Catalytic properties of supramolecular systems based on polyoxyethylated calixarenes and amines

The rate of carboxylic ester cleavage by amphiphilic low-molecular-weight and polymeric amines in the presence of polyoxyethylated calix[4]arenes with different degrees of oxyethylation is determined by the formation of mixed aggregates, by the shift of pK a of the amine, and the character of the distribution of the reactants in functional micelles. All of the systems show a high substrate specificity. In the case of octyl- and decylamines, the reaction of p-nitrophenyl acetate is catalyzed and the reaction of more hydrophobic p-nitrophenyl laurate is inhibited. An opposite situation is observed in the systems based on branched polyethyleneimine: the reaction of p-nitrophenyl acetate is inhibited and the process involving p-nitrophenyl laurate is accelerated.