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1.
Nature ; 602(7897): 496-502, 2022 02.
Artigo em Inglês | MEDLINE | ID: mdl-35110732

RESUMO

Gasdermins, a family of five pore-forming proteins (GSDMA-GSDME) in humans expressed predominantly in the skin, mucosa and immune sentinel cells, are key executioners of inflammatory cell death (pyroptosis), which recruits immune cells to infection sites and promotes protective immunity1,2. Pore formation is triggered by gasdermin cleavage1,2. Although the proteases that activate GSDMB, C, D and E have been identified, how GSDMA-the dominant gasdermin in the skin-is activated, remains unknown. Streptococcus pyogenes, also known as group A Streptococcus (GAS), is a major skin pathogen that causes substantial morbidity and mortality worldwide3. Here we show that the GAS cysteine protease SpeB virulence factor triggers keratinocyte pyroptosis by cleaving GSDMA after Gln246, unleashing an active N-terminal fragment that triggers pyroptosis. Gsdma1 genetic deficiency blunts mouse immune responses to GAS, resulting in uncontrolled bacterial dissemination and death. GSDMA acts as both a sensor and substrate of GAS SpeB and as an effector to trigger pyroptosis, adding a simple one-molecule mechanism for host recognition and control of virulence of a dangerous microbial pathogen.


Assuntos
Exotoxinas , Piroptose , Animais , Proteínas de Bactérias/metabolismo , Exotoxinas/genética , Exotoxinas/metabolismo , Camundongos , Streptococcus pyogenes
2.
Proc Natl Acad Sci U S A ; 121(25): e2400546121, 2024 Jun 18.
Artigo em Inglês | MEDLINE | ID: mdl-38857407

RESUMO

Reduction of carbon dioxide (CO2) by renewable electricity to produce multicarbon chemicals, such as ethylene (C2H4), continues to be a challenge because of insufficient Faradaic efficiency, low production rates, and complex mechanistic pathways. Here, we report that the rate-determining steps (RDS) on common copper (Cu) surfaces diverge in CO2 electroreduction, leading to distinct catalytic performances. Through a combination of experimental and computational studies, we reveal that C─C bond-making is the RDS on Cu(100), whereas the protonation of *CO with adsorbed water becomes rate-limiting on Cu(111) with a higher energy barrier. On an oxide-derived Cu(100)-dominant Cu catalyst, we reach a high C2H4 Faradaic efficiency of 72%, partial current density of 359 mA cm-2, and long-term stability exceeding 100 h at 500 mA cm-2, greatly outperforming its Cu(111)-rich counterpart. We further demonstrate constant C2H4 selectivity of >60% over 70 h in a membrane electrode assembly electrolyzer with a full-cell energy efficiency of 23.4%.

3.
Proc Natl Acad Sci U S A ; 120(31): e2306399120, 2023 08.
Artigo em Inglês | MEDLINE | ID: mdl-37487070

RESUMO

Toll-like receptor 4 (TLR4) sensing of lipopolysaccharide (LPS), the most potent pathogen-associated molecular pattern of gram-negative bacteria, activates NF-κB and Irf3, which induces inflammatory cytokines and interferons that trigger an intense inflammatory response, which is critical for host defense but can also cause serious inflammatory pathology, including sepsis. Although TLR4 inhibition is an attractive therapeutic approach for suppressing overexuberant inflammatory signaling, previously identified TLR4 antagonists have not shown any clinical benefit. Here, we identify disulfiram (DSF), an FDA-approved drug for alcoholism, as a specific inhibitor of TLR4-mediated inflammatory signaling. TLR4 cell surface expression, LPS sensing, dimerization and signaling depend on TLR4 binding to MD-2. DSF and other cysteine-reactive drugs, previously shown to block LPS-triggered inflammatory cell death (pyroptosis), inhibit TLR4 signaling by covalently modifying Cys133 of MD-2, a key conserved residue that mediates TLR4 sensing and signaling. DSF blocks LPS-triggered inflammatory cytokine, chemokine, and interferon production by macrophages in vitro. In the aggressive N-methyl-4-phenyl-1,2,3,6-tetrahydropyridine mouse model of Parkinson's disease (PD) in which TLR4 plays an important role, DSF markedly suppresses neuroinflammation and dopaminergic neuron loss, and restores motor function. Our findings identify a role for DSF in curbing TLR4-mediated inflammation and suggest that DSF and other drugs that target MD-2 might be useful for treating PD and other diseases in which inflammation contributes importantly to pathogenesis.


