bluuebunny/crossref_metadata_2025_split huggingface dataset:
Metal Cocatalyst Engineering in Metal‐Semiconductor Hybrid Photocatalysts Achieves a Fivefold Enhancement of Hydrogen Evolution
Authors: Park Bumjin , Park Won‐Woo , Choi Ji Yong , Bang Kodong , Kim Sungjoo , Choi Ye‐Jin , Sul Soohwan , Kwon Oh‐Hoon , Song Hyunjoon 
Published: August 2024

AbstractThis study explores the optimal morphology of photochemical hydrogen evolution catalysts in a one‐dimensional system. Systematic engineering of metal tips on precisely defined CdSe@CdS dot‐in‐rods is conducted to exert control over morphology, composition, and both factors. The outcome yields an optimized configuration, a Au−Pt core‐shell structure with a rough Pt surface (Au@r‐Pt), which exhibits a remarkable fivefold increase in quantum efficiency, reaching 86 % at 455 nm and superior hydrogen evolution rates under visible and AM1.5 G irradiation conditions with prolonged stability. Kinetic investigations using photoelectrochemical and time‐resolved measurements demonstrate a greater extent and extended lifetime of the charge‐separated state on the tips as well as rapid water reduction kinetics on high‐energy surfaces. This approach sheds light on the critical role of cocatalysts in hybrid photocatalytic systems for achieving high performance.
Steric Engineering of Rotaxane Catalysts: Benefits and Limits of Using the Mechanical Bond in Catalyst Design
Authors: Struth F. Robin , Jansen Dennis , Pairault Noël , Schumacher Marcel , Uteschil Florian , Linders Jürgen , Mayer Christian , Gröschel André H. , Goldup Stephen M. , Niemeyer Jochen 
Published: August 2024

AbstractThe mechanical bond is emerging as a novel design element in catalyst development. Here, we report a series of 1,1’‐binaphthyl‐2,2’‐diol (BINOL) based catalysts in which the number of interlocked macrocycles is varied. Unsurprisingly, the macrocycles have a profound steric influence on the catalytic performance of these molecules. However, in the enantioselective transformations examined, the macrocycles are detrimental to catalyst stereoselectivity whereas in lactide polymerization, they increase the molecular weight of the polymeric product.
Developing Allosteric Inhibitors of SARS‐CoV‐2 RNA‐Dependent RNA Polymerase
Authors: Chayka Artem , Danda Matěj , Dostálková Alžběta , Spiwok Vojtěch , Klimešová Anna , Kapisheva Marina , Zgarbová Michala , Weber Jan , Ruml Tomáš , Rumlová Michaela , Janeba Zlatko 
Published: August 2024

AbstractThe use of Fpocket and virtual screening techniques enabled us to identify potential allosteric druggable pockets within the SARS‐CoV‐2 RNA‐dependent RNA polymerase (RdRp). Of the compounds screened, compound 1 was identified as a promising inhibitor, lowering a SARS‐CoV‐2 RdRp activity to 57 % in an enzymatic assay at 10 μM concentration. The structure of compound 1 was subsequently optimized in order to preserve or enhance inhibitory activity. This involved the substitution of problematic ester and aromatic nitro groups with more inert functionalities. The N,N’‐diphenylurea scaffold with two NH groups was identified as essential for the compound's activity but also exhibited high toxicity in Calu‐3 cells. To address this issue, a scaffold hopping approach was employed to replace the urea core with potentially less toxic urea isosteres. This approach yielded several structural analogues with notable activity, specifically 2,2’‐bisimidazol (in compound 55 with residual activity RA=42 %) and (1H‐imidazol‐2‐yl)urea (in compounds 59 and 60, with RA=50 and 28 %, respectively). Despite these advances, toxicity remained a major concern. These compounds represent a promising starting point for further structure‐activity relationship studies of allosteric inhibitors of SARS‐CoV‐2 RdRp, with the goal of reducing their cytotoxicity and improving aqueous solubility.
Nanoradiopharmaceuticals: An Attractive Concept in Oncotherapy
Authors: Hou Ruitong , Liu Ning , Li Feize 
Published: August 2024

