药学学报

Number	Trade name	Sample	Geographical origin
1	Ludangshen (LD)	PS1	Pingshun, Changzhi, Shanxi
2		PS2	Pingshun, Changzhi, Shanxi
3		PS3	Pingshun, Changzhi, Shanxi
4		PS4	Pingshun, Changzhi, Shanxi
5		PS5	Pingshun, Changzhi, Shanxi
6		PS6	Pingshun, Changzhi, Shanxi
7		HG1	Huguan, Changzhi, Shanxi
8		HG2	Huguan, Changzhi, Shanxi
9		HG3	Huguan, Changzhi, Shanxi
10		HG4	Huguan, Changzhi, Shanxi
11		HG5	Huguan, Changzhi, Shanxi
12		HG6	Huguan, Changzhi, Shanxi
13		HG7	Huguan, Changzhi, Shanxi
14		HG8	Huguan, Changzhi, Shanxi
15		LC1	Lingchuan, Jincheng, Shanxi
16		LC2	Lingchuan, Jincheng, Shanxi
17		LC3	Lingchuan, Jincheng, Shanxi
18		LC4	Lingchuan, Jincheng, Shanxi
19		LC5	Lingchuan, Jincheng, Shanxi
20		LC6	Lingchuan, Jincheng, Shanxi
21		LC7	Lingchuan, Jincheng, Shanxi
22		LC8	Lingchuan, Jincheng, Shanxi
23		LC9	Lingchuan, Jincheng, Shanxi
24	Baitiaodang (GS)	GS1	Weiyuan, Dingxi, Gansu
25		GS2	Weiyuan, Dingxi, Gansu
26		GS3	Weiyuan, Dingxi, Gansu
27		GS4	Weiyuan, Dingxi, Gansu
28		GS5	Weiyuan, Dingxi, Gansu
29		GS6	Weiyuan, Dingxi, Gansu

Number	Trade name	Sample	Geographical origin
1	Ludangshen (LD)	PS1	Pingshun, Changzhi, Shanxi
2		PS2	Pingshun, Changzhi, Shanxi
3		PS3	Pingshun, Changzhi, Shanxi
4		PS4	Pingshun, Changzhi, Shanxi
5		PS5	Pingshun, Changzhi, Shanxi
6		PS6	Pingshun, Changzhi, Shanxi
7		HG1	Huguan, Changzhi, Shanxi
8		HG2	Huguan, Changzhi, Shanxi
9		HG3	Huguan, Changzhi, Shanxi
10		HG4	Huguan, Changzhi, Shanxi
11		HG5	Huguan, Changzhi, Shanxi
12		HG6	Huguan, Changzhi, Shanxi
13		HG7	Huguan, Changzhi, Shanxi
14		HG8	Huguan, Changzhi, Shanxi
15		LC1	Lingchuan, Jincheng, Shanxi
16		LC2	Lingchuan, Jincheng, Shanxi
17		LC3	Lingchuan, Jincheng, Shanxi
18		LC4	Lingchuan, Jincheng, Shanxi
19		LC5	Lingchuan, Jincheng, Shanxi
20		LC6	Lingchuan, Jincheng, Shanxi
21		LC7	Lingchuan, Jincheng, Shanxi
22		LC8	Lingchuan, Jincheng, Shanxi
23		LC9	Lingchuan, Jincheng, Shanxi
24	Baitiaodang (GS)	GS1	Weiyuan, Dingxi, Gansu
25		GS2	Weiyuan, Dingxi, Gansu
26		GS3	Weiyuan, Dingxi, Gansu
27		GS4	Weiyuan, Dingxi, Gansu
28		GS5	Weiyuan, Dingxi, Gansu
29		GS6	Weiyuan, Dingxi, Gansu

Peak No.	Metabolite	Formula	t_R/min	m/z	Ion	VIP	P	Log₂FC	Regulated
1	Dipivefrin	C₁₉H₂₉NO₅	14.367	351.205	+	12.450	0.028	-1.986	Up
2	1-Linoleoylglycerophosphocholine	C₂₆H₅₀NO₇P	23.701	519.333	+	10.167	0.016	1.587	Down
3	Proline	C₅H₉NO₂	1.039	115.064	-	8.709	0.008	2.138	Down
4	1-Palmitoylglycerophosphocholine	C₂₄H₅₀NO₇P	24.151	495.333	+	8.708	0.002	1.571	Down
5	Codonopsinol B	C₁₃H₁₉NO₄	5.769	253.131	+	6.774	0.013	1.466	Down
6	Propanidid	C₁₈H₂₇NO₅	12.224	337.189	-	6.401	0.001	-2.165	Up
7	D-Raffinose	C₁₈H₃₂O₁₆	1.510	504.169	-	6.366	0.009	1.241	Down
8	Codonopsinol A	C₁₃H₁₉NO₅	2.633	269.126	+	6.059	0.008	1.392	Down
9	Ethopabate	C₁₂H₁₅NO₄	2.662	237.100	-	6.031	0.008	1.395	Down
10	L-Pyroglutamic acid	C₅H₇NO₃	0.974	129.042	-	5.881	0.001	-1.835	Up
11	9,11-Octadecadienoicacid	C₁₈H₃₂O₄	24.872	294.220	+	5.701	0.022	1.409	Down
12	Atractylenolide Ⅲ	C₁₅H₂₀O₃	22.520	248.141	-	5.580	0.017	-2.435	Up
13	Tangshenoside Ⅰ	C₂₉H₄₂O₁₈	11.347	678.633	+	4.728	0.024	-1.910	Up
14	L-Glutamic acid	C₅H₉NO₄	0.979	147.053	-	4.654	0.002	-1.134	Up
15	Afegostat	C₆H₁₃NO₃	1.098	147.090	-	4.258	0.001	-2.410	Up
16	Pipecolic acid	C₆H₁₁NO₂	1.102	129.079	+	4.246	0.001	-2.409	Up
17	D(-)-Amygdalin	C₂₈H₃₀N₈O₅	13.847	558.231	-	3.937	0.008	3.071	Down
18	Bis-D-fructose	C₁₂H₂₀O₁₀	1.537	324.105	-	3.910	0.002	3.001	Down
19	(+/-)9,10-Dihydroxy-12Z-octadecenoic acid	C₁₈H₃₄O₄	23.108	314.246	-	3.837	0.004	2.200	Down
20	Renardine	C₁₉H₂₇NO₆	10.681	365.184	-	3.805	0.007	-1.421	Up
21	Maltopentaose	C₃₀H₅₂O₂₆	1.595	850.257	-	3.266	0.017	1.532	Down
22	Maltotetraose	C₂₄H₄₂O₂₁	1.542	688.204	+	3.174	0.010	1.170	Down
23	Syringin	C₁₇H₂₄O₉	10.078	372.367	-	3.049	0.003	-2.521	Up
24	O-Succinyl-L-homoserine	C₈H₁₃NO₆	0.986	219.074	+	2.925	0.016	1.371	Down
25	Chlorogenic acid	C₁₆H₁₈O₉	8.604	354.095	-	2.903	0.005	1.635	Down
26	Muramic acid	C₉H₁₇NO₇	0.990	269.111	-	2.870	0.026	1.541	Down
27	D-Arabinonate	C₅H₁₀O₆	0.996	166.048	+	2.842	0.000	1.390	Down
28	N-alpha-Acetylarginine	C₈H₁₆N₄O₃	1.541	216.123	-	2.814	0.023	2.136	Down
29	N-D-Glucosylarylamine	C₁₂H₁₇NO₅	1.536	255.111	+	2.812	0.024	1.153	Down
30	Lotaustralin	C₁₁H₁₉NO₆	1.532	261.121	+	2.6153	2.202	1.762	Down
31	Coniferin	C₁₆H₂₂O₈	9.841	342.131	+	2.553	0.004	3.534	Down
32	Rosmarinine	C₁₈H₂₇NO₆	10.127	353.184	-	2.453	0.014	-2.822	Up
33	Ascorbyl stearate	C₂₄H₄₂O₇	25.375	442.293	-	2.261	0.021	1.825	Down
34	2-Isopropylmalic acid	C₇H₁₂O₅	8.035	176.068	-	2.166	0.024	4.105	Down
35	Phloionolic acid	C₁₈H₃₆O₅	21.305	332.256	-	2.160	0.044	2.837	Down
36	2-Oxovalericacid	C₅H₈O₃	8.025	116.047	-	2.160	0.024	4.089	Down
37	N-linoleoyl-4-aminobutyric acid	C₂₂H₃₉NO₃	25.876	365.293	+	2.137	0.002	3.177	Down
38	1-Hydroxycholic acid	C₂₄H₄₀O₆	25.374	424.282	-	2.116	0.016	1.849	Down
39	1-alpha-D-Galactosyl-myo-inositol	C₁₂H₂₂O₁₁	1.541	342.116	-	2.097	0.015	2.879	Down
40	Picrotoxinin	C₁₅H₁₆O₆	10.023	292.094	+	1.9508	0.009	1.992	Down
41	Alloxydim	C₁₇H₂₅NO₅	9.249	323.173	+	1.887	0.015	-3.124	Up
42	9,12,13-Trihydroxy 10,15-octadecadienoic acid	C₁₈H₃₂O₅	21.033	328.225	+	1.806	0.010	1.968	Down
43	Miglitol	C₈H₁₇NO₅	0.979	207.111	-	1.750	0.035	1.627	Down
44	1,4-D-Xylobiose	C₁₀H₁₈O₉	1.514	282.095	+	1.697	0.011	1.126	Down
45	L-Lathyrine	C₇H₁₀N₄O₂	1.030	182.080	+	1.678	0.029	1.770	Down
46	Biphenyl	C₁₂H₁₀	13.417	154.078	-	1.661	0.015	2.407	Down
47	Linoleoyl ethanolamide	C₂₀H₃₇NO₂	25.777	323.282	-	1.574	0.001	2.002	Down
48	Adenine	C₅H₅N₅	1.085	135.055	+	1.574	0.030	1.538	Down
49	3-Methylcrotonylglycine	C₇H₁₁NO₃	1.074	157.074	+	1.561	0.011	2.324	Down
50	Uridine	C₉H₁₂N₂O₆	2.040	244.069	-	1.536	0.013	1.325	Down
51	Methyl cinnamate	C₁₀H₁₀O₂	9.754	162.068	+	1.516	0.011	2.860	Down
52	Secologanin	C₁₇H₂₄O₁₀	8.156	388.137	+	1.404	0.008	3.179	Down
53	Methyldopa	C₁₀H₁₃NO₄	9.606	211.084	-	1.383	0.005	1.302	Down
54	Sinapoylcholine	C₁₆H₂₃NO₅	7.867	309.158	+	1.341	0.042	-1.955	Up
55	Palmitoylglucuronide	C₂₂H₄₂O₇	25.989	418.293	-	1.315	0.004	1.078	Down
56	1,3-Dihydroxy-1-(7-methoxy-2-oxo-2H-chromen-6-yl)-3-methylbutan-2-yl 3-methylbutanoate	C₂₀H₂₆O₇	12.982	400.150	-	1.308	0.020	1.606	Down
57	cis-Aconitic acid	C₆H₆O₆	1.639	174.016	-	1.283	0.004	2.109	Down
58	Cortol	C₂₁H₃₆O₅	23.948	368.256	+	1.258	0.018	1.149	Down
59	AtractylenolideI	C₁₅H₁₈O₂	23.917	230.131	-	1.241	0.023	-2.809	Up
60	Dubinidine	C₁₅H₁₇NO₄	8.556	275.116	-	1.234	0.036	3.356	Down
61	9-Oxo-ODE	C₁₈H₃₀O₃	22.554	294.220	+	1.234	0.001	1.700	Down
62	Amylose	C₁₄H₂₆O₁₁	2.828	370.148	-	1.222	0.022	2.169	Down
63	3,4-Dihydroxymandelaldehyde	C₈H₈O₄	1.055	168.042	+	1.212	0.028	1.008	Down
64	N-Acetyl-D-sphingosine	C₂₀H₃₉NO₃	26.458	341.293	-	1.204	0.003	1.975	Down
65	(E)-Glutaconate	C₅H₆O₄	1.626	130.027	-	1.201	0.001	1.302	Down
66	Palmitoleic Acid	C₁₆H₃₀O₂	20.864	276.209	+	1.186	0.012	1.165	Down
67	Carbofuran	C₁₂H₁₅NO₃	6.271	221.105	-	1.161	0.004	2.209	Down
68	7-Hydroxycoumarine	C₉H₆O₃	8.605	162.032	-	1.155	0.005	1.494	Down
69	(+/-)12(13)-DiHOME	C₁₈H₃₄O₄	21.325	296.235	+	1.124	0.049	2.456	Down
70	Fenipentol	C₁₁H₁₆O	25.444	164.12	+	1.121	0.032	-3.960	Up
71	Linoleic acid	C₁₈H₃₂O₂	25.380	280.240	-	1.119	0.040	1.569	Down
72	5-Methyldeoxycytidine	C₁₀H₁₅N₃O₄	4.551	241.106	-	1.108	0.030	1.150	Down

