Sensing of digestive proteins in saliva with a molecularly imprinted poly(ethylene-co-vinyl alcohol) thin film coated quartz crystal microbalance sensor

The quartz crystal microbalance (QCM) has a sensitivity comparable to that of the surface plasmon resonance (SPR) transducer. Molecularly imprinted polymers (MIPs) have a much lower cost than natural antibodies, they are easier to fabricate and more stable, and they exhibit satisfactory recognition ability when integrated onto sensing transducers. Hence, MIP-based QCM sensors have been used to recognize small molecules and, recently, microorganisms, but only a few have been adopted in protein sensing. In this work, a mixed salivary protein and poly(ethylene-co-vinyl alcohol), EVAL, solution is coated onto a QCM chip and a molecularly imprinted EVAL thin film formed by thermally induced phase separation (TIPS). The optimal ethylene mole ratios of the commercially available EVALs for the imprinting of amylase, lipase and lysozyme were found to be 32, 38, and 44 mol %, respectively. Finally, the salivary protein-imprinted EVAL-based QCM sensors were used to detect amylase, lipase and lysozyme in real samples (saliva) and their effectiveness was compared with that of a commercial ARCHITECT ci 8200 chemical analysis system. The limits of detection (LOD) for those salivary proteins were as low as ∼pM.