药学学报

Sample No.	Sample name	Geographical origin	Sample type
JY-ZP-1	E. sagittatum	Leishan, Guizhou Province	Cultivation
JY-ZP-2	E. sagittatum	Leishan, Guizhou Province	Cultivation
JY-ZP-3	E. sagittatum	Leishan, Guizhou Province	Cultivation
JY-ZP-4	E. sagittatum	Leishan, Guizhou Province	Cultivation
JY-0403	E. sagittatum	Xinning, Hunan Province	Wild (corresponding to cultivation)
JY-0501	E. sagittatum	Jinzhai, Anhui Province	Wild
JY-0514	E. sagittatum	Quanzhou, Guangxi Province	Wild
JY-20181005	E. sagittatum	Shangli, Jiangxi Province	Wild
JY-0509	E. sagittatum	Anji, Zhejiang Province	Wild
JY-0507	E. sagittatum	Huangshan, Anhui Province	Wild
JY-0506	E. sagittatum	Xiuning, Anhui Province	Wild
JY-0516	E. sagittatum	Lianzhou, Ghuangdong Province	Wild
JY-201214	E. sagittatum	Luotian, Hubei Province	Wild
JY-0515	E. sagittatum	Jianghua, Hunan Province	Wild
TPS-ZP-1	E. myrianthum	Leishan, Guizhou Province	Cultivation
TPS-ZP-2	E. myrianthum	Leishan, Guizhou Province	Cultivation
TPS-ZP-3	E. myrianthum	Leishan, Guizhou Province	Cultivation
TPS-ZP-4	E. myrianthum	Leishan, Guizhou Province	Cultivation
TPS-ZP-5	E. myrianthum	Leishan, Guizhou Province	Cultivation
TPS-ZP-6	E. myrianthum	Leishan, Guizhou Province	Cultivation
TPS-0338	E. myrianthum	Yanhe, Guizhou Province	Wild (corresponding to cultivation)
TPS-0324	E. myrianthum	Shibing, Guizhou Province	Wild
TPS-0415	E. myrianthum	Zhijiang, Hunan Province	Wild
TPS-0323	E. myrianthum	Wanshan, Guizhou Province	Wild
TPS-0325	E. myrianthum	Yuping, Guizhou Province	Wild
TPS-0406	E. myrianthum	Tianzhu, Guizhou Province	Wild
TPS-0401	E. myrianthum	Duyun, Guizhou Province	Wild
TPS-0421	E. myrianthum	Sangzhi, Hunan Province	Wild
TPS-0405	E. myrianthum	Huitong, Hunan Province	Wild
TPS-0465	E. myrianthum	Enshi, Hubei Province	Wild
RM-ZP-1	E. pubescens	Leshan, Sichuan Province	Cultivation
RM-ZP-2	E. pubescens	Leshan, Sichuan Province	Cultivation
RM-ZP-3	E. pubescens	Leshan, Sichuan Province	Cultivation
RM-LS	E. pubescens	Leshan, Sichuan Province	Wild (corresponding to cultivation)
RM-0456	E. pubescens	Nanzheng, Shaanxi Province	Wild
RM-0525	E. pubescens	Bazhong, Sichuan Province	Wild
RM-0616	E. pubescens	Hongya, Sichuan Province	Wild
RM-0535	E. pubescens	Chengdu, Sichuan Province	Wild
RM-0711-15	E. pubescens	Jiange, Sichuan Province	Wild
RM-0711-17	E. pubescens	Tongnan, Chongqin City	Wild
RM-0711-8	E. pubescens	Qionglai, Sichuang Province	Wild
RM-0711-11	E. pubescens	Pingwu, Sichuan Province	Wild
RM-0711-18	E. pubescens	Longchang, Sichuan Province	Wild
RM-0711-16	E. pubescens	Dazu, Chongqin City	Wild
RM-0711-9	E. pubescens	Beichuan, Sichuan Province	Wild

Sample No.	Sample name	Geographical origin	Sample type
JY-ZP-1	E. sagittatum	Leishan, Guizhou Province	Cultivation
JY-ZP-2	E. sagittatum	Leishan, Guizhou Province	Cultivation
JY-ZP-3	E. sagittatum	Leishan, Guizhou Province	Cultivation
JY-ZP-4	E. sagittatum	Leishan, Guizhou Province	Cultivation
JY-0403	E. sagittatum	Xinning, Hunan Province	Wild (corresponding to cultivation)
JY-0501	E. sagittatum	Jinzhai, Anhui Province	Wild
JY-0514	E. sagittatum	Quanzhou, Guangxi Province	Wild
JY-20181005	E. sagittatum	Shangli, Jiangxi Province	Wild
JY-0509	E. sagittatum	Anji, Zhejiang Province	Wild
JY-0507	E. sagittatum	Huangshan, Anhui Province	Wild
JY-0506	E. sagittatum	Xiuning, Anhui Province	Wild
JY-0516	E. sagittatum	Lianzhou, Ghuangdong Province	Wild
JY-201214	E. sagittatum	Luotian, Hubei Province	Wild
JY-0515	E. sagittatum	Jianghua, Hunan Province	Wild
TPS-ZP-1	E. myrianthum	Leishan, Guizhou Province	Cultivation
TPS-ZP-2	E. myrianthum	Leishan, Guizhou Province	Cultivation
TPS-ZP-3	E. myrianthum	Leishan, Guizhou Province	Cultivation
TPS-ZP-4	E. myrianthum	Leishan, Guizhou Province	Cultivation
TPS-ZP-5	E. myrianthum	Leishan, Guizhou Province	Cultivation
TPS-ZP-6	E. myrianthum	Leishan, Guizhou Province	Cultivation
TPS-0338	E. myrianthum	Yanhe, Guizhou Province	Wild (corresponding to cultivation)
TPS-0324	E. myrianthum	Shibing, Guizhou Province	Wild
TPS-0415	E. myrianthum	Zhijiang, Hunan Province	Wild
TPS-0323	E. myrianthum	Wanshan, Guizhou Province	Wild
TPS-0325	E. myrianthum	Yuping, Guizhou Province	Wild
TPS-0406	E. myrianthum	Tianzhu, Guizhou Province	Wild
TPS-0401	E. myrianthum	Duyun, Guizhou Province	Wild
TPS-0421	E. myrianthum	Sangzhi, Hunan Province	Wild
TPS-0405	E. myrianthum	Huitong, Hunan Province	Wild
TPS-0465	E. myrianthum	Enshi, Hubei Province	Wild
RM-ZP-1	E. pubescens	Leshan, Sichuan Province	Cultivation
RM-ZP-2	E. pubescens	Leshan, Sichuan Province	Cultivation
RM-ZP-3	E. pubescens	Leshan, Sichuan Province	Cultivation
RM-LS	E. pubescens	Leshan, Sichuan Province	Wild (corresponding to cultivation)
RM-0456	E. pubescens	Nanzheng, Shaanxi Province	Wild
RM-0525	E. pubescens	Bazhong, Sichuan Province	Wild
RM-0616	E. pubescens	Hongya, Sichuan Province	Wild
RM-0535	E. pubescens	Chengdu, Sichuan Province	Wild
RM-0711-15	E. pubescens	Jiange, Sichuan Province	Wild
RM-0711-17	E. pubescens	Tongnan, Chongqin City	Wild
RM-0711-8	E. pubescens	Qionglai, Sichuang Province	Wild
RM-0711-11	E. pubescens	Pingwu, Sichuan Province	Wild
RM-0711-18	E. pubescens	Longchang, Sichuan Province	Wild
RM-0711-16	E. pubescens	Dazu, Chongqin City	Wild
RM-0711-9	E. pubescens	Beichuan, Sichuan Province	Wild

