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 highli…
Structure and dynamics of dibutylphosphate/n-propylamine ionic liquid: A multi-scale theoretical study
Abstract Owing to the amphiphilic nature of their constituent molecules, binary mixtures of pure liquid surfactants are usually characterized by enhanced nano-segregation and thus can exhibit interesting transport properties and complex macroscopic behavior. In this ambit it was recently shown by Turco Liveri et al. (2018) that mixtures of short aliphatic chains compounds at room temperature, such as dibutyl phosphate (DBP) and n-propylamine (PA) liquids, display ionic liquid–like behavior ascribed to phosphate-to-amine proton transfer. To gain a detailed molecular picture of the system structure and dynamics and to understand the molecular mechanisms at the basis of the observed behavior, …
Structural and Optical Properties of Novel Surfactant Coated TiO2Ag Based Nanoparticles
Stable dispersions of surfactant-coated TiO2–Ag based nanoparticles in apolar medium have been prepared by performing sequentially the hydrolysis of titanium(IV) isopropoxide and the reduction of Ag? in the confined space of sodium bis(2-ethylhexyl)sulfosuccinate (NaAOT) reverse micelles. Depending on the sequence length, this novel procedure allowed the synthesis of semiconductor–metal nanoparticles, nominally indicated as TiO2/Ag, TiO2/Ag/TiO2, and TiO2/Ag/TiO2/ Ag, stabilized by a monolayer of oriented surfactant molecules. The structural characterization of these nanoparticles has been performed by High Resolution Transmission Electron Microscopy (HR-TEM), while optical properties were …
Molecular association of small amphiphiles: Origin of ionic liquid properties in dibutyl phosphate/propylamine binary mixtures
Abstract Binary mixtures of liquid surfactants, owing to the amphiphilic nature of the molecules involved, can exhibit nano-segregation and peculiar transport properties. The amphiphilicity, and consequently the resulting self-assembly, can be tuned by changing the length of the alkyl chains and the nature of the polar head group. So, in the present study, the structural and dynamic properties of dibutyl phosphate/propylamine liquid mixtures at various compositions have been investigated by Wide Angle X-ray Scattering (WAXS), FT-IR, rheometry and dielectric spectroscopy in order to study the intermolecular association taking place when alkylphosphates and alkylamines with a small apolar par…
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.…
Folate targeted coated SPIONs as efficient tool for MRI
The development of more sensitive diagnostic tools allowing an early-stage and highly efficient medical imaging of tumors remains a challenge. Magnetic nanoparticles seem to be the contrast agents with the highest potential, if properly constructed. Therefore, in this study, hybrid magnetic nanoarchitectures were developed using a new amphiphilic inulin-based graft copolymer (INU-LAPEG-FA) as coating material for 10-nm spinel iron oxide (magnetite, Fe3O4) superparamagnetic nanoparticles (SPION). Folic acid (FA) covalently linked to the coating copolymer in order to be exposed onto the nanoparticle surface was chosen as the targeting agent because folate receptors are upregulated in many can…
Synthesis and physico-chemical characterization of Au/TiO2 nanostructures formed by novel "cold" and "hot" nanosoldering of Au and TiO2 nanoparticles dispersed in water
Abstract A novel approach to synthesize Au/TiO2 nanostructures with interesting optical properties is presented and discussed. It is based on the nanoparticle “cold” or “hot” nanosoldering occurring when two water suspensions of Au and TiO2 nanoparticles are merely mixed at room temperature or laser irradiated after mixing. Thanks to the high fraction and mutual reactivity of surface species, immediately after the mixing process, the encounters between Au and TiO2 nanoparticles in liquid phase are enough for “cold” nanosoldering of gold nanoparticles onto TiO2 nanoparticles to occur. The optical characterizations show that this fast process (timescale less than 1 min) is followed by a slowe…
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…
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 (X-NOA) have been investigated by SAXS, WAXS, IR, dielectric spectroscopy and polarized optical microscopy. In the 0 <= X-NOA < 0.5 range, mixtures are transparent liquids, while the abrupt formation of a waxy solid characterized by an hexagonal bidimensional structure occurs at X-NOA = 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 X-NOA. Mainly driven by an HDEHP to NOA proton transfer, the increase of structural order with X-NO…
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 ha…
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…
Novel atrazine-binding biomimetics inspired to the D1 protein from the photosystem II of Chlamydomonas reinhardtii.
