药学学报

No.	t_R/min	m/z	Ion mode	Mass error(×10^-6)	Formula	Identification	Fragment	Class	Origin
1	2.07	422.025 5	[M−H]⁻	7.4	C₁₁H₂₁NO₁₀S₃	Glucoiberin	358, 259, 96	E	YCQZ
2	2.97	193.034 4	[M−H]⁻	5.29	C₆H₁₀O₇	Galaturonate	131, 113	E	YCQZ
3	3.63	191.018 8	[M−H]⁻	4.92	C₆H₈O₇	Citric acid	173	E	DKXR, CZSZ, CBS, GT
4	5.35	331.065 3	[M−H]⁻	5.23	C₁₃H₁₆O₁₀	6-O-Galloyl-glucose	169, 125	D	CBS
5	5.69	257.498 6	[M+H]⁺	2.36	C₁₆H₃₂O₂	Palmitic acid	257, 221	E	CZSZ, HQ
6	8.98	165.056 0	[M+H]⁺	8.26	C₉H₈O₃	trans-p-Hydroxycinnamic acid	119	D	HQ
7	9.33	493.251 3	[M−H]⁻	4.56	C₁₉H₂₆O₁₅	Galloylsucrose	331, 169, 125	D	CBS
8	9.56	166.087 6	[M+H]⁺	7.19	C₉H₁₁NO₂	L-Phenylalanine	120, 103	E	CZSZ
9	10.23	167.456 2	[M−H]⁻	8.78	C₈H₈O₄	Vanillic acid	123	D	CZSZ
10	14.62	194.081 9	M	5.89	C₁₀H₁₀O₄	Ferulate	176, 148, 133	D	MMH, CZSZ, CBS, GT, HQ
11	15.04	438.157 9	[M+H]⁺	0.54	C₃₀H₄₆O₂	Ganoderol A	293, 259, 137	B	CZSZ
12	20.78	502.151 9	[M+FA]⁻	6.58	C₂₀H₂₇NO₁₁	D-Amygdalin	323, 294, 221, 179	E	DKXR
13	20.78	186.928 5	[M−H]⁻	9.5	C₁₁H₂₂O₂	Hexyl 2-methylbutyrate	164	E	DKXR
14	20.78	413.768 3	[M−H]⁻	4.6	C₂₉H₅₀O	beta-Sitosterol	414, 326, 283	E	DKXR, MMH
15	21.86	171.029 8	[M+H]⁺	4.26	C₇H₆O₅	Gallic acid	171, 153, 127, 117	D	DKXR, CZSZ, CBS, YCQZ
16	22.62	123.015 7	[M+H]⁺	5.12	C₇H₆O₂	Benzoic acid	105, 110	D	CBS
17	22.88	353.085 4	[M−H]⁻	8.85	C₁₆H₁₈O₉	Chlorogenic acid	353, 191, 173, 135	D	DKXR, MMH, CBS, GT
18	22.88	358.111 4	[M−H]⁻	5.6	C₂₀H₂₂O₆	Pinoresinol	312	E	DKXR
19	23.91	474.234 3	[M+H]⁺	0.89	C₂₀H₂₃N₇O₇	Folinic acid	414, 223	E	CBS, YCQZ
20	24.70	373.110 9	[M−H]⁻	8.26	C₁₆H₂₂O₁₀	Geniposidic acid	373, 211, 149, 123	F	YCQZ, HQ
21	24.85	206.046 3	[M+H]⁺	7.82	C₁₀H₇NO₄	6-Hydroxy-4-oxoquinoline-2-carboxylic acid	206, 188, 160, 132, 104	C	MMH
22	25.78	589.118 2	[M−H]⁻	8.52	C₃₀H₃₂O₁₇S	Galloyl paeoniflorin sulfite	259, 167	E	CBS
23	25.89	444.479 5	[M+H]⁺	2.05	C₃₀H₅₀O₂	Betulin	425, 191, 235	B	CZSZ
24	26.54	268.088 2	[M+H]⁺	2.59	C₁₀H₁₃N₅O₄	Adenosine	136, 133, 119	E	DKXR, CZSZ
25	27.37	166.123 1	[M+H]⁺	7.41	C₁₀H₁₅NO	Ephedrine	148, 133, 117, 115	C	MMH
26	27.52	135.044 7	[M+H]⁺	1.26	C₇H₆O	Benzaldehyde	107, 79	E	MMH
27	28.40	148.113 2	M	0.85	C₉H₈O₂	Cinnamic acid	132, 115, 100	D	CBS
28	28.41	166.158 9	[M+H]⁺	5.36	C₁₀H₁₅NO	Pseudoephedrine	148, 133, 117, 115	C	MMH
29	30.09	543.112 7	[M−H]⁻	0.56	C₂₃H₂₈O₁₃S	Paeoniflorin sulfite	497, 375, 121	B	CBS
30	30.24	224.129 8	[M+H]⁺	7.9	C₁₂H₁₇NO₃	Maokonine	206, 135, 117	C	MMH
31	30.32	180.139 5	[M+H]⁺	7.01	C₁₁H₁₇NO	Methylephedrine	162, 147, 117, 115	C	MMH
32	30.56	311.401 2	[M−H]⁻	2.03	C₁₉H₂₂N₂O₂	Peraksine	293, 224	C	YCQZ
33	30.96	465.101 2	[M−H]⁻	5.86	C₂₁H₂₂O₁₂	Taxifolin 7-O-glucoside	437, 177	A	HQ
34	31.12	305.068 9	[M+H]⁺	5.26	C₁₅H₁₂O₇	Taxifolin	305, 195, 108	A	CBS
35	31.56	134.098 2	[M+H]⁺	8.95	C₉H₁₀O	m-Methylacetophenone	135, 120, 92, 78	E	MMH
36	31.61	183.028 9	[M−H]⁻	5.56	C₈H₈O₅	Methyl gallate	183, 124	E	CBS
37	31.96	497.201 5	[M+H]⁺	0.29	C₂₃H₂₈0₁₂	Oxypaeoniflorin	197, 179, 139, 195	B	CBS
38	35.16	462.256 3	[M−H]⁻	5.69	C₂₁H₁₈O₁₂	Luteolin-3-glucuronide	285, 175	A	CZSZ
39	35.89	438.057 0	[M+H]⁺	8.45	C₁₂H₂₃O₁₀NS₃	Glucoraphanin	372, 274, 259, 195, 96, 74	E	CLFZ
40	36.12	103.150 0	[M−H]⁻	6.23	C₈H₈	Styrene	105, 79, 91	E	MMH
41	36.18	345.119 9	[M−H]⁻	3.46	C₁₅H₂₂O₉	Aucubin	345, 183, 139, 101	F	YCQZ
42	36.22	134.060 3	[M+H]⁺	2.59	C₈H₇NO	Mandelonitrile	106, 78	E	DKXR
43	36.22	407.046 2	[M+Na]^-	4.7	C₂₀H₂₆O₆	Secoisolariciresinol	462	E	DKXR
44	38.56	593.189 6	[M−H]⁻	5.11	C₃₀H₂₆O₁₃	(+)-Catechin-(4α→8)-(−)-epigallocatechin	467, 425, 407	A	HQ
45	42.56	95.080 0	[M−H]⁻	0.26	C₅H₄O₂	Furfural	97, 69, 55	E	MMH
46	43.44	197.456 1	[M−H]⁻	4.23	C₉H₁₀O₅	Ethyl gallate	169, 125, 124	E	CBS
47	44.56	134.521 3	[M+H]⁺	2.36	C₁₀H₁₂	4-Phenyl-1-butene	103, 89	E	MMH
48	45.12	255.897 4	[M+H]⁺	5.62	C₁₅H₁₀O₄	Daidzein	137	A	CBS
49	45.18	261.456 8	[M+H]⁺	8.95	C₁₁H₂₀N₂O₅	N-L-gamma-Glutamyl-L-leucine	244, 197, 131, 86	E	CZSZ
50	45.19	477.456 0	[M−H]⁻	3.26	C₁₇H₂₂N₂O₁₀S₂	Neoglucobrassicin	446, 259, 234, 96	E	CLFZ
51	45.69	301.567 9	[M−H]⁻	2.56	C₁₆H₁₄O₆	5, 7, 4′-Trihydroxy 6-methoxyflavanone	284	A	HQ
52	46.63	191.071 6	[M+H]⁺	4.56	C₁₃H₁₈O	beta-Damascenone	213, 195, 135	B	MMH
53	47.50	481.174 1	[M+H]⁺	0.79	C₂₃H₂₈O₁₁	Paeoniflorin	525, 481, 197, 105	B	CBS
54	47.57	325.489 1	[M+H]⁺	4.08	C₂₀H₂₀O₄	Glabridin	325, 307, 289, 135, 107	A	DKXR
55	47.57	330.072 7	M	2.8	C₁₉H₂₂O₅	Gibberellin A5	/	B	DKXR
56	47.57	340.100 9	[M−H₂O]	5.21	C₂₀H₂₂O₆	Matairesinol	340, 332	E	DKXR
57	48.22	281.479 6	[M+H]⁺	6.59	C₁₈H₃₄O₂	Elaidic acid	/	E	YCQZ
58	48.67	443.568 9	[M−Na]⁻	2.99	C₂₁H₂₂O₁₂	Plantagoside	443	B	YCQZ
59	48.94	311.171 1	[M+H]⁺	5.46	C₁₄H₁₄O₈	2-Hydroxy-2-[(E)-3-(4-hydroxy-3-methoxyphenyl)prop-2-enoyl] butanedioic acid	251	E	CLFZ
60	50.89	385.111 5	[M−H]⁻	6.25	C₁₇H₂₂O₁₀	Sinapic acid glucoside	325, 223	D	HQ, CLFZ
61	53.06	278.456 9	[M+H]⁺	2.56	C₁₈H₃₀O₂	Linolenic acid	279, 149, 123, 109	E	DKXR, YCQZ, HQ
62	53.69	525.135 6	[M−H]⁻	0.89	C₂₄H₃₀O₁₃	Mudanpioside E	327, 121	B	CBS
63	53.79	481.256 3	[M+H]⁺	7.54	C₂₃H₂₈O₁₁	Albiflorin	381, 451, 359, 329, 123	B	CBS
64	53.81	463.163 1	[M+H]⁺	0.57	C₂₃H₂₆O₁₀	Lactiflorin	179, 151	B	CBS
65	53.82	165.589 6	[M−H]⁻	6.58	C₈H₆O₄	Phthalic acid	152, 136, 121	D	DKXR, CBS
66	53.82	341.265 4	[M+Na]⁺	2.6	C₁₅H₁₀O₈	Myricetin	318	A	GT
67	54.69	240.361 0	[M−H]⁻	5.43	C¹²H²¹N³O²	Plantagoguanidinic acid	208, 226	C	YCQZ
68	54.70	593.136 8	[M−H]⁻	6.8	C₂₇H₃₀O₁₅	Schaftoside	473, 443, 413, 383	A	YCQZ
69	54.89	287.590 0	[M+H]⁺	11.28	C₁₅H₁₀O₆	Luteolin	151, 133175	A	CZSZ
70	55.69	754.569 1	[M+H]⁺	5.69	C₃₄H₄₂O₁₉	3′, 6-Disinapoyl sucrose	207, 175, 147, 119, 91, 65	E	CLFZ
71	55.92	563.135 8	[M−H]⁻	8.65	C₂₆H₂₈O₁₄	Apiin	269, 227, 161, 117	A	CZSZ, CBS, YCQZ
72	56.02	285.481 2	[M+H]⁺	2.59	C₁₈H₃₆O₂	Stearic acid	285, 60	E	DKXR, CZSZ
73	56.18	457.113 3	[M+H]⁺	8.46	C₃₀H₄₈O₃	Ursolic acid	913, 439, 411, 393	B	CBS, GT, YCQZ, HQ
74	56.26	373.856 3	[M−H]⁻	5.02	C₁₉H₁₈O₈	Skullcapflavon Ⅱ	419, 373, 345, 360, 327	A	HQ
75	56.89	223.456 8	[M−H]⁻	5.14	C₁₂H₁₆O₄	Senkyunolide Ⅰ	179, 161, 151	B	CBS
76	58.13	651.489 7	[M−H]⁻	1.26	C₃₁H₄₀O₁₅	Isomartynoside	605, 475, 175	E	YCQZ
77	58.29	223.061 1	[M−H]⁻	5.69	C₁₁H₁₂_O5	Sinapic acid	179, 135	D	CLFZ
78	58.33	369.121 9	[M+H]⁺	5.11	C₁₇H₂₄N₂O₅S	Sinapine thiocyanate	301, 225	C	CLFZ
79	58.47	641.568 5	[M−H]⁻	8.13	C₂₉H₃₈O₁₆	Isomaltopaeoniflorin	641, 525, 479, 283, 161	B	CBS
80	58.59	374.598 6	[M+H]⁺	4.25	C₁₁H₁₉NO₉S₂	Gluconapin	259, 195, 130, 96, 74	E	CLFZ
81	59.38	281.093 5	[M−H]⁻	5.89	C₁₈H₃₄O₂	Oleic acid	263, 183	E	CZSZ, GT, HQ
82	60.11	300.997 2	[M−H]⁻	6.13	C₁₄H₆O₈	Ellagic acid	300, 185, 257	D	CBS
83	60.23	593.145 6	[M−H]⁻	8.56	C₂₇H₃₀O₁₅	Kaempferol 3-rutinoside	447	A	CZSZ, CBS
84	61.03	134.220 3	[M−H]⁻	5.39	C₁₀H₁₄	2-Ethyl-1, 4-dimethylbenzene	135, 105, 91, 77	E	MMH
85	61.44	283.061 9	[M−H]⁻	5.46	C₁₆H₁₂O₅	Oroxylin A	283, 268	A	HQ
86	61.87	465.105 6	[M+H]⁺	6.56	C₂₁H₂₀O₁₂	Hyperoside	303, 257	A	CBS
87	62.55	753.220 2	[M−H]⁻	6.08	C₃₄H₄₂O₁₉	1, 2-Disinapoylgentiobiose	223, 190	E	CLFZ
88	62.87	151.111 8	[M+H]⁺	2.59	C₉H₁₃NO	Phenylpropanolamine	134, 117	C	MMH
89	63.19	463.085 2	[M−H]⁻	6.59	C₂₁H2₀O₁₂	Herbacetin 7-glucoside	301, 271	A	MMH
90	63.56	338.256 4	[M+H]⁺	2.59	C₂₂H₄₃NO	Erucylamide	321, 303, 296	E	CBS
91	63.57	463.089 5	[M+H]⁺	5.43	C₂₁H₁₈O₁₂	Luteolin-7-O-glucuronide	287, 463	A	CZSZ
92	63.76	137.023 8	[M−H]⁻	4.76	C₇H₆O₃	Protocatechualdehyde	137, 109	E	CZSZ
93	65.78	547.140 8	[M−H]⁻	9.22	C₂₆H₂₈O₁₃	Chrysin 6-C-glucoside 8-C-α-Larabinoside	487, 457, 427, 367	A	HQ
94	65.91	624.193 4	[M−H]⁻	7.52	C₂₉H₃₆O₁₅	Acteoside	623, 461, 179, 161, 135	E	YCQZ, HQ
95	66.43	289.089 4	[M+H]⁺	5.46	C₁₅H₁₂O₆	Carthamidin	169, 147	A	HQ
96	66.47	251.092 2	[M+Na]⁺	5.29	C₁₄H₂₈O₂	Tetradecanoic acid	251, 215, 159, 145, 131	E	DKXR
97	66.56	181.564 9	[M−H]⁻	5.22	C₆H₁₄O₆	Sorbitol	119, 101, 89	E	YCQZ
98	69.52	639.561 3	[M−H]⁻	5.69	C₂₉H₃₆O₁₆	Plantainoside D	621, 529	B	YCQZ
99	71.03	195.587 4	[M+H]⁺	8.23	C₁₂H₁₈O₂	Cnidilide	177, 149, 131, 125	E	CBS
100	72.09	297.079 1	[M+H]⁺	2.17	C₁₃H₁₂O₈	Caffeoylmalic acid	173	D	MMH
101	72.61	461.070 7	[M−H]⁻	4.15	C21H18O12	Scutellarin	285, 267, 239, 119, 113	A	CZSZ, HQ
102	74.16	205.589 6	[M+H]⁺	6.13	C₁₂H₁₂O₃	3-Butylidene-7-hydroxyphthalide	187, 147	B	CBS
103	74.23	415.214 6	[M+H]⁺	7.6	C₂₄H₃₀O₆	Bis (4-ethylbenzylidene) sorbitol	119	E	DKXR
104	74.91	509.486 3	[M−H]⁻	4.23	C₂₄H₃₀O₁₂	Mudanpioside D	509, 463, 121, 77	B	CBS
105	75.13	479.563 2	[M+H]⁺	1.03	C₂₃H₂₆O₁₁	Plantainoside A	461, 334, 307, 263, 179	B	YCQZ
106	76.17	153.031 2	[M−H]⁻	3.5	C₁₀H₁₈O	Terpineol	180, 153	B	DKXR
107	76.17	361.589 6	[M+H]⁺	2.59	C₁₈H₁₆O₈	Rosmarinic acid	197, 179, 161, 135, 133	E	CZSZ, CBS
108	76.36	431.525 9	[M−H]⁻	5.03	C₂₁H₂₀O₁₀	Apigenin-7-O-β-D-glucoside	151, 239, 240, 268, 432	A	HQ
109	76.95	647.139 3	[M−H]⁻	7.15	C₃₀H₃₂O₁₄S	Benzoylpaeoniflorin sulfite	259	B	CBS
110	77.36	191.018 3	[M−H]⁻	1.2	C₁₃H₂₀O	beta-Ionone	191, 111	B	DKXR
111	77.36	369.236 5	[M+H]⁺	5.26	C₂₁H₂₄N₂O₄	18, 19-Dehydrocorynoxinic acid	369, 351	E	GT
112	79.99	295.060 9	[M+Na]⁺	1.02	C₁₆H₃₂O₃	2-Hydroxypalmitic acid	295, 277, 259, 231	E	DKXR
113	79.99	383.198 3	[M+H]⁺	10.08	C₂₂H₂₆N₂O₄	Corynoxeine	351, 201	C	GT
114	80.05	447.123 1	[M−H]⁻	2.01	C₂₁H₂₀O₁₁	Plantaginin	284	A	YCQZ
115	80.06	325.006 3	[M−H]⁻	5.46	C₁₅H₁₈O₈	4-O-beta-Glucopyranosyl-cis-coumaric acid	163, 119	D	CZSZ
116	80.23	357.147 9	[M+H]⁺	0.28	C₂₀H₂₀O₆	Coniferylferulate	311, 149	E	CBS
117	82.55	269.048 9	[M−H]⁻	6.59	C₁₅H₁₀O₅	Baicalein	241, 197	A	HQ
118	82.62	445.074 6	[M−H]⁻	6.88	C₂₁H₁₈O₁₁	Baicalin	891, 445, 269, 251	A	HQ
119	83.29	615.421 3	[M−H]⁻	8.46	C₃₀H₃₂O₁₄	Mudanpioside H	615, 493, 169	B	CBS
120	84.50	291.088 5	[M+H]⁺	1.02	C₁₅H₁₄O₆	Catechin	161, 123, 139	A	DKXR
121	84.55	385.214 9	[M+H]⁺	4.89	C₂₂H₂₉N₂O₄	Rhynchophylline	353, 268, 160, 110	C	GT
122	84.64	286.080 1	[M+H]⁺	2.05	C₁₇H₁₉NO₃	Coclaurine	286, 269, 254, 237, 209	C	DKXR
123	84.64	385.214 9	[M+H]⁺	4.89	C₂₂H₂₈N₂O₄	Isorhynchophylline	353, 268, 160, 110	C	GT
124	85.13	178.001 2	[M−H]⁻	2.36	C₉H₆O₄	Cichorigenin	149, 133, 105	E	CZSZ
125	85.13	313.269 9	[M−H]⁻	4.09	C₁₇H₁₄O₆	Skullcapflavon Ⅰ	313, 298, 113	A	HQ
126	85.16	473.158 9	[M+H]⁺	1.05	C₃₀H₄₈O₄	Hederagenin	200, 270	B	CZSZ
127	85.16	406.468 1	[M−H]⁻	3.89	C₁₁H₂₁NO₉S₃	3-Methylthiopropyl glucosinolate	259, 195, 96, 74	E	CLFZ
128	85.16	651.289 6	[M−H]⁻	8.99	C₃₁H₄₀O₁₅	Martynoside	605, 475, 175	E	YCQZ
129	85.23	639.853 6	[M−H]⁻	1.25	C2₉H₃₆O₁₆	Plantamajoside	477, 179, 161, 135, 315	B	YCQZ
130	85.26	487.100 2	[M+H]⁺	5.01	C₂₁H₂₈O₁₃	cis-Tanoside F	179, 135	E	YCQZ
131	85.36	315.410 2	[M−H]⁻	4.69	C₁₃H₁₆O₉	1-O-(3, 4-Dihydroxybenzoyl)-beta-D-glucopyranose	152, 108	D	CLFZ
132	85.40	421.235 6	[M−H]⁻	1.11	C₁₉H₁₈O₁₁	Isomangiferin	/	A	YCQZ
133	85.46	301.567 8	[M−H]⁻	8.96	C₁₅H₁₀O₇	Quercetin	178, 151	A	CZSZ
134	85.56	593.788 5	[M+H]⁺	4.56	C₂₈H₃₂O₁₄	Linarin	565, 447, 285	A	CZSZ
135	86.70	447.095 6	[M−H]⁻	7.39	C₂₁H₂₀O₁₁	Dihydrobaicalin	271, 243	A	HQ
136	87.18	133.013 9	[M−H]⁻	−2.9	C₄H₆O₅	Malic acid	115, 133	E	DKXR
137	87.18	612.495 0	[M+2H]⁺	6.9	C₂₇H₃₀O₁₆	Rutin	589, 566	A	HQ
138	87.39	257.045 8	[M+H]⁺	8.46	C₁₅H₁₂O₄	Isoliquiritigenin	239, 137	A	HQ
139	87.46	423.893 5	[M+H]⁺	10.25	C₃₀H₄₆O	Glochidone	405, 215	B	CZSZ
140	87.98	273.077 1	[M+H]⁺	7.15	C₁₅H₁₂O₅	Naringenin	169, 131	A	MMH, CBS
141	87.98	273.098 7	[M+H]⁺	7.16	C₁₅H₁₂O₅	Pinobanksin	273, 151	A	HQ
142	88.23	623.589 6	[M−H]⁻	5.13	C₂₉H₃₆O₁₅	Forsythiaside A	461, 161, 135	D	YCQZ
143	88.75	445.045 6	[M−H]⁻	6.23	C₂₁H₁₈O₁₁	Glychionide A	445, 269	A	HQ
144	89.45	583.269 7	[M−H]⁻	2.58	C₃₀H₃₂O₁₂	Benzoylpaeoniflorin	431, 387, 121	B	CBS
145	89.46	463.469 8	[M−H]⁻	5.11	C₁₆H₂₀N₂O₁₀S₂	4-Hydroxy-3-indolylmethyl glucosinolate	285, 267, 195, 96, 74	E	CLFZ
146	89.56	125.465 0	[M−H]⁻	2.56	C₆H₆O₃	Pyrogallol	79, 96	E	CBS
147	89.57	209.585 6	[M+H]⁺	5.69	C₁₂H₁₆O₃	β-Asarone	191, 163, 153	E	CBS
148	90.13	299.054 9	[M−H]⁻	3.87	C₁₆H₁₂O₆	Tenaxin Ⅱ	283, 227	A	HQ
149	90.13	299.054 9	[M−H]⁻	3.59	C₁₆H₁₂O₆	Kaempferide	299, 228	A	MMH, CBS
150	90.18	445.112 5	[M−H]⁻	3.23	C₂₂H₂₂O₁₀	Wogonin-5-O-D-glucoside	269	A	HQ
151	90.59	227.489 6	[M+H]⁺	2.59	C₁₂H₂₂N₂O₂	Cyclo (Leu-Leu)	209, 114	E	CZSZ
152	90.88	307.058 5	[M+H]⁺	2.18	C₁₅H₁₄O₇	Leucocyanidin	307, 163, 139, 121	A	MMH
153	91.26	183.563 1	[M−H]⁻	5.69	C₁₁H₂₀O₂	2-Undecenoic acid	207, 192, 175, 147, 133, 77	E	DKXR
154	91.26	455.213 6	[M+H]⁺	5.69	C₃₀H₄₈O₃	Oleanolic acid	377	B	GT
155	92.07	459.105 6	[M−H]⁻	7.59	C₂₂H₂₀O₁₁	Oroxyloside	283, 169	A	HQ
156	92.08	429.169 6	[M−H]⁻	5.16	C₂₁H₁₈O₁₀	Chrysin-7-O-β-D glucoronide	253, 175	A	HQ
157	92.15	283.059 2	[M−H]⁻	6.88	C₁₆H₁₂O₅	Wogonin	268, 240, 239, 167, 139	A	HQ
158	95.27	419.156 0	[M+H]⁺	1.28	C₂₁H₂₂O₉	Liquiritin	419, 257, 239, 211, 147	A	DKXR
159	95.27	369.194 9	[M+H]⁺	6.52	C₂₂H₂₈N₂O₃	Hirsutine	543, 497, 265	C	GT
160	96.05	461.109 7	[M+H]⁺	4.15	C₂₂H₂₀O₁₁	Apigenin-7-O-methylglucuronide	461, 271	A	HQ
161	96.14	193.256 4	[M+H]⁺	1.56	C₁₂H₁₆O₂	Sedanenolide	175, 147, 137, 93	B	CBS
162	97.11	629.784 6	[M−H]⁻	1.56	C₃₁H₃₄O₁₄	Mudanpioside B	583, 553, 431, 165, 121, 77	B	CBS
163	97.56	313.065 9	[M−H]⁻	6.59	C₁₇H₁₄O₆	Dihydroxy-dimethoxyflavone	298, 255	A	HQ
164	98.56	783.154 8	[M−H]⁻	5.12	C₃₇H₃₆O₁₉	3′, 6′-di-O-Galloylpaeoniflorin	783, 765, 631, 465, 313	B	CBS
165	99.56	451.896 3	[M−H]⁻	8.59	C₁₃H₂₅NO₁₀S₃	1-Thio-β-D-glucopyranose 1-(6-(methylsulfinyl)-N-(sulfooxy)hexanimi date)	386, 259, 208, 96, 74	E	CLFZ
166	100.26	300.256 9	[M+H]⁺	3.65	C₁₈H₃₇NO₂	Palmidrol	283, 255	E	CBS
167	101.79	115.891 1	[M−H]⁻	2.56	C₅H₈O₃	Levulinic acid	117, 102, 89, 74	E	DKXR, CBS
168	101.79	355.203 4	[M+H]⁺	5.1	C₂₁H₂₆N₂O₃	Yohimbine	355, 212, 144	C	GT
169	103.47	499.207 9	[M+H]⁺	6.84	C₂₆H₃₀N₂O₈	Strictosamide	337, 267	C	GT
170	104.32	432.256 3	[M+H]⁺	6.77	C₁₉H₂₈O₁₁	Benzyl-β-gentiobioside	327, 255	E	CLFZ
171	104.75	167.071 3	[M+H]⁺	5.12	C₉H₁₀O₃	Paeonol	167, 149, 121	D	CBS
172	105.25	287.145 6	[M−H]⁻	8.96	C₁₅H₁₂O₆	Dihydrokaempferol	287, 93, 193, 175	A	CBS
173	107.89	477.120 3	[M−H]⁻	50.56	C₂₃H₂₆O₁₁	Calceolarioside A	360, 325, 290, 203, 163	E	YCQZ
174	108.36	477.889 9	[M−H]⁻	64.88	C₂₃H₂₆O₁₁	Calceolarioside B	/	E	YCQZ

