几种4-氨基吡啶衍生物的多级质谱裂解途径  

Fragmentation pathway of several 4-aminopyridine derivatives in multistage mass spectrometry

作　　者：方华[1] 谢全灵[1] 黄晓燕[1] 晋文慧[1] 张怡评[1] 洪专[1] 

机构地区：[1]国家海洋局第三海洋研究所,福建厦门361005

出　　处：《化学研究》2013年第5期512-515,518,共5页Chemical Research

基　　金：海洋公益性行业科研专项经费项目(201205022-8);国家海洋局青年基金(2012537);厦门市重大科技创新平台项目(3502Z20111001)

摘　　要：为获得高效的海洋生物毒素河豚毒素(TTX)解毒剂,合成了一系列4-氨基吡啶类衍生物N-二异丙基磷酰化氨基酸-N-4-氨基吡啶;研究了N-二异丙基磷酰化氨基酸-N-4-氨基吡啶的多级质谱(ESI-MS/MS)裂解方式;提出了碎片离子m/z=95的裂解途径,并推测了其重排机理.结果表明,该类化合物具有相同分子量的碎片离子c/c′,是由两种母离子a或b离子裂解得到的.通过在吡啶环上引入氯原子可证实该裂解途径;而碎片离子m/z=95源于离子重排.A series of novel 4-aminopyridine derivatives containing N-diisopropyloxyphosphoryl amino acid unit were synthesized as highly efficient antidotes of tetradotoxin, a marine organ- ism toxin. The fragmentation pathway of as-synthesized N-diisopropyloxyphosphoryl amino acid-N-4-aminopyridines was investigated by means of positive ion electrospray ionization mass spectrometry （ESI-MS） in conjunction with tandem mass spectrometry （MS/MS）. Moreover, the fragmentation pathway of fragment ion m/z = 95 was proposed, and its possible rearrange ment mechanism was supposed. Results indicate that all the compounds under investigation have fragment ion c/c＇ with the same molecular weight, and fragment ion c/c＇ is derived from precursor ions a and b. Such a fragmentation pathway can be verified by introducing tracer ele ment C1 onto the pyridine ring of the title derivatives, while the fragment ion m/z = 95 is generated by way of ion rearrangement

关 键 词：河豚毒素解毒剂 4氨基吡啶衍生物 多级质谱（ESI—MS MS） 裂解途径 

分 类 号：O657.63[理学—分析化学]