bluuebunny/crossref_metadata_2025 huggingface dataset:
Perfil de resistência a antibióticos de Rothia aeria e Rothia dentocariosa isoladas de canais radiculares dentários
Authors: Brandão Letícia Beatriz dos Santos , Santos Mateus Leite , Antón Ana Rita Sokolonski
Published: December 2023

Introdução: os microrganismos do gênero Rothia spp., apesar de presentes no microbioma da cavidade bucal, estão associados a infecções como endocardite infecciosa, osteomielite vertebral e tubercolose. São bactérias pouco estudadas, e seu perfil de sensibilidade a antibióticos ainda é pouco explorado. Objetivo: no presente estudo, realizou-se uma análise do perfil de sensibilidade a antibióticos de isolados bucais de Rothia, através do ensaio de microdiluição em caldo, após identificação bacteriana. Metodologia: brevemente, dois isolados bacterianos oriundos de canais radiculares em tratamento foram identificados por MALDI Biotyper (Bruker Daltonics Inc, Inglaterra), e a sensibilidade aos antibióticos amoxicilina, gentamicina, clindamicina, e azitromicina foi testada em concentrações que variaram de 1,955 a 1000, e avaliada através de ensaio de microdiluição em caldo, de acordo com o protocolo CLSI M7-A632. Resultados: um dos isolados foi identificado como Rothia aerea e o outro como Rothia dentocariosa. Esses isolados foram altamente sensíveis aos antibióticos testados. Atividades bactericidas puderam ser observadas contra a Rothia aerea com todos os antibióticos testados, em suas menores concentrações. Conclusão: deve-se acompanhar isolados dessas bactérias para verificar o possível desenvolvimento de resistência. Este trabalho vem adicionar informações sobre o gênero Rothia, o qual ainda é pouco estudado e pode causar infecções sistêmicas graves.
A ritualística da masculinidade e da violência em 'Os meninos de Nápoles', de Roberto Saviano
Authors: Da Silva Claudimar Pereira
Published: December 2023

Este artigo objetiva a análise das masculinidades e da violência no romance Os meninos de Nápoles (2019), do escritor italiano Roberto Saviano. Publicado em 2016, o romance narra o surgimento de uma gangue de garotos na cidade de Nápoles, ligada à Camorra, uma das ramificações da máfia italiana. Partindo-se dos pressupostos teóricos de Raewyn Connell (2005), Eve Kosofsky Sedgwick (1985), Frederic M. Trasher (1963), Michael Kimmel (2005) e Daniel Welzer-Lang (2001), pretende-se analisar os sentidos de masculinidade experimentados pelo microcosmo homossocial da gangue, e o modo como eles se articulam à violência, ao territorialismo, ao sexismo, à homofobia e à manutenção da masculinidade hegemônica.
Reporting of Factorial Randomized Trials
Authors: Kahan Brennan C. , Hall Sophie S. , Beller Elaine M. , Birchenall Megan , Chan An-Wen , Elbourne Diana , Little Paul , Fletcher John , Golub Robert M. , Goulao Beatriz , Hopewell Sally , Islam Nazrul , Zwarenstein Merrick , Juszczak Edmund , Montgomery Alan A.
Published: December 2023

Importance

Transparent reporting of randomized trials is essential to facilitate critical appraisal and interpretation of results. Factorial trials, in which 2 or more interventions are assessed in the same set of participants, have unique methodological considerations. However, reporting of factorial trials is suboptimal.

Objective

To develop a consensus-based extension to the Consolidated Standards of Reporting Trials (CONSORT) 2010 Statement for factorial trials.

Design

Using the Enhancing the Quality and Transparency of Health Research (EQUATOR) methodological framework, the CONSORT extension for factorial trials was developed by (1) generating a list of reporting recommendations for factorial trials using a scoping review of methodological articles identified using a MEDLINE search (from inception to May 2019) and supplemented with relevant articles from the personal collections of the authors; (2) a 3-round Delphi survey between January and June 2022 to identify additional items and assess the importance of each item, completed by 104 panelists from 14 countries; and (3) a hybrid consensus meeting attended by 15 panelists to finalize the selection and wording of items for the checklist.