Peak No.	Metabolite	Formula	t_R/min	m/z	Ion	VIP	P	Log₂FC	Regulated
1	Dipivefrin	C₁₉H₂₉NO₅	14.367	351.205	+	12.450	0.028	-1.986	Up
2	1-Linoleoylglycerophosphocholine	C₂₆H₅₀NO₇P	23.701	519.333	+	10.167	0.016	1.587	Down
3	Proline	C₅H₉NO₂	1.039	115.064	-	8.709	0.008	2.138	Down
4	1-Palmitoylglycerophosphocholine	C₂₄H₅₀NO₇P	24.151	495.333	+	8.708	0.002	1.571	Down
5	Codonopsinol B	C₁₃H₁₉NO₄	5.769	253.131	+	6.774	0.013	1.466	Down
6	Propanidid	C₁₈H₂₇NO₅	12.224	337.189	-	6.401	0.001	-2.165	Up
7	D-Raffinose	C₁₈H₃₂O₁₆	1.510	504.169	-	6.366	0.009	1.241	Down
8	Codonopsinol A	C₁₃H₁₉NO₅	2.633	269.126	+	6.059	0.008	1.392	Down
9	Ethopabate	C₁₂H₁₅NO₄	2.662	237.100	-	6.031	0.008	1.395	Down
10	L-Pyroglutamic acid	C₅H₇NO₃	0.974	129.042	-	5.881	0.001	-1.835	Up
11	9,11-Octadecadienoicacid	C₁₈H₃₂O₄	24.872	294.220	+	5.701	0.022	1.409	Down
12	Atractylenolide Ⅲ	C₁₅H₂₀O₃	22.520	248.141	-	5.580	0.017	-2.435	Up
13	Tangshenoside Ⅰ	C₂₉H₄₂O₁₈	11.347	678.633	+	4.728	0.024	-1.910	Up
14	L-Glutamic acid	C₅H₉NO₄	0.979	147.053	-	4.654	0.002	-1.134	Up
15	Afegostat	C₆H₁₃NO₃	1.098	147.090	-	4.258	0.001	-2.410	Up
16	Pipecolic acid	C₆H₁₁NO₂	1.102	129.079	+	4.246	0.001	-2.409	Up
17	D(-)-Amygdalin	C₂₈H₃₀N₈O₅	13.847	558.231	-	3.937	0.008	3.071	Down
18	Bis-D-fructose	C₁₂H₂₀O₁₀	1.537	324.105	-	3.910	0.002	3.001	Down
19	(+/-)9,10-Dihydroxy-12Z-octadecenoic acid	C₁₈H₃₄O₄	23.108	314.246	-	3.837	0.004	2.200	Down
20	Renardine	C₁₉H₂₇NO₆	10.681	365.184	-	3.805	0.007	-1.421	Up
21	Maltopentaose	C₃₀H₅₂O₂₆	1.595	850.257	-	3.266	0.017	1.532	Down
22	Maltotetraose	C₂₄H₄₂O₂₁	1.542	688.204	+	3.174	0.010	1.170	Down
23	Syringin	C₁₇H₂₄O₉	10.078	372.367	-	3.049	0.003	-2.521	Up
24	O-Succinyl-L-homoserine	C₈H₁₃NO₆	0.986	219.074	+	2.925	0.016	1.371	Down
25	Chlorogenic acid	C₁₆H₁₈O₉	8.604	354.095	-	2.903	0.005	1.635	Down
26	Muramic acid	C₉H₁₇NO₇	0.990	269.111	-	2.870	0.026	1.541	Down
27	D-Arabinonate	C₅H₁₀O₆	0.996	166.048	+	2.842	0.000	1.390	Down
28	N-alpha-Acetylarginine	C₈H₁₆N₄O₃	1.541	216.123	-	2.814	0.023	2.136	Down
29	N-D-Glucosylarylamine	C₁₂H₁₇NO₅	1.536	255.111	+	2.812	0.024	1.153	Down
30	Lotaustralin	C₁₁H₁₉NO₆	1.532	261.121	+	2.6153	2.202	1.762	Down
31	Coniferin	C₁₆H₂₂O₈	9.841	342.131	+	2.553	0.004	3.534	Down
32	Rosmarinine	C₁₈H₂₇NO₆	10.127	353.184	-	2.453	0.014	-2.822	Up
33	Ascorbyl stearate	C₂₄H₄₂O₇	25.375	442.293	-	2.261	0.021	1.825	Down
34	2-Isopropylmalic acid	C₇H₁₂O₅	8.035	176.068	-	2.166	0.024	4.105	Down
35	Phloionolic acid	C₁₈H₃₆O₅	21.305	332.256	-	2.160	0.044	2.837	Down
36	2-Oxovalericacid	C₅H₈O₃	8.025	116.047	-	2.160	0.024	4.089	Down
37	N-linoleoyl-4-aminobutyric acid	C₂₂H₃₉NO₃	25.876	365.293	+	2.137	0.002	3.177	Down
38	1-Hydroxycholic acid	C₂₄H₄₀O₆	25.374	424.282	-	2.116	0.016	1.849	Down
39	1-alpha-D-Galactosyl-myo-inositol	C₁₂H₂₂O₁₁	1.541	342.116	-	2.097	0.015	2.879	Down
40	Picrotoxinin	C₁₅H₁₆O₆	10.023	292.094	+	1.9508	0.009	1.992	Down
41	Alloxydim	C₁₇H₂₅NO₅	9.249	323.173	+	1.887	0.015	-3.124	Up
42	9,12,13-Trihydroxy 10,15-octadecadienoic acid	C₁₈H₃₂O₅	21.033	328.225	+	1.806	0.010	1.968	Down
43	Miglitol	C₈H₁₇NO₅	0.979	207.111	-	1.750	0.035	1.627	Down
44	1,4-D-Xylobiose	C₁₀H₁₈O₉	1.514	282.095	+	1.697	0.011	1.126	Down
45	L-Lathyrine	C₇H₁₀N₄O₂	1.030	182.080	+	1.678	0.029	1.770	Down
46	Biphenyl	C₁₂H₁₀	13.417	154.078	-	1.661	0.015	2.407	Down
47	Linoleoyl ethanolamide	C₂₀H₃₇NO₂	25.777	323.282	-	1.574	0.001	2.002	Down
48	Adenine	C₅H₅N₅	1.085	135.055	+	1.574	0.030	1.538	Down
49	3-Methylcrotonylglycine	C₇H₁₁NO₃	1.074	157.074	+	1.561	0.011	2.324	Down
50	Uridine	C₉H₁₂N₂O₆	2.040	244.069	-	1.536	0.013	1.325	Down
51	Methyl cinnamate	C₁₀H₁₀O₂	9.754	162.068	+	1.516	0.011	2.860	Down
52	Secologanin	C₁₇H₂₄O₁₀	8.156	388.137	+	1.404	0.008	3.179	Down
53	Methyldopa	C₁₀H₁₃NO₄	9.606	211.084	-	1.383	0.005	1.302	Down
54	Sinapoylcholine	C₁₆H₂₃NO₅	7.867	309.158	+	1.341	0.042	-1.955	Up
55	Palmitoylglucuronide	C₂₂H₄₂O₇	25.989	418.293	-	1.315	0.004	1.078	Down
56	1,3-Dihydroxy-1-(7-methoxy-2-oxo-2H-chromen-6-yl)-3-methylbutan-2-yl 3-methylbutanoate	C₂₀H₂₆O₇	12.982	400.150	-	1.308	0.020	1.606	Down
57	cis-Aconitic acid	C₆H₆O₆	1.639	174.016	-	1.283	0.004	2.109	Down
58	Cortol	C₂₁H₃₆O₅	23.948	368.256	+	1.258	0.018	1.149	Down
59	AtractylenolideI	C₁₅H₁₈O₂	23.917	230.131	-	1.241	0.023	-2.809	Up
60	Dubinidine	C₁₅H₁₇NO₄	8.556	275.116	-	1.234	0.036	3.356	Down
61	9-Oxo-ODE	C₁₈H₃₀O₃	22.554	294.220	+	1.234	0.001	1.700	Down
62	Amylose	C₁₄H₂₆O₁₁	2.828	370.148	-	1.222	0.022	2.169	Down
63	3,4-Dihydroxymandelaldehyde	C₈H₈O₄	1.055	168.042	+	1.212	0.028	1.008	Down
64	N-Acetyl-D-sphingosine	C₂₀H₃₉NO₃	26.458	341.293	-	1.204	0.003	1.975	Down
65	(E)-Glutaconate	C₅H₆O₄	1.626	130.027	-	1.201	0.001	1.302	Down
66	Palmitoleic Acid	C₁₆H₃₀O₂	20.864	276.209	+	1.186	0.012	1.165	Down
67	Carbofuran	C₁₂H₁₅NO₃	6.271	221.105	-	1.161	0.004	2.209	Down
68	7-Hydroxycoumarine	C₉H₆O₃	8.605	162.032	-	1.155	0.005	1.494	Down
69	(+/-)12(13)-DiHOME	C₁₈H₃₄O₄	21.325	296.235	+	1.124	0.049	2.456	Down
70	Fenipentol	C₁₁H₁₆O	25.444	164.12	+	1.121	0.032	-3.960	Up
71	Linoleic acid	C₁₈H₃₂O₂	25.380	280.240	-	1.119	0.040	1.569	Down
72	5-Methyldeoxycytidine	C₁₀H₁₅N₃O₄	4.551	241.106	-	1.108	0.030	1.150	Down

