Imidazole Catalyses in Aqueous Systems. I. The Enzyme-like Catalysis in the Hydrolysis of a Phenyl Ester by Imidazole-Containing Copolymers

Toyoki Kunitake, Fumiko Shimada, Chuji Aso

研究成果: Contribution to journalArticle査読

52 被引用数 (Scopus)

抄録

Hydrolyses of 3-nitro-4-acetoxybenzoic acid catalyzed by copolymers of 1-vinyl-2-methylimidazole with 1-vinylpyrrolidone (copolymer A) and with acrylamide (copolymer B) were studied at 30° and mostly at pH 8.0 in 1.0 M aqueous KCl. The rate of the catalytic hydrolysis could be described by Michaelis-Menten kinetics, showing substrate saturation phenomena at high substrate concentrations, as in enzymatic reactions. Copolymer A of low (<20%) imidazole contents showed the same kinetic pattern, independent of the copolymer composition, and gave Km (dissociation constants of the catalyst-substrate complex) of 9.3 mM and k3 (first-order rate constant of the pseudo-intramolecular product formation) of 0.038 min-1. Copolymer B gave Km of 63 mM and k3 of 0.11 min-1. When, however, copolymer A contained higher amounts of the imidazole unit, the kinetic pattern was not the simple Michaelis-Menten type and the over-all catalytic efficiency decreased, suggesting the presence of the catalytic site of a differing nature. The substrate binding was attributed to hydrophobic interaction, since the electrostatic interaction between catalyst and substrate was found negligible. The kinetic characteristics of copolymer A were reasonably explained by assuming the loop formation of the polymer segment surrounding the substrate molecule. Finally, probable reasons for the relatively small k3 value for copolymer A were discussed, taking the nature of the catalytic site into consideration.

本文言語英語
ページ(範囲)2716-2723
ページ数8
ジャーナルJournal of the American Chemical Society
91
10
DOI
出版ステータス出版済み - 5 1969

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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