Photo-lithographic patterning of biomimetic molecularly imprinted polymer thin films onto silicon wafers

This investigation describes the design and synthesis of molecularly imprinted polymers (MIPs) as patterned thin films, based on molecular modelling of functional monomer-template interactions and validation by NMR-spectroscopy. Several MIP thin films were prepared from a solution containing the template N-boc-l-phenylalanine and functional acrylic monomers at varying ratios with a cross-linker and initiator in a porogenic solvent. This solution was then spin-coated onto 3-(trimethoxysilyl)propyl methacrylate-functionalised silicon wafers and subsequently the film was photo-polymerised. After template extraction, the film thickness and topography of a methacrylic acid MIP was characterised with atomic force microscopy. A 4-vinylpyridine-MIP thin film was then made by depositing the pre-polymerisation solution on top of the methacrylic acid MIP by spin-coating. Photo-lithographic etching through a gold grid and extraction of non-polymerised solution from under the gold mask yielded a grid-patterned surface, in which two different MIPs alternate with dimensionality at the micro- or submicro-meter scale. Selectivity differences between the two MIP surfaces towards fluorescent template analogue N-dansyl-l-phenylalanine were documented using fluorescence microscopy. This side-by-side comparison on the same thin film allows fast and cost-effective assessment of the two very different MIP selectivities towards various biomolecules.