Karlheinz Graf

Fabrication of microvessels and microlenses from polymers by solvent droplets

A process for the fabrication of microvessels and microlenses in polymers is presented. A drop of solvent (diameter between 15 and 150μm) is deposited by an ink-jet method onto a flat polymer substrate. After evaporation of the solvent a lenticular cavity of dimensions comparable to the former drop size is created. This cavity can be employed as a microreaction vessel, as a concave lens, or as a template for a convex lens. Diameter, depth, position, and arrangement of the microvessels on the surface can be controlled.

Molecular adhesion interactions between Langmuir monolayers and solid substrates

Abstract Substrate-monolayer adhesion interactions between differently prepared SiO2 surfaces and Langmuir monolayers were investigated. From the relation between the contact angle and the surface tension of a Langmuir monolayer in the configuration of Langmuir wetting the work of adhesion between the substrate and the monolayer as a function of the molecular packing and the transfer ratios was determined. Thus the molecular work of adhesion of different SiO2-dimyristoylphosphatidylethanolamine surfaces was quantified. The relation between the local adhesion interactions and the molecular packing and structure is presented and substrate-induced phase transitions are discussed.

Evaporation dynamics of microdroplets on self-assembled monolayers of dialkyl disulfides.

We present a study of the static wettability and evaporation dynamics of sessile microdroplets of water on self-assembled monolayers (SAMs) prepared with unsymmetric dialkyl disulfides CH(3)-(CH(2))(11+m)-S-S-(CH(2))(11)-OH (m = 0, +/- 2, +/- 4, +/- 6) on gold-covered mica. The advancing and receding contact angles decrease linearly with increasing hydrophilicity of the SAM. The latter was changed either via the molar ratio or via the chain length of the hydroxyl-terminated alkyl chains in the monolayer. In contrast to SAMs made of thiols, the contact angle hysteresis was 10 degrees for all disulfides, irrespective of their chain lengths. During evaporation of single droplets, a transition from pinning to constant contact angle mode was observed. The transition time between the modes increases with the surface hydrophilicity, leading to longer pinning. This way, the time for complete droplet evaporation decreases by approximately 30% owing to the fact that during pinning the overall droplet area stays large for a longer time. For single droplets the measured total evaporation times agree well with the calculated ones, showing the validity of the standard evaporation model for both evaporation modes. In contrast to the results for single droplets, many droplets with different initial volumes show a power-law dependence on the total evaporation time with an exponent different from 1.5 as expected from the standard model. For disulfides with m not equal 0, the exponent is in the range of 1.40-1.47 increasing with the surface hydrophilicity. For the SAMs with m = 0 the exponent increases up to 1.61 for the most hydrophilic surface. We explain this deviation from the standard evaporation model with the presence of a liquid precursor film around the droplet, which either enhances or decelerates evaporation. Our results suggest that SAMs of dialkyl disulfides offer the possibility to tune the wettability of gold surfaces in a more controlled way than thiols do.

Microstructures on soluble polymer surfaces via drop deposition of solvent mixtures

We report a single step procedure for aspheric shaped microlens formation. By means of the ink-jet printing technique, microdroplets of mixtures of solvents with different volatilities are deposited on a soluble polymer substrate. The generated microstructures (diameter in range of about 200μm–5mm) exhibit a pronounced focusing effect. The method can be extended to one-dimensional and two-dimensional microlens arrays.

Microstructuring of polystyrene surfaces with nonsolvent sessile droplets.

Herein, we study the microstructuring of toluene-vapor-softened polystyrene surfaces with nonsolvent sessile droplets. Arrays of microvessels are obtained by depositing non-evaporating droplets of ethylene glycol/water on the original polystyrene surfaces and subsequently exposing them to saturated toluene vapor. The droplets act as a mask on the polymer, thereby impeding the toluene vapor to diffuse and soften the polystyrene surface below them. Alternatively, the formation of microcraters at random positions--with an average depth-to-width aspect ratio of 0.5 and a diameter as small as 1.5 microm--is achieved by condensing water droplets on a softened polystyrene surface. The cross-sections of the microvessels and the contact angle of the sessile water droplets suggest that the structures are formed by the combined action of the Laplace pressure at the bottom of the droplet and the surface tension acting at the three-phase contact line of the droplets. As a support, the rim height and the depth of the microvessels are fitted with an elastic theory to provide Youngs modulus of the softened polystyrene surface.

Interfacial forces between a silica particle and phosphatidylcholine monolayers at the air-water interface.

