The influence of macromolecular architecture on the critical aggregation concentration of large amphiphilic starch derivatives

A range of hyperbranched emulsifiers were prepared by reaction between starch and 2-octen-1-yl succinic anhydride (OSA, commonly used in the food industry), under slightly basic conditions in water, leading to starches bearing hydrophobic OSA groups randomly distributed along the chains. By using different starch backbones and varying the amount of OSA during the synthesis, amphiphilic OSA-modified starches were obtained that formed aggregates in water and having controlled structural parameters. These parameters were characterized using 1H NMR, multiple-angle laser light scattering and size-exclusion chromatography. The critical aggregation concentration (CAC) was measured for samples with different levels of OSA modification, of macromolecular size and degree of starch branching. Increasing the dispersity in macromolecular size and/or degree of OSA substitution noticeably decreased the CAC. The results are interpreted in terms of the branching structure and conformation of the modified starches: all findings can be understood in terms of the various influences of molecular size, composition and flexibility. The structural factors affecting the CAC of large hyperbranched surfactants are found to be similar to those seen with smaller and simpler branched synthetic surfactants.