Screening of Biomarkers and Quality Control of Shaoyao Gancao Decoction Using UPLC-MS/MS Combined with Network Pharmacology and Molecular Docking Technology

Table 3

Negative mode for 53 compounds by UPLC-Q-TOF-MS/MS.

No	Rt (min)	Formula	Mass (Da)	Ppm	MS/MS fragments	Identification	Source
71^d	3.51	C9H8O4	180.0423	−3.9	134.9873[M-H-CH2O2]^–	Caffeic acid	GC
72^d	3.88	C9H10O5	198.0528	−2.6	152.5018[M-H-C2H6O]^–	Ethyl gallate	BS
73^d	4.09	C8H8O5	184.0372	−3.4	123.0118[M-H-C2H6O2]^–	Methyl gallate	BS
74^c	5.45	C23H28O12	496.158	−1	495.1509[M-H]^–; 465.1404[M-H-CH2O]^–; 333.1006[M-H-C6H10O5]^–; 195.0680[M-H-C13H16O8]^–; 177.0547[M-H-C17H18O6]^–; 165.0554[M-H-C14H18O9]^–; 137.0242[M-H-C16H22O9]^–	Oxy paeoniflorin	BS
75^a	7.51	C21H20O11	448.1005	−0.2	447.0961[M-H]^–; 285.0405[M-H-C6H10O5]^–; 265.8768[M-H-C6H14O6]^–; 130.9660[M-H-C16H12O7]^–; 109.0305[M-H-C15H14O9]^–	Kaempferol-3-O-β-D-glucoside	BS
76^a	7.51	C21H20O11	448.1005	−0.2	447.0961[M-H]^–; 285.0405[M-H-C6H10O5]^–; 265.8768[M-H-C6H14O6]^–; 130.9660[M-H-C16H12O7]^–	Kaempferol-7-O-β-D-glucoside	BS
77^c	8.32	C23H28O11	480.1631	−0.6	327.1093[M-H-C8H8O3]^–; 167.0562[M-H-C14H18O8]^–; 121.0299[M-H-C16H22O9]^–	Albiflorin	BS
78^d	8.32	C16H18O9	309.0969	0.2	309.0969[M-COOH]^–	Chlorogenic acid	GC
79^d	8.32	C16H18O9	309.0969	0.2	309.0969[M-COOH]^–	Neochlorogenic acid	BS
80^a	8.8	C27H30O14	578.1635	0.4	577.1589[M-H]^–; 487.1256[M-H-C3H6O3]^–; 473.1098[M-H-C4H8O3]^–; 457.1160[M-H-C4H8O4]^–; 413.0884[M-H-C6H12O5]^–; 395.0789[M-H-C6H14O6]^–	Isoviolanthin	BS
81^c	11.51	C16H24O8	344.357	−2.4	208.8396[M-H-C5H10O4]^–; 165.0559[M-H-C6H10O6]^–; 101.0234[M-H-C12H18O5]^–	Mudanpioside F	GC
82^a	12.21	C27H30O16	609.1440	−3.4	609.1440[M-H]^–	Rutin	BS
83^a	14.11	C21H20O12	464.0955	−1.3	463.0877[M-H]^–; 417.0979[M-H-CH2O2]^–; 265.1488[M-H-C6H14O7]^–; 174.9527[M-H-C12H16O8]^–; 130.9658[M-H-C16H12O8]^–	Quercetin-3-O-β-D-glucoside	GC
84^a	14.37	C16H12O5	284.0685	2.7	283.0629[M-H]^–; 267.0298[M-H-CH4]^–; 239.0352[M-H-C2H4O]^–; 211.0397[M-H-C3H4O2]^–; 183.0457[M-H-C5H8O2]^–; 135.0083[M-H-C9H8O2]^–	Calycosin	GC
85^c	14.43	C30H32O14	616.1792	−1.7	615.1719[M-H]^–; 597.1627[M-H-H2O]^–; 493.1346[M-H-C7H6O2]^–; 475.1250[M-H-C7H8O3]^–; 376.8781[M-H-C11H10O6]^–; 313.0538[M-H-C6H14O6]^–; 174.9550[M-H-C6H7O6]^–; 151.0032[M-H-C8H7O3]^–	Mudanpioside H	GC
