bluuebunny/crossref_metadata_2025_split huggingface dataset:
Interfacial Ir‐V Direct Metal Bonding Enhanced Hydrogen Evolution Activity in Vanadium Oxides Supported Catalysts
Authors: Zheng Yijuan , Geng Wei , Xiao Sutong , Ma Tian , Cheng Chong , Liao Yaozu , Zeng Zhiyuan , Li Shuang , Zhao Changsheng 
Published: June 2024

AbstractTuning the interfacial structure of metal oxide substrates is an essential strategy to induce electronic structure reconstruction of supported catalysts, which is of great importance in optimizing their catalytic activities. Herein, vanadium oxides‐supported Ir catalysts (Ir‐V2O3, Ir‐VO2, and Ir‐V2O5) with different interfacial bonding environments (Ir‐V, Ir‐Obri, and Ir‐O, respectively) were investigated for hydrogen evolution reaction (HER). The regulating mechanism of the influence of different interfacial bonding environments on HER activity was investigated by both experimental results and computational evidence. Benefiting from the unique advantages of interfacial Ir‐V direct metal bonds in Ir‐V2O3, including enhanced electron transfer and electron donation ability, an optimized HER performance can be obtained with lowest overpotentials of 16 and 26 mV at 10 mA cm−2, high mass activities of 11.24 and 6.66 A mg−1, and turnover frequency values of 11.20 and 6.63 s−1, in acidic and alkaline conditions respectively. Furthermore, the assembled Ir‐V2O3||RuO2 anion exchange membrane (AEM) electrolyzer requires only 1.92 V to achieve a high current density of 500 mA cm−2 and realizes long‐term stability. This study provides essential insights into the regulating mechanism of interfacial chemical bonding in electrocatalysts and offers a new pathway to design noble metal catalysts for different applications.
Synthesis and evaluation of oleic acid‐derived hyperbranched polyester as an efficient plasticizer for PVC
Authors: Zhang Chao , Yu Erlei , Wang Heyun , Huang Dong , Ding Guojun , Zhao Zhonghua , Wei Zhong 
Published: June 2024

AbstractIn response to the health and environmental concerns associated with the plasticizer dioctyl phthalate (DOP), this research explores the utilization of methyl oleate (MO) derived from plant oil, 1,2,4‐Benzeneticarboxylic anhydride (TMA) and isobutyric anhydride (IA) as a precursor for synthesizing a hyperbranched polyester named IA‐MO‐TMA. This polyester serves as an alternative plasticizer for Polyvinyl chloride (PVC). The chemical structure of IA‐MO‐TMA was thoroughly characterized using Fourier Transform Infrared Spectrometer (FTIR) and nuclear magnetic resonance hydrogen spectra, and its molecular weight was assessed. The PVC film, plasticized with IA‐MO‐TMA, underwent comprehensive testing using techniques such as differential scanning calorimetry, scanning electron microscopy, and thermogravimetric analysis. Notably, the glass transition temperature (Tg) of the plasticized PVC film exhibited a significant reduction from 75°C to −6.7°C. The plasticized film demonstrated an elongation at break of 318.1%, a tensile strength of 19.2 MPa, and a plasticizing efficiency of 109.9%. Moreover, the use of IA‐MO‐TMA as a plasticizer increased the initial decomposition temperature of PVC film from 235.6 to 264.1°C. Additionally, the extraction rate of IA‐MO‐TMA in petroleum ether was found to be 35.6% lower than that of DOP.
Universal Dimensionality of Ferroelectric Domain Walls in Ultrathin Films
Authors: Kale Somnath , Petraru Adrian , Kohlstedt Hermann , Soni Rohit 
Published: June 2024

