Table 5.

Identification of markers in the HPLC fingerprint of the formula by LC-MS analysis

			APCI MS Data (Positive Ion)
Peak	Identification	Time (min)	M/QMIPa	Other Peaks	MS2 of M/QMIP	Plant Sourceb	Content in formulation (mg/kg)
1	Esculin	6.4	341 (M+H)+	179	179	FR
2	Chlorogenic acid	10.3	355 (M+H)+	163	163	AS
3	Aesculetin	12.0	179 (M+H)+		134, 123, 109	FR	310
4	Paeoniflorin	18.8	498 (M+H2O)+	301, 179	301, 179	PL
5	prim-O-Glucosylcimifugin	23.8	469 (M+H)+		307	SD
6	Magnoflorine	32.2	342 (M)+		297, 265	CC, PA
7	Liquiritin	35.9	419 (M+H)+	307, 257		GU
8	5-O-Methylvisamminoside	49.9	453 (M+H)+	291	290	SD
9	Hesperidin	52.0	610 (M)+	465, 449, 303	463	CR	1460
10	Columbamine	60.2	338 (M)+		323, 294	CC
11	Jatrorrhizine	61.3	338 (M)+		323, 294	CC
12	Epiberberine	61.3	336 (M)+			CC
13	Coptisine	61.4	320 (M)+		304, 292	CC
14	Palmatine	66.5	352 (M)+		337, 308	CC, PA	420
15	Berberine	67.3	336 (M)+		321, 292	CC, PA	1620
16	Glycyrrhizic acid	76.2	823 (M+H)+	647, 471, 453, 406		GU	780
17	Schisandrin	81.8	433 (M+H)+	415		SC	140
18	Honokiol	93.3	266 (M)+	263		MO	63
19	Magnolol	98.6	266 (M)+	261		MO	93
20	Schisandrin A	107.7	417 (M+H)+		402, 347, 316	SC

Note: Peak number refers to the chromatographic fingerprint of the clinical preparation (Figure 4). Peaks 6, 10, 12, and13 were identified by LC-MS/MS2 analysis based on the literature values [17,18] and other peaks were identified by comparison of authentic chemicals. Jatrorrhizine and epiberberine (peaks 11, 12) were co-eluted with the same retention times.

^a Molecular or quasi-molecular ion peak; ^b FR: Fraxinus rhynchophylla; AS: Artemisia scoparia; PL: Paeonia lactiflora; SD: Saposhinikovia divaricata; GU: Glycyrrhiza uralensis; CR: Citrus reticulata; CC: Coptis chinensis; PA: Phellodendron amurense; SC: Schisandra chinensis; MO: Magnolia officinalis.