Table 1.

Mass spectral data and plausible identities of the chemical compounds from Epimedium plants by OLE–UHPLC–IT-TOF-MS.

No.	tR (min)	Molecular Formula	[M–H]−	Error (ppm)	MS/MS	Esa	Eko	Epu	Putative Identity
1	8.665	C21H20O13	479.0822	−1.88	317.0082[M–H–Glc]−	√	√	√	myricetin-3-O-glc
2	9.242	C21H20O13	463.0867	−3.23	301.0200[M–H–Glc]−;283.0111[M–H–Glc–H2O]−;255.0173[M–H–Glc–CO–H2O]−	√	√	√	quercetin-3-O-gal
3	9.283	C21H20O13	463.0872	−2.16	301.9988[M–H–Glc]−;273.0003[M–H–Glc–CO]−;254.9923[M–H–Glc–CO–H2O]−	√	√	√	quercetin-7-O-glc
4	9.353	C32H40O16	679.2232	−1.77	517.1674[M–H–Glc]−;355.1254[M–H–2Glc]−;337.1009[M–H–2Glc–H2O]−;327.1169[M–H–2Glc–CO]−;311.1223[M–H–2Glc–CO2]−;283.1262[M–H–2Glc–CO–CO2]−;219.0596[1,3A]−	-	√	-	dihydrodemethylicaritin-7-O-glc-glc
5	9.658	C32H38O16	677.2095	1.18	515.1480[M–H–Glc]−;369.0903[M–H–2Glc–Rha]−;219.0586[1,3A]−	-	√	-	3′,4′-hydroxyicariine-3-O-rha-glc-7-O-glc
6	9.765	C32H38O16	677.2096	1.33	515.1478[M–H–Glc]−;353.0952[M–H–2Glc]−;323.0838[M–H–2Glc–CHO]−;297.0987[M–H–2Glc–CHO–C4H8]−	√	√	-	demethylanhydroicaritin-3-O-glc-7-O-glc
7	10.182	C26H28O15	579.1359	0.69	301.1319[M–H–Glc–Xyl]−;283.0337[M–H–Glc–Xyl–H2O]−;255.0192[M–H–Glc–Xyl–H2O–CO]−;151.0047[1,3A]−	√	-	√	quercetin-3-O-rha-xyl
8	10.640	C38H48O19	807.2696	−2.60	661.2279[M–H–Rha]−;645.2201[M–H–Glc]−;499.1581[M–H–Rha–Glc]−;353.0942[M–H–2Rha–Glc]−;323.0910[M–H–2Rha–Glc–CHO]−;297.0972[M–H–2Rha–Glc–C4H8]−	√	√	√	demethylanhydroicaritin-3-O-rha-rha-7-O-glc
9	10.747	C21H20O11	447.0934	0.22	285.0337[M–H–Glc]−;257.0192[M–H–Glc–CO]−	√	√	√	kaempferol-7-O-glc
10	10.865	C27H30O15	593.1499	−2.19	447.0937[M–H–Rha]−;301.0341[M–H–2Rha]−	√	-	√	quercetin-3-O-rha-7-O-rha
11	10.918	C21H20O7	383.1168	8.35	237.0686[1,3A+H2O]−;219.0578[1,3A]−	-	√	-	aglycone
12	10.950	C38H48O20	823.2679	1.58	661.2143[M–H–Glc]−;515.1463[M–H–Glc–Rha]−;353.1012[M–H–2Glc–Rha]−;297.09658[M–H–2Glc–Rha–C4H8]−	√	√	√	ikarisoside C
13	11.313	C37H46O19	793.2564	0.38	631.1978[M–H–Glc]−;499.1496[M–H–Glc–Xyl]−;353.0946[M–H–Glc–Xyl–Rha]−;281.0386[M–H–Glc–Xyl–Rha–C5H12]−	√	-	√	epimedoside E
14	11.463	C38H48O19	807.2707	−1.24	645.2193[M–H–Glc]−;499.1482[M–H–Glc–Rha]−;353.1007[M–H–Glc–2Rha]−;281.0442[M–H–Glc–2Rha–C5H12]−;219.0506[1,3A]−	√	√	√	demethylanhydroicaritin-3-O-rha(1-3)-rha-7-O-glc
15	11.538	C32H38O15	661.2146	1.21	515.1517[M–H–Glc]−;353.1037[M–H–Glc–Rha]−;323.0909[M–H–Glc–Rha–CHO]−	√	√	√	icarisoside B
