An ab initio study of the vibronic, spin-orbit, and magnetic hyperfine structure in the X2Pi electronic state of NCO

In the present study we give the results of the ab initio calculations on the vibronic, spin-orbit, and magnetic hyperfine structure in the X (2)Pi electronic state of the NCO radical. The calculations of the potential surfaces and the electronic mean values of the hyperfine coupling constants are carried out by means of the density functional theory approach (B3LYP functional combined with an atomic orbital basis set suitable for calculations of the hyperfine structure). The vibronic levels, spin-orbit splitting, and the vibronic mean values of the components of the hyperfine tensor in the vibronic species are calculated using a variational method. The results of the calculations are in good agreement with the available experimental data.     

Trinuclear pyrazine-bridged ruthenium complexes: syntheses, electrochemistry, NIR-Vis spectra, and their interpretation in terms of a 5-orbital-3-parameter model

A study of absorption spectra in the near-infrared (NIR) and visible (vis) regions of trinuclear Ru complexes containing pyrazine (pyz) as bridging ligand, trans-[(Ru(NH(3))(5)pyz)(2)Ru(NH(3))(4)](m+)(m = 6-9), is reported. The spectra were recorded on aqueous solutions containing the described species formed in situ by stoichiometric additions of a standard solution of Ce(SO(4))(2). They were interpreted in terms of a simple 5-orbital-3-parameter model which includes the effects of d-pi interaction and electronic correlation. The model is shown to account for the observed NIR-vis spectra of the complex ions. The 6+ parent species was synthesized by an improved literature method and fully characterized. The novel 8+ complex was also prepared and characterized. The 9+ ion was established to be slowly reduced by water, with dioxygen formation. Electrochemical (CV and DPV) studies were performed on the trinuclear 6+ complex, as well as on its constituent fragments [Ru(NH(3))(5)(pyz)](2+) and trans-[Ru(NH(3))(4)(pyz)(2)](2+).     

Spectrophotometric method for the determination of demeclocycline using sodium molybdate as analytical reagent

By means of spectroscopic methods it has been found that demeclocycline reacts with molybdate ions forming a complex compound [MoO₃HDMTC]^2–. The relative stability constant of this compound has been determined by applying spectrophotometric methods. Under optimum conditions for complex formation a very sensitive spectrophotometric method for the estimation of demeclocycline in the concentration range 5.0–35.1 g/ml is proposed. The detection limit of the method is 2.5 g/ml of demeclocycline. The relative standard deviation (n=10) varies between 0.76% and 1.46%. The method proved to be accurate and sensitive for the analysis of the demeclocycline content in tablets.     

Practical aspects of splitless injection of semivolatile compounds in fast gas chromatography

Possibilities and practical aspects of implementation of splitless injection of larger volumes for fast GC purposes utilizing narrow-bore column, hydrogen as carrier gas, fast temperature programming under programmed flow conditions and commercial instrumentation were searched. As a model sample semivolatile compounds of a broad range of volatility and polarity (7 n-alkanes and 19 pesticides) were chosen. Peak shapes, peak broadening and peak areas and its repeatability were evaluated under various experimental set-ups (liner/injection technique combinations). Various factors, such as liner design, injection technique, retention gap length, compound volatility and polarity, the solvent used, initial oven temperature influenced compound focusation and/or maximal injection volume. Combination of analytical column (CP-Sil 13 CB 25 m long, 0.15 mm i.d., film thickness 0.4 microm) with normal-bore retention gap (1 m long, 0.32 mm i.d.) allowed maximal injection volume 8 microl for 4 mm i.d. liner used without any peak distortion when solvent recondensation in the retention gap was employed.     

Assessment of Chemical Composition and Anti-Penicillium Activity of Vapours of Essential Oils from Abies Alba and Two Melaleuca Species in Food Model Systems

