Design of supramolecular biomimetic catalysts of high substrate specificity by noncovalent self-assembly of calix[4]arenes with amphiphilic and polymeric amines

Supramolecular biomimetic catalysts of high substrate specificity are developed based on amphiphilic oxyethylated calix[4]arene bearing iso-nonyl fragments at the upper rim and hexadeca(ethylene glycol) fragments at lower rim (9CO16), and amines of amphiphilic or polymeric nature. Two critical concentrations determined by tensiometry and dye solubilization methods are probably reflect the onset of association process and transition from bimodal to monomodal size distribution revealed by the dynamic light scattering method. Amine components used may form aggregates as well, which is mediated by hydrophobic effect due to occurrence of long-chain alkyl tails. The micellar rate effect of the designed systems toward the cleavage of carboxylic acid ester is shown to be contributed by the formation of mixed aggregates with the reactive functional groups, as well as by the pK(a) shift of the amine and the character of the distribution of reagents in functional micelles. In the case of long-chain primary amines, an inversion of micellar rate effect (catalysis to inhibition) occurs upon transferring from the less hydrophobic substrate, p-nitrophenyl acetate, to the more hydrophobic analogs, p-nitrophenyl laurate and p-nitrophenyl caprinate. The opposite effect (inhibition of the reaction of p-nitrophenyl acetate and the acceleration of the process of hydrophobic analogs) was observed in systems based on polyethyleneimine. (C) 2014 Elsevier B.V. All rights reserved.