Chemical Characterization and Metabolic Profiling of the Compounds in the Chinese Herbal Formula Li Chang Decoction by UPLC-QTOF/MS

Table 2

Identification of the major components present in LCD by UPLC-QTOF-MS.

No.	Compound	Formula	Rt (min)	Ion mode	Cal m/z	ESI-m/z	ppm	Fragment ions (m/z)	Ion mode	Cal m/z	ESI+m/z	ppm	Fragment ions (m/z)	Compound class	Source	Reference
P1	Choline	C5H13NO	1.25	—	—	—	—	—	[M + H]^+	104.1070	104.1065	−4.8	60, 59	Choline	CR	[11]
P2	Arginine	C6H14N4O2	1.21	[M - H]^-	173.1039	173.1040	0.6	173.131	[M + H]^+	175.1190	175.1189	−0.6	130, 116, 70, 60	Amino acid	CR	[11]
P3	Asparagine	C4H8N2O3	1.24	[M - H]^-	131.0457	131.0462	3.8	114, 113, 95, 72.58	[M + H]^+	133.0608	133.0606	−1.5	74	Amino acid	CR	[11]
P4	Fructose	C6H12O6	1.33	[M - H]^-	179.0556	179.0555	−0.6	161, 131, 101, 85, 59	[M + Na]^+	203.0526	203.0524	−1.0	158.88.70	Saccharides	CR	[11]
P5	Trigonelline	C7H7NO2	1.36	—	—	—	—	—	[M + H]^+	138.0550	138.0546	−2.9	94, 92, 78,	Alkaloids	CR	[11]
P6	Sucrose	C12H22O11	1.43	[M - H]^-	341.1089	341.1089	0.0	179, 89	—	—	—	—	—	Saccharides	CR	[11]
P7	Raffinose	C18H32O16	1.51	[M - H]^-	503.1618	503.1606	−2.4	323, 191, 179	[M + NH4]+	522.2029	522.2019	−1.9	325, 289, 163, 145, 127	Saccharides	CR	[11]
P8	Stachyose	C24H42O21	1.65	[M - H]^-	665.2146	665.2133	−2.0	341, 323, 179, 161	[M + NH4]+	684.2557	684.2549	−1.2	487, 325, 289, 163, 145, 127	Saccharides	CR	[11]
P9	L-Malic acid	C4H6O5	1.66	[M - H]^-	133.0142	133.0142	0.0	115, 89, 71	—	—	—	—	—	Carboxylic acids	TP/CS	[23, 40]
P10	Citric acid	C6H8O7	1.69	[M - H]^-	191.0197	191.0200	1.6	111, 85, 73	—	—	—	—	—	Carboxylic acids	TP	[40]
P11	Valine	C5H11NO2	1.69	—	—	—	—	—	[M + H]^+	118.0863	118.0854	−7.6	72, 55	Amino acid	TP	[41]
P12	Adenine nucleoside	C10H13N5O4	1.76/3.20	—	—	—	—	—	[M + H]^+	268.1040	268.1038	−0.7	136, 119	Nucleoside	CR	[11]
P13	Chebulic acid	C14H12O11	1.80/2.27	[M - H]^-	355.0307	355.0296	−3.1	337, 293, 249, 205	—	—	—	—	—	Carboxylic acids	CF	[42]
P14	Verbascose	C30H52O26	2.00	[M - H]^-	827.2669	827.2674	0.6	665, 503, 341, 179, 161	[M + Na]^+	851.2639	851.2618	−2.5	689	Saccharides	CR	[11]
P15	Isoleucine	C6H13NO2	2.07	—	—	—	—	—	[M + H]+	132.1019	132.1013	−4.5	86, 85	Amino acid	CR	[11]
P16	L-Pyroglutamic acid	C5H7NO3	2.41	[M - H]^-	128.0348	128.0353	3.9	82	[M + H]+	130.0499	130.0493	−4.6	84.56	Amino acid	CR	[11]
P17	Uridine	C9H12N2O6	2.66	[M - H]^-	243.0623	243.0623	0.0	200, 152, 110	[M + H]+	245.0768	245.0770	0.8	113, 70	Nucleoside	TP	[12]
