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1.
J Am Chem Soc ; 146(1): 878-883, 2024 Jan 10.
Artigo em Inglês | MEDLINE | ID: mdl-38154046

RESUMO

Molecular Ir catalysts have emerged as an important class of model catalysts for understanding structure-activity relationships in water oxidation, a reaction that is central to renewable fuel synthesis. Prior efforts have mostly focused on controlling and elucidating the emergence of active species from prepared precursors. However, the development of efficient and stable molecular Ir catalysts also necessitates probing of reaction intermediates. To date, relatively little is known about the key intermediates in the cycles of the molecular Ir catalysts. Herein, we probed the catalytic cycle of a homogeneous Ir catalyst ("blue dimer") at a Au electrode/aqueous electrolyte interface by combining surface-enhanced infrared absorption spectroscopy (SEIRAS) with phase-sensitive detection (PSD). Cyclic voltammograms (CVs) from 1.4 to 1.7 VRHE (RHE = reversible hydrogen electrode) give rise to a band at ∼818 cm-1, whereas CVs from 1.4 to ≥1.85 VRHE generate an additional band at ∼1146 cm-1. Isotope labeling experiments indicate that the bands at ∼818 and ∼1146 cm-1 are attributable to oxo (IrV═O) and superoxo (IrIV-OO•) moieties, respectively. This study establishes PSD-SEIRAS as a sensitive tool for probing water oxidation cycles at electrode/electrolyte interfaces and demonstrates that the relative abundance of two key intermediates can be tuned by the thermodynamic driving force of the reaction.

2.
J Am Chem Soc ; 146(19): 13438-13444, 2024 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-38687695

RESUMO

The Baeyer-Villiger oxidation of ketones is a crucial oxygen atom transfer (OAT) process used for ester production. Traditionally, Baeyer-Villiger oxidation is accomplished by thermally oxidizing the OAT from stoichiometric peroxides, which are often difficult to handle. Electrochemical methods hold promise for breaking the limitation of using water as the oxygen atom source. Nevertheless, existing demonstrations of electrochemical Baeyer-Villiger oxidation face the challenges of low selectivity. We report in this study a strategy to overcome this challenge. By employing a well-known water oxidation catalyst, Fe2O3, we achieved nearly perfect selectivity for the electrochemical Baeyer-Villiger oxidation of cyclohexanone. Mechanistic studies suggest that it is essential to produce surface hydroperoxo intermediates (M-OOH, where M represents a metal center) that promote the nucleophilic attack on ketone substrates. By confining the reactions to the catalyst surfaces, competing reactions (e.g., dehydrogenation, carboxylic acid cation rearrangements, and hydroxylation) are greatly limited, thereby offering high selectivity. The surface-initiated nature of the reaction is confirmed by kinetic studies and spectroelectrochemical characterizations. This discovery adds nucleophilic oxidation to the toolbox of electrochemical organic synthesis.

