Lissoclinum patella

Schmidt, E.W., Nelson, J.T., Rasko, D.A. et al. (2005) Patellamide A and C biosynthesis by a microcin-like pathway in Prochloron didemni, the cyanobacterial symbiont of Lissoclinum patella. Proceedings of the National Academy of Sciences of the United States of America, 102, 7315. 

Bodoi, C.D.J. Pattenden, G. (2000) Total syntheses and re-assignment of configurations of the cyclopeptides lissoclinamide and lissoclinamide 5 from Lissoclinum patella. J. Ch n. Soc., Perkin Trans. 1, 875-82. 

The heptapeptide ulicyclamide (15) and the octapeptide ulithiacyclamide (16) were the first representatives of a series of cyclic peptides to be isolated from Lissoclinum patella. Their structures were elucidated by interpretation of spectral data [44], A revised structure was later put forward for ulicyclamide (15) as a result of a detailed analysis of the fast atom bombardment (FAB) mass spectrum. The same paper reported the isolation of two more polar cyclic peptides and another, which was present as a minor component. These heptapeptides were called lissoclinamides 1-3 (17-19) [45]. An unidentified tunicate from the Great Barrier Reef contained ulithiacyclamide (16) and ascidiacyclamide (14) [46]. Two syntheses of ulithiacyclamide (16)... 

A series of macrolides bearing a thiazole moiety have been isolated from tunicates and sponges. The tunicate Lissoclinum patella has afforded the patellazoles A-C (428-430), which were found to be potent cytotoxins in the NCI human cell line protocol with mean IC50 values of 10-3—10-6 pg/ml as well as exhibiting antifungal activity [334, 335]. Furthermore, patellazole B (429) exhibited very potent antiviral activity against Herpes symplex viruses [334],... 

Two cyclic peptides that were isolated from the marine tunicate Lissoclinum patella,30 named ulicyclamide and ulithiacyclamide, have structures (33) and (34). 

Schmidt EW, Nelson JT, Rasko DA, Sudek S, Eisen JA, Haygood MG, Ravel J (2005) Patellamide A and C Biosynthesis by a Microcin-like Pathway in Prochloron didemni, the Cyanobacterial Symbiont of Lissoclinum patella. Proc Natl Acad Sci USA 102 7315... 

Ascidians are marine filter feeders with a rich natural products chemistry that five commonly associated with symbiotic bacteria (88, 89, 109). A well-studied symbiosis consists of photosynthetic Prochloron spp. cyanobacteria that occur in ascidians of the family Didemnidae (110). Prochloron spp. also can be found in bacterial mat structures of stromatoliths (111) but so far have not been detected outside of such structured environments. From didemnid ascidians, numerous cytotoxic cyclic peptides of the patellamide group (Fig. 5) were isolated (109, 112, 113). Mechanical separation of the Prochloron sp. symbiont from its host Lissoclinum patella and subsequent genome sequencing revealed a set of biosynthetic genes that after transfer into E. coli enabled this bacterium to produce two different patellamides (114). The genes also were identified in an independent study by screening a library of Prochloron sp. DNA... 

Figure 1. Structures o/Lissoclinum patella cyclic peptides...

As all the cyclic peptides isolated from Lissoclinum patella had been found to bind both copper and zinc in the circular dichroism study it was decided to further investigate... 

The text of this was modified from the PhD thesis of L. A. Morris, Studies on the Cu(II) and Zn(II) binding properties of cyclic peptides from the ascidian Lissoclinum patella, Aberdeen University, Aberdeen, 1999. 

The cyclamides are small cyclic peptides that characteristically contain multiple thiazole, thiazoline, oxazole, and oxazoline rings, which are derived from cysteine, serine, and threonine residues. Some of the first examples of this class to be described were the patellamides (53-55) from the tunicate Lissoclinum patella, although it was later determined they were produced by the symbiotic cyanobacterium Prochloron sp. The structures were solved by a combination of acid hydrolysis and GC analysis, coupled with 2D NMR. Smaller cyclic peptides from this class include the hexapeptides westiellamide (56) and microcyclamide (57) from M. aeruginosa Many members of the class possess cytotoxic properties, although their biological function or mechanism of action is not fully understood. In contrast to many cyanobacterial peptides, aside from the unusual heterocyclic residues, these peptides generally contain only ribosomal amino acids. 

A review describes the pharmacological properties of l,2-benzisothiazoles. In connection with thiazoles, we find several reviews or papers thiazoles in food aromas patellamides, which are antineoplastic cyclic peptides, from the marine tunicate Lissoclinum patella, which contain an unusual fused oxazoline-thiazole unit and polythiazole-containing peptide antibiotics. An interesting total synthesis of the aglycon of bleomycin A2 should also be mentioned. ... 

Patellazoles A-C (77-79), 24-membered thiazole-containing macrolides, were isolated from two specimens of didemnid tunicate, Lissoclinum patella, which were collected from the Fiji Islands [148] and Piti Bomb Holdes, Guam [149]. The patellazoles were potent cytotoxins in the NCI human cell line protocol with mean IC50 values of 10" to 10 pg/ml and antifungal activity against Candida albicans. 

Corley, D. G., Moore, R. E., and Paul, V. J. (1988). Patellazole B A novel cytotoxic thiazole-containing macrolide from the marine tunicate Lissoclinum patella. J. Am. Chem. Soc. 110, 7920-7922. 

Cyclopeptide from the marine tunicate Lissoclinum patella. Cytotoxic. Amorph. solid, [aj +40 (c, 0.1 in MeOH). 

Wasylyk, J. M., J. E. Biskupiak, C. E. Costello, and C. M. Ireland Cyclic peptide structures from the Tunicate Lissoclinum Patella by FAB mass spectrometry. J. Organ. Chem. (USA) 48, 4445 (1983). 

Remember that this species, which can be regarded as fixed, was discovered through the symbiotic relationship that it maintains with ascidians of the family Didemnidae, in particular Diplosoma similis and D. virens, Lissoclinum patella and I. voeltzkowi, Trididemnum cyclops and, more recentiy, the genus Polysyncraton (Duclaux, Lafargue, and Wahl, 1998). These relations have considerable importance insofar as the Didemnidae frequently contain antiviral and antitumor substances whose true origin is probably Prochloron. In our current state of knowledge, it has not yet been possible to cultivate in vitro-isolated... 

Cyclic peptides and depsipeptides constitute the bulk of the nitrogenous metabolites of didemnid tunicates and several publications have been devoted to them, either wholly or in part, such as Ireland et al. (1989), Davidson (1993) and Lehrer et al. (2003). However, many publications devoted to cyclic peptides of Didemnidae are concerned with only three species, Didemnum molle, Lissoclinum bistratum and Lissoclinum patella, which is the most prolific didemnid as regards cyclic peptides. The two Lissoclinum species were harvested in the Western Pacific (Australia, Fiji, Guam, Indonesia, Palau, Philippines, Pohnpei and Singapore) and Didemnum molle in the Indian Ocean (Comoros, Mozambique). 

Lissoclinum bistratum contains mostly cyclic hexapepti-des/ but Lissoclinum patella has yielded patellamides A-G (Figure 28.15), which are regarded as octapeptides, as well as ulithiacyclamides A and B and pre-ulithiacydamide these last three peptides are characterized by the presence of an intracyclic disulfide bridge. Lissoclinum patella has also yielded asddiacydamide, which had been isolated in 1983 from an tmdetermined ascidian, and tawicyclamides A and which appear to be currently the only cyclic peptides containing only thiazoles or thiazolines. These... 

Figure 28.15 Examples of cyclic peptides isolated from Lissoclinum patella.

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