Studies on the molecular interaction of safranin-T with surfactants

The spectrophotometric studies of safranin-T (Saf-T) dye in an aqueous solution containing three different types of surfactants such as CTAB (cationic), SLS (anionic) and Triton X-100 (TX-100), Tween-20, 40, 60 and 80 (nonionic) show that Saf-T forms a 1:1 molecular complex with TX-100, Tweens and SLS. Such a type of interaction is absent in Saf-T and CTAB. The thermodynamic and spectrophotometric properties of these complexes suggest that Saf-T forms a strong charge transfer (CT) complex with TX-100 and Tweens, whereas the interaction of Saf-T with SLS is coulombic in nature. Photogalvanic and photoconductometric studies also support the above interactions. In addition to this, the electron-donating ability among the nonionic surfactants i.e. TX-100 and Tweens towards dye, role of surface in CT interaction, the site of CT interaction and the intensity and stability of CT interaction between Saf-T and nonionic surfactants have been pointed out.     

Photophysics of xanthene dyes in surfactant solution

The spectral (both absorption and fluorescence) and photoelectrochemical studies of some anionic xanthene dyes namely erythrosine B, rose bengal and eosin have been carried out in micellar solution of cationic cetyl trimethyl ammonium bromide (CTAB), anionic sodium dodecyl sulphate (SDS) and neutral triton X-100 (TX-100). The results show that all these dyes form 1:1 electron-donor-acceptor (EDA) or charge-transfer (CT) complexes with TX-100, which acts as an electron donor. There is no interaction of these dyes with SDS, whereas the interaction with CTAB is mainly electrostatic in nature. In presence of TX-100, these dyes show enhancement of fluorescence intensity with a red shift and develop photovoltage in a photoelectrochemical cell. A good correlation has been found among the photovoltage generation in the systems consisting of these dyes and TX-100, spectral shift due to complex formation and thermodynamic properties of these complexes.     

Spectral and photophysical studies of thiazine dyes in triton X-100

The absorption spectra of several thiazine dyes such as thionine, azure A, azure B, azure C and methylene blue in aqueous solution of Triton X-100 show that dyes as electron acceptors form 11 charge-transfer (CT) or electron-donor-acceptor (EDA) complexes with Triton X-100, which acts as an electron donor. From the thermodynamic and spectrophotometric properties of these complexes, the abilities of dyes to accept an electron are in the order: azure C > thionine > azure A > azure B > methylene blue. The photogalvanic effect in the aqueous solution dye-surfactant has been studied. Generation of photovoltage supports a CT or EDA interaction between thiazine dyes and Triton X-100. There is a good correlation among the photophysical (photovoltage), spectral and thermodynamic properties of these complexes.     

Studies on the molecular interaction of Erythrosine ‘B’ with surfactants

The spectroscopic investigation on anionic dye, Erythrosine ‘B’(EB) with three different types of surfactants such as CTAB (cationic), sodium lauryl sulphate (SLS; anionic) and Triton X-100 (TX-100),Tween-20, 40, 60 and 80 (nonionic) in aqueous media shows that EB forms a 1:1 molecular complex with TX-100, Tweens and CTAB. No interaction is observed between EB and SLS. The thermodynamic and spectrophotometric properties of these complexes suggest that EB forms a strong charge transfer (CT) complex with TX-100 and Tweens whereas the interaction of EB with CTAB is coulombic in nature. Photogalvanic and photoconductometric studies also support the above interactions. In addition to this, the electron-donating ability among the nonionic surfactants, i.e. TX-100 and Tweens towards dye, role of surface in CT interaction, the site of CT interaction and the intensity and stability of CT interaction between EB and nonionic surfactants have been pointed out.     

