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81.
The examination of 19F chemical shifts for ca. 650 F-alkylated compounds of general formula CF3(CF2)nCF2X led to the following conclusions: the CF2 groups α to X are very sensitive to the nature of X, and are spread over a range of 85 ppm. The effect of the length of the F-alkyl chain decreases rapidly, so that δCF2(α) can already be considered as characteristic of X for n = 1 or 2 for most practical purposes. Solvent effects (in 9 different solvents having ε = 1.8 to 52.1) were found to be rather small except for the F-alkyl iodides. A chart which indicates the domain in which the CF2(α) resonance signal is to be expected is given for 42 different series of F-alkylated compounds; it is expected to provide the synthetic chemist with a useful tool for the identification and characterization of such compounds. 相似文献
82.
Andrzej Małecki Jalees A.K. Tareen Jean Pierre Doumerc Louis Rabardel Jean Claude Launay 《Journal of solid state chemistry》1985,56(1):49-57
Kinetics of thermal decomposition in vacuum of Co3O4 powder as well as single crystals has been investigated. Discrepancies with the results of previous authors have been discussed. Decomposition of Co3O4 proceeds through formation of a compact layer of CoO and hence diffusion is the rate-limiting factor. The experimental curves α(t) be described for 0.05 < α < 0.85 using a modified Ginstling-Brounshtein equation: 1 ? 2α/3 ? (1 ? α)2/3 = ktn where the activation energy varies with the degree of decomposition. 相似文献
83.
Eupatorium cannabinum subsp. corsicum (L.), an aromatic plant, is an endemic subspecies from Corsica. The essential oil from aerial parts of E. cannabinum subsp. corsicum was studied by GC, GC/MS and 13C NMR. One hundred and forty-seven components were identified representing 93.6% of the total amount. The main constituents are germacrene D (28.5%), alpha-phellandrene (19.0%) and para-cymene (5.2%). A particularity of this essential oil is the presence of monoterpene esters derived from nerol, lavandulol, borneol, thymol and 8,9-dehydrothymol. These compounds have been investigated using GC/MS in different ionization modes like electron impact (EI), positive chemical ionization (PCI) and negative chemical ionization (NCI). 相似文献
84.
Kohtani M Jones TC Schneider JE Jarrold MF 《Journal of the American Chemical Society》2004,126(24):7420-7421
High-temperature ion mobility measurements have been performed for alpha-helical Ac-A15K+H+ and globular Ac-KA15+H+ peptides. The alpha-helical and globular conformations do not melt into random coils as the temperature is raised. Instead, both conformations survive to the point where the peptide signals vanishes due to fragmentation. This occurs at 600 K for the globular Ac-KA15+H+ peptide and at 725 K for the alpha-helical Ac-A15K+H+. For the helical Ac-A15K+H+ peptide it appears that fragmentation is triggered by disruption of the helical conformation. 相似文献
85.
Harold C. Beachell Jean C. Peterson 《Journal of polymer science. Part A, Polymer chemistry》1969,7(8):2021-2029
A linear polyurethane of high molecular weight was prepared in solution by the polyaddition of equimolar amounts of ethylene glycol and methylene bis(4-phenyl isocyanate). The polymer was fractionated by using a direct sequential extraction procedure, with a solvent–nonsolvent system consisting of N,N′-dimethylformamide (DMF) and acetone (A). The resulting fractions were characterized by viscosity and lightscattering measurements. The relationship between the intrinsic viscosity and molecular weight was found in DMF at 25°C. to be [η] = 3.64 × 10?4M0.71. The unperturbed polymer chain dimensions were determined from intrinsic viscosity measurements carried out under experimentally determined theta conditions. 相似文献
86.
Jean Pierre Brun Michle Ricard Madeleine Corval Catherine Schaal 《Journal of mass spectrometry : JMS》1977,12(6):348-350
The mass spectral fragmentation processes of 2-phenyloxetane have been studied by means of isotopic labelling. The origin of the benzoyl ion, which is the base peak, is discused 相似文献
87.
Jean‐Louis Schmitt Adrian‐Mihail Stadler Nathalie Kyritsakas Jean‐Marie Lehn 《Helvetica chimica acta》2003,86(5):1598-1624
Control over the folding of molecular strands may be achieved by appropriate choice of the constituting subunits, in particular for chains of specific heterocycles such as sequences of directly connected pyridine (py) and pyrimidine (pym) rings, which are known to fold into extended helical structures. Since the hydrazone (hyz) group represents an isomorphic analogue of a py site, the condensation of hydrazine and carboxaldehyde derivatives of pym offers a very efficient approach to strands incorporating hyz instead of py units and constituted by sequences of alternating hyz and pym groups. A series of such strands of different lengths, up to ten hyz units, i.e., 1 – 7 , were synthesized. Their spectral properties indicate that they fold indeed into helical shapes. Extensive characterization was performed in solution by 1HNMR spectroscopy and in the solid state by determination of the crystal structures of eight such strands. They all display the expected helical geometry with up to 3 1/3 turns and direct stacking contacts. The efficiency and flexibility of the synthetic approach as well as its wide potential for generation of diversity through lateral decoration make the (hyz? pym) subunit a particularly attractive helicity codon. 相似文献
88.
89.
The equilibrium C-H bond length has been determined up to now for about 40 polyatomic molecules. These data are used to demonstrate the existence of quantitative correlations betweenr
e(C-H), isolated C-H bond stretching frequency and average distancer
g. It is also shown that ab initio calculations are often reliable to calculate the absolute value ofr
e(C-H), if an empirical correction is made. Some other correlations are also discussed. Finally, accurater
e(C-H) values are predicted for simple molecules. 相似文献
90.