Characterization and Identification of Prenylated Flavonoids from Artocarpus heterophyllus Lam. Roots by Quadrupole Time-Of-Flight and Linear Trap Quadrupole Orbitrap Mass Spectrometry
Abstract
:1. Introduction
2. Results and Discussion
2.1. Fragment Naming Rules
2.2. Fragmentation of PFs 1–3
2.3. Fragmentation of PFs 4 and 5
2.4. Fragmentation of PFs 6–9
2.5. Fragmentation of PFs 10 and 11
2.6. Fragmentation of PFs 12–15
2.7. Rapid Identification of PFs in the Extract of A. heterophyllus Roots
3. Materials and Methods
3.1. Plant Material
3.2. Model Molecules and Reagents
3.3. Sample Preparation
3.4. Ultra-High Performance Liquid Chromatography (UPLC)-Q-TOF-MS/MS and UPLC-LTQ-Orbitrap-MSn Analysis of PFs
3.5. Data Preprocessing Analysis
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Conflicts of Interest
References
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Sample Availability: Samples of the compounds (PFs 1–15) are available from the authors. |
Compounds | MSn | Precursor Ions | Product Ions m/z (Relative Abundance, %) |
---|---|---|---|
PF 1 | MS/MS | 367 [M − H]− | 175 (3.4); 233 (3.9); 265 (4.2); 297 (18.9); 309 (77.7); 337 (1.6); 352 (1.7); 367 (100.0) |
MS3 | 233 | 133 (20.4); 165 (61.7); 189 (23.7); 217 (100.0) | |
309 | 175 (61.7); 265 (100.0); 291 (26.7) | ||
MS4 | 265 | 173 (100.0); 193 (36.4); 215 (62.1); 221 (75.1); 237 (70.1) | |
PF 2 | MS/MS | 353 [M − H]− | 133 (6.8); 297 (15.5); 309 (15.5); 353 (100.0) |
MS3 | 297 | 225 (20.1); 227 (21.4); 253 (97.5); 255 (83.4); 269 (100.0) | |
309 | 265 (18.8); 267 (19.9); 309 (100.0) | ||
MS4 | 269 | 225 (53.4); 227 (35.2); 241 (75.7); 251 (100.0); 269 (39.3) | |
267 | 211 (10.4); 223 (17.9); 239 (44.7); 252 (20.5); 267 (100.0) | ||
PF 3 | MS/MS | 353 [M − H]− | 133 (2.0); 219 (9.8);309 (3.1); 353 (100.0) |
MS3 | 219 | 133 (80); 151 (39.4); 175 (100.0) | |
MS4 | 175 | 65 (13.4); 133 (100.0) | |
PF 4 | MS/MS | 421 [M − H]− | 133 (12.7); 161 (8.9); 255(9.4); 269 (8.7); 297 (100.0); 323(12.4); 337 (12.0); 421 (21.9) |
MS3 | 297 | 163 (9.8); 225(22.8); 227 (22.1); 253(100.0); 255 (84.4); 269 (95.9) | |
MS4 | 253 | 211 (10.7); 225 (100.0); 253 (22.9) | |
PF 5 | MS/MS | 435 [M − H]− | 133 (6.7); 269 (8.); 297(84.5); 309 (30.1); 311 (13.5); 323(21.1); 351 (100.0); 420 (35.4); 435 (32.8) |
MS3 | 297 | 163 (9.0); 225(20.9); 227 (21.0); 253(88.6); 255 (75.6); 269 (100.0) | |
351 | 307 (9.2); 309 (19.1); 333 (24.0); 351 (100.0) | ||
MS4 | 253 | 211 (8.38); 225 (100.0); 253 (20.2) | |