Biomimetic design represents an emerging field for improving knowledge of natural molecules, as well as to project novel artificial tools with specific functions for biosensing. Effective strategies have been exploited to design artificial bioreceptors, taking inspiration from complex supramolecular assemblies. Among them, size-minimization strategy sounds promising to provide bioreceptors with tuned sensitivity, stability, and selectivity, through the ad hoc manipulation of chemical species at the molecular scale. Herein, a novel biomimetic peptide enabling herbicide binding was designed bioinspired to the D1 protein of the Photosystem II of the green alga Chlamydomonas reinhardtii. The D1…
Nano-demixing as a novel strategy for magnetic field responsive systems: the case of dibutyl phosphate/bis(2-ethylhexyl)amine systems
Pure surfactant liquids and their binary mixtures, owing to the amphiphilic nature of the molecules involved, can exhibit nano-segregation and peculiar transport properties. The possibility of opportunely choosing the amphiphiles should lead to the formation of anisotropic aggregates that can be oriented by an external factor like a magnetic field. In this case some properties, like optical birefringence, can be induced by the use of a magnetic field. Dynamic features of dibutyl phosphate (DBP)/bis(2-ethylhexyl)amine (BEEA) mixtures have been investigated by FT-IR, NMR, rheometry, Brillouin scattering, and magnetically-induced birefringence measurements as a function of the BEEA mole fracti…
Dissolution of nitrones in alkylphosphates: A structural study
Nitrones are chemical compounds with well-established anti-oxidant and spin-trapping properties. Their low solubility in water for many of them limits their applications, so opportune solvents must be found. In this study, two recently synthetized oxindole nitrones with proven antiproliferative and antioxidant activity have been dissolved in several liquid amphiphiles, chosen as model solvents. The effect of the polar head nature and the alkyl chain length/type have been investigated by a combined experimental (solubility, UV–vis spectroscopy) / computational (molecular dynamics) approach. The different chemical structures of the various solvents offer different chemical environments to the…
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 natur…
Synthesis of Yb nanoparticles by laser ablation of ytterbium target in sodium bis(2-ethylhexyl)sulfosuccinate reverse micellar solution
Abstract Surfactant-coated ytterbium nanoparticles were produced by Nd:YAG laser ablation of a Yb bulk target immersed in sodium bis(2-ethylhexyl)sulfosuccinate (AOT)/ n -heptane micellar solution. In our experimental conditions, as highlighted by IR spectroscopy, AOT molecules are not decomposed by the intense laser pulses but play a pivotal role in the stabilisation of Yb nanoparticles. The formation of Yb nanoparticles in the liquid phase was monitored by UV–Vis spectroscopy whereas the Yb/AOT composites obtained by evaporation of the organic solvent were characterised by XPS and TEM. Data analysis consistently shows the presence of surfactant-coated, nearly spherical and non-interacting…
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…
Non-ideal mixing behavior in dibutyl phosphate-propylamine binary liquids: Dielectric and nuclear magnetic resonance investigations
Abstract Owing to the amphiphilic nature of their constituent molecules, binary mixtures of pure liquid surfactants are usually characterized by enhanced nano-segregation and thus can exhibit interesting transport properties and complex macroscopic behavior. In this ambit it was recently shown by Turco Liveri et al. (J. Mol. Liq. 263 (2018) 274–281) at room temperature that mixtures of short aliphatic chains compounds, such as dibutyl phosphate (DBP) and n-propylamine (PA) liquids, due to their ability to allow for phosphate-to-amine proton transfer, display ionic liquid–like behavior with composition-dependent enhanced conductivity, viscosity, and magnetically-induced birefringence. To und…
Anti-Arrhenian behaviour of conductivity in octanoic acid–bis(2-ethylhexyl)amine systems: a physico-chemical study
Pure surfactant liquids and their binary mixtures, owing to the amphiphilic nature of the molecules involved, can exhibit nano-segregation and peculiar transport properties. The structural and dynamic properties of octanoic acid (OA)–bis(2-ethylhexyl)amine (BEEA) liquid mixtures at various compositions have been studied by Wide Angle X-ray Scattering (WAXS), 1H-NMR and broadband dielectric spectroscopy as a function of temperature. It was found that the self-assembly occurs via proton exchange between the OA COOH group and the BEEA NH one; such self-assembled local structures are affected anisotropically by a temperature increase so that the thermal dilatation is more marked in a direction …
Self-assembly in surfactant-based liquid mixtures: Octanoic acid/Bis(2-ethylhexyl)amine systems
