Cooperativity in bimolecular micelle-catalyzed reactions. Inhibition of catalysis by high concentrations of detergent

Piszkiewicz, Dennis

doi:10.1021/ja00465a046

Cited by 74 publications

(40 citation statements)

References 3 publications

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“…The Piszkiewicz model, 15,[31][32][33] analogous to the Hill model applied to the enzyme-catalyzed reactions 34 may be considered here with some modifications. According to this model, it is assumed that substrate molecule, MG …”

Section: Resultsmentioning

confidence: 99%

Kinetics Study of Malachite Green Fading in the Presence of TX-100, DTAB and SDS

2009

Bulletin of the Korean Chemical Society

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The rate constants of alkaline fading of malachite green (MG + ) was measured in the presence of nonionic (TX-100), cationic (DTAB) and anionic (SDS) surfactants. This reaction was studied under pseudo-first-order conditions at 283∼303 K. The rate of fading reaction showed noticeable dependence on the electrical charge of the used surfactants. It was observed that the reaction rate constants were increased in the presence of TX-100 and DTAB and decreased in the presence of SDS. According to Hughs-Ingold rules for nucleophilic substitution reactions, the electric charge of MG/surfactant compound along with decrease in dielectric constant of MG + micro-environment in this compound varies the rate of fading reaction. Binding constants of surfactant molecules to MG + were calculated using cooperativity, pseudo-phase ion exchange and classical models and the related thermodynamic parameters were obtained by classical model. The results show that the binding of MG + to TX-100 is exothermic and binding of MG + to DTAB and SDS in some concentration ranges of the used surfactants is endothermic and in the other ones is exothermic.

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Section: Resultsmentioning

confidence: 99%

Kinetics Study of Malachite Green Fading in the Presence of TX-100, DTAB and SDS

2009

Bulletin of the Korean Chemical Society

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“…Both bind substrate in a non-covalent manner. The kinetics of micellar catalysis also resembles that of enzyme catalysis as described in various investigations [6,7,[25][26][27].…”

Section: General Mechanism Of Reaction Of Dyes With Cyanide Ionmentioning

confidence: 88%

Kinetic studies on sodium dodecyl sulfate micelle inhibited reactions of triphenylmethyl carbocations with cyanide ion

Singh¹,

Luwang

Srivastava

2011

Reac Kinet Mech Cat

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The kinetics of the decolorization reactions of triphenylmethane dyes (BG, MG and PRH) with the cyanide ion (nucleophile) were studied in the presence of anionic micelles of sodium dodecyl sulfate (SDS). The reactions follow pseudofirst order kinetics. The rate constant depends on surfactant concentration. SDS micelles inhibit the overall rate of the reaction between the dye carbocation with the nucleophile. Quantitative analysis of the micellar data obtained has been done by applying a positive cooperativity model of enzyme catalysis. For all the dyes under study, the value of n (index of cooperativity) has been found to be greater than one. The inhibitory effect has been explained in terms of hydrophobic and electrostatic interactions of various species present in the reaction systems.

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“…5) may be explained with the idea of positive cooperativity in the enzymatic reaction. On the basis of the Piszkiewicz model, it may be thought that the substrate molecule and a small number of surfactant molecule aggregate to form catalytic micelles [46], which are somewhat different from normal micelles consisting of a larger number of surfactant molecules. These catalytic micelles react with the oxidant to yield the products at a faster rate.…”

Section: Discussionmentioning

confidence: 99%

Effects of nonionic micellar aggregates on the electron transfer reaction between l‐glutamic acid and gold(III) complexes

Sen

Gani

Midya

et al. 2012

Int J of Chemical Kinetics

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The effect of nonionic micelles of Triton X-100 on the oxidative decarboxylation of L-glutamic acid by chloroaurate(III) complexes has been investigated in acetate buffer medium. The reaction is first order with respect to Au(III), but a complex order with respect to glutamate. H + ion has both accelerating and retarding effects in the pH range 3.72-4.80, whereas a Cl − ion has an inhibiting effect in the range 0.02-0.56 mol dm −3 . Under the experimental conditions, AuCl − 4 and AuCl 3 (OH) − are the predominant and effective oxidizing species, whereas the zwitterion (H 2 A) and mononegative anion (HA − ) are the predominant reducing species of the amino acid. The reaction involves a one-step two-electron transfer process and passes through the intermediate formation of iminic cation. In the presence of surfactant, the reaction passes through a maximum and it appears to follow Berezin's model, where both the oxidant and the substrate are partitioned between the aqueous and the micellar phase and then react. The binding constants between the reactants and the surfactant have been evaluated at different temperatures. Compensation between substrate-water interaction and substrate-micelle interaction plays an important role in such redox reactions in the presence of a surfactant.

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Cooperativity in bimolecular micelle-catalyzed reactions. Inhibition of catalysis by high concentrations of detergent

Cited by 74 publications

References 3 publications

Kinetics Study of Malachite Green Fading in the Presence of TX-100, DTAB and SDS

Kinetics Study of Malachite Green Fading in the Presence of TX-100, DTAB and SDS

Kinetic studies on sodium dodecyl sulfate micelle inhibited reactions of triphenylmethyl carbocations with cyanide ion

Effects of nonionic micellar aggregates on the electron transfer reaction between l‐glutamic acid and gold(III) complexes

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