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41.
42.
Renaud Beaudegnies Alain De Mesmaeker Aurélie Mallinger Myriam Baalouch André Goetz 《Tetrahedron letters》2010,51(20):2741-3222
We report the design and the efficient synthesis of novel spirocyclopropyl cyclohexane-1,3-dione and -1,3,5-trione units to be incorporated into potent HPPD inhibitors. New routes involving original combinations of synthetic equivalents of α-cyclopropyl ketone-α-anion and α-cyclopropyl ester-β-cation are described. 相似文献
43.
De Winter J Lemaur V Ballivian R Chirot F Coulembier O Antoine R Lemoine J Cornil J Dubois P Dugourd P Gerbaux P 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(35):9738-9745
Ion mobility spectrometry coupled with mass spectrometry was used to experimentally determine the three-dimensional structure of multiply charged sodium cationized polylactides (PLA). In particular, the experiments were conducted to evaluate the influence of the charge state and the size on the gas-phase conformation of cationized PLA. The measured collision cross sections were then compared to calculated values obtained by computational chemistry methods. The most striking feature was the experimental and theoretical observation of a breaking point in the quasilinear relationship between the average collision cross sections and the number of monomer units for the triply charged cations. This breaking point was theoretically demonstrated, for the doubly and triply charged cations, to be associated with a significant folding of the polymer chains around the cationizing agents. The occurrence of such breaking points could be exploited to correlate the charge state of the most intense ion series observed upon electrospray ionization with the number-average molecular mass of a polymer. 相似文献
44.
Elizabeth Renaud Christian Robelin Aïmen E. Gheribi Patrice Chartrand 《The Journal of chemical thermodynamics》2011,43(8):1286-1298
A complete critical evaluation of all available phase diagram and thermodynamic data has been performed for all condensed phases of the (LiF + LiCl + NaF + NaCl + KF + KCl + MgF2 + MgCl2 + CaF2 + CaCl2 + SrF2 + SrCl2) system, and optimized model parameters have been found. The (LiCl + NaCl + KCl + MgCl2 + CaCl2 + SrCl2), (LiF + NaF + KF + MgF2 + CaF2 + SrF2), and (LiF + LiCl + NaF + NaCl + KF + KCl + MgF2 + MgCl2 + CaF2 + CaCl2) subsystems have been critically evaluated previously. The model parameters for the common-ion binary, common-anion ternary, and reciprocal ternary subsystems (i.e. systems with two cations and two anions) can be used to predict thermodynamic properties and phase equilibria for the multicomponent reciprocal system. The Modified Quasichemical Model in the Quadruplet Approximation was used for the molten salt phase. This model takes into account both first-nearest-neighbor (cation–anion) and second-nearest-neighbor (cation–cation and anion–anion) short-range ordering, and the coupling between them. Finally, the CaFCl–SrFCl solid solution was modeled using the Compound Energy Formalism. 相似文献
45.
Radical alkylation of 2-(tert-butyl)-2-methyldioxolan-4-one, a chiral equivalent of glycolic acid, occurs with good to high diastereoselectivity that compares favorably with the corresponding enolate alkylation. The importance of the position of the transition state position, early or late, is highlighted. 相似文献
46.
Hoffer L Renaud JP Horvath D 《Combinatorial chemistry & high throughput screening》2011,14(6):500-520
Fragment-based screening is an emerging technology which is used as an alternative to high-throughput screening (HTS), and often in parallel. Fragment screening focuses on very small compounds. Because of their small size and simplicity, fragments exhibit a low to medium binding affinity (mM to μM) and must therefore be screened at high concentration in order to detect binding events. Since some issues are associated with high-concentration screening in biochemical assays, biophysical methods are generally employed in fragment screening campaigns. Moreover, these techniques are very sensitive and some of them can give precise information about the binding mode of fragments, which facilitates the mandatory hit-to-lead optimization. One of the main advantages of fragment-based screening is that fragment hits generally exhibit a strong binding with respect to their size, and their subsequent optimization should lead to compounds with better pharmacokinetic properties compared to molecules evolved from HTS hits. In other words, fragments are interesting starting points for drug discovery projects. Besides, the chemical space of low-complexity compounds is very limited in comparison to that of drug-like molecules, and thus easier to explore with a screening library of limited size. Furthermore, the "combinatorial explosion" effect ensures that the resulting combinations of interlinked binding fragments may cover a significant part of "drug-like" chemical space. In parallel to experimental screening, virtual screening techniques, dedicated to fragments or wider compounds, are gaining momentum in order to further reduce the number of compounds to test. This article is a review of the latest news in both experimental and in silico virtual screening in the fragment-based discovery field. Given the specificity of this journal, special attention will be given to fragment library design. 相似文献
47.
