bluuebunny/crossref_metadata_2025_split huggingface dataset:
The Best DFT Functional Is the Ensemble of Functionals
Authors: Rui Yuting , Chen Yuxinxin , Ivanova Elena , Kumar Vignesh Balaji , Śmiga Szymon , Grabowski Ireneusz , Dral Pavlo O. 
Published: October 2024

AbstractThe development of better density functional theory (DFT) methods is one of the most active research areas, given the importance of DFT for ubiquitous molecular and materials simulations. However, this research primarily focuses on improving a specific exchange‐correlation Kohn–Sham density functional. Here, a robust procedure is proposed for constructing transferable ensembles of density functionals that perform superior to any constituent individual density functional. It is shown that such ensembles built only with the density functionals predating the GMTKN55 benchmark of 2017 can reach a record‐low weighted error of 1.62 kcal mol−1 on this benchmark compared to 3.08 kcal mol−1 of the best constituent density functional. The DENS24 density functional ensembles are also introduced as practical DFT methods with consistently accurate performance for various simulations at affordable cost. DENS24 ensembles are open‐source and can be used for simulations online. Additionally, it is shown that the ensembles can be integrated into the SCF procedure by creating mixed DENS24 functionals, which have the same accuracy but are faster than ensembles of independent functionals.
Improved Charge‐Transfer Doping in Crystalline Polymer for Efficient and Stable Perovskite Solar Cells
Authors: Liu Huifen , Zhang Yu , Huang Zijian , Wu Yuetong , Wang Lan , Liu Guilin , Chen Yanrun , Li Kailin , Zhang Wenhua , Zhou Huanping 
Published: October 2024

AbstractPerovskite solar cells (PSCs) have significant potential for next‐generation photovoltaic technology applications. However, the instability of hole transport layers (HTLs) becomes the major obstacle to long‐term operational devices, which are affected by the intrinsic thermal instability and loose structure of hole transport materials, as well as the hygroscopicity and migration of dopants. Here, poly(3‐hexylthiophene‐2,5‐diyl) (P3HT) is used as a model crystalline polymer to thoroughly investigate effective p‐type doping strategies and the underlying mechanism. According to Hard–Soft‐Acid–Base theory, the soft base P3HT is more likely to form a stable Lewis acid–base adduct with the reactive soft acid radical, resulting in a strong charge‐transfer interaction, thereby enhancing conductivity and regulating the energy band of the HTL. Meanwhile, the radical cation salt can promote pre‐nucleation to optimize the crystallization orientation of P3HT. The resulting PSCs exhibited the efficiency of 25.16%, which is the highest efficiency reported so far based on doped P3HT. In addition, the resulting devices demonstrated excellent stability, maintaining 96.5%, 96%, and 91% of their initial efficiency after aging under continuous illumination for 2028 h, at 85 °C for 1080 h, and at maximum power point (MPP) tracking under continuous 1 Sun illumination at 85 °C for 528 h, respectively.
Continental sampling reveals core bacterial and environmentally driven fungal leaf endophytes in Heuchera
Authors: Pantinople Dexcem J. , Conner Reagan , Sutton‐Dauber Stephanie , Broussard Kelli , Siniscalchi Carolina M. , Engle‐Wrye Nicholas J. , Jordan Heather R. , Folk Ryan A. 
Published: October 2024

