Table 1.
Characterization of chemical constituents of STP by HPLC-Q-TOF-MS/MS.
| No. | Source | Identification | Rt (min) | Formula | Negative Ion (m/z) | |||
|---|---|---|---|---|---|---|---|---|
| [M − H]− | Quasi-Molecular Ion | Error (ppm) | MSMS (m/z) | |||||
| 1 | C & B | Taurine | 3.7 | C2H7NO3S | 124.0063 | 124.0065 | 2 | |
| 2 | R | Salvianolic acid A | 23.8 | C26H22O10 | 493.1129 | 493.1133 | 1 | |
| 3 | C & B | Bilirubin | 24.2 | C33H35N4O6 | 583.2551 | 583.2518 | 6 | 583.2518, 469.3944,356.4968, 243.8168 |
| 4 | G | Ginsenoside Rk3 | NA | C36H60O8 | 619.4204 | NA | ||
| 5 | G | Ginsenoside Rd | 24.9 | C48H82O18 | 945.5417 | 945.5405 | 1 | |
| 6 | R | Tanshinaldehyde | NA | C19H16O4 | 307.0965 | NA | ||
| 7 | G | Ginsenoside Rg6 | NA | C42H70O12 | 765.4784 | NA | ||
| 8 a | R | Salvianolic acid B | 25.5 | C36H30O16 | 717.1450 | 717.1454 | 0 | 717.1454, 537.0995, 527.9935, 493.1069, 339.0521, 321.0405, 295.0633 |
| 9 a | V | Arenobufagin | 28.7 | C24H32O6 | 415.2115 | 415.2115 | 0 | 415.2115, 397.2063, 371.2165, 353.2112, 277.1492, 196.5435, 151.0702 |
| 10 a | C & B | TDCANa | 33.8 | C26H44NNaO6S | 498.2884 | 498.2885 | 0 | 498.2907, 475.3216, 458.8943, 391.5463 |
| 11 a | C & B | TCA | 33.8 | C26H44NO7S | 514.2833 | 514.2856 | 4 | 514.2856, 496.2486, 482.3441, 124.1263 |
| 12 | G | Ginsenoside Rf | NA | C35H76O19 | 799.4897 | NA | ||
| 13 | V | Gamabufotalin | NA | C24H34O5 | 401.2323 | NA | ||
| 14 | G | Notoginsenoside R2 | NA | C41H70O13 | 769.4733 | NA | ||
| 15 | G | Ginsenoside Rb1 | 40.5 | C54H92O23 | 1107.5946 | 1107.5927 | 2 | 1107.5927, 945.5389, 783.4901, 765.4580, 621.4343, 553.2887, 472.2575, 459.3803, 323.0972, 263.0742, 221.0678, 179.0538, 179.0538, 161.0395, 143.0272, 131.0323, 125.0221, 119.0351, 113.0260, 101.0208 |
| 16 | V | Bufotalin | 41.1 | C26H36O6 | 443.2428 | 443.2452 | 5 | 443.2452, 407.2732, 380.9754, 375.2916, 256.8133, 203.8251, 167.9242, 138.0325 |
| 17 a | G | Ginsenoside Rh1 | 41.8 | C37H64O11 | 683.4403 | 683.4384 | 3 | 683.4384, 637.4330, 475.3704, 179.0470, 161.0398 |
| 18 | C & B | GCA | 42.6 | C26H43NO6 | 464.3007 | 464.3015 | 2 | |
| 19 a | C & B | TDCA | 42.8 | C26H45NO6S | 498.2884 | 498.2907 | 5 | 498.2907, 464.2945, 451.3111, 391.1261, 321.1686, 201.2573 |
| 20 | V | Resibufagin | NA | C24H30O5 | 397.2010 | NA | ||
| 21 | G | Ginsenoside Rb2 | 43.7 | C53H90O22 | 1077.5840 | 1077.5795 | 4 | 1077.5795, 945.5318, 915.1144, 783.0026, 765.1212, 621.3652, 311.9821, 293.6514, 191.8123, 149.1853 |
| 22 | G | Ginsenoside Re | 47.2 | C48H82O18 | 945.5417 | 945.5433 | 2 | 945.5433, 880.9436, 799.2672, 765.1661, 637.2542, 475.2767, 218.9817 |
| 23 | G | Ginsenoside Rk1 | NA | C42H70O12 | 765.4784 | NA | ||
| 24 a | V | Bufalin | NA | C24H34O4 | 385.2373 | NA | ||
| 25 a | C & B | CA | 52.1 | C24H40O5 | 407.2792 | 407.2811 | 5 | 407.2811, 389.2677, 363.2526, 325.6244, 289.2744, 233.8977, 215.3690, 205.9169 |
