Properties of aqueous solutions for two binary mixed systems between two kinds of bile salts and nonionic surfactants

The micellar properties of aqueous binary mixed solutions for two systems consisting of sodium cholate (NaC)-octaoxyethylene glycol mono n-decyl ether (C₁₀E₈) and sodium glycocholate (NaGC)-C₁₀E₈ have been studied on the basis of surface tensions, polarity of the micelle interior and the mean aggregation number. Application of two theoretical treatments, based on regular solution and excess thermodynamic quantities for critical micellar concentration (CMC) data from surface tension curves of two mixed systems showed that the mole fraction of each bile salt in the mixed micelles near the CMC is lower than that of the corresponding prepared mole fraction in the mixed solution. The polarity of the interior suggested that the hydrophobicity of intramicelles increased with the increase of the mole fraction of bile salt in the mixed solution and that the mixed micelles become dramatically more hydrophobic at a mole fraction of 0.68 for NaGC−C₁₀E₈ system and 0.75 for NaC−C₁₀E₈ system, respectively. This implies that the micelles become richer in the bile salt molecules and the tendency appears strongly for NaGC−C₁₀E₈ system due to the strong cohesion between the conjugated glycines in the NaGC molecules. The decrease of aggregation number with the increase of the mole fraction of bile salts shows that the micelles approach those of the single system of each bile salt. This supports the previously mentioned facts.     

Solubilization of cholesterol in two binary mixed micelles of bile salt and nonionic surfactant

The saturated amounts of solubilized cholesterol (C_ch) in mixed micelles of sodium cholate (NaC) and octaoxy-ethylene glycol monon-decyl ether (C₁₀E₈) and of sodium zyme assay at 25, 29, 33 and 37°C. The C_ch values in both systems increase with the total surfactant concentration. Because the mixed micelles for both systems tend to form C₁₀E₈-rich micelles near the critical micellar concentration (CMC) of the mixed system, the curves of cholesterol solubility approached the C_ch curve for C₁₀E₈ alone near the CMC. The tendency of C_ch to decrease in both systems with increasing mole fractions of bile salts resembled that of the mean aggregation number of micelles. Thermodynamic analyses of cholesterol solubilization showed that the free energy of solubilization, if considered as the transfer of cholesterol from solid state to micellar environment, increased with increasing mole fraction of bile salt. The enthalpy of cholesterol solubilization (ΔH_S→M) decreased with the mole fraction of bile salts and showed break points around the mole fraction of 0.75 for the NaC−C₁₀E₈ system and at 0.60 for the NaDC−C₁₀E₈ system, respectively. These phenomena resemble earlier hydrophobicity data for mixed micelles by fluorescence measurements. Furthermore, C_ch values for the NaDC−C₁₀E₈ system were larger than those for the NaC−C₁₀E₈ system because of the structural differences at the 7α hydroxyl group between NaC and NaDC. This fact was confirmed by thermodynamic calculations.     

Micellar and Interfacial Behavior of Cationic Benzalkonium Chloride and Nonionic Polyoxyethylene Alkyl Ether Based Mixed Surfactant Systems

Micellar and interfacial properties of mixed surfactant systems comprising benzalkonium chloride, a cationic surfactant and nonionic polyoxyethylene alkyl ether surfactants (POE: C₁₀E₇, C₁₀E₈, C₁₀E₉, C₁₀E₁₀) have been investigated by surface tension, fluorescence and dynamic light scattering techniques. Critical micelle concentration (CMC) for different mixing mole fractions has been investigated by surface tension and fluorescence measurements. Ideal CMC, mixed micellar composition (X ₁ ^m , X ₁ ^σ ), interaction parameters for mixed micelles (β ^m) and adsorption monolayer (β ^σ ), surface excess concentration (Г_max), minimum area per molecule (A _min) and related thermodynamic properties have also been determined. Lowering of the CMC and negative interaction parameter values indicate synergism in the mixed micelle and monolayer formed, whereas, thermodynamic parameters evaluated for the proposed mixed systems indicate stability of the resulting micelles and monolayer. Micellar aggregation number (N _agg) and hydrodynamic diameter (D _h) computed from fluorescence and dynamic light scattering measurements respectively illustrate micellar growth in the mixed state. Results obtained for the proposed mixed systems can be helpful in designing smart materials for industrial surfactant based formulations.     

