药学学报

No.	t_R/min	m/z	Mode	Annotation		No.	t_R/min	m/z	Mode	Annotation
1	0.92	225.060 2	-	Glucoheptonic acid		133	6.42	579.207 9	-	Eleutheroside E1
2	0.97	191.055 0	-	Quinic acid	134	6.42	580.061 3	-	Coumaroyl glucoraphenin
3	0.97	345.118 0	-	Aucubin	135	6.44	415.103 6	-	Puerarin
4	0.99	166.123 1	+	Pseudoephedrine^*		6.52	417.119 2	+
5	1.12	169.013 2	-	Gallic acid	136	6.45	431.096 9	-	Apigenin 7-O-β-D-glucoside
6	1.29	152.107 5	+	Norephedrine		6.45	433.114 3	+
7	1.29	166.123 1	+	(−)-Ephedrine^*	137	6.48	639.155 0	-	Isorhamnetin-3, 7-diglucoside
8	1.32	169.013 1	-	Gallic acid	138	6.48	461.073 0	-	Scutellarein-6-O-glucuronide
9	1.42	180.138 7	+	Methylephedrine		6.80	463.088 0	+
10	1.45	372.042 4	-	Gluconapin	139	6.49	610.070 2	-	Feruloyl glucoraphenin
11	1.46	373.113 6	-	Geniposidic acid^*	140	6.50	640.082 6	-	Sinapoyl glucoraphenin
	1.47	397.110 8	+		141	6.51	515.132 1	-	Isochlorogenic acid^*
12	1.48	422.024 4	-	Glucoiberin	142	6.56	205.085 5	-	4-Hydroxy-3-(3-methylbut-2-enyl)benzoic acid
13	1.48	452.034 2	-	4-Methylsulfonylbutyl glucosinolate	143	6.57	637.213 0	-	Plantainoside C
14	1.52	434.025 4	-	Glucoraphenin		6.80	639.229 6	+
15	1.57	176.020 2	+	Sulforaphene	144	6.58	799.229 2	-	3', 6-Disinapoylsucrose
16	1.65	450.020 1	-	4-Methylsulfonyl-3-butenyl glucosinolate		6.62	777.221 1	+
17	1.65	434.025 4	-	Glucoraphenin	145	6.61	449.107 5	-	Eriodictyol-7-O-glucoside
18	1.67	388.037 1	-	Epiprogoitrin	146	6.63	505.134 6	-	Isorinic acid-3'-O-glucoside
19	1.77	461.166 8	-	Decaffeoylverbascoside	147	6.65	387.128 9	+	Sinapoylglucose
20	1.78	450.056 6	-	5-Methylsulfinyl-n-pentyl glucosinolate	148	6.65	538.050 6	-	Glucoraphenin benzoate
21	1.90	375.129 5	-	Loganic acid		6.73	540.065 7	+
	1.78	399.127 7	+		149	6.71	1445.426 5	-	1-Sinapoyl-2-feruloyl gentiobiose
22	1.93	153.017 9	-	Protocatechuic acid^*	150	6.72	417.120 0	-	Glucoliquiritigenin
23	2.10	353.087 6	-	Neochlorogenic acid	151	6.75	693.202 8	-	Helonioside A
	2.07	355.103 1	+		152	6.75	187.096 1	-	Azelaic acid
24	2.10	577.135 1	-	Procyanidin B2	153	6.77	435.129 7	-	Phloridzin
	2.12	579.150 5	+			5.22	437.142 4	+
25	2.12	310.165 1	+	Sinapine^*	154	6.79	359.077 0	-	Rosmarinic acid^*
26	2.35	618.203 3	-	Triglucosyl cyanogen glycoside		6.90	361.092 2	+
27	2.54	411.127 7	+	Secologanin	155	6.84	509.164 2	-	Paeobrin
28	2.55	289.070 9	-	Epicatechin	156	6.86	177.017 9	-	Esculetin
29	2.58	305.066 5	-	Gallocatechin		6.13	179.034 3	+
30	2.69	289.070 9	-	Epicatechin	157	6.95	181.050 1	+	Caffeic acid
31	3.17	547.165 8	-	Sibiricose A1	158	6.95	477.102 4	-	Hesperetin 3'-O-glucuronide
32	3.25	456.150 5	-	Amygdalin^*		7.01	479.118 4	+
	3.32	475.191 8	+		159	6.97	607.201 6	-	Osmanthuside J
33	3.25	618.203 4	-	Triglucosyl cyanogen glycoside	160	7.00	475.087 8	-	Hispidulin 7-glucuronide
34	3.44	177.017 8	-	Dihydroxycoumarin		6.98	477.103 5	+
35	3.45	355.103 5	+	Chlorogenic acid^*	161	7.05	753.227 0	-	3', 6-Disinapoylsucrose
	3.46	353.087 4	-		162	7.06	461.108 5	-	Homoplantaginin
36	3.57	369.182 1	+	Mitraphylline		7.14	463.123 5	+
37	3.65	353.087 6	-	4-O-Caffeoylquinic acid	163	7.078	507.148 8	-	Lactiflorin
	3.65	355.103 4	+		164	7.171	637.212 9	-	Leucosceptoside A
38	3.61	179.034 4	-	Caffeic acid^*		7.282	639.229 3	+
39	3.73	387.129 1	-	Miscanthoside	165	7.203	505.099 7	-	Tricin-7-glucuronoside
40	3.92	593.150 3	-	Apigenin-6, 8-di-C-glycoside		7.291	507.115 4	+
	3.93	595.166 9	+		166	7.213	511.053 7	-	Baicalein 7-O-glucoside 5-O-sulfate
41	3.93	371.196 7	+	Rhyncophyllic acid	167	7.226	287.056 1	-	Eriodictyol
42	3.93	411.125 6	+	Geniposide^*		7.326	289.070 4	+
43	4.03	635.086 9	-	1, 3, 6-Tri-O-galloylglucose	168	7.333	477.103 5	+	Hispidulin 7-O-glucuronide
44	4.08	521.202 6	-	Isolariciresinol 4-O-glucopyranoside	169	7.439	369.180 9	+	Speciophylline
45	4.12	327.108 2	-	Ethyl vanillin glucoside	170	7.422	431.097 1	-	Oroxin A
46	4.14	381.116 5	+	Sweroside		7.475	433.114 3	+
47	4.16	547.166 1	-	Sibiricose A6	171	7.432	345.060 2	-	Viscidulin Ⅲ
48	4.16	294.098 4	-	Prulaurasin		7.521	347.076 9	+
49	4.18	420.045 7	-	Glucoerucin	172	7.595	445.078 0	-	Baicalin^*
50	4.23	207.138 6	+	Sinapoylmalate		7.695	447.092 6	+
51	4.36	525.161 1	-	Paeoniflorin^*	173	7.673	651.230 3	-	Compound NP-002173
	4.35	481.171 2	+			7.752	675.227 3	+
52	4.36	641.209 5	-	Isomaltopaeoniflorin	174	7.722	477.102 6	-	Homoeriodictyol glucuronide
53	4.37	609.146 4	-	Luteolin-3', 7-di-O-glucoside		7.81	479.120 8	+
	4.47	611.161 6	+		175	7.77	287.055 1	-	Maesopsin
54	4.48	369.182 1	+	Isomitraphylline	176	7.78	505.097 3	-	Tricin 7-O-glucuronide
55	4.46	593.147 4	-	Vitexin 4-O-glucoside		7.86	507.113 1	+
56	4.51	343.139 8	-	Dihydroconiferin	177	7.91	447.092 8	-	Naringenin-4'-O-glucuronide
57	4.56	639.192 3	-	Plantamajoside D		7.99	449.107 7	+
58	4.57	785.251 7	-	Echinacoside	178	7.99	445.113 7	-	Wogonin 7-O-glucoside
59	4.59	327.144 4	-	Perilloside B		8.63	447.128 5	+
60	4.60	563.138 0	-	Schaftoside^*	179	8.02	415.103 8	-	Daidzin
	4.63	565.154 5	+			8.02	417.119 4	+
61	4.65	495.150 8	-	Oxypaeoniflorin	180	8.02	591.206 6	-	Osmanthuside B6
	4.67	497.165 7	+		181	8.08	477.102 6	-	Hesperetin-7-O-glucuronide
62	4.67	525.161 0	-	Albiflorin^*	182	8.15	445.075 8	-	Baicalein 6-O-glucuronide
	4.75	503.153 4	+		183	8.16	461.108 4	-	Peonidin 3-galactoside
63	4.71	401.208 4	+	Isorhynchophylline N-oxide		8.24	463.123 3	+
64	4.72	543.116 5	-	Paeoniflorinsulfonic acid	184	8.18	651.230 0	-	Compound NP-002173
65	4.73	447.092 6	-	Luteolin 7-glucoside		8.28	653.245 7	+
	4.82	471.090 5	+		185	8.23	285.039 7	-	Luteolin^*
66	4.74	593.147 3	-	Pelargonin	186	8.24	431.098 9	-	Kaempferol-7-O-rhamnoside
	4.80	595.166 8	+			8.27	433.114 7	+
67	4.84	563.141 0	-	Isoschaftoside	187	8.28	445.077 8	-	Baicalein 5-O-glucuronide
	4.69	565.154 5	+			8.24	447.092 5	+
68	4.93	495.151 3	-	Oxypaeoniflorin	188	8.36	475.087 8	-	Hispidulin 7-glucuronide
69	4.93	371.196 6	+	Rhyncophyllic acid		8.44	477.103 6	+
70	4.96	401.208 1	+	Isorhynchophylline N-oxide	189	8.40	345.061 5	-	5, 7, 3', 4'-Tetrahydroxy-6, 8-dimethoxyflavone
71	4.96	367.102 6	-	3-O-Feruloylquinic acid^*		8.70	347.077 0	+
72	4.99	787.263 9	-	Liriodendrin	190	8.52	429.081 8	-	Chrysin-7-O-glucuronide
73	5.00	639.154 4	-	Dactylin		8.60	431.098 1	+
74	5.01	577.154 8	-	Chrysin 8-C-glucoside 6-C-glucoside	191	8.52	459.093 8	-	Oroxylin A-7-O-glucuronide
	5.04	579.173 0	+			8.64	461.107 6	+
75	5.07	369.182 0	+	Mitraphylline	192	8.55	591.206 6	-	Osmanthuside B6
76	5.13	621.180 7	-	Isocrenatoside	193	8.64	511.054 0	-	Baicalein 7-O-glucoside 6-O-sulfate
77	5.15	509.130 3	+	Syringetin 3-glucoside	194	8.71	475.087 8	-	Hispidulin 7-glucuronide
78	5.15	433.113 9	-	Naringenin-7-O-glucoside		8.78	477.103 6	+
79	5.20	755.239 7	-	Compound NP-000173	195	8.82	445.077 3	-	Baicalein 6-O-glucuronide
80	5.21	465.103 9	-	Plantagoside		8.88	447.094 2	+
81	5.23	431.101 1	-	Apigenin-8-C-glucoside	196	8.88	459.093 8	-	Wogonoside^*
	5.24	433.114 4	+			8.95	461.107 5	+
82	5.25	441.082 2	-	Catechin gallate	197	9.04	489.102 3	-	Comanthoside B
83	5.25	447.092 7	-	Plantaginin		9.07	491.119 5	+
	5.29	449.109 3	+		198	9.09	345.060 2	-	Viscidulin Ⅲ
84	5.57	319.118 4	+	Paeoniflorigenone		9.19	347.075 7	+
85	5.29	609.181 9	-	Calceolarioside C	199	9.16	629.186 2	-	Benzoylpaeoniflorin
86	5.32	207.138 6	+	Sinapoylmalate		9.16	607.180 1	+
87	5.37	441.082 4	-	Epicatechin gallate	200	9.29	475.123 5	+	6'-O-Acetylgenistin
88	5.39	433.113 9	-	Naringenin-7-O-glucoside		8.28	653.245 7	+
	5.39	435.127 9	+		201	9.31	629.186 1	-	Benzoylpaeoniflorin
89	5.39	491.119 1	-	Tricin 7-O-glucoside^*		9.36	607.180 5	+
90	5.47	547.145 0	-	Chrysin 6-C-glucoside 8-C-arabinoside	202	9.35	315.180 2	-	Perilloside C
	5.51	549.159 3	+		203	9.42	549.125 7	-	Chrysosplenetin 5-O-glucuronide
91	5.58	383.197 5	+	Isocorynoxeine^*	204	9.47	299.055 3	-	Tectorigenin
92	5.48	607.073 4	-	Glucoraphenin-5-hydroxyindole-3-acetic acid		9.48	301.071 2	+
	5.49	609.088 9	+		205	9.48	223.075 4	-	Hydroxychalcone
93	5.49	577.154 4	-	2-O-Rhamnosylvitexin	206	9.51	269.044 8	-	Apigenin^*
	5.65	579.173 3	+			9.73	271.060 7	+
94	5.53	596.055 5	-	Caffeoyl glucoraphenin	207	9.66	269.044 9	-	Apigenin isomers
95	5.57	521.203 0	-	Lariciresinol 4-O-glucoyranoside		9.64	271.060 6	+
96	5.58	434.061 6	-	Glucoberteroin	208	9.76	285.039 7	-	Kaempferol^*
97	5.60	573.210 0	-	5β-Carboxystrictosidine		9.85	287.055 5	+
98	5.62	463.086 7	-	Quercetin-4'-O-glucoside	209	9.80	299.055 3	-	Chrysoeriol
	5.63	465.102 8	+			9.82	301.071 2	+
99	5.65	431.097 2	-	Isovitexin	211	9.81	395.204 0	-	Tsangane 3-glucoside
	5.67	433.114 0	+		212	9.90	329.066 5	-	Tricin
100	5.71	623.196 8	-	Acteoside^*		9.97	331.081 0	+
	5.71	647.196 3	+		213	9.98	299.055 4	-	Hispidulin
101	5.71	621.180 9	-	Crenatoside	214	10.06	359.077 3	-	Sideritoflavone
102	5.72	607.130 7	-	Baicalein-6-O-glucose-7-O-glucuronide		10.04	361.092 7	+
103	5.72	939.109 1	-	Penta-O-galloyl-β-glucose	215	10.09	303.050 3	-	Taxifolin
104	5.73	521.129 5	-	Salviaflaside		10.24	305.066 3	+
105	5.74	631.166 4	-	Galloylpaeoniflorin	216	10.12	269.044 9	-	Baicalein^*
	5.74	655.165 5	+			10.22	271.060 7	+
106	5.80	431.097 1	-	Oroxin A	217	10.13	285.039 8	-	Luteolin
107	5.81	509.130 5	+	Syringetin 3-glucoside		10.21	287.055 3	+
	5.82	531.112 8	+		218	10.24	299.055 3	-	Scutellarein 4'-methyl ether
108	5.83	477.062 6	-	1-Methoxyindol-3-ylmethyl glucosinolate	219	10.42	329.066 6	-	4', 5, 7-Trihydroxy-3, 6-dimethoxyflavone
109	5.84	351.170 4	+	Strychnine N-oxide		10.42	331.082 3	+
110	5.85	547.145 0	-	Chrysin 8-C-glucoside 6-C-arabinoside	220	10.46	327.087 0	+	Usnic acid
	5.90	549.159 2	+		221	10.53	223.075 4	-	Hydroxychalcone
111	5.94	383.197 5	+	Corynoxeine^*	222	10.61	299.055 4	-	Tectorigenin
112	5.93	461.072 9	-	Scutellarin^*		10.72	301.071 2	+
	5.95	463.088 0	+		223	11.08	329.066 6	-	3, 4'-Dimethoxy-5, 7, 3'-trihydroxyflavone
113	5.96	463.086 8	-	Quercetin-4'-O-glucoside		11.18	331.082 4	+
114	5.98	351.170 3	+	Strychnine N-oxide	224	11.31	313.107 9	+	Baicalein trimethyl ether
115	5.98	475.124 1	-	Plantasioside	225	11.56	359.077 3	-	3, 5, 7-Trihydroxy-3', 4', 5'-trimethoxyflavone
116	6.00	723.212 8	-	1-Sinapoyl-2-feruloylgentiobiose	11.66	361.092 5	+
117	6.00	385.213 1	+	Isorhyncophylline^*	226	11.67	821.397 6	-	Uralsaponin A
118	6.01	477.102 3	-	Petunidin-3-O-β-glucopyranoside		11.68	823.412 5	+
119	6.02	353.185 4	+	Ajmalicine	227	11.68	343.082 4	-	Tricin methyl ether
120	6.10	181.049 6	+	Caffeic acid		11.79	345.097 3	+
121	6.11	415.103 7	-	Daidzein-6-C-glucoside	228	11.74	255.065 9	-	Dihydrodaidzein
	6.11	417.119 1	+		229	11.98	283.060 4	-	Wogonin^*
122	6.11	640.082 8	-	Sinapinic acid 4-methylsulfinyl-3-butenyl glucosinolate		12.10	285.076 0	+
123	6.13	623.197 1	-	Isoacteoside^*	230	11.99	313.070 9	-	3, 7-Dihydroxy-3', 4'-dimethoxyflavone
	6.14	647.196 2	+		231	12.13	253.049 7	-	Chrysin^*
124	6.15	339.070 9	-	Sinapoyl malate		12.26	253.049 7	+
125	6.19	461.108 1	-	Tectoridin	232	12.20	255.065 7	-	Pinocembrine
	6.418	463.123 1	+		233	12.21	373.091 6	-	Skullcapflavone Ⅱ
126	6.22	642.099 4	-	Sinapinic acid glucoraphanin		12.23	375.108 4	+
127	6.22	653.208 6	-	Campneoside	234	12.22	313.070 7	-	Pectolinarigenin
128	6.26	565.190 7	-	Simplocosin		12.21	315.086 0	+
129	6.28	515.132 0	-	3, 4-Di-O-caffeoylquinic acid	235	12.45	313.070 7	-	Cirsimaritin
130	6.34	385.211 4	+	Rhynchophylline^*		12.48	315.086 3	+
131	6.34	631.166 4	-	Galloylalbiflorin	236	12.47	283.060 3	-	Oroxylin A
	6.37	655.165 8	+			12.56	285.076 0	+
132	6.40	339.144 9	-	Isoprenylhydroquinone glucoside	237	12.93	343.080 9	-	Eupatilin
						13.05	345.097 6	+

