Fijian Marine Sponge Research Articles

Antiparasitic Activity of Bromotyrosine Alkaloids and New Analogues Isolated from the Fijian Marine Sponge Aplysinella rhax.

Ten bromotyrosine alkaloids were isolated and characterised from the marine sponge Aplysinella rhax (de Laubenfels 1954) collected from the Fiji Islands, which included one new bromotyrosine analogue, psammaplin P and two other analogues, psammaplin O and 3-bromo-2-hydroxy-5-(methoxycarbonyl)benzoic acid, which have not been previously reported from natural sources. HR-ESI-MS, 1D and 2D NMR spectroscopic methods were used in the elucidation of the compounds. Bisaprasin, a biphenylic dimer of psammaplin A, showed moderate activity with IC50 at 19±5 and 29±6 μM against Trypanzoma cruzi Tulahuen C4, and the lethal human malaria species Plasmodium falciparum clone 3D7, respectively, while psammaplins A and D exhibited low activity against both parasites. This is the first report of the antimalarial and antitrypanosomal activity of the psammaplin-type compounds. Additionally, the biosynthesis hypotheses of three natural products were proposed.

Marine Natural Occurring 2,5-Diketopiperazines: Isolation, Synthesis and Optical Properties

Seven 2,5-diketopiperazines (DKPs) were isolated from the Fijian marine sponge Acanthella cavernosa. NMR and circular dichroism (CD) comparison with synthetic L-L DKPs allowed us to determine unambiguously the L-L absolute configuration of the natural DKPs. This work initiated the setting up of an optical properties database of natural DKPs, including specific rotation and CD. 2,5-Diketopiperazines (DKPs) are cyclic secondary metabolites directly resulted from the primary peptidic metabolites. They have been detected in beverages, foods and microorganisms. As the smallest cyclic peptides, DKPs provide interesting biological properties such as organoleptical, antitumoral, antifungal, antibacterial, antifouling and antiviral activities. 2 Many natural metabolites including alkaloids are biosynthetically derived from diketopiperazines by oxidation and rearrangement reactions. They represent an interesting tool for medicinal chemistry since their heterocyclic cores provide a good template for further chemical and stereochemical modification. Proline (Pro) and arginine (Arg) units are usually found in biologically active DKPs. Despite the increasing interest of DKPs, their stereochemical information was not well documented. DKP derivatives have attracted significant attention because of their potential rule as important class of multifunctional biomolecules. Their putative roles as signaling molecules in the chemical ecology context is more and more considered. Thus, determination of absolute configuration of cyclic dipeptides is of significant importance. As a part of our on-going research on bioactive natural compounds from Pacific Axinellidae marine sponges, a scrutinized study of secondary metabolites of a Fijian sample of the marine sponge Acanthella HETEROCYCLES, Vol. 90, No. 2, 2015 1351

Production and purification of a bioactive substance against multi-drug resistant human pathogens from the marine-sponge-derived Salinispora sp.

ABSTRACT Objective To isolate, purify, characterize, elucidate structure and evaluate bioactive compounds from the sponge-derived Salinispora sp. FS-0034. Methods The symbiotic actinomycete strain FS-0034 with an interesting bioactivity profile was isolated from the Fijian marine sponge Theonella sp. Based on colony morphology and obligatory requirement of seawater for growth, and mycelia morphological characteristics the isolate FS-0034 was identified as a Salinispora sp. The bioactive compound was identified by using various spectral analysis of ultraviolet, high resolution electrospray ionization mass spectroscopy, 1 H nuclear magnetic resonance, correlated spectroscopy and heteronuclear multiple bond coherence spectral data. A minimum inhibitory concentration assay were performed to evaluate the biological properties of the pure compound against multi-drug resistant pathogens. Results Bioassay guided fractionation of the ethyl acetate extract of the culture of Salinispora sp. FS-0034 by different chromatographic methods yielded the isolation of an antibacterial compound, which was identified as rifamycin W (compound 1). Rifamycin W was reported for its potent antibacterial activity against methicillin-resistant Staphylococcus aureus , wild type Staphylococcus aureus and vancomycin-resistant Enterococcus faecium and displayed minimum inhibitory concentrations of 15.62, 7.80 and 250.00 μg/mL, respectively. Conclusions The present study reported the rifamycin W from sponge-associated Salinispora sp. and it exhibited appreciable antibacterial activity against multi-drug resistant human pathogens which indicated that sponge-associated Actinobacteria are significant sources of bioactive metabolites.

