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1.
Heliyon ; 10(5): e26792, 2024 Mar 15.
Artículo en Inglés | MEDLINE | ID: mdl-38434273

RESUMEN

Background: Contrast retention (CR) is an important predictor of left atrial appendage thrombus (LAAT) and stroke in patients with non-valvular atrial fibrillation (AF). We sought to explore the underlying mechanisms of CR using computational fluid dynamic (CFD) simulations. Methods: A total of 12 patients with AF who underwent both cardiac computed tomography angiography (CTA) and transesophageal echocardiography (TEE) before left atrial appendage occlusion (LAAO) were included in the study. The patients were allocated into the CR group or non-CR group based on left atrial appendage (LAA) angiography. Patient-specific models were reconstructed to evaluate time-averaged wall shear stress (TAWSS), oscillatory shear index (OSI), relative residence time (RRT), and endothelial cell activation potential (ECAP). Additionally, the incidence of thrombosis was predicted using residence time (RT) at different time-points. Results: TAWSS was lower [median (Interquartile Range) 0.27 (0.19-0.47) vs 1.35 (0.92-1.79), p < 0.001] in LAA compared to left atrium. In contrast, RRT [1438 (409.70-13869) vs 2.23 (1.81-3.14), p < 0.001] and ECAP [122.70 (30.01-625.70) vs 0.19 (0.16-0.27), p < 0.001)] was higher in the LAA. The patients in the CR group had significantly higher RRT [(mean ± SD) 16274 ± 11797 vs 639.70 ± 595.20, p = 0.009] and ECAP [610.80 ± 365.30 vs 54.26 ± 54.38, p = 0.004] in the LAA compared to the non-CR group. Additionally, patients with CR had a wider range of thrombus-prone regions [0.44(0.27-0.66)% vs 0.05(0.03-0.27)%, p = 0.009] at the end of the 15th cardiac cycle. Conclusions: These findings suggest that CR might be an indicator of high-risk thrombus formation in the LAA. And CT-based CFD simulation may be a feasible substitute for the evaluation of LAA thrombotic risk in patients with AF, especially in patients with CR.

2.
Eur J Clin Pharmacol ; 80(6): 827-838, 2024 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-38483545

RESUMEN

INTRODUCTION: Since the first experimentally proven tyrosine kinase inhibitor (TKI) imatinib was introduced in the clinical setting, TKIs have attracted widespread attention because of their remarkable therapeutic effects and improvement of survival rates. TKIs are small-molecule, multi-target, anti-cancer agents that target different tyrosine kinases and block downstream signaling. ADVERSE REACTIONS AND CONCERNS: However, with in-depth research on TKI drugs, the adverse reactions-for example, thyroid dysfunction-have become a concern and thus have attracted the attention of numerous researchers. Thyroid dysfunction, especially hypothyroidism, that occurs in high incidence during TKI therapy has a close relationship with treatment efficacy, but the mechanism of TKI-induced thyroid dysfunction is obscure. DISCUSSION: This review discusses the epidemiology, possible mechanisms, and clinical significance of hypothyroidism in cancer patients treated with TKI.


Asunto(s)
Antineoplásicos , Hipotiroidismo , Inhibidores de Proteínas Quinasas , Humanos , Hipotiroidismo/inducido químicamente , Inhibidores de Proteínas Quinasas/efectos adversos , Antineoplásicos/efectos adversos , Proteínas Tirosina Quinasas/antagonistas & inhibidores , Neoplasias/tratamiento farmacológico , Animales
3.
Heliyon ; 10(1): e23769, 2024 Jan 15.
Artículo en Inglés | MEDLINE | ID: mdl-38192873

RESUMEN

In the context of the growing environmental pollution and resource depletion caused by traditional manufacturing industries, the need for sustainable and eco-friendly practices has become a critical issue for the upgrading and transformation of the manufacturing industry worldwide. Based on data from listed manufacturing companies in China, which is the world's largest manufacturing country and exhibits significant diversity regarding the ownership, scale and level of enterprises, the impact of manufacturing output servitization on green total factor productivity (GTFP), which is a measurement of economic efficiency that takes into account environmental impacts, is analyzed in this article. The results show that manufacturing output servitization can improve the GTFP of enterprises, and this can be achieved through mechanisms such as increased profitability and innovation capabilities. The positive effect on the GTFP of enterprises in less developed regions is greater than that in developed regions and is more significant for private and foreign-funded enterprises than for state-owned enterprises. The companies that adhere to the Global Reporting Initiative framework for environmental, social and governance reporting experience a more significant positive impact on GTFP as a result of their manufacturing output servitization efforts. This research offers valuable insights into the potential of servitization as a strategy for enhancing GTFP and provides actionable guidance for policy-makers and industry stakeholders seeking to align manufacturing practices with sustainability goals.

