Synthesis and Antifouling Activity Evaluation of Analogs of Bromosphaerol, a Brominated Diterpene Isolated from the Red Alga Sphaerococcus coronopifolius

Marine biofouling is an epibiotic biological process that affects almost any kind of submerged surface, causing globally significant economic problems mainly for the shipping industry and aquaculture companies, and its prevention so far has been associated with adverse environmental effects for non-target organisms. Previously, we have identified bromosphaerol (1), a brominated diterpene isolated from the red alga Sphaerococcus coronopifolius, as a promising agent with significant antifouling activity, exerting strong anti-settlement activity against larvae of Amphibalanus (Balanus) amphitrite and very low toxicity. The significant antifouling activity and low toxicity of bromosphaerol (1) motivated us to explore its chemistry, aiming to optimize its antifouling potential through the preparation of a number of analogs. Following different synthetic routes, we successfully synthesized 15 structural analogs (2–16) of bromosphaerol (1), decorated with different functional groups. The anti-settlement activity (EC50) and the degree of toxicity (LC50) of the bromosphaerol derivatives were evaluated using cyprids and nauplii of the cirriped crustacean A. amphitrite as a model organism. Derivatives 2, 4, and 6–16 showed diverse levels of antifouling activity. Among them, compounds 9 and 13 can be considered as well-performing antifoulants, exerting their activity through a non-toxic mechanism.

Using Virtual AChE Homology Screening to Identify Small Molecules With the Ability to Inhibit Marine Biofouling

The search for effective yet environmentally friendly strategies to prevent marine biofouling is hampered by the large taxonomic diversity amongst fouling organisms and a lack of well-defined conserved molecular targets. The acetylcholinesterase enzyme catalyses the breakdown of the neurotransmitter acetylcholine, and several natural antifouling allelochemicals have been reported to display acetylcholinesterase inhibitory activity. Our study is focussed on establishing if acetylcholinesterase can be used as a well-defined molecular target to accelerate discovery and development of novel antifoulants via sequential high-throughput in silico screening, in vitro enzymatic studies of identified compound libraries, and in vivo assessment of the most promising lead compounds. Using this approach, we identified potent cholinesterase inhibitors with inhibitory concentrations down to 3 μM from a 10,000 compound library. The most potent inhibitors were screened against five microfouling marine bacteria and marine microalgae and the macrofouling tunicate Ciona savignyi. No activity was seen against the microfoulers but a potent novel inhibitor of tunicate settlement and metamorphosis was discovered. Although only one of the identified active cholinesterase inhibitors displayed antifouling activity suggesting the link between cholinesterase inhibition and antifouling is limited to certain compound classes, the study highlights how in silico screening employed regularly for drug discovery can also facilitate discovery of antifouling leads.

From Natural Xanthones to Synthetic C-1 Aminated 3,4-Dioxygenated Xanthones as Optimized Antifouling Agents

Biofouling, which occurs when certain marine species attach and accumulate in artificial submerged structures, represents a serious economic and environmental issue worldwide. The discovery of new non-toxic and eco-friendly antifouling systems to control or prevent biofouling is, therefore, a practical and urgent need. In this work, the antifouling activity of a series of 24 xanthones, with chemical similarities to natural products, was exploited. Nine (1, 2, 4, 6, 8, 16, 19, 21, and 23) of the tested xanthones presented highly significant anti-settlement responses at 50 μM against the settlement of mussel Mytilus galloprovincialis larvae and low toxicity to this macrofouling species. Xanthones 21 and 23 emerged as the most effective larval settlement inhibitors (EC50 = 7.28 and 3.57 µM, respectively). Additionally, xanthone 23 exhibited a therapeutic ratio (LC50/EC50) > 15, as required by the US Navy program attesting its suitability as natural antifouling agents. From the nine tested xanthones, none of the compounds were found to significantly inhibit the growth of the marine biofilm-forming bacterial strains tested. Xanthones 4, 6, 8, 16, 19, 21, and 23 were found to be non-toxic to the marine non-target species Artemia salina (<10% mortality at 50 μM). Insights on the antifouling mode of action of the hit xanthones 21 and 23 suggest that these two compounds affected similar molecular targets and cellular processes in mussel larvae, including that related to mussel adhesion capacity. This work exposes for the first time the relevance of C-1 aminated xanthones with a 3,4-dioxygenated pattern of substitution as new non-toxic products to prevent marine biofouling.

