Electrochemical Self-Assembled Gold Nanoparticle SERS Substrate Coupled with Diazotization for Sensitive Detection of Nitrite

The accurate determination of nitrite in food samples is of great significance for ensuring people’s health and safety. Herein, a rapid and low-cost detection method was developed for highly sensitive and selective detection of nitrite based on a surface-enhanced Raman scattering (SERS) sensor combined with electrochemical technology and diazo reaction. In this work, a gold nanoparticle (AuNP)/indium tin oxide (ITO) chip as a superior SERS substrate was obtained by electrochemical self-assembled AuNPs on ITO with the advantages of good uniformity, high reproducibility, and long-time stability. The azo compounds generated from the diazotization-coupling reaction between nitrite, 4-aminothiophenol (4-ATP), and N-(1-naphthyl) ethylenediamine dihydrochloride (NED) in acid condition were further assembled on the surface of AuNP/ITO. The detection of nitrite was realized using a portable Raman spectrometer based on the significant SERS enhancement of azo compounds assembled on the AuNP/ITO chip. Many experimental conditions were optimized such as the time of electrochemical self-assembly and the concentration of HAuCl₄. Under the optimal conditions, the designed SERS sensor could detect nitride in a large linear range from 1.0 × 10⁻⁶ to 1.0 × 10⁻³ mol L⁻¹ with a low limit of detection of 0.33 μmol L⁻¹. Additionally, nitrite in real samples was further analyzed with a recovery of 95.1−109.7%. Therefore, the proposed SERS method has shown potential application in the detection of nitrite in complex food samples.