E- and Z-Isomers of New Phytoecdysteroid Conjugates from French Polynesian Microsorum membranifolium (Polypodiaceae) Fronds
Abstract
:1. Introduction
2. Results and Discussion
Phytoecdysteroid | Retention time (min) | ||
---|---|---|---|
System A | System B | System C | |
1 | 25.7 | 15.9 | 15.6 |
2 | 26.7 | 12.3 | 17.6 |
3 | 34.0 | 9.2 | 14.2 |
4 | 32.0 | 25.2 | 13.5 |
5 | 33.5 | 19.2 | 16.0 |
6 | 41.0 | 12.7 | 12.7 |
20-hydroxyecdysone | 7.5 | 16.0 | 9.4 |
2-deoxy-20-hydroxyecdysone | 15.4 | 8.3 | 6.0 |
2-deoxyecdysone | 24.1 | 6.1 | 5.0 |
3. Experimental
3.1. General
3.2. Plant Material
3.3. Extraction and Isolation
3.4. Analytical HPLC Methods
δH (1) | δH (2) | δH (3) | δH (4) | δH (5) | δH (6) | |
---|---|---|---|---|---|---|
Hax−1 | 1.46 | 1.46 | ||||
Heq-1 | 1.76 | 1.76 | ||||
Hax-2 | 1.87 | 1.87 | 1.77 | |||
Heq-2 | 1.94 | 1.94 | ||||
Heq-3 | 5.16 (s, br, w1/2 = 13) | 5.18 (s, br, w1/2 = 13) | 5.16 (s, br, w1/2 = 14) | 5.12 (s, br, w1/2 = 13) | 5.11 (s, br, w1/2 = 13) | 5.11 (s, br, w1/2 = 13) |
Hax-4 | 1.77 | 1.77 | 1.77 | 1.77 | ||
Heq-4 | 1.87 | 1.87 | 1.87 | 1.87 | ||
H-5 | 2.38 (d, d, 12.3, 4.0) | 2.40 (d, d, 12.3, 4.0) | 2.41 (d, d, 12.6, 4.2) | 2.15 | 2.2 | 2.2 |
H-7 | 5.84 (d, 2.1) | 5.84 (d, 2.4) | 5.85 (d, 2.0) | 5.80 (d, 2.1) | 5.81 (d, 2.1) | 5.81 (d, 2.1) |
Hax-9 | 3.28 | 3.27 | 3.27 (m, w1/2 = 26) | 3.21 | 3.23 | 3.21 |
Hax-11 | 1.68 | 1.68 | 1.67 | 1.63 | 1.67 | |
Heq-11 | 1.76 | 1.76 | 1.78 | 1.71 | 1.78 | |
Hax-12 | 2.15 | 2.15 (t, d, 13.0, 4.8) | 2.13 (t, d, 13.0, 4.8) | 2.13 | 2.13 | |
Heq-12 | 1.86 | 1.88 | 1.78 | 1.87 | ||
Hax-15 | 2.00 | 2.00 | 1.98 | 2.00 | 1.98 | |
Heq-15 | 1.63 | 1.63 | 1.62 | 1.63 | 1.62 | |
Hax-16 | 2.00 | 2.00 | 1.98 | 2.00 | 2.00 | 1.98 |
Heq-16 | 1.76 | 1.76 | 1.51 | 1.76 | 1.76 | 1.51 |
H-17 | 2.42 (t, 9.9) | 2.42 (t, 9.9) | 2.06 | 2.42 | 2.42 | 2.06 |
Me-18 | 0.908 (s) | 0.907 (s) | 0.745 (s) | 0.880 (s) | 0.890 (s) | 0.735 (s) |
Me-19 | 1.010 (s) | 1.010 (s) | 1.010 (s) | 0.890 (s) | 0.910 (s) | 0.910 (s) |
H-20 | 1.77 | 1.77 | ||||
Me-21 | 1.203 (s) | 1.203 (s) | 0.957 (d, 6.6) | 1.203 (s) | 1.203 (s) | 0.950 (d, 6.6) |
H-22 | 3.36 | 3.35 | 3.61 (d, br, 10.1) | 3.36 | 3.35 | 3.61 |
Ha-23 | 1.31 | 1.31 | 1.33 | 1.31 | 1.31 | 1.33 |
Hb-23 | 1.69 | 1.69 | 1.55 | 1.69 | 1.69 | 1.55 |
Ha-24 | 1.81 | 1.81 | 1.79 | 1.81 | 1.81 | 1.79 |
Hb-24 | 1.44 | 1.46 | 1.42 | 1.44 | 1.46 | 1.42 |
Me-26 | 1.197 (s) | 1.197 (s) | 1.200 (s) | 1.197 (s) | 1.197 (s) | 1.195 (s) |
