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.     

Effect of tartrazine dye on micellisation of cationic surfactants: conductometric,spectrophotometric, and tensiometric studies

The interactions between anionic dye (tartrazine) and cationic surfactants (dodecyltrimethylammonium bromide and cetyltrimethylammonium bromide) have been studied by conductometric, spectrophotometric, and tensiometric techniques. The conductance and surface tension of dodecyltrimethylammonium bromide and cetyltrimethylammonium bromide in pure water as well as in aqueous tartrazine when plotted with surfactant concentration gave values of the critical micelle concentration at different temperatures. As well as increasing the length of the carbon chain of surfactants, the presence of tartrazine reduces the critical micelle concentration. From specific conductivity data, the counterion dissociation constant, standard free energy, enthalpy, entropy of micellisation, surface excess concentration, surface tension at critical micelle concentration, minimum area per molecule, surface pressure at critical micelle concentration, and Gibbs energy of adsorption were evaluated. Spectroscopic studies reveal that the binding of dye to micelles brings a bathochromic shift in dye absorption spectra that indicates dye–surfactant interaction.     

Solubilisation of dyes by surfactant micelles. Part 3; A spectroscopic study of azo dyes in surfactant solutions†

A spectroscopic study (UV–vis and adsorption) has been made of the interactions of select model azo dyes with a range of surfactant types or their mixtures both above and below their respective critical micelle concentrations. All surfactants inhibit adsorption of the dyes to cotton above their critical micelle concentrations due to incorporation in micelles. However, formation of 1;1 complexes between dyes and cationic or zwitterionic surfactants in sub‐micellar regions results in enhanced deposition on cotton. It is shown that attractive or repulsive electrostatic interactions play a key role in dye binding to micelles. Unusually, spectra of complexes formed between the dye and cationic surfactant are typical of those of the azo tautomeric form as opposed to the hydrazone form that is prevalent in aqueous media. Addition of anionic surfactant to micellar solutions of nonionic or zwitterionic surfactants results in successive displacement of dye from the respective micelles, i.e. binding is competitive.     

Solubilisation of dyes by surfactant micelles. Part 1; Molecular interactions of azo dyes with nonionic and anionic surfactants

An ultraviolet-visible spectroscopic investigation has been made of the interactions of a specially synthesised series of substituted, model arylazonaphthol dyes with nonionic and anionic surfactants. Changes in spectral features were recorded above the critical micelle concentrations, suggesting specific interactions of dyes with micelles of the respective surfactants. The affinity of the dye for the surfactant micelles increased when various p -substituent were incorporated in to the dyes. Similarly, there was a shift in azo–hydrazone tautomeric equilibria and an increase in measured dye p K _a values. Models are proposed for the location of dyes in nonionic or anionic micelles. Unlike earlier studies, it is concluded that the solubilised dye experiences only one environment in nonionic micelles but the specific location, i.e. whether preferentially incorporated in the hydrophobic micellar interior or in the more hydrophilic, outer polyoxyethylene layer, depends upon the nature of the substituent.     

Effect of Inorganic Additives on a Conventional Anionic–Nonionic Mixed Surfactants System in Aqueous Solution

The interaction between an anionic surfactant (sodium dodecyl sulfate) and a nonionic surfactant [polyoxyethylene (9.5) octyl phenyl ether] in aqueous salt solution was investigated using the surface tension method. The critical micelle concentration values were determined for the individual surfactants and their corresponding mixtures. The interaction parameter between the surfactants in the mixed micelles, the activity and activity coefficients in the mixed micelles, and the thermodynamic parameters were calculated using various approaches, viz., Clint, Rubingh, and Maeda models. It was observed that the critical micelle concentration of the mixed surfactants system reveals little deviation from ideality.     

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.     

Solubilisation of dyes by surfactant micelles. Part 2; Molecular interactions of azo dyes with cationic and zwitterionic surfactants

A UV–vis spectroscopic investigation has been made of the interactions of a specially synthesised series of o - and p -substituted, model arylazonaphthol dyes with the cationic and zwitterionic surfactants above and below their critical micelle concentrations at pH 10. Spectra of dyes incorporated in micelles of zwitterionic surfactant or cationic surfactant at pHs < 8 are similar to those found in nonionic micelles, i.e. dye substituents control its location similarly for all the micelle types. However, the common anion is selectively favoured in cationic micelle solutions at pH 10, due to electrostatic interactions within the micellar surface. Introduction of polar groups at either end of the molecule confines the dyes to the surface of either zwitterionic or cationic micelles and are characterised by atypical p K _A shifts. Electrostatic complexes between dyes and cationic or zwitterionic surfactants were formed in sub-micellar regions, those with cationic surfactant being sparingly soluble.     

