Table 1.
ID 1 | Compound Group | Compound Name 1 |
Chemical Formula 2 | MW (g/mol) | [M–H]– | Main MS/MS Fragments (m/z) 3,4 | λmax (CH3OH) (nm) | Detection Mode 5 | Tissue Distribution 6 | ||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|
LEAVES | STEMS | CANES | WOODS | ROOTS | |||||||||
1 | Hydroxybenzoic acid | Quinic acid | C7H12O6 | 192.167 | 191 | 111, 173, 85, 127 | 308, 280 | MS | ✓ | ||||
2 | Hydroxybenzoic acid | Gallic acid | C7H6O5 | 170.120 | 169 | 125, 124, 79, 51 | 278, 214 | MS, NMR, DAD | ✓ | ✓ | ✓ | ||
4 | Hydroxybenzoic acid | Protocatechuic acid | C7H6O4 | 154.121 | 153 | 109, 108 | 297, 258 | MS | ✓ | ✓ | |||
7 | Hydroxybenzoic acid | p-Hydroxybenzoic acid | C7H6O3 | 138.122 | 137 | 93, 60, 79, 108, 118, 137 | 272, 310sh | MS | ✓ | ✓ | |||
8 | Hydroxybenzoic acid | Gentisic acid | C7H6O4 | 154.121 | 153 | 109, 81, 42, 108 | 281, 228, 330sh | MS | ✓ | ||||
9 | Hydroxybenzoic acid | γ-Resorcylic acid | C7H6O4 | 154.121 | 153 | 109, 136, 154, 110, 52, 80, 137, 39, 155 | 313, 245 | MS | ✓ | ||||
30 | Hydroxybenzoic acid | Vanillic acid | C8H8O4 | 168.149 | 167 | 123, 152, 108, 91 | 292, 260 | MS, NMR, DAD | ✓ | ✓ | |||
36 | Hydroxybenzoic acid | Syringic acid | C9H10O5 | 198.174 | 197 | 182, 153, 167, 138 | 276 | MS, NMR, DAD | ✓ | ✓ | ✓ | ||
50 | Hydroxybenzoic acid | Ellagic acid | C14H6O8 | 302.194 | 301 | 284, 300, 257, 229, 184 | 367, 256, 301sh | MS | ✓ | ✓ | |||
14 | Hydroxycinnamic acid | 1-O-Sinapoyl-β-D-glucose | C17H22O10 | 386.353 | 385 | 223, 205, 341, 265, 190, 179, 119, 247 | 282 | MS | ✓ | ||||
16 | Hydroxycinnamic acid | 1-O-(4-Coumaroyl)-glucose | C15H18O8 | 326.301 | 325 | 163, 145, 119, 187, 265, 205 | 322 | MS | ✓ | ✓ | |||
20 | Hydroxycinnamic acid | 1-Caffeoyl-β-D-glucose | C15H18O9 | 342.300 | 341 | 179, 161, 143, 149, 131, 135 | 290, 304sh, 328 | MS | ✓ | ✓ | |||
21 | Hydroxycinnamic acid | Ferulic acid pentose | NA | NA | 325 | 149, 178, 193 | 326, 275 | MS | ✓ | ✓ | |||
22 | Hydroxycinnamic acid | Caftaric acid isomer | C13H11O9 | 311.224 | 311 | 179, 135, 149 | 325, 286 | MS | ✓ | ||||
24 | Hydroxycinnamic acid | Caftaric acid | C13H12O9 | 312.230 | 311 | 179, 135, 149, 267, 161, 237 | 326, 298sh, 243 | MS, NMR, DAD | ✓ | ✓ | ✓ | ||
27 | Hydroxycinnamic acid | Coutaric acid | C13H12O8 | 296.231 | 295 | 163, 149, 119 | 316, 234, 300sh | MS, DAD | ✓ | ✓ | |||
28 | Hydroxycinnamic acid | Chlorogenic acid | C16H18O9 | 354.311 | 353 | 191, 179, 135, 161, 335, 172, 284 | 328, 244, 303sh | MS, DAD | ✓ | ||||
