Ni–Fe and Ni–Fe–Co mixed-metal oxide (MMO) films were investigated as electrocatalysts for the oxygen evolution reaction (OER) in 0.1 M KOH. In an effort to optimize MMO morphology, aniline was used ...as a capping agent to produce high-surface-area Ni–Fe–Co films on Raney nickel supports. This catalyst exhibits enhanced mass activity in comparison to the Ni–Fe OER electrocatalysts reported to date. Cyclic voltammetry shows changes in the potential of the Ni2+/3+ transitions in Fe- or Co-containing MMO films. In situ X-ray absorption spectroscopy (XAS) analysis confirms that Fe acts to stabilize Ni in the 2+ oxidation state, while Co facilitates oxidation to the 3+ state. The results of this study support the recent claims that Fe (not Ni) is the OER active site. The OER enhancement of the ternary Ni–Fe–Co catalyst results from two effects: (1) the charge-transfer effects of Co result in the formation of the conductive NiIIIOOH phase at lower overpotential, thus activating the Fe sites which are otherwise inaccessible to electron transfer in the nonconductive NiII(OH)2 host lattice, and (2) XAS analysis shows that the presence of Co effectively “shrinks” the Ni and Fe local geometry, likely resulting in an optimized Fe–OH/OOH bond strength. In addition, analysis of heat-treatment effects indicates that calcination at 400 °C improves the OER activity of Ni–Fe–Co but deactivates Ni–Fe. Annealing studies under argon show that MMO surfaces with a hydrated Ni(OH)2 phase and a crystalline NiO phase exhibit nearly identical OER activities. Finally, the morphology of the MMO catalyst film on Raney Ni support provides excellent catalyst dispersion and should result in high active-site utilization for use in technologically relevant gas-diffusion electrodes.
Despite the fundamental and practical significance of the hydrogen evolution and oxidation reactions (HER/HOR), their kinetics in base remain unclear. Herein, we show that the alkaline HER/HOR ...kinetics can be unified by the catalytic roles of the adsorbed hydroxyl (OHad)-water-alkali metal cation (AM+) adducts, on the basis of the observations that enriching the OHad abundance via surface Ni benefits the HER/HOR; increasing the AM+ concentration only promotes the HER, while varying the identity of AM+ affects both HER/HOR. The presence of OHad-(H2O) x -AM+ in the double-layer region facilitates the OHad removal into the bulk, forming OH–-(H2O) x -AM+ as per the hard–soft acid–base theory, thereby selectively promoting the HER. It can be detrimental to the HOR as per the bifunctional mechanism, as the AM+ destabilizes the OHad, which is further supported by the CO oxidation results. This new notion may be important for alkaline electrochemistry.
Dengue is a leading cause of severe illness and hospitalization in Vietnam. This study sought to elucidate the linkage between climate factors, mosquito indices and dengue incidence.
Monthly data on ...dengue cases and mosquito larval indices were ascertained between 2004 and 2008 in the Dak Lak province (Vietnam). Temperature, sunshine, rainfall and humidity were also recorded as monthly averages. The association between these ecological factors and dengue was assessed by the Poisson regression model with adjustment for seasonality.
During the study period, 3,502 cases of dengue fever were reported. Approximately 72% of cases were reported from July to October. After adjusting for seasonality, the incidence of dengue fever was significantly associated with the following factors: higher household index (risk ratio RR: 1.66; 95% confidence interval CI: 1.62-1.70 per 5% increase), higher container index (RR: 1.78; 95% CI: 1.73-1.83 per 5% increase), and higher Breteau index (RR: 1.57; 95% CI: 1.53-1.60 per 5 unit increase). The risk of dengue was also associated with elevated temperature (RR: 1.39; 95% CI: 1.25-1.55 per 2 °C increase), higher humidity (RR: 1.59; 95% CI: 1.51-1.67 per 5% increase), and higher rainfall (RR: 1.13; 95% CI: 1.21-1.74 per 50 mm increase). The risk of dengue was inversely associated with duration of sunshine, the number of dengue cases being lower as the sunshine increases (RR: 0.76; 95% CI: 0.73-0.79 per 50 hours increase).
These data suggest that indices of mosquito and climate factors are main determinants of dengue fever in Vietnam. This finding suggests that the global climate change will likely increase the burden of dengue fever infection in Vietnam, and that intensified surveillance and control of mosquito during high temperature and rainfall seasons may be an important strategy for containing the burden of dengue fever.
