Identification and Quantitative Characterization of PSORI-CM01, a Chinese Medicine Formula for Psoriasis Therapy, by Liquid Chromatography Coupled with an LTQ Orbitrap Mass Spectrometer

Shao-Dan Chen; Chuan-Jian Lu; Rui-Zhi Zhao

doi:10.3390/molecules20011594

PMC full text:

Molecules. 2015 Jan; 20(1): 1594–1609.

Published online 2015 Jan 19. doi: 10.3390/molecules20011594

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Table 1

Identification of the chemical constituents of PSORI-CM01 by UHPLC-ESI-MSⁿ analysis.

Peak No.	tR (min)	SelectedIon	ObservedMass (m/z)	CalculatedMass (m/z)	Formula	MS/MS PatternsFragmentation	Identifieation	Source ^a	Reference
1	0.41	[M−H]	191.0559	191.0556	C₇H₁₂O₆	191→173, 127, 109	quinic acid	Sa	[8]
2	0.51	[M−H]	133.0140	133.0137	C₄H₆O₅	133→115, 87, 71	malic acid	M
3	0.60	[M−H]	173.0451	173.0450	C₇H₁₀O₅	173→155, 145, 129	shikimic acid	Sm	[9]
4	0.88	[M−H]	191.0198	191.0192	C₆H₈O₇	191→173, 155→111	citric acid	M
5	0.98	[M−H]	115.0037	115.0031	C₄H₄O₄	115→97, 71	fumaric acid	Sa	[8]
6	2.16	[M−H]	169.0142	169.0137	C₇H₆O₅	169→125	gallic acid	P	[24,25]
7	2.60	[M−H]	331.0663	331.0665	C₁₃H₁₆O₁₀	331→169	gallic acid-1-O-glucoside	P
8	3.28	[M−H]	315.0716	315.0716	C₁₃H₁₆O₉	315→297, 247,153	protocatechuic acid-4-O-glucoside	P, C
9	3.64	[M−H]	197.0453	197.0450	C₉H₁₀O₅	197→153, 123	syringic acid	Sa, Sm	[9]
10	3.69	[M−H]	315.0716	315.0716	C₁₃H₁₆O₉	315→169	gallic acid-1-O-rhamnoside	P
11	3.78	[M−H]	153.0192	153.0188	C₇H₆O₄	153→109	protocatechuic acid	Sa,Sm,C	[8,9]
12	3.82	[M−H]	493.1208	493.1193	C₁₉H₂₆O₁₅	493→313, 169	gallic acid-1-O-glucosyl-(6→1)-glucoside	P
13	4.02	[M−H]	359.0977	359.0978	C₁₅H₂₀O₁₀	359→197, 179	syringic acid-4-O-glucoside	Sa, Sm	[9]
14	4.83	[M−H]	181.0495	181.0450	C₉H₁₀O₅	197→169, 133	3,5-dimethoxy-4-hydroxy-benzaldehyde	Sa
15	4.93	[M−H]	137.0243	137.0239	C₇H₆O₃	137→109, 93	4-hydroxybenzoic acid	C, M, Sm, Sa,
16	5.01	[M−H]	353.0873	353.0873	C₁₆H₁₈O₉	353→191, 179→135	3-O-caffeoylquinic acid	Sa	[8]
17	5.24	[M−H]	165.0556	165.0552	C₉H₁₀O₃	165→151, 135	paeonal	P	[24,25]
18	5.31	[M−H]	345.1182	345.1186	C₁₅H₂₂O₉	345→183	(3,5-dimethoxy-4-hydroxyphenyl)methy-O-glucoside	Sa
19	5.59	[M−H]	183.0296	183.0293	C₈H₈O₅	183→124	methyl gallate	P
20	6.20	[M−H]	609.1445	609.1456	C₂₇H₃₀O₁₆	609→445, 301	rutin	M
21	6.20	[M−H]	495.1498	495.1503	C₂₃H₂₈O₁₂	495→465,333,281	oxypaeoniflorin	P
22	6.12	[M−H]	353.0872	353.0873	C₁₆H₁₈O₉	353→191, 179, 135	5-O-caffeoylquinic acid	Sa	[8]
23	6.17	[M−H]	289.0713	289.0712	C₁₅H₁₄O₆	289→245, 205, 179	(+)-catechin	P, Sm	[9]
24	6.18	[M−H]	335.0767	335.0767	C₁₆H₁₆O₈	335→289, 179, 135, 111	3-O-caffeoylshikimic acid	Sa, Sm	[9]
