Interior Hotspot Engineering in Ag-Au Bimetallic Nanocomposites by In Situ Galvanic Replacement Reaction for Rapid and Sensitive Surface-Enhanced Raman Spectroscopy Detection

Int J Mol Sci. 2022 Oct 3;23(19):11741. doi: 10.3390/ijms231911741.

Abstract

Engineering of interior hotspots provides a paradigm shift from traditional surface-enhanced Raman spectroscopy (SERS), in which the detection sensitivity depends on the positioning of adsorbed molecules. In the present work, we developed an Ag-Au bimetallic nanocomposite (SGBMNC) SERS platform with interior hotspots through facile chemical syntheses. Ag nanoparticles replaced by Au via the galvanic replacement reaction (GRR) provided hotspot regions inside the SGBMNC that remarkably enhanced the plasmonic activity compared to the conventional SERS platforms without the internal hotspots. The diffusion of analytes into the proposed interior hotspots during the GRR process enabled sensitive detections within 10 s. The SERS behaviors of the SGBMNC platform were investigated using methylene blue (MB) as a Raman probe dye. A quantitative study revealed excellent detection performance, with a limit of detection (LOD) of 42 pM for MB dye and a highly linear correlation between peak intensity and concentration (R2 ≥ 0.91). The SGBMNC platform also enabled the detection of toxic benzyl butyl phthalate with a sufficient LOD of 0.09 ppb (i.e., 280 pM). Therefore, we believe that the proposed methodology can be used for SERS assays of hazardous materials in practical fields.

Keywords: benzyl butyl phthalate; cellulose acetate paper; galvanic replacement reaction; silver-gold bimetallic nanocomposites; surface-enhanced Raman spectroscopy.

MeSH terms

  • Gold / chemistry
  • Hazardous Substances
  • Metal Nanoparticles* / chemistry
  • Methylene Blue
  • Nanocomposites*
  • Silver / chemistry
  • Spectrum Analysis, Raman / methods

Substances

  • Hazardous Substances
  • Silver
  • Gold
  • Methylene Blue

Grants and funding

This study was supported financially by the National R & D Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Science and ICT (NRF-2021R1A2C2011048, NRF-2021M3H4A1A02051036). This research was supported by the Korea Health Technology R&D Project through the Korea Health Industry Development Institute (KHIDI) and Korea Dementia Research Center (KDRC), funded by the Ministry of Health & Welfare and Ministry of Science and ICT, Republic of Korea (grant number: HU21C0335).