Mixed Micellar and Interfacial Interactions of a Triblock Polymer (EO37PO56EO37) with a Series of Monomeric and Dimeric Surfactants

The mixed micellar and interfacial properties of mixtures of triblock polymer (TBP) with a series of monomeric (dodecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, and cetyltrimethylammonium bromide, and dimeric (dimethylene bis[alkyldimethylammonium bromide], m-2-m, where m = 10, 12, and 14) cationic surfactants were investigated using surface tension and viscosity measurements in aqueous solutions at different temperatures. Various physicochemical properties such as critical micelle concentration, mixed micellar mole fraction, interaction parameter, interfacial, and thermodynamic parameters were evaluated. All the binary mixtures exhibit synergistic interactions which increase with temperature and pass through a minimum with the increase in hydrophobic chain length of the cationic surfactants. The contribution of TBP in mixed micelle formation also increases with the hydrophobic chain length of the surfactants. The interfacial and thermodynamic parameters reveal that the adsorption of the surfactant mixtures at the air–solution interface is more favorable than that of micelle formation and the unfavorable enthalpy changes are overwhelmed by favorable entropy changes. Further, the mixtures of TBP with smaller chain length surfactants show a sharp rise in relative viscosity at higher mole fractions of these surfactants.     

Synthesis and Surface Active Properties of Gemini Cationic Surfactants and Interaction with Anionic Azo Dye (AR52)

A homologous series of new gemini cationic surfactants were synthesized and characterized using micro elemental analysis, FTIR, ¹H-NMR and mass spectra. The surface activities of these amphiphiles were determined based on the data of surface tension. Critical micelle concentration, effectiveness of the surface tension reduction, efficiency of adsorption, maximum surface excess, minimum surface area and critical packing parameter were evaluated. The effect of cationic micelles on solubilization of anionic azo dye, sulforhodamine B (Acid Red 52) in aqueous micellar solution of the synthesized gemini cationic surfactants was studied at pH 6.9 ± 0.5 and 25 °C. The results showed that the solubility of dye rose with increasing surfactant concentration as a consequence of some association between the dye and the micelles. It was also observed that the aggregation of surfactant and dye takes place at a surfactant concentration below the CMC of the individual surfactant. The partition coefficients between the bulk water and surfactant micelles as well as the Gibbs energies of distribution of dye between the bulk water and surfactant micelles were calculated using a pseudo-phase model. The effect of the hydrophobic chain length of Gemini cationic surfactants on the distribution parameters was also reported. The results show favorable solubilization of dye in cationic micelles.     

The study of Sunset Yellow anionic dye interaction with gemini and conventional cationic surfactants in aqueous solution

In the present study, the interaction of an anionic azo dye, Sunset Yellow, with two cationic gemini surfactants with different spacer lengths (s = 3, 6 methylene groups) and their monomeric counterpart, dodecyl trimethyl ammonium bromide (DTAB), was investigated by surface tension, UV–Vis spectroscopy, and zeta potential measurements. The critical micelle concentration (CMC) was determined from plots of the surface tension (γ) as a function of the logarithm of total surfactant concentration. Moreover, the values of binding constants (K_b) of dye-surfactant complexes were calculated by UV–Vis spectroscopy. The UV–Vis spectra showed that the dye–surfactant interaction occurred in the solution at concentrations far below the CMC of each surfactant. The gemini surfactant with a shorter spacer showed stronger interaction with dye in comparison to DTAB and the gemini with longer spacer. The effect of surfactant chemical structure on solubilization of dye-surfactant aggregates at surfactant concentration above CMC was investigated by zeta potential.     

Physicochemical investigation and spectral properties of Sunset Yellow dye in cetyltrimethylammonium bromide micellar solution under different pH conditions

To mimic binding to biological membranes, the extent of interaction of the efficient food dye Sunset Yellow with a cationic surfactant, cetyltrimethylammonium bromide, was probed by quantifying its absorption and fluorescence emission spectra as a function of premicellar to post‐micellar surfactant concentration. The characteristics of the partition behaviour and spectral‐luminescent properties of Sunset Yellow–surfactant have been evaluated qualitatively as well as quantitatively for various cetyltrimethylammonium bromide concentrations. With the help of mathematical models, the water–micelle partition coefficient, the Sunset Yellow–cetyltrimethylammonium bromide binding constant, the binding capacity, and the degree of counterion binding were calculated at 25 °C under various pH conditions. The solubilisation of Sunset Yellow is also discussed from the thermodynamics viewpoint by considering the standard free energy change of dye solubilisation and the Sunset Yellow–cetyltrimethylammonium bromide binding energy. The high values of all these interactions indicate that the dye, being organic in nature, is partitioned largely from the aqueous environment to the palisade layer of the micelle. The solubilisation of the dye is enhanced by switching the pH to suppress the self‐aggregation of dye molecules. Combined with electrostatic forces, the hydrophobic interactions also play a promising role in the solubilisation of Sunset Yellow in the outer core of the micellar interior.     

