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.     

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.     

Electrochemical behavior of anthraquinone in aqueous solution in presence of a non-ionic surfactant

Cyclic voltammetric behavior of anthraquinone in aqueous medium has been studied in presence of a non-ionic surfactant, Triton X-100 (TX-100) using sodium salt of anthraquinone-2-sulphonic acid (AQS) as the electro-active species. When cathodic potential is applied, the anthraquinone (AQ) group of AQS is reduced to its dianion. In the reverse scan, the oxidation of AQ²⁻ gives AQ. The electrochemical behavior shows a profound influence from the dissolved state of TX-100 in aqueous media. Spectrophotometric results indicate interaction between AQ and TX-100. A CEC (chemical–electrochemical–chemical) mechanism with the electrochemical reaction coupled with preceding interaction of AQS with TX-100 and following protonation reaction of reduced AQ has been proposed.     

Studies on the molecular interaction of phenazine dyes with Triton X-100

The absorption spectra of phenazine dyes such as phenosafranin (PSF), safranin-O (Saf-O), and safranin-T (Saf-T) in aqueous solution of Triton X-100 (TX-100) show that phenazine dyes form 1:1 charge-transfer (CT) or electron-donor-acceptor (EDA) complex with TX-100. The photogalvanic and photoconductivity studies also support the above interaction. From the thermodynamic, spectrophotometric and photophysical parameters of these complexes, the abilities of dyes to accept electron are found to be in the order: PSF > Saf-O > Saf-T. There is a good correlation among the spectral and thermodynamic properties of these complexes.     

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.     

Unique liquid crystal behavior in water of anionic fluorocarbon-hydrocarbon hybrid surfactants containing oxyethylene units

In this present study, we report on new methodology for determining the Critical Micelle Concentration (CMC) of a neutral surfactant Triton X-100 (TX-100) both in aqueous and non-aqueous media based on a non-invasive approach. The presence of the phenyl moiety of TX-100 was made use of as an intrinsic fluorophore and steady-state and time-resolved spectroscopy has been used to characterize the micellar systems. There are reports that external fluorophores may bring about some structural changes in the systems and the perturbations caused by these fluorophores in micellar systems may affect the shape and size of the micelles. We have also used three probes namely ANS, Rh6G and C-480 to determine the CMC of TX-100 both in aqueous and non-aqueous media and the values obtained agree very well with those estimated by the non-invasive techniques. Interestingly, for our system, we have conclusively proved that the external probes have almost no effect on the process of micellization. Although, both the invasive and non-invasive technologies report almost the same values of CMC, yet the latter methodology is free from any external perturbations and this makes the micellar/reverse micellar system, which may interact with other biological systems less prone to any physical distortions.     

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.     

Suitable combination of promoter and micellar catalyst for chromic acid oxidation of formaldehyde to formic acid in aqueous acid media at room temperature

The chromic acid oxidation of formaldehyde in micellar solution of sodium dodecyl sulphate (SDS)/TX-100 at room temperature has been investigated under pseudo first-order condition. Heterocyclic bases such as picolinic acid (PA), 2,2′-bipyridine (bipy), 1,10-phenanthroline (phen) have been employed which acts as a promoter. The rate of this oxidation reaction increased 50 times by combination of bipy and SDS micelle compared to rate in pure aqueous media. Here, we can avoid hazardous organic solvents, high pressure and temperature which are required for conventional preparation of formic acid. The catalytic effect of SDS/TX-100 micelle has been explained.     

Absorption spectra of 7, 7, 8, 8-tetracyanoquinodimethane in micellar solutions.

The absorption spectra of 7, 7, 8, 8-tetracyanoquinodimethane (TCNQ) with nonionic surfactant. Triton X-100, anionic surfactant, SLS and cationic surfactant, CTAB in aqueous and nonaqueous media have been studied. The spectral studies show that TCNQ forms 1:1 charge-transfer (CT) complex with Triton X-100 in both media. The aqueous solution of TCNQ shows an absorption maxima at 610 nm, which is unperturbed in the presence of SLS but is shifted to 650 nm in the presence of CTAB, indicating the interaction of TCNQ with the cationic surfactant and not with the anionic surfactant. In addition to this, the stability of TCNQ-Triton X-100 complex has been determined and the probable site of CT interaction has been pointed out.     

Temperature induced phase separation of luminescent silica nanoparticles in Triton X-100 solutions

The aggregation and cloud point behavior of Tb(III)-doped silica nanoparticles has been studied in Triton X-100 (TX-100) solutions at various concentration conditions by fluorimetry, dynamic light scattering, electrophoresis and transmission electron microscopy methods. The temperature responsive behavior of nanoparticles is observed at definite concentration of TX-100, where the aggregation of TX-100 at the silica/water interface is evident from the increased size of the silica nanoparticles. The reversible dehydration of TX-100 aggregates at the silica/water interface should be assumed as the main reason of the temperature induced phase separation of silica nanoparticles. The distribution of nanoparticles between aqueous and surfactant rich phases at the phase separation conditions can be modified by the effect of additives.     

