Self aggregation of binary mixtures of sodium dodecyl sulfate and polyoxyethylene alkyl ethers in aqueous solution

The mixed micelles of sodium dodecyl sulphate (SDS) with Brij35 and Brij 97 were studied separately by fluorescence measurement using pyrene as fluorescent probe. In the range of 0–1.0 mole fraction (X) of added SDS to Brij solutions, the cmc value of the mixed micelles varies from 0.085 to 8 mmol with Brij 35 and 0.04 to 8 mmol with Brij 97. The aggregation number also changes. A measure of the stability of mixed micelles is also presented. The interaction parameter ₁₂ and the chain–chain contribution parameter (B₁) are extracted from the analysis of the results. This parameter B₁ is related to the standard free energy change associated with the introduction of one ionic species into a nonionic micelle coupled with the release of one nonionic species from the micelle. The clouding behaviour of Brij 97 in the presence of SDS was investigated and the associated thermodynamic parameters of clouding were generated and discussed.     

Development of predictive quantitative retention–activity relationship models of alkaloids by mixed micellar liquid chromatography

The mixed micellar liquid chromatography is a mode that uses mixed micellar system of Brij35/SDS (85 : 15) as a mobile phase under adequate experimental conditions, can simulate the resting membrane potential and the conformation of the long hydrophilic polyoxyethylene chains remains unchanged. In this article, the applications of biopartitioning micellar chromatography, using mixed micellar system to describe and estimate bioactivities of alkaloids, has been focused. The BMC_Brij35/SDS‐QRAR models of half‐life time, volume of distribution, plasma clearance and area under concentration–time curve were obtained using Brij35‐SDS retention data. The aim is to take a look at the capability of the mixed micellar liquid chromatography model to describe and/or estimate the bioactivity of alkaloids. Copyright © 2009 John Wiley & Sons, Ltd.     

Molecular dynamics study of solubilization of cyclohexane,benzene, and phenol into mixed micelles composed of sodium dodecyl sulfate and octaethylene glycol monododecyl ether

Molecular dynamics calculations of a mixed micelle composed of sodium dodecyl sulfate (SDS) and octaethylene glycol monododecyl ether (C₁₂E₈) were performed for six compositions (SDS/C₁₂E₈ = 100/0, 80/20, 60/40, 40/60, 20/80, and 0/100) to investigate the composition dependence of the mixed micelle structure and solubilization of cyclohexane, benzene, and phenol molecules by the micelle. The radial density distribution of the hydrophilic polyoxyethylene (POE) group of C₁₂E₈ as a function of distance from the micelle center is very sharp for micelles with high SDS content because the POE group captures a Na⁺ ion in solution and wraps around it to form a compact crown-ether-like complex. The hydrophobic dodecyl groups of SDS and C₁₂E₈ were separately distributed in the mixed micelle core. ΔG(r) evaluated for each solute showed that despite the structural changes of the micelle the binding strength of the solute molecules to the micelle did not change significantly. © 2019 Wiley Periodicals, Inc.     

THE EFFECT OF MIXED MICELLES OF SURFACTANTS ON THE ALKALINE HYDROLYSIS OF ESTERS

The alkaline hydrolysis of aromatic and normal aliphatic acid esters have been studied at 25°C In mixed micellar solution of surfactants (Brij35—SDS, Brij35 — DTAB, Brij35—TTAB.Brij35-CTAB. Triton X—100 —CTAB, Triton X— 100 —SDS) with UV spectrophotometry and the method of thermokinetics The critical mice liar concentrations of the corresponding systems have also been measured with UV spectrophotometry in this paper. K_jnln micellar pseudo-phase has been calculated- The ratios of ki.to ki.for all mixed micellar systems Investigated are less than 1. The results indicate that these reactions are inhibited by the mixed micelles and the mixed micelles exhibit a greater effect of Inhibition on the reactions than those do In corresponding single ones. The reason for this is that the micropolarity of the compact Stern layer of mixed micelle is lower, and the micro viscidity Is higher. The Inhibition effect! also depend on the hydrophobic chain length of the surfactants and the hydrophobicity of the substrate.     

