Solubilization of Aminoanthraquinone Disperse Dyes in Micelle of Nonionic Surfactant and Their Streaming Dichroism (Part 2)
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A spectrophotometric method has been used to study the interactions of some monoazo anionic dyes with a series of nonionic surfactants of different ethylene oxide chain length. The interaction between the dyes and the surfactants has been shown to be hydrophobic in nature with the extent of interaction increasing with increasing hydrophobicity of alky I side–chains on the dyes.
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Abstract Interaction of sulphone based reactive dyes, designated as dye-1 and dye-2, with cationic micellar system of cetyltrimethylammonium bromide (CTAB), has been investigated by spectroscopic and conductometeric measurements. Efficiency of the selected micellar systems is assessed by the values of binding constant ( K b ), partition coefficient ( K x ) and respective Gibbs energies. Critical micelle concentration (CMC) of surfactant, electrostatic and hydrophobic interactions as well as polarity of the medium plays significant role in this phenomenon. The negative values of Gibbs energies of binding (∆G b ) and partition (∆G p ) predicts the feasibility and spontaneity of respective processes. Similarly negative values of ∆G m and ∆H m and positive values of ∆S m , calculated from conductometeric data, further, revealed the exothermicity, spontaneity and, thus, stability of system. The results, herein, have disclosed the strong interaction between dye and surfactant molecules. The dye-2 has been observed to be solubilized to greater extent, as compared to dye 1, due to strong interaction i th hydrophiles of CTAB and accommodation of its molecules in palisade layer of micelle closer to the micelle/water interface.
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The solubilization of a monoazo disperse dye based on naphthalimide containing an ester group in the presence of DTAB and two gemini cationic surfactants was investigated. The results showed that the solubilization power of gemini surfactants micelles was greater than that of conventional surfactant micelles (DTAB) for this dye. The nature of the visible absorption spectra in aqueous surfactant solutions above CMC was very similar to those in the ethanol solution. The solubilization power is strongly dependent on the surfactant structure and nature of micelles. The absorption of used disperse dye into polyester fabrics in the presence of cationic surfactants increased in the order of DTAB>12-4-12>14-414, once again confirming the higher solubilization power for gemini surfactants even at elevated temperatures.
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Carboxymethyl cellulose
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In this paper, the use of surfactants for solubilization of hydrophobic organic dyes (mainly solvent and disperse dyes) has been reviewed. The effect of parameters such as the chemical structures of the surfactant and the dye, addition of salt and of polyelectrolytes, pH, and temperature on dye solubilization has been discussed. Surfactant self-assemble into micelles in aqueous solution and below the concentration where this occurs—the critical micelle concentration (CMC)—there is no solubilization. Above the CMC, the amount of solubilized dye increases linearly with the increase in surfactant concentration. It is demonstrated that different surfactants work best for different dyes. In general, nonionic surfactants have higher solubilization power than anionic and cationic surfactants. It is likely that the reason for the good performance of nonionic surfactants is that they allow dyes to be accommodated not only in the inner, hydrocarbon part of the micelle but also in the headgroup shell. It is demonstrated that the location of a dye in a surfactant micelle can be assessed from the absorption spectrum of the dye-containing micellar solution.
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Abstract 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.
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Part 1 Overview: overview and history of the study of solubilization. Part 2 Solubilization in micelles: solubilization of gases thermodynamics of solubilization of polar additives in micellar solutions solubilization of uncharged molecules in ionic micellar solutions - toward an understanding at the molecular level solubilization in mixed micelles solubilization in amphiphilic copolymer solutions kinetics of solubilization in surfactant-based systems. Part 3 Solubilization in nonmicellar surfactant aggregates: adsolubilization solubilization in micelles and vesicles studied by fluorescence techniques, interplay between the microproperties of the aggregates and the locus and extent of solubilization solubilization of organic compounds by vesicles. Part 4 Methods of measuring solubilization: solubilization, as studied by nuclear spin relaxation and NMR-based self-diffusion techniques the partitioning of neutral solutes between micelles and water as deduced from critical micelle concentration determinations vapor pressure studies of solubilization comparison of experimental methods for the determination of the partition coefficients of n-alcohols in SDS and DTAB micelles. Part 5 Applications of solubilization: solubilization and detergency solubilization in micellar separations.
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This chapter focuses on solubilization of dyes in polyion-surfactant complexes, considers the solubilization of water insoluble dyes, spectroscopy of solubilizates, and energy transfer between solubilized donor-acceptor pairs. Interactions of nonionic polymers with ionic surfactants, and of ionic polymers with nonionic surfactants are observed at relatively high concentrations of polymers and/or surfactants due to the weak interactions. The binding isotherms of ionic surfactants by polyions of opposite charge are characterized by a very sharp rise at a critical equilibrium concentration of free surfactant. The formation of hydrophobic domains by polymer-surfactant complexes in aqueous solution may be expected to solubilize water-insoluble materials. Many dye molecules form aggregates in aqueous solution, with their molecular shape leading to a "stacking" arrangement. The stacking tendency of the dye ions in the polymer domain can be demonstrated for instance from the fluorescence spectrum of pyrene covalently bound to polymer, which exhibits excimer emission in the absence of surfactant.
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As a fundamental study on the solvent-dying, the solubility of disperse dyes in nonpolar solvents and in nonaqueous surfactant solutions was measured. The solubility of dyes nonpolar solvents was from 10-5 to 10-3 (mol/kg solvent) and was in the order of benzene>cyclohexane>n-heptane. Furthermore, a linear relation was observed between logarism of the solubility and inorganic/organic properties of dye molecules. On the other hand, the solubility of dyes in surfactant solutions was estimated in terms of the number of dye molecule dissolved by a surfactant molecule present. The solubility of an azo dye in benzene solutions of surfactants was in the order of cationic>nonionic>anionic surfactants. The solubility in anionic surfactant solutions was independent on the counter ions and bulkiness of hydrocarbon chain of surfactant molecules, but those in cationic and nonionic surfactant solutions depended on the counter ions and the ethylene oxide chain length, increasing in the order Cl-salt>Br-salt>I-salt and NP=10>NP=6>NP=4. The solubility of aminoanthraquinone dyes in anionic surfactant solutions decreased with increase of the number of amino group of dyes. The effect of solvents on the solubility of an azo dye in anionic surfactant solutions was in the order of benzene>cyclohexane>n-heptane, but it was not remarkedly affected by temperature.
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