<Journal of Chromatography A>

Supporting Information

Integration of multicomponent characterization, untargeted

metabolomics and mass spectrometry imaging to unveil the holistic

chemical transformations and key markers associated with wine

steaming of Ligustri Lucidi Fructus

Mengrong Li a,b,1, Xiaoyan Wang a,b,1, Lifeng Han a,b,1, Li Jia a,b, Erwei Liu a,b,*, Zheng

Li a,c, Heshui Yu a,c, Yucheng Wang a,b, Xiumei Gao a, Wenzhi Yang a,b,*

a Tianjin State Key Laboratory of Modern Chinese Medicine, Tianjin University of

Traditional Chinese Medicine, 312 Anshanxi Road, Tianjin 300193, China

b Tianjin Key Laboratory of TCM Chemistry and Analysis, Tianjin University of

Traditional Chinese Medicine, 312 Anshanxi Road, Tianjin 300193, China

c College of Pharmaceutical Engineering of Traditional Chinese Medicine, Tianjin

University of Traditional Chinese Medicine, Tianjin 300193, China

1These authors contributed equally to this work.

*Corresponding authors:

E-mail addresses: liuwei628@hotmail.com (E.-w. Liu), wzyang0504@tjutcm.edu.cn

(W.-z. Yang).

Contents

Fig. S1 Chemical structures of 27 reference standard compounds used in the current

work.

Fig. S2 Permutation tests for the OPLS-DA models established based on the negative

and positive ESI-MS1 data.

Fig. S3 Longitudinal section figure of LLF (A) and MSI of nine different ions (B) as

the typical cases to show their spatial distribution in the fruits. [1] m/z 193.09, [2] m/z

649.42, [3] m/z 455.35, [4] m/z 191.07, [5] m/z 721.21, [6] m/z 729.43, [7] m/z 833.52,

[8] m/z 758.24, and [9] m/z 375.19.

Table S1 Detailed information of 27 reference compounds used in the current work.

Table S2 Information of the commercially purchased raw Ligustri Lucidi Fructus (LLF)

and the wine-processed LLF samples analyzed in the current work.

Table S3 Information of 139 compounds identified or tentatively characterized from

Ligustri Lucidi Fructus by UHPLC/Q-Orbitrap-MS in the ESI‒ mode.

Table S4 Information of 19 compounds identified or tentatively characterized from

Ligustri Lucidi Fructus by UHPLC/Q-Orbitrap-MS in the ESI+ mode.

Table S5 Information of 42 differential metabolic features detected in the ESI‒ mode

(VIP cutoff: 2.0).

Table S6 Information of 38 differential metabolic features detected in the ESI+ mode

(VIP cutoff: 2.0).

Table S7 Variations of 20 differential components among the raw and processed

Ligustri Lucidi Fructus (LLF) samples. showing 8 major identifying points (by

calculating the peak area ratios of M2, M4, M7, M8, M9, M11, M17, and M18, to

oleuropein aglycone).

Fig. S1 Chemical structures of 27 reference standard compounds used in the current

work.

Fig. S2 Permutation tests for the OPLS-DA models established based on the negative

and positive ESI-MS1 data.

Fig. S3 Longitudinal section figure of LLF (A) and MSI of nine different ions (B) as

the typical cases to show their spatial distribution in the fruits. [1] m/z 193.09, [2] m/z

649.42, [3] m/z 455.35, [4] m/z 191.07, [5] m/z 721.21, [6] m/z 729.43, [7] m/z 833.52,

[8] m/z 758.24, and [9] m/z 375.19.

Table S1 Detailed information of 27 reference compounds used in the current work.

No. Compound Formula Exact Mass Structure

subclass

1 hydroxyltyrosol C8H10O3 154.0625 Phenylethanol

2 salidroside C14H20O7 300.1204 Phenylethanol

3 verbascoside C29H36O15 624.2049 Phenylethanol

4 echinacoside C35H46O20 786.2577 Phenylethanol

5 specnuezhenide C31H42O17 686.2417 Iridoid

6 oleuropein C25H32O13 540.1837 Iridoid

7 nuezhenidic acid C17H24O14 452.1161 Iridoid

8 oleoside 11-methyl ester C17H24O11 404.1313 Iridoid

9 oleuropeinic acid C25H30O15 570.1579 Iridoid

10 ligulucidumoside A C26H34O12 538.2045 Iridoid

11 G13 C48H64O27 1072.3630 Iridoid

12 6'-O-trans-cinnamoyl-8-

epikingisidic acid C25H28O12 520.1575 Iridoid

13 ligulucidumoside C C19H26O13 462.1368 Iridoid

14 oleonuezhenide C48H64O27 1072.3630 Iridoid

15 ligustroflavone C33H40O18 724.2209 Iridoid

16 apigenin C15H10O5 270.0523 Flavonoid

17 luteoline C15H10O6 286.0472 Flavonoid

18 quercetin C15H10O7 302.0421 Flavonoid

19 luteolin-7-O-glucoside C21H20O11 448.1000 Flavonoid

20 quercitrin C21H20O11 448.1000 Flavonoid

21 rutin C27H30O16 610.1528 Flavonoid

22 oleanolic acid C30H48O3 456.3598 Triterpenoid

23 ursolic acid C30H48O3 456.3598 Triterpenoid

24 3β-O-acetylpomolic acid C32H50O5 514.3653 Triterpenoid

25 betulin C30H50O2 442.3805 Triterpenoid

26 protocatechuic acid C7H6O4 154.0261 Phenolic acid

27 physcion C16H12O5 284.0679 Anthraquinone

Table S2 Information of the commercially purchased raw Ligustri Lucidi Fructus (LLF)

and the wine-processed LLF samples analyzed in the current work.

No. Raw/Processed Batch

number

Producing

region Collection time

S1 raw Hebei 2017.08.15

S2 raw Hebei 2017.08.15

S3 raw Hebei 2017.08.15

S4 raw Henan 2017.08.15

S5 raw Henan 2017.08.15

S6 raw 170801 Sichuan 2017.08.20

S7 raw 161201 Sichuan 2016.12.21

S8 raw Jiangsu 2017.08.15

S9 raw Jiangsu 2017.08.15

S10 raw Anhui 2017.08.15

S11 raw Shanxi 2017.08.15

S12 wine-processed 180509 Henan 2018.05.09

S13 wine-processed 181001 Shanxi 2018.10.31

S14 wine-processed 180901 Zhejiang 2018.09.17

S15 wine-processed 181010 Anhui 2018.10.13

S16 wine-processed 181001 Zhejiang 2018.10.02

S17 wine-processed Hubei 2017.08.15

S18 wine-processed 180302161 Guangxi 2018.03.09

S19 wine-processed Shandong 2017.08.15

S20 wine-processed 180920 Anhui 2018.09.26

S21 wine-processed 180501 Sichuan 2018.05.02

Table S3 Information of 137 compounds identified or tentatively characterized from Ligustri Lucidi Fructus by UHPLC/Q-Orbitrap-MS in the

