title: Determination of nitrogen mustard hydrolysis products, ethanolamines by gas chromatography-mass spectrometry after tert-butyldimethylsilyl derivatization.
abstract: A method for determining N-ethyldiethanolamine (EDEA), N-methyldiethanolamine (MDEA) and triethanolamine (TEA), hydrolysis products of nitrogen mustards, in water, urine and blood samples using gas chromatography-mass spectrometry (GC-MS) after derivatization by tert-butyldimethylsilylation (TBDMS) is described. The sample solution was evaporated to dryness, and reacted with N-methyl-N-(tert-butyldimethylsilyl)trifluoroacetamide (MTBSTFA) at 60 degrees C for 1h. The TBDMS derivatives were separated on a DB-5 column and detected by electron-ionization MS. The quantitation of EDEA, MDEA and TEA was performed by measuring the respective peak areas on the extracted ion chromatograms of m/z 216, m/z 202 and m/z 346, respectively, using nonadecane (C19), the peak area of which was measured at m/z 268, as an internal standard. When the water sample was initially analyzed, considerable loss of EDEA, MDEA and TEA occurred by evaporation. The addition of hydrochloric acid (HCl) to the water sample (final 1 mM), however, permitted quantitative recoveries to be achieved (88%, 88% and 79% for EDEA-(TBDMS)2, MDEA-(TBDMS)2 and TEA-(TBDMS)3, respectively). The limits of detections (LODs, scan mode, S/N = 3) were 2.5, 2.5 and 10 ng/ml for EDEA, MDEA and TEA, respectively. Ethanolamines could be also determined in urine samples (volume 0.1 ml), with reasonable recoveries of 72-100% by the addition of HCl (final 1 mM). For the analysis of serum samples, the sample was precipitated by the addition of perchloric acid (final 3.2%), and the resulting supernatant was neutralized with potassium carbonate, and then acidified by the addition of HCl. The recovery of TBDMS derivatives of ethanolamines was found to rather low (7-31%).
authors.affiliation: National Research Institute of Police Science, 6-3-1 Kashiwanoha, Kashiwa, Chiba 277-0882, Japan. ohsawa@nrips.go.jp
authors.forename: Isaac
authors.initials: I
authors.lastname: Ohsawa
authors.forename: Yasuo
authors.initials: Y
authors.lastname: Seto
mesh_terms: D000081:Acetamides; D002138:Calibration; D004983:Ethanolamines / Q000032:analysis* / Q000097:blood / Q000652:urine; D005463:Fluoroacetates; D008401:Gas Chromatography-Mass Spectrometry / Q000295:instrumentation / Q000379:methods*; D006801:Humans; D006868:Hydrolysis; D008466:Mechlorethamine / Q000032:analysis / Q000737:chemistry*; D017646:Organosilicon Compounds / Q000737:chemistry*; D015203:Reproducibility of Results; D014269:Trifluoroacetic Acid / Q000737:chemistry
chemical_list: D000081:Acetamides; D004983:Ethanolamines; D005463:Fluoroacetates; D017646:Organosilicon Compounds; C008430:N-methyldiethanolamine; D008466:Mechlorethamine; C059151:N-methyl-N-(tert-butyldimethylsilyl)trifluoroacetamide; C009546:triethanolamine; D014269:Trifluoroacetic Acid