Mixed monolayer and mixed micelle formation in binary mixture of surfactants—Systems for trioxyethylenated dodecyl sulfonate and some polyoxyethylenated fatty alcohol ether nonionic surfactants

The interaction and synergism of some polyoxyethylenated fatty alcohol ether (POE) nonionic surfactants (C₁₂E₂, C₁₂E₃, C₁₀E₅, C₁₀E₇, where C_x indicates number of carbon atoms in the chain and E_y indicates number of oxyethylene glycol ethers) with trioxyethylenated dodecyl sulfonate (C₁₂E₃S) in mixed monolayer formation at the surface and in mixed micelle formation in aqueous solutions were studied at 25 and 40°C by calculating interaction parameters (β_α, β_M) from surface tension-concentration data by use of Rosen's equations based on the nonideal solution theory. All the systems investigated adapt reasonably well to the nonideal model, with negative values of β_σ and β_M (where M means micelle and σ refers to the air-liquid interface) indicating a favorable interaction between the mixed surfactants. Either at a monolayer or in a mixed micelle, the attractive interaction becomes stronger when the alkyl chain in the POE surfactant is longer, i.e., when the POE becomes more hydrophobic. The interaction increases in the order C₁₀E₇<C₁₀E₅<C₁₂E₃, C₁₂E₂. For the two C₁₀E _n (n= 5,7)/C₁₂E₃S systems, as temperature increases from 25 to 40°C, the interaction increases in a mixed micelle, but it decreases in a mixed monolayer. Synergism in mixed micelle formation exists for C₁₂E₃S/C₁₀E _n mixtures when X₁ ^M , the mole fraction of POE in a mixed micelle, is ≈0.4–0.8, whereas synergism does not occur in the systems of C₁₂E₃S/C₁₂E _m due to the large difference between CMC₁ and CMC₂, i.e., large |In(C ₁ ^M /C ₂ ^M )| value (where CMC=critical micelle concentration). The degree of synergism in mixed micelle formation is temperature independent and is 0.23, 0.18, and close to zero for C₁₀E₅/C₁₂E₃S, C₁₀E₇/C₁₂E₃S, and C₁₂E _m (m=2,3)/C₁₂E₃S systems, respectively. Synergism in surface tension reduction effectiveness occurs in C₁₂E₃S/C₁₂E₂ and C₁₂E₃S/C₁₂E₃ systems. The mole fractions of POE in the solution phase are 0.302 and 0.333 for the two mixtures at the point of maximum synergism.     

α-Sulfonato palmitic acid methyl ester-hexaoxyethylene monododecyl ether mixed surfactant system: Interfacial,thermodynamic, and performance property study

Interfacial, thermodynamic, and performance properties of aqueous binary mixtures of α-sulfonato palmitic acid methyl ester, C₁₄H₂₉CH(SO₃Na)COOCH₃(PES), and hexaoxyethylene monododecyl ether, CH₃(CH₂)₁₁(OCH₂CH₂)₆OH (C₁₂E₆), were investigated with tensiometric, conductometric, fluorimetric, and viscometric techniques. The critical micelle concentration (CMC), maximum surface excess, minimum area per molecule of surfactant at the air/water interface, and the thermodynamics of micellization and adsorption were determined. The CMC was very low for mixed systems, indicating probable use as a detergent with less effect on the environment because of surfactant biodegradability and less amount in the environment. The interaction parameter β^m, computed by using the theory of Rubingh and Maeda, indicated an attractive interaction (synergism) between the surfactant molecules, which was also confirmed by proton nuclear magnetic resonance studies in the mixed micelle. The micellar aggregation number (N _agg), determined by using a steady-state fluorescence quenching method at a total surfactant concentration of about ∼10 mM at 25°C, was almost independent of the surfactant mixture composition. The micropolarity and the binding constant (K _sv) for the C₁₂E₆/PES mixed system were determined by the ratio of the intensities (I ₁/I ₃) of the pyrene fluorescence emission spectrum, and the local microenvironment inside the micelle was found to be polar. The viscosity of the mixed system at all mole fractions suggested that mixed micelles are nonspherical in nature. The cloud point of oxyethylene group-containing surfactants was increased by the addition of PES. Foaming was temperature dependent, and a 1∶1 mixed system showed minimum foaming. All performance properties were composition dependent.     

