bluuebunny/crossref_metadata_2025_split huggingface dataset:
Steering the Selectivity of CORR from Acetate to Ethanol via Tailoring the Thermodynamic Activity of Water
Authors: Liu Jia , Zhang Bao , Chen Derong , Peng Ouwen , Ma Haibin , Xi Shibo , Wu Chao , Hu Qikun , Zhang Kun , Feng Junyuan , Ping Loh Kian 
Published: August 2024

AbstractThe electrochemical conversion of carbon monoxide (CO) into oxygenated C2+ products at high rates and selectivity offers a promising approach for the two‐step conversion of carbon dioxide (CO2). However, a major drawback of the CO electrochemical reduction in alkaline electrolyte is the preference for the acetate pathway over the more valuable ethanol pathway. Recent research has shed light on the significant impact of thermodynamic water activity on the electrochemical CO2 reduction reaction pathways, but less is understood for the electrochemical reduction of CO. In this study, we investigated how the water activity at the electrified interface can be enhanced to adjust the selectivity between acetate and ethanol. We employed an ionomer modifier to lower the local concentration of alkali ions (via Donnan exclusion), successfully enhancing ethanol production while suppressing acetate formation. We observed a remarkable improvement in the Faradaic efficiency of ethanol and alcohol (i. e. ethanol, propanol etc), which reached 42.5 % and 55.1 %, respectively, at a current density of 700 mA cm−2. The partial current densities of ethanol and alcohol reached 698 and 942 mA cm−2 at 2000 mA cm−2. Furthermore, we achieved a 3.7‐fold increase in the ethanol/acetate ratio, providing clear evidence of our successful modulation of product selectivity.
Intermolecular Anionic Mixed‐Valence and π‐Dimer Complexes of ortho‐Pentannulated Bisazacoronene Diimide
Authors: David Arthur H. G. , Roger Maxime , Alévêque Olivier , Melnychenko Heorhii , Le Bras Laura , Allain Magali , Gapin Adèle , Canevet David , Ségut Olivier , Levillain Eric , Goujon Antoine 
Published: August 2024

AbstractThis study reports the serendipitous discovery of intermolecular anionic mixed‐valence (MV) and π‐dimer species in ortho‐pentannulated BisAzaCoroneneDiimides (BACDs) during their electrochemical reduction in a non‐aqueous solvent. A library of nitrogen‐containing extended PDIs was synthesized via an aza‐benzannulation reaction followed by a Pd‐catalysed ortho‐pentannulation reaction. Ortho‐pentannulated BACDs revealed strong aggregation abilities in solution. Concentration‐dependent UV/Vis absorption spectra, variable temperature 1H NMR experiments, and atomic force microscopy coupled to molecular dynamics support their self‐assembly into columnar aggregates. Cyclic voltammetry experiments in dichloromethane reveal prominent splitting of the first reduction wave, attributed to the formation of unprecedented intermolecular anionic MV and π‐dimers in organic solvent. These species were thoroughly characterized by real‐time spectroelectrochemistry, electrochemical simulations and theoretical calculations. Remarkably, this work underscores the tuneable nature of AzaBenzannulatedPerylene Diimides (AzaBPDIs) and BACDs, emphasizing their potential as a promising scaffold for designing supramolecular materials with long‐range radical anion delocalization. The observation of this phenomenon provides insights into the fundamental behaviour of supramolecular organic semiconductors, thereby paving the way for the development of novel electronic devices and electron‐deficient materials.
Strain‐Induced Structural Rearrangement Towards a White‐Light‐Emitting Adamantane‐Type Cluster Dimer
Authors: Wang Jie , Rojas‐Leon Iran , Rinn Niklas , Guggolz Lukas , Ziese Ferdinand , Sanna Simone , Rosemann Nils W. , Dehnen Stefanie 
Published: August 2024

