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1.
Phys Chem Chem Phys ; 2024 Jun 27.
Artigo em Inglês | MEDLINE | ID: mdl-38932574

RESUMO

Exploring efficient and low-cost oxygen reduction and oxygen evolution reaction (ORR/OER) bifunctional catalysts is essential for the development of energy storage and conversion devices. Herein, enlightened by the experimentally synthesized cobalt(II) meso-tetraethynylporphyrins (Co-TEP) molecule, we designed a novel 2D covalent organic framework (COF), namely a 2D Co-TEP monolayer, by dimensional expansion. The 2D Co-TEP monolayer, with Co atoms distributed separately and stabilized by uniform pyrrolic-N coordination, features metal-nitrogen-carbon single-atom catalyst activity and shows tunable catalytic activity for the electrochemical ORR/OER by axial ligand (O, OH, Cl, CN, CH3, NO, F) modulation. By means of the state-of-the-art constant-potential first-principles computations and microkinetic simulations, we demonstrated that 2D Co-TEP-CN exhibits good ORR/OER performance in both acidic and alkaline conditions. The difference between the onset-potential for the OER and the half-wave potential for the ORR is only 0.85 V at pH = 1, smaller than that of Pt/IrO2 electrocatalysts. The good electrocatalytic performance is maintained by replacing the center metal atoms with Mn, Fe and/or Ni. Our investigation highlights the role of the pyrrolic-N coordination and the ligands in improving the catalytic activity of 2D COFs and provides new insights into the rational design of efficient bifunctional ORR/OER catalysts.

2.
Proc Natl Acad Sci U S A ; 118(51)2021 12 21.
Artigo em Inglês | MEDLINE | ID: mdl-34916292

RESUMO

Microtubules are dynamic cytoskeletal polymers that spontaneously switch between phases of growth and shrinkage. The probability of transitioning from growth to shrinkage, termed catastrophe, increases with microtubule age, but the underlying mechanisms are poorly understood. Here, we set out to test whether microtubule lattice defects formed during polymerization can affect growth at the plus end. To generate microtubules with lattice defects, we used microtubule-stabilizing agents that promote formation of polymers with different protofilament numbers. By employing different agents during nucleation of stable microtubule seeds and the subsequent polymerization phase, we could reproducibly induce switches in protofilament number and induce stable lattice defects. Such drug-induced defects led to frequent catastrophes, which were not observed when microtubules were grown in the same conditions but without a protofilament number mismatch. Microtubule severing at the site of the defect was sufficient to suppress catastrophes. We conclude that structural defects within the microtubule lattice can exert effects that can propagate over long distances and affect the dynamic state of the microtubule end.


Assuntos
Microtúbulos/metabolismo , Moduladores de Tubulina/metabolismo , Fenômenos Biológicos , Proteínas Associadas aos Microtúbulos/química , Proteínas Associadas aos Microtúbulos/metabolismo , Microtúbulos/química , Microtúbulos/ultraestrutura , Paclitaxel/metabolismo , Polimerização , Ligação Proteica , Tubulina (Proteína)/química , Tubulina (Proteína)/metabolismo , Moduladores de Tubulina/química
3.
Angew Chem Int Ed Engl ; 63(7): e202315157, 2024 Feb 12.
Artigo em Inglês | MEDLINE | ID: mdl-38143245

RESUMO

Methanol steam reforming (MSR) provides an alternative way for efficient production and safe transportation of hydrogen but requires harsh conditions and complicated purification processes. In this work, an efficient electrochemical-assisted MSR reaction for pure H2 production at lower temperature (~140 °C) is developed by coupling the electrocatalysis reaction into the MSR in a polymer electrolyte membrane electrolysis reactor. By electrochemically assisted, the two critical steps including the methanol dehydrogenation and water-gas shift reaction are accelerated, which is attributed to decreasing the methanol dehydrogenation energy and promoting the dissociation of H2 O to OH* by the applied potential. Furthermore, the reduced H2 partial pressure by the hydrogen oxidation and reduction process further promotes MSR. The combination of these advantages not only efficiently decreases the MSR temperature but also achieves the high rate of hydrogen production of 505 mmol H2 g Pt -1 h-1 with exceptionally high H2 selectivity (99 %) at 180 °C and a low voltage (0.4 V), and the productivity is about 30-fold than that of traditional MSR. This study opens up a new avenue to design novel electrolysis cells for hydrogen production.

