药学学报

No.	RT/min	Formula	Adduct	Mass	m/z	Score	Error/×10^-6	Compound	Category	Source
1	0.699 0	C₁₅H₁₈O₁₀	[M+Na]⁺	358.091 4	381.081 1	72.860 0	-3.890 0	Pyrimethacin	Coumarin	YC
2	1.030 0	C₁₅H₁₄O₄	[M+H]⁺	258.086 2	259.095 0	82.510 0	5.070 0	Rhamnosyl-3,3',5-trihydroxy-4'-methoxystilbene	Phenol	DH
3	1.071 0	C₅H₉NO₂	[M+H]⁺	115.063 8	116.071 0	86.500 0	-3.820 0	Proline	Amino acid	YC
4	2.461 0	C₉H₁₁NO₂	[M+H]⁺	165.079 7	166.087 0	84.630 0	-4.560 0	Phenylalanine	Amino acid	YC
5	2.932 0	C₁₂H₂₀O₂	[M+Na]⁺	196.146 1	219.135 2	86.710 0	1.500 0	Geranyl acetate	Volatile oil	YC
6	3.627 0	C₉H₆O₃	[M+H]⁺	162.031 7	163.039 1	87.280 0	-0.970 0	7-Hydroxy-coumarin	Coumarin	YC
7	3.817 0	C₆H₆O₃	[M+H]⁺	126.031 8	127.038 6	46.700 0	3.010 0	1,2,4-Benzenetriol	Phenol
8	3.892 0	C₁₀H₁₀O₄	[M+H]⁺	194.058 3	195.064 1	92.280 0	4.720 0	Ferulic acid	Phenylpropanoid	YC
9	3.892 0	C₂₁H₂₄O₁₁	[M+H]⁺	452.131 2	453.139 2	88.150 0	0.270 0	Catechin-5-O-β-D-glucopyranoside	Flavonoid	DH
10	4.131 0	C₉H₇NO	[M+H]⁺	145.052 4	146.059 7	79.520 0	3.240 0	4-Formylindole	Alkaloid	YC
11	4.471 0	C₃₀H₂₆O₁₂	[M+H]⁺	578.143 0	579.148 9	91.340 0	1.850 0	Proanthocyanidin B1	Flavonoid	DH
12	4.471 0	C₃₀H₂₆O₁₂	[M+H]⁺	578.143 0	579.148 9	91.340 0	1.850 0	Proanthocyanidin B2	Flavonoid	DH
13	4.471 0	C₃₀H₂₆O₁₂	[M+H]⁺	578.143 0	579.148 9	91.340 0	1.850 0	Proanthocyanidin B3	Flavonoid	DH
14	4.471 0	C₃₀H₂₆O₁₂	[M+H]⁺	578.143 0	579.148 9	91.340 0	1.850 0	Proanthocyanidin B4	Flavonoid	DH
15	4.471 0	C₃₀H₂₆O₁₂	[M+H]⁺	578.143 0	579.148 9	91.340 0	1.850 0	Proanthocyanidin B7	Flavonoid	DH
16	4.471 0	C₂₈H₂₈O₁₂	[M+Na]⁺	556.158 1	579.149 4	69.400 0	-3.410 0	Deoxyearth rhein-8-O-gallate	Phenol	DH
17	4.744 0	C₁₅H₁₄O₆	[M+H]⁺	290.079 0	291.086 9	97.620 0	-2.050 0	Catechins	Flavonoid	DH
18	4.876 0	C₉H₁₄O₄	[M+Na]⁺	186.089 2	209.081 3	70.670 0	-16.050 0	Azelaic acid	Fatty acid	YC
19	4.975 0	C₁₇H₂₂O	[M+Na]⁺	242.166 5	265.154 9	50.460 0	12.450 0	Dehydrofusarinol	Polyacetylene alcohol	YC
20	5.124 0	C₁₀H₁₆O	[M+H]⁺	152.120 8	153.128 2	74.050 0	-4.530 0	Arborone	Volatile oil	YC
21	5.190 0	C₂₇H₃₀O₁₅	[M+H]⁺	594.159 0	595.166 5	96.570 0	-0.820 0	Nicotilorin	Flavonoid	YC
22	5.232 0	C₁₀H₈O₃	[M+H]⁺	176.047 3	177.055 1	84.560 0	-2.450 0	7-Methoxy-coumarin	Coumarin	YC
23	5.232 0	C₁₁H₁₄O₅	[M+H]⁺	226.084 1	227.092 4	95.620 0	-3.860 0	Genipine	Terpenoid	ZZ
24	5.232 0	C₁₆H₂₄O₁₀	[M+H]⁺	376.139 1	377.146 8	78.580 0	-5.830 0	Mussaenosidic acid	Terpenoid	ZZ
25	5.323 0	C₂₇H₃₀O₁₆	[M+H]⁺	610.154 5	611.161 9	93.460 0	-1.900 0	Rutin	Flavonoid	YC
26	5.562 0	C₁₆H₂₆O₇	[M+H]⁺	330.168 2	331.175 1	77.220 0	-2.190 0	Epijasminoside A	Quinone	ZZ
27	5.653 0	C₈H₈O₂	[M+H]⁺	136.052 4	137.059 4	75.990 0	0.750 0	Anisaldehyde	Volatile oil	ZZ
28	5.926 0	C₁₂H₁₀O₅	[M+H]⁺	234.053 1	235.060 3	81.610 0	-1.000 0	2-Methyl-5-carboxymethyl-7-hydroxychromone	Quinone	DH
29	6.017 0	C₁₅H₁₀O₇	[M+H]⁺	302.044 0	303.051 1	74.000 0	-3.480 0	Quercetin	Flavonoid	YC
30	6.059 0	C₁₀H₈O₄	[M+H]⁺	192.042 3	193.050 1	84.460 0	-3.140 0	7-Methylchestnut baretin	Coumarin	YC
31	6.059 0	C₁₀H₈O₄	[M+H]⁺	192.042 3	193.050 1	84.460 0	-3.140 0	Scopolamine	Coumarin	YC
32	6.059 0	C₁₀H₈O₄	[M+H]⁺	192.042 3	193.050 1	84.460 0	-3.140 0	Isoscopolamine	Coumarin	YC
33	6.059 0	C₁₅H₁₀O₇	[M+H]⁺	302.042 7	303.051 0	76.000 0	-3.150 0	Mulberry pigment	Flavonoid	YC
34	6.059 0	C₂₁H₂₀O₁₂	[M+H]⁺	464.095 5	465.105 3	35.150 0	-5.470 0	Hypericin	Flavonoid	YC
35	6.208 0	C₂₁H₂₂O₉	[M+H]⁺	418.126 9	419.134 4	96.440 0	-1.200 0	Gardenia	Flavonoid	ZZ
36	6.208 0	C₁₉H₂₄O₉	[M+Na]⁺	396.145 5	419.134 4	60.190 0	-7.300 0	2-(2'-Hydroxypropyl)-5-methyl-7-hydroxychromotone-7-O-β-D-glucopyranoside	Phenol	DH
37	6.282 0	C₂₈H₃₂O₁₆	[M+H]⁺	624.168 8	625.175 8	72.530 0	0.510 0	Narcissine	Flavonoid	YC
38	6.373 0	C₁₃H₁₂O₄	[M+H]⁺	232.074 8	233.082 1	73.050 0	-4.790 0	2-Methyl-5-propanyl-7-hydroxychromoketone	Quinone	DH
39	6.398 0	C₁₃H₁₄O₄	[M+H]⁺	234.090 2	235.097 7	89.320 0	-5.530 0	2-(2'-Hydroxypropyl)-5-methyl-7-hydroxychromone	Phenol	DH
40	6.414 0	C₂₂H₂₂O₁₂	[M+H]⁺	478.111 1	479.118 8	98.430 0	-0.510 0	Isorhamnein-3-O-galactoside	Flavonoid	YC
41	6.414 0	C₂₂H₂₂O₁₂	[M+H]⁺	478.111 1	479.118 8	98.430 0	-0.510 0	Isorhamnein-3-O-glucoside	Flavonoid	YC
42	6.414 0	C₂₂H₂₂O₁₂	[M+H]⁺	478.111 1	479.118 2	80.180 0	0.170 0	2-O-Coumaryl-1-O-galloyl-β-D-glucose	Tannin	DH
43	6.497 0	C₁₆H₁₂O₇	[M+H]⁺	316.060 0	317.067 9	65.160 0	3.390 0	Capillarisin	Flavonoid	YC
44	6.671 0	C₁₁H₁₀O₄	[M+H]⁺	206.058 6	207.066 3	69.780 0	3.390 0	Inchen chromogenone	Coumarin	YC
45	6.985 0	C₁₁H₁₀O₃	[M+H]⁺	190.063 6	191.071 0	91.540 0	-3.760 0	2,5-Dimethyl-7-hydroxychromoton	Quinone	DH
46	7.696 0	C₂₀H₂₄O₉	[M+H]⁺	408.143 5	409.151 5	66.150 0	-5.090 0	Casidone-8-O-β-D-glucopyranoside	Phenol	DH
