Table 2. Identification details of the ingredients in KYQG represented by 38 peaks using a UFLC-Q-TOF-MS/MS technique.
| Variables | Retention time (min) | Attributiona | Ingredients | Molecular formula | [M + H]+ | [M − H]− | Positive mode | Negative mode |
|---|---|---|---|---|---|---|---|---|
| P1 | 4.92 | AL | Lysineb | C6H14N2O2 | 147.1128 (−0.4) | 130.0867[M+H-NH3]+, 84.0826[M+H-NH3-HCOOH]+, 67.0566[M+H-2NH3-HCOOH] + | ||
| P2 | 5.27 | AL | Arginineb | C6H14N4O2 | 175.1190 (0) | 173.1058 (8.1) | 158.0934[M+H-NH3]+, 130.0985[M+H-COOH]+, 70.681[M+H- NH3-C3H6NO2]+, 60.0594[M+H-C5H10NO2]+ | 156.0767[M-H-NH3]−, 131.0827[ M-H-C3H6]− |
| P317,19 | 5.32 | AL | Asparagine | C4H8N2O3 | 133.0606 (−1.4) | 116.0336[M+H-NH3]+, 87.0565[M+H-HCOOH]+, 74.0259[M+H-C2H5NO]+, 70.0312[M+H-HCOOH-NH3]+ | ||
| P4 | 5.36 | AL | Aspartic acidb | C4H7NO4 | 134.0451 (0.3) | 132.0315 (1.2) | 116.0338[M+H-H2O]+, 88.0404[M+H-HCOOH]+, 74.0256[M+H-NH3-CO-CH3]+ | 115.0045[M-H-NH3]−, 88.0413[M-H-CO2]−, 71.0154[M-H- CO2-NH3]− |
| P5 | 5.59 | AL | Citrullineb | C6H13N3O3 | 176.1029 (−0.5) | 159.0765[M+H-NH3]+, 113.0709[M+H-NH3-HCOOH]+, 70.0673[M+H-NH3-CO2-CH3NO]+ | ||
| P618 | 5.66 | AL | γ-aminobutyric acid | C4H9NO2 | 104.0706 (−0.1) | 87.0457[M+H-NH3]+, 69.0359[M+H-NH3-H2O]+, 60.0835[M+H-CO2]+ | ||
| P719 | 6.05 | AL | Proline | C5H9NO2 | 116.0709 (0.8) | 70.0677[M+H-HCOOH]+, 68.0521[M+H-HCOOH-H2O]+ | ||
| P8 | 6.61 | RA/RO | Chelidonic acidb | C7H4O6 | 185.0082 (0.7) | 182.9939 (1.8) | 141.0173[M+H-CO2]+, 97.0297[M+H-2CO2]+, 71.0152[M+H-2CO2-C2H2]+ | 139.0038[M-H-CO2]−, 68.9988[M-H-C4H2O4]−, 67.0207[M-H-2CO2-CO]− |
| P920 | 10.20 | AL | Pyroglutamic acid | C5H7NO3 | 130.0500 (1.1) | 84.0461[M+H-HCOOH]+, 56.0531[M+H-HCOOH-CO]+ | ||
| P10 | 11.13 | AL | Tyrosineb | C9H11NO3 | 182.0811 (−0.2) | 165.0543[M+H-NH3]+, 147.0435[M+H-NH3-H2O]+, 136.0755[[M+H-HCOOH]+, 119.0490[[M+H-HCOOH-NH3]+, 91.0553[M+H-HCOOH-NH3-CO]+, 77.0403[M+H-HCOOH-NH3-CO-CH2]+, 65.04111[M+H-HCOOH-NH3-CO-C2H2]+ | ||
| P11 | 15.28 | AL | Phenylalanineb | C9H11NO2 | 166.0864 (0.9) | 164.0725 (4.6) | 120.0816[M+H-HCOOH]+, 103.0554[M+H-HCOOH-NH3]+ | 165.0760[M], 147.0445[M-H-NH3]−, 103.0555[M-H-NH3-CO2]−, 72.0096[M-H-NH3-C6H5]− |
| P12 | 15.35 | RS | Harpagideb | C15H24O10 | 363.1282 (−1.2) | 387.1256[M+Na]+ | 409.1338[M+COOH]−, 201.0760[M-H-Glc]−, 183.0656[M-H-Glc-H2O]−, 165.0549[M-H-Glc-H2O-H2O]−, 139.0388[M-H-Glc-H2O-H2O-C2H2]− | |
