Table 3.
High resolution mass spectrometry (MS) data and positive ion MS2, MS3, and MS4 fragmentation of anthocyanins identified in Vranac wine (W) and berry skin (E) extracts.
| No | tR, min | Anthocyanins | Molecular Formula, M+ (m/z) | Calculated Mass, M+ (m/z) | Exact Mass, M+ (m/z) | Δ ppm | MS2 Fragments, (% Base Peak) | MS3 Fragments, (% Base Peak) | MS4 Fragments, (% Base Peak) | W | E |
|---|---|---|---|---|---|---|---|---|---|---|---|
| Peonidin Derivatives | |||||||||||
| 1’ | 3.95 | Peonidin 3,5-di-O-hexoside | C28H33O16+ | 625.17631 | 625.17548 | 1.33 | 464 (20), 463 (100), 302 (10), 301 (60), 265 (5) | 301 (100) | 286 (100), 258 (5) | − | + |
| 2’ | 5.62 | Peonidin 3-O-hexoside isomer | C22H23O11+ | 463.12349 | 463.12288 | 1.32 | 302 (10), 301 (100) | 287 (10), 286 (100) | 268 (20), 258 (100), 230 (25), 202 (5) | + | + |
| 3’ | 5.15 | Peonidin 3-O-glucosidea | C22H23O11+ | 463.12349 | 463.12231 | 2.55 | 302 (10), 301 (100) | 287 (10), 286 (100) | 268 (20), 258 (100), 230 (25), 202 (5) | + | + |
| 4’ | 5.70 | Peonidin 3-O-hexoside-pyruvate | C25H25O13+ | 531.11332 | 531.11255 | 1.45 | 370 (15), 369 (100) | 354 (100), 326 (10) | 336 (25), 326 (100), 298 (30), 253 (30) | + | + |
| 5’ | 6.08 | Peonidin 3-O-(6”-acetyl)hexoside | C24H25O12+ | 505.13405 | 505.13358 | 0.93 | 302 (10), 301 (100) | 287 (10), 286 (100) | 268 (20), 258 (100), 230 (25), 202 (5) | + | + |
| 6’ | 6.48 | Peonidin 3-O-(6”-caffeloyl)hexoside | C31H29O14+ | 625.15518 | 625.15369 | 2.38 | 317 (10), 302 (15), 301 (100), 286 (10) | 287 (5), 286 (100) | 268 (20), 258 (100), 257 (20), 230 (30), 202 (10) | − | + |
| 7’ | 6.80 | Peonidin 3-O-(6”-p-coumaroyl)hexoside | C31H29O13+ | 609.16027 | 609.15796 | 3.79 | 302 (10), 301 (100) | 287 (10), 286 (100) | 268 (20), 258 (100), 230 (25), 202 (5) | + | + |
| Delphinidin Derivatives | |||||||||||
| 8’ | 4.50 | Delphinidin 3-O-glucosidea | C21H21O12+ | 465.10275 | 465.10123 | 3.27 | 304 (15), 303 (100) | 285 (10), 275 (10), 257 (100), 247 (15), 229 (30) | 239 (5), 229 (100), 213 (25), 201 (25), 173 (20) | + | + |
| 9’ | 4.85 | Delphinidin 3-O-hexoside-pyruvate | C24H21O14+ | 533.09258 | 533.09113 | 2.72 | 372 (10), 371 (100) | 371 (30), 353 (10), 343 (10), 325 (100), 315 (10) | 297 (100), 281 (80) | + | + |
| 10’ | 5.45 | Delphinidin 3-O-(6”-acetyl)hexoside | C23H23O13+ | 507.11332 | 507.11270 | 1.22 | 304 (10), 303 (100) | 303 (20), 285 (10), 257 (100), 247 (10), 229 (30) | 229 (100), 213 (25), 201 (30), 173 (15) | + | + |
| 11’ | 6.22 | Delphinidin 3-O-(6”-p-coumaroyl)hexoside | C30H27O14+ | 611.13953 | 611.13904 | 0.80 | 304 (10), 303 (100) | 303 (20), 285 (10), 257 (100), 247 (10), 229 (30) | 229 (100), 213 (25), 201 (30), 173 (15) | + | + |
| 12’ | 6.53 | Delphinidin 3-O-hexoside isomer | C21H21O12+ | 465.10275 | 465.10202 | 1.57 | 304 (15), 303 (100) | 285 (60), 275 (10), 257 (100), 247 (30), 229 (80) | 239 (5), 229 (100), 213 (5), 201 (10), 173 (5) | + | + |
| 13’ | 6.56 | Delphinidin 3-O-hexuronide | C21H19O13+ | 479.08202 | 479.08124 | 1.63 | 304 (10), 303 (100) | 285 (50), 274 (20), 257 (100), 247 (30), 229 (80) | 229 (100), 201 (10) | + | + |
