Micellization and surface activity of Triton X-100 in water–orthophosphoric medium

The adsorption isotherms of Triton X-100 for air/water–orthophosphoric acid interfaces were determined by the stripping method. The surface chemical parameters, Γ_max, F and ΔG°_A, and the aggregation ones, CMC and the ΔG_M, are determined in different H₂O/H₃PO₄ mixtures. For concentrations higher than 4 M, the values of the CMC, ΔG_M, Γ_max and ΔG°_A increase with increasing acid concentrations due to the occurring changes in the medium structure. ©2000 Académie des sciences / Éditions scientifiques et médicales Elsevier SASsurface tension / non-ionic surfactant / micellization / orthophosphoric acid     

Influences of Triton X-100 on Hemoglobin Behaviors in Hemoglobin/Acyclovir/Triton X-100/H2O System

The influences of Triton X-100 on hemoglobin （Hb） behaviors were studied by the methods of UV-Vis spectrum, fluorescence spectrum, HPLC, conductivity, zeta potential and negative-staining transmission electron microscope in Hb/acyclovir/Triton X-100/H2O system. With the increase of Triton X-100 concentration in the system, the percentage of the free acyclovir increased from 58%--63% to 90%--94%. The static quenching constant and the association number of acyclovir to Hb decreased. The fluorescence spectrum, conductivity, zeta potential, fluorescence polarization and negative-staining morphology of Hb tended to recover to those of the original state of Hb in the same concentration of Hb. The interaction between Triton X-100 and Hb is stronger than that between acyclovir and Hb. Most Triton-X-100 was associated with Hb at low Triton X-100 concentration. But the interaction of Triton X-100 with Hb was apparently dominant in high Triton X-100 concentration. The Hb structure was unfolded and finally denatured.     

Catalyzed oxidation of 2,6-dimethylphenol in Triton X- 100 micellar solution

The oxidative coupling reaction of 2,6-dimethylphenol with H2O2 catalyzed by a copper(Ⅱ) Schiff complex in aqueous and Triton X-100 micellar solution under mild conditions was investigated. The kinetics of formation of 3,3′,5,5′-tetramethyl-4,4′-diphenoquinone (DPQ) was studied. Rate constant k2 were obtained. The optimum pH for DPQ generation reaction is 7.25. The main product was DPQ in aqueous buffer solution, but PPE and the oxidized products of PPE remained in Triton X-100 micellar solution.     

Determination of β-sitosterol and cholesterol in oils after reverse micelles with Triton X-100 coupled with ultrasound-assisted back-extraction by a water/chloroform binary system prior to gas chromatography with flame ionization detection

Ultrasonic back-extraction of Triton X-100 reverse micelles by a water/chloroform binary system and gas chromatography with flame ionization detection (GC-FID) was developed for extraction and determination of β-sitosterol and cholesterol in soybean and sunflower oil samples. After the homogenization of the oil samples with Triton X-100, an aliquot of 200 μL of methanol was added to the samples to form two phases. The clear Triton X-100 extract obtained by centrifugation was treated with a mixture of water (1000 μL) and chloroform (300 μL) for back-extraction of the analytes into the chloroform phase by ultrasonication. After centrifugation, the sedimented chloroform layer was withdrawn easily by a microsyringe and directly injected into the GC-FID system. The influence of several important parameters on the extraction efficiencies of the analytes was evaluated. Under optimized experimental conditions, the calibration graphs were linear in the range of 1.0–30.0 mg L⁻¹ with coefficient of determination more than 0.994 for both analytes. The method detection limit values were in the range of 0.2–0.7 mg L⁻¹. The lower limit of quantification values were in the range of 0.7–2.4 mg L⁻¹. Intra-day relative standard deviations were in the range of 1.0–2.7%. This procedure was successfully applied with satisfactory results to the determination of β-sitosterol and cholesterol in spiked oil samples. The relative mean recoveries of oil samples ranged from 93.6% to 105.0%.     

Steric Considerations in Supramolecular Inclusion of Modified β-cyclodextrins with Triton X-100 and α-bromonaphthalene

Supramolecular inclusion of modified β-cyclodextrin (β-CD) with Triton X-100 (TX) and α-bromonaphthalene (BN) was studied by fluorescence and phosphorescence measurements. Major differences were observed in the magnitude of the apparent stability constants and quenching constants of the inclusion complexes. Methyl substitution on the rims of β-CD increased the binding of TX with β-CD but was unfavorable to the protection of the phenyl group of TX from fluorescence quenching and further accommodation of BN for steric considerations. According to the overall molecular size of β-CD, TX and BN, further inclusion of BN in the cavity of β-CD occupied by TX may force the flexible tert-octyl chain of TX to deform to a greater extent and close packing complexes were obtained. Phosphorescence of BN arising from intermolecular energy transfer between BN and the phenyl group of TX was observed when the phenyl group of TX was irradiated. In the case of heptakis(2,6-di-O-methyl)-β-CD, BN failed to penetrate into the cavity because of the steric hindrance of the methyl substituents at the rim of the β-CD cavity.     

