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. 2018 Mar;19(3):227–244. doi: 10.1631/jzus.B1700105

Table 2.

Metabolites identified in bio-samples from rats after oral administration of danshen extract

No. t R (min) Ion Theoretical mass (m/z) Experimental mass (m/z) Formula [M−H]−/[M+H]+ Error (ppm) MS/MS fragment Identification Plasma Urine Feces Bile
Phenolic acids
1 2.11 [M−H]− 277.0013 277.0020 C9H9O8S 2.8 MS2[277]: 259(57), 215(35), 197(100) Sulfate danshensu × × √ ×
2 4.26 [M−H]− 277.0013 277.0010 C9H9O8S −0.8 MS2[277]: 215(40), 197(100) MS3[196]: 179(100) Sulfate danshensu × √ × ×
3 4.77 [M−H]− 197.0444 197.0446 C9H9O5 0.6 MS2[197]: 179(100) MS3[179]: 135(100) Danshensua,b √ √ √ ×
4 7.35 [M−H]− 211.0601 211.0603 C10H11O5 0.9 MS2[211]: 193(100), 165(23) MS3[193]: 149(29), 134(100) Methyl danshensu √ √ √ √
5 7.47 [M−H]− 179.0339 179.0344 C9H7O4 3.1 MS2[179]: 135(100) MS3[135]: 135(100) Demethyl ferulic acid × √ × ×
6 7.52 [M−H]− 137.0233 137.0236 C7H5O3 1.7 MS2[137]: 137(100) Protocatechuic aldehydea,b × × √ ×
7 7.62 [M−H]− 181.0495 181.0502 C9H9O4 3.7 MS2[181]: 163(100) MS3[162]: 119(100) Dihydro caffeic acid × √ √ ×
8 8.29 [M−H]− 179.0339 179.0341 C9H7O4 1.2 MS2[179]: 135(100) MS3[135]: 135(100) Acetylated protocatechuic aldehyde × √ × ×
9 8.59 [M−H]− 165.0546 165.0550 C9H9O3 2.4 MS2[165]: 121(100) MS3[121]: 121(100) Decarbonyl ferulic acid × √ × ×
10 9.38 [M−H]− 361.0918 361.0910 C18H17O8 −2.2 MS2[361]: 317(39), 273(41), 239(100), 221(68) MS3[239]: 195(100), 151(19) Dihydro rosmarinic acid × × √ ×
11 9.86 [M−H]− 193.0495 193.0502 C10H9O4 3.5 Ferulic acid/isoferulic acida,b × × √ ×
12 12.03 [M−H]− 343.0812 343.0806 C18H15O7 −1.8 MS2[343]: 299(100) MS3[299]: 255(100) Hydroxyl and methyl salvianolic acid F × × √ ×
13 13.62 [M−H]− 535.1082 535.1072 C24H23O14 −1.9 MS2[535]: 359(100) MS3[359]: 197(23), 179(20), 161(100) Rosmarinic acid glucuronide conjugate × √ × ×
14 13.99 [M−H]− 539.1184 539.1169 C27H23O12 −2.7 MS2[539]: 399(100), 297(67) MS3[297]: 219(100), 201(70) Dihydro salvianolic acid H/I × √ √ ×
15 14.67 [M−H]− 537.1028 537.1025 C27H21O12 −0.4 MS2[537]: 339(100), 295(38) Salvianolic acid H/Ib × × √ ×
16 15.03 [M−H]− 735.1556 735.1539 C36H31O17 −2.3 Hydrated salvianolic acid Bb × × √ ×
17 15.17 [M−H]− 343.0812 343.0806 C18H15O7 −1.7 MS2[343]: 255(100) MS3[255]: 237(91), 148(100) Hydroxyl and methyl salvianolic acid F × × √ ×
18 16.55 [M−H]− 555.1133 555.1125 C27H23O13 −1.5 MS2[555]: 375(100), 357(39) MS3[375]: 331(100), 269(60) Hydrated salvianolic acid H/I × × √ ×
