Poly(Neutral Red)-Silver Nanorods-Carbon Nanotubes Composite-Based Ratiometric Electrochemical Sensor for Rapid Detection of Histamine in Crayfish
Abstract
A ratiometric electrochemical sensor based on poly(neutral red)-silver nanorods-carbon nanotubes (PNR-AgNRs/CNTs) composite was constructed for rapid, sensitive, and an-ti-interference detection of histamine in crayfish (Procambarus clarkii). Silver nanorods (AgNRs) were synthesized via a liquid-phase reduction method using 2-mercaptobenzoic acid (2-MBA) as both reducing and stabilizing agent, and subse-quently composited with carbon nanotubes (CNTs) through ultrasonic dispersion to form a three-dimensional conductive network. Poly(neutral red) (PNR) was electro-chemically polymerized onto the AgNRs-CNTs modified glassy carbon electrode (GCE) surface via cyclic voltammetry, serving as an electrochemical signal probe. The resulting PNR-AgNRs-CNTs/GCE exhibited significantly enhanced electrochemical performance with approximately 5-fold increase in electrochemically active surface area compared to bare GCE. Histamine competitively inhibited the electrochemical signal of PNR without affecting the AgNRs signal, enabling ratiometric detection based on the current signal ratio (IPNR/IAgNRs). Under optimized conditions (pH 6.0, adsorption time 6 min, material loading 0.08 mg/cm²), the IPNR/IAgNRs ratio exhibited a good linear relationship with the logarithm of histamine concentration in the range of 1–150 μmol/L, with a linear equa-tion of I/I = −0.3152 ln(C) + 5.0613, correlation coefficient R² = 0.995, and detection limit of 0.16 μmol/L (S/N = 3). The sensor demonstrated…
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