bluuebunny/crossref_metadata_2025_split huggingface dataset:
Heart rate fragmentation and brain MRI markers of small vessel disease in MESA
Authors: Heckbert Susan R. , Jensen Paul N. , Erus Guray , Nasrallah Ilya M. , Rashid Tanweer , Habes Mohamad , Austin Thomas R. , Floyd James S. , Schaich Christopher L. , Redline Susan , Bryan R. Nick , Costa Madalena D. 
Published: November 2023

AbstractINTRODUCTIONHeart rate (HR) fragmentation indices quantify breakdown of HR regulation and are associated with atrial fibrillation and cognitive impairment. Their association with brain magnetic resonance imaging (MRI) markers of small vessel disease is unexplored.METHODSIn 606 stroke‐free participants of the Multi‐Ethnic Study of Atherosclerosis (mean age 67), HR fragmentation indices including percentage of inflection points (PIP) were derived from sleep study recordings. We examined PIP in relation to white matter hyperintensity (WMH) volume, total white matter fractional anisotropy (FA), and microbleeds from 3‐Tesla brain MRI completed 7 years later.RESULTSIn adjusted analyses, higher PIP was associated with greater WMH volume (14% per standard deviation [SD], 95% confidence interval [CI]: 2, 27%, P = 0.02) and lower WM FA (–0.09 SD per SD, 95% CI: –0.16, –0.01, P = 0.03).DISCUSSIONHR fragmentation was associated with small vessel disease. HR fragmentation can be measured automatically from ambulatory electrocardiogram devices and may be useful as a biomarker of vascular brain injury.
A Dual Anion Chemistry‐Based Superionic Glass Enabling Long‐Cycling All‐Solid‐State Sodium‐Ion Batteries
Authors: Lin Xiaoting , Zhao Yang , Wang Changhong , Luo Jing , Fu Jiamin , Xiao Biwei , Gao Yingjie , Li Weihan , Zhang Shumin , Xu Jiabin , Yang Feipeng , Hao Xiaoge , Duan Hui , Sun Yipeng , Guo Jinghua , Huang Yining , Sun Xueliang 
Published: November 2023

AbstractGlassy Na‐ion solid‐state electrolytes (GNSSEs) are an important group of amorphous SSEs. However, the insufficient ionic conductivity of state‐of‐the‐art GNSSEs at room temperature lessens their promise in the development of all‐solid‐state Na‐ion batteries (ASSNIBs) with high energy density and improved safety. Here we report the discovery of a new sodium superionic glass, 0.5Na2O2‐TaCl5 (NTOC), based on dual‐anion sublattice of oxychlorides. The unique local structures with abundant bridging and non‐bridging oxygen atoms contributes to a highly disordered Na‐ion distribution as well as low Na+ migration barrier within NTOC, enabling an ultrahigh ionic conductivity of 4.62 mS cm−1 at 25 °C (more than 20 times higher than those of previously reported GNSSEs). Moreover, the excellent formability of glassy NTOC electrolyte and its high electrochemical oxidative stability ensure a favourable electrolyte‐electrode interface, contributing to superior cycling stability of ASSNIBs for over 500 cycles at room temperature. The discovery of glassy NTOC electrolyte would reignite research enthusiasm in superionic glassy SSEs based on multi‐anion chemistry.
Enzymatische Peptid‐ und Proteinbromierung: Der BromoTrp Tag
Authors: Montua Nicolai , Thye Paula , Hartwig Pia , Kühle Matthias , Sewald Norbert 
Published: November 2023

