药学学报

No.	Identification	t_R/min	Formula	Ion adduction	Measured mass (m/z)	Error/10^-6	Fragment (m/z)	Source
1	3S-1-N-β-D-Glucopyranosyl-3- hydroxy-indole-3-acetic acid/3R- 1-N-β-D-glucopyranosyl-3-hydroxy-indole-3-acetic acid^[11]	4.54	C₁₆H₁₉NO₉	[M+H]⁺	370.113 0	-0.7	212.067 4, 188.069 6, 146.059 2, 128.049 3	SZR
2	Protocatechuic acid^[11]	5.20	C₇H₆O₄	[M-H]^-	153.019 5	0.8	107.015 9, 124.016 5	SZR
3	6-Glu-coclaurine^[12]	7.13	C₂₃H₂₉NO₈	[M+H]⁺	448.196 7	-1.0	286.142 8, 269.115 8, 175.074 6, 107.049 5	SZR
4	4-Hydroxybenzoic acid^[12]	8.94	C₇H₆O₃	[M-H]^-	137.025 0	4.5	108.022 9, 136.016 7	SZR
5	Epicatechin^[13]	9.80	C₁₅H₁₄O₆	[M-H]^-	289.071 6	-0.5	221.081 2, 203.071 1, 123.044 9, 109.030 1	SZR
6	Coclaurine^{[11, 12]}	10.61	C₁₇H₁₉NO₃	[M+H]⁺	286.143 9	0.4	107.049 6, 175.075 3	SZR
7	Magnoflorine^[12]	11.52	C₂₀H₂₃NO₄	[M+H]⁺	342.169 7	-0.7	297.109 7, 282.086 2, 265.083 2, 222.088 7	SZR
8	Catechine^[13]	12.00	C₁₅H₁₄O₆	[M-H]^-	289.071 6	-0.7	221.082 6, 203.070 7, 187.039 2, 109.030 2	SZR
9	Hovetrichoside C^[11]	12.44	C₂₁H₂₂O₁₁	[M-H]^-	449.108 5	-0.9	259.060 0, 269.046 2, 125.023 9, 287.056 5	SZR
10	Kaempferol-3-O-rutinoside^{[11, 14]}	14.50	C₂₇H₃₀O₁₅	[M+H]⁺	595.164 6	-1.9	433.111 9, 337.068 9, 313.069 2, 283.058 3	SZR
11	Puerarin^[11]	14.70	C₂₁H₂₀O₉	[M-H]^-	415.103 7	-0.9	252.041 3, 25.053 1,	SZR
12	Spinosin^{a [11, 14, 15]}	15.33	C₂₈H₃₂O₁₅	[M+H]⁺	609.180 1	-2.2	327.085 2, 351.085 9, 297.075 3, 447.127 9, 285.075 3, 411.107 5, 609.178 6	SZR
13	Camelliaside B^[11]	15.45	C₃₂H₃₈O₁₉	[M-H]^-	725.194 9	1.9	284.033 4, 575.153 3	SZR
14	Caaverine^[11]	15.78	C₁₇H₁₇NO₂	[M+H]⁺	268.133 1	-0.3	251.105 4, 236.082 6, 219.079 4, 208.087 4, 191.084 5, 190.076 6, 189.068 8, 165.069 6	SZR
15	6'''-Vanilloylspinosin^{[11, 13]}	17.57	C₃₆H₃₈O₁₈	[M+H]⁺	759.211 7	-1.8	639.168 3, 429.117 7, 351.085 2, 327.085 4, 297.075 4	SZR
16	6'''-p-Hydroxylbenzoyspinosin^[11-13]	18.39	C₃₅H₃₆O₁₇	[M+H]⁺	729.200 8	-2.4	609.165 7, 429.117 1, 351.086 0, 327.084 9, 297.074 0, 121.028 5	SZR
17	Vitexin-4''-O-glucoside^[11-14]	18.43	C₂₇H₃₀O₁₅	[M+H]⁺	595.164 2	-2.6	287.054 9, 595.163 7	SZR
18	6'''-O-(3R-1-N-β-D-Glucopyranosyl-2-oxo-3-hydroxy-indole-3-acetyl) spinosin^[11]	19.06	C₄₄H₄₉NO₂₃	[M-H]^-	958.266 5	4.5	649.177 4	SZR
19	6'''-Sinapoylspinosin^[11-13]	19.39	C₃₉H₄₂O₁₉	[M+H]⁺	815.237 3	-2.5	635.170 3, 447.127 3, 429.118 6, 393.094 2, 351.088 6, 327.085 4, 297.075 5, 207.063 0, 175.038 6	SZR
20	6'''-Feruloylspinosin^{a [11-14, 16]}	19.91	C₃₈H₄₀O₁₈	[M+H]⁺	785.227 6	-1.5	327.084 6, 351.084 5, 177.053 7, 297.074 3, 429.116 5, 665.184 6, 785.223 7	SZR
21	6'''-p-Coumaroylspinosin^[11-13]	19.97	C₃₇H₃₈O₁₇	[M+H]⁺	755.217 4	-1.0	447.127 5, 429.116 5, 351.085 4, 327.085 7, 297.074 9, 147.044 3	SZR
22	epi-6'''-(N-β-D-Glucopyranosyl)-2'''', 3''''-dihydro-2''''-oxo-3''''-yl-acetate spinosin^[11]	20.22	C₄₄H₄₉NO₂₂	[M+H]⁺	944.279 9	-2.1	782.225 5, 764.216 2, 489.137 7, 393.095 6, 351.085 5, 327.085 2	SZR
23	N-Nornuciferine^[11]	21.10	C₁₈H₁₉NO₂	[M+H]⁺	282.148 6	-0.9	265.120 6, 250.097 2, 235.073 9, 234.101 9, 191.084 4, 189.068 5, 178.076 4	SZR
24	6''-O-Feruloylspinosin^{[11-14, 16]}	21.19	C₃₈H₄₀O₁₈	[M+H]⁺	785.226 6	-2.8	489.141 2, 447.127 1, 327.085 3, 285.074 3	SZR
25	Amphibine D/Lotusine B^[12]	22.46	C₃₆H₄₉N₅O₅	[M+H]⁺	632.379 0	-2.6	148.112 1, 289.190 4, 261.196 0, 316.199 6, 344.196 0, 632.377 1	SZR
26	Jujuboside A^{a [11-14, 16]}	23.30	C₅₈H₉₄O₂₆	[M-H]^-	1 205.600 2	3.4	911.527 3	SZR
27	Jujuboside B^{a [11-14, 16]}	24.15	C₅₂H₈₄O₂₁	[M-H]^-	1 043.549 3	5.0	911.505 5	SZR
28	Neomangiferin^{a [11, 14, 15]}	8.35	C₂₅H₂₈O₁₆	[M-H]^-	583.130 6	0.2	301.034 4, 331.044 6, 463.086 2, 493.096 8	ZM
29	Mangiferin^{a [11, 14-16]}	11.22	C₁₉H₁₈O₁₁	[M-H]^-	421.077 3	-0.8	301.034 4, 331.0450, 259.025 2, 271.024 4, 421.075 6	ZM
30	Timosaponin D^{[11, 14, 16]}	19.55	C₄₅H₇₄O₁₉	[M+H]⁺	919.488 0	-1.9	289.214 9, 271.204 8, 433.329 1, 757.433 5	ZM
31	Timosaponin N^{[11, 17]}	19.63	C₄₅H₇₆O₂₀	[M+HCOO]^-	981.494 1	4.0	773.442 0	ZM
32	Timosaponin E1^{[11, 17]}	20.29	C₄₅H₇₆O₂₀	[M+HCOO]^-	981.495 0	4.9	773.436 5, 360.571 1	ZM
33	Timosaponin BII^{a [11, 16, 17]}	20.70	C₄₅H₇₆O₁₉	[M-H]^-	919.490 8	3.0	919.493 6	ZM
34	Gurilioside H^[11]	20.76	C₅₁H₈₆O₂₃	[M+HCOO]^-	1 111.556 2	2.8	919.490 3, 757.446 4	ZM
35	Timosaponin BIII^{[11, 14, 16]}	20.88	C₄₅H₇₄O₁₈	[M+H]⁺	903.492 1	-3.0	273.218 5, 255.208 3, 417.332 3, 399.322 2, 579.384 3, 741.433 6	ZM
36	Timosaponin AI^[14]	20.89	C₃₃H₅₄O₈	[M+H]⁺	579.387 6	-2.8	273.220 6, 255.210 6, 417.336 3, 301.142 8	ZM
37	(25S)-26-O-β-D-Glucopyranosyl- 22-hydroxy-5β-furostanol alkenyl-3β, 26-diol3-O-β-D-glucopyranosyl- (1-2)-O-β-D-galactopyranoside^{[11, 14, 16]}	21.52	C₄₅H₇₄O₁₉	[M-H]^-	917.478 3	3.4	755.422 7, 917.477 7	ZM
38	Timosaponin BⅣ^{[11, 17]}	22.65	C₅₁H₈₄O₂₃	[M+HCOO]^-	1 109.541 9	4.1	901.492 6, 739.438 6	ZM
39	2, 6, 4'-Trihydroxy-4-methoxybenzophenone^[11]	22.82	C₁₄H₁₂O₅	[M-H]^-	259.061 1	-0.6	165.018 6, 149.995 3	ZM
40	Timosaponin AIII^{[11, 14, 17]}	23.74	C₃₉H₆₄O₁₃	[M+H]⁺	741.439 9	-2.8	381.314 0, 399.325 4	ZM
41	Anemarrhenasaponin Ⅱ^[11, ^7]	24.01	C₃₉H₆₆O₁₄	[M+HCOO]^-	803.445 1	3.5	757.439 2, 595.385 5, 757.439 2	ZM
42	3β, 16α-Dihydroxy-lanosta-7, 9(11), 24-trien-21-oic acid^{[11, 14, 16]}	24.17	C₃₀H₄₆O₄	[M+H]⁺	471.346 2	-1.4	317.208 5, 453.347 6, 471.269 2	FL
43	Poricoic acid A^{[11, 14]}	28.55	C₃₁H₄₆O₅	[M-H]^-	497.327 4	0.3	479.313 3, 497.326 6	FL
44	Poricoic acid B^{[11, 14]}	32.75	C₃₀H₄₄O₅	[M-H]^-	483.311 2	-0.8	409.272 3, 483.310 2	FL
45	Polyporenic acid C^{[11, 14]}	38.58	C₃₁H₄₆O₄	[M-H]^-	481.332 3	0.0	421.305 1, 481.330 3	FL
46	Pachymic acid^{[11, 14]}	47.55	C₃₃H₅₂O₅	[M+H]⁺	529.386 3	-4.6	451.353 8, 295.243 2	FL
47	Adenine^[11]	1.69	C₅H₅N₅	[M+H]⁺	136.061 7	-0.7	119.036 4, 136.063 0	CX
48	Vanillic acid^11]	4.69	C₈H₈O₄	[M+H]⁺	169.049 5	-1.7	151.033 8, 105.034 7	CX
49	Neochlorogenic acid/Chlorogenic acid^[11]	9.43	C₁₆H₁₈O₉	[M-H]^-	353.087 8	0.1	191.056 2, 179.035 3	CX
50	Caffeic acid^[11]	11.31	C₉H₈O₄	[M-H]^-	179.034 8	-0.8	135.044 8, 179.034 7	CX
51	Ferulic acid^{a[11, 14, 15]}	16.65	C₁₀H₁₀O₄	[M-H]^-	193.050 7	0.1	134.036 7, 178.026 5, 149.058 0, 193.050 2	CX
52	Senkyunolide J^{[11, 14]}	17.86	C₁₂H₁₈O₄	[M+H]⁺	227.127 7	-0.2	153.053 8, 163.110 6, 191.106 2, 209.116 4	CX
53	Dicaffeoylquinic acid^[14]	19.80	C₂₅H₂₄O₁₂	[M-H]^-	515.119 3	-0.4	191.055 6, 353.087 5, 179.035 1, 515.119 0	CX
54	Senkyunolide D^{[11, 14]}	20.11	C₁₂H₁₄O₄	[M+H]⁺	223.096 3	-1.0	205.085 3, 223.089 1, 105.034 7	CX
55	Naringenin^[11]	20.27	C₁₅H₁₂O₅	[M+H]⁺	273.075 5	-0.8	153.018 9, 147.045 8, 119.047 8	CX
56	Senkyunolide Ⅰ^{a[11, 14]}	20.83	C₁₂H₁₆O₄	[M+H]⁺	225.111 8	0.5	225.111 8, 207.102 5	CX
57	Senkyunolide F^{[11, 14]}	20.84	C₁₂H₁₄O₃	[M+H]⁺	207.101 4	-1.0	207.101 9, 189.091 3, 119.085 7, 105.071 1, 133.064 8, 128.061 8, 161.096 9, 128.061 8, 179.107 0	CX
58	3-Butyl-4-hydroxyphthalide^{[11, 14]}	21.45	C₁₂H₁₄O₃	[M+H]⁺	207.101 4	-1.0	207.101 9, 189.091 3, 161.096 9, 128.061 8, 179.107 0	CX
59	Daidzein^[11]	21.81	C₁₅H₁₀O₄	[M+H]⁺	255.065 0	-0.9	145.029 1, 137.023 0, 119.051 3	CX
60	E-Butylidenephthalide^{[11, 14]}	23.78	C₁₂H₁₂O₂	[M+H]⁺	189.091 0	-0.1	115.055 2, 171.080 4, 189.091 6	CX
61	Butylidenephthalide^{[11, 14]}	25.77	C₁₂H₁₂O₂	[M+H]⁺	189.091 0	-0.5	171.079 5, 189.089 0	CX
62	Senkyunolide A^{a [11, 14]}	28.70	C₁₂H₁₆O₂	[M+H]⁺	193.122 1	-0.4	137.059 1, 119.085 5, 147.115 9, 175.111 2, 193.121 7, 109.064 5	CX
63	Cnidilide^{[14, 18]}	30.73	C₁₂H₁₈O₂	[M+H]⁺	195.137 9	-0.1	107.085 9, 125.059 0, 149.132 8, 177.126 4	CX
64	Z/E-Ligustilide or 3- butylphthalide^{[11, 14]}	31.00	C₁₂H₁₄O₂	[M+H]⁺	191.106 5	-0.7	105.070 5, 115.054 5, 117.070 1, 145.101 1, 173.095 4, 149.060 0	CX
65	Ligustilide dimer^[11]	35.90	C₂₄H₃₀O₄	[M+H]⁺	383.221 3	-1.0	191.106 7, 135.042 9	CX
66	Riligustilide/Z, Z'-6, 8', 7, 3'- Diligustilide^[14]	39.83	C₂₄H₂₈O₄	[M+H]⁺	381.205 7	-0.9	191.107 2, 135.043 1	CX
67	Glycyrrhizin-7, 4'-diglucoside^[11]	10.17	C₂₇H₃₂O₁₄	[M-H]^-	579.172 2	0.4	135.012 8, 255.067 0, 417.118 1	GC
68	Shaftoside/isoshaftoside^[14]	13.40	C₂₆H₂₈O₁₄	[M-H]^-	563.141 2	0.9	353.063 7, 383.074 8, 443.095 8, 473.113 9, 503.119 1	GC
69	Glucoliquiritin^[11]	13.94	C₂₇H₃₂O₁₄	[M-H]^-	579.172 2	0.4	255.066 5, 579.174 4	GC
70	Isoliquiritin apioside^{[11, 14, 16]}	15.66	C₂₆H₃₀O₁₃	[M-H]^-	549.161 9	0.9	255.066 9, 135.009 3	GC
71	Liquiritin apioside^{a [11, 14, 16]}	16.22	C₂₆H₃₀O₁₃	[M-H]^-	549.161 3	-0.1	255.066 3, 135.008 0	GC
72	Liquiritin^{a [11, 14, 16, 18]}	16.53	C₂₁H₂₂O₉	[M-H]^-	417.119 5	0.9	119.050 2, 135.008 3, 255.065 3, 417.117 6	GC
73	5-Hydroxyliquiritin^{[11, 14]}	20.34	C₂₁H₂₂O₁₀	[M-H]^-	433.113 6	-0.9	271.060 9, 177.018 7, 151.004 3, 119.051 5, 433.114 1	GC
74	Isoliquiritin^{[11, 14-16]}	21.42	C₂₁H₂₂O₉	[M-H]^-	417.118 9	-0.4	119.051 0, 135.008 7, 255.066 1, 417.117 9, 148.017 4	GC
75	Licorice glycoside A^[11]	21.61	C₃₆H₃₈O₁₆	[M-H]^-	725.210 8	2.9	255.065 0, 531.143 8, 549.161 0, 726.214 0, 175.040 3	GC
76	Licorice glycoside B^[11]	21.62	C₃₅H₃₆O₁₅	[M-H]^-	695.199 6	2.0	549.195 9, 531.152 6, 255.065 3, 135.008 6	GC
77	Licorice glycoside E^[14]	22.34	C₃₅H₃₅NO₁₄	[M-H]^-	692.199 6	1.5	255.066 6, 531.153 5, 549.160 7	GC
78	5, 7-Dihydroxyflavanone/ Pinocembrin/Liquiritigenin^{[11, 14, 16]}	22.79	C₁₅H₁₂O₄	[M-H]^-	255.066 1	-0.6	119.050 2, 135.008 0, 255.063 4	GC
79	24-Hydroxy-licorice-saponin E2^[11]	23.34	C₄₂H₆₀O₁₇	[M-H]^-	835.378 8	3.6	351.055 7, 193.036 0	GC
80	Licorice saponine G2^[14]	23.77	C₄₂H₆₂O₁₇	[M-H]^-	837.394 9	4.2	351.056 6, 837.394 5	GC
81	Uralsaponin B^{[11, 14]}	24.16	C₄₂H₆₂O₁₆	[M+H]⁺	823.408 8	-2.7	453.334 0, 647.376 6	GC
82	Echinatin^{[14, 18]}	24.24	C₁₆H₁₄O₄	[M-H]^-	269.081 3	-2.2	133.031 1, 161.020 0	GC
83	Glycyrrhizic acid^{a[11, 14]}	24.38	C₄₂H₆₂O₁₆	[M-H]^-	821.399 6	3.8	351.055 4, 821.399 3	GC
84	Licochalcone B^[11]	25.21	C₁₆H₁₄O₅	[M-H]^-	285.076 4	1.6	285.078 8, 150.037 8	GC
85	Isoliquiritigenin^{[11, 14, 16]}	25.48	C₁₅H₁₂O₄	[M-H]^-	255.066 3	-0.6	255.066 3, 135.008 6, 119.050 7	GC
86	Formononetin^{[14, 18]}	25.76	C₁₆H₁₂O₄	[M-H]^-	267.066 0	-1.0	252.042 5, 223.039 6, 267.065 7, 195.045 0	GC
87	(-)-Vestitol^[16]	25.83	C₁₆H₁₆O₄	[M-H]^-	271.097 3	-1.0	235.044 8, 109.031 1, 271.095 0, 149.062 1, 238.069 9, 121.032 4, 241.061 8, 255.068 8	GC
88	Glycycoumarin^[11]	27.37	C₂₁H₂₀O₆	[M-H]^-	367.118 6	-0.2	309.040 4, 367.118 5, 297.039 9, 284.032 2, 265.051 2, 139.039 7, 201.018 9	GC
89	Genkwanin^[11]	27.86	C₁₆H₁₂O₅	[M-H]^-	283.061 0	-0.8	268.037 0, 239.035 6, 211.036 7	GC
90	Kumatakenin^[14]	28.27	C₁₇H₁₄O₆	[M-H]^-	313.071 8	0.0	283.024 0, 255.029 6, 298.046 6, 313.239 3, 183.045 5, 295.226 9	GC
91	Glycyrin/Licoricone^{[11, 14]}	28.66	C₂₂H₂₂O₆	[M-H]^-	381.134 2	-0.6	351.087 5, 201.019 5, 323.092 6	GC
92	Lupiwighteone^{[11, 18]}	29.16	C₂₀H₁₈O₅	[M-H]^-	337.107 9	-0.7	282.052 7, 281.045 5	GC
93	Neo/Glycyrol/Isoglycyrol^[11]	29.24	C₂₁H₁₈O₆	[M-H]^-	365.102 8	-0.8	307.024 2, 295.024 2, 365.102 0, 282.016 3, 335.056 2	GC
94	Gancaonin A^[14]	29.63	C₂₁H₂₀O₅	[M-H]^-	351.123 4	-1.1	281.045 1, 308.104 3, 336.100 8, 293.082 1, 253.049 3, 307.098 7	GC
95	Glabrol^[14]	31.91	C₂₅H₂₈O₄	[M-H]^-	391.191 2	-0.8	187.114 6, 203.070 8, 391.191 2, 132.058 5	GC
96	Glyinflanin A^[14]	34.54	C₂₅H₂₈O₅	[M-H]^-	407.186 1	-0.8	187.112 3, 133.063 7, 175.075 2	GC
97	Glabric acid^[14]	38.10	C₃₀H₄₆O₅	[M+H]⁺	487.346 9	-2.3	487.330 6, 423.324 7, 451.321 9	GC
98	Licorisoflavan A^[14]	41.72	C₂₇H₃₄O₅	[M+H]⁺	439.247 7	-0.4	191.104 5, 371.182 2	GC
99	Gancaonin H^{[11, 12, 14]}	44.90	C₂₅H₂₄O₆	[M-H]^-	419.150 1	0.2	219.066 0, 419.148 5	GC
100	Vicenin Ⅱ^{[11, 12, 14]}	11.35	C₂₇H₃₀O₁₅	[M+H]⁺	595.164 2	-2.6	559.143 9, 511.124 9, 457.112 6, 337.068 9, 325.069 4, 295.060 1	SZR/GC
101	Saponarin^{[11, 12, 14]}	14.77	C₂₇H₃₀O₁₅	[M-H]^-	593.151 5	0.5	293.044 7, 413.087 4, 341.064 6	SZR/GC
102	Vitexin^{[11, 14]}	15.93	C₂₁H₂₀O₁₀	[M+H]⁺	433.112 6	-0.8	415.0985, 397.082 6, 379.082 6, 337.070 1, 313.068 9, 295.061 1, 283.059 8	SZR/GC
103	Isovitexin^{[11, 14]}	16.23	C₂₁H₂₀O₁₀	[M-H]^-	431.098 1	-0.6	311.055 2, 341.067 9, 323.058 5	SZR/GC

