Isolation and Identification of Chemical Constituents from Zhideke Granules by Ultra-Performance Liquid Chromatography Coupled with Mass Spectrometry

Table 1

Characterization of chemical constituents from the ethyl acetate extract of Zhideke granules by UPLC coupled with hybrid quadrupole-orbitrap MS.

Type of compounds	No.	tR (min)	Adduct ions	Theoretical (m/z)	Measured (m/z)	Mass error (ppm)	Molecular formula	MS/MS (m/z)	Identification compounds	Source
Flavonoids and glycosides	1	10.21	M-H	463.0882	463.087	−2.5133	C21H20O12	255.0291 [M^-H-Glc-O-CHO]^− 271.0241 [M-Glc-CHO]^−	Isoquercitrin	Bupleurum chinense, Eriobotrya japonica (Thunb.), Sauropus spatulifolius Beille. [37]
	2	10.82	M + HCO2	461.1089	461.1078	−2.5426	C22H22O11	298.0472 [M-H-C6H10O5]^− 284.0317 [M-H-C6H10O5-CH3]^−	Tectoridin	Belamcanda chinensis (L.) Redouté [32]
	3	11.34	M + H	417.118	417.1159	−4.9715	C21H20O9	267.0640 [M + H-2H2O-CH2O-C4H4O2]^+ 297.0743 [M + H-C4H8O4]^+ 307.0941 [M + H-2H2O-C2H4O]^+ 351.0847 [M + H-2H2O-CH2O]^+ 399.1055 [M + H-H2O]^+	Puerarin	Bupleurum chinense [18]
	4	11.65	M-H	607.1668	607.1653	−2.5640	C28H32O15	299.0550 [M-H-C12H21O9]^−	Diosmin	Mentha haplocalyx Briq. [38]
	5	11.75	M-H	609.1825	609.1812	−2.1958	C28H34O15	301.0707 [M-H-rutinoses]^−	Hesperidin	Eriobotrya japonica (Thunb.), Mentha haplocalyx Briq., Nepeta cataria L., Nervilia fordii (Hance) Schltr. [15]
	6	11.82	M-H	461.0726	461.0714	−2.6024	C21H18O12	285.0395 [M-H-C6H8O6]^−	Luteolin 7-glucuronide	Mentha haplocalyx Briq. [39]
	7	11.95	M + H	523.1446	523.1423	−4.4864	C24H26O13	361.0899 [M + H-C6H10O5	Iridin	Belamcanda chinensis (L.) Redouté [33, 40]
	8^a	12.52	M + H	447.0922	447.0901	−4.6335	C21H18O11	169.0124 [M + H-C6H8O6-C8H6]^+ 225.0541 [M + H-C6H8O6-H2O-CO]^+ 271.0588 [M + H-C6H8O6]^+	Baicalin	Scutellaria baicalensis Georgi.， Bupleurum chinense [15]
	9	12.58	M-H	285.0405	285.0395	−3.511	C15H10O6	165.0185 [M-H-C8H8O]^+ 239.0343 [M-H-H2O-CO]^+	Scutellarein	Scutellaria baicalensis Georgi. [41]
	10	12.83	M-H	287.0561	287.0552	−3.0419	C15H12O6	267.0290 [M-H-H2O]^+ 135.0446 [M-H-C7H4O4]^−	Eriodictyol	Unknown [24]
	11	13.91	M-H	301.0354	301.0343	−3.6832	C15H10O7	107.0135 [M-H-C7H6O2-CO-CO2]^− 151.0031 [M-H-C7H6O2-CO]^− 178.9978 [M-H-C7H6O2]^− 273.0396 [M-H-CO]^−	Quercetin	Nepeta cataria L., Bupleurum chinense, Eriobotrya japonica (Thunb.), Sauropus spatulifolius Beille. [16]
	12	13.94	M-H	315.051	315.05	−3.1143	C16H12O7	300.0175 [M-H-CH3]^−	Eupafolin	Scutellaria baicalensis Georgi. [42]
	13	14.10	M + H	593.1865	593.1837	−4.7628	C28H32O14	242.0559M + H-C12H20O9-CH3-CO]^+ 285.0742 [M + H-C12H20O9]^+ 447.1261 [M + H-C6H10O4]^+	Linarin	Mentha haplocalyx Briq. [43]
	14	14.36	M + H	595.2021	595.1993	−4.7887	C28H34O14	287.0900 [M + H-Rha- Glc]^+	Didymin	Mentha haplocalyx Briq. [15]
