Schopfer Lawrence M, Masson Patrick, Lamourette Patricia, Simon Stéphanie, Lockridge Oksana
Eppley Institute, University of Nebraska Medical Center, Omaha, NE 68198, USA.
Eppley Institute, University of Nebraska Medical Center, Omaha, NE 68198, USA.
Anal Biochem. 2014 Sep 15;461:17-26. doi: 10.1016/j.ab.2014.05.021. Epub 2014 Jun 2.
Flight crews complain of illness following a fume event in aircraft. A chemical in jet engine oil, the neurotoxicant tri-o-cresyl phosphate, after metabolic activation to cresyl saligenin phosphate makes a covalent adduct on butyrylcholinesterase (BChE). We developed a mass spectrometry method for detection of the cresyl phosphate adduct on human BChE as an indicator of exposure. Monoclonal mAb2, whose amino acid sequence is provided, was crosslinked to cyanogen bromide-activated Sepharose 4B and used to immunopurify plasma BChE treated with cresyl saligenin phosphate. BChE was released with acetic acid, digested with pepsin, and analyzed by liquid chromatography-tandem mass spectrometry (LC-MSMS) on the Triple TOF 5600 mass spectrometer. Peptide FGES198AGAAS with an added mass of 170 Da from cresyl phosphate on serine 198 (Ser198) was detected as parent ion 966.4 Da. When characteristic daughter ions were monitored in the MSMS spectrum, the limit of detection was 0.1% cresyl saligenin phosphate inhibited plasma BChE. This corresponds to 2×10(-9) g in 0.5 ml or 23×10(-15) moles of inhibited BChE in 0.5 ml of plasma. In conclusion, a sensitive assay for exposure to tri-o-cresyl phosphate was developed. Laboratories that plan to use this method are cautioned that a positive result gives no proof that tri-o-cresyl phosphate is toxic at low levels.
在飞机发生烟雾事件后,机组人员抱怨患病。喷气发动机油中的一种化学物质,即神经毒剂三邻甲苯基磷酸酯,在代谢活化生成磷酸甲酚基水杨酯后,会与丁酰胆碱酯酶(BChE)形成共价加合物。我们开发了一种质谱方法,用于检测人BChE上的磷酸甲酚酯加合物,以此作为暴露的指标。提供了氨基酸序列的单克隆抗体mAb2与溴化氰活化的琼脂糖4B交联,并用于免疫纯化经磷酸甲酚基水杨酯处理的血浆BChE。用乙酸释放BChE,用胃蛋白酶消化,然后在Triple TOF 5600质谱仪上通过液相色谱-串联质谱(LC-MSMS)进行分析。在丝氨酸198(Ser198)处添加了来自磷酸甲酚酯的170 Da质量的肽FGES198AGAAS被检测为母离子966.4 Da。当在MSMS谱图中监测特征性子离子时,检测限为0.1%磷酸甲酚基水杨酯抑制的血浆BChE。这相当于0.5 ml中2×10(-9) g或0.5 ml血浆中23×10(-15)摩尔受抑制的BChE。总之,开发了一种用于检测三邻甲苯基磷酸酯暴露的灵敏检测方法。计划使用该方法的实验室需注意,阳性结果并不能证明低水平的三邻甲苯基磷酸酯具有毒性。