Chemical bibliographic databases: the influence of term indexing policies on topic searches

International audienceA comparative study of the three main chemical information systems (Scifinder, Web of Science and Scopus) was performed by studying the indexing policies of titles, abstracts and keywords within selected literature articles. Various chemical expressions were introduced as topic searches to illustrate the different search tools related to term indexing. The resulting article lists were compared two-by-two by means of a script designed to identify common reference lists and specific ones to each editor. Analyzing these specific reference lists reveals that only partial coverage areas of references should be expected when querying a single platform. The discussion covers the term and keyword indexing policies, their influence on the retrievability of references and on the retrievability of the highly cited papers

Preparation of gem-difluorinated retrohydroxamic-fosmidomycin

International audienceFrom several decades, some organophosphorus compounds specifically designed to alterbiological systems were introduced on market as agrochemicals (ie glyphosate and glufosinate asherbicides). Nevertheless, it becomes necessary to find new compounds in order to counter plantresistances already observed with glyphosate. Fosmidomicyn and its N-acetyl analogues FR-900098 were perceived as starting points for elaboration of new herbicide candidates, targetingthe second enzyme of the non-mevalonate pathway in plants, the 1-deoxy-D-xylulose 5-phosphate reductoisomerase (DOXP reductoisomerase or DXR). It is expected that theenhancement of bioactivity compared to the parent compounds, might be reached by insertion oftwo fluorine atoms close to the phosphonate function. Indeed, the presence of both fluorineatoms could improve the lipophilicity, affect the pKa of the phosphonic acid function and theninduce better activities. Herein, the synthesis of gem-difluorinated analogues of retrohydroxamicfosmidomycin and FR-900098-ester is reported using a radical addition mediated by acobaloxime comple

Mechanochemical synthesis of mononuclear gold(I) halide complexes of diphosphine ligands with tuneable luminescent properties

A mechanochemical method is reported for the synthesis of Au(diphos)X complexes of diphosphine (diphos = XantPhos and N-XantPhos) ligands and halide ions (X = Cl and I). The Au(XantPhos)X (1: X = Cl; 2: X = I) and Au(N-XantPhos)Cl (3) complexes exhibited either yellowish green (1) or bluish green (2) emission, whereas 3 was seemingly non-emissive in the solid state at room temperature. Blue- (2B) and bluish green (2G) luminescent concomitant solvates of 2 were obtained by recrystallization. Luminescent colour changes from blue (2B) or bluish green (2G) to yellow were observed when these forms were subjected to mechanical stimulus, while the original emission colour can be recovered in the presence of solvent vapours. Moreover, the luminescence of 2B can be reversibly altered between blue and yellow by heating/cooling-cycles. These results demonstrate the power of mechanochemistry in the rapid (4 min reaction time), efficient (up to 98% yield) and greener synthesis of luminescent and stimuli-responsive gold(I) complexes

A field expansions method for scattering by periodic multilayered media

The interaction of acoustic and electromagnetic waves with periodic structures plays an important role in a wide range of problems of scientific and technological interest. This contribution focuses upon the robust and high-order numerical simulation of a model for the interaction of pressure waves generated within the earth incident upon layers of sediment near the surface. Herein described is a boundary perturbation method for the numerical simulation of scattering returns from irregularly shaped periodic layered media. The method requires only the discretization of the layer interfaces (so that the number of unknowns is an order of magnitude smaller than finite difference and finite element simulations), while it avoids not only the need for specialized quadrature rules but also the dense linear systems characteristic of boundary integral/element methods. The approach is a generalization to multiple layers of Bruno and Reitich’s “Method of Field Expansions” for dielectric structures with two layers. By simply considering the entire structure simultaneously, rather than solving in individual layers separately, the full field can be recovered in time proportional to the number of interfaces. As with the original field expansions method, this approach is extremely efficient and spectrally accurate