5.
J Am Chem Soc ; 145(33): 18439-18446, 2023 Aug 23.
Artículo en Inglés | MEDLINE | ID: mdl-37552880

RESUMEN

OH adspecies are involved in numerous electrocatalytic reactions, such as CO, H2, methanol, and ethanol oxidation and oxygen reduction reactions, as a reaction intermediate and/or reactant. In this work, we have, for the first time, identified the OH stretching band of OH adspecies on Pt, Ru, and Pt/Ru electrodes with surface-enhanced infrared absorption spectroscopy (SEIRAS) in a flow cell through potential modulation and CO displacement. We found that while Ru had a relatively constant OH coverage at potentials between 0.1 and 0.8 V, Pt had a maximum OH coverage at 0.6 V in 0.1 M HClO4 and 0.7 V in 0.1 M KOH. CO oxidation kinetics on Ru were sluggish, although adsorbed OH appeared on Ru at very low potentials. Binary Pt/Ru electrodes promote CO oxidation through a synergistic effect in which Ru promotes OH adsorption and Pt catalyzes the reaction between the CO and OH adspecies. In addition, water coadsorbed with CO at Ru sites of Pt/Ru also plays an important role. These new spectroscopic results about OH adspecies could advance the understanding of the mechanism of fuel cell related electrocatalysis.

6.
Macromol Rapid Commun ; 44(19): e2300244, 2023 Oct.
Artículo en Inglés | MEDLINE | ID: mdl-37465937

RESUMEN

Photothermal tumor therapy (PTT) and photoacoustic imaging (PA) have emerged as promising noninvasive diagnostic and therapeutic approaches for cancer treatment. However, the development of efficient PTT agents with high photostability and strong near-infrared (NIR) absorption remains challenging. This study synthesizes three isoindigo-based dual-acceptor conjugated polymers (CPs) (P-IIG-TPD, P-IIG-DPP, and P-IIG-EDOT-BT) via a green and nontoxic direct arylation polymerization (DArP) method and characterizes their optical, electrochemical, and NIR photothermal conversion properties. By incorporating two acceptors into the backbone, the resulting polymers exhibit enhanced photothermal conversion efficiency (PCE) due to improved synergy among conjugation length, planarity, and intramolecular charge transfer (ICT). The nanoparticles (NPs) of P-IIG-EDOT-BT and P-IIG-DPP have a uniform size distribution around 140 nm and exhibit remarkable NIR absorption at 808 nm. In addition, P-IIG-EDOT-BT and P-IIG-DPP NPs exhibit high PCEs of 62% and 78%, respectively. This study promotes the molecular design of CPs as NIR photothermal conversion materials and provides guidance for the development of novel dual-acceptor CPs for tumor diagnosis and treatment.


Asunto(s)
Nanopartículas , Neoplasias , Humanos , Polímeros/química , Nanopartículas/química , Indoles
7.
Anal Biochem ; 675: 115214, 2023 08 15.
Artículo en Inglés | MEDLINE | ID: mdl-37353066

RESUMEN

Fructus Choerospondiatis (FC), a Mongolian medicine, was mainly used in Mongolian medical theory for the treatment of coronary heart disease (CHD). Nonetheless, the main components and mechanisms of action of FC in the treatment of coronary artery disease have not been studied clearly. AIM OF THE STUDY: The aim of this study is to identify the components of FC and analyze the pathways affected by the targets of these components to probe into the potential mechanisms of action of FC on coronary heart disease. MATERIALS AND METHODS: Identification of compounds in FC employing high performance liquid chromatography quadrupole time-of-flight tandem mass spectrometry (HPLC-QTOF-MS) method, then further investigate the network pharmacology and molecular docking to obtain potential targets and elucidate the potential mechanism of action of FC in the therapy of CHD. Experimental validation was established to verify the mechanism of FC in vitro. RESULTS: 21 FC components were identified and 65 overlapping targets were gained. In addition, these ingredients regulated AMPK and PPAR signaling pathway by 65 target genes including IL6, AKT1 and PPARg, etc. Molecular docking displayed that the binding ability of the key target PPARg to FC components turned out to be better. Experimental validation proved that FC treatment decreased the expression of PPARg (p < 0.05) compare with model group, which may be involved in the PPAR signaling pathway. CONCLUSIONS: This study was the first to elucidate the mechanism of action of components of FC for the treatment of CHD using network pharmacology. It alleviated CHD by inhibiting the expression of PPARg to attenuate hypoxia/reoxygenation injury, and the results give a basis for elucidating the molecular mechanism of action of FC for the treatment of coronary heart disease.