Three bioactive sesquiterpene quinones from the Fijian marine sponge of the genus Hippospongia

A sesquiterpenoid quinone, epi-ilimaquinone (1), and two sesquiterpene amino quinones, smenospongine (2) and glycinylilimaquinone (3), were isolated from the Fijian marine sponge Hippospongia sp. The structures of these compounds were determined by spectroscopic analysis. Compounds 1 and 3 were reported for the first time in this study from the sponge of the genus Hippospongia. Compound 1 displayed potent cytotoxic activity and showed antibacterial activity against methicillin-resistant Staphylococcus aureus, wild type S. aureus and vancomycin-resistant Enterococcus faecium and displayed antifungal activity against amphotericin-resistant Candida albicans while compounds 2 and 3 showed moderate cytotoxic activity. However, compound 1 did not show appreciable antifungal activity against wild type C. albicans, Cryptococcus neoformans, Aspergillus niger, Penicillium sp., Rhizopus sporangia or Sordaria sp.

Aurantoside K, a New Antifungal Tetramic Acid Glycoside from a Fijian Marine Sponge of the Genus Melophlus

A new tetramic acid glycoside, aurantoside K, was isolated from a marine sponge belonging to the genus Melophlus. The structure of the compound was elucidated on the basis of spectroscopic analysis (1H NMR, 1H–1H COSY, HSQC, and HMBC, as well as high-resolution ESILCMS). Aurantoside K did not show any significant activity in antimalarial, antibacterial, or HCT-116 cytotoxicity assays, but exhibited a wide spectrum of antifungal activity against wild type Candida albicans, amphotericin-resistant C. albicans, Cryptococcus neoformans, Aspergillus niger, Penicillium sp., Rhizopus sporangia and Sordaria sp.

Dibenzofurans from the marine sponge-derived ascomycete Super1F1-09

Three dibenzofurans hitherto undescribed from nature and one known butyrolactone were isolated from the extract of the ascomycete Super1F1-09 isolated from the Fijian marine sponge Acanthella cavernosa . The isolated compounds were identified as 3,9-dimethyldibenzo[ b,d ]furan-1,7-diol ( 1 ), 3-(hydroxymethyl)-9-methyldibenzo[ b,d ]furan-1,7-diol ( 2 ), 1,7-dihydroxy-9-methyldibenzo[ b,d ]furan-3-carboxylic acid ( 3 ), and the known butyrolactone I ( 4 ) using different NMR spectroscopic techniques and accurate mass spectrometric analysis. 1 was synthesized together with structurally related dibenzofurans 6 – 8 . 1 and 4 had moderate antibacterial activity toward Mycobacterium marinum and Staphylococcus aureus , whereas 2 and 3 proved inactive. In addition, all compounds had moderate inhibitory properties against epidermal growth factor receptor tyrosine kinase.

Three New Spongian Diterpenes from the Fijian Marine Sponge Spongia sp

Chemical investigation of the marine sponge Spongia sp., collected from the Fiji Islands resulted in the isolation of three new furanoditerpenoids 1-3, along with the known compounds epispongiatriol (4) and 17,19-dihydroxyspongia-13(16),14-dien-2,3-dione (5) While 1 is a new spongian diterpene with a modified oxidation pattern, compounds 2 and 3 represent two new ring A-contracted spongians, displaying a novel and unprecedented nor-spongian carbon skeleton. Despite their labile nature the structures could be established through a combined strategy including complete analysis of spectroscopic data (NMR, MS), molecular modeling and quantum-mechanical calculations.

Spongosoritin A: A New Polyketide from a Fijian Marine Sponge, Spongosorites sp.

A new polyketide, spongosoritin A, with a rare vinylagous α,β-unsaturated γ-lactone moiety was isolated from a Fijian marine sponge, Spongosorites sp., and the structure assigned by detailed spectroscopic analysis.

Spongosoritin A: A New Polyketide from a Fijian Marine Sponge, Spongosorites sp.

A new polyketide, spongosoritin A, with a rare vinylagous α,β-unsaturated γ-lactone moiety was isolated from a Fijian marine sponge, Spongosorites sp., and the structure assigned by detailed spectroscopic analysis.