PF 6 | MS/MS | 353 [M − H]− | 109 (16.7); 125 (30.6); 151 (24.8); 231 (100.0); 243 (13.2); 283 (11.6); 284 (62.0); 353 (50.5) |
MS3 | 231 | 145 (23.1); 147 (23.2); 149 (24.0); 151 (76.7); 163 (23.0); 187 (100.0); 189 (28.2) | |
284 | 256 (100.0) | ||
MS4 | 256 | 122 (100.0); 212 (56.7); 227 (43.6); 228 (38.3) | |
PF 7 | MS/MS | 421 [M − H]− | 193 (8.91); 219 (1.9); 227 (1.8); 283 (2.4); 297 (7.7); 299 (20.9); 309 (38.8); 311 (3.1); 421 (100.0) |
MS3 | 193 | 125 (43.1); 149 (100.0); 151 (36.2) | |
309 | 175 (92.2); 265 (100.0) | ||
MS4 | 149 | 107 (100.0) | |
265 | 173 (59.8); 175 (44.4); 215 (74.5); 221 (76.7); 223 (100.0); 237 (56.2) | ||
PF 8 | MS/MS | 421 [M − H]− | 193 (7.1); 293 (7.7); 299 (27.7); 309 (47.1); 421 (100.0) |
MS3 | 299 | 244 (90.0) | |
309 | 175 (10.2); 244 (100.0); 256 (19.7); 299 (78.7) | ||
MS4 | 299 | 244 (100.0); 299 (58.0) | |
244 | 123 (100.0); 149 (35.3); 150 (69.0); 203 (53.3); 215 (35.8); 216 (77.4); 229 (99.11) | ||
PF 9 | MS/MS | 489 [M − H]− | 261 (6.1); 351 (6.0); 365 (10.3); 367 (100.0); 377 (75.9); 489 (90.4) |
MS3 | 367 | 257 (10.6); 269 (24.5); 312 (100.0); 367 (71.2) | |
377 | 269 (10.1); 312 (31.5); 367 (100.0) | ||
MS4 | 312 | 257 (51.4); 269 (100.0) | |
PF 10 | MS/MS | 417 [M − H]− | 199 (2.3); 217 (3.0); 333 (7.3); 347 (2.4); 361 (11.7); 373 (6.29); 387 (2.8); 401 (3.3) |
MS3 | 361 | 319 (7.5); 334 (13.5); 343 (100.0); 346 (59.4) | |
MS4 | 343 | 199 (22.1); 287 (36.2); 299 (10.0); 315 (24.2); 343 (100.0) | |
PF 11 | MS/MS | 501 [M − H]− | 285 (3.8); 429 (3.7); 457 (43.22); 473 (3.3); 501 (100.0) |
MS3 | 285 | 285 (5.2); 243 (22.0); 241 (100.0); 217 (8.5) | |
457 | 402 (20.1); 439 (100.0); 442 (10); 457 (18.7) | ||
MS4 | 241 | 133 (67.5); 157 (32.2); 173 (77.2); 193 (26.6); 197 (100.0); 213 (32.5) | |
439 | 357 (58.70); 383 (21.73); 395 (53.51); 411 (100.0); 424 (20.26) | ||
MS5 | 411 | 329 (35.9); 341 (87.8); 354 (73.8); 356 (87.3); 367 (54.4); 383 (76.9); 393 (58.3); 396 (100.0); 411 (22.5) | |
PF 12 | MS/MS | 501 [M − H]− | 415 (8); 417 (5.0); 429 (7.3); 445 (14.8); 457 (4.2); 471 (13.0); 483 (4.4); 501 (100.0) |
MS3 | 445 | 355 (25.3); 373 (38.8); 399 (39.0); 403 (26.7); 417 (100.0); 427 (94.2); 445 (74.6) | |
485 | 429 (100.0); 442 (60.3); 457 (29.9); 469 (46.5); 471 (85.7) | ||
MS4 | 427 | 355 (53.9); 383 (10.5); 399 (100.0); 427 (34.5) | |
429 | 401 (100.0); 411 (31.5); 414 (20.5) | ||
MS5 | 399 | 343 (52.5); 355 (100.0); 356 (41.6) | |
401 | 357 (88.5); 373 (100.0); 383 (26.6); 386 (70.6); 401 (19.3) | ||
PF 13 | MS/MS | 433 [M − H]− | 373 (11.3); 389 (37.0); 390 (63.2); 405 (25.3); 417 (11.2); 433 (100.0) |