4.
J Am Chem Soc ; 145(4): 2195-2206, 2023 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-36629383

RESUMO

Copper-based catalysts are widely explored in electrochemical CO2 reduction (CO2RR) because of their ability to convert CO2 into high-value-added multicarbon products. However, the poor stability and low selectivity limit the practical applications of these catalysts. Here, we proposed a simple and efficient asymmetric low-frequency pulsed strategy (ALPS) to significantly enhance the stability and the selectivity of the Cu-dimethylpyrazole complex Cu3(DMPz)3 catalyst in CO2RR. Under traditional potentiostatic conditions, Cu3(DMPz)3 exhibited poor CO2RR performance with the Faradaic efficiency (FE) of 34.5% for C2H4 and FE of 5.9% for CH4 as well as the low stability for less than 1 h. We optimized two distinguished ALPS methods toward CH4 and C2H4, correspondingly. The high selectivities of catalytic product CH4 (FECH4 = 80.3% and above 76.6% within 24 h) and C2H4 (FEC2H4 = 70.7% and above 66.8% within 24 h) can be obtained, respectively. The ultralong stability for 300 h (FECH4 > 60%) and 145 h (FEC2H4 > 50%) was also recorded with the ALPS method. Microscopy (HRTEM, SAED, and HAADF) measurements revealed that the ALPS method in situ generated and stabilized extremely dispersive and active Cu-based clusters (∼2.7 nm) from Cu3(DMPz)3. Meanwhile, ex situ spectroscopies (XPS, AES, and XANES) and in situ XANES indicated that this ALPS method modulated the Cu oxidation states, such as Cu(0 and I) with C2H4 selectivity and Cu(I and II) with CH4 selectivity. The mechanism under the ALPS methods was explored by in situ ATR-FTIR, in situ Raman, and DFT computation. The ALPS methods provide a new opportunity to boost the selectivity and stability of CO2RR.

5.
Angew Chem Int Ed Engl ; 62(49): e202313954, 2023 Dec 04.
Artigo em Inglês | MEDLINE | ID: mdl-37867149

RESUMO

Due to the robust oxidation conditions in strong acid oxygen evolution reaction (OER), developing an OER electrocatalyst with high efficiency remains challenging in polymer electrolyte membrane (PEM) water electrolyzer. Recent theoretical research suggested that reducing the coordination number of Ir-O is feasible to reduce the energy barrier of the rate-determination step, potentially accelerating the OER. Inspired by this, we experimentally verified the Ir-O coordination number's role at model catalysts, then synthesized low-coordinated IrOx nanoparticles toward a durable PEM water electrolyzer. We first conducted model studies on commercial rutile-IrO2 using plasma-based defect engineering. The combined in situ X-ray absorption spectroscopy (XAS) analysis and computational studies clarify why the decreased coordination numbers increase catalytic activity. Next, under the model studies' guidelines, we explored a low-coordinated Ir-based catalyst with a lower overpotential of 231 mV@10 mA cm-2 accompanied by long durability (100 h) in an acidic OER. Finally, the assembled PEM water electrolyzer delivers a low voltage (1.72 V@1 A cm-2 ) as well as excellent stability exceeding 1200 h (@1 A cm-2 ) without obvious decay. This work provides a unique insight into the role of coordination numbers, paving the way for designing Ir-based catalysts for PEM water electrolyzers.