3.
BMC Cardiovasc Disord ; 24(1): 183, 2024 Mar 27.
Artigo em Inglês | MEDLINE | ID: mdl-38539069

RESUMO

BACKGROUND: Myocardial ischemia is a prevalent cardiovascular disorder associated with significant morbidity and mortality. While prompt restoration of blood flow is essential for improving patient outcomes, the subsequent reperfusion process can result in myocardial ischemia-reperfusion injury (MIRI). Mitophagy, a specialized autophagic mechanism, has consistently been implicated in various cardiovascular disorders. However, the specific connection between ischemia-reperfusion and mitophagy remains elusive. This study aims to elucidate and validate central mitophagy-related genes associated with MIRI through comprehensive bioinformatics analysis. METHODS: We acquired the microarray expression profile dataset (GSE108940) from the Gene Expression Omnibus (GEO) and identified differentially expressed genes (DEGs) using GEO2R. Subsequently, these DEGs were cross-referenced with the mitophagy database, and differential nucleotide sequence analysis was performed through enrichment analysis. Protein-protein interaction (PPI) network analysis was employed to identify hub genes, followed by clustering of these hub genes using cytoHubba and MCODE within Cytoscape software. Gene set enrichment analysis (GSEA) was conducted on central genes. Additionally, Western blotting, immunofluorescence, and quantitative polymerase chain reaction (qPCR) analyses were conducted to validate the expression patterns of pivotal genes in MIRI rat model and H9C2 cardiomyocytes. RESULTS: A total of 2719 DEGs and 61 mitophagy-DEGs were identified, followed by enrichment analyses and the construction of a PPI network. HSP90AA1, RPS27A, EEF2, EIF4A1, EIF2S1, HIF-1α, and BNIP3 emerged as the seven hub genes identified by cytoHubba and MCODE of Cytoscape software. Functional clustering analysis of HIF-1α and BNIP3 yielded a score of 9.647, as determined by Cytoscape (MCODE). In our MIRI rat model, Western blot and immunofluorescence analyses confirmed a significant elevation in the expression of HIF-1α and BNIP3, accompanied by a notable increase in the ratio of LC3II to LC3I. Subsequently, qPCR confirmed a significant upregulation of HIF-1α, BNIP3, and LC3 mRNA in the MIRI group. Activation of the HIF-1α/BNIP3 pathway mediates the regulation of the degree of Mitophagy, thereby effectively reducing apoptosis in rat H9C2 cardiomyocytes. CONCLUSIONS: This study has identified seven central genes among mitophagy-related DEGs that may play a pivotal role in MIRI, suggesting a correlation between the HIF-1α/BNIP3 pathway of mitophagy and the pathogenesis of MIRI. The findings highlight the potential importance of mitophagy in MIRI and provide valuable insights into underlying mechanisms and potential therapeutic targets for further exploration in future studies.


Assuntos
Isquemia Miocárdica , Traumatismo por Reperfusão Miocárdica , Humanos , Ratos , Animais , Traumatismo por Reperfusão Miocárdica/metabolismo , Mitofagia/genética , Mapas de Interação de Proteínas/genética , Biologia Computacional
4.
J Am Chem Soc ; 145(2): 769-773, 2023 01 18.
Artigo em Inglês | MEDLINE | ID: mdl-36594824

RESUMO

Oxidative methane (CH4) carbonylation promises a direct route to the synthesis of value-added oxygenates such as acetic acid (CH3COOH). Here, we report a strategy to realize oxidative CH4 carbonylation through immobilized Ir complexes on an oxide support. Our immobilization approach not only enables direct CH4 activation but also allows for easy separation and reutilization of the catalyst. Furthermore, we show that a key step, methyl migration, that forms a C-C bond, is sensitive to the electrophilicity of carbonyl, which can be tuned by a gentle reduction to the Ir centers. While the as-prepared catalyst that mainly featured Ir(IV) preferred CH3COOH production, a reduced catalyst featuring predominantly Ir(III) led to a significant increase of CH3OH production at the expense of the reduced yield of CH3COOH.


Assuntos
Irídio , Metano , Irídio/química , Metano/química , Oxirredução , Catálise , Óxidos
5.
Angew Chem Int Ed Engl ; 62(34): e202307909, 2023 Aug 21.
Artigo em Inglês | MEDLINE | ID: mdl-37382150

RESUMO

Solar water oxidation is a critical step in artificial photosynthesis. Successful completion of the process requires four holes and releases four protons. It depends on the consecutive accumulation of charges at the active site. While recent research has shown an obvious dependence of the reaction kinetics on the hole concentrations on the surface of heterogeneous (photo)electrodes, little is known about how the catalyst density impacts the reaction rate. Using atomically dispersed Ir catalysts on hematite, we report a study on how the interplay between the catalyst density and the surface hole concentration influences the reaction kinetics. At low photon flux, where surface hole concentrations are low, faster charge transfer was observed on photoelectrodes with low catalyst density compared to high catalyst density; at high photon flux and high applied potentials, where surface hole concentrations are moderate or high, slower surface charge recombination was afforded by low-density catalysts. The results support that charge transfer between the light absorber and the catalyst is reversible; they reveal the unexpected benefits of low-density catalyst loading in facilitating forward charge transfer for desired chemical reactions. It is implied that for practical solar water splitting devices, a suitable catalyst loading is important for maximized performance.