LSST: from Science Drivers to Reference Design and Anticipated Data Products

(Abridged) We describe here the most ambitious survey currently planned in the optical, the Large Synoptic Survey Telescope (LSST). A vast array of science will be enabled by a single wide-deep-fast sky survey, and LSST will have unique survey capability in the faint time domain. The LSST design is driven by four main science themes: probing dark energy and dark matter, taking an inventory of the Solar System, exploring the transient optical sky, and mapping the Milky Way. LSST will be a wide-field ground-based system sited at Cerro Pach\'{o}n in northern Chile. The telescope will have an 8.4 m (6.5 m effective) primary mirror, a 9.6 deg$^2$ field of view, and a 3.2 Gigapixel camera. The standard observing sequence will consist of pairs of 15-second exposures in a given field, with two such visits in each pointing in a given night. With these repeats, the LSST system is capable of imaging about 10,000 square degrees of sky in a single filter in three nights. The typical 5$\sigma$ point-source depth in a single visit in $r$ will be $\sim 24.5$ (AB). The project is in the construction phase and will begin regular survey operations by 2022. The survey area will be contained within 30,000 deg$^2$ with $\delta<+34.5^\circ$, and will be imaged multiple times in six bands, $ugrizy$, covering the wavelength range 320--1050 nm. About 90\% of the observing time will be devoted to a deep-wide-fast survey mode which will uniformly observe a 18,000 deg$^2$ region about 800 times (summed over all six bands) during the anticipated 10 years of operations, and yield a coadded map to $r\sim27.5$. The remaining 10\% of the observing time will be allocated to projects such as a Very Deep and Fast time domain survey. The goal is to make LSST data products, including a relational database of about 32 trillion observations of 40 billion objects, available to the public and scientists around the world.Comment: 57 pages, 32 color figures, version with high-resolution figures available from https://www.lsst.org/overvie

Targeting of the 1-Deoxy-D-Xylulose-5-Phosphate Reductoisomerase (DXR) enzyme (design and synthesis of new Fosmidomycin analogues as potential herbicides)

La synthèse enzymatique de terpénoides chez les mammifères provient de la voie mevalonique. Récemment une voie différente a été découverte et s'est révélée être prépondérante pour de nombreux organismes comme les plantes et bactéries. L'identification d'un inhibiteur de cette cascade enzymatique permettrait le développement d'une nouvelle famille d'herbicide. Les caractéristiques de la 1-déoxy-D-xylulose 5-phosphate réductoisomérase (DXR) font de cette enzyme très spécifique une cible pour la synthèse de nouveaux composés. La Fosmidomycine ainsi que son analogue acétylé le plus proche, FR-900098 restent des références pour l'inhibition de la DXR. Dans ce contexte, l'ensemble des molécules décrites dans la littérature en tant qu'inhibiteurs a été classé en fonction des modifications apportées sur le substrat naturel ou la Fosmidomycine. A partir de l'ensemble de ces informations, cinq familles ont été synthétisées pour trouver un nouveau motif complexant. Pour deux d'entre elles, le squelette de base contient un acide phosphonique et un acide phosphinique sur lequel a été introduit la diversité moléculaire grâce aux réactions de Pudovik et de couplage pallado-catalysé. Les autres motifs complexant originaux sont constitués d'une fonction carbonyle et d'un hétérocycle en a ou b. Après optimisation de la synthèse des précurseurs, la diversité a été introduite à l'aide, par exemple, d'une réaction de trois composantes permettant la préparation d'hétérocycle. Enfin, deux modifications ont été faites sur le bras espaceur : l'introduction d'atomes de fluor pour modifier les propriétés physicochimiques ou d'un atome d'azote, point d'attache de nouveaux groupements.The non-mevalonate pathway is widely found in higher plants and in many eubacteria, including pathogenic ones, but not in mammals. Identifying a non-mevalonate pathway inhibitor would greatly contribute to the search for new herbicides. The unique properties of 1-Deoxy-D-xylulose 5-phosphate reductoisomerase make it remarkable and rational target for drug design. The phosphonohydroxamic acid Fosmidomycin, which acts through inhibition of DXR, is a natural compound produced in the fermentation of Streptomyces and still remains, with its N-acetyl homologue FR900098, one of the most active compounds. First of all, the enzyme and all the potential inhibitors tested in literature were classified in order to understand the global quest for therapeutically useful compounds. In this context, we designed and synthesized five different families of Fosmidomycin analogues containing a new chelating unit. Two targets molecules families bearing a phosphinophonic acid as common core were imagined. Divergent approach allowed the introduction of the chemical diversity thank to powerful pallado-catalyzed coupling reaction. The other families containing carbonyl group and heterocycle in a and b position were regarded as highly potent complexing units. Chemical diversity was introduced mainly at the end of the synthesis. For one of them convergent ring formation using three-components reaction was developed. Finally two modifications of the Fosmidomycin linker were performed by the introduction of fluorine atoms on the parent structure as well as the replacement of a carbon by a nitrogen atom in order to create a new point of modifications.MONTPELLIER-Ecole Nat.Chimie (341722204) / SudocSudocFranceF

31.40 Product Class 40: Arylphosphinic acids and derivatives

ISBN 978-3-13-142651-

Anomalous reactivity of diphenylhydroxymethylphosphine oxide in the synthesis of a phosphorylated ether by oxa- Michael reaction

International audienceVinylic phosphorus compounds were found to react as Michael olefins with alcohols in basic catalytic conditions. Several phosphorylated polyethers were obtained in such a way. In analogous conditions, the hydroxymethylphosphine oxide used as alcoholic reagent looses formaldehyde leading to 1,2-diphosphorus compound formation