6.
Small ; 18(44): e2204015, 2022 11.
Artigo em Inglês | MEDLINE | ID: mdl-36123142

RESUMO

The catalytic activity and selectivity of single-atom sites catalysts is strongly dependent on the supports structure and central metal coordination environment. However, the further optimization of electronic configuration to improve the catalytic performance is usually hampered by the strong coordination effect between the support and metal atoms. Herein, it is discovered that enzyme-mimicking catalytic performance can be enhanced at the fixed coordination single-atom Fe sites by regulating the Fe spin states. The X-ray absorption fine structure, 57 Fe Mössbauer spectrum, and temperature-dependent magnetization measurements reveal that the spin states of Fe in single FeN4  sites can be well manipulated via changing the pyrolysis temperature. The intermediate-spin Fe sites catalyst (t2g 4 eg 1) demonstrates a much higher peroxidase-mimicking activity in comparison with high-spin structure (t2g 3 eg 2). More importantly, the based enzymes system realizes sensitive detection of H2 O2  and glucose by colorimetric sensors with high catalytic activity and selectivity. Furthermore, theoretical calculations unveil that the intermediate-spin FeN4  promotes the OH* desorption process, thus greatly reducing the reaction energy barrier. These findings provide a route to design highly active enzyme-mimicking catalysts and an engineering approach for regulating spin states of metal sites to enhance their catalytic performance.


Assuntos
Ferro , Peroxidase , Ferro/química , Oxirredução , Catálise , Oxirredutases , Peroxidases
7.
Angew Chem Int Ed Engl ; 61(12): e202115636, 2022 03 14.
Artigo em Inglês | MEDLINE | ID: mdl-34939730

RESUMO

Integrating biomass upgrading and hydrogen production in an electrocatalytic system is attractive both environmentally and in terms of sustainability. Conventional electrolyser systems coupling anodic biosubstrate electrooxidation with hydrogen evolution reaction usually require electricity input. Herein, we describe the development of an electrocatalytic system for simultaneous biomass upgrading, hydrogen production, and electricity generation. In contrast to conventional furfural electrooxidation, the employed low-potential furfural oxidation enabled the hydrogen atom of the aldehyde group to be released as gaseous hydrogen at the anode at a low potential of approximately 0 VRHE (vs. RHE). The integrated electrocatalytic system could generate electricity of about 2 kWh per cubic meter of hydrogen produced. This study may provide a transformative technology to convert electrocatalytic biomass upgrading and hydrogen production from a process requiring electricity input into a process to generate electricity.


Assuntos
Eletricidade , Furaldeído , Biomassa , Eletrodos , Hidrogênio
8.
J Am Chem Soc ; 143(30): 11317-11324, 2021 Aug 04.
Artigo em Inglês | MEDLINE | ID: mdl-34293258

RESUMO

The development of atomically precise dinuclear heterogeneous catalysts is promising to achieve efficient catalytic performance and is also helpful to the atomic-level understanding on the synergy mechanism under reaction conditions. Here, we report a Ni2(dppm)2Cl3 dinuclear-cluster-derived strategy to a uniform atomically precise Ni2 site, consisting of two Ni1-N4 moieties shared with two nitrogen atoms, anchored on a N-doped carbon. By using operando synchrotron X-ray absorption spectroscopy, we identify the dynamically catalytic dinuclear Ni2 structure under electrochemical CO2 reduction reaction, revealing an oxygen-bridge adsorption on the Ni2-N6 site to form an O-Ni2-N6 structure with enhanced Ni-Ni interaction. Theoretical simulations demonstrate that the key O-Ni2-N6 structure can significantly lower the energy barrier for CO2 activation. As a result, the dinuclear Ni2 catalyst exhibits >94% Faradaic efficiency for efficient carbon monoxide production. This work provides bottom-up target synthesis approaches and evidences the identity of dinuclear sites active toward catalytic reactions.

9.
Cancer Sci ; 112(4): 1402-1416, 2021 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-33529452

RESUMO

Human papillomavirus (HPV) is an important etiological factor of head and neck squamous cell carcinoma (HNSCC). HPV+ HNSCC patients usually have a better prognosis, which probably results from the higher infiltration of B lymphocytes. This study was purposed to detect the infiltration of B lymphocyte subsets and the correlation between B lymphocyte subsets and the prognosis in HPV-related HNSCC. In this study, 124 HPV+ and 513 HPV- HNSCC samples were obtained from the Gene Expression Omnibus (GEO) database and The Cancer Genome Atlas (TCGA) database for transcriptomic analysis. Infiltration of B lymphocytes subsets was detected with 7 HPV+ HNSCC and 13 HPV- HNSCC tissues through immunohistochemistry and immunofluorescence. One HPV- HNSCC sample was detected with single-cell sequencing for chemokine analysis. In the results, the infiltration of plasma cells (CD19+ CD38+ ) and memory B cells (MS4A1+ CD27+ ) was higher in HPV+ HNSCC samples. High infiltration of plasma cells and memory B cells was related to a better prognosis. High density of B lymphocytes was positively correlated with high CXCL13 production mainly from CD4+ T lymphocytes in HNSCC. These results indicated that a high density of plasma cells and memory B cells could predict excellent prognosis. CD4+ T lymphocytes might affect B lymphocytes and their subsets through the CXCL13/CXCR5 axis in HNSCC.


