Table 3.
Chromatographic, UV/Vis, and mass spectrometric characteristics of carotenoids from orange juice, obtained by HPLC-DAD-APCI- MSn.
| Peak | Compound | tRa (min) | λmax (nm) | %III/II | [M+H]+ (m/z) | HPLC/APCI (+)-MSn (Relative Intensity) |
|---|---|---|---|---|---|---|
| 1a | (all-E)-auroxanthin | 3.86 | 380, 404, 424 | 100 | 601 | |
| 1 | (Z)-mutatoxanthin isomer I | 4.50 | 404, 426, 453 | 11 | 585 | |
| 1b | (Z)-mutatoxanthin isomer II | 4.52 | 404, 426, 453 | 11 | 585 | |
| 1c | n.i. b | 4.87 | 406, 424, 541 | 20 | nd c,d | |
| 2 | (all-E)-mutatoxanthin | 5.27 | 407sh e, 430, 453 | 15 | 585 | MS2 [585]: 567 (100), 549 (20), 529 (10), 493 (13), 425(10), 377 (16), 221 (22) MS3 [585→567]: 549 (100),487 (10), 455 (10), 411 (12), 377 (12), 237 (11), 203 (12) |
| 2a | apocarotenoid | 5.41 | 426sh e, 448, nd c | nd c,f | 435 | MS2 [435]: 417 (8), 407 (90), 393 (59), 379 (100), 323 (76), 305 (38), 267 (37), 233 (32), 229 (29), 219 (35), 201 (36) MS3 [435→407]: 365 (10), 351 (100), 295 (21), 247 (11), 233 (22), 219 (28), 201 (50), 159 (10) MS3 [435→379]: 351 (8), 323 (100), 267 (32), 229 (5), 173 (9) MS3 [435→323]: 305 (10), 281 (11), 267 (100), 225 (8), 211 (20), 163 (5), 99 (26) |
| 3 | (all-E)-lutein | 6.00 | 420, 446, 473 | 42 | nd c,d | MS2 [551]: 533 (100), 495 (26), 459 (10), 429 (22), 411 (22), 397 (15), 345 (14), 175 (10) MS3 [551→533]: 421 (100), 365 (16), 315 (5), 259 (5), 219 (6) |
| 4 | (all-E)-zeaxanthin | 6.49 | 424, 449, 475 | 38 | 569 | MS2 [569]: 551 (10), 513 (10), 476 (36), 429 (12), 415 (10), 363 (10), 209 (8) MS3 [569→551]: 533 (100), 495 (23), 443 (17), 429 (22), 415 (20), 413 (19), 399 (18), 397 (22), 291 (15) |
| 5 | mutatoxanthin ester | 12.57 | 406, 424, 446 | nd c,f | nd c,d | 549 |
| 6 | n.i. b | 15.29 | 402, 420, 446 | 63 | nd c,d | |
| 7 | n.i. b | 16.03 | 417, 440, 469 | 93 | nd c,d | |
| 8 | n.i. b | 16.76 | 400, 424, 444 | nd c,f | nd c,d | |
| 9 | n.i. b | 17.26 | 392, 424, 444 | nd c,f | nd c,d | |
| 10 | n.i. b | 17.65 | 411, 436, 463 | 27 | nd c,d | |
| 11 | n.i. b | 17.98 | 413, 435, 463 | 55 | nd c,d | |
| 11a | n.i. b | 17.72 | 411, 437, 461 | 52 | nd c,d | |
| 11b | n.i. b | 18.02 | 410, 435, 462 | 39 | nd c,d | |
| 12 | n.i. b | 18.39 | 401, 424, 446 | 21 | nd c,d | |
| 13 | n.i. b | 18.81 | 399, 421, 447 | 78 | nd c,d | |
| 13a | n.i. b | 18.53 | 401, 421, 449 | 26 | nd c,d | |
| 13b | n.i. b | 18.81 | 401, 419, 448 | 34 | nd c,d | |
| 14 | n.i. b | 19.11 | 399, 424, 447 | 45 | nd c,d | |
| 15 | luteoxanthin ester | 19.46 | 393, 424, 448 | nd c,f | 755 | 565; 547 |
| 16 | violaxanthin ester | 20.09 | 417, 441, 469 | 83 | nd c,d | 565 |
| 17 | (all-E)-zeinoxanthin | 20.56 | 430sh e, 449, 477 | 58 | 533 | MS2 [553]: 535 (100), 497 (25), 461 (86), 429 (40), 400 (5), 399 (22), 347 (20), 285 (12) MS3 [553→535]: 493 (76), 479 (100), 465 (50), 425 (72), 399 (78), 369 (65), 345 (50), 269 (44), 235 (43), 187 (48), 173 (32) |
