Impact of model perfumes on surfactant and mixed surfactant self-assembly

The impact of some model perfumes on surfactant self-assembly has been investigated, using small-angle neutron scattering. A range of different model perfumes, with differing degrees of hydrophilicity/hydrophobicity, have been explored, and in order of increasing hydrophobicity include phenyl ethanol (PE), rose oxide (RO), limonene (LM), linalool (LL), and dihydrogen mercenol (DHM). The effect of their solubilization on the nonionic surfactant micelles of dodecaethylene monododecyl ether (C12EO12) and on the mixed surfactant aggregates of C12EO12 and the cationic dialkyl chain surfactant dihexadecyl dimethyl ammonium bromide (DHDAB) has been quantified. For PE and LL the effect of their solubilization on the micelle, mixed micelle/lamellar and lamellar regimes of the C12EO12/DHDAB mixtures, has also been determined. For the C12EO12 and mixed DHDAB/C12EO12 micelles PE is solubilized predominantly at the hydrophilic/hydrophobic interface, whereas the more hydrophobic perfumes, from RO to DHM, are solubilized predominantly in the hydrophobic core of the micelles. For the C12EO12 micelles, with increasing perfume concentration, the more hydrophobic perfumes (RO to DHM) promote micellar growth. Relatively modest growth is observed for RO and LM, whereas substantial growth is observed for LL and DHM. In contrast, for the addition of PE the C12EO12 micelles remain as relatively small globular micelles, with no significant growth. For the C12EO12/DHDAB mixed micelles, the pattern of behavior with the addition of perfume is broadly similar, except that the micellar growth with increasing perfume concentration for the more hydrophobic perfumes is less pronounced. In the Lbeta (Lv) region of the DHDAB-rich C12EO12/DHDAB phase diagram, the addition of PE results in a less structured (less rigid) lamellar phase, and ultimately a shift toward a structure more consistent with a sponge or bicontinuous phase. In the mixed L1/Lbeta region of the phase diagram PE induces a slight shift in the coexistence from Lbeta toward L1. The addition of LL to the Lbeta (Lv) region of the DHDAB-rich C12EO12/DHDAB phase diagram also results in a reduction in the lamellar structure (less rigid lamellae), and a shift toward a structure more consistent with a sponge or bicontinuous phase, or a coexisting phase of small vesicles. For the mixed L1/Lbeta region of the phase diagram LL induces a shift toward a greater L beta component.     

Antiadhesive action of a marine microbial surfactant

The antiadhesive action of a lipopeptide biosurfactant from a marine bacterium was investigated. The effect of cultivation conditions on the adhesion property of few bacterial strains was studied. It was observed that the static cultures showed greater adhesion due to scarcity of oxygen. The biosurfactant upon surface conditioning was found to be effective in removal of the microbial adhesion at a concentration as low as 0.1 g L⁻¹. The percentages of inhibition of adhesion against different test bacterial strains ranged from 15 to 89% using 0.1–10 g L⁻¹ of purified biosurfactant. These percentages of adhesion inhibition were found to be significantly higher than the previously reported values. The antiadhesive efficacy of the biosurfactant was also evident from confocal laser scanning microscopy studies.     

Highly-ordered selective self-assembly of a trimeric cationic surfactant on a mica surface

Novel trimeric cationic surfactant tri(dodecyldimethylammonioacetoxy)diethyltriamine trichloride (DTAD) has been synthesized, and its self-assembly morphology on a mineral surface has been studied. From its micelle solution, highly ordered bilayer patterns are obtained on a mica surface, whereas randomly distributed bilayer patches are formed on a silica substrate. The highly ordered bilayer patterns on mica are first caused by the matching of the special structure of DTAD headgroups with the negative charge sites on mica, which leads to the specific nucleation of DTAD on the mica surface via electrostatic interaction. Furthermore, hydrophobic interaction among the DTAD hydrocarbon chains results in the formation of the bilayer structure, and intermolecular hydrogen-bonding among the DTAD headgroups promotes the directional growth of such bilayer structures.     

Nanorod shape separation using surfactant assisted self-assembly

High quality single size nanorods can be separated from polydisperse samples using surfactant-assisted nanorod self-assembly.     

