title: A column-switching LC-MS/MS method for simultaneous quantification of biomarkers for 1,3-butadiene exposure and oxidative damage in human urine.
abstract: 1,3-Butadiene (BD) is a ubiquitous environmental pollutant found in tobacco smoke. In vivo, BD is mainly metabolized to form monohydroxybutenylmercapturic acid (MHBMA) and N-acetyl-S-(3, 4-dihydroxybutyl) cysteine (DHBMA). The accurate quantification of MHBMA and DHBMA in urine may provide important insights into the actual internal exposure of the general population to BD. 8-Hydroxy-2-deoxyguanosine (8-OHdG) is the biomarker of oxidative damage. In this study, a column-switching LC-MS/MS method was developed and validated for the simultaneous quantification of MHBMA, DHBMA derived from BD exposure and 8-OHdG in human urine. Urine samples were loaded on a LiChrospher(®) RP-8 ADS (25μm) 25×4mm RAM column for the extraction and clean-up of analytes. The separation was achieved using a SUPELCO(®) LC-18-DB column (75mm×3.0mm, 3μm). The analytes were ionized in negative electrospray ionization mode and analyzed in multiple reaction monitoring mode. Under optimum conditions, recoveries ranged from 78.9% to 101.7%, with relative standard deviations less than 11%. The limits of quantification ranged from 0.15 to 0.27ng/mL, highlighting the high sensitivity of this simple method. The validated method was successfully applied to analysis urine samples from 56 non-smokers and 233 smokers who smoked cigarettes with 3 different tar yields. There was a correlation between urinary MHBMA, DHBMA and 8-OHdG. This method did not require any preparation process and efficiently removed interference from the matrix by using column-switching. The developed method is applicable to epidemiological studies.
authors: Institute of Applied Technology, Hefei Institutes of Physical Science, Chinese Academy of Sciences, Hefei 230031, China; China National Tobacco Quality Supervision & Test Centre, Zhengzhou 450001, China.
authors: Xiaotao
authors: X
authors: Zhang
authors: China National Tobacco Quality Supervision & Test Centre, Zhengzhou 450001, China. Electronic address: qsfctc@163.com.
authors: Hongwei
authors: H
authors: Hou
authors: China National Tobacco Quality Supervision & Test Centre, Zhengzhou 450001, China.
authors: Huan
authors: H
authors: Chen
authors: China National Tobacco Quality Supervision & Test Centre, Zhengzhou 450001, China.
authors: Yong
authors: Y
authors: Liu
authors: Institute of Applied Technology, Hefei Institutes of Physical Science, Chinese Academy of Sciences, Hefei 230031, China. Electronic address: wangan@aiofm.ac.cn.
authors: An
authors: A
authors: Wang
authors: Institute of Applied Technology, Hefei Institutes of Physical Science, Chinese Academy of Sciences, Hefei 230031, China; China National Tobacco Quality Supervision & Test Centre, Zhengzhou 450001, China. Electronic address: huqy1965@163.com.
authors: Qingyuan
authors: Q
authors: Hu
mesh_terms: D015415:Biomarkers / Q000652:urine*; D002070:Butadienes / Q000633:toxicity*; D002853:Chromatography, Liquid / Q000379:methods*; D006801:Humans; D018384:Oxidative Stress; D053719:Tandem Mass Spectrometry / Q000379:methods*
chemical_list: D015415:Biomarkers; D002070:Butadienes; C031763:1,3-butadiene
keywords: 1,3-Butadiene; Biomarker; Column-switching; LC–MS/MS; Oxidative damage