Systematically Characterizing Chemical Profile and Potential Mechanisms of Qingre Lidan Decoction Acting on Cholelithiasis by Integrating UHPLC-QTOF-MS and Network Target Analysis

Table 1

Characterization of the chemical constituents in QRLDD by UHPLC–QTOF–MS.

Peak; No	(min)	Identification	Formula			Negative ion					Positive ion			Source ^a
				Quasi-molecular ion	Observed mass (Da)	Calculated mass (Da)	ppm	Fragment ions	Quasi-molecular ion	Observed mass (Da)	Calculated mass (Da)	ppm	Fragment ions
1	1.54	Galloyl glucose	C13H16O10	[M-H]^-	331.0678	331.0671	2.11	287[M-H-CO2]	[M+Na]^+	355.0644	355.0636	2.25	311[M+Na-CO2]^+	RRR
								169[M-H-C6H10O5]					338[M+Na-OH]^+
								125[M-H-C6H10O5-CO2]					193[M+Na-C6H10O5]^+
2 ^b	1.69	Gallic acid	C7H6O5	[M-H]^-	169.0147	169.0142	2.96	151[M-H-H2O]	[M+H]^+	171.0289	171.0288	0.58	153[M+H-H2O]^+	EA
								108[M-H-CHO2]					127[M+H-CO2]^+
								125[M-H-CO2]
3^b	3.32	Protocatechuic acid	C7H6O4	[M-H]^-	153.0200	153.0193	4.57	109[M-H-CO2]	—	—	—	—		SR/EA
4	3.58	Shanzhiside methyl ester	C17H26O11	[M-H]^-	405.1400	405.1402	-0.49	361[M-H-CO2]	[M+Na]^+	429.1387	429.1367	4.66		GF
								317[M-H-2CO2]
								225[M-H-gla-H2O]
5	3.68	Shanzhiside	C16H24O11	[M-H]^-	391.1243	391.1246	-0.77	229[M-H-C6H10O5]	—	—	—	—		GF
								185[M-H-C6H10O5-CO2]
								167[M-H-C6H10O5-H2O-CO2]
6	4.26	Gardenoside	C17H24O11	[M+HCOO]^-	449.1308	449.1301	1.56	403.289[M-H-C2H10O5]	[M+Na]^+	427.1176	427.1211	-8.19		GF
				[M-H]^-	403.1265	403.1246	4.71
7	4.44	Neochlorogenic acid	C17H24O11	[M-H]^-	353.0882	353.0878	1.13	191[M-H-C9H6O3]	—	—	—	—		GF
8	4.65	Jasminoside D	C16H26O8	[M-H]^-	345.1568	345.1555	3.77		[M+H]^+	347.1683	347.1700	-4.90	311[M+H-2H2O]^+	GF
9	4.72	Scandoside methyl ester	C17H24O11	[M+HCOO]^-	449.1300	449.1301	-0.22	241[M-H-C6H10O5]	[M+Na]^+	427.1186	427.1211	-5.85		GF
				[M-H]^-	403.1271	403.1246	6.20
10 ^b	4.80	4-Hydroxybenzoic acid	C7H6O3	[M-H]^-	137.0246	137.0244	1.46	93[M-H-CO2]	[M+H]^+	139.0383	139.0390	-5.03		SR/EA
11	5.40	Procyanidin B2	C30H26O12	[M-H]^-	577.1351	577.1351	0.00	559[M-H-H2O]	[M+H]^+	579.1469	579.1497	-4.83		RRR
								535[M-H-C2H2O]
12	5.93	Jasminoside B	C16H26O8	[M+HCOO]^-	391.1618	391.1610	2.05	183[M-H-C6H10O5]	—	—	—	—		GF
				[M-H]^-	345.1560	345.1555	1.45	165[M-H-C6H10O5-H2O]
				[M+Cl]^-	381.1327	381.1322	1.31	121[M−H−C6H10O5−CO2]
