The Scientific World Journal

Research Article

Qualitative and Quantitative Analysis of the Major Constituents in Chinese Medical Preparation Lianhua-Qingwen Capsule by UPLC-DAD-QTOF-MS

Table 2

Characterization of compounds in LQC by UPLC-DAD-QTOF-MS.


Peak number	(min)	(nm)	Formula	ES⁻ ()		ES⁺ ()			Identification	Reference
Peak number	(min)	(nm)	Formula	[M–H]⁻ (ppm)	MS^2b	[M + H]⁺(ppm)	[M + Na]⁺	MS^2b	Identification	Reference

1	0.817		C₇H₁₂O₆	191.0555 (−0.5)					Quinic acid	[12]

2	0.982	223, 287	C₆H₈O₇	191.0198 (3.1)	173.0099 [M–H–H₂O]⁻, 111.0088 [M–H–2H₂O–CO₂]⁻				Citric acid	[13]

3^a	1.545	216, 271	C₇H₆O₅	169.0142 (3.0)	125.0241 [M–H–CO₂]⁻				Gallic acid	[14]

4^a	3.010	325	C₁₆H₁₇O₉	353.0878 (1.4) 375.0695 [M–2H + Na]⁻, 707.1830 [2M–H]⁻	191.0497 [M–H–Ca]⁻, 179.0312 [Caffeic acid–H]⁻, 135.0359 [Caffeic acid–H–CO₂]⁻				Neochlorogenic acid	[13]

5^a	3.639	254	C₁₆H₂₄O₁₀	375.1302 (2.9), 751.2667 [2M–H]⁻	213.0773 [M–H–Glc]⁻, 151.0878 [M–H–Glc–CO₂–H₂O]⁻, 125.0721 [M–H–Glc–2CO₂]⁻				Loganic acid	[15]

6^a	4.048	224, 278	C₁₄H₂₀O₇	299.1133 (0.7)	179.0447 [M–H–C₈H₈O]⁻, 119.0246 [M–H–Glc–H₂O]⁻				Salidroside	[16]

7^a	4.557		C₂₀H₃₀O₁₂	461.1674 (3.3)	315.1348 [M–H–Rha]⁻, 297.1589 [M–H–Rha–H₂O]⁻, 153.0644 [M–H–Rha–Glc]⁻, 135.0573 [M–H–Rha–Glc–H₂O]⁻	463.1220 (−4.3)	485.1568	137.0599 [M + H–Rha–Glc–H₂O]⁺	Forsythoside E	[17]

8^a	4.749	327	C₁₆H₁₇O₉	353.0880 (2.0)	191.0556 [M–H–Ca]⁻, 179.0224 [Caffeic acid–H]⁻	355.1028 (−0.3)	377.0857		Chlorogenic acid	[18]

9^a	5.281	325	C₁₆H₁₇O₉	353.0880 (2.0)	179.0348 [Caffeic acid–H]⁻, 173.0461 [Quinic acid–H–H₂O]⁻, 191.0417 [M–H–Ca]⁻				Cryptochlorogenic acid	[18]

10	6.435	270	C₁₇H₂₆O₁₀	389.1096 (3.1)		391.2176 (−0.8)	413.1067	395.2354 [M + Na–H₂O]⁺ 229.0835 [M + H–Glc]⁺	Loganin	[19]

11	6.749		C₁₄H₂₃O₉	335.0776 (2.7)	173.0459 [M–H–Glc]⁻, 161.0373 [Glc–H–H₂O]⁻, 133.0408 [Glc–H–H₂O–CO]⁻	337.0883 (5.3)	359.0686	163.0419 [Glc + H–H₂O]⁺	Rengynic acid-1^′-O-β-D- glucoside	[20]

12	7.222		C₂₁H₂₀O₉	415.1261 (5.1)			439.1207	255.0879 [M + H–Glc]⁺	Isomer of chrysophanol glucoside	[21]

13^a	7.428	245		357.1208 (6.2), 403.1263 M + HCOO, 393.0938 M + Cl		359.1337 (−1.4)	381.1154		Sweroside	[15]

14	7.859		C₁₄H₂₃O₉	335.0871 (4.2)	193.0506, 161.0377, 133.0423	337.0774 (0.9)	359.0225	163.0416 [Glc + H–H₂O]⁺	Isomer of rengynic acid-1^′-O-β-D-glucoside

15	8.106	306	C₂₀H₂₂O₈	389.1458 (2.6), 435.1519 [M + HCOO]⁻	227.0943 [M–H–Glc]⁻				Polydatin	[22]