Spectroscopic Investigation of the Interaction of BSA with Cationic Surfactants

The interactions between dodecyltrimethylammonium bromide (DTAB), tetradecyltrimethylammonium bromide (TTAB), cetyltrimethylammonium bromide (CTAB), and hexadecylpyridinium chloride (HDPC) with bovine serum albumin (BSA) in an aqueous solution (pH = 7.0, 0.001 M HEPES buffer) were studied by fluorescence and circular dichroism (CD) measurements. These categories of surfactants were used to elucidate the effect of hydrophilic group and length of hydrophobic chain surfactant on the mechanism of binding to BSA. The result revealed that for all surfactants, at low concentrations, the Stern‐Volmer plots have an upward curvature and in high concentrations, the quenching efficiency was decreased with increase in surfactant concentration. The activation energy of the interaction between cationic surfactants and BSA was measured. The results of CD show that the conformation of BSA has been changed in the presence of cationic surfactants.     

Wetting and adsorption properties of cetyltrimethylammonium bromide and Triton X-100 mixture with short-chain alcohol in polymer–solution–air system

Measurements of the contact angle of the aqueous solutions of Triton X-100 (TX-100) and cetyltrimethylammonium bromide (CTAB) mixture with methanol or propanol on the polytetrafluoroethylene (PTFE) and nylon-6 surfaces were made. On the basis of the obtained results, the Gibbs surface excess concentration of alcohol and TX-100 + CTAB mixture at the polymer–solution and polymer–air interfaces was calculated and compared to that at the solution–air one. The standard Gibbs free energy of alcohol adsorption was determined by different methods. For TX-100 and CTAB mixture, this energy was calculated using the values of critical micelle concentration (CMC) of that mixture, the surface tension and contact angle of aqueous solution of alcohol as well as the surface tension and contact angle of the aqueous solution of TX-100 and CTAB mixture with alcohol at CMC. The polymer–solution interfacial tension, the adhesion tension, and the adhesion work of the studied solutions to the polymer surface were also determined. From the obtained data, it results that the studied solutions can wet completely only the nylon-6 surface and that below alcohol critical aggregation concentration the adsorption of surfactants and alcohols at the polymer–water and water–air interfaces is similar for PTFE and different for nylon-6.     

二元表面活性剂体系微乳液的相行为及热力学研究

用表面张力法研究了苯乙烯基酚聚氧乙烯聚氧丙烯醚嵌段型非离子表面活性剂(PEP)分别与十二烷基硫酸钠(SDS)、十二烷基三甲基溴化铵(CTAB)复配体系分子间的相互作用,并根据测定的临界胶束浓度(CMC)及正规溶液理论计算了复配体系分子间相互作用参数及分子交换能,考察了表面活性剂、助表面活性剂、温度等因素对复配表面活性剂体系微乳液形成过程的相行为及热力学性质的影响。结果表明,二元组分(PEP+SDS)及(PEP+CTAB)复配体系在胶束中和表面吸附层中的都存在较强的增效作用,体系的能量降低,且前者的增效作用大于后者。(PEP+SDS)/正己醇/正庚烷/水微乳液的W/O微乳区域面积最大,温度对该微乳液的相行为影响很小。在此微乳液形成的过程中,助表面活性剂醇从连续油相进入微乳液界面层的标准自由能变化ΔGs0;标准焓变-ΔHs=0,为无热效应过程,ΔGs是由醇分子的混乱度熵变ΔSs决定的。     

Interaction of Azo Dye with Cationic Surfactant Under Different pH Conditions

The aggregation induced by Alizarin Yellow R (AYR) in the cationic surfactant, cetyltrimethylammonium bromide (CTAB), was investigated by measuring their UV–visible absorption spectra. Conductance measurements as a function of surfactant concentration below and above the critical micelle concentration (CMC) were studied. CTAB aggregation takes place at the concentration far below its normal CMC in the presence of AYR. Both hydrophobic and electrostatic interactions affect the aggregation process in aqueous solution. The dye effect on the CMC of CTAB was noted by a specific conductivity method as well. AYR–CTAB binding constant (K_s) and water–micelle partition co-efficient (K_x) were quantified with the help of mathematical models employed to determine the partitioning of organic additives in the micellar phase. The number of dye molecules per micelle was estimated at particular CTAB concentrations above CMC, during this study.     

