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Biomedical subjects

Georg Papastavrou

Publications and source records attributed to Georg Papastavrou.

7 recordsLinked to original sources

Decomposing bridging adhesion between polyelectrolyte layers into single molecule contributions.

A novel approach to analyze the force response of multiple polymer strands, which are bridged between two surfaces, is proposed. The response of single polymer strands is experimentally accessible by measuring the force upon separation of two polymer-coated surfaces with the atomic force microscope. Our approach is based on the decomposition of the stretching and desorption sequence into contributions of independently bridged chains and of the elimination of loops formed on the opposite surface during contact. This approach was applied to investigate the bridging adhesion of surfaces coated with poly(vinylamine) (PVA). The force response of single PVA molecules was described on the basis of a recently proposed model, which accounts for the discrete chain character of the polymer at higher extension forces. As exemplary results, we determined the length distributions of the individual chains and the loop number distribution of these bridging chains on the polyelectrolyte-coated surfaces. The former were compared with scaling theories of polymer adsorption.

Journal Article↗

Deposition of nanosized latex particles onto silica and cellulose surfaces studied by optical reflectometry.

Deposition of positively charged nanosized latex particles onto planar silica and cellulose substrates was studied in monovalent electrolyte solutions at pH 9.5. The deposition was probed in situ with optical reflectometry in a stagnation point flow cell. The surface coverage can be estimated reliably with island film theory as well as with a homogeneous film model, as confirmed with atomic force microscopy (AFM). The deposition kinetics on the bare surface was of first order with respect to the particle concentration, whereby the deposition rate was close to the value expected for a perfect collector. The efficiency coefficient, which was defined as the ratio of the experimental and theoretical deposition rate constants, was in the range from 0.3 to 0.7. Subsequently, the surface saturated and a limiting maximum coverage was attained (i.e., blocking). These trends were in qualitative agreement with predictions of the random sequential absorption (RSA) model, where electrostatic interactions between the particles were included. It was observed, however, that the substrate strongly influenced the maximum coverage, which was substantially higher for silica than for cellulose. The major conclusion of this work was that the nature of the substrate played an important role in a saturated layer of deposited colloidal particles.

Cellulose↗

Close approximation of two platelet factor 4 tetramers by charge neutralization forms the antigens recognized by HIT antibodies.

OBJECTIVE: Heparin-induced thrombocytopenia (HIT) is a prothrombotic drug reaction caused by antibodies that recognize positively charged platelet factor 4 (PF4), bound to the polyanion, heparin. The resulting immune complexes activate platelets. Unfractionated heparin (UFH) causes HIT more frequently than low-molecular-weight heparin (LMWH), whereas the smallest heparin-like molecule (the pentasaccharide, fondaparinux), induces anti-PF4/heparin antibodies as frequently as LMWH, but without exhibiting cross-reactivity with these antibodies. To better understand these findings, we analyzed the molecular structure of the complexes formed between PF4 and UFH, LMWH, or fondaparinux. METHODS AND RESULTS: By atomic force microscopy and photon correlation spectroscopy, we show that with any of the 3 polyanions, but in the order, UFH>LMWH>>fondaparinux--PF4 forms clusters in which PF4 tetramers become closely apposed, and to which anti-PF4/heparin antibodies bind. By immunoassay, HIT antibodies bind strongly to PF4/H/PF4 complexes, but only weakly to single PF4/heparin molecules. CONCLUSIONS: HIT antigens are formed when charge neutralization by polyanion allows positively charged PF4 tetramers to undergo close approximation. Whereas such a model could explain why all 3 polyanions form antibodies with similar specificities, the striking differences in the relative size and amount of complexes formed likely correspond to the observed differences in immunogenicity (UFH>LMWH approximately fondaparinux) and clinically relevant cross-reactivity (UFH>LMWH>>fondaparinux).

Adsorption↗

Probing the validity of the Derjaguin approximation for heterogeneous colloidal particles.