Findings

This CONSORT extension for factorial trials modifies 16 of the 37 items in the CONSORT 2010 checklist and adds 1 new item. The rationale for the importance of each item is provided. Key recommendations are (1) the reason for using a factorial design should be reported, including whether an interaction is hypothesized, (2) the treatment groups that form the main comparisons should be clearly identified, and (3) for each main comparison, the estimated interaction effect and its precision should be reported.

Conclusions and Relevance

This extension of the CONSORT 2010 Statement provides guidance on the reporting of factorial randomized trials and should facilitate greater understanding of and transparency in their reporting.
Objective Sleep Duration and All-Cause Mortality Among People With Obstructive Sleep Apnea
Authors: Lin Yiqi , Wu Yongxi , Lin Qianwen , Wing Yun Kwok , Xu Lili , Ge Junbo , Wu Qinwei , Li Zhen , Wu Qingjie , Lin Beiwei , Wei Shichao
Published: December 2023

Importance

The association between sleep duration and all-cause mortality remains unclear among people with obstructive sleep apnea (OSA).

Objective

To explore whether there is an association between sleep duration and all-cause mortality among people with OSA.

Design, Setting, and Participants

This cohort study investigated participants with OSA from the Sleep Heart Health Study (SHHS) in which participants were enrolled between 1995 and 1998 with questionnaires and polysomnography (PSG) assessment and followed up for a median of 11.8 years. SHHS was a multicenter community-based study; 2574 participants with OSA defined by apnea-hypopnea index (AHI) greater than or equal to 15 from SHHS were found; all of them had all-cause mortality data and were included in the study. Data were analyzed from November 2022 to October 2023.

Exposures

Participants were divided into 4 groups with objective sleep duration of (1) at least 7 hours, (2) 6 to less than 7 hours, (3) 5 to less than 6 hours, and (4) less than 5 hours, which was determined by total sleep time on PSG at baseline.

Main Outcomes and Measures

All-cause mortality was defined as deaths from any cause and its risk was compared among 4 OSA groups using Cox regression models.

Results

A total of 2574 participants with OSA were included (1628 [63.2%] men and 946 [36.8%] women; mean [SD] age, 65.4 [10.7] years; 211 [8.2%] Black, 2230 [86.6%] White, 133 [5.2%] other race). Overall, 688 all-cause deaths were observed in participants. Compared with the group sleeping at least 7 hours, the groups sleeping 6 to less than 7 hours (hazard ratio [HR], 1.53 [95% CI, 1.13-2.07]), 5 to less than 6 hours (HR, 1.40 [95% CI, 1.03-1.90]), and less than 5 hours (HR, 1.64 [95% CI, 1.20-2.24]) had significantly higher risks of all-cause mortality independent of AHI. Sensitivity analyses were performed among participants with available data of positive airway pressure treatment during follow-up and the finding was mostly consistent, albeit the HR for the group of 5 to less than 6 hours was not statistically significant.

Conclusions and Relevance

In this cohort study of 2574 participants with OSA, those with shorter objective sleep duration had higher risk of all-cause mortality independent of AHI compared with those sleeping at least 7 hours. Further studies would be needed to investigate health benefits of extending sleep length among people with OSA with short sleep duration.
Consensus Statement for Protocols of Factorial Randomized Trials
Authors: Kahan Brennan C. , Hall Sophie S. , Beller Elaine M. , Birchenall Megan , Elbourne Diana , Juszczak Edmund , Little Paul , Fletcher John , Golub Robert M. , Goulao Beatriz , Hopewell Sally , Islam Nazrul , Zwarenstein Merrick , Chan An-Wen , Montgomery Alan A.
Published: December 2023

Importance

Trial protocols outline a trial’s objectives as well as the methods (design, conduct, and analysis) that will be used to meet those objectives, and transparent reporting of trial protocols ensures objectives are clear and facilitates appraisal regarding the suitability of study methods. Factorial trials, in which 2 or more interventions are assessed in the same set of participants, have unique methodological considerations. However, no extension of the Standard Protocol Items: Recommendations for Interventional Trials (SPIRIT) 2013 Statement, which provides guidance on reporting of trial protocols, for factorial trials is available.

Objective

To develop a consensus-based extension to the SPIRIT 2013 Statement for factorial trials.

