de Jong A P, Kok R M, Cramers C A, Wadman S K
J Chromatogr. 1986 Oct 31;382:19-30. doi: 10.1016/s0378-4347(00)83500-8.
A method for the assay of acidic catecholamine metabolites in biological fluids using capillary gas chromatography--electron-capture negative-ion mass spectrometry is described. The method combines acetylation of phenolic hydroxy groups in buffered aqueous solution followed by pentafluorobenzyl ester formation and acetylation of aliphatic hydroxy groups under anhydrous conditions. The resulting per-O-acetyl carboxypentafluorobenzyl esters provided excellent negative-ion mass spectra with intense and diagnostic anions. The sensitivity of the analysis using electron-capture negative-ion mass spectrometry exceeds that using electron-impact mass spectrometry by two to three orders of magnitude. Analysis of acidic catecholamine metabolites in human lumbar cerebrospinal fluid and plasma were performed with good precision (sigma rel less than 5%) at the low nanomoles per litre level.
描述了一种使用毛细管气相色谱 - 电子捕获负离子质谱法测定生物流体中酸性儿茶酚胺代谢物的方法。该方法包括在缓冲水溶液中对酚羟基进行乙酰化，随后形成五氟苄酯，并在无水条件下对脂肪族羟基进行乙酰化。所得的全 - O - 乙酰基羧基五氟苄酯提供了具有强诊断性阴离子的出色负离子质谱图。使用电子捕获负离子质谱法的分析灵敏度比使用电子轰击质谱法高两到三个数量级。在人腰椎脑脊液和血浆中对酸性儿茶酚胺代谢物进行分析时，在每升低纳摩尔水平下具有良好的精密度（相对标准偏差小于5%）。