31 | Hydroxycinnamic acid | Chicoric acid | C22H18O12 | 474.374 | 473 | 311, 293, 179, 149, 135, 219 | 328, 305sh, 279 | MS | ✓ | ||||
32 | Hydroxycinnamic acid | Fertaric acid | C14H14O9 | 326.259 | 325 | 193, 175, 149, 281, 134 | 314, 279 | MS | ✓ | ||||
35 | Hydroxycinnamic acid | Caffeic acid | C9H8O4 | 180.159 | 179 | 135, 134, 96 | 324, 299sh, 240 | MS, NMR, DAD | ✓ | ✓ | ✓ | ||
43 | Hydroxycinnamic acid | p-Coumaric acid | C9H8O3 | 164.160 | 163 | 119, 104, 93 | 310, 225, 211, 310sh | MS, NMR, DAD | ✓ | ✓ | ✓ | ||
46 | Hydroxycinnamic acid | Ferulic acid | C10H10O4 | 194.186 | 193 | 134, 149, 178, 116 | 323, 289, 238sh | MS, NMR, DAD | ✓ | ✓ | ✓ | ||
48 | Hydroxycinnamic acid | Sinapic acid | C11H12O5 | 224.212 | 223 | 164, 149, 208, 164, 193, 179 | 318, 238 | MS | ✓ | ✓ | |||
83 | Hydroxycinnamic acid | Cinnamic acid | C9H8O2 | 148.161 | 147 | 103, 77, 87, 129 | 276, 215, 203 | DAD | ✓ | ||||
3 | Flavan-3-ol | Gallocatechin | C15H14O7 | 306.270 | 305 | 179, 221, 219, 165, 261, 125, 137 | 274, 370 | MS | ✓ | ||||
6 | Flavan-3-ol | Procyanidin B1 | C30H26O12 | 578.526 | 577 | 425, 407, 289, 451, 287, 245, 451 | 275, 322 | MS, NMR, DAD | ✓ | ✓ | ✓ | ||
10 | Flavan-3-ol | Procyanidin A1 | C30H24O12 | 576.501 | 575 | 449, 289, 423, 539, 477, 407, 441 | 280 | MS | ✓ | ✓ | ✓ | ||
15 | Flavan-3-ol | Epigallocatechin | C15H14O7 | 306.270 | 305 | 179, 165, 219, 221, 261, 125, 261, 125 | 274, 212, 235 | MS | ✓ | ||||
18 | Flavan-3-ol | Procyanidin C1 | C45H38O18 | 866.778 | 865 | 695, 407, 577, 287, 713, 739, 575, 425, 289 | 279 | MS, DAD | ✓ | ✓ | |||
19 | Flavan-3-ol | Procyanidin T2 | C45H38O18 | 866.778 | 865 | 577, 713, 289, 287, 425, 575, 695, 407, 739 | 280 | MS, DAD | ✓ | ✓ | |||
23 | Flavan-3-ol | Catechin | C15H14O6 | 290.271 | 289 | 245, 203, 179, 205, 227, 109, 123, 165, 125, 151 | 275, 222 | MS, NMR, DAD | ✓ | ✓ | ✓ | ||
25 | Flavan-3-ol | Procyanidin B3 | C30H26O12 | 578.526 | 577 | 425, 407, 289, 151, 559, 445 | 270, 330 | MS, NMR, DAD | ✓ | ✓ | |||
26 | Flavan-3-ol | Procyanidin B4 | C30H26O12 | 578.526 | 577 | 425, 407, 289 | 280, 240 | MS, DAD | ✓ | ✓ | |||
29 | Flavan-3-ol | Procyanidin B2 | C30H26O12 | 578.526 | 577 | 425, 407, 289, 451, 287, 245, 125 | 280, 240, 370 | MS, NMR, DAD | ✓ | ✓ | ✓ | ||
37 | Flavan-3-ol | Epigallocatechin gallate | C22H18O11 | 458.375 | 457 | 305, 219, 261, 221, 359, 169, 305, 289, 271, 125, 331 | 274, 238 | MS, DAD | ✓ | ||||