| Malvidin Derivatives | |||||||||||
| 14’ | 4.62 | Malvidin 3,5-di-O-glucoside a | C29H35O17+ | 655.18688 | 655.18469 | 3.34 | 494 (15), 493 (100), 332 (10), 331 (70) | 331 (100) | 316 (80), 315 (100), 299 (90), 298 (30), 287 (70) | + | + |
| 15’ | 5.35 | Malvidin 3-O-glucoside a | C23H25O12+ | 493.13405 | 493.13300 | 2.13 | 332 (10), 331 (100) | 316 (80), 315 (100), 299 (90), 298 (30), 287 (70) | 313 (90), 299 (25), 287 (100), 285 (70), 257 (60) | + | + |
| 16’ | 5.66 | Malvidin 3-O-hexoside-acetaldehyde(Vitisin B) | C25H25O12+ | 517.13405 | 517.13336 | 1.33 | 356 (15), 355 (100) | 339 (100), 322 (40), 311 (15), 294 (45), 266 (20) | 337 (50), 321 (35), 311 (100), 309 (95), 293 (10) | + | + |
| 17’ | 5.69 | Malvidin 3-O-pentoside | C22H23O11+ | 463.12349 | 463.12347 | 0.04 | 332 (5), 331 (100), 301 (10) | 316 (90), 315 (100), 299 (85), 298 (30), 287 (60) | 313 (90), 299 (25), 287 (100), 285 (70), 257 (60) | + | + |
| 18’ | 5.77 | Malvidin 3-O-hexoside-pyruvate(Vitisin A) | C26H25O14+ | 561.12388 | 561.12244 | 2.57 | 400 (10), 399 (100) | 383 (100), 367 (70), 355 (30), 338 (80), 310 (40) | 381 (60), 365 (40), 355 (100), 337 (15), 325 (20) | + | + |
| 19’ | 5.91 | Malvidin 3-O-hexoside-acetone | C26H27O12+ | 531.14970 | 531.14911 | 1.11 | 370 (10), 369 (100), 325 (5) | 353 (100), 336 (20), 325 (10), 308 (25), 280 (15) | 351 (60), 335 (30), 325 (100), 323 (80), 295 (25) | + | + |
| 20’ | 6.03 | Malvidin 3-O-(6”-acetyl)hexoside-pyruvate | C28H27O15+ | 603.13445 | 603.13416 | 0.48 | 400 (15), 399 (100) | 383 (100), 367 (80), 355 (40), 338 (80), 310 (40) | 381 (60), 365 (40), 355 (100), 337 (20), 325 (20) | + | − |
| 21’ | 6.13 | Malvidin 3-O-(6”-acetyl)hexoside | C25H27O13+ | 535.14462 | 535.14331 | 2.45 | 332 (10), 331 (100) | 316 (80), 315 (100), 299 (90), 298 (30), 287 (70) | 313 (100), 299 (30), 287 (90), 285 (80), 257 (60) | + | + |
| 22’ | 6.39 | Malvidin 3-O-(6”-caffeoyl)hexoside | C32H31O15+ | 655.16575 | 655.16406 | 2.58 | 332 (10), 331 (100) | 316 (80), 315 (100), 299 (90), 298 (30), 287 (70) | 313 (90), 299 (25), 287 (100), 285 (70), 257 (60) | − | + |
| 23’ | 6.70 | Malvidin 3-O-(6”-p-coumaroyl)hexoside-pyruvate | C35H31O16+ | 707.16066 | 707.15979 | 1.23 | 400 (10), 399 (100) | 383 (100), 367 (70), 355 (30), 338 (80), 310 (40) | 381 (60), 365 (40), 355 (100), 337 (15), 325 (20) | + | + |
| 24’ | 6.76 | Malvidin 3-O-hexoside-4-vinylcatechol (Pinotin A) | C31H29O14+ | 625.15518 | 625.15440 | 1.25 | 464 (15), 463 (100) | 448 (50), 447 (100), 419 (10), 402 (20), 374 (20) | 447 (50), 445 (65), 429 (20), 419 (100), 417 (95) | + | − |
| 25’ | 6.84 | Malvidin 3-O-(6”-p-coumaroyl)hexoside | C32H31O14+ | 639.17083 | 639.16996 | 1.36 | 332 (10), 331 (100) | 316 (80), 315 (100), 299 (90), 298 (30), 287 (70) | 313 (90), 299 (25), 287 (100), 285 (70), 257 (60) | + | + |
| 26’ | 6.89 | Malvidin 3-O-(6”-feruloyl)hexoside | C33H33O15+ | 669.18140 | 669.17857 | 4.23 | 332 (10), 331 (100) | 316 (80), 315 (100), 299 (90), 298 (30), 287 (70) | 313 (90), 299 (25), 287 (100), 285 (70), 257 (60) | − | + |
