Table 2.
High resolution MS data and negative ion MS2, MS3, and MS4 fragmentation of phenolic compounds identified in Vranac wine (W), grape (seed (S), pulp (P), and skin (E)) and leaf (L) extracts.
| No | tR, min | Compound Name | Molecular Formula, [M–H]– | Calculated Mass, [M–H]– | Exact Mass, [M–H]– | Δ ppm | MS2 Fragments, (% Base Peak) | MS3 Fragments, (% Base Peak) | MS4 Fragments, (% Base Peak) | W | S | P | E | L |
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| Phenolic Acids and Their Derivatives | ||||||||||||||
| 1 | 2.89 | Dihydroxybenzoic acid hexoside isomer 1 | C13H15O9– | 315.07216 | 315.07135 | 2.57 | 153 (100), 152 (50), 109 (15), 108 (10) | 109 (100) | 123 (25), 109 (10), 85 (10), 81 (100) | – | + | + | + | – |
| 2 | 3.01 | Gallic acid a | C7H5O5– | 169.01425 | 169.01369 | 3.31 | 125 (100) | 107 (100) | – | − | + | – | – | + |
| 3 | 3.86 | Protocatechuic acid a | C7H5O4– | 153.01933 | 153.01906 | 1.76 | 109 (100), 95 (75), 79 (20), 59 (10) | 81 (100), 68 (25), 65 (15) | – | + | + | + | + | + |
| 4 | 4.20 | Caffeoyltartaric acid | C13H11O9– | 311.04031 | 311.04001 | 0.97 | 179 (40), 177 (15), 149 (100) | 131 (50), 103 (90), 87 (100), 59 (25) | 59 (100) | + | + | + | + | + |
| 5 | 4.60 | Gallic acid hexoside | C13H15O10– | 331.06707 | 331.06638 | 2.08 | 169 (100), 125 (5) | 125 (100) | 110 (10), 97 (30), 81 (100), 53 (30) | + | + | + | – | + |
| 6 | 4.62 | Hydroxybenzoic acid hexoside isomer 1 | C13H15O8– | 299.07724 | 299.07648 | 2.54 | 137 (100) | 93 (100) | – | + | + | + | + | + |
| 7 | 4.72 | Chlorogenic acid hexoside | C22H27O14– | 515.14008 | 515.13917 | 1.77 | 353 (40), 341 (100), 335 (25), 191 (15), 179 (45) | 179 (100), 135 (10) | 135 (100) | – | – | – | – | + |
| 8 | 4.81 | Caffeic acid hexoside | C15H17O9– | 341.08781 | 341.08659 | 3.58 | 191 (10), 179 (100), 135 (10) | 135 (100) | 135 (100), 107 (50) | + | – | – | – | + |
| 9 | 4.84 | Dihydroxybenzoic acid hexosyl pentoside isomer 1 | C18H23O13– | 447.11441 | 447.11353 | 1.97 | 315 (100), 285 (10), 153 (10) | 153 (100), 123 (10) | 123 (100) | – | – | – | – | + |
| 10 | 4.90 | Chlorogenic acid a | C16H17O9– | 353.08781 | 353.08633 | 4.19 | 191 (100), 179 (30), 135 (10) | 173 (75), 127 (100), 111 (40), 93 (60), 85 (90) | 109 (30), 99 (40), 85 (100) | + | + | – | – | + |
| 11 | 4.95 | Coumaroyltartaric acid isomer 1 | C13H11O8– | 295.04594 | 295.04532 | 2.10 | 163 (100), 149 (10), 119 (5) | 119 (100) | 119 (100), 93 (50) | + | + | + | + | + |
| 12 | 4.96 | Gallic acid methyl ester | C8H7O5– | 183.02990 | 183.02931 | 3.22 | 168 (100), 124 (15) | 124 (100) | 95 (100) | + | − | − | − | − |