Micellization Behavior of Cationic Gemini Surfactants in Aqueous-Ethylene Glycol Solution

The micellization behavior of gemini surfactants i.e. alkanediyl-α,ω-bis(cetyldimethylammonium bromide) (C₁₆-s-C₁₆,2Br⁻ where s = 3, 4, 10) in 10% (v/v) ethylene glycol solution was investigated by surface tension and conductometric measurements at 300 K. The critical micelle concentration, degree of micellar ionization, surface excess concentration, minimum surface area per molecule of surfactant, surface pressure at the CMC and Gibbs energy of adsorption of the dimeric surfactants have also been determined in the presence of different salts (NaCl, NaBr and NaI). The critical micelle concentration and degree of micellar ionization values decrease significantly in the presence of sodium halides and follows the sequence NaCl < NaBr < NaI. The free energy, enthalpy and entropy of micellization of dimeric surfactants in 10% (v/v) ethylene glycol solution were determined using the temperature dependence of the critical micelle concentration. The standard free energy of micellization was found to be negative in all the cases.     

On the measurement of critical micelle concentrations of pure and technical-grade nonionic surfactants

The critical micelle concentrations (CMC) of nine commercial nonionic surfactants (Tween 20, 22, 40, 60, and 80; Triton X-100; Brij 35, 58, and 78) and two pure nonionics [C₁₂(EO)₅ and C₁₂(EO)₈] were determined by surface tension and dye micellization methods. Commercially available nonionic surfactants (technical grade) usually contain impurities and have a broad molecular weight distribution owing to the degree of ethoxylation. It was shown that the surface tension method (Wilhelmy plate) is very sensitive to the presence of impurities. Much lower CMC values were obtained with the surface tension method than with the dye micellization method (up to 6.5 times for Tween 22). In the presence of highly surfaceactive impurities, the air/liquid interface is already saturated at concentrations well below the true CMC, leading to a wrong interpretation of the break in the curve of surface tension (γ) vs. concentration of nonionic surfactant (log C). The actual onset of micellization happens at higher concentrations, as measured by the dye micellization method. Furthermore, it was shown that when a commercial surfactant sample (Tween 20) is subjected to foam fractionation, thereby removing species with higher surface activity, the sample yields almost the same CMC values as measured by surface tension and dye micellization methods. It was found that for monodisperse pure nonionic surfactants, both CMC determination methods yield the same results. Therefore, this study indicates that precaution should be taken when determining the CMC of commercial nonionic surfactants by the surface tension method, as it indicates the surface concentration of all surface-active species at the surface only, whereas the dye method indicates the presence of micelles in the bulk solution.     

Properties of aqueous solution of a fluorocarbon surfactant and a nonionic surfactant,and their mixtures

The surface tensions of aqueous solutions of lithium perfluorooctane sulfonate (LiFOS) and hexaethyleneglycoln-dodecylether (6ED), and of their mixtures, were measured. The effect of each surfactant additives on the adsorption and the micelle formation was discussed on the basis of the surface tension values using the Langmuir adsorption equation for the mixture of both surfactants and the modified Szyszkowski equation. From these results, in the range of low concentrations of 6ED or LiFOS, some of the 6ED molecules which had already adsorbed on the solution surface were found to be replaced by LiFOS molecules in an addition of LiFOS surfactant and vice-versa. In the ranges of higher concentration above critical micelle concentration (CMC) of each surfactant, it was concluded that the mixed micelle could be formed in the mixed system of both surfactants as well as in the mixed system of two kinds of ordinary hydrocarbon surfactants.     

