bluuebunny/crossref_metadata_2025_split huggingface dataset:
Adaptive safe reinforcement learning‐enabled optimization of battery fast‐charging protocols
Authors: Chowdhury Myisha A. , Al‐Wahaibi Saif S.S. , Lu Qiugang 
Published: September 2024

AbstractOptimizing charging protocols is critical for reducing battery charging time and decelerating battery degradation in applications such as electric vehicles. Recently, reinforcement learning (RL) methods have been adopted for such purposes. However, RL‐based methods may not ensure system (safety) constraints, which can cause irreversible damages to batteries and reduce their lifetime. To this end, this article proposes an adaptive and safe RL framework to optimize fast charging strategies while respecting safety constraints with a high probability. In our method, any unsafe action that the RL agent decides will be projected into a safety region by solving a constrained optimization problem. The safety region is constructed using adaptive Gaussian process (GP) models, consisting of static and dynamic GPs, that learn from online experience to adaptively account for any changes in battery dynamics. Simulation results show that our method can charge the batteries rapidly with constraint satisfaction under varying operating conditions.
Exploring the Relationship Between Stress, Salivary C‐Reactive Protein, and Embodied Physiological Responses in a Nigerian Population
Authors: Winful Taiye , Sorunke Modupe , Benn Torres Jada 
Published: September 2024

ABSTRACTObjectivesThe impacts of stress on inflammation, although hypothesized, have not been thoroughly examined, especially in relation to social and environmental factors and particularly within Black populations. This study aims to explore the biological mechanisms of embodiment linking stress and health to understand physiological changes in the body's response to psychological stress in a Nigerian population. Through a multidisciplinary approach, this study queries the relationship between stress, cortisol, and salivary C‐reactive protein (sCRP), a biomarker of inflammation, while also validating the use of sCRP as a potential and accurate stress indicator in the field.MethodsIn this cross‐sectional study, 138 passive drool saliva samples (n
female = 89 n
male = 49) were collected and assessed for sCRP and cortisol levels in adults. Participants also completed a short demographic survey and, to measure psychological stress, the General Health Questionnaire 12 (GHQ‐12). Relationships between sCRP and stress‐related variables (i.e., cortisol, GHQ‐12, and demographic data) were assessed using Spearman's correlations, simple regression, multivariable linear regression, and exploratory factor analysis.ResultssCRP levels ranged from 20.57 to 6879.41 pg/mL across all samples, with significant differences between female and male participants. The GHQ‐12 was not a significant predictor of sCRP variability. However, socio‐demographic factors such as body mass index (BMI), age, self‐reported sex, ethnic identity, and cortisol were significant predictors, collectively explaining 24%–27% of the variation in sCRP.ConclusionSocio‐demographic predictors like BMI, age, sex, and particularly ethnic group experience in Nigeria encapsulate aspects of embodied stress, that significantly affect sCRP variability.
Circadian Rhythms Correlated in DNA Methylation and Gene Expression Identified in Human Blood and Implicated in Psychiatric Disorders
Authors: Tang Haiyan , Chen Shanshan , Yi Liu , Xu Sheng , Yang Huihui , Li Zongchang , He Ying , Liao Yanhui , Chen Xiaogang , Liu Chunyu , Gu Lin , Yuan Ning , Chen Chao , Tang Jinsong 
Published: September 2024

