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Trimethylselenonium ion determination in human urine by high-performance liquid chromatography–hydride generation–atomic fluorescence spectrometry optimization of the hydride generation step

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Abstract

This work describes the intricacies of the determination of the trimethylselenonium ion (TMSe) in human urine via high-performance liquid chromatography–hydride generation–atomic fluorescence spectrometry (HPLC-HG-AFS). By definition, this technique requires that the separated TMSe can be online converted into a volatile compound. Literature data for the determination of TMSe via the hydride generation technique are contradictory; i.e., some authors claim that direct formation of volatile compounds is possible under reduction with NaBH4, whereas others reported that a digestion step is mandatory prior to conversion. We studied and optimized the conditions for online conversion by varying the mobile phase composition (pyridine, phosphate, and acetate), testing different reaction coils, and optimizing the hydride generation conditions, although technically no hydride (H2Se) is formed but a dimethylselenide (DMSe). The optimized conditions were used for the analysis of 64 urine samples of 16 (unexposed) volunteers and the determination of low amounts of TMSe (LOD = 0.2 ng mL−1). Total (specific gravity–corrected) selenium concentrations in the urine samples ranged from 7.9 ± 0.7 to 29.7 ± 5.0 ng mL−1 for individual volunteers. Four volunteers were characterized as TMSe producers (hINMT genotype GA) and 12 were non-producers (hINMT genotype GG). Urine of TMSe producers contained 2.5 ± 1.7 ng mL−1 of TMSe, compared to 0.2 ± 0.2 ng mL−1 for non-producers.

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Acknowledgements

The work was a part of a research program funded by the Slovenian Research Agency (P1-0143).

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Authors and Affiliations

  1. Department of Environmental Sciences, Jožef Stefan Institute, Jamova 39, Ljubljana, Slovenia

    Zdenka Šlejkovec, Anja Stajnko, Darja Mazej, Marta Jagodic Hudobivnik & Ingrid Falnoga

  2. Faculty of Chemical Engineering, Department of Analytical Chemistry, University of Chemistry and Technology, Prague, Czech Republic

    Oto Mestek

  3. Institute of Chemistry, Analytical Chemistry for Health and Environment, University of Graz, Universitätsplatz 3, 8010, Graz, Austria

    Bassam Lajin & Walter Goessler

  4. Institute of Chemistry, ChromICP, University of Graz, Universitaetsplatz 1, 8010, Graz, Austria

    Bassam Lajin

  5. Department of Analytical Chemistry, National Institute of Chemistry, Hajdrihova 19, 1000, Ljubljana, Slovenia

    Johannes T. van Elteren

Authors
  1. Zdenka Šlejkovec
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  2. Anja Stajnko
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  3. Darja Mazej
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  9. Ingrid Falnoga
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Correspondence to Ingrid Falnoga.

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Sampling was performed following the ethical standards (Declaration of Helsinki) and written consent was obtained from all participants. The protocol was approved by the National Medical Ethics Committee of the Republic of Slovenia (number of accordance: 0120–431/2018/4).

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Šlejkovec, Z., Stajnko, A., Mazej, D. et al. Trimethylselenonium ion determination in human urine by high-performance liquid chromatography–hydride generation–atomic fluorescence spectrometry optimization of the hydride generation step. Anal Bioanal Chem 415, 317–326 (2023). https://doi.org/10.1007/s00216-022-04408-6

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  • DOI: https://doi.org/10.1007/s00216-022-04408-6

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