ISSN:
0360-6376
Keywords:
Physics
;
Polymer and Materials Science
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The solvolytic reactions of anionic activated esters (Sn-) catalyzed by dodecane-block-poly[ethylenimine-graft-4(5)-methylimidazole] and related model compounds were investigated. Hydrolysis of 4-acetyl-3-nitrobenzoic acid (S2-) as a function of pH suggested that electrostatic interactions are operative only in the higher molecular weight polymers. Apolar interactions were evident from the greater catalytic rates observed for the hydrolysis of a series of 4-acetoxy-3-nitrobenzoic acid substrates (Sn-). The largest rate enhancements were reflected by catalysts that make effective use of the electrostatic interaction and also provide an apolar binding site. Dodecane-block-poly[ethylenimine-graft-4(5)-methylimidazole], with a DP = 85, catalyzed hydrolysis of Sn-(n = 2, 4, and 7), in excess substrate, exhibited saturation kinetics and followed a simple Michaelis-Menten-type mechanism. Inhibition of the catalyst in the hydrolysis of S12- was observed and can be rationalized by analogy to certain multisite enzymatic reactions.
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/pol.1981.170190715
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