Asunto(s)
Enfermedad Coronaria , Medicamentos Herbarios Chinos , Humanos , Simulación del Acoplamiento Molecular , Farmacología en Red , PPAR gamma , Enfermedad Coronaria/tratamiento farmacológico , Cromatografía Líquida de Alta Presión , Medicamentos Herbarios Chinos/farmacología , Medicamentos Herbarios Chinos/uso terapéutico
8.
J Am Chem Soc ; 145(11): 6330-6338, 2023 Mar 22.
Artículo en Inglés | MEDLINE | ID: mdl-36898001

RESUMEN

Ethanol is a promising alternative fuel to methanol for direct alcohol fuel cells. However, the complete electrooxidation of ethanol to CO2 involves 12 electrons and C-C bond splitting so that the detailed mechanism of ethanol decomposition/oxidation remains elusive. In this work, a spectroscopic platform, combining SEIRA spectroscopy with DEMS, and isotopic labeling were employed to study ethanol electrooxidation on Pt under well-defined electrolyte flow conditions. Time- and potential-dependent SEIRA spectra and mass spectrometric signals of volatile species were simultaneously obtained. For the first time, adsorbed enolate was identified with SEIRA spectroscopy as the precursor for C-C bond splitting during ethanol oxidation on Pt. The C-C bond rupture of adsorbed enolate led to the formation of CO and CHx ad-species. Adsorbed enolate can also be further oxidized to adsorbed ketene at higher potentials or reduced to vinyl/vinylidene ad-species in the hydrogen region. CHx and vinyl/vinylidene ad-species can be reductively desorbed only at potentials below 0.2 and 0.1 V, respectively, or oxidized to CO2 only at potentials above 0.8 V, and thus they poison Pt surfaces. These new mechanistic insights will help provide design criteria for higher-performing and more durable electrocatalysts for direct ethanol fuel cells.

9.
Nature ; 614(7947): 262-269, 2023 02.
Artículo en Inglés | MEDLINE | ID: mdl-36755171

RESUMEN

Carbon dioxide electroreduction facilitates the sustainable synthesis of fuels and chemicals1. Although Cu enables CO2-to-multicarbon product (C2+) conversion, the nature of the active sites under operating conditions remains elusive2. Importantly, identifying active sites of high-performance Cu nanocatalysts necessitates nanoscale, time-resolved operando techniques3-5. Here, we present a comprehensive investigation of the structural dynamics during the life cycle of Cu nanocatalysts. A 7 nm Cu nanoparticle ensemble evolves into metallic Cu nanograins during electrolysis before complete oxidation to single-crystal Cu2O nanocubes following post-electrolysis air exposure. Operando analytical and four-dimensional electrochemical liquid-cell scanning transmission electron microscopy shows the presence of metallic Cu nanograins under CO2 reduction conditions. Correlated high-energy-resolution time-resolved X-ray spectroscopy suggests that metallic Cu, rich in nanograin boundaries, supports undercoordinated active sites for C-C coupling. Quantitative structure-activity correlation shows that a higher fraction of metallic Cu nanograins leads to higher C2+ selectivity. A 7 nm Cu nanoparticle ensemble, with a unity fraction of active Cu nanograins, exhibits sixfold higher C2+ selectivity than the 18 nm counterpart with one-third of active Cu nanograins. The correlation of multimodal operando techniques serves as a powerful platform to advance our fundamental understanding of the complex structural evolution of nanocatalysts under electrochemical conditions.