ESI‒ mode.

tR

(min)

[M−H]−

(m/z)

Mass

error

(ppm)

M.F. Identification MS2 fragments Classification

1 0.75 191.0555 2.436 C7H12O6 quinic acid 191.0554, 173.0085, 147.0292, 117.0181, 111.0075, 105.0180, 85.0282 Other

2 4.56 389.1093 3.783 C16H22O11 oleoside/secologanoside or isomer 254.0883, 209.0444, 181.0496, 165.0550, 137.0597, 121.0644,

111.0075, 101.0229 Iridoid

3 4.74 315.1084 3.129 C14H20O8 3,4-dihydroxyphenethyl-β-D-glucoside

or isomer

315.1084, 229.1127, 153.0547, 135.0441, 123.0440, 119.0337,

101.0233 Phenylethanol

4 4.78 451.1066 -3.684 C17H24O14 nuezhenidic acid isomer 451.1066, 225.0405, 209.0451, 195.0294, 181.0499, 165.0550,

151.0391, 123.0438, 113.0233, 107.0490, 101.0232 Iridoid

5* 4.85 153.0547 0.845 C8H10O3 hydroxyltyrosol 153.0547, 137.0234, 123.0440, 109.0283 Phenylethanol

6 4.89 389.1089 2.704 C16H22O11 oleoside/secologanoside or isomer 389.1089, 227.0562, 183.0548, 165.0548, 139.0755, 121.0647,

113.0231, 89.0231 Iridoid

7 4.92 315.1088 4.303 C14H20O8 3,4-dihydroxyphenethyl-β-D-glucoside

or isomer 315.1088, 153.0547, 135.0440, 123.0439, 113.-236 Phenylethanol

8 4.95 137.0597 -3.973 C8H10O2 tyrosol 137.0233, 121.0280, 111.0075, 109.0282, 92.9187, Phenylethanol

9* 4.96 153.0184 1.012 C7H6O4 protocatechuic acid 153.0184, 123.0440, 109.0283 Phenolic acids

10 5.14 375.1298 3.243 C16H24O10 loganic acid or isomer 395.2031, 375.13137, 191.0555, 151.0750, 119.0344, 113.0233,

101.0229, 85.0282, 71.0125, 59.0125 Iridoid

11 5.20 213.0762 -0.509 C10H14O5 nuzhenal A or isomer 215.0094, 213.0762, 169.0861, 151.0760, 139.0754, 125.0960,

111.0076, 107.0854, 95.0438, 69.0332 Iridoid

12* 5.20 451.1096 3.144 C17H24O14 nuezhenidic acid

451.1096, 433.0981, 401.0752, 389.1087, 271.0457, 239.0197,

227.0555, 209.0449, 195.0292, 165.0548, 151.0390, 123.0440,

107.0490, 101.0490

Iridoid

13 5.50 375.1286 -0.009 C16H24O10 loganic acid or isomer 375.1286, 195.0656, 191.0552, 151.0755, 123.0437, 119.0336,

113.0232, 101.0231, 89.0231, 71.0125, 59.0125 Iridoid

14 5.70 433.0981 0.884 C18H26O12 10-hydroxyoleoside dimethylester or

isomer

433.0981, 403.0885, 359.0969, 347.1349, 313.0927, 271.0464,

221.0087, 209.0450, 179.0343, 165.0548, 151.0391, 135.0440,

125.0232, 101.0232

Iridoid

15 5.71 375.1285 -0.249 C16H24O10 loganic acid or isomer 375.1285, 195.0653, 151.0654, 123.0443, 119.0336, 113.0234,

101.0232, 89.0230, 71.0125, 59.0125 Iridoid

16* 5.84 299.1137 3.847 C14H20O7 salidroside 299.1137, 179.0557, 161.0457, 137.0590, 119.0340, 113.0232,

101.0232, 89.0232 Phenylethanol

17 6.07 389.1091 3.321 C16H22O11 oleoside/secologanoside or isomer 304.1184, 209.0441, 183.0655, 179.0707, 165.0548, 151.0392,

123.0439, 113.0233, 101.0232 Iridoid

18 6.07 433.0989 2.939 C18H26O12 10-hydroxyoleoside dimethylester

433.0989, 401.0732, 389.1086, 345.1188, 313.0913, 271.0461,

221.0087, 209.0451, 183.0654, 177.0185, 165.0548, 149.0233,

133.0283, 113.0232, 101.0231, 71.0125, 59.0125

Iridoid

19 6.08 213.0763 0.054 C10H14O5 nuzhenal A or isomer 215.0094, 213.0763, 183.0654, 168.8863, 151.0754, 139.0755,

125.0958, 122.8931, 107.0856, 95.854 Iridoid

20 6.12 433.0989 2.801 C18H26O12 10-hydroxyoleoside

dimethylester/isomer

433.0989, 401.0732, 389.1086, 345.1188, 313.0913, 271.0087,

221.0087, 209.0451, 177.0185, 165.0548, 149.0233, 133.0283,

101.0231

Iridoid

21 6.22 137.0233 -3.495 C7H6O3 protocatechualdehyde 137.0233, 119.0125, 109.0284, 93.0333, 81.0331 Phenolic acids

22 6.24 375.1299 3.403 C16H24O10 loganic acid or isomer 191.0192, 151.0754, 119.0339, 119.0339, 113.0230, 105.0182,

101.0232, 89.0232, 85.0282, 71.0125, 59.0125 Iridoid

23 6.39 431.1563 3.460 C19H28O11 osmanthuside H or isomer 431.1561, 299.1139, 209.0448, 191.0567, 165.0548, 149.0445,

131.0336, 119.0489, 113.0232, 101.0231 Phenylethanol

24 6.53 537.1993 4.891 C26H34O12 ligulucidumoside A 537.1993, 375.1457, 225.3316, 191.0194, 147.0284, 85.0282 Iridoid

25 6.60 431.1568 3.043 C19H28O11 osmanthuside H or isomer 299.1138, 209.0460, 177.0189, 165.0549, 149.0446, 131.0343,

119.0489, 113.0233, 101.0231 phenylethanols

26 6.64 403.1223 -2.922 C17H24O11 oleoside 11-methyl ester or isomer 403.1223, 339.0714, 223.0607, 193.0498, 181.0865, 179.054, 161.0446,

143.0338, 113.0233, 101.0231, 89.0231 Iridoid

27 6.85 403.1229 -1.558 C17H24O11 oleoside 11-methyl ester isomer 405.1417, 359.1353, 299.0927, 281.0826, 223.0612, 181.0717,

