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.     

Epoxy-silica/clay nanocomposite for silver-based antibacterial thin coatings: structure and ionic mobility

Journal of Solid State Electrochemistry - A novel material was developed using sol-gel chemistry and an environmental-friendly grafting process of clay nanoparticles. In a previous work of our...     

Packing Non-Zero A-Paths In Group-Labelled Graphs

Let G=(V,E) be an oriented graph whose edges are labelled by the elements of a group Γ and let A⊂V. An A-path is a path whose ends are both in A. The weight of a path P in G is the sum of the group values on forward oriented arcs minus the sum of the backward oriented arcs in P. (If Γ is not abelian, we sum the labels in their order along the path.) We are interested in the maximum number of vertex-disjoint A-paths each of non-zero weight. When A = V this problem is equivalent to the maximum matching problem. The general case also includes Mader's S-paths problem. We prove that for any positive integer k, either there are k vertex-disjoint A-paths each of non-zero weight, or there is a set of at most 2k −2 vertices that meets each of the non-zero A-paths. This result is obtained as a consequence of an exact min-max theorem. These results were obtained at a workshop on Structural Graph Theory at the PIMS Institute in Vancouver, Canada. This research was partially conducted during the period the first author served as a Clay Mathematics Institute Long-Term Prize Fellow.     

Diameter graphs of polygons and the proof of a conjecture of Graham

We show that for an n-gon with unit diameter to have maximum area, its diameter graph must contain a cycle, and we derive an isodiametric theorem for such n-gons in terms of the length of the cycle. We then apply this theorem to prove Graham's 1975 conjecture that the diameter graph of a maximal 2m-gon (m?3) must be a cycle of length 2m−1 with one additional edge attached to it.     

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.     

Elastic instability of the nano-structured state as an intrinsic probe to study the early formation stages of sol–gel derived (Pb<Subscript>1-x</Subscript>Ca<Subscript>x</Subscript>)TiO<Subscript>3</Subscript> thin films

A novel method to investigate the early formation stages of polycrystalline (Pb_1-xCa_x)TiO₃ (PCT) perovskite films by means of traditional Brillouin and micro-Brillouin spectroscopy (BS, mBS) is described in the present work. The films were prepared by chemical solution deposition (CSD) onto oxidized (100)Si substrates and treated at temperatures between 350–650 °C by rapid thermal processing (RTP). The elastic instability observed by Brillouin spectroscopy at the nano-structured state of the PCT films was used here to determine their crystallization temperatures. Coexistence of different nanocrystalline phases (e.g., pyrochlore, perovskite) in the films could also be detected by this technique. The reliability of these results is demonstrated by complementary information obtained by X-ray diffraction (XRD) and scanning force microscopy (SFM). The effects of the annealing temperature and of the Ca²⁺ content on the crystallization process of these films are also discussed. PACS 78.35.+c; 77.84.-s; 61.82.Rx     

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.     

The Role of a Specific Response of Media in the Vavilov-Cherenkov Effect

It is shown that the condition υ > υ_p (ω), which is necessary in order to trigger the Vavilov-Cherenkov effect, determines the interval of radiated frequencies and it alone cannot establish a strong restriction to the velocity of the particle. It is exhibited that it is possible to define a general lower bound for the velocity of the particle, which does not depend on the frequency when both, a specific response of the medium is taken into account and the mentioned condition is considered. The minimum value of the phase velocity of light in the medium determines the existence of such general lower bound.     

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.