No.	Identification	t_R/min	Formula	Ion adduction	Measured mass (m/z)	Error/10^-6	Fragment (m/z)	Source
1	3S-1-N-β-D-Glucopyranosyl-3- hydroxy-indole-3-acetic acid/3R- 1-N-β-D-glucopyranosyl-3-hydroxy-indole-3-acetic acid^[11]	4.54	C₁₆H₁₉NO₉	[M+H]⁺	370.113 0	-0.7	212.067 4, 188.069 6, 146.059 2, 128.049 3	SZR
2	Protocatechuic acid^[11]	5.20	C₇H₆O₄	[M-H]^-	153.019 5	0.8	107.015 9, 124.016 5	SZR
3	6-Glu-coclaurine^[12]	7.13	C₂₃H₂₉NO₈	[M+H]⁺	448.196 7	-1.0	286.142 8, 269.115 8, 175.074 6, 107.049 5	SZR
4	4-Hydroxybenzoic acid^[12]	8.94	C₇H₆O₃	[M-H]^-	137.025 0	4.5	108.022 9, 136.016 7	SZR
5	Epicatechin^[13]	9.80	C₁₅H₁₄O₆	[M-H]^-	289.071 6	-0.5	221.081 2, 203.071 1, 123.044 9, 109.030 1	SZR
6	Coclaurine^{[11, 12]}	10.61	C₁₇H₁₉NO₃	[M+H]⁺	286.143 9	0.4	107.049 6, 175.075 3	SZR
7	Magnoflorine^[12]	11.52	C₂₀H₂₃NO₄	[M+H]⁺	342.169 7	-0.7	297.109 7, 282.086 2, 265.083 2, 222.088 7	SZR
8	Catechine^[13]	12.00	C₁₅H₁₄O₆	[M-H]^-	289.071 6	-0.7	221.082 6, 203.070 7, 187.039 2, 109.030 2	SZR
9	Hovetrichoside C^[11]	12.44	C₂₁H₂₂O₁₁	[M-H]^-	449.108 5	-0.9	259.060 0, 269.046 2, 125.023 9, 287.056 5	SZR
10	Kaempferol-3-O-rutinoside^{[11, 14]}	14.50	C₂₇H₃₀O₁₅	[M+H]⁺	595.164 6	-1.9	433.111 9, 337.068 9, 313.069 2, 283.058 3	SZR
11	Puerarin^[11]	14.70	C₂₁H₂₀O₉	[M-H]^-	415.103 7	-0.9	252.041 3, 25.053 1,	SZR
12	Spinosin^{a [11, 14, 15]}	15.33	C₂₈H₃₂O₁₅	[M+H]⁺	609.180 1	-2.2	327.085 2, 351.085 9, 297.075 3, 447.127 9, 285.075 3, 411.107 5, 609.178 6	SZR
13	Camelliaside B^[11]	15.45	C₃₂H₃₈O₁₉	[M-H]^-	725.194 9	1.9	284.033 4, 575.153 3	SZR
14	Caaverine^[11]	15.78	C₁₇H₁₇NO₂	[M+H]⁺	268.133 1	-0.3	251.105 4, 236.082 6, 219.079 4, 208.087 4, 191.084 5, 190.076 6, 189.068 8, 165.069 6	SZR
15	6'''-Vanilloylspinosin^{[11, 13]}	17.57	C₃₆H₃₈O₁₈	[M+H]⁺	759.211 7	-1.8	639.168 3, 429.117 7, 351.085 2, 327.085 4, 297.075 4	SZR
16	6'''-p-Hydroxylbenzoyspinosin^[11-13]	18.39	C₃₅H₃₆O₁₇	[M+H]⁺	729.200 8	-2.4	609.165 7, 429.117 1, 351.086 0, 327.084 9, 297.074 0, 121.028 5	SZR
17	Vitexin-4''-O-glucoside^[11-14]	18.43	C₂₇H₃₀O₁₅	[M+H]⁺	595.164 2	-2.6	287.054 9, 595.163 7	SZR
18	6'''-O-(3R-1-N-β-D-Glucopyranosyl-2-oxo-3-hydroxy-indole-3-acetyl) spinosin^[11]	19.06	C₄₄H₄₉NO₂₃	[M-H]^-	958.266 5	4.5	649.177 4	SZR
19	6'''-Sinapoylspinosin^[11-13]	19.39	C₃₉H₄₂O₁₉	[M+H]⁺	815.237 3	-2.5	635.170 3, 447.127 3, 429.118 6, 393.094 2, 351.088 6, 327.085 4, 297.075 5, 207.063 0, 175.038 6	SZR
20	6'''-Feruloylspinosin^{a [11-14, 16]}	19.91	C₃₈H₄₀O₁₈	[M+H]⁺	785.227 6	-1.5	327.084 6, 351.084 5, 177.053 7, 297.074 3, 429.116 5, 665.184 6, 785.223 7	SZR
21	6'''-p-Coumaroylspinosin^[11-13]	19.97	C₃₇H₃₈O₁₇	[M+H]⁺	755.217 4	-1.0	447.127 5, 429.116 5, 351.085 4, 327.085 7, 297.074 9, 147.044 3	SZR
22	epi-6'''-(N-β-D-Glucopyranosyl)-2'''', 3''''-dihydro-2''''-oxo-3''''-yl-acetate spinosin^[11]	20.22	C₄₄H₄₉NO₂₂	[M+H]⁺	944.279 9	-2.1	782.225 5, 764.216 2, 489.137 7, 393.095 6, 351.085 5, 327.085 2	SZR
23	N-Nornuciferine^[11]	21.10	C₁₈H₁₉NO₂	[M+H]⁺	282.148 6	-0.9	265.120 6, 250.097 2, 235.073 9, 234.101 9, 191.084 4, 189.068 5, 178.076 4	SZR
24	6''-O-Feruloylspinosin^{[11-14, 16]}	21.19	C₃₈H₄₀O₁₈	[M+H]⁺	785.226 6	-2.8	489.141 2, 447.127 1, 327.085 3, 285.074 3	SZR
25	Amphibine D/Lotusine B^[12]	22.46	C₃₆H₄₉N₅O₅	[M+H]⁺	632.379 0	-2.6	148.112 1, 289.190 4, 261.196 0, 316.199 6, 344.196 0, 632.377 1	SZR
26	Jujuboside A^{a [11-14, 16]}	23.30	C₅₈H₉₄O₂₆	[M-H]^-	1 205.600 2	3.4	911.527 3	SZR
27	Jujuboside B^{a [11-14, 16]}	24.15	C₅₂H₈₄O₂₁	[M-H]^-	1 043.549 3	5.0	911.505 5	SZR
28	Neomangiferin^{a [11, 14, 15]}	8.35	C₂₅H₂₈O₁₆	[M-H]^-	583.130 6	0.2	301.034 4, 331.044 6, 463.086 2, 493.096 8	ZM
29	Mangiferin^{a [11, 14-16]}	11.22	C₁₉H₁₈O₁₁	[M-H]^-	421.077 3	-0.8	301.034 4, 331.0450, 259.025 2, 271.024 4, 421.075 6	ZM
30	Timosaponin D^{[11, 14, 16]}	19.55	C₄₅H₇₄O₁₉	[M+H]⁺	919.488 0	-1.9	289.214 9, 271.204 8, 433.329 1, 757.433 5	ZM
31	Timosaponin N^{[11, 17]}	19.63	C₄₅H₇₆O₂₀	[M+HCOO]^-	981.494 1	4.0	773.442 0	ZM
32	Timosaponin E1^{[11, 17]}	20.29	C₄₅H₇₆O₂₀	[M+HCOO]^-	981.495 0	4.9	773.436 5, 360.571 1	ZM
33	Timosaponin BII^{a [11, 16, 17]}	20.70	C₄₅H₇₆O₁₉	[M-H]^-	919.490 8	3.0	919.493 6	ZM
34	Gurilioside H^[11]	20.76	C₅₁H₈₆O₂₃	[M+HCOO]^-	1 111.556 2	2.8	919.490 3, 757.446 4	ZM
35	Timosaponin BIII^{[11, 14, 16]}	20.88	C₄₅H₇₄O₁₈	[M+H]⁺	903.492 1	-3.0	273.218 5, 255.208 3, 417.332 3, 399.322 2, 579.384 3, 741.433 6	ZM
36	Timosaponin AI^[14]	20.89	C₃₃H₅₄O₈	[M+H]⁺	579.387 6	-2.8	273.220 6, 255.210 6, 417.336 3, 301.142 8	ZM
37	(25S)-26-O-β-D-Glucopyranosyl- 22-hydroxy-5β-furostanol alkenyl-3β, 26-diol3-O-β-D-glucopyranosyl- (1-2)-O-β-D-galactopyranoside^{[11, 14, 16]}	21.52	C₄₅H₇₄O₁₉	[M-H]^-	917.478 3	3.4	755.422 7, 917.477 7	ZM
38	Timosaponin BⅣ^{[11, 17]}	22.65	C₅₁H₈₄O₂₃	[M+HCOO]^-	1 109.541 9	4.1	901.492 6, 739.438 6	ZM
39	2, 6, 4'-Trihydroxy-4-methoxybenzophenone^[11]	22.82	C₁₄H₁₂O₅	[M-H]^-	259.061 1	-0.6	165.018 6, 149.995 3	ZM
40	Timosaponin AIII^{[11, 14, 17]}	23.74	C₃₉H₆₄O₁₃	[M+H]⁺	741.439 9	-2.8	381.314 0, 399.325 4	ZM
41	Anemarrhenasaponin Ⅱ^[11, ^7]	24.01	C₃₉H₆₆O₁₄	[M+HCOO]^-	803.445 1	3.5	757.439 2, 595.385 5, 757.439 2	ZM
42	3β, 16α-Dihydroxy-lanosta-7, 9(11), 24-trien-21-oic acid^{[11, 14, 16]}	24.17	C₃₀H₄₆O₄	[M+H]⁺	471.346 2	-1.4	317.208 5, 453.347 6, 471.269 2	FL
43	Poricoic acid A^{[11, 14]}	28.55	C₃₁H₄₆O₅	[M-H]^-	497.327 4	0.3	479.313 3, 497.326 6	FL
44	Poricoic acid B^{[11, 14]}	32.75	C₃₀H₄₄O₅	[M-H]^-	483.311 2	-0.8	409.272 3, 483.310 2	FL
45	Polyporenic acid C^{[11, 14]}	38.58	C₃₁H₄₆O₄	[M-H]^-	481.332 3	0.0	421.305 1, 481.330 3	FL
46	Pachymic acid^{[11, 14]}	47.55	C₃₃H₅₂O₅	[M+H]⁺	529.386 3	-4.6	451.353 8, 295.243 2	FL
47	Adenine^[11]	1.69	C₅H₅N₅	[M+H]⁺	136.061 7	-0.7	119.036 4, 136.063 0	CX
48	Vanillic acid^11]	4.69	C₈H₈O₄	[M+H]⁺	169.049 5	-1.7	151.033 8, 105.034 7	CX
49	Neochlorogenic acid/Chlorogenic acid^[11]	9.43	C₁₆H₁₈O₉	[M-H]^-	353.087 8	0.1	191.056 2, 179.035 3	CX
50	Caffeic acid^[11]	11.31	C₉H₈O₄	[M-H]^-	179.034 8	-0.8	135.044 8, 179.034 7	CX
51	Ferulic acid^{a[11, 14, 15]}	16.65	C₁₀H₁₀O₄	[M-H]^-	193.050 7	0.1	134.036 7, 178.026 5, 149.058 0, 193.050 2	CX
52	Senkyunolide J^{[11, 14]}	17.86	C₁₂H₁₈O₄	[M+H]⁺	227.127 7	-0.2	153.053 8, 163.110 6, 191.106 2, 209.116 4	CX
53	Dicaffeoylquinic acid^[14]	19.80	C₂₅H₂₄O₁₂	[M-H]^-	515.119 3	-0.4	191.055 6, 353.087 5, 179.035 1, 515.119 0	CX
54	Senkyunolide D^{[11, 14]}	20.11	C₁₂H₁₄O₄	[M+H]⁺	223.096 3	-1.0	205.085 3, 223.089 1, 105.034 7	CX
55	Naringenin^[11]	20.27	C₁₅H₁₂O₅	[M+H]⁺	273.075 5	-0.8	153.018 9, 147.045 8, 119.047 8	CX
56	Senkyunolide Ⅰ^{a[11, 14]}	20.83	C₁₂H₁₆O₄	[M+H]⁺	225.111 8	0.5	225.111 8, 207.102 5	CX
57	Senkyunolide F^{[11, 14]}	20.84	C₁₂H₁₄O₃	[M+H]⁺	207.101 4	-1.0	207.101 9, 189.091 3, 119.085 7, 105.071 1, 133.064 8, 128.061 8, 161.096 9, 128.061 8, 179.107 0	CX
58	3-Butyl-4-hydroxyphthalide^{[11, 14]}	21.45	C₁₂H₁₄O₃	[M+H]⁺	207.101 4	-1.0	207.101 9, 189.091 3, 161.096 9, 128.061 8, 179.107 0	CX
59	Daidzein^[11]	21.81	C₁₅H₁₀O₄	[M+H]⁺	255.065 0	-0.9	145.029 1, 137.023 0, 119.051 3	CX
60	E-Butylidenephthalide^{[11, 14]}	23.78	C₁₂H₁₂O₂	[M+H]⁺	189.091 0	-0.1	115.055 2, 171.080 4, 189.091 6	CX
61	Butylidenephthalide^{[11, 14]}	25.77	C₁₂H₁₂O₂	[M+H]⁺	189.091 0	-0.5	171.079 5, 189.089 0	CX
62	Senkyunolide A^{a [11, 14]}	28.70	C₁₂H₁₆O₂	[M+H]⁺	193.122 1	-0.4	137.059 1, 119.085 5, 147.115 9, 175.111 2, 193.121 7, 109.064 5	CX
63	Cnidilide^{[14, 18]}	30.73	C₁₂H₁₈O₂	[M+H]⁺	195.137 9	-0.1	107.085 9, 125.059 0, 149.132 8, 177.126 4	CX
64	Z/E-Ligustilide or 3- butylphthalide^{[11, 14]}	31.00	C₁₂H₁₄O₂	[M+H]⁺	191.106 5	-0.7	105.070 5, 115.054 5, 117.070 1, 145.101 1, 173.095 4, 149.060 0	CX
65	Ligustilide dimer^[11]	35.90	C₂₄H₃₀O₄	[M+H]⁺	383.221 3	-1.0	191.106 7, 135.042 9	CX
66	Riligustilide/Z, Z'-6, 8', 7, 3'- Diligustilide^[14]	39.83	C₂₄H₂₈O₄	[M+H]⁺	381.205 7	-0.9	191.107 2, 135.043 1	CX
67	Glycyrrhizin-7, 4'-diglucoside^[11]	10.17	C₂₇H₃₂O₁₄	[M-H]^-	579.172 2	0.4	135.012 8, 255.067 0, 417.118 1	GC
68	Shaftoside/isoshaftoside^[14]	13.40	C₂₆H₂₈O₁₄	[M-H]^-	563.141 2	0.9	353.063 7, 383.074 8, 443.095 8, 473.113 9, 503.119 1	GC
69	Glucoliquiritin^[11]	13.94	C₂₇H₃₂O₁₄	[M-H]^-	579.172 2	0.4	255.066 5, 579.174 4	GC
70	Isoliquiritin apioside^{[11, 14, 16]}	15.66	C₂₆H₃₀O₁₃	[M-H]^-	549.161 9	0.9	255.066 9, 135.009 3	GC
71	Liquiritin apioside^{a [11, 14, 16]}	16.22	C₂₆H₃₀O₁₃	[M-H]^-	549.161 3	-0.1	255.066 3, 135.008 0	GC
72	Liquiritin^{a [11, 14, 16, 18]}	16.53	C₂₁H₂₂O₉	[M-H]^-	417.119 5	0.9	119.050 2, 135.008 3, 255.065 3, 417.117 6	GC
73	5-Hydroxyliquiritin^{[11, 14]}	20.34	C₂₁H₂₂O₁₀	[M-H]^-	433.113 6	-0.9	271.060 9, 177.018 7, 151.004 3, 119.051 5, 433.114 1	GC
74	Isoliquiritin^{[11, 14-16]}	21.42	C₂₁H₂₂O₉	[M-H]^-	417.118 9	-0.4	119.051 0, 135.008 7, 255.066 1, 417.117 9, 148.017 4	GC
75	Licorice glycoside A^[11]	21.61	C₃₆H₃₈O₁₆	[M-H]^-	725.210 8	2.9	255.065 0, 531.143 8, 549.161 0, 726.214 0, 175.040 3	GC
76	Licorice glycoside B^[11]	21.62	C₃₅H₃₆O₁₅	[M-H]^-	695.199 6	2.0	549.195 9, 531.152 6, 255.065 3, 135.008 6	GC
77	Licorice glycoside E^[14]	22.34	C₃₅H₃₅NO₁₄	[M-H]^-	692.199 6	1.5	255.066 6, 531.153 5, 549.160 7	GC
78	5, 7-Dihydroxyflavanone/ Pinocembrin/Liquiritigenin^{[11, 14, 16]}	22.79	C₁₅H₁₂O₄	[M-H]^-	255.066 1	-0.6	119.050 2, 135.008 0, 255.063 4	GC
79	24-Hydroxy-licorice-saponin E2^[11]	23.34	C₄₂H₆₀O₁₇	[M-H]^-	835.378 8	3.6	351.055 7, 193.036 0	GC
80	Licorice saponine G2^[14]	23.77	C₄₂H₆₂O₁₇	[M-H]^-	837.394 9	4.2	351.056 6, 837.394 5	GC
81	Uralsaponin B^{[11, 14]}	24.16	C₄₂H₆₂O₁₆	[M+H]⁺	823.408 8	-2.7	453.334 0, 647.376 6	GC
82	Echinatin^{[14, 18]}	24.24	C₁₆H₁₄O₄	[M-H]^-	269.081 3	-2.2	133.031 1, 161.020 0	GC
83	Glycyrrhizic acid^{a[11, 14]}	24.38	C₄₂H₆₂O₁₆	[M-H]^-	821.399 6	3.8	351.055 4, 821.399 3	GC
84	Licochalcone B^[11]	25.21	C₁₆H₁₄O₅	[M-H]^-	285.076 4	1.6	285.078 8, 150.037 8	GC
85	Isoliquiritigenin^{[11, 14, 16]}	25.48	C₁₅H₁₂O₄	[M-H]^-	255.066 3	-0.6	255.066 3, 135.008 6, 119.050 7	GC
86	Formononetin^{[14, 18]}	25.76	C₁₆H₁₂O₄	[M-H]^-	267.066 0	-1.0	252.042 5, 223.039 6, 267.065 7, 195.045 0	GC
87	(-)-Vestitol^[16]	25.83	C₁₆H₁₆O₄	[M-H]^-	271.097 3	-1.0	235.044 8, 109.031 1, 271.095 0, 149.062 1, 238.069 9, 121.032 4, 241.061 8, 255.068 8	GC
88	Glycycoumarin^[11]	27.37	C₂₁H₂₀O₆	[M-H]^-	367.118 6	-0.2	309.040 4, 367.118 5, 297.039 9, 284.032 2, 265.051 2, 139.039 7, 201.018 9	GC
89	Genkwanin^[11]	27.86	C₁₆H₁₂O₅	[M-H]^-	283.061 0	-0.8	268.037 0, 239.035 6, 211.036 7	GC
90	Kumatakenin^[14]	28.27	C₁₇H₁₄O₆	[M-H]^-	313.071 8	0.0	283.024 0, 255.029 6, 298.046 6, 313.239 3, 183.045 5, 295.226 9	GC
91	Glycyrin/Licoricone^{[11, 14]}	28.66	C₂₂H₂₂O₆	[M-H]^-	381.134 2	-0.6	351.087 5, 201.019 5, 323.092 6	GC
92	Lupiwighteone^{[11, 18]}	29.16	C₂₀H₁₈O₅	[M-H]^-	337.107 9	-0.7	282.052 7, 281.045 5	GC
93	Neo/Glycyrol/Isoglycyrol^[11]	29.24	C₂₁H₁₈O₆	[M-H]^-	365.102 8	-0.8	307.024 2, 295.024 2, 365.102 0, 282.016 3, 335.056 2	GC
94	Gancaonin A^[14]	29.63	C₂₁H₂₀O₅	[M-H]^-	351.123 4	-1.1	281.045 1, 308.104 3, 336.100 8, 293.082 1, 253.049 3, 307.098 7	GC
95	Glabrol^[14]	31.91	C₂₅H₂₈O₄	[M-H]^-	391.191 2	-0.8	187.114 6, 203.070 8, 391.191 2, 132.058 5	GC
96	Glyinflanin A^[14]	34.54	C₂₅H₂₈O₅	[M-H]^-	407.186 1	-0.8	187.112 3, 133.063 7, 175.075 2	GC
97	Glabric acid^[14]	38.10	C₃₀H₄₆O₅	[M+H]⁺	487.346 9	-2.3	487.330 6, 423.324 7, 451.321 9	GC
98	Licorisoflavan A^[14]	41.72	C₂₇H₃₄O₅	[M+H]⁺	439.247 7	-0.4	191.104 5, 371.182 2	GC
99	Gancaonin H^{[11, 12, 14]}	44.90	C₂₅H₂₄O₆	[M-H]^-	419.150 1	0.2	219.066 0, 419.148 5	GC
100	Vicenin Ⅱ^{[11, 12, 14]}	11.35	C₂₇H₃₀O₁₅	[M+H]⁺	595.164 2	-2.6	559.143 9, 511.124 9, 457.112 6, 337.068 9, 325.069 4, 295.060 1	SZR/GC
101	Saponarin^{[11, 12, 14]}	14.77	C₂₇H₃₀O₁₅	[M-H]^-	593.151 5	0.5	293.044 7, 413.087 4, 341.064 6	SZR/GC
102	Vitexin^{[11, 14]}	15.93	C₂₁H₂₀O₁₀	[M+H]⁺	433.112 6	-0.8	415.0985, 397.082 6, 379.082 6, 337.070 1, 313.068 9, 295.061 1, 283.059 8	SZR/GC
103	Isovitexin^{[11, 14]}	16.23	C₂₁H₂₀O₁₀	[M-H]^-	431.098 1	-0.6	311.055 2, 341.067 9, 323.058 5	SZR/GC