THE EFFECT OF SURFACTANT MICELLES ON THE ALKALINE HYDROLYSIS OF DIMETHYLFORMAMIDE

The alkaline hydrolysis of dimethylformamide has been studied at 40'C in micellar solutions of single surfactant (CTAB. SDS. Brij 35) with the analog thermoanalytical curve method of thermokinetics. A kinetic equation of micellar catalysis under the condition of highter reactant concentration than micellar concentration ([S]>[M]) has been derived from the pseudophase model of micellar catalysis and some relative assumptions, The kinetic parameters. k_m, k_2mand the association constant of reactant with micelle K₁, have been calculated in this way. the results indicate that these surfactant micelles exhibit catalytic effect on the reaction. This is attributed to the micropolarity and local concentration effect of micelles.     

THE EFFECTS OF MIXED MICELLES OF SURFACTANTS ON POLYMERIZATION OF ACRYLAMIDE

The polymerization of acrylamide in mixed micellar solutions of surfactants, initiated by NaHSO₃ has been studied at 20 and 3Q° C with time variable method of thermokinetics for 1. 5-order reaction. The results indicate that the mixed micellar systems of cationic or anionic with zwitterionic surfactants (SLS/ CTAB, SLS/ TTAB, SLS/ SDS) and cationic with nonionic surfactants (Brij 357sol; CTAB, Bri-J35/TTAB, Brij35/ DTAB) have catalytic effect on the polymerization in the order, at 20° C. SLS/ SDS SLS/ TTAB SLS/ CTAB Brij35/ CTAB at 30° C SLS/ SDS SLS/ TTAB≈ / CTAB Bri-j35/ DTAB= sBrij35/ TTAB as Brij35/ CTAB, while Brij35/ SDS mixed micellar system has inhibition. These effects are attributed to the effect of the Stern layer of mixed micelles on the step of initiator (HSOT) to form free radical.     

Solubilization of Aliphatic Carboxylic Acids (C3-C6) by Sodium Dodecyl Sulfate and Brij 35 Micellar Pseudophases

The apparent dissociation constants of 1-propanoic, 1-butanoic, 1-pentanoic and 1-hexanoic acids were obtained for the first time in Brij 35 micellar solutions with concentration from 0.03 to 0.20 mol⋅L⁻¹ and sodium dodecyl sulfate (SDS) micellar solutions with concentrations from 0.01 to 0.30 mol⋅L⁻¹. A pronounced effect of Brij 35 micelles on the acid-base properties of aliphatic acids was observed. The binding constants, K _b, of carboxylic acids to micellar pseudophases of SDS and Brij 35 were estimated within the framework of the pseudophase model. The dependences of Gibbs energies of transfer from water to the micellar pseudophases were constructed, and Gibbs energies were evaluated for methylene and carboxylic group transfers into Brij 35 and SDS micelles. Comparison of the Gibbs energies of methylene group transfer from water to Brij 35 and SDS suggests that the mechanisms of hydrocarbon group transfer into the core of nonionic and anionic micelles involving the same monomer hydrophobic tail length are similar.     

Decreased surfactant activity coefficients in polymer-surfactant mixtures

The SDS unimer concentration in a series of mixed anionic/non-ionic surfactant solutions comprising sodium dodecylsulphate (SDS) and sugar-based dodecyl bis-N-methyl gluconamides (C₁₂BNMG) have been studied using an anionic surfactant selective electrode, both in the presence and absence of the polyampholyte gelatin. The activity of the SDS has been calculated at the critical micelle concentration (CMC) in the gelatin-free studies and at CMC(1) in the gelatin studies. From the known solution composition, the activity coefficients can be calculated; these show deviations from unity around a solution mole fraction (_SDS) of 0.95 SDS in both cases. The deviation is significantly greater in the presence of gelatin, to an extent that the SDS activity versus _SDS curve exhibits a maximum and a minimum in the region _SDS=0.8–1.0, consistent with the possibility of coexisting micelle types, in agreement with our earlier NMR study (Griffiths et al. (1998) J Chem Soc Chem Comm 1:53).     