16	8.222		C₂₉H₃₆O₁₆	639.2219 (−1.7)	477.1894 [M–H–Glc]⁻, 179.0546 [M–Rha–C₁₇H₁₄O₆]⁻, 161.0328 [Glc–H–H₂O]⁻,				R-suspensaside	[23]

17^a	8.320		C₂₁H₂₀O₉	415.1253 (3.1)	253.0542 [M–H–Glc]⁻	417.1394 (−0.7)	439.1200	255.0864 [M + H–Glc]⁺	Chrysophanol glucoside	[21]

18	8.874		C₂₉H₃₆O₁₆	639.2002 (−2.7)	161.0328 [Glc–H–H₂O]⁻, 179.0349 [M–Rha–C₁₇H₁₄O₆]⁻				S-suspensaside	[24]

19	9.054		C₂₉H₃₆O₁₅	623.1999 (−1.2)	311.2176	625.2137 (0.8)	647.1942	479.1562, 471.1479, 325.0925, 163.0394	Isomer of forsythoside A

20^a	9.470	235	C₁₇H₂₄O₁₁	403.1261 (5.2)		405.1331 (−1.7)	427.1203	243.0871 [M + H–Glc]⁺	Secoxyloganin	[19]

21	9.552	276, 313	C₂₁H₂₂O₉	417.1205 (4.6), 835.2331 [2M–H]⁻	255.0652 [M–H–Glc]⁻,		441.1132	257.0811 [M + H–Glc]⁺	Liquiritin	[25]

22^a	9.886	277, 312	C₂₆H₃₀O₁₃	549.1627 (3.5)		551.2823 (4.7)	573.1737	257.0822 [M + H–Api–Glc]⁺	Liquiritin apioside	[26]

23	9.995		C₂₆H₃₀O₁₃	549.1629 (3.8)		551.3403 (−5.1)	573.1735	257.0815 [M + H–Api–Glc]⁺	Isomer of liquiritin apioside	[26]

24	10.088		C₂₇H₃₀O₁₆	609.1844 (−1.8)			633.1712		Rhodiosin	[27]

25^a	10.384	250, 300	C₂₂H₂₂O₉	429.1410 (3.0)			453.1176	269.0974 [M + H–Glc]⁺	Ononin	[28, 29]

26^a	10.722	360	C₂₁H₂₀O₁₂	463.0905 (2.8)	301.0464 [M–H–Glc]⁻	465.1033 (5.2)	487.0333	303.0515 [M + H–Glc]⁺	Hyperin	[24]

27^a	10.819	326	C₂₅H₂₄O₁₂	515.1205 (2.9)	353.0751 [M–H–Ca]⁻	517.1296 (1.7)	539.1156	499.1187 [M + H–H₂O]⁺, 163.0395 [M + H–Ca–Quinic acid]⁺	3,5-Dicaffeoylquinic acid	[30]

28	10.931		C₂₉H₃₆O₁₅	623.1999 (−1.9)	461.1378, 161.0185		647.1941	471.1497, 325.0925, 163.0415	Isomer of forsythoside A

29^a	11.10	256, 354	C₂₇H₃₀O₁₆	609.1465 (1.5)		611.1573 (3.3)	633.1404	465.0982 [M + H–Rha]⁺ 303.0495 [M + H–Rut]⁺	Rutin	[31]

30^a	11.220	280	C₂₉H₃₆O₁₅	623.2001 (−1.6)	461.1920 [M–H–Ca]⁻, 161.0328 [Caffeic acid–H–H₂O]⁻		647.1927	163.0386 [Caffeic acid + H–H₂O]⁺	Forsythoside A	[32]

31	11.589	283	C₂₇H₃₀O₁₅	593.1534 (−1.3)	285.0677 [M–H–Rut]⁻	595.1694 (−0.7)		287.0936 [M + H–Rut]⁺	Kaempferol-3-O-rutinoside	[13]

32	11.692		C₁₉H₃₅O₁₆	519.1884 (3.5), 565.1953 [M + HCOO]⁻	357.1366 [M–H–Glc]⁻		543.1855	359.1454 [M + H–Glc]⁺, 341.1411 [M + H–Glc–H₂O]⁺	(+)-Pinoresinol-β-D-glucoside	[33]

33^a	12.213	210, 262	C₂₀H₂₇NO₁₁	456.1523 (3.7)		458.1641 (−4.6)		296.1124 [M + H–Glc]⁺, 162.0862 [M + H–Glc–HCT]⁺	Amygdalin	[13]

34^a	12.659	326	C₂₅H₂₄O₁₂	515.1162 (−5.4)	353.0786 [M–H–Ca]⁻	517.1348 (0.4)	539.1193	499.1248 [M + H–H₂O]⁺, 163.0387 [M + H–Ca–Quinic acid]⁺	3,4-Dicaffeoylquinic acid	[30]