AbstractBioorthogonale Reaktionen von Proteinen und ungeschützten Peptiden sind von hohem Wert für die chemische Biologie. Die Kombination aus enzymatischer Halogenierung und übergangsmetallkatalysierter Kreuzkupplung bietet einen praktikablen Ansatz zur Modifizierung von Proteinen und ungeschützten Peptiden. Durch semirationales Protein Engineering, wurden Varianten der Tryptophan 6‐Halogenase Thal identifiziert, welche die Bromierung von Peptiden mit einem C‐terminalen Tryptophanrest ermöglichen. Das Substratspektrum wurde anhand von Di‐, Tri‐ und Tetrapeptid‐Bibliotheken charakterisiert, und ein optimierter Peptid‐Tag identifiziert, dem wir den Namen BromoTrp‐Tag gegeben haben. Dieser Tag wurde in drei Modellproteine eingeführt. Deren präparative, posttranslationale Bromierung mit nur einem Kultivierungs‐ und Aufreinigungsschritt wurde durch das bromierende E. coli Koexpressionssystem Brocoli ermöglicht. Pd‐katalysierte Suzuki–Miyaura Kreuzkupplung war mittels Pd‐Nanopartikeln als Katalysator bei 37 °C möglich, was das vielversprechende Potential dieser Strategie zum Zweck bioorthogonaler Funktionalisierung und Konjugation demonstriert.
Preserving Structurally Labile Peptide Nanosheets After Molecular Functionalization of the Self‐Assembling Peptides
Authors: Chen Xin , Xia Cai , Guo Pan , Wang Chenru , Zuo Xiaobing , Jiang Yun‐Bao , Jiang Tao 
Published: November 2023

AbstractA significant challenge in creating supramolecular materials is that conjugating molecular functionalities to building blocks often results in dissociation or undesired morphological transformation of their assemblies. Here we present a facile strategy to preserve structurally labile peptide assemblies after molecular modification of the self‐assembling peptides. Sheet‐forming peptides are designed to afford a staggered alignment with the segments bearing chemical modification sites protruding from the sheet surfaces. The staggered assembly allows for simultaneous separation of attached molecules from each other and from the underlying assembly motifs. Strikingly, using PEGs as the external molecules, PEG400‐ and PEG700‐peptide conjugates directly self‐associate into nanosheets with the PEG chains localized on the sheet surfaces. In contrast, the sheet formation based on in‐register lateral packing of peptides does not recur upon the peptide PEGylation. This strategy allows for fabrication of densely modified assemblies with a variety of molecules, as demonstrated using biotin (hydrophobic molecule), c(RGDfK) (cyclic pentapeptide), and nucleic acid aptamer (negatively charged ssDNA). The staggered co‐assembly also enables extended tunability of the amount/density of surface molecules, as exemplified by screening ligand‐appended assemblies for cell targeting. This study paves the way for functionalization of historically challenging fragile assemblies while maintaining their overall morphology.
New Reaction Pathway of Superoxide Disproportionation Induced by a Soluble Catalyst in Li‐O2 Batteries
Authors: Jiang Zhuoliang , Wen Bo , Huang Yaohui , Guo Yihe , Wang Yuzhe , Li Fujun 
Published: November 2023

AbstractAprotic Li‐O2 battery has attracted considerable interest for high theoretical energy density, however the disproportionation of the intermediate of superoxide (O2−) during discharge and charge leads to slow reaction kinetics and large voltage hysteresis. Herein, the chemically stable ruthenium tris(bipyridine) (RB) cations are employed as a soluble catalyst to alternate the pathway of O2− disproportionation and its kinetics in both the discharge and charge processes. RB captures O2− dimer and promotes their intramolecular charge transfer, and it decreases the energy barrier of the disproportionation reaction from 7.70 to 0.70 kcal mol−1. This facilitates the discharge and charge processes and simultaneously mitigates O2− and singlet oxygen related side reactions. These endow the Li‐O2 battery with reduced discharge/charge voltage gap of 0.72 V and prolonged lifespan for over 230 cycles when coupled with RuO2 catalyst. This work highlights the vital role of superoxide disproportionation for Li‐O2 battery.
Internal Dynamics and Modular Peripheral Binding in Stimuli‐Responsive 3 : 2 Host:Guest Complexes
Authors: Yin Hang , Rosas Roselyne , Viel Stéphane , Giorgi Michel , Monnier Valerie , Charles Laurence , Siri Didier , Gigmes Didier , Nassar Youssef , Chevallier Floris , Bucher Christophe , Wang Ruibing , Kermagoret Anthony , Bardelang David 
Published: November 2023

