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The use of chemical derivatization to enhance liquid chromatography/tandem mass spectrometric determination of 1‐hydroxypyrene, a biomarker for polycyclic aromatic hydrocarbons in human urine
Author(s) -
Li Yinghe,
Li Austin C.,
Shi Haihong,
Zhou Shaolian,
Shou Wilson Z.,
Jiang Xiangyu,
Naidong Weng,
Lauterbach John H.
Publication year - 2005
Publication title -
rapid communications in mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.528
H-Index - 136
eISSN - 1097-0231
pISSN - 0951-4198
DOI - 10.1002/rcm.2196
Subject(s) - chemistry , derivatization , chromatography , dansyl chloride , analyte , mass spectrometry , electrospray ionization , chemical ionization , sample preparation , electrospray , liquid chromatography–mass spectrometry , ionization , organic chemistry , ion
This article presents an analytical approach that used chemical derivatization to enhance mass spectrometric (MS) response in electrospray ionization (ESI) mode of 1‐hydroxypyrene (1‐OHP), a commonly used biomarker to monitor human exposure to polycyclic aromatic hydrocarbons (PAHs). The enhancement successfully enabled the desired detection of 50 pg/mL in human urine. The introduction of an MS‐friendly dansyl group to 1‐OHP enhanced both ionization efficiency in the ESI source and collision‐activated dissociation (CAD) in the collision cell. The response increase was estimated to be at least 200‐fold, and enabled the reduction of sample size to only 100 µL. The selective MS detection also facilitated a fast (run time 3 min) liquid chromatography (LC) method which successfully resolved the analyte and interferences. The sample processing procedure included enzymatic hydrolysis of glucuronide and sulfate conjugates, liquid‐liquid extraction, derivatization with dansyl chloride and a final liquid‐liquid extraction to generate clean extracts for LC/MS/MS analysis. This approach has been validated as sensitive, linear (50–1000 pg/mL), accurate and precise for the quantitation of 1‐OHP in human urine. This is the first report of using chemical derivatization to enhance MS/MS detection with fast chromatography in the determination of 1‐OHP in human urine. Copyright © 2005 John Wiley & Sons, Ltd.