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Cu dissolution has been identified as the dominant process that causes cathode degradation and losses even under cathodic conditions involving methylamine. Despite extensive experimental research, our fundamental and theoretical understanding of the atomic-scale mechanism for Cu dissolution under electrochemical conditions, eventually coupled with surface restructuring processes, is limited. Here, driven by the observation that the working Cu electrode is corroded using mixtures of acetone and methylamine even under reductive potential conditions (-0.75 V vs. RHE), we employed Grand Canonical density functional theory to understand this dynamic process under potential from a microscopic perspective. We show that amine ligands in solution directly chemisorb on the electrode, coordinate with the metal center, and drive the rearrangement of the copper surface by extracting Cu as adatoms in low coordination positions, where other amine ligands can coordinate and stabilize a surface copper-ligand complex, finally forming a detached Cu-amine cationic complex in solution, even under negative potential conditions. Calculations predict that dissolution would occur for a potential of -1.1 V vs. RHE or above. Our work provides a fundamental understanding of Cu dissolution facilitated by surface restructuring in amine solutions under electroreduction conditions, which is required for the rational design of durable Cu-based cathodes for electrochemical amination or other amine involving reduction processes.
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The electrochemical hydrogenation (e-hydrogenation) of unsaturated compounds like imines or carbonyls presents a benign reduction method. It enables direct use of electrons as reducing agent, water as proton source, while bypassing the need for elevated temperatures or pressures. In this contribution, we discuss the nature of active sites in electrocatalytic reductive amination with the transformation of acetone and methylamine as model reaction. Surprisingly, lead impurities in the ppm-range proved to possess a significant effect in e-hydrogenation. Accordingly, the influence of applied potential and cathode material in presence of 1 ppm Pb was investigated. Finally, we transferred the insights to the reduction of acetone manifesting comparable observations as for imine reduction. The results suggest that previous studies on electrochemical reduction in the presence of lead electrodes should be re-evaluated.
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The aggregation of amino acids into amyloid-like structures is a critical phenomenon for understanding the pathophysiology of various diseases, including inborn errors of metabolism (IEMs) associated with amino acid imbalances. Previous studies have primarily focused on self-assembly of aromatic amino acids, leading to a limited understanding of nonaromatic, polar amino acids in this context. To bridge this gap, our study investigates the self-assembly and aggregation behavior of specific nonaromatic charged and uncharged polar amino acids l-glutamine (Gln), l-aspartic acid (Asp), and l-glutamic acid (Glu), which have not been reported widely in the context of amyloid aggregation. Upon aging these amino acids under controlled conditions, we observed the formation of uniform, distinct aggregates, with Gln forming fibrillar gel-like structures and Glu exhibiting fibrous globular morphologies. Computational simulations validated these findings, identifying Gln as the most potent in forming stable aggregates, followed by Glu and Asp. These simulations elucidated the driving forces behind the distinct morphologies and stabilities of the aggregates. Thioflavin T assays were employed to confirm the amyloid-like nature of these aggregates, suggesting their potential cytotoxic impact. To assess toxicity, we performed in vitro studies on neural cell lines and in vivo experiments in Caenorhabditis elegans (C. elegans), which demonstrated measurable cytotoxic effects, corroborated by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide and heat shock survival assays. Importantly, this study fills a critical gap in our understanding on the role of nonaromatic amino acids in amyloidogenesis and its implications for IEMs. Our findings provide a foundation for future investigations into the mechanisms of diseases associated with amino acid accumulation and offer potential avenues for the development of targeted therapeutic strategies.