161.0442, 143.0339, 113.0233, 101.0232, 89.0232 Iridoid

28 6.92 389.1091 3.244 C16H22O11 oleoside/secologanoside or isomer 389.1091, 345.1188, 209.0451, 183.0654, 165.0547, 121.0647, 69.0332 Iridoid

29 6.95 433.0983 1.392 C18H26O12 10-hydroxyoleoside

dimethylester/isomer

433.0983, 401.0721, 389.1075, 345.1194, 313.0925, 271.0466,

221.0087, 209.0450, 177.0185, 165.0548, 133.0283, 101.0230 Iridoid

30 7.45 461.1305 3.237 C19H26O13 sibiricose A3 or isomer 461.1305, 385.1156, 281.0670, 237.0774, 223.0601, 193.0863,

175.0757, 161.0598, 143.0338 Triterpenoid

31 7.56 387.1301 2.527 C17H24O10 8-demethyl-7-ketoliganin or isomer 389.1076, 341.1247, 299.1144, 281.1035, 225.0767, 181.0856,

161.0444, 137.0954, 113.0231, 101.0233 Iridoid

32* 7.74 403.1237 0.756 C17H24O11 oleoside 11-methyl ester 403.1237, 371.0962, 333.0831, 241.0721, 223.0609, 197.0814,

179.0556, 161.0448, 143.0340, 131.0338, 113.0232, 101.0232, 89.0231 Iridoid

33 7.80 609.1468 2.020 C27H30O16 quercetin-3-O-rutinoside/rutin 447.6329, 369.0624, 247.9982, 197.0856, 101.0235 Flavonoid

34 8.01 377.1458 2.753 C16H26O10 oleuropein aglycone or isomer 377.1453, 197.0813, 153.0911, 113.0232, 101.0231, 89.0230 Iridoid

35 8.16 377.1458 2.673 C16H26O10 oleuropein aglycone or isomer 377.1415, 315.1379, 197.0816, 191.0191, 153.0909, 147.0287,

129.0181, 101.0233, 85.0282 Iridoid

36 8.23 387.1301 2.450 C17H24O10 8-demethyl-7-ketoliganin or isomer 389.1099, 341.1232, 281.1033, 259.6801, 223.0461, 191.0190,

147.0291, 113.0232, 85.0282 Iridoid

37 8.23 609.1462 1.019 C27H30O16 quercetin-3-O-rutinoside/rutin 571.1731, 313.0351, 151.0392, 123.0441, 101.0231 Flavonoid

38 8.32 375.1301 4.150 C16H24O10 loganic acid or isomer 377.1402, 191.0191, 153.0912, 85.0282, 71.0122, 59.0126 Iridoid

39 8.48 593.1506 0.798 C27H30O15 unknown 593.1506, 473.1067, 383.0778, 353.0662, 325.0717, 297.0775,

191.0335 Iridoid

40 8.56 241.0717 4.254 C11H14O6 elenolic acid or isomer 241.0717, 207.0292, 171.0290, 165.0549, 139.0026, 127.0389,

121.0283, 101.0232, 95.0489, 68.9968 Iridoid

41 8.95 609.1469 2.217 C27H30O16 quercetin-3-O-rutinoside/rutin 609.1393, 447.0941, 403.1231, 285.0411, 175.3520, 121.0280,

101.0227 Flavonoid

42 8.95 639.1902 -3.629 C29H36O16 β-hydroxyverbascoside or isomer 639.1902, 605.0587, 431.0999, 269.0477, 179.0343, 161.0235,

135.0436 Phenylethanol

43* 9.10 461.1308 4.040 C19H26O13 ligulucidumoside C

461.1308, 403.1252, 299.0804, 281.0670, 267.0531, 223.0609,

191.0188, 179.0551, 161.0444, 149.0234, 131.0341, 119.0338,

113.0233, 101.0232, 89.0231

Iridoid

44 9.11 375.1300 3.803 C16H24O10 loganic acid or isomer 191.0188, 173.0091, 147.0289, 129.0180, 85.0282, 71.0126, 59.0332 Iridoid

45 9.17 639.1909 -2.581 C29H36O16 β-hydroxyverbascoside or isomer 639.1909, 489.3706, 203.0343, 179.0342, 161.0235, 151.0392,

135.0441, 113.0232 Triterpenoid

46* 9.20 785.2520 2.649 C35H46O20 echinacoside 482.1223, 179.0345, 161.0235, 153.0545, 135.0440, 89.0232 Iridoid

47 9.24 341.1243 3.447 C16H22O8 β-D-glucopyranoside-2-(4-

hydroxyphenethyl)-6-acetate

341.1256, 299.1141, 281.1032, 179.0708, 161.0445, 143.0336,

119.0490, 113.0232 Phenylethanol

48 9.24 387.1300 2.269 C17H24O10 8-demethyl-7-ketoliganin or isomer 341.1241, 299.1154, 281.1032, 161.0457, 119.0490, 113.0233, 101.233,

89.0232 Iridoid

49 9.27 639.1935 1.612 C29H36O16 β-hydroxyverbascoside or isomer 179.0344, 161.0233, 151.0392, 135.0440 Phenylethanol

50 9.41 447.0936 3.159 C21H20O11 [M-H+CH3COOH]- oleoside 11-methyl

ester

447.0936,403.1246, 333.0821, 283.0202, 282.0172, 223.0612,

179.0551, 151.0389, 101.0230 Iridoid

51 9.45 403.1246 2.833 C17H24O11 oleoside 11-methyl ester isomer

403.1246, 371.0967, 357.1184, 333.0821, 301.0928, 241.0714,

229.1441, 223.0607, 197.0817, 179.0551, 161.0444, 153.0179,

143.0337, 131.0334, 113.0232, 101.0232, 89.0231

Iridoid

52 9.67 241.0716 3.797 C11H14O6 elenolic acid or isomer 241.0716, 223.0607, 207.0290, 199.0606, 179.0707, 167.0342,

153.0547, 139.0026, 121.0283, 101.0232, 95.0490, 69.0333 Iridoid

53 9.84 701.2307 2.808 C31H42O18 neonuezhenide or isomer 299.1136, 239.0561, 195.0661, 179.0550, 153.0548, 137.0230,

121.0280, 113.0232, 101.0231, Iridoid

54 9.89 609.1473 2.824 C27H30O16 quercetin-3-O-rutinoside/rutin 317.1065, 285.0407, 125.2215, 101.0233 Flavonoid

55 9.89 739.2062 -3.211 C33H40O19 10-hydroxy ligustroflavone or isomer 423.1388, 385.1150, 315.0760, 275.5430, 223.0614, 161.0458,

153.0542, 151.0392, 121.0286, 113.0235, 101.0231, 89.0232 Iridoid

56 9.92 639.1940 2.379 C29H36O16 β-hydroxyverbascoside or isomer 457.1334, 251.0566, 179.0343, 161.0237, 135.0439, 113.0439 Phenylethanol

