Evaluation of natural resveratrol multimers as marine antifoulants.

In the current study we investigate the antifouling potential of three polyphenolic resveratrol multimers (-)-hopeaphenol, vaticanol B and vatalbinoside A, isolated from two species of Anisoptera found in the Papua New Guinean rainforest. The compounds were evaluated against the growth and settlement of eight marine microfoulers and against the settlement and metamorphosis of Amphibalanus improvisus barnacle cyprids. The two isomeric compounds (-)-hopeaphenol and vaticanol B displayed a high inhibitory potential against the cyprid larvae metamorphosis at 2.8 and 1.1 µM. (-)-Hopeaphenol was also shown to be a strong inhibitor of both microalgal and bacterial adhesion at submicromolar concentrations with low toxicity. Resveratrol displayed a lower antifouling activity compared to the multimers and had higher off target toxicity against MCR-5 fibroblasts. This study illustrates the potential of natural products as a valuable source for the discovery of novel antifouling leads with low toxicity.

Mechanically Enhanced Salmo salar Gelatin by Enzymatic Cross-linking: Premise of a Bioinspired Material for Food Packaging, Cosmetics, and Biomedical Applications.

Marine animal by-products of the food industry are a great source of valuable biomolecules. Skins and bones are rich in collagen, a protein with various applications in food, cosmetic, healthcare, and medical industries in its native form or partially hydrolyzed (gelatin). Salmon gelatin is a candidate of interest due to its high biomass production available through salmon consumption, its biodegradability, and its high biocompatibility. However, its low mechanical and thermal properties can be an obstacle for various applications requiring cohesive material. Thus, gelatin modification by cross-linking is necessary. Enzymatic cross-linking by microbial transglutaminase (MTG) is preferred to chemical cross-linking to avoid the formation of potentially cytotoxic residues. In this work, the potential of salmon skin gelatin was investigated, in a comparative study with porcine gelatin, and an enzymatic versus chemical cross-linking analysis. For this purpose, the two cross-linking methods were applied to produce three-dimensional, porous, and mechanically reinforced hydrogels and sponges with different MTG ratios (2%, 5%, and 10% w/w gelatin). Their biochemical, rheological, and structural properties were characterized, as well as the stability of the material, including the degree of syneresis and the water-binding capacity. The results showed that gelatin enzymatically cross-linked produced material with high cross-linking densities over 70% of free amines. The MTG addition seemed to play a crucial role, as shown by the increase in mechanical and thermal resistances with the production of a cohesive material stable above 40 °C for at least 7 days and comparable to porcine and chemically cross-linked gelatins. Two prototypes were obtained with similar thermal resistances but different microstructures and viscoelastic properties, due to different formation dynamics of the covalent network. Considering these results, the enzymatically cross-linked salmon gelatin is a relevant candidate as a biopolymer for the production of matrix for a wide range of biotechnological applications such as food packaging, cosmetic patch, wound healing dressing, or tissue substitute.

Antifouling Activity of Halogenated Compounds Derived from the Red Alga Sphaerococcus coronopifolius: Potential for the Development of Environmentally Friendly Solutions.

Nowadays, biofouling is responsible for enormous economic losses in the maritime sector, and its treatment with conventional antifouling paints is causing significant problems to the environment. Biomimetism and green chemistry approaches are very promising research strategies for the discovery of new antifouling compounds. This study focused on the red alga Sphaerococcus coronopifolius, which is known as a producer of bioactive secondary metabolites. Fifteen compounds, including bromosphaerol (1), were tested against key marine biofoulers (five marine bacteria and three microalgae) and two enzymes associated with the adhesion process in macroalgae and invertebrates. Each metabolite presented antifouling activity against at least one organism/enzyme. This investigation also revealed that two compounds, sphaerococcinol A (4) and 14R-hydroxy-13,14-dihydro-sphaerococcinol A (5), were the most potent compounds without toxicity towards oyster larvae used as non-target organisms. These compounds are of high potential as they are active towards key biofoulers and could be produced by a cultivable alga, a fact that is important from the green chemistry point of view.

Antifouling Activity of Meroterpenes Isolated from the Ascidian Aplidium aff. densum.

The settlement and growth of fouling organisms on man-made surfaces can be prevented by the application of antifouling paints containing active compounds (biocides, heavy metals), most of which are toxic to non-target organisms. As part of our research program in chemical ecology and blue biotechnology, we are conducting studies to investigate the natural defence mechanisms of marine organisms that are free from epibionts, with the aim of isolating molecules involved in surface defence that could be good candidates as antifouling agents. Ascidians were selected for our investigation because previous studies have shown that they contain abundant and diverse secondary metabolites, which play a defensive role and have been applied to drug discovery. It is therefore relevant to study the role of such secondary metabolites in surface protection. In this study, 5 meroterpenoids (cordiachromene A, didehydroconicol, epiconicol, methoxyconidiol, conidione) from Aplidium aff. densum (ascidian) were investigated as potential antifoulants towards the inhibition of bacterial growth and settlement inhibition of barnacles. Cardiochromene A (IC50 barnacle settlement = 6.04 µg/mL; MIC Gram positive = 125 µg/mL; MIC Gram negative = 32 µg/mL) and epiconicol (IC50 barnacle settlement = 8.05 µg/mL; MIC Bacillus = 63 µg/mL; MIC other strains = 32 µg/mL) were the most promising compounds among those tested in this study.

Quorum Sensing Inhibitory and Antifouling Activities of New Bromotyrosine Metabolites from the Polynesian Sponge Pseudoceratina n. sp.

