Search results for "Redox"
showing 10 items of 619 documents
Dissociative adsorption of water on Au/MgO/Ag(001) from first principles calculations
2015
Abstract The molecular and dissociative adsorption of water on a Ag-supported 1 ML, 2 ML and 3 ML-a six atomic layer-thick MgO films with a single Au adatom is investigated using density functional theory calculations. The obtained results are compared to a bulk MgO(001) surface with an Au atom. On thin films the negatively charged Au strengthens the binding of the polar water molecule due to the attractive Au–H interaction. The adsorption energy trends of OH and H with respect to the film thickness depend on an adsorption site. In the case OH or H binds atop Au on MgO/Ag(001), the adsorption becomes more exothermic with the increasing film thickness, while the reverse trend is seen when th…
Experimental calibration and implications of olivine-melt vanadium oxybarometry for hydrous basaltic arc magmas
2018
The strong dependence of vanadium partitioning between olivine and silicate melt (DVOl-M) on redox conditions (fO2) can be used as sensitive oxybarometer in magmatic systems. Here we extend the experimental database on DVOl-M, obtained so far at high temperatures (mainly above 1250 °C), to lower temperatures that are typical for island-arc basalts. Crystallization experiments were performed using a composition from Mutnovsky volcano (Kamchatka), and the investigated temperature, pressure, and oxygen fugacity ranges were 1025–1150 °C, 0.1 and 0.3 GPa, and ΔQFM of –0.5 to +3.2, respectively. The water content in melts ranged from 0.6 to ∼6.5 wt% H2O. The data demonstrate a strong negative cor…
The compositional variability of eudialyte-group minerals
2011
AbstractEudialyte-group minerals (EGM) represent the most important index minerals of persodic agpaitic systems. Results are presented here of a combined EPMA, Mössbauer spectroscopy and LA-ICP-MS study and EGM which crystallized in various fractionation stages from different parental melts and mineral assemblages in silica over- and undersaturated systems are compared. Compositional variability is closely related to texture, allowing for reconstruction of locally acting magmatic to hydrothermal processes. Early-magmatic EGM are invariably dominated by Fe whereas hydrothermal EGM can be virtually Fe-free and form pure Mn end-members. Hence the Mn/Fe ratio is the most suitable fractionation …
The Thermodynamics of Insertion Electrochemical Electrodes—A Team Play of Electrons and Ions across Two Separate Interfaces
2018
Insertion electrochemical electrodes exhibit simultaneous electron and ion transfer, with the two transfers proceeding across different interfaces. Herein the thermodynamics of the overall electrochemical electrode reaction is discussed with respect to the thermodynamics of these two charge-transfer equilibria. This Minireview includes insertion electrochemical systems where the redox centers are in a solid phase and the ions are transferred between that phase and a solution, and also systems where the redox centers are in a liquid phase that is immiscible with another liquid phase and ions are transferred between the two liquid phases. The Minireview is intended to spark similar studies on…
New Reactions of Amino-Functionalized 3-Vinyl-1H-indoles and Tetrahydropyridin-4-yl Analogues with Dienophiles
1991
Reactions of 3-[2-(morpholin-4-yl)vinyl]-1H-indole (1), the 1,2-dihydro-9H-carbazole 2, as well as the 3-(tetrahydropyridin-4-yl)-1H-indoles 3a and 3b with some carbo- and heterodienophiles are described. The scope and limitations of the synthetic utility of these amino- (or homoamino)-functionalized 3-vinyl-1H-indoles are reported and some MO calculations for the qualitative prediction of their reactivities are presented. The reactions gave rise to substitution products, redox products, Diels-Alder adducts, ene adducts, and Michael-type adducts (Schemes 2 and 3).
The effect of N-tetradecyl-N,N-dimethylamine oxide micelles on the kinetics of the electron transfer reaction of Ce(IV) with substituted malonic acids
2009
Abstract The kinetics of the oxidation of malonic acid and (its substituted compounds, methyl-, ethyl-, butyl- and benzyl-malonic acid) by ceric ions has been studied at 20.0 °C in the absence and the presence of the surfactant N-tetradecyl-N,N-dimethylamine oxide (C 14 DMAO). The addition of increasing amounts of C 14 DMAO influences the rate of the redox process to an extent that significantly depends on the hydrophobicity of the reducing species. The reactivity data together with the estimated binding constants and the standard transfer free energies of the malonic acids from water to the micelles suggest that the malonic acid is confined to the aqueous pseudo-phase while for the other s…
Synthesis and Characterization of a Stable Copper(I) Complex for Radiopharmaceutical Applications
2014
A highly stable copper(I) complex was obtained starting from a copper(II) salt. This compound was characterized by a combination of several analytical techniques (UV/Vis spectroscopy, energy-dispersive X-ray spectroscopy, electrochemistry, and X-ray photoelectron spectroscopy) and was shown to present an N4Cu structure. These results were confirmed by a density functional calculations study of the binding energy and the electronic structure of model ligand and copper complexes. Preliminary tests of complexation showed a high ability of the corresponding ligand to chelate 64Cu in very diluted medium, which is of interest for developing new positron emission tomography imaging agents. The sta…
The Link between Oxidative Stress, Redox Status, Bioenergetics and Mitochondria in the Pathophysiology of ALS
2021
Amyotrophic lateral sclerosis (ALS) is the most common neurodegenerative disease of the motor system. It is characterized by the degeneration of both upper and lower motor neurons, which leads to muscle weakness and paralysis. ALS is incurable and has a bleak prognosis, with median survival of 3–5 years after the initial symptomatology. In ALS, motor neurons gradually degenerate and die. Many features of mitochondrial dysfunction are manifested in neurodegenerative diseases, including ALS. Mitochondria have shown to be an early target in ALS pathophysiology and contribute to disease progression. Disruption of their axonal transport, excessive generation of reactive oxygen species, disruptio…
Electronic aspects of the hydride transfer mechanism. Ab initio analytical gradient studies of the cyclopropenyl‐cation/lithium hydride model reactan…
1985
The electronic mechanisms of a model hydride transfer reaction are theoretically studied with ab inito RHF and UHF SCF MO procedures at the 4‐31G basis set level and analytical gradient methods. The model system describes the reduction of cyclopropenyl cation to cyclopropene by the oxidation of lithium hydride to lithium cation. The molecular fragments corresponding to the asymptotic reactive channels characterizing the stepwise mechanisms currently discussed in the literature have been characterized. The binding energy between the fragments is estimated within a simple electrostatic approximate scheme. The results show that a hydride‐ion mechanism is a likely pathway for this particular sy…
Placing metal micronutrients in context: transport and distribution in plants
2008
Plants have developed finely tuned mechanisms to efficiently acquire and balance the concentrations of essential metal micronutrients including iron, zinc, copper, and manganese, both at the cellular and systemic levels. The application of new emerging technologies to the study of Arabidopsis thaliana is providing a novel spatiotemporal view of plant metal homeostasis. These advances are uncovering unexpected links of metal homeostasis to central cellular processes, such as compartmentalization, daily redox oscillations, or transcriptional regulation. The intracellular compartmentalization of metals seems essential for optimizing the use of micronutrients during development and in response …