Table 1.
Compound Name | RT (min) | Detected Mass | Theoretical Mass | Adduct | Formula | MS/MS Fragment | VIP | p-Value | |Log2 FC| | FC |
---|---|---|---|---|---|---|---|---|---|---|
Flavan-3-ols | ||||||||||
Epiafzelechin 3-O-gallate | 4.30 | 426.0945 | 426.0951 | [M-H2O-H]- | C22H18O9 | 169, 125 | 1.38 | 2.00 × 10−9 | 1.30 | 2.46 |
Epicatechin 3-O-gallate | 4.49 | 442.0925 | 442.0905 | [M-H2O-H]- | C22H18O10 | 123, 139, 153 | 1.37 | 3.00 × 10−8 | 1.97 | 3.91 |
Catechin * | 4.60 | 290.0785 | 290.0790 | [M+H]+ | C15H14O6 | 95,97,109,123,125 | 1.23 | 2.00 × 10−4 | 0.83 | 1.78 |
Epigallocatechin gallate * | 5.02 | 458.0831 | 458.0849 | [M+H]+ | C22H18O11 | 139, 151, 289 | 1.45 | 4.00 × 10−3 | 1.31 | 0.40 |
Epigallocatechin 3-(3”-methylgallate) | 5.96 | 472.1006 | 472.1006 | [M-H]- | C23H20O11 | 139, 140, 167 | 1.38 | 4.00 × 10−9 | 6.06 | 66.66 |
Epicatechin 3-O-(3-O-methylgallate) | 7.32 | 456.1055 | 456.1056 | [M-H]- | C23H20O10 | 109, 124, 168, 183, 289 | 1.38 | 2.00 × 10−8 | 7.61 | 195.68 |
Epicatechin * | 7.34 | 290.0793 | 290.0790 | [M-H]- | C15H14O6 | 123, 139, 147, 207 | 1.37 | 2.00 × 10−8 | 3.57 | 11.87 |
Epigallocatechin 3-p-coumaroate | 8.12 | 452.1109 | 452.1107 | [M-H]- | C24H20O9 | 196, 255 | 1.37 | 5.00 × 10−8 | 1.60 | 3.03 |
Proanthocyanins | ||||||||||
Epigallocatechin-(4beta->8)-epicatechin 3-O-gallate | 4.27 | 746.1481 | 746.1483 | [M+H]+ | C37H30O17 | 305, 443, 579 | 1.36 | 3.00 × 10−7 | 1.73 | 3.32 |
Procyanidin B5 | 5.25 | 578.1430 | 578.1424 | [M-H2O-H]- | C30H26O12 | 289, 469 | 1.37 | 8.00 × 10−8 | 3.05 | 8.29 |
3-O-beta-D-Galactopyranosylproanthocyanidin A5′ | 5.50 | 738.1771 | 738.1796 | [M+Na]+ | C36H34O17 | 195, 455, 723 | 1.31 | 8.00 × 10−6 | 9.93 | 976.56 |
Prodelphinidin B | 6.01 | 610.1335 | 610.1323 | [M+H]+ | C30H26O14 | 309, 757 | 1.38 | 2.00 × 10−9 | 2.46 | 5.49 |
Epigallocatechin 3-O-gallate-(4beta->6)-epicatechin 3-O-gallate | 6.67 | 898.1590 | 898.1593 | [M+H]+ | C44H34O21 | 433, 741 | 1.32 | 5.00 × 10−6 | 1.39 | 2.62 |
Epiafzelechin 3-O-gallate-(4beta->6)-epigallocatechin 3-O-gallate | 7.41 | 882.1608 | 882.1643 | [M+H]+ | C44H34O20 | 271, 441, 591 | 1.25 | 8.00 × 10−5 | 1.53 | 2.89 |
Flavonol and flavone glycosides | ||||||||||
Myricetin | 3.65 | 318.0383 | 318.0376 | [M-H2O-H]- | C15H8O7 | 125, 169, 241 | 1.39 | 9.00 × 10−10 | 4.31 | 19.85 |