Me-27 | 1.211 (s) | 1.211 (s) | 1.210 (s) | 1.211 (s) | 1.211 (s) | 1.205 (s) |
H-1' | 4.86 (d, 7.3) | 4.98 (d, 7.3) | 4.98 (d, 7.3) | 4.82 (d, 7.3) | 4.96 (d, 7.3) | 4.96 (d, 7.3) |
H-2' | 3.53 | 3.53 (d, d, 9.0, 7.5) | 3.53 (d, d, 9.0, 7.5) | 3.48 | 3.53 | |
H-3' | 3.48 | 3.48 (t, 9.0) | 3.48 (t, 9.0) | 3.48 | ||
H-4' | 3.42 | 3.43 (d, d, 9.5, 8.6) | 3.43 (d, d, 9.5, 8.6) | 3.43 | ||
H-5' | 3.46 | 3.45 (d, d, d, 9.5, 5.2, 2.2) | 3.45 (d, d, d, 9.5, 5.2, 2.2) | 3.46 | 3.44 | |
H-6' | 3.72 (d, d, 12.5, 5.3) | 3.70 (d, d, 12.0, 5.0) | 3.70 (d, d, 12.0, 5.0) | 3.72 (d, d, 12.5, 5.3) | 3.70 (d, d, 12.0, 5.0) | 3.70 (d, d, 12.0, 5.0) |
H-6' | 3.91 (d, d, 12.2, 1.8) | 3.89 (d, d, 12.2, 1.8) | 3.89 (d, d, 12.2, 1.8) | 3.91 (d, d, 12.5, 2.0) | 3.89 (d, d, 12.2, 1.8) | 3.89 (d, d, 12.2, 1.8) |
H-2" | 7.14 (d, 1.8) | 7.31 (s, w1/2 = 3) | 7.31 (s, w1/2 = 3) | 7.15 (s, w1/2 = 3) | 7.56 (s, w1/2 = 3) | 7.56 (s, w1/2 = 3) |
H-5" | 7.21 (d, 8.6) | 7.19 | 7.19 | 7.19 (d,8.6) | 7.17 (d,8.6) | 7.17 (d, 8.6) |
H-6" | 7.08 (d, d, 8.3, 1.8) | 7.19 | 7.19 | 7.00 (d, d, 8.3, 1.8) | 7.13 (d, d, 8.6, 1.8) | 7.13 (d, d, 8.6, 1.8) |
H-7" | 7.60 (d, 16.1) | 7.66 (d, 16.0) | 7.66 (d, 15.8) | 6.97 (d, 12.8) | 6.97 (d, 12.8) | 6.97 (d, 12.8) |
H-8" | 6.40 (d, 16.1) | 6.50 (d, 16.0) | 6.50 (d, 15.8) | 5.90 (d, 12.8) | 5.93 (d, 12.8) | 5.93 (d, 12.8) |
H-10" | 3.92 (s) | 3.92 (s) | 3.87 (s) | 3.87 (s) |
Multiplicity | δC (1) | δC (2) | δC (3) | δC (4) | δC (5) | δC (6) | |
---|---|---|---|---|---|---|---|
C-1 | CH2 | 30.1 | 30.1 | 30.1 | 30.1 | 30.4 | |
C-2 | CH2 | 26.3 | 26.3 | 26.3 | |||
C-3 | CH | 69.5 | 69.4 | 69.4 | 69.5 | 69.4 | 69.4 |
C-4 | CH2 | 26.3 | 30.3 | ||||
C-5 | CH | 53.1 | 53.0 | 53.1 | 52.8 | 52.9 | 53.0 |
C-6 | C | * | 206.1 | 205.6 | * | * | * |
C-7 | CH | 121.8 | 121.7 | 121.5 | 121.8 | 121.7 | 121.5 |
C-8 | C | * | * | * | * | * | * |
C-9 | CH | 37.8 | 37.3 | 37.4 | 37.8 | 37.5 | |
C-10 | C | 37.3 | 37.4 | ||||
C11 | CH2 | 21.4 | 21.5 | 21.5 | |||
C12 | CH2 | 32.4 | 32.5 | 32.0 | 32.4 | 32.5 | 32.1 |
C-13 | C | 49.0 | 49.0 | 48.2 | 49.0 | 49.0 | 47.4 |
C-14 | C | 85.6 | 85.4 | 85.4 | 85.6 | 85.6 | 85.4 |
C-15 | CH2 | 31.6 | 31.7 | 31.6 | 31.6 | 31.7 | 31.6 |
C-16 | CH2 | 21.4 | 21.4 | 26.9 | 21.4 | 21.4 | 26.9 |
C-17 | CH | 50.5 | 50.5 | 48.6 | 50.5 | 50.5 | 48.6 |
C-18 | CH3 | 17.9 | 17.9 | 15.9 | 17.9 | 17.9 | 15.9 |
C-19 | CH3 | 24.2 | 24.2 | 24.2 | 24.2 | 24.2 | 24.2 |
C-20 | C | 77.7 | 77.7 | 43.3 CH | 77.7 | 43.3 CH | |