Assuntos
Alphapapillomavirus/imunologia , Linfócitos B/imunologia , Carcinoma de Células Escamosas/imunologia , Neoplasias de Cabeça e Pescoço/imunologia , Carcinoma de Células Escamosas de Cabeça e Pescoço/imunologia , Idoso , Linfócitos T CD4-Positivos/imunologia , Carcinoma de Células Escamosas/virologia , Quimiocina CXCL13/imunologia , Feminino , Neoplasias de Cabeça e Pescoço/virologia , Humanos , Masculino , Pessoa de Meia-Idade , Infecções por Papillomavirus/imunologia , Infecções por Papillomavirus/virologia , Prognóstico , Receptores CXCR5/imunologia , Carcinoma de Células Escamosas de Cabeça e Pescoço/virologia
10.
Nat Mater ; 19(3): 355-365, 2020 03.
Artigo em Inglês | MEDLINE | ID: mdl-31819210

RESUMO

Microtubules are polymers of tubulin dimers, and conformational transitions in the microtubule lattice drive microtubule dynamic instability and affect various aspects of microtubule function. The exact nature of these transitions and their modulation by anticancer drugs such as Taxol and epothilone, which can stabilize microtubules but also perturb their growth, are poorly understood. Here, we directly visualize the action of fluorescent Taxol and epothilone derivatives and show that microtubules can transition to a state that triggers cooperative drug binding to form regions with altered lattice conformation. Such regions emerge at growing microtubule ends that are in a pre-catastrophe state, and inhibit microtubule growth and shortening. Electron microscopy and in vitro dynamics data indicate that taxane accumulation zones represent incomplete tubes that can persist, incorporate tubulin dimers and repeatedly induce microtubule rescues. Thus, taxanes modulate the material properties of microtubules by converting destabilized growing microtubule ends into regions resistant to depolymerization.


Assuntos
Microtúbulos/efeitos dos fármacos , Microtúbulos/metabolismo , Taxoides/farmacologia , Células HeLa , Humanos , Cinética , Tubulina (Proteína)/metabolismo
11.
PLoS Pathog ; 15(10): e1008048, 2019 10.
Artigo em Inglês | MEDLINE | ID: mdl-31600347

RESUMO

Kinesin-8 proteins are microtubule motors that are often involved in regulation of mitotic spindle length and chromosome alignment. They move towards the plus ends of spindle microtubules and regulate the dynamics of these ends due, at least in some species, to their microtubule depolymerization activity. Plasmodium spp. exhibit an atypical endomitotic cell division in which chromosome condensation and spindle dynamics in the different proliferative stages are not well understood. Genome-wide shared orthology analysis of Plasmodium spp. revealed the presence of two kinesin-8 motor proteins, kinesin-8X and kinesin-8B. Here we studied the biochemical properties of kinesin-8X and its role in parasite proliferation. In vitro, kinesin-8X has motility and depolymerization activities like other kinesin-8 motors. To understand the role of Plasmodium kinesin-8X in cell division, we used fluorescence-tagging and live cell imaging to define its location, and gene targeting to analyse its function, during all proliferative stages of the rodent malaria parasite P. berghei life cycle. The results revealed a spatio-temporal involvement of kinesin-8X in spindle dynamics and an association with both mitotic and meiotic spindles and the putative microtubule organising centre (MTOC). Deletion of the kinesin-8X gene revealed a defect in oocyst development, confirmed by ultrastructural studies, suggesting that this protein is required for oocyst development and sporogony. Transcriptome analysis of Δkinesin-8X gametocytes revealed modulated expression of genes involved mainly in microtubule-based processes, chromosome organisation and the regulation of gene expression, supporting a role for kinesin-8X in cell division. Kinesin-8X is thus required for parasite proliferation within the mosquito and for transmission to the vertebrate host.


