TABLE 2.

Characterization of constituents by LC-MSn analysis in negative-ion modes.

No	tR (min)	Formula	Mass error (ppm)	Fragment ion MS (m/z) in negative ion mode	Identification	Structural formula
Caffeoylquinic acid and caffeic acid						R3	R4	R5
1	7.03	C16H18O9	−1.8	353.0871[M-H]−, 91.0559, 135.0452	Neochlorogenic acid	H	H	C
2	9.89	C16H18O9	−3.3	353.0866[M-H]−, 191.0562	Chlorogenic acid	C	H	H
3	10.24	C16H18O9	−1.7	353.0875[M-H]−, 191.0562	Cryptochlorogenic acid	H	C	H
4	12.14	C9H8O4	0.8	179.0351[M-H]−, 135.0451	Caffeic acid
9	23.96	C25H24O12	−3.6	515.1175[M-H]−, 353.0871, 191.0558, 135.0455	3,4-Dicaffeoylquinic acid	C	C	H
10	26.28	C25H24O12	−3.3	515.1177[M-H]−, 353.0853, 191.0544, 135.0446	3,5-Dicaffeoylquinic acid	C	H	C
13	32.22	C25H24O12	−3.0	515.1179[M-H]−, 353.0845, 191.0536	4,5-Dicaffeoylquinic acid	H	C	C
Flavonoid glycoside						R7	R3’	R4’
5	18.86	C27H30O15	−1.0	593.1496[M-H]− 447.0950[M-H-rhamnose]−, 285.0393 [M-H-rutinoside]−	Luteolin-7-O-rutinoside	−Rutinose	OH	OH
6	20.45	C21H20O11	1.0	447.0911[M-H]− 285.0393[M-H-glucose]−	Luteolin-7-O-glucoside	−Glucoside	OH	OH
7	21.13	C21H18O12	−3.4	461.0712[M-H]− 357.0614[M-H-rutinoside]− 285.0380[M-H-glucuronide]−	Luteolin-7-O-glucuronide	−Glucuronide	OH	OH
11	29.01	C21H20O10	−2.2	431.0954[M-H]− 269.0437[M-H-glucose]−	Apigenin-7-O-glucoside	−Glucose	H	OH
15	38.12	C22H22O11	−3.8	461.1067[M-H]− 299.0540[M-H-glucose]− 284.0300[M-H-glucose-CH3]−	Diosmetin-7-O-glucoside	−Glucose	OH	OCH3
16	45.96	C24H22O13	0.2	517.0945[M-H]− 473.1068[M-H-CO2l]− 431.0970[M-H-malonyl]− 269.0437[M-H-malonyl-glucose]−	Apigenin-7-O-(6″-malonyl)glucoside	−(6″-malonyl) glucose	H	OH
18	52.45	C27H30O15	0.1	591.1681[M-H]− 283.0586[M-H-rutinose]− 268.0350[M-H-rutinose-CH3]	Linarin (acacetin-7O-rutinoside)	−Rutinose	H	OCH3