Table 1 Metabolites annotated in the different licorice root samples extracts using UPLC-MS/MS in positive and negative ionization modes

1

1.14

Phenol, dimethoxy-4-(2-propenyl)

₁₄O₁₁H₃C

Melanoidin

[M-H]⁻

175 (M-H-H₂O), 162 (M-H-OCH₃), 131 (M-H-2 OCH₃), 152 (M-H-C₃H₅)

2

1.21

Pyran-4-one, dihydro-dihydroxy-methyl

₇O₆H₄C

Melanoidin

[M-H]⁻

124 (M-H₂O), 127 (M-CH₃), 114 (M-CO)

3

1.36

Furanmethanol

₆O₅H₂C

Melanoidin

[M-H]⁻

79 (M-H-H₂O), 69 (M-H-CO), 65 (M-H-CH₃OH)

4

1.37

Phenethylamine, methyl-N-vanillyl

₂₁O₂N₁₇HC

Melanoidin

[M + H]⁺

254 (M + H-H₂O), 241 (M + H-OCH₃), 153 (M + H-C₉H₁₁)

5

1.4

Dihydroxyacetophenone

₈O₈H₃C

Melanoidin

[M-H]⁻

137 (C₇H₅O₃), 109 (C₆H₅O₂)

6

1.42

Dihydro-methylpyrrolopyrimidinone

C₈H₁₀N₂O

pyrimidine derivative

[M + H]⁺

136 (M + H-CH₃), 123 (M + H-CO)

7

1.45

Dihydro-3-methylfuran

₈O₅HC

Melanoidin

[M-H]⁻

68 (M-H-CH₃), 55 (M-H-CO), 54 (C₄H₆)

8

1.47

2-(Methyl-butenyl)-5-(phenylethyl)-benzenediol

₂₂O₁₉H₂C

Resorcinol

[M-H]⁻

212(M-H- C₅H₉), 109 (M-H- C₁₃H₁₆), 80 (C₆H₈), 68 (C₅H₈)

9

1.49

Pentyl-2-prenyl-benzenediol-3-Me ether

₂₆O ₁₇H₂C

Resorcinol

[M-H]⁻

192 (M-H-C₅H₉), 123 (M-H-C₁₀H₂₀), 80 (C₆H₈), 68 (C₅H₈)

10

1.52

Dihydroxybenzoic acid- Xylopyranosyl ester

₁₄O₁₂H₈C

Phenolic acid ester

[M-H]⁻

267(M-H-H₂O), 153 (M-H-xylopyranose), 109 (M-H-xylopyranose-CO₂)

11

1.546

Hydroxy-Bis(3-methyl-2-butenyl)-5-(2-phenylethenyl)-benzenediol

C₂₄H₂₈O₃

Stilbene

[M + H]⁺

227 (M + H-2 isoprenyl unit), 296 (M + H-isoprenyl unit)

12

1.56

1-(4-Hydroxyphenyl)-3-(7-methoxybenzofuran-6-yl) propanone

₁₆O₁₈H₄C

Aliphatic ketone

[M-H]⁻

202 (C₁₂H₁₀O₃), 174 (C₁₁H₁₀O₂), 120 (C₇H₄O₂)

13

1.57

3-Methyl-3-hepten-2-one

₁₄O₈HC

Aliphatic ketone

[M + H]⁺

112 (C₇H₁₂O), 84 (C₆H₁₂)

14

1.69

3-(4-Hydroxyphenyl)-phenyl-propenone

C₁₅H₁₂O₂

Chalcone

[M-H]⁻

146 (X2), 118 (Y2), 104 (Y1), 76 (X1) (Figure S2)

15

2.03

Thujanol

C₁₀H₁₈O

Monoterpene alcohol

[M + H]⁺

137 (M + H-H₂O), 140 (M + H-CH₃)

16

2.05

Trihydroxy-4-methoxybibenzyl

C₁₅H₁₆O₄

Stilbene

[M-H]⁻

241 (M-H-H₂O), 228 (M-H-OCH₃)

17

7.74

Dihydroxyflavanone-Di-O-hexoside

C₂₇H₃₂O₁₄

Flavanone glycosides

[M + H]⁺

419 (M + H-hexose), 257 (M + H-2 hexose), 239 (M + H-2 hexose -H₂O), 229 (M + H-2 hexose -CO), 213 (M + H -2 hexose -CO₂), 137 (^1,3 A⁺), 163 (M + H -2 hexose-ring B)

18

8.1

Amorfrutin 1/A^a

C₂₁H₂₄O₄

Stilbene

[M-H]⁻

225 (C₁₅H₁₃O₂), 295 (M-H-CO₂), 270 (M-H-isoprenyl unit)

