Spectrophotometric study of anionic azo-dye light yellow (X6G) interaction with surfactants and its micellar solubilization in cationic surfactant micelles

Solubilization and interaction of azo-dye light yellow (X6G) at/with cationic surfactants cetyltrimethylammonium bromide (CTAB) and cetylpyridinium chloride (CPC) was investigated spectrophotometricaly. The effect of cationic micelles on solubilization of anionic azo dye in aqueous micellar solutions of cationic surfactants was studied at pH 7 and 25 degrees C. The binding of dye to micelles implied a bathochromic shift in dye absorption spectra that indicates dye-surfactant interaction. The results showed that the solubility of dye increased with increasing surfactant concentration, as a consequence of the association between the dye and the micelles. The binding constants, K(b), were obtained from experimental absorption spectra. By using pseudo-phase model, the partition coefficients between the bulk water and surfactant micelles, K(x), were calculated. Gibbs energies of binding and distribution of dye between the bulk water and surfactant micelles were estimated. The results show favorable solubilization of dye in CTAB micelles.     

Interaction of Quercus Infectoria Natural Dye with Cationic and Anionic Surfactants: Adsorption/Micellization of Dye

The interaction of Indian natural dye, that is, Himalaya (Quercus infectoria) with cationic surfactant (cetyl trimethyl ammonium bromide) and anionic surfactant (sodium lauryl sulphate) has been studied. The spectrophotometric data showed an interaction between the natural dye and surfactants. Critical micelle concentration (CMC) of the surfactants, determined by measurement of specific conductance and surface tension methods, was found to be increase in case of anionic surfactant while that was found to decrease in case of cationic surfactant. Thermodynamic and surface parameters showed domination of micellization of dye in case of cetyl trimethyl ammonium bromide and domination of adsorption of dye in case of sodium lauryl sulphate.     

Interaction of ionic surfactants with cornea-mimicking anionic liposomes

The interaction of surface-active molecules with lipid bilayers is ubiquitous both in biological systems and also in several technological applications. Here we explore the interaction of ionic surfactants with liposomes whose composition mimics the ocular epithelia. In this study, liposomes with a composition mimicking ocular epithelia are loaded with calcein dye above the self-quenching concentration. The liposomes are then exposed to surfactants, and the rate of dye leaked from the liposomes due to the interaction of surfactants is measured. Both cationic and anionic surfactants at various concentrations and ionic strengths are explored. Results show that the liposome bilayer permeability to the dye increases on exposure to the surfactants, leading to the release of the dye trapped in the core. However, the dye release stops after a finite time, suggesting a transient increase in permeability followed by healing. The leakage profiles exhibit two different timescales for the cationic surfactant but only one timescale for the anionic surfactant. The total dye leakage increases with surfactant concentration, and at a given concentration, the dye leakage is significantly higher for the cationic surfactants. The timescale for the healing decreases with increasing surfactant concentration, and increasing ionic strength increases the dye leakage for the anionic surfactant. These results show that the surfactant binding to the lipid bilayer increases the permeability while the bilayers heal likely because of the surfactant jump from the outer to the inner leaflet and/or rearrangement into tighter aggregates.     

Sorption of a fluorescent whitening agent (Tinopal CBS) onto modified cellulose fibers in the presence of surfactants and salt

The combined effect of salt (10 mmol L(-1)) and surfactants on the sorption of the fluorescent brightener 4,4'-distyrylbiphenyl sodium sulfonate (Tinopal CBS) onto modified cellulose fibers was studied. Sorption efficiencies with both cationic and anionic surfactants were evaluated. Emission spectroscopy was used for quantitative analysis since Tinopal has an intense fluorescence. The sorption efficiency of the brightener is greater for solutions containing a cationic surfactant (DTAC) below the critical micelle concentration (cmc), while for an anionic surfactant (SDS) above its cmc the efficiency is greater. The profile of the sorption isotherms were interpreted in terms of the evolution of surfactant aggregation at the fiber/solution interface. Salt influences the efficiency of the Tinopal sorption on the modified cellulose fibers either because it decreases the cmc of the surfactants or because the ions screen the surface charges of the fiber which decreases the electrostatic interaction among the charged headgroup of the surfactant and the charged fiber surface.     

