Table 2 Characterization of compounds in Siwu decoction categorized formulae by UPLC-QTOF-MS/MS

1

1.42

171 [M + H]⁺

169 [M-H]^-, 125 [M-HCOO]^-, 97 [M-H-CO₂-CO]^-

216, 270

Gallic acid

A, B, C, D, E

2

3.07

355 [M + H]⁺, 377 [M + Na]⁺

353 [M-H]^-, 191[M-C₉H₇O₃]^-, 179[M-C₇H₁₁O₅]^-, 173 [M-C₉H₇O₃-H₂O]^-

326

Chlorogenic acid

A, B, C, D, E

3

4.10

181 [M + H]⁺

179 [M-H]^-, 135 [M-HCOO]^-

320, 240

Caffeic acid

A, B, C, D, E

4

3.52

169 [M + H]⁺

167 [M-H]^-, 153 [M-CH₃]^-, 137 [M-OCH₃]^-, 123 [M-HCOO]^-

290

Vanillic acid

A, B, C, D, E

5

4.90

195 [M + H]⁺

193 [M-H]^-, 178 [M-H-CH₃]^-, 149 [M-H-CO₂]^-, 134 [M-HCOO]^-

320

Ferulic acid

A, B, C, D, E

6

8.90

195 [M + H]⁺

193 [M-H]^-, 237 [M-H + HCOO]^-, 179 [M-CH₃]^-

310

Isoferulic acid

A, B, C, D, E

7

4.68

-

153 [M-H]^-, 141 [M-H-CH₃]^-, 109 [M-H-CO₂]^-

310

Protocatechuic acid

A, B, C, D, E

8

9.44

-

163 [M-H]^-, 117 [M-H-HCOO]^-

Coumaric acid

A, B

9

2.98

139 [M + H]⁺, 161 [M + Na]⁺

137 [M-H]^-, 119 [M-H-H₂O]^-

p-hydroxy benzoic acid

A, B

10

7.02

-

121 [M-H]^-

238, 272

Benzoic acid

A, B

11

1.47

361 [M + H]⁺

359 [M-H]^-, 493 [M-H + HCOO]^-, 405 [M + HCOO]^-, 197 [M-H-glu]^-, 179 [M-H-glu-H₂O]^-

210, 270

1-O-β-D- glucopyranosyl -paeonisuffrone

A, B

12

1.51

517 [M + Na]⁺

493 [M-H]^-, 457 [M-H-2H₂O]^-, 443 [M-H-2H₂O- CH₃]^-, 331 [M-2H-glu]^-, 169 [M-sucrose]^-

220, 270

1^′-O-galloylsucrose

A

13

2.89

562 [M + Na]⁺, 383 [M + H-glu]⁺, 261[M + H-glu-benzoyl]⁺, 197[M + H-glu-benzoyl-SO₂]⁺

543[M-H]^-, 495[M-CH₂OH-H₂O]^-, 461[M-SO₂-H₂O-H]^-, 341[M-SO₂-C₇H₅O-2OH]^-, 243[M-glu-benzoyl-H₂O-CH₃]^-

232

Paeoniflorin sulfonate

A, B

14

3.85

481 [M + H]⁺, 319 [M + H - glu]⁺, 197 [M + H -glu-benzoyl]⁺, 161 [M + H -glu-benzoyl-2H₂O]⁺, 133 [M + H -glu-benzoyl-2H₂O-CO]⁺

479 [M-H]^-, 525 [M + HCOO]^-, 416 [M-CH₂OH-CH₃-H₂O]^-, 283[M- glu-H₂O-OH]^-, 177[M-glu-benzoyl-2H₂O]^-

233

Albiflorin

A, B, C, D, E

15

4.29

-

695[M-H]^-, 631[M-SO₂-H]^-, 525[M-galloyl-H₂O]^-, 519[M-benzoyl-4H₂O]^-, 479[M-galloyl-SO₂]^-, 449[M-galloyl-SO₂-CO-H]^-

275

Galloylpaeoniflorin sulfonate

A, B

16

5.84

481 [M + H]⁺, 503 [M + Na]⁺, 397, 319, 197

479[M-H]^-, 525[M + HCOO]^-, 449[M-CH₂OH]^-, 416[M-CH₂OH-CH₃-H₂O]^-, 327[M-benzoyl-CH₂OH-CH₃-2H]^-, 176[M-benzoyl-glu-2H₂O-H]^-,121[benzoyl]^-

