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41.
Gérald Perron François Quirion Daniel Lambert Jean Ledoux Lahouari Ghaicha R. Bennes Mireille Privat Jacques E. Desnoyers 《Journal of solution chemistry》1993,22(2):107-124
Phase diagrams, volumes and heat capacities of aqueous mixtures of 2,6-dimethylpyridine (2,6-L) and 2-isobutoxyethanol (iBE) and activities of 2,6-L in aqueous mixtures were measured in the monophasic region near the lower critical solution temperature (LCST). With 2,6-L some measurement were also made just above the LCST. From the temperature dependence of these data, partial molar relative enthalpies (2,6-L), expansibilities and the temperature derivative of heat capacities were calculated and show that iBE undergoes a microphase transition at low concentration which is not related to the phase separation. On the other hand, the properties of 2,6-L in the water-rich region at temperatures well below the LCST indicates that this solute has only a slight tendency to associate. The heat capacities of 2,6-L show an important increase near the LCST. Such changes are not observed for iBE and other alkoxyethanols and amines since these systems already exist in the form of microphases; the partial molar properties of iBE near the LCST are nearly equal to the molar values of the pure liquid, and the changes in thermodynamic properties corresponding to the macroscopic phase transition, are therefore too small to be measured by the present techniques. 相似文献
42.
Jacques Dunoguès Elisabeth Jousseaume Jean-Paul Pillot Raymond Calas 《Journal of organometallic chemistry》1973,52(2):C11-C17
The trimethylchlorosilane/magnesium/hexamethylphosphoric triamide (HMPT) system reacts with some functional polychlorinated compounds (chloral, hexachloroacetone, acetone chloroform) affording a partial reduction accompanied by silylation and leads to new functional silylated derivatives.These reactions exhibit reductive properties of magnesium, in HMPT, towards the CCl bond. 相似文献
43.
Roland Bonneau Philippe Fornier de Violet Jacques Joussot-Dubien 《Photochemistry and photobiology》1974,19(2):129-132
Abstract— The pH dependence of the apparent reactivity of thiazine dyes in their triplet states has been studied in aqueous solutions, using as electron donor HY-3 , the trianionic species of ethylene diamine tetraacetic acid (EDTA), in the pH range 4–8. The pH dependence is found to be related to a change in the degree of protonation of the triplet excited dye. The apparent reactivity and lifetime of two differently protonated forms of thionine, azur B and methylene blue were determined by classical and dye-laser flash techniques, making it possible to evaluate the rate constant for electron abstraction of these molecules in their triplet states. It is found that: (a) protonation on the ring nitrogen increases the electron-abstraction rate constant of the triplet-state species about twenty-fold, and (b) methylation on the side amino groups decreases it. 相似文献
44.
Micheline Grignon-Dubois Jacques Dunogues Raymond Calas 《Journal of organometallic chemistry》1979,181(2):285-291
Studies of the electrophilic substitution on two 1-sila-3-cyclopentenes and their cyclopropane homologues revealed the important role of silicon and provided a new route to alkenylfluorosilanes and novel β,γ or especially γ,δ-unsaturated silylated ketones. 相似文献
45.
Ahmed El Abed Etienne Gaudin Jacques Darriet 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(10):i138-i140
Single crystals of Sr4Mn2.09Cu0.91O9 have been grown by flux synthesis and the structure, closely related to the hexagonal perovskite 2H, was solved from single‐crystal X‐ray data in space group P321. The structure of Sr4Mn2CuO9 is composed of chains of face‐sharing polyhedra with a sequence of two octahedra and one trigonal prism. The octahedra are filled by Mn atoms and the Cu atoms are randomly distributed at the centres of the square faces of the trigonal prism. A stacking fault is observed within one of the two chains, which can be attributed to a shifting of the chain along the c axis. 相似文献
46.
Bretonnière Y Mazzanti M Pécaut J Olmstead MM 《Journal of the American Chemical Society》2002,124(31):9012-9013
The simple asymmetric tetradentate ligand 2,2':6',2' '-terpyridine-6-carboxylic acid leads to the self-assembly of the first europium nanowheel containing europium ions in two different coordination environments. Moreover the self-assembly of bis(terpyridinecarboxylate) europium species to form a hexameric wheel capable of strongly binding LnIII cations is controlled by the ligand/cation ratio. 相似文献
47.
