Table 4.
Metabolites identified in PF, PC, and PD extracts.
| n | Rt (min) | Compound | Molecular Formula | Error (ppm) | [M − H]− (m/z) | (−)HRMS/MS | [M + H]+ (m/z) | (+)HRMS/MS | PF | PC | PD |
|---|---|---|---|---|---|---|---|---|---|---|---|
| 1 | 1.72 | Hexose sugar alcohol | C6H14O6 | 0.34 | 181.0708 | 163.0601 (C6H11O5), 101.0231 (C4H5O3), 89.0231 (C3H5O3), 71.0125 (C3H3O2), 59.0126 (C2H3O2) | √√ | √√ | √√ | ||
| 2 | 1.79 | Quinic acid | C7H12O6 | 0.71 | 191.0551 | 173.0445 (C7H9O5), 127.0389 (C6H7O3), 111.0440 (C6H7O2), 93.0333 (C6H5O), 85.0282 (C4H5O2) | √√ | √√ | √√ | ||
| 3 | 1.82 | (Hexosyl sugar alcohol)-malic acid | C10H18O10 | 0.32 | 297.0823 | 181.0708 (C6H13O6), 133.0131 (C4H5O5), 115.0024 (C4H3O4), 101.0231 (C4H5O3), 89.0231 (C3H5O3), 71.0125 (C3H3O2), 59.0125 (C2H3O2) | 321.0793 [M + Na]+ | 205.0687 (C6H14O6Na), 187.0582 (C6H12O5Na), 157.0111 (C4H6O5Na) | √√ | √√ | √√ |
| 4 | 1.85 | Ketohexosyl-malic acid | C10H16O10 | −0.81 | 295.0669 | 179.0553 (C6H11O6), 133.0130 (C4H5O5), 101.0231 (C4H5O3), 89.0231 (C3H5O3), 71.0125 (C3H3O2), 59.0125 (C2H3O2) | 319.0633 [M + Na]+ | 301.0535 (C10H14O9Na), 259.0432 (C8H12O8Na), 229.0321 (C7H10O7Na), 203.0530 (C6H12O6Na), 185.0424 (C6H10O5Na), 157.0110 (C4H6O5Na) | √√ | √√ | √√ |
| 5 | 2.61 | Citric acid | C6H8O7 | 2.15 | 191.0190 | 111.0075 (C5H3O3), 87.0074 (C3H3O3) | √√ | √√ | √√ | ||
| 6 | 7.63 | 3-(cis)-O-caffeoylquinic acid | C16H18O9 | 3.87 | 353.0881 | 191.0553 (C7H11O6), 179.0340 (C9H7O4), 135.0440 (C8H7O2) | √√ | √√ | √ | ||
| 7 | 7.94 | 3-(trans)-O-Caffeoylquinic acid | C16H18O9 | 3.86 | 353.0881 | 191.0552 (C7H11O6), 179.0341 (C9H7O4), 135.0440 (C8H7O2) | √√ | √√ | √ | ||
| 8 | 8.43 | Caffeoyl hexoside | C15H18O9 | 3.94 | 341.0880 | 179.0339 (C9H7O4), 161.0233 (C9H5O3) | √√ | √√ | √ | ||
| 9 | 8.65 | Coumaroyl dihexoside | C21H28O13 | 3.82 | 487.1465 | 307.0817 (C15H15O7), 163.0399 (C9H7O3), 145.0283 (C9H5O2) | √√ | √√ | √ | ||
| 10 | 8.74 | Cyanidin 3-O-hexoside | C21H21O11 | 1.52 | 447.0939 [M − 2H]− | 449.1085 [M]+ | 287.0556 (C15H11O6) | √√ | √√ | √√ | |
| 11 | 8.80 | Dimeric B-type proanthocyanidins | C30H26O12 | 3.49 | 577.1361 | 289.0721 (C15H13O6) | √√ | √ | — | ||