MS3 | 389 | 361 (15.2); 372 (100.0); 373 (34.3); 375 (17.5); 389 (27.9) | |
405 | 335 (17.4); 350 (32.9); 361 (27.9); 360 (30.4); 372 (21.9); 389 (15.1); 405 (100.0) | ||
MS4 | 372 | 326 (34.9); 327 (35.9); 343 (71.7); 371 (100.0) | |
350 | 309 (21.6); 335 (100.0); 349 (22.2) | ||
MS5 | 343 | 299 (13.9); 343 (100.0) | |
335 | 276 (16.0); 291 (68.1); 308 (25.6); 317 (34.2); 335 (100.0) | ||
MS6 | 299 | 263 (14.0); 276 (100.0); 291 (16.7) | |
291 | 263 (14.0); 276 (100.0); 291 (16.7) | ||
PF 14 | MS/MS | 435 [M − H]− | 349 (34.2); 363 (5.0); 377 (20.7); 379 (12.4); 391 (12.4); 393 (6.3); 419 (6.3); 435 (100.0) |
MS3 | 349 | 277 (21.4); 305 (15.0); 321 (32.9); 349 (100.0) | |
391 | 337 (29.5); 349 (100.0); 363 (23.9); 377 (17.8) | ||
MS4 | 321 | 264 (100.0); 276 (40.7); 279 (62.5); 293 (90.0) | |
337 | 309 (100.0) | ||
MS5 | 309 | 237 (21.1); 263 (32.6); 365 (23.3); 279 (27.0); 281 (70.3); 291 (100.0); 309 (31.4) | |
PF 15 | MS/MS | 501 [M − H]− | 417 (5.0); 429 (5.5); 443 (5.8); 445 (12.2); 457 (7.3); 471 (7.7); 485 (14.8); 501 (100.0) |
MS3 | 445 | 355 (27.4); 373 (41.3); 399 (38.9); 417 (99.6); 427 (100.0); 445 (80.8) | |
485 | 429 (100.0); 442 (60.8); 457 (34.2); 469 (47.9); 471 (88.0) | ||
MS4 | 427 | 355 (26.4); 371 (56.0); 385 (27.2); 399 (100.0) | |
429 | 357 (26.3); 374 (19.6); 401 (100.0); 411 (29.9) | ||
MS5 | 399 | 355 (100.0); 384 (18.3) | |
401 | 357 (91.0); 373 (100.0); 383 (32.7); 385 (48.8); 401 (21.8) |
Peak No. | Compounds | RT (min) | Molecular Formula | [M − H]− (m/z) | Error (Δppm) | Product Ions (m/z) | Error (Δppm) | Fragment Ions Identified |
---|---|---|---|---|---|---|---|---|
1 | 6-(3-Methylbutyl-2-enyl)apigenin [23] | 3.49 | C20H18O5 | 337.10903 | 2.6 | 219.0681 | 8.2 | [M – H − 1,3B]− |
281.0473 | 6.4 | [M − H − C4H8]− | ||||||
2 | Artonin K [24] | 4.14 | C21H18O7 | 381.09924 | 3.3 | 337.0738 | 5.9 | [M – H − C2H4O]− |
365.0687 | 5.5 | [M – H − CH4]− | ||||||
3 | Albanin A [25] | 4.66 | C20H18O6 | 353.10459 | 4.3 | 125.0246 | 4.8 | [M – H − 1,4B]− |
231.0668 | 2.2 | [M – H − 1,4A]− | ||||||
4 | 14-Hydroxyartonin E [26] | 4.87 | C25H24O8 | 451.14188 | 4.5 | 393.0999 | 4.8 | [M – H − C3H6O]− |
433.1289 | 0.9 | [M − H − H2O]− | ||||||
5 | Artoindonesianin P [27] | 5.22 | C22H20O7 | 395.11548 | 4.7 | 337.0736 | 5.3 | [M – H − C3H6O]− |
351.0515 | 1.4 | [M – H − 3·CH3]− | ||||||
6 | Artonin J [28] | 5.47 | C25H24O7 | 435.14663 | 3.9 | 379.0839 | 4.2 | [M – H − C4H8]− |
365.0681 | 3.8 | [M – H − C5H10]− | ||||||
