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Biofouling on marine surfaces causes immense material and financial harm for maritime vessels and related marine industries. Previous reports have shown the effectiveness of amphiphilic coating systems based on poly(dimethylsiloxane) (PDMS) against such marine foulers. Recent studies on biofouling mechanisms have also demonstrated acidic microenvironments in biofilms and stronger adhesion at low-pH conditions. This report presents the design and utilization of amphiphilic polymer coatings with buffer functionalities as an active disruptor against four different marine foulers. Specifically, this study explores both neutral and zwitterionic buffer systems for marine coatings, offering insights into coating design. Overall, these buffer systems were found to improve foulant removal, and unexpectedly were the most effective against the diatom Navicula incerta.

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Orthopedic implants such as knee and hip implants are one of the most important types of medical devices. Currently, the surface of the most advanced implants consists of titanium or titanium-alloys with high porosity at the bone-contacting surface leading to superior mechanical properties, excellent biocompatibility, and the capability of inducing osseointegration. However, the increased surface area of porous titanium provides a nidus for bacteria colonization leading to implant-related infections, one of the main reasons for implant failure. Here, two readily applicable titanium-coatings based on hydrophilic carboxybetaine polymers that turn the surface stealth thereby preventing bacterial adhesion and colonization are developed. These coatings are biocompatible, do not affect cell functionality, exhibit great antifouling properties, and do not cause additional inflammation during the healing process. In this way, the coatings can prevent implant-related infections, while at the same time being completely innocuous to its biological environment. Thus, these coating strategies are a promising route to enhance the biocompatibility of orthopedic implants and have a high potential for clinical use, while being easy to implement in the implant manufacturing process.

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The poly(3,4-ethylenedioxythiophene) (PEDOT) interface, renowned for its biocompatibility and intrinsic conductivity, holds substantial potential in biosensing and cellular modulation. Through strategic functionalization, PEDOT derivatives can be adaptable for multifaceted applications. Notably, integrating phosphorylcholine (PC) groups into PEDOT, mimicking the hydrophilic headgroups from cell membranes, confers exceptional antifouling properties on the coating. This study systematically investigated biomolecule interactions with distinct forms of PEDOT, incorporating variations in surface modifications and structure. Zwitterionic PEDOT-PC was electropolymerized on smooth and nanostructured surfaces using various feeding ratios in electrolytes to finely control the antifouling properties of the interface. Precise electropolymerization conditions governed the attainment of smooth and nanostructured filamentous surfaces. The study employed a quartz crystal microbalance with dissipation (QCM-D) to assess protein binding behavior. Bovine serum albumin (BSA), lysozyme (LYZ), cytochrome c (cyt c), and fibronectin (FN) were used to evaluate their binding affinities for PEDOT films. FN, a pivotal extracellular matrix component, was included for connecting to cell adhesion behavior. Furthermore, the cellular adhesion behaviors on PEDOT interfaces were evaluated. Three cell lines─MG-63 osteosarcoma, HeLa cervical cancer, and fibroblast NIH/3T3 were examined. The presence of PC moieties significantly altered the adhesive response, including the number of attached cells, their morphologies, and nucleus shrinkage. MG-63 cells exhibited the highest tolerance for PC moieties. A feeding ratio of PEDOT-PC exceeding 70% resulted in cell apoptosis. This study contributes to understanding biomolecule adsorption on PEDOT surfaces of diverse morphologies and degrees of the antifouling moiety. Meanwhile, it also sheds light on the responses of various cell types.

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Marine biofouling is an undeniable challenge for aquatic systems since it is responsible for several environmental and ecological problems and economic losses. Several strategies have been developed to mitigate fouling-related issues in marine environments, including developing marine coatings using nanotechnology and biomimetic models, and incorporating natural compounds, peptides, bacteriophages, or specific enzymes on surfaces. The advantages and limitations of these strategies are discussed in this review, and the development of novel surfaces and coatings is highlighted. The performance of these novel antibiofilm coatings is currently tested by in vitro experiments, which should try to mimic real conditions in the best way, and/or by in situ tests through the immersion of surfaces in marine environments. Both forms present their advantages and limitations, and these factors should be considered when the performance of a novel marine coating requires evaluation and validation. Despite all the advances and improvements against marine biofouling, progress toward an ideal operational strategy has been slow given the increasingly demanding regulatory requirements. Recent developments in self-polishing copolymers and fouling-release coatings have yielded promising results which set the basis for the development of more efficient and eco-friendly antifouling strategies.

