|
Peak number | (min) | (nm) | Formula |
ES− () |
ES+ () | Identification | Reference |
[M–H]− (ppm) | MS2b | [M + H]+(ppm) | [M + Na]+ | MS2b |
|
1 | 0.817 | | C7H12O6 | 191.0555 (−0.5) | | | | | Quinic acid | [12] |
|
2 | 0.982 | 223, 287 | C6H8O7 | 191.0198 (3.1) | 173.0099 [M–H–H2O]−, 111.0088 [M–H–2H2O–CO2]− | | | | Citric acid | [13] |
|
3
a | 1.545 | 216, 271 | C7H6O5 | 169.0142 (3.0) | 125.0241 [M–H–CO2]− | | | | Gallic acid | [14] |
|
4
a | 3.010 | 325 | C16H17O9 | 353.0878 (1.4) 375.0695 [M–2H + Na]−, 707.1830 [2M–H]− | 191.0497 [M–H–Ca]−, 179.0312 [Caffeic acid–H]−, 135.0359 [Caffeic acid–H–CO2]− | | | | Neochlorogenic acid | [13] |
|
5
a | 3.639 | 254 | C16H24O10 | 375.1302 (2.9), 751.2667 [2M–H]− | 213.0773 [M–H–Glc]−, 151.0878 [M–H–Glc–CO2–H2O]−, 125.0721 [M–H–Glc–2CO2]− | | | | Loganic acid | [15] |
|
6
a | 4.048 | 224, 278 | C14H20O7 | 299.1133 (0.7) | 179.0447 [M–H–C8H8O]−, 119.0246 [M–H–Glc–H2O]− | | | | Salidroside | [16] |
|
7
a | 4.557 | | C20H30O12 | 461.1674 (3.3) | 315.1348 [M–H–Rha]−, 297.1589 [M–H–Rha–H2O]−, 153.0644 [M–H–Rha–Glc]−, 135.0573 [M–H–Rha–Glc–H2O]− | 463.1220 (−4.3) | 485.1568 | 137.0599 [M + H–Rha–Glc–H2O]+ | Forsythoside E | [17] |
|
8
a | 4.749 | 327 | C16H17O9 | 353.0880 (2.0) | 191.0556 [M–H–Ca]−, 179.0224 [Caffeic acid–H]− | 355.1028 (−0.3) | 377.0857 | | Chlorogenic acid | [18] |
|
9
a | 5.281 | 325 | C16H17O9 | 353.0880 (2.0) | 179.0348 [Caffeic acid–H]−, 173.0461 [Quinic acid–H–H2O]−, 191.0417 [M–H–Ca]− | | | | Cryptochlorogenic acid | [18] |
|
10 | 6.435 | 270 | C17H26O10 | 389.1096 (3.1) | | 391.2176 (−0.8) | 413.1067 | 395.2354 [M + Na–H2O]+ 229.0835 [M + H–Glc]+ | Loganin | [19] |
|
11 | 6.749 | | C14H23O9 | 335.0776 (2.7) | 173.0459 [M–H–Glc]−, 161.0373 [Glc–H–H2O]−, 133.0408 [Glc–H–H2O–CO]− | 337.0883 (5.3) | 359.0686 | 163.0419 [Glc + H–H2O]+ | Rengynic acid-1′-O-β-D- glucoside | [20] |
|
12 | 7.222 | | C21H20O9 | 415.1261 (5.1) | | | 439.1207 | 255.0879 [M + H–Glc]+ | Isomer of chrysophanol glucoside | [21] |
|
13
a | 7.428 | 245 | | 357.1208 (6.2), 403.1263 M + HCOO, 393.0938 M + Cl | | 359.1337 (−1.4) | 381.1154 | | Sweroside | [15] |
|
14 | 7.859 | | C14H23O9 | 335.0871 (4.2) | 193.0506, 161.0377, 133.0423 | 337.0774 (0.9) | 359.0225 | 163.0416 [Glc + H–H2O]+ | Isomer of rengynic acid-1′-O-β-D-glucoside | |
|
15 | 8.106 | 306 | C20H22O8 | 389.1458 (2.6), 435.1519 [M + HCOO]− | 227.0943 [M–H–Glc]− | | | | Polydatin | [22] |
|
16 | 8.222 | | C29H36O16 | 639.2219 (−1.7) | 477.1894 [M–H–Glc]−, 179.0546 [M–Rha–C17H14O6]−, 161.0328 [Glc–H–H2O]−, | | | | R-suspensaside | [23] |