基于超高效液相色谱串联高分辨质谱技术的不同产地党参的非靶向代谢组学研究

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牛媛婧 , 温嘉琪 , 姬惠鑫 , 李建宽 , 高敏 , 白云娥 ^* , 高建平 ^*

药学学报 | 研究论文 2023,58(7): 1842-1850

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药学学报 | 研究论文 2023, 58(7): 1842-1850

基于超高效液相色谱串联高分辨质谱技术的不同产地党参的非靶向代谢组学研究

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牛媛婧, 温嘉琪, 姬惠鑫, 李建宽, 高敏, 白云娥^*, 高建平^*

作者信息

山西医科大学药学院, 山西太原 030001

通讯作者:

*白云娥, Tel: 86-351-3985190, E-mail: baiyune@hotmail.com;

高建平, Tel: 86-351-3985244, E-mail: jpgao123@163.com

Study on untargeted metabolomics of Codonopsis pilosula from different producing areas based on ultra-performance liquid chromatography tandem high resolution mass spectrometry

Yuan-jing NIU, Jia-qi WEN, Hui-xin JI, Jian-kuan LI, Min GAO, Yun-e BAI^*, Jian-ping GAO^*

Affiliations

School of Pharmaceutical Science, Shanxi Medical University, Taiyuan 030001, China

出版时间: 2023-07-12 doi: 10.16438/j.0513-4870.2022-1238

文章导航

摘要

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潞党参为中药党参的传统道地药材, 主产于山西上党(今长治) 地区, 与其同基原的白条党主产于甘肃地区。党参含有苯丙素类、聚炔类、生物碱类、萜类、脂肪酸类、黄酮类等多种小分子化学成分, 产地对其化学成分的影响目前尚未发现系统报道。本研究基于四级杆-静电场轨道肼高分辨质谱联用(UPLC-Q-Exactive) 技术, 通过非靶向代谢组学方法分析不同产地党参之间的差异代谢物。采用主成分分析(PCA)、正交偏最小二乘判别分析(OPLS-DA) 的方法, 结合在线和本地数据库(Thermo mzcloud) 进行化学成分鉴定, 根据数据库(HMDB、PubChem、Chemspider、KEGG) 中的信息检索, 进一步筛选差异代谢物并分析其代谢通路。研究筛选得到72种差异代谢物, 产于山西省的潞党参相对甘肃省的白条党含量增加的差异代谢物有15种, 含量降低的差异代谢物有57种。KEGG富集分析到排名前30的代谢通路, 富集程度最高的代谢通路为苯丙素生物合成, 提示苯丙素生物合成途径以及相关中间代谢物可以作为区分潞党参和不同产地党参的特征。本研究为分析产地对党参化学成分的影响及合理评价党参质量提供了依据, 也为阐述潞党参的道地性提供新思路。

关键词

非靶向代谢组学 / 党参 / 小分子化学成分 / 苯丙素化合物

Abstract

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Lu Dangshen, a traditional authentic medicinal material of Codonopsis Radix is mainly produced in Shangdang (Changzhi) area of Shanxi Province. Baitiao Dangshen is mainly produced in Gansu Province. Codonopsis Radix contains many kinds of components such as phenylpropanoids, polyalkynes, alkaloids, terpenes, fatty acids, flavonoids, and so on. At present, the effect of producing areas on its chemical compositions has not been systematically studied. This study analyzed the differences of metabolites among Codonopsis pilosula from different producing areas by UPLC-HRMS. PCA, OPLS-DA coupled with Thermo mzcloud online and local databases were used to compare the overall differences of metabolites among Codonopsis pilosula from different producing areas, and the chemical constituents were identified to further screen and find out the different metabolites and analyze the metabolic pathways by information retrieval in HMDB, PubChem, Chemspider and KEGG databases. The results showed that 72 differential metabolites were identified in this study. There were 15 kinds of up-regulated and 57 kinds of down-regulated metabolites of Lu Dangshen compared with Baitiao Dangshen. The top 30 metabolic pathways were analyzed by KEGG enrichment, and the most important metabolic pathways were phenylpropanoid biosynthesis, which was demonstrated that phenylpropanoid biosynthesis pathway and related intermediate metabolites could be used as the characteristics of distinguishing Lu Dangshen from different habitats of Codonopsis pilosula. The present study provided a basis for analyzing the influence of producing areas on the chemical components of Codonopsis pilosula and reasonably evaluating the quality of Codonopsis Radix, and also provided a new idea for expounding the authenticity of Lu Dangshen.

