Cystophloroketals A-E, Unusual Phloroglucinol-Meroterpenoid Hybrids from the Brown Alga Cystoseira tamariscifolia.

Cystophloroketals A-E (1-5), five new phloroglucinol-meroditerpenoid hybrids, have been isolated together with their putative biosynthetic precursor, the monocyclic meroditerpenoid 6, from the Mediterranean brown alga Cystoseira tamariscifolia. They represent the first examples of meroditerpenoids linked to a phloroglucinol through a 2,7-dioxabicyclo[3.2.1]octane moiety. The chemical structures, including absolute configurations, were elucidated on the basis of extensive spectroscopic analysis (HR-ESIMS, 1D and 2D NMR, and ECD) and TDDFT ECD calculations. Compounds 1-6 were tested for their antifouling activity against several marine colonizing species (bacteria, fungi, invertebrates, micro- and macroalgae). Compound 6 showed high potency for the inhibition of macrofoulers (invertebrates and macroalgae), while cystophloroketals B (2) and D (4) displayed strong inhibition of the germination of the two macroalgae tested and moderate antimicrobial activities (bacteria, microalgae, and fungi).

Diterpenoids from the Mediterranean brown alga Dictyota sp. evaluated as antifouling substances against a marine bacterial biofilm.

Four new cyclized diterpenes, one xenicane (1) and three dolabellanes (2-4), were isolated, along with seven previously reported metabolites [3beta-hydroxydilophol (5), dictyols E (6) and C (7), hydroxycrenulide (8), 9-acetoxy-15-hydroxy-1,6-dollabelladiene (9), hydroxyacetyldictyolal (10), and fucoxanthin], from a Mediterranean species of Dictyota sp. collected in Le Brusc Lagoon (French Mediterranean coast). Their structures, as well as their relative configurations, were determined through extensive spectrometric (IR, HRESIMS, 1D and 2D NMR) data analysis and molecular modeling studies and by comparison with those reported in literature. Some of the isolated metabolites were evaluated for their antiadhesion activity against a marine bacterial biofilm (Pseudoalteromonas sp. D41).

Meroditerpenoids and derivatives from the brown alga Cystoseira baccata and their antifouling properties.

The brown alga Cystoseira baccata harvested along the Atlantic coasts of Morocco yielded seven new meroditerpenoids (1-4) and derivatives (5-7), whose chemical structures were elucidated mainly by 2D NMR and mass spectrometry. Surprisingly, for all these compounds, which possess a bicyclo[4.3.0]nonane ring system, a trans fusion of the bicyclic system was deduced by stereochemical studies even though such compounds isolated from Cystoseira species are known to have a typical cis orientation for the bridgehead methyls. The antifouling and antibacterial activities of compounds 1-5 and 7 were evaluated, as well as their toxicity toward nontarget species. Compounds 4, 5, and 7 showed antifouling activities against growth of microalgae, macroalgal settlement, and mussel phenoloxidase activity, while being nontoxic to larvae of sea urchins and oysters.

Antifouling activity of meroditerpenoids from the marine brown alga Halidrys siliquosa.

Nine tetraprenyltoluquinol-related metabolites (1-9) have been isolated from the organic extract of the temperate brown alga Halidrys siliquosa that exhibits antifouling properties. The planar structure of compounds 1-9 was elucidated on the basis of extensive spectroscopic analysis and by comparison of the data with those of related metabolites. Antifouling and toxicity tests were conducted on these compounds: the most active (compounds 2, 6, and 9) inhibited both the growth of four strains of bacteria (MICs < 2.5 microg/mL) and settlement of cyprids of Balanus amphitrite (EC50 < 5 microg/mL), the latter at nontoxic concentrations (LC50 > 5 microg/mL).

Determination of total sterols in brown algae by Fourier transform infrared spectroscopy.

A procedure is proposed for the determination of the total amount of sterols in brown algae Bifurcaria bifurcata, Cladostephus hirsitus, Dictyota dichotoma and Cystoseira sedoides, globally determined as fucosterol, which is the major sterol contained in these algae. The method involves the use of cholesterol as reference standard and a correction factor of 1.259+/-0.003, which represents the ratio between the slopes of calibration lines obtained from fucosterol and cholesterol. The method provides precise and accurate results for the IR analysis of real samples.

Comparison of various extraction methods for identification and determination of volatile metabolites from the brown alga Dictyopteris membranacea.

Three different methods: hydrodistillation (HD), focused microwave-assisted hydrodistillation (FMAHD) and supercritical fluid extraction (SFE) have been applied, for the first time together, for the extraction of volatile metabolites of the brown alga Dictyopteris membranacea. The oils obtained were analyzed by GC-MS (identification and determination of metabolites) and the results were compared. The main chemical classes of compounds identified were C11 hydrocarbons for HD method, sesquiterpenes for FMAHD method and sulphur compounds for SFE method.

FTIR-determination of sterols from the red alga Asparagopsis armata: Comparative studies with HPLC.

An analytical procedure was developed for the determination of the total amount of sterols in the red alga Asparagopsis armata, globally determined as cholesterol, which is the major sterol contained in red algae. Samples, previously saponified with KOH were preconcentrated on DSC-18 solid phase cartridges (SPE) and eluted with dichloromethane stabilized with beta-amylene. Fourier transform infrared (FTIR) spectrometry was employed for selective detection at 1049cm(-1) with a baseline established between 1000 and 1079cm(-1). The results were compared to those obtained by high performance liquid chromatography (HPLC). The concentration obtained in actual samples from alga was 3.37% (w/w) by FTIR and 3.30% (w/w) by HPLC, showing a good comparability between the two methods.

Polar acyclic diterpenoids from Bifurcaria bifurcata (Fucales, Phaeophyta).

From the lipophilic extract of the brown alga Bifurcaria bifurcata collected off the Atlantic coast of Southern Brittany (Quiberon, France), five polar linear diterpenoids have been isolated. These metabolites have been identified as hydroxylated derivatives of 13-oxo- and 13-hydroxygeranylgeraniol. Their structures were characterized on the basis of chemical and spectral evidence including two-dimensional NMR experiments and mass spectrometric techniques. The absolute configuration of the 13-position has been determined, for the 13-hydroxygeranylgeraniol derivatives, to be R by means of a modified Mosher's method and therefore that of 13-hydroxygeranylgeraniol (eleganediol) has been revised. Along with these compounds, three related known geranylgeraniol derivatives were also identified, and these data were used for chemotaxonomical purposes.

Trihydroxylated linear diterpenes from the brown alga Bifurcaria bifurcata.

Two novel polar diterpenes were isolated from the brown alga Bifurcaria bifurcata collected off the Atlantic coast of Morocco, and their structures established by spectral methods. Both compounds are trihydroxylated acyclic diterpenes derived from 12-hydroxygeranylgeraniol. They were tested in vitro for their cytotoxicity and proved to be active against the NSCLC-N6 cell line. Their absolute configuration at the C-12 position has been determined with a modified Mosher's method [J. Am. Chem. Soc. 113 (1991) 4092] and that of the 12-hydroxygeranylgeraniol (bifurcadiol) has been revised.