86^b	14.82	C36H38O16	726.2159	1	725.2122[M-H]^–; 549,1637[M-H-C10H8O3]^–; 531.1518[M-H-C10H10O4]^–; 417.1194[M-H-C15H16O7]^–; 399.1085[M-H-C15H18O8]^–; 255.0668[M-H-C21H26O12]^–; 193.0504[M-H-C16H28O12]^–; 175.0402[M-H-C26H30O13]^–; 135.0091[M-H-C29H34O13]^–	Licorice glycoside C2	GC
	15.22	C16H10O6	298.0477	1.7	297.0421[M-H]^–; 197.0259[M-H-C5H8O2]^–	Isotrifoliol	GC
	15.22	C16H12O6	300.0634	−0.6	299.0565[M-H]^–; 255.0305[M-H-CO2]^–; 199.0415[M-H-C5H8O2]^–	7,2′,4′-trihydroxy-3-(5-meth oxy phenyl) chromen-2-one	GC
89^a	15.83	C27H30O13	562.1686	0.9	561.1614[M-H]^–; 267.0668[M-H-C11H18O9]^–	Glycyroside	GC
90^a	16.48	C20H18O7	370.1053	0.5	369.1000[M-H]^–; 243.0681[M-H-C6H6O3]^–; 219.0674[M-H-C7H2O4]^–; 191.0724[M-H-C11H14O2]^–; 175.0753[M-H-C9H6O5]^–; 151.0048[M-H-C13H14O3]^–; 125.0266[M-H-C14H12O4]^–; 109.0289[M-H-C13H8O6]^–; 107.0154[M-H-C14H14O4]^–	Uralenol	GC
91^a	17.29	C16H12O4	268.0735	0.9	267.0674[M-H]^–; 251.0359[M-H-CH4]^–; 223.0404[M-H-C2H4O]^–; 135.0083[M-H-C9H8O]^–	Formononetin	GC
92^b	17.92	C48H72O21	985.073	1.5	983.4542[M-H]^–; 821.3998[M-H-C6H10O5]^–	Licoricesaponin A3	GC
93^a	18.71	C15H12O4	256.0735	2.2	255.0663[M-H]^–; 119.0508[M-H-C7H4O3]^–; 135.0093[M-H-C8H8O]^–	Pinocembrin	GC
94^a	19.93	C16H14O4	270.0892	1.2	269.0817[M-H]^–; 253.0532[M-H-CH4]^–; 237.0538[M-H-CH4O]^–; 225.0596[M-H-C2H4O]^–; 175.0408[M-H-C6H6O]^–; 161.0248[M-H-C7H8O]^–; 149.0240[M-H-C7H4O2]^–; 133.0289[M-H-C8H8O2]^–; 117.0352[M-H-C8H8O3]^–; 107.0128[M-H-C10H10O2]^–; 105.0342[M-H-C9H8O3]^–	Retrochalcone	GC
95^b	20.17	C42H60O16	820.3881	0.5	819.3884[M-H]^–; 351.0593[M-H-C36H44O4]^–	Licoricesaponin E2	GC
96^b	20.3	C50H76O21	1012.2879	0.3	1011.4853[M-H]^–; 497.1146[M-H-C38H50O5]^–; 146.9654[M-H-C50H64O17]^–	Licoricesaponin D3	GC
97^b	21.28	C42H62O16	822.4038	2.3	821.4106[M-H]^–; 351.0577[M-H-C30H46O4]^–; 193.0363[M-H-C6H9O7]^–	Glycyrrhizic acid	GC
98^b	21.28	C42H62O16	822.5038	2.3	821.4106[M-H]^–; 351.0577[M-H-C30H46O4]^–; 193.0363[M-H-C6H9O7]^–	Licoricesaponin H2	BS
99^b	21.28	C42H62O16	822.4038	2.3	821.4106[M-H]^–; 351.0577[M-H-C30H46O4]^–; 193.0363[M-H-C6H9O7]^–	Licoricesaponin K2	GC
100^a	21.6	C21H20O6	368.1259	−0.2	367.1196[M-H]^–; 337.0718[M-H-CH2O]^–; 309.0416[M-H-C3H6O]^–; 297.0409[M-H-C5H10]^–; 281.0456[M-H-C5H10O]^–; 265.0507[M-H-C6H14O]^–; 203.0712[M-H-C9H8O3]^–	Licoarylcoumarin	GC