35^a	13.082	276	C₁₅H₁₂O₄	255.0654 (−1.2)		257.0659 (−0.8)		147.0621 [M + H–RL]⁺, 137.0422 [M + H–VP]⁺, 119.0691 [M + H–RL–CO]⁺	Liquiritigenin	[34]

36^a	13.251	243, 372	C₂₆H₃₀O₁₃	549.1621 (2.4)		551.1725 (3.4)	573.1563	419.1360 [M + H–Api]⁺, 257.0814 [M + H–Api–Glc]⁺	Isoliquiritin apioside	[35]

37^a	13.300	242, 362	C₂₁H₂₂O₉	417.1198 (2.9)	255.0518 [M–H–Glc]⁻	419.1314 (−6.7)	441.1150	257.0823 [M + H–Glc]⁺, 229.1357 [M + H–Glc–CO]⁺	Isoliquiritin	[26]

38	13.479	280	C₂₇H₃₄O₁₁	579.2103 [M + HCOO]⁻			557.1987	552.2463 [M + NH₄]⁺, 355.1516 [M + H–Glc–H₂O]⁺	Arctiin	[36]

39^a	14.161	277	C₂₇H₃₄O₁₁	579.2106 M + HCOO]⁻	371.1826 [M–H–Glc]⁻, 356.1547 [M–H–Glc–H₂O]⁻	552.2444 M + NH₄]⁺	557.1991	373.1563 [M + H–Glc]⁺, 355.1544 [M + H–Glc–H₂O]⁺	Phillyrin	[37, 38]

40	14.678	372, 255	C₁₅H₁₀O₇	301.0355 (2.3)	151.0137 [M–H–C₈H₆O₃]⁻	303.0520 (4.9)			Quercetin	[39]

41	15.039	284	C₂₈H₃₄O₁₅	609.1522 (1.3)	301.0582 [M–H–Rut]⁻				Hesperidin	[13]

42	15.402	265, 366	C₁₅H₁₀O₆	285.0406 (2.5)		287.0721 (4.5)		153.0469 [M + H–HEP]⁺	Kaempferol	[13]

43	16.627	255	C₁₅H₁₀O₄	253.0507 (2.4)	225.0741 [M–H–CO]⁻, 210.0494 [M–H–CO–CH₃]⁻, 182.0542 [M–H–2CO–CH₃]⁻, 154.0553 [M–H–3CO–CH₃]⁻				Chrysophanol	[40]

44	17.035		C₁₅H₁₀O₄	253.0512 (4.3)	225.0752, 210.0474, 182.0485, 154.0531				Isomer of chrysophanol	[40]

45^a	17.347	254, 287, 426	C₂₁H₂₀O₁₀	431.0989 (2.6)	269.0673 [M–H–Glc]⁻, 241.0719 [M–H–Glc–CO]⁻, 225.0753 [M–H–Glc–CO₂]⁻, 210.0578 [M–H–Glc–CO₂–CH₃]⁻, 197.0771 [M–H–Glc–CO–CO₂]⁻, 182.0486 [M–H–Glc–CO₂–CH₃–CO]⁻		455.1010	271.0715 [M + H–Glc]⁺	Emodin-8-O-glucoside	[41]

46	17.396	240, 330, 395	C₁₅H₁₂O₄	255.0639 (−7.1)		257.0812 (−0.8)			Isoliquiritigenin	[26]

47^a	18.385	250, 304	C₁₆H₁₂O₄	267.0653 (−1.5)		269.0827 (4.8)	291.0751		Formononetin	[42]

48	18.804			895.4082 (2.8)	719.3849 [M–H–GlcA]⁻ 351.0630 [2GlcA–H]⁻	897.4107 (1.2)	919.3925		22β-Acetoxy licorice saponin B2/uralsaponin F	[43]

49	19.194	271, 421		445.1168 (−5.6)	283.0632 [M–H–Glc]⁻		469.1128	285.0775 [M + H–Glc]⁺	Physcion-8-O-β-D-glucopyranoside	[41]

50	19.603	248	C₄₂H₆₀O₁₆	819.3843 (0.6)	351.0699 [2GlcA–H]⁻	821.3994 (−0.1)	843.3996	645.3612 [M + H–GlcA]⁺, 469.3302 [M + H–2GlcA]⁺, 451.3211 [M + H–2GlcA–H₂O]⁺	Licorice saponin E2	[35]

