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Table 1 Tentative identification of the chemical constituents of Erdong decoction by UHPLC- MS in the negative mode

From: The combination of UHPLC-HRMS and molecular networking improving discovery efficiency of chemical components in Chinese Classical Formula

Peak no.

TR (min)

Formula

Adduct ion

Experimental mass m/z

Theoretical mass m/z

Mass error (ppm)

Fragment ions

Identification

Source

1

2.21

C25H28O16

[M−H]

583.1306

583.1294

2.039

493.0986, 463.0880, 301.0355, 259.0246, 244.0359

Neomangiferin

A

2

2.54

C21H22O12

[M−H]

465.1032

465.1028

0.984

303.0524, 285.0406, 177.0184

Spiraeoside

S

3

4.13

C19H18O11

[M−H]

421.0778

421.0765

2.974

331.0460, 301.0355, 285.0410, 271.0248, 259.0247

Mangiferin

A

4

4.33

C21H21O11

[M−H]

449.1087

449.1078

1.987

287.0553, 259.0620, 171.3426, 151.5096, 125.0229

Taxifolin 7-rhamnoside

N

5

4.49

C19H18O11

[M−H]

421.0778

421.0765

3.045

331.0461, 301.0355, 285.0404, 258.0169

Isomangiferin

A

6

6.30

C27H32O14

[M−H]

579.1721

579.1708

2.224

255.0662

Liquiritigenin 7,4'-di-O-glucopyranoside

G

7

6.65

C26H28O14

[M−H]

563.1406

563.1395

1.826

503.1202, 473.1099, 443.0980, 383.0772, 353.0668, 203.0360

Apigenin 6-C-glucoside-8-C-arabinoside

S

8

7.12

C26H28O16

[M−H]

595.1307

595.1294

2.317

300.0277, 271.0249, 243.0286, 178.9976

Quercetin-3-O-sambubioside

N

9

8.01

C21H22O9

[M−H]

417.1194

417.1180

3.288

255.0661, 153.0180, 135.0074, 119.0487

Neoliquiritin

G

10

8.43

C27H30O14

[M−H]

577.9597

577.9599

− 0.502

541.9865, 506.0078, 479.0923, 255.0665

5-Hydroxy-2-(4-hydroxyphenyl)-4-oxo-4H-chromen-7-yl 2-O-(6-deoxy-α-l-mannopyranosyl)-β-d-glucopyranoside

G

11

8.46

C21H22O9

[M−H]

417.1191

417.1180

2.640

255.0661, 153.0180, 135.0074, 119.0487

Liquiritin

G

12

8.50

C26H14O12

[M−H]

517.0400

517.0402

− 0.217

471.0382, 255.0655, 153.0182, 135.0076, 119.0488

1,1',3,4',5,6',8,8'-Octahydroxy-9H,9'H-2,2'-bixanthene-9,9'-dione

G

13

8.67

C26H28O13

[M−H]

547.1458

547.1446

2.180

487.1227, 457.1145, 427.1230, 367.0822, 337.0720

Isomer of chrysin 6-C-arabinoside-8-C-glucoside

S

14

8.78

C26H30O13

[M−H]

549.1614

549.1603

2.135

417.1192, 255.0661, 153.0180, 135.0074, 119.0486

Liquiritin apioside

G

15

8.86

C32H40O18

[M−H]

711.2114

711.2131

− 2.335

549.1617, 255.0660, 153.0176, 135.0073, 119.0487

Glucoliquirtin asioside

G

16

9.22

C21H20O12

[M−H]

463.0884

463.0871

2.694

301.0346, 300.0276, 272.0300, 271.0249, 255.0298, 178.9979, 151.0024

Hyperoside

N

17

9.23

C27H30O16

[M−H]

609.1450

609.1450

0.015

300.0277, 271.0251, 255.0297, 178.9977

Rutin

N

18

9.26

C21H20O10

[M−H]

431.0972

431.0973

− 0.100

341.0667, 311.0565, 283.0613, 269.0455

Baicalein 7-O-β-d-glucoside

S

19

9.33

C26H28O13

[M−H]

547.1457

547.1446

1.961

487.1252, 457.1140, 427.1031, 367.0822, 337.0718

Chrysin 6-C-arabinoside-8-C-glucoside

S

20

9.42

C26H30O14

[M−H]