16	11.998	C27H30O14	577.1564	0.17	431.0907[M–H–Rha]−;285.0330[M–H–2Rha]−;255.0225[M–H–2Rha–CH2O]−	√	√	√	kaempferol-3-O-rha-7-O-rha
17	12.158	C26H28O14	563.1407	0.18	431.0899[M–H–Xyl]−;285.0301[M–H–Xyl–Rha]−;255.0258[M–H–Xyl–Rha–CH2O]−	√	-	√	kaempferol-7-O-rha-xyl
18	13.257	C21H20O10	431.0987	0.70	285.0394[M–H–Rha]−;255.0339[M–H–Rha–CH2O]−;227.0342[M–H–Rha–CH2O–CO]−;151.0028[1,3A]−	√	√	√	kaempferol-3-O-rha
19	13.707	C39H50O20	837.2842	2.27	675.2303[M–H–Glc]−;383.1121[M–H–Glc–2Rha]−;353.1037[M–H–Glc–2Rha–CH2O]−	√	√	√	3′-hydroxyicariine-3-O-rha-rha-7-O-glc
20	14.038	C26H30O11	517.1719	0.77	355.1273[M–H–Glc]−;327.1228[M–H–Glc–CO]−;311.1286[M–H–Glc–CO2]−;283.1331[M–H–Glc–CO–CO2]−	-	√	-	dihydrodemethylicaritin-7-O-glc
21	14.070	C33H40O16	691.2255	1.59	545.1596[M–H–Rha]−;529.1649[M–H–Glc]−;383.1059[M–H–Glc–Rha]−	√	√	√	3′-hydroxyicariine-3-O-rha-7-O-glc
* 22	14.770	C39H48O20	835.2676	1.20	691.2228[M–H–C6H8O4]−;545.1645[M–H–C6H8O4–Rha]−;383.1126[M–H–C6H8O4–Rha–Glc]−;312.0547[M–H–C6H8O4–Rha–Glc–C4H8–CH3·]−	-	√	-	3′-hydroxyicariine-3-O- rha-C6H8O4-7-O-glc
* 23	14.958	C38H46O19	805.2588	3.35	661.2142[M–H–C6H8O4]−;515.1533[M–H–C6H8O4–Rha]−;353.1028[M–H–C6H8O4–Rha–Glc]−	√	√	√	demethylanhydroicaritin-3-O-rha-glc-C6H8O4
24	16.065	C39H50O20	837.2836	1.56	675.2288[M–H–Glc]−;529.1688[M–H–Glc–Rha]−;367.1177[M–H–2Glc–Rha]−;352.0950[M–H–2Glc–Rha–CH3·]−	√	√	√	hexandroside F
25	16.958	C42H52O22	907.2888	1.21	745.2351[M–H–Glc]−;703.2230[M–H–Glc(OAc)]−;515.1547[M–H–Glc(OAc)–Rha(OAc)]−;353.1024[M–H–Glc(OAc)–Rha(OAc)–Glc]−	-	-	√	demethylanhydroicaritin-3-O-rha(OAc)-glc(OAc)-7-O-glc
a 26	17.142	C39H50O20	837.2849	3.10	675.2307[M–H–Glc]−;367.1169[M–H–2Glc–Rha]−;352.0932[M–H–2Glc–Rha–CH3·]−;323.0905[M–H–2Glc–Rha–CH3·–CHO]−;311.0542[M–H–2Glc–Rha–C4H8]−	√	√	√	epimedium A
27	17.335	C33H40O15	675.2302	1.18	513.1752[M–H–Glc]−;367.1185[M–H–Glc–Rha]−;352.0942[M–H–Glc–Rha–CH3·]−;323.0921[M–H–Glc–Rha–CH3·–CHO]−;295.0614[M–H–Glc–Rha–CH3·–CHO–CO]−;279.1027[M–H–Glc–Rha–CH3·–CHO–CO–H2O]−	√	√	√	icariin isomer
28	17.752	C40H50O21	865.2784	1.39	703.2242[M–H–Glc]−;661.2138[M–H–Glc(OAc)]−;353.0939[M–H–Glc(OAc)–Glc–Rha]−;323.0908[M–H–Glc(OAc)–Glc–Rha–CHO·]−	-	√	-	demethylanhydroicaritin-3-O-rha-glc(OAc)-7-O-glc