Assuntos
Alcoolismo , Dissulfiram , Animais , Camundongos , Receptor 4 Toll-Like , Lipopolissacarídeos , Transdução de Sinais , Citocinas
4.
Proc Natl Acad Sci U S A ; 120(51): e2312876120, 2023 Dec 19.
Artigo em Inglês | MEDLINE | ID: mdl-38085783

RESUMO

Electrochemical synthesis of valuable chemicals and feedstocks through carbon dioxide (CO2) reduction in acidic electrolytes can surmount the considerable CO2 loss in alkaline and neutral conditions. However, achieving high productivity, while operating steadily in acidic electrolytes, remains a big challenge owing to the severe competing hydrogen evolution reaction. Here, we show that vertically grown bismuth nanosheets on a gas-diffusion layer can create numerous cavities as electrolyte reservoirs, which confine in situ-generated hydroxide and potassium ions and limit inward proton diffusion, producing locally alkaline environments. Based on this design, we achieve formic acid Faradaic efficiency of 96.3% and partial current density of 471 mA cm-2 at pH 2. When operated in a slim continuous-flow electrolyzer, the system exhibits a full-cell formic acid energy efficiency of 40% and a single pass carbon efficiency of 79% and performs steadily over 50 h. We further demonstrate the production of pure formic acid aqueous solution with a concentration of 4.2 weight %.

5.
J Am Chem Soc ; 2024 Jul 16.
Artigo em Inglês | MEDLINE | ID: mdl-39011931

RESUMO

Scarce and expensive iridium oxide is still the cornerstone catalyst of polymer-electrolyte membrane electrolyzers for green hydrogen production because of its exceptional stability under industrially relevant oxygen evolution reaction (OER) conditions. Earth-abundant transition metal oxides used for this task, however, show poor long-term stability. We demonstrate here the use of nitrogen-doped cobalt oxide as an effective iridium substitute. The catalyst exhibits a low overpotential of 240 mV at 10 mA cm-2 and negligible activity decay after 1000 h of operation in an alkaline electrolyte. Incorporation of nitrogen dopants not only triggers the OER mechanism switched from the traditional adsorbate evolution route to the lattice oxygen oxidation route but also achieves oxygen nonbonding (ONB) states as electron donors, thereby preventing structural destabilization. In a practical anion-exchange membrane water electrolyzer, this catalyst at anode delivers a current density of 1000 mA cm-2 at 1.78 V and an electrical efficiency of 47.8 kW-hours per kilogram hydrogen.

6.
Small ; 20(16): e2306914, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38041488

RESUMO

Electrocatalysts with high activity and durability for acidic oxygen evolution reaction (OER) play a crucial role in achieving cost-effective hydrogen production via proton exchange membrane water electrolysis. A novel electrocatalyst, Te-doped RuO2 (Te-RuO2) nanotubes, synthesized using a template-directed process, which significantly enhances the OER performance in acidic media is reported. The Te-RuO2 nanotubes exhibit remarkable OER activity in acidic media, requiring an overpotential of only 171 mV to achieve an anodic current density of 10 mA cm-2. Furthermore, they maintain stable chronopotentiometric performance under 10 mA cm-2 in acidic media for up to 50 h. Based on the experimental results and density functional calculations, this significant improvement in OER performance to the synergistic effect of large specific surface area and modulated electronic structure resulting from the doping of Te cations is attributed.