ABSTRACTCircadian rhythms modulate the biology of many human tissues and are driven by a nearly 24‐h transcriptional feedback loop. Dynamic DNA methylation may play a role in driving 24‐h rhythms of gene expression in the human brain. However, little is known about the degree of circadian regulation between the DNA methylation and the gene expression in the peripheral tissues, including human blood. We hypothesized that 24‐h rhythms of DNA methylation play a role in driving 24‐h RNA expression in human blood. To test this hypothesis, we analyzed DNA methylation levels and RNA expression in blood samples collected from eight healthy males at six‐time points over 24 h. We assessed 442,703 genome‐wide CpG sites in methylation and 12,364 genes in expression for 24‐h rhythmicity using the cosine model. Our analysis revealed significant rhythmic patterns in 6345 CpG sites and 21 genes. Next, we investigated the relationship between methylation and expression using powerful circadian signals. We found a modest negative correlation (ρ = −0.83, p = 0.06) between the expression of gene TXNDC5 and the methylation at the nearby CpG site (cg19116172). We also observed that circadian CpGs significantly overlapped with genetic risk loci of schizophrenia and autism spectrum disorders. Notably, one gene, TXNDC5, showed a significant correlation between circadian methylation and expression and has been reported to be association with neuropsychiatric diseases.
Reversibility of cognitive worsening observed with BACE inhibitor umibecestat in the Alzheimer's Prevention Initiative (API) Generation Studies
Authors: Tariot Pierre N. , Riviere Marie‐Emmanuelle , Salloway Stephen , Burns Jeffrey M. , Snaedal Jón G. , Borowsky Beth , Lopez Cristina Lopez , Liu Fonda , Rouzade‐Dominguez Marie‐Laure , Cazorla Pilar , Mousseau Marie‐Catherine , Arkuszewski Michal , Ricart Javier , Viglietta Vissia , Sui Yihan , Caputo Angelika , Langbaum Jessica B. , Reiman Eric M. , Graf Ana 
Published: September 2024

AbstractINTRODUCTIONThe Alzheimer's Prevention Initiative (API) Generation Studies evaluated the BACE inhibitor umibecestat for Alzheimer's disease (AD) prevention. The studies were terminated early, and the reversibility of umibecestat's side effects was assessed.METHODSCognitively unimpaired 60‐ to 75‐year‐old apolipoprotein E (APOE) ε4 homozygotes and heterozygotes (the latter with elevated brain amyloid deposition) (n = 1556) received umibecestat (50 or 15 mg daily) or placebo for 7 months on average and were followed for a median (interquartile range) of 4 (3 to 6) months after washout.RESULTSCompared to placebo, umibecestat‐treated participants had small, non‐progressive, but statistically significant decline in performance on certain cognitive batteries including Repeatable Battery for the Assessment of Neuropsychological Status (RBANS) and API Preclinical Composite Cognitive test, but not Clinical Dementia Rating‐Sum of Boxes. RBANS differences were no longer significant at the end of follow‐up.DISCUSSIONIn people at genetic risk for AD, high‐dose beta‐site amyloid precursor protein cleaving enzyme (BACE) inhibition was associated with early mild cognitive worsening, which reversed shortly after washout, suggesting a symptomatic side effect not associated with neurodegeneration. Fully anonymized data, images, and samples are available upon request for further research on BACE inhibition.Highlights
This is the first trial with blinded assessment of reversibility of BACE inhibitor side effects.
Umibecestat was tested in cognitively unimpaired persons at genetic risk for AD.
Umibecestat led to early mild cognitive decline that reversed shortly after washout.
This suggests a potentially manageable effect not associated with neurodegeneration.
Further research may determine the future of BACE inhibition in AD prevention.
Die Azid‐Wittig Reaktion
Authors: Kushik  , Petrov A. , Ranieri D. , Edelmann L. , Beweries T. , Hering‐Junghans C. 
Published: September 2024

