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Gold nanorods for in-drop colorimetric determination of thiomersal after photochemical decomposition

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Abstract

This work reports on the implementation of gold nanorods (AuNRs) in headspace solvent microextraction for colorimetric determination of volatile analyte derivatives in a single drop. The exposure of AuNRs to both H2Se and elemental mercury (Hg0) results in a shift of the longitudinal plasmonic band, unlike a number of volatiles. Accordingly, a method is reported for the determination of Hg0 with potential applicability to the determination of thiomersal (sodium ethylmercurithiosalicylate). It is based on the photochemical decomposition of thiomersal into Hg(II) and subsequent exposure of AuNRs-containing microdrop to in situ generated Hg0. Colorimetric analysis of the enriched drop was carried out without dilution by means of a cuvetteless microvolume UV-vis spectrometer. Under optimal conditions, the limit of detection was 0.5 ng mL−1 (as Hg). The repeatability, expressed as relative standard deviation, was 8.4% (for n = 10). AuNRs exposed to increasing concentrations of the analyte were characterized by means of transmission electron microscopy and UV-vis spectrophotometry to ascertain the mechanism of detection. The method was finally applied to the determination of thiomersal in various pharmaceutical samples and showed quantitative recoveries.

Schematic illustration of a miniaturized colorimetric method based on the use of a microdrop of gold nanorods (AuNRs) for thiomersal determination in pharmaceuticals. It is based on the photochemical decomposition of thiomersal and subsequent Hg0 generation with in-drop amalgamation.

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Acknowledgements

Financial support from the Spanish Ministry of Economy and Competitiveness (Project CTQ2015-68146-P) (MINECO/FEDER) is gratefully acknowledged. F. Pena-Pereira thanks Xunta de Galicia for financial support as a post-doctoral researcher of the I2C program. The CACTI facilities (University of Vigo) are also acknowledged for obtaining TEM and SEM images and performing EDS analyses.

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Authors and Affiliations

  1. Analytical and Food Chemistry Department, Faculty of Chemistry, University of Vigo, Campus As Lagoas-Marcosende s/n, 36310, Vigo, Spain

    Manuel Martín-Alonso, Francisco Pena-Pereira, Isela Lavilla & Carlos Bendicho

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  1. Manuel Martín-Alonso
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  2. Francisco Pena-Pereira
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  3. Isela Lavilla
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  4. Carlos Bendicho
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Correspondence to Carlos Bendicho.

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Martín-Alonso, M., Pena-Pereira, F., Lavilla, I. et al. Gold nanorods for in-drop colorimetric determination of thiomersal after photochemical decomposition. Microchim Acta 185, 221 (2018). https://doi.org/10.1007/s00604-018-2760-3

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