Table 1.
Metabolites annotated in aerial part of Geum rivale L. by reversed phase ultra-high-performance liquid chromatography—tandem mass spectrometry (RP-UHPLC-QqTOF-MS/MS).
| # | tR
a (min) |
[M−H]−obs
b (m/z) |
[M−H]−calc
c (m/z) |
EC d | Fragmentation Patterns e | Δm (ppm) | Assignment | Extract Fraction |
Ref. f |
|---|---|---|---|---|---|---|---|---|---|
| Phenolic acids derivatives | |||||||||
| 1 | 4.2 | 635.0908 | 635.0890 | C27H25O18 | 169.0125 (5%), 313.0553 (7%), 465.0676 (20%), 483.0735 (4%), 635.0908 (100%) | −2.6 | Trigalloyl hexose | EA | [25,26,27] |
| 2 | 4.3 | 457.0907 | 457.0988 | C19H21O13 | 179.0333 (100%), 341.0802 (70%), 457.0907 (30%) | 17.7 | Caffeoyl-hexoside malate | A | [25] |
| 3 | 5.9 | 300.9959 | 300.9999 | C14H6O8 | 117.0333 (9%), 145.0282 (8%), 173.0226 (15%), 185.0230 (20%), 201.0170 (20%), 229.0110 (23%), 245.0060 (18%), 283.9932 (40%), 299.9874 (42%), 300.9959 (100%) | 10 | Ellagic acid | EA | [28] |
| 4 | 5.7 | 433.0366 | 433.0412 | C19H14O12 | 299.9888 (40%), 300.9965 (100%), 313.0684 (25%), 343.0769 (10%), 433.0359 (50%) | 10.6 | Ellagic acid pentoside | EA | [25] |
| Flavonoids and their derivatives | |||||||||
| 5 | 4.2 | 653.0976 | 653.0996 | C27H26O19 | 301.0343 (10%), 477.0649 (13%), 653.0976 (100%) | 2.6 | Quercetin-bis-hexuronide | A | [27] |
| 6 | 6.3 | 477.0638 | 477.0675 | C21H18O13 | 301.0376 (100%), 477.0638 (5%) | 5.6 | Quercetin-hexuronide | A | [25,29] |
| 7 | 6.2 | 953.1265 | 953.1266 | C42H34O26 | 301.0336 (5%), 477.0647 (100%), 953.1265 (70%) | −6.8 | Quercetin-hexuronide dimer | EA | [30] |
| 8 | 5.2 | 637.1003 | 637.1046 | C27H27O18 | 285.0384 (17%), 461.0686 (45%), 637.1003 (100%) | −1.0 | Kaempferol-bis-hexuronide | EA | [20] |
| 9 | 6.8 | 923.1519 | 923.1523 | C42H35O24 | 285.0394 (10%), 461.0708 (100%), 923.1519 (70%) | 4.2 | Dihydrokaempferol-kaempferol-hexuronide dimer | EA | [30] |
| 10 | 9.7 | 285.0344 | 285.0405 | C15H10O6 | 93.0333 (22%), 108.0190 (10%), 117.0321 (8%), 154.0374 (9%), 159.0433 (15%), 169.0626 (10%), 185.0576 (25%), 187.0360 (17%), 211.0351 (10%), 227.0295 (13%), 239.0295 (15%), 285.0344 (100%) | 21.7 | Kaempferol | EA | [31] |
| 11 | 5.6 | 461.0692 | 461.0725 | C21H18O22 | 285.0385 (100%), 461.0692 (15%) | 3.2 | Kaempferol-hexuronide | A | [32,33] |
| 12 | 5.0 | 667.1106 | 667.1152 | C28H28O19 | 315.0487 (15%), 491.0797 (30%), 667.1106 (100%) | 6.8 | Isorhamnetin-bis-hexuronide | A | [20] |
| 13 | 5.8 | 491.0818 | 491.0831 | C22H20O13 | 300.0261 (10%), 315.0501 (100%), 491.0818 (6%), | 2.6 | Isorhamnetin-hexuronide | A | [34,35] |
| Tannins | |||||||||
| 14 | 0.6 | 481.0615 | 481.0624 | C20H19O14 | 300.9988 (70%), 481.0606 (100%), 275.0195 (40%), 133.0143 (20%) | 1.9 | HHDP-hexoside | EA | [25,36,37] |
| 15 | 3.5 | 577.1263 | 577.1351 | C30H26O12 | 289.0673 (16%), 407.0704 (18%), 425.0803 (30%), 577.1263 (100%) | 15.3 | Proantocyanidin dimer | EA | [25,38] |
| 16a | 3.2 | 783.0634 | 783.0686 | C34H25O22 | 300.9967 (4%), 783.0634 (100%) | 6.6 | Pedunculagin I | EA | [25,36,37] |
| 16b | 4.7 | 783.0680 | 783.0686 | C34H25O22 | 300.9982 (100%), 633.0714 (75%), 783.0680 (100%) | 0.7 | Pedunculagin I | A | [25,36,37] |
| 17 | 4.9 | 935.0780 | 935.0796 | C41H28O26 | 300.9988 (30%), 767.0745 (2%), 935.0780 (100%) | 1.7 | Galloyl-bis-HHDP-hexose | A | [25,36,37] |
a the analytes are listed in the order of their elution; b the m/z values were derived from the acquired spectra; c the m/z values were calculated based on the predicted elemental composition (EC); d the elemental compositions were predicted with mass tolerance of 10 ppm; e MS/MS fragmentation patterns are provided as m/z values of the fragment ions (their relative intensities); f literature references providing information on the elemental compositions and MS/MS fragmentation patterns of the annotated compounds; EA- compounds were found in the ethyl acetate extract of water avens; A—compounds were found in the aqueous extract of water avens; HHDP—hexahydroxydiphenoyl group.