	15	16.39	M-H	359.0772	359.0761	−3.1446	C18H16O8	301.0347 [M-H-2CH3- CO]^−	Irigenin	Belamcanda chinensis (L.) Redouté [33]
	16	16.78	M-H	269.0456	269.0446	−3.4689	C15H10O5	223.0594 [M-H-H2O-CO]^−	Baicalein	Scutellaria baicalensis Georgi. [41]
	17	19.42	M-H	283.0612	283.0602	−3.6011	C16H12O5	240.0426 [M + H-CH3- CO]^−	Wogonin	Scutellaria baicalensis Georgi. [44, 45]
	18	19.54	M + H	403.1387	403.1368	−4.8624	C21H22O8	327.0849 [M + H-2CH3- H2O-CO]^+ 373.0900 [M + H-2CH3]^+ 119.0497 [M-H-C3O2- C4H2O]^−	Nobiletin	Unknown [17]
	19	19.74	M-H	253.0506	253.0498	−3.1409	C15H10O4	143.0495 [M-H-C3O2- C2H2O]^− 181.0652 [M-H-CO2- CO]^− 209.0599 [M-H-CO2]^− 107.0133 [M-H-C8H8- CO2]^−	Chrysin	Mentha haplocalyx Briq., Scutellaria baicalensis Georgi. [46]
	20	20.1 4	M-H	255.0663	255.0655	−2.9149	C15H12O4	145.0652 [M-H-C3O2- C2H2O]^− 171.0448 [M-H- 2C2H2O]^− 211.0753 [M-H-CO2]^−	Pinocembrin	Unknown [46]
Organic acids	21	20.54	M-H	299.0561	299.0551	−3.5321	C16H12O6	227.0344 [M-H-CO2^-CO]^− 255.0292 [M-H-CO2]^−	Tectorigenin	Belamcanda chinensis (L.) Redouté [33]
	22	1.50	M-H	169.0142	169.0136	−3.7817	C7H6O5	69.0343 [M-H-C3O4]^− 97.0291 [M-H-C2O3]^− 125.0239 [M-H-CO]^−	Gallic acid	Eriobotrya japonica (Thunb.) [16, 47]
	23	1.86	M-H	125.0244	125.0239	−3.892	C6H6O3	81.0187 [M-H-H2O-CO]^−	Pyrogallol	Unknown [48]
	24	2.19	M-H	197.0456	197.0448	−3.8072	C9H10O5	134.0369 [M-H-H2O-CO2]^− 151.0401 [M-H-H2O-CO]^− 179.0342 [M-H-H2O]-	Danshensu	Mentha haplocalyx Briq. [19]
	25	8.62	M^−H	163.0401	163.0395	−3.4654	C9H8O3	119.0497 [M-H-CO2]^−	p-Hydroxy-cinnamic acid	Unknown [37]
	26	9.85	M-H	537.1038	537.1024	−2.7817	C27H22O12	295.0602 [M-H-CO2-C9H10O5]^− 313.0711 [M-H-C9H8O4]^−	Lithospermic acid	Mentha haplocalyx Briq. [20]
	27	11.68	M-H	187.0976	187.0968	−4.1596	C9H16O4	69.0342 [M-H-CO2-H2O-C4H8]^− 83.0501 [M-H-CO2-H2O-C3H6]^− 97.0654 [M-H-CO2-H2O-C2H4]^− 125.0967 [M-H-CO2-H2O]^− 143.1070 [M-H-CO2]^−	Azelaic acid	Cynanchum glaucescens (Decne.) Hand-Mazz [21]
Volatile components	28	13.37	M-H	493.114	493.1129	−2.1789	C26H22O10	185.0238295.0601 [M-H-C15O7H16]^− 295.0601 [M-H-C9O5H1O]^− 313.0709 [M-H-C9O4H8]^−	Salvianolic acid A	Mentha haplocalyx Briq. [22]
	29	13.47	M-H	263.1289	263.128	−3.2636	C15H20O4	204.1147 [M-H-CO2-CH3]	Abscisic acid	Unknown [16]
	30	14.16	M-H	491.0984	491.0971	−2.6341	C26H20O10	135.0446 [M-H-C18H12O8]^− 179.0342 [M-H-C17H12O6]^− 197.0971 [M-H-C17H10O5]^− 265.0501 [M-H-C9H8O4-COOH]^− 293.0448 [M-H-C9H10O5]^− 311.0554 [M-H-C9H8O4]^−	Salvianolic acid C	Mentha haplocalyx Briq. [22]
	31	2.17	M + H	127.039	127.0385	−3.5959	C6H6O3	53.0392 [M + H-H2O-2CO]^+ 81.0337 [M + H-H2O-CO]^+ 97.0285 [M + H-CH2OH]^+	5-Hydroxymethylfurfural	Belamcanda chinensis (L.) Redouté, Cynanchum glaucescens (Decne.) Hand-Mazz. [49]