| 26 | V | Argentinogenin-3-lutarate-arginine | 53.6 | C38H58N408 | 697.4171 | 697.4121 | 7 | 697.4121, 651.4153, 535.5406, 489.3649, 179.0546 |
| 27 | C & B | TLCA | 55.0 | C22H44NO10 | 482.2960 | 482.2918 | 9 | |
| 28 | G | Ginsenoside Rg1 | 55.3 | C43H72O14 | 811.4838 | 811.4813 | 3 | 811.4813, 775.8988, 765.4577, 619.3911, 421.2024, 391.2774 |
| 29 | C & B | DCA | 55.8 | C24H40O4 | 391.2843 | 391.2854 | 3 | |
| 30 | C & B | GCDGA | 56.2 | C26H43NO5 | 448.3058 | 448.3065 | 2 | 448.3065, 409.2741, 391.2853, 389.2658, 365.3004 |
| 31 a | C & B | UDCA | 56.8 | C24H40O4 | 391.2843 | 391.2848 | 1 | 409.2741, 391.2739, 373.8139, 354.4757, 152.9965 |
| 32 a | C & B | HDCA | 57.4 | C24H40O4 | 391.2843 | 391.2851 | 2 | 409.2741, 391.2853, 389.2658, 118.1248 |
| 33 a | V | Resibufogenin | NA | C24H32O4 | 383.2217 | NA | ||
| 34 | G | Ginsenoside Rs3 | NA | C44H74O14 | 825.4995 | NA | ||
| 35 a | V | Cinobufagin | NA | C26H34O6 | 441.2272 | NA | ||
| 36 | G | Chikusetsusaponin Iva | 61.6 | C42H66O14 | 793.4374 | 793.4330 | 6 | 793.4330, 598.6542, 481.7612, 524.4589 |
| 37 | G | Ginsenoside 20S-Rg3 | NA | C42H72O13 | 783.4889 | NA | ||
| 38 a | G | ginsenoside Rg2 | 68.9 | C42H72O13 | 783.4889 | 783.4873 | 2 | 783.4873, 765.1686, 617.0004, 409.2952, 391.2852, 313.1097 |
| 39 a | C & B | CDCA | 68.9 | C24H40O4 | 391.2843 | 391.2853 | 3 | 391.2739, 345.4757, 329.1213, 97.0589 |
| 40 | C & B | LCA | 89.4 | C24H40O3 | 375.2894 | 375.2888 | 2 | |
| 41 a | R | Tanshinone IIA | NA | C19H18O3 | 293.1172 | NA | ||
| No. | Source | Identification | Rt (min) | Formula | Positive Ion (m/z) | |||
| [M + H]+ | Quasi-Molecular Ion | Error (ppm) | MSMS (m/z) | |||||
| 1 | C & B | Taurine | 3.7 | C2H7NO3S | 126.0219 | 126.0222 | 2 | 126.0222, 115.3256, 108.8434, 97.2221, 91.7216 |
| 2 | R | Salvianolic acid A | NA | C26H22O10 | 495.1286 | NA | ||
| 3 | C & B | Bilirubin | NA | C33H35N4O6 | 584.2629 | NA | ||
| 4 | G | Ginsenoside Rk3 | 24.5 | C36H60O8 | 621.4361 | 621.4362 | 0 | |
| 5 | G | Ginsenoside Rd | 24.6 | C48H82O18 | 947.5574 | 947.5501 | 8 | |
| 6 | R | Tanshinaldehyde | 24.6 | C19H16O4 | 309.1121 | 309.1147 | 8 | |
| 7 | G | Ginsenoside Rg6 | 24.6 | C42H70O12 | 767.4940 | 767.4931 | 1 | |
| 8 a | R | Salvianolic acid B | 25.8 | C36H30O16 | 719.1607 | 719.1613 | 1 | 719.1613, 323.0496, 295.0572, 181.0460 |
| 9 a | V | Arenobufagin | 28.4 | C24H32O6 | 417.2272 | 417.2273 | 0 | 417.2273, 399.2188, 362.7495, 223.1056 |
| 10 a | C & B | TDCANa | 33.2 | C26H44NNaO6S | 500.4245 | NA | ||
| 11 a | C & B | TCA | 33.5 | C26H44NO7S | 516.2990 | 516.2984 | 1 | |
| 12 | G | Ginsenoside Rf | 34.0 | C35H76O19 | 801.5054 | 801.5075 | 3 | |
| 13 | V | Gamabufotalin | 38.9 | C24H34O5 | 403.2251 | 403.2267 | 4 | 403.2267, 385.9531, 367.1296, 349.4632, 331.8123 |
| 14 | G | Notoginsenoside R2 | 39.0 | C41H70O13 | 771.4889 | 771.4861 | 4 | |