Buffi N Merulla D Beutier J Barbaud F Beggah S van Lintel H Renaud P van der Meer JR 《Lab on a chip》2011,11(14):2369-2377
Contamination with arsenic is a recurring problem in both industrialized and developing countries. Drinking water supplies for large populations can have concentrations much higher than the permissible levels (for most European countries and the United States, 10 μg As per L; elsewhere, 50 μg As per L). Arsenic analysis requires high-end instruments, which are largely unavailable in developing countries. Bioassays based on genetically engineered bacteria have been proposed as suitable alternatives but such tests would profit from better standardization and direct incorporation into sensing devices. The goal of this work was to develop and test microfluidic devices in which bacterial bioreporters could be embedded, exposed and reporter signals detected, as a further step towards a complete miniaturized bacterial biosensor. The signal element in the biosensor is a nonpathogenic laboratory strain of Escherichia coli, which produces a variant of the green fluorescent protein after contact to arsenite and arsenate. E. coli bioreporter cells were encapsulated in agarose beads and incorporated into a microfluidic device where they were captured in 500 × 500 μm(2) cages and exposed to aqueous samples containing arsenic. Cell-beads frozen at -20 °C in the microfluidic chip retained inducibility for up to a month and arsenic samples with 10 or 50 μg L(-1) could be reproducibly discriminated from the blank. In the 0-50 μg L(-1) range and with an exposure time of 200 minutes, the rate of signal increase was linearly proportional to the arsenic concentration. The time needed to reliably and reproducibly detect a concentration of 50 μg L(-1) was 75-120 minutes, and 120-180 minutes for a concentration of 10 μg L(-1). 相似文献
48.
R. Parentani 《International Journal of Theoretical Physics》2002,41(11):2175-2200
In the semiclassical treatment, i.e. in a classical black hole geometry, Hawking quanta emerge from trans-Planckian configurations because of scale invariance. There is indeed no scale to stop the blueshift effect encountered in the backward propagation toward the event horizon. On the contrary, when taking into account the gravitational interactions neglected in the semiclassical treatment, a new UV scale could be dynamically engendered and could stop the focusing. To show that this is the case, we use the large-N limit, where N is the number of matter fields. In this limit, the semiclassical treatment is the leading contribution. Nonlinear gravitational effects appear in the next orders and in the first of these, the effects are governed by the two-point correlation function of the energy–momentum tensor evaluated in the vacuum. In this case they can also be obtained by considering light propagation in a stochastic ensemble of metrics whose mean fluctuating properties are determined by this two-point function. 相似文献
49.
A practical synthesis of both enantiomers of 2-(tert-butyl)-2-methyl-1,3-dioxolan-4-one starting from D -mannitol is reported. These compounds are chiral equivalents of glycolic acid (= hydroxyacetic acid) which are configurationally stable and can be alkylated via their enolates. 相似文献
50.
Radical addition to 7-oxabicylco[2.2.1]hept-5-en-2-one ( 1 ) was examined from a regiochemical point of view, and despite the small electronic anisotropy of the double bond, electrophilic radicals were found to add preferentially at C(5) with selectivities of up to 5:1. We also report the first case of an inversion of the regioselectivity of a radical reaction using Lewis acids. 相似文献