Self-Assembled Lubricin (PRG-4)-Based Biomimetic Surface-Enhanced Raman Scattering Sensor for Direct Droplet Detection of Melamine in Undiluted Milk

Abstract

Surface-enhanced Raman scattering (SERS) is a powerful optical sensing platform that amplifies the target signals by Raman scattering. Despite SERS enabling a meager detection limit, even at the single-molecule level, SERS also tends to equally enhance unwanted molecules due to the non-specific binding of noise molecules in clinical samples, which complicates its use in complex samples such as bodily fluids, environmental water, or food matrices. To address this, we developed a novel non-fouling biomimetic SERS sensor by self-assembling an anti-adhesive, anti-fouling, and size-selective Lubricin (LUB) coating on gold nanoparticle (AuNP) functionalized glass slide surfaces via a simple drop-casting method. Compared to a conventional AuNPs-SERS substrate, the biomimetic SERS meets the requirements of simple preparation and enables direct droplet detection without any sample pre-treatment. Atomic force microscopy was used to confirm the self-assembled Lubricin coating on the AuNP surface, acting as an anti-fouling and size-selective protection layer. A series of Raman spectra were collected using melamine as the target analyte, which was spiked into 150 mM NaCl solution or undiluted milk. It was demonstrated that the LUB coating effectively prevents the detrimental fouling generated by the proteins and fats in milk, ensuring the clear detection of melamine. Our sensor showed high selectivity and could detect melamine in milk at concentrations as low as 1 ppm. Given that the EU/US legal limit for melamine in food is 2.5 ppm, this sensor offers a promising, cost-effective solution for routine screening and has potential applications for detecting food adulteration in the food safety, environmental monitoring, aquaculture, and biomedical fields.