mutants, four IITA genotypes, and three South African genotypes were associated with high values for protein, manganese, phytic acid, molar ratios of phytic acid with Fe and Zn, and ash. The identified superior cowpea mutants, IITA and South African genotypes could be a good source of the essential minerals and should be further studied for adaptability in South African agroecologies.
Polymers from Cellulosic Waste: Direct Polymerization of Levoglucosenone using DBU as a Catalyst
Authors: Pollard Brett , Gardiner Michael G. , Banwell Martin G. , Connal Luke A. 
Published: December 2023

AbstractThe bio‐based platform molecule levoglucosenone (LGO) is now produced at multi‐ton scale by the pyrolysis of cellulosic waste. As such it has become an industrially viable, non‐petroleum‐derived chemical feedstock. Herein we report the direct (one‐step) and operationally simple polymerization of LGO that provides a highly sustainable method for polymer synthesis. Specifically, the ability of LGO to act as an electrophile has been harnessed so as to deliver high molecular weight polymers (Mn=236,000 g/mol, Đ=2.4) possessing excellent thermal stabilities (TD5 %=249 °C). Furthermore, there is a significant capacity for the effective chemical manipulation of these polymers as exemplified by treatment of them under Baeyer‐Villiger conditions and so creating a simple and green route to hydrophilic materials. These one‐ and two‐step transformations provide the most direct route to new, LGO‐derived polymer scaffolds yet reported. E‐factors of ca. 0.012 and atom economies of up to 99 % have been realized.
Nitrile‐functionalized Poly(siloxane) as Electrolytes for High‐Energy‐Density Solid‐State Li Batteries
Authors: Okur Faruk , Sheima Yauhen , Zimmerli Can , Zhang Huanyu , Helbling Patrick , Fäh Ashling , Mihail Iacob , Tschudin Jacqueline , Opris Dorina M. , Kovalenko Maksym V. , Kravchyk Kostiantyn V. 
Published: December 2023

AbstractIn the quest to replace liquid Li‐ion electrolytes with safer and non‐toxic solid counterparts for Li‐ion batteries, polysiloxane polymers have attracted considerable attention as they offer low glass transition temperatures, stability with metallic lithium, and versatility in chemical functionalization of the backbone. Herein, we present the synthesis of Li‐ion conductive polysiloxane‐based polymers functionalized with 60 % nitrile groups per chain unit. The synthesis procedure is based on the reaction of poly‐(dimethylsiloxane‐co‐methylvinylsiloxane) polymer with 2‐cyanoethanethiol, followed by the addition of lithium bis (trifluoromethanesulfonyl) imide. The presented polysiloxane‐based polymers exhibit exceptionally high ionic conductivity up to 0.375 mS cm−1 at 60 °C and Li+ ion transfer number of 0.73, one of the highest reported for polymer Li‐ion conducting electrolytes. Their electrochemical performance was evaluated in both symmetrical and full‐cell configurations to test the utility of synthesized polymers as electrolytes in Li‐ion batteries.