| 13 | 5.01 | Hydroxybenzoic acid hexoside isomer 2 | C13H15O8– | 299.07724 | 299.07593 | 4.38 | 137 (100) | 93 (100) | – | + | – | – | – | + |
| 14 | 5.04 | Dihydroxybenzoic acid hexosyl pentoside isomer 2 | C18H23O13– | 447.11441 | 447.11356 | 1.90 | 315 (100), 285 (60), 153 (50), 149 (25) | 153 (100), 123 (10) | 123 (100), 109 (5) | – | – | – | – | + |
| 15 | 5.26 | p-Hydroxybenzoic acid a | C7H5O3– | 137.02442 | 137.02385 | 4.16 | 109 (10), 93 (100) | 93 (100) | – | + | + | + | – | + |
| 16 | 5.32 | Coumaric acid hexoside isomer 1 | C15H17O8– | 325.09289 | 325.09167 | 3.75 | 163 (100), 119 (10) | 119 (100) | – | + | – | – | + | + |
| 17 | 5.36 | Coumaroyltartaric acid isomer 2 | C13H11O8– | 295.04594 | 295.04501 | 3.15 | 163 (30), 149 (100), 119 (5) | 131 (50), 103 (90), 87 (100), 59 (30) | – | + | – | – | – | + |
| 18 | 5.44 | Dihydroxybenzoic acid hexoside isomer 2 | C13H15O9– | 315.07216 | 315.07123 | 2.95 | 153 (100), 135 (10), 109 (10) | 135 (100), 109 (50) | 91 (100) | + | – | – | – | – |
| 19 | 5.47 | 3-O-p-Coumaroylquinic acid | C16H17O8– | 337.09289 | 337.09171 | 3.50 | 191 (10), 173 (10), 163 (100), 119 (10) | 119 (100) | – | + | – | – | – | + |
| 20 | 5.51 | Coumaric acid hexoside isomer 2 | C15H17O8– | 325.09289 | 325.09164 | 3.85 | 289 (20), 265 (20), 187 (40), 163 (80), 145 (100) | 117 (100) | – | + | – | – | + | + |
| 21 | 5.62 | Feruloyltartaric acid | C14H13O9– | 325.05651 | 325.05518 | 4.09 | 193 (100), 113 (5) | 178 (65), 149 (100), 134 (40) | 134 (100) | + | – | – | – | + |
| 22 | 5.66 | Ferulic acid pentoside | C15H17O8– | 325.09289 | 325.09135 | 4.74 | 193 (100) | 178 (60), 149 (100), 134 (30) | 134 (100) | + | – | – | – | – |
| 23 | 5.66 | Ferulic acid hexoside | C16H19O9– | 355.10346 | 355.10199 | 4.14 | 217 (60), 193 (100), 175 (40), 134 (10) | 178 (20), 149 (40), 134 (100) | 134 (50), 106 (100) | + | – | – | – | + |
| 24 | 5.67 | p-Hydroxyphenylacetic acid a | C8H7O3– | 151.04007 | 151.03996 | 0.73 | 136 (100), 95 (5) | 108 (25), 92 (100) | 108 (100) | + | – | – | – | − |
| 25 | 5.67 | Ellagic acid hexoside | C20H15O13– | 463.05181 | 463.05078 | 2.22 | 302 (15), 301 (100), 300 (50), 289 (10), 273 (10) | 301 (70), 284 (20), 257 (100), 229 (65), 185 (30) | 229 (50), 213 (30), 185 (100) | – | + | – | – | + |
| 26 | 5.82 | Caffeoylthreonic acid | C13H13O8– | 297.06159 | 297.06030 | 4.34 | 179 (15), 135 (100) | 117 (100), 89 (90), 75 (80) | 89 (100) | + | – | – | – | + |
| 27 | 5.84 | Caffeic acid a | C9H7O4− | 179.03498 | 179.03436 | 3.46 | 135 (100), 117 (10), 91 (20), 59 (15) | 107 (100), 59 (50) | – | + | + | – | + | + |
| 28 | 5.89 | Vanillic acid a | C8H7O4– | 167.03498 | 167.03433 | 3.89 | 153 (10), 152 (80), 124 (10), 123 (100), 108 (20) | 108 (100) | 79 (100) | + | + | + | + | + |
