Comprehensive Profiling and Quantification of Ginsenosides in the Root, Stem, Leaf, and Berry of Panax ginseng by UPLC-QTOF/MS
Abstract
:1. Introduction
2. Materials and Methods
2.1. Standard Constituents and Reagents
2.2. Panax ginseng Samples
2.3. Extraction of Ginsenosides
2.4. UPLC-QTOF/MS Conditions for Ginsenoside Profiling
2.5. Data Processing and Multivariate Analysis
3. Results and Discussion
3.1. UPLC-QTOF/MS with an In-House Library to Profile Various Ginsenosides
3.2. Profiling of Various Ginsenosides from the Roots, Stems, Leaves, and Berries of Panax ginseng
3.3. Quantification of Ginsenosides from the Roots, Stems and Leaves, and Berries of Panax ginseng
4. Conclusions
Supplementary Materials
Acknowledgments
Author Contributions
Conflicts of Interest
References
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Sample Availability: Samples of the compounds are not available from the authors. |
No. | RT (min) | Ginsenosides | Molecular Formula | Expected Neutral Mass (Da) | Observed Neutral Mass (Da) | QTOF/MS (ESI-) (m/z) | Mass Accuracy (ppm) | Adducts |
---|---|---|---|---|---|---|---|---|
1 | 3.58 | 20-O-Glucoginsenoside Rf (gRf) | C48H82O19 | 962.545 | 962.5453 | 1007.5435 | 0.26 | +HCOO |
2 | 4.07 | Notoginsenoside R1 (nR1) | C47H80O18 | 932.5345 | 932.5343 | 977.5325 | 0.2 | +HCOO |
3 | 5.36 | Ginsenoisde Rg1 (Rg1) | C42H72O14 | 800.4922 | 800.4908 | 845.489 | 1.62 | +HCOO |
4 | 5.66 | Ginsenoside Re (Re) | C48H82O18 | 946.5501 | 946.5503 | 991.5485 | 0.16 | +HCOO |
5 | 8.05 | Floralginsenoside Ka (fKa) | C36H62O11 | 670.4292 | 670.4295 | 715.4277 | 0.34 | +HCOO |
6 | 8.46 | Ginsenoside Rh6 (Rh6) | C36H62O11 | 670.4292 | 670.4291 | 715.4273 | 0.19 | +HCOO |
7 | 10.72 | Ginsenoside Rh23 (Rh23) | C37H64O10 | 668.4499 | 668.4507 | 713.4489 | 1.06 | +HCOO |
8 | 11.2 | Vinaginsenoside R4 (vR4) | C48H82O19 | 962.545 | 962.5452 | 1007.5434 | 0.19 | +HCOO |
9 | 11.94 | Pseudo-ginsenoside F11 (pF11) | C42H72O14 | 800.4922 | 800.4932 | 845.4914 | 1.22 | +HCOO |
10 | 12.11 | Ginsenoside Rf (Rf) | C42H72O14 | 800.4922 | 800.4922 | 845.4904 | 0.01 | +HCOO |
11 | 12.81 | Notoginsenoside R2 (nR2) | C41H70O13 | 770.4816 | 770.4823 | 815.4805 | 0.83 | +HCOO |
12 | 13.15 | Notoginsenoside R4 (nR4) | C59H100O27 | 1240.6452 | 1240.6455 | 1285.6437 | 0.2 | +HCOO |
13 | 13.43 | Ginsenoside F5 (F5) | C41H70O13 | 770.4816 | 770.4819 | 815.4801 | 0.33 | +HCOO |
14 | 13.56 | Ginsenoside Rh1 (Rh1) | C36H62O9 | 638.4394 | 638.4392 | 683.4374 | 0.31 | +HCOO |
15 | 13.58 | 20(R)-Notoginsenoside R2 (nR2-R) | C41H70O13 | 770.4816 | 770.4815 | 815.4797 | 0.18 | +HCOO |