AbstractDie Einführung von Heteroatomen in konjugierte organische Moleküle ist eine wichtige Strategie, um deren Reaktivität und physikalischen Eigenschaften zu beeinflussen. In diesem Zusammenhang sind Triazabutadiene (TBDs) mit der allgemeinen Formel R2C=N−N=NR′ eine interessante Verbindungsklasse, für deren Darstellung es jedoch nur begrenzte allgemeingültige Syntheseprotokolle gibt. Basierend auf der zufälligen Entdeckung, dass das sterisch gehinderte Azid Mes*N3 (Mes*=2,4,6‐tBu3C6H2) mit PMe3 in Gegenwart eines aromatischen Aldehyds zu einem TBD reagierte, berichten wir nun über die „Azid‐Wittig“‐Reaktion. Diese Azid‐Wittig‐Reaktion hat sich als vielseitiges Werkzeug für die Synthese einer Vielzahl von TBDs erwiesen und eine breite Palette von Aldehyden und organischen Aziden werden als Kupplungspartner toleriert. Die Präferenz für die Azid‐Wittig‐ gegenüber der Aza‐Wittig‐Reaktivität wurde mithilfe von theoretischen Methoden untermauert. Diese Studie zeigt, wie der Reaktionspfad durch kinetische Kontrolle erheblich verändert kann, wodurch von einem Aza‐Wittig‐ zu einem Azid‐Wittig‐Regime gewechselt wird.
Rational Construction of Cyanide‐Functionalized D‐A‐π‐D Covalent Organic Framework for Highly Efficient Overall H2O2 Photosynthesis from Air and Water
Authors: Guo Liecheng , Gong Lele , Yang Yuting , Huang Zhecheng , Liu Xing , Luo Feng 
Published: September 2024

AbstractSacrificial‐agent‐free overall photosynthesis of H2O2 from water and air represents currently a promising route to reform the industrial anthraquinone production manner, but, still blocks by the requirement of pure O2 feedstock, due to the insufficient oxygen supply from water under air. Herein, we report a rational molecule design on COFs (covalent organic frameworks) equiped with cyanide‐functionalized D−A‐π‐D system for highly efficient overall H2O2 production from air and water through photocatalytic oxygen reduction reactions (ORR) and water oxidation reaction (WOR). Without using any sacrificial agent, the as‐synthesized D−A‐π‐D COF is found to enable a H2O2 production rate as high as 4742 μmol h−1 g−1 from water and air and an O2 utilization and conversion rate up to 88 %, exceeding the other D−A‐π‐A COF by respectively 1.9‐ and 1.3‐fold. Such high performance is attributed to the tuned electronic structure and prolonged charge lifetime facilitated by the unique D−A‐π‐D structure and cyanide groups. This work highlights a fundamental molecule design on advanced photocatalytic COFs with complicated D–A system for low‐cost and massive H2O2 production.
Multivalent Weak Protections Ultimately Enable Customizable DNA Grafting on Pristine Ag Colloids for Nanoplasmonics
Authors: Song Lei , Song Xiaojun , Li Yanjuan , Hao Yan , Wang Song , Deng Zhaoxiang 
Published: September 2024

AbstractSilver nanoparticles (AgNPs) have superior plasmonic properties surpassing other metals. However, a long‐standing difficulty in valence/density‐tunable DNA grafting of AgNPs disfavors their use in DNA‐directed nanoplasmonics. Herein a close‐to‐ideal surface protection of pristine AgNPs against various notorious stability issues of Ag is achieved based on multidentate weak nucleobase bindings of non‐programming FSDNA (fish sperm DNA). This further allows grafting of thiolated DNA with tunable valence/density on AgNPs. The end‐on format of the thiolated DNA grafts and the very thin FSDNA layer benefit DNA hybridization and plasmon coupling, respectively. Significantly promoted optical coupling and Raman enhancing are achieved. The compatibility of FSDNA‐capped AgNPs with Au enables DNA‐bonded symmetry‐broken Au−Ag heterodimers with strong near‐field coupling and an easily seen Fano‐induced feature. Our work provides a treasured freedom of using AgNPs in DNA‐programmed, better‐behaving plasmonic devices.
Allylic Epoxides Increase the Strain Energy of Cyclic Olefin Monomers for Ring‐Opening Metathesis Polymerization
Authors: Sylvester Kyle R. , Zovinka Jessa R. , Milrod Maya L. , Stubin Alexandra K. , Rojas‐Merchan Angela , Alexander Kayla , Elling Benjamin R. 
Published: September 2024