Abstract 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., …
Induced Chirality in Confined Space on Halogen Gold Complexes
The solubilization of HAuCl4 in toluene within optically active reverse micelles and lamellar structures formed by (1R,2S)-Dodecyl(2-hydroxy-1-methyl-2-phenylethyl)- dimethylammonium bromide (DMEB) has allowed us to evidence the complex phenomenology accompanying the confinement of Au salt within these nanostructures. Together with a chloride/bromide exchange process occurring in the first coordination sphere of an Au ion, UV−vis and electronic circular dichroism (ECD) spectra reveal the appearance of an induced dichroic signal attributable to Au complexes entrapped in the hydrophilic domain of the DMEB chiral nanostructures. Interestingly, change of the effective oxidation state and coordi…
Bis(2-ethylhexyl)phosphoric acid/bis(2-ethylhexyl)amine mixtures as solvent media for lithium-ions: A dynamical study
Abstract The self-diffusion coefficient, the spin-lattice relaxation times and ionic conductivity of lithium ions in liquid mixtures composed of bis(2-ethylhexyl)amine (BEEA) and bis(2-ethylhexyl)phosphoric acid (HDEHP) have been thoroughly investigated as a function of composition and temperature by NMR spectroscopy and conductometry. While the temperature and composition dependence of diffusion coefficients of lithium ions follow the same trend observed for those of the surfactant molecules, the spin-lattice relaxation times of lithium ions and 1 H are remarkably different. The observed behavior has been interpreted in terms of lithium ions diffusion occurring through its association with…
How self-assembly of amphiphilic molecules can generate complexity in the nanoscale
Abstract Given the importance of nanomaterials and nanostructures in modern technology, in the past decades much effort has been directed to set up efficient bottom up protocols for the piloted self-assembly of molecules. However, molecules are generally disinclined to adopt the desired structural organization because they behave according to their own specific intermolecular interactions. Thus, only some selected classes of chemical compounds are capable to lead to useful self-assembled structures. Amphiphiles, simultaneously possessing polar and apolar moieties within their molecular architecture, can give a wide scenario of possible intermolecular interactions: polar–polar, polar–apolar,…
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…
Composite Nanoparticles
International audience; Composite nanoparticles are advanced materials having recently gained increasing attention due to their scientific and technological importance.They find awide variety of applications such as catalysts with huge activity and specificity,metal semiconductor junctions, optical sensors, and modifiers of polymeric films for packaging.
Decoupling of Dynamic Processes in Surfactant-Based Liquid Mixtures: The Case of Lithium-Containing Bis(2- ethylhexyl)phosphoric Acid/Bis(2-ethylhexyl)amine Systems
Pure surfactant liquids and their binary mixtures, because of the amphiphilic nature of the molecules involved, can exhibit nanosegregation and peculiar transport properties. The idea that inspired this work is that the possibility of including in such media salts currently used for technological applications should lead to a synergy between the properties of the salt and those of the medium. Therefore, the dynamic features of bis(2-ethylhexyl)amine (BEEA) and bis(2-ethylhexyl)phosphoric acid (HDEHP) liquid mixtures were investigated as a function of composition and temperature by (1)H nuclear magnetic resonance (NMR) spectroscopy and rheometry. Inclusion of litium trifluoromethanesulfonate…
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 nanocomposi…
Spectroscopic and structural characterization of pure and FeCl3-containing tri-n-butyl phosphate
The spectroscopic properties and liquid structure of pure tri-n-butyl phosphate (TBP) and FeCl3/TBP solutions have been investigated by Uv–Vis and Raman spectroscopies, X-ray diffraction and conductometry. Uv–Vis and Raman spectra, supported by conductometric measurements, consistently indicate that the solubilized salt is present mostly as TBP n [FeCl3 − n ] n+ and FeCl4 − complex ions due to specific interaction with the TBP phosphate group. Thanks to this interaction, a high amount of salt (up to 13 % w/w) can be dissolved despite the relatively low dielectric constant of TBP. The X-ray diffractogram of pure TBP has been interpreted in terms of three main contributions which can be attri…
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…
Effect of additives on the structural organization of asphaltene aggregates in bitumen
