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341.
Durka M Tikad A Périon R Bosco M Andaloussi M Floquet S Malacain E Moreau F Oxoby M Gerusz V Vincent SP 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(40):11305-11313
L-Heptoses (L-glycero-D-manno-heptopyranoses) are constituents of the inner core of lipolysaccharide (LPS), a molecule playing key roles in the mortality of many infectious diseases as well as in the virulence of many human pathogens. The inhibition of the first enzymes of the bacterial heptose biosynthetic pathway is an almost unexplored field to date although it appears to be a very novel way for the development of antivirulence drugs. We report the synthesis of a series of D-glycero-D-manno-heptopyranose 7-phosphate (H7P) analogues and their inhibition properties against the isomerase GmhA and the the kinase HldE, the two first enzymes of the bacterial heptose biosynthetic pathway. The heptose structures have been modified at the 1-, 2-, 6- and 7-positions to probe the importance of the key structural features of H7P that allow a tight binding to the target enzymes; H7P being the product of GmhA and the substrate of HldE, the second objective was to find structures that could simultaneously inhibit both enzymes. We found that GmhA and HldE were extremely sensitive to structural modifications at the 6- and 7- positions of the heptose scaffold. To our surprise, the epimeric analogue of H7P displaying a D-glucopyranose configuration was found to be the best inhibitor of both enzymes but also the only molecule of this series that could inhibit GmhA (IC(50)=34 μM) and HldE (IC(50)=9.4 μM) in the low micromolar range. Noteworthy, this study describes the first inhibitors of GmhA ever reported, and paves the way to the design of a second generation of molecules targeting the bacterial virulence. 相似文献
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343.
The present contribution investigates the dynamics generated by the two-dimensional Vlasov-Poisson-Fokker-Planck equation for charged particles in a steady inhomogeneous background of opposite charges. We provide global in time estimates that are uniform with respect to initial data taken in a bounded set of a weighted \(L^2\) space, and where dependencies on the mean-free path \(\tau \) and the Debye length \(\delta \) are made explicit. In our analysis the mean free path covers the full range of possible values: from the regime of evanescent collisions \(\tau \rightarrow \infty \) to the strongly collisional regime \(\tau \rightarrow 0\). As a counterpart, the largeness of the Debye length, that enforces a weakly nonlinear regime, is used to close our nonlinear estimates. Accordingly we pay a special attention to relax as much as possible the \(\tau \)-dependent constraint on \(\delta \) ensuring exponential decay with explicit \(\tau \)-dependent rates towards the stationary solution. In the strongly collisional limit \(\tau \rightarrow 0\), we also examine all possible asymptotic regimes selected by a choice of observation time scale. Here also, our emphasis is on strong convergence, uniformity with respect to time and to initial data in bounded sets of a \(L^2\) space. Our proofs rely on a detailed study of the nonlinear elliptic equation defining stationary solutions and a careful tracking and optimization of parameter dependencies of hypocoercive/hypoelliptic estimates. 相似文献
344.
Trinuclear copper(II) complex [CuII3(NIT2PhO)2Cl4] was synthesized with p-cresol-substituted bis(α-nitronyl nitroxide) biradical: 4-methyl-2,6-bis(1-oxyl-3-oxido-4,4,5,5-tetramethyl-2-imidazolin-2-yl)phenol (NIT2PhOH). The crystal structure of this heterospin complex was determined using single-crystal X-ray diffraction analysis and exhibits four unusual seven-membered metallocycles formed from the coordination of oxygen atoms of the N-O groups and of bridging phenoxo (µ-PhO−) moieties with copper(II) ions. The crystal structure analysis reveals an incipient agostic interaction between a square planar copper center and a hydrogen-carbon bond from one methyl group carried on the coordinated nitronyl-nitroxide radical. The intramolecular Cu∙∙∙H-C interaction involves a six-membered metallocycle and may stabilize the copper center in square planar coordination mode. From the magnetic susceptibility measurements, the complex, which totals seven S = 1/2 spin carriers, has almost a ground state spin S = 1/2 at room temperature ascribed to strong antiferromagnetic interaction between the nitronyl nitroxide moieties and the copper(II) centers and in between the copper(II) centers through the bridging phenoxo oxygen atom. 相似文献
345.
Kim Anh Nguyen Emilie Lesur Maxime Ribéraud Antoine Sallustrau Davide Audisio Frédéric Taran 《Helvetica chimica acta》2023,106(3):e202200187
The synthesis of four clickable sydnone-heptamethine cyanine derivatives is described in this article. The synthetic route is based on a palladium-cross coupling reactions of sydnone boronates affording the desired sydnone-cyanine conjugates in only five steps. These compounds were shown to react smoothly with cyclooctynes to form the corresponding pyrazoles clicked products quantitatively at room temperature and with rate constants up to 18 m −1 ⋅ s−1, affording interesting new tools for biorthogonal fluorescent labelling of (bio)molecules. Fluorescence properties of both sydnone- and pyrazole-cyanines are described, as well. 相似文献
346.
Alexandre Labiche Augustin Malandain Maxime Molins Dr. Frédéric Taran Dr. Davide Audisio 《Angewandte Chemie (International ed. in English)》2023,62(36):e202303535
In contrast to stable and natural abundant carbon-12, the synthesis of organic molecules with carbon (radio)isotopes must be conceived and optimized in order to navigate through the hurdles of radiochemical requirements, such as high costs of the starting materials, harsh conditions and radioactive waste generation. In addition, it must initiate from the small cohort of available C-labeled building blocks. For long time, multi-step approaches have represented the sole available patterns. On the other side, the development of chemical reactions based on the reversible cleavage of C−C bonds might offer new opportunities and reshape retrosynthetic analysis in radiosynthesis. This review aims to provide a short survey on the recently emerged carbon isotope exchange technologies that provide effective opportunity for late-stage labeling. At present, such strategies have relied on the use of primary and easily accessible radiolabeled C1-building blocks, such as carbon dioxide, carbon monoxide and cyanides, while the activation principles have been based on thermal, photocatalytic, metal-catalyzed and biocatalytic processes. 相似文献
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348.
Maxime Robin Stephane Mialhe Valerie Pique Robert Faure Jean‐Pierre Galy 《ChemInform》2002,33(38):153-153