AbstractNow that the chemistry of 1 : 1 host:guest complexes is well‐established, it is surprising to note that higher stoichiometry (oligomeric) complexes, especially those with excess host, remain largely unexplored. Yet, proteins tend to oligomerize, affording new functions for cell machinery. Here, we show that cucurbit[n]uril (CB[n]) macrocycles combined with symmetric, linear di‐viologens form unusual 3 : 2 host:guest complexes exhibiting remarkable dynamic properties, host self‐sorting, and external ring‐translocation. These results highlight the structural tunability of cucurbit[8]uril (CB[8]) based 3 : 2 host:guest complexes in water and their responsiveness toward several stimuli (chemicals, pH, redox).
Structure and Defect Engineering Synergistically Boost High Solar‐to‐Chemical Conversion Efficiency of Cerium oxide/Au Hollow Nanomushrooms for Nitrogen Photofixation
Authors: Li Hua , Zhang Junwei , Deng Xia , Wang Yantao , Meng Genping , Liu Ruitong , Huang Junfeng , Tu Mudong , Xu Cailing , Peng Yong , Wang Baodui , Hou Yanglong 
Published: November 2023

AbstractPhotocatalytic nitrogen fixation using solar illumination under ambient conditions is a promising strategy for production of the indispensable chemical NH3. However, due to the catalyst‘s limitations in solar energy utilization, loss of hot electrons during transfer, and low nitrogen adsorption and activation capacity, the unsatisfactory solar‐to‐chemical conversion (SCC) efficiencies of most photocatalysts limit their practical applications. Herein, cerium oxide nanosheets with abundant strain‐VO defects were anchored on Au hollow nanomushroom through atomically sharp interfaces to construct a novel semiconductor/plasmonic metal hollow nanomushroom‐like heterostructure (denoted cerium oxide‐AD/Au). Plasmonic Au extended the absorption of light from the visible to the second near‐infrared region. The superior interface greatly enhanced the transfer efficiency of hot electrons. Abundant strain‐VO defects induced by interfacial compressive strain promoted adsorption and in situ activation of nitrogen, and such synergistic promotion of strain and VO defects was further confirmed by density functional theory calculations. The judicious structural and defect engineering co‐promoted the efficient nitrogen photofixation of the cerium oxide‐AD/Au heterostructures with a SCC efficiency of 0.1 % under simulated AM 1.5G solar illumination, which is comparable to the average solar‐to‐biomass conversion efficiency of natural photosynthesis by typical plants, thus exhibiting significant potential as a new candidate for artificial photosynthesis.
Construction of Bridged Benzazepines via Photo‐Induced Dearomatization
Authors: Song Ting‐Ting , Mei Yong‐Kang , Liu Yan , Wang Xiao‐Yu , Guo Shi‐Yu , Ji Ding‐Wei , Wan Boshun , Yuan Weiming , Chen Qing‐An 
Published: November 2023

AbstractBridged benzazepine scaffolds, possessing unique structural and physicochemical activities, are widespread in various natural products and drugs. The construction of these skeletons often requires elaborate synthetic effort with low efficiency. Herein, we develop a simple and divergent approach for constructing various bridged benzazepines by a photocatalytic intermolecular dearomatization of naphthalene derivatives with readily available α‐amino acids. The bridged motif is created via a cascade sequence involving photocatalytic 1,4‐hydroaminoalkylation, alkene isomerization and cyclization. Interestingly, the diastereoselectivity can be regulated through different reaction modes in the cyclization step. Moreover, aminohydroxylation and its further bromination have also been demonstrated to access highly functionalized bridged benzazepines. Preliminary mechanistic studies have been performed to get insights into the mechanism. This method provides a divergent synthetic approach for construction of highly functionalized bridged benzazepines, which have been otherwise difficult to access.
Ultralight Ultrafast Enzymes**
Authors: Zhang Xuepei , Meng Zhaowei , Beusch Christian M. , Gharibi Hassan , Cheng Qing , Lyu Hezheng , Di Stefano Luciano , Wang Jijing , Saei Amir A. , Végvári Ákos , Gaetani Massimiliano , Zubarev Roman A. 
Published: November 2023