The Presence of Marine Filamentous Fungi on a Copper-Based Antifouling Paint

Marine biofouling is undesirable growth on submerged substances, which causes a major problem for maritime industries. Antifouling paints containing toxic compounds such as copper are used to prevent marine biofouling. However, bacteria and diatoms are usually found in biofilms developed on such paints. In this study, plastic panels painted with a copper-based self-polishing antifouling paint were exposed to biofouling for 6 months in the Marina Bandar Rowdha, Sea of Oman. Clean panels were used as a control substratum. Marine filamentous fungi from protected and unprotected substrate were isolated on a potato dextrose agar. Pure isolates were identified using sequences of the ITS region of rDNA. Six fungal isolates (Alternaria sp., Aspergillus niger, A. terreus, A. tubingensis, Cladosporium halotolerans, and C. omanense) were obtained from the antifouling paint. Four isolates (Aspergillus pseudodeflectus, C. omanense, and Parengyodontium album) were isolated from clean panels and nylon ropes. This is the first evidence of the presence of marine fungi on antifouling paints. In comparison with isolates from the unprotected substrate, fungi from the antifouling paint were highly resistant to copper, which suggests that filamentous fungi can grow on marine antifouling paints.

The Application of UVC Used in Synergy with Surface Material to Prevent Marine Biofouling

Biofouling is problematic for the shipping industry and can lead to functional and financial setbacks. One possible means of biofouling prevention is the use of ultraviolet-C (UVC) light. Previous studies have investigated UVC with marine coatings, but the synergistic effect with color and surface material, specifically reflectance, has yet to be determined. This study comprised three parts: UVC and color (red vs. white), UVC and reflectance (stainless steel vs. polycarbonate), and UVC and exposure intervals (weekly intervals and 10 min intervals). There was no variance in the biofouling communities for colored surfaces when exposed to 254 nm UVC. Reflectance studies demonstrated that the surface material plays a role in biofouling settlement. Stainless steel panels had significantly greater macrofouling settlement than polycarbonate, specifically among encrusting bryozoan, tubeworms, and tunicate communities. Panels of both surface materials exposed to indirect UVC significantly differed from controls and those exposed directly to UVC. Exposure intervals were also found to reduce biofouling settlement especially with long frequent intervals (i.e., 10 min/day). UVC can be utilized on various colored surfaces and different surface types, but the effectiveness in preventing biofouling is ultimately determined by the duration and frequency of UVC exposure.

Continuous bubble streams for controlling marine biofouling on static artificial structures

Biofouling accumulation is not proactively managed on most marine static artificial structures (SAS) due to the lack of effective options presently available. We describe a series of laboratory and field trials that examine the efficacy of continuous bubble streams in maintaining SAS free of macroscopic biofouling and demonstrate that this treatment approach is effective on surface types commonly used in the marine environment. At least two mechanisms were shown to be at play: the disruption of settlement created by the bubble stream, and the scouring of recently settled larvae through shear stress. Field trials conducted over a one-year period identified fouling on diffusers as a major issue to long-term treatment applications. Field measurements suggest that noise associated with surface mounted air blowers and sub-surface diffusers will be highly localised and of low environmental risk. Future studies should aim to develop and test systems at an operational scale.

Gaseous Plastron on Natural and Biomimetic Surfaces for Resisting Marine Biofouling

In recent years, various biomimetic materials capable of forming gaseous plastron on their surfaces have been fabricated and widely used in various disciplines and fields. In particular, on submerged surfaces, gaseous plastron has been widely studied for antifouling applications due to its ecological and economic advantages. Gaseous plastron can be formed on the surfaces of various natural living things, including plants, insects, and animals. Gaseous plastron has shown inherent anti-biofouling properties, which has inspired the development of novel theories and strategies toward resisting biofouling formation on different surfaces. In this review, we focused on the research progress of gaseous plastron and its antifouling applications.