Physicochemical investigation of acrylamide solubilization in sodium bis(2-ethylhexyl)sulfosuccinate and lecithin reversed micelles.

The state of acrylamide confined within dry sodium bis(2-ethylhexyl)sulfosuccinate (AOT) and lecithin reversed micelles dispersed in CCl4 has been investigated by FTIR and H-1 NMR spectroscopy. Measurements have been performed at 25 degreesC as a function of the acrylamide-to-surfactant molar ratio (R) at a fixed surfactant concentration (0.1 mol kg(-1)). The analysis of experimental data, corroborated by the results of SAXS measurements, is consistent with the hypothesis that acrylamide is quite uniformly distributed among reversed micelles mainly located in proximity to the surfactant head-group region and that its presence induces significant unidimensional growth of micellar aggregates.…

Molecular dynamics of electrosprayed water nanodroplets containing sodium bis(2-ethylhexyl)sulfosuccinate

The behavior of aqueous solutions of sodium bis(2-ethylhexyl)sulfosuccinate (AOTNa) subject to electrospray ionization (ESI) has been investigated by molecular dynamics (MD) simulations at three temperatures (350, 500 and 800 K). We consider several types of water nanodroplets containing AOTNa molecules and composed of a fixed number of water molecules (1000), N(AOT)(0) AOT(-) anions (N(AOT)(0) =  0, 5, 10) and N(Na)(0) sodium ions (N(Na)(0) =  0, 5, 10, 15, 20): in a short time scale (less than 1 ns), the AOTNa molecules, initially forming direct micelles in the interior of the water nanodroplets, are observed in all cases to diffuse nearby the nanodroplet surface, so that the hydrophilic …

Synthesis and physico-chemical characterization of gold nanoparticles softly coated by AOT

Size-controlled gold nanoparticles/surfactant stable systems were prepared by the combined action of the solvated metal atom dispersion (SMAD) technique and confinement in anhydrous sodium bis(2-ethylhexyl)sulfosuccinate (AOT) micellar solution. From liquid samples, by evaporation of the organic solvent, solid gold nanoparticle-surfactant liquid crystals composites were obtained. Sample characterization was performed by X-ray diffraction (SAXS and WAXS), XPS spectroscopy and UV-vis-NIR spectroscopy. All experimental data consistently revealed the coexistence of two gold nanoparticle size populations: bigger nanoparticles (size 20-50 angstrom) and smaller ones (size of few angstrom). The two…

Triggering Dissymmetry in Achiral Dye Molecules by Chiral Solvents:Circular Dichroism Experiments and DFT Calculations

Synthesis and characterization of ZnS nanoparticles in water/AOT/n-heptane microemulsions

ZnS nanoparticles were synthetized using water-containing AOT reversed micelles as nanoreactors and characterized by UV-Vis spectrophotometry, HRTEM (high-resolution transmission electron microscopy), SAED (selected-area electron diffraction), and digital image processing. The experimental data evidence a slow growing process of fractal-like ZnS nanoparticles’ coupled with a change of their photophysical properties. Both these processes are well described by power laws. The nanoparticles size is mainly controlled by the micellar size. After evaporation of the organic solvent, it has been found that the deposit is constituted by smaller and more stable ZnS nanoparticles bathed in a surfactan…

Physicochemical Investigation of the Solubilization of Ytterbium Nitrate in AOT Reverse Micelles and Liquid Crystals

A wide investigation of the solubilization of the water-soluble salt Yb(NO3)(3) in sodium bis(2-ethylhexyl)sulfosuccinate (AOT) reverse micelles and AOT liquid crystals has been carried out. After saturation of water/AOT/organic solvent w/o microemulsions with pure Yb(NO3)(3), the Yb(NO3)(3)/AOT composites were prepared by complete evaporation under vacuum of the volatile components (water and organic solvent) of the salt-containing microemulsions. It was observed that these composites can be totally dissolved in pure n-heptane or CCl4, allowing the solubilization of a noticeable amount of Yb(NO3)(3) in quite dry apolar media. By UV-vis-NIR, FT-IR, and H-1 NMR spectroscopies, some informati…

Degrees of freedom effect on fragmentation in tandem mass spectrometry of singly charged supramolecular aggregates of sodium sulfonates

The characteristic collision energy (CCE) to obtain 50% fragmentation of positively and negatively single charged noncovalent clusters has been measured. CCE was found to increase linearly with the degrees of freedom (DoF) of the precursor ion, analogously to that observed for synthetic polymers. This suggests that fragmentation behavior (e.g. energy randomization) in covalent molecules and clusters are similar. Analysis of the slope of CCE with molecular size (DoF) indicates that activation energy of fragmentation of these clusters (loss of a monomer unit) is similar to that of the lowest energy fragmentation of protonated leucine-enkephalin. Positively and negatively charged aggregates be…

Orientation and molecular contacts of melatonin confined into AOT and lecithin reversed micellar systems

Abstract The state of increasing amounts of melatonin (MLT) confined in dry AOT or lecithin reversed micelles dispersed in CCl 4 has been investigated by UV–vis and 1 H NMR spectroscopies. The experimental results are consistent with MLT totally entrapped in reversed micelles, as a consequence of specific melatonin/surfactant interaction; the main driving force of the MLT solubilization in the core of reversed micelles is the establishment of H-bonding between the MLT NH groups (both indolic and amidic) and the head group of surfactants. The short contacts deduced from intermolecular NOEs are accounted for by favourable interactions between the surfactant's polar head and the H7–NH–H2 fragm…