No.	t_R/min	m/z	Ion mode	Mass error(×10^-6)	Formula	Identification	Fragment	Class	Origin
1	2.07	422.025 5	[M−H]⁻	7.4	C₁₁H₂₁NO₁₀S₃	Glucoiberin	358, 259, 96	E	YCQZ
2	2.97	193.034 4	[M−H]⁻	5.29	C₆H₁₀O₇	Galaturonate	131, 113	E	YCQZ
3	3.63	191.018 8	[M−H]⁻	4.92	C₆H₈O₇	Citric acid	173	E	DKXR, CZSZ, CBS, GT
4	5.35	331.065 3	[M−H]⁻	5.23	C₁₃H₁₆O₁₀	6-O-Galloyl-glucose	169, 125	D	CBS
5	5.69	257.498 6	[M+H]⁺	2.36	C₁₆H₃₂O₂	Palmitic acid	257, 221	E	CZSZ, HQ
6	8.98	165.056 0	[M+H]⁺	8.26	C₉H₈O₃	trans-p-Hydroxycinnamic acid	119	D	HQ
7	9.33	493.251 3	[M−H]⁻	4.56	C₁₉H₂₆O₁₅	Galloylsucrose	331, 169, 125	D	CBS
8	9.56	166.087 6	[M+H]⁺	7.19	C₉H₁₁NO₂	L-Phenylalanine	120, 103	E	CZSZ
9	10.23	167.456 2	[M−H]⁻	8.78	C₈H₈O₄	Vanillic acid	123	D	CZSZ
10	14.62	194.081 9	M	5.89	C₁₀H₁₀O₄	Ferulate	176, 148, 133	D	MMH, CZSZ, CBS, GT, HQ
11	15.04	438.157 9	[M+H]⁺	0.54	C₃₀H₄₆O₂	Ganoderol A	293, 259, 137	B	CZSZ
12	20.78	502.151 9	[M+FA]⁻	6.58	C₂₀H₂₇NO₁₁	D-Amygdalin	323, 294, 221, 179	E	DKXR
13	20.78	186.928 5	[M−H]⁻	9.5	C₁₁H₂₂O₂	Hexyl 2-methylbutyrate	164	E	DKXR
14	20.78	413.768 3	[M−H]⁻	4.6	C₂₉H₅₀O	beta-Sitosterol	414, 326, 283	E	DKXR, MMH
15	21.86	171.029 8	[M+H]⁺	4.26	C₇H₆O₅	Gallic acid	171, 153, 127, 117	D	DKXR, CZSZ, CBS, YCQZ
16	22.62	123.015 7	[M+H]⁺	5.12	C₇H₆O₂	Benzoic acid	105, 110	D	CBS
17	22.88	353.085 4	[M−H]⁻	8.85	C₁₆H₁₈O₉	Chlorogenic acid	353, 191, 173, 135	D	DKXR, MMH, CBS, GT
18	22.88	358.111 4	[M−H]⁻	5.6	C₂₀H₂₂O₆	Pinoresinol	312	E	DKXR
19	23.91	474.234 3	[M+H]⁺	0.89	C₂₀H₂₃N₇O₇	Folinic acid	414, 223	E	CBS, YCQZ
20	24.70	373.110 9	[M−H]⁻	8.26	C₁₆H₂₂O₁₀	Geniposidic acid	373, 211, 149, 123	F	YCQZ, HQ
21	24.85	206.046 3	[M+H]⁺	7.82	C₁₀H₇NO₄	6-Hydroxy-4-oxoquinoline-2-carboxylic acid	206, 188, 160, 132, 104	C	MMH
22	25.78	589.118 2	[M−H]⁻	8.52	C₃₀H₃₂O₁₇S	Galloyl paeoniflorin sulfite	259, 167	E	CBS
23	25.89	444.479 5	[M+H]⁺	2.05	C₃₀H₅₀O₂	Betulin	425, 191, 235	B	CZSZ
24	26.54	268.088 2	[M+H]⁺	2.59	C₁₀H₁₃N₅O₄	Adenosine	136, 133, 119	E	DKXR, CZSZ
25	27.37	166.123 1	[M+H]⁺	7.41	C₁₀H₁₅NO	Ephedrine	148, 133, 117, 115	C	MMH
26	27.52	135.044 7	[M+H]⁺	1.26	C₇H₆O	Benzaldehyde	107, 79	E	MMH
27	28.40	148.113 2	M	0.85	C₉H₈O₂	Cinnamic acid	132, 115, 100	D	CBS
28	28.41	166.158 9	[M+H]⁺	5.36	C₁₀H₁₅NO	Pseudoephedrine	148, 133, 117, 115	C	MMH
29	30.09	543.112 7	[M−H]⁻	0.56	C₂₃H₂₈O₁₃S	Paeoniflorin sulfite	497, 375, 121	B	CBS
30	30.24	224.129 8	[M+H]⁺	7.9	C₁₂H₁₇NO₃	Maokonine	206, 135, 117	C	MMH
31	30.32	180.139 5	[M+H]⁺	7.01	C₁₁H₁₇NO	Methylephedrine	162, 147, 117, 115	C	MMH
32	30.56	311.401 2	[M−H]⁻	2.03	C₁₉H₂₂N₂O₂	Peraksine	293, 224	C	YCQZ
33	30.96	465.101 2	[M−H]⁻	5.86	C₂₁H₂₂O₁₂	Taxifolin 7-O-glucoside	437, 177	A	HQ
34	31.12	305.068 9	[M+H]⁺	5.26	C₁₅H₁₂O₇	Taxifolin	305, 195, 108	A	CBS
35	31.56	134.098 2	[M+H]⁺	8.95	C₉H₁₀O	m-Methylacetophenone	135, 120, 92, 78	E	MMH
36	31.61	183.028 9	[M−H]⁻	5.56	C₈H₈O₅	Methyl gallate	183, 124	E	CBS
37	31.96	497.201 5	[M+H]⁺	0.29	C₂₃H₂₈0₁₂	Oxypaeoniflorin	197, 179, 139, 195	B	CBS
38	35.16	462.256 3	[M−H]⁻	5.69	C₂₁H₁₈O₁₂	Luteolin-3-glucuronide	285, 175	A	CZSZ
39	35.89	438.057 0	[M+H]⁺	8.45	C₁₂H₂₃O₁₀NS₃	Glucoraphanin	372, 274, 259, 195, 96, 74	E	CLFZ
40	36.12	103.150 0	[M−H]⁻	6.23	C₈H₈	Styrene	105, 79, 91	E	MMH
41	36.18	345.119 9	[M−H]⁻	3.46	C₁₅H₂₂O₉	Aucubin	345, 183, 139, 101	F	YCQZ
42	36.22	134.060 3	[M+H]⁺	2.59	C₈H₇NO	Mandelonitrile	106, 78	E	DKXR
43	36.22	407.046 2	[M+Na]^-	4.7	C₂₀H₂₆O₆	Secoisolariciresinol	462	E	DKXR
44	38.56	593.189 6	[M−H]⁻	5.11	C₃₀H₂₆O₁₃	(+)-Catechin-(4α→8)-(−)-epigallocatechin	467, 425, 407	A	HQ
45	42.56	95.080 0	[M−H]⁻	0.26	C₅H₄O₂	Furfural	97, 69, 55	E	MMH
46	43.44	197.456 1	[M−H]⁻	4.23	C₉H₁₀O₅	Ethyl gallate	169, 125, 124	E	CBS
47	44.56	134.521 3	[M+H]⁺	2.36	C₁₀H₁₂	4-Phenyl-1-butene	103, 89	E	MMH
48	45.12	255.897 4	[M+H]⁺	5.62	C₁₅H₁₀O₄	Daidzein	137	A	CBS
49	45.18	261.456 8	[M+H]⁺	8.95	C₁₁H₂₀N₂O₅	N-L-gamma-Glutamyl-L-leucine	244, 197, 131, 86	E	CZSZ
50	45.19	477.456 0	[M−H]⁻	3.26	C₁₇H₂₂N₂O₁₀S₂	Neoglucobrassicin	446, 259, 234, 96	E	CLFZ
51	45.69	301.567 9	[M−H]⁻	2.56	C₁₆H₁₄O₆	5, 7, 4′-Trihydroxy 6-methoxyflavanone	284	A	HQ
52	46.63	191.071 6	[M+H]⁺	4.56	C₁₃H₁₈O	beta-Damascenone	213, 195, 135	B	MMH
53	47.50	481.174 1	[M+H]⁺	0.79	C₂₃H₂₈O₁₁	Paeoniflorin	525, 481, 197, 105	B	CBS
54	47.57	325.489 1	[M+H]⁺	4.08	C₂₀H₂₀O₄	Glabridin	325, 307, 289, 135, 107	A	DKXR
55	47.57	330.072 7	M	2.8	C₁₉H₂₂O₅	Gibberellin A5	/	B	DKXR
56	47.57	340.100 9	[M−H₂O]	5.21	C₂₀H₂₂O₆	Matairesinol	340, 332	E	DKXR
57	48.22	281.479 6	[M+H]⁺	6.59	C₁₈H₃₄O₂	Elaidic acid	/	E	YCQZ
58	48.67	443.568 9	[M−Na]⁻	2.99	C₂₁H₂₂O₁₂	Plantagoside	443	B	YCQZ
59	48.94	311.171 1	[M+H]⁺	5.46	C₁₄H₁₄O₈	2-Hydroxy-2-[(E)-3-(4-hydroxy-3-methoxyphenyl)prop-2-enoyl] butanedioic acid	251	E	CLFZ
60	50.89	385.111 5	[M−H]⁻	6.25	C₁₇H₂₂O₁₀	Sinapic acid glucoside	325, 223	D	HQ, CLFZ
61	53.06	278.456 9	[M+H]⁺	2.56	C₁₈H₃₀O₂	Linolenic acid	279, 149, 123, 109	E	DKXR, YCQZ, HQ
62	53.69	525.135 6	[M−H]⁻	0.89	C₂₄H₃₀O₁₃	Mudanpioside E	327, 121	B	CBS
63	53.79	481.256 3	[M+H]⁺	7.54	C₂₃H₂₈O₁₁	Albiflorin	381, 451, 359, 329, 123	B	CBS
64	53.81	463.163 1	[M+H]⁺	0.57	C₂₃H₂₆O₁₀	Lactiflorin	179, 151	B	CBS
65	53.82	165.589 6	[M−H]⁻	6.58	C₈H₆O₄	Phthalic acid	152, 136, 121	D	DKXR, CBS
66	53.82	341.265 4	[M+Na]⁺	2.6	C₁₅H₁₀O₈	Myricetin	318	A	GT
67	54.69	240.361 0	[M−H]⁻	5.43	C¹²H²¹N³O²	Plantagoguanidinic acid	208, 226	C	YCQZ
68	54.70	593.136 8	[M−H]⁻	6.8	C₂₇H₃₀O₁₅	Schaftoside	473, 443, 413, 383	A	YCQZ
69	54.89	287.590 0	[M+H]⁺	11.28	C₁₅H₁₀O₆	Luteolin	151, 133175	A	CZSZ
70	55.69	754.569 1	[M+H]⁺	5.69	C₃₄H₄₂O₁₉	3′, 6-Disinapoyl sucrose	207, 175, 147, 119, 91, 65	E	CLFZ
71	55.92	563.135 8	[M−H]⁻	8.65	C₂₆H₂₈O₁₄	Apiin	269, 227, 161, 117	A	CZSZ, CBS, YCQZ
72	56.02	285.481 2	[M+H]⁺	2.59	C₁₈H₃₆O₂	Stearic acid	285, 60	E	DKXR, CZSZ
73	56.18	457.113 3	[M+H]⁺	8.46	C₃₀H₄₈O₃	Ursolic acid	913, 439, 411, 393	B	CBS, GT, YCQZ, HQ
74	56.26	373.856 3	[M−H]⁻	5.02	C₁₉H₁₈O₈	Skullcapflavon Ⅱ	419, 373, 345, 360, 327	A	HQ
75	56.89	223.456 8	[M−H]⁻	5.14	C₁₂H₁₆O₄	Senkyunolide Ⅰ	179, 161, 151	B	CBS
76	58.13	651.489 7	[M−H]⁻	1.26	C₃₁H₄₀O₁₅	Isomartynoside	605, 475, 175	E	YCQZ
77	58.29	223.061 1	[M−H]⁻	5.69	C₁₁H₁₂_O5	Sinapic acid	179, 135	D	CLFZ
78	58.33	369.121 9	[M+H]⁺	5.11	C₁₇H₂₄N₂O₅S	Sinapine thiocyanate	301, 225	C	CLFZ
79	58.47	641.568 5	[M−H]⁻	8.13	C₂₉H₃₈O₁₆	Isomaltopaeoniflorin	641, 525, 479, 283, 161	B	CBS
80	58.59	374.598 6	[M+H]⁺	4.25	C₁₁H₁₉NO₉S₂	Gluconapin	259, 195, 130, 96, 74	E	CLFZ
81	59.38	281.093 5	[M−H]⁻	5.89	C₁₈H₃₄O₂	Oleic acid	263, 183	E	CZSZ, GT, HQ
82	60.11	300.997 2	[M−H]⁻	6.13	C₁₄H₆O₈	Ellagic acid	300, 185, 257	D	CBS
83	60.23	593.145 6	[M−H]⁻	8.56	C₂₇H₃₀O₁₅	Kaempferol 3-rutinoside	447	A	CZSZ, CBS
84	61.03	134.220 3	[M−H]⁻	5.39	C₁₀H₁₄	2-Ethyl-1, 4-dimethylbenzene	135, 105, 91, 77	E	MMH
85	61.44	283.061 9	[M−H]⁻	5.46	C₁₆H₁₂O₅	Oroxylin A	283, 268	A	HQ
86	61.87	465.105 6	[M+H]⁺	6.56	C₂₁H₂₀O₁₂	Hyperoside	303, 257	A	CBS
87	62.55	753.220 2	[M−H]⁻	6.08	C₃₄H₄₂O₁₉	1, 2-Disinapoylgentiobiose	223, 190	E	CLFZ
88	62.87	151.111 8	[M+H]⁺	2.59	C₉H₁₃NO	Phenylpropanolamine	134, 117	C	MMH
89	63.19	463.085 2	[M−H]⁻	6.59	C₂₁H2₀O₁₂	Herbacetin 7-glucoside	301, 271	A	MMH
90	63.56	338.256 4	[M+H]⁺	2.59	C₂₂H₄₃NO	Erucylamide	321, 303, 296	E	CBS
91	63.57	463.089 5	[M+H]⁺	5.43	C₂₁H₁₈O₁₂	Luteolin-7-O-glucuronide	287, 463	A	CZSZ
92	63.76	137.023 8	[M−H]⁻	4.76	C₇H₆O₃	Protocatechualdehyde	137, 109	E	CZSZ
93	65.78	547.140 8	[M−H]⁻	9.22	C₂₆H₂₈O₁₃	Chrysin 6-C-glucoside 8-C-α-Larabinoside	487, 457, 427, 367	A	HQ
94	65.91	624.193 4	[M−H]⁻	7.52	C₂₉H₃₆O₁₅	Acteoside	623, 461, 179, 161, 135	E	YCQZ, HQ
95	66.43	289.089 4	[M+H]⁺	5.46	C₁₅H₁₂O₆	Carthamidin	169, 147	A	HQ
96	66.47	251.092 2	[M+Na]⁺	5.29	C₁₄H₂₈O₂	Tetradecanoic acid	251, 215, 159, 145, 131	E	DKXR
97	66.56	181.564 9	[M−H]⁻	5.22	C₆H₁₄O₆	Sorbitol	119, 101, 89	E	YCQZ
98	69.52	639.561 3	[M−H]⁻	5.69	C₂₉H₃₆O₁₆	Plantainoside D	621, 529	B	YCQZ
99	71.03	195.587 4	[M+H]⁺	8.23	C₁₂H₁₈O₂	Cnidilide	177, 149, 131, 125	E	CBS
100	72.09	297.079 1	[M+H]⁺	2.17	C₁₃H₁₂O₈	Caffeoylmalic acid	173	D	MMH
101	72.61	461.070 7	[M−H]⁻	4.15	C21H18O12	Scutellarin	285, 267, 239, 119, 113	A	CZSZ, HQ
102	74.16	205.589 6	[M+H]⁺	6.13	C₁₂H₁₂O₃	3-Butylidene-7-hydroxyphthalide	187, 147	B	CBS
103	74.23	415.214 6	[M+H]⁺	7.6	C₂₄H₃₀O₆	Bis (4-ethylbenzylidene) sorbitol	119	E	DKXR
104	74.91	509.486 3	[M−H]⁻	4.23	C₂₄H₃₀O₁₂	Mudanpioside D	509, 463, 121, 77	B	CBS
105	75.13	479.563 2	[M+H]⁺	1.03	C₂₃H₂₆O₁₁	Plantainoside A	461, 334, 307, 263, 179	B	YCQZ
106	76.17	153.031 2	[M−H]⁻	3.5	C₁₀H₁₈O	Terpineol	180, 153	B	DKXR
107	76.17	361.589 6	[M+H]⁺	2.59	C₁₈H₁₆O₈	Rosmarinic acid	197, 179, 161, 135, 133	E	CZSZ, CBS
108	76.36	431.525 9	[M−H]⁻	5.03	C₂₁H₂₀O₁₀	Apigenin-7-O-β-D-glucoside	151, 239, 240, 268, 432	A	HQ
109	76.95	647.139 3	[M−H]⁻	7.15	C₃₀H₃₂O₁₄S	Benzoylpaeoniflorin sulfite	259	B	CBS
110	77.36	191.018 3	[M−H]⁻	1.2	C₁₃H₂₀O	beta-Ionone	191, 111	B	DKXR
111	77.36	369.236 5	[M+H]⁺	5.26	C₂₁H₂₄N₂O₄	18, 19-Dehydrocorynoxinic acid	369, 351	E	GT
112	79.99	295.060 9	[M+Na]⁺	1.02	C₁₆H₃₂O₃	2-Hydroxypalmitic acid	295, 277, 259, 231	E	DKXR
113	79.99	383.198 3	[M+H]⁺	10.08	C₂₂H₂₆N₂O₄	Corynoxeine	351, 201	C	GT
114	80.05	447.123 1	[M−H]⁻	2.01	C₂₁H₂₀O₁₁	Plantaginin	284	A	YCQZ
115	80.06	325.006 3	[M−H]⁻	5.46	C₁₅H₁₈O₈	4-O-beta-Glucopyranosyl-cis-coumaric acid	163, 119	D	CZSZ
116	80.23	357.147 9	[M+H]⁺	0.28	C₂₀H₂₀O₆	Coniferylferulate	311, 149	E	CBS
117	82.55	269.048 9	[M−H]⁻	6.59	C₁₅H₁₀O₅	Baicalein	241, 197	A	HQ
118	82.62	445.074 6	[M−H]⁻	6.88	C₂₁H₁₈O₁₁	Baicalin	891, 445, 269, 251	A	HQ
119	83.29	615.421 3	[M−H]⁻	8.46	C₃₀H₃₂O₁₄	Mudanpioside H	615, 493, 169	B	CBS
120	84.50	291.088 5	[M+H]⁺	1.02	C₁₅H₁₄O₆	Catechin	161, 123, 139	A	DKXR
121	84.55	385.214 9	[M+H]⁺	4.89	C₂₂H₂₉N₂O₄	Rhynchophylline	353, 268, 160, 110	C	GT
122	84.64	286.080 1	[M+H]⁺	2.05	C₁₇H₁₉NO₃	Coclaurine	286, 269, 254, 237, 209	C	DKXR
123	84.64	385.214 9	[M+H]⁺	4.89	C₂₂H₂₈N₂O₄	Isorhynchophylline	353, 268, 160, 110	C	GT
124	85.13	178.001 2	[M−H]⁻	2.36	C₉H₆O₄	Cichorigenin	149, 133, 105	E	CZSZ
125	85.13	313.269 9	[M−H]⁻	4.09	C₁₇H₁₄O₆	Skullcapflavon Ⅰ	313, 298, 113	A	HQ
126	85.16	473.158 9	[M+H]⁺	1.05	C₃₀H₄₈O₄	Hederagenin	200, 270	B	CZSZ
127	85.16	406.468 1	[M−H]⁻	3.89	C₁₁H₂₁NO₉S₃	3-Methylthiopropyl glucosinolate	259, 195, 96, 74	E	CLFZ
128	85.16	651.289 6	[M−H]⁻	8.99	C₃₁H₄₀O₁₅	Martynoside	605, 475, 175	E	YCQZ
129	85.23	639.853 6	[M−H]⁻	1.25	C2₉H₃₆O₁₆	Plantamajoside	477, 179, 161, 135, 315	B	YCQZ
130	85.26	487.100 2	[M+H]⁺	5.01	C₂₁H₂₈O₁₃	cis-Tanoside F	179, 135	E	YCQZ
131	85.36	315.410 2	[M−H]⁻	4.69	C₁₃H₁₆O₉	1-O-(3, 4-Dihydroxybenzoyl)-beta-D-glucopyranose	152, 108	D	CLFZ
132	85.40	421.235 6	[M−H]⁻	1.11	C₁₉H₁₈O₁₁	Isomangiferin	/	A	YCQZ
133	85.46	301.567 8	[M−H]⁻	8.96	C₁₅H₁₀O₇	Quercetin	178, 151	A	CZSZ
134	85.56	593.788 5	[M+H]⁺	4.56	C₂₈H₃₂O₁₄	Linarin	565, 447, 285	A	CZSZ
135	86.70	447.095 6	[M−H]⁻	7.39	C₂₁H₂₀O₁₁	Dihydrobaicalin	271, 243	A	HQ
136	87.18	133.013 9	[M−H]⁻	−2.9	C₄H₆O₅	Malic acid	115, 133	E	DKXR
137	87.18	612.495 0	[M+2H]⁺	6.9	C₂₇H₃₀O₁₆	Rutin	589, 566	A	HQ
138	87.39	257.045 8	[M+H]⁺	8.46	C₁₅H₁₂O₄	Isoliquiritigenin	239, 137	A	HQ
139	87.46	423.893 5	[M+H]⁺	10.25	C₃₀H₄₆O	Glochidone	405, 215	B	CZSZ
140	87.98	273.077 1	[M+H]⁺	7.15	C₁₅H₁₂O₅	Naringenin	169, 131	A	MMH, CBS
141	87.98	273.098 7	[M+H]⁺	7.16	C₁₅H₁₂O₅	Pinobanksin	273, 151	A	HQ
142	88.23	623.589 6	[M−H]⁻	5.13	C₂₉H₃₆O₁₅	Forsythiaside A	461, 161, 135	D	YCQZ
143	88.75	445.045 6	[M−H]⁻	6.23	C₂₁H₁₈O₁₁	Glychionide A	445, 269	A	HQ
144	89.45	583.269 7	[M−H]⁻	2.58	C₃₀H₃₂O₁₂	Benzoylpaeoniflorin	431, 387, 121	B	CBS
145	89.46	463.469 8	[M−H]⁻	5.11	C₁₆H₂₀N₂O₁₀S₂	4-Hydroxy-3-indolylmethyl glucosinolate	285, 267, 195, 96, 74	E	CLFZ
146	89.56	125.465 0	[M−H]⁻	2.56	C₆H₆O₃	Pyrogallol	79, 96	E	CBS
147	89.57	209.585 6	[M+H]⁺	5.69	C₁₂H₁₆O₃	β-Asarone	191, 163, 153	E	CBS
148	90.13	299.054 9	[M−H]⁻	3.87	C₁₆H₁₂O₆	Tenaxin Ⅱ	283, 227	A	HQ
149	90.13	299.054 9	[M−H]⁻	3.59	C₁₆H₁₂O₆	Kaempferide	299, 228	A	MMH, CBS
150	90.18	445.112 5	[M−H]⁻	3.23	C₂₂H₂₂O₁₀	Wogonin-5-O-D-glucoside	269	A	HQ
151	90.59	227.489 6	[M+H]⁺	2.59	C₁₂H₂₂N₂O₂	Cyclo (Leu-Leu)	209, 114	E	CZSZ
152	90.88	307.058 5	[M+H]⁺	2.18	C₁₅H₁₄O₇	Leucocyanidin	307, 163, 139, 121	A	MMH
153	91.26	183.563 1	[M−H]⁻	5.69	C₁₁H₂₀O₂	2-Undecenoic acid	207, 192, 175, 147, 133, 77	E	DKXR
154	91.26	455.213 6	[M+H]⁺	5.69	C₃₀H₄₈O₃	Oleanolic acid	377	B	GT
155	92.07	459.105 6	[M−H]⁻	7.59	C₂₂H₂₀O₁₁	Oroxyloside	283, 169	A	HQ
156	92.08	429.169 6	[M−H]⁻	5.16	C₂₁H₁₈O₁₀	Chrysin-7-O-β-D glucoronide	253, 175	A	HQ
157	92.15	283.059 2	[M−H]⁻	6.88	C₁₆H₁₂O₅	Wogonin	268, 240, 239, 167, 139	A	HQ
158	95.27	419.156 0	[M+H]⁺	1.28	C₂₁H₂₂O₉	Liquiritin	419, 257, 239, 211, 147	A	DKXR
159	95.27	369.194 9	[M+H]⁺	6.52	C₂₂H₂₈N₂O₃	Hirsutine	543, 497, 265	C	GT
160	96.05	461.109 7	[M+H]⁺	4.15	C₂₂H₂₀O₁₁	Apigenin-7-O-methylglucuronide	461, 271	A	HQ
161	96.14	193.256 4	[M+H]⁺	1.56	C₁₂H₁₆O₂	Sedanenolide	175, 147, 137, 93	B	CBS
162	97.11	629.784 6	[M−H]⁻	1.56	C₃₁H₃₄O₁₄	Mudanpioside B	583, 553, 431, 165, 121, 77	B	CBS
163	97.56	313.065 9	[M−H]⁻	6.59	C₁₇H₁₄O₆	Dihydroxy-dimethoxyflavone	298, 255	A	HQ
164	98.56	783.154 8	[M−H]⁻	5.12	C₃₇H₃₆O₁₉	3′, 6′-di-O-Galloylpaeoniflorin	783, 765, 631, 465, 313	B	CBS
165	99.56	451.896 3	[M−H]⁻	8.59	C₁₃H₂₅NO₁₀S₃	1-Thio-β-D-glucopyranose 1-(6-(methylsulfinyl)-N-(sulfooxy)hexanimi date)	386, 259, 208, 96, 74	E	CLFZ
166	100.26	300.256 9	[M+H]⁺	3.65	C₁₈H₃₇NO₂	Palmidrol	283, 255	E	CBS
167	101.79	115.891 1	[M−H]⁻	2.56	C₅H₈O₃	Levulinic acid	117, 102, 89, 74	E	DKXR, CBS
168	101.79	355.203 4	[M+H]⁺	5.1	C₂₁H₂₆N₂O₃	Yohimbine	355, 212, 144	C	GT
169	103.47	499.207 9	[M+H]⁺	6.84	C₂₆H₃₀N₂O₈	Strictosamide	337, 267	C	GT
170	104.32	432.256 3	[M+H]⁺	6.77	C₁₉H₂₈O₁₁	Benzyl-β-gentiobioside	327, 255	E	CLFZ
171	104.75	167.071 3	[M+H]⁺	5.12	C₉H₁₀O₃	Paeonol	167, 149, 121	D	CBS
172	105.25	287.145 6	[M−H]⁻	8.96	C₁₅H₁₂O₆	Dihydrokaempferol	287, 93, 193, 175	A	CBS
173	107.89	477.120 3	[M−H]⁻	50.56	C₂₃H₂₆O₁₁	Calceolarioside A	360, 325, 290, 203, 163	E	YCQZ
174	108.36	477.889 9	[M−H]⁻	64.88	C₂₃H₂₆O₁₁	Calceolarioside B	/	E	YCQZ

