Novel amperometric sensors for nitrite detection using electrodes modified with PEDOT prepared in ionic liquids

Journal of Solid State Electrochemistry - Novel amperometric sensors based on poly-3,4-ethylenedioxythiophene (PEDOT) were prepared and characterized for nitrite detection. An experimental matrix...     

Two shock and wear systems under repair standing a finite number of shocks

A shock and wear system standing a finite number of shocks and subject to two types of repairs is considered. The failure of the system can be due to wear or to a fatal shock. Associated to these failures there are two repair types: normal and severe. Repairs are as good as new. The shocks arrive following a Markovian arrival process, and the lifetime of the system follows a continuous phase-type distribution. The repair times follow different continuous phase-type distributions, depending on the type of failure. Under these assumptions, two systems are studied, depending on the finite number of shocks that the system can stand before a fatal failure that can be random or fixed. In the first case, the number of shocks is governed by a discrete phase-type distribution. After a finite (random or fixed) number of non-fatal shocks the system is repaired (severe repair). The repair due to wear is a normal repair. For these systems, general Markov models are constructed and the following elements are studied: the stationary probability vector; the transient rate of occurrence of failures; the renewal process associated to the repairs, including the distribution of the period between replacements and the number of non-fatal shocks in this period. Special cases of the model with random number of shocks are presented. An application illustrating the numerical calculations is given. The systems are studied in such a way that several particular cases can be deduced from the general ones straightaway. We apply the matrix-analytic methods for studying these models showing their versatility.     

Multicomponent phosphate invert glasses with improved processing

Owing to their structure of small phosphate units, phosphate invert glasses have high crystallisation tendencies, which make processing of the melt challenging. The aim was to improve their processing by (1) increasing the number of glass components and (2) incorporating intermediate oxides (TiO₂, MgO and ZnO). Glasses (P₂O₅–CaO–MgO–Na₂O) were produced by a melt-quench route. In series 1, TiO₂ was partially substituted for Na₂O, and the number of components was increased by partially substituting strontium for calcium, zinc for magnesium and potassium for sodium on a molar base. In series 2, the MgO + ZnO content in the multicomponent glass was varied between 0 and 20 mol% in exchange for CaO + SrO. Differential scanning calorimetry showed a significant increase of the processing window in the multicomponent glasses, explained by an increased energy barrier for crystallisation owing to increased entropy of mixing. The MgO + ZnO content also significantly improved the processing window from 117 K (0 mol% MgO + ZnO) to 185 K (20 mol%), owing to their large field strength. These results show that the processing of phosphate invert glasses for biomedical applications can be improved significantly by incorporating ions such as strontium or zinc which are also known to have therapeutic effects.     

A reliability system under different types of shock governed by a Markovian arrival process and maintenance policy K

A reliability system subject to shocks producing damage and failure is considered. The source of shocks producing failures is governed by a Markovian arrival process. All the shocks produce deterioration and some of them failures, which can be repairable or non-repairable. Repair times are governed by a phase-type distribution. The number of deteriorating shocks that the system can stand is fixed. After a fatal failure the system is replaced by another identical one. For this model the availability, the reliability, and the rate of occurrence of the different types of failures are calculated. It is shown that this model extends other previously published in the literature.     

Bulk and surface structures of V2O5/ZrO2 catalysts for n-butane oxidative dehydrogenation

The present investigation focuses on the structural properties and reactivity of zirconia-supported vanadium oxide catalysts, prepared by equilibrium adsorption in basic (pH 10) or in acid (pH 2.7) conditions with vanadium content up to 6 wt.% (pH 10) and up to 11.6 wt.% (pH 2.7). The samples, heated at 823 K for 5 h in air, were characterized by X-ray diffraction, Raman spectroscopy and TPR, both as prepared and after leaching with an ammonia solution to remove species not anchored to the zirconia surface. Some representative samples were also tested for the n-butane oxidative dehydrogenation (ODH) reaction. Depending on vanadium content, various vanadium species were identified by Raman spectroscopy that reacted differently on exposure to H₂. At similar loading, the fraction of vanadium in a dispersed state and thus interacting with the support was higher in samples prepared at pH 10 than in those at pH 2.7. Samples prepared at pH 2.7 contained a higher fraction of large polymeric structures in addition to ZrV₂O₇ and V₂O₅.In line with literature data for propane ODH on similar catalysts, our catalytic results suggested that the active sites for the ODH reaction are associated with the V–O–V bonds of the polymeric exposed structures, whereas the Zr–O–V sites favour alkane combustion.     

Photophysical properties of blue - emitting silicon nanoparticles

Silicon nanoparticles with strong blue photoluminescence were synthesized by electrochemical etching of silicon wafers and ultrasonically removed under N(2) atmosphere in organic solvents to produce colloids. Thermal treatment leads to the formation of colloidal Si particles of 3 ± 1 nm diameter, which upon excitation with 340 - 380 nm light exhibited room temperature luminescence in the range from 400 to 500 nm. The emission and the one- and two-photon excitation spectra of the particles are not sensitive to surface functionalization with methyl 2-methylprop-2-enoate. However, the derivatized particles show higher emission quantum yields in air-saturated suspensions (44%) than the underivatized particles (27%), as well as higher stability of its dispersions.FTIR and XPS spectra indicate a significant surface oxidation of the particles. The Si:O:C ratio at the surface of the derivatized particles estimated from XPS is Si(3)O(6)(C(5)O(2)H(y))(1), with y = 7 - 8. Vibronic spacing is observed in both the emission and excitation spectra. The information obtained from one-photon excitation experiments (emission and excitation spectra, photoluminescence quantum yields, luminescence decay lifetimes and anisotropy correlation lifetimes), as well as from two-photon excitation fluorescence correlation spectroscopy (brightness and diffusion coefficients) and TEM indicate that the blue-emitting particles are monodisperse and ball-shaped. Particle size clearly determines the emission and excitation spectral region, as expected from quantum confinement, but the presence and extent of Si-O species on the silicon networks seem crucial for determining the spectrum features and intensity of emission. The nanoparticles could hold great potential as quantum dots for applications as luminescence sensors in biology and environmental science.     

Homomorphisms and polynomial invariants of graphs

This paper initiates a general study of the connection between graph homomorphisms and the Tutte polynomial. This connection can be extended to other polynomial invariants of graphs related to the Tutte polynomial such as the transition, the circuit partition, the boundary, and the coboundary polynomials. As an application, we describe in terms of homomorphism counting some fundamental evaluations of the Tutte polynomial in abelian groups and statistical physics. We conclude the paper by providing a homomorphism view of the uniqueness conjectures formulated by Bollobás, Pebody and Riordan.