Compound	Degree	Source		Compound	Degree	Source
Jujuboside A^{[19, 20]}	21	SZR		Magnoflorine^[20]	13	SZR
Jujuboside B^[20]	14	SZR	Vicenin Ⅱ^[25]	14	SZR/GC
Spinosin^[20]	26	SZR	Isovitexin^[25]	15	SZR/GC
6'''-Feruloylspinosin^[20]	25	SZR	Timosaponin BII^{[19, 20]}	21	ZM
Coclaurine^[20]	14	SZR	Timosaponin BⅢ^[26]	15	ZM
Mangiferin^[19]	27	ZM	Isoliquiritin^[25]	3	GC
Neomangiferin^[21]	28	ZM	Liquiritin apioside^[25]	9	GC
Timosaponin AⅢ^[19]	16	ZM	Isoliquiritin apioside^[25]	15	GC
Senkyunolide Ⅰ^[22]	14	CX	Licorice glycoside B^[25]	2	GC
Senkyunolide A^[23]	13	CX	Uralsaponin B^[25]	2	GC
Ferulic acid^[24]	25	CX	Glycyrin^[25]	16	GC
Senkyunolide F^[21]	12	CX	Neoglycyrol^[25]	11	GC
Glycyrrhizic acid^[24]	23	GC	Licorice saponin G2^[25]	15	GC
Liquiritin^[19]	24	GC

Compound	Degree	Source		Compound	Degree	Source
Jujuboside A^{[19, 20]}	21	SZR		Magnoflorine^[20]	13	SZR
Jujuboside B^[20]	14	SZR	Vicenin Ⅱ^[25]	14	SZR/GC
Spinosin^[20]	26	SZR	Isovitexin^[25]	15	SZR/GC
6'''-Feruloylspinosin^[20]	25	SZR	Timosaponin BII^{[19, 20]}	21	ZM
Coclaurine^[20]	14	SZR	Timosaponin BⅢ^[26]	15	ZM
Mangiferin^[19]	27	ZM	Isoliquiritin^[25]	3	GC
Neomangiferin^[21]	28	ZM	Liquiritin apioside^[25]	9	GC
Timosaponin AⅢ^[19]	16	ZM	Isoliquiritin apioside^[25]	15	GC
Senkyunolide Ⅰ^[22]	14	CX	Licorice glycoside B^[25]	2	GC
Senkyunolide A^[23]	13	CX	Uralsaponin B^[25]	2	GC
Ferulic acid^[24]	25	CX	Glycyrin^[25]	16	GC
Senkyunolide F^[21]	12	CX	Neoglycyrol^[25]	11	GC
Glycyrrhizic acid^[24]	23	GC	Licorice saponin G2^[25]	15	GC
Liquiritin^[19]	24	GC

