药学学报

Component	Polarity	m/z	DP/V	CE/V
Schisandrol B	ES⁺	416.1	314.2	66	37
Schizandrin A	ES⁺	417.2	316.2	6	35
Schisandrin C	ES⁺	385.1	285.2	206	33
Methylophiopogonone A	ES⁺	341.1	219.3	1	31
Ophiogonanone A	ES⁺	330.1	136.3	11	25
1-O-Acetyl britannilactone	ES⁺	309.2	185.4	11	23
Britannin	ES⁺	367.1	247.3	56	15
Clarithromycin	ES⁺	748.5	590.3	41	29

Component	Polarity	m/z	DP/V	CE/V
Schisandrol B	ES⁺	416.1	314.2	66	37
Schizandrin A	ES⁺	417.2	316.2	6	35
Schisandrin C	ES⁺	385.1	285.2	206	33
Methylophiopogonone A	ES⁺	341.1	219.3	1	31
Ophiogonanone A	ES⁺	330.1	136.3	11	25
1-O-Acetyl britannilactone	ES⁺	309.2	185.4	11	23
Britannin	ES⁺	367.1	247.3	56	15
Clarithromycin	ES⁺	748.5	590.3	41	29

Component	Linear regression equation	r²	Linear range/ng·mL^-1
Schisandrol B	Y = 1 117.3X - 2 346.5	0.992 1	12.207-195.312
Schizandrin A	Y = 280 477X - 554 583	0.999 6	6.470-103.516
Schisandrin C	Y = 1 157.9X - 10 010	0.999 3	6.104-781.250
Methylophiopogonone A	Y = 264 984X - 1 000 000	0.999 8	5.920-378.906
Ophiogonanone A	Y = 1 076.6X - 7 745.3	0.998 2	11.963-382.812
1-O-Acetyl britannilactone	Y = 13 159X - 119 404	0.999 5	6.287-804.687
Britannin	Y = 2 888.7X - 8 384.8	0.997 3	6.714-214.844

Component	Linear regression equation	r²	Linear range/ng·mL^-1
Schisandrol B	Y = 1 117.3X - 2 346.5	0.992 1	12.207-195.312
Schizandrin A	Y = 280 477X - 554 583	0.999 6	6.470-103.516
Schisandrin C	Y = 1 157.9X - 10 010	0.999 3	6.104-781.250
Methylophiopogonone A	Y = 264 984X - 1 000 000	0.999 8	5.920-378.906
Ophiogonanone A	Y = 1 076.6X - 7 745.3	0.998 2	11.963-382.812
1-O-Acetyl britannilactone	Y = 13 159X - 119 404	0.999 5	6.287-804.687
Britannin	Y = 2 888.7X - 8 384.8	0.997 3	6.714-214.844

No.	Identification	t_R /min	Formula	Adducts	Precursor ion/m/z	Error /×10⁶	Fragment ion/m/z	Origin plant
1	Verbascoside	0.589	C₃₀H₅₂O₂₆	[M+Na]⁺	851.261 4	-3.6	689.212 4, 365.103 0, 163.064 4	Yong (SDH)
2	Rehmannioside A	0.888	C₂₁H₃₂O₁₅	[M+Na]⁺	547.164 1	0.4	365.106 9, 238.074 4, 146.059 1	Yong (SDH)
3	Raffinose	0.930	C₁₈H₃₂O₁₆	[M+Na]⁺	527.159 3	0.9	325.116 5, 163.063 5	Yong (SDH)
4	Adenine	0.940	C₅H₅N₅	[M+H]⁺	136.062 1	-1.5	119.035 4	Yong (MD)
5	2′-Acetylacteoside	0.982	C₃₁H₃₈O₁₆	[M+Na]⁺	689.204 2	-2.3	649.194 1, 365.111 4, 325.110 3	Yong (SDH)
6	Fructose	0.992	C₆H₁₂O₆	[M+Na]⁺	203.052 5	-3.4	163.058 3, 145.048 8, 127.039 5	Yong (SDH)
7	Adenosine	1.063	C₁₀H₁₃N₅O₄	[M+H]⁺	268.105 3	2.6	136.060 6, 119.033 8	Yong (SDH)
8	Arginine	3.729	C₆H₁₄N₄O₂	[M+H]⁺	175.120 0	2.9	112.084 3, 116.069 9	Hua (XX)
9	Citric acid	1.457	C₆H₈O₇	[M-H]^-	191.020 1	4.7	111.009 6	Yong (WWZ, SDH)
10	Stachyose	1.528	C₂₄H₄₂O₂₁	[M+H]⁺	667.228 7	-1.5	527.156 9, 275.078 6, 203.057 1	Yong (SDH)
11	Catalpol	1.538	C₁₅H₂₂O₁₀	[M+Na]⁺	385.112 3	3.1	136.061 5, 119.034 6	Yong (SDH)
12	Rehmannioside D	1.693	C₂₇H₄₂O₂₀	[M-H]^-	685.219 8	1.0	505.149 9, 341.112 9, 263.077 6, 179.055 3	Yong (SDH)
13	Melittoside	1.995	C₂₁H₃₂O₁₅	[M-H]^-	523.167 5	2.3	163.041 3, 135.045 9	Yong (SDH)
14	Protocatechuic acid	2.139	C₇H₆O₄	[M-H]^-	153.019 4	3.9	109.028 8	Ti (XFH), Yong (WWZ, DZY, SDH)
15	Geniposidic acid	2.139	C₁₆H₂₂O₁₀	[M-H]^-	373.112 6	-2.4	211.061 2, 123.048 7	Yong (SDH)
16	Dihydroferulic acid	2.758	C₁₀H₁₂O₄	[M+H]⁺	197.081 5	0.5	179.072 9, 167.071 4	Yong (SDH)
17	Salidroside	2.779	C₁₄H₂₀O₇	[M+Na]⁺	323.109 6	-3.4	224.061 5	Yong (SDH)
18	Vanillic acid	2.892	C₈H₈O₄	[M-H]^-	167.035 1	4.2	122.991 1, 151.984 6	Yong (SDH)
19	Ajugol	3.201	C₁₅H₂₄O₉	[M-H]^-	347.135 2	2.9	113.025 9, 167.033 7, 181.050 6, 303.107 2	Yong (SDH)
20	Quinic acid	3.254	C₇H₁₂O₆	[M-H]^-	191.056 2	3.1	109.031 7, 127.040 7, 173.045 8, 191.056 7	Yong (WWZ)
21	5-Hydroxymethylfurfural	3.482	C₆H₆O₃	[M+H]⁺	127.039 1	-3.1	109.030 8	Yong (MD, WWZ)
22	Neochlorogenic acid	5.040	C₁₆H₁₈O₉	[M-H]^-	353.087 8	1.4	127.033 0, 135.045 6, 161.027 9, 179.036 3, 191.057 4	Ti (XFH), Yong (DZY)
23	5-Hydroxymethyl-2-furaldehyde	5.163	C₆H₆O₃	[M-H]^-	125.023 6	-2.4	109.040 7	Yong (WWZ)
24	Decaffeoyl-verbascoside	5.237	C₂₀H₃₀O₁₂	[M-H]^-	461.164 9	-2.2	135.047 7, 123.041 9	Yong (SDH)
25	8-Epiloganic acid	5.630	C₁₆H₂₄O₁₀	[M-H]^-	375.128 9	-0.5	213.076 1, 169.088 4, 151.077 2	Yong (SDH)
26	Protocatechualdehyde	5.753	C₇H₆O₃	[M-H]^-	137.024 5	4.4	108.020 8, 109.025 7	Ti (XFH)
27	Acetylcatalpol	5.785	C₁₇H₂₄O₁₁	[M-H]^-	403.124 0	0.0	165.053 1, 139.039 6	Yong (SDH)
28	3,7-Dihydroxycoumarin	5.929	C₉H₆O₄	[M-H]^-	177.019 4	3.4	105.033 7, 133.028 4, 149.022 4	Ti (XFH)
29	Geniposide	6.239	C₁₇H₂₄O₁₀	[M+Na]⁺	411.127 7	2.4	149.057 8, 103.048 8	Yong (SDH)
30	Schisandrol A	6.889	C₂₄H₃₂O₇	[M+H]⁺	433.223 8	2.8	384.181 9, 353.161 3, 218.087 7	Yong (WWZ)
31	Cistanoside F	6.910	C₂₁H₂₈O₁₃	[M-H]^-	487.144 1	-2.3	179.033 5, 161.027 4, 135.046 9	Yong (SDH)
32	Caffeic acid	7.065	C₉H₈O₄	[M-H]^-	179.035 1	3.9	107.048 7, 109.029 8, 117.035 7, 134.039 4, 135.046 2, 136.084 1	Ti (XFH, ZGH), Yong (SDH)
33	Echinacoside	7.466	C₃₅H₄₆O₂₀	[M+Na]⁺	809.247 1	-1.1	287.072 6, 163.038 7	Yong (SDH)
34	sec-Hydroxyaeginetic acid	7.860	C₁₅H₂₄O₅	[M-H]^-	283.155 7	4.2	163.107 6, 181.099 3, 203.162 4, 239.123 3, 265.127 2	Yong (SDH)
35	Cryptochlorogenic acid	7.962	C₁₆H₁₈O₉	[M-H]^-	353.088 2	2.5	111.048 6, 135.045 8, 155.036 4, 173.047 1, 179.037 1, 191.057 6	Ti (XFH), Yong (DZY)
36	Naringenin	8.263	C₁₅H₁₂O₅	[M-H]^-	271.061 7	4.1	151.004 3, 119.050 2	Yong (DZY))
37	5,7,4′-Trihydroxy-3′-methoxy-6,8-dimethyl-homisoflavanone	8.542	C₁₉H₂₀O₆	[M+H]⁺	345.133 1	-2.0	137.053 3, 299.084 2	Yong (MD)
38	Liquiritin	8.562	C₂₁H₂₂O₉	[M-H]^-	417.118 4	-0.5	255.067 8, 161.024 0, 148.017 2	Ti (ZGC)
39	Chlorogenic acid	9.006	C₁₆H₁₈O₉	[M-H]^-	353.087 8	1.4	191.057 8, 179.036 5, 173.043 8	Ti (XFH), Yong (WWZ, DZY)
40	Prim-O-glucosylcimifugin	9.069	C₂₂H₂₈O₁₁	[M+H]⁺	469.170 8	-0.4	235.060 4, 189.041 2	Yong (SDH)
41	Kaempferol-3-rutinoside	9.843	C₂₇H₃₀O₁₅	[M+H]⁺	595.165 8	-0.8	415.089 1, 463.105 5	Ti (ZGC)
42	1,3-Dicaffeoylquinic acid	10.121	C₂₅H₂₄O₁₂	[M-H]^-	515.119 0	0.0	191.057 4, 179.036 2, 135.045 9	Ti (XFH)
43	Verbascoside	10.401	C₂₉H₃₆O₁₅	[M+Na]⁺	647.196 0	1.2	501.139 9, 485.137 5, 339.090 7, 163.037 5	Yong (SDH)
44	Rutin	10.637	C₂₇H₃₀O₁₆	[M+H]⁺	611.161 2	0.0	129.066 9, 257.068 3, 303.052 9, 465.106 9	Yong (DZY)
45	Neo-rehmannioside E	10.690	C₂₁H₃₄O₁₀	[M-H]^-	445.208 9	3.4	161.025 4, 265.099 2	Yong (SDH)
46	Isoschaftoside	11.052	C₂₆H₂₈O₁₄	[M+H]⁺	565.154 9	-1.4	295.059 8, 325.071 0, 337.071 4, 391.081 7, 409.090 6, 427.100 8, 565.154 0	Ti (ZGC), Yong (DZY)
47	Schaftoside	11.062	C₂₆H₂₈O₁₄	[M-H]^-	563.139 5	-1.1	473.111 5, 383.078 5	Ti (ZGC)
48	Loliolid	11.123	C₁₁H₁₆O₃	[M+H]⁺	197.117 8	0.0	105.075 8, 115.052 3, 133.099 6, 161.100 2, 179.103 5	Ti (XFH)
49	Quercetagetin-7-O-glucoside	11.207	C₂₁H₂₀O₁₃	[M+H]⁺	481.097 0	-2.5	319.043 5	Ti (XFH)
50	5,7,2′-Trihydroxy-8-methyl-3-(3′,4′-methylenedioxybenzyl)-chromone	11.238	C₁₈H₁₄O₇	[M+H]⁺	343.080 4	-4.1	205.046 7, 177.054 3, 149.056 7	Yong (MD)
51	Methyl eugenol	11.238	C₁₁H₁₄O₂	[M+H]⁺	179.106 9	-1.7	117.062 9, 143.073 7, 144.080 6	Hua (XX)
52	Isoorientin	11.361	C₂₁H₂₀O₁₁	[M+H]⁺	449.108 7	0.7	299.054 2, 166.021 8, 300.062 1	Yong (DZY)
53	Orientin	11.414	C₂₁H₂₀O₁₁	[M-H]^-	447.093 0	0.7	327.051 3, 357.064 0, 297.040 0	Yong (DZY)
54	Cistanoside A	11.671	C₃₆H₄₈O₂₀	[M-H]^-	799.263 7	-3.0	623.218 9, 175.037 8	Yong (SDH)
55	2-O-β-D-Glucopyranosyl atractyligenin	11.702	C₂₅H₃₈O₉	[M-H]^-	481.244 4	1.2	301.181 3, 320.184 0	Ti (XFH)
56	Rehmannioside C	11.723	C₁₉H₃₂O₈	[M+Na]⁺	411.199 9	1.0	245.194 6	Yong (SDH)
57	Rehmapicroside	11.949	C₁₆H₂₆O₈	[M-H]^-	345.154 5	-1.2	165.054 5	Yong (SDH)
58	Liquiritigenin	12.156	C₁₅H₁₂O₄	[M-H]^-	255.066 0	1.2	135.048 0, 119.050 9	Ti (ZGC)
59	Liquiritin apioside	12.363	C₂₆H₃₀O₁₃	[M-H]^-	546.161 1	0.5	417.119 6, 255.067 4, 135.010 1	Ti (ZGC)
60	Afzelin	12.423	C₂₁H₂₀O₁₀	[M-H]^-	431.098 3	1.2	283.062 0, 311.056 1, 323.052 8	Ti (ZGC)
61	Isovitexin	12.434	C₂₁H₂₀O₁₀	[M+H]⁺	433.113 4	-0.2	433.112 1, 313.072 1, 415.103 6	Yong (DZY)
62	Vitexin	12.444	C₂₁H₂₀O₁₀	[M-H]^-	431.097 0	-1.9	117.035 0, 283.061 1, 161.022 9	Yong (DZY)
63	Taxifolin	12.704	C₁₅H₁₂O₇	[M-H]^-	303.051 4	3.0	107.016 0, 125.026 2, 175.035 5, 217.054 2	Ti (XFH)
64	Quercetin-3-O-glucuronide	12.796	C₂₁H₁₈O₁₃	[M+H]⁺	479.082 4	-0.4	303.048 9	Ti (XFH)
65	Quercetin	12.859	C₁₅H₁₀O₇	[M-H]^-	301.034 8	0.0	229.047 9, 178.997 2, 151.004 5	Ti (XFH), Yong (DZY)
66	Hyperoside	13.013	C₂₁H₂₀O₁₂	[M-H]^-	463.087 7	0.0	151.005 2, 255.031 6, 271.025 8, 300.028 1, 301.035 2	Ti (XFH)
67	Isoquercitrin	13.024	C₂₁H₂₀O₁₂	[M-H]^-	463.087 9	0.4	107.014 6, 151.004 6, 178.998 9, 255.029 7, 300.028 4, 301.033 9	Ti (XFH)
68	Patulitrin	13.231	C₂₂H₂₂O₁₃	[M+H]⁺	495.114 1	0.4	318.035 9, 333.059 7	Ti (XFH)
69	Jiocarotenoside B1	13.415	C₃₇H₅₀O₂₀	[M-H]^-	813.280 3	-1.7	637.236 2, 175.032 2	Yong (SDH)
70	Azelaic acid	13.446	C₉H₁₆O₄	[M-H]^-	187.096 0	-5.3	125.095 4	Yong (MD)
71	Neo-rehmannioside B	13.633	C₁₅H₂₄O₆	[M-H]^-	299.149 3	-0.7	139.073 5	Yong (SDH)
72	Isorhamnetin-3-O-glucoside	13.675	C₂₂H₂₂O₁₂	[M-H]^-	477.103 7	0.8	107.021 1, 151.002 7, 285.040 5, 314.043 7, 315.051 7	Ti (XFH)
73	1,5-Dicaffeoylquinic acid	13.808	C₂₅H₂₄O₁₂	[M-H]^-	515.119 5	1.0	335.078 9, 191.056 4, 179.035 3	Ti (XFH)
74	Forsythoside A	14.026	C₂₉H₃₆O₁₅	[M-H]^-	623.198 1	0.8	177.017 3, 119.048 2	Yong (SDH)
75	Isochlorogenic acid A	15.214	C₂₅H₂₄O₁₂	[M-H]^-	515.119 5	1.0	203.037 2, 191.057 1, 179.036 2	Ti (XFH)
76	5-Methoxy-6-methyl-7-oxhydryl-8-methoxy-3-(2′-oxhydryl-4′-methoxybenzyl)-4-chromanone	15.429	C₂₀H₂₂O₇	[M-H]^-	373.129 8	2.9	153.019 6, 168.046 0	Yong (MD)
77	5,7-Dihydroxy-3-(4′-methoxybenzyl)-4-chromone	15.865	C₁₇H₁₄O₅	[M-H]^-	297.075 2	-3.7	203.037 1, 175.046 9	Yong (MD)
78	Aegineticacid	15.957	C₁₅H₂₄O₄	[M+H]⁺	269.176 4	4.1	167.010 4	Yong (SDH)
79	Formononetin	16.122	C₁₆H₁₁O₄	[M-H]^-	267.066 0	1.1	252.044 8	Ti (ZGC)
80	Ophiopogonanone E	16.308	C₁₉H₂₀O₇	[M-H]^-	359.113 6	1.4	208.034 1, 138.035 6	Yong (MD)
81	5,7-Dihydroxy-6,8-dimethyl-3-(3′,5′-dimethoxy-4′-hydroxybenzyl)-4-chromanone	16.339	C₂₀H₂₂O₇	[M-H]^-	373.130 0	3.5	207.064 6, 179.070 1, 135.046 6	Yong (MD)
82	5,7-Dihydroxy-8-methyl-3-(3′,4′-dimethoxybenzyl)-4-chromone	16.410	C₁₈H₁₄O₆	[M-H]^-	325.071 8	1.8	297.073 3, 131.053 8, 203.035 9	Yong (MD)
83	Neoliquiritin	16.474	C₂₁H₂₂O₉	[M+H]⁺	419.132 6	-3.8	119.047 6, 137.022 1, 239.069 7, 257.080 6	Ti (ZGC)
84	Isoliquiritin	16.959	C₂₁H₂₂O₉	[M+H]⁺	419.135 1	2.1	137.023 2, 239.070 8, 257.082 5	Ti (ZGC)
85	Isoliquiritigenin	16.969	C₁₅H₁₂O₄	[M+H]⁺	257.081 0	-1.6	137.023 8	Ti (ZGC)
86	Martynoside	17.103	C₃₁H₄₀O₁₅	[M-H]^-	651.228 5	-0.6	193.048 0, 175.042 1	Yong (SDH)
87	Spinacetin	17.216	C₁₇H₁₄O₈	[M-H]^-	345.061 6	1.7	315.014 5, 330.038 3	Ti (XFH)
88	5-Oxhydryl-6-methyl-7-methoxy-3-(3′,4′-dihydroxyphenyl)-4-chromone	17.546	C₁₈H₁₆O₆	[M-H]^-	327.086 5	-1.2	164.049 8, 327.084 9	Yong (MD)
89	Uralsaponin F	17.693	C₄₄H₆₄O₁₉	[M-H]^-	895.399 4	3.4	853.394 4, 821.353 5, 351.059 5	Ti (ZGC)
90	1-O-Acetyl britannilactone	18.354	C₁₇H₂₄O₅	[M+H]⁺	309.169 2	-3.2	291.050 0, 231.136 9, 203.141 2	Ti (XFH)
91	Luteolin	18.404	C₁₅H₁₀O₆	[M-H]^-	285.039 7	-0.7	175.035 6, 151.004 5, 133.026 6	Ti (XFH), Yong (DZY)
92	Eupafolin	18.684	C₁₆H₁₂O₇	[M-H]^-	315.051 3	2.5	300.027 4	Ti (XFH)
93	Rosmarinic acid	20.563	C₁₈H₁₆O₈	[M-H]^-	359.077 4	1.9	133.029 3, 135.044 2, 161.025 6, 193.014 4	Ti (XFH)
94	Licorice saponin A3	20.770	C₄₈H₇₂O₂₁	[M+H]⁺	985.467 6	3.2	453.336 4, 471.348 0, 615.389 4, 809.433 9	Ti (ZGC)
95	Diosmetin	21.069	C₁₆H₁₂O₆	[M-H]^-	299.056 9	4.3	227.037 1, 256.039 1, 284.032 8	Yong (DZY)
96	Ophiopogonin D	21.070	C₄₄H₇₀O₁₆	[M+H]⁺	855.471 6	-3.0	251.178 2, 287.200 7, 431.313 8, 559.363 5, 577.379 1, 711.368 9, 723.434 0	Yong (MD)
97	Licorice saponin G2	21.153	C₄₂H₆₂O₁₇	[M+H]⁺	839.408 6	2.5	451.320 7, 469.331 2, 487.341 5, 663.377 1	Ti (ZGC)
98	Licorice saponin E2	21.193	C₄₂H₆₀O₁₆	[M+H]⁺	821.395 8	-0.2	451.323 1, 469.332 6, 645.364 4	Ti (ZGC)
99	Gancaonin G	21.203	C₂₁H₂₀O₅	[M+H]⁺	353.139 8	2.5	267.063 7, 297.108 2	Ti (ZGC)
100	Glycyrrhetinic acid	21.266	C₃₀H₄₆O₄	[M+H]⁺	471.346 2	-2.5	407.329 5, 435.326 9, 453.337 0	Ti (ZGC)
101	Neobritannilactone B	21.276	C₁₅H₂₀O₃	[M-H]^-	247.133 8	1.6	203.148 3, 201.132 8, 135.083 1	Ti (XFH)
102	Methylophiopogonone A	21.286	C₁₉H₁₆O₆	[M-H]^-	339.087 3	1.2	311.093 4, 217.208 3	Yong (MD)
103	Ophiopogonanone B	21.328	C₁₉H₂₀O₅	[M-H]^-	327.124 5	4.0	178.066 9	Yong (MD)
104	Glycyrrhizic acid	21.389	C₄₂H₆₂O₁₆	[M-H]^-	821.396 3	0.4	351.055 0, 193.034 8, 469.344 7	Ti (ZGC)
105	Pregomisin	21.431	C₂₂H₃₀O₆	[M+H]⁺	391.212 2	0.3	327.143 6, 275.084 7, 229.096 2	Yong (WWZ)
106	Uralsaponin C	21.473	C₄₂H₆₄O₁₆	[M+H]⁺	825.428 1	1.0	455.351 0, 473.361 4	Ti (ZGC)
107	8-Formyl ophiopogonone B	21.534	C₂₀H₂₂O₇	[M+H]⁺	375.143 9	-1.3	109.062 1, 251.090 2, 357.133 8	Yong (MD)
108	Casticin	21.699	C₁₉H₁₈O₈	[M+H]⁺	375.107 6	-1.1	360.082 6, 375.103 9, 377.116 6	Ti (XFH)
109	Schisandrol B	21.751	C₂₃H₂₈O₇	[M+H]⁺	417.192 3	2.4	368.147 1, 399.179 9	Yong (WWZ)
110	Diosgenin	21.804	C₂₇H₄₂O₃	[M+H]⁺	415.321 5	0.7	157.095 5	Yong (MD)
111	Ilicic acid	21.824	C₁₅H₂₄O₃	[M-H]^-	251.165 8	4.4	207.173 2	Ti (XFH)
112	Japonicones D	21.885	C₃₄H₄₄O₉	[M+H]⁺	597.305 9	-0.8	211.109 5, 185.132 0	Ti (XFH)
113	Gomisin D	21.896	C₂₈H₃₄O₁₀	[M+H]⁺	531.224 5	2.8	401.158 9, 383.149 2, 341.101 3	Yong (WWZ)
114	Gomisin R	21.906	C₂₂H₂₄O₇	[M+H]⁺	401.159 3	-1.7	337.106 6, 341.102 8, 383.148 2	Yong (WWZ)
115	Gomisin J	21.927	C₂₂H₂₈O₆	[M+H]⁺	389.194 5	-4.9	227.075 0, 287.092 0, 137.060 1	Yong (WWZ)
116	5-Oxhydryl-6-aldehyde-7-methoxy-8-methyl-3-(4′-methoxybenzyl)-4-chromanone	21.937	C₂₀H₂₀O₆	[M-H]^-	355.120 0	5.1	217.052 1, 150.031 8	Yong (MD)
117	Ruscogenin	21.938	C₂₇H₄₂O₄	[M+H]⁺	431.316 8	1.6	251.177 6, 269.185 4, 139.078 6	Yong (MD)
118	Sesamin	21.959	C₂₀H₁₈O₆	[M+H]⁺	355.117 9	-0.8	179.035 7, 268.985 4	Hua (XX)
119	Angeloylgomisin H	22.029	C₂₈H₃₆O₈	[M+H]⁺	501.248 9	0.2	370.173 1, 355.154 4, 337.142 4	Yong (WWZ)
120	Schisantherin B	22.071	C₂₈H₃₄O₉	[M+H]⁺	515.227 9	-0.4	385.165 4, 355.152 5, 343.116 8	Yong (WWZ)
121	Benzoylgomisin H	22.155	C₃₀H₃₄O₈	[M+H]⁺	523.231 3	-3.6	441.181 5, 409.159 0, 386.174 3	Yong (WWZ)
122	Gedunin	22.155	C₂₈H₃₄O₇	[M+H]⁺	483.238 3	0.0	381.133 3, 395.149 1, 367.117 2	Yong (WWZ)
123	Schisandrin B	22.155	C₂₃H₂₈O₆	[M+H]⁺	401.195 8	-1.5	386.174 3, 370.177 3	Yong (WWZ)
124	Alantolactone	22.195	C₁₅H₂₀O₂	[M+H]⁺	233.153 9	1.7	159.114 6, 118.071 1, 106.073 7	Ti (XFH)
125	Schisanhenol B	22.237	C₂₂H₂₆O₆	[M+H]⁺	387.179 7	-2.8	355.154 1, 326.150 7, 271.060 4	Yong (WWZ)
126	Schisandrin C	22.350	C₂₂H₂₄O₆	[M+H]⁺	385.166 2	2.9	257.080 8, 199.074 8, 184.051 5	Yong (WWZ)
127	Schisantherin A	22.381	C₃₀H₃₂O₉	[M+H]⁺	537.209 6	-5.4	415.173 3, 397.163 7, 371.148 9	Yong (WWZ)
128	Schisandrin A	22.753	C₂₄H₃₂O₆	[M+H]⁺	417.226 5	-2.9	402.203 2, 386.204 3, 371.184 9	Yong (WWZ)
129	Schisanhenol	22.504	C₂₃H₃₀O₆	[M+H]⁺	403.211 0	-2.7	302.116 8, 271.093 8	Yong (WWZ)
130	Asarinin	22.940	C₂₀H₁₈O₆	[M+NH₄]⁺	372.144 4	-0.8	128.060 9, 135.038 8, 161.063 1	Hua (XX)
131	5,7,2′-Trihydroxy-6,8-dimethyl-3-(3′,4′-methylenedioxybenzyl)-chromone	22.961	C₁₉H₁₆O₇	[M+H]⁺	357.097 2	-0.6	339.097 9	Yong (WWZ)
132	Dibutyl phthalate	23.239	C₁₆H₂₂O₄	[M+H]⁺	279.160 9	4.7	149.022 3, 121.027 8	Yong (WWZ)