19 16.71 [M−H]− 359.0761 359.0761 C18H15O8 −0.2 MS2[359]: 271(100) MS3[271]: 149(100), 135(46), 121(74) Rosmarinic acida,b √ × × ×
20 17.01 [M−H]− 523.1235 523.1225 C27H23O11 −1.9 MS2[523]: 505(53), 281(100) MS3[281]: 263(26), 174(100) Demethyl and hydroxyl salvianolic acid A × × √ ×
21 17.14 [M−H]− 315.0863 315.0863 C17H15O6 0.0 MS2[315]: 297(18), 285(100), 267(12) Dihydro salvianolic acid F × √ × ×
22 17.46 [M−H]− 493.1129 493.1130 C26H21O10 0.1 MS2[493]: 295(100) MS3[295]: 277(56), 159(100) Iso salvianolic acid Ab √ √ √ ×
23 19.02 [M−H]− 717.1450 717.1439 C36H29O16 −1.5 MS2[717]: 519(100), 321(17) MS3[519]: 339(22), 321(100) Salvianolic acid Ba,b × √ √ ×
24 20.40 [M−H]− 763.1869 763.1854 C38H35O17 −1.9 MS2[763]: 565(100), 520(57), 321(15) Hydrated dimethyl salvianolic acid B × × √ ×
25 20.80 [M−H]− 717.1450 717.1441 C36H29O16 −1.3 MS2[717]: 519(100), 321(19) MS3[519]: 339(23), 321(100) Salvianolic acid Eb × √ √ ×
26 21.26 [M−H]− 493.1129 493.1129 C26H21O10 −0.1 MS2[493]: 295(100) MS3[295]: 277(59), 159(100) Salvianolic acid Aa,b √ √ √ ×
27 21.70 [M−H]− 551.1184 551.1177 C28H23O12 −1.3 MS2[551]: 519(43), 371(100), 353(51), 339(73) Methyl salvianolic acid H/I × × √ ×
28 22.20 [M−H]− 731.1607 731.1597 C37H31O16 −1.4 MS2[731]: 533(100) MS3[533]: 353(49), 335(100) Methyl salvianolic acid Bb √ √ √ ×
29 24.15 [M−H]− 491.0973 491.0971 C26H19O10 −0.3 MS2[491]: 293(100) MS3[293]: 276(33), 264(100), 249(91) Iso salvianolic acid Cb × × √ ×
30 24.35 [M−H]− 565.1341 565.1334 C29H25O12 −1.1 MS2[565]: 519(84), 367(78), 321(100) Dimethyl lithospermateb × × √ ×
31 25.16 [M−H]− 565.1341 565.1331 C29H25O12 −1.7 MS2[565]: 519(87), 367(79), 321(100) Dimethyl lithospermateb √ √ √ ×
32 26.60 [M−H]− 565.1341 565.1331 C29H25O12 −1.8 Dimethyl lithospermateb × √ × ×
33 27.21 [M−H]− 491.0973 491.0972 C26H19O10 −0.1 MS2[491]: 293(100) Salvianolic acid Ca,b × × √ ×
Tanshinones
34 9.08 [M+H]+ 345.0969 345.0976 C18H17O7 2.0 MS2[345]: 327(100), 281(53) MS3[327]: 309(14), 281(100) Demethyl and trihydroxyl tanshinone IIB × × √ ×
35 12.06 [M+H]+ 517.1704 517.1683 C26H29O11 −2.1 Methyl dihydrotanshinonate glucuronide conjugate × √ × ×
36 12.77 [M+H]+ 343.0812 343.0814 C18H15O7 0.5 MS2[343]: 325(92), 297(100) MS3[297]: 279(100), 255(56) Demethyl and carboxylated tanshindiol A/B/C × × √ ×
37 13.06 [M+H]+ 329.1020 329.1023 C18H17O6 1.1 MS2[329]: 311(100), 265(58) MS3[311]: 283(25), 265(100) Demethyl and two hydroxyl tanshinone IIB × × √ ×
38 13.37 [M+H]+ 620.1909 620.1917 C28H34O11N3S 1.3 MS2[620]: 602(55), 584(32), 455(100) Tanshindiol A/B/C glutathione conjugate × × × √
39 13.66 [M+H]+ 343.0812 343.0814 C18H15O7 0.5 MS2[343]: 325(95), 297(100) MS3[297]: 279(100), 255(60) Demethyl and carboxylated tanshindiol A/B/C × × √ ×
