Marine Antibiofouling Research Articles

Defect Engineered Bi2Te3 Nanosheets with Enhanced Haloperoxidase Activity for Marine Antibiofouling.

Defective bismuth telluride (Bi2Te3) nanosheets, an artificial nanozyme mimicking haloperoxidase activity (hPOD), show promise as eco-friendly, bactericidal, and antimicrofouling materials by enhancing cytotoxic hypohalous acid production from halides and H2O2. Microscopic and spectroscopic characterization reveals that controlled NaOH (upto X = 250µL) etching of the nearly inactive non-transition metal chalcogenide Bi2Te3 nanosheets creates controlled defects (d), such as Bi3+species, in d-Bi2Te3-X that induces enhanced hPOD activity. d-Bi2Te3-250 exhibits approximately eight-fold improved hPOD than the as-grown Bi2Te3 nanosheets. The antibacterial activity of d-Bi2Te3-250 nanozymes, studied by bacterial viability, show 1, and 45% viability for Staphylococcus aureus and Pseudomonas aeruginosa, respectively, prevalent in marine environments. The hPOD mechanism is confirmed using scavengers, implicating HOBr and singlet oxygen for the effect. The antimicrofouling property of the d-Bi2Te3-250 nanozyme has been studied on Pseudomonas aeruginosa biofilm in a lab setting by multiple assays, and also on titanium (Ti) plates coated with the nanozyme mixed commercial paint, exposed to seawater in a real setting. All studies, including direct microscopic evidence, exhibit inhibition of microfouling, up to ≈73%, in the presence of nanozymes. This approach showcases that defect engineering can induce antibacterial, and antimicrofouling activity in non-transition metal chalcogenides, offering an inexpensive alternative to noble metals.

A type of multifunctional cellulose nanocrystal composite silicone-based polymer coating for marine antibiofouling

Nanocomposite polymer coatings are being used as a new generation of marine antibiofouling coatings because of their toxin-free chemical composition and ease of large-scale adoption. Cellulose nanocrystal (CN) exhibits significant potential for composite reinforcement. Herein, CN was surface-modified via α,ω-bis(3-(2-hydroxyl-terminated polydimethylsiloxane (HTPDMS), resulting in dihydroxyl-terminated poly(dimethylsiloxane)-grafted CN (HP-g-CN). The amine-terminated PDMS as the foundational component was sequentially reacted with isophorone diisocyanate, isophthalaldehyde, and carbon disulfide to produce PDMS-based poly (urea-thiourea-imine) (PDMS-PUTI). Subsequently, a composite (PDMS-PUTI/HP-g-CN) was produced through physical blending. The intrinsic imine bonds and dynamic hydrogen-bonding network were responsible for the self-healing properties, which achieved a healing efficiency of up to 89.2 %. HP-g-CN was grafted with the non-leaching lubricant, HTPDMS, resulting in improved mechanical properties (1.38 MPa of ultimate strength) and adhesion strength (2.43 MPa), along with the self-cleaning and self-lubricating performance (0.700 coefficient) of the coating. Additionally, the fouling resistance to bovine serum albumin (BSA, 10.44 μg cm−2), bacteria (∼97.08 % and ∼ 98.05 % reduction for Pseudomonas sp. (P. sp.) and Shewanella sp. (S. sp.), respectively), and diatoms (∼27 cells mm−2) was further enhanced. Marine field tests conducted over 90 days revealed that the coatings were static fouling-resistant for an extended period. This study demonstrated a multifunctional, high-performance, and environmentally friendly nanocomposite polymer coating for preventing marine biofouling.

Burgeoning Single-Atom Nanozymes for Efficient Bacterial Elimination.