10.
RSC Adv ; 12(42): 27525-27533, 2022 Sep 22.
Artículo en Inglés | MEDLINE | ID: mdl-36276052

RESUMEN

At a fundamental level, the broad application of raw and stir-fried Arctii Fructus products as anti-tumor and anti-inflammatory agents is commonly recognized. In order to understand some of the discrepancies pertaining to their therapeutic functions, an associated study of pharmacokinetics is required. In this study, a reliable ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) method was initially developed for the concurrent determination of seven compounds from Arctii Fructus in plasma. By virtue of its acceptable performance, the developed method was incorporated in assessing the pharmacokinetic differences of the compounds following the oral administration of raw and stir-fried Arctii Fructus. Subsequently, the results highlighted potential improvements to the exposure of the seven compounds, and the enriched bioavailability of arctiin through the process of stir-frying, which are deemed essential constituents of Arctii Fructus. This study represents the initial attempt at assessing the influence of stir-frying on the pharmacokinetic behaviors of the primary Arctii Fructus composition. Furthermore, the results could be instrumental in expanding the clinical applications of diverse Arctii Fructus products, and reveal the inherent processing mechanism.

11.
J Am Chem Soc ; 144(39): 17783-17791, 2022 10 05.
Artículo en Inglés | MEDLINE | ID: mdl-36137298

RESUMEN

Hydrogen-atom transfer mediated by earth-abundant transition-metal hydrides (M-Hs) has emerged as a powerful tool in organic synthesis. Current methods to generate M-Hs most frequently rely on oxidatively initiated hydride transfer. Herein, we report a reductive approach to generate Co-H, which allows for canonical hydrogen evolution reactions to be intercepted by hydrogen-atom transfer to an alkene. Electroanalytical and spectroscopic studies provided mechanistic insights into the formation and reactivity of Co-H, which enabled the development of two new alkene hydrofunctionalization reactions.


Asunto(s)
Alquenos , Hidrógeno , Alquenos/química , Catálisis , Electrones , Hidrógeno/química , Estructura Molecular
12.
J Pharm Biomed Anal ; 219: 114938, 2022 Sep 20.
Artículo en Inglés | MEDLINE | ID: mdl-35850015

RESUMEN

OBJECTIVE: We sought to develop and optimize a targeted bile acids (BAs) metabolomics method based on a dynamic multiple reaction monitoring (dMRM) strategy and explored the dynamic alterations of BAs in diarrhea induced by capecitabine in a mouse model. METHOD: The targeted metabolomics method was developed using an Agilent 6460A triple quadrupole mass spectrometer, and 41 types of BAs were monitored in negative ionization mode. The mass spectrometer detection was optimized using dMRM to enhance the responses, separation, and peak shape and to shorten the analysis time. A mouse model of diarrhea was established by multiple administration of capecitabine, and plasma samples were collected at baseline and the end of drug administration for subsequent BAs analysis. RESULTS: The targeted BA metabolomics method achieved shorter chromatographic separation time (10 min) for 41 BAs, with good peak shapes and response increases of 3- to 10-fold after application of dMRM. The mouse model of capecitabine-induced diarrhea was established, and the three BAs 23-norcholic acid, isolithocholic acid, and isodeoxycholic acid in the baseline samples contributed the most to differentiating mice with diarrhea from those without diarrhea. For mice that ultimately developed diarrhea, apocholic acid, isodeoxycholic acid, and 7-ketodeoxycholic acid exhibited the largest change in concentrations compared with their baseline concentrations. CONCLUSION: The dMRM strategy has obvious advantages compared with common MRM. The results in model mice showed that a differentiated profile of BAs in the baseline may indicate biomarkers of diarrhea induced by capecitabine, and disturbed homeostasis may explain the metabolomic mechanism of diarrhea occurrence.


Asunto(s)
Ácidos y Sales Biliares , Metabolómica , Animales , Capecitabina/efectos adversos , Cromatografía Líquida de Alta Presión/métodos , Diarrea/inducido químicamente , Metabolómica/métodos , Ratones
13.
J Am Chem Soc ; 144(18): 8106-8114, 2022 05 11.
Artículo en Inglés | MEDLINE | ID: mdl-35486896