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Two types of amphiphilic random terpolymers, poly(ethylene glycol methyl ether methacrylate)-ran-poly(2,2,6,6-tetramethylpiperidinyloxy methacrylate)-ran-poly(polydimethyl siloxane methacrylate) (PEGMEMA-r-PTMA-r-PDMSMA), were synthesized and evaluated for antifouling (AF) and fouling-release (FR) properties using diverse marine fouling organisms. In the first stage of production, the two respective precursor amine terpolymers containing (2,2,6,6-tetramethyl-4-piperidyl methacrylate) units (PEGMEMA-r-PTMPM-r-PDMSMA) were synthesized by atom transfer radical polymerization using various comonomer ratios and two initiators: alkyl halide and fluoroalkyl halide. In the second stage, these were selectively oxidized to introduce nitroxide radical functionalities. Finally, the terpolymers were incorporated into a PDMS host matrix to create coatings. AF and FR properties were examined using the alga Ulva linza, the barnacle Balanus improvisus, and the tubeworm Ficopomatus enigmaticus. The effects of comonomer ratios on surface properties and fouling assay results for each set of coatings are discussed in detail. There were marked differences in the effectiveness of these systems against the different fouling organisms. The terpolymers had distinct advantages over monopolymeric systems across the different organisms, and the nonfluorinated PEG and nitroxide combination was identified as the most effective formulation against B. improvisus and F. enigmaticus.

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Due to its several economic and ecological consequences, biofouling is a widely recognized concern in the marine sector. The search for non-biocide-release antifouling coatings has been on the rise, with carbon-nanocoated surfaces showing promising activity. This work aimed to study the impact of pristine graphene nanoplatelets (GNP) on biofilm development through the representative marine bacteria Cobetia marina and to investigate the antibacterial mechanisms of action of this material. For this purpose, a flow cytometric analysis was performed and a GNP/polydimethylsiloxane (PDMS) surface containing 5 wt% GNP (G5/PDMS) was produced, characterized, and assessed regarding its biofilm mitigation potential over 42 days in controlled hydrodynamic conditions that mimic marine environments. Flow cytometry revealed membrane damage, greater metabolic activity, and endogenous reactive oxygen species (ROS) production by C. marina when exposed to GNP 5% (w/v) for 24 h. In addition, C. marina biofilms formed on G5/PDMS showed consistently lower cell count and thickness (up to 43% reductions) than PDMS. Biofilm architecture analysis indicated that mature biofilms developed on the graphene-based surface had fewer empty spaces (34% reduction) and reduced biovolume (25% reduction) compared to PDMS. Overall, the GNP-based surface inhibited C. marina biofilm development, showing promising potential as a marine antifouling coating.

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The development of environmentally friendly antifouling strategies for marine applications is of paramount importance, and the fabrication of innovative nanocomposite coatings is a promising approach. Moreover, since Optical Coherence Tomography (OCT) is a powerful imaging technique in biofilm science, the improvement of its analytical power is required to better evaluate the biofilm structure under different scenarios. In this study, the effect of carbon nanotube (CNT)-modified surfaces in cyanobacterial biofilm development was assessed over a long-term assay under controlled hydrodynamic conditions. Their impact on the cyanobacterial biofilm architecture was evaluated by novel parameters obtained from three-dimensional (3D) OCT analysis, such as the contour coefficient, total biofilm volume, biovolume, volume of non-connected pores, and the average size of non-connected pores. The results showed that CNTs incorporated into a commercially used epoxy resin (CNT composite) had a higher antifouling effect at the biofilm maturation stage compared to pristine epoxy resin. Along with a delay in biofilm development, a decrease in biofilm wet weight, thickness, and biovolume was also achieved with the CNT composite compared to epoxy resin and glass (control surfaces). Additionally, biofilms developed on the CNT composite were smoother and presented a lower porosity and a strictly packed structure when compared with those formed on the control surfaces. The novel biofilm parameters obtained from 3D OCT imaging are extremely important when evaluating the biofilm architecture and behavior under different scenarios beyond marine applications.