Analyte	Linearity
Neomangiferin	19.35-386.9	y = 3.077 9x - 2.852 2	0.999 8
Mangiferin	13.59-271.9	y = 4.556 6x - 7.191 8	0.999 8
Ferulic acid	2.216-44.32	y = 8.265x - 2.566 7	0.999 8
Senkyunolide Ⅰ	1.437-28.74	y = 18.867x - 2.224 3	0.999 8
Spinosin	4.657-93.15	y = 5.985x - 0.093 2	0.999 9
6'''-Feruloylspinosin	1.694-33.87	y = 7.618 4x - 0.753 1	0.999 8

Analyte	Linearity
Neomangiferin	19.35-386.9	y = 3.077 9x - 2.852 2	0.999 8
Mangiferin	13.59-271.9	y = 4.556 6x - 7.191 8	0.999 8
Ferulic acid	2.216-44.32	y = 8.265x - 2.566 7	0.999 8
Senkyunolide Ⅰ	1.437-28.74	y = 18.867x - 2.224 3	0.999 8
Spinosin	4.657-93.15	y = 5.985x - 0.093 2	0.999 9
6'''-Feruloylspinosin	1.694-33.87	y = 7.618 4x - 0.753 1	0.999 8

No.	Content/%
S1	0.012 19	0.138 5	0.074 95	6.655	0.016 73	4.926
S2	0.030 19	0.113 2	0.061 30	9.08	0.015 49	5.009
S3	0.113 5	0.078 98	0.042 76	9.51	0.015 27	5.263
S4	0.010 24	0.053 61	0.012 48	6.303	0.015 60	5.296
S5	0.109 2	0.078 32	0.042 40	8.17	0.015 33	5.223
S6	0.026 77	0.143 6	0.077 76	12.49	0.015 25	5.111
S7	0.103 2	0.087 5	0.047 39	5.907	0.016 12	5.792
S8	0.093 2	0.098 8	0.053 46	7.445	0.017 46	4.859
S9	0.024 54	0.144 5	0.078 20	13.60	0.016 16	6.330
S10	0.101 6	0.084 4	0.045 66	11.92	0.020 07	6.766
Mean ± SD	0.062 46 ± 0.040 4	0.102 1 ± 0.028 5	0.053 64 ± 0.018 44	9.11 ± 2.476	0.016 35 ± 0.001 349	5.458 ± 0.557 3

No.	Content/%
S1	0.012 19	0.138 5	0.074 95	6.655	0.016 73	4.926
S2	0.030 19	0.113 2	0.061 30	9.08	0.015 49	5.009
S3	0.113 5	0.078 98	0.042 76	9.51	0.015 27	5.263
S4	0.010 24	0.053 61	0.012 48	6.303	0.015 60	5.296
S5	0.109 2	0.078 32	0.042 40	8.17	0.015 33	5.223
S6	0.026 77	0.143 6	0.077 76	12.49	0.015 25	5.111
S7	0.103 2	0.087 5	0.047 39	5.907	0.016 12	5.792
S8	0.093 2	0.098 8	0.053 46	7.445	0.017 46	4.859
S9	0.024 54	0.144 5	0.078 20	13.60	0.016 16	6.330
S10	0.101 6	0.084 4	0.045 66	11.92	0.020 07	6.766
Mean ± SD	0.062 46 ± 0.040 4	0.102 1 ± 0.028 5	0.053 64 ± 0.018 44	9.11 ± 2.476	0.016 35 ± 0.001 349	5.458 ± 0.557 3

基于网络药理学的复方酸枣仁汤的药效物质筛选及其含量测定

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王茜 , 杨肖 , 张倩 , 李清 ^*

药学学报 | 研究论文 2021,56(11): 3130-3140

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药学学报 | 研究论文 2021, 56(11): 3130-3140

基于网络药理学的复方酸枣仁汤的药效物质筛选及其含量测定

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王茜, 杨肖, 张倩, 李清^*

作者信息

沈阳药科大学药学院, 辽宁沈阳 110016

通讯作者:

*李清, Tel: 86-24-43510589, E-mail: lqyxym@hotmail.com

Screening and determination of effective components in Compound Suanzaoren Decoction based on network pharmacology

Qian WANG, Xiao YANG, Qian ZHANG, Qing LI^*

Affiliations

School of Pharmacy, Shenyang Pharmaceutical University, Shenyang 110016, China

出版时间: 2021-11-12 doi: 10.16438/j.0513-4870.2021-0723

文章导航

摘要

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本文拟构建“化学成分-疾病靶点”网络筛选复方酸枣仁汤治疗失眠的药效物质，并建立高效、快速的方法对其进行含量测定。采用液质联用技术鉴定了复方酸枣仁汤中的103个化合物，针对其中27个潜在药效物质进行网络药理学分析，选取成分度值最大的前6个成分：新芒果苷、芒果苷、洋川芎内酯Ⅰ、斯皮诺素、6'''-阿魏酰斯皮诺素、阿魏酸作为药效物质。建立UHPLC法对药效物质进行含量测定，采用Waters CORTECS T3（2.1 mm×150 mm，1.6 μm）色谱柱，流动相为0.1%磷酸水-乙腈，分析方法验证结果表明所建立的方法专属性好，各成分在考察范围内线性关系良好（r > 0.999 0），方法具有良好的灵敏度、精密度、准确度、耐用性和稳定性。结果表明该方法能够用于复方酸枣仁汤的药效物质的筛选和含量测定，为基于药效的中药质量评价提供了依据。

关键词

复方酸枣仁汤 / 失眠 / HPLC-Q-TOF MS/MS / 网络药理学 / 含量测定

Abstract

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This article intended to build a component-target network to screen the effective components of Compound Suanzaoren Decoction, and to establish an efficient and rapid method for the determination of effective components. 103 compounds in the Compound Suanzaoren Decoction were identified by HPLC-Q-TOF MS/MS. 27 potential effective substances were analyzed by network pharmacology. The first six components with the largest degree were selected as effective components, including neomangiferin, mangiferin, ferulic acid, senkyunolide Ⅰ, spinosin, and 6'''-feruloylspinosin. A UHPLC method was established for determination. The chromatographic separation was performed on a Waters CORTECS T3 column (2.1 mm×150 mm, 1.6 μm) with the mobile phase of 0.1% phosphoric acid solution and acetonitrile. The results showed that the specificity was good with no interference for the chromatographic peaks. The linear was excellent within the scope of investigation, with the values of r higher than 0.999 0 for all analytes. The method had been verified to have good sensitivity, precision, accuracy, durability and stability. Therefore, the results showed that the method established was suitable for the screening and determination of effective components in Compound Suanzaoren Decoction, which provided a basis for the quality evaluation of traditional Chinese medicine.

Key words

Compound Suanzaoren Decoction / insomnia / HPLC-Q-TOF MS/MS / network pharmacology / determination

引用本文

王茜, 杨肖, 张倩, 李清. 基于网络药理学的复方酸枣仁汤的药效物质筛选及其含量测定. 药学学报, 2021 , 56 (11) : 3130 -3140 . DOI: 10.16438/j.0513-4870.2021-0723

Qian WANG, Xiao YANG, Qian ZHANG, Qing LI. Screening and determination of effective components in Compound Suanzaoren Decoction based on network pharmacology[J]. Acta Pharmaceutica Sinica, 2021 , 56 (11) : 3130 -3140 . DOI: 10.16438/j.0513-4870.2021-0723

正文

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失眠是影响身心健康的一大重要问题^[1]。据统计, 全世界至少有6%的人遭受失眠和睡眠紊乱的困扰^[2]。临床上常用镇静催眠类化学药治疗失眠, 但该类药物不良反应强, 依赖性高, 并存在戒断反应^[3], 因此, 不良反应小、疗效好的中药越来越受到人们的关注。

复方酸枣仁汤是治疗失眠的经典名方, 张仲景《金匮要略·血痹虚劳病脉证并治》^[4]记载“虚劳虚烦不得眠, 酸枣仁汤主之”。该方剂临床疗效显著, 沿用至今。复方酸枣仁汤由酸枣仁、知母、茯苓、川芎、甘草五味药组成, 方中酸枣仁养血补肝, 为君药; 茯苓安神通阴, 知母滋阴润燥、清热除烦, 二者共为臣药; 川芎调肝血疏肝气, 为佐药; 甘草和中缓急, 调和诸药, 为使药^[5], 各药味相辅相成, 能够起到养血补肝, 治疗失眠的功效。

复方酸枣仁汤成分繁多, 目前含量测定指标的选取未能很好地揭示药物与靶点、疾病之间的关联性, 不能体现中药复方“多靶点、多通路”的作用特点^[6], 因此, 本研究采用HPLC-Q-TOF MS/MS法鉴定了复方酸枣仁汤的化学成分, 采用网络药理学方法建立了“化学成分-疾病靶点”相关性网络^[7], 预测了复方酸枣仁汤的药效物质, 并根据传统水提取方法, 建立了基于药效物质的高效、快速的含量测定方法, 为复方酸枣仁汤质量评价体系的完善提供参考。

材料与方法

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仪器 Agilent 1260 Infinity Ⅱ (美国安捷伦公司)-Q-TOF 5600 (AB Sciex公司)、Agilent 1290 Infinity Ⅱ (美国安捷伦公司); PeakViewTM v 1.1软件(AB Sciex公司); AB135-S十万分之一天平(Mettler TOLEDO仪器有限公司); DZTW电子调温加热套(北京市永光明医疗仪器有限公司); TDZ24 WS低速台式离心机(湖南湘仪实验室仪器开发有限公司); EYELA N-1100型旋转蒸发仪(日本东京理化器械株式会社); SHZ-Ⅲ型循环水真空泵(上海亚荣生化仪器厂); KQ-300E型超声波清洗器(昆山市超声仪器有限公司)。

试剂酸枣仁皂苷A (批号CHB191210); 酸枣仁皂苷B (批号CHB190125); 斯皮诺素(批号CHB171011); 6'''-阿魏酰斯皮诺素(批号CHB180324); 知母皂苷BⅡ (批号CHB18115); 新芒果苷(批号CHB160910); 芒果苷(批号CHB160628); 阿魏酸(批号CHB180206); 洋川芎内酯A (批号CHB180615); 洋川芎内酯Ⅰ (批号CHB170926); 甘草苷(批号CHB180608); 甘草酸(CHB170606); 芹糖甘草苷(批号CHB180109)。所有的对照品均购自成都克洛玛生物有限公司, 含量质量分数均不低于98.0%。纯净水(杭州娃哈哈有限公司); 乙腈(色谱纯, 美国Fisher有限公司); 甲酸(色谱纯, 天津市博迪试剂有限公司); 甲醇(色谱纯, 美国Sigma-Aldrich公司); 磷酸(色谱纯, 天津市科密欧化学试剂有限公司)。

材料酸枣仁、知母、茯苓、甘草饮片均由某企业提供, 川芎饮片购自沈阳市各大药房, 所有饮片均由沈阳药科大学中药学院王东教授鉴定, 分别为鼠李科植物酸枣Ziziphus jujuba Mill. var. spinosa (Bunge) Hu ex H. F. Chou的干燥成熟种子、百合科植物知母Anemarrhena asphodeloides Bge.的干燥根茎、多孔菌科真菌茯苓Poria cocos (Schw.) Wolf的干燥菌核、豆科植物甘草Glycyrrhiza uralensis Fisch.的干燥根和根茎、伞形科植物川芎Ligusticum chuanxiong Hort.的干燥根茎。

化学成分鉴定

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色谱条件色谱柱: Aglient Zorbax Eclipse Plus C18 (150 mm × 4.6 mm, 3.5 μm); 流动相: 0.1%甲酸水溶液(A)-乙腈(B); 流速为1.0 mL·min^-1, 柱温30 ℃, 梯度洗脱, 洗脱程序: 0~3 min, 7%~9% B; 3~8 min, 9%~15% B; 8~16 min, 15%~20% B; 16~28 min, 20%~55% B; 28~38 min, 55%~70% B; 38~48 min, 70%~90% B; 48~51 min, 90% B。进样量: 5 μL。

质谱条件采用AB Sciex Q TOF系统, 离子源为电喷雾离子源(ESI源); 检测方式为正、负离子检测; 离子喷雾电压为-4 500 V和5 000 V; 离子源温度: 550 ℃; 雾化气(N₂) 压力: 55 psi (1 psi ≈ 6.9 kPa); 辅助气(N₂) 压力: 55 psi; 气帘气(N₂) 压力: 35 psi; TOF MS模式下扫描范围为m/z 100~1 500 Da; 去簇电压(DP): 60 V (正离子)/-60 V (负离子); 碰撞能(CE): 10 V (正离子)/-10 V (负离子); TOF MS/MS模式下扫描范围为m/z 100~1 000 Da; 去簇电压(DP): 60 V (正离子)/-60 V (负离子); 碰撞能(CE): 35 V (正离子)/-35 V (负离子)。

对照品溶液的制备分别取酸枣仁皂苷A、酸枣仁皂苷B、斯皮诺素、6'''-阿魏酰斯皮诺素、知母皂苷BⅡ、芒果苷、新芒果苷、阿魏酸、洋川芎内酯Ⅰ、洋川芎内酯A、甘草苷、甘草酸、芹糖甘草苷13种对照品适量, 用甲醇溶解, 摇匀配制成浓度均为25 μg·mL^-1的混合对照品溶液。

供试品溶液的制备将收集的酸枣仁、知母、茯苓、川芎、甘草多批饮片按复方酸枣仁汤处方比例, 随机组合成10批次样品。精密称取各味饮片于圆底烧瓶中, 加入8倍体积的水, 浸泡80 min, 加热回流30 min, 采用七号药筛滤过。向药渣中继续加入6倍体积的水, 加热回流25 min, 滤过, 合并两次滤液, 减压浓缩至0.83 g·mL^-1 (生药材), 即得复方酸枣仁汤。精密量取复方酸枣仁汤2.0 mL于10 mL量瓶, 加入甲醇适量, 超声20 min, 放冷, 定容, 摇匀, 4 000 r·min^-1离心5 min, 取上清, 过0.22 μm微孔滤膜, 取续滤液即得。

按照上述色谱条件和质谱条件, 进样分析, 通过与对照品保留时间、高分辨准分子离子及碎片离子等信息进行比对, 并参考文献, 进行结构鉴定。

网络药理学分析流程 通过查阅文献, 在已鉴定出来的化合物中, 寻找复方酸枣仁汤组方饮片水提入血成分, 作为潜在的活性成分。通过PubChem^[8]查询潜在活性成分的3D结构, 导入PharmMapper数据库^[9]预测成分的靶点(仅选择“人源基因”)。通过GeneCards数据库和OMIM数据库, 以“insomnia”和“sleepless”为关键词, 搜索与失眠有关的靶点。成分靶点与疾病靶点取交集得到共同靶点, 将这些共同靶点视为复方酸枣仁汤治疗失眠的关键靶点, 利用Cytoscape 3.7.2软件^[10]构建“化学成分-疾病靶点”网络并进行通路富集分析, 筛选药效物质。