16 | 13.7 | Ginsenoside Rg2 (Rg2) | C42H72O13 | 784.4973 | 784.4984 | 829.4966 | 1.38 | +HCOO |
17 | 13.9 | Ginsenoside F3 (F3) | C41H70O13 | 770.4816 | 770.4811 | 815.4793 | 0.63 | +HCOO |
18 | 14.03 | 20(R)-Ginsenoside Rg2 (Rg2-R) | C42H72O13 | 784.4973 | 784.496 | 829.4942 | 1.58 | +HCOO |
19 | 14.03 | 20(R)-Ginsenoside Rh1 (Rh1-R) | C36H62O9 | 638.4394 | 638.4397 | 683.4379 | 0.47 | +HCOO |
20 | 14.35 | Ginsenoside Ra2 (Ra2) | C58H98O26 | 1210.6346 | 1210.6346 | 1255.6328 | 0.01 | +HCOO |
21 | 14.51 | Ginsenoside Ra3 (Ra3) | C59H100O27 | 1240.6452 | 1240.6447 | 1285.6429 | 0.36 | +HCOO |
22 | 14.53 | Ginsenoside Rb1 (Rb1) | C54H92O23 | 1108.6029 | 1108.6006 | 1153.5988 | 2.02 | +HCOO |
23 | 14.58 | Gypenoside XLIX (XLIX) | C52H86O21 | 1046.5662 | 1046.5658 | 1091.564 | 0.31 | +HCOO |
24 | 15.04 | Malonyl ginsenoside Rb1 (M-Rb1) | C57H94O26 | 1194.6033 | 1194.6057 | 1193.5984 | 2 | –H |
25 | 15.25 | Ginsenoside Rc (Rc) | C53H90O22 | 1078.5924 | 1078.5925 | 1123.5907 | 0.1 | +HCOO |
26 | 15.47 | Ginsenoside Ra1 (Ra1) | C58H98O26 | 1210.6346 | 1210.633 | 1255.6312 | 1.27 | +HCOO |
27 | 15.69 | Ginsenoside Ro (Ro) | C48H76O19 | 956.4981 | 956.4978 | 955.4905 | 0.28 | –H |
28 | 15.8 | Ginsenoside F1 (F1) | C36H62O9 | 638.4394 | 638.4395 | 683.4377 | 0.11 | +HCOO |
29 | 15.9 | Malonyl ginsenoside Rc (M-Rc) | C56H92O25 | 1164.5928 | 1164.5947 | 1163.5874 | 1.6 | –H |
30 | 16.25 | Ginsenoside Rb2 (Rb2) | C53H90O22 | 1078.5924 | 1078.5913 | 1123.5895 | 0.99 | +HCOO |
31 | 16.6 | Ginsenoside Rb3 (Rb3) | C53H90O22 | 1078.5924 | 1078.5915 | 1123.5897 | 0.81 | +HCOO |
32 | 16.9 | Malonyl ginsenoside Rb2 (M-Rb2) | C56H92O25 | 1164.5928 | 1164.5923 | 1163.585 | 0.4 | –H |
33 | 18.28 | Gypenoside A (GyA) | C46H74O17 | 898.4926 | 898.4915 | 943.4897 | 1.21 | +HCOO |
34 | 18.29 | Ginsenoside Rd (Rd) | C48H82O18 | 946.5501 | 946.5495 | 991.5477 | 0.59 | +HCOO |
35 | 18.97 | Malonyl ginsenoside Rd (M-Rd) | C51H84O21 | 1032.5505 | 1032.5498 | 1031.5425 | 0.7 | –H |
36 | 20.4 | Gypenoside XVII (GyXVII) | C48H82O18 | 946.5501 | 946.5497 | 991.5479 | 0.47 | +HCOO |
37 | 21.96 | Notoginsenoisde Fe (nFe) | C47H80O17 | 916.5396 | 916.5393 | 961.5375 | 0.22 | +HCOO |
38 | 23.29 | Compound O (CO) | C47H80O17 | 916.5396 | 916.5396 | 961.5378 | 0.1 | +HCOO |
39 | 23.46 | Ginsenoside Rg4 (Rg4) | C42H70O12 | 766.4867 | 766.4875 | 811.4857 | 0.91 | +HCOO |
40 | 23.84 | Ginsenoside Rk3 (Rk3) | C36H60O8 | 620.4288 | 620.4292 | 665.4274 | 0.51 | +HCOO |
41 | 24.28 | Ginsenoside F4 (F4) | C42H70O12 | 766.4867 | 766.4865 | 811.4847 | 0.27 | +HCOO |
