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71.
Apparent molal heat capacities
of some piperidine, morpholine, and piperazine derivatives in aqueous solution have been determined by adiabatic calorimetry
in the temperature range 20–55°C and in the molality range 0.2–1m. Comparison of experimental
values with those calculated through group contributions, found for monofunctional compounds, indicates strong interactions
between the hydrophilic centers. An interpretation is given of the possible mechanism of this interaction. Also, values of
ΔC
p
for the addition reaction of proton to nitrogen centers of mono- and bifunctional organic compounds are examined. 相似文献
72.
Le Guennic B Neugebauer J Reiher M Autschbach J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(5):1677-1686
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. 相似文献
73.
Nicolas Le Calvez 《中国化学会会志》2002,49(4):585-592
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. 相似文献
74.
75.
76.
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. 相似文献
77.
78.
J. Kuriplach L. Lešták M. Rotter B. Sedlák M. Trhlík M. Finger T. Lešner J. Dupák P. Novák M. Vobecký 《Hyperfine Interactions》1987,34(1-4):339-342
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. 相似文献
79.
80.
Carlier J Arscott S Thomy V Camart JC Cren-Olivé C Le Gac S 《Journal of chromatography. A》2005,1071(1-2):213-222
We report here on an integrated microfabricated device dedicated to the preparation of biological samples prior to their on-line analysis by electrospray ionization-mass spectrometry (ESI-MS). This microfluidic device is fabricated using the negative photoresist SU-8 by microtechnology techniques. The device includes a chromatographic module plus an ESI interface for MS. The chromatographic module is dedicated to sample purification and is based on a polymer monolithic phase which includes hydrophobic moieties. The ESI interface is integrated onto the chip and is based on a capillary slot. We present here the integration of these different modules onto a single system that is fabricated via a SU-8-based microtechnology route. We present also their testing for the purification of peptide samples. This started with a partial integration step with the combination of at least two of the modules (microsystem + monolith; microsystem + nib) and their test before the fabrication and testing of fully integrated microsystems. 相似文献