P18	Succinic acid	C4H6O4	2.70	[M - H]^-	117.0193	117.0192	−0.9	73	—	—	—	—	—	Carboxylic acids	TP	[40]
P19	p-Coumaric acid	C9H8O3	2.86	—	—	—	—	—	[M + H]+	165.0546	165.0541	−3.0	162.123.77	Phenylpropanoids	CR/CS	[11, 53]
P20	Leucine	C6H13NO2	3.10	—	—	—	—	—	[M + H]+	132.1019	132.1014	−3.8	86	Amino acid	TP	[41]
P21	Guanosine	C10H13N5O5	3.74	[M - H]^-	282.0838	282.0841	1.1	150, 133, 107	—	—	—	—	—	Nucleoside	CR/TP	[11, 12]
P22	Gastrodin	C13H18O7	3.85	—	—	—	—	—	[M + NH4]+	304.1391	304.1396	1.6	108, 107, 105	Glycoside	BR	[17]
P23	Gallic acid	C7H6O5	4.17	[M - H]^-	169.0142	169.0146	2.4	125	[M + H]^+	171.0288	171.0281	−4.1	153, 107	Carboxylic acids	CF/CS	[23, 43]
P24	Phenylalanine	C9H11NO2	5.12	[M - H]^-	164.0717	164.0718	0.6	147, 103, 72	[M + H]^+	166.0863	166.0859	−2.4	120, 103, 77	Amino acid	TP	[41]
P25	Codonopsine	C14H21NO4	6.27	—	—	—	—	—	[M + H]^+	268.1543	268.1546	1.1	161, 121, 88, 58	Alkaloids	CR	[11]
P26	5-Galloylshikimic acid	C14H14O9	6.74	[M - H]^-	325.0565	325.0570	1.5	169, 125	—	—	—	—	—	Carboxylic acids	CF	[44]
P27	3, 4-Dihydroxybenzoic acid	C7H6O4	6.93	[M - H]^-	153.0193	153.0197	2.6	109, 108	—	—	—	—	—	Carboxylic acids	TP	—
P28	Hamamelitannin	C20H20O14	7.95	[M - H]^-	483.0780	483.0773	−1.4	271, 211, 169, 125	—	—	—	—	—	Tannins	CF	[46]
P29	1, 6-Di-O-galloyl-β-D-glucose	C20H20O14	8.52/8.91/9.09/9.25	[M - H]^-	483.0780	483.0779	−0.2	423, 271, 211, 169	—	—	—	—	—	Tannins	CF	[47]
P30	5-Hydroxyferulic acid	C10H10O5	8.99	[M - H]^-	209.0456	209.0461	2.4	165, 121, 59	—	—	—	—	—	Carboxylic acids	AMR	-
P31	4-Hydroxybenzoic acid	C7H6O3	9.16	[M - H]^-	137.0244	137.0241	−2.2	93	—	—	—	—	—	Carboxylic acids	BR	[16]
P32	Soyamaloside C	C23H32O16	9.61	[M - H]^-	563.1618	563.1614	−0.7	461, 419	—	—	—	—	—	Glycoside	SF	[19]
P33	Brevifolincarboxylic acid	C13H8O8	9.73	[M - H]^-	291.0141	291.0147	2.1	247, 219, 191	—	—	—	—	—	Carboxylic acids	CF	[45]
P34	Chebulanin(1-O-galloyl-2, 4-O-chebuloyl-b-D-Glc)	C27H24O19	9.98	[M - H]^-	651.0834	651.0839	0.8	633, 481, 275, 169	—	—	—	—	—	Tannins	CF	[44]
P35	6, 7-Dihydroxycoumarin	C9H6O4	10.04	[M - H]^-	177.0188	177.0192	2.3	177, 133, 105, 89	—	—	—	—	—	Coumarins	GRR	[34]
P36	Corilagin	C27H22O18	10.18	[M - H]^-	633.0704	633.0732	4.4	463, 300, 169	[M + NH4]+	652.1145	652.1140	−0.7	465, 363, 303, 277	Tannins	CF	[48]