Key words

untargeted metabolomics / Codonopsis pilosula (Franch.) Nannf / small molecular chemical component / phenylpropanoid

引用本文

牛媛婧, 温嘉琪, 姬惠鑫, 李建宽, 高敏, 白云娥, 高建平. 基于超高效液相色谱串联高分辨质谱技术的不同产地党参的非靶向代谢组学研究. 药学学报, 2023 , 58 (7) : 1842 -1850 . DOI: 10.16438/j.0513-4870.2022-1238

Yuan-jing NIU, Jia-qi WEN, Hui-xin JI, Jian-kuan LI, Min GAO, Yun-e BAI, Jian-ping GAO. Study on untargeted metabolomics of Codonopsis pilosula from different producing areas based on ultra-performance liquid chromatography tandem high resolution mass spectrometry[J]. Acta Pharmaceutica Sinica, 2023 , 58 (7) : 1842 -1850 . DOI: 10.16438/j.0513-4870.2022-1238

正文

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党参为桔梗科植物党参Codonopsis pilosula (Franch.) Nannf.、素花党参Codonopsis pilosula Nannf var.modesta (Nannf.) L. T. Shen或川党参Codonopsis tangshen Oliv.的干燥根^[1], 具有补脾益肺、生津养血的传统功效及调节肠胃运动^[2]、增强免疫、增强造血和抗炎镇痛^[3]等现代药理作用, 主要分布在山西省、甘肃省、湖北省、四川省等地^[4]。党参含有糖类^[5]、炔类^[6]、苯丙素类^[7]、生物碱及含氮类^[8]、萜类^[9]、脂肪酸类^[10]等化学成分。《本草从新》^[11]记载: “参须上党者佳”, 这说明山西上党地区(今长治) 为党参的道地产区。潞党参是业界公认的优质药材, 基原为党参Codonopsis pilosula (Franch.) Nannf., 同时, 产自甘肃省的白条党在党参药材市场中有较大份额, 两者基原相同, 但由于生长环境、气候条件、栽培加工方式等因素的影响, 前期的研究结果不太一致。Tang等^[12]利用中药指纹图谱技术分析了18批不同商品规格的党参, 表明山西省潞党参和甘肃省白条党的差异不大, 所含化学成分基本相同; 而Guan等^[13]分析54批党参并建立潞党参的指纹图谱, 发现潞党参指纹图谱相似度与白条党差异较大, 且苍术内酯Ⅲ和党参苷Ⅰ含量均明显高于白条党, 党参炔苷的含量高于白条党, 从这些成分看潞党参与白条党存在明显差异。然而, 对于两者的差异性化学成分至今未见系统研究, 严重影响了党参的质量评价。

中药的质量评价从优形、优质两个角度来研究, 内在品质影响外观性状。中药指纹图谱技术只能从宏观角度对不同中药的化学成分进行系统研究, 关注的是样本之间的相似性, 缺乏对差异性方面的研究。非靶向代谢组学技术是评价中药质量的新技术之一, 它能对样品中所有相对分子质量在1 000以内的小分子代谢物同时进行定性和定量分析, 同时关注样本之间的相似性、聚类情况及差异性^[14]。它通过液质联用、气质联用、核磁共振波谱等多项技术, 从整体上客观全面地分析中药所含有的化学成分, 结合多元统计方法分析植物体内初级代谢物和次级代谢物并筛选差异代谢物, 利用生物信息学解释说明其可能的代谢机制, 为后续酶催化反应的解释、生物合成途径的分析等提供依据。代谢组学技术已被应用于白术^[15]、沉香^[16]、何首乌^[17]、半枫荷^[18]等的研究, 如产地、炮制方法、栽培环境等对其质量的影响。但文献只有对同一种商品规格^[3]、不同药用部位^[19]的党参的相关报道, 尚未见对多产地党参差异化学成分的系统性比较研究。

本研究以产自山西省的潞党参和甘肃省渭源县的白条党为实验材料, 基于UPLC-Q-Exactive的非靶向代谢组学技术, 分析研究产地对党参化学成分的影响, 利用PCA、OPLS-DA、热图分析等统计方法, 筛选出潞党参与白条党的差异代谢物, 并分析其代谢通路, 为解释产地对党参化学成分的影响提供理论依据, 也为不同规格党参的质量评价及潞党参的道地性研究提供可借鉴的依据。

材料与方法

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药材本研究所用实验材料为产于山西省的潞党参和产于甘肃省的白条党, 共收集29批党参(表 1)。实验材料经山西医科大学白云娥教授鉴定为桔梗科植物党参C. pilosula的干燥根。存于山西医科大学生药学研究室。

仪器与试剂 质谱仪(德国Thermo公司); 超高效液相色谱仪(美国Waters公司); DS-3510DTH型超声波提取仪(上海生析超声仪器有限公司); CP213型电子天平(常州奥豪斯仪器有限公司); GZX-9070MBE型电热鼓风干燥箱(上海博迅实业有限公司医疗设备厂); 甲醇、乙腈、甲酸(均为色谱纯, 天津市科密欧化学试剂有限公司)。

色谱检测条件 UPLC流动相: 乙腈(A)-0.1%甲酸水(B); 色谱柱: ACQUITY UPLC HSST3柱(150 mm × 2.1 mm, 1.7 μm); 梯度洗脱条件: 0 min (2% B), 0~2 min (2% B), 2~5 min (2%~10% B), 5~8 min (10%~15% B), 8~10 min (15%~20% B), 10~18 min (20%~35% B), 18~20 min (35%~60% B), 20~26 min (60%~95% B), 26~27 min (95% B), 27~27.5 min (95%~2% B), 27.5~30 min (2% B); DAD检测器扫描范围为190~400 nm; 柱温40 ± 5 ℃; 流速0.3 mL·min^-1; 进样量5 μL。

质谱检测条件 电喷雾离子源(ESI), Full Scan/dd-MS2正负离子全扫描方式, 采集范围为m/z 200~2 000, 质量分辨率70 000; 喷雾电压3.5 kV; 毛细管温度320 ℃; 加热器温度300 ℃; 鞘气流速45 psi, 辅助气流15 psi。

供试品溶液的制备 党参药材烘干后粉碎。精密称取党参粉末(过4号筛) 约6 g, 置于具塞锥形瓶中。精密加入甲醇25 mL, 超声提取30 min, 静置至室温, 过滤取上清液, 即得。置于4 ℃冰箱中保存。过0.22 μm的微孔滤膜后进样。另取上述测试样品各10 μL混合, 制备质量控制(QC) 样品, 用于检测仪器的稳定性。

数据处理与统计分析 将所得到的29批党参药材的总离子流图导入Compound Discoverer 3.1和Xcalibur 3.0软件中进行峰提取、峰匹配、峰鉴定与峰归属等分析, 利用Thermo在线和本地数据库进行物质鉴定; 将归一化后的数据导入到SIMCA-P 14.1软件进行PCA分析和OPLS-DA分析; 利用OPLS-DA和t检验、单因素方差分析相结合的方法筛选差异倍数值(|FC|) ≥ 1、P < 0.05且OPLS-DA模型第一主成分的变量投影重要度(VIP) > 1的代谢物; 利用生物学数据库HMDB (http://www.hmdb.ca)、Pubchem (https://pubchem.ncbi.nlm.nih.gov/)、Chemspider (http://www.chemspider.com/) 和KEGG (http://www.genome.jp) 进行代谢物鉴定及代谢通路分析。

结果与讨论

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1 党参化学成分指认

通过比较产于山西省的潞党参(LD) 和产于甘肃省的党参(GS) 的UPLC-MS/MS总离子流图(图 1), 发现样本化学成分种类基本相似, 但含量有所差异。共指认到5 046个离子峰, 鉴定得到117种化合物。