25	6.21	[M−H]	321.0246	321.0247	C₁₄H₁₀O₉	321→169	p-digallic acid	P
26	6.41	[M−H]	353.0873	353.0873	C₁₆H₁₈O₉	353→191, 179, 135	4-O-caffeoylquinic acid	Sa	[8]
27	6.43	[M−H]	469.1129	469.1135	C₂₄H₂₂O₁₀	469→423, 371, 315, 289	8-[β-(3,4-dihydroxyphenyl)-α-carboxyl-3-xoxpropyl]-substituted catechin	Sm	[9]
28	6.45	[M−H]	179.0345	179.0344	C₉H₈O₄	179→135, 85	caffeic acid	Sa, Sm, A	[8,9]
29	6.59	[M+COOH]	447.1500	447.1503	C₁₈H₂₆O₁₀	447→401, 349, 317, 191	phenylmethyl-glucoside-(6→1)-apiose	M
30	6.62	[M−H]	221.0452	221.0450	C₁₁H₁₀O₅	221→206	fraxidin	Sa	[8]
31	6.67	[M−H]	369.0821	369.0822	C₁₆H₁₈O₁₀	369→207	fraxin	Sa	[8]
32	6.87	[M−H]	435.1289	435.1291	C₂₁H₂₄O₁₀	435→273	isoliquiritigenin-7-O-glucoside	Sa, P	[8]
33	6.87	[M−H]	431.1914	431.1917	C₂₀H₃₂O₁₀	431→385, 223, 205, 153	drovomifoliol-O-glucopyranoside	Sa	[8]
34	6.96	[M−H]	433.2070	433.2074	C₂₀H₃₄O₁₀	433→387, 369 , 225	dihydrovomifoliol-O-glucoside	Sa	[8]
35	7.13	[M−H]	335.0767	335.0767	C₁₆H₁₆O₈	335→289, 179, 135, 111	4-O-caffeoylshikimic acid	Sa, Sm	[9]
36	7.20	[M−H]	289.0712	289.0712	C₁₅H₁₄O₆	289→245, 205, 179	epi-catechin	P, Sm	[9]
37	7.23	[M+COOH]	525.1604	481.1710	C₂₃H₃₀O₁₁	525→479, 465, 121	albiflorin	P	[24]
38	7.28	[M−H]	207.0296	207.0293	C₁₀H₈O₅	207→192	fraxetin	Sa	[8]
39	7.38	[M−H]	335.0767	335.0767	C₁₆H₁₆O₈	335→289, 179, 135, 111	5-O-caffeoylshikimic acid	Sa, Sm	[9]
40	7.61	[M+COOH]	525.1604	481.1710	C₂₃H₃₀O₁₁	525→479, 327, 283,161	paeoniflorin	P	[24,25]
41	7.72	[M−H]	471.1863	471.1866	C₂₂H₃₂O₁₁	471→425, 263	sarcaglaboside G	Sa	[8]
42	7.81	[M−H]	339.0715	339.0716	C₁₅H₁₆O₉	339→193, 165,137	6,7,8-trihydroxycoumarin-7-rhamnoside	Sa, Sm	[9]
43	7.94	[M−H]	629.1514	629.1506	C₃₀H₃₀O₁₅	629→483, 475, 449, 303, 285	8-[β-(3,4-dihydroxyphenyl)-α-carboxyl-3-oxopropyl]-substituted neoastilbin	Sm	[9]
44	8.05	[M−H]	473.2022	473.2023	C₂₂H₃₄O₁₁	473.202	sarcaglaboside H	Sa	[8]
45	8.16	[M−H]	629.1514	629.1506	C₃₀H₃₀O₁₅	629→483, 475, 449, 303, 285	8-[β-(3,4-dihydroxyphenyl)-α-carboxyl-3-oxopropyl]-substituted astilbin	Sm	[9]
46	8.18	[M−H]	565.1552	565.1557	C₂₆H₃₀O₁₄	565→313, 193	(2R/2S)-naringenin-6-C-β-d-glucopy ranoside-(6-1)-apiose	Sa	[8]
47	8.27	[M−H]	537.1025	537.1033	C₂₇H₂₂O₁₂	537→493, 295, 159, 109	lithospermic acid	A
48	8.33	[M−H]	565.1550	565.1557	C₂₆H₃₀O₁₄	565→313, 193	(2R/2S)-naringenin-6-C-glucopyranoside-(6-1)-apiose	Sa	[9]
49	8.52	[M−H]	629.1514	629.1506	C₃₀H₃₀O₁₅	629→483, 475, 449, 303, 285	8-[β-(3,4-dihydroxyphenyl)-α-carboxyl-3-oxopropyl]-substituted	Sm	[9]
50	8.57	[M−H]	221.0452	221.0450	C₁₁H₁₀O₅	221→206, 191, 163	isofraxidin	Sa	[8]