7 | Artelastoxanthone [18] | 6.67 | C25H22O7 | 433.12925 | −0.1 | 405.1399 | −1.2 | [M – H − CO]− |
389.1017 | 3.6 | [M – H − CO2]− | ||||||
8 | Artobiloxanthone [29] | 6.68 | C25H22O7 | 433.13224 | 6.8 | 405.1364 | 4.9 | [M – H − CO]− |
403.0850 | 6.7 | [M – H − 2CH3]− | ||||||
9 | Artonin E [28] | 7.23 | C25H24O7 | 435.14663 | 3.9 | 379.0841 | 4.7 | [M – H − C4H8]− |
351.0887 | 3.7 | [M – H − C5H4O]− | ||||||
10 | Cyclocommunol [30] | 7.31 | C20H16O6 | 351.08818 | 2.2 | 199.0777 | 6.0 | [M – H − 1,3A]− |
295.0259 | 3.7 | [M – H − C4H8]− | ||||||
11 | Artoindonesianin Q [4] | 7.47 | C22H22O7 | 397.12891 | −0.9 | 137.0247 | −2.2 | [M – H − 1,4B]− |
313.0345 | 2.9 | [M – H − CH3 − C5H9]− | ||||||
311.0195 | 0.6 | [M – H − OCH3 − C4H7]− | ||||||
365.1021 | −2.2 | [M – H − OCH3]− | ||||||
12 | Artoindonesianin R [31] | 7.49 | C22H22O7 | 397.13136 | 5.1 | 313.0357 | 1.0 | [M – H − C6H12]− |
137.0242 | −1.5 | [M – H − 1,4B]− | ||||||
13 | Artonol E [32] | 7.91 | C26H24O7 | 447.14548 | 1.2 | 415.1155 | −7.7 | [M – H − OCH4]− |
391.0831 | 2.0 | [M – H − C4H8]− | ||||||
14 | Artoindonesianin T [31] | 8.31 | C22H20O7 | 395.11548 | 4.7 | 339.0518 | 2.4 | [M – H − C4H8]− |
365.0655 | −3.3 | [M – H − 2CH3]− | ||||||
15 | Cycloartobiloxanthone [27] | 10.48 | C25H22O7 | 433.13134 | 4.7 | 391.0824 | 0.3 | [M – H − C3H6]− |
415.1177 | −2.4 | [M – H − H2O]− | ||||||
16 | Artoindonesianin B [33] | 10.92 | C26H28O8 | 467.17322 | 4.4 | 261.0758 | −3.8 | [M – H − 1,4A]− |
451.1399 | 0.2 | [M – H − CH4]− | ||||||
17 | Artocarpetin A [34] | 13.07 | C21H20O6 | 367.11769 | −2.8 | 233.0829 | −4.3 | [M – H − 1,3B]− |
297.0410 | −1.7 | [M – H − C5H10]− | ||||||
309.0763 | 1.6 | [M – H − C3H4O]− | ||||||
18 | Heteroflavanone C [35] | 13.44 | C23H26O7 | 413.16078 | 0.5 | 247.0975 | −0.4 | [M – H − C9H10O3]− |
235.0982 | 2.6 | [M – H − 1,2B]− | ||||||
19 | Artocarpesin [36] | 13.48 | C20H18O5 | 337.10903 | 2.6 | 133.0294 | −0.8 | [M – H − 1,3A]− |
281.0477 | 7.8 | [M – H − C4H8]− | ||||||
20 | 6-(3-Methylbut-2-enyl) Apigenin [18] | 13.5 | C20H18O5 | 337.10809 | −0.2 | 281.0464 | −3.2 | [M – H − C4H8]− |
117.0349 | −2.6 | [M – H − 1,3A]− | ||||||
21 | Styracifolin D [4] | 13.88 | C30H32O8 | 519.20258 | 0.3 | 461.1583 | 5.0 | [M – H − C3H6O]− |
491.2075 | 0.0 | [M – H − CO]− | ||||||
501.1919 | 0.0 | [M – H − H2O]− | ||||||
22 | Cycloartocarpesin [37] | 14.28 | C20H16O5 | 335.09274 | 0.7 | 133.0301 | 4.5 | [M – H − 1,3A]− |
305.0462 | 2.3 | [M – H − 2CH3]− | ||||||
