Ultra-Thin Plasma-Polymerized Functional Coatings for Biosensing: Polyacrylic Acid, Polystyrene and Their Co-Polymer

Recently, many efforts have been done to chemically functionalize sensors surface to achieve selectivity towards diagnostics targets, such as DNA, RNA fragments and protein tumoural biomarkers, through the surface immobilization of the related specific receptor. Especially, some kind of sensors such as microcantilevers (gravimetric sensors) and one-dimensional photonics crystals (optical sensors) able to couple Bloch surface waves are very sensitive. Thus, any kind of surface modifications devoted to functionalize them has to be finely controlled in terms of mass and optical characteristics, such as refractive index, to minimize the perturbation, on the transduced signal, that can affect the response sensitivity towards the detected target species. In this work, the study and optimization of ultra-thin plasma polymers and copolymers, compatible with these constrains and obtained from the vapours of acrylic acid containing a carboxylic (−COOH) group and styrene (an aromatic molecule with a vinyl as substituent at the ring), are reported. The obtained plasma polyacrylic acid (PPAA), plasma polystyrene (PPST) and their copolymer (PPAA–ST), characterized through optical contact angle analysis (OCA), Fourier transform infrared (FTIR) spectroscopy in attenuated total reflection (ATRFTIR), X-ray photoelectrons spectroscopy (XPS), and atomic force microscopy (AFM), are shown to match specific and critical requirements, such as low thickness (∼40 nm) and refractive index (∼1.5), high surface density of reactive groups (1015–1016 COOH/cm2), bioantifouling properties where required, reproducibility, and chemical resistance and stability.