AbstractGroup 14/16 adamantane‐type hybrid clusters of the type [(RT)4E6] (T=group 14 element, E=group 16 element, R=organic group) have been reported to emit white‐light when irradiated in an amorphous state with a continuous‐wave (CW) infrared laser diode. This effect is enhanced if the cluster core is varied from a binary to a more complex composition. To further explore this phenomenon, we synthesized clusters with a multinary R/R’‐T/T’‐E/E’ composition, including isolobal replacement of E with CH2, in [(2‐NpSi){CH2Sn(S)Ph}3] (1, Np=naphthyl). When expanding one of the CH2 moieties to a C2H4 group, thus generating a R/R’‐T/T’‐E/E’/E’’ cluster composition, we unexpectedly observed a dimerization of the initially formed, yet non‐isolable adamantane‐like cluster [(2‐NpSi){CH2Sn(S)Ph}2{C2H4Sn(S)Ph}] (2) to [(2‐NpSi){CH2Sn(S)Ph}2{C2H4Sn(S)Ph}]2 (3), exhibiting a heretofore unprecedented cluster architecture. Both monomeric 1 and dimeric 3, show white‐light emission as thin films. The nonlinear optical response of the compounds was also modelled with DFT methods.
Collective Asymmetric Synthesis of Thiosilvatins
Authors: Liu Jian , Ekberg Robin , Koning Nicolas R. , Strand Daniel 
Published: August 2024

AbstractThiosilvatins are a family of biologically active sulfenylated diketopiperazine natural products. The first members were reported over 40 years ago, but total synthesis of a thiosilvatin has remained elusive. Here, we describe the first, collective, synthesis of the parent epidithiodiketopiperazine (−)‐dithiosilvatin and ten related thiosilvatins. Several of the targets are structurally revised. A catalytic asymmetric sulfenylation of triketopiperazines efficiently controls absolute configuration at the thioaminal units. Further synthetic highlights include a diastereoconvergent installation of the requisite cis‐orientation of the sulfur atoms and a tandem epidisulfide formation/O‐prenylation under mild Mitsunobu conditions. The described methods for late‐stage diversification of sensitive bis(methylthio)diketopiperazines offer a blueprint for systematically exploring this interesting 3D‐pharmacophore in stereochemically pure form.
Hofmann Clathrates: A “Blue Box” Approach to Modulate Spin‐Crossover Properties
Authors: Getzner Livia , Vendier Laure , Molnár Gábor , Rotaru Aurelian , Cobo Saioa , Bousseksou Azzedine 
Published: August 2024

AbstractHofmann coordination polymers (CPs) with cationic ligands provide an innovative strategy for recognizing π‐electron‐rich aromatic molecules – similar to the “little blue box”. In this study, we demonstrate that hydroquinone molecules can be incorporated into these coordination polymers when redox‐active bipyridinium derivatives are used as axial ligands. The insertion leads to a significant structural modification, resulting in a shift of the spin transition by 150 K and an approximate 23 % increase in volume, caused by the strong donor‐acceptor π‐π stacking interaction formed between the ligands and the guest molecule. These findings have been confirmed through temperature‐dependent single crystal X‐ray diffraction, magnetic measurements and optical reflectivity measurements.
Hydrogen Bonding Chemistry in Aqueous Ammonium Ion Batteries
Authors: Zhou Mengmeng , Huang Xinjun , Li Hui , Duan Xiaoguang , Zhao Qin , Ma Tianyi 
Published: August 2024

AbstractAqueous ammonium ion batteries (AIBs) pose the advantages of high safety, low cost, and high efficiency, capturing substantial research interest. The intrinsic chemical properties of NH4+ promote the formation of hydrogen bonds with other constituents in AIBs, critically influencing the processes of NH4+ transfer, storage, and diffusion. This review delves into the pivotal role of hydrogen bonding chemistry in AIBs. Firstly, the principles of hydrogen bond are elucidated as the dominant chemical interaction governing NH4+ dynamics in AIBs. Subsequently, a detailed analysis is conducted on the impacts of hydrogen bonds in both electrolytes and electrode materials. Furthermore, the practical applications of hydrogen bonding chemistry within the context of AIBs are assessed. Finally, strategic insights and future research directions are proposed to harness hydrogen bonding effects for optimizing AIB performance. This review aims to define the mechanisms and impacts of hydrogen bonds in AIBs, providing robust strategies to enhance electrochemical performance, deepen the understanding of energy storage mechanisms, and guide the future advancement of AIBs technology.
Eggshell bio‐filler integration in jute/banana fiber‐reinforced epoxy hybrid composites: Fabrication and characterization
Authors: Dev Barshan , Rahman Md Ashikur , Khan Ayub Nabi , Siddique Abu Bakr , Alam Md Rubel , Rahman Md Zillur 
Published: August 2024

