ABSTRACT
HYPOTHESIS: Film formation and film structure in films formed on solutions of cationic surfactants with polyethylenimine is influenced by the surfactant structure, including both the tail length and the nature of the headgroup, which alter the micelle properties. EXPERIMENTS: A series of cationic surfactants were synthesized and conductivity measurements were used to compare the critical micelle concentrations for these surfactants and their behaviour with and without polyethylenimine at high pH. Small angle neutron scattering measurements were used to characterise the size and shape of the micelles in the presence and absence of the polymer. Film formation between polyethylenimine and the various surfactants was trialled, and the interfacial film structures measured using neutron reflectivity. FINDINGS: Film formation is shown to depend on surfactant tail length, with thicker films forming for surfactants with longer hydrophobic tails. The surfactant headgroup structure affects counterion binding to the micelles, and in the case of the aromatic headgroups, the headgroup affects the extent of micellar growth when polymer is added. Films with the greatest mesostructural ordering were grown using hexadecylpyridinium bromide surfactants.
ABSTRACT
Polymer/silica composite films, stable to calcination, were produced using catanionic surfactant mixtures (hexadecyltrimethylammonium bromide (CTAB) and sodium dodecyl sulfate (SDS)) and polymers (polyethylenimine (PEI) or polyacrylamide (PAAm)) at the air/water interface. Film formation processes were probed by time-resolved neutron reflectivity measurements. Grazing incidence X-ray diffraction (GID) measurements indicate that the mesophase geometry of the interfacial films could be controlled to give lamellar, 2D hexagonal, and several cubic phases (Pn3¯m, Fm3¯m, and Im3¯m) by varying the polyelectrolyte molecular weight, polyelectrolyte chemical nature, or the cationic:anionic surfactant molar ratio. On the basis of GID results, a phase diagram for the catanionic surfactant/polyelectrolyte/TMOS film system was drawn. These films can be easily removed from the interface and mesoporous silica films which retain the film geometry can be obtained after calcination; moreover, this film preparation method provides a simple way to impart polymer functionality into the mesostructured silica wall, which means these films have potential applications in a variety of fields such as catalysis, molecular separation, and drug delivery.
ABSTRACT
We have investigated the spontaneous self-assembly of solid, mesostructured films that form at the air-solution interface on solutions containing a neutral water-soluble polymer and catanionic surfactant mixtures of hexadecyl-trimethylammonium bromide (CTAB) and sodium dodecylsulphate (SDS). The formation processes and structures were probed using neutron reflectivity, X-ray reflectivity, off-specular time-resolved scattering, and grazing incidence diffraction. The mesostructures of films prepared with polyethylene oxide, polyethylenimine, and polyacrylamide at various cationic/anionic surfactant molar ratios are compared. The results suggest that polymers having a weak interaction with the surfactants cause a depletion aggregation process that results in a lamellar phase, whereas polymers having a stronger interaction with the surfactants produce more complex mesostructures in the films.
ABSTRACT
Chemically surface-modified (tosyl-functionalized) carbon nanoparticles (Emperor 2000 from Cabot Corp.) are employed for the extraction and electrochemical determination of phenolic impurities such as benzophenone-3 (2-hydroxy-4-methoxybenzophenone) or triclosan (5-chloro-2-(2,4-dichlorophenoxy)phenol). The hydrophilic carbon nanoparticles are readily suspended and separated by centrifugation prior to deposition onto suitable electrode surfaces and voltammetric analysis. Voltammetric peaks provide concentration information over a 10-100microM range and an estimated limit of detection of ca. 10microM (or 2.3ppm) for benzophenone-3 and ca. 20microM (or 5.8ppm) for triclosan. Alternatively, analyte-free carbon nanoparticles immobilized at a graphite or glassy carbon electrode surface and directly immersed in analyte solution bind benzophenone-3 and triclosan (both with an estimated Langmuirian binding constants of K approximately 6000mol(-1)dm(3) at pH 9.5) and they also give characteristic voltammetric responses (anodic for triclosan and cathodic for benzophenone-3) with a linear range of ca. 1-120microM. The estimated limit of detection is improved to ca.5microM (or 1.2ppm) for benzophenone-3 and ca. 10microM (or 2.3ppm) for triclosan. Surface functionalization is discussed as the key to further improvements in extraction and detection efficiency.