Four new brominated tyrosine metabolites, aplyzanzines C-F (1-4), were isolated from the French Polynesian sponge Pseudoceratina n. sp., along with the two known 2-aminoimidazolic derivatives, purealidin A (5) and 6, previously isolated, respectively, from the sponges Psammaplysilla purpurea and Verongula sp. Their structures were assigned based on the interpretation of their NMR and HRMS data. The compounds exhibited quorum sensing inhibition (QSi) and antifouling activities against several strains of bacteria and microalgae. To our knowledge, the QSi activity of this type of bromotyrosine metabolite is described here for the first time.

The Sponge-Associated Fungus Eurotium chevalieri MUT 2316 and its Bioactive Molecules: Potential Applications in the Field of Antifouling.

The need for new environmentally friendly antifouling and the observation that many marine organisms have developed strategies to keep their surface free of epibionts has stimulated the search for marine natural compounds with antifouling activities. Sponges and in particular fungi associated with them represent one of the most appropriate sources of defence molecules and could represent a promising biomass for the supply of new antifouling compounds. The objective of this work was therefore to evaluate the antifouling potency of 7 compounds isolated from the sponge derived fungus Eurotium chevalieri MUT 2316. The assessment of their activity targeted the inhibition of the adhesion and/or growth of selected marine bacteria (5) and microalgae (5), as well as the inhibition of the mussel's byssus thread formation (tyrosinase activity). The 7 compounds showed bioactivity, with various levels of selectivity for species. Cyclo-L-Trp-L-Ala was the most promising active compound, and led to the inhibition, at very low concentrations (0.001 µg ml-1 in 61.5% of cases), of adhesion and growth of all the microalgae, of selected bacteria, and towards the inhibition of tyrosinase. Promising results were also obtained for echinulin, neoechinulin A, dihydroauroglaucin and flavoglaucin, respectively, leading to inhibition of adhesion and/or growth of 9, 7, 8 and 8 microfouling species at various concentrations.

From Ecology to Biotechnology, Study of the Defense Strategies of Algae and Halophytes (from Trapani Saltworks, NW Sicily) with a Focus on Antioxidants and Antimicrobial Properties.

This study aimed at the characterization of the antioxidant power of polyphenol extracts (PE) obtained from the algae Cystoseira foeniculacea (CYS) (Phaeophyta) and from the halophyte Halocnemum strobilaceum (HAL), growing in the solar saltworks of western Sicily (Italy), and at the evaluation of their anti-microfouling properties, in order to correlate these activities to defense strategies in extreme environmental conditions. The antioxidant properties were assessed in the PE based on the total antioxidant activity test and the reducing power test; the anti-microfouling properties of the two PE were evaluated by measuring the growth inhibition of marine fish and shellfish pathogen bacteria as well as marine surface fouling bacteria and microalgae exposed to the fractions. Similar polyphenol content (CYS 5.88 ± 0.75 and HAL 6.03 ± 0.25 mg gallic acid equivalents (GAE) g-1 dried weight, DW) and similar reducing power percentage (93.91 ± 4.34 and 90.03 ± 6.19) were recorded for both species, even if they exhibited a different total antioxidant power (measured by the percentage of inhibition of the radical 2,2 diphenyl-1-picrylhydrazyl DPPH), with CYS (79.30) more active than HAL (59.90). Both PE showed anti-microfouling properties, being inhibitors of adhesion and growth of marine fish and shellfish pathogen bacteria (V. aestuarianus, V. carchariae, V. harveyi, P. elyakovii, H. aquamarina) and fouling bacteria (V. natriegens, V. proteolyticus, P. iirgensii, R. litoralis) with minimum inhibitory concentrations comparable to the commercial antifouling products used as a positive control (SEA-NINE™ 211N). Only CYS was a significant inhibitor of the microalgae strains tested, being able to reduce E. gayraliae and C. closterium growth (MIC 10 µg·mL-1) and the adhesion of all three strains tested (E. gayraliae, C. closterium and P. purpureum), suggesting its promise for use as an antifouling (AF) product.

Phenolic compounds in the brown seaweed Ascophyllum nodosum: distribution and radical-scavenging activities.

INTRODUCTION: Phenolic compounds are metabolites exhibited at high levels in Phaeophyceae. Although several studies have been conducted on total phenol contents, no one to our knowledge has dealt with the contents of phenolic compounds and antioxidant activities on purified fractions. OBJECTIVE: The purpose of this study was the extraction and purification of phenolic compounds from the brown seaweed Ascophylllum nodosum, to determine both their distribution and their radical-scavenging activities, and to obtain a sufficiently purified oligophenolic fraction to perform an RP-HPLC analysis on molecules with a molecular weight (MW) < 2 kDa. METHODOLOGY: Phenolic compounds were separated and purified by liquid-liquid extraction, tangential ultrafiltration and dialysis. Then, the contents of both phenolic compounds and radical-scavenging activities were measured by the Folin-Ciocalteu reagent, and DPPH and ABTS assays. NMR analysis was performed to validate the process. RP-HPLC with a C(18) column was performed on the oligophenolic fraction, using a novel method developed in this study. RESULTS: Seven fractions were obtained as a function of polarity and molecular weight. Among them, the fraction containing phenolic compounds with a MW ≥ 50 kDa appeared to be the most active, correlated with the content of phenolic compounds. CONCLUSION: This work constitutes a step forward in the separation and purification of bioactive phlorotannins and represents a prerequisite for further investigations into their structural characterisation and distribution in A. nodosum.