scholarly journals The Role of Ruthenium on Carbon‐Supported PtRu Catalysts for Electrocatalytic Glycerol Oxidation under Acidic Conditions

ChemCatChem ◽  
2017 ◽  
Vol 9 (9) ◽  
pp. 1683-1690 ◽  
Author(s):  
Youngmin Kim ◽  
Hyun Woo Kim ◽  
Seonhwa Lee ◽  
Jisu Han ◽  
Daewon Lee ◽  
...  
2017 ◽  
Vol 398 (3) ◽  
pp. 319-329 ◽  
Author(s):  
Christine C. Helms ◽  
Xiaohua Liu ◽  
Daniel B. Kim-Shapiro

Abstract Nitrite was once thought to be inert in human physiology. However, research over the past few decades has established a link between nitrite and the production of nitric oxide (NO) that is potentiated under hypoxic and acidic conditions. Under this new role nitrite acts as a storage pool for bioavailable NO. The NO so produced is likely to play important roles in decreasing platelet activation, contributing to hypoxic vasodilation and minimizing blood-cell adhesion to endothelial cells. Researchers have proposed multiple mechanisms for nitrite reduction in the blood. However, NO production in blood must somehow overcome rapid scavenging by hemoglobin in order to be effective. Here we review the role of red blood cell hemoglobin in the reduction of nitrite and present recent research into mechanisms that may allow nitric oxide and other reactive nitrogen signaling species to escape the red blood cell.


Author(s):  
Jeanette A. Krause ◽  
Daoli Zhao ◽  
Sayandev Chatterjee ◽  
Bonnie M. Yeung ◽  
William B. Connick ◽  
...  

Different extended packing motifs of dichlorido[2-(pyridin-2-yl)-1,10-phenanthroline]copper(II), [CuCl2(C17H11N3)], are obtained, depending on the crystallization conditions. A triclinic form, (I), is obtained from dimethylformamide–diethyl ether or methanol, whereas crystallization from dimethylformamide–water yields a monoclinic form, (II). In each case, the CuIIcentre is in a five-coordinate distorted square-pyramidal geometry. The extended packing for both forms can be described as a highly offset π-stacking arrangement, with interlayer distances of 3.674 (3) and 3.679 (3) Å for forms (I) and (II), respectively. The reaction of diprotonated Pt(tmpip2NCN)Cl [tmpip2NCN = 2,6-bis(2,2,6,6-tetramethylpiperidylmethyl)benzyl] with AgPF6under acidic conditions, followed by the addition of 2-(pyridin-2-yl)-1,10-phenanthroline, results in a hydrogen-bonded cocrystal, 2,2,6,6-tetramethyl-4-oxopiperidinium hexafluorophosphate–2-(pyridin-2-yl)-1,10-phenanthroline (1/1), C9H18NO+·PF6−·C17H11N3, (III). The extended packing maximizes π–π interactions in a parallel face-to-face arrangement, with an interlayer stacking distance of 3.4960 (14) Å.


2008 ◽  
Vol 74 (8) ◽  
pp. 2370-2378 ◽  
Author(s):  
Maarten Mols ◽  
Tjakko Abee

ABSTRACT The presence and activities of urease genes were investigated in 49 clinical, food, and environmental Bacillus cereus isolates. Ten strains were shown to have urease genes, with eight of these strains showing growth on urea as the sole nitrogen source. Two of the urease-positive strains, including the sequenced strain ATCC 10987, could not use urea for growth, despite their capacities to produce active urease. These observations can be explained by the inability of the two strains to use ammonium as a nitrogen source. The impact of urea hydrolysis on acid stress resistance was subsequently assessed among the ureolytic B. cereus strains. However, none of the strains displayed increased fitness under acidic conditions or showed enhanced acid shock survival in the presence of urea. Expression analysis of urease genes in B. cereus ATCC 10987 revealed a low level of expression of these genes and a lack of pH-, nitrogen-, urea-, oxygen-, and growth phase-dependent modulation of mRNA transcription. This is in agreement with the low urease activity observed in strain ATCC 10987 and the other nine strains tested. Although a role for B. cereus ureolytic activity in acid survival cannot be excluded, its main role appears to be in nitrogen metabolism, where ammonium may be provided to the cells in nitrogen-limited, urea-containing environments.