19

9.1

Dihydroxyflavanone-O-hydroxypropanoyl hexoside

C₂₄H₂₆O₁₁

Flavanone glycosides

[M-H]⁻

257(M-H-Hydroxypropanoyl hexose), 135 (^1,3 A⁻), 161((M-H-Hydroxypropanoyl hexose-ring B)

20

9.86

3-(3,4-Dihydroxyphenyl)-2-propenoic acid- docosyl ester

₅₂O₃₁H₄C

Phenolic acid ester

[M + H]⁺

471 (M + H-H₂O), 180 (M + H-docosanol), 136 (M + H-docosanol-CO₂), 118 (M + H-docosanol-CO₂ -H₂O)

21

9.93

Tetrahydroxyflavan-O-pentoside

C₂₀H₂₂O₉

Flavane glycosides

[M-H]⁻

273 (M-H-pentose), 295 (M-H-pentose-ring B)

22

10

Dihydroxy dimethoxy-O-hexoside

C₂₃H₂₄O₁₁

Isoflavone glycosides

[M + H]⁺

315 (M + H-hexose), 297 (M + H -hexose -H₂O), 287 (M + H -hexose -CO), 271 (M + H-hexose-CO₂), 285 (M + H-hexose − 2CH₃), 167 (^1,3 A⁺), 149 (^1,3B⁺)

23

10.27

Trihydroxychalcone-O -Rhamnopyranosyl glucopyranoside]

C₂₇H₃₂O₁₃

Chalcone glycoside

[M + H]⁺

419 (M + H-rhamnose), 257 (M + H-rhamnoglucose), 137 (ring A)

24

10.28

Dihydroxyflavanone-O-rutinoside^a

C₂₇H₃₂O₁₃

Flavanone glycosides

[M-H]⁻

257 (M-H- rhamnoglucose) ,135 (^1,3 A⁻), 161 (M-H-ring B)

25

10.59

Dihydroxyflavone-O-pentosyl hexoside

C₂₆H₂₈O₁₃

Flavone glycosides

[M-H]⁻

253 (M-H-pentohexose), 135 (^1,3 A⁻), 120 (^1,3B⁻), 235 (M-H- pentohexose -H₂O), 209 (M-H- pentohexose- CO₂)

26

10.66

Trihydroxyflavone-O-Rhamnopyranoside (afzelin) ^a

C₂₁H₂₀O₁₀

Flavone glycosides

[M + H]⁺

287 (M + H-rhamnose), 153 (^1,3 A⁺), 122 (^1,3B⁺), 269 (M + H-rhamnose- H₂O), 243(M + H-rhamnose -CO₂)

27

10.9

Dihydroxyflavanone-O-pentosyl hexoside

C₂₆H₃₀O₁₃

Flavanone glycosides

[M-H]⁻

255(M-H- pentohexose), 135 (^1,3 A⁻), 161(M-H- pentohexose -ring B)

28

11.05

Isoliquiritin apioside^a

C₂₆H₃₀O₁₃

Chalcone glycoside

[M-H]⁻

255 (M-H- apioglucose), 135 (ring A), 119 (ring B)

29

11.15

Dihydroxy methoxy flavanone-O-hexoside

C₂₂H₂₄O₉

Flavanone glycosides

[M-H]⁻

269 (M-H-hexose), 251 (M-H-hexose H₂O), 241 (M-H-hexose-CO), 225 (M-H-hexose-CO₂), 137 (^1,3 A⁻) ,161 (M-H-hexose-ring B)

30

11.21

Vitexin-O-rhamnoside^a

C₂₁H₂₀O₁₀

Flavone-C-glycosides

[M-H]⁻

431 (M-H- rhamnose), 341 (Cross link cleavage in glucose unit), 311 (Cross link cleavage in glucose unit)

31

11.46

Dihydroxy flavanone-O-hexoside

C₂₁H₂₂O₉

Flavanone glycosides

[M + H]⁺

257 (M + H-hexose), 239 (M + H-hexose-H₂O), 229 (M + H-hexose-CO), 213 (M + H-hexose- CO₂),137 (^1,3 A⁺), 163 (M + H-hexose -ring B)

32

11.93

Yunganoside G1

C₄₈H₇₄O₂₁

Triterpene Saponin (oleanane type)

[M-H]⁻

840 (M-H-rhamnose), 489 (M-H-di-glucouronic residue- rhamnose),470 ((M-H-di-glucouronic residue- rhamnose-H₂O), 497 (rhamnose di-glucouronic residue -H), 458 (M-H- di-glucouronic residue- rhamnose-CH₂O), 351 (di-glucouronic residue -H)

33

12.12

Trihydroxyflavanone-O-pentosyl hexoside

C₂₆H₃₀O₁₄

Flavanone glycosides

[M-H]⁻

271 (M-H-pentohexose),155 (^1,3 A⁻), 177 (M-H-pentohexose-ring B)