AbstractInorganic materials depleted of heavy stable isotopes are known to deviate strongly in some physicochemical properties from their isotopically natural counterparts. Here we explored for the first time the effect of simultaneous depletion of the heavy carbon, hydrogen, oxygen and nitrogen isotopes on the bacterium E. coli and the enzymes expressed in it. Bacteria showed faster growth, with most proteins exhibiting higher thermal stability, while for recombinant enzymes expressed in depleted media, faster kinetics was discovered. At room temperature, luciferase, thioredoxin and dihydrofolate reductase and Pfu DNA polymerase showed up to a 250 % increase in activity compared to the native counterparts, with an additional ∼50 % increase at 10 °C. Diminished conformational and vibrational entropy is hypothesized to be the cause of the accelerated kinetics. Ultralight enzymes may find an application where extreme reaction rates are required.
Characterization of polar groups in polyvinyl chloride–ethyl vinyl acetate blends using coincidence Doppler broadening spectroscopy
Authors: Ghasemifard Mahdi , Ghamari Misagh 
Published: November 2023

AbstractCoincidence Doppler broadening spectroscopy (CDBS), known for its exceptional precision, is extensively employed in examining the electronic states of polymers. In this study, polyvinyl chloride (PVC)–ethyl vinyl acetate (EVA) polymers blends were prepared using conventional techniques, following specific ratios (75:25, 50:50, and 25:75, respectively). Spectroscopic analysis reveals that the longitudinal component of linear momentum surpasses the momentum unit (i.e., 10−3 m0c) when considering the ratio curve associated with the participation of oxygen core electrons. When compared to non‐polymer samples, the PVA polymer and PVA–EVA polymer blend exhibit greater free volume voids in contrast to non‐polymer structural defects. Furthermore, the annihilation of ortho‐positronium with core electrons, likely EVA oxygen core electrons, contributes to the measured free volume voids. An increased annihilation of positrons or positroniums by oxygen in the CDBS spectrum leads to higher calculated W parameter values. Conversely, as the PVC content increases, the W parameter decreases, suggesting reduced ortho‐positronium annihilation and consequently, enhanced formation of para‐positronium in the overall annihilation process. In summary, this investigation demonstrates the utility of CDBS in elucidating the electronic states and free volume voids in PVC and EVA polymers.
Selective analysis of resistance and susceptibility to duck hepatitis A virus genotype 3 in Pekin duck
Authors: Liang Suyun , Zhang Jiaojiao , Wang Xiaoyan , Xing Guangnan , Guo Zhanbao , Zhang Qi , Huang Wei , Xie Ming , Hou Shuisheng 
Published: November 2023