7.
Acc Chem Res ; 56(12): 1445-1457, 2023 Jun 20.
Artigo em Inglês | MEDLINE | ID: mdl-37170082

RESUMO

ConspectusLow-temperature ion-exchange membrane hydrogen fuel cells, as zero-emission power sources, can largely preserve the merits of gasoline engines, including rapid fueling, extended cruising range, and low maintenance cost. To enable the widespread prevalence of fuel-cell automobiles, the U.S. Department of Energy (DOE) has set a long-term fuel-cell system cost target of US$30 kW-1. Over past decades, proton-exchange membrane fuel cell (PEMFC) technology has developed rapidly, resulting in the first commercial sales of fuel-cell-powered vehicles. Although there has been great success, the mass market penetration of PEMFCs is currently hindered by the excessive reliance on expensive platinum group metal (PGM) catalysts. Anion-exchange membrane fuel cells (AEMFCs), because of the alkaline environment that permits the use of PGM-free catalysts, have become an alternative technology with inherent long-term cost advantages. Thus far, significant progress has been made in the exploration of PGM-free catalysts for the oxygen reduction reaction at the AEMFC cathode, some of which have shown intrinsic catalytic properties comparable to PGM catalysts. However, the development of PGM-free catalysts for the anodic hydrogen oxidation reaction (HOR) has lagged behind, presumably owing to its sluggish kinetics in alkali. In alkaline media, the HOR kinetics is about 2 orders of magnitude slower than that in acid, which demands higher PGM loadings to reach similar fuel-cell performance in PEMFCs. Since Raney nickel (Ni) was explored for alkaline HOR catalysis in 1960s, research on Ni-based HOR catalysts has begun and now is flourishing, primarily thanks to their favorable adsorption energies of key HOR intermediates (e.g., Ni-Had and Ni-OHad). At present, a number of strategies have been developed to improve HOR performances of Ni-based materials, such as alloying, Ni nitridation, and alloy amorphization, which yield cost-effective HOR catalysts that rival or even exceed the activity and stability of PGM counterparts.In this Account, we describe our recent research endeavors toward the development of efficient Ni-based HOR catalysts for practical AEMFC anodes. First, we briefly highlight the important merits of AEMFC technology and why Ni-based materials are appealing for alkaline HOR catalysis. Critical innovations in the design of Ni-based nanostructured and bulky catalysts were then discussed, showing their great promise to catalyze alkaline HOR that traditionally relied on PGMs. To demonstrate utility, performances of the elaborately designed Ni-based catalysts under realistic fuel-cell conditions were examined, along with an initial effort to develop a CO-tolerant AEMFC anode. We conclude by outlining future research directions that allow access to next-generation PGM-free HOR catalysts for advanced AEMFCs.

8.
Opt Express ; 32(3): 4537-4552, 2024 Jan 29.
Artigo em Inglês | MEDLINE | ID: mdl-38297653

RESUMO

In this paper, we propose and demonstrate a 0.5-bit/s/Hz fine-grained adaptive orthogonal frequency division multiplexing (OFDM) modulation scheme for bandlimited underwater visible light communication (UVLC) systems. Particularly, integer spectral efficiency is obtained by conventional OFDM with quadrature amplitude modulation (QAM) constellations, while fractional spectral efficiency is obtained by two newly proposed dual-frame OFDM designs. More specifically, OFDM with dual-frame binary phase-shift keying (DF-BPSK) is designed to achieve a spectral efficiency of 0.5 bit/s/Hz, while OFDM with dual-frame dual-mode index modulation (DF-DMIM) is designed to realize the spectral efficiencies of 0.5+n bits/s/Hz with n being a positive integer (i.e., n = 1, 2, …). The feasibility and superiority of the proposed 0.5-bit/s/Hz fine-grained adaptive OFDM modulation scheme in bandlimited UVLC systems are successfully verified by simulations and proof-of-concept experiments. Experimental results demonstrate that a significant achievable rate gain of 18.6 Mbps can be achieved by the proposed 0.5-bit/s/Hz fine-grained adaptive OFDM modulation in comparison to the traditional 1-bit/s/Hz granularity adaptive OFDM scheme, which corresponds to a rate improvement of 22.1%.

