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Structural characterization of iridoid glucosides by ultra-performance liquid chromatography/electrospray ionization quadrupole time-of-flight tandem mass spectrometry.
Rapid Commun Mass Spectrom. 2008 Jun; 22(12):1941-54.RC

Abstract

The mass spectral fragmentation behavior of ten iridoid glucosides (IGs) has been studied using electrospray ionization (ESI), collision-induced dissociation (CID), and quadrupole time-of-flight tandem mass spectrometry (Q-TOF MS/MS). In the negative ESI mass spectra, the deprotonated [M-H](-) ion was observed for all of the ten IGs except gardoside methyl ester, while the formate adduct [M+HCOO](-) ion appeared to be favored by the presence of a methyl ester or a lactone group in the C-4 position when formic acid was added to the mobile phase. The CID MS/MS spectra of the [M-H](-) ions have been used for structural elucidation. Ring cleavages of the aglycone moiety have been observed in the MS/MS spectra, corresponding to (1,4)F(-), (2,6)F(-), (2,7)F(-), and (2,7)F(0) (-) ions, based on accurate mass measurements and the elemental compositions of the product ions. These characteristic ions gave valuable information on the basic structural skeletons. Furthermore, on the basis of the relative abundances of the fragment ions (1,4)F(-) and (2,7)F(-), different sub-classes, such as cyclopentane-type and 7,8-cyclopentene-type IGs, can be differentiated. Ring cleavage of the sugar moieties was also observed, yielding useful information for their characterization. In addition, the neutral losses, such as H(2)O, CO(2), CH(3)OH, CH(3)COOH, and glucosidic units, have proved useful for confirming the presence of functional substituents in the structures of the IGs. Based on the fragmentation patterns of these standard IGs, twelve IGs have been characterized in an extract of Hedyotis diffusa Willd. by means of ultra-performance liquid chromatography/Q-TOF MS/MS, of which six have been unambiguously identified and the other six have been tentatively identified.

Authors+Show Affiliations

Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, People's Republic of China.No affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info available

Pub Type(s)

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

Language

eng

PubMed ID

18491284

Citation

Li, Cun-Man, et al. "Structural Characterization of Iridoid Glucosides By Ultra-performance Liquid Chromatography/electrospray Ionization Quadrupole Time-of-flight Tandem Mass Spectrometry." Rapid Communications in Mass Spectrometry : RCM, vol. 22, no. 12, 2008, pp. 1941-54.
Li CM, Zhang XL, Xue XY, et al. Structural characterization of iridoid glucosides by ultra-performance liquid chromatography/electrospray ionization quadrupole time-of-flight tandem mass spectrometry. Rapid Commun Mass Spectrom. 2008;22(12):1941-54.
Li, C. M., Zhang, X. L., Xue, X. Y., Zhang, F. F., Xu, Q., & Liang, X. M. (2008). Structural characterization of iridoid glucosides by ultra-performance liquid chromatography/electrospray ionization quadrupole time-of-flight tandem mass spectrometry. Rapid Communications in Mass Spectrometry : RCM, 22(12), 1941-54. https://doi.org/10.1002/rcm.3579
Li CM, et al. Structural Characterization of Iridoid Glucosides By Ultra-performance Liquid Chromatography/electrospray Ionization Quadrupole Time-of-flight Tandem Mass Spectrometry. Rapid Commun Mass Spectrom. 2008;22(12):1941-54. PubMed PMID: 18491284.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Structural characterization of iridoid glucosides by ultra-performance liquid chromatography/electrospray ionization quadrupole time-of-flight tandem mass spectrometry. AU - Li,Cun-Man, AU - Zhang,Xiu-Li, AU - Xue,Xing-Ya, AU - Zhang,Fei-Fang, AU - Xu,Qing, AU - Liang,Xin-Miao, PY - 2008/5/21/pubmed PY - 2008/7/24/medline PY - 2008/5/21/entrez SP - 1941 EP - 54 JF - Rapid communications in mass spectrometry : RCM JO - Rapid Commun Mass Spectrom VL - 22 IS - 12 N2 - The mass spectral fragmentation behavior of ten iridoid glucosides (IGs) has been studied using electrospray ionization (ESI), collision-induced dissociation (CID), and quadrupole time-of-flight tandem mass spectrometry (Q-TOF MS/MS). In the negative ESI mass spectra, the deprotonated [M-H](-) ion was observed for all of the ten IGs except gardoside methyl ester, while the formate adduct [M+HCOO](-) ion appeared to be favored by the presence of a methyl ester or a lactone group in the C-4 position when formic acid was added to the mobile phase. The CID MS/MS spectra of the [M-H](-) ions have been used for structural elucidation. Ring cleavages of the aglycone moiety have been observed in the MS/MS spectra, corresponding to (1,4)F(-), (2,6)F(-), (2,7)F(-), and (2,7)F(0) (-) ions, based on accurate mass measurements and the elemental compositions of the product ions. These characteristic ions gave valuable information on the basic structural skeletons. Furthermore, on the basis of the relative abundances of the fragment ions (1,4)F(-) and (2,7)F(-), different sub-classes, such as cyclopentane-type and 7,8-cyclopentene-type IGs, can be differentiated. Ring cleavage of the sugar moieties was also observed, yielding useful information for their characterization. In addition, the neutral losses, such as H(2)O, CO(2), CH(3)OH, CH(3)COOH, and glucosidic units, have proved useful for confirming the presence of functional substituents in the structures of the IGs. Based on the fragmentation patterns of these standard IGs, twelve IGs have been characterized in an extract of Hedyotis diffusa Willd. by means of ultra-performance liquid chromatography/Q-TOF MS/MS, of which six have been unambiguously identified and the other six have been tentatively identified. SN - 0951-4198 UR - https://www.unboundmedicine.com/medline/citation/18491284/Structural_characterization_of_iridoid_glucosides_by_ultra_performance_liquid_chromatography/electrospray_ionization_quadrupole_time_of_flight_tandem_mass_spectrometry_ L2 - https://doi.org/10.1002/rcm.3579 DB - PRIME DP - Unbound Medicine ER -