UHPLC法测定6种药效物质

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UHPLC色谱条件色谱柱: Waters Cortecs T3 (2.1 mm × 150 mm, 1.6 μm); 流动相: 0.1%磷酸水溶液(A)-乙腈(B); 流速为0.3 mL·min^-1, 柱温30 ℃, 梯度洗脱, 洗脱程序: 0~3 min, 7%~8% B; 3~8 min, 8%~8.5% B; 8~13 min, 8.5% B; 13~16 min, 8.5%~9% B; 16~20 min, 9% B; 20~23 min, 9%~10% B; 23~27 min, 10%~11% B; 27~40 min, 11%~15% B; 40~55 min, 15%~17% B; 55~60 min, 17%~19% B; 60~62 min, 19%~22% B; 62~66 min, 22%~90% B。进样量1 μL, 检测波长275 nm。

混合对照品溶液的制备分别取新芒果苷、芒果苷、阿魏酸、洋川芎内酯Ⅰ、斯皮诺素、6'''-阿魏酰斯皮诺素对照品适量, 精密称定, 用甲醇溶解、稀释定容, 配制成质量浓度分别为386.9、271.9、44.32、28.74、93.15和33.87 μg·mL^-1的混合对照品溶液。

供试品溶液的制备按照“化学成分鉴定”项下“供试品溶液的制备”方法, 制备供试品溶液。

缺味对照溶液的制备按照“化学成分鉴定”项下“供试品溶液的制备”方法, 分别制备缺少酸枣仁饮片、缺少知母饮片、缺少川芎饮片的缺味对照溶液。

系统适用性取混合对照品溶液, 按照“UHPLC色谱条件”, 连续进样6次, 记录理论塔板数(n)、相邻色谱峰的分离度(R)、各色谱峰信噪比、拖尾因子、计算各待测成分峰面积的RSD。

分析方法验证

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专属性分别取混合对照品溶液、供试品溶液、各缺味对照溶液, 按照“UHPLC色谱条件”, 进样分析, 比较色谱图。

线性与范围分别精密量取上述混合对照品溶液0.5、1.0、2.0、5.0和7.5 mL置于10 mL量瓶中, 用甲醇定容至刻度, 将这5种溶液及“混合对照品溶液的制备”项下的溶液作为标准系列溶液。按照“UHPLC色谱条件”进样分析, 记录峰面积。

检测限和定量限取混合对照品溶液, 用甲醇进行逐步稀释, 以信噪比为3∶1和10∶1为参考, 配制溶液, 分别测得各化合物的检测限和定量限。

稳定性取供试品溶液, 4 ℃放置, 分别于0、2、4、8、12和24 h进样分析, 计算各待测成分峰面积的RSD。

精密度精密量取同一批复方酸枣仁汤1.0、2.0和3.0 mL, 按“化学成分鉴定”项下“供试品溶液的制备”方法, 制备低、中、高3个浓度的供试品溶液, 每一种浓度平行制备3份, 按照“UHPLC色谱条件”进样分析, 计算各成分含量, 并计算RSD, 作为重复性实验。精密量取同一批复方酸枣仁汤2.0 mL, 按“化学成分鉴定”项下“供试品溶液的制备”方法, 每天制备相同浓度的供试品溶液3份, 平行制备3天, 按照“UHPLC色谱条件”连续3天进样分析, 计算各成分含量, 并计算RSD, 作为中间精密度实验。

准确度取已知各待测成分含量的复方酸枣仁汤9份, 精密量取1.0 mL, 分别按约为已知含量的50%、100%和150%等3个水平加入对照品, 制备低、中、高3种不同浓度的供试品溶液, 每一种浓度平行制备3份, 按照“UHPLC色谱条件”进样分析。计算各待测成分的平均回收率及RSD。

耐用性分别考察色谱条件在不同进样体积(0.9、1和1.1 μL), 不同检测波长(274、275和276 nm), 不同体积分数的磷酸溶液流动相(体积分数为0.09%磷酸溶液、体积分数为0.10%磷酸溶液和体积分数为0.11%磷酸溶液), 不同柱温(29、30和31 ℃) 的条件下, 测定待测成分的含量, 并计算不同条件的RSD。

含量测定 分别取混合对照品溶液, 按供试品溶液制备方法制备10批不同批次饮片提取的复方酸枣仁汤供试品, 按“UHPLC色谱条件”进样分析, 记录各待测成分峰面积, 采用外标法计算各待测成分的含量。

结果

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1 化学成分鉴定

在复方酸枣仁汤中初步鉴定了103个化合物, 通过与对照品保留时间、高分辨准分子离子及碎片离子等信息进行比对, 准确鉴定了13个化合物, 所有化合物的质量误差均小于5.0×10^-6。鉴定结果及成分信息如表 1^[11-18]所示。对103个化合物的来源进行归属^[16-18], 发现有27个化合物来源于酸枣仁, 14个来自知母, 5个来自茯苓, 20个来自川芎, 33个来源于甘草, 化合物100、101、102、103为酸枣仁和甘草两种饮片的共有成分。

2 网络药理学分析

依据实验室的前期研究成果^[13]以及文献报道, 在已鉴定的化合物中查找到入血成分27个, 如表 2^[19-26]所示, 每种成分选取排名靠前的35个靶点。以“insomnia”和“sleepless”为关键词, 得到与失眠有关的靶点5 052个。成分靶点与疾病靶点取交集得到156个关键靶点, 将27个入血成分及关键靶点导入Cytoscape 3.7.2, 构建“化学成分-疾病靶点”的可视化网络, 该网络有183个节点, 460条边, 如图 1所示。图中绿色菱形代表关键靶点, 粉色圆形代表入血成分。针对关键靶点进行通路富集分析, 筛选P < 0.01的通路, 最终富集到49条信号通路, 如图 2所示。选取度值高于24的6个成分作为复方酸枣仁汤的药效物质对其进行质量控制, 它们依次为新芒果苷(28)、芒果苷(27)、洋川芎内酯Ⅰ (27)、斯皮诺素(26)、6'''-阿魏酰斯皮诺素(25)、阿魏酸(25)。

3 系统适用性

结果显示按新芒果苷峰计, 理论塔板数(n) 均大于4.2×10⁴, 相邻色谱峰的分离度(R) 均大于1.5, 各色谱峰信噪比(S/N) 均大于10, 拖尾因子均介于0.95~1.05之间。新芒果苷、芒果苷、阿魏酸、洋川芎内酯Ⅰ、斯皮诺素、6'''-阿魏酰斯皮诺素峰面积的RSD分别为0.8%、0.8%、0.8%、0.6%、0.9%、1.0%, 表明仪器的精密度良好。

4 分析方法验证

4.1 专属性

通过对比混合对照品溶液、供试品溶液、缺味对照溶液, 结果显示, 新芒果苷、芒果苷来自知母, 阿魏酸、洋川芎内酯Ⅰ来自川芎, 斯皮诺素、6'''-阿魏酰斯皮诺素来自酸枣仁, 该方法专属性良好, 阴性溶液无干扰。典型色谱图见图 3。

4.2 线性与范围

以各对照品质量浓度(μg·mL^-1) 为横坐标(x), 以峰面积A为纵坐标(y), 绘制标准曲线, 计算回归方程。新芒果苷、芒果苷、阿魏酸、洋川芎内酯Ⅰ、斯皮诺素、6'''-阿魏酰斯皮诺素在考察范围内线性关系良好, 相关系数均大于0.999 0, 结果见表 3。

4.3 检测限与定量限

结果显示, 新芒果苷、芒果苷、阿魏酸、洋川芎内酯Ⅰ、斯皮诺素和6'''-阿魏酰斯皮诺素的检测限质量浓度分别为0.201 5、0.504 5、0.372 2、0.191 9、0.284 7和0.188 9 μg·mL^-1, 各成分定量限质量浓度分别为0.604 6、0.756 8、0.744 5、0.383 8、0.569 4和0.377 9 μg·mL^-1, 表明方法灵敏度良好。

4.4 稳定性

新芒果苷、芒果苷、阿魏酸、洋川芎内酯Ⅰ、斯皮诺素和6'''-阿魏酰斯皮诺素峰面积的RSD分别为1.6%、1.4%、2.0%、1.6%、1.4%和1.6%, 各成分在24 h内稳定(RSD < 2.0%)。

4.5 精密度

重复性实验中新芒果苷、芒果苷、阿魏酸、洋川芎内酯Ⅰ、斯皮诺素和6'''-阿魏酰斯皮诺素含量的RSD分别为2.1%、1.2%、1.1%、0.8%、1.1%、1.3%, 表明方法重复性良好(RSD < 3.0%)。中间精密度实验中各成分含量的RSD分别为0.6%、0.8%、1.0%、0.5%、0.7%和1.2%, 表明方法中间精密度良好(RSD < 3.0%)。

4.6 准确度

测得新芒果苷、芒果苷、阿魏酸、洋川芎内酯Ⅰ、斯皮诺素和6'''-阿魏酰斯皮诺素的平均回收率在104.2%~108.9%, RSD均不高于2.1%, 表明方法准确度良好。

4.7 耐用性

各色谱条件下, 新芒果苷、芒果苷、阿魏酸、洋川芎内酯Ⅰ、斯皮诺素和6'''-阿魏酰斯皮诺素含量的RSD均不超过2.5%, 表明方法耐用性良好。

5 含量测定结果

测得10批复方酸枣仁汤中新芒果苷、芒果苷、阿魏酸、洋川芎内酯Ⅰ、斯皮诺素和6'''-阿魏酰斯皮诺素的含量, 结果如表 4所示。

讨论

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实验研究表明, 失眠与体内神经递质如5-HT (5-羟色胺)、NO (一氧化碳)、GABA (γ-氨基丁酸) 等密切相关^[27]。5-HT是引发睡眠的重要神经递质, 中缝核内的5-HT能神经元分泌的5-HT与快眼动睡眠时间成正比^[28]。研究发现, 长期使用地西泮治疗失眠, 能够使神经活性配体-受体相互作用信号通路显著变化, 证明该通路和失眠存在很强相关性^[29]。本研究网络药理学中通路富集分析结果最显著的是5-羟色胺能突触通路, 其次是神经活性配体-受体相互作用通路, 这与文献报道结果吻合。除此之外, 富集得到的通路还包含TNF信号通路、多巴胺能信号通路、cAMP信号通路、钙信号通路等。因而推断复方酸枣仁汤治疗失眠可能是多通路协同作用。

网络药理学中“成分-靶点-通路”相互作用不但可以预测中药复方制剂治疗疾病的机制, 还能够辅助中药复方制剂中有效成分的筛选^[30-32]。有研究表明, 6'''-阿魏酰斯皮诺素能够不同程度地改变大鼠的自主活动、入睡数量和睡眠时间^[33], 斯皮诺素能够作用于5-HT1A, 增强戊巴比妥钠诱导的小鼠的翻正反射丧失^[34]。阿魏酸能够提高脑内5-HT的浓度^[35], 影响大脑活动, 诱导睡眠。通过“化学成分-疾病靶点”网络, 推测这些化合物促进睡眠作用的发挥可能是通过作用于MAOB、PTGS1、PTGS2等靶点参与5-羟色胺能通路。大量研究发现, 细胞因子能够调节睡眠^[36]。长期失眠的患者由于细胞内的炎症反应, 体内细胞因子发生明显变化, 例如IL-6、TNF-α等明显增加, 导致睡眠质量下降^[37], 而芒果苷、新芒果苷、洋川芎内酯Ⅰ可以通过调节MAPK8、CASP3、MMP3、PIK3CG等靶点参与TNF信号通路, 发挥抗炎作用^[38-40], 从而改善睡眠质量。这体现了中药复方“多成分、多靶点、多通路”的作用特点, 同时也为复方酸枣仁汤药效物质的选择提供了依据。

《中华人民共和国药典》2020年版^[41]并未收载复方酸枣仁汤相关制剂, 只对单味饮片含量测定指标进行了规定, 酸枣仁、知母、川芎饮片中非皂苷类成分含量测定的指标分别为斯皮诺素、芒果苷和阿魏酸, 本研究依据“化学成分-疾病靶点”网络分析结果, 从质量控制指标的选择原则和实际操作出发, 选取了酸枣仁中的斯皮诺素和6'''-阿魏酰斯皮诺素, 知母中的新芒果苷和芒果苷, 川芎中的阿魏酸和洋川芎内酯Ⅰ这6种度值大于24的药效物质对其进行含量测定。所建立的UHPLC法能够高效、简单、快速地完成对10批复方酸枣仁汤中6种药效物质的含量测定, 为基于药效的复方酸枣仁汤的质量评价提供了依据。

作者贡献: 王茜主要进行了本文的选题与设计、方法建立、实验数据处理、撰写文章等。杨肖在前期方法摸索及数据处理方面提供了帮助。张倩对本文的实验思路、方法建立提供了指导。李清对本文选题与设计、实验思路、方法建立及文章修改提供了宝贵意见。

利益冲突: 无任何利益冲突。

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2021年第56卷第11期

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doi: 10.16438/j.0513-4870.2021-0723

接收时间：2021-05-18
首发时间：2025-12-18
出版时间：2021-11-12

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收稿日期：2021-05-18
修回日期：2021-08-15

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沈阳药科大学药学院, 辽宁沈阳 110016

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*李清, Tel: 86-24-43510589, E-mail: lqyxym@hotmail.com

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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TxT