Abstract Bitumens are composite materials whose complex organization hinders the rational understanding of their relationships between composition, structure and performances. So, research attempting to shed more light in this field is required. In this work Wide Angle X ray Scattering (WAXS) has been used to explore the influence of six opportunely chosen additives on the bitumen structure with the aim to ultimately correlate the findings with the bitumen performances. Diagnostic fingerprints have been observed in the WAXS profile: asphaltenes form stuck of about 18 A and constituted by about 6 asphaltene units on average. Such stucks are, in turn, organized at higher levels of complexity …
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…
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…
Morphology and local organization of water-containing (1R,2S)-Dodecyl(2-hydroxy-1-methyl-2-phenylethyl)dimethylammonium bromide reverse micelles dispersed in toluene
The structure of (1R,2S)-dodecyl(2-hydroxy-1-methyl-2-phenylethyl)dimethylammonium bromide (DMEB) reverse micelles, at various water-to-surfactant molar ratio (R-w, R-w = [water]/[DMEB]) and DMEB concentrations, has been investigated by small angle X-ray scattering (SAXS) and extended X-ray absorption fine structure spectroscopy (EXAFS). SAXS data of dry reverse micelles are consistent with a model of spherical hydrophilic core surrounded by DMEB alkyl chains whose polydispersity decreases significantly with surfactant concentration. By adding water, a sphere to cylinder transition occurs leading to a one-dimensional growth of reverse micellar cores with R-w and surfactant concentration. Th…
Physicochemical Investigation of Lightfast AgCl and AgBr Nanoparticles Synthesized by a Novel Solid−Solid Reaction
Small size AgX (X = Br, Cl) nanoparticles have been synthesized by a novel solid−solid reaction performed by mixing two dry dispersions of AgNO3 and KX nanoparticles in AOT/n-heptane solutions. UV−vis investigation ascertained that formation of nanosized particles taking place after the mixing process is fast and complete. Microcalorimetric measurements of the thermal effect coupled with the mixing process suggest the occurrence of confinement effects and adsorption of the surfactant molecules at the nanoparticle surface, hinting at formation of charged nonstoichiometric surfactant-coated nanoparticles. The analysis of SAXS spectra shows that salt-containing AOT reversed micelles are slight…
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…
Quantum dots functionalised artificial peptides bioinspired to the D1 protein from the Photosystem II of Chlamydomonas reinhardtii for endocrine disruptor optosensing
Herein we describe the design and synthesis of novel artificial peptides mimicking the plastoquinone binding niche of the D1 protein from the green photosynthetic alga Chlamydomonas reinhardtii, also able to bind herbicides. In particular, molecular dynamics (MD) simulations were performed to model in silico the behaviour of three peptides, D1Pep70-H, D1Pep70-S264K and D1Pep70-S268C, as genetic variants with different affinity towards the photosynthetic herbicide atrazine. Then the photosynthetic peptides were functionalised with quantum dots for the development of a hybrid optosensor for the detection of atrazine, one of the most employed herbicides for weed control in agriculture as well …
Iron and lithium-iron alkyl phosphates as nanostructured material for rechargeable batteries
Abstract Inorganic/organic hybrid materials composed by iron atoms bonded to an alkyl phosphate can be easily synthesized by mixing at 110 °C iron chlorides with tri-alkyl phosphates. Since structural information on these products are lacking and taking into account that lithium/iron organic hybrid materials are important in lithium ion battery technology we report here the physico-chemical characterization of different hybrid lithium/iron butylphosphates. These materials are characterized by the presence of elongated hexagonal crystals stable up to 315 °C. The insertion of lithium does not affect the local structure. Thanks to such structures the material can be electrochemically-cycled an…
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…
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.
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…
Complex permittivity of FeCl3/AOT/CCl4 microemulsions probed by AC impedance spectroscopy
Abstract The complex permittivity of FeCl 3 /AOT/CCl 4 microemulsions in the 1–10 5 Hz frequency range has been measured by the conventional AC complex impedance technique. Measurements as a function of the volume fraction of the dispersed phase (FeCl 3 + AOT) and temperature at fixed salt-to-AOT molar ratio ( R , R = 0.5) show that the entrapment of FeCl 3 clusters significantly enhances the local permittivity of the AOT reverse micelles and the number density of charge carriers resulting from the peculiar state of the confined inorganic salt. An estimate of the apparent static permittivity of the FeCl 3 ionic clusters entrapped in the core of AOT reverse micelles gives the very high an…