Selectivity features of molecularly imprinted polymers recognising the carbamate group

The molecular recognition properties of molecular imprinted polymers which bind the carbamate function were studied. Functional monomers potentially able to form non-covalent interactions with the model molecule N,O-dibenzylcarbamate were selected on the basis of a computational approach describing possible interactions between the template and a small library of vinylic monomers. These results were in accordance with N,O-dibenzylcarbamate batch-rebinding measurements performed on several miniMIPs prepared with the same library. From these preliminary results, four polymers were prepared by thermoinduced radical polymerization, using ethylene dimethacrylate as a cross-linker, chloroform (MIP1, MIP3) or acetonitrile (MIP2, MIP4) as porogens and methacrylic acid (MIP1, MIP2) or acrylamide (MIP3, MIP4) as functional monomers. Molecular recognition features of these materials were studied by high-performance liquid chromatography. In this manner selectivity was evaluated by considering the column retention of a library of sixteen structural analogues of dibenzylcarbamate, characterized by the transformation of the carbamate into a related function, or by the alteration of the molecular structure. The experimental results show that methacrylic acid is more efficient than acrylamide as a functional monomer (imprinting factors: MIP1 = 24.1, MIP2 = 25.6, MIP3 = 13.3, MIP4 = 2.44), and that chloroform enhances polymer selectivity. As regards structural motifs which conditionate the selectivity, the carbamate function strictly controls the presence/absence of molecular recognition, while shape and dimension of the substituents modulate the recognition itself. In particular, a marked recognition for analogs which were slightly bigger than the template was observed (N-benzyl-O-phenethylcarbamate: MIP1 alpha = 1.13, MIP2 alpha = 1.41, MIP3 alpha = 0.97; N-phenethyl-N-benzylcarbamate: MIP1 alpha = 1.61, MIP2 alpha = 1.17, MIP3 alpha = 0.81; N,O-diphenethylcarbamate: MIP1 alpha = 0.89, MIP2 alpha = 1.20, MIP3 alpha = 0.55). (C) 2004 Elsevier B.V. All rights reserved.