New methodologies in the preparation of imprinted polymers

Molecular imprinting is a rapidly emerging method for the creation of recognition sites in synthetic polymers, and the resultant materials offer considerable promise as selective adsorbents in a number of applications. The technique exploits the principle of using elements of a target molecule to create its own recognition site. This is achieved by the formation of a highly cross-linked polymeric matrix around a template, which can be the target molecule itself or a close structural analogue. The key to this procedure is to ensure that, during the polymerization, functional groups of the template molecule are fully engaged in interactions with ‘complementary functionality’ of polymer-forming components. These interactions are then ‘locked in’ by the incorporation of the whole assembly into the polymer structure. Subsequent removal of the template reveals the newly created binding sites containing functional groups in the precise stereochemical arrangement to ensure recognition of the target in a highly selective manner (Scheme 1). The first reports of molecular imprinting in organic polymers involved the templating of protected sugars, in the form of esters with a polymerizable boronic acid (however, see Ref. 18 for an earlier example of the imprinting concept) into a cross-linked polymer ‘scaffold’, and variations of the basic technique have now been adopted by many research groups around the world. In general, molecularly imprinted polymers (MIPs) are prepared by thermal or photochemical free-radical routes, employing acrylic or vinylic monomers in a solvent chosen to ensure that the final matrix is microporous. The numbers and types of molecules which have now been imprinted is very large, but a key factor in the preparation of MIP materials with the desired recognition properties is still the chemical nature of the link between the template and the polymer backbone. Consequently, strategies by which the template can be securely fixed in space as the growing matrix forms around it, yet be readily removed to generate the recognition site after polymer synthesis is complete, are of particular interest.