Conformational studies of free and Li+ complexed jasplakinolide, a cyclic depsipeptide from the Fijian marine sponge Jaspis splendens

The complexation of Li+ to jasplakinolide, a marine sponge derived cyclic depsipeptide showed preferential binding to two out of four carbonyl oxygens (C-10, C-14) and the electrons of the aromatic system of the beta-tyrosine amino acid residue. This is in contrast to previous results obtained by others who proposed complexation to three out of four available carbonyl oxygens (C-1, C-10, C-14). The structure of the complex in CD3CN was determined by NOE restrained molecular dynamic calculations. Structures of the uncomplexed jasplakinolide were calculated in CDCl3 and CD3CN for comparison.

Two Distinct Conformers of the Cyclic Heptapeptide Phakellistatin 2 Isolated from the Fijian Marine Sponge Stylotella aurantium.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Two distinct conformers of the cyclic heptapeptide phakellistatin 2 isolated from the fijian marine sponge stylotellaaurantium.

The isolation, structure determination, and solution conformation of two conformers of the cyclic heptapeptide phakellistatin 2 (cyclo-[Phe1-cis-Pro2-Ile3-Ile4-cis-Pro5-Tyr6-cis-Pro7]) isolated from the Fijian marine sponge Stylotella aurantium are reported. The conformers can be isolated separately by HPLC and are stable in methanol solution over a period of weeks as determined by NMR. Their NMR spectra and mass spectral fragmentation patterns differ significantly. Their solution conformations were determined by NOE-restrained molecular dynamics calculations and indicated that the two conformers had different folds, hydrogen bonding patterns, and solvent accessible surfaces. These factors may contribute to the independent stability of the two conformers, and may explain the variable biological activity previously reported for phakellistatin 2.

Purealidin S and purpuramine J, bromotyrosine alkaloids from the Fijian marine sponge Druinella sp.

Two bromotyrosine alkaloids, purealidin S (2) and purpuramine J (5), were isolated from the Fijian marine sponge Druinella sp. Eight known bromotyrosine compounds were also isolated. This is the first report of a bromotyrosine N-oxide containing alkaloid. These two compounds were found to have moderate cytotoxic activity. In addition, bioassay data for the eight known bromotyrosine metabolites are reported.

Axinellin C, a proline-rich cyclic octapeptide isolated from the Fijian marine sponge Stylotella aurantium

The structure of a new cyclic octapeptide, axinellin C, (cyclo[Thr 1-Val 2-Pro 3-Trp 4-Pro 5-Phe 6-Pro 7-Leu 8]), with all- trans peptide bond geometry, was elucidated by a combination of 2D NMR methods and tandem mass spectrometry. The solution state conformation was determined by ROE restrained molecular dynamics calculations. The structural features were found to be similar to those of the crystal structure of the cyclic decapeptide, phakellistatin 8, despite differing peptide sequences.

Wainunuamide, a histidine-containing proline-rich cyclic heptapeptide isolated from the Fijian marine sponge Stylotella aurantium

The isolation and structure determination of an unusual cyclic heptapeptide, wainunuamide, from a Fijian marine sponge, Stylotella aurantium, is reported. The peptide contains three proline residues and a histidine residue, which is rare in cyclic peptides and has only previously been reported in a cyclic peptide isolated from the cyanobacterium Oscillatoria agardhii, suggesting a possible source of the peptide. Wainunuamide is found to have weak cytotoxic activity.

Psammaplin A, a chitinase inhibitor isolated from the fijian marine sponge Aplysinella rhax

Several brominated tyrosine derived compounds, psammaplins A (1), K (2) and L (3) as well as bisaprasin (4) were isolated from the Fijian marine sponge Aplysinella rhax during a bioassay guided isolation protocol. Their structures were determined using NMR and MS techniques. Psammaplin A was found to moderately inhibit chitinase B from Serratia marcescens, the mode of inhibition being non-competitive. Crystallographic studies suggest that a disordered psammaplin A molecule is bound near the active site. Interestingly, psammaplin A was found to be a potent antifungal agent.

Stelliferin riboside, a triterpene monosaccharide isolated from the Fijian sponge Geodia globostellifera.

A triterpene monosaccharide, stelliferin riboside (1), was isolated from the Fijian marine sponge Geodia globostellifera. In addition, stellettins A and B (2, 3) were also isolated. This is the first report of a stelliferin from this species and the first example of a saccharide derivative of a stelliferin.