Reversible binding of multivalent ions by surfactant self-assembly

High molecular weight nonionic surfactants have been chemically modified to bind multivalent ions reversibly by using a moderate temperature stimulus as an on/off mechanism. Only above the critical micellization temperature (CMT) does binding of multivalent ions take place, whereas below the CMT, no binding occurs to the free surfactant molecules. Different calorimetric techniques have been used to prove the reversible binding of multivalent ions. This tunable binding of multivalent metal ions allows for the improvement of many ion-exchange processes and offers attractive opportunities in the biomedical field.     

XAS study of a metal-induced phase transition by a microbial surfactant

The metal-induced micelle-to-vesicle phase change that the ferric complex of the microbially produced amphiphile, marinobactin E (M(E)), undergoes has been investigated by X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS). Marinobactin E is one member of the suite of siderophores, marinobactins A-E, that are used by the source bacterium to facilitate iron acquisition. Fe(III)-M(E) undergoes a micelle-to-multilamellar vesicle transition in the presence of Cd(II) and Zn(II). XRD measurements indicate the interlamellar repeat distance of the Cd(II)- and Zn(II)-induced multilamellar vesicles is approximately 5.3 nm. XAS spectra of the sedimented Cd(II)- and Zn(II)-induced multilamellar vesicles suggests hexadentate coordination of Cd(II) and Zn(II) consisting of two monodentate carboxylate ligands and four water ligands. This coordination environment supports the hypothesis that Cd(II) and Zn(II) bridge the terminal carboxylate moiety of two Fe(III)-M(E) headgroups, pulling the headgroups together in an arrangement that favors vesicle formation over the formation of micelles. XAS spectra of the Fe(III) center in the sedimented Cd(II)- and Zn(II)-induced vesicles confirm the anticipated six-coordinate geometry of Fe(III) by the M(E) headgroup via the two hydroxamate groups and the alpha-hydroxy amide moiety.     

A rheological investigation of the self-assembly and adsorption behavior of a surfactant salt

The properties of a surfactant salt obtained by neutralizing oleic acid with an ethoxylated stearylamine were determined in blends of water and propylene glycol. The adsorption of this surfactant salt onto the surface of a commercial TiO(2) dispersed in blends of water and propylene glycol was studied using a rheometer. At low propylene glycol content the dispersions exhibited Newtonian behavior, but became shear-thinning fluids with high viscosity at propylene glycol contents above a critical concentration. The observed behavior is consistent with a model involving a surfactant bilayer below the critical point, moving to a monolayer above the critical point. The high viscosity above the critical point is generated by reversible flocculation via hydrophobic forces. The viscosity of the dispersion flocculated by the hydrophobic forces was found to be much higher than that caused by flocculation via van der Waals forces in the absence of surfactant. Changing both the total concentration of the surfactant in the dispersion and the dispersion temperature resulted in a reversible transition between the bilayer and the monolayer. Although the surfactant was always above its critical micelle concentration (CMC) the amount on the particle surface varied appreciably with both propylene glycol and surfactant concentration.     

Supramolecular self-assembly of block copolymer based on rigid surfactant

The supramolecular self-assembling of pyridine-containing amphiphilic block copolymers (PS-b- P4VP and PS-PI-P2VP) and 4-biphenylcarboxylic acid (BPCA) in selective solvents has been systematically studied. BPCA molecules are able to complex with the vinylpyridine (VP) moieties through hydrogen bonding, which leads to a transformation of spherical block copolymer micelles into structured nanofibers in solutions. The effects of molar ratio of BPCA to the VP repeat units, solvent selectivity, and copolymer composition on the supramolecular complex nanofiber formation have been systematically investigated by atomic force microscopy (AFM), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). The formation mechanism of supramolecular self-assembly nanofibers was discussed.     

