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21.
Katharina M. Fromm Estelle D. Gueneau Adeline Y. Robin William Maudez Jorge Sague Rmi Bergougnant 《无机化学与普通化学杂志》2005,631(10):1725-1740
This contribution gives an overview on the different subjects treated in our group. One of our fundamental interests lies in the synthesis and study of low‐dimensional polymer and molecular solid state structures. We have chosen several synthetic approaches in order to obtain such compounds. Firstly, the concept of cutting out structural fragments from a solid state structure of a binary compound will be explained on behalf of BaI2. Oxygen donor ligands, used as chemical scissors on BaI2, allow obtaining three‐, two‐, one‐ and zero‐dimensional derived compounds depending on their size and concentration. Thus, a structural genealogy tree for BaI2 can be established. This method, transferred to alkali halides using crown ethers and calix[n]arenes as delimiting ligands, leads us to the subject of one‐dimensional ionic channels. A second chapter deals with the supramolecular approach for the synthesis of different dimensional polymer structures derived from alkaline earth metal iodides, and based on the combination of metal ion coordination with hydrogen bonding between the cationic complexes and their anions. Under certain circumstances, rules can be established for the prediction of the dimensionality of a given compound, thus contributing to the fundamental problem of structure prediction in crystal engineering. A third part describes a fundamentally new synthetic pathway for generating pure alkaline earth metal cage compounds as well as alkali and alkaline earth mixed metal clusters. In a first step, different molecular precursors, such as solvated alkaline earth metal halides are investigated as a function of the ligand size and reactivity. They are then reacted with some alkali metal compound in order to partially eliminate alkali halide and to form the clusters. The so obtained unique structures of ligand stabilized metal halide, hydroxide and/or alkoxide and aryloxide aggregates are of interest as potential precursors for oxide materials. Approaches to two synthetic methods of the latter, sol‐gel and (MO)‐CVD, are investigated with our compounds. In order to generate single source precursors for oxide materials, we started to investigate transition metal ions, especially Cu and Ag, using multitopic ligands. This has led us into the fundamental problematic of “crystal engineering” and solid state structure prediction and we found ourselves confronted to numerous interesting cases of polymorphism and pseudo‐polymorphism. Weak interactions, such as π‐stacking, H‐bonding and metal‐metal interactions, and solvent, counter ion and concentration effects seem to play important roles in the construction of such low‐dimensional structures. Finally, the physical properties of some of our compounds are described qualitatively in order to show the wide spectrum of possibilities and potential applications for the chemistry in this field. 相似文献
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ABSTRACT The Witting reaction of (carbethoxymethylene)triphenylphosphorane with perbenzylated sugar δ-lactones and their 2-acetamido-2-deoxy derivatives is described. It is shown that this olefination occurred readily with the galacto and gluco derivatives, leading stereoselectively to Z-C-glycosylidenes in good yields. However, the same reaction with the perbenzylated 2-deoxy-D-arabino-hexono-1,5-lactone and the mannonolactones worked poorly. Reduction over Pd/C followed by acetylation of the obtained C-glycosylidenes led stereoselectively to peracetylated β-C-glycosides and amino β-C-glycosides. The olefin function could also be reduced selectively by Raney nickel or NiCl2/NaBH4, affording the perbenzylated C-glycosides and amino β-C-glycosides. Other transformation of the enol ether function is also reported. 相似文献
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This work presents expeditious synthesis of C-glycoside amphiphiles in aqueous media from unprotected di- or mono-saccharides. A Horner-Wadsworth-Emmons/Michael addition/Barbier allylation sequence led to C-glycosides that exhibit hydrotropic properties. The hydrotropic and solubilizing properties of these homoallylic alcohols including a β-C-glycoside moiety as well as additional β-C-glycosidic ketones with a short (C7) alkyl chain are also described and compared with those of commercial O-glucoside references. 相似文献
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Rombouts Y Elass E Biot C Maes E Coddeville B Burguière A Tokarski C Buisine E Trivelli X Kremer L Guérardel Y 《Journal of the American Chemical Society》2010,132(45):16073-16084