P37	Quercetin 3-O-glucosyl-rutinoside	C33H40O21	10.37	[M - H]^-	771.1993	771.1990	−0.4	300	[M + H]^+	773.2136	773.2134	−0.3	465, 303	Flavonoids	SF	[21]
P38	Euphormisin M3	C27H24O18	10.55	[M - H]^-	635.0890	635.0891	0.2	483, 465, 169, 125	[M + NH4]+	654.1301	654.1280	−3.3	467, 297, 171, 153	Glycoside	CF	[46]
P39	Manghaslin	C33H40O20	10.58	[M - H]^-	755.2040	755.2041	0.1	609, 447, 299	[M + H]^+	757.2187	757.2179	−1.0	661, 449, 303	Flavonoids	SF	[22]
P40	3,4,8,9,10-Pentahydroxydibenzo[b,d]pyran-6-one	C13H8O7	10.96	[M - H]^-	275.0192	275.0201	3.3	258, 257, 229, 201, 173, 145,	—	—	—	—	—	Carboxylic acids	CF	[44]
P41	Chebulagic acid	C41H30O27	11.05	[M - H]^-	953.0896	953.0903	0.7	301, 275	—	—	—	—	—	Tannins	CF	[46]
P42	Typhaneoside	C34H42O20	11.25	[M - H]^-	769.2197	769.2194	−0.4	623, 314, 189	[M + H]^+	771.2343	771.2327	−2.1	625, 479, 317	Flavonoids	TP	[40]
P43	Rutin	C27H30O16	11.56	[M - H]^-	609.1461	609.1459	−0.3	301	[M + H]^+	611.1607	611.1607	−0.1	465, 303, 85, 71	Flavonoids	SF/TP/CS	[23–25]
P44	Licuraside/liquiritin apioside	C26H30O13	11.65	[M - H]^-	549.1608	549.1611	0.5	255,135	[M + H]^+	551.1765	551.1741	−4.4	257,137	Flavonoids	GRR	[31]
P45	Hyperoside	C21H20O12	11.87	[M - H]^-	463.0882	463.0869	−2.8	300, 301	[M+H]^+	465.1028	465.1021	−1.5	303	Flavonoids	SF	[26]
P46	Liquiritin	C21H22O9	11.85	[M - H]^-	417.1191	417.1184	−1.7	255, 135	[M + NH4]^+	436.1603	436.1592	−2.5	257, 137	Flavonoids	GRR	[31]
P47	Dactylorhin A	C40H56O22	12.06	[M - H]^-	887.3190	887.3181	−1.0	707, 619, 439	[M + NH4]^+	906.3603	906.3601	−0.3	621, 537, 459, 431, 403, 375, 325, 297, 269, 213, 191, 107	Lignans	BR	[16]
P48	Nicotiflorin	C27H30O15	12.18	[M - H]^-	593.1512	593.1502	−1.7	285	[M + H]^+	595.1658	595.1657	−0.2	449, 431, 287	Flavonoids	SF	[27]
P49	Isorhamnetin-3-O-rutinoside-7-O-rhamnoside	C34H40O20	12.23	[M - H]^-	767.2040	767.2046	0.8	705, 665, 623, 314, 299, 271, 179	—	—	—	—	—	Flavonoids	TP	[24]
P50	Narcissin	C28H32O16	12.27	[M - H]^-	623.1618	623.1600	−2.9	315, 314, 300, 285, 271, 255, 151	[M + H]^+	625.1763	625.1754	−1.4	317	Flavonoids	TP/SF	[24, 28]
P51	Vanillic acid	C8H8O4	12.60	[M - H]^-	167.0350	167.0347	−1.8	152,108	—	—	—	—	—	Carboxylic acids	TP/CS	[23]
P52	Isorhamnetin-3-O-beta-galactoside	C22H22O12	12.70	[M - H]^-	477.1038	477.1027	−2.3	314, 285	[M + H]^+	479.1184	479.1168	−3.3	317	Flavonoids	TP	[40]
P53	Choerospodin	C21H22O10	12.83	[M - H]^-	433.1140	433.1151	2.5	271, 151	[M + H]^+	435.1286	435.1268	−4.1	273, 153	Flavonoids	GRR	[35]