Peering into the self-assembly of surfactant templated thin-film silica mesophases

It is now recognized that self-assembly is a powerful synthetic approach to the fabrication of nanostructures with feature sizes smaller than achievable with state of the art lithography and with a complexity approaching that of biological systems. For example, recent research has shown that silica/surfactant self-assembly combined with evaporation (so-called evaporation induced self-assembly EISA) can direct the formation of porous and composite thin-film mesostructures characterized by precise periodic arrangements of inorganic and organic constituents on the 1-50-nm scale. Despite the potential utility of these films for a diverse range of applications such as sensors, membranes, catalysts, waveguides, lasers, nano-fluidic systems, and low dielectric constant (so-called low k) insulators, the mechanism of EISA is not yet completely understood. Here, using time-resolved grazing incidence small-angle X-ray scattering (GISAXS) combined with gravimetric analysis and infrared spectroscopy, we structurally and compositionally characterize in situ the evaporation induced self-assembly of a homogeneous silica/surfactant/solvent solution into a highly ordered surfactant-templated mesostructure. Using CTAB (cetyltrimethylammonium bromide) as the structure-directing surfactant, a two-dimensional (2-D) hexagonal thin-film mesophase (p6mm) with cylinder axes oriented parallel to the substrate surface forms from an incipient lamellar mesophase through a correlated micellar intermediate. Comparison with the corresponding CTAB/water/alcohol system (prepared without silica) shows that, for acidic conditions in which the siloxane condensation rate is minimized, the hydrophilic and nonvolatile silicic acid components replace water maintaining a fluidlike state that avoids kinetic barriers to self-assembly.     

Mesoscopic simulation of self-assembly in surfactant oligomers by dissipative particle dynamics

Self-assembling properties of surfactant oligomers in an aqueous medium is simulated by dissipative particle dynamics (DPD). The critical micellar concentration (CMC) of dimeric (oligomerization = 2) and trimeric (oligomerization = 3) surfactant is much lower than their single-chain counterpart. All surfactants form spherical micelles at the concentration not far above their CMC. The transition from spherical to cylindrical micelles exhibits with increasing surfactant concentration. Lamellar micelles will appear with further increasing the surfactant concentration. For dimeric and trimeric surfactants, cylindrical micelles transform into extremely long “wormlike” or “threadlike” micelles before the transition to lamellar micelles. These results are in qualitative agreement with laboratory experiment. Average aggregation numbers (AN) of micelles increase with a power law of AN  c when the surfactant concentration c CMC. The self-diffusion coefficients will drop with a power law of D  c⁻ when wormlike micelles are formed.     

Cosurfactant and cosolvent effects on surfactant self-assembly in supercritical carbon dioxide

The impact of alcohol additives on the self-assembly of surfactants in supercritical carbon dioxide is investigated using lattice Monte Carlo simulations. We observe that all studied (model) alcohols reduce the critical micelle concentration. The reduction is stronger the longer the hydrocarbon chain of the alcohol, and the higher the alcohol concentration. Short-chain alcohols are found to concentrate in the surfactant layer of the aggregates, replacing surfactant molecules and leading to a strong decrease of the aggregation number and a large increase of the number of aggregates. On the other hand, only a small number of alcohol molecules with longer chain length are found in the aggregates, leading to a slight increase in the aggregation number. However, structural properties such as size and density profiles of aggregates at the same aggregation number are not influenced markedly. Consequently, short-chain alcohols act as cosurfactants, directly influencing the properties of the aggregates, while alcohols with longer hydrocarbon chains work as cosolvents, altering the properties of the solvent. However, the transition between both extremes is gradual.     

Hydrotropic salt promotes anionic surfactant self-assembly into vesicles and ultralong fibers

Molecular self-assembly has become a versatile approach to create complex and functional nanoarchitectures. In this work, the self-assembly behavior of an anionic surfactant (sodium dodecylbenzene sulfonate, SDBS) and a hydrotropic salt (benzylamine hydrochloride, BzCl) in aqueous solution is investigated. Benzylamine hydrochloride is found to facilitate close packing of surfactants in the aggregates, inducing the structural transformation from SDBS micelles into unilamellar vesicles, and multilamellar vesicles. The multilamellar vesicles can transform into macroscale fibers, which are long enough to be visualized by the naked eye. Particularly, these fibers are robust enough to be conveniently separated from the surfactant solution. The combined effect of non-covalent interactions (e.g., hydrophobic effect, electrostatic attractions, and π-π interactions) is supposed to be responsible for the robustness of these self-assembled aggregates, in which π-π interactions provide the directional driving force for one-dimensional fiber formation.     