6.
Sensors (Basel) ; 21(5)2021 Mar 05.
Artigo em Inglês | MEDLINE | ID: mdl-33807518

RESUMO

This communication provides an integrated process route of smelting gallium-based liquid metal (GBLM) in a high vacuum, and injecting GBLM into the antenna channel in high-pressure protective gas, which avoids the oxidation of GBLM during smelting and filling. Then, a frequency-reconfigurable antenna, utilizing the thermal expansion characteristic of GBLM, is proposed. To drive GBLM into an air-proof space, the thermal expansion characteristics of GBLM are required. The dimensions of the radiating element of the liquid metal antenna can be adjusted at different temperatures, resulting in the reconfigurability of the operating frequency. To validate the proposed concept, an L-band antenna prototype was fabricated and measured. Experimental results demonstrate that the GBLM in the antenna was well filled, and the GBLM was not oxidized. Due to the GBLM being in an air-proof channel, the designed liquid metal antenna without electrolytes could be used in an air environment for a long time. The antenna is able to achieve an effective bandwidth of over 1.25-2.00 GHz between 25 °C and 100 °C. The maximum radiation efficiency and gain in the tunable range are 94% and 2.9 dBi, respectively. The designed antenna also provides a new approach to the fabrication of a temperature sensor that detects temperature in some situations that are challenging for conventional temperature sensing technology.

7.
Biochemistry ; 59(10): 1093-1103, 2020 03 17.
Artigo em Inglês | MEDLINE | ID: mdl-32100530

RESUMO

Epigallocatechin-3-gallate (EGCG) is a catechin found in green tea that can inhibit the amyloid formation of a wide variety of proteins. EGCG's ability to prevent or redirect the amyloid formation of so many proteins may reflect a common mechanism of action, and thus, greater molecular-level insight into how it exerts its effect could have broad implications. Here, we investigate the molecular details of EGCG's inhibition of the protein ß-2-microglobulin (ß2m), which forms amyloids in patients undergoing long-term dialysis treatment. Using size-exclusion chromatography and a collection of mass spectrometry-based techniques, we find that EGCG prevents Cu(II)-induced ß2m amyloid formation by diverting the normal progression of preamyloid oligomers toward the formation of spherical, redissolvable aggregates. EGCG exerts its effect by binding with a micromolar affinity (Kd ≈ 5 µM) to the ß2m monomer on the edge of two ß-sheets near the N-terminus. This interaction destabilizes the preamyloid dimer and prevents the formation of a tetramer species previously shown to be essential for Cu(II)-induced ß2m amyloid formation. EGCG's binding at the edge of the ß-sheets in ß2m is consistent with a previous hypothesis that EGCG generally prevents amyloid formation by binding cross-ß-sheet aggregation intermediates.


Assuntos
Amiloide/química , Catequina/análogos & derivados , Microglobulina beta-2/química , Amiloide/metabolismo , Proteínas Amiloidogênicas/química , Amiloidose/metabolismo , Catequina/metabolismo , Catequina/farmacologia , Catequina/fisiologia , Cromatografia em Gel/métodos , Cobre/metabolismo , Humanos , Espectrometria de Massas/métodos , Modelos Moleculares , Conformação Proteica em Folha beta/fisiologia , Multimerização Proteica/efeitos dos fármacos , Microglobulina beta-2/antagonistas & inibidores , Microglobulina beta-2/metabolismo
8.
Anal Chem ; 92(9): 6637-6644, 2020 05 05.
Artigo em Inglês | MEDLINE | ID: mdl-32250591