29	17.848	C38H48O19	807.2736	2.35	645.2190[M–H–Glc]−;366.1096[M–H–Glc–Rha–Xyl–H·]·−;351.0857[M–H–Glc–Rha–Xyl–CH3·–H·]·−;323.0898[M–H–Glc–Rha–Xyl–CH3·–CO–H·]·−;311.0558[M–H–Glc–Rha–Xyl–C4H8]−;295.0609[M–H–Glc–Rha–Xyl–CH3·–2CO–H·]·−;279.1021[M–H–Glc–Rha–Xyl–CH3·–2CO–H2O–H·]·−;219.0509[1,3A]−	√	√	-	epimedin B isomer
30	17.998	C32H38O14	645.219	0.15	513.1758[M–H–Xyl]−;367.1173[M–H–Xyl–Rha]−;352.0929[M–H–Xyl–Rha–CH3·]−;323.0917[M–H–Xyl–Rha–CH3·–CHO]−;311.0557[M–H–Xyl–Rha–C4H8]−;295.0611[M–H–Xyl–Rha–CH3·–CHO–CO]−;279.1023[M–H–Xyl–Rha–CH3·–CHO–CO–H2O]−	√	√	√	sagittatoside B isomer
a 31	18.052	C38H48O19	807.2734	−4.70	645.2189[M–H–Glc]−;367.1151[M–H–Glc–Rha–Xyl]−;351.0858[M–H–Glc–Rha–Xyl–CH3·]−;323.0907[M–H–Glc–Rha–Xyl–CH3·–CHO]−;311.0539[M–H–Glc–Rha–Xyl–C4H8]−;295.0607[M–H–Glc–Rha–Xyl–CH3·–CHO–CO]−;279.1031[M–H–Glc–Rha–Xyl–CH3·–CHO–CO]−	√	√	√	epimedin B
a 32	18.293	C39H50O19	821.2897	−2.19	675.1032[M–H–Rha]−;659.2358[M–H–Glc]−;366.1093[M–H–Glc–2Rha–H·]·−;351.0858[M–H–Glc–2Rha–CH3·–H·]·−;323.0910[M–H–Glc–2Rha–CH3·–CO–H·]·−;311.0543[M–H–Glc–2Rha–C4H8]−;295.0613[M–H–Glc–2Rha–CH3·–2CO–H·]·−;268.0767[M–H–Glc–2Rha–CH3·–C4H8–C2H2O–H·]·−;240.0981[M–H–Glc–2Rha–CH3·–C4H8–C2H2O–CO–H·]·−	√	√	√	epimedium C
33	18.405	C39H50O19	821.2874)	−6.08	659.2367[M–H–Glc]−;366.1097[M–H–Glc–2Rha–H·]·−;351.0857[M–H–Glc–2Rha–CH3·–H·]·−;323.0905[M–H–Glc–2Rha–CH3·–CO–H·]·−;311.0553[M–H–Glc–2Rha–C4H8]−;295.0606[M–H–Glc–2Rha–CH3·–2CO–H·]·−;279.1015[M–H–Glc–2Rha–CH3·–2CO–H2O–H·]·−	√	√	√	hexandroside D
* 34	18.982	C39H48O19	819.2725	0.98	657.2186[M–H–Glc]−;513.1760[M–H–Glc–C6H8O4]−;367.1174[M–H–Glc–C6H8O4–Rha]−;323.0893[M–H–Glc–C6H8O4–Rha–CH3·–CO]−	√	√	√	anhydroicaritin-3-O-rha-C6H8O4-7-O-glc isomer
a 35	19.187	C33H40O15	721.2378	4.02	529.1713[M–H–Rha]−;513.1766[M–H–Glc]−;366.1077[M–H–Glc–Rha–H·]·−;351.0839[M–H–Glc–Rha–CH3·–H·]·−;323.0569[M–H–Glc–Rha·–CH3·–CO–H·]·−;311.0534[M–H–Glc–Rha–C4H8]−	√	√	√	icariin
36	19.282	C41H52O21	879.2958	3.41	717.2405[M–H–Glc]−;675.2573[M–H–Glc–OAc]−;513.1764[M–H–2Glc–OAc]−;367.1182[M–H–2Glc–Rha(OAc)]−;349.1131[M–H–2Glc–Rha(OAc)–H2O]−	-	√	-	anhydroicaritin-3-O-rha(1-4OAc)-(1-3)glc-7-O-glc
37	19.528	C39H46O18	801.2631	2.5	639.2079[M–H–Glc]−;513.1766[M–H–Glc–3OAc]−;367.1184[M–H–Glc–Rha(3OAc)]−;352.0862[M–H–Glc–Rha(3OAc)–CH3·]−;323.0907[M–H–Glc–Rha(3OAc)–CH3·–CHO]−	-	√	√	anhydroicaritin-3-O- glc-7-O-rha-3OAc
* 38	19.795	C39H48O19	819.2738	2.56	657.2188[M–H–Glc]−;513.1760[M–H–Glc–C6H8O4]−;367.1178[M–H–Glc–C6H8O4–Rha]−;352.0920[M–H–Glc–C6H8O4–Rha–CH3·]−	√	√	√	anhydroicaritin-3-O-rha-C6H8O4-7-O-glc