| 27’ | 6.99 | Malvidin 3-O-hexoside-4-vinylphenol | C31H29O13+ | 609.16027 | 609.16022 | 0.08 | 448 (25), 447 (100) | 432 (50), 431 (100), 414 (15), 386 (20), 358 (20) | 431 (50), 429 (65), 413 (20), 403 (100), 401 (95) | + | − |
| 28’ | 7.19 | Malvidin 3-O-hexoside-pyranone | C25H25O13+ | 533.12897 | 533.12677 | 4.13 | 372 (10), 371 (100) | 356 (15), 343 (100), 339 (10), 311 (30), 283 (20) | 311 (100), 283 (60), 265 (5), 255 (15) | + | − |
| 29’ | 7.30 | Malvidin 3-O-(6”-acetyl)hexoside-4-vinylphenol | C33H31O14+ | 651.17083 | 651.17035 | 0.74 | 448 (25), 447 (100) | 432 (50), 431 (100), 414 (15), 403 (10), 386 (20) | 431 (50), 429 (65), 413 (20), 403 (100), 401 (95) | + | − |
| 30’ | 7.40 | Malvidin-pyruvate | C20H15O9+ | 399.07106 | 399.07031 | 1.88 | 382 (20), 381 (100) | 366 (10), 353 (100), 337 (10), 325 (90), 297 (60) | 338 (5), 325 (100), 309 (10), 297 (25) | + | − |
| 31’ | 7.55 | Malvidin 3-O-(6”-p-coumaroyl)hexoside-4-vinylphenol | C40H35O15+ | 755.19705 | 755.19592 | 1.50 | 448 (25), 447 (100) | 432 (50), 431 (100), 414 (15), 403 (10), 386 (20) | 431 (50), 429 (65), 413 (20), 403 (100), 401 (95) | + | − |
| 32’ | 7.30 | Malvidin 3-O-(6”-p-coumaroyl)hexoside-4-vinylcatechol | C40H35O16+ | 771.19196 | 771.19055 | 1.83 | 464 (15), 463 (100) | 448 (50), 447 (100), 430 (15), 419 (10), 402 (20) | 447 (50), 445 (65), 429 (20), 419 (100), 417 (95) | + | − |
| Cyanidin Derivatives | |||||||||||
| 33’ | 4.78 | Cyanidin 3-O-glucoside a | C21H21O11+ | 449.10784 | 449.10684 | 2.23 | 288 (10), 287 (100) | 269 (25), 259 (40), 241 (50), 231 (70), 213 (100) | 195 (10), 185 (100), 167 (10), 157 (20), 141 (20) | + | + |
| 34’ | 5.04 | Cyanidin 3-O-arabinoside a | C20H19O10+ | 419.09727 | 419.09613 | 2.72 | 288 (10), 287 (100) | 269 (25), 259 (40), 241 (50), 231 (70), 213 (100) | 195 (10), 185 (100), 167 (10), 157 (20), 141 (20) | + | + |
| 35’ | 6.43 | Cyanidin 3-O-(6”-p-coumaroyl)hexoside | C30H27O13+ | 595.14462 | 595.14374 | 1.48 | 288 (10), 287 (100) | 269 (25), 259 (40), 241 (50), 231 (70), 213 (100) | 195 (10), 185 (100), 167 (10), 157 (20), 141 (20) | − | + |
| Petunidin Derivatives | |||||||||||
| 36’ | 4.89 | Petunidin 3-O-hexoside | C22H23O12+ | 479.11840 | 479.11655 | 3.86 | 318 (10), 317 (100) | 302 (100), 274 (5) | 274 (100), 246 (10), 228 (10), 218 (10) | + | + |
| 37’ | 5.79 | Petunidin 3-O-(6”-acetyl)hexoside | C24H25O13+ | 521.12897 | 521.12872 | 0.48 | 318 (10), 317 (100) | 302 (100), 285 (30), 274 (10) | 285 (10), 274 (100), 246 (15), 153 (20) | + | + |
| Pelargonidin Derivatives | |||||||||||
| 38’ | 5.17 | Pelargonidin 3-O-(6”-rhamnosyl)glucoside a | C27H31O14+ | 579.17083 | 579.16989 | 1.62 | 434 (5), 433 (15), 272 (10), 271 (100) | 271 (100), 253 (40), 225 (60), 215 (70), 197 (80) | 197 (5), 169 (100), 153 (5), 141 (30) | + | + |
a Confirmed using standards, the other compounds were identified according to 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.