42 | 24.68 | Ginsenoside Rh4 (Rh4) | C36H60O8 | 620.4288 | 620.4275 | 665.4257 | 2.01 | +HCOO |
43 | 25.15 | Gypenoside L (GyL) | C42H72O14 | 800.4922 | 800.4905 | 845.4887 | 2.1 | +HCOO |
44 | 25.19 | Ginsenoside F2 (F2) | C42H72O13 | 784.4973 | 784.4968 | 829.495 | 0.6 | +HCOO |
45 | 25.34 | Gypenoside LI (GyLI) | C42H72O14 | 800.4922 | 800.4909 | 845.4891 | 1.6 | +HCOO |
46 | 25.57 | Notoginsenoside Ft1 (nFt1) | C47H80O17 | 916.5396 | 916.5417 | 961.5399 | 2.26 | +HCOO |
47 | 25.78 | Protopanaxatiol (PPT) | C30H52O4 | 476.3866 | 476.3862 | 521.3844 | 0.71 | +HCOO |
48 | 26.01 | 20(S)-Ginsenoside Rg3 (Rg3) | C42H72O13 | 784.4973 | 784.498 | 829.4962 | 0.9 | +HCOO |
49 | 26.2 | 20(R)-Ginsenoside Rg3 (Rg3-R) | C42H72O13 | 784.4973 | 784.4989 | 829.4971 | 1.97 | +HCOO |
50 | 26.37 | Ginsenoisde Mc (Mc) | C41H70O12 | 754.4867 | 754.4867 | 799.4849 | 0 | +HCOO |
51 | 26.52 | Compound Y (CY) | C41H70O12 | 754.4867 | 754.4849 | 799.4831 | 2.3 | +HCOO |
52 | 27.35 | Compound K (CK) | C36H62O8 | 622.4445 | 622.4433 | 667.4415 | 1.8 | +HCOO |
53 | 27.43 | Ginsenoside Rk1 (Rk1) | C42H70O12 | 766.4867 | 766.4861 | 811.4843 | 0.81 | +HCOO |
54 | 27.55 | Ginsenoside Rg5 (Rg5) | C42H70O12 | 766.4867 | 766.4873 | 811.4855 | 0.73 | +HCOO |
55 | 27.7 | Ginsenoside Rh2 (Rh2) | C36H62O8 | 622.4445 | 622.4441 | 667.4423 | 0.52 | +HCOO |
56 | 29.04 | Ginsenoside Rk2 (Rk2) | C36H60O7 | 604.4339 | 604.4341 | 649.4323 | 0.35 | +HCOO |
57 | 29.15 | Ginsenoside Rh3 (Rh3) | C36H60O7 | 604.4339 | 604.434 | 649.4322 | 0.17 | +HCOO |
58 | 30.04 | Protopanaxadiol (PPD) | C30H52O3 | 460.3916 | 460.3917 | 505.3899 | 0.19 | +HCOO |
No. | Ginsenosides | Roots | Stems and Leaves | Berries | No. | Ginsenosides | Root | Stems and Leaves | Berry |
---|---|---|---|---|---|---|---|---|---|
1 | gRf | 1.8 ± 0.1 | 0.3 ± 0.1 | 3.6 ± 1.1 | 21 | Ro | 0.15 ± 0.01 | 0.014 ± 0.002 | 0.014 ± 0.002 |
2 | nR1 | 0.06 ± 0.01 | 0.03 ± 0.01 | 1.2 ± 0.2 | 22 | M-Rc | 0.9 ± 0.1 | 1.08 ± 0.04 | 4.7 ± 0.5 |
3 | Rg1 | 3.1 ± 0.2 | 9.6 ± 0.5 | 8.9 ± 4.3 | 23 | Rb2 | 0.6 ± 0.1 | 2.8 ± 0.1 | 2.3 ± 0.6 |
4 | Re | 3.0 ± 0.3 | 17 ± 1 | 26 ± 8 | 24 | Rb3 | not detected | 0.5 ± 0.1 | not detected |
5 | vR4 | 0.007 ± 0.001 | 1.2 ± 0.1 | 0.9 ± 0.1 | 25 | M-Rb2 | 0.9 ± 0.1 | 1.6 ± 0.1 | 6.8 ± 0.5 |
6 | Rf | 4.6 ± 0.2 | 0.30 ± 0.01 | 3.4 ± 1.1 | 26 | Rd | 0.15 ± 0.01 | 7.1 ± 0.2 | 2.3 ± 0.5 |
7 | nR2 | 1.1 ± 0.1 | 0.7 ± 0.1 | 4.5 ± 1.3 | 27 | M-Rd | 0.014 ± 0.001 | 3.1 ± 0.1 | 5.3 ± 0.4 |
8 | nR4 | 0.14 ± 0.02 | not detected | not detected | 28 | CO | 0.06 ± 0.01 | 12.6 ± 0.1 | 0.4 ± 0.1 |
