Chitosan/alkylethoxy carboxylates: a surprising variety of structures

In this work, we present a comprehensive structural characterization of long-term stable complexes formed by biopolycation chitosan and oppositely charged nonaoxyethylene oleylether carboxylate. These two components are attractive for many potential applications, with chitosan being a bioderived polymer and the surfactant being ecologically benign and mild. Experiments were performed at different mixing ratios Z (ratio of the nominal charges of surfactant/polyelectrolyte) and different pH values such that the degree of ionization of the surfactant is largely changed whereas that of chitosan is only slightly affected. The structural characterization was performed by combining static and dynamic light scattering (SLS and DLS) and small-angle neutron scattering (SANS) to cover a large structural range. Highly complex behavior is observed, with three generic structures formed that depend on pH and the mixing ratio, namely, (i) a micelle-decorated network at low Z and pH, (ii) rodlike complexes with the presence of aligned micelles at medium Z and pH, and (iii) compacted micellar aggregates forming a supraaggregate surrounded by a chitosan shell at high Z and pH. Accordingly, the state of aggregation in these mixtures can be tuned structurally over quite a range only by rather small changes in pH.