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Whenever an artificial surface comes into contact with blood, proteins are rapidly adsorbed onto its surface. This phenomenon, termed fouling, is then followed by a series of undesired reactions involving activation of complement or the coagulation cascade and adhesion of leukocytes and platelets leading to thrombus formation. Thus, considerable efforts are directed towards the preparation of fouling-resistant surfaces with the best possible hemocompatibility. Herein, a comprehensive hemocompatibility study after heparinized blood contact with seven polymer brushes prepared by surface-initiated atom transfer radical polymerization is reported. The resistance to fouling is quantified and thrombus formation and deposition of blood cellular components on the coatings are analyzed. Moreover, identification of the remaining adsorbed proteins is performed via mass spectroscopy to elucidate their influence on the surface hemocompatibility. Compared with an unmodified glass surface, the grafting of polymer brushes minimizes the adhesion of platelets and leukocytes and prevents the thrombus formation. The fouling from undiluted blood plasma is reduced by up to 99%. Most of the identified proteins are connected with the initial events of foreign body reaction towards biomaterial (coagulation cascade proteins, complement component, and inflammatory proteins). In addition, several proteins that are not previously linked with blood-biomaterial interaction are presented and discussed.

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Conducting polymers (CPs) are of great interests to researchers around the world in biomedical applications owing to their unique electrical and mechanical properties. Besides, they are easy to fabricate and have long-term stability. These features make CPs a powerful building block of modern biomaterials. Peptide functionalization has been a versatile tool for the development of CP-based biomaterials. With the aid of peptide modifications, the biocompatibility, target selectivity, and cellular interactions of CPs can be greatly improved. Reflecting these aspects, an increasing number of studies on peptide-integrated conducting polymers have been reported recently. In this review, various kinds of peptide immobilization strategies on CPs are introduced. Moreover, the aims of peptide modification are discussed in three aspects: enhancing the specific selectivity, avoiding nonspecific adhesion, and mimicking the environment of extracellular matrix. We highlighted recent studies in the applications of peptide-integrated CPs in electrochemical sensors, antifouling surfaces, and conductive biointerfaces. These studies have shown great potentials from the integration of peptide and CPs as a versatile platform for advanced biological and clinical applications in the near future.

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The buildup of organic matter and organisms on surfaces exposed to marine environments, known as biofouling, is a disruptive and costly process affecting maritime operations. Previous research has identified some of the surface characteristics particularly suited to the creation of antifouling and fouling-release surfaces, but there remains room for improvement against both macrofouling and microfouling organisms. Characterization of their adhesives has shown that many rely on oxidative chemistries. In this work, we explore the incorporation of the stable radical 2,2,6,6-tetramethylpipiderin-1-oxyl (TEMPO) as a component in an amphiphilic block copolymer system to act as an inhibitor for marine cements, disrupting adhesion of macrofouling organisms. Using polystyrene-b-poly(dimethylsiloxane-r-vinylmethysiloxane) block copolymers, pendent vinyl groups were functionalized with TEMPO and poly(ethylene glycol) to construct an amphiphilic material with redox active character. The antifouling and fouling-release performance of these materials was investigated through settlement and removal assays of three model fouling organisms and correlated to surface structure and chemistry. Surfaces showed significant antifouling character and fouling-release performance was increased substantially toward barnacles by the incorporation of stable radicals, indicating their potential for marine antifouling applications.

