| | min | m/z | m/z | | | % | m/z | |
Hydrastine | Parent | 37.3 | 384.1447 | 384.1430 | C21H20NO6 | 625 ± 390 | 100 | 190.0892b | |
293.0850 |
323.0825 |
M1 | C-C reduction | 14.2 | 192.1024 | 192.1018 (+1.0) | C11H13NO2 | 261 ± 135 | 34 | 177.0787 | Hydrohydrastinin |
162.0776 |
M2 | C-C reduction | 25.5 | 195.0657 | 195.0661 (2.0) | C10H11O4 | 45 ± 19 | 6 | 180.0443 | Meconine |
162.0320 |
M3 | C-C reduction, dehydrogenation/C-C reduction, C-O reduction, aromatization | 15.4, 15.8 | 190.0868 | 190.0866 (−1.0), 190.0879 (+5.7) | C11H12NO2 | 1167 ± 509; 778 ± 312 | 151 | M3: 175.0633 | |
147.0677 |
154.0508 |
132.0365 |
M4 | | | | | | | 101 | M4: 175.0626 |
160.0755 |
149.0581 |
132.0365 |
M5 | C-C reduction, aromatization | 15.6 | 188.0712 | 188.0714 (+1.0) | C11H10NO2 | 3860 ± 1442 | 500 | 130.0555, 160.0676 | Hydrastonine |
M7 | C-C reduction, N-demethylation and N-sulfation | 11.9 | 258.0436 | 258.0434 (−0.8) | C10H12NO6S | 137 ± 72 | 18 | 178.0868 | |
M9 | C-C reduction, N-demethylation, hydroxylation and O-glucuronidation | 22.4 | 370.1138 | 370.1138 (0) | C16H20NO9 | 99 ± 77 | 13 | 194.0812 | |
M10 | C-C dehydrogenation | 30.8 | 382.1291 | 382.1278 (−3.4) | C21H20NO6 | 74 ± 42 | 10 | 334.0744 | |
322.1118 |
292.1011 |
278.0926 |
188.0712b |
M11 | Lactone hydrolysis, alcohol dehydrogenation | 27.6 | 400.1396 | 400.1388 | C21H22NO7 (−2.0) | 186 ± 59 | 24 | 382.1301 | |
190.0866b |
M12 | Hydroxylation | 37.3 | 400.1396 | 400.1402 | C21H22NO7 (+1.5) | 304 ± 157 | 39 | 190.0866b | |
311.0924 |
323.0917 |
335.0938 |
353.1053 |
M13,14 | Lactone hydrolysis, dehydrogenation, acyl glucuronidation | 27.2, 28.8 | 576.1717 | 576.1706 (−1.9), 576.1705 (−2.1) | C27H30NO13 | 72 ± 50 | 9 | M13: | |
382.1235 |
188.0721b |
M14: 382.1181 |
188.0697b |
M15 | C-C dehydrogenation | 32.4 | 382.1291 | 382.1289 (−0.5) | C21H20NO6 | 154 ± 98 | 20 | 322.1089 | CAS: 858196-25-5 |
307.1242 |
292.0983 |
278.0943 |
280.1007 |
190.0882b |
M16 | C-O reduction, O-demethylation | 21.4 | 372.1447 | 372.1437 (−2.7) | C20H22NO6 | 178 ± 100 | 23 | 354.1255 | CAS: 58298-46-7 |
323.0909 |
311.0941 |
178.0859b |
M18 | O-demethylation, O-sulfation | 27.4 | 450.0860 | 450.0851 (−1.8) | C20H20NO9S | 73 ± 70 | 9 | 370.1304 | |
309.0805 |
190.0887b |
M19 | O-demethylation, O-glucuronidation | 19.9 | 546.1612 | 546.1607 (−0.9) | C26H28NO12 | 508 ± 359 | 66 | 370.1288 | |
309.0797 |
190.0874b |