No.	Identification	t_R/min	Formula	Ion adduction	Measured mass (m/z)	Error/10^-6	Fragment (m/z)	Source
1	3S-1-N-β-D-Glucopyranosyl-3- hydroxy-indole-3-acetic acid/3R- 1-N-β-D-glucopyranosyl-3-hydroxy-indole-3-acetic acid^[11]	4.54	C₁₆H₁₉NO₉	[M+H]⁺	370.113 0	-0.7	212.067 4, 188.069 6, 146.059 2, 128.049 3	SZR
2	Protocatechuic acid^[11]	5.20	C₇H₆O₄	[M-H]^-	153.019 5	0.8	107.015 9, 124.016 5	SZR
3	6-Glu-coclaurine^[12]	7.13	C₂₃H₂₉NO₈	[M+H]⁺	448.196 7	-1.0	286.142 8, 269.115 8, 175.074 6, 107.049 5	SZR
4	4-Hydroxybenzoic acid^[12]	8.94	C₇H₆O₃	[M-H]^-	137.025 0	4.5	108.022 9, 136.016 7	SZR
5	Epicatechin^[13]	9.80	C₁₅H₁₄O₆	[M-H]^-	289.071 6	-0.5	221.081 2, 203.071 1, 123.044 9, 109.030 1	SZR
6	Coclaurine^{[11, 12]}	10.61	C₁₇H₁₉NO₃	[M+H]⁺	286.143 9	0.4	107.049 6, 175.075 3	SZR
7	Magnoflorine^[12]	11.52	C₂₀H₂₃NO₄	[M+H]⁺	342.169 7	-0.7	297.109 7, 282.086 2, 265.083 2, 222.088 7	SZR
8	Catechine^[13]	12.00	C₁₅H₁₄O₆	[M-H]^-	289.071 6	-0.7	221.082 6, 203.070 7, 187.039 2, 109.030 2	SZR
9	Hovetrichoside C^[11]	12.44	C₂₁H₂₂O₁₁	[M-H]^-	449.108 5	-0.9	259.060 0, 269.046 2, 125.023 9, 287.056 5	SZR
10	Kaempferol-3-O-rutinoside^{[11, 14]}	14.50	C₂₇H₃₀O₁₅	[M+H]⁺	595.164 6	-1.9	433.111 9, 337.068 9, 313.069 2, 283.058 3	SZR
11	Puerarin^[11]	14.70	C₂₁H₂₀O₉	[M-H]^-	415.103 7	-0.9	252.041 3, 25.053 1,	SZR
12	Spinosin^{a [11, 14, 15]}	15.33	C₂₈H₃₂O₁₅	[M+H]⁺	609.180 1	-2.2	327.085 2, 351.085 9, 297.075 3, 447.127 9, 285.075 3, 411.107 5, 609.178 6	SZR
13	Camelliaside B^[11]	15.45	C₃₂H₃₈O₁₉	[M-H]^-	725.194 9	1.9	284.033 4, 575.153 3	SZR
14	Caaverine^[11]	15.78	C₁₇H₁₇NO₂	[M+H]⁺	268.133 1	-0.3	251.105 4, 236.082 6, 219.079 4, 208.087 4, 191.084 5, 190.076 6, 189.068 8, 165.069 6	SZR
15	6'''-Vanilloylspinosin^{[11, 13]}	17.57	C₃₆H₃₈O₁₈	[M+H]⁺	759.211 7	-1.8	639.168 3, 429.117 7, 351.085 2, 327.085 4, 297.075 4	SZR
16	6'''-p-Hydroxylbenzoyspinosin^[11-13]	18.39	C₃₅H₃₆O₁₇	[M+H]⁺	729.200 8	-2.4	609.165 7, 429.117 1, 351.086 0, 327.084 9, 297.074 0, 121.028 5	SZR
17	Vitexin-4''-O-glucoside^[11-14]	18.43	C₂₇H₃₀O₁₅	[M+H]⁺	595.164 2	-2.6	287.054 9, 595.163 7	SZR
18	6'''-O-(3R-1-N-β-D-Glucopyranosyl-2-oxo-3-hydroxy-indole-3-acetyl) spinosin^[11]	19.06	C₄₄H₄₉NO₂₃	[M-H]^-	958.266 5	4.5	649.177 4	SZR
19	6'''-Sinapoylspinosin^[11-13]	19.39	C₃₉H₄₂O₁₉	[M+H]⁺	815.237 3	-2.5	635.170 3, 447.127 3, 429.118 6, 393.094 2, 351.088 6, 327.085 4, 297.075 5, 207.063 0, 175.038 6	SZR
20	6'''-Feruloylspinosin^{a [11-14, 16]}	19.91	C₃₈H₄₀O₁₈	[M+H]⁺	785.227 6	-1.5	327.084 6, 351.084 5, 177.053 7, 297.074 3, 429.116 5, 665.184 6, 785.223 7	SZR
21	6'''-p-Coumaroylspinosin^[11-13]	19.97	C₃₇H₃₈O₁₇	[M+H]⁺	755.217 4	-1.0	447.127 5, 429.116 5, 351.085 4, 327.085 7, 297.074 9, 147.044 3	SZR
22	epi-6'''-(N-β-D-Glucopyranosyl)-2'''', 3''''-dihydro-2''''-oxo-3''''-yl-acetate spinosin^[11]	20.22	C₄₄H₄₉NO₂₂	[M+H]⁺	944.279 9	-2.1	782.225 5, 764.216 2, 489.137 7, 393.095 6, 351.085 5, 327.085 2	SZR
23	N-Nornuciferine^[11]	21.10	C₁₈H₁₉NO₂	[M+H]⁺	282.148 6	-0.9	265.120 6, 250.097 2, 235.073 9, 234.101 9, 191.084 4, 189.068 5, 178.076 4	SZR
24	6''-O-Feruloylspinosin^{[11-14, 16]}	21.19	C₃₈H₄₀O₁₈	[M+H]⁺	785.226 6	-2.8	489.141 2, 447.127 1, 327.085 3, 285.074 3	SZR
25	Amphibine D/Lotusine B^[12]	22.46	C₃₆H₄₉N₅O₅	[M+H]⁺	632.379 0	-2.6	148.112 1, 289.190 4, 261.196 0, 316.199 6, 344.196 0, 632.377 1	SZR
26	Jujuboside A^{a [11-14, 16]}	23.30	C₅₈H₉₄O₂₆	[M-H]^-	1 205.600 2	3.4	911.527 3	SZR
27	Jujuboside B^{a [11-14, 16]}	24.15	C₅₂H₈₄O₂₁	[M-H]^-	1 043.549 3	5.0	911.505 5	SZR
28	Neomangiferin^{a [11, 14, 15]}	8.35	C₂₅H₂₈O₁₆	[M-H]^-	583.130 6	0.2	301.034 4, 331.044 6, 463.086 2, 493.096 8	ZM
29	Mangiferin^{a [11, 14-16]}	11.22	C₁₉H₁₈O₁₁	[M-H]^-	421.077 3	-0.8	301.034 4, 331.0450, 259.025 2, 271.024 4, 421.075 6	ZM
30	Timosaponin D^{[11, 14, 16]}	19.55	C₄₅H₇₄O₁₉	[M+H]⁺	919.488 0	-1.9	289.214 9, 271.204 8, 433.329 1, 757.433 5	ZM
31	Timosaponin N^{[11, 17]}	19.63	C₄₅H₇₆O₂₀	[M+HCOO]^-	981.494 1	4.0	773.442 0	ZM
32	Timosaponin E1^{[11, 17]}	20.29	C₄₅H₇₆O₂₀	[M+HCOO]^-	981.495 0	4.9	773.436 5, 360.571 1	ZM
33	Timosaponin BII^{a [11, 16, 17]}	20.70	C₄₅H₇₆O₁₉	[M-H]^-	919.490 8	3.0	919.493 6	ZM
34	Gurilioside H^[11]	20.76	C₅₁H₈₆O₂₃	[M+HCOO]^-	1 111.556 2	2.8	919.490 3, 757.446 4	ZM
35	Timosaponin BIII^{[11, 14, 16]}	20.88	C₄₅H₇₄O₁₈	[M+H]⁺	903.492 1	-3.0	273.218 5, 255.208 3, 417.332 3, 399.322 2, 579.384 3, 741.433 6	ZM
36	Timosaponin AI^[14]	20.89	C₃₃H₅₄O₈	[M+H]⁺	579.387 6	-2.8	273.220 6, 255.210 6, 417.336 3, 301.142 8	ZM
37	(25S)-26-O-β-D-Glucopyranosyl- 22-hydroxy-5β-furostanol alkenyl-3β, 26-diol3-O-β-D-glucopyranosyl- (1-2)-O-β-D-galactopyranoside^{[11, 14, 16]}	21.52	C₄₅H₇₄O₁₉	[M-H]^-	917.478 3	3.4	755.422 7, 917.477 7	ZM
38	Timosaponin BⅣ^{[11, 17]}	22.65	C₅₁H₈₄O₂₃	[M+HCOO]^-	1 109.541 9	4.1	901.492 6, 739.438 6	ZM
39	2, 6, 4'-Trihydroxy-4-methoxybenzophenone^[11]	22.82	C₁₄H₁₂O₅	[M-H]^-	259.061 1	-0.6	165.018 6, 149.995 3	ZM
40	Timosaponin AIII^{[11, 14, 17]}	23.74	C₃₉H₆₄O₁₃	[M+H]⁺	741.439 9	-2.8	381.314 0, 399.325 4	ZM
41	Anemarrhenasaponin Ⅱ^[11, ^7]	24.01	C₃₉H₆₆O₁₄	[M+HCOO]^-	803.445 1	3.5	757.439 2, 595.385 5, 757.439 2	ZM
42	3β, 16α-Dihydroxy-lanosta-7, 9(11), 24-trien-21-oic acid^{[11, 14, 16]}	24.17	C₃₀H₄₆O₄	[M+H]⁺	471.346 2	-1.4	317.208 5, 453.347 6, 471.269 2	FL
43	Poricoic acid A^{[11, 14]}	28.55	C₃₁H₄₆O₅	[M-H]^-	497.327 4	0.3	479.313 3, 497.326 6	FL
44	Poricoic acid B^{[11, 14]}	32.75	C₃₀H₄₄O₅	[M-H]^-	483.311 2	-0.8	409.272 3, 483.310 2	FL
45	Polyporenic acid C^{[11, 14]}	38.58	C₃₁H₄₆O₄	[M-H]^-	481.332 3	0.0	421.305 1, 481.330 3	FL
46	Pachymic acid^{[11, 14]}	47.55	C₃₃H₅₂O₅	[M+H]⁺	529.386 3	-4.6	451.353 8, 295.243 2	FL
47	Adenine^[11]	1.69	C₅H₅N₅	[M+H]⁺	136.061 7	-0.7	119.036 4, 136.063 0	CX
48	Vanillic acid^11]	4.69	C₈H₈O₄	[M+H]⁺	169.049 5	-1.7	151.033 8, 105.034 7	CX
49	Neochlorogenic acid/Chlorogenic acid^[11]	9.43	C₁₆H₁₈O₉	[M-H]^-	353.087 8	0.1	191.056 2, 179.035 3	CX
50	Caffeic acid^[11]	11.31	C₉H₈O₄	[M-H]^-	179.034 8	-0.8	135.044 8, 179.034 7	CX
51	Ferulic acid^{a[11, 14, 15]}	16.65	C₁₀H₁₀O₄	[M-H]^-	193.050 7	0.1	134.036 7, 178.026 5, 149.058 0, 193.050 2	CX
52	Senkyunolide J^{[11, 14]}	17.86	C₁₂H₁₈O₄	[M+H]⁺	227.127 7	-0.2	153.053 8, 163.110 6, 191.106 2, 209.116 4	CX
53	Dicaffeoylquinic acid^[14]	19.80	C₂₅H₂₄O₁₂	[M-H]^-	515.119 3	-0.4	191.055 6, 353.087 5, 179.035 1, 515.119 0	CX
54	Senkyunolide D^{[11, 14]}	20.11	C₁₂H₁₄O₄	[M+H]⁺	223.096 3	-1.0	205.085 3, 223.089 1, 105.034 7	CX
55	Naringenin^[11]	20.27	C₁₅H₁₂O₅	[M+H]⁺	273.075 5	-0.8	153.018 9, 147.045 8, 119.047 8	CX
56	Senkyunolide Ⅰ^{a[11, 14]}	20.83	C₁₂H₁₆O₄	[M+H]⁺	225.111 8	0.5	225.111 8, 207.102 5	CX
57	Senkyunolide F^{[11, 14]}	20.84	C₁₂H₁₄O₃	[M+H]⁺	207.101 4	-1.0	207.101 9, 189.091 3, 119.085 7, 105.071 1, 133.064 8, 128.061 8, 161.096 9, 128.061 8, 179.107 0	CX
58	3-Butyl-4-hydroxyphthalide^{[11, 14]}	21.45	C₁₂H₁₄O₃	[M+H]⁺	207.101 4	-1.0	207.101 9, 189.091 3, 161.096 9, 128.061 8, 179.107 0	CX
59	Daidzein^[11]	21.81	C₁₅H₁₀O₄	[M+H]⁺	255.065 0	-0.9	145.029 1, 137.023 0, 119.051 3	CX
60	E-Butylidenephthalide^{[11, 14]}	23.78	C₁₂H₁₂O₂	[M+H]⁺	189.091 0	-0.1	115.055 2, 171.080 4, 189.091 6	CX
61	Butylidenephthalide^{[11, 14]}	25.77	C₁₂H₁₂O₂	[M+H]⁺	189.091 0	-0.5	171.079 5, 189.089 0	CX
62	Senkyunolide A^{a [11, 14]}	28.70	C₁₂H₁₆O₂	[M+H]⁺	193.122 1	-0.4	137.059 1, 119.085 5, 147.115 9, 175.111 2, 193.121 7, 109.064 5	CX
63	Cnidilide^{[14, 18]}	30.73	C₁₂H₁₈O₂	[M+H]⁺	195.137 9	-0.1	107.085 9, 125.059 0, 149.132 8, 177.126 4	CX
64	Z/E-Ligustilide or 3- butylphthalide^{[11, 14]}	31.00	C₁₂H₁₄O₂	[M+H]⁺	191.106 5	-0.7	105.070 5, 115.054 5, 117.070 1, 145.101 1, 173.095 4, 149.060 0	CX
65	Ligustilide dimer^[11]	35.90	C₂₄H₃₀O₄	[M+H]⁺	383.221 3	-1.0	191.106 7, 135.042 9	CX
66	Riligustilide/Z, Z'-6, 8', 7, 3'- Diligustilide^[14]	39.83	C₂₄H₂₈O₄	[M+H]⁺	381.205 7	-0.9	191.107 2, 135.043 1	CX
67	Glycyrrhizin-7, 4'-diglucoside^[11]	10.17	C₂₇H₃₂O₁₄	[M-H]^-	579.172 2	0.4	135.012 8, 255.067 0, 417.118 1	GC
68	Shaftoside/isoshaftoside^[14]	13.40	C₂₆H₂₈O₁₄	[M-H]^-	563.141 2	0.9	353.063 7, 383.074 8, 443.095 8, 473.113 9, 503.119 1	GC
69	Glucoliquiritin^[11]	13.94	C₂₇H₃₂O₁₄	[M-H]^-	579.172 2	0.4	255.066 5, 579.174 4	GC
70	Isoliquiritin apioside^{[11, 14, 16]}	15.66	C₂₆H₃₀O₁₃	[M-H]^-	549.161 9	0.9	255.066 9, 135.009 3	GC
71	Liquiritin apioside^{a [11, 14, 16]}	16.22	C₂₆H₃₀O₁₃	[M-H]^-	549.161 3	-0.1	255.066 3, 135.008 0	GC
72	Liquiritin^{a [11, 14, 16, 18]}	16.53	C₂₁H₂₂O₉	[M-H]^-	417.119 5	0.9	119.050 2, 135.008 3, 255.065 3, 417.117 6	GC
73	5-Hydroxyliquiritin^{[11, 14]}	20.34	C₂₁H₂₂O₁₀	[M-H]^-	433.113 6	-0.9	271.060 9, 177.018 7, 151.004 3, 119.051 5, 433.114 1	GC
74	Isoliquiritin^{[11, 14-16]}	21.42	C₂₁H₂₂O₉	[M-H]^-	417.118 9	-0.4	119.051 0, 135.008 7, 255.066 1, 417.117 9, 148.017 4	GC
75	Licorice glycoside A^[11]	21.61	C₃₆H₃₈O₁₆	[M-H]^-	725.210 8	2.9	255.065 0, 531.143 8, 549.161 0, 726.214 0, 175.040 3	GC
76	Licorice glycoside B^[11]	21.62	C₃₅H₃₆O₁₅	[M-H]^-	695.199 6	2.0	549.195 9, 531.152 6, 255.065 3, 135.008 6	GC
77	Licorice glycoside E^[14]	22.34	C₃₅H₃₅NO₁₄	[M-H]^-	692.199 6	1.5	255.066 6, 531.153 5, 549.160 7	GC
78	5, 7-Dihydroxyflavanone/ Pinocembrin/Liquiritigenin^{[11, 14, 16]}	22.79	C₁₅H₁₂O₄	[M-H]^-	255.066 1	-0.6	119.050 2, 135.008 0, 255.063 4	GC
79	24-Hydroxy-licorice-saponin E2^[11]	23.34	C₄₂H₆₀O₁₇	[M-H]^-	835.378 8	3.6	351.055 7, 193.036 0	GC
80	Licorice saponine G2^[14]	23.77	C₄₂H₆₂O₁₇	[M-H]^-	837.394 9	4.2	351.056 6, 837.394 5	GC
81	Uralsaponin B^{[11, 14]}	24.16	C₄₂H₆₂O₁₆	[M+H]⁺	823.408 8	-2.7	453.334 0, 647.376 6	GC
82	Echinatin^{[14, 18]}	24.24	C₁₆H₁₄O₄	[M-H]^-	269.081 3	-2.2	133.031 1, 161.020 0	GC
83	Glycyrrhizic acid^{a[11, 14]}	24.38	C₄₂H₆₂O₁₆	[M-H]^-	821.399 6	3.8	351.055 4, 821.399 3	GC
84	Licochalcone B^[11]	25.21	C₁₆H₁₄O₅	[M-H]^-	285.076 4	1.6	285.078 8, 150.037 8	GC
85	Isoliquiritigenin^{[11, 14, 16]}	25.48	C₁₅H₁₂O₄	[M-H]^-	255.066 3	-0.6	255.066 3, 135.008 6, 119.050 7	GC
86	Formononetin^{[14, 18]}	25.76	C₁₆H₁₂O₄	[M-H]^-	267.066 0	-1.0	252.042 5, 223.039 6, 267.065 7, 195.045 0	GC
87	(-)-Vestitol^[16]	25.83	C₁₆H₁₆O₄	[M-H]^-	271.097 3	-1.0	235.044 8, 109.031 1, 271.095 0, 149.062 1, 238.069 9, 121.032 4, 241.061 8, 255.068 8	GC
88	Glycycoumarin^[11]	27.37	C₂₁H₂₀O₆	[M-H]^-	367.118 6	-0.2	309.040 4, 367.118 5, 297.039 9, 284.032 2, 265.051 2, 139.039 7, 201.018 9	GC
89	Genkwanin^[11]	27.86	C₁₆H₁₂O₅	[M-H]^-	283.061 0	-0.8	268.037 0, 239.035 6, 211.036 7	GC
90	Kumatakenin^[14]	28.27	C₁₇H₁₄O₆	[M-H]^-	313.071 8	0.0	283.024 0, 255.029 6, 298.046 6, 313.239 3, 183.045 5, 295.226 9	GC
91	Glycyrin/Licoricone^{[11, 14]}	28.66	C₂₂H₂₂O₆	[M-H]^-	381.134 2	-0.6	351.087 5, 201.019 5, 323.092 6	GC
92	Lupiwighteone^{[11, 18]}	29.16	C₂₀H₁₈O₅	[M-H]^-	337.107 9	-0.7	282.052 7, 281.045 5	GC
93	Neo/Glycyrol/Isoglycyrol^[11]	29.24	C₂₁H₁₈O₆	[M-H]^-	365.102 8	-0.8	307.024 2, 295.024 2, 365.102 0, 282.016 3, 335.056 2	GC
94	Gancaonin A^[14]	29.63	C₂₁H₂₀O₅	[M-H]^-	351.123 4	-1.1	281.045 1, 308.104 3, 336.100 8, 293.082 1, 253.049 3, 307.098 7	GC
95	Glabrol^[14]	31.91	C₂₅H₂₈O₄	[M-H]^-	391.191 2	-0.8	187.114 6, 203.070 8, 391.191 2, 132.058 5	GC
96	Glyinflanin A^[14]	34.54	C₂₅H₂₈O₅	[M-H]^-	407.186 1	-0.8	187.112 3, 133.063 7, 175.075 2	GC
97	Glabric acid^[14]	38.10	C₃₀H₄₆O₅	[M+H]⁺	487.346 9	-2.3	487.330 6, 423.324 7, 451.321 9	GC
98	Licorisoflavan A^[14]	41.72	C₂₇H₃₄O₅	[M+H]⁺	439.247 7	-0.4	191.104 5, 371.182 2	GC
99	Gancaonin H^{[11, 12, 14]}	44.90	C₂₅H₂₄O₆	[M-H]^-	419.150 1	0.2	219.066 0, 419.148 5	GC
100	Vicenin Ⅱ^{[11, 12, 14]}	11.35	C₂₇H₃₀O₁₅	[M+H]⁺	595.164 2	-2.6	559.143 9, 511.124 9, 457.112 6, 337.068 9, 325.069 4, 295.060 1	SZR/GC
101	Saponarin^{[11, 12, 14]}	14.77	C₂₇H₃₀O₁₅	[M-H]^-	593.151 5	0.5	293.044 7, 413.087 4, 341.064 6	SZR/GC
102	Vitexin^{[11, 14]}	15.93	C₂₁H₂₀O₁₀	[M+H]⁺	433.112 6	-0.8	415.0985, 397.082 6, 379.082 6, 337.070 1, 313.068 9, 295.061 1, 283.059 8	SZR/GC
103	Isovitexin^{[11, 14]}	16.23	C₂₁H₂₀O₁₀	[M-H]^-	431.098 1	-0.6	311.055 2, 341.067 9, 323.058 5	SZR/GC

