Chlorinated Didemnins from the Tunicate Trididemnum solidum
Abstract
:1. Introduction
2. Results and Discussion
2.1. Bioassay-Guided Isolation
2.2. Structural Elucidation of the New Compounds
1 a | 2 b | ||||
---|---|---|---|---|---|
Subunit | C# | δC | δH (J in Hz) | δC | δH (J in Hz) |
IsoSta or norSta | NH | - | 7.62 (d, 9.5) | - | 7.8 (d, 9.8) |
CO | 169.1 | - | 169.7 | - | |
C2H2 | 40.7 | 2.9 (m)/4.06 (d, 17.0) | 40.8 | 3.02 (m)/4.03 (d, 18.0) | |
C3H | 67.1 | 4.68 (t, 10) | 67.6 | 4.69 (t, 10.2) | |
C4H | 56.3 | 4.66 (brt, 9.5) | 57.7 | 4.51 (brt, 9.7) | |
C5H | 34.5 | 2.51 (m) | 27.7 | 2.5 (m) | |
C6H2/C6H3 | 28.1 | 1.45/1.73 (m) | 17.2 | 1.16 (d, 6.6) | |
C7H3 | 12.1 | 1.07 (t, 7.5) | - | - | |
C5CH3 | 14.6 | 1.18 (d, 7.0) | 22.1 | 1.22 (d, 6.3) | |
Hip | CO | 172.2 | - | 172.5 | - |
C2H | 49.4 | 4.27 * | 49.9 | 4.34 (q, 6.9) | |
C3 | 204.6 | - | 208.8 | - | |
C4H | 80.2 | 5.63 (d, 4.0) | 80.4 | 5.61 (d, 4.0) | |
C5H | 29.6 | 2.39 m | 29.8 | 2.43 (m) | |
C6H3 | 18.9 | 0.86 (d, 6.0) | 19.2 | 0.83 * | |
C5CH3 | 16.9 | 0.84 (d, 6.0) | 17.1 | 0.85 * | |
C2CH3 | 14.8 | 1.49 (d, 7.0) | 15.2 | 1.53 (d, 6.7) | |
Leu | NH | - | 8.31 (d, 9.0) | - | 8.35 (d, 9.0) |
CO | 171.2 | - | 171.4 | - | |
CαH | 49.4 | 5.21 (brt, 9.5) | 49.8 | 5.22 (brt, 9.4) | |
CβH2 | 41.8 | 1.96/1.68 (m) | 41.9 | 1.79/1.48 (m) | |
CγH | 24.7 | 1.70 (m) * | 24.9 | 1.9 (m) | |
CδH3 | 20.9 | 0.83 (d, 6.0) | 21.3 | 0.94 * | |
Cδ′H3 | 22.0 | 1.03 (d, 6.0) | 21.5 | 1.03 * | |
Pro | CO | 170.6 | - | 169.3 | - |
CαH | 57.8 | 4.83 (m) | 58.8 | 4.83 (m) | |
CβH2 | 27.7 | 1.96 (m),1.71 (m) | 27.9 | 2.04 (m), 1.78 (m) | |
CγH2 | 24.8 | 1.63 (m), 1.91 (m) | 24.9 | 1.58 (m), 1.90 (m) | |
CδH2 | 47.3 | 3.50 (m), 3.60 (m) | 47.5 | 3.50 (m), 3.58 (m) | |
Cl-N,O-Me2Tyr | CO | 170.6 | - | 170.9 | - |
NCH3 | 38.4 | 2.67 (s) | 38.8 | 2.66 (s) | |
CαH | 65.3 | 4.28 * | 65.7 | 4.26 (dd, 9.5, 5.2) | |
CβH2 | 33.9 | 3.50 (m) | 33.9 | 3.55 (m) | |
Cγ | 131.6 | - | 131.2 | - | |
CσH | 131.5 | 7.43 (s) | 131.8 | 7.44 (s) | |
Cε | 122.1 | - | 122.4 | - | |
Cξ | 154.1 | - | 154.5 | - | |
CρH | 112.7 | 7.02 (d, 8.0) | 113.2 | 7.02 (d, 8.0) | |
CψH | 129.3 | 7.26 (d, 8.0) | 129.7 | 7.28 (d, 8.0) | |
OCH3 | 55.9 | 3.78 (s) | 56.3 | 3.80 (s) | |
Thr | CO | 168.9 | - | 169.3 | - |
NH | - | 10.3 (d, 6.0) | - | 10.3 (d, 6.1) | |
CαH | 57.8 | 5.37 (brd, 6.5) | 58.1 | 5.38 (brd, 6.5) | |
CβH | 70.4 | 5.74 (brd, 5.5) | 70.5 | 5.77 (brd, 6.3) | |
Cβ-CH3 | 15.9 | 1.64 (d, 6.0) | 16.2 | 1.69 (d, 6.0) | |
MeLeu | CO | 169.6 | - | 170.6 | - |
NCH3 | 31.2 | 3.14 (s) | 31.8 | 3.15(s) | |
CαH | 59.6 | 4.8 * | 59.1 | 4.84 (m) | |
CβH2 | 39.5 | 2.15 (m) | 39.5 | 2.6 (m) | |
CγH | 25.0 | 1.68 (m) | 25.2 | 1.8 (m) | |
CδH3 | 23.4 | 0.84 (d, 6.0) | 23.7 | 0.94 (d, 5.6) | |
Cδ′H3 | 21.8 | 0.92 (d, 6.0) | 22.9 | 1.03 * |
Compound | iNOS | NF-κB |
---|---|---|
1 | 0.4 | 0.26 |
2 | 0.42 | 0.62 |
3 | 0.19 | 0.19 |
4 | 0.002 | 0.03 |
Parthenolide α | 2.8 | 2.8 |
Compound | SK-MEL | KB | BT-549 | SK-OV-3 | VERO |
---|---|---|---|---|---|
1 | 0.12 | 0.26 | 0.16 | 0.26 | 4.8 |
2 | 0.06 | 0.42 | 0.16 | 0.38 | 2.08 |
3 | 0.055 | 0.16 | 0.07 | 0.16 | 4.78 |
4 | 0.022 | 0.09 | 0.02 | 0.1 | 0.15 |
Doxorubicin α | 1.1 | 1.66 | 1.01 | 1.66 | 14 |
2.3. Acid Hydrolysis and Marfey Analysis
3. Experimental Section
3.1. General
3.2. Tunicate Material
3.3. Extraction and Isolation
3.4. Biological Assays
4. Conclusions
Acknowledgments
Conflicts of Interest
References
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Ankisetty, S.; Khan, S.I.; Avula, B.; Gochfeld, D.; Khan, I.A.; Slattery, M. Chlorinated Didemnins from the Tunicate Trididemnum solidum. Mar. Drugs 2013, 11, 4478-4486. https://doi.org/10.3390/md11114478
Ankisetty S, Khan SI, Avula B, Gochfeld D, Khan IA, Slattery M. Chlorinated Didemnins from the Tunicate Trididemnum solidum. Marine Drugs. 2013; 11(11):4478-4486. https://doi.org/10.3390/md11114478
Chicago/Turabian StyleAnkisetty, Sridevi, Shabana I. Khan, Bharathi Avula, Deborah Gochfeld, Ikhlas A. Khan, and Marc Slattery. 2013. "Chlorinated Didemnins from the Tunicate Trididemnum solidum" Marine Drugs 11, no. 11: 4478-4486. https://doi.org/10.3390/md11114478