9.
Opt Lett ; 49(5): 1221-1224, 2024 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-38426978

RESUMO

This paper reports an optical strain sensor that integrates a self-powered mechanoluminescent (ML) elastic fiber with a flexible circuit. The inclusion of an alumina nanoparticle as the additive results in seven-fold enhancement of ML intensity while maintaining flexibility of 120% strain. The sensor facilitates the detection of strain and stretching speed. It attains a sensitivity of 0.0022 lx/(1% strain) and a resolution of 0.2% strain, respectively. We have successfully applied it to detect bending motions of the finger, wrist, and elbow. This wearable strain sensor holds promise for diverse applications in wearable technology.

10.
Cell Mol Biol (Noisy-le-grand) ; 70(4): 77-84, 2024 Apr 28.
Artigo em Inglês | MEDLINE | ID: mdl-38678623

RESUMO

This study aimed to determine lncRNA SNHG14 and miR-206 in Thyroid Cancer ( TC) and to explore the related mechanisms. Sixty-four samples of thyroid tissue were collected from patients with TC. TC cell lines and a normal human thyroid cell line (HTori-3) were bought. lncRNA SNHG14-siRNA (si-lncRNA SNHG14), lncRNA SNHG14-shRNA (sh-lncRNA SNHG14), blank plasmid (siRNA-NC), miR-206-inhibitor, miR-206-mimics were transfected into BHT101 and Ocut-2C cells. qRT-PCR quantified the expression of lncRNA SNHG14 and miR-206, and the expression of vimentin, Snail, N-cadherin, Slug, E-cadherin and ZO-1 proteins were identified via WB. MTT assay, flow cytometry, and Transwell were employed to determine cellular proliferation, apoptosis, and invasion, separately. The high expression of lncRNA SNHG14 and low expression of miR-206 were exhibited in patients with TC. lncRNA SNHG14 and miR-206 were related to lymph node metastases, TNM staging, as well as differentiation of TC. Silencing lncRNA SNHG14 and over-expressing miR-206 inhibited cell EMT, proliferation, and invasion, but accelerated apoptosis. WB demonstrated that silencing lncRNA SNHG14 and over-expressing miR-206 suppressed the expression of Akt, p-ERK1/2, p-p38, p-4EBP1, p-Akt, PI3K, vimentin, Snail, N-cadherin, and Slugn, as well as up-regulated the expression of E-cadherin and ZO-1. Rescue experiment showed that after BHT101 and Ocut-2C cells were transfected with either sh-lncRNA SNHG14+miR-206-mimics or si-lncRNA SNHG14+miR-206-inhibitor, the cellular proliferative, invasive, and apoptotic activities weren't different from those transfected with siRNA-NC. Suppression of lncRNA SNHG14 up-regulates miR-206 and affects EMT, as well as proliferative, invasive, and apoptotic activities of cells, which may become an underlying treatment target for TC.


Assuntos
Regulação Neoplásica da Expressão Gênica , MicroRNAs , RNA Longo não Codificante , Neoplasias da Glândula Tireoide , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Apoptose/genética , Linhagem Celular Tumoral , Movimento Celular , Proliferação de Células , Transição Epitelial-Mesenquimal , Metástase Linfática/genética , MicroRNAs/genética , MicroRNAs/metabolismo , Invasividade Neoplásica/genética , RNA Longo não Codificante/genética , RNA Longo não Codificante/metabolismo , Transdução de Sinais/genética , Neoplasias da Glândula Tireoide/genética , Neoplasias da Glândula Tireoide/patologia , Neoplasias da Glândula Tireoide/metabolismo
11.
Phytopathology ; 114(5): 930-954, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38408117

RESUMO

Sustainable production of pome fruit crops is dependent upon having virus-free planting materials. The production and distribution of plants derived from virus- and viroid-negative sources is necessary not only to control pome fruit viral diseases but also for sustainable breeding activities, as well as the safe movement of plant materials across borders. With variable success rates, different in vitro-based techniques, including shoot tip culture, micrografting, thermotherapy, chemotherapy, and shoot tip cryotherapy, have been employed to eliminate viruses from pome fruits. Higher pathogen eradication efficiencies have been achieved by combining two or more of these techniques. An accurate diagnosis that confirms complete viral elimination is crucial for developing effective management strategies. In recent years, considerable efforts have resulted in new reliable and efficient virus detection methods. This comprehensive review documents the development and recent advances in biotechnological methods that produce healthy pome fruit plants. [Formula: see text] Copyright © 2024 The Author(s). This is an open access article distributed under the CC BY-NC-ND 4.0 International license.


