Formation and structure of chitosan–poly(sodium methacrylate) complex nanoparticles

Abstract

ABSTRACTInterpolyelectrolyte complex (IPEC) dispersions were prepared from chitosan and poly(sodium acrylate), NaPMA, by mixing their solutions, at different carboxyl-to-aminium molar ratios, rCA. Gyration radius was determined by small angle x-ray scattering (SAXS) and showed that, as rCA was increased, IPEC dimensions decreased and reached a minimum at rCA = 0.75, which was considered the ratio at which IPEC cluster dimensions were minimum, following collapse, phase segregation, nucleation, and growth of larger particles. Pair distance distributions, P(r), became narrower up to rCA = 0.75, increasing its width from this point. Relaxation-related parameters from dynamic light scattering (DLS) intensity correlation functions (ICFs) identified three main relaxation processes. The fast process, related to free polyelectrolyte molecules random motion disappeared as rCA, was increased. The other two relaxation processes also were a function of rCA and presented marked changes at rCA = 0.75. At the same value of rCA, the energy of activation for the average relaxation rate showed the occurrence of a clear change in the nature of IPEC-related interactions. As hydrodynamic diameter, determined by DLS, was much larger than the gyration radius determined by SAXS, IPEC particles could be described as being composed by a core, rich in segregated, insoluble material, enveloped by IPEC soluble clusters, possibly in the form of water-rich gels.