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The protein/cell interactions with the surface at the blood-biomaterial interface generally control the efficiency of biomedical devices. A wide range of active processes and slow kinetics occur simultaneously with many biomaterials in healthcare applications, leading to multiple biological reactions and reduced clinical functions. In this work, we present a brief review of studies as the interface between proteins and biomaterials. These include mechanisms of resistance to proteins, protein-rejecting polyelectrolyte multilayers, and coatings of hydrophilic, polysaccharide and phospholipid nature. The mechanisms required to attain surfaces that resist adhesion include steric exclusion, water-related effects, and volume effects. Also, approaches in the use of hydrophilic, highly hydrated, and electrically neutral coatings have demonstrated a good ability to decrease cell adhesion. Moreover, amongst the available methods, the approach of layer-by-layer deposition has been known as an interesting process to manipulate protein and cell adhesion behavior.

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Although laboratory assays provide valuable information about the antifouling effectiveness of marine surfaces and the dynamics of biofilm formation, they may be laborious and time-consuming. This study aimed to determine the potential of short-time adhesion assays to estimate how biofilm development may proceed. The initial adhesion and cyanobacterial biofilm formation were evaluated using glass and polymer epoxy resin surfaces under different hydrodynamic conditions and were compared using linear regression models. For initial adhesion, the polymer epoxy resin surface was significantly associated with a lower number of adhered cells compared with glass (-1.27 × 105 cells.cm-2). Likewise, the number of adhered cells was significantly lower (-1.16 × 105 cells.cm-2) at 185 than at 40 rpm. This tendency was maintained during biofilm development and was supported by the biofilm wet weight, thickness, chlorophyll a content and structure. Results indicated a significant correlation between the number of adhered and biofilm cells (r = 0.800, p < 0.001). Moreover, the number of biofilm cells on day 42 was dependent on the number of adhered cells at the end of the initial adhesion and hydrodynamic conditions (R2 = 0.795, p < 0.001). These findings demonstrate the high potential of initial adhesion assays to estimate marine biofilm development.

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Ultralow protein fouling behavior is a common target for new high-performance materials. Ultralow fouling is often defined based on the amount of irreversibly adsorbed protein (< 5 ng cm-2) measured by a surface ensemble averaging method. However, protein adsorption at solid interfaces is a dynamic process involving multiple steps, which may include adsorption, desorption, and irreversible protein denaturation. In order to better optimize the performance of antifouling surfaces, it is imperative to fully understand how proteins interact with surfaces, including kinetics of adsorption and desorption, conformation, stability, and amount of adsorbed proteins. Defining ultralow fouling surfaces based on a measurement at or near the limit of detection of a surface-averaged measurement may not capture all of this behavior. Single-molecule microscopy techniques can resolve individual protein-surface interactions with high temporal and spatial resolution. This information can be used to tune the properties of surfaces to better resist protein adsorption. In this work, we demonstrate how combining surface plasmon resonance, X-ray photoelectron spectroscopy, atomic force microscopy, and single-molecule localization microscopy provides a more complete picture of protein adsorption on low fouling and ultralow fouling polyelectrolyte multilayer and polymer brush surfaces, over different regimes of protein concentration. In this case, comparing the surfaces using surface plasmon resonance alone is insufficient to rank their resistance to protein adsorption. Our results suggest a revision of the accepted definition of ultralow fouling surfaces is timely: with the advent of time-resolved studies of protein adsorption kinetics at the single-molecule level, it is neither necessary nor sufficient to rely on a surface averaging techniques to qualify ultralow fouling surfaces. Since protein adsorption is a dynamic process, understanding how surface properties affect the kinetics of protein adsorption will enable the design of future generations of advanced antifouling materials. STATEMENT OF SIGNIFICANCE: The design of ultralow fouling surfaces is often optimized based on a single surface-averaging technique measuring the amount of irreversibly adsorbed protein. This work provides a critical comparison of alternative techniques for evaluating protein adsorption on low fouling and ultralow fouling surfaces, and demonstrates how additional information about the dynamics of protein-surface interactions at the interface can be obtained by application of single-molecule microscopy. This approach could be used to better elucidate mechanisms of protein resistance and design principles for advanced ultralow fouling materials.