P54	Naringenin-7-O-glucoside	C21H22O10	12.95	[M - H]^-	433.1140	433.1151	2.5	433, 271, 151	[M + H]^+	435.1286	435.1274	−2.8	153,147	Flavonoids	GRR	[31]
P55	Notoginsenoside E	C48H82O20	12.96	[M - H]^-	977.5321	977.5308	−1.3	931	—	—	—	—	—	Saponins	NRR	[13]
P56	Gymnoside III	C42H58O23	13.22	[M - H]^-	975.3351	975.3336	−1.5	707, 661, 439	[M + NH4]^+	948.3709	948.3692	−1.8	825, 663, 635, 501, 473, 395, 367, 297, 205, 107	Lignans	BR	—
P57	Lobetyolin	C20H28O8	13.24	—	—	—	—	—	[M + NH4]^+	414.2124	414.2121	−0.6	199, 155	Glycoside	CR	[11]
P58	Ginsenoside Re	C48H82O18	13.34/15.12/16.09/16.51	[M + COOH]^-	991.5483	991.5459	−2.4	783, 621	[M + H]^+	947.5577	947.5544	−3.5	767, 749, 605, 587, 443, 407, 325	Saponins	NRR	[14]
P59	Ginsenoside Rg1	C42H72O14	13.40	[M + COOH]^-	845.4904	845.4899	−0.6	799, 637	[M + H]^+	801.4998	801.4983	−1.8	621, 603, 441, 423, 405, 325	Saponins	NRR	[14]
P60	Violanthin	C27H30O14	13.65	[M - H]^-	577.1563	577.1553	−1.7	515, 475, 433, 145	[M+H]^+	579.1708	579.1701	−1.2	453, 291, 147	Flavonoids	GRR	[31]
P61	Militarine	C34H46O17	13.65	[M + COOH]^-	771.2717	771.2702	−1.9	725, 457, 285, 153	[M + NH4]^+	744.3075	744.3069	−0.8	107	Lignans	BR	[17]
P62	Ononin/ononin isomer	C22H22O9	13.73	—	—	—	—	—	[M + H]^+	431.1342	431.1337	−1.2	269	Flavonoids	GRR	[36]
P63	Licorice glycoside B/D1	C35H36O15	13.73	[M - H]^-	695.1981	695.1961	−2.9	255, 399, 531, 549	—	—	—	—	—	Flavonoids	GRR	[34]
P64	Licorice glycoside C2	C36H38O16	13.81	[M - H]^-	725.2087	725.2076	−1.5	549, 531, 255, 193	[M + H]^+	727.2233	727.2233	0.0	309,297,245	Flavonoids	GRR	[34]
P65	N, N′-diferuloylputrescine	C24H28N2O6	14.17	[M - H]^-	439.1875	439.1885	2.3	289, 149	[M + H]^+	441.2020	441.2009	−2.5	265, 177	Amino acid	SF	[18]
P66	Licorice glycoside E	C35H35NO14	14.34	[M - H]^-	692.1985	692.1983	−0.3	549, 531	[M + H]^+	694.2130	694.2114	−2.3	240, 144	Flavonoids	GRR	[34]
P67	Pallidiflorin	C16H12O4	14.42	[M - H]^-	267.0663	267.0661	−0.7	267, 252, 195, 132	—	—	—	—	—	Flavonoids	GRR	[31]
P68	Decanedioic acid	C10H18O4	14.45	[M - H]^-	201.1132	201.1125	−3.5	183, 139,	—	—	—	—	—	Carboxylic acids	TP	[41]
P69	Isoliquiritigenin	C15H12O4	14.46	[M - H]^-	255.0663	255.0655	−3.1	255, 135, 119, 91	[M + H]^+	257.0808	257.0816	3.1	257, 147, 137, 119, 81	Flavonoids	GRR	[31]
P70	Quercetin	C15H10O7	14.67	[M - H]^-	301.0354	301.0346	−2.7	179, 151	[M + H]^+	303.0499	303.0503	1.3	245, 301, 106, 151	Flavonoids	SF/CS/AC	[23, 29, 30]
