Table 2.
Identification of compounds in Danshen by HPLC-MSn.
| ID | tR (min) | Mass Ion (m/z) | Data-Dependent MSn Data (m/z) | Identification |
|---|---|---|---|---|
| 1 a | 4.79 | [M − H]⁻ 197.0452 | MS2：178.9395 MS3: 134.9681, 106.9022 | Danshensu |
| 2 | 6.19 | [M − H]⁻ 153.0191 | MS2: 109.0295 | Protocatechuic acid |
| 3 | 7.98 | [M − H]⁻ 341.1076 | MS2：178.9334, 160.8835, 112.8926 | 1-O-caffeoyl glucose |
| 4 a | 8.96 | [M − H]⁻ 137.0242 | MS2: 109.0310 | Protocatechuic aldehyde |
| 5 | 13.43 | [M − H]⁻ 179.0344 | MS2: 135.0451 | Caffeic acid |
| 6 | 15.10 | [M − H]⁻ 683.1226 | MS2: 665.2238, 621.3198, 441.1573 | 3,4-Dihydroxy-(1α,3α,4α,5β)-1-carboxy-4-hydroxy-1,3,5-cyclohexanetriyl ester-benzenepropanoic acid |
| 7 | 15.74 | [M − H]⁻ 313.0707 | MS2: 269.0386, 158.9700, 108.8062 | Salvianolic acid F |
| 8 | 17.97 | [M − H]⁻ 539.1178 | MS2: 521.1625, 495.3337, 359.1708, 341.1323, 297.1190 | Yunnaneic acid D/isomer |
| 9 | 19.34 | [M − H]⁻ 521.1287 | MS2: 498.5744, 477.9366, 359.1708, 341.1323, 297.1190 | Salviaflaside |
| 10 | 22.09 | [M − H]⁻ 339.0501 | MS2: 320.9998, 294.9889, 184.9634 | Salvianolic acid G |
| 11 | 22.76 | [M − H]⁻ 735.1541 | MS2: 716.9385, 537.1756, 519.1987, 555.0787 | Hydrosalvianolic acid B |
| 12 | 25.17 | [M − H]⁻ 717.1436 | MS2: 693.3942, 519.1561, 321.0740, 537.1210 | Iso salvianolic acid E |
| 13 a | 26.43 | [M − H]⁻ 359.0763 | MS2: 341.1426, 160.8524, 197.0617, 178.8373 MS3: 160.9093, 132.8333 |
Rosmarinic acid |
| 14 | 28.12 | [M − H]⁻ 537.1038 | MS2: 493.1133, 313.0726, 295.0606 | Lithospermic acid |
| 15 | 28.51 | [M − H]⁻ 749.1708 | MS2: 717.2390, 551.2418, 321.1771 | 8-Hydroxy-9''-methyl-salvianolate B |
| 16 a | 32.67 | [M − H]⁻ 717.1426 | MS2: 519.1459, 321.1666 MS3: 359.1635, 322.9468 |
Salvianolic acid B |
| 17 | 33.94 | [M − H]⁻ 717.1445 | MS2: 519.1002, 321.1299 | Iso salvianolic acid B |
| 18 | 37.06 | [M − H]⁻ 717.1447 | MS2: 673.0787, 519.1280, 321.0964 | Salvianolic acid L |
| 19 | 38.03 | [M − H]⁻ 493.1127 | MS2: 475.0607, 313.1490, 295.0408 | Salvianolic acid A |
| 20 | 39.86 | [M − H]⁻ 731.1599 | MS2: 713.0930, 533.1845, 335.1095 | Methyl salvianolic acid B |
| 21 | 40.50 | [M − H]⁻ 551.1185 | MS2: 519.1639, 353.0330, 321.0014 | Methyl salvianolic acid I/H |
| 22 | 45.70 | [M − H]⁻ 717.6401 | MS2: 673.2368, 617.6599, 519.1243, 321.1423 | Salvianolic acid E |
| 23 | 64.63 | [M − H]⁻ 505.1127 | MS2: 473.1639, 321.1718 | Methyl salvianolate C |
| 24 | 21.35 | [M + H]+ 315.1228 | MS2: 297.0677, 266.9693, 249.0071 | 17-Hydroxytanshindiol B |
