scholarly journals Thermodynamic and kinetic studies on saccharide binding to soya-bean agglutinin

1986 ◽  
Vol 234 (3) ◽  
pp. 515-522 ◽  
Author(s):  
M J Swamy ◽  
M V Krishna Sastry ◽  
M I Khan ◽  
A Surolia
Keyword(s):  
Thermodynamic Parameters ◽  
Specific Binding ◽  
Activation Parameters ◽  
Kinetic Studies ◽  
Blue Shift ◽  
Single Step ◽  
Soya Bean ◽  
Saccharide Binding ◽  
Delta G ◽  
Kinetics Of

The fluorescence of N-dansylgalactosamine [N-(5-dimethylaminonaphthalene-1-sulphonyl)galactosamine] was enhanced 11-fold with a 25 nm blue-shift in the emission maximum upon binding to soya-bean agglutinin (SBA). This change was used to determine the association constants and thermodynamic parameters for this interaction. The association constant of 1.51 × 10(6) M-1 at 20 degrees C indicated a very strong binding, which is mainly due to a relatively small entropy value, as revealed by the thermodynamic parameters: delta G = −34.7 kJ × mol-1, delta H = −37.9 kJ × mol-1 and delta S = −10.9 J × mol-1 × K-1. The specific binding of this sugar to SBA shows that the lectin can accommodate a large hydrophobic substituent on the C-2 of galactose. Binding of non-fluorescent ligands, studied by monitoring the fluorescence changes when they are added to a mixture of SBA and N-dansylgalactosamine, indicates that a hydrophobic substituent at the anomeric position increases the affinity of the interaction. The C-6 hydroxy group also stabilizes the binding considerably. Kinetics of binding of N-dansylgalactosamine to SBA studied by stopped-flow spectrofluorimetry are consistent with a single-step mechanism and yielded k+1 = 2.4 × 10(5) M-1 × s-1 and k-1 = 0.2 s-1 at 20 degrees C. The activation parameters indicate an enthalpicly controlled association process.

scholarly journals Kinetics of solvolysis in water of four secondary alkyl nitrates

1982 ◽  
Vol 60 (13) ◽  
pp. 1780-1785 ◽  
Author(s):  
Ross Elmore Robertson ◽  
Kalvelil Matthew Koshy ◽  
Adrianne Annessa ◽  
Jan N. Ong ◽  
John Marshall William Scott ◽  
...  
Keyword(s):  
Heat Capacity ◽  
Rate Constant ◽  
Analytical Methods ◽  
Kinetic Data ◽  
Activation Parameters ◽  
Single Step ◽  
Alkyl Nitrates ◽  
Two Stage ◽  
Kinetics Of ◽  
Single Step Reaction

Kinetic data are reported for the solvolysis in water of propane-2-nitrate, butane-2-nitrate, cyclopentyl nitrate, and cyclohexyl nitrate. In each case, the dependence of rate constant on temperature is analysed in terms of two mechanisms for the solvolytic reaction. First it is assumed that the rate constant describes a single step reaction, the analysis leading to estimates of the heat capacity of activation ΔCp≠. Three different analytical methods are discussed in this regard. Second it is assumed that the rate constant describes a two stage mechanism, the first stage being reversible. In this case the explanation of the ΔCp≠ term calculated according to the first mechanism is quite different. We comment on the alternative explanations of trends in activation parameters.

Kinetics of In-111-Platelets in the Baboon: I. Isolation and Labelling of a Viable and Representative Platelet Population

1985 ◽  
Vol 53 (03) ◽  
pp. 404-407 ◽  
Author(s):  
H F Kotzé ◽  
M G Lötter ◽  
P N Badenhorst ◽  
A du P Heyns
Keyword(s):  
Life Span ◽  
Kinetic Studies ◽  
Single Step ◽  
Differential Centrifugation ◽  
Platelet Survival ◽  
The Mean ◽  
Kinetics Of

