Search results for "intermediate"
showing 10 items of 440 documents
Das erste persistenteβ-Silyl-substituierte Vinyl-Kation
1991
Electrospray Ionization Mass Spectrometry Studies on the Mechanism of Hydrosilylation of Terminal Alkynes Using an N-Heterocyclic Carbene Complex of …
2006
A new pyridine-4,5-dichloroimidazol-2-ylidene complex of Ir(I) has been obtained, and its catalytic activity toward hydrosilylation of phenylacetylene and 4-aminophenylacetylene has been studied. T...
A Superoxovanadium(V) Complex Linking the Peroxide and Dioxygen Chemistry of Vanadium.
2001
A missing link: A superoxovanadium(V) complex is the first reaction intermediate in the oxidative conversion of a peroxovanadium(V) complex into a vanadyl(IV) complex and molecular oxygen. The superoxo species appears also to play an essential role in the formation of the peroxovanadium(V) complex from the vanadyl(IV) complex and molecular oxygen.
Dual effects of increased glycogen synthase kinase-3β activity on adult neurogenesis
2013
Adult neurogenesis, the generation of new neurons during the adulthood, is a process controlled by several kinases and phosphatases among which GSK3β exerts important functions. This protein is particularly abundant in the central nervous system, and its activity deregulation is believed to play a key role in chronic disorders such as Alzheimer's disease. Previously, we reported that in vivo overexpression of GSK3β (Tet/GSK3β mice) causes alterations in adult neurogenesis, leading to a depletion of the neurogenic niches. Here, we have further characterized those alterations, finding a delay in the switching-off of doublecortin marker as well as changes in the survival and death rates of imm…
Production and chronobiology of emergence of the cercariae of Euparyphium albuferensis (Trematoda: Echinostomatidae).
1999
The production and the chronobiology of emergence of the cercariae of Euparyphium albuferensis from Gyraulus chinensis experimentally infected with a single miracidium were established during 28 consecutive days from the first day of cercarial shedding. Moreover, the effect of a sudden change in light-dark cycling was investigated. Although the daily cercarial shedding rates show great variability, a progressive increase in cercarial production was observed in the first weeks of the cercarial shedding periods, probably in relation to the demography of intramollusean larval stages. Under 12:12 light-dark cycling condition;, it, albuferensis cercariae emerged in the light, and the rhythm was …
MINDO/3 Study of the Rearrangement of 1-Methylcyclohexyl Cation to 1,2-Dimethylcyclopentyl Cation
1986
The rearrangement of the 1-methylcyclohexyl cation to the 1,2-dimethylcyclopentyl cation has been studied by MINDO/3 calculations, as an application of the branching mechanism model for cycloalkanes. Possible intermediates and transition states have been characterized by diagonalization of their Hessian matrixes. Two nonequivalent pathways, α and β scissions, are relatively close in energy. The calculated transition states are almost equivalent in energy to those found for cyclohexyl cation. Hence, the energy barriers are higher for the rearrangement of the 1-methyl than for cyclohexyl cation, because the former is less stable than the latter.
Interacting processes in protein coagulation
1999
A strong interest is currently focused on protein self-association and deposit. This usually involves conformational changes of the entire protein or of a fragment. It can occur even at low concentrations and is responsible for pathologies such as systemic amyloidosis, Alzheimer's and Prion diseases, and other neurodegenerative pathologies. Readily available proteins, exhibiting at low concentration self-association properties related to conformational changes, offer very convenient model systems capable of providing insight into this class of problems. Here we report experiments on bovine serum albumin, showing that the process of conformational change of this protein towards an intermedia…
Competitive gold-activation modes in terminal alkynes: an experimental and mechanistic study.
2013
The competition between π- and dual σ,π-gold-activation modes is revealed in the gold(I)-catalyzed heterocyclization of 1-(o-ethynylaryl)urea. A noticeable effect of various ligands in gold complexes on the choice of these activation modes is described. The cationic [Au(IPr)](+) (IPr=2,6-bis(diisopropylphenyl)imidazol-2-ylidene) complex cleanly promotes the π activation of terminal alkynes, whereas [Au(PtBu3 )](+) favors intermediate σ,π species. In this experimental and mechanistic study, which includes kinetic and cross-over experiments, several σ-gold, σ,π-gold, and other gold polynuclear reaction intermediates have been isolated and identified by NMR spectroscopy, X-ray diffraction, or …
Spectroscopic and DFT Characterization of a Highly Reactive Nonheme FeV–Oxo Intermediate
2018
The reaction of [(PyNMe3)FeII(CF3SO3)2], 1, with excess peracetic acid at −40 °C generates a highly reactive intermediate, 2b(PAA), that has the fastest rate to date for oxidizing cyclohexane by a nonheme iron species. It exhibits an intense 490 nm chromophore associated with an S = 1/2 EPR signal having g-values at 2.07, 2.01, and 1.94. This species was shown to be in a fast equilibrium with a second S = 1/2 species, 2a(PAA), assigned to a low-spin acylperoxoiron(III) center. Unfortunately, contaminants accompanying the 2(PAA) samples prevented determination of the iron oxidation state by Mossbauer spectroscopy. Use of MeO-PyNMe3 (an electron-enriched version of PyNMe3) and cyclohexyl pero…