Table 1.
Tentative characterization of chemical constituents of two species of GRR by UHPLC-LTQ-Orbitrap/MS in negative ion mode.
No | Name | Formula | m/z | Adduction | Fragment Ion | RT | Scabra | Rigescens |
---|---|---|---|---|---|---|---|---|
Iridoid | ||||||||
1 | Secologanic acid | C16H22O10 | 373.11 | [M-H] | 179/108/204/282 | 8.40 | + | |
2 | Longanic acid * | C16H24O10 | 375.13 | [M-H] | 371/179 | 2.35 | + | |
3 | Gentiolactone | C10H12O5 | 211.10 | [M-H] | 167 | 7.50 | + | + |
4 | Gentiopicroside* | C16H20O9 | 401.11 | [M-H+HCOOH] | 179/355/149/119 | 5.22 | + | + |
5 | Sweroside * | C16H22O9 | 403.12 | [M-H+HCOOH] | 357/195/179/125 | 5.63 | + | + |
6 | 8-epikingside | C17H24O11 | 403.12 | [M-H] | 371/223/179 | 7.49 | + | |
7 | Caryptoside | C17H26O11 | 405.14 | [M-H+HCOOH] | 179 | 2.26 | + | + |
8 | Swertiamarin * | C16H22O10 | 419.12 | [M-H+HCOOH] | 179/355/211/119 | 3.85 | + | + |
9 | Loganin * | C17H26O10 | 435.22 | [M-H+HCOOH] | 389.22 | 7.17 | + | |
10 | Secoxyloganin | C17H24O11 | 449.13 | [M-H+HCOOH] | 179/241/359/403 | 2.66 | + | |
11 | Morroniside | C17H26O11 | 451.14 | [M-H+HCOOH] | 405/243/179/ | 2.94 | + | |
12 | 2′-O-(2,3-dihyrben)-gentiopicroside | C20H28O14 | 491.14 | [M-H] | 167/323/459 | 4.59 | + | + |
13 | 2′-O-(2,3-dihyben)-swertamairn | C23H26O13 | 509.13 | [M-H] | 153/297/315/367 | 10.53 | + | |
14 | 3′-O-(2,3-dihyben)-swertamairn | C23H26O13 | 509.22 | [M-H] | 153/517/411/321 | 6.11 | + | |
15 | Deglu-noneacetylate-rindoiside | C23H26O13 | 509.22 | [M-H] | 153/297/315/367 | 9.53 | + | |
16 | Rigenolide A | C25H28O12 | 519.15 | [M-H] | 307 | 11.20 | + | |
17 | 4-glu+D97RT | C26H34O11 | 521.20 | [M-H] | 359/329 | 9.44 | + | |
18 | Lacriciresinol | C26H34O11 | 521.20 | [M-H] | 473/355/375/415 | 15.26 | + | |
19 | 6′-O-d-glu swertiamarin | C25H28O13 | 535.14 | [M-H] | 409/491/153/339 | 14.39 | + | |
20 | 6′-O-d-glu-Loganic acid | C22H34O15 | 537.18 | [M-H] | 213 | 2.05 | + | + |
21 | Dideacetylate-deglu-rindoside | C25H28O14 | 551.14 | [M-H] | 491/409/509 | 12.34 | + | |
22 | Gentianaside | C22H36O13 | 553.13 | [M-H+HCOOH] | 507 | 5.03 | + | |
23 | 6-O-d-glu-gentiopicroside | C22H30O14 | 563.16 | [M-H+HCOOH] | 341/517 | 5.69 | + | + |
24 | Tortoside B | C28H38O13 | 581.15 | [M-H] | 401/357/313/269 | 1.47 | + | |
25 | Gentiabavaroside | C26H30O15 | 581.16 | [M-H] | 401/357/313/221 | 1.47 | + | |
26 | 6-O-d-glu-swertianmarin | C22H32O15 | 581.17 | [M-H+HCOOH] | 341/535/517/179 | 2.83 | + | |
27 | Deacetylate-deglu-rindoside | C27H30O15 | 593.15 | [M-H] | 451/531/551 | 19.54 | + | + |
28 | Deglu-trifloroside | C29H32O15 | 619.17 | [M-H] | 577 | 24.5 | + | + |