Peak No.	t_R /min	Precursor ion	Experimental mass	Error (mDa)	Formula	Fragment ion	Identification	E. s	E. m	E. p	Ref.
1	0.56	[M-H]^-	353.086 7	-0.7	C₁₆H₁₈O₉	191, 179, 173, 135 (-)	Chlorogenic acid	-	+	+	[19, 20]
2	0.75	[M-H]^-	337.093 2	0.9	C₁₆H₁₈O₈	191, 173, 163, 137 (-)	5-p-Coumaroylquinic acid	+	+	+	[19]
3	1.05	[M-H]^-	463.087 3	-0.4	C₂₁H₂₀O₁₂	301 (-)	Hyperoside	+	+	+	[19, 20]
4	1.10	[M-H]^- [M+H]⁺	577.154 8 579.171 0	-0.9 -0.4	C₂₇H₃₀O₁₄	431, 285 (-) 433, 287 (+)	Kaempferol-3-O-dirhamnoside or its isomers	+	+	+	[19]
5	1.53	[M-H]^- [M+H]⁺	447.093 5 449.108 4	-0.8 -1.1	C₂₁H₂₀O₁₁	301, 271, 255 (-) 303, 273, 257 (+)	Quercetin-3-O-α-L-rhamnoside	+	+	+	[19, 20]
6	1.68	[M-H]^- [M+H]⁺	677.208 8 679.222 6	0.6 -1.2	C₃₂H₃₈O₁₆	515, 353 (-) 517, 355 (+)	Hexandraside E	+	+	+	[19, 20]
7	1.79	[M-H]^- [M+H]⁺	823.264 9 825.278 9	-1.2 -2.8	C₃₈H₄₈O₂₀	661, 515, 353 (-) 663, 517, 355 (+)	Diphylloside A or its isomers	+	+	+	[19]
8	1.95	[M-H]^- [M+H]⁺	563.138 4 565.156 6	-1.7 0.9	C₂₆H₂₈O₁₄	284 (-) 433, 287 (+)	Kaempferol-7-O-rhamnopyranosyl-xylopyranoside	+	+	+	[22]
9	2.14	[M-H]^- [M+H]⁺	431.098 1 433.110 9	0.3 -2.4	C₂₁H₂₀O₁₀	285 (-) 287 (+)	Kaempferol-3-O-α-L-rhamnoside	+	+	+	[20]
10	2.21	[M-H]^- [M+H]⁺	661.214 3 663.226 8	1.1 -2.1	C₃₂H₃₈O₁₅	499, 353 (-) 517, 355 (+)	Epimedoside A	+	+	+	[19]
11	3.32	[M-H]^- [M+H]⁺	837.281 5 839.297 4	-0.2 2.3	C₃₉H₅₀O₂₀	675, 529, 383 (-) 693, 547, 385 (+)	Sagittasine A	+	+	+	[19]
12	3.92	[M-H]^- [M+H]⁺	837.281 5 839.293 4	-0.2 -4.0	C₃₉H₅₀O₂₀	675, 367, 352 (-) 677, 531, 369, 313 (+)	Epimedin A I^*	+	+	-	[19, 20]
13	4.20	[M-H]^- [M+H]⁺	837.281 5 839.297 4	-0.2 -1.4	C₃₉H₅₀O₂₀	675, 367, 352 (-) 677, 531, 369, 313 (+)	Epimedin A^*	+	+	+	[19, 20]
14	4.29	[M-H]^- [M+H]⁺	807.270 0 809.281 5	-1.2 -5.3	C₃₈H₄₈O₁₉	645, 367, 352 (-) 677, 531, 369, 313 (+)	Isomer of 15	-	+	+
15	4.41	[M-H]^- [M+H]⁺	807.270 1 809.281 5	-1.2 -5.3	C₃₈H₄₈O₁₉	645, 367, 352 (-) 677, 531, 369, 313 (+)	Epimedin B^*	+	+	+	[19, 20]
16	4.62	[M-H]^- [M+H]⁺	821.285 2 823.297 6	-1.6 -4.9	C₃₉H₅₀O₁₉	659, 513, 367, 351 (-) 677, 531, 369, 313 (+)	Epimedin C^*	+	+	+	[19, 20]
17	4.79	[M+HCOO]^- [M+H]⁺	721.235 6 677.240 0	1.2 -4.5	C₃₃H₄₀O₁₅	513, 367, 351 (-) 531, 369, 313 (+)	Icariin^*	+	+	+	[19, 20]
18	4.92	[M-H]^- [M+HCOO]^-	819.271 5 865.276 9	0.3 0.3	C₃₉H₄₈O₁₉	657, 513, 367, 352 (-)	Isomer of 19	+	+	-	[19]
19	5.51	[M-H]^- [M+H]⁺	819.271 5 821.285 9	0.3 -0.9	C₃₉H₄₈O₁₉	657, 513, 367, 352 (-) 531, 369, 313 (+)	3'''-Carbonyl-2''-β-L-quinovosyl-icariin^*	+	+	+
20	5.54	[M-H]^- [M+H]⁺	819.271 5 821.285 9	0.3 -0.9	C₃₉H₄₈O₁₉	657, 513, 367, 352 (-) 531, 369, 313 (+)	Isomer of 19	+	-	+
21	5.66	[M-H]^-	821.288 8	2.0	C₃₉H₅₀O₁₉	659, 513, 367, 352 (-)	Baohuoside VI	+	+	-	[19]
22	5.93	[M-H]^- [M+HCOO]^-	717.239 3 763.244 9	-0.2 -0.1	C₃₅H₄₂O₁₆	571, 513, 367, 351 (-)	Anhydroicaritin-3-O-(acetyl)-glucopyranoside-7-O-rhamnopyranoside	+	-	+	[22]
23	6.25	[M-H]^-	819.271 5	0.3	C₃₉H₄₈O₁₉	657, 513, 367, 352 (-)	Isomer of 19	+	-	+
24	7.87	[M-H]^- [M+H]⁺	675.217 3 677.244 5	-1.2 -1.2	C₃₃H₄₀O₁₅	367, 352 (-) 369, 313 (+)	Sagittatoside A ^*	+	+	+	[19, 20]
25	8.14	[M-H]^- [M+H]⁺	645.217 3 647.234 1	-1.0 -0.1	C₃₂H₃₈O₁₄	367, 352 (-) 369, 313 (+)	Sagittatoside B ^*	-	+	+	[19, 20]
26	8.24	[M-H]^- [M+H]⁺	659.234 6 661.249 6	0.6 -1.5	C₃₃H₄₀O₁₄	367, 352 (-) 369, 313 (+)	2''-O-rhamnopyranosyl Icariside Ⅱ ^*	+	+	+	[19, 20]
27	8.73	[M-H]^- [M+H]⁺	513.175 9 515.191 0	-0.2 -0.7	C₂₇H₃₀O₁₀	366, 351, 323 (-) 369, 313 (+)	Icariside Ⅱ^*	+	+	+	[21]
28	9.80	[M-H]^- [M+H]⁺	337.107 2 339.123 2	-0.4 -2.2	C₂₀H₁₈O₅	282 (-) 283 (+)	Yinyanghuo D or its isomers	+	+	+	[23]
29	10.62	[M-H]^- [M+H]⁺	421.166 8 423.178 5	1.7 -2.3	C₂₅H₂₆O₆	351, 296 (-) 405, 353, 296 (+)	Yinyanghuo B or its isomers	+	+	-	[20, 23]
30	10.71	[M-H]^-	367.118 4	0.2	C₂₁H₂₀O₆	309, 297, 281 (-)	Icaritin	+	+	+	[20]
31	10.77	[M-H]^- [M+H]⁺	405.170 3 407.185 6	0.1 -0.2	C₂₅H₂₆O₅	350 (-) 351, 295 (+)	5, 7, 4'-Trihydroxy-8, 3'-di- prenyl-flavone or its isomers	+	+	+	[21]
32	10.94	[M-H]^- [M+H]⁺	405.170 3 407.185 6	0.1 -0.2	C₂₅H₂₆O₅	350 (-) 351, 295 (+)	5, 7, 4'-Trihydroxy-8, 3'-di- prenyl-flavone or its isomers	+	+	+	[21]