34

12.43

Trihydroxyflavanone-O-hexoside

C₂₁H₂₂O₁₀

Flavanone glycosides

[M + H]⁺

273 (M + H-hexose), 169 (^1,3 A⁺), 195 (M + H-hexose-ring B)

35

12.58

Trihydroxychalcone-O-Apiofuranosyl glucopyranoside

C₂₆H₃₀O₁₃

Chalcone glycoside

[M + H]⁺

419 (M + H-apiose), 257 (M + H- apioglucose), 137 (ring A)

36

12.6

Uralsaponin E^a

C₄₂H₆₀O₁₇

Triterpene Saponin (oleanane type)

[M-H]⁻

659 (M-H-glucouronic residue), 483 (M-H– di-glucouronic residue),

465 (M-H-di-glucouronic residue- H₂O), 437 (M-H-di-glucouronic residue- H₂O- CH₂O), 447 (M-H-di-glucouronic residue − 2H₂O), 176 (glucouronic residue)

37

12.74

Trihydroxyflavone-glucoside^a

C₂₁H₁₈O₁₁

Flavone glycosides

[M-H]⁻

269 (M-H-glucose), 105 (^1,3B⁻), 167 (^1,3 A⁻), 265 (M-H-glucose-H₂O), 239 (M-H-glucose-CO₂)

38

12.83

Dihydroxyisoflavone-dimethoxy-O-hydroxyphenyl)propanoyl-glucoside

C₃₂H₃₂O₁₃

Isoflavone glycosides

[M-H]⁻

309 (M-H-hydroxy phenyl propanoyl glucose), 291 (M-H- hydroxy phenyl propanoyl glucose -H₂O), 281 (M-H- hydroxy phenyl propanoyl glucose -CO), 265 (M-H- hydroxy phenyl propanoyl glucose -CO₂), 165 (^1,3 A⁻), 147 (^1,3B⁻)

39

13.01

licorice glucoside D1^a

C₃₅H₃₆O₁₅

Flavanone glycosides

[M-H]⁻

255 (M-H-coumaroyl apioglucose),135 (^1,3 A⁻), 119 (ring B)

40

13.05

Trihydroxychalcone-O-Hydroxycinnamoyl-apiofuranosyl-glucopyranoside

C₃₅H₃₆O₁₅

Chalcone glycoside

[M-H]⁻

401 (M-H- apioglucose), 255 (M-H-hydroxycinnamoyl apioglucose), 135 (ring A)

41

13.12

Hydroxy methoxy isoflavone-O-hexoside

C₂₂H₂₂O₉

Isoflavone glycosides

[M-H]⁻

269 (M-H-hexose), 251(M-H-hexose-H₂O), 241 (M-H-hexose -CO), 225 (M-H-hexose -CO₂), 137 (^1,3 A⁻), 133 (^1,3B⁻)

42

13.2

Licorice glycoside C1

4’,7-Dihydroxyflavanone; (S)-form, 4’-O-[4-Hydroxy-3-methoxycinnamoyl-(→5)-β-D-apiofuranosyl-(1→2)-β-D-glucopyranoside]

C₃₆H₃₈O₁₆

Flavanone glycosides

[M-H]⁻

710 (M-H-CH₃), 255 (M-H- Hydroxy methoxycinnamoyl apioglucose), 135 (^1,3 A⁻), 119 (^1,3B⁻)

43

13.34

Yunganosides L 1 or J1

C₄₈H₇₂O₂₀

Triterpene Saponin (oleanane type)

[M-H]⁻

950 (M-H- H₂O), 833 (M-H- C₄H₆O₅), 645 (M-H- C₄H₆O₅-C₈H₁₂O₅), 497 (rhamnose di-glucouronic residue–H), 453(M-H -di-glucouronic rhamnose -H₂O), 176 (glucouronic residue), 162 (glucose residue)

44

13.42

Liquorice saponin F3

C₄₈H₇₂O₁₉

Triterpene Saponin (oleanane type)

[M-H]⁻

497 (rhamnose di-glucouronic residue -H),

436 (M-H-di-glucouronic-rhamnose-H₂O), 418(M-H-di-glucouronic-rhamnose − 2 H₂O), 454 (M-H-di-glucouronic-rhamnose), 176 (glucouronic residue)

45

13.44

Uralsaponin F^a

C₄₄H₆₄O₁₉

Triterpene Saponin (oleanane type)

[M-H]⁻

719 (M-H-glucouronic residue), 543 (M-H-di-glucouronic residue), 525 (M-H-di-glucouronic residue-H₂O), 507 (M-H-di-glucouronic residue- 2 H₂O), 497 (rhamnose di-glucouronic residue -H), 495(M-H-di-glucouronic residue-H₂O-CH₂O) 465 (M-H- di-glucouronic residue- H₂O-acetyl residue), 447(M-H- di-glucouronic residue − 2H₂O-acetyl residue)

46

13.52

Liquorice saponin J2^a

C₄₂H₆₄O₁₆

Triterpene Saponin (oleanane type)

