Ethyl chloroformate mediated gas chromatographic-mass spectrometric biomonitoring of acidic biomarkers of occupational exposure and endogenous metabolites in human urine

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60076658%3A12110%2F21%3A43902687" target="_blank" >RIV/60076658:12110/21:43902687 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/60077344:_____/21:00545721 RIV/00216275:25310/21:39917750 RIV/75010330:_____/21:00013575

Výsledek na webu

<a href="https://www.sciencedirect.com/science/article/pii/S0021967321006713" target="_blank" >https://www.sciencedirect.com/science/article/pii/S0021967321006713</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1016/j.chroma.2021.462547" target="_blank" >10.1016/j.chroma.2021.462547</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Ethyl chloroformate mediated gas chromatographic-mass spectrometric biomonitoring of acidic biomarkers of occupational exposure and endogenous metabolites in human urine

Popis výsledku v původním jazyce

Numerous industrial organic pollutants such as aromates, alkoxyalcohols, other organic solvents and monomers are absorbed, metabolized, and finally excreted in urine mostly as carboxylic acids that are determined as biomarkers of exposure. For a number of these xenometabolites, biological limits (levels of biomarkers in biological material) have been established to prevent damage to human health. Till now, most of the analytical procedures used have been optimized for one or a few analytes. Here, we report a more comprehensive approach enabling rapid GC-MS screening of sixteen acidic biomarkers in urine that are metabolized in the human body from several important industrial chemicals; benzene, toluene, styrene, xylenes, alkoxyalcohols, carbon disulfide, furfural and N,N-dimethylformamide. The new method involves immediate in situ derivatization – liquid liquid microextraction of urine by an ethyl chloroformate-ethanol-chloroform-pyridine medium and GC-MS analysis of the derivatized analytes in the lower organic phase. The xenometabolite set represents diverse chemical structures and some of hippuric and mercapturic acids also provided unusual derivatives that were unambiguously elucidated by means of new ethyl chloroformates labeled with stable isotopes and by synthesis of the missing reference standards. In the next step, an automated routine was developed for GC-MS/MS analysis using a MetaboAuto® sample preparation workstation and the new method was validated for fourteen metabolites over the relevant concentration range of each analyte in the spiked pooled human urine. It shows good linearity (R2 ≥ 0.982), accuracy (from 85% to 120%), precision (from 0.7% to 20%) and recovery (from 89% to 120%). The method performance was further successfully proved by GC-MS/MS analysis of the certified IP45 and RM6009 reference urines. Moreover, we show that the new method opens up the possibility for biomonitoring of combined and cumulative occupational exposures as well as for urinary metabolite profiling of persons exposed to harmful industrial chemicals.

Název v anglickém jazyce

Ethyl chloroformate mediated gas chromatographic-mass spectrometric biomonitoring of acidic biomarkers of occupational exposure and endogenous metabolites in human urine

Popis výsledku anglicky

Numerous industrial organic pollutants such as aromates, alkoxyalcohols, other organic solvents and monomers are absorbed, metabolized, and finally excreted in urine mostly as carboxylic acids that are determined as biomarkers of exposure. For a number of these xenometabolites, biological limits (levels of biomarkers in biological material) have been established to prevent damage to human health. Till now, most of the analytical procedures used have been optimized for one or a few analytes. Here, we report a more comprehensive approach enabling rapid GC-MS screening of sixteen acidic biomarkers in urine that are metabolized in the human body from several important industrial chemicals; benzene, toluene, styrene, xylenes, alkoxyalcohols, carbon disulfide, furfural and N,N-dimethylformamide. The new method involves immediate in situ derivatization – liquid liquid microextraction of urine by an ethyl chloroformate-ethanol-chloroform-pyridine medium and GC-MS analysis of the derivatized analytes in the lower organic phase. The xenometabolite set represents diverse chemical structures and some of hippuric and mercapturic acids also provided unusual derivatives that were unambiguously elucidated by means of new ethyl chloroformates labeled with stable isotopes and by synthesis of the missing reference standards. In the next step, an automated routine was developed for GC-MS/MS analysis using a MetaboAuto® sample preparation workstation and the new method was validated for fourteen metabolites over the relevant concentration range of each analyte in the spiked pooled human urine. It shows good linearity (R2 ≥ 0.982), accuracy (from 85% to 120%), precision (from 0.7% to 20%) and recovery (from 89% to 120%). The method performance was further successfully proved by GC-MS/MS analysis of the certified IP45 and RM6009 reference urines. Moreover, we show that the new method opens up the possibility for biomonitoring of combined and cumulative occupational exposures as well as for urinary metabolite profiling of persons exposed to harmful industrial chemicals.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10406 - Analytical chemistry

Projekt

<a href="/cs/project/GA17-22276S" target="_blank" >GA17-22276S: Nové metody pro metabolomickou analýzu obtížně stanovitelných metabolitů</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2021

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Journal of Chromatography A

ISSN

0021-9673

e-ISSN

—

Svazek periodika

1656

Číslo periodika v rámci svazku

October 2021

Stát vydavatele periodika

NL - Nizozemsko

Počet stran výsledku

16

Strana od-do

462547

Kód UT WoS článku

000701668500002

EID výsledku v databázi Scopus

2-s2.0-85115224235