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-MS_n) 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 MS_n 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.

Key words: ESI-IT-TOF-MS_n, Fragmentation rules, Secoiridoid trimers, Swerilactones H-K, Retro-Diels-Alder (RDA) cleavage

摘要： 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-MS_n) 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 MS_n 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.

关键词: ESI-IT-TOF-MS_n, Fragmentation rules, Secoiridoid trimers, Swerilactones H-K, Retro-Diels-Alder (RDA) cleavage