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A novel MWCNT-PNIPAAm nanocomposite membrane was developed with an excellent cleaning efficiency of thermo-responsive surface. The thermo-responsive N-isopropyle acryleamide (NIPAAm) monomer was polymerized on the surface of MWCNT via free radical polymerization. The prepared MWCNT-PNIPAAm nanocomposite was characterized by FTIR, SEM and TGA analyses. Various amounts of the prepared nanocomposite were incorporated into the membrane matrix by the physical blending method. The resultant membranes showed better surface wettability and pure water flux compared to pristine Polyethersulfone (PES) membrane. Furthermore, after filtration, the COD value of dairy wastewater was reduced to around 90% for all membranes. The thermo-responsive cleaning method was employed to investigate the cleaning efficiency of MWCNT-PNIPAAm membrane for dairy wastewater. The 99.9% flux recovery ratio was obtained for MWCNT-PNIPAAm-0.05% membranes. All these results confirmed that the presence of MWCNT-PNIPAAm nanocomposite in the membrane matrix improves the membrane hydrophilicity and antifouling properties.

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This systematic review examines effects of surface texture on marine biofouling and characterizes key research methodologies. Seventy-five published articles met selection criteria for qualitative analysis; experimental data from 36 underwent quantitative meta-analysis. Most studies investigated fouling mechanisms and antifouling performance only in laboratory assays with one to several test species. Textures were almost exclusively a single layer of regularly arranged geometric features rather than complex hierarchical or irregular designs. Textures in general had no effect or an inconclusive effect on fouling in 46% of cases. However, effective textures more often decreased (35%) rather than increased (19%) fouling. Complex designs were more effective against fouling (51%) than were regular geometric features (32%). Ratios of feature height, width, or pitch to organism body length were significant influences. The authors recommend further research on promising complex and hierarchical texture designs with more test species, as well as field studies to ground-truth laboratory results.

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The remarkable underwater adhesion capacity of the invasive freshwater mussel species Dreissena polymorpha (zebra mussel) causes extensive damage each year. The adhesive interface between the substrate surface and the mussels' adhesive plaques plays a key role in zebra mussel biofouling. Silicone-oil-infused polydimethylsiloxane (iPDMS), an omniphobic material in the class of liquid-infused slippery surfaces, has been shown to develop a uniform, microscale, antifouling surface oil layer, which we hypothesized would be effective against zebra mussel fouling. iPDMS substrates with varying levels of oil saturation were tested for their ability to disrupt mussel adhesion by characterizing zebra mussel reattachment in a simulated freshwater environment for 3 days. On fully saturated iPDMS samples or those near full saturation, zebra mussels showed no reattachment, compared to 41% reattachment on PDMS controls (no oil infusion). For lower saturation levels, the frequency of reattachment was decreased relative to PDMS controls. Mussel detachment forces decreased in iPDMS as compared to PDMS, and adhesive failures occurred more frequently with higher iPDMS saturations. Surface analysis of the subsaturated iPDMS substrates showed incomplete coverage of the surface oil layer. After 3 days of immersion in artificial freshwater, subsaturated iPDMS substrates showed a decrease in slipperiness (measured by water slide angle), whereas in fully saturated iPDMS, the slipperiness was unchanged, despite no observed oil loss in either group. The decrease in slipperiness is attributed to microfouling of the subsaturated substrates, consistent with incomplete surface oil layer coverage, and supports the notion that full oil layer coverage is required for effective antifouling properties. Employing iPDMS as an antifouling coating shows promise against freshwater mussel adhesion, and this work further aids in understanding the antifouling mechanism of iPDMS and the role of the plaque-substrate interface in freshwater mussel adhesion.