RESUMO

A new covalent labeling (CL) reagent based on an α,ß-unsaturated carbonyl scaffold has been developed for studying protein structure and protein-protein interactions when coupled with mass spectrometry. We show that this new reagent scaffold can react with up to 13 different types of residues on protein surfaces, thereby providing excellent structural resolution. To illustrate the value of this reagent scaffold, it is used to identify the residues involved in the protein-protein interface that is formed upon Zn(II) binding to the protein ß-2-microglobulin. The modular design of the α,ß-unsaturated carbonyl scaffold allows facile variation of the functional groups, enabling labeling kinetics and selectivity to be tuned. Moreover, by introducing isotopically enriched functional groups into the reagent structure, labeling sites can be more easily identified by MS and MS/MS. Overall, this reagent scaffold should be a valuable CL reagent for protein higher order structure characterization by MS.


Assuntos
Aminoácidos/química , Anidrases Carbônicas/química , Lactoglobulinas/química , Mioglobina/química , Microglobulina beta-2/química , Aminoácidos/síntese química , Animais , Bovinos , Cavalos , Humanos , Espectrometria de Massas , Modelos Moleculares , Ligação Proteica , Conformação Proteica
9.
Anal Chem ; 91(23): 15248-15254, 2019 12 03.
Artigo em Inglês | MEDLINE | ID: mdl-31664819

RESUMO

Hydrogen-deuterium exchange (HDX) mass spectrometry (MS) and covalent labeling (CL) MS are typically considered to be complementary methods for protein structural analysis, because one probes the protein backbone, while the other probes side chains. For protein-ligand interactions, we demonstrate in this work that the two labeling techniques can provide synergistic structural information about protein-ligand binding when reagents like diethylpyrocarbonate (DEPC) are used for CL because of the differences in the reaction rates of DEPC and HDX. Using three model protein-ligand systems, we show that the slower time scale for DEPC labeling makes it only sensitive to changes in solvent accessibility and insensitive to changes in protein structural fluctuations, whereas HDX is sensitive to changes in both solvent accessibility and structural fluctuations. When used together, the two methods more clearly reveal binding sites and ligand-induced changes to structural fluctuations that are distant from the binding site, which is more comprehensive information than either technique alone can provide. We predict that these two methods will find widespread usage together for more deeply understanding protein-ligand interactions.


Assuntos
Dietil Pirocarbonato/química , Espectrometria de Massa com Troca Hidrogênio-Deutério , Proteínas/química , Ligantes , Modelos Moleculares
10.
Methods ; 144: 79-93, 2018 07 15.
Artigo em Inglês | MEDLINE | ID: mdl-29630925

RESUMO

Using mass spectrometry (MS) to obtain information about a higher order structure of protein requires that a protein's structural properties are encoded into the mass of that protein. Covalent labeling (CL) with reagents that can irreversibly modify solvent accessible amino acid side chains is an effective way to encode structural information into the mass of a protein, as this information can be read-out in a straightforward manner using standard MS-based proteomics techniques. The differential reactivity of proteins under two or more conditions can be used to distinguish protein topologies, conformations, and/or binding sites. CL-MS methods have been effectively used for the structural analysis of proteins and protein complexes, particularly for systems that are difficult to study by other more traditional biochemical techniques. This review provides an overview of the non-specific CL approaches that have been combined with MS with a particular emphasis on the reagents that are commonly used, including hydroxyl radicals, carbenes, and diethylpyrocarbonate. We describe the reagent and protein factors that affect the reactivity of amino acid side chains. We also include details about experimental design and workflow, data analysis, recent applications, and some future prospects of CL-MS methods.


