Characterization of ZnO and Zn0.95Co0.05O prepared by sol-gel method using PAC spectroscopy

We report on the first NMR study of ⁷³Ge nuclear spin decoherence in germanium single crystals with different abundance of the ⁷³Ge isotope. Hahn echo decays are well fit by a superposition of two exponentials. The deviation from the single exponential is more pronounced in the more spin-diluted sample, causing long-lived echoes. We show that the decay of these echoes becomes slower with the reduction of ⁷³Ge abundance and is therefore caused by dipole–dipole interaction, reflecting the fundamental decoherence process in the spin system. The fast decay at the beginning of the relaxation process is shown to be mainly caused by the quadrupole interaction. Our experimental findings are supported by the calculations of Hahn echo decays in the germanium crystals under study. Quite good agreement between the theory and experiment is demonstrated.     

Sensitivity analysis of the moments of the profit on an Income Protection Policy

The main purpose of this paper is to perform a sensitivity analysis where we quantify and analyse the effects on the mean of the profit on an Income Protection policy and two risk measures of changing the values of the transition intensities. All the calculations carried out are based on a multiple state model for Income Protection proposed in Continuous Mortality Investigation Committee (Continuous Mortality Investigation Reports 1991; 12 ). Within this model, we derive a formula for the mean of the profit, which enables to evaluate it more efficiently. In order to calculate the two risk measures we use the numerical algorithms for the calculation of the moments of the profit proposed by Waters (Insurance: Mathematics and Economics 1990; 9 :101–113). We carry out the sensitivity analysis considering two different situations: in the first situation, we update the premium rates used to calculate the moments of the profit, according to the changes in the values of the transition intensities; in the second one, we do not update the premium rates. Both analyses are of practical interest to insurance companies selling Income Protection policies. Copyright © 2009 John Wiley & Sons, Ltd.     

Thermal characterization of usnic acid/collagen-based films

The purpose of this study was to evaluate the physical–chemical properties of collagen (CL) and usnic acid/collagen-based (UAC) films, using differential thermal analysis (DTA), thermogravimetry (TG/DTG), infrared spectroscopy (FTIR), and scanning electron microscopy (SEM). Both films were prepared by casting process using polyethylene glycol 1500 (PEG 1500) as plasticizer. In the spectrum of UAC, similar bands of the usnic acid are observed, indicating that the polymerization (film formation) did not affect the stability of the drug. Distinctly, DTA curve of UAC did not show an endothermic peak at 201 °C, indicative that the drug was incorporated into the polymeric system. These results were corroborated by the scanning electron microscopy (SEM). The TG/DTG curves of UAC presented a different thermal decomposition profile compared to the individual compounds and CL. These findings suggest the occurrence of molecular dispersion or solubilization of the drug in the collagen film.     

On the stability of metal–aminoacid complexes in water based on water–ligand exchange reactions and electronic properties: Detailed study on iron–glycine hexacoordinated complexes

Thermodynamic stability of metal–aminoacid complexes in water is discussed in terms of the Gibbs free energy of water–ligand exchange processes, and the electronic stabilizing factors thoroughly investigated by means of 1‐electron and 2‐electron density properties. Hexacoordinated complexes formed between iron cations and glycine molecules acting as monodentate or bidentate ligands have been chosen as targets for the current study. Results agree with experimental findings, and complexes formed with bidentate ligands are found to be more stable than those formed with monodentate ones. The larger the number of the coordinated glycine molecules the more stable is the complex. Fe(III) complexes are more stable than Fe(II) ones, but differences are small and the Fe³⁺/Fe²⁺ exchange process appears to be energetically feasible for these complexes. Formation of the second glycine–iron interaction involving the amino nitrogen in the bidentate ligands is enthalpycally unfavorable but takes place due to the large entropy rise of the process. The larger stability of Fe(III) complexes is due however to the balance between energetic and solvation terms, which is favorable to these complexes. Electron density properties account satisfactorily for the electronic energy changes along the complex formation in terms of ligand–metal electron transfer and covalent bond orders. © 2010 Wiley Periodicals, Inc. J Comput Chem 2010     

Influence of the purification process on the stability of <Emphasis Type="Italic">Jatropha curcas</Emphasis> biodiesel

The aim of this work was to evaluate the influence of the purification process on the stability of Jatropha curcas biodiesel. The biodiesel was obtained using a variety of purification processes: three wet methods with different drying processes (vacuum oven, conventional oven and anhydrous sodium sulfate) and one dry method (purification with adsorbent magnesium silicate). Biodiesel was characterized through the analysis of carbon residue, acidity index, infrared and gas chromatography. The composition J. curcas oil indicated 56.3 % of unsaturated fatty acids and 43.7 % of saturated fatty acids. Jatropha oil presented high quantity of saturated acids, which are less susceptible at oxidation. The biodiesel sample that was chemically purified (PUsq) presented better purity, indicating be the process more efficient in remove the residues of synthesis. Thermogravimetric curves of purified biodiesel by wet method, PUsq, with chemical drying using anhydrous sodium sulfate, and PUsv, with vacuum drying, showed the highest initial decomposition temperatures, indicating higher thermal stability. The carbon residue and infrared analyses suggested that contamination by catalyst residue is a determining factor in reduction of the oxidative stability of biodiesel. The oxidative stability was evaluated using Rancimat and pressure differential scanning calorimetry. Biodiesel samples showing better oxidative stability were purified using PUsq and PUsv, which obtained stability of 6 h using the Rancimat technique, the minimum limit set by Brazilian legislation, without the addition of antioxidant, suggesting that these methods least influenced the stability of biodiesel.     