AbstractPremiseEndophytic plant‐microbe interactions range from mutualistic relationships that confer important ecological and agricultural traits to neutral or quasi‐parasitic relationships. In contrast to root‐associated endophytes, the role of environmental and host‐related factors in the acquisition of leaf endophyte communities at broad spatial and phylogenetic scales remains sparsely studied. We assessed endofoliar diversity to test the hypothesis that membership in these microbial communities is driven primarily by abiotic environment and host phylogeny.MethodsWe used a broad geographic coverage of North America in the genus Heuchera L. (Saxifragaceae), representing 32 species and varieties across 161 populations. Bacterial and fungal communities were characterized using 16S and ITS amplicon sequencing, respectively, and standard diversity metrics were calculated. We assembled environmental predictors for microbial diversity at collection sites, including latitude, elevation, temperature, precipitation, and soil parameters.ResultsAssembly patterns differed between bacterial and fungal endophytes. Host phylogeny was significantly associated with bacteria, while geographic distance was the best predictor of fungal community composition. Species richness and phylogenetic diversity were consistent across sites and species, with only fungi showing a response to aridity and precipitation for some metrics. Unlike what has been observed with root‐associated microbial communities, in this system microbes show no relationship with pH or other soil factors.ConclusionsOverall, this work improves our understanding of the large‐scale patterns of diversity and community composition in leaf endophytes and highlights the relative significance of environmental and host‐related factors in driving different microbial communities within the leaf microbiome.
The Secondary Sex Ratio and Male Mortality at Pre‐Reproductive Ages: A Test of Selection In Utero
Authors: Bonham Jason , Schacht Ryan , Smith Ken , Bruckner Tim A. 
Published: October 2024

ABSTRACTObjectivesThe secondary sex ratio (i.e., the ratio of male to female live births; hereafter referred to as the SSR) falls in populations encountering ambient stressors. Much theory and some empirical work indicates that males born to low SSR cohorts may be “positively selected” in that excess culling in utero may correspond with greater than expected survival among live‐born males in that cohort. We extend prior work by testing, in historical Utah, whether the SSR varies positively with male mortality at pre‐reproductive ages.MethodsThis study uses detailed records from the Utah Population Database to focus on Utahns born 1850–1940. We use rigorous time‐series methods, which control for strong secular declines in mortality as well as ambient perturbations shared equally among males and females, to investigate the male culling inference.ResultsWe observe a positive relation between the SSR and male mortality during youth (i.e., 5 to < 20 years; p < 0.05) but not in infancy or early childhood.ConclusionsIn this historical population, the SSR appears to gauge hardiness of surviving male cohorts. However, whether the high fertility and/or family structure context of Latter‐day Saints in historical Utah explains the age‐specific pattern of male mortality warrants further scrutiny.
Everyone Is a Tomato: Metagnostic Narratives of Genetic Revelation
Authors: Spencer Danielle 
Published: October 2024

ABSTRACTThis essay explores the narrative characteristics of genetic revelations as instances of “metagnosis.” Contrasting the scientific narrative of increasing knowledge with a series of different stories—including fictional tales—demonstrates the complexity of receiving information that changes one's conception of self, whatever the nature of the revelation. Such narrative awareness can help to communalize such experiences, reducing feelings of isolation and bewilderment.
Modifikation eines Cu‐Pd‐Schaufelrad‐Metall‐Organischen Gerüsts für die selektive CO2‐Elektroreduktion
Authors: Zhang Ruirui , Liu Yan , Ding Pan , Huang Juanjuan , Dierolf Martin , Kelly Shelly D. , Qiu Xinqi , Chen Yishuo , Hussain Mian Zahid , Li Weijin , Bunzen Hana , Achterhold Klaus , Pfeiffer Franz , Sharp Ian D. , Warnan Julien , Fischer Roland A. 
Published: October 2024

