On the mechanism of marine fouling-prevention performance of oil-containing silicone elastomers.

For many decades, silicone elastomers with oil incorporated have served as fouling-release coating for marine applications. In a comprehensive study involving a series of laboratory-based marine fouling assays and extensive global field studies of up to 2-year duration, we compare polydimethylsiloxane (PDMS) coatings of the same composition loaded with oil via two different methods. One method used a traditional, one-pot pre-cure oil addition approach (o-PDMS) and another method used a newer post-cure infusion approach (i-PDMS). The latter displays a substantial improvement in biofouling prevention performance that exceeds established commercial silicone-based fouling-release coating standards. We interpret the differences in performance between one-pot and infused PDMS by developing a mechanistic model based on the Flory-Rehner theory of swollen polymer networks. Using this model, we propose that the chemical potential of the incorporated oil is a key consideration for the design of future fouling-release coatings, as the improved performance is driven by the formation and stabilization of an anti-adhesion oil overlayer on the polymer surface.

Tea stains-inspired initiator primer for surface grafting of antifouling and antimicrobial polymer brush coatings.

Inspired by tea stains, plant polyphenolic tannic acid (TA) was beneficially employed as the primer anchor for functional polymer brushes. The brominated TA (TABr) initiator primer was synthesized by partial modification of TA with alkyl bromide functionalities. TABr with trihydroxyphenyl moieties can readily anchor on a wide range of substrates, including metal, metal oxide, polymer, glass, and silicon. Concomitantly, the alkyl bromide terminals serve as initiation sites for atom transfer radical polymerization (ATRP). Cationic [2-(methacryloyloxy)ethyl]trimethylammonium chloride (META) and zwitterionic 2-methacryloyloxyethyl phosphorylcholine (MPC) and N-(3-sulfopropyl)-N-(methacryloxyethyl)-N,N-dimethylammonium betaine (SBMA) were graft-polymerized from the TABr-anchored stainless steel (SS) surface. The cationic polymer brushes on the modified surfaces are bactericidal, while the zwitterionic coatings exhibit resistance against bacterial adhesion. In addition, microalgal attachment (microfouling) and barnacle cyprid settlement (macrofouling) on the functional polymer-grafted surfaces were significantly reduced, in comparison to the pristine SS surface. Thus, the bifunctional TABr initiator primer provides a unique surface anchor for the preparation of functional polymer brushes for inhibiting both microfouling and macrofouling.

Sulfobetaine-based polymer brushes in marine environment: is there an effect of the polymerizable group on the antifouling performance?

Three different zwitterionic polymer brush coatings for marine biofouling control were prepared by surface-initiated atom transfer radical polymerization (ATRP) of sulfobetaine-based monomers including methacrylamide (SBMAm), vinylbenzene (SBVB) and vinylimidazolium (SBVI). None of these brush systems have been assessed regarding marine antifouling performance. Antifouling tests performed indicate that surfaces featuring these three brush systems substantially reduce the adhesion of the marine microalgae, Amphora coffeaeformis, and the settlement of cyprid larvae of the barnacle, Amphibalanus amphitrite, in a similar way, displaying comparable performance. Thus, it appears that the chemical structure of the polymerizable group has no substantial influence on marine antifouling performance.

Barnacle cement as surface anchor for "clicking" of antifouling and antimicrobial polymer brushes on stainless steel.

