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21.
Beitone L Marrot J Loiseau T Férey G Henry M Huguenard C Gansmuller A Taulelle F 《Journal of the American Chemical Society》2003,125(7):1912-1922
A new fluorinated gallium phosphate, MIL-50, has been synthesized under mild hydrothermal conditions using 1,6-diaminohexane. The chemical formula of MIL-50 is Rb(2)Ga(9)(PO(4))(8)(HPO(4))(OH)F(6).2N(2)C(6)H(18).7H(2)O. The structure is a network of hexameric units of Ga(3)(PO(4))(3)F(2) and Ga(3)(PO(4))(2)(HPO(4))F(3) via corner sharing. It creates a three-dimensional open-framework delimiting 6- and 18-ring channels running along the c axis. The diprotonated 1,6-diaminohexane and water molecules are trapped within the 18-ring pores, whereas the rubidium cations reside in the 6-ring ones. A double quantum (31)P NMR experiment and partial charge calculations indicate that water molecules are present under the form of periodic small clusters, lowering the multiplicity of one phosphorus site, P3. Though water hops within the clusters, the motion leaves the water pattern periodic. Rubidium is so tightly embedded into the framework that water moving in the large 18-ring channels does not reach it, leaving it therefore dry. The crystal framework may be ascribed to the orthorhombic space group Cmc2(1) (n degrees 36), a = 32.1510(2), b = 17.2290(3), c = 10.2120(1) A. The periodic water pattern has a different symmetry than that of the framework. A method has been devised to superpose the two sublattices that coexist in the same unit cell in order to have full occupancy of each site and to perform Madelung summations. This original method is of general interest for most zeolitic materials exhibiting a different symmetry for the framework and the template sublattices. 相似文献
22.
Photoinduced morphism of gemini surfactant aggregates 总被引:5,自引:0,他引:5
Faure D Gravier J Labrot T Desbat B Oda R Bassani DM 《Chemical communications (Cambridge, England)》2005,(9):1167-1169
The photochemical behaviour of an azobenzene chromophore inserted in a gemini surfactant imparts photocontrol to the resulting amphiphile assemblies, including the collapse, upon irradiation, of the multi lamellar vesicles formed in aqueous solution. 相似文献
23.
Wagner J Andres H Rohrbach S Wagner D Oberer L France J 《The Journal of organic chemistry》2005,70(23):9588-9590
[Reaction: see text]. Sanglifehrin A is a novel complex natural product showing strong immunosuppressive activity and remarkably high affinity for cyclophilin A. To assess its pharmacokinetic properties in vivo, an efficient synthetic route was developed to introduce a tritium label in position C35 of sangliferin A via an oxidation/reduction strategy. The synthetic approach is particularly attractive, because the C35-oxo intermediate 7 is available in good yield on large scale and the reducing agent, lithium tri-sec-butylborotritide, is readily available. An attempt to apply a similar strategy to the alcohol in position C31 led primarily to C31-epi-hydroxy sanglifehrin A under a variety of conditions. 相似文献
24.
25.
Workman JA Garrido NP Sançon J Roberts E Wessel HP Sweeney JB 《Journal of the American Chemical Society》2005,127(4):1066-1067
The first examples of highly enantioselective [2,3]-sigmatropic rearrangements of acyclic allylic ammonium ylids are reported. Thus, a range of N-{2'-[(N'-allyl-N',N'-dialkyl)ammonium]}acetyl camphor sultams undergo rearrangement at 0 degrees C in DME solution with high diastereofacial control (up to 99:1 dr) to give allylglycines in generally high yield. The power of the method has been demonstrated in a rapid and efficient synthesis of (R)-allyl glycine. 相似文献
26.
Massue J Bellec N Chopin S Levillain E Roisnel T Clérac R Lorcy D 《Inorganic chemistry》2005,44(24):8740-8748
The reaction of tris(alkylthio)tetrathiafulvalene thiolates with 3-chloro-2,4-pentanedione affords tetrathiafulvalene (TTF) moieties substituted by the acetylacetone function (TTFSacacH), precursors of novel redox-active ligands: the acetylacetonate ions (TTFSacac). These TTFSacacHs have been characterized by X-ray diffraction analyses, and similar trends have been observed, such as a TTF core almost planar and the acetylacetone substituent located in a plane almost perpendicular to the plane formed by the TTF core. Their chelating ability has been demonstrated by the formation of the corresponding M(TTFSacac)2(pyridine)2 complexes in the presence of M(II)(OAc)2.H2O (M = Ni2+, Zn2+). These complexes with TTFSacac moieties, Ni(TTFSacac)2(pyridine)2, 6b, and Zn(TTFSacac)2(pyridine)2, 7b, have been characterized by X-ray diffraction analyses, showing in all structures the metal(II) center chelated by two TTFacac units in the equatorial plane and the octahedral coordination geometry around the metal completed by two axial pyridine ligands. Cyclic voltammetry and UV-visible-near infrared spectroscopic measurements have evidenced a sizable interaction between the two electroactive ligands and the stabilization of a mixed-valence state in the one-electron oxidized complexes. 相似文献
27.
28.
Treatment of 2-methylphenols with chloro(diphenyl)-lambda(3)-iodane led to their regioselective dearomatizing 2-phenylation into cyclohexa-2,4-dienone derivatives via a proposed ligand coupling reaction. In the same vein of investigation, treatment of 2-methylanilines with the lambda(5)-iodane 2-iodoxybenzoic acid IBX reagent led to their regioselective dearomatization into previously undescribed ortho-quinol imines. 相似文献
29.
30.
Hauke Harms Julien Rime Olivier Leupin Stephan J. Hug Jan Roelof van der Meer 《Mikrochimica acta》2005,151(3-4):217-222
A luminescent bacterial biosensor was used to quantify bioavailable arsenic in artificial groundwater. Its light production
above the background emission was proportional to the arsenite concentration in the toxicologically relevant range of 0 to
0.5 μM. Effects of the inorganic solutes phosphate, Fe(II) and silicate on the biosensor signal were studied. Phosphate at
a concentration of 0.25 g L−1 phosphate slightly stimulated the light emission, but much less than toxicologically relevant concentrations of the much
stronger inducer arsenite. No effect of phosphate was oberved in the presence of arsenite. Freshly prepared sodium silicate
solution at a concentration of 10 mg L−1 Si reduced the arsenite-induced light production by roughly 37%, which can be explained by transient polymerization leading
to sequestration of some arsenic. After three days of incubation, silicate did not have this effect anymore, probably because
depolymerization occurred. In the presence of 0.4 mg L−1 Fe(II), the arsenite-induced light emission was reduced by up to 90%, probably due to iron oxidation followed by arsenite
adsorption on the less soluble Fe(III) possibly along with some oxidation to the stronger adsorbing As(V). Addition of 100 μM
EDTA was capable of releasing all arsenic from the precipitate and to transform it into the biologically measurable, dissolved
state. The biosensor also proved valuable for monitoring the effectiveness of an arsenic removal procedure based on water
filtration through a mixture of sand and iron granules. 相似文献