Determination of pK a Values of Oxocholanoic Acids by Potentiometric Titration

The pK _a and the maximum solubility values of cholic, deoxycholic salts and their oxo-derivatives have been measured by the method of potentiometric titration. In the monomer phase (under the critical micellar concentration, CMC), the bile salts have different pK _a values, as a result of their structural differences (the number of hydroxyl and oxo groups in the steroid skeleton) and different hydration properties of the acid anions. In the micellar phase (above the CMC), the bile salts have higher pK _a values than in the monomer phase (under the CMC). This increase in the pK _a values is greater in more hydrophobic bile salts (cholate and deoxycholate), than in less hydrophobic oxo derivatives, which can be explained by the different aggregation numbers of these bile salts. The oxo-derivatives are more likely to form dimeric micelles, where the carboxylic groups are situated on the two sides of the micelle, not causing any electrostatic repulsion. In the more hydrophobic bile salts, aggregation numbers are higher, which causes electrostatic repulsion of the nearby situated carboxylic anions and consequential protonation of these anions (which leads to the stabilization of the micelle). The maximum solubility values are higher for the oxo-derivatives. If the steroid skeleton of the bile salt is more hydrophobic, the capacity to solubilize the unionized bile acid is higher, i.e. a smaller amount of the bile acid anion is needed for the solubilization of the bile acid monomer. The oxo-derivatives are less hydrophobic, but alongside their hydrophobicity, the structure of the micelle determines the solubilization capacities.     

Aggregation Behavior of Perfluorononanoic Acid/Sodium Dodecyl Sulfate Mixtures

The mixed system of an anionic hydrocarbon surfactant, sodium dodecyl sulfate, and a perfluorinated surfactant, perfluorononanoic acid (PFNA), was investigated by a combination of methods. The critical micellar concentrations (CMC) were determined over a wide range of sample compositions by surface tension, conductivity and UV–visible spectrophotometry using N-(4-nitrophenyl)perfluorononanamide as a molecular probe. The values of CMC obtained by different techniques were in good agreement. In addition, the aggregation numbers were determined in the mixtures with a low content of hydrocarbon surfactant, by measuring the fluorescence quenching of pyrene. The hydrodynamic radii of the aggregates were estimated through the diffusion ordered ¹⁹F- and ¹H-NMR spectroscopy. The values obtained are in agreement with those expected according to the measured aggregation numbers. The analysis of the data with different aggregation models suggests the formation of a non-ideal mixed micelle that is enriched in the perfluorinated surfactant when its mole fraction increases, and that is practically formed by PFNA only at mole fractions higher than 0.8.     

Synthesis and surface-active properties of trimeric-type anionic surfactants derived from tris(2-aminoethyl)amine

Trimeric-type anionic surfactants (3C_ntaAm, where n is a hydrocarbon chain length of 8, 10, or 12) with three hydrocarbon chains and three carboxylate headgroups were synthesized from tris(2-aminoethyl)amine, and their properties were investigated by surface tension, electrical conductivity, dynamic and static light-scattering, fluorescence of pyrene, and emulsification power techniques. The critical micelle concentrations (CMC) of 3C_ntaAm were 0.00092–0.00834 mmol dm⁻³, and the surface tensions at the CMC were 33.3–39.9 mN m⁻¹. The areas per molecule occupied by 3C₁₀taAm and 3C₁₂taAm were extremely small, showing they were highly compact at the air/water interface. In addition, adsorption or micellization behavior of 3C_ntaAm was estimated by parameters such as pC ₂₀ (the efficiency of surface adsorption), CMC/C ₂₀ (the ease of adsorption relative to the ease of micellization), and ΔG _M ^o (Gibbs energy of micellization). Dynamic and static light-scattering mesurements of 3C_ntaAm showed a hydrodynamic radius of 45–61 nm above the CMC and aggregation numbers of 10–82 at the CMC, respectively. The fluorescence intensity ratio of the first to the third band in the emission spectra of pyrene started to lower from far above the CMC for 3C₈taAm and 3C₁₀taAm, and below the CMC for 3C₁₂taAm. This suggests that loose micelles or premicellar aggregates are formed in solutions. Mixtures of aqueous solutions of 3C_ntaAm and toluene formed oil-in-water-type emulsions, and the stabilizing abilities were in the order of 3C₈taAm>3C₁₀taAm>3C₁₂taAm. The degree of emulsification of 3C₈taAm remained at 69% after 24 h of standing. Thus, 3C_ntaAm exhibited unique properties superior to monomeric or dimeric surfactants that were significantly influenced by their hydrocarbon chain lengths.     

