bluuebunny/crossref_metadata_2025_split huggingface dataset:
Nonfullerene Acceptors Bearing Spiro‐Substituted Bithiophene Units in Organic Solar Cells: Tuning the Frontier Molecular Orbital Distribution to Reduce Exciton Binding Energy
Authors: Wang Kai , Jinnai Seihou , Urakami Takumi , Sato Hirofumi , Higashi Masahiro , Tsujimura Sota , Kobori Yasuhiro , Adachi Rintaro , Yamakata Akira , Ie Yutaka 
Published: August 2024

AbstractThe development of nonfullerene acceptors (NFAs), represented by ITIC, has contributed to improving the power conversion efficiency (PCE) of organic solar cells (OSCs). Although tuning the electronic structures to reduce the exciton binding energy (Eb) is considered to promote photocharge generation, a rational molecular design for NFAs has not been established. In this study, we designed and developed two ITIC‐based NFAs bearing spiro‐substituted bithiophene or biphenyl units (named SpiroT‐DCI and SpiroF‐DCI) to tune the frontier molecular orbital (FMO) distribution of NFAs. While the highest occupied molecular orbitals (HOMOs) of SpiroF‐DCI and ITIC are delocalized in the main π‐conjugated framework, the HOMO of SpiroT‐DCI is distributed on the bithiophene unit. Reflecting this difference, SpiroT‐DCI exhibits a smaller Eb than either SpiroF‐DCI or ITIC, and exhibits greater external quantum efficiency in single‐component OSCs. Furthermore, SpiroT‐DCI shows improved PCEs for bulk‐heterojunction OSCs with a donor of PBDB‐T, compared with that of either SpiroT‐DCI or ITIC. Time‐resolved spectroscopy measurements show that the photo‐induced intermolecular charge separation is effective even in pristine SpiroT‐DCI films. This study highlights the introduction of spiro‐substituted bithiophene units that are effective in tuning the FMOs of ITIC, which is desirable for reducing the Eb and improving the PCE in OSCs.
Nacre‐Inspired Structure Enables Ultrahigh ‘Strong‐Tough’ Design of Phosphorus Anode
Authors: Sun Baoyu , Wang Shuai , Mao Caiwang , Qiao Rui , Ravivarma Mahalingam , Liu Shude , Fan Hao , Xie Jingying , Song Jiangxuan 
Published: August 2024

AbstractRed phosphorus anode, attributed to its high specific capacity of 2596 mAh g−1, is expected to improve the energy density of Na‐ion batteries. However, the P anode currently is unsatisfactory for practical usage due to the large volume expansion beyond 300 %, which brings out uncontrolled brittle failure. To address this challenge, we here design a nacre‐like phosphorus anode by resilient graphene oxide staggered together. The staggered structure simultaneously offers mechanical strength and interwoven toughness. Finite element modeling reveals that the sodiation stress from P nanoparticles will be transferred into interlayer pillars as the elastic medium to release sodiation stress. The prepared anode achieves an ultrahigh areal capacity of 13 mAh cm−2 at a mass loading of 5.8 mg cm−2. Notably, the volume change of the anode is limited to approximately 8.1 % at full sodiation, significantly lower than that of the traditional phosphorus electrodes.
Oxyanion Engineering on RuO2 for Efficient Proton Exchange Membrane Water Electrolysis
Authors: Duan Ying , Wang Lin‐Lin , Zheng Wen‐Xing , Zhang Xiao‐Long , Wang Xiao‐Ran , Feng Guo‐Jin , Yu Zi‐You , Lu Tong‐Bu 
Published: August 2024