Calorimetric study of the solubilization of ethylenediamine, N,N-dimethylaminoethylamine and N,N,N?,N?-tetramethylethylenediamine by reversed AOT micelles

Distribution constants and standard enthalpies of transfer of ethylenediamine (en), N,N-dimethylaminoethylamine (dmen) and N,N,N′,N′-tetramethylethylenediamine (tmen) partitioned between n-heptane and water containing reversed sodium bis(2-ethylhexyl) sulfosuccinate (AOT) micelles as a function of the molar concentration ratio R (R=[water]/[AOT]) were evaluated by a calorimetric method. The results show that en, dmen and tmen molecules, solubilized in the reversed micelles, are distributed between the micellar aqueous core and the micellar palisade layer. An analysis of the thermodynamic parameters of the partition process demonstrates the peculiar solvent properties of the water containing…

Physicochemical investigation of surfactant-coated gold nanoparticles synthesized in the confined space of dry reversed micelles

Abstract Gold nanoparticle/surfactant composites have been synthesized by a novel reduction reaction in the confined space of dry sodium bis(2- ethylhexyl)sulfosuccinate (AOT) or lecithin reversed micelles dispersed in n-heptane and cyclohexane, respectively. The reaction was carried out by adding an opportune amount of anhydrous hydrazine/tetrahydrofuran solution to a suspension of HAuCl4-containing dry reversed micelles dispersed in organic solvent. UV–vis investigation ascertained the formation of stable metal gold nanoparticles and the analysis of FT-IR spectra highlighted the formation of an oriented surfactant monolayer at the nanoparticle surface. Simple evaporation under vacuum of t…

Study of lecithin reverse micelles by FT-IR spectroscopy

FT-IR spectra of water/lecithin/deuterated cyclohexane microemulsions as a function of water/lecithin molar ratio R (R=[water]/[lecithin]) at various lecithin volume fractions (φ) have been recorded. After elimination of the spectral contributions due to the deuterated cyclohexane and normalization, the band parameters of the CO and PO4 vibrational modes due to lecithin have been found dependent only upon R. This behaviour has been interpreted in terms of a progressive structural modification of the water/lecithin interface superimposed to the progressive hydration of CO and PO4 groups. Moreover, no correlation between the CO and PO4 band parameters and the formation of gel-like micellar so…

Physicochemical investigation of cobalt?iron cyanide nanoparticles synthesized by a novel solid?solid reaction in confined space

Cobalt–iron cyanide (Cox[Fe(CN)6]) nanoparticles have been synthesized by a novel solid–solid reaction in the confined space of dry sodium bis(2-ethylhexyl)sulfosuccinate (AOT) reversed micelles dispersed in n-heptane. The reaction has been carried out by mixing two dry AOT/n-heptane solutions containing CoCl2 and K4Fe(CN)6 or K3Fe(CN)6 nanoparticles in the micellar core, respectively. By UV-Vis spectroscopy it was ascertained that, after the mixing process, the formation of stable nanoparticles is fast and complete. Microcalorimetric measurements of the thermal effect due to the Cox[Fe(CN)6] nanoparticle formation allowed the determination of the stoichiometric ratio (x) and of the molar e…

Refractive index of water-AOT-n-heptane microemulsions

Refractive index measurements on water/AOT/n-heptane microemulsions as a function of the volume fraction ϕ of the dispersed phase (water plus AOT) and of the water/AOT molar ratio R have been performed at 25°C. The refractive index was found to vary monotonically with ϕ without any change in rate during the crossover of the percolation threshold. Such a behavior suggested that, well above the percolation threshold, the water-AOT-n-heptane microemulsions are still formed by water-containing AOT reversed micelles dispersed in the oil phase. The analysis of the experimental data allowed an evaluation the fraction of the water molecules bonded to the AOT head group as a function of R.

Effect of tetrahydrofuran on the conductance and ion-pairing of hydrogen chloride in wet and dry methanol mixtures

The molar conductance of dilute solutions of HCl in wet (68.5% methanol + 31.5% tetrahydrofurane mixtures at 25°C have been measured. The data were analyzed using the Fuoss-Hsia equation to calculate the infinite dilution molar conductances and association constants. The trend of the limiting conductances in these mixtures as a function of the water content shows, once more, the peculiar minimum due to the anomalous proton conductance mechanism. From these data the limiting molar conductance in the anhydrous binary solvent system was evaluated. The percentage excess proton mobility with respect to potassium ion has also been determined. All these data are compared to those found in a binary…

FT-IR Investigation of the Urea State in AOT Reversed Micelles

Abstract FT-IR spectra of the urea/sodium bis(2-ethylhexyl) sulfosuccinate (AOT)/CCl 4 system as a function of the urea-to-AOT molar ratio ( R urea ) at a fixed AOT concentration ([AOT]=0.1 mol·kg −1 ) have been recorded at 25°C. The experimental data are consistent with the hypothesis that at low R urea values urea is dispersed as monomers among the hydrophilic core of AOT reversed micelles, whereas at R urea >0.13 it is encapsulated as small molecular clusters. These clusters display some departures from the H-bonded structure of the pure solid urea attributable to their small size and to urea–AOT head group interactions. The stretching modes of AOT sulfonate groups are affected by the pr…

