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111.
The kinetics of radical telomerization of VDF at 141 °C, initiated by ditertbutylperoxide, in the presence of three chain transfer agents (CTAs), HCCl3, CCl4 and CCl3Br, are presented. The values of the chain transfer constants were assessed as 35, 0.25 and 0.06 at 141 °C for CCl3Br, CCl4 and HCCl3, respectively. The values of the degree of polymerization (DPn) were obtained for each CTA and were compared for the same CTA concentration. Hence, CCl3Br behaved as an efficient CTA towards VDF and usually afforded the monoadduct selectively, but in certain conditions the VDF diadduct can also be produced. In contrast, HCCl3 was not so efficient since a polymeric structure was identified as the major product. 相似文献
112.
In order to analyse metal complexation with polyfunctional phenolic compounds as ligand models of natural substances, a detailed examination is described for five simple binary complexes and three ternary mixed ligand complexes at 25°C (μ = 0.1 M NaClO4). The ligands are tyrosine, 4,5-dihydroxy-1,3-benzene disulfonic acid, disodium salt (tiron), 3,4-dihydroxycinnamic acid (caffeic acid), 3,4,5-trihydroxy-1 -cyclohexene-1 -carboxylic acid (shikimic acid) and 1,3,4,5-tetrahydroxycyclohexanecarboxylic acid 3-(3,4-dihydroxycinnamate) (chlorogenic acid). The ternary systems are Cu(II)/HqA/tiron, where HqA is tyrosine, caffeic or chlorogenic acids. Potentiometric data were used successively to evaluate the protonation of each individual ligand, to detect simple and mixed complexes (including protonated species) and to determine their stability constants (a set of 33 values of constants with several original data is provided). The calculated distribution (speciation) of each species as a function of pH is indicated. Mixed coordination enhances the stability of complexes and the stabilization is expressed in terms of various parameters. The results emphasize that mixed ligand complex formation is essential to studies of multiple equilibria. 相似文献
113.
Abdallah Aissa Michel Gruselle René Thouvenot Rainer Traksmaa 《Journal of solid state chemistry》2007,180(8):2273-2278
The reaction between phenyl phosphonic dichloride (C6H5P(O)Cl2) and synthetic calcium hydroxy- and fluorapatite has been investigated. The presence of mono- or polymeric (C6H5PO) fragment bound to hydroxyapatite was evidenced by IR, and solid-state 31P NMR spectroscopy. X-ray powder analysis has shown that the apatitic structure remains unchanged during the reaction. In contrast, no reaction was found using fluorapatite. According to the results found for these two different apatites a mechanism was proposed for the formation of covalent P-O-P bonds as the result of a reaction between the C6H5P(O)Cl2 organic reagent and (HPO4)− and/or OH− ions of the hydroxyapatite. 相似文献
114.
Cianetti S Négrerie M Vos MH Martin JL Kruglik SG 《Journal of the American Chemical Society》2004,126(43):13932-13933
Cytochrome c (cyt c) is an electron-transfer heme protein that also binds nitric oxide (NO). In resting cyt c, two endogenous ligands of the heme iron are histidine-18 (His) and methionine-80 (Met) side chains, and NO binding requires the cleavage of one of the axial bonds. Previous femtosecond transient absorption studies suggested the photolysis of either Fe-His or Fe-Met bonds. We aimed at unequivocally identifying the internal side chain that is photodissociated in ferrous cyt c and at monitoring heme structural dynamics, by means of time-resolved resonance Raman (TR3) spectroscopy with approximately 0.6 ps time resolution. The Fe-His stretching mode at 216 cm-1 has been observed in photoproduct TR3 spectra for the first time for a c-type heme. The same transient mode was observed for a model ferrous cyt c N-fragment (residues 1-56) ligated with two His in the resting state. Our TR3 data reveal that upon ferrous cyt c photoexcitation, (i) distal Met side chain is instantly released, producing a five-coordinated domed heme structure, (ii) proximal His side chain, coupled to the heme, exhibits distortion due to strain exerted by the protein, and (iii) alteration in heme-cysteine coupling takes place along with the relaxation of the protein-induced deformations of the heme macrocycle. 相似文献
115.
116.
[reaction: see text] A short synthesis of intermediates possessing the tricyclic core of natural madangamines, bioactive alkaloids found in marine sponges, is described. The key reaction entails the condensation of the sodium salt of diethylacetonedicarboxylate with a dihydropyridinium salt derivative. This new approach is modeled on a biogenetic proposal linking madangamines to ircinals, related alkaloids occurring in sponges of the same order. 相似文献
117.
Roger Azria Yvonnick Le Coat Jean-Pierre Ziesel Jean-Pierre Guillotin Brahim Mharzi Michel Tronc 《Chemical physics letters》1994,220(6):417-422
Absolute kinetic energy distributions and yields associated with ground state 3P and excited state 1D oxygen atoms have been obtained for O− anion electron stimulated desorption from condensed O2 in the electron energy range 6–15 eV. The observed yields are understood as resulting essentially from dissociative electron attachment reactions via the two lowest 2Σ+g O−2 resonance states through adiabatic and non-adiabatic transitions to the limits O−(2P) + O(3P) and O−(2P) + O(1D). The kinetic energy distributions show the prominent role of electron multiple collision processes and post-dissociation interactions of the O− anions in the condensed phase. 相似文献
118.
The crystal structure of the fluorozirconate SmZrF7 has been determined from single crystal X-ray data; the final R value is 0.028. In this compound, isotypic with all the fluorozirconates LnZrF7 (Ln = rare earth), the symmetry of the cell is monoclinic (space group: P21). The Zr atoms are surrounded by six fluorine atoms forming an almost perfect octahedron: the average distance ZrF is 2.006 Å. The Sm atoms are surrounded by a 8 fluorine atoms polyhedron, the distances SmF lie from 2.221 to 2.411 Å. The association of these two polyhedra by sharing corner forms slabs with an approximately ReO3 type arrangement: the thickness of the slabs is two octahedra.These slabs with the composition M2X7 are held together so that the top fluorine atoms at the surface of a slab increase the coordination of the Sm atom of an adjacent slab. This MX3.5 phase corresponds to a new structural type between MX3 (ReO3 type) and MX4 (SnF4 type). 相似文献
119.
Euzenat L Horhant D Ribourdouille Y Duriez C Alcaraz G Vaultier M 《Chemical communications (Cambridge, England)》2003,(18):2280-2281
Thermal decomposition of hindered amine-borane adducts leads in high yields to monomeric (dialkylamino)boranes R1R2N-BH2 (R1 and R2 = alkyl) that are new and efficient boron-sources in the Pd0 catalyzed borylation reaction affording monomeric aryl(dialkylamino)boranes R1R2N-BHR3 (R3 = aryl). 相似文献
120.
Musangu Mbuyi Michel Evers Guy Tihange Andr Luxen Lon Christiaens 《Tetrahedron letters》1983,24(52):5873-5876
We describe the synthesis of a new heterocyclic system : the 1,3-benzotellurazole, and some of its substituted derivatives. 相似文献