Stern Layer Of Micelles Research Articles

Water Structure and Dynamics in the Stern Layer of Micelles: Femtosecond Mid-Infrared Pump-Probe Spectroscopy Study.

Molecular-level understanding of the water structure and dynamics in the Stern layer of micelles is important to elucidate the active role of water in biological processes on membrane surfaces. Micelles and reverse micelles are considered to be excellent membrane model systems. Here, to address the question of whether or not the spatial confinement effect on water in reverse micelles and nanometric water pool systems plays a role in modulating water dynamics, we consider four different aqueous micelle solutions and study the water dynamics in the Stern layer of micelles using a femtosecond mid-infrared pump-probe spectroscopy technique. Vibrational energy relaxation and rotational dynamics of the O?D stretch mode of HDO and the azido stretch mode of hydrazoic acid are critically dependent on the charge, polarity, and chemical structure of the surfactant head group. In particular, water molecules in the Stern layer of micelles, which are not in spatially confined environments, are notably different from those in bulk water. This finding clearly indicates that changes in the vibrational and rotational dynamics of water molecules, even in spatially confined systems, are mainly induced by surface effects instead of spatial confinement effects. We believe that the present experimental results are of importance for understanding water-involved biochemical processes on biological membranes.

Effect of Polymethylene Spacer of Cationic Gemini Surfactants on Solvation Dynamics and Rotational Relaxation of Coumarin 153 in Aqueous Micelles.

The present work demonstrates the solvation dynamics and rotational relaxation of Coumarin 153 (C-153) in the micelles of a series of cationic gemini surfactants, 12-s-12, 2Br(-) containing a hydrophobic polymethylene spacer with s = 3, 4, 6, 8, 12. Steady-state and time-correlated single-photon counting (TCSPC) fluorescence spectroscopic techniques have been used to carry out this study. Steady-state and TCSPC fluorescence data suggest that C-153 molecules are located at the Stern layer of micelles. While probe molecules feel more or less the same micropolarity in the micellar phase, the microviscosity of micelles decreases with spacer chain length. Solvation dynamics at the Stern layer is bimodal in nature with fast solvation as a major component. Counter ions and water molecules bonded with the polar headgroups of surfactant molecules are responsible for the slow component. Average solvation time increases with spacer chain length because of the increased degree of counter ion dissociation. Some water molecules are involved in the solvation of counter ions themselves, resulting in the decrease in "free" water molecules to be available for the solvation of C-153. The hydrophobic spacer chain also has an effect on increasing the solvation time with increasing chain length. The average rotational relaxation time for C-153 decreases with spacer chain length with a rapid decrease at s > 4. The anisotropy decay of C-153 in micelles is biexponential in nature. The slow rotational relaxation is due to the lateral diffusion of C-153 in micelles. Lateral diffusion is much faster than the rotational motion of a micelle as a whole. The rotational motion of the micelle as a whole becomes faster with the decreasing size of micelles.

Computational Study of the Structure and Behavior of Aqueous Mixed System Sodium Unsaturated Carboxylate-dodecyltrimethylammonium Bromide

The mixed surfactant system sodium 10-undecenoate (SUD)-dodecyltrimethylammonium bromide (DTAB) was studied by computational simulation to determine the composition and structure of the mixed microstructures. Results were contrasted with experimental data obtained from literature and our own laboratory. The modelization predicts spherical or cylindrical micelles with a preferential composition of SUD-DTAB of about 1:2, while the system predicts a lamellar structure with a proportion of 1:1 when SUD is replaced by the saturated soap sodium undecanoate. The model also predicts the deep inclusion of bromide ions in the micelle Stern layer. All predictions were in agreement with previous experimental results.

Pressure Effect on Solvation Dynamics in Micellar Environment

Solvation dynamics of an excited solvatochromic probe molecule in micellar environment has been studied as a function of pressure. In addition to steady-state spectrum, time-dependent fluorescence Stokes shift of coumarin 153 in aqueous solution of typical neutral surfactant Triton X-100 was measured at high pressures using time-correlated single-photon counting techniques with a time-resolution of 20 ps. It was found that polarity of the microenvironment decreases with increasing pressure. The solvation dynamics exhibits bimodal relaxation behavior with two characteristic time constants of 198 ps and 1.63 ns at atmospheric pressure. The solvation time becomes shorter with increasing pressure. The bimodal relaxation and its pressure dependence is considered as closely connected with the pressure effect on the hydrogen bonding of water molecules. And also the model assuming an equilibrium between “bound water” and “free water” within the Stern layer of micelles is discussed.