Peak No.	t_R /min	Precursor ion	Experimental mass	Error (mDa)	Formula	Fragment ion	Identification	E. s	E. m	E. p	Ref.
1	0.56	[M-H]^-	353.086 7	-0.7	C₁₆H₁₈O₉	191, 179, 173, 135 (-)	Chlorogenic acid	-	+	+	[19, 20]
2	0.75	[M-H]^-	337.093 2	0.9	C₁₆H₁₈O₈	191, 173, 163, 137 (-)	5-p-Coumaroylquinic acid	+	+	+	[19]
3	1.05	[M-H]^-	463.087 3	-0.4	C₂₁H₂₀O₁₂	301 (-)	Hyperoside	+	+	+	[19, 20]
4	1.10	[M-H]^- [M+H]⁺	577.154 8 579.171 0	-0.9 -0.4	C₂₇H₃₀O₁₄	431, 285 (-) 433, 287 (+)	Kaempferol-3-O-dirhamnoside or its isomers	+	+	+	[19]
5	1.53	[M-H]^- [M+H]⁺	447.093 5 449.108 4	-0.8 -1.1	C₂₁H₂₀O₁₁	301, 271, 255 (-) 303, 273, 257 (+)	Quercetin-3-O-α-L-rhamnoside	+	+	+	[19, 20]
6	1.68	[M-H]^- [M+H]⁺	677.208 8 679.222 6	0.6 -1.2	C₃₂H₃₈O₁₆	515, 353 (-) 517, 355 (+)	Hexandraside E	+	+	+	[19, 20]
7	1.79	[M-H]^- [M+H]⁺	823.264 9 825.278 9	-1.2 -2.8	C₃₈H₄₈O₂₀	661, 515, 353 (-) 663, 517, 355 (+)	Diphylloside A or its isomers	+	+	+	[19]
8	1.95	[M-H]^- [M+H]⁺	563.138 4 565.156 6	-1.7 0.9	C₂₆H₂₈O₁₄	284 (-) 433, 287 (+)	Kaempferol-7-O-rhamnopyranosyl-xylopyranoside	+	+	+	[22]
9	2.14	[M-H]^- [M+H]⁺	431.098 1 433.110 9	0.3 -2.4	C₂₁H₂₀O₁₀	285 (-) 287 (+)	Kaempferol-3-O-α-L-rhamnoside	+	+	+	[20]
10	2.21	[M-H]^- [M+H]⁺	661.214 3 663.226 8	1.1 -2.1	C₃₂H₃₈O₁₅	499, 353 (-) 517, 355 (+)	Epimedoside A	+	+	+	[19]
11	3.32	[M-H]^- [M+H]⁺	837.281 5 839.297 4	-0.2 2.3	C₃₉H₅₀O₂₀	675, 529, 383 (-) 693, 547, 385 (+)	Sagittasine A	+	+	+	[19]
12	3.92	[M-H]^- [M+H]⁺	837.281 5 839.293 4	-0.2 -4.0	C₃₉H₅₀O₂₀	675, 367, 352 (-) 677, 531, 369, 313 (+)	Epimedin A I^*	+	+	-	[19, 20]
13	4.20	[M-H]^- [M+H]⁺	837.281 5 839.297 4	-0.2 -1.4	C₃₉H₅₀O₂₀	675, 367, 352 (-) 677, 531, 369, 313 (+)	Epimedin A^*	+	+	+	[19, 20]
14	4.29	[M-H]^- [M+H]⁺	807.270 0 809.281 5	-1.2 -5.3	C₃₈H₄₈O₁₉	645, 367, 352 (-) 677, 531, 369, 313 (+)	Isomer of 15	-	+	+
15	4.41	[M-H]^- [M+H]⁺	807.270 1 809.281 5	-1.2 -5.3	C₃₈H₄₈O₁₉	645, 367, 352 (-) 677, 531, 369, 313 (+)	Epimedin B^*	+	+	+	[19, 20]
16	4.62	[M-H]^- [M+H]⁺	821.285 2 823.297 6	-1.6 -4.9	C₃₉H₅₀O₁₉	659, 513, 367, 351 (-) 677, 531, 369, 313 (+)	Epimedin C^*	+	+	+	[19, 20]
17	4.79	[M+HCOO]^- [M+H]⁺	721.235 6 677.240 0	1.2 -4.5	C₃₃H₄₀O₁₅	513, 367, 351 (-) 531, 369, 313 (+)	Icariin^*	+	+	+	[19, 20]
18	4.92	[M-H]^- [M+HCOO]^-	819.271 5 865.276 9	0.3 0.3	C₃₉H₄₈O₁₉	657, 513, 367, 352 (-)	Isomer of 19	+	+	-	[19]
19	5.51	[M-H]^- [M+H]⁺	819.271 5 821.285 9	0.3 -0.9	C₃₉H₄₈O₁₉	657, 513, 367, 352 (-) 531, 369, 313 (+)	3'''-Carbonyl-2''-β-L-quinovosyl-icariin^*	+	+	+
20	5.54	[M-H]^- [M+H]⁺	819.271 5 821.285 9	0.3 -0.9	C₃₉H₄₈O₁₉	657, 513, 367, 352 (-) 531, 369, 313 (+)	Isomer of 19	+	-	+
21	5.66	[M-H]^-	821.288 8	2.0	C₃₉H₅₀O₁₉	659, 513, 367, 352 (-)	Baohuoside VI	+	+	-	[19]
22	5.93	[M-H]^- [M+HCOO]^-	717.239 3 763.244 9	-0.2 -0.1	C₃₅H₄₂O₁₆	571, 513, 367, 351 (-)	Anhydroicaritin-3-O-(acetyl)-glucopyranoside-7-O-rhamnopyranoside	+	-	+	[22]
23	6.25	[M-H]^-	819.271 5	0.3	C₃₉H₄₈O₁₉	657, 513, 367, 352 (-)	Isomer of 19	+	-	+
24	7.87	[M-H]^- [M+H]⁺	675.217 3 677.244 5	-1.2 -1.2	C₃₃H₄₀O₁₅	367, 352 (-) 369, 313 (+)	Sagittatoside A ^*	+	+	+	[19, 20]
25	8.14	[M-H]^- [M+H]⁺	645.217 3 647.234 1	-1.0 -0.1	C₃₂H₃₈O₁₄	367, 352 (-) 369, 313 (+)	Sagittatoside B ^*	-	+	+	[19, 20]
26	8.24	[M-H]^- [M+H]⁺	659.234 6 661.249 6	0.6 -1.5	C₃₃H₄₀O₁₄	367, 352 (-) 369, 313 (+)	2''-O-rhamnopyranosyl Icariside Ⅱ ^*	+	+	+	[19, 20]
27	8.73	[M-H]^- [M+H]⁺	513.175 9 515.191 0	-0.2 -0.7	C₂₇H₃₀O₁₀	366, 351, 323 (-) 369, 313 (+)	Icariside Ⅱ^*	+	+	+	[21]
28	9.80	[M-H]^- [M+H]⁺	337.107 2 339.123 2	-0.4 -2.2	C₂₀H₁₈O₅	282 (-) 283 (+)	Yinyanghuo D or its isomers	+	+	+	[23]
29	10.62	[M-H]^- [M+H]⁺	421.166 8 423.178 5	1.7 -2.3	C₂₅H₂₆O₆	351, 296 (-) 405, 353, 296 (+)	Yinyanghuo B or its isomers	+	+	-	[20, 23]
30	10.71	[M-H]^-	367.118 4	0.2	C₂₁H₂₀O₆	309, 297, 281 (-)	Icaritin	+	+	+	[20]
31	10.77	[M-H]^- [M+H]⁺	405.170 3 407.185 6	0.1 -0.2	C₂₅H₂₆O₅	350 (-) 351, 295 (+)	5, 7, 4'-Trihydroxy-8, 3'-di- prenyl-flavone or its isomers	+	+	+	[21]
32	10.94	[M-H]^- [M+H]⁺	405.170 3 407.185 6	0.1 -0.2	C₂₅H₂₆O₅	350 (-) 351, 295 (+)	5, 7, 4'-Trihydroxy-8, 3'-di- prenyl-flavone or its isomers	+	+	+	[21]

基于UHPLC-PDA-Q-TOF/MS^E技术的栽培淫羊藿质量研究

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周茗 ¹^,²^,³ , 郑伟 ² , 郭宝林 ³^,^* , 陈安家 ¹^,^* , 马百平 ²^,^*

药学学报 | 研究论文 2020,55(5): 995-1003

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药学学报 | 研究论文 2020, 55(5): 995-1003

基于UHPLC-PDA-Q-TOF/MS^E技术的栽培淫羊藿质量研究

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周茗¹^,²^,³, 郑伟², 郭宝林³^,^*, 陈安家¹^,^*, 马百平²^,^*

作者信息

1.山西医科大学, 山西太原 030001

2.军事科学院军事医学研究院辐射医学研究所, 北京 100850

3.中国医学科学院、北京协和医学院药用植物研究所, 北京 100193

通讯作者:

*郭宝林, Tel:86-10-57833172, E-mail:guobaolin010@163.com;

陈安家, Tel:86-351-4690071, E-mail:chenanjia888@163.com;

马百平, Tel:86-10-66930265, E-mail:mabaiping@sina.com

Evaluation of cultivated and wild Herba Epimedii using UHPLC-PDA-Q-TOF/MS^E

Ming ZHOU¹^,²^,³, Wei ZHENG², Bao-lin GUO³^,^*, An-jia CHEN¹^,^*, Bai-ping MA²^,^*

Affiliations

1. Shanxi Medical University, Taiyuan 030001, China

2. Institute of Radiation Medicine, Academy of Military Medical Sciences, Academy of Military Sciences, Beijing 100850, China

3. Institute of Medicinal Plant Development, Chinese Academy of Medical Science, Peking Union Medical College, Beijing 100193, China