Evidence Review

The SPIRIT extension for factorial trials was developed using the Enhancing the Quality and Transparency of Health Research (EQUATOR) methodological framework. First, a list of reporting recommendations was generated using a scoping review of methodological articles identified using a MEDLINE search (inception to May 2019), which was supplemented with relevant articles from the personal collections of the authors. Second, a 3-round Delphi survey (January to June 2022, completed by 104 panelists from 14 countries) was conducted to assess the importance of items and identify additional recommendations. Third, a hybrid consensus meeting was held, attended by 15 panelists to finalize selection and wording of the checklist.

Findings

This SPIRIT extension for factorial trials modified 9 of the 33 items in the SPIRIT 2013 checklist. Key reporting recommendations were that the rationale for using a factorial design should be provided, including whether an interaction is hypothesized; the treatment groups that will form the main comparisons should be identified; and statistical methods for each main comparison should be provided, including how interactions will be assessed.

Conclusions and Relevance

In this consensus statement, 9 factorial-specific items were provided that should be addressed in all protocols of factorial trials to increase the trial’s utility and transparency.
Hydrophobic Trinuclear Copper Cluster‐Containing Organic Framework for Synergetic Electrocatalytic Synthesis of Amino Acids
Authors: Li Ning , Pan Chenliang , Lu Guang , Pan Houhe , Han Yuesheng , Wang Kang , Jin Peng , Liu Qingyun , Jiang Jianzhuang
Published: December 2023

Electrocatalytic synthesis of amino acids provides a promising green and efficient pathway to manufacture the basic substances of life. Herein, reaction of 2,5‐perfluroalkyl‐terepthalohydrazide and tris(4‐µ2‐O‐carboxaldehyde‐pyrazolato‐N, N′)‐tricopper affords a crystalline trinuclear copper cluster‐containing organic framework, named F‐Cu3‐OF. Incorporation of abundant hydrophobic perfluroalkyl groups inside the channels of F‐Cu3‐OF is revealed to successfully suppress the hydrogen evolution reaction via preventing H+ cation with large polarity from the framework of F‐Cu3‐OF and in turn increasing the adsorption of other substrates with relatively small polarity like NO3− and keto acids on the active sites. The copper atoms with short distance in the trinuclear copper clusters of F‐Cu3‐OF enable simultaneous activization of NO3− and keto acids, facilitating the following synergistic and efficient C─N coupling on the basis of in situ spectroscopic investigations together with theoretical calculation. Combination of these effects leads to efficient electroproduction of various amino acids including glycine, alanine, leucine, valine, and phenylalanine from NO3− and keto acids with a Faraday efficiency of 42%–71% and a yield of 187–957 µmol cm−2 h−1, representing the thus far best performance. This work shall be helpful for developing economical, eco‐friendly, and high‐efficiency strategy for the production of amino acids and other life substances.
In‐Depth Compositional Analysis of the Carbon‐Rich Fine‐Grain Layer in Solution‐Processed CZTSSe Films Accessed by a Photonic Lift‐Off Process
Authors: Javed Ahmed , Jones Michael , Campbell Stephen , Yerci Selcuk , Barrioz Vincent , Qu Yongtao
Published: December 2023

The existence of a fine‐grain (FG) sub‐layer between the top large‐grain (LG) layer and the back contact is widely observed in kesterite absorbers prepared with organic solvents. In this paper, the distinguishing features of the lifted‐off carbon‐rich FG layer are investigated through direct analysis with a series of characterization techniques, including X‐ray photoelectron spectroscopy (XPS), attenuated total reflectance, X‐ray diffraction, and scanning electron microscopy. To access the FG layer for direct probing, a scalable and repeatable photonic lift‐off method is developed for carrying out the separation of the kesterite absorber layer from the Mo‐coated glass substrate. A very high light intensity of 4 kW cm−2for a short interval of 1 ms is optimized by COMSOL simulations, and successful implementation is demonstrated. The XPS analysis has revealed significant carbon content at the exposed FG surface, which explains the hindrance of grain growth due to carbon abundance. The variations in cations and anions concentrations from FG layer leading into LG region are explored through argon ions (Ar+) assisted XPS depth profiling. The observed significant differences between the composition of FG and LG regions are speculated to negatively impact the performance of solar cells.
Determinants of municipal‐level household food waste
Authors: Deng Wen‐Shuenn , Lin Yi‐Chen
Published: December 2023