RESUMEN

Pd-based electrocatalysts are considered to be a promising alternative to Pt in anion-exchange membrane fuel cells (AEMFCs), although major challenges remain. Most of the Pd-based electrocatalysts developed for the sluggish oxygen reduction reaction (ORR) have been exclusively evaluated by rotating disk electrode (RDE) voltammetry at room temperature, rather than in membrane electrode assemblies (MEAs), making it challenging to apply them in practical fuel cells. We have developed a series of carbon-supported novel PdHx nanosheets (PdHx NS), which displayed outstanding ORR performance in room-temperature RDE tests. Specifically, a sample synthesized at 190 °C displayed a mass activity of 0.67 A mg-1 and a specific activity of 1.07 mA cm-2 at 0.95 V vs RHE, representing the highest reported value among Pd-based ORR electrocatalysts in alkaline media and higher than Pt-based catalysts reported in the literature. Furthermore, we employed PdHx NS and commercial Pd/C as model catalysts to systematically study the effects of temperature on their ORR activity in RDE measurements and subsequently evaluated their performance in MEA testing. Our observations indicate/demonstrate how oxidative stability affected the ORR performance of Pd-based electrocatalysts, which provided some critical insights into future ORR catalyst development for alkaline fuel cell applications.


Asunto(s)
Oxígeno , Paladio , Catálisis , Estrés Oxidativo
14.
J Pharm Biomed Anal ; 213: 114691, 2022 May 10.
Artículo en Inglés | MEDLINE | ID: mdl-35257982

RESUMEN

Depression is a mental health disorder characterized by chronic negative mood, and depression has become a major threat to human health and quality of life. Anyupeibo capsule, a fifth-class new Chinese medicine, was prepared with extracts of Piper laetispicum C.DC. (Piperaceae), and the alkaloid K6 (5'-methoxy-3',4'-methyl-enedioxycinnamic-acidisob-utylamide-isobutylamide) was found to be the main active component. Using high-performance liquid chromatography coupled with triple-quadrupole tandem mass spectrometry (LC-MS/MS), we developed a method to quantify the concentration of K6 in serum samples from patients with depression. Pretreatment of samples was completed based on solid-phase extraction, and the mobile phase for subsequent LC analysis consisted of aqueous ammonium acetate (0.1 mmol/L, phase A) and acetonitrile (phase B) with isocratic elution at 60% B. Chromatographic separation of K6 was achieved within 3 min with an Agilent ZORBAX SB-C18 column (2.1 × 150 mm, 3.5 µm) at a flow rate of 0.3 mL/min. A linear regression equation for K6 yielded correlation coefficients of r2 > 0.99 within a linear range 0.0503-100.5000 ng/mL. Extraction recovery ranged from 85.33% to 101.18%, and the matrix effect ranged from 87.15% to 100.28%. The inter-day and intra-day precision values-expressed as relative standard deviation-were less than 15%, and the corresponding accuracy values were within ±15%. All validation results for stability, specificity, and carry-over met the requirements of Pharmacopoeia. The LC-MS/MS method was applied to determine the K6 concentration in serum samples from patients with depression in a phase III clinical trial of Anyupeibo capsule.


Asunto(s)
Calidad de Vida , Espectrometría de Masas en Tándem , Cromatografía Líquida de Alta Presión , Cromatografía Liquida/métodos , Depresión , Humanos , Reproducibilidad de los Resultados , Espectrometría de Masas en Tándem/métodos
15.
J Mater Chem B ; 10(9): 1418-1426, 2022 03 02.
Artículo en Inglés | MEDLINE | ID: mdl-35142757

RESUMEN

The development of a multifunctional single molecule phototherapeutic agent with excellent fluorescence imaging, photothermal therapy and photodynamic therapy at the same time is still a challenging task, which mainly arises from the low absorbance of the molecule, and the complexity of energy dissipation and molecular design. Herein, four donor-acceptor (D-A) compounds were synthesized by linking triphenylamine (TPA), thiophene/thieno[3,2-b]thiophene and different cyano acceptor structures. In this design, we propose a molecular design strategy to redshift absorption and increase the molar extinction coefficient (ε) by enhancing electron-withdrawing acceptors and enlarging the π-conjugation plane unit. Due to the twisted structure of TPA, these compounds exhibit aggregation-induced emission (AIE) characteristics. Notably, these AIEgens have long emission wavelengths, excellent photostability, biocompatibility, photothermal stability and singlet oxygen (1O2) generation performance. Among them, the photothermal conversion efficiency of a compound (named TCF-SS-TPA NPs) can reach 84.5%. Cellular internalization and therapy showed that TCF-SS-TPA NPs have good biocompatibility, excellent cell bioimaging and cancer phototherapy capabilities in vitro. This study will stimulate the molecular design of multifunctional phototherapeutics to realize effective synergistic cancer therapy.