出版时间: 2020-05-15 doi: 10.16438/j.0513-4870.2019-0885

文章导航

摘要

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采用UHPLC-PDA-Q-TOF/MS^E通过定性和相对定量方法对栽培箭叶淫羊藿、天平山淫羊藿、柔毛淫羊藿进行质量研究。本文以箭叶、天平山、柔毛淫羊藿的栽培种质、相应野生种质以及来自国内其他野生种质为研究对象，采用UHPLC-Q-TOF/MS^E结合UNIFI数据分析平台快速鉴定淫羊藿中化合物32个，同时利用主成分分析（PCA）法对3个种栽培及野生样本进行比较，结果表明栽培与相应野生样本化学成分组成比较一致。最后利用UHPLC-PDA对所有样本中12个黄酮类成分及总黄酮进行相对定量，结果表明3个种的栽培与相应野生种质化学成分相对含量较相似，且栽培后淫羊藿质量稳定性较好。本文利用UHPLC-PDA-Q-TOF/MS^E结合UNIFI数据分析平台和PCA方法建立的定性和相对定量方法可用于栽培淫羊藿的质量研究，同时研究结果也为淫羊藿药材的栽培推广和资源合理开发利用提供了科学依据。

关键词

淫羊藿 / 栽培 / UHPLC-PDA-Q-TOF/MS^E / 质量研究

Abstract

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Qualitative and relatively quantitative methods were used to study the quality of cultivated Epimedium sagittatum (Sieb. et Zucc.) Maxim., Epimedium myrianthum Stearn, and Epimedium pubescens Maxim by ultra high-performance liquid chromatography coupled with photo-diode array and quadrupole time-of-flight mass spectrometry (UHPLC-PDA-Q-TOF/MS^E). Thirty-two compounds in cultivated and wild samples of E. sagittatum, E. myrianthum and E. pubescens were identified using UHPLC-Q-TOF/MS^E combined with the UNIFI data analysis platform. Principal component analysis (PCA) was used to compare the cultivated and wild samples of these three species. The results show that the chemical compositions of cultivated samples were consistent with the corresponding wild samples. UHPLC-PDA was used to determine the relative content of 12 flavonoids as well as total flavonoids in all samples. The results show that the relative chemical content of these flavonoids in cultivated and wild samples is similar and the quality of cultivated Epimedium is more stable. These qualitative and relatively quantitative methods using UHPLC-PDA-Q-TOF/MS^E combined with the UNIFI data analysis platform and PCA can be used to study the quality of cultivated Herba Epimedii. This research provides a scientific basis for the cultivation and rational development and utilization of Epimedium medicinal materials.

Key words

Epimedium / cultivation / UHPLC-PDA-Q-TOF/MS^E / quality study

引用本文

周茗, 郑伟, 郭宝林, 陈安家, 马百平. 基于UHPLC-PDA-Q-TOF/MS^E技术的栽培淫羊藿质量研究. 药学学报, 2020 , 55 (5) : 995 -1003 . DOI: 10.16438/j.0513-4870.2019-0885

Ming ZHOU, Wei ZHENG, Bao-lin GUO, An-jia CHEN, Bai-ping MA. Evaluation of cultivated and wild Herba Epimedii using UHPLC-PDA-Q-TOF/MS^E[J]. Acta Pharmaceutica Sinica, 2020 , 55 (5) : 995 -1003 . DOI: 10.16438/j.0513-4870.2019-0885

正文

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淫羊藿作为我国传统中药已有上千年的药用历史, 始载于《神农本草经》, 具有补肾阳、强筋骨、祛风湿的作用, 常用于治疗肾阳虚衰、阳痿遗精、筋骨萎软、风湿麻痹等^[1]。现代药理学研究表明, 淫羊藿在调节免疫、改善心血管功能、抗癌、抗骨质疏松、抗衰老等方面均有很好的疗效^[2-6]。除2015版《中国药典》淫羊藿项下收录的4种淫羊藿外, 该属植物还有其他种作为药材商品在市场上流通^{[7, 8]}, 其中天平山淫羊藿于1998年由Stearn^[9]从箭叶淫羊藿变种宽序淫羊藿Epimedium sagittatum var. pyramidale (Franch) Stearn提升为独立种, 被《贵州省中药材、民族药材质量标准》收载作为“黔淫羊藿”药用来源之一, 因其优异的质量而受到广泛关注^[10-12]。该物种和箭叶淫羊藿关系非常密切, 药材性状难以区分, 在贵州、重庆、湖南、湖北等地资源量很大, 常被作为箭叶淫羊藿应用。由于淫羊藿属植物种内变异大, 关系复杂, 一直有物种分类过细的问题, 部分物种经分类学研究后被合并^[13], 天平山淫羊藿可能作为箭叶淫羊藿的一个变种更为合适, 分类学工作正在进行中。

目前, 淫羊藿药材需求日益增加^{[14, 15]}, 野生资源的过度采挖, 已经导致资源严重短缺, 价格不断飙升, 而淫羊藿属植物含有的有效成分, 淫羊藿苷类化合物在不同种类, 甚至同一个物种的不同居群中变异极大^[12]。因此, 选择优良种质大规模栽培是解决淫羊藿药材需求的有效途径之一^[16-18]。本实验前期对野生箭叶、天平山、柔毛淫羊藿进行了全国范围内的资源调查和优良种质遴选, 最终分别确定了箭叶、天平山、柔毛淫羊藿质量较优异的野生种质进行栽培。但生长方式变化对栽培后淫羊藿化学成分组成的影响以及规模化种植后淫羊藿化学成分的含量变化还有待研究。因此, 本文以箭叶、天平山、柔毛淫羊藿的栽培种质、相应野生种质以及来自国内其他野生种质为研究对象, 采用UHPLC-PDA-Q-TOF/MS^E结合UNIFI数据分析平台和主成分分析(PCA)方法对栽培淫羊藿进行了较全面的质量研究, 旨在为淫羊藿药材栽培推广以及资源合理开发利用提供科学依据。

材料与方法

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仪器 Waters ACQUITY I-Class超高效液相色谱系统(Waters公司, Milford, MA, 美国); VION-IMS-QTOF质谱系统(Waters公司, Wilmslow, 英国); UNIFI 1.9.4软件、Umetrics Ezinfo 3.0软件(Waters公司, Manchester, 英国); Waters ACQUITY^TM超高效液相色谱系统和Waters ACQUITY^TM PDA检测器(Waters公司, Milford, MA, 美国); Heatmap Illustrator软件。色谱柱: Waters ACQUITY^TM HSS T3 C18 (2.1 mm×100 mm, 1.8 μm, Waters, 爱尔兰); Sartorius BP211D 1/10万电子天平(美国Sartorius公司); 舒美KQ-600E数控超声波清洗器(江苏昆山市超声仪器有限公司); 0.22 μm微孔滤膜(上海兴亚净化材料厂)。

试剂与样品 乙腈(色谱纯, Fisher, 美国); 甲酸(色谱纯, Acros Co. Ltd., NJ, 美国); 屈臣氏蒸馏水(广州屈臣氏蒸馏水有限公司)。其他试剂均为市售分析纯。对照品朝藿定AI、朝藿定A、朝藿定B、朝藿定C、淫羊藿苷、3′′′-羰基-2′′-β-L-喹诺糖基淫羊藿苷、淫羊藿次苷Ⅱ、2′′-O-鼠李糖基淫羊藿次苷Ⅱ、箭藿苷A、箭藿苷B均为本实验室自制, HPLC面积归一化法测定纯度大于98%。

样品包括箭叶、天平山、柔毛淫羊藿的栽培种质、相应野生种质以及国内其他野生种质, 详见表 1, 其中栽培箭叶淫羊藿样本引种年限为8年, 种源来自湖南新宁; 栽培天平山淫羊藿样本引种年限为7年, 种源来自贵州沿河; 栽培柔毛淫羊藿样本引种年限为5年, 种源来自四川乐山。各样本均由中国医学科学院药用植物研究所郭宝林研究员鉴定为小檗科植物箭叶淫羊藿Epimedium sagittatum (Sieb. et Zucc.) Maxim.、天平山淫羊藿Epimedium myrianthum Stearn、柔毛淫羊藿Epimedium pubescens Maxim.的干燥叶。

色谱条件 色谱柱: Waters ACQUITY^TM HSS T3 C18 (2. 1 mm×100 mm, 1.8 μm); 流动相: 0.1%甲酸水溶液(A)-乙腈(B); 梯度洗脱(0~1.5 min, 21%~24% B; 1.5~3 min, 24%~25% B; 3~4 min, 25%~29% B; 4~5 min, 29% B; 5~6.5 min, 29%~32% B; 6.5~7 min, 32%~44% B; 7~8 min, 44%~45% B; 8~9 min, 45%~46% B; 9~11 min, 46%~95% B; 流速0.6 mL·min^-1; 柱温40 ℃; 进样量2 μL; PDA检测波长270 nm。