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Amiloide , Ácido Aspártico , Ácido Glutámico , Glutamina , Ácido Aspártico/metabolismo , Ácido Aspártico/química , Ácido Glutámico/metabolismo , Glutamina/metabolismo , Animales , Amiloide/metabolismo , Caenorhabditis elegans , HumanosRESUMEN
The growing concern over the escalating levels of anthropogenic CO2 emissions necessitates effective strategies for its conversion to valuable chemicals and fuels. In this research, we embark on a comprehensive investigation of the nature of zirconia on a copper inverse catalyst under the conditions of CO2 hydrogenation to methanol. We employ density functional theory calculations in combination with the Grand Canonical Basin Hopping method, enabling an exploration of the free energy surface including a variable amount of adsorbates within the relevant reaction conditions. Our focus centers on a model three-atom Zr cluster on a Cu(111) surface decorated with various OH, O, and formate ligands, noted Zr3Ox (OH)y (HCOO)z/Cu(111), revealing major changes in the active site induced by various reaction parameters such as the gas pressure, temperature, conversion levels, and CO2/H2 feed ratios. Through our analysis, we have unveiled insights into the dynamic behavior of the catalyst. Specifically, under reaction conditions, we observe a large number of composition and structures with similar free energy for the catalyst, with respect to changing the type, number, and binding sites of adsorbates, suggesting that the active site should be regarded as a statistical ensemble of diverse structures that interconvert.
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High-power, short-duration (HPSD) radiofrequency (RF) ablation is expected to be more effective and safer than low-power, long-duration (LPLD) RF ablation in treating atrial fibrillation (AF). Given the limited data available, the findings are controversial. This meta-analysis evaluated whether the clinical effects of HPSD outweigh those of LPLD. A systematic search of PubMed, Embase, and Google Scholar databases identified studies comparing HPSD to LPLD ablation. All the analyses used the random-effects model. This analysis included 21 studies with a total of 4,169 patients. Pooled analyses revealed that HPSD was associated with a lower recurrence of atrial tachyarrhythmias (ATAs) at 1 year (relative risk [RR], 0.62; 95% confidence interval [CI], 0.50-0.78; P = .00001; I2 = 0%). Furthermore, the HPSD approach reduced the risk of AF recurrence (RR, 0.64; 95% CI, 0.40-1.01; P = .06; I2 = 86%). The HPSD approach was associated with a lower risk of esophageal thermal injury (ETI) (RR, 0.78; 95% CI, 0.58-1.04; P = .09; I2 = 73%). The HPSD strategy increased first-pass pulmonary vein (PV) isolation (PVI) and decreased acute PV reconnection (PVR), both of which were predominantly manifested in bilateral and left PVs. HPSD facilitated a reduction in procedural time, number of lesions created during PVI, and fluoroscopy time. The HPSD method reduces ETI, PVR, and recurrent AF. The HPSD approach also reduced the procedural time, number of lesions created during PVI, fluoroscopy time, and post-ablation AF relapse in 1 year, improving patient outcomes and safety.
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A combination of density functional theory (DFT) and experiments with atomically size-selected Ptn clusters deposited on indium-tin oxide (ITO) electrodes was used to examine the effects of applied potential and Ptn size on the electrocatalytic activity of Ptn (n = 1, 4, 7, and 8) for the hydrogen evolution reaction (HER). Activity is found to be negligible for isolated Pt atoms on ITO, increasing rapidly with Ptn size such that Pt7/ITO and Pt8/ITO have roughly double the activity per Pt atom compared to atoms in the surface layer of polycrystalline Pt. Both the DFT and experiment find that hydrogen under-potential deposition (Hupd) results in Ptn/ITO (n = 4, 7, and 8) adsorbing â¼2H atoms/Pt atom at the HER threshold potential, equal to ca. double the Hupd observed for Pt bulk or nanoparticles. The cluster catalysts under electrocatalytic conditions are hence best described as a Pt hydride compound, significantly departing from a metallic Pt cluster. The exception is Pt1/ITO, where H adsorption at the HER threshold potential is energetically unfavorable. The theory combines global optimization with grand canonical approaches for the influence of potential, uncovering the fact that several metastable structures contribute to the HER, changing with the applied potential. It is hence critical to include reactions of the ensemble of energetically accessible PtnHx/ITO structures to correctly predict the activity vs Ptn size and applied potential. For the small clusters, spillover of Hads from the clusters to the ITO support is significant, resulting in a competing channel for loss of Hads, particularly at slow potential scan rates.
