Study of the State of Water and Oil in Frozen Emulsions Using Time Domain NMR

Here T(1) and T(2)(*) relaxation time measurements by low-field NMR have been used to quantify the state of oil and water in frozen emulsions. Water-in-oil and oil-in-water emulsions have been studied. A discrete method (NLREG program) and a continuous method (CONTIN program) have been used to analyze the FID and inversion-recovery relaxation curves. The FID signal (T(2)(*)) analysis allowed us to calculate the global solid-intermediate-liquid ratio, and the state of the solid and liquid phases was determined by the T(1) values. Thus we have been able to show that the major part of water ( approximately 99%) is in a solid state in such emulsions (average droplet diameter of about 1.5 &mgr;m). This result was confirmed by the study of a solid paraffin-Span 80-water emulsion and a heavy water-caseinate-triolein emulsion. These first results have shown the interest of this new method for the study of the state of water and oil in frozen emulsions. Copyright 2000 Academic Press.     

PHOTOCHEMICAL INTERACTIONS BETWEEN NITROXIDE FREE RADICALS AND PHENOTHIAZINES IN SOLUTION

Abstract— Ultraviolet irradiation of photosensitive molecules like phenothiazine derivatives leads to the formation of short lived free radicals which are able to reduce stable nitroxide free radicals generally used as spin labels. The measurement of the electron spin resonance signal decay of nitroxides offers a tool for studying the photochemical reaction of phenothiazine derivatives in solution at room temperature, in a 10^-5 to 10^-2 M concentration range. Analysis of the reaction mechanism shows that the paramagnetic nitroxide is an efficient quencher of the phenothiazine triplet state; this reaction was used to demonstrate the influence of the solvent, quenching by oxygen and the role of the chemical structure of six phenothiazine derivatives on their photoreactivity in solution.     

The "invisible" 13C NMR chemical shift of the central carbon atom in [(Ph3PAu)6C]2+: a theoretical investigation

The experimental 13C NMR chemical shift of the central carbon atom in the octahedral [(Ph3PAu)6C]2+ cluster was investigated on the basis of relativistic density functional calculations. In order to arrive at independent model conclusions regarding the value of the chemical shift, a systematic study of the dependence of the cluster structure on the phosphine ligands, the chosen density functionals, and the basis set size was conducted. The best structures obtained were then used in the NMR calculations. Because of the cage-like cluster structure a pronounced deshielding of the central carbon nucleus could have been expected. However, upon comparison with the 13C NMR properties of the related complex [C{Au[P(C6H5)2(p-C6H4NMe2)]}6]2+, Schmidbaur et al. have assigned a signal at delta=135.2 ppm to the interstitial carbon atom. Our calculations confirm this value in the region of the aromatic carbon atoms of the triphenylphosphine ligands. The close-lying signals of the 108 phenyl carbon atoms can explain the difficulties of assigning them experimentally.     

Determination of Organochlorine Pesticides in Sediments from Authie Bay Using Microwave Assisted Solvent Extraction

The aim of this study was to develop an analytical method to determine the organochlorine concentrations in sediments. Combination of Microwave assisted Solvent Extraction (MASE) and capillary gas chromatography with specific detection (electron capture detector) was a viable approach for the determination of pesticides in solid matrixes. In this study, MASE development was focused on the selection of a suitable extraction solvent for all the target analytes. MASE procedure was validated by comparison with conventional methods such as Soxhlet and sonication extraction. The proposed method was then applied to determine the organochlorine insecticides concentrations in samples from Authie Bay (France). Environmental water samples were analysed and five target analytes were detected in concentrations from 0.03 to 0.56 ng/g of dry sediment. These investigations showed the accumulation and the persistency of these products in sediments in spite of the fact they were banned a few decades ago.     

低温原子化石墨炉原子吸收法测定环境和生物样中的镉

本文描述了以氩/氢混合气体作保护气体,测定环境和生物样品中痕量镉的石墨炉原子吸收法。实验证明,与纯氩气作保护气体相比较用氩/氢混合气体作保护气体,能够降低镉的原子化温度(100℃),并且减少基体物质如MgCl_2和NaClO_4的干扰。这种改善氯化物和高氯酸盐基体干扰的机理,主要是由于氢的存在与基体中的氯形成高离解能的氯化氢,从而避免了通常在镉原子化之前形成易挥发的氯化镉而损失。用本方法测定了七种标准参考物质,结果与标准值一致,证明方法是可靠的。     

Etude asymptotique des enlacements du mouvement brownien autour des droites de l'espace

Summary The existence of a joint asymptotic distribution for the windings of a three-dimensional Brownian motion around a finite number of straight lines is obtained. This complements the recent studies, by Pitman- Yor, and the authors, of the joint asymptotic distribution for the windings of planar Brownian motion around a finite number of points.The following principle governs the passage from results in the plane to results in space:Let B be a three-dimensional Brownian motion, and P ₁, ..., P _k, k planes which intersect two by two. Then, the convergences in distribution concerning the planar Brownian motions B ⁱ (1ik), defined respectively as the orthogonal projections of B on P _i (1ik), take place jointly, and the corresponding limit variables are independent.     

160Tb nuclear orientation in yttrium single crystal

First experimental results of¹⁶⁰Tb nuclear orientation in yttrium single crystal matrix are described. The influence of external magnetic field in combination with the crystal field interaction is discussed.     

On the relationship between differentiability and absolute continuity of measures on ℝn

Summary We give an elementary proof of the fact that a finite Borel measure on ⁿ is absolutely continuous with a C ¹ density if and only if it has directional derivatives which are continuous almost everywhere. The Radon-Nikodym derivative of a differentiable measure is given in terms of the directional derivatives.