<p>Three polymer-surfactant systems comprised of branched polyethylene imine (PEI) with an anionic surfactant (sodium dodecylsulfate; SDS), a cationic surfactant (tetradecyltrimethylammonium bromide; TTAB), and a zwitterionic surfactant (<italic>N</italic>-tetradecyl-<italic>N</italic>,<italic>N</italic>-dimethyl-3-ammonio-1-propanesulfonate; SB3-14) were studied based on the properties of surface tension, pyrene fluorescence emission, dynamic light scattering, pH, and zeta potential measurements. The critical aggregation concentration (<italic>cac</italic>) and polymer saturation point (<italic>psp</italic>) were determined for all three systems. The effect of these surfactants on the physico-chemical characteristics (diameter and surface charge) of the complexes formed was determined. Polymer-surfactant interactions occurred in all of the systems studied, with the strongest interactions, electrostatic in nature, occurring in the SDS-PEI system. After the neutralization of the polymer charges with the addition of the surfactant, the hydrophobic effect started to control the interlacing of the polymer chains. For the PEI-TTAB system, a very dense film was formed at surfactant concentrations above 2.0 mmol L^-1. In this case, the bromide counter-ion interacted with both the positively-charged PEI and the head of the surfactant, which is responsible for the formation of double layer coordination complexes. For the system composed of PEI and the zwitterionic surfactant, less cooperative associations occurred in comparison with the other systems.</p>

A formação de complexos supramoleculares em solução aquosa pela associação do polieletrólito poli(etilenoimina) (PEI) com misturas do biossurfactante colato de sódio (NaC) e o surfactante aniônico dodecil sulfato de sódio (SDS) foi aqui investigado usando as técnicas de condutivimetria, tensiometria, fluorimetria, espalhamento de raios X a baixos ângulos (SAXS) e medidas de pH. Os resultados de fluorimetria, condutivimetria e medidas de pH levaram à conclusão de que os monômeros de NaC e SDS ligam-se primeiramente em sítios específicos das cadeias do polieletrólito PEI via interação eletrostática e posteriormente através de associação cooperativa. A interação do NaC com o PEI é mais fraca do que a interação do SDS com o PEI, porém, a adição de SDS ao sistema NaC-PEI levou à formação de micelas mistas SDS-NaC que interagiram fortemente com o polieletrólito PEI. Os resultados de SAXS sugeriram que o complexo supramolecular possui característica elipsoidal e essa forma não depende da concentração de surfactante nem da χNaC.

The formation of supramolecular complexes produced by association of poly(ethyleneimine) (PEI) and mixtures of sodium cholate (NaC) and sodium dodecyl sulfate (SDS) was investigated by pH, electrical conductivity, fluorescence spectroscopy and small angle X-ray scattering (SAXS) measurements. The fluorescence linked to previously measured values of pH and conductivity led to the conclusion that NaC and SDS molecules firstly bind to specific sites of the PEI chains via electrostatic interaction and secondly undergo self-assembly through regular cooperative association. The interaction of NaC with the polyelectrolyte PEI is weaker than that of SDS and the addition of SDS to the NaC-PEI system led to the formation of mixed NaC-SDS micelles which stronger interact with PEI. The SAXS results suggested that the micellar aggregates have a considerably ellipsoidal characteristic and the micellar shape is not affected by the surfactant concentration nor by χNaC.

Mixed-micelle formation between sodium chlolate (NaC) and the anionic surfactant sodium dodecanoate (SDoD) in Tris-HCl buffer solutions, pH 9.00, varying the molar fraction of the surfactants, was investigated by means of electrical conductivity and steady-state fluorescence of pyrene. The critical micelar concentration (cmc) was measured from the equivalent conductance versus the square root of the molar surfactant concentration plots and the regular solution theory (RST) was used to predict the mixing behavior. The I1/I3 pyrene ratio-surfactant concentration plots were used as an additional technique to follow the behavior and the changes in the micropolarity of the mixed micelles.