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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 leading to the formation of esters with a lower number of alkyl chains and the protonated orthophosphoric acid as ending product. Interestingly, the presence of charged species with mass-over-charge (m/z) values larger than the parent ion is also observed in dibutyl and bis-2-ethylhexyl phosphate, suggesting the existence of their dimers in the gas phase. This has been rationalized, with the aid of ab-initio DFT calculations, in terms of the capability of these molecules to form H-bonds. The photo-induced reactivity in the gas phase has been clarified, and its similarity with the natural bacterial degradation has been pointed out.

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 basic knowledge to be used to design novel materials with planned physicochemical properties.

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. On the other hand, the fragmentation of negatively doubly charged NaAOT aggregates is always characterized by a structural collapse of the entire ensemble leading to the formation of small-size singly charged fragments. The analysis of the collision energy required to fragment the 50% (CE 50% ) of positively and negatively charged NaAOT aggregates allows to emphasize the role of electrostatic repulsion, degree of freedom and statistical effects as determining factors of the aggregation number and charge state dependence of CE 50% values. Overall, the observed behavior of positively and negatively multicharged NaAOT aggregates in gas phase has been rationalized in terms of the electrostatic interactions between sodium counterions and negatively charged surfactant heads mainly responsible of the reverse-micelle like structural arrangement of these non-covalent aggregates and of their stability.

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 aggregates in gas phase show identical structural features. Analogous conclusions can be drawn analyzing the infrared multiple photon dissociation (IRMPD) spectra of AOTNa solutions in water/methanol and n-hexane. Moreover, according to the idea that gas phase can be considered an apolar environment par excellence, data consistently suggest a reverse micelle-like aggregation. Some peculiarities of the mechanisms leading to aggregate formation through electrospray ionization of surfactant solutions in solvent media with different polarity have been also discussed. Copyright © 2011 John Wiley & Sons, Ltd.

Binary mixtures of the amphiphilic materials octanoic acid and bis(2-ethylhexyl) amine, have been investigated by broadband dielectric spectroscopy as a function of temperature. Depending on the composition, the dc conductivity of the mixture is several orders of magnitude higher than that of the pure components at room temperature. The higher the conductivity of the mixture, the lower is the relaxation frequency at which the dielectric relaxation occurs. Moreover, non Arrhenius trends of the dc conductivity and of the dielectric relaxation time vs. temperature have been observed for some of the mixtures above their melting temperature. The formation of transient eteroadducts of OA and BEEA molecules, most likely 2(OA):BEEA, could be responsible for the conductivity enhancement versus composition, as well as for the increase of the viscosity, and for the slowing down of the dielectric relaxation. This picture, supported by the results of Wide Angle X rays Scattering and 1H-NMR measurements, can also account for the peculiar temperature dependence of the dc conductivity and of the dielectric relaxation.

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 the organic solvent leads to the preparation of very interesting gold nanoparticle/surfactant liquid crystal composites. Such nanocomposites, characterized by WAXS and SAXS, showed the presence of small (radius∼14 A° ) and stable gold nanoparticles dispersed in the surfactant matrix. It has been also emphasized that a simple washing process with ethanol is a suitable method to eliminate the excess of surfactant leaving a novel nanomaterial constituted by gold nanoparticles coated by a monolayer of opportunely oriented surfactant molecules. © 2005 Elsevier B.V. All rights reserved.

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 hydrophilic groups both of Vitamin E and surfactant. Moreover, the RVE dependence of the Vitamin E distribution constant and of the micellar size suggest that the inclusion of increasing amounts of Vitamin E in reversed micelles involves substantial changes in the structural and dynamical properties of the micellar aggregates. The occurrence of mutual effects and the partitioning of Vitamin E between hydrophilic/hydrophobic interfaces and apolar domains allow to infer some important biological implications concerning the capacity of Vitamin E to scavenge free radicals arising from hydrophilic and/or hydrophobic domains, possible variations of its local reactivity respect to that observed in bulk as well as its significant influence on the stability of biomembranes.

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.

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 inhibition can be achieved at any moment of the process leading to an easy and fine size control. The main advantage of this procedure is that the BEA-coated CdS nanoparticles can be easily separated from the reaction medium and dispersed in nonpolar media such as heptane and in polar media such as an aqueous surfactant solution.

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 the AOT reversed micelles. The insertion of urea in the micellar core causes a significant increase of the aggregate size along the minor-axis direction. FT-IR data indicates that, quite independently from the urea and AOT concentrations, the encapsulation of urea clusters in the AOT micellar core involves some changes ...

