Self-assembly in surfactant-based mixtures driven by acid–base reactions: bis(2-ethylhexyl) phosphoric acid– n-octylamine systems

Structural and dynamic features of bis(2-ethylhexyl) phosphoric acid (HDEHP)–n-octylamine (NOA) mixtures as a function of the NOA mole fraction (XNOA) have been investigated by SAXS, WAXS, IR, dielectric spectroscopy and polarized optical microscopy. In the 0 ¡ XNOA , 0.5 range, mixtures are transparent liquids, while the abrupt formation of a waxy solid characterized by an hexagonal bidimensional structure occurs at XNOA = 0.5. Such a composition-induced phase transition results from the synergetic effect of the progressive increase in number density of ordered HDEHP–NOA nanodomains with XNOA. Mainly driven by an HDEHP to NOA proton transfer, the increase of structural order with XNOA arises from the progressive substitution of loosely hydrogen bonded HDEHP–HDEHP aggregates with strongly bonded NOA–HDEHP ones. Analysis of SAXS patterns at temperatures in the 10–70 uC range emphasized that these local structures are scarcely impacted by an increase of thermal fluctuations. Effects due to the steric compatibility between HDEHP and NOA apolar moieties have been highlighted. Overall, the results allow us to emphasize the role of specific polar and apolar interactions joined to steric effects in regulating the molecular organization in surfactant mixtures and can be used to design novel materials with planned physico-chemical properties

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 divalentmetal ions (MII) with stoichiometry [AOTMIICl2]– 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 [C4HO6SMIICl]–• so produced have been characterized by MS3 experiments. Density functional theory calculations have been carried out for investigating structure and stability of the ionic species formed in the decomposition pathways

Dibutyl phosphate/propylamine mixtures show supra-molecular slow building up under magnetic field

Liquids with anisotropic local nanostructures which are able to be oriented by a magnetic field can give birefringence. Usually magnetically-induced birefringence is low owing to the low magnetic energy of molecules and to the averaging effect due to thermal agitation. At the same time, the response is usually very fast given the typical timescales of molecular orientational dynamics (nanoseconds). However, we show that the dibutyl phosphate/propylamine liquid mixture is characterized by an extremely slow response (hours) to the magnetic field and by an intense overall effect (Δn/λ ≈ −0.1m-1at 1 Tesla).This surprising behavior has been interpreted as a manifestation of a novel phenomenon of progressive building up of larger and larger internally ordered hetero-associates driven by the magnetic field and involving strongly interacting amphiphiles

Dynamic evolution of the oscillatory Belousov-Zhabotinsky reaction upon addition of a non-ionic polymer

The dynamic evolution of the oscillatory Belousov-Zhabotinsky reaction upon addition of increasing amount of the non-ionic polymer polypropylene glycol with molecular weight 425 g mol(-1) (PPG-425) was investigated in a stirred-batch reactor by monitoring the Ce(IV) absorbance changes. The oscillatory parameters are significantly altered by the presence of the polymer. The findings obtained in the present work revealed that the PPG-425 is not only more effective, than other polymer previously [R. Lombardo, C. Sbriziolo, M.L. Turco Liveri, K. Pelle, M. Wittmann, Z. Noszticzius, in: J.A. Pojman, Q. Tran-Cong-Miyata (Eds.), Nonlinear Dynamics in Polymeric Systems, American Chemical Society, Washington, DC, 869 (2004) 292] studied, in perturbing the BZ systems but also more capable of producing key radical species, which in turn can be exploited for the preparation of new polymeric materials

Deconvolution procedure of the UV-vis spectra. A powerful tool for the estimation of the binding of a model drug to specific solubilisation loci of bio-compatible aqueous surfactant-forming micelle

UV-vis-spectra evolution of Nile Red loaded into Tween 20 micelles with pH and [Tween 20] have been analysed in a non-conventional manner by exploiting the deconvolution method. The number of buried sub-bands has been found to depend on both pH and bio-surfactant concentration, whose positions have been associated to Nile Red confined in aqueous solution and in the three micellar solubilisation sites. For the first time, by using an extended classical two-pseudo-phases-model, the robust treatment of the spectrophotometric data allows the estimation of Nile Red binding constant to the available loci. Hosting capability towards Nile Red is exalted by the pH enhancement. Comparison between binding constant values classically evaluated and those estimated by the deconvolution protocol unveiled that overall binding values perfectly match with the mean values of the local binding sites. This result suggests that deconvolution procedure provides more precise and reliable values, which are more representative of drug confinement

Nonlinear Response of a Batch BZ Oscillator to the Addition of the Anionic Surfactant Sodium Dodecyl Sulfate

