Adsorption of heavy metals by layered double hydroxides grown in situ on Al foam

We investigated the adsorption of heavy metal ions on a nanostructured coating of zinc-aluminum layered double hydroxides (Zn-Al LDHs) grown on aluminum foam by one-step hydrothermal process. This approach aimed to increase the interactive surface and provide a more practical medium for removal of toxic heavy metals from aqueous media. The foam coated with LDH was characterized by using scanning electron microscopy and X-ray diffraction. After immersion in a copper-rich water solution, X-ray photoelectron spectroscopy demonstrated the occurrence of adsorbed copper on the LDH-coated foam with two oxidation states: particles of metallic copper Cu⁰ with oxidized surface Cu⁺¹. X-ray diffraction showed the presence of Cu⁺² in the LDH structure.     

Unsaturated Phosphorus Compounds: Spatial and,Electronic Structure on the Base of Electrical and Electrooptical Methods

Abstract

The influence of classical systems connected with phosphorus atom: >P(Y)-C(R)=C<, >P(Y)-C[tbnd]S- and unusual ones, -P=E and P[tbnd]S- on spatial and electronic structure of or-ganophosphorus compounds has been considered. On the complex analysis ground of polarity and polarizability data, obtained for model olefines, imines, acetylenes and nitriles the existence of nonformal similarity between this compounds classes has been demonstrated. It is reflected in analogy of conformational behaviour and electron effects, realized with participation of multiple carbon, nitrogen and phosphorus bonds:     

Synthesis,binding and fluorescence studies of a new neutral H-bonding receptor for anions based on 3,5-bis(trifluoromethyl)phenylurea

The synthesis and anion binding studies of the new neutral receptor 1,1′-(2,2′-(4,10-dimethyl-1,4,7,10-tetraazacyclododecane-1,7-diyl)bis(2-oxoethane-2,1-diyl))bis(3-(3,5-bis(trifluoromethyl)phenyl)urea) (L1) are reported. L1 is a macrocyclic ligand containing the 3,5-trifluoromethylphenylureido-binding fragment attached as a side arm on the tetraazacyclododecane. L1 is soluble in numerous organic solvents; the binding properties of L1 towards several simple anions (G) were investigated by NMR, UV–vis and fluorescence techniques in DMSO and CH₃CN solutions. L1 is able to bind F^? , Cl^?  and AcO^?  in both solvents; in addition, it binds Br^?  in CH₃CN. Fluoride shows the highest constant values in the halide series (F^?  > Cl^?  > Br^? ) and AcO^?  is the most strongly bound among all the anions investigated. L1 is able to signal the presence of the anions in solution by fluorescence change; in the case of acetate, this occurs in the visible range.     

Compatibility study of the acetylsalicylic acid with different solid dosage forms excipients

This study is part of a research project aimed to find and optimize methods by which drug-excipient compatibility can be reliably and quickly assessed. The objective of the present study was to evaluate the compatibility of the acetylsalicylic acid (ASA), an non-steroidal anti-inflammatory drug, with pharmaceutical excipients of common use including diluents, binders, disintegrants, lubricants and solubilising agents. In order to investigate the possible interactions between ASA and eleven excipients differential scanning calorimetry (DSC) and thermogravimetry/derivative thermogravimetry analysis completed by Fourier transform infrared spectroscopy (FT-IR) and X-ray powder diffraction were used for compatibility study. The DSC has proven to be, among the selected analytical techniques, the most sensitive and specific in assessing the compatibility. The samples, as physical mixtures, were prepared by mixing the analyte and excipients in a proportion of 1:1 (w:w). On the basis of thermal results (especially DSC), confirmed by FT-IR and X-ray analysis, a possible chemical interaction was found between the ASA with polyvinylpyrrolidone K30 (PVP) and magnesium stearate, respectively a possible physical interaction with colloidal silicon dioxide and stearic acid (Ac. St.).     

Quantum‐Chemical and Electrochemical Investigation of the Electrochemical Windows of Halogenated Carborate Anions

The range of electrochemical stability of a series of weakly coordinating halogenated (Hal=F, Cl, Br, I) 1‐carba‐closo‐dodecaborate anions, [1‐R‐CB₁₁X₅Y₆]^? (R=H, Me; X=H, Hal, Me; Y=Hal), has been established by using quantum chemical calculations and electrochemical methods. The structures of the neutral and dianionic radicals, as well as the anions, have been optimized by using DFT calculations at the PBE0/def2‐TZVPP level. The calculated structures are in good agreement with existing experimental data and with previous calculations. Their gas‐phase ionization energies and electron affinities were calculated based on their optimized structures and were compared with experimental (cyclic and square‐wave) voltammetry data. Electrochemical oxidation was performed in MeCN at room temperature and in liquid sulfur dioxide at lower temperatures. All of the anions show a very high resistance to the onset of oxidation (2.15–2.85 V versus Fc^0/+), with only a minor dependence of the oxidation potential on the different halogen substituents. In contrast, the reduction potentials in MeCN are strongly substituent dependent (?1.93 to ?3.32 V versus Fc^0/+). The calculated ionization energies and electron affinities correlate well with the experimental redox potentials, which provide important verification of the thermodynamic validity of the mostly irreversible redox processes that are observed for this series. The large electrochemical windows that are afforded by these anions indicate their suitability for electrochemical applications, for example, as supporting electrolytes.     