Synthesis and characterization of nanosized NiO2 and NiO using Triton® X-100

Nanosized NiO₂ particles with an average diameter of 15 nm are prepared by treating of Ni(NO₃)₂ · 6H₂O with an aqueous solution of KClO in the presence of Triton® X-100. This black fine powder of nickel peroxide was characterized by XRD diffraction, energy dispersive spectroscopy (EDS) and scanning electron microscopy (SEM). The as-prepared NiO₂ can be easily transformed to nanosized NiO merely by washing it with acetone. The obtained NiO has an average diameter of 40 nm and was characterized by the same means used for NiO₂. The nanoparticles of NiO₂ and NiO were obtained in high yields and purities.      

Triton X-100-stabilized "oil-in-water" emulsions as suitable media for alkalimetric determination of hydrophobic organic acids

The protolytic properties of fat row carbonic acids in Triton X-100-stabilized "oil-in-water" (O/W) emulsions were studied. The differential influence of emulsions on the force of acids was shown to depend on the length of the hydrocarbon radical. The conditions for separate alkalimetric determinations of acids with different hydrophobicities in their mixtures using emulsions stabilized by non-ionic surfactant were suggested. The procedure for the determination of 4-chloro- N-(2-furilmethyl)-5-sulfamoylanthranilic acid (furosemide) main substance content in pharmaceuticals using Triton X-100-stabilized emulsion was proposed.     

Micelle–monomer equilibria in solutions of ionic surfactants and in ionic–nonionic mixtures: A generalized phase separation model

On the basis of a detailed physicochemical model, a complete system of equations is formulated that describes the equilibrium between micelles and monomers in solutions of ionic surfactants and their mixtures with nonionic surfactants. The equations of the system express mass balances, chemical and mechanical equilibria. Each nonionic surfactant is characterized by a single thermodynamic parameter — its micellization constant. Each ionic surfactant is characterized by three parameters, including the Stern constant that quantifies the counterion binding. In the case of mixed micelles, each pair of surfactants is characterized with an interaction parameter, β, in terms of the regular solution theory. The comparison of the model with experimental data for surfactant binary mixtures shows that β is constant — independent of the micelle composition and electrolyte concentration. The solution of the system of equations gives the concentrations of all monomeric species, the micelle composition, ionization degree, surface potential and mean area per head group. Upon additional assumptions for the micelle shape, the mean aggregation number can be also estimated. The model gives quantitative theoretical interpretation of the dependence of the critical micellization concentration (CMC) of ionic surfactants on the ionic strength; of the CMC of mixed surfactant solutions, and of the electrolytic conductivity of micellar solutions. It turns out, that in the absence of added salt the conductivity is completely dominated by the contribution of the small ions: monomers and counterions. The theoretical predictions are in good agreement with experimental data.     

Interactions of surfactants in nonionic/anionic reverse hexagonal mesophases and solubilization of α-chymotrypsinogen A

In an attempt to form H_II mesophases at room temperature we prepared lyotropic liquid crystals with two surfactants of the same lipophilic tails (glycerol monooleate, GMO, and oleyl lactate, OL) but differing in the size and charge of the headgroups.Increasing OL concentration significantly affected the hydration of the headgroups and subsequently the lipids packing. At low OL content the cubic mesophase was formed, while at higher OL contents the formation of hexagonal mesophase was favored. It was assumed that OL competed on the water binding, tuning the headgroups’ curvature and the packing parameter inducing the formation of reverse hexagonal mesophase. It was detected that cubic mesophase transformed upon heating to hexagonal structures. The hexagonal mesophases, which were formed both immediately after preparation and after aging, remained stable at elevated temperatures.α-Chymotrypsinogen was solubilized into the obtained LLCs at relatively high concentration (up to 1 wt%). The lattice parameter of the host LLCs exhibited a decrease as a function of the protein content. This process was assigned to partial dehydration of the GMO polar moieties in favor to CTA hydration.Generally speaking, the present study indicated that adding anionic to nonionic lipid is highly beneficial to gain additional compositional and structural characteristics of LLCs.     

