Table 1.
HPLC-MS/MS data and identification of components of danshen
| No. | t R (min) | Ion | Theoretical mass (m/z) | Experimental mass (m/z) | Error (ppm) | Formula [M−H]−/[M+H]+ | MS/MS fragment | Identification | ||
| Phenolic acids | ||||||||||
| 1 | 4.83 | [M−H]− | 197.0444 | 197.0441 | −1.6 | C9H9O5 | MS2[197]: 179(100) MS3[179]: 135(100) | Danshensua | ||
| 2 | 5.70 | [M−H]− | 153.0182 | 153.0184 | 0.9 | C7H5O4 | Protocatechuic acida | |||
| 3 | 7.58 | [M−H]− | 137.0233 | 137.0236 | 1.7 | C7H5O3 | MS2[137]: 137(100) | Protocatechuic aldehydea | ||
| 4 | 9.16 | [M−H]− | 179.0339 | 179.0336 | −1.3 | C9H7O4 | MS2[179]: 135(100) | Caffeic acida | ||
| 5 | 10.08 | [M−H]− | 193.0495 | 193.0493 | −1.2 | C10H9O4 | MS2[193]: 178(100), 149(38), 134(81) MS3[178]: 134(100) | Ferulic acid/isoferulic acida | ||
| 6 | 14.42 | [M−H]− | 735.1556 | 735.1552 | −0.5 | C36H31O17 | MS2[735]: 537(100), 519(20) MS3[519]: 519(51), 357(73), 321(65), 297(100) | Hydrated salvianolic acid B | ||
| 7 | 14.76 | [M−H]− | 537.1028 | 537.1028 | 0.1 | C27H21O12 | MS2[537]: 339(100), 295(37) MS3[339]: 321(33), 295(100) | Salvianolic acid H/I | ||
| 8 | 15.02 | [M−H]− | 735.1556 | 735.1553 | −0.4 | C36H31O17 | MS2[735]: 537(100), 519(49) MS3[537]: 519(51), 339(20), 321(70), 297(100) | Hydrated salvianolic acid B | ||
| 9 | 16.74 | [M−H]− | 359.0761 | 359.0758 | −1.0 | C18H15O8 | MS2[359]: 197(24), 179(23), 161(100) MS3[161]: 161(38), 133(100) | Rosmarinic acida | ||
| 10 | 17.45 | [M−H]− | 493.1129 | 493.1129 | 0.0 | C26H21O10 | MS2[493]: 295(100) MS3[295]: 280(13), 277(65), 159(100) | Salvianolic acid A isomer | ||
| 11 | 19.07 | [M−H]− | 717.1450 | 717.1434 | −2.2 | C36H29O16 | MS2[717]: 519(100), 321(15) MS3[519]: 339(21), 321(100) | Salvianolic acid Ba | ||
| 12 | 20.89 | [M−H]− | 717.1450 | 717.1450 | 0.0 | C36H29O16 | MS2[717]: 519(100), 321(18) MS3[519]: 339(21), 321(100) | Salvianolic acid E | ||
| 13 | 21.32 | [M−H]− | 493.1129 | 493.1135 | 1.1 | C26H21O10 | MS2[493]: 295(100) MS3[295]: 280(14), 277(66), 159(100) | Salvianolic acid Aa | ||
| 14 | 22.26 | [M−H]− | 731.1607 | 731.1598 | −1.2 | C37H31O16 | MS2[731]: 533(100) MS3[533]: 353(51), 335(100) | Methyl salvianolic acid B | ||
| 15 | 23.68 | [M−H]− | 565.1341 | 565.1341 | 0.1 | C29H25O12 | MS2[565]: 519(87), 367(87), 339(15), 321(100) | Dimethyl lithospermate | ||
| 16 | 24.23 | [M−H]− | 491.0973 | 491.0982 | 1.9 | C26H19O10 | MS2[491]: 311(60), 293(100) MS3[293]: 276(32), 275(11), 265(100), 249(89), 247(13) | Isosalvianolic acid C | ||