Barnacle cement (BC) was utilized 'beneficially' as a surface anchor on stainless steel (SS) for coupling of functional polymer brushes via "click" reactions in both "grafting-to" and "grafting-from" processes. Ethylene sulfide (ES), propargyl carbonylimidazole (PPC) and azidoethyl carbonylimidazole (AEC) reacted with amine and/or hydroxyl groups in BC to introduce the corresponding thiol, alkyne, and azide groups on SS surfaces (SS-thiol, SS-alkyne, and SS-azide, respectively). Antifouling zwitterionic SS-PMPC surface was prepared by thiol-ene photopolymerization of 2-methacryloyloxyethyl phosphorylcholine (MPC) from the SS-thiol surface. Protein-resistant SS-PPEGMA and protein-adsorbing SS-PPFS surfaces were prepared by coupling of the respective azide-functionalized poly(poly(ethylene glycol)methyl ether methacrylate) (azido-PPEGMA) and poly(2,3,4,5,6-pentafluorostyrene) (azido-PPFS) polymer brushes in azide-alkyne "click" reaction. Antifouling alkyne-functionalized poly(N-hydroxyethyl acrylamide) (alkynyl-PHEAA) and antibacterial alkyne-functionalized poly(2-(methacryloyloxy)ethyl trimethylammonium chloride) (alkynyl-PMETA) polymer brushes were clicked on the SS-azide surface. Adsorption of bovine serum albumin and bacteria fouling of Gram-negative Escherichia coli ( E. coli ) and Gram-positive Staphylococcus epidermidis ( S. epidermidis ) were investigated on the polymer-functionalized SS surfaces. The versatile bioanchor and functional polymer brush coatings are stable in an abiotic aqueous environment for over a month.

Inhibition of barnacle cyprid settlement using low frequency and intensity ultrasound.

Low frequency, low intensity ultrasound was demonstrated as an effective inhibitor of barnacle cyprid settlement. When the same substratum vibration amplitude (10.05 nm) and acoustic pressure (5 kPa) were applied, ultrasound at a frequency of 23 kHz significantly reduced cyprid settlement. The mechanism appeared to differ from the ultrasonic cavitation induced inhibition previously reported as no increased mortality was observed, and no change in the exploratory behaviour of cyprids was observed when they were exposed to this continuous ultrasonic irradiation regime. The application of ultrasound treatment in an intermittent mode of '5 min on and 20 min off' at 20-25 kHz and at the low intensity of 5 kPa produced the same effect as the continuous application of 23 kHz. This energy efficient approach to the use of low frequency, low intensity ultrasound may present a promising and efficient strategy regarding irradiation treatment for antifouling applications.

Biomimetic anchors for antifouling and antibacterial polymer brushes on stainless steel.

Barnacle cement (BC) was beneficially applied on stainless steel (SS) to serve as the initiator anchor for surface-initiated polymerization. The amine and hydroxyl moieties of barnacle cement reacted with 2-bromoisobutyryl bromide to provide the alkyl halide initiator for the surface-initiated atom transfer radical polymerization (ATRP) of 2-hydroxyethyl methacrylate (HEMA). The hydroxyl groups of HEMA polymer (PHEMA) were then converted to carboxyl groups for coupling of chitosan (CS) to impart the SS surface with both antifouling and antibacterial properties. The surface-functionalized SS reduced bovine serum albumin adsorption, bacterial adhesion, and exhibited antibacterial efficacy against Escherichia coli (E. coli). The effectiveness of barnacle cement as an initiator anchor was compared to that of dopamine, a marine mussel inspired biomimetic anchor previously used in surface-initiated polymerization. The results indicate that the barnacle cement is a stable and effective anchor for functional surface coatings and polymer brushes.

Natural antifoulants from the marine cyanobacterium Lyngbya majuscula.

Filamentous benthic marine cyanobacteria are a prolific source of structurally unique bioactive secondary metabolites. A total of 12 secondary metabolites, belonging to the mixed polyketide-polypeptide structural class, were isolated from the marine cyanobacterium, Lyngbya majuscula, and were tested to determine if they showed activity against barnacle larval settlement. The assays revealed four compounds, dolastatin 16, hantupeptin C, majusculamide A, and isomalyngamide A, that showed moderate to potent anti-larval settlement activities, with EC(50) values ranging from 0.003 to 10.6 microg ml(-1). In addition, field testing conducted over a period of 28 days (using the modified Phytagel method) based on the cyanobacterial compound, dolastatin 16, showed significantly reduced barnacle settlement as compared to controls at all the concentrations tested. The results of this study highlight the importance of marine cyanobacteria as an underexplored source of potential environmentally friendly antifoulants.