Activity Coefficients of Electrolytes from Liquid Membrane Cells. XII. Magnesium,Lanthanum, and Tris(ethylenediamine)cobalt(III) Salts of the 1,5-Naphthalenedisulfonate Anion at 298.15 K

Activity coefficients of the highly charged electrolytes Mgds, La₂ds₃, and [Co(en)₃]₂ds₃ (en = ethylenediamine, ds²⁻=1,5-naphthalenedisulfonate anion), were determined at 298.15 K using liquid-membrane cells. These salts are found not to display large negative deviations from the Debye-Hückel limiting slope in the dilute regions, which characterize the corresponding sulfate salts. Theoretical calculations based on the primitive model (charged hard spheres in an unstructured dielectric medium) reproduce the behavior of these salts correctly up to concentrations of 0.01 mol⋅kg⁻¹ or more (0.1 mol⋅kg⁻¹ for Mgds), although ds²⁻, far from resembling a charged sphere, is a planar ion with charges distant from one another. The Pitzer model parameter values are reported for the activity and osmotic coefficients.     

Modification of poly(vinyl chloride) with new aromatic thiol compounds. Synthesis and characterization

Different thiol compounds were tested for the synthesis of poly(vinyl chloride) (PVC) with halogen groups and the course of the modification reactions followed under different conditions by NMR spectroscopy and elemental analysis. It is shown that PVC can be modified without side reactions using 4-fluorothiophenol, 4-chlorothiophenol, 4-bromothiophenol, 3,4-di-fluorothiophenol, penta-fluorothiophenol and penta-chlorothiophenol. The reactivities and final degrees of modification of the different nucleophiles are compared showing that, when the thiolate salt is preformed, the bromine derivative reacts quicker and higher degrees of modification are reached than with its smaller homologues. On the other hand, using the thiol compounds in combination with potassium carbonate this order is inverted and highest degrees of modification are achieved with 4-fluorothiophenol. Glass transition temperatures and thermal stabilities of the new compounds are compared.     

Simple and rapid instrumental characterization of sensory attributes of virgin olive oil based on the direct coupling headspace-mass spectrometry

A methodology for obtaining reliable qualitative and quantitative information about negative (fusty, muddy sediment, musty, rancid and vinegary) and positive (fruity) sensory attributes of virgin olive oils (lampante and extra) has been developed. The procedure implies the joint use of a headspace autosampler, a mass spectrometer and an adequate chemometric data treatment. For this purpose, soft independent modelling of class analogy (SIMCA) and partial least squares (PLS) regression approaches were used for attribute identification and quantification, respectively. InStep application was employed to generate a decision tree by the combination of both models in order to provide the joint prediction of the sensory attributes of a given virgin olive oil and their respective intensities by means of a single output result. The good prediction results obtained when the decision tree generated were applied to a new set of virgin olive oil samples (viz, a specificity of 100%, an average sensitivity of 86% and a RMSEP<0.8% in the quantification task) reveals its potential applicability in routine analysis.     

Determination of zearalenone and its metabolites in urine samples by liquid chromatography with electrochemical detection using a carbon nanotube-modified electrode

A simple and sensitive method for the separation and determination of zearalenone (ZON) and its secondary metabolites, namely beta-zearalenol (beta-ZAL), beta-zearalanol (beta-ZOL), alpha-zearalenol (alpha-ZAL), alpha-zearalanol (alpha-ZOL) and zearalanone (ZAN) in urine (human, bovine and swine) samples is proposed. The method comprises previous clean-up and pre-concentration on C(18) adsorption cartridges of the analytes followed by liquid chromatographic separation and direct electrochemical detection at +0.85mV using a carbon nanotube-modified glassy carbon electrode (CNT-GCE). This method allows the determination of beta-ZAL, beta-ZOL, alpha-ZAL, alpha-ZOL, ZAN and ZON in a linear range between 5 and 50ngmL(-1), with relative standard deviation values lower than 6.9% (intra-day) and 7.1% (inter-day), in all cases. Detection limits ranging between 1.3ngmL(-1) (beta-ZOL, alpha-ZAL, alpha-ZOL) and 1.4ngmL(-1) (beta-ZAL, ZAN, ZON) were achieved. The usefulness of the proposed method was demonstrated by the analysis of spiked and natural samples of human, bovine and swine urine samples.     

