Table 2.
Identification of flavonoid metabolites in human urine after the consumption of 250 mL ECG extract by UFLC-Q-TOF-MS/MS.
| No. | Identified Metabolites | Formula | RT (min) | [M − H]− (Error, ppm) | Fragment Ions in Negative (−) Ion Mode a |
|---|---|---|---|---|---|
| Naringenin metabolites | |||||
| M1 | Naringenin b | C15H12O5 | 13.6 | 271.0623 (3.5) | 177.0184[M − H-C6H6O]−, 151.0031[M − H-C8H8O]−, 119.0505[M − H-C7H4O4]−, 107.0145[M − H-C8H8O-CO2]−, 93.0356[M − H-C9H6O4]− |
| M2 | Naringenin-4′,7-O-diglucuronide | C27H28O17 | 8.8 | 623.1321 (3.7) | 447.0966[M − H-GlcUA]−, 313.0733[M − H-GlcUA-C4H6O5]−, 271.0621[M − H-2GlcUA]−, 175.0301[M − H-NE-GlcUA]−, 151.0046[M − H-2GlcUA-C8H8O]−, 113.0233[M − H-NE-GlcUA-CO2-H2O]− |
| M3 | Naringenin-5,7-O-diglucuronide | C27H28O17 | 9.4 | 623.1348 (-1.2) | 447.0989[M − H-GlcUA]−, 271.0641[M − H-2GlcUA]−, 175.0259[M − H-NE-GlcUA]−, 151.0054[M − H-2GlcUA-C8H8O]−, 113.0258[M − H-NE-GlcUA-CO2-H2O]− |
| M4 | Naringenin-4′,5-O-diglucuronide | C27H28O17 | 10.7 | 623.1338 (2.9) | 447.0966[M − H-GlcUA]−, 313.0709[M − H-GlcUA-C4H6O5]−, 271.0619[M − H-2GlcUA]−, 175.0320[M − H-NE-GlcUA]−, 151.0028[M − H-2GlcUA-C8H8O]−, 113.0198[M − H-NE-GlcUA-CO2-H2O]− |
| M5 | Naringenin-O-glucoside-O-sulfate | C21H22O13S | 9.3 | 513.0744 (0.6) | 433.1198[M − H-SO3]−, 313.0704[M − H-SO3-C4H8O4]−, 271.0635[M − H-SO3-Glc]−, 151.0025[M − H-SO3-Glc-C8H8O]− |
| M6 | Naringenin-O-glucoside-O-sulfate | C21H22O13S | 9.9 | 513.0761 (1.5) | 433.1186[M − H-SO3]−, 351.0199[M − H-Glc]−, 313.0727[M − H-SO3-C4H8O4]−, 271.0624[M − H-SO3-Glc]−, 151.0031[M − H-SO3-Glc-C8H8O]−, 119.0108[M − H-SO3-Glc-C7H4O4]− |
| M7 | Naringenin-O-glucoside-O-glucuronide | C27H30O16 | 9.4 | 609.1517 (2.9) | 489.1078[M − H-C4H8O4]−, 447.0964[M − H-Glc]−, 429.0871[M − H-Glc-H2O]−, 313.0716[M − H-Glc-C4H6O5]−, 271.0622[M − H-Glc-GlcUA]−, 175.0248[M − H-NE-Glc]−, 151.0040[M − H-Glc-GlcUA-C8H8O]−, 113.0249[M − H-NE-Glc-CO2-H2O]−, 99.0554, 85.0336[M − H-NE-Glc-CO2-H2O-CO]− |
| M8 | Naringenin-O-glucuronide-O-sulfate | C21H20O14S | 10.1 | 527.0545 (0.7) | 447.0957[M − H-SO3]−, 351.0192[M − H-GlcUA]−, 271.0611[M − H-SO3-GlcUA]−, 175.0222[M − H-NE-SO3]−, 151.0030[M − H-SO3-GlcUA-C8H8O]−, 113.0250[M − H-NE-SO3-CO2-H2O]− |
| M9 | Naringenin-4′-O-sulfate | C15H12O8S | 10.3 | 351.0192 (-0.8) | 271.0615[M − H-SO3]−, 177.0203[M − H-SO3-C6H6O]−, 151.0034[M − H-SO3-C8H8O]−, 119.0322[M − H-SO3-C7H4O4]−, 107.0156[M − H-SO3-C8H8O-CO2]−, 93.0244[M − H-SO3-C9H6O4]− |
| M10 | Naringenin-7-O-sulfate | C15H12O8S | 12.3 | 351.0198 (1.3) | 271.0620[M − H-SO3]−, 177.0198[M − H-SO3-C6H6O]−, 151.0043[M − H-SO3-C8H8O]−, 119.0509[M − H-SO3-C7H4O4]−, 107.0144[M − H-SO3-C8H8O-CO2]−, 93.0212[M − H-SO3-C9H6O4]− |