|
17
a | 8.320 | | C21H20O9 | 415.1253 (3.1) | 253.0542 [M–H–Glc]− | 417.1394 (−0.7) | 439.1200 | 255.0864 [M + H–Glc]+ | Chrysophanol glucoside | [21] |
|
18 | 8.874 | | C29H36O16 | 639.2002 (−2.7) | 161.0328 [Glc–H–H2O]−, 179.0349 [M–Rha–C17H14O6]− | | | | S-suspensaside | [24] |
|
19 | 9.054 | | C29H36O15 | 623.1999 (−1.2) | 311.2176 | 625.2137 (0.8) | 647.1942 | 479.1562, 471.1479, 325.0925, 163.0394 | Isomer of forsythoside A | |
|
20
a | 9.470 | 235 | C17H24O11 | 403.1261 (5.2) | | 405.1331 (−1.7) | 427.1203 | 243.0871 [M + H–Glc]+ | Secoxyloganin | [19] |
|
21 | 9.552 | 276, 313 | C21H22O9 | 417.1205 (4.6), 835.2331 [2M–H]− | 255.0652 [M–H–Glc]−, | | 441.1132 | 257.0811 [M + H–Glc]+ | Liquiritin | [25] |
|
22
a | 9.886 | 277, 312 | C26H30O13 | 549.1627 (3.5) | | 551.2823 (4.7) | 573.1737 | 257.0822 [M + H–Api–Glc]+ | Liquiritin apioside | [26] |
|
23 | 9.995 | | C26H30O13 | 549.1629 (3.8) | | 551.3403 (−5.1) | 573.1735 | 257.0815 [M + H–Api–Glc]+ | Isomer of liquiritin apioside | [26] |
|
24 | 10.088 | | C27H30O16 | 609.1844 (−1.8) | | | 633.1712 | | Rhodiosin | [27] |
|
25
a | 10.384 | 250, 300 | C22H22O9 | 429.1410 (3.0) | | | 453.1176 | 269.0974 [M + H–Glc]+ | Ononin | [28, 29] |
|
26
a | 10.722 | 360 | C21H20O12 | 463.0905 (2.8) | 301.0464 [M–H–Glc]− | 465.1033 (5.2) | 487.0333 | 303.0515 [M + H–Glc]+ | Hyperin | [24] |
|
27
a | 10.819 | 326 | C25H24O12 | 515.1205 (2.9) | 353.0751 [M–H–Ca]− | 517.1296 (1.7) | 539.1156 | 499.1187 [M + H–H2O]+, 163.0395 [M + H–Ca–Quinic acid]+ | 3,5-Dicaffeoylquinic acid | [30] |
|
28 | 10.931 | | C29H36O15 | 623.1999 (−1.9) | 461.1378, 161.0185 | | 647.1941 | 471.1497, 325.0925, 163.0415 | Isomer of forsythoside A | |
|
29
a | 11.10 | 256, 354 | C27H30O16 | 609.1465 (1.5) | | 611.1573 (3.3) | 633.1404 | 465.0982 [M + H–Rha]+ 303.0495 [M + H–Rut]+ | Rutin | [31] |
|
30
a | 11.220 | 280 | C29H36O15 | 623.2001 (−1.6) | 461.1920 [M–H–Ca]−, 161.0328 [Caffeic acid–H–H2O]− | | 647.1927 | 163.0386 [Caffeic acid + H–H2O]+ | Forsythoside A | [32] |
|
31 | 11.589 | 283 | C27H30O15 | 593.1534 (−1.3) | 285.0677 [M–H–Rut]− | 595.1694 (−0.7) | | 287.0936 [M + H–Rut]+ | Kaempferol-3-O-rutinoside | [13] |
|
32 | 11.692 | | C19H35O16 | 519.1884 (3.5), 565.1953 [M + HCOO]− | 357.1366 [M–H–Glc]− | | 543.1855 | 359.1454 [M + H–Glc]+, 341.1411 [M + H–Glc–H2O]+ | (+)-Pinoresinol-β-D-glucoside | [33] |
|
33
a | 12.213 | 210, 262 | C20H27NO11 | 456.1523 (3.7) | | 458.1641 (−4.6) | | 296.1124 [M + H–Glc]+, 162.0862 [M + H–Glc–HCT]+ | Amygdalin | [13] |
