药学学报

No.	t_R /min	Compound	Formula	Precursor ion (m/z)	Error /×10^-6	Adducts	MS/MS (m/z)	Origion plant
1	1.540	Sucrose	C₁₂H₂₂O₁₁	341.109 2	2.3	[M-H]^-	323.235 7, 266.930 6, 179.056 2, 161.046 7, 119.035 8	B, S
2	1.592	Albiflorin*	C₂₃H₂₈O₁₁	525.180 7	-0.4	[M+HCOO]^-	357.126 8, 121.034 4	B
3	1.592	Desbenzoylpaeoniflorin	C₁₆H₂₄O₁₀	375.130 2	2.9	[M-H]^-	345.118 5, 195.060 2, 165.054 0	B
4	1.592	Quinic acid	C₇H₁₂O₆	191.055 1	-2.6	[M-H]^-	173.038 5, 127.045 3, 111.006 6, 93.034 2	G
5	1.643	p-Coumaric acid	C₉H₈O₃	165.054 9	-1.8	[M+H]⁺	147.082 8, 119.070 3	G
6	1.712	Tufulingoside	C₁₅H₁₆O₉	339.071 8	0.6	[M-H]^-	268.960 0, 193.014 1, 164.012 2, 136.016 2, 121.026 1, 108.020 1	T
7	1.780	Proanthocyanidin B23'-gallate	C₃₇H₃₀O₁₆	729.143 7	-2.6	[M-H]^-	515.132 0, 169.006 7	B
8	1.849	11-O-Galloylbergenin	C₂₁H₂₀O₁₃	479.080 7	-4.0	[M-H]^-	327.079 7, 151.005 2	B
9	1.900	1, 3, 6-O-Trigalloylglucose	C₂₇H₂₄O₁₈	635.090 9	3.9	[M-H]^-	331.065 5, 313.058 8, 169.012 0, 125.026 5	B
10	2.324	Citric acid	C₆H₈O₇	191.019 3	0.5	[M-H]^-	173.008 9, 165.054 0, 129.019 9, 111.006 6	B
11	2.546	Dihydroisoferulic acid	C₁₀H₁₂O₄	195.065 9	1.0	[M-H]^-	136.053 3, 121.030 3	G
12	3.124	6-O-Galloyl arbutin	C₁₉H₂₀O₁₁	423.092 5	-0.5	[M-H]^-	169.017 3	S
13	3.227	(-)-Epicatechin gallate	C₂₂H₁₈O₁₀	441.082 6	0.9	[M-H]^-	332.160 8, 271.064 4, 169.017 3	G
14	3.535	3-Galloylquinic acid	C₁₄H₁₆O₁₀	343.065 4	-3.2	[M-H]^-	301.234 6, 169.017 3, 123.046 5	G
15	4.473	Woodorien	C₁₄H₁₈O₉	329.088 2	2.7	[M-H]^-	167.036 4, 152.009 9, 123.044 3, 108.020 1	T
16	4.919	N₁-Caffeoyl, N₃-dihydrocaffeoyl	C₂₅H₃₅N₃O₆	472.245 0	0.4	[M-H]^-	287.053 5, 153.015 4	G
17	5.188	Ethyl gallate	C₉H₁₀O₅	197.045 3	1.5	[M-H]^-	182.022 2, 169.017 3, 168.863 1, 166.999 4, 153.020 5, 125.024 2	G
18	5.222	(+)-Catechin-5-O-glucoside	C₂₁H₂₄O₁₁	451.124 5	1.1	[M-H]^-	331.087 9, 289.070 9, 245.079 5	G
19	5.359	Protocatechuic acid-3-glucoside	C₁₃H₁₆O₉	315.071 0	-1.9	[M-H]^-	153.020 5, 123.046 5, 109.030 3	G
20	6.074	6-O-trans-Feruloyl-2-O-β-D-glucopyranosyl-α-D-glucopyranoside	C₂₂H₃₀O₁₄	517.153 7	-3.9	[M-H]^-	271.061 0, 193.048 2, 175.038 4	G
21	6.194	Paeoniflorin	C₂₃H₂₆O₁₀	461.143 2	-3.5	[M-H]^-	447.129 1	B
22	6.262	Oxypaeoniflorin	C₂₃H₂₈O₁₂	496.156 4	-3.4	[M-H]^-	465.136 4, 345.110 9, 333.093 6, 137.025 0	B
23	6.279	3, 4-di-O-Caffeoylquinic acid	C₂₂H₂₈O₁₄	515.141 2	2.1	[M-H]^-	353.076 7, 323.066 6, 164.043 6	G
24	6.468	Mudanpioside H	C₃₀H₃₂O₁₄	615.173 4	3.3	[M-H]^-	281.078 1, 191.032 5	B
25	6.502	p-Coumaric acid-glycosides isomer	C₁₅H₁₈O₈	325.092 2	-0.3	[M-H]^-	651.163 6, 163.039 0, 119.049 2	G
26	6.588	Catechin*	C₁₅H₁₄O₆	289.070 9	-1.0	[M-H]^-	289.070 9, 179.034 3, 151.040 3	G
27	7.989	Caffeic acid	C₉H₈O₄	179.034 3	-0.6	[M-H]^-	135.042 1	G
28	8.103	Silymarin	C₂₅H₂₂O₁₀	481.113 2	-0.6	[M-H]^-	407.077 9, 297.041 7, 283.022 7, 269.047 2, 256.034 1, 243.030 8, 180.010 2, 152.012 4	T
29	8.429	(3β, 20α)-3-Hydroxy-11-oxoolean-12-en-29-oic acid	C₃₀H₄₆O₄	469.333 1	2.8	[M-H]^-	311.164 9	B
30	8.437	Chlorogenic acid	C₁₆H₁₈O₉	353.088 2	2.5	[M-H]^-	353.088 2, 191.060 7, 179.034 3, 161.041 5, 135.044 5	G
31	9.040	Eugenin-3-glucoside	C₂₃H₂₄O₁₃	509.130 9	2.7	[M+H]⁺	345.064 4, 327.055 8	G
32	9.418	Gambiriin A₁ or A₆	C₃₀H₂₆O₁₁	561.141 9	3.9	[M-H]^-	407.073 8, 289.070 9, 273.075 6, 245.079 5, 203.069 7, 188.049 8, 179.034 3, 165.017 2, 151.040 3, 137.025 0, 125.021 9, 109.030 3	T
33	9.924	Paeoniflorin*	C₂₃H₂₈O₁₁	479.152 2	2.9	[M-H]^-	479.152 2, 449.140 9, 357.120 7, 327.105 6, 121.102 8	B
34	9.692	3, 5-di-O-Caffeoylquinic acid	C₂₂H₂₈O₁₄	515.141 2	2.1	[M-H]^-	353.084 4, 191.066 4, 179.031 6	G
35	10.012	Paeoniflorin R₁	C₂₃H₂₈O₁₁	479.156 7	2.9	[M-H]^-	283.091 6, 121.028 3	B
36	10.458	Isorhamnetin 3-O-rutinoside	C₂₈H₃₂O₁₆	625.179 2	3.7	[M+H]⁺	317.059 9	G
40.195	623.159 7	-2.4	[M-H]^-	315.060 1
37	10.630	(+)-Procyanidin B₂ or B₁	C₃₀H₂₆O₁₂	577.132 4	-3.8	[M-H]^-	407.086 2, 339.086 9, 289.070 9, 245.079 5, 205.048 2, 175.035 7, 161.026 0, 137.022 6, 125.021 9	T
38	10.733	Taxifolin-3-glucopyranoside	C₂₁H₂₂O₁₂	465.104 6	2.8	[M-H]^-	335.079 2, 293.018 2, 269.007 0, 256.997 4, 234.988 1, 216.981 9, 196.976 4, 161.023 4	T
39	10.767	Quercetin-3-O-galactoside	C₂₁H₂₀O₁₂	463.087 0	-1.5	[M-H]^-	301.032 3	G
40	10.870	Anthocyanin	C₂₇H₃₀O₁₅	593.149 2	-2.4	[M-H]^-	264.073 8, 263.070 8	G
41	11.053	3-O-Caffeoylshikimic acid	C₁₆H₁₆O₈	335.075 4	-3.9	[M-H]^-	203.069 7, 187.038 3, 161.026 0, 135.044 5, 133.028 9, 123.042 0	T
42	11.430	Mudanpioside E	C₂₄H₃₀O₁₃	525.158 7	-4.0	[M-H]^-	495.154 4, 193.053 9	B
43	19.359	Galloylpaeoniflorin	C₃₀H₃₂O₁₅	631.168 3	3.2	[M-H]^-	613.150 5, 491.120 1, 313.058 8, 169.014 7, 165.059 2	B
44	25.499	Kaempferol	C₁₅H₁₀O₆	285.039 7	-0.7	[M-H]^-	268.038 1, 267.030 9	B, S
45	25.516	Nicotiflorin	C₂₁H₂₀O₁₁	447.092 4	-0.7	[M-H]^-	285.039 7, 269.040 5, 257.043 3, 241.048 0, 177.022 6, 151.002 6	G
46	25.550	Neoastilbin^*	C₂₁H₂₂O₁₁	449.109 9	3.3	[M-H]^-	303.051 8, 285.039 7, 267.030 9, 241.051 1, 175.041 1, 150.031 3, 133.028 9, 123.044 3	T
47	25.584	Kaempferol-3-O-glucoside	C₂₁H₂₀O₁₁	447.092 4	-0.7	[M-H]^-	284.035 5, 191.066 4	G
48	25.601	Hydroxybenzoyl-O-benzoin	C₂₁H₂₀O₁₁	447.092 4	-0.7	[M-H]^-	249.037 9, 207.030 4, 192.012 1	S
49	29.197	Mudanpioside D	C₂₄H₃₀O₁₂	509.164 1	-3.5	[M-H]^-	121.028 3	B
50	37.795	Smilaside L	C₄₂H₄₆O₂₀	869.247 9	-2.9	[M-H]^-	804.449 7, 513.141 9, 499.145 7, 193.053 9, 175.041 1, 146.038 8	T
51	38.012	Engeletin	C₂₁H₂₂O₁₀	433.114 3	1.8	[M-H]^-	289.070 9, 269.043 9, 259.061 2, 215.072 5, 180.007 4, 152.009 9	T
52	38.201	Bis (galloyl)-O-cryptoxanthin	C₂₈H₂₄O₁₇	631.092 4	-1.7	[M-H]^-	461.077 3, 169.012 0	U
53	38.449	Notoginsenoside R₁	C₄₇H₈₀O₁₈	931.522 6	2.4	[M-H]^-	931.522 6, 799.484 7, 637.433 7, 475.380 0	S
54	38.801	Iristectorin A	C₂₃H₂₄O₁₂	491.120 1	2.2	[M-H]^-	285.039 7, 180.004 7, 151.002 6	T
55	38.818	Diacetyl-saikosaponin A or D	C₄₆H₇₂O₁₅	863.479 2	-0.1	[M+H]⁺	821.488 2, 779.475 3	C
56	38.835	Ginsenoside Rg₁	C₄₂H₇₂O₁₄	799.484 7	0.4	[M-H]^-	799.484 7, 637.428 6, 475.380 0	S
38.920	823.484 4	2.9	[M+Na]⁺	643.418 0, 203.057 7
57	38.835	Quinic acid	C₂₄H₂₀O₉	451.102 8	-0.2	[M-H]^-	281.047 2, 217.012 0, 203.034 7, 189.018 9, 177.019 8, 161.026 0, 151.040 3, 147.044 3, 133.028 9, 123.044 3, 109.028 2	T
58	38.886	Ar-Curcumene	C₁₅H₂₂	203.180 2	1.0	[M+H]⁺	201.166 7, 159.117 7, 121.102 0, 95.084 8	Y
59	38.887	Ginsenoside Rh₁	C₃₆H₆₂O₉	637.429 9	-2.7	[M-H]^-	637.428 6, 475.380 0	S
60	38.967	Astilbin sulfate	C₂₁H₂₂O₁₄S	529.066 6	2.6	[M-H]^-	383.004 8, 364.996 4, 285.039 7, 230.966 1, 228.980 6, 216.987 9, 181.052 0, 167.036 4, 151.005 2	T
61	39.001	Astilbin sulfate isomer	C₂₁H₂₂O₁₄S	529.066 6	2.6	[M-H]^-	383.004 8, 365.004 2, 285.039 7, 228.974 4, 212.986 4, 201.992 5, 177.017 1, 167.036 4, 151.002 6	T
62	39.293	Saikosaponin X	C₄₂H₆₆O₁₅	809.430 2	-2.6	[M-H]^-	809.430 2, 780.423 7, 779.418 2, 617.362 3	C
63	39.413	(Z)-(1S, 5R)-β-pinen-10-yl β-vicianoside	C₂₁H₃₄O₁₀	445.208 4	-2.2	[M-H]^-	293.088 3, 233.066 4, 191.055 1	B
64	39.636	Smilaside B	C₃₄H₄₀O₁₈	735.216 4	3.8	[M-H]^-	500.074 0, 418.060 5, 375.043 0, 337.093 2, 301.074 9, 265.072 1, 193.048 2, 175.038 4	T
65	39.721	Mururin A	C₂₄H₁₆O₉	447.070 8	-1.8	[M-H]^-	323.022 5, 295.021 3, 282.018 6, 267.027 6, 251.040 4, 240.045 3, 223.038 6, 211.038 2, 195.045 9	T
66	39.841	Linoleic acid	C₁₈H₃₂O₂	279.232 4	0.0	[M-H]^-	125.092 8, 71.014 9	S
67	39.893	Benzoyloxypeoniflorin	C₃₀H₃₂O₁₃	599.178 3	3.0	[M-H]^-	447.222 2, 313.066 1, 293.088 3, 165.054 0, 137.025 0, 121.028 3	S
68	39.910	Quercetin	C₁₅H₁₀O₇	301.035 9	3.7	[M-H]^-	301.035 9, 283.022 7, 255.026 8, 178.998 7, 151.002 6, 107.012 5	G, S
69	39.973	Caffeoyl-O-benzoin	C₂₃H₂₂O₁₂	489.104 6	2.7	[M-H]^-	249.037 9, 207.030 4, 192.009 2	S
70	40.042	Smilaside A	C₃₆H₄₂O₁₉	777.226 5	3.0	[M-H]^-	735.205 3, 717.205 3, 625.082 3, 559.166 4, 513.141 9, 499.145 7, 193.048 2, 175.038 4, 160.015 1	T
71	40.093	Benzoylpaeoniflorin	C₃₀H₃₂O₁₂	583.181 6	0.0	[M-H]^-	553.164 5, 461.121 2, 431.132 5, 327.083 4	B
72	40.162	Mudanpioside C	C₃₀H₃₂O₁₃	599.178 3	3.0	[M-H]^-	581.157 7, 477.130 2, 447.122 7, 137.015 4, 121.028 3	B
73	40.247	Ginsenoside Rc	C₅₃H₉₀O₂₂	1 077.585 3	0.7	[M-H]^-	1 077.585 3, 945.536 5, 783.484 4, 621.430 5, 459.387 5	S
74	40.299	Mudanpioside B	C₃₁H₃₄O₁₄	629.186 0	-1.6	[M-H]^-	583.181 6, 341.128 1, 121.028 3	B
75	40.325	Ginsenoside Rb₁	C₅₄H₉₂O₂₃	1 107.589 0	0.6	[M-H]^-	1 107.589 0, 945.542 8, 783.484 4, 621.435 5, 459.387 5	S
76	40.419	Notoginsenoside R₂	C₄₁H₇₀O₁₃	769.472 0	-2.3	[M-H]^-	769.472 0, 637.433 7, 475.375 6, 391.284 8, 101.022 7	S
77	40.470	Smilaside C	C₄₁H₄₄O₁₉	839.238 5	-1.7	[M-H]^-	693.209 4, 663.184 0, 645.189 5, 517.158 4, 499.141 1, 483.137 1, 337.089 5, 193.048 2, 175.038 4	T
78	40.590	Naringenin	C₁₅H₁₂O₅	271.061 0	1.5	[M-H]^-	270.061 0	G
79	40.590	3'-O-Acetylsaikosaponin A	C₄₄H₇₀O₁₄	821.468 2	-0.6	[M-H]^-	821.468 2, 779.452 5, 761.446 0, 617.403 0	C
80	40.607	trans-N-(4-Dihydroxy-3-methoxyphenethyl) feruloyloctopamine	C₁₆H₂₂O₈	343.139 8	1.5	[M-H]^-	283.129 5	G
81	40.676	Ginsenoside Ro	C₄₈H₇₆O₁₉	955.489 4	-0.9	[M-H]^-	955.489 4, 793.445 4, 569.381 4	S
82	40.676	Ginsenoside Rg₂	C₄₂H₇₂O₁₃	783.490 1	0.8	[M-H]^-	783.490 1, 637.423 4, 475.380 0, 391.284 8	S
83	40.693	Saikosaponin C	C₄₈H₇₈O₁₇	925.513 1	-3.2	[M-H]^-	925.513 1, 779.452 5, 771.499 4	C
84	40.830	Ginsenoside Re	C₄₈H₈₂O₁₈	945.542 8	0.5	[M-H]^-	945.542 8, 783.484 4, 637.423 4, 475.380 0	S
85	40.916	6-O-Galloylglucose	C₁₃H₁₆O₁₀	331.065 5	-3.0	[M-H]^-	331.065 5, 271.054 3, 211.026 3, 169.014 7	B
86	40.945	Ginsenoside Rh₂	C₃₆H₆₂O₈	621.435 5	-1.8	[M-H]^-	621.430 5, 459.387 5	S
87	40.962	Phenylpropanoid glycosides	C₃₈H₄₄O₂₀	819.232 2	-3.2	[M-H]^-	777.237 9, 760.232 7, 584.170 0, 559.166 4, 193.048 2, 175.038 4	T
88	41.048	Acetyl-saikosaponin A or D	C₅₀H₈₂O₁₈	969.541 7	-0.6	[M-H]^-	807.469 8, 499.305 7	C
89	41.476	Curcumolide A	C₁₅H₂₀O₃	249.150 1	4.0	[M+H]⁺	81.070 6	Y
90	41.631	Saikosaponin A	C₄₂H₆₈O₁₃	779.458 2	0.0	[M-H]^-	779.458 2, 617.403 0, 439.322 8	C
41.819	781.483 6	-2.0	[M+H]⁺	781.483 6, 619.431 2, 473.369 5
91	42.671	Saikosaponin E	C₄₂H₆₈O₁₂	763.462 7	-0.8	[M-H]^-	763.462 7, 601.413 9, 161.046 7	C
92	42.914	Curcumin*	C₂₁H₂₀O₆	369.133 0	-2.2	[M+H]⁺	159.084 2, 114.092 6	Y
93	43.128	Curzerene	C₁₅H₂₀O	217.160 0	3.7	[M+H]⁺	147.085 3, 119.088 2, 95.086 8, 79.058 3	Y
94	48.056	Ginsenoside Rk₁	C₄₂H₇₀O₁₂	765.476 4	-3.3	[M-H]^-	603.422 4	S
95	48.159	Saikosaponin B₄	C₄₃H₇₂O₁₄	811.486 1	2.1	[M-H]^-	811.486 1	C
96	49.268	Dibutyl phthalate	C₁₆H₂₂O₄	277.144 1	0.4	[M-H]^-	285.219 4, 148.055 7	B
97	52.303	Bisdemethoxycurcumin	C₁₉H₁₆O₄	309.112 3	-1.3	[M+H]⁺	177.051 1	Y
98	52.783	Cinnamic acid	C₉H₈O₂	149.059 9	-2.7	[M+H]⁺	130.067 1	G
99	52.801	23-Hydroxybetulinic acid	C₃₀H₄₈O₄	471.347 4	0.0	[M-H]^-	363.231 9, 241.219 5, 195.143 1, 171.111 7	B
100	53.258	Palmitic acid	C₁₆H₃₂O₂	255.232 7	1.2	[M-H]^-	241.219 5	B
101	53.653	Saikosaponin F	C₄₈H₈₀O₁₇	927.530 7	-1.1	[M-H]^-	927.530 7	C
102	53.738	Xanthohumol glucoside	C₁₇H₁₆O₉	365.086 7	-1.6	[M+H]⁺	305.092 3	U