AbstractRadiopharmaceuticals are of significant importance in the fields of tumor imaging and therapy. In recent decades, the increasing role of nanotechnology has led to the attractive concept of nanoradiopharmaceuticals. Consequently, it is imperative to provide a concise summary of the necessary guidelines to facilitate the translation of nanoradiopharmaceuticals. In this work, we have presented the contents of radiolabeling strategies and some applications of nanoradiopharmaceuticals. Such a framework can assist researchers in identifying more pertinent insights or making more informed decisions in the study of nanoradiopharmaceuticals.
One‐Year Follow‐Up: Schema Therapy for Patients With Borderline Personality Disorder and Comorbid Alcohol Use Disorder
Authors: Boog Michiel , Visser Mette C. , Clarijs Loes , Franken Ingmar H. A. , Arntz Arnoud 
Published: August 2024

ABSTRACTThis article describes the 1‐year follow‐up of a study into the effectiveness of Schema Therapy (ST) for borderline personality disorder (BPD) and comorbid alcohol use disorder (AUD). In the original study, 20 of these patients participated in a multiple baseline case series design study. The results of the original study were promising (a significant decrease of BPD and AUD symptoms). The present study is aimed at examining the longer term benefits of ST for BPD and comorbid AUD. One year after the cessation of the investigational therapy, 17 of the original participants agreed to participate in this follow‐up study. T‐ or Wilcoxon signed rank tests were performed to compare 1‐year follow‐up to start of therapy (baseline). The results suggest that the main therapeutic improvements were generally preserved at 1‐year follow‐up. These findings add to the idea that integrated ST for BPD and comorbid AUD might be effective, also in the long term. A randomized clinical trial is indicated to substantiate this idea.
Cellulose Acetates in Hydrothermal Carbonization: A Green Pathway to Valorize Residual Bioplastics
Authors: Ischia Giulia , Marchelli Filippo , Bazzanella Nicola , Ceccato Riccardo , Calvi Marco , Guella Graziano , Gioia Claudio , Fiori Luca 
Published: August 2024

AbstractBioplastics possess the potential to foster a sustainable circular plastic economy, but their end‐of‐life is still challenging. To sustainably overcome this problem, this work proposes the hydrothermal carbonization (HTC) of residual bioplastics as an alternative green path. The focus is on cellulose acetate – a bioplastic used for eyewear, cigarette filters and other applications – showing the proof of concept and the chemistry behind the conversion, including a reaction kinetics model. HTC of pure and commercial cellulose acetates was assessed under various operating conditions (180–250 °C and 0–6 h), with analyses on the solid and liquid products. Results show the peculiar behavior of these substrates under HTC. At 190–210 °C, the materials almost completely dissolve into the liquid phase, forming 5–hydroxymethylfurfural and organic acids. Above 220 °C, intermediates repolymerize into carbon‐rich microspheres (secondary char), achieving solid yields up to 23 %, while itaconic and citric acid form. A comparison with pure substrates and additives demonstrates that the amounts of acetyl groups and derivatives of the plasticizers are crucial in catalyzing HTC reactions, creating a unique environment capable of leading to a total rearrangement of cellulose acetates. HTC can thus represent a cornerstone in establishing a biorefinery for residual cellulose acetate.
Punctuated aggradation and flow criticality in deep water channel systems
Authors: Kneller Ben , Valdez Buso Victoria 
Published: August 2024

AbstractSubmarine channels are conduits for the transfer of material to deep water by sediment gravity flows. Some channels clearly show meandering patterns in planform that have attracted comparisons with fluvial systems. Many submarine channels, however, are aggradational. Transitions from meandering (at grade) channels to aggradational channels have been described in the subsurface, from seismic data. A field example is presented here in which these meandering and aggradational states may alternate several times during the overall development of a fourth‐order sequence before the system is temporarily or permanently abandoned. This implies a change in flow state from one where successive flows behave similarly over extended periods, to one in which the flow parameters are progressively changing. The cause of these cyclic changes is unclear. The generation of sedimentary architectures so strikingly comparable to those of meandering fluvial systems provides strong evidence in favour of stably stratified, essentially two‐layer flows, in which the lower high‐density part is channel‐confined, with a normal (i.e. fluvial‐like) secondary circulation, and the upper, low‐density part extends onto the overbank regions adjacent to the channel, with minimal mixing and entrainment. Such flows are described as subcritical, in line with published experimental and numerical work, allowing that the critical Froude number in such settings may not be unity. The switch to an aggradational state may be linked to changes in flow criticality, but the ultimate driver for these alternations in flow properties remains unknown.
Hierarchies of stratigraphic discontinuity surfaces in siliciclastic, carbonate and mixed siliciclastic‐bioclastic tidalites: Implications for fluid migration in reservoir quality assessment
Authors: Chiarella Domenico , Longhitano Sergio G. , Spalluto Luigi , Martinius Allard W. 
Published: August 2024

