bluuebunny/crossref_metadata_2025_split huggingface dataset:
Phosphorescence by Trapping Defects in Boric Acid Induced by Thermal Processing
Authors: Stagi Luigi , Malfatti Luca , Zollo Alessia , Livraghi Stefano , Carboni Davide , Chiriu Daniele , Corpino Riccardo , Ricci Pier Carlo , Cappai Antonio , Carbonaro Carlo Maria , Enzo Stefano , Khaleel Abbas , Adamson Abdulmuizz , Gervais Christel , Falqui Andrea , Innocenzi Plinio 
Published: November 2023

AbstractThe phosphorescence of boric acid (BA, H3BO3) at room temperature is a puzzling phenomenon subject to controversial interpretations although the role of structural defects has not yet been considered. Heat treatments of boric acid cause its transformation into the metaboric phase and amorphous boron oxide (B2O3). The structural changes after thermal processing can create defects that become centers of luminescence and recombination channels in the visible range. In the present work, commercial boric acid is thermally processed at different temperatures. Samples treated between 200 and 400 °C exhibit remarkable phosphorescence in the visible range. At ≈480 and 528 nm, two distinct phosphorescent emissions occur, associated with trapped charge carriers recombinations identified by thermoluminescence (TL) and electron paramagnetic resonance spectroscopy (EPR). The structural and optical studies suggest that the activation of boric acid phosphorescence after heat treatment is correlated with the presence of defects. The afterglow results from a trapping and detrapping process, which delays the recombination at the active optical centers. Time‐dependent density functional study (DFT) of defective BOH molecules and clusters shows the emergence of near UV and blue optical transitions in absorption. These defects trigger the photoluminescence in thermally processed boric acid samples.
“Bobbit Worm”‐Inspired Soft Adaptive Grasper with Self‐Generated Triboelectric Force Sensor
Authors: Zhu Zhisen , Dai Keren , Wang Mingchuan , Jiang Liangjing , Bian Leixiang , Zhang Wenling , Tian Yu 
Published: November 2023

AbstractSoft actuators can realize delicate adaptive grasping of fragile and irregularly shaped objects, which are essential in biological and engineering systems. Yet, critical concerns in the frontier soft graspers are insufficient grasping ability and functional limitations. Here, we propose a Bobbit worm‐inspired multimodal‐sensing adaptive soft grasper (MSASG) enabled by harnessing the Miura‐origami skeleton integrated with self‐generated triboelectric force sensors (TFSs). The Miura‐origami skeleton endows the soft grasper a high grasping force while provides an energy‐efficient way to passively embrace an object without extra energy input. A multimodal TFSs with tactile sensing (TFS‐1) and pressure‐feedback (TFS‐2) functions is constructed by directly packaging a pyramid‐pattern elastic film on the Miura‐origami skeleton. The MSASG implement fast grasping or releasing action by evaluating pressures of various approaching prey, including hermit crabs, crickets, and beetle, etc. And its sensitivity greater than 0.18 V mN−1. In particular, the grasping performances and triboelectric sensing capacity can be optimized by modulating topological parameters (crease length, and surface film thickness, etc.), using a combination of theoretical modeling, finite element simulations, and experiments. The bionic design of soft graspers broadens the future applications for versatile human‐robot‐environment interaction scenarios, such as adaptive robots, reconfigurable architectures, medical devices, and deep‐sea explorations.
In Situ Formed Amorphous Bismuth Sulfide Cathodes with a Self‐Controlled Conversion Storage Mechanism for High Performance Hybrid Ion Batteries
Authors: Zhang Wei , Sun Yuanhe , Ren Zhiguo , Zhao Yuanxin , Yao Zeying , Lei Qi , Si Jingying , Li Zhao , Ren Xiaochuan , Li Xiaolong , Li Aiguo , Wen Wen , Zhu Daming 
Published: November 2023