47	7.895 0	C₁₅H₁₀O₄	[M+H]⁺	254.059 2	255.066 5	79.670 0	-5.130 0	Chrysophanol	Quinone	DH
48	8.416 0	C₁₆H₁₂O₅	[M+H]⁺	284.069 6	285.077 4	75.400 0	-5.120 0	Physcion	Quinone	DH
49	15.190 0	C₁₈H₃₀O₂	[M+H]⁺	278.225 4	279.233 2	68.450 0	-4.540 0	Linolenic acid or its isomer	Fatty acid	YC
50	0.674 0	C₂₆H₃₀O₁₂	[M-H]^-	534.176 1	533.168 8	71.030 0	-4.350 0	p-Coumaryl genipin	Terpenoid	ZZ
51	1.601 0	C₁₃H₁₆O₁₀	[M-H]^-	332.075 4	331.068 8	67.170 0	-3.690 0	1-O-Gallic acyl fructose	Tannin	DH
52	1.601 0	C₇H₆O₅	[M-H]^-	170.021 5	169.015 0	96.620 0	-3.960 0	Gallic acid	Tannin	DH
53	3.429 0	C₁₉H₂₆O₁₅	[M-H]^-	494.125 5	493.118 9	96.660 0	1.920 0	1-O-Gallic acyl sucrose	Tannin	DH
54	3.577 0	C₁₆H₁₈O₉	[M-H]^-	354.095 1	355.102 5	97.520 0	-0.920 0	Chlorogenic acid	Phenylpropanoid	ZZ, YC
55	3.577 0	C₁₆H₁₈O₉	[M-H]^-	354.095 1	355.102 5	97.520 0	-0.920 0	Cryptochlorogenic acid	Phenylpropanoid	ZZ, YC
56	3.577 0	C₁₆H₁₈O₉	[M-H]^-	354.095 1	355.102 5	97.520 0	-0.920 0	Neochlorogenic acid	Phenylpropanoid	ZZ, YC
57	3.577 0	C₁₀H₁₂O₇	[M-H]^-	244.058 3	243.050 4	45.960 0	2.600 0	1-O-Gallic acylglycerol	Tannin	DH
58	3.875 0	C₁₆H₂₂O₁₀	[M-H]^-	373.113 0	374.121 3	72.000 0	1.410 0	Geniposide acid	Terpenoid	ZZ
59	3.875 0	C₁₆H₂₄O₁₁	[M-H]^-	392.132 2	391.125 0	92.130 0	-1.200 0	Mountain gardenoside	Terpenoid	ZZ
60	3.917 0	C₁₆H₂₂O₁₀	[M+Cl]^-	374.121 2	409.090 7	75.820 0	0.110 0	Gardenia new nucleoside	Terpenoid	ZZ
61	4.264 0	C₁₆H₂₆O₈	[M-H]^-	346.162 8	345.156 2	95.530 0	-1.030 0	Saffron picylate-β-D-glucopyranose	Terpenoid	ZZ
62	4.264 0	C₁₆H₂₆O₈	[M-H]^-	346.163 1	345.156 2	95.530 0	-1.030 0	Jasminoside B	Terpenoid	ZZ
63	4.727 0	C₃₁H₃₂O₁₆	[M+HCOO]^-	660.169 0	705.169 8	61.010 0	-4.250 0	3,5-Dicaffeyl-5-(3-hydroxy-3-methylglutaryl) quinic acid	Tannin	ZZ
64	4.727 0	C₃₁H₃₂O₁₆	[M+HCOO]^-	660.169 0	705.169 8	61.010 0	-4.250 0	3,4-Dio-cafeyl-5-O-(3-hydroxy-3-methyl) glutaryl quinic acid	Tannin	ZZ
65	4.727 0	C₃₁H₃₂O₁₆	[M+HCOO]^-	660.169 0	705.169 8	61.010 0	-4.250 0	3,5,6,4'-Tetrahydroxy 3',5'-dimethoxy flavone	Flavonoid	ZZ
66	4.727 0	C₃₁H₃₂O₁₆	[M+HCOO]^-	660.169 0	705.169 8	61.010 0	-4.250 0	3,5-Di-O-caffeyl-4-O-(3-hydroxy-3-methyl) alutaryl quinic acid	Tannin	ZZ
67	4.727 0	C₃₁H₃₂O₁₆	[M+HCOO]^-	660.169 0	705.169 8	61.010 0	-4.250 0	3-O-Ferulyl-4-O-(3-hydroxyl, 3-methyl) glutaryl-5-O-caffeyl quinic acid	Tannin	ZZ
68	4.744 0	C₁₄H₁₂O₄	[M+HCOO]^-	244.074 7	289.073 1	79.050 0	-4.840 0	Piceatannol	Phenol	DH
69	4.876 0	C₂₃H₃₄O₁₅	[M+HCOO]^-	550.193 4	595.192 0	76.820 0	-6.850 0	Genipin gentian diglycoside	Terpenoid	ZZ
70	4.984 0	C₂₃H₃₄O₁₅	[M+Cl]^-	550.193 4	585.163 7	72.240 0	-6.190 0	Genipin diglucopyranoside	Terpenoid	ZZ
71	5.017 0	C₉H₈O₄	[M-H]^-	180.043 4	179.036 1	79.040 0	-5.800 0	Caffeic acid	Phenylpropanoid	ZZ
72	5.240 0	C₁₇H₂₄O₁₀	[M+Cl]^-	388.140 8	423.110 0	75.980 0	-8.320 0	Geniposide methyl	Terpenoid	ZZ
73	5.240 0	C₁₇H₂₄O₁₀	[M+Cl]^-	388.140 8	423.110 0	75.980 0	-8.320 0	Geniposide	Terpenoid	ZZ
74	5.687 0	C₈H₈O₂	[M-H]^-	136.053 1	135.045 9	83.880 0	-4.670 0	p-Hydroxyacetophenone	Phenol	YC
75	6.009 0	C₂₅H₂₄O₁₂	[M-H]^-	516.126 8	515.121 7	74.530 0	-5.770 0	Dicaffeyl quinic acid isomers	Tannin	ZZ, YC
76	6.613 0	C₁₉H₂₆O₁₁	[M+HCOO]^-	430.146 7	475.144 9	85.300 0	-0.530 0	6'-O-Acetylgenipinside	Terpenoid	ZZ
77	6.613 0	C₁₉H₂₆O₁₁	[M+HCOO]^-	430.146 7	475.144 9	85.300 0	-0.530 0	10-Acetylgenipinside	Terpenoid	ZZ
78	6.621 0	C₂₅H₂₄O₁₂	[M-H]^-	516.127 6	515.119 8	88.230 0	-1.710 0	3,4-O-Dicaffeoyl quinic acid	Tannin	ZZ, YC
79	6.621 0	C₂₅H₂₄O₁₂	[M-H]^-	516.127 6	515.119 8	88.230 0	-1.710 0	1,4-Dicaffeyl quinic acid	Tannin	ZZ, YC
80	6.621 0	C₂₅H₂₄O₁₂	[M-H]^-	516.127 6	515.119 8	88.230 0	-1.710 0	Isochlorogenic acid A	Phenylpropanoid	ZZ, YC
81	6.621 0	C₂₅H₂₄O₁₂	[M-H]^-	516.127 6	515.119 8	88.230 0	-1.710 0	Isochlorogenic acid C	Phenylpropanoid	ZZ, YC
82	6.654 0	C₃₂H₄₀O₁₇	[M+Cl]^-	696.226 5	731.197 5	68.990 0	-3.460 0	6"-O-p-Coumaryl gentiobiglycoside	Terpenoid	ZZ
83	6.655 0	C₃₂H₄₀O₁₇	[M-H]^-	696.228 7	695.216 4	37.760 0	4.080 0	6"-O-trans-p-Coumaryl gentibiglycoside	Terpenoid	ZZ
84	7.027 0	C₂₁H₂₀O₉	[M+HCOO]^-	416.110 7	461.136 8	47.180 0	1.030 0	Chrysophanol-1-O-glucoside	Quinone	DH
85	7.027 0	C₂₁H₂₀O₉	[M+HCOO]^-	416.110 7	461.136 8	47.180 0	1.030 0	Chrysophanol-8-O-glucoside	Quinone	DH
86	7.515 0	C₂₂H₂₂O₁₁	[M-H]^-	462.118 0	461.111 5	81.940 0	-4.990 0	2-O-Cinnamyl-1-O-galloyl-β-D-glucose	Tannin	DH
87	8.788 0	C₁₆H₁₂O₅	[M-H]^-	284.068 5	283.062 5	41.600 0	-4.640 0	5,4'-Dihydroxy-7-methoxyflavone	Flavonoid	ZZ
88	9.955 0	C₁₅H₈O₆	[M-H]^-	284.032 1	283.025 1	78.820 0	-2.770 0	Emodin	Quinone	DH
89	11.328 0	C₁₅H₁₀O₅	[M-H]^-	270.052 8	269.047 3	69.020 0	-6.080 0	Rhein	Quinone	DH
90	11.344 0	C₁₅H₁₀O₅	[M-H]^-	270.054 0	269.047 4	67.920 0	-5.280 0	Aloe-emodin	Quinone	DH