565.1558

565.1552

1.023

438.8078, 295.0642, 271.0612

Hydroxyliquiritin apioside

G

21

9.48

C21H18O13

[M−H]

477.0676

477.0664

2.585

302.0389, 301.0354, 283.0245, 255.0300, 227.0338, 178.9976, 151.0024

Quercetin-3-O-glucuronide

N

22

9.59

C26H28O15

[M−H]

579.1363

579.1344

3.183

284.0328, 255.0293, 227.0346, 151.0025

Leucoside

N

23

9.68

C23H24O13

[M−H]

507.1151

507.1133

3.595

345.0613, 330.0382, 315.0154

Viscidulin III-6'-O-β-d-glucopyranoside

S

24

9.74

C21H20O12

[M−H]

463.0884

463.0871

2.694

300.0276, 271.0250, 255.0296, 178.9976, 151.0024

Isoquercitrin

N

25

9.86

C21H18O12

[M−H]

461.0716

461.0715

0.234

285.0407, 267.0296, 175.0238

Scutellarin

S

26

10.61

C26H28O13

[M−H]

547.1457

547.1446

1.961

457.1138, 427.1029, 367.0823, 337.0719

Chrysin 6-C-glucoside-8-C-arabinoside

S

27

11.11

C26H28O13

[M−H]

547.1458

547.1446

2.070

457.1140, 427.1028, 367.0822, 337.0720

Isomer of chrysin 6-C-arabinoside-8-C-glucoside

S

28

11.26

C27H28O16

[M−H]

607.1306

607.1294

2.074

431.0992, 269.0456

Trihydroxyflavone-glycoside glucuronide

S

29

11.35

C27H28O16

[M−H]

607.1303

607.1294

1.563

445.0771, 431.0983, 269.0455

Trihydroxyflavone-glycoside glucuronide

S

30

11.59

C21H20O9

[M−H]

415.1035

415.1024

2.629

295.0613, 267.0663, 251.0709, 223.0758

Chrysin 8-C-β-glucoside

S

31

11.82

C23H24O10

[M−H]

459.1299

459.1286

2.781

255.0661, 153.0181, 135.0073, 119.0487

6'-Acetyliquiritin

G

32

11.91

C23H24O13

[M−H]

507.1144

507.1133

2.037

344.0537, 329.0306, 316.0585

Viscidulin III-2'-O-β-d-glucopyranoside

S

33

12.35

C27H30O13

[M−H]

561.1610

561.1603

1.324

471.1297, 441.1179, 281.0830

5-Hydroxy-7-methoxyflavone 6-C-arabinoside-8-C-glucoside or 7-hydroxy-5-methoxyflavone 6-C-arabinoside-8-C-glucoside

S

34

12.36

C22H20O12

[M−H]

475.0880

475.0871

1.847

299.0563, 284.0327

Isomer of hydroxyl oroxylin A 7-O-glucuronide or hydroxyl wogonoside

S

35

12.37

C45H76O20

[M−H]

935.4862

935.4846

1.699

773.4357, 611.3790, 449.3284

Timosaponin E

A

36

12.59

C51H84O25

[M−H]

1095.5241

1095.5218

2.059

933.4723, 771.4182, 404.0874

(2α,3β,5α,6β,25R)-2,6-Dihydroxyspirostan-3-yl-β-d-glucopyranosyl-(1 → 2)-[β-d-glucopyranosyl-(1 → 3)]-β-d-glucopyranosyl-(1 → 4)-β-d-galactopyranosid

A

37

12.65

C32H26O11

[M−H]

585.1365

585.1391

− 4.440

549.1618, 539.2637, 417.1174, 297.0774, 255.0662

{3-(4-Hydroxy-3-methoxyphenyl)-6-[(2R,3R)-3,5,7-trihydroxy-4-oxo-3,4-dihydro-2H-chromen-2-yl]-2,3-dihydro-1,4-benzodioxin-2-yl}methyl benzoate

G

38

12.66

C26H30O13

[M−H]

549.1614

549.1603

2.026

255.0661, 153.0180, 135.0074, 119.0487

Isoliquiritin apioside

G

39

12.67

C56H92O29

[M−H]