AbstractThe use of waste‐based bio‐fillers in composite manufacturing has increased in recent years due to their sustainable and biodegradable characteristics. The current study fabricates jute/banana (JB) fiber‐reinforced epoxy composites incorporating waste‐derived eggshell (ES) bio‐filler and investigates the effect of ES bio‐filler on the mechanical, morphological, and water absorption properties of the composites. JB fibers (1:1) and varying ES filler contents (5, 10, 15, and 20 wt%) were used to manufacture the composites using the hand lay‐up technique. Their tensile, flexural, and impact properties, microstructure, chemical compositions, and water absorption are then examined. It is found that the composite composed of 15 wt% ES exhibits better tensile and flexural properties with a tensile modulus and strength of 4.42 GPa and 95.27 MPa, and a flexural modulus and strength of 3.96 GPa and 117.47 MPa, respectively, whereas the composite filled with 5 wt% ES shows a maximum impact strength of 46.83 kJ/m2 and drops with increasing bio‐fillers. Scanning electron microscopy reveals that composite failures occur due to jute and banana fiber fractures, filler–fiber‐matrix debonding, fiber pullout, and ES filler agglomeration. Moreover, water absorption reduces as the ES content rises, and the 20 wt% ES filler‐based composite shows a minimum water absorption of 7.67% after 240 h. This study provides some insights to promote the usage of ES bio‐filler in natural fiber composites to improve their mechanical and water absorption properties and their potential applications in the internal structures of automobiles, aircraft, and construction.
Enhanced Type 1 Interferon Signature in Axial Spondyloarthritis Patients Unresponsive to Secukinumab Treatment
Authors: Pacheco Addison , Maguire Sinead , Qaiyum Zoya , Tang Michael , Bridger Adam , Lim Melissa , Tavasolian Fataneh , Yau Enoch , Crome Sarah Q. , Haroon Nigil , Inman Robert D. 
Published: August 2024

ObjectiveAxial spondyloarthritis (axSpA) is an inflammatory disease in which overactive interleukin (IL)‐17A–producing cells are implicated in a central role. Therapeutically, biologics that target IL‐17A, such as secukinumab, have demonstrated improved clinical outcomes. Despite this translational success, there is a gap in understanding why some patients with axSpA do not respond to IL‐17A–blocking therapy. Our study aims to discriminate immune profiles between secukinumab responders (SEC‐R) and nonresponders (SEC‐NR).MethodsPeripheral blood mononuclear cells were collected from 30 patients with axSpA before and 24 weeks after secukinumab treatment. Frequency of CD4+ subsets were compared between SEC‐R and SEC‐NR using flow cytometry. Mature CD45RO+CD45RA‐CD4+ T cells were fluorescent‐activated cell sorting sorted, and RNA was measured using NanoString analysis.ResultsSEC‐NR had an increased frequency of IL‐17A–producing RORγt+CD4+ T cells compared to healthy controls before secukinumab treatment (P < 0.01). SEC‐NR had a significant increase of CXCR3+ CD4+ T cells before secukinumab treatment compared to SEC‐R (P < 0.01). Differentially expressed gene analysis revealed up‐regulation of type 1 interferon (IFN)‐regulated genes in SEC‐NR patients compared to SEC‐R patients after receiving the biologic. SEC‐R patients had an up‐regulated cytotoxic CD4+ T cell gene signature before receiving secukinumab treatment compared to SEC‐NR patients.ConclusionThe increased frequency of IL‐17A–producing cells in SEC‐NR patients suggests a larger inflammatory burden than SEC‐R patients. With treatment, SEC‐NR patients have a more pronounced type 1 IFN signature than SEC‐R patients, suggesting a mechanism contributing to this larger inflammatory burden. The results point toward more immune heterogeneity in axSpA than has been recognized and highlights the need for precision therapeutics in this disease.image
Efficient Synthesis and Iodine‐Functionalization of Pyrazoles via KIO3/PhSeSePh System under Acidic Conditions
Authors: Peglow Thiago J. , Thomaz João Pedro S. S. C. , Nobre Patrick C. , Scimmi Cecilia , Santi Claudio , Nascimento Vanessa 
Published: August 2024

AbstractThis manuscript reports a novel method for the direct iodination of the C‐4 pyrazole ring generated in situ by the reaction of 1,1,3,3‐tetramethoxypropane and various hydrazines. In this approach, potassium iodate (KIO3) is used as the iodinating agent and (PhSe)2 is used as catalysts under acidic conditions. This protocol provides a convenient method for the efficient synthesis of 4‐iodo‐1‐aryl‐1H‐pyrazoles, valuable intermediates for several different coupling reactions.
Evaluating the quality characteristics of intermediate wheatgrass grown in the Canadian prairies
Authors: Ferguson Mackenzie , Valsalan Anashwar , Cattani Douglas , Malalgoda Maneka 
Published: August 2024

