Table 1.
Structural Information of the Metabolites of δ-, γ-, α-Tocopherols Obtained by LC-MSn in Negative ESI Sourcea
| Compound | Rt1 (min) | Rt2 (min) | MSn fragments (relative intensity, %) |
|---|---|---|---|
| δ-CEHC | 6.1 | 5.3 |
MS2/249: 205 (100), 157 (10); MS3/205: 190 (30), 135 (100), 122 (15). |
| γ-CEHC | 7.4 | 6.2 |
MS2/263: 245 (5), 219 (100), 171 (15); MS3/219: 204 (30), 149 (100), 136 (10). |
| α-CEHC | 8.1 | 8.0 |
MS2/277: 259 (30), 233 (100), 185 (50); MS3/233: 218 (40), 176 (10), 163 (100), 150 (15). |
| δ-CMBHC | 11.0 | 9.3 |
MS2/291: 273 (10), 247 (100), 135 (5), 122 (20); MS3/247: 229 (18), 148 (80), 135 (100). |
| γ-CMBHC | 12.6 | 11.5 |
MS2/305: 287 (15), 261 (100), 149 (5), 136 (45); MS3/261: 191 (40), 162 (80), 149 (100). |
| α-CMBHC | 13.9 | 13.0 |
MS2/319: 301 (40), 275 (100), 163 (10), 150 (10); MS3/275: 176 (50), 163 (100), 150 (20). |
| δ-CMHHC | 15.0 | 15.4 | MS2/319: 301 (100), 183 (15), 135(20), 122 (25). |
| γ-CMHHC | 16.5 | 17.0 | MS2/333: 315 (100), 183 (20), 149 (35), 136 (25). |
| α-CMHHC | 18.0 | 18.0 | MS2/347: 329 (100), 183 (20), 163 (20), 150 (15). |
| δ-CDMOHC | 19.1 | 18.9 |
MS2/361: 343 (100), 225 (35), 135 (35), 122 (35); MS3/343: 188 (60), 174 (60), 148 (20), 135 (100). |
| γ-CDMOHC | 20.1 | 20.0 | MS2/375: 357 (100), 225 (70), 149 (70), 136 (50). |
| α-CDMOHC | 20.9 | 20.7 | MS2/389: 371 (100%), 225 (10), 163 (10), 150 (10). |
| δ-CDMDHC | 22.2 | 23.8 |
MS2/389: 371 (100), 253 (15), 135 (15), 122 (10); MS3/371: 188 (40), 174 (40), 148 (20), 135 (100). |
| γ-CDMDHC | 23.0 | 25.8 |
MS2/403: 385 (100), 341 (20), 253 (25), 149 (25), 136 (15). |
| α-CDMDHC | 23.8 | 26.0 |
MS2/417: 399 (100), 253 (40), 163 (15), 150 (10); MS3/399: 202 (10), 163 (100). |
| Carboxyl δ-tocopherol | 23.8 | 24.8 |
MS2/431: 413 (100), 295 (49), 135 (15), 122 (10); MS3/413: 202 (20), 174 (80), 135 (100). |
| Carboxyl γ-tocopherol | 24.8 | 26.7 | MS2/445: 427 (100), 295 (75), 149 (35), 136 (35). |
| Carboxyl α-tocopherol | 26.0 | 28.5 |
MS2/459: 441 (100), 295 (70), 163 (90), 150 (90); MS3/441: 202 (5), 186 (5), 163 (100), 150 (10). |
| δ-tocopherol | 35.6 | 36.7 | MS2/401: 386 (100), 135 (20). |
| γ-tocopherol | 37.9 | 37.7 | MS2/415: 400 (100), 149 (30). |
| α-tocopherol | 40.6 | 38.9 | MS2/429: 414 (20), 163 (100). |
a
The retention times on LC–MS/MS (Rt1) and on HPLC/EC (Rt2) are shown. The retention times in these two separations were different, but the elution sequences were the same.