Fluorescence quenching of eosin upon adsorption by colloidal silver mediated in aqueous solution and reverse micelles

The optical effects of the adsorption of eosin on the colloidal silver particle have been investigated in aqueous solutions. It was found that upon adsorption the fluorescence of eosin was effectively quenched. This was explained as the photoinduced interfacial electron transfer from the excited singlet state of eosin to the silver particle. Decreasing pH of the solution favors the adsorption of eosin and so enhances the fluorescence quenching. For comparison, the fluorescence quenching in reverse micelles was also investigated. The quenching behavior was much different from that mediated in aqueous solution. This was attributed to the unique microenvironment of reverse micelles.     

Temperature-induced phase separation in pseudoternary mixtures of Triton X-100–butanol–kerosene–water

The transparent Winsor IV domain in the phase diagram of the mixtures of emulsifier (Triton X-100 and butanol), oil (kerosene), and water is found to be 34% of the total phase diagram in presence of emulsifier with surfactant:cosurfactant::1:1, and is water dominant. Increase in cosurfactant/surfactant ratio inverts the Winsor IV domain to become oil rich. The plot of conductance of the microemulsions prepared by substituting water by brine against water content depicts the existence of three distinct phases like oil-in-water, bicontinuous, and water-in-oil microemulsion in the phase diagram. The phase contrast micrographs of the mixtures of different compositions in these three different phases reveal the existence of microdroplets of oil dispersed in water and water dispersed in oil. Further, the dynamic light scattering studies of these solutions reveal an inhomogeneity in the size distribution of the droplets. A temperature-induced clouding in the microemulsion domain leading to phase separation has been observed. Additives like glucose, sucrose, and sodium chloride decrease the cloud point (CP), while addition of ammonium thiocyanate increases it. A quantitative relationship of the clouding temperature with the composition of the microemulsion has been established. With increase in oil and emulsifier, the cloud point of the microemulsion increases. The separated phases after the clouding have been used for preconcentration of water-soluble metal ions as well as oil-soluble dyes. The turbid systems on heating led to separation into three isotropic phases which are found to be stable at ambient temperature. The stability of these phases is ascribed to the formation of stable microemulsions by mass transfer from one phase to other.     

Do ionic charges in ESI MS provide useful information on macromolecular structure?

Multiple charging is an intrinsic feature of electrospray ionization (ESI) of macromolecules. While multiple factors influence the appearance of protein ion charge state distributions in ESI mass spectra, physical dimensions of protein molecules in solution are the major determinants of the extent of multiple charging. This article reviews the information that can be obtained by analyzing ionic charge state distributions in ESI MS, as well as potential pitfalls and limitations of this powerful technique. We also discuss future areas of growth with particular emphasis on applications in structural biology, biotechnology (protein-polymer conjugates), and nanomedicine.     

Mutual influence of cetyltrimethylammonium bromide and Triton X-100 on their adsorption at the water–air interface

On the basis of surface tension values of the aqueous solution of cetyltrimethylammonium bromide (CTAB) and Triton X-100 (TX-100) mixtures measured at 293 K as a function of CTAB or TX-100 concentration at constant TX-100 or CTAB concentration, respectively, the real surface area occupied by these surfactants at the water–air interface was established which is inaccessible in the literature. It appeared that at the concentration of the CTAB and TX-100 mixture in the bulk phase corresponding to the unsaturated monolayer at the water air-interface this area is the same as in the monolayer formed by the single surfactant at the same concentration as in the mixture. In the saturated mixed monolayer at this interface the area occupied by both surfactants is lower than that in the single surfactant monolayer corresponding to the same concentration in the aqueous solution. However, the decrease of the CTAB adsorption is lower than that of TX-100 and the total area occupied by the mixture of surfactants is also lower than that of the single one. The area of particular surfactants in the mixed saturated monolayer changes as a function of TX-100 and CTAB mixture concentration and at the concentrations close to CMC or higher the area occupied by both surfactants is the same. The changes of the composition of the mixed surface monolayer are connected with the synergetic effect in the reduction of the water surface tension by the adsorption of CTAB and TX-100 at the water–air interface. This effect was confirmed by the values of the standard Gibbs free energy of adsorption of both individual surfactants and their mixtures with different compositions in the bulk phase determined by using the Langmuir equation if RT instead of nRT was applied in this equation.     