Adsorption of alizarinate–micelle complexes on Na-montmorillonite

The adsorption on Na-montmorillonite of the monovalent anion alizarinate and its complexes with micelles of cationic surfactants was investigated. Micelles were prepared from octadecyltrimethylammonium (ODTMA) and benzyldimethylhexadecyl-ammonium (BDMHDA). Alizarinate–micelle complexes are much more efficient for the adsorption of the dye than alizarinate alone, e.g., from 0.05 mM alizarinate solution 12.5 mmol per 100 g clay was adsorbed in the presence of micelles, whereas only 4 mmol per 100 g clay was adsorbed in their absence. However, unlike the adsorption of alizarinate on the clay, where its adsorbed fraction increased with the concentration of the clay, in the presence of micelles, the concentration of the clay should be optimized for achieving maximal adsorption of alizarinate. This effect is due to monomer adsorption on excessive clay sites, which leads to the decomposition of micelles, and consequently, the adsorption of alizarinate is reduced.Visible spectra of alizarinate–micelle complexes in water and adsorbed on montmorillonite were recorded. The absorption band of alizarinate in aqueous solutions at 522 nm was red-shifted in the presence of ODTMA and BDMHDA micelles due to the effect of the micelle microenvironment. Further shifts were observed in the presence of montmorillonite indicating that the alizarinate–micelle complexes were adsorbed on the clay. Significant spectroscopic changes were observed after the adsorption of alizarinate–BDMHDA-micelle complex on the clay indicating that the adsorption leads to changes in the micelle. This observation suggests that the dye may serve as a probe in visible-spectroscopy study of the adsorption of micelles on clay minerals.     

Preparation and Characterization of Copolymer Micelles Formed by Poly(ethylene glycol)-Polylactide Block Copolymers as Novel Drug Carriers

Diblock copolymer poly(ethylene glycol) methyl ether-polylactide (MePEG-PLA) micelles were prepared by dialysis against water. Indomethacin (IMC) as a model drug was entrapped into the micelles by dialysis method. The critical micelle concentration (CMC) of the prepared micelles in distilled water investigated by fluorescence spectroscopy was 0.0051 mg/mL which is lower than that of common low molecular weight surfactants. The diameters of MePEG-PLA micelles and IMC loaded MePEG-PLA micelles in number-averaged scale measured by dynamic light scattering were 52.4 and 53.7 nm respectively. Transmission electron microscope and scanning electron microscope observation showed that the appearance of MePEG-PLA micelles was in a spherical shape. The content of IMC incorporated in the core portion of the micelles was 18 wt.%. The effects of the synthesis method of the copolymer on the polydispersity of the micelles and the yield of the micelles formation were discussed.     

A spectroscopic and modelling study of polymer/dye interactions†

A spectroscopic study has been made of the comparative effectiveness of nonionic, zwitterionic and cationic polymers in binding model dyes. Addition of polymer produces smaller changes in the UV–vis spectra than observed in micellar solutions. Upon binding to polymers, the measured pK_A values of the model dyes decrease. The results of modelling and spectroscopic studies of the interaction between the model arylazonaphthol dyes are discussed in this paper. Addition of anionic surfactants, e.g. SDS, below their critical micelle concentrations disrupts polymer/dye binding, resulting in relocation of model dye to new sites formed from polymer/surfactant interactions. These sites are more apolar and produce spectra similar to those in corresponding micelles but with higher dye pK_A values and binding affinities. For the previous paper in this series see page 140; for parts 1 and 2 see refs 1 and 2, respectively.     

Influence of Nonionic Surfactant on Hydrolysis of Vinyl Sulfone Reactive Dye

Nonionic surfactants are widely used in reactive dyeing processes, and the interaction between surfactants and reactive dyes affect the hydrolytic property of reactive dyes. In this study, reactive brilliant blue KN‐R (C.I. reactive blue 19) was employed as a model dye, and fatty alcohol polyoxyethylene ether (AEO‐9) was selected as a model nonionic surfactant. The interaction was first investigated in aqueous solutions by a UV‐spectrophotometry method, then the effect of surfactant concentration on the hydrolytic behavior of KN‐R was studied using high performance liquid chromatography method. Below the critical micelle concentration, the surfactant served as dispersant; the hydrolysis of reactive dye was accelerated. However, when the concentration of surfactant was above its critical micelle concentration, the dye was solubilized into the micellar phase, which was revealed from the changes in absorbance intensity and wavelength of the maximum absorbance. This led to slowed hydrolysis of reactive dye. These findings are useful in understanding the effect of concentration of nonionic surfactant on the hydrolysis of vinyl sulfone reactive dyes.     

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.     

季铵盐双子表面活性剂与HPC在水溶液中的相互作用

采用稳态荧光和电导方法研究了系列季铵盐阳离子双子表面活性剂C12-S-C12·2Br(S代表亚甲基的个数)与水溶性高分子羟丙基纤维素(Hydroxypropyl cellulose,HPC)在水溶液中的相互作用。实验结果表明:在低于双子表面活性剂自身临界胶团浓度(Critical miceue concentration,cmc)时,在HPC分子上发生了聚集。当E12-S-C12·2Br/HPC体系混合溶液中C12-S-C12·2Br。的浓度达到c2(c2>cmc)时才有表面活性剂自由胶团生成。揭示了临界聚集浓度(Critical aggregation concentration,cac)和C12-S-C12·2Br/HPC体系混合溶液中自由胶团生成浓度c2与系列C12-S-C12·2Br表面活性剂cmc的比例关系及与链接链S的关联。     

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.     

