Clustering of oil droplets in o/w emulsions: Controlling cluster size and interaction strength

Clustering of oil droplets changes the rheological properties of oil-in-water (o/w) emulsions and can be used as a tool to structure foods. The aim of this study was to manipulate both oil droplet cluster size and cluster strength in liquid o/w emulsions, and to investigate the effect of these parameters on the rheological properties. Clustered emulsions were prepared using three different methods: (i) clustering by protein-proanthocyanidin interactions, (ii) clustering by hetero-aggregation of oppositely-charged emulsion droplets, and (iii) enzymatic clustering of protein-stabilised droplets using transglutaminase. Clustering by protein-proanthocyanidin interactions allowed to control oil droplet cluster size from 1 to 140 μm. Clusters decreased in size upon both an increase and decrease in pH, but were stable against changes in ionic strength. Hetero-aggregation of oppositely-charged oil droplets (gelatine/whey protein and gelatine/DATEM) allowed to control cluster size from 1 to 40 μm. Clusters showed a strong decrease in size in response to changes in pH and a small decrease in size with increasing ionic strength. Enzymatic clustering did not allow to control cluster size. Cluster strength of proanthocyanidin-stabilised clusters was found to be higher than that of hetero-aggregated clusters. Stabilisation of clusters was likely induced by different protein-proanthocyanidin interactions such as H-bridges, π-π stacking, and hydrophobic interactions, whereas hetero-aggregation is based on electrostatic interactions. Upon clustering, emulsion viscosity increased by up to three orders of magnitude. We conclude that protein-proanthocyanidin interactions and hetero-aggregation are effective methods to tune droplet cluster size and strength in o/w emulsions, and that cluster size and interaction strength control the rheological properties of o/w emulsions with clustered oil droplets.