9 | F5 | not detected | 5.8 ± 0.2 | 2.8 ± 0.3 | 29 | Rg4 | not detected | not detected | 0.06 ± 0.03 |
10 | Rh1 | 0.021 ± 0.002 | 0.24 ± 0.01 | 0.04 ± 0.02 | 30 | F4 | not detected | 0.4 ± 0.1 | 2.1 ± 0.8 |
11 | Rg2 | 0.17 ± 0.01 | 0.61 ± 0.03 | 0.6 ± 0.5 | 31 | F2 | 0.0019 ± 0.0006 | 2.7 ± 0.3 | 0.03 ± 0.01 |
12 | F3 | not detected | 5.3 ± 0.2 | 4.1 ± 0.4 | 32 | Rg3 | 0.0004 ± 0.0002 | 0.09 ± 0.01 | 0.007 ± 0.001 |
13 | Rg2-R | not detected | 0.008 ± 0.001 | 0.06 ± 0.03 | 33 | Mc | not detected | 0.24 ± 0.04 | not detected |
14 | F1 | not detected | not detected | 0.005 ± 0.001 | 34 | CY | not detected | 0.08 ± 0.02 | not detected |
15 | Ra2 | 3.2 ± 0.1 | not detected | not detected | 35 | CK | 0.0010±0.0004 | 0.003±0.001 | 0.002 ± 0.001 |
16 | Ra3 | 0.9 ± 0.1 | not detected | not detected | 36 | Rk1 | not detected | 1.18±0.02 | 1.153 ± 0.004 |
17 | Rb1 | 3.8 ± 0.3 | 0.08 ± 0.01 | 2.8 ± 0.6 | 37 | Rg5 | 0.031 ± 0.004 | not detected | 0.08 ± 0.01 |
18 | M-Rb1 | 4.7 ± 0.5 | 0.7 ± 0.1 | 9.9 ± 1.2 | 38 | Rh2 | not detected | 0.011 ± 0.002 | not detected |
19 | Rc | 0.9 ± 0.1 | 3.5 ± 0.1 | not detected | 39 | Rh1-R | not detected | 0.0028 ± 0.0004 | not detected |
20 | Ra1 | 0.6 ± 0.2 | not detected | not detected |
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Lee, J.W.; Choi, B.-R.; Kim, Y.-C.; Choi, D.J.; Lee, Y.-S.; Kim, G.-S.; Baek, N.-I.; Kim, S.-Y.; Lee, D.Y. Comprehensive Profiling and Quantification of Ginsenosides in the Root, Stem, Leaf, and Berry of Panax ginseng by UPLC-QTOF/MS. Molecules 2017, 22, 2147. https://doi.org/10.3390/molecules22122147
Lee JW, Choi B-R, Kim Y-C, Choi DJ, Lee Y-S, Kim G-S, Baek N-I, Kim S-Y, Lee DY. Comprehensive Profiling and Quantification of Ginsenosides in the Root, Stem, Leaf, and Berry of Panax ginseng by UPLC-QTOF/MS. Molecules. 2017; 22(12):2147. https://doi.org/10.3390/molecules22122147
Chicago/Turabian StyleLee, Jae Won, Bo-Ram Choi, Young-Chang Kim, Doo Jin Choi, Young-Seob Lee, Geum-Soog Kim, Nam-In Baek, Seung-Yu Kim, and Dae Young Lee. 2017. "Comprehensive Profiling and Quantification of Ginsenosides in the Root, Stem, Leaf, and Berry of Panax ginseng by UPLC-QTOF/MS" Molecules 22, no. 12: 2147. https://doi.org/10.3390/molecules22122147
APA StyleLee, J. W., Choi, B.-R., Kim, Y.-C., Choi, D. J., Lee, Y.-S., Kim, G.-S., Baek, N.-I., Kim, S.-Y., & Lee, D. Y. (2017). Comprehensive Profiling and Quantification of Ginsenosides in the Root, Stem, Leaf, and Berry of Panax ginseng by UPLC-QTOF/MS. Molecules, 22(12), 2147. https://doi.org/10.3390/molecules22122147