| P13 21 | 18.38 | FL | Neochlorogenic acid | C16H18O9 | 355.1025 (−1.9) | 353.0877 (−0.8) | 163.0396[M+H- C7H12O6]+, 145.0288[M+H- C7H12O6-H2O ]+, 117.0342[ M+H-C7H12O6-H2O-CO]+, 89.0402[M+H-C7H12O6-H2O-CO-CO]+ | 191.0557[M-H-C9H6O3]−, 179.0344[M-H-C7H10O5]−, 135.0450[M-H- C7H10O5-CO2]− |
| P14 | 23.65 | FL | Chlorogenic acidb | C16H18O9 | 355.1026 (0.6) | 353.0891 (−1.3) | 163.0394[M+H-C7H12O6]+, 145.0290[M+H-C7H12O6-H2O]+, 117.0344[M+H-C7H12O6-H2O-CO]+, 89.0405[M+H-C7H12O6-H2O-2CO]+ | 191.0561[M-H-C9H6O3]− |
| P15 21 | 24.69 | FL | Cryptochlorogenic acid | C16H18O9 | 355.1027 (0.9) | 353.0869 (−0.5) | 163.0390[M+H-C7H12O6]+, 145.0284[M+H-C7H12O6-H2O]+, 117.0338[M+H-C7H12O6-H2O-CO]+ | 191.0548[M-H-C9H6O3]−, 173.0442[M-H-C9H6O3-H2O]−, 135.0441[M-H-C7H10O5-CO2]−, 93.0345[M-H-C9H7O4-2H2O-COOH]− |
| P16 | 28.59 | FL | Caffeic acidb | C9H8O4 | 181.0409 (−0.7) | 179.0354 (0.2) | 163.0387[M+H-H2O]+, 135.0439[M+H-H2O-CO]+, 89.3980[M+H-H2O-CO-HCOOH]+ | 135.0446[M-H-CO2]− |
| P17 | 42.04 | RG | Liquiritinb | C21H22O9 | 419.1334 (−0.7) | 417.1189 (−0.6) | 257.0803[M+H-Glc]+, 137.0224[M+H-C14H18O6]+ | 255.0645[M-H-Glc]−, 135.0077[M-H-C14H18O6]−, 119.0489[M-H-C14H18O6-Glc]− |
| P18 | 42.69 | FL | Isoquercitrinb | C21H20O12 | 465.1027 (−0.1) | 463.0876 (−1.3) | 303.0489[M+H-Glc]+ | 301.0351[M-H-Glc]-, 271.0240[M-Glc-CHO]−, 255.0285[M-H-Glc-O-CHO]−, 151.0016[M-H-C7H3O3]− |
| P19 | 43.44 | FL | Luteolin-7-O-glucosideb | C21H20O11 | 449.1077 (−0.3) | 447.0917 (−2.3) | 287.0554[M+H-Glc]+ | 285.0404[M-H-Glc]− |
| P20 22 | 46.33 | FL | 3,4-Dicaffeoylquinic acid | C25H24O12 | 517.1335 (−1.0) | 515.1178 (−1.3) | 499.1231[M+H-H2O]+, 163.0389[M+H-C6H18O9]+, 145.0286[M+H-C6H18O9-H2O]+ | 353.0853[M-H-C9H6O3]−, 191.0541[M-H-2C9H6O3]−, 173.0435[M-H-2C9H6O3-H2O]− |
| P21 22 | 48.29 | FL | 3,5-Dicaffeoylquinic acid | C25H24O12 | 517.1325 (−0.6) | 515.1195 (−2.5) | 499.1229[M+H-H2O]+, 163.0390[M+H-C6H18O9]+, 145.0280[M+H-C6H18O9-H2O]+ | 353.0867[M-H-C9H6O3]−, 191.0546[M-H-2C9H6O3]−, 173.0437[M-H-2C9H6O3-H2O]− |
| P22 22 | 52.11 | FL | 4,5-Dicaffeoylquinic acid | C25H24O12 | 517.1336 (2.4) | 515.1181 (−3.4) | 499.1240[M+H-H2O]+, 163.0397[M+H-C16H18O9]+, 145.0289[M+H-C16H18O9-H2O]+ | 353.0853[M-H-C9H6O3]−, 191.0541[M-H-2C9H6O3]−, 173.0435[M-H-2C9H6O3-H2O]− |
