Hydride generation atomic fluorescence spectrometric determination of ultratraces of selenium and tellurium in cow milk

A sensitive procedure has been developed for selenium and tellurium determination in milk by hydride generation atomic fluorescence spectrometry (HG-AFS) after microwave-assisted sample digestion. The method provides sensitivity values of 1591 and 997 fluorescence units ng⁻¹ ml⁻¹ with detection limits of 0.005 and 0.015 ng ml⁻¹ for Se and Te, respectively. The application of the developed methodology to the analysis of cow milk samples of the Spanish market evidenced the presence of concentration ranges from 11.1 to 26.0 ng ml⁻¹ for Se, and from 1.04 to 9.7 ng ml⁻¹ for Te having found a good comparability with data obtained after dry-ashing of samples.     

Sample preparation improvement in polycyclic aromatic hydrocarbons determination in olive oils by gel permeation chromatography and liquid chromatography with fluorescence detection

The determination of 15 polycyclic aromatic hydrocarbons (PAHs) in olive oil samples has been improved in order to obtain a fast methodology with a low limit of detection through the combination of liquid-liquid extraction with acetonitrile and preparative gel permeation chromatography (GPC) prior to the injection of purified extracts into a C18 column. Acetonitrile-water was used as the mobile phase with a gradient from 50 to 95%, w/w, acetonitrile in 30 min. The oven temperature was maintained at 15 degrees C, and fluorometric detection was made at a fixed excitation wavelength of 264 nm and variable, optimal emission wavelength for each analyte ranging from 352 nm for 11-H-benzo(b)fluorene to 500 nm for indeno(1,2,3-cd)pyrene. Recovery for all the compounds studied varied from 75 to 111%, and limit of detection values from 0.05 ng/g for benzo(k)fluoranthene to 0.48 ng/g for indeno(1,2,3-cd)pyrene, corresponding to 0.09 ng/g benzo(a)pyrene. Results were compared with those obtained by liquid-liquid extraction followed by a cleanup on silica and a direct GPC treatment of oil samples diluted in dichloromethane, 2 other methodologies that are appropriate for quantifying PAHs in olive oils. However, the proposed method improves the determination limits, reduces the time of analysis, and provides a highly stable baseline for sample chromatograms.     

Saturn's Great White Spots

The term, Great White Spot, is used for large and unusual atmospheric disturbances on the planet Saturn. The phenomenology has been recorded only in five occasions during the last century, and its evolution can be described in terms of four different phases: (i) Onset (first week), outburst and rapid growth of a very bright cloud up to a size of approximately 20 000 km; (ii) planetary disturbance (相似文献   

Traveling patterns in cellular automata

A method to identify the invariant subsets of bi-infinite configurations of cellular automata that propagate rigidly with a constant velocity nu is described. Causal traveling configurations, propagating at speeds not greater than the automaton range, mid R:numid R:相似文献   

Solubility and equilibria of silver chloride

An hyperbolic cosine method for the study of the solubility equilibria of silver chloride in the presence of sodium chloride is reported in this paper. Various approximations are usually performed in a study of this kind of system in order to carry out single calculations. However, the method proposed considers all solubility data simultaneously, being as a result either more rigorous or simpler than the methods previously used.     

Holo- and hemidirected lead(II) in the polymeric [Pb(4)(mu-3,4-TDTA)2(H2O)2]*4H2O complex. N,N,N',N'-tetraacetate ligands derived from o-phenylenediamines as sequestering agents for lead(II)

The coordinating ability of the ligands 3,4-toluenediamine-N,N,N',N'-tetraacetate (3,4-TDTA), o-phenylenediamine-N,N,N',N'-tetraacetate (o-PhDTA), and 4-chloro-1,2-phenylenediamine-N,N,N',N'-tetraacetate (4-Cl-o-PhDTA) (H4L acids) toward lead(II) is studied by potentiometry (25 degrees C, I = 0.5 mol x dm(-3) in NaClO4), UV-vis spectrophotometry, and 207Pb NMR spectrometry. The stability constants of the complex species formed were determined. X-ray diffraction structural analysis of the complex [Pb4(mu-3,4-TDTA)4(H2O)2]*4H2O (1) revealed that 1 has a 2-D structure. The layers are built up by the polymerization of centrosymmetric [Pb4L2(H2O)2] tetranuclear units. The neutral layers have the aromatic rings of the ligands pointing to the periphery, whereas the metallic ions are located in the central part of the layers. In compound 1, two types of six-coordinate lead(II) environments are produced. The Pb(1) is coordinated to two nitrogen atoms and four carboxylate oxygens from the ligand, whereas Pb(2) has an O6 trigonally distorted octahedral surrounding. The lead(II) ion is surrounded by five carboxylate oxygens and a water molecule. The carboxylate oxygens belong to four different ligands that are also joined to four other Pb(1) ions. The selective uptake of lead(II) was analyzed by means of chemical speciation diagrams as well as the so-called conditional or effective formation constants K(Pb)eff. The results indicate that, in competition with other ligands that are strong complexing agents for lead(II), our ligands are better sequestering agents in acidic media.     