| 29 | 5.99 | Caffeoylshikimic acid | C16H15O8– | 335.07724 | 335.07654 | 2.09 | 179 (100), 135 (25) | 135 (100) | 107 (100) | + | + | – | – | + |
| 30 | 6.11 | Ellagic acid pentoside | C19H13O12– | 433.04125 | 433.04080 | 1.04 | 301 (100), 300 (80) | 301 (95), 284 (25), 257 (100), 229 (70), 185 (40) | 229 (70), 213 (30), 201 (15), 185 (100) | – | – | – | – | + |
| 31 | 6.20 | Syringic acid a | C9H9O5− | 197.04555 | 197.04474 | 4.11 | 183 (100), 153 (40), 138 (10) | 167 (100), 138 (10), 123 (5) | – | + | – | + | + | + |
| 32 | 6.25 | Coumaric acid hexoside isomer 3 | C15H17O8– | 325.09289 | 325.09180 | 3.35 | 289 (10), 163 (100), 161 (50), 119 (60), 101 (20) | 91 (100) | – | + | – | – | – | – |
| 33 | 6.50 | p-Coumaric acid a | C9H7O3– | 163.04007 | 163.03951 | 3.43 | 119 (100) | 119 (60), 101 (20), 93 (25), 91 (100), 72 (10) | – | + | + | – | + | + |
| 34 | 6.58 | Gallic acid ethyl ester | C9H9O5– | 197.04555 | 197.04480 | 3.81 | 169 (100) | 125 (100) | 107 (10), 97 (40), 81 (100) | + | + | − | − | − |
| 35 | 6.75 | Ellagic acid a | C14H5O8– | 300.99899 | 300.99805 | 3.12 | 284 (40), 271 (60), 257 (100), 229 (85), 185 (40) | 229 (100), 213 (20), 185 (85) | 201 (100), 185 (95), 157 (30), 145 (20), 129 (10) | + | + | – | – | + |
| 36 | 6.76 | Sinapic acid a | C11H11O5− | 223.06120 | 223.06047 | 3.27 | 208 (100), 179 (30), 164 (20) | 193 (10), 164 (100), 149 (15), 135 (5) | 149 (100), 135 (35) | − | + | – | – | − |
| 37 | 7.05 | Ferulic acid a | C10H9O4– | 193.05063 | 193.04995 | 3.52 | 178 (70), 149 (100), 134 (50) | 134 (100) | 106 (100) | + | + | – | – | + |
| 38 | 7.67 | Caffeoylcoumaroylquinic acid | C25H23O11– | 499.12404 | 499.12375 | 0.58 | 361 (5), 337 (100), 163 (10) | 191 (10), 173 (60), 163 (100), 119 (10) | 119 (100) | – | + | – | – | – |
| 39 | 8.01 | Dihydroxybenzoic acid ethyl ester | C9H9O4– | 181.05063 | 181.05011 | 2.87 | 153 (100), 109 (10) | 109 (100) | – | + | − | − | + | − |
| 40 | 8.02 | Caffeic acid methyl ester | C10H9O4– | 193.05063 | 193.05019 | 2.28 | 178 (30), 161 (100), 134 (70), 111 (10) | 133 (100) | – | + | − | − | − | + |
| 41 | 8.96 | Cinnamic acid a | C9H7O2− | 147.04515 | 147.04480 | 2.38 | 104 (10), 103 (100), 87 (10) | 119 (100) | – | – | + | – | – | + |
| 42 | 9.12 | p-Coumaric acid methyl ester | C10H9O3– | 177.05572 | 177.05504 | 3.84 | 177 (10), 162 (40), 145 (100), 118 (50) | 177 (100) | – | + | − | − | + | + |
| Flavan-3-ols | ||||||||||||||
| 43 | 4.14 | (Epi)catechin hexoside isomer 1 | C21H23O11- | 451.12404 | 451.12378 | 0.58 | 289 (100), 161 (5) | 245 (100), 205 (40), 179 (15) | 227 (30), 203 (100), 187 (30), 175 (10), 161 (20) | – | + | – | – | – |