AbstractDie Optimierung der Bindungsenergie zwischen dem Intermediat und dem aktiven Zentrum ist ein entscheidender Faktor, um die katalytische Produktselektivität und Aktivität bei der elektrochemischen Kohlendioxidreduktion (CO2RR) zu steuern. Es ist bekannt, dass Kupferatome als aktive Zentren CO2 zu Kohlenwasserstoffen und Sauerstoffverbindungen reduzieren, jedoch unter schlechter Produktselektivität leiden, da mehrere Intermediate nur moderate Bindungsenergien aufweisen. Hier berichten wir über eine Ionenaustauschstrategie zur Konstruktion von Cu−Pd‐Schaufelrad‐Dimeren innerhalb von Cu‐basierten metallorganischen Gerüsten (MOFs), [Cu3‐xPdx(BTC)2] (BTC=1,3,5‐Benzoltricarbonsäure), ohne die strukturellen Eigenschaften des MOFs zu verändern. Im Vergleich zum reinen Cu‐MOF ([Cu3(BTC)2], HKUST‐1) verlagert der Cu−Pd‐MOF die Produkte der CO2‐Elektroreduktion von einer Vielzahl chemischer Spezies hin zu einer selektiven CO‐Erzeugung. Eine in situ‐Röntgenabsorptions‐Feinstrukturanalyse der Oxidationsstufe des Katalysators und der lokalen Geometrie, kombiniert mit theoretischen Berechnungen, zeigt, dass die Einfügung von Pd in die Knotenpunkte der Cu‐Schaufelradstruktur des MOFs die Adsorption des Schlüsselintermediats COOH* am Cu‐Zentrum fördert. Dies ermöglicht CO‐selektive katalytische Mechanismen und verbessert somit unser Verständnis über das Zusammenspiel von Struktur und Aktivität bei der elektrochemischen CO2‐Reduktion unter Verwendung molekularer Katalysatoren.
Room‐temperature Magnetocapacitance Spanning 97K Hysteresis in Molecular Material
Authors: Gui Ling‐Ao , Chen Jiawei , Zhang Yi‐Fan , Li Long‐He , Li Jian‐Rong , Hu Zhao‐Bo , Zhang Shi‐Yong , Zhang Jinlei , Zhang Zhenyi , Ye Heng‐Yun , Peng Yan , Ma Jing , Song You 
Published: October 2024

AbstractMagnetic capacitor, as a new type of device, has broad application prospects in fields such as magnetic field sensing, magnetic storage, magnetic field control, power electronics and so on. Traditional magnetic capacitors are mostly assembled by magnetic and capacitive materials. Magnetic capacitor made of a single material with intrinsic properties is very rare. This intrinsic property is magnetocapacitance (MC). The studies on MC effect have mainly focused on metal oxides so far. No study was reported in molecular materials. Herein, two complexes: (CETAB)2[CuCl4] (1) and (CETAB)2[CuBr4] (2) (CETAB=(2‐chloroethyl)trimethylammonium) are reported. There exist strong H−Br and Br−Br interactions and other weak interactions in complex 2, so the phase transition energy barrier is high, resulting in the widest thermal hysteresis loop on a molecular level to date. Furthermore, complexes 1 and 2 show large MC parameters of 0.247 and 1.614, respectively, which is the first time to observe MC effect in molecular material.
Nature‐Inspired N, O Co‐Coordinated Manganese Single‐Atom Catalyst for Efficient Hydrogen Peroxide Electrosynthesis
Authors: Zeng Yuan , Tan Xin , Zhuang Zewen , Chen Chen , Peng Qing 
Published: October 2024

AbstractThe two‐electron oxygen reduction reaction (2e− ORR) is a pivotal pathway for the distributed production of hydrogen peroxide (H2O2). In nature, enzymes containing manganese (Mn) centers can convert reactive oxygen species into H2O2. However, Mn‐based heterogeneous catalysts for 2e− ORR are scarcely reported. Herein, we developed a nature‐inspired single‐atom electrocatalyst comprising N, O co‐coordinated Mn sites, utilizing carbon dots as the modulation platform (Mn CD/C). As‐synthesized Mn CD/C exhibited exceptional 2e− ORR activity with an onset potential of 0.786 V and a maximum H2O2 selectivity of 95.8 %. Impressively, Mn CD/C continuously produced 0.1 M H2O2 solution at 200 mA/cm2 for 50 h in the flow cell, with negligible loss in activity and H2O2 faradaic efficiency, demonstrating practical application potential. The enhanced activity was attributed to the incorporation of Mn atomic sites into the carbon dots. Theoretical calculations revealed that the N, O co‐coordinated structure, combined with abundant oxygen‐containing functional groups on the carbon dots, optimized the binding strength of intermediate *OOH at the Mn sites to the apex of the catalytic activity volcano. This work illustrates that carbon dots can serve as a versatile platform for modulating the microenvironment of single‐atom catalysts and for the rational design of nature‐inspired catalysts.
Redox‐Selbstequilibrierung in molekularen Vanadiumoxid‐ Mischungen ermöglicht Multi‐ Elektronenspeicherung
Authors: Remmers Moritz , Mashtakov Boris , Repp Stefan , Rein Alexandra Stefanie Jessica , Wang Ke , Anjass Montaha , Chen Zhengfan , Carrella Luca M. , Rentschler Eva , Streb Carsten 
Published: October 2024

