scholarly journals The kinetics and mechanism of the organo-iridium-catalysed enantioselective reduction of imines

2016 ◽  
Vol 14 (14) ◽  
pp. 3614-3622 ◽  
Author(s):  
Matthew J. Stirling ◽  
Gemma Sweeney ◽  
Kerry MacRory ◽  
A. John Blacker ◽  
Michael I. Page
Keyword(s):  
Enantiomeric Excess ◽  
Zero Order ◽  
Kinetics And Mechanism ◽  
First Order ◽  
Enantioselective Reduction ◽  
First Order Kinetics

The enantiomeric excess (ee) for the organo-iridium catalysed reduction of imines decreases during the reaction because the rate of formation of the (R)-product amine follows first-order kinetics whereas that for the (S)-enantiomer is zero-order.

Ag nanoparticles stabilized on cubic polyhedral oligomeric silsesquioxane cross-linked poly(N-isopropyl acrylamide-co-itaconic acid): An efficient catalyst for 4-nitrophenol reduction

2020 ◽  
Vol 13 (07) ◽  
pp. 2051040
Author(s):  
Vahid Rahimkhoei ◽  
Ali Akbari ◽  
Maryam Zirak ◽  
Bagher Eftekhari-Sis
Keyword(s):  
Itaconic Acid ◽  
Ag Nanoparticles ◽  
Zero Order ◽  
Polymeric Support ◽  
Efficient Catalyst ◽  
First Order ◽  
First Order Kinetics ◽  
Isopropyl Acrylamide ◽  
Nitrophenol Reduction ◽  
Oligomeric Silsesquioxane

Ag nanoparticles were synthesized and stabilized on a polymeric support, poly([Formula: see text]-isopropyl acrylamide-co-itaconic acid)/POSS, by simply reducing Ag[Formula: see text] ions adsorbed in the interior of the polymeric network. The prepared Ag@p(NIPAM-IA)/POSS was used as an efficient and recyclable catalyst for removal of the 4-nitrophenol (4-NP) contaminant by NaBH4-induced reduction to 4-aminophenol (4-AP) in aqueous solution. Different conditions including Ag content and amount of the nanocomposite, and also temperature of the 4-NP reduction were investigated. Also, two kinetic models, zero-order and first-order kinetics, were studied for the reduction of 4-NP to 4-AP.

Kinetics and mechanism of the osmium-tetroxide-catalysed oxidation of mandelate ion by hexacyanoferrate(III) ion

1968 ◽  
Vol 21 (12) ◽  
pp. 2913 ◽  
Author(s):  
NP Singh ◽  
VN Singh ◽  
MP Singh
Keyword(s):  
Benzoic Acid ◽  
Oxidation Product ◽  
Osmium Tetroxide ◽  
Reaction Rate ◽  
Zero Order ◽  
Ion Concentration ◽  
First Order ◽  
First Order Kinetics ◽  
Catalysed Oxidation ◽  
Hydroxyl Ion

The osmium-tetroxide-catalysed oxidation of mandelate ion by hexacyanoferrate(111) ion has been studied kinetically. The reaction rate has been found to be independent of hexacyanoferrate(111) ion while the order with respect to both osmium tetroxide and mandelate ion comes out to be unity. The reaction rate follows first-order kinetics at low hydroxyl ion concentration and becomes zero order at higher concentrations. The course of the reaction has been considered to proceed through the formation of an activated mandelate-OsO4, complex which decomposes in alkaline medium giving reduced osmium(V1) followed by a fast oxidation by hexacyanoferrate(111) ion. The probable course of the reactions is also described with the help of its oxidation product, benzoic acid.

Parameters Effect on Photocatalytic Reduction Kinetics of Bromate in Aqueous Dispersion of TiO2

2013 ◽  
Vol 779-780 ◽  
pp. 1658-1665
Author(s):  
Rong Shu Zhu ◽  
Fei Tian ◽  
Ling Ling Zhang ◽  
Ling Min Yu
Keyword(s):  
Aqueous Dispersion ◽  
Zero Order ◽  
Photocatalytic Reduction ◽  
Reduction Kinetics ◽  
First Order ◽  
First Order Kinetics ◽  
Zero Order Kinetics ◽  
Experimental Parameters ◽  
Pseudo First Order ◽  
Kinetics Of

This paper studied the photocatalytic reduction kinetics of bromate in aqueous dispersion of TiO2 and investigated the effects of experimental parameters, including initial concentration of BrO3-, pH, TiO2 dosage, anion and cation. The results indicate that the process of photocatalytic reduction of bromate follows a zero-order kinetics. In all the investigated experimental parameters, the initial bromate concentration, pH and anion have great effect on the photocatalytic reduction kinetics. The processes of photocatalytic reduction of bromate show the pseudo first-order kinetics at initial bromate concentration of 0.39 μmolL-1, pH=5.0, or in presence of HCO3-/CO32-, NO3-, SO42-, respectively.

Use of purified lyophilized human lactate dehydrogenase isoenzymes in a study of the measurement of lactate dehydrogenase activity.