| 44 | 4.41 | Prodelphinidin dimer B type | C30H25O13– | 593.13006 | 593.12958 | 0.81 | 467 (15), 425 (100), 407 (30), 289 (20) | 407 (100), 381 (5), 273 (10) | 389 (30), 297 (30), 285 (100), 243 (70) | + | + | – | – | – |
| 45 | 4.70 | Procyanidin dimer A type isomer 1 | C30H23O12– | 575.11950 | 575.11857 | 1.62 | 449 (80), 423 (70), 407 (100), 289 (15), 287 (35), 285 (25) | 389 (20), 297 (30), 285 (100), 243 (30) | 257 (100), 213 (10) | + | + | – | – | – |
| 46 | 4.81 | (Epi)catechin hexoside isomer 2 | C21H23O11- | 451.12404 | 451.12387 | 0.38 | 289 (100), 161 (5) | 245 (100), 205 (40), 179 (15) | 227 (30), 203 (100), 187 (30), 175 (10), 161 (20) | – | + | – | – | – |
| 47 | 4.83 | Gallocatechin a | C15H13O7− | 305.06668 | 305.06592 | 2.49 | 261 (50), 221 (70), 219 (70), 179 (100), 165 (35) | 164 (100), 151 (40), 135 (30) | 120 (100), 108 (20) | + | + | – | – | – |
| 48 | 4.85 | Procyanidin dimer B type isomer 1 | C30H25O12– | 577.13515 | 577.13391 | 2.15 | 559 (10), 451 (30), 425 (100), 407 (50), 289 (25), 287 (10) | 407 (100), 381 (5), 273 (10) | 389 (30), 297 (30), 285 (100), 243 (70) | + | + | + | + | – |
| 49 | 4.94 | Procyanidin dimer A type isomer 2 | C30H23O12– | 575.11950 | 575.11850 | 1.74 | 449 (70), 423 (100), 407 (60), 289 (10), 287 (20), 285 (5) | 405 (100), 313 (35), 297 (45), 285 (25), 243 (30) | 387 (10), 283 (10), 243 (100) | + | + | – | – | – |
| 50 | 5.01 | Procyanidin trimer B type isomer 1 | C45H37O18- | 865.19854 | 865.19684 | 1.96 | 695 (100), 577 (60), 425 (30), 407 (30), 287 (30) | 543 (100), 451 (45), 243 (60) | 525 (100), 391 (40) | + | + | – | – | – |
| 51 | 5.07 | Chalcan-flavan 3-ol dimer isomer 1 | C30H27O12– | 579.15079 | 579.14984 | 1.64 | 289 (100), 245 (10) | 245 (100), 205 (30), 179 (15) | 227 (30), 203 (100), 187 (30), 175 (10), 161 (20) | + | + | – | – | – |
| 52 | 5.13 | Procyanidin dimer B type isomer 2 | C30H25O12- | 577.13515 | 577.13403 | 1.94 | 559 (10), 451 (30), 425 (100), 407 (50), 289 (25), 287 (10) | 407 (100), 381 (5), 273 (10) | 389 (30), 297 (30), 285 (100), 243 (70) | + | + | + | – | – |
| 53 | 5.25 | Procyanidin dimer A type isomer 3 | C30H23O12– | 575.11950 | 575.11830 | 2.09 | 449 (50), 423 (100), 407 (30), 289 (5), 287 (20), 285 (10) | 405 (100), 313 (50), 297 (30), 285 (45), 243 (40) | 387 (20), 361 (20), 243 (100) | + | + | – | – | – |
| 54 | 5.26 | Catechin a | C15H13O6– | 289.07176 | 289.07080 | 3.32 | 271 (5), 245 (100), 205 (40), 179 (15), 125 (5) | 227 (30), 203 (100), 187 (25), 175 (10), 161 (20) | 188 (70), 185 (20), 175 (100), 161 (40), 157 (10) | + | + | + | + | + |
