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Uniform arrangement of gold nanoparticles on magnetic core particles with a metal-organic framework shell as a substrate for sensitive and reproducible SERS based assays: Application to the quantitation of Malachite Green and thiram

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Abstract

Magnetite (Fe3O4) spheres acting as a core were evenly decorated with gold nanoparticles (AuNPs) and coated with a shell of a metal organic framework (MOF) of type MIL-100(Fe). The resulting hybrid nanomaterial of type Fe3O4-Au@MIL-100(Fe) hybrid is shown to be a viable new SERS substrate. The integration of magnetic core, build-in plasmonic gold nanoparticles and a MOF shell endows the Fe3O4-Au@MIL-100(Fe) with highly efficient magnetic separation and enrichment ability, abundant interparticle hotspots, and significant chemical enhancement effect. This leads to a large enhancement, and greatly improved reproducibility of the SERS signals as shown for Malachite Green (MG) and the fungicide thiram. MG in solution can be quantified with a 50-fold lower detection limit (0.14 nM for peak at 1398 cm−1) and largely improved reproducibility (RSD = 9%, 1398 cm−1) when compared to the use of (a) AuNPs anchored on MIL-100(Fe) (RSD = 27%, 1186 cm−1), or (b) AuNPs embedded in MIL-100(Fe) (RSD = 36%, 1398 cm−1). The method was applied to the quantitation of MG and thiram in spiked water samples. The lower limits of detection are 4.4 nM for MG (1398 cm−1) and 15 nM for thiram (1380 cm−1), respectively, and signals’ RSDs are 13% (1398 cm−1) and 5% (1380 cm−1) for MG and thiram, respectively. The substrate is recyclable.

Schematic illustration of the preparation and SERS molecule sensing application of Fe3O4-Au@MIL-100(Fe) hybrid. PMMA: poly(methacrylic acid; BPEI: branched poly(ethyleneimine); BTC: 1,3,5-tricarboxybenzene.

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Acknowledgements

This work is financially supported by the National Natural Science Foundation of China (21705063, 21665011), Natural Science Foundation of Jiangxi Province (20161BAB203088).

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Authors and Affiliations

  1. College of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang, 330022, People’s Republic of China

    Huasheng Lai, Wenjuan Shang, Yuyin Yun, Danjiao Chen, Liqian Wu & Fugang Xu

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  1. Huasheng Lai
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  2. Wenjuan Shang
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Correspondence to Fugang Xu.

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Lai, H., Shang, W., Yun, Y. et al. Uniform arrangement of gold nanoparticles on magnetic core particles with a metal-organic framework shell as a substrate for sensitive and reproducible SERS based assays: Application to the quantitation of Malachite Green and thiram. Microchim Acta 186, 144 (2019). https://doi.org/10.1007/s00604-019-3257-4

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