Chen Bud-Gen, Wang Sheng-Meng, Liu Ray H
Department of Medical Technology, Fooyin University, Kaohsiung Hsien 831-02, Taiwan.
J Mass Spectrom. 2007 Aug;42(8):1012-23. doi: 10.1002/jms.1227.
Opiates such as hydrocodone, hydromorphone, oxycodone, noroxycodone, and oxymorphone reportedly may interfere with the analysis of morphine and codeine. The analysis of these compounds themselves also is an important issue. Thus, double derivatization approaches utilizing methoxyamine and hydroxylamine to first form oxime products with keto-opiates, followed by the derivatization with trimethylsilyl (TMS) or propionyl groups, have been developed for the simultaneous analysis of these compounds. However, these studies have not included all compounds of interest and resulted in inadequate chromatographic resolution or significant intensity cross-contribution between the ions designating the analyte and its deuterated internal standard for certain compounds. By exploring three-step derivatization approaches with the combination of various derivatization groups and orders, this study concluded that application of methoxyimino/propionyl/TMS groups, in the order listed, facilitated the simultaneous analysis of eight opiates (morphine, 6-acetylmorphine, hydromorphone, oxymorphone, codeine, hydrocodone, oxycodone and noroxycodone) in urine samples, achieving satisfactory limits of quantitation and detection. In addition, the adapted approach resulted in two usable products for morphine and codeine providing alternatives, should interferences render any of these products non-usable.
据报道，诸如氢可酮、氢吗啡酮、羟考酮、去甲羟考酮和羟吗啡酮等阿片类药物可能会干扰吗啡和可待因的分析。对这些化合物本身的分析也是一个重要问题。因此，已开发出利用甲氧基胺和羟胺首先与酮类阿片形成肟产物，然后用三甲基硅烷基（TMS）或丙酰基进行衍生化的双衍生化方法，用于同时分析这些化合物。然而，这些研究并未涵盖所有感兴趣的化合物，并且对于某些化合物而言，导致了色谱分辨率不足或指定分析物及其氘代内标的离子之间存在显著的强度交叉贡献。通过探索结合各种衍生化基团和顺序的三步衍生化方法，本研究得出结论，按所列顺序应用甲氧基亚氨基/丙酰基/TMS基团有助于同时分析尿液样本中的八种阿片类药物（吗啡、6-乙酰吗啡、氢吗啡酮、羟吗啡酮、可待因、氢可酮、羟考酮和去甲羟考酮），实现了令人满意的定量和检测限。此外，调整后的方法为吗啡和可待因产生了两种可用产物，在干扰导致这些产物中的任何一种无法使用时提供了替代方案。