| 55 | 5.31 | Procyanidin dimer B type isomer 3 | C30H25O12- | 577.13515 | 577.13397 | 2.04 | 425 (25), 407 (10), 329 (10), 289 (100), 287 (80) | 245 (100), 205 (30), 179 (15) | 227 (30), 203 (100), 187 (30), 175 (10), 161 (20) | + | + | + | – | – |
| 56 | 5.36 | Epigallocatechin a | C15H13O7– | 305.06668 | 305.06552 | 3.80 | 261 (40), 247 (20), 221 (90), 219 (80), 179 (100) | 164 (100), 151 (35), 135 (30) | 120 (100), 108 (25) | + | + | – | + | – |
| 57 | 5.39 | Procyanidin trimer B type isomer 2 | C45H37O18- | 865.19854 | 865.19592 | 3.03 | 695 (100), 577 (80), 425 (30), 407 (40), 287 (35) | 543 (100), 451 (45), 243 (60) | 525 (100), 391 (40) | + | + | – | – | – |
| 58 | 5.59 | Chalcan-flavan 3-ol dimer isomer 2 | C30H27O12– | 579.15079 | 579.15002 | 1.33 | 289 (100), 245 (10) | 245 (100), 205 (30), 179 (15) | 227 (30), 203 (100), 187 (30), 175 (10), 161 (20) | + | + | – | – | – |
| 59 | 5.64 | Procyanidin trimer B type isomer 3 | C45H37O18- | 865.19854 | 865.19818 | 0.41 | 695 (100), 577 (70), 425 (30), 407 (40), 287 (30) | 543 (100), 451 (45), 243 (60) | 525 (100), 391 (40) | + | + | – | – | – |
| 60 | 5.91 | Epicatechin a | C15H13O6– | 289.07176 | 289.07085 | 3.15 | 271 (5), 245 (100), 205 (40), 179 (15), 125 (5) | 227 (35), 203 (100), 187 (30), 175 (15), 161 (25) | 188 (60), 185 (20), 175 (100), 161 (35), 157 (15) | + | + | + | + | + |
| 61 | 6.20 | Procyanidin trimer B type isomer 4 | C45H37O18- | 865.19854 | 865.19672 | 2.10 | 695 (100), 577 (80), 425 (35), 407 (35), 287 (30) | 543 (100), 451 (45), 243 (60) | 525 (100), 391 (40) | + | + | – | – | – |
| 62 | 6.50 | Catechin 3-O-gallate a | C22H17O10− | 441.08272 | 441.08209 | 1.43 | 331 (10), 289 (100), 271 (10), 169 (25) | 271 (5), 245 (100), 205 (40), 179 (20) | 227 (20), 203 (100), 187 (20), 175 (10), 161 (20) | – | + | – | – | – |
| 63 | 6.68 | (Epi)gallocatechin 3-O-gallate methyl ether | C23H19O11– | 471.09328 | 471.09219 | 2.31 | 439 (50), 287 (100), 269 (20), 169 (20) | 243 (15), 161 (20), 125 (100) | 57 (100) | – | + | + | – | – |
| 64 | 7.68 | (Epi)catechin 3-O-vanillate | C23H19O9– | 439.10346 | 439.10275 | 1.62 | 289 (100), 287 (90), 271 (50), 269 (30), 167 (10) | 245 (100), 205 (30), 179 (15) | 227 (30), 203 (100), 187 (30), 175 (10), 161 (20) | – | + | – | – | – |
| 65 | 8.12 | (Epi)catechin 3-O-coumarate | C24H19O8− | 435.10854 | 435.10828 | 0.60 | 341 (15), 289 (100), 269 (25), 165 (20) | 245 (100), 205 (30), 179 (15) | 227 (30), 203 (100), 187 (30), 175 (10), 161 (20) | – | + | – | – | – |
| Flavanols | ||||||||||||||
| 66 | 6.09 | Myricetin 7-O-pentoside | C20H17O12– | 449.07255 | 449.07162 | 2.07 | 317 (100) | 299 (10), 289 (60), 273 (100), 255 (40) | 255 (100), 211 (90) | – | – | – | + | + |
