Wide Angle X-ray Scattering as a Technique of Choice to Probe Asphaltene Hierarchical Structures.

Bitumens are composite systems extensively used in road pavements. Due to their complex nature, a rational understanding of the relationships between composition, structure and performances of these materials is still far from being achieved, so research attempting to shed more light in this field is required. Here, we exploit Wide Angle X-ray Scattering (WAXS) as a technique of choice to shed light on the bitumen structure at different length scales. Diagnostic fingerprints, characterizing the WAXS profile, are correlated to specific Bragg distances which can be reasonably attributed to the molecular and supramolecular aggregation taking place at various levels of complexity leading to the formation of hierarchical structures. Due to the inherent instability of these materials some indications are given to obtain reliable structural data.

Electrospray ion mobility mass spectrometry of positively charged sodium bis[2-ethythexyl)sulfosuccinate aggregates.

Collision cross-sections (CCS) of positively singly and multiply charged aggregates of the surfactant sodium bis(2-ethylhexyl)sulfosuccinate (AOTNa) in the gas phase have been measured by quadrupole ion mobility time-of-flight mass spectrometry. Calibration of the observed drift times to the CCS of the AOTNa non-covalent aggregates was achieved by collecting, under the same experimental conditions, the drift times of a range of singly and multiply charged polyalanine peptides whose CCS had been obtained by conventional ion mobility spectrometry. Together with an obvious increase of the aggregate cross-section with the aggregation number, it was found that the aggregate cross-section increases with the charge state due to the sodium counterions steric effect and the augmented electrostatic repulsion. This finding is consistent with the result of a previous molecular dynamics study on positively charged AOTNa aggregates in the gas phase showing that, by increasing the charge state, the aggregates become progressively more oblate; implying a rise of their CCS. Moreover, the occurrence at each aggregation number and extra charge of a unique value of cross section points toward aggregates whose conformations do not show discernible shape change in the experiment time scale.

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 heads and sodium ions become surrounded by water molecules, whereas the alkyl chains lay at the droplet surface. Meanwhile, evaporation of water molecules and of solvated sodium ions occurs, leading to a decrease of the droplet size and charge. At 350 K, no ejection of neutral or charged surfactant molecules is observed, whereas at 500 K, some fragmentation occurs, and at 800 K, this event becomes more frequent. The interplay of all these processes, which depend on the values of temperature, N(AOT)(0) and N(Na)(0) eventually leads to anhydrous charged surfactant aggregates with prevalence of monocharged ones, in agreement with experimental results of ESI mass spectrometry. The quantitative analysis of the MD trajectories allows to evidence molecular details potentially useful in designing future ESI experimental conditions.

Surfactant self-assembling in the gas phase: bis(2-ethylhexyl)-sulfosuccinate divalent metal ion anionic aggregates.

RATIONALE: Investigation of fundamental aspects driving surfactant self-assembling and of the capability of including guest molecules or ions in their micellar aggregates is an exciting research field for theoretical and technological reasons. In this light, assembling and chelating properties of sodium bis(2-ethylhexyl)sulfosuccinate (AOTNa) towards divalent metal ion chlorides have been investigated in the gas phase by electrospray ionization mass spectrometry in negative ion mode, tandem mass spectrometry and energy-resolved mass spectrometry. METHODS: Water/methanol solutions of AOTNa and chloride salts of nickel, magnesium, calcium and manganese, with different AOTNa/metal salt ratios, were infused into the electrospray source of a LCQ DECA ion trap mass spectrometer, operating in negative ion mode, at a flow rate of 5 µL/min. Low energy collision-induced dissociations were carried out by using helium with collision energy in the range 1-5 eV. RESULTS: A variety of negatively singly charged monometallated and mixed metal aggregates have been observed, some of which were able to incorporate the metal counter ion of the inorganic salt used. The stability of these aggregates was evaluated by energy-resolved mass spectrometry which showed, for the anions [AOTM(II)Cl(2)](-), a stability order Ca > Mn > Mg > Ni. Their decomposition pathways show the unusual formation of the radical anions [C(4)HO(6)SM(II)Cl](-•). CONCLUSIONS: This study shed some light on the assembling and chelating properties of AOT(-) towards divalent metal ions to form negatively charged assemblies, some of them incorporating the metal counter ion of the inorganic salt used. Differently from what was observed with positively charged AOT-M(II) aggregates, solvated species were not detectable. An exception to the even-electron rule was observed in the decomposition pathway of [AOTM(II)Cl(2)](-).