No.	t_R/min	m/z	Mode	Annotation		No.	t_R/min	m/z	Mode	Annotation
1	0.92	225.060 2	-	Glucoheptonic acid		133	6.42	579.207 9	-	Eleutheroside E1
2	0.97	191.055 0	-	Quinic acid	134	6.42	580.061 3	-	Coumaroyl glucoraphenin
3	0.97	345.118 0	-	Aucubin	135	6.44	415.103 6	-	Puerarin
4	0.99	166.123 1	+	Pseudoephedrine^*		6.52	417.119 2	+
5	1.12	169.013 2	-	Gallic acid	136	6.45	431.096 9	-	Apigenin 7-O-β-D-glucoside
6	1.29	152.107 5	+	Norephedrine		6.45	433.114 3	+
7	1.29	166.123 1	+	(−)-Ephedrine^*	137	6.48	639.155 0	-	Isorhamnetin-3, 7-diglucoside
8	1.32	169.013 1	-	Gallic acid	138	6.48	461.073 0	-	Scutellarein-6-O-glucuronide
9	1.42	180.138 7	+	Methylephedrine		6.80	463.088 0	+
10	1.45	372.042 4	-	Gluconapin	139	6.49	610.070 2	-	Feruloyl glucoraphenin
11	1.46	373.113 6	-	Geniposidic acid^*	140	6.50	640.082 6	-	Sinapoyl glucoraphenin
	1.47	397.110 8	+		141	6.51	515.132 1	-	Isochlorogenic acid^*
12	1.48	422.024 4	-	Glucoiberin	142	6.56	205.085 5	-	4-Hydroxy-3-(3-methylbut-2-enyl)benzoic acid
13	1.48	452.034 2	-	4-Methylsulfonylbutyl glucosinolate	143	6.57	637.213 0	-	Plantainoside C
14	1.52	434.025 4	-	Glucoraphenin		6.80	639.229 6	+
15	1.57	176.020 2	+	Sulforaphene	144	6.58	799.229 2	-	3', 6-Disinapoylsucrose
16	1.65	450.020 1	-	4-Methylsulfonyl-3-butenyl glucosinolate		6.62	777.221 1	+
17	1.65	434.025 4	-	Glucoraphenin	145	6.61	449.107 5	-	Eriodictyol-7-O-glucoside
18	1.67	388.037 1	-	Epiprogoitrin	146	6.63	505.134 6	-	Isorinic acid-3'-O-glucoside
19	1.77	461.166 8	-	Decaffeoylverbascoside	147	6.65	387.128 9	+	Sinapoylglucose
20	1.78	450.056 6	-	5-Methylsulfinyl-n-pentyl glucosinolate	148	6.65	538.050 6	-	Glucoraphenin benzoate
21	1.90	375.129 5	-	Loganic acid		6.73	540.065 7	+
	1.78	399.127 7	+		149	6.71	1445.426 5	-	1-Sinapoyl-2-feruloyl gentiobiose
22	1.93	153.017 9	-	Protocatechuic acid^*	150	6.72	417.120 0	-	Glucoliquiritigenin
23	2.10	353.087 6	-	Neochlorogenic acid	151	6.75	693.202 8	-	Helonioside A
	2.07	355.103 1	+		152	6.75	187.096 1	-	Azelaic acid
24	2.10	577.135 1	-	Procyanidin B2	153	6.77	435.129 7	-	Phloridzin
	2.12	579.150 5	+			5.22	437.142 4	+
25	2.12	310.165 1	+	Sinapine^*	154	6.79	359.077 0	-	Rosmarinic acid^*
26	2.35	618.203 3	-	Triglucosyl cyanogen glycoside		6.90	361.092 2	+
27	2.54	411.127 7	+	Secologanin	155	6.84	509.164 2	-	Paeobrin
28	2.55	289.070 9	-	Epicatechin	156	6.86	177.017 9	-	Esculetin
29	2.58	305.066 5	-	Gallocatechin		6.13	179.034 3	+
30	2.69	289.070 9	-	Epicatechin	157	6.95	181.050 1	+	Caffeic acid
31	3.17	547.165 8	-	Sibiricose A1	158	6.95	477.102 4	-	Hesperetin 3'-O-glucuronide
32	3.25	456.150 5	-	Amygdalin^*		7.01	479.118 4	+
	3.32	475.191 8	+		159	6.97	607.201 6	-	Osmanthuside J
33	3.25	618.203 4	-	Triglucosyl cyanogen glycoside	160	7.00	475.087 8	-	Hispidulin 7-glucuronide
34	3.44	177.017 8	-	Dihydroxycoumarin		6.98	477.103 5	+
35	3.45	355.103 5	+	Chlorogenic acid^*	161	7.05	753.227 0	-	3', 6-Disinapoylsucrose
	3.46	353.087 4	-		162	7.06	461.108 5	-	Homoplantaginin
36	3.57	369.182 1	+	Mitraphylline		7.14	463.123 5	+
37	3.65	353.087 6	-	4-O-Caffeoylquinic acid	163	7.078	507.148 8	-	Lactiflorin
	3.65	355.103 4	+		164	7.171	637.212 9	-	Leucosceptoside A
38	3.61	179.034 4	-	Caffeic acid^*		7.282	639.229 3	+
39	3.73	387.129 1	-	Miscanthoside	165	7.203	505.099 7	-	Tricin-7-glucuronoside
40	3.92	593.150 3	-	Apigenin-6, 8-di-C-glycoside		7.291	507.115 4	+
	3.93	595.166 9	+		166	7.213	511.053 7	-	Baicalein 7-O-glucoside 5-O-sulfate
41	3.93	371.196 7	+	Rhyncophyllic acid	167	7.226	287.056 1	-	Eriodictyol
42	3.93	411.125 6	+	Geniposide^*		7.326	289.070 4	+
43	4.03	635.086 9	-	1, 3, 6-Tri-O-galloylglucose	168	7.333	477.103 5	+	Hispidulin 7-O-glucuronide
44	4.08	521.202 6	-	Isolariciresinol 4-O-glucopyranoside	169	7.439	369.180 9	+	Speciophylline
45	4.12	327.108 2	-	Ethyl vanillin glucoside	170	7.422	431.097 1	-	Oroxin A
46	4.14	381.116 5	+	Sweroside		7.475	433.114 3	+
47	4.16	547.166 1	-	Sibiricose A6	171	7.432	345.060 2	-	Viscidulin Ⅲ
48	4.16	294.098 4	-	Prulaurasin		7.521	347.076 9	+
49	4.18	420.045 7	-	Glucoerucin	172	7.595	445.078 0	-	Baicalin^*
50	4.23	207.138 6	+	Sinapoylmalate		7.695	447.092 6	+
51	4.36	525.161 1	-	Paeoniflorin^*	173	7.673	651.230 3	-	Compound NP-002173
	4.35	481.171 2	+			7.752	675.227 3	+
52	4.36	641.209 5	-	Isomaltopaeoniflorin	174	7.722	477.102 6	-	Homoeriodictyol glucuronide
53	4.37	609.146 4	-	Luteolin-3', 7-di-O-glucoside		7.81	479.120 8	+
	4.47	611.161 6	+		175	7.77	287.055 1	-	Maesopsin
54	4.48	369.182 1	+	Isomitraphylline	176	7.78	505.097 3	-	Tricin 7-O-glucuronide
55	4.46	593.147 4	-	Vitexin 4-O-glucoside		7.86	507.113 1	+
56	4.51	343.139 8	-	Dihydroconiferin	177	7.91	447.092 8	-	Naringenin-4'-O-glucuronide
57	4.56	639.192 3	-	Plantamajoside D		7.99	449.107 7	+
58	4.57	785.251 7	-	Echinacoside	178	7.99	445.113 7	-	Wogonin 7-O-glucoside
59	4.59	327.144 4	-	Perilloside B		8.63	447.128 5	+
60	4.60	563.138 0	-	Schaftoside^*	179	8.02	415.103 8	-	Daidzin
	4.63	565.154 5	+			8.02	417.119 4	+
61	4.65	495.150 8	-	Oxypaeoniflorin	180	8.02	591.206 6	-	Osmanthuside B6
	4.67	497.165 7	+		181	8.08	477.102 6	-	Hesperetin-7-O-glucuronide
62	4.67	525.161 0	-	Albiflorin^*	182	8.15	445.075 8	-	Baicalein 6-O-glucuronide
	4.75	503.153 4	+		183	8.16	461.108 4	-	Peonidin 3-galactoside
63	4.71	401.208 4	+	Isorhynchophylline N-oxide		8.24	463.123 3	+
64	4.72	543.116 5	-	Paeoniflorinsulfonic acid	184	8.18	651.230 0	-	Compound NP-002173
65	4.73	447.092 6	-	Luteolin 7-glucoside		8.28	653.245 7	+
	4.82	471.090 5	+		185	8.23	285.039 7	-	Luteolin^*
66	4.74	593.147 3	-	Pelargonin	186	8.24	431.098 9	-	Kaempferol-7-O-rhamnoside
	4.80	595.166 8	+			8.27	433.114 7	+
67	4.84	563.141 0	-	Isoschaftoside	187	8.28	445.077 8	-	Baicalein 5-O-glucuronide
	4.69	565.154 5	+			8.24	447.092 5	+
68	4.93	495.151 3	-	Oxypaeoniflorin	188	8.36	475.087 8	-	Hispidulin 7-glucuronide
69	4.93	371.196 6	+	Rhyncophyllic acid		8.44	477.103 6	+
70	4.96	401.208 1	+	Isorhynchophylline N-oxide	189	8.40	345.061 5	-	5, 7, 3', 4'-Tetrahydroxy-6, 8-dimethoxyflavone
71	4.96	367.102 6	-	3-O-Feruloylquinic acid^*		8.70	347.077 0	+
72	4.99	787.263 9	-	Liriodendrin	190	8.52	429.081 8	-	Chrysin-7-O-glucuronide
73	5.00	639.154 4	-	Dactylin		8.60	431.098 1	+
74	5.01	577.154 8	-	Chrysin 8-C-glucoside 6-C-glucoside	191	8.52	459.093 8	-	Oroxylin A-7-O-glucuronide
	5.04	579.173 0	+			8.64	461.107 6	+
75	5.07	369.182 0	+	Mitraphylline	192	8.55	591.206 6	-	Osmanthuside B6
76	5.13	621.180 7	-	Isocrenatoside	193	8.64	511.054 0	-	Baicalein 7-O-glucoside 6-O-sulfate
77	5.15	509.130 3	+	Syringetin 3-glucoside	194	8.71	475.087 8	-	Hispidulin 7-glucuronide
78	5.15	433.113 9	-	Naringenin-7-O-glucoside		8.78	477.103 6	+
79	5.20	755.239 7	-	Compound NP-000173	195	8.82	445.077 3	-	Baicalein 6-O-glucuronide
80	5.21	465.103 9	-	Plantagoside		8.88	447.094 2	+
81	5.23	431.101 1	-	Apigenin-8-C-glucoside	196	8.88	459.093 8	-	Wogonoside^*
	5.24	433.114 4	+			8.95	461.107 5	+
82	5.25	441.082 2	-	Catechin gallate	197	9.04	489.102 3	-	Comanthoside B
83	5.25	447.092 7	-	Plantaginin		9.07	491.119 5	+
	5.29	449.109 3	+		198	9.09	345.060 2	-	Viscidulin Ⅲ
84	5.57	319.118 4	+	Paeoniflorigenone		9.19	347.075 7	+
85	5.29	609.181 9	-	Calceolarioside C	199	9.16	629.186 2	-	Benzoylpaeoniflorin
86	5.32	207.138 6	+	Sinapoylmalate		9.16	607.180 1	+
87	5.37	441.082 4	-	Epicatechin gallate	200	9.29	475.123 5	+	6'-O-Acetylgenistin
88	5.39	433.113 9	-	Naringenin-7-O-glucoside		8.28	653.245 7	+
	5.39	435.127 9	+		201	9.31	629.186 1	-	Benzoylpaeoniflorin
89	5.39	491.119 1	-	Tricin 7-O-glucoside^*		9.36	607.180 5	+
90	5.47	547.145 0	-	Chrysin 6-C-glucoside 8-C-arabinoside	202	9.35	315.180 2	-	Perilloside C
	5.51	549.159 3	+		203	9.42	549.125 7	-	Chrysosplenetin 5-O-glucuronide
91	5.58	383.197 5	+	Isocorynoxeine^*	204	9.47	299.055 3	-	Tectorigenin
92	5.48	607.073 4	-	Glucoraphenin-5-hydroxyindole-3-acetic acid		9.48	301.071 2	+
	5.49	609.088 9	+		205	9.48	223.075 4	-	Hydroxychalcone
93	5.49	577.154 4	-	2-O-Rhamnosylvitexin	206	9.51	269.044 8	-	Apigenin^*
	5.65	579.173 3	+			9.73	271.060 7	+
94	5.53	596.055 5	-	Caffeoyl glucoraphenin	207	9.66	269.044 9	-	Apigenin isomers
95	5.57	521.203 0	-	Lariciresinol 4-O-glucoyranoside		9.64	271.060 6	+
96	5.58	434.061 6	-	Glucoberteroin	208	9.76	285.039 7	-	Kaempferol^*
97	5.60	573.210 0	-	5β-Carboxystrictosidine		9.85	287.055 5	+
98	5.62	463.086 7	-	Quercetin-4'-O-glucoside	209	9.80	299.055 3	-	Chrysoeriol
	5.63	465.102 8	+			9.82	301.071 2	+
99	5.65	431.097 2	-	Isovitexin	211	9.81	395.204 0	-	Tsangane 3-glucoside
	5.67	433.114 0	+		212	9.90	329.066 5	-	Tricin
100	5.71	623.196 8	-	Acteoside^*		9.97	331.081 0	+
	5.71	647.196 3	+		213	9.98	299.055 4	-	Hispidulin
101	5.71	621.180 9	-	Crenatoside	214	10.06	359.077 3	-	Sideritoflavone
102	5.72	607.130 7	-	Baicalein-6-O-glucose-7-O-glucuronide		10.04	361.092 7	+
103	5.72	939.109 1	-	Penta-O-galloyl-β-glucose	215	10.09	303.050 3	-	Taxifolin
104	5.73	521.129 5	-	Salviaflaside		10.24	305.066 3	+
105	5.74	631.166 4	-	Galloylpaeoniflorin	216	10.12	269.044 9	-	Baicalein^*
	5.74	655.165 5	+			10.22	271.060 7	+
106	5.80	431.097 1	-	Oroxin A	217	10.13	285.039 8	-	Luteolin
107	5.81	509.130 5	+	Syringetin 3-glucoside		10.21	287.055 3	+
	5.82	531.112 8	+		218	10.24	299.055 3	-	Scutellarein 4'-methyl ether
108	5.83	477.062 6	-	1-Methoxyindol-3-ylmethyl glucosinolate	219	10.42	329.066 6	-	4', 5, 7-Trihydroxy-3, 6-dimethoxyflavone
109	5.84	351.170 4	+	Strychnine N-oxide		10.42	331.082 3	+
110	5.85	547.145 0	-	Chrysin 8-C-glucoside 6-C-arabinoside	220	10.46	327.087 0	+	Usnic acid
	5.90	549.159 2	+		221	10.53	223.075 4	-	Hydroxychalcone
111	5.94	383.197 5	+	Corynoxeine^*	222	10.61	299.055 4	-	Tectorigenin
112	5.93	461.072 9	-	Scutellarin^*		10.72	301.071 2	+
	5.95	463.088 0	+		223	11.08	329.066 6	-	3, 4'-Dimethoxy-5, 7, 3'-trihydroxyflavone
113	5.96	463.086 8	-	Quercetin-4'-O-glucoside		11.18	331.082 4	+
114	5.98	351.170 3	+	Strychnine N-oxide	224	11.31	313.107 9	+	Baicalein trimethyl ether
115	5.98	475.124 1	-	Plantasioside	225	11.56	359.077 3	-	3, 5, 7-Trihydroxy-3', 4', 5'-trimethoxyflavone
116	6.00	723.212 8	-	1-Sinapoyl-2-feruloylgentiobiose	11.66	361.092 5	+
117	6.00	385.213 1	+	Isorhyncophylline^*	226	11.67	821.397 6	-	Uralsaponin A
118	6.01	477.102 3	-	Petunidin-3-O-β-glucopyranoside		11.68	823.412 5	+
119	6.02	353.185 4	+	Ajmalicine	227	11.68	343.082 4	-	Tricin methyl ether
120	6.10	181.049 6	+	Caffeic acid		11.79	345.097 3	+
121	6.11	415.103 7	-	Daidzein-6-C-glucoside	228	11.74	255.065 9	-	Dihydrodaidzein
	6.11	417.119 1	+		229	11.98	283.060 4	-	Wogonin^*
122	6.11	640.082 8	-	Sinapinic acid 4-methylsulfinyl-3-butenyl glucosinolate		12.10	285.076 0	+
123	6.13	623.197 1	-	Isoacteoside^*	230	11.99	313.070 9	-	3, 7-Dihydroxy-3', 4'-dimethoxyflavone
	6.14	647.196 2	+		231	12.13	253.049 7	-	Chrysin^*
124	6.15	339.070 9	-	Sinapoyl malate		12.26	253.049 7	+
125	6.19	461.108 1	-	Tectoridin	232	12.20	255.065 7	-	Pinocembrine
	6.418	463.123 1	+		233	12.21	373.091 6	-	Skullcapflavone Ⅱ
126	6.22	642.099 4	-	Sinapinic acid glucoraphanin		12.23	375.108 4	+
127	6.22	653.208 6	-	Campneoside	234	12.22	313.070 7	-	Pectolinarigenin
128	6.26	565.190 7	-	Simplocosin		12.21	315.086 0	+
129	6.28	515.132 0	-	3, 4-Di-O-caffeoylquinic acid	235	12.45	313.070 7	-	Cirsimaritin
130	6.34	385.211 4	+	Rhynchophylline^*		12.48	315.086 3	+
131	6.34	631.166 4	-	Galloylalbiflorin	236	12.47	283.060 3	-	Oroxylin A
	6.37	655.165 8	+			12.56	285.076 0	+
132	6.40	339.144 9	-	Isoprenylhydroquinone glucoside	237	12.93	343.080 9	-	Eupatilin
						13.05	345.097 6	+

