Hydration and Chain Entanglement Determines the Optimum Thickness of Poly(HEMA-co-PEG(10)MA) Brushes for Effective Resistance to Settlement and Adhesion of Marine Fouling Organisms

Understanding how surface physicochemical properties influence the settlement and adhesion of marine fouling organisms is important for the development of effective and environmentally benign marine antifouling coatings. We demonstrate that the thickness of random poly(HEMA-co-PEG(10)DMA) copolymer brushes affect antifouling behavior. Films of thicknesses ranging from 50 to 1000 angstrom were prepared via surface-initiated atom-transfer radical polymerization and characterized using infrared spectroscopy, ellipsometry, atomic force microscopy and contact angle measurements. The fouling resistance of these films was investigated by protein adsorption, attachment of the marine bacterium Cobetia marina, settlement and strength of attachment tests of zoospores of the marine alga Ulva linza and static immersion field tests. These assays show that the polymer film thickness influenced the antifouling performance, in that there is an optimum thickness range, 200-400 angstrom (dry thickness), where fouling of all types, as well as algal spore adhesion, was lower. Field test results also showed lower fouling within the same thickness range after 2 weeks of immersion. Studies by quartz crystal microbalance with dissipation and underwater captive bubble contact angle measurements show a strong correlation between lower fouling and higher hydration, viscosity and surface energy of the poly(HEMA-co-PEG(10)MA) brushes at thicknesses around 200-400 angstrom. We hypothesize that the reduced antifouling performance is caused by a lower hydration capacity of the polymer for thinner films, and that entanglement and crowding in the film reduces the conformational freedom, hydration capacity and fouling resistance for thicker films.Funding Agencies|European Community [237997]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009-00971]</p

Hydration and chain entanglement determines the optimum thickness of poly(HEMA-co-PEG10MA) brushes for effective antifouling properties

The generation of subject–verb agreement is a central component of grammatical encoding. It is sensitive to conceptual and grammatical influences, but the interplay between these factors is still not fully understood. We investigate how semantic integration of the subject noun phrase (‘the secretary of/with the governor’) and the Local Noun Number (‘the secretary with the governor/governors’) affect the ease of selecting the verb form. Two hypotheses are assessed: according to the notional hypothesis, integration encourages the assignment of the singular notional number to the noun phrase and facilitates the choice of the singular verb form. According to the lexical interference hypothesis, integration strengthens the competition between nouns within the subject phrase, making it harder to select the verb form when the nouns mismatch in number. In two experiments, adult speakers of Dutch completed spoken preambles (Experiment 1) or selected appropriate verb forms (Experiment 2). Results showed facilitatory effects of semantic integration (fewer errors and faster responses with increasing integration). These effects did not interact with the effects of the Local Noun Number (slower response times and higher error rates for mismatching than for matching noun numbers). The findings thus support the notional hypothesis and a model of agreement where conceptual and lexical factors independently contribute to the determination of the number of the subject noun phrase and, ultimately, the verb

Charged hydrophilic polymer brushes and their relevance for understanding marine biofouling

The resistance of charged polymers to biofouling was investigated by subjecting cationic (PDMAEMA), anionic (PSPMA), neutral (PHEMA-co-PEG10MA), and zwitterionic (PSBMA) brushes to assays testing protein adsorption; attachment of the marine bacterium Cobetia marina; settlement and adhesion strength of zoospores of the green alga Ulva linza; settlement of barnacle (Balanus amphitrite and B. improvisus) cypris larvae; and field immersion tests. Several results go beyond the expected dependence on direct electrostatic attraction; PSPMA showed good resistance towards attachment of C. marina, low settlement and adhesion of U. linza zoospores, and significantly lower biofouling than on PHEMA-co-PEG10MA or PSBMA after a field test for one week. PDMAEMA showed potential as a contact-active anti-algal coating due to its capacity to damage attached spores. However, after field testing for eight weeks, there were no significant differences in biofouling coverage among the surfaces. While charged polymers are unsuitable as antifouling coatings in the natural environment, they provide valuable insights into fouling processes, and are relevant for studies due to charging of nominally neutral surfaces.Funding agencies:This study has received funding from the European Community's Seventh Framework Program FP7/2007-2013 [ grant agreement number 237997] (SEACOAT). TE acknowledges financial support from the Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [Faculty Grant SFO-Mat-LiU #2009-00971].</p

Hydration and Chain Entanglement Determines the Optimum Thickness of Poly(HEMA-<i>co</i>-PEG₁₀MA) Brushes for Effective Resistance to Settlement and Adhesion of Marine Fouling Organisms

Understanding how surface physicochemical properties influence the settlement and adhesion of marine fouling organisms is important for the development of effective and environmentally benign marine antifouling coatings. We demonstrate that the thickness of random poly­(HEMA-<i>co</i>-PEG₁₀MA) copolymer brushes affect antifouling behavior. Films of thicknesses ranging from 50 to 1000 Å were prepared via surface-initiated atom-transfer radical polymerization and characterized using infrared spectroscopy, ellipsometry, atomic force microscopy and contact angle measurements. The fouling resistance of these films was investigated by protein adsorption, attachment of the marine bacterium Cobetia marina, settlement and strength of attachment tests of zoospores of the marine alga Ulva linza and static immersion field tests. These assays show that the polymer film thickness influenced the antifouling performance, in that there is an optimum thickness range, 200–400 Å (dry thickness), where fouling of all types, as well as algal spore adhesion, was lower. Field test results also showed lower fouling within the same thickness range after 2 weeks of immersion. Studies by quartz crystal microbalance with dissipation and underwater captive bubble contact angle measurements show a strong correlation between lower fouling and higher hydration, viscosity and surface energy of the poly­(HEMA-<i>co</i>-PEG₁₀MA) brushes at thicknesses around 200–400 Å. We hypothesize that the reduced antifouling performance is caused by a lower hydration capacity of the polymer for thinner films, and that entanglement and crowding in the film reduces the conformational freedom, hydration capacity and fouling resistance for thicker films

Charged hydrophilic polymer brushes and their relevance for understanding marine biofouling

The resistance of charged polymers to biofouling was investigated by subjecting cationic (PDMAEMA), anionic (PSPMA), neutral (PHEMA-co-PEG10MA), and zwitterionic (PSBMA) brushes to assays testing protein adsorption; attachment of the marine bacterium Cobetia marina; settlement and adhesion strength of zoospores of the green alga Ulva linza; settlement of barnacle (Balanus amphitrite and B. improvisus) cypris larvae; and field immersion tests. Several results go beyond the expected dependence on direct electrostatic attraction; PSPMA showed good resistance towards attachment of C. marina, low settlement and adhesion of U. linza zoospores, and significantly lower biofouling than on PHEMA-co-PEG10MA or PSBMA after a field test for one week. PDMAEMA showed potential as a contact-active anti-algal coating due to its capacity to damage attached spores. However, after field testing for eight weeks, there were no significant differences in biofouling coverage among the surfaces. While charged polymers are unsuitable as antifouling coatings in the natural environment, they provide valuable insights into fouling processes, and are relevant for studies due to charging of nominally neutral surfaces.Funding agencies:This study has received funding from the European Community's Seventh Framework Program FP7/2007-2013 [ grant agreement number 237997] (SEACOAT). TE acknowledges financial support from the Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [Faculty Grant SFO-Mat-LiU #2009-00971].</p