Formation et réactivité de carbanions α phosphoramides. Mise en évidence d'une nouvelle réaction d'élimination

The reactivity of (diethoxy)-N-methyl-N-benzyl phosphoramide (I) and bis(dinethylamino)-N-methyl-N-benzylphosphoramide (II) when treated with strong bases (RLi, R₂NLi) is very different: (I) gives a novel elimination, whereas (II) under the same experimental conditions gives a stable carbanion whose reactivity has been investigated.     

Action du chlorure de nitrosyle sur le trichloréthylène et sur le tétrachloréthylène

Nitrosyl chloride is only chlorinating in darkness and above 100°. In the sun light and at room temperature it reacts as a chlorinating, nitrosating, nitrating and oxidizing agent. With trichlorethylene in fact pentachlorethane 1,1,1,2-tetrachloro-2-nitrosoethane, 1,1,1,2-tetrachloro-2-nitroethane, dichloracetic acid and a compound of empirical formula C₄H₂Cl₅NO₂ are obtained. Tetrachloroethylene carried to hexachlorethane, pentachloronitrosoethane and tetrachloro-2-(pentachlorethyl)-1,2-oxazetidine. Introduced nitrosyl chloride provided nitrogen monoxide prouved by gaz chromatography. This monoxide reacted afterwards to give nitrogen which is the single nitrogenous gazeous compound. Carbondioxide is a minor component of the gaz.     

Halogenation in Fungi: What Do We Know and What Remains to Be Discovered?

In nature, living organisms produce a wide variety of specialized metabolites to perform many biological functions. Among these specialized metabolites, some carry halogen atoms on their structure, which can modify their chemical characteristics. Research into this type of molecule has focused on how organisms incorporate these atoms into specialized metabolites. Several families of enzymes have been described gathering metalloenzymes, flavoproteins, or S-adenosyl-L-methionine (SAM) enzymes that can incorporate these atoms into different types of chemical structures. However, even though the first halogenation enzyme was discovered in a fungus, this clade is still lagging behind other clades such as bacteria, where many enzymes have been discovered. This review will therefore focus on all halogenation enzymes that have been described in fungi and their associated metabolites by searching for proteins available in databases, but also by using all the available fungal genomes. In the second part of the review, the chemical diversity of halogenated molecules found in fungi will be discussed. This will allow the highlighting of halogenation mechanisms that are still unknown today, therefore, highlighting potentially new unknown halogenation enzymes.     

The Linear Rational Pseudospectral Method with Preassigned Poles

We present a linear rational pseudospectral (collocation) method with preassigned poles for solving boundary value problems. It consists in attaching poles to the trial polynomial so as to make it a rational interpolant. Its convergence is proved by transforming the problem into an associated boundary value problem. Numerical examples demonstrate that the rational pseudospectral method is often more efficient than the polynomial method.     

Differential Simplicity in Polynomial Rings and Algebraic Independence of Power Series

Let k be a field of characteristic zero, f(X,Y), g(X,Y)k[X,Y],g(X,Y) (X,Y) and d:=g(X,Y)/X + f(X,Y)/Y. A connection is establishedbetween the d-simplicity of the local ring k[X,Y]_(X,Y) and thetranscendency of the solution in tk[[t]] of the algebraic differentialequation g(t,y(t))·(/t)y(t)+f(t,y(t)). This connectionis used to obtain some interesting results in the theory ofthe formal power series and to construct new examples of differentiallysimple rings.     

Embedding optimisation algorithms with Mosel

Algebraic modelling languages allow models to be implemented in such a way that they can easily be understood and modified. They are therefore a working environment commonly used by practitioners in Operations Research. Having once developed models, they need to be integrated inside the company information system. This step often involves embedding a model into a programming language environment: many existing algebraic modelling languages make possible to run parameterised models and subsequently retrieve their results, but without any facility for interacting with the model during the model generation or solution process.In this paper we show how to use the Mosel environment to implement complex algorithms directly in the modelling language.The Office cleaning problem is solved by a branch-and-cut algorithm, implemented entirely in the modelling language (including the definition of the callback function for the solver). Secondly, a cutting stock problem is solved by column generation, also implemented in the modelling language.AMS classification: 90Cxx, 65K05, 68N15     

Behaviour of (−Δ−k2−i0+)−1 outside fading obstacles,independant scattering hypothesis and applications

This paper deals with the behaviour of k‐outgoing solutions of ?Δu?k²u=f outside a fading soft obstacle. We extend an approach using the so‐called Lax–Phillips construction and the well‐known properties of the capacity of smooth obstacles. So, classical results are recovered in a straightforward manner. The previous approach enables us to consider the case of obstacles composed of many tiny spheres. Roughly speaking, we prove that the scattering amplitude is approximately the sum of the scattering amplitudes scattered by each isolated sphere, which is an alternative form of the first Born approximation. As a consequence, two inverse problems are solved. Copyright © 2003 John Wiley & Sons, Ltd.     

Solvent effects on charge spatial extent in DNA and implications for transfer

To clarify the role played by water in facilitating long-range DNA charge transport, carefully designed, state-of-the-art, self-interaction corrected density-functional quantum mechanical and molecular mechanical (SIC-QM/MM) simulations are performed for the first time on two ionized adenine:thymine bridge models in explicit water solvent at finite temperature. For random solvent configurations, the charge is partially delocalized. However, a charge localization on different, well-separated adenines can be induced and is correlated with a restructuring of their first solvation shells. Thus, the importance of water in the mechanism of long-range charge transport is explicitly demonstrated, and the microscopic conditions for a charge localization are revealed.