Table 1.
UHPLC-ESI-MS data of G. officinalis herb components in negative and/or positive ion mode.
| Peak No. | tR [min] | λmax [nm] | [M – H]− (m/z) | Error [ppm] | MS/MS (m/z) | Identification Proposal |
|---|---|---|---|---|---|---|
| [M + H]+ (m/z) | ||||||
| 1 | 0.89 | 200 | 209.0309 | −1.6 | 165 [M − 44/CO2 − H]− | Hexaric acid |
| 2 | 1.28 | 250 | 191.0203 | −1.8 | 111 [M − 44/CO2 − 36/2xH2O − H]− | Hexaric acid monolactone |
| 3 | 1.49 | – | 144.1132 | −1.2 | - | Hydroxygalegine |
| 4 | 4.32 | 325 | 371.0618 | 0.4 | 209 [M − 162/caffeoyl − H]−, 191 [209 − 18/H2O − H]−, 147 [209 − 18/H2O − 44/CO2 − H]−, 179 [CA − H]−, 135 [CA − 44/CO2 − H]−, 129 [209 − 44/CO2 − 36/2xH2O − H]−, 111 [209 − 44/CO2 − 54/3xH2O − H]− |
Monocaffeoylhexaric acid 1 |
| 5 | 5.48 | – | 205.0977 | −2.9 | 187 [M − 18/H2O + H]+ | Vasicinol |
| 6 | 7.5 | – | 128.1185 | −2.2 | - | Galegine |
| 7 | 8.34 | 325 | 371.0613 | 1.8 | 209 [M − 162/caffeoyl − H]−, 191 [209 − 18/H2O − H]−, 147 [209 − 18/H2O − 44/CO2 − H]−, 179 [CA − H]−, 135 [CA − 44/CO2 − H]−, 129[209 − 44/CO2 − 36/2xH2O − H]−, 111 [209 − 44/CO2 − 54/3xH2O − H]− |
Monocaffeoylhexaric acid 2 |
| 8 | 8.74 | 206, 285 | 189.1029 | −3.5 | 171 [M − 18/H2O + H]+, 144 [M − 18/H2O − 27/CHN + H]+, 118 [M − 18/H2O − 27/CHN − 26/C2H2 + H]+ |
Vasicine |
| 9 | 9.49 | 325 | 371.0621 | −0.1 | 209 [M − 162/caffeoyl − H]−, 191 [209 − 18/H2O − H]−, 147 [209 − 18/H2O − 44/CO2 − H]−, 179 [CA − H]−, 135 [CA − 44/CO2 − H]−, 129[209 − 44/CO2 − 36/2xH2O − H]−, 111 [209 − 44/CO2 − 54/3xH2O − H]− |
Monocaffeoylhexaric acid 3 |
| 10 | 11.84 | 313 | 355.0671 | 0.9 | 209 [M − 146/coumaroyl − H]−, 191 [209 − 18/H2O − H]−, 147 [209 − 18/H2O − 44/CO2 − H]−, 163 [CuA − H]−, 129 [209 − 44/CO2 − 36/2xH2O − H]−, 119 [CuA − 4/CO2 − H]−, 111 [209 − 44/CO2 − 54/3xH2O − H]− |
Monocoumaroylhexaricacid 1 |
| 11 | 11.92 | 285 | 285.0617 | 0.6 | 152/153 a [M − 132/pentose − H]−, 108/109 a [PA − 44/CO2 − H]− |
Protocatechuic acid O-pentoside |
| 12 | 12.31 | 208 | 351.1565 | −0.2 | 189 [M − 162/hexose + H]+, 171 [M − 162/hexose − 18/H2O + H]+ |
Vasicine-O-hexoside |
| 13 | 12.43 | 325 | 371.0614 | 1.6 | 209 [M − 162/caffeoyl − H]−, 191 [209 − 18/H2O − H]−, 147 [209 − 18/H2O − 44/CO2 − H]−, 179 [CA − H]−, 135 [CA − 44/CO2 − H]−, 129[209 − 44/CO2 − 36/2xH2O − H]−, 111 [209 − 44/CO2 − 54/3xH2O − H]− |
Monocaffeoylhexaric acid 4 |
