Formation of polyelectrolyte complex particles from self-complexation of N-sulfated chitosan

This work investigated the elaboration of biocompatible nanoparticles from the pH-induced self-complexation of the amphoteric polysaccharide N-sulfated chitosan. The acidification of aqueous solutions of chitosan having a degree of acetylation of 24% and a degree of sulfation of 34% or 56% was followed stepwise by turbidimetry, dynamic light scattering, and electrophoresis. With the highest sulfated chitosan, no turbidity was recorded between pH = 7.8 and 2.0, traducing a high apparent solubility of the polymer chains in this domain of pH. With the lowest sulfated chitosan, a steady increase in turbidity was monitored from pH = 6.90 to 6.15 followed by the flocculation of the polymer at pH approximately 6.0. In this range of pH, the polymer phase separated to yield particles having hydrodynamic diameters decreasing from 350 to 260 nm and an almost constant negative charge. These particles were assembled by electrostatic interactions between the protonated amino residues and the sulfate functions and stabilized by an excess of surface sulfate groups. The particles could be separated from the reaction medium and concentrated by centrifugation-redispersion cycles without alteration of their structure.