The Esterolytic activity of poly(1-methyl-4- and -5-vinylimidazole) in water

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dc.contributor.author Overberger, C. en_US
dc.contributor.author Smith, Thomas en_US
dc.date.accessioned 2006-08-18T20:55:12Z en_US
dc.date.available 2006-08-18T20:55:12Z en_US
dc.date.issued 1975-07 en_US
dc.identifier.citation Macromolecules 8N4 (1975) 416-424 en_US
dc.identifier.issn 1520-5835 en_US
dc.identifier.uri http://hdl.handle.net/1850/2347 en_US
dc.description.abstract The water solubility of poly(1-Me-5-VIm) has made it possible to achieve phenomenal rate enhancements and to gain even greater insight into the mechanism of catalysis by polymeric imidazoles. The poly(l-Me-5-V1m)-catalyzed hydrolysis of S12- exhibited saturation in excess catalyst and in excess substrate. Inhibition of the poly( 1-Me-5-Vim) catalyzed hydrolysis of Sn- type substrates by analog inhibitors was also observed. The saturation apparently did not follow a simple Michaelis-Menten mechanism; however, the results could be rationalized by analogy to certain enzymatic systems. Multisite enzymes have long been known to display kinetic patterns different from that exhibited by enzymes with only one active site, i.e., such phenomena as sigmoidal rate vs. [S] plots. These phenomena may arise entirely as a result of the multisite nature of the enzyme. Consequently, a synthetic macromolecular catalyst with multiple sites might also be expected to display such characteristics. The poly(1-Me-5-VIm)-catalyzed hydrolysis of Sl2- is apparently the first synthetic system in which such phenomena have been observed. The intermediacy of an apolar polymer substrate complex for the poly(l-Me-5-VIm)-catalyzed hydrolysis of S12- in water was given support by studies of the effect of temperature on the rate of hydrolysis. Activation parameters were determined for catalysis by 1,5-DMIm and by poly(1-Me-5-VIm). These results showed that the rate enhancement exhibited by the polymer was due entirely to a favorable entropy term. en_US
dc.format.extent 31371 bytes en_US
dc.format.mimetype application/pdf en_US
dc.language.iso en_US en_US
dc.publisher American Chemical Society: Macromolecules en_US
dc.subject Esterolysis en_US
dc.subject Hydrolysis en_US
dc.subject Polymers en_US
dc.title The Esterolytic activity of poly(1-methyl-4- and -5-vinylimidazole) in water en_US
dc.type Abstract en_US
dc.identifier.url http://dx.doi.org/10.1021/ma60046a008

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