13^b	6.16	(+)-Catechin	C15H14O6	[M-H]^-	289.0727	289.0718	3.11	245[M-H-CO2]	[M+H]^+	291.0841	291.0863	-7.56		AF/RRR
				[M+Cl]^-	325.0489	325.0484	1.54	247[M-H-C2H2O]
								179[M-H-C6H6O2]
								271[M-H-H2O]
14	6.23	Gardenone	C12H20O3	[M+HCOO]^-	257.1393	257.1394	-0.39	213[M-H-CO2]	—	—	—	—		GF
15 ^b	6.30	Chlorogenic acid	C16H18O9	[M-H]^-	353.0890	353.0878	3.40	191[M-H-C9H6O3]	[M+H]^+	355.1003	355.1024	-5.91		GF
				[2M-H]^-	707.1834	707.1829	0.71	179[M-H-C9H10O5]
								135[M-H-C8H10O7]
16	6.46	Darendoside A	C19H28O11	[M-H]^-	431.1561	431.1559	0.46		—	—	—	—		SR
17 ^b	6.74	Caffeic acid	C9H8O4	[M-H]^-	179.0357	179.0350	3.91	135[M-H-CO2]	[M+H]^+	181.0483	181.0495	-6.63		SR/EA
18	6.85	Cryptochlorogenic acid	C16H18O9	[M-H]^-	353.0883	353.0878	1.42	179[M-H-C9H10O5]	—	—	—	—		GF
19	7.11	Genipin-1-β-gentiobioside	C23H34O15	[M-H]^-	549.1830	549.1825	0.91	225[M-H-2C6H10O5]	[M+Na]^+	573.1794	573.1790	0.70	541[M+Na-C2H2O]^+	GF
				[M+HCOO]^-	595.1879	595.1880	-0.17	207[M-H-2C6H10O5-H2O]	—	—	—	—
20 ^b	7.60	Syringin	C17H24O9	[M+HCOO]^-	417.1401	417.1402	-0.24	373[M-H-CO2]	[M+Na]^+	395.1300	395.1313	-3.29		RA
21 ^b	8.11	Geniposide	C17H24O10	[M-H]^-	387.1308	387.1297	2.84	225[M-H-C6H10O5]	[M+Na]^+	411.1286	411.1262	5.84		GF
				[M+HCOO]^-	433.1351	433.1352	-0.23	207[M-H-C6H10O5-H2O]
								123[M-H-C10H16O8]
								101[M-H-C13H18O7]
22 ^b	8.16	(-)-Epicatechin	C15H14O6	[M-H]^-	289.0721	289.0718	1.04	245[M-H-CO2]	[M+H]^+	291.0868	291.0863	1.72		AF
				[M+Cl]^-	325.0488	325.0484	1.23	179[M-H-C6H6O2]	—	—	—	—
23	8.17	Genipin	C11H14O5	[M-H]^-	225.0772	225.0768	1.78	207[M-H-H2O]	[M+H]^+	227.0917	227.0914	1.32	209[M+H-H2O]^+	GF
								163[M-H-H2O-CO2]
24	9.05	p-Coumaric acid	C9H8O3	[M-H]^-	163.0406	163.0401	3.07	119[M-H-CO2]	[M+H]^+	165.0547	165.0546	0.61	147[M+H-H2O]^+	SR
25	9.06	Nicotiflorin	C27H30O15	[M-H]^-	593.1518	593.1512	1.01	285[M-H-rha-glu]	[M+H]^+	595.1657	595.1657	0.00		GF
								151[M-H-C19H22O12]
26	9.22	Khelloside	C19H20O10	[M-H]^-	407.1010	407.0984	6.39		[M+H]^+	409.1119	409.1129	-2.44		AF
27	10.58	Schaftoside/Isoschaftoside	C26H28O14	[M-H]^-	563.1407	563.1406	0.18	503[M-H-C2H4O2],	[M+H]^+	565.1544	565.1552	-1.42	547[M+H-H2O]^+	SR/EA
								443[M-H-2C2H4O2]					529[M+H-CO2]^+
28	11.25	Rhoifolin	C27H30O14	[M-H]^-	577.1562	577.1563	-0.17		[M+H]^+	579.1700	579.1708	-1.38		AF
29 ^b	12.21	Rutin	C27H30O16	[M-H]^-	609.1466	609.1461	0.82	301[M-H-rha-gla]	[M+H]^+	611.1593	611.1607	-2.29	303[M+H-rha-glc]^+	GF/EA