[M-H]⁻

453 (M-H-di-glucouronic residue -H₂O), 471(M-H- di-glucouronic residue), 647(M-H-glucouronic residue)

47

13.83

Tetrahydroxychalcone-Me ether

C₁₆H₁₄O₅

Chalcone

[M-H]⁻

270 (M-H-CH₃), 151 (ring A), 133 (ring B)

48

13.94

Trihydroxychalcone-O-Hydroxy-methoxycinnamoyl-apiofuranosyl glucopyranoside

C₃₆H₃₈O₁₆

Chalcone glycoside

[M + H]⁺

433 (M + H- apioglucose), 257 (M + H-hydroxy methoxycinnamoyl apioglucose), 137 (ring A)

49

14.03

Yunganoside K1

C₄₈H₇₂O₂₁

Triterpene Saponin (oleanane type)

[M-H]⁻

497 (rhamnose di-glucouronic residue–H), 486 (M-H- di-glucouronic-rhamnose), 176 (glucouronic residue)

50

14.3

Polypodoside B

C₃₉H₆₂O₁₃

Triterpene Saponin (cholestane type)

[M + H]⁺

593 (M + H-rhamnose), 577(M + H-glucose), 431 (M + H-glucose-rhamnose)

51

14.55

Yunganoside G2^a

C₄₂H₆₄O₁₇

Triterpene Saponin (oleanane type)

[M-H]⁻

777 (M-H-H₂O-CO₂), 487 (M-H-di-glucouronic), 469 (M-H-di-glucouronic-H₂O), 351(di-glucouronic residue-H),

52

14.68

Dihydroxy-dimethoxyflavone

C₁₇H₁₄O₆

Flavone

[M + H]⁺

297 (M + H-H₂O), 271 (M + H-CO₂), 153 (^1,3 A⁺), 166 (^1,3B⁺)

53

15.03

Uralsaponin M

C₄₄H₆₄O₁₈

Triterpene Saponin (oleanane type)

[M-H]⁻

703 (M-H-glucouronic residue), 527(M-H-di-glucouronic residue)

54

15.22

(Licorice saponin G2) 24-Hydroxyglycyrrhizin^a

C₄₂H₆₂O₁₇

Triterpene Saponin (oleanane type)

[M + H]⁺

821(M + H-H₂O), 777 (M + H-H₂O-CO₂), 663 (M + H- glucouronic residue), 351(di-glucouronic residue -H)

55

15.24

Yunganoside P^a

C₄₂H₆₀O₁₇

Triterpene Saponin (oleanane type)

[M-H]⁻

483 (M-H- di-glucouronic residue), 465 (M-H- di-glucouronic residue -H₂O), 434 (M-H- di-glucouronic residue -H₂O-OCH₃), 176 (glucouronic residue)

56

15.43

Dihydroxyflavanone-O-Indolylcarbonyl-pentosyl hexoside

C₃₅H₃₅NO₁₄

Flavanone glycoside

[M-H]⁻

400 (M-H-pentohexose), 241(M-H- indolylcarbonyl pentohexose), 135 (^1,3 A⁻), 161 (M-H- indolylcarbonyl pentohexose -ring B)

57

15.54

Yunganoside N1

C₄₂H₆₄O₁₄

Triterpene Saponin (oleanane type)

[M + H]⁺

617(M + H-glucouronic residue),

441((M + H-di-glucouronic residue), 353 (di-glucouronic residue + H),

58

15.8

Licorice saponin B2 or Isomer of licorice saponin B2

C₄₂H₆₄O₁₅

Triterpene Saponin (oleanane type)

[M-H]⁻

789(M-H-H₂O), 613(M-H-glucouronyl residue-H₂O), 351(di-glucouronic residue -H)

59

16.45

Dihydroxy methoxy isoflavane

C₁₆H₁₆O₄

Isoflavane

[M-H]⁻

258 (M-H-CH₃), 123 (ring A), 149 (M-H-ring B)

60

16.68

Dihydroxy methoxy-prenylisoflavone

C₂₁H₂₀O₅

Isoflavone

[M-H]⁻

333 (M-H-H₂O), 323 (M-H-CO), 307 (M-H-CO₂), 336 (M-H-CH₃), 281(M-H- isoprenyl unit), 117 (^1,3B⁻), 218 (^1,3 A⁻)

61

17.35

Licoricesaponin K2

C₄₂H₆₂O₁₆

Triterpene Saponin (oleanane type)

[M + H]⁺

647(M + H- glucouronic residue), 471 (M + H- di-glucouronic residue), 453(M + H- di-glucouronic residue - H₂O)

62

17.65

Macedonoside D

C₄₂H₆₀O₁₆

Triterpene Saponin (oleanane type)

[M-H]⁻

467(M-H-di-glucouronic residue), 449(M-H- di-glucouronic residue -H₂O)