Organic‐acid mediated bulk polymerization of ε‐caprolactam and its copolymerization with ε‐caprolactone

Polyamides (PA) constitute one of the most important classes of polymeric materials and have gained strong position in different areas, such as textiles, fibers, and construction materials. Whereas most PA are synthesized by step‐growth polycondensation, PA 6 is synthesized by ring opening polymerization (ROP) of ε‐caprolactam (ε‐CLa). The most popular ROP methods involve the use of alkaline metal catalyst difficult to handle at large scale. In this article, we propose the use of organic acids for the ROP of ε‐CLa in bulk at 180 °C (below the polymer's melting point). Among evaluated organic acids, sulfonic acids were found to be the most effective for the polymerization of ε‐CLa , being the Brønsted acid ionic liquid: 1‐(4‐sulfobutyl)?3‐methylimidazolium hydrogen sulfate the most suitable due to its higher thermal stability. End‐group analysis by ¹H nuclear magnetic resonance and model reactions provided mechanistic insights and suggested that the catalytic activity of sulfonic acids was a function of not only the acid strength, but of the nucleophilic character of conjugate base as well. Finally, the ability of sulfonic acid to promote the copolymerization of ε‐CLa and ε‐caprolactone is demonstrated. As a result, poly(ε‐caprolactam‐co‐ε‐caprolactone) copolymers with considerably randomness are obtained. This benign route allows the synthesis of poly(ester amide)s with different thermal and mechanical properties. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2394–2402     

Miscible blends of poly(ethylene oxide) with brush copolymers of poly(vinyl alcohol)‐graft‐poly(l‐lactide)

Even though poly(ethylene oxide) (PEO) is immiscible with both poly(l ‐lactide) (PLLA) and poly(vinyl alcohol) (PVA), this article shows a working route to obtain miscible blends based on these polymers. The miscibility of these polymers has been analyzed using the solubility parameter approach to choose the proper ratios of the constituents of the blend. Then, PVA has been grafted with l ‐lactide (LLA) through ring‐opening polymerization to obtain a poly(vinyl alcohol)‐graft‐poly(l ‐lactide) (PVA‐g‐PLLA) brush copolymer with 82 mol % LLA according to ¹H and ¹³C NMR spectroscopies. PEO has been blended with the PVA‐g‐PLLA brush copolymer and the miscibility of the system has been analyzed by DSC, FTIR, OM, and SEM. The particular architecture of the blends results in DSC traces lacking clearly distinguishable glass transitions that have been explained considering self‐concentration effects (Lodge and McLeish) and the associated concentration fluctuations. Fortunately, the FTIR analysis is conclusive regarding the miscibility and the specific interactions in these systems. Melting point depression analysis suggests that interactions of intermediate strength and PLOM and SEM reveal homogeneous morphologies for the PEO/PVA‐g‐PLLA blends. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1217–1226     

A Flory–Huggins thermodynamic approach for predicting sorption equilibrium in ternary polymer systems

The Flory–Huggins theory as modified by Pouchlý has been applied to calculate preferential (λ) and total (Y) sorption coefficients for a ternary polymer system. The ternary interaction function (?₁?₂?₃G_T(u₁, ?₃)) is described as the product of three independent binary functions. This expression allows prediction of λ and Y from binary interaction parameters χ, χ, g, g, and g₁₂(?₁₀). Three ternary polymer systems are used to check the validity of the expression. Moreover for polymer systems in which the parameters g and/or g are unknown, a procedure to evaluate them has been developed and verified on systems for which sufficient experimental information is available.