Table 1.
UHPLC-PDA-ESI-MS3 identification data of polyphenols detected in the dry extracts from S. aucuparia flowers.
| No. | Analyte | R t (min) | UV λmax (nm) | [M–H]– (m/z) | MS2/MS3 fragmentation | Extract | References |
|---|---|---|---|---|---|---|---|
| 1 | Protocatechuic acida | 3.0 | 259, 294 | 153 | DEF, EAF | ||
| 2 | (Epi)catechin-B-(epi)catechinb,c | 3.4 | 280 | 577 | 451 (46), 425 (100), 407 (33) | DEF, EAF | [29] |
| 3 | 3-O-Caffeoylquinic acid (neochlorogenic acid)a | 3.5 | 216, 324 | 353 | 191 (100), 179 (30), 135 (3) | ME, BF, WR | [9, 11, 26] |
| 4 | (Epi)catechin-B-(epi)catechinb,c | 4.2 | 279 | 577 | 451 (60), 425 (100), 407 (28) | ME, DEF, EAF | [29] |
| 5 | p-Hydroxybenzoic acida | 4.6 | 255 | 137 | DEF | ||
| 6 | (+)-Catechina,b | 4.9 | 278 | 289 | 245 (100), 205 (21) | ME, DEF, EAF | |
| 7 | 5-O-Caffeoylquinic acid (chlorogenic acid, CHA)a | 5.4 | 216, 325 | 353 | 191 (100), 179 (3) | ME, DEF, EAF, BF, WR | [9, 11, 26] |
| 8 | 4-O-Caffeoylquinic acid (cryptochlorogenic acid)a | 6.3 | 216, 325 | 353 | 191 (50), 179 (49), 173 (100) | ME, EAF, BF, WR | [26] |
| 9 | Caffeic acida | 6.4 | 215, 323 | 179 | DEF | ||
| 10 | Procyanidin B2 (PB2)b | 6.8 | 280 | 577 | 451 (44), 425 (100), 407 (23) | DEF, EAF, BF | [29] |
| 11 | Unidentified | 7.8 | 261 | 360 | 313 (100), 151 (49) | EAF, BF | |
| 12 | (–)-Epicatechin (ECA)a,b,c | 8.1 | 279 | 289 | 245 (100), 205 (32) | ME, DEF, EAF | |
| 13 | Eriodictyol O-hexosideb,c | 8.2 | 279, 330sh | 449 | 287 (100), 269 (25), 259 (31) | BF | [31] |
| 14 | Unidentified | 8.4 | 249, 297 | 641 | 461 (17), 317 (100) | ME, BF | |
| 15 | 5-O-p-Coumaroylquinic acidb,c | 9.0 | 207, 311 | 337 | 191 (100), 163 (13) | EAF, BF | [26] |
| 16 | 5-O-Caffeoylshikimic acidb,c | 9.2 | 211, 325 | 335 | 291 (25), 179 (100), 135 (11) | ME, DEF, EAF, BF | [30] |
| 17 | Vanillic acida,b,c | 9.6 | 260, 293 | 167 | DEF | ||
| 18 | Sexangularetin di-O-hexosideb,c | 9.7 | 272, 326 | 639 | 519 (25), 477 (100), 315 (21) | ME, BF | [31] |
| 19 | p-Coumaric acida | 10.5 | 222, 309 | 163 | DEF | ||
| 20 | Quercetin 3-O-β-sophorosidea | 11.6 | 255, 353 | 625 | 463 (23), 445 (39), 301 (100) | ME, EAF, BF | |
| 21 | Coumaric acid isomerb,c | 11.9 | 293 | 163 | DEF | ||
| 22 | Quercetin O-dihexosideb,c | 12.3 | 255, 352 | 625 | 463 (35), 445 (60), 301 (100) | ME, EAF, BF | [31] |
| 23 | 4-O-Feruloylquinic acidb,c | 12.7 | 214, 323 | 367 | 191 (37), 179 (100), 135 (35) | DEF, EAF | [26] |
| 24 | Sexangularetin O-dihexosideb,c | 14.2 | 270, 337 | 639 | 477 (16), 459 (86), 315 (100) | BF | [31] |
| 25 | Quercetin O-pentosylhexosideb,c | 14.3 | 270, 340 | 595 | 463 (12), 445 (25), 301 (100) | EAF, BF | [31] |