M20 | C-O reduction, O-demethylation, O-glucuronidation | 12.1 | 548.1768 | 548.1740 (−5.1) | C26H30NO12 | 355 ± 211 | 46 | 372.1447 | |
368.1266 |
311.0951 |
294.1451 |
192.1035b |
M21 | C-O reduction, O-demethylation, O-glucuronidation | 12.5 | 548.1768 | 548.1758 (−1.8) | C26H30NO12 | 533 ± 316 | 69 | 372.1425 | |
323.0960 |
311.0886 |
192.1035b |
165.0651 |
144.0820 |
M22 | C-O reduction, O-demethylation, O-sulfation | 18.8 | 452.1016 | 452.1016 (0) | C20H22NO9S | 117 ± 81 | 15 | 372.1456 | |
323.0952 |
311.0924 |
192.1018b |
M25 | N-demethylation, O-demethylation, O-glucuronidation | 19.3 | 532.1455 | 532.1452 (−0.6) | C25H26NO12 | 220 ± 138 | 29 | 514.1329 | |
356.1135 |
338.1030 |
176.0707b |
M 27 | C-O reduction, N-demethylation, O-demethylation, O-sulfation | 16.9 | 438.0860 | 438.0851 (−1.8) | C19H20NO9S | 145 ± 88 | 19 | 358.1266 | |
258.0418 |
297.0751 |
178.0871b |
M 29 | C-O reduction, N-demethylation, O-demethylation, O-sulfation | 18.6 | 438.0860 | 438.0867 (1.8) | C19H20NO9S | 48 ± 26 | 6 | 358.1269 | |
178.0868b |
M 30 | C-O reduction, N-demethylation, O-demethylation, O-glucuronidation | 12.7 | 534.1612 | 534.1601 (−2.1) | C25H28NO12 | 74 ± 73 | 10 | 516.1489 | |
358.1084 |
340.1005 |
178.0872b |
M 31 | N-demethylation, C-O reduction | 31.2 | 372.1447 | 372.1447 (0) | C20H22NO6 | 280 ± 128 | 36 | 354.1348 | |
178.0875b |
323.1196 |
M 32 | N-demethylation, C-O reduction, O-glucuronidation | 16.7 | 548.1768 | 548.1755 (−2.4) | C26H30NO12 | 579 ± 489 240 ± 108 | 75 | M32: 372.1442 | |
354.1183 |
178.0866b |
M 33 | 17.3 | 548.1753 (−2.7) | 31 | M33: 372.1435 |
354.1173 |
178.0865b |
M34 | N-demethylation | 34.3 | 370.1290 | 370.1300 | C20H20NO6 | | | 176.0796b | Norhydrastine |
321.1010 |
352.1186 |
M 36 | Lactone hydrolysis | 34.0 | 402.1553 | 402.1543 (−2.5) | C21H24NO7 | 329 ± 209 | 28 | 384.1447 | |
366.1384 |
353.1024 |
335.0919 |
323.0924 |
M 37 | Lactone hydrolysis, C-O reduction, O-glucuronidation | 15.9 | 580.2030 | 580.2019 (−1.9) | C27H34NO13 | 768 ± 504 | 100 | 562.1642 | |
404.1642 |
386.1659 |
368.1326 |
192.1000b |
M 39 | Hydroxylation, O-glucuronidation | 27.7 | 576.1717 | 576.1705 (−2.1) | C27H30NO13 | 235 ± 125 | 38 | 400.1353 | |
206.0389b |
451.2171 |
467.1917 |
M 40 | C-O reduction | 25.8 | 386.1604 | 386.1605 (0.3) | C21H24NO6 | 482 ± 246 | 62 | 368.1318 | |
337.1096 |
325.1057 |
192.1013b |
M 41 | C-O reduction, O-glucuronidation | 18.4 | 562.1925 | 562.1921 (−0.4) | C27H32NO12 | 2389 ± 1145 | 309 | 386.1584 | |
368.1327 |
325.1041 |
192.1028b |