1227.5653

1227.5641

1.024

1065.51123, 933.47205、771.41693, 447.31555

3-O-β-d-xylopyranosyl(1 → 4)-[β-d-glucopyranosyl(1 → 2)]-β-d-glucopyranosyl-26-O-β-d-glucopyranosyl-(25S)-5β-furostane-22-methoxy-3β,26-diol

As

40

12.69

C48H82O19

[M−H]

961.5383

961.5367

1.678

799.4863, 637.4363, 475.3780, 391.2874

20-Glc-Rf

P

41

12.75

C45H74O19

[M−H]

917.4751

917.4741

1.138

755.4233, 593.3687, 553.3922, 364.0068, 319.1408

Timosaponin D

A

42

12.80

C51H84O24

[M−H]

1079.5287

1079.5269

1.677

933.4645, 917.4766, 771.4186, 609.3615

Alliumoside B

A

43

12.87

C23H24O10

[M−H]

459.1300

459.1286

3.107

255.0660, 153.0180, 135.0073, 119.0488

6'-acetylisoliquiritin

G

44

12.91

C21H22O9

[M−H]

417.1190

417.1180

2.281

255.0661, 153.0179, 119.0487

Isoliquiritin

G

45

12.93

C21H18O11

[M−H]

445.0776

445.0765

2.477

270.0490, 269.0455, 251.0349, 241.0509, 223.0393

Baicalin

S

46

12.95

C26H30O13

[M−H]

549.1620

549.1603

3.137

255.0659, 153.0182, 135.0073, 119.0490

Licuraside

G

47

13.01

C45H76O20

[M−H]

935.4857

935.4846

1.111

773.4354, 611.3803, 449.3252

Timosaponin E1

A

48

13.36

C21H22O9

[M−H]

417.1195

417.1180

3.599

255.0662

Neoisoliquiritin

G

49

13.41

C23H22O13

[M−H]

505.0992

505.0977

3.055

329.0667, 314.0435, 299.0198, 271.0250, 255.0291, 227.0344, 175.0237

5,6'-Dihydroxy-6,7-dimethoxyflavone 2'-O-β-d-glucuronide

S

50

13.53

C21H20O11

[M−H]-

447.0930

447.0922

1.861

271.0613, 243.0660

Dihydrobaicalin

S

51

13.60

C42H72O14

[M−H+HCOOH]

845.4905

845.4893

1.381

799.4837, 637.4315, 475.3803, 273.3054

Ginsenoside Rg1

P

52

13.61

C48H82O18

[M−H+HCOOH]

991.5499

991.5472

2.671

945.5428, 783.4907, 637.4326, 475.3786

Ginsenoside Re

P

53

13.69

C35H36O15

[M−H]

695.1979

695.1970

1.199

549.1608, 531.1499, 255.0664, 153.0185, 135.0074, 119.0486

Licorice-glycoside B

G

54

13.81

C36H38O16

[M−H]

725.2089

725.2076

1.722

549.1630, 531.1491, 255.0660, 153.0179, 135.0072, 119.0488

Licorice-glycoside A

G

55

13.92

C21H18O11

[M−H]

445.0761

445.0765

− 0.961

270.0488, 269.0455, 249.0541, 241.0501, 225.0548

Apigenin 7-O-glucuronide

S

56

14.12

C50H84O23

[M−H]

1051.5342

1051.5320

2.107

919.4982, 889.4860, 757.4376, 595.3851, 433.3344

Officinalisnin-II

As

57

14.20

C45H76O19

[M−H]

919.4907

919.4897

1.103

757.4378, 595.3847, 433.3319

3-O-β-d-glucopyranosyl (1 → 2)-β-d-glucopyranosyl-26-O-β-d-glucopyranosyl-(25S)-5β-furostane-3β,22α,26-triol

As

58

14.24

C50H84O23

[M−H]

1051.5327

1051.5320

0.709

919.4877, 889.4722, 757.4381, 594.6215, 418.5930

25-Epi-officinalisnin II

As

59

14.28

C45H76O21

[M−H]

951.4787

951.4795

− 0.878

633.9669, 475.0884

(2α,3β,5α,22S)-26-(β-d-Glucopyranosyloxy)-2,5,22-trihydroxyfurostan-3-yl 4-O-β-d-glucopyranosyl-β-d-glucopyranoside