吲哚方酸菁染料在表面活性剂水溶液中的光降解

考察了4种含有不同N位取代基的对称吲哚方酸菁染料在阳离子表面活性剂十六烷基三甲基溴化铵(CTAB)、阴离子表面活性剂十二烷基硫酸钠(SDS)和非离子表面活性剂曲拉通(TX-100)水溶液中的光降解行为,结果表明,表面活性剂对染料分子具有保护作用,其影响大小为CTAB>TX-100>SDS,分子中有羧基的染料受影响程度最大。在表面活性剂浓度较低时,染料光降解程度随着表面活性剂浓度的增加而增加,但形成胶束后,染料的光降解程度则随着表面活性剂浓度的升高而降低。     

Photophysical studies of some dyes in aqueous solution of triton X-100

The spectral (both absorption and fluorescence) and photoelectrochemical studies of a few selective dyes, namely, anionic erythrosin B, neutral riboflavin and cationic safranin O have been carried out in aqueous solution of triton X-100, a neutral surfactant. The results show that the ionic dyes, erythrosin B and safranin O form 1:1 electron donor-acceptor (EDA) or charge-transfer (CT) complexes with triton X-100 both in the ground and excited states, whereas neutral dye riboflavin in its excited state forms 1:1 complex with triton X-100. In these complexes, the dyes act as electron acceptors whereas triton X-100 acts as an electron donor. The fluorescence spectra of erythrosin B and safranin O in presence of triton X-100 show enhancement of fluorescence intensity with red and blue shifts respectively while riboflavin shows normal quenching of fluorescence. A good correlation has been found among photovoltage generation of the systems consisting of these dyes and triton X-100, spectral shift due to complex formation and thermodynamic properties of these complexes.     

Formation and microstructure transition of F127/TX-100 complex

Formation and structure transition of the complex composed of triblock copolymer F127 and nonionic surfactant TX-100 have been investigated by 1H NMR spectroscopy, dynamic light scattering (DLS), and isothermal titration calorimetry (ITC). Three TX-100 concentration regions are identified, within which TX-100/20 mg/mL F127 complex undergoes different temperature-induced structure transitions. In low concentration region (< 9.42 mM), F127 single molecular species (unimers) wrap around TX-100 micelles forming F127/TX-100 complex with TX-100 micelle as the skeleton at a lower temperature (5 degrees C), and the skeleton transfers to F127 micelle at higher temperature (40 degrees C); in intermediate TX-100 concentration region (9.42-94.85 mM), the skeleton of F127/TX-100 complex transfers from TX-100 micelle successively into F127 micelle and TX-100 micelle again upon heating. The interaction of F127 with TX-100 is saturated in high TX-100 concentration region (> 157.57 mM), and free TX-100 micelles coexist with larger clusters of F127/TX-100 complexes. In addition, TX-100-induced F127/TX-100 complex formation and structure transition are also investigated at constant temperatures. The results show that within 5-10 degrees C, F127 unimers mainly adsorb on the surface of TX-100 micelles just like normal water soluble polymers; in the temperature region of 15-25 degrees C, TX-100 micelles prompts F127 micelle formation. Within 30-40 degrees C, TX-100 inserts into F127 micelles leading to the breakdown of F127 aggregates at higher TX-100 concentrations, and the obtained unimers thread through TX-100 micelles forming complex with TX-100 micelle as skeleton.     

Clouding Behavior and Thermodynamic Study of Nonionic Surfactants in Presence of Additives

The present study investigates the effect of different additives on the cloud point (CP) of nonionic surfactants Triton X-100 (TX-100) and Triton X-114 (TX-114) in aqueous solutions. The thermodynamic parameters of these mixtures were calculated at different additive concentrations. The cloud point of nonionic surfactants TX-100 and TX-114 decreased with the increment of electrolyte concentrations and increased with alcohol concentrations. The standard Gibbs free energy was found to be positive for both the surfactants, whereas the enthalpy and the entropy of the clouding phenomenon were found to be positive with alcohols and negative with electrolytes. The overall clouding process was endothermic for alcohols and exothermic for electrolytes.     

