Application of chemical, physical and chemometric analytical techniques to the study of ancient ceramic oil lamps

A chemical, mineralogical and morphological characterization of 54 fragments of oil lamps found in two Spanish archaeological sites (Cordoba and Herrera de Pisuerga (Palencia)) has been performed. Flame atomic absorption and emission spectrometry were used for the determination of Al₂O₃, CaO, Fe₂O₃, K₂O, MgO, MnO, Na₂O and TiO₂ as major constituents and Cu, Cr, Ni, Pb and Zn as minor and trace selected elements. Physical, mineralogical and morphological analyses were made by using dilatometry at constant heating rate for the thermal behaviour, X-ray diffraction spectrometry for the mineralogical composition and, in a group of selected samples, scanning electron microscopy and polarizing petrographic microscopy for the observation of thin layers and mineral identification. Separations of light and heavy minerals were carried out with bromoform and X-ray diffraction analysis was applied to both fractions. Multivariate statistical analysis was used to establish correlations between variables and to deduce factors which allow the gathering of oil lamp samples in groups as a function of their composition.The results of these analyses allow the comparison among pieces and the establishment of conclusions about several aspects of their manufacture, the origin of the raw materials and the provenance of the oil lamps (local or imported). They provide information supporting certain archaeological hypothesis. For example, some oil lamps found in Herrera de Pisuerga showed a clearly different physicochemical composition. They were probably brought from Italy by the Roman Legions together with their initial furniture household.     

The mechanism of the homogeneous,unimolecular gas‐phase elimination kinetic of 1,1‐dimethoxycyclohexane: experimental and theoretical studies

The gas‐phase elimination of 1,1‐dimethoxycyclohexane yielded 1‐methoxy‐1‐cyclohexene and methanol. The kinetics were determined in a static system, with the vessels deactivated with allyl bromide, and in the presence of the free radical inhibitor cyclohexene. The working temperature was 310–360 °C and the pressure was 25–85 Torr. The reaction was found to be homogeneous, unimolecular, and follows a first‐order rate law. The temperature dependence of the rate coefficients is given by the following Arrhenius equation: log k(s^?1) = [(13.82 ± 0.07) – (193.9 ± 1.0)(kJ mol^?1)](2.303RT)^?1; r = 0.9995. Theoretical calculations were carried out using density functional theory (DFT) functionals B3LYP, MPW1PW91, and PBE with the basis set 6‐31G(d,p) and 6‐31G++(d,p). The calculated values for the energy of activation and enthalpy of activation are in reasonably good agreement with the experimental values using the PBE/6‐31G (d,p) level of theory. Both experimental results and theoretical calculations suggest a molecular mechanism involving a concerted polar four‐membered cyclic transition state. The transition state structure of methanol elimination from 1,1‐dimethoxycyclohexane is characterized by a significantly elongated C? O bond, while the C_β? H bond is stretched to a smaller extent, as compared to the reactant. The process can be described as moderately asynchronic with some charge separation in the TS. Copyright © 2010 John Wiley & Sons, Ltd.     

The Pauson-Khand reaction, a powerful synthetic tool for the synthesis of complex molecules

There are still some synthetic chemists who hesitate to use metal-mediated or -catalysed reactions. The Pauson-Khand reaction (PKR) is a powerful transformation that has now been sufficiently well developed to be routinely considered when planning a synthesis, especially of polycyclic complex molecules. This tutorial review aims to encourage the use of this process explaining the best ways of performing a PKR both in the stoichiometric and the catalytic version, showing the scope of the process and its limitations. Additionally, asymmetry can be introduced in the reaction using several strategies, which will be discussed. The most recent examples of the synthetic applications of the PKR in natural product synthesis will give the reader an idea of the great usefulness of this reaction.     

Cyclic allene intermediates in intramolecular dehydro Diels-Alder reactions: labeling and theoretical cycloaromatization studies

A comprehensive theoretical and experimental investigation of dehydro Diels-Alder reactions examining the evolution of the cyclic allene intermediates under conditions for intramolecular and ionic and radical intermolecular cycloaromatization processes is reported. Theoretical calculations showed that the most favored intramolecular path for cycloaromatization of 1,2,4-cyclohexatriene 4 and its benzoannulated derivative 14, strained cyclic allenes, consists of a pair of successive [1,2] H shifts rather than a [1,5] shift. Cycloaromatization of cyclic allenes may follow both inter- and intramolecular pathways, depending on the experimental conditions (use of protic or aprotic solvents). For synthetic purposes, the best procedure is to use a protic solvent to promote the ionic intermolecular route, the fastest and highest yielding. When the reaction is carried out in CCl4, intermolecular radical addition of chlorine to the cyclic allene competes with intramolecular aromatization paths. Theoretical calculations predict a low barrier for the reaction of cyclic allenes with carbon tetrachloride, and that the cyclic allenes act as nucleophiles in this reaction.     