Vitexin 2″-O-rhamnoside-4‴-acetate | 3.77 | 620.1727 | 620.1741 | [M-H2O-H]- | C29H32O15 | 339, 449, 493 | 1.16 | 9.00 × 10−4 | 0.69 | 1.61 |
Kaempferol 3-O-arabinoside | 4.05 | 418.0891 | 418.0900 | [M+H]+ | C20H18O10 | 211, 401 | 1.37 | 7.00 × 10−8 | 5.07 | 33.57 |
Quercetin 3-galloylglucosyl-arabinofuranoside | 4.32 | 748.1520 | 748.1487 | [M-H]- | C33H32O20 | 229, 285 | 1.38 | 8.00 × 10−9 | 2.46 | 5.50 |
Myricetin 3-rhamnoside-3′-glucoside | 4.95 | 626.1495 | 626.1483 | [M-H]- | C27H30O17 | 178, 316 | 1.05 | 5.00 × 10−3 | 0.72 | 1.64 |
Isovitexin 2″-O-rhamnoside | 4.95 | 578.1621 | 578.1636 | [M+H]+ | C27H30O14 | 247, 291, 409, 427 | 1.24 | 1.00 × 10−4 | 2.67 | 6.36 |
Kaempferol 3-glucoside | 5.27 | 448.1007 | 448.1006 | [M-H2O-H]- | C21H20O11 | 145, 301, 377 | 1.29 | 2.00 × 10−5 | 1.34 | 2.52 |
Kaempferol 7,4′-dirhamnoside | 5.50 | 578.1629 | 578.1636 | [M-H]- | C27H30O14 | 245, 289 | 1.26 | 6.00 × 10−5 | 2.75 | 6.72 |
Pelargonidin 3-rhamnoside 5-glucoside | 5.50 | 579.1722 | 579.1714 | [M-H]- | C27H31O14 | 154, 245, 289, 469 | 1.25 | 1.00 × 10−4 | 2.79 | 6.90 |
Cyanidin 3-sambubioside | 5.63 | 581.1510 | 581.1506 | [M-H]- | C26H29O15 | 419, 435, 449, 458 | 1.28 | 3.00 × 10−5 | 0.99 | 1.99 |
Quercetin 3-rutinoside-4′-glucoside | 5.90 | 772.2045 | 772.2062 | [M-H]- | C33H40O21 | 151, 255, 271, 301, 300 | 1.31 | 7.00 × 10−6 | 9.73 | 849.64 |
Cyanidin 3-diglucoside 5-glucoside | 5.90 | 773.2145 | 773.2140 | [M-H]- | C33H41O21 | 277, 513 | 1.30 | 1.00 × 10−5 | 11.33 | 2579.02 |
Kaempferol 3-(2″-hydroxypropionylglucoside)-4′-glucoside | 5.94 | 682.1734 | 682.1745 | [M-H2O-H]- | C30H34O18 | 213, 249, 327 | 1.36 | 3.00 × 10−7 | 4.87 | 29.33 |
Delphinidin 3-(6-p-coumaroylgalactoside) | 6.01 | 611.1379 | 611.1401 | [M+H]+ | C30H27O14 | 138, 331, 409 | 1.38 | 2.00 × 10−9 | 2.65 | 6.29 |
Quercetagetin 7-methylether 6-glucoside | 6.04 | 494.1060 | 494.1060 | [M-H]- | C22H22O13 | 163, 319, 337 | 1.30 | 1.00 × 10−5 | 2.04 | 4.10 |
Quercetin 3-arabinoside | 6.11 | 434.0853 | 434.0849 | [M-H]- | C20H18O11 | 343, 313 | 1.36 | 1.00 × 10−7 | 2.15 | 4.43 |
Delphinidin-3-O-arabinoside | 6.12 | 435.0933 | 435.0927 | [M-H]- | C20H19O11 | 165, 289, 341 | 1.26 | 8.00 × 10−5 | 2.11 | 4.33 |
