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Synthesis and esterolytic chemistry of some (dialkylamino) pyridine-functionalized micellar aggregates. Evidence of catalytic turnover

Bhattacharya, Santanu and Snehalatha, Karnam (1995) Synthesis and esterolytic chemistry of some (dialkylamino) pyridine-functionalized micellar aggregates. Evidence of catalytic turnover. In: Langmuir, 11 (12). pp. 4653-4660.

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Official URL: http://pubs.acs.org/doi/abs/10.1021/la00012a013

Abstract

Four new (dialkylamino)pyridine-functionalized surfactants have been synthesized. Micelles were generated either from the surfactant alone in aqueous buffer (pH 8.5 or 9.0) or by comicellization in 1 x 10(-3)-1 x 10(-4) M aqueous micellar cetyltrimethylammonium bromide (CTABr) solution at pH 8.5 or 9.0. Such aggregates were used to cleave p-nitrophenyl alkanoates or p-nitrophenyl diphenylphosphate. The nucleophilic reagents and the second-order ''catalytic'' rate constants toward esterolysis of the substrate p-nitrophenyl octanoate (at 25 degrees C, pH 9.0) were [cat.] = 1 x 10(-4) M, [CTABr] = 1 x 10(-3) M, and k(cat.) = 440.13 M(-1) s(-1) for 1b, [cat.] = 5 x 10(-4) M, [CTABr] = 5 x 10(-4) M, and k(cat.) = 30.8 M(-1) s(-1) for 1c, [cat.] = 5 x 10(-4) M, [CTABr] = 5 x 10(-3) M, and k(cat.) = 183.64 M(-1) s(-1) for 2a, and [cat.] = 3 x 10(-4) M and k(cat.) = 54.1 M(-1) s(-1) for 2b. The catalytic systems, especially 1b/CTABr and 2a/CTABr, also conferred significantly greater reactivity toward the esters derived from alkanoic acids of moderate chain length (C-6-C-10) during hydrolytic cleavages relative to their shorter and longer counterparts. Importantly, the catalytic systems comprising the coaggregates of either neutral 1b and CTABr (1:10) or anionic 2a and CTABr (1:10) conformed to the Michaelis-Menten kinetic scheme and demonstrated turnover behavior in the presence of excess substrate.

Item Type: Journal Article
Additional Information: Copyright of this article belongs to American Chemical Society.
Department/Centre: Division of Chemical Sciences > Organic Chemistry
Date Deposited: 26 May 2011 06:38
Last Modified: 26 May 2011 06:38
URI: http://eprints.iisc.ernet.in/id/eprint/37941

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