| 15 | G | Ginsenoside Rb1 | 39.9 | C54H92O23 | 1109.6102 | 1109.6030 | 6 | 1109.6030, 935.5613, 878.7854, 646.6751, 443.3798, 407.3652, 325.1114, 217.1888, 163.0566, 145.0507, 127.0384, 85.0294 |
| 16 | V | Bufotalin | 41.1 | C26H36O6 | 445.2585 | 445.2585 | 0 | |
| 17 a | G | Ginsenoside Rh1 | NA | C37H64O11 | 685.4521 | NA | ||
| 18 | C & B | GCA | 42.3 | C26H43NO6 | 466.3163 | 466.3132 | 7 | 466.3132, 337.2523, 319.2353, 295.2026, 288.1602, 213.1621, 209.1339, 201.1658 |
| 19 a | C & B | TDCA | 42.8 | C26H45NO6S | 500.3040 | 500.3042 | 0 | |
| 20 | V | Resibufagin | 42.8 | C24H30O5 | 399.2166 | 399.2158 | 2 | 399.2158, 387.2519, 297.7655, 223.1439, 211.1011, 145.0999, 131.0982, 179.0841, 105.0709, 91.0525 |
| 21 | G | Ginsenoside Rb2 | 43.1 | C53H90O22 | 1079.5997 | 1079.5942 | 5 | |
| 22 | G | Ginsenoside Re | 46.5 | C48H82O18 | 947.5574 | 947.5510 | 7 | |
| 23 | G | Ginsenoside Rk1 | 46.6 | C42H70O12 | 767.4940 | 767.4931 | 1 | |
| 24 a | V | Bufalin | 49.1 | C24H34O4 | 387.253 | 387.2527 | 1 | 387.2527, 370.9842, 352.9666, 340.2608, 255.2028 |
| 25 a | C & B | CA | NA | C24H40O5 | 409.2949 | NA | ||
| 26 | V | Argentinogenin-3-lutarate-arginine | 53.2 | C38H58N408 | 699.4327 | 699.4299 | 4 | 699.4299, 681.4053, 598.7017, 582.3791, 331.2027, 278.1446, 250.1590, 175.1200, 157.1072 |
| 27 | C & B | TLCA | NA | C22H44NO10 | 483.3038 | NA | ||
| 28 | G | Ginsenoside Rg1 | NA | C43H72O14 | 813.4995 | NA | ||
| 29 | C & B | DCA | NA | C24H40O4 | 393.3000 | NA | ||
| 30 | C & B | GCDGA | 56.1 | C26H43NO5 | 450.3214 | 450.3204 | 2 | 450.3204, 415.3174, 321.2607, 278.7283, 215.1679, 175.1452, 161.1349, 147.1140, 107.0885 |
| 31 a | C & B | UDCA | NA | C24H40O4 | 393.3000 | NA | ||
| 32 a | C & B | HDCA | NA | C24H40O4 | 393.3000 | NA | ||
| 33 a | V | Resibufogenin | 57.7 | C24H32O4 | 385.2373 | 385.2369 | 1 | 385.2369, 367.2214, 350.2243, 341.2244, 332.2025 |
| 34 | G | Ginsenoside Rs3 | 57.8 | C44H74O14 | 827.5151 | 827.5165 | 2 | |
| 35 a | V | Cinobufagin | 57.9 | C26H34O6 | 443.2428 | 443.2425 | 1 | 443.2425, 401.2288, 385.2322, 367.2210, 349.2129, 187.1473, 151.0382 |
| 36 | G | Chikusetsusaponin Iva | NA | C42H66O14 | 795.4525 | NA | ||
| 37 | G | Ginsenoside 20S-Rg3 | 68.6 | C42H72O13 | 785.5046 | 785.5063 | 2 | 785.5063, 621.6871, 357.2785, 339.2647, 321.2458, 275.2027, 221.1526, 161.1345 |
| 38 a | G | ginsenoside Rg2 | NA | C42H72O13 | 785.5046 | NA | ||
| 39 a | C & B | CDCA | NA | C24H40O4 | 393.3000 | NA | ||
| 40 | C & B | LCA | NA | C24H40O3 | 377.3050 | NA | ||
| 41 a | R | Tanshinone IIA | 92.3 | C19H18O3 | 295.1269 | 295.1266 | 0 | 295.1266, 280.4501, 277.1173, 266.0878, 262.0933, 249.1212, 235.0725, 225.1178, 221.1251, 207.0771 |
G: Ginsenoside; V: Venenum bufonis; R: Red-rooted salvia; C: Calculus bovis; B: Bear gall; a Compared with a reference standard.