No.	Identification	t_R /min	Formula	Adducts	Precursor ion/m/z	Error /×10⁶	Fragment ion/m/z	Origin plant
1	Verbascoside	0.589	C₃₀H₅₂O₂₆	[M+Na]⁺	851.261 4	-3.6	689.212 4, 365.103 0, 163.064 4	Yong (SDH)
2	Rehmannioside A	0.888	C₂₁H₃₂O₁₅	[M+Na]⁺	547.164 1	0.4	365.106 9, 238.074 4, 146.059 1	Yong (SDH)
3	Raffinose	0.930	C₁₈H₃₂O₁₆	[M+Na]⁺	527.159 3	0.9	325.116 5, 163.063 5	Yong (SDH)
4	Adenine	0.940	C₅H₅N₅	[M+H]⁺	136.062 1	-1.5	119.035 4	Yong (MD)
5	2′-Acetylacteoside	0.982	C₃₁H₃₈O₁₆	[M+Na]⁺	689.204 2	-2.3	649.194 1, 365.111 4, 325.110 3	Yong (SDH)
6	Fructose	0.992	C₆H₁₂O₆	[M+Na]⁺	203.052 5	-3.4	163.058 3, 145.048 8, 127.039 5	Yong (SDH)
7	Adenosine	1.063	C₁₀H₁₃N₅O₄	[M+H]⁺	268.105 3	2.6	136.060 6, 119.033 8	Yong (SDH)
8	Arginine	3.729	C₆H₁₄N₄O₂	[M+H]⁺	175.120 0	2.9	112.084 3, 116.069 9	Hua (XX)
9	Citric acid	1.457	C₆H₈O₇	[M-H]^-	191.020 1	4.7	111.009 6	Yong (WWZ, SDH)
10	Stachyose	1.528	C₂₄H₄₂O₂₁	[M+H]⁺	667.228 7	-1.5	527.156 9, 275.078 6, 203.057 1	Yong (SDH)
11	Catalpol	1.538	C₁₅H₂₂O₁₀	[M+Na]⁺	385.112 3	3.1	136.061 5, 119.034 6	Yong (SDH)
12	Rehmannioside D	1.693	C₂₇H₄₂O₂₀	[M-H]^-	685.219 8	1.0	505.149 9, 341.112 9, 263.077 6, 179.055 3	Yong (SDH)
13	Melittoside	1.995	C₂₁H₃₂O₁₅	[M-H]^-	523.167 5	2.3	163.041 3, 135.045 9	Yong (SDH)
14	Protocatechuic acid	2.139	C₇H₆O₄	[M-H]^-	153.019 4	3.9	109.028 8	Ti (XFH), Yong (WWZ, DZY, SDH)
15	Geniposidic acid	2.139	C₁₆H₂₂O₁₀	[M-H]^-	373.112 6	-2.4	211.061 2, 123.048 7	Yong (SDH)
16	Dihydroferulic acid	2.758	C₁₀H₁₂O₄	[M+H]⁺	197.081 5	0.5	179.072 9, 167.071 4	Yong (SDH)
17	Salidroside	2.779	C₁₄H₂₀O₇	[M+Na]⁺	323.109 6	-3.4	224.061 5	Yong (SDH)
18	Vanillic acid	2.892	C₈H₈O₄	[M-H]^-	167.035 1	4.2	122.991 1, 151.984 6	Yong (SDH)
19	Ajugol	3.201	C₁₅H₂₄O₉	[M-H]^-	347.135 2	2.9	113.025 9, 167.033 7, 181.050 6, 303.107 2	Yong (SDH)
20	Quinic acid	3.254	C₇H₁₂O₆	[M-H]^-	191.056 2	3.1	109.031 7, 127.040 7, 173.045 8, 191.056 7	Yong (WWZ)
21	5-Hydroxymethylfurfural	3.482	C₆H₆O₃	[M+H]⁺	127.039 1	-3.1	109.030 8	Yong (MD, WWZ)
22	Neochlorogenic acid	5.040	C₁₆H₁₈O₉	[M-H]^-	353.087 8	1.4	127.033 0, 135.045 6, 161.027 9, 179.036 3, 191.057 4	Ti (XFH), Yong (DZY)
23	5-Hydroxymethyl-2-furaldehyde	5.163	C₆H₆O₃	[M-H]^-	125.023 6	-2.4	109.040 7	Yong (WWZ)
24	Decaffeoyl-verbascoside	5.237	C₂₀H₃₀O₁₂	[M-H]^-	461.164 9	-2.2	135.047 7, 123.041 9	Yong (SDH)
25	8-Epiloganic acid	5.630	C₁₆H₂₄O₁₀	[M-H]^-	375.128 9	-0.5	213.076 1, 169.088 4, 151.077 2	Yong (SDH)
26	Protocatechualdehyde	5.753	C₇H₆O₃	[M-H]^-	137.024 5	4.4	108.020 8, 109.025 7	Ti (XFH)
27	Acetylcatalpol	5.785	C₁₇H₂₄O₁₁	[M-H]^-	403.124 0	0.0	165.053 1, 139.039 6	Yong (SDH)
28	3,7-Dihydroxycoumarin	5.929	C₉H₆O₄	[M-H]^-	177.019 4	3.4	105.033 7, 133.028 4, 149.022 4	Ti (XFH)
29	Geniposide	6.239	C₁₇H₂₄O₁₀	[M+Na]⁺	411.127 7	2.4	149.057 8, 103.048 8	Yong (SDH)
30	Schisandrol A	6.889	C₂₄H₃₂O₇	[M+H]⁺	433.223 8	2.8	384.181 9, 353.161 3, 218.087 7	Yong (WWZ)
31	Cistanoside F	6.910	C₂₁H₂₈O₁₃	[M-H]^-	487.144 1	-2.3	179.033 5, 161.027 4, 135.046 9	Yong (SDH)
32	Caffeic acid	7.065	C₉H₈O₄	[M-H]^-	179.035 1	3.9	107.048 7, 109.029 8, 117.035 7, 134.039 4, 135.046 2, 136.084 1	Ti (XFH, ZGH), Yong (SDH)
33	Echinacoside	7.466	C₃₅H₄₆O₂₀	[M+Na]⁺	809.247 1	-1.1	287.072 6, 163.038 7	Yong (SDH)
34	sec-Hydroxyaeginetic acid	7.860	C₁₅H₂₄O₅	[M-H]^-	283.155 7	4.2	163.107 6, 181.099 3, 203.162 4, 239.123 3, 265.127 2	Yong (SDH)
35	Cryptochlorogenic acid	7.962	C₁₆H₁₈O₉	[M-H]^-	353.088 2	2.5	111.048 6, 135.045 8, 155.036 4, 173.047 1, 179.037 1, 191.057 6	Ti (XFH), Yong (DZY)
36	Naringenin	8.263	C₁₅H₁₂O₅	[M-H]^-	271.061 7	4.1	151.004 3, 119.050 2	Yong (DZY))
37	5,7,4′-Trihydroxy-3′-methoxy-6,8-dimethyl-homisoflavanone	8.542	C₁₉H₂₀O₆	[M+H]⁺	345.133 1	-2.0	137.053 3, 299.084 2	Yong (MD)
38	Liquiritin	8.562	C₂₁H₂₂O₉	[M-H]^-	417.118 4	-0.5	255.067 8, 161.024 0, 148.017 2	Ti (ZGC)
39	Chlorogenic acid	9.006	C₁₆H₁₈O₉	[M-H]^-	353.087 8	1.4	191.057 8, 179.036 5, 173.043 8	Ti (XFH), Yong (WWZ, DZY)
40	Prim-O-glucosylcimifugin	9.069	C₂₂H₂₈O₁₁	[M+H]⁺	469.170 8	-0.4	235.060 4, 189.041 2	Yong (SDH)
41	Kaempferol-3-rutinoside	9.843	C₂₇H₃₀O₁₅	[M+H]⁺	595.165 8	-0.8	415.089 1, 463.105 5	Ti (ZGC)
42	1,3-Dicaffeoylquinic acid	10.121	C₂₅H₂₄O₁₂	[M-H]^-	515.119 0	0.0	191.057 4, 179.036 2, 135.045 9	Ti (XFH)
43	Verbascoside	10.401	C₂₉H₃₆O₁₅	[M+Na]⁺	647.196 0	1.2	501.139 9, 485.137 5, 339.090 7, 163.037 5	Yong (SDH)
44	Rutin	10.637	C₂₇H₃₀O₁₆	[M+H]⁺	611.161 2	0.0	129.066 9, 257.068 3, 303.052 9, 465.106 9	Yong (DZY)
45	Neo-rehmannioside E	10.690	C₂₁H₃₄O₁₀	[M-H]^-	445.208 9	3.4	161.025 4, 265.099 2	Yong (SDH)
46	Isoschaftoside	11.052	C₂₆H₂₈O₁₄	[M+H]⁺	565.154 9	-1.4	295.059 8, 325.071 0, 337.071 4, 391.081 7, 409.090 6, 427.100 8, 565.154 0	Ti (ZGC), Yong (DZY)
47	Schaftoside	11.062	C₂₆H₂₈O₁₄	[M-H]^-	563.139 5	-1.1	473.111 5, 383.078 5	Ti (ZGC)
48	Loliolid	11.123	C₁₁H₁₆O₃	[M+H]⁺	197.117 8	0.0	105.075 8, 115.052 3, 133.099 6, 161.100 2, 179.103 5	Ti (XFH)
49	Quercetagetin-7-O-glucoside	11.207	C₂₁H₂₀O₁₃	[M+H]⁺	481.097 0	-2.5	319.043 5	Ti (XFH)
50	5,7,2′-Trihydroxy-8-methyl-3-(3′,4′-methylenedioxybenzyl)-chromone	11.238	C₁₈H₁₄O₇	[M+H]⁺	343.080 4	-4.1	205.046 7, 177.054 3, 149.056 7	Yong (MD)
51	Methyl eugenol	11.238	C₁₁H₁₄O₂	[M+H]⁺	179.106 9	-1.7	117.062 9, 143.073 7, 144.080 6	Hua (XX)
52	Isoorientin	11.361	C₂₁H₂₀O₁₁	[M+H]⁺	449.108 7	0.7	299.054 2, 166.021 8, 300.062 1	Yong (DZY)
53	Orientin	11.414	C₂₁H₂₀O₁₁	[M-H]^-	447.093 0	0.7	327.051 3, 357.064 0, 297.040 0	Yong (DZY)
54	Cistanoside A	11.671	C₃₆H₄₈O₂₀	[M-H]^-	799.263 7	-3.0	623.218 9, 175.037 8	Yong (SDH)
55	2-O-β-D-Glucopyranosyl atractyligenin	11.702	C₂₅H₃₈O₉	[M-H]^-	481.244 4	1.2	301.181 3, 320.184 0	Ti (XFH)
56	Rehmannioside C	11.723	C₁₉H₃₂O₈	[M+Na]⁺	411.199 9	1.0	245.194 6	Yong (SDH)
57	Rehmapicroside	11.949	C₁₆H₂₆O₈	[M-H]^-	345.154 5	-1.2	165.054 5	Yong (SDH)
58	Liquiritigenin	12.156	C₁₅H₁₂O₄	[M-H]^-	255.066 0	1.2	135.048 0, 119.050 9	Ti (ZGC)
59	Liquiritin apioside	12.363	C₂₆H₃₀O₁₃	[M-H]^-	546.161 1	0.5	417.119 6, 255.067 4, 135.010 1	Ti (ZGC)
60	Afzelin	12.423	C₂₁H₂₀O₁₀	[M-H]^-	431.098 3	1.2	283.062 0, 311.056 1, 323.052 8	Ti (ZGC)
61	Isovitexin	12.434	C₂₁H₂₀O₁₀	[M+H]⁺	433.113 4	-0.2	433.112 1, 313.072 1, 415.103 6	Yong (DZY)
62	Vitexin	12.444	C₂₁H₂₀O₁₀	[M-H]^-	431.097 0	-1.9	117.035 0, 283.061 1, 161.022 9	Yong (DZY)
63	Taxifolin	12.704	C₁₅H₁₂O₇	[M-H]^-	303.051 4	3.0	107.016 0, 125.026 2, 175.035 5, 217.054 2	Ti (XFH)
64	Quercetin-3-O-glucuronide	12.796	C₂₁H₁₈O₁₃	[M+H]⁺	479.082 4	-0.4	303.048 9	Ti (XFH)
65	Quercetin	12.859	C₁₅H₁₀O₇	[M-H]^-	301.034 8	0.0	229.047 9, 178.997 2, 151.004 5	Ti (XFH), Yong (DZY)
66	Hyperoside	13.013	C₂₁H₂₀O₁₂	[M-H]^-	463.087 7	0.0	151.005 2, 255.031 6, 271.025 8, 300.028 1, 301.035 2	Ti (XFH)
67	Isoquercitrin	13.024	C₂₁H₂₀O₁₂	[M-H]^-	463.087 9	0.4	107.014 6, 151.004 6, 178.998 9, 255.029 7, 300.028 4, 301.033 9	Ti (XFH)
68	Patulitrin	13.231	C₂₂H₂₂O₁₃	[M+H]⁺	495.114 1	0.4	318.035 9, 333.059 7	Ti (XFH)
69	Jiocarotenoside B1	13.415	C₃₇H₅₀O₂₀	[M-H]^-	813.280 3	-1.7	637.236 2, 175.032 2	Yong (SDH)
70	Azelaic acid	13.446	C₉H₁₆O₄	[M-H]^-	187.096 0	-5.3	125.095 4	Yong (MD)
71	Neo-rehmannioside B	13.633	C₁₅H₂₄O₆	[M-H]^-	299.149 3	-0.7	139.073 5	Yong (SDH)
72	Isorhamnetin-3-O-glucoside	13.675	C₂₂H₂₂O₁₂	[M-H]^-	477.103 7	0.8	107.021 1, 151.002 7, 285.040 5, 314.043 7, 315.051 7	Ti (XFH)
73	1,5-Dicaffeoylquinic acid	13.808	C₂₅H₂₄O₁₂	[M-H]^-	515.119 5	1.0	335.078 9, 191.056 4, 179.035 3	Ti (XFH)
74	Forsythoside A	14.026	C₂₉H₃₆O₁₅	[M-H]^-	623.198 1	0.8	177.017 3, 119.048 2	Yong (SDH)
75	Isochlorogenic acid A	15.214	C₂₅H₂₄O₁₂	[M-H]^-	515.119 5	1.0	203.037 2, 191.057 1, 179.036 2	Ti (XFH)
76	5-Methoxy-6-methyl-7-oxhydryl-8-methoxy-3-(2′-oxhydryl-4′-methoxybenzyl)-4-chromanone	15.429	C₂₀H₂₂O₇	[M-H]^-	373.129 8	2.9	153.019 6, 168.046 0	Yong (MD)
77	5,7-Dihydroxy-3-(4′-methoxybenzyl)-4-chromone	15.865	C₁₇H₁₄O₅	[M-H]^-	297.075 2	-3.7	203.037 1, 175.046 9	Yong (MD)
78	Aegineticacid	15.957	C₁₅H₂₄O₄	[M+H]⁺	269.176 4	4.1	167.010 4	Yong (SDH)
79	Formononetin	16.122	C₁₆H₁₁O₄	[M-H]^-	267.066 0	1.1	252.044 8	Ti (ZGC)
80	Ophiopogonanone E	16.308	C₁₉H₂₀O₇	[M-H]^-	359.113 6	1.4	208.034 1, 138.035 6	Yong (MD)
81	5,7-Dihydroxy-6,8-dimethyl-3-(3′,5′-dimethoxy-4′-hydroxybenzyl)-4-chromanone	16.339	C₂₀H₂₂O₇	[M-H]^-	373.130 0	3.5	207.064 6, 179.070 1, 135.046 6	Yong (MD)
82	5,7-Dihydroxy-8-methyl-3-(3′,4′-dimethoxybenzyl)-4-chromone	16.410	C₁₈H₁₄O₆	[M-H]^-	325.071 8	1.8	297.073 3, 131.053 8, 203.035 9	Yong (MD)
83	Neoliquiritin	16.474	C₂₁H₂₂O₉	[M+H]⁺	419.132 6	-3.8	119.047 6, 137.022 1, 239.069 7, 257.080 6	Ti (ZGC)
84	Isoliquiritin	16.959	C₂₁H₂₂O₉	[M+H]⁺	419.135 1	2.1	137.023 2, 239.070 8, 257.082 5	Ti (ZGC)
85	Isoliquiritigenin	16.969	C₁₅H₁₂O₄	[M+H]⁺	257.081 0	-1.6	137.023 8	Ti (ZGC)
86	Martynoside	17.103	C₃₁H₄₀O₁₅	[M-H]^-	651.228 5	-0.6	193.048 0, 175.042 1	Yong (SDH)
87	Spinacetin	17.216	C₁₇H₁₄O₈	[M-H]^-	345.061 6	1.7	315.014 5, 330.038 3	Ti (XFH)
88	5-Oxhydryl-6-methyl-7-methoxy-3-(3′,4′-dihydroxyphenyl)-4-chromone	17.546	C₁₈H₁₆O₆	[M-H]^-	327.086 5	-1.2	164.049 8, 327.084 9	Yong (MD)
89	Uralsaponin F	17.693	C₄₄H₆₄O₁₉	[M-H]^-	895.399 4	3.4	853.394 4, 821.353 5, 351.059 5	Ti (ZGC)
90	1-O-Acetyl britannilactone	18.354	C₁₇H₂₄O₅	[M+H]⁺	309.169 2	-3.2	291.050 0, 231.136 9, 203.141 2	Ti (XFH)
91	Luteolin	18.404	C₁₅H₁₀O₆	[M-H]^-	285.039 7	-0.7	175.035 6, 151.004 5, 133.026 6	Ti (XFH), Yong (DZY)
92	Eupafolin	18.684	C₁₆H₁₂O₇	[M-H]^-	315.051 3	2.5	300.027 4	Ti (XFH)
93	Rosmarinic acid	20.563	C₁₈H₁₆O₈	[M-H]^-	359.077 4	1.9	133.029 3, 135.044 2, 161.025 6, 193.014 4	Ti (XFH)
94	Licorice saponin A3	20.770	C₄₈H₇₂O₂₁	[M+H]⁺	985.467 6	3.2	453.336 4, 471.348 0, 615.389 4, 809.433 9	Ti (ZGC)
95	Diosmetin	21.069	C₁₆H₁₂O₆	[M-H]^-	299.056 9	4.3	227.037 1, 256.039 1, 284.032 8	Yong (DZY)
96	Ophiopogonin D	21.070	C₄₄H₇₀O₁₆	[M+H]⁺	855.471 6	-3.0	251.178 2, 287.200 7, 431.313 8, 559.363 5, 577.379 1, 711.368 9, 723.434 0	Yong (MD)
97	Licorice saponin G2	21.153	C₄₂H₆₂O₁₇	[M+H]⁺	839.408 6	2.5	451.320 7, 469.331 2, 487.341 5, 663.377 1	Ti (ZGC)
98	Licorice saponin E2	21.193	C₄₂H₆₀O₁₆	[M+H]⁺	821.395 8	-0.2	451.323 1, 469.332 6, 645.364 4	Ti (ZGC)
99	Gancaonin G	21.203	C₂₁H₂₀O₅	[M+H]⁺	353.139 8	2.5	267.063 7, 297.108 2	Ti (ZGC)
100	Glycyrrhetinic acid	21.266	C₃₀H₄₆O₄	[M+H]⁺	471.346 2	-2.5	407.329 5, 435.326 9, 453.337 0	Ti (ZGC)
101	Neobritannilactone B	21.276	C₁₅H₂₀O₃	[M-H]^-	247.133 8	1.6	203.148 3, 201.132 8, 135.083 1	Ti (XFH)
102	Methylophiopogonone A	21.286	C₁₉H₁₆O₆	[M-H]^-	339.087 3	1.2	311.093 4, 217.208 3	Yong (MD)
103	Ophiopogonanone B	21.328	C₁₉H₂₀O₅	[M-H]^-	327.124 5	4.0	178.066 9	Yong (MD)
104	Glycyrrhizic acid	21.389	C₄₂H₆₂O₁₆	[M-H]^-	821.396 3	0.4	351.055 0, 193.034 8, 469.344 7	Ti (ZGC)
105	Pregomisin	21.431	C₂₂H₃₀O₆	[M+H]⁺	391.212 2	0.3	327.143 6, 275.084 7, 229.096 2	Yong (WWZ)
106	Uralsaponin C	21.473	C₄₂H₆₄O₁₆	[M+H]⁺	825.428 1	1.0	455.351 0, 473.361 4	Ti (ZGC)
107	8-Formyl ophiopogonone B	21.534	C₂₀H₂₂O₇	[M+H]⁺	375.143 9	-1.3	109.062 1, 251.090 2, 357.133 8	Yong (MD)
108	Casticin	21.699	C₁₉H₁₈O₈	[M+H]⁺	375.107 6	-1.1	360.082 6, 375.103 9, 377.116 6	Ti (XFH)
109	Schisandrol B	21.751	C₂₃H₂₈O₇	[M+H]⁺	417.192 3	2.4	368.147 1, 399.179 9	Yong (WWZ)
110	Diosgenin	21.804	C₂₇H₄₂O₃	[M+H]⁺	415.321 5	0.7	157.095 5	Yong (MD)
111	Ilicic acid	21.824	C₁₅H₂₄O₃	[M-H]^-	251.165 8	4.4	207.173 2	Ti (XFH)
112	Japonicones D	21.885	C₃₄H₄₄O₉	[M+H]⁺	597.305 9	-0.8	211.109 5, 185.132 0	Ti (XFH)
113	Gomisin D	21.896	C₂₈H₃₄O₁₀	[M+H]⁺	531.224 5	2.8	401.158 9, 383.149 2, 341.101 3	Yong (WWZ)
114	Gomisin R	21.906	C₂₂H₂₄O₇	[M+H]⁺	401.159 3	-1.7	337.106 6, 341.102 8, 383.148 2	Yong (WWZ)
115	Gomisin J	21.927	C₂₂H₂₈O₆	[M+H]⁺	389.194 5	-4.9	227.075 0, 287.092 0, 137.060 1	Yong (WWZ)
116	5-Oxhydryl-6-aldehyde-7-methoxy-8-methyl-3-(4′-methoxybenzyl)-4-chromanone	21.937	C₂₀H₂₀O₆	[M-H]^-	355.120 0	5.1	217.052 1, 150.031 8	Yong (MD)
117	Ruscogenin	21.938	C₂₇H₄₂O₄	[M+H]⁺	431.316 8	1.6	251.177 6, 269.185 4, 139.078 6	Yong (MD)
118	Sesamin	21.959	C₂₀H₁₈O₆	[M+H]⁺	355.117 9	-0.8	179.035 7, 268.985 4	Hua (XX)
119	Angeloylgomisin H	22.029	C₂₈H₃₆O₈	[M+H]⁺	501.248 9	0.2	370.173 1, 355.154 4, 337.142 4	Yong (WWZ)
120	Schisantherin B	22.071	C₂₈H₃₄O₉	[M+H]⁺	515.227 9	-0.4	385.165 4, 355.152 5, 343.116 8	Yong (WWZ)
121	Benzoylgomisin H	22.155	C₃₀H₃₄O₈	[M+H]⁺	523.231 3	-3.6	441.181 5, 409.159 0, 386.174 3	Yong (WWZ)
122	Gedunin	22.155	C₂₈H₃₄O₇	[M+H]⁺	483.238 3	0.0	381.133 3, 395.149 1, 367.117 2	Yong (WWZ)
123	Schisandrin B	22.155	C₂₃H₂₈O₆	[M+H]⁺	401.195 8	-1.5	386.174 3, 370.177 3	Yong (WWZ)
124	Alantolactone	22.195	C₁₅H₂₀O₂	[M+H]⁺	233.153 9	1.7	159.114 6, 118.071 1, 106.073 7	Ti (XFH)
125	Schisanhenol B	22.237	C₂₂H₂₆O₆	[M+H]⁺	387.179 7	-2.8	355.154 1, 326.150 7, 271.060 4	Yong (WWZ)
126	Schisandrin C	22.350	C₂₂H₂₄O₆	[M+H]⁺	385.166 2	2.9	257.080 8, 199.074 8, 184.051 5	Yong (WWZ)
127	Schisantherin A	22.381	C₃₀H₃₂O₉	[M+H]⁺	537.209 6	-5.4	415.173 3, 397.163 7, 371.148 9	Yong (WWZ)
128	Schisandrin A	22.753	C₂₄H₃₂O₆	[M+H]⁺	417.226 5	-2.9	402.203 2, 386.204 3, 371.184 9	Yong (WWZ)
129	Schisanhenol	22.504	C₂₃H₃₀O₆	[M+H]⁺	403.211 0	-2.7	302.116 8, 271.093 8	Yong (WWZ)
130	Asarinin	22.940	C₂₀H₁₈O₆	[M+NH₄]⁺	372.144 4	-0.8	128.060 9, 135.038 8, 161.063 1	Hua (XX)
131	5,7,2′-Trihydroxy-6,8-dimethyl-3-(3′,4′-methylenedioxybenzyl)-chromone	22.961	C₁₉H₁₆O₇	[M+H]⁺	357.097 2	-0.6	339.097 9	Yong (WWZ)
132	Dibutyl phthalate	23.239	C₁₆H₂₂O₄	[M+H]⁺	279.160 9	4.7	149.022 3, 121.027 8	Yong (WWZ)

