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	Fragmentation of pentacoordinate spirobicyclic aminoacylphosphoranes (P-AAs) by electrospray ionization tandem mass spectrometry concerning P-O and P-N bond cleavage
	Hu, Xiaomei ; Gao, Xiang ; Zhu, Jun ; Zeng, Zhiping ; Zhang, Xinghua ; Lin, Zhiwei ; Xu, Pengxiang ; Liu, Yan ; Zhao, Yufen ; Zhao YF(赵玉芬)
	2011-09-26
英文摘要	The fragmentation pathways of both protonated and sodiated pentacoordinate spirobicyclic aminoacylphosphoranes (P-AAs) have been studied by electrospray ionization multi-stage mass spectrometry (ESI-MS(n)) in positive mode. The possible pathways and their mechanisms are elucidated through the combination of ESI-MS/MS, isotope ((15) N and (2)H) labeling and high-resolution Fourier transform ion cyclotron resonance (FTICR)-MS/MS. The relative Gibbs free energies (Delta G) of the product ions and possible fragmentation pathways are estimated at the B3LYP/6-31 G(d) level of theory. The theoretical calculations show that both protonated and sodiated P-AAs would quickly fragment before Berry pseudorotation. For protonated P-AAs, they have different tendencies to P-O or P-N bond cleavage. For sodiated P-AAs, the P-N bond is easier to cleave and produces the tetracoordinated phosphorus ion H. These results to some extent may give a clue to the chemistry of the active sites of phosphoryl transfer enzymes and will enrich the gas-phase ESI-MS ion chemistry of pentacoordinate phosphoranes. Copyright (C) 2011 John Wiley & Sons, Ltd.; National Natural Science Foundation of China[21075103, 20972130, 20805037, 20732004]; Xiamen University
语种	英语
出版者	WILEY-BLACKWELL
内容类型	期刊论文
源URL	[http://dx.doi.org/doi:10.1002/rcm.5210]
专题	化学化工－已发表论文
推荐引用方式 GB/T 7714	Hu, Xiaomei,Gao, Xiang,Zhu, Jun,et al. Fragmentation of pentacoordinate spirobicyclic aminoacylphosphoranes (P-AAs) by electrospray ionization tandem mass spectrometry concerning P-O and P-N bond cleavage[J],2011.
APA	Hu, Xiaomei.,Gao, Xiang.,Zhu, Jun.,Zeng, Zhiping.,Zhang, Xinghua.,...&赵玉芬.(2011).Fragmentation of pentacoordinate spirobicyclic aminoacylphosphoranes (P-AAs) by electrospray ionization tandem mass spectrometry concerning P-O and P-N bond cleavage..
MLA	Hu, Xiaomei,et al."Fragmentation of pentacoordinate spirobicyclic aminoacylphosphoranes (P-AAs) by electrospray ionization tandem mass spectrometry concerning P-O and P-N bond cleavage".(2011).

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