Coupling chemical reaction to electrospray: a novel preparation of gold nanostructures

The simultaneous reduction of Au(III) to Au(0), synthesis of gold nanoparticles and their deposition onto boron-doped silicon target have been attained by the electrospray technique. In this way the overall process can be considered as a novel chemical/physical hybrid method which synergically exploits the merits of both approaches. Various experimental conditions have been explored to optimize the process: it has been found that, by applying a negative high voltage to the boron-doped silicon target and with the presence of the surfactant Bis(2-ethylhexyl)sulfosuccinate sodium salt in the solution, a quantitative transformation of Au(III) to Au(0) nanoparticles has been obtained. The deposi…

Structural and dynamical investigation of gelation containing water-in-oil microemulsions

The gelatin (Bloom 300)/water/AOT/n-heptane system has been investigated at fixed water/AOT molar ratioR (R=31.1) as a function of the gelatin content. Several experimental techniques (densitometry, refractometry, conductometry, rheology, dielectrometry, ultrasonics, hypersonics) have been used to investigate the role played by the gelatin molecule in the observed sol-gel transition above a critical gelatin content. The results appear consistent with the hypothesis of a rigid network of gelatin-water rods coated by surfactant molecules coexisting with gelatin-free AOT reversed micelles at the gelation point.

Precipitation of slightly soluble silver salts in reversed AOT micelles: Calorimetric investigation

The enthalpies of precipitation, of AgCl, Agl, Ag2S and silver tetraphenylborate (AgTPB) in water containing reversed sodium bis(2-ethylhexyl) sulfosuccinate (AOT) micelles as a function of the molar concentration ratio R (R=[water]/[AOT]) at various concentrations of AOT and reagent salts, were measured by a calorimetric technique. The molar enthalpies of precipitation are independent of the surfactant concentration but are dependent on the concentration of the reagent salts and the R value. The molar enthalpies for the same processes in bulk water are not approached even at the highest R value. Effects due to the smallness of the microcrystals and to the interactions between ions and mice…

Preparation and characterisation of Na 2 S and ZnSO 4 nanoparticles in water/sodium bis(2-ethylhexyl)sulphosuccinate/ n -heptane microemulsions

The preparation procedure for nanoparticles of the water-soluble salts Na2S and ZnSO4, two commonly used reagents to synthesise ZnS nanoparticles, by evaporation of volatile components of salt-containing water-in-oil microemulsions is described. In suitable conditions, the evaporation leads to the formation of dry salt–surfactant composites and to the formation of Na2S or ZnSO4 nanoparticles. It was found that the salt–surfactant composites can be totally redissolved in a dry apolar organic solvent allowing the formation of virtually water-free solutions containing a considerable amount of the water-soluble salts. The presence of nanoparticles in these solutions and in the composites has be…

Do electrospray mass spectra of surfactants mirror their aggregation state in solution?

One important feature in the gas phase chemistry of surfactants is to ascertain whether their aggregates produced by electrospray ionization reflect those formed in the starting solution. With this aim, we have performed ESI-MS, ESI-MS/MS and ER-MS spectra of bis(2-ethylhexyl)sulfosuccinate (AOTNa) solutions in different solvents, i.e. water, water/methanol, methanol and n-hexane. The results clearly indicate that, notwithstanding the strongly different aggregation state in solution (direct micelles in water and in water/methanol, molecular dispersion in methanol and reverse micelles in n-hexane) and marked effects of the solvent polarity on the total ionic current, the surfactant aggregate…

FT-IR investigation of the acetamide state in AOT reversed micelles

The state of acetamide nanoparticles encapsulated in the hydrophilic core of sodium bis(2-ethylhexyl) sulfosuccinate (AOT) reversed micelles and dispersed in CCl4 has been investigated by Fourier transform infrared spectroscopy. The analysis of the vibrational spectra reveals even at the higher acetamide to AOT molar ratio some changes of the typical H-bonded structure of solid acetamide ascribable to their small size, confinement effects, and acetamide-AOT head group interactions. The stretching modes of acetamide CO and AOT sulfonate groups indicate unambiguously specific acetamide-AOT head group interactions.

Collision induced fragmentations of multiply charged sodium bis(2-ethylhexyl)-sulfosuccinate aggregates in gas phase: neutral loss versus charge separation

Abstract Stability and fragmentation patterns of multicharged aggregates of sodium bis(2-ethylhexyl)-sulfosuccinate (NaAOT) in gas phase have been investigated by ion mobility mass spectrometry (IM-MS) and tandem mass spectrometry (MS-MS). Positively doubly charged NaAOT aggregates show at low collision energy a preference for the loss of NaAOT molecules, whereas fragmentation through charge separation process is favored at higher collision energy. By increasing the charge state of the aggregates, the fragmentation through charge separation tends to predominate especially at low aggregation number and only charge separation fragmentation is observed for positively quadruply charged species.…

