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Biomedical subjects

S U Egelhaaf

Publications and source records attributed to S U Egelhaaf.

11 recordsLinked to original sources

Non-equilibrium behavior of sticky colloidal particles: beads, clusters and gels.

To understand the non-equilibrium behavior of colloidal particles with short-range attraction, we studied salt-induced aggregation of lysozyme. Optical microscopy revealed four regimes: bicontinuous texture, 'beads', large aggregates, and transient gelation. The interaction of a metastable liquid-liquid binodal and an ergodic to non-ergodic transition boundary inside the equilibrium crystallization region can explain our findings.

Colloids↗

Structure of strongly interacting polyelectrolyte diblock copolymer micelles.

The structure of spherical micelles of the diblock poly(styrene-block-acrylic acid) [PS-b-PA] copolymer in water was investigated up to concentrations where the polyelectrolyte coronal layers have to shrink and/or interpenetrate in order to accommodate the micelles in the increasingly crowded volume. We obtained the partial structure factors pertaining to the core and corona density correlations with small angle neutron scattering and contrast matching in the water. The counterion structure factor was obtained with small angle x-ray scattering (SAXS) with a synchrotron radiation source. Furthermore, we have measured the flow curves and dynamic visco-elastic moduli. The functionality of the micelles is fixed with a 9 nm diameter PS core and a corona formed by around 100 PA arms. As shown by the SAXS intensities, the counterions are distributed in the coronal layer with the same density profile as the corona forming segments. Irrespective ionic strength and micelle charge, the corona shrinks with increasing packing fraction. At high charge and minimal screening conditions, the polyelectrolyte chains remain almost fully stretched and they interdigitate once the volume fraction exceeds the critical value 0.53+/-0.02. Interpenetration of the polyelectrolyte brushes also controls the fluid rheology: The viscosity increases by three orders of magnitude and the parallel frequency scaling behavior of the dynamic moduli suggests the formation of a physical gel. In excess salt, the coronal layers are less extended and they do not interpenetrate in the present concentration range.

Journal Article↗

Do spherical polyelectrolyte brushes interdigitate?

The structure of spherical micelles of the diblock copolymer poly(styrene-block-acrylic acid) in water was investigated with small angle neutron scattering and contrast matching. We have monitored intermicelle correlation and the extension of the polyelectrolyte chains in the coronal layer through the overlap concentration. Irrespective of ionic strength, the corona shrinks with increasing packing fraction. Furthermore, at high charge and minimal screening conditions, the corona layers interpenetrate once the volume fraction exceeds the critical value 0.53+/-0.02.

Journal Article↗

Crystallization of a globular protein in lipid cubic phase.

We studied the crystallization of a globular protein, lysozyme, in the cubic phase of the lipid mono-olein. The solubility of lysozyme in salt solution decreased by a factor of approximately 4 when confined in cubic phase. Monte Carlo simulations and calculations show that this can be explained by the confinement of lysozyme molecules to the narrow water cells in the cubic phase.

Crystallization↗

Glasses in hard spheres with short-range attraction.

We report a detailed experimental study of the structure and dynamics of glassy states in hard spheres with short-range attraction. The system is a suspension of nearly hard-sphere colloidal particles and nonadsorbing linear polymer which induces a depletion attraction between the particles. Observation of crystallization reveals a reentrant glass transition. Static light scattering shows a continuous change in the static structure factors upon increasing attraction. Dynamic light scattering results, which cover 11 orders of magnitude in time, are consistent with the existence of two distinct kinds of glasses, those dominated by interparticle repulsion and caging, and those dominated by attraction. Samples close to the "A3 point" predicted by mode coupling theory for such systems show very slow, logarithmic dynamics.

Journal Article↗

Structure of peptide solutions: a light scattering and numerical study.

We investigated the interactions between protein molecules in solution, in particular for low salt concentrations and thus strong electrostatic interactions where a treatment based on the second virial coefficient is not sufficient. Static and dynamic light scattering experiments on solutions containing the peptide human calcitonin (hCT) were combined with calculations based on the Ornstein-Zernike equation with the hypernetted chain (HNC) closure and computer simulations within the primitive electrolyte model. The simulation illustrates the distribution of proteins in solution and the formation of (transient) protein aggregates. It furthermore allows us to predict the physical stability of hCT solutions in dependence of ionic strength, pH and hCT concentration.

Calcitonin↗

Kinetics of the micelle-to-vesicle transition: aqueous lecithin-bile salt mixtures.