Component	Content/mg·g^-1
Schisandrol B	0.93 ± 0.04
Schizandrin A	0.37 ± 0.07
Schisandrin C	1.15 ± 0.11
Methylophiopogonone A	2.62 ± 0.31
Ophiogonanone A	3.00 ± 0.23
1-O-Acetyl britannilactone	2.37 ± 0.06
Britannin	0.73 ± 0.13

Component	Content/mg·g^-1
Schisandrol B	0.93 ± 0.04
Schizandrin A	0.37 ± 0.07
Schisandrin C	1.15 ± 0.11
Methylophiopogonone A	2.62 ± 0.31
Ophiogonanone A	3.00 ± 0.23
1-O-Acetyl britannilactone	2.37 ± 0.06
Britannin	0.73 ± 0.13

基于UPLC-QTOF-MS/MS和网络药理学分析大补肺汤体-用-化配伍治疗COPD稳定期的物质基础和作用机制

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韩昱 ¹ , 罗月月 ¹ , 黄圣如 ¹ , 宿树兰 ¹^,^* , 刘培 ¹ , 尚尔鑫 ¹ , 刘永琦 ² , 段金廒 ¹

药学学报 | 研究论文 2026,61(5): 1804-1818

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药学学报 |研究论文 2026 , 61 (5) : 1804 -1818