质谱条件 电喷雾电离离子源(ESI), 离子化模式为正、负离子模式, 离子源温度为110.0 ℃, 脱溶剂气体为氮气, 流速为850 L·h^-1, 温度为450 ℃。正离子模式下毛细管电压为3 kV, 负离子模式下毛细管电压为2.5 kV, 锥孔电压为50 V, 扫描范围为100~1 600 Da。低能量扫描时能量为4 eV, 高能量扫描时能量为30~50 eV。准确质量数用leucineenk ephalin作校正液。

混合对照品溶液的制备 称取朝藿定AI、朝藿定A、朝藿定B、朝藿定C、淫羊藿苷、3′′′-羰基-2′′-β-L-喹诺糖基淫羊藿苷、淫羊藿次苷Ⅱ、2′′-O-鼠李糖基淫羊藿次苷Ⅱ、箭藿苷A、箭藿苷B各0.3 mg, 分别加入70%甲醇1 mL溶解, 摇匀, 制得各对照品储蓄液。再分别取各对照品储蓄液100 μL, 混匀即得。

供试品溶液的制备 取淫羊藿药材粉末0.2 g (过40目筛), 精密称定, 置于100 mL具塞锥形瓶中, 精密加入50%乙醇溶液20 mL, 密塞, 摇匀, 称重, 超声处理1 h, 冷却至室温, 用50%乙醇补足失重, 0.22 μm针式过滤器滤过, 取续滤液, 即得。

UNIFI数据库及分析方法的建立 应用UNIFI 1.9.4软件的数据库管理系统, 建立淫羊藿药材全化学成分数据库(249个化合物), 包括化合物中英文名称、分子式、化学结构式和碎片离子信息等, 并导入UNIFI软件中, 构建淫羊藿化学成分专属数据库。分析方法中设定3D峰检测参数的强度阈值(高能量为25计数, 低能量为200计数), 加合离子峰的种类(负离子模式为[M-H]^-、[M+HCOO]^-, 正离子模式为[M+H]⁺、[M+Na]⁺、[M+H-H₂O]⁺)。

PCA分析 利用Umetrics Ezinfo 3.0软件对采集到的所有淫羊藿样品在0~11 min内的UHPLC-Q-TOF/MS^E指纹图谱进行主成分分析, 得到PCA得分图以便更直观的了解栽培与野生箭叶、天平山、柔毛淫羊藿样本间的差异情况。

结果

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1 淫羊藿化学成分的鉴定

采用所建立的UHPLC-Q-TOF/MS^E方法快速分析箭叶、天平山、柔毛淫羊藿, 样品BPI图见图 1。在UNIFI软件中创建分析方法并对采集数据进行分析, 软件自动标识经处理后的可信数据, 给出保留时间、化学式、质量数误差、标识的高能量碎片数目等信息。通过与对照品总结得出的裂解规律及相关文献[19-23]的匹配与确证, 共利用UNIFI鉴定箭叶、天平山、柔毛淫羊藿中化合物32个, 见表 2。

淫羊藿中主要化学成分多为8-异戊烯基取代的黄酮苷类成分, 在C-3位和C-7位多连有糖基, 糖基种类多为葡萄糖、鼠李糖和木糖。通过对照品的裂解碎片可知, 在负离子模式下出现[M-H]^-的准分子离子峰, 且大多数化合物会伴随较高丰度的[M+HCOO]^-以及[M+2H₂O-H]^-加合离子峰。此外在负离子模式下先丢失7位所连糖基, 而在正离子模式下更倾向于丢失3位上的糖基。

色谱峰10在负离子模式下存在m/z 661.214 3 [M-H]^-、707.219 4 [M+HCOO]^-和697.189 5 [M+2H₂O-H]^-的母离子以及碎片离子m/z 499.159 9 [M-H-162]^-和353.103 5 [M-H-162-146]^-。正离子模式下显示m/z 663.226 8 [M+H]⁺的准分子离子峰以及碎片离子m/z 517.168 9 [M+H-146]⁺和355.117 4 [M+H-146-162]⁺, 推测其3位连有1个甲基五碳糖(鼠李糖), 7位连有1个六碳糖(葡萄糖), 与文献核对后认为其为epimedoside A, 同时与UNIFI自动鉴定结果一致, 最终确定色谱峰10为epimedoside A。

在负离子模式下, 色谱峰20存在m/z 819.271 5 [M-H]^-、865.276 9 [M+HCOO]^-和855.245 7 [M+2H₂O-H]^-的准分子离子峰, 负离子高能量时依次出现碎片离子m/z 657.218 7 [M-H-162]^-、513.175 9 [M-H-162-144]^-和367.118 4 [M-H-162-144-146]^-以及母核4'位上甲基断裂后碎片离子m/z 352.093 6 [M-H-162-144-146-CH₃]^-。正离子模式下显示母离子m/z 821.285 9 [M+H]⁺以及碎片离子m/z 531.184 9 [M+H-144-146]⁺和369.132 0 [M+H-144-146-162]⁺以及母核8位上异戊烯基断裂后碎片离子m/z 313.070 5 [M+H-144-146-162-C₄H₇]⁺, 推测该化合物7位连有一个葡萄糖, 3位连有一个鼠李糖和与3′′′-羰基-2′′-β-L-喹诺糖分子量相同的基团。该化合物母离子及碎片裂解信息与峰19相同, 因此判断该化合物与峰19互为同分异构体。

2 栽培与相应野生淫羊藿指纹图谱与PCA分析

采用所建立的UHPLC-Q-TOF/MS^E方法快速分析所有淫羊藿样品, 并将采集的所有样品在0~11 min内指纹图谱进行PCA分析, 所得PCA得分图见图 2。图中的点代表不同的样品, 较为聚集表示其化学成分组成相似, 反之, 则差异较大。PCA结果表明栽培与相应野生的箭叶、天平山、柔毛淫羊藿化学成分差异较小, 说明栽培环境和生长方式等因素的改变并没有对栽培后淫羊藿化学成分组成产生较大影响。

3 栽培与野生淫羊藿化学成分相对含量分析

采用所建立的UHPLC-PDA方法对所有淫羊藿样品在紫外(λ=270 nm)下有较高响应的12个黄酮类化合物进行相对定量(以12个化合物峰面积值代表其相对含量), 这12个化合物分别为峰10 (epimedoside A)、峰12 (epimedin A I)、峰13 (epimedin A)、峰14 (isomer of epimedin B)、峰15 (epimedin B)、峰16 (epimedin C)、峰17 (icariin)、峰19 (3'''-carbonyl-2''-β-L-quinovosyl-icariin)、峰24 (sagittatoside A)、峰25 (sagittatoside B)、峰26 (2''-O-rhamnopyranosyl icariside Ⅱ)、峰27 (icariside Ⅱ), 所得UHPLC-PDA图见图 3。将箭叶、天平山、柔毛淫羊藿的栽培与相应野生以及其他野生样本中12个黄酮类化合物相对含量结果分别以热图形式呈现, 其中黄色字编号代表栽培淫羊藿, 紫色字编号代表与栽培相应的野生淫羊藿, 黑色字编号代表其他野生淫羊藿, 结果见图 4。

由于选择栽培的相应野生箭叶、天平山、柔毛淫羊藿样本是从大量野生样本中遴选出的较优种质, 其淫羊藿苷(Peak17)相对含量较其他野生样本高。由图 4可知, 栽培与相应野生的箭叶、天平山、柔毛淫羊藿分别聚为一类, 说明二者有着相似的化合物含量分布。其次栽培样本的淫羊藿苷相对含量也较高, 说明人工栽培及生长方式等因素的改变并未对栽培淫羊藿化学成分含量产生较大变化, 且相应野生样本的高含量特性可以遗传和延续。

4 栽培与野生淫羊藿总黄酮相对含量分析

将12个黄酮类成分的相对含量相加得到总黄酮相对含量^{[24, 25]}, 栽培与相应野生以及其他野生箭叶、天平山、柔毛淫羊藿总黄酮相对含量如图 5所示, 其中黄色代表栽培样本, 紫色代表与栽培相应的野生样本, 蓝色代表其他野生样本。

由于选择栽培的相应野生淫羊藿为较优种质, 其总黄酮相对含量均高于其他野生箭叶、天平山、柔毛淫羊藿。将该野生种质进行大规模栽培后, 栽培箭叶、天平山、柔毛淫羊藿样本总黄酮相对含量与相应野生样本较接近, 且与其他野生箭叶、天平山、柔毛淫羊藿相比, 栽培淫羊藿样本质量稳定性较好。