Mechanical derivation of the Wenzel and Cassie equations using a statistical interpretation of drop dispensation

The global mechanical equilibrium condition of a liquid on a rough and chemically heterogeneous surface was derived for three-dimensional situations from a statistical outlook of dispensation of many drops and the assumption of local mechanical equilibrium. Unlike the conventional thermodynamic derivations from variational methods, the current proof is based on vector algebra rather than differential geometry. The mechanics-based derivation becomes less intricate although the minimum energy condition is not established. An effective contact angle is computed from the directional sampling of three-phase lines after local drop dispensations. The final expression is a combined mechanical version of the Wenzel and Cassie equations.     

Synthesis of cobalt ferrite core/metallic shell nanoparticles for the development of a specific PNA/DNA biosensor

Controlled synthesis of cobalt ferrite superparamagnetic nanoparticles covered with a gold shell has been achieved by an affinity and trap strategy. Magnetic nanoparticles are functionalized with a mixture of amino and thiol groups that facilitate the electrostatic attraction and further chemisorption of gold nanoparticles, respectively. Using these nanoparticles as seeds, a complete coating shell is achieved by gold salt-iterative reduction leading to monodisperse water-soluble gold-covered magnetic nanoparticles, with an average diameter ranging from 21 to 29 nm. These constitute a versatile platform for immobilization of biomolecules via thiol chemistry, which is exemplified by the immobilization of peptide nucleic acid (PNA) oligomers that specifically hybridize with complementary DNA molecules in solution. Hybridation with DNA probes has been measured using Rhodamine 6G fluorescence marker and the detection of a single nucleotide mutation has been achieved. These results suggest the PNA-nanoparticles application as a biosensor for DNA genotyping avoiding commonly time-consuming procedures employed.     

Iminium salts of omega-dithiafulvenylpolyenals: an easy entry to the corresponding aldehydes and doubly proaromatic nonlinear optic-phores

A short, high-yielding route to omega-dithiafulvenylpolyenals (1) via the corresponding iminium salts (2) and starting from trimethyl-1,3-dithiolium tetrafluoroborate is reported. The Knoevenagel reactions of either 1 or 2 with isoxazolone-containing acceptors afford merocyanines 7 and 9, in a process that is often accompanied by a vinylene-shortening side reaction. Experimental and theoretical studies reveal that compounds 7 and 9, featuring two proaromatic end groups, are strongly polarized and show good second-order nonlinear optical responses.     

Epoxyamide-based strategy for the synthesis of polypropionate-type frameworks

A new approach to the stereoselective synthesis of polypropionate-type frameworks is reported utilizing reactions of amide-stabilized sulfur ylides with chiral aldehydes. To establish a new strategy for macrolide fragment synthesis, the stereoselectivity of these reactions in the construction of epoxy amides was the most important aspect of this study. In this aspect, we found a strong influence of the protecting groups employed in the starting aldehydes upon the stereochemical outcome of their reactions with the sulfur ylide 1. Thus, numerous aldehydes showed remarkable stereofacial differentiation, providing a major diastereoisomer, in contrast to others that displayed a poor or no stereoselectivity. Despite the difficulties encountered for some cases with respect to their diastereomeric yields, we were able to prepare various stereotetrads and stereopentads, thus enhancing the synthetic value of this new methodology for the preparation of typical polypropionate frameworks found in many natural products, in particular the macrolide class of antibiotics.     

Unexpected solid-state photochemistry of an alpha-thiophenyl-alpha'-thiophenyl-S,S-dioxo-substituted ketone

Samples of 2,4-dimethyl-2-(thiophen-3-yl)-4-(thiophen-3-yl-S,S-dioxo)pentan-3-one 2 were obtained by controlled MCPBA oxidation of 2,4-dimethyl-2,4-di(thiophen-3-yl)pentan-3-one 1. Rather than the expected photodecarbonylation, UV--vis irradiation of 2 led to the intramolecular 2 + 2 photocycloaddition product 5 in quantitative yields (by GC and NMR) both in solution and in crystalline solid state. Detailed X-ray powder diffraction analyses revealed that the solid-state reaction of sulfone 2 occurs with a loss of long-range order despite retaining some birefringence under polarized microscopy.