The solubilization of alcohols in micellar solutions

The specific conductivities of dodecyldimethylbenzylammonium bromide (C12BBr) have been determined in aqueous butanol and aqueous benzyl alcohol solutions in the temperature range of 5-40°C. From these data the temperature dependent critical micelle concentration (cmc) was determined. The molar fraction of alcohol in the micelle was estimated using the theory suggested by Motomura et al. for surfactant binary mixtures. The thermal properties such as standard Gibbs free energy, enthalpy and entropy of solubilization of alcohols in the micelles were estimated for the phase separation model. The change in heat capacity upon solubilization of alcohol in the micelle has been estimated form the above properties. This revised version was published online in July 2006 with corrections to the Cover Date.     

Interaction of bovine serum albumin with nonionic surfactant Tween 80 in aqueous solutions: Complexation and association

It is shown by the methods of precision tensiometry, quasi-elastic light scattering, and UV, IR, and fluorescent spectroscopies that the properties of binary aqueous solutions with a constant concentration of bovine serum albumin and different concentrations of the nonionic surfactant Tween 80 (1 × 10^–7−6 × 10⁻² M) are determined mainly by the complexation and formation of a new phase. The complexation occurs owing to specific interactions (hydrogen bonding) between polar groups of Tween 80 and protein molecules. The solubility in water and surface activity of a 1: 1 Tween 80-protein complex are determined. At the concentrations above the break point on surface tension isotherms (conditionally corresponding to critical association concentration), the particles are formed with radii varying from 16 to 350 nm. At a molar nonionic surfactant/protein ratio in the range of 6–10, the additional binding of Tween 80 molecules by the particles of the new phase due to hydrophobic interactions is observed. Original Russian Text ? N.M. Zadymova, G.P. Yampol’skaya, L.Yu. Filatova, 2006, published in Kolloidnyi Zhurnal, 2006, Vol. 68, No. 2, pp. 187–197.     

Two-photon absorption in aqueous micellar solutions

Addition of the surfactant sodium dodecyl sulfate at concentrations above the critical micelle concentration increases the fluorescence quantum yield and the two-photon absorption cross-section of charged [2.2]paracyclophane chromophores containing pairs of D-pi-D chromophores. The resulting spectra in the micellar solutions are very similar to those obtained for neutral isostructural analogues in toluene. The measured etadelta values are 1300 GM for 1C and 1920 GM for 2C, which are comparable or larger to those in toluene. These results highlight possible misleading interpretation of two-photon-induced emission for evaluating the concentration of labeled substrates used in two-photon microscopy and provide guidelines for designing molecular structures with optimized two-photon action cross-sections in water.     

Thermal analysis of aqueous micellar solutions

A micro differential temperature scanning calorimeter was used to characterize the structural changes between different types of micelles in aqueous solutions of ionic surfactants: anionic — sodium dodecylsulfate (SDS) — and cationic — hexadecyltrimethyl ammonium bromide (CTAB). Moreover, this technique allowed to confirm the existence of peculiar types of complexes between surfactants and selected solutes. In SDS solutions containing polyethylene glycols (PEG), the presence of complexes formed by small micelles adsorbed along the chains of the polymers was evidenced in the case of long enough polymer chains. In CTAB-phenol solutions, due to strong interactions between the polar heads of surfactant and phenol, molecular complexes of a composition of 1:1 molar ratio have been characterized. Depending on the ratio [phenol]/[CTAB], the rheological behaviour was found to change from fluid to viscoelastic and gel-like solutions, owing to the growth of elongated rod-like micelles. With entangled worm-like micelles, the important role of kinetics to reach the thermodynamic equilibria was shown.     

Viscosity of aqueous micellar solutions of surfactants

The viscosity of aqueous micellar solutions of two long-chain surfactants, C₂₄H₄₃N₂ClO and C₂₁H₃₈NCl, is studied in a concentration range of 10^?4?C10^?2 mol/L and a temperature range of 20?C40°C. It is established that, in the region of critical micelle concentration, the viscosity is a nonmonotonic function of concentration and has minima and maxima.     