To fight against antibacterial-resistant bacteria-induced infections, the development of highly efficient antibacterial agents with a low risk of inducing resistance is exceedingly urgent. Nanozymes can rapidly kill bacteria with high efficiency by generating reactive oxygen species via enzyme-mimetic catalytic reactions, making them promising alternatives to antibiotics for antibacterial applications. However, insufficient catalytic activity greatly limits the development of nanozymes to eliminate bacterial infection. By increasing atom utilization to the maximum, single-atom nanozymes (SAzymes) with an atomical dispersion of active metal sites manifest superior enzyme-like activities and have achieved great results in antibacterial applications in recent years. In this review, the latest advances in antibacterial SAzymes are summarized, with specific attention to the action mechanism involved in antibacterial applications covering wound disinfection, osteomyelitis treatment, and marine antibiofouling. The remaining challenges and further perspectives of SAzymes for practical antibacterial applications are also discussed.

Facile fabrication of durable and fluorine-free liquid infused surfaces on aluminum substrates with excellent anti-icing, anticorrosion, and antibiofouling properties

Marine biofouling has a significant impact on marine industry and activities. Various slippery liquid-infused porous surfaces (SLIPS) for marine antibiofouling have been reported in recent years. However, these surfaces are limited to a few substrates, require a complicated construction procedure, and have a low durability. In this regard, simple, efficient and eco-environmental-friendly methods were used to fabricate SLIPS coatings on aluminum substrates with durable and efficient properties. The chemically etched and grinded aluminum substrates were modified to fabricate hydrophobic surfaces by the application of stearic acid (SA) and polydimethylsiloxane (PDMS) porous coatings. Both SA-modified and PDMS-modified porous hydrophobic surfaces were infused with silicone oil to obtain SLIPS (SLIPS-SA and SLIPS-PDMS). The qualities of two hydrophobic surfaces (SA and PDMS) and their corresponding slippery surfaces (SLIPS-SA and SLIPS-PDMS) were investigated. Wetting studies revealed that the as-prepared slippery surfaces have hydrophobic properties and a low sliding angle, suggesting the formation of a homogeneous and smooth oil layer. Furthermore, results showed that both SLIPS are durable and could retain their slippery properties even after 30 days of immersion in artificial acid rain and saturated saline solution. The optimum SLIPS with very low ice adhesion prolonged the water droplet freezing time over two times compared to the bare aluminum substrate. The hydrophobic surfaces displayed inferior anti-icing, anticorrosion, and antibiofouling performance; however, the lubricant-infused surfaces revealed considerably enhanced anti-icing, anticorrosion, and antibiofouling performance. This approach can be applicable to a wide variety of metal substrates and alloys because of its simplicity, which is critical for the production of SLIPS and expanding their applications in marine environments.

Capsaicin-Modified Fluorosilicone Based Acrylate Coating for Marine Anti-Biofouling

Capsaicin has been extensively studied for its excellent antifouling activity and very low environmental toxicity. However, mixing natural capsaicin with coatings can cause rapid capsaicin leakage, severely shortening its antifouling cycle. In this study, we describe the preparation and performance of a new capsaicin-modified marine antifouling organofluorosilicone, which is based on silicone and fluorine acrylate monomers covalently bound to an organic antimicrobial monomer, HMBA (N-(4-hydroxy-3-methoxybenzyl)-acrylamide) on a polymer network. The chemical grafting of HMBA into the polymer has improved the problem of short antifouling life of the coating due to antifouling agent leakage and the environmental pollution caused by the leakage. The study focused on the synthesis of pristine acrylate monomers with organic bioactive groups prepared from vanillin amine salts and their co-polymerization in the presence of distal acrylate oligomers. The resulting cross-linked films were characterized using infrared spectroscopy, contact angle, and adhesion analyses. The results indicate that the materials had good adhesion, low surface energy, and were resistant to prolonged immersion in water. The polyacrylate coating synthesized from acrylate exhibited antibacterial and anti-algae activity. Biological tests on the marine microorganisms, Pseudomonas species, Shewanella species, and Navicula incerta, revealed a 97%, 98%, and 99% reduction compared to the blank control group, respectively, indicating that the coating has strong anti-adhesive ability. This work is expected to develop a promising material for marine antifouling.

Simple Preparation of Polydimethylsiloxane and Polyurethane Blend Film for Marine Antibiofouling Application.