Assuntos
Produtos Agrícolas , Frutas , Doenças das Plantas , Viroides , Doenças das Plantas/virologia , Doenças das Plantas/prevenção & controle , Frutas/virologia , Produtos Agrícolas/virologia , Viroides/genética , Viroides/fisiologia , Vírus de Plantas/fisiologia , Biotecnologia/métodos , Prunus domestica/virologia
12.
BMC Geriatr ; 24(1): 440, 2024 May 20.
Artigo em Inglês | MEDLINE | ID: mdl-38769502

RESUMO

BACKGROUND: The World Health Organization (WHO) published the Integrated Care for Older People (ICOPE) framework to help healthcare providers cope with the population aging crisis. However, the relevant evidence on the demands of older people and the compensatory capacity of the environment is limited. This study reports for the first time the level of the ICOPE demand in Western China that includes the impact of geographic accessibility of medical resources (GAMR) on ICOPE demand and the potential mechanism of health status. METHODS: A cross-sectional questionnaire survey was conducted among 1200 adults aged 60 years and older selected through multi-stage stratified cluster sampling to obtain relevant data, including ICOPE demand, health status, and GAMR. Propensity score matching (PSM) was used to analyze the impact of GAMR on ICOPE demand among older people and those with different health statuses. RESULTS: Among the prospective research participants, 1043 were eligible for the study. The mean score of ICOPE demand among all participants was 3.68 (standard deviation [SD] = 0.78). After adjusting for covariates between high and low GAMR groups (1:1 match), ICOPE demand was significantly higher in the low GAMR group than in the high GAMR group (average treatment effect on the treated [ATT] = 0.270, p < 0.05). For both good and poor self-rated health status, the ICOPE demand of the low GAMR group was significantly higher than that in the high GAMR group (ATT = 0.345, p < 0.05; ATT = 0.190, p < 0.05). For chronic diseases, the ICOPE demand of older people with multimorbidity in the low GAMR group was significantly higher than that in the high GAMR group (ATT = 0.318, p < 0.01). CONCLUSIONS: The older population in Western China has a relatively high demand for ICOPE. Low GAMR is a key factor in ICOPE demand growth in this region. It accelerates demand release for both older people with multimorbidity and self-perceptions of health.


Assuntos
Prestação Integrada de Cuidados de Saúde , Acessibilidade aos Serviços de Saúde , Nível de Saúde , Humanos , Estudos Transversais , Idoso , China/epidemiologia , Masculino , Feminino , Pessoa de Meia-Idade , Necessidades e Demandas de Serviços de Saúde/tendências , Idoso de 80 Anos ou mais , Inquéritos e Questionários , Recursos em Saúde , Serviços de Saúde para Idosos , Estudos Prospectivos
13.
Chem Soc Rev ; 52(13): 4343-4380, 2023 Jul 03.
Artigo em Inglês | MEDLINE | ID: mdl-37318005