IMEP-24 analysis of eight trace elements in toys

The International Measurement Evaluation Program (IMEP) organised the IMEP-24 interlaboratory comparison after reports in the media about high levels of lead in toys. The aim of this comparison was to verify the laboratories’ capacity to evaluate trace-element levels in a possible toy-like material according to the European Standard EN 71-3:1994. As test material, it used a former certified reference material containing levels of antimony, arsenic, barium, cadmium, chromium, mercury, lead and selenium around the limits set in the standard.Four expert laboratories confirmed the reference values (Xref) for all elements but Hg, and established a reference value for Hg. The scatter of the results reported by the participants was large, as expected, but showed a close to normal distribution around the reference values for five of the eight trace elements. The spread of results was mainly attributed to sampling and sample preparation.One major issue observed in this exercise was the lack of legislative rules about how to report the result, or, more specifically, the use of the analytical correction, which was introduced in EN 71-3:1994 to achieve consistent interpretation of results and which is to be applied when values are equal to or above the maximum limits set in the standard. Its application by the participants was very inconsistent and led to problems in their evaluation. There is clearly a need for clarification and for more formal regulations with regard to result reporting in order to minimise the risk of confusion.Participants were also asked to give their opinion with regard to the acceptability of the test material for the market. The majority correctly considered the material as non-compliant. However, almost one-third incorrectly assessed the material as compliant.     

IMEP-24 analysis of eight trace elements in toys

The International Measurement Evaluation Program (IMEP) organized the IMEP-24 interlaboratory comparison after reports in the media about high levels of lead in toys. The aim of this comparison was to verify the laboratories’ capacity to evaluate trace-element levels in a possible toy-like material according to the European Standard EN 71-3:1994. As test material, it used a former certified reference material containing levels of antimony, arsenic, barium, cadmium, chromium, mercury, lead and selenium around the limits set in the standard.Four expert laboratories confirmed the reference values (Xref) for all elements but Hg, and established a reference value for Hg. The scatter of the results reported by the participants was large, as expected, but showed a close to normal distribution around the reference values for five of the eight trace elements. The spread of results was mainly attributed to sampling and sample preparation.One major issue observed in this exercise was the lack of legislative rules about how to report the result, or, more specifically, the use of the analytical correction, which was introduced in EN 71-3:1994 to achieve consistent interpretation of results and which is to be applied when values are equal to or above the maximum limits set in the standard. Its application by the participants was very inconsistent and led to problems in their evaluation. There is clearly a need for clarification and for more formal regulations with regard to result reporting in order to minimize the risk of confusion.Participants were also asked to give their opinion with regard to the acceptability of the test material for the market. The majority correctly considered the material as non-compliant. However, almost one-third incorrectly assessed the material as compliant.     

Design and characterization of bi-soft segmented polyurethane microparticles for biomedical application

Bi-soft segmented poly(ester urethane urea) microparticles were prepared and characterized aiming a biomedical application. Two different formulations were developed, using poly(propylene glycol), tolylene 2,4-diisocyanate terminated pre-polymer (TDI) and poly(propylene oxide)-based tri-isocyanated terminated pre-polymer (TI). A second soft segment was included due to poly(?-caprolactone) diol (PCL). Infrared spectroscopy, used to study the polymeric structure, namely its H-bonding properties, revealed a slightly higher degree of phase separation in TDI-microparticles. TI-microparticles presented slower rate of hydrolytic degradation, and, accordingly, fairly low toxic effect against macrophages. These new formulations are good candidates as non-biodegradable biomedical systems.     

Heparin Binding by Murine Recombinant Prion Protein Leads to Transient Aggregation and Formation of RNA-Resistant Species

The conversion of cellular prion protein (PrP(C)) into the pathological conformer PrP(Sc) requires contact between both isoforms and probably also requires a cellular factor, such as a nucleic acid or a glycosaminoglycan (GAG). Little is known about the structural features implicit in the GAG-PrP interaction. In the present work, light scattering, fluorescence, circular dichroism, and nuclear magnetic resonance (NMR) spectroscopy were used to describe the chemical and physical properties of the murine recombinant PrP 23-231 interaction with low molecular weight heparin (LMWHep) at pH 7.4 and 5.5. LMWHep interacts with rPrP 23-231, thereby inducing transient aggregation. The interaction between murine rPrP and heparin at pH 5.5 had a stoichiometry of 2:1 (LMWHep:rPrP 23-231), in contrast to a 1:1 binding ratio at pH 7.4. At binding equilibrium, NMR spectra showed that rPrP complexed with LMWHep had the same general fold as that of the free protein, even though the binding can be indicated by significant changes in few residues of the C-terminal domain, especially at pH 5.5. Notably, the soluble LMWHep:rPrP complex prevented RNA-induced aggregation. We also investigated the interaction between LMWHep and the deletion mutants rPrP Δ51-90 and Δ32-121. Heparin did not bind these constructs at pH 7.4 but was able to interact at pH 5.5, indicating that this glycosaminoglycan binds the octapeptide repeat region at pH 7.4 but can also bind other regions of the protein at pH 5.5. The interaction at pH 5.5 was dependent on histidine residues of the murine rPrP 23-231. Depending on the cellular milieu, the PrP may expose different regions that can bind GAG. These results shed light on the role of GAGs in PrP conversion. The transient aggregation of PrP may explain why some GAGs have been reported to induce the conversion into the misfolded, scrapie conformation, whereas others are thought to protect against conversion. The acquired resistance of the complex against RNA-induced aggregation explains some of the unique properties of the PrP interaction with GAGs.