Mixed Micellization and Interfacial Properties of Ionic Liquid‐Type Imidazolium Gemini Surfactant with Amphiphilic Drug Amitriptyline Hydrochloride and its Thermodynamics

The thermodynamics of mixed micellization of amitriptyline hydrochloride (AMT) with ionic liquid‐type imidazolium gemini surfactant ([C₁₀‐4‐C₁₀im] Br₂), was investigated at different mole fractions and temperatures by surface tension measurements. The deviation of the critical micelle concentration (CMC) from the ideal critical micelle concentration (CMC * ), micellar mole fraction () from ideal micellar mole fraction (), the values of interaction parameter () and activity coefficients () (for both mixed micelles and mixed monolayer) explained the non‐ideal behavior (i.e., synergistic behavior) of binary mixtures. The excess free energy (?G_ex) for the AMT‐[C₁₀‐4‐C₁₀im] Br₂ binary mixtures explained the mixed micelles stability in comparison to micelles of [C₁₀‐4‐C₁₀im] Br₂ and pure AMT. Interfacial parameters, i.e., Gibbs surface excess (), minimum head group area at air/water interface (), free energy of micellization (), and standard Gibbs energy of adsorption (?G_ads^o) were also evaluated for the systems. The standard entropy of adsorption (?S_ads^o) was found higher than the standard entropy of micellization (?S_m^o) at all mole fractions of AMT (α₁).     

Conductometric Probe Analysis of the Effect of Benzyldimethylhexadecylammonium Chloride on the Micellization Behavior of Dodecyltrimethylammonium Bromide in Aqueous/Urea Solution: Investigation of Concentration and Temperature Effect

Surfactant mixtures are used in many different industrial formulations. In this study, the mixed micelle formation behavior of 2 different cationic surfactants, namely dodecyltrimethylammonium bromide (DTAB) and benzyldimethylhexadecylammonium chloride (BDHAC), in the absence and presence of urea at various temperatures (298.15–318.15 K) was studied using the conductometric method. The attractive interaction between DTAB and BDHAC was estimated from the values of critical micelle concentration (CMC) and the CMC for ideal mixing (CMC^id). Urea increases the CMC value as a result of the enrichment in the surface charge of the micelles/mixed micelles. The values of micellar mole fraction (X₁^Rub [Rubingh], X₁^M [Motomura], X₁^Rod [Rodenas]) and ideal micellar (X₁^id) of surfactant BDHAC were obtained by different models and are shown to exhibit the high contribution or effective involvement of BDHAC in mixed micelles and increase with increasing BDHAC mole fraction (α₁). Activity coefficients (f₁ and f₂) were also evaluated from the relevant formula given in the literature. The negative values of the interaction parameters (β) show the attractive interaction among the studied components. Excess Gibbs free energy (?G_ex) of micellization revealed that the stability of mixed micelles is higher in aqueous solution than in urea solution. The thermodynamic parameters, namely the Gibbs free energy change, enthalpy change, and entropy change (?G^o_m, ΔH^o_m, and ?S^o_m, respectively), were also calculated from the conventional standard equations.     