| 14 | 12.71 | 314 | 355.0671 | 0.4 | 209 [M − 146/coumaroyl − H]−, 191 [209 − 18/H2O − H]−, 147 [209 − 18/H2O − 44/CO2 − H]−, 163 [CuA–H]−, 129 [209 − 44/CO2 − 36/2xH2O − H]−, 119 [CuA − 44/CO2 − H]−, 111 [209 − 44/CO2 − 54/3xH2O − H]− |
Monocoumaroylhexaricacid 2 |
| 15 | 13.24 | 325 | 385.0765 | 0.9 | 209 [M − 176/feruloyl − H]−, 193 [FeA − 191 − H]−, 191 [M − 193 − H or 209 − 18/H2O − H]−, 147 [209 − 18/H2O − 44/CO2 − H]−, 111 [209 − 44/CO2 − 54/3xH2O − H]− |
Monoferuloylhexaric acid 1 |
| 16 | 14.3 | 325 | 385.0775 | 1.0 | 209 [M − 176/feruloyl − H]−, 193 [FeA − H]−, 191 [M − 193 − H or 209 − 18/H2O − H]−, 147 [209 − 18/H2O − 44/CO2 − H]−, 111 [209 − 44/CO2 − 54/3xH2O − H]− |
Monoferuloylhexaric acid 2 |
| 17 | 14.82 | 325 | 385. 0773 | 0.7 | 209 [M − 176/feruloyl − H]−, 193 [FeA − H]−, 191 [M − 193 − H or 209 − 18/H2O − H]−, 149 [194v − 44/CO2 − H]−, 147 [209 − 18/H2O − 44/CO2 − H]−, 111 [209 − 44/CO2 − 54/3xH2O − H]− | Monoferuloylhexaric acid 3 |
| 18 | 15.1 | 315 | 325.0922 | 1.5 | 163 [M − 162/hexose − H]−, 119 [CuA − 44/CO2 − H]− | Coumaric acid O-hexoside |
| 19 | 15.12 | 285 | 417.1050 | −1.6 | 152/153 a [M − 264/2 pentose − H]−, 108/109 a [PA − 44/CO2 − H]− |
Protocatechuic acid O-di-pentoside |
| 20 | 15.21 | 312 | 355.0665 | 1.2 | 209 [M − 146/coumaroyl − H]−, 191 [209 − 146–18/H2O − H]−, 147 [209 − 18 − 44/CO2 − H]−, 163 [CuA − H]−, 129 [209 − 44/CO2 − 36/2xH2O − H]−, 119 [CuA − 44/CO2 − H]−, 111 [209 − 44/CO2 − 54/3xH2O − H]− |
Monocoumaroylhexaricacid 3 |
| 21 | 15.58 | 211 | 203.0825 | −4.2 | 185 [M–18/H2O+H]+ | Vasicinone |
| 22 | 16.54 | 325 | 385.0753 | 1.3 | 209 [M − 176/feruloyl − H]−, 193 [385 − 191 − H]−, 191 [M − 193 − H]−, 147 [191 − 44/CO2 − H]−, 111 [209 − 44/CO2 − 54/3xH2O − H]− |
Monoferuloylhexaric acid 4 |
| 23 | 17.59 | 325 | 353.0512 | 1.8 | 191 [M − 162/caffeoyl − H]−, 179 [CA − H]−, 111 [QA − 44/CO2 − 36/2xH2O − H]− |
Chlorogenicacid S |
| 24 | 18.39 | 312 | 163.0401 | −0.1 | 119 [M − 44/CO2 − H]− | p-Coumaricacid S |
| 25 | 19.98 | 290 | 465.1030 | 1.8 | 303 [M − 162/hexose − H]−, 285 [M − 162/hexose − 18/H2O − H]− |
Taxifolin-3-O-hexoside |
| 26 | 20.94 | 254, 354 | 755.2036 | 1.2 | 609 [M − 146/deoxyhexose − H]−, 300/301 a [M − 2 × 146/dideoxyhexose − 162/hexose − H]− |
Quercetin-3-O-dideoxyhexosyl– hexoside 1 |
| 757.2224 | 1.3 | 611[M − 146/deoxyhexose + H]+, 303 [M − 2 × 146/dideoxyhexose − 162/Hexose + H]+ |
||||
| 27 | 21.06 | 254, 354 | 755.2038 | 0.4 | 609 [M − 146/deoxyhexose − H]−, 300/301 a [M – 2 × 146/dideoxyhexose – 162/Hexose – H]− |
