Pirnay Stephane, Ricordel Ivan, Libong Danielle, Bouchonnet Stéphane
Laboratoire de Toxicologie de la Préfecture de Police, Paris, France.
J Chromatogr A. 2002 Apr 19;954(1-2):235-45. doi: 10.1016/s0021-9673(02)00190-5.
A gas chromatography-ion trap tandem mass spectrometry method for simultaneous detection of 22 benzodiazepines is presented. Four operating modes were first optimized: the electron impact ionization and chemical ionization modes were compared on both underivatized and trimethylsilylated drugs. Results were compared in terms of sensitivity in MS-MS experiments. The trimethylsilylation of benzodiazepines including a protic functional group allows decreasing their detection threshold by a factor of 10-100. In terms of sensitivity, the comparison between both ionization modes shows that the most efficient one depends on the benzodiazepine considered. The use of an ion trap analyzer allows switching from an ionization mode to another one during the chromatographic process. It also provides a great selectivity owing to the MS-MS and multiple reaction monitoring acquisition modes. The detection thresholds are in the range 10-500 pg/microl for all the studied benzodiazepines but the three "triazolo" ones: estazolam, alprazolam and triazolam, have a detection threshold of 1 ng/microl. The applicability of the method on whole blood and urine extracts was demonstrated on an example implying five benzodiazepines among the most frequently encountered in forensic toxicology: nordazepam, oxazepam, bromazepam, flunitrazepam and prazepam.
本文介绍了一种同时检测22种苯二氮䓬类药物的气相色谱-离子阱串联质谱法。首先优化了四种操作模式：在未衍生化和三甲基硅烷化的药物上比较电子轰击电离模式和化学电离模式。在MS-MS实验中，根据灵敏度对结果进行比较。对含有质子官能团的苯二氮䓬类药物进行三甲基硅烷化处理，可使其检测限降低10至100倍。就灵敏度而言，两种电离模式的比较表明，最有效的模式取决于所考虑的苯二氮䓬类药物。使用离子阱分析仪可在色谱过程中从一种电离模式切换到另一种电离模式。由于采用了MS-MS和多反应监测采集模式，该方法还具有很高的选择性。除了三种“三唑”类药物（艾司唑仑、阿普唑仑和三唑仑）的检测限为1 ng/μL外，所有研究的苯二氮䓬类药物的检测限都在10至500 pg/μL范围内。通过一个涉及法医毒理学中最常遇到的五种苯二氮䓬类药物（去甲西泮、奥沙西泮、溴西泮、氟硝西泮和普拉西泮）的实例，证明了该方法在全血和尿液提取物中的适用性。
