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Jürgen Rühe

Publications and source records attributed to Jürgen Rühe.

13 recordsLinked to original sources

Memory of surface patterns in mixed polymer brushes: simulation and experiment.

The correlation between the morphology of mixed polymer brushes and fluctuations of the grafting points is investigated by single-chain-in-mean-field simulations and experiments. The local topography of two types of mixed polystyrene-polymethylmethacrylate (PS-PMMA) brushes that differ in their modes of attachment has been studied during repeated microphase separation into laterally structured and homogeneous morphologies upon changing solvents. In the first type of brush (conventional), each of the surface-attached initiator groups starts the growth of either a PS or a PMMA chain in a random fashion. In the second case (Y-shaped mixed brushes), two chains of different types are attached to the same anchor group on the substrate. Whereas in the first case statistical fluctuations of the chemical composition occur on a local scale, such composition fluctuations are strongly suppressed in the latter case. The microphase-separated morphology is similar in both cases, but Y-shaped brushes exhibit a significantly weaker domain memory than do conventional PS-PMMA mixed brushes. The results of the experiment are compared with simulations, and a simple phenomenological argument and qualitative agreement are found. The observations demonstrate that small fluctuations in the grafting points are amplified by the microphase separation and nucleate the location of the domains in the mixed brush.

Journal Article↗

Domain registration in raft-mimicking lipid mixtures studied using polymer-tethered lipid bilayers.

The degree of domain registration in a liquid-ordered/liquid-disordered phase-separating lipid mixture consisting of 1-stearoyl-2-oleoyl-sn-3-phosphocholine, egg sphingomyelin, and cholesterol (molar mixing ratio of 1:1:1) was studied using three different planar lipid bilayer architectures distinguished by their bilayer-substrate distance d using epifluorescence microscopy. The bilayer systems, which were built layer by layer using Langmuir-Blodgett/Schaefer film depositions, included a solid-supported bilayer (d approximately 15 A) and two polymer-supported bilayers with d approximately 30 A and d approximately 58 A, respectively. Complete domain registration between Langmuir-Blodgett and Schaefer monolayer domains was observed for d approximately 58 A but not in the cases when d approximately 15 A and d approximately 30 A. Building the bilayer layer by layer guaranteed that any preexisting domains were not in registration initially; our data show that the domain registration observed was not caused by lipid flip-flop or by lateral rearrangement of preexisting large-scale domains. Instead, additional studies on bilayer systems with asymmetric lipid composition indicate that preexisting domains in the Langmuir-Blodgett monolayer induce the formation of completely registered domains in the opposite Schaefer monolayer. This study provides insight into possible biophysical mechanisms of transbilayer domain coupling. Our findings support the concept that the formation of transbilayer signaling platforms based on registered raft domains may occur without the active involvement of membrane-spanning proteins.

Cholesterol↗

Fabrication of chemically microstructured polymer brushes.

In this paper, a new and simple pathway to fabricate polymer brush layers with lateral control over the chemical composition is described. The process combines two subsequent free radical grafting from steps: in the first step, a micropatterned polymer brush is grown by photochemical initiation of the polymer growth from the surface through a mask in direct contact. The uncoated areas are then backfilled with a second polymer brush by using the unreacted surface-bound initiator molecules to thermally trigger a second polymerization. As an example for the overall process, the co-assembly of a micropatterned, soft, water-swellable layer consisting of the two-brush system poly(methacrylic acid) (PMAA)-poly(hydroxyethyl methacrylate) (PHEMA) is demonstrated.

Journal Article↗

Advancing and receding motion of droplets on ultrahydrophobic post surfaces.

We have fabricated a range of silicon post surfaces where post width and spacing have been systematically varied. As one subset, we have generated surfaces where the post spacings in x and y assume different values. On these surfaces, the dynamic contact angles become anisotropic. A fluoropolymer monolayer is photochemically attached to the microstructured silicon, leading to the appearance of ultrahydrophobic properties. On one side, the advancing contact angles on these surfaces are not affected by variations in the geometric parameters. This furthers the conclusion that, during the advancing motion, a true contact angle of 180 degrees is reached. On the other side, the receding angles are strongly influenced by the post size and spacing. We quantitatively analyze this dependence and relate variations in the receding angle to the shape and movement of the three-phase contact line. It is suggested that during the receding motion the meniscus successively dewets from one post at a time, with a step function running along the contact line until it has receded from a row of posts over its entire length.

Hydrophobic and Hydrophilic Interactions↗

Tunable Bragg filters based on polymer swelling.