AbstractRing‐opening metathesis polymerization (ROMP) is an effective method for synthesizing functional polymers, but since the technique typically relies on high ring strain cyclic olefins, the most common monomers are norbornene derivatives. The reliance on one class of monomer limits the obtainable properties of ROMP polymers. In this work, we investigate new bicyclic monomers synthesized via epoxidation of commercial dienes. DFT estimates of these monomers’ ring strains suggests a significant increase in strain for cyclic olefins containing allylic epoxides. We found that the eight‐membered (3,4‐COO) and five‐membered (CPO) cyclic olefins were particularly effective for ROMP. CPO was of especially intriguing due to its excellent polymerizability when compared to the limited reactivity of other five‐membered rings. Unlike polynorbornenes, the resulting polymers of both monomers displayed glass transition temperatures well below room temperature. Interestingly, poly(3,4‐COO) showed both high stereo‐ and regioregularity while poly(CPO) showed little regularity. Both polymers could be readily modified via post‐polymerization ring‐opening of the reactive allylic epoxides. With a high epoxide density in poly(CPO), CPO is an exciting new ROMP monomer that is easily synthesized, can be polymerized to high conversion at room temperature, and may be facilely modified to yield a wide range of functional materials.
Chemo‐Enzymatische Depolymerisation von funktionalisiertem niedermolekularem Polyethylen
Authors: Oiffer Thomas , Leipold Friedemann , Süss Philipp , Breite Daniel , Griebel Jan , Khurram Muhammad , Branson Yannick , de Vries Erik , Schulze Agnes , Helm Christiane A. , Wei Ren , Bornscheuer Uwe T. 
Published: September 2024

AbstractPolyethylen (PE) ist der weltweit am häufigsten verwendete Kunststoff und trägt erheblich zur Kunststoffabfallkrise bei. Ein mikrobieller Abbau von PE in natürlicher Umgebung ist unwahrscheinlich, da die gesättigten Kohlenstoff‐Kohlenstoff‐Grundgerüste inert sind und von Enzymen nur schwer abgebaut werden können, was die Entwicklung einer biokatalytischen Recyclingmethode für PE‐Abfälle erschwert. In diesem Artikel demonstrieren wir die Depolymerisation von niedermolekularem PE (LMWPE) mit Hilfe einer Enzymkaskade, die eine Katalase‐Peroxidase, eine Alkoholdehydrogenase, eine Baeyer–Villiger‐Monooxygenase und eine Lipase umfasst, nachdem das Polymer mit m‐Chlorperoxybenzoesäure (mCPBA) und Ultraschall chemisch vorbehandelt wurde. In einem präparativen Experiment mit vorbehandeltem Polymer im Gramm‐Maßstab konnte mittels GC‐MS‐ und Gewichtsverlustbestimmungen ein Polymerabbau von ~27 % bestätigt werden. Dabei wurde die Bildung von funktionalisierten Molekülen mittlerer Größe wie ω‐Hydroxycarbonsäuren und α,ω‐Carbonsäuren erreicht. Zusätzliche Analysen von LMWPE‐Nanopartikeln mittels Rasterkraftmikroskopie (AFM) zeigten, dass die enzymatische Depolymerisation die Größe dieser mCPBA‐ und enzymbehandelten LMWPE‐Nanopartikel reduzierte. Dieses katalytische Multi‐Enzym‐Konzept mit unterschiedlichen chemischen Schritten stellt einen einzigartigen Ausgangspunkt für die künftige Entwicklung biobasierter Recyclingmethoden für Polyolefinabfälle dar.
Investigating Competing Inner‐ and Outer‐Sphere Electron‐Transfer Pathways in Copper Photoredox‐Catalyzed Atom‐Transfer Radical Additions: Closing the Cycle
Authors: Pham Le Nhan , Olding Angus , Ho Curtis C. , Bissember Alex C. , Coote Michelle L. 
Published: September 2024