57 10.25 555.1727 3.419 C25H32O14 10-hydroxyoleuropein/ligustaloside A 55.1718, 533.2538, 403.1267, 361.0970, 323.0772, 291.0880, 223.0609,

179.0552, 165.0548, 151.0391, 101.0232, 89.0232 Iridoid

58 10.43 701.2306 2.637 C31H42O18 neonuzhenideor isomer 315.1089, 285.0618, 223.0605, 153.0546, 149.0233, 135.0440,

121.0283, 101.0233 Iridoid

59 10.43 739.2051 -3.957 C33H40O19 10-hydroxy ligustroflavone or isomer 687.6474, 620.0386, 581.8336, 500.9204, 315.1092, 291.0577,

149.0242, 135.0440, 121.0285, 101.0233, 89.0234 Iridoid

60* 10.57 569.1517 2.870 C25H30O15 oleuropeinic acid 569.1517, 525.1616, 389.0876, 363.1088, 331.0824, 221.0087,

209.0450, 177.0185, 151.0391, 133.0284, 123.0439 Iridoid

61 10.57 593.1505 0.697 C27H30O15 luteolin-7-O-rutinoside 593.1505, 333.2920, 285.0403, 202.9975, 177.0185, 151.0393,

135.0437, 123.0443, 101.0231 Iridoid

62* 10.57 609.1466 1.725 C27H30O16 rutin 609.3173, 436.2551, 358.5579, 301.0334, 300.0275, 271.0249,

255.0302, 151.0392, 123.0438, 101.0231 Iridoid

63 10.64 461.1307 3.780 C19H26O13 ligulucidumoside C or isomer 416.1307, 403.1239, 345.1564, 279.1641, 215.2371, 121.0282,

101.0299, 89.0230 Triterpenoid

64* 10.71 463.0870 -0.199 C21H20O12 hyperoside 436.0870,301.0349, 175.0024, 151.0024, 121.0286 Iridoid

65 10.85 555.1727 3.419 C25H32O14 10-hydroxyoleuropein/ligustaloside A 555.1727, 393.1195, 361.0932, 343.0829, 307.0826, 273.0773,

239.0562, 181.0499, 163.0389, 137.0235, 111.0440, 101.0233 Iridoid

66 10.85 685.2355 2.399 C31H42O17 specnuezhenide or isomer

685.2293, 523.1856, 453.1400, 421.1494, 315.0739, 299.1137,

281.1028, 223.0608, 179.0552, 153.0546, 121.0283, 119.0339,

113.0232, 101.0232, 89.0231

Iridoid

67 10.85 723.2099 -4.412 C33H40O18 Ligustroflavone or isomer 299.1124, 223.0614, 149.0245, 143.0231, 121.0282, 119.0039,

113.0234, 89.0231 Iridoid

68* 10.96 623.1995 3.873 C29H36O15 verbascoside 623.1995, 449.4269, 337.6332, 179.0343, 161.0235, 137.0234,

135.0440, 133.0285, 113.0232, 85.0230 Phenylethanol

69* 10.99 447.0935 2.957 C21H20O11 luteolin-O-glucoside 447.0935, 285.0405, 269.1385, 227.2466, 101.4084 Flavonoid

70 10.99 463.0872 0.124 C21H20O12 Hyperoside or isomer 436.0872, 301.0346, 300.0270, 271.0258, 255.0294, 151.0029,

121.0285 Iridoid

71 11.10 481.1719 3.121 C23H30O11 nuzhenal B 481.1719, 447.0952, 390.1913, 299.1133, 285.0416, 195.0660,

181.0499, 153.0548, 121.0283, 111.0075 Triterpenoid

72 11.38 523.1852 2.862 C25H32O12 p-hydroxyphenethyl 7-β-D -glucoside

elenolic acid ester or isomer

453.1438, 421.1497, 299.1122, 223.0617, 153.0183, 139.0025,

119.0490, 101.0231, 89.0230 Iridoid

73* 11.41 723.2097 -4.661 C33H40O18 ligustroflavone 453.1415, 421.1517, 299.1125, 259.2776, 223.0606, 179.0552,

153.0177, 137.0591, 121.0286, 89.0279 Iridoid

74* 11.42 685.2352 2.049 C31H42O17 specnuezhenide 523.1844, 453.1397, 421.1493, 299.1130, 223.0609, 181.0503,

179.0561, 153.0186, 121.0284, 89.0231 Phenylethanol

75 11.49 701.2302 2.024 C31H42O18 neonuzhenideor isomer 623.0955, 539.1736, 469.1343, 223.0608, 149.0234, 101.0231 Iridoid

76* 11.59 623.1968 -0.332 C29H36O15 isoverbascoside 623.1968, 461.1711, 417.1538, 299.1137, 179.0342, 161.0234,

153.0548, 135.0440, 133.0283, 113.0231, 85.0282 Triterpenoid

77 11.63 577.1539 -2.273 C27H30O14 apigenin-7-O-rutinoside 577.1539, 417.1555, 269.046, 181.0499, 153.0510, 119.2548, Iridoid

78 11.77 523.1818 1.562 C25H32O12 p-hydroxyphenethyl 7-β-D -glucoside

elenolic acid ester or isomer

523.1818, 453.1412, 421.1508, 299.1142, 223.0605, 153.0185,

121.0283, 101.0231, 89.0231 Iridoid

79 11.77 723.2118 -4.744 C33H40O18 Ligustroflavone or isomer 299.1139, 223.0605, 151.0385, 121.0281, 119.0336, 89.0232 Iridoid

80 11.80 553.1552 0.051 C25H30O14 ligustrosidic acid

553.1552, 509.1675, 373.0927, 347.1138, 329.1032, 315.0880,

289.0725, 235.0247, 209.0450, 195.0291, 177.0185, 165.0548,

151.0390, 137.0595, 101.0231

Iridoid

81 11.84 541.1934 3.423 C25H34O13 lucidumoside B 299.112, 183.0703, 139.0387, 121.0286, 101.0232 Iridoid

82 11.84 685.2356 2.589 C31H42O17 specnuezhenide or isomer 523.1830, 453.1411, 421. 1519, 299.1138, 223.0608, 179.0558,

153.0185, 143.0339, 137.0597, 119.0340, 101.0232, 89.0231 Iridoid

83 11.94 241.0713 2.719 C11H14O6 elenolic acid or isomer 241.0713, 209.0446, 171.0289, 165.0549, 139.0026, 127.0389,