				—	—	—	—	151[M-H-C20H27O12]	[M+Na]^+	633.1425	633.1426	-0.16
								178[M-H-C19H27O11]
30	12.60	Scutellarin	C21H18O12	[M-H]^-	461.0724	461.0725	-0.22	285[M-H-glc]	[M+H]^+	463.0877	463.0871	1.30		SR
31	12.74	Carthamidin	C15H12O6	—	—	—	—		[M+H]^+	289.0693	289.0707	-4.84		SR
32	12.78	Neoeriocitrin	C27H32O15	[M-H]^-	595.1671	595.1668	0.50		[M+H]^+	597.1824	597.1814	1.67		AF
33	13.13	Isoquercitrin	C21H20O12	[M-H]^-	463.0880	463.0882	-0.43	301[M-H-C6H10O5]	[M+H]^+	465.1053	465.1028	5.38		GF/EA
								300[M-H-C6H11O5]
34	13.66	Acteoside	C29H36O15	[M-H]^-	623.1969	623.1981	-1.93	461[M-H-C6H10O5]	[M+Na]^+	647.1916	647.1946	-4.64		SR
								315[M-H-rha]
35	14.09	Narirutin	C27H32O14	[M-H]^-	579.1709	579.1719	-1.73	271[M-H-rha-gla]	[M+H]^+	581.1852	581.1865	-2.24		AF
				[M+Cl]^-	615.1490	615.1486	0.65		[M+Na]^+	603.1682	603.1684	-0.33
36	14.36	Kaempferol	C15H10O6	[M-H]^-	285.0410	285.0405	1.75	241[M-H-CO2]	[M+H]^+	287.0544	287.0550	-2.09	153[M+H-C8H6O2]^+	EA
37	14.86	Naringin	C27H32O14	[M-H]^-	579.1728	579.1719	1.55	271[M-H-rha-gla]	[M+H]^+	581.1847	581.1865	-3.10	435[M+H-C6H10O4]^+	AF
				[M+Cl]^-	615.1482	615.1486	-0.65	151[M-H-C20H28O10]	[M+Na]^+	603.1672	603.1684	-1.99	273[M+H-rha-gla]^+
								119[M-H-C19H24O13]
								107[M-H-C20H28O10-CO2]
								259[M-H-rha-gla-C3O2]
								203[M-H-rha-gla-C3O2-C2H2O]
38	15.25	Isorhoifolin	C27H30O14	[M-H]^-	577.1566	577.1563	0.52		[M+H]^+	579.1701	579.1708	-1.21		AF
39	15.37	Jasminoside S/H/I	C22H36O12	[M+HCOO]^-	537.2186	537.2189	-0.56	375[M-H-C6H10O5]	[M+Na]^+	515.2085	515.2099	-2.72		GF
				[M+Cl]^-	527.1899	527.1901	-0.38	167[M-H-2C6H10O5]	—	—	—	—
				[M-H]^-	491.2123	491.2134	-2.24		—	—	—	—
40 ^b	15.65	Hesperidin	C28H34O15	[M-H]^-	609.1829	609.1825	0.66	301[M-H-gla-rha]	[M+H]^+	611.1954	611.1970	-2.62	449[M+H-gla^+	AF
				[M+Cl]^-	645.1600	645.1592	1.24		[M+Na]^+	633.1781	633.1790	-1.42	303[M+H-gla-rha]^+
41 ^b	16.44	Neohesperidin	C28H34O15	[M-H]^-	609.1823	609.1825	-0.33	463[M-H-rha]	[M+H]^+	611.1961	611.1970	-1.47	449[M+H-gla]^+	AF
				[M+Cl]^-	645.1587	645.1592	-0.78	301[M-H-gla-rha]	[M+Na]^+	633.1782	633.1790	-1.26	303[M+H-gla-rha]^+
42	16.71	Viscidulin III	C17H14O8	[M-H]^-	345.0626	345.0616	2.90	301[M-H-CO2]	[M+H]^+	347.0748	347.0761	-3.75		SR
43 ^b	17.60	Baicalin	C21H18O11	[M-H]^-	445.0773	445.0776	-0.67	269[M-H-gluA]	[M+Na]^+	469.0731	469.0741	-2.13		SR