No.	Compound	Degree	Origin
1	Baicalein	65	HQ
2	Tenaxin Ⅱ	65	HQ
3	Skullcapflavon Ⅱ	63	HQ
4	Skullcapflavon Ⅰ	62	HQ
5	Glabridin	60	DKXR
6	Quercetin	60	CZSZ
7	Dihydroxy-dimethoxyflavone	60	HQ
8	Matairesinol	59	DKXR
9	Luteolin	59	CZSZ
10	Wogonin	59	HQ
11	Oroxylin A	59	HQ
12	Myricetin	58	GT
13	Yohimbine	57	GT
14	Kaempferide	56	MMH, CBS
15	Naringenin	52	MMH, CBS
16	Sinapine thiocyanate	52	CLFZ
17	Rhynchophylline	51	GT
18	Isorhynchophylline	51	GT
19	Corynoxeine	50	GT
20	Hirsutine	47	GT

No.	Compound	Degree	Origin
1	Baicalein	65	HQ
2	Tenaxin Ⅱ	65	HQ
3	Skullcapflavon Ⅱ	63	HQ
4	Skullcapflavon Ⅰ	62	HQ
5	Glabridin	60	DKXR
6	Quercetin	60	CZSZ
7	Dihydroxy-dimethoxyflavone	60	HQ
8	Matairesinol	59	DKXR
9	Luteolin	59	CZSZ
10	Wogonin	59	HQ
11	Oroxylin A	59	HQ
12	Myricetin	58	GT
13	Yohimbine	57	GT
14	Kaempferide	56	MMH, CBS
15	Naringenin	52	MMH, CBS
16	Sinapine thiocyanate	52	CLFZ
17	Rhynchophylline	51	GT
18	Isorhynchophylline	51	GT
19	Corynoxeine	50	GT
20	Hirsutine	47	GT

基于液质联用技术、网络药理学及实验验证探讨XKZ2305颗粒治疗小儿咳喘症的作用机制

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王力媛 ¹ , 高新雨 ²^,³^,⁴ , 刘秋容 ²^,³^,⁴ , 张珂蒙 ¹ , 周福军 ²^,³^,⁴ , 龚苏晓 ²^,³^,⁴ , 田成旺 ²^,³^,⁴ , 马儒 ⁵^,^* , 陈金鹏 ²^,³^,⁴^,^*

药学学报 | 专题报道: 儿童哮喘中医药防治的机制与转化研究 2026,61(9): 3245-3260

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药学学报 |专题报道: 儿童哮喘中医药防治的机制与转化研究 2026 , 61 (9) : 3245 -3260

基于液质联用技术、网络药理学及实验验证探讨XKZ2305颗粒治疗小儿咳喘症的作用机制

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王力媛¹, 高新雨²^,³^,⁴, 刘秋容²^,³^,⁴, 张珂蒙¹, 周福军²^,³^,⁴, 龚苏晓²^,³^,⁴, 田成旺²^,³^,⁴, 马儒⁵^,^*, 陈金鹏²^,³^,⁴^,^*

