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8 pages, 273 KiB

Open AccessArticle

Quantification of a Sulfated Marine-Inspired Antifouling Compound in Several Aqueous Matrices: Biodegradation Studies and Leaching Assays from Polydimethylsiloxane Coatings

by Cátia Vilas-Boas, Virgínia Gonçalves, Paolo De Marco, Emília Sousa, Madalena Pinto, Elisabete R. Silva, Maria Elizabeth Tiritan and Marta Correia-da-Silva

Mar. Drugs 2022, 20(9), 548; https://doi.org/10.3390/md20090548 - 25 Aug 2022

Cited by 1 | Viewed by 1879

Abstract

The development of marine-inspired compounds as non-toxic antifouling (AF) agents has been pursued in the last years. Sulfur is the third most common element in seawater. Sulfur is present in oxygenated seawater as sulfate anion (SO₄²⁻), which is the most [...] Read more.

The development of marine-inspired compounds as non-toxic antifouling (AF) agents has been pursued in the last years. Sulfur is the third most common element in seawater. Sulfur is present in oxygenated seawater as sulfate anion (SO₄²⁻), which is the most stable combination of sulfur in seawater, and several promising AF secondary metabolites with sulfate groups have been described. However, sulfated compounds proved to be an analytical challenge to quantify by HPLC. Taking these facts into consideration, this work presents the development and validation of a method for the quantification of gallic acid persulfate (GAP) in seawater and ultrapure water matrix, based on hydrophilic interaction liquid chromatography (HILIC). This method was used to evaluate GAP stability following several abiotic and biotic degradation assays, and to quantify its release in seawater from room-temperature-vulcanizing polydimethylsiloxane commercial coating. GAP was very stable in several water matrices, even at different pH values and in the presence/absence of marine microorganisms and presented a leaching value lower than 0.5%. This work discloses HILIC as an analytical method to overcome the difficulties in quantifying sulfated compounds in water matrices and highlights the potential of GAP as a promising long-lasting coating. Full article

(This article belongs to the Special Issue Marine Natural Products with Antifouling Activity, 2nd Edition)

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12 pages, 2155 KiB

Open AccessArticle

Antifouling Marine Coatings with a Potentially Safer and Sustainable Synthetic Polyphenolic Derivative

by Ana R. Neves, Luciana C. Gomes, Sara I. Faria, João Sousa, Raquel Ruivo, Inês Páscoa, Madalena Pinto, Emília Sousa, Miguel M. Santos, Elisabete R. Silva, Marta Correia-da-Silva and Filipe Mergulhão

Mar. Drugs 2022, 20(8), 507; https://doi.org/10.3390/md20080507 - 5 Aug 2022

Cited by 8 | Viewed by 3101

Abstract

The development of harmless substances to replace biocide-based coatings used to prevent or manage marine biofouling and its unwanted consequences is urgent. The formation of biofilms on submerged marine surfaces is one of the first steps in the marine biofouling process, which facilitates [...] Read more.

The development of harmless substances to replace biocide-based coatings used to prevent or manage marine biofouling and its unwanted consequences is urgent. The formation of biofilms on submerged marine surfaces is one of the first steps in the marine biofouling process, which facilitates the further settlement of macrofoulers. Anti-biofilm properties of a synthetic polyphenolic compound, with previously described anti-settlement activity against macrofoulers, were explored in this work. In solution this new compound was able to prevent biofilm formation and reduce a pre-formed biofilm produced by the marine bacterium, Pseudoalteromonas tunicata. Then, this compound was applied to a marine coating and the formation of P. tunicata biofilms was assessed under hydrodynamic conditions to mimic the marine environment. For this purpose, polyurethane (PU)-based coating formulations containing 1 and 2 wt.% of the compound were prepared based on a prior developed methodology. The most effective formulation in reducing the biofilm cell number, biovolume, and thickness was the PU-based coating containing an aziridine-based crosslinker and 2 wt.% of the compound. To assess the marine ecotoxicity impact of this compound, its potential to disrupt endocrine processes was evaluated through the modulation of two nuclear receptors (NRs), peroxisome proliferator-activated receptor γ (PPARγ), and pregnane X receptor (PXR). Transcriptional activation of the selected NRs upon exposure to the polyphenolic compound (10 µM) was not observed, thus highlighting the eco-friendliness towards the addressed NRs of this new dual-acting anti-macro- and anti-microfouling agent towards the addressed NRs. Full article