Dispersed Molecular Aggregates

Colloidal dispersions of tungstic acid (H(2)WO(4)) have been prepared in water/(TX-100+alkanol)/n-heptane water-in-oil microemulsion media by reacting Na(2)WO(4) with HCl. The effects of alkanol chain length, TX-100/alkanol mass ratio, temperature, and dilution at different [water]/[TX-100] mole ratios (omega) have been studied by the dynamic light scattering technique. The formation of H(2)WO(4) in the microwater pool has been established by FT-IR measurements. The particle sizes and shapes in microemulsion media and in isolated states have been measured by TEM and SEM techniques. The enthalpy of formation of H(2)WO(4) in the water pool of the microemulsions has also been determined microcalorimetrically. Copyright 2001 Academic Press.     

A probable hydrogen-bonded Meisenheimer complex: an unusually high S(N)Ar reactivity of nitroaniline derivatives with hydroxide ion in aqueous media

Observations show that nitroanilines exhibit an unusually high S(N)Ar reactivity with OH(-) in aqueous media in reactions that produce nitrophenols. S(N)Ar reaction of 4-nitroaniline (2a) in aqueous NaOH for 16 h yields 4-nitrophenol (4a) quantitatively, whereas a similar reaction of 4-nitrochlorobenzene (1a) gave 4a in 2% yield together with recovered 1a in 97%, suggesting that the leaving ability of the NH(2) group far surpasses that of Cl under these conditions. An essential feature of S(N)Ar reactions of nitroanilines is probably that the NH(2) leaving group participates in a hydrogen-bonding interaction with H(2)O. Density functional theory (DFT) calculations for a set of 4-nitroaniline, OH(-), and H(2)O suggest a possible formation of a Meisenheimer complex stabilized by hydrogen-bonding interactions and a six-membered ring structure. The results obtained here contrast with conventional S(N)Ar reactivity profiles in which nitroanilines are nearly unreactive with nucleophiles in organic solvents.     

Sono-electroanalysis of copper: enhanced detection and determination in the presence of surfactants

Surfactant adsorption has been shown to have a passivating effect on the electrode surface during anodic stripping voltammetric measurements. In the present work the feasibility of sono-anodic stripping analysis for the determination of copper in aqueous media contaminated with surfactant has been studied at an unmodified bare glassy carbon electrode. We illustrate the deleterious effect of three common surfactants, sodium dodecyl sulfate (SDS), dodecyl pyridinium chloride (DPC) and Triton-X 100 (TX-100) on conventional electroanalysis. The analogous sono-electroanalytical response was investigated for each surfactant at ultrasound intensities above and below the cavitation threshold. The enhancement in the stripping signal observed is attributed to the increased mass transport due to acoustic streaming and above the cavitation threshold the intensity of cavitational events is significantly increased leading to shearing of adsorbed surfactant molecules from the surface. As a result accurate analyses for SDS concentrations up to 100 ppm are possible, with analytical signals visible in solutions of SDS and TX-100 of 1000 ppm. Analysis is reported in high concentration of surfactant with use of sono-solvent double extraction. The power of this technique is clearly illustrated by the ability to obtain accurate measurements of copper concentration from starting solutions containing 1000 ppm SDS or TX-100. This was also exemplified by analysis of the low concentration 0.3 microM Cu(II) solution giving a percentage recovery of 94% in the presence of 1000 ppm SDS or TX-100.     

Effect of addition of hydrophilic ionic liquid 3-methyl-1-pentylimidazolium tetrafluoroborate ([C5mim][BF4]) on an aqueous solution of triton X-100

The effect of addition of 3-methyl-1-pentylimidazolium tetrafluoroborate ([C₅mim][BF₄]) on the micellization of a nonionic surfactant, Triton X-100 (TX-100), has been investigated. The techniques employed to study the aggregation behavior are fluoremetry, dynamic light scattering (DLS), and transmission electron microscopy (TEM) and the concentration range covered is 0–2?wt% [C₅mim][BF₄]. The probes, viz. pyrene and pyrene-1-carboxaldehyde (PyCHO), have been used for fluorescence analysis. According to the findings, the addition of pentyl-chained ionic liquid (IL) to aqueous TX-100 results in a dramatic increase in critical micelle concentration (cmc) decrease in micellar size, and aggregation number pointing toward an overall “unfavorable” aggregation process.     