We report on the optical properties of Bragg mirrors and filters fabricated from photo-cross-linked standard optical polymers. The transmittance spectra of these devices in the visible to near-infrared spectral range were measured. We demonstrate efficient tuning of the filter peak of the polymer Bragg filters over several hundred nanometers by adding organic solvents to the surrounding atmosphere of the filter. This represents what we believe to be a novel tuning principle for Bragg filters relying on the use of polymeric materials.

Journal Article↗

Domain memory of mixed polymer brushes.

The nano-phase-separation in mixed polymer brushes consisting of polystyrene and poly(methyl methacrylate) (PS-PMMA) chains attached to a silicon surface is studied. The topographies of the mixed brushes are examined after they have been exposed to solvents which induce or erase nano-phase-separation. It is discussed whether the brush locally forms the same pattern every time the transition from the smooth and featureless to the nanopatterned state occurs ("domain memory") or if the local assembly of the domains emerges in a different arrangement after each cycle of topography switching. A memory measure parameter is introduced, which characterizes quantitatively the domain memory effect in the nanopattern. It is shown that at constant grafting density but with increasing molecular weight of the brush chains the memory measure parameter decreases. In contrast to this, brushes with constant molecular weight, but differing in grafting density, all have a similar domain memory. We discuss a possible origin of the domain memory effect in the mixed brush systems studied and point out its impact on the motion of nanoparticles adsorbed on top of such systems.

Journal Article↗

Immobilization and AFM of single 4 x 6-mer tarantula hemocyanin molecules.

The high molecular mass respiratory protein of the tarantula Eurypelma californicum, a 4 x 6-mer hemocyanin, was investigated by atomic force microscopy (AFM). Various substrates and methods were evaluated for immobilization of individual hemocyanin molecules on a solid surface. Samples were imaged after physisorption on mica and self-assembled monolayers, and after chemisorption on Au(111) and N-hydroxy-succinimide (NHS) functionalized surfaces. AFM measurements were carried out preferable in solution and contact mode, but also in Tapping mode and on air-dried samples. Adsorption of the protein on mica followed by drying and carrying out the measurements in Tapping mode gave the best results. In the AFM images the four hexamers of the native 4 x 6-mer hemocyanin have been defined. The results were compared with independent available structural data and represent a validation case for this technique applied for the first time on such giant and complex molecules. As observable in images taken by transmission electron microscopy and also proposed from SAXS data, 4 x 6-mers could be found where the half-molecules are tilted against each other. This study is a step in resolving conformational heterogeneities, involved in oxygen binding of hemocyanins, at the single-molecule level by AFM.

Air↗

Modification of micronozzle surfaces using fluorinated polymeric nanofilms for enhanced dispensing of polar and nonpolar fluids.

In this work, we report on the surface modification of a micronozzle surface to enhance fluid dispensing in the nanoliter range. Unmodified dispensing chips usually suffer from lateral wetting of the nozzle surfaces by low surface tension liquids resulting in poor control of the volume of the dispensed fluid. Covalent attachment of a fluorinated acrylate polymer to the outer surface of the micronozzle using a novel UV irradiation process helps to overcome capillary and adhesive forces and results in an enhancement of the control on fluid dispensing in the nanoliter range. The modified nozzles have been tested with a variety of fluids having a wide range of surface tensions. The surface modification allows precise control of the dispensing of nanoliter droplets with a high degree of reproducibility.

Fluorine Compounds↗

On the formation of molecular terraces.

Langmuir-Blodgett-Kuhn films of poly(amic acid) with azobenzene-chromophore side groups (azo-PAA) have been examined using atomic force microscopy (AFM). If films were deposited at specific conditions, i.e., at transfer pressures (pi = 10-26 mN/m) and at transfer rates (nu = 2-10 mm/min), unusual patterns were formed. While the first few transferred layers of azo-PAA exhibited uniform coverage of the underlying surface with a flat topography, successive layers form a pattern of parallel terraces with micrometer width, which are assembled in a pyramid-like structure. The height of the pyramidal steps is 1.6 nm, which corresponds to the thickness of an azo-PAA monolayer. Each even step of such a pyramid has a hydrophobic surface, and each odd step has a hydrophilic surface. The width of the terraces varies significantly from terrace to terrace; however, the width of an individual terrace remains constant over hundreds of micrometers. The orientation of the pyramidal terraces is governed by the film deposition process and is always perpendicular to the transfer direction.

Journal Article↗

Azobenzene-containing polyamic acid with excellent Langmuir-Blodgett-Kuhn film formation behavior suitable for all-optical switching.

