Biomimetic properties and surface studies of a piezoelectric caffeine sensor based on electrosynthesized polypyrrole.

An approach for preparing a chemical sensor for caffeine through the combination of molecularly imprinted polypyrrole and a piezoelectric quartz transducer was proposed. The caffeine-imprinted polymer was synthesized using galvanostatic electropolymerization of pyrrole monomer directly onto one of the gold electrodes of a 9MHz AT-cut quartz crystal in the presence of caffeine. The optimum conditions for the electrosynthesis of the reagent phase were established. Caffeine molecules were entrapped in the matrix of polymer film, and were removed by subsequent washing with water, leaving behind pores capable of recognizing the target analyte molecule. The caffeine sensor was fixed in a measuring cell and measurement of the resonant frequency of the quartz crystal as it comes in contact with the caffeine solution was carried out in a stopped flow mode. A steady-state response was achieved in about 10min. The sensor exhibited a linear relationship between the frequency shift and the ln of caffeine concentration in the range of 0.1-10mg/mL (correlation coefficient, r=0.9882). The sensitivity of the sensor was about 255Hz/ln concentration (mg/mL). A good repeatability, R.S.D.=9 (n=6) for 0.5mg/mL caffeine solution was also observed. The use of the sensor can present a potential low-cost option for determining caffeine. Surface analytical techniques such as scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) were performed on the polymer coating in order to elucidate the imprinting process and rebinding of caffeine to the polymer matrix during the sensing process. The SEM micrographs and XPS spectra revealed features and structures that could support the imprinting and recognition of caffeine molecule by the imprinted polymer.