63

18.14

Flavestin B^a

₂₀O₁₉H₂C

Resorcinol

[M + H]⁺

212 (M + H-isoprenyl unit), 111 (M + H-isoprenyl unit- C₈H₅), 82 (C₆H₁₀), 70 (C₅H₁₀), 54 (C₄H₆)

64

18.2

Macedonoside B

C₄₂H₆₂O₁₇

Triterpene Saponin (oleanane type)

[M-H]⁻

819 (M-H-H₂O), 485 (M-H- diglucouronic residue), 351(diglucouronic residue -H)

65

18.35

Uralsaponin B

C₄₂H₆₂O₁₆

Triterpene Saponin (oleanane type)

[M + H]⁺

647 (M + H − glucouronic residue), 471(M-H- di-glucouronic residue), 351(di-glucouronic residue-H)

66

18.87

Isoliquiritigenin^a

C₁₅H₁₂O₄

Chalcone

[M-H]⁻

135 (ring A), 119 (ring B), 93 (ring B fragment)

67

19.1

Glycyrrhizin^a

C₄₂H₆₂O₁₆

Triterpene Saponin (oleanane type)

[M-H]⁻

803 (M -H-H₂O), 759 (M-H-H₂O-CO₂), 645(M -H- glucouronic residue), 351 (di-glucuronic acid residue -H)

68

19.5

Trihydroxycoumestan-Me ether

C₁₆H₁₀O₆

Coumestan

[M + H]⁺

268 (M + H- OCH₃), 281(M + H-H₂O)

69

19.59

Dihydroxy dimethoxyisoflavone

C₁₇H₁₄O₆

Isoflavone

[M-H]⁻

297 (M-H-H₂O), 287 (M-H-CO), 271 (M-H-CO₂), 285 (M-H-2 CH₃), 167 ((^1,3 A⁻), 149 (^1,3B⁻)

70

19.62

Hydroxy methoxyisoflavone

C₁₆H₁₂O₄

Isoflavone

[M-H]⁻

251 (M-H-H₂O), 241 (M-H-CO), 225 (M-H-CO₂), 137 (^1,3 A⁻), 133 ((^1,3B⁻)

71

19.66

Licodione^a

C₁₅H₁₂O₅

Chalcone

[M-H]⁻

162 (X2), 136 (Y1), 134 (Y2),108 (X1) (Figure S2)

72

19.81

Licoriphenone-O-De-Me

₂₂O₂₀H₆C

Aliphatic ketone

[M + H]⁺

290 (M + H-isoprenyl unit), 250 (C₁₄H₁₈O₄), 222 (C₁₃H₁₈O₃), 138 (C₇H₆O₃)

73

19.9

Dihydroxy-oleanadienoic acid-diglycoside

C₄₂H₆₂O₁₄

Triterpene Saponin (oleanane type)

[M-H]⁻

447 (M-H-2 hexose − 2 H₂O), 465 (M-H-2 hexose)

74

20.26

Xambioona

C₂₅H₂₄O₄

Flavanone

[M-H]⁻

369 (M-H-H₂O), 359 ((M-H-CO), 343 (M-H-CO₂), 201 (^1,3 A⁻), 227 (M-H-ring B)

75

20.44

Trihydroxy-oleanadienoic acid-diglycoside

C₄₂H₆₄O₁₅

Triterpene Saponin (oleanane type)

[M-H]⁻

483 (M-H-2 hexose), 465 (M-H-2 hexose -H₂O), 447 (M-H-2 hexose − 2 H₂O)

76

20.76

Glycyrrhizin isomer

C₄₂H₆₂O₁₆

Triterpene Saponin (oleanane type)

[M-H]⁻

803(M-H-H₂O), 759 (M-H-H₂O-CO₂), 645 (M- H-glucouronic residue), 351(di-glucouronic residue - H)

77

20.94

Tetrahydroxy-prenylchalcone

C₂₀H₂₀O₅

Chalcone

[M-H]⁻

270 (M-H-isoprenyl unit), 203 (ring B), 135 (ring A)

78

21.07

Trihydroxy methoxy-prenylisoflavone

C₂₁H₂₀O₆

prenyl Isoflavone

[M-H]⁻

351 (M-H-H₂O), 341 (M-H-CO), 325 (M-H-CO₂), 354 (M-H-CH₃), 298 (M-H-isoprenyl unit), 149 (^1,3B⁻), 222 (M-H- ring A)

79

21.1

Trihydroxy-prenylflavanone

C₂₀H₂₀O₅

Flavanone

[M + H]⁺

323 (M + H-H₂O), 313 (M + H-CO), 297 (M + H-CO₂), 272 (M + H-isoprenyl unit), 221 (^1,3 A⁻), 247 (M + H-ring B)