Tween 80-based mixed micelles as felodipine carriers in aqueous medium

UV spectroscopy, precise turbidimetry, and refractometry are employed to measure the solubilization of the lipophilic compounds felodipine (F) (drug) and nonionic surfactants glyceryl monooleate (GMO) and glyceryl monolaurate (GML) (efficient promoters of skin permeability (enhancers)) in aqueous solutions of Tween 80 (Tw). An increase in the concentration of Tw makes it possible to enhance the solubility of the drug by a factor of 10²–10³ and above as compared to F solubility in water. The effect becomes stronger in the presence of an enhancer. The following properties of Tw + F, Tw + GMO, Tw + GML, Tw + GMO + F, and Tw + GML + F micelles are studied: the aggregation numbers of the components, localization of solubilizates, diffusion coefficients, sizes, and degrees of hydration. Experimental data on the kinetics of drug mass transfer by micelles are in good agreement with the calculations performed within the framework of diffusion theory. Tw-based mixed micelles are found to be efficient carriers of F and enhancers in aqueous media, which is of importance for the creation of systems for delivery of lipophilic drugs in a bioavailable form.     

Micellization and solubilization of a model hydrophobic drug nimesulide in aqueous salt solutions of Tetronic T904

The micellar and phase behavior of an ethylene oxide-propylene oxide branched octablock copolymer Tetronic T 904 (hereafter written as T904) in water and NaCl solutions was examined. The copolymer shows a cloud point (CP) ranging from 74-65°C in the concentration range of 1-10% and forms aggregates (micelles) with a hydrodynamic diameter around 10-12nm in the temperature range 30-40°C. Stable, bluish solutions containing aggregates of variable size (several hundred nm in some cases) were observed even at temperatures much less than the critical micellization temperature (CMT=30°C for a 2% solution in water). The CP and the CMT markedly decrease in the presence of NaCl due to the dehydration of the polyethylene oxide shell. The size of the micelles in water or salt solutions increases at temperatures close to the CP as inferred from viscosity measurments. A model drug compound (nimesulide, NIM) was solubilized in T904 micelles which showed a remarkable increase in solubilization at higher temperature; however, a decrease in solubilization was observed in salt solutions. The thermodynamic parameters for solubilization were obtained, and the location of NIM in the copolymer micelles was investigated by UV-Visible spectroscopy.     

Solubility and hydrolytic stability of indomethacin in aqueous micellar solutions

Russian Chemical Bulletin - The solubility of the indomethacin drug in aqueous micellar solutions of a series of dicationic surfactants was characterized by spectrophotometry. The use of these...     

Pyrene-N,N-dimethylaniline heteroexcimer systems in aqueous micellar solutions

Strong quenching of fluoroscence of pyrene by N,N-dimethylaniline as well as N,N-dimethylaniline sulfonate has been observed in aqueous micellar solutions. Photoinduced electron transfer from the anilines to excited pyrene near the micelle-water interface has been demonstrated by means of laser photolysis studies.     

Paclitaxel solubility in aqueous dispersions and mixed micellar solutions of lecithin

The aim of this study was to find a biocompatible, lecithin-based carrier for paclitaxel (PTX) suitable for intravenous infusion and ensuring a soluble PTX concentration of 100 mg/100 ml or higher for at least 24 h. Aqueous dispersions of egg or soya lecithin (water-lecithin dispersions, WLD), mixed micellar (MM) solutions of egg lecithin and sodium deoxycholate, and formulations containing lecithin plus the co-surfactants and co-solvents poloxamer, polysorbate, Span, benzalkonium chloride, and macrogol were investigated. Amorphous PTX was prepared by lyophilization. PTX co-lyophilized with surfactants was also studied. Unlike crystalline PTX, the drug in an amorphous form is easily soluble in 1-5% (w/w) WLD or in MM. The highest solubility (up to 570 mg/100 ml) was achieved in 5% WLD. Dissolved PTX precipitated from all tested formulations over 24 h. Despite this, concentrations of dissolved PTX of 100 mg/100 ml or higher were observed after 24 h in 5% egg WLD, 1-5% soya WLD, and in 5% MM (lecithin : deoxycholate ratio 1 : 1 w/w). When four different batches of 5% egg WLD were prepared, containing PTX in clinically relevant concentration of 100 mg/100 ml, no precipitation of PTX was observed within 24 h and this formulation is the most promising candidate for further in vivo studies. Neither additional surfactants nor co-lyophilization increased PTX solubility in the lecithin-based carriers. The use of parenteral emulsions as solvents for the co-lyophilized PTX also failed to increase the solubility of the drug up to the target concentration.     