38 | Flavan-3-ol | Prodelphinidin A-type | C30H26O13 | 594.527 | 593 | 425, 441, 573, 423, 407, 289, 531, 273, 339, 245, 177, 161 | 276, 228, 320 | MS | ✓ | ✓ | |||
39 | Flavan-3-ol | Procyanidin dimer gallate | NA | NA | 729 | 577, 407, 559, 451, 711, 289, 593, 437, 425 | 280 | MS, DAD | ✓ | ✓ | |||
40 | Flavan-3-ol | Epicatechin | C15H14O6 | 290.271 | 289 | 245, 203, 109, 179, 205, 123, 125, 151 | 277, 226 | MS, NMR, DAD | ✓ | ✓ | ✓ | ||
42 | Flavan-3-ol | Gallocatechin gallate | C22H18O11 | 458.375 | 457 | 169, 161, 359, 331, 169, 305, 193 | 276, 240 | MS | ✓ | ||||
47 | Flavan-3-ol | Epicatechin gallate | C22H18O10 | 442.376 | 441 | 289, 245, 205, 169, 125, 331, 271, 179 | 278, 240 | MS, NMR, DAD | ✓ | ✓ | |||
61 | Flavan-3-ol | Catechin gallate | C22H18O10 | 442.376 | 441 | 289, 245, 205, 331, 169, 125, 425, 271, 395, 169, 193, 405 | 278 | MS | ✓ | ✓ | |||
33 | Anthocyanin | Delphinidin-3-O-glucoside | C21H21O12+ | 465.387 | 463 | 301, 300, 271, 125 | 526, 361, 277, 402sh | DAD | ✓ | ||||
34 | Anthocyanin | Cyanidin-3-O-glucoside | C21H21O11+ | 449.388 | 447 | 284, 211, 285, 255, 147, 227 | 516, 262, 301sh | MS, DAD | ✓ | ||||
44 | Anthocyanin | Petunidin-3-O-glucoside | C22H23O12+ | 479.414 | 477 | 314, 315, 299, 300 | 526, 344sh, 277 | DAD | ✓ | ||||
45 | Anthocyanin | Peonidin-3-O-glucoside | C22H23O11+ | 463.415 | 461 | 299, 298, 284, 255, 227, 211 | 517, 280, 330sh, 421sh | MS, DAD | ✓ | ||||
52 | Anthocyanin | Malvidin-3-O-glucoside | C23H25O12+ | 493.441 | 491 | 329, 314, 299 | 528, 348sh, 288 | MS, DAD | ✓ | ✓ | |||
59 | Anthocyanin | Petunidin-3-(6-O-acetyl)glucoside | C24H25O13+ | 521.451 | 519 | 315, 302, 274, 149 | 528, 270, 350sh | DAD | ✓ | ||||
62 | Anthocyanin | Peonidin-3-(6-O-acetyl)glucoside | C24H25O12+ | 505.452 | 504 | 301 , 286, 230, 258, 268 | 522, 280 | DAD | ✓ | ||||
67 | Anthocyanin | Malvidin-3-(6-O-acetyl)glucoside | C25H27O13+ | 535.478 | 533 | 329, 315 | 522, 344, 278 | DAD | ✓ | ||||
72 | Anthocyanin | Cyanidin-3-(6-O-coumaroyl)glucoside | C30H27O13+ | 595.533 | 593 | 287 , 259, 231, 213, 259 | 524, 314, 284, 449sh | DAD | ✓ | ||||
80 | Anthocyanin | Petunidin-3-(6-O-coumaroyl)glucoside | C31H29O14+ | 625.553 | 624 | 317 , 302, 274, 218, 228, 246 | 534, 282, 313 | DAD | ✓ | ||||
81 | Anthocyanin | Peonidin-3-(6-O-coumaroyl)glucoside | C31H29O13+ | 609.554 | 608 | 301 , 286, 230, 258, 268 | 522, 312 | MS, DAD | ✓ | ||||
85 | Anthocyanin | Malvidin-3-(6-O-coumaroyl)glucoside | C32H31O14+ | 639.586 | 637 | 329, 299, 281 | 534, 318 | DAD | ✓ | ||||