| 26 | Kaempferol O-dihexosideb,c | 15.0 | 267, 340 | 609 | 447 (6), 429 (27), 285 (100) | BF | [31] |
| 27 | Kaempferol O-dihexosideb,c | 15.5 | 266, 343 | 609 | 447 (13), 429 (86), 285 (100) | BF | [31] |
| 28 | Quercetin O-hexosylpentosideb,c | 16.2 | 269, 342 | 595 | 433 (10), 415 (35), 301 (100) | ME, BF | [31] |
| 29 | Sexangularetin O-rhamosylhexosideb,c | 16.3 | 273, 333 | 623 | 477 (15), 459 (61), 315 (100) | ME, EAF, BF | [31] |
| 30 | Quercetin O-rhamosylhexosideb,c | 16.9 | 255, 353 | 609 | 301 (100) | ME, EAF, BF | [31] |
| 31 | Cinchonain I isomerb,c | 17.0 | 280 | 451 | 341 (100) | DEF | [32] |
| 32 | (Epi)catechin derivativeb,c | 17.3 | 279 | 483 | 451 (45), 341 (17), 289 (100) | DEF | |
| 33 | Quercetin 3-O-(6″-O-α-l-rhamnosyl)-β-d-glucoside (rutin, RT)a | 17.5 | 256, 353 | 609 | 301 (100) | ME, BF | [11] |
| 34 | Quercetin 3-O-β-d-galactoside (hyperoside)a | 17.6 | 255, 354 | 463 | 301 (100) | ME, DEF, EAF, BF | [11] |
| 35 | Quercetin 3-O-β-d-glucoside (isoquercitrin, IQ)a | 18.6 | 256, 353 | 463 | 301 (100) | ME, DEF, EAF, BF | [11] |
| 36 | Unidentified | 19.0 | 312 | 193 | DEF | ||
| 37 | (Epi)catechin-B-(epi)catechinb,c | 19.2 | 279 | 577 | 451 (60), 425 (100), 407 (28) | EAF | [29] |
| 38 | (Epi)catechin derivativeb,c | 19.4 | 256 | 483 | 451 (77), 341 (37), 289 (100) | DEF | |
| 39 | Unidentified | 19.6 | 280, 333sh | 597 | 477 (75), 387 (75), 357 (100) | BF | |
| 40 | Kaempferol O-rhamosylhexosideb,c | 19.8 | 277, 335 | 593 | 447 (11), 285 (100) | BF | [31] |
| 41 | Unidentifiedb,c | 19.9 | 282 | 519 | 309 (100) | DEF | |
| 42 | Ferulic acida,b,c | 20.2 | 217, 321 | 193 | DEF | ||
| 43 | Kaempferol O-hexosideb,c | 21.0 | 264, 344 | 447 | 285 (100) | DEF, EAF | [31] |
| 44 | Eriodictyol O-glucuronideb,c | 21.5 | 283 | 463 | 287 (100) | ME, BF | [9] |
| 45 | Sexangularetin 3-O-β-d-glucoside (sorbaroside)a | 21.8 | 270, 350 | 477 | 315 (100) | ME, DEF, EAF, BF | |
| 46 | Kaempferol 3-O-β-d-glucoside (astragalin)a,b,c | 22.9 | 265, 343 | 447 | 285 (100) | ME, DEF, EAF, BF | |
| 47 | Unidentified | 23.2 | 273, 350 | 507 | 491 (100), 345 (40), 329 (36) | EAF, BF | |
| 48 | Cinchonain I isomerb,c | 23.2 | 279 | 451 | 341 (100), 299 (23) | ME, DEF | [32] |
| 49 | Cinchonain I isomerb,c | 23.3 | 279 | 451 | 341 (100) | ME, DEF | [32] |
| 50 | Quercetin acetylhexosideb,c | 24.3 | 255, 350 | 505 | 463 (21), 301 (100) | ME, DEF, EAF, BF | [28] |
| 51 | 3,5-O-Dicaffeoylquinic acidb,c | 25.4 | 217, 326 | 515 | 353 (100), 191 (100)d, 179 (47)d | ME, DEF, EAF, BF | [27] |