Asunto(s)
Nanopartículas , Neoplasias , Fotoquimioterapia , Humanos , Nanopartículas/química , Neoplasias/diagnóstico por imagen , Neoplasias/tratamiento farmacológico , Imagen Óptica , Tiofenos
16.
Chem Rev ; 122(6): 6117-6321, 2022 03 23.
Artículo en Inglés | MEDLINE | ID: mdl-35133808

RESUMEN

Hydrogen energy-based electrochemical energy conversion technologies offer the promise of enabling a transition of the global energy landscape from fossil fuels to renewable energy. Here, we present a comprehensive review of the fundamentals of electrocatalysis in alkaline media and applications in alkaline-based energy technologies, particularly alkaline fuel cells and water electrolyzers. Anion exchange (alkaline) membrane fuel cells (AEMFCs) enable the use of nonprecious electrocatalysts for the sluggish oxygen reduction reaction (ORR), relative to proton exchange membrane fuel cells (PEMFCs), which require Pt-based electrocatalysts. However, the hydrogen oxidation reaction (HOR) kinetics is significantly slower in alkaline media than in acidic media. Understanding these phenomena requires applying theoretical and experimental methods to unravel molecular-level thermodynamics and kinetics of hydrogen and oxygen electrocatalysis and, particularly, the proton-coupled electron transfer (PCET) process that takes place in a proton-deficient alkaline media. Extensive electrochemical and spectroscopic studies, on single-crystal Pt and metal oxides, have contributed to the development of activity descriptors, as well as the identification of the nature of active sites, and the rate-determining steps of the HOR and ORR. Among these, the structure and reactivity of interfacial water serve as key potential and pH-dependent kinetic factors that are helping elucidate the origins of the HOR and ORR activity differences in acids and bases. Additionally, deliberately modulating and controlling catalyst-support interactions have provided valuable insights for enhancing catalyst accessibility and durability during operation. The design and synthesis of highly conductive and durable alkaline membranes/ionomers have enabled AEMFCs to reach initial performance metrics equal to or higher than those of PEMFCs. We emphasize the importance of using membrane electrode assemblies (MEAs) to integrate the often separately pursued/optimized electrocatalyst/support and membranes/ionomer components. Operando/in situ methods, at multiscales, and ab initio simulations provide a mechanistic understanding of electron, ion, and mass transport at catalyst/ionomer/membrane interfaces and the necessary guidance to achieve fuel cell operation in air over thousands of hours. We hope that this Review will serve as a roadmap for advancing the scientific understanding of the fundamental factors governing electrochemical energy conversion in alkaline media with the ultimate goal of achieving ultralow Pt or precious-metal-free high-performance and durable alkaline fuel cells and related technologies.


Asunto(s)
Suministros de Energía Eléctrica , Protones , Hidrógeno/química , Oxígeno/química , Agua
17.
J Chem Phys ; 156(3): 034703, 2022 Jan 21.
Artículo en Inglés | MEDLINE | ID: mdl-35065580

RESUMEN

Methanol and formic acid electro-oxidation on Pt has been studied under well-defined flow conditions by a spectroscopic platform that combines differential electrochemical mass spectrometry (DEMS) and attenuated total reflection-Fourier transform infrared (ATR-FTIR) spectroscopy. The volatile soluble products from methanol and formic acid oxidation on Pt have been detected by DEMS, while adsorbed intermediates have been identified with ATR-FTIR spectroscopy. Besides CO2 and methylformate, which were detected by DEMS, other non-volatile soluble intermediates such as formaldehyde and formic acid were also generated during methanol oxidation on Pt. Besides water adsorption bands, linearly bonded CO, bridge-bonded CO, adsorbed formate, adsorbed formic acid, and adsorbed CHO bands were observed by ATR-FTIR spectroscopy during methanol and formic acid oxidation on Pt. Formic acid adsorption suppressed the formate and water adsorption. Our results suggest that formate could be an inactive adsorbed species, rather than an active intermediate, for both methanol and formic acid oxidation. Pb modification of Pt significantly enhanced formic acid oxidation through the direct pathway due to the third-body effect and electronic effects. Formic acid oxidation took place mainly at Pb modified low-coordinated defect sites at low potentials. Formic acid decomposition to form adsorbed CO occurred only in the hydrogen region, and Pb modification also slightly enhanced the successive oxidation of adsorbed CO. A double-peak infrared band was observed for linearly bound CO on the Pt film and was simulated with the Fresnel equations and Bruggeman effective medium theory.