P71	Licorice saponin A3	C48H72O21	14.69	[M - H]^-	983.4493	983.4455	−3.9	821, 645, 351	[M + H]^+	985.4642	985.4644	0.3	809, 647, 615, 471, 453	Saponins	GRR	[31]
P72	Ginsenoside Rb1	C54H92O23	15.13	[M + HCOOH–2H]2-	599.2997	599.2987	−1.7	1107, 945, 783, 553, 161	[M + H]^+	1109.6106	1109.6078	−2.5	767, 649, 605, 487, 425, 407, 325, 289	Saponins	NRR	[14]
P73	Licorice saponin G2	C42H62O17	15.24	[M - H]^-	837.3914	837.3898	−1.9	351	[M + H]^+	839.4062	839.4046	−1.9	839, 663, 487, 469	Saponins	GRR	[31]
P74	Notoginsenoside R2	C41H70O13	15.31	[M + COOH]^-	815.4799	815.4787	−1.5	769, 637	—	—	—	—	—	Saponins	NRR	[13]
P75	Naringenin	C15H12O5	15.57	[M - H]^-	271.0604	271.0612	3.0	151, 119	[M + H]^+	273.0757	273.0760	1.1	153, 147	Flavonoids	GRR	[34]
P76	20S-Ginsenoside Rh1	C36H62O9	15.71	[M + COOH]^-	683.4376	683.4359	−2.5	673, 475	—	—	—	—	—	Saponins	NRR	[15]
P77	Ginsenoside Rh4/Rk3	C36H60O8	15.76	—	—	—	—	—	[M + H]^+	621.4364	621.4361	−0.4	441, 423, 405, 221, 203, 187	Saponins	NRR	[15]
P78	Licorice saponin G2 isomer	C42H62O17	15.83	[M - H]^-	837.3914	837.3901	−1.6	351	[M + H]^+	839.4062	839.4065	0.3	839, 663, 645, 487, 469	Saponins	GRR	[31]
P79	Isorhamnetin	C16H12O7	15.95	—	—	—	—	—	[M + H]^+	317.0656	317.0659	0.9	302, 153	Flavonoids	SF	[22]
P80	Raho glycyrrhizin	C48H72O20	15.96	[M - H]^-	967.4544	967.4517	−2.8	329	[M + H]^+	969.4692	969.4650	−4.4	621, 453, 435, 405, 217	Saponins	GRR	[32]
P81	Betulin	C30H50O2	16.10	[M - H]^-	—	—	—	—	[M + H]^+	443.3884	443.3886	0.5	443, 425, 407, 271, 207, 175, 59	Triterpenoids	SF	[20]
P82	Ginsenoside Rd	C48H82O18	16.11	[M + COOH]^-	991.5483	991.5459	−2.4	783, 621	—	—	—	—	—	Saponins	NRR	[13]
P83	Yunganoside G1	C48H74O21	16.14	—	—	—	—	—	[M + H]^+	987.4798	987.4779	−1.9	841, 665, 629, 471, 453, 441, 353	Saponins	GRR	[33]
P84	Glycyrrhizic acid	C42H62O16	16.31	[M - H]^-	821.3965	821.3942	−2.8	759, 351, 193	[M + H]^+	823.4113	823.4111	−0.2	823, 647, 471, 453, 194	Saponins	GRR	[31]
P85	Glycyrrhizic isomer /uralsaponin A/licorice saponin K2/licorice saponin H2	C42H62O16	16.82/17.02	[M - H]^-	821.3965	821.3953	−1.5	351, 193	[M + H]^+	823.4113	823.4111	−0.2	823, 647, 471, 453, 194	Saponins	GRR	[31]
P86	Kaikasaponin III	C48H78O17	17.15	[M + COOH]^-	971.5221	971.5194	−2.8	925	[M + NH4]^+	944.5580	944.5553	−2.9	503, 485, 425, 407, 309, 287, 147	Saponins	SF	[19]