A key way to prevent undesirable fouling of any structure in the marine environment, without harming any microorganisms, is to use a polymer film with high hydrophobicity. The polymer film, which was simply prepared from a blend of hydrophobic polydimethylsiloxane elastomer and hydrophilic polyurethane, showed improved properties and economic viability for antifouling film for the marine industry. The field emission scanning electron microscope and energy dispersive X-ray spectrometer (FESEM and EDX) results from the polymer blend suggested a homogenous morphology and good distribution of the polyurethane disperse phase. The PDMS:PU blend (95:5) film gave a water contact angle of 103.4° ± 3.8° and the PDMS film gave a water contact angle of 109.5° ± 4.2°. Moreover, the PDMS:PU blend (95:5) film could also be modified with surface patterning by using soft lithography process to further increase the hydrophobicity. It was found that PDMS:PU blend (95:5) film with micro patterning from soft lithography process increased the contact angle to 128.8° ± 1.6°. The results from a field test in the Gulf of Thailand illustrated that the bonding strength between the barnacles and the PDMS:PU blend (95:5) film (0.07 MPa) were lower than the bonding strength between the barnacles and the carbon steel (1.16 MPa). The barnacles on the PDMS:PU blend (95:5) film were more easily removed from the surface. This indicated that the PDMS:PU blend (95:5) exhibited excellent antifouling properties and the results indicated that the PDMS:PU blend (95:5) film with micro patterning surface could be employed for antifouling application.

Silicone Elastomer with Self-Generating Zwitterions for Antifouling Coatings.

Silicone elastomer-based fouling release coatings have been gaining increased attention in marine antibiofouling. However, the lack of fouling resistance limits their application. Introducing a zwitterionic polymer into silicone enhances its fouling resistance, but their incompatibility makes this challenging. In this work, a silicone elastomer with zwitterionic pendant chains has been prepared by grafting a telomer of tertiary carboxybetaine dodecafluoroheptyl ester ethyl acrylate (TCBF) and 3-mercaptopropyltriethoxysilane to the bis-silanol-terminated poly(dimethylsiloxane) (PDMS). The fluorocarbon groups drive the telomer onto the surface in the film formation process, while the TCBF groups hydrolyze and generate zwitterions on the surface, which is confirmed by attenuated total reflection infrared spectra analysis and water contact angle measurements. Bioassays using marine bacteria (Pseudomonas sp.) and diatoms (Navicula incerta) demonstrate that the antifouling efficacy is improved as the telomer content increases. The bacteria and diatom adhesion decreases by 95 and 81%, respectively, for the PDMS with 30 wt % telomer compared with the unmodified PDMS control. Meanwhile, the fouling release performance of PDMS is maintained with a pseudobarnacle removal strength of ∼0.1 MPa. This work provides a facile way to fabricate efficient silicone-based antifouling coatings.

Marine Antibiofouling Properties of TiO2 and Ti-Cu-O Films Deposited by Aerosol-Assisted Chemical Vapor Deposition

The actual interest in developing light-induced catalytic coatings to act as an antibiofouling alternative has recently prompted interest in the incorporation of Cu into TiO2 films, working as a visible light sensitizer catalyst. TiO2 and new Ti-Cu-O films with Cu contents ranging between 16% and 75% Cu/(Cu + Ti) are deposited by aerosol-assisted metalorganic chemical vapor deposition at a substrate temperature of 550 °C. The films are composed of TiO2 anatase phase, mixed with Cu2O when including Cu in the composition. Pure TiO2 films’ morphologies are characterized by the formation of microflower-like structures with nanometric petals, which induce a high specific surface. These features are not present in Ti-Cu-O films. A UV-Visible study revealed that the optical band gap energy decreases with increasing Cu content. Interestingly, Ti-Cu-O films presented a highly photo-catalytic activity in the orange-G degradation. Marine biofouling field tests in Lorient’s Harbor in France and in vitro tests were carried out in order to evaluate the antifouling performance of the films, revealing that topography and chemical composition can act differently on different species. Field tests revealed that TiO2 microflowers reduced the fouling coverage. Besides, Ti-Cu-O films with 16 at.% Cu presented lower fouling coverage than films containing 58 at.% Cu. In vitro tests using two diatoms (P. tricornutum and N. perminuta) showed that the spaces between microflowers play a significant role in the adhesion of diatoms: microalgae adhere less when spaces are bigger than their cells, compared to when spaces are of the same size as cells. Films containing Cu did not alter N. perminuta growth nor adhesion, while they affected P. tricornutum by lowering its growth rate and adhesion without noticeable toxicity. Indeed, Cu-Ti-O is a very promising non-toxic fouling release film for marine and industrial applications.