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Dostopno za:
DOBA, IZUM, KILJ, NUK, PILJ, PNG, SAZU, SIK, UILJ, UKNU, UL, UM, UPUK
Schweinfurthins (SWs) are naturally occurring prenylated stilbenes with promising anticancer properties. They act through a novel mechanism of action similar to that of other families of natural ...compounds. Their known target, oxysterol-binding protein (OSBP), plays a crucial role in controlling the intracellular distribution of cholesterol. We synthesized 15 analogues of SWs and demonstrated for the first time that their cytotoxicity as well as that of natural derivatives correlates with their affinity for OSBP. Through this extensive SAR study, we selected one synthetic analogue obtained in one step from SW-G. Using its fluorescence properties, we showed that this compound recapitulates the effect of natural SW-G in cells and confirmed that it leads to cell death via the same mechanism. Finally, after pilot PK experiments, we provided the first evidence of its in vivo efficacy in combination with temozolomide in a patient-derived glioblastoma xenograft model.
With the aim of discovering new cytotoxic prenylated stilbenes of the schweinfurthin series, Macaranga tanarius was selected for detailed phytochemical investigation among 21 Macaranga species ...examined by using a molecular networking approach. From an ethanol extract of the fruits, seven new prenylated stilbenes, schweinfurthins K–Q (7–13), were isolated, along with vedelianin (1), schwenfurthins E–G (2–4), mappain (5), and methyl-mappain (6). The structures of the new compounds were established by spectroscopic data analysis. The relative configurations of compounds 8, 12, and 13 were determined based on ROESY NMR spectroscopic analysis. The cytotoxic activities of compounds 1–13 were evaluated against the human glioblastoma (U87) and lung (A549) cancer cell lines.
We report an interesting new class of bifunctional electrocatalysts, Pd/C-CeO2, with excellent activity and stability for the hydrogen oxidation reaction (HOR) under alkaline conditions. The unique ...structure of palladium deposited onto a mixed support of Vulcan XC-72 carbon and CeO2 consists of Pd metal preferable deposited on the ceria regions of the catalyst. The CeO2-Pd interaction leads to enhanced HOR kinetics and increased stability. Here we compare catalysts with three different Pd loadings and show that the 10wt% Pd sample has optimized activity. Hydrogen pumping and fuel cell experiments based on this catalyst show higher activities as compared to a Pd/C sample without ceria. Metal dissolution tests and identical location transmission microscopy experiments show that the catalyst stability under harsh potential cycling experiments in alkaline medium is significantly improved as compared to Pd/C, making this material one of the best options for use as highly active and highly stable electrocatalysts for the HOR in anion exchange membrane fuel cells.
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•A new class of electrocatalyst for H2 oxidation in alkaline media is described.•Unique structure of Pd deposited on a mixed support of carbon and CeO2.•Hydrogen pump and fuel cell tests show enhanced activity.•Identical location transmission electron microscopy show improved stability.
The main objective of this research is to assess the impact of intra-class spectral variation on the accuracy of soft classification and super-resolution mapping. The accuracy of both analyses was ...negatively related to the degree of intra-class spectral variation, but the effect could be reduced through the use of spectral sub-classes. The latter is illustrated in mapping the shoreline at a sub-pixel scale from Landsat ETM+ data. Reducing the degree of intra-class spectral variation increased the accuracy of soft classification, with the correlation between predicted and actual class coverage rising from 0.87 to 0.94, and super-resolution mapping, with the RMSE in shoreline location decreasing from 41.13 m to 35.22 m.
For the hydrogen oxidation reaction (HOR), platinum group metal (PGM) catalysts are still the norm, and their large initial catalytic activity is counterbalanced by their uncertain durability in ...alkaline environments: harsh degradations proceed, like detachment and agglomeration of metallic nanoparticles from the carbon support, as witnessed from dedicated accelerated stress tests (AST). Herein, a strategy to increase such catalysts’ durability is provided, using carbon layers surrounding the Pd-based carbon-supported nanoparticles. The robustness of such catalysts, baring 0.5- or 0.7-nm-thick carbon cap over the Pd nanoparticles, is evaluated from AST combined with several pre/post-test characterization techniques: identical location transmission electron microscopy (IL-TEM), ex situ X-ray photoelectron spectroscopy (XPS) and ex situ inductively coupled plasma mass spectrometry (ICP-MS). The carbon layer protection limits the Pd-based nanoparticles’ agglomeration, detachment, and metal leaching, improving long-term catalyst durability in HOR-like operation. Thicker carbon layers surrounding the Pd nanoparticles lead to higher materials durability and lower degradation rate (larger performance stability) upon AST, compared to thinner carbon layers. In addition, the carbon-capped catalysts enable to maintain better the required Pd/PdO state of the surface that is essential for fast HOR, resulting in superior intrinsic HOR activity versus unprotected Pd/C. Overall, this work demonstrates that the activity-durability relationship can be tuned for carbon-capped catalysts.
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