AbstractIn acidic proton exchange membrane water electrolysis (PEMWE), the anode oxygen evolution reaction (OER) catalysts rely heavily on the expensive and scarce iridium‐based materials. Ruthenium dioxide (RuO2) with lower price and higher OER activity, has been explored for the similar task, but has been restricted by the poor stability. Herein, we developed an anion modification strategy to improve the OER performance of RuO2 in acidic media. The designed multicomponent catalyst based on sulfate anchored on RuO2/MoO3 displays a low overpotential of 190 mV at 10 mA cm−2 and stably operates for 500 hours with a very low degradation rate of 20 μV h−1 in acidic electrolyte. When assembled in a PEMWE cell, this catalyst as an anode shows an excellent stability at 500 mA cm−2 for 150 h. Experimental and theoretical results revealed that MoO3 could stabilize sulfate anion on RuO2 surface to suppress its leaching during OER. Such MoO3‐anchored sulfate not only reduces the formation energy of *OOH intermediate on RuO2, but also impedes both the surface Ru and lattice oxygen loss, thereby achieving the high OER activity and exceptional durability.
Modulating Magnetic Performance in DyIII Single Ion Magnets With N5O2 Ligands
Authors: Fondo Matilde , Oreiro‐Martínez Paula , Corredoira‐Vázquez Julio , García‐Deibe Ana M. , Sanmartín‐Matalobos Jesús , Aravena Daniel 
Published: August 2024

ABSTRACT[Dy (LMe)(H2O)]CF3SO3·0.25H2O (1·0.25H2O), where H2LMe is the reported ligand 2,2′‐(((pyridine‐2,6‐diylbis (methylene))bis((pyridin‐2‐ylmethyl)azanediyl))bis (methylene))bis(4‐methylphenol), shows the DyIII ion in an N5O3 environment, with triangular dodecahedral geometry (D2d symmetry). 1·0.25H2O is a single ion magnet (SIM) with an energy barrier for spin reversal of 510 K, and open hysteresis loops up to 8 K. The magnetostructural comparison of 1·0.25H2O with some closely related complexes and with other eight‐coordinated SIMs with high energy barriers (> 300 K) allows to draw some conclusions to enhance the magnetic performance in these nanomagnets with non‐purely axial geometries. Ab initio calculations complement and support the experimental results.
Efficacy Versus Effectiveness: The HORIZON‐Pivotal Fracture Trial and Its Emulation in Claims Data
Authors: D'Andrea Elvira , Schneeweiss Sebastian , Franklin Jessica M. , Kim Seoyoung C. , Glynn Robert J. , Lee Su Been , Wang Shirley V. 
Published: August 2024

ObjectiveThe objective of this study is to evaluate the concordance of results between the Health Outcomes and Reduced Incidence with Zoledronic Acid Once Yearly (HORIZON)–Pivotal Fracture Trial (PFT) and a nonrandomized database study designed to emulate the trial.MethodsHORIZON‐PFT evaluated the efficacy of zoledronic acid versus placebo in reducing the risk of hip fractures and found a 41% risk reduction over a three‐year treatment period (hazard ratio [HR] = 0.59; 95% confidence interval [95% CI] 0.42–0.83). Using two US claims databases from August 2007 to December 2020 or June 2021, we applied eligibility criteria from HORIZON‐PFT and identified women with osteoporosis who initiated zoledronic acid or raloxifene as a proxy for placebo. The study protocol was registered on ClinicalTrials.gov (NCT04736693) before inferential analyses. We compared HORIZON‐PFT and database study results using prespecified metrics.ResultsBecause of low adherence in clinical practice, on‐treatment follow‐up was truncated at 18 months in the database study. The hip fracture risk after 18 months was 9.3 in 1,000 in the trial and 8.3 in 1,000 in the database analysis. In the database study, zoledronic acid was associated with a 28% reduction in hip fractures risk compared with raloxifene (HR = 0.72; 95% CI 0.51–0.92). The attenuated effect of zoledronic acid in the database study may be explained by its shorter follow‐up, because the interpolated estimate of the effect in HORIZON‐PFT at 18 months was HRRCT (randomized controlled trial), 0.74, nearly identical to the observational estimate HRdatabase 0.72.ConclusionReal‐world emulation of the HORIZON‐PFT found that zoledronic acid reduced hip fractures risk over an 18‐month follow‐up period. Limited adherence in clinical practice diminished the magnitude of its preventive effect and precluded long‐term estimation of effectiveness in this setting.
Adjusting the Covalency of Metal‐Oxygen Bonds in CuBi2O4 by Zn Cation Doping to Achieve Highly Efficient Photocathodes
Authors: Zhang Yuheng , Xu Yusheng , Zhang Kejing , Li Zhixue , Lin Zeze , Hu Junhua , Song Angang 
Published: August 2024