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Single-atom catalysts (SACs) have attracted attention for their high catalytic activity and selectivity, but the nature of their active sites under realistic reaction conditions, involving various ligands, is not well-understood. In this study, we use density functional theory calculations and grand canonical basin hopping to theoretically investigate the active site for the oxygen evolution reaction (OER) on a single Pt atom supported on indium tin oxide, including the influence of the electrochemical potential. We show that the ligands on the Pt atom change from Pt-OH in the absence of electrochemical potential to PtO(OH)4 in electrochemical conditions. This change of the chemical state of Pt is associated with a decrease of 0.3 V for the OER overpotential. This highlights the importance of accurately identifying the nature of the active site under reaction conditions and the impact of adsorbates on the electrocatalytic activity. This theoretical investigation enhances our understanding of SACs for the OER.
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Hydrazine-assisted water electrolysis offers a feasible path for low-voltage green hydrogen production. Herein, the design and synthesis of ultrathin RhRu0.5 -alloy wavy nanowires as bifunctional electrocatalysts for both the anodic hydrazine oxidation reaction (HzOR) and the cathodic hydrogen evolution reaction (HER) is reported. It is shown that the RhRu0.5 -alloy wavy nanowires can achieve complete electrooxidation of hydrazine with a low overpotential and high mass activity, as well as improved performance for the HER. The resulting RhRu0.5 bifunctional electrocatalysts enable, high performance hydrazine-assisted water electrolysis delivering a current density of 100 mA cm-2 at an ultralow cell voltage of 54 mV and a high current density of 853 mA cm-2 at a cell voltage of 0.6 V. The RhRu0.5 electrocatalysts further demonstrate a stable operation at a high current density of 100 mA cm-2 for 80 hours of testing period with little irreversible degradation. The overall performance greatly exceeds that of the previously reported hydrazine-assisted water electrolyzers, offering a pathway for efficiently converting hazardous hydrazine into molecular hydrogen.
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Electrochemical partial oxidation of methane to methanol is a promising approach to the transformation of stranded methane resources into a high-value, easy-to-transport fuel or chemical. Transition metal oxides are potential electrocatalysts for this transformation. However, a comprehensive and systematic study of the dependence of methane activation rates and methanol selectivity on catalyst morphology and experimental operating parameters has not been realized. Here, we describe an electrochemical method for the deposition of a family of thin-film transition metal (oxy)hydroxides as catalysts for the partial oxidation of methane. CoOx, NiOx, MnOx, and CuOx are discovered to be active for the partial oxidation of methane to methanol. Taking CoOx as a prototypical methane partial oxidation electrocatalyst, we systematically study the dependence of activity and methanol selectivity on catalyst film thickness, overpotential, temperature, and electrochemical cell hydrodynamics. Optimal conditions of low catalyst film thickness, intermediate overpotentials, intermediate temperatures, and fast methanol transport are identified to favor methanol selectivity. Through a combination of control experiments and DFT calculations, we show that the oxidized form of the as-deposited (oxy)hydroxide catalyst films are active for the thermal oxidation of methane to methanol even without the application of bias potential, demonstrating that high valence transition metal oxides are intrinsically active for the activation and oxidation of methane to methanol at ambient temperatures. Calculations uncover that electrocatalytic oxidation enables reaching an optimum potential window in which methane activation forming methanol and methanol desorption are both thermodynamically favorable, methanol desorption being favored by competitive adsorption with hydroxide anion.
