Pulse radiolysis study of the initial steps of the polymerization of cyclohexyl acrylate and cyclohexyl methacrylate

Pulse radiolysis with kinetic spectroscopic detection was applied to study the kinetics of the first steps of radiation induced polymerization of cyclohexyl acrylate and cyclohexyl methacrylate in cyclohexane solvent. The reactions were initiated by cyclohexyl radicals produced in the radiolysis of the solvent. The transient absorption spectra of the -carboxyalkyl type radicals produced in addition reaction show maxima around 300 nm. This shifts to longer wavelength with time after the pulse. This phenomenon was explained by the oligomerization reaction. From the kinetic curves average rate coefficients of termination for the oligomer radicals (2k_t) were determined as a function of time elapsed after the electron pulse. The values obtained were compared with those calculated for other (acrylate and methacrylate type) monomers.     

Stochastic analysis in life office management: applications to large annuity portfolios

The paper deals with the riskiness analysis for a large portfolio of life annuities. By means of the limiting distribution of the present value of the portfolio, in the first part of the paper a model for evaluating the investment and the projection risks is presented. In the second part, with regard to the investment risk's effects, the insolvency risk is measured considering the cumulative probability distribution function of the discounted average cost per policy. Copyright © 2003 John Wiley & Sons, Ltd.     

On the pivot structure for the weighing matrix W(12,11)

In the present article we concentrate our study on the growth problem for the weighing matrix W(12,11) and show that the unique W(12,11) has three pivot structures. An improved algorithm for extending a k × k (0,+,-) matrix to a W(n,n-1), if possible, has been developed to simplify the proof. For the implementation of the algorithm special emphasis is given to the notions of data structures and parallel processing.     

Spectrophotometric Study of Luminol in Dimethyl Sulfoxide–Potassium Hydroxide

The spectrophotometric study of luminol (LH₂) in dimethyl sulfoxide (DMSO), DMSO-water solutions, and alkaline DMSO and DMSO-water solutions has been done, focusing on the effect of the KOH additon on LH₂ absorption and fluorescence properties. The absorption spectra indicate an acid-base equilibrium, and the luminol dianion (L^2–) formation at 3 × 10^–4 – 2.4 × 10^–3 M KOH. The decrease of the fluorescence intensity and the variation of the excitation spectra of LH₂-DMSO-KOH solutions with KOH concentration have been similarly explained. The acid-base process is reversible. The addition of HCl to the solution with 3.0 × 10^–3 M KOH leads to an increase of the fluorescence intensity to its highest value, observed in pure DMSO. The addition of HCl to the LH₂-DMSO solution leads to the decrease of the fluorescence intensity as a result of the LH⁺ ₃ cation formation. In LH₂-DMSO-water, the fluorescence band is shifted from 405 nm to 424 nm and increased in the intensity. In the presence of KOH (in LH₂-DMSO-water-KOH solution) a new band appears, with the maximum at 485 nm and the band at 405 nm decreased. The changes in fluorescence lifetimes also evidence the different chemical species formed.     

Mössbauer study of spin-glass Fe x Zn1−x F2 system

⁵⁷Fe Mössbauer effect measurements in the diluted Ising antiferromagnet Fe _x Zn_1?x F₂ withx=0.25 andx=0.57 at temperatures between 4.2 and 55 K, are reported. DC suceptibility measurements show a spin-glass (SG) phase at low temperatures forx≤0.31. Our Mössbauer spectra show a phase transition to a SG state with antiferromagnetic order (AFSG) forx=0.25 and only antiferromagnetic order forx=0.57.     

High-performance liquid chromatography and thin-layer chromatography assays for Devil's Club (Oplopanax horridus)

Devil's root, Oplopanax horridus, is a widely used folk medicine in Alaska and British Columbia. The inner bark of the root and stem has been used to treat colds, cough, fever, and diabetes. The present study involves the development of high-pressure liquid chromatography (HPLC) and thin-layer chromatography (TLC) methods to detect the presence of trans-nerolidol and sterols in the root bark. The HPLC and TLC analytical methods presented are suitable for the characterization and identification of Oplopanax horridus.     

Application of amperometric sol-gel biosensor to flow injection determination of glucose

A glucose biosensor with enzyme immobilised by sol–gel technology was constructed and evaluated. The glucose biosensor reported is based on encapsulated GOX within a sol–gel glass, prepared with 3-aminopropyltriethoxy silane, 2-(3,4-epoxycyclohexyl)-ethyltrimetoxy silane and HCl. A flow system incorporating the amperometric biosensor constructed was developed for the determination of glucose in the 1×10⁻⁴–5×10⁻³ mol l⁻¹ range with a precision of 1.5%. The results obtained for the analysis of electrolytic solution for iv administration and human serum samples showed good agreement between the proposed method and the reference procedure, with relative error <5%.     

Thermal and mechanical properties of PE/organoclay nanocomposites

Polyethylene/montmorillonite clay nanocomposites were obtained via direct melt intercalation. The clay was organically modified with four different types of quaternary ammonium salts. The objective of this work is to study the use of montmorillonite clay in the production of nanocomposites by means on rheological, mechanical and crystallization properties of nanocomposites and to compare to the properties of the matrix and PE/unmodified clay nanocomposites. In general, the tensile test showed that the yield strength and modulus of the nanocomposites are close to the pure PE. Apparently, the mixture with Dodigen salt seems to be more stable than the pure PE and PE/unmodified clay.     

Mechanism of ferromagnetic coupling in copper(II)-gadolinium(III) complexes

This paper offers the first series of state-of-the-art quantum chemical calculations (CASSCF, CASPT2, MS-CASPT2) and analytical models for the well-known problem of quasi-general ferromagnetic coupling in copper-gadolinium complexes. A system chosen from the chemical report of Costes et al. was taken as prototype. At the CASSCF level, calculated results for the experimental structure reproduced the magnetic coupling constant well (J(calcd)( )()= +7.67 cm(-)(1) vs J(exp)( )()= +7.0 cm(-)(1)). For more insight, the study molecule was further idealized by geometry optimization to C(2)(v)() symmetry. Systematic ab initio computation experiments were designed and performed. Owing to specific problems related to the non-aufbau ground configuration of the [CuL-Gd] complexes, the calculations were conducted in a nonstandard manner. We found that the qualitative mechanism of Kahn, assigned to the electron jump from 3d of Cu(II) to 5d shell of Gd(III), can be presented effectively as the cause of the phenomenon, if CASPT2 MOs are taken as magnetic orbitals. We showed that the ferromagnetic coupling is also matched and magnified by spin polarization effects over the ligand, in line with the early assumption of Gatteschi. To be distinguished from the initial hypothesis of Gatteschi, which assumed the role of 6s AO of Gd(III), we found that one 5d-type AO is actually involved in the polarization scheme. In fact, the Gatteschi and Kahn mechanisms are not mutually contradictory, but are even interconvertible with appropriate changes of the magnetic orbitals. Within C(2)(v)() symmetry of complexes, the ferromagnetic coupling can be qualitatively regarded as the preponderant influence of interaction channels exhibiting orbital orthogonality (four 3d-4f contacts) over the nonorthogonal ones (two 3d-4f contacts). The effective preponderance from ferromagnetic pathways is supported by CASPT2 results. One may explain the generality of Cu(II)-Gd(III) ferromagnetic coupling as being correlated with the large occurrence of approximate pseudo-C(2)(v)() geometry of complexes. The observed orbital regularity is lost in lower symmetries. Thus, the antiferromagnetic exceptions occur when the molecular asymmetry is advanced (e.g., owing to strong chemical nonequivalence of the donor atoms).