AbstractThe dimensionality of dynamic interfaces—domain walls (DWs) —is greatly influenced by symmetry and physical dimensions, irrespective of the microscopic details of the system. To address this fundamental question for the ferroelectric model system, the DW scaling criticality and dimensionality is investigated in ultrathin films of varied ferroelectric materials, compositions, and electrode–ferroelectric interfaces, grown on nominally flat and vicinal substrates. In spite of significant variations among ferroelectric systems, the observed prevalence of 1D DWs is consistent with a random bond disorder, elucidated through a scenario of 2D nucleation and growth‐driven DW creep. These findings highlight the thickness size‐dominated universal behavior of ferroelectric DWs, uncovering fascinating prospects for dimensionally engineered DW‐based nanoelectronics.
Hydroxychloroquine Dose and Hospitalizations for Active Lupus
Authors: Nestor Jacquelyn , Choi Hyon , Mancini Christian , Zhou Baijun , Zhang Yuqing , Costenbader Karen H. , Jorge April 
Published: June 2024

ObjectiveWe sought to determine the impact of hydroxychloroquine (HCQ) dose on the risk of hospitalizations for systemic lupus erythematosus (SLE).MethodsWe conducted a case‐crossover study within an academic health system, including patients with SLE who used HCQ and had ≥1 hospitalization for active SLE between January 2011 and December 2021. Case periods ended in hospitalization for SLE, whereas control periods did not. The exposures were the average weight‐based HCQ dose, categorized as ≤5 or >5 mg/kg/day, and non–weight‐based HCQ dose, categorized as <400 or 400 mg/day, assessed during each six‐month case or control period. Odds ratios (ORs) were calculated using conditional logistic regression and adjusted for prior disease activity, kidney function, glucocorticoid use, and other immunosuppressant use.ResultsOf 2,974 patients with SLE who used HCQ (mean age 36.5 years; 92% female), 584 had ≥1 hospitalization with primary discharge diagnosis of SLE. Of these, 122 had ≥1 hospitalization for active SLE while using HCQ and had ≥1 control period with HCQ use during the study period. Lower HCQ weight‐based dose (≤5 vs >5 mg/kg/day) and non–weight‐based dose (<400 vs 400 mg/day) were each associated with increased hospitalizations for active SLE (adjusted OR 4.20, 95% confidence interval [CI] 1.45–12.19, and adjusted OR 3.39, 95% CI 1.31–8.81).ConclusionThe use of lower doses of HCQ was associated with an increased risk of hospitalizations for active SLE. Although the long‐term risk of HCQ retinopathy must be acknowledged, this must be balanced with the short‐term and cumulative risks of increased SLE activity.image
Oxidative status: A general but overlooked indicator of welfare across animal species?
Authors: Beaulieu Michaël 
Published: June 2024

AbstractBecause of their ubiquity, plasticity, and direct effects on the nervous system, markers of oxidative status may be of great value to assess animal welfare across species and conditions in the wild. However, welfare biologists have not yet seized this opportunity, possibly because the validity of these markers as welfare indicators remains questionable. A validation process was, therefore, performed here using a meta‐analytical approach considering three conditions assumed to impair the welfare of animals. With very few exceptions, two of the four considered markers consistently varied across these negatively‐valenced conditions. By highlighting the current underrepresentation of markers of oxidative status in animal welfare studies, and by concretely illustrating that some of these markers can consistently reflect negative affective states, this article aims to encourage biologists to include these physiological markers in their toolbox to better measure, monitor, and perhaps also improve the welfare of animals in their natural habitat.
Elucidating solvent effects on lipase‐catalyzed peroxyacid synthesis through activity‐based kinetics and molecular dynamics
Authors: Brandolín Salvador E. , Scilipoti José A. , Magario Ivana 
Published: June 2024

