唾液中鸦片类毒品的衍生化GC/MS-SIM分析研究

目的: 建立灵敏度高、重复性好、操作简便的唾液中鸦片类毒品的硅烷化和酰化GC/MS-SIM检测方法。 方法: 以乙基吗啡为内标,用混合溶剂氯仿-异丙醇-正庚烷(50∶ 33∶ 17)对添加吗啡、可待因和6-单乙酰吗啡的唾液进行提取后,经MBTFA或MSTFA衍生化,采用气相色谱/质谱-选择离子法(GC/MS-SIM)检测。 结果: 添加吗啡、可待因和6-单乙酰吗啡的唾液药物浓度在10~1000 ng·mL^-1范围内均获得了良好的线性(r＞0.99),3种成分日内精密度试验的RSD均在16%以内,提取回收率均在80%~120%之间,最小定量限均为10 ng·mL^-1,最小检测限MSTFA衍生化吗啡和可待因为1 ng·mL^-1、6-单乙酰吗啡为0.5 ng·mL^-1,MBTFA衍生化吗啡为0.5 ng·mL^-1、可待因和6-单乙酰吗啡为2 ng·mL^-1;采用该方法对服用治疗剂量的甘草片(内含无水吗啡成分)者的唾液检材进行检测,检测出吗啡。 结论: 该方法操作简单,灵敏度高,稳定可靠,可用于对吸毒者唾液中鸦片类毒品的检测和分析。

Objective: To establish a simple and reliable method in which use gas chromatography/mass spectrometry-selected ion monitoring(GC/MS-SIM) after silylation and acetylation for identifying and quantifying opiates including morphine, 6-acetylmorphine and codeine in human saliva. Methods: Using ethyl morphine as an internal standard, morphine, 6-acetylmorphine and codeine spiked in blank saliva were extracted with a mixed solvent of chloroform-isopropyl alcohol-n-heptane(50∶ 33∶ 17). The extracts were evaporated to dryness followed by being derivatized with MSTFA or MBTFA, and then it was analyzed directly by GC/MS in selected ion mode. Results: The method was validated in the range 10-1000 ng·mL^-1 with the drug-spiked saliva,the reactor responded linearly over the studied range(r>0.99 for the 3 drugs); RSDs of intra-day precision test were less than 16%,the extraction recoveries were varying from 80% to 120%;the LODs were 1 ng·mL^-1 for morphine and codeine,and 0.5 ng·mL^-1 for 6-acetylmorphine,respectively after MSTFA derivatization;While for MBTFA derivatization,the LODs were 2 ng·mL^-1 for both codeine and 6-acetylmorphine, and 0.5 ng·mL^-1 for morphine,respectively.Saliva after administering a therapy dose of cough drop was collected from a healthy male volunteer and analyzed with the established method,in it morphine was detected. Conclusion: It is showing that the method can be applied in detecting trace amount of opiates in human saliva.