Search results for "rate constant"
showing 10 items of 224 documents
Quantum dynamics of 16O in collision with ortho- and para-17O17O
2017
Abstract We report full quantum dynamical observables, such as integral and differential cross sections and rate constants, for the 16 O + 17 O 17 O reactive collision process. We particularly emphasize the effect coming from the nonzero nuclear spin of 17 O, leading to two nuclear spin isomers of 34 O 2 , ortho- and para- 34 O 2 which can be studied independently and behave differently. A comparison with the 16 O + 18 O 18 O collision is given. We find that processes involving 17 O 17 O are always faster than with 18 O 18 O.
Quantum Dynamics of the 17O + 32O2 Collision Process
2016
We report full quantum integral and differential cross sections and rate constants for the 17O + 32O2 reactive process. This constitutes the first quantum scattering study of the 17O16O16O system. We emphasize the comparison with the 18O + 32O2 collision in close connection to the mass-independent fractionation (hereafter referred to as MIF) puzzle for ozone in atmospheric chemistry. We find similar general trends in the cross sections and rate constants for both rare isotopes, but we note some singular behaviors peculiar to the use of 17O isotope, particularly at the lowest collision energies.
Comparative assessment of a foam-based method for ISCO of coal tar contaminated unsaturated soils
2019
Abstract In situ delivery of liquid reagents in vadose zone is limited by gravity and soil anisotropy. A new foam-based delivery method of persulfate (PS) solutions in unsaturated soils was previously shown to overcome these limitations. The goal of this paper is to demonstrate the efficiency of this method regarding contaminant removal. Hence, the comparative oxidation of 200 mg.kg−1 coal tar artificially contaminated soils with thermally activated PS was carried out after PS-delivery using foam, surfactant solution and pure water. The foam-based method was compared in unfavorable conditions to the reference methods. Especially, in the latter, soil and oxidant solutions were thoroughly mix…
Warhead Reactivity Limits the Speed of Inhibition of the Cysteine Protease Rhodesain.
2021
Viral and parasitic pathogens rely critically on cysteine proteases for host invasion, replication, and infectivity. Their inhibition by synthetic inhibitors, such as vinyl sulfone compounds, has emerged as a promising treatment strategy. However, the individual reaction steps of protease inhibition are not fully understood. Using the trypanosomal cysteine protease rhodesain as a medically relevant target, we design photoinduced electron transfer (PET) fluorescence probes to detect kinetics of binding of reversible and irreversible vinyl sulfones directly in solution. Intriguingly, the irreversible inhibitor, apart from its unlimited residence time in the enzyme, reacts 5 times faster than …
Partition of Indicaxanthin in Membrane Biomimetic Systems. A Kinetic and Modeling Approach
2009
The solubilization site of indicaxanthin (Ind) in lipid bilayers was investigated by the kinetics of Ind oxidation by peroxyl radicals in water and in aqueous/L-alpha-dipalmitoyl-phosphatidylcholine (DPPC) vesicles, pH 7.4, and 37.0 and 48.0 degrees C, that is, in a gel-like and a crystal liquidlike bilayer state, respectively. The time-dependent Ind absorbance decay, matched with a successful simulation of the reaction kinetic mechanism by Gepasi software, supported a multistep pathway. Computer-assisted analysis allowed calculation of the rate constants associated with the reactions involved, the values of which decreased with increasing DPPC concentration. The binding constant calculated…
Kinetics of the intestinal uptake of zinc acexamate in normal and zinc-depleted rats.
1990
Abstract The uptake of zinc as acexamic acid salt in the small intestine of the anaesthetized rat was shown to be a two-phase process in normal animals. The first phase is rapid mucosal binding which satisfies the Freundlich isotherm equation and which involves about 30 per cent of the initially perfused zinc. The second phase was characterized as an apparent absorption step which obeys Michaelis-Menten and first-order combined kinetics, with the following parameters: Vm = 6.51 mg h−1; Km = 2.96 mg; ka = 0.306 h−1. In largely non-saturated conditions, an apparent global rate constant of about 2.50 h−1 was calculated. No significant interference due to endogenous zinc excretion into the smal…
Synthesis of polymeric derivatives of isoniazid: characterization and in vitro release from a water-soluble adduct with polysuccinimide.
1989
Coupling of isoniazid with polysuccinimide afforded a water-insoluble polymeric pro-drug; by reaction with ethanolamine it was chemically transformed in a water-soluble adduct. The in vitro release of isoniazid from the drug-polymer adduct was studied by using an artificial stomach wall lipid membrane. The transfer rate constant from simulated gastric juice to simulated plasma was defined and compared with that of an equivalent dose of pure drug.
Chromo-Fluorogenic Detection of Nerve-Agent Mimics Using Triggered Cyclization Reactions in Push-Pull Dyes
2010
A family of azo and stilbene derivatives (1-9) are synthesized, and their chromo-fluorogenic behavior in the presence of nerve-agent simulants, diethylchlorophosphate (DCP), diisopropylfluorophosphate (DFP), and diethylcyanophosphate (DCNP) in acetonitrile and mixed solution of water/acetonitrile (3:1 v/v) buffered at pH 5.6 with MES, is investigated. The prepared compounds contain 2-(2-N,N-dimethylaminophenyl)ethanol or 2-[(2-N,N-dimethylamino)phenoxy]ethanol reactive groups, which are part of the conjugated pi-system of the dyes and are able to give acylation reactions with phosphonate substrates followed by a rapid intramolecular N-alkylation. The nerve-agent mimic-triggered cyclization …
Kinetics and mechanism of group transfer polymerization of N-butyl acrylate catalyzed by Hgl2 /(CH3 )3 Sil in toluene
1994
The group transfer polymerization (GTP) of n-butyl acrylate (nBuA) using 1-methoxy-1-(trimethylsiloxy)-2-methyl-1-propene (MTS) as an initiator, mercuric iodide (HgI2) as a catalyst in toluene at room temperature gives a very good control of molecular weight and narrow molecular weight distribution. (Mw/Mn < 1.2). Kinetic studies in this system reveal that this reaction is rather slow, half-lives being in the range of hours. The kinetic order of the apparent rate constant of propagation with respect to initiator and catalyst concentrations were found to be near to unity. However, the first-order time-conversion plots exhibit considerable induction periods. Upon addition of trimethylsilyl io…
Pharmacokinetics of atenolol in relation to renal function
1981
The plasma levels and urinary excretion of carteolol and its main metabolites 8-hydroxycarteolol and carteolol glucuronide were investigated in 6 healthy subjects and 9 patients with varying degrees of renal impairment following a single oral dose of 30 mg carteolol hydrochloride. In healthy subjects the half-life of carteolol was 7.1 h. 63% of the administered dose was recovered unchanged in urine, and in all 84% was excreted by the kidneys. The renal clearance of carteolol was 255 ml/min. In chronic renal failure (CRF) the terminal half-life was increased to a maximum of 41 h. Both the elimination rate constant and renal clearance were closely related to the creatinine clearance. In CRF t…