Christian Moitzi

Internal structure and colloidal behaviour of covalent whey protein microgels obtained by heat treatment

Covalently cross-linked whey protein microgels (WPM) were produced without the use of a chemical cross-linking agent. The hierarchical structure of WPM is formed by a complex interplay of heat denaturation, aggregation, electrostatic repulsion, and formation of disulfide bonds. Therefore, well-defined spherical particles with a diameter of several hundreds of nanometers and with relatively low polydispersity are formed in a narrow pH regime (5.8–6.2) only. WPM production was carried out on large scale by heating a protein solution in a plate-plate heat exchanger. Thereafter, the microgels were concentrated by microfiltration and spray dried into a powder. The spherical structure of the WPM was conserved in the powder. After re-dispersion, the microgel dispersions fully recovered their initial structure and size distribution. Due to the formation of disulfide bonds the particles were internally covalently cross-linked and were remarkably stable in a large pH range. Because of the pH dependent charge of the constituents the particles underwent significant size changes upon shifting the pH. Small angle X-ray scattering experiments were used to reveal their internal structure, and we report on the pH-induced structural changes occurring on different length scale. Our experiments showed that close analogies could be drawn to internally cross-linked and pH-responsive microgels based on weak polyelectrolytes. WPM also exhibited a pronounced swelling at pH values below the isoelectric point (IEP), and a collapse at the IEP. However, in contrast to classical microgels, WPM are not build up by simple polymer chains but possess a complex hierarchical structure consisting of strands formed by clusters of aggregated denatured proteins that act as primary building blocks. They were flexible enough to respond to changes of the environment, and were stable enough to tolerate pH values where the proteins were highly charged and the strands were stretched.

Improved cooperativity of spin-Labile iron(III) centers by self-assembly in solution

Supramolecular principles have been applied for improving the spin crossover activity of metal centers due to cooperative effects in solution. Thus, incorporation of alkyloxy tails at the phenyl group of Fe(sal2trien) 2a provides amphiphilic complexes Fe(sal-OR2trien) 2b-d (b, R = C6H13; c, R = C8H17; d, R = C18H37) comprising an apolar group for supramolecular organization and a polar headgroup with potential spin crossover activity due to the presence of a spin-labile iron(III) center. Self-assembly of these complexes in solution resulted in the formation of microsize and submicrosize particles when the alkyl chain was long enough (2d) but not with shorter chains (2a-c). Solutions of 2d showed enhanced spin crossover activity as compared to complexes 2a-c, both in terms of transition temperature and steepness of the transition. This observation has been correlated to an improved cooperativity of the metal centers in 2d due to self-assembly, thus facilitating a tandem spin transition.

The pH induced sol-gel transition in skim milk revisited. a detailed study using time-resolved light and X-ray scattering experiments

We present a detailed study of the evolution of the size, structure and stability of casein micelles upon acidification of skim milk typically applied in yogurt-making processes using a combination of time-resolved light and small-angle X-ray scattering experiments. While most of the available light scattering studies on casein acidification have been restricted to transparent and therefore highly diluted samples, we now profit from a newly developed multiangle 3D light scattering instrument, which allows for time-resolved measurements in highly turbid samples. Our experiments clearly demonstrate the presence of two parallel pH-dependent processes, micellar reassembly and aggregation. Using a systematic investigation of the effect of casein concentration, acidification rate, and ionic strength, we are able to decouple these two processes and obtain detailed information about the pH-induced restructuration of the casein micelle structure that occurs prior to destabilization. Moreover, our experiments also unambiguously demonstrate that these micellar reassembly processes are highly concentration dependent, and that typical light scattering studies conducted under highly diluted conditions are resulting in findings that may not be relevant for the situation encountered in industrial processes at higher concentrations. Experiments conducted with covalently cross-linked micelles, where the pH-induced reassembly has been suppressed, further confirm our findings.