Assuntos
Espectrometria de Massas/métodos , Conformação Proteica , Proteínas/metabolismo , Sítios de Ligação , Mapeamento de Interação de Proteínas , Proteínas/química , Proteômica
11.
Analyst ; 143(6): 1434-1443, 2018 Mar 12.
Artigo em Inglês | MEDLINE | ID: mdl-29468243

RESUMO

Polymeric reverse micelles can be used to selectively extract peptides from complex mixtures via a two-phase extraction approach. In previous work, we have shown that the charge polarity of the hydrophilic functional group that is in the interior of the reverse micelle dictates the extraction selectivity. To investigate how the extraction is influenced by the inherent pKa of the functional group, we designed and tested a series of polymeric reverse micelles with variations in the hydrophilic functional group. From this series of polymers, we find that the extraction capability of the reverse micelles in an apolar phase is directly related to the aqueous phase pKa of the interior functional group, suggesting that the functional groups maintain their inherent chemistry even in the confined environment of the reverse micelle interior. Because these functional groups maintain their inherent pKa in the reverse micelle interior, they provide predictable extraction selectivity upon changes in aqueous phase pH. We exploit this finding to demonstrate that sulfonate-containing polymers can be used to remove basic peptides from complex mixtures, thereby allowing the improved detection of acidic peptides. Using these new materials, we also demonstrate a new means of isoelectric point (pI) bracketing that allows the mass spectrometric detection of peptides with a defined and narrow range of pI values.

12.
Anal Chem ; 89(21): 11583-11591, 2017 11 07.
Artigo em Inglês | MEDLINE | ID: mdl-29028328

RESUMO

Amyloid aggregates are associated with several debilitating diseases, and there are numerous efforts to develop small molecule treatments against these diseases. One challenge associated with these efforts is determining protein binding site information for potential therapeutics because amyloid-forming proteins rapidly form oligomers and aggregates, making traditional protein structural analysis techniques challenging. Using ß-2-microglobulin (ß2m) as a model amyloid-forming protein along with two recently identified small molecule amyloid inhibitors (i.e., rifamycin SV and doxycycline), we demonstrate that covalent labeling and mass spectrometry (MS) can be used to map small-molecule binding sites for a rapidly aggregating protein. Specifically, three different covalent labeling reagents, namely diethylpyrocarbonate, 2,3-butanedione, and the reagent pair EDC/GEE, are used together to pinpoint the binding sites of rifamycin SV, doxycycline, and another molecule, suramin, which binds but does not inhibit Cu(II)-induced ß2m amyloid formation. The labeling results reveal binding sites that are consistent with the known effects of these molecules on ß2m amyloid formation and are in general agreement with molecular docking results. We expect that this combined covalent labeling approach will be applicable to other protein/small molecule systems that are difficult to study by traditional means.


Assuntos
Amiloide/química , Amiloide/metabolismo , Espectrometria de Massas , Simulação de Acoplamento Molecular , Agregados Proteicos/efeitos dos fármacos , Sítios de Ligação , Doxiciclina/metabolismo , Doxiciclina/farmacologia , Humanos , Ligação Proteica , Conformação Proteica , Proteólise , Rifamicinas/metabolismo , Rifamicinas/farmacologia , Coloração e Rotulagem , Suramina/metabolismo , Suramina/farmacologia , Microglobulina beta-2/química , Microglobulina beta-2/metabolismo
13.
Int J Radiat Biol ; 100(10): 1416-1425, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-39101819