AbstractThis integrated computational and experimental study comprehensively examines the viability of competing inner‐sphere electron transfer (ISET) and outer‐sphere electron transfer (OSET) processes in [Cu(dap)2]+‐mediated atom‐transfer radical additions (ATRA) of olefins and CF3SO2Cl that can deliver both R−SO2Cl and R−Cl products. Five sterically‐ and electronically‐varied representative alkenes were selected from which to explore and reconcile a range of experimentally observed outcomes. Findings are consistent with photoexcited [Cu(dap)2]+ initiating photoelectron transfer via ISET and the subsequent regeneration of the oxidized catalyst via ISET in the ground state to close the catalytic cycle and liberate products. R−SO2Cl/R−Cl product ratios appear to be primarily governed by the relative rates of direct catalyst regeneration {i.e., [Cu(dap)2SO2Cl]⋅++R⋅} and ligand exchange {i.e., [Cu(dap)2SO2Cl]⋅++Cl− }. Through this work, a more consistent and more complete conceptual framework has been developed to better understand this chemistry and how catalyst regeneration occurs. It is this important ground state process, which closes the catalytic cycle, and ultimately controls the enantioselectivity of ATRA reactions employing chiral copper photocatalysts.
The Azide‐Wittig Reaction
Authors: Kushik  , Petrov A. , Ranieri D. , Edelmann L. , Beweries T. , Hering‐Junghans C. 
Published: September 2024

AbstractThe introduction of heteroatoms into conjugated organic molecules is an important strategy to tune their reactivity and physical properties. In this realm triazabutadienes (TBDs) of the general from R2C=N−N=NR’ are an interesting class of compounds, however, general synthetic protocols for their generation are limited. Based on the serendipitous finding that the sterically encumbered azide Mes*N3 (Mes*=2,4,6‐tBu3C6H2) reacted with PMe3 in the presence of an aromatic aldehyde to form a TBD, we now report on the “Azide‐Wittig” reaction. This azide‐Wittig reaction is shown to be a versatile tool for the synthesis of a variety of TBDs, tolerating a wide range of aldehydes and organic azides as coupling partners. The preference for azide‐Wittig, rather than aza‐Wittig reactivity was rationalized using computational methods. This study shows how kinetic control can significantly alter the reaction pathway, thereby switching from an aza‐Wittig to an azide‐Wittig regime.
Ligand‐Insertion Strategy for Constructing 2D Conjugated Metal–Organic Framework with Large Pore Size for Electrochemical Analytics
Authors: Wang Xiu‐Zhen , Chen Yue , Cao Xiao‐Min , Li Ru‐Yi , Chen Wei‐Yan , Li Yue , Guo Dong‐Sheng 
Published: September 2024

AbstractTwo‐dimensional conjugated metal–organic frameworks (2D c‐MOFs) have shown great promise in various electrochemical applications due to their intrinsic electrical conductivity. A large pore aperture is a favorable feature of this type of material because it facilitates the mass transport of chemical species and electrolytes. In this work, we propose a ligand insertion strategy in which a linear ligand is inserted into the linkage between multitopic ligands, extending the metal ion into a linear unit of ‐M‐ligand‐M‐, for the construction of 2D c‐MOFs with large pore apertures, utilizing only small ligands. As a proof‐of‐concept trial of this strategy, a 2D c‐MOF with mesopores of 3.2 nm was synthesized using commercially available ligands hexahydrotriphenylene and 2,5‐dihydroxybenzoquinone. The facilitation of the diffusion of redox species by the large pore size of this MOF was demonstrated through a series of probes. With this feature, it showed superior performance in the electrochemical analysis of a variety of biological species.
Oriented Titanium‐MOF Membrane for Hydrogen Purification
Authors: Chen Sixing , Wahiduzzaman Mohammad , Ji Taotao , Liu Yi , Li Yang , Wang Chen , Sun Yanwei , He Gaohong , Maurin Guillaume , Wang Sujing , Liu Yi 
Published: September 2024