Emerging dynamics in surfactant-based liquid mixtures: octanoic acid/bis(2-ethylhexyl) amine systems.

This work focuses on the dynamic phenomena emerging in self-assembled transient intermolecular networks formed when two different surfactants are mixed. In particular, the relaxation processes in liquid mixtures composed by bis(2-ethylhexyl)amine (BEEA) and octanoic acid (OA) in the whole composition range has been investigated by dielectric spectroscopy and Brillouin spectroscopy. A thorough analysis of all the experimental data consistently suggests that, mainly driven by acid-base interactions arising when the two surfactants are mixed, supra-molecular aggregates formation causes the slowing down of molecular dynamics. This, in turn, reflects to longer-range relaxations. These changes have been found to be composition-dependent, involving strong departures of the mixture physico-chemical properties from an ideal behaviour, and reflecting the structural and dynamical features of local structures. In particular, the peculiar dynamic processes occurring in these local inter-molecular structures, have been found to be the factors responsible for the observed and quite surprising increase of direct-current conductivity which occurs when two different (and pretty non-conductive) surfactants are mixed. The discovery can be used not only to design novel materials for application purposes but also to shed more light on the basic principles regulating charge migration in structured liquid systems.

Characterization of gas phase aggregates of bis(2-ethylhexyl)sulfosuccinate (AOT) and divalent metal ions. Elimination of radical species in the decomposition pathways of even-electron [AOTMIICl2]- anions.

Structure and properties of even-electron anionic species formed by bis(2-ethylhexyl)sulfosuccinate (AOT) and divalent metal ions (M(II)) with stoichiometry [AOTM(II)Cl(2)](-) have been investigated by using electrospray ionization and different mass spectrometry techniques, such as high resolution, accurate mass measurements, collision-induced dissociation (CID) multiple-stage mass spectrometry. Owing to CID, eliminations of neutrals, mainly consisting in hydrochloric acid, 2-ethyl-1-hexene and 2-ethylhexanol, and an unexpected loss of an alkyl radical have been observed. The radical anions [C(4)HO(6)SM(II)Cl](-•) so produced have been characterized by MS(3) experiments. Density functional theory calculations have been carried out for investigating structure and stability of the ionic species formed in the decomposition pathways.

Self-assembly in surfactant-based liquid mixtures: octanoic acid/Bis(2-ethylhexyl)amine systems.

The physico-chemical properties of Bis(2-ethylhexyl)amine (BEEA) plus octanoic acid (OA) mixtures have been investigated by IR, SAXS, WAXS, viscosimetry, and AC complex impedance spectroscopy in the whole composition range. Mainly driven by proton transfer from the acidic OA to the basic BEEA, the formation of stoichiometrically well-defined adducts takes place in the mixtures. This causes the slowing down of molecular dynamics and the increase in charge carrier number density. Interestingly, while the pure components possess no significant conductivity (about 10(-12) S cm(-1) at 25 °C), their mixtures show a composition-dependent enhanced conductivity (up to about 10(-5) S cm(-1)), i.e., more than seven orders of magnitude higher than that of the pure components. The comparison of the composition dependence of viscosity, direct-current conductivity, and static permittivity indicates the concurrence of contributions of different adducts and that the dynamics controlling molecular reorientation and momentum and charge transfer, even if ultimately related to the proton transfer from OA to BEEA, are different. The results can be used not only to design novel materials for application purposes, but also to shed more light on the principles regulating molecular self-assembly in surfactant-based liquid systems.