AbstractPeroxyacid synthesis is the first step in Prilezhaev epoxidation, which is an industrial method to form epoxides. Motivated by the development of a kinetic model as a tool for solvent selection, the effect of solvent type and acid chain length on the lipase‐catalyzed peroxyacid synthesis was studied. A thermodynamic activity‐based ping‐pong kinetic expression was successfully applied to predict the effect of the reagent loadings in hexane. The activity‐based reaction quotients provided a prediction of solvent‐independent equilibrium constants. However, this strategy did not achieve satisfactory estimations of initial rates in solvents of higher polarity. The lack of compliance with some assumptions of this methodology could be confirmed through molecular dynamics calculations i.e. independent solvation energies and lack of solvent interaction with the active site. A novel approach is proposed combining the activity‐based kinetic expression and the free binding energy of the solvent with the active site to predict kinetics upon solvent change. Di‐isopropyl ether generated a strong interaction with the enzyme's active site, which was detrimental to kinetics. On the other hand, toluene or limonene gave moderate interaction with the active site rendering improved catalytic yield compared with less polar solvents, a finding sharpened when peroctanoic acid was produced.
(Ni or/and Co) Supported over Praseodymia as Oxygen Carriers for Chemical Looping Syngas Production
Authors: Santos Lucía Herráez , Caracena María Murcia , Marhuenda Daniel Sanchiz , Sigüenza María Pilar Yeste , García Avelina García 
Published: June 2024

AbstractThe present research describes one of the processes outlined in the literature, known as Chemical Looping Dry Reforming of Methane, which is currently to gain attraction to produce clean fuels from natural gas using a metal oxide support as a catalyst. This two‐step method offers distinct advantages by physically separating the reaction steps. This spatial separation effectively eliminates undesirable side reactions, leading to highly efficient syngas production with minimal carbon deposition. Crucial to optimizing this process is a deep understanding of the oxygen storage capacity (OSC) of the support (oxygen carrier) that will work in synergy with the supported active phase. Among the candidates, praseodymium stands out due to its favourable redox properties and exceptional OSC characteristics, making it a promising option for cleaner fuel technologies. In particular, this study emphasizes the significant influence of the nature of the active phases (Ni, Co or their bimetallic combinations), with bimetallic phases being the most promising (even without reduction, they can exhibit activity that equals or improves that of the Ru as benchmark), underscoring the fundamental role of catalyst design in achieving optimal performance. The results indicate that these compositions have high activities to generate the products, remaining close to the activity of ruthenium and generating minimal coke deposits in one reaction cycle.
Intramolecularly O,N,O‐Coordinated Tin(II) Salts: Syntheses, Structures, Cyclization, and Transition Metal Complexation
Authors: Alnasr Hazem , Mroß David , Platzek André , Nayyar Bastian , Řičica Tomáš , Schollmeyer Dieter , Jambor Roman , Hoffmann Alexander , Jurkschat Klaus 
Published: June 2024

AbstractWe report the syntheses of tin(II) salts of the types [L1SnX]SnX3 [L1=2,6‐{(i‐PrO)2(O)P}2C5H3N: 1, X=Cl; 2, X=Br], [L2SnCl]SnCl3 [L2=2‐{(i‐PrO)Ph(O)P}‐6‐{(i‐PrO)2(O)P}C5H3N: 3], [L3SnX]SnX3 [L3=2,6‐{MeO(O)C}2C5H3N: 4, X=Cl; 5, X=Br], [L4SnX]SnX3 [L4=2,6‐{Et2N(O)C}2C5H3N: 6, X=Cl; 7, X=Br]. These compounds were obtained by addition of SnX2 to the corresponding ligand inducing autoionization of the respective tin(II) halide. The thermal stability of 1, 3, and 4 was elucidated, giving, under ester cleavage and cyclisation, the tin(II) derivatives 8–12. The reaction of [L1SnCl]SnCl3 (1) with W(CO)4(thf)2 afforded the tungsten tetracarbonyl complex [{L1SnCl}{SnCl3}W(CO)4] (13), representing the first example in which a tin(II) stannate anion and a tin(II) stannylium cation simultaneously coordinate to a transition metal centre. The compounds were characterized by single crystal X‐ray diffraction analyses and in part by elemental analyses, IR and NMR spectroscopy, electrospray ionization mass spectrometry. DFT calculations accompany the experimental work.
Photochemical Aerobic Upcycling of Polystyrene Plastics via Synergistic Indirect HAT Catalysis
Authors: Mountanea Olga G. , Skolia Elpida , Kokotos Christoforos G. 
Published: June 2024

