scholarly journals Kinetics of the Reversible Transformation of 2,3-Dioxogulonic Acid into its Enol as a Function of the pH of the Medium

1978 ◽  
Vol 33 (10) ◽  
pp. 1184-1189
Author(s):  
J. Zuluaga ◽  
P. Martínez
Keyword(s):  
Kinetic Study ◽  
Equilibrium Constant ◽  
Rate Constants ◽  
Disodium Salt ◽  
Stopped Flow ◽  
Free Energies ◽  
Reversible Transformation ◽  
Flow Method ◽  
Kinetic Coefficients ◽  
Kinetics Of

Abstract 2,3-dioxogulonic acid and the disodium salt of its enol were synthesised, isolated and identified both chemically and spectroscopically. A kinetic study was carried out on its equilibrium by means of the “stopped flow” method for rapid processes, and the rate constants for the forward and backward reaction were determined as a function of the pH of the medium. The kinetic coefficients involved, equilibrium constant and Gibbs free energies were also determined.

Mechanism of bromination of a quaternary pyrimidinium cation. Change of rate determining step with acidity

1978 ◽  
Vol 56 (23) ◽  
pp. 2970-2976 ◽  
Author(s):  
Oswald S. Tee ◽  
David C. Thackray ◽  
Charles G. Berks
Keyword(s):  
Kinetic Study ◽  
Rate Constants ◽  
Aqueous Media ◽  
Stopped Flow ◽  
Flow Method ◽  
High Acidity ◽  
Rate Determining Step ◽  
Kinetics Of ◽  
Good Agreement

The kinetics of bromination of the 1,2-dihydro-1,3-dimethyl-2-oxopyrimidinium cation (Q+) in aqueous media (pH 0–5) have been studied using the stopped-flow method. At the higher acidities (pH < 2) the results are consistent with rate determining attack by bromine upon the pseudobase (QOH), whereas at low acidities (pH > 4) it appears that pseudobase formation is rate determining. The change occurs because at high acidity the reversal of the pseudobase QOH to the cation is fast relative to bromine attack, whereas at low acidity the converse is true. Results obtained at intermediate acidities (pH 2–4) are consistent with this interpretation.A separate kinetic study of pseudobase formation (and decomposition) yielded rate constants in good agreement with those derived from the bromination study.

The kinetics of partial processes in the oxidation of ascorbic acid catalyzed by vanadyl tetrasulphophthalocyanine

1982 ◽  
Vol 47 (3) ◽  
pp. 744-754 ◽  
Author(s):  
Dana M. Wagnerová ◽  
Jaroslav Votruba ◽  
Jürgen Blanck ◽  
Josef Vepřek-Šiška
Keyword(s):  
Experimental Data ◽  
Ascorbic Acid ◽  
Reaction Mechanism ◽  
Rate Constants ◽  
Stopped Flow ◽  
Adaptive Identification ◽  
Flow Method ◽  
Acid Catalyzed ◽  
Kinetics Of

The rapid partial reactions of the oxidation of ascorbic acid by dioxygen with vanadyl tetrasulphophthalocyanine as a catalyst were studied by the stopped-flow method. The experimental data were treated on a computer and compared with the kinetic implications resulting from the proposed mechanism. Application of the adaptive identification method led to quantitative solution of the mechanism, i.e. determination of the values of all the isolated rate constants of the reaction mechanism.

scholarly journals Metal Enolates – Enamines – Enol Ethers: How Do Enolate Equivalents Differ in Nucleophilic Reactivity?

Synthesis ◽  
2019 ◽  
Vol 51 (05) ◽  
pp. 1157-1170 ◽  
Author(s):  
Artem Leonov ◽  
Daria Timofeeva ◽  
Armin Ofial ◽  
Herbert Mayr
Keyword(s):  
Rate Constants ◽  
Correlation Equation ◽  
Stopped Flow ◽  
Quinone Methides ◽  
Enol Ethers ◽  
Reactivity Descriptors ◽  
Silyl Enol Ethers ◽  
Nucleophilic Reactivity ◽  
Kinetics Of ◽  
Least Squares Minimization

The kinetics of the reactions of trimethylsilyl enol ethers and enamines (derived from deoxybenzoin, indane-1-one, and α-tetralone) with reference electrophiles (p-quinone methides, benzhydrylium and indolylbenzylium ions) were measured by conventional and stopped-flow photometry in acetonitrile at 20 °C. The resulting second-order rate constants were subjected to a least-squares minimization based on the correlation equation lg k = s N(N + E) for determining the reactivity descriptors N and s N of the silyl enol ethers and enamines. The relative reactivities of structurally analogous silyl enol ethers, enamines, and enolate anions towards carbon-centered electrophiles are determined as 1, 107, and 1014, respectively. A survey of synthetic applications of enolate ions and their synthetic equivalents shows that their behavior can be properly described by their nucleophilicity parameters, which therefore can be used for designing novel synthetic transformations.

scholarly journals The Kinetics of Peroxynitrite on Insulin Nitration Damage

2020 ◽  
Author(s):  
Congxiao Zhang ◽  
Fusheng Sun ◽  
Congjiang Zhang ◽  
Yunjing Luo
Keyword(s):  
Activation Energy ◽  
Biological Activity ◽  
Glucose Metabolism ◽  
Rate Constants ◽  
The Body ◽  
Stopped Flow ◽  
Tyrosine Nitration ◽  
Protein Nitration ◽  
Physiological Conditions ◽  
Kinetics Of

