Imprinted polymeric nanoparticles as artificial enzymes for ester hydrolysis at room temperature and pH 7

Replication of the extraordinary catalysis of enzymes in synthetic systems is a long-standing goal of scientists. Here we report a synthetic mimic of carbonic anhydrase capable of hydrolyzing nonactivated alkyl esters at room temperature and neutral pH, while more reactive aryl esters stay intact in the same solution. This type of catalysis normally occurs only in enzymes but becomes possible with synthetic catalysts when a basic group is placed accurately near a zinc-bound water molecule to activate the latter for the nucleophilic attack on the ester substrate. Basicity and charge character of the proton acceptor determine the catalytic mechanism and its window of operation, as well as the type of esters to be hydrolyzed. The distance between the catalytic groups dictates the rate of hydrolysis for the benchmarking p-nitrophenyl ester, with a change by a single bond length impacting the rate more than changing the basicity of the active site base by20 orders of magnitude.