No.	RT/min	Formula	Adduct	Mass	m/z	Score	Error/×10^-6	Compound	Category	Source
1	0.699 0	C₁₅H₁₈O₁₀	[M+Na]⁺	358.091 4	381.081 1	72.860 0	-3.890 0	Pyrimethacin	Coumarin	YC
2	1.030 0	C₁₅H₁₄O₄	[M+H]⁺	258.086 2	259.095 0	82.510 0	5.070 0	Rhamnosyl-3,3',5-trihydroxy-4'-methoxystilbene	Phenol	DH
3	1.071 0	C₅H₉NO₂	[M+H]⁺	115.063 8	116.071 0	86.500 0	-3.820 0	Proline	Amino acid	YC
4	2.461 0	C₉H₁₁NO₂	[M+H]⁺	165.079 7	166.087 0	84.630 0	-4.560 0	Phenylalanine	Amino acid	YC
5	2.932 0	C₁₂H₂₀O₂	[M+Na]⁺	196.146 1	219.135 2	86.710 0	1.500 0	Geranyl acetate	Volatile oil	YC
6	3.627 0	C₉H₆O₃	[M+H]⁺	162.031 7	163.039 1	87.280 0	-0.970 0	7-Hydroxy-coumarin	Coumarin	YC
7	3.817 0	C₆H₆O₃	[M+H]⁺	126.031 8	127.038 6	46.700 0	3.010 0	1,2,4-Benzenetriol	Phenol
8	3.892 0	C₁₀H₁₀O₄	[M+H]⁺	194.058 3	195.064 1	92.280 0	4.720 0	Ferulic acid	Phenylpropanoid	YC
9	3.892 0	C₂₁H₂₄O₁₁	[M+H]⁺	452.131 2	453.139 2	88.150 0	0.270 0	Catechin-5-O-β-D-glucopyranoside	Flavonoid	DH
10	4.131 0	C₉H₇NO	[M+H]⁺	145.052 4	146.059 7	79.520 0	3.240 0	4-Formylindole	Alkaloid	YC
11	4.471 0	C₃₀H₂₆O₁₂	[M+H]⁺	578.143 0	579.148 9	91.340 0	1.850 0	Proanthocyanidin B1	Flavonoid	DH
12	4.471 0	C₃₀H₂₆O₁₂	[M+H]⁺	578.143 0	579.148 9	91.340 0	1.850 0	Proanthocyanidin B2	Flavonoid	DH
13	4.471 0	C₃₀H₂₆O₁₂	[M+H]⁺	578.143 0	579.148 9	91.340 0	1.850 0	Proanthocyanidin B3	Flavonoid	DH
14	4.471 0	C₃₀H₂₆O₁₂	[M+H]⁺	578.143 0	579.148 9	91.340 0	1.850 0	Proanthocyanidin B4	Flavonoid	DH
15	4.471 0	C₃₀H₂₆O₁₂	[M+H]⁺	578.143 0	579.148 9	91.340 0	1.850 0	Proanthocyanidin B7	Flavonoid	DH
16	4.471 0	C₂₈H₂₈O₁₂	[M+Na]⁺	556.158 1	579.149 4	69.400 0	-3.410 0	Deoxyearth rhein-8-O-gallate	Phenol	DH
17	4.744 0	C₁₅H₁₄O₆	[M+H]⁺	290.079 0	291.086 9	97.620 0	-2.050 0	Catechins	Flavonoid	DH
18	4.876 0	C₉H₁₄O₄	[M+Na]⁺	186.089 2	209.081 3	70.670 0	-16.050 0	Azelaic acid	Fatty acid	YC
19	4.975 0	C₁₇H₂₂O	[M+Na]⁺	242.166 5	265.154 9	50.460 0	12.450 0	Dehydrofusarinol	Polyacetylene alcohol	YC
20	5.124 0	C₁₀H₁₆O	[M+H]⁺	152.120 8	153.128 2	74.050 0	-4.530 0	Arborone	Volatile oil	YC
21	5.190 0	C₂₇H₃₀O₁₅	[M+H]⁺	594.159 0	595.166 5	96.570 0	-0.820 0	Nicotilorin	Flavonoid	YC
22	5.232 0	C₁₀H₈O₃	[M+H]⁺	176.047 3	177.055 1	84.560 0	-2.450 0	7-Methoxy-coumarin	Coumarin	YC
23	5.232 0	C₁₁H₁₄O₅	[M+H]⁺	226.084 1	227.092 4	95.620 0	-3.860 0	Genipine	Terpenoid	ZZ
24	5.232 0	C₁₆H₂₄O₁₀	[M+H]⁺	376.139 1	377.146 8	78.580 0	-5.830 0	Mussaenosidic acid	Terpenoid	ZZ
25	5.323 0	C₂₇H₃₀O₁₆	[M+H]⁺	610.154 5	611.161 9	93.460 0	-1.900 0	Rutin	Flavonoid	YC
26	5.562 0	C₁₆H₂₆O₇	[M+H]⁺	330.168 2	331.175 1	77.220 0	-2.190 0	Epijasminoside A	Quinone	ZZ
27	5.653 0	C₈H₈O₂	[M+H]⁺	136.052 4	137.059 4	75.990 0	0.750 0	Anisaldehyde	Volatile oil	ZZ
28	5.926 0	C₁₂H₁₀O₅	[M+H]⁺	234.053 1	235.060 3	81.610 0	-1.000 0	2-Methyl-5-carboxymethyl-7-hydroxychromone	Quinone	DH
29	6.017 0	C₁₅H₁₀O₇	[M+H]⁺	302.044 0	303.051 1	74.000 0	-3.480 0	Quercetin	Flavonoid	YC
30	6.059 0	C₁₀H₈O₄	[M+H]⁺	192.042 3	193.050 1	84.460 0	-3.140 0	7-Methylchestnut baretin	Coumarin	YC
31	6.059 0	C₁₀H₈O₄	[M+H]⁺	192.042 3	193.050 1	84.460 0	-3.140 0	Scopolamine	Coumarin	YC
32	6.059 0	C₁₀H₈O₄	[M+H]⁺	192.042 3	193.050 1	84.460 0	-3.140 0	Isoscopolamine	Coumarin	YC
33	6.059 0	C₁₅H₁₀O₇	[M+H]⁺	302.042 7	303.051 0	76.000 0	-3.150 0	Mulberry pigment	Flavonoid	YC
34	6.059 0	C₂₁H₂₀O₁₂	[M+H]⁺	464.095 5	465.105 3	35.150 0	-5.470 0	Hypericin	Flavonoid	YC
35	6.208 0	C₂₁H₂₂O₉	[M+H]⁺	418.126 9	419.134 4	96.440 0	-1.200 0	Gardenia	Flavonoid	ZZ
36	6.208 0	C₁₉H₂₄O₉	[M+Na]⁺	396.145 5	419.134 4	60.190 0	-7.300 0	2-(2'-Hydroxypropyl)-5-methyl-7-hydroxychromotone-7-O-β-D-glucopyranoside	Phenol	DH
37	6.282 0	C₂₈H₃₂O₁₆	[M+H]⁺	624.168 8	625.175 8	72.530 0	0.510 0	Narcissine	Flavonoid	YC
38	6.373 0	C₁₃H₁₂O₄	[M+H]⁺	232.074 8	233.082 1	73.050 0	-4.790 0	2-Methyl-5-propanyl-7-hydroxychromoketone	Quinone	DH
39	6.398 0	C₁₃H₁₄O₄	[M+H]⁺	234.090 2	235.097 7	89.320 0	-5.530 0	2-(2'-Hydroxypropyl)-5-methyl-7-hydroxychromone	Phenol	DH
40	6.414 0	C₂₂H₂₂O₁₂	[M+H]⁺	478.111 1	479.118 8	98.430 0	-0.510 0	Isorhamnein-3-O-galactoside	Flavonoid	YC
41	6.414 0	C₂₂H₂₂O₁₂	[M+H]⁺	478.111 1	479.118 8	98.430 0	-0.510 0	Isorhamnein-3-O-glucoside	Flavonoid	YC
42	6.414 0	C₂₂H₂₂O₁₂	[M+H]⁺	478.111 1	479.118 2	80.180 0	0.170 0	2-O-Coumaryl-1-O-galloyl-β-D-glucose	Tannin	DH
43	6.497 0	C₁₆H₁₂O₇	[M+H]⁺	316.060 0	317.067 9	65.160 0	3.390 0	Capillarisin	Flavonoid	YC
44	6.671 0	C₁₁H₁₀O₄	[M+H]⁺	206.058 6	207.066 3	69.780 0	3.390 0	Inchen chromogenone	Coumarin	YC
45	6.985 0	C₁₁H₁₀O₃	[M+H]⁺	190.063 6	191.071 0	91.540 0	-3.760 0	2,5-Dimethyl-7-hydroxychromoton	Quinone	DH
46	7.696 0	C₂₀H₂₄O₉	[M+H]⁺	408.143 5	409.151 5	66.150 0	-5.090 0	Casidone-8-O-β-D-glucopyranoside	Phenol	DH
47	7.895 0	C₁₅H₁₀O₄	[M+H]⁺	254.059 2	255.066 5	79.670 0	-5.130 0	Chrysophanol	Quinone	DH
48	8.416 0	C₁₆H₁₂O₅	[M+H]⁺	284.069 6	285.077 4	75.400 0	-5.120 0	Physcion	Quinone	DH
49	15.190 0	C₁₈H₃₀O₂	[M+H]⁺	278.225 4	279.233 2	68.450 0	-4.540 0	Linolenic acid or its isomer	Fatty acid	YC
50	0.674 0	C₂₆H₃₀O₁₂	[M-H]^-	534.176 1	533.168 8	71.030 0	-4.350 0	p-Coumaryl genipin	Terpenoid	ZZ
51	1.601 0	C₁₃H₁₆O₁₀	[M-H]^-	332.075 4	331.068 8	67.170 0	-3.690 0	1-O-Gallic acyl fructose	Tannin	DH
52	1.601 0	C₇H₆O₅	[M-H]^-	170.021 5	169.015 0	96.620 0	-3.960 0	Gallic acid	Tannin	DH
53	3.429 0	C₁₉H₂₆O₁₅	[M-H]^-	494.125 5	493.118 9	96.660 0	1.920 0	1-O-Gallic acyl sucrose	Tannin	DH
54	3.577 0	C₁₆H₁₈O₉	[M-H]^-	354.095 1	355.102 5	97.520 0	-0.920 0	Chlorogenic acid	Phenylpropanoid	ZZ, YC
55	3.577 0	C₁₆H₁₈O₉	[M-H]^-	354.095 1	355.102 5	97.520 0	-0.920 0	Cryptochlorogenic acid	Phenylpropanoid	ZZ, YC
56	3.577 0	C₁₆H₁₈O₉	[M-H]^-	354.095 1	355.102 5	97.520 0	-0.920 0	Neochlorogenic acid	Phenylpropanoid	ZZ, YC
57	3.577 0	C₁₀H₁₂O₇	[M-H]^-	244.058 3	243.050 4	45.960 0	2.600 0	1-O-Gallic acylglycerol	Tannin	DH
58	3.875 0	C₁₆H₂₂O₁₀	[M-H]^-	373.113 0	374.121 3	72.000 0	1.410 0	Geniposide acid	Terpenoid	ZZ
59	3.875 0	C₁₆H₂₄O₁₁	[M-H]^-	392.132 2	391.125 0	92.130 0	-1.200 0	Mountain gardenoside	Terpenoid	ZZ
60	3.917 0	C₁₆H₂₂O₁₀	[M+Cl]^-	374.121 2	409.090 7	75.820 0	0.110 0	Gardenia new nucleoside	Terpenoid	ZZ
61	4.264 0	C₁₆H₂₆O₈	[M-H]^-	346.162 8	345.156 2	95.530 0	-1.030 0	Saffron picylate-β-D-glucopyranose	Terpenoid	ZZ
62	4.264 0	C₁₆H₂₆O₈	[M-H]^-	346.163 1	345.156 2	95.530 0	-1.030 0	Jasminoside B	Terpenoid	ZZ
63	4.727 0	C₃₁H₃₂O₁₆	[M+HCOO]^-	660.169 0	705.169 8	61.010 0	-4.250 0	3,5-Dicaffeyl-5-(3-hydroxy-3-methylglutaryl) quinic acid	Tannin	ZZ
64	4.727 0	C₃₁H₃₂O₁₆	[M+HCOO]^-	660.169 0	705.169 8	61.010 0	-4.250 0	3,4-Dio-cafeyl-5-O-(3-hydroxy-3-methyl) glutaryl quinic acid	Tannin	ZZ
65	4.727 0	C₃₁H₃₂O₁₆	[M+HCOO]^-	660.169 0	705.169 8	61.010 0	-4.250 0	3,5,6,4'-Tetrahydroxy 3',5'-dimethoxy flavone	Flavonoid	ZZ
66	4.727 0	C₃₁H₃₂O₁₆	[M+HCOO]^-	660.169 0	705.169 8	61.010 0	-4.250 0	3,5-Di-O-caffeyl-4-O-(3-hydroxy-3-methyl) alutaryl quinic acid	Tannin	ZZ
67	4.727 0	C₃₁H₃₂O₁₆	[M+HCOO]^-	660.169 0	705.169 8	61.010 0	-4.250 0	3-O-Ferulyl-4-O-(3-hydroxyl, 3-methyl) glutaryl-5-O-caffeyl quinic acid	Tannin	ZZ
68	4.744 0	C₁₄H₁₂O₄	[M+HCOO]^-	244.074 7	289.073 1	79.050 0	-4.840 0	Piceatannol	Phenol	DH
69	4.876 0	C₂₃H₃₄O₁₅	[M+HCOO]^-	550.193 4	595.192 0	76.820 0	-6.850 0	Genipin gentian diglycoside	Terpenoid	ZZ
70	4.984 0	C₂₃H₃₄O₁₅	[M+Cl]^-	550.193 4	585.163 7	72.240 0	-6.190 0	Genipin diglucopyranoside	Terpenoid	ZZ
71	5.017 0	C₉H₈O₄	[M-H]^-	180.043 4	179.036 1	79.040 0	-5.800 0	Caffeic acid	Phenylpropanoid	ZZ
72	5.240 0	C₁₇H₂₄O₁₀	[M+Cl]^-	388.140 8	423.110 0	75.980 0	-8.320 0	Geniposide methyl	Terpenoid	ZZ
73	5.240 0	C₁₇H₂₄O₁₀	[M+Cl]^-	388.140 8	423.110 0	75.980 0	-8.320 0	Geniposide	Terpenoid	ZZ
74	5.687 0	C₈H₈O₂	[M-H]^-	136.053 1	135.045 9	83.880 0	-4.670 0	p-Hydroxyacetophenone	Phenol	YC
75	6.009 0	C₂₅H₂₄O₁₂	[M-H]^-	516.126 8	515.121 7	74.530 0	-5.770 0	Dicaffeyl quinic acid isomers	Tannin	ZZ, YC
76	6.613 0	C₁₉H₂₆O₁₁	[M+HCOO]^-	430.146 7	475.144 9	85.300 0	-0.530 0	6'-O-Acetylgenipinside	Terpenoid	ZZ
77	6.613 0	C₁₉H₂₆O₁₁	[M+HCOO]^-	430.146 7	475.144 9	85.300 0	-0.530 0	10-Acetylgenipinside	Terpenoid	ZZ
78	6.621 0	C₂₅H₂₄O₁₂	[M-H]^-	516.127 6	515.119 8	88.230 0	-1.710 0	3,4-O-Dicaffeoyl quinic acid	Tannin	ZZ, YC
79	6.621 0	C₂₅H₂₄O₁₂	[M-H]^-	516.127 6	515.119 8	88.230 0	-1.710 0	1,4-Dicaffeyl quinic acid	Tannin	ZZ, YC
80	6.621 0	C₂₅H₂₄O₁₂	[M-H]^-	516.127 6	515.119 8	88.230 0	-1.710 0	Isochlorogenic acid A	Phenylpropanoid	ZZ, YC
81	6.621 0	C₂₅H₂₄O₁₂	[M-H]^-	516.127 6	515.119 8	88.230 0	-1.710 0	Isochlorogenic acid C	Phenylpropanoid	ZZ, YC
82	6.654 0	C₃₂H₄₀O₁₇	[M+Cl]^-	696.226 5	731.197 5	68.990 0	-3.460 0	6"-O-p-Coumaryl gentiobiglycoside	Terpenoid	ZZ
83	6.655 0	C₃₂H₄₀O₁₇	[M-H]^-	696.228 7	695.216 4	37.760 0	4.080 0	6"-O-trans-p-Coumaryl gentibiglycoside	Terpenoid	ZZ
84	7.027 0	C₂₁H₂₀O₉	[M+HCOO]^-	416.110 7	461.136 8	47.180 0	1.030 0	Chrysophanol-1-O-glucoside	Quinone	DH
85	7.027 0	C₂₁H₂₀O₉	[M+HCOO]^-	416.110 7	461.136 8	47.180 0	1.030 0	Chrysophanol-8-O-glucoside	Quinone	DH
86	7.515 0	C₂₂H₂₂O₁₁	[M-H]^-	462.118 0	461.111 5	81.940 0	-4.990 0	2-O-Cinnamyl-1-O-galloyl-β-D-glucose	Tannin	DH
87	8.788 0	C₁₆H₁₂O₅	[M-H]^-	284.068 5	283.062 5	41.600 0	-4.640 0	5,4'-Dihydroxy-7-methoxyflavone	Flavonoid	ZZ
88	9.955 0	C₁₅H₈O₆	[M-H]^-	284.032 1	283.025 1	78.820 0	-2.770 0	Emodin	Quinone	DH
89	11.328 0	C₁₅H₁₀O₅	[M-H]^-	270.052 8	269.047 3	69.020 0	-6.080 0	Rhein	Quinone	DH
90	11.344 0	C₁₅H₁₀O₅	[M-H]^-	270.054 0	269.047 4	67.920 0	-5.280 0	Aloe-emodin	Quinone	DH

