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.     

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.     

Adsorption of dyes to cotton and inhibition by surfactants, polymers and surfactant–polymer mixtures

A wide-ranging investigation has been made of the adsorption of direct dyes to cotton and of inhibition by surfactants, polymers and polymer–surfactant mixtures. Generally, the selected polymers are extremely effective at inhibiting adsorption of most of the direct dyes to cotton but are less effective at inhibiting adsorption of small, model azo dyes. Micellar solutions of zwitterionic and cationic surfactants can inhibit adsorption of both small dyes and commercial dyes. It is shown that anionic surfactants at sub-micellar concentrations can inhibit polymer-dye interactions due to displacement of dye and/or relocation into micelle-like polymer–surfactant complexes. New insights have been obtained into the interactions of dyes with cotton and with polymers, surfactants or their mixtures, particularly into observed dye selectivities.     

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.     

Adsorption of dyes to cotton and inhibition by polymers

This paper addresses some key factors that control the transfer of dyes between garments during detergency. It is shown that adsorption of a series of substituted arylazo-2-naphthol dyes to cotton under simulated detergency conditions is influenced by the log P fragment value of the dye substituent; this suggests that hydrophobic interactions make an important contribution to the binding free energy. The comparative effectiveness of nonionic, zwitterionic and cationic polymers in inhibiting adsorption of dye to cotton was also investigated. Increase in polymer concentration reduces dye adsorption to cotton; increase in polymer molecular weight at constant polymer concentration also inhibits dye adsorption up to a molecular weight of ca. 20000, above which there is no further change. Anionic surfactants reduce the efficacy of polymers by displacing dyes from polymers. Surprisingly, certain dyes become relocated in polymer/surfactant complexes; binding is much more effective than in corresponding surfactant micelles.     

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.     

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 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 cotton substrate characteristics upon surfactant adsorption

It is shown that the reported differences in anionic surfactant adsorption on cotton can be largely attributed to the presence of variable amounts of natural wax on the fiber surface. High adsorption values with peaks near critical micelle concentration (cmc) result from surfactant adsorption on the wax surface. Wax-free surfaces fail either to show the same high maxima or the same relative magnitude of adsorption. At surfactant cmc the adsorption relationship for waxy cotton (millimoles/g. of cotton) cationic: nonionic: anionic was roughly 66 to 17 to 74. For dewaxed cotton, this became 40 to 10 to nil. Confirming the findings of others, no adsorption by cotton of sodium tripolyphosphate occurs either with waxy or wax-free cotton. Also addition of tripolyphosphate decreased the adsorption of several anionic surfactants. At concentrations greater than cmc and at sufficiently-high solution temperature, anionic surfactants can solubilize cotton wax, leaving a less waxy substrate upon which adsorption is then reduced.     

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.     

Bordeaux-R interactions with surfactants: thermochromic investigations of proton ionisation in cationic, nonionic and anionic surfactant solutions

Apparent thermodynamic parameters for the hydroxy proton ionisation of Bordeaux-R were obtained in micellar solutions using the thermochromic method. The effect of addition of the surfactants CTAB, TX-100 and SDS was investigated in buffered solutions in the pH range of 6–13. Ionisation constants in water and in the presence of surfactants were determined spectrophotometrically and the p K ' of Bordeaux-R in water was found to be 10.90 in the absence of surfactant. However, at concentrations above critical micelle concentration, p K ' dropped to 10.14 with CTAB, increased to 11.29 with TX-100 but was insensitive to SDS addition. Standard enthalpies and entropies of ionisation were obtained using the thermochromic method. This method, in conjunction with p K and spectral measurements and comparison with different azo dyes, has been shown to provide detailed information on the mechanism of dye–surfactant interaction.     

Interactions between dyes and surfactants in inkjet ink used for textiles

Optimal preparation of inkjet ink should be possible through the elucidation of the relationship between dye/additive interactions and ink performance. In the present study, the interactions between the dyes and surfactant additives were investigated. To investigate the physical properties of the surfactants used, the critical micelle concentration (cmc) and the aggregation number (N) were determined using electron spin resonance, static light-scattering, and fluorescence spectroscopy. On the basis of the cmc and N values, the visible absorption spectra of aqueous acid dye solutions (C. I. Acid Red 88, 13, and 27) containing surfactants (i.e., Surfynol 465 (S465), octaethylene glycol monododecyl ether (OGDE), and sodium dodecyl sulfate (SDS)) were measured. From the dependence of the spectra on the surfactant concentration, the binding constants, K(bind), of the acid dyes with the surfactant micelles were calculated: the K(bind) values decreased in the order of C. I. Acid Red 88 > C. I. Acid Red 13 > C. I. Acid Red 27, which correlates with the number of sulfonate groups. For all the dyes, the K(bind) values with the nonionic surfactants, S465 and OGDE, were much larger than those with the anionic surfactant, SDS. The thermodynamic parameters of the binding, i.e., the enthalpy change, ΔH(bind), and entropy change, ΔS(bind), were determined via the temperature dependence of the binding constants. The positive ΔH(bind) value for S465 indicates an endothermic binding process, while the negative ΔH(bind) values for SDS and OGDE indicate exothermic binding processes.     