AbstractPolyoxometallate (POM) sind ideale Komponenten für die reversible Multielektronenspeicherung in der Energietechnik. Bislang werden in den meisten Redox‐Anwendungen nur einzelne POM‐Spezies verwendet, was die Anzahl der Elektronen, die innerhalb eines bestimmten Potenzialfensters gespeichert werden können, begrenzt. Hier berichten wir, dass eine spontane Redox‐ Selbstequilibrierung während der Clustersynthese zur Bildung von zwei strukturell verwandten Polyoxovanadaten führt, die anschließend zu Ko‐Kristallen aggregieren. Dies führt zu Systemen mit deutlich erhöhter Redox‐Reaktivität. Das gemischte POM‐System wurde durch nichtwässrige Selbstassemblierung einer Vanadat‐Vorstufe in Gegenwart von Mg2+ gebildet, was zu zwei gemischtvalenten (VIV/V) Spezies führte, [(MgOH)V13O33Cl]4− (={MgV13}) und der Di‐Vanadium‐funktionalisierten Spezies [V14O34Cl]4− (={V14}), die in einer 1 : 1‐Molstöchiometrie ko‐kristallisieren. Experimentelle Daten zeigen, dass {MgV13} im nativen Zustand um drei Elektronen und {V14} um fünf Elektronen reduziert ist. Elektrochemische Untersuchungen in Lösung zeigen, dass das System reversibel bis zu vierzehn Redoxübergänge (vorläufig zwölf 1‐Elektronen‐Prozesse und zwei 2‐Elektronen‐Prozessen zugeordnet) im Potenzialbereich zwischen −2,15 V und +1,35 V (gegen Fc+/Fc) durchlaufen kann. Die Studie zeigt, wie hochgradig redoxaktive, wohldefinierte Mischungen aus gemischtvalenten molekularen Metalloxiden durch Redox‐ Selbstequilibrierung während der Synthese zugänglich gemacht werden können, was neue Möglichkeiten für die molekulare Energiespeicherung eröffnet.
Redox Self‐Equilibration in Molecular Vanadium Oxide Mixtures Enables Multi‐Electron Storage
Authors: Remmers Moritz , Mashtakov Boris , Repp Stefan , Rein Alexandra Stefanie Jessica , Wang Ke , Anjass Montaha , Chen Zhengfan , Carrella Luca M. , Rentschler Eva , Streb Carsten 
Published: October 2024

AbstractPolyoxometalates (POMs) are ideal components for reversible multi‐electron storage in energy technologies. To‐date, most redox‐applications employ only single, individual POM species, which limits the number of electrons that can be stored within a given potential window. Here, we report that spontaneous redox self‐equilibration during cluster synthesis leads to the formation of two structurally related polyoxovanadates which subsequently aggregate into co‐crystals. This results in systems with significantly increased redox reactivity. The mixed POM system was formed by non‐aqueous self‐assembly of a vanadate precursor in the presence of Mg2+, resulting in two mixed‐valent (VIV/V) species, [(MgOH)V13O33Cl]4− (={MgV13}) and the di‐vanadium‐functionalized species [V14O34Cl]4− (={V14}), which co‐crystallize in a 1 : 1 molar stoichiometry. Experimental data indicate that in the native state, {MgV13} is reduced by three electrons, and {V14} is reduced by five electrons. Electrochemical studies in solution show, that the system can reversibly undergo up to fourteen redox transitions (tentatively assigned to twelve 1‐electron processes and two 2‐electron processes) in the potential range between −2.15 V to +1.35 V (vs Fc+/Fc). The study demonstrates how highly redox‐active, well‐defined molecular mixtures of mixed‐valent molecular metal oxides can be accessed by redox‐equilibration during synthesis, opening new avenues for molecular energy storage.
Influence of Plasmonic Au@Cl/N Co‐doped Carbon Dots on the Performance of Dye‐Sensitized Solar Cells
Authors: Hezarkhani Zeinab , Ghadari Rahim 
Published: October 2024

