Table 1.
Putative annotation of 71 ginsenosides in our untargeted LC-MS/MS analysis of the berries and roots of 60 P. ginseng accessions.
| no. | identification | tR (min) | Measured m/z [M−H]− |
Theoretical m/z [M−H]− |
Molecular formula (neutral) | Structure (PubChem CID) | Major fragment ions (m/z) |
|---|---|---|---|---|---|---|---|
| G1 | ginsenoside Re3 | 3.45 | 961.5363 | 961.5378 | C48H82O19 | 10605931 | 799.48 [M−Glc−H]− 637.43 [M−2Glc−H]− 475.38 [M−3Glc−H]− |
| G2 | ginsenoside Re4 or isomer | 4.50 | 931.5253 | 931.5272 | C47H80O18 | 162861378 or its isomer | 799.48 [M−Ara−H]− 637.43 [M−Ara−Glc−H]− 475.38 [M−Ara−2Glc−H]− |
| G3 | floralginsenoside N or O | 4.76 | 1077.5854 | 1077.5851 | C53H90O22 | 101423541 or 101423542 | 945.54 [M−Ara−H]− 931.53 [M−Rha−H]− 799.48 [M−Rha−Ara−H]− 783.49 [M−Ara−Glc−H]− 637.43 [M−Rha−Ara−Glc−H]− 475.38 [M−Rha−Ara−2Glc−H]− |
| G4 | 20-O-glucosyl-ginsenoside Rf | 4.93 | 961.5372 | 961.5378 | C48H82O19 | 24721561 | 799.48 [M−Glc−H]− 637.43 [M−2Glc−H]− 475.38 [M−3Glc−H]− |
| G5 | ginsenoside Re4 or isomer | 5.39 | 931.5258 | 931.5272 | C47H80O18 | 162861378 or its isomer | 637.43 [M−Ara−Glc−H]− 475.38 [M−Ara−2Glc−H]− |
| G6 | notoginsenoside R1 | 5.77 | 931.5236 | 931.5272 | C47H80O18 | 441934 | 799.48 [M−Xyl−H]− 637.43 [M−Xyl−Glc−H]− 475.38 [M−Xyl−2Glc−H]− |
| G7 | floralginsenoside N or O | 5.94 | 1077.5854 | 1077.5851 | C53H90O22 | 101423541 or 101423542 | 945.54 [M−Ara−H]− 931.53 [M−Rha−H]− 799.48 [M−Rha−Ara−H]− 783.49 [M−Ara−Glc−H]− 637.43 [M−Rha−Ara−Glc−H]− 475.38 [M−Rha−Ara−2Glc−H]− |
| G8 | ginsenoside Re1 | 6.36 | 961.5349 | 961.5378 | C48H82O19 | 122397102 | 799.48 [M−Glc−H]− 637.43 [M−2Glc−H]− 475.38 [M−3Glc−H]− |
| G9 | ginsenoside Re2 | 7.45 | 961.5356 | 961.5378 | C48H82O19 | 101717751 | 637.43 [M−2Glc−H]− 475.38 [M−3Glc−H]− |
| G10 | ginsenoside Rg1a | 8.47 | 799.4848 | 799.4849 | C42H72O14 | 441923 | 637.43 [M−Glc−H]− 475.38 [M−2Glc−H]− |
| G11 | ginsenoside Rea | 8.88 | 945.5432 | 945.5423 | C48H82O18 | 441921 | 783.49 [M−Glc−H]− 637.43 [M−Glc−Rha−H]− 475.38 [M−2Glc−Rha –H]− |
| G12 | 6′-O-acetyl-ginsenoside Rg1 or isomer | 11.69 | 841.4950 | 841.4955 | C44H74O15 | N/A | 799.48 [M−acetyl(Ac)−H]− 637.43 [M−Ac−Glc−H]− 475.38 [M−Ac−2Glc−H]− |
| G13 | malonyl-ginsenoside Re isomer | 12.09 | 1031.5435 | 1031.5432 | C51H84O21 | N/A | 987.55 [M−CO2–H]− 945.54 [M−malonyl(m)−H]− 637.43 [M−(m-Glc)−Rha−H]− 475.38 [M−(m-Glc)−Rha−Glc−H]− |