2 多元统计分析

2.1 主成分分析(PCA)

由正负离子模式下的PCA得分图(图 2) 可知, LD组和GS组较为分散且分布于不同区域, 说明LD组和GS组差异较大。而且产于山西省长治市平顺县(PS4-6) 和壶关县(HG6-8) 的样本与其他组的潞党参相距一定距离, 与甘肃省的样本(GS1-6) 距离更远。LD vs GS样本中, PC1和PC2的贡献率分别为28.4%和21.2%, 样本之间PCA得分差异显著且位于95%置信区间内。由此可见, 产于山西省的潞党参与产于甘肃省的党参所含化学成分具有明显差异。

2.2 正交偏最小二乘法判别分析(OPLS-DA)

为了进一步明确两组间的差异性成分, 消除无关变量的影响, 采用OPLS-DA的方法对实验结果进一步分析。结果见图 3。在OPLS-DA得分图(图 3A) 中, R²X = 0.981, R²Y = 1, Q² = 0.947, 表明该模型建立较好, 且样本区分非常显著, 样本基本全部处于95%置信区间内; 在OPLS-DA模型验证图(图 3B) 中, R² = 0.733, Q² = -0.608, 表明该模型拟合有效。

3 差异代谢物筛选与分析

3.1 差异代谢物筛选

选择|FC| ≥ 1、P < 0.05、VIP > 1的差异代谢物, 绘制差异表达火山图(图 4)。图 4中每一个点代表一个变量, 横坐标代表该组对比各物质的FC值, 纵坐标表示t检验的P值, 散点大小代表OPLS-DA模型的VIP值, 散点越大VIP值越大, 筛选得到的差异表达变量越可靠。最终, 筛选得到LD组相对GS组的差异变量共有263种, 上调差异表达变量有59种, 下调差异表达变量有204种。

3.2 差异代谢物的聚类热图分析

为进一步了解LD组和GS组代谢物的变化规律, 对两组样本的263种显著性差异变量归一化处理, 并绘制聚类热图, 如图 5所示。红色部分表示上调差异表达变量, 紫色部分表示下调差异表达变量, 且颜色越深的部分表明差异越显著。其中, LD组相对GS组有59种差异变量上调, 即相对含量增加, 占全部差异变量的22.43%, 包括α-D-吡喃葡萄糖基-2-O-(2-甲基丁酰基)-α-D-葡萄糖苷、苍术内酯Ⅰ、10-亚硝酸酯、13S-羟基-9Z, 11E, 15Z十八碳三烯酸、L-谷氨酸、芥子胆碱等; 有204种差异变量下调, 即相对含量减少, 占全部差异变量的77.57%, 包括codonopsinol B、codonopsinol A、棉子糖、9,10-二羟基-12Z-十八烯酸、9-氧代-10E, 12Z十八碳二烯酸、亚油酸、7-羟基香豆素等。

将263种差异变量按照结构进行分类, 得到苯丙素类55个、羧酸类10个、萜类24个、三萜类4个、醚类2个、脂肪酸类25个、糖苷类38个、生物碱类40个、酯类17个、氨基酸类28个、黄酮类5个、其他类15个, 各类化合物的占比情况分别为苯丙素类21%、羧酸类4%、萜类9%、三萜类2%、醚类1%、脂肪酸类10%、糖苷类14%、生物碱类15%、酯类6%、氨基酸类11%、黄酮类2%、其他类5%。

将263种差异变量结合前期根据离子峰鉴定得到的117种化合物进行比对, 最终筛选得到72种差异代谢物。按照VIP值从大到小对72种差异代谢物进行排序, 见表 2。

4 代谢通路分析

4.1 KEGG通路富集

通过KEGG数据库对LD组和GS组样本的263种差异变量进行通路富集分析, 富集到排名前30的代谢通路, 如图 6所示。图中越大越红的圆点为差异代谢物主要的代谢通路, 分别为苯丙素生物合成、乙醛酸及二羧酸代谢、谷胱甘肽代谢、半乳糖代谢和精氨酸和脯氨酸代谢; 还有富集较显著的且包含差异代谢物数量较多的代谢通路为氨基酰基-tRNA生物合成; 富集程度最显著的代谢通路为嘌呤代谢、嘧啶代谢、半胱氨酸和蛋氨酸代谢、黄酮类生物合成和脂肪酸生物合成; 富集程度最大的代谢通路为亚油酸代谢和吲哚生物碱生物合成。

4.2 KEGG通路注释

本研究发现苯丙素生物合成是最主要的代谢通路。苯丙素类是由苯丙氨酸的碳骨架衍生而来的一组化合物, 参与植物防御、结构支持和生存等^[20]。其中, 木质素类化合物是苯丙素类化合物的一种, 它是简单酚类的醇衍生物(如香豆醇、松柏醇、芥子醇、5-羟基阿魏醇) 的聚合物, 其生物合成是多途径共同作用的结果, 经氧化聚合的单体生成相应的三种木质素: 对-羟基苯基木质素、紫丁香基木质素和愈创木基木质素^[21], 紫丁香基木质素是党参中最主要的木质素成分, 比如紫丁香苷、丁香脂素、党参苷Ⅰ等。本课题组前期研究结果表明, 党参苷Ⅰ在潞党参中的含量显著高于白条党、纹党、刀党^[22]。芥子醇是紫丁香基木质素生物合成的一个中间产物, 本研究结果表明, LD相对GS的芥子胆碱含量显著上调, 而芥子胆碱含量上调会促进芥子酸升高; LD相对GS的松柏苷含量下调, 促进松柏醇下调, 在植物木质素合成酶和儿茶酚-O-甲基转移酶的作用下, 会影响终产物(紫丁香苷) 的含量。可见, 这两条通路共同为紫丁香苷等木质素类化合物的合成发挥作用, 也进一步说明木质素的生物合成是多途径协同发挥作用。

芥子胆碱的生物合成过程由酶催化反应得到, LD组的党参中芥子胆碱含量升高, 会进一步水解释放胆碱形成1-O-芥子酰基-β-D-葡萄糖, 而芥子酸通过酶SGT催化芥子醇葡萄糖的合成, 从而促进芥子胆碱的合成。酶SGT是UDP-糖基转移酶(UGTs) 的家族分支之一。本课题组前期研究表明, 党参糖基转移酶在UGT分支中数量最多, 且潞党参相关基因的表达均显著高于白条党^[23], 这与本研究结果一致, 进一步说明苯丙素类化合物可以作为区分产于山西省的潞党参和产于甘肃省的白条党的特征。

小结

收起

潞党参与白条党的基原均为党参, 二者产地不同。前者产于山西省长治市和晋城市, 后者产于甘肃省定西市渭源县。前者的平均海拔为1 100 m, 位于北纬N: 36°08′34.63″, 东经E: 113°26′42.77″, 年平均低温为4 ℃, 平均高温为17 ℃; 后者渭源县的平均海拔为2 080 m, 位于北纬N: 35°8′11.364″, 东经E: 104°12′51.66″, 年平均低温为1 ℃, 平均高温为13 ℃。已有研究结果表明, 经纬度和海拔对植物的生长均有影响且各不相同, 纬度主要是通过光照、温度等来影响化学成分的积累^[24], 海拔主要是通过影响温度、降雨量等影响植物生长。另外, 土壤中的无机元素、微量元素等也有可能会对不同产地党参的化学成分有影响^[25]。总之, 地区海拔高度、经纬度、温度、光照、降雨量、土壤条件等环境因子均对党参的化学成分有影响。

苯丙素类化合物作为次级代谢产物, 不参与光合作用、呼吸作用、蛋白质与核酸合成等基础细胞过程, 但实际上, 苯丙素生物合成途径对植物来说是不可或缺的一环^[20]。本实验结果显示, 在潞党参与白条党的263种差异变量中, 苯丙素类化合物共有55种, 如芥子胆碱、松柏苷、紫丁香苷等。党参中含有多种苯丙素类化合物, 如党参苷Ⅰ~Ⅵ、紫丁香苷等。韩国学者^[26]利用高效液相紫外检测法建立38批党参的指纹图谱, 确定了党参苷Ⅰ、党参炔醇和党参炔苷可以作为党参质量评价的标志物。日本学者^[27]研究发现, 党参苷Ⅰ和两种生物碱类化合物可以作为区别川党参、素花党参与党参的化学标志物。Hu等^[28]以紫丁香苷为指标化合物区分纹党与白条党。Gao等^[3]也发现色氨酸、紫丁香苷、党参苷Ⅰ、codonopyrrolidium A、党参炔苷宁和两个未知化合物可能是党参造血免疫功能的潜在生物活性标志物, 可推荐作为指标化合物。由此可见, 紫丁香苷和党参苷Ⅰ都可以作为党参的化学标志物来评价党参质量, 而且紫丁香苷还对结肠炎^[29]、急性肺损伤^[30]等疾病具有保护作用。以上研究进一步说明, 苯丙素生物合成途径以及相关中间代谢物可以作为潞党参区别不同产区党参的重要特征。