23 | Artonin U [38] | 15.17 | C21H20O5 | 351.12462 | 2.4 | 281.0469 | 5.0 | [M – H − C5H10]− |
24 | Norartocarpin [39] | 17.16 | C25H26O6 | 421.16567 | 0 | 227.0725 | 4.8 | [M – H − 1,4A]− |
309.0391 | −4.5 | [M – H − C8H16]− | ||||||
365.1009 | -6.0 | [M – H − C4H8]− | ||||||
25 | Mulberrochromene [40] | 17.50 | C25H24O6 | 419.15040 | 0.9 | 199.0781 | 8.0 | [M – H − 1,3A]− |
349.0726 | 2.3 | [M – H − C5H10]− | ||||||
26 | Dihydroisocycloartomunin [31] | 17.79 | C26H26O7 | 449.16080 | 0.5 | 191.0715 | 0.5 | [M – H − 1,4B]− |
365.0694 | 7.4 | [M – H − C6H12]− | ||||||
27 | Morusin [41] | 18.48 | C25H24O6 | 419.15040 | 0.9 | 191.0728 | 7.3 | [M – H − 1,4B]− |
217.0515 | 4.1 | [M – H − 1,3B]− | ||||||
227.0725 | 4.8 | [M – H − 1,4A]− | ||||||
28 | Heterophyllin [17] | 20.55 | C30H32O7 | 503.20842 | 2.1 | 217.0879 | 4.1 | [M – H − 1,3A]− |
243.0662 | −0.4 | [M – H − 1,4A]− | ||||||
259.1351 | 4.2 | [M – H − 1,4B]− | ||||||
285.1112 | 5.6 | [M – H − 1,3B]− | ||||||
29 | Artocarpetin B [42] | 20.72 | C22H22O6 | 381.13518 | 2.2 | 233.0806 | −5.6 | [M – H − 1,3B]− |
311.0549 | −3.9 | [M – H − C5H10]− | ||||||
30 | Artelastofuran [43] | 21.07 | C30H34O7 | 505.22363 | 0.9 | 277.1455 | 3.6 | [M – H − 1,4B]− |
285.1147 | 5.3 | [M – H − 0,3B]− | ||||||
31 | 5’-Hydroxycudraflavone A [17] | 21.81 | C25H22O7 | 433.12925 | −0.1 | 389.1372 | 5.7 | [M – H − CO2]− |
415.1192 | −1.2 | [M – H − H2O]− | ||||||
217.0516 | −4.6 | [M – H − 1,3A]− | ||||||
377.0663 | 1.1 | [M – H − C3H4O]− | ||||||
32 | Artonin F [44] | 22.04 | C30H30O7 | 501.19231 | 0.9 | 429.1343 | −0.2 | [M – H − C4H8O]− |
473.1945 | −5.3 | [M – H − CO]− | ||||||
33 | Isocycloheterophyllin [45] | 22.23 | C30H30O7 | 501.19290 | −2.0 | 445.1267 | −2.2 | [M – H − CH4]− |
485.1615 | −1.9 | [M – H − C3H4O]− | ||||||
443.1511 | −2.5 | [M – H − C3H6O]− | ||||||
34 | Artoindonesianin I [46] | 22.70 | C30H34O7 | 505.22363 | 0.9 | 285.1137 | 1.8 | [M – H − 0,3B]− |
447.1806 | −1.6 | [M – H − C3H6O]− | ||||||
35 | Artocarpin [47] | 23.48 | C26H28O6 | 435.18167 | 0.8 | 207.1039 | 5.8 | [M – H − 1,4B]− |
233.0818 | −0.4 | [M – H − 1,3B]− | ||||||
36 | Cannflavin C [20] | 23.59 | C26H28O6 | 435.18022 | −2.5 | 351.0878 | −1.1 | [M – H − C6H12]− |
323.0939 | −4.3 | [M – H − C6H7 − OCH3]− | ||||||
313.1452 | −2.2 | [M – H − C9H14]− | ||||||
37 | Artonin H [44] | 25.10 | C30H34O7 | 505.22363 | 0.9 | 191.0728 | 7.3 | [M – H − 1,4B]− |
217.0512 | 2.8 | [M – H − 1,3B]− | ||||||
38 | Artonin S [38] | 25.36 | C26H28O7 | 451.17621 | 0.0 | 393.1357 | 3.3 | [M – H − C3H6O]− |
421.1311 | 4.3 | [M – H − 2CH3]− | ||||||