No.

Identification

t_R/min

Formula

Ion adduction

Measured mass (m/z)

Error/10^-6

Fragment (m/z)

Source

3S-1-N-β-D-Glucopyranosyl-3- hydroxy-indole-3-acetic acid/3R- 1-N-β-D-glucopyranosyl-3-hydroxy-indole-3-acetic acid^[11]

4.54

C₁₆H₁₉NO₉

[M+H]⁺

370.113 0

-0.7

212.067 4, 188.069 6, 146.059 2, 128.049 3

SZR

Protocatechuic acid^[11]

5.20

C₇H₆O₄

[M-H]^-

153.019 5

0.8

107.015 9, 124.016 5

SZR

6-Glu-coclaurine^[12]

7.13

C₂₃H₂₉NO₈

[M+H]⁺

448.196 7

-1.0

286.142 8, 269.115 8, 175.074 6, 107.049 5

SZR

4-Hydroxybenzoic acid^[12]

8.94

C₇H₆O₃

[M-H]^-

137.025 0

4.5

108.022 9, 136.016 7

SZR

Epicatechin^[13]

9.80

C₁₅H₁₄O₆

[M-H]^-

289.071 6

-0.5

221.081 2, 203.071 1, 123.044 9, 109.030 1

SZR

Coclaurine^{[11, 12]}

10.61

C₁₇H₁₉NO₃

[M+H]⁺

286.143 9

0.4

107.049 6, 175.075 3

SZR

Magnoflorine^[12]

11.52

C₂₀H₂₃NO₄

[M+H]⁺

342.169 7

-0.7

297.109 7, 282.086 2, 265.083 2, 222.088 7

SZR

Catechine^[13]

12.00

C₁₅H₁₄O₆

[M-H]^-

289.071 6

-0.7

221.082 6, 203.070 7, 187.039 2, 109.030 2

SZR

Hovetrichoside C^[11]

12.44

C₂₁H₂₂O₁₁

[M-H]^-

449.108 5

-0.9

259.060 0, 269.046 2, 125.023 9, 287.056 5

SZR

Kaempferol-3-O-rutinoside^{[11, 14]}

14.50

C₂₇H₃₀O₁₅

[M+H]⁺

595.164 6

-1.9

433.111 9, 337.068 9, 313.069 2, 283.058 3

SZR

Puerarin^[11]

14.70

C₂₁H₂₀O₉

[M-H]^-

415.103 7

-0.9

252.041 3, 25.053 1,

SZR

Spinosin^{a [11, 14, 15]}

15.33

C₂₈H₃₂O₁₅

[M+H]⁺

609.180 1

-2.2

327.085 2, 351.085 9, 297.075 3, 447.127 9, 285.075 3, 411.107 5, 609.178 6

SZR

Camelliaside B^[11]

15.45

C₃₂H₃₈O₁₉

[M-H]^-

725.194 9

1.9

284.033 4, 575.153 3

SZR

Caaverine^[11]

15.78

C₁₇H₁₇NO₂

[M+H]⁺

268.133 1

-0.3

251.105 4, 236.082 6, 219.079 4, 208.087 4, 191.084 5, 190.076 6, 189.068 8, 165.069 6

SZR

6'''-Vanilloylspinosin^{[11, 13]}

17.57

C₃₆H₃₈O₁₈

[M+H]⁺

759.211 7

-1.8

639.168 3, 429.117 7, 351.085 2, 327.085 4, 297.075 4

SZR

6'''-p-Hydroxylbenzoyspinosin^[11-13]

18.39

C₃₅H₃₆O₁₇

[M+H]⁺

729.200 8

-2.4

609.165 7, 429.117 1, 351.086 0, 327.084 9, 297.074 0, 121.028 5

SZR

Vitexin-4''-O-glucoside^[11-14]

18.43

C₂₇H₃₀O₁₅

[M+H]⁺

595.164 2

-2.6

287.054 9, 595.163 7

SZR

6'''-O-(3R-1-N-β-D-Glucopyranosyl-2-oxo-3-hydroxy-indole-3-acetyl) spinosin^[11]

19.06

C₄₄H₄₉NO₂₃

[M-H]^-

958.266 5

4.5

649.177 4

SZR

6'''-Sinapoylspinosin^[11-13]

19.39

C₃₉H₄₂O₁₉

[M+H]⁺

815.237 3

-2.5

635.170 3, 447.127 3, 429.118 6, 393.094 2, 351.088 6, 327.085 4, 297.075 5, 207.063 0, 175.038 6

SZR

6'''-Feruloylspinosin^{a [11-14, 16]}

19.91

C₃₈H₄₀O₁₈

[M+H]⁺

785.227 6

-1.5

327.084 6, 351.084 5, 177.053 7, 297.074 3, 429.116 5, 665.184 6, 785.223 7

SZR

6'''-p-Coumaroylspinosin^[11-13]

19.97

C₃₇H₃₈O₁₇

[M+H]⁺

755.217 4

-1.0

447.127 5, 429.116 5, 351.085 4, 327.085 7, 297.074 9, 147.044 3

SZR

epi-6'''-(N-β-D-Glucopyranosyl)-2'''', 3''''-dihydro-2''''-oxo-3''''-yl-acetate spinosin^[11]

20.22

C₄₄H₄₉NO₂₂

[M+H]⁺

944.279 9

-2.1

782.225 5, 764.216 2, 489.137 7, 393.095 6, 351.085 5, 327.085 2

SZR

N-Nornuciferine^[11]

21.10

C₁₈H₁₉NO₂

[M+H]⁺

282.148 6

-0.9

265.120 6, 250.097 2, 235.073 9, 234.101 9, 191.084 4, 189.068 5, 178.076 4

SZR

6''-O-Feruloylspinosin^{[11-14, 16]}

21.19

C₃₈H₄₀O₁₈

[M+H]⁺

785.226 6

-2.8

489.141 2, 447.127 1, 327.085 3, 285.074 3

SZR

Amphibine D/Lotusine B^[12]

22.46

C₃₆H₄₉N₅O₅

[M+H]⁺

632.379 0

-2.6

148.112 1, 289.190 4, 261.196 0, 316.199 6, 344.196 0, 632.377 1

SZR

Jujuboside A^{a [11-14, 16]}

23.30

C₅₈H₉₄O₂₆

[M-H]^-

1 205.600 2

3.4

911.527 3

SZR

Jujuboside B^{a [11-14, 16]}

24.15

C₅₂H₈₄O₂₁

[M-H]^-

1 043.549 3

5.0

911.505 5

SZR

Neomangiferin^{a [11, 14, 15]}

8.35

C₂₅H₂₈O₁₆

[M-H]^-

583.130 6

0.2

301.034 4, 331.044 6, 463.086 2, 493.096 8

Mangiferin^{a [11, 14-16]}

11.22

C₁₉H₁₈O₁₁

[M-H]^-

421.077 3

-0.8

301.034 4, 331.0450, 259.025 2, 271.024 4, 421.075 6

Timosaponin D^{[11, 14, 16]}

19.55

C₄₅H₇₄O₁₉

[M+H]⁺

919.488 0

-1.9

289.214 9, 271.204 8, 433.329 1, 757.433 5

Timosaponin N^{[11, 17]}

19.63

C₄₅H₇₆O₂₀

[M+HCOO]^-

981.494 1

4.0

773.442 0

Timosaponin E1^{[11, 17]}

20.29

C₄₅H₇₆O₂₀

[M+HCOO]^-

981.495 0

4.9

773.436 5, 360.571 1

Timosaponin BII^{a [11, 16, 17]}

20.70

C₄₅H₇₆O₁₉

[M-H]^-

919.490 8

3.0

919.493 6

Gurilioside H^[11]

20.76

C₅₁H₈₆O₂₃

[M+HCOO]^-

1 111.556 2

2.8

919.490 3, 757.446 4

Timosaponin BIII^{[11, 14, 16]}

20.88

C₄₅H₇₄O₁₈

[M+H]⁺

903.492 1

-3.0

273.218 5, 255.208 3, 417.332 3, 399.322 2, 579.384 3, 741.433 6

Timosaponin AI^[14]

20.89

C₃₃H₅₄O₈

[M+H]⁺

579.387 6

-2.8

273.220 6, 255.210 6, 417.336 3, 301.142 8

(25S)-26-O-β-D-Glucopyranosyl- 22-hydroxy-5β-furostanol alkenyl-3β, 26-diol3-O-β-D-glucopyranosyl- (1-2)-O-β-D-galactopyranoside^{[11, 14, 16]}

21.52

C₄₅H₇₄O₁₉

[M-H]^-

917.478 3

3.4

755.422 7, 917.477 7

Timosaponin BⅣ^{[11, 17]}

22.65

C₅₁H₈₄O₂₃

[M+HCOO]^-

1 109.541 9

4.1

901.492 6, 739.438 6

2, 6, 4'-Trihydroxy-4-methoxybenzophenone^[11]

22.82

C₁₄H₁₂O₅

[M-H]^-

259.061 1

-0.6

165.018 6, 149.995 3

Timosaponin AIII^{[11, 14, 17]}

23.74

C₃₉H₆₄O₁₃

[M+H]⁺

741.439 9

-2.8

381.314 0, 399.325 4

Anemarrhenasaponin Ⅱ^[11, ^7]

24.01

C₃₉H₆₆O₁₄

[M+HCOO]^-

803.445 1

3.5

757.439 2, 595.385 5, 757.439 2

3β, 16α-Dihydroxy-lanosta-7, 9(11), 24-trien-21-oic acid^{[11, 14, 16]}

24.17

C₃₀H₄₆O₄

[M+H]⁺

471.346 2

-1.4

317.208 5, 453.347 6, 471.269 2

Poricoic acid A^{[11, 14]}

28.55

C₃₁H₄₆O₅

[M-H]^-

497.327 4

0.3

479.313 3, 497.326 6

Poricoic acid B^{[11, 14]}

32.75

C₃₀H₄₄O₅

[M-H]^-

483.311 2

-0.8

409.272 3, 483.310 2

Polyporenic acid C^{[11, 14]}

38.58

C₃₁H₄₆O₄

[M-H]^-

481.332 3

0.0

421.305 1, 481.330 3

Pachymic acid^{[11, 14]}

47.55

C₃₃H₅₂O₅

[M+H]⁺

529.386 3

-4.6

451.353 8, 295.243 2

Adenine^[11]

1.69

C₅H₅N₅

[M+H]⁺

136.061 7

-0.7

119.036 4, 136.063 0

Vanillic acid^11]

4.69

C₈H₈O₄

[M+H]⁺

169.049 5

-1.7

151.033 8, 105.034 7

Neochlorogenic acid/Chlorogenic acid^[11]

9.43

C₁₆H₁₈O₉

[M-H]^-

353.087 8

0.1

191.056 2, 179.035 3

Caffeic acid^[11]

11.31

C₉H₈O₄

[M-H]^-

179.034 8

-0.8

135.044 8, 179.034 7

Ferulic acid^{a[11, 14, 15]}

16.65

C₁₀H₁₀O₄

[M-H]^-

193.050 7

0.1

134.036 7, 178.026 5, 149.058 0, 193.050 2

Senkyunolide J^{[11, 14]}

17.86

C₁₂H₁₈O₄

[M+H]⁺

227.127 7

-0.2

153.053 8, 163.110 6, 191.106 2, 209.116 4

Dicaffeoylquinic acid^[14]

19.80

C₂₅H₂₄O₁₂

[M-H]^-

515.119 3

-0.4

191.055 6, 353.087 5, 179.035 1, 515.119 0

Senkyunolide D^{[11, 14]}

20.11

C₁₂H₁₄O₄

[M+H]⁺

223.096 3

-1.0

205.085 3, 223.089 1, 105.034 7

Naringenin^[11]