AbstractBackground and ObjectivesIntermediate wheatgrass (IWG) is an underutilized perennial grain in the Canadian market with excellent nutritional and environmental benefits. The aim of this study was to assess the impact of the growing environment on the physiochemical and functional properties of IWG grown in three different growing locations in the Canadian prairies. IWG flours were compared between growing locations and years as well as alongside Canada Western Red Spring Wheat whole meal (CWRS‐WM) and refined flour.FindingsThe proximate composition of IWG flours between years and growing locations had significant (p < .05) differences for protein, fiber, and ash content but showed little difference for starch content. Owing to differences in proximate composition, variances in mixing parameters, starch pasting properties, and protein profiles were observed. Overall IWG performed poorly in a bread system at 100% incorporation largely due to its lack of high molecular weight glutenin.ConclusionUnderstanding the impacts that growing location and year have on the proximate composition and therefore working parameters will aid in the development of new wheat products fortified with IWG. These products will contribute to a more resilient and diverse food system, that will provide nutrient‐dense food options for consumers.Significance and NoveltyThere is very limited research on IWG grown in the Canadian prairies, and this study is among the first studies focused on characterizing IWG grown in Canada.
Genital rash: A manifestation of metastatic Crohn's disease
Authors: Chetwood John David , Arzivian Arteen , Shin Joo‐Shik , Tamilarasan Aravind Gokul 
Published: August 2024

Key Clinical MessageMetastatic Crohn's disease is the rarest cutaneous manifestation of Crohn's disease, it presents as cutaneous lesions in areas that are anatomically non‐contiguous with the gastrointestinal tract. It requires a high index of suspicion for diagnosis which is confirmed on histopathology. Infliximab can be an effective treatment.
An unusual case of crusted scabies in an immunocompetent adult: A case report
Authors: Agyei Martin , Opare‐Addo Priscilla Abrafi , Ofori Afua , Kyem Gloria , Gyabaah Solomon , Asare‐Bediako Serwaa 
Published: August 2024

Key Clinical MessageAlthough rare, crusted scabies can affect immunocompetent individuals with no identifiable risk factors. A high index of suspicion, regardless of an individual's immunological status or absence of traditional risk factors, should be maintained by health professionals to facilitate prompt referral to a dermatologist.AbstractCrusted scabies is an uncommon variant of human scabies characterized by extensive crusted and scaly hyperkeratotic papules, and plaques resulting from profound proliferation of mites in the skin. It is highly contagious and typically occurs in immunocompromised individuals. Reports of cases in healthy adults are rare. It is often resistant to routine treatment. We report a case of a 30‐year‐old immunocompetent male who presented to us with an extensive pruritic papular rash that started in the inter‐digital web spaces of his hands. Within 3 months from onset, the lesions progressed, and became hyperkeratotic, scaly, non‐pruritic, spreading to involve his entire body (sparing his face only). Crusty scabies was eventually diagnosed and treated by a dermatologist after months of misdiagnosis at peripheral facilities. Although rare, crusted scabies can affect immunocompetent individuals. A high index of suspicion is required, regardless of immunological status. Among immunocompetent individuals, a thorough search for traditional risk factors is imperative.
Synergetic Effect of Ni‐CeO₂ Bimetallic Catalyst for an Effective Decomposition of Methane to Hydrogen and Filamentous Nanocarbons
Authors: Ahmad Adeel , Reyaz Hamdani Iqra , Pillantakath Abdul Rasheed , Shoaibi Ahmed Al , Chandrasekar Srinivasakannan , Hossain Mohammad Mozahar 
Published: August 2024

AbstractThe work attempts to synthesis nickel‐ceria bimetallic catalysts supported on porous carbon template, thermally stable at 850 °C, for dehydrogenation of methane to hydrogen and carbon nanostructures. A series of bimetallic Ni catalysts were synthesized by varying the % ceria content (30Ni‐5CeO2/AC, 30Ni‐10CeO2/AC, and 30Ni‐15CeO2/AC) using the incipient wetness impregnation approach. Among the set of bimetallic catalysts, the 30Ni‐5CeO2/AC catalyst was found to offer highest methane conversion and stability. A maximum conversion of 90 % was achieved with 40 % methane feed concentration along with good catalyst stability. The promoter ceria at low concentration enhanced the dispersion of metal over the catalytic surface, resulting in adequate metal‐support interaction. The ability of the carbon support along with promoter ceria enhanced the thermal stability of the Ni catalyst up to 850 °C, offering high conversion and catalyst stability has been the highlight of the work. Advanced analytical techniques were used to characterize the catalyst's structural, textural, and morphological properties both before and after the reaction. The morphological study of the best‐performing catalyst demonstrated the formation of dense carbon nanotubes through tip‐growth mechanism exhibiting a high aspect ratio.
Trustworthiness assessment of published clinical trials: Literature review of domains and questions
Authors: Alfirevic Zarko , Weeks Jo 
Published: August 2024