No.	RT/min	Formula	Adduct	Mass	m/z	Score	Error	Compound	Category	Source
1	0.498 0	C₁₅H₁₀O₄	[M+H]⁺	254.057 9	255.065 6	95.870 0	-1.430 0	Chrysophanol	Quinone	DH
2	1.193 0	C₂₈H₂₈O₁₂	[M+Na]⁺	556.158 1	579.152 2	64.420 0	-5.120 0	Deoxyrhaponticin 2'-O-gallate	Phenol	DH
3	1.499 0	C₁₆H₂₄O₁₀	[M+H]⁺	376.136 9	377.145 6	86.290 0	0.050 0	Mussaenosidic acid	Terpene	ZZ
4	1.739 0	C₁₀H₈O₃	[M+H]⁺	176.047 3	177.054 5	64.550 0	3.720 0	Herniarin	Coumarin	YC
5	12.610 0	C₁₅H₈O₆	[M+COOH]^－	284.032 1	329.035 4	51.100 0	-16.620 0	Emodin	Quinone	DH

No.	RT/min	Formula	Adduct	Mass	m/z	Score	Error	Compound	Category	Source
1	0.498 0	C₁₅H₁₀O₄	[M+H]⁺	254.057 9	255.065 6	95.870 0	-1.430 0	Chrysophanol	Quinone	DH
2	1.193 0	C₂₈H₂₈O₁₂	[M+Na]⁺	556.158 1	579.152 2	64.420 0	-5.120 0	Deoxyrhaponticin 2'-O-gallate	Phenol	DH
3	1.499 0	C₁₆H₂₄O₁₀	[M+H]⁺	376.136 9	377.145 6	86.290 0	0.050 0	Mussaenosidic acid	Terpene	ZZ
4	1.739 0	C₁₀H₈O₃	[M+H]⁺	176.047 3	177.054 5	64.550 0	3.720 0	Herniarin	Coumarin	YC
5	12.610 0	C₁₅H₈O₆	[M+COOH]^－	284.032 1	329.035 4	51.100 0	-16.620 0	Emodin	Quinone	DH

基于UPLC-QTOF/MS的茵陈蒿汤体外成分鉴定和急性肝损伤防护作用入血成分研究

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姚一青 ^# , 曹奇 ^# , 王璇 , 马荟琳 , 陈玉苗 , 赵思怡 , 郭珉萱 , 胡伽濛 , 王冬尧 ^* , 吕狄亚 ^*