|
34
a | 12.659 | 326 | C25H24O12 | 515.1162 (−5.4) | 353.0786 [M–H–Ca]− | 517.1348 (0.4) | 539.1193 | 499.1248 [M + H–H2O]+, 163.0387 [M + H–Ca–Quinic acid]+ | 3,4-Dicaffeoylquinic acid | [30] |
|
35
a | 13.082 | 276 | C15H12O4 | 255.0654 (−1.2) | | 257.0659 (−0.8) | | 147.0621 [M + H–RL]+, 137.0422 [M + H–VP]+, 119.0691 [M + H–RL–CO]+ | Liquiritigenin | [34] |
|
36
a | 13.251 | 243, 372 | C26H30O13 | 549.1621 (2.4) | | 551.1725 (3.4) | 573.1563 | 419.1360 [M + H–Api]+, 257.0814 [M + H–Api–Glc]+ | Isoliquiritin apioside | [35] |
|
37
a | 13.300 | 242, 362 | C21H22O9 | 417.1198 (2.9) | 255.0518 [M–H–Glc]− | 419.1314 (−6.7) | 441.1150 | 257.0823 [M + H–Glc]+, 229.1357 [M + H–Glc–CO]+ | Isoliquiritin | [26] |
|
38 | 13.479 | 280 | C27H34O11 | 579.2103 [M + HCOO]− | | | 557.1987 | 552.2463 [M + NH4]+, 355.1516 [M + H–Glc–H2O]+ | Arctiin | [36] |
|
39
a | 14.161 | 277 | C27H34O11 | 579.2106 M + HCOO]− | 371.1826 [M–H–Glc]−, 356.1547 [M–H–Glc–H2O]− | 552.2444 M + NH4]+ | 557.1991 | 373.1563 [M + H–Glc]+, 355.1544 [M + H–Glc–H2O]+ | Phillyrin | [37, 38] |
|
40 | 14.678 | 372, 255 | C15H10O7 | 301.0355 (2.3) | 151.0137 [M–H–C8H6O3]− | 303.0520 (4.9) | | | Quercetin | [39] |
|
41 | 15.039 | 284 | C28H34O15 | 609.1522 (1.3) | 301.0582 [M–H–Rut]− | | | | Hesperidin | [13] |
|
42 | 15.402 | 265, 366 | C15H10O6 | 285.0406 (2.5) | | 287.0721 (4.5) | | 153.0469 [M + H–HEP]+ | Kaempferol | [13] |
|
43 | 16.627 | 255 | C15H10O4 | 253.0507 (2.4) | 225.0741 [M–H–CO]−, 210.0494 [M–H–CO–CH3]−, 182.0542 [M–H–2CO–CH3]−, 154.0553 [M–H–3CO–CH3]− | | | | Chrysophanol | [40] |
|
44 | 17.035 | | C15H10O4 | 253.0512 (4.3) | 225.0752, 210.0474, 182.0485, 154.0531 | | | | Isomer of chrysophanol | [40] |
|
45
a | 17.347 | 254, 287, 426 | C21H20O10 | 431.0989 (2.6) | 269.0673 [M–H–Glc]−, 241.0719 [M–H–Glc–CO]−, 225.0753 [M–H–Glc–CO2]−, 210.0578 [M–H–Glc–CO2–CH3]−, 197.0771 [M–H–Glc–CO–CO2]−, 182.0486 [M–H–Glc–CO2–CH3–CO]− | | 455.1010 | 271.0715 [M + H–Glc]+ | Emodin-8-O-glucoside | [41] |
|
46 | 17.396 | 240, 330, 395 | C15H12O4 | 255.0639 (−7.1) | | 257.0812 (−0.8) | | | Isoliquiritigenin | [26] |
|
47
a | 18.385 | 250, 304 | C16H12O4 | 267.0653 (−1.5) | | 269.0827 (4.8) | 291.0751 | | Formononetin | [42] |
|
48 | 18.804 | | | 895.4082 (2.8) | 719.3849 [M–H–GlcA]− 351.0630 [2GlcA–H]− | 897.4107 (1.2) | 919.3925 | | 22β-Acetoxy licorice saponin B2/uralsaponin F | [43] |
|
49 | 19.194 | 271, 421 | | 445.1168 (−5.6) | 283.0632 [M–H–Glc]− | | 469.1128 | 285.0775 [M + H–Glc]+ | Physcion-8-O-β-D-glucopyranoside | [41] |