				[2M-H]^-	891.1628	891.1625	0.34	251[M-H-H2O]	[M+H]^+	447.0920	447.0922	-0.45
								241[M-H-CO]
								225[M-H-CO2]
								223[M-H-H2O-CO]
								207[M-H-H2O-CO2]
44	18.03	Crocin-1	C44H64O24	[M-H]^-	975.3737	975.3715	2.26	651[M-H-2C6H10O5]	—	—	—	—		GF
				[M+Cl]^-	1011.3496	1011.3482	1.38	327[M-H-4C6H10O5]	—	—	—	—
45	18.694	Dihydrobaicalin	C21H20O11	[M-H]^-	447.0942	447.0933	2.01	411[M-H-2H2O]	[M+H]^+	449.1069	449.1078	-2.00		SR
				[2M-H]^-	895.1931	895.2012	-9.05	271[M-H-glua]	[M+Na]^+	471.0884	471.0898	-2.97
								253[M-H-gluA-H2O]
46	19.51	Cistanoside D	C31H40O15	[M-H]^-	651.2281	651.2294	-2.00	475[M-H-gluA]	[M+Na]^+	675.2240	675.2259	-2.81		SR
				[M+Cl]^-	687.2063	687.2061	0.29		—	—	—	—
47 ^b	19.54	Quercetin	C15H10O7	[M-H]^-	301.0363	301.0354	2.99	151[M-H-C6H8O3]	[M+H]^+	303.0492	303.0499	-2.31	285[M+H-H2O]^+	GF/EA
													257[M+H-H2O-CO]^+
48	20.13	Crocin-2	C38H54O19	[M-H]^-	813.3186	813.3187	-0.12	651[M-H-C6H10O5]	[M+Na]^+	837.3156	837.3152	0.48		GF
								489[M-H-2C6H10O5]
								327[M-H-3C6H10O5]
49	20.68	Wogonoside	C22H20O11	[M-H]^-	459.0953	459.0933	4.36	283[M-H-gluA]	[M+H]^+	461.1091	461.1078	2.82	443[M+H-H2O]^+	SR
								268[M-H-gluA-CH3]	[M+Na]^+	483.0879	483.0898	-3.93	285[M+H-gluA]^+
													270[M+H-gluA-CH3]^+
50	20.75	Cistanoside C	C31H40O15	[M-H]^-	651.2295	651.2294	0.15	475[M-H-gluA]	[M+Na]^+	675.2255	675.2259	-0.59		SR
				[M+Cl]^-	687.2066	687.2061	0.73
51	21.26	Pectolinarin		[M-H]^-	621.1812	621.1825	-2.09		[M+H]^+	623.1958	623.1970	-1.93		AF
52	21.69	Baicalein O-gluA	C22H20O11	[M-H]^-	459.0949	459.0933	3.49		[M+H]^+	461.1086	461.1078	1.73		SR
		methylester		—	—	—	—		[M+Na]^+	483.0886	483.0898	-2.48
53	23.62	Hesperetin	C16H14O6	[M-H]^-	301.0723	301.0718	1.66		[M+H]^+	303.0851	303.0863	-3.96		AF
54	23.99	Tenaxin II	C16H12O6	[M-H]^-	299.0569	299.0561	2.68	284[M-H-CH3]	[M+H]^+	301.0701	301.0707	1.99	-286[M+H-CH3]^+	SR
55 ^b	24.20	Baicalein	C15H10O5	[M-H]^-	269.0455	269.0455	0.00	251[M-H-H2O]	[M+H]^+	271.0579	271.0601	-8.12		GF
								241[M-H-CO]
								181[M-H-CO-O-CO2]
								225[M-H-CO-O]
								223[M-H-H2O-CO]
56	24.49	Crocin-4	C44H64O24	[M-H]^-	975.3725	975.3715	1.03		—	—	—	—		GF
57	24.89	Tenaxin II isomer	C16H12O6	[M-H]^-	299.0558	299.0561	-1.00	284[M-H-CH3]	[M+H]+	301.0697	301.0707	-3.32	286[M+H-CH3]^+	SR