Premicellar and micelle formation behavior of dye surfactant ion pairs in aqueous solutions: deprotonation of dye in ion pair micelles

The premicellar and micelle formation behavior of dye surfactant ion pairs in aqueous solutions monitored by surface tension and spectroscopic measurements has been described. The measurements have been made for three anionic sulfonephthalein dyes and cationic surfactants of different chain lengths, head groups, and counterions. The observations have been attributed to the formation of closely packed dye surfactant ion pairs which is similar to nonionic surfactants in very dilute concentrations of the surfactant. These ion pairs dominate in the monolayer at the air-water interface of the aqueous dye surfactant solutions below the CMC of the pure surfactant. It has been shown that the dye in the ion pair deprotonates on micelle formation by the ion pair surfactants at near CMC but submicellar surfactant concentrations. The results of an equilibrium study at varying pH agree with the model of deprotonated 1:1 dye-surfactant ion pair formation in the near CMC submicellar solutions. At concentrations above the CMC of the cationic surfactant the dye is solubilized in normal micelles and the monolayer at the air-water interface consists of the cationic surfactant alone even in the presence of the dyes.     

Role of surfactants in the sorption of the whitening agent Tinopal CBS onto viscose fibers: a fluorescence spectroscopy study

In the present work, we studied the role of an anionic surfactant, sodium dodecyl sulfate, and a cationic surfactant, dodecyltrimethylammonium chloride, in the sorption of 4,4'-distyrylbiphenyl sodium sulfonate (Tinopal CBS) onto modified cellulose fibers. Fluorescence spectroscopy was used to quantify the amount of sorbed Tinopal CBS on the fiber surface. Differences in the spectral properties and the efficiency of sorption of the whitener/surfactant/fiber system are explained in terms of electrostatic interactions. Our results also show that the sorption efficiency is greater for solutions containing cationic surfactants only below the critical micelle concentration, while anionic surfactants show a smooth influence on the sorption process.     

Interaction studies of styrene—ethylene oxide block copolymers with ionic surfactants in aqueous solution

The interaction of styrene—ethylene oxide block copolymers with four anionic surfactants (sodium dodecyl sulfate, sodium dodecanoate, sodium dodecylbenzenesulfonate, and sodium dodecanoyl sarcosinate), and two cationic surfactants (tetradecyl- and hexadecyl-trimethylammonium bromide), was studied and each surfactant showed a distinct interaction with the copolymer in aqueous solution. Usually two transitions, one below and one above the critical micelle concentration, CMC, of the surfactants, were observed from conductance, surface tension, and dye solubilization measurements. These transitions indicate the beginning and completion of polymer—surfactant interaction. The viscometric results showed the formation of a polyelectrolyte complex. The interaction between copolymer and sodium dodecyl sulfate was also examined by ¹H NMR. The influence of the molecular characteristics of the block copolymers, the nature and type of surfactants, temperature and added salt on the interaction is described. A possible mechanism for such an interaction is proposed.     

The Hofmeister series effect in adsorption of cationic surfactants--theoretical description and experimental results

Interfacial properties of cationic surfactants show strong dependence on the type of surfactant counterion or on the type of anion of a salt added to the surfactant solution. In the paper, the models of ionic surfactant adsorption that can take into account ionic specific effects are reviewed. Model of ionic surfactant adsorption based on the assumption that the surfactant ions and counterions undergo nonequivalent adsorption within the Stern layer was selected to describe experimental surface tension isotherms of aqueous solutions of a number of cationic surfactants. The experimental isotherms for: n-alkyl trimethylammonium cationic surfactants, namely: C(16)TABr (CTABr or CTAB), C(16)TACl, C(16)TAHSO(4), C(10)TABr and C(12)TABr as well as decyl- and dodecylpyridinium salts with and without various electrolyte anions as Cl(-), Br(-), F(-), I(-), NO(3)(-), ClO(4)(-) and CH(3)COO(-) were described in terms of the model and a good agreement between the theory and experiment was obtained for a wide range of surfactants and added electrolyte concentrations. A very pronounced Hofmeister effect in dependence of surface tension of cationic surfactants on the type of anion was found. Analysing this dependence in terms of the proposed model of ionic surfactant adsorption, strong correlation between "anion surface activity" (the model parameter accounting for ion penetration into the Stern layer), and the ion polarizability was obtained. That suggests that the mechanism related to the dispersive interaction of polarized ion with electric field at interface is responsible for Hofmeister series effects in surface activity of cationic surfactants. The same mechanism was proposed recently to explain the dependence of surface tension increase with electrolyte concentration on anion and cation type.     