No.	t_R /min	Compound	Formula	Precursor ion (m/z)	Error /×10^-6	Adducts	MS/MS (m/z)	Origion plant
1	1.540	Sucrose	C₁₂H₂₂O₁₁	341.109 2	2.3	[M-H]^-	323.235 7, 266.930 6, 179.056 2, 161.046 7, 119.035 8	B, S
2	1.592	Albiflorin*	C₂₃H₂₈O₁₁	525.180 7	-0.4	[M+HCOO]^-	357.126 8, 121.034 4	B
3	1.592	Desbenzoylpaeoniflorin	C₁₆H₂₄O₁₀	375.130 2	2.9	[M-H]^-	345.118 5, 195.060 2, 165.054 0	B
4	1.592	Quinic acid	C₇H₁₂O₆	191.055 1	-2.6	[M-H]^-	173.038 5, 127.045 3, 111.006 6, 93.034 2	G
5	1.643	p-Coumaric acid	C₉H₈O₃	165.054 9	-1.8	[M+H]⁺	147.082 8, 119.070 3	G
6	1.712	Tufulingoside	C₁₅H₁₆O₉	339.071 8	0.6	[M-H]^-	268.960 0, 193.014 1, 164.012 2, 136.016 2, 121.026 1, 108.020 1	T
7	1.780	Proanthocyanidin B23'-gallate	C₃₇H₃₀O₁₆	729.143 7	-2.6	[M-H]^-	515.132 0, 169.006 7	B
8	1.849	11-O-Galloylbergenin	C₂₁H₂₀O₁₃	479.080 7	-4.0	[M-H]^-	327.079 7, 151.005 2	B
9	1.900	1, 3, 6-O-Trigalloylglucose	C₂₇H₂₄O₁₈	635.090 9	3.9	[M-H]^-	331.065 5, 313.058 8, 169.012 0, 125.026 5	B
10	2.324	Citric acid	C₆H₈O₇	191.019 3	0.5	[M-H]^-	173.008 9, 165.054 0, 129.019 9, 111.006 6	B
11	2.546	Dihydroisoferulic acid	C₁₀H₁₂O₄	195.065 9	1.0	[M-H]^-	136.053 3, 121.030 3	G
12	3.124	6-O-Galloyl arbutin	C₁₉H₂₀O₁₁	423.092 5	-0.5	[M-H]^-	169.017 3	S
13	3.227	(-)-Epicatechin gallate	C₂₂H₁₈O₁₀	441.082 6	0.9	[M-H]^-	332.160 8, 271.064 4, 169.017 3	G
14	3.535	3-Galloylquinic acid	C₁₄H₁₆O₁₀	343.065 4	-3.2	[M-H]^-	301.234 6, 169.017 3, 123.046 5	G
15	4.473	Woodorien	C₁₄H₁₈O₉	329.088 2	2.7	[M-H]^-	167.036 4, 152.009 9, 123.044 3, 108.020 1	T
16	4.919	N₁-Caffeoyl, N₃-dihydrocaffeoyl	C₂₅H₃₅N₃O₆	472.245 0	0.4	[M-H]^-	287.053 5, 153.015 4	G
17	5.188	Ethyl gallate	C₉H₁₀O₅	197.045 3	1.5	[M-H]^-	182.022 2, 169.017 3, 168.863 1, 166.999 4, 153.020 5, 125.024 2	G
18	5.222	(+)-Catechin-5-O-glucoside	C₂₁H₂₄O₁₁	451.124 5	1.1	[M-H]^-	331.087 9, 289.070 9, 245.079 5	G
19	5.359	Protocatechuic acid-3-glucoside	C₁₃H₁₆O₉	315.071 0	-1.9	[M-H]^-	153.020 5, 123.046 5, 109.030 3	G
20	6.074	6-O-trans-Feruloyl-2-O-β-D-glucopyranosyl-α-D-glucopyranoside	C₂₂H₃₀O₁₄	517.153 7	-3.9	[M-H]^-	271.061 0, 193.048 2, 175.038 4	G
21	6.194	Paeoniflorin	C₂₃H₂₆O₁₀	461.143 2	-3.5	[M-H]^-	447.129 1	B
22	6.262	Oxypaeoniflorin	C₂₃H₂₈O₁₂	496.156 4	-3.4	[M-H]^-	465.136 4, 345.110 9, 333.093 6, 137.025 0	B
23	6.279	3, 4-di-O-Caffeoylquinic acid	C₂₂H₂₈O₁₄	515.141 2	2.1	[M-H]^-	353.076 7, 323.066 6, 164.043 6	G
24	6.468	Mudanpioside H	C₃₀H₃₂O₁₄	615.173 4	3.3	[M-H]^-	281.078 1, 191.032 5	B
25	6.502	p-Coumaric acid-glycosides isomer	C₁₅H₁₈O₈	325.092 2	-0.3	[M-H]^-	651.163 6, 163.039 0, 119.049 2	G
26	6.588	Catechin*	C₁₅H₁₄O₆	289.070 9	-1.0	[M-H]^-	289.070 9, 179.034 3, 151.040 3	G
27	7.989	Caffeic acid	C₉H₈O₄	179.034 3	-0.6	[M-H]^-	135.042 1	G
28	8.103	Silymarin	C₂₅H₂₂O₁₀	481.113 2	-0.6	[M-H]^-	407.077 9, 297.041 7, 283.022 7, 269.047 2, 256.034 1, 243.030 8, 180.010 2, 152.012 4	T
29	8.429	(3β, 20α)-3-Hydroxy-11-oxoolean-12-en-29-oic acid	C₃₀H₄₆O₄	469.333 1	2.8	[M-H]^-	311.164 9	B
30	8.437	Chlorogenic acid	C₁₆H₁₈O₉	353.088 2	2.5	[M-H]^-	353.088 2, 191.060 7, 179.034 3, 161.041 5, 135.044 5	G
31	9.040	Eugenin-3-glucoside	C₂₃H₂₄O₁₃	509.130 9	2.7	[M+H]⁺	345.064 4, 327.055 8	G
32	9.418	Gambiriin A₁ or A₆	C₃₀H₂₆O₁₁	561.141 9	3.9	[M-H]^-	407.073 8, 289.070 9, 273.075 6, 245.079 5, 203.069 7, 188.049 8, 179.034 3, 165.017 2, 151.040 3, 137.025 0, 125.021 9, 109.030 3	T
33	9.924	Paeoniflorin*	C₂₃H₂₈O₁₁	479.152 2	2.9	[M-H]^-	479.152 2, 449.140 9, 357.120 7, 327.105 6, 121.102 8	B
34	9.692	3, 5-di-O-Caffeoylquinic acid	C₂₂H₂₈O₁₄	515.141 2	2.1	[M-H]^-	353.084 4, 191.066 4, 179.031 6	G
35	10.012	Paeoniflorin R₁	C₂₃H₂₈O₁₁	479.156 7	2.9	[M-H]^-	283.091 6, 121.028 3	B
36	10.458	Isorhamnetin 3-O-rutinoside	C₂₈H₃₂O₁₆	625.179 2	3.7	[M+H]⁺	317.059 9	G
40.195	623.159 7	-2.4	[M-H]^-	315.060 1
37	10.630	(+)-Procyanidin B₂ or B₁	C₃₀H₂₆O₁₂	577.132 4	-3.8	[M-H]^-	407.086 2, 339.086 9, 289.070 9, 245.079 5, 205.048 2, 175.035 7, 161.026 0, 137.022 6, 125.021 9	T
38	10.733	Taxifolin-3-glucopyranoside	C₂₁H₂₂O₁₂	465.104 6	2.8	[M-H]^-	335.079 2, 293.018 2, 269.007 0, 256.997 4, 234.988 1, 216.981 9, 196.976 4, 161.023 4	T
39	10.767	Quercetin-3-O-galactoside	C₂₁H₂₀O₁₂	463.087 0	-1.5	[M-H]^-	301.032 3	G
40	10.870	Anthocyanin	C₂₇H₃₀O₁₅	593.149 2	-2.4	[M-H]^-	264.073 8, 263.070 8	G
41	11.053	3-O-Caffeoylshikimic acid	C₁₆H₁₆O₈	335.075 4	-3.9	[M-H]^-	203.069 7, 187.038 3, 161.026 0, 135.044 5, 133.028 9, 123.042 0	T
42	11.430	Mudanpioside E	C₂₄H₃₀O₁₃	525.158 7	-4.0	[M-H]^-	495.154 4, 193.053 9	B
43	19.359	Galloylpaeoniflorin	C₃₀H₃₂O₁₅	631.168 3	3.2	[M-H]^-	613.150 5, 491.120 1, 313.058 8, 169.014 7, 165.059 2	B
44	25.499	Kaempferol	C₁₅H₁₀O₆	285.039 7	-0.7	[M-H]^-	268.038 1, 267.030 9	B, S
45	25.516	Nicotiflorin	C₂₁H₂₀O₁₁	447.092 4	-0.7	[M-H]^-	285.039 7, 269.040 5, 257.043 3, 241.048 0, 177.022 6, 151.002 6	G
46	25.550	Neoastilbin^*	C₂₁H₂₂O₁₁	449.109 9	3.3	[M-H]^-	303.051 8, 285.039 7, 267.030 9, 241.051 1, 175.041 1, 150.031 3, 133.028 9, 123.044 3	T
47	25.584	Kaempferol-3-O-glucoside	C₂₁H₂₀O₁₁	447.092 4	-0.7	[M-H]^-	284.035 5, 191.066 4	G
48	25.601	Hydroxybenzoyl-O-benzoin	C₂₁H₂₀O₁₁	447.092 4	-0.7	[M-H]^-	249.037 9, 207.030 4, 192.012 1	S
49	29.197	Mudanpioside D	C₂₄H₃₀O₁₂	509.164 1	-3.5	[M-H]^-	121.028 3	B
50	37.795	Smilaside L	C₄₂H₄₆O₂₀	869.247 9	-2.9	[M-H]^-	804.449 7, 513.141 9, 499.145 7, 193.053 9, 175.041 1, 146.038 8	T
51	38.012	Engeletin	C₂₁H₂₂O₁₀	433.114 3	1.8	[M-H]^-	289.070 9, 269.043 9, 259.061 2, 215.072 5, 180.007 4, 152.009 9	T
52	38.201	Bis (galloyl)-O-cryptoxanthin	C₂₈H₂₄O₁₇	631.092 4	-1.7	[M-H]^-	461.077 3, 169.012 0	U
53	38.449	Notoginsenoside R₁	C₄₇H₈₀O₁₈	931.522 6	2.4	[M-H]^-	931.522 6, 799.484 7, 637.433 7, 475.380 0	S
54	38.801	Iristectorin A	C₂₃H₂₄O₁₂	491.120 1	2.2	[M-H]^-	285.039 7, 180.004 7, 151.002 6	T
55	38.818	Diacetyl-saikosaponin A or D	C₄₆H₇₂O₁₅	863.479 2	-0.1	[M+H]⁺	821.488 2, 779.475 3	C
56	38.835	Ginsenoside Rg₁	C₄₂H₇₂O₁₄	799.484 7	0.4	[M-H]^-	799.484 7, 637.428 6, 475.380 0	S
38.920	823.484 4	2.9	[M+Na]⁺	643.418 0, 203.057 7
57	38.835	Quinic acid	C₂₄H₂₀O₉	451.102 8	-0.2	[M-H]^-	281.047 2, 217.012 0, 203.034 7, 189.018 9, 177.019 8, 161.026 0, 151.040 3, 147.044 3, 133.028 9, 123.044 3, 109.028 2	T
58	38.886	Ar-Curcumene	C₁₅H₂₂	203.180 2	1.0	[M+H]⁺	201.166 7, 159.117 7, 121.102 0, 95.084 8	Y
59	38.887	Ginsenoside Rh₁	C₃₆H₆₂O₉	637.429 9	-2.7	[M-H]^-	637.428 6, 475.380 0	S
60	38.967	Astilbin sulfate	C₂₁H₂₂O₁₄S	529.066 6	2.6	[M-H]^-	383.004 8, 364.996 4, 285.039 7, 230.966 1, 228.980 6, 216.987 9, 181.052 0, 167.036 4, 151.005 2	T
61	39.001	Astilbin sulfate isomer	C₂₁H₂₂O₁₄S	529.066 6	2.6	[M-H]^-	383.004 8, 365.004 2, 285.039 7, 228.974 4, 212.986 4, 201.992 5, 177.017 1, 167.036 4, 151.002 6	T
62	39.293	Saikosaponin X	C₄₂H₆₆O₁₅	809.430 2	-2.6	[M-H]^-	809.430 2, 780.423 7, 779.418 2, 617.362 3	C
63	39.413	(Z)-(1S, 5R)-β-pinen-10-yl β-vicianoside	C₂₁H₃₄O₁₀	445.208 4	-2.2	[M-H]^-	293.088 3, 233.066 4, 191.055 1	B
64	39.636	Smilaside B	C₃₄H₄₀O₁₈	735.216 4	3.8	[M-H]^-	500.074 0, 418.060 5, 375.043 0, 337.093 2, 301.074 9, 265.072 1, 193.048 2, 175.038 4	T
65	39.721	Mururin A	C₂₄H₁₆O₉	447.070 8	-1.8	[M-H]^-	323.022 5, 295.021 3, 282.018 6, 267.027 6, 251.040 4, 240.045 3, 223.038 6, 211.038 2, 195.045 9	T
66	39.841	Linoleic acid	C₁₈H₃₂O₂	279.232 4	0.0	[M-H]^-	125.092 8, 71.014 9	S
67	39.893	Benzoyloxypeoniflorin	C₃₀H₃₂O₁₃	599.178 3	3.0	[M-H]^-	447.222 2, 313.066 1, 293.088 3, 165.054 0, 137.025 0, 121.028 3	S
68	39.910	Quercetin	C₁₅H₁₀O₇	301.035 9	3.7	[M-H]^-	301.035 9, 283.022 7, 255.026 8, 178.998 7, 151.002 6, 107.012 5	G, S
69	39.973	Caffeoyl-O-benzoin	C₂₃H₂₂O₁₂	489.104 6	2.7	[M-H]^-	249.037 9, 207.030 4, 192.009 2	S
70	40.042	Smilaside A	C₃₆H₄₂O₁₉	777.226 5	3.0	[M-H]^-	735.205 3, 717.205 3, 625.082 3, 559.166 4, 513.141 9, 499.145 7, 193.048 2, 175.038 4, 160.015 1	T
71	40.093	Benzoylpaeoniflorin	C₃₀H₃₂O₁₂	583.181 6	0.0	[M-H]^-	553.164 5, 461.121 2, 431.132 5, 327.083 4	B
72	40.162	Mudanpioside C	C₃₀H₃₂O₁₃	599.178 3	3.0	[M-H]^-	581.157 7, 477.130 2, 447.122 7, 137.015 4, 121.028 3	B
73	40.247	Ginsenoside Rc	C₅₃H₉₀O₂₂	1 077.585 3	0.7	[M-H]^-	1 077.585 3, 945.536 5, 783.484 4, 621.430 5, 459.387 5	S
74	40.299	Mudanpioside B	C₃₁H₃₄O₁₄	629.186 0	-1.6	[M-H]^-	583.181 6, 341.128 1, 121.028 3	B
75	40.325	Ginsenoside Rb₁	C₅₄H₉₂O₂₃	1 107.589 0	0.6	[M-H]^-	1 107.589 0, 945.542 8, 783.484 4, 621.435 5, 459.387 5	S
76	40.419	Notoginsenoside R₂	C₄₁H₇₀O₁₃	769.472 0	-2.3	[M-H]^-	769.472 0, 637.433 7, 475.375 6, 391.284 8, 101.022 7	S
77	40.470	Smilaside C	C₄₁H₄₄O₁₉	839.238 5	-1.7	[M-H]^-	693.209 4, 663.184 0, 645.189 5, 517.158 4, 499.141 1, 483.137 1, 337.089 5, 193.048 2, 175.038 4	T
78	40.590	Naringenin	C₁₅H₁₂O₅	271.061 0	1.5	[M-H]^-	270.061 0	G
79	40.590	3'-O-Acetylsaikosaponin A	C₄₄H₇₀O₁₄	821.468 2	-0.6	[M-H]^-	821.468 2, 779.452 5, 761.446 0, 617.403 0	C
80	40.607	trans-N-(4-Dihydroxy-3-methoxyphenethyl) feruloyloctopamine	C₁₆H₂₂O₈	343.139 8	1.5	[M-H]^-	283.129 5	G
81	40.676	Ginsenoside Ro	C₄₈H₇₆O₁₉	955.489 4	-0.9	[M-H]^-	955.489 4, 793.445 4, 569.381 4	S
82	40.676	Ginsenoside Rg₂	C₄₂H₇₂O₁₃	783.490 1	0.8	[M-H]^-	783.490 1, 637.423 4, 475.380 0, 391.284 8	S
83	40.693	Saikosaponin C	C₄₈H₇₈O₁₇	925.513 1	-3.2	[M-H]^-	925.513 1, 779.452 5, 771.499 4	C
84	40.830	Ginsenoside Re	C₄₈H₈₂O₁₈	945.542 8	0.5	[M-H]^-	945.542 8, 783.484 4, 637.423 4, 475.380 0	S
85	40.916	6-O-Galloylglucose	C₁₃H₁₆O₁₀	331.065 5	-3.0	[M-H]^-	331.065 5, 271.054 3, 211.026 3, 169.014 7	B
86	40.945	Ginsenoside Rh₂	C₃₆H₆₂O₈	621.435 5	-1.8	[M-H]^-	621.430 5, 459.387 5	S
87	40.962	Phenylpropanoid glycosides	C₃₈H₄₄O₂₀	819.232 2	-3.2	[M-H]^-	777.237 9, 760.232 7, 584.170 0, 559.166 4, 193.048 2, 175.038 4	T
88	41.048	Acetyl-saikosaponin A or D	C₅₀H₈₂O₁₈	969.541 7	-0.6	[M-H]^-	807.469 8, 499.305 7	C
89	41.476	Curcumolide A	C₁₅H₂₀O₃	249.150 1	4.0	[M+H]⁺	81.070 6	Y
90	41.631	Saikosaponin A	C₄₂H₆₈O₁₃	779.458 2	0.0	[M-H]^-	779.458 2, 617.403 0, 439.322 8	C
41.819	781.483 6	-2.0	[M+H]⁺	781.483 6, 619.431 2, 473.369 5
91	42.671	Saikosaponin E	C₄₂H₆₈O₁₂	763.462 7	-0.8	[M-H]^-	763.462 7, 601.413 9, 161.046 7	C
92	42.914	Curcumin*	C₂₁H₂₀O₆	369.133 0	-2.2	[M+H]⁺	159.084 2, 114.092 6	Y
93	43.128	Curzerene	C₁₅H₂₀O	217.160 0	3.7	[M+H]⁺	147.085 3, 119.088 2, 95.086 8, 79.058 3	Y
94	48.056	Ginsenoside Rk₁	C₄₂H₇₀O₁₂	765.476 4	-3.3	[M-H]^-	603.422 4	S
95	48.159	Saikosaponin B₄	C₄₃H₇₂O₁₄	811.486 1	2.1	[M-H]^-	811.486 1	C
96	49.268	Dibutyl phthalate	C₁₆H₂₂O₄	277.144 1	0.4	[M-H]^-	285.219 4, 148.055 7	B
97	52.303	Bisdemethoxycurcumin	C₁₉H₁₆O₄	309.112 3	-1.3	[M+H]⁺	177.051 1	Y
98	52.783	Cinnamic acid	C₉H₈O₂	149.059 9	-2.7	[M+H]⁺	130.067 1	G
99	52.801	23-Hydroxybetulinic acid	C₃₀H₄₈O₄	471.347 4	0.0	[M-H]^-	363.231 9, 241.219 5, 195.143 1, 171.111 7	B
100	53.258	Palmitic acid	C₁₆H₃₂O₂	255.232 7	1.2	[M-H]^-	241.219 5	B
101	53.653	Saikosaponin F	C₄₈H₈₀O₁₇	927.530 7	-1.1	[M-H]^-	927.530 7	C
102	53.738	Xanthohumol glucoside	C₁₇H₁₆O₉	365.086 7	-1.6	[M+H]⁺	305.092 3	U