ABSTRACTThe synergistic influence of the LSPR (localized surface plasmon resonance) of gold nanoparticles (Au NPs) and the effect of nitrogen and chlorine co‐doped carbon dots (Cl/N‐CQDs) on dye‐sensitized solar cells (DSSCs) performance are investigated. The gold NPs are coated with a thin layer of Cl/N‐CQDs to produce the Au@Cl/N‐CQDs structure. DSSCs are fabricated by using Au@Cl/N‐CQDs as co‐sensitizer. The focus of this work is to examine the effects of plasmonic Au NPs and carbon dots in addition to their synergistic effect by capping the Au NPs with Cl/N‐CQDs, and track their influence in DSSCs. N719 as ruthenium‐based dye, and natural dyes including betanin, crocin, carthamin, curcumin, chlorophyll, mallow, and lawsone are selected and applied in the DSSCs co‐sensitized by Au@Cl/N‐CQDs. The power conversion efficiency (PCE) of DSSCs using all of the selected dyes is enhanced upon using the Au@Cl/N‐CQDs. It is due to the improvement in VOC (open circuit voltage) and JSC (short circuit photocurrent densities) relative to the use of dyes alone. Based on computational results, Au@Cl/N‐CQDs cause a red‐shift in comparison with pure dyes. The TD‐DFT (time‐dependent density functional theory) results show that the orbitals from the Au@Cl/N‐CQDs in dye/Au@Cl/N‐CQDs have contribution in most of the absorptions. In other words, electrons from HOMO (highest occupied molecular orbital) of Au@Cl/N‐CQDs is transferred to the LUMO (lowest unoccupied molecular orbital) of dye, in most cases.
In silico–guided synthesis of a new, highly soluble, and anti‐melanoma flavone glucoside: Skullcapflavone II‐6′‐O‐β‐glucoside
Authors: Chang Te‐Sheng , Ding Hsiou‐Yu , Wang Tzi‐Yuan , Wu Jiumn‐Yih , Tsai Po‐Wei , Suratos Khyle S. , Tayo Lemmuel L. , Liu Guan‐Cheng , Ting Huei‐Ju 
Published: October 2024

AbstractGuided by in silico analysis tools and biotransformation technology, new derivatives of natural compounds with heightened bioactivities can be explored and synthesized efficiently. In this study, in silico data mining and molecular docking analysis predicted that glucosides of skullcapflavone II (SKII) were new flavonoid compounds and had higher binding potential to oncogenic proteins than SKII. These benefits guided us to perform glycosylation of SKII by utilizing four glycoside hydrolases and five glycosyltransferases (GTs). Findings unveiled that exclusive glycosylation of SKII was achieved solely through the action of GTs, with Bacillus subtilis BsUGT489 exhibiting the highest catalytic glycosylation efficacy. Structure analysis determined the glycosylated product as a novel compound, skullcapflavone II‐6′‐O‐β‐glucoside (SKII‐G). Significantly, the aqueous solubility of SKII‐G exceeded its precursor, SKII, by 272‐fold. Furthermore, SKII‐G demonstrated noteworthy anti‐melanoma activity against human A2058 cells, exhibiting an IC50 value surpassing that of SKII by 1.4‐fold. Intriguingly, no substantial cytotoxic effects were observed in a murine macrophage cell line, RAW 264.7. This promising anti‐melanoma activity without adverse effects on macrophages suggests that SKII‐G could be a potential candidate for further preclinical and clinical studies. The in silico tool–guided synthesis of a new, highly soluble, and potent anti‐melanoma glucoside, SKII‐G, provides a rational design to facilitate the future discovery of new and bioactive compounds.
Untersuchung von Naturkautschuklatex‐ (NRL‐) Verbundstoffen durch Druckversuche für erneuerbare und nachhaltige Baumaterialien
Authors: Qdeimat Malik , Pranjic Andrija , Trautz Martin 
Published: October 2024