80

21.2

Gancaonin Y^a

C₂₁H₂₂O₄

Isoflavane

[M + H]⁺

324(M + H-CH₃), 123 (^1,3 A⁺) ,149 (M + H-ring B)

81

21.3

Glabrocoumarin^a

C₂₀H₁₆O₅

Coumarin

[M + H]⁺

163 (C₉H₇O₃), 119 (C₈H₇O)

82

21.6

Gancaonin V

C₁₉H₂₀O₄

Prenylated dihydrophenanthrene

[M + H]⁺

244 (M + H-isoprenyl unit), 285 (M + H-CO)

83

21.74

Arabo/Apioglycyrrhizin

C₄₁H₆₂O₁₄

Triterpene Saponin (oleanane type)

[M-H]⁻

715(M-H H₂O-CO₂), 645(M-H-arabinose)

84

21.91

Uralsaponin C^a

C₄₂H₆₄O₁₆

Triterpene Saponin (oleanane type)

[M-H]⁻

647(M-H- glucouronic residue), 471[M-H-di- glucouronic residue], 453[M-H–di- glucouronic residue -H₂O], 435(M-H–di-glucouronic residue − 2H₂O), 417[M-H– di-glucouronic residue − 3H₂O)

85

21.96

Tetrahydroxy-prenylflavanone

C₂₀H₁₈O₆

Flavanone

[M + H]⁺

337 (M + H-H₂O), 327 (M + H-CO), 311 (M + H-CO₂), 286 (M + H-isoprenyl unit), 221 (^1,3 A⁺), 245(M + H-ring B)

86

22.01

Chiricanin B

C₁₉H₂₀O₃

Stilbene

[M + H]⁺

279 (M + H- H₂O), 205 (C₁₂H₁₃O₃), 89 (C₇H₅)

87

22.54

Liquorice saponin C2

C₄₂H₆₂O₁₅

Triterpene Saponin (oleanane type)

[M-H]⁻

787(M-H-H₂O), 629 (M- H- glucouronic residue), 351(di-glucouronic residue -H)

88

22.74

Isoderrone

C₂₀H₁₆O₅

Pyranoisoflavone

[M + H]⁺

319 (M + H-H₂O), 309 (M + H-CO), 293 (M + H-CO₂), 322 (M + H-CH₃), 153 (^1,3 A⁺), 201 (^1,3B⁺)

89

22.8

Licochalcone E^a

C₂₁H₂₂O₄

Chalcone

[M + H]⁺

324 (M + H-CH₃), 270 (M + H-isoprenyl unit), 231 (X2-CH₃), 203 (Y2-CH₃), 122 (Y1), 94 (C₆H₆O X1) (Figure S2)

90

22.9

Tetrahydroxy-diprenylflavanone

C₂₅H₂₈O₆

Flavanone

[M-H]⁻

405 (M-H-H₂O), 395 (M-H-CO), 379 (M-H-CO₂), 285 (M-H-2 isoprenyl unit), 151 (^1,3 A⁻), 181(M-H-ring B)

91

23.03

Trihydroxy methoxy isoflavone

C₁₆H₁₂O₆

isoflavone

[M + H]⁺

283 (M + H-H₂O), 273 (M + H-CO), 257 (M + H-CO₂), 286 (M + H-CH₃), 153 (^1,3 A⁺), 149 (^1,3B⁺)

92

23.1

Yunganoside I2

C₄₂H₆₄O₁₅

Triterpene Saponin (oleanane type)

[M-H]⁻

745 (M- H₂O-CO₂-H), 631(M-H- glucouronic residue), 613(M-H-glucouronic residue -H₂O), 351(di-glucouronic residue -H)

93

23.26

Trihydroxy-prenylchalcone-Me ether

C₂₁H₂₂O₄

Chalcone

[M-H]⁻

268 (M-H-isoprenyl unit), 229 (X2-CH₃), 201 (Y-CH₃), 120 (Y1), 92 (X1) (Figure S2)

94

23.5

Dihydroxy-prenylflavanone

C₂₀H₂₀O₄

flavanone

[M + H]⁺

307 (M + H-H₂O), 297 (M + H-CO), 281 (M + H-CO₂), 256 (M + H-isoprenyl unit), 220 (^1,3 A⁺), 247 (M + H-ring B)

95

24.13

Phaseol^a

C₂₀H₁₆O₅

coumestan

[M-H]⁻

250 (M-H- C₄H₈-CHO), 251(M-H- C₄H₈-CO), 279 (M- H-C₄H₈), 280(M-H-C₄H₇)

96

24.51

kanzonol A^a

C₂₀H₂₀O₅

Chalcone

[M-H]⁻

270 (M-H-isoprenyl unit), 108 (X1), 230 (X2), 136 (Y1), 202 (Y2) (Figure S2)

97

24.624

Glycyrrhizol B^a

C₂₁H₁₈O₅

Pterocarpan

[M-H]⁻

212 (C₁₄H₁₂O₂), 188 (C₁₂H₁₂O₂), 174 (C₁₀H₆O₃)