AbstractDuck viral hepatitis (DVH), mainly caused by duck hepatitis A virus genotype 3 (DHAV‐3) in China, is an important disease affecting Pekin ducks. Using artificial selection breeding based on genealogical and phenotypic observations, a susceptible line (Z7) and a resistant line (Z8) of Pekin ducks to DHAV‐3 were identified. Here, we performed a genome‐wide analysis to identify selected genes in the genomes of Pekin ducks underlying resistance/susceptible breeding. Following selection, the mortality rate of the Z8 line reduced from 59.2% to 7.8% in the fourth generation (Z8G4), whereas the death rate of the Z7 line increased from 67.5% to 81% in the third generation (Z7G3). Moreover, directed breeding caused the allele frequencies of Z8 and Z7 changing in opposite direction, accompanied by declines in genomic genetic diversity. With the G0 generation as the reference group, a total of 49 selected genes were identified in the Z7‐susceptible population and 109 selected genes in the Z8‐resistant population based on the top 5% FST and PI ratio, and two candidate key genes were further fine‐mapped. Susceptibility selection led to 17 mutations in the LRIG3 gene in the Z7 population (chr1: 169,757,982–169,772,687), and resistance selection led to 134 mutations in the CRHR2 gene in the Z8 population (chr2: 4,190,154–4,273,970). Our results provide new insights into the resistance and susceptibility to DHAV‐3 and lay a theoretical foundation for further research on the mechanism of resistance/susceptibility of Pekin ducks to DHAV‐3.
Coordination Chemistry of Bis‐Cyclic Alkyl(Amino) Carbene (cAAC)‐Supported Di‐Phosphorus (P2): An Efficient Route to Donor Base‐Stabilized Elusive Di‐Phosphorus‐Monoxide(P2O)‐Gold Complex
Authors: Francis Maria , Nag Ekta , Roy Sudipta 
Published: November 2023

AbstractThe stability and reactivity studies of heavier di‐atomic group‐15 congeners of alkynes, e. g., the di‐phosphorus (P≡P) compounds have been the topic of huge interest because of their contrasting transient properties and lower stability compared to those of the stable molecular di‐nitrogen (N≡N). Herein, we depict the reactivity studies of the bis‐cAAC‐stabilized di‐phosphorus (P2) having an inversely polarized phosphaalkene nature featuring the C=P double bonds with Au(I)Cl. Both the mono‐, and the di‐aurated phosphaalkenes with the formulae [(Me2‐cAAC=P)2(AuCl)] (2), and [(Me2‐cAAC=P)2(AuCl)2] (3), respectively have been isolated in the solid state. Moreover, for the first time, we have been able to isolate the cAAC‐stabilized tetra‐aurated elusive di‐phosphorus‐monoxide (P2O) with the formula [(Cy‐cAAC=P)−O−(P=cAAC−Cy)(AuCl)4] (5) in presence of oxygen. Complexes 2–3, 5 have been structurally characterized by single crystal X‐ray diffraction, and further studied by NMR spectroscopy. Our findings reveal significant elongation of the CcAAC−P bonds in 2–3, 5, and the presence of aurophilic interaction in 5. Quantum chemical calculations, including density functional theory (DFT), and energy decomposition analysis coupled with natural orbitals for chemical valence (EDA‐NOCV) have been performed to study the electron densities distribution and nature of bonding in 2–3, 5.
Lung patterning: Is a distal‐to‐proximal gradient of cell allocation and fate decision a general paradigm?
Authors: Zhang Kuan , Aung Thin , Yao Erica , Chuang Pao‐Tien 
Published: November 2023

AbstractRecent studies support a model in which the progeny of SOX9+ epithelial progenitors at the distal tip of lung branches undergo cell allocation and differentiation sequentially along the distal‐to‐proximal axis. Concomitant with the elongation and ramification of lung branches, the descendants of the distal SOX9+ progenitors are distributed proximally, express SOX2, and differentiate into cell types in the conducting airways. Amid subsequent sacculation, the distal SOX9+ progenitors generate alveolar epithelial cells to form alveoli. Sequential cell allocation and differentiation are integrated with the branching process to generate a functional branching organ. This review focuses on the roles of SOX9+ cells as precursors for new branches, as the source of various cell types in the conducting airways, and as progenitors of the alveolar epithelium. All of these processes are controlled by multiple signaling pathways. Many mouse mutants with defective lung branching contain underlying defects in one or more steps of cell allocation and differentiation of SOX9+ progenitors. This model provides a framework to understand the molecular basis of lung phenotypes and to elucidate the molecular mechanisms of lung patterning. It builds a foundation on which comparing and contrasting the mechanisms employed by different branching organs in diverse species can be made.
Origin and development of primary animal epithelia
Authors: Doerr Sophia , Zhou Phillip , Ragkousi Katerina 
Published: November 2023