基于分子网络与体内非靶标成分谱的降气平哮方治疗哮喘药效物质与作用解析

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杨河 ¹ , 严花 ¹^,² , 单祎文 ¹^,² , 董莹莹 ¹ , 许景 ¹^,² , 谢彤 ¹^,^* , 赵霞 ¹^,²^,^*

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): 3261-3275

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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) : 3261 -3275

基于分子网络与体内非靶标成分谱的降气平哮方治疗哮喘药效物质与作用解析

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杨河¹, 严花¹^,², 单祎文¹^,², 董莹莹¹, 许景¹^,², 谢彤¹^,^*, 赵霞¹^,²^,^*

作者信息

¹南京中医药大学第一临床医学院，儿童健康与中医药省高校重点实验室，江苏南京 210023

²南京中医药大学附属医院，江苏南京 210029

通讯作者:

谢彤， E-mail: xietong@njucm.cn

赵霞， E-mail: zhaoxiahy@126.com

作者简介:

作者贡献:

杨河、董莹莹、许景负责实验实施; 严花、单祎文负责实验技术指导; 谢彤负责数据分析及文章撰写; 赵霞负责实验整体设计和文章审阅。

Integrating molecular networking and in vivo exposure profiling to reveal the material basis and mechanism of Jiangqi Pingxiao Formula against asthma

He YANG¹, Hua YAN¹^,², Yi-wen SHAN¹^,², Ying-ying DONG¹, Jing XU¹^,², Tong XIE¹^,^*, Xia ZHAO¹^,²^,^*

Affiliations

¹Jiangsu Key Laboratory of Children's Health and Chinese Medicine, The First Clinical Medical College, Nanjing University of Chinese Medicine, Nanjing 210023, China

²Affiliated Hospital of Nanjing University of Chinese Medicine, Nanjing 210029, China

出版时间: 2026-09-12 doi: 10.16438/j.0513-4870.2026-0201

文章导航

摘要

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为系统表征降气平哮方治疗儿童支气管哮喘的药效物质及作用机制, 本研究构建了基于特征的分子网络策略, 共检测出237个化学成分; 通过体内非靶标成分谱分析, 比较了小儿降气平哮合剂和传统水煎液的差异, 发现合剂中环烯醚萜类和萜类丰度更高, 而传统水煎液则利于苷类溶出。进一步体内分布的研究表明, 麻黄碱、黄芩苷、芍药苷等24种成分表现出较高的肺内分布, 是发挥药效的直接物质; 同时, 原儿茶酸、钩藤碱等48种成分在结肠内容物中呈现延迟暴露, 表明其可能通过调节肠道菌群稳态发挥“肺肠同治”的协同效应。进一步对候选物质的药效和作用机制进行解析, 发现该方通过调控CCL2、PTGS2、TNF等核心靶点, 不仅在TNF等抗炎通路上发挥作用, 还通过抑制程序性细胞死亡、调控14-3-3蛋白信号转导以及调节脂代谢与流体剪切应力, 发挥对氧化应激及气道重塑的干预。本研究系统阐明了降气平哮方“多成分、多靶点、多途径”的作用模式, 为该方的临床应用、剂型优化及“肺?肠轴”理论提供了科学依据(本实验所有动物实验均获得南京中医药大学动物实验伦理委员会批准, 批准号: 202210A028)。

关键词

哮喘 / 分子网络 / 非靶标成分谱 / 降气平哮方 / 气道重塑

Abstract

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To characterize the material basis of Jiangqi Pingxiao Formula (JQPXF), this study employed feature-based molecular networking (FBMN), identifying a total of 237 chemical components. Based on FBMN, we further compared the chemical profiles of clinical Pediatric Jiangqi Pingxiao Mixture (HJ) and water decoction mixture (JJ) via non-targeted HRMS. The results revealed distinct chemical signatures in iridoids and terpenoids for the mixture, while the decoction showed preferential extraction of glycosides. Notably, in vivo exposure studies demonstrated that 24 components exhibited high pulmonary distribution, suggesting their potential as the direct material basis. Concurrently, 48 components showed delayed exposure in colonic contents, suggesting a potential effect for modulating gut microbiota against asthma through lung-gut axis. Further mechanistic analysis revealed a total of 11 core targets. Beyond classical anti-inflammatory pathways (e. g., TNF signaling), the formula may intervene in oxidative stress and airway remodeling through multiple mechanisms, including the inhibition of programmed cell death, modulation of 14-3-3 protein signaling, and regulation of lipid metabolism and fluid shear stress. This study comprehensively elucidates the "multi-component and multi-pathway" characteristics of JQPXF, providing a scientific foundation for its clinical application and formulation optimization (All animal experiments in this study were approved by the Animal Experimental Ethics Committee of Nanjing University of Chinese Medicine, Ethics No.: 202210A028).