作者信息

¹天津中医药大学, 天津 301617

²天津药物研究院, 和光中药科技 (天津) 有限公司, 天津 300462

³天津市中药质量标志物重点实验室, 天津 300462

⁴药物成药性评价与系统转化全国重点实验室, 天津 300462

⁵联成迅康 (珠海横琴) 药业有限公司, 广东珠海 519000

通讯作者:

陈金鹏， E-mail: chenjp@tjipr.com

马儒， E-mail: maruok@163.com

作者简介:

作者贡献:

王力媛进行整体实验、数据分析并撰写论文; 高新雨、刘秋容、张珂蒙、周福军、龚苏晓参与整体实验和数据分析; 田成旺、马儒参与指导实验方案设计; 陈金鹏参与指导实验方案设计、数据分析并修改论文。

Exploring the mechanism of XKZ2305 Granules in treating pediatric cough and asthma syndrome based on chemical composition analysis and integration of network pharmacology combined with experimental validation

Li-yuan WANG¹, Xin-yu GAO²^,³^,⁴, Qiu-rong LIU²^,³^,⁴, Ke-meng ZHANG¹, Fu-jun ZHOU²^,³^,⁴, Su-xiao GONG²^,³^,⁴, Cheng-wang TIAN²^,³^,⁴, Ru MA⁵^,^*, Jin-peng CHEN²^,³^,⁴^,^*

Affiliations

¹Tianjin University of Traditional Chinese Medicine, Tianjin 301617, China

²Tianjin Institute of Materia Medica, Heguang Chinese Medicine Technology (Tianjin) Co., Ltd., Tianjin 300462, China

³Tianjin Key Laboratory of Quality Markers of Traditional Chinese Medicine, Tianjin 300462, China

⁴National Key Laboratory of Drug Druggability Evaluation and Systematic Transformation, Tianjin 300462, China

⁵Liancheng Xunkang (Zhuhai Hengqin) Pharmaceutical Co., Ltd., Zhuhai 519000, China

出版时间: 2026-09-12 doi: 10.16438/j.0513-4870.2025-1453

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摘要

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为探究XKZ2305颗粒治疗小儿咳喘症的潜在活性成分和作用机制, 建立HPLC-Q-TOF-MS/MS方法, 采用电喷雾离子源(ESI) 正负离子扫描模式, 对XKZ2305颗粒中的化学成分进行快速解析。结果共鉴别出174个化合物, 其中黄酮类46种、萜类30种、生物碱类16种、酚酸类18种以及其他成分64种。结合网络药理学分析, 通过中药系统药理数据库及分析平台(TCMSP)、Swiss Target Prediction、GeneCards、人类孟德尔遗传数据库(OMIM) 数据库分别获取化学成分靶点和疾病靶点, 进行相应筛选后获得交集靶点451个, 通过STRING数据库进行蛋白互作分析(PPI), 利用Cytoscape软件进行PPI及药物?成分?靶点网络的可视化处理并获取核心靶点29个。利用DAVID数据库进行GO (gene ontology) 功能富集和KEGG (Kyoto encyclopedia of genes and genomes) 通路分析, 证明XKZ2305颗粒治疗小儿咳喘症的机制主要是黄芩素、汉黄芩素、槲皮素、芥子碱硫氰酸盐和钩藤碱等成分作用于TP53、IL6、IL1B、HIF1A、GAPDH、BCL2和AKT1等靶点, 以HIF-1信号通路、PI3K/AKT信号通路、AGE-RAGE信号通路、MAPK信号通路, 实现多组分?多靶点?多通路联合作用。动物实验显示, XKZ2305颗粒能明显改善卵清白蛋白(OVA) 诱导哮喘幼龄小鼠的行为学变化, 明显降低模型小鼠血清中IgE含量以及BALF中TNF-α含量, 有升高IL-10含量的趋势, 改善OVA诱导哮喘引起的炎症, 进而缓解小儿咳喘病症。本实验所涉及动物实验已获得天津药物研究院实验动物管理与使用委员会的批准(No: TIPR-2025-2361PD9)。

关键词

XKZ2305颗粒 / 小儿咳喘症 / 化学成分 / 网络药理学 / 药效学

Abstract

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The study aims to investigate the potential active ingredients and mechanism of action of XKZ2305 Granules in treating pediatric cough and asthma syndrome. An HPLC-Q-TOF-MS/MS method was established to rapidly identify the chemical constituents in XKZ2305 Granules using electrospray ionization (ESI) source in both positive and negative ion scanning modes. A total of 174 compounds were identified, including 46 flavonoids, 30 terpenoids, 16 alkaloids, 18 phenolic acids, and 64 other components. Integrated with network pharmacology analysis, potential targets of these chemical components and asthma-related disease targets were retrieved from the TCMSP, Swiss Target Prediction, GeneCards, and OMIM databases, respectively. After screening, 451 overlapping targets were obtained. Protein-protein interaction (PPI) analysis was performed using the STRING database, and visualization of the PPI network and the "herb-compound-target" network was conducted using Cytoscape software, leading to the identification of 29 core targets. GO (gene ontology) functional enrichment and KEGG (Kyoto encyclopedia of genes and genomes) pathway analyses via the DAVID database revealed that the therapeutic mechanism of XKZ2305 Granules against pediatric cough and asthma syndrome components, including baicalein, wogonin, quercetin, sinapine thiocyanate, and rhynchophylline, act on targets such as TP53, IL6, IL1B, HIF1A, GAPDH, BCL2, and AKT1, primarily through the HIF-1, PI3K/AKT, AGE-RAGE, and MAPK signaling pathway. Animal experiments demonstrated that XKZ2305 Granules significantly improved behavioral changes in juvenile asthmatic mice induced by ovalbumin (OVA), markedly reduced serum IgE levels and TNF-α content in bronchoalveolar lavage fluid (BALF), showed a trend toward increasing IL-10 levels, alleviated OVAinduced airway inflammation, and consequently mitigated pediatric asthma and cough syndrome. This study comprehensively identified the chemical constituents of XKZ2305 Granules. The animal experiments involved in this study have been approved by the Institutional Animal Care and Use Committee of Tianjin Institute of Pharmaceutical Research (Approval No.: TIPR-2025-2361PD9).

Key words

XKZ2305 Granule / pediatric asthma and cough syndrome / chemical constituent / network pharmacology / pharmacodynamics

引用本文

王力媛, 高新雨, 刘秋容, 张珂蒙, 周福军, 龚苏晓, 田成旺, 马儒, 陈金鹏. 基于液质联用技术、网络药理学及实验验证探讨XKZ2305颗粒治疗小儿咳喘症的作用机制. 药学学报, 2026 , 61 (9) : 3245 -3260 . DOI: 10.16438/j.0513-4870.2025-1453

Li-yuan WANG, Xin-yu GAO, Qiu-rong LIU, Ke-meng ZHANG, Fu-jun ZHOU, Su-xiao GONG, Cheng-wang TIAN, Ru MA, Jin-peng CHEN. Exploring the mechanism of XKZ2305 Granules in treating pediatric cough and asthma syndrome based on chemical composition analysis and integration of network pharmacology combined with experimental validation[J]. Acta Pharmaceutica Sinica, 2026 , 61 (9) : 3245 -3260 . DOI: 10.16438/j.0513-4870.2025-1453

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小儿咳喘症(pediatric cough and asthma syndrome, PCAS) 是儿科临床常见的呼吸系统疾病, 在中医理论中通常与外感风邪、内生痰热等因素相关, 临床主要表现为发热、咳嗽、气喘、痰黄黏稠等症状^[1], 若治疗不及时或不当, 则易导致脓胸、脓气胸、脑水肿、呼吸衰竭和心力衰竭等并发症, 严重影响儿童健康^[2]。目前西医治疗主要采取止咳、化痰、抗炎、抗感染等对症疗法, 孟鲁司特钠作为常用的白三烯受体拮抗剂, 能够有效抑制炎症介质释放, 缓解气道高反应性, 改善患儿临床症状^[3]。但单一药物治疗存在起效慢、复发率高及长期用药依从性差等局限性^[4], 且有研究表明儿童长期服用该药物会引起情绪行为异常, 如易怒、注意力不集中和睡眠障碍等不良反应以及皮疹、血管性水肿等皮肤疾病^{[5, 6]}。目前, 中医将小儿咳喘症归为喘嗽、哮喘范畴, 认为其病机主要为痰热壅肺、肺气失宣^[7], 《景岳全书》载“: 六气皆令人咳, 风寒为主”^[8]。《素问·咳论篇》云“: 五脏六腑皆令人咳, 非独肺也”, 《景岳全书·咳嗽》亦云“: 内伤之咳, 先因伤脏, 故必由脏以及肺, 此脏为本而肺为标也”^[9]。说明本病的发生在外与感受邪气有关, 在内与脏腑功能内伤失调有关^[10], 治疗需以轻疏外邪、清热化痰、宣肺平喘为核心。中药具有多成分、多靶点的特点, 对该病具有良好的治疗或辅助治疗效果。而对于小儿支气管哮喘急性发作期, 目前市面上可供选择的中成药仅有小儿定喘口服液, 适用于中医辨证属痰热壅肺证的患儿^[11]。

XKZ2305颗粒可降气平喘, 止咳化痰, 解表清里, 适用于3~12岁轻中度哮喘急性发作外寒内热证儿童患者, 由蜜麻黄、燀苦杏仁、黄芩、炒紫苏子、炒莱菔子、盐车前子、炒白芍、钩藤、盐车前子组方而成。处方中蜜麻黄、燀苦杏仁和黄芩为君药, 蜜麻黄其味辛性温, 归肺、膀胱经, 发汗散寒, 宣肺平喘, 润肺止咳, 燀苦杏仁味苦性微温, 具降气止咳平喘之功, 黄芩味苦性寒, 清热燥湿, 泻火解毒; 炒紫苏子独入肺经, 降气化痰, 止咳平喘, 炒莱菔子消食除胀, 降气化痰, 盐车前子清热化痰清肝明目, 三者共为臣药, 可助君药清热泻火, 止咳平喘; 炒白芍柔肝止痛, 平抑肝阳, 钩藤息风定惊, 清热平肝, 共为佐使药; 诸药合用, 共奏宣肺化痰、清热平喘之功。

为了揭示XKZ2305颗粒治疗小儿咳喘症的药效物质基础及作用机制, 本研究通过高效液相色谱−四极杆−飞行时间串联质谱(HPLC-Q-TOF-MS/MS) 和网络药理学方法并结合动物实验, 探究XKZ2305颗粒改善小儿咳喘症的潜在药效成分及作用机制, 为XKZ2305颗粒深入开发利用提供依据。

材料与方法

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仪器

X500R QTOF型液相色谱−质谱联用仪(美国AB Sciex公司); ML104/02型电子天平[梅特勒−托利多仪器(上海) 有限公司]; BT125D型电子天平[赛多利斯科学仪器(北京) 有限公司]; DNA103A型电子天平、ECC2201型电子天平(南京伯尼塔科学仪器有限公司); YLS-8A型多功能诱咳引喘仪(济南益延科技发展有限公司); RT-6100型酶标仪(深圳雷杜生命科学股份有限公司); Sorvall ST 17R型台式冷冻离心机(美国Thermo Scientific); EMS-8C型恒温、数显、加热磁力搅拌器(天津市欧诺仪器仪表有限公司); HistoCore Arcadia H+C石蜡包埋机[徕卡显微系统(上海) 有限公司]; Aperio GT450病理切片扫描仪(德国Leica Biosystems Imaging Inc.)。

试剂与试药

蜜麻黄(53024005)、炒紫苏子(32524003)、炒莱菔子(24924003) 购自河北仁心药业有限公司; 燀苦杏仁(240031, 安徽普仁中药饮片有限公司); 黄芩(C3022406001)、钩藤(C0542403001)、盐车前子(C4822311003)、炒白芍(C3992406001) 购自河北荷花池药业有限公司; 色谱纯甲醇(梯度级, 240428)、色谱纯乙腈(梯度级, 240107) 购自天津康科德科技有限公司; 色谱纯甲酸[HPLC级, 214911, 赛默飞世尔科技(中国) 有限公司]; 卵清白蛋白(OVA, 54240511003) 和磷酸盐缓冲液(PBS, 20230911) 购自索莱宝生物科技有限公司; 完全弗氏佐剂(CFA, SLCL6285, 美国Sigma公司); 酶联免疫吸附试验(ELISA) 试剂盒免疫球蛋白E (IgE, Feb2025)、ELISA试剂盒肿瘤坏死因子-α (TNF-α, Feb2025)、ELISA试剂盒白介素-4 (IL-4, Feb2025)、ELISA试剂盒IL-10 (Feb2025)、ELISA试剂盒干扰素-γ (IFN-γ, Feb2025) 购自上海酶联生物科技有限公司; Harris苏木素染色液(C240903)、伊红染色液(醇溶性, C240701) 购自珠海贝索生物技术有限公司; 孟鲁司特钠颗粒(K2309051, 江苏正大丰海制药有限公司); 小儿定喘口服液[241022, 荣昌制药(淄博) 有限公司]。

动物

3日龄SPF级BALB/c小鼠, 雌雄各半, 购自北京维通利华实验动物技术有限公司, 许可证号: SCXK (京) 2021-0006, 经天津药物研究院实验动物管理与使用委员会的批准(No.: TIPR-2025-2361PD9), 饲养于天津天诚药物评价有限公司屏障级动物房, 温度20~25 ℃, 相对湿度50%~60%, 12 h/12 h照明黑暗交替, 动物自由摄食和饮水。

XKZ2305颗粒制备

处方饮片(盐车前子包煎)加10倍量水, 浸泡1 h, 提取3次, 每次2 h, 合并3次滤液; 减压浓缩后减压干燥; 所得浸膏粉, 加辅料适量, 混合均匀, 干法制粒, 即得。

化学成分分析供试品溶液制备

取XKZ2305颗粒混匀, 研细, 取约2 g, 精密称定, 置于25 mL量瓶中, 加入适量10% 甲醇, 超声处理60 min, 放冷, 加10% 甲醇至刻度, 摇匀, 离心(4 000 r·min^-1) 10 min, 滤过, 精密吸取10 mL至25 mL量瓶, 用10% 甲醇定容, 摇匀, 微孔滤膜(0.22 µm) 滤过, 取续滤液, 即得。

液相色谱−质谱条件

Zafex JX-C18色谱柱(250 mm × 4.6 mm, 5 μm), 柱温30 ℃; 流速1.0 mL·min^-1; 进样5.0 µL, 流动相为0.1%甲酸(A)−乙腈(B), 梯度洗脱(0~10 min, 1% B; 10~15 min, 1%~2% B; 15~20 min, 2%~7% B; 20~25 min, 7%~8% B; 25~40 min, 8% B; 40~50 min, 8%~15% B; 50~70 min, 15%~20% B; 70~100 min, 20%~30% B; 100~101 min, 30%~90% B; 101~109 min, 90% B; 109~110 min, 90%~1% B; 110~125 min, 1% B)。

电喷雾离子源(ESI), 正、负离子采集模式。以氮气为离子源气和气帘气, 离子源气1和2均为60 psi, 气帘气35 psi, 去溶剂气温度600 ℃。正离子模式参数:喷雾电压5.5 kV, 一级谱去簇电压50 V, 一级碰撞能3 V; 二级谱去簇电压80 V, 二级碰撞能30 V。负离子模式参数: 喷雾电压−4.5 kV, 一级谱去簇电压−80 V, 一级碰撞能−3 V; 二级谱去簇电压−80 V, 二级碰撞能−30 V。一级谱的扫描范围为100~1 500 Da, 二级谱的扫描范围均为100~1 200 Da, 累积时间均为0.25 s, 当基峰离子强度高于100 cps时, 触发二级扫描。

数据处理

采用ProteoWizard软件套装中的MSConvert工具, 将AB Sciex OS工作站的原始输出文件(*.wiff2) 转换为通用格式(*.mzML), 再利用MSDial软件对转换后的文件进行去卷积化。总离子流图中各质谱峰的保留时间、信号强度和精确质荷比数据采用MZmine软件导出, 去卷积化后的质谱数据由MS-Dial软件导出, 最后将精确质荷比输入至MS Interpreter软件中估算对应的分子式。

主要活性成分及靶点筛选

基于液质联用数据结果, 将鉴定得到的化学成分通过PubChem (https://pubchem.ncbi.nlm.nih.gov/) 数据库检索SMILE式, 进一步利用Swiss Target Prediction (http://swisstargetprediction.ch/) 数据库, 设定选择物种类型为homo sapiens, 根据化学成分作用于该靶点产生活性的概率(即prob‐ ability > 0) 阈值作为筛选条件以预测其作用靶点。如有化合物在Swiss Target Prediction数据库无法查询, 则通过中药系统药理数据库及分析平台(Traditional Chinese Medicine Systems Pharmacology Database and Analysis Platform, TCMSP, https://www. tcmsp-e. com/)“Related Targets”收集药效成分相关靶点, 再通过UniProt (https://www.uniprot.org/) 数据库将其转换为GeneSymbol。

疾病相关靶点获取

以lung heat in children、asthma in children和cough in children为关键词, 在Genecards (https://www.tcmsp-e.com/) 数据库和人类孟德尔遗传数据库(Online Mendelian Inheritance in Man, OMIM)进行检测。经Genecards数据库检索得到的相关靶点根据“Relevance score”值进行两次中位数筛选后, 与OMIM数据库得到的相关靶点合并剔除重复基因, 即得小儿咳喘症的疾病靶点库。

蛋白互作分析(PPI) 及“药物−成分−靶点−疾病”网络构建、核心活性成分获取

为明确XKZ2305颗粒的活性成分与疾病相关靶点间的相互作用, 将上述获取的成分和疾病靶点, 导入微生信平台(https://www. bioinformatics.com.cn/) 绘制文恩图, 获取活性成分和疾病交集靶点。将得到的交集靶点导入STRING 11.0数据库, 筛选条件为homo sapiens物种, 置信度为0.70, 绘制PPI网络图, 然后使用Cytoscape3.7.1软件相关功能对该网络进一步分析。利用CytoNCA插件进行分析, 筛选条件为大于介数中心性(BC)、接近中心性(CC)、连接度(degree)、特征向量中心性(EC)、本地平均连接度方法(LAC) 和网络中心度(NC) 各项中位数, 经两次筛选得到相关靶点; 再利用Mcode模块分析, 设置Degree Cutoff为2, Node Score Cutoff为0.2, K-Core为2, Max.Depth为100^[12], 确定XKZ2305颗粒治疗小儿咳喘症的相关靶点。将以上筛选得到的靶点取并集, 即为XKZ2305颗粒治疗小儿咳喘症的核心靶点。将活性成分及其靶点的基因信息导入Cytoscape 3.7.1软件中进行可视化处理, 利用CytoNCA插件进行网络分析, 取Degree值前二十的活性成分作为XKZ2305颗粒的核心活性成分。

GO功能与KEGG通路富集分析

利用DAVID数据库(https://davidbioinformatics.nih.gov/) 对获取的交集靶点进行Gene ontology (GO) 功能富集与KEGG通路富集分析。在GO功能分析中, 依次进行生物过程(BP)、细胞组成(CC) 和分子功能(MF) 分析, 根据−Log₁₀ (P value) 值排名前十筛选出富集条目, 绘制GO分析图。Kyoto encyclopedia of genes and genomes (KEGG) 通路富集分析以−Log₁₀ (FDR) 值排名前25的通路进行可视化分析。根据靶点与KEGG信号通路间的关系, 使用Cytoscape3.7.1软件构建“药物−活性成分−核心靶点−通路”网络图。

