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A Fragmentation Study on Four Unusual Secoiridoid Trimers, Swerilactones H-K, by Electrospray Tandem Mass Spectrometry |
| Chang-An Geng1,2, Ji-Jun Chen1,2 |
1. State Key Laboratory of Phytochemistry and Plant Resources in West China, Kunming Institute of Botany, Chinese Academy of Sciences, No. 132 Lanhei Road, Kunming 650201, China;
2. Yunnan Key Laboratory of Natural Medicinal Chemistry, Kunming 650201, China |
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Abstract Swerilactones H-K (1-4) as four unprecedented secoiridoid trimers represent a new type of natural product, which has attracted much interest of natural chemists due to their novel skeletons and promising bioactivity. In order to well understand their MS fragmentation behaviors, they were investigated by electrospray ionization ion-trap time-of-flight multistage product ion mass spectrometry (ESI-IT-TOF-MSn) for the first time. The protonated molecules ([M+H]+) of swerilactones J and K, and deprotonated molecules ([M-H]-) of swerilactones H, J and K were readily observed in the conventional single-stage mass spectra (MS); however only the[M+Cl]-ion for swerilactone I was obtained in negative mode. Based on the MSn study, the fragmentation pathways of swerilactones H and I in negative mode, and swerilactones J and K in both positive and negative modes were proposed. The neutral losses of H2O, CO, CO2 and C2H4O moieties are the particular elimination from the precursor ions due to the presence of hydroxyl, δ-lactone and 1-O-ethyl moieties in their structures, of which the retro-Diels-Alder cleavage was the most particular dissociation. The fragment ions at m/z 341 and 291 in negative mode can be considered as the diagnostic ions for secoiridoid trimers. This investigation will provide valuable information for their fast characterization from complicated natural mixtures and extensive understanding their structural architectures.
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| Keywords
ESI-IT-TOF-MSn
Fragmentation rules
Secoiridoid trimers
Swerilactones H-K
Retro-Diels-Alder (RDA) cleavage
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| Fund:This study was financed by the Youth Innovation Promotion Association (CAS),the West Light Foundation of CAS (Western Youth Scholars "A" );the Hundred Talents Program of CAS,and the Program of Yunling Scholarship |
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Issue Date: 31 January 2018
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