AbstractConversion‐type electrodes offer a promising multielectron transfer alternative to intercalation hosts with potentially high‐capacity release in batteries. However, the poor cycle stability severely hinders their application, especially in aqueous multivalence‐ion systems, which can fundamentally impute to anisotropic ion diffusion channel collapse in pristine crystals and irreversible bond fracture during repeated conversion. Here, an amorphous bismuth sulfide (a‐BS) formed in situ with unprecedentedly self‐controlled moderate conversion Cu2+ storage is proposed to comprehensively regulate the isotropic ion diffusion channels and highly reversible bond evolution. Operando synchrotron X‐ray diffraction and substantive verification tests reveal that the total destruction of the Bi─S bond and unsustainable deep alloying are fully restrained. The amorphous structure with robust ion diffusion channels, unique self‐controlled moderate conversion, and high electrical conductivity discharge products synergistically boosts the capacity (326.7 mAh g−1 at 1 A g−1), rate performance (194.5 mAh g−1 at 10 A g−1), and long‐lifespan stability (over 8000 cycles with a decay rate of only 0.02 ‰ per cycle). Moreover, the a‐BS Cu2+‖Zn2+ hybrid ion battery can well supply a stable energy density of 238.6 Wh kg−1 at 9760 W kg−1. The intrinsically high‐stability conversion mechanism explored on amorphous electrodes provides a new opportunity for advanced aqueous storage.
Designing Polymer Electrolytes via Ring‐Opening Polymerization for Advanced Lithium Batteries
Authors: Wang Shi , Zhang Lei , Zeng Qinghui , Guan Jiazhu , Gao Haiqi , Zhang Liaoyun , Zhong Jin , Lai Wen‐Yong , Wang Qian 
Published: November 2023

AbstractReplacing liquid electrolytes with solid‐state polymer electrolytes (SPEs) can solve the safety hazards of Li metal batteries (LMBs) while increasing their energy density. However, there has been limited success so far in preparing advanced SPEs with controllable molecular structure and chemical composition, posing great obstacles to further promoting its application in LMBs. Recently, ring‐opening polymerization (ROP), including cationic ROP, anionic ROP, and ring‐opening metathesis polymerization, has become a dazzling new star in achieving SPEs due to its mild polymerization conditions and controllable chemical composition (molecular structure, functional group), etc. Besides, there is no small molecule released during the polymerization process, which means reduced interfacial side reaction. Hence, in this review, the merits of ROP in preparing SPEs and its mechanism as well as interfering factors, etc are evaluated from the perspective of synthetic chemistry. Furthermore, the review focuses on outlining the existing cases related to ROP as much as possible and summarize them from different ring structures (from triple ring to multivariate ring) and polymerization methods, hoping to provide a comprehensive understanding and serve as strategic guidance for designing high‐performance SPEs. Challenges and opportunities regarding this burgeoning field are also discussed at the end.
Optimizing the cask effect in multicomponent natural gas purification to provide high methane productivity
Authors: Chen Yuxin , Jiang Yunjia , Li Jiahao , Hong Xianghao , Ni Haofei , Wang Lingyao , Ma Nan , Tong Mingman , Krishna Rajamani , Zhang Yuanbin 
Published: November 2023

AbstractThe efficient separation of CH4 from natural gas containing C2H6 and C3H8 impurities is an important topic. Previous work on the separation of CH4/C2H6/C3H8 mixtures often focuses on the C3H8/CH4 selectivity, inadvertently sidelining the critical importance of C2H6/CH4 selectivity. This oversight results in reduced CH₄ productivity and compromised separation efficiency, a phenomenon often termed as the “cask effect.” Herein, we fine‐tune the interrelationship between thermodynamics and kinetics, targeting enhanced CH4 production. A synergistic thermodynamic–kinetic C3H8/CH4 and C2H6/CH4 selectivity is achieved using dynamic breakthrough experiments, underpinned by the stable metal–organic framework TIFSIX‐Cu‐TPA. The CH4 productivity in TIFSIX‐Cu‐TPA is up to 5 mmol g−1, surpassing most of the popular materials. Detailed density functional theory and molecular dynamics computational insights reveal a counteractive thermodynamic–kinetic relationship, proving pivotal for the simultaneous breakthrough of C2H6 and C3H8 under optimal conditions. Moreover, precise adsorption sites of C2H6 and C3H8 are clearly determined through in situ single‐crystal structures.
Not just females and males: Unravelling the complex sex determinism of the hemp palm, Trachycarpus fortunei
Authors: Jousson Antoine , Naciri Yamama , Christe Camille , Marazzi Brigitte , Stauffer Fred 
Published: November 2023