SummaryA fully representative and viable platelet population was isolated from the blood of 15 baboons by a multiwash procedure, and labelled with In-lll-oxine. The recovery of the total platelet population in the circulation was 85% ± 9. Mean platelet life span was 146 hr ± 13. Correcting for plasma radioactivity (always less than 3.5%) did not significantly affect the estimate of platelet life span (145 hr ± 16) or recovery (85% ± 12). Platelet survival estimates, repeated at different times, were reproducible. In 5 baboons, platelets were also harvested by a single step differential centrifugation. The mean life span of a representative platelet population was significantly longer than that of platelets harvested by a single step. Recovery values of the representative and non-representative population were similar. We conclude that it may be important to harvest and label a fully representative platelet population for kinetic studies. The proposed method is simple and reproducible, and may be applied in studies in humans.

Etude du système acridine orange – poly(C) et de son interaction avec les complexes du palladium(II)

1984 ◽  
Vol 62 (9) ◽  
pp. 1681-1686 ◽  
Author(s):  
Robert Ménard ◽  
Miklos Zador
Keyword(s):  
Acridine Orange ◽  
Thermodynamic Parameters ◽  
Rate Constant ◽  
Kinetic Studies ◽  
Stopped Flow ◽  
Flow Method ◽  
Polycytidylic Acid ◽  
Low Concentrations ◽  
C Complex ◽  
Kinetics Of

The complex formed between acridine orange (AO) and polycytidylic acid (poly(C)) was studied by spectrophotometry and spectrofluorometry. The complex was characterized by its stoichiometry, structure, and the thermodynamic parameters of its formation. The results are in agreement with an external aggregation of the protonated dye along the negatively charged poly(C) chain and indicate that approximately two AO molecules are bound per nucleotide unit of poly(C). The kinetics of the reaction between this complex and a Pd(II) complex was studied by the stopped-flow method. The addition of (dien)Pd(II) to the AO–poly(C) complex leads to the dissociation of the latter, due to fixation of the Pd(II) complex to the N3 site of the cytosine base of poly(C). The rate constant for the AO liberation, extrapolated at zero AO concentration, corresponds to the rate constant of Pd(II) fixation on poly(C). This indicates that AO can be used as an indicator for this reaction and allows kinetic studies at very low concentrations (≤ 5 × 10−6 M).

Kinetics and Mechanism of the 2+ 2 Cycloaddition of Tetracyanoethylene to 2,5-Dimethyl-2,4-Hexadiene

1988 ◽  
Vol 43 (5) ◽  
pp. 435-441 ◽  
Author(s):  
Adel N. Asaad ◽  
Gunnar Aksnes
Keyword(s):  
Complex Formation ◽  
Transition State ◽  
Thermodynamic Parameters ◽  
Cycloaddition Reaction ◽  
Activation Parameters ◽  
Reaction Rates ◽  
Kinetics And Mechanism ◽  
Eda Complex ◽  
Kinetics Of ◽  
Cyclobutane Derivative

The kinetics of the 2 + 2 cycloaddition reaction between tetracyanoethylene and 2,5-dimethyl- 2,4-hexadiene in different solvents has been studied by following the disappearance of the intermediate EDA-complex spectrophotometrically. It is concluded that the EDA-complex is transformed through a concerted cyclicpolar transition state to give the vinyl cyclobutane derivative (III). The effects of various solvents on the reaction rates have been analysed using a multiparameter approach. The thermodynamic parameters (ΔH0 and ΔS0), of EDA-complex formation and the activation parameters (ΔH# and ΔS#) of the cycloaddition have been discussed.

scholarly journals All You Need to Know about the Kinetics of Thermally Stimulated Reactions Occurring on Cooling

Molecules ◽  
2019 ◽  
Vol 24 (10) ◽  
pp. 1918
Author(s):  
Tatsiana Liavitskaya ◽  
Sergey Vyazovkin
Keyword(s):  
Activation Energy ◽  
Differential Scanning Calorimetry ◽  
Kinetic Studies ◽  
Isoconversional Method ◽  
Single Step ◽  
Scanning Calorimetry ◽  
Practical Advice ◽  
Heating And Cooling ◽  
Theoretical Considerations ◽  
Kinetics Of

