TABLE 4
Predicted metabolites of canadaline detected in urine following consumption of goldenseal supplement
| Identifier | Reaction | tR | Expected Ion | Measured Ion | Formula | Peak Area | MS/MS Fragments | Proposed Structure |
|---|---|---|---|---|---|---|---|---|
| min | m/z | m/z | m/z | |||||
| Canadaline | 41.6 | 370.1654 | 370.1656 (0.5) | C21H23NO5 | 470 | 190.0868a |  | |
| M43 | C-O reduction, O-demethylation | 35.1 | 358.1654 | 358.1651 (−0.8) | C20H24NO5 | 177 ± 79, 311 | 340.1559 |  |
| 192.1015 | ||||||||
| M44 | C-O reduction, O-demethylation, O-glucuronidation | 18.9 | 534.1975 | 534.1969 (−1.1) | C26H32NO11 | 29 ± 24, 50 | 358.1 |  |
| 192.1a | ||||||||
| M45 | C-O reduction, O-demethylation, O-glucuronidation | 24.8 | 534.1975 | 534.1959 (−3.0) | C26H32NO11 | 18 ± 11, 31 | 358.1 |  |
| 354.1 | ||||||||
| 178.1 | ||||||||
| M46, M47 | C-O reduction | 33.3 33.7 | 372.1811 | 372.1809 (−0.5) | C21H26NO5 | 106 ± 39, 186; 136 ± 68, 225 | 192.1 |  |
| 272.1 | ||||||||
| 354.1 | ||||||||
| M48 | C-O reduction, O-glucuronidation | 24.5, 27.0 | 548.2132 | 548.2111 (−3.8) | C27H34NO11 | 128 ± 68, 225; 549 ± 285, 964 | 372.1809 | 
 |
| M49 | 548.2117 (−2.7) | 368.1339 | ||||||
| 192.1034 | ||||||||
| M50 | C-O reduction, O-sulfation | 33.3 | 452.1379 | 452.1360 (−4.5) | C21H26NO8S | 500 ± 268, 877 | 372.1799 |  |
| 354.1687 | ||||||||
| 272.0598 | ||||||||
| 192.1031 |
↵a Diagnostic fragment ion. See Figure 3 for proposed fragmentation mechanism.