James Kevin J, Crowley Janet, Hamilton Brett, Lehane Mary, Skulberg Olav, Furey Ambrose
PROTEOBIO, Mass Spectrometry Centre for Proteomics and Biotoxin Research, Department of Chemistry, Cork Institute of Technology, Bishopstown, Cork, Ireland.
Rapid Commun Mass Spectrom. 2005;19(9):1167-75. doi: 10.1002/rcm.1894.
The potent neurotoxins from cyanobacteria, anatoxin-a (AN), its methyl analogue, homoanatoxin-a (HMAN), and their degradation products, have been studied using nano-electrospray hybrid quadrupole time-of-flight mass spectrometry (QqTOF-MS). The anatoxin degradation products, which are readily produced in vivo by either reduction or epoxidation, were also examined in this study. The high mass accuracy QqTOF-MS data was used to confirm formula assignments for major product ions and quadrupole ion-trap (QIT)-MS was used to construct fragmentation pathways for anatoxins. Significant differences between these fragmentation pathways were observed. Comparisons between the spectra of compounds that differ in side-chain length (the AN and HMAN series) were used to identify ions that are characteristic of the homologues. The application to forensic samples in which the principal neurotoxin had undergone rapid biodegradation has been demonstrated and used to confirm anatoxin poisoning of dogs.
利用纳米电喷雾混合四极杆飞行时间质谱仪（QqTOF-MS）对蓝藻产生的强效神经毒素类毒素-a（AN）、其甲基类似物高类毒素-a（HMAN）及其降解产物进行了研究。本研究还检测了类毒素降解产物，这些产物可通过体内还原或环氧化反应轻易生成。利用高质量精度的QqTOF-MS数据确认主要产物离子的分子式，并利用四极杆离子阱（QIT）-MS构建类毒素的裂解途径。观察到这些裂解途径之间存在显著差异。通过比较侧链长度不同的化合物（AN和HMAN系列）的光谱，来鉴定同系物特有的离子。已证明该方法可应用于主要神经毒素已快速生物降解的法医样本，并用于确认犬类毒素中毒。