m-6-m型Gemini双季铵盐表面活性剂与DNA的相互作用

合成了5种m-6-m型Gemini双季铵盐表面活性剂,在对产物结构和表面活性进行分析的基础上,分别采用紫外分光光度法和荧光分光光度法考察了m-6-m型Gemini双季铵盐表面活性剂与DNA的相互作用.结果表明,m-6-m型Gemini表面活性剂的CMC随烷基疏水链的增长呈逐渐下降趋势.几种表面活性剂均没有使DNA的紫外吸收峰发生红移或蓝移现象,说明复合物无嵌插作用或氢键形成,表面活性剂与DNA作用后的吸光度随表面活性剂浓度的增大而增强,当表面活性剂的浓度相同时,吸光度随疏水链的增大而逐渐减弱.Gemini表面活性剂浓度增大导致荧光强度降低,表面活性剂与DNA作用时的猝灭为静态猝灭,随着疏水链长度的增长,荧光猝灭常数降低,表面活性剂与DNA之间的作用力减弱.     

Effect of supramolecular interactions with cationic surfactants on adsorption of flavonoids on highly dispersed silica surface

The effect of the cationic surfactants decamethoxine and miramistin on the physicochemical properties of the natural flavonoids quercetin and rutin is studied spectrophotometrically in the range of physiological pH values. It is established that the interaction with these cationic surfactants changes the spectral characteristics of the flavonoids in solutions and essentially increases their adsorption on the surface of highly dispersed silica as compared with their aqueous solutions. It is shown that the efficiency of flavonoid adsorption from decamethoxine and miramistin solutions is governed by solution pH, flavonoid hydrophobicity, and the nature of a cationic surfactant.     

Studies on the interaction of bacterial capsular polysaccharide- Klebsiella K16 with cationic and mixed surfactants

The spectral studies of cationic dyes, pinacyanol chloride (PCYN) and acridine orange (AO) with capsular polysaccharide Klebsiella K16 (PK16) biopolymer in micellar media reveal many interesting phenomena. Intensity of the metachromatic band (μ) at 490 nm decreases gradually on addition of cationic single surfactant to the biopolymer PK16–dye system of P/D = 30, whereas the intensity of α and β bands reach to the value of original pure dye. As a result, the cationic surfactant destroys the metachromatic compound and forms a new complex with biopolymer PK16 by freeing the dye molecule. Enhancement of fluorescence intensity of AO-PK16 system with cationic surfactant is another evidence for the binding between the biopolymer and the surfactant. Interaction between the biopolymer and mixed surfactant has also been studied. Finally, the binding ability of cationic surfactants with or without non ionic surfactant, the idea of the critical aggregation concentration (cac) of the surfactant, mole fraction and the charge density of mixed surfactant for binding with PK16 and also the site of interaction have been pointed out.     

Growth, stability, optical and photoluminescent properties of aqueous colloidal ZnS nanoparticles in relation to surfactant molecular structure

The interaction between organic molecules and the surface of nanoparticles (NPs) strongly affects the size, properties and applications of surface-modified metal sulfide semiconductor nanocrystals. From this viewpoint, we compared the influence of cationic surfactants with various chain lengths and anionic surfactants with different head groups, as surface modifiers during synthesis of ZnS NPs in aqueous medium. The surfactant adsorbs on the surface of the particles as micelle-like aggregates. These aggregates can form even at the concentration lower than critical micelle concentration (cmc) due to interaction between the polar groups and the NPs. The nature of interaction depends specifically on the surfactant polar group. The ability of surfactant to form the micelle-like aggregates on the surface of the NPs correlates with their cmc. This leads to the fact that the surfactant with longer tail stabilizes the NPs better since its cmc is lower. The adsorption of the surfactant on the NPs also stabilizes them by the change of their charge which is in accordance with the correlation of zeta potential with the particles stability. The energetics of surface states generating interesting photoluminescence (PL) properties in ZnS NPs has been governed by the nature of surfactant molecules. In general, the size, structure, and stability of the ZnS NPs can be controlled by the choice of suitable surfactant.     