Gas phase charged aggregates of bis(2-ethylhexyl)sulfosuccinate (AOT) and divalent metal ions: first evidence of AOT solvated aggregates.

Assembling and chelating properties of sodium bis(2-ethylhexyl)sulfosuccinate (AOTNa) towards divalent metal ions have been investigated in the gas phase by electrospray ionization mass spectrometry. A variety of positively charged monometallated and mixed metal aggregates are formed. Interestingly, several ions contain solvent (MeOH, H(2)O) molecules and constitute the most abundant AOT cationic aggregates not containing sodium. These species are the first example of solvated AOT-metal ion aggregates in the gas phase. By increasing the surfactant aggregation number, the abundance of solvated species becomes lower than that of unsolvated ones. Decompositions of ionic species have been studied by tandem mass spectrometry, and their stability has been determined through energy resolved mass spectrometry. In contrast with positively charged AOT-alkaline metal ion aggregates, whose decompositions are dominated by the loss of individual surfactant molecules, AOTNa-divalent ion aggregates mainly dissociate through the cleavage of the AOT H(2)C-O bond followed by further intramolecular fragmentations. This finding, that is consistent with an enhanced chelation of divalent ions with AOT(-) head groups, has been taken as an indication that such aggregates are characterized by a reverse micelle-like organization with a ionic core formed by the metal cations interacting with the negatively charged surfactant polar heads, whereas the surfactant alkyl chains point outside.

Triggering dissymmetry in achiral dye molecules by chiral solvents: Circular dichroism experiments and DFT calculations.

The electronic circular dichroism spectra of achiral product "Lumogen F Red" (ROT-300) in four different chiral solvents are recorded at different temperatures. DFT calculations allow to identify two enantiomeric conformers for ROT-300. In vacuo they are equally populated; in chiral solvents one enantiomer prevails. Thermodynamic quantities involved in the chiral preference are derived.

Gas phase infrared multiple photon dissociation spectra of positively charged sodium bis(2-ethylhexyl)sulfosuccinate reverse micelle-like aggregates.

The capability of infrared multiple photon dissociation (IRMPD) spectroscopy to gain structural information on surfactant-based supramolecular aggregates has been exploited to elucidate intermolecular interactions and local organization of positively charged sodium bis(2-ethylhexyl)sulfosuccinate (AOTNa) aggregates in the gas phase. A detailed analysis of the stretching modes of the AOTNa CO and SO(3)(-) head groups allows one to directly probe their interactions with sodium counterions and to gain insight in their organization within the aggregate. Similarities and differences of the IRMPD spectra as compared to the infrared absorption spectrum of micellized AOTNa in CCl(4) have been analyzed. They strongly suggest a reverse micelle-like organization of AOTNa charged aggregates in the gas phase. Apart from low-abundance fragmentation channels of the AOTNa (molecule) itself, the main dissociation pathway of singly charged surfactant aggregates is the loss of neutral surfactant molecules, while doubly charged aggregates dissociate preferentially by charge separation forming singly charged species. In both cases, decomposition leads to the formation of the most energetically stable charged fragments.

Effects of the net charge on abundance and stability of supramolecular surfactant aggregates in gas phase.