| 18 | (all-E)-β-cryptoxanthin | 21.24 | 430sh e, 454, 479 | 26 | 553 | MS2 [553]: 535 (100), 497 (14), 461 (85), 429 (20), 399 (24), 400 (12), 347 (24), 209 (10), 177 (12) MS3 [553→535]: 479 (100), 411 (34), 397 (60), 383 (30), 371 (62), 359 (50), 277 (40), 211 (26), 223 (21), 161 (20) MS3 [553→413]: 357(78), 343 (100), 293 (50), 275 (72), 221 (55), 199 (60), 147 (35) |
| 19 | (all-E)-violaxanthin laureate (C12:0) | 21.99 | 417, 439, 469 | 73 | 783 | 565; 547 |
| 20 | (Z)-luteoxanthin laureate (C12:0) | 22.24 | 389, 418, 445 | 78 | 783 | 565 |
| 21 | (all-E)-luteoxanthin laureate (C12:0) | 22.66 | 400, 418, 445 | 65 | 783 | MS2 [783]: 765 (100), 691 (12), 583 (46), 565 (26), 547 (8), 445 (4,) 375 (5) MS3 [783→765]: 747 (29), 673 (33), 565 (100), 547 (18), 417 (8), 357 (10), 221 (8) |
| 22 | (9Z)-violaxanthin laureate (C12:0) | 23.05 | 417, 439, 469 | 67 | 783 | 565; 547 |
| 23 | violaxanthin ester | 23.50 | 414, 436, 468 | 36 | nd c,d | 565 |
| 24 | violaxanthin ester | 24.14 | nd c, 433, 464 | 46 | nd c,d | 565 |
| 25 | (Z)-violaxanthin myristate (C14:0) | 24.61 | 419, 439, 469 | 73 | 811 | 565; 547 |
| 26 | (all-E)-violaxanthin myristate (C14:0) | 25.13 | 422, 443, 468 | nd c,f | 811 | 565; 547 |
| 27 | (all-E)-luteoxanthin myristate (C14:0) | 25.56 | 399, 419, 446 | 72 | 811 | MS2 [811]: 793 (100), 719 (10), 583 (52), 565 (20), 547 (5), 431 (5), 375 (6) MS3 [811→793]: 775 (35), 701 (30), 565 (100), 547 (25), 443 (4), 385 (5) |
| 28 | (9Z)-violaxanthin myristate (C14:0) | 26.10 | 413, 434, 464 | 32 | 811 | MS2 [811]: 793 (100), 719 (13), 583 (90), 565 (25), 547 (5), 431 (8), 375 (8) MS3 [811→793]: 775 (50), 701 (12), 565 (100), 547 (12), 497 (5), 431 (5), 429 (10) |
| 29 | carotenoid ester g | 26.52 | 416, 444, 469 | nd c,f | nd c,d | |
| 30 | carotenoid ester g | 26.84 | 400, 424, 446 | nd c,f | nd c,d | |
| 31 | mutatoxanthin laureate (C12:0) | 27.27 | 404, 424, 450 | 20 | 767 | 567; 549 |
| (31) | (all-E)-violaxanthin palmitate (C16:0) | 27.47 | 418, 438, 469 | 67 | 839 | 565; 547 |
| 32 | antheraxanthin laureate (C12:0) | 27.80 | 423, 443, 473 | nd c,f | 767 | 567; 549 |
| 33 | luteoxanthin palmitate (C16:0) | 28.25 | 399, 419, 447 | 76 | 839 | MS2 [839]: 583 (100), 565 (40), 547 (8), 393 (9) MS3 [839→821]: 803 (32), 729 (33), 565 (100), 547 (20), 375 (9) |
| (33) | luteoxanthin oleate (C18:1) | 28.25 | 399, 419, 447 | 76 | 865 | MS2 [865]: 847 (100), 829 (6), 773 (10), 583 (45), 565 (25), 547 (5), 485 (5),357 (5) MS3 [865→847]: 829 (32), 755 (40), 689 (8), 565 (100), 547 (10), 509 (8), 357 (10), 259 (8) |
| 34 | (9Z)-violaxanthin palmitate (C16:0) | 28.73 | 413, 434, 464 | 70 | 839 | MS2 [839]: 821 (82), 583 (100), 565 (20), 547 (5), 459 (5) MS3 [839→583]: 565 (100), 547 (12), 525 (14), 403 (18), 393 (8), 375 (20), 273 (12) |