| 67 | 6.17 | Myricetin a | C15H9O8− | 317.03029 | 317.02942 | 2.74 | 299 (10), 273 (35), 207 (100), 163 (95) | 179 (100), 151 (15) | 151 (100) | – | – | – | + | + |
| 68 | 6.20 | Myricetin 3-O-hexoside | C21H19O13– | 479.08311 | 479.08176 | 2.82 | 317 (90), 316 (100) | 287 (30), 271 (100), 179 (20), 151 (10) | 271 (10), 243 (100), 227 (30), 215 (10), 199 (10) | + | – | – | + | + |
| 69 | 6.21 | Quercetin 3-O-hexuronide-7-O-hexoside | C27H27O18– | 639.12029 | 639.11902 | 1.99 | 505 (10), 477 (100), 463 (30), 301 (50) | 301 (100) | 273 (20), 257 (20), 179 (100), 151 (75) | + | – | – | – | + |
| 70 | 6.23 | Quercetin 3-O-(6”-rhamnosyl)hexoside a | C27H29O16– | 609.14611 | 609.14508 | 1.69 | 343 (5), 301 (100), 300 (30), 271 (10), 255 (5) | 273 (25), 257 (20), 179 (100), 151 (75) | 151 (100) | – | – | – | + | + |
| 71 | 6.38 | Myricetin 3-O-hexuronide-7-O-hexoside | C27H27O19– | 655.11520 | 655.11359 | 2.46 | 521 (20), 493 (100), 479 (30), 317 (50) | 317 (100) | 193 (10), 179 (100), 151 (30) | – | – | – | + | + |
| 72 | 6.60 | Myricetin 7-O-hexuronide | C21H17O14– | 493.06238 | 493.06100 | 2.80 | 359 (10), 317 (100) | 179 (100), 151 (40) | 151 (100) | – | – | – | + | + |
| 73 | 6.67 | Quercetin 3-O-galactoside a | C21H19O12– | 463.08820 | 463.08655 | 3.56 | 301 (100), 300 (30) | 273 (25), 257 (20), 179 (100), 151 (75) | 151 (100) | + | + | + | + | + |
| 74 | 6.81 | Kaempferol 7-O-(6”-rhamnosyl)hexoside | C27H29O15– | 593.15119 | 593.14905 | 3.61 | 285 (100) | 267 (40), 257 (100), 241 (30), 229 (40), 213 (30) | 255 (10), 239 (30), 229 (100), 163 (40) | – | – | – | – | + |
| 75 | 6.88 | Isorhamnetin 3-O-(6”-rhamnosyl)hexoside | C28H31O16– | 623.16176 | 623.15973 | 3.26 | 315 (100), 300 (20), 271 (10), 255 (5) | 300 (100), 287 (5), 272 (5) | 271 (100), 255 (50), 151 (5) | – | – | – | – | + |
| 76 | 6.99 | Kaempferol 3-O-glucoside a | C21H19O11– | 447.09329 | 447.09219 | 2.46 | 327 (20), 285 (80), 284 (100), 255 (10) | 255 (100), 227 (10) | 227 (100), 211 (60) | + | – | – | + | + |
| 77 | 6.99 | Syringetin 3-O-hexoside | C23H23O13– | 507.11441 | 507.11346 | 1.87 | 479 (10), 387 (20), 345 (80), 345 (60), 344 (100), 299 (15) | 330 (90), 316 (100), 301 (90), 287 (10), 273 (70) | 301 (100), 300 (20), 287 (10), 273 (60) | + | – | – | + | – |
| 78 | 7.01 | Isorhamnetin 3-O-hexoside | C22H21O12– | 477.10385 | 477.10275 | 2.31 | 357 (20), 315 (50), 314 (100), 300 (5), 299 (5) | 300 (30), 285 (100), 271 (75), 257 (10), 243 (25) | 270 (100) | – | + | + | + | – |
| 79 | 7.11 | Quercetin 3-O-hexuronide | C21H17O13– | 477.06692 | 477.06503 | 3.96 | 301 (100) | 273 (20), 257 (20), 179 (100), 151 (75) | 151 (100) | + | + | + | + | + |
