Table 3.
Phenolic compounds identified in raw and bioprocessed hemp by HPLC-DAD-ESI-QTOF-MS. H, untreated hemp dough; HX, hemp dough treated with xylanase Depol 761P (1% wt/wt of fiber); HP, hemp dough treated with protease VeronPS (2.5% wt/wt of protein); HF, hemp dough fermented by Lactiplantibacillus plantarum 18S9 and Leuconostoc mesenteroides 12MM1 (ratio 1:1, final cell density of circa 7 log10 cfu/g). All treated samples were incubated at 30 °C for 24 h.
| N° | Polar Compound | RT (min) | Molecular Formula | m/z Expected | m/z Calculated | Error (ppm) | Score (%) | Fragments (MS2) |
|---|---|---|---|---|---|---|---|---|
| Free compounds | ||||||||
| 1 | Protocatechuic acid-glucoside isomer 1 | 2.946 | C13H16O9 | 315.0703 | 315.0716 | −4.1 | 99.78 | |
| 2 | Protocatechuic acid-glucoside isomer 2 | 3.281 | C13H16O9 | 315.0713 | 315.0716 | −1 | 98.96 | |
| 3 | Catechol | 4.560 | C6H6O2 | 109.0288 | 109.0290 | −1.8 | 92.24 | |
| 4 | 4-vinyl catechol | 4.730 | C8H8O2 | 135.0435 | 135.0446 | −8.1 | 87.98 | |
| 5 | Tuberonic acid glucoside isomer 1 | 7.939 | C18H28O9 | 387.1649 | 387.1655 | −1.5 | 94.94 | |
| 6 | 4-vinyl guaiacol | 8.178 | C9H10O2 | 149.0603 | 149.1770 | −14.1 | 79.88 | |
| 7 | Tuberonic acid glucoside isomer 2 | 8.295 | C18H28O9 | 387.1642 | 387.1655 | −3.4 | 94.94 | |
| 8 | 3-(3-Hydroxyphenyl)propionic acid | 8.530 | C9H10O3 | 165.0543 | 165.0552 | −5.5 | 92.86 | |
| 9 | 4-vinyl phenol | 8.543 | C8H8O0 | 119.0489 | 119.0497 | −6.7 | 81.46 | |
| 10 | Tuberonic acid glucoside isomer 3 | 8.783 | C18H28O9 | 387.1646 | 387.1655 | −2.3 | 94.94 | |
| 11 | Tuberonic acid glucoside isomer 4 | 8.882 | C18H28O9 | 387.1656 | 387.1655 | 0.3 | 94.94 | |
| 12 | Tuberonic acid glucoside isomer 5 | 9.797 | C18H28O9 | 387.1652 | 387.1655 | −0.8 | 94.94 | |
| 13 | N-caffeoyltyramine | 12.3 | C17H17NO4 | 298.1074 | 298.1079 | −1.7 | 99.54 | |
| 14 | Luteolin | 12.63 | C15H9O6 | 285.0396 | 285.0396 | −1.1 | 98.68 | |
| 15 | N-caffeoyltyramine | 13.81 | C17H17NO4 | 298.1074 | 298.1079 | −1.7 | 99.54 | |
| 16 | Cannabisin B isomer 1 | 15.98 | C34H32N2O8 | 595.2066 | 595.2080 | −2.4 | 78.54 | 432.1450, 322.1068, 269.0814 |
| 17 | Cannabisin B isomer 2 | 16.18 | C34H32N2O8 | 595.2076 | 595.2080 | −0.7 | 78.54 | 432.1450, 322.1068, 269.0814 |
| 18 | Cannabisin B isomer 3 | 16.81 | C34H32N2O8 | 595.2079 | 595.2080 | −0.1 | 78.54 | |
| 19 | Cannabisin B isomer 4 | 17.3 | C34H32N2O8 | 595.209 | 595.2080 | 1.7 | 78.54 | 432.1450, 322.1068, 269.0814 |
| 20 | Cannabisin C isomer 1 | 17.61 | C35H34N2O8 | 609.2242 | 609.2237 | 0.8 | 76.51 | |
| 21 | Cannabisin C isomer 2 | 17.87 | C35H34N2O8 | 609.2249 | 609.2237 | 2 | 76.51 | 446.1611, 283.0970, 268.0736 |
| 22 | Cannabisin C isomer 3 | 18.38 | C35H34N2O8 | 609.2243 | 609.2237 | 1 | 76.51 | |
| 23 | Cannabisin D isomer 1 | 19.04 | C36H36N2O8 | 623.2393 | 623.2393 | 0 | 70.77 | 460.1760, 445.1523 |
