With the increasing awareness of environmental protection, it is necessary to develop natural product extracts as antifouling (AF) agents for alternatives to toxic biocides or metal-based AF paints to control biofouling. This paper briefly summarizes the latest developments in the natural product extracts and their derivatives or analogues from marine microorganisms to terrestrial plants as AF agents in the last five years. Moreover, this paper discusses the structures-activity relationship of these AF compounds and expands their AF mechanisms. Inspired by the molecular structure of natural products, some derivatives or analogues of natural product extracts and some novel strategies for improving the AF activity of protective coatings have been proposed as guidance for the development of a new generation of environmentally friendly AF agents.

Benzoxazine resins are new thermosetting resins with excellent thermal stability, mechanical properties, and a flexible molecular design, demonstrating promise for applications in marine antifouling coatings. However, designing a multifunctional green benzoxazine resin-derived antifouling coating that combines resistance to biological protein adhesion, a high antibacterial rate, and low algal adhesion is still challenging. In this study, a high-performance coating with a low environmental impact was synthesized using urushiol-based benzoxazine containing tertiary amines as the precursor, and a sulfobetaine moiety into the benzoxazine group was introduced. This sulfobetaine-functionalized urushiol-based polybenzoxazine coating (poly(U-ea/sb)) was capable of clearly killing marine biofouling bacteria adhered to the coating surface and significantly resisting protein attachment. poly(U-ea/sb) exhibited an antibacterial rate of 99.99% against common Gram negative bacteria (e.g., Escherichia coli and Vibrio alginolyticus) and Gram positive bacteria (e.g., Staphylococcus aureus and Bacillus sp.), with >99% its algal inhibition activity, and it effectively prevented microbial adherence. Here, a dual-function crosslinkable zwitterionic polymer, which used an \"offensive-defensive\" tactic to improve the antifouling characteristics of the coating was presented. This simple, economic, and feasible strategy provides new ideas for the development of green marine antifouling coating materials with excellent performance.

By introducing thiourea and ether groups into MQ silicone resin polymer via free radical polymerization, a polyether-thiourea-siloxane (PTS) copolymer was synthesized. The characterization of the synthesized copolymer indicated the occurrence of H-bonding interactions and a narrow molecular weight polydispersity index. Antifouling coatings were produced by incorporating the synthesized copolymer and phenylmethylsilicone oil (PSO). The addition of a minute amount of copolymer enhanced the hydrophobicity of the coating by increasing its surface roughness. However, excessive addition of copolymer resulted in a significant deterioration of the coating surface smoothness. The copolymer improved the mechanical properties of the coating, but excessive addition decreased the crosslinking density and weakened the mechanical performance. With increasing copolymer addition, the leaching of PSO was significantly improved due to the change in the storage form of PSO in the coating caused by the copolymer. Based on the H-bonding interaction of the copolymer, the adhesion strength between the coating and the substrate was significantly improved. However, excessive addition of copolymer did not infinitely enhance the adhesion strength. The antifouling performance demonstrated that an appropriate amount of copolymer could obtain adequate PSO leaching efficiency, thereby effectively enhancing the antifouling performance of the coating. In this study, the prepared coating P12 (12 g of PTS in 100 g of PDMS) showed the most effective antifouling performance.

Polyelectrolyte multilayer (PEM) assembly is a versatile tool to construct low-fouling coatings. For application in the marine environment, their structure needs to be stabilized by covalent linkage. Here, we introduce an approach for spin coating of silane-based sol-gel chemistries using layer-by-layer assembly of polysaccharide-based hybrid polymer coatings (LBLHPs). The silane sol-gel chemistry allows the films to be cross-linked under water-based and mild reaction conditions. Two different silanes were used for this purpose, a conventional triethoxymethyl silane and a de novo synthesized zwitterionic silane. The polysaccharide-silane hybrid polymer coatings were thoroughly characterized with spectroscopic ellipsometry, water contact angle (WCA) goniometry, attenuated total reflection-Fourier transform infrared spectroscopy, and atomic force microscopy. The coatings showed good stability in seawater, smooth surfaces, a high degree of hydration, and WCAs below or close to the Berg limit. LBLHPs showed low-fouling properties in biological assays against nonspecific protein adsorption, attachment of the diatom Navicula perminuta, and settlement of zoospores of the macroalga Ulva linza.

Marine biofouling is a ubiquitous problem that accompanies human marine activities and marine industries. It exerts detrimental impacts on the economy, environment, ecology, and safety. Traditionally, mainstream approaches utilize metal ions to prevent biological contamination, but this also leads to environmental pollution and damage to the ecosystem. Efficient and environmentally friendly coatings are urgently needed to prevent marine devices from biofouling. Since nature is always the best teacher for humans, it offers us delightful thoughts on the research and development of high-efficiency, broad-spectrum and eco-friendly antifouling coatings. In this work, we focus on the research frontier of marine antifouling coatings from a bionic perspective. Enlightened by three distinctive dimensions of bionics: chemical molecule bionic, physiological mechanism bionic, and physical structure bionic, the research status of three main bioinspired strategies, which are natural antifoulants, bioinspired polymeric antifouling coatings, and biomimetic surface microtopographies, respectively, are demonstrated. The antifouling mechanisms are further interpreted based on biomimetic comprehension. The main fabrication methods and antifouling performances of these coatings are presented along with their advantages and drawbacks. Finally, the challenges are summarized, and future research prospects are proposed. It is believed that biomimetic antifouling strategies will contribute to the development of nontoxic antifouling techniques with exceptional repellency and stability.

