Fabrication of zein-based biodegradable surface enhanced Raman spectroscopy biosensor platforms for the detection of food toxins

Identifying and detecting health hazards in food products, especially contaminants and toxic substances such as allergens, food toxins and agricultural residues from pesticides, remains a challenge. Increasing demand for food products and growing health consciousness necessitate rapid and accurate measurements which can be easily conducted on-site without long measurement times and high costs. Due to their ease of use, accuracy sample preparation and rapidity, biosensors have started to outcompete time-consuming lab-scale analytical devices. However, as the use of biosensors increase, a concern of the amount of plastics and synthetic polymers used in the fabrication of these biosensors rises. In this dissertation, new ways to create biodegradable and eco-friendly plant-based SERS biosensor platforms from corn protein, zein, are presented. Its higher hydrophobicity and film forming capability make zein a very suitable biopolymer for fabricating biosensors. In the first part of this dissertation, chemical crosslinking was tested to improve the surface hydrophobicity, surface roughness (using AFM), mechanical properties, kinetics of gelation and film formation of zein films, and as a result zein-film based SERS platforms with fewer defects could be fabricated. In the second part, the detection sensitivity of the zein film-based SERS platforms was increased with metallic nanoparticle decoration (gold, silver or silver-shelled-gold). The addition of all three types of nanoparticles significantly increased the SERS enhancement factors of the platforms, with silver-shelled-gold nanoparticles giving the highest enhancement factor of 10⁵. In the last part of this thesis, a novel approach was tested, where electrospun zein nanofibers decorated with metallic nanoparticles were used as a SERS biosensor platform. Due to their higher surface area-to-volume ratios, electrospun zein nanofibers gave a higher SERS enhancement factor (10⁶). This enhancement factor enabled the detection of acrylamide, a food carcinogen, with a 10⁴ times lower detection limit than nanophotonic based nanoimprinted zein, acrylamide sensor platform. Overall, this dissertation successfully shows the fabrication of biodegradable and eco-friendly SERS sensor platforms that have comparable detection sensitivities to those of non-biodegradable ones.