The possibilities of the practical utilization of essential oils (EOs) from various plant species in the food industry have attracted the attention of the scientific community. Following our previous studies, the antifungal activities of three further commercial EOs, Melaleuca armillaris subsp. armillaris (rosalina; REO), Melaleuca quinquenervia (niaouli; NEO), and Abies alba (fir; FEO), were evaluated in the present research in respect to their chemical profiles, over four different concentrations, 62.5 μL/L, 125 μL/L, 250 μL/L, and 500 μL/L. The findings revealed that the major compounds of REO, NEO, and FEO were linalool (47.5%), 1,8-cineole (40.8%), and α-pinene (25.2%), respectively. In vitro antifungal determinations showed that the inhibition zones of a Penicillium spp. mycelial growth ranged from no inhibitory effectiveness (00.00 ± 00.00 mm) to 16.00 ± 1.00 mm, indicating a very strong antifungal activity which was detected against P. citrinum after the highest REO concentration exposure. Furthermore, the in situ antifungal efficacy of all EOs investigated was shown to be dose-dependent. In this sense, we have found that the highest concentration (500 µL/L) of REO, NEO, and FEO significantly reduced (p < 0.05) the growth of all Penicillium strains inoculated on the bread, carrot, and potato models. These results indicate that the investigated EOs may be promising innovative agents in order to extend the shelf life of different types of food products, such as bread, carrot and potato.     

Nonexistence of global solutions to new ordinary differential inequality and applications to nonlineardispersive equations

A new ordinary differential inequality without global solutions is proposed. Comparison with similar differential inequalities in the well‐known concavity method is performed. As an application, finite time blow up of the solutions to nonlinear Klein–Gordon equation and generalized Boussinesq equation is proven. The initial energy is arbitrary high positive. The structural conditions on the initial data generalize the assumptions used in the literature for the time being. Copyright © 2015 John Wiley & Sons, Ltd.     

XANES speciation of mercury in three mining districts – Almadén,Asturias (Spain), Idria (Slovenia)

The mobility, bioavailability and toxicity of mercury in the environment strongly depend on the chemical species in which it is present in soil, sediments, water or air. In mining districts, differences in mobility and bioavailability of mercury mainly arise from the different type of mineralization and ore processing. In this work, synchrotron‐based X‐ray absorption near‐edge spectroscopy (XANES) has been taken advantage of to study the speciation of mercury in geological samples from three of the largest European mercury mining districts: Almadén (Spain), Idria (Slovenia) and Asturias (Spain). XANES has been complemented with a single extraction protocol for the determination of Hg mobility. Ore, calcines, dump material, soil, sediment and suspended particles from the three sites have been considered in the study. In the three sites, rather insoluble sulfide compounds (cinnabar and metacinnabar) were found to predominate. Minor amounts of more soluble mercury compounds (chlorides and sulfates) were also identified in some samples. Single extraction procedures have put forward a strong dependence of the mobility with the concentration of chlorides and sulfates. Differences in efficiency of roasting furnaces from the three sites have been found.     

Interaction of Naproxen with Crystalline and Amorphous Methylated β-Cyclodextrin in the Liquid and Solid State

Abstract

Interactions of naproxen (NAP) with amorphous, randomly methylated β-cyclodextrin at a degree of substitution per anhydroglucose unit of 1.8 (RAMEB) and with crystalline heptakis-(2,6-di-O-methyl)-β-cyclodextrin (DIMEB) were studied in aqueous solution and in the solid state using, respectively, phase-solubility analysis (at 25 °C, 37 °C and 47 °C) and differential scanning calorimetry (DSC) supported by X-ray powder diffractometry. RAMEB and DIMEB displayed similar solubilizing and complexing abilities towards NAP, suggesting analogous inclusion modes of the drug in the host cavity in aqueous solution. Differences were instead observed in interactions in the solid state, where the amorphizing capacity of RAMEB toward NAP (evaluated by DSC) was about twice that of DIMEB at each drug-to-carrier ratio. Assuming that inclusion complexation is also involved in solid-state interactions, molecular modelling accounted for the experimental results in terms of structural features of DIMEB, i.e. the particular inwards orientation of O-6-C-8 groups of three alternate glucoses on the primary hydroxyl side which hampers a deep penetration of NAP in the DIMEB cavity in the solid state. On the contrary, no obstruction of the cavity apparently occurs with RAMEB due its noncrystalline state. The aqueous dissolution rate of NAP from NAP-RAMEB and NAP-DIMEB blends containing 0.59, 0.73, 0.85, and 0.92 mass fraction of carrier linearly increased at decreasing drug-to-carrier ratios. The improvement was 5 to 20 times (from powders) and 50 to 200 times (from discs) the dissolution rate of NAP alone for both carrier. Therefore the choice of the amorphous RAMEB in pharmaceutical formulations can be recommended mainly for economic reasons, though the anhydrous and non-hygroscopic nature of crystalline DIMEB might be of particular advantage in case of moisture sensitive formulations.