Selective Detection of Mg2+ for Sensing Applications in Drinking Water

A new series of ligands containing the 2-(2-hydroxy-3- naphthyl)-4-methylbenzoxazole (HNBO) fluorophore showed selectivity for Mg²⁺ ions, without the interference of Ca²⁺. The most promising representative L3 resulted the best performing sensor for Mg²⁺ both in solution and embedded in an all-solid-state optode, especially towards real samples of drinkable water.     

Work function and negative electron affinity of ultrathin barium fluoride films

Thin films of barium fluorides with different thicknesses were deposited on GaAs substrate by electron beam evaporation. The aim of the work was to identify the best growth conditions for the production of coatings with a low work function suitable for the anode of hybrid thermionic-photovoltaic (TIPV) devices. The chemical composition and work function φ of the films with different thicknesses were investigated by X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS). The lowest value of φ = 2.1 eV was obtained for the film with a thickness of ~2 nm. In the valence band spectra of the films at low kinetic energy, near the cutoff, a characteristic peak of negative electron affinity was present. This effect contributed to a further reduction of the film's work function.     

XPS study of Cr segregation in a martensitic stainless steel

Cr martensitic steels are promising materials for structural applications in future nuclear fusion reactors. Because the embrittlement after tempering treatments can be a serious problem, the fracture mode of a steel with 10.5 wt% of Cr treated at 700°C for 18 h has been investigated through Charpy tests in the temperature range from −100°C to +150°C. X-ray photoelectron spectroscopy (XPS) analyses carried out on the fracture surfaces evidenced the segregation of Cr in both ductile and brittle (quasicleavage) fields. The unexpected result indicates that Cr segregation weakens the atomic bonds; thus, the fracture path in both the cases corresponds to the zones with higher Cr content.     

Probing the Conformational Stability of Two Different Copper Proteins: A Dynamic Fluorescence Study on Azurin and Ascorbate Oxidase

Tryptophan fluorescence is extremely useful to monitor structural conformational transitions in proteins. Denaturant-induced unfolding of azurin and ascorbate oxidase has been studied by dynamic fluorescence measurements in the frequency domain and the results have been interpreted in terms of continuous distribution of lifetimes. The data add new information on the unfolding mechanism that was previously analyzed by steady-state emission spectroscopy. In particular, the existence of multiple, parallel unfolding pathways may be envisaged and correlated, in both cases, to the two protein structures. The effect of metal depletion has been also characterized by fluorescence lifetime measurements. In the case of azurin, a monomeric protein, the data demonstrate that copper removal yields a totally different unfolding pathways with respect to the holo protein, indicating that metal ion plays a fundamental structural role in the wild type, native protein. In the case of ascorbate oxidase a dimer of 140 kDa, only minor effects have been detected by copper removal. However, the analysis of the fluorescence decay in presence of different amounts of guanidinium hydrochloride gives new important insights on the unfolding intermediates. In particular the data support the hypothesis of a partial exposure of an outer layer of dimer at intermediate denaturant concentration. This ability of dynamic fluorescence to pinpoint the presence of structural micro-heterogeneity in the unfolding pathways of proteins demonstrates the greater power of this technique compared to the most commonly used steady-state measurements.     

catena-Poly­[[di­aqua(1,10-phen­anthroline-N,N′)­manganese(II)]-μ-(thiosulfato-O:S)] and bis(2,2′-bipyridyl-N,N′)(tetra­thionato-O,O′)manganese(II)

The structures of [Mn(S₂O₃)₂(C₁₂H₈N₂)(H₂O)₂] and [Mn(S₄O₆)(C₁₀H₈N₂)₂] are presented. The former consists of pairs of polymeric chains formed by manganese polyhedra bridged by bidentate thio­sulfate anions, which are in turn related to each other by a pseudo-twofold screw axis. The latter has crystallographic twofold symmetry and consists of monomers in which manganese displays its typical octahedral coordination provided by the bidentate bites of two bi­pyridine bases and a tetra­thionate anion, which is, to our knowledge, the first chelating tetra­thionate to be reported in the literature.