40 14.04 [M+H]+ 471.1286 471.1286 C24H23O10 0.1 MS2[471]: 295(57), 277(23), 267(100) MS3[267]: 249(50), 237(100) Hydroxyl and glucuronidated dihydrotanshinone I × √ × ×
41 14.25 [M−H]− 487.1235 487.1232 C24H23O11 −0.6 MS2[487]: 311(100) MS3[311]: 283(30), 281(100) Hydroxyl and glucuronidated tanshinol B × √ × ×
42 14.64 [M+H]+ 473.1442 473.1440 C24H25O10 −0.5 MS2[473]: 297(80), 279(100), 251(39) MS3[279]: 261(100), 251(100) Hydroxyl and glucuronidated danshenxinkun B × √ × ×
43 16.60 [M+H]+ 327.0863 327.0866 C18H15O6 0.7 MS2[327]: 309(100), 281(67), 265(12) MS3[309]: 291(13), 281(100) Hydroxyl and dehydro tanshindiol A/B/C × × √ ×
44 18.89 [M+H]+ 345.1333 345.1338 C19H21O6 1.5 MS2[345]: 327(100), 309(23) MS3[327]: 309(100), 281(19) Hydrated and hydroxyl tanshinone IIB × √ × ×
45 19.32 [M+H]+ 301.1434 301.1433 C18H21O4 −0.4 MS2[301]: 283(100) Demethyl neocryptotanshinone √ × × ×
46 19.43 [M+H]+ 301.1434 301.1439 C18H21O4 1.6 MS2[301]: 283(100) MS3[283]: 265(100), 255(26) Demethyl and two hydroxyl miltirone × √ × ×
47 19.81 [M−H]− 313.0707 313.0708 C17H13O6 0.4 MS2[313]: 269(27), 252(100) Demethyl and two hydroxyl tanshinol B × × √ ×
48 20.40 [M+H]+ 355.1176 355.1157 C20H19O6 −2.0 MS2[355]: 337(100), 309(45) Hydroxyl methyltanshinonate × √ × ×
49 20.47 [M+H]+ 489.1391 489.1397 C24H25O11 1.1 MS2[489]: 313(100), 295(57) Tanshindiol A/B/C glucuronide conjugate √ × × ×
50 21.17 [M+H]+ 313.1071 313.1077 C18H17O5 2.0 MS2[313]: 295(100), 265(78) Tanshindiol A/B/Cb √ × √ ×
51 21.54 [M+H]+ 339.1227 339.1209 C20H19O5 −1.8 MS2[339]: 321(100) Methyl tanshinonate × √ × ×
52 22.00 [M+H]+ 297.1121 297.1129 C18H17O4 2.4 MS2[297]: 279(100), 251(49), 237(36) Hydrated dihydrotanshinone I × √ × ×
53 22.49 [M+H]+ 313.1071 313.1077 C18H17O5 2.0 MS2[313]: 295(100), 267(7) MS3[295]: 267(100) Tanshindiol A/B/Cb √ √ √ ×
54 22.98 [M+H]+ 309.0758 309.0763 C18H13O5 1.8 MS2[309]: 291(18), 265(20), 235(100) MS3[235]: 207(18), 179(100) Dihydroxyl tanshinone I × √ × ×
55 23.60 [M+H]+ 295.0601 295.0603 C17H11O5 0.6 MS2[295]: 267(100) MS3[267]: 239(100) Demethyl and two hydroxyl tanshinone I × × √ ×
56 23.87 [M+H]+ 299.1278 299.1281 C18H19O4 0.5 MS2[299]: 281(42), 271(49), 253(100) Demethyl and hydroxyl cryptotanshinone × √ × ×
57 23.89 [M−H]− 311.0914 311.0915 C18H15O5 0.3 MS2[311]: 283(32), 281(100) MS3[281]: 253(100) Hydroxyl tanshinol B × √ × ×
58 24.85 [M+H]+ 299.1278 299.1284 C18H19O4 1.1 MS2[299]: 281(19), 271(44), 253(100) Demethyl and hydroxyl cryptotanshinone √ √ × ×
