Trimethylselenonium ion determination in human urine by high-performance liquid chromatography–hydride generation–atomic fluorescence spectrometry optimization of the hydride generation step
(2023) In Analytical and Bioanalytical Chemistry 415(2). p.317-326- 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... (More)
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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- author
- Šlejkovec, Zdenka ; Stajnko, Anja LU ; Mazej, Darja ; Hudobivnik, Marta Jagodic ; Mestek, Oto ; Lajin, Bassam ; Goessler, Walter ; van Elteren, Johannes T. and Falnoga, Ingrid
- publishing date
- 2023-01
- type
- Contribution to journal
- publication status
- published
- keywords
- Hydride generation, Reaction coil, TMSe, Trimethylselenonium ion, Urine
- in
- Analytical and Bioanalytical Chemistry
- volume
- 415
- issue
- 2
- pages
- 317 - 326
- publisher
- Springer Science and Business Media B.V.
- external identifiers
-
- scopus:85141500072
- pmid:36348039
- ISSN
- 1618-2642
- DOI
- 10.1007/s00216-022-04408-6
- language
- English
- LU publication?
- no
- additional info
- Publisher Copyright: © 2022, Springer-Verlag GmbH Germany, part of Springer Nature.
- id
- 42425e47-f1d8-43b8-bb75-65a83393290f
- date added to LUP
- 2025-02-21 21:44:07
- date last changed
- 2025-05-31 05:42:40
@article{42425e47-f1d8-43b8-bb75-65a83393290f,
abstract = {{<p>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 NaBH<sub>4</sub>, 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 (H<sub>2</sub>Se) 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<sup>−1</sup>). Total (specific gravity–corrected) selenium concentrations in the urine samples ranged from 7.9 ± 0.7 to 29.7 ± 5.0 ng mL<sup>−1</sup> 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<sup>−1</sup> of TMSe, compared to 0.2 ± 0.2 ng mL<sup>−1</sup> for non-producers.</p>}},
author = {{Šlejkovec, Zdenka and Stajnko, Anja and Mazej, Darja and Hudobivnik, Marta Jagodic and Mestek, Oto and Lajin, Bassam and Goessler, Walter and van Elteren, Johannes T. and Falnoga, Ingrid}},
issn = {{1618-2642}},
keywords = {{Hydride generation; Reaction coil; TMSe; Trimethylselenonium ion; Urine}},
language = {{eng}},
number = {{2}},
pages = {{317--326}},
publisher = {{Springer Science and Business Media B.V.}},
series = {{Analytical and Bioanalytical Chemistry}},
title = {{Trimethylselenonium ion determination in human urine by high-performance liquid chromatography–hydride generation–atomic fluorescence spectrometry optimization of the hydride generation step}},
url = {{http://dx.doi.org/10.1007/s00216-022-04408-6}},
doi = {{10.1007/s00216-022-04408-6}},
volume = {{415}},
year = {{2023}},
}