Insights on the Molecular Characteristics of Molecularly Imprinted Polymers as Monitored by Sum Frequency Generation Spectroscopy

Sensing in molecularly imprinted polymers (MIPs) requires specific interactions of the imprinted polymer and the approaching template molecule. These interactions are affected by the morphology of the polymer surface, the affinity of the template molecule to the polymer network, and the steric approach. In this particular study, a template molecule, metronidazole, is studied with respect to the typically used methacrylic acid-based imprinted polymer using a combination of bulk and surface techniques. The resulting infrared (IR) spectra exhibited the presence of the template molecule in the polymer matrix as well as their efficient removal after washing. Dipping of the MIP according to what is expected of facile sensing in an aqueous solution of metronidazole did not show any presence of the template molecule in the bulk of the MIP, as observed by IR spectroscopy. However, using sum frequency generation (SFG) spectroscopy, the CH aromatic stretch of the imidazole ring positioned at ∼3100 cm^-1 was observed at the polymer surface, including its inner pores or cavities, and at the buried polymer-fused silica interface after dipping. SFG studies have also shown the vibrational signatures of the polymer matrix, the presence of the template molecule on the surface, and the detection of residual template molecules after washing. Increasing the washing time to 50 min has proven to be less effective than increasing the washing cycles to three. However, after the third cycle, reorganization of the polymer matrix was evident as also the complete removal of the template molecule. The observed changes from the acquired images using scanning electron microscopy and atomic force microscopy show the structural morphologies of MIPs and a good distribution of the pores across the MIP surface. The study demonstrates the importance of combining both bulk and surface characterization in providing insight into the template molecule-polymer network interactions.