几种4-氨基吡啶衍生物的多级质谱裂解途径

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.

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

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