Interaction of Phenol Red with cetyltrimethylammonium bromide in aqueous solution

This paper studies the interaction of anionic dye Phenol Red with cationic surfactant cetyltrimethylammonium bromide in aqueous solution and its influence on the formation of cetyltrimethylammonium bromide micelles for the first time. We obtain a series of thermodynamic parameters of the interaction by establishing a reasonable physical model of the association. Moreover, an in‐depth study on the variation in the absorption spectrum finds that the value of absorbance at the maximum absorption peak changes regularly with increase in the cetyltrimethylammonium bromide concentration. By establishing the micellisation models and measuring the changes in electrical conductivity with different cetyltrimethylammonium bromide concentrations, the critical micelle concentration values are obtained, which are essentially the same as the range of concentrations of regular change in absorbance, which shows that the formation of the cetyltrimethylammonium bromide micelles have an impact on the association interaction between Phenol Red and cetyltrimethylammonium bromide. All these data and phenomena illustrate a strong interaction between Phenol Red and cetyltrimethylammonium bromide.     

Solubilisation study of water‐insoluble dye in cationic single/dimeric surfactant micelles: effect of headgroup,non‐polar tail,and spacer chain in aqueous and salt solution

The solubilisation of hydrophobic azo dye Orange OT in aqueous/salt solution in several cationic surfactant micelles was studied using UV‐vis spectroscopy. An attempt was made to correlate dye solubilising strength with adsorption/micellar characteristics. In our experiments we determined the change in solubilisation of hydrophobic dye when added to an aqueous solution of oppositely charged quaternary‐salt‐based cationic surfactants (conventional and gemini) and remarked on the probable location of the solubilised dye in the surfactant micelle. Results highlight the onset of dye solubilisation around the critical micelle concentration of each surfactant, which is influenced by the non‐polar tail, spacer, and polar headgroup, while no dye could be solubilised at concentrations below the critical micelle concentration. Orange OT solubilised almost linearly with increase in surfactant concentration at and above the critical micelle concentration. The change in colour intensity of the dye (darker below the critical micelle concentration, lighter at and above the critical micelle concentration) could be attributed to dye–surfactant interactions. Further dye solubilisation was observed in the presence of salt.     

Ein Beitrag zur Messung der kritischen Micellkonzentration in nichtwäßrigen Lösungsmitteln

A Contribution on the Measurement of Critical Micelle Concentration in Non-Aqueous Solvents According to the known concepts, many surfactants form micelles even in organic solvents. A simple method for the determination of critical micelle concentration is based on the fact that dyes, when held in surfactant micelles, exhibit colour changes which can be measured conveniently by photometry. The critical micelle concentration of lauryl alcoholpolyglycolether(7) in dioxane, benzene, 1,2,4-trichlorobenzene and in carbon tetrachloride is in the region of 200-250 mg/l. The observed values are independent of the nature of dye (iodine, fluorescein and eosine). Traces of water increase the value. In aqueous solutions of surfactants the method based on the measurement of surface tension and the method employing a dye yield comparable values of critical micelle concentration which are in the region of 50 mg/l.     

Interactions of Polyacrylamide with Cationic Surfactants: Thermodynamic and Surface Parameters

The aggregation behaviour of two cationic surfactants, viz. cetyl trimethyl ammonium bromide (CTAB) and N-cetyl pyridinium chloride (CPC), in different concentrations of water-soluble polyacrylamide has been studied in alkaline medium by electrical conductivity and surface tension measurements. A decrease in the critical micelle concentration (CMC) of the surfactant with an increase in polymer content in the mixture was observed. The thermodynamic and surface parameters have been determined and discussed. The results indicate that micellisation becomes more favourable at higher polymer content.     

The Tail Effect of Some Prepared Cationic Surfactants on Silver Nanoparticle Preparation and Their Surface,Thermodynamic Parameters,and Antimicrobial Activity

The surface parameters of some cationic surfactants having different hydrophobic alkyl chains were assessed in aqueous solution using different techniques; surface tension, ultraviolet-Visible (UV–Vis) spectroscopy, and conductivity measurements. The obtained critical micelle concentration (CMC) for N-(2-((3,4-dimethoxybenzylidene)amino)ethyl)-N,N-dimethyloctan-1-aminium bromide (DBAO), N-(2-((3,4-dimethoxybenzylidene)amino)ethyl)-N,N-dimethyldodectan-1-aminium bromide (DBAD), and N-(2-((3,4-dimethoxybenzylidene)amino)ethyl)-N,N-dimethylhexadectan-1-aminium bromide (DBAH) in aqueous solution using three techniques are nearly the same. Increasing the hydrophobic chain length enhances micelle formation. Raising the solution temperature from 25 to 65 °C also shows the same trend. The thermodynamic calculations outlined the adsorption propensity of the surfactants at the surface compared to their affinity to form micelles. Both micellization and adsorption processes are enhanced with both the hydrocarbon elongation and with raising the solution temperature. The effect of the surfactant tail on the preparation process of the silver nanoparticles (AgNP) was assessed and confirmed using transmission electron microscope (TEM), dynamic light scattering (DLS), and UV–Vis spectra. Increasing the surfactant tail leads to a smaller particle size with a narrow distribution. The stability of the prepared AgNP is enhanced with hydrophobic surfactant tail elongation as proved with increasing the zeta-potential of the prepared AgNP colloid. The foaming power, interfacial tension, and emulsification stability of the DBAO, DBAD, and DBAH surfactants were determined. The DBAO, DBAD, and DBAH surfactants showed good antimicrobial activities against both bacteria (Gram positive and negative) and fungi, which have been enhanced because of incorporation of AgNP.     