UPLC-Q-TOF/MS^E分析鉴定肝豆扶木汤化学成分

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黄蕾 ¹ , 王倪 ¹ , 董婷 ²^,^* , 曹仕健 ² , 蒋羽鸽 ³^,⁴ , 吴欢 ³^,⁴ , 周安 ¹^,³^,⁴^,^*

药学学报 | 研究论文 2025,60(3): 771-783

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药学学报 | 研究论文 2025, 60(3): 771-783

UPLC-Q-TOF/MS^E分析鉴定肝豆扶木汤化学成分

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黄蕾¹, 王倪¹, 董婷²^,^*, 曹仕健², 蒋羽鸽³^,⁴, 吴欢³^,⁴, 周安¹^,³^,⁴^,^*

作者信息

1.安徽中医药大学药学院, 安徽合肥 230012

2.安徽中医药大学第一附属医院, 安徽合肥 230031

3.新安医学教育部重点实验室, 安徽合肥 230012

4.食药用菌功能活性与资源利用安徽省联合共建学科重点实验室, 安徽六安 237399

通讯作者:

^*董婷, E-mail: dongting2002@sina.com

周安, Tel: 86-551-65169752, E-mail: anzhou@ahtcm.edu.cn

Identification of chemical components in Gandoufumu Decoction by UPLC-Q-TOF/MS^E

Lei HUANG¹, Ni WANG¹, Ting DONG²^,^*, Shi-jian CAO², Yu-ge JIANG³^,⁴, Huan WU³^,⁴, An ZHOU¹^,³^,⁴^,^*

Affiliations

1. School of Pharmacy, Anhui University of Chinese Medicine, Hefei 230012, China

2. The First Affiliated Hospital of Anhui University of Chinese Medicine, Hefei 230031, China

3. Key Laboratory of Xin'An Medicine, Ministry of Education, Hefei 230012, China

4. Functional Activity and Resource Utilization on Edible and Medicinal Fungi Joint Laboratory of Anhui Province, Lu'an 237399, China

出版时间: 2025-03-12 doi: 10.16438/j.0513-4870.2024-0917

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摘要

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通过超高效液相色谱串联四极杆飞行时间质谱技术(UPLC-Q-TOF/MS^E) 对肝豆扶木汤的化学成分进行分析鉴定; 采用ZORBAX RRHD Eclipse Plus C₁₈色谱柱(2.1 mm × 100 mm, 1.8 μm), 以0.1%甲酸水-乙腈为流动相进行梯度洗脱, 流速为0.2 mL·min^-1, 柱温35 ℃。质谱分析采用电喷雾电离源(ESI) 的方式, 在正、负离子模式下, 通过UPLC-Q-TOF/MS^E分析鉴定肝豆扶木汤的化学成分。共鉴定出102种化合物, 其中黄酮类成分26个, 萜类成分22个, 皂苷类成分19个, 苯丙素类成分10个和其他类成分25个。本研究所建立的定性分析方法能快速、高效地对肝豆扶木汤的化学成分进行分析鉴定, 为肝豆扶木汤的质量评价和临床应用提供了科学依据。

关键词

肝豆扶木汤 / UPLC-Q-TOF/MS^E / 化学成分 / 定性分析 / 裂解规律

Abstract

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The main chemical components of Gandoufumu Decoction (GDFMD) were analyzed and identified using ultra-performance liquid chromatography quadrupole time-of-flight mass spectrometry (UPLC-Q-TOF/MS^E). We utilized a ZORBAX RRHD Eclipse Plus C₁₈ column (2.1 mm × 100 mm, 1.8 μm) with a gradient elution of 0.1% formic acid in water and acetonitrile as mobile phase at a flow rate of 0.2 mL·min^-1 and a column temperature of 35 ℃. The mass spectrometry was analyzed using an electrospray ionization source (ESI) in positive and negative ion modes. The UPLC-Q-TOF/MS^E was used to detect and analyze the complex mass spectra and the chemical composition of the GDFMD. The results show that 102 compounds were identified in GDFMD, 26 flavonoids, 22 terpenoids, 19 saponins, 10 phenylpropanoids, and 25 other components. The established qualitative method can rapidly and efficiently identify the chemical components of GDFMD, providing a scientific basis for the quality evaluation and clinical application of GDFMD.

Key words

Gandoufumu Decoction / UPLC-Q-TOF/MS^E / chemical composition / qualitative analysis / fragmentation pattern

引用本文

黄蕾, 王倪, 董婷, 曹仕健, 蒋羽鸽, 吴欢, 周安. UPLC-Q-TOF/MS^E分析鉴定肝豆扶木汤化学成分. 药学学报, 2025 , 60 (3) : 771 -783 . DOI: 10.16438/j.0513-4870.2024-0917

Lei HUANG, Ni WANG, Ting DONG, Shi-jian CAO, Yu-ge JIANG, Huan WU, An ZHOU. Identification of chemical components in Gandoufumu Decoction by UPLC-Q-TOF/MS^E[J]. Acta Pharmaceutica Sinica, 2025 , 60 (3) : 771 -783 . DOI: 10.16438/j.0513-4870.2024-0917

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威尔逊病(Wilson's disease, WD), 又称肝豆状核变性, 是一种由铜代谢障碍引起的遗传性疾病^[1]。该病发病机制为患者体内ATP7B基因突变致使铜蓝蛋白合成障碍无法排出体内的铜, 进而引起铜在多个器官沉积, 造成大脑和肝脏为主的器官质性损害^{[2, 3]}。WD的临床药物治疗主要以青霉胺为代表的重金属螯合剂, 金属螯合剂药物可通过络合铜离子发挥促进铜体内排泄作用, 然而该类药物不良反应较多, 药物安全性较差, 约20%~30%接受青霉胺治疗的患者出现了神经系统症状恶化，临床应用受到了很大限制^[4]。

肝豆扶木汤(Gandoufumu Decoction, GDFMD) 是安徽中医药大学第一附属医院杨文明教授经多年的临床实践拟定方剂, 临床实践证实该方可通过促进体内铜排泄从而显著改善WD患者的肝纤维化症状, 临床效果显著^[5]。GDFMD联合常规保肝排铜药(二巯丙磺钠、还原型谷胱甘肽) 治疗, 能有效地改善患者肝纤维化相关指标, 对于逆转WD肝纤维化进程起到有效的临床干预作用^[6]。动物和细胞实验表明, GDFMD可通过调控TGF-β1/Smad、SLC7A11/GPX4等信号通路相关因子的蛋白及基因表达, 抑制肝细胞铁死亡, 有效防治WD肝损伤的发生^{[7, 8]}。

尽管GDFMD治疗WD疗效显著, 但关于系统分析鉴定GDFMD中化学成分的研究相对较少, 对该汤剂中化合物成分质谱裂解规律总结分析尚未见报道, 限制了对其物质基础及作用机制的深入研究。已有文献^[9]报道采用超高效液相色谱-四极杆/静电场轨道阱高分辨质谱法对GDFMD中的化学成分进行鉴定, 共鉴别出了82个化合物, 包括酚类、生物碱、皂苷、倍半萜、游离酚和有机酸, 但其缺少主要类别化合物的裂解途径、研究范围主要为酚类和皂苷类, 不能全面反映GDFMD的整体化学成分。超高效液相色谱串联四极杆飞行时间质谱(UPLC-Q-TOF/MS^E) 具有高分离性能、高分辨率和高灵敏度等特点, 可以快速简便地分析鉴定中药化合物信息, 对复杂中药成分进行全面筛选分析, 广泛应用于中药成分分析^{[10, 11]}。

本研究以GDFMD为研究对象, 采用UPLC-Q-TOF/MS^E对其成分进行快速分析鉴定并对化合物进行归类和归属, 为GDFMD的药效物质基础与临床应用提供理论依据和数据支持。

材料与方法

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仪器 Waters Acquity UPLC超高效液相色谱系统和Waters Xevo G2QTOF高分辨率飞行时间质谱仪(美国Waters公司); RE-2000A旋转蒸发仪(上海亚荣生化仪器厂); ALPHA1-2LD真空冷冻干燥机(德国CHRIST公司), Milli-Q超纯水净化系统(美国Milli-Q公司)。

饮片白芍为毛茛科植物芍药(Paeonia lactiflora Pall.) 的干燥根, 产地安徽, 批号: 2308067; 枸杞子为茄科植物宁夏枸杞(Lycium barbarum L.) 的干燥成熟果实, 产地宁夏, 批号: 220902; 土茯苓为百合科植物光叶菝葜(Smilax glabra Roxb.) 的干燥根茎, 产地广西, 批号: 221001; 三七为五加科植物三七[Panax notoginseng (Burk.) F. H. Chen] 的干燥根和根茎, 产地云文山, 批号: 210702; 柴胡为伞形科植物柴胡(Bupleurum chinense DC.) 的干燥根, 产地甘肃, 批号: 231203; 郁金为姜科植物温郁金(Curcuma rcenyujin Y, H. Chenet C. Ling) 的干燥块根, 产地广西, 批号: 2209027, 均购于合肥市同仁堂大药房, 由安徽中医药大学药学院生药系俞年军教授鉴定。

试药儿茶素(批号: S01HB191501)、落新妇苷(批号: D26GB172582)、芍药苷(批号: M28GB143089)、姜黄素(批号: M13GB148382) 均购于上海源叶生物科技有限公司; 芍药内酯苷(批号: 39011900) 购于上海同田生物技术股份有限公司, 纯度均≥ 98%。甲酸(LC-MS级) 购于美国Sigma-Aldrich公司; 甲醇(HPLC级) 和乙腈(LC-MS级) 购自德国Merck公司; 超纯水由Milli-Q超纯水净化系统(美国Milli-Q公司) 制得。GDFMD样品为实验室制备得到。

GDFMD提取物与标准品溶液制备

GDFMD提取物制备取白芍15 g、枸杞12 g、土茯苓12 g、三七3 g、柴胡10 g、郁金10 g, 合计62 g, 加超纯水10倍(620 mL), 浸泡1 h后, 煮沸, 再以文火煎煮两次, 每次30 min, 过滤, 合并两次滤液。旋转浓缩至一定体积, 放置-80 ℃冰箱进行冷冻处理, 真空冷冻干燥制备得到GDFMD冻干粉, 得率为31.65%, 低温避光保存; 取1.0 g冻干粉(相当于3.1 g生药材), 加30 mL甲醇, 超声提取30 min, 并加甲醇补足重量, 进样前用0.22 μm微孔滤膜过滤作为供试品溶液备用。取复方同比例单味药材，按上述方法制备各单味药材供试品供质谱分析使用。

对照品混合溶液的制备分别精密称取儿茶素、芍药苷、芍药内酯苷、落新妇苷和姜黄素约1.0 mg, 加甲醇配制成浓度为1 mg·mL^-1的对照品储备液, 精密吸取各储备液混合, 并稀释成各对照品浓度约20 µg·mL^-1的混合对照品溶液, 经0.22 µm滤膜过滤后进样分析。

色谱条件 色谱柱: Agilent Eclipse Plus C₁₈ (2.1 mm × 100 mm, 1.8 μm), 流动相: 0.1%甲酸水(A) 和乙腈(B), 洗脱梯度: 0~5 min, 95%~87% A; 5~10 min, 87% A; 10~20 min, 87%~86% A; 20~35 min, 86%~85% A; 35~40 min, 85%~49% A; 40~50 min, 49%~40% A; 50~52 min, 40%~5% A; 52~54 min, 5% A; 54~56 min, 5%~95% A。流速: 0.2 mL·min^-1, 进样体积: 2 μL, 柱温: 35 ℃。

质谱条件 质谱扫描范围m/z 50~1 200, 毛细电压3.0 kV (ESI⁺) 或2.5 kV (ESI^-), 锥孔电压40 V, 离子源温度120 ℃, 去溶剂化温度350 ℃, 溶剂气流量600 L·h^-1。MS^E低碰撞能量设置为6 V, 高碰撞能量设置为20~80 V。在进样分析前, 利用调谐液校正QTOF-MS/MS质量轴, 数据采集过程中使用亮氨酸脑啡肽进行实时校准。在ESI⁺模式下选择[(M+H)⁺ = 556.277 1], ESI^-模式下选择[(M-H)^- = 554.261 5] 分别对质谱进行校正, 校正通过后采集数据。

GDFMD化学成分数据库的建立 对PubMed、Chemspider、SciFinder、CNKI等数据库进行系统性的检索, 收集GDFMD中6味药材(即白芍、枸杞、三七、土茯苓、柴胡和郁金) 的化学成分信息, 共收集352种化合物的信息, 包括化合物的名称、结构、化学式、精确分子量等信息, 将其制成Excel电子表格, 同时用ChemDraw绘制结构式并保存.mol文件即得GDFMD化学成分自建数据库。

结果

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1 GDFMD化学成分分析

按上述色谱质谱条件进样供试品和对照品, MassLynx 4.1软件(Waters) 质谱工作站采用化学成分数据信息, 得到各色谱峰的保留时间、精确分子量、碎片峰信息。在GDFMD中共鉴定出102种化合物, 含黄酮类成分26个, 萜类成分22个, 皂苷类成分19个, 苯丙素类成分10个和其他类成分25个。正、负离子模式下获取样品总离子流图, 详见图 1, 最终筛查到的化学成分和药材归属, 见表 1。

