Suzuki O, Hattori H, Liu J, Seno H, Kumazawa T
Department of Legal Medicine, Hamamatsu University School of Medicine, Japan.
Forensic Sci Int. 1990 Jul;46(3):169-80. doi: 10.1016/0379-0738(90)90303-g.
Positive-ion electron impact (PIEI), positive-ion chemical ionization (PICI) and negative-ion chemical ionization (NICI) mass spectra of 9 carbamate pesticides are presented. In the PIEI mode, the spectra showed small molecular peaks, intense or base peaks due to M - CH3NHCO + H and peaks at m/z 58 due to CH3NHCO. In the PICI mode, peaks due to M + H, M + C2H5, M - CH3NHCO + 2H, CH3NHCO(m/z 58) and M-28 appeared. The cations at m/z 58 found in both PIEI and PICI modes seem very useful for screening of a carbamate. In the NICI mode, the spectra showed peaks due to M - CH3NHCO and characteristic anions appearing at mass numbers higher than molecular ones, which were probably due to dimerization of [M - CH3NHCO]-followed by hydrogen attachment. Carbamates, which had been added to urine, plasma, whole blood, the liver, kidney and brain, could be rapidly isolated by use of Sep-Pak C18 cartridges with chloroform as an elution solvent. They could be detected by wide-bore capillary gas chromatography with a SPB-5 column, with satisfactory separation from impurities in their underivatized forms.
本文给出了9种氨基甲酸酯类农药的正离子电子轰击(PIEI)、正离子化学电离(PICI)和负离子化学电离(NICI)质谱图。在PIEI模式下,质谱图显示出小分子峰、因M - CH3NHCO + H产生的强峰或基峰以及因CH3NHCO产生的m/z 58处的峰。在PICI模式下,出现了因M + H、M + C2H5、M - CH3NHCO + 2H、CH3NHCO(m/z 58)和M - 28产生的峰。在PIEI和PICI模式下均发现的m/z 58处的阳离子似乎对氨基甲酸酯的筛选非常有用。在NICI模式下,质谱图显示出因M - CH3NHCO产生的峰以及出现在质量数高于分子质量数处的特征性阴离子,这可能是由于[M - CH3NHCO]-二聚化后加氢所致。添加到尿液、血浆、全血、肝脏、肾脏和大脑中的氨基甲酸酯类物质,可使用Sep - Pak C18柱以氯仿作为洗脱溶剂快速分离。它们可以通过使用SPB - 5柱的宽口径毛细管气相色谱法进行检测,在未衍生化形式下能与杂质实现令人满意的分离。