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Comprehensive profiling of mercapturic acid metabolites from dietary acrylamide as short-term exposure biomarkers for evaluation of toxicokinetics in rats and daily internal exposure in humans using isotope dilution ultra-high performance liquid chromatography tandem mass spectrometry.
Anal Chim Acta. 2015 Sep 24; 894:54-64.AC

Abstract

Mercapturic acid metabolites from dietary acrylamide are important short-term exposure biomarkers for evaluating the in vivo toxicity of acrylamide. Most of studies have focused on the measurement of two metabolites, N-acetyl-S-(2-carbamoylethyl)-L-cysteine (AAMA) and N-acetyl-S-(2-carbamoyl-2-hydroxyethyl)-L-cysteine (GAMA). Thus, the comprehensive profile of acrylamide urinary metabolites cannot be fully understood. We developed an isotope dilution ultra-high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) method for the simultaneous determination of all four mercapturic acid adducts of acrylamide and its primary metabolite glycidamide under the electroscopy ionization negative (ESI-) mode in the present study. The limit of detection (LOD) and limit of quantification (LOQ) of the analytes ranged 0.1-0.3 ng/mL and 0.4-1.0 ng/mL, respectively. The recovery rates with low, intermediate and high spiking levels were calculated as 95.5%-105.4%, 98.2%-114.0% and 92.2%-108.9%, respectively. Acceptable within-laboratory reproducibility (RSD<7.0%) substantially supported the use of current method for robust analysis. Rapid pretreatment procedures and short run time (8 min per sample) ensured good efficiency of metabolism profiling, indicating a wide application for investigating short-term internal exposure of dietary acrylamide. Our proposed UHPLC-MS/MS method was successfully applied to the toxicokinetic study of acrylamide in rats. Meanwhile, results of human urine analysis indicated that the levels of N-acetyl-S-(2-carbamoylethyl)-L-cysteine-sulfoxide (AAMA-sul), which did not appear in the mercapturic acid metabolites in rodents, were more than the sum of GAMA and N-acetyl-S-(1-carbamoyl-2-hydroxyethyl)-L-cysteine (iso-GAMA). Thus, AAMA-sul may alternatively become a specific biomarker for investigating the acrylamide exposure in humans. Current proposed method provides a substantial methodology support for comprehensive profiling of toxicokinetics and daily internal exposure evaluations of acrylamide in vivo.

Authors+Show Affiliations

Department of Food Science and Nutrition, College of Biosystems Engineering and Food Science, Zhejiang University, Hangzhou 310058, Zhejiang, China; Zhejiang Key Laboratory for Agro-Food Processing, Zhejiang R & D Center for Food Technology and Equipment, Fuli Institute of Food Science, Zhejiang University, Hangzhou 310058, Zhejiang, China.Department of Food Science and Nutrition, College of Biosystems Engineering and Food Science, Zhejiang University, Hangzhou 310058, Zhejiang, China.Department of Food Science and Nutrition, College of Biosystems Engineering and Food Science, Zhejiang University, Hangzhou 310058, Zhejiang, China.Zhejiang Provincial Center for Disease Control and Prevention, Hangzhou 310051, Zhejiang, China.Zhejiang Provincial Center for Disease Control and Prevention, Hangzhou 310051, Zhejiang, China.Zhejiang Provincial Center for Disease Control and Prevention, Hangzhou 310051, Zhejiang, China. Electronic address: renyiping@263.net.

Pub Type(s)