Solution properties of mixed surfactant system sodium dodecyl sulfate and alkyl polyoxyethylene ether system

The effect of oxyethylene groups in a nonionic surfactant on the solution properties of anionicnonionic systems is described; these systems are sodium dodecyl sulfate (SDS)—hexadecyl polyoxyethylene ethers (C₁₆POE_n, where n=10, 20, 30 and 40). The degree of ionic dissociation of the mixed micelles decreases with increasing numbers of oxyethylene groups in the nonionic surfactant. As polyoxyethylene chain lengths increase, the electrical conductivities of the mixed surfactant solutions decrease, in spite of the decrease in activation energy for conduction. The radius of the mixed micelle with the electric double layer is larger for a nonionic surfactant having a shorter polyoxyethylene chain length than for one having a long polyoxyethylene chain. This may be attributed to the fact that the mixed micelle is formed more easily by a nonionic surfactant with a shorter polyoxyethylene chain length than by one with a longer chain.     

An octaethylene glycol monododecyl ether-based mixed micellar assay for determining the lipid acyl hydrolase activity of patatin

Patatin was extracted from potato tubers (Solanum tuberosum L. cv. Spunta) and purified to homogeneity by ammonium sulfate salt fractionation and one sole chromatographic step. A spectrophotometric mixed micellar assay for patatin lipid acyl hydrolase (LAH) activity was designed with the detergent octaethylene glycol monododecyl ether (C₁₂E₈). Patatin LAH used p-nitrophenyl butyrate (PNP-butyrate) as substrate when solubilized in (C₁₂E₈) micelles. In the mixed micellar system, patatin LAH responds to the PNP-butyrate surface concentration expressed as mol% (=[PNP-butyrate]·100/([detergent]-critical micellar concentration)) and not to the molarity of PNP-butyrate. The kinetic parameters were determinined; V _max was independent of the mixed micelle concentration, as was K _m, when expressed as mol%. However, K _m was dependent on C₁₂E₈ concentration when expressed in molar concentration. C₁₂E₈/PNP-butyrate proved to be a reliable system for assaying patatin LAH activity and is superior to the commonly used Triton X-100 and SDS methods. It permits investigation of the substrate requirements of patatin LAH activity because the concentration-independent K _m can be determined both in mol% and as the absolute number of substrate molecules per micelle. In addition, the detergent did not affect the enzyme activity.     

Adsorption Behavior of Fatty Alcohol Ether Sulfonate at Different Interfaces

The equilibrium surface tension, dynamic surface tension, and interfacial tension (IFT) of fatty alcohol ether sulfonates (C_mE_nSO) were measured to investigate their adsorption behavior. The effect of NaCl and CaCl₂ concentrations on the IFT was also studied. The results showed that the number of EO units has no significant effect on the critical micelle concentration (CMC) and CMC decreases with increasing the length of the hydrophobic group. The surface tension at the CMC increases with the increase of the number of EO units and the length of the hydrophobic group. At dilute surfactant concentration, the adsorption process for C_mE_nSO is controlled by diffusion; at higher concentration, it becomes a mixed diffusion‐kinetic adsorption mechanism. The IFT between C_mE_nSO solution and dodecane remains around 10^?1 mN/m over a wide range of electrolyte concentrations (NaCl concentration from 25 to 210 g/L, CaCl₂ concentration from 0.1 to 10 g/L).     

Precipitation in solutions containing mixtures of synthetic anionic surfactant and soap. I. Effect of sodium octanoate on hardness tolerance of sodium dodecyl sulfate

The effect of sodium octanoate (SO) and pH on the precipitation of sodium dodecyl sulfate (SDS) with calcium (hardness tolerance) in water was investigated. SO can exist as octanoate anion (O⁻) or as the protonated nonionic fatty acid (HO) with the HO/O⁻ ratio increasing with decreasing pH. At intermediate pH levels, SO or SO/SDS systems are composed of mixtures of anionic and nonionic surfactants, resulting in enhancement of micelle formation due to nonideal mixed micelle formation. Above the critical micelle concentration (CMC), the highest hardness tolerance at each pH level occurs at a mole ratio of 80∶20 SDS/SO due to synergism in the SDS/SO mixtures. This synergism also results in an increase in hardness tolerance of SDS with decreasing pH above the CMC.     