230

Paeoniflorin

A, B, C, D, E

17

4.36

497 [M + H]⁺, 519 [M + Na]⁺, 381 [M + Na–pOHBA]⁺, 357 [M + Na–Glc]⁺, 323 [M + Na–aglycone]⁺, 271 [M + Na–C₁₃H₁₂O₅]⁺

495[M-H]^-, 449[M-CH₃-CH₂OH-H]^-, 479[M-OH]^-, 327[M-p-hydroxybenzoyl-CH₂OH-OH]^-

235, 322

Oxypaeoniflorin

A

18

3.91

481 [M + H]⁺, 503 [M + Na]⁺

479 [M-H]^-, 525[M + HCOO]^-, 449[M-CH₂OH]^-, 327[M-benzoyl-CH₂OH-OH]^-

220, 275

Isopaeoniflorin / albiflorin R1

A

19

4.97

633 [M + H]⁺, 655 [M + Na]⁺, 153[galloyl + H-H₂O]⁺

631[M-H]^-, 525[M-benzoyl-2H]^-, 449[M-galloy-HCHO]^-

275

Galloylpaeoniflorin

A, B

20

4.87

-

939 [M-H]^-, 631 [M-2galloyl-3H]^-, 469 [M- 2galloyl -3H-glu]^-

220, 280

Pentagalloylglucose

A, B,C

21

5.20

-

623[M-H]^-, 515[M-C₆H₅O₂]^-

Acteoside/isoacteoside / forsythoside A

A, B

22

5.78

481[M + H]⁺, 319[M + H-glu]⁺, 197[aglycone + H]⁺, 179[aglycone + H-H₂O]⁺, 161[aglycone + H-2H₂O]⁺, 133[aglycone + H-2H₂O-CO]⁺

479[M-H]^-, 463[M-OH]^-, 341[M-benzoyl-2OH]^-

Mudanpioside I

A, B

23

6.67

647[M-H]^-, 513[M-benzoyl-HCHO]^-, 507[M-benzoyl-2H₂O]^-, 391[M-2benzoyl-HCHO-OH]^-

Benzoypaeoniflorin sulfonate

A, B

24

9.29

585[M + H]⁺, 607 [M + Na]⁺, 602[M + H₂O], 463[M + H-benzoyl]⁺, 301[M + H-glu]⁺, 179[M + H-benzoyl-glu]⁺, 151[M + H-benzoyl-glu-CO]⁺

583[M-H]^-, 629[M + HCOO]^-

220, 270

Benzoylpaeoniflorin

A, C

25

8.09

583[M-H]^-, 629[M + HCOO]^-

220, 270

Isobenzoylpaeoniflorin

A, B

26

4.20

-

799[M-H]^-, 637[M-caffeoyl]^-, 525, 479, 449

cistanoside A or jionoside A1/A2

A

27

3.66

660[M + H₂O], 625[M + H-H₂O]⁺, 341[M + H-H₂O-glu-benzoyl]⁺, 301[M + H-H₂O-2glu]⁺

641[M-H]^-, 687[M + HCOO]^-, 611[M-CH₂OH]^-, 593[M-CH₂OH-H₂O]^-, 341[maltosyl]^-, 497[M-benzoyl-2H₂O-4H]^-