RESUMO

BACKGROUND: Ultrasound-stimulated microbubble (USMB) therapy has proven efficacy of targeting tumor vasculature and enhancing the effect of radiation in tumor xenografts. In this investigation, we studied whether this treatment enhances the sensitivity of cervical cancer to radiation. METHODS: Human cervical cancer (ME-180 and SiHa) cells were treated with USMB or exposed to radiation (0, 2, 4, 6 and 8 Gy) or radiation (8 Gy) in combination with USMB. Clone formation assay and CCK-8 assay were used to analyze the proliferation capacity of cells. Apoptosis and DNA double-strand breaks were detected using flow cytometry and immunofluorescence staining of gamma-H2AX (γ-H2AX), respectively. Matrigel tubule formation was performed to evaluate the angiogenesis of human umbilical vein endothelial cells. In xenograft model of SiHa cells, tumor tissue expression of CD31 was detected by immunohistochemistry. RESULTS: USMB and radiation synergistically restrained the growth of ME-180 and SiHa cells. USMB promoted radiation-induced apoptosis by enhancing the levels of proapoptotic proteins. Furthermore, USMB enhanced radiation-induced γ-H2AX foci to induce DNA double-strand breaks in cervical cancer cells. USMB in combination with radiation reduced the angiogenic capacity of endothelial cells in vitro. Moreover, USMB strengthened the inhibitory effect of radiation on tumor growth and angiogenesis in xenograft models. CONCLUSION: In conclusion, USMB exposure effectively enhanced the destructive effect of radiation on cervical cancer, suggesting that USMB might be a promising sensitizer of radiotherapy to treat cervical cancer.


Assuntos
Apoptose , Microbolhas , Tolerância a Radiação , Neoplasias do Colo do Útero , Neoplasias do Colo do Útero/radioterapia , Neoplasias do Colo do Útero/irrigação sanguínea , Neoplasias do Colo do Útero/patologia , Neoplasias do Colo do Útero/metabolismo , Neoplasias do Colo do Útero/diagnóstico por imagem , Microbolhas/uso terapêutico , Humanos , Feminino , Animais , Linhagem Celular Tumoral , Apoptose/efeitos da radiação , Camundongos , Quebras de DNA de Cadeia Dupla/efeitos da radiação , Células Endoteliais da Veia Umbilical Humana , Ondas Ultrassônicas , Camundongos Nus , Terapia por Ultrassom/métodos , Histonas/metabolismo , Ensaios Antitumorais Modelo de Xenoenxerto , Neovascularização Patológica/radioterapia , Proliferação de Células/efeitos da radiação
14.
Microbiol Spectr ; : e0149024, 2024 Oct 15.
Artigo em Inglês | MEDLINE | ID: mdl-39404486

RESUMO

Exploring the link between gut microbiota and chronic gastritis (CG), and assessing the potential mediating influence of blood metabolites. Using aggregated data from genome-wide association studies (GWAS), we performed a two-sample Mendelian randomization (MR) analysis to explore the genetic links between gut microbiota (412 types) and CG (623,822 cases). Furthermore, we utilized a two-step MR approach to measure the extent to which blood metabolites (1,400 types) mediate the impact of gut microbiota on CG. Through MR, we identified that three genetically predicted gut microbiota increased the risk of CG: the ubiquinol-8 biosynthesis pathway (OR 1.149, 95%CI 1.022-1.291), Odoribacter from the Porphyromonadaceae family (OR 1.260, 95%CI 1.044-1.523), and Coprococcus from the Lachnospiraceae family (OR 1.125, 95%CI 1.010-1.253). Currently, there is no evidence to suggest that genetically predicted CG affects the risk of gut microbiota. Four blood metabolites mediated the proportionate changes in genetically predicted gut microbiota: levels of 4-hydroxyphenylacetate levels by 14.9% (95% CI -0.559%, 30.3%), palmitoleate (16:1n7) levels, and the phosphate to alanine ratio together mediated the same microbiota by 6.97% (95% CI -1.61%, 15.6%) and 7.91% (95% CI -1.67%, 17.5%), while the phosphate to alanine ratio and X-12839 levels together mediated the same microbiota by 8.48% (95% CI -2.87%, 19.8%) and 10.7% (95% CI 0.353%, 21.1%). In conclusion, our research has confirmed a causal link between gut microbiota, blood metabolites, and CG. Metabolites such as 4-hydroxyphenylacetate levels, palmitoleate (16:1n7) levels, the phosphate to alanine ratio, and X-12839 levels have relatively significant mediating roles between gut microbiota and CG. These metabolites may influence the occurrence and development of CG by regulating inflammatory responses, energy metabolism, and gut barrier function. However, the majority of the influence of gut microbiota on CG remains unclear, necessitating further research into other potential mediating risk factors. Clinically, it is crucial to focus on patients suffering from CG who exhibit dysbiosis of gut microbiota.IMPORTANCEThe results indicate that interactions between particular gut microbiota and blood metabolites may significantly contribute to the onset and progression of CG. These findings offer new insights and potential targets for early diagnosis, personalized treatment, and prevention of CG.

