Anomalous self-assembly of gelatin in ethanol-water marginal solvent.

Light scattering, rheology, and atomic force microscope (AFM) studies have been performed on solutions of a polyampholyte (gelatin) prepared in water-ethanol marginal solvent. At ethanol concentration approximately 45+/-2% v/v anomalous aggregation led to formation of fractal (on hydrophilic substrates; glass, quartz and silicon) aggregate of polypeptide molecules having fractal dimension d(f) in 2D=1.60+/-0.08. The time evolution morphology of these self-assembled and self-organized structures formed on hydrophilic substrates was driven by selective ethanol evaporation and was observed by an AFM. These fractal aggregates eventually transformed into near-spherical clusters with fractal corona having same fractal dimension (d(f)=1.58+/-0.05) and finally, the corona separated and regular aggregates were formed. The kinetics of aggregation on substrates could be modeled through random sequential adsorption of particles with continuum power-law size distribution. The temporal growth of aggregate hydrodynamic radius R(h)(t) and scattered intensity I(s)(t) measured in the bulk were observed to exhibit; R(h)-t(z) and I(s)-t(z)-with z=1/d(f), giving a fractal dimension d(f) in 3D approximately equal to 2.6+/-0.2, which is discussed within the framework of Smoluchowski aggregation kinetics. This growth in R(h) is accompanied by narrowing down of the particle size distribution. Solution rheology at this ethanol concentration revealed minimum thixotropy and maximum infinite shear viscosity features.