212, 277

Isomaltopaeoniflorin/6^′-O-β-D-glucopyranosylalbiflorin

A

28

2.75

729[M + Na]⁺

705[M-H]^-, 495, 443, 341, 271, 193

215

Isomaltopaeoniflorin sulfonate

A

29

4.14

463[M + H]⁺, 484[M + Na]⁺, 498, 301, 179

461[M-H]^-, 525, 479, 449, 327

232

decaffeoyl-verbascoside

A

30

5.68

363[M + H]⁺, 385[M + Na]⁺, 340, 319, 197

361[M-H]^-, 407[M + HCOO]^-, 311, 287

232

6-O-β-D-glucopyranosyl lactinolide

A

31

1.40

687 [M + H]⁺

685[M-H]^-, 731 [M-H + HCOO]^-, 493 [M-H-glu- HCOO]^-

215, 273

Rehmannioside D

A, B

32

7.18

525 [M + H]⁺, 207

523[M-H]^-, 569 [M + HCOO]^-, 407, 341, 183

Melittoside

A, B

33

3.71

-

785[M-H]^-, 687[M-98]^-

236, 279

Echinacoside

A

34

4.55

435[M + HCOO]^-, 389[M-H]^-, 327[M-3CH₃-H₂O]^-, 178[M-C₁₃H₂₄O₂]^-

-

Rehmaionoside A/B

A, B

35

4.94

-

813[M-H]^-, 515[M-C₆H₁₂O₄-C₉H₁₀O₂-H]^-, 469[M-glu-feruloyl]^-

Jionoside B1/B2

A, B

36

6.51

653[M + H]⁺

651[M-H]^-, 505[M-rhamnosyl-H]^-

276

Martynoside isomer

A

37

4.98

653[M + H]⁺

651[M-H]^-, 445[M-ferulic acid-2CH₃]^-, 389[M-feruloyl-HCHO-3H₂O-2H]^-

235, 322

Martynoside

A

38

5.52

347[M + H]⁺

345[M-H]^-, 391[M + HCOO]^-, 183[M-gku]^-, 179[M-C₁₀H₁₅O₂]^-

-

Rehmapicroside

A,E

39

7.21

207[M + Na]⁺

183[M-H]^-, 165[M-H₂O-H]^-, 139[M-HCOO]^-

-

Rehmapicrogenin

A,E

40

3.20

459[M + H]⁺, 325, 163

457[M-H]^-, 323

215,237

Amygdalin

B

41

6.09

249[M + Na]⁺, 227[M + H]⁺, 209[M-H₂O + H]⁺, 191[M-2H₂O + H]⁺, 181[M-H₂O-CO + H]⁺

225[M-H]^-, 195, 125

277

Senkyunolide J

A, B, C, D,E

42

6.26

225[M + H]⁺, 247[M + Na]⁺, 207.1014[M-H₂O + H]⁺, 189.0889[M + H-2H₂O]⁺, 165.0890 [M + H-H₂O-C₃H₆]⁺

223[M-H]^-, 205, 177

270

Senkyunolide I

A, B, C, D, E

43

6.61

225[M + H]⁺, 247[M + Na]⁺, 207[M-H₂O + H]⁺, 189[M + H-2H₂O]⁺, 165[M + H-H₂O-C₃H₆]⁺

223[M-H]^-

270

Senkyunolide H

A, B, C, D, E

44

10.82

191[M + H]⁺, 173, 149, 135

189[M-H]^-, 207[M-H + H₂O]^-

295, 325

E-ligustilide

A, B, C, D, E

45

13.74

191[M + H]⁺, 173, 149, 135

-

295, 325

Z-ligustilide

A, B, C, D, E

46

9.44

381[M + H]⁺, 426[M + 2Na]⁺, 191[C₁₂H₁₅O₂]⁺

-

280

Z-ligustilide dimmer E-232

A, B, C, D, E

47

13.62

381[M + H]⁺, 426[M + 2Na]⁺, 191[C₁₂H₁₅O₂]⁺

-

296

Z,Z^′-3,3^′,8,8^′-Diligustilide

A, B, C, D

48

10.33

203[M + H]⁺, 225[M + Na]⁺

-

-

3-butylidene-7-hydroxyphthalide

A, B, C, D, E

49

8.04

189[M + H]⁺, 171[M-H₂O + H]⁺, 153[M-2H₂O + H]⁺, 117[M + 3H-H₂O-CO-C₂H₄]⁺

187[M-H]^-

260, 310

E-Butylideniphthalide

A, B, C, D, E

50

9.31

189[M + H]⁺, 161[M-CO + H]⁺, 133[M + H-CO-C₂H₄]⁺

187[M-H]^-, 205[M-H + H₂O]^-

260, 310

Z-Butylidenephthalide

A, B, C, D, E

51

12.90

381[M + H]⁺, 426[M + H + HCOO]⁺, 236, 191

379[M-H]^-, 424[M-H + HCOO]^-, 397[M-H + H₂O]^-

282

Angelicide

A

52

13.65

381[M + H]⁺, 403[M + Na]⁺, 426[M + 2Na]⁺, 191[C₁₂H₁₅O₂]⁺

379[M-H]^-, 411

284

Riligustilide

A

53

14.70

381[M + H]⁺, 403[M + Na]⁺, 191[C₁₂H₁₅O₂]⁺