Quercetin 3-galactoside | 6.14 | 464.0944 | 464.0955 | [M+H]+ | C21H20O12 | 138, 303 | 1.08 | 3.00 × 10−3 | 0.91 | 1.88 |
Cyanidin 3-(6″-acetylglucoside)-5-glucoside | 6.31 | 652.1641 | 652.1639 | [M-H2O-H]- | C29H32O17 | 207, 315, 515 | 1.08 | 3.00 × 10−3 | 0.63 | 1.55 |
Pelargonidin 3-sophoroside 5-glucoside | 6.32 | 757.2184 | 757.2191 | [M+H]+ | C33H41O20 | 287, 433, 595 | 1.39 | 5.00 × 10−10 | 5.98 | 63.09 |
Cyanidin 3-O-(6-O-p-coumaroyl)glucoside | 6.46 | 594.1373 | 594.1373 | [M+H]+ | C30H26O13 | 166, 273, 424, 442, 527 | 1.39 | 2.00 × 10−10 | 2.17 | 4.49 |
Kaempferol 3-(6″-ferulylglucoside) | 6.51 | 624.1464 | 624.1479 | [M+H]+ | C31H28O14 | 317, 165, 203 | 1.33 | 2.00 × 10−6 | 8.49 | 360.45 |
Pelargonidin 3-coumarylglucoside-5-acetylglucoside | 6.52 | 782.2061 | 782.2058 | [M-H2O-H]- | C38H38O18 | 457, 461, 337 | 1.31 | 1.00 × 10−5 | 3.73 | 13.26 |
Kaempferol 3-O-[2″-(4‴--acetyl-rhamnosyl)-6″-glucosyl] glucoside | 6.53 | 798.2216 | 798.2219 | [M+H]+ | C35H42O21 | 519, 524 | 1.36 | 2.00 × 10−7 | 4.01 | 16.15 |
Kaempferol 3-glucoside-7-xyloside | 6.83 | 580.1452 | 580.1428 | [M+H]+ | C26H28O15 | 271, 396 | 1.33 | 2.00 × 10−6 | 3.93 | 15.27 |
Kaempferol 3-(4″-acetyl-6″-p-coumarylglucoside) | 8.14 | 636.1456 | 636.1479 | [M-H2O-H]- | C29H32O16 | 313, 465, 483 | 1.36 | 2.00 × 10−7 | 3.16 | 8.93 |
Quercetin 3,3′-dimethyl ether 4′-glucoside | 8.58 | 510.1369 | 510.1373 | [M-H2O-H]- | C23H26O13 | 285, 442, 599 | 1.18 | 5.00 × 10−4 | 1.04 | 2.05 |
Kaempferol | 8.90 | 286.0465 | 286.0477 | [M+H]+ | C15H10O6 | 121, 165, 241 | 1.55 | 4.00 × 10−3 | 1.80 | 0.29 |
Phenolic acids | ||||||||||
Phenol | 0.74 | 94.0414 | 94.0419 | [M+H]+ | C6H6O | 62, 73, 82 | 1.23 | 4.00 × 10−3 | 1.24 | 0.42 |
5-O-Caffeoylquinic acid | 1.51 | 354.0955 | 354.0951 | [M-H]+ | C16H18O9 | 103, 175 | 1.36 | 2.00 × 10−7 | 2.33 | 5.02 |
Chlorogenic acid | 2.42 | 354.0933 | 354.0951 | [M+Na]+ | C16H18O9 | 93, 135, 173, 191 | 1.47 | 4.00 × 10−3 | 0.71 | 0.61 |
Salicylic acid | 4.24 | 138.0309 | 138.0317 | [M+H]+ | C7H6O3 | 56, 65, 116, 139, 140 | 1.52 | 4.00 × 10−3 | 1.44 | 0.37 |
4-Hydroxybenzoic acid | 5.02 | 138.0312 | 138.0317 | [M+H]+ | C7H6O3 | 56, 111, 116, 139, 140 | 1.40 | 4.00 × 10−3 | 0.69 | 0.62 |
3-O-Methylgallate | 7.35 | 184.0376 | 184.0372 | [M-H]- | C8H8O5 | 124, 139, 168 | 1.33 | 3.00 × 10−6 | 0.97 | 1.97 |