Spectrophotometric study of interaction and solubilization of procaine hydrochloride in micellar systems

The interaction of Procaine hydrochloride (PC) with cationic, anionic and non-ionic surfactants; cetyltrimethylammonium bromide (CTAB), sodium dodecyl sulfate (SDS) and triton X-100, were investigated. The effect of ionic and non-ionic micelles on solubilization of Procaine in aqueous micellar solution of SDS, CTAB and triton X-100 were studied at pH 6.8 and 29°C using absorption spectrophotometry. By using pseudo-phase model, the partition coefficient between the bulk water and micelles, K_x, was calculated. The results showed that the micelles of CTAB enhanced the solubility of Procaine higher than SDS micelles (K_x = 96 and 166 for SDS and CTAB micelles, respectively) but triton X-100 did not enhanced the solubility of drug because of weak interaction with Procaine. From the resulting binding constant for Procaine-ionic surfactants interactions (K_b = 175 and 128 for SDS and CTAB surfactants, respectively), it was concluded that both electrostatic and hydrophobic interactions affect the interaction of surfactants with cationic procaine. Electrostatic interactions have a great role in the binding and consequently distribution of Procaine in micelle/water phases. These interactions for anionic surfactant (SDS) are higher than for cationic surfactant (CTAB). Gibbs free energy of binding and distribution of procaine between the bulk water and studied surfactant micelles were calculated.      

Removal of cadmium ions using micellar-enhanced ultrafiltration with mixed anionic-nonionic surfactants

Micellar-enhanced ultrafiltration (MEUF) was used to remove cadmium ions from wastewater efficiently. In this study the nonionic surfactants polyoxyethyleneglycol dodecyl ether (Brij35) and polyoxyethylene octyl phenyl ether (TritonX-100) were for micellar-enhanced ultrafiltration to lower the dosage of the anionic surfactant sodium dodecyl sulfate (SDS). The surfactant critical micelle concentration (CMC) and the degree of micelle counterion binding were investigated. The effects of nonionic surfactant addition on the efficiency of cadmium removal, the residual quantities of surfactant, the permeate flux and the secondary membrane resistance were investigated. A comparison between MEUF with SDS and MEUF with mixed anionic–nonionic surfactants was undertaken. The results show that the addition of Brij35 or TritonX-100 reduced the CMC of SDS and the degree of counterion binding for the micelles. Due to these variations the Cd²⁺ rejection efficiency was at a maximum when the Brij35:SDS and the TritonX-100:SDS molar ratio was 0.5. The Cd²⁺ rejection efficiency in MEUF with SDS is higher than for MEUF with mixed surfactants when the total dose of surfactant is constant. The permeate flux of MEUF with SDS is higher than that for MEUF with mixed surfactants while the secondary resistance of MEUF with SDS is less than that of MEUF with mixed surfactants.     

Effects of Nonionic, Cationic, and Mixed Nonionic-Cationic Surfactants on the Acid-Base Behavior of Phenyl Salicylate

The effects of Brij 35 micelles, CTABr micelles, and mixed Brij 35–CTABr micelles on the acid–base behavior of phenyl salicylate (PST) have been studied in aqueous solution containing 2% v/v acetonitrile. The apparent pK_b (pK^app_b) of PST is decreased by 1.5 pK units with the increase in [Brij 35] from 0 to 0.02 M which is attributed to micellar medium effect. The values of pK^app_b remain almost independent of [CTABr] within its range 0.01–0.03 M. The increase in [CTABr] from 0 to 0.03 M in aqueous solution containing 0.02 M Brij 35 has not resulted in a change in pK^app_b. This shows that the characeristic structural features of nonionic Brij 35 micelles remain essentially unchanged on addition of CTABr under the present experimental conditions.     

