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Fragmentation pathways of protonated coumarin by ESI‐QE‐Orbitrap‐MS/MS coupled with DFT calculations
Author(s) -
Sun Changhai,
Wang Yazhuo,
Sun Shiyuan,
Chen Xin,
Shi Xinlei,
Fang Hongzhuang,
Zhang Yu,
Fang Zhou
Publication year - 2020
Publication title -
journal of mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 1076-5174
DOI - 10.1002/jms.4496
Subject(s) - chemistry , orbitrap , protonation , fragmentation (computing) , electrospray ionization , coumarin , mass spectrometry , carbocation , electrospray , computational chemistry , photochemistry , ion , analytical chemistry (journal) , chromatography , organic chemistry , computer science , operating system
Coumarin is one of the basic structures of naturally oxygen heterocyclic compound, which was investigated in this paper for its gas‐phase fragmentation behaviors using electrospray quadrupole extractive orbitrap mass spectrometry in the positive mode. The possible fragmentation pathways were proposed based on electrospray ionization (ESI)‐ mass spectrometry (MS)/MS data and theory calculation. The elimination of two CO and CO 2 was observed for protonated coumarin, which was followed by the formation of a stabilized seven‐, six‐, and five‐membered ring carbocation by loss of C2H2. The possible protonation sites occurred at Oxygen 11 atom of coumarin were the main fragmentation pathways. The relative abundance of characteristic fragment ions and the energy‐resolved breakdown curves were used to confirm the cleavage mechanism of protonated coumarin. The methodology and results of present work would contribute to the chemical structure identification of other coumarins.