Dye aggregation and influence of pre-micelles on heterogeneous catalysis: A photophysical approach

Common cationic dyes used for laser and fluorescent probes present low solubility in water. In order to increase the dye concentration in aqueous solutions, anionic surfactant can be added. The strong interaction between anionic surfactant and cationic dye can affect drastically the dye absorption and fluorescence properties. Here we observed that the fluorescence of the species in aqueous solution is maximized at condition of complete micellization of surfactants at critical micelle concentration (CMC). In addition, combined measurements of absorption, emission and fluorescence lifetime provide fundamental information on the critical concentration of H-aggregates formation and monomer separation, induced by pre-micelles and homomicelles on different surfactant sodium dodecylsulphate (SDS) concentration. The experimental results show how to find precisely the critical concentration of H-aggregates by optical method in two different xanthene-derived molecules: rhodamine 6G and rhodamine B. The adequate transference of electron from excited dye to the conduction band of semiconductor (TiO₂) promotes the creation of reactive species that provides the degradation of dye with advantage of use of irradiation in the visible region and strong photobleaching with direct exposure to the visible light irradiation in a scale of time of 10 min.     

The modification of the triple helical structure of gelatin in aqueous solution 3. The influence of cationic surfactants

The interaction between cationic surfactants (hexadecyl and dodecyl trimethyl ammonium bromide) and gelatin was characterized by measuring the circular dichroism. The interaction between the cationic surfactants and gelatin is weak in comparison to that of anionic surfactants. When the concentration of cationic surfactants is sufficiently low, refolding of the gelatin-strands to the triple helical structure by rechilling the solution from 298 K to 283 K is complete. The triple helical content of the solution is affected more strongly by the cationic surfactants in acidic solution than at pHs 7 or 10. The interaction depends on the apolar group of the surfactant and is found to be stronger for DTAB than for CTAB at 298 K. Coagulation of the hydrophobic gelatin-cationic surfactant complexes does not comprise that pan of gelatin which is able to refold the triple helical structure. Therefore, the gelatin-strands of lower molecular weights are thought to react favorably with the surfactant ions.     

Spectral behaviour of eosin Y in different solvents and aqueous surfactant media

Photophysical behaviour of the anionic xanthene dye, eosin Y (EY) was investigated in solvents of different polarities as well as in the presence of aqueous cationic surfactants. From the correlation between E(T)(30) and Kosower Z values of EY in different solvents, subsequent parameters for EY were determined in the presence of surfactants. A red shift, both in the absorption and emission spectra of EY, was observed with decreasing solvent polarity. Dimerisation of EY was found to be dependent on solvent polarity. Cationic surfactants retarded the process of dimerisation, which were evident from the lower dimerisation constant (K(D)) values, compared to that of in pure water. Dye-surfactant interaction constants were determined at different temperatures (298-318 K) and subsequently the thermodynamic parameters, viz., ΔG°, ΔH° and ΔS° were evaluated using the interaction constant values. The fluorescence spectra of EY followed the same trend as in the absorption spectra, although with lesser extents. Stokes shifts were calculated and correlated with the polarity of the medium. Fluorescence of EY was initially quenched by the cationic surfactants in their pre-micellar region, which then followed a red shift with intensity enhancement. Fluorescence quenching was found to be of Stern-Volmer type where the excited state lifetime of EY remained unchanged in different surfactant media. However, the anisotropy value of EY was changed in the post micellar region of surfactants.     