Effects of surfactant micelles on solubilization and DPPH radical scavenging activity of Rutin

The interaction of the antioxidant Rutin with the radical DPPH (2,2-diphenyl-1-picrylhydrazyl) in presence of cationic (CTAB, TTAB, DTAB), non-ionic (Brij78, Brij58, Brij35), anionic (SDS) and mixed surfactant systems (CTAB-Brij58, DTAB-Brij35, SDS-Brij35) has been followed by spectrophotometric and tensiometric methods to evaluate the DPPH radical scavenging activity (RSA) of Rutin in these model self-assembled structures. The results show that the solubilization capacity of various single surfactant systems for both DPPH as well as Rutin followed the order cationics > non-ionics > anionic. The radical scavenging activity of Rutin in the solubilized form was higher within ionic micelles than in non-ionic micelles. However, the antioxidant exhibited enhanced activity for the radical in mixed cationic-non-ionic micelles compared with any of the single component micelles. In contrast, anionic-non-ionic mixed micelles modulated the activity of Rutin in-between that seen for pure anionic and non-ionic micelles only.     

Studies on the Physicochemical Properties of 3-Alkoxyl-2-hydroxypropyl Trimethylammonium Chloride–Sodium Dodecyl Sulfonate Binary-Surfactant Aqueous Systems

Surface tension, micelle formation, surface adsorption, and solubilization of dimethylaminoazobenzene (DMAB) are studied in aqueous solutions of 3-alkoxyl-2-hydroxypropyl trimethylammonium chloride (alkoxyl = C_nH_2n+1O, n = 8, 12, 14, 16), of sodium dodecyl sulfonate, and of mixtures of these cationic surfactants and the anionic surfactant at 40°C. Synergistic effects on micelle formation, surface tension reduction, and solubilization enhancement of DMAB are observed in the cationic–anionic mixed surfactant systems. The experimental results are discussed in the light of the interactions between the two kinds of surfactant ions.     

Micellae catalysis of the oxidation of 1,4-dihydro-nicotinamides by methylene blue part 2

The oxidation of 1-R-1,4-dihydronicotinamides (1a: R = benzyl, 1b:R = octyl, 1c:R = cetyl) by methylene blue has been studied in the presence of micelles of cetyltrimethylammonium bromide (CTAB), polyoxyethylene[23]lauryl ether (Brij^® 35) and sodium dodecylbenzenesulfonate (SDBS). In CTAB, a small rate enhancement was observed below the cmc, followed by a gradual decrease above the cmc. Brij 35 has little effect on the reaction rate. The rate vs. concentration profile in SDBS shows a very sharp maximum near the cmc for 1b and 1c, whereas a more moderate increase in rate is observed for 1a. The effects are analyzed in terms of the pseudophase model for micellar catalysis, and it appears that the observed rate enhancements can be completely ascribed to increments of the reactant concentration in the micellar pseudophase. Comparison with rate effects in sodium dodecylsulfate (SDS) micelles reveals that the reaction in SDBS micelles proceeds in a more polar environment. This provides kinetic evidence that the aryl moiety in SDBS allows a deeper penetration of water molecules into the micelle, thus giving rise to a more open surface for SDBS micelles than for SDS micelles.     

Effects of Inorganic Salts on Micellization and Solubilization in an Aqueous Solution of Poly(ethylene oxide)/Poly(propylene oxide)/Poly(ethylene oxide) Triblock Copolymer

The effects of inorganic salts on micellization and solubilization of prednisolone in aqueous solution of poly(ethylene oxide)/poly(propylene oxide)/poly(ethylene oxide) triblock copolymer (Pluronic P85) were studied. The effect of inorganic salts on decrease in the cloud point and the critical micelle concentration (cmc) of Pluronic P85 was the order of Na₂HPO₄ > NaH₂PO₄ > NaCl > NaBr. Moreover, it was found that Pluronic P85 forms two kinds of micelles: monomolecular micelles and polymolecular micelles. The polymolecular micelle increased with increasing amount of added inorganic salts. Moreover, solubilization behavior is explained from the standpoint of salting out for prednisolone and association characteristics of Pluronic P85.     

