Abstract
In this study, hydrodynamic chromatography coupled to inductively coupled plasma mass spectrometry has been evaluated for the simultaneous determination of dissolved and nanoparticulate species of gold and silver. Optimization of mobile phase was carried out with special attention to the column recovery of the different species and the resolution between them. Addition of 0.05 mM penicillamine to the mobile phase allowed the quantitative recovery of ionic gold and gold nanoparticles up to 50 nm, whereas 1 mM penicillamine was necessary for quantitative recovery of ionic silver and silver nanoparticles up to 40 nm. The resolution achieved between ionic gold and 10-nm gold nanoparticles was 0.7, whereas it ranged between 0.31 and 0.93 for ionic silver and 10-nm silver nanoparticles, depending on the composition of mobile phase. Best-case mass concentration detection limits for gold and silver species were 0.05 and 0.75 μg L−1, respectively. The developed methods allowed the simultaneous detection of nanoparticulate and dissolved species of gold and silver in less than 10 min. Size determination and quantification of gold and silver species were carried out in different dietary supplements, showing good agreement with the results obtained by electron microscopy and total and ultrafiltrable contents, respectively. Due to the attainable resolution, the quality of the quantitative results is affected by the relative abundance of nanoparticulate and dissolved species of the element and the size of the nanoparticles if present.
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The authors would like to acknowledge the use of Servicio General de Apoyo a la Investigación-SAI, Universidad de Zaragoza.
Funding
This work was supported by the Spanish Ministry of Science Innovation and Universities and the European Regional Development Fund, project RTI2018-096111-B-I00 (MICINN/FEDER) and project EFA 183/16/OUTBIOTICS, Program Interreg-POCTEFA 2014-2020, funded by FEDER.
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M.S. Jimenez is the supervisor and coordinator of all experimental work and data revision. She did the experimental work regarding the analysis of gold dietary supplement. She is responsible of writing the manuscript.
M. Bakir is responsible for the experimental work regarding the characterization and quantification of silver nanoparticles and dissolved silver and the analysis of silver dietary supplements. She is the author of all figures.
D. Isabal did the experimental work regarding the characterization of gold nanoparticles and dissolved gold.
M.T. Gómez is the coordinator of the work in the group laboratory, being responsible for the supplies and has collaborated in the writing and revision of the manuscript.
J. Perez-Arantegui is responsible for FESEM and TEM measurements and data interpretation. She has collaborated in the revision of the manuscript.
F. Laborda is the main researcher of project RTI2018-096111-B-I00 (MICINN/FEDER). He has supervised the experimental work and the writing and revision of the manuscript.
J.R. Castillo is the main researcher of project EFA 183/16/OUTBIOTICS, Program Interreg-POCTEFA 2014-2020, funded by FEDER. He has supervised the writing and revision of the manuscript.
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In memory of Juan R. Castillo who passed away a few days before the publication of this article.
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Jiménez, M.S., Bakir, M., Isábal, D. et al. Evaluation of hydrodynamic chromatography coupled to inductively coupled plasma mass spectrometry for speciation of dissolved and nanoparticulate gold and silver. Anal Bioanal Chem 413, 1689–1699 (2021). https://doi.org/10.1007/s00216-020-03132-3
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DOI: https://doi.org/10.1007/s00216-020-03132-3