Flavyliumsalze als Sonden zur Charakterisierung anionischer Tensidlösungen

Flavylium Salts as Probes for the Characterization of Anionic Micelles Flavylium salts are suitable probe molecules for the fluorimetric investigation of the critical micelle concentration (CMC); for the absorption-spectroscopic investigation of the surface potential; and also the microacidity in the Stern-layer of anionic micelles. The reaction rates of the hydrolytic cleavage of the 7-hydroxy-4′-methoxyflavyliumion 1a and the equilibrium between 1a and the 2,4-dihydroxy-4′-methoxychalcone 5a formed were studied in acidic water solutions and in micellar surfactant solutions. Both measurements resulted in comparable values of the microacidity on the surface of the sodium dodecylsulfate micelles (SDS). The calculated surface-potential of SDS-micelles corresponds to literature data. The surface-potentials of p-dialkylbenzenesulfonate micelles (p-DABS) depend on the structure of these surfactants in a characteristic manner.     

Photochemische Primärprozesse von Xanthenfarbstoffen. II. Blitzlichtspektroskopische Untersuchungen zum Einfluß von anionischen Mizellen auf die photochemischen Primärprozesse von Selenopyronin

Photochemical Primary Processes of Xanthene Dyes. II. Investigations of the Influence of Anionic Micelles on the Primary Processes of Selenopyronine by Flash Excitation In aqueous solutions containing anionic micelles, the dye cations of selenopyronine are present at the micellar surface. If the concentration of the dye ions is much lower than the concentration of micelles, only monomolecular triplet decay (k₁^aM = 2 · 10⁻³s⁻¹) is observed. Under these conditions, the half-oxidized and half-reduced form of selenopyronin is not formed. If the concentration of the dye ions is much higher than the concentration of micelles, two or more dye ions are present at every micelle, and a fast bimolecular decay of the triplet state during the flash is observed. The quenching of the triplet state with p-benzoquinone (k₇^aM = 1,9 · 10⁹ l/mol s), DABCO (k₁₀^aM = 1,6 · 10⁷ l/mol s) and EDTA (k₁₁^aM = 1,3 · 10⁵ l/mol s) and the decay processes of the half-reduced and half-oxidized form in the micellar solution are investigated.     

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.     

Mixed micelles of some metal dodecyl sulfates and triton X-100 in aqueous media

Tensiometric studies on several binary surfactant mixtures containing anionic surfactants, viz., metal (lithium, sodium, potassium, copper, cobalt, and magnesium) dodecyl sulfates and a nonionic surfactant (Triton X-100) in water at different mole fractions (0–1) provide critical micelle concentration (CMC) values. The composition of mixed micelles and the interaction parameter, β, evaluated from the CMC data for different systems using Rubingh's theory, are discussed. Marked interaction is observed with monovalent dodecyl sulfates. The influence of counter-ion valence on the formation of mixed micelles was investigated for anionic-nonionic systems, and results indicated that mixed systems with bivalent counter-ions in metal dodecyl sulfate resembled nonionic-nonionic systems where weak/negligible interaction has been reported. Salt addition revealed the weakening of interaction in the mixed systems, which is attributed to the head group charge neutralization and the dehydration of the ethylene oxide units of the nonionic surfactants. A few cloud point and viscosity data are also reported.     

Solubilisation of dyes by surfactant micelles. Part 4: Influence of dye fixatives

Dye loss from unfixed dyed fabrics has been found to be insensitive to change in surfactant type or concentration. There was accompanying dye transfer to white fabric but this was reduced by Synperonic A7 in the case of fabrics dyed with CI Direct Green 26, due to solubilisation of the dye in nonionic micelles. The anionic surfactant, SDS, selectively displaced dye from fixed dyed fabrics, paralleling its behaviour with water soluble polymers. Similarly, dye loss was related to concentration of surfactant monomer, the effect increasing with SDS concentration up to its critical micelle concentration. Other anionic surfactants have been found to exhibit a similar trend, the effect increasing with their increasing surface activity. The commercial polymeric fixatives, Tinofix ECO and Indosol E50, were the most effective of those studied and the single-chain cationic surfactant, CTAB, was the least effective.     

Effect of nonionic surfactants on the polarographic maximum and electrocapillary curves: A comparative study

The polarographic and electrocapillary curve methods have been used to determine the maximum suppression point (MSP), polarographic micelle point (PMP) and critical micelle concentration (cmc) of some polyoxyethylated nonionic surfactants, viz., Tween 20, Tween 40 and Tween 80. The cmc values thus obtained have been compared with the values obtained by surface tension, iodine solubilization, spectral dye and radiometric methods.