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 overhauser enhancements (NOEs) were observed between urea amidic protons and AOT protons located in the proximity of the sulfonate group, thus proving that the solubilizate/surfactant interaction is mainly localized around the polar head of AOT within the micellar core. Long-range NOEs were also detected between urea NH 2 and methyl group of the β-alkyl chain of AOT, suggesting that the two alkyl chains of the surfactant play different roles in the interaction with urea and the bulk solvent. Some changes to the structural and dynamical properties were observed during solubilization in AOT-reversed micelles.

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 head group interactions. On the other hand, analysis of the CO stretching band suggests that the urea CO groups are not engaged in urea-surfactant head group interactions.

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.

The state of N-methylurea (NMU) confined within the hydrophilic core of sodium bis(2-ethylhexyl) sulfosuccinate (AOT) reversed micelles (radius 1.5–1.8 nm) has been investigated by Fourier transform infrared spectroscopy. The analysis of the spectral features leads to the hypothesis that NMU is encapsulated in the micellar core as small-sized molecular clusters. As a consequence of their small size and of NMU–AOT head group interactions, these clusters display marked departures from the H-bonded structure of the pure solid NMU even at the higher NMU to AOT molar ratio. The stretching modes of NMU CO, AOT CO and sulfonate groups indicate unambiguously specific NMU–AOT head group interactions.

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 deposited nanoparticles structure has been studied by Wide Angle X-Ray Scattering. The molecular processes underlying the simultaneous gold reduction and nanoparticle deposition have been discussed.

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 presence of urea, indicating specific urea–AOT head group interactions. On the other hand, analysis of the AOT CO stretching band provides evidence that these groups are not significantly involved in urea–AOT interactions.

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 been proved by small-angle X-ray scattering and transmission electron microscopy, respectively. By mixing these solutions, the solid–solid reaction between Na2S and ZnSO4 nanoparticles leading to the formation of very small-sized ZnS nanoparticles has been ascertained by UV spectrophotometry.

Fourier transform infrared (FT-IR) spectroscopy and time domain reflectometry (TDR) have been employed to study nano-confinement effects in water–tetraethylene glycol monododecyl ether (C12E4) system as a function of the water to surfactant molar ratio (R) at 25 °C. The study emphasises that, at low R values, the vibrational dynamics of water entrapped between equidistant parallel bilayers of oriented surfactant molecules is significantly different from that of pure water whereas at R>7 it becomes practically indistinguishable. On the other hand, even at the higher R values investigated, the dielectric properties of the aqueous domain confined in water–C12E4 liquid crystals are found to be strongly affected by confinement effects. The observed single relaxation processes with a symmetrical distribution of relaxation time are discussed in terms of effects due to interfacial interactions and topological restrictions on water-surfactant head group dynamics in liquid crystals. Correlation between the structur...

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 interface polarisation is controlled by the fast translational dynamics of sodium counterions and the slow orientational dynamics of the AOT ionic head groups.

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 of bis(2-ethylhexyl) phosphate acid (DEPA) leading to the formation of stable nanosized calcium monohydrogen phosphate particles coated by an oriented monolayer of chemically bonded DEPA molecules. After evaporation of the volatile components of the microemulsions, it was observed by transmission electron microscopy that CaHPO 4 nanoparticles embedded in the surfactant matrix are still present.

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.

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.

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 evidence the pivotal role of the water-triggered interactions between the counterion and the surfactant anion on driving the structural and dynamical evolution of reversed micelles.

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 micremulsion-gels. This result indicates that the building-up of the micellar network mainly arises from topological entanglements and steric hindrances among the lecithin reversed micelles. Attribution of the molar enthalpy of solution of water essentially to the thermal effect arising from the intermicellar aggregation process induced by the water addition allowed a rough estimation of the scission energy (the energy necessary to break an Avogadro's number of micelles) and of the micellar aggregation number.

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 modification of the structural and dynamical properties of formamide and n -methylformamide accompanying their solubilization within AOT reversed micelles has also been observed.

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.

Gold nanoparticles, synthesized within AOT reversed micelles, have been imaged by an atomic force microscope (AFM) operating in the contact mode in air at room temperature. The AFM images show an attractive interaction among gold nanoparticles leading to the formation of well distinct aggregates where, however, each nanoparticle retains its individuality. Moreover, the AFM images show that the mean size of gold nanoparticles is a function of the size of the AOT reverse micelles and offer evidence of a stabilization mechanism of the nanoparticles due, most probably, to the formation of an adsorbed layer of surfactant molecules at the nanoparticle surface. This stabilization mechanism results in being active even at high nanoparticle concentration.