RESUMO

The electrocatalytic carbon dioxide reduction reaction (CO2RR) presents a sustainable route to convert renewable electricity to value-added fuels and feedstocks in the form of chemical energy. However, the selectivity and rate of conversion of CO2 to desirable carbon-based products, especially multicarbon products, remain below the requirement for its implementation at the commercial scale, which primarily originates from inadequate reactants and intermediates near catalytic surfaces during the CO2RR. The enrichment of reactants and intermediates provides one of the coping guidelines to improve CO2RR performance by accelerating the reaction rate and improving product selectivity. Herein, we discuss strategies to achieve the enrichment of reactants and intermediates through catalyst design, local microenvironment modulation, electrolyte regulation, and electrolyzer optimization. The structure and properties of CO2 are first presented, showing the necessity and feasibility of enriching reactants and intermediates. Next, the influence of the enrichment effect on CO2 electrolysis, i.e., accelerating the reaction rate and improving product selectivity, are comprehensively discussed. Then, catalyst design from micrometer scale to atom scale, including wettability and morphology regulation, surface modification, and tandem structure construction, as well as surface atom engineering, is highlighted to implement the enrichment of reactants and intermediates. Catalyst restructuring during the CO2RR process and its impact on the enrichment of intermediates and reactants are also discussed. Subsequently, enriching CO2 reactants and intermediates by modulating the local microenvironment to achieve high carbon utilization for the CO2RR to produce multicarbon products is reviewed. After that, insights into enriching reactants and intermediates through electrolyte regulation are provided by investigating various electrolytes, including aqueous solutions, organic solvents, and ionic liquids. Additionally, the key role of electrolyzer optimization in promoting the enrichment effect is considered. We end the review by outlining the remaining technological challenges and providing feasible suggestions aimed at directing the future employment of enrichment strategies to propel the practical implementation of CO2 electrolysis technology.

14.
Nano Lett ; 23(1): 107-115, 2023 01 11.
Artigo em Inglês | MEDLINE | ID: mdl-36541945

RESUMO

In comparison to the well-developed proton-exchange-membrane fuel cells, anion-exchange-membrane fuel cells (AEMFCs) permit adoption of platinum-group-metal (PGM)-free catalysts due to the alkaline environment, giving a substantial cost reduction. However, previous AEMFCs have generally shown unsatisfactory performances due to the lack of effective PGM-free catalysts that can endure harsh fuel cell conditions. Here we report a plasma-assisted synthesis of high-quality nickel nitride (Ni3N) and zirconium nitride (ZrN) employing dinitrogen as the nitrogen resource, exhibiting exceptional catalytic performances toward hydrogen oxidation and oxygen reduction in an alkaline enviroment, respectively. A PGM-free AEMFC assembled by using Ni3N as the anode and ZrN as the cathode delivers power densities of 256 mW cm-2 under an H2-O2 condition and 151 mW cm-2 under an H2-air condition. Furthermore, the fuel cell shows no evidence of degradation after 25 h of operation. This work creates opportunities for developing high-performance and durable AEMFCs based on metal nitrides.


Assuntos
Níquel , Platina , Membranas , Membrana Celular , Ânions , Prótons
15.
Psychogeriatrics ; 24(3): 529-541, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38351289

RESUMO

BACKGROUND: The purpose of this research was to stratify the level of frailty to examine the risk factors associated with reversible cognitive frailty (RCF) and potentially reversible cognitive frailty (PRCF) in nursing homes to provide a basis for hierarchical management in different stages of frailty. METHODS: The study was a cross-sectional study conducted from September to November 2022; 504 people were selected by stratified random sampling after convenience selection from the Home for the Aged Guangzhou. The structured questionnaire survey was conducted through face-to-face interviews using the general data questionnaire, Fried Frailty Phenotype, Montreal Cognitive Assessment Scale. RESULTS: In total, 452 individuals were included for analysis. A total of 229 cases (50.7%) were PRCF, 70 (15.5%) were RCF. Multivariate logistic regression analysis showed that in pre-frailty, the Geriatric Depression Scale (GDS-15) score (odds ratio (OR) 1.802; 95% CI 1.308-2.483), Instrumental Activities of Daily Living Scale (IADL) score (0.352; 0.135-0.918) and energy (0.288; 0.110-0.755) were influencing factors of RCF. GDS-15 score (1.805; 1.320-2.468), IADL score (0.268; 0.105-0.682), energy (0.377; 0.150-0.947), lack of intellectual activity (6.118; 1.067-35.070), admission time(>3 years) (9.969; 1.893-52.495) and low education (3.465; 1.211-9.912) were influencing factors of PRCF. However, RCF with frailty was associated with the Short-Form Mini-Nutritional Assessment (MNA-SF) score (0.301; 0.123-0.739) and low education time (0 ~ 12 years) (0.021; 0.001-0.826). PRCF with frailty was associated with age (1.327; 1.081-1.629) and weekly exercise time (0.987; 0.979-0.995). CONCLUSIONS: The prevalence of RCF and PRCF was high among pre-frail and frail older adults in nursing homes. Different levels of frailty had different influencing factors for RCF and PRCF. Depression, daily living ability, energy, intellectual activity, admission time, education level, nutrition status, age and exercise time were associated with RCF and PRCF. Hierarchical management and intervention should be implemented for different stages of frailty to prevent or delay the progression of cognitive frailty.