| 17 | 24.44 | [M−H]− | 565.1341 | 565.1341 | 0.1 | C29H25O12 | MS2[565]: 367(76), 339(17), 321(100) | Dimethyl lithospermate | ||
| 18 | 25.23 | [M−H]− | 565.1341 | 565.1345 | 0.7 | C29H25O12 | MS2[565]: 519(88), 339(15), 321(100) MS3[321]: 293(31), 277(100), 249(76) | Dimethyl lithospermate | ||
| 19 | 26.65 | [M−H]− | 565.1341 | 565.1345 | 0.7 | C29H25O12 | MS2[565]: 367(100) | Dimethyl lithospermate | ||
| 20 | 27.27 | [M−H]− | 491.0973 | 491.0977 | 0.9 | C26H19O10 | MS2[491]: 311(22), 293(100) MS3[293]: 276(24), 275(18), 265(100), 249(21), 247(36) | Salvianolic acid Ca | ||
| 21 | 27.65 | [M−H]− | 745.1763 | 745.1760 | −0.5 | C38H33O16 | MS2[745]: 547(87), 519(100), 321(73) | Dimethyl salvianolic acid B | ||
| 22 | 28.62 | [M−H]− | 745.1763 | 745.1762 | −0.1 | C38H33O16 | MS2[745]: 547(87), 519(100), 321(74) | Dimethyl salvianolic acid B | ||
| 23 | 28.97 | [M−H]− | 313.0707 | 313.0709 | 0.8 | C17H13O6 | MS2[313]: 269(36), 161(100) MS3[161]: 161(29), 133(100) | Salvianolic acid F | ||
| Tanshinones | ||||||||||
| 24 | 33.73 | [M−H]− | 295.0965 | 295.0970 | 1.7 | C18H15O4 | MS2[295]: 277(16), 267(27), 265(100) MS3[265]: 265(100) | Tanshinol Ba | ||
| 25 | 21.24 | [M+H]+ | 313.1071 | 313.1056 | −4.8 | C18H17O5 | MS2[313]: 295(100), 267(22), 265(87) MS3[295]: 277(100), 267(40), 249(98) | Tanshindiol A/B/C | ||
| 26 | 22.57 | [M+H]+ | 313.1071 | 313.1056 | −4.6 | C18H17O5 | MS2[313]: 295(100), 267(7) MS3[295]: 267(100) | Tanshindiol A/B/C | ||
| 27 | 26.14 | [M+H]+ | 313.1071 | 313.1056 | −4.7 | C18H17O5 | MS2[313]: 295(100), 267(9) MS3[295]: 267(100) | Tanshindiol A/B/C | ||
| 28 | 27.01 | [M+H]+ | 293.0808 | 293.0797 | −3.9 | C18H13O4 | MS2[293]: 249(100) MS3[249]: 234(18), 221(24), 193(100), 178(39) | Hydroxyl tanshinone I | ||
| 29 | 28.49 | [M+H]+ | 313.1434 | 313.1422 | −3.9 | C19H21O4 | MS2[313]: 269(100) MS3[269]: 254(25), 251(16), 223(22), 199(100) | Hydroxyl cryptotanshinone | ||
| 30 | 29.28 | [M+H]+ | 283.0965 | 283.0954 | −3.7 | C17H15O4 | MS2[283]: 265(51), 255(27), 241(15), 237(100) MS3[237]: 222(11), 219(100), 209(87), 191(35), 181(25) | Dihydronortanshinone | ||
| 31 | 30.79 | [M+H]+ | 293.0808 | 293.0799 | −3.3 | C18H13O4 | MS2[293]: 249(100) MS3[249]: 234(18), 221(23), 193(100), 178(38) | Przewaquinone B | ||
| 32 | 30.97 | [M+H]+ | 295.0965 | 295.0953 | −4.1 | C18H15O4 | MS2[295]: 277(100), 267(44), 24(51) MS3[277]: 259(82), 249(100), 231(27) | Hydrated tanshinone I/trijuganone A | ||
| 33 | 32.08 | [M+H]+ | 295.0965 | 295.0951 | −4.8 | C18H15O4 | MS2[295]: 277(100), 249(11) MS3[277]: 249(100), 221(17) | Hydrated tanshinone I/trijuganone A | ||