To generate command surfaces for all-optical switching, highly ordered polymeric Langmuir-Blodgett-Kuhn (LBK) multilayers were fabricated onto silicon substrates and gold-coated optical glass slides from novel azobenzene-bearing polyamic acid systems. Pronounced Bragg peaks and well-defined Kiessig fringes observed in the X-ray reflectivity measurement for samples on silicon substrates indicate that these films possess a regularly repeated Y-type LBK multilayer structure and ultrasmooth surfaces. Fourier transform infrared (FT-IR) spectra taken by grazing incidence reflection suggest specific orientations of the functional groups in the layers. The excellent film-forming properties of the polyamic acid allow for a smooth buildup of several hundreds of layers of the LBK films onto gold-coated glass slides, which in turn allows for determining the geometrical thickness and the anisotropic refractive indices of the films by using optical waveguide spectroscopy. Interestingly, the probe laser beam induced a distinct fluorescence signal from the films, which remained even after the film underwent a thermal imidization process at 160 degrees C for 8 h in vacuo. LBK films fabricated from these compounds can be successfully applied for all-optically switching the alignment of liquid crystals by irradiation with light of different wavelengths.

Journal Article↗

A facile photochemical surface modification technique for the generation of microstructured fluorinated surfaces.

We describe a simple photochemical process which allows fluoropolymers to be chemically bound at room temperature onto SiO2 surfaces. To achieve this, at first a benzophenone silane is used to form a self-assembled monolayer on the surface of the substrate, which is subsequently coated with the fluoropolymer and irradiated with UV light of wavelength 365 nm. Using this very simple approach, we have been able to create ultrahydrophobic surfaces with very low surface free energies together with a good degree of control in thickness and composition as well as strong adhesion to the monolayer. The use of a UV-based process to attach the films on SiO2 surfaces opens the door for photopatterning of surfaces with fluorinated and nonfluorinated compounds to yield well-defined microstructures with spatial control of the wetting properties of the substrates.

Journal Article↗

[Cultivation of human cells on polymer covered biomaterial--a new concept to improve the implant characteristics. Results of an in-vitro-investigation].

BACKGROUND AND PURPOSE: Calcific degeneration with the resulting need for operative replacement remains the major drawback of bioprostheses. Previous studies have shown that cellular surface seeding decreases calcium uptake in vitro and in vivo, but complete coverage remains difficult to achieve. A new approach is presented, masking glutaraldehyde residues with a covalently bound polymer layer thus facilitating cell seeding. The aim of this study was to evaluate different polymers for their ability to promote surface cell adhesion and formation of complete monolayers. MATERIAL AND METHODS: Ten ultrathin polymers, covalently bound to glass and exhibiting different physicochemical characteristics (thickness, molecular weight, hydrophilic properties, electrical charge) were seeded with human endothelial cells. Four of the ten polymers were also seeded with fibroblasts. As a reference, both cell types were seeded on glass surface. Quality of cell growth and coverage was evaluated by light and scanning electron microscopy. RESULTS: Five of ten polymers and glass exhibited excellent growth and complete surface coverage after 2 weeks, two allowed less cell adherence than glass reference, and three showed only poor cellular growth without adherence. Scanning electron microscopy demonstrated an intact monolayer for the five polymers with excellent cell coverage. Fibroblasts grew well on glass but not on the four tested polymers. No correlation was found between molecular weight, thickness, hydrophilic or charge characteristics of the polymers. CONCLUSION: Several ultrathin polymers, seeded with human endothelial cells, permit complete monolayer formation, but without any apparent correlation to physicochemical characteristics. Polymers covalently bound to biologic tissue appear as a promising approach to prevent calcific degeneration of bioprostheses.

Blood Vessel Prosthesis↗

Ultrathin polymer monolayers for promotion of cell growth on bioprosthetic materials -- evolution of a new concept to improve long term performance of biologic heart vales.

Reoperation of aldehyde tanned bioprotheses due to calcific degeneration remains their major drawback. Based on experiments studying mechanisms and factors that influence the time phase, extent and progression of calcification and evaluating the efficiency of anticalcification treatments and the effects of surface seeding with vital cells a new concept to avoid calcification emerged: masking aldehyde-residues with a covalently bound polymer that supports surface cell seeding. Different covalently bound polymers were tested for their suitability to grow cells. Dense cell growth was achieved on some polymers but without correlation to physico-chemical properties. Ultrathin coating of biological materials appears a promising approach to achieve lining with vital cells.

Aldehydes↗