Ultrasensitive iodide detection in biofluids based on hot electron-induced reduction of p-Nitrothiophenol on Au@Ag core-shell nanoparticles

Biosens Bioelectron. 2023 Sep 1:235:115365. doi: 10.1016/j.bios.2023.115365. Epub 2023 May 10.

Abstract

Surveillance of iodine intake is important because either inadequate or excessive amount of iodine may lead to thyroid malfunctions. Herein, we report a method for fast iodide quantification based on a plasmonic hot electron-driven chemical reaction, which occurs on Au@Ag core-shell nanoparticles (NPs) coated with p-nitrothiophenol (PNTP) molecules. Upon resonant light illumination, hot electron-hole pairs are generated in the NPs. The hot holes capture iodide ions (I-) and form AgI which decomposes under light; while the hot electrons are shifted to the electron orbital (LUMO) of PNTP and trigger its reduction to p-aminothiophenol (PATP). By measuring characteristic surface-enhanced Raman spectroscopic (SERS) peaks of PNTP and PATP, the concentration of I- in water can be quantitatively determined, with a linear response in the 0.5-20 μM range and a detection limit of 0.30 μM. The Au@Ag nanosensor was then applied for I- detection in various biofluids including urine, serum and saliva, exhibiting superior detection sensitivity and high selectivity. This sensing assay requires a small sample volume of ∼10 μL and completes the entire detection process in ∼2 min, and therefore holds significant potential for application in point-of-care settings.

Keywords: Au@Ag nanosensors; Hot electrons; Iodide detection; Photosensitive; Surface-enhanced Raman spectroscopy.

MeSH terms

  • Antibodies
  • Biosensing Techniques*
  • Electrons
  • Gold / chemistry
  • Iodides
  • Metal Nanoparticles* / chemistry
  • Silver / chemistry

Substances

  • Iodides
  • Gold
  • Silver
  • Antibodies
  • 4-aminothiophenol