讨论

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UHPLC是一种具高分离度和高速度特性的现代分离技术, 具有良好的分离效果和更高的峰容量; Q-TOF/MS^E作为检测器具有高灵敏度的特点, 在优化的条件下可以使中药中大多数结构类型的化合物均有响应, 并通过测定精确分子量推测化合物的元素组成及分子式, 还可通过解析其中碎片离子信息了解化合物裂解的碎片结构, 从而进行化合物的结构鉴定。UHPLC-Q-TOF/MS^E技术可以更好地用于中药指纹图谱的表征与化学成分的快速鉴定, UHPLC-Q-TOF/MS指纹图谱具有表征全成分的特点, 进行质量分析可以体现中药成分组成的整体性; 结合PCA分析方法可以全面了解多基原、多产地等中药所含化学成分的差异性问题^{[26, 27]}。再将其与UHPLC-PDA相结合, 对中药化学成分进行相对定量, 从而对药材进行较全面的质量分析和控制^[28]。

本文基于UHPLC-PDA-Q-TOF/MS^E从定性和相对定量两方面成功建立了栽培淫羊藿药材的质量分析方法, 实现了对栽培箭叶、天平山、柔毛淫羊藿化学成分的整体性评价。结果表明栽培后箭叶、天平山、柔毛淫羊藿化学成分组成及含量与相应野生淫羊藿较相似, 从而说明栽培环境和生长方式等因素的改变并未对大规模栽培后淫羊藿样本化学成分组成及含量产生较大影响, 且通过大量野生样本遴选出的优质种质的高含量特性可以遗传和延续, 因此对箭叶、天平山、柔毛淫羊藿的栽培是成功的。本实验为淫羊藿药材栽培推广及资源合理开发利用提供了科学依据, 同时也为其他中药材的质量评价提供了一种方法和模式。

致谢本论文的栽培样品来自于国药集团同济堂(贵州)药业有限公司贵州雷山基地和四川乐山基地, 由杨相波、李砾、姜志海和金华提供。

基金

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健康科技创新工程经费资助(2017-I2M-3-013)

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2020年第55卷第5期

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doi: 10.16438/j.0513-4870.2019-0885

接收时间：2019-11-07
首发时间：2026-01-21
出版时间：2020-05-15

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收稿日期：2019-11-07
修回日期：2019-12-29

基金

健康科技创新工程经费资助(2017-I2M-3-013)

作者信息

1.山西医科大学, 山西太原 030001

2.军事科学院军事医学研究院辐射医学研究所, 北京 100850

3.中国医学科学院、北京协和医学院药用植物研究所, 北京 100193

通讯作者:

*郭宝林, Tel:86-10-57833172, E-mail:guobaolin010@163.com;

陈安家, Tel:86-351-4690071, E-mail:chenanjia888@163.com;

马百平, Tel:86-10-66930265, E-mail:mabaiping@sina.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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Sample No.	Sample name	Geographical origin	Sample type
JY-ZP-1	E. sagittatum	Leishan, Guizhou Province	Cultivation
JY-ZP-2	E. sagittatum	Leishan, Guizhou Province	Cultivation
JY-ZP-3	E. sagittatum	Leishan, Guizhou Province	Cultivation
JY-ZP-4	E. sagittatum	Leishan, Guizhou Province	Cultivation
JY-0403	E. sagittatum	Xinning, Hunan Province	Wild (corresponding to cultivation)
JY-0501	E. sagittatum	Jinzhai, Anhui Province	Wild
JY-0514	E. sagittatum	Quanzhou, Guangxi Province	Wild
JY-20181005	E. sagittatum	Shangli, Jiangxi Province	Wild
JY-0509	E. sagittatum	Anji, Zhejiang Province	Wild
JY-0507	E. sagittatum	Huangshan, Anhui Province	Wild
JY-0506	E. sagittatum	Xiuning, Anhui Province	Wild
JY-0516	E. sagittatum	Lianzhou, Ghuangdong Province	Wild
JY-201214	E. sagittatum	Luotian, Hubei Province	Wild
JY-0515	E. sagittatum	Jianghua, Hunan Province	Wild
TPS-ZP-1	E. myrianthum	Leishan, Guizhou Province	Cultivation
TPS-ZP-2	E. myrianthum	Leishan, Guizhou Province	Cultivation
TPS-ZP-3	E. myrianthum	Leishan, Guizhou Province	Cultivation
TPS-ZP-4	E. myrianthum	Leishan, Guizhou Province	Cultivation
TPS-ZP-5	E. myrianthum	Leishan, Guizhou Province	Cultivation
TPS-ZP-6	E. myrianthum	Leishan, Guizhou Province	Cultivation
TPS-0338	E. myrianthum	Yanhe, Guizhou Province	Wild (corresponding to cultivation)
TPS-0324	E. myrianthum	Shibing, Guizhou Province	Wild
TPS-0415	E. myrianthum	Zhijiang, Hunan Province	Wild
TPS-0323	E. myrianthum	Wanshan, Guizhou Province	Wild
TPS-0325	E. myrianthum	Yuping, Guizhou Province	Wild
TPS-0406	E. myrianthum	Tianzhu, Guizhou Province	Wild
TPS-0401	E. myrianthum	Duyun, Guizhou Province	Wild
TPS-0421	E. myrianthum	Sangzhi, Hunan Province	Wild
TPS-0405	E. myrianthum	Huitong, Hunan Province	Wild
TPS-0465	E. myrianthum	Enshi, Hubei Province	Wild
RM-ZP-1	E. pubescens	Leshan, Sichuan Province	Cultivation
RM-ZP-2	E. pubescens	Leshan, Sichuan Province	Cultivation
RM-ZP-3	E. pubescens	Leshan, Sichuan Province	Cultivation
RM-LS	E. pubescens	Leshan, Sichuan Province	Wild (corresponding to cultivation)
RM-0456	E. pubescens	Nanzheng, Shaanxi Province	Wild
RM-0525	E. pubescens	Bazhong, Sichuan Province	Wild
RM-0616	E. pubescens	Hongya, Sichuan Province	Wild
RM-0535	E. pubescens	Chengdu, Sichuan Province	Wild
RM-0711-15	E. pubescens	Jiange, Sichuan Province	Wild
RM-0711-17	E. pubescens	Tongnan, Chongqin City	Wild
RM-0711-8	E. pubescens	Qionglai, Sichuang Province	Wild
RM-0711-11	E. pubescens	Pingwu, Sichuan Province	Wild
RM-0711-18	E. pubescens	Longchang, Sichuan Province	Wild
RM-0711-16	E. pubescens	Dazu, Chongqin City	Wild
RM-0711-9	E. pubescens	Beichuan, Sichuan Province	Wild

Sample No.

Sample name

Geographical origin

Sample type

JY-ZP-1

E. sagittatum

Leishan, Guizhou Province

Cultivation

JY-ZP-2

E. sagittatum

Leishan, Guizhou Province

Cultivation

JY-ZP-3

E. sagittatum

Leishan, Guizhou Province

Cultivation

JY-ZP-4

E. sagittatum

Leishan, Guizhou Province

Cultivation

JY-0403

E. sagittatum

Xinning, Hunan Province

Wild (corresponding to cultivation)

JY-0501

E. sagittatum

Jinzhai, Anhui Province

Wild

JY-0514

E. sagittatum

Quanzhou, Guangxi Province

Wild

JY-20181005

E. sagittatum

Shangli, Jiangxi Province

Wild

JY-0509

E. sagittatum

Anji, Zhejiang Province

Wild

JY-0507

E. sagittatum

Huangshan, Anhui Province

Wild

JY-0506

E. sagittatum

Xiuning, Anhui Province

Wild

JY-0516

E. sagittatum

Lianzhou, Ghuangdong Province

Wild

JY-201214

E. sagittatum

Luotian, Hubei Province

Wild

JY-0515

E. sagittatum

Jianghua, Hunan Province

Wild

TPS-ZP-1

E. myrianthum

Leishan, Guizhou Province

Cultivation

TPS-ZP-2

E. myrianthum

Leishan, Guizhou Province

Cultivation

TPS-ZP-3

E. myrianthum

Leishan, Guizhou Province

Cultivation

TPS-ZP-4

E. myrianthum

Leishan, Guizhou Province

Cultivation

TPS-ZP-5

E. myrianthum

Leishan, Guizhou Province

Cultivation

TPS-ZP-6

E. myrianthum

Leishan, Guizhou Province

Cultivation

TPS-0338

E. myrianthum

Yanhe, Guizhou Province

Wild (corresponding to cultivation)