Evaluation Study
Journal Article
Research Support, Non-U.S. Gov't

Language

eng

PubMed ID

26423628

Citation

Zhang, Yu, et al. "Comprehensive Profiling of Mercapturic Acid Metabolites From Dietary Acrylamide as Short-term Exposure Biomarkers for Evaluation of Toxicokinetics in Rats and Daily Internal Exposure in Humans Using Isotope Dilution Ultra-high Performance Liquid Chromatography Tandem Mass Spectrometry." Analytica Chimica Acta, vol. 894, 2015, pp. 54-64.
Zhang Y, Wang Q, Cheng J, et al. Comprehensive profiling of mercapturic acid metabolites from dietary acrylamide as short-term exposure biomarkers for evaluation of toxicokinetics in rats and daily internal exposure in humans using isotope dilution ultra-high performance liquid chromatography tandem mass spectrometry. Anal Chim Acta. 2015;894:54-64.
Zhang, Y., Wang, Q., Cheng, J., Zhang, J., Xu, J., & Ren, Y. (2015). Comprehensive profiling of mercapturic acid metabolites from dietary acrylamide as short-term exposure biomarkers for evaluation of toxicokinetics in rats and daily internal exposure in humans using isotope dilution ultra-high performance liquid chromatography tandem mass spectrometry. Analytica Chimica Acta, 894, 54-64. https://doi.org/10.1016/j.aca.2015.08.033
Zhang Y, et al. Comprehensive Profiling of Mercapturic Acid Metabolites From Dietary Acrylamide as Short-term Exposure Biomarkers for Evaluation of Toxicokinetics in Rats and Daily Internal Exposure in Humans Using Isotope Dilution Ultra-high Performance Liquid Chromatography Tandem Mass Spectrometry. Anal Chim Acta. 2015 Sep 24;894:54-64. PubMed PMID: 26423628.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Comprehensive profiling of mercapturic acid metabolites from dietary acrylamide as short-term exposure biomarkers for evaluation of toxicokinetics in rats and daily internal exposure in humans using isotope dilution ultra-high performance liquid chromatography tandem mass spectrometry. AU - Zhang,Yu, AU - Wang,Qiao, AU - Cheng,Jun, AU - Zhang,Jingshun, AU - Xu,Jiaojiao, AU - Ren,Yiping, Y1 - 2015/08/25/ PY - 2015/07/28/received PY - 2015/08/16/accepted PY - 2015/10/2/entrez PY - 2015/10/2/pubmed PY - 2016/4/14/medline KW - Acrylamide KW - Glycidamide KW - Internal exposure KW - Mercapturic acid metabolites KW - Toxicokinetics KW - Urinary biomarkers SP - 54 EP - 64 JF - Analytica chimica acta JO - Anal Chim Acta VL - 894 N2 - Mercapturic acid metabolites from dietary acrylamide are important short-term exposure biomarkers for evaluating the in vivo toxicity of acrylamide. Most of studies have focused on the measurement of two metabolites, N-acetyl-S-(2-carbamoylethyl)-L-cysteine (AAMA) and N-acetyl-S-(2-carbamoyl-2-hydroxyethyl)-L-cysteine (GAMA). Thus, the comprehensive profile of acrylamide urinary metabolites cannot be fully understood. We developed an isotope dilution ultra-high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) method for the simultaneous determination of all four mercapturic acid adducts of acrylamide and its primary metabolite glycidamide under the electroscopy ionization negative (ESI-) mode in the present study. The limit of detection (LOD) and limit of quantification (LOQ) of the analytes ranged 0.1-0.3 ng/mL and 0.4-1.0 ng/mL, respectively. The recovery rates with low, intermediate and high spiking levels were calculated as 95.5%-105.4%, 98.2%-114.0% and 92.2%-108.9%, respectively. Acceptable within-laboratory reproducibility (RSD<7.0%) substantially supported the use of current method for robust analysis. Rapid pretreatment procedures and short run time (8 min per sample) ensured good efficiency of metabolism profiling, indicating a wide application for investigating short-term internal exposure of dietary acrylamide. Our proposed UHPLC-MS/MS method was successfully applied to the toxicokinetic study of acrylamide in rats. Meanwhile, results of human urine analysis indicated that the levels of N-acetyl-S-(2-carbamoylethyl)-L-cysteine-sulfoxide (AAMA-sul), which did not appear in the mercapturic acid metabolites in rodents, were more than the sum of GAMA and N-acetyl-S-(1-carbamoyl-2-hydroxyethyl)-L-cysteine (iso-GAMA). Thus, AAMA-sul may alternatively become a specific biomarker for investigating the acrylamide exposure in humans. Current proposed method provides a substantial methodology support for comprehensive profiling of toxicokinetics and daily internal exposure evaluations of acrylamide in vivo. SN - 1873-4324 UR - https://www.unboundmedicine.com/medline/citation/26423628/Comprehensive_profiling_of_mercapturic_acid_metabolites_from_dietary_acrylamide_as_short_term_exposure_biomarkers_for_evaluation_of_toxicokinetics_in_rats_and_daily_internal_exposure_in_humans_using_isotope_dilution_ultra_high_performance_liquid_chromatography_tandem_mass_spectrometry_ DB - PRIME DP - Unbound Medicine ER -