| 52 | Caffeic acid derivativeb,c | 25.9 | 218, 328 | 437 | 377 (30), 275 (100), 179 (5) | ME, DEF, EAF | |
| 53 | Cinchonain I isomerb,c | 27.4 | 281 | 451 | 341 (100) | DEF | [32] |
| 54 | Sexangularetin O-acetylhexosideb,c | 27.9 | 271, 348 | 519 | 315 (100), 301 (60) | ME, BF | [28] |
| 55 | Quercetin O-acetylhexosideb,c | 28.3 | 260, 348 | 505 | 463 (50), 301 (100) | DEF | [28] |
| 56 | Sexangularetin O-acetylhexosideb,c | 28.5 | 271, 333 | 519 | 505 (32), 315 (100) | ME, DEF | [28] |
| 57 | 4,5-O-Dicaffeoylquinic acidb,c | 28.9 | 218, 325 | 515 | 353 (100), 179 (60)d, 173 (100)d | ME, DEF, EAF, BF | [27] |
| 58 | Kaempferol O-acetylhexosideb,c | 30.0 | 265, 335 | 489 | 327 (12), 285 (100) | DEF | [28] |
| 59 | Cinchonain I isomerb,c | 31.4 | 280 | 451 | 341 (100) | DEF | [32] |
| 60 | 3-O-Caffeoyl-5-O-feruloylquinic acidb,c | 31.7 | 308 | 529 | 367 (100), 191 (100)d, 179 (70)d | DEF | [27, 30] |
| 61 | 3-O-Feruloyl-5-O-caffeoylquinic acidb,c | 32.8 | 322 | 529 | 367 (100), 353 (84), 193 (100)d | DEF | [27, 30] |
| 62 | 3-O-Caffeoyl-4-O-p-coumaroilquinic acidb,c | 34.4 | 324 | 499 | 337 (100), 179 (100)d, 173 (97)d | DEF | [27, 30] |
| 63 | Caffeic acid derivativeb,c | 34.9 | 218, 328 | 437 | 377 (30), 275 (100), 179 (5) | BF | |
| 64 | Quercetina | 35.0 | 268, 364 | 301 | DEF | ||
| 65 | Tricoumaroyl spermidine isomerb,c | 39.0 | 285 | 582 | 462 (100), 342 (12) | DEF | [33] |
| 66 | Dicoumaroyl-caffeoyl spermidine isomerb,c | 39.7 | 288 | 598 | 478 (70), 462 (100), 342 (26) | DEF | [33] |
| 67 | Dicoumaroyl-caffeoyl spermidine isomerb,c | 41.1 | 313 | 598 | 478 (47), 462 (100), 342 (30) | ME, DEF, EAF | [33] |
| 68 | Tricoumaroyl spermidine isomerb,c | 41.6 | 293 | 582 | 462 (100), 342 (14) | DEF | [33] |
| 69 | Tricoumaroyl spermidine isomerb,c | 43.0 | 289 | 582 | 462 (100), 342 (9) | DEF, EAF | |
| 70 | Kaempferola | 43.6 | 272, 373 | 285 | DEF | ||
| 71 | Tricoumaroyl spermidine isomerb,c | 44.1 | 291 | 582 | 462 (100), 342 (12) | DEF | [33] |
| 72 | Tricoumaroyl spermidine isomerb,c | 45.2 | 293 | 582 | 462 (100), 342 (24) | ME, DEF, EAF | [33] |
R t: retention time. UV λmax: absorbance maxima in PDA spectra. [M–H]–: pseudomolecular ions in MS spectra recorded in a negative mode. MS2: secondary ions (the most abundant ions were subjected to MS3 fragmentation). Intensities of particular ions are given in parentheses. The nomenclature of the pseudodepsides of quinic acid and shikimic acid is given according to IUPAC [26, 27, 30]. aCompounds identified with authentic standards. bCompounds detected for the first time in S. aucuparia flowers. cCompounds detected for the first time in S. aucuparia. dMS3 ions.