Colorimetric determination of arylamines and sulphonamides by diazotization and coupling in a micellar solution

The use of a micellar solution as a means for improving the colorimetric determination of arylamines by diazotization and coupling is studied. Sodium dodecylsulphate (SDS), Triton X-100 (TX-100) and N-cetylpyridinium chloride (NCPC), together with the diazotizable substances aniline and sulphanilic acid and the coupling agents 1-naphthylamine and N-(1-naphthyl)ethylenediamine are used as model compounds. The protonation constants of the dyes follow the order SDS>H₂O>TX-100>NCPC. In an SDS micellar solution the coupling rate increases greatly, allowing the rapid formation of the protonated dyes in an acetate buffer. Other advantages are the possibility of analysing very non-polar samples and of using a wider range of diazotizable substances and substrates. A procedure for the determination of 10–100 μg of aniline in an SDS micellar solution is proposed. The procedure is applied to the determination of sulphonamides in pharmaceutical preparations.     

Spectral studies of N-nonyl acridine orange in anionic, cationic and neutral surfactants

The spectroscopic and photophysical properties of N-nonyl acridine orange - a metachromatic dye useful as a mitochondrial probe in living cells - are reported in water and microheterogeneous media: anionic sodium dodecylsulfate (SDS), cationic cetyltrimethylammonium bromide (CTAB) and neutral octylophenylpolyoxyethylene ether (TX-100). The spectral changes of N-nonyl acridine orange were observed in the presence of varying amount of SDS, CTAB and TX-100 and indicated formation of a dye-surfactant complex. The spectral changes were also regarded to be caused by the incorporation of dye molecules to micelles. It was proved by calculated values K(b) and f in the following order: K(bTX-100)>K(bCTAB)>K(bSDS) and f(TX-100)>f(CTAB)>f(SDS). NAO binds to the micelle regardless the micellar charge. There are two types of interactions between NAO and micelles: hydrophobic and electrostatic. The hydrophobic interactions play a dominant role in binding of the dye to neutral TX-100. The unexpected fact of the binding NAO to cationic CTAB can be explained by a dominant role of hydrophobic interactions over electrostatic repulsion. Therefore, the affinity of NAO to CTAB is smaller than TX-100. Electrostatic interactions play an important role in binding of NAO to anionic micelles SDS. We observed a prolonged fluorescence lifetime after formation of the dye-surfactant complex tau(SDS)>tau(TX-100)>tau(CTAB)>tau(water), the dye being protected against water in this environment. TX-100 is found to stabilize the excited state of NAO which is more polar than the ground state. Spectroscopic and photophysical properties of NAO will be helpful for a better understanding of the nature of binding and distribution inside mammalian cells.     

Effect of micellar environment on Marcus correlation curves for photoinduced bimolecular electron transfer reactions

Photoinduced electron transfer (ET) between coumarin dyes and aromatic amine has been investigated in two cationic micelles, namely, cetyltrimethyl ammonium bromide (CTAB) and dodecyltrimethyl ammonium bromide (DTAB), and the results have been compared with those observed earlier in sodium dodecyl sulphate (SDS) and triton-X-100 (TX-100) micelles for similar donor-acceptor pairs. Due to a reasonably high effective concentration of the amines in the micellar Stern layer, the steady-state fluorescence results show significant static quenching. In the time-resolved (TR) measurements with subnanosecond time resolution, contribution from static quenching is avoided. Correlations of the dynamic quenching constants (k(q) (TR)), as estimated from the TR measurements, show the typical bell-shaped curves with the free-energy changes (DeltaG(0)) of the ET reactions, as predicted by the Marcus outersphere ET theory. Comparing present results with those obtained earlier for similar coumarin-amine systems in SDS and TX-100 micelles, it is seen that the inversion in the present micelles occurs at an exergonicity (-DeltaG(0)> approximately 1.2-1.3 eV) much higher than that observed in SDS and TX-100 micelles (-DeltaG(0)> approximately 0.7 eV), which has been rationalized based on the relative propensities of the ET and solvation rates in different micelles. In CTAB and DTAB micelles, the k(q) (TR) values are lower than the solvation rates, which result in the full contribution of the solvent reorganization energy (lambda(s)) towards the activation barrier for the ET reaction. Contrary to this, in SDS and TX-100 micelles, k(q) (TR) values are either higher or comparable with the solvation rates, causing only a partial contribution of lambda(s) in these cases. Thus, Marcus inversion in present cationic micelles is inferred to be the true inversion, whereas that in the anionic SDS and neutral TX-100 micelles are understood to be the apparent inversion, as envisaged from two-dimensional ET theory.     