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 groups of lecithin form strong hydrogen bonds whereas the added water is confined in bulk-like water domains.

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.

The formation enthalpy of gold nanoparticles in water/sodium bis(2-ethylhexyl) sulfosuccinate ( AOT ) n- heptane microemulsions as a function of the water AOT molar ratio R(R = [water] [AOT] ) was measured by a calorimetric technique at various AOT concentrations. The size of Au nanoparticles was determined by transmission electron microscopy. The results indicate that both the energetic state and the dimensions of the gold nanoparticles are influenced by the radius and the concentration of the reversed AOT micelles. Analysis of the decay of the calorimetric signal provides evidence of some interesting features of the growing process of the Au nanoparticles in water/AOT/n-heptane microemulsions.

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.

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.

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.

The enthalpies of precipitation of calcium carbonate and calcium fluoride in water/sodium bis-2-ethylhexyl sulfosuccinate/ n -heptane, water/didodecyldimethylammonium bromide/ n -heptane and water/tetraethyleneglycol-mono- n -dodecyl ether/isooctane microemulsions were measured by a calorimetric technique. The results indicate that the energetic state of CaCO 3 and CaF 2 nanocrystals encapsulated in the aqueous microregions of these microemulsions is strongly different from that in bulk water. Effects due to the smallness of the nanocrystals, interactions between nanocrystals and water/surfactant interfaces and changes of the thermodynamic parameters in nanoscopic water environments are discussed.

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 aggregates in gas phase show identical structural features. Analogous conclusions can be drawn analyzing the infrared multiple photon dissociation (IRMPD) spectra of AOTNa solutions in water/methanol and n-hexane. Moreover, according to the idea that gas phase can be considered an apolar environment par excellence, data consistently suggest a reverse micelle-like aggregation. Some peculiarities of the mechanisms leading to aggregate formation through electrospray ionization of surfactant solutions in solvent media with different polarity have been also discussed.

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.

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 frequencies, was attributed to the rotational dynamics of the solvated solute molecules.

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 and the PAHy macromolecule.

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.

In this paper we present some results from Brillouin scattering measurements on lecithin-based gels. The normalized hypersound absorption data give clear evidence of the establishement of an extended network at temperatures lower than 25 o C, when the micelle size reaches a threshold value. The transition between the two regions is interpreted as originated by a delicate balance between the breading and re-forming mechanisms of the micelles and the system polydispersivity on which the collisional effects play the main role

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 reversed AOT micelles.

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. At each R, α was found to be nearly the same for percolated and unpercolated microemulsions. This suggests that the water/AOT/n-heptane microemulsions well above the percolation threshold are still formed by water-containing AOT reversed micelles dispersed in the oil phase.

Amantadine was modified by direct acylation with succinic and glutaric anhydrides and the covalent bond with α,β-poly( N -hydroxyethyl)-DL-aspartamide (PHEA) was realized. The amount of amantadine in the obtained copolymers was evaluated by hydrolysis of the conjugates. The enthalpic effect due to the interaction between the two synthesized polymeric prodrugs and sodium dodecylsulphate micelles as a simple system mimicking the cellular membrane, was measured by the calorimetric technique and compared with that of PHEA. Binding of PHEA-succinylamantadine (PHEA-S-AMA) to surfactant micelles appeared to be stronger than that shown by PHEA-glutarylamantadine (PHEA-G-AMA).

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 stoichiometry, stability constant and molar enthalpy of their complex formation. The thermodynamic parameters indicate that stoichiometry and complex stability are strongly influenced by entropic contributions.

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 organic solvent.

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, showed the presence of subnanometer sized cobalt nanoparticles aggregated together to form elongated structures coated by the surfactant molecules.

The ultrasonic absorption in water/sodium bis(2‐ethylhexyl) sulfosuccinate (AOT)/n‐heptane system has been measured at 25 °C, as a function of the water/AOT molar ratio (X) and of the volume fraction (φ) of the micellar phase. The ultrasonic spectra have been found strongly dependent on φ and nearly independent on X. In particular, as φ increases, ultrasonic dynamics shifts from a single to a distribution of relaxation times with occurrence of viscoelastic effects. Such findings have been correlated to the increased connectivity of the micellar network.

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 micellar interface are discussed.