Anthony B. Brennan

Engineered antifouling microtopographies – effect of feature size, geometry, and roughness on settlement of zoospores of the green alga Ulva

Abstract The effect of feature size, geometry, and roughness on the settlement of zoospores of the ship fouling alga Ulva was evaluated using engineered microtopographies in polydimethylsiloxane elastomer. The topographies studied were designed at a feature spacing of 2 μm and all significantly reduced spore settlement compared to a smooth surface. An indirect correlation between spore settlement and a newly described engineered roughness index (ERI) was identified. ERI is a dimensionless ratio based on Wenzels roughness factor, depressed surface fraction, and the degree of freedom of spore movement. Uniform surfaces of either 2 μm diameter circular pillars (ERI = 5.0) or 2 μm wide ridges (ERI = 6.1) reduced settlement by 36% and 31%, respectively. A novel multi-feature topography consisting of 2 μm diameter circular pillars and 10 μm equilateral triangles (ERI = 8.7) reduced spore settlement by 58%. The largest reduction in spore settlement, 77%, was obtained with the Sharklet AF™ topography (ERI = 9.5).

Engineered antifouling microtopographies - : correlating wettability with cell attachment

Abstract Bioadhesion and surface wettability are influenced by microscale topography. In the present study, engineered pillars, ridges and biomimetic topography inspired by the skin of fast moving sharks (Sharklet AF™) were replicated in polydimethylsiloxane elastomer. Sessile drop contact angle changes on the surfaces correlated well (R2 = 0.89) with Wenzel and Cassie and Baxters relationships for wettability. Two separate biological responses, i.e. settlement of Ulva linza zoospores and alignment of porcine cardiovascular endothelial cells, were inversely proportional to the width (between 5 and 20 μm) of the engineered channels. Zoospore settlement was reduced by ∼85% on the finer (ca 2 μm) and more complex Sharklet AF™ topographies. The response of both cell types suggests their responses are governed by the same underlying thermodynamic principles as wettability.

Non-toxic antifouling strategies

The term fouling generally refers to an undesirable process in which a surface becomes encrusted with material from the surrounding environment. In the case of biofouling, that material consists of organisms and their by-products e.g., extracellular polysaccharides and metabolites. Biofouling limits the performance of devices in numerous applications; however, this review focuses on antifouling biomaterials for marine and biomedical applications. The surface chemistry and physical properties of the substratum are both crucial to preventing the recruitment of biofouling organisms. Natural antifouling surfaces exhibit both chemical and physical attributes. The chemical structure is discussed briefly as it relates to both anti-fouling and fouling-release properties. However, our focus has been to study physical cues as they relate to the initial attachment of fouling organisms.

Impact of engineered surface microtopography on biofilm formation of Staphylococcus aureus

The surface of an indwelling medical device can be colonized by human pathogens that can form biofilms and cause infections. In most cases, these biofilms are resistant to antimicrobial therapy and eventually necessitate removal or replacement of the device. An engineered surface microtopography based on the skin of sharks, Sharklet AFTM, has been designed on a poly(dimethyl siloxane) elastomer (PDMSe) to disrupt the formation of bacterial biofilms without the use of bactericidal agents. The Sharklet AFTM PDMSe was tested against smooth PDMSe for biofilm formation of Staphylococcus aureus over the course of 21 days. The smooth surface exhibited early-stage biofilm colonies at 7 days and mature biofilms at 14 days, while the topographical surface did not show evidence of early biofilm colonization until day 21. At 14 days, the mean value of percent area coverage of S. aureus on the smooth surface was 54% compared to 7% for the Sharklet AFTM surface (p<0.01). These results suggest that surface modification of indwelling medical devices and exposed sterile surfaces with the Sharklet AFTM engineered topography may be an effective solution in disrupting biofilm formation of S. aureus.

Species-specific engineered antifouling topographies: correlations between the settlement of algal zoospores and barnacle cyprids

Abstract Novel, non-toxic antifouling technologies are focused on the manipulation of surface topography to deter settlement of the dispersal stages of fouling organisms. This study investigated the effect of the aspect ratio (feature height/feature width) of topographical features engineered in polydimethylsiloxane, on the settlement of cyprids of Balanus amphitrite and zoospores of Ulva linza. The correlation of relative aspect ratios to antifouling efficacy was proven to be significant. An increase in aspect ratio resulted in an increase of fouling deterrence for both zoospores and cyprids. The spore density of Ulva was reduced 42% with each unit increase in aspect ratio of the Ulva-specific Sharklet AF™ topography. Similarly, the number of settled cyprids was reduced 45% with each unit increase in aspect ratio. The newly described barnacle-specific Sharklet AF™ topography (40 μm feature height, aspect ratio of 2) reduced cyprid settled by 97%. Techniques have been developed to superimpose the smaller Ulva-specific topographies onto the barnacle-specific surfaces into a hierarchical structure to repel both organisms simultaneously. The results for spore settlement on first-generation hierarchical surfaces provide insight for the efficacious design of such structures when targeting multiple settling species.