Key words

asthma / molecular networking / non-targeted profiling / Jiangqi Pingxiao Formula / airway remodeling

引用本文

杨河, 严花, 单祎文, 董莹莹, 许景, 谢彤, 赵霞. 基于分子网络与体内非靶标成分谱的降气平哮方治疗哮喘药效物质与作用解析. 药学学报, 2026 , 61 (9) : 3261 -3275 . DOI: 10.16438/j.0513-4870.2026-0201

He YANG, Hua YAN, Yi-wen SHAN, Ying-ying DONG, Jing XU, Tong XIE, Xia ZHAO. Integrating molecular networking and in vivo exposure profiling to reveal the material basis and mechanism of Jiangqi Pingxiao Formula against asthma[J]. Acta Pharmaceutica Sinica, 2026 , 61 (9) : 3261 -3275 . DOI: 10.16438/j.0513-4870.2026-0201

正文

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支气管哮喘是世界范围内常见的慢性气道炎症性疾病^[1], 影响着全球1%~18% 的人口^[2]。近三十年来我国儿童哮喘患病率呈明显上升趋势, 已成为重要的公共卫生问题^[3]。根据最新指南, 吸入性糖皮质激素虽是急性期及缓解期的首选^{[4, 5]}, 但在临床实践中, 部分患儿对激素敏感性较低, 且长期应用可能带来安全隐患^[6]。中医认为哮喘病机复杂, 常为本虚标实, 发作期多以“痰、气、风、火”等邪实壅塞气道为关键。中药复方治疗哮喘, 疗效确切。气道重塑是导致哮喘患者肺功能不可逆损害的关键因素, 而中医药在干预气道重塑等方面展现出独特优势。但是, 中药复方成分复杂, 且体内过程动态变化, 是限制其机制阐明和创新药物转化的瓶颈。因此, 突破传统单成分−单靶点研究模式的局限, 阐明复方协同作用的科学内涵显得尤为重要。

降气平哮方由麻黄(Ephedra sinica Stapf)、苦杏仁(Prunus armeniaca L. var. ansu Maxim.)、黄芩(Scutellariabaicalensis Georgi)、白芍(Paeonia lactiflora Pall.)、钩藤[Uncaria rhynchophylla (Miq.) Miq. ex Havil.]、紫苏子[Perilla frutescens (L.) Britton]、莱菔子(Raphanus sativus L.)、车前子(Plantago asiatica L.) 八味药物配伍而成, 体现了中医“降气平喘、解表清里、平肝息风”的治疗思想^[7], 治疗轻中度儿童哮喘效果显著^[8], 但是其物质基础仍不明确。本研究通过全球天然产物社区的分析工具, 结合非靶标成分谱的关联分析, 系统表征降气平哮方的化学组分。区别于传统的成分鉴定, 本研究通过分子网络技术解析复杂的组分, 旨在从化学家族中识别发挥治疗儿童哮喘的关键物质; 同时, 通过解析原型成分在体内的时空分布特征, 揭示复杂成分的动态过程。在此基础上进一步解析药效及其作用机制, 通过成分−靶标−通路来探究降气平哮方治疗儿童哮喘的多组分协同机制, 进而为降气平哮方治疗哮喘的药效物质基础提供科学依据。

材料与方法

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仪器

UPLC-Q Exactive Orbitrap型高效液相色谱−质谱联用系统(含Ultimate 3000型色谱仪、Q-Exactive型高分辨质谱仪; 美国赛默飞世尔科技有限公司); Millipore Synergy型超纯水系统(德国Merck公司); CPA225D型电子天平(德国Statrorius公司); Allegra 64R centrifuge型超高速冷冻离心机(美国Beckman Coulter公司); 旋转蒸发仪(上海Eyela公司); SPD1010- 230型离心浓缩仪(美国Thermo Fisher公司); VortexGenie 2涡旋振荡器(美国Scientific Industries公司)。

药品与试剂

小儿降气平哮合剂(苏药制备字Z20220012003, 简称合剂, HJ), 购自江苏省中医院, 批号: 2405003。质谱级乙腈和甲醇(批号: l1392130508、l1406607512, 德国默克公司), 质谱级甲酸(批号: F6124-0500, 阿拉丁试剂有限公司), 质谱级乙醇(批号: 190409383K, 南京化学试剂股份有限公司), 超纯水(娃哈哈集团有限公司)。对照品异钩藤碱(批号: JB261014)、原儿茶酸(批号: W10D10B104178)、苦杏仁苷(批号: Y08O10K96808)、木犀草素(批号: S08GB160295)、钩藤碱(批号: N08IB231532)、京尼平苷酸(批号: O30IB228770) 购自上海源叶生物科技有限公司; 绿原酸(批号: 110753-201314)、阿魏酸(批号: 110753-201314)、咖啡酸(批号: 110885-20170)、芍药内酯苷(批号: J223121703)、迷迭香酸(批号: 111871- 201404)、麻黄碱(批号: 171241-20150) 均购自中国食品药品检定研究院; 芍药苷(批号: 110715-200212)、黄芩素(批号: H-018-120623)、汉黄芩素(批号: H-029- 121022)、没食子酸(批号: 110831-200803)、栀子苷(批号: 110749-201919) 购自成都瑞芬思生物科技有限公司; 黄芩苷(批号: 16092401) 购自成都普菲德生物技术有限公司。内标12-[(环己基氨基甲酰) 氨基]十二烷酸(CUDA, 批号: 479413-68-8) 购买于Cayman Chemical公司。

降气平哮水煎剂的制备

降气平哮方的组成如下: 蜜麻黄4 g, 燀苦杏仁10 g, 黄芩8 g, 炒白芍12 g, 钩藤10 g, 炒紫苏子10 g, 炒莱菔子10 g, 盐车前子10 g, 以上药材均购自江苏省中医院。取上述药材, 加入10倍量蒸馏水浸泡2 h, 加热煎煮30 min, 滤出药液。药渣再加入8倍量水, 二次煎煮30 min并过滤, 合并两次药液。利用旋转蒸发仪在60 ℃条件、转速70 r·min^-1条件下减压浓缩, 制备成含生药量为1.48 g·mL^-1的浓缩液, 即降气平哮水煎剂(简称水煎液, JJ) 置于4 ℃冰箱保存备用。

混合对照品和供试品的制备

精密称取对照品10.0 mg, 置于10 mL量瓶中, 加甲醇超声处理使其完全溶解, 加甲醇定容至刻度, 配置成浓度为1 mg·mL^-1的对照品储备液。精密取适量对照品储备液, 用甲醇稀释, 制成质量浓度为2 µg·mL^-1的混合对照品溶液, 用于UPLC-Q Exactive进样。供试品的制备, 精密量取1.48 g·mL^-1的降气平哮水煎液和降气平哮合剂, 用甲醇稀释10倍, 涡旋5 min, 18 000 r·min^-1离心10 min, 取上清液进样。

动物实验

SPF级BALB/c雌性小鼠35只, 4周龄, 体重14~16 g, 购自江苏华创信诺医药科技有限公司, 实验动物生产许可证号: SCXK (苏) 2020-0009。动物饲养于南京中医药大学实验动物中心, 伦理批号: 202210A028。饲养温度控制在(22 ± 2) ℃左右, 湿度(55 ± 2) %左右, 保持采光通风良好, 自由饮水饮食。实验前, 小鼠禁食不禁水12 h。HJ组和JJ组小鼠分别灌胃给予22.2 g·kg^-1的药物(临床等效剂量的1.5倍), 于给药后15 min、3 h及10 h采集各组小鼠(n = 5) 血浆(肝素钠抗凝)、肺、结肠和结肠内容物样本, 并置于−80 ℃冰箱保存待用。

生物样品的处理方法

血浆样本处理方法: 取50 μL血浆样品, 加入150 μL含内标(CUDA, 25 ng·mL^-1) 甲醇溶液, 涡旋2 min混合均匀, 18 000 r·min^-1、4 ℃离心10 min, 取上清液进行检测。组织样本处理方法: 称取肺组织(或肠、肠内容物) 25 mg, 剪碎, 加入250 µL去离子水, 20 r·min^-1匀浆10 min。取100 µL匀浆液(即10 mg组织), 加入400 µL含内标的甲醇溶液混匀, 涡旋5 min, 18 000 r·min^-1离心10 min, 取上清液400 µL于真空离心浓缩仪中挥干。加入150 µL甲醇溶液复溶, 涡旋5 min, 18 000 r·min^-1离心10 min, 取上清液进样。

色谱分离条件

采用Waters ACQUITY UPLC CSH C₁₈色谱柱(100 mm × 2.1 mm, 1.7 μm); 流动相为0.1%甲酸水溶液(A) 和0.1%甲酸乙腈溶液(B)。色谱分离采用梯度洗脱, 具体程序为0~0.5 min, 10% B; 0.5~ 16 min, 10%~85% B; 16~17 min, 85%~10% B; 17~ 20 min, 10% B。流速为0.3 mL·min^-1, 柱温为45 ℃, 进样量5 μL。

质谱检测条件

采用电喷雾离子源(ESI), 分别在正、负离子模式下进行检测。正离子模式的喷雾电压为4 000 V, 负离子模式下的喷雾电压为3 400 V; 鞘气和辅助气均为氮气, 鞘气流速设定为60 arb, 辅助气流速为15 arb; 离子源的毛细管温度和气化室温度均为300 ℃。质谱的扫描范围设定为m/z 150~1 200, 一级扫描(full MS) 分辨率70 000, 二级扫描(dd-MS²) 分辨率为17 500, 自动增益控制(AGC target) 设定为5.0×10⁴。采用数据依赖型采集(DDA) 模式获取二级谱图, 归一碰撞能量(NCE) 梯度梯度为25、35、50 eV。

构建分子网络

按照检测条件对降气平哮水煎液、合剂以及混合对照品进行分析, 生成的原始数据(.raw) 导入MS-DIAL (v4.9) 软件进行预处理。根据仪器类型设定参数, 选择相应的检测模式。通过软件进行峰检测、解卷积和峰面积归一化。完成预处理后, 导出含有特征峰列表(.csv) 和二级谱图文件(.mgf)。将.mgf文件上传至全球天然产物社交分子网络平台GNPS (http://gnps.ucsd.edu), 采用基于特征的分子网络(feature-based molecular networking, FBMN) 构建分子网络。关键参数设定为: 前体离子质量误差与二级碎片离子误差均设定为0.02 Da, 最小匹配碎片数设定为4, 余弦相似度评分阈值设定为0.7。最后, 将生成的网络文件(.graphml) 导入Cytoscape (v3.10.3) 软件进行可视化及拓扑结构分析。

非靶标成分谱的数据处理

为了分析降气平哮各成分在血浆、肺、结肠和结肠内容物中的分布差异, 原始的质谱数据经过MS-DIAL (v4.6) 进行峰提取、对齐及背景扣除。在统计分析前, 将原始峰面积按照血浆体积及各组织质量进行校正。随后, 为了消除数据的偏态分布并使方差齐性, 原始峰面积响应值导入MetaboAnalyst软件(v6.0) 中进行log₂对数转化和Pareto标准化处理。组间显著性差异采用Benjamini-Hochberg方法控制错误发现率(FDR), 以FDR＜0.05和变化倍数(fold change, FC) 筛选差异性化合物。

时程变化与Mfuzz聚类分析

为了研究复方成分在体内的动态变化, 本研究采用R语言的Mfuzz软件包(Bioconductor) 对测得成分的丰度值进行分析。得到的原始数据经过标准化处理以消除不同成分之间绝对含量对聚类结果的影响。采用Fuzzy C-means算法对成分的时间轨迹进行归类。通过可视化趋势图, 识别出具有相似性排泄或吸收模式的成分簇, 表征其在结肠内容物中持续积累的成分, 以及在血浆中呈现出快速吸收−缓慢代谢趋势的成分。

核心靶点筛选和作用通路分析

对降气平哮方体内成分在TCMSP (https://tcmsp-e.com/) 筛选活性成分并获取靶点信息; 同时结合HIT (http://hit2.baddcao.net/) 数据库基于文献报道的成分−靶点关系补充靶点数据, 并对所得靶点进行去重及标准化处理筛选作用靶点。通过GeneCards数据库(https://www.genecards.org)、OMIM数据库(https://omim.org) 和TTD数据库(http://db.idrblab.net/ttd/) 获得哮喘(关键词为asthma)相关的靶点基因。利用R软件(R-4.4.1) 对降气平哮方体内成分相关靶点和哮喘相关靶点取交集。筛选到的交集靶基因导入STRING网站(http://string-db.org/), 物种选择为“Homo sapiens”, 最低相互作用评分设为0.4, 获得蛋白相互作用信息, 通过Cytoscape 3.8.0软件构建PPI, 通过CytoNCA (MCODE) 插件进行分析, 对分析出的结果进行2次中位数筛选后得到核心靶基因。利用R软件(R-4.4.1) 对交集基因进行GO功能富集分析和KEGG通路富集分析按照P＜0.05进行筛选, 用微生信可视化和迪基奥云工具平台进行作图。

结果

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1　构建基于FBMN的分子网络系统解析复杂物质组

本研究基于FBMN分子网络策略, 对降气平哮方的复杂化学成分进行系统分析。通过整合水煎液与合剂的质谱数据构建分子网络: 在正离子模式下, 识别出423个分子网络(不含单节点), 包含2 816个节点和5 629条边; 在负离子模式下, 产生483个分子网络(不含单节点), 包含3 074个节点和5 655条边。依托GNPS数据库进行在线谱库比对, 在正、负离子模式下分别鉴定出213个和190个化合物, 对应获得149个和137个有效SMILES结构式。对匹配得到的成分进行化学归类, 结果显示黄酮类成分占比最高, 此外还涵盖糖类、多肽、核酸及苯乙醇苷等(图 1A)。鉴于GNPS数据库对中药成分谱图的覆盖有限, 仅部分成分能被鉴定, 为全面表征降气平哮方中的物质基础, 本研究对生成的分子网络进行更深入的分析。