AbstractZn doped CuBi2O4 photocathodes are prepared by using a low‐cost solution‐based spray pyrolysis method. The doping of Zn in CuBi2O4 promotes the separation and migration of carriers and effectively increases the carrier density. Compared with CuBi2O4 alone, the photoelectrochemical activity of the Zn doped CuBi2O4 photoelectrode is improved with the photocurrent density of −0.56 mA/cm2 at 0.4 V vs. RHE. This improvement is due to the lower electronegativity of Zn, which leads to the covalent increase of Cu−O and Bi−O bonds in CuBi2O4, which limits the recombination of photogenerated electrons and holes and improves charge separation and transport. This study presents an innovative approach to enhance the charge separation efficiencies of photocathodes by implementing element doping strategies, which may contribute to further research on photocatalytic water splitting.
Exploring the Impact of Oxygen Vacancies in Co/Pr‐CeO2 Catalysts on H2 Production via the Water‐Gas Shift Reaction
Authors: Saini Pallavi , Koley Paramita , Damma Devaiah , Jampaiah Deshetti , Bhargava Suresh K. 
Published: August 2024

AbstractIn this study, we utilized various Pr‐doped CeO2 catalysts (Pr=5, 10, 20, and 30 wt.%) as a support medium for the dispersion of cobalt (Co) nanoparticles, aiming to investigate the impact of oxygen vacancies on the water‐gas shift (WGS) reaction. Different characterization techniques were employed to understand the insights into the structure‐activity relationship governing the performance of Pr doped ceria supported Co catalysts towards WGS reaction. Our findings reveal that Co/Pr‐CeO2 catalysts at optimum Pr loading (10 wt.%) exhibit a superior CO conversion (88 %) facilitated by the presence of more oxygen vacancies induced by Pr doping into the CeO2 lattice, as opposed to the performance of the pure Co/CeO2 catalytic system. It was also found that the highest activity was obtained at increased intrinsic oxygen vacancies and strong synergy between Co and Pr/CeO2 support, fostering more favorable CO activation at the interfacial sites, thus accounting for the observed enhanced activity.
Bewertung von Steinschlagschutzzäunen für Niedrigenergiebereiche
Authors: Koch Andreas , Berger Simon , Hofmann Robert , Jansen Philipp 
Published: August 2024

AbstractAktuelle Untersuchungen zum Thema Steinschlagschutzverbauungen konzentrieren sich i. d. R. auf mittlere bis hohe Einwirkungsenergien. Für flexible Steinschlagschutzzäune existieren bereits Systeme mit einer Energieaufnahmefähigkeit in einer Größenordnung bis ca. 10.000 kJ. In vielen Regionen ist die Stein‐ und Blockschlaggefahr aber oft mit deutlich geringeren Energien verbunden. Dies ist insbesondere entlang von Infrastruktur wie Verkehrswegen der Fall. Die Bayerische Staatsbauverwaltung hat demzufolge Drahtzäune als Abrollschutz im Einsatz, welche explizit den Bereich mit einer Energieaufnahmefähigkeit bis 60 kJ abdecken. Die Drahtzäune bestehen aus handelsüblichen und bei entsprechenden Fachfirmen lagernden Komponenten und wurden durch die Zentralstelle Ingenieurbauwerke und Georisiken (ZIG) mit einer Bauhöhe von 2,30 m in einem Steinbruch nahe Passau getestet. Während der Versuche wurden von der Universität Innsbruck, Arbeitsbereich Geotechnik, die maßgeblichen Seilkräfte gemessen und die Kinematik der Versuchsblöcke über Videoanalysen ausgewertet. Der Beitrag beschreibt die Konstruktionsdetails des Drahtzauns, die Randbedingungen der 1 : 1‐Belastungsversuche, die Auswertung der Messdaten sowie die weiteren Erkenntnisse für die Ausführung. Zusätzlich wird der zeitliche Verlauf der Kräfte bei der Bestimmung der Bemessungseinwirkungen auf Verankerungen bzw. Fundationen untersucht.
Bauen im Bestand unter Berücksichtigung des zeitabhängigen Tragverhaltens von Gründungen
Authors: Reul Oliver , Ganal Aljoscha , Kissel Wolfgang , Ramm Hendrik 
Published: August 2024