121.0283, 101.0232, 95.0489, 68.9969 Iridoid

84 12.08 539.1771 2.231 C25H32O13 oleuropein or isomer

539.1771, 401.1086, 377.1244, 359.1151, 315.1090, 291.0875,

275.0930, 239.0543, 197.0812, 179.0551, 149.0231, 139.0025,

113.0236, 101.0232, 89.0231

Iridoid

85 12.20 431.0992 4.493 C21H20O10 apigenin-7-O-glucoside 431.0962, 269.0439, 268.0379, 240.0414, 171.0455, 151.0026,

117.0334, 107.0125 Flavonoid

86 12.26 555.1725 2.987 C25H32O14 10-hydroxyoleuropein/ligustaloside A 553.1564, 391.1041, 359.0787, 321.0619, 289.0728, 241.0713,

209.0450, 167.0341, 149.0234, 101.0231 Iridoid

87 12.26 685.2355 2.487 C31H42O17 specnuezhenide or isomer 523.1779, 453.1397, 421.1507 385.1164, 299.1140, 223.0606,

179.0561, 153.0185, 121.0283, 119.0338, 113.0233, 89.0229 Iridoid

88 12.37 553.1566 2.600 C25H30O14 ligustrosidic acid or isomer 553.1566, 391.1057, 359.0771, 321.0617, 289.0729, 209.0450,

181.0497, 167.0341, 149.0234, 101.0231 Iridoid

89 12.55 541.1943 4.994 C25H34O13 lucidumoside B 539.1757, 377.1247, 361.1296, 291.0881, 275.0930, 225.0764,

193.0498, 181.0862, 149.0601, 121.0648, 101.0232 Iridoid

90 12.55 727.2466 3.010 C33H44O18 acetylnicotiflorineor isomer 453.1455, 421.1501, 299.1135, 223.0609, 153.0186, 121.0285, 89.0231 Iridoid

91 12.81 685.2357 2.764 C31H42O17 specnuezhenide or isomer 523.1821, 453.1414, 421.1507, 385.1134, 299.1137, 223.0609,

179.0551, 153.0186, 121.0285, 119.0489, 101.0232, 89.0231 Iridoid

92 12.84 701.2277 -1.455 C31H42O18 neonuzhenideor isomer 701.2277, 607.2241, 487.0345, 275.0928, 223.0606, 197.0812,

149.0234, 121.0284, 113.0231, 101.0075 Iridoid

93 12.84 727.2466 3.093 C33H44O18 acetylnicotiflorineor isomer 565.1903, 523.1799, 495.1393, 421.1497, 341.1236, 299.11433,

281.1035, 223.0607, 191.0338, 153.0182, 121.0442, 113.0182, 89.0232 Iridoid

94* 12.88 447.0938 3.628 C21H20O11 luteolin-O-glucoside 447.0938, 313.0424, 285.0406, 153.7867, 95.0487 Flavonoid

95 12.99 1071.3564 1.239 C48H64O27 G13/oleonuezhenide or isomer

1071.3564, 839.2614, 771.2354, 685.2358, 547.1669, 523.1826,

453.1406, 421.1519, 403.1248, 315.0739, 299.1138,223.0608,

153.0184, 121.0283

Iridoid

96* 13.07 539.1760 0.209 C25H32O13 oleuropein

539.1760, 423.1300, 377.1242, 345.0983, 307.0824, 275.0924,

223.0606, 197.0812, 179.0553, 149.0231, 113.0232,101.0231, 95.0490,

89.0230

Iridoid

97 13.13 685.2352 2.049 C31H42O17 specnuezhenide or isomer 523.1803, 453.1402, 421.1536, 299.1139, 223.0608, 179.0557,

153.0181, 121.0284, 119.0486, 101.0232, 89.0231 Phenylethanol

98 13.13 723.2098 -4.578 C33H40O18 Ligustroflavone or isomer 453.1406, 403.3139, 299.1116, 223.0607, 193.0501, 121.0283,

119.0489, 113.0232, 89.0232 Iridoid

99 13.27 299.1136 3.546 C14H20O7 salidroside or isomer 299.1136, 255.0654, 185.1175, 179.0556, 137.0596, 131.0336,

119.0339, 101.0232, 89.0231 Phenylethanol

100 13.31 565.1568 2.863 C26H30O14 isojaslanceoside B 385.0930,341.1025, 337.1098, 231.0663, 213.0754, 195.0657,

179.0554, 163.0391, 145.0287, 119.0340, 113.0232, 101.0231 Iridoid

101 13.31 1071.3573 2.032 C48H64O27 G13/oleonuezhenide or isomer 1071.3573, 685.2349, 523.1804, 453.1408, 421.1503, 299.1142,

223.0608, 121.0283 Iridoid

102 13.60 525.1989 4.184 C25H34O12 lucidumoside A 525.1995, 421.1504, 349.1511, 299.1138, 223.0603, 193.0500,

175.0394, 149.0602, 117.0332 Iridoid

103 13.74 539.1777 3.251 C25H32O13 oleuropein or isomer

539.1797, 437.1478, 403.1248, 315.1086, 307.0837, 275.0937,

223.0618, 181.0502, 149.0233, 139.0391, 121.0285, 113.0231,

101.0232, 89.0231

Iridoid

104 13.89 727.2462 2.419 C33H44O18 acetylnicotiflorineor isomer 495.1477, 453.1406, 341.1240, 299.1136, 281.1031, 223.0607,

191.0343, 121.0283, 113.0231, 89.0231 Iridoid

105 13.92 583.2038 2.860 C27H36O14 [M-H+HCOOH]-ligulucidumoside A 550.3119, 403.1236, 379.4923, 223.0617, 151.0391, 123.0438,

101.0232 Flavonoid

106 14.07 583.2036 2.534 C27H36O14 [M-H+HCOOH]-ligulucidumoside A 526.3138, 403.1248, 265.0445, 223.0614, 165.0549, 151.0391,

123.0440, 101.0232 Iridoid

107 14.11 1071.3501 -4.688 C48H64O27 G13/oleonuezhenide or isomer 1071.3501, 909.3157, 771.2349, 685.2346, 523.1831, 453.1401,

421.1507, 403.1240, 315.0723, 299.1133, 223.0607, 121.0282 Phenylethanol

108* 14.29 1071.3557 0.548 C48H64O27 G13 1071.3557, 685.2376, 523.1822, 453.1425, 421.1490, 403.1275,

299.1139, 223.0604, 181.1675, 153.0184, 121.0283 Iridoid

109 14.36 727.2461 2.337 C33H44O18 acetylnicotiflorineor isomer 495.1478, 341.1246, 299.1153, 281.1038, 223.0608, 191.0350,

153.0547, 121.0284, 89.0231 Iridoid

110 14.43 539.1751 -1.497 C25H32O13 oleuropein or isomer 539.1751, 377.1267, 307.0826, 275.0922, 149.0230, 139.0389,