Hydrodynamic Properties of Magnetic Nanoparticles with Tunable Shape Anisotropy: Prediction and Experimental Verification

We describe the characterization of the hydrodynamic properties of anisotropic magnetic nanoparticles using a combination of transmission electron microscopy (TEM) and dynamic as well as depolarized dynamic light scattering (DLS/DDLS). The particles used are nearly monodisperse hematite spindles with an average length of 280 nm and a minor axis of 57 nm, coated with a layer of silica of variable thickness that allows us to tune the particle aspect ratio between 5 and 2. Their geometrical dimensions can thus be determined easily and quantitatively from TEM. Moreover, their size is ideal to employ DLS and DDLS to measure the translational and rotational diffusion coefficients D(T) and D(R), while the presence of a magnetic core opens a plethora of opportunities for future studies and applications. We demonstrate that we can successfully predict the hydrodynamic properties of the different particles based on a TEM characterization of their size distribution and using established theoretical models for the hydrodynamic properties of anisotropic particles. When compared with the theoretical predictions, our light scattering measurements are in quantitative agreement. This agreement between theory and experiment is achieved without having to invoke any adjustable free parameter, as the TEM results are used to calculate the corresponding diffusion coefficients on an absolute scale. We demonstrate that this is achieved due to a new and simple method for the statistical weighting of the TEM information, and the use of the correct hydrodynamic models for the observed particle shape. In addition, we also demonstrate an enhanced sensitivity of the rotational diffusion for the surface properties of ellipsoidal nanoparticles, and point out that this may serve as an ideal tool toward characterizing functionalized surfaces.

Material transfer in cubosome-emulsion mixtures: effect of alkane chain length.

We present here results on the transfer kinetics of monoglyceride and n-alkanes in water. Transfer kinetics between cubosomes and emulsion droplets were followed using time-resolved small-angle X-ray scattering measurements, while dynamic light scattering was used to study the changes in the particle radii. The effect of the initial size of cubosomes and emulsion droplets on the final droplet size of the mixed components was investigated. Decane was transferred into the cubosomes with the disappearance of all emulsion droplets, with no detectable transfer of monoglyceride. Cubosomes were even found to absorb bulk decane into the solution from a surface layer, which raises the possibility of using cubosomes to bind hydrophobic molecules from the bulk phase. In mixtures with longer alkanes, transfer of both monoglyceride and oil was observed; while with octadecane the transfer of monoglyceride into emulsion droplets dominated. Calculating the point at which the transfer of monoglyceride becomes dominant over that of oil as the alkane chain length is increased shows that, in compositional ripening, monoglyceride behaves as an alkane with 15.3 carbons. These results further our understanding of the interactions of internally self-assembled particles in various media and suggest possible ways of controlling the size of the particles.

A new instrument for time-resolved static and dynamic light-scattering experiments in turbid media

We present a new 3D cross-correlation instrument that not only allows for static and dynamic scattering experiments with turbid samples but measures at four angles simultaneously. It thus extends the application of cross-correlation light scattering to time-resolved studies where we can, for example, efficiently investigate the temporal evolution of aggregating or phase separating turbid dispersions. The combination of multiangle 3D and on-line transmission measurements is an essential prerequisite for such studies. This not only provides time-resolved information about the overall size and shape of the particles through measurements of the mean apparent radius of gyration and hydrodynamic radius, but also on the weight-average apparent molar mass via the absolute forward scattering intensity. We present an efficient alignment strategy based on the novel design of the instrument and then the application range of the instrument using well-defined model latex suspensions. The effectiveness of the cross-correlation multiangle technique to monitor aggregation processes in turbid suspensions is finally shown for the acidification of skim milk during the yoghurt-making process. Due to the self-assembled nature of the casein micelles an understanding of the sol-gel process induced by the acidification is only feasible if time-resolved light-scattering experiments on an absolute scale are possible under industrially relevant conditions, where the casein solutions are highly turbid.

Structure and Dynamics of Soft Repulsive Colloidal Suspensions in the Vicinity of the Glass Transition

We use a combination of different scattering techniques and rheology to highlight the link between structure and dynamics of dense aqueous suspensions of soft repulsive colloids in the vicinity of a glass transition. Three different latex formulations with an increasing amount of the hydrophilic component resulting in either purely electrostatically or electrosterically stabilized suspensions are investigated. From the analysis of the static structure factor measured by small-angle X-ray scattering, we derive an effective volume fraction that includes contributions from interparticle interactions. We further investigate the dynamics of the suspensions using 3D cross-correlation dynamic light scattering (3DDLS) and rheology. We analyze the data using an effective hard sphere model and in particular compare the linear viscoelasticity and flow behavior to the predictions of mode coupling theory, which accounts for a purely kinetic glass transition determined by the equilibrium structure factor. We demonstrate that seemingly very different colloidal systems exhibit the same generic behavior when the effects from interparticle interactions are incorporated using an effective volume fraction description.