AbstractThe hierarchies of the stratigraphic discontinuity surfaces observed in ancient tidalites are qualitatively assessed, aiming to evaluate their role as possible preferential conduits for fluid migration. Three outcrop examples are presented from microtidal settings of southern Italy: (i) siliciclastic tidalites consisting of quartz‐rich cross‐stratified sandstones generated by strong two‐directional tidal currents flowing along a tidal strait; (ii) carbonate tidalites, which accumulated in a Cretaceous lagoon and tidal flat where peritidal cycles formed vertically‐stacked sequences of biopeloidal and fenestral packstones, wackestones and bindstones during repeated phases of Milankovitch‐scale sea‐level changes; (iii) mixed, siliciclastic‐bioclastic tidalites, deposited in a bay and recording offshore‐transition, to shoreface wave‐dominated and tide‐influenced environments. Observations made during this study suggest that fluid movement can be controlled by the presence of main bounding surfaces that occur at different dimensions, from large (hectometre)‐scale, to medium (decametre)‐scale, to smaller (metre)‐scales. These surfaces produced either by depositional or erosional processes, are characterised by different features and geometries in siliciclastic, carbonate and mixed siliciclastic‐bioclastic tidalites arguably revealing complex internal pathways for fluid flows. These results suggest that fluids propagating along the main discontinuities follow a dominant sub‐horizontal direction of propagation, associated with minor sub‐vertical movements, due to local internal surface geometries and interconnections and a general lack of fractures. This surface‐based approach to the study of fluid‐flow transmission within stratified rocks represents a conceptual attempt to predict fluid mobility and reservoir potential in tidalite‐bearing siliciclastic, carbonate and mixed reservoir rocks.
Expression and Transcriptional Targets of TGFβ‐RII in Paracentrotus lividus Larval Skeletogenesis
Authors: Goloe Daniel , Gildor Tsvia , Ben‐Tabou de‐Leon Smadar 
Published: August 2024

ABSTRACTOrganisms from the five kingdoms of life use minerals to harden their tissues and make teeth, shells and skeletons, in the process of biomineralization. The sea urchin larval skeleton is an excellent system to study the biological regulation of biomineralization and its evolution. The gene regulatory network (GRN) that controls sea urchin skeletogenesis is known in great details and shows similarity to the GRN that controls vertebrates' vascularization while it is quite distinct from the GRN that drives vertebrates' bone formation. Yet, transforming growth factor beta (TGF‐β) signaling regulates both sea urchin and vertebrates' skeletogenesis. Here, we study the upstream regulation and identify transcriptional targets of TGF‐β in the Mediterranean Sea urchin species, Paracentrotus lividus. TGF‐βRII is transiently active in the skeletogenic cells downstream of vascular endothelial growth factor (VEGF) signaling, in P. lividus. Continuous perturbation of TGF‐βRII activity significantly impairs skeletal elongation and the expression of key skeletogenic genes. Perturbation of TGF‐βRII after skeletal initiation leads to a delay in skeletal elongation and minor changes in gene expression. TGF‐β targets are distinct from its transcriptional targets during vertebrates' bone formation, suggesting that the role of TGF‐β in biomineralization in these two phyla results from convergent evolution.
Generation of an Armcx1 Conditional Knockout Mouse
Authors: Bright Cora L. , Bomze Howard M. , Bhaumik Mantu , Kay Jeremy N. , Cartoni Romain , Gospe Sidney M. 
Published: August 2024