* 39	19.848	C39H48O19	865.2804	3.7	657.2187[M–H–Glc]−;513.1763[M–H–Glc–C6H8O4]−;367.1183[M–H–Glc–C6H8O4–Rha]−;352.0933[M–H–Glc–C6H8O4–Rha–CH3·]−;323.0902[M–H–Glc–C6H8O4–Rha–CH3·–CHO]−	√	√	√	anhydroicaritin-3-O-rha-7-O-rha-C6H8O4
* 40	20.105	C39H48O21	851.264	2.94	689.2095[M–H–Glc]−;513.1757[M–H–Glc–C6H8O6]−;367.1178[M–H–Glc–C6H8O6–Rha]−	√	-	-	anhydroicaritin-3-O-rha-C6H8O6-7-O-glc
41	20.672	C44H54O23	949.3009	2.74	787.2455[M–H–Glc]−;745.2338[M–H–Glc(OAc)]−;515.1537[M–H–Glc(OAc)–Rha(2OAc)]−;353.1026[M–H–Glc(OAc)–Rha(2OAc)–Glc]−	-	√	-	demethylanhydroicaritin-3-O-rha(2OAc)-glc(OAc)-7-O-glc
42	20.722	C32H38O16	677.2045	−6.2	515.1427[M–H–Glc]−;369.0838[M–H–Glc–Rha]−	√	-	-	3′,4′-hydroxyicariine-7-O-rha-glc
* 43	20.758	C39H48O19	865.2811	4.51	657.2185[M–H–Glc]−;513.1768[M–H–Glc–C6H8O4]−;367.1188[M–H–Glc–C6H8O4–Rha]−	√	√	√	anhydroicaritin-3-O-rha-7-O-glc-C6H8O4
* 44	20.768	C39H48O21	851.2637	2.58	689.2068[M–H–Glc]−;513.1756[M–H–Glc–C6H8O6]−;367.1175[M–H–Glc–C6H8O6–Rha]−	√	√	-	anhydroicaritin-3-O-glc-7-O-rha-C6H8O6
45	20.875	C35H42O16	717.2399	−0.14	513.1752[M–H–Glc(OAc)]−;367.1176[M–H–Glc(OAc)–Rha]−;352.0943[M–H–Glc(OAc)–Rha–CH3·]−;323.0902[M–H–Glc(OAc)–Rha–CH3·–CO]−;311.0559[M–H–Glc(OAc)–Rha–C4H8]−	-	√	-	anhydroicaritin-3-O-glc(OAc)-7-o-rha
46	20.928	C44H54O23	949.3003	2.11	787.2454[M–H–Glc]−;745.2341[M–H–Glc(OAc)]−;515.1541[M–H–Glc(OAc)–Rha(2OAc)]−;353.1022[M–H–Glc(OAc)–Rha(2OAc)–Glc]−	-	√	-	demethylanhydroicaritin-3-O-rha(2OAc)-glc(OAc)-7-O-glc
47	21.035	C39H50O19	821.2846	−3.4	659.1975[M–H–Glc]−;367.1174[M–H–Glc–Rha–Rha]−	√	√	√	epimedium C isomer
48	21.228	C39H48O20	835.2709	5.15	673.2146[M–H–Glc]−;529.1706[M–H–Glc–C6H8O4]−;367.1191[M–H–2Glc–C6H8O4]−;352.0939[M–H–2Glc–C6H8O4–CH3·]−	√	√	√	anhydroicaritin-3-O- glc-C6H9O4-glc
* 49	21.400	C39H48O19	819.2755	4.64	657.2186[M–H–Glc]−;513.1757[M–H–Glc–C6H8O4]−;367.1185[M–H–Glc–C6H8O4–Rha]−;352.0794[M–H–Glc–C6H8O4–Rha–CH3·]−;323.1232[M–H–Glc–C6H8O4–Rha–C3H7]−;311.0689[M–H–Glc–C6H8O4–Rha–C4H8]−;308.0608[M–H–Glc–C6H8O4–Rha–C3H7–CH3·]−	√	√	√	anhydroicaritin-3-O-rha-C6H8O4-7-O-glc
* 50	21.853	C39H48O19	819.2741	2.93	657.2186[M–H–Glc]−;513.1758[M–H–Glc–C6H8O4]−;367.1185[M–H–Glc–C6H8O4–Rha]−	√	√	√	anhydroicaritin-3-O-glc-7-O-rha-C6H8O4