51	8.62	[M−H]	417.1186	417.1186	C₂₁H₂₂O₉	417→255	liquiritin	G	[26]
52	8.62	[M−H]	549.1607	549.1608	C₂₆H₃₀O₁₃	549→429, 255	liquiritin apioside	G	[26]
53	8.77	[M−H]	451.1025	451.1029	C₂₄H₂₀O₉	451→341, 299	cinchonain Ia	Sm
54	8.80	[M−H]	303.0505	303.0505	C₁₅H₁₂O₇	303→285	taxifolin	Sm	[9]
55	8.82	[M−H]	300.9986	300.9984	C₁₄H₆O₈	301→257	gallogen	P
56	8.84	[M−H]	449.1088	449.1084	C₂₁H₂₂O₁₁	449→303, 285	neoastilbin	Sa, Sm	[8,9]
57	8.98	[M−H]	629.1514	629.1506	C₃₀H₃₀O₁₅	629→483, 475, 449, 303, 285	8-[β-(3,4-dihydroxyphenyl)-α-carboxyl-3-oxopropyl]-substituted isoastilbin	Sm	[9]
58	8.96	[M−H]	631.1656	631.1663	C₃₀H₃₂O₁₅	631→613, 491, 399, 169	galloyl paeoniflorin	P
59	9.02	[M−H]	477.0668	477.0669	C₂₁H₁₈O₁₃	477→301	quercetin-3-O-glucruronide	Sa	[8]
60	9.02	[M−H]	449.1088	449.1084	C₂₁H₂₂O₁₁	449→303, 285	astilbin	Sa, Sm	[8,9]
61	9.05	[M−H]	521.1295	521.1295	C₂₄H₂₆O₁₃	521→359, 197	rosmarinic acid-4-O-glucoside	Sa
62	9.38	[M−H]	939.1089	939.1104	C₄₁H₃₂O₂₆	939→769, 617, 393, 317	penta-O-galloyl-glucose	P
63	9.49	[M−H]	515.1184	515.1190	C₂₅H₂₄O₁₂	515→353	dicaffeoylquinic acid	Sa
64	9.64	[M−H]	449.1088	449.1084	C₂₁H₂₂O₁₁	449→303, 285	neoisoastilbin	Sa, Sm	[8,9]
65	9.68	[M−H]	717.1442	717.1456	C₃₆H₃₀O₁₆	717→519, 475, 321	caffeic acid tetramer	A
66	9.78	[M−H]	187.0974	187.0970	C₉H₁₆O₄	187→142, 125	nonandioic acid	P, G
67	9.84	[M−H]	449.1088	449.1084	C₂₁H₂₂O₁₁	449→303, 285	isoastilbin	Sa, Sm	[8,9]
68	9.87	[M−H]	451.1025	451.1029	C₂₄H₂₀O₉	451→341, 299	cinchonain Ib	Sm
69	9.95	[M−H]	717.1442	717.1456	C₃₆H₃₀O₁₆	717→519, 475, 321	caffeic acid tetramer isomer	A
70	9.96	[M−H]	597.1605	597.1608	C₃₀H₃₀O₁₃	597→451, 341, 217	glabraoside C	Sa	[8]
71	9.95	[M−H]	719.1599	719.1512	C₃₆H₃₂O₁₆	719→539, 359	dirosmarinic acid	Sa
72	10.08	[M−H]	433.1131	433.1135	C₂₁H₂₂O₁₀	433→343, 313, 271, 179	(2R/2S)-naringenin-6-C-glucopyranoside	Sa	[8]
73	10.17	[M−H]	433.1131	433.1135	C₂₁H₂₂O₁₀	433→343, 313, 271, 179	(2R/2S)-naringenin-6-C-glucopyranoside	Sa	[8]
74	10.36	[M−H]	587.2327	587.2340	C₂₇H₄₀O₁₄	587→451, 341, 217	sarcaglaboside D	Sa	[8]
75	10.61	[M−H]	515.1184	515.1190	C₂₅H₂₄O₁₂	515→353	dicaffeoylquinic acid	Sa
76	10.64	[M−H]	359.0768	359.0767	C₁₈H₁₆O₈	359→197, 161	rosmarinic acid	Sa, Sm	[8,9]
77	10.73	[M−H]	279.1234	279.1232	C₁₅H₂₀O₅	279→235, 139	zedoalactone D	Sa	[8]
78	10.97	[M+COOH]	507.1497	461.1448	C₂₃H₂₆O₁₀	461→417, 295	lactiflorin	P
79	11.03	[M−H]	433.1132	433.1135	C₂₁H₂₂O₁₀	433→287, 269	engeletin	Sm	[9]
80	11.41	[M−H]	423.1653	423.1655	C₂₁H₂₈O₉	423→261, 243	chloranoside A	Sa	[8]
81	11.80	[M−H]	549.1603	549.1608	C₂₆H₃₀O₁₃	549→417, 255	isoliquiritin apioside	G	[26]