AbstractEpithelia are the first organized tissues that appear during development. In many animal embryos, early divisions give rise to a polarized monolayer, the primary epithelium, rather than a random aggregate of cells. Here, we review the mechanisms by which cells organize into primary epithelia in various developmental contexts. We discuss how cells acquire polarity while undergoing early divisions. We describe cases where oriented divisions constrain cell arrangement to monolayers including organization on top of yolk surfaces. We finally discuss how epithelia emerge in embryos from animals that branched early during evolution and provide examples of epithelia‐like arrangements encountered in single‐celled eukaryotes. Although divergent and context‐dependent mechanisms give rise to primary epithelia, here we trace the unifying principles underlying their formation.
Removing barriers to plastic waste valorisation in Africa: Towards policies for value creation and capture in business ecosystems
Authors: Derks Milou , Romijn Henny 
Published: November 2023

AbstractStimulating plastic waste valorisation is suggested as an important way to address the growing waste problem in low‐income countries. However, policy interventions have not led to substantial waste valorisation, and the reasons for this have not been thoroughly analysed. We address this through a qualitative study of plastic waste in urban Zambia, which is representative of the policy and practice challenges in African plastic waste management. Using extensive data gathered through interviews, site visits and stakeholder meetings, we first conduct a business ecosystem analysis which provides a holistic view on value creation, capture, and destruction processes across all actors involved in the plastics lifecycle. Next, we map the barriers to value creation and capture by the system's main actors. Aggregation of these barriers reveals a low‐value trap, in which individual actors are disincentivized to increase waste valorisation activities. Finally, we analyse the reasons why policies aimed at waste valorisation have failed to break through this status quo. We find that policies have insufficiently addressed the barriers that keep the low‐value trap in place. Hence, they have not acted effectively on the root causes of systemic stagnation. By combining a business ecosystems analysis with an identification of barriers facing the individual actors in that ecosystem, our study is able to show why substantial plastic waste valorisation has not emerged despite policy incentives. Our analysis points toward concrete policy actions aimed at value redistribution and value increase, as key leverage points in the system to increase valorisation.
A pilot RCT of an online mindfulness‐based cognitive intervention for chemsex
Authors: Banbury Samantha , Lusher Joanne , Chandler Chris , Zervoulis Karyofyllis 
Published: November 2023

AbstractObjectivesChemsex is a term used to describe sex acts using psychoactive substances to enhance the sexual experience/arousal and predominates among men who have sex with men (MSM). Chemsex drugs predominantly include γ‐hydroxybutyric acid (GHB) and analogues, methamphetamine, mephedrone and erectile dysfunction agents (e.g., Sildenafil). Mindfulness‐based cognitive therapy (MBCT) combines cognitive therapy and mindfulness and has been shown to help support both sexual functioning and methamphetamine use. However, limited clinical trials have evaluated the use of cognitive mindfulness for chemsex in MSM. The present study assessed the effectiveness of an online mindfulness‐based cognitive intervention (MBCI) among 29 MSM aged 18–30 years engaged in chemsex.Design and SettingA mixed methods approach consisted of a randomised waitlist‐controlled trial and a content analysis reviewing participants' feedback on MBCI. The design of the intervention was based on a behavioural taxonomy mapped to selected behaviour change techniques (BCTs) to support the reliability of MBCI in its delivery.Main Outcome MeasuresParticipants completed assessments measuring levels of chemsex, mindfulness, sexual self‐efficacy and well‐being, taken at Weeks 0, 8 and 12 (follow‐up).ResultsParticipants reported lower levels of chemsex and higher levels of cognitive mindfulness, sexual self‐efficacy and well‐being postintervention and at the 12‐week follow‐up. The content analysis feedback responses yielded favourable outcomes, suggesting that participants developed a sense of self‐compassion, confidence and positive identity.ConclusionsThe MBCI effectively reduced chemsex; however, this study warrants replication with a larger, more diverse group of participants.