3-O-p-Coumaroylquinic acid | 7.54 | 338.1000 | 338.1002 | [M-H2O-H]- | C16H18O8 | 93, 119, 173, 191 | 1.15 | 1.00 × 10−3 | 1.31 | 2.48 |
Shikimic acid | 9.49 | 174.0521 | 174.0528 | [M-H2O-H]- | C7H10O5 | 61, 67, 93, 173 | 1.33 | 4.00 × 10−3 | 0.68 | 0.62 |
Amino acids | ||||||||||
Lysine | 0.63 | 146.1050 | 146.1055 | [M+H]+ | C6H14N2O2 | 72, 84, 128, 130 | 1.36 | 4.00 × 10−3 | 1.01 | 0.50 |
Alanine | 0.72 | 89.0472 | 89.0477 | [M+H]+ | C3H7NO2 | 68, 77 | 1.27 | 4.00 × 10−3 | 0.88 | 0.54 |
Aspartic acid | 0.74 | 133.0371 | 133.0375 | [M+H]+ | C4H7NO4 | 74, 88, 102, 116 | 1.15 | 4.00 × 10−3 | 1.84 | 0.28 |
Methionine | 1.04 | 149.0503 | 149.0510 | [M+H]+ | C5H11NO2S | 102, 131 | 1.23 | 4.00 × 10−3 | 1.37 | 0.39 |
Valine | 1.05 | 117.0785 | 117.0790 | [M+H]+ | C5H11NO2 | 58, 59, 118, 119 | 1.32 | 4.00 × 10−3 | 1.04 | 0.49 |
Isoleucine | 1.92 | 131.0939 | 131.0946 | [M+H]+ | C6H13NO2 | 69, 72, 86, 90 | 1.39 | 4.00 × 10−3 | 0.89 | 0.54 |
Tyrosine | 2.76 | 181.1882 | 181.1885 | [M-H]- | C9H11NO3 | 91, 119, 123, 136, 165 | 1.37 | 7.00 × 10−8 | 3.57 | 11.84 |
Cysteine | 5.63 | 121.1586 | 121.1582 | [M-H]- | C3H7NO2S | 74, 100, 98 | 1.22 | 2.00 × 10−4 | 0.90 | 1.87 |
Alkaloids | ||||||||||
Adenine | 0.63 | 135.0556 | 135.0545 | [M-H]- | C5H5N5 | 119 | 1.28 | 4.00 × 10−3 | 0.84 | 0.56 |
2-Acetylpyrazine | 1.04 | 122.0475 | 122.0480 | [M+H]+ | C6H6N2O | 80, 95, 96, 123 | 1.28 | 4.00 × 10−3 | 1.91 | 0.27 |
3-Methylxanthine | 1.15 | 166.0487 | 166.0491 | [M+H]+ | C6H6N4O2 | 120 | 1.28 | 4.00 × 10−5 | 3.17 | 9.01 |
Ellagic acid | 3.86 | 302.0048 | 302.0063 | [M+H]+ | C14H6O8 | 57, 275, 285, 303 | 1.20 | 4.00 × 10−3 | 1.71 | 0.31 |
2-Acetylpyrrole | 4.27 | 109.0526 | 109.0528 | [M+Hac-H]- | C6H7NO | 67, 83 | 1.29 | 4.00 × 10−3 | 1.42 | 0.37 |
Theophylline | 6.27 | 180.0641 | 180.0647 | [M-H2O+H]- | C7H8N4O2 | 135, 146, 161, 164 | 1.50 | 4.00 × 10−3 | 0.62 | 0.65 |
Aquifoliunine EII | 6.32 | 721.2591 | 721.2582 | [M+K]+ | C34H43NO16 | 231, 273, 411 | 1.39 | 2.00 × 10−10 | 4.82 | 28.31 |
Caffeine * | 9.54 | 194.0800 | 194.0804 | [M-H2O-H]- | C8H10N4O2 | 85, 93 | 1.30 | 4.00 × 10−3 | 0.59 | 0.66 |
Note: Fold change (FC) is based on comparing the mass intensity of metabolites between ZJT and YKT; metabolite marked with * is confirmed by standards.