Synchronous alternate multilayered adsorption of poly(4-vinyl-N-n-butylpyridinium) cations and poly(styrene sulfonate) anions on polystyrene colloidal spheres

Alternate multiple adsorbed layers of up to six macrocations [poly(4-vinyl-N-n-butyl-pyridinium bromide)] and macroanions [sodium poly(styrene sulfonate)] are formed on monodispersed polystyrene colloidal spheres above the critical concentration of the macroions, m*. The m* value is the minimum number of macroions needed to reverse the sign of the ζ potential of the spheres in the first adsorption step. Alternate sign reversal in the ζ potential and expansive–contractive thickness changes are observed on the repeated and alternate addition of macrocations first and macroanions next. When the macroanions are added first, sign reversal in the ζ potential and reversible expansion and contraction do not occur. Breaking of the alternate multiple-type adsorption also occurs when equivalency in the number of dissociative groups of macrocations and macroanions is broken. Synchronous conformational changes of macrocations and macroanions in the multiple-adsorbed layers occurs only when the conformational rigidities with the multiple electrostatic and hydrophobic attraction and/or repulsion between macrocations and macroanions are delicately balanced.