HAuCl4/K4Fe(CN)6 reaction mediated silver nanosol as SERS substrate for robust detection of malachite green residue in seafood

in: Microchemical Journal (2024)
Wu, Long; Zeng, Wei; Liu, Chen; Popp, Jürgen; Cialla-May, Dana
Irreproducibility is considered as a significant obstacle to the widespread use of surface enhanced Raman spectroscopy (SERS) as a sensing platform. However, in terms of the SERS performance in applications, less attention has been paid on the stability, i.e., repeatability and reproducibility compared to sensitivity. Here, based on HAuCl4/K4Fe(CN)6 reaction and silver nanosol (Ag NS), a reaction mediated SERS (R-SERS) platform was proposed for the detection of malachite green residue (MG) in aquatic products, aiming to improve both the sensitivity and stability of SERS. Wherein, the HAuCl4/K4Fe(CN)6 reaction produced Au0 grows on Ag NPs and provided additional “hot spots” to enhance signal intensity. Meanwhile, the reaction system released cyano group (-C≡N) will cap on the surface of Ag or Au NPs and act as an internal signal at ~2100 cm− 1 to adjust the background signal. As a proof of principle, adenine (Ade, 730 cm− 1 ), ceftriaxone (Cef, 1345 cm− 1 ) and MG (1170 cm− 1 ) were selected as targets to discuss the detection performance, with linear ranges of 0.1 ~ 20 μM, 0.1 ~ 10 μM and 0.1 ~ 2 μM and limit of detection (LOD, 3σ/M) of 0.079 μM, 0.050 μM and 0.032 μM, respectively. In practical applications, MG residue in aquatic products were detected with the recoveries ranged from 85 % to 98 % and the coefficient of variations of intra-assay below 6.6 %. The R-SERS platform, therefore, was demonstrated to enhance SERS intensity and stability with in situ growth of label on Ag NPs, suggesting its potential applications in SERS sensing.

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