Search results for "Colloid"
showing 10 items of 1288 documents
Reversible complexation of ethylene by a silylene under ambient conditions.
2014
Treatment of toluene solutions of the silylenes Si(SArMe6)2 (ArMe6 = C6H3-2,6(C6H2-2,4,6-Me3)2, 1) or Si(SArPri4)2 (ArPri4 = C6H3-2,6(C6H3-2,6-Pri2)2, 2) with excess ethylene gas affords the siliranes (ArMe6S)2tiebar above startSiCH2tiebar above endCH2 (3) or (ArPri4S)2tiebar above startSiCH2tiebar above endCH2 (4). Silirane 4 evolves ethylene spontaneously at room temperature in toluene solution. A Van’t Hoff analysis by variable-temperature 1H NMR spectroscopy showed that ΔGassn = −24.9(2.5) kJ mol–1 for 4. A computational study of the reaction mechanism using a model silylene Si(SPh)2 (Ph = C6H5) was in harmony with the Van’t Hoff analysis, yielding ΔGassn = −24 kJ mol–1 and an activatio…
Theoretical Study of the Gas Phase Decomposition of Glycolic, Lactic, and 2-Hydroxyisobutyric Acids
1997
The reaction mechanism associated with the decomposition of three α-hydroxycarboxylic acids (glycolic, lactic, and 2-hydroxyisobutyric) in the gas phase to form carbon monoxide, water, and the corresponding carbonyl compounds has been theoretically characterized by using ab initio analytical gradients at the MP2 level of theory with the 6-31G** and 6-31++G** basis sets. A detailed characterization of the potential energy surface points out the existence of three competitive reaction pathways for the decomposition process. The first pathway describes a two-step mechanism, with water elimination and formation of an α-lactone intermediate, achieved by the nucleophilic attack of the carbonylic …
Mechanistic Studies on the Metal-Free Activation of Dihydrogen by Antiaromatic Pentarylboroles
2012
The perfluoro- and perprotiopentaphenylboroles 1 and 2 react with dihydrogen to effect H-H bond cleavage and formation of boracyclopentene products. The mechanism of this reaction has been studied experimentally through evaluation of the kinetic properties of the slower reaction between 2 and H(2). The reaction is first-order in both [borole] and [H(2)] with activation parameters of ΔH(‡) = 34(8) kJ/mol and ΔS(‡) = -146(25) J mol(-1) K(-1). A minimal kinetic isotope effect of 1.10(5) was observed, suggesting an asynchronous geometry for H-H cleavage in the rate-limiting transition state. To explain the stereochemistry of the observed products, a ring-opening/ring-closing mechanism is propos…
Dynamics and reactivity in Thermus aquaticus N6-adenine methyltransferase.
2014
M.TaqI is a DNA methyltransferase from Thermus aquaticus that catalyzes the transfer of a methyl group from S-adenosyl-l-methionine to the N6 position of an adenine, a process described only in prokaryotes. We have used full atomistic classical molecular dynamics simulations to explore the protein–SAM–DNA ternary complex where the target adenine is flipped out into the active site. Key protein–DNA interactions established by the target adenine in the active site are described in detail. The relaxed structure was used for a combined quantum mechanics/molecular mechanics exploration of the reaction mechanism using the string method. According to our free energy calculations the reaction takes…
Theoretical study of phosphodiester hydrolysis in nucleotide pyrophosphatase/phosphodiesterase. Environmental effects on the reaction mechanism.
2010
We here present a theoretical study of the alkaline hydrolysis of methyl p-nitrophenyl phosphate (MpNPP(-)) in aqueous solution and in the active site of nucleotide pyrophosphatase/phosphodiesterase (NPP). The analysis of our simulations, carried out by means of hybrid quantum mechanics/molecular mechanics (QM/MM) methods, shows that the reaction takes place through different reaction mechanisms depending on the environment. Thus, while in aqueous solution the reaction occurs by means of an A(N)D(N) mechanism, the enzymatic process takes place through a D(N)A(N) mechanism. In the first case, we found associative transition-state (TS) structures, while in the enzyme TS structures have dissoc…
Mechanism of four-electron reduction of dioxygen to water by ferrocene derivatives in the presence of perchloric acid in benzonitrile, catalyzed by c…
2004
The selective two-electron reduction of dioxygen occurs in the case of a monocobalt porphyrin [Co(OEP)], whereas the selective four-electron reduction of dioxygen occurs in the case of a cofacial dicobalt porphyrin [Co(2)(DPX)]. The other cofacial dicobalt porphyrins [Co(2)(DPA), Co(2)(DPB), and Co(2)(DPD)] also catalyze the two-electron reduction of dioxygen, but the four-electron reduction is not as efficient as in the case of Co(2)(DPX). The micro-superoxo species of cofacial dicobalt porphyrins were produced by the reactions of cofacial dicobalt(II) porphyrins with dioxygen in the presence of a bulky base and the subsequent one-electron oxidation of the resulting micro-peroxo species by…
Rate-retarding effects of mixed anionic/non-ionic micelles on the alkaline hydrolysis of the chloropentamminocobalt(III) complex
2006
Abstract Rate data for the alkaline hydrolysis of the chloropentaamminecobalt(III) cation in the presence of mixed micelles composed of (i) anionic sodium decylsulphate (SDeS) and non-ionic dodecylpenta(oxyethylene glycol) monoether (C 12 E 5 ) surfactants and (ii) anionic sodium perfluorooctanoate (SPFO) and non-ionic C 12 E 5 surfactants has been obtained at T 298 K and constant electrolyte concentration 0.08 mol dm −3 ([NaOH] = 0.01 mol dm −3 , [NaClO 4 ] = 0.07 mol dm −3 ) over a wide range of total surfactant concentration ( C t ) and anionic mole fraction ( χ ). The critical micelle concentrations (c.m.c.s) of the mixed micelles have been determined over the entire χ range by means of…
Zr, Hf and REE distribution in river water under different ionic strength conditions
2018
International audience; The Platani River flowing in south-central Sicily, interacting with evaporite rocks, generates a wide range of ionic strength in the water catchment from 0.1 to 5.0 mol kg−1. We sampled 38 river sites and analysed the composition for the dissolved fraction filtered through 0.45 μm, the truly dissolved fraction obtained through ultrafiltration (10 kDa) and the relative included colloidal fraction.This study was focused on the recognition of Zr, Hf and REE behaviour under changing ionic strength conditions, since this is one of parameters responsible for colloid stability in natural waters. In turn, this phenomenon leads to REE release from the colloidal fraction and t…
Comparative evaluation of antibacterial effect of nanoparticles and lasers against Endodontic Microbiota: An in vitro study
2018
Background Present study was conducted with the aim of evaluating antimicrobial efficacy of silver (AgNP) and gold nanoparticles (AuNP) with and without Nd: YAG laser (L) irradiation against experimentally inoculated Enterococcus faecalis in infected human root dentin. Material and Methods 120 extracted single rooted human teeth were prepared and inoculated with E. faecalis for 24 hrs. The teeth were then randomly divided into 4 experimental group: AgNPs group: irrigation for 3minutes with 50 μl of 100 ppm, the AuNPs group: irrigation with 50 μl of 100 ppm, the AgNPs & Nd: YAG lasers group: irrigation with 50 μl of 100 ppm + irradiation with 1.5W laser for 60 seconds, the AuNPs & Nd: YAG la…