Tuning surface-cross-linking of molecularly imprinted cross-linked micelles for molecular recognition in water.

Molecular recognition in water is an important challenge in supramolecular chemistry. Surface-core double cross-linking of template-containing surfactant micelles by the click reaction and free radical polymerization yields molecularly imprinted nanoparticles (MINPs) with guest-complementary binding sites. An important property of MINP-based receptors is the surface-cross-linking between the propargyl groups of the surfactants and a diazide cross-linker. Decreasing the number of carbons in between the two azides enhanced the binding affinity of the MINPs, possibly by keeping the imprinted binding site more open prior to the guest binding. The depth of the binding pocket can be controlled by the distribution of the hydrophilic/hydrophobic groups of the template and was found to influence the binding in addition to electrostatic interactions between oppositely charged MINPs and guests. Cross-linkers with an alkoxyamine group enabled two-stage double surface-cross-linking that strengthened the binding constants by an order of magnitude, possibly by expanding the binding pocket of the MINP into the polar region. The binding selectivity among very similar isomeric structures also improved.