AbstractBackgroundHistorically, peer reviewing has focused on the importance of research questions/hypotheses, appropriateness of research methods, risk of bias, and quality of writing. Until recently, the issues related to trustworthiness—including but not limited to plagiarism and fraud—have been largely neglected because of lack of awareness and lack of adequate tools/training. We set out to identify all relevant papers that have tackled the issue of trustworthiness assessment to identify key domains that have been suggested as an integral part of any such assessment.MethodsWe searched the literature for publications of tools, checklists, or methods used or proposed for the assessment of trustworthiness of randomized trials. Data items (questions) were extracted from the included publications and transcribed on Excel including the assessment domain. Both authors then independently recategorised each data item in five domains (governance, plausibility, plagiarism, reporting, and statistics).ResultsFrom the 41 publications we extracted a total of 284 questions and framed 77 summary questions grouped in five domains: governance (13 questions), plausibility (17 questions), plagiarism (4 questions), reporting (29 questions), and statistics (14 questions).ConclusionThe proposed menu of domains and questions should encourage peer reviewers, editors, systematic reviewers and developers of guidelines to engage in a more formal trustworthiness assessment. Methodologists should aim to identify the domains and questions that should be considered mandatory, those that are optional depending on the resources available, and those that could be discarded because of lack of discriminatory power.
From Meteorite to Life's Building Blocks: A possible Electrochemical Pathway to Amino Acids and Peptide Bonds
Authors: Fernandez Lucas , Yari Farzaneh , Hesser Günter , Schöfberger Wolfgang 
Published: August 2024

AbstractThis study explores the electrochemical properties of the carbonaceous Allende CV3 meteorite, focusing on its potential as a Fe‐based catalyst derived from Mackinawite iron sulfide for electrocatalytic reactions facilitating nitrogen (N2) fixation into ammonia. Through comprehensive analysis, we not only monitored the evolution of key compounds such as CN‐, sulfur/H2S, H2 and carbonyl compounds, but also identified potential reagent carriers, indicating significant implications for the Strecker synthesis of amino acids in space environments. Initial examination revealed the presence of polypeptides, notably sequences including dimer Ala‐α‐HO‐Gly, pentamer Gly3‐Ala2, and hexamer Gly4‐(HO‐Gly)2. These discoveries greatly enhance our understanding of astrobiological chemistry, offering valuable insights into prebiotic processes and the potential presence of life‐building blocks throughout the universe.
Low‐Temperature Synthesis of GeTe Nanoparticles
Authors: Bouška Marek , Milasheuskaya Yaraslava , Šlouf Miroslav , Knotek Petr , Pechev Stanislav , Prokeš Lubomír , Pečinka Lukáš , Havel Josef , Novák Miroslav , Jambor Roman , Němec Petr 
Published: August 2024

AbstractNanoparticles can offer an alternative approach to fabricate phase‐change materials. The chemical synthesis of GeTe nanoparticles using organometallic precursors exploits high‐boiling solvents and relatively high temperatures (close or even above crystallization temperatures), as reported in the available literature. The aim of this work is the preparation of GeTe nanoparticles by a low‐temperature synthetic method exploiting new organometallic precursors and common organic solvents. Indeed, different preparation methods and characterization of GeTe nanoparticles is discussed. The characterization of the prepared nanomaterial was performed on the basis of X‐ray diffraction, transmission electron microscopy, scanning electron microscopy with energy dispersive X‐ray spectroscopy, laser ablation time‐of‐flight mass spectrometry, Raman scattering spectroscopy, and dynamic light scattering. The results show that the low‐temperature synthetic route leads to amorphous GeTe nanoparticles. Exploited organometallic precursor is stabilised by neutral ligand which can be isolated after the reaction and repeatedly used for further reactions. Furthermore, GeTe nanoparticle size can be tuned by the conditions of the synthesis.