The importance of size and shape in imprinted polymers

The existence of shape selectivity in non-covalent molecularly imprinted polymers has been proven using molecular probes. A series of amines varying with different structural motifs and secondary amines with different sized side chains were imprinted, and binding evaluated by HPLC for each amine on polymers imprinted with similar amines. Trends in the binding relationships revealed two major contributions of cavity structure on selectivity afforded by molecularly imprinted polymers (MIPs). First, sterics play a dominant role in cases where a molecules structure is too big too fit into an imprinted site formed from a smaller template molecule. Second, molecular structures that are equal to or smaller than those of the template molecule are selected by maximizing Van der Waals interactions within the MIP binding site.