This research investigates the long‐run determinants of per capita food waste, using a monthly time series dataset collected from the Taipei City Food Scraps Recycling Program, covering a span of 19 years. In addition, this research introduces a new proxy for the food wastage rate, gauged by the ratio of edible‐to‐inedible food scraps. The results of time‐series cointegration analysis show that per capita edible food scraps and socioeconomic factors are bound together over the long run. Specifically, per capita edible food waste displays a positive co‐movement with food price, the working‐age share, and household size, while exhibiting a negative co‐movement with the old‐age share. This insight empowers policymakers with the ability to foresee and tackle the food waste problem by acting on the municipality's demographic and economic structural change. Our analysis complements the existing studies that depend on cross‐sectional individual‐level data by adopting a long‐run municipal‐level time series perspective. [EconLit Citations: Q11, Q13, Q18, D1].
Development and assessment of a stair ascension challenge as a measure of aging and physical function in nonhuman primates
Authors: Scarberry Shannon R. , Prutchi Hannah , Frye Brett M. , Herr Justin , Scott Christie , Long Chrissy M. , Jorgensen Matthew J. , Shively Carol A. , Kavanagh Kylie
Published: December 2023

Nonhuman primates (NHPs) are valuable models for studying healthspan, including frailty development. Frailty metrics in people centers on functional measures, including usual gait speed which can be predictive of all‐cause mortality. This concept that physical competencies are able to prognosticate an individual's health trajectory over chronologic aging is well‐accepted and has led to refinements in how physical function is evaluated, and include measures of strength and power along with walking speed. NHP studies of aging require evaluation of physical function, which can be difficult in field and research settings. We compared stair climb velocity to usual walking speed in 28 peri‐geriatric to geriatric NHPs, as incorporating a climbing obstacle integrates multiple components of physical function: isolated leg and back strength, proprioception, balance, and range of motion. We find that stair climbing speed was reliable between observers, and whether timing was in‐person take from video capture. The stair climb rates were 50% more associated with chronological age than walking speed (R = −0.68 vs. −0.45) and only stair climbing speeds were retained as predictive of age when walking speed and bodyweight were included in multivariate models (overall R2 = 0.44; p < 0.0001). When comparing young (10−16 years) versus geriatric (16−29 years) stair climbing speed was significantly different (p < 0.001), while walking speeds only tended to be slower (p = 0.12) suggesting that the additional challenge of a stair climb better unmasks subclinical frailty development that usual walking speed.
Porous Single‐crystalline Centimeter‐sized α‐Al2O3Monoliths for Selective and Durable Non‐oxidative Dehydrogenation of Ethane
Authors: Li Xue , Li Wenting , Zhang Jie , Yin Wen , Xia Yuanguang , Xie Kui
Published: December 2023

Alpha alumina (α‐Al2O3) are inert materials with outstanding thermal, chemical and mechanical stability. Herein, we fabricate porous single‐crystalline (PSC) α‐Al2O3monoliths at centimeter scale to endow them with high catalytic activity while maintaining their stability. We reduce PSC α‐Al2O3monoliths to create oxygen vacancies in lattice and stabilize them by the ordered lattice to construct unsaturated Al−O coordination structures for enhancing the catalytic activity. The generation of oxygen vacancy at 18e wyckoff position contributes to the unsaturated Al−O coordination. As a case study, we demonstrate the outstanding performance with conversion (≈34 %) and selectivity (≈95 %) toward non‐oxidative dehydrogenation of ethane to ethylene at 700 °C. We achieve the outstanding performance without obvious degradation even after a continuous operation over 1000 hours at 700 °C.
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

This 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

Rechargeable 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

The 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

In 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

Iron‐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

Amide 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

The 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

Graphitic 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

Boronic 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

With 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

The 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

Gele 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

Along 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

Seed 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

Cowpea [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

The 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

In 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.
Copper Single Atoms Chelated on Ligand‐Modified Carbon for Ullmann‐type C−O Coupling
Authors: Ruta Vincenzo , Di Liberto Giovanni , Moriggi Francesco , Ivanov Yurii P. , Divitini Giorgio , Bussetti Gianlorenzo , Barbera Vincenzina , Bajada Mark A. , Galimberti Maurizio , Pacchioni Gianfranco , Vilé Gianvito
Published: December 2023