1.1　黄酮类的分子网络

在正、负离子检测模式下均产生了黄酮类特征的分子网络。该类成分的质谱裂解规律主要表现为糖基片段的中性丢失。以图 1B所示的负离子模式网络为例, 该簇中聚类了黄芩苷、野黄芩苷、黄芩素-6-O-葡萄糖醛酸苷与野黄芩素-6-O-葡萄糖醛酸苷的节点。此外, 网络中不同形式的加合离子进一步验证了物质鉴定的准确性。如黄芩苷的[M−H]⁻ (m/z 445.078 0) 与其二聚体离子[2M−H]⁻ (m/z 891.124 8)互为印证。基于FBMN的拓扑关联, 在该簇中还进一步鉴定出黄芩素-6-O-葡萄糖-7-O-葡萄糖醛酸苷(baicalein-6-O-glucoside-7-O-glucuronide) 和甲基槲皮素-6-O-葡萄糖-7-O-葡萄糖醛酸苷(methylquercetin-6-O-glucoside-7-O-glucuronide)。这些成分主要来源于黄芩, 在所有鉴定出的成分中, 黄酮类化合物共计108种, 构成了降气平哮方主要的化学成分群。

1.2　苯丙素类及其衍生物的分子网络

苯丙素类及其衍生物主要包括苯乙醇苷类和苯丙醇苷类成分。该类成分以毛蕊花糖苷(acteoside)、异毛蕊花糖苷(isoacteo‐ side) 和迷迭香酸(rosmarinic acid) 等为代表, 分子网络如图 1C所示, 这些物质在质谱中呈现出糖苷键断裂及咖啡酰基、阿魏酰基等酰基丢失的典型裂解模式。共鉴定出26种苯丙素类成分, 主要来源于车前子和紫苏子。

1.3　硫代葡萄糖苷类的分子网络

在负离子检测模式, 共鉴定出20种硫代葡萄糖苷(glucosinolates) 成分, 主要来源于莱菔子, 其分子网络如图 1D所示。硫代葡萄糖苷由β-D-硫代葡萄糖、磺肟基团和可变侧链R基通过硫苷键连接而成。在二级质谱中, 这类化合物的特征裂解行为表现为磺酸基团的中性丢失。以萝卜硫苷(glucoerucin) 为例, 其[M−H]⁻峰m/z 420.046 2 (C₁₂H₂₂NO₉S₃⁻) 在碰撞诱导解离后, 产生了特征性碎片离子m/z 96.960 1 (HSO₄⁻) 和m/z 79.957 4 (SO₃⁻)。

1.4　色氨酸生物碱类的分子网络

色氨酸类生物碱主要来源于钩藤, 在正离子模式下共鉴定出24种色氨酸类生物碱, 其分子网络如图 1E所示。以去氢钩藤碱(corynoxheine) 为例, 质子化的[M+H]⁺峰m/z 383.196 5 (C₂₂H₂₇N₂O₄^⁺), 在碰撞诱导解离后, 中性丢失CH₃OH, 产生了特征碎片离子m/z 351.170 3; 随后进一步碎裂, 形成了m/z 267.149 2、201.102 2、187.086 6和160.075 7等特征离子。其中, 二级质谱图中出现的m/z 132.044 4是该类生物碱的诊断离子, 对应于结构中的3H-吲哚母核。

1.5　萜类的分子网络

萜类成分主要来源于白芍, 包括芍药苷(paeoniflorin)、芍药内酯苷(albiflorin) 等一系列单萜苷及其衍生物, 其裂解以糖苷键和内酯键的断裂为主。在正、负离子下均能检测到, 共鉴定出27个萜类化合物(图 1F)。

除了上述主要结构类别外, 本研究通过FBMN分子网络, 在降气平哮方中还鉴定出环烯醚萜类(源自车前子)、氰甙类(源自苦杏仁)、伪生物碱(源自麻黄)以及多种有机酚酸类成分。尽管这些组分形成的分子簇规模较小, 但其特征性的裂解行为仍为复杂组分的快速归属提供了重要依据。

经过分析和比对, 本研究共鉴定出237种化学成分(表 1), 涵盖了黄酮类、苯丙素类、硫苷类、萜类、生物碱类、环烯醚萜类、有机酸类及氰苷类等多种结构类型。混合对照品及水煎液、合剂的提取离子流图见图 2。

2　降气平哮合剂和水煎液的比较分析

降气平哮合剂是江苏省中医院院内制剂, 与传统水煎液虽组方一致, 但化学成分与微观变化往往不同。为了阐明不同制备方法对药物物质基础的影响, 本研究基于非靶标方法, 采用主成分分析(PCA) 对两组样本进行整体成分谱分析。PCA得分图结果显示(图 3A), 在正、负离子模式下, 两组样本呈现出显著的组间聚类趋势。其中, 第一主成分(PC1) 解释了82.5%的总体差异, 表明两组在整体化学轮廓上存在差异。

本研究对检测到的237种化学成分按结构类型进行分类归属。鉴于非靶向分析中不同化合物的质谱响应因子存在差异, 在两组生药浓度(0.148 mg·mL^-1) 一致的前提下, 通过计算同一成分在两组间的响应比值来反映制备方法对成分溶出的影响。结果显示, 环烯醚萜和萜类成分在合剂中的响应值显著高于水煎液(FDR＜0.05), 平均比值分别为5.95和1.25。这提示这些类别的成分在合剂的制备过程中可能更易溶出。相反, 硫苷类与氰苷类成分在水煎液中的响应值更高, 平均比值为0.52 (FDR＜0.05)。其余类别如苯丙素、酚酸、生物碱等成分在合剂与水煎剂中的差异不大(图 3B)。

进一步对峰面积前20的化合物进行分析。这些组分在峰面积归一化后, 两组的比较中均表现出显著差异(FDR＜0.001)。图 3C展示了各成分在合剂和水煎液中的平均峰面积情况, 并标注了组间变化的倍数。结果显示, 来自莱菔苷、4-甲基亚磺酰基-3-丁烯基硫苷、毛蕊花糖苷及迷迭香酸在水煎液中响应显著高于合剂(FDR＜0.05); 而芍药苷、汉黄芩素、黄芩素-5-O-葡萄糖醛酸苷以及京尼平苷酸的响应在水煎液中低于合剂(FDR＜0.05), 提示该成分在合剂制备过程中可能更易溶出或稳定保留。综上所述, 合剂与水煎液的成分种类相同, 但部分成分的含量存在显著差异。

3　体内物质组分析及肺内暴露偏好表征

小儿降气平哮合剂和水煎液均为临床上广泛应用的制剂形式。为了探究合剂和水煎液中各成分在体内的分布, 进一步对血浆、肺及肠组织中的原型成分进行分析。结果显示, 合剂与水煎液中分别有24种和20种原型成分在血浆、肺及肠组织中共同暴露(图 4A)。进一步研究24种成分在血浆与肺组织间的动态分布差异, 以峰面积归一化后的Log₂ (Ratio_Lung/Plasma) 为横坐标, FDR值为纵坐标绘制火山图。结果表明, 粗毛豚草素7-O-葡萄糖醛酸(hispidulin 7-O-glucuronide) 在血浆中更易于被检测到; 而汉黄芩素(wogonin)、千层纸素A (oroxylin A)、芍药苷(paeoniflorin)、钩藤碱(corynoxeine)、异钩藤碱(isocorynoxeine)、奎宁酸(quinic acid) 及莱菔素(sulforaphene) 等成分在肺组织中更易于被检测到, 提示其具有较高肺内分布。需要说明的是, 本研究基于非靶标代谢组学策略, 未对成分进行绝对定量。由于肺组织与血浆基质效应的差异, 本结果主要反映方中各成分间相对分布差异, 而非各成分在血或肺组织的绝对分布(图 4B)。

24种成分的时程分布情况如图 4C所示。其动力学特征可归纳成两类, 一是快速分布与消除, 以麻黄碱(ephedrine)、莱菔素(sulforaphene) 及普鲁拉斯苷(prulaurasin) 为代表。此类成分表现出肺部快速分布特征, 在给药后15 min即达峰, 随后迅速降低。另一类是持续暴露与延迟达峰的成分, 以黄芩苷(baicalin)、汉黄芩苷(wogonoside)、芍药苷(paeoniflo‐ rin) 及异钩藤碱(isorhynchophylline) 为代表。此类成分在肺内的暴露随时间推移持续升高, 在10 h达到峰值。究其原因, 一方面, 黄酮苷类组分受肝肠循环的影响, 在肠道会再吸收, 因此在肺内持续暴露; 另一方面, 肠道内前体物质(如提取液中的氧化芍药苷等) 经菌群代谢转化为芍药苷后被肠道二次吸收进入循环, 而后在肺内暴露, 这种代谢转化机制有效延长了芍药苷等成分在肺组织中的暴露时长, 为其发挥平喘药效提供物质保障。

4　结肠内容物中的分布及代谢转归行为表征

图 5是合剂与水煎液中原型成分在血浆、结肠和结肠内容物中的分布特征。结果显示, 合剂与水煎液中分别有38种和47种成分表现出结肠内容物分布(图 5A)。为进一步探究这些成分的体内行为及代谢转归, 本研究采用Fuzzy C-means聚类算法对其时程演变趋势进行分析, 将结肠内容物的分布成分归纳为三种类型(图 5B)。第一类是结肠内持续高水平分布的成分。以黄芩素和山柰酚为代表的黄酮类成分, 在给药后3~10 h在结肠内容物中持续较高水平。虽然有文献^[9]报道黄芩素可经肠道吸收入血, 但是其水溶性较低, 大部分苷元滞留于肠道。此外, 此类成分及其葡萄糖醛酸结合物在体内显著的肝肠循环, 进一步维持了其在结肠内的持续暴露。咖啡酸和原儿茶酸也属于血中未检测到, 而在结肠内容物中持续暴露的组分, 推测与其在复方中原始含量极低有关。另外, 迷迭香酸、咖啡酰基奎宁酸及毛蕊花糖苷等酚酸前体成分进入肠道后, 在肠道菌群的作用下降解转化, 也是导致咖啡酸和原儿茶酸持续分布的原因。钩藤碱(rhynchophylline)和毛钩藤碱(mitraphylline) 等吲哚生物碱类, 受到P-糖蛋白等多种ABC转运体外排转运影响, 导致跨膜吸收受阻, 因此长时间滞留在结肠中^[10]。第二类为结肠延时暴露成分, 其结肠内容物分布的峰值主要集中在给药后3 h。该类成分主要是芍药苷衍生物(如氧化芍药苷、没食子酰基芍药内酯苷、芍药苷元酮等)。这类原型成分因方中原始含量低、吸收差, 且进入肠道后经肠道菌群水解, 转化为芍药内酯苷或其苷元, 进而导致其只能在结肠内容物中被检测到。与之情况类似还有莱菔子中的芥子油苷类成分(4-甲硫基丁基芥子油苷和5-甲硫戊基硫苷)。此外, 方中原始含量较高的毛蕊花糖苷和异毛蕊花糖苷吸收差, 进入肠道到被代谢产生咖啡酸等产物, 也表现出结肠延时暴露的特征。第三类为结肠瞬时暴露成分, 其主要在给药后的15 min暴露, 而后快速消除。这些成分一方面在原方中的原始含量较低, 另一方面可能由于汤药的理化特征使其在短时间内到达结肠内(图 5C)。

5　候选药效物质的活性确证研究

5.1　降气平哮方治疗哮喘的靶点筛选

降气平哮方在哮喘治疗中疗效确切。为阐明其药效机制, 本研究以LC-MS/MS鉴定并能进入体内的化学成分为研究对象, 结合HIT (http://hit2.baddcao.net/) 和TCMSP (https://tcmsp-e.com/) 数据库共检索到104个潜在作用靶点。将其与通过疾病数据库筛选出的2 649个哮喘相关靶点取交集, 最终确定了71个与入肺成分紧密关联的共有靶点(图 6A)。利用STRING数据库物种设为Homo sapiens, 最低相互作用评分设为0.4, 构建蛋白间相互作用网络, 经两次中位数拓扑分析筛选, 获得11个核心靶点。基于HIT2.0数据库, 对这11个核心靶点进一步通过文献进行手动验证^[11]。结果显示, 成分可直接作用的靶点包括PTGS2、BCL2、PPARG、IL-6、IL-1B、TNF、IFNG; 间接调控的靶点包括HMOX1、TP53和CCL2; 可对其进行上升的靶点包括ESR1 (图 6B)。

5.2　GO和KEGG通路富集分析

对11个核心靶点进行富集分析(图 6C)。结果显示, 生物学过程(bio‐ logical process, BP) 主要富集于NO生物合成过程、活性氮代谢和平滑肌细胞增殖调控; 细胞组分(cellular component, CC) 主要涉及Bcl-2家族蛋白复合物、细胞器外膜和外膜; 分子功能(molecular function, MF) 则涉及蛋白磷酸酶2A结合、核受体活性和细胞因子活性。KEGG通路富集共筛选出88条信号通路(图 6D), 除典型的TNF及IL-17炎症信号通路外, 还包括流体剪切应力和脂质等。

