Acrylic acid and vinylamine copolymers: Anomalous acidity and association with short polyacids

Abstract

Acrylic acid and vinylamine copolymers represent one of the simplest polyampholyte structures. The acid-base and solution properties of these copolymers are hardly studied, and there are no works devoted to the synthesis of a set of copolymers with different compositions. We have synthesized a set of acrylic acid and vinylamine copolymers containing from 21 to 95 mol% acrylic acid units. The copolymers show the hydrodynamic properties and solubility of typical polyampholytes. Potentiometric titration revealed unusual acid-base properties of the new copolymers. The addition of HCl to the copolymers in the form of sodium/potassium salt results in only partial protonation of carboxyl anions and amine groups, including the acidic range (pH 2.5). This abnormally high acidity of acrylic acid and vinylamine copolymers is probably due to the formation of strong intra- and intermolecular hydrogen or ionic bonds between partially protonated and protonated groups: ∼COO−+H3N∼, COOH∙∙∙:NH2∼, ∼H2N:∙∙∙ +H3N∼. Poly(vinylamine) and copolymers are able to stabilize curcumin in aqueous medium, significantly increasing its concentration in the neutral pH range. Polymers with high content of amine groups prevent curcumin degradation, probably by converting it to a more stable anionic form. New copolymers are promising substances for the creation of nucleic acid carriers for gene therapy and genetic engineering. The copolymer containing 21 % acrylic acid is comparable to poly(vinylamine) in terms of interaction with oligonucleotides, but yields more homogeneous polyplexes without the impurity of positively charged and potentially toxic particles.