药效学供试品溶液制备

XKZ2305颗粒(浸膏粉) 含量为每克浸膏粉相当于5.60 g生药。精密称取XKZ2305颗粒(浸膏粉) 置于研钵中, 加入少量超纯水充分研磨, 转移至量筒中, 以超纯水重复清洗研钵至基本无药液残留, 最后加入超纯水至20 mL, 得终浓度分别为0.31、0.63、1.25 g·mL^-1 (按原生药克重计) 的药液。孟鲁司特钠颗粒规格为8 mg·g^-1, 取孟鲁司特钠颗粒1袋(0.5 g: 4 mg) 置于研钵中, 加入少量超纯水充分研磨, 转移至量筒中, 以超纯水重复清洗研钵至基本无药液残留, 最后加入超纯水至26.7 mL, 所得即为终浓度约为0.15 mg·mL^-1的药液。小儿定喘口服液规格为每1 mL相当于饮片1.0 g; 取9.0 mL小儿定喘口服液加入适量超纯水混合均匀, 继续加入适量超纯水至20 mL, 所得即为终浓度为0.45 g·mL^-1 (按原生药克重计) 的药液。

模型构建与给药

选用健康BALB/c小鼠28窝(每窝为1只母鼠伴随雌雄共5只崽鼠), 3日龄, 雌雄各半, 适应性饲养5天, 于适应期末日(7日龄), 随机选取4窝为正常对照组, 其余动物分别于小鼠腹部皮下及左、右背部皮下各注射100 μL OVA致敏液致敏, 后将动物放入YLS-8A多功能引喘仪中, 由仪器喷雾8% OVA雾化液雾化激发, 每次30 min, 连续7天, 见图 1。本实验设7个组, 分别为正常对照组(Con组)、模型对照组(Mod组)、XKZ2305样品(剂量设置分别为12.5、25、50 g·kg^-1)、孟鲁司特钠颗粒组(6.0 mg·kg^-1, Mon组) 和小儿定喘口服液组(18.0 g·kg^-1, XRDC组), 每组12只, 雌雄各半。各给药组分别灌胃相应的药物, 给药体积均为每次40 mL·kg^-1, 每日2次, 雾化激发期间伴随给药7天。正常对照组和模型对照组灌胃等体积超纯水。

体征观察及行为学实验

检测小鼠给药前、给药后及给药7天体重。于末次雾化10 min后, 开始观察10 min内各组小鼠的哮喘行为并评分, 计数小鼠抓鼻和挠痒次数, 评分标准为: 无抓鼻、挠痒等动作或其他哮喘行为学表现记0分; 抓鼻或挠痒1~3次, 口唇紫绀、呼吸急促等轻微哮喘行为学记1分; 抓鼻或挠痒4~6次, 出现呼吸急促、呼吸频率明显加快或焦躁不安等哮喘典型症状记2分; 抓鼻或挠痒7次及7次以上, 出现严重的呼吸困难、急促点头、腹式呼吸、俯状不动、反应迟钝等哮喘症状记3分。

血清中免疫球蛋白含量测定

于末次给药结束后, 小鼠禁食过夜, 眼球取血, 离心(3 500 r·min^-1) 10 min, 取上清, 按相应试剂盒说明书, 采用ELISA法检测IgE。

肺泡灌洗液(BALF) 中炎症因子含量测定

于采血后, 剪开小鼠胸腔, 从气管插入注射器, 吸取0.5 mL预冷PBS经气管进入左肺, 反复抽吸3次, 回收的液体放入EP管内收集, 重复3次。收集到的BALF离心(1 500 r·min^-1、4 ℃) 10 min, 取上清, 按相应试剂盒说明书, 采用ELISA法检测BALF中的TNF-α、INF-γ、IL-4、IL-10。

组织病理学检查

剪取未灌洗的小鼠右肺, 10%中性甲醛固定, 石蜡包埋, HE染色, 进行组织病理学检查。

数据处理

计量资料以均值±标准误(mean ± SEM) 表示, 采用SPSS 25.0软件进行统计。方差齐做单因素方差分析, 有显著差异时采用LSD (least significant difference) 检验进行两两比较; 方差不齐做KruskalWallis (KW) 非参数检验, 并进行两两比较; LSD、KW检验无显著性差异时进行独立样本t检验进行两两比较。检验水准a为0.05, P＜0.05为差异有统计学意义。

结果与讨论

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1　化学成分分析

基于液相色谱−质谱条件进样, 得到XKZ2305颗粒的质谱总离子流图谱, 见图 2。在XKZ2305颗粒中共鉴定出174个化合物, 包括黄酮类成分46种、萜类成分30种、生物碱类成分16种、酚酸类成分18种和其他成分64种。此外, 对各成分的来源进行了归属, 鉴定结果见表 1。

2　网络药理学分析

2.1　成分−疾病交集靶点获取

汇总Swiss Target Pre‐ diction和TCMSP数据库药物相关靶点以及GeneCards和OMIM数据库小儿肺热、小儿咳嗽和小儿哮喘相关靶点, 去除重复项, 得到药物相关靶点1 023个、疾病相关靶点3 272个。获取XKZ2305活性成分与小儿咳喘症的潜在靶点共451个(图 3A)。

2.2　PPI网络分析及关键靶点获取

通过STRING数据库对交集靶点进行PPI分析绘制蛋白互作网络, 该网络中共包含434个节点、3 893条边, 图中节点颜色深浅和大小与度值有关, 颜色越深, 节点越大, 度值越大, 代表其在网络中的地位越重要。其中通过CytoNCA插件经3次中位数筛选, 得到11个靶点(图 3B); Mcode模块筛选得到25个靶点(图 3C)。取并集后共得到29个核心靶点(图 3D)。其中p53肿瘤抑制基因(TP53)、白介素(IL)-6、IL1B、缺氧诱导因子-1α (HIF1A)、甘油醛-3-磷酸脱氢酶(GAPDH)、B细胞淋巴瘤/白血病-2基因(BCL2) 和蛋白激酶Bα (AKT1) 可能是XKZ2305颗粒治疗小儿咳喘症的核心靶点。

2.3　关键活性成分的获取

构建药物−活性成分−潜在治疗靶点−疾病的关系, 借助Cytoscape3.7.1软件得到XKZ2305颗粒治疗小儿咳喘症的网络图(图 3E)。网络由5 167条边和677个节点(其中8个为药物节点、217个为活性成分节点、451个为靶点和1个为疾病节点) 组成。其中得到的核心成分主要为黄芩素、槲皮素等黄酮类以及芥子碱、钩藤碱等生物碱类成分, 见表 2。

2.4　靶点生物功能富集及通路分析

将获取的交集靶点导入DAVID数据库进行GO功能富集与KEGG通路富集分析, 应用微生信平台绘制GO功能富集条形图和KEGG通路富集气泡图(图 4A、B)。并借助Cytoscape3.7.1软件构建药物−活性成分−核心靶点−通路网络图(图 4C)。GO分析表明, BP主要涉及对异生素刺激的反应、蛋白质磷酸化、凋亡过程负调控等; CC主要涉及质膜、膜筏和受体复合物等; MF主要涉及蛋白质激酶活性、ATP结合和血管内皮生长因子受体活性等。KEGG分析表明, HIF-1信号通路、磷脂酰肌醇3-激酶/蛋白激酶B (PI3K/AKT) 信号通路、高级糖基化终末产物−受体(AGE-RAGE) 信号通路、丝裂原活化蛋白激酶(MAPK) 信号通路、脂质与动脉粥样硬化和化学致癌−受体激活通路等是XKZ2305颗粒治疗小儿咳喘症的主要信号通路。

3　药效学实验

3.1　XKZ2305颗粒对OVA诱导幼龄小鼠哮喘模型体重与哮喘行为学评分的影响

结果显示, 与Con组比较, Mod组小鼠体重显著降低(P＜0.01), 与Mod组比较, 各给药组给药7天体重未见显著性差异(P＞0.05), 见图 5A。给药7天后, 与Con组比较, Mod组小鼠哮喘行为学评分显著升高(P＜0.01), 抓鼻和挠痒次数显著增多(P＜0.01); 与Mod组比较, XKZ2305 25、50 g·kg^-1组小鼠哮喘行为学评分显著降低(P＜0.01), 抓鼻和挠痒次数显著减少(P＜0.05或P＜0.01); Mon组小鼠哮喘行为学评分显著降低(P＜0.01), 抓鼻和挠痒次数显著减少(P＜0.01); XRDC组小鼠哮喘行为学评分显著降低(P＜0.05), 抓鼻和挠痒次数显著减少(P＜0.05), 见图 5B、C。

3.2　XKZ2305颗粒对OVA诱导幼龄小鼠哮喘模型血清中免疫球蛋白含量

结果显示, 与Con比较, Mod组小鼠血清中IgE含量显著升高(P＜0.01); 与Mod组比较, 供试品XKZ2305 50 g·kg-1组小鼠血清内IgE的含量明显降低(P＜0.05), 供试品XKZ2305 25 g·kg^-1组小鼠血清内IgE含量亦有明显降低的趋势, 但未见显著性差异(P＞0.05); Mon组小鼠血清内IgE的含量显著降低(P＜0.01), XRDC组有降低趋势, 未见显著差异(P＞0.05), 见图 5D。

3.3　XKZ2305颗粒对OVA诱导幼龄小鼠哮喘模型BALF中炎症因子含量的影响

试验结果显示, 与Con组比较, Mod组小鼠BALF内TNF-α含量显著升高(P＜0.05)、IL-10的含量有降低的趋势, 未见显著性差异(P＞0.05); 与Mod组比较, 供试品XKZ2305 50 g·kg^-1组小鼠BALF内TNF-α含量明显降低(P＜0.05), IL-10的含量有升高的趋势, 未见显著性差异(P＞0.05); XKZ2305 25 g·kg-1组有相同改善趋势, 未见显著性差异(P＞0.05)。Mon组小鼠BALF内TNF-α含量明显降低(P＜0.05), 对IL-10的含量有升高趋势, 未见显著差异(P＞0.05); XRDC组对TNF-α有降低趋势, 对IL-10的含量有升高趋势, 未见显著差异(P＞0.05), 见图 5E~H。

3.4　对OVA诱导幼龄小鼠哮喘模型肺脏组织病变分级的影响

结果显示, 连续给药7天后剖杀, Con组动物肺脏各级支气管、肺泡管、肺泡结构完整, 细胞形态清晰, 间质未见明显异常。与Con组比较, Mod组12/ 12例动物均见不同程度的间质炎细胞浸润、肺泡隔增宽的肺脏病变症状, 表明造模成功。与Mod组比较, XKZ2305 25、50 g·kg^-1组和Mon、XRDC组肺脏病变均有不同程度的改善(图 5I)。

讨论

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支气管哮喘是由多种诱因引发的常见慢性气道炎症性疾病, 其临床表现以反复发作的喘息、气促为主, 部分患者可能伴随的胸闷或咳嗽等症状, 通常在夜间或凌晨加重, 并具有可逆性^[13]。儿童群体由于自身抵抗力较弱, 免疫系统尚未发育完全, 加之室内外空气污染、季节交替、过敏原暴露和呼吸道感染等多种因素的影响, 易成为支气管哮喘的高发人群, 且该病的发生对患儿的生命健康状态和正常生长发育造成严重的不良影响^[14]。当前研究表明, T2-high炎症尤其多见于儿童哮喘及过敏性哮喘, 该类型以气道嗜酸性粒细胞浸润、辅助性T淋巴细胞2 (Th2) 细胞因子升高、IgE水平升高、气道重塑和气道高反应性为主要特征, 而OVA诱导是目前广泛应用的模拟T2-high型炎症表型的传统哮喘动物模型^[15]。目前, 西医主要以抑制炎症、缓解支气管痉挛、止咳等手段治疗, 通常使用糖皮质激素、支气管舒张剂、白三烯受体拮抗剂等药物^[16]。中医药具有悠久的小儿咳喘防治历史, 其标本兼治、综合治疗的独特优势使其在小儿咳喘的防治中发挥了巨大的作用。近年来, 口服中成药在儿童支气管肺炎的治疗方面取得了一些成果, 目前已有20余种口服中成药被研发并应用于儿童支气管肺炎的治疗中, 如小儿定喘口服液、复方鱼腥草颗粒、金振口服液和小儿消积止咳口服液等^[2]。XKZ2305颗粒内含蜜麻黄、燀苦杏仁、炒白芍、黄芩、炒紫苏子、炒莱菔子、钩藤、盐车前子等多味药材, 诸药合用, 共奏降气平喘、清热化痰、调和营卫之功效, 适用于轻中度哮喘急性发作外寒内热证儿童患者。

本研究基于液质联用技术首次对XKZ2305颗粒的化学成分进行了系统研究, 依据特征性碎片离子以及不同类型化合物的裂解规律, 共鉴定出化学成分174个, 其中黄酮类成分46种、萜类成分30种、生物碱类成分16种、酚酸类成分18种和其他成分64种。网络药理学分析结果显示, 共有靶点451个、核心靶点29个。其中黄芩素、汉黄芩素、槲皮素、钩藤碱和芥子碱硫氰酸盐等为XKZ2305颗粒治疗小儿咳喘症的关键活性成分。黄芩素、汉黄芩素和槲皮素是重要的黄酮类活性成分, 具有神经保护、抗氧化、抗炎、抗过敏等多种药理活性。黄芩素生物活性和脂溶性较高于其他黄酮类成分^[17], 研究表明黄芩素可显著降低IL-4、IL-13、INF-γ及IgE等炎症因子水平, 逆转Th1/Th2失衡, 显著降低炎症通路相关蛋白MAPK、PI3K、AKT、核转录因子κB (NF-κB) 的磷酸化形式, 激活相关通路, 减轻哮喘小鼠气道炎症和气道重塑^{[18, 19]}。汉黄芩素可诱导MAPK/AKT通路的核心分子, 诱导中性粒细胞胱天蛋白酶(caspase)依赖性凋亡, 减少气道及肺组织中的中性粒细胞浸润, 降低OVA特异性IgE、TNF-α、IL-6及高迁移率族蛋白1 (HMGB1) 等炎症介质的生成, 缓解气道高反应性^[20]。槲皮素能显著下调PI3K/AKT信号通路关键蛋白PI3K、AKT1、p-AKT1、哺乳动物雷帕霉素靶蛋白(mTOR) 的表达, AKT是PI3K/AKT信号通路极为重要的下游效应分子, PI3K/AKT活化后能激活下游mTOR, 上调HIF1A^[21], 纠正Th1/Th2免疫失衡, 抑制嗜酸性粒细胞(EOS) 等炎症细胞在气道内浸润^{[22, 23]}。钩藤碱已被证实具有明确的抗过敏性支气管哮喘作用, 作用机制依赖于其对转化生长因子-β (TGF-β1) 诱导的Smad和MAPK信号转导通路的抑制^[24]; 并通过抑制自噬来减轻炎症、气道重塑和氧化应激, 进而减轻哮喘症状^[25]。芥子碱的主要存在形式为芥子碱硫氰酸盐, 现有研究表明芥子碱硫氰酸盐通过放松支气管平滑肌和抑制毛细血管通透性, 具有很强的抗哮喘、镇咳和祛痰作用^[26]。研究证实芥子碱硫氰酸盐经穴位给药后能够下调前列腺素−内过氧化物合酶2 (PTGS2)、基质金属蛋白酶9 (MMP-9)、IL-2水平, 减少哮喘小鼠肺组织炎症因子表达, 以及抑制黏蛋白5AC (Muc5ac) 表达, 减轻气道黏液高分泌, 进而缓解哮喘症状^{[27, 28]}。

PPI网络显示, XKZ2305颗粒可能作用于TP53、IL6、IL1B、HIF1A、GAPDH、BCL2和AKT1等关键靶点对小儿咳喘症起治疗作用。TP53是一种应激反应性转录因子, 通过抑制BCL2、激活BCL2相关X蛋白(Bax), 致使Bax/BCL2比值增大, 从而促使细胞凋亡, 缓解哮喘引起的气道炎症和气道重塑^{[29, 30]}。此外, p53的凋亡功能可受HIF1A的状态调控, 且在缺氧条件下, 阻断HIF1A的表达能够诱导p53介导的细胞死亡^[31]。IL-6和IL1B是调控气道炎症应答的核心促炎细胞因子, 主要通过IL-6/mIL-6R信号通路和NF-κB信号通路促进炎症因子生成, 诱导Th17分化, 抑制调节性T淋巴细胞(Treg) 增殖, 在哮喘发病过程中起到抑制增殖、调节诱导细胞分化、增加气道黏液、加重气道炎症等作用^[32]。Akanksha等^[33]研究发现IL1B可通过NF-κB通路发挥作用, 与IFN-γ、糖皮质激素协同诱导Toll样受体2 (TLR2) 表达, 加剧气道炎症, 进一步导致气道狭窄、黏液分泌增加等病理现象。HIF1A是NOD样受体热蛋白结构域相关蛋白3 (NLRP3) 炎症小体激活的重要上游调控因子, 可通过抑制HIF1A活性, 阻断NLRP3炎症小体激活, 进而减轻支气管上皮细胞炎症^[34]; 同时HIF1A可调节血管内皮生长因子(VEGF)、生长因子(EGF) 等相关因子的表达, 促进气道平滑肌(ASMC)的增殖, 从而增加气道壁血管生成、平滑肌细胞增厚和肥大引起气道重塑^{[35, 36]}; 还可通过导致Th17/Treg失衡, 引起中性粒细胞炎症并导致气道高反应性和分泌增加^[37]。BCL2是参与炎性细胞凋亡的主要调控因子, BCL2 mRNA表达升高时, EOS、巨噬细胞等炎症细胞凋亡数量显著减少, 致使不断释放炎症因子, 促使气道炎症发生发展, 同时气道平滑肌增厚、上皮细胞损伤, 加剧哮喘病症^{[30, 38]}。

KEGG结果显示, XKZ2305颗粒作用于小儿咳喘症的通路主要包括HIF-1信号通路、PI3K/AKT信号通路、MAPK信号通路和AGE-RAGE信号通路等。PI3K/ AKT信号通路通过调控炎症浸润、免疫应答平衡、细胞自噬及氧化应激等多重机制介导气道炎症与重塑, 其激活可经mTOR/HIF1A/VEGF轴及EOS分化诱导过敏性炎症, 而抑制该通路则能降低IgE、TGF-β1、HIF1A、VEGF水平, 缓解黏液高分泌并改善气道重塑^[39-41]。MAPK信号通路包含ERK、JNK和p38三个亚家族, 是哮喘中炎症信号传递的关键载体, 其激活可直接推动促炎因子生成与炎症细胞功能异常^[42-44]。p38与JNK1/2常协同激活p53凋亡通路, 促进促凋亡蛋白Bax的表达及转位。在缺氧耐受细胞中, HIF1A也可抑制p38/JNK的过度激活, 避免细胞过度凋亡, 维持细胞存活^[45]。HIF-1是机体在缺氧条件下产生的氧依赖性缺氧反应元件, α亚基和β亚基共同构成稳定的HIF-1。HIF-1作为炎症效应的主要调节因子, IL-1α、TNF-α及各种生长因子均能激活其表达^[46]。现有研究表明, 哮喘小鼠体内AKT/HIF1A信号通路, 导致下游VEGFA和MMP9的表达增多, 肺组织肺泡间胶原沉积增多, 从而引起气道重塑^{[47, 48]}。