| G14 | 6‴-O-acetyl-ginsenoside Re or isomer | 12.66 | 987.5521 | 987.5534 | C50H84O19 | N/A | 945.54 [M−Ac−H]− 799.48 [M−Ac−Rha−H]− 783.49 [M−Ac−Glc−H]− 637.43 [M−Ac−Glc−Rha−H]− 475.38 [M−Ac−2Glc−Rha –H]− |
| G15 | malonyl-ginsenoside Re | 12.89 | 1031.5435 | 1031.5432 | C51H84O21 | N/A | 987.55 [M−CO2–H]− 945.54 [M−m−H]− 799.48 [M−m−Rha−H]− 783.49 [M−(m-Glc)−H]− 637.43 [M−(m-Glc)−Rha−H]− 475.38 [M−(m-Glc)−Rha−Glc−H]− |
| G16 | notoginsenoside A | 12.96 | 1123.5919 | 1123.5906 | C54H92O24 | 6451129 | 637.43 [M−3Glc−H]− 475.38 [M−4Glc−H]− |
| G17 | unknown 1 | 13.68 | 883.5037 | 883.5061 | C46H76O16 | N/A | 637.43 475.38 |
| G18 | floralginsenoside P | 13.80 | 1093.5785 | 1093.5800 | C53H90O23 | 101423543 | 961.54 [M−Ara−H]− 799.48 [M−Ara−Glc−H]− 637.43 [M−Ara−2Glc−H]− 475.38 [M−Ara−3Glc−H]− |
| G19 | floralginsenoside C | 13.95 | 815.4809 | 815.4799 | C42H72O15 | 16655212 | 637.43 [M−Glc−H]− 475.38 [M−2Glc−H]− |
| G20 | notoginsenoside N | 14.87 | 961.5374 | 961.5378 | C48H82O19 | 101717750 | 799.48 [M−Glc−H]− 637.43 [M−2Glc−H]− 475.38 [M−3Glc−H]− |
| G21 | unknown 2 | 15.35 | 929.5466 | 929.5479 | C48H82O17 | N/A | 783.49 637.43 |
| G22 | ginsenoside Rfa | 15.87 | 799.4847 | 799.4849 | C42H72O14 | 441922 | 637.43 [M−Glc−H]− 475.38 [M−2Glc−H]− |
| G23 | ginsenoside Ra3 | 16.42 | 1239.6366 | 1239.6379 | C59H100O27 | 73157064 | 1107.60 [M−Xyl−H]− 1077.59 [M−Glc−H]− 945.54 [M−Xyl−Glc−H]− |
| G24 | ginsenoside F3 | 16.86 | 769.4733 | 769.4744 | C41H70O13 | 46887678 | 637.43 [M−Ara−H]− 475.38 [M−Ara−Glc−H]− |
| G25 | ginsenoside Ra0 | 17.25 | 1269.6455 | 1269.6485 | C60H102O28 | 102601548 | 1107.60 [M−Glc−H]− 945.54 [M−2Glc−H]− |
| G26 | ginsenoside F5 | 17.90 | 769.4740 | 769.4744 | C41H70O13 | 46887590 | 637.43 [M−Glc –H]− 475.38 [M−Ara−Glc –H]− |
| G27 | 20(S)-ginsenoside Rg2a | 18.29 | 783.4881 | 783.4900 | C42H72O13 | 12912322 | 637.43 [M−Rha−H]− 475.38 [M−Rha−Glc –H]− |
| G28 | ginsenoside Ra2 | 18.74 | 1209.6260 | 1209.6274 | C58H98O26 | 100941543 | 1077.59 [M−Xyl−H]− 1047.57 [M−Glc−H]− 945.54 [M−Xyl−Ara−H]− 783.49 [M−Xyl−Ara−Glc−H]− |
| G29 | notoginsenoside R2 | 18.81 | 769.4756 | 769.4744 | C41H70O13 | 21599925 | 475.38 [M−Xyl−Glc –H]− |
| G30 | ginsenoside Rb1a | 19.21 | 1107.5928 | 1107.5957 | C54H92O23 | 9898279 | 945.54 [M−Glc−H]− 783.49 [M−2Glc−H]− 621.44 [M−3Glc−H]− 459.38 [M−4Glc−H]− |
