Intramolecular inverse electron-demand [4+2] cycloadditions of ynamidyl-tethered pyrimidines: Comparative studies in trifluorotoluene and sulfolane

International audienceThree representative 6,7-dihydro-5H-cyclopenta[b]pyridin-4-amines were synthesized using an intramolecular inverse electron demand heteroeDielseAlder/retroeDielseAlder sequence between pyrimidines (acting as azadienes) and ynamides (acting as dienophiles). Two solvents of this reaction, sulfolane and trifluorotoluene, were compared at 210 C and the former consistently led to higher yields. In addition, these studies confirmed the importance of the steric bulk of the C5-position of the pyrimidinyl cycloaddition precursor

Coupling techniques for nonlinear hyperbolic equations. III. The well-balanced approximation of thick interfaces

We continue our analysis of the coupling between nonlinear hyperbolic problems across possibly resonant interfaces. In the first two parts of this series, we introduced a new framework for coupling problems which is based on the so-called thin interface model and uses an augmented formulation and an additional unknown for the interface location; this framework has the advantage of avoiding any explicit modeling of the interface structure. In the present paper, we pursue our investigation of the augmented formulation and we introduce a new coupling framework which is now based on the so-called thick interface model. For scalar nonlinear hyperbolic equations in one space variable, we observe that the Cauchy problem is well-posed. Then, our main achievement in the present paper is the design of a new well-balanced finite volume scheme which is adapted to the thick interface model, together with a proof of its convergence toward the unique entropy solution (for a broad class of nonlinear hyperbolic equations). Due to the presence of a possibly resonant interface, the standard technique based on a total variation estimate does not apply, and DiPerna's uniqueness theorem must be used. Following a method proposed by Coquel and LeFloch, our proof relies on discrete entropy inequalities for the coupling problem and an estimate of the discrete entropy dissipation in the proposed scheme.Comment: 21 page

Inverse Electron-Demand [4 + 2]-Cycloadditions of Ynamides: Access to Novel Pyridine Scaffolds

Functionalized polycyclic aminopyridines are central to the chemical sciences, but their syntheses are still hampered by a number of shortcomings. These nitrogenated heterocycles can be efficiently prepared by an intramolecular inverse electron demand hetero Diels–Alder ( ih DA) cycloaddition of ynamides to pyrimidines. This ihDA/rDA sequence is general in scope and affords expedient access to novel types of aminopyridinyl scaffolds that hold great promise in terms of exit vector patterns

Tests of achromatic phase shifters performed on the SYNAPSE test bench: a progress report

The achromatic phase shifter (APS) is a component of the Bracewell nulling interferometer studied in preparation for future space missions (viz. Darwin/TPF-I) focusing on spectroscopic study of Earth-like exo-planets. Several possible designs of such an optical subsystem exist. Four approaches were selected for further study. Thales Alenia Space developed a dielectric prism APS. A focus crossing APS prototype was developed by the OCA, Nice, France. A field reversal APS prototype was prepared by the MPIA in Heidelberg, Germany. Centre Spatial de Li\`ege develops a concept based on Fresnel's rhombs. This paper presents a progress report on the current work aiming at evaluating these prototypes on the SYNAPSE test bench at the Institut d'Astrophysique Spatiale in Orsay, France

OrthoSelect: a protocol for selecting orthologous groups in phylogenomics

Background: Phylogenetic studies using expressed sequence tags (EST) are becoming a standard approach to answer evolutionary questions. Such studies are usually based on large sets of newly generated, unannotated, and error-prone EST sequences from different species. A first crucial step in EST-based phylogeny reconstruction is to identify groups of orthologous sequences. From these data sets, appropriate target genes are selected, and redundant sequences are eliminated to obtain suitable sequence sets as input data for tree-reconstruction software. Generating such data sets manually can be very time consuming. Thus, software tools are needed that carry out these steps automatically. Results: We developed a flexible and user-friendly software pipeline, running on desktop machines or computer clusters, that constructs data sets for phylogenomic analyses. It automatically searches assembled EST sequences against databases of orthologous groups (OG), assigns ESTs to these predefined OGs, translates the sequences into proteins, eliminates redundant sequences assigned to the same OG, creates multiple sequence alignments of identified orthologous sequences and offers the possibility to further process this alignment in a last step by excluding potentially homoplastic sites and selecting sufficiently conserved parts. Our software pipeline can be used as it is, but it can also be adapted by integrating additional external programs. This makes the pipeline useful for non-bioinformaticians as well as to bioinformatic experts. The software pipeline is especially designed for ESTs, but it can also handle protein sequences. Conclusion: OrthoSelect is a tool that produces orthologous gene alignments from assembled ESTs. Our tests show that OrthoSelect detects orthologs in EST libraries with high accuracy. In the absence of a gold standard for orthology prediction, we compared predictions by OrthoSelect to a manually created and published phylogenomic data set. Our tool was not only able to rebuild the data set with a specificity of 98%, but it detected four percent more orthologous sequences. Furthermore, the results OrthoSelect produces are in absolut agreement with the results of other programs, but our tool offers a significant speedup and additional functionality, e.g. handling of ESTs, computing sequence alignments, and refining them. To our knowledge, there is currently no fully automated and freely available tool for this purpose. Thus, OrthoSelect is a valuable tool for researchers in the field of phylogenomics who deal with large quantities of EST sequences. OrthoSelect is written in Perl and runs on Linux/Mac OS X

Mechanisms and Evolutionary Patterns of Mammalian and Avian Dosage Compensation

A large-scale comparative gene expression study reveals the different ways in which the chromosome-wide gene dosage reductions resulting from sex chromosome differentiation events were compensated during mammalian and avian evolution

The human phylome

The human phylome, which includes evolutionary relationships of all human proteins and their homologs among thirty-nine fully sequenced eukaryotes, is reconstructed

Adolescents issus de la migration: génération spontanée?

Le Journal des Psychologueinfo:eu-repo/semantics/nonPublishe