51	21.945	C33H40O16	691.2246	0.29	545.1596[M–H–Rha]−;529.1678[M–H–Glc]−;383.1042[M–H–Glc–Rha]−	-	-	√	3′-hydroxyicariine-3-O-glc-7-O-rha
52	22.318	C43H54O22	921.3065)	3.36	759.2501[M–H–Glc]−;717.2369[M–H–Glc(OAc)]−;367.1175[M–H–Glc(OAc)–Rha(OAc)–Glc]−;352.0932[M–H–Glc(OAc)–Rha(OAc)–Glc–CH3·]−;323.0888[M–H–Glc(OAc)–Rha(OAc)–Glc–CH3·–CHO]−	-	√	-	epimedokoreanoside I
53	22.565	C26H28O11	515.1556	−0.58	369.0957[M–H–Rha]−;219.0661[1,3A]−	-	√	-	3′,4′-hydroxyicariine-3-O-rha
54	22.942	C32H38O15	661.2143	0.76	499.1478[M–H–Glc]−;353.1006[M–H–Glc–Rha]−;323.0909[M–H–Glc–Rha–CHO]−;297.0409[M–H–Glc–Rha–C4H8]−;281.0452[M–H–Glc–Rha–C5H12]−;255.0299[M–H–Glc–Rha–C5H12–CH2CO]−	√	√	√	icarisoside B isomer
55	23.198	C32H38O15	661.2163	3.78	529.1716[M–H–Xyl]−;383.1125[M–H–Xyl–Rha]−;313.0654[[M–H–Xyl–Rha–C4H7–CH3·]−;179.0703[0,3B]−	√	√	√	3′-hydroxyicariine-3-O-rha-xyl
56	23.883	C26H28O11	515.1561	0.39	353.0991[M–H–Glc]−;323.0906[M–H–Glc–CHO]−;297.0969[M–H–Glc–Rha–C4H8]−	√	√	√	demethylanhydroicaritin-7-O-glc
57	24.155	C43H54O22	921.3052	1.95	759.2502[M–H–Glc]−;717.2382[M–H–Glc(OAc)]−;529.1704[M–H–Glc(OAc)–Rha(OAc)]−;367.1176[M–H–Glc(OAc)–Rha(OAc)–Glc]−;352.0936[M–H–Glc(OAc)–Rha(OAc)–Glc–CH3·]−;323.0905[M–H–Glc(OAc)–Rha(OAc)–Glc–CH3·–CHO]−	-	√	-	epimedokoreanoside I isomer
58	24.326	C40H50O20	849.2837	1.65	687.2276[M–H–Glc]−;555.2006[M–H–Glc–Xyl]−;513.1631[M–H–Glc–Xyl–OAc]−;367.1170[M–H–Glc–Xyl–Rha(OAc)]−	-	√	-	anhydroicaritin-3-O-rha(OAc)-xyl-7-O-glc
59	24.508	C43H54O22	921.3049	1.62	759.2512[M–H–Glc]−;367.1176[M–H–Glc(OAc)–Rha(OAc)–Glc]−;352.0945[M–H–Glc(OAc)–Rha(OAc)–Glc–CH3·]−;323.0888[M–H–Glc(OAc)–Rha(OAc)–Glc–CH3·–CHO]−	-	√	-	epimedokoreanoside I isomer
60	24.572	C40H50O20	849.2841	2.12	687.2276[M–H–Glc]−;513.0634[M–H–Glc–Xyl–OAc]−;367.1120[M–H–Glc–Xyl–Rha(OAc)]−	-	√	-	anhydroicaritin-3-O-rha-7-O-glc-xyl(OAc)
61	24.685	C31H36O14	631.2044	1.90	499.1482[M–H–Xyl]−;353.0961[M–H–Xyl–Rha]−;323.0914[M–H–Xyl–Rha–CHO·]−;281.0453[M–H–Xyl–Rha–C5H12]−;255.0293[M–H–Xyl–Rha–C5H12–CH2CO]−	√	√	√	demethylanhydroicaritin-3-O-rha(1-2)xyl
62	24.726	C32H38O14	645.22	1.70	499.1596[M–H–Rha]−;353.0993[M–H–2Rha]−;281.0448[M–H–2Rha–C5H12]−;255.0294[M–H–2Rha–C5H12–CH2CO]−	√	√	√	demethylanhydroicaritin-3-O-rha-(1-2)rha
63	24.845	C36H42O17	745.2363	1.88	583.1817[M–H–Glc]−;367.1188[M–H–Glc–Xyl(2OAc)]−;352.0941[M–H–Glc–Xyl(2OAc)–CH3·]−;323.0909[M–H–Glc–Xyl(2OAc)–CH3·–CHO]−	√	√	√	anhydroicaritin-3-O-xyl(2OAc)-7-O-glc