AbstractPlastic pollution constitutes an evergrowing urgent environmental problem, since overaccumulation of plastic waste, arising from the immense increase of the production of disposable plastic products, overcame planet's capacity to properly handle them. Chemical upcycling of polystyrene constitutes a convenient method for the conversion of plastic waste into high‐added value chemicals, suggesting an attractive perspective in dealing with the environmental crisis. We demonstrate herein a novel, easy‐to‐perform organocatalytic photoinduced aerobic protocol, which proceeds via synergistic indirect hydrogen atom transfer (HAT) catalysis under LED 390 nm Kessil lamps as the irradiation source. The developed method employs a BrCH2CN‐thioxanthone photocatalytic system and was successfully applied to a variety of everyday‐life plastic products, leading to the isolation of benzoic acid after simple base‐acid work up in yields varying from 23–49 %, while a large‐scale experiment was successfully performed, suggesting that the photocatalytic step is susceptible to industrial application.
Transition Behaviors of Isostructural Hydrogen‐Bonded Frameworks Composed of Naphthalene, Quinoxaline, and Pyrazinopyrazine Derivatives
Authors: Kubo Haruka , Konishi Shunsuke , Oketani Ryusei , Hayashi Takashi , Hisaki Ichiro 
Published: June 2024

AbstractA series of isostructural reticular frameworks with systematic differences on chemical structures allows us to disclose correlations between specific structural factors and properties, providing insights for designing novel porous materials. However, even slight differences in the molecular structure often lead to non‐isostructural polymorphic frameworks particularly in the case of hydrogen‐bonded organic frameworks (HOFs) because the structures of HOFs are based on a subtle balance of reversible interactions. In this study, we found that three simple analogues of tetracarboxylic acids with naphthalene, quinoxaline, and pyrazinopyrazine cores (NT, QX, and PP, respectively) yielded isostructural solvated HOFs (NT‐1, QX‐1, and PP‐1, respectively), where hydrogen‐bonded sql‐networked sheets were slip‐stacked with closely similar manners. More importantly, these isostructural HOFs underwent structural transformations in different manners upon removal of the guest solvents. Comparison of the crystal structures of the HOFs before and after the transformation revealed that intermolecular interactions of the core significantly affected on rearrangements of hydrogen bonds in the transformation. The results suggest the potential to control the properties and functions of isostructural HOFs by elements in the core.
Chemical characterization of submicron particulate matter (PM1) and its source apportionment using positive matrix factorization
Authors: Jhamaria Charu , Sharma Shivani , Yadav Manish , Tiwari Suresh , Singh Namrata 
Published: June 2024

AbstractThe present study was conducted to address four key questions: (i) What are the levels of submicron particulate matter at the study area?, (ii) which are the major contributing sources of these particles?, and (iii) is there any seasonal changes in the levels of pollutants at the study site? Thus, the study was conducted at an urban residential site of Jaipur City, India, to determine the elemental and ionic composition of toxic elements associated with PM1 using inductively coupled plasma optical emission spectroscopy and ion chromatography to reveal specific sources. Monitoring was done for a period of 8 months between October 2020 and May 2021 considering three seasons: winter (December–February), pre‐monsoon (March–May), and post‐monsoon (October–November). PM1 samples were found to be highly enriched with Ag, Cd, B, Ni, and Zn. PM1 mass concentrations were observed to be greater in winter (104.13 ± 30.16 µg m−3) and lower in the pre‐monsoon season (83.62 ± 19.40 µg m−3). Ion concentrations (Cl−, NO32−, and SO42−) followed a similar pattern to PM1 concentrations. Source apportionment by positive matrix factorization at the study site revealed six major sources of pollutants (soil dust, agro‐based industry, automobile industry, salt aerosols, industrial activities, and biomass burning).
Chemical Modifications on the αvβ6 Integrin Targeting A20FMDV2 Peptide: A Review
Authors: Siow Andrew , Kowalczyk Renata , Hong Jiwon , Harris Paul W. R. 
Published: June 2024