51	19.704		C₁₆H₂₄O₇	327.2180 (2.8)	164.9664 [M–H–Glc]⁻		351.2133		Rhododendrol-4^′-O-β-D-glucopyranoside	[44]

52	20.000	254	C₄₄H₆₄O₁₈	879.4062 (1.3)	351.0806 [M–H–22AG]⁻	881.4170 (−0.1)		705.3897 [M + H–GlcA]⁺, 529.3588 [M + H–2GlcA]⁺, 511.3395 [M + H–2GlcA–H₂O]⁺	22-Acetoxyglycyrrhizin	[42]

53	20.573	352	C₁₇H₁₄O₇	329.2341 (3.9)			353.2280	301.1443 [M + H–CH₂O]⁺, 287.2002 [M + H–CO₂]⁺, 259.1248 [M + H–CO₂–CO]⁺	Tricin	[45]

54^a	21.199	260	C₁₅H₈O₆	283.0262 (6.7)	239.0359 [M–H–CO₂]⁻	285.0515 (−13.0)			Rhein	[46]

55	21.540	253		837.3977 (1.2)	819.4404 [M–H–H₂O]⁻, 661.4100 [M–H–GlcA]⁻, 351.0815 [2GlcA–H]⁻, 289.0840 [2GlcA–H–H₂O–CO₂]⁻	839.4061 (−0.5)	861.3890	663.3868 [M + H–GlcA]⁺, 487.3395 [M + H–2GlcA]⁺, 469.3286 [M + H–2GlcA–H₂O]⁺	Licorice saponin G2	[42]

56	21.626	236, 327, 370, 384	C₂₁H₂₀O₆	367.1208 (7.1)	309.1566 [M–H–CO–CH₂O]⁻, 265.0635 [M–H–CO–CH₂O–CO₂]⁻, 221.0221 [M–H–CO–CH₂O–2CO₂]⁻	369.1369 (−7.6)	391.1176		Glycycoumarin	[47]

57	22.087	249	C₄₂H₆₂O₁₆	821.3977 (1.7)	803.4501 [M–H–H₂O]⁻, 759.4542 [M–H–H₂O–CO₂]⁻, 645.4102 [M–H–GlcA]⁻, 627.4000 [M–H–GlcA–H₂O]⁻, 469.3705 [M–H–2GlcA]⁻, 351.0809 [2GlcA–H]⁻, 289.0758 [2GlcA–H–H₂O–CO₂]⁻	823.4128 (1.5)	845.4557	647.3797 [M + H–GlcA]⁺, 471.3480 [M + H–2GlcA]⁺, 453.3365 [M + H–2GlcA–H₂O]⁺	Glycyrrhizic acid	[48]

58	22.188	252	C₄₂H₆₂O₁₆	821.3986 (−1.1)	351.0768 [M–H–GA]⁻	823.4134 (−2.1)	845.4127	647.3823 [M + H–GlcA]⁺, 471.3365 [M + H–2GlcA]⁺, 453.3324 [M + H–2GlcA–H₂O]⁺	Licorice saponin H2	[26]

59	22.389	248	C₄₂H₆₄O₁₅	807.4197 (−0.6)	745.4601 [M–H–Glc]⁻, 631.4210 [M–H–GlcA]⁻, 351.0699 [M–H–GA]⁻	809.4410 (−0.9)	831.4138		Licorice saponin B2	[49]

60	22.623	252	C₄₂H₆₂O₁₆	821.3997 (0.2)	351.0837 [M–H–GA]⁻	823.4105 (−1.3)	845.3900	647.3838 [M + H–GlcA]⁺, 471.3288 [M + H–2GlcA]⁺, 453.3279 [M + H–2GlcA–H₂O]⁺	Licorice saponin K2	[50]

61^a	23.230	288, 439	C₁₅H₁₀O₅	269.0462 (4.5)	241.0669 [M–H–CO]⁻, 225.0723 [M–H–CO₂]⁻, 210.0427 [M–H–CO₂–CH₃]⁻, 197.0695 [M–H–CO–CO₂]⁻, 182.0477 [M–H–CO₂–CH₃–CO]⁻, 154.0552 [M–H–CO₂–CH₃–2CO]⁻				Emodin	[40]

Compared with reference compounds.
^b22AG: 22-acetoxyglycyrrhizin; Api: apiose; Ca: caffeoyl; GA: glycyrrhetinic acid; Glc: glucose; GlcA: glucuronic acid; HCT: 4-(hydroxymethyl)cyclobutane-1,2,3-triol; HEP: 4-(hydroxyethynyl) phenol; Rha: rhamnose; RL: resorcinol; Rut: rutinose; VP: 4-vinylphenol.