Westfarrell2213
Due to the metal-support interactions of this peculiar support, the catalyst exhibited the oxidation of CO with a turnover frequency as high as 0.17 s-1 at a temperature of 100 °C.The complex α-[Fe(mcp)(OTf)2] (mcp = N,N'-dimethyl-N,N'-bis(pyridin-2-ylmethyl)-cyclohexane-1,2-diamine and OTf = trifluoromethanesulfonate anion) was reported in 2011 by some of us as an active water oxidation (WO) catalyst in the presence of sacrificial oxidants. However, because chemical oxidants are likely to take part in the reaction mechanism, mechanistic electrochemical studies are critical in establishing to what extent previous studies with sacrificial reagents have actually been meaningful. In this study, the complex α-[Fe(mcp)(OTf)2] and its analogues were investigated electrochemically under both acidic and neutral conditions. All the systems under investigation proved to be electrochemically active toward the WO reaction, with no major differences in activity despite the structural changes. Our findings show that WO-catalyzed by mcp-iron complexes proceeds via homogeneous species, whereas the analogous manganese complex forms a heterogeneous deposit on the electrode surface. Mechanistic studies show that the reaction proceeds with a different rate-determining step (rds) than what was previously proposed in the presence of chemical oxidants. Moreover, the different kinetic isotope effect (KIE) values obtained electrochemically at pH 7 (KIE ∼ 10) and at pH 1 (KIE = 1) show that the reaction conditions have a remarkable effect on the rds and on the mechanism. We suggest a proton-coupled electron transfer (PCET) as the rds under neutral conditions, whereas at pH 1 the rds is most likely an electron transfer (ET).Metallic two-dimensional transition-metal dichalcogenides (TMDs) of the group 5 metals are emerging as catalysts for an efficient hydrogen evolution reaction (HER). The HER activity of the group 5 TMDs originates from the unsaturated chalcogen edges and the highly active surface basal planes, whereas the HER activity of the widely studied group 6 TMDs originates solely from the chalcogen- or metal-unsaturated edges. However, the batch production of such nanomaterials and their scalable processing into high-performance electrocatalysts is still challenging. Herein, we report the liquid-phase exfoliation of the 2H-TaS2 crystals by using 2-propanol to produce single/few-layer (1H/2H) flakes, which are afterward deposited as catalytic films. A thermal treatment-aided texturization of the catalytic films is used to increase their porosity, promoting the ion access to the basal planes of the flakes, as well as the number of catalytic edges of the flakes. The hybridization of the H-TaS2 flakes and H-TaSe2 flakes tunes the Gibbs free energy of the adsorbed atomic hydrogen onto the H-TaS2 basal planes to the optimal thermo-neutral value. In 0.5 M H2SO4, the heterogeneous catalysts exhibit a low overpotential (versus RHE, reversible hydrogen electrode) at the cathodic current of 10 mA cm-2 (η10) of 120 mV and high mass activity of 314 A g-1 at an overpotential of 200 mV. In 1 M KOH, they show a η10 of 230 mV and a mass activity of 220 A g-1 at an overpotential of 300 mV. Our results provide new insight into the usage of the metallic group 5 TMDs for the HER through scalable material preparation and electrode processing.The use of high-valent antimony-oxo porphyrins as visible-light photocatalysts operating via direct hydrogen atom transfer has been demonstrated. Computational analysis indicates that the triplet excited state of these complexes shows an oxyl radical behavior, while the SbV center remains in a high-valent oxidation state, serving uniquely to carry the oxo moiety and activate the coordinated ligands. This porphyrin-based system has been exploited upon irradiation to catalyze C-H to C-C bond conversion via the addition of hydrogen donors (ethers and aldehydes) onto Michael acceptors in a redox-neutral fashion without the need of any external oxidant. Laser flash photolysis experiments confirmed that the triplet excited state of the photocatalyst triggers the desired C-H cleavage.The 2019-2020 SARS-related coronavirus-2 (SARS-CoV-2) pandemic has brought unprecedented challenges to healthcare sectors around the world. As of November 2020, there have been over 64 million confirmed cases and approaching 2 million deaths globally. Despite the large number of positive cases, there are very limited established standards of care and therapeutic options available. To date, there is still no Food and Drug Administration (FDA) approved vaccine for COVID-19, although there are several options in various clinical trial stages. Herein, we have performed a global review evaluating the roles of age and sex on COVID-19 hospitalizations, ICU admissions, deaths in hospitals, and deaths in nursing homes. We have identified a trend in which elderly and male patients are significantly affected by adverse outcomes. There is evidence suggesting that sex hormone levels can influence immune system function against SARS-CoV-2 infection, thus reducing the adverse effects of COVID-19. Since older adults have lower levels of these sex hormones, we therefore speculate, within rational scientific context, that sex steroids, such as estrogen and progesterone, needs further consideration for use as alternative therapeutic option for treating COVID-19 elderly patients. To our knowledge, this is the first comprehensive article evaluating the significance of sex hormones in COVID-19 outcomes in older adults.Worldwide COVID-19 infection poses an enormous risk to public health and an alarming global socioeconomic burden. JSH-150 The impact of the COVID-19 pandemic on individuals with underlying health conditions as well as on the elderly population is extensive and effective strategies are needed to understand the mechanism behind it. Cellular senescence defines as an irreversible cell cycle arrest due to DNA damage leading to accumulation of senescent cells in the elderly population and may result in worsening of COVID-19 mediated increased mortality. However, whether this variation in senescence levels, in different aged populations, translation to COVID-19 infection is unknown. The spike protein of SARS-CoV-2 has been recently identified to be responsible for inducing pathogenic signals, although a clear understanding of how the host receptor interacts with SARS-CoV-2 protein and mediates the immune responses is not clear. In this review, we address the epidemiology of SARS-CoV-2 and the cellular senescence responding immune response to pathogenic SARS-CoV-2.