PFG-NMR self-diffusion in casein dispersions: Effects of probe size and protein aggregate size

The self-diffusion coefficients of different molecular weight PEGs (Polyethylene glycol) and casein particles were measured, using a pulsed-gradient nuclear magnetic resonance technique (PFG-NMR), in native phosphocaseinate (NPC) and sodium caseinate (SC) dispersions where caseins are not structured into micelles. The dependence of the PEG self-diffusion coefficient on the PEG size, casein concentration, the size and the mobility of casein obstacle particles are reported. Wide differences in the PEG diffusion coefficients were found according to the casein particle structure. The greatest reduction in diffusion coefficients was found in sodium caseinate suspensions. Moreover, sodium caseinate aggregates were found to diffuse more slowly than casein micelles for casein concentrations >9 g/100 g H₂O. Experimental PEG and casein diffusion findings were analyzed using two appropriate diffusion models: the Rouse model and the Speedy model, respectively. According to the Speedy model, caseins behave as hard spheres below the close packing limit (10 g/100 g H₂O for SC (Farrer & Lips, 1999) and 15 g/100 g H₂O for NPC (Bouchoux et al., 2009)) and as soft particles above this limit. Our results provided a consistent picture of the effects of diffusant mass, the dynamics of the host material and of the importance of the casein structure in determining the diffusion behavior of probes in these systems.