2017 ◽  
Vol 21 (10) ◽  
pp. 680-691
Author(s):  
Kaarin K. Evens ◽  
Kathryn E. Splan

The addition of arylethynyl groups to the porphyrin macrocycle represents an effective strategy with which to enhance the light-harvesting properties of porphyrins. We now extend this modification to arylethynyl porphyrins with two or four [Formula: see text]-hydroxyphenyl substituents. Arylethynyl porphyrins bearing four, but not two, [Formula: see text]-hydroxyphenyl substituents show evidence of aggregation under acidic conditions. Under basic conditions, deprotonation of the peripheral hydroxyphenyl substituents results in substantially red-shifted spectral features and enhanced absorption in the Q-band region. When the hydroxyphenyl groups are appended to the porphyrin macrocylce via the ethynyl spacers, the spectral shifts observed upon deprotonation are significantly enhanced relative to those observed for hydroxyphenylporphyrins, highlighting the role of expanded conjugation in altering porphyrin photophysics.


2016 ◽  
Vol 44 (1) ◽  
pp. 13-17 ◽  
Author(s):  
Cristina Azevedo ◽  
Adolfo Saiardi

Post-translational modifications (PTMs) add regulatory features to proteins that help establish the complex functional networks that make up higher organisms. Advances in analytical detection methods have led to the identification of more than 200 types of PTMs. However, some modifications are unstable under the present detection methods, anticipating the existence of further modifications and a much more complex map of PTMs. An example is the recently discovered protein modification polyphosphorylation. Polyphosphorylation is mediated by inorganic polyphosphate (polyP) and represents the covalent attachment of this linear polymer of orthophosphate to lysine residues in target proteins. This modification has eluded MS analysis as both polyP itself and the phosphoramidate bonds created upon its reaction with lysine residues are highly unstable in acidic conditions. Polyphosphorylation detection was only possible through extensive biochemical characterization. Two targets have been identified: nuclear signal recognition 1 (Nsr1) and its interacting partner, topoisomerase 1 (Top1). Polyphosphorylation occurs within a conserved N-terminal polyacidic serine (S) and lysine (K) rich (PASK) cluster. It negatively regulates Nsr1–Top1 interaction and impairs Top1 enzymatic activity, namely relaxing supercoiled DNA. Modulation of cellular levels of polyP regulates Top1 activity by modifying its polyphosphorylation status. Here we discuss the significance of the recently identified new role of inorganic polyP.


1994 ◽  
Vol 30 (9) ◽  
pp. 47-57 ◽  
Author(s):  
Shuzo Tanaka ◽  
Uttam Kumar Saha

The effects of pH on the photocatalytic decomposition of 2,4,6-trichlorophenol (TCP) were investigated in the presence of titanium dioxide suspensions illuminated by a high pressure mercury lamp over the wavelength range of 302-405 nm. Higher degradation rate was observed under alkaline conditions than acidic conditions. Although a rapid adsorption of TCP onto the TiO2 surface was observed at low pH and no adsorption at high pH, the role of adsorption of TCP was found insignificant in photocatalysis. With sodium chloride addition, a decrease in reaction rate was observed at pH 5 due to Cl− ions inhibition, but at pH 10 the same anions had no adverse effect on the measured photocatalytic efficiency and Na+ ions enhanced the degradation rate of TCP. With no oxygen, however, the photocatalytic decomposition of TCP in sodium chloride solution gives lower degradation rate than with dissolved oxygen and no sodium chloride at various pH. Complete mineralization requires a longer illumination time than the decomposition of the parent compound. A mechanism for the reaction based on photogeneration of hydroxyl radicals was proposed.