(This article belongs to the Special Issue Marine Natural Products with Antifouling Activity, 2nd Edition)

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14 pages, 2778 KiB

Open AccessArticle

Effective Synthesis and Antifouling Activity of Dolastatin 16 Derivatives

by Loida O. Casalme, Keisuke Katayama, Yoshiki Hayakawa, Kensuke Nakamura, Arisa Yamauchi, Yasuyuki Nogata, Erina Yoshimura, Fuyuhiko Matsuda and Taiki Umezawa

Mar. Drugs 2022, 20(2), 124; https://doi.org/10.3390/md20020124 - 4 Feb 2022

Cited by 6 | Viewed by 2634

Abstract

Some derivatives of dolastatin 16, a depsipeptide natural product first obtained from the sea hare Dolabella auricularia, were synthesized through second-generation synthesis of two unusual amino acids, dolaphenvaline and dolamethylleuine. The second-generation synthesis enabled derivatizations such as functionalization of the aromatic ring [...] Read more.

Some derivatives of dolastatin 16, a depsipeptide natural product first obtained from the sea hare Dolabella auricularia, were synthesized through second-generation synthesis of two unusual amino acids, dolaphenvaline and dolamethylleuine. The second-generation synthesis enabled derivatizations such as functionalization of the aromatic ring in dolaphenvaline. The derivatives of fragments and whole structures were evaluated for antifouling activity against the cypris larvae of Amphibalanus amphitrite. Small fragments inhibited the settlement of the cypris larvae at potent to moderate concentrations (EC₅₀ = 0.60-4.62 μg/mL), although dolastatin 16 with a substituent on the aromatic ring (24) was much less potent than dolastatin 16. Full article

(This article belongs to the Special Issue Marine Natural Products with Antifouling Activity, 2nd Edition)

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16 pages, 1320 KiB

Open AccessArticle

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

by Maxence Quémener, Stefanos Kikionis, Marilyne Fauchon, Yannick Toueix, Fanny Aulanier, Antonios M. Makris, Vassilios Roussis, Efstathia Ioannou and Claire Hellio

Mar. Drugs 2022, 20(1), 32; https://doi.org/10.3390/md20010032 - 28 Dec 2021

Cited by 12 | Viewed by 2863

Abstract

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. [...] Read more.

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. Full article

(This article belongs to the Special Issue Marine Natural Products with Antifouling Activity, 2nd Edition)

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650 KiB

Open AccessArticle

New Marine Antifouling Compounds from the Red Alga Laurencia sp.

by Yuko Oguri, Mami Watanabe, Takafumi Ishikawa, Takashi Kamada, Charles S. Vairappan, Hiroshi Matsuura, Kensuke Kaneko, Takahiro Ishii, Minoru Suzuki, Erina Yoshimura, Yasuyuki Nogata and Tatsufumi Okino

Mar. Drugs 2017, 15(9), 267; https://doi.org/10.3390/md15090267 - 28 Aug 2017

Cited by 28 | Viewed by 6301

Abstract

Six new compounds, omaezol, intricatriol, hachijojimallenes A and B, debromoaplysinal, and 11,12-dihydro-3-hydroxyretinol have been isolated from four collections of Laurencia sp. These structures were determined by MS and NMR analyses. Their antifouling activities were evaluated together with eight previously known compounds isolated from [...] Read more.

Six new compounds, omaezol, intricatriol, hachijojimallenes A and B, debromoaplysinal, and 11,12-dihydro-3-hydroxyretinol have been isolated from four collections of Laurencia sp. These structures were determined by MS and NMR analyses. Their antifouling activities were evaluated together with eight previously known compounds isolated from the same samples. In particular, omaezol and hachijojimallene A showed potent activities (EC₅₀ = 0.15–0.23 µg/mL) against larvae of the barnacle Amphibalanus amphitrite. Full article

(This article belongs to the Special Issue Antifouling Marine Natural Products)

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861 KiB

Open AccessArticle

Design, Synthesis, and Antifouling Activity of Glucosamine-Based Isocyanides

by Taiki Umezawa, Yuki Hasegawa, Ira S. Novita, Junya Suzuki, Tatsuya Morozumi, Yasuyuki Nogata, Erina Yoshimura and Fuyuhiko Matsuda

Mar. Drugs 2017, 15(7), 203; https://doi.org/10.3390/md15070203 - 29 Jun 2017

Cited by 7 | Viewed by 6196

Abstract

Biofouling, an undesirable accumulation of organisms on sea-immersed structures such as ship hulls and fishing nets, is a serious economic issue whose effects include oil wastage and clogged nets. Organotin compounds were utilized since the 1960s as an antifouling material; however, the use [...] Read more.