| 12 | 8.98 | Cyanidin 3-O- hexoside | C21H21O11 | −0.24 | 447.0937 [M − 2H]− | 449.1077 [M]+ | 287.0553 (C15H11O6) | √√ | √√ | √√ | |
| 13 | 9.05 | (Benzyl)hexose-hexoside | C19H28O11 | 2.46 | 431.1559/477.1615 [(M + FA) − H]− | 269.1037 (C13H17O6), 161.0445 (C6H9O5), 113.0231 (C5H5O3), 101.0231 (C4H5O3) | √√ | √√ | √√ | ||
| 14 | 9.10 | Coumaroyl dihexoside | C21H28O13 | 2.57 | 487.1459 | 163.0390 (C9H7O3), 145.0283 (C9H5O2) | √√ | √√ | √ | ||
| 15 | 9.13 | Cyanidin 3-O-rutinoside | C27H31O15 | −0.26 | 593.1517 [M − 2H]− | 284.0324 (C15H8O6) | 595.1656 [M]+ | 449.1083 (C21H21O11), 287.0551 (C15H11O6) | √√ | √ | √√ |
| 16 | 9.38 | dimeric B-type proanthocyanidins | C30H26O12 | 3.72 | 577.1362 | 289.0724 (C15H13O6) | √√ | √ | — | ||
| 17 | 9.45 | 3-O-coumaroylquinic acid | C16H18O8 | 3.16 | 337.0929 | 191.0552 (C7H11O6), 163.0390 (C9H7O3), 119.0490 (C8H7O) | √√ | √√ | √ | ||
| 18 | 9.72 | 5-(trans)-O-caffeoylquinic acid | C16H18O9 | 3.74 | 353.0880 | 191.0553 (C7H11O6) | √√ | √√ | √ | ||
| 19 | 9.82 | 4-O-caffeoylquinic acid | C16H18O9 | 3.86 | 353.0881 | 191.0553 (C7H11O6), 179.0338 (C9H7O4), 173.0445 (C7H9O5), 135.0440 (C8H7O2) | √√ | √√ | √ | ||
| 20 | 9.83 | Catechin/Epicatechin | C15H14O6 | 2.89 | 289.0715 | 245.0815 (C14H13O4), 205.0500 (C11H9O4), 179.0344 (C9H7O4) | √√ | √√ | √ | ||
| 21 | 10.03 | 5-O-Feruloylquinic acid | C17H20O9 | 3.40 | 367.1036 | 193.0499 (C10H9O4), 191.1560 (C7H11O6), 173.0448 (C7H9O5), 161.0231 (C9H5O3), 134.0363 (C8H6O2) | √√ | √√ | — | ||
| 22 | 10.19 | Coumaroyl-(acetyl)hexose-hexoside isomer | C23H30O14 | 3.70 | 529.1571 | 341.1092 (C12H21O11), 307.0825 (C15H15O7), 163.0389 (C9H7O3), 145.0284 (C9H5O2) | √√ | √√ | √ | ||
| 23 | 10.35 | Dimeric B-type proanthocyanidins | C30H26O12 | 1.12 | 577.1347 | 289.0720 (C15H13O6) | √√ | √ | — | ||
| 24 | 10.40 | Benzylhexose pentoside | C18H26O10 | −1.36 | 401.1450/447.1504 [(M + FA) − H]− | 269.1031 (C13H17O6), 161.0446 (C6H9O5) | 425.1412 [M + Na]+ | 293.0997 (C13H18O6Na) | √√ | √√ | √√ |
| 25 | 10.48 | Feruloyl hexoside isomer | C16H20O9 | 3.69 | 355.1037 | 193.0496 (C10H9O4), 175.0391 (C10H7O3) | √√ | √√ | — | ||
| 26 | 10.49 | (Benzyl)hexose-dihexoside | C25H38O16 | 2.00 | 593.2089 | 415.1607 (C19H27O10), 269.1032 (C13H17O6) | √√ | √√ | √√ | ||