| 34 | 32.26 | [M+H]+ | 313.1423 | 313.1423 | −3.5 | C19H21O4 | MS2[313]: 295(100), 267(73) MS3[295]: 277(100), 267(55), 249(52) | Hydroxyl cryptotanshinone | ||
| 35 | 32.44 | [M+H]+ | 301.1434 | 301.1424 | −3.6 | C18H21O4 | MS2[301]: 283(100) MS3[283]: 265(100), 255(26) | Salvianonol | ||
| 36 | 32.61 | [M+H]+ | 311.1278 | 311.1264 | −4.6 | C19H19O4 | MS2[311]: 293(100), 283(22), 267(80), 225(12) MS3[293]: 278(16), 275(100), 265(19), 251(80) | Tanshinone IIBa | ||
| 37 | 32.77 | [M+H]+ | 311.1278 | 311.1263 | −4.6 | C19H19O4 | MS2[311]: 293(14), 275(11), 267(100) MS3[267]: 252(100), 239(11), 225(63), 185(47) | Hydroxyl tanshinone IIA | ||
| 38 | 33.46 | [M+H]+ | 341.1384 | 341.1371 | −3.8 | C20H21O5 | MS2[341]: 281(100), 263(43) MS3[281]: 263(100), 235(19) | Methyl dihydrotanshinonate | ||
| 39 | 33.69 | [M+H]+ | 327.1214 | 327.1248 | −3.9 | C19H19O5 | MS2[327]: 309(100) MS3[309]: 265(100) | Hydroxyl tanshinone IIB | ||
| 40 | 34.56 | [M+H]+ | 281.1536 | 281.1524 | −4.1 | C19H21O2 | MS2[281]: 266(38), 263(50), 253(28), 239(100) MS3[239]: 224(22), 221(100), 193(54) | Dehydromiltirone | ||
| 41 | 34.64 | [M+H]+ | 293.1172 | 293.1159 | −4.4 | C19H17O3 | MS2[293]: 275(100), 265(11), 247(39) MS3[275]: 260(13), 247(100) | Dehydrotanshinone IIA | ||
| 42 | 35.19 | [M+H]+ | 279.1016 | 279.1004 | −4.3 | C18H15O3 | MS2[279]: 261(100), 233(5) MS3[261]: 233(100) | Dihydrotanshinone Ia | ||
| 43 | 35.71 | [M+H]+ | 315.1591 | 315.1576 | −4.7 | C19H23O4 | MS2[315]: 297(100) MS3[297]: 279(100), 251(57) | Neocryptotanshinone | ||
| 44 | 35.84 | [M+H]+ | 281.1172 | 281.1160 | −4.2 | C18H17O3 | MS2[281]: 263(100), 253(7), 235(71) MS3[263]: 248(16), 245(10), 235(100) | Danshenxinkun Ba | ||
| 45 | 35.98 | [M+H]+ | 339.1227 | 339.1219 | −2.3 | C20H19O5 | MS2[339]: 279(100) MS3[279]: 261(100) | Methyl tanshinonate | ||
| 46 | 36.24 | [M+H]+ | 295.1329 | 295.1319 | −3.3 | C19H19O3 | MS2[295]: 277(100), 267(15), 249(47) MS3[277]: 249(100) | Dehydrocryptotanshinone | ||
| 47 | 37.34 | [M+H]+ | 297.1485 | 297.1474 | −3.7 | C19H21O3 | MS2[297]: 279(100), 251(81) MS3[279]: 251(100) | Cryptotanshinonea | ||
| 48 | 37.62 | [M+H]+ | 277.0859 | 277.0850 | −3.5 | C18H13O3 | MS2[277]: 249(100), 231(13) | Tanshinone Ia | ||
| 49 | 38.84 | [M+H]+ | 279.1016 | 279.1003 | −4.7 | C18H15O3 | MS2[279]: 261(100), 233(6) MS3[261]: 233(100), 205(3) | Dihydrotanshinone I | ||
| 50 | 38.98 | [M+H]+ | 293.1172 | 293.1166 | −2.2 | C19H17O3 | MS2[293]: 275(100), 265(11), 247(38) MS3[275]: 260(13), 247(100) | Dehydrotanshinone IIA | ||
