Kinetic evidence of a common mechanism in the oxidations of diethyl sulfide by dichromates and halochromates of heterocyclic bases

The oxidations of diethyl sulfide by potassium dichromate, pyridinium dichromate, quinolinium dichromate, imidazolium dichromate, nicotinium dichromate, isonicotinium dichromate, pyridinium fluorochromate, quinolinium fluorochromate, imidazolium fluorochromate, pyridinium chlorochromate, quinolinium chlorochromate, and pyridinium bromochromate follow identical kinetic orders—first‐order each with respect to the chromium(VI) reagents, sulfide and hydrogen ion, and moderately inhibited by manganese(II) ion. The energy of activation varies linearly with the logarithm of frequency factor and so does the enthalpy of activation with the entropy of activation. Also, the activation free energies do not differ significantly. The dichromates and halochromates of heterocyclic bases oxidize diethyl sulfide via a common mechanism. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 35: 1–8, 2003     

Role of the microstructure on the transport properties of Y-doped zirconia and Gd-doped ceria

Transmission electron microscopy characterizations and XPS analyses have allowed us to show the influence of the microstructure and nanochemistry on the transport properties of Y₂O₃-(9 mol%)-stabilized zirconia (YSZ) and Gd₂O₃ (10 mol%)-doped ceria (GDC). The grain boundary electrical conductivity (σ_gb) and oxygen diffusion coefficient (D_o) of conventional YSZ ceramics increase with the grain size, while an opposite behavior was found for GDC samples. This difference was attributed to glassy precipitates present at YSZ grain boundaries. Furthermore, it was shown that kinetic demixing processes take place during cooling, at the end of sintering. This causes important changes in the cationic species distribution at interfaces and plays an important role on the transport properties of these two materials. Paper presented at the 9th EuroConference on Ionics, Ixia, Rhodes, Greece, Sept. 15 – 21, 2002.     

Use of traps to study positron annihilation in astrophysically relevant media

We discuss possible experiments which can exploit recently-developed techniques to accumulate, store, and manipulate low-energy positrons to measure the parameters associated with positron annihilation radiation from media of astrophysical interest. Media discussed include collections of dust grains, partially ionized gases, He, H₂, and other molecular gases and gas mixtures, including polycyclic aromatic hydrocarbon (PAH) molecules relevant to the interstellar medium.     

Future contributions toJournal of Crystallographic and Spectroscopic Research

Future contributions toJournal of Crystallographic and Spectroscopic Research     

Theory of mixed-polarization propagation in anisotropic cubic media

Polarization dynamics are considered in the presence of an anisotropic Kerr non-linearity in the most common semiconductor waveguide geometry. The equations of motion are formulated in terms of Stokes polarization parameters and their Hamiltonian form is derived. Stationary solutions and their stability are found for plane-wave propagation. It is found that the non-integrable problem of mixed-polarization spatial soliton dynamics can be largely explained in terms of the equivalent plane-wave solutions.     

Role of Na(+)-Ca2+ exchange system in the pathogenesis of myocardial ischemia-reperfusion damage

Results from a systematic experiment on isolated perfused rat heart and isolated myocytes of adult rat showed that the mechanism of calcium influx during myocardial ischemia-reperfusion is due to the development of intracellular sodium overload during ischemic period; on reperfusion, the high intracellular Na+ content activated the reverse direction of Na(+)-Ca2+ exchange over myocardial sarcolemma (SL), thus a large quantity of extracellular Ca2+ fluxed over the SL to the intracellular space, forming a condition of intracellular Ca2+ overload, which leads to irreversible damage of the myocardium.     

Dielectric relaxation and aging effect in interpenetrating network polymers of poly(urethane)-poly(methyl methacrylate)

The permittivity and loss of poly(methyl methacrylate) (PMMA) network crosslinked with trimethylol-1,1,1 propane and its interpenetrating network polymers with 10, 34, and 50% (by weight) poly(urethane) have been measured from 100 to 400 K over a frequency range of 12 to 1 × 10⁵ Hz. Two relaxation processes, γ and β, are observed in the PMMA network, and a third process, α_pu, in the 10% poly(urethane) IPN. At higher concentrations of poly(urethane), the γ process is removed from the temperature-frequency range of our study. Crosslinking in pure PMMA slows the segmental motions involved in the β process and raises its activation energy. Physical aging of the 10 wt% poly(urethane)-PMMA causes its γ process to become indiscernible and the α_pu process to become better resolved. A discussion of these results in terms of local regions of segmental motion is provided.