Flux flow in current driven mesoscopic superconductors: size effects

Flux-flow phenomena in a superconducting mesoscopic stripe submitted to an appliedcurrent and external magnetic field is studied. The time-dependent Ginzburg-Landauequations are solved numerically to obtain the electric and magnetic response of thesystem. It is shown that the I-V curves, for the wider strips, present a universalbehaviour. The dependence of the flux-flow resistivity on the magnetic field and widthallow us to propose a criterion characterizing, both, the macroscopic and mesoscopicregimes. The power spectrum of the average voltage permits identifying the effect ofsurface currents in vortices movement. Based on the maximum value of the power spectrumfirst harmonic we propose a geometric condition for matching between the sample dimensionsand the vortex lattice parameter.     

Heuristic Procedures for Solving the Discrete Ordered Median Problem

We present two heuristic methods for solving the Discrete Ordered Median Problem (DOMP), for which no such approaches have been developed so far. The DOMP generalizes classical discrete facility location problems, such as the p-median and p-center. The first procedure proposed in this paper is based on a genetic algorithm developed by Moreno Vega (1996) for p-median and p-center problems. Additionally, a second heuristic approach based on the Variable Neighborhood Search metaheuristic (VNS) proposed by Hansen and Mladenović (1997) for the p-median problem is described. An extensive numerical study is presented to show the efficiency of both heuristics and compare them.     

Electrochemically assisted anion insertion in Au(I)–Cu(I) heterotrimetallic clusters bearing ferrocenyl groups: Application to the fluoride/chloride discrimination in aqueous media

The heterotrimetallic Au(I)–Cu(I) aggregate [{Au₃Cu₂(C₂C₆H₄Fc)₆}Au₃(PPh₂C₆H₄PPh₂)₃](PF₆)₂ exhibits a well-defined solid state electrochemistry in contact with aqueous media, based on ferrocenyl-centred oxidation processes involving anion insertion. Upon attachment of microparticulate deposits of the cluster to graphite electrodes, distinctive electrochemical responses can be obtained for fluoride and chloride ions in aqueous media.     

Metabolomic profiling of serum in the progression of Alzheimer's disease by capillary electrophoresis–mass spectrometry

There is high interest in the discovery of early diagnostic biomarkers of Alzheimer's disease, for which metabolomics exhibits a great potential. In this work, a metabolomic approach based on ultrafiltration and analysis by CE‐MS has been used to obtain representative fingerprints of polar metabolites from serum samples in order to distinguish between patients with Alzheimer's disease, mild cognitive impairment, and healthy controls. By the use of partial least squares discriminant analysis it was possible to classify patients according to the disease stage and then identify potential markers. Significant increase was observed with progression of disease in levels of choline, creatinine, asymmetric dimethyl‐arginine, homocysteine‐cysteine disulfide, phenylalanyl‐phenylalanine, and different medium chain acylcarnitines. On the other hand, asparagine, methionine, histidine, carnitine, acetyl‐spermidine, and C5‐carnitine were reduced in these serum samples. In this way, multiple essential pathways were found implicated in the underlying pathology, such as oxidative stress or defects in energy metabolism. However, the most interesting results are related to the association of several vascular risk factors with Alzheimer's disease.     

Amperometric determination of sulfite using screen-printed electrodes modified with metallic nanoparticles

We report on the amperometric determination of sulfite using screen-printed carbon electrodes (SPCEs) modified with gold and silver nanoparticles that were deposited on the electrode to improve the capabilities of detection. The electrode is fairly selective and responds to sulfite with an oxidation current (at 300 mV and pH 6) in the 9.80 to 83.33 μM concentration range. The precision in terms of repeatability and reproducibility is 14.4 % and 10.7 % in the case of SPCEs modified by gold nanoparticles. The method was applied to the determination of sulfite in drinking water, pickle juice and vinegar. Recoveries ranged from 96 % to 104 %.

A screen-printed disposable biosensor for selective determination of putrescine

We have developed screen-printed carbon electrodes for the determination of putrescine (Put) via the enzyme monoamine oxidase that was immobilized on the surface of the electrode by cross-linking it with bovine serum albumin using glutaraldehyde. A mixture of 5 % of tetrathiofulvalene (TTF) and carbon ink was used for the fabrication of the screen-printed working electrode. Put was amperometrically detected by measurement of the current due to the oxidation of the mediator TTF. The use of TTF lowers the working potential to +250 mV (vs. a screen-printed Ag/AgCl reference electrode). Response is linear in the range from 16 to 101 μM, and the detection limit is 17.2?±?4.6 μM, with a reproducibility of 9.6 % (n?=?4) in terms of relative standard deviation. The effects of potentially interfering biogenic amines such as cadaverine, histamine, spermine, spermidine and tryptamine were also evaluated. The biosensor was successfully applied to the determination of Put in zucchini and anchovies.