| 35 | antheraxanthin myristate (C14:0) | 29.31 | 421, 446, 469 | 23 | 795 | 567; 549 |
| 36 | (all-E)-mutatoxanthin myristate (C14:0) | 29.94 | 406sh e, 424, 452 | 41 | 795 | MS2 [795]: 777 (72), 567 (100), 549 (16), 511 (8), 359 (8) MS3 [795→567]: 549 (68), 511 (100), 432 (60), 378 (50), 359 (48), 313 (44), 273 (45), 253 (32) |
| 37 | (9Z)-mutatoxanthin myristate (C14:0) | 30.40 | 407sh e, 424, 449 | 33 | 795 | MS2 [795]: 777 (83), 567 (100), 549 (12), 511 (10) 359 (12) MS3 [795→567]: 549 (100), 511 (20), 445 (25), 387 (28), 359 (28), 221 (30) |
| 38 | carotenoid ester g | 30.93 | 400, 424, 447 | 8 | nd c,d | |
| 39 | carotenoid ester g | 31.23 | 400, 426, 446 | nd c,f | nd c,d | |
| 39a | phytoene | 31.38 | 277sh e, 286, 297 | nd c,f | 545 | MS2 [545]: 489 (60), 463 (100), 421 (65), 395 (61), 353 (62), 325 (50), 297 (51),285 (60), 271 (38), 257 (34), 203 (28) MS3 [545→463]: 407 (40), 381 (40), 353 (50), 339 (51), 311 (90), 271 (85), 255 (60), 243 (60), 215 (100), 172 (41), 158 (42) |
| 39b | phytofluene | 31.53 | 330, 348, 367 | 77 | 543 | MS2 [543]: 461 (100), 419 (70), 393 (90), 351(70), 325 (78), 283 (75), 269 (48), 257 (38) MS3 [543→461]: 419 (71), 351 (100), 339 (44), 283 (56), 241 (88), 187 (42) |
| 40 | antheraxanthin palmitate (C16:0) | 31.85 | 422, 446, 473 | 57 | 823 | 567; 549 |
| 40a | (all-E)-ζ-carotene | 31.94 | 379, 398, 423 | 65 | 541 | MS2 [541]: 485 (50), 459 (94), 447 (50), 417 (75), 403 (100), 391 (94), 363 (47), 349 (96), 337 (75), 321 (40) MS3 [541→403]: 347 (100), 321 (54), 319 (46), 265 (92), 249 (48), 245 (35) |
| 41 | (Z)-mutatoxanthin palmitate (C16:0) | 32.41 | 400, 424, 452 | 25 | 823 | 567; 549 |
| 42 | (all-E)-mutatoxanthin palmitate (C16:0) | 32.82 | 407sh e, 424, 450 | 30 | 823 | MS2 [823]: 805 (78), 711 (10), 567 (100), 549 (18), 511 (12), 359 (10) MS3 [823→567]: 549 (100), 511 (55), 445 (20), 418 (34), 359 (25), 299 (24), 239 (24) |
| 43 | (all-E)-α-carotene | 33.42 | 409sh e, 434, 469 | 32 | 537 | 481; 444 |
| 44 | (all-E)-β-carotene | 33.98 | 426sh e, 449, 473 | 20 | 537 | MS2 [537]: 481 (12), 445 (100), 413 (40), 399 (38), 361 (19), 347 (32), 335 (18), 281 (68), 269 (16), 177 (20) MS3 [537→445]: 430 (70), 339 (100), 308 (72), 293 (38), 267 (40), 255 (30), 225 (35), 202 (20), 173 (20) |
| 45 | carotenoid ester g | 34.54 | 375, 395, 416 | 60–76 | nd c,d | |
| 46 | carotenoid ester g | 34.94 | 399, 414, 442 | 41 | nd c,d | |
| 47 | (Z)-violaxanthin caprate-laureate (C10:0-C12:0) | 35.43 | 414, 435, 465 | 79 | 937 | MS2 [937]: 919 (36), 765 (100), 737 (91), 565 (12), 547 (15), 375 (10) MS3 [937→765]: 747 (40), 565 (100), 547 (34), 403 (18), 375 (11), 349 (9) MS3 [937→737]: 719 (30), 565 (100), 547 (26), 375 (18), 349 (7) |