P87	Uralsaponin C/licorice saponin J2	C42H64O16	17.22	—	—	—	—	—	[M + H]^+	825.4270	825.4248	−2.6	825, 613, 455, 409, 397, 317, 177, 159, 141	Saponins	GRR	[31]
P88	Kaikasaponin I	C42H68O13	17.73	—	—	—	—	—	[M + NH4]^+	798.5001	798.4988	−1.6	425, 407, 339, 163	Saponins	SF	[19]
P89	Paniculatumoside A/paniculatumoside B	C28H40O9	18.00	—	—	—	—	—	[M + H]+	521.2747	521.2739	−1.5	331, 145, 113	Saponins (steroidal glycoside)	CPRR	[39]
P90	Glyasperin C	C21H24O5	18.09	—	—	—	—	—	[M + H]^+	357.1697	357.1693	−1.1	283, 165, 137, 123	Flavonoids	GRR	[37]
P91	Ginsenoside F2	C42H72O13	18.57	[M - H]^-	779.4587	779.4575	−1.5	799	[M + Na]^+	807.4868	807.4835	−4.1	785, 767, 443, 407, 325	Saponins	NRR	[15]
P92	Atractylenolide III	C15H20O3	18.62	—	—	—	—	—	[M + H]^+	249.1497	249.1487	−4.0	231, 175, 163, 185, 161, 105, 79	Lactone	CR/AMR	[11, 49]
P93	Sophoraisoflavone A/semilicoisoflavone B	C20H16O6	19.91	—	—	—	—	—	[M + H]^+	353.1020	353.1018	−0.6	335, 311, 299, 215, 199, 153	Flavonoids	GRR	[38]
P94	7-[4-(11-hydroxy-undecyloxy)-phenyl]-7-pyridin-3-yl-hept-6-enoic acid ethyl ester	C31H45NO4	20.82	—	—	—	—	—	[M + H]^+	496.3421	496.3392	−5.8	478, 184, 104	Esters	AMR	[49]
P95	Pseudolaroside B	C14H18O9	6.73	[M - H]^-	329.08781	329.0883	1.49	163	—	—	—	—	—	Carboxylic acids	CS	—
P96	Quinic acid	C7H12O6	1.42	[M - H]^-	191.05611	191.0561	−0.05	191	—	—	—	—	—	Carboxylic acids	CS	[23]
P97	Protocatechuic acid	C7H6O4	6.93	[M - H]^-	153.01933	153.01936	0.20	109, 91	—	—	—	—	—	Carboxylic acids	CS	[50]
P98	Caffeic acid	C9H8O4	10.13	[M - H]^-	179.03498	179.0349	−0.45	135	—	—	—	—	—	Carboxylic acids	CS	[50]
P99	Nonanedioic acid	C9H16O4	13.2	[M - H]^-	187.09758	187.0978	1.18	187, 169, 125, 97, 57	[M + H]^+	189.1121	189.1122	0.53	171, 125, 97, 55	Carboxylic acids	CS/AC	[51]
P100	1-Caffeoylquinic acid	C17H20O9	9.72	[M - H]^-	367.10346	367.1027	−2.07	193, 173	[M+H]^+	369.118	369.1183	0.81	177, 145	Carboxylic acids	CS	[52]
P101	3-O-Feruloylquinic acid	C17H20O9	10.89	[M - H]^-	367.10346	367.1032	−0.71	193, 191, 173	[M + H]^+	369.118	369.1183	0.81	177, 145	Carboxylic acids	CS	[52]
P102	Adenosine	C10H13N5O4	3.35	—	—	—	—	—	[M + H]^+	268.104	268.1042	0.75	136	Nucleoside	CS	[53]
P103	Kaempferol	C15H10O6	15.72	—	—	—	—	—	[M + H]^+	287.055	287.0552	0.70	231, 213, 165, 153, 121	Flavonoids	CS/AC	[29, 50]
P104	20-R-hydroxydammara-24-en-3-one	C30H50O2	16.08	—	—	—	—	—	[M + H]^+	443.3884	443.3881	−0.68	425, 221, 207, 189, 133	Terpenes	AC	—

: compounds verified by standards