2 黄酮类化合物鉴定

GDFMD中检出数量占比最高的化合物为黄酮类化合物, 这是一类具有C₆-C₃-C₆结构的化合物^{[12, 13]}, 常见的取代基有酚羟基、甲氧基、甲基、异戊烯基等^[14], 此类化合物往往具有较强的抗氧化活性, 如山柰酚、槲皮素等^[15]。在碎裂MS/MS谱图中, 黄酮类除了常见的小分子中性丢失外, 特征反应包括C环发生的逆狄尔斯-阿尔德反应(RDA) 裂解和氢重排^[16], 即C₁与C₂位和C₃与C₄位断裂, 生成A环和B环两个碎片离子。此外, 黄酮苷类化合物在二级质谱中通常表现为脱去糖基形成苷元离子^[17]。根据以上裂解特征结合对照品质谱信息共鉴定出GDFMD中26种黄酮类化合物, 包括化合物6、12、13、15、18、19、26、28、32、36、37、38、39、40、44、45、46、47、51、54、60、61、65、68、78、102, 含黄烷醇类1种。

以化合物68为例, 在负离子模式下, 准分子离子[M-H]^-的m/z为301.035 9, 推测其化学式为C₁₅H₁₀O₇。该化合物的C环的^{1, 4}B键、^{1, 3}A键和^{1, 3}B键发生RDA裂解形成178.998 7 [M-H-C₇H₆O₂]^-、151.002 6 [M-H-C₈H₆O₃]^-, 该碎片离子继续中性丢失CO₂产生特征碎片离子m/z 107.012 5。化合物中性丢失一分子H₂O产生m/z 283.022 7碎片离子, 该碎片继续中性丢失CO产生特征碎片离子m/z 255.026 8。基于上述裂解特征判定该化合物为槲皮素, 其二级质谱及裂解途径^[18]见图 2A。

黄烷醇类生源上是由二氢黄酮醇类还原而来, 可看成是脱去C₄位羰基氧原子后的二氢黄酮醇类, 又称为儿茶素类^[19]。儿茶素类化合物是一类含有两个或两个以上的芳香环和多个羟基的化合物, 具有清除自由基、抗氧化, 调节血糖血脂, 抗炎抗肿瘤等生物活性^[19]。以特征性化合物26为例, 其准分子离子[M-H]^-的m/z为289.070 9, 推测其化学式为C₁₅H₁₄O₆。在质谱的高碰撞能作用下碎片离子主要发生了C环的逆狄尔斯-阿尔德裂解和B环丢失分别产生特征碎片离子125.026 5 [M-H-C₇H₄O₄-C₉H₈O₄]^-和179.034 3 [M-H-C₇H₄O₄-C₅H₂O₄]^-, 特征碎片离子中性丢失一分子CO可产生碎片离子m/z 151.040 3。综合以上裂解规律, 结合对照品信息判定该化合物为儿茶素, 如图 2B。

3 萜类化合物鉴定

从GDFMD复方中分离得到22个萜类化学成分, 分别为化合物2、3、21、22、24、29、31、33、35、42、43、49、58、63、67、71、72、74、79、89、93、99, 这些化合物分为单萜类、倍半萜类和三萜类。单萜类化合物在质谱裂解中常丢失H₂O和CH₂O分子, 或失去糖基分子, 在该过程中常伴随着分子重排裂解, 尤其以麦氏重排多见^{[20, 21]}, 常出现失去苯甲酸的离子碎片的情况; 倍半萜类化合物和三萜类化合物常以游离形式或以糖结合成苷或酯的形式存在, 其质谱裂解规律以糖苷键的断裂为主, 裂解过程中可能会丢失1个或多个H₂O^{[16, 22]}。

以化合物33为例, 准分子离子[M-H]^-的m/z为479.152 2, 推测其化学式为C₂₃H₂₈O₁₁。在负离子模式下, 由一、二级质谱数据可知m/z 479.152 2为[M-H]^-峰, 二级质谱有m/z 449.140 9 [M-H-CH₂O]^-、m/z 357.120 7 [M-H-C₇H₆O₂]^-、m/z 327.105 6 [M-H-HCHO-C₇H₆O₂]^-、m/z 121.102 8 [M-H-C₁₆H₂₂O₉]⁺等碎片离子。对照文献^[23-25]及对照品质谱信息, 鉴定化合物33为芍药苷, 如图 3。

4 皂苷类化合物鉴定

GDFMD中鉴定的皂苷类化合物有19个, 包括化合物53、55、56、59、62、73、75、76、81、82、83、84、86、88、90、91、94、95、101。皂苷类化合物在质谱分析过程中会经历一系列复杂的化学反应和断裂过程, 主要包括糖丢失的过程及苷元的进一步裂解。

4.1 I型皂苷

人参皂苷Rc、Rb₁、Rh₂、Rk₁ (化合物73、75、86、94) 这四种物质均为I型皂苷, 即原人参二醇型皂苷。它们的特点是糖链部分通常连接苷元C-3位和C-20位, 而C-6位未被取代, 在一级质谱中产生强度较高的[M+HCOO]^-和[M-H]^-离子峰。据报道^[26], 在多数的人参皂苷裂解规律研究中仅发现皂苷上糖的断裂, 而未发现负离子模式下苷元的进一步裂解, 主要可能是因为四环三萜皂苷具有较稳定的、难以破坏的皂苷元结构。

以化合物75为例, 准分子离子[M-H]^-的m/z为1 107.589 0, 推测其化学式为C₅₄H₉₂O₂₃。该分子离子峰相继失去四分子葡萄糖, 得到m/z 945.542 8、783.484 4、621.435 5、459.387 5这些主要碎片离子, m/z 459.387 5为其苷元。与文献^[27]报道的人参皂苷Rb₁相近, 推测75为人参皂苷Rb₁, 如图 4所示。

4.2 II型皂苷

三七皂苷R₁、R₂, 人参皂苷Rg₁、Rh₁、Rg₂、Re (化合物53、76、56、59、82、84) 均为II型人参皂苷, 即原人参三醇型三萜皂苷。与I型皂苷结构母核不同的是, II型人参皂苷C-6位有羟基且由糖链取代, 而C-3无取代^[28]。尽管二者结构上的差别不大, 但在裂解碎片离子上的差别较大。II型皂苷特征碎片离子为m/z 475.37和m/z 391.28。其中, 苷元碎片离子m/z 475.37同I型皂苷相同, 四环上的烷基取代C-17支链容易失去, 从而得到去掉C-17支链丰度较大的m/z 391.28碎片离子。

以化合物53为例, 准分子离子[M-H]^-的m/z为931.522 6, 推测其化学式为C₄₇H₈₀O₁₈。其C-6位羟基和C-20位羟基分别有2个糖链, C-6位R₁为二糖, 由葡萄糖和木糖通过2→1键连接的, 而C-20位为一分子葡萄糖。在一级质谱中, 基峰为[M-H]^-的m/z 931.522 6。在二级质谱中, m/z 799.484 7、637.433 7和475.380 0分别为[M-H-xyl]^-、[M-H-xyl-glc]^-、[M-H-xyl-glc-glc]^-苷元。与文献^[27]报道的三七皂苷R₁相近, 推测53为三七皂苷R₁, 如图 5所示。

4.3 三萜皂苷类

柴胡皂苷在结构上属于五环三萜类化合物, 同时也是齐墩果烷型衍生物^[28]。包括化合物55、62、81、83、88、90、91、95、101。通过对化合物90进行质谱分析, 确定了其正离子m/z 781.483 6 [M+H]⁺和负离子m/z 779.458 2 [M-H]^-, 由此得到该化合物的相对分子质量为780.466 0, 分子式为C₄₂H₆₈O₁₃。正离子模式下, 在二级质谱图中可以观察到准分子离子峰781.483 6 [M+H]⁺丢失1分子葡萄糖基形成619.431 2 [M+H-Glc]⁺碎片离子; 丢失1分子葡萄糖基和一分子岩藻糖基形成473.369 5 [M+H-Glc-Fuc]⁺碎片离子(图 6A)。在负离子模式下, 准分子离子峰为m/z 779.458 2 [M-H]^-, 进一步分析二级碎片信息发现, 该分子离子先丢失一分子六碳糖形成m/z 617.403 0, 再丢失一分子脱氧六碳糖和一分子CH₃OH形成m/z 439.322 8 (图 6B), 与文献^{[29, 30]}中柴胡皂苷A二级碎片基本吻合, 因此确定90号峰为柴胡皂苷A。

5 苯丙素类化合物鉴定

苯丙素类化合物广泛分布于药用植物中, 是一类苯环与3个直链碳连接(C6-C3基团) 构成的化合物^[31]。共鉴定出10个苯丙素类, 包括化合物5、25、30、50、64、70、77、80、87、98。以化合物30为例, 其准分子离子峰[M-H]^-为353.088 2, 分子式为C₁₆H₁₈O₉。由于C₉H₆O₃和C₇H₁₀O₅的损失, 产生了m/z 191.060 7 [M-H-C₉H₆O₃]^-的奎宁碎片和179.034 3 [M-H-C₇H₁₀O₅]^-的咖啡酸碎片。此外, 产物离子161.041 5 [M-H-C₇H₁₀O₅-H₂O]^-、135.044 5 [M-H-C₇H₁₀O₅-CO₂]^-是由m/z 179.034 3通过咖啡碎片继续丢失1分子H₂O或CO₂而得到的。根据上述信息与文献^[32]信息, 推测化合物30为绿原酸, 其MS²图和碎片裂解途径如图 7所示。

6 其他类化合物鉴定

其他类别化合物共25种, 包括姜黄素类、酯类、鞣质类、酚酸类等。举例来说, 以化合物4为例, 其在负离子模式下形成一个准分子离子, 该离子的质量数为191.055 1, 推测其分子式为C₇H₁₂O₆; 进一步分析其二级质谱可发现, 一系列的碎片离子连续丢失包括H₂O、HCOOH、O、H₂O₂得碎片离子m/z 173.038 5 [M-H-H₂O]^-, m/z 127.045 3 [M-H-H₂O-HCOOH]^-, m/z 111.006 6 [M-H-H₂O-HCOOH-O]^-, m/z 93.034 2 [M-H-H₂O-HCOOH-O-H₂O]^-。根据上述信息与文献^[33]信息, 推测化合物4为奎宁酸。

讨论

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本研究通过UPLC-Q-TOF/MS^E对GDFMD中主要化学成分进行了全面的分析与鉴定。从GDFMD中鉴定出102种化合物, 正离子模式下检测到化合物13个, 负离子模式下的化合物有90个, 主要原因是该方中化合物在正离子模式下质谱响应信号较低, 在裂解规律分析中, 二级质谱信号较弱, 共有13个化合物能进行较好匹配。在负离子模式下, 大部分化合物响应较好, 能较准确地确定二级离子。本研究选择了儿茶素、落新妇苷、芍药苷、芍药内酯苷和姜黄素这五种成分, 其中儿茶素、落新妇苷属于黄酮类化合物, 芍药苷和芍药内酯苷属于萜类化合物, 姜黄素属于其他类, 包含了该方主要的三种类型化合物, 可进一步验证化学数据库及鉴定结果的准确性。在鉴定到的化合物中, 26种黄酮类成分、10种苯丙素类成分主要来源于枸杞和土茯苓; 22种萜类成分主要来源于白芍和土茯苓; 19种皂苷类成分主要来源于柴胡和三七; 25种其他类成分主要来源于白芍、枸杞和三七。药理学研究表明, 黄酮类化合物中的儿茶素能调节心肌细胞增殖、降低炎症反应, 对神经系统和肝肾组织起保护作用^[34]; 萜类化合物中的芍药苷和芍药内酯苷, 研究表明具有保护神经抗抑郁、保肝、保护胃肠黏膜、调节胃肠功能等作用^[35]; 皂苷类化合物中的柴胡皂苷A、人参皂苷Rg₁、三七皂苷R₁均具有抗炎、保护肝脏、抗菌、抗肿瘤等作用^{[36, 37]}; 苯丙素类成分具有抗菌、预防和治疗癌症等功效^[33]。以上研究表明, GDFMD中的各种药物活性成分可协同或互补发挥作用, 实现抗肝纤维化和抗炎等临床疗效。与之前研究者应用超高效液相色谱-四极杆/静电场轨道阱高分辨质谱法对GDFMD中的多类别化合物进行化学成分鉴定相比, 较全面完整地分析鉴定了该方剂中化学成分, 同时对方剂中的化学成分质谱裂解规律进行了系统分析总结。为进一步深入探究其药效物质基础、作用机制和临床应用奠定了坚实的理论基础。

作者贡献: 黄蕾负责数据库构建、样品测试及文章撰写; 王倪负责样品制备及文献查询; 曹仕健、蒋羽鸽、吴欢负责结构解析; 董婷、周安负责课题监管、文章撰写、文章审阅及技术指导。

利益冲突: 本文中所有作者声明无任何利益冲突。

基金

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国家自然科学基金项目(81872976)
安徽省卫生与健康研究(AHWJ2022b062)
安徽省红十字会中医药传承创新与发展研究项目(2022ZYYD06)
安徽省临床医学研究转化专项(202204295107020043)

参考文献

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2025年第60卷第3期

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doi: 10.16438/j.0513-4870.2024-0917

接收时间：2024-09-19
首发时间：2025-11-06
出版时间：2025-03-12

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收稿日期：2024-09-19
修回日期：2024-12-17

基金

国家自然科学基金项目(81872976)

