SERS-based Detection of an Organochlorine Pesticide Through Surface Plasmon-Induced C-C Coupling

The palladium-catalyzed Suzuki-Miyaura cross-coupling is among the most widely used process for C-C bond formation by coupling between C-halide compounds and boronic acids. The modification of nanoparticles (NPs) with 4-mercaptophenylboronic acid (4-MPBA) opens the possibility for the SERS analysis of organochlorine pesticides (OPs) through C-C bond formation. Herein, the SERS-based detection of OPs was achieved through surface plasmon-induced Suzuki-Miyaura C-C cross-coupling, catalyzed by 4-MPBA-functionalized AgNPs with varying Pd loading (AgPdx mol%NPs). The results showed that catalytic activity increases linearly as a function of the Pd loading, due to the efficient injection of Surface Plasmon-generated hot electrons into surface Pd atoms in close contact with Ag atoms and consequent delay of deboronation side reaction; while SERS activity diminishes exponentially as a function of Pd content, due to the damping of surface plasmon resonance arising from Ag. Optimized reactional parameters considering the base concentration in the reactional mixture, the incoming laser power density, and Pd content in AgPdx mol%NPs were employed for SERS detection of an OP via cross-coupling at micromolar levels. This work provides a viable methodology for the SERS-based detection of halogenated pesticide residues and related compounds in water samples.

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