基于UPLC-QTOF-MS/MS和网络药理学分析大补肺汤体-用-化配伍治疗COPD稳定期的物质基础和作用机制

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韩昱¹, 罗月月¹, 黄圣如¹, 宿树兰¹^,^*, 刘培¹, 尚尔鑫¹, 刘永琦², 段金廒¹

作者信息

¹南京中医药大学, 江苏省方剂功效物质与创新药物发现重点实验室, 中药资源产业化与方剂创新药物国家地方联合工程研究中心, 江苏省中药资源产业化过程协同创新中心, 中药制药过程控制与智能制造技术全国重点实验室, 江苏南京 210023

²甘肃中医药大学, 敦煌医学与转化教育部重点实验室, 甘肃兰州 730050

通讯作者:

宿树兰，E-mail: sushulan@njucm.edu.cn

作者简介:

作者贡献:

宿树兰负责课题总体设计及文章修改等; 刘永琦负责项目总体设计; 段金廒给予研究思路和学术指导; 韩昱负责实验操作、数据处理及论文撰写; 罗月月、黄圣如协助实验完成; 刘培、尚尔鑫负责实验技术指导。

Study on the material basis and mechanism of "Ti-Yong-Hua" compatibility of Dabufei Decoction in treating the stable phase of COPD based on UPLC-QTOF-MS/MS and network pharmacology

Yu HAN¹, Yue-yue LUO¹, Sheng-ru HUANG¹, Shu-lan SU¹^,^*, Pei LIU¹, Er-xin SHANG¹, Yong-qi LIU², Jin-ao DUAN¹

Affiliations

¹Nanjing University of Chinese Medicine, Jiangsu Key Laboratory for High Technology Research of Traditional Chinese Medicine Formulae, National-Local Joint Engineering Research Center of Resources Industrialization of Chinese Medica and Prescription-Oriented Innovative Drugs, Jiangsu Collaborative Innovation Center of Chinese Medicinal Resources Industrialization, State Key Laboratory of Technologies for Chinese Medicine Pharmaceutical Process Control and Intelligent Manufacture, Nanjing 210023, China

²Gansu University of Chinese Medicine, Dunhuang Key Laboratory of Medicine and Traditional Education of the Ministry of Education, Lanzhou 730050, China

出版时间: 2026-05-12 doi: 10.16438/j.0513-4870.2025-1278

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摘要

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采用超高效液相-四级杆-飞行时间高分辨质谱联用(UPLC-QTOF-MS/MS) 技术对大补肺汤的化学成分进行分析和鉴定, 并结合网络药理学探究大补肺汤作用于慢性阻塞性肺疾病(chronic obstructive pulmonary disease, COPD) 稳定期的作用机制。在正、负离子模式下, 通过化合物精确分子量、MS/MS裂解规律和文献报道数据等信息对大补肺汤中的化学成分进行鉴定, 再结合TCMSP数据库、文献挖掘大补肺汤有效成分和作用靶点, 通过OMIM、Gene Cards数据库获得COPD稳定期靶点, 筛选出药物靶点和疾病靶点的交集靶点, 导入STRING数据库及Cytoscape 3.10.3构建PPI网络, 通过Metascape数据库对核心靶点进行GO和KEGG富集分析。结果显示, 大补肺汤中共鉴定出132个化学成分, 有87种成分来自“用”组药味, 49种来自“体”组药味, 4种来自“化”组药味, 8种成分为体、用组药味共有成分。基于Swiss ADME胃肠道吸收和类药性五项原则筛选出大补肺汤中84个潜在活性成分, 与COPD稳定期有294个共同靶点, 基于Cytoscape计算得到87个核心靶点, KEGG富集通路主要包括PI3K-AKT信号通路、HIF-1α信号通路、AGE-RAGE信号通路、EGFR酪氨酸激酶抑制剂耐药性、MAPK信号通路等发挥治疗COPD稳定期的作用, 其中体组药味主要作用于C型凝集素受体信号通路, 用组药味作用于PI3K-AKT信号通路, 化组药味作用于Th17细胞的分化过程。研究结果为该方临床应用及深入研究提供科学依据与支撑。

关键词

大补肺汤 / 慢性阻塞性肺疾病稳定期 / 网络药理 / 化学成分 / 作用机制 / 辅行诀

Abstract

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Ultra-high performance liquid chromatography-quadrupole-time-of-flight tandem mass spectrometry (UPLC-QTOF-MS/MS) was used to analyze and identify the chemical components of Dabufei Decoction (DBFT). Combined with network pharmacology, the mechanism of action of DBFT in the stable phase of chronic obstructive pulmonary disease (COPD) was explored. Under positive and negative ion modes, the chemical components of DBFT were identified based on information such as the accurate molecular weight of compounds, MS/MS fragmentation rules, and literature-reported data. Then, combined with the TCMSP database and literature mining, the active components and action targets of DBFT were obtained. Targets related to the stable phase of COPD were retrieved from the OMIM and Gene Cards databases. The overlapping targets between drug targets and disease targets were screened out, imported into the STRING database and Cytoscape 3.10.3 to construct a protein-protein interaction (PPI) network, and Gene Ontology (GO) and Kyoto Encyclopedia of Genes and Genomes (KEGG) enrichment analyses of core targets were performed using the Metascape database. The results showed that a total of 132 chemical components were identified in DBFT, among which 87 components were derived from the "Yong" group of herbs, 49 from the "Ti" group of herbs, 4 from the "Hua" group of herbs, and 8 components were shared by the "Ti" and "Yong" groups of herbs. A total of 84 potential active components of DBFT were screened out based on the Swiss ADME gastrointestinal absorption and five principles of druggability. There were 294 common targets with the stable phase of COPD, and 87 core targets were obtained through calculation using Cytoscape. The KEGG-enriched pathways mainly included the PI3K-AKT signaling pathway, HIF-1α signaling pathway, AGE-RAGE signaling pathway, EGFR tyrosine kinase inhibitor resistance, and MAPK signaling pathway, which played a role in the treatment of the stable phase of COPD. Among them, the "Ti" group of herbs mainly acted on the C-type lectin receptor signaling pathway, the "Yong" group of herbs acted on the PI3K-AKT signaling pathway, and the "Hua" group of herbs acted on the differentiation process of Th17 cells. The research results provide a scientific basis and support for the clinical application and in-depth study of this prescription.

Key words

Dabufei Decoction / stable phase of chronic obstructive pulmonary disease / network pharmacology / chemical component / mechanism of action / Fuxingjue

引用本文

韩昱, 罗月月, 黄圣如, 宿树兰, 刘培, 尚尔鑫, 刘永琦, 段金廒. 基于UPLC-QTOF-MS/MS和网络药理学分析大补肺汤体-用-化配伍治疗COPD稳定期的物质基础和作用机制. 药学学报, 2026 , 61 (5) : 1804 -1818 . DOI: 10.16438/j.0513-4870.2025-1278

Yu HAN, Yue-yue LUO, Sheng-ru HUANG, Shu-lan SU, Pei LIU, Er-xin SHANG, Yong-qi LIU, Jin-ao DUAN. Study on the material basis and mechanism of "Ti-Yong-Hua" compatibility of Dabufei Decoction in treating the stable phase of COPD based on UPLC-QTOF-MS/MS and network pharmacology[J]. Acta Pharmaceutica Sinica, 2026 , 61 (5) : 1804 -1818 . DOI: 10.16438/j.0513-4870.2025-1278

正文

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慢性阻塞性肺疾病(chronic obstructive pulmonary disease, COPD), 简称慢阻肺, 是一种异质性疾病, 特征主要为慢性呼吸道症状(呼吸困难、咳嗽、咳痰), 这是由于气道(支气管炎、细支气管炎) 和/或肺泡异常(肺气肿) 所致, 引起持续加重的气流受限^[1]。全球疾病负担(global burden of disease, GBD) 的数据显示, COPD全球患病率为10.3%^[2-4], 我国40岁及以上成年人患病率高达13.7%, 且随着人口老龄化的加剧和吸烟率的上升, 慢阻肺的患病率在未来呈现持续上升的趋势^[5]。目前, 我国慢阻肺的治疗多采用吸入支气管舒张剂、口服β₂受体激动剂、茶碱类药物等方法, 但不良反应明显, 易引起心动过速、心律失常、肌肉震颤等问题。近年来, 研究表明中医药能够通过调控炎症反应、改善免疫调节、降低氧化应激等多途径治疗COPD。

《辅行诀脏腑用药法要》是一部总结商代伊尹的《汤液经法》辨五脏病证及组方用药规律的书籍, 以“汤液经法图”作为组方配伍的核心机制, 基于五脏虚实辨证采用五味体用补泻的治疗方法^{[6, 7]}。《辅行诀》认为病因正气亏损而成, 治法着力于调和五脏体用之平衡, 其中蕴含着富有特色的“体-用-化”治法理论。《辅行诀》中提及的脏之体和用, 根据《素问·脏气法时论》中天人合一的思想, 可认为用为五脏的功用, 体为发生功用的物质基础, 简而言之, 脏之用是不可见的、偏功能性的现象, 脏之体是可见的、有形质的物质基础^[8]。脏之化为调和, 虚实兼治, 为五味配伍转换关系, 即在体用交换过程中, 体用合二为一而形成的新的质体, 以平和脏腑。COPD稳定期在中医论治中属于“肺虚”, 从《辅行诀》补泻治法来看, 虚需补之, 补本脏或补母脏, 故重用用味、轻用体味。大补肺汤由五味子、麦冬、生地黄、淡竹叶、旋覆花、炙甘草、细辛7味药组成, 共四补两泻一化, 主治烦热汗出, 少气不足息, 口干、耳聋, 脉虚而快。其中, 五味子补肺用; 麦冬补母脏脾土; 地黄、竹叶, 补子脏肾水; 旋覆花泻肺体, 以防滋腻; 甘草补母脏, 培土生金; 细辛入肺脏化味, 调肺虚^{[9, 10]}。目前, 对于大补肺汤治疗慢阻肺稳定期的药效物质基础及其作用机制研究尚不深入。

根据课题组^[11]前期研究, 本文基于UPLC-Q-TOF-MS/MS技术对大补肺汤的化学成分进行分析鉴定, 通过网络药理学方法对大补肺汤及体、用、化各组治疗慢阻肺稳定期的潜在活性成分及分子机制进行预测分析, 以期为大补肺汤的临床应用和深入研究提供科学依据。

材料与方法

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仪器 UPLC-Q-TOF-MS/MS (ESI) 串联质谱仪、MassLynx^TM v4.2 (Waters Corp.) 分析软件、Waters ACQUITY UPLC系统(包括四元泵溶剂, 在线脱气机和自动进样器; 美国Waters公司); AB Triple Quad 6500 Plus三重四级杆线性离子阱质谱仪系统(美国AB SCIEX公司), 配有电喷雾离子源及Analyst1.6.3软件; 微型涡旋混合仪(上海沪西分析仪器厂有限公司); ML105型电子天平(赛多利斯科学仪器北京有限公司); Unique-R40多功能超纯水系统(厦门锐思捷水纯化技术有限公司); Anke GL-16G型离心机(上海安亭科学仪器厂)。

药品与试剂 大补肺汤中五味子(批号240401, 产地辽宁)、麦冬(批号240316, 产地四川)、生地黄(批号240320, 产地河南)、淡竹叶(批号240119, 产地浙江)、旋覆花(批号240115, 产地江苏)、炙甘草(批号240315, 产地内蒙古)、细辛(批号240228, 产地辽宁) 7味药材均购自苏州市天灵中药饮片有限公司, 经南京中医药大学段金廒教授鉴定为正品药材饮片。对照品五味子甲素(批号: J10GB151096)、五味子丙素(批号: N04GB166743)、五味子醇乙(批号: JB247585)、甲基麦冬黄酮A (批号: A28IB214114)、麦冬黄烷酮A (批号: F26HB176323)、1-O-乙酰旋覆花内酯(批号: KB356710)、大花旋覆花素(批号: Z04A9L57509)、克拉霉素(批号: Y31M7C12157)均购自上海源叶生物科技有限公司。色谱级乙腈和甲醇(德国Merck公司), 色谱级甲酸(美国Thermo Fisher Scientific公司), 屈臣氏蒸馏水购自南京何苗生物科技有限公司。

对照品溶液 称取适量对照品五味子醇乙、五味子甲素、五味子丙素、甲基麦冬黄酮A、麦冬黄烷酮A、1-O-乙酰旋覆花内酯、大花旋覆花素加甲醇溶解后定容, 混匀, 即得单一成分对照品储备液。

标准曲线溶液 精密吸取对照品溶液储备液适量, 混匀制成混合标准品溶液, 并用甲醇稀释成一系列浓度, 得到定量标准曲线溶液。

标准曲线溶液 精密称取对照品克拉霉素适量, 用甲醇溶解并稀释至500 ng·mL^-1作为内标溶液。

供试品溶液 根据该方的临床用法, 采用水煎煮的方法进行样品制备。称取五味子9 g、麦冬9 g、生地黄3 g、淡竹叶3 g、旋覆花9 g、炙甘草3 g、细辛3 g, 第一次加入10倍量水浸泡30 min, 沸腾后煎煮1 h, 过滤收集药液, 再加入10倍量水煎煮1 h, 过滤合并滤液, 浓缩至每1 mL含1 g生药的大补肺汤水提液样品。精密吸取大补肺汤水提液样品1 mL, 加入4 mL甲醇后涡旋混匀, 4 ℃下13 000 r·min^-1离心15 min, 取上清液经0.22 μm孔径滤膜过滤得供试品溶液, 备用。

色谱条件 采用Waters ACQUITY UPLC BEH C₁₈色谱柱(100 mm × 2.1 mm, 1.7 μm); 流动相: 0.1%甲酸水(A)-乙腈(B); 梯度洗脱: 0~3 min, 5%~30% B; 20~22 min, 30%~100% B; 22~24 min, 100%~5% B; 24~25 min, 5% B; 柱温: 30 ℃; 流速: 0.4 mL·min^-1; 进样量: 2 μL。

UPLC-Q-TOF-MS/MS质谱条件采用电喷雾离子源(ESI) 正、负离子扫描模式, 毛细管电压3.0 kV, 离子源温度120 ℃, 脱溶剂温度400 ℃, 锥孔电压15 V, 锥孔气流量50 L·h^-1, 脱溶剂流量80 L·h^-1, 质量扫描范围m/z 100~1 000, MS/MS源内碰撞诱导解离电压为20~30 V。

AB Triple Quad 6500 Plus质谱条件采用电喷雾离子源(ESI) 正离子扫描模式, 检测模式为多反应检测(MRM) 模式, 正离子电喷雾电压: 5 500 V, 雾化气压力40 kPa, 气帘气压力40 kPa, 离子源温度450 ℃, 碰撞气: Medium, 7种被测物质及1种内标物质MRM参数见表1。

线性关系考察 对不同浓度混合对照品溶液进样测定, 以对照品与内标峰面积之比为纵坐标(Y), 以各成分质量浓度(ng·mL^-1) 为横坐标(X) 进行线性回归, 绘制标准曲线, 结果见表2, 可知各成分在各自浓度范围内线性关系良好。

大补肺汤活性成分的获取 选取UPLC-Q-TOF-MS/MS鉴定的全部成分为目标成分, 并结合TCMSP、中国知网(https://www.cnki.net)、PubMed (https://pubmed.ncbi.nlm.nih.gov) 等数据库, 筛选条件为类药性(drug-likeness, DL) ≥ 0.18, 口服生物利用度(oral bioavailability, OB) ≥ 30%, 在Pub Chem数据库(https://pubchem.ncbi.nlm.nih.gov/) 中检索各成分的SDF结构与SMILES号, 在Swiss ADME (http://www.swissadme.ch/) 中以GI absorption=High, Lipinski、Ghose、Veber、Egan、Muegge中两种及以上类药性原则为“yes”为条件进一步筛选获得潜在活性成分。

疾病靶点预测 分别在Gene Cards数据库(https://www.genecards.org/)、OMIM数据库(https://www.omim.org/) 中, 以慢性阻塞性肺疾病稳定期(stable phase of chronic obstructive pulmonary disease) 为关键词进行搜索, 取Gene Cards数据库前25%的靶点, 整合所有靶点并去重, 得到COPD稳定期的靶点。

疾病蛋白相互作用网络及“成分-靶点”网络的构建 利用Jvenn网站分别对拆方各组作用靶点与COPD稳定期取交集, 将交集靶点分别导入STRING数据库(https://cn.string-db.org/), Organisms选择“homo sapiens”, “minimum required interaction score”选择0.9, 构建蛋白相互作用(protein-protein interaction, PPI) 网络, 将数据导入Cytoscape 3.10.3软件进行分析, 根据度值(degree)、中介中心性(betweenness centrality, BC)、接近中心性(closeness centrality, CC) 筛选出大补肺汤改善COPD稳定期的核心靶点。运用Cytoscape 3.10.3软件构建“成分-靶点”网络图, 并筛选得到大补肺汤及其各组分发挥药效的核心成分。

作用靶点基因富集分析 对上述取得的作用靶点基因进行富集分析, 将筛选出的靶点导入Metascape数据库(https://metascape.org/gp/index.html/) 进行GO生物功能富集分析和KEGG通路富集分析, 以P < 0.05为显著性结果。

结果

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1　大补肺汤化学组成分析

1.1　大补肺汤化学成分定性分析

采用UPLC-Q-TOF-MS/MS技术对大补肺汤中的化学成分进行定性分析, 总离子流图见图1。通过一级和二级质谱信息分析并结合相关文献及Pubchem数据库^[12-18], 从大补肺汤样品图谱中共鉴定和表征出132个化学成分, 主要为苯丙素类、有机酸类、黄酮类、皂苷类、环烯醚萜类、酚酸类等成分, 见表3。其中, 有87种成分来自“用”组, 49种来自“体”组, 4种来自“化”组, 8种成分为体、用组共有成分。以上分析可以得知, 配伍后的化学成分呈现以体用为主的作用特点。

1.2　大补肺汤化学成分的质谱裂解特征分析

1.2.1　木脂素类化合物的鉴定

化合物128在正离子模式下检出, 保留时间为22.753 min, 准分子离子峰为m/z 417.226 5 [M+H]⁺, 推测化学式为C₂₄H₃₂O₆。裂解时脱去CH₃生成m/z 402.203 2 [M+H-CH₃]⁺, 后又再脱去O生成m/z 386.204 3 [M+H-CH₃-O]⁺, 继续脱去CH₃生成m/z 371.184 9 [M+H-CH₃-O-CH₃]⁺, 结合数据库及文献^[19]报道, 推测该化合物为五味子甲素, 其可能的裂解方式见图2A。

