A Simple and Convenient Method for Cleavage of Silyl Esthers

Cleavage of silyl ethers can be efficiently effected using FeCl₃, SnCl₂, Cu(NO₃)₂ and Ce(NO₃)₃ at room temperature.     

DFT study of ferroelectric properties of the copolymers: Poly(vinylideneflouride‐trifluoroethylene) and poly(vinylidene fluoride‐chlorotrifluoroethylene)

A theoretical study of poly(vinylidene flouride‐trifluoroethylene) and poly(vinylidene fluoride‐chlorotrifluoroethylene, is presented. By density functional theory calculations, some of the properties of these materials have been obtained. Among such properties, the dipolar moment and the energies associated to the structural changes. The B3LYP functional and 6311+G(d,p) bases set were used with Gaussian program. Calculations associated to different conformations were carried out to get insight about the involved phase changes. The energetic, charges, and dipole moment were calculated. The conformations, namely, I = T_p, II = TG_a, and III = TG_p, where T means trans and G means gauche, for the two polymers aforementioned were compared with the poly(vinilydene fluoride) studies previously obtained. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem 110:2411–2417, 2010     

International comparison of the determination of the mass fraction of cadmium, chromium, mercury and lead in polypropylene: the Comité Consultatif pour la Quantité de Matière pilot study CCQM-P106

The CCQM-P106 pilot study was organized by the inorganic working group of the Comité Consultatif pour la Quantité de Matière (CCQM) as a feasibility comparison to study the applicability of different analysis methods to the polypropylene sample and test the abilities of the participants for measuring the Cd, Cr, Hg and Pb in polypropylene. National Institute of Metrology P.R. China (NIM) acted as the coordinating laboratory of this pilot study. There were 21 laboratories that submitted the final results. The median values of the mass fraction of Cd, Cr, Hg and Pb were 36.12 mg kg^?1 (the median absolute deviation about the median (MADe) = 0.46 mg kg^?1), 252.5 mg kg^?1 (MADe = 3.4 mg kg^?1), 387.0 mg kg^?1 (MADe = 10.1 mg kg^?1) and 466.2 mg kg^?1 (MADe = 8.9 mg kg^?1), respectively. Isotope dilution mass spectrometry (IDMS), inductively coupled plasma-mass spectrometry (ICP-MS), inductively coupled plasma-optical emission spectrometry (ICP-OES), atomic absorption spectrometry (AAS), instrumental neutron activation analysis (INAA) and X-ray fluorescence (XRF) measurement methods were used, and microwave digestion was used by the most of the participants. In general, very good agreement of the results was observed. Moreover, compared to the results of other methods, the results of IDMS still showed less spread amongst laboratories and had a smaller uncertainty. In addition, the results of some analytes used by XRF and INAA also got satisfactory agreement with the median value.     

Electrochemical preparation and characterisation of CoPt magnetic particles

CoPt particles of different size and modulate magnetic properties have been prepared by electrodeposition. Particles of growing size from 50 nm until continuous deposits have been obtained and their composition, crystalline structure and magnetic properties have been analyzed. The prepared CoPt particles from 50 nm to 250 nm showed ferromagnetic behaviour so did the continuous deposits. However, drastic changes in magnetism have been detected related to the size of the particles: the smallest particles presented lower coercivity which increases with increasing size, with a maximum value for particles of 150–250 nm diameter. The coercivity decreased when continuous deposits were attained due to the disordered growing and the loss of the surface anisotropy.     

Magnetic properties of nanocrystalline CoPt electrodeposited films. Influence of P incorporation

Platinum-rich CoPt films have been electrodeposited with the aim of preparing hard magnetic films on silicon-based substrates without the need for subsequent annealing. Electrodeposition conditions have permitted the crystalline structure of the films to be controlled. Pt percentages of up to 60–65 wt.% have been attained while maintaining the hexagonal Co phase, leading to CoPt films with moderate coercivity and good corrosion resistance. However, when low deposition potentials were used, CoPt films with higher Pt percentages were obtained, but in this case, the films exhibited an fcc structure, having lower coercivity and less corrosion resistance. The presence of hypophosphite in the solution limited the platinum percentage in the deposited CoPtP films, but an hexagonal close-packed (hcp) structure was always observed in this case. The incorporation of P into the deposits led to increases in both the coercivity of the films and the corrosion resistance of the coatings, with respect to pure CoPt. The highest coercivity was obtained for hcp CoPtP deposits with 40 wt.% of Pt.     

