Aplysina

The only known example of an activated defense in sponges arises from investigations of the defensive chemistry of Aplysina aerophoba. A wound-activated transformation of stored pro-toxins was found after disruption of compart-mentalization of this sponge [157,158]. 

Scheme 21 Wound-activated bioconversion of brominated isoxazoline alkaloids by the sponge Aplysina aerophoba...

One of the first biosynthetic investigations undertaken in the Djerassi laboratory dealt with the sponge Aplysina fistularis. This sponge contains sterols with side-chain alkylations at C-24 and C-26, the aplysterols [37], The biosynthesis of these unconventional sterols was shown (Scheme 7) to proceed by a conversion of desmosterol (34) to epicodisterol (51) [but not its C-24 epimer, codisterol (52)] followed by methylation to 25(27)-dehydroaplysterol (53). Sterol... 

Gulavita, N.K. Pranponi, S.A. Wright, A.E. Garay, M. Sills, M.A. (1995) Aplysillin A, athrombin receptor antagonist from the marine sponge Aplysina fistularis fidva. J. Nat. Prod., 58, 954-7. 

Kloppel, A., Pfannkuchen, M., Putz, A., Proksch, P., and Brummer, F. (2008). Ex situ cultivation of Aplysina aerophoba close to in situ conditions Ecological, biochemical and histological aspects. Mar. Ecol. 29, 259-272. 

In addition to the sponge Terpios, many other kinds of sponges, soft corals, and algae cover corals compete for survival, including the sponges Dysidea sp. and Aplysina sp. 

Similarly, Aplysina sp.(Fig. 10.7), which show a dramatic change in color from yellow to black when exposed to air, contain cytotoxic compounds including bromotyrosine-derivative alkaloids, purealidins (Ishibashi et ah, 1991 Yagi et ah, 1993), aplysamine 2 (Xynas and Capon, 1989), and purpuramin G (Fattorusso et ah, 1970 Fig. 10.8). 

Fattorusso, E., Minale, L., Sodano, G., Moody, K., and Thomson, R. H. (1970). Aeroplysinin-I, a new bromo-compound from Aplysina aerophoba.. Chem. Soc. Chem. Commun. 751-752. 

Hernandez-Guerrero, C. J., Zubra, E., Ortega, M. J., and Carballob, J. L. (2007). Cytotoxic dibromotyrosine-derived metabolites from the sponge Aplysina gerardogreeni. Bioorg. Med. Chem. 15, 5275-5282. 

Xynas, R. and Capon, R. J. (1989). Two new bromotyrosine-derived metabolites from an Australian marine sponge, Aplysina sp. Aust. ]. Chem. 42,1427-1433. 

Aplysillin A (527), with unknown double bond geometries was isolated from Aplysina fistularis and is a weak thrombin receptor antagonist [442]. 

Other biologically active bromotyrosine-derived metabolites of marine origin include aeroplysinin, Fig. (48) as cytotoxic and tyrosine kinase inhibitor [382,383], fistularin isolated from Aplysina circheri which exhibited antiviral activity [384], and ceratinamides A and B, antifouling metabolites from Pseudoceratina purpurea [385],... 

A dibromotyrosin-derived metabolite present at 1.0% sponge dry weight, aerothionin (148), from Aplysina fistularis completely inhibits fish feeding when assayed in a 1.0% food pellet [115]. 

Fig. 3.31 Aplysina archeri, a Caribbean sponge containing several bromotyrosines, including 2100 and archerine (2101) (Photo J. R. Pawlik)...

The Mexican sponge Aplysina gerardogreeni contains calafianin (2106) (1880) (structure revised and confirmed by total synthesis, (1881-1883)), the known aerothionin, and the new phenylacetic acid 2107 (1880). These studies confirm that calafianin (2106) and aerothionin have the same absolute configuration (1883). Whereas aerothionin displays antibacterial activity against Mycobacterium tuberculosis, calafianin does not (1884). The Brazilian sponge Aplysina caissara contains the new caissarines A (2108) and B (2109) (1885). 

Fig. 6.1 Aplysina fistularis, a sponge rich in bromophenols and bromotyrosines (Photo F. J. Schmitz)...

Friedrich AB, Merkert H, Fendert T, Hacker J, Proksch P, Hentschel U (1999) Microbial Diversity in the Marine Sponge Aplysina cavernicola (formerly Verongia cavernicola) Analyzed by Fluorescence in Situ Hybridization (FISH). Mar Biol 134 461... 

Thoms C, Horn M, Wagner M, Hentschel U, Proksch P (2003) Monitoring Microbial Diversity and Natural Product Profiles of the Sponge Aplysina cavernicola Following Transplantation. Mar Biol 142 685... 

Hentschel U, Schmid M, Wagner M, Fieseler L, Gemert C, Hacker J (2001) Isolation and Phylogenetic Analysis of Bacteria with Antimicrobial Activities from the Mediterranean Sponges Aplysina aerophoba and Aplysina cavernicola. FEMS Microbiol Ecol 35 305... 

Friedrich AB, Fischer I, Proksch P, Hacker J, Hentschel U (2001) Temporal Variation of the Microbial Community Associated with the Mediterranean Sponge Aplysina aerophoba. FEMS Microbiol Ecol 38 105... 

Gulavita NK, Pomponi SA, Wright AE, Garay M, Sills MA (1995) Aplysillin A, a Thombin Receptor Antagonist from the Marine Sponge Aplysina fistularis fulva. J Nat Prod 58 954... 

Ciminiello P, Fattorusso E, Magno S, Pansini M (1996) Chemistry of Verongida Sponges VI. Comparison of the Secondary Metabolic Composition of Aplysina insularis and Aplysina fulva. Biochem Syst Ecol 24 105... 

Compagnone RS, Avila R, Suarez AI, Abrams OV, Rangel HR, Arvelo F, Pina IC, Merentes E (1999) ll-Deoxyfistularin-3, a New Cytotoxic Metabolite from the Caribbean Sponge Aplysina fistularis insularis. J Nat Prod 62 1443... 

Fendert T, Wray V, van Soest RWM, Proksch P (1999) Bromoisoxazoline Alkaloids from the Caribbean Sponge Aplysina insularis. Z Naturforsch 54c 246... 

Ciminiello P, Dell Aversano C, Fattorusso E, Magno S (2001) Archerine, a Novel Anti-Histaminic Bromotyrosine-Derived Compound from the Caribbean Marine Sponge Aplysina archeri. Eur J Org Chem 55... 

Encamacion RD, Sandoval E, Malmstr0m J, Christophersen C (2000) Calafianin, a Bromotyrosine Derivative from the Marine Sponge Aplysina gerardogreeni. J Nat Prod 63 874... 

Ogamino T, Nishiyama S (2005) Synthesis and Structure Revision of Calafianin, a Member of the Spiroisoxazole Family Isolated from the Marine Sponge, Aplysina gerardogreeni. Tetrahedron Lett 46 1083... 

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