Biofouling, an undesirable accumulation of organisms on sea-immersed structures such as ship hulls and fishing nets, is a serious economic issue whose effects include oil wastage and clogged nets. Organotin compounds were utilized since the 1960s as an antifouling material; however, the use of such compounds was later banned by the International Maritime Organization (IMO) due to their high toxicity toward marine organisms, resulting in masculinization and imposex. Since the ban, there have been extensive efforts to develop environmentally benign antifoulants. Natural antifouling products obtained from marine creatures have been the subject of considerable attention due to their potent antifouling activity and low toxicity. These antifouling compounds often contain isocyano groups, which are well known to have natural antifouling properties. On the basis of our previous total synthesis of natural isocyanoterpenoids, we envisaged the installation of an isocyano functional group onto glucosamine to produce an environmentally friendly antifouling material. This paper describes an effective synthetic method for various glucosamine-based isocyanides and evaluation of their antifouling activity and toxicity against cypris larvae of the barnacle Amphibalanus amphitrite. Glucosamine isocyanides with an ether functionality at the anomeric position exhibited potent antifouling activity, with EC₅₀ values below 1 μg/mL, without detectable toxicity even at a high concentration of 10 μg/mL. Two isocyanides had EC₅₀ values of 0.23 and 0.25 μg/mL, comparable to that of CuSO₄, which is used as a fouling inhibitor (EC₅₀ = 0.27 μg/mL). Full article

(This article belongs to the Special Issue Antifouling Marine Natural Products)

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Review

Jump to: Research

25 pages, 3251 KiB

Open AccessReview

Anti-Larval and Anti-Algal Natural Products from Marine Microorganisms as Sources of Anti-Biofilm Agents

by Kai-Ling Wang, Zheng-Rong Dou, Gao-Fen Gong, Hai-Feng Li, Bei Jiang and Ying Xu

Mar. Drugs 2022, 20(2), 90; https://doi.org/10.3390/md20020090 - 21 Jan 2022

Cited by 20 | Viewed by 5252

Abstract

Bacteria growing inside biofilms are more resistant to hostile environments, conventional antibiotics, and mechanical stresses than their planktonic counterparts. It is estimated that more than 80% of microbial infections in human patients are biofilm-based, and biofouling induced by the biofilms of some bacteria [...] Read more.

Bacteria growing inside biofilms are more resistant to hostile environments, conventional antibiotics, and mechanical stresses than their planktonic counterparts. It is estimated that more than 80% of microbial infections in human patients are biofilm-based, and biofouling induced by the biofilms of some bacteria causes serious ecological and economic problems throughout the world. Therefore, exploring highly effective anti-biofilm compounds has become an urgent demand for the medical and marine industries. Marine microorganisms, a well-documented and prolific source of natural products, provide an array of structurally distinct secondary metabolites with diverse biological activities. However, up to date, only a handful of anti-biofilm natural products derived from marine microorganisms have been reported. Meanwhile, it is worth noting that some promising antifouling (AF) compounds from marine microbes, particularly those that inhibit settlement of fouling invertebrate larvae and algal spores, can be considered as potential anti-biofilm agents owing to the well-known knowledge of the correlations between biofilm formation and the biofouling process of fouling organisms. In this review, a total of 112 anti-biofilm, anti-larval, and anti-algal natural products from marine microbes and 26 of their synthetic analogues are highlighted from 2000 to 2021. These compounds are introduced based on their microbial origins, and then categorized into the following different structural groups: fatty acids, butenolides, terpenoids, steroids, phenols, phenyl ethers, polyketides, alkaloids, flavonoids, amines, nucleosides, and peptides. The preliminary structure-activity relationships (SAR) of some important compounds are also briefly discussed. Finally, current challenges and future research perspectives are proposed based on opinions from many previous reviews. Full article