药学学报 | 专题报道: 中药活性成分与作用机制 2023,58(5): 1173-1180

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药学学报 | 专题报道: 中药活性成分与作用机制 2023, 58(5): 1173-1180

基于UPLC-QTOF/MS的茵陈蒿汤体外成分鉴定和急性肝损伤防护作用入血成分研究

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姚一青^#, 曹奇^#, 王璇, 马荟琳, 陈玉苗, 赵思怡, 郭珉萱, 胡伽濛, 王冬尧^*, 吕狄亚^*

作者信息

海军军医大学药学系, 上海 200433

通讯作者:

*王冬尧, Tel: 13391376186, E-mail: wangdongyao@smmu.edu.cn;

吕狄亚, Tel: 15802192958, E-mail: lvdy2020@smmu.edu.cn

Identification of constituents in vitro and blood-absorbed ingredients of protective effect on acute liver injury from Yin Chen Hao decoction based on UPLC-QTOF/MS

Yi-qing YAO, Qi CAO, Xuan WANG, Hui-lin MA, Yu-miao CHEN, Si-yi ZHAO, Min-xuan GUO, Jia-meng HU, Dong-yao WANG^*, Di-ya LÜ^*

Affiliations

School of Pharmacy, Naval Medical University, Shanghai 200433, China

出版时间: 2023-05-12 doi: 10.16438/j.0513-4870.2022-1139

文章导航

摘要

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鉴定茵陈蒿汤体外活性成分和体内入血成分, 为探究其对急性肝损伤防护作用和防治机制提供了科学依据。利用超高效液相色谱-四极杆飞行时间质谱(UPLC-QTOF/MS) 技术, 鉴定茵陈蒿汤水煎液及口服预防给药14天后, 刀豆蛋白A (con-A) 所致急性肝损伤小鼠的血清样本(本研究中所有实验动物的使用获得海军军医大学伦理委员会批准, 批号19YF1459400) 中的化学成分。初步鉴定茵陈蒿汤水煎液含90个化合物, 主要为黄酮类、萜类、鞣质类、醌类等, 血清样本中含5个原形成分, 包括大黄酚、脱氧土大黄苷-8-O-没食子酸盐、玉叶金花苷酸、7-甲氧基-香豆素、大黄素。本文所建立的UPLC-QTOF/MS方法能高效灵敏地鉴别茵陈蒿汤的体外成分及其入血成分, 初步阐明茵陈蒿汤保肝作用的药效物质基础, 可为茵陈蒿汤的质量标志物筛选和药理作用研究提供科学依据。

关键词

超高效液相色谱串联四极杆飞行时间质谱 / 化学成分 / 入血成分 / 茵陈蒿汤 / 急性肝损伤 / 保肝作用

Abstract

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To identify the active constituents in vitro and blood-absorbed ingredients in vivo from Yin Chen Hao decoction provides scientific evidence for probing its prevention and treatment mechanism on acute liver injury. An ultrahigh performance liquid chromatography quadrupole-time of flight-mass spectrometry (UPLC-QTOF/MS) method was applied for analysis of Yin Chen Hao decoction and the serum samples of mice with con-A induced acute liver injury after preventive oral administration for 14 days (the use of all laboratory animals in this study was approved by the Ethics Committee of the Naval Medical University, 19YF1459400). A total of 90 chemical constituents were identified from Yin Chen Hao decoction, mainly were flavonoids, terpenoids, tannins, quinones. 5 prototype compounds were identified in the serum, including chrysophanol, deoxyrhapontin-8-O-gallate, mussaenosidic acid, herniarin, emodin. The established UPLC-QTOF/MS method could efficiently and sensitively identify the constituents in vitro and blood-absorbed ingredients of Yin Chen Hao decoction, primarily clarify the material basis of its hepatoprotective effect, and provided a scientific basis for the quality marker selection and the pharmacodynamic material basis research on the decoction.

Key words

UPLC-QTOF/MS / chemical constituent / blood-absorbed ingredient / Yin Chen Hao decoction / acute liver injury / hepatoprotective effect

引用本文

姚一青, 曹奇, 王璇, 马荟琳, 陈玉苗, 赵思怡, 郭珉萱, 胡伽濛, 王冬尧, 吕狄亚. 基于UPLC-QTOF/MS的茵陈蒿汤体外成分鉴定和急性肝损伤防护作用入血成分研究. 药学学报, 2023 , 58 (5) : 1173 -1180 . DOI: 10.16438/j.0513-4870.2022-1139

Yi-qing YAO, Qi CAO, Xuan WANG, Hui-lin MA, Yu-miao CHEN, Si-yi ZHAO, Min-xuan GUO, Jia-meng HU, Dong-yao WANG, Di-ya LÜ. Identification of constituents in vitro and blood-absorbed ingredients of protective effect on acute liver injury from Yin Chen Hao decoction based on UPLC-QTOF/MS[J]. Acta Pharmaceutica Sinica, 2023 , 58 (5) : 1173 -1180 . DOI: 10.16438/j.0513-4870.2022-1139

正文

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急性肝损伤(acute liver injury, ALI) 指既往无肝病且出现肝脏异常不足6个月的患者, 其肝细胞大量死亡或者肝功能丧失。随着肝细胞的减少, 急性肝损伤可能会进一步发展成肝性脑病, 最终导致严重的肝衰竭^[1], 危害人类健康。目前, 临床常用于治疗急性肝损伤的药物有N-乙酰半胱氨酸、甲基吡唑、亚甲蓝、二甲双胍等。然而, 它们药效有限而且使用剂量较高, 常会在使用时失去效应或出现过敏、恶心、高铁红血症等不良作用。中药在增强肝抗氧化能力和启动细胞自噬等保护机制上具有独特优势, 因此, 需要更广泛的研究来推进中药在急性肝损伤方面的应用^[2]。

茵陈蒿汤出自《伤寒论》, 由茵陈、大黄、栀子三味药材组成, 具有清热、利湿、退黄之功效, 主治湿热黄疸证。目前, 茵陈蒿汤被证实具有良好的保肝作用, 能够改善四氯化碳所致的急性肝损伤^[3], 并且能够通过促进白细胞迁移以提高机体免疫功能^[4], 但还未见其在刀豆蛋白A (con-A) 免疫性肝损伤保护作用中的活性成分的相关报道。

中药复方体内与体外之间化学成分具有重要关联, 针对复方进入机体内的化学成分群进行分析是发现活性物质的有效手段^[5]。中药血中移行成分含量极低, 传统的成分鉴定和体内代谢分析一般采用液相色谱-单极杆质谱^[6], 对于中药复杂体系缺乏足够的精确度。四极杆飞行时间质谱结合了四极杆质谱和飞行时间质谱两种仪器的优势, 较其他方法可结合多种统计软件建立精确质量数据库, 通过“精确质量数-分子式”的匹配实现半自动化的成分鉴定, 并且能够在缺乏对照品的情况下利用库检索快速准确地进行定性检测^[7]。

因此, 本研究采用长期预防给药茵陈蒿汤水煎液的方式, 运用UPLC-QTOF/MS技术鉴定茵陈蒿汤中具有保肝作用的入血成分, 旨在阐明茵陈蒿汤防护急性肝损伤的药效物质基础, 以期为推进茵陈蒿汤的药效研究提供基础。

材料与方法

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仪器 UPLC-Q-TOF/MS, 包含Infinity-6538 UHD及Accurate-Mass QTOF系统、Agilent 6538 UHD飞行时间质谱仪(美国Agilent公司); 离心机(美国ThermoFisher公司); Milli-QA10超纯水制备系统(美国Millipore公司); 涡旋机(美国Scientific Industries公司)。

药品与试剂 色谱纯乙腈(德国Merck Chemicals公司); 色谱纯甲酸和色谱纯三氟乙酸(美国Tedia公司); 甲醇等试剂购自中国医药集团上海化学试剂公司; 茵陈蒿汤组方饮片(茵陈、栀子和大黄) 均购自上海长海医院; con-A (货号C5275, 德国Sigma公司)。

样品制备 称量茵陈约18 g、栀子约9 g、大黄约6 g, 粉碎栀子和大黄。茵陈加入适量蒸馏水浸泡50 min, 之后先取茵陈加入蒸馏水600 mL, 煮沸后慢煎至300 mL, 大约20 min, 再加入栀子和大黄煎煮大约30 min, 趁热过滤。再加入蒸馏水600 mL煎煮30 min, 趁热过滤。合并滤液, 浓缩至330 mL, 相当于生药浓度0.1 g·mL^-1。经0.22 µm微孔滤膜过滤, 于4 ℃冰箱待测。

实验动物 C57BL/6J小鼠购买于上海斯莱克动物有限责任公司, 许可证号: SYXK (沪) 2017-0004。18只小鼠(体重18~22 g, 年龄6~8周), 随机分为3组: 空白组(6只)、给药组(6只)、模型组(6只), 饲养环境保持12 h光照与黑暗循环, 环境温度20~25 ℃, 相对湿度50%~70%, 期间自由饮水进食, 实验前禁食12 h, 自由饮水。本实验动物饲养于海军军医大学药学系动物实验中心, 本研究中所有实验动物的使用获得海军军医大学伦理委员会批准, 批号19YF1459400。

预防给药及急性肝损伤模型建立 给药组按照体重灌胃给药茵陈蒿汤水煎液(30 mL·kg^-1), 连续14天; 模型组与空白组相同剂量灌胃无菌生理盐水。末次灌胃后, 模型组与给药组小鼠给予尾静脉注射con-A构建急性肝损伤模型, 按照小鼠体重15 mg·kg^-1的剂量^[8]; 空白组小鼠给予等量的无菌生理盐水。两组实验小鼠禁食不禁水。