20.27

C₁₅H₁₂O₅

[M+H]⁺

273.075 5

-0.8

153.018 9, 147.045 8, 119.047 8

Senkyunolide Ⅰ^{a[11, 14]}

20.83

C₁₂H₁₆O₄

[M+H]⁺

225.111 8

0.5

225.111 8, 207.102 5

Senkyunolide F^{[11, 14]}

20.84

C₁₂H₁₄O₃

[M+H]⁺

207.101 4

-1.0

207.101 9, 189.091 3, 119.085 7, 105.071 1, 133.064 8, 128.061 8, 161.096 9, 128.061 8, 179.107 0

3-Butyl-4-hydroxyphthalide^{[11, 14]}

21.45

C₁₂H₁₄O₃

[M+H]⁺

207.101 4

-1.0

207.101 9, 189.091 3, 161.096 9, 128.061 8, 179.107 0

Daidzein^[11]

21.81

C₁₅H₁₀O₄

[M+H]⁺

255.065 0

-0.9

145.029 1, 137.023 0, 119.051 3

E-Butylidenephthalide^{[11, 14]}

23.78

C₁₂H₁₂O₂

[M+H]⁺

189.091 0

-0.1

115.055 2, 171.080 4, 189.091 6

Butylidenephthalide^{[11, 14]}

25.77

C₁₂H₁₂O₂

[M+H]⁺

189.091 0

-0.5

171.079 5, 189.089 0

Senkyunolide A^{a [11, 14]}

28.70

C₁₂H₁₆O₂

[M+H]⁺

193.122 1

-0.4

137.059 1, 119.085 5, 147.115 9, 175.111 2, 193.121 7, 109.064 5

Cnidilide^{[14, 18]}

30.73

C₁₂H₁₈O₂

[M+H]⁺

195.137 9

-0.1

107.085 9, 125.059 0, 149.132 8, 177.126 4

Z/E-Ligustilide or 3- butylphthalide^{[11, 14]}

31.00

C₁₂H₁₄O₂

[M+H]⁺

191.106 5

-0.7

105.070 5, 115.054 5, 117.070 1, 145.101 1, 173.095 4, 149.060 0

Ligustilide dimer^[11]

35.90

C₂₄H₃₀O₄

[M+H]⁺

383.221 3

-1.0

191.106 7, 135.042 9

Riligustilide/Z, Z'-6, 8', 7, 3'- Diligustilide^[14]

39.83

C₂₄H₂₈O₄

[M+H]⁺

381.205 7

-0.9

191.107 2, 135.043 1

Glycyrrhizin-7, 4'-diglucoside^[11]

10.17

C₂₇H₃₂O₁₄

[M-H]^-

579.172 2

0.4

135.012 8, 255.067 0, 417.118 1

Shaftoside/isoshaftoside^[14]

13.40

C₂₆H₂₈O₁₄

[M-H]^-

563.141 2

0.9

353.063 7, 383.074 8, 443.095 8, 473.113 9, 503.119 1

Glucoliquiritin^[11]

13.94

C₂₇H₃₂O₁₄

[M-H]^-

579.172 2

0.4

255.066 5, 579.174 4

Isoliquiritin apioside^{[11, 14, 16]}

15.66

C₂₆H₃₀O₁₃

[M-H]^-

549.161 9

0.9

255.066 9, 135.009 3

Liquiritin apioside^{a [11, 14, 16]}

16.22

C₂₆H₃₀O₁₃

[M-H]^-

549.161 3

-0.1

255.066 3, 135.008 0

Liquiritin^{a [11, 14, 16, 18]}

16.53

C₂₁H₂₂O₉

[M-H]^-

417.119 5

0.9

119.050 2, 135.008 3, 255.065 3, 417.117 6

5-Hydroxyliquiritin^{[11, 14]}

20.34

C₂₁H₂₂O₁₀

[M-H]^-

433.113 6

-0.9

271.060 9, 177.018 7, 151.004 3, 119.051 5, 433.114 1

Isoliquiritin^{[11, 14-16]}

21.42

C₂₁H₂₂O₉

[M-H]^-

417.118 9

-0.4

119.051 0, 135.008 7, 255.066 1, 417.117 9, 148.017 4

Licorice glycoside A^[11]

21.61

C₃₆H₃₈O₁₆

[M-H]^-

725.210 8

2.9

255.065 0, 531.143 8, 549.161 0, 726.214 0, 175.040 3

Licorice glycoside B^[11]

21.62

C₃₅H₃₆O₁₅

[M-H]^-

695.199 6

2.0

549.195 9, 531.152 6, 255.065 3, 135.008 6

Licorice glycoside E^[14]

22.34

C₃₅H₃₅NO₁₄

[M-H]^-

692.199 6

1.5

255.066 6, 531.153 5, 549.160 7

5, 7-Dihydroxyflavanone/ Pinocembrin/Liquiritigenin^{[11, 14, 16]}

22.79

C₁₅H₁₂O₄

[M-H]^-

255.066 1

-0.6

119.050 2, 135.008 0, 255.063 4

24-Hydroxy-licorice-saponin E2^[11]

23.34

C₄₂H₆₀O₁₇

[M-H]^-

835.378 8

3.6

351.055 7, 193.036 0

Licorice saponine G2^[14]

23.77

C₄₂H₆₂O₁₇

[M-H]^-

837.394 9

4.2

351.056 6, 837.394 5

Uralsaponin B^{[11, 14]}

24.16

C₄₂H₆₂O₁₆

[M+H]⁺

823.408 8

-2.7

453.334 0, 647.376 6

Echinatin^{[14, 18]}

24.24

C₁₆H₁₄O₄

[M-H]^-

269.081 3

-2.2

133.031 1, 161.020 0

Glycyrrhizic acid^{a[11, 14]}

24.38

C₄₂H₆₂O₁₆

[M-H]^-

821.399 6

3.8

351.055 4, 821.399 3

Licochalcone B^[11]

25.21

C₁₆H₁₄O₅

[M-H]^-

285.076 4

1.6

285.078 8, 150.037 8

Isoliquiritigenin^{[11, 14, 16]}

25.48

C₁₅H₁₂O₄

[M-H]^-

255.066 3

-0.6

255.066 3, 135.008 6, 119.050 7

Formononetin^{[14, 18]}

25.76

C₁₆H₁₂O₄

[M-H]^-

267.066 0

-1.0

252.042 5, 223.039 6, 267.065 7, 195.045 0

(-)-Vestitol^[16]

25.83

C₁₆H₁₆O₄

[M-H]^-

271.097 3

-1.0

235.044 8, 109.031 1, 271.095 0, 149.062 1, 238.069 9, 121.032 4, 241.061 8, 255.068 8

Glycycoumarin^[11]

27.37

C₂₁H₂₀O₆

[M-H]^-

367.118 6

-0.2

309.040 4, 367.118 5, 297.039 9, 284.032 2, 265.051 2, 139.039 7, 201.018 9

Genkwanin^[11]

27.86

C₁₆H₁₂O₅

[M-H]^-

283.061 0

-0.8

268.037 0, 239.035 6, 211.036 7

Kumatakenin^[14]

28.27

C₁₇H₁₄O₆

[M-H]^-

313.071 8

0.0

283.024 0, 255.029 6, 298.046 6, 313.239 3, 183.045 5, 295.226 9

Glycyrin/Licoricone^{[11, 14]}

28.66

C₂₂H₂₂O₆

[M-H]^-

381.134 2

-0.6

351.087 5, 201.019 5, 323.092 6

Lupiwighteone^{[11, 18]}

29.16

C₂₀H₁₈O₅

[M-H]^-

337.107 9

-0.7

282.052 7, 281.045 5

Neo/Glycyrol/Isoglycyrol^[11]

29.24

C₂₁H₁₈O₆

[M-H]^-

365.102 8

-0.8

307.024 2, 295.024 2, 365.102 0, 282.016 3, 335.056 2

Gancaonin A^[14]

29.63

C₂₁H₂₀O₅

[M-H]^-

351.123 4

-1.1

281.045 1, 308.104 3, 336.100 8, 293.082 1, 253.049 3, 307.098 7

Glabrol^[14]

31.91

C₂₅H₂₈O₄

[M-H]^-

391.191 2

-0.8

187.114 6, 203.070 8, 391.191 2, 132.058 5

Glyinflanin A^[14]

34.54

C₂₅H₂₈O₅

[M-H]^-

407.186 1

-0.8

187.112 3, 133.063 7, 175.075 2

Glabric acid^[14]

38.10

C₃₀H₄₆O₅

[M+H]⁺

487.346 9

-2.3

487.330 6, 423.324 7, 451.321 9

Licorisoflavan A^[14]

41.72

C₂₇H₃₄O₅

[M+H]⁺

439.247 7

-0.4

191.104 5, 371.182 2

Gancaonin H^{[11, 12, 14]}

44.90

C₂₅H₂₄O₆

[M-H]^-

419.150 1

0.2

219.066 0, 419.148 5

100

Vicenin Ⅱ^{[11, 12, 14]}

11.35

C₂₇H₃₀O₁₅

[M+H]⁺

595.164 2

-2.6

559.143 9, 511.124 9, 457.112 6, 337.068 9, 325.069 4, 295.060 1

SZR/GC

101

Saponarin^{[11, 12, 14]}

14.77

C₂₇H₃₀O₁₅

[M-H]^-

593.151 5

0.5

293.044 7, 413.087 4, 341.064 6

SZR/GC

102

Vitexin^{[11, 14]}

15.93

C₂₁H₂₀O₁₀

[M+H]⁺

433.112 6

-0.8

415.0985, 397.082 6, 379.082 6, 337.070 1, 313.068 9, 295.061 1, 283.059 8

SZR/GC

103

Isovitexin^{[11, 14]}

16.23

C₂₁H₂₀O₁₀

[M-H]^-

431.098 1

-0.6

311.055 2, 341.067 9, 323.058 5

SZR/GC

Compound	Degree	Source		Compound	Degree	Source
Jujuboside A^{[19, 20]}	21	SZR		Magnoflorine^[20]	13	SZR
Jujuboside B^[20]	14	SZR	Vicenin Ⅱ^[25]	14	SZR/GC
Spinosin^[20]	26	SZR	Isovitexin^[25]	15	SZR/GC
6'''-Feruloylspinosin^[20]	25	SZR	Timosaponin BII^{[19, 20]}	21	ZM
Coclaurine^[20]	14	SZR	Timosaponin BⅢ^[26]	15	ZM
Mangiferin^[19]	27	ZM	Isoliquiritin^[25]	3	GC
Neomangiferin^[21]	28	ZM	Liquiritin apioside^[25]	9	GC
Timosaponin AⅢ^[19]	16	ZM	Isoliquiritin apioside^[25]	15	GC
Senkyunolide Ⅰ^[22]	14	CX	Licorice glycoside B^[25]	2	GC
Senkyunolide A^[23]	13	CX	Uralsaponin B^[25]	2	GC
Ferulic acid^[24]	25	CX	Glycyrin^[25]	16	GC
Senkyunolide F^[21]	12	CX	Neoglycyrol^[25]	11	GC
Glycyrrhizic acid^[24]	23	GC	Licorice saponin G2^[25]	15	GC
Liquiritin^[19]	24	GC

Compound

Degree

Source

Compound

Degree

Source

Jujuboside A^{[19, 20]}

SZR

Magnoflorine^[20]

SZR

Jujuboside B^[20]

SZR

Vicenin Ⅱ^[25]

SZR/GC

Spinosin^[20]

SZR

Isovitexin^[25]

SZR/GC

6'''-Feruloylspinosin^[20]

SZR

Timosaponin BII^{[19, 20]}

Coclaurine^[20]

SZR

Timosaponin BⅢ^[26]

Mangiferin^[19]

Isoliquiritin^[25]

Neomangiferin^[21]

Liquiritin apioside^[25]

Timosaponin AⅢ^[19]

Isoliquiritin apioside^[25]

Senkyunolide Ⅰ^[22]

Licorice glycoside B^[25]

Senkyunolide A^[23]

Uralsaponin B^[25]

Ferulic acid^[24]

Glycyrin^[25]

Senkyunolide F^[21]

Neoglycyrol^[25]

Glycyrrhizic acid^[24]

Licorice saponin G2^[25]

Liquiritin^[19]

Analyte	Linearity
Neomangiferin	19.35-386.9	y = 3.077 9x - 2.852 2	0.999 8
Mangiferin	13.59-271.9	y = 4.556 6x - 7.191 8	0.999 8
Ferulic acid	2.216-44.32	y = 8.265x - 2.566 7	0.999 8
Senkyunolide Ⅰ	1.437-28.74	y = 18.867x - 2.224 3	0.999 8
Spinosin	4.657-93.15	y = 5.985x - 0.093 2	0.999 9
6'''-Feruloylspinosin	1.694-33.87	y = 7.618 4x - 0.753 1	0.999 8

Analyte

Linearity

Range/μg·mL^-1

Equation

Neomangiferin

19.35-386.9

y = 3.077 9x - 2.852 2

0.999 8

Mangiferin

13.59-271.9

y = 4.556 6x - 7.191 8

0.999 8

Ferulic acid

2.216-44.32

y = 8.265x - 2.566 7

0.999 8

Senkyunolide Ⅰ

1.437-28.74

y = 18.867x - 2.224 3

0.999 8

Spinosin

4.657-93.15

y = 5.985x - 0.093 2

0.999 9

6'''-Feruloylspinosin

1.694-33.87

y = 7.618 4x - 0.753 1

0.999 8

No.	Content/%
S1	0.012 19	0.138 5	0.074 95	6.655	0.016 73	4.926
S2	0.030 19	0.113 2	0.061 30	9.08	0.015 49	5.009
S3	0.113 5	0.078 98	0.042 76	9.51	0.015 27	5.263
S4	0.010 24	0.053 61	0.012 48	6.303	0.015 60	5.296
S5	0.109 2	0.078 32	0.042 40	8.17	0.015 33	5.223
S6	0.026 77	0.143 6	0.077 76	12.49	0.015 25	5.111
S7	0.103 2	0.087 5	0.047 39	5.907	0.016 12	5.792
S8	0.093 2	0.098 8	0.053 46	7.445	0.017 46	4.859
S9	0.024 54	0.144 5	0.078 20	13.60	0.016 16	6.330
S10	0.101 6	0.084 4	0.045 66	11.92	0.020 07	6.766
Mean ± SD	0.062 46 ± 0.040 4	0.102 1 ± 0.028 5	0.053 64 ± 0.018 44	9.11 ± 2.476	0.016 35 ± 0.001 349	5.458 ± 0.557 3

No.

Content/%

Neomangiferin

Mangiferin

Ferulic acid

Senkyunolide Ⅰ/×10^-3

Spinosin

6'''-Feruloylspinosin/×10^-3

0.012 19

0.138 5

0.074 95

6.655

0.016 73

4.926

0.030 19

0.113 2

0.061 30

9.08

0.015 49

5.009

0.113 5

0.078 98

0.042 76

9.51

0.015 27

5.263

0.010 24

0.053 61

0.012 48

6.303

0.015 60

5.296

0.109 2

0.078 32

0.042 40

8.17

0.015 33

5.223

0.026 77

0.143 6

0.077 76

12.49

0.015 25

5.111

0.103 2

0.087 5

0.047 39

5.907

0.016 12

5.792

0.093 2

0.098 8

0.053 46

7.445

0.017 46

4.859

0.024 54

0.144 5

0.078 20

13.60

0.016 16

6.330

S10

0.101 6

0.084 4

0.045 66

11.92

0.020 07

6.766

Mean ± SD

0.062 46 ± 0.040 4

0.102 1 ± 0.028 5

0.053 64 ± 0.018 44

9.11 ± 2.476

0.016 35 ± 0.001 349

5.458 ± 0.557 3