As

60

14.41

C45H74O17

[M−CO2−H]

841.4950

841.4944

0.716

781.4773, 637.4346, 475.3789

Ginsenoside mRg1

P

61

14.45

C48H74O20

[M−H]

969.4695

969.4690

0.525

922.5041, 825.9856, 760.4498, 471.1639, 351.0573

(3β,22β)-22-(β-d-Glucopyranosyloxy)-11-oxoolean-12-en-3-yl 2-O-β-d-glucopyranuronosyl-β-d-glucopyranosiduronic acid

G

62

14.46

C56H92O27

[M−H+HCOOH]

1241.5817

1241.5797

1.584

1241.5817, 1195.5740, 1079.5382, 1033.5212, 917.4714, 755.4238, 455.1436

Ophiopojaponin G

O

63

14.55

C21H18O11

[M−H]

445.0772

445.0765

2.409

270.0491, 269.0456, 251.0346, 241.0503, 225.0552, 223.0392

Isomer of baicalin

S

64

14.60

C45H76O19

[M−H]

919.4914

919.4897

1.831

757.4382, 595.3838, 433.3329

3-O-β-d-Glucopyranosyl (1 → 2)-β-d-glucopyranosyl-26-O-β-d-glucopyranosyl-(25R)-5β-furostane-3β,22α,26-triol

As

65

14.61

C51H86O24

[M−H]

1081.5433

1081.5425

0.740

919.4806, 757.4385, 595.3859

26-(Hexopyranosyloxy)-22-hydroxyfurostan-3-yl hexopyranosyl-(1 → 2)hexopyranosyl-(1 → 4)hexopyranoside

A

66

14.65

C21H18O10

[M−H]

429.0821

429.0816

1.018

253.0505, 175.0236, 113.0229

Chrysin-7-O-β-d-glucuronid

S

67

14.79

C22H20O11

[M−H]

459.0937

459.0922

3.338

283.0614, 269.0411, 268.0377, 241.0481, 175.0235

Oroxylin A-7-O-β-d-glucuronide

S

68

14.81

C51H84O23

[M−H]

1063.5324

1063.5320

0.362

901.4807, 755.4263, 468.3537, 423.1946

Timosaponin BIV

A

69

14.91

C22H20O12

[M−H]

475.0882

475.0871

2.247

299.0563, 284.0327

Isomer of hydroxylwogonin glucuronide

S

70

14.93

C56H92O28

[M−H]

1211.5714

1211.5691

1.875

1079.5255, 917.4763, 865.0001, 755.4222

Timosaponin C1

A

71

15.02

C45H76O19

[M−H]

919.4921

919.4897

2.571

841.4293, 757.4416, 595.3847, 459.0930

Timosaponin BII

A

72

15.59

C22H20O11

[M−H]

459.0932

459.0922

2.205

283.0614, 269.0431, 268.0378, 240.0425, 175.0237

Wogonoside

S

73

15.70

C57H94O27

[M−H]

1209.5912

1209.5899

1.088

1047.5446, 901.4795, 883.4755, 755.4213, 737.4127, 431.3182

(2α,3β,5α,25R)-2-Hydroxyspirostan-3-yl β-d-glucopyranosyl-(1 → 2)-[4-O-[(2S,3R,4S)-3-hydroxy-4-(hydroxymethyl)-4-methyltetrahydro-2-furanyl]-β-d-glucopyranosyl-(1 → 3)]-β-d-glucopyranosyl-(1 → 4)-β-d-galactopyranoside

A

74

15.91

C51H84O22

[M−H]

1047.5380

1047.5371

0.868

901.4722, 885.4497, 755.4229

Protoneodioscin

As

75

16.06

C51H84O22

[M−H]

1047.5382

1047.5371

1.107

901.4749, 883.4813, 755.4178, 413.2992

Protodioscin

As

76

16.09

C50H84O25

[M−H]

1083.5170

1083.5218

− 4.452

1047.5375, 901.4825, 802.9248, 755.4275, 487.1885

(2α,3β,5α,22S,25R)-26-(β-d-Glucopyranosyloxy)-2,5,22-trihydroxyfurostan-3-yl β-d-xylopyranosyl-(1- > 3)-β-d-glucopyranosyl-(1- > 4)-β-d-galactopyranoside