ABSTRACTArmadillo repeat‐containing X‐linked protein‐1 (Armcx1) is a poorly characterized transmembrane protein that regulates mitochondrial transport in neurons. Its overexpression has been shown to induce neurite outgrowth in embryonic neurons and to promote retinal ganglion cell (RGC) survival and axonal regrowth in a mouse optic nerve crush model. In order to evaluate the functions of endogenous Armcx1 in vivo, we have created a conditional Armcx1 knockout mouse line in which the entire coding region of the Armcx1 gene is flanked by loxP sites. This Armcx1fl line was crossed with mouse strains in which Cre recombinase expression is driven by the promoters for β‐actin and Six3, in order to achieve deletion of Armcx1 globally and in retinal neurons, respectively. Having confirmed deletion of the gene, we proceeded to characterize the abundance and morphology of RGCs in Armcx1 knockout mice aged to 15 months. Under normal physiological conditions, no evidence of aberrant retinal or optic nerve development or RGC degeneration was observed in these mice. The Armcx1fl mouse should be valuable for future studies investigating mitochondrial morphology and transport in the absence of Armcx1 and in determining the susceptibility of Armcx1‐deficient neurons to degeneration in the setting of additional heritable or environmental stressors.
Size‐dependent effects of dams on river ecosystems and implications for dam removal outcomes
Authors: Brown Rebecca L. , Charles Don , Horwitz Richard J. , Pizzuto James E. , Skalak Katherine , Velinsky David J. , Hart David D. 
Published: August 2024

AbstractUnderstanding the relationship between a dam's size and its ecological effects is important for prioritization of river restoration efforts based on dam removal. Although much is known about the effects of large storage dams, this information may not be applicable to small dams, which represent the vast majority of dams being considered for removal. To better understand how dam effects vary with size, we conducted a multidisciplinary study of the downstream effect of dams on a range of ecological characteristics including geomorphology, water chemistry, periphyton, riparian vegetation, benthic macroinvertebrates, and fish. We related dam size variables to the downstream–upstream fractional difference in measured ecological characteristics for 16 dams in the mid‐Atlantic region ranging from 0.9 to 57 m high, with hydraulic residence times (HRTs) ranging from 30 min to 1.5 years. For a range of physical attributes, larger dams had larger effects. For example, the water surface width below dams was greater below large dams. By contrast, there was no effect of dam size on sediment grain size, though the fraction of fine‐grained bed material was lower below dams independently of dam size. Larger dams tended to reduce water quality more, with decreased downstream dissolved oxygen and increased temperature. Larger dams decreased inorganic nutrients (N, P, Si), but increased particulate nutrients (N, P) in downstream reaches. Aquatic organisms tended to have greater dissimilarity in species composition below larger dams (for fish and periphyton), lower taxonomic diversity (for macroinvertebrates), and greater pollution tolerance (for periphyton and macroinvertebrates). Plants responded differently below large and small dams, with fewer invasive species below large dams, but more below small dams. Overall, these results demonstrate that larger dams have much greater impact on the ecosystem components we measured, and hence their removal has the greatest potential for restoring river ecosystems.
Daily Physical Activity Does Not Contribute to Differences in Muscle Oxidative Capacity Between Overweight and Obesity
Authors: Simon Abigayle B. , Derella Cassandra C. , Looney Jacob C. , Norland Kimberly , Wang Xiaoling , Harris Ryan A. 
Published: August 2024