Dielectric properties of solutions of antimony (III) halides in methanol

The complex permittivities obtained by time domain reflectometry (TDR) measurements in the frequency range 0.1–15 GHz are reported for solutions of SbF3, SbCl3 and SbBr3 in methanol at 25°C. By increasing the concentration of the solutes, a marked increase of the main relaxation time and of the static permittivity of methanol is observed. These effects have been attributed to the ability of antimony (III) halides to strengthen the hydrogen bonding in methanol and to promote the shift of the dynamic equilibria among the various populations of hydrogen bonded methanol aggregates toward those characterized by a parallel orientation of neighboring dipoles. A second relaxation, occurring at low …

Interactions of α-tocopherol with biomembrane models: Binding to dry lecithin reversed micelles

Abstract The state of α-tocopherol (Vitamin E) in solutions of dry lecithin reversed micelles dispersed in an apolar medium has been investigated as a function of the Vitamin E to surfactant molar ratio (RVE) at fixed surfactant concentration by FT-IR, 1H NMR and SAXS with the aim to emphasize the role played by anisotropic intermolecular interactions and confinement effects as driving forces of its partitioning between apolar bulk solvent and polar nanodomains and of mutual Vitamin E/reversed micelle effects. It has been found that its binding strength to reversed micelles, triggered by steric and orientational constrains, is mainly regulated by specific interactions between the hydrophili…

Calorimetric investigation of the interaction between a macromolecular prodrug of diflunisal and human platelets

The thermal effect due to the interaction between human platelets and α,β poly(N-hydroxy-ethyl)-DL-aspartamide (PHEA) or the PHEA-Diflunisal conjugate was measured by the calorimetric technique at 25°C. The experimental data confirm that PHEA is a biocompatible macromolecule and that its conjugate influences the physiological activity of human platelets.

Calorimetric study on the solubilization of some primary alcohols by reversed AOT micelles

A calorimetric method to evaluate, at the same time, the distribution constant and the standard enthalpy of transfer of a solute partitioned between organic phase and reversed micelles is proposed. The method was applied to the partition of methanol, 1-propanol and 1-pentanol between n-heptane and AOT reversed micelles containing water at 25°C. The results show that the distribution constant decreases as the alcohol alkyl chain length increases and that the solubilization site can change as the water content of reversed AOT micelles increases. In particular, at sufficiently high water content, methanol seems to be preferably solubilized in the aqueous pseudophase whereas 1-pentanol prefers …

Synthesis, size control, and passivation of CdS nanoparticles in water/AOT/n-heptane microemulsions

Abstract CdS nanoparticles have been synthesised by adding tetrabutylammonium hydrogen sulphide to water/sodium bis(2-ethylhexyl) sulfosuccinate/ n -heptane microemulsions containing CdSO 4 . Analysis of UV–Vis absorption spectra recorded at various times indicates that an initial rapid formation of CdS nanoparticles is followed by a very slow growth process which can be well described by a power law. The growth process is totally inhibited by the addition of an appropriate amount of bis(2-ethylhexyl)amine (BEA) leading to the formation of stable nanosized CdS particles coated by an oriented monolayer of chemically bonded BEA molecules. Depending on the BEA addition time, the growth inhibit…

Mass action model for solute distribution between water and micelles. Partial molar volumes of butanol and pentanol in dodecyl surfactant solutions

The densities of 1-butanol and 1-pentanol were measured in aqueous solutions of dodecyltrimethylammonium bromide and dodecyldimethylamine oxide and the partial molar volumes at infinite dilution of the alcohols in aqueous surfactants solutions were obtained. The observed trends of this quantity as a function of the surfactant concentration were rationalized using a mass-action model for the alcohol distribution between the aqueous and the micellar phase. At the same time, the model was revised to account for the alcohol effect on the surfactant micellization equilibrium. The partial molar volume of alcohols in the aqueous and in the micellar phases and the ratios between the binding constan…

Electrical conductivity and permittivity of water-AOT-n-heptane microemulsions

Measurements of the electrical conductivity and of the complex permittivity of water-sodium bis(2-ethylhexyl) sulfosuccinate (AOT)-n-heptane microemulsions are reported. The experimental results are rationalized in terms of a hopping mechanism of AOT anions within clusters of reversed micelles. The dependence of the hopping rate and of the cluster dimensions upon the ratio [water]/[AOT] and temperature is discussed.

Physico-chemical investigation of the state of cyanamide confined in AOT and lecithin reversed micelles

Sodium bis(2-ethylhexyl)sulfosuccinate (AOT) and lecithin reversed micelles containing cyanamide have been investigated by small-angle X-ray scattering, FT-IR, and 1H NMR spectroscopy at various cyanamide-to-surfactant molar ratio (X) and at fixed surfactant concentration (0.1 mol kg-1). Experimental data are consistent with a model of cyanamide molecules confined in reversed micelles, quite uniformly distributed among them and mainly located among surfactant headgroups. SAXS data analysis leads also to hypothesize a unidimensional growth of the reversed micelles with increasing the X value. Moreover, the cyanamide state and the cyanamide/cyanamide interactions in reversed micelles have bee…

Calorimetric investigation on the formation of palladium nanoparticles in water/AOT/n-heptane microemulsions

The formation enthalpy of palladium nanoparticles in water/sodium bis(2-ethylhexyl) sulfosuccinate (AOT)n-heptane microemulsions as a function of the waterAOT molar ratio (R = [water][AOT]) was measured by a calorimetric technique. The results indicate that at R < 10 the energetic state of the palladium nanoparticles compartmentalized within the reversed AOT micelles is signficantly different from that in bulk water. Effects due to the small size of the palladium nanoparticles and to interactions between nanoparticles and the waterAOT interface are discussed.