TPS-0324

E. myrianthum

Shibing, Guizhou Province

Wild

TPS-0415

E. myrianthum

Zhijiang, Hunan Province

Wild

TPS-0323

E. myrianthum

Wanshan, Guizhou Province

Wild

TPS-0325

E. myrianthum

Yuping, Guizhou Province

Wild

TPS-0406

E. myrianthum

Tianzhu, Guizhou Province

Wild

TPS-0401

E. myrianthum

Duyun, Guizhou Province

Wild

TPS-0421

E. myrianthum

Sangzhi, Hunan Province

Wild

TPS-0405

E. myrianthum

Huitong, Hunan Province

Wild

TPS-0465

E. myrianthum

Enshi, Hubei Province

Wild

RM-ZP-1

E. pubescens

Leshan, Sichuan Province

Cultivation

RM-ZP-2

E. pubescens

Leshan, Sichuan Province

Cultivation

RM-ZP-3

E. pubescens

Leshan, Sichuan Province

Cultivation

RM-LS

E. pubescens

Leshan, Sichuan Province

Wild (corresponding to cultivation)

RM-0456

E. pubescens

Nanzheng, Shaanxi Province

Wild

RM-0525

E. pubescens

Bazhong, Sichuan Province

Wild

RM-0616

E. pubescens

Hongya, Sichuan Province

Wild

RM-0535

E. pubescens

Chengdu, Sichuan Province

Wild

RM-0711-15

E. pubescens

Jiange, Sichuan Province

Wild

RM-0711-17

E. pubescens

Tongnan, Chongqin City

Wild

RM-0711-8

E. pubescens

Qionglai, Sichuang Province

Wild

RM-0711-11

E. pubescens

Pingwu, Sichuan Province

Wild

RM-0711-18

E. pubescens

Longchang, Sichuan Province

Wild

RM-0711-16

E. pubescens

Dazu, Chongqin City

Wild

RM-0711-9

E. pubescens

Beichuan, Sichuan Province

Wild

Peak No.	t_R /min	Precursor ion	Experimental mass	Error (mDa)	Formula	Fragment ion	Identification	E. s	E. m	E. p	Ref.
1	0.56	[M-H]^-	353.086 7	-0.7	C₁₆H₁₈O₉	191, 179, 173, 135 (-)	Chlorogenic acid	-	+	+	[19, 20]
2	0.75	[M-H]^-	337.093 2	0.9	C₁₆H₁₈O₈	191, 173, 163, 137 (-)	5-p-Coumaroylquinic acid	+	+	+	[19]
3	1.05	[M-H]^-	463.087 3	-0.4	C₂₁H₂₀O₁₂	301 (-)	Hyperoside	+	+	+	[19, 20]
4	1.10	[M-H]^- [M+H]⁺	577.154 8 579.171 0	-0.9 -0.4	C₂₇H₃₀O₁₄	431, 285 (-) 433, 287 (+)	Kaempferol-3-O-dirhamnoside or its isomers	+	+	+	[19]
5	1.53	[M-H]^- [M+H]⁺	447.093 5 449.108 4	-0.8 -1.1	C₂₁H₂₀O₁₁	301, 271, 255 (-) 303, 273, 257 (+)	Quercetin-3-O-α-L-rhamnoside	+	+	+	[19, 20]
6	1.68	[M-H]^- [M+H]⁺	677.208 8 679.222 6	0.6 -1.2	C₃₂H₃₈O₁₆	515, 353 (-) 517, 355 (+)	Hexandraside E	+	+	+	[19, 20]
7	1.79	[M-H]^- [M+H]⁺	823.264 9 825.278 9	-1.2 -2.8	C₃₈H₄₈O₂₀	661, 515, 353 (-) 663, 517, 355 (+)	Diphylloside A or its isomers	+	+	+	[19]
8	1.95	[M-H]^- [M+H]⁺	563.138 4 565.156 6	-1.7 0.9	C₂₆H₂₈O₁₄	284 (-) 433, 287 (+)	Kaempferol-7-O-rhamnopyranosyl-xylopyranoside	+	+	+	[22]
9	2.14	[M-H]^- [M+H]⁺	431.098 1 433.110 9	0.3 -2.4	C₂₁H₂₀O₁₀	285 (-) 287 (+)	Kaempferol-3-O-α-L-rhamnoside	+	+	+	[20]
10	2.21	[M-H]^- [M+H]⁺	661.214 3 663.226 8	1.1 -2.1	C₃₂H₃₈O₁₅	499, 353 (-) 517, 355 (+)	Epimedoside A	+	+	+	[19]
11	3.32	[M-H]^- [M+H]⁺	837.281 5 839.297 4	-0.2 2.3	C₃₉H₅₀O₂₀	675, 529, 383 (-) 693, 547, 385 (+)	Sagittasine A	+	+	+	[19]
12	3.92	[M-H]^- [M+H]⁺	837.281 5 839.293 4	-0.2 -4.0	C₃₉H₅₀O₂₀	675, 367, 352 (-) 677, 531, 369, 313 (+)	Epimedin A I^*	+	+	-	[19, 20]
13	4.20	[M-H]^- [M+H]⁺	837.281 5 839.297 4	-0.2 -1.4	C₃₉H₅₀O₂₀	675, 367, 352 (-) 677, 531, 369, 313 (+)	Epimedin A^*	+	+	+	[19, 20]
14	4.29	[M-H]^- [M+H]⁺	807.270 0 809.281 5	-1.2 -5.3	C₃₈H₄₈O₁₉	645, 367, 352 (-) 677, 531, 369, 313 (+)	Isomer of 15	-	+	+
15	4.41	[M-H]^- [M+H]⁺	807.270 1 809.281 5	-1.2 -5.3	C₃₈H₄₈O₁₉	645, 367, 352 (-) 677, 531, 369, 313 (+)	Epimedin B^*	+	+	+	[19, 20]
16	4.62	[M-H]^- [M+H]⁺	821.285 2 823.297 6	-1.6 -4.9	C₃₉H₅₀O₁₉	659, 513, 367, 351 (-) 677, 531, 369, 313 (+)	Epimedin C^*	+	+	+	[19, 20]
17	4.79	[M+HCOO]^- [M+H]⁺	721.235 6 677.240 0	1.2 -4.5	C₃₃H₄₀O₁₅	513, 367, 351 (-) 531, 369, 313 (+)	Icariin^*	+	+	+	[19, 20]
18	4.92	[M-H]^- [M+HCOO]^-	819.271 5 865.276 9	0.3 0.3	C₃₉H₄₈O₁₉	657, 513, 367, 352 (-)	Isomer of 19	+	+	-	[19]
19	5.51	[M-H]^- [M+H]⁺	819.271 5 821.285 9	0.3 -0.9	C₃₉H₄₈O₁₉	657, 513, 367, 352 (-) 531, 369, 313 (+)	3'''-Carbonyl-2''-β-L-quinovosyl-icariin^*	+	+	+
20	5.54	[M-H]^- [M+H]⁺	819.271 5 821.285 9	0.3 -0.9	C₃₉H₄₈O₁₉	657, 513, 367, 352 (-) 531, 369, 313 (+)	Isomer of 19	+	-	+
21	5.66	[M-H]^-	821.288 8	2.0	C₃₉H₅₀O₁₉	659, 513, 367, 352 (-)	Baohuoside VI	+	+	-	[19]
22	5.93	[M-H]^- [M+HCOO]^-	717.239 3 763.244 9	-0.2 -0.1	C₃₅H₄₂O₁₆	571, 513, 367, 351 (-)	Anhydroicaritin-3-O-(acetyl)-glucopyranoside-7-O-rhamnopyranoside	+	-	+	[22]
23	6.25	[M-H]^-	819.271 5	0.3	C₃₉H₄₈O₁₉	657, 513, 367, 352 (-)	Isomer of 19	+	-	+
24	7.87	[M-H]^- [M+H]⁺	675.217 3 677.244 5	-1.2 -1.2	C₃₃H₄₀O₁₅	367, 352 (-) 369, 313 (+)	Sagittatoside A ^*	+	+	+	[19, 20]
25	8.14	[M-H]^- [M+H]⁺	645.217 3 647.234 1	-1.0 -0.1	C₃₂H₃₈O₁₄	367, 352 (-) 369, 313 (+)	Sagittatoside B ^*	-	+	+	[19, 20]
26	8.24	[M-H]^- [M+H]⁺	659.234 6 661.249 6	0.6 -1.5	C₃₃H₄₀O₁₄	367, 352 (-) 369, 313 (+)	2''-O-rhamnopyranosyl Icariside Ⅱ ^*	+	+	+	[19, 20]
27	8.73	[M-H]^- [M+H]⁺	513.175 9 515.191 0	-0.2 -0.7	C₂₇H₃₀O₁₀	366, 351, 323 (-) 369, 313 (+)	Icariside Ⅱ^*	+	+	+	[21]
28	9.80	[M-H]^- [M+H]⁺	337.107 2 339.123 2	-0.4 -2.2	C₂₀H₁₈O₅	282 (-) 283 (+)	Yinyanghuo D or its isomers	+	+	+	[23]
29	10.62	[M-H]^- [M+H]⁺	421.166 8 423.178 5	1.7 -2.3	C₂₅H₂₆O₆	351, 296 (-) 405, 353, 296 (+)	Yinyanghuo B or its isomers	+	+	-	[20, 23]
30	10.71	[M-H]^-	367.118 4	0.2	C₂₁H₂₀O₆	309, 297, 281 (-)	Icaritin	+	+	+	[20]
31	10.77	[M-H]^- [M+H]⁺	405.170 3 407.185 6	0.1 -0.2	C₂₅H₂₆O₅	350 (-) 351, 295 (+)	5, 7, 4'-Trihydroxy-8, 3'-di- prenyl-flavone or its isomers	+	+	+	[21]
32	10.94	[M-H]^- [M+H]⁺	405.170 3 407.185 6	0.1 -0.2	C₂₅H₂₆O₅	350 (-) 351, 295 (+)	5, 7, 4'-Trihydroxy-8, 3'-di- prenyl-flavone or its isomers	+	+	+	[21]

Peak
No.

t_R
/min

Precursor
ion

Experimental
mass

Error
(mDa)

Formula

Fragment ion

Identification

E. s

E. m

E. p

Ref.