Oxidation of nonionic surfactants with molecular oxygen

Kinetic regularities are studied for the air oxidation of surfactants that are widely used in the food industry, such as natural phosphatidylcholine (egg lecithin, PC) and synthetic nonionic surfactants Triton X-100 (ТХ-100), Tween 65, and Pluronic F68. Azobis(amidinopropane)-dichloride-initiated oxidation of these surfactants in an aqueous medium at 37°C develops via the chain free-radical mechanism. The chain length is equal to 5–10 units, depending on the initiator-to-surfactant concentration ratio. The rate of surfactant oxidation in an aqueous medium is proportional to the rate of radical initiation. At the same mass concentrations of the reagents, the rate of PC oxidation is several times higher than the oxidation rates of the other surfactants. The addition of TX-100 to PC liposomes decelerates the oxidation; i.e., TX-100 plays the role of an antioxidant for PC. The superposition of the oxidation rates of individual and mixed PC and TX-100 with the sizes of the microaggregates formed in their aqueous solutions shows that the antioxidation action of TX-100 is realized via the formation of a protective layer composed of its ethylene oxide groups, which shields PC liposomes from radicals, which are initiated in the bulk of an aqueous phase due to the decomposition of azobis(amidinopropane) dichloride.     

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.     

Mechanism of the oxidation of d-glucose onto colloidal MnO2 surface in the absence and presence of TX-100 micelles

Aqueous colloidal manganese dioxide (MnO₂) was prepared via titration by using potassium permanganate and sodium thiosulphate in aqueous neutral medium. The kinetics of oxidation of d-glucose onto the surface of colloidal MnO₂ have been studied spectrophotometrically. The results show that the rate of initial stage (nonautocatalytic path) increases with increasing the [d-glucose], [H⁺], and temperature and also upon addition of nonionic surfactant Triton X-100 (TX-100), which indicates that the surfactant enhances the concentration of d-glucose at the surface of the colloidal MnO₂. Hydrogen bonding interaction seemingly arises between –OH groups of d-glucose and oxygen of the ether linkages of polyoxyethylene chain of TX-100. A possible mechanism of the oxidative degradation of d-glucose is discussed in terms of d-glucose/TX-100 and colloidal MnO₂ interaction.     

Effect of added ionic liquid on aqueous Triton X-100 micelles

Addition of ionic liquids to aqueous surfactant solutions can alter/modify physicochemical properties of such systems in favorable manner. Changes in the properties of aqueous solutions of a useful nonionic surfactant Triton X-100 (TX-100) are assessed upon addition of 2.1 wt% of a common and popular ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate (bmimPF6). It is shown that the solubility of 'hydrophobic' bmimPF6 in aqueous TX-100 increases with TX-100 concentration. This observation combined with the conductivity data strongly indicates partitioning of bmimPF6 into TX-100 micellar phase. Behavior of a variety of molecular absorbance [methyl orange, phenol blue, and N,N-diethyl-4-nitroaniline] and fluorescence [phenyl on the TX-100, pyrene, pyrene-1-carboxaldehyde, 2-(p-toluidino)naphthalene-6-sulfonate, and 1,3-bis-(1-pyrenyl)propane] probes further confirm this observation. Statistically insignificant increase in critical micelle concentration (cmc) and decrease in aggregation number (N(agg)) of TX-100 micelles are observed upon addition of 2.1 wt% bmimPF6. Based on the overall data, it is inferred that ionic liquid bmimPF6 partitions into the TX-100 micellar phase; presence of bmimPF6 both close to the core as well as in the palisade layer of TX-100 micelles is suggested. Presence of favorable interactions (e.g., H-bonding, dipole-induced dipole, among others) between bmimPF6 and TX-100 is proposed to be the reason for these observations.     

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.     

Interaction between Anionic Dye ECAB,Micelle of Triton X-100 in Aqueous Solution and Hemimicelie at Solid/Liquid Interface

Abstract

Interaction between dye (ECAB), nonionic surfactant (TX-100) micelle in aqueous solution and TX-100 hemimicelie at solid (SiO₂)/liquid interface has been investigated quantitatively. There are linear relationships between concentrations of free ECAB(C_a), ECAB bound with TX-100 micelles in solution(C_m) and ECAB bound with TX-100 hemimicelles at interface of solid/liquid(C_hm). The slopes of the three straight lines are 0.32 for C_hm～C_a -1.32 for C_m～C_a and -1.00 for (C_m+C_hm～C_a respectively. The linear relationships can be described by three linear equations as follows: C_hm=0.32 (C_a?O.88×10^?5),C_m.=4.0×10^?5-l.33 C_a and C_hm+C_m=3.742×l0^?5-C_a,. It is inferred that the interaction between ECAB, TX-100 micelles and TX-100 hemimicelles is essentially partition of ECAB molecules in solution, TX-100 micelles and hemimicelles. The concentration of ECAB bound with TX-100 micelles well as electronic repulsion. Additionally, A quantitative method to determine adsorbance of surfactant TX-100 on silica gel by spectroscopy in coadsorption conditions of dye (ECAB) and TX-100 was proposed.