AbstractIntegrin proteins have received a significant increase in attention in recent scientific endeavors. The current trend uses the pre‐established knowledge that the arginyl‐glycyl‐aspartic acid (RGD) structural motif present in the A20FMDV2 peptide is highly selective for the integrin class αvβ6 which is overexpressed in many cancer types. This review will provide an extensive overview of the existing literature research to date to the best of our knowledge, highlighting significant improvements and drawbacks of structure‐activity relationships (SAR) work undertaken, aiding future research to identify established SAR for an informed design of future A20FMDV2 mimetic inhibitors. Herein, the review aims to collate the existing structural chemical modifications present on A20FMDV2 in the literature to highlight key structural analogues that display more potent biological activity.
Glass Box and Black Box Machine Learning Approaches to Exploit Compositional Descriptors of Molecules in Drug Discovery and Aid the Medicinal Chemist
Authors: Robson Barry , Cooper Richard 
Published: June 2024

AbstractThe synthetic medicinal chemist plays a vital role in drug discovery. Today there are AI tools to guide next syntheses, but many are “Black Boxes” (BB). One learns little more than the prediction made. There are now also AI methods emphasizing visibility and “explainability” (thus explainable AI or XAI) that could help when “compositional data” are used, but they often still start from seemingly arbitrary learned weights and lack familiar probabilistic measures based on observation and counting from the outset. If probabilistic methods were used in a complementary way with BB methods and demonstrated comparable predictive power, they would provide guidelines about what groups to include and avoid in next syntheses and quantify the relationships in probabilistic terms. These points are demonstrated by blind test comparison of two main types of BB methods and a probabilistic “Glass Box” (GB) method new outside of medicine, but which appears well suited to the above. Because many probabilities can be involved, emphasis is on the predictive power of its simplest explanatory models. There are usually more inactive compounds by orders of magnitude, often a problem for machine learning methods. However, the approaches used here appear to work well for such “real world data”.
Innovative Approaches for Manufacturing Epoxy‐Modified Wood and Cellulose Fiber Composites: A Comparison between Injection Molding and 3D Printing
Authors: Lemos Cosse Renato , van den Berg Thijs , Voet Vincent , Folkersma Rudy , Loos Katja 
Published: June 2024

AbstractThe current study focused on improving the properties of polylactic acid (PLA) for wider application in load‐bearing scenarios. Various methods were explored to optimize the interaction between PLA and natural fibers, particularly wood fibers (WFs). Alkalized and epoxy‐impregnated WFs were evaluated against untreated WFs and cellulose fibers in both injection molding (IM) and fused deposition modeling (FDM). FTIR analysis revealed the removal of hemicellulose and lignin in alkalized WFs and uniform epoxy curing. Addition of fibers reduced PLA's thermal stability while acting as nucleating agents. Additionally, fibers augmented the storage modulus of biocomposites, with alkalized fibers exhibiting the highest tensile modulus in IM. FDM samples with a 0° raster angle showed superior impact resistance compared to IM counterparts. Moreover, raster angle significantly influenced FDM biocomposite properties, enhancing the tensile strength and modulus of untreated WF and cellulose fibers at 0°. Although FDM did not produce alkalized WF samples, epoxy impregnation emerged as a promising method for enhancing PLA/WF composite mechanical properties in the IM process, offering valuable insights for composite material development.
Explore new quinoxaline pharmacophore tethered sulfonamide fragments as in vitro α‐glucosidase, α‐amylase, and acetylcholinesterase inhibitors with ADMET and molecular modeling simulation
Authors: Ragab Ahmed , Salem Mohamed A. , Ammar Yousry A. , Aboulthana Wael M. , Helal Mohamed H. , Abusaif Moustafa S. 
Published: June 2024