86 | Anthocyanin | Malvidin-3-(6-O-caffeoyl)glucoside | C32H31O15+ | 655.581 | 655 | 331, 299, 637, 315, 475 | 532, 324, 284 | MS | ✓ | ||||
87 | Anthocyanin | Malvidin-3-O-rutinoside | C29H35O16+ | 639.583 | 637 | 331 | 526, 288 | MS | ✓ | ||||
41 | Flavanone | Taxifolin | C15H12O7 | 304.254 | 303 | 285, 125, 177, 275, 151, 259, 217 | 290, 326sh | MS | ✓ | ||||
55 | Flavanone | Taxifolin-O-pentoside | C20H20O11 | 436.371 | 435 | 303, 285, 399, 151, 241, 217, 175 | 274, 317 | MS | ✓ | ||||
56 | Flavanone | Taxifolin-3-O-glucoside | C21H22O12 | 466.395 | 465 | 285, 303, 151, 339, 177, 259, 447 | 290 | MS | ✓ | ||||
57 | Flavanone | Taxifolin-3-O-rhamnoside | C21H22O11 | 450.396 | 449 | 303, 285, 151, 323, 431 | 292, 235 | MS | ✓ | ||||
88 | Flavanone | Hesperetin | C16H14O6 | 302.282 | 301 | 258, 143, 157, 137, 286 | 284, 324sh, 221 | MS | ✓ | ||||
95 | Flavanone | Eriodictyol-7-O-glucoside | C21H22O11 | 450.396 | 449 | 287, 269, 151, 135, 259, 225, 209, 431 | 281, 327 | MS | ✓ | ||||
103 | Flavanone | Naringenin | C15H12O5 | 272.256 | 271 | 151, 177, 119, 165, 125, 107, 227, 191 | 289, 228, 336sh | MS | ✓ | ||||
104 | Flavanone | Naringenin-7-O-glucoside | C21H22O10 | 434.397 | 433 | 271, 269, 313, 177, 151, 119, 107 | 282, 222 | MS | ✓ | ||||
49 | Flavonol | Myricetin-3-O-galactoside | C21H20O13 | 480.378 | 479 | 317, 316, 178, 271 | 360, 265 | MS, DAD | ✓ | ||||
51 | Flavonol | Myricetin-3-O-glucuronide | C21H18O14 | 494.361 | 493 | 317 | 353, 300sh, 261 | MS, DAD | ✓ | ||||
53 | Flavonol | Myricetin-3-O-glucoside | C21H20O13 | 480.378 | 479 | 317, 316, 169, 271, 303, 227, 179, 151 | 362, 298sh, 260 | MS, DAD | ✓ | ||||
54 | Flavonol | Quercetin-3-O-rutinoside | C27H30O16 | 610.521 | 609 | 301, 300, 271, 255, 179, 343, 151 | 353, 256, 294sh | MS, NMR, DAD | ✓ | ✓ | |||
58 | Flavonol | Quercetin-3-O-galactoside | C21H20O12 | 464.379 | 463 | 301, 300, 179, 273, 257, 151 | 362, 256, 301sh | MS, NMR, DAD | ✓ | ✓ | ✓ | ||
60 | Flavonol | Quercetin-3-O-glucoside | C21H20O12 | 464.379 | 463 | 301, 300, 271, 161, 179, 255, 151 | 358, 256, 300sh | MS, NMR, DAD | ✓ | ✓ | |||
63 | Flavonol | Quercetin-3-O-glucuronide | C21H18O13 | 478.362 | 477 | 301, 179, 151, 283, 459, 431, 501 | 356, 254, 300sh | MS, NMR, DAD | ✓ | ✓ | |||
65 | Flavonol | Myricetin-3-O-rhamnoside | C21H20O12 | 464.379 | 463 | 317, 316, 271, 300, 179, 287, 151 | 372, 302sh, 248 | MS | ✓ | ||||