| 24 | Cannabisin D isomer 2 | 19.35 | C36H36N2O8 | 623.2386 | 623.2393 | −1.1 | 70.77 | 460.1760, 445.1523 |
| 25 | Cannabisin D isomer 3 | 20.73 | C36H36N2O8 | 623.2386 | 623.2393 | −1.1 | 70.77 | |
| 26 | Trihydroxyoctadeceno ic acid | 21.11 | C18H34O5 | 329.2320 | 329.2328 | −2.4 | 98.65 | |
| 27 | Trihydroxyoctadeceno ic acid | 21.21 | C18H34O5 | 329.2319 | 329.2328 | −0.9 | 98.65 | |
| 28 | Trihydroxyoctadeceno ic acid | 21.32 | C18H34O5 | 329.2326 | 329.2328 | −0.2 | 98.65 | |
| 29 | Cannabisin D isomer 4 | 21.57 | C36H36N2O8 | 623.2393 | 623.2393 | 0 | 70.77 | 460.1760, 445.1523 |
| 30 | Cannabisin D isomer 5 | 21.74 | C36H36N2O8 | 623.2409 | 623.2393 | 2.6 | 70.77 | |
| 31 | Cannabidiolic acid glucoside | 23.35 | C28H40O9 | 519.2593 | 519.2594 | −0.2 | 56.29 | 373.1255 |
| 32 | Cannabielsoic acid | 23.61 | C22H30O5 | 373.2012 | 373.2015 | −0.8 | 97.08 | |
| 33 | Cannabielsoic acid | 23.65 | C22H30O5 | 373.2014 | 373.2015 | −0.3 | 97.08 | |
| 34 | Cannabielsoic acid | 23.86 | C22H30O5 | 373.2008 | 373.2015 | −0.7 | 97.08 | |
| 35 | Cannabielsoic acid | 23.97 | C22H30O5 | 373.2015 | 373.2015 | 0 | 97.08 | |
| 36 | Cannabielsoic acid | 24.12 | C22H30O5 | 373.2008 | 373.2015 | −0.7 | 97.08 | |
| 37 | Cannabielsoic acid | 24.41 | C22H30O5 | 373.2013 | 373.2015 | −0.5 | 97.08 | |
| 38 | Cannabielsoic acid | 24.92 | C22H30O5 | 373.2025 | 373.2015 | 2.7 | 97.08 | |
| 39 | THCA derivative | 25.18 | C46H58O8 | 737.4056 | 737.4053 | 0.4 | 96.53 | |
| 40 | Fatty acid C18:3 | 25.77 | C18H30O2 | 277.2158 | 277.2168 | −3.6 | 99.75 | |
| 41 | Fatty acid C18:3 | 25.806 | C18H30O2 | 277.2164 | 277.2168 | −1.4 | 97.64 | |
| 42 | Fatty acid C18:2 | 26.117 | C18H32O2 | 279.232 | 279.2324 | −1.14 | 91.75 | |
| Bound compounds | ||||||||
| 1 | Citric acid | 0659 | C6H8O7 | 191.0182 | 191.0192 | −5.2 | 79.55 | 111.0079 |
| 2 | Citric acid | 0.882 | C6H8O8 | 191.0185 | 191.0192 | −3.7 | 79.55 | 111.0079 |
| 3 | Protocatechuic acid derivative | 3.231 | C15H8O9 | 331.0024 | 331.256 | 1.2 | 98.65 | 153.0186, 109.0287 |
| 4 | Protocatechuic acid glucoside | 4.357 | C13H16O9 | 315.0654 | 315.0716 | −19.7 | 70.77 | |
| 5 | Salicylic acid derivative | 4.849 | C15H8O7 | 299.0131 | 299.0192 | −17.7 | 98.65 | 137.0233 |
| 6 | Benzoic acid aldehyde | 6.566 | C7H6O2 | 121.0283 | 121.029 | −5.8 | 79.27 | 92.0246 |
| 7 | Catechin | 6.619 | C15H14O6 | 289.0702 | 289.0712 | −3.5 | 75.65 | |
| 8 | Xerocomic acid | 8.659 | C18H12O8 | 355.0442 | 355.0454 | −3.1 | 86.29 | 337.0336, 311.0544, 267.0651 |
| 9 | trans p-Coumaric acid | 9.24 | C9H8O3 | 163.0388 | 163.0395 | −4.3 | 98.97 | 119.0485 |
| 10 | cis p-Coumaric acid | 9.47 | C9H8O3 | 163.0386 | 163.0395 | −5.5 | 96.28 | 119.0485 |
| 11 | Coumaric acid derivative | 9.84 | C18H16O6 | 327.0858 | 327.0869 | −4.3 | 95.71 | 163.039, 119.0481 |
