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<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.