Adhesion and motility of fouling diatoms on a silicone elastomer

Recent demands for non-toxic antifouling technologies have led to increased interest in coatings based on silicone elastomers that ‘release’ macrofouling organisms when hydrodynamic conditions are sufficiently robust. However, these types of coatings accumulate diatom slimes, which are not released even from vessels operating at high speeds ( > 30 knots). In this study, adhesion strength and motility of three common fouling diatoms (Amphora coffeaeformis var. perpusilla (Grunow) Cleve, Craspedostauros australis Cox and Navicula perminuta Grunow) were measured on a polydimethylsiloxane elastomer (PDMSE) and acid-washed glass. Adhesion of the three species was stronger to PDMSE than to glass but the adhesion strengths varied. The wall shear stress required to remove 50% of cells from PDMSE was 17 Pa for Craspedostauros, 24 Pa for Amphora and >> 53 Pa for Navicula; the corresponding values for glass were 3, 10 and 25 Pa. In contrast, the motility of the three species showed little or no correlation between the two surfaces. Craspedostauros moved equally well on glass and PDMSE, Amphora moved more on glass initially before movement ceased and Navicula moved more on PDMSE before movement ceased. The results show that fouling diatoms adhere more strongly to a hydrophobic PDMSE surface, and this feature may contribute to their successful colonization of low surface energy, foul-release coatings. The results also indicate that diatom motility is not related to adhesion strength, and motility does not appear to be a useful indicator of surface preference by diatoms.

Antifouling Potential of Lubricious, Micro-engineered, PDMS Elastomers against Zoospores of the Green Fouling Alga Ulva (Enteromorpha)

The settlement and release of Ulva spores from chemically modified, micro-engineered surface topographies have been investigated using poly(dimethyl siloxane) elastomers (PDMSe) with varying additions of non-network forming poly(dimethyl siloxane) based oils. The topographic features were based on 5 μm wide pillars or ridges separated by 5, 10, or 20 μm wide channels. Pattern depths were 5 or 1.5 μm. Swimming spores showed no marked difference in settlement on smooth surfaces covered with excess PDMS oils. However, incorporation of oils significantly reduced settlement density on many of the surfaces with topographic features, in particular, the 5 μm wide and deep channels. Previous results, confirmed here, demonstrate preferences by the spores to settle in channels and against pillars with spatial dimensions of 5 μm, 10 μm and 20 μm. The combination of lubricity and pillars significantly reduced the number of attached spores compared to the control, smooth, unmodified PDMSe surfaces when exposed to turbulent flow in a flow channel. The results are discussed in relation to the energy needs for spores to adhere to various surface features and the concepts of ultrahydrophobic surfaces. A factorial, multi-level experimental design was analyzed and a 2nd order polynomial model was regressed for statistically significant effects and interactions to determine the magnitude and direction of influence on the spore density measurements between factor levels.

Engineered nanoforce gradients for inhibition of settlement (attachment) of swimming algal spores.

Current antifouling strategies are focused on the development of environmentally friendly coatings that protect submerged surfaces from the accumulation of colonizing organisms (i.e., biofouling). One ecofriendly approach is the manipulation of the surface topography on nontoxic materials to deter settlement of the dispersal stages of fouling organisms. The identification of effective antifouling topographies typically occurs through trial-and-error rather than predictive models. We present a model and design methodology for the identification of nontoxic, antifouling surface topographies for use in the marine environment by the creation of engineered nanoforce gradients. The design and fabrication of these gradients incorporate discrete micrometer-sized features that are associated with the species-specific surface design technique of engineered topography and the concepts of mechanotransduction. The effectiveness of designed nanoforce gradients for antifouling applications was tested by evaluating the settlement behavior of zoospores of the alga Ulva linza. The surfaces with nanoforce gradients ranging from 125 to 374 nN all significantly reduced spore settlement relative to a smooth substrate, with the highest reduction, 53%, measured on the 374 nN gradient surface. These results confirm that the designed nanoforce gradients may be an effective tool and predictive model for the design of unique nontoxic, nonfouling surfaces for marine applications as well as biomedical surfaces in the physiological environment.

Structure-property behaviour of sol-gel derived hybrid materials: effect of a polymeric acid catalyst

Abstract Poly(styrene sulphonic acid) is used to prepare ceramers based upon poly(tetramethylene oxide) oligomers and tetraethyl orthosilicate. These hybrid network materials prepared by sol-gel processing demonstrate the successful use of a polymeric acid catalyst to prepare these previously described optically clear hybrid materials. The mechanical properties of the polymeric acid-catalysed ceramers are improved over systems of the same composition catalysed with HCl. The loss dispersion behaviour of these materials as well as general morphological features, evaluated by small-angle X-ray scattering, are quite similar to those of the ceramers catalysed with HCl. Some comparisons of their thermogravimetric behaviour are also made.

A model that predicts the attachment behavior of Ulva linza zoospores on surface topography

A predictive model for the attachment of spores of the green alga Ulva on patterned topographical surfaces was developed using a constant refinement approach. This ‘attachment model’ incorporated two historical data sets and a modified version of the previously-described Engineered Roughness Index. Two sets of newly-designed surfaces were used to evaluate the effect of two components of the model on spore settlement. Spores attached in fewer numbers when the area fraction of feature tops increased or when the number of distinct features in the design increased, as predicted by the model. The model correctly predicted the spore attachment density on three previously-untested surfaces relative to a smooth surface. The two historical data sets and two new data sets showed high correlation (R 2 = 0.88) with the model. This model may be useful for designing new antifouling topographies.