Influence of Polarity and Activation Energy in Microwave–Assisted Organic Synthesis (MAOS)

The aim of this work was to determine the parameters that have decisive roles in microwave-assisted reactions and to develop a model, using computational chemistry, to predict a priori the type of reactions that can be improved under microwaves. For this purpose, a computational study was carried out on a variety of reactions, which have been reported to be improved under microwave irradiation. This comprises six types of reactions. The outcomes obtained in this study indicate that the most influential parameters are activation energy, enthalpy, and the polarity of all the species that participate. In addition to this, in most cases, slower reacting systems observe a much greater improvement under microwave irradiation. Furthermore, for these reactions, the presence of a polar component in the reaction (solvent, reagent, susceptor, etc.) is necessary for strong coupling with the electromagnetic radiation. We also quantified that an activation energy of 20–30 kcal mol⁻¹ and a polarity (μ) between 7–20 D of the species involved in the process is required to obtain significant improvements under microwave irradiation.     

X-ray diffraction study of some mesogenic copper, nickel and vanadyl complexes

We present a comparative study of various metallomesogenic complexes, using X-ray diffraction methods. For a given ligand linked to different metal atoms (Cu, Ni, VO), the nature of this central atom influences mainly the magnetic susceptibilities of the mesophases. With different ligands, which keep the close neighbourhood of the metal atom unchanged, the apparent length of the mesogenic unit is longer for short ligands than for longer ones. This unexpected behaviour is qualitatively well explained by taking into account the global shape of the different complexes.     

Representation of Cubic Lattices by Symmetric Implication Algebras

In this paper a cubic lattice L(S) is endowed with a symmetric implication structure and it is proved that L(S) \ {0} is a power of the three-element simple symmetric implication algebra. The Metropolis–Rota’s symmetries are obtained as partial terms in the language of symmetric implication algebras.     

Automatic detection and identification of shocks in Gaussian state‐space models: a Bayesian approach

An automatic monitoring and intervention algorithm that permits the supervision of very general aspects in an univariate linear Gaussian state–space model is proposed. The algorithm makes use of a model comparison and selection approach within a Bayesian framework. In addition, this algorithm incorporates the possibility of eliminating earlier interventions when subsequent evidence against them comes to light. Finally, the procedure is illustrated with two empirical examples taken from the literature. Copyright © 2005 John Wiley & Sons, Ltd.     

Multicommuted fluorometric multiparameter sensor for simultaneous determination of naproxen and salicylic acid in biological fluids.

A combined approach based on solid-phase optosensing and multicommutation principles has been applied to develop a method for the simultaneous analysis of two pharmaceuticals (naproxen and salicylic acid) in biological fluids. The multicommuted flow-through optosensor was based on direct native fluorescence measurements of both analgesics using a non-polar sorbent (C18 silica gel) as a solid sensing zone. The flow system was controlled by Java-written home-made software and designed using three-way solenoid valves for an independent automated manipulation of sample and carrier solutions. Using an optimized sampling time, the method was calibrated in the range of 1 - 25 and 5 - 200 ng mL(-1). The obtained detection limits were 0.3 and 1.3 ng mL(-1) for naproxen and salicylic acid, respectively, with RSD (%) values of better than 2% for both analytes. The proposed methodology was successfully applied to urine, serum and pharmaceutical preparations. Recovery percentages ranging from 96.1 to 104% were obtained for both analytes.     

Correct structures of Diels-Alder adducts from the natural cyclolignan thuriferic acid and its 8-epimer

A detailed analysis of one- and two-dimensional ¹H and ¹³C NMR data for the endo and the exo adducts, obtained by Diels-Alder reaction of thuriferic and epithuriferic acids with cyclopentadiene is described. The unequivocal spectral data assignment of the endo and exo structures was complemented with molecular modelling studies and confirmed through X-ray diffraction studies.     

Thermal behaviour of a polyhedral oligomeric silsesquioxane with epoxy resin cured by diamines

A new material belongs to the family of polyhedral oligomeric silsesquioxanes, the 1-(3-glycidyl) propoxy-3,5,7,9,11,13,15-isobutylpentacyclo-[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane (glycidylisobutyl-POSS) is characterized by differential scanning calorimetry, thermogravimetric analysis and atomic force microscopy. Epoxy systems based on diglycidyl ether of bisphenol A (DGEBA) cured with the diamines, 4,4'-diamine-diphenylmethane (DDM) and 1,4-phenylenediamine (pPDA), were kinetically studied by differential scanning calorimetry in isothermal and dynamic modes. The thermal behaviour of these systems as the glycidylisobutyl-POSS was added, is discussed later. This revised version was published online in July 2006 with corrections to the Cover Date.     

Vapor-particle partitioning of hydrocarbons in Western Mediterranean urban and marine atmospheres

An analytical procedure is described for a comprehensive determination of the composition of hydrocarbons in the atmosphere, based on: (a) aerosol filtration and subsequent adsorption of the vapor phase onto active charcoal and polyurethane foam; (b) GPC and HPLC fractionation of the extracts, and (c) analysis of the fractions by GC-MS under EI and NICI modes. Special emphasis is placed onn-alkanes, PAHs and their oxygenated derivatives.The characterization of samples collected in a coastal urban area (Barcelona city), and far away over the Western Mediterranean, at sea level and at 1100 m of altitude, revealed significant changes in the aerosol composition, mainly attributed to initial vapor-particle partitioning processes, influenced by ambient temperature variations, and to others taking place during long-range atmospheric transport, related with the different compound photoreactivities and with an unexplained source-decoupling phenomenon.     

Molybdenum(VI) and molybdenum(V) mononuclear and dinuclear complexes with 1,3-diphenyl-1,3-propanedione

Summary The synthesis and the dinuclear or mononuclear nature of several molybdenum(VI) and molybdenum(V) oxocomplexes derived from 1,3-diphenyl-1,3-propanedione (HLL) are described. These complexes were identified by i.r. and electronic spectra, magnetic susceptibility and analytical data, and are assigned the following formulae: [MoO₂(LL)₂], [Mo₂O₅(LL)₂], [Mo₂O₄(LL)₂], [MoOCl(LL)₂], [MoCl₂(LL)] and [MoO(OH)(LL)₂)]. The low magnetic moments of the dinuclear complexes are due, in part, to intramolecular interactions. The i.r. data show that the dionate is bound by two oxygen atoms forming a chelate six-membered ring.