64	25.048	C32H38O14	645.2205	2.48	499.1587[M–H–Rha]−;353.0994[M–H–2Rha]−;323.0902[M–H–2Rha–CHO·]−;297.0967[M–H–2Rha–C4H8]−	√	√	√	demethylanhydroicaritin-3-O-rha-7-rha
65	25.133	C27H30O11	529.1720	0.94	383.1124[M–H–Rha]−;312.0632[M–H–Rha–C4H8–CH3·]−;297.0400[M–H–Rha–C3H7–CO–CH3·]−;296.0313[M–H–Rha–C3H7–2CO–CH3·]−	√	√	√	caohuoside C
66	25.152	C29H32O11	555.1856	−2.88	366.1094[M–H–Rha(OAc)–H·]·−;351.0856[M–H–Rha(OAc)– CH3·–H·]·−	-	-	√	anhydroicaritin-3-O-rha(OAc)
67	25.315	C35H42O16	717.2381	−2.65	555.1867[M–H–Glc]−;529.1711[M–H–Rha(OAc)]−;367.1174[M–H–Glc–Rha(OAc)]−	√	-	-	anhydroicaritin-3-O-rha(OAc)-7-O-glc
68	25.337	C39H46O18	801.2628	2.12	759.2488[M–H–OAc]−;555.1848[M–H–Glc(2OAc)]−;367.1185[M–H–Glc(OAc)–Rha(OAc)]−;352.0937[M–H–Glc(OAc)–Rha(OAc)–CH3·]−;311.0547[M–H–Glc(OAc)–Rha(OAc)–C4H8]−	-	√	-	anhydroicaritin-3-O-rha(OAc)-glc(2OAc)
69	25.380	C45H56O23	963.3155	1.56	801.2606[M–H–Glc]−;759.2482[M–H–Glc(OAc)]−;367.1173[M–H–Glc(2OAc)–Rha(OAc)–Glc]−;352.0937[M–H–Glc(2OAc)–Rha(OAc)–Glc–CH3·]−	-	√	-	caohuoside B
70	26.192	C26H28O10	499.1603	−1.40	353.1030[M–H–Rha]−;297.0657[M–H–Rha–C4H8]−	√	√	√	icarisoside A
71	26.508	C45H56O23	963.3176	3.74	801.1617[M–H–Glc]−;759.2498[M–H–Glc(OAc)]−;367.1174[M–H–Glc(2OAc)–Rha(OAc)–Glc]−;352.0937[M–H–Glc(2OAc)–Rha(OAc)–Glc–CH3·]−	-	√	-	caohuoside A
72	26.555	C26H28O10	499.1625	3.01	353.1027[M–H–Rha]−;297.0652[M–H–Rha–C4H8]−	√	√	√	demethylanhydroicaritin-3-O-rha
73	26.972	C34H40O16	703.2242	−0.28	541.1032[M–H–Glc]−;499.1396[M–H–Glc–OAc]−;353.0995[M–H–Glc–Rha(OAc)]−	-	√	-	demethylanhydroicaritin-3-O-rha(OAc)-glc
74	27.065	C27H30O11	529.1715	0	383.1104[M–H–Rha]−;327.0467[M–H–Rha–C4H8]−;283.0258[M–H–Rha–C4H8–CO2]−	√	√	√	caohuoside C isomer
75	27.132	C26H28O11	515.1547	−2.33	353.1021[M–H–Glc]−;297.0472[M–H–Glc–C4H8]−	-	√	√	demethylanhydroicaritin-7-O-glc
76	27.282	C45H56O23	963.3157	1.76	801.2633[M–H–Glc]−;759.2513[M–H–Glc(OAc)]−;529.1707[M–H–Glc(2OAc)–Rha(OAc)]−;367.1181[M–H–Glc(2OAc)–Rha(OAc)–Glc]−;352.0937[M–H–Glc(2OAc)–Rha(OAc)–Glc–CH3·]−;323.0921[M–H–Glc(2OAc)–Rha(OAc)–Glc–CH3·–CHO]−	-	√	-	korepimedoside B
77	27.528	C33H40O15	675.2314	2.96	513.1635[M–H–Glc]−;367.1178[M–H–Glc–Rha]−;352.0934[M–H–Glc–Rha–CH3·]−;323.0912[M–H–Glc–Rha–CH3·–CHO]−;311.0554[M–H–Glc–Rha–C4H8]−	√	√	√	icariin isomer