98

24.7

Yunganoside L

C₃₆H₅₄O₁₀

Triterpene Saponin (oleanane type)

[M + H]⁺

471 (M + H-glucouronic residue), 176 (glucouronic residue)

99

24.86

Gancaonin W^a

C₂₁H₂₀O₆

isoflavone

[M-H]⁻

298 (M-H-isoprenyl unit), 339(M-H-CO), 323(M-H-CO₂)

100

25.19

Trihydroxy-prenylstilbene

C₁₉H₂₀O₃

Stilbene

[M-H]⁻

189 (C₁₂H₁₃O₂), 226 (M-H- isoprenyl unit)

101

25.3

Licoisoflavone B^a

C₂₀H₁₆O₆

Pyranoisoflavone

[M-H]⁻

333 (M-H-H₂O), 323 (M-H-CO), 307 (M-H-CO₂), 336 (M-H-CH₃), 151 (^1,3 A⁻), 215 (^1,3B⁻)

102

25.44

Kanzonol U

C₁₉H₁₆O₄

2-arylbenzofuran flavonoids

[M-H]⁻

289 (M-H-H₂O), 263 (M-H-CO₂)

103

25.65

Flavestin G

C₁₉H₂₀O₂

Stilbene

[M-H]⁻

189 (C₁₂H₁₃O₂), 210 (M-H-isoprenyl unit)

104

25.86

Licoagrodione^a

C₂₀H₂₀O₆

Stilbene

[M-H]⁻

150 (C₈H₆O₃), 204 (C₁₂H₁₂O₃)

105

26.14

Licoagroisoflavone^a

C₂₀H₁₆O₅

isoflavone

[M-H]⁻

317 (M-H-H₂O), 307 (M-H-CO), 291 (M-H-CO₂), 117 (^1,3B⁻), 201(^1,3 A⁻)

106

26.23

Trihydroxy-prenylpterocarpan-Me ether

C₂₁H₂₂O₅

Pterocarpan

[M-H]⁻

284 (M-H-isoprenyl unit), 244 (C₁₅H₁₆O₃), 146 (C₉H₆O₂), 122 (C₇H₆O₂)

107

26.43

Trihydroxy-prenylpterocarpan-Didehydro-Me ether

C₂₁H₂₀O₅

Pterocarpan

[M-H]⁻

282 (M-H-isoprenyl unit), 242 (C₁₅H₁₄O₃), 122 (C₇H₆O₂)

108

26.59

Glycyrrhizaisoflavone C

C₂₁H₂₀O₆

isoflavone

[M-H]⁻

349 (M-H-H₂O), 339 (M-H-CO), 323 (M-H-CO₂),135 (^1,3 A⁻), 245 (^1,3B⁻)

109

26.88

Glycyrrhizaflavonol A

C₂₀H₁₈O₇

Pyranoflavonol

[M-H]⁻

341(M-H-CO), 354 (M-H-CH₃), 325 (M-H-CO₂), 351 (M-H-H₂O), 151 (ring A)

110

26.97

Glabridin^a

C₂₀H₂₀O₄

Pyranoisoflavan

[M-H]⁻

295 (M-H-CO), 279 (M-H-CO₂), 187 (^1,3 A⁻), 135 (^1,3B⁻)

111

27.26

Glabrone^a

C₂₀H₁₆O₅

Pyranoisoflavone

[M-H]⁻

319 (M-H-CH₃), 290 (M-H-CO₂), 136 (^1,3 A⁻), 199 (^1,3B⁻), 213 (^1,4B⁻-H₂O)

112

27.32

Hydroxy-prenylflavanone

C₂₀H₂₀O₃

flavanone

[M + H]⁺

291(M + H-H₂O), 281(M + H-CO), 265 (M + H-CO₂), 240 (M + H-isoprenyl unit), 204 (^1,3 A⁺), 231(M + H-ring B)

113

27.82

Dihydroxy-diprenylflavanone

C₂₅H₂₈O₄

flavanone

[M + H]⁺

375 (M + H-H₂O), 365 (M + H-CO), 349 (M + H-CO₂), 255 (M + H-2 isoprenyl unit), 204 (^1,3 A⁺), 231(M + H-ring B)

114

28.03

Glyasperin G

C₂₁H₂₄O₅

coumestan

[M + H]⁺

301 (M + H-C₄H₈), 283 (M + H-C₄H₈-H₂O), 191 (C₁₁H₁₁O₃)

115

28.13

Cyclolicocoumarone

₂₀O₂₀H ₅ C

Resorcinol

[M-H]⁻

109 (M-H-C₁₄H₁₆O₃), 80 (C₆H₈), 68 (C₅H₈), 52 (C₄H₄)