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An Embryonic stem line was engineered with CRISPR mediated knock-in to tag the endogenous locus of Sox2 with tdTomato and Gata6 with GFP. The site-specific knock-ins were genotyped by PCR and DNA sequencing. The timely expression of Gata6 and loss of Sox2 upon differentiation in cells and Embryoid bodies (EBs) were studied by microscopy. The GFP and tdtomato expressing population from day 4 EBs showed exclusive expression of GATA6 and SOX2 protein, confirming the appropriate expression of the fluorescent reporters in the cell line.
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Células Madre Embrionarias , Endodermo , Animales , Ratones , Endodermo/metabolismo , Células Madre Embrionarias/metabolismo , Células Madre Embrionarias de Ratones/metabolismo , Factor de Transcripción GATA6/genética , Factor de Transcripción GATA6/metabolismo , Repeticiones Palindrómicas Cortas Agrupadas y Regularmente Espaciadas , Proteína Fluorescente RojaRESUMEN
Two-dimensional superconductors attract great interest both for their fundamental physics and for their potential applications, especially in the rapidly growing field of quantum computing. Despite intense theoretical and experimental efforts, materials with a reasonably high transition temperature are still rare. Even more rare are those that combine superconductivity with a nontrivial band topology that could potentially give rise to exotic states of matter. Here, we predict a remarkably high superconducting critical temperature of 21 K in the easily exfoliable, topologically nontrivial 2D semimetal W2N3. By studying its electronic and superconducting properties as a function of doping and strain, we also find large changes in the electron-phonon interactions that make this material a unique platform to study different coupling regimes and test the limits of current theories of superconductivity. Last, we discuss the possibility of tuning the material to achieve coexistence of superconductivity and topologically nontrivial edge states.
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Background Dental fluorosis has a negative impact on the facial esthetics of adolescents and is a worldwide oral health concern. Objective To assess the prevalence and associated risk factors for dental fluorosis in early adolescents in India. Methods This was a cross-sectional study carried out on 800 adolescent school children selected from the Jhabua and Dhar districts of Madhya Pradesh, India. The children were in the of 12-15-year age group. A total of eight schools from both Jhabua and Dhar districts were included in the study. A self-administered questionnaire collected information on demographic characteristics, oral hygiene practices and various risk factors for dental fluorosis. Water samples were collected from each zone and sent to a laboratory for water fluoride estimation. Dental fluorosis was assessed using the Dean index. Chi-squared (χ2) and logistic regression analysis were performed. Results The overall prevalence of dental fluorosis was found to be 40.5% in early adolescents. The prevalence of dental fluorosis was found to be 45% in the Jhabua district and 36% in the Dhar district. The water fluoride content was found to be the strongest predictor for dental fluorosis followed by the method of water storage. Conclusion Dental fluorosis affects a large number of adolescents in both the Jhabua and Dhar districts of Madhya Pradesh. Effective policies focusing on oral health education and prevention of dental fluorosis need to be drafted.
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Electrochemical water (H2O) splitting is one of the most promising technologies for energy storage by hydrogen (H2) generation but suffers from the requirement of high overpotential in the anodic half-reaction (oxygen evolution), which is a four-electron process. Though transition-metal oxides and oxysulfides are increasingly researched and used as oxygen evolution electrocatalysts, the bases of their differential activities are not properly understood. In this article, we have synthesized NiCo2O4 and NiCo2O x S4-x by a chemical bath deposition technique, and the latter has shown better oxygen evolution performance, both in terms of stability and activity, under alkaline conditions. Comprehensive analysis through time-dependent cyclic voltammetry, microscopy, and elemental analysis reveal that the higher activity of NiCo2O x S4-x may be attributed to the lower metal-sulfur bond energy that facilitates the activation process to form the active metal hydroxide/oxyhydroxide species, higher electrochemically active surface area, higher pore diameter and rugged morphology that prevents corrosion. This work provides significant insights on the advantages of sulfur-containing materials as electrochemical precatalysts over their oxide counterparts for oxygen evolution reaction.