113.0235, 101.0229, 95.0487, 89.0230 Iridoid

111 14.50 523.1230 2.499 C25H32O12 ligustroside 523.1838, 453.1441, 361.1295, 291.0878, 259.0978, 223.0607,

171.0289, 139.0393, 101.0231 Iridoid

112 14.57 519.1507 1.921 C25H28O12 6'-O-cis-cinnamoyl 8-epikingisidic acid 519.1507, 371.0992, 227.0553, 209.0446, 189.0545, 183.0655, Triterpenoid

or isomer 165.0548, 161.0555, 147.0441, 121.0647

113 14.65 1071.3538 -1.272 C48H64O27 G13/oleonuezhenide or isomer 1071.3538, 771.2288, 685.2338, 523.1823, 453.1403, 299.1137,

179.0552, 121.0283 Iridoid

114* 14.94 1071.3512 1.821 C48H64O27 oleonuezhenide

1071.3512, 909.3033, 839.2543, 771.2328, 685.2328, 523.1823,

453.1404, 421.1516, 403.1268, 299.1136, 223.0608, 179.0553,

147.0441, 121.0283

Iridoid

115 14.97 523.1820 1.925 C25H32O12 p-hydroxyphenethyl 7-β-D -glucoside

elenolic acid ester or isomer

523.1820, 453.1404, 421.1501, 395.1444, 299.1137, 223.0609,

179.0556, 153.0184, 121.0282, 101.0231, 89.0230 Iridoid

116* 15.11 519.1497 0.033 C25H28O12 6'-O-trans-cinnamoyl -8-epikingisidic

acid

519.1497, 227.0555, 209.0453, 189.0551, 183.0654, 165.0550,

161.0600, 147.0442, 121.0647 Triterpenoid

117 15.16 1457.4792 1.566 C65H86O37 oleopolynuzhenide A 1457.4792, 1157.3430, 1071.3616, 771.2346, 685.2349, 523.1815,

453.1400, 421.1526, 385.1138, 299.1136, 223.0608 Iridoid

118* 15.22 285.0406 4.194 C15H10O6 luteoline 285.0406, 267.0305, 241.0506, 217.0497, 199.0393, 175.0394,

151.0025, 133.0285, 107.0124 Flavonoid

119* 15.29 301.0356 4.421 C15H10O7 quercetin 301.0356, 285.0401, 259.1089, 215.1186, 181.0496, 167.0705,

151.0026, 121.0284,107.0491 Flavonoid

120 15.38 1457.4727 -2.956 C65H86O37 oleopolynuzhenide A 1457.4727, 1157.3488, 1071.3527, 909.3137, 771.2351, 685.2347,

523.1814, 453.1402, 421.1514, 385.1142, 299.1139, 223.0606 Iridoid

121 15.66 519.1511 2.730 C25H28O12 6'-O-cis-cinnamoyl 8-epikingisidic acid

or isomer

519.1511, 475.1620, 327.1085, 209.0449, 189.0550, 165.0549,

161.0599, 147.0441, 121.0647 Iridoid

122 15.83 909.3047 2.695 C42H54O22 6’-elenolylnicotiflorine 685.2339, 523.1815, 453.1409, 421.1505, 299.1146, 223.0609,

153.0186, 121.0283 Iridoid

123* 15.91 269.0455 4.015 C15H10O5 apigenin 269.0455, 225.0552, 201.0551, 183.0441, 151.0028, 117.0333,

107.0123, Flavonoid

124 16.19 377.1245 2.221 C19H22O8 oleuropein aglycone 345.0982, 327.0826, 307.0826, 275.0927, 209.0463, 191.0348,

175.1142, 149.0234, 139.0390, 127.0389, 111.0075, 101.0231, 95.0489 Iridoid

125* 17.07 283.0612 3.745 C16H12O5 physcion 285.0673, 283.0612, 265.1816, 240.0425, 145.0929 Anthraquinone

126 17.66 487.3434 3.178 C30H48O5 tormentic acid 487.3434, 423.3255, 173.0084, 111.0076, 87.0076 Triterpenoid

127 18.70 285.0406 4.405 C15H10O6 kaempferol 285.0406, 257.0459, 241.0499, 217.0503, Flavonoid

128 19.06 633.3777 -1.311 C39H54O7 3-O-cis-p-coumaroyltormentic acid/3-O-

trans-p-coumaroyltormentic acid 633.3777, 168.9162, 163.0390, 145.0284, 119.0490, 112.9845 Phenylethanol

129 19.20 471.3483 2.744 C30H48O4

2α-hydroxy oleanic acid/ 2α-

hydroxyursolic acid /19α-hydroxyursolic

acid）

471.3483, 224.4577, 160.8412 Flavonoid

130 19.38 471.3488 3.954 C30H48O4 2α-hydroxy oleanic acid 471.3488, 227.2174, 226.0802, 165.7648 Triterpenoid

131 19.70 471.3484 3.126 C30H48O4 2α-hydroxy oleanic acid 471.3479, 165.5337, 118.7743 Flavonoid

132 20.20 513.3597 4.459 C32H50O5 19α-hydroxy-3-acetylursolic acid or

isomer 513.3597, 482.0439, Triterpenoid

133 20.42 617.3852 0.298 C39H54O6

3β-O-trans-p-coumaroylmaslinicacid or

isomer/3β-O-cis-p-coumaroylmaslinic

acid or isomer

617.3839, 145.0285, 119.0489, 95.0269 Triterpenoid

134 20.64 617.3846 1.481 C39H54O6

3β-O-trans-p-coumaroylmaslinicacid or

isomer/3β-O-cis-p-coumaroylmaslinic

acid or isomer

617.3846, 255.1267, 145.0285, 119.0489 Flavonoid

135 20.77 617.3815 -3.459 C39H54O6

3β-O-trans-p-coumaroylmaslinicacid or

isomer/3β-O-cis-p-coumaroylmaslinic

acid or isomer

617.3815, 197.0814, 161.0535, 153.0907, 145.0285, Flavonoid

136* 20.84 513.3590 3.037 C32H50O5 3β-O-acetylpomolic acid 513.3519, 511.3433, 465.3359, 242.1781, 138.1565 Triterpenoid

137 21.07 513.3578 0.660 C32H50O5 19α-hydroxy-3-acetyl-ursolic

acid/Acetyl pomolic acid 513.3578, 396.0992, 369.1432, 227.3712, 107.1490 Iridoid

*: compounds identified by comparison with the reference compounds.

Table S4 Information of 21 compounds identified or tentatively characterized from Ligustri Lucidi Fructus by UHPLC/Q-Orbitrap-MS in the ESI+

mode.