18.
Toxicol Appl Pharmacol ; 435: 115845, 2022 01 15.
Artículo en Inglés | MEDLINE | ID: mdl-34953898

RESUMEN

Chronic exposure to arsenic promotes lung cancer. Human studies have identified immunosuppression as a risk factor for cancer development. The immune checkpoint pathway of Programmed cell death 1 ligand (PD-L1) and its receptor (programmed cell death receptor 1, PD-1) is the most studied mechanism of immunosuppression. We have previously shown that prolonged arsenic exposure induced cell transformation of BEAS-2B cells, a human lung epithelial cell line. More recently our study further showed that arsenic induced PD-L1 up-regulation, inhibited T cell effector function, and enhanced lung tumor formation in the mice. In the current study, using arsenic-induced BEAS-2B transformation as a model system we investigated the mechanism underlying PD-L1 up-regulation by arsenic. Our data suggests that Lnc-DC, a long non-coding RNA, and signal transducer and activator of transcription 3 (STAT3) mediates PD-L1 up-regulation by arsenic.


Asunto(s)
Arsénico/toxicidad , Antígeno B7-H1/biosíntesis , Antígeno B7-H1/genética , Animales , Línea Celular , Femenino , Humanos , Neoplasias Pulmonares/inducido químicamente , Neoplasias Pulmonares/patología , Ratones , ARN Largo no Codificante/biosíntesis , ARN Largo no Codificante/genética , Factor de Transcripción STAT3/efectos de los fármacos , Factor de Transcripción STAT3/genética , Transducción de Señal/efectos de los fármacos , Linfocitos T/efectos de los fármacos , Regulación hacia Arriba/efectos de los fármacos
19.
Sensors (Basel) ; 21(22)2021 Nov 14.
Artículo en Inglés | MEDLINE | ID: mdl-34833637

RESUMEN

Economic globalization is developing more rapidly than ever before. At the same time, economic growth is accompanied by energy consumption and carbon emissions, so it is particularly important to estimate, analyze and evaluate the economy accurately. We compared different nighttime light (NTL) index models with various constraint conditions and analyzed their relationships with economic parameters by linear correlation. In this study, three indices were selected, including original NTL, improved impervious surface index (IISI) and vegetation highlights nighttime-light index (VHNI). In the meantime, all indices were built in a linear regression relationship with gross domestic product (GDP), employed population and power consumption in southeast China. In addition, the correlation coefficient R2 was used to represent fitting degree. Overall, comparing the regression relationships with GDP of the three indices, VHNI performed best with the value of R2 at 0.8632. For the employed population and power consumption regression with these three indices, the maximum R2 of VHNI are 0.8647 and 0.7824 respectively, which are also the best performances in the three indices. For each individual province, the VHNI perform better than NTL and IISI in GDP regression, too. When taking employment population as the regression object, VHNI performs best in Zhejiang and Anhui provinces, but not all provinces. Finally, for power consumption regression, the value of VHNI R2 is better than NTL and IISI in every province except Hainan. The results show that, among the indices under different constraint conditions, the linear relationships between VHNI and GDP and power consumption are the strongest under vegetation constraint in southeast China. Therefore, VHNI index can be used for fitting analysis and prediction of economy and power consumption in the future.


Asunto(s)
Dióxido de Carbono , Carbono , Dióxido de Carbono/análisis , China , Fenómenos Físicos , Análisis de Regresión
20.
Chemphyschem ; 22(13): 1397-1406, 2021 07 02.
Artículo en Inglés | MEDLINE | ID: mdl-33831274

RESUMEN

The hydroxide ion concentration dependence of the methanol oxidation reaction at Pt was studied using microelectrode voltammetry and rotating disk electrode voltammetry. Both methods suggest that the rate of methanol oxidation is limited by hydroxide mass transport at low hydroxide concentrations, while it is inhibited by hydroxide adsorption at high concentrations. It was possible to shift from the transport-limited regime to the inhibitory regime by varying the bulk concentration of hydroxide or by varying mass transport to the electrode. Rotating ring-disk electrode voltammetry was employed to qualitatively assess changes in the diffusion layer pH. The results indicated a decrease in the surface pH during methanol oxidation, as expected, but also that the pH reached a steady state during hydroxide transport limited methanol oxidation.

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