Assuntos
Cinesinas/metabolismo , Malária/parasitologia , Malária/transmissão , Oocistos/citologia , Plasmodium/fisiologia , Proteínas de Protozoários/metabolismo , Fuso Acromático/fisiologia , Animais , Segregação de Cromossomos , Feminino , Cinesinas/genética , Masculino , Camundongos Endogâmicos BALB C , Microtúbulos/metabolismo , Mitose , Oocistos/fisiologia , Proteínas de Protozoários/genética
12.
Nano Lett ; 20(7): 5482-5489, 2020 Jul 08.
Artigo em Inglês | MEDLINE | ID: mdl-32515969

RESUMO

Single-atom site catalysts (SACs) have aroused enormous attention and brought about new opportunities for many applications. Herein, we report a versatile strategy to rhodium (Rh) SAC by a facile cation exchange reaction. Remarkably, the Rh SAC modified CuO nanowire arrays on copper foam (Rh SAC-CuO NAs/CF) show unprecedented alkaline oxygen evolution reaction (OER) activity with a high current density of 84.5 mA cm-2@1.5 V vs reversible hydrogen electrode (RHE), 9.7 times that of Ir/C/CF. More strikingly, when used as an anode and a cathode for overall water splitting, the Rh SAC-CuO NAs/CF can achieve 10 mA cm-2 at only 1.51 V. Density functional theory calculations reveal that the high OER and HER intrinsic catalytic activities result from moderate adsorption energy of intermediates on Rh SAC. Finally, we demonstrate the general synthesis of different single-atom noble-metal catalysts on CuO NAs (M SAC-CuO NAs/CF, where M = Ru, Ir, Os, and Au).

13.
Zhongguo Zhong Yao Za Zhi ; 46(14): 3705-3711, 2021 Jul.
Artigo em Zh | MEDLINE | ID: mdl-34402295

RESUMO

To observe the effect of Xinfeng Capsules on rheumatoid arthritis (RA) B lymphocytes,inflammatory mediators,FAK/CAPN/PI3K pathway,in order to explore the mechanism of Xinfeng Capsules in improving clinical symptoms of RA.Joint and systemic symptoms of RA patients were observed,and laboratory indicators[hemoglobin (HGB),platelet count (PLT),erythrocyte sedimentation (ESR),immunoglobulin (Ig) G,Ig A,Ig M,rheumatoid factor (RF),anti-cyclic citrulline antibody (CCP-AB),C-reactive protein (CRP)]were detected.ELISA was used to detect serum interleukin (IL)-1ß,IL-10,IL-33,chemokine 5 (CCL5),and vascular endothelial growth factor (VEGF).CD3~-CD19~+B cells were measured by flow cytometry.Western blot was used to detect FAK,p-FAK,CAPN,PI3K protein.The results showed that Xinfeng Capsules could significantly alleviate RA joint and systemic symptoms and improve clinical efficacy.And Xinfeng Capsules could increase HGB,decrease PLT,CCP-AB,CRP,ESR index,upregulate IL-10 expression,and down-regulate IL-1ß,IL-33,CCL5,VEGF,CD3~-CD19~+B cells,FAK,p-FAK,CAPN,PI3K expressions (P<0.01).Based on the above results,Xinfeng Capsules may reduce the expression of CD3~-CD19~+,regulate the balance of inflammatory cytokines and chemokines,inhibit abnormal activation of FAK/CAPN/PI3K pathway,and improve clinical symptoms of RA.