Thermodynamics of non-ionic surfactant Triton X-100-cationic surfactants mixtures at the cloud point

This study investigates the effects of gemini and conventional cationic surfactants on the cloud point (CP) of the non-ionic surfactant Triton X-100 (TX-100) in aqueous solutions. Instead of visual observation, a spectrophotometer was used for measurement of the cloud point temperatures. The thermodynamic parameters of these mixtures were calculated at different cationic surfactant concentrations. The gemini surfactants of the alkanediyl-α-ω-bis (alkyldimethylammonium) dibromide type, on the one hand, with different alkyl groups containing m carbon atoms and an ethanediyl spacer, referred to as “m-2-m” (m = 10, 12, and 16) and, on the other hand, with –C₁₆ alkyl groups and different spacers containing s carbon atoms, referred to as “16-s-16” (s = 6 and 10) were synthesized, purified and characterized. Additions of the cationic surfactants to the TX-100 solution increased the cloud point temperature of the TX-100 solution. It was accepted that the solubility of non-ionic surfactant containing polyoxyethylene (POE) hydrophilic chain was a maximum at the cloud point so that the thermodynamic parameters were calculated at this temperature. The results showed that the standard Gibbs free energy , the enthalpy and the entropy of the clouding phenomenon were found positive in all cases. The standard free energy increased with increasing hydrophobic alkyl chain for both gemini and conventional cationic surfactants; however, it decreased with increasing surfactant concentration.     

Cloud-point extraction of rhodamine 6G by using Triton X-100 as the non-ionic surfactant

Cloud-point extraction (CPE) using the non-ionic surfactant Triton X-100 was used successfully to remove a highly toxic dye, rhodamine 6G (R6G), from water and wastewater. The effects of different analytical parameters such as pH, concentration of Triton X-100 (TX-100) and salts, equilibrium temperature, and incubation time on the efficiency of the extraction of R6G were studied in detail, and optimum conditions for dye extraction were obtained. Thermodynamic parameters including changes in Gibbs free energy, enthalpy, and entropy were also calculated, and these parameters indicated that the CPE of R6G was feasible, spontaneous, and endothermic in the temperature range of 75-95 degrees C. The equilibrium solubilization capacity of TX-100 was found to be 1.10 mmol/mol by using Langmuir isotherm models. No significant interference effects were observed in the presence of phenol and its derivatives, some acidic and basic dyes and most of the anions and cations. It was concluded that the CPE process described in this paper can be an alternative technique for removal of dyes and other pollutants from waters and wastewaters.     

Surfactant assisted hydrothermal synthesis of SnO nanoparticles with enhanced photocatalytic activity

SnO nanoparticles have been successfully synthesized in the presence of Triton-X 100 (TX-100) surfactant via hydrothermal method for the first time, and the photocatalytic activity under UV and visible light irradiation for the degradation of Methylene Blue (MB) and Rhodamine B (RdB) organic textile dyes was investigated. The structural, morphological and chemical characterizations were investigated by using X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), selected area electron diffraction (SAED), energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), Fourier Transform Infrared Spectroscopy (FTIR), UV–vis. diffuse reflectance spectroscopy (UV–vis DRS) and photoluminescence (PL) analysis. The results reveal that the addition of surfactant, TX-100, in the precursor solutions leads to reduction in crystallite size with significant changes in morphological structure of SnO nanoparticles. The synthesized SnO nanoparticles show excellent photocatalytic activity under UV or visible light irradiation. MB and RdB dyes degraded completely under UV irradiation after 90 and 150 min, respectively. Also, MB and RdB dyes degraded only 150 min later under visible light illumination with a little amount of photocatalyst (0.8 g/L). Hence, this work explores the facile route to synthesizing efficient SnO nanoparticles for degrading organic compound under both UV and visible light irradiations.     