Assuntos
Atividades Cotidianas , Disfunção Cognitiva , Idoso Fragilizado , Fragilidade , Avaliação Geriátrica , Instituição de Longa Permanência para Idosos , Casas de Saúde , Humanos , Casas de Saúde/estatística & dados numéricos , Masculino , Feminino , Idoso , Idoso Fragilizado/estatística & dados numéricos , Idoso Fragilizado/psicologia , Estudos Transversais , Fatores de Risco , Prevalência , Avaliação Geriátrica/métodos , Fragilidade/epidemiologia , Fragilidade/psicologia , Idoso de 80 Anos ou mais , Disfunção Cognitiva/epidemiologia , China/epidemiologia , Instituição de Longa Permanência para Idosos/estatística & dados numéricos , Inquéritos e Questionários
16.
Angew Chem Int Ed Engl ; : e202407613, 2024 May 12.
Artigo em Inglês | MEDLINE | ID: mdl-38736299

RESUMO

Anion-exchange membrane fuel cells provide the possibility to use platinum group metal-free catalysts, but the anodic hydrogen oxidation reaction (HOR) suffers from sluggish kinetics and its source is still debated. Here, over nickel-tungsten (Ni-W) alloy catalysts, we show that the Ni : W ratio greatly governs the HOR performance in alkaline electrolyte. Experimental and theoretical studies unravel that alloying with W can tune the unpaired electrons in Ni, tailoring the potential of zero charge and the catalytic surface to favor hydroxyl adsorption (OHad). The OHad species coordinately interact with potassium (K+) ions, which break the K+ solvation sheath to leave free water molecules, yielding an improved connectivity of hydrogen-bond networks. Consequently, the optimal Ni17W3 alloy exhibits alkaline HOR activity superior to the state-of-the-art platinum on carbon (Pt/C) catalyst and operates steadily with negligible decay after 10,000 cycles. Our findings offer new understandings of alloyed HOR catalysts and will guide rational design of next-generation catalysts for fuel cells.

17.
J Am Chem Soc ; 145(31): 17485-17494, 2023 Aug 09.
Artigo em Inglês | MEDLINE | ID: mdl-37526148

RESUMO

Converting hydrogen chemical energy into electrical energy by fuel cells offers high efficiencies and environmental advantages, but ultrapure hydrogen (over 99.97%) is required; otherwise, the electrode catalysts, typically platinum on carbon (Pt/C), will be poisoned by impurity gases such as ammonia (NH3). Here we demonstrate remarkable NH3 resistivity over a nickel-molybdenum alloy (MoNi4) modulated by chromium (Cr) dopants. The resultant Cr-MoNi4 exhibits high activity toward alkaline hydrogen oxidation and can undergo 10,000 cycles without apparent activity decay in the presence of 2 ppm of NH3. Furthermore, a fuel cell assembled with this catalyst retains 95% of the initial peak power density even when NH3 (10 ppm)/H2 was fed, whereas the power output reduces to 61% of the initial value for the Pt/C catalyst. Experimental and theoretical studies reveal that the Cr modifier not only creates electron-rich states that restrain lone-pair electron donation but also downshifts the d-band center to suppress d-electron back-donation, synergistically weakening NH3 adsorption.