| 80 | 7.24 | Quercetin 3-O-hexuronide methyl ether | C22H19O13– | 491.08311 | 491.08102 | 4.26 | 473 (10), 315 (50), 301 (100), 300 (60) | 283 (15), 272 (20), 256 (10), 179 (100), 151 (75) | 151 (100) | – | – | – | + | + |
| 81 | 7.36 | Quercetin 3-O-(6”-malonyl)hexoside | C24H21O15– | 549.08859 | 549.08710 | 2.71 | 505 (100) | 463 (30), 301 (100), 300 (50) | 273 (15), 257 (15), 179 (100), 151 (85) | – | – | – | – | + |
| 82 | 7.44 | Kaempferol 7-O-hexuronide | C21H17O12– | 461.07200 | 461.07101 | 2.15 | 285 (100) | 267 (40), 257 (100), 241 (30), 229 (50), 213 (25) | 255 (10), 239 (30), 229 (100), 163 (60) | + | – | – | + | + |
| 83 | 7.73 | Kaempferol 3-O-hexuronide methyl ether | C22H19O12− | 475.08820 | 475.08667 | 3.22 | 327 (10), 301 (10), 285 (70), 284 (100), 255 (35) | 255 (100), 227 (10) | 227 (100), 211 (60) | – | – | – | – | + |
| 84 | 7.84 | Kaempferol 7-O-(6”-malonyl)hexoside | C24H21O14– | 533.09368 | 533.09204 | 3.08 | 489 (100) | 285 (100) | 267 (50), 257 (100), 241 (40), 229 (60), 213 (30) | – | – | – | – | + |
| 85 | 8.60 | Quercetin a | C15H9O7− | 301.03537 | 301.03391 | 4.85 | 283 (15), 271 (60), 257 (25), 179 (100), 151 (80) | 151 (100) | 107 (100), 83 (10) | + | + | – | + | + |
| 86 | 9.49 | Kaempferol a | C15H9O6− | 285.04046 | 285.03958 | 3.09 | 255 (100), 227 (10) | 211 (100), 195 (5), 167 (15) | 211 (40), 137 (100) | + | – | – | – | + |
| Stilbenes | ||||||||||||||
| 87 | 7.11 | Resveratrol hexoside | C20H21O8− | 389.12419 | 389.12230 | 4.86 | 227 (100) | 185 (100), 183 (40), 159 (35), 157 (30), 143 (20) | − | + | + | – | – | + |
| 88 | 8.01 | Resveratrol a | C14H11O3− | 227.07137 | 227.07054 | 3.66 | 185 (100), 159 (30), 143 (20) | 157 (10), 143 (100), 117 (5) | 115 (100) | + | + | – | + | + |
| 89 | 8.50 | Resveratrol tetramer | C56H41O12− | 905.26035 | 905.25586 | 4.96 | 811 (100), 717 (50), 451 (15), 359 (15) | 717 (100), 357 (10) | 699 (50), 675 (100), 623 (30), 611 (60), 357 (80) | + | + | – | – | – |
| 90 | 8.97 | Resveratrol dimer | C28H21O6− | 453.13436 | 453.13229 | 4.57 | 435 (10), 369 (10), 359 (30), 347 (100), 333 (40) | 329 (10), 305 (20), 253 (100), 240 (30), 225 (10) | 225 (100), 209 (10) | + | + | – | – | – |
| 91 | 9.07 | Resveratrol trimer | C42H31O9− | 679.19736 | 679.19412 | 4.77 | 585 (100), 491 (10) | 491 (100), 479 (20), 385 (10) | 473 (40), 447 (30), 421 (20), 397 (25), 385 (100) | + | + | – | – | – |
a Confirmed using standards, the other compounds were identified according high resolution mass spectrometry (HRMS) and MSn; tR—retention time; Δ ppm—mean mass accuracy errors; + stands for detected and − stands for not detected compound.