	32	10.98	M + H	153.1274	153.1267	−4.2481	C10H16O	135.1165 [M + H-H2O]^+	Camphor	Eriobotrya japonica (Thunb.), Bupleurum chinense, Scutellaria baicalensis Georgi., Mentha haplocalyx Briq., Cynanchum glaucescens (Decne.) Hand-Mazz. [24]
Nitrogen-containing compounds	33	12.95	M + H	191.1067	191.1058	−4.3172	C12H14O2	145.1006 [M + H-H2O-CO]^+ 163.1110 [M + H-C2H4]^+ 173.0953 [M + H-H2O]^+	Ligustilide	Bupleurum chinense [25]
	34	25.35	M + HCO2	315.2541	315.2528	−3.9393	C17H34O2	127.1122 [M-H-C8H15O2]^− 141.1279 [M-H-C7H13O2]^− 171.1020 [M-H-C7H15]^−	Methyl palmitate	Scutellaria baicalensis Georgi., Bupleurum chinense, Belamcanda chinensis (L.) Redouté [23]
	35	0.32	M + H	195.0876	195.0867	-4.7109	C8H10N4O2	56.0500 [M + H-C6H6N2O2]^+ 69.0451 [M + H-C5H10N3O]^+ 110.0711 [M + H-C4H10N2]^+ 138.0656 [M + H-C2H4N2]^+	Caffeine	Unknown [36]
	36	0.90	M + H	136.0618	136.0612	−4.5036	C5H5N5	92.0244 [M-CH3N2] 109.0507 [M-CN]^+	Adenine	Unknown [27]
	37	1.26	M + H	123.0553	123.0549	−3.2842	C6H6N2O	80.0497 [M + H-CO-NH2]^+ 95.0605 [M + H-CO]^+ 105.0449 [M + H-NH3]^+	Nicotinamide	Sauropus spatulifolius Beille. [28]
Other compounds	38	0.85	M-H	181.0718	181.0711	−3.7806	C6H14O6	59.0136 [M-H-H2O-C4H8O3]^− 71.0135 [M-H-2H2O-aC3H6O2]^− 89.0241 [M-H-H2O-C3H6O2]^− 101.0240 [M-H-H2O-C2H6O2]^− 163.0604 [M-H-H2O]^−	Mannitol	Sauropus spatulifolius Beille. [29]
	39	0.85	M-H	341.1089	341.1078	−3.4371	C12H22O11	71.0135 [M-H-C9H16O8-H2O]^− 89.0241 [M-H-C9H16O8]^−	Sucrose	Cynanchum glaucescens (Decne.) Hand-Mazz. [25]
	40	4.56	M-H	137.0244	137.0238	−4.2749	C7H6O3	93.0341 [M-H-CO2]^−	Protocatechualdehyde	Mentha haplocalyx Briq., Nepeta cataria L. [30]
	41	6.30	M-H	177.0193	177.0186	−4.0350	C9H6O4	133.0290 [M-H-CO2]^− 149.0237 [M-H-CO]^−	Esculetin	Bupleurum chinense, Nervilia fordii (Hance) Schltr. [31]
	42	7.50	M-H	421.0776	421.0766	−2.5207	C19H18O11	258.0161 [M-H-C6H10O5]^−	Isomangiferin	Belamcanda chinensis (L.) Redouté [33]
	43	10.61	M-H	243.0663	243.0655	−3.3727	C14H12O4	173.0601 [M-H-C2H2O-CO]^− 201.0549 [M-H-C2H2O]^− 225.0549 [M-H-H2O]^−	Piceatannol	Unknown [34]
	44 a	11.07	M-H	623.1981	623.1963	−2.9701	C29H36O15	161.0238 [M-H-C20H28O11-H2O]^− 179.0341 [M-H-C20H28O11]^− 461.1656 [M-H-C9H6O3]^−	Forsythoside A	Cynanchum glaucescens (Decne.) Hand-Mazz. [35]
	45	12.22	M-H	191.035	191.0343	−3.3107	C10H8O4	163.0393 [M-H-CO]^−	5,7-Dihydroxy-4-methylcoumarin	Unknown [32]
	46	12.61	M + HCO2	441.1766	441.1754	−2.8004	C20H28O8	89.0241 [M-C13H22O8]^− 159.0811 [M-H-C6H10O6-CH2O-C3H6O]^− 185.0963 [M-H-C6H10O6-CH2O]^−	Lobetyolin	Platycodon grandiflorus (Jacq.) A. DC. [36]
	47	14.86	M + H	209.0808	209.0799	−4.5197	C11H12O4	134.0593 [M-H-C2H4O-CH3]^+ 149.0492 [M-H-C2H4O2]^+ 177.0540 [M-H-CH4O]^+	Ferulic acid methyl ester	Unknown [12]

Note.^aIdentification confirmed with reference compound.