0.56

[M-H]^-

353.086 7

-0.7

C₁₆H₁₈O₉

191, 179, 173, 135 (-)

Chlorogenic acid

[19, 20]

0.75

[M-H]^-

337.093 2

0.9

C₁₆H₁₈O₈

191, 173, 163, 137 (-)

5-p-Coumaroylquinic acid

[19]

1.05

[M-H]^-

463.087 3

-0.4

C₂₁H₂₀O₁₂

301 (-)

Hyperoside

[19, 20]

1.10

[M-H]^-
[M+H]⁺

577.154 8
579.171 0

-0.9
-0.4

C₂₇H₃₀O₁₄

431, 285 (-)
433, 287 (+)

Kaempferol-3-O-dirhamnoside or its isomers

[19]

1.53

[M-H]^-
[M+H]⁺

447.093 5
449.108 4

-0.8
-1.1

C₂₁H₂₀O₁₁

301, 271, 255 (-)
303, 273, 257 (+)

Quercetin-3-O-α-L-rhamnoside

[19, 20]

1.68

[M-H]^-
[M+H]⁺

677.208 8
679.222 6

0.6
-1.2

C₃₂H₃₈O₁₆

515, 353 (-)
517, 355 (+)

Hexandraside E

[19, 20]

1.79

[M-H]^-
[M+H]⁺

823.264 9
825.278 9

-1.2
-2.8

C₃₈H₄₈O₂₀

661, 515, 353 (-)
663, 517, 355 (+)

Diphylloside A or its isomers

[19]

1.95

[M-H]^-
[M+H]⁺

563.138 4
565.156 6

-1.7
0.9

C₂₆H₂₈O₁₄

284 (-)
433, 287 (+)

Kaempferol-7-O-rhamnopyranosyl-xylopyranoside

[22]

2.14

[M-H]^-
[M+H]⁺

431.098 1
433.110 9

0.3
-2.4

C₂₁H₂₀O₁₀

285 (-)
287 (+)

Kaempferol-3-O-α-L-rhamnoside

[20]

2.21

[M-H]^-
[M+H]⁺

661.214 3
663.226 8

1.1
-2.1

C₃₂H₃₈O₁₅

499, 353 (-)
517, 355 (+)

Epimedoside A

[19]

3.32

[M-H]^-
[M+H]⁺

837.281 5
839.297 4

-0.2
2.3

C₃₉H₅₀O₂₀

675, 529, 383 (-)
693, 547, 385 (+)

Sagittasine A

[19]

3.92

[M-H]^-
[M+H]⁺

837.281 5
839.293 4

-0.2
-4.0

C₃₉H₅₀O₂₀

675, 367, 352 (-)
677, 531, 369, 313 (+)

Epimedin A I^*

[19, 20]

4.20

[M-H]^-
[M+H]⁺

837.281 5
839.297 4

-0.2
-1.4

C₃₉H₅₀O₂₀

675, 367, 352 (-)
677, 531, 369, 313 (+)

Epimedin A^*

[19, 20]

4.29

[M-H]^-
[M+H]⁺

807.270 0
809.281 5

-1.2
-5.3

C₃₈H₄₈O₁₉

645, 367, 352 (-)
677, 531, 369, 313 (+)

Isomer of 15

4.41

[M-H]^-
[M+H]⁺

807.270 1
809.281 5

-1.2
-5.3

C₃₈H₄₈O₁₉

645, 367, 352 (-)
677, 531, 369, 313 (+)

Epimedin B^*

[19, 20]

4.62

[M-H]^-
[M+H]⁺

821.285 2
823.297 6

-1.6
-4.9

C₃₉H₅₀O₁₉

659, 513, 367, 351 (-)
677, 531, 369, 313 (+)

Epimedin C^*

[19, 20]

4.79

[M+HCOO]^-
[M+H]⁺

721.235 6
677.240 0

1.2
-4.5

C₃₃H₄₀O₁₅

513, 367, 351 (-)
531, 369, 313 (+)

Icariin^*

[19, 20]

4.92

[M-H]^-
[M+HCOO]^-

819.271 5
865.276 9

0.3
0.3

C₃₉H₄₈O₁₉

657, 513, 367, 352 (-)

Isomer of 19

[19]

5.51

[M-H]^-
[M+H]⁺

819.271 5
821.285 9

0.3
-0.9

C₃₉H₄₈O₁₉

657, 513, 367, 352 (-)
531, 369, 313 (+)

3'''-Carbonyl-2''-β-L-quinovosyl-icariin^*

5.54

[M-H]^-
[M+H]⁺

819.271 5
821.285 9

0.3
-0.9

C₃₉H₄₈O₁₉

657, 513, 367, 352 (-)
531, 369, 313 (+)

Isomer of 19

5.66

[M-H]^-

821.288 8

2.0

C₃₉H₅₀O₁₉

659, 513, 367, 352 (-)

Baohuoside VI

[19]

5.93

[M-H]^-
[M+HCOO]^-

717.239 3
763.244 9

-0.2
-0.1

C₃₅H₄₂O₁₆

571, 513, 367, 351 (-)

Anhydroicaritin-3-O-(acetyl)-glucopyranoside-7-O-rhamnopyranoside

[22]

6.25

[M-H]^-

819.271 5

0.3

C₃₉H₄₈O₁₉

657, 513, 367, 352 (-)

Isomer of 19

7.87

[M-H]^-
[M+H]⁺

675.217 3
677.244 5

-1.2
-1.2

C₃₃H₄₀O₁₅

367, 352 (-)
369, 313 (+)

Sagittatoside A ^*

[19, 20]

8.14

[M-H]^-
[M+H]⁺

645.217 3
647.234 1

-1.0
-0.1

C₃₂H₃₈O₁₄

367, 352 (-)
369, 313 (+)

Sagittatoside B ^*

[19, 20]

8.24

[M-H]^-
[M+H]⁺

659.234 6
661.249 6

0.6
-1.5

C₃₃H₄₀O₁₄

367, 352 (-)
369, 313 (+)

2''-O-rhamnopyranosyl Icariside Ⅱ ^*

[19, 20]

8.73

[M-H]^-
[M+H]⁺

513.175 9
515.191 0

-0.2
-0.7

C₂₇H₃₀O₁₀

366, 351, 323 (-)
369, 313 (+)

Icariside Ⅱ^*

[21]

9.80

[M-H]^-
[M+H]⁺

337.107 2
339.123 2

-0.4
-2.2

C₂₀H₁₈O₅

282 (-)
283 (+)

Yinyanghuo D or its isomers

[23]

10.62

[M-H]^-
[M+H]⁺

421.166 8
423.178 5

1.7
-2.3

C₂₅H₂₆O₆

351, 296 (-)
405, 353, 296 (+)

Yinyanghuo B or its isomers

[20, 23]

10.71

[M-H]^-

367.118 4

0.2

C₂₁H₂₀O₆

309, 297, 281 (-)

Icaritin

[20]

10.77

[M-H]^-
[M+H]⁺

405.170 3
407.185 6

0.1
-0.2

C₂₅H₂₆O₅

350 (-)
351, 295 (+)

5, 7, 4'-Trihydroxy-8, 3'-di-
prenyl-flavone or its isomers

[21]

10.94

[M-H]^-
[M+H]⁺

405.170 3
407.185 6

0.1
-0.2

C₂₅H₂₆O₅

350 (-)
351, 295 (+)

5, 7, 4'-Trihydroxy-8, 3'-di-
prenyl-flavone or its isomers

[21]