抑制炎症是治疗哮喘急性期的主要手段^[12-15], 炎症相关靶点已被广泛研究。除抗炎外, 降气平哮方是否存在其他作用靶点尚不明确。为此, 本研究剔除典型的炎症因子, 对余下的7个核心靶点进行二次富集分析。结果显示, 两次分析的CC富集结果一致; 在BP层面, 富集条目转变为上皮细胞凋亡、平滑肌细胞凋亡及缺氧相关应答过程; 在MF层面, 富集条目集中于14-3-3蛋白结合和配体激活的转录因子活性。第二次KEGG富集结果不仅验证了前期结果, 还新增富集至内分泌耐药、铁死亡、长寿调节通路和鞘脂信号通路。

讨论

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降气平哮方以三拗汤和三子养亲汤为基础, 经加减变化而来, 用于治疗儿童哮喘发作期外寒内热证, 疗效显著^[7]。本研究利用分子网络技术系统解析了降气平哮方的物质基础, 并运用非靶向成分分析方法阐明了各成分在血、肺及肠道中的移行变化规律, 进而探讨了候选药效物质的多靶点协同调控机制。

本研究基于分子网络共鉴定出237个化学成分。在此基础上, 比较了小儿降气平哮合剂与传统水煎液的成分谱。结果显示, 两种剂型的成分种类一致, 但各种类的相对含量存在显著差异。合剂中环烯醚萜类和萜类成分含量高, Ratio_HJ/JJ分别为5.95和1.25, 推测合剂的制备工艺有利于脂溶性成分的提取; 而水煎液中硫苷类及伪生物碱类含量高, Ratio _HJ/JJ分别为0.52和0.76, 推测此类成分在煎煮过程中易溶出。参照中国药典(2025年版), 对方中各药材的标志性成分进行定量评价。进一步的分析还发现, 京尼平苷酸(源自车前子) 的含量低于药典规定的限量标准。这除了受药材因素影响外, 还可能与京尼平苷酸在煎煮过程中的稳定性有关。血浆和肺组织成分的关联分析显示, 有24种成分在肺内分布较高。其中, 黄芩苷等成分可经肝肠循环或代谢转化被二次吸收, 以多途径方式实现在肺内蓄积^[16]。结肠内容物的检测结果显示, 有48种成分分布于肠腔中。其中毛蕊花糖苷等成分经肠道菌群代谢生成咖啡酸和原儿茶酸, 表现为延迟性的肠内暴露。而黄芩素等成分因溶解度低而滞留于肠道, 也表现为延迟性的肠内暴露。

研究表明, 结肠内的中药成分可通过“肺−肠轴”发挥治疗哮喘的作用。例如原儿茶酸^[17]和咖啡酸^[18]可显著增加肠中益生菌水平, 进而调节免疫细胞抑制肺部炎症。此外, 有研究发现, 钩藤碱可拮抗胆碱能受体^[19], 而胆碱能神经的过度激活是哮喘气道高反应性的重要病理机制^{[20, 21]}。由此推测, 肠道内高暴露的钩藤碱, 可通过拮抗肠神经的胆碱能受体, 经外周神经降低气道的高反应性, 进而发挥治疗哮喘的作用, 体现了“从肠论治”的理念。不过, 这一机制有待进一步验证。

麻黄碱和苦杏仁苷是降气平哮方的主要药效成分, 已有研究阐明其通过肾上腺素能受体和胆碱能受体发挥平喘作用^[22-24]。在此经典靶点的基础上, 本研究进一步富集到炎症反应、程序性细胞死亡、14-3-3蛋白通路及代谢重编程等通路。炎症反应是哮喘急性期的主要病理表现。研究表明, CCL2受NF-κB和JAK/ STAT等上游信号调控, 是临床评估哮喘严重程度的生物标志物^[25]; PTGS2是炎症反应中的关键限速酶, 其过度表达与IL-1β和TNF-α等炎症因子的释放直接相关^{[26, 27]}, 进而导致哮喘的炎症级联放大效应^[28]。本研究筛选出CCL2、PTGS2、TNF、IL6、IL1B和IFNG等相关炎症靶点, 进一步说明降气平哮方具有显著的抗炎作用。炎症与氧化应激密切相关, 本研究还富集到NO生物合成和活性氮代谢条目, 提示降气平哮方可能通过靶向HMOX1进而抑制氧化应激^[29]。

上皮细胞损伤与平滑肌细胞异常增殖引发的气道重塑, 是哮喘的另一重要病理表现。研究表明, BCL2介导的内源性细胞凋亡通路, 在维持气道结构方面发挥重要作用^[30]; TP53作为P53蛋白家族成员, 参与细胞周期与凋亡调控, 从而影响气道上皮损伤; 铁过载诱发的脂质过氧化, 在哮喘气道重塑过程中发挥重要作用。本实验富集到的AGE-RAGE信号通路和铁死亡通路提示, 降气平哮方可通过调控上皮细胞的程序性死亡以及氧化应激信号通路, 减轻上皮细胞损伤并改善气道重塑。研究表明14-3-3蛋白可以结合HSP20促进气道平滑肌舒张^[31]; 且14-3-3蛋白通过螯合凋亡蛋白Bax, 阻止其向线粒体转移^[32]。结合本实验富集到的14-3-3蛋白通路, 表明降气平哮方可能通过调控14- 3-3蛋白通路参与细胞凋亡过程, 改善气道平滑肌功能异常并抑制凋亡。另外, 哮喘与代谢紊乱(如肥胖或胰岛素耐受) 存在复杂的共病关系。鞘脂(如S1P) 已被证实是诱发气道重塑的关键脂质介质^[33]。本研究也发现降气平哮方对脂质以及鞘脂信号通路有调控作用。

糖皮质激素是儿童哮喘的一线药物, 长期使用会出现继发性激素耐药^{[34, 35]}。研究表明, 糖皮质激素受体磷酸化, 导致受体配体亲和力降低是激素耐药的主要机制^[36]。本实验富集到的ESR1和PPARG核心靶点, 提示降气平哮方可通过PI3K/Akt和MAPK/ERK抑制糖皮质激素受体磷酸化^[37], 促进其核转位, 增加免疫细胞对激素的敏感性^{[38, 39]}。

综上所述, 本研究运用分子网络和体内非靶向成分分析, 系统揭示了降气平哮方多成分在体内的裂解规律、组织分布、时间分布以及其潜在作用靶点和通路, 为降气平哮方治疗哮喘提供更多潜在活性成分和作用机制。

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2026年第61卷第9期

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doi: 10.16438/j.0513-4870.2026-0201

接收时间：2026-02-25
首发时间：2026-10-22
出版时间：2026-09-12

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收稿日期：2026-02-25
修回日期：2026-06-16

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¹南京中医药大学第一临床医学院，儿童健康与中医药省高校重点实验室，江苏南京 210023

²南京中医药大学附属医院，江苏南京 210029

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谢彤， E-mail: xietong@njucm.cn

