Five D:C-friedo-oleanane triterpenes from the seeds of Trichosanthes kirilowii Maxim. and their anti-inflammatory effects.

Five triterpenes with a D:C-friedo-oleanane skeleton, D:C-friedo-oleana-7,9(11)-diene-3 beta,29-diol (3-epikarounidiol), 7-oxo-D:C-friedo-olean-8-en-3 beta-ol (7-oxoisomultiflorenol), 7-oxo-8 beta-D:C-friedo-olean-9(11)-ene-3 alpha,29-diol, D:C-friedo-olean-8-ene-3 alpha,29-diol (3-epibryonolol), and D:C-friedo-olean-8-ene-3 beta,29-diol (bryonolol), the first four of which are new naturally occurring compounds, were isolated from the seeds of Trichosanthes kirilowii Maxim. The structures were determined by spectral and chemical methods. 3-Epikarounidiol, 7-oxoisomultiflorenol, and 3-epibryonolol showed marked inhibitory activity against 12-O-tetradecanoylphorbol-13-acetate (TPA)-induced ear inflammation in mice. The 50% inhibitory dose of these triterpenes for TPA-induced inflammation (1 microgram) was 0.2-0.6 mg/ear.

Brominated polyacetylenic acids from the marine sponge Xestospongia muta: inhibitors of HIV protease.

The EtOAc extract of the sponge Xestospongia muta collected in Colombus Island, Bahamas, yielded eleven straight-chain unsaturated, polyacetylenic, brominated acids, seven of which were identified on the basis of spectral data, including the unknown acids 2-7. These acetylenic acids are the first known examples that have been shown to inhibit HIV protease, a critical enzyme in the replication of human immunodeficiency virus.

7-Oxodihydrokarounidiol [7-oxo-D:C-friedo-olean-8-ene-3 alpha,29-diol], a novel triterpene from Trichosanthes kirilowii.

The structure of 7-oxodihydrokarounidiol [7-oxo-D:C-friedo-olean-8-ene-3 alpha,29-diol], isolates from the seeds of Trichosanthes kirilowii (Cucurbitaceae), was determined by chemical correlation with karounidiol [D:C-friedo-oleana-7,9(11)-diene-3 alpha,29-diol] from the same source. Two other natural products, viz. bryonolic acid (3 beta-hydroxy-D:C-friedo-olean-8-en-29-oic acid) and bryononic acid (3-oxo-D:C-friedo-olean-8-en-29-oic acid), were also correlated with karounidiol.

The crystal structure of 3 beta-hydroxy-4 alpha, 23R, 24R-trimethyl-5 alpha-cholestane (23R, 24R-5 alpha-dinostanol) from dinoflagellates.

An x-ray crystal structure determination of a dinostanol from the dinoflagellate Protoceratium reticulatum and zooxanthellae from Orbulina universa was completed. The novel sterol was shown to be 3 beta-hydroxy-4 alpha, 23R,24R-trimethyl-5 alpha-cholestane and may be one of the molecular fossils found in sediment cores from the deepest Black Sea trench.

Minor and trace sterols in marine invertebrates 53 (1): Further novel marine sterols resulting from triple and quadruple biomethylation of the cholesterol side-chain.

The isolation and structure elucidation of nine new trace sterols with highly branched side chains from a Pseudaxinyssa species from the Australian Great Barrier Reef are described.

On the origin of terpenes in symbiotic associations between marine invertebrates and algae (zooxanthellae). Culture studies and an application of 13C/12C isotope ratio mass spectrometry.

13C/12C ratios of sets of compounds, algal sterols and terpenes, isolated from dinoflagellate symbiont (zooxanthellae)-bearing soft corals and gorgonians were determined. In most cases, a significant difference was found between the delta 13C values of the terpenes and of the algal sterols from the same set, the algal sterols containing less 13C than the terpenes. These results can only be explained if terpenes are synthesized by the host. Cultured zooxanthellae, isolated from symbiotic associations, do not make terpenes. Algal sterols of the various sets do not all have the same delta 13C value: average values range from -18.2 to -24.3%. A consistent difference of about 7% in the delta 13C values of sterols of cultured symbionts isolated from two of the gorgonians was found. This has potential applications for the taxonomy of zooxanthellae, most of which are believed by some specialists to be one discrete species.

Sterols of the cultured euglenid Eutreptia viridis: a novel delta 23-unsaturated sterol.

The sterol mixture isolated from the marine alga Eutreptia viridis consists mainly of delta 5,7-dienes which account for 80% of the free sterols. Eighteen different sterols were detected, including a novel sterol with the rare delta 23-unsaturation, viz. 24-ethylcholesta-5,7,23Z-trien-3 beta-o1.

Sterols of the cultured dinoflagellate Pyrocystis lunula.

Eighteen components of the sterol fraction of Pyrocystis lunula have been identified. In addition to 4 alpha-methyl sterols (typical dinoflagellate sterols), regular sterols, both with a saturated and delta 5-unsaturated skeleton, were isolated, together with delta 4-3-keto steroids including the hitherto unknown 23,24R-dimethyl-4,22E-cholestadien-3-one.

Sterol patterns of cultured zooxanthellae isolated from marine invertebrates: Synthesis of gorgosterol and 23-desmethylgorgosterol by aposymbiotic algae.

QUANTITATIVE STEROL COMPOSITIONS OF CULTURED ZOOXANTHELLAE ISOLATED FROM VARIOUS PACIFIC AND ATLANTIC INVERTEBRATE HOSTS: Zoanthus sociatus (a zoanthid), Oculina diffusa (a scleractian coral), Tridacna gigas (a giant clam), Melibe pilosa (a nudibranch), and Aiptasia pulchella (a sea anemone) are reported. The results clearly demonstrate large differences in sterol patterns of zooxanthellae and that there is no obvious relationship between the taxonomic affiliation of the host and the sterol pattern of its isolated symbiont. The sterols of the zooxanthellae of O. diffusa (Cnidaria) and T. gigas (Mollusca) are qualitatively equivalent. Based on the structures of the two major free sterols synthesized by each alga, the zooxanthellae from different hosts were separated into three distinct groups. It was also found that an aposymbiotic alga can synthesize the unique marine sterols gorgosterol and 23-desmethylgorgosterol. Most of the sterols were identified by using mass spectroscopy and 360-MHz proton magnetic resonance. Spectroscopic data are reported for four novel sterols-(23,24R)-dimethyl-5alpha-cholest-(22E)-en-3beta-o l, 23-methyl-5alpha-cholest-22E-en-3beta-ol, cholesta-5,14-dien-3beta-ol, and 4alpha-methyl-5alpha-cholesta-8(14)-24-dien-3beta-ol.

Isolation of two new C30 sterols, (24E)-24-N-propylidenecholesterol and 24 epsilon-N-propylcholesterol, from a cultured marine Chrysophyte.

Two new sterols, (24E)-24-n-propylidenecholesterol and 24 epsilon-n-propylcholesterol, were isolated from a cultured marine Chrysophyte. Since most of the steroids found in marine invertebrates are unchanged or modified sterols of algal or symbiotic origin, the discovery of these two unusual sterols in a unicellular alga grown under well-defined conditions contributes to our knowledge of sterols in marine food chains and offers a potential substrate for biosynthetic labeling experiments.