Although lipo-oligosaccharides (LOSs) are recognized as major parietal components in many mycobacterial species, their involvement in the host-pathogen interactions have been scarcely documented. In particular, the biological implications arising from the high degree of structural species-specificity of these glycolipids remain largely unknown. Growing recognition of the Mycobacterium marinum-Danio rerio as a specific host-pathogen model devoted to the study of the physiopathology of mycobacterial infections prompted us to elucidate the structure-to-function relationships of the elusive end-product, LOS-IV, of the LOS biosynthetic pathway in M. marinum. Combination of physicochemical and molecular modeling methods established that LOS-IV resulted from the differential transfer on the caryophyllose-containing LOS-III of a family of very unusual N-acylated monosaccharides, naturally present as different diastereoisomers. In agreement with the partial loss of pathogenecity previously reported in a LOS-IV-deficient M. marinum mutant, we demonstrated that this terminal monosaccharide conferred to LOS-IV important biological functions, including macrophage activating properties. 相似文献
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We study the class of state-space models and perform maximum likelihood estimation for the model parameters. We consider a stochastic approximation expectation–maximization (SAEM) algorithm to maximize the likelihood function with the novelty of using approximate Bayesian computation (ABC) within SAEM. The task is to provide each iteration of SAEM with a filtered state of the system, and this is achieved using an ABC sampler for the hidden state, based on sequential Monte Carlo methodology. It is shown that the resulting SAEM-ABC algorithm can be calibrated to return accurate inference, and in some situations it can outperform a version of SAEM incorporating the bootstrap filter. Two simulation studies are presented, first a nonlinear Gaussian state-space model then a state-space model having dynamics expressed by a stochastic differential equation. Comparisons with iterated filtering for maximum likelihood inference, and Gibbs sampling and particle marginal methods for Bayesian inference are presented. 相似文献
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Vijaya Bhaskara Reddy Iska Shashi Kant Tiwari Gadamsetti Surendra Babu Adeline Adrien 《Tetrahedron letters》2007,48(40):7102-7107
Chiral cyclic and acyclic allyl aminosulfoxonium ylides have been generated from aminosulfoxonium-substituted β,γ-unsaturated α-amino acids (method A) and 1-alkenyl aminosulfoxonium salts (method B) upon treatment with DBU. Their application to the asymmetric aziridination of N-tert-butyl-sulfonyl imino ester, generated either in situ (method A) or externally added (method B), gave the corresponding alkenyl aziridine carboxylates with medium to high diastereoselectivity and enantioselectivity. A highly stereoselective Pd(0)-catalyzed isomerization of an E,trans-configured alkenyl aziridine methanol derivative to its E-cis-isomer is described, which proceeded with retention of the double bond configuration. 相似文献
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Perro A Reculusa S Pereira F Delville MH Mingotaud C Duguet E Bourgeat-Lami E Ravaine S 《Chemical communications (Cambridge, England)》2005,(44):5542-5543
Janus silica nanoparticles, regioselectively functionalized by two different chemical groups, were synthesized through a multistep procedure based on the use of a polystyrene nodule as a protecting mask. 相似文献
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Chun Kiang Chua Adeline Huiling Loo Prof. Martin Pumera 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(17):5969-5975
Tailoring and enhancing electrocatalytic activity is of the utmost importance from the viewpoints of sustainable energy and sensing. MoS2 and graphene show great promise for the electrocatalysis of many reactions. Given that both graphene and MoS2 are highly anisotropic in nature, with edge planes that are several orders of magnitude more catalytically active than basal planes, a new hybrid material with maximized edge‐plane density to provide efficient electron transfer, high catalytic activity, and conductive cores was engineered. The hybrid material consists of radial MoS2 nanosheets with a high density of edge planes and unsaturated active sulfur atoms as well as interspersed with conductive graphene nanoplatelets. This hybrid material exhibits excellent activity for the hydrogen evolution reaction and the detection of DNA nucleobases. Such a nanoengineered, nanostructured hybrid material may play a major role in future electrocatalytic devices. 相似文献
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All-cis pentamethanolcyclopentane has been obtained in six steps by Diels–Alder condensation of maleic anhydride with (benzyloxymethyl)cyclopenta-2,4-diene, reduction of the anhydride to a diol that was protected as the acetonide. Then, ozonolysis of the double bond, followed by reduction led to a cis-diol. Then successive deprotections of the three other methanol groups gave the cis,cis,cis,cis-1,2,3,4,5-pentakis(hydroxymethyl)cyclopentane. 相似文献