29 | Deglu-gelidoside | C29H32O16 | 635.16 | [M-H] | 551/451/593 | 23.19 | + | + |
30 | Gentiotrifloroside | C29H36O17 | 655.19 | [M-H] | 315/493/529 | 7.41 | + | + |
31 | Deglu-scabraside | C34H34O15 | 681.18 | [M-H] | 639/475/153 | 28.45 | + | + |
32 | Gentrigeoside A | C36H60O12 | 683.40 | [M-H] | 640/622 | 28.46 | + | |
33 | 2,3-deacetyl-trifloroside | C32H40O17 | 695.18 | [M-H] | 315 | 13.78 | + | |
34 | 6′-O-ace-3-O-glu-2-hy-sweroside | C31H38O18 | 697.17 | [M-H] | 315/535/571/315 | 14.25 | + | |
35 | Trideacetylate-trifloroside | C31H38O18 | 697.18 | [M-H+HCOOH] | 505/651/313/269 | 8.78 | + | |
36 | Scabran G3 | C28H40O19 | 725.21 | [M-H] | 341/383/503/679 | 2.55 | + | + |
37 | 2-deaceyl-trifloroside | C33H38O19 | 737.19 | [M-H] | 315/575/693 | 16.1 | + | |
38 | Dedihydroxybenzoate-Macrophylloside | C33H40O19 | 739.20 | [M-H] | 697/577/613/535 | 15.76 | + | + |
39 | Deacetylate-Trifloroside | C33H40O19 | 739.20 | [M-H] | 697/577/613/535 | 14.7 | + | + |
40 | Deacetylate-Rindoside | C33H40O20 | 755.20 | [M-H] | 593/315/713 | 13.92 | + | + |
41 | Trifloroside * | C35H42O20 | 781.22 | [M-H] | 619/739/577/315 | 18.44 | + | |
42 | Dideacetylate-Macophylloside | C36H40O20 | 791.24 | [M-H] | 521/629/315 | 15.11 | + | |
43 | Rindoside * | C35H42O21 | 797.21 | [M-H] | 315/493/635/755 | 17.19 | + | + |
44 | Deacetylate-scabraside | C38H42O19 | 801.22 | [M-H] | 639/597 | 18.41 | + | |
45 | Acetylate-trifloroside | C37H44O21 | 823.23 | [M-H] | 619/577/781 | 21.59 | + | |
46 | Deacetylatemacrophylloside A | C38H42O21 | 833.21 | [M-H] | 671/697/535/315 | 15.33 | + | + |
47 | Scabraside | C40H44O20 | 843.24 | [M-H] | 681/639/315/801 | 21.66 | + | + |
48 | Dideacetylate-4′-glu-trifloroside | C37H48O23 | 859.23 | [M-H] | 697 | 19.31 | + | + |
49 | Macrophylloside A | C40H44O22 | 875.22 | [M-H] | 739/577/535 | 18,74 | + | + |
50 | Deacetylate-4′-glu-trifloroside | C39H50O24 | 901.26 | [M-H] | 577/459/535/859 | 13.36 | + | |
51 | 4-O-β-d-trifloroside | C41H52O25 | 943.27 | [M-H] | 459/619/901/577 | 16.29 | + | + |
52 | Acetylate-4′-glu-scabraside | C46H54O25 | 1005.29 | [M-H] | 963/681/639/477 | 20.73 | + | |
53 | 4″-O-β-d-glucopyranosy1-6′-O-(4-O-β-d-glu-caffeoyl) linearroside | C46H56O25 | 1007.30 | [M-H] | 845/801/487/639 | 11.59 | + | |
54 | Benzoxy-4″-O-β-d-glucopyranosy1-6′-O-(4-O-β-d-glucopyranosylcaffeoyl)linearroside | C53H60O26 | 1111.33 | [M-H] | 845/487/639/801 | 15.03 | + | |
Flavonoids | ||||||||
55 | Isovitexin | C21H20O10 | 431.10 | [M-H] | 9.7 | + | + | |
56 | Isoorientin(Homoorientin) * | C21H20O11 | 447.15 | [M-H] | 327/357/429 | 8.29 | + | + |
57 | Isoscoparin | C22H22O11 | 507.17 | [M-H+COOH] | 461 | 6.66 | + | |
