Axel Rosenhahn

Settlement and adhesion of algal cells to hexa(ethylene glycol)-containing self-assembled monolayers with systematically changed wetting properties

Protein resistance of self-assembled monolayers (SAMs) of hexa(ethylene glycols) (EG6) 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 EG6OH 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.

Physicochemical properties of (Ethylene Glycol)-Containing Self-Assembled Monolayers Relevant for Protein and Algal Cell Resistance

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.

Slippery liquid-infused porous surfaces showing marine antibiofouling properties.

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.

pH-amplified exponential growth multilayers: a facile method to develop hierarchical micro- and nanostructured surfaces.

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.

Coherent imaging of biological samples with femtosecond pulses at the free-electron laser FLASH

Coherent x-ray imaging represents a new window to imaging non- crystalline, biological specimens at unprecedented resolutions. The advent of free-electron lasers (FEL) allows extremely high flux densities to be delivered to a specimen resulting in stronger scattered signal from these samples to be measured. In the best case scenario, the diffraction pattern is measured before the sample is destroyed by these intense pulses, as the processes involved in radiation damage may be substantially slower than the pulse duration. In this case, the scattered signal can be interpreted and reconstructed to yield a faithful image of the sample at a resolution beyond the conventional radiation damage limit. We employ coherent x-ray diffraction imaging (CXDI) using the free-electron

Digital In-line Holography as a Three-Dimensional Tool to Study Motile Marine Organisms During Their Exploration of Surfaces

The swimming patterns of zoospores of the green alga Ulva linza in the vicinity of a surface were investigated by digital in-line holography. Full 3D motion patterns were retrieved from measurements and the traces obtained were compared with known swimming patterns of spores of the brown alga Hincksia irregularis and the green alga Ulva linza as seen in a conventional optical microscope. Quantitative information such as swimming velocity was calculated from the 3D traces. The results demonstrate the potential of digital in-line holography to image and quantify exploratory patterns of behavior of motile spores close to surfaces. This technique can give detailed insight into mechanisms of surface colonization by spores and larvae of fouling organisms in response to changes in surface properties.

Advanced nanostructures for the control of biofouling: The FP6 EU Integrated Project AMBIO

The colonization of man made structures by marine or freshwater organisms or “biofouling” is a problem for maritime and aquaculture industries. Increasing restrictions on the use of toxic coatings that prevent biofouling, create a gap in the market that requires new approaches to produce novel nonbiocidal alternatives. This review details the systematic strategy adopted by an FP6 EU Integrated Project “AMBIO” to develop fundamental understanding of key surface properties that influence settlement and adhesion of fouling organisms. By this approach the project contributes to the understanding of fundamental phenomena involved in biofouling, and to the development of environmentally benign solutions by coating manufacturers within the consortium.

Adhesion of marine fouling organisms on hydrophilic and amphiphilic polysaccharides.

Polysaccharides are a promising material for nonfouling surfaces because their chemical composition makes them highly hydrophilic and able to form water-storing hydrogels. Here we investigated the nonfouling properties of hyaluronic acid (HA) and chondroitin sulfate (CS) against marine fouling organisms. Additionally, the free carboxyl groups of HA and CS were postmodified with the hydrophobic trifluoroethylamine (TFEA) to block free carboxyl groups and render the surfaces amphiphilic. All coatings were tested with respect to their protein resistance and against settlement and adhesion of different marine fouling species. Both the settlement and adhesion strength of a marine bacterium (Cobetia marina), zoospores of the seaweed Ulva linza, and cells of a diatom (Navicula incerta) were reduced compared to glass control surfaces. In most cases, TFEA capping increased or maintained the performance of the HA coatings, whereas for the very well performing CS coatings the antifouling performance was reduced after capping.

Al2O3-films on Ni3Al(111): a template for nanostructured cluster growth

In scanning tunnelling microscope images of thin Al2O3-films grown on Ni3Al(111) at 1000 K two super-lattices with periodicities of 2.6 and 4.5 nm, respectively, can be identified. These well-ordered nanostructures can be used as nucleation centres for metal particle growth. It can be shown that both nanostructures act as a template for the fabrication of ordered assemblies of metal clusters by mere physical vapour deposition. The degree of ordering of these nanostructures is largely dependent on the metal deposited. Here we report on the growth of Cu, Ag, Au, Mn, and V clusters on the Al2O3-films. The best results as far as ordering of the clusters is concerned was reached for V deposition at 550 K, which resulted in a nearly perfect hexagonal array of clusters with a spacing of 2.6 nm.

Spatial and temporal coherence properties of single free-electron laser pulses

The experimental characterization of the spatial and temporal coherence properties of the free-electron laser in Hamburg (FLASH) at a wavelength of 8.0 nm is presented. Double pinhole diffraction patterns of single femtosecond pulses focused to a size of about 10×10 μm(2) were measured. A transverse coherence length of 6.2 ± 0.9 μm in the horizontal and 8.7 ± 1.0 μm in the vertical direction was determined from the most coherent pulses. Using a split and delay unit the coherence time of the pulses produced in the same operation conditions of FLASH was measured to be 1.75 ± 0.01 fs. From our experiment we estimated the degeneracy parameter of the FLASH beam to be on the order of 10(10) to 10(11), which exceeds the values of this parameter at any other source in the same energy range by many orders of magnitude.