	22.79	C12H16O2	192.115	−3.5	190.8612[M-H]^–; 162.8911[M-H-C2H4]^–; 102.9487[M-H-C4H8O2]^–	Cuminyl acetate	GC
102^a	23.02	C20H20O4	324.1362	2.9	323.1280[M-H]^–; 213.0929[M-H-C6H6O2]^–; 187.0765[M-H-C8H8O2]^–; 185.0609[M-H-C8H10O2]^–; 175.0754[M-H-C9H8O2]^–; 147.0446[M-H-C11H12O2]^–; 135.0455[M-H-C13H16O]^–; 107.0502[M-H-C14H16O2]^–	Isobavachalcone	GC
103^a	23.02	C20H20O4	324.1362	2.9	323.1280[M-H]^–; 213.0929[M-H-C6H6O2]^–; 201.0922[M-H-C7H6O2]^–; 187.0765[M-H-C8H8O2]^–; 175.0754[M-H-C9H8O2]^–; 147.0446[M-H-C11H12O2]^–; 135.0455[M-H-C13H16O]^–; 107.0502[M-H-C14H16O2]^–	Glabridin	GC
104^a	23.38	C20H18O6	354.1103	1.9	353.1046[M-H]^–; 285.1144[M-H-C5H8]^–; 267.1041[M-H-C5H10O]^–; 243.1037[M-H-C6H6O2]^–; 201.0925[M-H-C9H12O2]^–	Licoflavonol	GC
105^a	23.38	C20H18O6	354.1103	1.9	353.1046[M-H]^–; 285.1144[M-H-C5H8]^–; 267.1041[M-H-C5H10O]^–; 243.1037[M-H-C6H6O2]^–; 227.0720[M-H-C6H6O3]^–; 201.0925[M-H-C9H12O2]^–; 125.0250[M-H-C14H12O3]^–	Glycyrrhisoflavone	GC
	23.38	C20H20O6	356.1259	0	355.1179[M-H]^–; 203.1076[M-H-C8H8O3]^–; 165.0551[M-H-C11H10O3]^–	Piperitol	GC
107^e	23.41	C21H20O6	368.1259	−0.2	367.1196[M-H]^–; 337.0718[M-H-CH2O]^–; 297.0409[M-H-C5H10]^–; 281.0456[M-H-C5H10O]^–; 265.0507[M-H-C6H14O]^–; 203.0712[M-H-C10H12O2]^–	Glycycoumarin	GC
108^a	23.52	C21H20O5	352.1311	0.7	351.1245[M-H]^–; 335.0948[M-H-CH4]^–; 321.0815[M-H-CH2O]^–; 307.0973[M-H-C2H4O]^–; 293.0810[M-H-C3H6O]^–; 281.0488[M-H-C5H10]^–; 251.1091[M-H-C6H12O]^–; 199.0767[M-H-C9H12O2]^–	Gancaonin M	GC
	23.67	C21H22O5	354.1467	2.5	353.1398[M-H]^–; 323.0924[M-H-CH2O]^–; 283.0617[M-H-C5H10]^–; 269.0443[M-H-C6H12]^–; 211.0384[M-H-C7H10O3]^–; 203.0734[M-H-C9H10O2]^–	Dehydroglyasperin C	GC
110^a	23.67	C21H22O5	354.1467	2.5	353.1398[M-H]^–; 323.0924[M-H-CH2O]^–; 283.0617[M-H-C5H10]^–; 269.0443[M-H-C6H12]^–; 241.0512[M-H-C5H4O3]^–	Licochalcone D	GC
	24.27	C25H26O5	406.178	0.8	405.1685[M-H]^–; 311.1714[M-H-C6H6O]^–	6,8-Diprenylgenistein	GC
112^a	24.27	C20H16O6	352.0947	3.8	351.0887[M-H]^–; 321.0413[M-H-C2H6]^–; 307.0981[M-H-C2H4O]^–; 283.0983[M-H-C5H8]^–; 265.0872[M-H-C5H10O]^–; 241.0877[M-H-C6H6O2]^–; 199.0768[M-H-C7H4O4]^–	Semilicoisoflavone B	GC
113^e	24.47	C22H22O6	382.1416	−0.2	381.1356[M-H]^–; 365.1063[M-H-CH3]^–; 351.0882[M-H-CH3O]^–; 335.0913[M-H-C2H6O]^–; 311.0587[M-H-C5H9]^–; 307.0978[M-H-C4H8O]^–; 295.0981[M-H-C5H10O]^–; 283.0975[M-H-C6H12O]^–; 255.0313[M-H-C10H12O]^–; 241.0875[M-H-C7H8O3]^–; 217.0528[M-H-C10H12O2]^–; 201.0200[M-H-C11H14O3]^–; 175.0391[M-H-C13H16O2]^–; 161.0249[M-H-C13H16O3]^–; 135.0098[M-H-C14H16O4]^–; 107.0508[M-H-C16H17O4]^–	Glucyrin	GC