Environmentally friendly antifouling coatings without biocide release need to be developed. Herein, a vertical array of nylon fibers coated with poly(sulfobetaine methacrylate) (PSBMA) was prepared by the electrostatic flocking technique and free radical polymerization catalyzed by Fe2+, which are called zwitterionic electrostatic flocking surfaces (ZEFS). The ZEFS showed resistance to diatoms because the fiber diameter was smaller than the diatom size. At the same time, the ZEFS prevented mussels adhesion. The number of plaques on the ZEFS was reduced by more than 98% and 96% compared with the glass surface and polydimethylsiloxane (PDMS) after a 4-day assay. The special surface morphology of the vertical arrangement of fibers makes it difficult for the mussels to empty seawater. Zwitterionic surface modification further enhanced the resistance to mussel adhesion. The ZEFS showed strong hydrophilicity with an underwater oil contact angle of up to 152 ± 2.4°, which reduces the adhesion work of mussel protein adhesion to the fibers and the wettability of the protein on the fiber surface. In addition, the zwitterionic layer exhibited good stability in artificial seawater, and it retained more than 96% stability after 30 days immersion in artificial seawater.

Polysaccharide multilayers consisting of hyaluronic acid and chitosan were prepared by layer-by-layer assembly. To be used in seawater, the multilayers were crosslinked to a different degree using thermal or chemical methods. ATR-FTIR revealed different amide densities as a result of the crosslinking conditions. AFM showed that the crosslinking affected the roughness and swelling behavior of the coatings. The stability and degradability of the multilayers in aqueous environments were monitored with spectroscopic ellipsometry. The resistance of the coatings against non-specific protein adsorption was characterized by SPR spectroscopy. Settlement assays using Ulva linza zoospores and removal assays using the diatom Navicula incerta showed that the slowly degradable coatings were less prone to fouling than the strongly crosslinked ones. Thus, the coatings were a suitable model system to show that crosslinking the multilayers under mild conditions and equipping the coatings with controlled degradation rates enhances their antifouling and fouling-release properties against marine fouling organisms.

Herein, several novel composite films consisting of three-dimensional (3D) Bi5O7I flower-like shaped microsphere and zwitterionic fluorinated polymer (ZFP) were successfully fabricated with the aim of achieving high anti-fouling performance. The prepared Bi5O7I flower-like shaped microsphere particles with diameters in the range of 2∼3 μm were uniformly distributed on the surface and in the internal of ZFP. Benefiting from the hydration layer formed by the ZFP and the efficient photocatalytic performance of Bi5O7I flower-like microsphere, the resultant optimized Bi5O7I/ZFP composite film exhibited an excellent diatom anti-settling performance and a high antibacterial rate of 99.09% and 99.66% towards Escherichia coli and Staphylococcus aureus. In addition, the composite films possessed the strengthened visible light absorption, the effectively separation and transfer of the photo-induced electrons and holes, the large number of hydroxyl (OH) radicals and superoxide radicals (O2-) all in Bi5O7I/ZFP systems, all of which were beneficial for the photocatalytic antifouling activity. More importantly, the synergistic hydration-photocatalytic effect of the Bi5O7I/ZFP composite films are answerable for the improvement of the antifouling property compared to the control. Thus, the synergistic hydration-photocatalytic contribution of Bi5O7I/ZFP composite film will shows promise for potential application in marine antifouling.

We report an effective and versatile approach to control marine fouling on artificial surfaces based on specific chemical interactions found in marine mussels. The approach consists of mussel-inspired polydopamine coating, spin-coating-assisted deposition of poly(ethylene glycol) (PEG) catechols, and their cross-linking via catechol-Fe3+-catechol interactions. Using this approach, multilayered PEG films that were highly resistant to marine diatom adhesion were successfully constructed on various substrates, such as stainless steel, nylon, titanium oxide, and silicon oxide. We believe that our results will provide a basis for the construction of a marine antifouling agent that can be applied by a large variety of industries owing to its applicability to different types of substrates and stability under marine environments.

An antifouling ethylene-vinyl acetate copolymer (EVA) coating with halloysite clay nanotubes loaded with maleimide (TCPM) is prepared. Such antifoulant encapsulation allowed for extended release of TCPM and a long-lasting, efficient protection of the coated surface against marine microorganisms proliferation. Halloysite also induces the composite\'s anisotropy due to parallel alignment of the nanotubes. The maleimide loaded halloysite incorporated into the polymer matrix allowed for 12-month release of the bacterial inhibitor preventing fouling; it is much longer than the 2-3 month protection when TCPM is directly admixed into EVA. The antifouling properties of the EVA-halloysite nanocomposites were tested by monitoring surface adhesion and proliferation of marine V. natriegens bacteria with SEM. As compared to the composite directly doped with TCPM-antifoulant, there were much less bacteria accumulated on the EVA-halloysite-TCPM coating after a 2-month exposure to seawater. Field tests at South China Sea marine station further confirmed the formulation efficiency. The doping of 28 wt % TCPM loaded halloysite drastically enhanced material antifouling property, which promises wide applications for protective marine coating.