赵霞， E-mail: zhaoxiahy@126.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	Mode	Annotation		No.	t_R/min	m/z	Mode	Annotation
1	0.92	225.060 2	-	Glucoheptonic acid		133	6.42	579.207 9	-	Eleutheroside E1
2	0.97	191.055 0	-	Quinic acid	134	6.42	580.061 3	-	Coumaroyl glucoraphenin
3	0.97	345.118 0	-	Aucubin	135	6.44	415.103 6	-	Puerarin
4	0.99	166.123 1	+	Pseudoephedrine^*		6.52	417.119 2	+
5	1.12	169.013 2	-	Gallic acid	136	6.45	431.096 9	-	Apigenin 7-O-β-D-glucoside
6	1.29	152.107 5	+	Norephedrine		6.45	433.114 3	+
7	1.29	166.123 1	+	(−)-Ephedrine^*	137	6.48	639.155 0	-	Isorhamnetin-3, 7-diglucoside
8	1.32	169.013 1	-	Gallic acid	138	6.48	461.073 0	-	Scutellarein-6-O-glucuronide
9	1.42	180.138 7	+	Methylephedrine		6.80	463.088 0	+
10	1.45	372.042 4	-	Gluconapin	139	6.49	610.070 2	-	Feruloyl glucoraphenin
11	1.46	373.113 6	-	Geniposidic acid^*	140	6.50	640.082 6	-	Sinapoyl glucoraphenin
	1.47	397.110 8	+		141	6.51	515.132 1	-	Isochlorogenic acid^*
12	1.48	422.024 4	-	Glucoiberin	142	6.56	205.085 5	-	4-Hydroxy-3-(3-methylbut-2-enyl)benzoic acid
13	1.48	452.034 2	-	4-Methylsulfonylbutyl glucosinolate	143	6.57	637.213 0	-	Plantainoside C
14	1.52	434.025 4	-	Glucoraphenin		6.80	639.229 6	+
15	1.57	176.020 2	+	Sulforaphene	144	6.58	799.229 2	-	3', 6-Disinapoylsucrose
16	1.65	450.020 1	-	4-Methylsulfonyl-3-butenyl glucosinolate		6.62	777.221 1	+
17	1.65	434.025 4	-	Glucoraphenin	145	6.61	449.107 5	-	Eriodictyol-7-O-glucoside
18	1.67	388.037 1	-	Epiprogoitrin	146	6.63	505.134 6	-	Isorinic acid-3'-O-glucoside
19	1.77	461.166 8	-	Decaffeoylverbascoside	147	6.65	387.128 9	+	Sinapoylglucose
20	1.78	450.056 6	-	5-Methylsulfinyl-n-pentyl glucosinolate	148	6.65	538.050 6	-	Glucoraphenin benzoate
21	1.90	375.129 5	-	Loganic acid		6.73	540.065 7	+
	1.78	399.127 7	+		149	6.71	1445.426 5	-	1-Sinapoyl-2-feruloyl gentiobiose
22	1.93	153.017 9	-	Protocatechuic acid^*	150	6.72	417.120 0	-	Glucoliquiritigenin
23	2.10	353.087 6	-	Neochlorogenic acid	151	6.75	693.202 8	-	Helonioside A
	2.07	355.103 1	+		152	6.75	187.096 1	-	Azelaic acid
24	2.10	577.135 1	-	Procyanidin B2	153	6.77	435.129 7	-	Phloridzin
	2.12	579.150 5	+			5.22	437.142 4	+
25	2.12	310.165 1	+	Sinapine^*	154	6.79	359.077 0	-	Rosmarinic acid^*
26	2.35	618.203 3	-	Triglucosyl cyanogen glycoside		6.90	361.092 2	+
27	2.54	411.127 7	+	Secologanin	155	6.84	509.164 2	-	Paeobrin
28	2.55	289.070 9	-	Epicatechin	156	6.86	177.017 9	-	Esculetin
29	2.58	305.066 5	-	Gallocatechin		6.13	179.034 3	+
30	2.69	289.070 9	-	Epicatechin	157	6.95	181.050 1	+	Caffeic acid
31	3.17	547.165 8	-	Sibiricose A1	158	6.95	477.102 4	-	Hesperetin 3'-O-glucuronide
32	3.25	456.150 5	-	Amygdalin^*		7.01	479.118 4	+
	3.32	475.191 8	+		159	6.97	607.201 6	-	Osmanthuside J
33	3.25	618.203 4	-	Triglucosyl cyanogen glycoside	160	7.00	475.087 8	-	Hispidulin 7-glucuronide
34	3.44	177.017 8	-	Dihydroxycoumarin		6.98	477.103 5	+
35	3.45	355.103 5	+	Chlorogenic acid^*	161	7.05	753.227 0	-	3', 6-Disinapoylsucrose
	3.46	353.087 4	-		162	7.06	461.108 5	-	Homoplantaginin
36	3.57	369.182 1	+	Mitraphylline		7.14	463.123 5	+
37	3.65	353.087 6	-	4-O-Caffeoylquinic acid	163	7.078	507.148 8	-	Lactiflorin
	3.65	355.103 4	+		164	7.171	637.212 9	-	Leucosceptoside A
38	3.61	179.034 4	-	Caffeic acid^*		7.282	639.229 3	+
39	3.73	387.129 1	-	Miscanthoside	165	7.203	505.099 7	-	Tricin-7-glucuronoside
40	3.92	593.150 3	-	Apigenin-6, 8-di-C-glycoside		7.291	507.115 4	+
	3.93	595.166 9	+		166	7.213	511.053 7	-	Baicalein 7-O-glucoside 5-O-sulfate
41	3.93	371.196 7	+	Rhyncophyllic acid	167	7.226	287.056 1	-	Eriodictyol
42	3.93	411.125 6	+	Geniposide^*		7.326	289.070 4	+
43	4.03	635.086 9	-	1, 3, 6-Tri-O-galloylglucose	168	7.333	477.103 5	+	Hispidulin 7-O-glucuronide
44	4.08	521.202 6	-	Isolariciresinol 4-O-glucopyranoside	169	7.439	369.180 9	+	Speciophylline
45	4.12	327.108 2	-	Ethyl vanillin glucoside	170	7.422	431.097 1	-	Oroxin A
46	4.14	381.116 5	+	Sweroside		7.475	433.114 3	+
47	4.16	547.166 1	-	Sibiricose A6	171	7.432	345.060 2	-	Viscidulin Ⅲ
48	4.16	294.098 4	-	Prulaurasin		7.521	347.076 9	+
49	4.18	420.045 7	-	Glucoerucin	172	7.595	445.078 0	-	Baicalin^*
50	4.23	207.138 6	+	Sinapoylmalate		7.695	447.092 6	+
51	4.36	525.161 1	-	Paeoniflorin^*	173	7.673	651.230 3	-	Compound NP-002173
	4.35	481.171 2	+			7.752	675.227 3	+
52	4.36	641.209 5	-	Isomaltopaeoniflorin	174	7.722	477.102 6	-	Homoeriodictyol glucuronide
53	4.37	609.146 4	-	Luteolin-3', 7-di-O-glucoside		7.81	479.120 8	+
	4.47	611.161 6	+		175	7.77	287.055 1	-	Maesopsin
54	4.48	369.182 1	+	Isomitraphylline	176	7.78	505.097 3	-	Tricin 7-O-glucuronide
55	4.46	593.147 4	-	Vitexin 4-O-glucoside		7.86	507.113 1	+
56	4.51	343.139 8	-	Dihydroconiferin	177	7.91	447.092 8	-	Naringenin-4'-O-glucuronide
57	4.56	639.192 3	-	Plantamajoside D		7.99	449.107 7	+
58	4.57	785.251 7	-	Echinacoside	178	7.99	445.113 7	-	Wogonin 7-O-glucoside
59	4.59	327.144 4	-	Perilloside B		8.63	447.128 5	+
60	4.60	563.138 0	-	Schaftoside^*	179	8.02	415.103 8	-	Daidzin
	4.63	565.154 5	+			8.02	417.119 4	+
61	4.65	495.150 8	-	Oxypaeoniflorin	180	8.02	591.206 6	-	Osmanthuside B6
	4.67	497.165 7	+		181	8.08	477.102 6	-	Hesperetin-7-O-glucuronide
62	4.67	525.161 0	-	Albiflorin^*	182	8.15	445.075 8	-	Baicalein 6-O-glucuronide
	4.75	503.153 4	+		183	8.16	461.108 4	-	Peonidin 3-galactoside
63	4.71	401.208 4	+	Isorhynchophylline N-oxide		8.24	463.123 3	+
64	4.72	543.116 5	-	Paeoniflorinsulfonic acid	184	8.18	651.230 0	-	Compound NP-002173
65	4.73	447.092 6	-	Luteolin 7-glucoside		8.28	653.245 7	+
	4.82	471.090 5	+		185	8.23	285.039 7	-	Luteolin^*
66	4.74	593.147 3	-	Pelargonin	186	8.24	431.098 9	-	Kaempferol-7-O-rhamnoside
	4.80	595.166 8	+			8.27	433.114 7	+
67	4.84	563.141 0	-	Isoschaftoside	187	8.28	445.077 8	-	Baicalein 5-O-glucuronide
	4.69	565.154 5	+			8.24	447.092 5	+
68	4.93	495.151 3	-	Oxypaeoniflorin	188	8.36	475.087 8	-	Hispidulin 7-glucuronide
69	4.93	371.196 6	+	Rhyncophyllic acid		8.44	477.103 6	+
70	4.96	401.208 1	+	Isorhynchophylline N-oxide	189	8.40	345.061 5	-	5, 7, 3', 4'-Tetrahydroxy-6, 8-dimethoxyflavone
71	4.96	367.102 6	-	3-O-Feruloylquinic acid^*		8.70	347.077 0	+
72	4.99	787.263 9	-	Liriodendrin	190	8.52	429.081 8	-	Chrysin-7-O-glucuronide
73	5.00	639.154 4	-	Dactylin		8.60	431.098 1	+
74	5.01	577.154 8	-	Chrysin 8-C-glucoside 6-C-glucoside	191	8.52	459.093 8	-	Oroxylin A-7-O-glucuronide
	5.04	579.173 0	+			8.64	461.107 6	+
75	5.07	369.182 0	+	Mitraphylline	192	8.55	591.206 6	-	Osmanthuside B6
76	5.13	621.180 7	-	Isocrenatoside	193	8.64	511.054 0	-	Baicalein 7-O-glucoside 6-O-sulfate
77	5.15	509.130 3	+	Syringetin 3-glucoside	194	8.71	475.087 8	-	Hispidulin 7-glucuronide
78	5.15	433.113 9	-	Naringenin-7-O-glucoside		8.78	477.103 6	+
79	5.20	755.239 7	-	Compound NP-000173	195	8.82	445.077 3	-	Baicalein 6-O-glucuronide
80	5.21	465.103 9	-	Plantagoside		8.88	447.094 2	+
81	5.23	431.101 1	-	Apigenin-8-C-glucoside	196	8.88	459.093 8	-	Wogonoside^*
	5.24	433.114 4	+			8.95	461.107 5	+
82	5.25	441.082 2	-	Catechin gallate	197	9.04	489.102 3	-	Comanthoside B
83	5.25	447.092 7	-	Plantaginin		9.07	491.119 5	+
	5.29	449.109 3	+		198	9.09	345.060 2	-	Viscidulin Ⅲ
84	5.57	319.118 4	+	Paeoniflorigenone		9.19	347.075 7	+
85	5.29	609.181 9	-	Calceolarioside C	199	9.16	629.186 2	-	Benzoylpaeoniflorin
86	5.32	207.138 6	+	Sinapoylmalate		9.16	607.180 1	+
87	5.37	441.082 4	-	Epicatechin gallate	200	9.29	475.123 5	+	6'-O-Acetylgenistin
88	5.39	433.113 9	-	Naringenin-7-O-glucoside		8.28	653.245 7	+
	5.39	435.127 9	+		201	9.31	629.186 1	-	Benzoylpaeoniflorin
89	5.39	491.119 1	-	Tricin 7-O-glucoside^*		9.36	607.180 5	+
90	5.47	547.145 0	-	Chrysin 6-C-glucoside 8-C-arabinoside	202	9.35	315.180 2	-	Perilloside C
	5.51	549.159 3	+		203	9.42	549.125 7	-	Chrysosplenetin 5-O-glucuronide
91	5.58	383.197 5	+	Isocorynoxeine^*	204	9.47	299.055 3	-	Tectorigenin
92	5.48	607.073 4	-	Glucoraphenin-5-hydroxyindole-3-acetic acid		9.48	301.071 2	+
	5.49	609.088 9	+		205	9.48	223.075 4	-	Hydroxychalcone
93	5.49	577.154 4	-	2-O-Rhamnosylvitexin	206	9.51	269.044 8	-	Apigenin^*
	5.65	579.173 3	+			9.73	271.060 7	+
94	5.53	596.055 5	-	Caffeoyl glucoraphenin	207	9.66	269.044 9	-	Apigenin isomers
95	5.57	521.203 0	-	Lariciresinol 4-O-glucoyranoside		9.64	271.060 6	+
96	5.58	434.061 6	-	Glucoberteroin	208	9.76	285.039 7	-	Kaempferol^*
97	5.60	573.210 0	-	5β-Carboxystrictosidine		9.85	287.055 5	+
98	5.62	463.086 7	-	Quercetin-4'-O-glucoside	209	9.80	299.055 3	-	Chrysoeriol
	5.63	465.102 8	+			9.82	301.071 2	+
99	5.65	431.097 2	-	Isovitexin	211	9.81	395.204 0	-	Tsangane 3-glucoside
	5.67	433.114 0	+		212	9.90	329.066 5	-	Tricin
100	5.71	623.196 8	-	Acteoside^*		9.97	331.081 0	+
	5.71	647.196 3	+		213	9.98	299.055 4	-	Hispidulin
101	5.71	621.180 9	-	Crenatoside	214	10.06	359.077 3	-	Sideritoflavone
102	5.72	607.130 7	-	Baicalein-6-O-glucose-7-O-glucuronide		10.04	361.092 7	+
103	5.72	939.109 1	-	Penta-O-galloyl-β-glucose	215	10.09	303.050 3	-	Taxifolin
104	5.73	521.129 5	-	Salviaflaside		10.24	305.066 3	+
105	5.74	631.166 4	-	Galloylpaeoniflorin	216	10.12	269.044 9	-	Baicalein^*
	5.74	655.165 5	+			10.22	271.060 7	+
106	5.80	431.097 1	-	Oroxin A	217	10.13	285.039 8	-	Luteolin
107	5.81	509.130 5	+	Syringetin 3-glucoside		10.21	287.055 3	+
	5.82	531.112 8	+		218	10.24	299.055 3	-	Scutellarein 4'-methyl ether
108	5.83	477.062 6	-	1-Methoxyindol-3-ylmethyl glucosinolate	219	10.42	329.066 6	-	4', 5, 7-Trihydroxy-3, 6-dimethoxyflavone
109	5.84	351.170 4	+	Strychnine N-oxide		10.42	331.082 3	+
110	5.85	547.145 0	-	Chrysin 8-C-glucoside 6-C-arabinoside	220	10.46	327.087 0	+	Usnic acid
	5.90	549.159 2	+		221	10.53	223.075 4	-	Hydroxychalcone
111	5.94	383.197 5	+	Corynoxeine^*	222	10.61	299.055 4	-	Tectorigenin
112	5.93	461.072 9	-	Scutellarin^*		10.72	301.071 2	+
	5.95	463.088 0	+		223	11.08	329.066 6	-	3, 4'-Dimethoxy-5, 7, 3'-trihydroxyflavone
113	5.96	463.086 8	-	Quercetin-4'-O-glucoside		11.18	331.082 4	+
114	5.98	351.170 3	+	Strychnine N-oxide	224	11.31	313.107 9	+	Baicalein trimethyl ether
115	5.98	475.124 1	-	Plantasioside	225	11.56	359.077 3	-	3, 5, 7-Trihydroxy-3', 4', 5'-trimethoxyflavone
116	6.00	723.212 8	-	1-Sinapoyl-2-feruloylgentiobiose	11.66	361.092 5	+
117	6.00	385.213 1	+	Isorhyncophylline^*	226	11.67	821.397 6	-	Uralsaponin A
118	6.01	477.102 3	-	Petunidin-3-O-β-glucopyranoside		11.68	823.412 5	+
119	6.02	353.185 4	+	Ajmalicine	227	11.68	343.082 4	-	Tricin methyl ether
120	6.10	181.049 6	+	Caffeic acid		11.79	345.097 3	+
121	6.11	415.103 7	-	Daidzein-6-C-glucoside	228	11.74	255.065 9	-	Dihydrodaidzein
	6.11	417.119 1	+		229	11.98	283.060 4	-	Wogonin^*
122	6.11	640.082 8	-	Sinapinic acid 4-methylsulfinyl-3-butenyl glucosinolate		12.10	285.076 0	+
123	6.13	623.197 1	-	Isoacteoside^*	230	11.99	313.070 9	-	3, 7-Dihydroxy-3', 4'-dimethoxyflavone
	6.14	647.196 2	+		231	12.13	253.049 7	-	Chrysin^*
124	6.15	339.070 9	-	Sinapoyl malate		12.26	253.049 7	+
125	6.19	461.108 1	-	Tectoridin	232	12.20	255.065 7	-	Pinocembrine
	6.418	463.123 1	+		233	12.21	373.091 6	-	Skullcapflavone Ⅱ
126	6.22	642.099 4	-	Sinapinic acid glucoraphanin		12.23	375.108 4	+
127	6.22	653.208 6	-	Campneoside	234	12.22	313.070 7	-	Pectolinarigenin
128	6.26	565.190 7	-	Simplocosin		12.21	315.086 0	+
129	6.28	515.132 0	-	3, 4-Di-O-caffeoylquinic acid	235	12.45	313.070 7	-	Cirsimaritin
130	6.34	385.211 4	+	Rhynchophylline^*		12.48	315.086 3	+
131	6.34	631.166 4	-	Galloylalbiflorin	236	12.47	283.060 3	-	Oroxylin A
	6.37	655.165 8	+			12.56	285.076 0	+
132	6.40	339.144 9	-	Isoprenylhydroquinone glucoside	237	12.93	343.080 9	-	Eupatilin
						13.05	345.097 6	+

No.

t_R/min

m/z

Mode

Annotation

No.