Solid-phase selenium-catalyzed selective allylic chlorination of polyprenoids: facile syntheses of biologically active terpenoids

Regioselective halogenation of the terminal isopropylidene unit of different acyclic polyolefinic polyprenoids (farnesyl acetate, geranylgeranyl acetate, squalene, etc.) using NCS/catalytic polymer-supported selenenyl bromide is described; good to excellent yields are obtained (68-96%). The first applications of this protocol include the concise synthesis of bioactive terpenoids 1-3.     

Extraction and analysis of ochratoxin A in bread using pressurised liquid extraction and liquid chromatography

A pressurised liquid extraction (PLE) method for the analysis of ochratoxin A (OTA) in bread samples is given. Parameters such as solvent, temperature, pressure and time were investigated thoroughly. The optimized PLE conditions were: methanol as extraction solvent, 80 degrees C, 2000 psi and a 5-min cycle. OTA was determined by liquid chromatography coupled with fluorescence detection and confirmed by methyl ester derivatization. Under these conditions OTA recovery is 92.3% with a RSD of 5%. Limits of detection and quantification were 0.02 and 0.06 microg/kg, respectively. The proposed method was applied to 20 bread samples, finding two positive samples with OTA levels below the maximum permitted levels by the European Union.     

A comprehensive probabilistic analysis of approximate SIR-type epidemiological models via full randomized discrete-time Markov chain formulation with applications

This paper provides a comprehensive probabilistic analysis of a full randomization of approximate SIR-type epidemiological models based on discrete-time Markov chain formulation. The randomization is performed by assuming that all input data (initial conditions, the contagion, and recovering rates involved in the transition matrix) are random variables instead of deterministic constants. In the first part of the paper, we determine explicit expressions for the so called first probability density function of each subpopulation identified as the corresponding states of the Markov chain (susceptible, infected, and recovered) in terms of the probability density function of each input random variable. Afterwards, we obtain the probability density functions of the times until a given proportion of the population remains susceptible, infected, and recovered, respectively. The theoretical analysis is completed by computing explicit expressions of important randomized epidemiological quantities, namely, the basic reproduction number, the effective reproduction number, and the herd immunity threshold. The study is conducted under very general assumptions and taking extensive advantage of the random variable transformation technique. The second part of the paper is devoted to apply our theoretical findings to describe the dynamics of the pandemic influenza in Egypt using simulated data excerpted from the literature. The simulations are complemented with valuable information, which is seldom displayed in epidemiological models. In spite of the nonlinear mathematical nature of SIR epidemiological model, our results show a strong agreement with the approximation via an appropriate randomized Markov chain. A justification in this regard is discussed.     

Monitoring the electrochemistry of single molecules by surface-enhanced Raman spectroscopy

Coherent control of chemical species in complex systems is always subject to intrinsic inhomogeneities from the environment. For example, slight chemical modifications can decisively affect transport properties of molecules on surfaces. Hence, single-molecule (SM) studies are the best solution to avoid these problems and to study diverse phenomena in biology, physics, and chemistry. Along these lines, monitoring SM redox processes has always been a "holy grail" in electrochemistry. To date, claims of SM electrochemistry by spectroscopy have come only from fluorescence quenching of polymers and redox-fluorescent molecules. In unconnected developments, the potential of the bianalyte surface-enhanced Raman scattering (SERS) method as a technique with SM sensitivity has been demonstrated. Raman spectroscopy has the potential to explore SM detection of any molecule, independent of its chemical nature. We provide definitive proof of SM events following redox cycles using SERS. The superior sensitivity and spectral richness of SERS makes it general enough to study, in principle, SM electron transfer of any (label-free) molecule.