What can you learn from a molecular probe? New insights on the behavior of C343 in homogeneous solutions and AOT reverse micelles

The behavior of C343, a common molecular probe utilized in solvation dynamics experiments, was studied in homogeneous media and in aqueous and nonaqueous reverse micelles (RMs). In homogeneous media, the Kamlet and Taft solvatochromic comparison method quantified solute-solvent interactions from the absorption and emission bands showing that the solvatochromic behavior of the dye depends not only on the polarity of the medium but also on the hydrogen-bonding properties of the solvent. Specifically, in the ground state the molecule displays a bathochromic shift with the polarity polarizability (pi) and the H-bond acceptor (beta) ability of the solvents and a hypsochromic shift with the hydrogen donor ability (alpha) of the media. The carboxylic acid group causes C343 to display greater sensitivity to the beta than to the pi polarity parameter; this sensitivity increases in the excited state, while the dependence on alpha vanishes. This demonstrates that C343 forms a stable H-bond complex with solvents with high H-bond acceptor ability (high beta) and low H-bond donor character (low alpha). Spectroscopy in nonpolar solvents reveals J-aggregate formation. With information from the Kamlet-Taft analysis, C343 was used to explore RMs composed of water or polar solvents/sodium 1,4-bis-2-ethylhexylsulfosuccinate (AOT)/isooctane using absorption, emission, and time-resolved spectroscopies. Sequestered polar solvents included ethylene glycol (EG), formamide (FA), N,N-dimethylformamide (DMF), and N,N-dimethylacetamide (DMA). Dissolved in the AOT RM systems at low concentration, C343 exists as a monomer, and when introduced to the RM samples in its protonated form, C343 remains protonated driving it to reside in the interface rather than the water pool. The solvathochromic behavior of the dye depends the specific polar solvent encapsulated in the RMs, revealing different types of interactions between the solvents and the surfactant. EG and water H-bond with the AOT sulfonate group destroying their bulk H-bonded structures. While water remains well segregated from the nonpolar regions, EG appears to penetrate into the oil side of the interface. In aqueous AOT RMs, C343 interacts with neither the sulfonate group nor the water, perhaps because of intramolecular H-bonding in the dye. DMF and DMA interact primarily through dipole-dipole forces, and the strong interactions with AOT sodium counterions destroy their bulk structure. FA also interacts with the Na+ counterions but retains its H-bond network present in bulk solvent. Surprisingly, FA appears to be the only polar solvent other than water forming a "polar-solvent pool" with macroscopic properties similar to the bulk.     

Composition of Surface Layer at the Water–Air Interface and Micelles of Triton X-100 + Rhamnolipid Mixtures

Measurements of the surface tensions, densities and viscosities of aqueous solutions of Triton X-100 (TX-100) and rhamnolipid (RL) mixtures, at constant concentration of RL or TX-100, were carried out. The measured values of the surface tension were compared to those determined using different theoretical models and on the basis of the surface tension of aqueous solutions of individual surfactants. From the surface tension isotherms, the Gibbs surface excess concentration of TX-100 and RL, the composition of surface layer and the standard Gibbs free energy of adsorption at the water–air interface were determined. Moreover, on the basis of surface tension, density and viscosity isotherms, the CMC of surfactants mixtures were evaluated. From the density isotherms, apparent and partial molar volumes of TX-100 and RL were also determined. These volumes were compared to those calculated from the sizes of TX-100 and RL molecules. There was observed a synergetic effect in the reduction of water surface tension and micelle formation, which was confirmed by the intermolecular interactions parameter. In the case of micelle formation, this effect was discussed based on the standard Gibbs free energy of micellization as well as of TX-100 and RL mixing in the micelles. The synergism of TX-100 and RL mixtures in the reduction of water surface tension and micelle formation was explained on the basis of electrostatic interactions between the hydrophilic part of TX-100 and RL molecules; this was supported by pH measurements.     

New insights on the photophysical behavior of PRODAN in anionic and cationic reverse micelles: from which state or states does it emit?