安徽省卫生与健康研究(AHWJ2022b062)

安徽省红十字会中医药传承创新与发展研究项目(2022ZYYD06)

安徽省临床医学研究转化专项(202204295107020043)

作者信息

1.安徽中医药大学药学院, 安徽合肥 230012

2.安徽中医药大学第一附属医院, 安徽合肥 230031

3.新安医学教育部重点实验室, 安徽合肥 230012

4.食药用菌功能活性与资源利用安徽省联合共建学科重点实验室, 安徽六安 237399

通讯作者:

^*董婷, E-mail: dongting2002@sina.com

周安, Tel: 86-551-65169752, E-mail: anzhou@ahtcm.edu.cn

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https://castjournals.cast.org.cn/joweb/yxxb/CN/10.16438/j.0513-4870.2024-0917

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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	Compound	Formula	Precursor ion (m/z)	Error /×10^-6	Adducts	MS/MS (m/z)	Origion plant
1	1.540	Sucrose	C₁₂H₂₂O₁₁	341.109 2	2.3	[M-H]^-	323.235 7, 266.930 6, 179.056 2, 161.046 7, 119.035 8	B, S
2	1.592	Albiflorin*	C₂₃H₂₈O₁₁	525.180 7	-0.4	[M+HCOO]^-	357.126 8, 121.034 4	B
3	1.592	Desbenzoylpaeoniflorin	C₁₆H₂₄O₁₀	375.130 2	2.9	[M-H]^-	345.118 5, 195.060 2, 165.054 0	B
4	1.592	Quinic acid	C₇H₁₂O₆	191.055 1	-2.6	[M-H]^-	173.038 5, 127.045 3, 111.006 6, 93.034 2	G
5	1.643	p-Coumaric acid	C₉H₈O₃	165.054 9	-1.8	[M+H]⁺	147.082 8, 119.070 3	G
6	1.712	Tufulingoside	C₁₅H₁₆O₉	339.071 8	0.6	[M-H]^-	268.960 0, 193.014 1, 164.012 2, 136.016 2, 121.026 1, 108.020 1	T
7	1.780	Proanthocyanidin B23'-gallate	C₃₇H₃₀O₁₆	729.143 7	-2.6	[M-H]^-	515.132 0, 169.006 7	B
8	1.849	11-O-Galloylbergenin	C₂₁H₂₀O₁₃	479.080 7	-4.0	[M-H]^-	327.079 7, 151.005 2	B
9	1.900	1, 3, 6-O-Trigalloylglucose	C₂₇H₂₄O₁₈	635.090 9	3.9	[M-H]^-	331.065 5, 313.058 8, 169.012 0, 125.026 5	B
10	2.324	Citric acid	C₆H₈O₇	191.019 3	0.5	[M-H]^-	173.008 9, 165.054 0, 129.019 9, 111.006 6	B
11	2.546	Dihydroisoferulic acid	C₁₀H₁₂O₄	195.065 9	1.0	[M-H]^-	136.053 3, 121.030 3	G
12	3.124	6-O-Galloyl arbutin	C₁₉H₂₀O₁₁	423.092 5	-0.5	[M-H]^-	169.017 3	S
13	3.227	(-)-Epicatechin gallate	C₂₂H₁₈O₁₀	441.082 6	0.9	[M-H]^-	332.160 8, 271.064 4, 169.017 3	G
14	3.535	3-Galloylquinic acid	C₁₄H₁₆O₁₀	343.065 4	-3.2	[M-H]^-	301.234 6, 169.017 3, 123.046 5	G
15	4.473	Woodorien	C₁₄H₁₈O₉	329.088 2	2.7	[M-H]^-	167.036 4, 152.009 9, 123.044 3, 108.020 1	T
16	4.919	N₁-Caffeoyl, N₃-dihydrocaffeoyl	C₂₅H₃₅N₃O₆	472.245 0	0.4	[M-H]^-	287.053 5, 153.015 4	G
17	5.188	Ethyl gallate	C₉H₁₀O₅	197.045 3	1.5	[M-H]^-	182.022 2, 169.017 3, 168.863 1, 166.999 4, 153.020 5, 125.024 2	G
18	5.222	(+)-Catechin-5-O-glucoside	C₂₁H₂₄O₁₁	451.124 5	1.1	[M-H]^-	331.087 9, 289.070 9, 245.079 5	G
19	5.359	Protocatechuic acid-3-glucoside	C₁₃H₁₆O₉	315.071 0	-1.9	[M-H]^-	153.020 5, 123.046 5, 109.030 3	G
20	6.074	6-O-trans-Feruloyl-2-O-β-D-glucopyranosyl-α-D-glucopyranoside	C₂₂H₃₀O₁₄	517.153 7	-3.9	[M-H]^-	271.061 0, 193.048 2, 175.038 4	G
21	6.194	Paeoniflorin	C₂₃H₂₆O₁₀	461.143 2	-3.5	[M-H]^-	447.129 1	B
22	6.262	Oxypaeoniflorin	C₂₃H₂₈O₁₂	496.156 4	-3.4	[M-H]^-	465.136 4, 345.110 9, 333.093 6, 137.025 0	B
23	6.279	3, 4-di-O-Caffeoylquinic acid	C₂₂H₂₈O₁₄	515.141 2	2.1	[M-H]^-	353.076 7, 323.066 6, 164.043 6	G
24	6.468	Mudanpioside H	C₃₀H₃₂O₁₄	615.173 4	3.3	[M-H]^-	281.078 1, 191.032 5	B
25	6.502	p-Coumaric acid-glycosides isomer	C₁₅H₁₈O₈	325.092 2	-0.3	[M-H]^-	651.163 6, 163.039 0, 119.049 2	G
26	6.588	Catechin*	C₁₅H₁₄O₆	289.070 9	-1.0	[M-H]^-	289.070 9, 179.034 3, 151.040 3	G
27	7.989	Caffeic acid	C₉H₈O₄	179.034 3	-0.6	[M-H]^-	135.042 1	G
28	8.103	Silymarin	C₂₅H₂₂O₁₀	481.113 2	-0.6	[M-H]^-	407.077 9, 297.041 7, 283.022 7, 269.047 2, 256.034 1, 243.030 8, 180.010 2, 152.012 4	T
29	8.429	(3β, 20α)-3-Hydroxy-11-oxoolean-12-en-29-oic acid	C₃₀H₄₆O₄	469.333 1	2.8	[M-H]^-	311.164 9	B
30	8.437	Chlorogenic acid	C₁₆H₁₈O₉	353.088 2	2.5	[M-H]^-	353.088 2, 191.060 7, 179.034 3, 161.041 5, 135.044 5	G
31	9.040	Eugenin-3-glucoside	C₂₃H₂₄O₁₃	509.130 9	2.7	[M+H]⁺	345.064 4, 327.055 8	G
32	9.418	Gambiriin A₁ or A₆	C₃₀H₂₆O₁₁	561.141 9	3.9	[M-H]^-	407.073 8, 289.070 9, 273.075 6, 245.079 5, 203.069 7, 188.049 8, 179.034 3, 165.017 2, 151.040 3, 137.025 0, 125.021 9, 109.030 3	T
33	9.924	Paeoniflorin*	C₂₃H₂₈O₁₁	479.152 2	2.9	[M-H]^-	479.152 2, 449.140 9, 357.120 7, 327.105 6, 121.102 8	B
34	9.692	3, 5-di-O-Caffeoylquinic acid	C₂₂H₂₈O₁₄	515.141 2	2.1	[M-H]^-	353.084 4, 191.066 4, 179.031 6	G
35	10.012	Paeoniflorin R₁	C₂₃H₂₈O₁₁	479.156 7	2.9	[M-H]^-	283.091 6, 121.028 3	B
36	10.458	Isorhamnetin 3-O-rutinoside	C₂₈H₃₂O₁₆	625.179 2	3.7	[M+H]⁺	317.059 9	G
40.195	623.159 7	-2.4	[M-H]^-	315.060 1
37	10.630	(+)-Procyanidin B₂ or B₁	C₃₀H₂₆O₁₂	577.132 4	-3.8	[M-H]^-	407.086 2, 339.086 9, 289.070 9, 245.079 5, 205.048 2, 175.035 7, 161.026 0, 137.022 6, 125.021 9	T
38	10.733	Taxifolin-3-glucopyranoside	C₂₁H₂₂O₁₂	465.104 6	2.8	[M-H]^-	335.079 2, 293.018 2, 269.007 0, 256.997 4, 234.988 1, 216.981 9, 196.976 4, 161.023 4	T
39	10.767	Quercetin-3-O-galactoside	C₂₁H₂₀O₁₂	463.087 0	-1.5	[M-H]^-	301.032 3	G
40	10.870	Anthocyanin	C₂₇H₃₀O₁₅	593.149 2	-2.4	[M-H]^-	264.073 8, 263.070 8	G
41	11.053	3-O-Caffeoylshikimic acid	C₁₆H₁₆O₈	335.075 4	-3.9	[M-H]^-	203.069 7, 187.038 3, 161.026 0, 135.044 5, 133.028 9, 123.042 0	T
42	11.430	Mudanpioside E	C₂₄H₃₀O₁₃	525.158 7	-4.0	[M-H]^-	495.154 4, 193.053 9	B
43	19.359	Galloylpaeoniflorin	C₃₀H₃₂O₁₅	631.168 3	3.2	[M-H]^-	613.150 5, 491.120 1, 313.058 8, 169.014 7, 165.059 2	B
44	25.499	Kaempferol	C₁₅H₁₀O₆	285.039 7	-0.7	[M-H]^-	268.038 1, 267.030 9	B, S
45	25.516	Nicotiflorin	C₂₁H₂₀O₁₁	447.092 4	-0.7	[M-H]^-	285.039 7, 269.040 5, 257.043 3, 241.048 0, 177.022 6, 151.002 6	G
46	25.550	Neoastilbin^*	C₂₁H₂₂O₁₁	449.109 9	3.3	[M-H]^-	303.051 8, 285.039 7, 267.030 9, 241.051 1, 175.041 1, 150.031 3, 133.028 9, 123.044 3	T
47	25.584	Kaempferol-3-O-glucoside	C₂₁H₂₀O₁₁	447.092 4	-0.7	[M-H]^-	284.035 5, 191.066 4	G
48	25.601	Hydroxybenzoyl-O-benzoin	C₂₁H₂₀O₁₁	447.092 4	-0.7	[M-H]^-	249.037 9, 207.030 4, 192.012 1	S