Oxidation of Methionine by Colloidal MnO2 in Aqueous and Micellar Media: A Kinetic Study

The oxidation of methionine by freshly prepared colloidal manganese dioxide in aqueous as well as micellar media was studied spectrophotometrically at 35°C. The reaction between methionine and MnO₂ in both media exhibits 1:1 stoichiometry (methionine:MnO₂). The oxidation reaction is first order with regard to the MnO₂ concentration, but is fractional-order in the methionine concentration and HClO₄ concentrations. A catalytic effect of nonionic surfactant TX-100 on the rate of oxidation was observed and reaction rate was found to be proportional to {k′ + k″ [TX-100]}, where k′ and k″ are the rate constants in absence and presence of surfactant, respectively. The use of surfactant micelles is highlighted as, in favorable cases; the micelles help the redox reactions by bringing the reactants in a close proximity through hydrogen bonding. The oxidation reaction in aqueous and micellar media is shown to proceed via methionine–MnO₂ and methionine–MnO₂–TX-100 complexes, respectively, which decomposes slowly in a rate determining step to give methionine sulfoxide as the product. A suitable mechanism is proposed for these observations.     

Absorption spectra of nitroanilines in micellar solution--II

The absorption spectra of nitroanilines (o-, m- and p-) in aqueous and nonaqueous solution of neutral surfactant-Triton X-100 (TX-100) reveal many interesting phenomena. Nitroanilines and TX-100 behave as electron acceptor and donor, respectively, in both media during charge-transfer (CT) complex formation though water plays an important role in aqueous media. The thermodynamic and spectrophotometric parameters of nitroanilines-TX-100 interactions in two media have been determined and the electron accepting capability among the nitroanilines have been also established. In addition to this, role of surface in CT interaction, the site of CT interaction, intensity and stability of CT interaction between nitroanilines and TX-100 have been pointed out.     

Micellization of sodium dodecyl sulfonate and Triton X-100 in polyacrylamide water solution studied by 1H NMR relaxation and two-dimensional nuclear overhauser enhancement spectroscopy

Micellization of Triton X-100 (TX-100) and sodium dodecyl sulfonate (SDSN) in the presence of partially hydrolyzed polyacrylamide (PAAM) was studied by ¹H NMR spin–spin and spin–lattice relaxation. Relaxation experiment results show that TX-100 behaves differently from SDSN in micellization in the presence of PAAM. PAAM causes a decrease in the critical micellar concentration of SDSN, while it has no influence on the critical micellar concentration of TX-100. The lack of cross peaks between protons of PAAM and those of TX-100 and SDSN in the 2D nuclear Overhauser enhancement spectroscopy (NOESY) spectra confirms self-aggregation of TX-100 and SDSN in the presence of PAAM. The identity of each of the corresponding interproton distances of TX-100 with and without the addition of PAAM further confirms the formation of normal TX-100 micelles in the presence of PAAM. Besides, the distances between protons on the hydrophilic and hydrophobic chains in TX-100 micelles, calculated from the 2D NOESY spectra, are remarkably shorter than those for an extended hydrophilic poly(oxyethylene) chain. This implies that the hydrophilic chain is curled upon micellization. Received: 2 February 1999 Accepted in revised form: 2 June 1999     

Complexes of functionalized dipyrido[3,2-a:2',3'-c]-phenazine: a synthetic, spectroscopic, structural, and density functional theory study