18.
J Am Chem Soc ; 2023 Apr 06.
Artigo em Inglês | MEDLINE | ID: mdl-37021910

RESUMO

Electrocatalytic carbon dioxide reduction (CO2R) in neutral electrolytes can mitigate the energy and carbon losses caused by carbonate formation but often experiences unsatisfied multicarbon selectivity and reaction rates because of the kinetic limitation to the critical carbon monoxide (CO)-CO coupling step. Here, we describe that a dual-phase copper-based catalyst with abundant Cu(I) sites at the amorphous-nanocrystalline interfaces, which is electrochemically robust in reducing environments, can enhance chloride-specific adsorption and consequently mediate local *CO coverage for improved CO-CO coupling kinetics. Using this catalyst design strategy, we demonstrate efficient multicarbon production from CO2R in a neutral potassium chloride electrolyte (pH ∼6.6) with a high Faradaic efficiency of 81% and a partial current density of 322 milliamperes per square centimeter. This catalyst is stable after 45 h of operation at current densities relevant to commercial CO2 electrolysis (300 mA per square centimeter).

19.
J Am Chem Soc ; 145(44): 24338-24348, 2023 Nov 08.
Artigo em Inglês | MEDLINE | ID: mdl-37880928

RESUMO

Carbon-carbon coupling electrochemistry on a conventional copper (Cu) catalyst still undergoes low selectivity among many different multicarbon (C2+) chemicals, posing a grand challenge to achieve a single C2+ product. Here, we demonstrate a laser irradiation synthesis of a gerhardtite mineral, Cu2(OH)3NO3, as a catalyst precursor to make a Cu catalyst with abundant stacking faults under reducing conditions. Such structural perturbation modulates electronic microenvironments of Cu, leading to improved d-electron back-donation to the antibonding orbital of *CO intermediates and thus strengthening *CO adsorption. With increased *CO coverage on the defect-rich Cu, we report an acetate selectivity of 56 ± 2% (compared to 31 ± 1% for conventional Cu) and a partial current density of 222 ± 7 mA per square centimeter in CO electroreduction. When run at 400 mA per square centimeter for 40 h in a flow reactor, this catalyst produces 68.3 mmol of acetate throughout. This work highlights the value of a Cu-containing mineral phase in accessing suitable structures for improved selectivity to a single desired C2+ product.

20.
Opt Express ; 31(3): 4783-4802, 2023 Jan 30.
Artigo em Inglês | MEDLINE | ID: mdl-36785437

RESUMO

In this work, authors have developed a portable, sensitive, and quick-response fiber optic sensor that is capable of detection of Aflatoxins B1 (AFB1) quantitatively and qualitatively. Using multi-mode fiber (MMF) and multi-core fiber (MCF), the MMF-MCF-MCF-MMF fiber structure based on symmetric transverse offset splicing and waist-expanded taper is fabricated. The evanescent waves are enhanced to form a strong evanescent field by etching the fiber surface with hydrofluoric acid. To successfully excite the localized surface plasmon resonance phenomenon, gold nanoparticles are deposited on the optical fiber probe's surface. Further, to modify the fiber optic probes, Niobium carbide (Nb2CTx) MXene and AFB1 antibodies are functionalized. Nb2CTx MXene is employed to strengthen the biocompatibility of the sensor and increase the specific surface area of the fiber probe, while AFB1 antibody is used to identify AFB1 micro-biomolecules in a specific manner. The reproducibility, reusability, stability, and selectivity of the proposed fiber probe are tested and validated using various concentration of AFB1 solutions. Finally, the linear range, sensitivity, and limit of detection of the sensing probe are determined as 0 - 1000 nM, 11.7 nm/µM, and 26.41 nM, respectively. The sensor offers an indispensable technique, low-cost solution and portability for AFB1-specific detection in agricultural products and their byproducts with its novel optical fiber structure and superior detecting capability. It is also useful for marine species like fish and consequently affecting health of human body.


Assuntos
Aflatoxina B1 , Nanopartículas Metálicas , Humanos , Aflatoxina B1/análise , Ouro/química , Nanopartículas Metálicas/química , Reprodutibilidade dos Testes , Ressonância de Plasmônio de Superfície
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