AbstractPrecise hydrogen sorting from purge gas (H2/N2) and coke gas (H2/CH4), commonly carried out by cryogenic distillation, still suffers from low separation efficiency, high energy consumption, and considerable capital cost. Though still in its infancy, membrane technology offers a potential to achieve more efficient hydrogen purification. In this study, an optimum separation of hydrogen towards both methane and nitrogen via a kinetically‐driven mechanism is realized through preferred orientation control of a MOF membrane. Relying on the 0.3 nm‐sized window aligned vertical to the substrate, b‐oriented Ti‐MOF membrane exhibits ultra‐high hydrogen selectivity, surpassing the upper bound limit of separating H2/N2 and H2/CH4 gas pairs attained so far by inorganic membranes. This spectacular selectivity is combined with a high H2 permeability owing to the synergistic effect of the 1 nm‐sized MOF channel.
The Key Descriptors for Predicting the Exciton Binding Energy of Organic Photovoltaic Materials
Authors: Zhu Lingyun , Huang Miaofei , Han Guangchao , Wei Zhixiang , Yi Yuanping 
Published: September 2024

AbstractExciton binding energy (Eb) is a key parameter to determine the mechanism and performance of organic optoelectronic devices. Small Eb benefits to reduce the interfacial energy offset and the energy loss of organic solar cells. However, quantum‐chemical calculations of the Eb in solid state with considering electronic polarization effects are extremely time‐consuming. Furthermore, current studies lack critical descriptors. Here, we use data‐driven machine learning (ML) to accelerate the computation and identify the key descriptors most relevant to the solid‐state Eb. The results verify two key descriptors associated with molecular and aggregation‐state properties for efficient prediction of the solid‐state Eb. Moreover, a very high accuracy is achieved by using the extreme gradient boosting algorithm, with the Pearson's correlation coefficient of 0.92. Finally, we use this ML model to predict the Eb of thin films, which is difficult to achieve using the current quantum‐chemical calculations due to the large structural disorder. Remarkably, the predicted thin‐film Eb values are fully consistent with the results of temperature‐dependent photoluminescence spectra. Therefore, our work provides an accurate and efficient approach to predict the solid‐state Eb and would be helpful to accelerate the exploitation of novel promising organic photovoltaic materials.
Chiral Au@CeO2 Helical Nanorods with Spatially Separated Structures for Polarization‐Dependent N2 Photofixation
Authors: Wang Fang , Yang Weimin , Ding Qi , Xing Xinhe , Xu Liguang , Lin Hengwei , Xu Chuanlai , Li Si 
Published: September 2024

AbstractChiral photocatalytic nanomaterials possess numerous unique properties and hold promise for various applications in chemical synthesis, environmental protection, energy conversion, and photoelectric devices. Nevertheless, it is uncommon to develop effective means to enhance the asymmetric catalytic performances of chiral plasmonic nanomaterials. In this study, a type of L/D‐Au@CeO2 helical nanorods (HNRs) was fabricated by selectively growing CeO2 on the surface of Au HNRs via a facile wet‐chemistry construction method. Chiral Au@CeO2 HNRs, featuring Au and CeO2 with spatially separated structures, exhibited the highest photocatalytic performance for N2 fixation, being 50.80±2.64 times greater than that of Au HNRs. Furthermore, when L‐Au@CeO2 HNRs were exposed to left circularly polarized light (CPL) and D‐Au@CeO2 HNRs were exposed to right CPL, their photocatalytic efficiency was enhanced by 3.06±0.06 times compared to the samples illuminated with the opposite CPL, which can be attributed to the asymmetrical generation of hot carriers upon CPL excitation. This study not only offers a simple approach to enhance the photocatalytic performance of chiral plasmonic nanomaterials but also demonstrates the potential of chiral plasmonic materials for application in specific photocatalytic reactions, such as N2 fixation.