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51.
The kinetics of the copolymerization of methyl methacrylate and maleic anhydride was investigated in benzenic solutions at 60 and 70° C and in bulk at 60°C. The microstructure of the copolymers was determined by 1H-NMR and IR spectrophotometry. In benzene solutions the mechanism of copolymerization involves the participation of an associative species between both comonomers. In bulk a terminal model is sufficient to explain all the results. 相似文献
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55.
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
56.
The stereochemistry of the reaction of silver benzoates on chiral di-O-aroyl-1,2 iododeoxy-3-sn-glycerols has been reinvestigated. The reaction proceeds either with or without neighbouring group participation, depending on : - possible electrophilic assistance by the silver ion to the ionisation of the substrate (occuring only with dissociated silver salts), - ability of substituants R1 and R2 on the substrates to stabilize a positive charge. Rearrangements are at minimum with R1 and R2 electronreleasing groups in the substrate, silver salts un-or weakly dissociated and bearing a good nucleophile. For one case, a regio- and stereo specific reaction is observed. 相似文献
57.
Claude F. Bernasconi 《Tetrahedron》1985,41(16):3219-3234
The Principle of Imperfect Synchronization (PIS) states that a product stabilizing factor will lower the intrinsic rate of a reaction if it develops late, but increase the intrinsic rate if the factor develops early. It is shown in this paper that much of the structure-reactivity behavior of proton transfers involving carbon acids can be understood in the context of this principle. The factors discussed include the effect of resonance near the reaction site as well as in remote substituents, the polar effect of mote substituents, and the effects of solvation of reactants and products A sample matheatical formalism is developed to describe the contribution of each factor to the intrinsic rate constant. The possible reasons why there is a lack of synchronization between the various events which occur during the reaction are also discussed 相似文献
58.
Yvon Pointud Claude Bernard Sébastien Touzain Lionel Astier Béatrice Sabatier Jean Juillard 《Journal of solution chemistry》1997,26(5):479-495
The standard Gibbs functions, enthalpies, and entropies for the formation of the complexes of monensin acid with monovalent
metal cations in acetonitrile were obtained using various methods (conductometry, potentiometry, and calorimetry). Complexation
is appreciable (from 2.0 to 4.5 in terms of association constant logarithm) and controlled mainly by the enthalpic effect.
Comparison with formation of the corresponding neutral complexes permits a comparison to the process of monensin mediated
transport of cation in membranes. A two-step process involving first the formation of the acidic complex is suggested. 相似文献
59.
Characterization of Two Light-Harvesting Subunits Isolated from the Brown Alga Pelvetia canaliculata: Heterogeneity of Xanthophyll Distribution 总被引:1,自引:0,他引:1
Alessandra De Martino Dominique Douady Bernard Rousseau Jean Claude Duval Lise Caron 《Photochemistry and photobiology》1997,66(2):190-197
The main light-harvesting fraction from Pelvetia canaliculata was isolated on a sucrose density gradient from digitonin-solubilized chloroplasts. After further solubilization by dodecyl maltoside, the bulk fraction was separated into two subunits by preparative isoelectric focusing. The more acidic brown fraction was mainly composed of 22 kDa polypeptides having an apparent pI of 4.55. Its pigment composition was very simple, containing chlorophyll (Chi) a, Chi c and fucoxanthin. The in vivo spectral properties of fucoxanthin, namely a shift in light absorption to the green and efficient energy transmission to Chi a, were conserved in this subunit. No xanthophyll associated with photoprotection was found in this band, even when obtained from photoinhibited thalli. The less acidic green band contained predominantly 22 kDa polypeptides that were resolved into numerous components by denaturing isoelectric focusing. Its pigment composition was more complex, containing, in addition, pigments of the so-called xanthophyll cycle. In photoinhibited thalli, about half of the violaxanthin was converted into antheraxanthin and zeaxanthin. All the pigments of the xanthophyll cycle were specifically associated with this subunit, and it may thus have a central role in the thermal dissipation of the absorbed light energy as postulated for light-harvesting complex II isolated from green plants. 相似文献
60.
Mosshine El Marackchi Claude Tissier Jean Juillard 《Journal of Electroanalytical Chemistry》1997,420(1-2)
Gibbs functions for transfer from water to methanol and to a full range of water + methanol mixtures were obtained for Cu2+, Cd2+, Pb2+, Hg2+, Zn2+, Mg2+, Ca2+, Sr2+ and Ba2+ using potentiometric or polarographic measurements in these solvents. In addition, data were obtained from the solubility products of the alkaline-earth iodates. From values obtained by the different methods and literature data, a table of selected values is given. 相似文献