AbstractIn diesem Aufsatz wird die innovative Verwendung von Naturkautschuklatex (NRL) als grundlegende Komponente bei der Entwicklung nachhaltiger und erneuerbarer Bauverbundwerkstoffe untersucht, wobei der Schwerpunkt auf der Einbeziehung von Holzspänen als Verstärkungspartikel liegt. Die Studie untersucht die mechanischen Druckeigenschaften verschiedener Verbundwerkstoffformulierungen und analysiert den Einfluss von NRL‐Gehalten und Partikeltypen unter Berücksichtigung verschiedener Holzarten, Formen und Größen. Schlüsselfaktoren wie die Partikelgeometrie, der NRL‐Gehalt und die Probenvorbereitungsmethoden werden als entscheidende Faktoren für die Verbesserung der mechanischen Eigenschaften dieser Verbundwerkstoffe identifiziert. Die Ergebnisse zeigen, dass NRL‐Verbundwerkstoffe besondere Eigenschaften wie nichtlineares Verhalten, Hysterese, Spannungsrelaxation und den Mullins‐Effekt bei Druckversuchen aufweisen. Die Bedeutung dieser Verbundwerkstoffe im Bauwesen wird durch die Möglichkeit erhöht, NRL aus anderen Pflanzen als Kautschukbäumen, wie z. B. Löwenzahn, zu verwenden und damit nachhaltige Baupraktiken zu fördern. Diese Forschung zielt darauf ab, die Aufmerksamkeit auf die Erforschung neuer, flexibler und hochgradig kundenspezifischer Verbundwerkstoffe unter Verwendung von Naturfasern und NRL für eine Reihe von Bauanwendungen zu richten.
Engineering GID4 for use as an N‐terminal proline binder via directed evolution
Authors: Ikonomova Svetlana P. , Yan Bo , Sun Zhiyi , Lyon Rachel B. , Zatopek Kelly M. , Marino John P. , Kelman Zvi 
Published: October 2024

AbstractNucleic acid sequencing technologies have gone through extraordinary advancements in the past several decades, significantly increasing throughput while reducing cost. To create similar advancement in proteomics, numerous approaches are being investigated to advance protein sequencing. One of the promising approaches uses N‐terminal amino acid binders (NAABs), also referred to as recognizers, that selectively can identify amino acids at the N‐terminus of a peptide. However, there are only a few engineered NAABs currently available that bind to specific amino acids and meet the requirements of a biotechnology reagent. Therefore, additional NAABs need to be identified and engineered to enable confident identification and, ultimately, de novo protein sequencing. To fill this gap, a human protein GID4 was engineered to create a NAAB for N‐terminal proline (Nt‐Pro). While native GID4 binds Nt‐Pro, its binding is weak (µmol/L) and greatly influenced by the identity of residues following the Nt‐Pro. Through directed evolution, yeast‐surface display, and fluorescence‐activated cell sorting, we identified sequence variants of GID4 with increased binding response to Nt‐Pro. Moreover, variants with an A252V mutation showed a reduced influence from residues in the second and third positions of the target peptide when binding to Nt‐Pro. The workflow outlined here is shown to be a viable strategy for engineering NAABs, even when starting from native Nt‐binding proteins whose binding is strongly impacted by the identity of residues following Nt‐amino acid.