15.
ChemSusChem ; 16(7): e202202319, 2023 Apr 06.
Artigo em Inglês | MEDLINE | ID: mdl-36602840

RESUMO

Molecular catalysts are promising oxygen evolution promoters in conjunction with photoanodes for solar water splitting. Maintaining the stability of both photoabsorber and cocatalyst is still a prime challenge, with many efforts tackling this issue through sophisticated material designs. Such approaches often mask the importance of the electrode-electrolyte interface and overlook easily tunable system parameters, such as the electrolyte environment, to improve efficiency. We provide a systematic study on the activity-stability relationship of a prominent Fe2 O3 photoanode modified with Ir molecular catalysts using in situ mass spectroscopy. After gaining detailed insights into the dissolution behavior of the Ir cocatalyst, a comprehensive pH study is conducted to probe the impact of the electrolyte on the performance. An inverse trend in Fe and Ir stability is found, with the best activity-stability synergy obtained at pH 9.7. The results bring awareness to the overall photostability and electrolyte engineering when advancing catalysts for solar water splitting.

16.
J Colloid Interface Sci ; 631(Pt B): 78-88, 2023 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-36395629

RESUMO

HYPOTHESIS: The high surface tension of liquid metal (LM) causes interface incompatibility and poor bonding strength with many substrates. Fine adjustment towards the properties of the surface area is sufficient to introduce strong bonding. Hence, we hypothesize that the interlocking structure using hydrophilic polyvinyl alcohol (PVA) as a "bridge" should be helpful for tight interfacial bonding of LM with polymeric substrates, thus achieving high-performance LM/polymer membranes, which have wide applications in the field of soft sensors and robotics. EXPERIMENTS: The bulk EGaIn was fabricated into LM nanoparticles (LMNPs@PVA) solution. Then, PVA molecules were "doped" into the surface crosslink of the plasma treated polymer substrate by an interfacial penetrating method. Afterward, the solution was evenly dropped on the surface of the treated substrate to obtain the LMNP/polymer membrane after the water evaporated. Photothermal actuators were fabricated based on the membranes. FINDINGS: During the interlocking structure, PVA macromolecules could be doped and trapped onto the top surfaces of various polymer substrates as binding "bridges" between the LMNPs and the matrix materials. The achieved LMNP membrane exhibites satisfactory bonding strength, durability and water-assisted erase-reprint, which can be used as soft photothermal actuators with remote laser control.


Assuntos
Nanopartículas Metálicas , Polímeros , Metais , Álcool de Polivinil , Água
17.
ChemSusChem ; 16(7): e202300406, 2023 Apr 06.
Artigo em Inglês | MEDLINE | ID: mdl-36960909

RESUMO

Invited for this month's cover is the group of Dunwei Wang from Boston College and Serhiy Cherevko from the Helmholtz Institute Erlangen-Nürnberg for Renewable Energy. The image illustrates the impact of different electrolyte environments on the stability of hematite decorated with an iridium molecular catalyst used for solar water splitting. The Research Article itself is available at 10.1002/cssc.202202319.

