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. 2019 Dec 15;24(24):4591.
doi: 10.3390/molecules24244591.

Characterization and Identification of Prenylated Flavonoids from Artocarpus heterophyllus Lam. Roots by Quadrupole Time-Of-Flight and Linear Trap Quadrupole Orbitrap Mass Spectrometry

Jin-Bao Ye  1 , Gang Ren  1 , Wen-Yan Li  1 , Guo-Yue Zhong  1 , Min Zhang  2 , Jin-Bin Yuan  2 , Ting Lu  1
Affiliations

Characterization and Identification of Prenylated Flavonoids from Artocarpus heterophyllus Lam. Roots by Quadrupole Time-Of-Flight and Linear Trap Quadrupole Orbitrap Mass Spectrometry

Jin-Bao Ye et al. Molecules. .

Abstract

In this study, a combination of quadrupole time-of-flight mass spectrometry (Q-TOF-MS) and linear trap quadrupole orbitrap mass spectrometry (LTQ-Orbitrap-MS) was performed to investigate the fragmentation behaviors of prenylated flavonoids (PFs) from Artocarpus plants. Fifteen PFs were selected as the model molecules and divided into five types (groups A-E) according to their structural characteristics in terms of the position and existing form of prenyl substitution in the flavone skeleton. The LTQ-Orbitrap-MSn spectra of the [M - H]- ions for these compounds provided a wealth of structural information on the five different types of compounds. The main fragmentation pathways of group A were the ortho effect and retro Diels-Alder (RDA), and common losses of C4H10, CO, and CO2. The compounds in group B easily lose C6H12, forming a stable structure of a 1,4-dienyl group, unlike those in group A. The fragmentation pathway for group C is characterized by obvious 1,4A-, 1,4B- cracking of the C ring. The diagnostic fragmentation for group D is obvious RDA cracking of the C ring and the successive loss of CH3 and H2O in the LTQ-Orbitrap-MSn spectra. Fragmentation with successive loss of CO or CO2, ·CH3, and CH4 in the LTQ-Orbitrap-MSn spectra formed the characteristics of group E. The summarized fragmentation rules were successfully exploited to identify PFs from Artocarpus heterophyllus, a well-known Artocarpus plant, which led to the identification of a total of 47 PFs in this plant.

Keywords: Artocarpus heterophyllus; LTQ-Orbitrap-MS; Q-TOF-MS; fragmentation rules; identification; prenylated flavonoids.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
Structures of the five groups of prenylated flavonoids (PFs) selected as model molecules from Artocarpus plants.
Figure 2
Figure 2
Nomenclature of the different C ring cleavages [21] occurring in the present study, illustrated by a typical flavonoid skeleton.
Figure 3
Figure 3
(−) ESI-Q-TOF-MS/MS and LTQ-Orbitrap-MSn (n = 3–4) spectra of PF 1 in group A and the fragmentation pathways proposed for PF 1. Q-TOF-MS (A), Q-TOF-MS2 (B), LTQ-Orbitrap-MS3 of the ions at m/z 233.0852 from m/z 367.1205 (C), LTQ-Orbitrap-MS3 of the ions at m/z 309.0417 from m/z 367.1205 (D), LTQ-Orbitrap-MS4 of the ions at m/z 265.0599 from m/z 309.0417 (E), and the proposed fragmentation pathways for PF 1 (F). RDA: retro Diels–Alder.
Figure 4
Figure 4
(−) ESI-Q-TOF-MS/MS and LTQ-Orbitrap-MSn (n = 3–4) spectra of PF 4 in group B and the fragmentation pathways proposed for PF 4. Q-TOF-MS (A), Q-TOF-MS2 (B), LTQ-Orbitrap-MS3 of the ions at m/z 297.0395 from m/z 421.1644 (C), LTQ-Orbitrap-MS4 of the ions at m/z 253.0483 from m/z 297.0395 (D), and the proposed fragmentation pathways for PF 4 (E).
Figure 5
Figure 5
(−)ESI-Q-TOF-MS/MS of PF 6 in group C and the fragmentation pathways proposed for PF 6. Q-TOF-MS (A), Q-TOF-MS2 (B), and the proposed fragmentation pathways for PF 6 (C). RDA: retro Diels–Alder.
Figure 6
Figure 6
(−)ESI-Q-TOF-MS/MS and LTQ-Orbitrap-MSn (n = 3–4) spectra of PF 10 in group B and the fragmentation pathways proposed for PF 10. Q-TOF-MS (A), Q-TOF-MS2 (B), LTQ-Orbitrap-MS3 of the ions at m/z 361.0731 from m/z 417.1358 (C), LTQ-Orbitrap-MS4 of the ions at m/z 343.0523 from m/z 361.073 (D), and the proposed fragmentation pathways for PF 10 (E). RDA: retro Diels–Alder.
Figure 7
Figure 7
(−)ESI-Q-TOF-MS/MS and LTQ-Orbitrap-MSn (n = 3–4) spectra of PF 12 in group B and the fragmentation pathways proposed for PF 12. Q-TOF-MS (A), Q-TOF-MS2 (B), LTQ-Orbitrap-MS3 of the ions at m/z 445.1296 from m/z 501.1939 (C), LTQ-Orbitrap-MS4 of the ions at m/z 427.0927 from at m/z 445.1296 (D), LTQ-Orbitrap-MS3 of the ions at m/z 485.1631 from m/z 501.1939 (E), LTQ-Orbitrap-MS4 of the ions at m/z 429.1201 from m/z 485.1631 (F), and the proposed fragmentation pathways for PF 12 (G).
Figure 8
Figure 8
Total ion chromatogram (A) and extracted ion chromatogram (B) of prenylated flavonoids in the extract of Artocarpus heterophyllus Lam. roots.
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