1. Linking molecular/ion structure, solvent mesostructure, the solvophobic effect and the ability of amphiphiles to self-assemble in non-aqueous liquidst
Emmy C Wijay, Tamar L Greaves, Calum J Drummon Faraday Discuss. 2013;167:191-215.doi: 10.1039/c3fd00077j.
Sixteen non-ionic molecular solvents have been found to exhibit the solvophobic effect and to support the formation of amphiphile self-assembly mesophases. The solvents were low molecular weight polar solvents which contained various combinations of amine, hydroxyl or ether moieties with relatively small proportions of hydrocarbon unit constituents. The studied amphiphiles were hexadecyltrimethylammonium bromide (CTAB), hexadecylpyridinium bromide (C16PyrBr) and tetraethylene glycol monohexadecyl ether (C16E4). Lyotropic liquid crystal mesophases with lamellar, normal hexagonal and normal bicontinuous cubic, with ordered one-, two- and three-dimensional periodic structure respectively, were identified in CTAB and C16PyrBr systems by using cross-polarised optical microscopy (CPOM). Mesophase diversity and thermal stability ranges correlated to the Gordon parameter (G) value, a proxy for the solvent cohesive energy density. Infrared spectroscopy confirmed that all the studied molecular solvents were associative liquids. Solvent mesostructure was studied by synchrotron small angle X-ray scattering. The small sub-set of neat solvents which were mesostructured, with polar and non-polar domain segregation, displayed the lowest G values, and amongst the lowest mesophase diversity and thermal stability ranges. It has been established that the G value is a good indicator of whether or not a molecular solvent is likely to behave as a co-surfactant, residing within the amphiphile-solvent interfacial region of self-assembled objects, thereby influencing specific mesophase structure formation. Structure-property behaviour has been explored and shows that beneficial solvent features for serving as amphiphile-self assembly media, with the potential for rich mesophase diversity, include the presence of hydroxyl > amine > ether moieties, while methyl moieties have an adverse effect larger than that of methylene moieties.
2. Multi-lamellar vesicle formation in a long-chain nonionic surfactant: C16E4/D2O system
Luigi Gentile, Kell Mortensen, Cesare Oliviero Rossi, Ulf Olsson, Giuseppe A Ranieri J Colloid Interface Sci. 2011 Oct 1;362(1):1-4.doi: 10.1016/j.jcis.2011.06.053.Epub 2011 Jul 2.
The temperature dependent rheological and structural behavior of a long-chain C(16)E(4) (tetraethylene glycol monohexadecyl ether) surfactant in D(2)O has been studied within the regime of low shear range. In the absence of shear flow, the system forms a lamellar liquid crystalline phase at relatively high temperatures. The present paper reports on the shear-induced multi-lamellar vesicle (MLV) formation in C(16)E(4)/D(2)O at 40 wt.% of surfactant in the temperature range of 40-55 °C. The transition from planar lamellar structure to multi-lamellar vesicles has been investigated by time-resolved experiments combining rheology and nuclear magnetic resonance (rheo-NMR), rheo small-angle neutron scattering (rheo-SANS) and rheometry. The typical transient viscosity behavior of MLV formation has been discovered at low shear rate value of 0.5s(-1).
3. Structural transitions induced by shear flow and temperature variation in a nonionic surfactant/water system
Luigi Gentile, Bruno F B Silva, Sandor Balog, Kell Mortensen, Ulf Olsson J Colloid Interface Sci. 2012 Apr 15;372(1):32-9.doi: 10.1016/j.jcis.2012.01.027.Epub 2012 Jan 24.
In this study, we investigate structural transitions of tetraethylene glycol monohexadecyl ether (C(16)E(4)) in D(2)O as a function of shear flow and temperature. Via a combination of rheology, rheo-small-angle neutron scattering and rheo-small-angle light scattering, we probe the structural evolution of the system with respect to shear and temperature. Multi-lamellar vesicles, planar lamellae, and a sponge phase were found to compete as a function of shear rate and temperature, with the sponge phase involving the formation of a new transient lamellar phase with a larger spacing, coexisting with the preceding lamellar phase within a narrow temperature-time range. The shear flow behavior of C(16)E(4) is also found to deviate from other nonionic surfactants with shorter alkyl chains (C(10)E(3) and C(12)E(4)), resembling to the C(16)E(7) case, of longer chain.