The possibility to design new composites associating biopolymers with mineral phases relies on the understanding and control of their mutual interactions. In this work, aqueous solutions of gelatine and sodium silicate were mixed at pH 5, 37 degrees C and left to stand at 20 degrees C for 1 day. At low gelatine and high silicate contents, precipitates were obtained, containing a fixed silicon/polymer molar ratio. Scanning electron microscopy (SEM) reveals that they are formed of large aggregates of platelets, constituted of closely-packed nanoparticles. For high gelatine contents, composite gels were formed consisting of silica particles dispersed in the biopolymer matrix. Swelling studies indicate that the addition of silica decreases the stability of the gels by inducing gelatine depletion in solution. Similar experiments conducted at pH 7 show that at this pH, silicates are more effective at precipitating gelatine. A model is proposed for the formation of the composites, based on the electrostatic interactions arising between silicates and polymer chains. These results are discussed in the context of hybrid biomaterials design and biosilicification processes. 相似文献
48.
Hamelin O Pécaut J Fontecave M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(10):2548-2554
Recently, we observed that the enantiopure Lambda form of the tributylammonium salt of the chiral anion tris[tetrachlorobenzene-1,2-bis(olato)]phosphate, also named Trisphat, was able to induce an efficient resolution of a Delta,Lambda racemic mixture of cis-[Ru(dmp)2(NCCH3)2](PF6)2 (dmp=2,9-dimethyl-1,10-phenanthroline) due to the spontaneous and selective precipitation of the heterochiral pair [Delta-Ru(dmp)2(CH3CN)2][Lambda-Trisphat]2. We report here that the combination of such a stereoselective precipitation process and irradiation results in the quantitative conversion of the initial [Ru(dmp)2(NCCH3)2]2+ racemate into only one of the two enantiomers. This is the first example in inorganic chemistry of an asymmetric transformation that leads to a chiral complex with no chiral ligand. Finally, three new racemic ruthenium bis(diimine) complexes, namely [Ru(dmp)2(NCCH3)Py](PF6)2 (Py=pyridine), [Ru(dmp)2(1,3-diaminopropane)](PF6)2, and [Ru(dmp)2(ethylenediamine)](PF6)2 were synthesized. For all of them, crystallization-induced asymmetric transformation proved to be an efficient way of obtaining the corresponding optically active chiral-at-metal complexes in high yields and with excellent stereoselectivities. 相似文献
49.
Two new enantioselective syntheses of the naphthopyranquinone antibiotic frenolicin B ( 1 ), of its enantiomer 2 , and of its diastereoisomers 3 and 4 were accomplished using two different routes from optically active β-Hydroxy esters (R)- and (S)- 11 and 18. β-Hydroxy esters (R)- and (S)- 11 were prepared stereoselectively from optically active sulfenylacetates (S)- and (R)- 10 , respectively (Scheme 2, Method A). Alternatively, compound 18 was obtained in excellent yield by enantioselective hydrogenation of the corresponding β-keto ester 17 , using a chiral ruthenium-complex catalyst (Scheme 3, Method B). Subsequently, compounds (S)- 11 and 18 were transformed into frenolicin B (1). In analogy, Stereoisomers 2–4 were prepared from (S)- and (R)- 11 in good yields. 相似文献
50.
Iványi T Vander Heyden Y Visky D Baten P De Beer J Lázár I Massart DL Roets E Hoogmartens J 《Journal of chromatography. A》2002,954(1-2):99-114
This paper focuses on the classification or differentiation of RP-HPLC columns based on measured chromatographic properties. A chemometric study has been conducted on a published data set consisting of 85 RP-HPLC columns and on a data set consisting of 47 self-tested columns. Principal component analysis enables determination of the number of parameters necessary for a rational differentiation. The results show that reducing the number of parameters for such differentiation still allows classification of the columns just as a higher number did. It is shown that three test parameters produce a classification similar to that obtained with five parameters. 相似文献