Cremese M, Wu A H, Cassella G, O'Connor E, Rymut K, Hill D W
Department of Pathology and Laboratory Medicine, Hartford Hospital, CT 06102, USA.
J Forensic Sci. 1998 Nov;43(6):1220-4.
An improved gas chromatographic/mass spectrometric (GC/MS) assay is described for the quantitation of codeine and morphine as trimethylsyl (TMS) derivatives. The TMS derivatization of ketone-containing opiates results in the formation of multiple derivatives. Some of these products have retention times close to those of codeine-TMS and morphine-TMS. When the keto-opiates are present in samples assayed for codeine and morphine in urine, they can interfere with the quantitation of these commonly targeted opiates. The assay was improved with the addition of a pre-BSTFA derivatization step, whereby hydroxylamine was used to convert the keto-opiates into the corresponding oxime derivative. These derivatives were then reacted with BSTFA to form the TMS ethers and TMS oxime derivatives. The oxime step enabled production of single derivatives for hydrocodone and hydromorphone. In addition, the retention times for the oxime-TMS derivatives were increased so that they no longer elute near the targeted drugs of codeine and morphine. The addition of the oxime step does not affect the sylation of codeine and morphine, and the accuracy and precision of this assay were unaffected.
本文描述了一种改进的气相色谱/质谱（GC/MS）分析法，用于定量测定可待因和吗啡的三甲基硅烷基（TMS）衍生物。含酮阿片类药物的TMS衍生化会形成多种衍生物。其中一些产物的保留时间与可待因-TMS和吗啡-TMS的保留时间相近。当在尿液中检测可待因和吗啡的样品中存在酮基阿片类药物时，它们会干扰这些常见目标阿片类药物的定量测定。通过添加BSTFA衍生化前步骤改进了该分析方法，其中使用羟胺将酮基阿片类药物转化为相应的肟衍生物。然后使这些衍生物与BSTFA反应形成TMS醚和TMS肟衍生物。肟步骤使得能够生成氢可酮和氢吗啡酮的单一衍生物。此外，肟-TMS衍生物的保留时间增加，因此它们不再在可待因和吗啡的目标药物附近洗脱。肟步骤的添加不影响可待因和吗啡的硅烷化，并且该分析方法的准确性和精密度不受影响。