Interfacial forces between a silica or borosilicate particle in water and phospholipids at the air-water interface were studied using the Monolayer Particle Interaction Apparatus. This instrument allowed the forces to be measured as the colloidal probe approached the monolayer from the liquid phase. The proper working principle of this setup was demonstrated by measuring the forces between a particle and a mica plate in 0.1 mM NaCl. The effect of the alkyl chain length on the adhesion between the particle and the monolayer was investigated using four different 1,2-dialkyl-sn-glycero-3-phosphocholines (DMPC, DPPC, DSPC, and DBPC), which had 14, 16, 18, and 22 carbon atoms per alkyl chain, respectively. The adhesion force increased with the square of the particle radius. The lipids in the liquid-expanded (LE) phase showed an attraction to the particle, explained by an electrostatic attraction and/or the formation of a three-phase contact line that lead to a capillary force. All monolayers showed an adhesion in their retract force curve, which decreased with an increased chain length and surface pressure. Interfacial stiffness was generally seen to increase with the phospholipid chain length and to decrease with surface pressure, explained by an increase in the intermolecular van der Waals interaction and a decrease in the interfacial tension, respectively. The adhesion between the particle and monolayer was concluded to be controlled by the contact area between the particle and monolayer, and therefore the monolayer stiffness and the electrostatic interactions.

Hydrophilic/hydrophobic nanostripes in lipopolymer monolayers.

The self-organization of macromolecules with a complex architecture is studied extensively in the last years, with the aim to nanostructure surfaces. Linear diblock copolymers with mutual antagonistic groups are a simple, much investigated system, since the respective block lengths determine the size of the nanostructure[1]. Yet little is known about the equilibrium structure when the forces from the two interfaces, and the intraand intermolecular interactions are all of comparable magnitude. An active control of the domain morphology as well as the possibility to manipulate the structures in situ would obviously improve our understanding.

Protein Diffusion Across the Interface in Aqueous Two-Phase Systems

We present a detailed study of the diffusive transport of proteins across a fluid phase boundary within aqueous two-phase systems. The aim of the work is to investigate whether local effects at the phase boundary cause a retardation of the diffusive transport between the phases. Possible modifications of interfacial mass transfer could be due to protein adsorption at the phase boundary or local electric fields from electric double layers. Experiments with a microfluidic system have been performed in which protein diffusion (bovine serum albumin and ovalbumin) within a bilaminated configuration of two phases containing polyethylene glycol and dextran is analyzed. A one-dimensional model incorporating phase-specific diffusion constants and the difference in chemical potential between the phases has been formulated. A comparison of experimental and simulation data shows a good overall agreement and suggests that a potential local influence of the phase boundary on protein transport is insignificant for the systems under investigation.

Design of Thermally Responsive Polymeric Hydrogels for Brackish Water Desalination: Effect of Architecture on Swelling, Deswelling, and Salt Rejection

In this work, we explore the ability of utilizing hydrogels synthesized from a temperature-sensitive polymer and a polyelectrolyte to desalinate salt water by means of reversible thermally induced absorption and desorption. Thus, the influence of the macromolecular architecture on the swelling/deswelling behavior for such hydrogels was investigated by tailor-made network structures. To this end, a series of chemically cross-linked polymeric hydrogels were synthesized via free radical-initiated copolymerization of sodium acrylate (SA) with the thermoresponsive comonomer N-isopropylacrylamide (NIPAAm) by realizing different structural types. In particular, two different polyNIPAAm macromonomers, either with one acrylate function at the chain end or with additional acrylate functions as side groups were synthesized by controlled polymerization and subsequent polymer-analogous reaction and then used as building blocks. The rheological behaviors of hydrogels and their estimated mesh sizes are discussed. The performance of the hydrogels in terms of swelling and deswelling in both deionized water (DI) and brackish water (2 g/L NaCl) was measured as a function of cross-linking degree and particle size. The salt content could be reduced by 23% in one cycle by using the best performing material.

Surface stress, thickness, and mass of the first few layers of polyelectrolyte

The effects of surface stress and mass loading upon the adsorption of polyelectrolytes onto flexible silicon micromechanical cantilever sensors (MCSs) were studied in situ. A self-assembled monolayer of 2-mercaptoethylamine chloride (2-MEA) on gold was used to achieve single-side adsorption on the MCS. Such a preparation gave a positive surface potential, whereas a bare SiOx surface gave a negative surface potential. Wide scan X-ray photoelectron spectroscopy confirmed that the adsorption of polystyrenesulfonate (PSS) and polyallylamine hydrochloride (PAH) followed the general rule expected from the electrostatic interaction between the substrate and the polyelectrolyte, whereas the adsorption polyethyleneimine (PEI) did not. The adsorption of PAH on SiO(x) from a 3 mM water solution containing 1 M NaCl was associated with a deflection of the MCS toward the polyelectrolyte monolayer (tensile surface stress) owing to the hydrogen bonding between neighboring amino groups. Here, a surface stress change of 1.4 +/- 0.1 N/m was estimated. The adsorption of PSS from a 3 mM water solution containing 1 M NaCl on a 2-MEA surface induced a deflection of the MCS away from the polyelectrolyte layer (compressive stress), toward the SiO(x) side. Here, a surface stress change of 3.1 +/- 0.3 N/m was determined. The formation of a PAH layer on top of the PSS layer resulted in a deflection of the MCS toward the PAH layer. This indicated that the adjacent PSS layer was deswelling, corresponding to a surface stress change of 0.5 +/- 0.1 N/m.