AbstractIm Zusammenhang mit der Modernisierung und Revitalisierung von Bestandsbauwerken sind zunehmend komplexe Aufgabenstellungen wie z. B. die Wiedernutzung von vorhandenen Gründungskörpern zu bearbeiten. In der Vergangenheit wurden bspw. in Frankfurt am Main verschiedene Vorhaben realisiert, bei denen Bestandsbauwerke nach Teilabbruch kraftschlüssig mit einem Neubau verbunden wurden. In einem Forschungsvorhaben wurden umfangreiche Untersuchungen zum Langzeitverformungsverhalten von Gründungen unter Wechselbeanspruchungen, wie sie u. a. bei teilweisem Abbruch und Wiederaufbau auftreten, durchgeführt. In diesem Zusammenhang wurde u. a. auf über mehrere Jahrzehnte reichende Messungen an Hochhausgründungen in Frankfurt am Main zurückgegriffen und das zeitabhängige Materialverhalten der überkonsolidierten tertiären Frankfurter Tone in einem umfassenden Laborprogramm untersucht sowie numerische Studien durchgeführt. Mit einer numerischen Parameterstudie wurden u. a. die Auswirkungen von Wechselbeanspruchungen, Konsolidation und Kriechen auf die Lastverteilung zwischen Pfählen und Fundamentplatte von Kombinierten Pfahl‐Plattengründungen (KPP) sowie auf die in der Ingenieurpraxis gebräuchlichen Bemessungskennwerte, nämlich Pfahlfedersteifigkeit und Bettungsmodul, untersucht. In diesem Beitrag werden zum einen im Rahmen der Parameterstudie gewonnene Erkenntnisse zusammengefasst und zum anderen die Projekte Park Tower und Leo in Frankfurt am Main vorgestellt.
Beitrag zur Durchmesserbestimmung an Pfählen auf der Grundlage des Thermal Integrity Profiling
Authors: Kindler Arne , Lübben Jasper 
Published: August 2024

AbstractIm Rahmen der Durchführung eines Thermal Integrity Profiling (TIP) wird oft davon gesprochen, dass das Profiling u. a. dazu dient, die Kubatur des erstellten Pfahls zu ermitteln. In den einschlägigen Veröffentlichungen zum TIP wird u. a. auch von Pile Dynamics, Inc. darauf hingewiesen, dass es sich nur um eine Abschätzung der Betondeckung bzw. des Überbetons während der Pfahlherstellung handelt. Insbesondere wird in diesem Fall davon ausgegangen, dass das verbaute Betonvolumen ebenfalls monitort werden muss, um dies den Messergebnissen entgegenzusetzen. Dies allein reicht jedoch aus Sicht der Autoren nicht, um einen fundierten Rückschluss auf die Pfahlkubatur aus den Temperaturaufzeichnungen zu ziehen. Insbesondre bei Sonderformen erscheint dieses Vorgehen als problematisch. Im Rahmen des 17. Hans‐Lorenz‐Symposiums 2023 an der Technischen Universität Berlin wurden erste „Neue Erkenntnisse zum Thermal Integrity Profiling (TIP) an tiefen Pfählen mit Sonderformen“ vorgestellt. Diese Erkenntnisse wurden im Rahmen weiterer Untersuchungen unter Anwendung der kommerziellen Software COMSOL Multiphysics ausgebaut und werden im Folgenden näher dargelegt. Im Ergebnis bleibt festzustellen, dass die Einflussfaktoren derart vielfältig sind, dass selbst bei deren Berücksichtigung nicht auf den Durchmesser rückgeschlossen werden kann. Dies wird durch die Autoren im Folgenden dezidiert vorgestellt.
Innovative Gründung von Schallschutzwänden
Authors: Boley Conrad , Pratter Paul , Mölter Tristan , Wistuba Matthias 
Published: August 2024