| 48 | carotenoid ester g | 36.00 | 400, 418, 445 | 23 | nd c,d | |
| 49 | carotenoid ester g | 36.57 | 379, 400, 431 | 45 | nd c,d | |
| 50 | (Z)-luteoxanthin oleate (C18:1) | 37.12 | 395, 418, 442 | 52 | 865 | MS2 [865]: 847 (68), 767 (10), 597 (48), 583 (100), 565 (5), 547 (5), 509 (11), 491 (6), 339 (5) MS3 [865→583]: 565 (82), 547 (42), 527 (78), 509 (100), 491 (28), 477 (10), 441 (11), 399 (16), 385 (12), 315 (13) |
| 51 | (Z)-violaxanthin dilaureate (C12:0-C12:0) | 37.42 | 413, 435, 465 | 79 | 965 | MS2 [965]: 947 (26), 793 (18), 765 (100), 747 (10), 737 (14), 565 (6), 547 (10), 469 (2), 403 (8), 375 (58), 393 (1) MS3 [965→765]: 747 (28), 565 (100), 547 (24), 403 (10), 375 (12), 357 (5) |
| 52 | carotenoid ester g | 37.95 | 401, 419, 445 | 41 | nd c,d | |
| 53 | carotenoid ester g | 38.25 | 401, 419, 445 | 98 | nd c,d | |
| 54 | carotenoid ester g | 38.52 | 414, 436, 463 | 25 | nd c,d | |
| 55 | mutatoxanthin diester (presumably caprate-laureate) (C10:0-C12:0) | 39.22 | 398, 418, 443 | 63 | 921 | 549 |
| 56 | (Z)-violaxanthin laureate-myristate (C12:0-C14:0) | 39.51 | 413, 436, 465 | 80 | 993 | MS2 [993]: 975 (35), 793 (100), 765 (98), 747 (12), 565 (11), 547 (9) MS3 [993→793]: 775 (30), 565 (100), 547 (26), 375 (20) MS3 [993→793]: 747 (30), 565 (100), 547 (31), 375 (10) |
| 57 | (all-E)-zeinoxanthin laureate (C12:0) | 40.05 | 424, 443, 473 | 47 | 735 | 535 |
| 58 | (all-E)-β-cryptoxanthin laureate (C12:0) | 40.44 | 431, 452, 474 | 38 | 735 | MS2 [535]: 479 (78), 439 (50), 411 (83), 399 (100), 359(80), 345 (60) MS3 [535→399]: 384 (58), 343 (77), 301 (70), 279 (94), 265 (91) |
| 59 | (all-E)-violaxanthin dimyristate (C14:0-C14:0) | 41.15 | 414, 443, 470 | 79 | 1021 | MS2 [1021]: 821 (22), 793 (100), 765 (31), 565(10), 547 (9), 431 (5) MS3 [1021→793]: 775 (39), 565 (100), 547 (39), 403 (10), 375 (10) |
| (59) | mutatoxanthin dilaureate (C12:0-C12:0) | 40.98 | 398, 418, 443 | 63 | 949 | 949 |
| 60 | (9Z)-violaxanthin dimyristate (C14:0-C14:0) | 41.48 | 418, 441, 470 | 79 | 1021 | MS2 [1021]: 821 (40), 793 (100), 765 (50), 747 (8), 565 (9), 547 (10), 431 (5) MS3 [1021→793]: 775 (38), 565 (100), 547 (30), 497 (5), 375 (16) MS2 [1003]: 911 (40), 803 (20), 775 (100), 747 (20), 547 (20) MS3 [1003→775]: 547 (100), 529 (5), 491 (3), 425 (4), 221 (3) |
| 61 | zeinoxanthin myristate or α-cryptoxanthin myristate (C14:0) | 42.13 | 424, 443, 469 | 34 | 763 | 671; 535 |
| 62 | β-cryptoxanthin myristate (C14:0) | 42.49 | 426sh e, 449, 474 | nd c,f | 763 | 671; 535 |
| 63 | (Z)-violaxanthin myristate-palmitate (C16:0) | 43.05 | 414, 437, 465 | 72 | 1049 | MS2 [1049]: 1031 (38), 821 (95), 793 (100), 775 (10), 565 (12), 547 (9) MS3 [1049→793]: 775 (32), 565 (100), 547 (28), 403 (8), 375 (18) |
