Direct detection of melamine in milk via surface-enhanced Raman scattering using gold-silver anisotropic nanostructures.

Abstract

As the degree of anisotropy in nanoparticle morphology increases, the resulting electromagnetic enhancement can be significantly intensified. Herein, we have attempted to develop anisotropic gold-silver (a-AuAg) nanoparticles deposited on a titanium sheet (a-AuAg@Ti) as a highly efficient Surface-enhanced Raman Spectroscopy (SERS) sensor for rapid detection of health-hazardous milk adulterants like melamine. Hierarchical a-AuAg nanoparticles have been synthesized via a facile seed and growth-mediated method, followed by immobilization on a titanium sheet using a drop-casting technique. The structural, morphological, chemical, and optical properties of a-AuAg@Ti sensors have been systematically investigated and correlated with their respective SERS performance. Morphological analysis revealed the occurrence of triangular, hexagonal, and pentagonal-shaped nanoparticles with an average particle size of ∼ 23 to 26 nm. Preliminary SERS analysis using Rhodamine 6G (R6G) probe molecule revealed significantly higher SERS activity for a-AuAg nanoparticles compared to their spherical counterparts. This could be attributed to the lightning rod effect associated with the synthesized anisotropic nanostructures. An enhancement factor of 1.7 x 10⁸ has been estimated for a-AuAg@Ti sensor with excellent signal reproducibility. Further, the efficacy of melamine detection has been investigated by spiking it into water and milk samples. The estimated lower detection limit (LDL) near picomolar and nanomolar concentrations have been obtained for melamine-spiked samples in water and milk, respectively. High-performance liquid chromatography analysis for melamine revealed an LDL of only 0.1 µM, indicating the higher sensitivity of a-AuAg@Ti SERS sensor. Moreover, we have also analyzed commercial milk products to verify the melamine contents, but none of them showed melamine-specific fingerprint bands. Our findings highlight the superior sensitivity of a-AuAg@Ti substrates for real-time melamine detection, making them excellent optical sensing tools for food safety analysis.