As

77

16.29

C50H84O22

[M−H]

1035.5374

1035.5371

0.289

903.5004, 889.4836, 757.4378, 595.3881, 433.3307

3-O-α-l-Rhamnopyranosyl(1 → 4)-[β-d-xylopyranosyl (1 → 2)]-β-d-glucopyranosyl-26-O-β-d-glucopyranosyl-(25S)-5β-furostane-3β,22α,26-trio

As

78

16.69

C51H86O23

[M−H]

1065.5487

1065.5476

1.028

903.4990, 757.4362, 595.3870, 445.8120

(5α,22R)-26-(β-d-Glucopyranosyloxy)-22-hydroxyfurostan-3-yl 6-deoxy-α-l-mannopyranosyl-(1 → 4)-[α-l-mannopyranosyl-(1 → 2)]-β-d-glucopyranoside

A

79

16.87

C48H72O22

[M−H]

999.4452

999.4431

2.041

837.3885, 351.0569

24-hydroxy-licoricesaponin A3

G

80

16.90

C51H86O23

[M−H]

1065.5483

1065.5476

0.680

903.4954, 757.4395, 739.4266, 595.3826, 433.3332

3-O-α-l-rhamnopyranosyl (1 → 4)-[β-d-glucopyranosyl(1 → 2)]-β-d-glucopyranosyl-26-O-β-d-glucopyranosyl(25R)-5β-furostane-3β,22α,26-triol

As

81

17.24

C45H76O18

[M−H]

903.4975

903.4948

0.363

757.4323, 595.3828, 433.3293

Aspacochioside A

As

82

17.47

C45H76O18

[M−H]

903.4968

903.4948

2.256

757.4388, 595.3868, 433.3327

Isomer of aspacochioside A

As

83

17.53

C44H64O19

[M−H]

895.3964

895.3958

0.619

456.4406, 429.6882, 351.0563

Hydroxy acetoxyglycyrrhizin

G

84

17.75

C42H62O18

[M−H]

853.3855

853.3852

0.303

351.0568

22-Hydroxy-licoricesaponin G2

G

85

19.31

C48H72O21

[M−H]

983.4494

983.4482

1.184

821.3983, 351.0575

Licorice-saponin A3

G

86

19.61

C42H60O17

[M−H]

835.3760

835.3747

1.560

801.4187, 443.5862, 381.5747, 351.0575

formylglycyrrhizin acid

G

87

19.71

C50H82O22

[M−H]

1033.5227

1033.5214

1.267

901.4716, 739.4283, 577.3704, 427.2860

3-O-β-d-xylopyranosyl (1 → 4)-[β-d-glucopyranosyl (1 → 2)]-β-d-glucopyranosyl-26-O-β-d-glucopyranosyl-(25S)-5β-furostane-20 (22)-ene-3β,26-diol

As

88

19.73

C44H64O18

[M−H]

879.4027

879.4009

2.068

351.0570, 193.0346, 175.0236, 113.0229

22β-Acetoxyglycyrrhizin

G

89

19.78

C45H74O18

[M−H]

901.4808

901.4791

1.873

739.4278, 577.3749, 356.5983

Xilingsaponin B

A

90

19.83

C42H62O17

[M−H]

837.3911

837.3903

0.935

351.0570

Licorice-saponin P2

G

91

19.89

C51H84O23

[M−H]

1063.5335

1063.5320

1.396

901.4749, 739.4255, 577.3785, 445.3186

3-O-β-d-xylopyranosyl(1 → 4)-[β-d-glucopyranosyl(1 → 2)-β-d-glucopyranosyl(1 → 2)]-β-d-glucopyranosyl-26-O-β-d-glucopyranosyl-(25S)-furostane-5-ene-22-methoxy-3β,26-diol

As

92

20.01

C57H94O26

[M-CO2-H]

1149.6069

1149.6051

1.566

1149.6069, 1107.5963, 945.5444, 783.4910, 621.4361, 459.3843

Ginsenoside mRb1

P

93

20.04

C47H80O17

[M-H+HCOOH]

