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931.
[structure: see text] New and facile synthesis of symmetric diindolocarbazoles was developed using the copper-catalyzed Ullmann reaction. The key step is a double-intramolecular cyclization reaction realized on N-alkyl-3,6-dibromo-2,7-bis(2'aminophenyl)carbazole derivatives which offers the desired symmetric ladder oligo(p-aniline)s. Depending upon the nature of the side- and/or end-groups, well-defined thin films and/or semiladder polymers could be obtained. These electroactive ladder oligomers may have great potential in organic electronics. 相似文献
932.
The structure and the dynamic organization of a mixed Langmuir film of glucose oxidase and stearylamine at the air–water interface have been studied. The film has been first characterized at the air–water interface by surface pressure/area isotherms. The dynamics of the mixed film was studied by following the evolution of the film area at a constant pressure and the evolution of the pressure at a constant area. After transfer of the films on solid substrates, the chemical composition of the mixed film has been quantified by UV–vis and IR spectroscopies. These characterizations were carried out in order to study the incorporation of glucose oxidase into the stearylamine film, and its influence on the structural evolution of the film. From these results, the dynamic organization of this mixed film may be described. For short times, glucose oxidase molecules interact with stearylamine molecules in solution or at the interface; these interactions would lead to the formation of a complex between stearylamine and glucose oxidase molecules. For long times (at least 3 h), a homogeneous mixed film constituted essentially of this complex is obtained at the air–water interface. A detailed analysis by atomic force microscopy allowed us to support this model and the existence of the glucose oxidase/stearylamine complex. 相似文献
933.
Mezzenga R Grigorov M Zhang Z Servais C Sagalowicz L Romoscanu AI Khanna V Meyer C 《Langmuir : the ACS journal of surfaces and colloids》2005,21(14):6165-6169
We report on the order-to-order transitions of lyotropic liquid crystals formed by self-assembled monogylcerides and water in the presence of polysaccharides of various molecular weights. The phase diagram of monoglyceride-water-polysaccharide systems, their morphology, and the topology of liquid crystalline structures were determined by combining optical cross-polarization, oscillatory shear rheometry, and small-angle X-ray scattering. The presence of hydrophilic mono-, oligo-, and polysaccharides in the water domains of liquid crystalline phases resulted in a general decrease of the cubic-to-hexagonal transition temperature. Provided that the sugar could fit within the water channels, the decrease was observed to be dependent on the polysaccharide concentration but independent of its molecular weight. For isotropic bicontinuous cubic phases, monomeric sugars such as glucose were reported to shrink the lattice parameter of the structure without inducing phase transitions. However, when a polymeric form of glucose was used, such as dextran, transitions from the gyroidal Ia3d cubic phase to double diamond Pn3m cubic phases were observed at well-defined molecular weights of polysaccharide. These results were interpreted in terms of size exclusions of polymer sugars by the water domains of the liquid crystal phases as well as the different topologies of water channels. Molecular dynamics simulations of polysaccharides in the water environment were performed to support these findings. 相似文献
934.
Unsaturated sultones have been synthesized from various primary or secondary alkenols by ring-closing metathesis of the corresponding unsaturated sulfonates. By treatment with a strong base, β,γ-unsaturated sultones can be metalated and subsequently alkylated with electrophiles. When iodomethylmagnesium chloride was selected as the electrophile, seven-membered ring β,γ-unsaturated sultones were converted into homoallylic conjugated (Z)-dienols. This methodology was applied to the racemic synthesis of the originally proposed structure of the marine natural product mycothiazole. 相似文献
935.
Messina P Dmitriev A Lin N Spillmann H Abel M Barth JV Kern K 《Journal of the American Chemical Society》2002,124(47):14000-14001
We report single-molecule level STM observations of chiral complexes generated by the assembly of achiral components at a metal surface. Following co-deposition of iron atoms and 1,3,5-tricarboxylic benzoic acid (trimesic acid, TMA) on Cu(100) in ultrahigh vaccum, TMA molecules react with the metal centers, and metal-ligand interactions stabilize R and S chiral complexes which are clearly distinguished by STM. 相似文献
936.
Alexandre Alexakis Farida Mhamdi Franz Lagasse Pierre Mangeney 《Tetrahedron: Asymmetry》1996,7(12):3343-3346
α,β-Ethylenic chiral acetals react regio- and stereoselectively with organolithium reagents. The obtained enol ether may be hydrolyzed into a chiral β-disubstituted aldehyde. 相似文献
937.
Sortais JB Ritleng V Voelklin A Holuigue A Smail H Barloy L Sirlin C Verzijl GK Boogers JA de Vries AH de Vries JG Pfeffer M 《Organic letters》2005,7(7):1247-1250
[reaction: see text] Ruthenacycles obtained by cyclometalation of enantiopure aromatic primary or secondary amines with [(eta6-benzene)RuCl2]2 or with [(eta6-p-cymene)RuCl2]2 are efficient catalysts for asymmetric transfer hydrogenation (TOF up to 190 h(-1) at room temperature). Enantioselectivities in the transfer hydrogenation of acetophenone ranged from 38% to 89%. It is possible to prepare the catalysts in situ, which allows the use of high throughput experimentation. 相似文献
938.
Grignard reagents undergo enantioselective (up to 86% ee) copper-catalyzed S(N)2' substitution on achiral allylic chlorides. The reaction is wide in scope for both the Grignard reagent and the allylic substrate. The resulting terminal alkene could be submitted to intra- or intermolecular metathesis to afford new chiral synthons. The experimental conditions are compatible with a one-pot overall substitution-metathesis procedure without loss of enantioselectivity. [reaction: see text] 相似文献
939.
Enantioselective addition of methyllithium to aromatic imines catalyzed by C2 symmetric tertiary diamines is described. Eleven diamines have been tested, for which dramatic effect of the nitrogen substitution has been observed. Diamines bearing hindered group close to the nitrogen led to racemic product while homologous hindered diamines led to the best results. Enantiomeric excess up to 74% could be achieved. An explanation of the absolute configuration of the product obtained is given considering the mechanism of the reaction. 相似文献
940.
Bruno Alonso Alexandre Vrain Elodie Beaubois Dominique Massiot 《Progress in Solid State Chemistry》2005,33(2-4):153-161
We have undertaken the synthesis of spray-dried mesoporous silica-based micrometric spheres using various synthetic procedures. In this article, we focus on the relationship between textural properties and small organic groups bound to the siloxane network (residual alkoxy groups or added functions). A correlation has been found between the characteristic XRD distance and the quantity of Si-bound organic groups (measured by 1H solid-state NMR) located at the surfactant–siloxane interface which demonstrates the effect of these organic groups. However, under certain circumstances, Si-bound organic groups can be trapped inside the siloxane network. They have then a different effect on the texture, and are less accessible for further applications. In that sense, this study can also be used in a predictive way for the synthesis of mesoporous spheres with surfaces of functionalised channels. 相似文献