IgE与肥大细胞和嗜碱性粒细胞受体结合导致机体致敏, 致支气管平滑肌收缩、黏液大量产生、黏膜水肿以及气道高反应性, 形成急性过敏性哮喘^[49]。TNF-α可促进炎症细胞黏附、游走、浸润及中性粒细胞脱颗粒, 引起肺上皮组织损伤。从中医理论视角分析, IL-6、TNF-α等细胞因子介导的炎症反应, 与外寒内热证哮喘的“寒邪束表、热邪壅肺”病机高度契合, 其介导的气道黏膜损伤、炎性细胞浸润及气道高反应性, 正是外寒内热证哮喘患者痰黄咳嗽、喘息等临床特征的重要病理基础^[15]。动物药效学实验结果表明, XKZ2305颗粒能明显改善哮喘模型小鼠的症状表现, 显著减少抓鼻和挠痒次数, 有效缓解小鼠哮喘行为, 降低血液中IgE水平和BALF中TNF-α的含量, 改善肺脏间质炎细胞浸润, 有效减轻气道炎症, 对OVA诱导幼龄小鼠哮喘模型有明显的治疗作用。

综上所述, 本研究首次通过液质联用技术结合网络药理学构建XKZ2305颗粒“药物−活性成分−靶点−疾病”网络, 其中黄芩素、汉黄芩素、槲皮素、钩藤碱和芥子碱等成分可能作用于TP53、IL6、IL1B、HIF1A、GAPDH、BCL2和AKT1等潜在靶点发挥抗炎, 缓解气道重塑和气道高反应性等疗效。通过动物实验证实XKZ2305颗粒能够明显改善OVA诱导哮喘幼鼠引起的呼吸困难、气道炎症等症状, 证实XKZ2305颗粒治疗小儿咳喘疾病有明显疗效。初步揭示了XKZ2305颗粒治疗小儿咳喘症的潜在物质基础及作用机制, 表明其治疗小儿咳喘症具有多成分、多靶点、多途径的特点, 为其进一步深入研究及拓展其临床应用奠定了基础。

本研究作为机制探索的初步阶段, 仍存在一定的局限性。网络药理学研究是一种实验性预测, 以各种数据库为基础, 目前对靶点及成分的筛选以及数据库的选择缺乏统一的标准, 导致结果存在一定的偏差; 且中药复方治疗疾病存在剂量效应, 不同的药味剂量配伍后产生的药效不同, 通过数据库检索中药成分忽略成分含量, 将各成分均一化, 存在将微量成分筛选出来, 而主要成分被排除的可能性, 因此后续可通过结合多种筛选标准和体外活性实验等多方面, 对核心成分进行更全面的筛选与评估; 未来需考虑化学成分的体内代谢过程, 在细胞水平深入探究核心信号网络中关键节点的调控细节及其相互作用, 解析核心药效成分间的相互作用模式, 阐明多成分协同机制; 动物模型与临床疾病存在差异, 需开展多中心、大样本随机对照临床试验, 系统评估该药治疗小儿哮喘的疗效和安全性。

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2026年第61卷第9期

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doi: 10.16438/j.0513-4870.2025-1453

接收时间：2025-12-03
首发时间：2026-10-22
出版时间：2026-09-12

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收稿日期：2025-12-03
修回日期：2026-03-20

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¹天津中医药大学, 天津 301617

²天津药物研究院, 和光中药科技 (天津) 有限公司, 天津 300462

³天津市中药质量标志物重点实验室, 天津 300462

⁴药物成药性评价与系统转化全国重点实验室, 天津 300462

⁵联成迅康 (珠海横琴) 药业有限公司, 广东珠海 519000

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陈金鹏， E-mail: chenjp@tjipr.com

马儒， E-mail: maruok@163.com

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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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No.	t_R/min	m/z	Ion mode	Mass error(×10^-6)	Formula	Identification	Fragment	Class	Origin
1	2.07	422.025 5	[M−H]⁻	7.4	C₁₁H₂₁NO₁₀S₃	Glucoiberin	358, 259, 96	E	YCQZ
2	2.97	193.034 4	[M−H]⁻	5.29	C₆H₁₀O₇	Galaturonate	131, 113	E	YCQZ
3	3.63	191.018 8	[M−H]⁻	4.92	C₆H₈O₇	Citric acid	173	E	DKXR, CZSZ, CBS, GT
4	5.35	331.065 3	[M−H]⁻	5.23	C₁₃H₁₆O₁₀	6-O-Galloyl-glucose	169, 125	D	CBS
5	5.69	257.498 6	[M+H]⁺	2.36	C₁₆H₃₂O₂	Palmitic acid	257, 221	E	CZSZ, HQ
6	8.98	165.056 0	[M+H]⁺	8.26	C₉H₈O₃	trans-p-Hydroxycinnamic acid	119	D	HQ
7	9.33	493.251 3	[M−H]⁻	4.56	C₁₉H₂₆O₁₅	Galloylsucrose	331, 169, 125	D	CBS
8	9.56	166.087 6	[M+H]⁺	7.19	C₉H₁₁NO₂	L-Phenylalanine	120, 103	E	CZSZ
9	10.23	167.456 2	[M−H]⁻	8.78	C₈H₈O₄	Vanillic acid	123	D	CZSZ
10	14.62	194.081 9	M	5.89	C₁₀H₁₀O₄	Ferulate	176, 148, 133	D	MMH, CZSZ, CBS, GT, HQ
11	15.04	438.157 9	[M+H]⁺	0.54	C₃₀H₄₆O₂	Ganoderol A	293, 259, 137	B	CZSZ
12	20.78	502.151 9	[M+FA]⁻	6.58	C₂₀H₂₇NO₁₁	D-Amygdalin	323, 294, 221, 179	E	DKXR
13	20.78	186.928 5	[M−H]⁻	9.5	C₁₁H₂₂O₂	Hexyl 2-methylbutyrate	164	E	DKXR
14	20.78	413.768 3	[M−H]⁻	4.6	C₂₉H₅₀O	beta-Sitosterol	414, 326, 283	E	DKXR, MMH
15	21.86	171.029 8	[M+H]⁺	4.26	C₇H₆O₅	Gallic acid	171, 153, 127, 117	D	DKXR, CZSZ, CBS, YCQZ
16	22.62	123.015 7	[M+H]⁺	5.12	C₇H₆O₂	Benzoic acid	105, 110	D	CBS
17	22.88	353.085 4	[M−H]⁻	8.85	C₁₆H₁₈O₉	Chlorogenic acid	353, 191, 173, 135	D	DKXR, MMH, CBS, GT
18	22.88	358.111 4	[M−H]⁻	5.6	C₂₀H₂₂O₆	Pinoresinol	312	E	DKXR
19	23.91	474.234 3	[M+H]⁺	0.89	C₂₀H₂₃N₇O₇	Folinic acid	414, 223	E	CBS, YCQZ
20	24.70	373.110 9	[M−H]⁻	8.26	C₁₆H₂₂O₁₀	Geniposidic acid	373, 211, 149, 123	F	YCQZ, HQ
21	24.85	206.046 3	[M+H]⁺	7.82	C₁₀H₇NO₄	6-Hydroxy-4-oxoquinoline-2-carboxylic acid	206, 188, 160, 132, 104	C	MMH
22	25.78	589.118 2	[M−H]⁻	8.52	C₃₀H₃₂O₁₇S	Galloyl paeoniflorin sulfite	259, 167	E	CBS
23	25.89	444.479 5	[M+H]⁺	2.05	C₃₀H₅₀O₂	Betulin	425, 191, 235	B	CZSZ
24	26.54	268.088 2	[M+H]⁺	2.59	C₁₀H₁₃N₅O₄	Adenosine	136, 133, 119	E	DKXR, CZSZ
25	27.37	166.123 1	[M+H]⁺	7.41	C₁₀H₁₅NO	Ephedrine	148, 133, 117, 115	C	MMH
26	27.52	135.044 7	[M+H]⁺	1.26	C₇H₆O	Benzaldehyde	107, 79	E	MMH
27	28.40	148.113 2	M	0.85	C₉H₈O₂	Cinnamic acid	132, 115, 100	D	CBS
28	28.41	166.158 9	[M+H]⁺	5.36	C₁₀H₁₅NO	Pseudoephedrine	148, 133, 117, 115	C	MMH
29	30.09	543.112 7	[M−H]⁻	0.56	C₂₃H₂₈O₁₃S	Paeoniflorin sulfite	497, 375, 121	B	CBS
30	30.24	224.129 8	[M+H]⁺	7.9	C₁₂H₁₇NO₃	Maokonine	206, 135, 117	C	MMH
31	30.32	180.139 5	[M+H]⁺	7.01	C₁₁H₁₇NO	Methylephedrine	162, 147, 117, 115	C	MMH
32	30.56	311.401 2	[M−H]⁻	2.03	C₁₉H₂₂N₂O₂	Peraksine	293, 224	C	YCQZ
33	30.96	465.101 2	[M−H]⁻	5.86	C₂₁H₂₂O₁₂	Taxifolin 7-O-glucoside	437, 177	A	HQ
34	31.12	305.068 9	[M+H]⁺	5.26	C₁₅H₁₂O₇	Taxifolin	305, 195, 108	A	CBS
35	31.56	134.098 2	[M+H]⁺	8.95	C₉H₁₀O	m-Methylacetophenone	135, 120, 92, 78	E	MMH
36	31.61	183.028 9	[M−H]⁻	5.56	C₈H₈O₅	Methyl gallate	183, 124	E	CBS
37	31.96	497.201 5	[M+H]⁺	0.29	C₂₃H₂₈0₁₂	Oxypaeoniflorin	197, 179, 139, 195	B	CBS
38	35.16	462.256 3	[M−H]⁻	5.69	C₂₁H₁₈O₁₂	Luteolin-3-glucuronide	285, 175	A	CZSZ
39	35.89	438.057 0	[M+H]⁺	8.45	C₁₂H₂₃O₁₀NS₃	Glucoraphanin	372, 274, 259, 195, 96, 74	E	CLFZ
40	36.12	103.150 0	[M−H]⁻	6.23	C₈H₈	Styrene	105, 79, 91	E	MMH
41	36.18	345.119 9	[M−H]⁻	3.46	C₁₅H₂₂O₉	Aucubin	345, 183, 139, 101	F	YCQZ
42	36.22	134.060 3	[M+H]⁺	2.59	C₈H₇NO	Mandelonitrile	106, 78	E	DKXR
43	36.22	407.046 2	[M+Na]^-	4.7	C₂₀H₂₆O₆	Secoisolariciresinol	462	E	DKXR
44	38.56	593.189 6	[M−H]⁻	5.11	C₃₀H₂₆O₁₃	(+)-Catechin-(4α→8)-(−)-epigallocatechin	467, 425, 407	A	HQ
45	42.56	95.080 0	[M−H]⁻	0.26	C₅H₄O₂	Furfural	97, 69, 55	E	MMH
46	43.44	197.456 1	[M−H]⁻	4.23	C₉H₁₀O₅	Ethyl gallate	169, 125, 124	E	CBS
47	44.56	134.521 3	[M+H]⁺	2.36	C₁₀H₁₂	4-Phenyl-1-butene	103, 89	E	MMH
48	45.12	255.897 4	[M+H]⁺	5.62	C₁₅H₁₀O₄	Daidzein	137	A	CBS
49	45.18	261.456 8	[M+H]⁺	8.95	C₁₁H₂₀N₂O₅	N-L-gamma-Glutamyl-L-leucine	244, 197, 131, 86	E	CZSZ
50	45.19	477.456 0	[M−H]⁻	3.26	C₁₇H₂₂N₂O₁₀S₂	Neoglucobrassicin	446, 259, 234, 96	E	CLFZ
51	45.69	301.567 9	[M−H]⁻	2.56	C₁₆H₁₄O₆	5, 7, 4′-Trihydroxy 6-methoxyflavanone	284	A	HQ
52	46.63	191.071 6	[M+H]⁺	4.56	C₁₃H₁₈O	beta-Damascenone	213, 195, 135	B	MMH
53	47.50	481.174 1	[M+H]⁺	0.79	C₂₃H₂₈O₁₁	Paeoniflorin	525, 481, 197, 105	B	CBS
54	47.57	325.489 1	[M+H]⁺	4.08	C₂₀H₂₀O₄	Glabridin	325, 307, 289, 135, 107	A	DKXR
55	47.57	330.072 7	M	2.8	C₁₉H₂₂O₅	Gibberellin A5	/	B	DKXR
56	47.57	340.100 9	[M−H₂O]	5.21	C₂₀H₂₂O₆	Matairesinol	340, 332	E	DKXR
57	48.22	281.479 6	[M+H]⁺	6.59	C₁₈H₃₄O₂	Elaidic acid	/	E	YCQZ
58	48.67	443.568 9	[M−Na]⁻	2.99	C₂₁H₂₂O₁₂	Plantagoside	443	B	YCQZ
59	48.94	311.171 1	[M+H]⁺	5.46	C₁₄H₁₄O₈	2-Hydroxy-2-[(E)-3-(4-hydroxy-3-methoxyphenyl)prop-2-enoyl] butanedioic acid	251	E	CLFZ
60	50.89	385.111 5	[M−H]⁻	6.25	C₁₇H₂₂O₁₀	Sinapic acid glucoside	325, 223	D	HQ, CLFZ
61	53.06	278.456 9	[M+H]⁺	2.56	C₁₈H₃₀O₂	Linolenic acid	279, 149, 123, 109	E	DKXR, YCQZ, HQ
62	53.69	525.135 6	[M−H]⁻	0.89	C₂₄H₃₀O₁₃	Mudanpioside E	327, 121	B	CBS
63	53.79	481.256 3	[M+H]⁺	7.54	C₂₃H₂₈O₁₁	Albiflorin	381, 451, 359, 329, 123	B	CBS
64	53.81	463.163 1	[M+H]⁺	0.57	C₂₃H₂₆O₁₀	Lactiflorin	179, 151	B	CBS
65	53.82	165.589 6	[M−H]⁻	6.58	C₈H₆O₄	Phthalic acid	152, 136, 121	D	DKXR, CBS
66	53.82	341.265 4	[M+Na]⁺	2.6	C₁₅H₁₀O₈	Myricetin	318	A	GT
67	54.69	240.361 0	[M−H]⁻	5.43	C¹²H²¹N³O²	Plantagoguanidinic acid	208, 226	C	YCQZ
68	54.70	593.136 8	[M−H]⁻	6.8	C₂₇H₃₀O₁₅	Schaftoside	473, 443, 413, 383	A	YCQZ
69	54.89	287.590 0	[M+H]⁺	11.28	C₁₅H₁₀O₆	Luteolin	151, 133175	A	CZSZ
70	55.69	754.569 1	[M+H]⁺	5.69	C₃₄H₄₂O₁₉	3′, 6-Disinapoyl sucrose	207, 175, 147, 119, 91, 65	E	CLFZ
71	55.92	563.135 8	[M−H]⁻	8.65	C₂₆H₂₈O₁₄	Apiin	269, 227, 161, 117	A	CZSZ, CBS, YCQZ
72	56.02	285.481 2	[M+H]⁺	2.59	C₁₈H₃₆O₂	Stearic acid	285, 60	E	DKXR, CZSZ
73	56.18	457.113 3	[M+H]⁺	8.46	C₃₀H₄₈O₃	Ursolic acid	913, 439, 411, 393	B	CBS, GT, YCQZ, HQ
74	56.26	373.856 3	[M−H]⁻	5.02	C₁₉H₁₈O₈	Skullcapflavon Ⅱ	419, 373, 345, 360, 327	A	HQ
75	56.89	223.456 8	[M−H]⁻	5.14	C₁₂H₁₆O₄	Senkyunolide Ⅰ	179, 161, 151	B	CBS
76	58.13	651.489 7	[M−H]⁻	1.26	C₃₁H₄₀O₁₅	Isomartynoside	605, 475, 175	E	YCQZ
77	58.29	223.061 1	[M−H]⁻	5.69	C₁₁H₁₂_O5	Sinapic acid	179, 135	D	CLFZ
78	58.33	369.121 9	[M+H]⁺	5.11	C₁₇H₂₄N₂O₅S	Sinapine thiocyanate	301, 225	C	CLFZ
79	58.47	641.568 5	[M−H]⁻	8.13	C₂₉H₃₈O₁₆	Isomaltopaeoniflorin	641, 525, 479, 283, 161	B	CBS
80	58.59	374.598 6	[M+H]⁺	4.25	C₁₁H₁₉NO₉S₂	Gluconapin	259, 195, 130, 96, 74	E	CLFZ
81	59.38	281.093 5	[M−H]⁻	5.89	C₁₈H₃₄O₂	Oleic acid	263, 183	E	CZSZ, GT, HQ
82	60.11	300.997 2	[M−H]⁻	6.13	C₁₄H₆O₈	Ellagic acid	300, 185, 257	D	CBS
83	60.23	593.145 6	[M−H]⁻	8.56	C₂₇H₃₀O₁₅	Kaempferol 3-rutinoside	447	A	CZSZ, CBS
84	61.03	134.220 3	[M−H]⁻	5.39	C₁₀H₁₄	2-Ethyl-1, 4-dimethylbenzene	135, 105, 91, 77	E	MMH
85	61.44	283.061 9	[M−H]⁻	5.46	C₁₆H₁₂O₅	Oroxylin A	283, 268	A	HQ
86	61.87	465.105 6	[M+H]⁺	6.56	C₂₁H₂₀O₁₂	Hyperoside	303, 257	A	CBS
87	62.55	753.220 2	[M−H]⁻	6.08	C₃₄H₄₂O₁₉	1, 2-Disinapoylgentiobiose	223, 190	E	CLFZ
88	62.87	151.111 8	[M+H]⁺	2.59	C₉H₁₃NO	Phenylpropanolamine	134, 117	C	MMH
89	63.19	463.085 2	[M−H]⁻	6.59	C₂₁H2₀O₁₂	Herbacetin 7-glucoside	301, 271	A	MMH
90	63.56	338.256 4	[M+H]⁺	2.59	C₂₂H₄₃NO	Erucylamide	321, 303, 296	E	CBS
91	63.57	463.089 5	[M+H]⁺	5.43	C₂₁H₁₈O₁₂	Luteolin-7-O-glucuronide	287, 463	A	CZSZ
92	63.76	137.023 8	[M−H]⁻	4.76	C₇H₆O₃	Protocatechualdehyde	137, 109	E	CZSZ
93	65.78	547.140 8	[M−H]⁻	9.22	C₂₆H₂₈O₁₃	Chrysin 6-C-glucoside 8-C-α-Larabinoside	487, 457, 427, 367	A	HQ
94	65.91	624.193 4	[M−H]⁻	7.52	C₂₉H₃₆O₁₅	Acteoside	623, 461, 179, 161, 135	E	YCQZ, HQ
95	66.43	289.089 4	[M+H]⁺	5.46	C₁₅H₁₂O₆	Carthamidin	169, 147	A	HQ
96	66.47	251.092 2	[M+Na]⁺	5.29	C₁₄H₂₈O₂	Tetradecanoic acid	251, 215, 159, 145, 131	E	DKXR
97	66.56	181.564 9	[M−H]⁻	5.22	C₆H₁₄O₆	Sorbitol	119, 101, 89	E	YCQZ
98	69.52	639.561 3	[M−H]⁻	5.69	C₂₉H₃₆O₁₆	Plantainoside D	621, 529	B	YCQZ
99	71.03	195.587 4	[M+H]⁺	8.23	C₁₂H₁₈O₂	Cnidilide	177, 149, 131, 125	E	CBS
100	72.09	297.079 1	[M+H]⁺	2.17	C₁₃H₁₂O₈	Caffeoylmalic acid	173	D	MMH
101	72.61	461.070 7	[M−H]⁻	4.15	C21H18O12	Scutellarin	285, 267, 239, 119, 113	A	CZSZ, HQ
102	74.16	205.589 6	[M+H]⁺	6.13	C₁₂H₁₂O₃	3-Butylidene-7-hydroxyphthalide	187, 147	B	CBS
103	74.23	415.214 6	[M+H]⁺	7.6	C₂₄H₃₀O₆	Bis (4-ethylbenzylidene) sorbitol	119	E	DKXR
104	74.91	509.486 3	[M−H]⁻	4.23	C₂₄H₃₀O₁₂	Mudanpioside D	509, 463, 121, 77	B	CBS
105	75.13	479.563 2	[M+H]⁺	1.03	C₂₃H₂₆O₁₁	Plantainoside A	461, 334, 307, 263, 179	B	YCQZ
106	76.17	153.031 2	[M−H]⁻	3.5	C₁₀H₁₈O	Terpineol	180, 153	B	DKXR
107	76.17	361.589 6	[M+H]⁺	2.59	C₁₈H₁₆O₈	Rosmarinic acid	197, 179, 161, 135, 133	E	CZSZ, CBS
108	76.36	431.525 9	[M−H]⁻	5.03	C₂₁H₂₀O₁₀	Apigenin-7-O-β-D-glucoside	151, 239, 240, 268, 432	A	HQ
109	76.95	647.139 3	[M−H]⁻	7.15	C₃₀H₃₂O₁₄S	Benzoylpaeoniflorin sulfite	259	B	CBS
110	77.36	191.018 3	[M−H]⁻	1.2	C₁₃H₂₀O	beta-Ionone	191, 111	B	DKXR
111	77.36	369.236 5	[M+H]⁺	5.26	C₂₁H₂₄N₂O₄	18, 19-Dehydrocorynoxinic acid	369, 351	E	GT
112	79.99	295.060 9	[M+Na]⁺	1.02	C₁₆H₃₂O₃	2-Hydroxypalmitic acid	295, 277, 259, 231	E	DKXR
113	79.99	383.198 3	[M+H]⁺	10.08	C₂₂H₂₆N₂O₄	Corynoxeine	351, 201	C	GT
114	80.05	447.123 1	[M−H]⁻	2.01	C₂₁H₂₀O₁₁	Plantaginin	284	A	YCQZ
115	80.06	325.006 3	[M−H]⁻	5.46	C₁₅H₁₈O₈	4-O-beta-Glucopyranosyl-cis-coumaric acid	163, 119	D	CZSZ
116	80.23	357.147 9	[M+H]⁺	0.28	C₂₀H₂₀O₆	Coniferylferulate	311, 149	E	CBS
117	82.55	269.048 9	[M−H]⁻	6.59	C₁₅H₁₀O₅	Baicalein	241, 197	A	HQ
118	82.62	445.074 6	[M−H]⁻	6.88	C₂₁H₁₈O₁₁	Baicalin	891, 445, 269, 251	A	HQ
119	83.29	615.421 3	[M−H]⁻	8.46	C₃₀H₃₂O₁₄	Mudanpioside H	615, 493, 169	B	CBS
120	84.50	291.088 5	[M+H]⁺	1.02	C₁₅H₁₄O₆	Catechin	161, 123, 139	A	DKXR
121	84.55	385.214 9	[M+H]⁺	4.89	C₂₂H₂₉N₂O₄	Rhynchophylline	353, 268, 160, 110	C	GT
122	84.64	286.080 1	[M+H]⁺	2.05	C₁₇H₁₉NO₃	Coclaurine	286, 269, 254, 237, 209	C	DKXR
123	84.64	385.214 9	[M+H]⁺	4.89	C₂₂H₂₈N₂O₄	Isorhynchophylline	353, 268, 160, 110	C	GT
124	85.13	178.001 2	[M−H]⁻	2.36	C₉H₆O₄	Cichorigenin	149, 133, 105	E	CZSZ
125	85.13	313.269 9	[M−H]⁻	4.09	C₁₇H₁₄O₆	Skullcapflavon Ⅰ	313, 298, 113	A	HQ
126	85.16	473.158 9	[M+H]⁺	1.05	C₃₀H₄₈O₄	Hederagenin	200, 270	B	CZSZ
127	85.16	406.468 1	[M−H]⁻	3.89	C₁₁H₂₁NO₉S₃	3-Methylthiopropyl glucosinolate	259, 195, 96, 74	E	CLFZ
128	85.16	651.289 6	[M−H]⁻	8.99	C₃₁H₄₀O₁₅	Martynoside	605, 475, 175	E	YCQZ
129	85.23	639.853 6	[M−H]⁻	1.25	C2₉H₃₆O₁₆	Plantamajoside	477, 179, 161, 135, 315	B	YCQZ
130	85.26	487.100 2	[M+H]⁺	5.01	C₂₁H₂₈O₁₃	cis-Tanoside F	179, 135	E	YCQZ
131	85.36	315.410 2	[M−H]⁻	4.69	C₁₃H₁₆O₉	1-O-(3, 4-Dihydroxybenzoyl)-beta-D-glucopyranose	152, 108	D	CLFZ
132	85.40	421.235 6	[M−H]⁻	1.11	C₁₉H₁₈O₁₁	Isomangiferin	/	A	YCQZ
133	85.46	301.567 8	[M−H]⁻	8.96	C₁₅H₁₀O₇	Quercetin	178, 151	A	CZSZ
134	85.56	593.788 5	[M+H]⁺	4.56	C₂₈H₃₂O₁₄	Linarin	565, 447, 285	A	CZSZ
135	86.70	447.095 6	[M−H]⁻	7.39	C₂₁H₂₀O₁₁	Dihydrobaicalin	271, 243	A	HQ
136	87.18	133.013 9	[M−H]⁻	−2.9	C₄H₆O₅	Malic acid	115, 133	E	DKXR
137	87.18	612.495 0	[M+2H]⁺	6.9	C₂₇H₃₀O₁₆	Rutin	589, 566	A	HQ
138	87.39	257.045 8	[M+H]⁺	8.46	C₁₅H₁₂O₄	Isoliquiritigenin	239, 137	A	HQ
139	87.46	423.893 5	[M+H]⁺	10.25	C₃₀H₄₆O	Glochidone	405, 215	B	CZSZ
140	87.98	273.077 1	[M+H]⁺	7.15	C₁₅H₁₂O₅	Naringenin	169, 131	A	MMH, CBS
141	87.98	273.098 7	[M+H]⁺	7.16	C₁₅H₁₂O₅	Pinobanksin	273, 151	A	HQ
142	88.23	623.589 6	[M−H]⁻	5.13	C₂₉H₃₆O₁₅	Forsythiaside A	461, 161, 135	D	YCQZ
143	88.75	445.045 6	[M−H]⁻	6.23	C₂₁H₁₈O₁₁	Glychionide A	445, 269	A	HQ
144	89.45	583.269 7	[M−H]⁻	2.58	C₃₀H₃₂O₁₂	Benzoylpaeoniflorin	431, 387, 121	B	CBS
145	89.46	463.469 8	[M−H]⁻	5.11	C₁₆H₂₀N₂O₁₀S₂	4-Hydroxy-3-indolylmethyl glucosinolate	285, 267, 195, 96, 74	E	CLFZ
146	89.56	125.465 0	[M−H]⁻	2.56	C₆H₆O₃	Pyrogallol	79, 96	E	CBS
147	89.57	209.585 6	[M+H]⁺	5.69	C₁₂H₁₆O₃	β-Asarone	191, 163, 153	E	CBS
148	90.13	299.054 9	[M−H]⁻	3.87	C₁₆H₁₂O₆	Tenaxin Ⅱ	283, 227	A	HQ
149	90.13	299.054 9	[M−H]⁻	3.59	C₁₆H₁₂O₆	Kaempferide	299, 228	A	MMH, CBS
150	90.18	445.112 5	[M−H]⁻	3.23	C₂₂H₂₂O₁₀	Wogonin-5-O-D-glucoside	269	A	HQ
151	90.59	227.489 6	[M+H]⁺	2.59	C₁₂H₂₂N₂O₂	Cyclo (Leu-Leu)	209, 114	E	CZSZ
152	90.88	307.058 5	[M+H]⁺	2.18	C₁₅H₁₄O₇	Leucocyanidin	307, 163, 139, 121	A	MMH
153	91.26	183.563 1	[M−H]⁻	5.69	C₁₁H₂₀O₂	2-Undecenoic acid	207, 192, 175, 147, 133, 77	E	DKXR
154	91.26	455.213 6	[M+H]⁺	5.69	C₃₀H₄₈O₃	Oleanolic acid	377	B	GT
155	92.07	459.105 6	[M−H]⁻	7.59	C₂₂H₂₀O₁₁	Oroxyloside	283, 169	A	HQ
156	92.08	429.169 6	[M−H]⁻	5.16	C₂₁H₁₈O₁₀	Chrysin-7-O-β-D glucoronide	253, 175	A	HQ
157	92.15	283.059 2	[M−H]⁻	6.88	C₁₆H₁₂O₅	Wogonin	268, 240, 239, 167, 139	A	HQ
158	95.27	419.156 0	[M+H]⁺	1.28	C₂₁H₂₂O₉	Liquiritin	419, 257, 239, 211, 147	A	DKXR
159	95.27	369.194 9	[M+H]⁺	6.52	C₂₂H₂₈N₂O₃	Hirsutine	543, 497, 265	C	GT
160	96.05	461.109 7	[M+H]⁺	4.15	C₂₂H₂₀O₁₁	Apigenin-7-O-methylglucuronide	461, 271	A	HQ
161	96.14	193.256 4	[M+H]⁺	1.56	C₁₂H₁₆O₂	Sedanenolide	175, 147, 137, 93	B	CBS
162	97.11	629.784 6	[M−H]⁻	1.56	C₃₁H₃₄O₁₄	Mudanpioside B	583, 553, 431, 165, 121, 77	B	CBS
163	97.56	313.065 9	[M−H]⁻	6.59	C₁₇H₁₄O₆	Dihydroxy-dimethoxyflavone	298, 255	A	HQ
164	98.56	783.154 8	[M−H]⁻	5.12	C₃₇H₃₆O₁₉	3′, 6′-di-O-Galloylpaeoniflorin	783, 765, 631, 465, 313	B	CBS
165	99.56	451.896 3	[M−H]⁻	8.59	C₁₃H₂₅NO₁₀S₃	1-Thio-β-D-glucopyranose 1-(6-(methylsulfinyl)-N-(sulfooxy)hexanimi date)	386, 259, 208, 96, 74	E	CLFZ
166	100.26	300.256 9	[M+H]⁺	3.65	C₁₈H₃₇NO₂	Palmidrol	283, 255	E	CBS
167	101.79	115.891 1	[M−H]⁻	2.56	C₅H₈O₃	Levulinic acid	117, 102, 89, 74	E	DKXR, CBS
168	101.79	355.203 4	[M+H]⁺	5.1	C₂₁H₂₆N₂O₃	Yohimbine	355, 212, 144	C	GT
169	103.47	499.207 9	[M+H]⁺	6.84	C₂₆H₃₀N₂O₈	Strictosamide	337, 267	C	GT
170	104.32	432.256 3	[M+H]⁺	6.77	C₁₉H₂₈O₁₁	Benzyl-β-gentiobioside	327, 255	E	CLFZ
171	104.75	167.071 3	[M+H]⁺	5.12	C₉H₁₀O₃	Paeonol	167, 149, 121	D	CBS
172	105.25	287.145 6	[M−H]⁻	8.96	C₁₅H₁₂O₆	Dihydrokaempferol	287, 93, 193, 175	A	CBS
173	107.89	477.120 3	[M−H]⁻	50.56	C₂₃H₂₆O₁₁	Calceolarioside A	360, 325, 290, 203, 163	E	YCQZ
174	108.36	477.889 9	[M−H]⁻	64.88	C₂₃H₂₆O₁₁	Calceolarioside B	/	E	YCQZ

