Molecular Imprints Frozen by Strong Intermolecular Interactions in Place of Cross-Linking.

A new way to freeze molecular imprints in a polymer material is reported. So far, molecular imprinted polymers (MIP) involve copolymerization of a functional monomer and large amounts of cross-linking agent, which keeps the template shape memory in rigid molecular imprints. MIP materials are prepared herein without cross-linking agent. Stiff chains of polyaniline grafted on a solid support as a brush-like material achieve the necessary rigidity. Differential adsorption to imprinted and non-imprinted materials provides evidence of molecular imprints. A correct adsorption isotherm for mobile adsorbed layers (Volmer isotherm) is introduced instead of the popular but inadequate Langmuir isotherm. Non-selective adsorption is entropic, whereas adsorption to molecular imprints has an enthalpic contribution coming from specific interactions. Fast adsorption kinetics are a definite benefit with regards to applications such as chromatographic separations and chemical sensors.