1.2.2　苯乙醇苷类化合物的鉴定

化合物43在正离子模式下检出, 保留时间为10.401 min, 准分子离子峰为m/z 647.196 0 [M+Na]⁺, 推测化学式为C₂₉H₃₆O₁₅。其裂解途径有2条, 途径一是裂解时脱去咖啡酰基C₉H₇O₃生成m/z 485.137 5 [M+Na-Caffeoyl]⁺, 后又脱去C₆H₁₀O₅生成m/z 339.090 7 [M+Na-Caffeoyl-C₆H₁₀O₅]⁺; 途径二是糖苷键断裂后脱去一分子鼠李糖生成m/z 501.139 9 [M+Na-Rha]⁺, 后脱去咖啡酰基生成m/z 339.090 7 [M+Na-Rha-Caffeoyl]⁺, m/z 163.037 5 [M+Na-C₂₀H₂₈O₁₂]⁺为其脱去的咖啡酰基, 结合数据库及文献^[20]报道, 推测该化合物为毛蕊花糖苷, 其可能的裂解方式见图2B。

1.2.3　黄酮类化合物的鉴定

化合物44在正离子模式下检出, 保留时间为10.637 min, 准分子离子峰为m/z 611.161 2 [M+H]⁺, 推测化学式为C₂₇H₃₀O₁₆。裂解时脱去一分子鼠李糖生成m/z 465.106 9 [M+H-Rha]⁺, 后又脱去一分子葡萄糖生成m/z 303.052 9 [M+H-Rha-Glc]⁺, 在碎片离子m/z 303.052 9 [M+H-Rha-Glc]⁺中丢失A环上一分子H₂O和C环上CO形成m/z 257.068 3 [M+H-Rha-Glc-H₂O-CO]⁺, 丢失A环和C环并发生重排后形成m/z 129.066 9 [M+H-Rha-Glc-CH₂O₂-C₈O₂]⁺, 结合数据库和文献^[21]报道, 推测该化合物为芦丁, 其可能的裂解方式见图2C。

1.2.4　甾体皂苷类化合物的鉴定

化合物96在正离子模式下检出, 保留时间为21.070 min, 准分子离子峰为m/z 855.471 6 [M+H]⁺, 推测化学式为C₄₄H₇₀O₁₆。其主要裂解途径有3条, 途径一是连续丢失糖基, 丢失木糖后生成m/z 723.434 0 [M+H-Xyl]⁺, 后失去一分子鼠李糖生成m/z 577.379 1 [M+H-Xyl-Rha]⁺, 脱去一分子H₂O生成m/z 559.363 5 [M+H-Xyl-Rha-H₂O]⁺; 途径二是糖苷键断裂, 丢失一分子木糖、一分子鼠李糖和一分子岩藻糖, 生成m/z 431.313 8 [M+H-Xyl-Rha-Fuc]⁺, 继而中性丢失C₈H₁₆O₂生成m/z 287.200 7 [M+H-Xyl-Rha-Fuc-C₈H₁₆O₂]⁺, 再丢失两分子H₂O生成m/z 251.178 2 [M+H-Xyl-Rha-Fuc-C₈H₁₆O₂-2H₂O]⁺; 途径三是首先特征中性丢失C₈H₁₆O₂生成m/z 711.362 8 [M+H-C₈H₁₆O₂]⁺, 后糖苷键断裂生成m/z 287.200 7 [M+H-C₈H₁₆O₂-Xyl-Rha-Fuc]⁺, 后又丢失两分子H₂O生成m/z 251.178 2 [M+H-C₈H₁₆O₂-Xyl-Rha-Fuc-2H₂O]⁺, 根据数据库及文献^[22]报道, 推测该化合物为麦冬皂苷D, 其可能裂解方式见图3A。

1.2.5　环烯醚萜类化合物的鉴定

化合物12在负离子模式下检出, 保留时间为1.693 min, 准分子离子峰为m/z 685.219 8 [M-H]^-, 推测化学式为C₂₇H₄₂O₂₀。裂解时丢失一分子H₂O和一分子葡萄糖生成m/z 505.149 9 [M-H-Glc-H₂O]^-, 后糖苷键断裂, 母核上中性丢失C₉H₈O₃生成m/z 341.112 9 [M-H-Glc-H₂O-C₉H₈O₃]^-, 再丢失一分子C₂H₆O₃生成m/z 263.077 6 [M-H-Glc-H₂O-C₉H₈O₃-C₂H₆O₃]^-, 或者在m/z 341.112 9 [M-H-Glc-H₂O-C₉H₈O₃]^-碎片离子上糖苷键断裂, 失去一分子葡萄糖生成m/z 179.055 3 [M-H-Glc-H₂O-C₉H₈O₃-Glc]^-, 结合数据库和文献^[23]报道, 推测该化合物为地黄苷D, 其可能裂解方式见图3B。

1.2.6　倍半萜内酯类化合物的鉴定

化合物90在正离子模式下检出, 保留时间为18.354 min, 准分子离子峰为m/z 309.169 2 [M+H]⁺, 推测化学式为C₁₇H₂₄O₅。裂解时失去一分子H₂O生成m/z 291.050 0 [M+H-H₂O]⁺, 后丢失一分子C₂H₄O₂生成m/z 231.136 9 [M+H-H₂O-C₂H₄O₂]⁺, 再脱去一分子CO生成m/z 203.141 2 [M+H-H₂O-C₂H₄O₂-CO]⁺, 结合数据库和文献^[24]报道, 推测该化合物为1-O-乙酰旋覆花内酯, 其可能裂解方式见图3C。

1.3　大补肺汤含量测定

取大补肺汤水提液, 配制成供试品溶液, 并测定其中7个成分的含量, 测定结果见表4。

2　大补肺汤网络药理学分析

2.1　大补肺汤潜在活性成分及作用靶点

大补肺汤体组、用组、化组分别收集到32、51、6个潜在活性成分, 其中体组和用组具有5个相同成分。体组、用组、化组分别获得508、679、138个作用靶点, 其中体组和用组作用于326个相同靶点, 体组和化组作用于15个相同靶点, 用组和化组作用于7个相同靶点, 体组、用组、化组共同作用于79个靶点。

2.2　大补肺汤及体-用-化各组潜在活性成分-COPD稳定期靶点网络构建与聚类分析

如图4所示, 共收集到2 142个与COPD稳定期相关的靶点, 其与大补肺汤有294个共同靶点, 与体组有212个共同靶点, 与用组有256个共同靶点, 与化组有55个共同靶点。对共同靶点进行PPI网络的构建与筛选后, 利用Cytoscape构建大补肺汤潜在活性成分-COPD稳定期靶点网络。其中, 根据度值排名前十的活性成分为槲皮素、五味子醇乙、五味子甲素、五味子丙素、甲基麦冬黄烷酮A、甲基麦冬黄酮A、麦冬黄烷酮A、1-O-乙酰旋覆花内酯、大花旋覆花素、甘草宁E, 推测可能为大补肺汤治疗COPD稳定期的核心成分。

如图5所示, 将大补肺汤治疗COPD稳定期的潜在靶点输入STRING数据库获得蛋白间相互作用关系, 导入Cytoscape软件并构建PPI网络图, 选取度值、BC、CC均为均值以上的靶点作为核心靶点, 得到STAT3、SRC、HSP90AA1、PIK3R1、PIK3CA、PIK3CB、PIK3CD、AKT1、ESR1、EGFR等87个核心靶点。将筛选得到的靶点导入Metascape数据库中进行GO生物功能富集分析和KEGG通路富集分析, GO功能富集分析得到3 223个条目, 提示大补肺汤治疗COPD稳定期主要以细胞迁移调控、信号转导、磷酸化作用为主的生物过程(BP), 以膜微区、激酶复合物、胞质与囊泡为主的细胞组分(CC) 和以激酶活性、激酶结合为主的分子功能(MF); KEGG信号通路分析结果表明大补肺汤治疗COPD稳定期可能与PI3K-AKT信号通路、HIF-1α信号通路、AGE-RAGE信号通路、EGFR酪氨酸激酶抑制剂耐药性、MAPK信号通路等相关。

分别对大补肺汤的体、用、化各组进行PPI网络的构建和GO生物功能富集分析及KEGG通路富集分析, 结果如图6所示。“体组”筛选得到STAT3、SRC、HSP90AA1、PIK3CA、PIK3CB等核心靶点, GO功能富集分析得到2 736个条目, 主要以信号转导、细胞迁移、腺体发育为主的生物过程, 以质膜、胞内囊泡为主的细胞组分和以蛋白相互作用、激酶活性、蛋白质磷酸化修饰为主的分子功能; KEGG信号通路分析结果表明体组可能与PI3K-AKT信号通路、HIF-1α信号通路、C型凝集素受体信号通路、Th17细胞的分化过程、FoxO信号通路等相关。“用组”筛选得到STAT3、SRC、PIK3R1、HSP90AA1、PIK3CA等核心靶点, GO功能富集分析得到3 034个条目, 主要以细胞运动与迁移、磷酸化作用、对外部刺激和细胞因子的响应为主的生物过程, 以膜微区、激酶复合物为主的细胞组分和以蛋白激酶活性、蛋白相互作用为主的分子功能; KEGG信号通路分析结果表明用组可能与PI3K-AKT信号通路、AGE-RAGE信号通路、HIF-1α信号通路、Ras信号通路等相关。“化组”筛选得到HSP90AA1、JAK2、JAK1、CREBBP、PIK3CB等核心靶点, GO功能富集分析得到980个条目, 主要以磷酸化作用、氧化应激作用、蛋白质核定位调控为主的生物过程, 以膜微区、神经元为主的细胞组分和以激酶活性、组蛋白表观调控为主的分子功能; KEGG信号通路分析结果表明化组可能与Th17细胞的分化过程、PI3K-AKT信号通路、Toll样受体信号通路、FoxO信号通路、细胞凋亡、Th1和Th2细胞分化等通路相关。通过物质基础分析得知, 用于治疗COPD稳定期的化学成分主要为用组的成分, 这为该方体-用-化配伍机制研究提供了依据和参考。

讨论

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根据《辅行诀脏腑用药法要》中的记载, 大补肺汤主治烦热汗出, 少气不足息, 口干, 耳聋, 脉虚而快等症, 可用于治疗肺肾两虚, 肃降无权所致的肺虚疾病中的“肺肾气阴两虚证”, 其功效为补益肺肾、纳气平喘, 在临床上已用于治疗COPD稳定期。全方由五味子、麦冬、生地黄、淡竹叶、旋覆花、炙甘草、细辛七味药组成, 麦门冬养阴润肺以通脉道、以除烦热; 五味子收降阴津、纳气平喘; 旋覆花降气消痰; 细辛宣肺止咳, 且细辛之辛开与五味子之酸敛, 一开一合, 开阖肺气, 化痰而不伤正; 地黄滋阴补肾, 竹叶除烦生津, 二者合用助肾水清降火热; 甘草助肾体, 助地黄益肾水以滋泽其肺燥, 甘草与旋覆花同用, 乃咸甘除燥之法, 使痰涎去而津液复。但大补肺汤的成分复杂, 治疗COPD稳定期的药效物质基础尚未明确, 不利于其临床应用与更为深入的研究。本实验分析了大补肺汤的化学成分, 结合网络药理学探讨大补肺汤治疗COPD稳定期的作用靶点, 并分别分析了体、用、化各组的作用靶点, 为大补肺汤的后续研究和临床应用提供数据支持。

通过UPLC-Q-TOF-MS/MS技术鉴定出132种化学成分, 并结合网络药理学筛选出槲皮素、五味子醇乙、五味子甲素、五味子丙素、甲基麦冬黄烷酮A、甲基麦冬黄酮A、麦冬黄烷酮A、1-O-乙酰旋覆花内酯、大花旋覆花素、甘草宁E等活性成分, 前10种核心成分7种来自用组, 4种来自体组, 槲皮素为体组、用组共有成分, 这与《辅行诀》中治疗COPD稳定期等肺虚之证采用补用为主、泻体为辅的治法相对应。其中槲皮素可以通过抑制Wnt5a/β-catenin信号通路、自噬过度和氧化应激, 从而减轻ASMC的线粒体损伤和表型转换, 在COPD中显示出潜在的治疗作用^[25]; 五味子甲素可以通过抑制α-SMA的表达的TGF-β信号通路在小鼠体内减弱BLM诱导的胶原沉积, 从而减轻小鼠肺纤维化的程度^[26]; 1-O-乙酰旋覆花内酯通过调节SRC/EGFR/MAPK信号通路抑制MUC5AC的表达并发挥抗炎作用, 在COPD小鼠体内显著抑制气管炎性细胞浸润和黏液分泌过多^[27]; 甘草宁E抑制了LPS诱导的RAW264.7细胞中NO和PGE2的产生, 显著降低了LPS诱导的A549细胞中COX-2和促炎细胞因子的表达, 通过抑制MAPK和NF-κB信号通路来缓解炎症反应, 可用于治疗肺部的炎症^[28]。

PPI分析结果显示大补肺汤与COPD稳定期相关联的核心靶点为STAT3、SRC、HSP90AA1、PIK3R1、PIK3CA、PIK3CB、PIK3CD、AKT1、ESR1、EGFR等, 这些靶点大多与细胞存活、细胞增殖、细胞代谢、炎症和免疫抑制等有关。STAT3是JAK2的下游靶点, 参与粒细胞生成过程中的中性粒细胞分化, STAT3抑制剂的使用显著降低了PPE诱导的小鼠肺部Siglec-F⁺中性粒细胞的数量, 显著缓解了小鼠肺气肿的症状, 同时还大幅减少了常规中性粒细胞的数量, 这反映了STAT3在Siglec-F⁺中性粒细胞分化和IL-17表达中的广泛应用, STAT3抑制可能通过抑制IL-17/CXCL-1轴, 从而减轻了中性粒细胞向肺部的整体迁移^{[29, 30]}; SRC家族激酶参与LPS和氧化应激对巨噬细胞的激活^[31], 香烟烟雾会激活SRC, 促进气道炎症和肺组织的破坏, PM2.5暴露会激活BEAS-2B细胞中SRC蛋白激酶的激活, 引起气道炎症, 引发支气管炎、哮喘和慢阻肺等疾病; PIK3CA、PIK3CB、PIK3CD是PI3K的催化亚基, PIK3R1是PI3K的调节亚基, PI3K通过促进炎症、氧化应激和组织重塑, 在COPD中发挥关键作用, 导致疾病的进展和恶化, PI3K抑制剂可以减少炎症并增强免疫调节, 防止血管重塑和纤维化^{[32, 33]}。其中体组、用组共同作用于PI3K各亚基、STAT3和SRC, 直接抑制了炎症的进一步发展, 并且通过调控细胞的生存状态, 阻止细胞在外界刺激下异常存活和增殖, 减缓气道重塑和肺气肿的进程。化组聚焦于JAK1和JAK2, 此为细胞因子(如白细胞介素、干扰素) 受体的关键激酶, 影响STAT3的表达, 从更深层次地调控了大补肺汤在治疗COPD稳定期时的抗炎通路。EGFR在COPD病程中的黏液高分泌和气道纤维化重塑起到了重要作用, 研究表明, IL-33激活RAGE/EGFR通路导致黏液相关基因的表达途径, 导致上皮细胞重塑过度、黏蛋白分泌过多、纤毛功能异常, 增加COPD病程恶化的风险, 大补肺汤体-用-化三组联用后可以调控EGFR的表达, 从而减轻COPD炎症的发生和气道阻塞程度^[34]。

慢阻肺的发病机制普遍认为与炎症、氧化应激、蛋白酶/抗蛋白酶失衡和免疫力下降有关。吸烟、PM2.5等诱导的氧化应激和蛋白酶过度生成是COPD发病的主要因素, 导致肺泡细胞死亡、肺泡细胞外基质破坏和肺泡结构丧失, 在呼吸道上主要表现为肺泡间隙扩大、气道重塑和黏液潴留, 进而导致肺功能的下降, 这涉及多种炎症细胞、炎性介质和相关信号通路^[35]。大补肺汤的体、用、化三组均可作用于PI3K-AKT信号通路, 该信号通路的激活可通过炎症和氧化应激来加剧COPD的进展^[36]。研究表明PI3K-AKT信号通路在COPD小鼠的肺泡巨噬细胞中被激活, 促使TNF-α、IL-1β、IL-6等促炎因子显著增加, 且促进了COPD小鼠肺部巨噬细胞M1到M2表型的极化, M2巨噬细胞比例的升高与肺部炎症有关^[37]。PI3K-AKT信号通路也会促进肺部的氧化应激和衰老, 香烟烟雾会刺激肺部细胞大量释放活性氧和活性氮, 在COPD早期诱导内源性氧化应激, 这种氧化应激的升高在慢阻肺患者戒烟后仍然存在, 引起内源性组织和细胞损伤, 从而导致慢性炎症和衰老^{[38, 39]}。Ras蛋白的功能主要在于调节细胞增殖、分化、衰老、细胞凋亡等生命过程, 在细胞信号转导过程中充当着重要的分子开关的作用。有研究表明Ras蛋白是调节上皮间充质转化(EMT) 的关键节点, 其失活可以抑制EMT过程的发生, 对肺纤维化具有调节作用。Zhang等^[40]研究表明, 黄芪甲苷Ⅳ可以通过靶向Ras蛋白下调Ras/FoxO信号通路, 抑制成纤维细胞转化为肌成纤维细胞, 同时减少EMT过程, 来预防与治疗肺纤维化, 从而控制COPD病程的发展并改善呼吸功能。根据关键靶点富集分析结果显示, “用组”主要聚焦在AGE-RAGE通路, 会进一步地引起慢性炎症、氧化应激、血管内皮细胞功能异常, 调控此信号通路可减轻COPD病程中的炎症反应和血管平滑肌细胞异常增殖; 同时可作用于Ras信号通路, 通过减少气道内黏液的分泌和气道重塑, 清除异常的成纤维细胞, 降低COPD肺纤维化的程度, 这与《辅行诀》中所记述的“用”为五脏之功用的理论相对应。“体组”主要聚焦在C型凝集素受体, 与病原体相关分子模式相互作用, 诱导细胞内信号转导, 触发细胞因子的产生, 诱导适应性免疫反应, 以减轻COPD中炎症反应的发生。“化组”主要聚焦在Th17细胞分化、Th1/Th2细胞分化和Toll样受体上, 从不同层面调节炎症通路, 减少肺部中性粒细胞等炎症细胞的浸润, 以减轻气道炎症生成, 改善COPD的临床症状。大补肺汤体-用-化三组合用后作用于MAPK信号通路和EGFR信号通路, 通过调控细胞的存活与增殖、分化、纤维化和黏液分泌来抑制气道成纤维细胞增殖、细胞外基质沉积, 这与气道重塑和纤维化密切相关。研究结果为该方的临床治疗COPD及其体-用-化配伍作用机制研究提供了科学依据和指引。