| 51 | 40.05 | [M+H]+ | 281.1536 | 281.1524 | −4.1 | C19H21O2 | MS2[281]: 266(17), 263(43), 253(82), 221(100) MS3[221]: 206(17), 193(100) | Dehydromiltirone | ||
| 52 | 40.28 | [M+H]+ | 293.1172 | 293.1159 | −4.5 | C19H17O3 | MS2[293]: 275(100), 265(11), 247(37) MS3[275]: 260(13), 247(100) | Dehydrotanshinone IIA | ||
| 53 | 41.17 | [M+H]+ | 295.1329 | 295.1317 | −4.0 | C19H19O3 | MS2[295]: 277(100), 249(14) MS3[277]: 249(100) | Tanshinone IIAa | ||
| 54 | 41.54 | [M+H]+ | 281.1536 | 281.1526 | −3.7 | C19H21O2 | MS2[281]: 266(18), 263(43), 253(93), 221(100) MS3[221]: 206(14), 193(100) | Dehydromiltirone | ||
| 55 | 42.34 | [M+H]+ | 283.1693 | 283.1682 | −3.6 | C19H23O2 | MS2[283]: 265(100), 241(47), 223(63) MS3[265]: 237(64), 223(100) | Miltirone | ||
| 56 | 45.75 | [M+H]+ | 557.1959 | 557.1942 | −3.1 | C36H29O6 | MS2[557]: 539(28), 529(100), 511(48) MS3[529]: 511(100), 501(81), 483(46) | Neoprzewaquinone A | ||
| Others | ||||||||||
| Un1 | 9.62 | [M−H]− | 509.2229 | 509.2230 | 0.2 | C22H37O13 | MS2[509]: 463(100) MS3[463]: 331(100), 161(27) | Unknown | ||
| Un2 | 10.91 | [M−H]− | 571.1082 | 571.1080 | −0.5 | C27H23O14 | MS2[571]: 527(21), 483(100), 439(73) | Unknown | ||
| Un3 | 11.73 | [M−H]− | 627.4044 | 627.4059 | 2.4 | C41H55O5 | MS2[627]: 610(14), 581(70), 564(100) | Unknown | ||
| Un4 | 12.96 | [M−H]− | 723.5042 | 723.5013 | −3.9 | C41H71O10 | MS2[723]: 678(100) MS3[678]: 659(100), 451(25), 338(25) | Unknown | ||
| Un5 | 14.07 | [M−H]− | 836.5856 | 836.5854 | −0.2 | C44H84O14 | MS2[836]: 791(100) MS3[791]: 773(100), 565(28) | Unknown | ||
| Un6 | 16.21 | [M−H]− | 717.1450 | 717.1452 | 0.3 | C36H29O16 | MS2[717]: 519(100), 321(16) MS3[519]: 339(22), 321(100) | Unknown | ||
| Un7 | 28.14 | [M−H]− | 341.1020 | 341.1023 | 0.9 | C19H17O6 | MS2[341]: 297(100), 253(14) MS3[297]: 253(100) | Unknown | ||
| Un8 | 28.33 | [M−H]− | 671.1395 | 671.1402 | 1.0 | C35H27O14 | MS2[671]: 473(100) MS3[473]: 429(100), 321(100) | Unknown | ||
| Un9 | 24.40 | [M+H]+ | 327.1227 | 327.1212 | −4.6 | C19H19O5 | MS2[327]: 283(100), 265(8) MS3[283]: 265(29), 254(100) | Unknown | ||
| Un10 | 25.27 | [M+H]+ | 369.0969 | 369.0955 | −3.7 | C20H17O7 | MS2[369]: 323(100), 295(77) MS3[323]: 295(100) | Unknown | ||
| Un11 | 34.38 | [M+H]+ | 297.1485 | 297.1471 | −4.7 | C19H21O3 | MS2[297]: 253(100) MS3[253]: 238(33), 211(100) | Unknown | ||
| Un12 | 42.22 | [M+H]+ | 283.1693 | 283.1677 | −5.4 | C19H23O2 | MS2[283]: 265(100), 241(47), 223(63) MS3[265]: 237(20), 223(100) | Unknown | ||
| Un13 | 50.83 | [M+H]+ | 587.2064 | 587.2059 | −0.9 | C37H31O7 | MS2[587]: 569(100), 541(24) MS3[569]: 551(100), 541(71) | Unknown | ||