-

280

Tokinolide B

A

54

12.60

381[M + H]⁺, 399[M + H₂O + H]⁺, 191[C₁₂H₁₅O₂]⁺

379[M-H]^-, 397[M-H + H₂O]^-

230, 276

Levistolide A

A, B, C, D, E

55

3.01

613[M + H]⁺, 635[M + Na]⁺, 451, 433, 163, 144

611[M-H]^-, 543, 353, 191

227

Hydroxysafflor yellow A

B

56

4.01

625[M + H]⁺, 593, 481, 433, 319, 301, 197

623[M-H]^-, 611, 525, 479, 395

232

Isorhamnetin-3-O-nehesperridin

B

57

2.56

803[M + H]⁺, 789, 627, 325

801[M-H]^-, 787, 593, 515, 236

230, 269, 328

6-hydroxy-keampferol −3, 6-O-7-O-glucuronide

B

58

3.85

627[M + H]⁺, 481, 319, 197

625[M-H]^-, 525, 479, 449

232

6- hydroxy-keampferol −3, 6 – O – glucoside

B

59

5.13

595[M + H]⁺, 617[M + Na]⁺, 449, 287

593[M-H]^-, 515, 449, 341, 193

241,265,330

Safflor yellow A

B

60

7.29

303[M + H]⁺

301[M-H]^-

275

Queretin

D

61

4.81

625[M + H]⁺, 317, 479

623[M-H]^-, 525, 315

253, 351

Isohammetin-3-O-neohesperidoside

D

62

5.25

625[M + H]⁺, 370, 356, 325, 317

623[M-H]^-, 515, 315, 309, 279, 181

244, 332

Isohammetin-3-O-rutinoside

D

63

4.40

771[M + H]⁺, 793[M + Na]⁺, 625[M + H-rha]⁺, 479[M + H-2rha]⁺, 317[M + H-3rha]⁺

769[M-H]^-, 525, 449, 327

253, 353

Typhaneoside

D

64

12.10

287[M + H]⁺

285[M-H]^-

279

Keampferol

D

65

5.64

317[M + H]⁺

315[M-H]^-

230, 273

Isohamnetin

D

66

4.90

463[M + H]⁺, 352, 322

461[M-H]^-, 285, 193

235, 323

Scutellarin

E

67

6.33

447[M + H]⁺, 336, 352, 271

445[M-H]^-, 891, 269

216, 277, 316

Baicalin

E

68

7.48

461[M + H]⁺, 285

459[M-H]^-, 919, 283

220, 273

Wogonoside

E

69

8.83

271[M + H]⁺

269[M-H]^-

275, 322

Baicalein

E

70

10.46

285[M + H]⁺

283[M-H]^-, 268[M-H-CH₃]^-

274

Wogonin

E

71

7.19

461[M + H]⁺, 285

459[M-H]^-, 283, 175

271, 310

Oroxylin-A-glucuroside

E

72

10.66

315, 373, 283

313[M-H]^-, 375, 285

271

6-dimethoxy-wogonin

E

73

0.64

136[M + H]⁺

134[M-H]^-

Tetramethylpyrazine

A, B, C, D, E

74

5.36

356[M + H]⁺, 338[M + H-H₂O]⁺, 312[M + H-CO₂]⁺

354[M-H]^-

239, 297

Tetrahydropalmatin

C, D, E

75

4.56

342[M + H]⁺, 311, 193, 179

-

237, 278

Tetrahydrocolumbamine

C, D

76

5.71

354[M + H]⁺, 376[M + Na]⁺, 340, 320

352[M-H]^-

238, 285

Protopine

C, D

77

5.26

370[M + H]⁺, 356[M + H-CH₂]⁺, 327[M + H-CH₃-CO]⁺, 326[M + H-CO₂]⁺

368[M-H]^-

245, 330

Allocryptopine

C, D, E

78

5.40

324[M + H]⁺, 338, 356

322[M-H]^-

-

Tetrahydrocoptisine

C, D, E

79

6.29

356[M + H]⁺, 207

354[M-H]^-

-

Glaucine

C, D, E

80

6.22

336[M + H]⁺, 207

354[M-H]^-

277

Berberine

C, D, E

81

6.48

366[M + H]⁺, 308

-

262, 332

Dehydrocorydaline

C, D, E

82

5.78

368[M + H]⁺, 352[M + H-H₂O]⁺

366[M-H]^-

239, 277, 331

Corydaline

C, D, E

83

6.52

339[M + H]⁺, 357[M + H + H₂O]⁺, 320[M-H₂O]

337[M-H]^-

237, 285

Jatrorrhizine

C, E

84

1.44

127[M + H]⁺, 149[M + Na]⁺

125[M-H]^-, 169[M-H + HCOO]^-

215, 272

5-hydroxymethyl-2-furfural (5-HMF)

A