58	25.72	Meranzin	C15H16O4	—	—	—	—		[M+Na]^+	283.0940	283.0941	-0.35		AF
59	26.03	Dikamaliartanes A	C30H44O6	—	—	—	—		[M+Na]^+	523.3043	523.3030	2.48	239[M+H-CO2]^+	GF
60 ^b	26.02	Aloe-emodin	C15H10O5	[M-H]^-	269.0466	269.0455	4.09	239[M-H-CH2O]	[M+H]+	271.0589	271.0601	-4.43		RRR
								211[M-H-CO]
								183[M-H-CO-CO]
61 ^b	26.71	Rhein	C15H8O6	[M-H]^-	283.0256	283.0248	2.83	255[M-H-CO]	—	—	—	—		RRR
								239[M-H-CO2]
								183[M-H-CO2-2CO]
								211[M-H-CO2-CO]
								183[M-H-CO-2CO]
62	26.76	Limonin	C26H30O8	[M-H]^-	469.1875	469.1868	1.49		[M+H]^+	471.2006	471.2013	-1.49		AF
				[M+Cl]^-	505.1631	505.1635	-0.79		—	—	—	—
63	27.11	Skullcapflavone	C18H16O7	[M-H]^-	343.0825	343.0823	0.58		[M+H]^+	345.0960	345.0969	-2.61		SR
64 ^b	27.20	Wogonin	C16H12O5	[M-H]^-	283.0620	283.0612	2.83	240[M-H-CH3-COH]	[M+H]^+	285.0745	285.0757	-4.21		SR
								239[M-H-CH3-COH]
								223[M-H-CH3-CO2H]
								212[M-H-CH3-2CO]
65	27.86	Skullcapflavon II	C19H18O8	[M-H]^-	373.0938	373.0929	2.41	358[M-H-CH3]	[M+H]^+	375.1073	375.1074	-0.27	345[M+H-2CH3]^+	SR
								343[M-H-2CH3]
								257[M-H-4CH3-2CO]
								328[M-H-3CH3]
								300[M-H-3CH3-CO]
								272[M-H-3CH3-2CO]
66	27.87	Oroxylin A	C16H12O5	[M-H]^-	283.0619	283.0612	2.47	268[M-H-CH3]	[M+H]^+	285.0754	285.0757	-1.05		SR
								239[M-H-COH]
67	28.67	Tenaxin I	C18H16O7	[M-H]^-	343.0831	343.0823	2.33	328[M-H-CH3]	[M+H]^+	345.0963	345.0969	-1.74		SR
								313[M-H-2CH3]
								298[M-H-3CH3]
68 ^b	30.24	Emodin	C15H10O5	[M-H]^-	269.0453	269.0455	-0.74	251[M-H-H2O]	[M+H]^+	271.0600	271.0601	-0.37		RRR/EA
								241[M-H-CO]
								225[M-H-CO-O]
								181[M-H-CO-O-CO2]
69	31.27	Costunolide	C15H20O2	—	—	—	—		[M+H]^+	233.1535	233.1536	-0.43	187[M+H-CH2O2]^+	RA
													215[M+H-H2O]^+
													159[M+H-C3H6O2]^+
70 ^b	31.80	Dehydrocostuslactone	C15H18O2	—	—	—	—		[M+H]^+	231.1357	231.1380	-9.95	185[M+H-CH2	RA
													213[M+H-H2O]^+
													157[M+H-C3H6O2]^+
													195[M+H-H2O4]^+
													175[M+H-C4H8]^+
71 ^b	32.99	Chrysophanol	C15H10O4	—	—	—	—		[M+H]^+	255.0638	255.0652	-5.49		RRR
72 ^b	34.51	Physcion	C16H12O5	—	—	—	—		[M+H]^+	285.0765	285.0757	2.81		RRR

^a RRR, Rhei Radix et Rhizoma; EA, Lysimachiae Herba; SR, Scutellariae Radix; GF, Gardeniae Fructus; AR, Aucklandiae Radix; AF, Aurantii Fructus.
^b Components identified with reference compounds comparison.