J. M. Hierrezuelo

On the urea action mechanism: a comparative study on the self-assembly of two sugar-based surfactants.

Studies on the effect of urea on micelle formation and structure of n-octyl-beta-D-thioglucoside (OTG) and N-decanoyl-N-methylglucamide (MEGA-10) were carried out by using the steady-state and time-resolved fluorescence techniques, together with combined static and dynamic light scattering measurements. A similar increase in the critical micelle concentration with the urea addition was observed for both surfactants. This behavior was attributed to a rise in the solubility of hydrocarbon tails and the increase of solvation of the headgroup of the surfactants in the presence of urea. Structural studies mainly based on the analysis of the hydrodynamic radius and aggregation number of micelles revealed that urea induces changes much more significant on micelles of OTG. Particularly, it was found that, whereas the surface area per headgroup of OTG increases with the urea concentration, it does decrease in the case of MEGA-10. This fact suggests that different action mechanisms operate for both surfactants. Accordingly, investigations on the micellar microstructure based on the study of microenvironmental properties such as micropolarity and microviscosity also indicated a more pronounced effect in the case of OTG. Although changes were not observed in the hydrophobic inner region of both micellar systems, a significant increase of polarity and viscosity in the micellar interface of OTG suggests a direct participation of urea in the micellar solvation layer. The differences between the observed behaviors for both micellar systems were interpreted on the basis of two features: the weaker hydration and greater rigidity of the OTG headgroup as compared with MEGA-10.

Role of the head group on the mixed micellization process in binary systems containing a sugar-based surfactant: decanoyl- N -methylglucamide

The mixed micelles of nonionic decanoyl-N-methylglucamide (MEGA-10) with the anionic sodium dodecyl sulphate (SDS), the cationic dodecyltrimetylammonium bromide (DTAB), and the nonionic octaoxyethylene monododecyl ether (C12E8) have been studied using the fluorescence probe technique. The critical micelle concentration of the three mixed systems in the whole composition range were determined by the pyrene 1:3 ratio method, and the experimental results were analysed in the context of the pseudophase separation model, by using the regular solution theory. It was found that the mixed micelles containing the anionic surfactant are more stable than the pure micelles. This fact was attributed to the occurrence of ion–dipole interactions between the head groups of the component surfactants in the mixed micelle. The static quenching method was used to determine the mean aggregation number of pure and mixed micelles. It was found that whereas mixed micelles containing SDS show a positive deviation from the ideal behaviour, those constituted by DTAB deviate negatively. This different tendency was interpreted on the basis of both steric and electrostatic interactions. The evolution of the microstructure of the mixed micelles upon the participation of the co-surfactant was followed through the micropolarity and microviscosity of the mixed systems. Although the micropolarity studies do not allow definite conclusions, the microviscosity assays indicate that the participation of the co-surfactant induces the formation of less ordered micelles, this effect being more pronounced in the case of mixtures with the anionic surfactant.

Exploring the affinity binding of alkylmaltoside surfactants to bovine serum albumin and their effect on the protein stability: A spectroscopic approach

Steady-state and time-resolved fluorescence together with circular dichroism (CD) spectroscopic studies was performed to examine the interactions between bovine serum albumin (BSA) and two alkylmaltoside surfactants, i.e. n-decyl-β-D-maltoside (β-C10G2) and n-dodecyl-β-D-maltoside (β-C12G2), having identical structures but different tail lengths. Changes in the intrinsic fluorescence of BSA from static as well as dynamic measurements revealed a weak protein-surfactant interaction and gave the corresponding binding curves, suggesting that the binding mechanism of surfactants to protein is essentially cooperative in nature. The behavior of both surfactants is similar, so that the differences detected were attributed to the more hydrophobic nature of β-C12G2, which favors the adsorption of micelle-like aggregates onto the protein surface. These observations were substantially demonstrated by data derived from synchronous, three-dimensional and anisotropy fluorescence experiments. Changes in the secondary structure of the protein induced by the interaction with surfactants were analyzed by CD to determine the contents of α-helix and β-strand. It was noted that whereas the addition of β-C10G2 appears to stabilize the secondary structure of the protein, β-C12G2 causes a marginal denaturation of BSA for a protein:surfactant molar ratio as high as 1 to 100.

