Performance enhancement of paper-based SERS chips by shell-isolated nanoparticle-enhanced Raman spectroscopy

doi:10.1016/j.jmst.2019.05.055

Abstract

Abstract:

Paper-based flexible surface-enhanced Raman scattering (SERS) chips have been demonstrated to have great potential for future practical applications in point-of-care testing (POCT) due to the potentials of massive fabrication, low cost, efficient sample collection and short signal acquisition time. In this work, common filter paper and Ag@SiO₂core-shell nanoparticles (NP) have been utilized to fabricate SERS chips based on shell‐isolated nanoparticle‐enhanced Raman spectroscopy (SHINERS). The SERS performance of the chips for POCT applications was systematically investigated. We used crystal violet as the model molecule to study the influence of the size of the Ag core and the thickness of the SiO₂coating layer on the SERS activity and then the morphology optimized Ag@SiO₂core-shell NPs was employed to detect thiram. By utilizing the smartphone as a miniaturized Raman spectral analyzer, high SERS sensitivity of thiram with a detection limit of 10^-9M was obtained. The study on the stability of the SERS chips shows that a SiO₂shell of 3 nm can effectively protect the as-prepared SERS chips against oxidation in ambient atmosphere without seriously weakening the SERS sensitivity. Our results indicated that the SERS chips by SHINERS had great potential of practical application, such as pesticide residues detection in POCT.

Key words: SERS chip, Point-of-Care test (POCT), Shell-core nanostructure, Stability

Mingze Sun, Binghan Li, Xiaojia Liu, Jiayin Chen, Taotao Mu, Lianqing Zhu, Jinhong Guo, Xing Ma. Performance enhancement of paper-based SERS chips by shell-isolated nanoparticle-enhanced Raman spectroscopy[J]. J. Mater. Sci. Technol., 2019, 35(10): 2207-2212.

Figures/Tables 5

Scheme 1. Schematic illustration of (a) the fabrication of Ag and Ag@SiO2 core-shell NPs and (b) preparation of paper-based Ag and Ag@SiO2 core-shell NPs chips and the detection of CV and thiram modules using smart phone Raman analyzer.

Fig. 1. SEM images of 0.275 mM PVP Ag NPs (a), size distribution (b), zeta-potential distribution (c), and UV-vis spectra (d) of the Ag NPs of three concentrations of PVP, (e) typical SERS spectra of CV (10-3 M) of paper-based chips with and without adsorption of Ag NPs, and (f) the relation between the SERS intensity at 1614 cm-1 and the PVP concentrations (the error bar indicates the standard deviation, N = 10).

Fig. 2. SEM images of optimal size Ag NPs (a), TEM images of Ag/SiO2 core-shell NPs for samples of 0.5 μL TEOS (b), and 1.5 μL TEOS (c), size distribution (d), Zeta-potential distribution (e), and UV-vis spectra (f) of Ag/SiO2 core-shell NPs.

Fig. 3. (a) SERS spectra of CV (10-3 M) of the Ag/SiO2 NPs, (b) the relation between the SERS intensity at 1614 cm-1 and the TEOS concentration of the Ag/SiO2 NPs, (c) SERS spectra of thiram (10-3-10-9 M) of 0.5 μL TEOS-Ag/SiO2 NPs and (d) relation between SERS intensity of thiram at 1379 cm-1 and log values of concentration of thiram (the error bar indicates the standard deviation, N = 10).

Fig. 4. Typical SERS spectra of CV (10-3 M) for Ag NPs (a), 0.5 μL TEOS-Ag/SiO2 NPs (b) and 1.5 μL TEOS-Ag/SiO2 NPs (c) measured on different days during aging in air and (d) average SERS intensity of crystal violate (10-3 M) at 1614 cm-1 measured during aging in air for 60 d.

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