	24.67	C21H18O6	366.1103	−1	365.1034[M-H]^–; 335.0567[M-H-CH2O]^–; 295.0251[M-H-C5H10]^–; 207.0453[M-H-C9H2O3]^–	Neoglycyrol	GC
	24.69	C20H16O5	336.0997	1.4	335.0928[M-H]^–; 319.0617[M-H-CH4]^–; 317.0816[M-H-H2O]^–; 305.0454[M-H-C2H6]^–; 291.0673[M-H-CO2]^–	Phaseol	GC
116^b	25.09	C30H46O5	486.3345	−1.7	485.3281[M-H]-; 441.3383[M-H-CO2]-; 355.2640[M-H-C6H10O3]-; 303.2334[M-H-C10H14O3]^–	Echinatic acid	GC
117^b	25.09	C30H46O5	486.3345	−1.7	485.3281[M-H]-; 441.3010[M-H-C2H4O]-; 355.2640[M-H-C6H10O3]-; 303.2334[M-H-C10H16O3]^–	Isoechinatic acid	GC
118^b	25.09	C30H46O5	486.683	−1.7	485.3281[M-H]-; 441.3383[M-H-CO2]-; 355.2640[M-H-C6H10O3]-; 303.2334[M-H-C10H14O3]^–	Triphyllic acid	BS
119^a	25.26	C20H18O4	322.1205	2.3	321.1138[M-H]^–; 305.0800[M-H-CH4]^–; 291.0663[M-H-C2H6]^–; 247.0724[M-H-C4H10O]^–; 175.0748[M-H-C9H6O2]^–; 145.0305[M-H-C11H12O2]^–; 130.9677[M-H-C12H14O2]^–	Licoflavone A	BS
	25.26	C20H18O4	322.1205	2.3	321.1138[M-H]^–; 305.0800[M-H-CH4]^–; 291.0663[M-H-C2H6]^–; 175.0748[M-H-C9H6O2]^–; 145.0305[M-H-C11H12O2]^–; 130.9677[M-H-C12H14O2]^–; 107.0502[M-H-C13H10O3]^–	Isobavachromene	GC
121^d	26.4	C16H22O4	278.1518	−1.5	205.1587[M-H-C4H80]^–; 165.0559[M-H-C8H16]^–; 147.0119[M-H-C8H18O]^–; 127.1123[M-H-C9H10O2]^–; 119.0122[M-H-C9H18O2]^–; 103.0170[M-H-C9H18O3]^–	Diisobutyl phthalate	GC
122^d	26.4	C16H22O4	278.1518	−1.5	205.1587[M-H-C4H80]^–; 165.0559[M-H-C8H16]^–; 147.0119[M-H-C8H18O]^–; 127.1123[M-H-C9H10O2]^–; 119.0122[M-H-C9H18O2]^–; 103.0170[M-H-C9H18O3]^–	Dibutyl phthalate	GC
	26.66	C25H28O4	392.1987	−1	391.1933[M-H]^–; 213.0934[M-H-C11H14O2]^–; 203.0717[M-H-C12H12O2]^–; 201.0605[M-H-C12H14O2]^–; 187.1130[M-H-C13H16O2]^–; 159.0835[M-H-C14H16O3]^–; 157.0661[M-H-C14H18O3]^–	Hispaglabridin A	GC
124^b	27.78	C30H46O4	470.3396	−1.7	469.3332[M-H]^-; 425.3438[M-H-CHO2]^–	Liquiritic acid
	28.79	C30H44O4	468.324	−2.6	467.3189[M-H]^-; 423.3266[M-H-O2]^–	Glabrolide
126^b	29.86	C30H48O3	456.3603	−3.1	455.3507[M-H]^–; 391.2371[M-H-CH4O2]^–	(3β)-3-hydroxyurs-12-en-30-oic acid

a: flavonoids, b: triterpenoids, c: monoterpenoid glycosides, d: other components, e: coumarins, indicates the first discovered component.