ChemCatChem ◽  
2009 ◽  
Vol 1 (4) ◽  
pp. 510-514 ◽  
Author(s):  
Alberto Villa ◽  
Di Wang ◽  
Dang Sheng Su ◽  
Laura Prati
Keyword(s):  

2009 ◽  
Vol 24 (2) ◽  
pp. 475-481 ◽  
Author(s):  
R. Ceccato ◽  
S. Dirè ◽  
T. Barone ◽  
G. De Santo ◽  
E. Cazzanelli

The structural evolution with temperature of some V2O5 gels and thin films is presented, and the role of the hydrolysis conditions is investigated. Several techniques, i.e., x-ray diffraction, differential thermal analysis, infrared, and temperature-dependent Raman spectroscopy, have been used to follow the thermal behavior of the samples. When the bulk xerogels begin to change from a nanocrystalline phase to the orthorhombic α-V2O5, in the temperature range 280 to 300 °C, a growth of vanadium oxide nanotubes also occurs, while at higher temperatures the crystallization into the α phase prevails. A slightly different evolution is observed for heat treated thin films, which show a structure containing polyvanadate chains near room temperature. They also present a growth of nanotubes for intermediate temperatures and a complete crystallization into the α phase when the temperature is further increased.


2017 ◽  
Author(s):  
Adam H. Stevens ◽  
Delma Childers ◽  
Mark Fox-Powell ◽  
Charles S. Cockell

1AbstractBiofilms improve microbes’ resistance to a variety of extreme physical and chemical conditions on Earth. The discovery of putative aqueous environments on other planetary bodies such as Mars motivates an interest in understanding the viability of life, and the potential role of biofilms, in previously unexplored geochemical extremes. We investigated the loss of viability of planktonic cells and biofilms ofSphingomonas desiccabilis(a Gram-negative, desiccation resistant, soil crust-forming organism) to simulated Martian brines. These brines were produced from geochemical modelling of past aqueous environments on Mars, and their high sulfate concentrations make them different to most terrestrial brines, although similar briny environments have been found in locations such as the Basque Lakes in Canada or in deep subsurface groundwater systems. Biofilms grown on basaltic scoria were subjected to the simulated martian brines and the viability of cells was measured over time and compared to equivalent planktonic cultures. Crystal violet assay was used to measure how the biomass of the biofilms changed over time in response to the brines. While certain brines were highly hostile to microbial viability, we found that biofilms that were desiccated prior to being treated with brines maintained viability over a longer treatment period when compared to planktonic cells. Our results show that biofilms confer short-term protection to the harsh osmotic, ionic, and acidic conditions of Mars-relevant brines. However, in the most extreme simulated brines, even biofilms eventually lost viability. By demonstrating that biofilms confer protection to conditions that are potentially analogous to current day recurrent slope lineae (thought to be produced by the flow of briny fluids) on Mars, our results show that contaminant biofilm-forming microorganisms may have a greater chance of surviving in so-called ‘Special Regions’ on Mars, with implications for planetary protection in missions that aim to explore these regions.


2021 ◽  
Vol 17 (4) ◽  
pp. e1009434
Author(s):  
Jan Bieri ◽  
Remo Leisi ◽  
Cornelia Bircher ◽  
Carlos Ros

The glycosphingolipid (GSL) globoside (Gb4) is essential for parvovirus B19 (B19V) infection. Historically considered the cellular receptor of B19V, the role of Gb4 and its interaction with B19V are controversial. In this study, we applied artificial viral particles, genetically modified cells, and specific competitors to address the interplay between the virus and the GSL. Our findings demonstrate that Gb4 is not involved in the binding or internalization process of the virus into permissive erythroid cells, a function that corresponds to the VP1u cognate receptor. However, Gb4 is essential at a post-internalization step before the delivery of the single-stranded viral DNA into the nucleus. In susceptible erythroid Gb4 knockout cells, incoming viruses were arrested in the endosomal compartment, showing no cytoplasmic spreading of capsids as observed in Gb4-expressing cells. Hemagglutination and binding assays revealed that pH acts as a switch to modulate the affinity between the virus and the GSL. Capsids interact with Gb4 exclusively under acidic conditions and dissociate at neutral pH. Inducing a specific Gb4-mediated attachment to permissive erythroid cells by acidification of the extracellular environment led to a non-infectious uptake of the virus, indicating that low pH-mediated binding to the GSL initiates active membrane processes resulting in vesicle formation. In summary, this study provides mechanistic insight into the interaction of B19V with Gb4. The strict pH-dependent binding to the ubiquitously expressed GSL prevents the redirection of the virus to nonpermissive tissues while promoting the interaction in acidic intracellular compartments as an essential step in infectious endocytic trafficking.


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