Rotational Diffusion of Coumarin 153 in Nanoscopic Micellar Environments of n-Dodecyl-β-d-maltoside and n-Dodecyl-hexaethylene-glycol Mixtures

The microstructure of mixed micelles containing n-dodecyl-β-D-maltoside and n-dodecyl-hexaethylene-glycol, two nonionic surfactants belonging to the alkyl polyglucoside and polyoxyethyelene alkyl ether families, respectively, has been investigated. With the aim of understanding how the micellar composition affects the microenvironmental properties of micelles, we have examined the photophysics and dynamics of the neutral probe coumarin 153 in the binary mixtures of the surfactants across the entire composition range. We present data on the steady-state absorption and emission spectra of the probe, as well as fluorescence lifetimes and both steady-state and time-resolved fluorescence anisotropies. These data indicate that the participation of the ethoxylated surfactant in the mixed micelle induces an increasing hydration in the palisade layer of the micelle, which forces the probe to migrate toward the inner micellar region, where it senses a slightly less polar environment. The time-resolved fluorescence anisotropy data were analyzed on the basis of the two-step and wobbling-in-cone model. The average reorientation time of the probe molecule was found to decrease with the presence of the ethoxylated surfactant, in good agreement with steady-state fluorescence anisotropy data, suggesting a reduction of the microviscosity in the solubilization site of the probe. The behavior of all diffusion reorientation parameters was analyzed on the basis of two factors: the micellar hydration and the headgroup flexibility of both surfactants. It was concluded that the increasing participation of the ethoxylated surfactant induces a greater hydration in the micellar palisade layer, producing the formation of a less compact microenvironment where the probe experiences a faster rotational reorientation.

Analysis of the Photophysical Behavior and Rotational-Relaxation Dynamics of Coumarin 6 in Nonionic Micellar Environments: The Effect of Temperature.

The photodynamics of Coumarin 6 have been investigated in three nonionic micellar assemblies, i.e., n-dodecyl-β-d-maltoside (β-C12G2), p-tert-octyl-phenoxy polyethylene (9.5) ether (Triton X-100 or TX100) and n-dodecyl-hexaethylene-glycol (C12E6), to assess their potential use as encapsulation vehicles for hydrophobic drugs. To evaluate the effect of the micellar size and hydration, the study used a broad temperature range (293.15–323.15 K). The data presented here include steady-state absorption and emission spectra of the probe, dynamic light scattering, together with fluorescence lifetimes and both steady-state, as well as time-resolved fluorescence anisotropies. The time-resolved fluorescence anisotropy data were analyzed on the basis of the well-established two-step model. Our data reveal that the molecular probe in all of the cases is solubilized in the hydration layer of micelles, where it would sense a relatively polar environment. However, the probe was found to undergo a slower rotational reorientation when solubilized in the alkylpolyglycoside surfactant, as a result of a more compact microenvironment around the probe. The behavior of the parameters of the reorientation dynamics with temperature was analyzed on the basis of both micellar hydration and the head-group flexibility of the surfactants.

Self-assembly, surface activity and structure of n-octyl-β-D-thioglucopyranoside in ethylene glycol-water mixtures.

The effect of the addition of ethylene glycol (EG) on the interfacial adsorption and micellar properties of the alkylglucoside surfactant n-octyl-β-d-thioglucopyranoside (OTG) has been investigated. Critical micelle concentrations (cmc) upon EG addition were obtained by both surface tension measurements and the pyrene 1:3 ratio method. A systematic increase in the cmc induced by the presence of the co-solvent was observed. This behavior was attributed to a reduction in the cohesive energy of the mixed solvent with respect to pure water, which favors an increase in the solubility of the surfactant with EG content. Static light scattering measurements revealed a decrease in the mean aggregation number of the OTG micelles with EG addition. Moreover, dynamic light scattering data showed that the effect of the surfactant concentration on micellar size is also controlled by the content of the co-solvent in the system. Finally, the effect of EG addition on the microstructure of OTG micelles was investigated using the hydrophobic probe Coumarin 153 (C153). Time-resolved fluorescence anisotropy decay curves of the probe solubilized in micelles were analyzed using the two-step model. The results indicate a slight reduction of the average reorientation time of the probe molecule with increasing EG in the mixed solvent system, thereby suggesting a lesser compactness induced by the presence of the co-solvent.

An Energetic Analysis of the Phase Separation in Non-Ionic Surfactant Mixtures: The Role of the Headgroup Structure

The main goal of this paper was to examine the effect of the hydrophilic surfactant headgroup on the phase behavior of non-ionic surfactant mixtures. Four mixed systems composed of an ethoxylated plus sugar-based surfactants, each having the same hydrophobic tail, were investigated. We found that the hydrophilicity of the surfactant inhibits the tendency of the system to phase separate, which is sensitive to the presence of NaCl. Applying a classical phase separation thermodynamic model, the corresponding energy parameters were evaluated. In all cases, the parameters were found to depend on the type of nonionic surfactant, its concentration in the micellar solution and the presence of NaCl in the medium. The experimental results can be explained by assuming the phase separation process takes place as a result of reduced hydration of the surfactant headgroup caused by a temperature increase. The enthalpy-entropy compensation plot exhibits excellent linearity. We found that all the mixed surfactant systems coincided on the same straight line, the compensation temperature being lower in the presence of NaCl.