| 25 | 37.09 | [M + H]+ 313.1072 | MS2: 294.9926, 264.9864, 247.0231 | Tanshinone A |
| 26 | 46.34 | [M + H]+ 297.1122 | MS2: 279.0668, 250.9774, 223.1107 | Tanshinone VI |
| 27 | 47.88 | [M + H]+ 297.1127 | MS2: 279.0222, 269.0689, 251.0355 | Danshenxinkun A |
| 28 | 48.81 | [M + H]+ 299.1283 | MS2: 281.0504, 263.0121 | 15,16-Dihydrotanshinol B |
| 29 | 56.29 | [M + H]+ 313.1437 | MS2: 295.0622, 277.0113, 267.0143 | Tanshindiol B |
| 30 | 60.48 | [M + H]+ 313.1440 | MS2: 295.0879, 277.0540, 267.0566, 249.0650 | Tanshindiol C |
| 31 | 65.82 | [M + H]+ 295.0967 | MS2: 276.9836, 267.0344, 252.9953,249.0193 | 3α-Hydroxymethylenetanshinquinone |
| 32 | 66.45 | [M + H]+ 297.1124 | MS2: 279.0198, 261.0336 | Tanshinol B |
| 33 | 70.11 | [M + H]+ 295.0966 | MS2: 277.0328, 267.0656 | Trijuganone A |
| 34 | 71.64 | [M + H]+ 311.1276 | MS2: 293.0745, 267.0956MS3: 275.0365, 251.0166 | Tanshinone IIB |
| 35 | 71.86 | [M + H]+ 311.1279 | MS2: 293.0213, 275.0118, 267.0738 | 3α-Hydroxytanshinone IIA |
| 36 | 74.83 | [M + H]+ 341.1381 | MS2: 281.0114, 263.0162 | Methyldihydronortanshinonate |
| 37 | 78.02 | [M + H]+ 309.1119 | MS2: 281.0635 | Tanshinaldehyde |
| 38 | 78.92 | [M + H]+ 311.1280 | MS2: 293.0916, 283.0533, 267.0832 | 17-Hydroxycryptotanshinone |
| 39 a | 79.33 | [M + H]+ 279.1015 | MS2: 260.9656, 233.0795 | 15,16-Dihydrotanshinone I |
| 40 | 80.23 | [M + H]+ 297.1483 | MS2: 269.1145, 279.0749, 251.1033 MS3: 251.0895, 241.0596 |
1-Oxomiltirone |
| 41 | 81.76 | [M + H]+ 281.1177 | MS2: 263.0103, 252.9724, 235.0020 MS3: 234.9965, 220.9875 |
Trijuganone B |
| 42 | 82.68 | [M + H]+ 339.1228 | MS2: 311.0540, 279.0392, 261.1021 MS3: 260.9993 |
Methyl tanshinonate |
| 43 | 85.19 | [M + H]+ 267.1381 | MS2: 249.0448, 224.9753 | 4-Methylenemiltirone |
| 44 a | 86.29 | [M + H]+ 297.1481 | MS2: 279.1028, 251.0883, 237.0703 MS3: 264.0307, 251.0550, 237.0704, |
Cryptotanshinone |
| 45 a | 87.42 | [M + H]+ 277.0855 | MS2: 249.0238, 231.058.9814 | Tanshinone I |
| 46 | 90.41 | [M + H]+ 279.1016 | MS2: 260.9862, 233.0613, 221.0357, 258.9814 | 1,2-Dihydrotanshinone I /3,4-dihydrotanshinone I |
| 47 | 93.18 | [M + H]+ 281.1539 | MS2: 220.9732, 253.0703, 263.1043, 239.0273 | 1,2-Didehydromiltirone |
| 48 a | 95.04 | [M + H]+ 295.1327 | MS2: 277.0313, 249.1205, 235.0146 | Tanshinone IIA |
| 49 | 97.18 | [M + H]+ 283.1689 | MS2: 265.0710, 241.0755, 237.0394, 223.0768 MS3: 250.0806,237.0400, 223.0643, 195.0449 |
Miltirone |
a Positively identified via comparison with reference standards.