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2026年第61卷第5期

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doi: 10.16438/j.0513-4870.2025-1278

接收时间：2025-10-30
首发时间：2026-09-21
出版时间：2026-05-12

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收稿日期：2025-10-30
修回日期：2026-01-11

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²甘肃中医药大学, 敦煌医学与转化教育部重点实验室, 甘肃兰州 730050

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宿树兰，E-mail: sushulan@njucm.edu.cn

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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Component	Polarity	m/z	DP/V	CE/V
Schisandrol B	ES⁺	416.1	314.2	66	37
Schizandrin A	ES⁺	417.2	316.2	6	35
Schisandrin C	ES⁺	385.1	285.2	206	33
Methylophiopogonone A	ES⁺	341.1	219.3	1	31
Ophiogonanone A	ES⁺	330.1	136.3	11	25
1-O-Acetyl britannilactone	ES⁺	309.2	185.4	11	23
Britannin	ES⁺	367.1	247.3	56	15
Clarithromycin	ES⁺	748.5	590.3	41	29

Component

Polarity

m/z

DP/V

CE/V

Precursor ion

Product ion

Schisandrol B

ES⁺

416.1

314.2

Schizandrin A

ES⁺

417.2

316.2

Schisandrin C

ES⁺

385.1

285.2

206

Methylophiopogonone A

ES⁺

341.1

219.3

Ophiogonanone A

ES⁺

330.1

136.3

1-O-Acetyl britannilactone

ES⁺

309.2

185.4

Britannin

ES⁺

367.1

247.3

Clarithromycin

ES⁺

748.5

590.3

Component	Linear regression equation	r²	Linear range/ng·mL^-1
Schisandrol B	Y = 1 117.3X - 2 346.5	0.992 1	12.207-195.312
Schizandrin A	Y = 280 477X - 554 583	0.999 6	6.470-103.516
Schisandrin C	Y = 1 157.9X - 10 010	0.999 3	6.104-781.250
Methylophiopogonone A	Y = 264 984X - 1 000 000	0.999 8	5.920-378.906
Ophiogonanone A	Y = 1 076.6X - 7 745.3	0.998 2	11.963-382.812
1-O-Acetyl britannilactone	Y = 13 159X - 119 404	0.999 5	6.287-804.687
Britannin	Y = 2 888.7X - 8 384.8	0.997 3	6.714-214.844

Component

Linear regression equation

r²

Linear range/ng·mL^-1

Schisandrol B

Y = 1 117.3X - 2 346.5

0.992 1

12.207-195.312

Schizandrin A

Y = 280 477X - 554 583

0.999 6

6.470-103.516

Schisandrin C

Y = 1 157.9X - 10 010

0.999 3

6.104-781.250

Methylophiopogonone A

Y = 264 984X - 1 000 000

0.999 8

5.920-378.906

Ophiogonanone A

Y = 1 076.6X - 7 745.3

0.998 2

11.963-382.812

1-O-Acetyl britannilactone

Y = 13 159X - 119 404

0.999 5

6.287-804.687

Britannin

Y = 2 888.7X - 8 384.8

0.997 3

6.714-214.844

No.	Identification	t_R /min	Formula	Adducts	Precursor ion/m/z	Error /×10⁶	Fragment ion/m/z	Origin plant
1	Verbascoside	0.589	C₃₀H₅₂O₂₆	[M+Na]⁺	851.261 4	-3.6	689.212 4, 365.103 0, 163.064 4	Yong (SDH)
2	Rehmannioside A	0.888	C₂₁H₃₂O₁₅	[M+Na]⁺	547.164 1	0.4	365.106 9, 238.074 4, 146.059 1	Yong (SDH)
3	Raffinose	0.930	C₁₈H₃₂O₁₆	[M+Na]⁺	527.159 3	0.9	325.116 5, 163.063 5	Yong (SDH)
4	Adenine	0.940	C₅H₅N₅	[M+H]⁺	136.062 1	-1.5	119.035 4	Yong (MD)
5	2′-Acetylacteoside	0.982	C₃₁H₃₈O₁₆	[M+Na]⁺	689.204 2	-2.3	649.194 1, 365.111 4, 325.110 3	Yong (SDH)
6	Fructose	0.992	C₆H₁₂O₆	[M+Na]⁺	203.052 5	-3.4	163.058 3, 145.048 8, 127.039 5	Yong (SDH)
7	Adenosine	1.063	C₁₀H₁₃N₅O₄	[M+H]⁺	268.105 3	2.6	136.060 6, 119.033 8	Yong (SDH)
8	Arginine	3.729	C₆H₁₄N₄O₂	[M+H]⁺	175.120 0	2.9	112.084 3, 116.069 9	Hua (XX)
9	Citric acid	1.457	C₆H₈O₇	[M-H]^-	191.020 1	4.7	111.009 6	Yong (WWZ, SDH)
10	Stachyose	1.528	C₂₄H₄₂O₂₁	[M+H]⁺	667.228 7	-1.5	527.156 9, 275.078 6, 203.057 1	Yong (SDH)
11	Catalpol	1.538	C₁₅H₂₂O₁₀	[M+Na]⁺	385.112 3	3.1	136.061 5, 119.034 6	Yong (SDH)
12	Rehmannioside D	1.693	C₂₇H₄₂O₂₀	[M-H]^-	685.219 8	1.0	505.149 9, 341.112 9, 263.077 6, 179.055 3	Yong (SDH)
13	Melittoside	1.995	C₂₁H₃₂O₁₅	[M-H]^-	523.167 5	2.3	163.041 3, 135.045 9	Yong (SDH)
14	Protocatechuic acid	2.139	C₇H₆O₄	[M-H]^-	153.019 4	3.9	109.028 8	Ti (XFH), Yong (WWZ, DZY, SDH)
15	Geniposidic acid	2.139	C₁₆H₂₂O₁₀	[M-H]^-	373.112 6	-2.4	211.061 2, 123.048 7	Yong (SDH)
16	Dihydroferulic acid	2.758	C₁₀H₁₂O₄	[M+H]⁺	197.081 5	0.5	179.072 9, 167.071 4	Yong (SDH)
17	Salidroside	2.779	C₁₄H₂₀O₇	[M+Na]⁺	323.109 6	-3.4	224.061 5	Yong (SDH)
18	Vanillic acid	2.892	C₈H₈O₄	[M-H]^-	167.035 1	4.2	122.991 1, 151.984 6	Yong (SDH)
19	Ajugol	3.201	C₁₅H₂₄O₉	[M-H]^-	347.135 2	2.9	113.025 9, 167.033 7, 181.050 6, 303.107 2	Yong (SDH)
20	Quinic acid	3.254	C₇H₁₂O₆	[M-H]^-	191.056 2	3.1	109.031 7, 127.040 7, 173.045 8, 191.056 7	Yong (WWZ)
21	5-Hydroxymethylfurfural	3.482	C₆H₆O₃	[M+H]⁺	127.039 1	-3.1	109.030 8	Yong (MD, WWZ)
22	Neochlorogenic acid	5.040	C₁₆H₁₈O₉	[M-H]^-	353.087 8	1.4	127.033 0, 135.045 6, 161.027 9, 179.036 3, 191.057 4	Ti (XFH), Yong (DZY)
23	5-Hydroxymethyl-2-furaldehyde	5.163	C₆H₆O₃	[M-H]^-	125.023 6	-2.4	109.040 7	Yong (WWZ)
24	Decaffeoyl-verbascoside	5.237	C₂₀H₃₀O₁₂	[M-H]^-	461.164 9	-2.2	135.047 7, 123.041 9	Yong (SDH)
25	8-Epiloganic acid	5.630	C₁₆H₂₄O₁₀	[M-H]^-	375.128 9	-0.5	213.076 1, 169.088 4, 151.077 2	Yong (SDH)
26	Protocatechualdehyde	5.753	C₇H₆O₃	[M-H]^-	137.024 5	4.4	108.020 8, 109.025 7	Ti (XFH)
27	Acetylcatalpol	5.785	C₁₇H₂₄O₁₁	[M-H]^-	403.124 0	0.0	165.053 1, 139.039 6	Yong (SDH)
28	3,7-Dihydroxycoumarin	5.929	C₉H₆O₄	[M-H]^-	177.019 4	3.4	105.033 7, 133.028 4, 149.022 4	Ti (XFH)
29	Geniposide	6.239	C₁₇H₂₄O₁₀	[M+Na]⁺	411.127 7	2.4	149.057 8, 103.048 8	Yong (SDH)
30	Schisandrol A	6.889	C₂₄H₃₂O₇	[M+H]⁺	433.223 8	2.8	384.181 9, 353.161 3, 218.087 7	Yong (WWZ)
31	Cistanoside F	6.910	C₂₁H₂₈O₁₃	[M-H]^-	487.144 1	-2.3	179.033 5, 161.027 4, 135.046 9	Yong (SDH)
32	Caffeic acid	7.065	C₉H₈O₄	[M-H]^-	179.035 1	3.9	107.048 7, 109.029 8, 117.035 7, 134.039 4, 135.046 2, 136.084 1	Ti (XFH, ZGH), Yong (SDH)
33	Echinacoside	7.466	C₃₅H₄₆O₂₀	[M+Na]⁺	809.247 1	-1.1	287.072 6, 163.038 7	Yong (SDH)
34	sec-Hydroxyaeginetic acid	7.860	C₁₅H₂₄O₅	[M-H]^-	283.155 7	4.2	163.107 6, 181.099 3, 203.162 4, 239.123 3, 265.127 2	Yong (SDH)
35	Cryptochlorogenic acid	7.962	C₁₆H₁₈O₉	[M-H]^-	353.088 2	2.5	111.048 6, 135.045 8, 155.036 4, 173.047 1, 179.037 1, 191.057 6	Ti (XFH), Yong (DZY)
36	Naringenin	8.263	C₁₅H₁₂O₅	[M-H]^-	271.061 7	4.1	151.004 3, 119.050 2	Yong (DZY))
37	5,7,4′-Trihydroxy-3′-methoxy-6,8-dimethyl-homisoflavanone	8.542	C₁₉H₂₀O₆	[M+H]⁺	345.133 1	-2.0	137.053 3, 299.084 2	Yong (MD)
38	Liquiritin	8.562	C₂₁H₂₂O₉	[M-H]^-	417.118 4	-0.5	255.067 8, 161.024 0, 148.017 2	Ti (ZGC)
39	Chlorogenic acid	9.006	C₁₆H₁₈O₉	[M-H]^-	353.087 8	1.4	191.057 8, 179.036 5, 173.043 8	Ti (XFH), Yong (WWZ, DZY)
40	Prim-O-glucosylcimifugin	9.069	C₂₂H₂₈O₁₁	[M+H]⁺	469.170 8	-0.4	235.060 4, 189.041 2	Yong (SDH)
41	Kaempferol-3-rutinoside	9.843	C₂₇H₃₀O₁₅	[M+H]⁺	595.165 8	-0.8	415.089 1, 463.105 5	Ti (ZGC)
42	1,3-Dicaffeoylquinic acid	10.121	C₂₅H₂₄O₁₂	[M-H]^-	515.119 0	0.0	191.057 4, 179.036 2, 135.045 9	Ti (XFH)
43	Verbascoside	10.401	C₂₉H₃₆O₁₅	[M+Na]⁺	647.196 0	1.2	501.139 9, 485.137 5, 339.090 7, 163.037 5	Yong (SDH)
44	Rutin	10.637	C₂₇H₃₀O₁₆	[M+H]⁺	611.161 2	0.0	129.066 9, 257.068 3, 303.052 9, 465.106 9	Yong (DZY)
45	Neo-rehmannioside E	10.690	C₂₁H₃₄O₁₀	[M-H]^-	445.208 9	3.4	161.025 4, 265.099 2	Yong (SDH)
46	Isoschaftoside	11.052	C₂₆H₂₈O₁₄	[M+H]⁺	565.154 9	-1.4	295.059 8, 325.071 0, 337.071 4, 391.081 7, 409.090 6, 427.100 8, 565.154 0	Ti (ZGC), Yong (DZY)
47	Schaftoside	11.062	C₂₆H₂₈O₁₄	[M-H]^-	563.139 5	-1.1	473.111 5, 383.078 5	Ti (ZGC)
48	Loliolid	11.123	C₁₁H₁₆O₃	[M+H]⁺	197.117 8	0.0	105.075 8, 115.052 3, 133.099 6, 161.100 2, 179.103 5	Ti (XFH)
49	Quercetagetin-7-O-glucoside	11.207	C₂₁H₂₀O₁₃	[M+H]⁺	481.097 0	-2.5	319.043 5	Ti (XFH)
50	5,7,2′-Trihydroxy-8-methyl-3-(3′,4′-methylenedioxybenzyl)-chromone	11.238	C₁₈H₁₄O₇	[M+H]⁺	343.080 4	-4.1	205.046 7, 177.054 3, 149.056 7	Yong (MD)
51	Methyl eugenol	11.238	C₁₁H₁₄O₂	[M+H]⁺	179.106 9	-1.7	117.062 9, 143.073 7, 144.080 6	Hua (XX)
52	Isoorientin	11.361	C₂₁H₂₀O₁₁	[M+H]⁺	449.108 7	0.7	299.054 2, 166.021 8, 300.062 1	Yong (DZY)
53	Orientin	11.414	C₂₁H₂₀O₁₁	[M-H]^-	447.093 0	0.7	327.051 3, 357.064 0, 297.040 0	Yong (DZY)
54	Cistanoside A	11.671	C₃₆H₄₈O₂₀	[M-H]^-	799.263 7	-3.0	623.218 9, 175.037 8	Yong (SDH)
55	2-O-β-D-Glucopyranosyl atractyligenin	11.702	C₂₅H₃₈O₉	[M-H]^-	481.244 4	1.2	301.181 3, 320.184 0	Ti (XFH)
56	Rehmannioside C	11.723	C₁₉H₃₂O₈	[M+Na]⁺	411.199 9	1.0	245.194 6	Yong (SDH)
57	Rehmapicroside	11.949	C₁₆H₂₆O₈	[M-H]^-	345.154 5	-1.2	165.054 5	Yong (SDH)
58	Liquiritigenin	12.156	C₁₅H₁₂O₄	[M-H]^-	255.066 0	1.2	135.048 0, 119.050 9	Ti (ZGC)
59	Liquiritin apioside	12.363	C₂₆H₃₀O₁₃	[M-H]^-	546.161 1	0.5	417.119 6, 255.067 4, 135.010 1	Ti (ZGC)
60	Afzelin	12.423	C₂₁H₂₀O₁₀	[M-H]^-	431.098 3	1.2	283.062 0, 311.056 1, 323.052 8	Ti (ZGC)
61	Isovitexin	12.434	C₂₁H₂₀O₁₀	[M+H]⁺	433.113 4	-0.2	433.112 1, 313.072 1, 415.103 6	Yong (DZY)
62	Vitexin	12.444	C₂₁H₂₀O₁₀	[M-H]^-	431.097 0	-1.9	117.035 0, 283.061 1, 161.022 9	Yong (DZY)
63	Taxifolin	12.704	C₁₅H₁₂O₇	[M-H]^-	303.051 4	3.0	107.016 0, 125.026 2, 175.035 5, 217.054 2	Ti (XFH)
64	Quercetin-3-O-glucuronide	12.796	C₂₁H₁₈O₁₃	[M+H]⁺	479.082 4	-0.4	303.048 9	Ti (XFH)
65	Quercetin	12.859	C₁₅H₁₀O₇	[M-H]^-	301.034 8	0.0	229.047 9, 178.997 2, 151.004 5	Ti (XFH), Yong (DZY)
66	Hyperoside	13.013	C₂₁H₂₀O₁₂	[M-H]^-	463.087 7	0.0	151.005 2, 255.031 6, 271.025 8, 300.028 1, 301.035 2	Ti (XFH)
67	Isoquercitrin	13.024	C₂₁H₂₀O₁₂	[M-H]^-	463.087 9	0.4	107.014 6, 151.004 6, 178.998 9, 255.029 7, 300.028 4, 301.033 9	Ti (XFH)
68	Patulitrin	13.231	C₂₂H₂₂O₁₃	[M+H]⁺	495.114 1	0.4	318.035 9, 333.059 7	Ti (XFH)
69	Jiocarotenoside B1	13.415	C₃₇H₅₀O₂₀	[M-H]^-	813.280 3	-1.7	637.236 2, 175.032 2	Yong (SDH)
70	Azelaic acid	13.446	C₉H₁₆O₄	[M-H]^-	187.096 0	-5.3	125.095 4	Yong (MD)
71	Neo-rehmannioside B	13.633	C₁₅H₂₄O₆	[M-H]^-	299.149 3	-0.7	139.073 5	Yong (SDH)
72	Isorhamnetin-3-O-glucoside	13.675	C₂₂H₂₂O₁₂	[M-H]^-	477.103 7	0.8	107.021 1, 151.002 7, 285.040 5, 314.043 7, 315.051 7	Ti (XFH)
73	1,5-Dicaffeoylquinic acid	13.808	C₂₅H₂₄O₁₂	[M-H]^-	515.119 5	1.0	335.078 9, 191.056 4, 179.035 3	Ti (XFH)
74	Forsythoside A	14.026	C₂₉H₃₆O₁₅	[M-H]^-	623.198 1	0.8	177.017 3, 119.048 2	Yong (SDH)
75	Isochlorogenic acid A	15.214	C₂₅H₂₄O₁₂	[M-H]^-	515.119 5	1.0	203.037 2, 191.057 1, 179.036 2	Ti (XFH)
76	5-Methoxy-6-methyl-7-oxhydryl-8-methoxy-3-(2′-oxhydryl-4′-methoxybenzyl)-4-chromanone	15.429	C₂₀H₂₂O₇	[M-H]^-	373.129 8	2.9	153.019 6, 168.046 0	Yong (MD)
77	5,7-Dihydroxy-3-(4′-methoxybenzyl)-4-chromone	15.865	C₁₇H₁₄O₅	[M-H]^-	297.075 2	-3.7	203.037 1, 175.046 9	Yong (MD)
78	Aegineticacid	15.957	C₁₅H₂₄O₄	[M+H]⁺	269.176 4	4.1	167.010 4	Yong (SDH)
79	Formononetin	16.122	C₁₆H₁₁O₄	[M-H]^-	267.066 0	1.1	252.044 8	Ti (ZGC)
80	Ophiopogonanone E	16.308	C₁₉H₂₀O₇	[M-H]^-	359.113 6	1.4	208.034 1, 138.035 6	Yong (MD)
81	5,7-Dihydroxy-6,8-dimethyl-3-(3′,5′-dimethoxy-4′-hydroxybenzyl)-4-chromanone	16.339	C₂₀H₂₂O₇	[M-H]^-	373.130 0	3.5	207.064 6, 179.070 1, 135.046 6	Yong (MD)
82	5,7-Dihydroxy-8-methyl-3-(3′,4′-dimethoxybenzyl)-4-chromone	16.410	C₁₈H₁₄O₆	[M-H]^-	325.071 8	1.8	297.073 3, 131.053 8, 203.035 9	Yong (MD)
83	Neoliquiritin	16.474	C₂₁H₂₂O₉	[M+H]⁺	419.132 6	-3.8	119.047 6, 137.022 1, 239.069 7, 257.080 6	Ti (ZGC)
84	Isoliquiritin	16.959	C₂₁H₂₂O₉	[M+H]⁺	419.135 1	2.1	137.023 2, 239.070 8, 257.082 5	Ti (ZGC)
85	Isoliquiritigenin	16.969	C₁₅H₁₂O₄	[M+H]⁺	257.081 0	-1.6	137.023 8	Ti (ZGC)
86	Martynoside	17.103	C₃₁H₄₀O₁₅	[M-H]^-	651.228 5	-0.6	193.048 0, 175.042 1	Yong (SDH)
87	Spinacetin	17.216	C₁₇H₁₄O₈	[M-H]^-	345.061 6	1.7	315.014 5, 330.038 3	Ti (XFH)
88	5-Oxhydryl-6-methyl-7-methoxy-3-(3′,4′-dihydroxyphenyl)-4-chromone	17.546	C₁₈H₁₆O₆	[M-H]^-	327.086 5	-1.2	164.049 8, 327.084 9	Yong (MD)
89	Uralsaponin F	17.693	C₄₄H₆₄O₁₉	[M-H]^-	895.399 4	3.4	853.394 4, 821.353 5, 351.059 5	Ti (ZGC)
90	1-O-Acetyl britannilactone	18.354	C₁₇H₂₄O₅	[M+H]⁺	309.169 2	-3.2	291.050 0, 231.136 9, 203.141 2	Ti (XFH)
91	Luteolin	18.404	C₁₅H₁₀O₆	[M-H]^-	285.039 7	-0.7	175.035 6, 151.004 5, 133.026 6	Ti (XFH), Yong (DZY)
92	Eupafolin	18.684	C₁₆H₁₂O₇	[M-H]^-	315.051 3	2.5	300.027 4	Ti (XFH)
93	Rosmarinic acid	20.563	C₁₈H₁₆O₈	[M-H]^-	359.077 4	1.9	133.029 3, 135.044 2, 161.025 6, 193.014 4	Ti (XFH)
94	Licorice saponin A3	20.770	C₄₈H₇₂O₂₁	[M+H]⁺	985.467 6	3.2	453.336 4, 471.348 0, 615.389 4, 809.433 9	Ti (ZGC)
95	Diosmetin	21.069	C₁₆H₁₂O₆	[M-H]^-	299.056 9	4.3	227.037 1, 256.039 1, 284.032 8	Yong (DZY)
96	Ophiopogonin D	21.070	C₄₄H₇₀O₁₆	[M+H]⁺	855.471 6	-3.0	251.178 2, 287.200 7, 431.313 8, 559.363 5, 577.379 1, 711.368 9, 723.434 0	Yong (MD)
97	Licorice saponin G2	21.153	C₄₂H₆₂O₁₇	[M+H]⁺	839.408 6	2.5	451.320 7, 469.331 2, 487.341 5, 663.377 1	Ti (ZGC)
98	Licorice saponin E2	21.193	C₄₂H₆₀O₁₆	[M+H]⁺	821.395 8	-0.2	451.323 1, 469.332 6, 645.364 4	Ti (ZGC)
99	Gancaonin G	21.203	C₂₁H₂₀O₅	[M+H]⁺	353.139 8	2.5	267.063 7, 297.108 2	Ti (ZGC)
100	Glycyrrhetinic acid	21.266	C₃₀H₄₆O₄	[M+H]⁺	471.346 2	-2.5	407.329 5, 435.326 9, 453.337 0	Ti (ZGC)
101	Neobritannilactone B	21.276	C₁₅H₂₀O₃	[M-H]^-	247.133 8	1.6	203.148 3, 201.132 8, 135.083 1	Ti (XFH)
102	Methylophiopogonone A	21.286	C₁₉H₁₆O₆	[M-H]^-	339.087 3	1.2	311.093 4, 217.208 3	Yong (MD)
103	Ophiopogonanone B	21.328	C₁₉H₂₀O₅	[M-H]^-	327.124 5	4.0	178.066 9	Yong (MD)
104	Glycyrrhizic acid	21.389	C₄₂H₆₂O₁₆	[M-H]^-	821.396 3	0.4	351.055 0, 193.034 8, 469.344 7	Ti (ZGC)
105	Pregomisin	21.431	C₂₂H₃₀O₆	[M+H]⁺	391.212 2	0.3	327.143 6, 275.084 7, 229.096 2	Yong (WWZ)
106	Uralsaponin C	21.473	C₄₂H₆₄O₁₆	[M+H]⁺	825.428 1	1.0	455.351 0, 473.361 4	Ti (ZGC)
107	8-Formyl ophiopogonone B	21.534	C₂₀H₂₂O₇	[M+H]⁺	375.143 9	-1.3	109.062 1, 251.090 2, 357.133 8	Yong (MD)
108	Casticin	21.699	C₁₉H₁₈O₈	[M+H]⁺	375.107 6	-1.1	360.082 6, 375.103 9, 377.116 6	Ti (XFH)
109	Schisandrol B	21.751	C₂₃H₂₈O₇	[M+H]⁺	417.192 3	2.4	368.147 1, 399.179 9	Yong (WWZ)
110	Diosgenin	21.804	C₂₇H₄₂O₃	[M+H]⁺	415.321 5	0.7	157.095 5	Yong (MD)
111	Ilicic acid	21.824	C₁₅H₂₄O₃	[M-H]^-	251.165 8	4.4	207.173 2	Ti (XFH)
112	Japonicones D	21.885	C₃₄H₄₄O₉	[M+H]⁺	597.305 9	-0.8	211.109 5, 185.132 0	Ti (XFH)
113	Gomisin D	21.896	C₂₈H₃₄O₁₀	[M+H]⁺	531.224 5	2.8	401.158 9, 383.149 2, 341.101 3	Yong (WWZ)
114	Gomisin R	21.906	C₂₂H₂₄O₇	[M+H]⁺	401.159 3	-1.7	337.106 6, 341.102 8, 383.148 2	Yong (WWZ)
115	Gomisin J	21.927	C₂₂H₂₈O₆	[M+H]⁺	389.194 5	-4.9	227.075 0, 287.092 0, 137.060 1	Yong (WWZ)
116	5-Oxhydryl-6-aldehyde-7-methoxy-8-methyl-3-(4′-methoxybenzyl)-4-chromanone	21.937	C₂₀H₂₀O₆	[M-H]^-	355.120 0	5.1	217.052 1, 150.031 8	Yong (MD)
117	Ruscogenin	21.938	C₂₇H₄₂O₄	[M+H]⁺	431.316 8	1.6	251.177 6, 269.185 4, 139.078 6	Yong (MD)
118	Sesamin	21.959	C₂₀H₁₈O₆	[M+H]⁺	355.117 9	-0.8	179.035 7, 268.985 4	Hua (XX)
119	Angeloylgomisin H	22.029	C₂₈H₃₆O₈	[M+H]⁺	501.248 9	0.2	370.173 1, 355.154 4, 337.142 4	Yong (WWZ)
120	Schisantherin B	22.071	C₂₈H₃₄O₉	[M+H]⁺	515.227 9	-0.4	385.165 4, 355.152 5, 343.116 8	Yong (WWZ)
121	Benzoylgomisin H	22.155	C₃₀H₃₄O₈	[M+H]⁺	523.231 3	-3.6	441.181 5, 409.159 0, 386.174 3	Yong (WWZ)
122	Gedunin	22.155	C₂₈H₃₄O₇	[M+H]⁺	483.238 3	0.0	381.133 3, 395.149 1, 367.117 2	Yong (WWZ)
123	Schisandrin B	22.155	C₂₃H₂₈O₆	[M+H]⁺	401.195 8	-1.5	386.174 3, 370.177 3	Yong (WWZ)
124	Alantolactone	22.195	C₁₅H₂₀O₂	[M+H]⁺	233.153 9	1.7	159.114 6, 118.071 1, 106.073 7	Ti (XFH)
125	Schisanhenol B	22.237	C₂₂H₂₆O₆	[M+H]⁺	387.179 7	-2.8	355.154 1, 326.150 7, 271.060 4	Yong (WWZ)
126	Schisandrin C	22.350	C₂₂H₂₄O₆	[M+H]⁺	385.166 2	2.9	257.080 8, 199.074 8, 184.051 5	Yong (WWZ)
127	Schisantherin A	22.381	C₃₀H₃₂O₉	[M+H]⁺	537.209 6	-5.4	415.173 3, 397.163 7, 371.148 9	Yong (WWZ)
128	Schisandrin A	22.753	C₂₄H₃₂O₆	[M+H]⁺	417.226 5	-2.9	402.203 2, 386.204 3, 371.184 9	Yong (WWZ)
129	Schisanhenol	22.504	C₂₃H₃₀O₆	[M+H]⁺	403.211 0	-2.7	302.116 8, 271.093 8	Yong (WWZ)
130	Asarinin	22.940	C₂₀H₁₈O₆	[M+NH₄]⁺	372.144 4	-0.8	128.060 9, 135.038 8, 161.063 1	Hua (XX)
131	5,7,2′-Trihydroxy-6,8-dimethyl-3-(3′,4′-methylenedioxybenzyl)-chromone	22.961	C₁₉H₁₆O₇	[M+H]⁺	357.097 2	-0.6	339.097 9	Yong (WWZ)
132	Dibutyl phthalate	23.239	C₁₆H₂₂O₄	[M+H]⁺	279.160 9	4.7	149.022 3, 121.027 8	Yong (WWZ)

