We developed highly sensitive surface-enhanced Raman scattering (SERS) probes based on SiO2@Au@Ag nanoparticles (NPs) using the Ag growth onto Au NP seeds method.

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In this study, SiO2@Au@4-MBA@Ag (4-mercaptobenzoic acid labeled gold-silver-alloy-embedded silica nanoparticles) nanomaterials were investigated for the detection of thiram, a pesticide. First, the presence of Au@4-MBA@Ag alloys on the surface of SiO2 was confirmed by the broad bands of ultraviolet-visible spectra in the range of 320–800 nm. The effect of the 4-MBA (4-mercaptobenzoic acid) concentration on the Ag shell deposition and its intrinsic SERS (surface-enhanced Raman scattering) signal was also studied. Ag shells were well coated on SiO2@Au@4-MBA in the range of 1–1000 µM. The SERS intensity of thiram-incubated SiO2@Au@4-MBA@Ag achieved the highest value by incubation with 500 µL thiram for 30 min, and SERS was measured at 200 µg/mL SiO2@Au@4-MBA@Ag. Finally, the SERS intensity of thiram at 560 cm−1 increased proportionally with the increase in thiram concentration in the range of 240–2400 ppb, with a limit of detection (LOD) of 72 ppb.

In this study, silica-coated magnetic iron oxide nanoparticles (MNPs@SiO2) were covalently conjugated onto graphene oxide (GO/MNP@SiO2) for protein isolation. First, MNPs were precisely coated with a silica layer on the surface by using the reverse microemulsion method, followed by incubation with 3-glycidyloxypropyltrimethoxysilane (GPTS) to produce the GPTS-functionalized MNPs@SiO2 (GPTS-coated MNPs@SiO2) that display epoxy groups on the surface. The silica shell on the MNPs was optimized at 300 µL of Igepal®CO-520, 5 mg of MNP, 100 µL of TEOS, 100 µL of NH4OH and 3% of 3-glycidyloxypropyltrimethoxysilane (GPTS). Simultaneously, polyethyleneimine (PEI) was covalently conjugated to GO to enhance the stability of GO in aqueous solutions and create the reaction sites with epoxy groups on the surface of GPTS-coated MNP@SiO2. The ratio of PEI grafted GO and GPTS-coated MNP@SiO2 (GO/MNP ratio) was investigated to produce GO/MNPs@SiO2 with highly saturated magnetization without aggregation. As a result, the GO/MNP ratio of 5 was the best condition to produce the GO/MNP@SiO2 with 9.53 emu/g of saturation superparamagnetization at a magnetic field of 2.0 (T). Finally, the GO/MNPs@SiO2 were used to separate bovine serum albumin (BSA) to investigate its protein isolation ability. The quantity of BSA adsorbed onto 1 mg of GO/MNP@SiO2 increased sharply over time to reach 628 ± 9.3 µg/mg after 15 min, which was 3.5-fold-higher than that of GPTS-coated MNP@SiO2. This result suggests that the GO/MNP@SiO2 nanostructure can be used for protein isolation.

Surface-enhanced Raman scattering (SERS) spectroscopy is attractive in various detection analysis fields. However, the quantitative method using SERS spectroscopy remains as an area to be developed. The key issues in developing quantitative analysis methods by using SERS spectroscopy are the fabrication of reliable SERS-active materials such as nanoparticle-based structures and the acquisition of the SERS signal without any disturbance that may change the SERS signal intensity and frequency. Here, the fabrication of seamless multilayered core–shell nanoparticles with an embedded Raman label compound as an internal standard (MLRLC dots) for quantitative SERS analysis is reported. The embedded Raman label compound in the nanostructure provides a reference value for calibrating the SERS signals. By using the MLRLC dots, it is possible to gain target analyte signals of different concentrations while retaining the Raman signal of the internal standard. The ML4‑BBT dots, containing 4-bromobenzenethiol (4-BBT) as an internal standard, are successfully applied in the quantitative analysis of 4-fluorobenzenethiol and thiram, a model pesticide. Additionally, ratiometric analysis was proved practical through normalization of the relative SERS intensity. The ratiometric strategy could be applied to various SERS substrates for quantitative detection of a wide variety of targets.