Table 2.

Chromatographic and mass spectral data of the 42 compounds analyzed by UPLC-QTOF-MS/MS.

Peak no.	Identification	tR (min)	Molecular formula	[M–H]−		Assigned adduct and fragment ions	Occurrence	Classification
				Measured mass (Da)	Mass accuracy (ppm)
1	p-Hydroxybenzyl malonic acid [28]	4.92	C10H10O5	209.0451	1.97	419.0975 [2M–H]− 165.0562 [M–H–CO2]− 121.0654 [M–H–2CO2]−	GR	Organic acid
2	Neomangiferin [5]	6.11	C25H28O16	583.1299	1.32	1167.2665 [2M–H]− 421.0770 [M–H–Glc]−	AR	Xanthone
3	Mangiferin [5]	7.94	C19H18O11	421.0769	1.85	843.1591 [2M–H]−	AR	Xanthone
4	Isomangiferin [5]	8.38	C19H18O11	421.0762	3.35	843.1595 [2M–H]−	AR	Xanthone
5	Vicenin-2 [29]	8.91	C27H30O15	593.1506	4.12	639.1584 [M–H+HCOOH]− 337.0384 [M–H–Glc–C6H6O]−	GR	Flavone
6	Iriflophenone [5]	10.27	C13H10O5	245.0450	2.06	491.0976 [2M–H]−	AR	Benzophenone
7	Neoliquiritin [29]	11.19	C21H22O9	417.1178	3.10	463.1210 [M–H+HCOOH]− 835.2416 [2M–H]−	GR	Flavanone
8	Liquiritin [6,29]	11.42	C21H22O9	417.1188	2.03	835.2425 [2M–H]− 255.0659 [M–H–Glc]− 135.0085 [M–H–Glc–C8H8O]−	GR	Flavanone
9	Liquiritin apioside [6,29]	11.67	C26H30O13	549.1598	2.92	1099.3267 [2M–H]− 417.1181 [M–H–Api]− 255.0661 [M–H–Api–Glc]− 135.0086 [M–H–Api–Glc–C8H8O]−	GR	Flavanone
10	Baohuoside I [30]	12.80	C27H30O10	—	0.29a	559.1821 [M–H+HCOOH]−	AR	Flavonol
11	15OH-timosaponin N (or isomer)/ 15OH-macrostemonoside J [31,32]	13.08	C45H76O21	951.4780	2.73	997.4830 [M–H+HCOOH]− 789.4241 [M–H–Glc]− 627.3734 [M–H–2Glc]− 465.3139 [M–H–2Glc–Gal]−	AR	Furostanol saponins
12	Timosaponin N + Rha or isomer [33]	13.41	C51H86O24	1081.5403	3.10	1127.5462 [M–H+HCOOH]− 935.4829 [M–H–Rha]− 773.4316 [M–H–Rha–Glc]− 611.3790 [M–H–Rha–2Glc]−	AR	Furostanol saponin
13	Timosaponin E1/timosaponin N (or isomer)/ hydroxyl-timosaponin BII/macrostemonoside J [31,32]	13.59	C45H76O20	935.4827	3.24	981.4878 [M–H+HCOOH]− 773.4315 [M–H–Glc]− 611.3791 [M–H–2Glc]− 449.3270 [M–H–2Glc–Gal]−	AR	Furostanol saponin
14	Karatavioside C [34]	13.81	C56H92O29	1227.5586	4.79	1095.5214 [M–H–Xyl]− 933.4705 [M–H–Xyl–Glc]− 771.4175 [M–H–Xyl–2Glc]−	AR	Furostanol saponin
15	Isoliquiritin apioside (licuraside) [29]	13.83	C26H30O13	549.1603	1.95	417.1164 [M–H–Api]− 255.0660 [M–H–Api–Glc]− 135.0084 [M–H–Api–Glc–C8H8O]−	GR	Chalcone
16	Isoliquiritin [29]	14.01	C21H22O9	417.1180	2.75	835.2420 [2M–H]− 255.0663 [M–H–Glc]− 135.0086 [M–H–Glc–C8H8O]−	GR	Chalcone
17	Timosaponin E1/27OH-timosaponin BII + Rha [33]	14.06	C45H76O20	935.4831	2.82	981.4881 [M–H+HCOOH]− 773.4316 [M–H–Glc]− 611.3791 [M–H–2Glc]−	AR	Furostanol saponin
18	Ononin [35,36]	14.22	C22H22O9	429.1187	0.88	475.1233 [M–H+HCOOH]− 267.0657 [M–H–Glc]−	GR	Isoflavone
19	2,4′,6-Trihydroxy-4-methoxybenzophenone (or isomer) [37]	14.32	C14H12O5	259.0607	1.76	519.1254 [2M–H]− 243.0290 [M–H–CH4]−	AR	Benzophenone
20	Licorice glycoside B [29]	14.42	C35H36O15	695.1963	2.68	1391.3971 [2M–H]− 417.1190 [M–H–C14H14O6]− 255.0661 [M–H–C14H14O6–Glc]−	GR	Flavonoid glycoside
21	Timosaponin BII [31]	14.66	C45H76O19	919.4903	1.70	965.4942 [M–H+HCOOH]− 757.4371 [M–H–Glc]− 595.3841 [M–H–2Glc]− 433.3301 [M–H–2Glc–Gal]−	AR	Furostanol saponin