The response of the Belousov-Zhabotinsy (BZ) system to the addition of increasing amounts of the anionic surfactant sodium dodecyl sulfate (SDS) was monitored at 25.0 °C in stirred batch conditions. The presence of SDS in the reaction mixture influences the oscillatory parameters, i.e., induction period and oscillation period, to an extent that depends on the surfactant concentration. The experimental results have shown that the induction period increases slightly on increasing surfactant concentration and, then, a further increase in the [SDS] leads to an enhancement while the oscillation period increases monotonously on increasing SDS concentration. It has been proposed that the response of the oscillatory BZ system to the addition of SDS is due to the peculiar capability of the organized surfactant assemblies to affect the reactivity by selectively sequestering some key reacting species. Indeed, explanations of the experimental results have been given on the basis of the role played by the micellar shape, which in turn dictates the hydrophobic nature. The suggested perturbation effects have been supported by performing viscosity measurements on the aqueous SDS solutions and by the spectrophotometric estimation of the binding constant of the bromine species to the micellar aggregates. This study has indirectly corroborated the existence of two kind of micelles and unambiguously revealed that the bromine species show a different affinity toward the spherical and rod-like micelles

Confinement of chiral molecules in reverse micelles:FT-IR,polarimetric and VCD investigation on the state of dimethyl tartrate in sodium bis(2-ethylhexyl) sulfosuccinate reverse micelles dispersed in carbon tetrachloride

The state of d and l-dimethyl tartrate confined within dry sodium bis(2-ethylhexyl) sulfosuccinate (AOT) reverse micelles dispersed in CCl4 has been investigated by FT-IR spectroscopy, polarimetry, and vibrational circular dichroism (VCD). Measurements have been performed at 25 ◦C as a function of the solubilizate-to-surfactant molar ratio (R) at a fixed AOT concentration (0.158 M). The analysis of experimental data is consistent with the hypothesis that both enantiomers of dimethyl tartrate are mainly entrapped in the reverse micelles and located in proximity to the surfactant head-group region. The formation of this interesting self-organized chiral nanostructure involves some changes of the typical H-bonding of dimethyl tartrates in the pure solid state or as monomers dispersed in CCl4 attributable to the establishment of specific solubilizate/surfactant head-group interactions and confinement effects

Thermal Frontal Polymerization with a Thermally Released Redox Catalyst

We studied thermal frontal polymerization using a redox systemin an attempt to lower the temperature of the frontally polymerizable system while increasing the front velocity so as to obtain a self-sustaining front in a thinner layer than without the redox components. A cobalt-containing polymer with a melting point of 63 C (Intelimer 6050X11) and cumene hydroperoxide were used with a triacrylate. The use of the Intelimer decreased the front velocity but allowed fronts to propagate in thinner layers and withmore filler while still having a pot life of days. Nonplanar modes of propagation occurred. Fronts propagated faster when 6-O-palmitoyl-L-ascorbic acid was used as a reductant. Interestingly, fronts were also faster with the reductant even without the Intelimer if kaolin clay was the filler; however, the pot life was significantly reduce

Peculiar Mechanism of Solubilization of a Sparingly Water Soluble Drug into Polymeric Micelles. Kinetic and Equilibrium Studies

Complementary kinetic and equilibrium studies on the solubilization process of the sparingly water soluble tamoxifen (TAM) drug in polymeric aqueous solutions have been performed by using the spectrophotometric method. In particular, the amphiphilic copolymers obtained by derivatization of polymeric chain of poly(N-2-hydroxyethyl)-DLaspartamide, PHEA, with poly(ethylene glycol)s, PEG (2000 or 5000 Da), and/or hexadecylamine chain, C16, namely PHEA-PEG2000-C16, PHEA-PEG5000-C16, PHEA-C16, have been employed. Preliminary to the kinetic and equilibrium data quantitative treatment, the molar absorption coefficient of TAM in polymeric micelle aqueous solution has been determined. By these studies the solubization sites of TAM into the polymeric micelles have been determined and the solubilization mechanism has been elucidated through a nonconventional approach by considering the TAM partitioned between three pseudophases, i.e., the aqueous pseudophase, the hydrophilic corona, and the hydrophobic core. The simultaneous solution of the rate laws associated with each step of the proposed mechanism allowed the calculation of the rate constants associated with the involved processes, the values of which are independent of both the copolymer concentration and nature, with the exception of the rate of the TAM transfer from the corona to the core. This has been attributed to the steric barrier, represented by the corona, which hampers the solubilization into the core. The binding constant values of the TAM to the hydrophilic corona of the polymeric micelles, calculated through the quantitative analysis of the equilibrium data, depend on the thickness of the hydrophilic headgroup, while those of the hydrophobic core are almost independent of the copolymer type. Further confirmation to the proposed solubilization mechanism has been provided by performing the kinetic and equilibrium measurements in the presence of PHEA-PEG2000 and PHEAPEG5000 copolymers

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 non-covalent 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 behave similarly, but the slope of the CCE vs DoF plot is steeper for positive ions, suggesting that these are more stable than their negative counterparts