Polymers Containing Hydroxamate Groups: Nanoreactors for Hydrolysis of Phosphoryl Esters

A polyhydroxamicalkanoate (PHA) polymer containing the functional groups hydroxamic acid and carboxylic acid with the ability to accelerate dephosphorylation reactions is proposed. The methodology used to prepare this polymer favored the position of the two functional groups next to each other, which allows for the cooperativity between these groups. This cooperative effect has an important role when one wants to mimic enzymes. The catalytic effect promoted by the polymer was evaluated on the cleavage of the bis(2,4-dinitrophenyl) phosphate (BDNPP) and diethyl 2,4-dinitrophenyl phosphate (DEDNPP) esters. Indeed, PHA was very efficient and promiscuous because it increased the rate of both reactions by a factor of up to 10(6)-fold. Isothermal titration calorimetry (ITC) experiments showed that the presence of PHA aids the formation of cetyltrimethylammonium bromide (CTABr) micelles. Thus, the effect of the cationic surfactant CTABr on the dephosphorylation of BDNPP by PHA was also investigated, and it was observed that, when CTABr is added to PHA, the reaction is ca. 15-fold faster compared to the reaction when only PHA is present.