成人汤剂给药剂量为6.67~10 mL·kg^-1, 换算成小鼠为60.5~91 mL·kg^-1, 考虑到小鼠胃容量大约为1~1.5 mL, 一次最大灌药量为0.9 mL, 所以给药剂量为30 mL·kg^{-1 [9-11]}。

血液样品处理 三组分别于造模后8 h眼眶取血0.3 mL于肝素钠离心管内静置2 h后, 于4 ℃下3 000 r·min^-1离心10 min。取上清, 加入3倍量-80 ℃预冷甲醇(含2 µg·mL^-1氯苯丙氨酸, 内标), 涡旋混匀3 min, 于4 ℃下12 000 r·min^-1离心15 min, 取上清液, 于冷冻浓缩仪浓缩, 进样前用100 µL甲醇复溶。

肝功能指标检测 血清样品分别采用谷丙转氨酶(ALT/GPT) 测试盒(货号C009-2-1微板法) 和谷草转氨酶(AST/GOT) 测试盒(货号C010-2-1微板法) 检测血清ALT和AST水平。

茵陈蒿汤化学成分数据库建立 通过检索中医药综合数据库TCMID (http://www.megabionet.org/tcmid/)、中药系统药理学数据库与分析平台TCMSP (https://old.tcmsp-e.com/tcmsp.php)、中国科学院上海有机化学研究所中药与化学成分库(http://www.chemcpd.csdb.cn/scdb/main/tcm_introduce.asp)、中医药整合药理学研究平台TCMIP (http://www.tcmip.cn/TCMIP/index.php/Home/Login/login.html)、Natural Product Activity and Species Source NPASS (https://bidd.group/NPASS/search.php), 整理茵陈蒿汤各组分药材化学成分, 查阅复方与单味药材化学成分鉴定文献, 完善成分表格。将整理好的茵陈蒿汤化学成分数据表格文件导入安捷伦的数据库构建软件MassHunter PCDL Manager B.08.00, 完成茵陈蒿汤化学成分数据库的建立, 具体信息包含序号、化合物名称、分子式、精确分子质量(由软件PCDL Manager计算得到)。

分析条件 色谱柱为ACQUITY UPLC BEH C18柱(2.1 mm × 100 mm, 2.5 μm, Xbridge爱尔兰), 流动相采用0.1%甲酸水(A)-0.1%甲酸乙腈(B) 溶液系统, 梯度洗脱条件为: 0~2 min, 2% B; 2~17 min, 2%~98% B; 17~20 min, 98% B。平衡时间5 min, 流速0.4 mL·min^-1, 柱温40 ℃, 自动进样器温度4 ℃, 进样量3 µL, 分析时间19 min。

质谱仪采用电喷雾离子源, 毛细管电压4 000 V (正离子)/3 500 V (负离子); 离子源温度: 350 ℃; 干燥气体流速: 11 L·min^-1; 雾化器压力: 45 psig; 碎片电压: 120 V; skimmer电压: 60 V。采集范围m/z 50~1 500, 参比离子正离子[M+H]⁺, 121.050 9和922.009 8; 负离子[M-H]^-, 119.036 3和966.000 7。所有数据均由Agilent Mass Hunter 10.0, Agilent PCDL 10.0软件处理。

统计学处理 数据以各组的均数±标准误差表示, 采用SPSS 19.0软件进行统计分析, 各组采用单因素方差分析, 统计显著性由Student's t检验确定, ^*P < 0.05表示差异具有统计学意义。

结果

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1 三组小鼠肝功能指标比较

临床常用血清中ALT和AST作为急性肝损伤的诊断指标, 含量的高低提示con-A造模是否成功以及茵陈蒿汤对con-A所致急性肝损伤是否具有保护作用。三组小鼠的血清ALT和AST水平结果如图 1所示。模型组较空白组血清ALT、AST水平均明显升高, 提示造模成功; 给药组较模型组血清ALT、AST水平均明显降低, 说明茵陈蒿汤对于急性肝损伤具有保护作用。

2 茵陈蒿汤体外成分分析

采用UPLC-QTOF/MS对茵陈蒿汤水煎液进行液质联用进样分析, 正、负离子模式下的总离子流图, 如图 2所示。建立了茵陈蒿汤化学成分数据库, 总共包含已知分子式和精确分子质量的498个化合物。采集与处理数据, 整理得到茵陈蒿汤体外成分共90个化合物, 如表 1所示。

从茵陈蒿汤水煎液中共鉴定出90个化合物, 分别为黄酮类19个、萜类16个、鞣质类13个、醌类11个、酚类8、苯丙素类7个、香豆素类7个、挥发油3个、氨基酸类2个、脂肪酸类2个、生物碱类1个、聚乙炔醇类1个。

体外成分的90个化合物中, 34个来源茵陈, 主要为黄酮类、香豆素类、苯丙素类; 29个来源大黄, 主要为黄酮类、醌类、酚类、鞣质类; 34个来源栀子, 主要为萜类、鞣质类、苯丙素类。其中, 有8个成分同时来源于栀子和茵陈, 表明三味药材在体外成分组成上, 既有共性成分, 又相互补充, 增加了复方化学成分群及其物质基础的的复杂性。

3 茵陈蒿汤入血成分分析

数据处理造模后8 h的给药组血清样品, 运用UPLC-QTOF/MS技术分别在正、负离子模式下得到茵陈蒿汤入血成分的总离子流图, 如图 3所示。采集与处理数据, 整理得到茵陈蒿汤原形入血成分共5个化合物, 如表 2所示。其中, 1个成分来源茵陈, 是7-甲氧基-香豆素; 3个成分来源大黄, 分别是大黄酚、脱氧土大黄苷-8-O-没食子酸盐、大黄素; 1个成分来源栀子, 是玉叶金花苷酸。原形入血成分多含有羟基, 特征离子峰多为[M+H]⁺与[M+Na]⁺, 因而正离子模式较负离子模式响应更优。保留时间在0.5~2 min内原形入血成分较多, 为酚酸类或苷类小分子化合物, 极性大、水溶性好, 较先出峰。

结论与讨论

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中药复方具有多成分、多靶点和多途径等鲜明特点, 而血清药物化学认为, 中药以血液为介质输送至靶点起效, 因此给药后入血成分可作为其活性成分。茵陈蒿汤化学成分成百上千, 为了回答茵陈蒿汤的药效物质基础, 建立一种既能体外分析茵陈蒿汤的化学成分, 又能辨识其入血成分的分析方法十分必要。

茵陈蒿汤体外成分90个, 原形入血成分共5个化合物, 分别是7-甲氧基-香豆素、大黄酚、脱氧土大黄苷-8-O-没食子酸盐、大黄素、玉叶金花苷酸。其中, 7-甲氧基-香豆素能够下调细胞凋亡水平, 减轻氧化应激, 对CCl₄诱导的肝损伤具有保护作用^[9]。大黄酚通过调控谷胱甘肽过氧化物酶和内质网应激反应能够修复肝纤维化^[10]。玉叶金花苷酸能够较强地抑制补体经典途径, 调节免疫功能, 在Fe²⁺-胱氨酸诱导的大鼠肝脏微粒体脂质过氧化中具有抗氧化活性^[11]。大黄素能够调控氧化应激途径、诱导细胞自噬对肝细胞起到保护作用, 降低肝组织损伤^{[12, 13]}。与茵陈蒿汤体外成分的种类数目相比较, 体内成分十分有限, 这也为方法优化提供了空间, 同时, 在后续的研究中将进一步探究上述成分预防保护急性肝损伤的靶点通路和作用机制。

对提取工艺考察时发现, 茵陈先浸泡可使植物膨胀吸水充分, 煎煮时香豆素类和挥发油更好溶出。大黄后下在煎煮时气味浓郁, 其游离型蒽醌成分和鞣质成分较多煎出, 然而结合型蒽醌成分未鉴定出。在原形入血成分中, 大黄的游离型蒽醌成分较多, 未出现鞣质类成分, 提示大黄保肝作用的药效物质基础可能为游离型蒽醌类。

目前急性肝损伤有多种动物模型, 不同模型有不同的病例特点和发病机制。con-A是一种从刀豆蛋白中提取的植物凝集素, 其发病机制主要为NKT细胞的细胞毒作用及细胞因子的肝损伤作用。其特征是可在8 h内观察到进行性肝炎、严重淋巴细胞浸润等特征^[14]。该模型简便快速, 是目前研究免疫介导肝损伤最广泛使用的工具之一, 很好地模拟了人类病毒性肝炎、自身免疫性肝病等疾病。

中医理论“上医治未病”阐明中药预防保护作用的重要性, 而中药的预防作用研究不多, 更少见复方的相应研究。本研究首先预防给药茵陈蒿汤, 之后造模急性肝损伤, 与中医“不治已乱治未乱”“扶正以助祛邪”的理念不谋而合。本研究采取连续14天长期给药的方式以期提高机体的免疫应答, 达到对急性肝损伤的预防与保护。相对于直接分析健康小鼠血清, 本研究对给药小鼠造模急性肝损伤, 更符合中医“辨证施治, 方证相应”的基本原则。

致谢: 上海市药物(中药) 代谢产物研究重点实验室给予帮助。

作者贡献: 本文由吕狄亚、王冬尧、曹奇负责研究思路设计; 姚一青、曹奇、王璇、马荟琳负责实验实施; 陈玉苗、赵思怡、胡伽濛、郭珉萱负责数据处理; 姚一青负责论文撰写; 吕狄亚负责论文修改。

利益冲突: 本文的作者和所涉及的内容不存在潜在的利益冲突。

基金

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国家自然科学基金资助项目(82174092)
上海市自然科学基金资助项目(21ZR1483000)
上海市自然科学基金资助项目(22ZR1476900)
海军军医大学本科创新能力孵化基地项目(FH2021116)
上海市浦江人才计划(21PJD083)
上海市科技人才计划项目(19YF1459400)