49	29.197	Mudanpioside D	C₂₄H₃₀O₁₂	509.164 1	-3.5	[M-H]^-	121.028 3	B
50	37.795	Smilaside L	C₄₂H₄₆O₂₀	869.247 9	-2.9	[M-H]^-	804.449 7, 513.141 9, 499.145 7, 193.053 9, 175.041 1, 146.038 8	T
51	38.012	Engeletin	C₂₁H₂₂O₁₀	433.114 3	1.8	[M-H]^-	289.070 9, 269.043 9, 259.061 2, 215.072 5, 180.007 4, 152.009 9	T
52	38.201	Bis (galloyl)-O-cryptoxanthin	C₂₈H₂₄O₁₇	631.092 4	-1.7	[M-H]^-	461.077 3, 169.012 0	U
53	38.449	Notoginsenoside R₁	C₄₇H₈₀O₁₈	931.522 6	2.4	[M-H]^-	931.522 6, 799.484 7, 637.433 7, 475.380 0	S
54	38.801	Iristectorin A	C₂₃H₂₄O₁₂	491.120 1	2.2	[M-H]^-	285.039 7, 180.004 7, 151.002 6	T
55	38.818	Diacetyl-saikosaponin A or D	C₄₆H₇₂O₁₅	863.479 2	-0.1	[M+H]⁺	821.488 2, 779.475 3	C
56	38.835	Ginsenoside Rg₁	C₄₂H₇₂O₁₄	799.484 7	0.4	[M-H]^-	799.484 7, 637.428 6, 475.380 0	S
38.920	823.484 4	2.9	[M+Na]⁺	643.418 0, 203.057 7
57	38.835	Quinic acid	C₂₄H₂₀O₉	451.102 8	-0.2	[M-H]^-	281.047 2, 217.012 0, 203.034 7, 189.018 9, 177.019 8, 161.026 0, 151.040 3, 147.044 3, 133.028 9, 123.044 3, 109.028 2	T
58	38.886	Ar-Curcumene	C₁₅H₂₂	203.180 2	1.0	[M+H]⁺	201.166 7, 159.117 7, 121.102 0, 95.084 8	Y
59	38.887	Ginsenoside Rh₁	C₃₆H₆₂O₉	637.429 9	-2.7	[M-H]^-	637.428 6, 475.380 0	S
60	38.967	Astilbin sulfate	C₂₁H₂₂O₁₄S	529.066 6	2.6	[M-H]^-	383.004 8, 364.996 4, 285.039 7, 230.966 1, 228.980 6, 216.987 9, 181.052 0, 167.036 4, 151.005 2	T
61	39.001	Astilbin sulfate isomer	C₂₁H₂₂O₁₄S	529.066 6	2.6	[M-H]^-	383.004 8, 365.004 2, 285.039 7, 228.974 4, 212.986 4, 201.992 5, 177.017 1, 167.036 4, 151.002 6	T
62	39.293	Saikosaponin X	C₄₂H₆₆O₁₅	809.430 2	-2.6	[M-H]^-	809.430 2, 780.423 7, 779.418 2, 617.362 3	C
63	39.413	(Z)-(1S, 5R)-β-pinen-10-yl β-vicianoside	C₂₁H₃₄O₁₀	445.208 4	-2.2	[M-H]^-	293.088 3, 233.066 4, 191.055 1	B
64	39.636	Smilaside B	C₃₄H₄₀O₁₈	735.216 4	3.8	[M-H]^-	500.074 0, 418.060 5, 375.043 0, 337.093 2, 301.074 9, 265.072 1, 193.048 2, 175.038 4	T
65	39.721	Mururin A	C₂₄H₁₆O₉	447.070 8	-1.8	[M-H]^-	323.022 5, 295.021 3, 282.018 6, 267.027 6, 251.040 4, 240.045 3, 223.038 6, 211.038 2, 195.045 9	T
66	39.841	Linoleic acid	C₁₈H₃₂O₂	279.232 4	0.0	[M-H]^-	125.092 8, 71.014 9	S
67	39.893	Benzoyloxypeoniflorin	C₃₀H₃₂O₁₃	599.178 3	3.0	[M-H]^-	447.222 2, 313.066 1, 293.088 3, 165.054 0, 137.025 0, 121.028 3	S
68	39.910	Quercetin	C₁₅H₁₀O₇	301.035 9	3.7	[M-H]^-	301.035 9, 283.022 7, 255.026 8, 178.998 7, 151.002 6, 107.012 5	G, S
69	39.973	Caffeoyl-O-benzoin	C₂₃H₂₂O₁₂	489.104 6	2.7	[M-H]^-	249.037 9, 207.030 4, 192.009 2	S
70	40.042	Smilaside A	C₃₆H₄₂O₁₉	777.226 5	3.0	[M-H]^-	735.205 3, 717.205 3, 625.082 3, 559.166 4, 513.141 9, 499.145 7, 193.048 2, 175.038 4, 160.015 1	T
71	40.093	Benzoylpaeoniflorin	C₃₀H₃₂O₁₂	583.181 6	0.0	[M-H]^-	553.164 5, 461.121 2, 431.132 5, 327.083 4	B
72	40.162	Mudanpioside C	C₃₀H₃₂O₁₃	599.178 3	3.0	[M-H]^-	581.157 7, 477.130 2, 447.122 7, 137.015 4, 121.028 3	B
73	40.247	Ginsenoside Rc	C₅₃H₉₀O₂₂	1 077.585 3	0.7	[M-H]^-	1 077.585 3, 945.536 5, 783.484 4, 621.430 5, 459.387 5	S
74	40.299	Mudanpioside B	C₃₁H₃₄O₁₄	629.186 0	-1.6	[M-H]^-	583.181 6, 341.128 1, 121.028 3	B
75	40.325	Ginsenoside Rb₁	C₅₄H₉₂O₂₃	1 107.589 0	0.6	[M-H]^-	1 107.589 0, 945.542 8, 783.484 4, 621.435 5, 459.387 5	S
76	40.419	Notoginsenoside R₂	C₄₁H₇₀O₁₃	769.472 0	-2.3	[M-H]^-	769.472 0, 637.433 7, 475.375 6, 391.284 8, 101.022 7	S
77	40.470	Smilaside C	C₄₁H₄₄O₁₉	839.238 5	-1.7	[M-H]^-	693.209 4, 663.184 0, 645.189 5, 517.158 4, 499.141 1, 483.137 1, 337.089 5, 193.048 2, 175.038 4	T
78	40.590	Naringenin	C₁₅H₁₂O₅	271.061 0	1.5	[M-H]^-	270.061 0	G
79	40.590	3'-O-Acetylsaikosaponin A	C₄₄H₇₀O₁₄	821.468 2	-0.6	[M-H]^-	821.468 2, 779.452 5, 761.446 0, 617.403 0	C
80	40.607	trans-N-(4-Dihydroxy-3-methoxyphenethyl) feruloyloctopamine	C₁₆H₂₂O₈	343.139 8	1.5	[M-H]^-	283.129 5	G
81	40.676	Ginsenoside Ro	C₄₈H₇₆O₁₉	955.489 4	-0.9	[M-H]^-	955.489 4, 793.445 4, 569.381 4	S
82	40.676	Ginsenoside Rg₂	C₄₂H₇₂O₁₃	783.490 1	0.8	[M-H]^-	783.490 1, 637.423 4, 475.380 0, 391.284 8	S
83	40.693	Saikosaponin C	C₄₈H₇₈O₁₇	925.513 1	-3.2	[M-H]^-	925.513 1, 779.452 5, 771.499 4	C
84	40.830	Ginsenoside Re	C₄₈H₈₂O₁₈	945.542 8	0.5	[M-H]^-	945.542 8, 783.484 4, 637.423 4, 475.380 0	S
85	40.916	6-O-Galloylglucose	C₁₃H₁₆O₁₀	331.065 5	-3.0	[M-H]^-	331.065 5, 271.054 3, 211.026 3, 169.014 7	B
86	40.945	Ginsenoside Rh₂	C₃₆H₆₂O₈	621.435 5	-1.8	[M-H]^-	621.430 5, 459.387 5	S
87	40.962	Phenylpropanoid glycosides	C₃₈H₄₄O₂₀	819.232 2	-3.2	[M-H]^-	777.237 9, 760.232 7, 584.170 0, 559.166 4, 193.048 2, 175.038 4	T
88	41.048	Acetyl-saikosaponin A or D	C₅₀H₈₂O₁₈	969.541 7	-0.6	[M-H]^-	807.469 8, 499.305 7	C
89	41.476	Curcumolide A	C₁₅H₂₀O₃	249.150 1	4.0	[M+H]⁺	81.070 6	Y
90	41.631	Saikosaponin A	C₄₂H₆₈O₁₃	779.458 2	0.0	[M-H]^-	779.458 2, 617.403 0, 439.322 8	C
41.819	781.483 6	-2.0	[M+H]⁺	781.483 6, 619.431 2, 473.369 5
91	42.671	Saikosaponin E	C₄₂H₆₈O₁₂	763.462 7	-0.8	[M-H]^-	763.462 7, 601.413 9, 161.046 7	C
92	42.914	Curcumin*	C₂₁H₂₀O₆	369.133 0	-2.2	[M+H]⁺	159.084 2, 114.092 6	Y
93	43.128	Curzerene	C₁₅H₂₀O	217.160 0	3.7	[M+H]⁺	147.085 3, 119.088 2, 95.086 8, 79.058 3	Y
94	48.056	Ginsenoside Rk₁	C₄₂H₇₀O₁₂	765.476 4	-3.3	[M-H]^-	603.422 4	S
95	48.159	Saikosaponin B₄	C₄₃H₇₂O₁₄	811.486 1	2.1	[M-H]^-	811.486 1	C
96	49.268	Dibutyl phthalate	C₁₆H₂₂O₄	277.144 1	0.4	[M-H]^-	285.219 4, 148.055 7	B
97	52.303	Bisdemethoxycurcumin	C₁₉H₁₆O₄	309.112 3	-1.3	[M+H]⁺	177.051 1	Y
98	52.783	Cinnamic acid	C₉H₈O₂	149.059 9	-2.7	[M+H]⁺	130.067 1	G
99	52.801	23-Hydroxybetulinic acid	C₃₀H₄₈O₄	471.347 4	0.0	[M-H]^-	363.231 9, 241.219 5, 195.143 1, 171.111 7	B
100	53.258	Palmitic acid	C₁₆H₃₂O₂	255.232 7	1.2	[M-H]^-	241.219 5	B
101	53.653	Saikosaponin F	C₄₈H₈₀O₁₇	927.530 7	-1.1	[M-H]^-	927.530 7	C
102	53.738	Xanthohumol glucoside	C₁₇H₁₆O₉	365.086 7	-1.6	[M+H]⁺	305.092 3	U

