The settlement and colonization of marine organisms on submerged man-made surfaces is a major economic problem for many marine industries. The most apparent detrimental effects of biofouling are increased fuel consumption of ships, clogging of membranes and heat exchangers, disabled underwater sensors, and growth of biofoulers in aquaculture systems. The presently common-but environmentally very problematic-way to deal with marine biofouling is to incorporate biocides, which use biocidal products in the surface coatings to kill the colonizing organisms, into the surface coatings. Since the implementation of the International Maritime Organization Treaty on biocides in 2008, the use of tributyltin (TBT) is restricted and thus environmentally benign but effective surface coatings are required. In this short review, we summarize the different strategies which are pursued in academia and industry to better understand the mechanisms of biofouling and to develop strategies which can be used for industrial products. Our focus will be on chemically "inert" model surface coatings, in particular oligo- and poly(ethylene glycol) (OEG and PEG) functionalized surface films. The reasons for choosing this class of chemistry as an example are three-fold: Firstly, experiments on spore settlement on OEG and PEG coatings help to understand the mechanism of non-fouling of highly hydrated interfaces; secondly, these studies defy the common assumption that surface hydrophilicity-as measured by water contact angles-is an unambiguous and predictive tool to determine the fouling behavior on the surface; and thirdly, choosing this system is a good example for "interfacial systems chemistry": it connects the behavior of unicellular marine organisms with the antifouling properties of a hydrated surface coating with structural and electronic properties as derived from ab initio quantum mechanical calculations using the electronic wave functions of oxygen, hydrogen, and carbon. This short review is written to outline for non-experts the hierarchical structure in length- and timescale of marine biofouling and the role of surface chemistry in fouling prevention. Experts in the field are referred to more specialized recent reviews.

Marine biofouling is a longstanding problem because of the constant challenges placed by various fouling species and increasingly restricted environmental regulations for antifouling coatings. Novel nonbiocidal strategies to control biofouling will necessitate a multifunctional approach to coating design. Here we show that slippery liquid-infused porous surfaces (SLIPSs) provide another possible strategy to obtaining promising antifouling coatings. Microporous butyl methacrylate-ethylene dimethacrylate (BMA-EDMA) surfaces are prepared via UV-initiated free-radical polymerization. Subsequent infusion of fluorocarbon lubricants (Krytox103, Krytox100, and Fluorinert FC-70) into the porous microtexture results in liquid-repellent slippery surfaces. To study the interaction with marine fouling organisms, settlement of zoospores of the alga Ulva linza and cypris larvae of the barnacle Balanus amphitrite is tested in laboratory assays. BMA-EDMA surfaces infused with Krytox103 and Krytox100 exhibit remarkable inhibition of settlement (attachment) of both spores and cyprids to a level comparable to that of a poly(ethylene glycol) (PEG)-terminated self-assembled monolayer. In addition, the adhesion strength of sporelings (young plants) of U. linza is reduced for BMA-EDMA surfaces infused with Krytox103 and Krytox100 compared to pristine (noninfused) BMA-EDMA and BMA-EDMA infused with Fluorinert FC-70. Immersion tests suggest a correlation between the stability of slippery coatings in artificial seawater and fouling resistance efficacy. The results indicate great potential for the application of this concept in fouling-resistant marine coatings.

Protein resistance of self-assembled monolayers (SAMs) of hexa(ethylene glycols) (EG(6)) has previously been shown to be dependent on the alkoxyl end-group termination of the SAM, which determines wettability [S. Herrwerth, W. Eck, S. Reinhardt, and M. Grunze, J. Am. Chem. Soc. 125, 9359 (2003)]. In the present study, the same series of hexa(ethylene glycols) was used to examine the correlation between protein resistance and the settlement and adhesion of eukaryotic algal cells, viz., zoospores of the macroalga Ulva and cells of the diatom Navicula, which adhere to the substratum through the secretion of protein-containing glues. Results showed that the initial settlement of Ulva zoospores was highest on the hydrophilic EG(6)OH but that cells were only weakly adhered. The number of Ulva zoospores and Navicula cells firmly adhered to the SAMs systematically increased with decreasing wettability, as shown for the protein fibrinogen. The data are discussed in terms of hydration forces and surface charges in the SAMs.