(This article belongs to the Special Issue Marine Natural Products with Antifouling Activity, 2nd Edition)

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3084 KiB

Open AccessReview

Mini-Review: Antifouling Natural Products from Marine Microorganisms and Their Synthetic Analogs

by Kai-Ling Wang, Ze-Hong Wu, Yu Wang, Chang-Yun Wang and Ying Xu

Mar. Drugs 2017, 15(9), 266; https://doi.org/10.3390/md15090266 - 28 Aug 2017

Cited by 79 | Viewed by 7886

Abstract

Biofouling causes huge economic loss and generates serious ecological issues worldwide. Marine coatings incorporated with antifouling (AF) compounds are the most common practices to prevent biofouling. With a ban of organotins and an increase in the restrictions regarding the use of other AF [...] Read more.

Biofouling causes huge economic loss and generates serious ecological issues worldwide. Marine coatings incorporated with antifouling (AF) compounds are the most common practices to prevent biofouling. With a ban of organotins and an increase in the restrictions regarding the use of other AF alternatives, exploring effective and environmentally friendly AF compounds has become an urgent demand for marine coating industries. Marine microorganisms, which have the largest biodiversity, represent a rich and important source of bioactive compounds and have many medical and industrial applications. This review summarizes 89 natural products from marine microorganisms and 13 of their synthetic analogs with AF EC₅₀ values ≤ 25 μg/mL from 1995 (the first report about marine microorganism-derived AF compounds) to April 2017. Some compounds with the EC₅₀ values < 5 μg/mL and LC₅₀/EC₅₀ ratios > 50 are highlighted as potential AF compounds, and the preliminary analysis of structure-relationship (SAR) of these compounds is also discussed briefly. In the last part, current challenges and future research perspectives are proposed based on opinions from many previous reviews. To provide clear guidance for the readers, the AF compounds from microorganisms and their synthetic analogs in this review are categorized into ten types, including fatty acids, lactones, terpenes, steroids, benzenoids, phenyl ethers, polyketides, alkaloids, nucleosides and peptides. In addition to the major AF compounds which targets macro-foulers, this review also includes compounds with antibiofilm activity since micro-foulers also contribute significantly to the biofouling communities. Full article

(This article belongs to the Special Issue Antifouling Marine Natural Products)

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3190 KiB

Open AccessReview

Antifouling Compounds from Marine Macroalgae

by Hans Uwe Dahms and Sergey Dobretsov

Mar. Drugs 2017, 15(9), 265; https://doi.org/10.3390/md15090265 - 28 Aug 2017

Cited by 89 | Viewed by 10545

Abstract

Marine macroalgae produce a wide variety of biologically-active metabolites that have been developed into commercial products, such as antibiotics, immunosuppressive, anti-inflammatory, cytotoxic agents, and cosmetic products. Many marine algae remain clean over longer periods of time, suggesting their strong antifouling potential. Isolation of [...] Read more.

Marine macroalgae produce a wide variety of biologically-active metabolites that have been developed into commercial products, such as antibiotics, immunosuppressive, anti-inflammatory, cytotoxic agents, and cosmetic products. Many marine algae remain clean over longer periods of time, suggesting their strong antifouling potential. Isolation of biogenic compounds and the determination of their structure could provide leads for the development of environmentally-friendly antifouling paints. Isolated substances with potent antifouling activity belong to fatty acids, lipopeptides, amides, alkaloids, lactones, steroids, terpenoids, and pyrroles. It is unclear as yet to what extent symbiotic microorganisms are involved in the synthesis of these compounds. Algal secondary metabolites have the potential to be produced commercially using genetic and metabolic engineering techniques. This review provides an overview of publications from 2010 to February 2017 about antifouling activity of green, brown, and red algae. Some researchers were focusing on antifouling compounds of brown macroalgae, while metabolites of green algae received less attention. Several studies tested antifouling activity against bacteria, microalgae and invertebrates, but in only a few studies was the quorum sensing inhibitory activity of marine macroalgae tested. Rarely, antifouling compounds from macroalgae were isolated and tested in an ecologically-relevant way. Full article

(This article belongs to the Special Issue Antifouling Marine Natural Products)

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557 KiB

Open AccessReview

Review on Molecular Mechanisms of Antifouling Compounds: An Update since 2012

by Lianguo Chen and Pei-Yuan Qian

Mar. Drugs 2017, 15(9), 264; https://doi.org/10.3390/md15090264 - 28 Aug 2017

Cited by 73 | Viewed by 6786

Abstract

Better understanding of the mechanisms of antifouling compounds is recognized to be of high value in establishing sensitive biomarkers, allowing the targeted optimization of antifouling compounds and guaranteeing environmental safety. Despite vigorous efforts to find new antifouling compounds, information about the mechanisms of [...] Read more.