ESR study of photooxidation of phenothiazines in aqueous micellar solutions

The mechanism of photooxidation of phenothiazine in liquid and frozen (77 K) aqueous micellar solutions of the surfactant (sodium dodecyl sulfate) was studied by ESR. The main reaction of electrons formed by the photochemical oxidation of phenothiazine in a liquid micellar solution of the anionic surfactant is the reduction of molecular oxygen dissolved in the aqueous bulk phase. 10-Methylphenothiazine was used as a stable radical cation probe in a liquid solution. The influence of electrolytes on the photoionization yield in both frozen and liquid solutions of the surfactant was studied.     

Enthalpies of reaction of calcium chloride and sodium oxalate in aqueous solution of Tween 80

The heats of mixing of dilute calcium chloride and sodium oxalate solutions in water and aqueous solutions of a nonionogenic surfactant, namely, polyoxyethylene (20) sorbitan monooleate (Tween 80) containing 1–5 wt % of the dissolved substance were measured at 298.15 K. The heats of dilution of calcium chloride solutions were determined, and the enthalpies of precipitation of calcium oxalate in water and surfactant solutions were calculated. The surfactant concentration was found to have almost no effect on the enthalpies of the processes under study; rather, it modifies the shape of the resultant deposit by preventing the agglomeration of calcium oxalate particles.     

Dielectric behavior of aqueous micellar solutions of betaine-type surfactants

Dielectric behavior was examined for aqueous solutions of the betaine-type surfactants dodecyldimethylcarbobetaine (C(12)DCB), tetradecyldimethylcarbobetaine (C(14)DCB), cetyldimethylcarbobetaine (C(16)DCB), and oleyldimethylcarbobetaine (OleyDCB) as a function of frequency from 1.00 x 10(6) to 2.00 x 10(10) Hz (6.28 x 10(6) to 1.26 x 10(11) rad s(-1)) with changing surfactant concentration (c(D)). Rotational relaxation times (tau) of the zwitterionic headgroups of the surfactants in aqueous solutions of C(12)DCB and C(14)DCB, which form spherical micelles, are determined to be 0.26 and 0.30 ns, respectively. Values of tau for aqueous solutions of C(16)DCB and OleyDCB, which form threadlike micelles, are identical at 0.44 ns. The tau values of all micellar solutions are constant irrespective of c(D). The increase in tau with increasing alkyl chain length is assigned to an increase of molecular density at the micellar surface. The magnitude of the relaxation strength for the surfactant solutions increases in proportion to c(D) and is not so different from that of an aqueous solution of glycine betaine (GB), which has the same chemical structure as betaine-type surfactants with zwitterionic headgroups but never forms micelles. This finding suggests that the zwitterionic headgroup rotating on the micellar surface possesses a dipole moment with a magnitude essentially the same as that of GB in aqueous solutions.     

Viscoelastic behavior of aqueous threadlike micellar solutions of oleyldimethylamineoxide

The viscoelastic behavior of aqueous oleyldimethylamineoxide (ODAO) solutions was examined by varying the concentration of ODAO, c_D, and the average degree of protonation, <!>, by adding hydrogen bromide to the system. ODAO forms long threadlike micelles in aqueous solution in spite of the absence of any additives. Therefore, the aqueous ODAO system shows pronounced viscoelastic behavior caused by entanglement between threadlike micelles as highly entangled polymer systems do. The frequency dependence of the storage and loss moduli for the system is perfectly described by that of a Maxwell model possessing only one set of relaxation time, F, and strength, G_N. G_N is proportional to the square of c_D as observed in concentrated liner polymer solutions, while F decreases with increasing c_D. On the other hand, the addition of HBr to control <!> remarkably increases F when G_N is constant. This suggest that <!> alters the inner structure of the threadlike micelles; association of head groups, dimers or trimers of ODAO are formed in the micelles owing to hydrogen bonding between protonated ODAO or between protonated and unprotonated ODAO. An increase in the number density of the associated head groups in the threadlike micelles increases F. Moreover, the flexibility of the threadlike micelles in the system is not affected so much by a change in the number density of the associated head groups, since G_N corresponding to the number density of entanglements in the system is kept constant.     

Kinetics of solubilization of n-decane and benzene by micellar solutions of sodium dodecyl sulfate

We observed the diminishing of single microscopic oil drops to study the kinetics of solubilization of n-decane and benzene by micellar solutions of sodium dodecyl sulfate (SDS). Each drop is located in a horizontal glass capillary of inner diameter 0.06 cm filled with a thermostated surfactant solution; the small vertical dimension of the cell prevents the appearance of uncontrollable thermal convections. The experiments show that the radius of an n-decane drop decreases linearly with time, whereas for benzene this dependence is nonlinear. To interpret the data, a kinetic model of solubilization is developed. It accounts for the diffusion and capturing of dissolved oil molecules by the surfactant micelles, as well as for the finite rate of oil dissolution at the oil-water interface. By processing the data, we determined the rate constant of solubilization for a given oil and surfactant. It turns out that the elementary act of catching a dissolved oil molecule by a surfactant micelle occurs under a barrier (rather than diffusion) control. The effective rate of solubilization is greater for the oil, which exhibits a higher equilibrium solubility in pure water (benzene), despite the lower value of the solubilization rate constant for this oil.     

