title: Analysis of heterocyclic amines in hair by on-line in-tube solid-phase microextraction coupled with liquid chromatography-tandem mass spectrometry.
abstract: Mutagenic and carcinogenic heterocyclic amines (HCAs) are formed during heating of various proteinaceous foods, but human exposure to HCAs has not yet been elucidated in detail. To assess long-term exposure to HCAs, we developed a simple and sensitive method for measuring HCAs in hair by automated on-line in-tube solid-phase microextraction (SPME) coupled with liquid chromatography-tandem mass spectrometry (LC-MS/MS). Using a Zorbax Eclipse XDB-C8 column, 16 HCAs were analyzed within 15 min. The optimum in-tube SPME conditions were 20 draw/eject cycles of 40 μL sample at a flow rate of 200 μL min(-1) using a Supel-Q PLOT capillary column as an extraction device. The extracted HCAs were easily desorbed from the column by passage of the mobile phase, with no carryover observed. This in-tube SPME LC-MS/MS method showed good linearity for HCAs in the range of 10-2000 pg mL(-1), with correlation coefficients above 0.9989 (n=18), using stable isotope-labeled HCA internal standards. The detection limits (S/N=3) of 14 HCAs except for MeAαC and Glu-P-1 were 0.10-0.79 pg mL(-1). This method was successfully utilized to analyze 14 HCAs in hair samples without any interference peaks, with quantitative limits (S/N=10) of about 0.17-1.32 pg mg(-1) hair. Using this method, we evaluated the exposure to HCAs in cigarette smoke and the suitability of using hair HCAs as exposure biomarkers.
authors.affiliation: School of Pharmacy, Shujitsu University, Nishigawara, Okayama 703-8516, Japan. hkataoka@shujitsu.ac.jp
authors.forename: Hiroyuki
authors.initials: H
authors.lastname: Kataoka
authors.forename: Tsutomu
authors.initials: T
authors.lastname: Inoue
authors.forename: Keita
authors.initials: K
authors.lastname: Saito
authors.forename: Hisato
authors.initials: H
authors.lastname: Kato
authors.forename: Kazufumi
authors.initials: K
authors.lastname: Masuda
mesh_terms: D000588:Amines / Q000032:analysis* / Q000737:chemistry; D002853:Chromatography, Liquid / Q000379:methods / Q000592:standards; D006197:Hair / Q000737:chemistry*; D006571:Heterocyclic Compounds / Q000032:analysis / Q000737:chemistry; D006801:Humans; D009153:Mutagens / Q000032:analysis* / Q000737:chemistry; D009862:Online Systems / Q000592:standards; D012907:Smoking / Q000378:metabolism; D052617:Solid Phase Microextraction / Q000379:methods* / Q000592:standards; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods / Q000592:standards; D053719:Tandem Mass Spectrometry / Q000379:methods* / Q000592:standards; D014028:Tobacco Smoke Pollution / Q000032:analysis*
chemical_list: D000588:Amines; D006571:Heterocyclic Compounds; D009153:Mutagens; D014028:Tobacco Smoke Pollution