No.

Identification

t_R
/min

Formula

Adducts

Precursor
ion/m/z

Error
/×10⁶

Fragment ion/m/z

Origin plant

Verbascoside

0.589

C₃₀H₅₂O₂₆

[M+Na]⁺

851.261 4

-3.6

689.212 4, 365.103 0, 163.064 4

Yong (SDH)

Rehmannioside A

0.888

C₂₁H₃₂O₁₅

[M+Na]⁺

547.164 1

0.4

365.106 9, 238.074 4, 146.059 1

Yong (SDH)

Raffinose

0.930

C₁₈H₃₂O₁₆

[M+Na]⁺

527.159 3

0.9

325.116 5, 163.063 5

Yong (SDH)

Adenine

0.940

C₅H₅N₅

[M+H]⁺

136.062 1

-1.5

119.035 4

Yong (MD)

2′-Acetylacteoside

0.982

C₃₁H₃₈O₁₆

[M+Na]⁺

689.204 2

-2.3

649.194 1, 365.111 4, 325.110 3

Yong (SDH)

Fructose

0.992

C₆H₁₂O₆

[M+Na]⁺

203.052 5

-3.4

163.058 3, 145.048 8, 127.039 5

Yong (SDH)

Adenosine

1.063

C₁₀H₁₃N₅O₄

[M+H]⁺

268.105 3

2.6

136.060 6, 119.033 8

Yong (SDH)

Arginine

3.729

C₆H₁₄N₄O₂

[M+H]⁺

175.120 0

2.9

112.084 3, 116.069 9

Hua (XX)

Citric acid

1.457

C₆H₈O₇

[M-H]^-

191.020 1

4.7

111.009 6

Yong (WWZ, SDH)

Stachyose

1.528

C₂₄H₄₂O₂₁

[M+H]⁺

667.228 7

-1.5

527.156 9, 275.078 6, 203.057 1

Yong (SDH)

Catalpol

1.538

C₁₅H₂₂O₁₀

[M+Na]⁺

385.112 3

3.1

136.061 5, 119.034 6

Yong (SDH)

Rehmannioside D

1.693

C₂₇H₄₂O₂₀

[M-H]^-

685.219 8

1.0

505.149 9, 341.112 9, 263.077 6, 179.055 3

Yong (SDH)

Melittoside

1.995

C₂₁H₃₂O₁₅

[M-H]^-

523.167 5

2.3

163.041 3, 135.045 9

Yong (SDH)

Protocatechuic acid

2.139

C₇H₆O₄

[M-H]^-

153.019 4

3.9

109.028 8

Ti (XFH), Yong (WWZ, DZY, SDH)

Geniposidic acid

2.139

C₁₆H₂₂O₁₀

[M-H]^-

373.112 6

-2.4

211.061 2, 123.048 7

Yong (SDH)

Dihydroferulic acid

2.758

C₁₀H₁₂O₄

[M+H]⁺

197.081 5

0.5

179.072 9, 167.071 4

Yong (SDH)

Salidroside

2.779

C₁₄H₂₀O₇

[M+Na]⁺

323.109 6

-3.4

224.061 5

Yong (SDH)

Vanillic acid

2.892

C₈H₈O₄

[M-H]^-

167.035 1

4.2

122.991 1, 151.984 6

Yong (SDH)

Ajugol

3.201

C₁₅H₂₄O₉

[M-H]^-

347.135 2

2.9

113.025 9, 167.033 7, 181.050 6, 303.107 2

Yong (SDH)

Quinic acid

3.254

C₇H₁₂O₆

[M-H]^-

191.056 2

3.1

109.031 7, 127.040 7, 173.045 8, 191.056 7

Yong (WWZ)

5-Hydroxymethylfurfural

3.482

C₆H₆O₃

[M+H]⁺

127.039 1

-3.1

109.030 8

Yong (MD, WWZ)

Neochlorogenic acid

5.040

C₁₆H₁₈O₉

[M-H]^-

353.087 8

1.4

127.033 0, 135.045 6, 161.027 9, 179.036 3, 191.057 4

Ti (XFH),
Yong (DZY)

5-Hydroxymethyl-2-furaldehyde

5.163

C₆H₆O₃

[M-H]^-

125.023 6

-2.4

109.040 7

Yong (WWZ)

Decaffeoyl-verbascoside

5.237

C₂₀H₃₀O₁₂

[M-H]^-

461.164 9

-2.2

135.047 7, 123.041 9

Yong (SDH)

8-Epiloganic acid

5.630

C₁₆H₂₄O₁₀

[M-H]^-

375.128 9

-0.5

213.076 1, 169.088 4, 151.077 2

Yong (SDH)

Protocatechualdehyde

5.753

C₇H₆O₃

[M-H]^-

137.024 5

4.4

108.020 8, 109.025 7

Ti (XFH)

Acetylcatalpol

5.785

C₁₇H₂₄O₁₁

[M-H]^-

403.124 0

0.0

165.053 1, 139.039 6

Yong (SDH)

3,7-Dihydroxycoumarin

5.929

C₉H₆O₄

[M-H]^-

177.019 4

3.4

105.033 7, 133.028 4, 149.022 4

Ti (XFH)

Geniposide

6.239

C₁₇H₂₄O₁₀

[M+Na]⁺

411.127 7

2.4

149.057 8, 103.048 8

Yong (SDH)

Schisandrol A

6.889

C₂₄H₃₂O₇

[M+H]⁺

433.223 8

2.8

384.181 9, 353.161 3, 218.087 7

Yong (WWZ)

Cistanoside F

6.910

C₂₁H₂₈O₁₃

[M-H]^-

487.144 1

-2.3

179.033 5, 161.027 4, 135.046 9

Yong (SDH)

Caffeic acid

7.065

C₉H₈O₄

[M-H]^-

179.035 1

3.9

107.048 7, 109.029 8, 117.035 7, 134.039 4, 135.046 2, 136.084 1

Ti (XFH, ZGH), Yong (SDH)

Echinacoside

7.466

C₃₅H₄₆O₂₀

[M+Na]⁺

809.247 1

-1.1

287.072 6, 163.038 7

Yong (SDH)

sec-Hydroxyaeginetic acid

7.860

C₁₅H₂₄O₅

[M-H]^-

283.155 7

4.2

163.107 6, 181.099 3, 203.162 4, 239.123 3, 265.127 2

Yong (SDH)

Cryptochlorogenic acid

7.962

C₁₆H₁₈O₉

[M-H]^-

353.088 2

2.5

111.048 6, 135.045 8, 155.036 4, 173.047 1, 179.037 1, 191.057 6

Ti (XFH),
Yong (DZY)

Naringenin

8.263

C₁₅H₁₂O₅

[M-H]^-

271.061 7

4.1

151.004 3, 119.050 2

Yong (DZY))

5,7,4′-Trihydroxy-3′-methoxy-6,8-dimethyl-homisoflavanone

8.542

C₁₉H₂₀O₆

[M+H]⁺

345.133 1

-2.0

137.053 3, 299.084 2

Yong (MD)

Liquiritin

8.562

C₂₁H₂₂O₉

[M-H]^-

417.118 4

-0.5

255.067 8, 161.024 0, 148.017 2

Ti (ZGC)

Chlorogenic acid

9.006

C₁₆H₁₈O₉

[M-H]^-

353.087 8

1.4

191.057 8, 179.036 5, 173.043 8

Ti (XFH), Yong (WWZ, DZY)

Prim-O-glucosylcimifugin

9.069

C₂₂H₂₈O₁₁

[M+H]⁺

469.170 8

-0.4

235.060 4, 189.041 2

Yong (SDH)