Mixed Micellar Properties and Related Interaction Parameters of Butanediyl-1,4-bis(dodecyl dimethyl ammonium bromide) Gemini Surfactant with Nonionic Amphiphiles

Mixed micellization of cationic gemini surfactant butanediyl-1,4-bis(dimethyldodecylammonium bromide) with nonionic surfactants (sorbitan esters, alcohols and phenol ethoxylates) and triblock copolymers has been studied tensiometrically. Various physicochemical parameters of the studied systems including ideal CMC values, experimental and ideal micellar compositions, interaction parameters, activity coefficients of the components, etc. have been evaluated by considering theoretical models of Clint, Rubingh, Rosen and Maeda. The experimental critical micelle concentration (CMC) values of the mixed micelles were lower than the CMC values of the individual components and showed a negative deviation from ideal CMC (CMC*) values. The analysis reveals that the mole fractions of gemini are lower compared to the nonionic surfactants/triblock polymers and the values of ΔG _m ^° , ΔG _ad ^° , G _min and ΔG _ex ^m show that the spontaneity of the studied mixed micelles relatively decreases as the content of the gemini in the bulk phase increases.     

Mixed Micellization and Mixed Monolayer Formation of Sodium Cholate and Sodium Deoxycholate in Presence of Hydrophobic Salts Under Physiological Conditions

Mixed micellization and mixed monolayer formation of two bile salts namely sodium cholate (NaC) and sodium deoxycholate (NaDC), in the presence of sodium chloride (NaCl) and three hydrophobic salts including sodium acetate (NaAc), sodium butanoate (NaBu) and sodium hexanoate (NaHx) in 10 mM phosphate buffer (pH 6.5) at 37 °C were investigated by means of surface tension measurements. The experimental results were utilized to evaluate various parameters like critical micellar concentration (CMC), micellar and monolayer interaction parameter (β and β ^σ), micellar and monolayer mole fractions (X and Z), activity coefficients of two bile salts in mixed micelles and monolayer (f and f _(σ)), surface excess (Γ_max) and minimum surface area per molecule of bile salt (A _min). Mixed micelles and mixed monolayer were found to show slight non-ideality and both these phenomena have been found to be affected differently in the presence of various additive salts with NaHx showing larger effects. Higher efficiency of NaHx in affecting both phenomena has been attributed to its appreciable hydrophobicity and surface activity, thus showing stronger interactions with bile salt molecules.     

Solubilization of carotenoids from carrot juice and spinach in lipid phases: II. Modeling the duodenal environment

We have been investigating the factors determining the bioavailability of carotenoids from vegetables. The previous paper [Rich, G.T., Bailey, A.L., Faulks, R.M., Parker, M.L., Wickham, M.S.J., and Fillery-Travis, A. (2003) Solubilization of Carotenoids from Carrot Juice and Spinach in Lipid Phases: I. Modeling the Gastric Lumen, Lipids 38, 933–945] modeled the gastric lumen and studied the solubilization pathway of carotenes and lutein from carrot juice and homogenized spinach to oil. Using the same vegetable preparations, we have extended our investigations to solubilization pathways potentially available in the duodenum and looked at the ease of solubilization of carotenes and lutein within simplified lipid micellar and oil phases present within the duodenum during digestion. Micellar solubility of raw spinach carotenoids was low and was enhanced by freezing, which involved a blanching step. The efficiency of solubilization of carotenoids in glycodeoxycholate micelles decreased in the order lutein_carrot>lutein_{blanched-frozen spinach}>carotene_{blanched-frozen spinach}>carotene_carrot. Frozen spinach carotenoids were less soluble in simple micelles of taurocholate than of glycodeoxycholate. The results comparing the solubility of the carotenoids in mixed micelles (bile salt with lecithin) with simple bile salt micelles are explained by the relative stability of the carotenoid in the organelle compared to that in the micelle. The latter is largely determined by the polarity of the micelle. Below their critical micelle concentration (CMC), bile salts inhibit transfer of carotenoids from tissue to a lipid oil phase. Above their CMC, the bile salts that solubilize a carotenoid can provide an additional route to the oil from the tissue for that carotenoid by virtue of the equilibrium between micellar phases and the interfacial pathway. Mixed micellar phases inhibit transfer of both carotenoids from the tissue to the oil phase, thereby minimizing this futile pathway.     