59 25.78 [M−H]− 325.0707 325.0706 C18H13O6 −0.3 MS2[325]: 297(31), 295(100), 268(30) MS3[294]: 267(100) Demethyl and carboxylated tanshinol B × √ × ×
60 26.06 [M+H]+ 313.1071 313.1074 C18H17O5 1.3 MS2[313]: 295(100) Tanshindiol A/B/Cb √ √ √ ×
61 26.21 [M+H]+ 345.1333 345.1341 C19H21O6 0.5 MS2[345]: 327(100) MS3[327]: 299(100), 281(13) Demethyl and carboxylated neocryptotanshinone × √ × ×
62 28.01 [M−H]− 297.1121 297.1124 C18H17O4 0.9 MS2[297]: 253(100), 239(74), 221(26) MS3[253]: 238(100) Dihydro tanshinol B × √ × ×
63 28.04 [M+H]+ 343.1176 343.1184 C19H19O6 0.1 MS2[343]: 325(100) Dihydroxyl tanshinone IIB × √ √ ×
64 28.27 [M+H]+ 372.1806 372.1811 C21H26O5N 1.7 MS2[372]: 354(100), 311(55), 283(60) MS3[354]: 326(100), 311(59) Neocryptotanshinone glycine conjugate × √ √ ×
65 28.44 [M+H]+ 313.1434 313.1437 C19H21O4 −0.5 MS2[313]: 269(100) MS3[269]: 254(25), 223(21), 199(100), 171(74) Hydroxyl cryptotanshinoneb √ √ √ ×
66 28.70 [M−H]− 471.1286 471.1286 C24H23O10 0.0 MS2[471]: 295(100) Tanshinol B glucuronide conjugate × √ × ×
67 28.73 [M+H]+ 331.1540 331.1545 C19H23O5 0.7 MS2[331]: 313(100), 295(38) Hydroxyl and methyl salvianonol √ × × ×
68 28.80 [M+H]+ 459.1286 459.1287 C23H23O10 1.5 MS2[459]: 283(100) MS3[283]: 265(25), 237(100) Dihydronortanshinone glucuronide conjugate × √ × ×
69 28.99 [M−H]− 471.1286 471.1286 C24H23O10 0.1 MS2[471]: 295(100) Tanshinol B glucuronide conjugate × √ × ×
70 29.00 [M+H]+ 618.2116 618.2119 C29H36O10N3S −0.4 MS2[618]: 471(44), 309(100) Tanshinone IIB glutathione conjugate × × × √
71 29.01 [M+H]+ 327.1227 327.1231 C19H19O5 1.6 MS2[327]: 309(24), 299(22), 281(100), 263(57) MS3[281]: 263(100), 235(36) Hydroxyl tanshinone IIB × √ × ×
72 29.41 [M+H]+ 309.1121 309.1121 C19H17O4 −2.0 MS2[309]: 265(100) MS3[265]: 247(51), 223(100), 195(18) Hydroxyl and dehydro tanshinone IIA √ × × ×
73 29.54 [M+H]+ 343.1176 343.1185 C19H19O6 1.1 MS2[343]: 325(100) Dihydroxyl tanshinone IIB × √ × ×
74 30.06 [M+H]+ 313.1434 313.1438 C19H21O4 1.1 MS2[313]: 269(35), 251(100) MS3[251]: 223(100) Hydroxyl cryptotanshinone × √ × ×
75 30.44 [M+H]+ 445.1857 445.1864 C24H29O8 −1.8 MS2[445]: 269(100) MS3[269]: 254(100), 239(14) Decarbonylated and glucuronidated cryptotanshinone × × × √
76 30.63 [M+H]+ 293.0808 293.0813 C18H13O4 2.4 MS2[293]: 275(22), 263(100), 249(23) MS3[263]: 235(100) Hydroxyl tanshinone I √ √ √ ×
77 31.05 [M+H]+ 295.0965 295.0966 C18H15O4 1.8 MS2[295]: 251(100) MS3[251]: 223(97), 195(95), 169(100) Hydrated tanshinone Ib √ √ × ×
78 31.08 [M+H]+ 297.1121 297.1124 C18H17O4 0.6 MS2[297]: 279(100), 261(36) MS3[279]: 261(100) Demethyl and hydroxyl tanshinone IIA √ √ √ ×