82	11.94	[M−H]	433.1132	433.1135	C₂₁H₂₂O₁₀	433→287, 269	isoengeletin	Sa, Sm	[8,9]
83	11.82	[M−H]	549.1607	549.1608	C₂₆H₃₀O₁₃	549→417, 255	liquiritin apioside	G	[26]
84	12.40	[M−H]	417.1183	417.1186	C₂₁H₂₂O₉	417→255	isoliquiritin	G	[26]
85	12.97	[M−H]	599.1756	599.1765	C₃₀H₃₂O₁₃	599→569	benzoyloxypaeoniflorin	P	[24]
86	12.98	[M−H]	451.1027	451.1029	C₂₄H₂₀O₉	451→341, 299	cinchonain Ic	Sm	[8]
87	13.06	[M−H]	255.0658	255.0657	C₁₅H₁₂O₄	255→135	liquiritigenin	G	[26]
88	13.14	[M−H]	451.1025	451.1029	C₂₄H₂₀O₉	451→341, 299	cinchonain Id	Sm	[8]
89	13.33	[M−H]	373.0918	373.0923	C₁₉H₁₈O₈	373→211, 161	methyl rosmarina	Sa, Sm	[8]
90	13.52	[M−H]	823.4102	823.4116	C₄₂H₆₄O₁₆	823→647, 351	uralsaponin C	G	[27]
91	13.86	[M−H]	835.3742	835.3752	C₄₂H₆₀O₁₇	823→661, 351	uralsaponin D	G	[27]
92	13.52	[M−H]	999.4421	999.4433	C₄₈H₇₂O₂₂	999→837, 645, 351	24-hydroxyl-licorice-saponin A3	G	[27]
93	13.64	[M−H]	895.3950	895.3964	C₄₄H₆₄O₁₉	895→719, 501,351	uralsaponin F	G	[27]
94	13.63	[M−H]	853.3845	853.3858	C₄₂H₆₂O₁₈	853→809, 791, 677, 351	22-hydroxyl-licorice-saponin G2	G	[27]
95	13.61	[M−H]	983.4470	983.4488	C₄₈H₇₂O₂₁	983→821, 645, 351	licorice saponin A3	G	[27]
96	13.68	[M−H]	1025.4579	1025.4593	C₅₀H₇₄O₂₂	1025→993, 833, 497	22-acetoxyl-rhaoglycyrrhizin	G	[27]
97	13.70	[M−H]	849.3538	849.3545	C₄₂H₅₈O₁₈	849→673, 479	uralsaponin E	G	[27]
98	13.76	[M−H]	879.3996	879.4014	C₄₄H₆₄O₁₈	879→861, 643, 351	22-acetoxyl-glycyrrhizin	G	[27]
99	13.77	[M−H]	837.3891	837.3909	C₄₂H₆₂O₁₇	837→819, 661, 351	24-hydroxyl-glycyrrhizin	G	[27]
100	13.78	[M−H]	271.0607	271.0606	C₁₅H₁₂O₅	271→254, 177	naringenin	Sm	[27]
101	13.86	[M−H]	835.3742	835.3752	C₄₂H₆₀O₁₇	823→661, 351	24-hydroxyl-licorice-saponin E2	G	[27]
102	14.00	[M−H]	837.3891	837.3909	C₄₂H₆₂O₁₇	837→819, 775, 661, 351	licorice saponin G2	G	[27]
103	14.00	[M−H]	967.4523	967.4539	C₄₈H₇₂O₂₀	967→805,497, 407, 321	rhaoglycyrrhizin	G	[27]
104	14.01	[M−H]	819.3787	819.3803	C₄₂H₆₀O₁₆	819→777, 643, 351	licorice saponin E2	G	[27]
105	14.06	[M−H]	863.4049	863.4065	C₄₄H₆₄O₁₇	863→819, 729, 687, 351, 289	22-acetoxyl-glycyrrhaldehyde	G	[27]
106	14.13	[M−H]	255.0660	255.0657	C₁₅H₁₂O₄	255→135	isoliquiritigenin	G	[27]
107	14.14	[M−H]	821.3945	821.3945	C₄₂H₆₂O₁₆	821→803, 759, 645, 351	glycyrrhizin	G	[27]
108	14.33	[M−H]	821.3945	821.3960	C₄₂H₆₂O₁₆	821→803, 759, 645, 351	18α-glycyrrhizin	G	[27]

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Note: ^a: A, Arnebiae radix; C, Curcumae rhizome; G, Glycyrrhizae radix et rhizome; M, Mume fructus; P, Paeoniae radix rubra; Sa, Sarcandrae Herba; Sm, Smilacis glabrae rhizome.