Assuntos
Artrite Reumatoide , Fosfatidilinositol 3-Quinases , Artrite Reumatoide/tratamento farmacológico , Linfócitos B , Cápsulas , Medicamentos de Ervas Chinesas , Humanos , Fator A de Crescimento do Endotélio Vascular
14.
J Proteome Res ; 19(9): 3750-3760, 2020 09 04.
Artigo em Inglês | MEDLINE | ID: mdl-32693607

RESUMO

Unclarified molecular mechanism and lack of practical diagnosis biomarkers hinder the effective treatment of non-small-cell lung cancer. Herein, we performed liquid chromatography-mass spectrometry-based nontargeted metabolomics analysis in 131 patients with their lung tissue pairs to study the metabolic characteristics and disordered metabolic pathways in lung tumor. A total of 339 metabolites were identified in metabolic profiling. Also, 241 differential metabolites were found between lung carcinoma tissues (LCTs) and paired distal noncancerous tissues; amino acids, purine metabolites, fatty acids, phospholipids, and most of lysophospholipids significantly increased in LCTs, while 3-phosphoglyceric acid, phosphoenolpyruvate, 6-phosphogluconate, and citrate decreased. Additionally, pathway enrichment analysis revealed that energy, purine, amino acid, lipid, and glutathione metabolism are markedly disturbed in lung cancer (LCa). Using binary logistic regression, we further defined candidate biomarkers for different subtypes of lung tumor. Xanthine and PC 35:2 were selected as combinational biomarkers for distinguishing benign from malignant lung tumors with a 0.886 area under curve (AUC) value, and creatine, myoinositol and LPE 16:0 were defined as combinational biomarkers for discriminating adenocarcinoma from squamous cell lung carcinoma with a 0.934 AUC value. Overall, metabolic characterization and pathway disturbance demonstrated apparent metabolic reprogramming in LCa. The defined candidate metabolite marker panels are useful for subtyping of lung tumors to assist clinical diagnosis.


Assuntos
Carcinoma Pulmonar de Células não Pequenas , Neoplasias Pulmonares , Biomarcadores , Biomarcadores Tumorais/metabolismo , Carcinoma Pulmonar de Células não Pequenas/diagnóstico , Cromatografia Líquida , Humanos , Neoplasias Pulmonares/diagnóstico , Espectrometria de Massas , Redes e Vias Metabólicas , Metabolômica
15.
Sichuan Da Xue Xue Bao Yi Xue Ban ; 51(2): 207-212, 2020 Mar.
Artigo em Zh | MEDLINE | ID: mdl-32220189

RESUMO

OBJECTIVE: To observe the changes of cardiac function in arthritic rats and the effect of triptolide on it. METHODS: Forty rats were divided in random into normal control (NC) group, model control (MC) group, leflunomide (LEF) group and triptolide (TP) group. Except for the normal group, rats in the other three groups were injected with Freund's complete adjuvant to create arthritic inflammation in the right hind paws, and the interventional drug was administered on the 12th day after the inflammation. By treating for 30 d, the cardiac function of rats was detected by left ventricular catheterization. The expressions of superoxide dismutase (SOD), malondialdehyde (MDA), reacitve oxygen species (ROS), total antioxidation (T-AOC), interleukin-10 (IL-10) and tumor necrosis factor-α (TNF-α) in serum were measured by enzyme-linked immunosorbent assay. The expressions of keap-like protein 1 ( Keap1), muscular aponeurotic fibrosarcom ( maf) and nuclear factor-E2 related factor2 ( Nrf2) mRNAs in cardiac tissue were detected by real-time PCR. The expressions of Keap1, maf and Nrf2 proteins in heart tissues were detected by Western blot. RESULTS: Comparing with the normal group, the heart rate (HR), heart index (HI), left ventricular systolic pressure (LVSP), and left ventricular end-diastolic pressure (LVEDP) of the model group were significantly increased, whereas the maximum change rate of ventricular pressure rise or decline (±dp/dtmax) was significantly decreased ( P<0.01). SOD, MDA, ROS, T-AOC, and TNF-α were all increased, and IL-10 was significantly decreased ( P<0.01). The mRNA and protein expressions of Keap1, maf and Nrf2 in heart tissues were increased ( P<0.01). Comparing with the model group, HR, HI, LVSP, and LVEDP in the triptolide group were significantly decreased, whereas the ±dp/dtmax was significantly increased ( P<0.01). SOD, MDA, T-AOC, ROS, TNF-α decreased while the IL-10 increased ( P<0.05, P<0.01). The expressions of Keap1, maf and Nrf2 mRNAs and proteins in the heart tissues of the triptolide group were decreased ( P<0.01). CONCLUSION: Triptolide could improve cardiac function in arthritic rats, and the mechanism may related to its ability of improving the anti-oxidationin cardiomyocytes, reducing oxidative stress damage, and inhibiting abnormal immune inflammatory response.