No.

t_R/min

m/z

Ion mode

Mass error(×10^-6)

Formula

Identification

Fragment

Class

Origin

2.07

422.025 5

[M−H]⁻

7.4

C₁₁H₂₁NO₁₀S₃

Glucoiberin

358, 259, 96

YCQZ

2.97

193.034 4

[M−H]⁻

5.29

C₆H₁₀O₇

Galaturonate

131, 113

YCQZ

3.63

191.018 8

[M−H]⁻

4.92

C₆H₈O₇

Citric acid

173

DKXR, CZSZ, CBS, GT

5.35

331.065 3

[M−H]⁻

5.23

C₁₃H₁₆O₁₀

6-O-Galloyl-glucose

169, 125

CBS

5.69

257.498 6

[M+H]⁺

2.36

C₁₆H₃₂O₂

Palmitic acid

257, 221

CZSZ, HQ

8.98

165.056 0

[M+H]⁺

8.26

C₉H₈O₃

trans-p-Hydroxycinnamic acid

119

9.33

493.251 3

[M−H]⁻

4.56

C₁₉H₂₆O₁₅

Galloylsucrose

331, 169, 125

CBS

9.56

166.087 6

[M+H]⁺

7.19

C₉H₁₁NO₂

L-Phenylalanine

120, 103

CZSZ

10.23

167.456 2

[M−H]⁻

8.78

C₈H₈O₄

Vanillic acid

123

CZSZ

14.62

194.081 9

5.89

C₁₀H₁₀O₄

Ferulate

176, 148, 133

MMH, CZSZ, CBS, GT, HQ

15.04

438.157 9

[M+H]⁺

0.54

C₃₀H₄₆O₂

Ganoderol A

293, 259, 137

CZSZ

20.78

502.151 9

[M+FA]⁻

6.58

C₂₀H₂₇NO₁₁

D-Amygdalin

323, 294, 221, 179

DKXR

20.78

186.928 5

[M−H]⁻

9.5

C₁₁H₂₂O₂

Hexyl 2-methylbutyrate

164

DKXR

20.78

413.768 3

[M−H]⁻

4.6

C₂₉H₅₀O

beta-Sitosterol

414, 326, 283

DKXR, MMH

21.86

171.029 8

[M+H]⁺

4.26

C₇H₆O₅

Gallic acid

171, 153, 127, 117

DKXR, CZSZ, CBS, YCQZ

22.62

123.015 7

[M+H]⁺

5.12

C₇H₆O₂

Benzoic acid

105, 110

CBS

22.88

353.085 4

[M−H]⁻

8.85

C₁₆H₁₈O₉

Chlorogenic acid

353, 191, 173, 135

DKXR, MMH, CBS, GT

22.88

358.111 4

[M−H]⁻

5.6

C₂₀H₂₂O₆

Pinoresinol

312

DKXR

23.91

474.234 3

[M+H]⁺

0.89

C₂₀H₂₃N₇O₇

Folinic acid

414, 223

CBS, YCQZ

24.70

373.110 9

[M−H]⁻

8.26

C₁₆H₂₂O₁₀

Geniposidic acid

373, 211, 149, 123

YCQZ, HQ

24.85

206.046 3

[M+H]⁺

7.82

C₁₀H₇NO₄

6-Hydroxy-4-oxoquinoline-2-carboxylic acid

206, 188, 160, 132, 104

MMH

25.78

589.118 2

[M−H]⁻

8.52

C₃₀H₃₂O₁₇S

Galloyl paeoniflorin sulfite

259, 167

CBS

25.89

444.479 5

[M+H]⁺

2.05

C₃₀H₅₀O₂

Betulin

425, 191, 235

CZSZ

26.54

268.088 2

[M+H]⁺

2.59

C₁₀H₁₃N₅O₄

Adenosine

136, 133, 119

DKXR, CZSZ

27.37

166.123 1

[M+H]⁺

7.41

C₁₀H₁₅NO

Ephedrine

148, 133, 117, 115

MMH

27.52

135.044 7

[M+H]⁺

1.26

C₇H₆O

Benzaldehyde

107, 79

MMH

28.40

148.113 2

0.85

C₉H₈O₂

Cinnamic acid

132, 115, 100

CBS

28.41

166.158 9

[M+H]⁺

5.36

C₁₀H₁₅NO

Pseudoephedrine

148, 133, 117, 115

MMH

30.09

543.112 7

[M−H]⁻

0.56

C₂₃H₂₈O₁₃S

Paeoniflorin sulfite

497, 375, 121

CBS

30.24

224.129 8

[M+H]⁺

7.9

C₁₂H₁₇NO₃

Maokonine

206, 135, 117

MMH

30.32

180.139 5

[M+H]⁺

7.01

C₁₁H₁₇NO

Methylephedrine

162, 147, 117, 115

MMH

30.56

311.401 2

[M−H]⁻

2.03

C₁₉H₂₂N₂O₂

Peraksine

293, 224

YCQZ

30.96

465.101 2

[M−H]⁻

5.86

C₂₁H₂₂O₁₂

Taxifolin 7-O-glucoside

437, 177

31.12

305.068 9

[M+H]⁺

5.26

C₁₅H₁₂O₇

Taxifolin

305, 195, 108

CBS

31.56

134.098 2

[M+H]⁺

8.95

C₉H₁₀O

m-Methylacetophenone

135, 120, 92, 78

MMH

31.61

183.028 9

[M−H]⁻

5.56

C₈H₈O₅

Methyl gallate

183, 124

CBS

31.96

497.201 5

[M+H]⁺

0.29

C₂₃H₂₈0₁₂

Oxypaeoniflorin

197, 179, 139, 195

CBS

35.16

462.256 3

[M−H]⁻

5.69

C₂₁H₁₈O₁₂

Luteolin-3-glucuronide

285, 175

CZSZ

35.89

438.057 0

[M+H]⁺

8.45

C₁₂H₂₃O₁₀NS₃

Glucoraphanin

372, 274, 259, 195, 96, 74

CLFZ

36.12

103.150 0

[M−H]⁻

6.23

C₈H₈

Styrene

105, 79, 91

MMH

36.18

345.119 9

[M−H]⁻

3.46

C₁₅H₂₂O₉

Aucubin

345, 183, 139, 101

YCQZ

36.22

134.060 3

[M+H]⁺

2.59

C₈H₇NO

Mandelonitrile

106, 78

DKXR

36.22

407.046 2

[M+Na]^-

4.7

C₂₀H₂₆O₆

Secoisolariciresinol

462

DKXR

38.56

593.189 6

[M−H]⁻

5.11

C₃₀H₂₆O₁₃

(+)-Catechin-(4α→8)-(−)-epigallocatechin

467, 425, 407

42.56

95.080 0

[M−H]⁻

0.26

C₅H₄O₂

Furfural

97, 69, 55

MMH

43.44

197.456 1

[M−H]⁻

4.23

C₉H₁₀O₅

Ethyl gallate

169, 125, 124

CBS

44.56

134.521 3

[M+H]⁺

2.36

C₁₀H₁₂

4-Phenyl-1-butene

103, 89

MMH

45.12

255.897 4

[M+H]⁺

5.62

C₁₅H₁₀O₄

Daidzein

137

CBS

45.18

261.456 8

[M+H]⁺

8.95

C₁₁H₂₀N₂O₅

N-L-gamma-Glutamyl-L-leucine

244, 197, 131, 86

CZSZ

45.19

477.456 0

[M−H]⁻

3.26

C₁₇H₂₂N₂O₁₀S₂

Neoglucobrassicin

446, 259, 234, 96

CLFZ

45.69

301.567 9

[M−H]⁻

2.56

C₁₆H₁₄O₆

5, 7, 4′-Trihydroxy 6-methoxyflavanone

284

46.63

191.071 6

[M+H]⁺

4.56

C₁₃H₁₈O

beta-Damascenone

213, 195, 135

MMH

47.50

481.174 1

[M+H]⁺

0.79

C₂₃H₂₈O₁₁

Paeoniflorin

525, 481, 197, 105

CBS

47.57

325.489 1

[M+H]⁺

4.08

C₂₀H₂₀O₄

Glabridin

325, 307, 289, 135, 107

DKXR

47.57

330.072 7

2.8

C₁₉H₂₂O₅

Gibberellin A5

DKXR

47.57

340.100 9

[M−H₂O]

