Table 2.
Compounds annotated in a collection of 52 hemp seed accessions.
| # | Rt | Class | Annotation | Molecular formula | Positive ionization | Positive MS2 ions (intensity) | Negative ionization | Negative MS2 ions (intensity) | Error (ppm) | Reference | MSIa |
|---|---|---|---|---|---|---|---|---|---|---|---|
| 1 | 1.65 | Sugars | Sucrose | C12H22O11 | [M+NH4]+ 360.15067 | 325 (100), 343 (46), 289 (17), 307 (11), 259 (7), 198 (7), 145 (5) | [M - H]- 341.10840 | 179 (100), 161 (21), 143 (16), 113 (14), 101 (7), 131 (6) | 0.04 | Current study | 1 |
| 2 | 2.50 | Organic acids | Citric acid | C6H8O7 | – | – | [M - H]- 191.01965 | 111 (100), 172 (24) | 2.46 | Current study | 1 |
| 3 | 4.02 | Phenolic acids | Protocatechuic acid hexoside | C13H16O9 | – | – | [M - H]- 315.07214 | 152 (100), 271 (21), 165 (13), 253 (12), 108 (12), 225 (9), 243 (7), 299 (5) | 1.69 | Kew database | 2 |
| 4 | 5.19 | Phenylpropionamides | Coumaroyl-amino butanol glucopyranoside | C19H27O8N | [M + H]+ 398.18103 | 147 (100), 309 (65), 291 (14), 236 (14) | – | – | 1.17 | (Moccia et al., 2020) | 2 |
| 5 | 6.84 | Glucosyl sulphates | Ferulic acid 4-O-glucosyl-6’-O-sulphate (Cannabigail) | C16H20O12S | – | – | [M - H]- 435.06061 | 241 (100), 223 (5), 193 (5) | 0.78 | Current study | 1 |
| 6 | 5.88 | Glucosyl sulphates | Caffeic acid glucosyl sulphate | C15H18O12S | – | – | [M - H]- 421.04361 | 241 (100), 179 (10) | 1.10 | Current study | 3 |
| 7 | 6.23 | Glucosyl sulphates | Cinnamic acid glucosyl sulphate (Cuinnabis) | C15H18O11S | – | – | [M - H]- 405.04938 | 241 (100), 325 (5), 223 (4), 139 (4), 163 (3) | 0.81 | Current study | 3 |
| 8 | 7.85 | Glucosyl sulphates | Dimethoxy cinnamic acid glucosyl sulphate | C17H22O13S | – | – | [M - H]- 465.07037 | 241 (100), 223 (5) | 0.18 | Current study | 3 |
| 9 | 8.44 | Glucosyl sulphates | Ferulic acid glucosyl sulphate isomer | C16H20O12S | – | – | [M - H]- 435.05972 | 241 (100), 193 (5) | 1.26 | Current study | 3 |
| 10 | 10.31 | Cinnamic acid amides | N-trans-feruloyltyramine glycoside | C24H29NO9 | [M + H]+ 476.19138 | 314 (100), 177 (8), 145 (2) | [M - H]- 474.17648 | 312 (100) | 1.42 | (Leonard et al., 2021b) | 2 |
| 11 | 11.69 | Cinnamic acid amides | N-trans-caffeoyltyramine | C17H17NO4 | [M + H]+ 300.12317 | 163 (100), 121 (10), 138 (9) | [M - H]- 298.10846 | 135 (100), 178 (46), 161 (38), 256 (12), 107 (6) | 1.38 | (Leonard et al., 2021b) | 2 |
| 12 | 13.13 | Cinnamic acid amides | N-trans-feruloyltyramine | C18H19NO4 | [M + H]+ 314.13882 | 177 (100), 145 (15) | [M - H]- 312.12427 | 297 (100), 178 (92), 135 (44), 148 (18), 270 (15), 176 (12), 191 (8), 312 (6), 253 (5), | 1.32 | (Leonard et al., 2021b) | 2 |
| 13 | 12.90 | Cinnamic acid amides | N-trans-coumaroyltyramine | C17H17NO3 | [M + H]+ 284.12814 | 147 (100) | [M - H]- 282.11328 | 119 (100), 145 (80), 162 (50), 134 (21), 240 (12) | 1.85 | (Leonard et al., 2021b) | 2 |
| 14 | 14.89 | Cinnamic acid amides | tri-p-coumaroylspermidine | C34H37N3O6 | [M + H]+ 584.27612 | 420 (100), 438 (80) | [M - H]- 582.26062 | 462 (100), 342 (12), 436 (9) | 0.09 | (Nigro et al., 2020) | 2 |
| 15 | 8.95 | Cinnamic acid amides | N-trans-caffeoyloctopamine | C17H17NO5 | [M + H]+ 316.11804 | 298 (100), 255 (10), 168 (8) | [M - H]- 314.10349 | 296 (100), 202 (10) | 1.44 | (Leonard et al., 2021b) | 2 |