Protein Leakage Induced Marine Antibiofouling Activity of Biosynthesized Zinc Oxide Nanoparticles

Marine biofouling cause huge economic losses in the aquaculture industries as well as in the marine installation. Biofilm formation is an initial stage of biofouling. Conventional antifoulants including biocides and heavy metal induce toxicity to the aquatic organisms. Marine microorganisms provide a wide range of non-toxic biologically active molecules that helps in synthesis of antimicrobial compounds. The present study was aimed to synthesize zinc oxide nanoparticles (ZnO NPs) using cell free supernatant of Bacillus paramycoides. UV–visible spectrum showed the characteristic surface plasmon resonance absorption band for ZnO NPs at 372 nm. X-ray diffraction shows planes of hexagonal wurtzite structure of ZnO NPs and narrow peaks confirm the crystalline nature of ZnO NPs. Field emission scanning electron microscopic image shows spherical shaped particles in the range of 35–90 nm. Biosynthesized ZnO NPs cause membrane damage in bacterial cells and subsequent protein leakage. ZnO NPs showed remarkable antimicrobial activity against four marine biofilm forming bacteria i.e., Aeromonas hydrophila, Halomonas aquamarina, Escherichia coli and Vibrio parahaemolyticus. Minimum inhibitory concentration value was observed as 10 μg ml−1 with all the bacterial strains. This study also highlights the rapid biosynthesis of ZnO NPs using cell free supernatant of B. paramycoides.

Robust Biomimetic Hierarchical Diamond Architecture with a Self-Cleaning, Antibacterial, and Antibiofouling Surface.

Biofouling is a worldwide problem from healthcare to marine exploration. Aggressive biofouling, wear, and corrosion lead to severe deterioration in function and durability. Here, micro- and nanostructured hierarchical diamond films mimicking the morphology of plant leaves were developed to simultaneously achieve superhydrophobicity, antibacterial efficacy, and marine antibiofouling, combined with mechanical and chemical robustness. These coatings were designed and successfully constructed on various commercial substrates, such as titanium alloys, silicon, and quartz glass via a chemical vapor deposition process. The unique surface structure of diamond films reduced bacteria attachment by 90-99%. In the marine environment, these biomimetic diamond films significantly reduced more than 95% adhesion of green algae. The structured diamond films retained mechanical robustness, superhydrophobicity, and antibacterial efficacy under high abrasion and corrosive conditions, exhibiting at least 20 times enhanced wear resistance than the bare commercial substrates even after long-term immersion in seawater.

Biomimetic Self-Renewal Polymer Brushes with Protein Resistance Inspired by Fish Skin.

Inspired by fish skin, biomimetic self-renewal poly[(ethylene oxide)-co-(ethylene carbonate)] (PEOC) brushes with protein resistance had been prepared via surface-initiated ring-opening polymerization (ROP). The results of hydrolytic degradation indicated that the PEOC brushes could degrade in artificial seawater. Ellipsometry, X-ray photoelectron spectrometry, and contact angle results demonstrated that the PEOC brushes degrade uniformly. By using a quartz crystal microbalance with dissipation, we studied the protein adsorption on the surfaces in artificial seawater at different degradation times. After 24, 48, 96, and 168 h of degradation, the PEOC surfaces showed nearly zero Δf and ΔD for bovine serum albumin, lysozyme, and fibrinogen. More importantly, there was a notably lower density of microorganisms adhered to the surface modified with PEOC compared with that of the surface without PEOC in natural seawater. The current study showed that the PEOC brushes exhibit a self-renewal property with persistent protein resistance and prevent the adhesion of microorganisms. Such a biomimetic polymer had a great potential in marine antibiofouling.