参考文献

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文献

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参考文献引证文献

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2023年第58卷第5期

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文章信息

doi: 10.16438/j.0513-4870.2022-1139

接收时间：2022-10-30
首发时间：2025-11-21
出版时间：2023-05-12

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作者

出版历史

收稿日期：2022-10-30
修回日期：2023-04-15

基金

国家自然科学基金资助项目(82174092)

上海市自然科学基金资助项目(21ZR1483000)

上海市自然科学基金资助项目(22ZR1476900)

海军军医大学本科创新能力孵化基地项目(FH2021116)

上海市浦江人才计划(21PJD083)

上海市科技人才计划项目(19YF1459400)

作者信息

海军军医大学药学系, 上海 200433

通讯作者:

*王冬尧, Tel: 13391376186, E-mail: wangdongyao@smmu.edu.cn;

吕狄亚, Tel: 15802192958, E-mail: lvdy2020@smmu.edu.cn

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https://castjournals.cast.org.cn/joweb/yxxb/CN/10.16438/j.0513-4870.2022-1139

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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.	RT/min	Formula	Adduct	Mass	m/z	Score	Error/×10^-6	Compound	Category	Source
1	0.699 0	C₁₅H₁₈O₁₀	[M+Na]⁺	358.091 4	381.081 1	72.860 0	-3.890 0	Pyrimethacin	Coumarin	YC
2	1.030 0	C₁₅H₁₄O₄	[M+H]⁺	258.086 2	259.095 0	82.510 0	5.070 0	Rhamnosyl-3,3',5-trihydroxy-4'-methoxystilbene	Phenol	DH
3	1.071 0	C₅H₉NO₂	[M+H]⁺	115.063 8	116.071 0	86.500 0	-3.820 0	Proline	Amino acid	YC
4	2.461 0	C₉H₁₁NO₂	[M+H]⁺	165.079 7	166.087 0	84.630 0	-4.560 0	Phenylalanine	Amino acid	YC
5	2.932 0	C₁₂H₂₀O₂	[M+Na]⁺	196.146 1	219.135 2	86.710 0	1.500 0	Geranyl acetate	Volatile oil	YC
6	3.627 0	C₉H₆O₃	[M+H]⁺	162.031 7	163.039 1	87.280 0	-0.970 0	7-Hydroxy-coumarin	Coumarin	YC
7	3.817 0	C₆H₆O₃	[M+H]⁺	126.031 8	127.038 6	46.700 0	3.010 0	1,2,4-Benzenetriol	Phenol
8	3.892 0	C₁₀H₁₀O₄	[M+H]⁺	194.058 3	195.064 1	92.280 0	4.720 0	Ferulic acid	Phenylpropanoid	YC
9	3.892 0	C₂₁H₂₄O₁₁	[M+H]⁺	452.131 2	453.139 2	88.150 0	0.270 0	Catechin-5-O-β-D-glucopyranoside	Flavonoid	DH
10	4.131 0	C₉H₇NO	[M+H]⁺	145.052 4	146.059 7	79.520 0	3.240 0	4-Formylindole	Alkaloid	YC
11	4.471 0	C₃₀H₂₆O₁₂	[M+H]⁺	578.143 0	579.148 9	91.340 0	1.850 0	Proanthocyanidin B1	Flavonoid	DH
12	4.471 0	C₃₀H₂₆O₁₂	[M+H]⁺	578.143 0	579.148 9	91.340 0	1.850 0	Proanthocyanidin B2	Flavonoid	DH
13	4.471 0	C₃₀H₂₆O₁₂	[M+H]⁺	578.143 0	579.148 9	91.340 0	1.850 0	Proanthocyanidin B3	Flavonoid	DH
14	4.471 0	C₃₀H₂₆O₁₂	[M+H]⁺	578.143 0	579.148 9	91.340 0	1.850 0	Proanthocyanidin B4	Flavonoid	DH
15	4.471 0	C₃₀H₂₆O₁₂	[M+H]⁺	578.143 0	579.148 9	91.340 0	1.850 0	Proanthocyanidin B7	Flavonoid	DH
16	4.471 0	C₂₈H₂₈O₁₂	[M+Na]⁺	556.158 1	579.149 4	69.400 0	-3.410 0	Deoxyearth rhein-8-O-gallate	Phenol	DH
17	4.744 0	C₁₅H₁₄O₆	[M+H]⁺	290.079 0	291.086 9	97.620 0	-2.050 0	Catechins	Flavonoid	DH
18	4.876 0	C₉H₁₄O₄	[M+Na]⁺	186.089 2	209.081 3	70.670 0	-16.050 0	Azelaic acid	Fatty acid	YC
19	4.975 0	C₁₇H₂₂O	[M+Na]⁺	242.166 5	265.154 9	50.460 0	12.450 0	Dehydrofusarinol	Polyacetylene alcohol	YC
20	5.124 0	C₁₀H₁₆O	[M+H]⁺	152.120 8	153.128 2	74.050 0	-4.530 0	Arborone	Volatile oil	YC
21	5.190 0	C₂₇H₃₀O₁₅	[M+H]⁺	594.159 0	595.166 5	96.570 0	-0.820 0	Nicotilorin	Flavonoid	YC
22	5.232 0	C₁₀H₈O₃	[M+H]⁺	176.047 3	177.055 1	84.560 0	-2.450 0	7-Methoxy-coumarin	Coumarin	YC
23	5.232 0	C₁₁H₁₄O₅	[M+H]⁺	226.084 1	227.092 4	95.620 0	-3.860 0	Genipine	Terpenoid	ZZ
24	5.232 0	C₁₆H₂₄O₁₀	[M+H]⁺	376.139 1	377.146 8	78.580 0	-5.830 0	Mussaenosidic acid	Terpenoid	ZZ
25	5.323 0	C₂₇H₃₀O₁₆	[M+H]⁺	610.154 5	611.161 9	93.460 0	-1.900 0	Rutin	Flavonoid	YC
26	5.562 0	C₁₆H₂₆O₇	[M+H]⁺	330.168 2	331.175 1	77.220 0	-2.190 0	Epijasminoside A	Quinone	ZZ
27	5.653 0	C₈H₈O₂	[M+H]⁺	136.052 4	137.059 4	75.990 0	0.750 0	Anisaldehyde	Volatile oil	ZZ
28	5.926 0	C₁₂H₁₀O₅	[M+H]⁺	234.053 1	235.060 3	81.610 0	-1.000 0	2-Methyl-5-carboxymethyl-7-hydroxychromone	Quinone	DH
29	6.017 0	C₁₅H₁₀O₇	[M+H]⁺	302.044 0	303.051 1	74.000 0	-3.480 0	Quercetin	Flavonoid	YC
30	6.059 0	C₁₀H₈O₄	[M+H]⁺	192.042 3	193.050 1	84.460 0	-3.140 0	7-Methylchestnut baretin	Coumarin	YC
31	6.059 0	C₁₀H₈O₄	[M+H]⁺	192.042 3	193.050 1	84.460 0	-3.140 0	Scopolamine	Coumarin	YC
32	6.059 0	C₁₀H₈O₄	[M+H]⁺	192.042 3	193.050 1	84.460 0	-3.140 0	Isoscopolamine	Coumarin	YC
33	6.059 0	C₁₅H₁₀O₇	[M+H]⁺	302.042 7	303.051 0	76.000 0	-3.150 0	Mulberry pigment	Flavonoid	YC
34	6.059 0	C₂₁H₂₀O₁₂	[M+H]⁺	464.095 5	465.105 3	35.150 0	-5.470 0	Hypericin	Flavonoid	YC
35	6.208 0	C₂₁H₂₂O₉	[M+H]⁺	418.126 9	419.134 4	96.440 0	-1.200 0	Gardenia	Flavonoid	ZZ
36	6.208 0	C₁₉H₂₄O₉	[M+Na]⁺	396.145 5	419.134 4	60.190 0	-7.300 0	2-(2'-Hydroxypropyl)-5-methyl-7-hydroxychromotone-7-O-β-D-glucopyranoside	Phenol	DH
37	6.282 0	C₂₈H₃₂O₁₆	[M+H]⁺	624.168 8	625.175 8	72.530 0	0.510 0	Narcissine	Flavonoid	YC
38	6.373 0	C₁₃H₁₂O₄	[M+H]⁺	232.074 8	233.082 1	73.050 0	-4.790 0	2-Methyl-5-propanyl-7-hydroxychromoketone	Quinone	DH
39	6.398 0	C₁₃H₁₄O₄	[M+H]⁺	234.090 2	235.097 7	89.320 0	-5.530 0	2-(2'-Hydroxypropyl)-5-methyl-7-hydroxychromone	Phenol	DH
40	6.414 0	C₂₂H₂₂O₁₂	[M+H]⁺	478.111 1	479.118 8	98.430 0	-0.510 0	Isorhamnein-3-O-galactoside	Flavonoid	YC
41	6.414 0	C₂₂H₂₂O₁₂	[M+H]⁺	478.111 1	479.118 8	98.430 0	-0.510 0	Isorhamnein-3-O-glucoside	Flavonoid	YC
42	6.414 0	C₂₂H₂₂O₁₂	[M+H]⁺	478.111 1	479.118 2	80.180 0	0.170 0	2-O-Coumaryl-1-O-galloyl-β-D-glucose	Tannin	DH