Effect of Counterions and Headgroup Hydrophobicity on Properties of Micelles Formed by Alkylpyridinium Surfactants. 2. Microcalorimetry

We report the influence of counterions and headgroup hydrophobicity on the enthalpies and heat capacities of micelle formation by 1-alkyl-4-n-dodecylpyridinium surfactants in aqueous solution. For micelle-forming 1-alkyl-4-n-dodecylpyridinium iodide surfactants (alkyl = C1−C3), enthalpies of micelle formation show no trend with respect to 1-alkyl chain length. Changes in molecular architecture of the counterion, however, have a large influence on the thermodynamics of micelle formation. It is shown that next to solvation, London dispersion interactions, counterion (substituent)−water interactions, and the microenvironment of counterions adsorbed to micellar surfaces play an important role in determining the exothermicities of micelle formation. Isobaric heat capacities of micelle formation show that the formation of wormlike micelles for salicylate-containing cationic surfactants is due to a favorable microenvironment for salicylate counterions in the Stern layer of micelles.

Pulse radiolysis study of redox reactions of safranine T in sodium dodecylsulphate (SDS) micellar medium

Reaction of hydrated electrons with safranine T (SF+), a phenazine dye useful as sensitizer in photogalvanic cell and the transient semireduced species formed by this reaction have been studied in SDS micellar medium using the technique of pulse radiolysis. Thee aq − reaction with SF+ in the micellar environment was only marginally slower (5.1 × 109 dm3 mol−1 s−1) as compared to that in homogeneous aqueous medium (2.2 × 1010 dm3 mol−1 s−1) explicable on the basis of our finding that although a large fraction of the dye gets localized near the micelle Stern layer where the molecule experiences a dielectric.constant of ≈40, a small but significant concentration of the dye exists in the aqueous bulk as charge pair complex with the anionic surfactant monomer (association constant for the formation of the complex being 2.8 × 104 dm3 mol−1). The transient semireduced absorption band observed in the micellar medium showed a red shift of ≈ 50 nm and also the decay of the transient, which was very fast with 2k = 1 × 109 dm3 mol−1 s−1 in aqueous medium, was stable in the SDS micellar medium over a few tens of milliseconds suggesting that the radical is incorporated deeper than the parent molecule in the SDS micelle. The effect of this stability on the photogalvanic conversion needs to be examined.

Surface potential measurements in pentanol–sodium dodecyl sulphate micelles

The surface potential of sodium dodecyl sulphate (SDS) micelles has been measured by the apparent pKa of a micelle solubilized acid–base indicator. The indicator used was 4-heptadecyl-7-hydroxycoumarin. The surface potentials were measured under conditions of changing surface charge density and bulk ionic strength and the results analysed by a Gouy–Chapman–Stern model for the double layer of the micelle. The results indicate that the sodium counterions in the micelle's Stern layer bind between the sulphate head groups. When pentanol is solubilized by the micelle the experimental potentials are smaller than predicted. The difference is attributed to an increase in the number of sites for counterion binding at the micelle surface.

Spectral and fluorimetric studies on the effect of surfactants on thionine

The effect of surfactants on the absorption and emission properties of thionine (TH+) have been studied in detail. Among the various surfactants investigated sodium lauryl sulphate (SLS) has marked effect on these properties. Changes in the absorption spectrum and the decrease in fluorescence intensity at [SLS] below the critical micelle concentration (CMC) are attributed to the formation of a dye-surfactant complex. At [SLS] above CMC, the restoration of dye spectrum with increased extinction coefficient at the λmax and a small but definite red shift of the λmax are interpreted as due to the incorporation of the dye into the SLS micelle. The absorbance and spectral shift data suggest the thionine cation to be localized near the micelle Stern layer in the case of SLS micelles but completely outside the micelle in the aqueous environment in the case of CTABr. From the absorbance and fluorescence data, the association constant for the formation of the TH+-SLS complex in the premicellar region, and the binding constant for the incorporation of the dye into the micelle in the micellar region have been computed. The values of both these constants were found to increase markedly in the presence of electrolytes.