RT

[M+H]+

(m/z)

Mass error

(ppm)

M.F. Identification MS2 fragments Structure

138 5.22 197.0808 -0.129 C10H12O4

1,2-

dihydroxybenze

n or isomer

197.0808, 179.0703, 161.0755,

149.0599, 133.0649, 123.0807,

113.9640, 109.0652, 105.0703

Phenylethanol

139 5.22 229.1070 -0.088 C11H16O5 nuzhenal C or

isomer

229.1070, 211.0964, 197.0810,

179.0702, 169.0860, 155.0703,

151.0755, 137.0597, 133.0651,

123.0806, 109.0651

Phenylethanol

140 6.24 197.0808 -0.027 C10H12O4

1,2-

dihydroxybenze

n or isomer

199.0955, 197.0807, 179.0703,

165.0546, 151.0754, 149.0596,

137.0597, 131.9743, 121.0650,

113.9639, 109.0651, 105.0703

Phenylethanol

141 7.79 229.1070 -0.262 C11H16O5 nuzhenal C or

isomer

229.1035, 211.0963, 197.0810,

179.0703, 169.0859, 161.0598,

155.0703, 151.0754, 137.0598,

133.0648, 121.0649, 109.0651,

105.0702

Phenylethanol

142 8.03 181.0858 -0.667 C10H12O3 tyrosyl acetate 180.1019, 163.0389, 159.9692,

141.9586 Iridoid

143 8.03 199.0965 -0.078 C10H14O4 d-valerolactone 199.0965, 181.0858, 153.0910, Iridoid

or isomer 135.0805, 117.0701, 109.1015,

107.0859, 81.0704

144 8.39 229.1060 -4.714 C11H16O5 nuzhenal C or

isomer

229.1060, 211.0968, 197.0812,

179.0698, 169.0859, 155.0703,

151.0753, 139.0754, 137.0597,

123.0804, 109.0651

Iridoid

145 8.61 229.1069 -0.786 C11H16O5 nuzhenal C or

isomer

229.1069, 211.0964, 197.0806,

179.0700, 169.0859, 155.0703,

151.0755, 137.0597, 125.0598,

109.0651

Iridoid

146 9.43 229.1060 -4.365 C11H16O5 nuzhenal C or

isomer

229.1060, 211.0958, 197.0811,

183.1018, 169.0859, 155.0703,

151.0755, 137.0598, 133.0654,

121.0652, 109.0650

Iridoid

147 9.72 197.0809 0.277 C10H12O4

1,2-

dihydroxybenze

n or isomer

197.0802, 179.0703, 161.0598,

151.0754, 133.0649, 123.0805,

113.9640, 105.0702

Iridoid

148 9.83 229.1069 -0.830 C11H16O5 nuzhenal C or

isomer

229.1069, 211.0968, 197.0815,

179.0704, 169.0859, 155.0703,

151.0754, 137.0598, 123.0804,

109.0651

Iridoid

149 9.99 199.0966 0.726 C10H14O4 d-valerolactone

or isomer

199.0966, 197.1173, 181.0860,

153.0910, 135.0805, 125.0597,

109.1015, 107.0859, 81.0705

Iridoid

150 17.49 455.3513 -1.563 C30H46O3 3-oxo-olean-12-

en-28-oic

455.3513, 429.2491, 261.4277,

217.1961, 201.1640, 191.1794, Triterpenoid

acid/3-keto-

oleanolic acid

177.1632, 135.1167, 109.1014,

95.0857

151 19.11 455.3516 -0.838 C30H46O3

3-oxo-olean-12-

en-28-oic

acid/3-keto-

oleanolic acid

455.3555, 437.3442, 409.3464,

391.3383, 249.1857, 229.1955,

203.1796, 201.1637, 191.1792,

189.1637, 177.1626, 159.1168,

133.1015, 109.1016, 95.0860

Triterpenoid

152 20.36 499.3765 -3.317 C32H52O4

acety loleanic

acid/ acetyl

ursolic acid

499.3765, 204.1837, 191.1797,

161.1329, 135.1181, 107.0863,

95.0862

Triterpenoid

153 20.55 455.3535 3.334 C30H46O3

3-oxo-olean-12-

en-28-oic

acid/3-keto-

oleanolic acid

455.3535, 437.3438, 409.3466,

321.2407, 282.2791, 191.1788,

189.1635, 175.1483, 135.1170,

119.0858, 109.1013

Triterpenoid

154* 20.58 443.3882 -0.400 C30H50O2 betulin

445.3683, 443.3874, 425.3788,

409.3471, 259.2406, 247.2074,

237.1865, 219.1741, 201.1640,

189.1637, 181.1585, 161.1328,

149.1325, 135.1167, 109.1015

Triterpenoid

155 21.04 455.3517 -0.707 C30H46O3

3-oxo-olean-12-

en-28-oic

acid/3-keto-

oleanolic acid

455.3517, 437.3406, 409.3466,

265.1786, 201.1637, 191.1794,

133.1011, 119.0858, 95.0860

Triterpenoid

156* 21.36 457.3518 -0.355 C30H48O3

ursolic

acid/oleanolic

acid

457.2339, 439.3579, 411.3629,

263.2575, 203.1795, 175.1478,

149.1328, 135.1166, 121.1012,

Triterpenoid

109.1015, 95.0861

157 21.61 457.3674 -0.485 C30H48O3

ursolic

acid/oleanolic

acid (or

isomer)

457.2325, 437.3403, 409.3456,

337.2740, 247.1687, 229.1946,

201.1633, 189.1637, 175.1473,

161.1324, 147.1166, 133.1012,

107.0859, 95.0859

Triterpenoid

158 22.85 443.3880 -0.874 C30H50O2 betulin

443.3880, 425.3784, 217.1945,

189.1638, 177.1632, 149.1323,

135.1168, 121.1168, 109.1014,

95.0861

Triterpenoid

Table S5 Information of 42 differential metabolic features detected in the ESI‒ mode

(VIP cutoff: 2.0).