78	28.708	C27H30O11	529.1714	−0.19	367.1173[M–H–Glc]−;352.0933[M–H–Glc–CH3·]−;323.0905[M–H–Glc–CH3·–CHO]−	√	√	√	anhydroicaritin-3-O-glc
79	28.717	C33H40O14	659.2363	2.73	513.1637[M–H–Rha]−;366.1114[M–H–2Rha–H·]·−;351.0875[M–H–2Rha–CH3·–H·]·−;323.0919[M–H–2Rha–CH3·–CO–H·]·−;311.0556[M–H–2Rha–C4H8]−;295.0607[M–H–2Rha–CH3·–2CO–H·]·−;268.0367[M–H–2Rha–C4H8–C2H2O–H·]·−	√	√	√	2″-O-rhamnosyl icariside II
80	28.732	C27H30O11	529.1712	−0.57	367.1176[M–H–Glc]−;352.0859[M–H–Glc–CH3·]−;323.0916[M–H–Glc–CH3·–CHO]−;311.0556[M–H–Glc–C4H8]−	√	√	√	anhydroicaritin-7-O-glc
81	28.847	C33H40O14	659.237	3.79	513.1598[M–H–Rha]−;366.1101[M–H–2Rha –H·]·−;351.0661[M–H–2Rha–CH3·–H·]·−;323.0914[M–H–2Rha–CH3·–CO–H·]·−;311.0553[M–H–2Rha–C4H8]−;295.0605[M–H–2Rha–CH3·–2CO]−;268.0367[M–H–2Rha–C4H8–C2H2O –H·]·−	√	√	√	2″-O-rhamnosyl icariside II isomer
82	29.093	C32H38O14	645.2207	2.79	366.1116[M–H–Xyl–Rha –H·]·−;351.0877[M–H–Xyl–Rha–CH3·–H·]·−;323.0918[M–H–Xyl–Rha–CH3·–CO–H·]·−;311.0553[M–H–Xyl–Rha–C4H8]−;295.0611[M–H–Xyl–Rha–CH3·–2CO –H·]·−	√	√	√	sagittatoside B
83	29.232	C36H42O17	745.2359	1.34	703.2227[M–H–OAc]−;541.0365[M–H–Glc(OAc)]−;353.1022[M–H–Glc(OAc)–Rha(OAc)]−;325.1063[M–H–Glc(OAc)–Rha(OAc)–CO]−	-	√	-	demethylanhydroicaritin-3-O-rha(OAc)-glc(OAc)
84	29.705	C33H40O14	659.234	−0.76	513.1694[M–H–Rha]−;366.1096[M–H–2Rha –H·]·−;351.0859[M–H–2Rha–CH3·–H·]·−;323.0908[M–H–2Rha–CH3·–CO–H·]·−;311.0550[M–H–2Rha–C4H8]−;295.0606[M–H–2Rha–CH3·–2CO –H·]·−	√	√	√	anhydroicaritin-3-O-rha-7-O-rha
85	30.048	C35H42O16	717.2426	3.63	675.2275[M–H–OAc]−;513.1716[M–H–Glc(OAc)]−;367.1175[M–H–Glc(OAc)–Rha]−;352.0931[M–H–Glc(OAc)–Rha–CH3·]−;323.0898[M–H–Glc(OAc)–Rha–CH3·–CHO]−;279.1010[M–H–Glc(OAc)–Rha–CH3·–CHO–CO2]−	√	-	-	anhydroicaritin-3-O-rha-glc(OAc)
a 86	31.183	C27H30O10	513.1783	3.31	366.1109[M–H–Rha–H·]·−;351.0879[M–H–Rha–CH3·–H·]·−;337.1072[M–H–Rha–CHO–H·]·−;323.0927[M–H–Rha–CH3·–CO–H·]·−;311.0558[M–H–Rha–C4H8]−;295.0609[M–H–Rha–CH3·–CO –H·]·−;279.1022[M–H–Rha–CH3·–CO2 –H·]·−	√	√	√	baohuoside I or icariin II
87	31.378	C34H42O15	689.2446	−0.72	513.1742[M–H–Glc–CH2]−;367.1139[M–H–Glc–CH3·–Rha]−	√	√	√	anhydroicaritin-3-O-rha-glc-CH3
* 88	31.937	C33H38O14	657.2201	1.83	513.1760[M–H–C6H8O4]−;367.1179[M–H–C6H8O4–Rha]−;352.0932[M–H–C6H8O4–Rha–CH3·]−;323.0910[M–H–C6H8O4–Rha–CH3·–CHO]−	√	√	√	anhydroicaritin-3-O-rha-C6H8O4