AbstractSchraubfundamente werden in der Geotechnik oftmals mit leichten Konstruktionen in Verbindung gebracht und sind weltweit als Gründungselement von Photovoltaikanlagen etabliert. Derzeit werden größere Bauformen der Schraubfundamente entwickelt und im Rahmen von Pilotprojekten erprobt. Diese Schraubfundamente weisen mit ca. 406 mm etwa den vierfachen Rohrdurchmesser der kleinen Bauform auf und sind damit als Pfahlgründung einzustufen und zu bemessen. Im Gegensatz zu konventionellen Rammrohren werden die Schraubfundamente erschütterungsfrei in den Boden eingedreht. Es liegt nahe, dass die Gründungselemente dort zum Einsatz kommen sollen, wo besonders auf Geräusch‐ und Erschütterungsemissionen geachtet werden muss. Beispielsweise als Gründungselement von Schallschutzwänden im Rahmen des Sonderprogramms Lärmsanierung Mittelrheintal. Das Pilotprojekt der Deutschen Bahn wird im vorliegenden Beitrag vorgestellt, Hinweise zur Bemessung der großen Schraubfundamente gegeben und die Vorteile des innovativen Gründungssystems aufgezeigt.
Achieving High‐Performance in Zinc Hybrid Capacitors with Zn(TFSI)2/PEGDME Molecular Crowding Electrolytes
Authors: Patil Nagaraj , Ciurduc Diana Elena , Landazábal F. J. , Marcilla Rebeca 
Published: August 2024

AbstractAqueous Zinc‐hybrid capacitors (ZHCs) are gaining attention for their high‐safety, low cost, easy maintenance, high‐power, and longevity. Despite various strategies to mitigate dendrites, corrosion, and HER, practical application remains challenging. Here, we utilize an advanced polyethylene glycol dimethyl ether (PEGDME)‐based molecular crowding electrolyte (MCE) to significantly enhance performance of ZHCs. Our MCE offers a wider electrochemical stability window (2.7 V), low HER activity, and superior Zn anti‐corrosion properties due to reduced water activity compared to conventional electrolyte. This results in higher coulombic efficiencies (98–100 %) at various areal capacities and current densities, and longer longevity of Zn//Cu and Zn//Zn symmetric cells with MCE compared to conventional and water‐in‐salt electrolytes. The Zn/MCE/AC displays an enhanced voltage window (∼2 V), achieving the highest capacitance (281 F/g), competitive energy density (138 Wh/kg), low self‐discharge, and excellent cyclability (19100 cycles at 1 A/g with 100 % capacity retention), indicating that MCE is a promising approach for practical energy storage applications.
Sample Size Calculation Under Nonproportional Hazards Using Average Hazard Ratios
Authors: Dormuth Ina , Pauly Markus , Rauch Geraldine , Herrmann Carolin 
Published: August 2024

ABSTRACTMany clinical trials assess time‐to‐event endpoints. To describe the difference between groups in terms of time to event, we often employ hazard ratios. However, the hazard ratio is only informative in the case of proportional hazards (PHs) over time. There exist many other effect measures that do not require PHs. One of them is the average hazard ratio (AHR). Its core idea is to utilize a time‐dependent weighting function that accounts for time variation. Though propagated in methodological research papers, the AHR is rarely used in practice. To facilitate its application, we unfold approaches for sample size calculation of an AHR test. We assess the reliability of the sample size calculation by extensive simulation studies covering various survival and censoring distributions with proportional as well as nonproportional hazards (N‐PHs). The findings suggest that a simulation‐based sample size calculation approach can be useful for designing clinical trials with N‐PHs. Using the AHR can result in increased statistical power to detect differences between groups with more efficient sample sizes.
Antioxidant and Antimicrobial Activities of 4H‐Chromene Based Indole‐Pyrimidine Hybrids: Synthesis and Molecular Docking Studies
Authors: Vanga Murali Krishna , Bhukya Rambabu , Thumma Vishnu , Tamalapakula Vani , Boddu Lakshmi Satya , Manga Vijjulatha 
Published: August 2024