39 | Artonin G [44] | 26.21 | C30H32O7 | 503.20862 | 2.2 | 447.1422 | −6.0 | [M – H − C4H8]− |
475.2103 | −4.8 | [M – H − CO]− | ||||||
40 | Artonin A [48] | 28.15 | C30H30O7 | 501.19231 | 0.9 | 457.1286 | −1.5 | [M – H − C3H8]− |
473.1950 | −4.2 | [M – H − CO]− | ||||||
41 | Artonin B [48] | 28.39 | C30H30O7 | 501.19230 | 0.8 | 485.1602 | 0.8 | [M – H − CH4]− |
445.1296 | −0.7 | [M – H − C3H4O]− | ||||||
42 | Cudraflavone A [49] | 28.41 | C25H22O6 | 417.13475 | 0.9 | 217.0515 | 4.1 | [M – H − 1,3B]− |
373.1072 | −2.4 | [M – H − C2H4O]− | ||||||
43 | Artoindonesianin G [46] | 29.45 | C30H32O6 | 487.21308 | 1.0 | 259.1351 | 4.2 | [M – H − 1,4B]− |
285.1116 | −5.6 | [M – H − 1,3B]− | ||||||
365.1762 | 1.1 | [M – H − C7H6O2]− | ||||||
44 | Cycloartocarpin [50] | 30.97 | C26H26O6 | 433.16608 | 1.0 | 199.0777 | 6.0 | [M – H − 1,3A]− |
363.0878 | 1.1 | [M – H − C5H10]− | ||||||
375.0878 | 1.1 | [M – H − C4H10]− | ||||||
45 | Artoindonesianin H [46] | 31.80 | C30H32O6 | 487.21308 | 1.0 | 227.0731 | 7.5 | [M – H − C9H18]− |
361.0731 | 3.6 | [M – H − 1,4A]− | ||||||
473.1966 | −0.8 | [M – H − CO]− | ||||||
46 | Cycloheterophyllin [17] | 33.05 | C30H30O7 | 501.19231 | 0.9 | 285.1145 | 4.6 | [M – H − 1,3B]− |
445.1281 | −2.7 | [M – H − C4H8]− | ||||||
473.1966 | −0.8 | [M – H − CO]− | ||||||
47 | Artelastochromene [43] | 36.01 | C30H30O6 | 485.19690 | −0.1 | 285.1145 | 4.6 | [M – H − 1,3B]− |
469.1659 | 0.4 | [M – H − CH4]− |
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Ye, J.-B.; Ren, G.; Li, W.-Y.; Zhong, G.-Y.; Zhang, M.; Yuan, J.-B.; Lu, T. Characterization and Identification of Prenylated Flavonoids from Artocarpus heterophyllus Lam. Roots by Quadrupole Time-Of-Flight and Linear Trap Quadrupole Orbitrap Mass Spectrometry. Molecules 2019, 24, 4591. https://doi.org/10.3390/molecules24244591
Ye J-B, Ren G, Li W-Y, Zhong G-Y, Zhang M, Yuan J-B, Lu T. Characterization and Identification of Prenylated Flavonoids from Artocarpus heterophyllus Lam. Roots by Quadrupole Time-Of-Flight and Linear Trap Quadrupole Orbitrap Mass Spectrometry. Molecules. 2019; 24(24):4591. https://doi.org/10.3390/molecules24244591
Chicago/Turabian StyleYe, Jin-Bao, Gang Ren, Wen-Yan Li, Guo-Yue Zhong, Min Zhang, Jin-Bin Yuan, and Ting Lu. 2019. "Characterization and Identification of Prenylated Flavonoids from Artocarpus heterophyllus Lam. Roots by Quadrupole Time-Of-Flight and Linear Trap Quadrupole Orbitrap Mass Spectrometry" Molecules 24, no. 24: 4591. https://doi.org/10.3390/molecules24244591