Lipid and surfactant self-assembly: Significance of NMR in developing our understanding

This review, devoted to the memory of Kåre Larsson, deals with surfactant and lipid self-assembly. The focus is on the crucial role of NMR techniques in the understanding, at a molecular level, molecular dynamics and microstructure. The strength of NMR self-diffusion in determining size and shape of supramolecular aggregates as well as microstructural features, in terms of water-in-oil, oil-in-water and bicontinuity, is emphasized.     

Hofmeister anion effects on surfactant self-assembly and the formation of mesoporous solids

Recent work on mesoporous silica formation using cationic and non-ionic templates has unveiled a large number of anion effects. Anions are seen to change the hydrolysis rates of the silicate precursors, affecting the surface properties and morphologies of the final products after calcination, and they often improve the hydrothermal stability of the silica materials. These advances are reviewed in connection with the Hofmeister series of anions and the known effects of anions on the self-assembly and phase behavior of cationic and non-ionic surfactants.     

Electrostatic self-assembly of neutral and polyelectrolyte block copolymers and oppositely charged surfactant

We investigated the phase behavior and the microscopic structure of the colloidal complexes constituted from neutral/polyelectrolyte diblock copolymers and oppositely charged surfactant by dynamic light scattering (DLS) and small-angle neutron scattering (SANS). The neutral block is poly(N-isopropylacrylamide) (PNIPAM), and the polyelectrolyte block is negatively charged poly(acrylic acid) (PAA). In aqueous solution with neutral pH, PAA behaves as a weak polyelectrolyte, whereas PNIPAM is neutral and in good-solvent condition at ambient temperature, but in poor-solvent condition above approximately 32 degrees C. This block copolymer, PNIPAM-b-PAA with a narrow polydispersity, is studied in aqueous solution with an anionic surfactant, dodecyltrimethylammonium bromide (DTAB). For a low surfactant-to-polymer charge ratio Z lower than the critical value ZC, the colloidal complexes are single DTAB micelles dressed by a few PNIPAM-b-PAA. Above ZC, the colloidal complexes form a core-shell microstructure. The core of the complex consists of densely packed DTA+ micelles, most likely connected between them by PAA blocks. The intermicellar distance of the DTA+ micelles is approximately 39 A, which is independent of the charge ratio Z as well as the temperature. The corona of the complex is constituted from the thermosensitive PNIPAM. At lower temperature the macroscopic phase separation is hindered by the swollen PNIPAM chains. Above the critical temperature TC, the PNIPAM corona collapses leading to hydrophobic aggregates of the colloidal complexes.     

Extension of the ladder model of self-assembly from cylindrical to disclike surfactant micelles

The ladder model of growth of cylindrical micelles gives expressions for the micellar size distribution and for the mean aggregation number, which are in good agreement with the experiment. Here, we consider this model and its extension to the case of disclike micelles. In analogy with the modeling of elongated micelles as sphero-cylinders, the disclike micelles can be modeled as toro-discs. Upon micelle growth, the hemispherical caps of a cylindrical aggregate remain unchanged, whereas the semitoroidal periphery of a disclike micelle expands. This effect can be taken into account in the expression for the size distribution of the disclike micelles, which predicts the dependence of the micelle mean aggregation number on the surfactant concentration. It turns out that disclike micelles could form in a limited range of surfactant concentrations, and that their mean aggregation number cannot exceed a certain maximal value. Large disclike micelles can exist only near the border with the domain of cylindrical micelles. Then, small variations in the experimental conditions could induce a transformation of the disclike micelles into cylindrical ones.     

Oligomeric polymer surfactant driven self-assembly of phenylene-bridged mesoporous materials and their physicochemical properties

The detailed synthesis of highly hydrophobic average pore benzene-bridged hybrid mesoporous silicas under an acidic medium is described. With the use of a 1,4-bis(triethoxysilane)benzene silsesquioxane precursor and biodegradable alkyl polyoxyethylene (Brij-56 or Brij-76) nonionic surfactant oligomers as supramolecular templates, no molecular scale periodicity was observed. The well-defined mesoporous materials could be synthesized with two-dimensional hexagonal (p6mm) symmetries. The textural and surface properties (adsorption isotherms of water and benzene vapors) were estimated and were compared to the analogous benzene-bridged mesoporous silica with molecular scale periodicity which was prepared using cationic surfactant under basic conditions. Different textural properties resulted for the two kinds of materials and revealed some important insights regarding the structure and nature of the materials.