Gireeshkumar Balakrishnan

Particles Trapped at the Droplet Interface in Water-in-Water Emulsions

Water-in-water emulsions were formed by mixing incompatible aqueous solutions of dextran and poly(ethylene oxide) (PEO) in the presence of latex or protein particles. It was found that particles with a radius as small as 0.1 μm become trapped at the interface between the PEO- and dextran-rich phases with interfacial tensions down to 10(-6) N/m. The particles were visualized at the interface of the emulsion droplets using confocal laser scanning microscopy (CLSM) allowing determination of the contact angle. Various degrees of coverage with particles could be observed. On densely covered droplets, the particles had a hexagonal crystalline order. At intermediate coverage, transient clustering of the particles was observed. The diffusion coefficient of the particles at the interface was determined using multiparticle tracking. Fusion of droplets was observed in all cases leading eventually to macroscopic phase separation.

Particle diffusion in globular protein gels in relation to the gel structure.

Globular protein gels with a variety of structures were prepared by heating β-lactoglobulin solutions at different concentrations and different ionic strengths. The structure was analyzed in terms of the pair correlation function of the protein concentration, and the volume fraction of the gels was determined. A strong coarsening of the gel structure was observed upon increasing the NaCl concentration between 0.1 and 0.25 M. The mean square displacement of spherical particles with diameters between 0.2 and 2 μm was determined in solutions and in gels by multiparticle tracking of confocal laser scanning microscopy images. Brownian diffusion or trapping of spheres with different sizes was observed, depending on the gel structure. In few cases the diffusion was anomalous. The relationship between gel structure and particle mobility is discussed.

Relation between the gel structure and the mobility of tracers in globular protein gels

Diffusion of fluorescent-labeled dextran with different molecular weights was investigated in β-lactoglobulin (β-lg) solutions and gels over a wide range of salt and protein concentrations at pH 7 by combining confocal laser scanning microscope (CLSM) with fluorescence recovery after photobleaching (FRAP). Effects of the protein concentration, the salt concentration and the tracer size were investigated in detail. Diffusion in turbid heterogeneous gels formed at 0.2M NaCl depended weakly on the probe size and the protein concentration and remained close to that in unheated solutions. A strong decrease of the diffusion coefficient with increasing tracer size and protein concentration was observed in more homogeneous gels formed at lower salt concentrations. Larger dextran chains were trapped in transparent gels formed at NaCl concentration below 0.1M. The present investigation complements an earlier study of tracer diffusion of larger spherical probes in β-lg gels using multi-particle tracking.

Specific effect of calcium ions on thermal gelation of aqueous micellar casein suspensions

Aqueous suspensions of micellar casein (MC) gel when heated above a critical temperature that depends on the pH. The effect of adding CaCl2 and EDTA on thermal gelation was studied in order to assess the effect of increasing or decreasing the amount of bound Ca2+ on the process. The effect of adding NaCl was investigated in order to distinguish the effect of Ca2+ binding from the effect of screening of electrostatic interactions. Shear moduli were measured as a function of the temperature during heating ramps up to 90 °C. Gel formation was characterized by a sharp increase of the storage modulus at a critical temperature (Tc). In most cases, prolonged heating at 90 °C did not cause a significant increase of the gel stiffness. Addition of CaCl2 caused a decrease of Tc, whereas addition of NaCl caused an increase of Tc. Chelation of Ca2+ by EDTA led to a strong increase of Tc even if the fraction of chelated Ca2+ was small and the micelles remained intact. The gel stiffness was found to increase weakly with increasing CaCl2 concentration up to 20 mM. The gels persisted during cooling to 20 °C with an increase of the elastic modulus by a factor between 4 and 6 depending on the CaCl2 concentration. The results demonstrate that Ca2+ plays a crucial role in thermal MC gelation.