道地药材为传统中医药的精髓, 近年来也是研究的热点之一。党参主产于山西省、甘肃省、四川省等地, 本研究结果表明同基原的潞党参与白条党因产地的不同, 初级代谢产物和次级代谢产物存在差异, 其生物合成过程与生态因子等环境因素密切相关。Yang等^[31]建立10批不同基原、不同地理分布引种到同一种植基地党参的指纹图谱, 说明环境变化对党参化学成分有影响。Gu等^[32]也将10批不同产地党参引种至同一中药材种植基地后, 苍术内酯Ⅲ和党参炔苷含量与原种植基地相比有所提高, 也说明党参化学成分很容易受到生长环境的影响。然而生态环境对于药材的道地性研究目前仅局限于几个化学成分, 而中药的药效物质基础多为活性化学成分群, 因此需要从整体上阐释中药道地性。

植物代谢组学技术是用于评价中药质量的新方法之一, 在中药活性成分群的鉴定方面发挥巨大优势, 与传统中药质量评价方法相比, 具有灵敏度高、准确度高、分析效率快等优点。另外, 它还可与分子生药学、生物遗传学等技术相结合, 进一步分析植物次级代谢产物, 解释传统中药的道地性。植物的次级代谢过程是复杂的, 需要关注次级代谢产物在植物与生物和非生物环境的相互作用。苯丙素类生物合成是多途径共同作用的结果, 其中MYB转录因子在苯丙素生物合成途径的调控中也发挥作用。在拟南芥中发现了一系列R2R3-MYB转录因子作为调节蛋白广泛参与植物苯丙素类次生代谢合成途径的调控^[33], MYB家族基因对木质素类的生物合成具有阻遏、催化等多重作用^[34]。本课题组前期对转录因子CpMYB14对党参多糖调控机制^[35]进行探索, 基于本研究中代谢途径的结果显示, 后期将以MYB家族其他基因对党参中苯丙素类化合物的调控机制进行研究。

代谢组学技术已经用于分析研究基原、产地、商品规格、生长年限等因素对中药黄芪、远志、黄芩等^[36]质量的影响。本研究采用UPLC-Q-Exactive非靶向代谢组学技术, 从PCA、OPLS-DA、差异代谢物的表达及分类、差异代谢通路KEGG富集注释等方面进行了系统分析, 探讨产地对党参小分子化学成分的影响, 为评价不同规格党参质量提供新思路, 也为后续潞党参道地性的深入研究奠定基础。

作者贡献: 牛媛婧主要负责进行液质联用实验、数据分析以及论文撰写; 温嘉琪和姬惠鑫主要负责样品信息的统计; 李建宽、高敏、白云娥、高建平主要负责整篇论文的选题、设计、修改以及提供基金支持。

利益冲突: 所有作者均声明没有利益冲突。

基金

收起

国家重点研发计划项目(2018YFC1706304)
国家重点研发计划项目(2019YFC1710800)
山西省高等学校科技创新计划项目(2021L235)
国家自然基金区域联合基金重点项目(U22A20375)
山西省重点研发计划(2022-2023年度中医药科技创新工程项目)
山西省中医药管理局科研项目(2022ZYYZ024)

参考文献

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文献

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2023年第58卷第7期

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doi: 10.16438/j.0513-4870.2022-1238

接收时间：2022-11-17
首发时间：2025-11-21
出版时间：2023-07-12

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作者

出版历史

收稿日期：2022-11-17
修回日期：2023-03-20

基金

国家重点研发计划项目(2018YFC1706304)

国家重点研发计划项目(2019YFC1710800)

山西省高等学校科技创新计划项目(2021L235)

国家自然基金区域联合基金重点项目(U22A20375)

山西省重点研发计划(2022-2023年度中医药科技创新工程项目)

山西省中医药管理局科研项目(2022ZYYZ024)

作者信息

山西医科大学药学院, 山西太原 030001

通讯作者:

*白云娥, Tel: 86-351-3985190, E-mail: baiyune@hotmail.com;

高建平, Tel: 86-351-3985244, E-mail: jpgao123@163.com

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https://castjournals.cast.org.cn/joweb/yxxb/CN/10.16438/j.0513-4870.2022-1238

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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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TxT

Number	Trade name	Sample	Geographical origin
1	Ludangshen (LD)	PS1	Pingshun, Changzhi, Shanxi
2		PS2	Pingshun, Changzhi, Shanxi
3		PS3	Pingshun, Changzhi, Shanxi
4		PS4	Pingshun, Changzhi, Shanxi
5		PS5	Pingshun, Changzhi, Shanxi
6		PS6	Pingshun, Changzhi, Shanxi
7		HG1	Huguan, Changzhi, Shanxi
8		HG2	Huguan, Changzhi, Shanxi
9		HG3	Huguan, Changzhi, Shanxi
10		HG4	Huguan, Changzhi, Shanxi
11		HG5	Huguan, Changzhi, Shanxi
12		HG6	Huguan, Changzhi, Shanxi
13		HG7	Huguan, Changzhi, Shanxi
14		HG8	Huguan, Changzhi, Shanxi
15		LC1	Lingchuan, Jincheng, Shanxi
16		LC2	Lingchuan, Jincheng, Shanxi
17		LC3	Lingchuan, Jincheng, Shanxi
18		LC4	Lingchuan, Jincheng, Shanxi
19		LC5	Lingchuan, Jincheng, Shanxi
20		LC6	Lingchuan, Jincheng, Shanxi
21		LC7	Lingchuan, Jincheng, Shanxi
22		LC8	Lingchuan, Jincheng, Shanxi
23		LC9	Lingchuan, Jincheng, Shanxi
24	Baitiaodang (GS)	GS1	Weiyuan, Dingxi, Gansu
25		GS2	Weiyuan, Dingxi, Gansu
26		GS3	Weiyuan, Dingxi, Gansu
27		GS4	Weiyuan, Dingxi, Gansu
28		GS5	Weiyuan, Dingxi, Gansu
29		GS6	Weiyuan, Dingxi, Gansu

Number

Trade name

Sample

Geographical origin

Ludangshen (LD)

PS1

Pingshun, Changzhi, Shanxi

PS2

Pingshun, Changzhi, Shanxi

PS3

Pingshun, Changzhi, Shanxi

PS4

Pingshun, Changzhi, Shanxi

PS5

Pingshun, Changzhi, Shanxi

PS6

Pingshun, Changzhi, Shanxi

HG1

Huguan, Changzhi, Shanxi

HG2

Huguan, Changzhi, Shanxi

HG3

Huguan, Changzhi, Shanxi

HG4

Huguan, Changzhi, Shanxi

HG5

Huguan, Changzhi, Shanxi

HG6

Huguan, Changzhi, Shanxi

HG7

Huguan, Changzhi, Shanxi

HG8

Huguan, Changzhi, Shanxi

LC1

Lingchuan, Jincheng, Shanxi

LC2

Lingchuan, Jincheng, Shanxi

LC3

Lingchuan, Jincheng, Shanxi

LC4

Lingchuan, Jincheng, Shanxi

LC5

Lingchuan, Jincheng, Shanxi

LC6

Lingchuan, Jincheng, Shanxi

LC7

Lingchuan, Jincheng, Shanxi

LC8

Lingchuan, Jincheng, Shanxi

LC9

Lingchuan, Jincheng, Shanxi

Baitiaodang (GS)

