A non-peroxide norsesterterpene from a marine spongeHyrtios erecta

Summary A new norsesterterpene, hyrtial4, and known sesterterpenes,1–3, have been isolated from an anti-inflammatory active crude extract of the spongeHyrtios erecta.This sponge,Hyrtios (Heteronema) erecta Keller 1889, collected in 1980/81, from Tonga was extremely abundant in the Vava'u Is. Group.We thank Prof. R. Jacobs and his research group at UCSB for this data.     

A potent actomyosin ATPase activator from the Okinawan marine spongeAgelas cf.nemoechinata

Summary A bromine-containing alkaloid, oxysceptrin, has been isolated as a potent actomyosin ATPase activator from the Okinawan marine spongeAgelas cf.nemoechinata, and the structure elucidated to be1 on the basis of the 2D NMR spectral data.Acknowledgments. We thank Mr Z. Nagahama for his help in sponge collecting and Ms M. Takamatsu for her technical assistance.     

Furodendin,a C22 degraded terpene from the spongePhyllospongia dendyi

Summary The structure of furodendin (5), a minor secondary metabolite of the spongePhyllospongia dendyi, has been solved by spectral methods. Furodendin is probably derived, biosynthetically, by elimination of a C₃ unit from a C₂₅ geranyl-farnesol precursor.Acknowledgment. We thank Dr C. Evans for sponge identification, RRIMP Museum number FN 1516/000.     

Luffariellolide,an anti-inflammatory sesterterpene from the marine spongeLuffariella sp.

Summary Luffariellolide (2) is a sesterterpene from the Palauan spongeLuffariella sp. that has useful anti-inflammatory properties. In contrast with the irreversible action of manoalide (1) on phospholipase A₂, luffariellolide (2) is a slightly less potent but partially reversible PLA₂ inhibitor.30 December 1986Acknowledgment We thank Edward Luedtke, Elise Clason and Ellen Snideman for performing some of the assays reported above. The sponge was identified by Dr. Klaus Rützler, Smithsonian Institution, Washington, D.C. The research was supported by grants from Allergan Pharmaceuticals and the California Sea Grant College Program (Projects R/MP-30 and R/MP-31).     

Antimicrobial metabolites of the marine spongeAxinella polycapella

Summary Extracts of the marine spongeAxinella polycapella contain 1,2,4-trihydroxybenzene (1) and 2,2,4,4,5,5-hexahydroxybiphenyl (3) as antimicrobial constituents. Methods of synthesizing3 by, oxidative dimerization of1 were examined.Acknowledgment. We are grateful to Dr Klaus Reutzler for identifying the sponge and one of us (SW) is pleased to acknowledge fellowship support (1-F32-AI_05883-02) from the Public Health Service.     

Possible origin of zeaxanthin in the marine sponge,Reniera japonica

As part of a study to clarify the origins of biologically active substances in marine sponges, the carotenoids produced by two species of marine bacteria,Flexibacter sp. strain number DK30213 and DK30223, associated with the marine sponge,Reniera japonica, were investigated. Both bacteria were found to produce zeaxanthin [(3R, 3R)-dihydroxy-,-carotene] which is widely distributed in marine organisms. This carotenoid was also detected in the host sponge, suggesting the transport of zeaxanthin from the microorganisms to the host. As zeaxanthin plays the role of a quencher and scavenger for active species of oxygen, it is presumed that the sponge accumulates the bacterial product as a defense substance against the active oxygen species produced under irradiation by strong sunlight. It is thought that the bacteria are symbionts of the host sponge and act by obtaining the solid substrate and medium needed for settlement and growth from the host, and by producing and transmitting the biologically active substance to the host. Zeaxanthin-producing bacteria are also considered to have potential for practical uses by the aquacultural, pharmaceutical and food industries.     