| G31 | malonyl-ginsenoside Ra2 | 19.58 | 1295.6262 | 1295.6278 | C61H100O29 | N/A | 945.54 [M−m−Xyl−Ara−H]− 783.49 [M−m−Xyl−Ara−Glc−H]− |
| G32 | malonyl-ginsenoside Rb1 | 20.00 | 1193.5964 | 1193.5961 | C57H94O26 | 118987129 | 1149.61 [M−CO2–H]− 1107.60 [M−m−H]− 1089.59 [M−m−H2O–H]− 945.54 [M−m−Glc−H]− 783.49 [M−m−2Glc−H]− |
| G33 | ginsenoside Roa | 20.17 | 955.4896 | 955.4908 | C48H76O19 | 11815492 | 793.44 [M−Glc−H]− 631.39 [M−2Glc−H]− 613.38 [M−2Glc−H2O–H]− 455.35 [M−2Glc−GlcA−H]− |
| G34 | ginsenoside Rca | 20.56 | 1077.5833 | 1077.5851 | C53H90O22 | 12855889 | 945.54 [M−Ara−H]− 783.49 [M−Ara−Glc−H]− 621.44 [M−Ara−2Glc−H]− 459.38 [M−Ara−3Glc−H]− |
| G35 | Ginsenoside Ra1 | 20.88 | 1209.6263 | 1209.6274 | C58H98O26 | 100941542 | 1077.60 [M−Xyl−H]− 1047.57 [M−Glc−H]− 945.54 [M−Xyl−Ara−H]− 915.53 [M−Xyl−Glc−H]− 783.49 [M−Xyl−Ara−Glc−H]− |
| G36 | malonyl-ginsenoside Rc | 21.37 | 1163.5824 | 1163.5855 | C56H92O25 | N/A | 1119.60 [M−CO2–H]− 1077.59 [M−m−H]− 945.54 [M−m−Ara−H]− 783.49 [M−m−Ara−Glc−H]− 621.44 [M−m−Ara−2Glc−H]− |
| G37 | malonyl-ginsenoside Rb1 isomer | 21.70 | 1193.5979 | 1193.5961 | C57H94O26 | an isomer of 118987129 | 1149.61 [M−CO2–H]− 1107.60 [M−m−H]− 945.54 [M−m−Glc−H]− 783.49 [M−m−2Glc−H]− |
| G38 | ginsenoside Rb2a | 22.18 | 1077.5826 | 1077.5851 | C53H90O22 | 6917976 | 945.54 [M−Ara−H]− 915.53 [M−Glc−H]− 783.49 [M−Ara−Glc−H]− 621.44 [M−Ara−2Glc−H]− 459.38 [M−Ara−3Glc−H]− |
| G39 | ginsenoside Rb3a | 22.63 | 1077.5818 | 1077.5851 | C53H90O22 | 12912363 | 945.54 [M−Xyl−H]− 915.53 [M−Glc−H]− 783.49 [M−Xyl−Glc−H]− 621.44 [M−Xyl−2Glc−H]− 459.38 [M−Xyl−3Glc−H]− |
| G40 | malonyl-ginsenoside Rb2 | 22.85 | 1163.5830 | 1163.5855 | C56H92O25 | N/A | 1119.60 [M−CO2–H]− 1077.59 [M−m−H]− 1059.57 [M−m−H2O–H]− 945.54 [M−m−Ara−H]− 915.53 [M−m−Glc−H]− 783.49 [M−m−Ara−Glc−H]− 621.44 [M−m−Ara−2Glc−H]− 459.38 [M−m−Ara−3Glc−H]− |
| G41 | malonyl-ginsenoside Rb3 | 23.10 | 1163.5836 | 1163.5855 | C56H92O25 | N/A | 1119.60 [M−CO2–H]− 1077.59 [M−m−H]− 1059.57 [M−m−H2O–H]− 945.54 [M−m−Xyl−H]− 783.49 [M−m−Xyl−Glc−H]− 621.44 [M−m−Xyl−2Glc−H]− 459.38 [M−m−Xyl−3Glc−H]− |
| G42 | ginsenoside Rb2 or Rb3 isomer | 23.32 | 1077.5829 | 1077.5851 | C53H90O22 | an isomer of 6917976 or 12912363 | 945.54 [M−pentose−H]− 783.49 [M−pentose−hexose−H]− 621.44 [M−pentose−2hexose−H]− |
