A conductance stopped-flow study of polyelectrolyte systems. Dynamic conformational change of synthetic macroions and their complexation with neutral polymers.
Two dynamic phenomena of polyelectrolyte systems, namely the rapid conformational changes of weak polyelectiolytes (polyacrylic acid (HPAA) and polyethylenimine, induced by pH-jump) and the complexation of HPAA with polyvinylpyrrolidone are first investigated by means of the conductance stopped-flow (kappa-SF) technique. The pH-induced relaxations observed by mixing an aqueous solution of HPAA or polyethylenimine with water containing a tiny amount of alkali or acid, are safely ascribed to the conformational transition of the macroions between the compact "coil" and the stretched "rod" forms. The relaxation times are large at high degrees of neutralization and for "rod" conformation. Tentative values for the thermodynamic parameters of the dynamic conformational changes are obtained and discussed. The reaction rates of the polymer complex formation and dissociation of HPAA with polyvinylpyrrolidone are also determined using the kappa-SF method. The association constant and the rates of formation and dissociation are 1.84 x 10(3) M(-1), 9.4 x 10(4) M(-1) s(-1) and 51 s(-1) at 10 degrees C, respectively. We then derive the thermodynamic parameters from the above results.
Okubo
T
T
Department of Polymer Chemistry, Kyoto University, Kyoto, Japan.