58 | 2-glu-isovitexin | C27H30O15 | 593.15 | [M-H] | 551/451/531/409 | 19.54 | + | |
59 | Isosaponarin | C27H30O16 | 593.15 | [M-H] | 311/431/473/503 | 7.68 | + | |
60 | Saponarin | C27H30O17 | 593.15 | [M-H] | 367 | 11.51 | + | |
61 | 4′-glu-isoorientin | C27H30O16 | 609.14 | [M-H] | 447 | 5.27 | + | |
62 | Lutonarin | C27H30O16 | 609.14 | [M-H] | 447/519/489/327 | 6.87 | + | |
63 | Rutin | C27H30O16 | 609.14 | [M-H] | 447/519/489/327 | 6.9 | + | |
64 | Keampferol | C15H10O6 | 331.04 | [M-H+HCOOH] | 285/165 | 22.50 | + | |
65 | 7-glu-isopyrenine | C29H34O17 | 653.17 | [M-H] | 315 | 10.06 | + | + |
66 | Hyperoside | C21H20O12 | 509.22 | [M-H+HCOOH] | 463 | 8.95 | + | |
67 | Lonicerin | C27H30O15 | 593.19 | [M-H] | 551/451 | 17.06 | + | |
Miscellaneous Compounds | ||||||||
68 | Caffeic acid | C9H8O4 | 179.03 | [M-H] | 135/109 | 9.25 | + | + |
69 | Ferulic acid | C10H10O4 | 193.02 | [M-H] | 149 | 3.77 | + | |
70 | Isoferulic acid | C10H10O4 | 193.02 | [M-H] | 149 | 4.01 | + | |
71 | Vanilloloside | C13H16O9 | 315.07 | [M-H] | 153 | 1.6 | + | + |
72 | Glu-2,3-dihydroxybenzoic acid | C14H20O8 | 315.11 | [M-H] | 187/297/253/145 | 22.81 | + | |
73 | Glu-2-hydro-3-methoben | C14H18O9 | 329.09 | [M-H] | 167 | 6.89 | + | + |
74 | Methyl-3-(β-d-glucopyranosyl)-2-hydroxybenzoate | C14H18O9 | 329.23 | [M-H] | 209/311 | 19.25 | + | |
75 | Glu-caffeic acid | C15H18O9 | 341.09 | [M-H] | 179/135/203/239 | 1.97 | + | |
76 | Syringin | C17H24O9 | 371.10 | [M-H] | 249 | 4.7 | + | |
77 | 3-[(6-O-Arabinopyranosyl)-β-d-glucopyranosyloxy]oct-1-en | C19H34O10 | 421.20 | [M-H] | 289/133 | 12.57 | + | |
78 | Methyl-3-[(6-O-β-d-glucopyranosyl)-β-d- glucopyranosyloxy]-2-hydroxybenzoate | C23H24O12 | 491.12 | [M-H] | 153/315/475 | 12.31 | + | |
79 | (+) Syringaresinol | C24H30O8 | 491.14 | [M-H+HCOOH] | 315/447/153 | 9.94 | + | |
80 | Lonicerin | C27H30O15 | 593.19 | [M-H] | 551/451/ | 16.68 | + | |
Xanthones | ||||||||
81 | Mangiferin * | C19H18O11 | 421.08 | [M-H] | 403/331/301 | 5.98 | + | |
82 | Gentianabavaroside | C26H30O15 | 581.16 | [M-H] | 401/357/313/ | 3.71 | + | |
Triterpenoids | ||||||||
83 | Gentrigeoside D | C36H60O13 | 745.40 | [M-H+HCOOH] | 699 | 11.99 | + | |
84 | Gentrigeoside C | C42H70O17 | 845.24 | [M-H] | 683/803 | 21.77 | + | |
85 | Glu-Gentigeoside C | C46H56O25 | 1007.31 | [M-H] | 845/801/639/487 | 11.52 | + | |
86 | Gentrigeoside A (Dammarane) | C36H60O12 | 683.40 | [M-H] | 640/622 | 28.46 | + | |
87 | Rha-Gentrigeoside | C46H54O27 | 1037.51 | [M-H+HCOOH] | 991 | 13.6 | + |
Annotation: + indicated the compound in the specie; * indicated compound compared with standards; blank indicated without the compound.