79 31.30 [M+H]+ 285.1485 285.1489 C18H21O3 1.0 MS2[285]: 243(100), 229(6) MS3[243]: 228(71), 225(92), 1815(100) Demethyl and hydroxyl miltirone √ √ × ×
80 31.32 [M−H]− 311.0914 311.0912 C18H15O5 −0.7 MS2[311]: 267(100), 223(29) Hydroxyl tanshinol B × √ × ×
81 31.36 [M+H]+ 473.1806 473.1806 C25H29O9 2.3 MS2[473]: 297(36), 269(100) MS3[269]: 241(100), 213(92), 199(87) Cryptotanshinone glucuronide conjugate × × √ ×
82 31.61 [M+H]+ 339.1227 339.1210 C20H19O5 1.2 MS2[339]: 321(100), 295(21) Methyl tanshinonate × √ × ×
83 32.13 [M+H]+ 459.2014 459.2012 C25H31O8 2.4 MS2[459]: 283(100) Miltirone glucuronide conjugate × × × √
84 32.36 [M+H]+ 381.1333 381.1318 C22H21O6 2.2 MS2[381]: 363(60), 337(100) Acetylated methyltanshinone √ × × ×
85 32.65 [M+H]+ 311.1278 311.1282 C19H19O4 1.4 MS2[311]: 293(40), 275(37), 267(100) MS3[267]: 252(100) Tanshinone IIBa,b √ √ √ √
86 32.84 [M+H]+ 287.1642 287.1645 C18H23O3 0.8 MS2[287]: 269(100) MS3[269]: 251(58), 241(100), 213(86) Decarbonylated neocryptotanshinone √ × × ×
87 33.16 [M+H]+ 299.1642 299.1646 C19H23O3 1.4 MS2[299]: 281(100), 255(68), 253(62) Hydroxyl miltirone × √ × ×
88 33.24 [M+H]+ 267.1016 267.1022 C17H15O3 0.3 MS2[267]: 249(100), 221(22) Decarbonylated hydrated tanshinone I √ × × ×
89 33.31 [M+H]+ 457.1493 457.1496 C24H25O9 0.5 MS2[457]: 281(100), 263(73), 261(41) MS3[281]: 263(100) Danshenxinkun B glucuronide conjugate × × × √
90 33.59 [M+H]+ 341.1384 341.1388 C20H21O5 1.2 MS2[341]: 281(100), 263(42) MS3[281]: 263(100), 235(18) Methyl dihydrotanshinonateb × × √ ×
91 33.67 [M+H]+ 279.1016 279.1021 C18H15O3 −0.2 MS2[279]: 261(100) MS3[261]: 233(100), 205(13) Dihydro tanshinone I √ × × √
92 33.69 [M−H]− 295.0965 295.0968 C18H15O4 1.2 MS2[295]: 277(17), 267(28), 265(100), 238(27) MS3[265]: 237(100) Tanshinol Ba,b √ √ √ √
93 33.73 [M+H]+ 309.1121 309.1120 C19H17O4 2.5 MS2[309]: 265(100) MS3[265]: 247(55), 223(100) Hydroxyl and dehydro tanshinone IIA √ √ × ×
94 34.29 [M+H]+ 297.1485 297.1489 C19H21O3 0.3 MS2[297]: 253(100) MS3[253]: 238(33), 225(24), 211(100), 209(16) Hydroxyl dehydromiltirone √ × × ×
95 34.61 [M+H]+ 293.1172 293.1174 C19H17O3 1.5 MS2[293]: 275(100), 247(39) MS3[275]: 247(100) Dehydrotanshinone IIAb × × √ ×
96 34.63 [M+H]+ 297.1485 297.1490 C19H21O3 1.6 MS2[297]: 279(100), 251(81) MS3[279]: 251(100), 237(67) Dihydro tanshinone IIA × × × √
97 34.72 [M+H]+ 311.1278 311.1284 C19H19O4 1.8 MS2[311]: 283(100) MS3[283]: 265(100), 237(17) Hydroxyl tanshinone IIA √ × × ×
98 35.14 [M+H]+ 279.1016 279.1020 C18H15O3 1.4 MS2[279]: 261(100), 233(5) MS3[261]: 233(100), 215(7), 205(14) Dihydrotanshinone Ib × √ √ √