Important routes to lipid vesicles (liposomes) are detergent removal techniques, such as dialysis or dilution. Although they are widely applied, there has been only limited understanding about the structural evolution during the formation of vesicles and the parameters that determine their properties. We use time-resolved static and dynamic light scattering to study vesicle formation in aqueous lecithin-bile salt mixtures. The kinetic rates and vesicle sizes are found to strongly depend on total amphiphile concentration and, even more pronounced, on ionic strength. The observed trends contradict equilibrium calculations, but are in agreement with a kinetic model that we present. This model identifies the key kinetic steps during vesicle formation: rapid formation of disk-like intermediate micelles, growth of these metastable micelles, and their closure to form vesicles once line tension dominates bending energy. A comparison of the rates of growth and closure provides a kinetic criterion for the critical size at which disks close and thus for the vesicle size. The model suggests that liposomes are nonequilibrium, kinetically trapped structures of very long lifetime. Their properties are hence controlled by kinetics rather than thermodynamics.

Animals↗

Multiple glassy states in a simple model system.

Experiments, theory, and simulation were used to study glass formation in a simple model system composed of hard spheres with short-range attraction ("sticky hard spheres"). The experiments, using well-characterized colloids, revealed a reentrant glass transition line. Mode-coupling theory calculations and molecular dynamics simulations suggest that the reentrance is due to the existence of two qualitatively different glassy states: one dominated by repulsion (with structural arrest due to caging) and the other by attraction (with structural arrest due to bonding). This picture is consistent with a study of the particle dynamics in the colloid using dynamic light scattering.

Journal Article↗

Shape of Ocr, the gene 0.3 protein of bacteriophage T7: modeling based on light scattering experiments.

Ocr, the first protein expressed by bacteriophage T7, inhibits type Iota DNA restriction enzymes by preventing them from binding to DNA. This inhibition allows the phage to successfully infect the host. The shape of ocr is modeled on the basis of static and dynamic light scattering measurements. The static light scattering data confirm previous observations that ocr exists in solution as a dimer. The diffusion constant determined by dynamic light scattering indicates a nonspherical shape of the ocr dimer. Hydrodynamic models of ellipsoids are presented, and it is argued that ocr is best described by a prolate ellipsoid with dimensions of 10.4 nm by 2.6 nm. The size and shape predicted by this model are consistent with ocr acting as a mimic of the DNA structure bound by type Iota restriction enzymes.

Bacteriophage T7↗

New controlled environment vitrification system for cryo-transmission electron microscopy: design and application to surfactant solutions.

A newly designed controlled environment vitrification system for cryo-transmission electron microscopy of vitrified samples (cryo TEM) is presented. It significantly reduces the lag-time from blotting to vitrification by means of an optimized blotting procedure. Furthermore, a modified transfer system allows rapid transfer of the vitrified sample into the microscope and reduces the equilibration time. The practicable throughput of samples is thereby markedly increased. This new equipment is used to determine the overall size of individual polymer-like mixed lecithin-bile salt micelles, which very critically depends on the composition of the sample. The quantitative agreement with the results from independent light scattering experiments on the same sample supports the validity and performance of the presented sample preparation and handling procedures. In addition, these experiments demonstrate that cryo TEM experiments not only provide direct structural information, but furthermore permit a quantitative determination of micellar properties.

Bile Acids and Salts↗

The solution structure of functionally active human proliferating cell nuclear antigen determined by small-angle neutron scattering.

The function of proliferating cell nuclear antigen (PCNA) in DNA replication and repair is to form a sliding clamp with replication factor C (RF-C) tethering DNA polymerase delta or epsilon to DNA. In addition, PCNA has been found to interact directly with various proteins involved in cell cycle regulation. The crystal structure of yeast PCNA shows that the protein forms a homotrimeric ring lining a hole through which double-stranded DNA can thread, thus forming a moving platform for DNA synthesis. Human and yeast PCNA are highly conserved at a structural and functional level. We determined the solution structure of functionally active human PCNA by small-angle neutron scattering. Our measurements strongly support a trimeric ring-like structure of functionally active PCNA in solution, and the data are in good agreement with model calculations based on the crystal structure from yeast PCNA. The human PCNA used in the small-angle neutron scattering experiments was active before and after the measurements in a RF-C independent and a RF-C dependent assay suggesting that the trimeric structure is the in vivo functional form.

Buffers↗