Cross‐coupling reactions are of great importance in chemistry due to their ability to facilitate the construction of complex organic molecules. Among these reactions, the Ullmann‐type C−O coupling between phenols and aryl halides is particularly noteworthy and useful for preparing diarylethers. However, this reaction typically relies on homogeneous catalysts that rapidly deactivate under harsh reaction conditions. In this study, we introduce a novel heterogeneous catalyst for the Ullmann‐type C−O coupling reaction, comprised of isolated Cu atoms chelated to a tetraethylenepentamine‐pyrrole ligand that is immobilized on graphite nanoplatelets. The catalytic study reveals the recyclability of the material, and demonstrates the crucial role of the pyrrole linker in stabilizing the Cu sites. The work expands the potential of single‐atom catalyst nanoarchitectures and underscores the significance of ligands in stabilizing metals in cationic forms, providing a novel, tailored catalyst for cross‐coupling chemistries.
Carbon isotope ratios of phenethylamine and its urinary metabolite phenylacetylglutamine
Authors: Piper Thomas , Krombholz Sophia , Thevis Mario
Published: December 2023

Phenethylamine (PEA) is a naturally occurring trace amine that acts as a modulator in the central nervous system. It is widely sold as a dietary supplement and advertised for its mood enhancing effects and should support weight loss. It is prohibited in sports and itemized as a stimulant on the Prohibited List issued by the World Anti‐Doping Agency (WADA). After oral administration of PEA, its urinary concentration is found only slightly elevated while metabolites of PEA show a significant increase. Besides 2‐(2‐hydroxyphenyl)acetamide sulfate, especially phenylacetylglutamine (PAG) was found at significantly elevated urinary concentrations after the administration. Due to large inter‐ and intra‐individual variations in urinary concentrations of all metabolites, establishing a concentration or concentration ratio‐based threshold remained complicated to unambiguously identify post‐administration samples. In accordance with the approach employed in detecting testosterone misuse, the applicability of isotope ratio mass spectrometry to differentiate between endogenously elevated concentrations and PEA administrations was investigated. A method encompassing solid‐phase extraction combined with acetylation and high‐performance liquid chromatography (HPLC)‐based clean‐up was developed and validated for PEA. The more abundant metabolite PAG was purified by a direct injection approach on the HPLC and could be analyzed without the need for derivatization. Both methods were validated considering applicable WADA regulations. A reference population encompassing n = 57 samples was investigated to establish population‐based thresholds considering the carbon isotope ratios (CIRs) found at natural abundance for PAG. The derived threshold was tested for its applicability by re‐analysis of numerous post‐administration samples encompassing single‐ and multi‐dose trials.
A facile ratiometric electrochemical sensing platform with in‐situ electropolymerized thionine on effective sensing of 5‐hydroxytryptamine
Authors: Chen Kankan , Xu Jiawei , Song Jingjing , Liu Zhonggang , Guo Zheng
Published: December 2023

The ratiometric electrochemical sensors have been highly explored to minimize system errors and environmental interference. However, it is extremely desirable on the development of an effective ratiometric electrochemical sensor in a facile approach without the complicated assembly process. In this work, an effective internal reference probe was coupled based on the polymerized thionine (pTh) via a one‐step electrodeposition method. The ratiometric electrochemical sensing platform was applied for 5‐hydroxytryptamine (5‐HT) detection, where the internal reference probe, Th, presented the robust redox signal and can be clearly distinguished from the oxidation signal of 5‐HT. The proposed pTh modified GCE presented the outstanding electrochemical performance on sensing 5‐HT in a wide concentration range with a detection limit of 8.4 nΜ. Further, the fabricated sensor was efficiently employed for the detection of 5‐HT in various human serum samples and the obtained results were consistent with the reported range in serum samples. This work offers the great possibility on the fabrication of efficient ratiometric sensors in a facile approach and presents great application prospects in clinical diagnosis.