No. VIP tR (min) m/z Variation Identification

Numbering of

potential

markers

1 7.15 13.07 539.1777 ↓ oleuropein 1#

2 5.86 6.15 433.0991 ↑ 10-hydroxyoleoside dimethylester 2#

3 5.42 6.15 867.2062 ↑

4 4.65 10.60 569.1518 ↓ oleuropeinic acid 3#

5 4.57 0.72 195.0505 ↑

6 4.38 10.46 701.2308 ↓ neonuzhenide or isomer 4#

7 4.29 7.78 403.1250 ↓ oleoside 11-methyl ester 5#

8 3.87 14.96 1071.3582 ↑ oleonuezhenide 6#

9 3.84 9.27 387.1301 ↑ 8-demethyl-7-ketoliganin 7#

10 3.80 5.88 345.1193 ↑

11 3.76 11.96 241.0717 ↑ elenolic acid 8#

12 3.27 10.97 623.1987 ↓ verbascoside or isomer 9#

13 3.09 5.88 335.0907 ↑

14 3.04 2.05 151.0392 ↑

15 2.98 1.83 191.0192 ↑

16 2.98 13.07 575.1543 ↓

17 2.95 0.78 191.0192 ↑

18 2.87 16.21 377.1245 ↑ oleuropein aglycone 10#

19 2.74 15.23 285.0408 ↓ luteoline 11#

20 2.70 10.30 555.1725 ↓ 10-hydroxyoleuropein/ligustaloside A 12#

21 2.64 13.07 602.1733 ↓

22 2.62 28.00 195.8106 ↑

23 2.61 7.78 807.2576 ↓

24 2.58 9.27 377.1012 ↑

25 2.56 11.81 553.1571 ↓ ligustrosidic acid 13#

26 2.56 6.99 389.1094 ↓ oleoside/secologanoside or isomer 14#

27 2.51 10.87 555.1724 ↓ 10-hydroxyoleuropein/ligustaloside A 15#

28 2.46 11.59 623.1988 ↑ verbascoside or isomer 16#

29 2.43 10.46 737.2075 ↓

30 2.41 5.52 419.1200 ↑

31 2.40 14.52 523.1827 ↓

32 2.40 5.88 299.1138 ↑ salidroside 17#

33 2.36 16.54 213.1128 ↓

34 2.35 11.67 775.2313 ↓

35 2.34 6.10 213.0765 ↓ nuzhenal A 18#

36 2.34 6.88 628.1736 ↓

37 2.25 10.60 1139.3108 ↓

38 2.16 0.78 191.0555 ↑ quinic acid 19#

39 2.13 5.87 393.1407 ↓

40 2.10 14.96 1107.3341 ↓

41 2.09 0.71 279.0488 ↑

42 2.05 7.78 439.1017 ↓

Table S6 Information of 38 differential metabolic features detected in the ESI+ mode

(VIP cutoff: 2.0).

No. VIP tR

(min) m/z Variation Identification

Numbering of potential

markers

1 6.04 15.00 542.2230 ↑

2 5.38 6.17 452.1396 ↑

3 4.21 9.29 360.1651 ↑

4 4.13 7.32 272.1644 ↓

5 4.00 13.09 137.0596 ↓

6 3.99 6.35 182.0811 ↑

7 3.64 7.80 165.0545 ↓

8 3.40 14.98 1090.3971 ↓

9 3.26 11.44 704.2755 ↓

10 3.11 13.09 361.1279 ↓

11 2.97 6.90 584.2186 ↓

12 2.91 22.44 593.2754 ↓

13 2.91 11.44 165.0545 ↓

14 2.70 14.99 593.1862 ↓

15 2.70 7.80 151.0389 ↓

16 2.66 5.95 210.0760 ↑

17 2.65 14.33 1090.3970 ↓

18 2.61 13.09 558.2181 ↓

19 2.61 10.62 588.1921 ↓

20 2.60 5.90 318.1546 ↑

21 2.52 1.56 152.0706 ↑

22 2.47 14.17 343.1651 ↑

23 2.44 10.62 137.0596 ↓

24 2.42 5.21 272.1279 ↑

25 2.34 3.00 210.1124 ↑

26 2.32 13.89 746.2863 ↑

27 2.30 15.17 521.1652 ↓ 6'-O-trans-cinnamoyl -

8-epikingisidic acid 20#

28 2.22 14.33 165.0545 ↓

29 2.22 5.08 288.1229 ↑

30 2.19 14.54 121.0649 ↓

31 2.14 7.94 242.1538 ↑

32 2.13 4.83 244.1332 ↑

33 2.12 2.27 138.0913 ↑

34 2.05 14.99 165.0545 ↓

35 2.04 11.82 704.2755 ↑

36 2.04 5.09 302.1385 ↓

37 2.03 22.19 609.2699 ↓

38 2.01 10.62 409.1127 ↓

Table S7 Variations of 20 differential components among the raw and processed

Ligustri Lucidi Fructus (LLF) samples. showing 8 major identifying points (by

calculating the peak area ratios of M2, M4, M7, M8, M9, M11, M17, and M18, to

oleuropein aglycone).

No. Compounds 0 h

In-house

wine-

processed

(12 h)

Commerc

-ial raw

Commercial

wine-processed

Identifying points

Raw

LLF

Processed

LLF

1# oleuropein 2.78-3.24 0.77-1.12

2#(M2)b 10-hydroxyoleoside

dimethylester 0.86-1.04 2.09-2.33 0.91-1.57 2.82-32.55 < 1.8 > 1.8

3# oleuropeinic acid 1.87-2.08 1.02-1.14

4#(M4) neonuzhenide or isomer 0.81-1.02 0.12-0.14 0.62-4.52 0.02-0.39 > 0.5 < 0.5

5# oleoside 11-methyl ester 0.88-0.98 0.15-0.18

6# oleonuezhenide 1.01-1.22 0.39-0.5

7#(M7) 8-demethyl-7-ketoliganin 0-0.01 0.47-0.6 0 0.1-1.31 <

0.05 > 0.05

8#(M8) elenolic acid 0.03-0.04 0.53-0.66 0.01-0.04 0.24-0.92 < 0.1 > 0.1

9#(M9) verbascoside or isomer 1.27-1.43 0.86-0.92 1.13-3.09 0.16-1 > 1.1 < 1.1

10# oleuropein aglycone 0.09-0.12 0.35-0.56

11#(M11) luteoline 0.39-0.41 0.08-0.1 0.30-1.07 0.04-0.1 > 0.2 < 0.2

12#

10-

Hydroxyoleuropein/ligustalosi

de A

0.36-0.62 0.11-0.14

13# ligustrosidic acid 0.65-0.68 0.34-0.37

14# oleoside/secologanoside (or

isomer) 1.10-1.34 0.76-0.91

15#

10-

Hydroxyoleuropein/ligustalosi

de A

0.44-0.48 0.15-0.21

16# verbascoside (or isomer) 0.10-0.13 0.3-0.4

17#(M17) salidroside 0.11-0.13 0.29-0.38 0.03-0.13 0.14-2.47 <

0.135 > 0.135

18#(M18) nuzhenal A 0.42-0.46 0.16-0.22 0.43-1.00 0.07-0.41 >

0.415 < 0.415

19# quinic acid 1.63-2.51 1.72-2.76

20# 6'-O-trans-cinnamoyl -8-

epikingisidic acid 0.87-0.97 0.68-0.83

a: Numbering of 20 differential components is consistent their annotations in Table S5 and Table S6.

“0 h” refers to six batches of raw LLF subsamples from Sample S1;

“12 h” refers to 36 batches of the in-house processed LLF products;

“commercial raw” refers to the other commercially purchased raw LLF samples as listed in Table

S2;

“commercial wine-processed” refers the commercially purchased processed LLF samples listed in

Table S2.