Self-assembling of amphiphilic molecules under electrospray ionization (ESI) conditions is characterized by quite unexpected phenomenology. The noticeable differences with respect to the condensed phase are attributable to the absence of the surfactant-solvent interactions, the presence of net charge in the aggregates, and the strong deviation from equilibrium conditions. Aiming to investigate the effects of the net charge on abundance and stability of supramolecular surfactant aggregates, positively and negatively charged aggregates of sodium bis(2-ethylhexyl)sulfosuccinate (AOT) and sodium methane sulfonate (MetS), butane sulfonate (ButS) and octane sulfonate (OctS) have been studied by ESI mass spectrometry, energy resolved mass spectrometry and density functional theory calculations. The negatively charged aggregates are found to be less stable than their positive counterparts. The results are consistent with a self-assembling pattern dominated by electrostatic interactions involving the counterions and head groups of the investigated amphiphilic compounds while the alkyl chains point outwards, protecting the aggregates from unlimited growth processes.

Self-assembly in surfactant-based liquid mixtures: bis(2-ethylhexyl)phosphoric acid/bis(2-ethylhexyl)amine systems.

Surfactant-based liquid mixtures constitute an interesting class of nanostructured materials with promising potential in specialized applications. Here, structural and conductometric properties of liquid mixtures composed of bis(2-ethylhexyl)amine (BEEA) and bis(2-ethylhexyl)phosphoric acid (HDEHP) have been thoroughly investigated with the aim to correlate structural features with system charge transport capability. The evolution of self-assembled local nanostructures with system composition has been investigated by FT-IR and XRD while the conductometric properties were probed by conventional AC complex impedance. Both pure components exhibit nano-segregation due to their amphiphilic nature but with only very low proton conductivities. However their mixtures, characterized by local organization of polar and apolar domains driven by acid-base interactions between HDEHP PO(4)H and BEEA NH groups, show enhanced structural order and proton conductivity.

Fluorescence emission and enhanced photochemical stability of Zn(II)-5-triethyl ammonium methyl salicylidene ortho-phenylendiiminate interacting with native DNA.

The photophysical and photochemical properties of the cationic Zn(II) complex of 5-triethyl ammonium methyl salicylidene ortho-phenylendiimine (ZnL(2+)) interacting with native DNA were investigated by steady state and time-resolved fluorescence spectroscopies. Experimental results indicate that, in the presence of DNA, ZnL(2+) is efficiently protected from a photochemical process, which occurs when it is in the free state dispersed in aqueous solution. The analysis of the absorption and emission spectra of ZnL(2+), both stored in the dark and after exposure to tungsten lamp light for 24 h, corroborated by quantum chemical calculations, allowed us to point out that ZnL(2+) undergoes a photoinduced two-electron oxidation process. According to this picture, the protective action of DNA toward the intercalated ZnL(2+) was attributed to an effective inhibition of the ZnL(2+) photooxidation. In this context, it can be considered that DNA-intercalated ZnL(2+) is located in a region more hydrophobic than that sensed in the bulk water solvent. Moreover, by a thorough analysis of steady state and time-resolved fluorescence spectra, the interaction process can be consistently explained in terms of a complete intercalation of the complex molecules and that the polarity of the environment sensed by intercalated ZnL(2+) is comprised between that of methanol and ethanol.

Sodium bis(2-ethylhexyl)sulfosuccinate self-aggregation in vacuo: molecular dynamics simulation.

Molecular dynamics (MD) simulations were conducted for systems in vacuo consisting of n AOT(-) anions (bis(2-ethylhexyl)sulfosuccinate ions) and n+/- 1 or n Na(+) ions up to n = 20. For n = 15, positively charged systems with Li(+), K(+), and Cs(+) cations were also considered. All systems were observed to form reverse micelle-like aggregates whose centre is occupied by cations and polar heads in a very compact solid-like way, while globally the aggregate has the form of an elongated and rather flat ellipsoid. Various types of statistical analyses were carried out on the systems to enlighten structural and dynamical properties including gyration radius, atomic pair correlation functions, atomic B-factor and moment of inertia tensor. For completeness and comparison the stability of reverse micelle is tested in the case of neutral n = 20 system in CCl(4) solution.

Fast proton conduction in hydrogen bonded microheterogeneous systems: bis(2-ethylhexyl)phosphoric acid/N-methyl formamide liquid mixtures.