| (63) | mutatoxanthin laureate-myristate (C12:0-C14:0) | 42.71 | 398, 418, 443 | 63 | 977 | MS2 [977]: 777 (100), 749 (95), 549 (20), 531 (5), 359 (5) MS3 [977→777]: 549 (100), 531 (8), 427 (6), 359 (10), 333 (5), 237 (4) |
| 64 | (all-E)-lutein laureate (C12:0) | 44.07 | 422, 445, 473 | 60 | 733 | MS2 [733]: 533 (100), 494 (10), 477 (7), 411 (10), 343 (8) MS3 [733→533]: 518 (40), 465 (40), 411 (100), 357 (60), 345 (25), 305 (50) |
| (64) | (all-E)-zeinoxanthin palmitate (C16:0) | 43.97 | 422, 445, 473 | 60 | 791 | 535; 479 |
| 65 | (all-E)-β-cryptoxanthin palmitate (C16:0) | 44.39 | 426sh e, 454, 475 | 17 | 791 | MS2 [791]: 698 (25), 535 (100), 443 (13), 411 (4) MS3 [791→535]: 520 (60), 479 (48), 439 (50), 411 (70), 397 (100) |
| 66 | antheraxanthin dimyristate (C14:0-C14:0) | 44.71 | 418, 439, 466 | 61 | 1005 | MS2 [1005]: 805 (30), 777 (100), 749 (25), 549 (12) MS3 [1005→777]: 549 (100), 531 (5), 413 (5), 359 (6) |
| (66) | (Z)-violaxanthin dipalmitate (C16:0-C16:0) | 44.71 | 418, 439, 466 | 61 | 1077 | MS2 [1077]: 1059 (15), 821 (100), 803 (10), 565 (5), 547 (4) MS3 [1077→821]: 803 (37), 631 (7), 565 (100), 547 (32), 375 (11), 357 (6) |
| (66) | (Z)-violaxanthin palmitate-oleate (C16:0-C18:1) | 44.71 | 418, 439, 466 | 61 | 1103 | MS2 [1103]: 1085 (25), 847 (100), 821 (85), 565 (11), 547 (8) MS3 [1103→847]: 829 (30), 565 (100), 547 (32), 389 (4), 375 (12), 357 (7) |
| 67 | (all-E)-lutein 3-O-myristate-3′-O-laureate(C14:0-C12:0) | 45.70 | 422, 445, 473 | 67 | 961 | 761; 733; 533 |
| 68 | antheraxanthin myristate-palmitate (C16:0) | 46.26 | 422sh e, 443, 469 | 34 | 1033 | MS2 [1033]: 1015 (2), 873 (5), 805 (100), 777 (80), 549 (18), 531 (4), 359 (4) MS3 [1033→805]: 787 (10), 549 (100), 531 (8), 413 (9), 359 (10) |
| 69 | (all-E)-lutein 3-O-myristate-3′-O-palmitate(C14:0-C16:0) | 47.18 | 423sh e, 446, 473 | 64 | 1017 | 789; 761; 533 |
| 70 | antheraxanthin dipalmitate (C16:0-C16:0) | 47.65 | 423sh e, 445, 469 | 37 | 1061 | MS2 [1061]: 1043 (4), 901 (2), 833 (10), 805 (100), 777 (6), 683 (2), 615 (3), 549 (10) MS3 [1061→805]: 699 (8), 645 (10), 549 (100), 485 (2), 455 (8), 427 (8), 357(10) |
| 71 | (all-E)-lutein 3-O-palmitate-3′-O-myristate (C16:0-C14:0) | 48.51 | 423, 446, 473 | 73 | 1017 | 789; 761; 533 |
| 72 | (all-E)-zeaxanthin myristate-palmitate (C14:0-C16:0) | 49.03 | 424, 450, 474 | 46 | 1017 | 789; 761; 533 |
| 73 | (all-E)-lutein dipalmitate (C16:0-C16:0) | 49.78 | 423sh e, 446, 474 | 73 | 1045 | 789; 533 |
| 74 | (all-E)-zeaxanthin dipalmitate (C16:0-C16:0) | 50.26 | 423sh e, 446, 474 | 47 | 1045 | 789; 533 |
a Retention time on Accucore C30 column. b n.i., not identified. c nd, not detected. d [M+H]+ or fragment ions were not detected. e shoulder. f %III/II could not be calculated because of poor resolution of the UV/vis spectrum. g Carotenoid esters were identified due to saponification.