摘 要: | Hydrolysis of various carboxylic esters of N-alkyl-3-hydroxypyridinium iodide(2—5) has been studied, both in the absence and in the presence of sodium carboxymethylamylose(NaCMA 1). In the absence of Na-CMA, the hydrolysis of all four substrates follows 2nd-order kinetics when HPO_4~- and CH_3CO_2~- ions are used as the attacking nucleophites. In the presence of 1, however, the course of the reaction depends on the structure of the substrates. For 2 and 3, the observed rate constants k_(obs) are independent of the eoncentration of 1 added, but for those with long hydrocarbon chains, i. e. 4 and 5, the hydrolysis follows MichaelisMenten kinetics. All other experimental results also indicate the formation of supramolecular(incluston) complexes between the Na-CMA host molecules in helical conformations and theesters 4 and 5. In comparison with the bimolecular processes in the bulk phase, the catalytic efficiencies(k_c/K_d) of these supramolecular systems are 3.7×10~4 and 1.7×10~4 times that of the aceta
|