AbstractA new series of quinoxaline‐sulfonamide derivatives 3–12 were synthesized using fragment‐based drug design by reaction of quinoxaline sulfonyl chloride (QSC) with different amines and hydrazines. The quinoxaline‐sulfonamide derivatives were evaluated for antidiabetic and anti‐Alzheimer's potential against α‐glucosidase, α‐amylase, and acetylcholinesterase enzymes. These derivatives showed good to moderate potency against α‐amylase and α‐glucosidase with inhibitory percentages between 24.34 ± 0.01%–63.09 ± 0.02% and 28.95 ± 0.04%–75.36 ± 0.01%, respectively. Surprisingly, bis‐sulfonamide quinoxaline derivative 4 revealed the most potent activity with inhibitory percentages of 75.36 ± 0.01% and 63.09 ± 0.02% against α‐glucosidase and α‐amylase compared to acarbose (IP = 57.79 ± 0.01% and 67.33 ± 0.01%), respectively. Moreover, the quinoxaline derivative 3 exhibited potency as α‐glucosidase and α‐amylase inhibitory with a minute decline from compound 4 and acarbose with inhibitory percentages of 44.93 ± 0.01% and 38.95 ± 0.01%. Additionally, in vitro acetylcholinesterase inhibitory activity for designed derivatives exhibited weak to moderate activity. Still, sulfonamide‐quinoxaline derivative 3 emerged as the most active member with inhibitory percentage of 41.92 ± 0.02% compared with donepezil (IP = 67.27 ± 0.60%). The DFT calculations, docking simulation, target prediction, and ADMET analysis were performed and discussed in detail.
The circadian syndrome is a predictor for cognition impairment in middle‐aged adults: Comparison with the metabolic syndrome
Authors: Shi Zumin , Stern Naftali , Liu Jianghong , Tuomilehto Jaakko , Kronfeld‐Schor Noga , El‐Osta Assam , Alberti George , Chai Zhonglin , Bilu Carmel , Einat Haim , Marcus Yonit , Zimmet Paul 
Published: June 2024

AbstractAimsCircadian syndrome (CircS) is considered a better predictor for cardiovascular disease than the metabolic syndrome (MetS). We aim to examine the associations between CircS and MetS with cognition in Chinese adults.MethodWe used the data of 8546 Chinese adults aged ≥40 years from the 2011 China Health and Retirement Longitudinal Study. MetS was defined using harmonised criteria. CircS included the components of MetS plus short sleep and depression. The cut‐off for CircS was set as ≥4. Global cognitive function was assessed during the face‐to‐face interview.ResultsCircS and MetS had opposite associations with the global cognition score and self‐reported poor memory. Compared with individuals without the CircS and MetS, the regression coefficients (95%CI) for global cognition score were −1.02 (−1.71 to −0.34) for CircS alone and 0.52 (0.09 to 0.96) for MetS alone in men; −1.36 (−2.00 to −0.72) for CircS alone and 0.60 (0.15 to 1.06) for MetS alone in women. Having CircS alone was 2.53 times more likely to report poor memory in men (95%CI 1.80–3.55) and 2.08 times more likely in women (95%CI 1.54–2.81). In contrast, having MetS alone was less likely to report poor memory (OR 0.64 (0.49–0.84) in men and 0.65 (0.52–0.81) in women). People with CircS and MetS combined were more likely to have self‐reported poor memory.ConclusionsCircS is a strong and better predictor for cognition impairment than MetS in Chinese middle‐aged adults. MetS without short sleep and depression is associated with better cognition.