Kaempferol-3-rutinoside

9.843

C₂₇H₃₀O₁₅

[M+H]⁺

595.165 8

-0.8

415.089 1, 463.105 5

Ti (ZGC)

1,3-Dicaffeoylquinic acid

10.121

C₂₅H₂₄O₁₂

[M-H]^-

515.119 0

0.0

191.057 4, 179.036 2, 135.045 9

Ti (XFH)

Verbascoside

10.401

C₂₉H₃₆O₁₅

[M+Na]⁺

647.196 0

1.2

501.139 9, 485.137 5, 339.090 7, 163.037 5

Yong (SDH)

Rutin

10.637

C₂₇H₃₀O₁₆

[M+H]⁺

611.161 2

0.0

129.066 9, 257.068 3, 303.052 9, 465.106 9

Yong (DZY)

Neo-rehmannioside E

10.690

C₂₁H₃₄O₁₀

[M-H]^-

445.208 9

3.4

161.025 4, 265.099 2

Yong (SDH)

Isoschaftoside

11.052

C₂₆H₂₈O₁₄

[M+H]⁺

565.154 9

-1.4

295.059 8, 325.071 0, 337.071 4, 391.081 7, 409.090 6, 427.100 8, 565.154 0

Ti (ZGC), Yong (DZY)

Schaftoside

11.062

C₂₆H₂₈O₁₄

[M-H]^-

563.139 5

-1.1

473.111 5, 383.078 5

Ti (ZGC)

Loliolid

11.123

C₁₁H₁₆O₃

[M+H]⁺

197.117 8

0.0

105.075 8, 115.052 3, 133.099 6, 161.100 2, 179.103 5

Ti (XFH)

Quercetagetin-7-O-glucoside

11.207

C₂₁H₂₀O₁₃

[M+H]⁺

481.097 0

-2.5

319.043 5

Ti (XFH)

5,7,2′-Trihydroxy-8-methyl-3-(3′,4′-methylenedioxybenzyl)-chromone

11.238

C₁₈H₁₄O₇

[M+H]⁺

343.080 4

-4.1

205.046 7, 177.054 3, 149.056 7

Yong (MD)

Methyl eugenol

11.238

C₁₁H₁₄O₂

[M+H]⁺

179.106 9

-1.7

117.062 9, 143.073 7, 144.080 6

Hua (XX)

Isoorientin

11.361

C₂₁H₂₀O₁₁

[M+H]⁺

449.108 7

0.7

299.054 2, 166.021 8, 300.062 1

Yong (DZY)

Orientin

11.414

C₂₁H₂₀O₁₁

[M-H]^-

447.093 0

0.7

327.051 3, 357.064 0, 297.040 0

Yong (DZY)

Cistanoside A

11.671

C₃₆H₄₈O₂₀

[M-H]^-

799.263 7

-3.0

623.218 9, 175.037 8

Yong (SDH)

2-O-β-D-Glucopyranosyl atractyligenin

11.702

C₂₅H₃₈O₉

[M-H]^-

481.244 4

1.2

301.181 3, 320.184 0

Ti (XFH)

Rehmannioside C

11.723

C₁₉H₃₂O₈

[M+Na]⁺

411.199 9

1.0

245.194 6

Yong (SDH)

Rehmapicroside

11.949

C₁₆H₂₆O₈

[M-H]^-

345.154 5

-1.2

165.054 5

Yong (SDH)

Liquiritigenin

12.156

C₁₅H₁₂O₄

[M-H]^-

255.066 0

1.2

135.048 0, 119.050 9

Ti (ZGC)

Liquiritin apioside

12.363

C₂₆H₃₀O₁₃

[M-H]^-

546.161 1

0.5

417.119 6, 255.067 4, 135.010 1

Ti (ZGC)

Afzelin

12.423

C₂₁H₂₀O₁₀

[M-H]^-

431.098 3

1.2

283.062 0, 311.056 1, 323.052 8

Ti (ZGC)

Isovitexin

12.434

C₂₁H₂₀O₁₀

[M+H]⁺

433.113 4

-0.2

433.112 1, 313.072 1, 415.103 6

Yong (DZY)

Vitexin

12.444

C₂₁H₂₀O₁₀

[M-H]^-

431.097 0

-1.9

117.035 0, 283.061 1, 161.022 9

Yong (DZY)

Taxifolin

12.704

C₁₅H₁₂O₇

[M-H]^-

303.051 4

3.0

107.016 0, 125.026 2, 175.035 5, 217.054 2

Ti (XFH)

Quercetin-3-O-glucuronide

12.796

C₂₁H₁₈O₁₃

[M+H]⁺

479.082 4

-0.4

303.048 9

Ti (XFH)

Quercetin

12.859

C₁₅H₁₀O₇

[M-H]^-

301.034 8

0.0

229.047 9, 178.997 2, 151.004 5

Ti (XFH), Yong (DZY)

Hyperoside

13.013

C₂₁H₂₀O₁₂

[M-H]^-

463.087 7

0.0

151.005 2, 255.031 6, 271.025 8, 300.028 1, 301.035 2

Ti (XFH)

Isoquercitrin

13.024

C₂₁H₂₀O₁₂

[M-H]^-

463.087 9

0.4

107.014 6, 151.004 6, 178.998 9, 255.029 7, 300.028 4, 301.033 9

Ti (XFH)

Patulitrin

13.231

C₂₂H₂₂O₁₃

[M+H]⁺

495.114 1

0.4

318.035 9, 333.059 7

Ti (XFH)

Jiocarotenoside B1

13.415

C₃₇H₅₀O₂₀

[M-H]^-

813.280 3

-1.7

637.236 2, 175.032 2

Yong (SDH)

Azelaic acid

13.446

C₉H₁₆O₄

[M-H]^-

187.096 0

-5.3

125.095 4

Yong (MD)

Neo-rehmannioside B

13.633

C₁₅H₂₄O₆

[M-H]^-

299.149 3

-0.7

139.073 5

Yong (SDH)

Isorhamnetin-3-O-glucoside

13.675

C₂₂H₂₂O₁₂

[M-H]^-

477.103 7

0.8

107.021 1, 151.002 7, 285.040 5, 314.043 7, 315.051 7

Ti (XFH)

1,5-Dicaffeoylquinic acid

13.808

C₂₅H₂₄O₁₂

[M-H]^-

515.119 5

1.0

335.078 9, 191.056 4, 179.035 3

Ti (XFH)

Forsythoside A

14.026

C₂₉H₃₆O₁₅

[M-H]^-

623.198 1

0.8

177.017 3, 119.048 2

Yong (SDH)

Isochlorogenic acid A

15.214

C₂₅H₂₄O₁₂

[M-H]^-

515.119 5

1.0

203.037 2, 191.057 1, 179.036 2

Ti (XFH)

5-Methoxy-6-methyl-7-oxhydryl-8-methoxy-3-(2′-oxhydryl-4′-methoxybenzyl)-4-chromanone

15.429

C₂₀H₂₂O₇

[M-H]^-

373.129 8

2.9

153.019 6, 168.046 0

Yong (MD)

5,7-Dihydroxy-3-(4′-methoxybenzyl)-4-chromone

15.865

C₁₇H₁₄O₅

[M-H]^-

297.075 2

-3.7

203.037 1, 175.046 9

Yong (MD)

Aegineticacid

15.957

C₁₅H₂₄O₄

[M+H]⁺

269.176 4

4.1

167.010 4

Yong (SDH)

Formononetin

16.122

C₁₆H₁₁O₄

[M-H]^-

267.066 0

1.1

252.044 8

Ti (ZGC)

Ophiopogonanone E

16.308

C₁₉H₂₀O₇

[M-H]^-

359.113 6

1.4

208.034 1, 138.035 6

Yong (MD)

5,7-Dihydroxy-6,8-dimethyl-3-(3′,5′-dimethoxy-4′-hydroxybenzyl)-4-chromanone

16.339

C₂₀H₂₂O₇

[M-H]^-

373.130 0

3.5

207.064 6, 179.070 1, 135.046 6

Yong (MD)

5,7-Dihydroxy-8-methyl-3-(3′,4′-dimethoxybenzyl)-4-chromone

16.410

C₁₈H₁₄O₆

[M-H]^-

325.071 8

1.8

297.073 3, 131.053 8, 203.035 9

Yong (MD)

Neoliquiritin

16.474

C₂₁H₂₂O₉

[M+H]⁺

419.132 6

-3.8

119.047 6, 137.022 1, 239.069 7, 257.080 6

Ti (ZGC)

Isoliquiritin

16.959

C₂₁H₂₂O₉

[M+H]⁺

419.135 1

2.1

137.023 2, 239.070 8, 257.082 5

Ti (ZGC)

Isoliquiritigenin

16.969

C₁₅H₁₂O₄

[M+H]⁺

257.081 0

-1.6

137.023 8

Ti (ZGC)

Martynoside

17.103

C₃₁H₄₀O₁₅

[M-H]^-

651.228 5

-0.6

193.048 0, 175.042 1

Yong (SDH)

Spinacetin

17.216

C₁₇H₁₄O₈

[M-H]^-

345.061 6

1.7

315.014 5, 330.038 3

Ti (XFH)

5-Oxhydryl-6-methyl-7-methoxy-3-(3′,4′-dihydroxyphenyl)-4-chromone

17.546

C₁₈H₁₆O₆

[M-H]^-

327.086 5

-1.2

164.049 8, 327.084 9

Yong (MD)

Uralsaponin F

17.693

C₄₄H₆₄O₁₉

[M-H]^-

895.399 4

3.4

853.394 4, 821.353 5, 351.059 5

Ti (ZGC)

1-O-Acetyl britannilactone

18.354

C₁₇H₂₄O₅

[M+H]⁺

309.169 2

-3.2

291.050 0, 231.136 9, 203.141 2

Ti (XFH)

Luteolin

18.404

C₁₅H₁₀O₆

[M-H]^-

285.039 7

-0.7

175.035 6, 151.004 5, 133.026 6

Ti (XFH), Yong (DZY)

Eupafolin

18.684

C₁₆H₁₂O₇

[M-H]^-

315.051 3

2.5

300.027 4

Ti (XFH)

Rosmarinic acid

20.563

C₁₈H₁₆O₈

[M-H]^-

359.077 4

1.9

133.029 3, 135.044 2, 161.025 6, 193.014 4

Ti (XFH)

Licorice saponin A3

20.770

C₄₈H₇₂O₂₁

[M+H]⁺

985.467 6

3.2

453.336 4, 471.348 0, 615.389 4, 809.433 9

Ti (ZGC)

Diosmetin

21.069

C₁₆H₁₂O₆

[M-H]^-

299.056 9

4.3

227.037 1, 256.039 1, 284.032 8

Yong (DZY)

Ophiopogonin D

21.070

C₄₄H₇₀O₁₆

[M+H]⁺

855.471 6

-3.0

251.178 2, 287.200 7, 431.313 8, 559.363 5, 577.379 1, 711.368 9, 723.434 0

Yong (MD)

Licorice saponin G2

21.153

C₄₂H₆₂O₁₇

[M+H]⁺

839.408 6

2.5

451.320 7, 469.331 2, 487.341 5, 663.377 1

Ti (ZGC)

Licorice saponin E2

21.193

C₄₂H₆₀O₁₆

[M+H]⁺

821.395 8

-0.2

451.323 1, 469.332 6, 645.364 4

Ti (ZGC)

Gancaonin G

21.203

C₂₁H₂₀O₅

[M+H]⁺

353.139 8

2.5

267.063 7, 297.108 2

Ti (ZGC)

100

Glycyrrhetinic acid

21.266

C₃₀H₄₆O₄

[M+H]⁺

471.346 2

-2.5

407.329 5, 435.326 9, 453.337 0

Ti (ZGC)

101

Neobritannilactone B

21.276

C₁₅H₂₀O₃

[M-H]^-

247.133 8

1.6

203.148 3, 201.132 8, 135.083 1

Ti (XFH)

102

Methylophiopogonone A

21.286

C₁₉H₁₆O₆

[M-H]^-

339.087 3

1.2

311.093 4, 217.208 3

Yong (MD)

103

Ophiopogonanone B

21.328

C₁₉H₂₀O₅

[M-H]^-

327.124 5

4.0

178.066 9

Yong (MD)

104

Glycyrrhizic acid

21.389

C₄₂H₆₂O₁₆

[M-H]^-

821.396 3

0.4

351.055 0, 193.034 8, 469.344 7

Ti (ZGC)

105

Pregomisin

21.431

C₂₂H₃₀O₆

[M+H]⁺

391.212 2

0.3

327.143 6, 275.084 7, 229.096 2

Yong (WWZ)

106

Uralsaponin C

21.473

C₄₂H₆₄O₁₆

[M+H]⁺

825.428 1

1.0

455.351 0, 473.361 4

Ti (ZGC)

107

8-Formyl ophiopogonone B

21.534

C₂₀H₂₂O₇

[M+H]⁺

375.143 9

-1.3

109.062 1, 251.090 2, 357.133 8

Yong (MD)

108

Casticin

21.699

C₁₉H₁₈O₈

[M+H]⁺

375.107 6

-1.1

360.082 6, 375.103 9, 377.116 6

Ti (XFH)

109

Schisandrol B

21.751

C₂₃H₂₈O₇

[M+H]⁺

417.192 3

2.4

368.147 1, 399.179 9

Yong (WWZ)

110

Diosgenin

21.804

C₂₇H₄₂O₃

[M+H]⁺

415.321 5

0.7

157.095 5

Yong (MD)

111

Ilicic acid

21.824

C₁₅H₂₄O₃

[M-H]^-

251.165 8

4.4

207.173 2

Ti (XFH)

112

Japonicones D

21.885

C₃₄H₄₄O₉

[M+H]⁺

597.305 9

-0.8

211.109 5, 185.132 0

Ti (XFH)

113

Gomisin D

21.896

C₂₈H₃₄O₁₀

[M+H]⁺

531.224 5

2.8

401.158 9, 383.149 2, 341.101 3

Yong (WWZ)

114

Gomisin R

21.906

C₂₂H₂₄O₇

[M+H]⁺

401.159 3

-1.7

337.106 6, 341.102 8, 383.148 2

Yong (WWZ)

115

Gomisin J

21.927

C₂₂H₂₈O₆

[M+H]⁺

389.194 5

-4.9

227.075 0, 287.092 0, 137.060 1

Yong (WWZ)

116

5-Oxhydryl-6-aldehyde-7-methoxy-8-methyl-3-(4′-methoxybenzyl)-4-chromanone

21.937

C₂₀H₂₀O₆

[M-H]^-

355.120 0

5.1

217.052 1, 150.031 8

Yong (MD)

117

Ruscogenin

21.938

C₂₇H₄₂O₄

[M+H]⁺

431.316 8

1.6

251.177 6, 269.185 4, 139.078 6

Yong (MD)

118

Sesamin

21.959

C₂₀H₁₈O₆

[M+H]⁺

355.117 9

-0.8

179.035 7, 268.985 4

Hua (XX)

119

Angeloylgomisin H

22.029

C₂₈H₃₆O₈

[M+H]⁺

501.248 9

0.2

370.173 1, 355.154 4, 337.142 4

Yong (WWZ)

120

Schisantherin B

22.071

C₂₈H₃₄O₉

[M+H]⁺

515.227 9

-0.4

385.165 4, 355.152 5, 343.116 8

Yong (WWZ)

121

Benzoylgomisin H

22.155

C₃₀H₃₄O₈

[M+H]⁺

523.231 3

-3.6

441.181 5, 409.159 0, 386.174 3

Yong (WWZ)

122

Gedunin

22.155

C₂₈H₃₄O₇

[M+H]⁺

483.238 3

0.0

381.133 3, 395.149 1, 367.117 2

Yong (WWZ)

123

Schisandrin B

22.155

C₂₃H₂₈O₆

[M+H]⁺

401.195 8

-1.5

386.174 3, 370.177 3

Yong (WWZ)

124

Alantolactone

22.195

C₁₅H₂₀O₂

[M+H]⁺

233.153 9

1.7

159.114 6, 118.071 1, 106.073 7

Ti (XFH)

125

Schisanhenol B

22.237

C₂₂H₂₆O₆

[M+H]⁺

387.179 7

-2.8

355.154 1, 326.150 7, 271.060 4

Yong (WWZ)

126

Schisandrin C

22.350

C₂₂H₂₄O₆

[M+H]⁺

385.166 2

2.9

257.080 8, 199.074 8, 184.051 5

Yong (WWZ)

127

Schisantherin A

22.381

C₃₀H₃₂O₉

[M+H]⁺

537.209 6

-5.4

415.173 3, 397.163 7, 371.148 9

Yong (WWZ)

128

Schisandrin A

22.753

C₂₄H₃₂O₆

[M+H]⁺

417.226 5

-2.9

402.203 2, 386.204 3, 371.184 9

Yong (WWZ)

129

Schisanhenol

22.504

C₂₃H₃₀O₆

[M+H]⁺

403.211 0

-2.7

302.116 8, 271.093 8

Yong (WWZ)

130

Asarinin

22.940

C₂₀H₁₈O₆

[M+NH₄]⁺

372.144 4

-0.8

128.060 9, 135.038 8, 161.063 1

Hua (XX)

131

5,7,2′-Trihydroxy-6,8-dimethyl-3-(3′,4′-methylenedioxybenzyl)-chromone

22.961

C₁₉H₁₆O₇

[M+H]⁺

357.097 2

-0.6

339.097 9

Yong (WWZ)

132

Dibutyl phthalate

23.239

C₁₆H₂₂O₄

[M+H]⁺

279.160 9

4.7

149.022 3, 121.027 8

Yong (WWZ)

Component	Content/mg·g^-1
Schisandrol B	0.93 ± 0.04
Schizandrin A	0.37 ± 0.07
Schisandrin C	1.15 ± 0.11
Methylophiopogonone A	2.62 ± 0.31
Ophiogonanone A	3.00 ± 0.23
1-O-Acetyl britannilactone	2.37 ± 0.06
Britannin	0.73 ± 0.13

Component

Content/mg·g^-1

Schisandrol B

0.93 ± 0.04

Schizandrin A

0.37 ± 0.07

Schisandrin C

1.15 ± 0.11

Methylophiopogonone A

2.62 ± 0.31

Ophiogonanone A

3.00 ± 0.23

1-O-Acetyl britannilactone

2.37 ± 0.06

Britannin

0.73 ± 0.13