C-21 | CH3 | 20.9 | 20.8 | 13.0 | 20.9 | 20.8 | 13.0 |
C-22 | CH | 78.3 | 78.3 | 75.0 | 78.3 | 78.3 | 75.0 |
C-23 | CH2 | 27.3 | 27.3 | 25.2 | 25.2 | ||
C-24 | CH2 | 42.3 | 42.2 | 42.2 | 42.3 | 42.2 | 42.2 |
C-25 | C | 71.3 | 71.1 | 71.1 | 71.3 | 71.1 | 71.1 |
C-26 | CH3 | 28.9 | 29.0 | 29.0 | 28.9 | 29.0 | 29.0 |
C-27 | CH3 | 29.7 | 29.3 | 29.3 | 29.7 | 29.3 | 29.3 |
C-1' | CH | 103.3 | 102.1 | 102.1 | 103.3 | 102.1 | 102.1 |
C-2' | CH | 74.6 | 74.9 | 74.9 | 74.6 | 74.9 | 74.9 |
C-3' | CH | 77.5 | 77.6 | 77.6 | 77.5 | 77.6 | 77.6 |
C-4' | CH | 71.2 | 71.29 | 71.3 | 71.2 | 71.29 | 71.3 |
C-5' | CH | 78.1 | 78.1 | 78.1 | 78.1 | 78.1 | 78.1 |
C-6' | CH2 | 62.3 | 62.4 | 62.2 | 62.3 | 62.4 | 62.2 |
C-1" | C | 131.0 | 130.4 | 130.4 | 132.1 | 131.2 | |
C-2" | CH | 115.9 | 112.3 | 112.3 | 117.8 | 114.9 | 114.8 |
C-3" | C | 148.4 | 150.7 | 150.7 | 147.8 | 150.1 | |
C-4" | C | 148.7 | 149.5 | 149.5 | 146.8 | 147.9 | 148.9 |
C-5" | CH | 117.9 | 117.1 | 117.1 | 117.6 | 117.0 | 117.0 |
C-6" | CH | 122.2 | 123.4 | 123.4 | 122.7 | 124.8 | 124.7 |
C-7" | CH | 146.0 | 145.8 | 145.8 | 143.5 | 143.8 | |
C-8" | CH | 117.3 | 117.5 | 117.5 | 119.9 | 119.4 | 119.5 |
C-9" | C | 168.1 | 168.0 | 168.0 | 162.2 | 167.5 | |
C-10" | CH3 | 56.7 | 56.7 | 56.3 | 56.7 |
4. Conclusions
Acknowledgments
- Samples Availability: Samples of E-2-deoxy-20-hydroxyecdysone 3-[4-(1-β-D-glucopyranosyl)]-caffeate, E-2-deoxy-20-hydroxyecdysone 3-[4-(1-β-D-glucopyranosyl)]-ferulate, E-2-deoxyecdysone 3-[4-(1-β-D-glucopyranosyl)]-ferulate are available from the authors.
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Ho, R.; Girault, J.-P.; Raharivelomanana, P.; Lafont, R. E- and Z-Isomers of New Phytoecdysteroid Conjugates from French Polynesian Microsorum membranifolium (Polypodiaceae) Fronds. Molecules 2012, 17, 11598-11606. https://doi.org/10.3390/molecules171011598
Ho R, Girault J-P, Raharivelomanana P, Lafont R. E- and Z-Isomers of New Phytoecdysteroid Conjugates from French Polynesian Microsorum membranifolium (Polypodiaceae) Fronds. Molecules. 2012; 17(10):11598-11606. https://doi.org/10.3390/molecules171011598
Chicago/Turabian StyleHo, Raimana, Jean-Pierre Girault, Phila Raharivelomanana, and René Lafont. 2012. "E- and Z-Isomers of New Phytoecdysteroid Conjugates from French Polynesian Microsorum membranifolium (Polypodiaceae) Fronds" Molecules 17, no. 10: 11598-11606. https://doi.org/10.3390/molecules171011598