Spectral studies of N-nonyl acridine orange in anionic, cationic and neutral surfactants

The spectroscopic and photophysical properties of N-nonyl acridine orange – a metachromatic dye useful as a mitochondrial probe in living cells – are reported in water and microheterogeneous media: anionic sodium dodecylsulfate (SDS), cationic cetyltrimethylammonium bromide (CTAB) and neutral octylophenylpolyoxyethylene ether (TX-100). The spectral changes of N-nonyl acridine orange were observed in the presence of varying amount of SDS, CTAB and TX-100 and indicated formation of a dye–surfactant complex. The spectral changes were also regarded to be caused by the incorporation of dye molecules to micelles. It was proved by calculated values K_b and f in the following order: K_b TX-100 > K_b CTAB > K_b SDS and f_TX-100 > f_CTAB > f_SDS. NAO binds to the micelle regardless the micellar charge. There are two types of interactions between NAO and micelles: hydrophobic and electrostatic. The hydrophobic interactions play a dominant role in binding of the dye to neutral TX-100. The unexpected fact of the binding NAO to cationic CTAB can be explained by a dominant role of hydrophobic interactions over electrostatic repulsion. Therefore, the affinity of NAO to CTAB is smaller than TX-100. Electrostatic interactions play an important role in binding of NAO to anionic micelles SDS. We observed a prolonged fluorescence lifetime after formation of the dye–surfactant complex τ_SDS > τ_TX-100 > τ_CTAB > τ_water, the dye being protected against water in this environment. TX-100 is found to stabilize the excited state of NAO which is more polar than the ground state. Spectroscopic and photophysical properties of NAO will be helpful for a better understanding of the nature of binding and distribution inside mammalian cells.     

Alterations in phospholipid bilayers caused by sodium dodecyl sulphate/triton X-100 mixed systems

The mechanisms governing the subsolubilizing and solubilizing interaction of sodium dodecyl sulphate (SDS)/Triton X-100 mixtures and phosphatidylcholine liposomes were investigated. Permeability alterations were detected as a change in 5(6)-carboxy-fluorescein (CF) released from the interior of vesicles and bilayer solubilization as a decrease in the static light-scattered by liposome suspensions. Three parameters were described as the effective surfactant/lipid molar ratios (Re) at which the surfactant system a) resulted in 50% of CF release (Re _50%CF); b) saturated the liposomes (Re _SAT;c) led to a complete solubilization of these structures (Re _SOL). From these parameters the corresponding surfactant partition coefficientsK _50%CF,K _SAT andK _SOL were determined. The free surfactant concentrationsS _W were lower than the mixed surfactant CMCs at subsolubilizing level, whereas they remained similar to these values during saturation and solubilization of bilayers in all cases. Although theRe increased as the mole fraction of the SDS rose (X _SDS), theK parameters showed a maximum atX _SDS values of about 0.6, 0.4 and 0.2 forK _50%CF,K _SAT andK _SOL respectively. Thus, the higher the surfactant contribution in surfactant/lipid system, the lower theX _SDS at which a maximum bilayer/water partitioning of mixed surfactant systems added took place and, consequently, the lower the influence of the SDS in this maximum bilayer/water partitioning.Abbreviations PC Phosphatidylcholine - PIPES piperazine-1,4 bis (2-ethanesulphonic acid) - SDS sodium dodecyl sulphate - X _SDS mole fraction of sodium dodecyl sulphate in the mixed system - CF 5(6)-carboxyfluorescein - Re effective surfactant/lipid molar ratio - Re _50%CF effective surfactant/lipid molar ratio for 50% CF release - Re _SAT effective surfactant/lipid molar ratio for bilayer saturation - Re _SOL effective surfactant/lipid molar ratio for bilayer solubilization - S _W surfactant concentration in the aqueous medium - S _{W, 50%CF} surfactant concentration in the aqueous medium for 50% CF release - S _{W, SAT} surfactant concentration in the aqueous medium for bilayer saturation - S _{W, SOL} surfactant concentration in the aqueous medium for bilayer solubilization - S _B surfactant concentration in the bilayers - K bilayer/aqueous phase surfactant partition coefficient - K _50%CF bilayer/aqueous phase surfactant partition coefficient for 50% CF release - K _SAT bilayer/aqueous phase surfactant partition coefficient for bilayer saturation - K _SOL bilayer/aqueous phase surfactant partition coefficient for bilayer solubilization - PL phospholipid TLC-FID, thin-layer chromatography/flame ionization detection system - PI polydispersity index - CMC critical micellar concentration - r ² regression coefficient     