Interaction between the water soluble poly{1,4-phenylene-[9,9-bis(4-phenoxy butylsulfonate)]fluorene-2,7-diyl} copolymer and ionic surfactants followed by spectroscopic and conductivity measurements

The interaction has been studied in aqueous solutions between a negatively charged conjugated polyelectrolyte poly{1,4-phenylene-[9,9-bis(4-phenoxybutylsulfonate)]fluorene-2,7-diyl} copolymer (PBS-PFP) and several cationic tetraalkylammonium surfactants with different structures (alkyl chain length, counterion, or double alkyl chain), with tetramethylammonium cations and with the anionic surfactant sodium dodecyl sulfate (SDS) by electronic absorption and emission spectroscopy and by conductivity measurements. The results are compared with those previously obtained on the interaction of the same polymer with the nonionic surfactant C12E5. The nature of the electrostatic or hydrophobic polymer-surfactant interactions leads to very different behavior. The polymer induces the aggregation with the cationic surfactants at concentrations well below the critical micelle concentration, while this is inhibited with the anionic SDS, as demonstrated from conductivity measurements. The interaction with cationic surfactants only shows a small dependence on alkyl chain length or counterion and is suggested to be dominated by electrostatic interactions. In contrast to previous studies with the nonionic C12E5, both the cationic and the anionic surfactants quench the PBS-PFP emission intensity, leading also to a decrease in the polymer emission lifetime. However, the interaction with these cationic surfactants leads to the appearance of a new emission band (approximately 525 nm), which may be due to energy hopping to defect sites due to the increase of PBS-PFP interchain interaction favored by charge neutralization of the anionic polymer by cationic surfactant and by hydrophobic interactions involving the surfactant alkyl chains, since the same green band is not observed by adding either tetramethylammonium hydroxide or chloride. This effect suggests that the cationic surfactants are changing the nature of PBS-PFP aggregates. The nature of the polymer and surfactant interactions can, thus, be used to control the spectroscopic and conductivity properties of the polymer, which may have implications in its applications.     

Adsorption of a cationic surfactant onto cellulosic fibers I. Surface charge effects

The adsorption of four cationic surfactants with different alkyl chain lengths on cellulose substrates was investigated. Cellulose fibers were used as model substrates, and primary alcohol groups of cellulose glycosyl units were oxidized into carboxylic groups to obtain substrates with different surface charges. The amount of surfactant adsorbed on the fiber surface, the fiber zeta-potential, and the amount of surfactant counterions (Cl(-)) released into solution were measured as a function of the surfactant bulk concentration, its molecular structure, the substrate surface charge, and the ionic strength. The contribution of each of these parameters to the shape of the adsorption isotherms was used to verify if surfactant adsorption and self-assembly models usually used to describe the behavior of surfactant/oxide systems can be applied, and with which limitations, to describe cationic surfactant adsorption onto oppositely charged cellulose substrates.     

Stability and Adsorption Properties of Suspensions of Finely Dispersed Silica in the Presence of Cationic Surfactants

Interrelation between the coagulation rate, adsorption and electrokinetic properties of silica polydisperse suspensions in the presence of cationic surfactants is studied. The highest coagulation rate is observed in a certain concentration range of the cationic surfactants. When pH values increases, an increasing amount of cationic surfactant is required to achieve maximal coagulation rate. For bisquaternary cationic surfactants, ethonium and decamethoxine, maximal coagulation rate is observed at concentrations by an order of magnitude lower than for monoquaternary cetyltrimethylammonium bromide. It is concluded that the suspensions lost their stability as a result of both neutralization of particle surface charge and flocculating effect of the cationic surfactants. Moreover, the flocculation mechanism depends on the cationic surfactant nature and physicochemical parameters of the medium, ionic strength and pH.     

Adsorption of Cationic Surfactants on Silica Surface: 2. Comparison of Theory with Experiment

Possible application of the SCFA lattice model to describe the adsorption of ionic surfactants on the surface whose charge and potential can be changed under the effect of adsorbing surfactant was theoretically studied. Calculated isotherms of surfactant adsorption were compared with experimental adsorption isotherms of dodecylpyridinium chloride on silica. It was shown that, upon the adsorption of cationic surfactants on SiO₂, the ionization of silanol surface groups is enhanced and the surface charge increases. The used set of parameters suggesting the interaction between the aliphatic tails of surfactant molecules and the surface made it possible to reach good agreement with the experiment.