Effect of polyacid architecture and polycation molecular weight on lateral diffusion within multilayer films

Despite the potential use of polyelectrolyte multilayers for biomedical, separation, and energy applications, their dynamic properties are not sufficiently understood. In this work, center-of-mass diffusion of a weak polyacid-poly(methacrylic acid) (PMAA) of linear and 8-arm architecture (L-PMAA and 8-PMAA, respectively) and matched molecular weight-was studied in layer-by-layer (LbL) assemblies with poly(diallyldimethylammonium) chloride (PDADMAC) of varied molecular weight. The film deposition at low-salt, acidic conditions when PMAA was only partially ionized yielded thicker, more diffused layers with shorter PDADMAC chains, and bilayer thickness decreased for multilayers constructed with longer PDADMAC. The molecular architecture of PMAA had a weak effect on film growth, with bilayer thickness being ∼20% larger for L-PMAA for the films constructed with the shortest PDADMAC (35 kDa) and identical film growth for L-PMAA and 8-PMAA with the longest PDADMAC (300 kDa). The exposure of the multilayer films to 0.2M NaCl triggered a reduction in PMAA ionization and significant lateral diffusivity of fluorescently labeled PMAA molecules (PMAA*), with diffusion coefficients D ranging from 10-13 to 10-12 cm2/s, as determined by the fluorescence recovery after photobleaching technique. For all the films, polymer mobility was higher for star polyacids as compared to their linear counterparts, and the dependence of PMAA diffusion coefficient D on PDADMAC molecular weight (D ∼ M-n) was relatively weak (n < 0.6). However, 8-PMAA demonstrated an approximately doubled power exponent compared to the L-PMAA chains, suggesting a stronger effect of the molecular connectivity of the partner polycation molecules on the diffusion of star polyelectrolytes.