6-propionyl-2-(N,N-dimethyl)aminonaphtahalene, PRODAN, is widely used as a fluorescent molecular probe because of its significant Stokes shift in polar solvents. It is an aromatic compound with intramolecular charge-transfer states (ICT) that can be particularly useful as a sensor. The nature of the emissive states has not yet been established despite the detailed experimental and theoretical investigations done on this fluorophore. In this work, we performed absorption, steady-state, time-resolved fluorescence (TRES) and time-resolved area normalized emission (TRANES) spectroscopies on the molecular probe PRODAN in the anionic water/sodium 1,4-bis-2-ethylhexylsulfosuccinate (AOT)/n-heptane and the cationic water/benzyl-n-hexadecyl dimethylammonium chloride (BHDC)/benzene reverse micelles (RMs). The experiments were done by varying the surfactant concentrations at a fixed molar ratio (W = [H2O]/[Surfactant]) and changing the water content at a constant surfactant concentration. The results obtained varying the surfactant concentration at W = 0 show a bathochromic shift and an increase in the intensity of the PRODAN emission band due to the PRODAN partition process between the external solvent and the RMs interface. The partition constants, Kp, are quantified from the changes in the PRODAN emission spectra and the steady-state anisotropy () with the surfactant concentration in both RMs. The Kp value is larger in the BHDC than the AOT RMs, probably due to the interaction between the cationic polar head of the surfactant and the aromatic ring of PRODAN. The partition process is confirmed with the TRES experiments, where the data fit to a continuous model, and with the time-resolved area normalized emission spectroscopy (TRANES) spectra, where only one isoemissive point is detected. On the other hand, the emission spectra at W = 10 and 20 show a dual fluorescence with a new band that emerges in the low-energy region of the spectra, a band that was previously assigned to the PRODAN emission from the water pool of RMs. Our studies demonstrate that this band is due to the emission from an ICT state of the molecular probe PRODAN located at the interface of the RMs. These results are also confirmed by the lifetime measurements, the TRES experiments where the results fit to a two-state model, and the time-resolved area normalized emission spectroscopy (TRANES) spectra where three or two isoemissive points are detected in the AOT and BHDC RMs, respectively. In the AOT RMs, Kp values obtained at W = 10 and 20 are almost independent of the water content; the values are higher for the BHDC RMs due to the higher micropolarity of this interface.     

When is water not water? Exploring water confined in large reverse micelles using a highly charged inorganic molecular probe

The interior water pool of aerosol OT (AOT) reverse micelles tends toward bulk water properties as the micelle size increases. Thus, deviations from bulk water behavior in large reverse micelles are less expected than in small reverse micelles. Probing the interior water pool of AOT reverse micelles with a highly charged decavanadate (V(10)) oligomer using (51)V NMR spectroscopy shows distinct changes in solute environment. For example, when an acidic stock solution of protonated V(10) is placed in a reverse micelle, the (51)V chemical shifts show that the V(10) is deprotonated consistent with a decreased proton concentration in the intramicellar water pool. Results indicate that a proton gradient exists inside the reverse micelles, leaving the interior neutral while the interfacial region is acidic.     

Do all the protic ionic liquids exist as molecular aggregates in the gas phase?

According to an EI-MS study of 1,1,3,3-tetramethylguanidium-based protic ionic liquids (PILs), it has been concluded that not all PILs exist as molecular aggregates in the gas phase. The detection of both ions of m/z 115.0 and m/z 116.0 for the 1,1,3,3-tetramethylguanidinium trifluoromethylsulfonate (TMGS) protic ionic liquid indicates that both the molecular and ionic aggregates co-exist in the gas phase, which is to say that the TMGS may also evaporate via the ionic aggregates just like aprotic ionic liquids. Furthermore, investigation on triethylamine-based and 1-methylimidazole-based PILs confirmed that the gas phase structure of PILs depends on both the acidity and basicity of the corresponding acid and base.     

Spectrophotometric study of the incorporation of NBD probes in micelles: is a long alkyl chain on the fluorophore an advantage?

Fluorescence spectroscopy is widely used as a tool for elucidating the structure and dynamics of the micellar medium. A prerequisite commonly encountered for quantitative approaches is that the fluorophore resides exclusively in the micellar phase. Providing the fluorophore with a long alkyl chain may appear advantageous with regard to fixing the probe into the micelle. The present work was aimed at determining which are the consequences of this process from a spectroscopic viewpoint. The nitrobenzoxadiazolyl (NBD) moiety, which leads to well known fluorescent probes, was directly grafted on three fatty amines, the chain length of which varied from 8 to 18 carbon atoms. The spectroscopic properties of these NBD derivatives were investigated in three different micellar media: SDS, CTAB and TX100. The dyes were incorporated into micelles, where they were located in the interfacial region, whatever the chain length. When the dyes were previously dissolved in ethanol, and subsequently placed in the presence of the surfactant solution, complete solubilization was obtained. However, when the surfactant solution was used to dissolve directly a thin film of dye, a certain amount of dye remained non-incorporated and formed microcrystals, whose quantity and size increased with chain length. These microcrystals were mainly detected by UV/Vis-absorption and fluorescence microscopy. They induced drastic errors in the determination of fluorescence quantum yields, although they hardly interfered with other steady-state measurements and with dynamical fluorescence measurements. In conclusion, it appeared that for a small, non-ionic fluorophore such as NBD, the presence of a long alkyl chain is not an advantage. It slows down the incorporation process, unless some alcohol is introduced in the medium. Short-chain probes are therefore best suited for the study of the micellar medium.