| 27 | 10.55 | Coumaroyl-(acetyl)hexose-hexoside isomer | C23H30O14 | 0.31 | 529.1570 | 341.1088 (C12H21O11), 307.0824 (C15H15O7), 163.0391 (C9H7O3), 145.0284 (C9H5O2) | 553.1530 [M + Na]+ | 391.1009 (C17H20O9Na), 349.0896 (C15H18O8Na) | √√ | √√ | √ |
| 28 | 10.56 | (Benzaldehyde)hexose-pentoside | C18H24O11 | 3.59 | 415.1250/461.1310 [(M + FA) − H]− | 121.0282 (C7H5O2) | √√ | √√ | √√ | ||
| 29 | 10.59 | Methyl caffeoylquinate isomer | C17H20O9 | 2.92 | 367.1034 | 179.0341 (C9H7O4), 173.0449 (C7H9O5), 161.0235 (C9H5O3) | √√ | √√ | — | ||
| 30 | 10.65 | 5-(cis)-O-caffeoylquinic acid | C16H18O9 | 3.60 | 353.0880 | 191.0553 (C7H11O6) | √√ | √√ | — | ||
| 31 | 10.81 | Feruloyl hexoside isomer | C16H20O9 | 3.27 | 355.1035 | 193.0502 (C10H9O4), 175.0391 (C10H7O3) | √√ | √√ | — | ||
| 32 | 10.85 | Coumaroyl-(acetyl)hexose-hexoside isomer | C23H30O14 | 3.75 | 529.1572 | 341.1088 (C12H21O11), 307.0824 (C15H15O7), 163.0391 (C9H7O3), 145.0284 (C9H5O2) | √√ | √√ | √ | ||
| 33 | 10.90 | 4-O-coumaroylquinic acid | C16H18O8 | 3.18 | 337.0929 | 191.0557 (C7H11O6), 173.0446 (C7H9O5), 163.0387 (C9H7O3) | √√ | √√ | √√ | ||
| 34 | 10.97 | Catechin/Epicatechin | C15H14O6 | 2.89 | 289.0715 | 245.0814 (C14H13O4), 205.0503 (C11H9O4), 179.0344 (C9H7O4) | √√ | √√ | √ | ||
| 35 | 11.00 | Feruloyl-(acetyl)hexose-hexoside isomer | C24H32O15 | 2.47 | 559.1671 | 175.0391 (C10H7O3) | √√ | √√ | — | ||
| 36 | 11.26 | Feruloyl-(acetyl)hexose-hexoside isomer | C24H32O15 | 2.85 | 559.1673 | 175.0392 (C10H7O3) | √√ | √√ | — | ||
| 37 | 11.43 | Coumaroyl-(acetyl)hexose-hexoside isomer | C23H30O14 | 3.75 | 529.1572 | 341.1095 (C12H21O11), 307.0820 (C15H15O7), 163.0394 (C9H7O3), 145.0284 (C9H5O2) | √√ | √√ | √ | ||
| 38 | 11.51 | Methyl coumaroylquinate isomer | C17H20O8 | 3.83 | 351.1088 | 145.0283 (C9H5O2) | √√ | √√ | √√ | ||
| 39 | 11.61 | Dimethyl-hydroxy-decadienedioate hexoside | C18H28O10 | 3.74 | 403.1614 | 241.1080 (C12H17O5), 197.1178 (C11H17O3), 181.0866 (C10H13O3), 59.0126 (C2H3O2) | √√ | √√ | √ | ||
| 40 | 11.81 | Methyl coumaroylquinate isomer | C17H20O8 | 3.83 | 351.1088 | 145.0284 (C9H5O2), 119.0492 (C8H7O) | √√ | √√ | √√ | ||
| 41 | 11.93 | Coumaroyl-(diacetyl)dihexoside isomer | C25H32O15 | 3.00 | 571.1675 | 307.0824 (C15H15O7), 163.0389 (C9H7O3), 145.0284 (C9H5O2) | √√ | √√ | √ | ||
