Application of time-of-flight mass spectrometry to forensic medicine:biochemical weapons and doping

1. LC-TOFMS仪器的设置和操作介绍了目前最先进的LC-TOFMS仪器。它的控制系统非常先进。由于它的质谱原理与四极杆和离子阱质谱仪有很大的不同，我们需要相当长的时间来熟悉该系统，以便毫无困难地操作。灵芝中裸盖菇素和裸盖菇素的分析裸盖菇素是一种低分子量、高毒性的化合物。裸盖菇素的前体裸盖菇素也显示出致幻活性。首先，我们建立了从复杂矩阵中提取它们的过程。其次，我们尝试用LC-TOFMS和LC-Qq- TOFMS同时检测裸盖菇素和裸盖菇素，并比较了它们的检测能力. LC-TOFMS和LC-Qq- TOFMS的灵敏度有显著性差异.检测限约为20 pg。为了得到更好的结果，我们采用了蟾毒肽（psilocin的异构体）作为内标。LC-TOFMSAMananitins的分析毒鹅膏菌和白鹅膏菌中所含的毒鹅膏菌毒素具有很高的毒性，几毫克就可以杀死一个成年人。这表明鹅膏蕈碱可用作化学战剂。鹅膏菌素的结构是分子量大于900道尔顿的环肽。以环孢素A为内标，建立了香菇中α-鹅膏蕈碱的液相色谱-飞行时间质谱分析方法。α-鹅膏蕈碱的检测限为50 pg/注射体积。MALDI质谱成像系统的建立及其在法医学中的应用我们已经建立了独特的系统，现在正试图将其应用于使用模型大鼠来阐明甲基苯丙胺和可卡因滥用引起的慢性精神症状的机制。

1. Setting up of the LC-TOFMS instrument and how to operate itThe instrument introduced was the state- of- the- art one. Its control system was highly advanced. Because its MS principle was quite different from those of the quadrupole and ion- trap MS instruments, we needed an appreciable time for familiarization to operate the system without any difficulty.2. Analysis of psilocin and psilocybin in magic mushroomsPsilocin is one of the most low- molecular and highly toxic compounds. Psilocybin, the precursor of psilocin, also shows hallucinogenic activities. Firstly, we established the procedure for their extraction from complicated matrices. Secondly, we tried to detect both psilocin and psilocybin by LC- TOFMS and LC- Qq- TOFMS, and compared their detection capabilities. There were notable differences in sensitivity between LC- TOFMS and LC- Qq- TOFMS. The detection limit was about 20 pg in an injected volume. Now we are using bufotenin, an isomer of psilocin, as internal standard to get better results.3. Analysis of amanitins by LC-TOFMSAmanitins being contained in Amanita virosa and Amanita verna are highly toxic; several milligrams of them can kill an adult human. This suggests that amanitins can be used as chemical warfare agents. The structures of amanitins are of cyclic peptides with molecular weights of more than 900 daltons. Using cyclosporine A as internal standard, a method for analysis of a - amanitin in mushrooms by LC-TOFMS was established. The detection limit of α- amanitin was about 50 pg in an injected volume.Setting up of a MALDI mass spectrometric imaging system and its application to forensjc medcineThe instrument QSTAR XL TOFMS introduced by the present Grant - in - Aid has an optional imaging system. We have set up the unique system, and are now trying to apply it to clarification of mechanisms for chronic psychiatric symptoms caused by methamphetamine and cocaine abuses using the model rats.