학술논문
High-resolution mass spectrometry provides novel insights into products of human metabolism of organophosphate and brominated flame retardants
Research Paper
Research Paper
Document Type
Report
Author
Source
Analytical and Bioanalytical Chemistry. March 2015, Vol. 407 Issue 7, p1871, 13 p.
Subject
Language
English
ISSN
1618-2642
Abstract
Author(s): Mohamed Abou-Elwafa Abdallah[sup.1] [sup.2] , Jinkang Zhang[sup.3] , Gopal Pawar[sup.1] , Mark R. Viant[sup.3] , J. Kevin Chipman[sup.3] , Kyle D'Silva[sup.4] , Maciej Bromirski[sup.5] , Stuart Harrad[sup.1] Author Affiliations: [...]
The high resolution, accurate mass, and fast scanning features of the Orbitrap.sup.TM mass spectrometer, combined with the separation power of ultrahigh-performance liquid chromatography were applied for the first time to study the metabolic profiles of several organic flame retardants (FRs) present in indoor dust. To mimic real-life exposure, in vitro cultured HepG2 human hepatocyte cell lines were exposed simultaneously to various FRs in an indoor dust extract for 24 h. Target parent FRs, hexabromocyclododecanes ([alpha]-, [beta]-, and [gamma]-HBCDs), tris-2-chloroethyl phosphate (TCEP), tris(1-chloro-2-propyl) phosphate (TCIPP), and tris(1,3-dichloro-2-propyl) phosphate (TDCIPP), were separated in a single run for the first time using alternating positive and negative heated ESI source. Further metabolite separation and identification was achieved using full scan (70,000 full width at half maximum (FWHM)), accurate mass (up to 1 ppm) spectrometry. Structural confirmation was performed via all ion fragmentation (AIF) spectra using the optional higher collisional dissociation (HCD) cell and MS/MS analysis. First insights into human metabolism of HBCDs revealed several hydroxylated and debrominated phase I metabolites, in addition to conjugated phase II glucuronides. Furthermore, various hydroxylated, oxidized, and conjugated metabolites of chlorinated phosphorous FRs were identified, leading to the suggestion of [alpha]-oxidation as a significant metabolic pathway for these compounds. Electronic supplementary material The online version of this article (doi:10.1007/s00216-015-8466-z) contains supplementary material, which is available to authorized users.
The high resolution, accurate mass, and fast scanning features of the Orbitrap.sup.TM mass spectrometer, combined with the separation power of ultrahigh-performance liquid chromatography were applied for the first time to study the metabolic profiles of several organic flame retardants (FRs) present in indoor dust. To mimic real-life exposure, in vitro cultured HepG2 human hepatocyte cell lines were exposed simultaneously to various FRs in an indoor dust extract for 24 h. Target parent FRs, hexabromocyclododecanes ([alpha]-, [beta]-, and [gamma]-HBCDs), tris-2-chloroethyl phosphate (TCEP), tris(1-chloro-2-propyl) phosphate (TCIPP), and tris(1,3-dichloro-2-propyl) phosphate (TDCIPP), were separated in a single run for the first time using alternating positive and negative heated ESI source. Further metabolite separation and identification was achieved using full scan (70,000 full width at half maximum (FWHM)), accurate mass (up to 1 ppm) spectrometry. Structural confirmation was performed via all ion fragmentation (AIF) spectra using the optional higher collisional dissociation (HCD) cell and MS/MS analysis. First insights into human metabolism of HBCDs revealed several hydroxylated and debrominated phase I metabolites, in addition to conjugated phase II glucuronides. Furthermore, various hydroxylated, oxidized, and conjugated metabolites of chlorinated phosphorous FRs were identified, leading to the suggestion of [alpha]-oxidation as a significant metabolic pathway for these compounds. Electronic supplementary material The online version of this article (doi:10.1007/s00216-015-8466-z) contains supplementary material, which is available to authorized users.