| 16 | 10.11 | Lignanamides | N- caffeoyltyramine/N- caffeoyloctopamine dimer | C34H32N2O9 | [M + H]+ 613.21814 | 595 (100), 460 (12), 476 (4) | [M - H]- 611.20239 | 593 (100), 430 (26), 501 (10), 320 (10), 448 (7) | 0.75 | (Nigro et al., 2020) | 3 |
| 17 | 12.31 | Lignanamides | Cannabisin B | C34H32N2O8 | [M + H]+ 597.22308 | 460 (100), 432 (4) | [M - H]- 595.20789 | – | 1.03 | (Leonard et al., 2021b) | 2 |
| 18 | 12.69 | Lignanamides | Cannabisin B isomer | C34H32N2O8 | [M + H]+ 597.22290 | 460 (100), 432 (20), 350 (9) | [M - H]- 595.20746 | 485 (100), 432 (15) 322 (15), 456 (4) | 1.33 | (Leonard et al., 2021b) | 3 |
| 19 | 12.91 | Lignanamides | Cannabisin B isomer | C34H32N2O8 | [M + H]+ 597.22369 | 460 (100), 297 (20), 434 (7), 418 (5), 279 (4) | [M - H]- 595.20728 | 485 (100), 432 (92) 322 (28), 458 (14), 416 (14), 269 (12) | 0.008 | (Leonard et al., 2021b) | 3 |
| 20 | 13.95 | Lignanamides | 3’3-demethylgrossamide | C34H32N2O8 | [M + H]+ 597.22357 | 434 (100), 297 (40), 460 (32), 323(13) 271 (8), 279 (6) | [M - H]- 595.20837 | 432 (100), 458 (19), 269 (12), 338 (5) | 0.21 | (Leonard et al., 2021b) | 2 |
| 21 | 14.82 | Lignanamides | Cannabisin M | C34H32N2O8 | [M + H]+ 597.22345 | 434 (100), 297 (78), 300 (44), 460 (39), 187 (8) | [M - H]- 595.20721 | 298 (100), 432 (5) | 0.41 | (Leonard et al., 2021b) | 2 |
| 22 | 14.96 | Lignanamides | Cannabisin Q | C34H32N2O8 | [M + H]+ 597.22327 | 434 (100), 297 (95), 460 (55), 300 (30) 279 (4), 187 (4) | [M - H]- 595.20715 | 298 (100), 432 (5) | 0.71 | (Leonard et al., 2021b) | 2 |
| 23 | 12.24 | Lignanamides | Cannabisin A | C34H30N2O8 | [M + H]+ 595.20770 | 458 (100), 350 (2) | [M - H]- 593.19159 | 456 (100), 430 (38), 293 (4) | 1.35 | (Nigro et al., 2020) | 2 |
| 24 | 12.04 | Lignanamides | Rac-sativamide A | C33H30N2O8 | [M + H]+ 583.20758 | 565 (100), 446 (87), 418 (33), 255 (8) | [M - H]- 581.19086 | 400 (100), 513 (8), 535 (7), 418 (6), 443 (5) | 0.76 | (Leonard et al., 2021b) | 2 |
| 25 | 12.69 | Lignanamides | Cannabisin H | C28H31NO8 | [M + H]+ 510.21204 | 492 (100), 312 (42), 462 (35), 355 (37), 177 (8), 201 (7), 474 (6), 338 (5) | [M - H]- 508.19772 | 312 (100), 460 (68), 490 (8), 366 (6) | 1.48 | (Leonard et al., 2021b) | 2 |
| 26 | 14.43 | Lignanamides | Grossamide K | C28H29NO7 | [M + H]+ 492.20178 | 462 (100), 325 (37), 337 (14), 355 (8) | [M - H]- 490.18640 | 472 (100), 460 (13) | 0.90 | (Leonard et al., 2021b) | 2 |
| 27 | 13.04 | Lignanamides | Cannabisin C | C35H34N2O8 | [M + H]+ 611.23846 | 474 (100), 446 (4) | [M - H]- 609.22308 | 446 (100), 283 (20), 499 (8) | 1.45 | (Leonard et al., 2021b) | 2 |
| 28 | 13.53 | Lignanamides | Cannabisin C isomer | C35H34N2O8 | [M + H]+ 611.23859 | 474 (100), 311 (32), 448 (12), 432 (6) | [M - H]- 609.22260 | 446 (100), 283 (12), 485 (5), 322 (5) | 1.23 | (Leonard et al., 2021b) | 3 |
| 29 | 14.56 | Lignanamides | Cannabisin N or isomer | C35H34N2O8 | [M + H]+ 611.24005 | 448 (100), 311 (34), 474 (29), 337 (19), 285 (8), 293 (5), 355 (4) | [M - H]- 609.22333 | 446 (100), 283 (15), 472 (5) | 1.45 | (Leonard et al., 2021b) | 3 |
| 30 | 15.48 | Lignanamides | Cannabisin N or isomer | C35H34N2O8 | [M + H]+ 611.23877 | 448 (100), 311 (60), 474 (42), 314 (32), 187 (10), 298 (7) | [M - H]- 609.22229 | 312 (100), 417 (76), 296 (69), 446 (32), 501 (16), 581 (16), 591 (10) | 0.94 | (Leonard et al., 2021b) | 3 |