1986 ◽  
Vol 32 (5) ◽  
pp. 758-762 ◽  
Author(s):  
D A Smith ◽  
G C Moses ◽  
A R Henderson
Keyword(s):  
Lactate Dehydrogenase ◽  
Zero Order ◽  
Lactate Dehydrogenase Activity ◽  
First Order ◽  
First Order Kinetics ◽  
Activity Concentrations ◽  
Zero Order Kinetics ◽  
Specific Activities ◽  
The Stability ◽  
Lactate Dehydrogenase Isoenzymes

Abstract We examined the stability of human lactate dehydrogenase (EC 1.1.1.27; LD) isoenzymes 1, 2, and 3--purified to specific activities of about 200 kU/g--when lyophilized in a buffered stabilized matrix of bovine albumin. Each isoenzyme was prepared at two activity concentrations and stored at -20, 4, 20, 37, and 56 degrees C for as long as six months. LD-1 activity decayed with zero-order kinetics, LD-2 and LD-3 with first-order kinetics. The extrapolated half-lives of these preparations at -20 degrees C varied between 80 and 530 years. Stability of reconstituted samples stored at 4 degrees C was excellent for LD-1 but poor for LD-2 and LD-3. We suggest that preparations of human LD-1 be further investigated as a possible reference material.

Kinetics and mechanism of dealkylation of coordinated isocyanide in Fe(PMe3)2(t-BuNC)3

2005 ◽  
Vol 83 (6-7) ◽  
pp. 626-633 ◽  
Author(s):  
Christine L Tennent ◽  
William D Jones
Keyword(s):  
Hydrogen Atom ◽  
Iron Complex ◽  
Kinetics And Mechanism ◽  
Zerovalent Iron ◽  
Mechanistic Studies ◽  
First Order ◽  
Tert Butyl ◽  
Preferential Formation ◽  
First Order Kinetics ◽  
Thermal Cleavage

The zerovalent iron complex Fe(PMe3)2(t-BuNC)3 undergoes thermal cleavage of the C—N bond to give Fe(PMe3)2(t-BuNC)2(H)(CN) and isobutylene. The reaction follows first order kinetics, and addition of the hydrogen-atom donor 1,4-cyclohexadiene leads to the preferential formation of isobutane rather than isobutylene. Mechanistic studies are consistent with a rate determining homolysis of the C—N bond, giving rise to tert-butyl radicals.Key words: iron, isocyanide, elimination, C—N cleavage.

Investigations into the kinetics and stoichiometry of bacterial oxidation of covellite (CuS) using a polarographic oxygen probe

1978 ◽  
Vol 24 (8) ◽  
pp. 998-1003 ◽  
Author(s):  
Pamela A. D. Rickard ◽  
Donald G. Vanselow
Keyword(s):  
Oxygen Uptake Rate ◽  
Zero Order ◽  
Bacterial Oxidation ◽  
Kinetics Of Oxidation ◽  
First Order ◽  
Cupric Ion ◽  
First Order Kinetics ◽  
Zero Order Kinetics ◽  
Cupric Sulphate ◽  
Kinetics Of

"Oxygraph" apparatus was used to measure quantitatively the kinetics of oxidation of synthetic covellite (CuS) in the presence and absence of Thiobacillus species. The expected stoichiometric relationship between oxygen consumed and cupric sulphate produced was verified by atomic absorption assays of cupric ion and sulphate ion. Thiobacillus cultures markedly increased the oxidation rate.The dependence of each oxygen-uptake rate on oxygen concentration was also measured. Sterile controls and some bacterial cultures showed first-order kinetics while other cultures showed zero-order kinetics.Addition of biological inhibitors to reacting slurries revealed that cultures showing first-order kinetics did not oxidize CuS itself but merely oxidized elemental sulphur formed by non-enzymic oxidation of CuS. Cultures showing zero-order kinetics oxidized CuS in a way that resulted in all oxygen reduction being enzymic. This mechanism possibly involves the cyclic oxidation and reduction of soluble iron.

Ring-Opening Polymerization of ε-Caprolactone Using Novel Tin(II) Alkoxide Initiators

2008 ◽  
Vol 55-57 ◽  
pp. 757-760 ◽  
Author(s):  
A. Kleawkla ◽  
Robert Molloy ◽  
W. Naksata ◽  
Winita Punyodom
Keyword(s):  
Solid State ◽  
Rate Constants ◽  
Ring Opening ◽  
Ring Opening Polymerization ◽  
Zero Order ◽  
Molecular Aggregation ◽  
First Order ◽  
First Order Kinetics ◽  
Zero Order Kinetics ◽  
Kinetics Of

Two novel tin(II) alkoxides, namely: tin(II) hexoxide, Sn(OC6H13)2, and tin(II) octoxide, Sn(OC8H17)2, have been synthesized for use as coordination-insertion initiators in the bulk ring-opening polymerization of ε-caprolactone. The kinetics of the polymerization reactions were studied at 140 °C by dilatometry. It was found that both alkoxides were slow to dissolve in the ε-caprolactone monomer due to their molecular aggregation in the solid state. As a result, the slow solubilization of the initiators gave rise to deviations from the expected first-order kinetics. Instead, the kinetic results adhered more closely to zero-order kinetics with apparent zero-order rate constants k0 of 6.58 x 10-2 and 4.63 x 10-2 mol l-1 min-1 for the hexoxide and octoxide respectively

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