Structural and dynamical properties of bis(2-ethylhexyl)phosphoric acid (HDEHP)/N-methyl formamide (NMF) liquid mixtures in the whole composition range have been investigated by Fourier Transform Infrared spectroscopy (FT-IR), X-rays Diffraction (XRD), and AC complex impedance spectroscopy. Driven by hydrogen bond interactions among HDEHP PO(4)H group and NMF CO and NH groups, and also by steric effects among the HDEHP alkyl chains, the system microstructure is mainly characterized by the coexistence of spatially separated hydrophilic and hydrophobic nanodomains showing local organization and short-range order. The evolution of this structural feature with system composition has been highlighted by FT-IR and XRD. On the other hand, the thermally activated proton mobility within these hydrophilic domains, as pointed out by AC complex impedance measurements, emphasizes the occurrence of a percolating behaviour characterized by percolation threshold at zero. Due to fast proton conduction across the interconnected network formed by the polar groups, some samples showed very high room-temperature conductivity up to 10(-3) S cm(-1).

Spectroscopic and structural investigation of the confinement of D and L dimethyl tartrate in lecithin reverse micelles.

The confinement of D and L dimethyl tartrate in lecithin reverse micelles dispersed in cyclohexane has been investigated by FT-IR, polarimetry, electronic and vibrational circular dichroism (ECD and VCD), 1H NMR, and small-angle X-ray scattering (SAXS). Measurements have been performed at room temperature as a function of the solubilizate-to-surfactant molar ratio (R) at fixed lecithin concentration. The analysis of experimental data indicates that the dimethyl tartrate molecules are solubilized within reverse micelles in proximity to the surfactant head groups in the same way for the D and L forms. The encapsulation of dimethyl tatrate within lecithin reverse micelles involves changes in its H-bonds, from what is observed in the pure solid or in CCl4 solutions; this is a consequence of the establishment of specific solute-surfactant headgroup interactions and of confinement effects. In the 0 < or = R < or = 1.7 range, SAXS profiles of dimethyl tartrate/lecithin/ cyclohexane micellar solutions are well-described by a model of interacting polydisperse spherical micellar cores whose mean radius does not change appreciably with R (i.e., it changes from about 18 to 20 angstroms). 1H NMR diffusion measurements of both dimethyl tartrates and lecithin were rationalized in terms of collective translational motions of the entire micellar aggregate and of their molecular diffusion among clusters of reverse micelles. The association of optically active lecithin with D and L dimethyl tartrate leads to the formation of self-organized supramolecular aggregates whose interesting chiroptical features are evidenced by polarimetry and CD.

Spatially ordered surfactant assemblies in the gas phase: negatively charged bis(2-ethylhexyl)sulfosuccinate-alkaline metal ion aggregates.

The formation and structural features of negatively charged aggregates of sodium bis(2-ethylhexyl)sulfosuccinate (AOTNa) surfactant molecules in the gas phase have been investigated by electrospray ionization mass spectrometry (ESI-MS) and density functional theory calculations. Mainly driven by the interactions of alkali metal ions both with the oxygen atoms of the sulfonate group and with the succinate moiety of the AOT- anion, spatially ordered supramolecular assemblies, characterized by an internal core composed of surfactant counterions and hydrophilic head groups surrounded by the surfactant alkyl chains pointing outwards, are formed. Calculations have shown that surfactant self-organization in the gas phase is energetically favoured, the energy of formation of negatively charged aggregates from isolated AOTNa and AOT- being linearly related to the aggregation number. Information on the chelating properties of AOTNa towards clusters of inorganic salts was achieved by infusion of solutions at various AOTNa/metal salt (NaCl, NaBr, NaI, LiI, KCl, CsI, RbI) ratios in the ESI source of a mass spectrometer. A wide variety of negatively charged AOT-metal aggregates, some of them also incorporating halide (X-) ions, has been observed. Calculations have shown that the capture of a halide anion to give the AOTMX- species is favoured but the energetics of the process depends on the alkali metal and halide types. The use of energy-resolved mass spectrometry has allowed us to evaluate the stability of different complexes and to evaluate the role played by the metal ion. Overall, the present investigation supports the idea that, in the gas phase, mainly driven by electrostatic interactions, surfactant molecules are present as molecular aggregates characterized by a reverse micelle-like organization with an internal core formed by the surfactant counterions and head groups surrounded by the surfactant alkyl chains. These peculiar aggregates are able to incorporate ionic clusters in their hydrophilic core.