116

28.22

Licoflavone A

C₂₀H₁₈O₄

Flavone

[M-H]⁻

252 (M-H-isoprenyl unit), 204 (^1,3 A⁻), 120 (^1,3B⁻)

117

28.38

Glabraisoflavanone A

C₂₅H₂₈O₄

isoflavanone

[M-H]⁻

373 (M-H-H₂O), 348 (M-H-CO₂), 363 (M-H-CO), 322 (M-H-isoprenyl unit), 204 (^1,3 A⁻)

118

28.5

Isoglabrolide

C₃₀H₄₄O₄

Triterpene Saponin (oleanane type)

[M + H]⁺

451(M + H-H₂O), 425 (M + H-CO₂), 413 (M + H- C₄H₈), 407 (M + H-CO₂-H₂O), 395 (M + H-C₄H₈-H₂O)

119

28.7

Licocoumarin A^a

C₂₅H₂₆O₅

Coumarin

[M-H]⁻

336 (M-H- isoprenyl unit), 267 (M-H-2 isoprenyl unit), 229 (C₁₄H₁₃O₃), 161 (C₉H₅O₃), 117 (C₈H₅O)

120

29.17

Kanzonol Z^a

₂₆O₂₅H ₅ C

Flavanone

[M-H]⁻

387 (M-H-H2O), 377 (M-H-CO), 361 (M-H-CO2), 336 (M-H-isoprenyl unit), 203 (^1,3 A⁻), 227 (M-H-ring B)

121

29.44

Kanzonol Y

C₂₅H₃₀O₅

Chalcone

[M-H]⁻

340 (M-H- isoprenyl unit), 271 (M-H- 2 isoprenyl unit), 232 (X2), 204 (Y1), 176 (X1) (Figure S2)

122

29.45

Licochalcone A, 2’-hydroxy

C₂₁H₂₂O₅

Chalcone

[M-H]⁻

338 (M-H-CH₃), 284 (M-H- isoprenyl unit), 217 (ring B), 135 (ring A)

123

30.24

Dihydrolicoisoflavone A

C₂₀H₂₀O₆

isoflavanone

[M-H]⁻

337 (M-H-H₂O), 327 (M-H-CO), 311 (M-H-CO₂), 286 (M-H-isoprenyl unit), 151 (^1,3 A⁻), 202 (^1,3B⁻)

124

30.95

Kanzonol B

₁₈O₂₀H₄C

Chalcone

[M + H]⁺

214 (X2), 187 (Y2), 138 (Y1), 110 (X1) (Figure S2)

125

31.24

Glabrene^a

C₂₀H₁₈O₄

Pyranoisoflavene

[M-H]⁻

121 (^1,3 A⁻), 199 (^1,3B⁻), 306 (M-H-CH₃), 293 (M-H-CO), 277 (M-H-CO₂)

126

32.09

Yunganoside E3

C₃₆H₅₂O₁₀

Triterpene Saponin (oleanane type)

[M-H]⁻

467 (M-H-glucouronic residue), 176 (glucouronic residue)

127

32.21

Shinpterocarpin^a

C₂₀H₁₈O₄

Pterocarpan

[M-H]⁻

212 (C₁₄H₁₂O₂), 146 (C₉H₆O₂), 122 (C₇H₆O₂)

128

32.2

Glycyrrhetinic acid

₃₀O₄₆H₄C

Triterpene Saponin

[M-H]⁻

450 (M-H-H₂O), 423 (M-H-COOH), 406 (M-H-CO₂-H₂O)

129

32.8

Hispaglabridin B

C₂₅H₂₆O₄

Pyranoisoflavan

[M + H]⁺

347 (M + H-CO₂), 363 (M + H-CO), 189 (^2,3B⁺)

130

33.57

Trihydroxy-diprenylisoflavan

C₂₅H₃₀O

Isoflavan

[M + H]⁺

367 (M + H-CO), 351 (M + H-CO₂), 257 (M + H-2 isoprenyl unit), 191 (^1,3 A⁺), 215 (M + H- ring B)

131

34.08

Glyinflanin A

C₂₅H₂₈O₅

Chalcone

[M-H]⁻

338 (M-H- isoprenyl unit), 269 (M-H-2 isoprenyl unit), 230 (X2), 204 (Y1), 202 (Y2), 176 (X1) [Figure S2]

132

34.1

Erypoegin B, O-De-Me

C₂₀H₁₈O₄

Pyranoisoflavene

[M-H]⁻

137 (^1,3 A⁻), 183((^1,3B⁻), 306 (M-H-CH₃), 293 (M-H-CO), 277 (M-H-CO₂)

133

34.2

Dihydroxy-dimethoxy prenylisoflavan

C₂₂H₂₆O₅

Isoflavan

[M + H]⁺

341 (M + H-2 OCH₃), 302 (M + H-isoprenyl unit), 153 (^1,3 A⁺), 179 (M + H-ring B)