Structure of Urea Clusters Confined in AOT Reversed Micelles

The structure of sodium bis(2-ethylhexyl)sulfosuccinate (AOT) and that of urea containing AOT reversed micelles has been investigated by small-angle neutron scattering (SANS) and Fourier transform infrared (FT-IR) spectroscopy at different AOT concentrations and urea/AOT molar ratios. For the AOT/n-heptane system, SANS data analysis indicates that AOT molecules form prolate ellipsoidal aggregates, which grow asymmetrically along the major axis upon increasing the surfactant concentration. For the urea/AOT/n-heptane system, the SANS results are consistent with the hypothesis that urea is encapsulated as small-sized ellipsoidal hydrogen-bonded clusters within the hydrophilic micellar core of …

A simple method to prepare solid nanoparticles of water-soluble salts using water-in-oil microemulsions

A new and simple method to prepare solid nanoparticles of water-soluble salts using water-in-oil microemulsions is described. In particular, starting from water/sodium bis(2-ethylhexyl)sulfosuccinate/n-heptane microemulsions carrying inside the aqueous core of the reversed micelles some water-soluble salts [CaCl2, Na2HPO4, Cu(NO3)2], after evaporation of the volatile components (water and apolar organic solvent), the resulting inorganic salt/surfactant composites were found to be totally dispersible in pure n-heptane. The presence of nanoparticles in these resuspended composites was ascertained by transmission electron microscopy observation of samples obtained by gentle evaporation of the …

Calorimetric investigation of the precipitation of calcium monohydrogen phosphate in water/AOT/n-heptane microemulsions

Abstract The molar enthalpies of precipitation of calcium monohydrogen phosphate (CaHPO 4 ) in water/sodium bis(2-ethylhexyl) sulfosuccinate (AOT)/ n -heptane microemulsions were measured at 25°C by a calorimetric technique as a function of the molar ratio R ( R  = [water]/[AOT]) at a fixed AOT concentration. Calorimetric data indicate the formation of CaHPO 4 nanoparticles encapsulated in the aqueous core of the AOT reversed micelles displaying a slow growing process with time. Their energetic state is initially different from that in bulk water approaching the value in water at longer times. The observed growing process results to be completely inhibited by the presence of small amounts o…

Structural Investigation of Water/Lecithin/Cyclohexane Microemulsions by FT-IR Spectroscopy

Abstract FT-IR spectra of water/lecithin/deuterated cyclohexane microemulsions as a function of water/lecithin molar ratio R ( R = [water]/[lecithin]) at various volume fractions ( O ) of the micellar phase have been recorded at 25°C. After elimination of the small spectral contributions due to deuterated cyclohexane and normalization, the shape of the C–H stretching band due to lecithin has been found dependent upon R and O whereas that of the O–H stretching band has been found dependent only upon R . The change in shape of the C–H band was interpreted in terms of a modification of the lecithin alkyl chain packing order. The analysis of the O–H band provides evidence that the hydroxylic gr…

Microstructure and magnetic properties of colloidal cobalt nano-clusters

The magnetic response of nanometer sized Co nanoparticles (NP) prepared using reverse micelle solutions are presented. The use of complementary structural and morphological probes (like transmission electron microscopy, high resolution electron microscopy, X-ray absorption spectroscopy) allowed to relate the magnetic properties to the size, morphology, composition and atomic structure of the nanoparticles. All data agree on the presence of a coreshell structure of NPs made of a metallic Co core surrounded by a thin Co-oxide layer. The coreshell microstructure of NPs affects its magnetic response mainly raising the anisotropy constant. (C) 2010 Elsevier B.V. All rights reserved.

Study of AOT-stabilized microemulsions of urea dispersed in carbon tetrachloride

Measurements of some physico-chemical properties (density, viscosity, permittivity) of the urea/sodium bis(2-ethylhexyl) sulfosuccinate (AOT)/CCl4 system as a function of the volume fraction of the dispersed phase (0<Φ<0.7) at various urea to AOT molar ratio (Rurea) have been carried out at 25 °C. The experimental data analysis are consistent with the hypothesis that urea is entrapped as small-size molecular clusters within the hydrophilic core of the AOT reversed micelles and that this structure is preserved well above a threshold Φ value where a percolative transition occurs. Besides, X-ray diffraction spectra of samples at Φ=1, obtained by complete evaporation under vacuum of the apolar …

Sensitization of nanocrystalline TiO2 with 3,4,9,10-perylene tetracarboxylic acid

Optical properties of 3,4,9,10-perylene tetracarboxylic acid (PTCA) in the presence of nanocrystalline TiO2 (nominal diameter 15 nm) have been investigated in ethanol solution and in the solid state by UV-Vis absorption spectroscopy and steady-state and time-resolved fluorescence. Experimental results show that, in ethanol, the presence of TiO2 nanoparticles causes significant changes in the typical absorption and fluorescence bands of PTCA and in the fluorescence relaxation time. Similar effects are also detected in solid samples, obtained by electrospray deposition technique. The nonlinear optical properties of the PTCA-TiO2 in ethanol solutions were investigated using the single-beam Z-s…

Spectrophotometric investigation of the binding of vitamin E to water-containing reversed micelles.