| G43 | quinquenoside R1 | 23.49 | 1149.6052 | 1149.6062 | C56H94O24 | 101679657 | 1107.60 [M−acetyl(Ac)−H]− 945.54 [M−Ac−Glc−H]− 783.49 [M−Ac−2Glc−H]− |
| G44 | malonyl-ginsenoside Rb2 or Rb3 isomer | 23.84 | 1163.5834 | 1163.5855 | C56H92O25 | N/A | 1119.60 [M−CO2–H]− 1077.59 [M−m−H]− 1059.57 [M−m−H2O–H]− 945.54 [M−m−pentose−H]− 915.53 [M−m−hexose−H]− 783.49 [M−m−pentose−hexose−H]− |
| G45 | malonyl-ginsenoside Rb2 or Rb3 isomer | 24.01 | 1163.5862 | 1163.5855 | C56H92O25 | N/A | 1119.60 [M−CO2–H]− 1077.59 [M−m−H]− 1059.57 [M−m−H2O–H]− 945.54 [M−m−pentose−H]− 915.53 [M−m−hexose−H]− 783.49 [M−m−pentose−hexose−H]− |
| G46 | ginsenoside Rda | 24.18 | 945.5409 | 945.5428 | C48H82O18 | 11679800 | 783.49 [M−Glc−H]− 621.44 [M−2Glc−H]− 459.38 [M−3Glc−H]− |
| G47 | malonyl-ginsenoside Rd | 24.55 | 1031.5415 | 1031.5432 | C51H84O21 | 14162967 | 987.55 [M−CO2–H]− 945.54 [M−m−H]− 927.53 [M−m−H2O–H]− 783.49 [M−m−Glc−H]− 621.44 [M−m−2Glc−H]− 459.38 [M−m−3Glc−H]− |
| G48 | malonyl-ginsenoside Rd isomer | 24.78 | 1031.5402 | 1031.5432 | C51H84O21 | an isomer of 14162967 | 987.55 [M−CO2–H]− 945.54 [M−m−H]− 927.53 [M−m−H2O–H]− 783.49 [M−m−hexose−H]− 621.44 [M−m−2hexose−H]− |
| G49 | ginsenoside Rs1 or Rs2 | 24.98 | 1119.5929 | 1119.5957 | C55H92O23 | 85044013 or 162343294 | 1077.59 [M−acetyl(Ac)−H]− 945.54 [M−Ac−Ara−H]− 783.49 [M−Ac−Ara−Glc−H]− 621.44 [M−Ac−Ara−2Glc−H]− |
| G50 | dimalonyl-ginsenoside Rd | 25.01 | 1117.5414 | 1117.5436 | C54H86O24 | N/A | 1073.55 [M−CO2–H]− 1029.56 [M−2CO2–H]− 987.55 [M−m−CO2–H]− 945.54 [M−2 m−H]− 783.49 [M−2 m−Glc−H]− 621.44 [M−2 m−2Glc−H]− 459.38 [M−2 m−3Glc−H]− |
| G51 | notoginsenoside O | 25.11 | 1047.5724 | 1047.5745 | C52H88O21 | 154497111 | 915.53 [M−Xyl−H]− 753.48 [M−Xyl−Glc−H]− |
| G52 | ginsenoside Rb2 or Rb3 isomer | 25.28 | 1077.5837 | 1077.5851 | C53H90O22 | an isomer of 6917976 or 12912363 | 945.54 [M−pentose−H]− 783.49 [M−pentose−hexose−H]− 621.44 [M−pentose−2hexose−H]− |
| G53 | malonyl-ginsenoside Rd isomer | 25.29 | 1031.5422 | 1031.5432 | C51H84O21 | an isomer of 14162967 | 987.55 [M−CO2–H]− 945.54 [M−m−H]− 927.53 [M−m−H2O–H]− 783.49 [M−m−hexose−H]− 621.44 [M−m−2hexose−H]− |
| G54 | gypenoside XVII | 25.38 | 945.5420 | 945.5428 | C48H82O18 | 44584555 | 783.49 [M−Glc−H]− 621.44 [M−2Glc−H]− 459.38 [M−3Glc−H]− |