ABSTRACTBackgroundThe interaction between physical activity, skeletal muscle health, and adiposity has been explored in normal weight and overweight/obesity grouped together; however, the overall risks associated with being overweight are less than those observed with obesity and can be confounded by disparities in both sex and race. Thus, the present study sought to investigate the intricate interplay of daily physical activity and skeletal muscle oxidative capacity (SMOC) in overweight and obesity, while exploring how sex and race impact this dynamic relationship.MethodsOne hundred and forty participants were grouped by body mass index (BMI) as overweight (n = 73; BMI >25–<30 kg/m2) or obese (n = 67; BMI ≥30 kg/m2). SMOC was assessed using near‐infrared spectroscopy and daily physical activity was assessed for 7 days using accelerometry.ResultsOverweight individuals exhibited a higher (p = 0.004) SMOC and engaged in more (p = 0.007) vigorous physical activity compared to obese individuals. In addition, SMOC was lower (p = 0.005) in obese non‐Hispanic Black (NHB) men compared to overweight NHB men. No relationships between physical activity and SMOC were observed.ConclusionPhysical activity is not associated with differences in SMOC in overweight and obesity. Obese individuals engage in less vigorous physical activity and exhibit lower SMOC compared to overweight individuals and these differences are emphasised in NHB men.
Copper(II) Complexes of Phenolate‐Bridged Dimeric Cyclam Ligands: Synthesis, Coordination and Electrochemical Study
Authors: Šrein Jakub , Koláčná Lucie , Kotek Jan , Kubíček Vojtěch , Ludvík Jiří 
Published: August 2024

AbstractBis(macrocyclic) complexes are investigated as artificial analogues of natural dinuclear metalloenzymes. Two ligands containing two cyclam rings connected through a p‐cresol or 4‐nitrophenol spacer were synthesized and their complexing properties were investigated. CuII complexes were prepared and their properties were studied by a combination of spectral, diffraction and electrochemical methods. The phenolate group is not or only weakly coordinated to the central CuII ion and the two macrocycles behave mostly as two independent complexing units. All the determined solid‐state structures showed cyclam adopting trans‐III geometry, however, solution study indicated the presence of more isomers in the solution whose abundance changes with pH. Electrochemical reduction of the complexes is irreversible and results in the reductive decomplexation to amalgamated Cu metal. The amalgamated metal is re‐oxidized to CuII during the anodic scan of CV and the metal ion is re‐coordinated. The ligand containing the nitro group shows an irreversible four‐electron reduction of the nitro group. The ligands and the complexes undergo also a slow degradation when incubated in the aqueous solutions for a prolonged time. The degradation relies on the “retro‐Mannich” cleavage of the methylene bridge connecting the cyclam ring with the phenol moiety.
Exploring the Stability of Primary Phosphine Oxides: Correlation with Primary Phosphine′s Air‐Stability?
Authors: Horký Filip , Bruhn Clemens , Pietschnig Rudolf 
Published: August 2024

AbstractTo better understand the stability of isolable primary phosphine oxides, new members of this family were synthesized through the oxidation of the corresponding phosphines. Specifically, the previously reported air‐stable primary phosphines (R)‐2‐phosphanyl‐2’‐methoxy‐1,1’‐binaphthyl, 9,10‐dihydro‐9,10‐etheno‐anthracen‐9‐yl phosphine, and 3‐phosphino‐2‐naphthol were treated with hydrogen peroxide or meta‐chloroperoxybenzoic acid to yield the new primary phosphine oxides. The compounds were characterized using NMR, MS, EA, and X‐ray crystallography. The oxides were further investigated in thermal disproportionation, and studied as ligands in half‐sandwich Ru(II) complexes bearing an auxiliary η6‐p‐cymene ligand.
Visible‐Light Induced and PIFA Enabled [4+2] Annulation of Alkenes with N‐Aryl Substituted Hydroxamic Acids
Authors: Wang Yu‐Zhao , Jiang Menglu , Zhang Feng , Zhang Hua‐Wei , Wu Yue , Yu Wei , Li Yan 
Published: August 2024

AbstractIn this paper, we reported a facile approach for the preparation of benzo[c][1,2]oxazine scaffolds via visible light induced phenyl iodine bis(trifluoroacetate) (PIFA) oxidative [4+2] annulation of vinyl benzenes with N‐aryl substituted hydroxamic acids. In the transformation, amidoxyl radicals are readily generated via covalent I−O bond formation and photo‐induced I−O cleavage from N‐aryl substituted hydroxamic acids, and their coupling with vinyl arenes in the form of [4+2] annulation delivers benzo[c]‐[1,2]oxazines derivatives. This reaction proceeds in the absence of transition metals and catalysts, exhibiting broad substrate scope of both alkenes and N‐aryl substituted hydroxamic acids.