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.     

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.     

Micellization and Interfacial Interaction Behaviors of Gemini Cationic Surfactants–CTAB Mixed Surfactant Systems

The interfacial and micellization behaviors of binary mixtures of two gemini cationic surfactants and conventional the cetyl trimethyl ammonium bromide surfactant were studied at various molar ratios. From the equilibrium surface tension measurements, the critical micelle concentrations (CMC) data were obtained as functions of the composition. Values of the CMC were analyzed according to the regular solution model developed by Rubingh for mixed micelles. Two interaction parameters were obtained for each system, the interaction at the interface, and in the micellar phase. The results showed that micellization and adsorption properties of the studied mixed systems depend on the spacer chain lengths of the gemini surfactants and their ratio in the mixed systems.     

Adsorption and fixation behaviour of CI Reactive Red 195 on cotton woven fabric in a nonionic surfactant Triton X‐100 reverse micelle

To achieve the goals of saving water and being salt‐free in the coloration of cotton fabric with reactive dye, nonionic reverse micelles were prepared and optimised with a surfactant, Triton X‐100, n‐octanol and isooctane by injecting a small amount of CI Reactive Red 195 aqueous solution. The adsorption, diffusion and fixation of this dye on cotton fabric in Triton X‐100 reverse micelle and bulk water were then investigated. The equilibrium and kinetic data of the dye adsorption process were evaluated. The colour strength and fixation rate of cotton fabrics dyed in the micelle and in bulk water were also examined and compared. The results indicated that the amount of dye adsorbed increased with the increasing temperature and the initial dye concentration. The dye adsorption process could be described using the Langmuir isotherm and pseudo‐second‐order kinetic equations. It was found that CI Reactive Red 195 showed a stronger adsorption property on cotton fabric in Triton X‐100 reverse micelle than in bulk water without the addition of sodium chloride. Using Triton X‐100 reverse micelle as the dyeing medium offered the reactive dye better diffusion performance within the cotton fibre as compared with bulk water. Moreover, higher fixation of the dyes absorbed on the cotton fibre was achieved when the optimum concentration of sodium carbonate was used as the alkali agent in Triton X‐100 reverse micelle.     

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.     

Acid-base equilibria of sulfonephthalein dyes in aqueous polymer-surfactant media

The acid-base equilibria of three anionic sulfonephthalein dyes, viz., bromothymol blue (BTB), thymol blue (TB), and cresol red (CR), were studied spectroscopically in aqueous media containing the water-soluble noninonic polymers polyvinyl alcohol (PVA) and polyethylene glycol (PEG) in the presence of an anionic surfactant, sodium dodecyl sulfate (SDS). A partition equilibrium method was used to determine the equilibrium constant of partition of the dyes between the micellar pseudo phase and aqueous phase in the presence of PVA and PEG. The critical aggregation concentrations (CAC) of the surfactants in buffered aqueous systems containing the neutral polymers were also determined. The CAC of the polymer-surfactant systems were found to be lower than the critical micelle concentration of such systems in the absence of polymer, in otherwise identical conditions. The pH-dependent association constants, K _ass, of the sulfonephthalein dyes with the SDS-PVA system increased with the increase in molecular weight of the polymer. The interactions of the dyes with the buffered aqueous SDS-PVA and SDS-PEG systems were found to be endothermic and entropy oriented. In the polymer domain, the head group region of the micelles was more exposed at lower concentrations of the polymer, but under excess polymer concentration they were increasingly shielded, which impaired their electrostatic interaction with the dyes.     

Solubility of Two Disperse Dyes Derived from <Emphasis Type="Italic">N</Emphasis>-Alkyl and <Emphasis Type="Italic">N</Emphasis>-Carboxylic Acid Naphthalimides in the Presence of Gemini Cationic Surfactants

The solubility of naphthalimide-based monoazo dyes containing N-ethyl and N-ethanoic acid groups was investigated in the presence of a conventional monomeric counterpart (DTAB) and two cationic gemini surfactants (12-4-12 or 14-4-14) individually. The effective parameters on dye solubility such as temperature, time and concentration of surfactants were investigated by UV–Visible spectrophotometry. The results demonstrate that the solubility of both dyes was considerably increased at concentrations above the surfactant CMC. The wavelength for the maximum absorbance of dyes in the aqueous solution shifts toward longer wavelengths with changes in the concentration of the cationic surfactants. A kinetic study of solubilization of dyes in cationic surfactants solution showed that the rate of solubilization follows the pseudo-first-order reactions. Rates of solubilization were in the range of 0.5 × 10⁻³ to 6.8 × 10⁻³ min⁻¹ for both dyes. The disperse dye containing a carboxylic acid group (dye 2) has a higher solubility rate than the dye containing an alkyl group (dye 1). The type of surfactant has a very low effect on adsorption of dye 1 onto the polyester fibers, whereas changing the surfactant type from DTAB to 12-4-12 or 14-4-14 causes adsorption of dye 2 on polyester to decrease.     

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.