| 12 | Coumaric acid derivative | 10.36 | C18H16O6 | 327.0858 | 327.0869 | −4.3 | 95.71 | 163.039, 119.0481 |
| 13 | Flavodic acid | 10.87 | C19H14O8 | 369.0589 | 369.061 | −5.7 | 96.08 | 337.0344, 265.0555 |
| 14 | Flavodic acid | 12.151 | C19H14O8 | 369.0589 | 369.061 | −2.4 | 95.98 | 337.0344. 265.0493 |
| 15 | Flavodic acid | 12.8 | C19H14O8 | 369.0589 | 369.061 | −2.4 | 95.98 | |
| 16 | N-caffeoyltyramine | 13.87 | C17H17NO4 | 298.1096 | 298.1079 | −5 | 98.29 | 178.0506, 135.0434 |
| 17 | Flavodic acid derivative | 14.11 | C20H16O8 | 383.0779 | 383.0767 | 3.1 | 95.56 | 337.0344, 351.0500, 263.0555 |
| 18 | Cannabisin B isomer 1 | 16.06 | C34H32N2O8 | 595.2089 | 595.208 | −1.3 | 97.08 | |
| 19 | Cannabisin B isomer 2 | 16.23 | C34H32N2O8 | 595.2089 | 595.208 | 1.5 | 97.08 | 432.1450, 322.1068, 269.0814 |
| 20 | N-trans-feryroyltyramine | 16.544 | C18H19NO4 | 312.1225 | 312.1236 | −3.5 | 92.64 | 190.0481, 135.0426, 178.0484 |
| 21 | Cannabisin B isomer 3 | 16.853 | C34H32N2O8 | 595.2092 | 595.208 | 2 | 97.08 | 432.1450, 322.1068, 269.0814 |
| 22 | Cannabisin B isomer 4 | 17.24 | C34H32N2O8 | 595.2092 | 595.208 | 1 | 97.08 | |
| 23 | Cannabisin B isomer 5 | 17.366 | C34H32N2O8 | 595.2072 | 595.208 | −1.3 | 97.08 | 485.1701, 432.1450, 322.1068, 269.0814 |
| 24 | Cannabisin C isomer 1 | 17.65 | C35H34N2O8 | 609.2229 | 609.2237 | −1.3 | 96.22 | |
| 25 | Cannabisin B isomer 6 | 17.773 | C34H32N2O8 | 595.2065 | 595.208 | −2.5 | 97.08 | 322.1068, 269.0814 |
| 26 | Cannabisin C isomer 2 | 17.93 | C35H34N2O8 | 609.2229 | 609.2237 | −1.1 | 96.22 | |
| 27 | Cannabisin C isomer 3 | 18.12 | C35H34N2O8 | 609.2229 | 609.2237 | −1.2 | 96.22 | |
| 28 | Cannabisin C isomer 4 | 18.42 | C35H34N2O8 | 609.2231 | 609.2237 | −1 | 96.22 | 446.1611, 283.0970, 268.0736 |
| 29 | Cannabisin D isomer 1 | 19.06 | C36H36N2O8 | 623.2392 | 623.2393 | −0.2 | 98.39 | 460.1760, 445.1523 |
| 30 | Cannabisin B isomer 7 | 19.19 | C34H32N2O8 | 595.2065 | 595.208 | −2.5 | 97.08 | 432.1450, 322.1068, 269.0814 |
| 31 | Cannabisin B isomer 8 | 19.55 | C34H32N2O8 | 595.2065 | 595.208 | −2.5 | 97.08 | 432.1450, 322.1068, 269.0814 |
| 32 | Cannabisin D isomer 2 | 19.378 | C36H36N2O8 | 623.2402 | 623.2393 | 1.4 | 98.39 | |
| 33 | Cannabisin E isomer 1 | 19.633 | C36H38N2O9 | 641.2493 | 641.2499 | 1.6 | 97.81 | 489.2026, 328.1187, 151.0380 |
| 34 | Cannabisin E isomer 2 | 19.92 | C36H38N2O9 | 641.2509 | 641.2499 | 1.6 | 97.81 | 489.2026, 328.1187, 151.0380 |
| 35 | Cannabisin C isomer 5 | 20.156 | C35H34N2O8 | 609.2242 | 609.2237 | 0.8 | 96.22 | |
| 36 | Cannabisin D isomer 3 | 20.21 | C36H36N2O8 | 623.2398 | 623.2393 | 0.8 | 98.39 | |
| 37 | Cannabisin C isomer 6 | 20.52 | C35H34N2O8 | 609.223 | 609.2237 | −1.1 | 96.22 | |
| 38 | Cannabisin D isomer 4 | 21.579 | C36H36N2O8 | 623.2405 | 623.2393 | 1.9 | 98.39 | |
| 39 | THCA derivative | 25.18 | C46H58O8 | 737.4056 | 737.4053 | 0.4 | 96.53 | |