Evaluation of electrodeposited alpha Mn2O3 as a catalyst for the Oxygen Evolution Reaction

alpha Mn2O3 is of interest as a low cost and environmentally benign electrocatalyst for the Oxygen Evolution Reaction OER in the process of water splitting. Mechanically stable alpha Mn2O3 electrodes are prepared by annealing of galvanostatically deposited MnOOHx layers on F SnO2 coated glass. The overpotential eta to achieve a current density of j 10 mA cm2 decreases from 590 to 340 mV with increasing layer thickness. Differential capacitance measurements reveal that this high OER activity can be attributed to the large electrochemically active surface area ECSA , which scales linearly with the thickness of these highly porous and electrolyte permeable films. The oxide layers exhibit a reversible oxidation behavior from Mn III to Mn IV , whereas only about 25 of the Mn III is oxidized to Mn IV before the OER reaction takes off. Although the intrinsic activity is small compared to that of other OER catalysts, such as NiFeOx, the combination of high ECSA and good electrical conductivity of these amp; 945; Mn2O3 films ensures that high OER activities can be obtained. The films are found to be stable for gt;2 h in alkaline conditions, as long as the potential does not exceed the corrosion potential of 1.7 V vs. RHE. These findings show that amp; 945; Mn2O3 is a promising OER catalyst for water splitting device

Formation and suppression of defects during heat treatment of BiVO4 photoanodes for solar water splitting

Metal oxide photoelectrodes typically suffer from poor carrier transport properties and extensive carrier recombination, which is caused by the presence of intrinsic or extrinsic defects in the material. Here, the influence of annealing temperature and atmosphere on the formation and suppression of defects in BiVO4 one of the best performing metal oxide photoanodes is elucidated. Annealing in argon has little or no effect on the photoelectrochemical performance due to the competing effects of an increase in grain size i.e., reduction of grain boundaries and the unfavorable formation of oxygen vacancies. When annealing in air, the formation of oxygen vacancies is suppressed, resulting in up to 1.5 fold enhancement of the photocurrent and an order of magnitude increase of the charge carrier mobility. However, vanadium leaves the BiVO4 lattice above 500 C, which leads to a decrease in carrier lifetime and photocurrent. This vanadium loss can be avoided by supplying excess vanadium in the gas phase during annealing. This leads to enhanced charge carrier mobility and lifetime, resulting in improved photocurrents. Overall, this strategy offers a general approach to prevent unfavorable changes of cation stoichiometry during high temperature treatment of complex metal oxide photoelectrode

Extending the Absorption Limit of BiVO4 Photoanodes with Hydrogen Sulfide Treatment

Bismuth vanadate is a promising photoanode material for photoelectrochemical water splitting due to its relative stability, low cost, and nontoxic properties. However, its performance is limited by the large bandgap Eg of 2.4 amp; 8201;eV, and the record photocurrent is already within 90 of its theoretical limit. Further photocurrent enhancement could only be obtained by increasing its optical absorption, for example, by reducing Eg. Herein, sulfur incorporated bismuth vanadate S BiVO4 thin films are synthesized via spray pyrolysis combined with post treatment in hydrogen sulfide environment. Under optimal H2S treatment conditions, sulfur can be incorporated successfully into the BiVO4 lattice, without the formation of any secondary phases. The use of reactive H2S, instead of solid sulfur powders, allows us to decrease the required annealing temperature and increase the kinetics for sulfur incorporation into BiVO4. The Eg of the resulting S BiVO4 films is decreased by gt;200 amp; 8201;meV vs. pristine BiVO4 , which theoretically corresponds to a 20 increase in the theoretical photocurrent limit. Finally, the stability limitation of S BiVO4 is overcome by introducing pulsed laser deposited NiOx protection layers. The modified S BiVO4 NiOx film exhibits higher photocurrent density with no reduction of photocurrent during the 9 amp; 8201;h stability test with AM1.5 illuminatio

On the Origin of the OER Activity of Ultrathin Manganese Oxide Films

There is an urgent need for cheap, stable, and abundant catalyst materials for photoelectrochemical water splitting. Manganese oxide is an interesting candidate as an oxygen evolution reaction OER catalyst, but the minimum thickness above which MnOx thin films become OER active has not yet been established. In this work, ultrathin lt;10 nm manganese oxide films are grown on silicon by atomic layer deposition to study the origin of OER activity under alkaline conditions. We found that MnOx films thinner than 1.5 nm are not OER active. X ray photoelectron spectroscopy shows that this is due to electrostatic catalyst support interactions that prevent the electrochemical oxidation of the manganese ions close to the interface with the support, while in thicker films, MnIII and MnIV oxide layers appear as OER active catalysts after oxidation and electrochemical treatment. From our investigations, it can be concluded that one MnIII,IV O monolayer is sufficient to establish oxygen evolution under alkaline conditions. The results of this study provide important new design criteria for ultrathin manganese oxide oxygen evolution catalyst

Long Non-Coding RNA ZFAS1 Is a Major Regulator of Epithelial-Mesenchymal Transition through miR-200/ZEB1/E-Cadherin, Vimentin Signaling in Colon Adenocarcinoma