Assuntos
Artrite/complicações , Diterpenos/farmacologia , Cardiopatias/tratamento farmacológico , Coração/efeitos dos fármacos , Imunossupressores/farmacologia , Miócitos Cardíacos/efeitos dos fármacos , Fenantrenos/farmacologia , Animais , Compostos de Epóxi/farmacologia , Cardiopatias/complicações , Proteína 1 Associada a ECH Semelhante a Kelch , Miócitos Cardíacos/fisiologia , Fator 2 Relacionado a NF-E2 , Estresse Oxidativo/efeitos dos fármacos , Ratos
16.
Angew Chem Int Ed Engl ; 58(51): 18388-18393, 2019 Dec 16.
Artigo em Inglês | MEDLINE | ID: mdl-31692199

RESUMO

A surface digging effect of supported Ni NPs on an amorphous N-doped carbon is described, during which the surface-loaded Ni NPs would etch and sink into the underneath carbon support to prevent sintering. This process is driven by the strong coordination interaction between the surface Ni atoms and N-rich defects. In the aim of activation of C-H bonds for methane oxidation, those sinking Ni NPs could be further transformed into thermodynamically stable and active metal-defect sites within the as-generated surface holes by simply elevating the temperature. In situ transmission electron microscopy images reveal the sunk Ni NPs dig themselves adaptive surface holes, which would largely prevent the migration of Ni NPs without weakening their accessibility. The reported two-step strategy opens up a new route to manufacture sintering-resistant supported metal catalysts without degrading their catalytic efficiency.

17.
Health Res Policy Syst ; 16(1): 58, 2018 Jul 06.
Artigo em Inglês | MEDLINE | ID: mdl-29980230

RESUMO

BACKGROUND: Gender is often neglected in health systems, yet health systems are not gender neutral. Within health systems research, gender analysis seeks to understand how gender power relations create inequities in access to resources, the distribution of labour and roles, social norms and values, and decision-making. This paper synthesises findings from nine studies focusing on four health systems domains, namely human resources, service delivery, governance and financing. It provides examples of how a gendered and/or intersectional gender approach can be applied by researchers in a range of low- and middle-income settings (Cambodia, Zimbabwe, Uganda, India, China, Nigeria and Tanzania) to issues across the health system and demonstrates that these types of analysis can uncover new and novel ways of viewing seemingly intractable problems. METHODS: The research used a combination of mixed, quantitative, qualitative and participatory methods, demonstrating the applicability of diverse research methods for gender and intersectional analysis. Within each study, the researchers adapted and applied a variety of gender and intersectional tools to assist with data collection and analysis, including different gender frameworks. Some researchers used participatory tools, such as photovoice and life histories, to prompt deeper and more personal reflections on gender norms from respondents, whereas others used conventional qualitative methods (in-depth interviews, focus group discussion). Findings from across the studies were reviewed and key themes were extracted and summarised. RESULTS: Five core themes that cut across the different projects were identified and are reported in this paper as follows: the intersection of gender with other social stratifiers; the importance of male involvement; the influence of gendered social norms on health system structures and processes; reliance on (often female) unpaid carers within the health system; and the role of gender within policy and practice. These themes indicate the relevance of and need for gender analysis within health systems research. CONCLUSION: The implications of the diverse examples of gender and health systems research highlighted indicate that policy-makers, health practitioners and others interested in enhancing health system research and delivery have solid grounds to advance their enquiry and that one-size-fits-all heath interventions that ignore gender and intersectionality dimensions require caution. It is essential that we build upon these insights in our efforts and commitment to move towards greater equity both locally and globally.