No.

t_R /min

Compound

Formula

Precursor ion (m/z)

Error /×10^-6

Adducts

MS/MS (m/z)

Origion plant

1.540

Sucrose

C₁₂H₂₂O₁₁

341.109 2

2.3

[M-H]^-

323.235 7, 266.930 6, 179.056 2, 161.046 7, 119.035 8

B, S

1.592

Albiflorin*

C₂₃H₂₈O₁₁

525.180 7

-0.4

[M+HCOO]^-

357.126 8, 121.034 4

1.592

Desbenzoylpaeoniflorin

C₁₆H₂₄O₁₀

375.130 2

2.9

[M-H]^-

345.118 5, 195.060 2, 165.054 0

1.592

Quinic acid

C₇H₁₂O₆

191.055 1

-2.6

[M-H]^-

173.038 5, 127.045 3, 111.006 6, 93.034 2

1.643

p-Coumaric acid

C₉H₈O₃

165.054 9

-1.8

[M+H]⁺

147.082 8, 119.070 3

1.712

Tufulingoside

C₁₅H₁₆O₉

339.071 8

0.6

[M-H]^-

268.960 0, 193.014 1, 164.012 2, 136.016 2, 121.026 1, 108.020 1

1.780

Proanthocyanidin B23'-gallate

C₃₇H₃₀O₁₆

729.143 7

-2.6

[M-H]^-

515.132 0, 169.006 7

1.849

11-O-Galloylbergenin

C₂₁H₂₀O₁₃

479.080 7

-4.0

[M-H]^-

327.079 7, 151.005 2

1.900

1, 3, 6-O-Trigalloylglucose

C₂₇H₂₄O₁₈

635.090 9

3.9

[M-H]^-

331.065 5, 313.058 8, 169.012 0, 125.026 5

2.324

Citric acid

C₆H₈O₇

191.019 3

0.5

[M-H]^-

173.008 9, 165.054 0, 129.019 9, 111.006 6

2.546

Dihydroisoferulic acid

C₁₀H₁₂O₄

195.065 9

1.0

[M-H]^-

136.053 3, 121.030 3

3.124

6-O-Galloyl arbutin

C₁₉H₂₀O₁₁

423.092 5

-0.5

[M-H]^-

169.017 3

3.227

(-)-Epicatechin gallate

C₂₂H₁₈O₁₀

441.082 6

0.9

[M-H]^-

332.160 8, 271.064 4, 169.017 3

3.535

3-Galloylquinic acid

C₁₄H₁₆O₁₀

343.065 4

-3.2

[M-H]^-

301.234 6, 169.017 3, 123.046 5

4.473

Woodorien

C₁₄H₁₈O₉

329.088 2

2.7

[M-H]^-

167.036 4, 152.009 9, 123.044 3, 108.020 1

4.919

N₁-Caffeoyl, N₃-dihydrocaffeoyl

C₂₅H₃₅N₃O₆

472.245 0

0.4

[M-H]^-

287.053 5, 153.015 4

5.188

Ethyl gallate

C₉H₁₀O₅

197.045 3

1.5

[M-H]^-

182.022 2, 169.017 3, 168.863 1, 166.999 4, 153.020 5, 125.024 2

5.222

(+)-Catechin-5-O-glucoside

C₂₁H₂₄O₁₁

451.124 5

1.1

[M-H]^-

331.087 9, 289.070 9, 245.079 5

5.359

Protocatechuic acid-3-glucoside

C₁₃H₁₆O₉

315.071 0

-1.9

[M-H]^-

153.020 5, 123.046 5, 109.030 3

6.074

6-O-trans-Feruloyl-2-O-β-D-glucopyranosyl-α-D-glucopyranoside

C₂₂H₃₀O₁₄

517.153 7

-3.9

[M-H]^-

271.061 0, 193.048 2, 175.038 4

6.194

Paeoniflorin

C₂₃H₂₆O₁₀

461.143 2

-3.5

[M-H]^-

447.129 1

6.262

Oxypaeoniflorin

C₂₃H₂₈O₁₂

496.156 4

-3.4

[M-H]^-

465.136 4, 345.110 9, 333.093 6, 137.025 0

6.279

3, 4-di-O-Caffeoylquinic acid

C₂₂H₂₈O₁₄

515.141 2

2.1

[M-H]^-

353.076 7, 323.066 6, 164.043 6

6.468

Mudanpioside H

C₃₀H₃₂O₁₄

615.173 4

3.3

[M-H]^-

281.078 1, 191.032 5

6.502

p-Coumaric acid-glycosides isomer

C₁₅H₁₈O₈

325.092 2

-0.3

[M-H]^-

651.163 6, 163.039 0, 119.049 2

6.588

Catechin*

C₁₅H₁₄O₆

289.070 9

-1.0

[M-H]^-

289.070 9, 179.034 3, 151.040 3

7.989

Caffeic acid

C₉H₈O₄

179.034 3

-0.6

[M-H]^-

135.042 1

8.103

Silymarin

C₂₅H₂₂O₁₀

481.113 2

-0.6

[M-H]^-

407.077 9, 297.041 7, 283.022 7, 269.047 2, 256.034 1, 243.030 8, 180.010 2, 152.012 4

8.429

(3β, 20α)-3-Hydroxy-11-oxoolean-12-en-29-oic acid

C₃₀H₄₆O₄

469.333 1

2.8

[M-H]^-

311.164 9

8.437

Chlorogenic acid

C₁₆H₁₈O₉

353.088 2

2.5

[M-H]^-

353.088 2, 191.060 7, 179.034 3, 161.041 5, 135.044 5

9.040

Eugenin-3-glucoside

C₂₃H₂₄O₁₃

509.130 9

2.7

[M+H]⁺

345.064 4, 327.055 8

9.418

Gambiriin A₁ or A₆

C₃₀H₂₆O₁₁

561.141 9

3.9

[M-H]^-

407.073 8, 289.070 9, 273.075 6, 245.079 5, 203.069 7, 188.049 8, 179.034 3, 165.017 2, 151.040 3, 137.025 0, 125.021 9, 109.030 3