The distribution constants of vitamin E partitioned between apolar organic phase and water-containing reversed micelles of sodium bis (2-ethylhexyl) sulfosuccinate (AOT), didodecyldimethylammonium bromide (DDAB), soybean phosphatidylcholine (lecithin) and tetraethylene glycol monododecyl ether (C12E4) have been evaluated by a spectrophotometric method. The results suggest that in the presence of domains from apolar organic solvent to surfactant and to water, vitamin E is partitioned between the micellar palisade layer and the organic solvent and also that its binding strength to reversed micelles depends mainly by specific interactions between the head group of vitamin E and that of the sur…

FT-IR and dielectric study of water/AOT liquid crystals

Abstract In order to explore the influence of microwave radiation on highly viscous microheterogeneous systems, the evolution of structural and dynamical properties of the water/sodium bis(2-ethylhexyl) sulfosuccinate (AOT) liquid crystals as a function of the molar ratio R (R=[water]/[AOT]) has been investigated by FT-IR spectroscopy and time domain reflectometry. The study emphasises how the progressive hydration of the surfactant head groups is mainly responsible for the structural and dynamical evolution of water/AOT liquid crystals. In particular, it has been found that the state of water at lower R values is strongly perturbed, bulk-like water appears only at R>23 and the water/AOT in…

Dielectric properties of water/lecithin/cyclohexane gels

Dielectric relaxation measurements in the frequency range 0.1–15 GHz have been carried out on water/lecithin/cyclohexane gels using a time domain reflectometry method (TDR). Dielectric dispersions describable in terms of a power law typical of percolated systems, but with exponents significantly different from those characterizing statically or dynamically percolated systems are observed. The dielectric dispersions, attributed to water and/or lecithin head group rotational motions, indicate that these motions are characterized by a wide spectrum of relaxation times.

Dynamical Properties of Self-Assembled Surfactant-Based Mixtures: Triggering of One-Dimensional Anomalous Diffusion in Bis(2-ethylhexyl)phosphoric Acid/n-Octylamine Systems

The dynamic features of bis(2-ethylhexyl)phosphoric acid (HDEHP)/n-octylamine (NOA) mixtures have been investigated as a function of the NOA mole fraction and temperature by (1)H NMR spectroscopy and rheometry. All data consistently suggest a composition-induced glass-forming behavior. The microscopic factors responsible for this behavior have been highlighted and have been explained in terms of driving forces given by HDEHP-to-NOA proton transfer, the tendency of the resulting species to establish H bonds and to spatially segregate the alkyl chains. The study sheds light on the molecular mechanism responsible for the peculiar behavior of transport properties in such systems and furnishes b…

FT-IR and nuclear overhauser enhancement study of the state of urea confined in AOT-reversed micelles

Abstract The system urea/sodium-bis(2-ethylhexyl)sulfosuccinate (AOT) dispersed in CCl 4 and benzene-d6 was investigated by viscosimetry, FT-IR and high-resolution 1 H NMR spectroscopy, as a function of urea/AOT molar ratio ( R urea ) at fixed AOT molal concentration (0.3467 mol kg −1 ) and as a function of AOT concentration at fixed R urea (0.5) at 25 °C. The experimental data are consistent with the hypothesis that urea is encapsulated as small-size hydrogen-bonded cluster in the hydrophilic micellar core of the AOT-reversed micelles and that this structure is maintained well above the volume fraction of the dispersed phase, where a percolative transition occurs. Intermolecular nuclear ov…

Photo-fragmentation of alkyl phosphates in the gas-phase

Abstract Alkyl phosphates are experiencing an ever increasing use due to the current arising of new applications. This implies their increasing presence in the environment so their stability and reactivity under high-energy photons, which are still unknown, need to be clarified. In this study, a mass spectrometric investigation of the ionization and fragmentation processes of four representative alkyl phosphates (dibutyl, tributyl, bis-2-ethylhexyl, and tris-2-ethylhexyl phosphate) induced by vacuum ultraviolet (VUV) radiation has been carried out. The experimental data show that fragmentation occurs through a stepwise cleavage of the bonds between the phosphate group and the alkyl chains l…

Water structure in water/AOT/n-heptane microemulsions by FT-IR spectroscopy

Abstract FT-IR spectra in the OH stretching region of water/sodium bis(2-ethylhexyl) sulfosuccinate (AOT)/n-heptane microemulsions as a function of the water/AOT molar ratio (R) and of the weight fraction (φ) of the micellar phase have been recorded at 25°C. After elimination of the unwanted CH contribution and correction for the water concentration, the shape of the normalized OH bands has been found to be dependent on R and practically independent of φ. The analysis of these bands in terms of “bound” and “bulk” water (representing, as a first approximation, the two water domains within the water pool) allowed the evaluation of the fraction (α) of the “bound” water as a function of R. A…

Physico-chemical characterization of Pd nanoparticles synthesized in w/o microemulsions

Abstract The long time stability of surfactant-coated Pd nanoparticles in w/o microemulsions has been investigated. It has been proven that in suitable conditions, the use of the functionalized surfactant Pd(AOT)2 allows to obtain very stable nanosized Pd particles and to finely control their average size.