Effect of alcohols on the micellar properties in aqueous solution of alkyltrimethylammonium bromides

The effect ofn-butanol,n-propanol, andn-hexanol on the critical micelle concentration (CMC) and degree of ionisation of the micelles of dodecyl-, tetradecyl- and hexadecyltrimethylammonium bromides in aqueous solution has been determined by conductimetric techniques. Increase of the molality of added alcohol over the concentration ranges examined (up to 0.3 mol kg^–1 butanol, 0.07 mol kg^–1 pentanol and 0.025 mol kg^–1 hexanol) caused a progressive decrease of CMC and increase of the degree of ionisation for each surfactant-alcohol system. At a constant molality of added alcohol the degree of ionisation increased with a) an increase of the chain length of the surfactant for each alcohol and b) an increase of the chain length of the alcohol for each surfactant. The distribution of each alcohol between the aqueous and micellar phases and the free energy of solubilization were determined from the change of CMC with molality of added alcohol.     

Kinetics of the Micellar Effects on the Alkaline Hydrolysis of 2-Chloro-quinoxaline in Acetonitrile-Water Mixtures at 35°C

Pseudo-first-order reaction rate for alkaline hydrolysis of 2-chloroquinoxaline (2-CQX) is carried out in acetonitrile (AN)-water (H₂O) mixtures at 35°C. Cationic surfactants as dodecyltrimethylammonium bromide (DOTAB) and an anionic surfactant as sodium dodecylsulphate (SDS) are used above their critical micelle concentration (cmc) to study the effect of micelles on reaction rate. When increasing the percentage of volume of AN, the rate profiles with DOTAB are shown to slightly increase with increasing surfactant concentration, while that with SDS are found to smoothly decrease. The micellar effect is explained in terms of a modified pseudo-phase ion exchange model. The binding constant (K_S) between 2-CQX and DOTAB as micelle showed a decrease by increasing percentage of volume of AN, while that with SDS increased. The counterion micellar coverage degrees (β) are found to be 0.55 and 0.85 with DOTAB and SDS systems, respectively, at all range of volume percentage of AN. Finally, the calculated ratio between rate constants in water to that in the micelle region k_w/k_M at different volume percentage of AN indicated that DOTAB enhances the reaction rate while SDS inhibits it.      

The effect of the nature of the surfactant on the location of 6-R-2,2,4-trimethyl-1,2-dihydroquinolines in micelles

The locus of solubilization of 6-R-2,2,4-trimethyl-1,2-dihydroquinoline molecules (R=Me, OEt) in sodium dodecyl sulfate (SDS) and cetyltrimethylammonium bromide (CTAB) has been determined by comparing the UV spectra of micellar solutions of the dihydroquinolines and their solutions in solvents of various polarities. The parameterR _pv (defined as the ratio of the absorbance of the long-wave band maximum to that at the adjacent valley) decreases with an increase in the solvent polarity in the order:n-heptane > 2-propanol > ethanol > H₂O. In SDS micellar solutions,R _pv is close to the corresponding value in water and does not depend on [SDS]. In CTAB micellar solutions,R _pv is essentially greater than in water and increases with [CTAB]. Thus, the solubilized dihydroquinoline molecules in SDS micelles reside in the Stern layer, and in CTAB micelles they are located both in the interior of the micelle and in the Stern layer; in this case the micelle packing begins from the core.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 948–950, May, 1994.