Colon adenocarcinoma is a common cause of cancer-related deaths worldwide. Epithelial-mesenchymal transition is a major regulator of cancer metastasis, and increased understanding of this process is essential to improve patient outcomes. Long non-coding RNA (lncRNA) are important regulators of carcinogenesis. To identify lncRNAs associated with colon carcinogenesis, we performed an exploratory differential gene expression analysis comparing paired colon adenocarcinoma and normal colon epithelium using an RNA-sequencing data set. This analysis identified lncRNA ZFAS1 as significantly increased in colon cancer compared to normal colon epithelium. This finding was validated in an institutional cohort using laser capture microdissection. ZFAS1 was also found to be principally located in the cellular cytoplasm. ZFAS1 knockdown was associated with decreased cellular proliferation, migration, and invasion in two colon cancer cell lines (HT29 and SW480). MicroRNA-200b and microRNA-200c (miR-200b and miR-200c) are experimentally validated targets of ZFAS1, and this interaction was confirmed using reciprocal gene knockdown. ZFAS1 knockdown regulated ZEB1 gene expression and downstream targets E-cadherin and vimentin. Knockdown of miR-200b or miR-200c reversed the effect of ZFAS1 knockdown in the ZEB1/E-cadherin, vimentin signaling cascade, and the effects of cellular migration and invasion, but not cellular proliferation. ZFAS1 knockdown was also associated with decreased tumor growth in an in vivo mouse model. These results demonstrate the critical importance of ZFAS1 as a regulator of the miR-200/ZEB1/E-cadherin, vimentin signaling cascade

Cost-effectiveness analysis of stand-alone or combined non-invasive imaging tests for the diagnosis of stable coronary artery disease: results from the EVINCI study

Aim: This study aimed at evaluating the cost-effectiveness of different non-invasive imaging-guided strategies for the diagnosis of obstructive coronary artery disease (CAD) in a European population of patients from the Evaluation of Integrated Cardiac Imaging in Ischemic Heart Disease (EVINCI) study. Methods and results: Cost-effectiveness analysis was performed in 350 patients (209 males, mean age 59 ± 9 years) with symptoms of suspected stable CAD undergoing computed tomography coronary angiography (CTCA) and at least one cardiac imaging stress-test prior to invasive coronary angiography (ICA) and in whom imaging exams were analysed at dedicated core laboratories. Stand-alone stress-tests or combined non-invasive strategies, when the first exam was uncertain, were compared. The diagnostic end-point was obstructive CAD defined as > 50% stenosis at quantitative ICA in the left main or at least one major coronary vessel. Effectiveness was defined as the percentage of correct diagnosis (cd) and costs were calculated using country-specific reimbursements. Incremental cost-effectiveness ratios (ICERs) were obtained using per-patient data and considering “no-imaging” as reference. The overall prevalence of obstructive CAD was 28%. Strategies combining CTCA followed by stress ECHO, SPECT, PET, or stress CMR followed by CTCA, were all cost-effective. ICERs values indicated cost saving from − 969€/cd for CMR-CTCA to − 1490€/cd for CTCA-PET, − 3092€/cd for CTCA-SPECT and − 3776€/cd for CTCA-ECHO. Similarly when considering early revascularization as effectiveness measure. Conclusion: In patients with suspected stable CAD and low prevalence of disease, combined non-invasive strategies with CTCA and stress-imaging are cost-effective as gatekeepers to ICA and to select candidates for early revascularization

The fate of acetic acid during glucose co-metabolism by the spoilage yeast Zygosaccharomyces bailii

Zygosaccharomyces bailii is one of the most widely represented spoilage yeast species, being able to metabolise acetic acid in the presence of glucose. To clarify whether simultaneous utilisation of the two substrates affects growth efficiency, we examined growth in single- and mixed-substrate cultures with glucose and acetic acid. Our findings indicate that the biomass yield in the first phase of growth is the result of the weighted sum of the respective biomass yields on single-substrate medium, supporting the conclusion that biomass yield on each substrate is not affected by the presence of the other at pH 3.0 and 5.0, at least for the substrate concentrations examined. In vivo(13)C-NMR spectroscopy studies showed that the gluconeogenic pathway is not operational and that [2-(13)C]acetate is metabolised via the Krebs cycle leading to the production of glutamate labelled on C(2), C(3) and C(4). The incorporation of [U-(14)C]acetate in the cellular constituents resulted mainly in the labelling of the protein and lipid pools 51.5% and 31.5%, respectively. Overall, our data establish that glucose is metabolised primarily through the glycolytic pathway, and acetic acid is used as an additional source of acetyl-CoA both for lipid synthesis and the Krebs cycle. This study provides useful clues for the design of new strategies aimed at overcoming yeast spoilage in acidic, sugar-containing food environments. Moreover, the elucidation of the molecular basis underlying the resistance phenotype of Z. bailii to acetic acid will have a potential impact on the improvement of the performance of S. cerevisiae industrial strains often exposed to acetic acid stress conditions, such as in wine and bioethanol production.This work was supported by Fundacao para a Ciencia e Tecnologia (FCT), Portugal Grant PTDC/AGR-ALI/102608/2008 and by project FCOMP-01-0124-FEDER- 007047 and by FEDER through POFC - COMPETE and national funds from FCT - project PEst-C/BIA/UI4050/2011. The funders had no role in study design, data collection and analysis, decision to publish, or preparation of the manuscript