| G55 | acetyl-ginsenoside Rd | 25.57 | 987.5525 | 987.5534 | C50H84O19 | N/A | 945.54 [M−Ac−H]− 783.49 [M−Ac−Glc−H]− 621.44 [M−Ac−2Glc−H]− 459.38 [M−Ac−3Glc−H]− |
| G56 | acetyl-malonyl-ginsenoside Rd isomer | 25.76 | 1073.5502 | 1073.5538 | C53H86O22 | N/A | 1029.56 [M−CO2–H]− 945.54 [M−Ac−m−H]− 783.49 [M−Ac−m−Glc−H]− 621.44 [M−Ac−m−2Glc−H]− |
| G57 | notoginsenoside O isomer | 25.77 | 1047.5713 | 1047.5745 | C52H88O21 | an isomer of 154497111 | 915.53 [M−pentose−H]− 753.48 [M−pentose−hexose−H]− |
| G58 | acetyl-malonyl-ginsenoside Rd isomer | 26.12 | 1073.5552 | 1073.5538 | C53H86O22 | N/A | 1029.56 [M−CO2–H]− 945.54 [M−Ac−m−H]− 783.49 [M−Ac−m−Glc−H]− 621.44 [M−Ac−m−2Glc−H]− |
| G59 | ginsenoside compound-Mc1 | 26.13 | 915.5294 | 915.5323 | C47H80O17 | 90657714 | 783.49 [M−Ara−H]− 621.44 [M−Ara−Glc−H]− 459.38 [M−Ara−2Glc−H]− |
| G60 | ginsenoside compound-O | 26.41 | 915.5323 | 915.5323 | C47H80O17 | 21672569 | 783.49 [M−Ara−H]− 621.44 [M−Ara−Glc−H]− 459.38 [M−Ara−2Glc−H]− |
| G61 | vinaginsenoside R16 | 26.55 | 915.5322 | 915.5323 | C47H80O17 | 131751558 | 783.49 [M−Xyl−H]− 621.44 [M−Xyl−Glc−H]− 459.38 [M−Xyl−2Glc−H]− |
| G62 | gypenoside IX | 26.69 | 915.5306 | 915.5323 | C47H80O17 | 46887681 | 783.49 [M−Xyl−H]− 621.44 [M−Xyl−Glc−H]− 459.38 [M−Xyl−2Glc−H]− |
| G63 | ginsenoside F2a | 27.66 | 783.4900 | 783.4900 | C42H72O13 | 9918692 | 621.44 [M−Glc−H]− 459.38 [M−2Glc−H]− |
| G64 | chikusetsusaponin IVa | 27.78 | 793.4370 | 793.4380 | C42H66O14 | 13909684 | 613.37 [M−Glc−H2O–H]− 455.35 [M−Glc−GlcA−H]− |
| G65 | 20(S)-ginsenoside Rg3a | 28.12 | 783.4877 | 783.4900 | C42H72O13 | 9918693 | 621.44 [M−Glc−H]− 459.38 [M−2Glc –H]− |
| G66 | ginsenoside Rs3 | 28.13 | 825.4987 | 825.5006 | C44H74O14 | 100937823 | 783.49 [M−Ac−H]− 765.48 [M−Ac−H2O–H]− 621.44 [M−Ac−Glc−H]− 459.38 [M−Ac−2Glc−H]− |
| G67 | ginsenoside compound-Mc | 28.36 | 753.4810 | 753.4795 | C41H70O12 | 9896928 | 621.44 [M−Ara−H]− 459.38 [M−Ara−Glc−H]− |
| G68 | calenduloside E | 28.45 | 631.3840 | 631.3852 | C36H56O9 | 176079 | 455.35 [M− GlcA−H]− |
| G69 | ginsenoside compound-Y | 28.50 | 753.4796 | 753.4795 | C41H70O12 | 21672570 | 459.38 [M−Ara−Glc−H]− |
| G70 | 20(S)-ginsenoside Rh2a | 29.09 | 621.4357 | 621.4372 | C36H62O8 | 119307 | 459.38 [M−Glc−H]− |
| G71 | 20(R)-ginsenoside Rh2a | 29.28 | 621.4351 | 621.4372 | C36H62O8 | 14081290 | 459.38 [M−Glc−H]− |
a
Identification of these compounds was confirmed using reference standards.