AbstractA series of 4H‐Chromene Based Indole‐Pyrimidine Hybrids synthesized using simple and efficient multicomponent reaction. The title molecules were evaluated for their invitro antioxidant and antimicrobial activities. Compounds 8 g containing bromo substituted naphthalene displayed potent antioxidant activity with IC50 value of 1.09±0.34 μM and 1.10±0.36 μM. Compound 10 a, a 4‐methylphenyl derivative presented potent activity with antioxidant activity with IC50 value of 1.29±0.35 μM and 1.43±0.38 μM. Subsequently, compounds 8 a, 8 b, 8 d and 10 g had shown prominent percentage of inhibition and derived effective IC50 values in comparison to reference drug Ascorbic Acid. The invitro antimicrobial activity carried out against two gram positive and two gram‐negative bacteria, and two fungal strains using Ampicillin and Itraconazole as refence drugs. Compound 10 f exhibited exceptional efficacy against all types of bacterial and fungal strains compared to Ampicillin and Itraconazole, compounds 8 e and 8 g showed activity against bacterial strains whereas compound 10 g exhibited the most effective zone of inhibition against fungal strains. The molecular docking study against crystal structure of NADPH oxidase obtained supporting docking scores and showed notable binding interactions such as H‐bond and hydrophobic.
Electrochemical Generation of Nitrogen‐centered Radicals and its Application for the Green Synthesis of Heterocycles
Authors: Titenkova Kseniia , Chaplygin Daniil A. , Fershtat Leonid L. 
Published: August 2024

AbstractElectrochemistry became a unique and powerful tool for the preparation of a plethora of valuable chemical species including functional materials, drug candidates and clinically approved pharmaceuticals. Organic electrosynthesis well satisfies main goals of green chemistry development and is considered as one of the useful approaches toward the creation of sustainable future. Since nitrogen heterocyclic scaffolds still retain their importance for the construction of novel materials and medications, one of the emerging trends in organic electrochemistry is the discovery of novel green and sustainable synthetic methods toward the assembly of heterocyclic subunits. In this regard, organic electrochemistry provides an efficient platform for environmentally benign generation of various nitrogen‐centered radicals which are prominent intermediates in the synthesis of nitrogen heterocycles. In this Review, recent developments in the creation of green synthetic methods for the construction of nitrogen heterocycles via electrochemical generation of nitrogen‐centered radicals are summarized. The special emphasis is devoted to the influence of solvent, electrodes and electrolytes on the electrochemical step, since these crucial parameters regulate the process efficiency.
Synthesis of 4‐(Phenylamino)quinazoline‐2(1H)‐thiones Using Green Solvents
Authors: Messire Gatien , Adolf Claudie , Berteina‐Raboin Sabine 
Published: August 2024

AbstractGiven the importance of quinazolines and quinazolinethiones in therapeutic and Food and Drug Administration (FDA)‐approved molecules, we thought interesting to consider their synthesis in green solvents. We have shown that obtain 4‐(arylamino)quinazoline‐2‐(1H)‐thiones and 4‐(arylamino)pteridine‐2‐(1H)‐thiones analogues was efficient in green solvents derived from biomass, especially eucalyptol. Although reaction times are somewhat long to achieve good yields, the products were obtained by simple filtration. This considerably limited the loss of atoms due to the use of large quantities of solvents for purification on silica gel columns, and makes our route a sustainable one.
Unraveling the Source of Self‐Induced Diastereomeric Anisochronism in Chiral Dipeptides
Authors: Spiaggia Fabio , Aiello Federica , Sementa Luca , Campagne Jean‐Marc , Marcia de Figueiredo Renata , Uccello Barretta Gloria , Balzano Federica 
Published: August 2024

AbstractMastering of analytical methods for accurate quantitative determinations of enantiomeric excess is a crucial aspect in asymmetric catalysis, chiral synthesis, and pharmaceutical applications. In this context, the phenomenon of Self‐Induced Diastereomeric Anisochronism (SIDA) can be exploited in NMR spectroscopy for accurate determinations of enantiomeric composition, without using a chiral auxiliary that could interfere with the spectroscopic investigation. This phenomenon can be particularly useful for improving the quantitative analysis of mixtures with low enantiomeric excesses, where direct integration of signals can be tricky. Here, we describe a novel analysis protocol to correctly determine the enantiomeric composition of scalemic mixtures and investigate the thermodynamic and stereochemical features at the basis of SIDA. Dipeptide derivatives were chosen as substrates for this study, given their central role in drug design. By integrating the experiments with a conformational stochastic search that includes entropic contributions, we provide valuable information on the dimerization thermodynamics, the nature of non‐covalent interactions leading to self‐association, and the differences in the chemical environment responsible for the anisochronism, highlighting the importance of different stereochemical arrangement and tight association for the distinction between homochiral and heterochiral adducts. An important role played by the counterion was pointed out by computational studies.