AbstractPremiseThe ornamental Asian palm Trachycarpus fortunei (Arecaceae: Coryphoideae) is widely planted in temperate regions. In Europe, it has spread outside of gardens, particularly on the southern side of the Alps. Sexual expression in the species is complex, varying from dioecy to polygamy. This study investigated (1) sexual floral development and (2) genetic markers implicated in sex determinism.MethodsThe morphology and anatomy of floral organs at different developmental stages were studied using SEM observations and anatomical section. Sex determinism was explored using a genome‐wide association study approach, searching for correlations between 31,000 single‐nucleotide polymorphisms and sex affiliation of 122 palms from 21 wild populations.ResultsWe observed that sexual differentiation appears late in floral development of T. fortunei. Morpho‐anatomical characters of flowers conducive to panmixia were observed, such as well‐differentiated septal nectaries that are thought to promote cross‐pollination. At the molecular level, homozygous and heterozygous allelic systems with closely linked regions were found for sex determinism in individuals with female and “dominant‐male” phenotypes, respectively. Through our wide sampling in the southern Alps, the closely linked genetic regions in males suggest that at least fifteen percent of wild palms are the direct offspring of “males” that can also produce fertile pistillate flowers.ConclusionsTrachycarpus fortunei is a further example of unstable sexual expression found in the family Arecaceae and represents an evolutionary path towards an XY genetic system. Our structural and genetic results may explain the high species dispersal ability in the southern Alps.
Differential sex‐association between PCSK1 polymorphisms and obesity risk in Portuguese children
Authors: Manco Licínio , Albuquerque David , Aranda Beatriz , Rodrigues Daniela , Machado‐Rodrigues Aristides M. , Padez Cristina 
Published: November 2023

AbstractObjectivesThe proprotein convertase subtilisin/Kexin type 1 gene (PCSK1) is implicated in hypothalamic appetite control. Several studies have addressed the relationship between PCSK1 polymorphisms and obesity, although conflicting results were observed. We tested the potential association of four PCSK1 variants with the risk of overweight/obesity and related variables in Portuguese children.MethodsThis is a case–control study, where four PCSK1 variants, rs6230 (c.−101T>C), rs6232 (p.N221D), rs6235 (p.S690T), and rs3811942 (c.*265T>C), were analyzed in Portuguese children (aged 5–13 years‐old). Anthropometric measures were objectively collected and used to provide weight‐for‐age, height‐for‐age, and body mass index (BMI) for age. The indices generated were compared to standard reference values of WHO to obtain the corresponding Z‐scores.ResultsLogistic regression, in the dominant model, revealed no significant associations between the four individual PCSK1 variants and the risk of overweight/obesity in the total population. However, stratifying the sample by sex, a marginally significant association was found between the rs6235 minor C‐allele and increased overweight/obesity in boys (n = 345) (OR 1.55 [1.01–2.38] p = .044), but not in girls (n = 340) (OR 0.73 [0.46–1.14] p = .169). Consistently, boys with genotype GG presented lower BMI Z‐score (0.62) when compared to those with the genotypes GC + CC (1.04). Testing for different effects in males versus females, a significant interaction was found between the rs6235 polymorphism and sex for BMI Z‐score (p = .025).ConclusionsResults of this study suggest for a sex‐differentiated association between PCSK1 rs6235 and overweight/ obesity in Portuguese children.
Synthesis of N‐Acylsulfenamides from (Hetero)Aryl Iodides and Boronic Acids by One‐Pot Sulfur‐Arylation and Dealkylation
Authors: Greenwood Nathaniel S. , Cerny Nicholas P. , Deziel Anthony P. , Ellman Jonathan A. 
Published: November 2023

AbstractA general one‐pot approach to diverse N‐acylsulfenamides from a common S‐phenethylsulfenamide starting material is reported. This approach was demonstrated by C−S bond formation utilizing commercially abundant (hetero)aryl iodides and boronic acids to provide sulfilimine intermediates that undergo thermal elimination of styrene. In contrast, all prior approaches to N‐acylsulfenamides rely on thiol inputs to introduce sulfenamide S‐substituents. A broad scope of reaction inputs was demonstrated including for approved drugs and drug precursors with dense display of functionality. Several different types of sulfur functionalization were performed on a sulfenamide derived from a complex precursor of the blockbuster anticoagulant drug apixaban, highlighting the utility of this approach for the introduction of high oxidation state sulfur groups in complex bioactive compounds. Mechanistic studies established that the key styrene elimination step proceeds by a concerted elimination that does not require reagents or catalysts, and therefore, this one‐pot approach should be applicable to the synthesis of N‐acylsulfenamides utilizing diverse electrophiles and reaction conditions for C−S bond formation.
Stereocontrolled Synthesis of α‐3‐Deoxy‐d‐manno‐oct‐2‐ulosonic Acid (α‐Kdo) Glycosides Using C3‐p‐Tolylthio‐Substituted Kdo Donors: Access to Highly Branched Kdo Oligosaccharides
Authors: Sun Ao , Li Zipeng , Wang Yuchao , Meng Shuai , Zhang Xiao , Meng Xiangbao , Li Shuchun , Li Zhongtang , Li Zhongjun 
Published: November 2023