| 31 | 15.75 | Lignanamides | Cannabisin N or isomer | C35H34N2O8 | [M + H]+ 611.23822 | 311 (100), 448 (78), 474 (56), 324 (6), 293 (6) | [M - H]- 609.22235 | 312 (100), 296 (62), 446 (38), 417 (12), 473 (10) | 1.84 | (Leonard et al., 2021b) | 3 |
| 32 | 13.71 | Lignanamides | Cannabisin D | C36H36N2O8 | [M + H]+ 625.25446 | 488 (100), 460 (6) | [M - H]- 623.23877 | 460 (100), 283 (7), 446 (7) | 0.85 | (Leonard et al., 2021b) | 2 |
| 33 | 14.21 | Lignanamides | Cannabisin G | C36H36N2O8 | [M + H]+ 625.25409 | 488 (100), 460 (6) | [M - H]- 623.23907 | 460 (100), 446 (20), 336 (12), 499 (9) | 1.44 | (Leonard et al., 2021b) | 2 |
| 34 | 15.46 | Lignanamides | Cannabisin F | C36H36N2O8 | [M + H]+ 625.25397 | 462 (100), 325 (41), 488 (10), 351 (9), 307 (5), 299 (5) | [M - H]- 623.23853 | 460 (100), 297 (20), 486 (12) | 1.64 | (Leonard et al., 2021b) | 2 |
| 35 | 16.08 | Lignanamides | Grossamide | C36H36N2O8 | [M + H]+ 625.25433 | 488 (100), 462 (48), 351 (13), 325 (7) | [M - H]- 623.23871 | 592 (100), 433 (37), 551 (28), 471 (24), 460 (22), 503 (12), 515 (8) | 1.06 | (Leonard et al., 2021b) | 2 |
| 36 | 14.35 | Lignanamides | Cannabisin E | C36H38N2O9 | [M + H]+ 643.26483 | 462 (100), 625 (19), 338 (7), 488 (5) | [M - H]- 641.24988 | 489(100), 623 (82), 431 (12), 312 (11), 460 (9), 328 (9), 517 (6) | 1.12 | (Leonard et al., 2021b) | 2 |
| 37 | 14.64 | Lignanamides | cis-Cannabisin E | C36H38N2O9 | [M + H]+ 643.26495 | 462 (100), 625 (24), 338 (8), 478 (8), 450 (5) | [M - H]- 641.24908 | 489 (100), 623 (75), 431 (11), 312 (11), 460 (10), 517 (6), | 0.94 | (Leonard et al., 2021b) | 2 |
| 38 | 16.25 | Lignanamides | Cannabisin O | C54H53N3O12 | [M + H]+ 936.36957 | 799 (100), 771 (5) | [M - H]- 934.35425 | 902 (100), 771 (80), 765 (54), 739 (38), 797 (25), 826 (10), 641 (8) | 1.23 | (Leonard et al., 2021b) | 2 |
| 39 | 21.82 | Cannabinoids | Cannabidiol or Tetrahydrocannabinol isomer | C21H30O2 | [M + H]+ 315.23193 | not fragmented | – | – | 1.51 | (Citti et al., 2019) | 3 |
| 40 | 23.35 | Cannabinoids | Tetrahydrocannabinol | C21H30O2 | [M + H]+ 315.23187 | 297 (28), 259 (100), 235 (40), 233 (42), 221 (32), 207 (22), 193 (82), 181 (32), 135 (32) | – | – | 1.70 | (Citti et al., 2019) | 3 |
| 41 | 22.16 | Cannabinoids | Tetrahydrocannabinolic acid | C22H30O4 | [M + H]+ 359.22186 | [MS2] 341 (100), [MS3] 299 (10), 285 (48), 261 (72), 247 (8), 233 (30), 219 (100), 207 (12), 135 (4) | – | – | 1.04 | (Citti et al., 2019) | 3 |
| 42 | 20.13 | Lipids | Unknown fatty acid | C18H32O4 | [M + H]+ 313.23755 | 295 (100), 277 (54), 227 (16), 209 (8), 259 (4) | – | – | 1.07 | – | 4 |
| 43 | 21.78 | Lipids | Unknown fatty acid | C18H30O3 | [M + H]+ 295.22678 | 277 (100), 257 (7), 237 (3), 221 (3) | – | – | 1.81 | – | 4 |
| 44 | 22.35 | Lipids | Unknown fatty acid | C18H32O3 | [M + H]+ 297.24258 | 279 (100), 261 (6), 243 (3), 163 (3) | – | – | 1.29 | – | 4 |
a
Confidence level of identification according to the Metabolomics standards initiative (1: Rt, HRMS and MS2 match with a pure standard; 2: HRMS and MS2 match with literature information; 3: tentative identity suggested by interpretation of MS2 spectra and literature information; unknown compounds).