Further sesterterpenes from the spongeSpongia nitens: 12-epi-scalaradial and 12,18-diepi-scalaradial

Summary 2 new tetracarbocyclic sesterterpenes, isomers of the previously² described scalaradial (1), have been isolated from the marine spongeSpongia nitens and their structures have been established to be2 and3; during the structural work, evidence on the stereochemistry of1,2 and3 has been obtained.This work is part of the Progetto Finalizzato per l'Oceanografia e i Fondi Marini, C.N.R., Roma. We thank the Zoological Station (Naples) for the collection of the sponge, A. Crispino, C. Di Pinto and A. Milone for their technical assistance and Prof. C. Santacroce for generous gifts of scalaradial.     

Furan fatty acid steryl esters from the marine spongeDictyonella incisa which show inflammatory activity

Summary Three new furan fatty acids, (9Z, 19Z)-3, 6-epoxyhexacosa-3,5,19-tetraenoic acid (1a), (8Z, 11Z, 14Z, 17Z)-3, 6-epoxyeicosa-3,5,8,11,14,17-hexaenoic acid (2a), and (8Z, 11Z, 14Z, 17E)-3, 6-epoxyeicosa-3,5,8,11,14,17-hexaenoic acid (3a), and a new polyunsaturated fatty acid (5Z, 8Z, 11Z, 14Z, 17E)-eicosa-5,8,11,14,17-pentaenoic acid (6a), present in the spongeDictyonella incisa as the respective steryl esters, have been isolated as methyl esters and their structures have been determined by spectral and chemical analysis. The furan fatty acid esters have shown a high inflammatory activity, which suggests their potential role as feeding deterrents.     

A novel xanthone as secondary metabolite fromCentaurium cachanlahuen

Summary From the plantCentaurium cachanlahuen, swertiaperenine1, swercherine2, decusatine4, oleanolic acid5 and the xanthone 1,8-dihydroxy-2,3,4,6-tetramethoxy-9H-xanthone3 were isolated and characterized.     

A new 9,11-secosterol,stellettasterol from a marine spongeStelletta sp

A new 9,11-secosteroid, stellettasterol (1) was isolated from a Japanese marine sponge,Stelletta sp.; its structure was determined by spectroscopic analysis. All NMR signals of1 were unambiguously assigned by application of various 2D NMR techniques. Stellettasterol exhibited antifungal activity againstMortieralla ramannianus.Part 62 of the Bioactive Marine Metabolites series. Part 61: Fusetani, N., Takahashi, M., and Matsunaga, S., Tetrahedron, in press.     

Isometachromin,a new cytotoxic sesquiterpenoid from a deep water sponge of the family Spongiidae

Isometachromin (1), a new sesquiterpene-quinone that is related structurally to metachromin C (2), and the known compounds ilimaquinone (3) and and 5-epi-ilimaquinone (4), were isolated from a deep water sponge in the family Spongiidae; the structure of isometachromin was elucidated by spectral methods. Isometachromin exhibits in vitro cytotoxicity against the human lung cancer cell line A 549 (IC₅₀=2.6 g/ml), but not against P 388 murine leukemia (IC₅₀10 g/ml) and also exhibits antimicrobial activity.This research is Harbor Branch Oceanographic Institution (HBOI) contribution number 911. We thank Drs S. A. Pomponi and M. Kelly-Borges (HBOI) for sponge taxonomy, and Dr P. McCarthy and T. Peterson (HBOI) for antimicrobial data.     

1,1-Dimethyl-5,6-dihydroxyindolinium chloride from a deep water marine sponge,Dercitus sp.

Summary 1,1-Dimethyl-5,6-dihydroxyindolinium chloride (1a)was identified from a deep water sample of the marine sponge,Dercitus sp., and its structure was elucidated by spectral methods.Acknowledgments. This is Harbor Branch Oceanographic Institution, Inc., SeaPharm Project Contribution No. 612. We thank Drs K. Rinehart, Jr, S. Pomponi and E. Armstrong for sponge collection.     