The Derjaguin approximation states that the interaction force between two curved surfaces is proportional to their effective radius, whereby the inverse effective radius is the arithmetic mean of the inverse curvature radii of the surfaces involved. The present study investigates the validity of this approximation with an atomic force microscope (AFM) by measuring interaction forces between colloidal particles of different sizes, but of identical composition. Forces were measured between silica particles of 2.0, 4.8 and 6.8 microm in diameter in KCl electrolyte solution with and without adsorbed poly(amido amine) (PAMAM) dendrimers. The Derjaguin approximation could be confirmed at all distances investigated, including those comparable with the characteristic length scales of the surface roughness or the surface charge heterogeneities. For the conditions investigated, the Derjaguin approximation turns out to be surprisingly robust.

Journal Article↗

Interaction forces and molecular adhesion between pre-adsorbed poly(ethylene imine) layers.

Interaction forces between pre-adsorbed layers of branched poly(ethylene imine) (PEI) of different molecular mass were studied with the colloidal probe technique, which is based on atomic force microscopy (AFM). During approach, the long-ranged forces between the surfaces are repulsive due to overlap of diffuse layers down to distances of a few nanometers, whereby regulation of the surface charge is observed. The ionic strength dependence of the observed diffuse layer potentials can be rationalized with a surface charge of 2.3 mC/m2. The forces remain repulsive down to contact, likely due to electro-steric interactions between the PEI layers. These electro-steric forces have a range of a few nanometers and appear to be superposed to the force originating from the overlap of diffuse layers. During retraction of the surfaces, erratic attractive forces are observed due to molecular adhesion events (i.e., bridging adhesion). The frequency of the molecular adhesion events increases with increasing the ionic strength. The force response of the PEI segments is dominated by rubber-like extension profiles. Strong adhesion forces are observed for low molecular mass PEI at short distances directly after separation, while for high molecular mass weaker adhesion forces at larger distances are more common. The work of adhesion was estimated by integrating the retraction force profiles, and it was found to increase with the ionic strength.

Journal Article↗

Atomic force microscopy study of the adsorption and electrostatic self-organization of poly(amidoamine) dendrimers on mica.

The adsorption behavior of poly(amidoamine) dendrimers to mica surfaces was investigated as a function of ionic strength and pH. The conformation and lateral distribution of the adsorbed dendrimers of generations G8 and G10 were obtained ex situ by tapping mode atomic force microscopy (AFM). The deposition kinetics of the dendrimers was found to follow a diffusion-limited process. Fractional surface coverage and pair correlation functions of the adsorbed dendrimers were obtained from the AFM images. The data are interpreted in terms of the random sequential adsorption (RSA) model, where electrostatic repulsion due to overlapping double layers is considered. Although the general trends typical for an RSA-determined process are well-reproduced, quantitative agreement is lacking at low ionic strengths.

Journal Article↗

Direct force measurements between cellulose surfaces and colloidal silica particles.

The interaction of cellulose layers with colloidal silica particles was investigated by direct force measurements with the atomic force microscope (AFM). Upon approach, repulsive forces were found between the negatively charged silica particles and the cellulose surface. The forces were interpreted quantitatively in terms of electrostatic interactions due to overlap of diffuse layers originating from negatively charged carboxylic groups on the cellulose surface. The diffuse layer charge density of cellulose was estimated to be 0.80 mC/m2 at pH 9.5 and 0.21 mC/m2 at pH 4. The forces upon retraction are characterized by molecular adhesion events, whereby individual cellulose chains desorb from the probe surface. The retraction profiles are dominated by well-defined force plateaus, which correspond to single-chain desorption forces of 35-42 pN. We surmise that adsorption of cellulose to probe surfaces is dominated by nonelectrostatic forces, probably originating from hydrogen bonding. Electrostatic contributions to desorption force could be detected only at high pH, where the silica surface is highly charged.

Adsorption↗