18.
ACS Appl Mater Interfaces ; 15(27): 33132-33139, 2023 Jul 12.
Artigo em Inglês | MEDLINE | ID: mdl-37379244

RESUMO

High-voltage lithium cobalt oxide (LiCoO2) has the highest volumetric energy density among commercial cathode materials in lithium-ion batteries due to its high working voltage and compacted density. However, under high voltage (4.6 V), the capacity of LiCoO2 fades rapidly due to parasitic reactions of high-valent cobalt with the electrolyte and the loss of lattice oxygen at the interface. In this study, we report a temperature-driven anisotropic doping phenomenon of Mg2+ that results in surface-populated Mg2+ doping to the side of the (003) plane of LiCoO2. Mg2+ dopants enter the Li+ sites, lower the valence state of Co ions with less hybridization between the O 2p and Co 3d orbitals, promote the formation of surface Li+/Co2+ anti-sites, and suppress lattice oxygen loss on the surface. As a result, the modified LiCoO2 demonstrates excellent cycling performance under 4.6 V, reaching an energy density of 911.2 Wh/kg at 0.1C and retaining 92.7% (184.3 mAh g-1) of its capacity after 100 cycles at 1C. Our results highlight a promising avenue for enhancing the electrochemical performance of LiCoO2 by anisotropic surface doping with Mg2+.

19.
Chem Sci ; 14(24): 6601-6607, 2023 Jun 21.
Artigo em Inglês | MEDLINE | ID: mdl-37350819

RESUMO

Heterogeneous water oxidation catalysis is central to the development of renewable energy technologies. Recent research has suggested that the reaction mechanisms are sensitive to the hole density at the active sites. However, these previous results were obtained on catalysts of different materials featuring distinct active sites, making it difficult to discriminate between competing explanations. Here, a comparison study based on heterogenized dinuclear Ir catalysts (Ir-DHC), which feature the same type of active site on different supports, is reported. The prototypical reaction was water oxidation triggered by pulsed irradiation of suspensions containing a light sensitizer, Ru(bpy)32+, and a sacrificial electron scavenger, S2O82-. It was found that at relatively low temperatures (288-298 K), the water oxidation activities of Ir-DHC on indium tin oxide (ITO) and CeO2 supports were comparable within the studied range of fluences (62-151 mW cm-2). By contrast, at higher temperatures (310-323 K), Ir-DHC on ITO exhibited a ca. 100% higher water oxidation activity than on CeO2. The divergent activities were attributed to the distinct abilities of the supporting substrates in redistributing holes. The differences were only apparent at relatively high temperatures when hole redistribution to the active site became a limiting factor. These findings highlight the critical role of the supporting substrate in determining the turnover at active sites of heterogeneous catalysts.

20.
Artigo em Inglês | MEDLINE | ID: mdl-35839288

RESUMO

As as emerging innovation, electronic textiles have shown promising potential in health monitoring, energy harvesting, temperature regulation, and human-computer interactions. To access broader application scenarios, numerous e-textiles have been designed with a superhydrophobic surface to steer clear of interference from humidity or chemical decay. Nevertheless, even the cutting-edge electronic textiles (e-textiles) still have difficulty in realizing superior conductivity and satisfactory water repellency simultaneously. Herein, a facile and efficient approach to integrate a hierarchical elastic e-textile is proposed by electroless silver plating on GaIn alloy liquid metal coated textiles. The continuous uneven surface of AgNPs and deposition of FAS-17 endow the textile with exceptional and robust superhydrophobic performance, in which the conductivity and the contact angle of the as-made textile could reach 2145 ± 122 S/cm and 161.5 ± 2.1°, respectively. On the basis of such excellent conductivity, the electromagnetic interference (EMI) shielding function is excavated and the average shielding efficiency (SE) reaches about 87.56 dB within frequencies of 8.2-12.4 GHz. Furthermore, due to its high elasticity and low modulus, the textile can serve as a wearable strain sensor for motion detection, health monitoring, and underwater message transmission. This work provides a novel route to fabricate high-performance hydrophobic e-textiles, in which the encapsulation strategy could be referenced for the further development of conductive textiles.

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