5.21

C₂₀H₂₂O₆

Matairesinol

340, 332

DKXR

48.22

281.479 6

[M+H]⁺

6.59

C₁₈H₃₄O₂

Elaidic acid

YCQZ

48.67

443.568 9

[M−Na]⁻

2.99

C₂₁H₂₂O₁₂

Plantagoside

443

YCQZ

48.94

311.171 1

[M+H]⁺

5.46

C₁₄H₁₄O₈

2-Hydroxy-2-[(E)-3-(4-hydroxy-3-methoxyphenyl)prop-2-enoyl] butanedioic acid

251

CLFZ

50.89

385.111 5

[M−H]⁻

6.25

C₁₇H₂₂O₁₀

Sinapic acid glucoside

325, 223

HQ, CLFZ

53.06

278.456 9

[M+H]⁺

2.56

C₁₈H₃₀O₂

Linolenic acid

279, 149, 123, 109

DKXR, YCQZ, HQ

53.69

525.135 6

[M−H]⁻

0.89

C₂₄H₃₀O₁₃

Mudanpioside E

327, 121

CBS

53.79

481.256 3

[M+H]⁺

7.54

C₂₃H₂₈O₁₁

Albiflorin

381, 451, 359, 329, 123

CBS

53.81

463.163 1

[M+H]⁺

0.57

C₂₃H₂₆O₁₀

Lactiflorin

179, 151

CBS

53.82

165.589 6

[M−H]⁻

6.58

C₈H₆O₄

Phthalic acid

152, 136, 121

DKXR, CBS

53.82

341.265 4

[M+Na]⁺

2.6

C₁₅H₁₀O₈

Myricetin

318

54.69

240.361 0

[M−H]⁻

5.43

C¹²H²¹N³O²

Plantagoguanidinic acid

208, 226

YCQZ

54.70

593.136 8

[M−H]⁻

6.8

C₂₇H₃₀O₁₅

Schaftoside

473, 443, 413, 383

YCQZ

54.89

287.590 0

[M+H]⁺

11.28

C₁₅H₁₀O₆

Luteolin

151, 133175

CZSZ

55.69

754.569 1

[M+H]⁺

5.69

C₃₄H₄₂O₁₉

3′, 6-Disinapoyl sucrose

207, 175, 147, 119, 91, 65

CLFZ

55.92

563.135 8

[M−H]⁻

8.65

C₂₆H₂₈O₁₄

Apiin

269, 227, 161, 117

CZSZ, CBS, YCQZ

56.02

285.481 2

[M+H]⁺

2.59

C₁₈H₃₆O₂

Stearic acid

285, 60

DKXR, CZSZ

56.18

457.113 3

[M+H]⁺

8.46

C₃₀H₄₈O₃

Ursolic acid

913, 439, 411, 393

CBS, GT, YCQZ, HQ

56.26

373.856 3

[M−H]⁻

5.02

C₁₉H₁₈O₈

Skullcapflavon Ⅱ

419, 373, 345, 360, 327

56.89

223.456 8

[M−H]⁻

5.14

C₁₂H₁₆O₄

Senkyunolide Ⅰ

179, 161, 151

CBS

58.13

651.489 7

[M−H]⁻

1.26

C₃₁H₄₀O₁₅

Isomartynoside

605, 475, 175

YCQZ

58.29

223.061 1

[M−H]⁻

5.69

C₁₁H₁₂_O5

Sinapic acid

179, 135

CLFZ

58.33

369.121 9

[M+H]⁺

5.11

C₁₇H₂₄N₂O₅S

Sinapine thiocyanate

301, 225

CLFZ

58.47

641.568 5

[M−H]⁻

8.13

C₂₉H₃₈O₁₆

Isomaltopaeoniflorin

641, 525, 479, 283, 161

CBS

58.59

374.598 6

[M+H]⁺

4.25

C₁₁H₁₉NO₉S₂

Gluconapin

259, 195, 130, 96, 74

CLFZ

59.38

281.093 5

[M−H]⁻

5.89

C₁₈H₃₄O₂

Oleic acid

263, 183

CZSZ, GT, HQ

60.11

300.997 2

[M−H]⁻

6.13

C₁₄H₆O₈

Ellagic acid

300, 185, 257

CBS

60.23

593.145 6

[M−H]⁻

8.56

C₂₇H₃₀O₁₅

Kaempferol 3-rutinoside

447

CZSZ, CBS

61.03

134.220 3

[M−H]⁻

5.39

C₁₀H₁₄

2-Ethyl-1, 4-dimethylbenzene

135, 105, 91, 77

MMH

61.44

283.061 9

[M−H]⁻

5.46

C₁₆H₁₂O₅

Oroxylin A

283, 268

61.87

465.105 6

[M+H]⁺

6.56

C₂₁H₂₀O₁₂

Hyperoside

303, 257

CBS

62.55

753.220 2

[M−H]⁻

6.08

C₃₄H₄₂O₁₉

1, 2-Disinapoylgentiobiose

223, 190

CLFZ

62.87

151.111 8

[M+H]⁺

2.59

C₉H₁₃NO

Phenylpropanolamine

134, 117

MMH

63.19

463.085 2

[M−H]⁻

6.59

C₂₁H2₀O₁₂

Herbacetin 7-glucoside

301, 271

MMH

63.56

338.256 4

[M+H]⁺

2.59

C₂₂H₄₃NO

Erucylamide

321, 303, 296

CBS

63.57

463.089 5

[M+H]⁺

5.43

C₂₁H₁₈O₁₂

Luteolin-7-O-glucuronide

287, 463

CZSZ

63.76

137.023 8

[M−H]⁻

4.76

C₇H₆O₃

Protocatechualdehyde

137, 109

CZSZ

65.78

547.140 8

[M−H]⁻

9.22

C₂₆H₂₈O₁₃

Chrysin 6-C-glucoside 8-C-α-Larabinoside

487, 457, 427, 367

65.91

624.193 4

[M−H]⁻

7.52

C₂₉H₃₆O₁₅

Acteoside

623, 461, 179, 161, 135

YCQZ, HQ

66.43

289.089 4

[M+H]⁺

5.46

C₁₅H₁₂O₆

Carthamidin

169, 147

66.47

251.092 2

[M+Na]⁺

5.29

C₁₄H₂₈O₂

Tetradecanoic acid

251, 215, 159, 145, 131

DKXR

66.56

181.564 9

[M−H]⁻

5.22

C₆H₁₄O₆

Sorbitol

119, 101, 89

YCQZ

69.52

639.561 3

[M−H]⁻

5.69

C₂₉H₃₆O₁₆

Plantainoside D

621, 529

YCQZ

71.03

195.587 4

[M+H]⁺

8.23

C₁₂H₁₈O₂

Cnidilide

177, 149, 131, 125

CBS

100

72.09

297.079 1

[M+H]⁺

2.17

C₁₃H₁₂O₈

Caffeoylmalic acid

173

MMH

101

72.61

461.070 7

[M−H]⁻

4.15

C21H18O12

Scutellarin

285, 267, 239, 119, 113

CZSZ, HQ

102

74.16

205.589 6

[M+H]⁺

6.13

C₁₂H₁₂O₃

3-Butylidene-7-hydroxyphthalide

187, 147

CBS

103

74.23

415.214 6

[M+H]⁺

7.6

C₂₄H₃₀O₆

Bis (4-ethylbenzylidene) sorbitol

119

DKXR

104

74.91

509.486 3

[M−H]⁻

4.23

C₂₄H₃₀O₁₂

Mudanpioside D

509, 463, 121, 77

CBS

105

75.13

479.563 2

[M+H]⁺

1.03

C₂₃H₂₆O₁₁

Plantainoside A

461, 334, 307, 263, 179

YCQZ

106

76.17

153.031 2

[M−H]⁻

3.5

C₁₀H₁₈O

Terpineol

180, 153

DKXR

107

76.17

361.589 6

[M+H]⁺

2.59

C₁₈H₁₆O₈

Rosmarinic acid

197, 179, 161, 135, 133

CZSZ, CBS

108

76.36

431.525 9

[M−H]⁻

5.03

C₂₁H₂₀O₁₀

Apigenin-7-O-β-D-glucoside

151, 239, 240, 268, 432

109

76.95

647.139 3

[M−H]⁻

7.15

C₃₀H₃₂O₁₄S

Benzoylpaeoniflorin sulfite

259

CBS

110

77.36

191.018 3

[M−H]⁻

1.2

C₁₃H₂₀O

beta-Ionone

191, 111

DKXR

111

77.36

369.236 5

[M+H]⁺

5.26

C₂₁H₂₄N₂O₄

18, 19-Dehydrocorynoxinic acid

369, 351

112

79.99

295.060 9

[M+Na]⁺

1.02

C₁₆H₃₂O₃

2-Hydroxypalmitic acid

295, 277, 259, 231

DKXR

113

79.99

383.198 3

[M+H]⁺

10.08

C₂₂H₂₆N₂O₄

Corynoxeine

351, 201

114

80.05

447.123 1

[M−H]⁻

2.01

C₂₁H₂₀O₁₁

Plantaginin

284

YCQZ

115

80.06

325.006 3

[M−H]⁻

5.46

C₁₅H₁₈O₈

4-O-beta-Glucopyranosyl-cis-coumaric acid

163, 119

CZSZ

116

80.23

357.147 9

[M+H]⁺

0.28

C₂₀H₂₀O₆

Coniferylferulate

311, 149

CBS

117

82.55

269.048 9

[M−H]⁻

6.59

C₁₅H₁₀O₅

Baicalein

241, 197

118

82.62

445.074 6

[M−H]⁻

6.88

C₂₁H₁₈O₁₁

Baicalin

891, 445, 269, 251

119

83.29

615.421 3

[M−H]⁻

8.46

C₃₀H₃₂O₁₄

Mudanpioside H

615, 493, 169

CBS

120

84.50

291.088 5

[M+H]⁺

1.02

C₁₅H₁₄O₆

Catechin

161, 123, 139

DKXR

121

84.55

385.214 9

[M+H]⁺

4.89

C₂₂H₂₉N₂O₄

Rhynchophylline

353, 268, 160, 110

122

84.64

286.080 1

[M+H]⁺

2.05

C₁₇H₁₉NO₃

Coclaurine

286, 269, 254, 237, 209

DKXR

123

84.64

385.214 9

[M+H]⁺

4.89

C₂₂H₂₈N₂O₄

Isorhynchophylline

353, 268, 160, 110

124

85.13

178.001 2

[M−H]⁻

2.36

C₉H₆O₄

Cichorigenin

149, 133, 105

CZSZ

125

85.13

313.269 9

[M−H]⁻

4.09

C₁₇H₁₄O₆

Skullcapflavon Ⅰ

313, 298, 113

126

85.16

473.158 9

[M+H]⁺

1.05

C₃₀H₄₈O₄

Hederagenin

200, 270

CZSZ

127

85.16

406.468 1

[M−H]⁻

3.89

C₁₁H₂₁NO₉S₃

3-Methylthiopropyl glucosinolate

259, 195, 96, 74

CLFZ

128

85.16

651.289 6

[M−H]⁻

8.99

C₃₁H₄₀O₁₅

Martynoside

605, 475, 175

YCQZ

129

85.23

639.853 6

[M−H]⁻

1.25

C2₉H₃₆O₁₆

Plantamajoside

477, 179, 161, 135, 315

YCQZ

130

85.26

487.100 2

[M+H]⁺

5.01

C₂₁H₂₈O₁₃

cis-Tanoside F

179, 135

YCQZ

131

85.36

315.410 2

[M−H]⁻

4.69

C₁₃H₁₆O₉

1-O-(3, 4-Dihydroxybenzoyl)-beta-D-glucopyranose

152, 108

CLFZ

132

85.40

421.235 6

[M−H]⁻

1.11

C₁₉H₁₈O₁₁

Isomangiferin

YCQZ

133

85.46

301.567 8

[M−H]⁻

8.96

C₁₅H₁₀O₇

Quercetin

178, 151

CZSZ

134

85.56

593.788 5

[M+H]⁺

4.56

C₂₈H₃₂O₁₄

Linarin

565, 447, 285

CZSZ

135

86.70

447.095 6

[M−H]⁻

7.39

C₂₁H₂₀O₁₁

Dihydrobaicalin

271, 243

136

87.18

133.013 9

[M−H]⁻

−2.9

C₄H₆O₅

Malic acid

115, 133

DKXR

137

87.18

612.495 0

[M+2H]⁺

6.9

C₂₇H₃₀O₁₆

Rutin

589, 566

138

87.39

257.045 8

[M+H]⁺

8.46

C₁₅H₁₂O₄

Isoliquiritigenin

239, 137

139

87.46

423.893 5

[M+H]⁺

10.25

C₃₀H₄₆O

Glochidone

405, 215

CZSZ

140

87.98

273.077 1

[M+H]⁺

7.15

C₁₅H₁₂O₅

Naringenin

169, 131

MMH, CBS

141

87.98

273.098 7

[M+H]⁺

7.16

C₁₅H₁₂O₅

Pinobanksin

273, 151

142

88.23

623.589 6

[M−H]⁻

5.13

C₂₉H₃₆O₁₅

Forsythiaside A

461, 161, 135

YCQZ

143

88.75

445.045 6

[M−H]⁻

6.23

C₂₁H₁₈O₁₁

Glychionide A

445, 269

144

89.45

583.269 7

[M−H]⁻

2.58

C₃₀H₃₂O₁₂

Benzoylpaeoniflorin

431, 387, 121

CBS

145

89.46

463.469 8

[M−H]⁻

5.11

C₁₆H₂₀N₂O₁₀S₂

4-Hydroxy-3-indolylmethyl glucosinolate

285, 267, 195, 96, 74

CLFZ

146

89.56

125.465 0

[M−H]⁻

2.56

C₆H₆O₃

Pyrogallol

79, 96

CBS

147

89.57

209.585 6

[M+H]⁺

5.69

C₁₂H₁₆O₃

β-Asarone

191, 163, 153

CBS

148

90.13

299.054 9

[M−H]⁻

3.87

C₁₆H₁₂O₆

Tenaxin Ⅱ

283, 227

149

90.13

299.054 9

[M−H]⁻

3.59

C₁₆H₁₂O₆

Kaempferide

299, 228

MMH, CBS

150

90.18

445.112 5

[M−H]⁻

3.23

C₂₂H₂₂O₁₀

Wogonin-5-O-D-glucoside

269

151

90.59

227.489 6

[M+H]⁺

2.59

C₁₂H₂₂N₂O₂

Cyclo (Leu-Leu)

209, 114

CZSZ

152

90.88

307.058 5

[M+H]⁺

2.18

C₁₅H₁₄O₇

Leucocyanidin

307, 163, 139, 121

MMH

153

91.26

183.563 1

[M−H]⁻

5.69

C₁₁H₂₀O₂

2-Undecenoic acid

207, 192, 175, 147, 133, 77

DKXR

154

91.26

455.213 6

[M+H]⁺

5.69

C₃₀H₄₈O₃

Oleanolic acid

377

155

92.07

459.105 6

[M−H]⁻

7.59

C₂₂H₂₀O₁₁

Oroxyloside

283, 169

156

92.08

429.169 6

[M−H]⁻

5.16

C₂₁H₁₈O₁₀

Chrysin-7-O-β-D glucoronide

253, 175

157

92.15

283.059 2

[M−H]⁻

6.88

C₁₆H₁₂O₅

Wogonin

268, 240, 239, 167, 139

158

95.27

419.156 0

[M+H]⁺

1.28

C₂₁H₂₂O₉

Liquiritin

419, 257, 239, 211, 147

DKXR

159

95.27

369.194 9

[M+H]⁺

6.52

C₂₂H₂₈N₂O₃

Hirsutine

543, 497, 265

160

96.05

461.109 7

[M+H]⁺

4.15

C₂₂H₂₀O₁₁

Apigenin-7-O-methylglucuronide

461, 271

161

96.14

193.256 4

[M+H]⁺

1.56

C₁₂H₁₆O₂

Sedanenolide

175, 147, 137, 93

CBS

162

97.11

629.784 6

[M−H]⁻

1.56

C₃₁H₃₄O₁₄

Mudanpioside B

583, 553, 431, 165, 121, 77

CBS

163

97.56

313.065 9

[M−H]⁻

6.59

C₁₇H₁₄O₆

Dihydroxy-dimethoxyflavone

298, 255

164

98.56

783.154 8

[M−H]⁻

5.12

C₃₇H₃₆O₁₉

3′, 6′-di-O-Galloylpaeoniflorin

783, 765, 631, 465, 313

CBS

165

99.56

451.896 3

[M−H]⁻

8.59

C₁₃H₂₅NO₁₀S₃

1-Thio-β-D-glucopyranose 1-(6-(methylsulfinyl)-N-(sulfooxy)hexanimi date)

386, 259, 208, 96, 74

CLFZ

166

100.26

300.256 9

[M+H]⁺

3.65

C₁₈H₃₇NO₂

Palmidrol

283, 255

CBS

167

101.79

115.891 1

[M−H]⁻

2.56

C₅H₈O₃

Levulinic acid

117, 102, 89, 74

DKXR, CBS

168

101.79

355.203 4

[M+H]⁺

5.1

C₂₁H₂₆N₂O₃

Yohimbine

355, 212, 144

169

103.47

499.207 9

[M+H]⁺

6.84

C₂₆H₃₀N₂O₈

Strictosamide

337, 267

170

104.32

432.256 3

[M+H]⁺

6.77

C₁₉H₂₈O₁₁

Benzyl-β-gentiobioside

327, 255

CLFZ

171

104.75

167.071 3

[M+H]⁺

5.12

C₉H₁₀O₃

Paeonol

167, 149, 121

CBS

172

105.25

287.145 6

[M−H]⁻

8.96

C₁₅H₁₂O₆

Dihydrokaempferol

287, 93, 193, 175

CBS

173

107.89

477.120 3

[M−H]⁻

50.56

C₂₃H₂₆O₁₁

Calceolarioside A

360, 325, 290, 203, 163

YCQZ

174

108.36

477.889 9

[M−H]⁻

64.88

C₂₃H₂₆O₁₁

Calceolarioside B

YCQZ

No.	Compound	Degree	Origin
1	Baicalein	65	HQ
2	Tenaxin Ⅱ	65	HQ
3	Skullcapflavon Ⅱ	63	HQ
4	Skullcapflavon Ⅰ	62	HQ
5	Glabridin	60	DKXR
6	Quercetin	60	CZSZ
7	Dihydroxy-dimethoxyflavone	60	HQ
8	Matairesinol	59	DKXR
9	Luteolin	59	CZSZ
10	Wogonin	59	HQ
11	Oroxylin A	59	HQ
12	Myricetin	58	GT
13	Yohimbine	57	GT
14	Kaempferide	56	MMH, CBS
15	Naringenin	52	MMH, CBS
16	Sinapine thiocyanate	52	CLFZ
17	Rhynchophylline	51	GT
18	Isorhynchophylline	51	GT
19	Corynoxeine	50	GT
20	Hirsutine	47	GT

No.

Compound

Degree

Origin

Baicalein

Tenaxin Ⅱ

Skullcapflavon Ⅱ

Skullcapflavon Ⅰ

Glabridin

DKXR

Quercetin

CZSZ

Dihydroxy-dimethoxyflavone

Matairesinol

DKXR

Luteolin

CZSZ

Wogonin

Oroxylin A

Myricetin

Yohimbine

Kaempferide

MMH, CBS

Naringenin

MMH, CBS

Sinapine thiocyanate

CLFZ

Rhynchophylline

Isorhynchophylline

Corynoxeine

Hirsutine