Table 1.
HPLC–ESI–MSn characterization of phytochemicals in extracts of Cornezuelo, Cornicabra and Picual olive fruits in different months of season 2018/2019.
| N° | tR(min) | [M-H]− m/z | m/z (% Base Peak) | Assigned Identification | Cornezuelo | Cornicabra | Picual | |||||||||
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| 1st | 2nd | 3rd | 4th | 1st | 2nd | 3rd | 4th | 1st | 2nd | 3rd | 4th | |||||
| 1 | 1.8 | 191 | MS2 [191]: 173 (37), 127 (7), 111 (100) | Citric acid | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ |
| 2 | 2.8 | 375 | MS2 [375]: 213 (100), 169 (13), 151 (3), 125 (23), 107 (4) MS3 [375→213]: 169 (7), 125 (100) |
Dihydrocominic acid | ✓ | ✓ | ||||||||||
| 3 | 3.5 | 315 | MS2 [315]: 153 (100), 135 (19), 123 (22) MS3 [315→153]: 123 (100) |
Hydroxytyrosol glucoside | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ |
| 4 | 4.1 | 407 | MS2 [407]: 389 (100), 375 (85), 357 (71), 313 (57) MS3 [407→389]: 357 (62), 313 (100), 161 (22) |
1-β-Glucosyl-acyclodihydroelenolic acid | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ |
| 5 | 7.3 | 389 | MS2 [389]: 345 (100), 209 (65), 165 (25), 121 (44) MS3 [389→345]: 183 (51), 165 (100), 119 (48) MS4 [389→345→165]: 121 (100) |
Oleoside/secologanoside | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ |
| 6 | 10.2 | 403 | MS2 [403]: 223 (100), 179 (69), 143 (24), 121 (21) MS3 [403→223]: 191 (11), 121 (100) |
Oleoside-11-methylester * | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ |
| 7 | 10.7 | 377 | MS2 [377]: 197 (100), 153 (25) MS3 [377→197]: 153 (100) |
Oleuropein aglycone | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ |
| 8 | 13.4 | 337 | MS2 [337]: 178 (41), 115 (6), 114 (100) | Unknown | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ||||||
| 9 | 13.6 | 403 | MS2 [403]: 371 (100), 223 (70), 179 (78), 121 (13) | Elenolic acid glucoside | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | |||||
| 10 | 17.6 | 525 | MS2 [525]: 481 (29), 319 (23), 301 (23), 195 (100) MS3 [525→195]: 193 (100), 192 (50) |
Dimethyl-oleuropein glucoside | ✓ | ✓ | ||||||||||
| 11 | 18.1 | 701 | MS2 [701]: 539 (34), 469 (29), 385 (17), 315 (100) MS3 [701→315]: 153 (100), 123 (24) MS4 [701→315→153]: 123 (100) |
Hydroxytyrosol glucoside derivative | ✓ | ✓ | ✓ | ✓ | ✓ | |||||||
| 12 | 19.4 | 609 | MS2 [609]: 301 (100) MS3 [609→301]: 179 (100), 151 (70) MS4 [609→301→179]: 151 (100) |
Rutin * | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ |
| 13 | 20.3 | 623 | MS2 [623]: 461 (100) MS3 [623→461]: 315 (58), 135 (100) |
Verbascoside * | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | |
| 14 | 20.8 | 447 | MS2 [447]: 285 (100) MS3 [447→285]: 241 (90), 175 (100) |
Luteolin-O-hexoside | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ |
|
15
|
21.2 | 543 | MS2 [543]: 525 (100), 513 (31), 389 (15)MS3 [543→525]: 389 (100), 357 (73), 313 (83) MS4 [543→525→389]: 357 (59), 313 (100) |
Dihydrooleuropein | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ |
| 16 | 22.1 | 701 | MS2 [701]: 539 (100), 377 (82), 307 (54), 275 (46) MS3 [701→539]: 507 (32), 377 (100), 307 (94), 275 (73) MS4 [701→539→377]: 275 (100) |
Oleuropein glucoside | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ |
| 17 | 23.1 | 701 | MS2 [701]: 539 (100), 377 (43), 307 (42), 275 (34) MS3 [701→539]: 377 (54), 307 (50), 275 (100) MS4 [701→539→275]: 139 (100), 113 (86) |
Oleuropein glucoside | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | |||||
| 18 | 24.3 | 551 | MS2 [551]: 507 (100), 341 (48), 281 (37), 251 (39), 179 (40) MS3 [551→507]: 341 (34), 179 (34), 161 (100) |
6′-β-hexopyranosyloleoside | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ |
| 19 | 25.4 | 377 | MS2 [377]: 307 (100), 275 (72) MS3 [377→307]: 275 (100), 139 (22) MS4 [377→307→275]: 113 (100) |
Oleuropein aglycone | ✓ | ✓ | ✓ | ✓ | ||||||||
| 20 | 26.0 | 569 | MS2 [569]: 537 (90), 403 (100), 223 (25) MS3 [569→403]: 371 (10), 223 (100), 179 (81), 143 (28) MS4 [569→403→223]: 121 (100), 101 (24) |
Elenolic acid glucoside derivative | ✓ | ✓ | ✓ | ✓ | ||||||||
| 21 | 27.0 | 539 | MS2 [539]: 377 (100), 307 (57), 275 (72) MS3 [539→377]: 307 (100), 275 (87), 149 (8) MS4 [539→377→307]: 275 (100) |
Oleuropein * | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ |
| 22 | 28.3 | 535 | MS2 [535]: 491 (100), 265 (36), 235 (28) MS3 [535→491]: 345 (46), 265 (46), 145 (100) |
Comselogoside isomer | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ |
| 23 | 29.4 | 539 | MS2 [539]: 377 (71), 307 (85), 275 (100) | Oleuropein isomer | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ |
| 24 | 30.1 | 535 | MS2 [535]: 491 (100), 265 (60), 235 (44), 209 (37) MS3 [535→491]: 345 (25), 235 (46), 206 (19), 145 (100) MS4 [535→491→145]: 143 (100) |
Comselogoside isomer | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ||||
| 25 | 30.6 | 473 | MS2 [473]: 358 (29), 195 (100), 178 (7) MS3 [473→195]: 135 (100) |
Unknown | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ||
| 26 | 32.2 | 523 | MS2 [523]: 361 (100), 291 (59), 259 (47) MS3 [523→361]: 291 (100), 259 (77), 223 (12) |
Ligstroside | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ |
| 27 | 36.3 | 557 | MS2 [557]: 513 (100), 345 (46), 209 (66), 185 (56) MS3 [557→513]: 345 (100), 199 (19), 185 (59) MS4 [557→513→345]: 183 (100) |
Oleoside/secologanoside derivative | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ✓ | ||
* Identified with analytical standard.