t_R/min

m/z

Mode

Annotation

0.92

225.060 2

Glucoheptonic acid

133

6.42

579.207 9

Eleutheroside E1

0.97

191.055 0

Quinic acid

134

6.42

580.061 3

Coumaroyl glucoraphenin

0.97

345.118 0

Aucubin

135

6.44

415.103 6

Puerarin

0.99

166.123 1

Pseudoephedrine^*

6.52

417.119 2

1.12

169.013 2

Gallic acid

136

6.45

431.096 9

Apigenin 7-O-β-D-glucoside

1.29

152.107 5

Norephedrine

6.45

433.114 3

1.29

166.123 1

(−)-Ephedrine^*

137

6.48

639.155 0

Isorhamnetin-3, 7-diglucoside

1.32

169.013 1

Gallic acid

138

6.48

461.073 0

Scutellarein-6-O-glucuronide

1.42

180.138 7

Methylephedrine

6.80

463.088 0

1.45

372.042 4

Gluconapin

139

6.49

610.070 2

Feruloyl glucoraphenin

1.46

373.113 6

Geniposidic acid^*

140

6.50

640.082 6

Sinapoyl glucoraphenin

1.47

397.110 8

141

6.51

515.132 1

Isochlorogenic acid^*

1.48

422.024 4

Glucoiberin

142

6.56

205.085 5

4-Hydroxy-3-(3-methylbut-2-enyl)benzoic acid

1.48

452.034 2

4-Methylsulfonylbutyl glucosinolate

143

6.57

637.213 0

Plantainoside C

1.52

434.025 4

Glucoraphenin

6.80

639.229 6

1.57

176.020 2

Sulforaphene

144

6.58

799.229 2

3', 6-Disinapoylsucrose

1.65

450.020 1

4-Methylsulfonyl-3-butenyl glucosinolate

6.62

777.221 1

1.65

434.025 4

Glucoraphenin

145

6.61

449.107 5

Eriodictyol-7-O-glucoside

1.67

388.037 1

Epiprogoitrin

146

6.63

505.134 6

Isorinic acid-3'-O-glucoside

1.77

461.166 8

Decaffeoylverbascoside

147

6.65

387.128 9

Sinapoylglucose

1.78

450.056 6

5-Methylsulfinyl-n-pentyl glucosinolate

148

6.65

538.050 6

Glucoraphenin benzoate

1.90

375.129 5

Loganic acid

6.73

540.065 7

1.78

399.127 7

149

6.71

1445.426 5

1-Sinapoyl-2-feruloyl gentiobiose

1.93

153.017 9

Protocatechuic acid^*

150

6.72

417.120 0

Glucoliquiritigenin

2.10

353.087 6

Neochlorogenic acid

151

6.75

693.202 8

Helonioside A

2.07

355.103 1

152

6.75

187.096 1

Azelaic acid

2.10

577.135 1

Procyanidin B2

153

6.77

435.129 7

Phloridzin

2.12

579.150 5

5.22

437.142 4

2.12

310.165 1

Sinapine^*

154

6.79

359.077 0

Rosmarinic acid^*

2.35

618.203 3

Triglucosyl cyanogen glycoside

6.90

361.092 2

2.54

411.127 7

Secologanin

155

6.84

509.164 2

Paeobrin

2.55

289.070 9

Epicatechin

156

6.86

177.017 9

Esculetin

2.58

305.066 5

Gallocatechin

6.13

179.034 3

2.69

289.070 9

Epicatechin

157

6.95

181.050 1

Caffeic acid

3.17

547.165 8

Sibiricose A1

158

6.95

477.102 4

Hesperetin 3'-O-glucuronide

3.25

456.150 5

Amygdalin^*

7.01

479.118 4

3.32

475.191 8

159

6.97

607.201 6

Osmanthuside J

3.25

618.203 4

Triglucosyl cyanogen glycoside

160

7.00

475.087 8

Hispidulin 7-glucuronide

3.44

177.017 8

Dihydroxycoumarin

6.98

477.103 5

3.45

355.103 5

Chlorogenic acid^*

161

7.05

753.227 0

3', 6-Disinapoylsucrose

3.46

353.087 4

162

7.06

461.108 5

Homoplantaginin

3.57

369.182 1

Mitraphylline

7.14

463.123 5

3.65

353.087 6

4-O-Caffeoylquinic acid

163

7.078

507.148 8

Lactiflorin

3.65

355.103 4

164

7.171

637.212 9

Leucosceptoside A

3.61

179.034 4

Caffeic acid^*

7.282

639.229 3

3.73

387.129 1

Miscanthoside

165

7.203

505.099 7

Tricin-7-glucuronoside

3.92

593.150 3

Apigenin-6, 8-di-C-glycoside

7.291

507.115 4

3.93

595.166 9

166

7.213

511.053 7

Baicalein 7-O-glucoside 5-O-sulfate

3.93

371.196 7

Rhyncophyllic acid

167

7.226

287.056 1

Eriodictyol

3.93

411.125 6

Geniposide^*

7.326

289.070 4

4.03

635.086 9

1, 3, 6-Tri-O-galloylglucose

168

7.333

477.103 5

Hispidulin 7-O-glucuronide

4.08

521.202 6

Isolariciresinol 4-O-glucopyranoside

169

7.439

369.180 9

Speciophylline

4.12

327.108 2

Ethyl vanillin glucoside

170

7.422

431.097 1

Oroxin A

4.14

381.116 5

Sweroside

7.475

433.114 3

4.16

547.166 1

Sibiricose A6

171

7.432

345.060 2

Viscidulin Ⅲ

4.16

294.098 4

Prulaurasin

7.521

347.076 9

4.18

420.045 7

Glucoerucin

172

7.595

445.078 0

Baicalin^*

4.23

207.138 6

Sinapoylmalate

7.695

447.092 6

4.36

525.161 1

Paeoniflorin^*

173

7.673

651.230 3

Compound NP-002173

4.35

481.171 2

7.752

675.227 3

4.36

641.209 5

Isomaltopaeoniflorin

174

7.722

477.102 6

Homoeriodictyol glucuronide

4.37

609.146 4

Luteolin-3', 7-di-O-glucoside

7.81

479.120 8

4.47

611.161 6

175

7.77

287.055 1

Maesopsin

4.48

369.182 1

Isomitraphylline

176

7.78

505.097 3

Tricin 7-O-glucuronide

4.46

593.147 4

Vitexin 4-O-glucoside

7.86

507.113 1

4.51

343.139 8

Dihydroconiferin

177

7.91

447.092 8

Naringenin-4'-O-glucuronide

4.56

639.192 3

Plantamajoside D

7.99

449.107 7

4.57

785.251 7

Echinacoside

178

7.99

445.113 7

Wogonin 7-O-glucoside

4.59

327.144 4

Perilloside B

8.63

447.128 5

4.60

563.138 0

Schaftoside^*

179

8.02

415.103 8

Daidzin

4.63

565.154 5

8.02

417.119 4

4.65

495.150 8

Oxypaeoniflorin

180

8.02

591.206 6

Osmanthuside B6

4.67

497.165 7

181

8.08

477.102 6

Hesperetin-7-O-glucuronide

4.67

525.161 0

Albiflorin^*

182

8.15

445.075 8

Baicalein 6-O-glucuronide

4.75

503.153 4

183

8.16

461.108 4

Peonidin 3-galactoside

4.71

401.208 4

Isorhynchophylline N-oxide

8.24

463.123 3

4.72

543.116 5

Paeoniflorinsulfonic acid

184

8.18

651.230 0

Compound NP-002173

4.73

447.092 6

Luteolin 7-glucoside

8.28

653.245 7

4.82

471.090 5

185

8.23

285.039 7

Luteolin^*

4.74

593.147 3

Pelargonin

186

8.24

431.098 9

Kaempferol-7-O-rhamnoside

4.80

595.166 8

8.27

433.114 7

4.84

563.141 0

Isoschaftoside

187

8.28

445.077 8

Baicalein 5-O-glucuronide

4.69

565.154 5

8.24

447.092 5

4.93

495.151 3

Oxypaeoniflorin

188

8.36

475.087 8

Hispidulin 7-glucuronide

4.93

371.196 6

Rhyncophyllic acid

8.44

477.103 6

4.96

401.208 1

Isorhynchophylline N-oxide

189

8.40

345.061 5

5, 7, 3', 4'-Tetrahydroxy-6, 8-dimethoxyflavone

4.96

367.102 6

3-O-Feruloylquinic acid^*

8.70

347.077 0

4.99

787.263 9

Liriodendrin

190

8.52

429.081 8

Chrysin-7-O-glucuronide

5.00

639.154 4

Dactylin

8.60

431.098 1

5.01

577.154 8

Chrysin 8-C-glucoside 6-C-glucoside

191

8.52

459.093 8

Oroxylin A-7-O-glucuronide

5.04

579.173 0

8.64

461.107 6

5.07

369.182 0

Mitraphylline

192

8.55

591.206 6

Osmanthuside B6

5.13

621.180 7

Isocrenatoside

193

8.64

511.054 0

Baicalein 7-O-glucoside 6-O-sulfate

5.15

509.130 3

Syringetin 3-glucoside

194

8.71

475.087 8

Hispidulin 7-glucuronide

5.15

433.113 9

Naringenin-7-O-glucoside

8.78

477.103 6

5.20

755.239 7

Compound NP-000173

195

8.82

445.077 3

Baicalein 6-O-glucuronide

5.21

465.103 9

Plantagoside

8.88

447.094 2

5.23

431.101 1

Apigenin-8-C-glucoside

196

8.88

459.093 8

Wogonoside^*

5.24

433.114 4

8.95

461.107 5

5.25

441.082 2

Catechin gallate

197

9.04

489.102 3

Comanthoside B

5.25

447.092 7

Plantaginin

9.07

491.119 5

5.29

449.109 3

198

9.09

345.060 2

Viscidulin Ⅲ

5.57

319.118 4

Paeoniflorigenone

9.19

347.075 7

5.29

609.181 9

Calceolarioside C

199

9.16

629.186 2

Benzoylpaeoniflorin

5.32

207.138 6

Sinapoylmalate

9.16

607.180 1

5.37

441.082 4

Epicatechin gallate

200

9.29

475.123 5

6'-O-Acetylgenistin

5.39

433.113 9

Naringenin-7-O-glucoside

8.28

653.245 7

5.39

435.127 9

201

9.31

629.186 1

Benzoylpaeoniflorin

5.39

491.119 1

Tricin 7-O-glucoside^*

9.36

607.180 5

5.47

547.145 0

Chrysin 6-C-glucoside 8-C-arabinoside

202

9.35

315.180 2

Perilloside C

5.51

549.159 3

203

9.42

549.125 7

Chrysosplenetin 5-O-glucuronide

5.58

383.197 5

Isocorynoxeine^*

204

9.47

299.055 3

Tectorigenin

5.48

607.073 4

Glucoraphenin-5-hydroxyindole-3-acetic acid

9.48

301.071 2

5.49

609.088 9

205

9.48

223.075 4

Hydroxychalcone

5.49

577.154 4

2-O-Rhamnosylvitexin

206

9.51

269.044 8

Apigenin^*

5.65

579.173 3

9.73

271.060 7

5.53

596.055 5

Caffeoyl glucoraphenin

207

9.66

269.044 9

Apigenin isomers

5.57

521.203 0

Lariciresinol 4-O-glucoyranoside

9.64

271.060 6

5.58

434.061 6

Glucoberteroin

208

9.76

285.039 7

Kaempferol^*

5.60

573.210 0

5β-Carboxystrictosidine

9.85

287.055 5

5.62

463.086 7

Quercetin-4'-O-glucoside

209

9.80

299.055 3

Chrysoeriol

5.63

465.102 8

9.82

301.071 2

5.65

431.097 2

Isovitexin

211

9.81

395.204 0

Tsangane 3-glucoside

5.67

433.114 0

212

9.90

329.066 5

Tricin

100

5.71

623.196 8

Acteoside^*

9.97

331.081 0

5.71

647.196 3

213

9.98

299.055 4

Hispidulin

101

5.71

621.180 9

Crenatoside

214

10.06

359.077 3

Sideritoflavone

102

5.72

607.130 7

Baicalein-6-O-glucose-7-O-glucuronide

10.04

361.092 7

103

5.72

939.109 1

Penta-O-galloyl-β-glucose

215

10.09

303.050 3

Taxifolin

104

5.73

521.129 5

Salviaflaside

10.24

305.066 3

105

5.74

631.166 4

Galloylpaeoniflorin

216

10.12

269.044 9

Baicalein^*

5.74

655.165 5

10.22

271.060 7

106

5.80

431.097 1

Oroxin A

217

10.13

285.039 8

Luteolin

107

5.81

509.130 5

Syringetin 3-glucoside

10.21

287.055 3

5.82

531.112 8

218

10.24

299.055 3

Scutellarein 4'-methyl ether

108

5.83

477.062 6

1-Methoxyindol-3-ylmethyl glucosinolate

219

10.42

329.066 6

4', 5, 7-Trihydroxy-3, 6-dimethoxyflavone

109

5.84

351.170 4

Strychnine N-oxide

10.42

331.082 3

110

5.85

547.145 0

Chrysin 8-C-glucoside 6-C-arabinoside

220

10.46

327.087 0

Usnic acid

5.90

549.159 2

221

10.53

223.075 4

Hydroxychalcone

111

5.94

383.197 5

Corynoxeine^*

222

10.61

299.055 4

Tectorigenin

112

5.93

461.072 9

Scutellarin^*

10.72

301.071 2

5.95

463.088 0

223

11.08

329.066 6

3, 4'-Dimethoxy-5, 7, 3'-trihydroxyflavone

113

5.96

463.086 8

Quercetin-4'-O-glucoside

11.18

331.082 4

114

5.98

351.170 3

Strychnine N-oxide

224

11.31

313.107 9

Baicalein trimethyl ether

115

5.98

475.124 1

Plantasioside

225

11.56

359.077 3

3, 5, 7-Trihydroxy-3', 4', 5'-trimethoxyflavone

116

6.00

723.212 8

1-Sinapoyl-2-feruloylgentiobiose

11.66

361.092 5

117

6.00

385.213 1

Isorhyncophylline^*

226

11.67

821.397 6

Uralsaponin A

118

6.01

477.102 3

Petunidin-3-O-β-glucopyranoside

11.68

823.412 5

119

6.02

353.185 4

Ajmalicine

227

11.68

343.082 4

Tricin methyl ether

120

6.10

181.049 6

Caffeic acid

11.79

345.097 3

121

6.11

415.103 7

Daidzein-6-C-glucoside

228

11.74

255.065 9

Dihydrodaidzein

6.11

417.119 1

229

11.98

283.060 4

Wogonin^*

122

6.11

640.082 8

Sinapinic acid 4-methylsulfinyl-3-butenyl glucosinolate

12.10

285.076 0

123

6.13

623.197 1

Isoacteoside^*

230

11.99

313.070 9

3, 7-Dihydroxy-3', 4'-dimethoxyflavone

6.14

647.196 2

231

12.13

253.049 7

Chrysin^*

124

6.15

339.070 9

Sinapoyl malate

12.26

253.049 7

125

6.19

461.108 1

Tectoridin

232

12.20

255.065 7

Pinocembrine

6.418

463.123 1

233

12.21

373.091 6

Skullcapflavone Ⅱ

126

6.22

642.099 4

Sinapinic acid glucoraphanin

12.23

375.108 4

127

6.22

653.208 6

Campneoside

234

12.22

313.070 7

Pectolinarigenin

128

6.26

565.190 7

Simplocosin

12.21

315.086 0

129

6.28

515.132 0

3, 4-Di-O-caffeoylquinic acid

235

12.45

313.070 7

Cirsimaritin

130

6.34

385.211 4

Rhynchophylline^*

12.48

315.086 3

131

6.34

631.166 4

Galloylalbiflorin

236

12.47

283.060 3

Oroxylin A

6.37

655.165 8

12.56

285.076 0

132

6.40

339.144 9

Isoprenylhydroquinone glucoside

237

12.93

343.080 9

Eupatilin

13.05

345.097 6