GS1

Weiyuan, Dingxi, Gansu

GS2

Weiyuan, Dingxi, Gansu

GS3

Weiyuan, Dingxi, Gansu

GS4

Weiyuan, Dingxi, Gansu

GS5

Weiyuan, Dingxi, Gansu

GS6

Weiyuan, Dingxi, Gansu

Peak No.	Metabolite	Formula	t_R/min	m/z	Ion	VIP	P	Log₂FC	Regulated
1	Dipivefrin	C₁₉H₂₉NO₅	14.367	351.205	+	12.450	0.028	-1.986	Up
2	1-Linoleoylglycerophosphocholine	C₂₆H₅₀NO₇P	23.701	519.333	+	10.167	0.016	1.587	Down
3	Proline	C₅H₉NO₂	1.039	115.064	-	8.709	0.008	2.138	Down
4	1-Palmitoylglycerophosphocholine	C₂₄H₅₀NO₇P	24.151	495.333	+	8.708	0.002	1.571	Down
5	Codonopsinol B	C₁₃H₁₉NO₄	5.769	253.131	+	6.774	0.013	1.466	Down
6	Propanidid	C₁₈H₂₇NO₅	12.224	337.189	-	6.401	0.001	-2.165	Up
7	D-Raffinose	C₁₈H₃₂O₁₆	1.510	504.169	-	6.366	0.009	1.241	Down
8	Codonopsinol A	C₁₃H₁₉NO₅	2.633	269.126	+	6.059	0.008	1.392	Down
9	Ethopabate	C₁₂H₁₅NO₄	2.662	237.100	-	6.031	0.008	1.395	Down
10	L-Pyroglutamic acid	C₅H₇NO₃	0.974	129.042	-	5.881	0.001	-1.835	Up
11	9,11-Octadecadienoicacid	C₁₈H₃₂O₄	24.872	294.220	+	5.701	0.022	1.409	Down
12	Atractylenolide Ⅲ	C₁₅H₂₀O₃	22.520	248.141	-	5.580	0.017	-2.435	Up
13	Tangshenoside Ⅰ	C₂₉H₄₂O₁₈	11.347	678.633	+	4.728	0.024	-1.910	Up
14	L-Glutamic acid	C₅H₉NO₄	0.979	147.053	-	4.654	0.002	-1.134	Up
15	Afegostat	C₆H₁₃NO₃	1.098	147.090	-	4.258	0.001	-2.410	Up
16	Pipecolic acid	C₆H₁₁NO₂	1.102	129.079	+	4.246	0.001	-2.409	Up
17	D(-)-Amygdalin	C₂₈H₃₀N₈O₅	13.847	558.231	-	3.937	0.008	3.071	Down
18	Bis-D-fructose	C₁₂H₂₀O₁₀	1.537	324.105	-	3.910	0.002	3.001	Down
19	(+/-)9,10-Dihydroxy-12Z-octadecenoic acid	C₁₈H₃₄O₄	23.108	314.246	-	3.837	0.004	2.200	Down
20	Renardine	C₁₉H₂₇NO₆	10.681	365.184	-	3.805	0.007	-1.421	Up
21	Maltopentaose	C₃₀H₅₂O₂₆	1.595	850.257	-	3.266	0.017	1.532	Down
22	Maltotetraose	C₂₄H₄₂O₂₁	1.542	688.204	+	3.174	0.010	1.170	Down
23	Syringin	C₁₇H₂₄O₉	10.078	372.367	-	3.049	0.003	-2.521	Up
24	O-Succinyl-L-homoserine	C₈H₁₃NO₆	0.986	219.074	+	2.925	0.016	1.371	Down
25	Chlorogenic acid	C₁₆H₁₈O₉	8.604	354.095	-	2.903	0.005	1.635	Down
26	Muramic acid	C₉H₁₇NO₇	0.990	269.111	-	2.870	0.026	1.541	Down
27	D-Arabinonate	C₅H₁₀O₆	0.996	166.048	+	2.842	0.000	1.390	Down
28	N-alpha-Acetylarginine	C₈H₁₆N₄O₃	1.541	216.123	-	2.814	0.023	2.136	Down
29	N-D-Glucosylarylamine	C₁₂H₁₇NO₅	1.536	255.111	+	2.812	0.024	1.153	Down
30	Lotaustralin	C₁₁H₁₉NO₆	1.532	261.121	+	2.6153	2.202	1.762	Down
31	Coniferin	C₁₆H₂₂O₈	9.841	342.131	+	2.553	0.004	3.534	Down
32	Rosmarinine	C₁₈H₂₇NO₆	10.127	353.184	-	2.453	0.014	-2.822	Up
33	Ascorbyl stearate	C₂₄H₄₂O₇	25.375	442.293	-	2.261	0.021	1.825	Down
34	2-Isopropylmalic acid	C₇H₁₂O₅	8.035	176.068	-	2.166	0.024	4.105	Down
35	Phloionolic acid	C₁₈H₃₆O₅	21.305	332.256	-	2.160	0.044	2.837	Down
36	2-Oxovalericacid	C₅H₈O₃	8.025	116.047	-	2.160	0.024	4.089	Down
37	N-linoleoyl-4-aminobutyric acid	C₂₂H₃₉NO₃	25.876	365.293	+	2.137	0.002	3.177	Down
38	1-Hydroxycholic acid	C₂₄H₄₀O₆	25.374	424.282	-	2.116	0.016	1.849	Down
39	1-alpha-D-Galactosyl-myo-inositol	C₁₂H₂₂O₁₁	1.541	342.116	-	2.097	0.015	2.879	Down
40	Picrotoxinin	C₁₅H₁₆O₆	10.023	292.094	+	1.9508	0.009	1.992	Down
41	Alloxydim	C₁₇H₂₅NO₅	9.249	323.173	+	1.887	0.015	-3.124	Up
42	9,12,13-Trihydroxy 10,15-octadecadienoic acid	C₁₈H₃₂O₅	21.033	328.225	+	1.806	0.010	1.968	Down
43	Miglitol	C₈H₁₇NO₅	0.979	207.111	-	1.750	0.035	1.627	Down
44	1,4-D-Xylobiose	C₁₀H₁₈O₉	1.514	282.095	+	1.697	0.011	1.126	Down
45	L-Lathyrine	C₇H₁₀N₄O₂	1.030	182.080	+	1.678	0.029	1.770	Down
46	Biphenyl	C₁₂H₁₀	13.417	154.078	-	1.661	0.015	2.407	Down
47	Linoleoyl ethanolamide	C₂₀H₃₇NO₂	25.777	323.282	-	1.574	0.001	2.002	Down
48	Adenine	C₅H₅N₅	1.085	135.055	+	1.574	0.030	1.538	Down
49	3-Methylcrotonylglycine	C₇H₁₁NO₃	1.074	157.074	+	1.561	0.011	2.324	Down
50	Uridine	C₉H₁₂N₂O₆	2.040	244.069	-	1.536	0.013	1.325	Down
51	Methyl cinnamate	C₁₀H₁₀O₂	9.754	162.068	+	1.516	0.011	2.860	Down
52	Secologanin	C₁₇H₂₄O₁₀	8.156	388.137	+	1.404	0.008	3.179	Down
53	Methyldopa	C₁₀H₁₃NO₄	9.606	211.084	-	1.383	0.005	1.302	Down
54	Sinapoylcholine	C₁₆H₂₃NO₅	7.867	309.158	+	1.341	0.042	-1.955	Up
55	Palmitoylglucuronide	C₂₂H₄₂O₇	25.989	418.293	-	1.315	0.004	1.078	Down
56	1,3-Dihydroxy-1-(7-methoxy-2-oxo-2H-chromen-6-yl)-3-methylbutan-2-yl 3-methylbutanoate	C₂₀H₂₆O₇	12.982	400.150	-	1.308	0.020	1.606	Down
57	cis-Aconitic acid	C₆H₆O₆	1.639	174.016	-	1.283	0.004	2.109	Down
58	Cortol	C₂₁H₃₆O₅	23.948	368.256	+	1.258	0.018	1.149	Down
59	AtractylenolideI	C₁₅H₁₈O₂	23.917	230.131	-	1.241	0.023	-2.809	Up
60	Dubinidine	C₁₅H₁₇NO₄	8.556	275.116	-	1.234	0.036	3.356	Down
61	9-Oxo-ODE	C₁₈H₃₀O₃	22.554	294.220	+	1.234	0.001	1.700	Down
62	Amylose	C₁₄H₂₆O₁₁	2.828	370.148	-	1.222	0.022	2.169	Down
63	3,4-Dihydroxymandelaldehyde	C₈H₈O₄	1.055	168.042	+	1.212	0.028	1.008	Down
64	N-Acetyl-D-sphingosine	C₂₀H₃₉NO₃	26.458	341.293	-	1.204	0.003	1.975	Down
65	(E)-Glutaconate	C₅H₆O₄	1.626	130.027	-	1.201	0.001	1.302	Down
66	Palmitoleic Acid	C₁₆H₃₀O₂	20.864	276.209	+	1.186	0.012	1.165	Down
67	Carbofuran	C₁₂H₁₅NO₃	6.271	221.105	-	1.161	0.004	2.209	Down
68	7-Hydroxycoumarine	C₉H₆O₃	8.605	162.032	-	1.155	0.005	1.494	Down
69	(+/-)12(13)-DiHOME	C₁₈H₃₄O₄	21.325	296.235	+	1.124	0.049	2.456	Down
70	Fenipentol	C₁₁H₁₆O	25.444	164.12	+	1.121	0.032	-3.960	Up
71	Linoleic acid	C₁₈H₃₂O₂	25.380	280.240	-	1.119	0.040	1.569	Down
72	5-Methyldeoxycytidine	C₁₀H₁₅N₃O₄	4.551	241.106	-	1.108	0.030	1.150	Down

Peak No.