Although zwitterionic chemistries are among the most promising materials for producing nonfouling surfaces, their structural diversity has been low until now. Here, we compare the in vitro fouling behavior of a set of four systematically varied sulfa-/sulfobetaine-containing zwitterionic hydrogel coatings against a series of proteins and nonmotile as well as motile marine organisms as model foulers. The coatings are prepared by simultaneous photoinduced cross-linking and surface anchoring to elucidate the effect of the molecular structure of the zwitterionic moieties on their antifouling activity. Analogously prepared coatings of poly­(butyl methacrylate) and poly­(oligoethylene glycol methacrylate) serve as references. Photoreactive polymers are synthesized by the statistical copolymerization of sulfobetaine or sulfabetaine methacrylates and methacrylamides with a benzophenone derivative of 2-hydroxyethyl methacrylate and are applied as a thin film coating. While keeping the density of the zwitterionic and cross-linker groups constant, the molecular structure of the zwitterionic side chains is varied systematically, as is the arrangement of the ion pairs in the side chain by changing the classical linear geometry to a novel Y-shaped geometry. All of the polyzwitterions strongly reduce fouling compared to poly­(butyl methacrylate). Overall, the sulfabetaine polyzwitterion coatings studied matches the high antifouling effectiveness of oligo­(ethylene glycol)-based ones used as a control. Nevertheless, performances varied individually for a given pair of polymer and fouler. The case of the polysulfobetaines exemplifies that minor chemical changes in the polymer structure affect the antifouling performance markedly. Accordingly, the antifouling performance of such polymers cannot be correlated simply to the type of zwitterion used (which could be generally ranked as better performing or poorer performing) but is a result of the polymer’s precise chemical structure. Our findings underline the need to enlarge the existing structural diversity of polyzwitterions for antifouling purposes to optimize the potential of their chemical structure.

We report a direct method to amplify the exponential growth of multilayers significantly by the alternating deposition of polyethylenimine (PEI) at high pH and poly(acrylic acid) (PAA) at low pH. The alternating pH switches the degree of ionization of the polyelectrolytes in the multilayers, which enhances the diffusion of PEI into and out of the film and hence increases the deposited mass per cycle. The synergetic action of the pH-tunable charge density and diffusivity of the weak polyelectrolytes provides a new method for the enhanced growth of multilayers with hierarchal micro- and nanostructured surfaces.

The influence of the number of repeating units in self-assembled monolayers (SAMs) of ethylene glycol and of their end-group termination on the settlement and adhesion of two types of algal cells, viz., zoospores of the macroalga Ulva and cells of the diatom Navicula , was studied. The findings are related to the resistance of these surfaces against fibrinogen adsorption. Results showed that settlement and adhesion of algal cells to oligo(ethylene glycol) (OEG; 2-6 EG units) and poly(ethylene glycol) (PEG; MW = 2000, 5000) SAMs was low, while resistance was less effective for mono(ethylene glycol) (EG(1)OH)-terminated surfaces. These findings concur with former protein adsorption studies. In situ microscopy showed that PEG surfaces inhibited the settlement of zoospores, i.e., zoospores did not attach to the surfaces and remained motile. In contrast, on EG(2-6)OH surfaces, although zoospores settled, i.e., they secreted adhesive and lost motility, adhesion between secreted adhesive and the surface was extremely weak, and the settled spores were unable to bond to the surfaces. The influence of surface properties such as hydration, conformational degrees of freedom, and interfacial characteristics of the SAMs is discussed to understand the underlying repulsive mechanisms occurring in (ethylene glycol)-based coatings.

The widespread occurrence of zwitterionic compounds in nature has incited their frequent use in designing biomimetic materials. Therefore, zwitterionic polymers are a thriving field. A particular interest for this particular polymer class has currently focused on their use in establishing neutral, low-fouling surfaces. After highlighting strategies to prepare model zwitterionic surfaces as well as those that are more suitable for practical purposes relying strongly on radical polymerization methods, we present recent efforts to diversify the structure of the hitherto quite limited variety of zwitterionic monomers and of the derived polymers. We identify key structural variables, consider their influence on essential properties such as overall hydrophilicity and long-term stability, and discuss promising targets for the synthesis of new variants.

The interaction of covalently coupled hyaluronic acid, alginic acid, and pectic acid with proteins, cells (hematopoietic KG1a and Jurkat cells), and marine organisms (algal zoospores and barnacle cypris larvae) is compared. In contrast to cells and proteins for which such polysaccharide coatings are known for their antiadhesive properties, marine algal spores and barnacle cyprids were able to colonize the surfaces. Of the three polysaccharides, hyaluronic acid showed the lowest settlement of both Ulva zoopores and barnacles. Photoelectron spectroscopy reveals that the polysaccharide coatings tend to bind bivalent ions, such as calcium, from salt water. Such pretreatment with a high salinity medium significantly changes the protein and hematopoietic cell resistance of the surfaces. Complexation of bivalent ions is therefore considered as one reason for the decreased resistance of polysaccharide coatings when applied in the marine environment.