68 | Flavonol | Myricetin | C15H10O8 | 318.237 | 317 | 151, 179, 137, 287, 271, 109, 192 | 372, 253, 303sh, 207 | MS, NMR, DAD | ✓ | ||||
69 | Flavonol | Quercetin-3-O-rhamnoside | C21H20O11 | 448.380 | 447 | 301, 300, 179, 151, 271, 257 | 354, 258, 307sh | MS, NMR, DAD | ✓ | ✓ | |||
70 | Flavonol | Kaempferol-3-O-galactoside | C21H20O11 | 448.380 | 447 | 285, 255, 227, 327 | 361, 260 | MS | ✓ | ||||
71 | Flavonol | Kaempferol-3-O-rutinoside | C27H30O15 | 594.522 | 593 | 285, 257, 151, 447, 199, 241, 93 | 354, 274 | MS, DAD | ✓ | ✓ | |||
73 | Flavonol | Kaempferol-3-O-glucuronide | C21H18O12 | 462.363 | 461 | 285, 267, 443, 417, 257, 229 | 348, 265 | MS, DAD | ✓ | ||||
74 | Flavonol | Quercetin-3-(6-O-acetyl)glucoside | C23H22O13 | 506.416 | 505 | 301, 300, 463, 271, 255 | 354, 256, 267sh, 298sh | MS | ✓ | ||||
75 | Flavonol | Quercetin-3-(3-O-arabinosyl)glucoside | C26H28O16 | 596.493 | 595 | 301, 517, 151, 300, 463, 179, 445, 271, 255 | 354, 260, 231 | MS | ✓ | ||||
76 | Flavonol | Quercetin-3-(7-O-glucosyl)glucuronide | C27H28O18 | 640.503 | 639 | 477, 301, 179, 151 | 361, 300, 268, 256 | DAD | ✓ | ||||
77 | Flavonol | Quercetin-3-O-arabinose | C20H18O11 | 434.350 | 433 | 301, 179, 151, 300, 283 | 358, 311 | MS | ✓ | ✓ | |||
78 | Flavonol | C33H40O21 | 772.662 | 771 | 609, 301 | 355, 259, 299sh, 204 | NMR, DAD | ✓ | |||||
79 | Flavonol | Kaempferol-3-O-glucoside | C21H20O11 | 448.380 | 447 | 285, 255, 151, 227, 327, 243 | 348, 263, 297sh | MS, DAD | ✓ | ✓ | |||
82 | Flavonol | Quercetin | C15H10O7 | 302.239 | 301 | 151, 179, 273, 193, 257, 229 | 372, 255, 202sh, 300sh | MS, NMR, DAD | ✓ | ✓ | |||
84 | Flavonol | Kaempferol | C15H10O6 | 286.239 | 285 | 187, 117, 211, 127, 257, 151, 169, 241 | 369, 258, 390 | MS, NMR, DAD | ✓ | ✓ | |||
89 | Flavonol | Kaempferol-3-O-xyloside | C20H18O10 | 418.354 | 417 | 285, 255, 227 | 350 | MS | ✓ | ||||
90 | Flavonol | Kaempferol-3-O-rhamnoside | C21H20O10 | 432.381 | 431 | 285 | 351, 264, 202, 294sh | MS | ✓ | ||||
91 | Flavonol | Dihydrokaempferol-3-O-rhamnoside | C21H22O10 | 434.397 | 433 | 269, 287, 259, 180, 151, 368 | 286, 230 | MS | ✓ | ||||
92 | Flavonol | Isorhamnetin-3-O-galactoside | C22H22O12 | 478.406 | 477 | 315,.314 271, 300, 357 | 366, 289, 259 | MS | ✓ | ||||
93 | Flavonol | Isorhamnetin-3-O-glucoside | C22H22O12 | 478.406 | 477 | 315, 314, 285, 357, 271 | 354, 265sh | MS, DAD | ✓ | ||||
94 | Flavonol | Quercetin-3-(6-O-rhamnosyl)galactoside | C27H30O16 | 610.517 | 609 | 301, 541, 463, 300, 271, 255, 179, 447, 151 | 356, 256, 300 | NMR, DAD | ✓ | ||||