Abstract3‐Deoxy‐d‐manno‐oct‐2‐ulosonic acid (Kdo) is an eight‐carbon monosaccharide found widely in bacterial lipopolysaccharides (LPSs) and capsule polysaccharides (CPSs). We developed an indirect method for the stereoselective synthesis of α‐Kdo glycosides with a C3‐p‐tolylthio‐substituted Kdo phosphite donor. The presence of the p‐tolylthio group enhanced the reactivity, suppressed the formation of elimination by‐products (2,3‐enes), and provided complete α‐stereocontrol. A variety of Kdo α‐glycosides were synthesized by our method in excellent yields (up to 98 %). After glycosylation, the p‐tolylthio group can be efficiently removed by free‐radical reduction. Subsequently, the orthogonality of the phosphite donor and thioglycoside donor was demonstrated by the one‐pot synthesis of a trisaccharide in Helicobacter pylori and Neisseria meningitidis LPS. Moreover, an efficient total synthesis route to the challenging 4,5‐branched Kdo trisaccharide in LPSs from several A. baumannii strains was highlighted. To demonstrate the high reactivity of our approach further, the highly crowded 4,5,7,8‐branched Kdo pentasaccharide was synthesized as a model molecule for the first time. Additionally, the reaction mechanism was investigated by DFT calculations.
Sulfonium Cation in the Service of π‐Acid Catalysis**
Authors: Li Ruiping , Zafar Mohammad , Danovich David , Subramaniyan Vasudevan , Tibika Françoise , Tulchinsky Yuri 
Published: November 2023

AbstractWhile still rare, cationic ligands offer much promise as tunable electron‐withdrawing ligands for π‐acid catalysis. Recently, we introduced pincer‐type sulfonium cations into the list of available strongly π‐acidic ancillary ligands. However, the M−S bond in sulfonium complexes of these ligands was found highly labile, precluding their catalytic applications. Herein we demonstrate that this obstacle can be overcome by increasing the rigidity of the sulfonium pincer scaffold. X‐ray analyses confirm that despite bearing a formal positive charge, the sulfur atom of this newly designed sulfonium ligand maintains its coordination to the Pt(II)‐center, while DFT calculations indicate that by doing so it strongly enhances the electrophilic character of the metal. Kinetic studies carried out on three model cycloisomerization reactions prove that such a tris‐cationic sulfonium‐Pt(II) complex is highly reactive, compared to its thioether‐based analogue. This proof‐of‐concept study presents the first example of employing sulfonium‐based ligands in homogeneous catalysis.
An Electrolyte with Less Space‐Occupying Diluent at Cathode Inner Helmholtz Plane for Stable 4.6 V Lithium‐Ion Batteries
Authors: Fang Mingming , Du Bingyuan , Zhang Xinran , Dong Xubing , Yue Xinyang , Liang Zheng 
Published: November 2023

AbstractReasonably elevating the working voltage (≥4.4 V vs. Li/Li+) of the cathode is one of the efficient approaches to maximize the energy density of lithium‐ion batteries (LIBs). As a preferred partner for high‐voltage LIB systems, localized high‐concentration electrolyte (LHCE), characterized by a stronger Li solvation structure, less free solvent, and robust electrode/electrolyte interphase has attracted much attention in academic circles. Herein, we systematically studied the role of the diluent in LHCE on the formation of the cathode electrolyte interphase (CEI) and elucidated that the existing anion‐diluent pairing in the inner Helmholtz plane (IHP) results in an uneven CEI and subsequent battery degradation under high voltage. A m‐fluorotoluene (mFT) diluent was further employed in the LHCE containing lithium difluoro(oxalato)borate (LiDFOB) to facilitate a uniform and rich‐anion‐derived CEI, since the weaker interaction of HmFT−BDFOB−, as compared to the HHhydrofluoroether−BDFOB−, reduces the influence of mFT in IHP or initial CEI formation. Consequently, the mFT‐dominated LHCE propels the high‐voltage performance of LIBs one step forward, endowing a 4.6 V‐class 1.2‐Ah graphite||LiNi0.8Co0.1Mn0.1O2 pouch cells a 90.4 % capacity retention after 130 cycles. Our study thus describes a new index affecting the CEI formation and proposes novel strategies to deeply optimize the high‐voltage LIBs.
Several biological properties and synthesis of 2‐(4‐methylthiazol‐5‐yl) ethoxy substitute zinc phthalocyanine
Authors: Solğun Derya Güngördü , Özdemir Sadin , Dündar Abdurrahman , Ağırtaş Mehmet Salih 
Published: November 2023