Quercetin-3-O-dideoxyhexosyl- hexoside 2 |
| 757.2215 | 0.4 | 465 [M–2 × 146/dideoxyhexose + H]+, 303 [M – 2 × 146/dideoxyhexose – 162/Hexose + H]+ | ||||
| 28 | 21.61 | 265, 344 | 447.0942 | −0.7 | 285 [M − 162/glucose – H]− | Kaempferol-3-O-glucoside (astragalin S) |
| 29 | 21.97 | 265, 344 | 739.2088 | 0.5 | 284/285 a [M – 2 × 146/dideoxyhexose − 162/hexose–H]− | Kaempferol-3-O-dideoxyhexosyl- hexoside 1 |
| 30 | 22.21 | 265, 344 | 739.2083 | 1.0 | 284/285 a [M – 2 × 146/dideoxyhexose − 162/hexose − H]− | Kaempferol-3-O-dideoxyhexosyl- hexoside 2 |
| 31 | 22.47 | 255, 353 | 609.1416 | −0.2 | 300/301 a [M − 308/rutinose − H]− | Quercetin-3-O-rutinoside (rutin S) |
| 611.1634 | 0,2 | 303 [M − 308/rutinose + H]+ | ||||
| 32 | 22.89 | 255, 353 | 463.0870 | 1.8 | 300/301 a [M − 162/galactose − H]− | Quercetin-3-O-galactoside (hyperoside S) |
| 465.1037 | −1.7 | 303 [M − 162 + H/galactose]+ | ||||
| 33 | 23.32 | 263, 368 | 593.1495 | 3.1 | 284/285 a [M − 308/rutinose − H]− | Kaempferol-3-O-deoxyhexosyl- hexoside 1 (nicotiflorin S) |
| 595.1681 | −3.4 | 287 [M − 308/rutinose + H]+ | ||||
| 34 | 24.12 | 263, 368 | 593.1505 | 1.0 | 284/285 a [M − 308/deoxyhexose-hexose − H]− | Kaempferol-3-O-deoxyhexosyl- hexoside 2 |
| 595.1683 | −3.8 | 287 [M − 308/deoxyhexose-hexose + H]+ | ||||
| 35 | 24.53 | 255, 353 | 623.1608 | 2.7 | 315 [M − 308/rutinose − H]−, 300 [M − 308/rutinose − 15/Me• − H]−• |
Isorhamnetin-3-O-rutinoside (narcissin S) |
| 625.1787 | −4.0 | 317 [M − 308/rutinose + H]+, 300 [M − 308/rutinose − 15/Me• + H]+• |
||||
| 36 | 24.66 | 254, 348 | 447.0924 | 2.9 | 300/301 a [M − 146/rhamnose − H]− | Quercetrin-3-O-rhamnoside (quercitrin S) |
| 37 | 25.96 | 255, 353 | 797.2135 | 2.5 | 300/301 a [M – 2 × 146/dideoxyhexose − 162/hexose − 42/acetyl − H]− | Quercetin-3-O-acetyl- dideoxyhexosyl-hexoside |
| 38 | 26.69 | 263, 368 | 431.0973 | 2.2 | 284/285 a [M − 146/deoxyhexose − H]− | Kaempferol-3-O-deoxyhexoside |
| 39 | 27.13 | 264, 368 | 781.2192 | −0.1 | 284/285 a [M – 2 × 146/dideoxyhexose − 162/hexose − 42/acetyl − H]− | Kaempferol-3-O-acetyl- dideoxyhexosyl-hexoside |
| 783.2373 | −2.7 | 287 [M – 2 × 146/dideoxyhexose − 162/hexose − 42/acetyl + H]+ |
tR, retention time; λmax, absorbance maximum in UV-Vis spectrum; a [Y0 − H]−•/[Y0]−; S reference standard; CA, caffeic acid; CuA, coumaric acid; FeA, ferulic acid; PA, protocatechuic acid; QA, quinic acid.