Modification of the reactivity of a small molecule by reversible association with a synthetic polymer. Inhibition of the hydrolysis of cationic esters by polyanions

The base‐catalyzed hydrolysis rate of the cationic esters obtained by quaternization of N,N,N′,N′‐tetramethylethylenediamine with phenylbromoacetate was studied in buffers and in solutions of partially neutralized polymeric acids. The polyanions were found to be powerful inhibitors of the reaction. This effect was interpreted as due to the association of the ester with the polyanion, from which the catalytically active hydroxyl groups are repelled. It is shown that kinetic data may be interpreted by a procedure similar to the Lineweaver‐Burk plot to yield the reactivity of the bound ester and the dissociation constant of the polymer–ester complex.