| 42 | 12.22 | Methyl caffeoylquinate isomer | C17H19O9 | 2.97 | 367.1034 | 179.0341 (C9H7O4), 161.0238 (C9H5O3) | √√ | √√ | — | ||
| 43 | 12.26 | Hexyl-dihexoside isomer | C18H34O11 | 3.27 | 471.2084 [(M + FA) − H]− | 263.1499 (C12H24O6), 161.0444 (C6H9O5), 101.0231 (C4H5O3) | √√ | √√ | √ | ||
| 44 | 12.37 | Coumaroyl-(diacetyl)dihexoside isomer | C25H32O15 | 2.65 | 571.1673 | 341.1088 (C12H21O11), 307.0834 (C15H15O7), 163.0388 (C9H7O3), 145.0283 (C9H5O2) | 595.1644 [M + Na]+ | 391.1009 (C17H20O9Na), 349.0900 (C15H18O8Na), 331.0790 (C15H16O7Na), 287.0756 (C10H16O8Na), 167.0315 (C6H8O4Na) | √√ | √√ | √ |
| 45 | 12.50 | Delphinidin-3-O-rutinoside | C27H31O16 | 0.18 | 609.1466 [M − 2H]− | 611.1608 [M]+ | 303.0501 (C15H11O7) | √√ | √ | √√ | |
| 46 | 12.59 | Dimethyl-octadienedioate hexoside | C16H24O9 | 2.93 | 359.1347 | 197.0810 (C10H13O4), 153.0910 (C9H13O2), 59.0125 (C2H3O2) | √√ | √√ | √ | ||
| 47 | 12.64 | Coumaroyl-(diacetyl)dihexoside isomer | C25H32O15 | 1.30 | 571.1665 | 341.1084 (C12H21O11), 307.0829 (C15H15O7), 163.0390 (C9H7O3), 145.0284 (C9H5O2) | 595.1636 [M + Na]+ | 391.1004 (C17H20O9Na), 349.0899 (C15H18O8Na), 331.0804 (C15H16O7Na), 287.0732 (C10H16O8Na), 167.0317 (C6H8O4Na) | √√ | √√ | √ |
| 48 | 12.66 | Delphinidin-3-O-hexoside | C21H21O12 | 0.34 | 465.1029 [M]+ | 303.0502 (C15H11O7) | √√ | √√ | √√ | ||
| 49 | 12.79 | Dimeric A-type proanthocyanidins | C30H24O12 | 1.45 | 575.1204 | 539.0960 (C30H19O10), 423.0726 (C22H15O9), 407.0771 (C22H15O8), 327.0513 (C17H11O7), 289.0723 (C15H13O6), 287.0562 (C15H11O6), 285.0409 (C15H9O6) | 577.1349 | 287.0552 (C15H11O6) | √√ | √√ | √ |
| 50 | 12.92 | Isorhamnetin 3-O-rutinoside | C28H32O16 | 3.78 | 623.1630 | 315.0503 (C16H11O7), 314.0431 (C16H10O7) | √√ | — | — | ||
| 51 | 13.08 | Quercetin-3-O-hexoside | C21H20O12 | 0.12 | 463.0889 | 301.0346 (C15H9O7) | 465.1028 | 303.0502 (C15H11O7) | √√ | √√ | √ |
| 52 | 13.12 | Isorhamnetin-3-O-pentose-hexoside | C27H30O16 | 1.18 | 609.1472 | 315.0509 (C16H11O7) | 611.1614 | 317.0657 (C16H13O7) | √√ | — | — |
| 53 | 13.20 | Abscisic acid hexoside | C21H30O9 | 1.59 | 449.1789 [M + Na]+ | 287.1258 (C15H20O4Na) | √√ | √√ | — | ||