| P23 | 53.51 | RS | Angoroside Cb | C36H48O19 | 783.2723 (0.7) | 807.2675 [M+Na]+ | 607.2276[M-H-C6H11O4-CHO]−, 193.0492[M-H-C26H38O15]−, 175.0383[M-H-C26H38O15-H2O]− | |
| P24 | 59.42 | RG | Isoliquiritosideb | C21H22O9 | 419.1334 (−0.7) | 417.1177 (−0.6) | 257.0812[M+H-Glc]+, 137.0224[M+H-Glc-C8H6O]+ | 255.0648[M-H-Glc]−, 119.0489[M-H-Glc-C8H6O-H2O]−, 92.0260[M-H-Glc-C9H7O3]− |
| P25 23 | 63.49 | RA | Saponin 1c | — | 1035.5357 | 1035.5371, 579.3893,417.3358 | ||
| P26 23 | 65.46 | RA | Saponin 2c | — | 903.4940 | 903.4922,741.4405,417.3335 | ||
| P27 | 70.83 | RS | Harpagosideb | C24H30O11 | 493.1679 (−4.9) | 517.1675[M+Na]+ | 539.1745[M+COOH]−, 147.0434[M-H-C15H22O9]− | |
| P28 | 73.23 | RS | Cinnamic acidb | C9H8O2 | 149.0598 (0) | 147.0452 (0.2) | 131.0490[M+H-H2O]+, 103.0550[M+H-HCOOH]+ | 103.0529[M-COOH]− |
| P29 | 74.34 | FL | Macranthoidin Bb | C65H106O32 | 1397.6515 (−3.9) | 1421.6554[M+Na]+ | 1443.6582[M+COOH]−, 1073.5507[M-H-2Glc]− | |
| P30 24 | 76.63 | FL | Macranthoside A | C47H76O17 | 913.5130 (−1.4) | 782.4876[M+H-H2O]+, 751.4601[M+H-Glc]+, 455.3512[M+H- Ara-Rha-Glc]+, 437.3398[M+H- Ara-Rha-Glc-H2O]+, 409.3510[M+H-Ara-Rha-Glc-HCOOH]+ | ||
| P31 | 79.46 | FL | Dipsacoside Bb | C53H86O22 | 1073.5561 (−2.1) | 1097.5470[M+Na]+ | 1119.5572[M+COOH]−, 749.4483[M-H-2Glc]− | |
| P32 | 99.32 | RG | Glycyrrhetic acidb | C30H46O4 | 469.3289 (−3.5) | 471.3460[M+Na]+ | 469.3289[M-H]− | |
| P33 | 99.33 | RG | Glycyrrhizic acidb | C42H62O16 | 823.4098 (−1.1) | 471.3453[M+H-2C6H8O6]+, 453.3362[M+H-2C6H8O6-H2O]+, | ||
| P34 25 | 105.34 | RG | Gancaonin B | C21H20O6 | 369.1334 (0.3) | 285.0765[M+H-C5H8O]+, 270.0525[M+H-C5H6O2]+, 255.0648[M+H-C5H6O2-CH3]+ | ||
| P35 | 108.09 | RA | Sarsasapogenin b | C27H44O3 | 417.3359 (−0.9) | 415.3218 (3.9) | 417.3353[M+H]+, 273.2216 225.2114 | |
| P36 | 108.92 | RO | Methylophiopogonanone Ab | C19H18O6 | 343.1170 (−4.1) | 207.0644[M+H-C8H8O2]+, 135.0436[M+H-C11H12O4]+ | ||
| P37 | 109.09 | RO | Ruscogeninb | C27H42O4 | 431.3157 (−0.1) | 429.3010 (−2.5) | 431.3133[M+H]+, 287.2005, 269.1899 | |
| P38 | 109.09 | RO | Ophiopogonin Db | C44H70O16 | 855.4745 (−2.8) | 431.3172[M-Man-Xyl-Gal-2O]+ 287.2007 |
aFL = Flos lonicerae; RS = Radix scrophulariae; RO = Radix ophiopogonis; RA = Radix asparagi; RG = Radix et rhizoma glycyrrhizae; AL = 5 herbs.
bIdentification compared with reference substances.
cSarsasapogenin as aglycone.