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A new method is demonstrated for preparing antifouling and low nonspecific adsorption surfaces on poorly reactive hydrophobic substrates, without the need for energy-intensive or environmentally aggressive pretreatments. The surface-active protein hydrophobin was covalently modified with a controlled radical polymerization initiator and allowed to self-assemble as a monolayer on hydrophobic surfaces, followed by the preparation of antifouling surfaces by Cu(0)-mediated living radical polymerization of poly(ethylene glycol) methyl ether acrylate (PEGA) performed in situ. By taking advantage of hydrophobins to achieve at the same time the immobilization of protein A, this approach allowed to prepare surfaces for IgG1 binding featuring greatly reduced nonspecific adsorption. The success of the surface modification strategy was investigated by contact angle, XPS, and AFM characterization, while the antifouling performance and the reduction of nonspecific binding were confirmed by QCM-D measurements.

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It is widely recognised that findings from experimental studies should be replicated before their conclusions are accepted as definitive. In many research areas, synthesis of results from multiple studies is carried out via systematic review and meta-analysis. Some fields are also moving away from null hypothesis significance testing, which uses p values to identify 'significant' effects, towards an estimation approach concerned with effect sizes and confidence intervals. This review argues that these techniques are underused in biofouling and antifouling (AF) research and discusses potential benefits of their adoption. They enable comparison of test surfaces even when these are not tested simultaneously, and allow results from repeated tests on the same surfaces to be combined. They also enable the use of published data to explore effects of different variables on the functioning of AF surfaces. AF researchers should consider using these approaches and reporting results in ways that facilitate future research syntheses.

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Platelets have a limited shelf life, due to the risk of bacterial contamination and platelet quality loss. Most platelet storage bags are made of a mixture of polyvinyl chloride with a plasticizer, denoted as pPVC. To improve biocompatibility of pPVC with platelets and to inhibit bacterial biofilm formation, an antifouling polymer coating is developed using mussel-inspired chemistry. A copolymer of N,N-dimethylacrylamide and N-(3-aminopropyl)methacrylamide hydrochloride is synthesized and coupled with catechol groups, named DA51-cat. Under mild aqueous conditions, pPVC is first equilibrated with an anchoring polydopamine layer, followed by a DA51-cat layer. Measurements show this coating decreases fibrinogen adsorption to 5% of the control surfaces. One-step coating with DA51-cat does not coat pPVC efficiently although it is sufficient for coating silicon wafers and gold substrates. The dual layer coating on platelet bags resists bacterial biofilm formation and considerably decreases platelet adhesion. A cationic antimicrobial peptide, E6, is conjugated to DA51-cat then coated on silicon wafers and introduces bactericidal activity to these surfaces. Time-of-flight second ion-mass spectroscopy is successfully applied to characterize these surfaces. pPVC is widely used in medical devices; this method provides an approach to controlling biofouling and bacterial growth on it without elaborate surface modification procedures.

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The preparation of a fluorine-containing synergistic nonfouling/fouling-release surface, using a b-PFMA-PEO asymmetric molecular brush possessing both poly(ethylene glycol) (PEO) and poly(2,2,2-trifluoroethyl methacrylate) (PFMA) side chains densely distributed on the same repeat unit along the polymeric backbone, is reported. On the basis of the poly(Br-acrylate-alkyne) macroagent comprising two functionalities (alkynyl and 2-bromopropionate), which is prepared by reversible addition-fragmentation chain transfer homopolymerization of a new trifunctional acrylate monomer of Br-acrylate-alkyne, b-PFMA-PEO asymmetric molecular brushes are obtained by concurrent atom transfer radical polymerization and Cu-catalyzed azide/alkyne cycloaddition "click" reaction in a one-shot system. A spin-cast thin film of the b-PFMA-PEO asymmetric molecular brush exhibits a synergistic antifouling property, in which PEO side chains endow the surface with a nonfouling characteristic, whereas PFMA side chains display the fouling-release functionality because of their low surface energy. Both protein adsorption and cell adhesion tests provided estimates of the antifouling activity of the asymmetric molecular brush surfaces, which was demonstrated to be influenced by the degree of polymerization of the backbone and the length of the PEO and PFMA side chains. With compositional heterogeneities, all asymmetric molecular brush surfaces show considerable antifouling performance with much less protein adsorption (at least 45% off, up to 75% off) and cell adhesion (at least 70% off, up to 90% off) in comparison with a bare surface.