Abstract Background: Insulin is one of the most important versatile hormones that is central to regulating the energy and glucose metabolism in the body. There has been accumulating evidence supporting that diabetes was associated with peroxynitrite and protein nitration, and insulin nitration induced by peroxynitrite affected its biological activity. Methods: In this paper, the kinetics of insulin nitration by peroxynitrite in physiological conditions was studied by the stopped flow technique. Results: We determined the values of the reactive rate constants of peroxynitrite decomposition and peroxynitrite-induced tyrosine nitration in the presence of insulin. The activation energy of peroxynitrite decomposition and 3-nitrotyrosine yield in the presence of insulin is 48.8 kJ·mol−1 and 42.7 kJ·mol−1 respectively. Conclusions: It is inferred that the glutamate residue of insulin accelerated peroxynitrite decomposition and tyrosine nitration by reducing the activation energy of reactions. The results could be beneficial for exploring the molecular mechanism of diabetes and offering a new target for diabetes therapies.

Kinetic Study of the Oxidation of Alcohols with Quaternary Ammonium Permanganates

1993 ◽  
Vol 58 (8) ◽  
pp. 1777-1781 ◽  
Author(s):  
Robert Šumichrast ◽  
Vladislav Holba
Keyword(s):  
Kinetic Study ◽  
Catalytic Reaction ◽  
Rate Constants ◽  
Quaternary Ammonium ◽  
Iterative Procedure ◽  
Activation Parameters ◽  
Reaction Products ◽  
Thermodynamic Activation Parameters ◽  
Oxidation Of Alcohols ◽  
Kinetics Of

Kinetics of the oxidation of 2-propanol, 1-butanol, and 1-pentanol with tetraalkylammonium permanganates have been investigated as function of temperature. The studied reactions are partly autocatalytic, colloidal manganese dioxide as one of the reaction products has been identified as the autocatalyst.A computerized iterative procedure has been used in order to obtained the rate constants of both non-catalytic and catalytic reaction steps together with the thermodynamic activation parameters.

scholarly journals KINETIC STUDY ON ANIONIC σ-COMPLEX FORMATION BETWEEN 2,4,6-TRINITROANISOLE AND METHOXIDE ION BY HIGH PRESSURE STOPPED-FLOW METHOD

1979 ◽  
Vol 8 (6) ◽  
pp. 671-674 ◽  
Author(s):  
Noboru Takisawa ◽  
Muneo Sasaki ◽  
Fujitsugu Amita ◽  
Jiro Osugi
Keyword(s):  
High Pressure ◽  
Complex Formation ◽  
Kinetic Study ◽  
Stopped Flow ◽  
Flow Method ◽  
Methoxide Ion

The retroaldol reaction of 3-methyl-2-butenal

1983 ◽  
Vol 61 (1) ◽  
pp. 171-178 ◽  
Author(s):  
J. Peter Guthrie ◽  
Brian A. Dawson
Keyword(s):  
Sodium Hydroxide ◽  
Equilibrium Constant ◽  
Rate Constants ◽  
Equilibrium Constants ◽  
Aqueous Sodium Hydroxide ◽  
Initial Increase ◽  
Aqueous Sodium ◽  
Rate Determining Step ◽  
Kinetics Of

In aqueous sodium hydroxide solutions at 25 °C, 3-methyl-2-butenal, 1c, undergoes retroaldol cleavage to acetone and acetaldehyde. The kinetics of the retroaldol reaction were followed spectrophotometrically at 242 nm and showed simple first order behavior. When 3-methyl-3-hydroxybutanal, 2c, was added to aqueous sodium hydroxide solutions at 25 °C, there was an initial increase in absorbance at 242 nm, attributed to formation of 1c, followed by a 20-fold slower decrease; the rate of the slow decrease matches the rate of disappearance of 1c under the same conditions. Analysis of the kinetics allows determination of the three rate constants needed to describe the system: khyd = 0.00342; kdehyd = 0.00832; kretro = 0.0564; all M−1 s−1. The equilibrium constant for enone hydration is 0.41. Rate constants for the analogous reactions for acrolein and crotonaldehyde could be obtained from the literature. There is a reasonable rate–equilibrium correlation for the retroaldol step. For the enone hydration step, rate and equilibrium constants respond differently to replacement of hydrogen by methyl. It is proposed that this results from release of strain after the rate-determining step by rotation about a single bond; this decrease in strain is reflected in the equilibrium constant but not in the rate constant.

Etude cinétique des systèmes Cu(II)•Adénosine et Cu(II)•D-Ribose

1972 ◽  
Vol 50 (19) ◽  
pp. 3117-3123 ◽  
Author(s):  
G. Boivin ◽  
M. Zador
Keyword(s):  
Kinetic Parameters ◽  
Acidic Medium ◽  
Temperature Jump ◽  
Strong Acid ◽  
Basic Medium ◽  
Stopped Flow ◽  
Acid Solutions ◽  
Flow Method ◽  
Kinetics Of ◽  
Adenine Base

The kinetics of the formation and dissociation of Cu(II) complexes of adenosine have been determined in acidic and basic medium. In acidic medium, the complex is formed between the Cu(II) and the adenine base and the kinetic parameters have been obtained in this case using a temperature jump method. In basic medium, only the dissociation of the complexes could be studied by a stopped-flow method, by addition of EDTA or strong acid solutions. In these complexes, Cu(II) is bridged with ribose hydroxyls. Finally, D-ribose has also been studied for comparison in the same conditions. The mechanism of these reactions is discussed.

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