22	Asparagoside G/petunioside N/terrestrosin H [33,38,39]	14.75	C51H86O24	1081.5411	2.32	1127.5484 [M–H+HCOOH]− 919.4909 [M–H–Glc]− 757.4372 [M–H–2Glc]− 595.3778 [M–H–2Glc–Gal]−	AR	Furostanol saponin
23	Timosaponin H1 [33]	14.83	C56H92O28	1211.5673	2.39	1257.5679 [M–H+HCOOH]− 1079.5268 [M–H–Xyl]−	AR	Furostanol saponins
24	Formononetin [35,36]	15.29	C16H12O4	267.0657	2.33	252.0425 [M–H–CH3]−	GR	Isoflavone
25	22-Acetoxyl licorice-saponin G2 [40]	15.80	C44H64O19	895.3943	2.87	837.3899 [M–H–C2H2O2]−	GR	Triterpene saponin
26	Licochalcone B [6]	15.90	C16H14O5	285.0760	3.07	571.164 [2M–H]−	GR	Chalcone
27	Licorice-saponin A3 (or isomer) [40]	16.18	C48H72O21	983.4465	2.89	821.3958 [M–H–Glc]−	GR	Triterpene saponin
28	22-Acetoxyl-glycyrrhizin [29]	16.49	C44H64O18	879.3994	2.93	351.0568 [2GlcA–2H2O–H]− 193.0351 [GlcA–H]−	GR	Triterpene saponin
29	Timosaponin C/timosaponon B/ macrostemonoside F/anemarsaponin C [33]	16.52	C45H74O18	901.4771	3.45	947.4827 [M–H+HCOOH]− 739.4267 [M–H–Glc]− 577.3723 [M–H–2Glc]−	AR	Furostanol saponin
30	Timosaponin C/timosaponon B/ macrostemonoside F/anemarsaponin C [33]	16.59	C45H74O18	901.4775	3.06	947.4824 [M–H+HCOOH]− 739.4269 [M–H–Glc]− 577.3743 [M–H–2Glc]−	AR	Furostanol saponin
31	Licorice-saponin G2 or isomer [40]	16.75	C42H62O17	837.3889	3.02	1675.7769 [2M–H]− 351.0572 [2GlcA–2H2O–H]− 193.0350 [GlcA–H]−	GR	Triterpene saponin
32	Liquiritigenin [36,40]	16.98	C15H12O4	255.0656	2.72	301.0706 [M–H+HCOOH]− 135.0085 [M–H–C8H8O]− 119.0500 [M–H–C7H4O3]−	GR	Flavanone
33	Licorice-saponin G2 or isomer [40]	17.49	C42H62O17	837.3885	3.46	1675.7826 [2M–H]− 351.0567 [2GlcA–2H2O−H]− 193.0349 [GlcA–H]−	GR	Triterpene saponin
34	Glycyrrhizic acid [36,40]	18.13	C42H62O16	821.3968	2.52	1643.7956 [2M–H]− 645.3623 [M–H–GlcA]− 469.3304 [M–H–2GlcA]− 351.0566 [2GlcA–2H2O–H]− 193.0353 [GlcA–H]−	GR	Triterpene saponin
35	Anemarrhena saponin I/II [31]	18.26	C39H66O14	757.4354	3.35	803.4418 [M–H+HCOOH]− 1515.8785 [2M–H]− 595.3840 [M–H–Glc]−	AR	Furostanol saponin
36	Licorice-saponin B2/dehydroxyl-uralsaponin C [40]	18.74	C42H64O15	807.4150	2.80	631.3819 [M–H–C6H8O6]− 351.0566 [2GlcA–2H2O–H]− 193.0354 [GlcA–H]−	GR	Triterpene saponin
37	Licorice-saponin H2/K2 [40]	18.87	C42H62O16	821.3939	3.16	351.0568 [2GlcA–2H2O−H]− 193.0351 [GlcA–H]−	GR	Triterpene saponin
38	Nyasol [5]	19.25	C17H16O2	251.1071	2.61	297.1122 [M–H+HCOOH]−	AR	Lignan
39	Timosaponin AII/anemarrhenasaponin III/ anemarrhenasaponin A2/timosaponin A2/ timosaponin G	19.99	C39H64O14	755.4200	3.05	801.4256 [M–H+HCOOH]− 593.3693 [M–H–Glc]−	AR	Spirostanol saponin
40	Gancaonin C [6]	20.25	C20H18O6	353.1021	2.73	323.0923 [M–H–CH2O]−	GR	Isoflavone
41	Licoisoflavone B/semilicoisoflavone B [6]	21.35	C20H16O6	351.0869	1.49	703.1801 [2M–H]−	GR	Flavone
42	Timosaponin AIII [31]	21.45	C39H64O13	739.4245	4.00	785.4298 [M–H+HCOOH]− 577.3737 [M–H–Glc]−	AR	Spirostanol saponin

UPLC-QTOF-MS = ultra-performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry.

^aCalculated by [M–H+HCOOH]⁻.