Gas-phase ion chemistry of protonated melatonin.

The gas-phase ion chemistry of protonated melatonin has been investigated by mass spectrometric (MS) techniques involving chemical ionisation, fast atom bombardment and electrospray ionisation. Either naturally- occurring or collision-induced decomposition e-D derivatives obtained by exchange with D(2)O. The analysis of experimental results allows definite pathways for the formation of the ion at m/z 174 to be assigned and sheds some more light on the overall fragmentation pathways. Experiments on labelled derivatives evidenced H-D scrambling processes during fragmentation.

The zero field self-organization of cobalt/surfactant nanocomposite thin films.

Cobalt nanostructures have been prepared by a chemical route based on the Co(II) reduction in the confined space of cobalt bis(2-ethylhexyl)sulfosuccinate (Co(DEHSS)(2)) reverse micelles dispersed in n-heptane. This procedure involves the rapid formation of surfactant softly coated Co nanostructures followed by a slow separation process of the magnetic-field responsive Co/surfactant nanocomposites from the liquid phase. The detailed structure of thin films of the Co/surfactant nanocomposites has been investigated by scanning force microscopy (SFM). The thin films were characterized by different anisotropic features. Micrometric long domains of self-aligned ellipsoidal NPs (tens of nanometers in size) have been observed, together with bendable micrometric long homogeneous nanofibers (NFs). The film structures were strongly dependent on the Co/surfactant ratio and, by increasing the Co percentage, the system was forced towards the formation of mutually connected superstructures consisting of anisotropic bands of self-aligned NFs and anisotropic 2D close packed Co-NP super-lattices. Transmission electron microscopy (TEM) showed that the NPs observed by SFM are in effect composed of almost spherical and oxygen-free cobalt nanoparticles, 1-3 nm in size, which typically assemble in larger ellipsoidal systems tens of nanometers in size. Magnetic force microscopy (MFM) demonstrates the magnetic response of these thin films, highlighting the different behavior (attractive/repulsive) of the Co-NPs aggregates towards the oscillating magnetized tip. The above structural findings have been interpreted in terms of nanostructures/matrix interaction along with a fine balance between short-range isotropic repulsions, van der Waals attractions and long-range anisotropic magnetic interactions.

Physico-chemical investigation of nanostructures in liquid phases: nickel chloride ionic clusters confined in sodium bis(2-ethylhexyl) sulfosuccinate reverse micelles.

The confinement of finite amounts of nickel chloride in the hydrophilic core of sodium bis(2-ethylhexyl) sulfosuccinate (AOT) reverse micelles dispersed in n-heptane has been investigated by FT-IR, UV-vis-NIR and fluorescence spectroscopies. The analysis of experimental data consistently leads to hypothesize that NiCl(2) forms small size ionic clusters stabilized by a monolayer of oriented surfactant molecules. Due to confinement and interfacial effects, these ionic clusters show peculiar photophysical properties, which are different from those possessed by the bulk material. From NiCl(2)/AOT/n-heptane solutions, by evaporation of the organic solvent, interesting salt/surfactant nanocomposites at various salt concentrations have been prepared and characterised by WAXS. On the other hand, after mix with Na(2)S-containing dry micellar systems, the formation of NiS nanoparticles have been ascertained by UV-vis spectroscopy.