| 54 | 13.26 | Dicrotalic acid (Benzyl)hexoside | C19H26O10 | 3.91 | 413.1458 | 269.1039 (C13H17O6) | √√ | √√ | √ | ||
| 55 | 13.36 | Quercetin-3-O-di-pentoside | C25H26O15 | 1.65 | 565.1207 | 301.0325 (C15 H9 O7) | 567.1354 | 303.0506 (C15 H11 O7+) | √√ | √√ | √ |
| 56 | 13.43 | Dimeric A-type proanthocyanidins | C30H24O12 | 1.35 | 575.1204 | 539.0959 (C30H19O10), 407.0771 (C22H15O8), 327.0507 (C17H11O7), 289.0719 (C15H13O6), 287.0560 (C15H11O6), 285.0405 (C15H9O6) | 577.1348 | 287.0553 (C15H11O6) | √√ | √√ | √ |
| 57 | 13.59 | Quercetin-3-O-pentoside | C20H18O11 | 1.98 | 433.0779 | 301.0345 (C15H9O7) | 435.0930 | 303.0503 (C15H11O7) | √√ | √√ | √ |
| 58 | 13.68 | Quercetin 3-O-rutinoside | C27H30O16 | 1.18 | 609.1468 | 301.0349 (C15H9O7) | 611.1614 | 303.0516 (C15H11O7) | √√ | √√ | √ |
| 59 | 13.84 | Coumaroyl-(triacetyl)dihexoside isomer | C27H34O16 | 3.81 | 613.1786 | 163.0387 (C9H7O3), 145.0284 (C9H5O2) | √√ | √√ | √ | ||
| 60 | 14.01 | Quercetin-3-O-pentoside | C20H18O11 | 1.06 | 433.0778 | 301.0349 (C15H9O7) | 435.0927/457.0744 [M + Na]+ | 303.0501 (C15H11O7) | √√ | √√ | √ |
| 61 | 14.16 | Coumaroyl-(triacetyl)dihexoside isomer | C27H34O16 | 1.21 | 613.1782 | 383.1196 (C14H23O12), 307.0813 (C15H15O7), 163.0393 (C9H7O3), 145.0284 (C9H5O2) | 637.1747 [M + Na]+ | 391.0995 (C17H20O9Na), 373.0882 (C17H18O8Na), 287.0734 (C10H16O8Na), 167.0315 (C6H8O4Na) | √√ | √√ | √ |
| 62 | 14.17 | Quercetin-3-O-deoxyhexoside | C21H20O11 | 3.36 | 447.0937 | 301.0349 (C15H9O7) | 449.1085 | √√ | √√ | √ | |
| 63 | 14.18 | Isorhamnetin 3-O-hexoside | C22H22O12 | 1.60 | 477.1044 | 314.0431 (C16H10O7) | 479.1192 | 317.0659 (C16H13O7) | √√ | — | — |
| 64 | 14.32 | Methyl (hexosyl)-O-coumarate isomer | C16H20O8 | 0.86 | 363.1054 [M + Na]+ | 201.0524 (C10H10O3Na), 185.0427 (C6H10O5Na) | √√ | √√ | — | ||
| 65 | 14.33 | Coumaroyl-(triacetyl)dihexoside isomer | C27H34O16 | 1.03 | 613.1783 | 341.1087 (C12H21O11), 163.0390 (C9H7O3), 145.0284 (C9H5O2) | 637.1746 [M + Na]+ | 391.0992 (C17H20O9Na), 373.0886 (C17H18O8Na), 287.0739 (C10H16O8Na), 167.0317 (C6H8O4Na) | √√ | √√ | √ |
| 66 | 14.36 | Quercetin-3-O-(acetyl)hexoside | C23H22O13 | 1.25 | 505.0996 | 300.0273 (C15H8O7) | 507.1140 | 303.0502 (C15H11O7) | √√ | √√ | √ |