Metabolite

Formula

t_R/min

m/z

Ion

VIP

Log₂FC

Regulated

Dipivefrin

C₁₉H₂₉NO₅

14.367

351.205

12.450

0.028

-1.986

1-Linoleoylglycerophosphocholine

C₂₆H₅₀NO₇P

23.701

519.333

10.167

0.016

1.587

Down

Proline

C₅H₉NO₂

1.039

115.064

8.709

0.008

2.138

Down

1-Palmitoylglycerophosphocholine

C₂₄H₅₀NO₇P

24.151

495.333

8.708

0.002

1.571

Down

Codonopsinol B

C₁₃H₁₉NO₄

5.769

253.131

6.774

0.013

1.466

Down

Propanidid

C₁₈H₂₇NO₅

12.224

337.189

6.401

0.001

-2.165

D-Raffinose

C₁₈H₃₂O₁₆

1.510

504.169

6.366

0.009

1.241

Down

Codonopsinol A

C₁₃H₁₉NO₅

2.633

269.126

6.059

0.008

1.392

Down

Ethopabate

C₁₂H₁₅NO₄

2.662

237.100

6.031

0.008

1.395

Down

L-Pyroglutamic acid

C₅H₇NO₃

0.974

129.042

5.881

0.001

-1.835

9,11-Octadecadienoicacid

C₁₈H₃₂O₄

24.872

294.220

5.701

0.022

1.409

Down

Atractylenolide Ⅲ

C₁₅H₂₀O₃

22.520

248.141

5.580

0.017

-2.435

Tangshenoside Ⅰ

C₂₉H₄₂O₁₈

11.347

678.633

4.728

0.024

-1.910

L-Glutamic acid

C₅H₉NO₄

0.979

147.053

4.654

0.002

-1.134

Afegostat

C₆H₁₃NO₃

1.098

147.090

4.258

0.001

-2.410

Pipecolic acid

C₆H₁₁NO₂

1.102

129.079

4.246

0.001

-2.409

D(-)-Amygdalin

C₂₈H₃₀N₈O₅

13.847

558.231

3.937

0.008

3.071

Down

Bis-D-fructose

C₁₂H₂₀O₁₀

1.537

324.105

3.910

0.002

3.001

Down

(+/-)9,10-Dihydroxy-12Z-octadecenoic acid

C₁₈H₃₄O₄

23.108

314.246

3.837

0.004

2.200

Down

Renardine

C₁₉H₂₇NO₆

10.681

365.184

3.805

0.007

-1.421

Maltopentaose

C₃₀H₅₂O₂₆

1.595

850.257

3.266

0.017

1.532

Down

Maltotetraose

C₂₄H₄₂O₂₁

1.542

688.204

3.174

0.010

1.170

Down

Syringin

C₁₇H₂₄O₉

10.078

372.367

3.049

0.003

-2.521

O-Succinyl-L-homoserine

C₈H₁₃NO₆

0.986

219.074

2.925

0.016

1.371

Down

Chlorogenic acid

C₁₆H₁₈O₉

8.604

354.095

2.903

0.005

1.635

Down

Muramic acid

C₉H₁₇NO₇

0.990

269.111

2.870

0.026

1.541

Down

D-Arabinonate

C₅H₁₀O₆

0.996

166.048

2.842

0.000

1.390

Down

N-alpha-Acetylarginine

C₈H₁₆N₄O₃

1.541

216.123

2.814

0.023

2.136

Down

N-D-Glucosylarylamine

C₁₂H₁₇NO₅

1.536

255.111

2.812

0.024

1.153

Down

Lotaustralin

C₁₁H₁₉NO₆

1.532

261.121

2.6153

2.202

1.762

Down

Coniferin

C₁₆H₂₂O₈

9.841

342.131

2.553

0.004

3.534

Down

Rosmarinine

C₁₈H₂₇NO₆

10.127

353.184

2.453

0.014

-2.822

Ascorbyl stearate

C₂₄H₄₂O₇

25.375

442.293

2.261

0.021

1.825

Down

2-Isopropylmalic acid

C₇H₁₂O₅

8.035

176.068

2.166

0.024

4.105

Down

Phloionolic acid

C₁₈H₃₆O₅

21.305

332.256

2.160

0.044

2.837

Down

2-Oxovalericacid

C₅H₈O₃

8.025

116.047

2.160

0.024

4.089

Down

N-linoleoyl-4-aminobutyric acid

C₂₂H₃₉NO₃

25.876

365.293

2.137

0.002

3.177

Down

1-Hydroxycholic acid

C₂₄H₄₀O₆

25.374

424.282

2.116

0.016

1.849

Down

1-alpha-D-Galactosyl-myo-inositol

C₁₂H₂₂O₁₁

1.541

342.116

2.097

0.015

2.879

Down

Picrotoxinin

C₁₅H₁₆O₆

10.023

292.094

1.9508

0.009

1.992

Down

Alloxydim

C₁₇H₂₅NO₅

9.249

323.173

1.887

0.015

-3.124

9,12,13-Trihydroxy 10,15-octadecadienoic acid

C₁₈H₃₂O₅

21.033

328.225

1.806

0.010

1.968

Down

Miglitol

C₈H₁₇NO₅

0.979

207.111

1.750

0.035

1.627

Down

1,4-D-Xylobiose

C₁₀H₁₈O₉

1.514

282.095

1.697

0.011

1.126

Down

L-Lathyrine

C₇H₁₀N₄O₂

1.030

182.080

1.678

0.029

1.770

Down

Biphenyl

C₁₂H₁₀

13.417

154.078

1.661

0.015

2.407

Down

Linoleoyl ethanolamide

C₂₀H₃₇NO₂

25.777

323.282

1.574

0.001

2.002

Down

Adenine

C₅H₅N₅

1.085

135.055

1.574

0.030

1.538

Down

3-Methylcrotonylglycine

C₇H₁₁NO₃

1.074

157.074

1.561

0.011

2.324

Down

Uridine

C₉H₁₂N₂O₆

2.040

244.069

1.536

0.013

1.325

Down

Methyl cinnamate

C₁₀H₁₀O₂

9.754

162.068

1.516

0.011

2.860

Down

Secologanin

C₁₇H₂₄O₁₀

8.156

388.137

1.404

0.008

3.179

Down

Methyldopa

C₁₀H₁₃NO₄

9.606

211.084

1.383

0.005

1.302

Down

Sinapoylcholine

C₁₆H₂₃NO₅

7.867

309.158

1.341

0.042

-1.955

Palmitoylglucuronide

C₂₂H₄₂O₇

25.989

418.293

1.315

0.004

1.078

Down

1,3-Dihydroxy-1-(7-methoxy-2-oxo-2H-chromen-6-yl)-3-methylbutan-2-yl 3-methylbutanoate

C₂₀H₂₆O₇

12.982

400.150

1.308

0.020

1.606

Down

cis-Aconitic acid

C₆H₆O₆

1.639

174.016

1.283

0.004

2.109

Down

Cortol

C₂₁H₃₆O₅

23.948

368.256

1.258

0.018

1.149

Down

AtractylenolideI

C₁₅H₁₈O₂

23.917

230.131

1.241

0.023

-2.809

Dubinidine

C₁₅H₁₇NO₄

8.556

275.116

1.234

0.036

3.356

Down

9-Oxo-ODE

C₁₈H₃₀O₃

22.554

294.220

1.234

0.001

1.700

Down

Amylose

C₁₄H₂₆O₁₁

2.828

370.148

1.222

0.022

2.169

Down

3,4-Dihydroxymandelaldehyde

C₈H₈O₄

1.055

168.042

1.212

0.028

1.008

Down

N-Acetyl-D-sphingosine

C₂₀H₃₉NO₃

26.458

341.293

1.204

0.003

1.975

Down

(E)-Glutaconate

C₅H₆O₄

1.626

130.027

1.201

0.001

1.302

Down

Palmitoleic Acid

C₁₆H₃₀O₂

20.864

276.209

1.186

0.012

1.165

Down

Carbofuran

C₁₂H₁₅NO₃

6.271

221.105

1.161

0.004

2.209

Down

7-Hydroxycoumarine

C₉H₆O₃

8.605

162.032

1.155

0.005

1.494

Down

(+/-)12(13)-DiHOME

C₁₈H₃₄O₄

21.325

296.235

1.124

0.049

2.456

Down

Fenipentol

C₁₁H₁₆O

25.444

164.12

1.121

0.032

-3.960

Linoleic acid

C₁₈H₃₂O₂

25.380

280.240

1.119

0.040

1.569

Down

5-Methyldeoxycytidine

C₁₀H₁₅N₃O₄

4.551

241.106

1.108

0.030

1.150

Down