In this tutorial overview article the authors share their original experience in studying the kinetics of thermally stimulated reactions under the conditions of continuous cooling. It is stressed that the kinetics measured on heating is similar to that measured on cooling only for single-step reactions. For multi-step reactions the respective kinetics can differ dramatically. The application of an isoconversional method to thermogravimetry (TGA) or differential scanning calorimetry (DSC) data allows one to recognize multi-step kinetics in the form of the activation energy that varies with conversion. Authors’ argument is supported by theoretical considerations as well as by experimental examples that include the reactions of thermal decomposition and crosslinking polymerization (curing). The observed differences in the kinetics measured on heating and cooling ultimately manifest themselves in the Arrhenius plots of the opposite curvatures, which means that the heating kinetics cannot be used to predict the kinetics on cooling. The article provides important background knowledge necessary for conducting successful kinetic studies on cooling. It includes a practical advice on optimizing the parameters of cooling experiments as well as on proper usage of kinetic methods for analysis of obtained data.

scholarly journals Kinetic Studies on the Oxidation of Someparaandmeta-Substituted Cinnamic Acids by Pyridinium Bromochromate in the Presence of Oxalic Acid (A Co-oxidation Study)

2009 ◽  
Vol 6 (3) ◽  
pp. 920-927 ◽  
Author(s):  
G. Vanangamudi ◽  
S. Srinivasan
Keyword(s):  
Oxalic Acid ◽  
Activation Parameters ◽  
Kinetic Studies ◽  
Cinnamic Acids ◽  
Kinetics Of Oxidation ◽  
Oxidation Study ◽  
Low Dielectric ◽  
Rate Of Reaction ◽  
Acetic Acid Water ◽  
Kinetics Of

The kinetics of oxidation of cinnamic acids by pyridinium bromochromate (PBC) in the presence of oxalic acid has been studied in acetic acid-water (60:40%) medium. The reaction shows unit order dependence each with respect to oxidant as well as oxalic acid [OX], the order with respect to [H+] and [CA] are fractional. The reaction is acid catalyzed and a low dielectric constant favours the reaction. Increase the ionic strength has no effect on the reaction rate. In the case of substituted cinnamic acids the order with respect to substrate vary depending upon the nature of the substituent present in the ring. In general, the electron withdrawing substituents retard the rate while the electron releasing substituents enhance the rate of reaction. From the kinetic data obtained the activation parameters have been computed and a suitable mechanism has been proposed.

scholarly journals Kinetic Treatment of the Reaction of Fructose and N-Bromosuccinimide in Cationic/Anionic/Nonionic Micelles

2014 ◽  
Vol 2014 ◽  
pp. 1-10
Author(s):  
Minu Singh
Keyword(s):  
Fractional Order ◽  
Activation Parameters ◽  
Kinetic Studies ◽  
Stoichiometric Ratio ◽  
Product Analysis ◽  
First Order ◽  
Order Dependence ◽  
Different Temperatures ◽  
Reaction Stoichiometry ◽  
Kinetics Of

The kinetics of oxidation of fructose by N-bromosuccinimide in acidic medium in the absence and presence of cationic, anionic, and nonionic surfactants has been measured iodometrically under pseudo-first-order condition. The oxidation kinetics of fructose by N-bromosuccinimide shows a first-order dependence on N-bromosuccinimide, fractional order dependence on fructose, and negative fractional order dependence on sulfuric acid. The kinetics is treated using Berezin’s micellar model that was previously used for the catalysis and inhibition of the reaction. The determined stoichiometric ratio was 1 : 1 (fructose : N-bromosuccinimide). The variation of Hg(OAC)2 and succinimide (reaction product) has insignificant effect on reaction rate. Effects of surfactants, added acrylonitrile, added salts, and solvent composition variation have been studied. Activation parameters for the reaction have been evaluated from Arrhenius plot by studying the reaction at different temperatures. The rate law has been derived on the basis of obtained data. A plausible mechanism has been proposed from the results of kinetic studies, reaction stoichiometry, and product analysis.