Better understanding of the mechanisms of antifouling compounds is recognized to be of high value in establishing sensitive biomarkers, allowing the targeted optimization of antifouling compounds and guaranteeing environmental safety. Despite vigorous efforts to find new antifouling compounds, information about the mechanisms of antifouling is still scarce. This review summarizes the progress into understanding the molecular mechanisms underlying antifouling activity since 2012. Non-toxic mechanisms aimed at specific targets, including inhibitors of transmembrane transport, quorum sensing inhibitors, neurotransmission blockers, adhesive production/release inhibitors and enzyme/protein inhibitors, are put forward for natural antifouling products or shelf-stable chemicals. Several molecular targets show good potential for use as biomarkers in future mechanistic screening, such as acetylcholine esterase for neurotransmission, phenoloxidase/tyrosinase for the formation of adhesive plaques, N-acyl homoserine lactone for quorum sensing and intracellular Ca²⁺ levels as second messenger. The studies on overall responses to challenges by antifoulants can be categorized as general targets, including protein expression/metabolic activity regulators, oxidative stress inducers, neurotransmission blockers, surface modifiers, biofilm inhibitors, adhesive production/release inhibitors and toxic killing. Given the current situation and the knowledge gaps regarding the development of alternative antifoulants, a basic workflow is proposed that covers the indispensable steps, including preliminary mechanism- or bioassay-guided screening, evaluation of environmental risks, field antifouling performance, clarification of antifouling mechanisms and the establishment of sensitive biomarkers, which are combined to construct a positive feedback loop. Full article

(This article belongs to the Special Issue Antifouling Marine Natural Products)

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3701 KiB

Open AccessReview

Antifouling Compounds from Marine Invertebrates

by Shu-Hua Qi and Xuan Ma

Mar. Drugs 2017, 15(9), 263; https://doi.org/10.3390/md15090263 - 28 Aug 2017

Cited by 59 | Viewed by 6234

Abstract

In this review, a comprehensive overview about the antifouling compounds from marine invertebrates is described. In total, more than 198 antifouling compounds have been obtained from marine invertebrates, specifically, sponges, gorgonian and soft corals. Full article

(This article belongs to the Special Issue Antifouling Marine Natural Products)

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1385 KiB

Open AccessReview

Off the Shelf Fouling Management

by Daniel Rittschof

Mar. Drugs 2017, 15(6), 176; https://doi.org/10.3390/md15060176 - 14 Jun 2017

Cited by 4 | Viewed by 3542

Abstract

This chapter tells the story of a research thread that identified and modified a pharmaceutical that could be a component of environmentally benign fouling management coatings. First, I present the background context of biofouling and how fouling is managed. The major target of [...] Read more.

This chapter tells the story of a research thread that identified and modified a pharmaceutical that could be a component of environmentally benign fouling management coatings. First, I present the background context of biofouling and how fouling is managed. The major target of the research is disrupting transduction of a complex process in all macrofouling organisms: metamorphosis. Using a bioassay directed approach we first identified a pharmaceutical candidate. Then, based on structure function studies coupled with laboratory and field bioassays, we simplified the molecule, eliminating halogens and aromatic rings to a pharmacophore that could be readily broken down by bacteria. Next, we did further structure function studies coupled to lab and field bioassays of modifications that enabled delivery of the molecule in a variety of coatings. The outcome is a different way of thinking about managing fouling and concepts in which molecules are designed to perform a function and then degrade. This work is discussed in the context of existing fouling management approaches and business models which use long-lived broad-spectrum biocides which have consequences for human, environmental health, and food security. Full article

(This article belongs to the Special Issue Antifouling Marine Natural Products)

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