Controllable self-assembled plasmonic vesicle-based three-dimensional SERS platform for picomolar detection of hydrophobic contaminants

Abstract

Hydrophobic contaminants in food and the environment seriously threaten human health. The ultrasensitive detection of these pollutants can minimize their damage. However, current ultrasensitive sensing strategies are limited to solid substrate-based surface-enhanced Raman spectroscopy (SERS) detection. Herein, we report a controllable and reproducible solution-based SERS detection platform for the direct and ultrasensitive detection of hydrophobic contaminants by using self-assembled three-dimensional plasmonic vesicles. To this end, amphiphilic gold nanoparticles (AuNPs) tethered with linear block copolymer (BCP) of polystyrene-b-poly (ethylene oxide) (PS-b-PEO) were designed, which display dual functions for improving detection sensitivity, including serving as building blocks for the construction of plasmonic vesicles to yield large numbers of hot-spots for SERS enhancement, and providing hydrophobic PS layers to enrich and concentrate target hydrophobic molecules for direct SERS detection with hydrophobic interaction. By modulating the AuNP size and the length of BCP chains, the ultrahigh detection sensitivity, down to the picomolar level, was obtained via using 80 nm AuNPs tethered with BCP of PEO₄₅-b-PS₉₀₀-SH. In addition, the proposed method exhibits excellent reproducibility, universality, practicability, as well as multiplexing detection capacity in actual contaminant-spiked soil samples. Briefly, the designed self-assembled plasmonic vesicle-based SERS platform provides an ideal generic methodology for the ultrasensitive detection of hydrophobic contaminants that can greatly accelerate on-site testing in food and environmental monitoring.