Synthesis,interfacial properties,and antimicrobial activity of a new cationic gemini surfactant

Tetramethylene-1,4-bis(N,N-dodecylammonium bromide), cationic gemini surfactant, (12-4-12) was first synthesized with an one-step and shortened procedure and its interfacial and antimicrobial properties were compared with a conventional single-chain cationic surfactant, cetyltrimethylammonium bromide (CTAB). The interfacial and thermodynamic properties of both surfactants reveal that critical micelle concentration (CMC) of this novel synthetic cationic dimeric surfactant is lower than that of cationic monomeric surfactant at almost 15 times of its magnitude, which is due to the increase in hydrophobicity of the surfactant molecules by having dual hydrocarbon chains. In comparison with CTAB, the produced compound 12-4-12 yields much better interfacial and thermodynamic properties. The antimicrobial activities of the synthesized gemini surfactant were tested against eight strains of bacteria, as well as two strains of fungi. The results showed that both 12-4-12 compound and CTAB exhibited higher inhibitory effects on the growth of Gram-positive bacteria and fungi than that of Gram-negative bacteria. The minimum inhibitory concentrations in molar of 12-4-12 against all tested Gram-negative bacteria were lower than those of CTAB, which is hypothetically due to the lower HLB together with smaller CMC values of our gemini surfactant.     

Influence of Spacer Nature on the Aggregation Properties of Anionic Gemini Surfactants in Aqueous Solutions

A series of anionic gemini surfactants with the same structure except the spacer nature have been studied. Their solution properties were characterized by the equilibrium surface tension and intrinsic fluorescence quenching method. The critical micelle concentrations (CMC), surface tension at cmc, C₂₀, and the micelle aggregation number (N) were obtained. The surface tension measurements indicate that these gemini surfactants have much lower cmc values and great efficiency in lowering the surface tension of water compared with those of conventional monomeric surfactants. Furthermore, the standard free energy of micellization for anionic gemini surfactants was also determined. The results showed that the nature of the spacer has an important effect on the aggregation properties of gemini surfactants in aqueous solutions. The surfactant with a hydrophilic, flexible spacer was more readily able to form micelle compared with the surfactant with a hydrophobic, rigid spacer, which leads to a lower CMC value, larger N, more negative free energy of micellization, and a more closely packed micelle structure.     

Micellar Extraction of Zinc with Di(2‐ethylhexyl)phosphoric Acid and the Addition of the Cationic Surfactant Cetyltrimethylammonium Bromide

The addition of surfactants can influence extraction processes. In cases where the surfactant concentration is above the critical micelle concentration, the mass transfer rate increases due to the formation of inverse micelles and, thus, through the mechanism of micellar extraction of zinc. The influence of the added surfactant cetyltrimethylammonium bromide on zinc extraction with the cation exchanger di(2‐ethylhexyl)phosphoric acid was analyzed based on extraction equilibrium and mass transfer experiments. The observed experimental results are explained phenomenologically.     

Natural dye–surfactant interactions: thermodynamic and surface parameters

The interaction of two Indian natural dyes, namely madder (Rubia cordifolia) and mallow (Punica granatum), with cationic surfactant cetyl trimethyl ammonium bromide and anionic surfactant sodium lauryl sulphate, has been studied. Spectrophotometric data showed a strong interaction between the natural dyes and the surfactants. The critical micelle concentration of the surfactants, determined by measurement of specific conductance and surface tension, was found to decrease on the addition of natural dyes in an aqueous solution of surfactants. The thermodynamic and surface parameters for the interaction have been evaluated.