min m/z m/z % m/z Hydrastine Parent 37.3 384.1447 384.1430 C21 H20 NO6 625 ± 390 100 190.0892b 293.0850 323.0825 M1 C-C reduction 14.2 192.1024 192.1018 (+1.0) C11 H13 NO2 261 ± 135 34 177.0787 Hydrohydrastinin162.0776 M2 C-C reduction 25.5 195.0657 195.0661 (2.0) C10 H11 O4 45 ± 19 6 180.0443 Meconine162.0320 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) C11 H12 NO2 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) C11 H10 NO2 3860 ± 1442 500 130.0555, 160.0676 HydrastonineM7 C-C reduction, N -demethylation and N -sulfation 11.9 258.0436 258.0434 (−0.8) C10 H12 NO6 S 137 ± 72 18 178.0868 M9 C-C reduction, N -demethylation, hydroxylation and O -glucuronidation 22.4 370.1138 370.1138 (0) C16 H20 NO9 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 C21 H22 NO7 (−2.0) 186 ± 59 24 382.1301 190.0866b M12 Hydroxylation 37.3 400.1396 400.1402 C21 H22 NO7 (+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) C27 H30 NO13 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) C21 H20 NO6 154 ± 98 20 322.1089 CAS: 858196-25-5307.1242 292.0983 278.0943 280.1007 190.0882b M16 C-O reduction, O -demethylation 21.4 372.1447 372.1437 (−2.7) C20 H22 NO6 178 ± 100 23 354.1255 CAS: 58298-46-7323.0909 311.0941 178.0859b M18 O -demethylation, O -sulfation27.4 450.0860 450.0851 (−1.8) C20 H20 NO9 S 73 ± 70 9 370.1304 309.0805 190.0887b M19 O -demethylation, O -glucuronidation19.9 546.1612 546.1607 (−0.9) C26 H28 NO12 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) C26 H30 NO12 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) C26 H30 NO12 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) C20 H22 NO9 S 117 ± 81 15 372.1456 323.0952 311.0924 192.1018b M25 N -demethylation, O -demethylation, O -glucuronidation19.3 532.1455 532.1452 (−0.6) C25 H26 NO12 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) C19 H20 NO9 S 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) C19 H20 NO9 S 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) C25 H28 NO12 74 ± 73 10 516.1489 358.1084 340.1005 178.0872b M 31 N -demethylation, C-O reduction31.2 372.1447 372.1447 (0) C20 H22 NO6 280 ± 128 36 354.1348 178.0875b 323.1196 M 32 N -demethylation, C-O reduction, O -glucuronidation16.7 548.1768 548.1755 (−2.4) C26 H30 NO12 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 -demethylation34.3 370.1290 370.1300 C20 H20 NO6 176.0796b Norhydrastine321.1010 352.1186 M 36 Lactone hydrolysis 34.0 402.1553 402.1543 (−2.5) C21 H24 NO7 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) C27 H34 NO13 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) C27 H30 NO13 235 ± 125 38 400.1353 206.0389b 451.2171 467.1917 M 40 C-O reduction 25.8 386.1604 386.1605 (0.3) C21 H24 NO6 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) C27 H32 NO12 2389 ± 1145 309 386.1584 368.1327 325.1041 192.1028b