Table 1. Compounds Detected with UHPLC-PDA-ESI-ITMS and UHPLC-PDA-ESI-FTMS after Incubation of GBG with Laccase from T. versicolor in the Presence or Absence of ABTS and HBTa.
| RT (min) | tentative annotation | molecular formula | ionization | observed/calculated mass | mass error (ppm) | MS2 fragments | λmax(nm) |
|---|---|---|---|---|---|---|---|
| Reaction Products of GBG Incubated with Laccase Alone | |||||||
| 20.8 | GBG | C17H20O6 | [M+Na]+ | 320.12556/320.12599 | –1.34 | 295 (55), 302 (16), 201 (8), 147 (6), 219 (5), 176 (4) | 278 |
| 34.8 | GBG dimer | C34H38O12 | [M–H]− | 638.23720/638.23633 | 1.36 | 589 (100), 483 (62), 513 (28), 435 (26), 329 (20), 465 (12), 541 (12), 359 (8) | 278 |
| 44.7 | GBG trimer | C51H56O18 | [M–H]− | 956.34775/956.34666 | 1.13 | 907 (100), 889 (60), 919 (30), 859 (20) | N.D. |
| Reaction Products of GBG Incubated with Laccase/HBT | |||||||
| 3.9 | HBT | C6H5N3O | [M–H]− | 135.04329/135.04326 | 0.23 | 106 (100), 78 (4) | 306, 276, 269 |
| [M+H]+ | 91 (63), 80 (40), 53 (18), 107 (8) | ||||||
| 7.2 | BT | C6H5N3 | [M+H]+ | 119.04832/119.04835 | –0.23 | N.D. | 260, 280 |
| 20.9 | GBG | C17H20O6 | [M+Na]+ | 320.12556/320.12599 | –1.34 | 295, 302, 201, 219, 147, 176 | 278 |
| 25.1 | GBG-HBT CP | C23H23N3O7 | [M–H]− | 453.15375/453.15360 | 0.33 | 404 (100), 328 (38), 298 (30) | 330 |
| 31.9 | GBG-HBT CPox | C23H21N3O7 | [M–H]− | 451.13838/451.13795 | 0.95 | 420 (100), 310 (27), 326 (15) | N.D. |
| 34.4 | GBG dimer | C34H38O12 | [M–H]− | 638.23720/638.23633 | 1.36 | 589 (100), 483 (62), 513 (28), 435 (26), 329 (20), 465 (12), 541 (12), 359 (8) | 278 |
| 44.7 | GBG trimer | C51H56O18 | [M–H]− | 956.34775/956.34666 | 1.13 | 907 (100), 889 (60), 919 (30), 859 (20) | N.D. |
| Reaction Products of GBG Incubated with Laccase/ABTS | |||||||
| 5.6 | ABTS CLP | C9H9NO4S2 | [M–H]− | 258.99757/258.99730 | 1.05 | 229 (37) | 256, 292, 285 |
| 8.7 | unknown | unknown | [M–H]− | 329.99756 | 302 (100), 238 (29), 222 (9) | 278 | |
| 17.0 | unknown | C25H25N4O8S4 | [M–2H]− | 637.05667/637.05553 | 1.79 | 363 (100), 378 (95), 228 (34), 605 (31), 405 (26), 257 (25), 335 (18) | 305 |
| 21.4 | ABTS | C18H18N4O6S4 | [M–2H]2– | 514* | N.D. | 342 | |
| 22.7 | GBG-ABTS CPII | C26H27N3O9S2 | [M–H]− | 589.11946/589.118876 | 0.99 | 242 (100), 214 (61), 228 (10) | 550 |
| 24.4 | GBG-ABTS CPIox | C35H35N4O12S4 | [M–3H]2– | 831.11369/831.11289 | 0.96 | 572 (100), 228 (43), 256 (42) | 305, 278 |
| [M–2H]− | N.D. | ||||||
| 28.3 | GBGox | C17H18O6 | [M–H]− | 318.11017/318.11034 | –0.52 | 287 (100), 193 (71) | 280, 311 |
| [M+H]+ | 167 (100), 149 (70), 271 (68), 151 (59), 195 (44), 269 (32), 177 (26), 289 (22) | ||||||
| [M+Na]+ | 311 (100), 218 (16), 146 (11), 187 (6) | ||||||
| 30.7 | GBG-ABTS CPIIox | C26H25N3O9S2 | [M–H]− | 587.10366/587.10322 | 0.76 | 242, 214, 556, 228 | 585, 448, 328 |
a
MS2 fragments and λmax were determined using UHPLC-PDA-ESI-ITMS. All other values were obtained using UHPLC-PDA-ESI-FTMS. Relative intensities of MS2 fragments are shown between brackets.* For ABTS, only data from UHPLC-PDA-ESI-ITMS were used, as FTMS only showed in-source fragmentation. N.D. = not detected.