The ligands 11-bromodipyrido[3,2-a:2',3'-c]phenazine and ethyl dipyrido[3,2-a:2',3'-c]phenazine-11-carboxylate have been prepared and coordinated to ruthenium(II), rhenium(I), and copper(I) metal centers. The electronic effects of substitution of dipyrido[2,3-a:3',2'-c]phenazine (dppz) have been investigated by spectroscopy and electrochemistry, and some photophysical properties have been studied. The crystal structures of [Re(L)(CO)(3)Cl] (L = ethyl dipyrido[3,2-a:2',3'-c]phenazine-11-carboxylate or 11-bromodipyrido[3,2-a:2',3'-c]phenazine) are presented. Density functional theory calculations on the complexes show only small deviations in bond lengths and angles (most bonds within 0.02 Angstroms, most angles within 2 degrees) from the crystallographic data. Furthermore, the vibrational spectra of the strongest Raman and IR bands are predicted to within an average 6 cm(-1) for the complexes [Re(L)(CO)(3)Cl] and [Cu(L)(triphenylphosphine)(2)]BF(4) (in the 1000-1700 cm(-1) region). Spectroscopic and electrochemical evidence suggest that reduction of the complex causes structural changes across the entire dppz ligand. This is unusual as dppz-based ligands typically have electrochemical properties that suggest charge localization with reduction on the phenazine portion of the ligand. The excited-state lifetimes of the complexes have been measured, and they range from ca. 200 ns for the [Ru(L)(2,2'-bipyridine)(2)](PF(6))(2) complexes to over 2 mus for [Cu(11-bromodipyrido[3,2-a:2',3'-c]phenazine)(PPh(3))(2)](BF(4)) at room temperature. The emission spectra suggest that the unusually long-lived excited states of the copper complexes result from metal-to-ligand charge transfer (MLCT) transitions as they are completely quenched in methanol. Electroluminescent films may be fabricated from these compounds; they show MLCT state emission even at low doping levels [<0.1% by weight in poly(vinylcarbazole) polymer matrix].     

Mono and binuclear Ag(I), Cu(II), Zn(II) and Hg(II) complexes of a new azo-azomethine as ligand: synthesis, potentiometric, spectral and thermal studies

New azo-azomethine dyes were prepared by reaction of p-aminobenzoic acid, o-anisidine, o-nitroaniline, and p-bromoaniline with salicylaldehyde respectively to form azo compounds and then condensation by urea to form 4-(R-arylazo 2-salicylaldene)-urea azo-azomethine derivatives (I(a-d)). The complexes of these ligands with Ag(I), Cu(II), Zn(II) and Hg(II) metal ions were prepared. The structure of the free ligands and their complexes were characterized by using elemental analysis (C, H, N), (1)H NMR, IR and UV-Vis-spectra. The proton dissociation constants of the ligands and the stability constant of their complexes have been determined potentiometrically in 40% (v/v) alcohol-water medium as well as the stoichiometry of complexes were determined conductometrically. The data reveal that the stoichiometries for all complexes were prepared in molar ratios (1:1) and (1:2) (M:L). The electrolytic and nonelectrolytic natures of the complexes were assigned based on molar conductance measurements. The thermogravimetric (TG), and differential thermal analyses (DTA) were studied in nitrogen atmosphere with heating rate 10°C/min. The kinetic and thermodynamic parameters for thermal decomposition of complexes have been calculated by graphical method using Coats-Redfern (CR) method.     

Energy transfer--a tool for probing micellar media

The non-ionic polyoxyethylene chain-containing surfactant Triton X-100 (TX-100) forms well-defined micelles and reverse micelles in aqueous and hydrocarbon media, respectively. Nonradiative energy transfer between two charged fluorescent dyes, fluorescein (FL) and acridine orange (AO) has been used to probe the micelles and reverse micelles of TX-100. In the energy transfer system employed, FL acts as the donor and AO as the acceptor. This is borne out by the fluorescence spectral data. Time-resolved studies further corroborate the steady-state results. As the fluorescence emission spectra of the two dyes show a considerable amount of overlap, they are resolved into individual donor and acceptor components using the principal component analysis (PCA) method. This study also focuses on the more important role played by hydrophobic forces (compared with electrostatic interactions) in promoting energy transfer between charged species in micellar media.