Assuntos
Atenção à Saúde , Países em Desenvolvimento , Identidade de Gênero , Equidade em Saúde , Política de Saúde , Sexismo , Camboja , Cuidadores , China , Feminino , Governo , Recursos em Saúde , Pesquisa sobre Serviços de Saúde , Humanos , Renda , Índia , Masculino , Nigéria , Pesquisa Qualitativa , Pesquisadores , Normas Sociais , Tanzânia , Uganda , Zimbábue
18.
BMC Health Serv Res ; 16(Suppl 7): 626, 2016 11 15.
Artigo em Inglês | MEDLINE | ID: mdl-28185601

RESUMO

BACKGROUND: The Chinese tradition of filial piety, which prioritized family-based care for the elderly, is transitioning and elders can no longer necessarily rely on their children. The purpose of this study was to identify community support for the elderly, and analyze the factors that affect which model of old-age care elderly people dwelling in communities prefer. METHODS: We used the database "Health and Social Support of Elderly Population in Community". Questionnaires were issued in 2013, covering 3 districts in Beijing. A group of 1036 people over 60 years in age were included in the study. The respondents' profile variables were organized in Andersen's Model and community healthcare resource factors were added. A multinomial logistic model was applied to analyze the factors associated with the desired aging care models. RESULTS: Cohabiting with children and relying on care from family was still the primary desired aging care model for seniors (78 %), followed by living in institutions (14.8 %) and living at home independently while relying on community resources (7.2 %). The regression result indicated that predisposing, enabling and community factors were significantly associated with the aging care model preference. Specifically, compared with those who preferred to cohabit with children, those having higher education, fewer available family and friend helpers, and shorter distance to healthcare center were more likely to prefer to live independently and rely on community support. And compared with choosing to live in institutions, those having fewer available family and friend helpers and those living alone were more likely to prefer to live independently and rely on community. Need factors (health and disability condition) were not significantly associated with desired aging care models, indicating that desired aging care models were passive choices resulted from the balancing of family and social caring resources. CONCLUSIONS: In Beijing, China, aging care arrangement preference is the result of balancing family care resources, economic and social status, and the accessibility of community resources. Community facilities and services supporting elderly were found to be insufficient. For China's future health system, efforts should be made to improve community capacity to provide integrated services to senior citizens.


Assuntos
Envelhecimento , Serviços de Saúde Comunitária , Serviços de Saúde para Idosos , Modelos Organizacionais , Apoio Social , Idoso , Idoso de 80 Anos ou mais , Pequim , China , Atenção à Saúde , Pessoas com Deficiência , Características da Família , Feminino , Humanos , Vida Independente , Modelos Logísticos , Masculino , Pessoa de Meia-Idade , Inquéritos e Questionários
19.
J Phys Chem Lett ; 15(23): 6216-6221, 2024 Jun 13.
Artigo em Inglês | MEDLINE | ID: mdl-38838259

RESUMO

Heterogeneous metal-nitrogen-carbon (M-N-C) single-atom catalysts (SACs) have garnered considerable attention in the two-electron CO2 reduction reaction (2e-CO2RR). Interestingly, almost M-N-C SACs mainly produce CO, while Sb is one of the few SACs reported so far that can produce HCOOH. Nevertheless, the underlying factors for different selectivities on Sb-N-C SAC remain controversial, and the lack of in-depth understanding of limiting factors hampers further regulations. Here, by using constant-potential first-principles calculations, we revealed that the high HCOOH selectivity of Sb-N-C SAC is mainly attributed to their weak charge accumulation ability. Remarkably, considering the highly tunable geometric structure of M-N-C SACs, we provide that Sb-N-C SAC with the SbN3S1 center is a promising candidate for CO production. Our work provides the mechanism insight into 2e-CO2RR selectivity and further paves the way toward electrocatalyst regulation and design.

20.
Nat Biotechnol ; 42(2): 247-252, 2024 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-37169966

RESUMO

We present a statistical simulator, scDesign3, to generate realistic single-cell and spatial omics data, including various cell states, experimental designs and feature modalities, by learning interpretable parameters from real data. Using a unified probabilistic model for single-cell and spatial omics data, scDesign3 infers biologically meaningful parameters; assesses the goodness-of-fit of inferred cell clusters, trajectories and spatial locations; and generates in silico negative and positive controls for benchmarking computational tools.


Assuntos
Benchmarking , Modelos Estatísticos , Projetos de Pesquisa
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