Self-Generating and Self-Renewing Zwitterionic Polymer Surfaces for Marine Anti-Biofouling.

Regeneration of antifouling polymer surfaces after contamination or damage is an important issue, especially in complex marine environments. Here, inspired by the self-renewal of silyl acrylate polymers and the protein resistance of zwitterionic polymers, we prepared a novel hydrolysis-induced zwitterionic monomer, tertiary carboxybetaine triisopropylsilyl ester ethyl acrylate (TCBSA), and copolymerized it with methyl methacrylate (MMA). Such a copolymer rapidly self-generates a zwitterionic surface and provides fouling resistance in marine environments. Furthermore, TCBSA was copolymerized with MMA and 2-methylene-1,3-dioxepane (MDO), where MDO causes degradation of the polymers. Our study demonstrates that the degradation of the polymer is controlled, and the degradation rate increases with the external enzyme concentration in the seawater, leading to a self-renewing dynamic surface. Quartz crystal microbalance with dissipation measurements show that the polymeric coating with self-generating zwitterions has excellent protein resistance in seawater. Bioassays demonstrate that the coating can effectively inhibit the adhesion of marine bacteria (Pseudomonas sp.) and diatoms (Navicula incerta). The coating with a self-generating and self-renewing zwitterionic surface is potential to find applications in marine anti-biofouling.

Specific Ion Effects on the Enzymatic Degradation of Polymeric Marine Antibiofouling Materials

It is expected that the widely dispersed ions in seawater would have strong influence on the performance of polymeric marine antibiofouling materials through the modulation of enzymatic degradation of the materials. In this work, poly(ε-caprolactone)-based polyurethane and poly(triisopropylsilyl methacrylate-co-2-methylene-1,3-dioxepane) have been employed as model systems to explore the specific ion effects on the enzymatic degradation of polymeric marine antibiofouling materials. Our study demonstrates that the specific ion effects on the enzymatic degradation of the polymer films are closely correlated with the ion-specific enzymatic hydrolysis of the ester. In the presence of different cations, the effectiveness of the enzyme to degrade the polymer films is dominated by the direct specific interactions between the cations and the negatively charged enzyme molecules. In the presence of different anions, the kosmotropic anions give rise to a high enzyme activity in the degradation of polymer films induced by the salting-out effect, whereas the chaotropic anions lead to a low enzyme activity in the degradation of the polymer films owing to the salting-in effect. This work highlights the opportunities available for the use of specific ion effects to modulate the enzymatic degradation of polymeric antibiofouling materials in the marine environment.

Biodegradable Poly(ester- co-acrylate) with Antifoulant Pendant Groups for Marine Anti-Biofouling.

Polymer resins are critical for marine anti-biofouling coatings. In this study, degradable poly(ester- co-acrylate) with antifoulant pendant groups has been prepared by the radical ring-opening polymerization of 2-methylene-1,3-dioxepane, methyl methacrylate, and N-methacryloyloxy methyl benzoisothiazolinone. Such a polymer containing main-chain esters can hydrolytically and enzymatically degrade. Both degradation rates increase with main-chain ester content. Moreover, since the antifoulant groups are chemically grafted to the degradable main chain, their release can be controlled by the degradation besides the hydrolysis of side groups. Our study shows that the copolymer coating is efficient in inhibiting the accumulation of marine bacterial biofilm of Pseudomonas sp. and diatom Navicular incerta. Marine field test reveals that the copolymer has excellent efficiency in preventing biofouling for more than 6 months.

Biodegradable Polymer with Hydrolysis-Induced Zwitterions for Antibiofouling.