| 67 | 14.65 | [(Dihydroxybenzoyloxy)-dihydroxyphenyl]acetate methyl ester | C16H14O8 | 1.54 | 333.0620 | 197.0446 (C9H9O5), 165.0183 (C8H5O4) | 335.0767 | 137.0235 (C7H5O3) | √√ | √√ | √ |
| 68 | 14.68 | Coumaroyl-(triacetyl)dihexoside isomer | C27H34O16 | 1.31 | 613.1783 | 383.1187 (C14H23O12), 341.1085 (C12H21O11), 163.0390 (C9H7O3), 145.0284 (C9H5O2) | 637.1747 [M + Na]+ | 391.0998 (C17H20O9Na), 373.0895 (C17H18O8Na), 287.0758 (C10H16O8Na) | √√ | √√ | √ |
| 69 | 14.91 | Coumaroyl-(triacetyl)dihexoside isomer | C27H34O16 | 1.31 | 613.1786 | 383.1197 (C14H23O12), 341.1094 (C12H21O11), 307.0833 (C15H15O7), 163.0391 (C9H7O3), 145.0283 (C9H5O2) | 367.1747 [M + Na]+ | 391.1006 (C17H20O9Na), 373.0890 (C17H18O8Na), 287.0744 (C10H16O8Na), 167.0317 (C6H8O4Na) | √√ | √√ | √ |
| 70 | 15.14 | Azelaic acid | C9H16O4 | 2.86 | 187.0970 | 125.0960 (C8H13O) | √√ | √√ | √√ | ||
| 71 | 15.28 | Quercetin-3-O-(Acetyl)rutinoside | C29H34O17 | 1.28 | 651.1583 | 301.0351 (C15H9O7) | 653.1721 | √√ | √√ | √ | |
| 72 | 16.62 | Coumaroyl-(tetraacetyl)dihexoside isomer | C29H36O17 | 1.04 | 655.1893 | 163.0390 (C9H7O3), 145.0284 (C9H5O2) | 679.1852 [M + Na]+ | 373.0889 (C17H18O8Na), 329.0846 (C12H18O9Na) | √√ | √√ | √ |
| 73 | 16.86 | Coumaroyl-(tetraacetyl)dihexoside isomer | C29H36O17 | 1.31 | 655.1892 | 163.0395 (C9H7O3), 145.0285 (C9H5O2) | 679.1854 [M + Na]+ | 433.1112 (C19H22O10Na), 373.0940 (C17H18O8Na), 209.0423 (C8H10O5Na) | √√ | √√ | √ |
| 74 | 17.17 | Coumaroyl-(tetraacetyl)dihexoside isomer | C29H36O17 | 0.69 | 655.1893 | 383.1197 (C14H23O12), 163.0393 (C9H7O3), 145.0284 (C9H5O2) | 679.1849 [M + Na]+ | 433.1115 (C19H22O10Na), 391.1004 (C17H20O9Na), 373.0901 (C17H18O8Na), 329.0835 (C12H18O9Na), 209.0422 (C8H10O5Na) | √√ | √√ | √ |
| 75 | 17.81 | Quercetin | C15H10O7 | 2.73 | 301.0351 | 178.9977 (C8H3O5), 151.0025 (C7H3O4), 121.0283 (C7H5O2) | √√ | √√ | — | ||
| 76 | 19.76 | Coumaroyl-(pentaacetyl)dihexoside isomer | C31H38O18 | 3.34 | 697.1998 | 145.0282 (C9H5O2) | √√ | √√ | — | ||
| 77 | 19.95 | Coumaroyl-(pentaacetyl)dihexoside isomer | C31H38O18 | 3.17 | 697.1996 | 145.0283 (C9H5O2) | √√ | √√ | — |
Legend: √√ = detectable; √ = detectable at low intensity level (1.1 × 103 < Normalized Level < 4.0 × 104); — = not detectable.