96 | Flavonol | Isorhamnetin-3-O-arabinose | C21H20O11 | 448.381 | 447 | 315, 314, 271, 243 | 345, 258 | MS | ✓ | ||||
97 | Flavonol | Isorhamnetin-3-O-glucuronide | C22H20O13 | 492.389 | 491 | 315, 255, 151 | 355, 265sh | MS | ✓ | ||||
98 | Flavonol | Isorhamnetin-3-O-rutinoside | C28H32O16 | 624.548 | 623 | 315, 300, 468 | 354, 256 | MS | ✓ | ||||
99 | Flavonol | Isorhamnetin-3-(6-O-feruloyl)glucoside | C32H30O15 | 654.577 | 653 | 315 | 320, 274 | MS | ✓ | ||||
100 | Flavonol | Isorhamnetin-3-(4-O-rhamnosyl)rutinoside | C34H42O20 | 770.685 | 769 | 461, 623, 163 | 354, 256 | MS, DAD | ✓ | ||||
101 | Flavonol | Kaempferol-3-(6-O-coumaroyl)glucoside | C30H26O13 | 594.525 | 593 | 285, 227, 255 | 317, 265, 356sh, 310sh | MS | ✓ | ||||
102 | Flavonol | Kaempferol-3 (7-O-glucosyl)galactoside | C27H30O16 | 610.521 | 609 | 447, 489, 285 | 343, 300sh, 265 | DAD | ✓ | ||||
105 | Flavonol | Diquercetin-3-(3-O-glucosyl)glucuronide | C42H36O24 | 924.722 | 923 | 765, 755, 837, 903, 935, 808 | 374 | MS | ✓ | ||||
64 | Flavone | Apigenin-7-O-glucoside | C21H20O10 | 432.381 | 431 | 269, 283, 311, 413, 231, 225, 201, 197, 149 | 335, 269, 253 | MS, NMR, DAD | ✓ | ||||
66 | Flavone | Luteolin-7-O-glucoside | C21H20O11 | 448.380 | 447 | 285, 226, 257, 217, 241, 198 | 349, 254sh, 205 | MS, NMR, DAD | ✓ | ||||
5 | Coumarin | Aesculin | C15H16O9 | 340.282 | 339 | 133, 177, 150 | 346, 289 | MS | ✓ | ||||
11 | Dihydrochalcone | Phlorizin | C21H24O10 | 436.413 | 435 | 273, 167, 229, 297 | 285, 230sh | MS | ✓ | ||||
12 | Coumarin | Fraxin | C16H18O10 | 370.310 | 369 | 207, 192, 354, 149, 123 | 332, 308sh | MS | ✓ | ||||
13 | Coumarin | Aesculetin | C9H6O4 | 178.143 | 177 | 149, 133, 105, 91, 115, 89, 65 | 334, 288sh | MS | ✓ | ||||
17 | Coumarin | Umbelliferone | C9H6O3 | 162.144 | 161 | 133, 117, 105, 51, 78 | 323, 236 | MS | ✓ |
1 Other reported names are found in Table S1, where compounds are numbered (ID) according to their elution patterns. 2 NA = not available or not applicable, MW = Molecular Weight. 3 MS-MS values in italic (compounds 62, 72, 80, 81) are reported in positive mode. 4 The most abundant fragments are highlighted in bold. 5 MS = mass spectrometry detection, NMR = nuclear magnetic resonance detection, DAD = diode array or ultraviolet detection. 6 In blue with √ are detected compounds; in light red are undetected compounds or unavailable information.