965.4387

965.4377

1.025

919.4950, 758.4404, 497.1143, 435.1156

Gypenoside IX

P

94

20.09

C48H76O19

[M−H]

955.4913

955.4897

1.699

793.4381, 731.4389, 613.3751, 569.3850, 523.3790, 455.3533

Ginsenoside Ro

P

95

20.11

C56H92O25

[M−CO2−H]

1119.5964

1119.5946

1.675

1077.5857, 945.5567, 915.5332, 783.4905, 621.4422, 459.3855

Ginsenoside mRb2

P

96

20.13

C45H74O17

[M−H]

885.4871

885.4842

3.199

739.4278, 577.3763, 484.2304

3-O-[{α-L-rhamnopyranosyl-(1 → 4)}{β-d-glucopyranosyl}]-26-O-[β-d-glucopyranosyl](25S)-5β-furost-20(22)-en-3β,26-diol

As

97

20.16

C42H60O16

[M−H]

819.3818

819.3815

2.085

351.0568, 193.0346, 175.0237, 113.0229

Licorice-saponin E2

G

98

20.18

C44H60O17

[M−H]

859.3739

859.3747

-0.904

837.3852, 797.3743, 351.0557

Methyllicorice-saponin Q2

G

99

20.19

C42H62O17

[M−H]

837.3916

837.3903

1.521

351.0570

Macedonoside A

G

100

20.28

C48H72O20

[M−H]

967.4548

967.4533

1.498

645.3641, 541.9834, 497.1151, 435.1159

(3β,22β)-23-Hydroxy-29-oxo-22,29-epoxyolean-12-en-3-yl 6-deoxy-α-L-mannopyranosyl-(1 → 2)-β-d-glucopyranuronosyl-(1 → 2)-β-d-glucopyranosiduronic acid

G

101

20.29

C44H64O17

[M−H]

863.4081

863.4082

2.575

351.0566, 193.0343, 175.0241, 113.0229

22β-Acetoxyglycyrrhaldehyde

G

102

20.45

C42H62O17

[M−H]

837.3915

837.3903

1.377

351.0568

Licorice-saponin Q2

G

103

20.47

C39H66O14

[M−H]

757.4377

757.4369

1.132

595.3846, 465.2493, 357.2007, 271.7701, 161.0441

Anemarrhenasaponin I or II

A

104

20.50

C42H62O16

[M−H]

821.3968

821.3954

1.678

352.0605, 351.0569, 193.0346, 175.0237, 113.0229

Glycyrrhizin acid

G

105

20.52

C42H64O16

[M−H]

823.4128

823.4111

1.778

721.3478, 351.0557, 193.0344, 175.0237, 113.0226

Licorice-saponin J2

G

106

20.74

C42H62O17

[M−H]

837.3918

837.3903

1.736

351.0573

Licorice-saponin G2

G

107

20.75

C39H62O14

[M−H+HCOOH]

799.4072

799.4111

− 4.869

799.4072, 753.4070, 205.0709, 163.0600, 119.0335

Ophiopojaponin Ra

O

108

20.79

C42H64O15

[M−H]

807.4177

807.4161

1.873

351.0572, 193.0346, 175.0236, 113.0230

Licorice-saponin B2

G

109

20.88

C42H62O16

[M−H]

821.3971

821.3954

2.043

352.0600, 351.0571, 193.0346, 175.0237, 113.0229

Licorice-saponin H2

G

110

20.95

C39H64O14

[M−H]

755.4227

755.4212

1.982

593.3716, 201.9089

Timosaponin AII

A

111

21.06

C42H62O16

[M−H]

821.3972

821.3954

2.201

352.0616, 351.0570, 193.0346, 175.0238, 113.0229

Licorice-saponin K2

G

112

21.13

C42H62O16

[M−H]

821.3970

821.3954

1.897

352.0634, 351.0573, 193.0345, 175.0237, 113.0229

Apioglycyrrhizin

G

113

21.57

C42H62O15

[M−H]

805.4006

805.4005

0.090

351.0572, 193.0349, 175.0240, 113.0229

Licorice-saponin C2

G

  1. A: Anemarrhe naerhizoma, S: Scutellariae radix, N: Nelumbinis folium, G: Glycyrrhizae radix, As: Asparagi radix, O: Ophiopogonis radix, P: Ginseng radix