Physico-Chemical Investigations of Mixed Micelles of Cationic Gemini and Conventional Surfactants: a Conductometric Study

The interaction of cationic gemini and cationic conventional surfactants by conductivity was systematically overviewed, paying attention to synergism observed in micellization. These mixed systems were found to show remarkable synergism in micelle formation. The experimental critical micelle concentration values being lower than the value predicted by ideal solution theory indicate that the mixed micellization is due to attractive interaction between the two components. Gemini/conventional systems form mixed micelle due to attractive interactions (negative β values). The values of micellar mole fraction of constituent 1 (X ₁) in surfactant mixtures are more than in the ideal state (X ₁ ^ideal ), which means that, the mixed micelles are rich in conventional surfactants in comparison to that in the ideal state.     

Aggregation of unsaturated long-chain fatty alcohols in nonaqueous systems

Aggregation and related phenomena in nonaqueous binary and ternary solutions containing unsaturated long-chain fatty alcohol amphiphiles have been studied. Six C₁₈ fatty alcohols were studied—oleyl alcohol (9Z-octadecen-1-ol), elaidyl alcohol (9E-octadecen-1-ol), linoleyl alcohol (9Z, 12Z-octadecadien-1-ol), elaidolinoleyl alcohol (9E, 12E-octadecadien-1-ol), linolenyl alcohol (9Z, 12Z, 15Z-octadecatrien-1-ol) and elaidolinolenyl alcohol (9E, 12E, 15E-octadecatrien-1-ol). Equivalent conductivity and photon correlation spectroscopy confirmed that unsaturated long-chain fatty alcohols form large and polydisperse aggregates in methanol. Critical micelle concentration (CMC) results showed that the degree of unsaturation and configuration of the double bonds in the fatty alcohol significantly influences aggregation. Aggregation of oleyl alcohol in a series of straight and branched medium-chainlength (C₃-C₈) alkanol solvents was studied. For shorter-chained alkanols (C₁-C₄), decreasing solvent dielectric constant decreases the CMC; however, for longer-chained alkanols (C₄-C₈), no significant effects occurred on the CMC. The effect of solubilized soybean oil on the viscosity of long-chain fatty alcohol/methanol solutions was also analyzed. Relative viscosity results were consistent with those expected for microemulsions. Although preliminary in nature, these results generally support the notion that soybean oil is solubilized by incorporation into large soybean oil-in-fatty alcohol aggregates in methanol solvent, resembling a nonaqueous detergentless microemulsion. Presented at the 67th Colloid and Surface Science Symposium, Toronto, Canada, June 20–23, 1993.     

Mixed micelles of hexadecylpyridinium bromide + tetradecyltrimethylammonium bromide in aqueous glycol oligomers

Conductances of hexadecylpyridinium bromide (HPyBr) + tetradecyltrimethylammonium bromide (TTAB) mixtures over the entire mole fraction range of HPyBr (α_HPyBr) were measured in pure water as well as in the presence of various aqueous ethylene glycol oligomers containing 10 and 30 wt% of each additive in their respective binary mixtures at 30°C. Each conductivity curve shows two breaks corresponding to two critical micelle concentrations (cmc; C₁ and C₂ over the whole mole fraction range of HPyBr + TTAB mixtures except in the presence of pure HPyBr and TTAB, where a single break was observed. From the conductivity data, various micellar paramelers in the absence and presence of glycol additives were computed. A variation in the micellar parameters in the presence of additive showed that additive introduction mainly influence the medium properties and therefore the micellar properties. However, no significant micelle-glycol interactions were observed even with an increase in the number of repeating units from ethylene glycol to polyethylene glycol 600. The mixing behavior of HPyBr + TTAB is close to nonideal and is identical in pure water and in the presence of various glycols. This has been attributed to the presence of synergistic interactions between unlike monomers at C₁ that are not influenced even by the presence of additives. The appearance of the second cmc is mainly attributed to structural transitions of the mixed micelles at C₁ with a further increase in surfactant concentration.