Growth Kinetics of Quantum Size ZnO Particles

1998 ◽  
Vol 536 ◽  
Author(s):  
E. M. Wong ◽  
J. E. Bonevich ◽  
P. C. Searson
Keyword(s):  
Growth Kinetics ◽  
Ostwald Ripening ◽  
Chemical Potential ◽  
Colloidal Suspensions ◽  
Green Emission ◽  
Blue Shift ◽  
Constant Current ◽  
Mass Model ◽  
Zno Particles ◽  
Kinetics Of

AbstractColloidal chemistry techniques were used to synthesize ZnO particles in the nanometer size regime. The particle aging kinetics were determined by monitoring the optical band edge absorption and using the effective mass model to approximate the particle size as a function of time. We show that the growth kinetics of the ZnO particles follow the Lifshitz, Slyozov, Wagner theory for Ostwald ripening. In this model, the higher curvature and hence chemical potential of smaller particles provides a driving force for dissolution. The larger particles continue to grow by diffusion limited transport of species dissolved in solution. Thin films were fabricated by constant current electrophoretic deposition (EPD) of the ZnO quantum particles from these colloidal suspensions. All the films exhibited a blue shift relative to the characteristic green emission associated with bulk ZnO. The optical characteristics of the particles in the colloidal suspensions were found to translate to the films.

Thermodynamic and Kinetic Investigation of the Solvent Effect on the Oxidation of [Co(en)2SCH2COO]+ with S2O82- In Water-Methanol and Water-tert-Butyl Alcohol Mixtures

1993 ◽  
Vol 58 (5) ◽  
pp. 1001-1006 ◽  
Author(s):  
Oľga Vollárová ◽  
Ján Benko
Keyword(s):  
Transfer Functions ◽  
Activation Parameters ◽  
Butyl Alcohol ◽  
Oxidation Of Co ◽  
Kinetics Of Oxidation ◽  
Tert Butyl ◽  
Tert Butyl Alcohol ◽  
Alcohol Mixtures ◽  
Kinetics Of

The kinetics of oxidation of [Co(en)2SCH2COO]+ with S2O82- was studied in water-methanol and water-tert-butyl alcohol mixtures. Changes in the reaction activation parameters ∆H≠ and ∆S≠ with varying concentration of the co-solvent depend on the kind of the latter, which points to a significant role of salvation effects. The solvation effect on the reaction is discussed based on a comparison of the transfer functions ∆Ht0, ∆St0 and ∆Gt0 for the initial and transition states with the changes in the activation parameters accompanying changes in the CO-solvent concentration. The transfer enthalpies of the reactant were obtained from calorimetric measurements.

Kinetics and Mechanism of Hexachloroiridate(IV) Oxidation of Arsenic(III) in Acidic Perchlorate Solutions

1992 ◽  
Vol 57 (7) ◽  
pp. 1451-1458 ◽  
Author(s):  
Refat M. Hassan
Keyword(s):  
Ionic Strength ◽  
Fractional Order ◽  
Activation Parameters ◽  
Order Reaction ◽  
First Order Reaction ◽  
Intermediate Complex ◽  
Constant Ionic Strength ◽  
Kinetics Of Oxidation ◽  
First Order ◽  
Kinetics Of

The kinetics of oxidation of arsenic(III) by hexachloroiridate(IV) at lower acid concentrations and at constant ionic strength of 1.0 mol dm-3 have been investigated spectrophotometrically. A first-order reaction in [IrCl62-] and fractional order with respect to arsenic(III) have been observed. A kinetic evidence for the formation of an intermediate complex between the hydrolyzed arsenic(III) species and the oxidant was presented. The results showed that decreasing the [H+] is accompanied by an appreciable acceleration of the rate of oxidation. The activation parameters have been evaluated and a mechanism consistent with the kinetic results was suggested.

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