Interactions of tryptophan and serotonin with biomembrane models: Binding to reversed micellar systems of ionic and non ionic surfactants

The interactions of Tryptophan (TRP) and Serotonin (5-HT), with water-containing sodium bis (2-ethylhexyl) sulfosuccinate (AOT), didodecyldimethylammonium bromide (DDAB) and tetraethylene glycol monododecyl ether (C12E4) reversed micelles have been investigated by UV absorption spectroscopy. Our results suggest that independently of the nature of the surfactant and the amount of the water encapsulated into the micellar core, TRP and 5-HT are solubilized in the micellar phase, preferring to be located in a shallow region constituted by the hydrated surfactant head groups. This is due to the amphiphilic nature of TRP and 5-HT and the biological implications are discussed.

Electrostatic contribution to the interaction of α, β poly (N-hydroxyethyl)-DL-aspartamide with sodium dodecylsulfate micelles

The enthalpic effect due to the interaction between α, β poly(N-hydroxyethyl)-DL-aspartamide (PHEA) and sodium dodecylsulfate (SDS) in aqueous solutions as a function of the surfactant concentration was measured by the calorimetric technique at various NaCl concentrations. A marked influence of the added electrolyte on the PHEA-SDS interaction was observed. An analysis of the experimental enthalpies allows to estimate the electrostatic and the hydrophobic contributions to the enthalpy of interaction between PHEA and SDS micelles. The results were rationalized in terms of effects due to the screening of the charges residing on PHEA and SDS micelles.

Combined small-angle x-ray scattering/extended x-ray absorption fine structure study of coated Co nanoclusters in bis(2-ethylhexyl)sulfosuccinate

Chemically stable cobalt nanostructures have been prepared with Co(II) reduction in the confined space of cobalt bis(2-ethylhexyl)sulfosuccinate, Co(AOT)2, reverse micelles dispersed in n-heptane. The reaction was carried out by adding a solution of sodium borohydride in ethanol (1% weight) to a 0.2M micellar solution of Co(AOT)2 in n-heptane at a reductant to Co(II) molar ratio of 4. This procedure involves the rapid formation of surfactant-coated Co nanoparticles followed by their slow separation as nanostructures embedded in a sodium bis(2-ethylhexyl)sulfosuccinate matrix. The resulting composites, characterized by extended x-ray absorption fine structure and small-angle x-ray scattering…

Structural and optical properties of novel surfactant-coated Yb-TiO2 nanoparticle

Abstract In this paper a novel hybrid approach to synthesise composite nanoparticles is presented. It is based on the laser ablation of a bulk target (Yb) immersed in a reversed micellar solution which contains nanoparticles of a different host material (TiO2 nanoparticles) previously synthesised by chemical method. This approach thus exploits the advantages of the chemical synthesis through reversed micellar solution (size control, nanoparticle stabilisation), and of the laser ablation (‘‘clean’’ synthesis, no side reactions). Central role is played by the microscopic processes controlling the deposition of the ablated Yb atoms onto the surface of TiO2 nanoparticles which actually behave a…

Physicochemical Properties of Copper(II) Bis(2-ethylhexyl) Sulfosuccinate Reversed Micelles

Abstract Measurements of some physicochemical properties (density, viscosity, conductance, UV–vis spectra, IR spectra) of the water/copper(II) bis(2-ethylhexyl) sulfosuccinate (Cu(DEHSS) 2 )/CCl 4 microemulsions, at a fixed surfactant molal concentration ([Cu (DEHSS) 2 ] = 0.05003 mol kg −1 ), as function of the molar ratio R ( R = [water]/[DEHSS − ]) have been performed at 25°C. Information on some structural and dynamical properties of the water-containing Cu(DEHSS) 2 reversed micelles and of their evolution with R are derived from the experimental results. The comparison with the same properties of water-containing sodium bis(2-ethylhexyl) sulfosuccinate reversed micelles allows to evide…

Calorimetric investigation of the complex formation between surfactants and α-, β- and γ-cyclodextrins

Abstract A calorimetric technique has been used to study complex formation between α-, β- and γ-cyclodextrins (αCD, βCD and γCD) and some surfactants (sodium dodecylsulphate (SDS), hexadecyl trimethylammonium bromide (CTAB) and p-(1,1,3,3-tetramethylbutyl) phenoxypoly(oxyethyleneglycol) (Triton X-100)). The experimental data indicate that some complexes (SDS-αCD, SDS-βCD and CTAB-αCD) are very stable and allow direct determination of their stoichiometry and molar enthalpy of complex formation. Those for other complexes closely fit a model based on an equilibrium reaction between surfactant, cyclodextrin and a single complex. According to the model, data analysis allows determination of the …

Study of the growth of ZnS nanoparticles in water/AOT/n-heptane microemulsions by UV-absorption spectroscopy

Abstract ZnS nanoparticles were synthesized at 25°C using water-containing AOT reversed micelles as nanoreactors and characterized by UV–vis spectroscopy. The time dependence of the spectra emphasizes a slow growing process of the ZnS nanoparticles coupled with a change of their photophysical properties. Both processes are well described by power laws. The nanoparticle size can be controlled by the molar ratio R ( R =[water]/[AOT]), i.e. by the micellar size. The deposits obtained by evaporation of the volatile components of the microemulsions are found to be composed of a surfactant matrix containing ZnS nanoparticles smaller and more stable than that in the corresponding microemulsions.