Versatility of aqueous micellar solutions for self-assembled monolayers engineering

Self-assembly of aliphatic as well as aromatic thiol-terminated molecules was achieved onto a variety of gold surfaces using aqueous micellar solutions. Scanning tunneling microscopy experiments allowed us to demonstrate that the increase in the density of self-assembled monolayers (SAMs) prepared from micellar aqueous solvent compared to that prepared from ethanol directly originates from the decrease in defect density in the SAM (etch pits, domain boundaries) and not from a denser local packing of the molecules. Extending the use of such an aqueous solvent to various conjugated molecules, we report for the first time the insertion of these molecules from an aqueous solution in a dodecanethiol (DT) SAM and the ligand-exchange on the surface of DT stabilized gold nanoparticles deposited as a Langmuir-Blodgett film. Finally, we show that aqueous micellar DT solutions allow the preparation of DT SAMs on gold through a micropatterned resist mask. These results make possible the use of water to deliver molecules on a solid substrate to build molecular devices in a way compatible with lithography requirements in microelectronic processes.     

Enthalpies of mixing of some nitriles aqueous solutions with dodecylsurfactants micellar solutions

The enthalpies of mixing of some n-nitriles (from acetonitrile to valeronitrile) aqueous solutions with dodecyltzimethylammonium bromide, sodium dodecylsulfate and dodecyltzimethylammonium oxide micellar solutions were determined. The measurements were performed by systematically changing the surfactant concentration at a given solute concentration. The experimental enthalpies were rationalized in terms of the standard enthalpy of transfer of solute from the aqueous to the micellar phase and of the distribution constant between the two phase. Information on the effect of the nature of the surfactant on the standard thermodynamic quantities of transfer(G _t ^o , H _t ^o , TS _t ^o ) is reported. The present data are compared to those previously reported for primary alcohols and the solubilizing properties shown by the different types of micelles are discussed.     

Acid-base properties and nucleophilicity of o-aminomethylphenols in aqueous micellar solutions and microemulsions

The pK _a values and constants of tautomeric equilibrium of several o-aminomethylphenols with different hydrophilic-lipophilic ability were measured in aqueous micellar solutions and in direct microemulsions based on cetyltrimethylammonium bromide. The kinetics of hydrolysis of p-nitrophenyl acetate at different pH and concentrations of aminomethylphenol and surfactant was studied. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1724–1729, October, 2006     

Dediazoniation of 1-naphthalenediazonium tetrafluoroborate in aqueous acid and in micellar solutions

We have measured the rates and product yields of dediazoniation of 1-naphthalenediazonium (1ND) tetrafluoroborate in the presence and absence of sodium dodecyl sulfate (SDS) micellar aggregates by employing a combination of UV–vis spectroscopy and high-performance liquid chromatography (HPLC) measurements. Kinetic data were obtained by a derivatization procedure with product yields were determined by HPLC. HPLC chromatograms show that in aqueous acid and in micellar solutions only one dediazoniation product is formed in significant quantities, 1-naphthol (NOH), and the observed rate constants (k_obs) are the same when 1ND loss is monitored spectrometrically and when NOH formation is monitored by HPLC. Activation parameters were obtained both in the presence and absence of SDS micellar aggregates. In both the systems, the enthalpies of activation are high and the entropies of activation are positive. The enthalpy of activation in the absence of SDS is very similar to that in the presence of SDS micelles, but the entropy of activation is lower by a factor of 4. As a consequence, SDS micelles speed up the thermal decomposition of 1ND and increase k_obs by a factor of 1.5 when [SDS] = 0.02 M. In contrast, results obtained in the presence of complexing systems such as crown ethers and polyethers show significant stabilization of the parent arenediazonium ions. Kinetic and HPLC data are consistent with the heterolytic D_N + A_N mechanism that involves the rate-determining fragmentation of the arenediazonium ion into a very reactive phenyl cation that reacts competitively with available nucleophiles. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 301–309, 2008