89	32.025	C37H44O17	759.2529	3.03	555.2210[M–H–Glc(OAc)]−;367.1194[M–H–Glc(OAc)–Rha(OAc)]−;352.0946[M–H–Glc(OAc)–Rha(OAc)–CH3·]−;323.0914[M–H–Glc(OAc)–Rha(OAc)–CH3·–CHO]−;311.0554[M–H–Glc(OAc)–Rha(OAc)–C4H8]−	-	√	-	anhydroicaritin-3-O-rha(1-4OAc)-glc(1-4OAc)
90	32.535	C34H42O14	673.2502	0	513.1752[M–H–Rha–CH2]−;367.1139[M–H–Rha–CH2–Rha]−	√	√	√	anhydroicaritin-3-O-rha-CH3-rha
91	33.305	C20H18O6	353.1026	−1.42	337.0697[M–H–H2O]−;281.0246[M–H–H2O–C4H8]−;153.0164[1,3A–isopentenyl]−	√	-	√	aglycone
92	33.432	C39H46O18	801.2636	3.12	759.2500[M–H–OAc]−;555.2135[M–H–Glc(2OAc)]−;367.1186[M–H–Glc(2OAc)–Rha(OAc)]−;352.0938[M–H–Glc(2OAc)–Rha(OAc)–CH3·]−;323.0909[M–H–Glc(2OAc)–Rha(OAc)–CH3·–CHO]−;311.0554[M–H–Glc(2OAc)–Rha(OAc)–C4H8]−;295.0608[M–H–Glc(2OAc)–Rha(OAc)–CH3·–2CO]−;279.1023[M–H–Glc(2OAc)–Rha(OAc)–CH3·–2CO–H2O]−	-	√	-	anhydroicaritin-3-O-rha(OAc)-glc(2OAc)
93	33.545	C35H42O16	717.2416	2.23	513.1721[M–H–Glc(OAc)]−;366.1093[M–H–Glc(OAc)–Rha –H·]·−;351.0860[M–H–Glc(OAc)–Rha–CH3·–H·]·−;323.0916[M–H–Glc(OAc)–Rha–CH3·–CO –H·]·−;311.0552[M–H–Glc(OAc)–Rha–C4H8]−;295.0610[M–H–Glc(OAc)–Rha·–CH3·–2CO–H·]·−	-	√	-	anhydroicaritin-3-O-rha-glc(OAc)
94	33.655	C29H32O11	555.187	−0.36	366.1093[M–H–Glc(OAc)–H·]·−;351.0853[M–H–Glc(OAc)–CH3·–H·]·−;323.0912[M–H–Glc(OAc)–CH3·–CO –H·]·−;311.0562[M–H–Glc(OAc)–C4H8]−	√	-	√	anhydroicaritin-3-O-rha(OAc)
95	33.853	C39H46O18	801.2624	1.62	759.2450[M–H–OAc]−;555.2543[M–H–Glc(2OAc)]−;367.1176[M–H–Glc(2OAc)–Rha(OAc)]−;352.0938[M–H–Glc(2OAc)–Rha(OAc)–CH3·]−;323.0911352.0938[M–H–Glc(2OAc)–Rha(OAc)–CH3·–CHO]−;311.0554[M–H–Glc(2OAc)–Rha(OAc)–C4H8]−;295.0612[M–H–Glc(2OAc)–Rha(OAc)–CH3·–CHO–CO]−;279.1019[M–H–Glc(2OAc)–Rha(OAc)–CH3·–CHO–CO–H2O]−	-	√	-	anhydroicaritin-3-O-rha(OAc)-glc(2OAc)
96	35.245	C25H26O6	421.1663	1.42	365.1022[M–H–C4H8]−;309.0555[M–H–C4H8–C4H8]−;151.0031[1,3A–isopenteny]−	√	√	√	epimedokoreanin B
97	35.568	C21H20O6	367.1194	1.91	352.2177[M–H–CH3·]−;219.0614[1,3A]−	√	√	√	anhydroicaritin
98	35.975	C25H26O5	405.1714	1.72	349.1060[M–H–C4H8]−;293.0601[M–H–C4H8–C4H8]−	-	-	√	4′,5,7-trihydroxy-5′,8-diisopentenylflavone or isomer
99	36.178	C25H26O5	405.171	0.74	349.1063[M–H–C4H8]−;293.0601[M–H–C4H8–C4H8]−	-	-	√	4′,5,7-trihydroxy-5′,8-diisopentenyl-flavone or isomer

Note: ^a: consolidated with standard reference; *: neutral loss of 144 Da; Esa: Epimedium sagittatum (Sieb. et Zucc.) Maxim; Eko: Epimedium koreanum Nakai; Epu: Epimedium pubescens Maxim.