Surfactant self-assembling in gas phase: electrospray ionization- and matrix-assisted laser desorption/ionization-mass spectrometry of singly charged AOT clusters.

The self-assembling of sodium bis (2-ethylhexyl) sulfosuccinate (AOT) in gas phase has been investigated by electrospray ionization- and matrix-assisted laser desorption/ionization mass spectrometry. Large surfactant clusters with an aggregation number close to that found in apolar media have been observed either as positive or negative ions. Moreover, the marked predominance of singly charged species as well as preliminary theoretical calculations strongly suggest an aggregate structure characterized by an internal hydrophilic core hosting the extra charge surrounded by an apolar shell constituted by the surfactant alkyl chains. This structure is similar to that of the more familiar revers…

FT-IR investigation of the urea state in lecithin and sodium bis(2-ethylhexyl)phosphate reversed micelles

Abstract FT-IR spectra of urea/lecithin/CCl4 and urea/sodium bis(2-ethylhexyl) phosphate (NaDEHP)/CCl4 systems as a function of the urea-to-surfactant molar ratio (Rurea) at a fixed surfactant concentration (0.1 mol kg−1) have been recorded at 25 °C. Analysis of the absorption spectra leads the to hypothesis that urea is confined within the hydrophilic micellar core of lecithin and NaDEHP reversed micelles. The encapsulation of urea involves some changes of the urea NH stretching band with respect to that of the pure solid urea, attributable to confinement effects. The stretching modes of the surfactant head group are affected by the presence of urea, indicating specific urea-surfactant hea…

Calorimetric investigation of water/lecithin/cyclohexane microemulsions

The enthalpies of dilution of water/lecithin/cyclohexane microemulsion-gels at variousR values (R=[water]/[lecithin]) and molar enthalpies of solution of water in lecithin/cyclohexane at a fixed lecithin concentration were determined calorimetrically at 25°C. Through a description of the process of dilution of water/lecithin/cyclohexane microemulsion-gels as one involving mainly the scission of lecithin reversed micelles in to smaller ones, the concentration dependence of the enthalpy was rationalized. Surprisingly, in order to account for the dilution enthalpies, it was not necessary to hypothesize a thermal effect arising from the breakage of the micellar network present in the micremulsi…

Calorimetric and viscosimetric investigation of the interaction between α,β-polyasparthydrazide and sodium dodecyl sulfate micelles

Abstract The interaction between α,β-polyasparthydrazide (PAHy) and sodium dodecyl sulfate (SDS) micelles in aqueous solution was investigated by calorimetry and viscosimetry. The dependence of the enthalpic effect due to this interaction upon the surfactant concentration was rationalized in terms of a progressive binding of SDS micelles to the polymeric backbone. The analysis of the calorimetric data allow evaluation of the binding ability of SDS micelles to the polymeric chain. The viscosimetric behavior of SDS plus PAHy aqueous solutions, discussed in terms of the parameter F [F = ηrel(PAHy) + ηrel(PAHy) − ηrel(SDS+PAHy)], confirms the occurence of the interaction between SDS micelles an…

Calorimetric investigation of the formation of ZnS nanoparticles in w/o microemulsions

The enthalpies of precipitation of ZnS nanoparticles within water containing reversed micelles of sodium bis(2-ethylhexyl) solfosuccinate, L-α phosphatidylcholine, tetraethyleneglycol-mono-n-dodecyl ether and didodecyldimethylammonium bromide as a function of the molar concentration ratioR (R=[water]/[surfactant]) were measured by calorimetric technique. The results indicate that the energetic state of ZnS nanoparticles confined in the aqueous core of the reversed micelles is different from that in bulk water. Effects due to nanoparticle size, adsorption of HS− ions on the nanoparticle surface and interactions between nanoparticles and water/surfactant interfaces are discussed.

Study of AOT-stabilized microemulsions of formamide and n-methylformamide dispersed in n-heptane

Abstract A wide investigation of some physicochemical properties (density, viscosity, conductance, IR spectra, permittivity) of AOT-stabilized dispersions of formamide and n -methylformamide in n -heptane has been performed. The experimental data are consistent with the hypothesis that these highly hydrophilic substances are encapsulated within AOT reversed micelles and that this structure is maintained for both systems well above the volume fraction of the dispersed phase where a percolative transition occurs. In addition, the observed properties of these microemulsions reveal the pivotal role of intermicellar attractive interactions in driving the percolative transition. A marked modifica…

Structural investigation of the confinement of finite amounts of trehalose in water-containing sodium bis(2-ethylhexyl)sulfosuccinate reversed micelles

The structural effect of trehalose confined in water-containing sodium bis(2-ethylhexyl)sulfosuccinate (AOT) reversed micelles at water to AOT molar ratio W = 5 and 10 as a function of the trehalose to AOT molar ratio T (0 < T < 0.1) has been investigated by small-angle neutron scattering (SANS). SANS data analysis is consistent with the hypothesis that trehalose is encapsulated within the quite spherical hydrophilic micellar cores of water-containing reversed micelles, causing an increase of the aggregate size and a decrease of the polydispersion. Moreover, SANS results suggest that the trehalose confinement in water-containing reversed micelles involves marked changes on the molecular pac…