Impact of Star Polyacid Branching on Polymer Diffusion within Multilayer Films

Abstract

A series of linear and star poly(acrylic acids) (LPAA and star PAAs) were synthesized to explore the effect of molecular architecture on the stratification and polymer dynamics of electrostatic layer-by-layer (LbL) films. Studies of LbL deposition of LPAA and star PAAs with poly[2-(dimethylamino)ethyl methacrylate] (PDMAEMA) at acidic pH showed an ∼30% increase in film dry thickness with increased polymer branching. Consistent with a greater mass of star polymer deposited within the films, in situ ellipsometric measurements of PAA uptake from solution revealed ∼3.5-fold greater diffusion coefficients for 8-arm PAA in comparison to linear PAA. For comparison, the dynamics of the linear PDMAEMA partner was explored via neutron reflectometry (NR) studies of stacked multilayers containing hydrogenated and deuterated polycations, hPDMAEMA and dPDMAEMA. The stacked multilayers deposited from low-ionic-strength solutions were stratified, exhibiting interfacial widths between hydrogenated and deuterated stacks of ∼15 and 10 nm for films constructed with star and linear PAAs, respectively, suggesting relatively low mobility of the polycation in both assemblies. Further exposure of these films to 0.5 M sodium chloride solutions enhanced the mobility of PDMAEMA, revealing an order magnitude faster diffusion of PDMAEMA in films of 8-arm PAA relative to linear PAA. The faster diffusion of polymers within films of star polyacids was correlated not only with the compactness of star polymers but also with an ∼2-fold lower ionization of assembled 8-arm PAA as determined by Fourier transform infrared spectroscopy and thus a lower number of polycation–polyacid ionic contacts in the case of star polymers as compared to their linear counterparts. The significant influence of molecular architecture on the number of polymer–polymer contacts was further confirmed by isothermal titration calorimetry studies of polyelectrolyte complexes in solution.