In this study, 4‐(2‐(4‐methylthiazol‐5‐yl) ethoxy) phthalonitrile (3) and zinc phthalocyanine complex (4) were synthesized and characterized. UV–vis and fluorescence spectra, aggregation, and fluorescence parameters of the zinc phthalocyanine compound were investigated. As biological properties, DPPH radical capture, antidiabetic, DNA cutting, antimicrobial, photodynamic antimicrobial, anti‐biofilm activities, and microbial cell viability parameters of the compounds were determined. The highest antioxidant activity was found as 62.80% at 100 mg/L concentration with compound 4, and compound 4 also showed the best antidiabetic activity as 65.17% at 400 mg/L concentration. In DNA cutting activity, it was determined that 3 and 4 cut DNA at all concentrations. For compounds 3–4, the minimum inhibitory concentration (MIC) values were found to be 32 and 16 mg/L for Enterococcus hirae and Enterococcus feacalis, respectively. The strongest MIC value of photodynamic antimicrobial activity was achieved as 4 mg/L for E. feacalis with 4. It was observed that both compounds inhibited the microbial viability activity of Escherichia coli by 100% at concentrations of 100 mg/L. Compound 4 inhibited biofilms of Pseudomonas aureginosa and Staphylococcus aureus as 92.48% and 98.56% at 50 mg/L concentration, respectively.
Efficient Analysis of Interdependencies in Electrode Manufacturing Through Joint Application of Design of Experiments and Explainable Machine Learning
Authors: Haghi Sajedeh , Keilhofer Josef , Schwarz Nico , He Pengdan , Daub Rüdiger 
Published: November 2023

AbstractBattery cell production is a key contributor to achieving a net‐zero future. A comprehensive understanding of the various process steps and their interdependencies is essential for speeding up the commercialization of newly developed materials and optimizing production processes. While several approaches have been employed to analyze and understand the complexity of the process chain and its interdependencies – ranging from expert‐ and simulation‐based to data‐driven – the latter holds significant potential for real‐time application. This is particularly relevant for inline process control and optimization. To streamline the development and implementation of data‐driven models, a holistic framework that encompasses all necessary steps – from identification of relevant parameters and generation of data to development of models – is imperative. This article aims to address this objective by presenting a comprehensive and systematic methodology, demonstrated for efficient cross‐process analysis in electrode manufacturing. Through the combined utilization of design of experiments methods, data‐driven models, and explainable machine learning methods, the interdependencies between production parameters and the physical, mechanical, and electrochemical characteristics of the electrodes were uncovered. These actionable insights are essential for enabling informed decision‐making, facilitating the selection of appropriate process parameters, and ultimately optimizing the production process.
Popular boys, the ideal schoolboy, and blended patterns of masculinity for 10‐ to 11‐year‐olds in two London schools
Authors: Swain Jon 
Published: November 2023

AbstractGenerating data from small group interviews with 41 boys aged 10–11 years from two London schools in 2022, this paper contributes to the field of gender by introducing a new form of non‐hegemonic and positive masculinity, which I am calling ‘blended’ masculinity, and which was the most common formation in each school. Although its features differed a little in each setting, this blended formulation broadly consisted of orthodox qualities of masculinity (e.g. athleticism, assertiveness, confidence, independence), combined with feminine‐associated traits (e.g. kindness, caring, sociability, emotional literacy). I argue that this blended form is different from previous conceptualisations of hybrid masculinity in the gender literature and is more akin to recent conceptions of hybrid femininity. There were no dominant forms of masculinity with hierarchical connotations of superiority, and no hegemony that legitimated unequal relations, with obvious subordination of other masculinities or femininities. Boys and girls generally got on well with each other and there was also no evidence of homophobia or misogyny. The paper also explores notions of peer‐group popularity, which was based on a series of resources, and delineates the characteristics of a fictional, ‘ideal’, schoolboy, whose features and attributes were connected to the different versions of masculinity on show.