43	6.497 0	C₁₆H₁₂O₇	[M+H]⁺	316.060 0	317.067 9	65.160 0	3.390 0	Capillarisin	Flavonoid	YC
44	6.671 0	C₁₁H₁₀O₄	[M+H]⁺	206.058 6	207.066 3	69.780 0	3.390 0	Inchen chromogenone	Coumarin	YC
45	6.985 0	C₁₁H₁₀O₃	[M+H]⁺	190.063 6	191.071 0	91.540 0	-3.760 0	2,5-Dimethyl-7-hydroxychromoton	Quinone	DH
46	7.696 0	C₂₀H₂₄O₉	[M+H]⁺	408.143 5	409.151 5	66.150 0	-5.090 0	Casidone-8-O-β-D-glucopyranoside	Phenol	DH
47	7.895 0	C₁₅H₁₀O₄	[M+H]⁺	254.059 2	255.066 5	79.670 0	-5.130 0	Chrysophanol	Quinone	DH
48	8.416 0	C₁₆H₁₂O₅	[M+H]⁺	284.069 6	285.077 4	75.400 0	-5.120 0	Physcion	Quinone	DH
49	15.190 0	C₁₈H₃₀O₂	[M+H]⁺	278.225 4	279.233 2	68.450 0	-4.540 0	Linolenic acid or its isomer	Fatty acid	YC
50	0.674 0	C₂₆H₃₀O₁₂	[M-H]^-	534.176 1	533.168 8	71.030 0	-4.350 0	p-Coumaryl genipin	Terpenoid	ZZ
51	1.601 0	C₁₃H₁₆O₁₀	[M-H]^-	332.075 4	331.068 8	67.170 0	-3.690 0	1-O-Gallic acyl fructose	Tannin	DH
52	1.601 0	C₇H₆O₅	[M-H]^-	170.021 5	169.015 0	96.620 0	-3.960 0	Gallic acid	Tannin	DH
53	3.429 0	C₁₉H₂₆O₁₅	[M-H]^-	494.125 5	493.118 9	96.660 0	1.920 0	1-O-Gallic acyl sucrose	Tannin	DH
54	3.577 0	C₁₆H₁₈O₉	[M-H]^-	354.095 1	355.102 5	97.520 0	-0.920 0	Chlorogenic acid	Phenylpropanoid	ZZ, YC
55	3.577 0	C₁₆H₁₈O₉	[M-H]^-	354.095 1	355.102 5	97.520 0	-0.920 0	Cryptochlorogenic acid	Phenylpropanoid	ZZ, YC
56	3.577 0	C₁₆H₁₈O₉	[M-H]^-	354.095 1	355.102 5	97.520 0	-0.920 0	Neochlorogenic acid	Phenylpropanoid	ZZ, YC
57	3.577 0	C₁₀H₁₂O₇	[M-H]^-	244.058 3	243.050 4	45.960 0	2.600 0	1-O-Gallic acylglycerol	Tannin	DH
58	3.875 0	C₁₆H₂₂O₁₀	[M-H]^-	373.113 0	374.121 3	72.000 0	1.410 0	Geniposide acid	Terpenoid	ZZ
59	3.875 0	C₁₆H₂₄O₁₁	[M-H]^-	392.132 2	391.125 0	92.130 0	-1.200 0	Mountain gardenoside	Terpenoid	ZZ
60	3.917 0	C₁₆H₂₂O₁₀	[M+Cl]^-	374.121 2	409.090 7	75.820 0	0.110 0	Gardenia new nucleoside	Terpenoid	ZZ
61	4.264 0	C₁₆H₂₆O₈	[M-H]^-	346.162 8	345.156 2	95.530 0	-1.030 0	Saffron picylate-β-D-glucopyranose	Terpenoid	ZZ
62	4.264 0	C₁₆H₂₆O₈	[M-H]^-	346.163 1	345.156 2	95.530 0	-1.030 0	Jasminoside B	Terpenoid	ZZ
63	4.727 0	C₃₁H₃₂O₁₆	[M+HCOO]^-	660.169 0	705.169 8	61.010 0	-4.250 0	3,5-Dicaffeyl-5-(3-hydroxy-3-methylglutaryl) quinic acid	Tannin	ZZ
64	4.727 0	C₃₁H₃₂O₁₆	[M+HCOO]^-	660.169 0	705.169 8	61.010 0	-4.250 0	3,4-Dio-cafeyl-5-O-(3-hydroxy-3-methyl) glutaryl quinic acid	Tannin	ZZ
65	4.727 0	C₃₁H₃₂O₁₆	[M+HCOO]^-	660.169 0	705.169 8	61.010 0	-4.250 0	3,5,6,4'-Tetrahydroxy 3',5'-dimethoxy flavone	Flavonoid	ZZ
66	4.727 0	C₃₁H₃₂O₁₆	[M+HCOO]^-	660.169 0	705.169 8	61.010 0	-4.250 0	3,5-Di-O-caffeyl-4-O-(3-hydroxy-3-methyl) alutaryl quinic acid	Tannin	ZZ
67	4.727 0	C₃₁H₃₂O₁₆	[M+HCOO]^-	660.169 0	705.169 8	61.010 0	-4.250 0	3-O-Ferulyl-4-O-(3-hydroxyl, 3-methyl) glutaryl-5-O-caffeyl quinic acid	Tannin	ZZ
68	4.744 0	C₁₄H₁₂O₄	[M+HCOO]^-	244.074 7	289.073 1	79.050 0	-4.840 0	Piceatannol	Phenol	DH
69	4.876 0	C₂₃H₃₄O₁₅	[M+HCOO]^-	550.193 4	595.192 0	76.820 0	-6.850 0	Genipin gentian diglycoside	Terpenoid	ZZ
70	4.984 0	C₂₃H₃₄O₁₅	[M+Cl]^-	550.193 4	585.163 7	72.240 0	-6.190 0	Genipin diglucopyranoside	Terpenoid	ZZ
71	5.017 0	C₉H₈O₄	[M-H]^-	180.043 4	179.036 1	79.040 0	-5.800 0	Caffeic acid	Phenylpropanoid	ZZ
72	5.240 0	C₁₇H₂₄O₁₀	[M+Cl]^-	388.140 8	423.110 0	75.980 0	-8.320 0	Geniposide methyl	Terpenoid	ZZ
73	5.240 0	C₁₇H₂₄O₁₀	[M+Cl]^-	388.140 8	423.110 0	75.980 0	-8.320 0	Geniposide	Terpenoid	ZZ
74	5.687 0	C₈H₈O₂	[M-H]^-	136.053 1	135.045 9	83.880 0	-4.670 0	p-Hydroxyacetophenone	Phenol	YC
75	6.009 0	C₂₅H₂₄O₁₂	[M-H]^-	516.126 8	515.121 7	74.530 0	-5.770 0	Dicaffeyl quinic acid isomers	Tannin	ZZ, YC
76	6.613 0	C₁₉H₂₆O₁₁	[M+HCOO]^-	430.146 7	475.144 9	85.300 0	-0.530 0	6'-O-Acetylgenipinside	Terpenoid	ZZ
77	6.613 0	C₁₉H₂₆O₁₁	[M+HCOO]^-	430.146 7	475.144 9	85.300 0	-0.530 0	10-Acetylgenipinside	Terpenoid	ZZ
78	6.621 0	C₂₅H₂₄O₁₂	[M-H]^-	516.127 6	515.119 8	88.230 0	-1.710 0	3,4-O-Dicaffeoyl quinic acid	Tannin	ZZ, YC
79	6.621 0	C₂₅H₂₄O₁₂	[M-H]^-	516.127 6	515.119 8	88.230 0	-1.710 0	1,4-Dicaffeyl quinic acid	Tannin	ZZ, YC
80	6.621 0	C₂₅H₂₄O₁₂	[M-H]^-	516.127 6	515.119 8	88.230 0	-1.710 0	Isochlorogenic acid A	Phenylpropanoid	ZZ, YC
81	6.621 0	C₂₅H₂₄O₁₂	[M-H]^-	516.127 6	515.119 8	88.230 0	-1.710 0	Isochlorogenic acid C	Phenylpropanoid	ZZ, YC
82	6.654 0	C₃₂H₄₀O₁₇	[M+Cl]^-	696.226 5	731.197 5	68.990 0	-3.460 0	6"-O-p-Coumaryl gentiobiglycoside	Terpenoid	ZZ
83	6.655 0	C₃₂H₄₀O₁₇	[M-H]^-	696.228 7	695.216 4	37.760 0	4.080 0	6"-O-trans-p-Coumaryl gentibiglycoside	Terpenoid	ZZ
84	7.027 0	C₂₁H₂₀O₉	[M+HCOO]^-	416.110 7	461.136 8	47.180 0	1.030 0	Chrysophanol-1-O-glucoside	Quinone	DH
85	7.027 0	C₂₁H₂₀O₉	[M+HCOO]^-	416.110 7	461.136 8	47.180 0	1.030 0	Chrysophanol-8-O-glucoside	Quinone	DH
86	7.515 0	C₂₂H₂₂O₁₁	[M-H]^-	462.118 0	461.111 5	81.940 0	-4.990 0	2-O-Cinnamyl-1-O-galloyl-β-D-glucose	Tannin	DH
87	8.788 0	C₁₆H₁₂O₅	[M-H]^-	284.068 5	283.062 5	41.600 0	-4.640 0	5,4'-Dihydroxy-7-methoxyflavone	Flavonoid	ZZ
88	9.955 0	C₁₅H₈O₆	[M-H]^-	284.032 1	283.025 1	78.820 0	-2.770 0	Emodin	Quinone	DH
89	11.328 0	C₁₅H₁₀O₅	[M-H]^-	270.052 8	269.047 3	69.020 0	-6.080 0	Rhein	Quinone	DH
90	11.344 0	C₁₅H₁₀O₅	[M-H]^-	270.054 0	269.047 4	67.920 0	-5.280 0	Aloe-emodin	Quinone	DH

No.

RT/min

Formula

Adduct

Mass

m/z

Score

Error/×10^-6

Compound