9.924

Paeoniflorin*

C₂₃H₂₈O₁₁

479.152 2

2.9

[M-H]^-

479.152 2, 449.140 9, 357.120 7, 327.105 6, 121.102 8

9.692

3, 5-di-O-Caffeoylquinic acid

C₂₂H₂₈O₁₄

515.141 2

2.1

[M-H]^-

353.084 4, 191.066 4, 179.031 6

10.012

Paeoniflorin R₁

C₂₃H₂₈O₁₁

479.156 7

2.9

[M-H]^-

283.091 6, 121.028 3

10.458

Isorhamnetin 3-O-rutinoside

C₂₈H₃₂O₁₆

625.179 2

3.7

[M+H]⁺

317.059 9

40.195

623.159 7

-2.4

[M-H]^-

315.060 1

10.630

(+)-Procyanidin B₂ or B₁

C₃₀H₂₆O₁₂

577.132 4

-3.8

[M-H]^-

407.086 2, 339.086 9, 289.070 9, 245.079 5, 205.048 2, 175.035 7, 161.026 0, 137.022 6, 125.021 9

10.733

Taxifolin-3-glucopyranoside

C₂₁H₂₂O₁₂

465.104 6

2.8

[M-H]^-

335.079 2, 293.018 2, 269.007 0, 256.997 4, 234.988 1, 216.981 9, 196.976 4, 161.023 4

10.767

Quercetin-3-O-galactoside

C₂₁H₂₀O₁₂

463.087 0

-1.5

[M-H]^-

301.032 3

10.870

Anthocyanin

C₂₇H₃₀O₁₅

593.149 2

-2.4

[M-H]^-

264.073 8, 263.070 8

11.053

3-O-Caffeoylshikimic acid

C₁₆H₁₆O₈

335.075 4

-3.9

[M-H]^-

203.069 7, 187.038 3, 161.026 0, 135.044 5, 133.028 9, 123.042 0

11.430

Mudanpioside E

C₂₄H₃₀O₁₃

525.158 7

-4.0

[M-H]^-

495.154 4, 193.053 9

19.359

Galloylpaeoniflorin

C₃₀H₃₂O₁₅

631.168 3

3.2

[M-H]^-

613.150 5, 491.120 1, 313.058 8, 169.014 7, 165.059 2

25.499

Kaempferol

C₁₅H₁₀O₆

285.039 7

-0.7

[M-H]^-

268.038 1, 267.030 9

B, S

25.516

Nicotiflorin

C₂₁H₂₀O₁₁

447.092 4

-0.7

[M-H]^-

285.039 7, 269.040 5, 257.043 3, 241.048 0, 177.022 6, 151.002 6

25.550

Neoastilbin^*

C₂₁H₂₂O₁₁

449.109 9

3.3

[M-H]^-

303.051 8, 285.039 7, 267.030 9, 241.051 1, 175.041 1, 150.031 3, 133.028 9, 123.044 3

25.584

Kaempferol-3-O-glucoside

C₂₁H₂₀O₁₁

447.092 4

-0.7

[M-H]^-

284.035 5, 191.066 4

25.601

Hydroxybenzoyl-O-benzoin

C₂₁H₂₀O₁₁

447.092 4

-0.7

[M-H]^-

249.037 9, 207.030 4, 192.012 1

29.197

Mudanpioside D

C₂₄H₃₀O₁₂

509.164 1

-3.5

[M-H]^-

121.028 3

37.795

Smilaside L

C₄₂H₄₆O₂₀

869.247 9

-2.9

[M-H]^-

804.449 7, 513.141 9, 499.145 7, 193.053 9, 175.041 1, 146.038 8

38.012

Engeletin

C₂₁H₂₂O₁₀

433.114 3

1.8

[M-H]^-

289.070 9, 269.043 9, 259.061 2, 215.072 5, 180.007 4, 152.009 9

38.201

Bis (galloyl)-O-cryptoxanthin

C₂₈H₂₄O₁₇

631.092 4

-1.7

[M-H]^-

461.077 3, 169.012 0

38.449

Notoginsenoside R₁

C₄₇H₈₀O₁₈

931.522 6

2.4

[M-H]^-

931.522 6, 799.484 7, 637.433 7, 475.380 0

38.801

Iristectorin A

C₂₃H₂₄O₁₂

491.120 1

2.2

[M-H]^-

285.039 7, 180.004 7, 151.002 6

38.818

Diacetyl-saikosaponin A or D

C₄₆H₇₂O₁₅

863.479 2

-0.1

[M+H]⁺

821.488 2, 779.475 3

38.835

Ginsenoside Rg₁

C₄₂H₇₂O₁₄

799.484 7

0.4

[M-H]^-

799.484 7, 637.428 6, 475.380 0

38.920

823.484 4

2.9

[M+Na]⁺

643.418 0, 203.057 7

38.835

Quinic acid

C₂₄H₂₀O₉

451.102 8

-0.2

[M-H]^-

281.047 2, 217.012 0, 203.034 7, 189.018 9, 177.019 8, 161.026 0, 151.040 3, 147.044 3, 133.028 9, 123.044 3, 109.028 2

38.886

Ar-Curcumene

C₁₅H₂₂

203.180 2

1.0

[M+H]⁺

201.166 7, 159.117 7, 121.102 0, 95.084 8

38.887

Ginsenoside Rh₁

C₃₆H₆₂O₉

637.429 9

-2.7

[M-H]^-

637.428 6, 475.380 0

38.967

Astilbin sulfate

C₂₁H₂₂O₁₄S

529.066 6

2.6

[M-H]^-

383.004 8, 364.996 4, 285.039 7, 230.966 1, 228.980 6, 216.987 9, 181.052 0, 167.036 4, 151.005 2

39.001

Astilbin sulfate isomer

C₂₁H₂₂O₁₄S

529.066 6

2.6

[M-H]^-

383.004 8, 365.004 2, 285.039 7, 228.974 4, 212.986 4, 201.992 5, 177.017 1, 167.036 4, 151.002 6

39.293

Saikosaponin X

C₄₂H₆₆O₁₅

809.430 2

-2.6

[M-H]^-

809.430 2, 780.423 7, 779.418 2, 617.362 3

39.413

(Z)-(1S, 5R)-β-pinen-10-yl β-vicianoside

C₂₁H₃₄O₁₀

445.208 4

-2.2

[M-H]^-

293.088 3, 233.066 4, 191.055 1

39.636

Smilaside B

C₃₄H₄₀O₁₈

735.216 4

3.8

[M-H]^-

500.074 0, 418.060 5, 375.043 0, 337.093 2, 301.074 9, 265.072 1, 193.048 2, 175.038 4

39.721

Mururin A

C₂₄H₁₆O₉

447.070 8

-1.8

[M-H]^-

323.022 5, 295.021 3, 282.018 6, 267.027 6, 251.040 4, 240.045 3, 223.038 6, 211.038 2, 195.045 9

39.841

Linoleic acid

C₁₈H₃₂O₂

279.232 4

0.0

[M-H]^-

125.092 8, 71.014 9

39.893

Benzoyloxypeoniflorin

C₃₀H₃₂O₁₃

599.178 3

3.0

[M-H]^-

447.222 2, 313.066 1, 293.088 3, 165.054 0, 137.025 0, 121.028 3

39.910

Quercetin

C₁₅H₁₀O₇

301.035 9

3.7

[M-H]^-

301.035 9, 283.022 7, 255.026 8, 178.998 7, 151.002 6, 107.012 5

G, S

39.973

Caffeoyl-O-benzoin

C₂₃H₂₂O₁₂

489.104 6

2.7

[M-H]^-

249.037 9, 207.030 4, 192.009 2

40.042

Smilaside A

C₃₆H₄₂O₁₉

777.226 5

3.0

[M-H]^-

735.205 3, 717.205 3, 625.082 3, 559.166 4, 513.141 9, 499.145 7, 193.048 2, 175.038 4, 160.015 1

40.093

Benzoylpaeoniflorin

C₃₀H₃₂O₁₂

583.181 6

0.0

[M-H]^-

553.164 5, 461.121 2, 431.132 5, 327.083 4

40.162

Mudanpioside C

C₃₀H₃₂O₁₃

599.178 3

3.0

[M-H]^-

581.157 7, 477.130 2, 447.122 7, 137.015 4, 121.028 3

40.247

Ginsenoside Rc

C₅₃H₉₀O₂₂

1 077.585 3

0.7

[M-H]^-

1 077.585 3, 945.536 5, 783.484 4, 621.430 5, 459.387 5

40.299

Mudanpioside B

C₃₁H₃₄O₁₄

629.186 0

-1.6

[M-H]^-

583.181 6, 341.128 1, 121.028 3

40.325

Ginsenoside Rb₁

C₅₄H₉₂O₂₃

1 107.589 0

0.6

[M-H]^-

1 107.589 0, 945.542 8, 783.484 4, 621.435 5, 459.387 5

40.419

Notoginsenoside R₂

C₄₁H₇₀O₁₃

769.472 0

-2.3

[M-H]^-

769.472 0, 637.433 7, 475.375 6, 391.284 8, 101.022 7

40.470

Smilaside C

C₄₁H₄₄O₁₉

839.238 5

-1.7

[M-H]^-

693.209 4, 663.184 0, 645.189 5, 517.158 4, 499.141 1, 483.137 1, 337.089 5, 193.048 2, 175.038 4

40.590

Naringenin

C₁₅H₁₂O₅

271.061 0

1.5

[M-H]^-

270.061 0

40.590

3'-O-Acetylsaikosaponin A

C₄₄H₇₀O₁₄

821.468 2

-0.6

[M-H]^-

821.468 2, 779.452 5, 761.446 0, 617.403 0

40.607

trans-N-(4-Dihydroxy-3-methoxyphenethyl) feruloyloctopamine

C₁₆H₂₂O₈

343.139 8

1.5

[M-H]^-

283.129 5

40.676

Ginsenoside Ro

C₄₈H₇₆O₁₉

955.489 4

-0.9

[M-H]^-

955.489 4, 793.445 4, 569.381 4

40.676

Ginsenoside Rg₂

C₄₂H₇₂O₁₃

783.490 1

0.8

[M-H]^-

783.490 1, 637.423 4, 475.380 0, 391.284 8

40.693

Saikosaponin C

C₄₈H₇₈O₁₇

925.513 1

-3.2

[M-H]^-

925.513 1, 779.452 5, 771.499 4

40.830

Ginsenoside Re

C₄₈H₈₂O₁₈

945.542 8

0.5

[M-H]^-

945.542 8, 783.484 4, 637.423 4, 475.380 0

40.916

6-O-Galloylglucose

C₁₃H₁₆O₁₀

331.065 5

-3.0

[M-H]^-

331.065 5, 271.054 3, 211.026 3, 169.014 7

40.945

Ginsenoside Rh₂

C₃₆H₆₂O₈

621.435 5

-1.8

[M-H]^-

621.430 5, 459.387 5

40.962

Phenylpropanoid glycosides

C₃₈H₄₄O₂₀

819.232 2

-3.2

[M-H]^-

777.237 9, 760.232 7, 584.170 0, 559.166 4, 193.048 2, 175.038 4

41.048

Acetyl-saikosaponin A or D

C₅₀H₈₂O₁₈

969.541 7

-0.6

[M-H]^-

807.469 8, 499.305 7

41.476

Curcumolide A

C₁₅H₂₀O₃

249.150 1

4.0

[M+H]⁺

81.070 6

41.631

Saikosaponin A

C₄₂H₆₈O₁₃

779.458 2

0.0

[M-H]^-

779.458 2, 617.403 0, 439.322 8

41.819

781.483 6

-2.0

[M+H]⁺

781.483 6, 619.431 2, 473.369 5

42.671

Saikosaponin E

C₄₂H₆₈O₁₂

763.462 7

-0.8

[M-H]^-

763.462 7, 601.413 9, 161.046 7

42.914

Curcumin*

C₂₁H₂₀O₆

369.133 0

-2.2

[M+H]⁺

159.084 2, 114.092 6

43.128

Curzerene

C₁₅H₂₀O

217.160 0

3.7

[M+H]⁺

147.085 3, 119.088 2, 95.086 8, 79.058 3

48.056

Ginsenoside Rk₁

C₄₂H₇₀O₁₂

765.476 4

-3.3

[M-H]^-

603.422 4

48.159

Saikosaponin B₄

C₄₃H₇₂O₁₄

811.486 1

2.1

[M-H]^-

811.486 1

49.268

Dibutyl phthalate

C₁₆H₂₂O₄

277.144 1

0.4

[M-H]^-

285.219 4, 148.055 7

52.303

Bisdemethoxycurcumin

C₁₉H₁₆O₄

309.112 3

-1.3

[M+H]⁺

177.051 1

52.783

Cinnamic acid

C₉H₈O₂

149.059 9

-2.7

[M+H]⁺

130.067 1

52.801

23-Hydroxybetulinic acid

C₃₀H₄₈O₄

471.347 4

0.0

[M-H]^-

363.231 9, 241.219 5, 195.143 1, 171.111 7

100

53.258

Palmitic acid

C₁₆H₃₂O₂

255.232 7

1.2

[M-H]^-

241.219 5

101

53.653

Saikosaponin F

C₄₈H₈₀O₁₇

927.530 7

-1.1

[M-H]^-

927.530 7

102

53.738

Xanthohumol glucoside

C₁₇H₁₆O₉

365.086 7

-1.6

[M+H]⁺

305.092 3