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New features on the fragmentation patterns of homoisoflavonoids in Ophiopogon japonicus by high-performance liquid chromatography/diode-array detection/electrospray ionization with multi-stage tandem mass spectrometry.
Rapid Commun Mass Spectrom. 2010 Aug 15; 24(15):2193-206.RC

Abstract

Homoisoflavonoids, a special class of flavonoids, are mainly distributed in the Liliaceae family and have various biological activities. Previously, very little research has been reported on the gas-phase fragmentation patterns of homoisoflavonoids by electrospray ionization mass spectrometry. In this paper, we report the use of high-performance liquid chromatography with a diode-array detector (HPLC-DAD) and electrospray ionization multi-stage tandem mass spectrometry (ESI-MS(n)) to study the fragmentation behavior of 11 homoisoflavonoid standards and to analyze homoisoflavonoids in Ophiopogon japonicus. In total, 28 homoisoflavonoids (including seven novel constituents) were characterized. The deprotonated [M--H](-) molecules of the homoisoflavonoids containing a saturated C2--C3 bond afforded the A or B product ion (base peak) according to whether the B-ring was substituted with a hydroxyl group. For the homoisoflavonoids containing a C-2-C-3 double bond, the product ions (A or C ion) were created from the precursor [M-H](-) ion as the base peak when the B-ring was substituted with a hydroxyl group. The homoisoflavonoids carrying a formyl group in the A-ring readily eliminated one molecule of CO to form the product ion [M + H-CO](-) (base peak) irrespective whether the C-2-C-3 bond was saturated or not. This product ion afforded the [M-H-CO-B-ring--CH(2) + H](-) ion by cleavage of the C3-C9 bond. This latter product ion always appeared in tandem mass (MS/MS) spectra of type I homoisoflavonoids. The common features of flavonoids observed during the gas-phase fragmentation mechanisms were the loss of the following groups: 15 Da (CH(3)), 18 Da (H(2)O), 28 Da (CO), 44 Da (CO(2)) and 46 Da (CH(2)O(2)). A retro-Diels-Alder (RDA)-like cleavage was also observed for the homoisoflavonoids. The different gas-phase fragmentation routes were characterized for the deprotonated molecules obtained from the various homoisoflavonoids and collision-induced dissociation (CID) fragmentation differences were noted for the different locations of the various substituents. In conclusion, we can say that this study allowed us to structurally elucidate and identify homoisoflavonoids distributed in related plants and their complex prescriptions.

Authors+Show Affiliations

Department of Complex Prescriptions of TCM, China Pharmaceutical University, Nanjing 210009, PR China.No affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info available

Pub Type(s)

Evaluation Study
Journal Article
Research Support, Non-U.S. Gov't

Language

eng

PubMed ID

20583326

Citation

Qi, Jin, et al. "New Features On the Fragmentation Patterns of Homoisoflavonoids in Ophiopogon Japonicus By High-performance Liquid Chromatography/diode-array Detection/electrospray Ionization With Multi-stage Tandem Mass Spectrometry." Rapid Communications in Mass Spectrometry : RCM, vol. 24, no. 15, 2010, pp. 2193-206.
Qi J, Xu D, Zhou YF, et al. New features on the fragmentation patterns of homoisoflavonoids in Ophiopogon japonicus by high-performance liquid chromatography/diode-array detection/electrospray ionization with multi-stage tandem mass spectrometry. Rapid Commun Mass Spectrom. 2010;24(15):2193-206.
Qi, J., Xu, D., Zhou, Y. F., Qin, M. J., & Yu, B. Y. (2010). New features on the fragmentation patterns of homoisoflavonoids in Ophiopogon japonicus by high-performance liquid chromatography/diode-array detection/electrospray ionization with multi-stage tandem mass spectrometry. Rapid Communications in Mass Spectrometry : RCM, 24(15), 2193-206. https://doi.org/10.1002/rcm.4608
Qi J, et al. New Features On the Fragmentation Patterns of Homoisoflavonoids in Ophiopogon Japonicus By High-performance Liquid Chromatography/diode-array Detection/electrospray Ionization With Multi-stage Tandem Mass Spectrometry. Rapid Commun Mass Spectrom. 2010 Aug 15;24(15):2193-206. PubMed PMID: 20583326.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - New features on the fragmentation patterns of homoisoflavonoids in Ophiopogon japonicus by high-performance liquid chromatography/diode-array detection/electrospray ionization with multi-stage tandem mass spectrometry. AU - Qi,Jin, AU - Xu,Deran, AU - Zhou,Yi-Feng, AU - Qin,Min-Jian, AU - Yu,Bo-Yang, PY - 2010/6/29/entrez PY - 2010/6/29/pubmed PY - 2010/10/6/medline SP - 2193 EP - 206 JF - Rapid communications in mass spectrometry : RCM JO - Rapid Commun Mass Spectrom VL - 24 IS - 15 N2 - Homoisoflavonoids, a special class of flavonoids, are mainly distributed in the Liliaceae family and have various biological activities. Previously, very little research has been reported on the gas-phase fragmentation patterns of homoisoflavonoids by electrospray ionization mass spectrometry. In this paper, we report the use of high-performance liquid chromatography with a diode-array detector (HPLC-DAD) and electrospray ionization multi-stage tandem mass spectrometry (ESI-MS(n)) to study the fragmentation behavior of 11 homoisoflavonoid standards and to analyze homoisoflavonoids in Ophiopogon japonicus. In total, 28 homoisoflavonoids (including seven novel constituents) were characterized. The deprotonated [M--H](-) molecules of the homoisoflavonoids containing a saturated C2--C3 bond afforded the A or B product ion (base peak) according to whether the B-ring was substituted with a hydroxyl group. For the homoisoflavonoids containing a C-2-C-3 double bond, the product ions (A or C ion) were created from the precursor [M-H](-) ion as the base peak when the B-ring was substituted with a hydroxyl group. The homoisoflavonoids carrying a formyl group in the A-ring readily eliminated one molecule of CO to form the product ion [M + H-CO](-) (base peak) irrespective whether the C-2-C-3 bond was saturated or not. This product ion afforded the [M-H-CO-B-ring--CH(2) + H](-) ion by cleavage of the C3-C9 bond. This latter product ion always appeared in tandem mass (MS/MS) spectra of type I homoisoflavonoids. The common features of flavonoids observed during the gas-phase fragmentation mechanisms were the loss of the following groups: 15 Da (CH(3)), 18 Da (H(2)O), 28 Da (CO), 44 Da (CO(2)) and 46 Da (CH(2)O(2)). A retro-Diels-Alder (RDA)-like cleavage was also observed for the homoisoflavonoids. The different gas-phase fragmentation routes were characterized for the deprotonated molecules obtained from the various homoisoflavonoids and collision-induced dissociation (CID) fragmentation differences were noted for the different locations of the various substituents. In conclusion, we can say that this study allowed us to structurally elucidate and identify homoisoflavonoids distributed in related plants and their complex prescriptions. SN - 1097-0231 UR - https://www.unboundmedicine.com/medline/citation/20583326/New_features_on_the_fragmentation_patterns_of_homoisoflavonoids_in_Ophiopogon_japonicus_by_high_performance_liquid_chromatography/diode_array_detection/electrospray_ionization_with_multi_stage_tandem_mass_spectrometry_ L2 - https://doi.org/10.1002/rcm.4608 DB - PRIME DP - Unbound Medicine ER -