We have studied the nano- and microparticles formed by complexation of PDAC [poly(diallyldimethyl-ammoniumchloride)] and SDS (sodium dodecyl sulfate). The complexation phenomenon was characterized by light scattering and zeta-potential measurements. The nature of the complexes was revealed by direct-imaging cryogenic temperature transmission electron microscopy (cryo-TEM), showing nanometric details of the complexes formed around the point of neutralization. The images also reveal how those aggregates are solubilized by excess surfactant, first into faceted particles with threadlike micelles attached to their surfaces, prior to complete solubilization, then into lacelike aggregates, and finally into spheroidal micelles. The nanostructure of the complexes strongly suggests they are made of a hexagonal liquid crystalline phase. This was further supported by small-angle X-ray scattering (SAXS).

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The formation of nanoparticles by interaction of an anionic polyelectrolyte, sodium polyacrylate (NaPA), was studied with a series of oppositely charged surfactants with different chain lengths, alkyltrimethylammonium bromide (CnTAB). The binding and formation of nanoparticles was characterized by dynamic light scattering, zeta-potential, and self-diffusion NMR. The inner nanostructure of the particles was observed by direct-imaging cryogenic-temperature transmission electron microscopy (cryo-TEM), indicating aggregates of hexagonal liquid crystal with nanometric size.

Synchrotron-X-ray and surface tension studies of a strong polyelectrolyte (PE) in the semi-dilute regime (∼0.1M monomer-charges) with varying surfactant concentrations show that minute surfactant concentrations induce the formation of a PE-surfactant complex at the gas/solution interface. X-ray reflectivity and grazing angle X-ray diffraction (GIXD) provide detailed information of the top most layer, where it is found that the surfactant forms a two-dimensional liquid-like monolayer, with a noticeable disruption of the structure of water at the interface. With the addition of salt (NaCl) columnar-crystals with distorted-hexagonal symmetry are formed.

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