Complex nanoparticles based on chitosan and ionic/nonionic strong polyanions: formation, stability, and application.
Interpolyelectrolyte complex (IPEC) nanoparticles formed between chitosan having different molar masses (470, 670, and 780 kDa) and two random copolymers of 2-(acrylamido)-2-methylpropanesulfonate (AMPS) with tert-butylacrylamide (TBA) [P(AMPS(54)-co-TBA(46)) and P(AMPS(37)-co-TBA(63))] were prepared by the dropwise addition of polyanion onto the chitosan solution. The effect of polyelectrolyte characteristics and the molar ratio between charges on the morphology of the complex nanoparticles and on their colloidal stability was deeply investigated by turbidimetric titration (optical density at 500 nm), dynamic light scattering, and atomic force microscopy. It was found that the lowest sizes of the IPEC nanoparticles were obtained, with both polyanions, when the chitosan having the lowest molar mass (470 kDa) was used as a major component. In this case, the particle sizes varied in a narrow range, even after the complex stoichiometry; i.e., when the polyanion was added in excess, the colloidal stability of these IPEC dispersions was very high. A mechanism of complex formation as a function of the ratio between charges was proposed. According to this mechanism, the nonstoichiometric complex nanoparticles formed at molar ratios between charges, n(-)/n+, lower than 0.2, i.e., far from the complex stoichiometry, would have a high density of positive charges in excess not only because of the chitosan in excess, which forms the shell, but also because of the mismatch of opposite charges, due to both the differences in the flexibility of complementary polyions and the presence of the hydrophobic comonomer, TBA, in the polyanion structure. Nonstoichiometric IPECs prepared at n(-)/n+ around 0.2 proved to be more efficient than chitosan in the destabilization of kaolin from a model suspension, with a lower optimum concentration flocculation and a much larger flocculation window being found compared with chitosan.
Dragan
Ecaterina Stela
ES
"Petru Poni" Institute of Macromolecular Chemistry, Aleea Grigore Ghica Voda 41 A, RO-700487 Iasi, Romania. sdragan@icmpp.ro
Mihai
Marcela
M
Schwarz
Simona
S
D000838:Anions; D048271:Chitosan / Q000737:chemistry*; D003102:Colloids / Q000737:chemistry*; D003460:Crystallization / Q000379:methods; D008422:Materials Testing; D053758:Nanoparticles / Q000737:chemistry* / Q000648:ultrastructure*; D010316:Particle Size
D000838:Anions; D003102:Colloids; D048271:Chitosan