Effect of Cosolvents DMSO and Glycerol on the Self-Assembly Behavior of SDBS and CPC: An Experimental and Theoretical Approach

Abstract

The study of the effect of cosolvents on the micellization of ionic surfactants is relevant in different industrial applications. In this article, we studied the effects of binary aqueous mixtures of DMSO and glycerol on the micellization and thermodynamic behavior of sodium dodecyl benzenesulfonate (SDBS) and cetylpyridinium chloride (CPC) in the range of (293.15–308.15) K. The electrical conductivity method was employed to determine the parameters of micellization such as the critical micellar concentration (CMC) and degree of counterion dissociation (α). The temperature dependence of CMC values was used to calculate other thermodynamic parameters of micellization such as the standard free energy of micellization (ΔG m 0), the standard enthalpy of micellization (ΔH m 0), and the standard entropy of micellization (ΔS m 0). Result analysis showed that the CMCs of both surfactants (SDBS and CPC) were directly proportional to the cosolvent concentration. The standard free energy of micellization (ΔG m 0) was negative in all cases, and it increased with increases in the cosolvent concentration, thereby reducing the driving force for micellization. Quantum chemical calculations and molecular dynamic (MD) simulations were essential to understanding the phenomena and provide a well-supported molecular picture of the micellization process. In this work, a combined experimental and molecular modeling study on the effect of cosolvents such as DMSO and glycerol on the self-assembly behavior of SDBS and CPC was performed. It was found that the supramolecular assembly is inhibited by the presence of glycerol and DMSO because hydrophobic regions in the solvent media increased with increasing concentration of the nonaqueous solvents, imparting cosolvency and promoting the decrease in amphiphilic assembly.

Physicochemical studies of polyethylene glycols in aqueous biotin solutions at different temperatures and constant pressure

“…The intermolecular free length, in table 3, indicates that the molecules are much more closely packed, thus implying the existence of the strong solute solvent interaction inside the mixture, evident from the figure 5. The presence of the strong binding forces inside the liquid system between solute and solvent is confirmed by the increasing values of Vander Waal's constants with the temperature, in table 3 [29][30][31][32].…”

Experimental and Theoretical Exploration of Volumetric Properties of Aminobutyric Acid and l-Valine in the Electrolytic Environment at T = 283.15 to 318.15 K and Pressure P = 0.1 MPa

“…The noncovalent interaction index (NCI) , was used to qualitatively identify the areas where weak interactions predominate, the origin of which may be dispersive in nature, hydrogen bonds, dipole–dipole interactions, or repulsive steric effects, which are based on the sign of the second eigenvalue (λ 2 ) of the electron density matrix (Hessian matrix) as is described in the literature. , We also calculate the intensity of the noncovalent interactions by using the independent gradient (IGM) approach. , In the framework of the IGM approach, the descriptor δ g inter identifies the gradient attenuation of the electronic density (ED) due to interactions resulting from the electron sharing between fragments. Plotting δ g inter isosurfaces provides a chemically intuitive picture of the noncovalent forces between such fragments.…”

Micellar Solution Behavior of Cetylpyridinium Surfactants in 2-Propanol–Water Mixed Media at Different Temperatures

“…A similar trend in ΔS m 0 values has been observed for other cationic surfactants in mixed media with an increase in temperature. 17,45,64,65 Unlike CPCl, a decrease in the values of ΔS m 0 was not observed with a rise in temperature for CPBr except at 7.5% PrOH−WR mixed media (Figure S4b; Supporting Information).…”

“…16 Sharma et al have shown that the micellization of cetylpyridinium chloride (CPCl) and sodium dodecyl benzenesulfonate (SDBS) is suppressed by the rise in temperature as well as the inclusion of cosolvents (dimethyl sulfoxide/glycerol) in the aqueous medium. 17 Furthermore, mixed media (ethylene glycol−water) has been reported as a promising media to remove the toxic flume SO 2 gas. 18 Considering the significance of surfactant aggregation in various polar organic solvents−water mixed media and useful outcome of the studies, it is significant to have knowledge on the surfactant's micellization in mixed media which can offer different polarities based on the compositions.…”

“…It has been found that even the aqueous free solvent system, such as a mixture of ethylene glycol and propylene glycol, has a significant impact on the extent of aggregation of nonionic surfactants where micelles tend to change the rodlike structure into ellipsoidal aggregates as the percentage of ethylene glycol increases . Sharma et al have shown that the micellization of cetylpyridinium chloride (CPCl) and sodium dodecyl benzenesulfonate (SDBS) is suppressed by the rise in temperature as well as the inclusion of cosolvents (dimethyl sulfoxide/glycerol) in the aqueous medium . Furthermore, mixed media (ethylene glycol–water) has been reported as a promising media to remove the toxic flume SO 2 gas .…”