| M11 | Naringenin-5-O-glucuronide | C21H20O11 | 10.7 | 447.0942 (2.5) | 326.2070,271.0619[M − H-GlcUA]−, 151.0038[M − H-GlcUA-C8H8O]−, 125.1002, 107.0114[M − H-GlcUA-C8H8O-CO2]− |
| M12 | Naringenin-7-O-glucuronide b | C21H20O11 | 11.4 | 447.0952 (0.9) | 271.0607[M − H-GlcUA]−, 175.0243[M − H-NE]−, 151.0029[M − H-GlcUA-C8H8O]−, 119.0323[M − H-GlcUA-C7H4O4]−, 113.0248[M − H-NE-CO2-H2O]−, 85.0384[M − H-NE-CO2-H2O-CO]− |
| M13 | Naringenin-4′-O-glucuronide b | C21H20O11 | 11.7 | 447.0943 (-1.1) | 429.0864[M − H-H2O]−, 385.0948[M − H-H2O-CO2]−, 271.0608[M − H-GlcUA]−, 175.0242[M − H-NE]−, 151.0025[M − H-GlcUA-C8H8O]−, 119.0354[M − H-GlcUA-C7H4O4]−, 113.0243[M − H-NE-CO2-H2O]−, 85.0311[M − H-NE-CO2-H2O-CO]− |
| Hesperetin metabolites | |||||
| M14 | Hesperetin-3′-O-sulfate b | C16H14O9S | 10.4 | 381.0301 (0.8) | 301.0712[M − H-SO3]−, 286.0487[M − H-SO3-CH3]−, 177.0188[M − H-SO3-C7H8O2]−, 151.0029[M − H-SO3-C9H10O2]−, 107.0145[M − H-SO3-C9H10O2-CO2]−, 83.0308 |
| M15 | Hesperetin-7-O-sulfate | C16H14O9S | 12.6 | 381.0311 (2.3) | 301.0730[M − H-SO3]−, 286.0498[M − H-SO3-CH3]−, 242.0581, 199.0603, 164.0117, 151.0032[M − H-SO3-C9H10O2]−, 134.0373 |
| M16 | Hesperetin-7-O-glucuronide b | C22H22O12 | 11.8 | 477.1083 (-2.2) | 379.0833, 301.0737[M − H-GlcUA]−, 286.0489[M − H-GlcUA-CH3]−, 175.0242[M − H-HE]−, 113.0252[M − H-HE-CO2-H2O]−, 96.0085 |
| M17 | Hesperetin-3′-O-glucuronide b | C22H22O12 | 12.3 | 477.1064 (1.1) | 301.0734[M − H-GlcUA]−, 175.0226[M − H-HE]−, 113.0248[M − H-HE-CO2-H2O]−, 85.0355[M − H-HE-CO2-H2O-CO]− |
| Eriodictyol metabolites | |||||
| M18 | Eriodictyol-O-glucuronide | C21H20O12 | 10.9 | 463.0929 (2.3) | 287.0563[M − H-GlcUA]−, 255.0668, 175.0233[M − H-EY]−, 151.0030[M − H-GlcUA-C8H8O2]−, 135.0451[M − H-GlcUA-C7H4O4]−, 113.0226[M − H-EY-CO2-H2O]−, 85.0326[M − H-EY-CO2-H2O-CO]− |
| M19 | Eriodictyol-O-sulfate | C15H12O9S | 12.5 | 367.0169 (4.2) | 287.0572[M − H-SO3]−, 151.0037[M − H-SO3-C8H8O2]−, 135.0451[M − H-SO3-C7H4O4]−, 107.0144[M − H-SO3-C8H8O2-CO2]− |
| Apigenin metabolites | |||||
| M20 | Apigenin-O-glucuronide | C21H18O11 | 12.6 | 445.2089 (0.6) | 269.0463[M − H-GlcUA]−, 175.0240[M − H-AE]−, 151.0028[M − H-GlcUA-C8H6O]−, 117.0240[M − H-GlcUA-C7H4O4]−, 113.0250[M − H-AE-CO2-H2O]−, 85.0312[M − H-AE-CO2-H2O-CO]− |
a The losses are: Glc = glucose moiety, GlcUA = glucuronyl moiety, NE = naringenin, NEG = naringenin glucuronide, HE = hesperetin, EY = eriodictyol, AE = apigenin. b Confirmation in comparison with authentic standards.