Zur Stereochemie der Propandioldehydrase-Reaktion

Summary Propanedioldehydrase is shown to convert both (+)-(S)-2-²H-propanediol,3, and (–)-(R)-1-²H₂-propanediol,5, to specimens of deuterated propion-aldehyde, for which the (S)-configuration has been established. Thus, in the propanedioldehydrase reaction migration of hydrogen atoms from C–1 to C–2 always occurs with inversion of configuration.     

Furospongolide,a new C21 furanoterpene from a marine organism

Summary The structure of a new linear C₂₁ furanoterpene, furospongolide (1), obtained from the marine spongeDysidea herbacea, was determined by spectral means.We thank Professor J. Vacelet for the identification and Dr Loya and Mr Benayahu for the collection of the sponge.     

Observations on the toxicity and metabolic relationships of polygodial,the chemical defense of the nudibranchDendrodoris limbata

Summary Polygodial (1), the defense metabolite stored in the skin of the nudibranchDendrodoris limbata, is toxic for the mollusc itself when injected into the hepatopancreas. Biosynthetic experiments using labeled mevalonic acid were devised to investigate a possible metabolic relationship between1 and the mixture of sesquiterpenoidic esters2, stored in the hepatopancreas. The results suggest that1 and2 are biosynthesized by independent pathways.Thanks are due to G. Villani for supplyingDendrodoris limbata and to A. Trabucco for technical assistance.     

Guggulsterol-like steroids from the Mediterranean gorgonianLeptogorgia sarmentosa

Summary Several polyoxygenated steroids (1, 2, 3) have been isolated from the marine gorgonianLeptogorgia sarmentosa. One of these (1) is the known guggulsterol III, previously found in the pharmacologically active resin from the treeCommiphora mukul; the others,2 and3, have not been found before in nature, and are closely related to1. During the structural work apparent anomalies in the CMR-spectra of1 were observed.The authors are grateful to Prof. Sukh Dev for the PMR-spectra of guggulsterol III. Thanks are also due to Zoological Station (Naples), for the collection of the gorgonian, to Centro Metodologie Chimico-Fisiche, Università di Napoli, for recording PMR-spectra on WH-270 Superconducting Spectrometer-Bruker, to Mr C. Di Pinto for the CMR-spectra and to Mr A. Milone for the MS spectral measurements.     

The structure of gephyrotoxin (GTX) 223AB

Summary The structure 3-butyl-5-propylindolizidine (2), tentatively assigned to a minor alkaloid in skin extracts from a number of poison frogs of the Neotropical genusDendrobates, has been confirmed and its stereochemistry determined as 5E, 9E (2d) by comparison on GC and GC-MS with the four synthetic diastereomers2a-2d.     

Transformation of progesterone byCaldariella acidophila,an extreme thermophilic bacterium

Summary Caldariella Acidophila, a thermophilic bacterium, converts porgesterone (1) to pregn-4-en-3,6,20-trione (2), 5a-pregnan-3, 6, 20-trione (3), pregn-4-en-20a-ol-3-one (4), pregn-4-6-ol-3, 20-dione (5) and pregn-4-en-6a-ol-3, 20-dione (6). Different patterns of these metabolites were obtained by modifying the incubation conditions and using differently treated biocatalysis.     

Latrunculin-A,ichthyotoxic constituent of the nudibranchChromodoris elisabethina

Summary Latrunculin-A, an ichthyotoxin previously described from a Red Sea sponge,Latrunculia magnifica, has been isolated from a Pacific nudibranch,Chromodoris elisabethina, for which it serves as a defense allomone.     

Palinurin,a new linear sesterterpene from a marine sponge

Summary The structure of a new linear sesterterpene, palinurin (1), obtained from the marine spongeIrcinia variabilis, was determined by spectral and chemical means.This work was carried out at the Progetto Finalizzato Oceanografia e Fondi Marini, C.N.R., Roma. We thank Professor M. Sarà (University of Genova) for the identification of the sponge, Mr C. Di Pinto for¹H-and¹³C-NMR, Mr G. Scognamiglio for technical assistance.