|
50 | 19.603 | 248 | C42H60O16 | 819.3843 (0.6) | 351.0699 [2GlcA–H]− | 821.3994 (−0.1) | 843.3996 | 645.3612 [M + H–GlcA]+, 469.3302 [M + H–2GlcA]+, 451.3211 [M + H–2GlcA–H2O]+ | Licorice saponin E2 | [35] |
|
51 | 19.704 | | C16H24O7 | 327.2180 (2.8) | 164.9664 [M–H–Glc]− | | 351.2133 | | Rhododendrol-4′-O-β-D-glucopyranoside | [44] |
|
52 | 20.000 | 254 | C44H64O18 | 879.4062 (1.3) | 351.0806 [M–H–22AG]− | 881.4170 (−0.1) | | 705.3897 [M + H–GlcA]+, 529.3588 [M + H–2GlcA]+, 511.3395 [M + H–2GlcA–H2O]+ | 22-Acetoxyglycyrrhizin | [42] |
|
53 | 20.573 | 352 | C17H14O7 | 329.2341 (3.9) | | | 353.2280 | 301.1443 [M + H–CH2O]+, 287.2002 [M + H–CO2]+, 259.1248 [M + H–CO2–CO]+ | Tricin | [45] |
|
54
a | 21.199 | 260 | C15H8O6 | 283.0262 (6.7) | 239.0359 [M–H–CO2]− | 285.0515 (−13.0) | | | Rhein | [46] |
|
55 | 21.540 | 253 | | 837.3977 (1.2) | 819.4404 [M–H–H2O]−, 661.4100 [M–H–GlcA]−, 351.0815 [2GlcA–H]−, 289.0840 [2GlcA–H–H2O–CO2]− | 839.4061 (−0.5) | 861.3890 | 663.3868 [M + H–GlcA]+, 487.3395 [M + H–2GlcA]+, 469.3286 [M + H–2GlcA–H2O]+ | Licorice saponin G2 | [42] |
|
56 | 21.626 | 236, 327, 370, 384 | C21H20O6 | 367.1208 (7.1) | 309.1566 [M–H–CO–CH2O]−, 265.0635 [M–H–CO–CH2O–CO2]−, 221.0221 [M–H–CO–CH2O–2CO2]− | 369.1369 (−7.6) | 391.1176 | | Glycycoumarin | [47] |
|
57 | 22.087 | 249 | C42H62O16 | 821.3977 (1.7) | 803.4501 [M–H–H2O]−, 759.4542 [M–H–H2O–CO2]−, 645.4102 [M–H–GlcA]−, 627.4000 [M–H–GlcA–H2O]−, 469.3705 [M–H–2GlcA]−, 351.0809 [2GlcA–H]−, 289.0758 [2GlcA–H–H2O–CO2]− | 823.4128 (1.5) | 845.4557 | 647.3797 [M + H–GlcA]+, 471.3480 [M + H–2GlcA]+, 453.3365 [M + H–2GlcA–H2O]+ | Glycyrrhizic acid | [48] |
|
58 | 22.188 | 252 | C42H62O16 | 821.3986 (−1.1) | 351.0768 [M–H–GA]− | 823.4134 (−2.1) | 845.4127 | 647.3823 [M + H–GlcA]+, 471.3365 [M + H–2GlcA]+, 453.3324 [M + H–2GlcA–H2O]+ | Licorice saponin H2 | [26] |
|
59 | 22.389 | 248 | C42H64O15 | 807.4197 (−0.6) | 745.4601 [M–H–Glc]−, 631.4210 [M–H–GlcA]−, 351.0699 [M–H–GA]− | 809.4410 (−0.9) | 831.4138 | | Licorice saponin B2 | [49] |
|
60 | 22.623 | 252 | C42H62O16 | 821.3997 (0.2) | 351.0837 [M–H–GA]− | 823.4105 (−1.3) | 845.3900 | 647.3838 [M + H–GlcA]+, 471.3288 [M + H–2GlcA]+, 453.3279 [M + H–2GlcA–H2O]+ | Licorice saponin K2 | [50] |
|
61
a | 23.230 | 288, 439 | C15H10O5 | 269.0462 (4.5) | 241.0669 [M–H–CO]−, 225.0723 [M–H–CO2]−, 210.0427 [M–H–CO2–CH3]−, 197.0695 [M–H–CO–CO2]−, 182.0477 [M–H–CO2–CH3–CO]−, 154.0552 [M–H–CO2–CH3–2CO]− | | | | Emodin | [40] |
|