99 35.36 [M+H]+ 293.0808 293.0815 C18H13O4 2.2 MS2[293]: 249(100) MS3[249]: 221(26), 193(100), 178(52) Hydroxyl hydrotanshinone I × × × √
100 35.69 [M+H]+ 315.1591 315.1594 C19H23O4 1.0 MS2[315]: 297(100) MS3[297]: 279(100), 268(13), 254(18), 251(58) Hydrated cryptotanshinone √ × × √
101 35.83 [M+H]+ 281.1172 281.1178 C18H17O3 2.2 MS2[281]: 263(100), 235(72) MS3[263]: 235(100) Danshenxinkun Ba b × √ √ ×
102 35.96 [M+H]+ 339.1227 339.1235 C20H19O5 2.5 MS2[339]: 279(100) MS3[279]: 261(100) Methyl tanshinonateb × × √ √
103 36.22 [M+H]+ 295.1329 295.1331 C19H19O3 0.9 MS2[295]: 277(100), 249(40) MS3[277]: 262(53), 249(100), 235(38) Dehydrocryptotanshinoneb × × √ ×
104 36.59 [M+H]+ 309.1121 309.1124 C19H17O4 0.8 MS2[309]: 265(100) MS3[265]: 247(52), 223(100) Hydroxyl and methyl dihydrotanshinone I × × × √
105 36.67 [M+H]+ 301.1798 301.1802 C19H25O3 1.4 MS2[301]: 271(100) MS3[271]: 256(100) Hydrated miltirone × × √ ×
106 36.96 [M+H]+ 313.1434 313.1439 C19H21O4 1.5 MS2[313]: 295(100), 277(31), 271(33), 267(25) MS3[295]: 277(100), 253(27), 249(23) Hydroxyl cryptotanshinone √ × × ×
107 37.31 [M+H]+ 297.1485 297.1488 C19H21O3 1.0 MS2[297]: 279(100), 251(81) MS3[279]: 251(100), 237(73) Cryptotanshinonea b × √ √ ×
108 37.58 [M+H]+ 277.0859 277.0863 C18H13O3 1.4 MS2[277]: 249(100), 231(13) MS3[249]: 234(18), 221(89), 193(100), 178(30) Tanshinone Ia b √ √ √ ×
109 38.82 [M+H]+ 279.1016 279.1017 C18H15O3 0.6 MS2[279]: 261(100) MS3[261]: 233(100) Dihydrotanshinone Ia b × √ √ √
110 38.97 [M+H]+ 293.1172 293.1178 C19H17O3 2.1 MS2[293]: 275(100), 247(40) MS3[275]: 247(100) Dehydrotanshinone IIAb √ √ √ √
111 40.01 [M+H]+ 281.1536 281.1540 C19H21O2 1.4 Dehydromiltironeb × × √ ×
112 40.23 [M+H]+ 293.1172 293.1175 C19H17O3 1.0 Dehydrotanshinone IIAb √ √ √ ×
113 40.58 [M−H]− 277.0859 277.0865 C18H13O3 2.1 MS2[277]: 249(100), 221(53) Dehydrated tanshinol B × × √ ×
114 41.15 [M+H]+ 295.1329 295.1331 C19H19O3 0.9 MS2[295]: 277(100), 249(14) MS3[277]: 262(29), 249(100) Tanshinone IIAa b √ √ √ √
115 41.27 [M−H]− 277.0859 277.0863 C18H13O3 1.4 MS2[277]: 249(100), 221(60) Dehydrated tanshinol B × × √ ×
116 42.32 [M+H]+ 283.1693 283.1694 C19H23O2 0.4 MS2[283]: 265(100), 241(47), 223(63) MS3[265]: 237(62), 223(100) Miltironeb × √ √ ×
117 42.70 [M+H]+ 269.1536 269.1537 C18H21O2 0.4 MS2[269]: 254(100) MS3[254]: 239(100) Demethyl miltirone × × √ ×
118 47.15 [M+H]+ 299.1642 299.1646 C19H23O3 1.3 MS2[299]: 281(100), 256(52), 253(49) Dihydro cryptotanshinone × × √ ×
Total 35 63 62 18
a

Confirmed by reference standards;

b

Original components in danshen extract.

"×":detected;"√":undetected