arXiv subjects

Matthias Ballauff

Publications and source records attributed to Matthias Ballauff.

27 records · Page 2Linked to original sources

arXiv2012

Sorption of proteins to charged microgels: characterizing binding isotherms and driving forces

We present a set of Langmuir binding models in which electrostatic cooperativity effects to protein sorption is incorporated in the spirit of Guoy-Chapman-Stern models, where the global substrate (microgel) charge state is modified by bound reactants (charged proteins). Application of this approach to lysozyme sorption to oppositely charged core-shell microgels allows us to extract the intrinsic, binding affinity of the protein to the gel, which is salt-concentration independent and mostly hydrophobic in nature. The total binding affinity is found to be mainly electrostatic in nature, changes many orders of magnitude during the sorption process, and is significantly influenced by osmotic deswelling effects. The intrinsic binding affinity is determined to be about 7 kBT for our system. We additionally show that Langmuir binding models and those based on excludedvolume interactions are formally equivalent for low to moderate protein packing, if the nature of the bound state is consistently defined. Having appreciated this, a more quantitative interpretation of binding isotherms in terms of separate physical interactions is possible in future for a wide variety of experimental approaches.

cond-mat.soft↗

arXiv2011

Quantifying the Reversible Association of Thermosensitive Nanoparticles

Under many conditions, biomolecules and nanoparticles associate by means of attractive bonds, due to hydrophobic attraction. Extracting the microscopic association or dissociation rates from experimental data is complicated by the dissociation events and by the sensitivity of the binding force to temperature (T). Here we introduce a theoretical model that combined with light-scattering experiments allows us to quantify these rates and the reversible binding energy as a function of T. We apply this method to the reversible aggregation of thermoresponsive polystyrene/poly(N-isopropylacrylamide) core-shell nanoparticles, as a model system for biomolecules. We find that the binding energy changes sharply with T, and relate this remarkable switchable behavior to the hydrophobic-hydrophilic transition of the thermosensitive nanoparticles.

cond-mat.soft↗

arXiv2011

Annealing of single lamella nanoparticles of polyethylene

We study the change of the size and structure of freely suspended single lamella nanoparticles of polyethylene during thermal annealing in aqueous solutions. Using small-angle x-ray scattering and cryogenic transmission electron microscopy, it is shown that a doubling of the crystalline lamella sandwiched between two amorphous polymer layers is obtained by annealing the nanoparticles at 125 C. This thickening of the crystalline lamella can be understood in terms of an unlooping of polymer chains within a single nanoparticle. In addition a variation of the annealing temperature from 90 C to 115 C demonstrates that the inverse of the crystalline lamellar thickness increases linearly with the annealing temperatures leading to a recrystallization line in a Gibbs-Thomson graph. Since the nanoparticles consist of about only eight polymer chains, they can be considered as a ideal candidates for the experimental realization of equilibrium polymer crystals.

cond-mat.soft↗

arXiv2010

A fluorescence correlation spectroscopy study of macromolecular tracer diffusion in polymer solutions

We discuss the manner in which the dynamics of tracer polystyrene chains varies with the concentration of matrix polystyrene chains dissolved in toluene. Using fluorescence correlation spectroscopy and theory, it is shown that the cooperative diffusion coefficient of the matrix polystyrene chains can be measured by fluorescence correlation spectroscopy in the semidilute entangled concentration regime. In addition the self-diffusion coefficient of the tracer polystyrene chains can be detected for arbitrary concentrations. The measured cooperative diffusion coefficient is independent of the molecular weight of the tracer polystyrene chains because it is a characteristic feature of the transient entanglement network.

cond-mat.soft↗

arXiv2010

Thermoresponsive Colloidal Molecules

We fabricated thermoresponsive colloidal molecules of ca. 250 nm size. Electron- and scanning force microscopy reveal the dumbbell-shaped morphology. The temperature dependence of the size and aspect ratio (ca. 1.4 to 1.6) is analyzed by depolarized dynamic light scattering and found to be in good agreement with microscopic evidence.

cond-mat.soft↗

arXiv2010

Self-diffusion and Cooperative Diffusion in Semidilute Polymer Solutions as measured by Fluorescence Correlation Spectroscopy

We present a comprehensive investigation of polymer diffusion in the semidilute regime by fluorescence correlation spectroscopy (FCS) and dynamic light scattering (DLS). Using single-labeled polystyrene chains, FCS leads to the self-diffusion coefficient while DLS gives the cooperative diffusion coefficient for exactly the same molecular weights and concentrations. Using FCS we observe a new fast mode in the semidilute entangled concentration regime beyond the slower mode which is due to self-diffusion. Comparison of FCS data with data obtained by DLS on the same polymers shows that the second mode observed in FCS is identical to the cooperative diffusion coefficient measured with DLS. An in-depth analysis and a comparison with current theoretical models demonstrates that the new cooperative mode observed in FCS is due to the effective long-range interaction of the chains through the transient entanglement network.

cond-mat.soft↗

arXiv2008

Viscoelasticity and shear flow of concentrated, non-crystallizing colloidal suspensions: Comparison with Mode-Coupling Theory

We present a comprehensive rheological study of a suspension of thermosensitive particles dispersed in water. The volume fraction of these particles can be adjusted by the temperature of the system in a continuous fashion. Due to the finite polydispersity of the particles (standard deviation: 17%), crystallization is suppressed and no fluid-crystal transition intervenes. Hence, the moduli $G'$ and $G"$ in the linear viscoelastic regime as well as the flow curves (shear stress $σ(\dotγ)$ as the function of the shear rate $\dotγ$) could be measured in the fluid region up to the vicinity of the glass transition. Moreover, flow curves could be obtained over a range of shear rates of 8 orders of magnitude while $G'$ and $G"$ could be measured spanning over 9 orders of magnitude. Special emphasis has been laid on precise measurements down to the smallest shear rates/frequencies. It is demonstrated that mode-coupling theory generalized in the integration through transients framework provides a full description of the flow curves as well as the viscoelastic behavior of concentrated suspensions with a single set of well-defined parameters.

cond-mat.soft↗

arXiv2005

Nonlinear rheology of dense colloidal dispersions: a phenomenological model and its connection to mode coupling theory

Rheological properties, especially 'shear-thinning', of dense colloidal dispersions are discussed on three different levels. A generalized phenomonological Maxwell model gives a broad framework connecting glassy dynamics to the linear and non-linear rheology of dense amorphous particle solutions. First principles mode coupling theory calculations for the time or frequency dependent shear modulus give quantitative results for dispersions of hard colloidal spheres in the linear regime. Schematic models extending mode coupling theory to the non-linear regime recover the phenomenology of the generalized Maxwell model, and predict universal features of flow curves, stress versus shear-rate.

cond-mat.soft↗

arXiv2005

Flow curves of dense colloidal dispersions: schematic model analysis of the shear-dependent viscosity near the colloidal glass transition

A recently proposed schematic model for the non--linear rheology of dense colloidal dispersions is compared to flow curves measured in suspensions that consist of thermosensitive particles. The volume fraction of this purely repulsive model system can be adjusted by changing temperature. Hence, high volume fractions ($ϕ\leq 0.63$) can be achieved in a reproducible manner. The quantitative analysis of the flow curves suggests that the theoretical approach captures the increase of the low shear viscosity with increasing density, the shear thinning for increasing shear rate, and the yielding of a soft glassy solid. Variations of the high shear viscosity can be traced back to hydrodynamic interactions which are not contained in the present approach but can be incorporated into the data analysis by an appropriate rescaling.

cond-mat.soft↗