Persistent protein resistance is critical for marine antibiofouling. We have prepared copolymer of 2-methylene-1,3-dioxepane (MDO), tertiary carboxybetaine ester (TCB), and 7-methacryloyloxy-4-methylcoumarin (MAMC) via radical ring-opening polymerization, where MDO, TCB, and MAMC make the polymer degradable, protein resistible, and photo-cross-linkable, respectively. Our study shows that the polymer can well adhere to the substrate with controlled degradation and water adsorption rate in artificial seawater (ASW). Particularly, the polymer film can generate zwitterions via surface hydrolysis in ASW. Quartz crystal microbalance with dissipation measurements reveal that such hydrolysis-induced zwitterionic surface can effectively resist nonspecific protein adsorption. Moreover, the surface can inhibit the adhesion of marine bacteria Pseudomonas sp. and Vibrio alginolyticus as well as clinical bacterium Escherichia coli.

Amphiphilic Polymer Platforms: Surface Engineering of Films for Marine Antibiofouling.

A range of amphiphilic polymers with diverse macromolecular architectures has been developed and incorporated into films and coatings with potential for marine antibiofouling applications, without resorting to addition of currently used biocidal, toxic agents. Novel "green" chemical technologies employ different building blocks to endow the polymer film with surface activity, functionality, structure, and reconstruction according to the outer environment as a result of a tailored amphiphilic character of the polymer platform. We emphasise how these features can interplay and add synergistically to affect antifouling and fouling-release against common, widespread marine micro- and macro-fouling organisms.

Biodegradable polymer as controlled release system of organic antifoulant to prevent marine biofouling

Abstract Controlled release of antifoulant is critical for marine antibiofouling. We have prepared polyurethane with degradable polyester segments consisting of poly(ethylene adipate) (PEA), poly(1,4-butylene adipate) (PBA) or poly(1,6-hexamethylene adipate) (PHA) and used it as the release system for organic antifoulants. The degradation rate of the polyurethane increases with the content of the degradable segments. On the other hand, as the segments change from PEA, PBA to PHA, the degradation rate decreases because the crystallinity increases but the ester group density decreases. Such degradable polyurethane allows the antifoulants to release at a constant rate, where the release rate can be regulated by varying the polyester segments. Marine field tests reveal that the polyurethane-antifoulant system has good antifouling performance. Particularly, the degradable polyurethane exhibits excellent adhesion to the substrate ensuring the long duration of the system.

Degradable Polymers for Marine Antibiofouling: Optimizing Structure To Improve Performance

Degradable polymers have proven effective for marine antibiofouling. It is important to improve their performance by optimizing their structures. We have prepared polyurethane with degradable polyester segments in the main chain and hydrolyzable poly(triisopropylsilyl acrylate) (PTSA) side chains and used it as the carrier of organic antifoulant (DCOIT). Our study demonstrates that the degradation rate of the polymer increases as the ester group density in the main chain or the length of side chain increases. On the other hand, the release rate of the organic antifoulant increases with the length of side chain. However, it shows a maximum as the ester group density increases. Marine field tests demonstrate that the antifouling of the system increases as the ester group density or the length of side chain increases.

Biodegradable polymers for marine antibiofouling: Poly(ε-caprolactone)/poly(butylene succinate) blend as controlled release system of organic antifoulant

Polymer carrier is critical for the controlled release of antifoulant in marine anti-biofouling. We have prepared biodegradable polymer blend consisting of poly(ε-caprolactone) (PCL) and poly(butylene succinate) (PBS) and used it as carrier of organic antifoulant (4,5-dichloro-2-octyl-isothiazolone). Polarizing optical microscope (POM) and differential scanning calorimetry (DSC) measurements show that the spherulite size of PCL decreases and its crystallinity slightly varies as PBS fraction increases leading the interfacial regions between PCL and PBS spherulites to increase in the total area. Our studies reveal that such amorphous interfacial regions allow the blend to degrade at a constant rate and the antifoulants to be uniformly dispersed in the blend. The antifoulants are released at a constant rate as the blend degrades in marine environment, which can be modulated by the blend composition. Marine field tests demonstrate that such a system has good marine anti-biofouling performance.

Progress in the Development of Environmentally Friendly Marine Anti-Biofouling Systems

Progress in the Development of Environmentally Friendly Marine Anti-Biofouling Systems