Characterization of the growth of polyelectrolyte multilayers formed at interfaces between aqueous phases and...

Polyelectrolyte multilayers (PEMs) formed at interfaces between aqueous solutions and thermotropic (water-immiscible) liquid crystals (LCs) offer the basis of a new method to tailor the nanometer-scale structure and chemical functionality of these interfaces. Toward this end, we report a study that compares the growth of PEMs formed at mobile and deformable interfaces defined by LCs relative to growth observed at model (rigid) solid surfaces. Experiments aimed at determining if polyelectrolytes such as poly(sodium-4-styrenesulfonate) (PSS) can partition from the aqueous phase into the bulk of the LC yielded no evidence of such partitioning. Whereas measurements of the growth of PEMs formed from poly(allylamine hydrochloride) (PAH) and PSS at the aqueous-LC interface revealed growth characteristics similar to those measured at both hydrophobic and hydrophilic interfaces of solids, the growth of PEMs from PAH and poly(acrylic acid) (PAA) at the aqueous-LC interface was found to differ substantially from the solids investigated: (i) the linear growth of PEMs of PAH/PAA that was measured at the aqueous-LC interface under conditions that did not lead to the growth of PEMs at the interface of octadecyltrichlorosilane (OTS)-treated glass (a hydrophobic solid surface), and (ii) in comparison to the growth of PEMs of PAH/PAA at the surface of glass (a hydrophilic charged surface), a higher rate of growth was observed at the aqueous-LC interface. The finding that the growth rate of PEMs of PAH/PAA at aqueous-LC interfaces is greater than on solid surfaces is supported by additional measurements of growth as a function of pH. Finally, the pH-triggered reorganization of PAH/PAA PEMs supported at the aqueous-LC interface led to changes in the order and optical properties of the LC. These data are discussed in light of the nature of aqueous-LC interfaces, including the mobility and deformability of the interface and recent measurements of the zeta-potentials of aqueous-LC interfaces.