Dioxo-2,5 pipérazines. 1. La synthèse des carboxythiazolo dioxo-2,5 pipérazines

A new and general synthesis of 2,5-dioxopiperazine condensed with the thiazolidine ring is described. The synthesis involves the use of N-ethoxy carbonyl-2-ethoxy-1-2-dihydroquinoleine (EEDQ) as activating agent to form the 2,5-diketopiperazine (EEDQ) as activating agent to form the 2,5-diketopiperazine ring. By this method 9-carbobutoxy-7,7-dimethyl-2,5-dioxo-8-this-1,4-diazabicyclo[4.3.0] nonane (6) and 9-carboxy-8,8 dimethyl-2,5-dioxo-7-thia-1,4-diazabicy clo [4.3.0] nonane (8) were obtained, with near quantitative yield, from 4-carboxy-2-carbobutoxy-5,5 dimethylthiazolidine (4). The former was transformed into acid 7 by hydrolysis with barium bydroxyde and the latter was esterified with diazornethane thus producing a methylester 9. The use of the ethy lester of N-(2-cabobutoxy-4-carboxy-5,5-dimethyl-thiazolidine)glycine (10) for synthesis of 6 was also successful. The spectromethric data were interpreted and confirm the proposed structure of the new compounds.     

The lowest-energy ligand to metal charge-transfer absorption band of trans-[OsO2(malonate)2]2-

The resolved structure of the lowest-energy oxo to osmium charge-transfer absorption band of trans-[OsO2(malonate)2]2- is analyzed on the basis of the exact molecular Ci symmetry determined from the structure of a crystal used for spectroscopy. The multiple progressions observed in the polarized spectra are rationalized in terms of the deviations from idealized D4h point group symmetry and compared to the spectra observed for complexes with D2h symmetry such as trans-[OsO2(oxalate)2]2- that show only a single dominant progression for this transition.     

A remark on analytic Fredholm alternative

We apply a recent result of Borichev–Golinskii–Kupin on the Blaschke-type conditions for zeros of analytic functions on the complex plane with a cut along the positive semi-axis to the problem of the eigenvalues distribution of the Fredholm-type analytic operator-valued functions.     

Fast reproducible identification and large-scale databasing of individual functional cognitive networks

Background  

Although cognitive processes such as reading and calculation are associated with reproducible cerebral networks, inter-individual variability is considerable. Understanding the origins of this variability will require the elaboration of large multimodal databases compiling behavioral, anatomical, genetic and functional neuroimaging data over hundreds of subjects. With this goal in mind, we designed a simple and fast acquisition procedure based on a 5-minute functional magnetic resonance imaging (fMRI) sequence that can be run as easily and as systematically as an anatomical scan, and is therefore used in every subject undergoing fMRI in our laboratory. This protocol captures the cerebral bases of auditory and visual perception, motor actions, reading, language comprehension and mental calculation at an individual level.     

Combining the use of solid‐supported transition metal catalysis with microwave irradiation in solution‐phase parallel library synthesis

Microwave heating methods have been combined with the use of solid-supported catalysts to produce small solution-phase libraries of medicinally-relevant compounds. Palladium supported on charcoal (Pd/C) has been used to produce libraries of pyrazole compounds for screening in COX II studies via Suzuki cross coupling reactions, while the same catalyst has been used also to produce styryl-based nAChR compounds using analogous chemistry. Although the reaction substrates are very different (aryl vs. vinyl), this catalyst system provided consistently good and reliable results. The use of a polystyrene-supported Ru catalyst for ring-closing metathesis (RCM) reactions was also evaluated to prepare benzolactam structures for evaluation as factor Xa inhibitors.     

Improved and isotropic resolution in tomographic diffractive microscopy combining sample and illumination rotation

Tomographic Diffractive Microscopy is a technique, which permits to image transparent living specimens in three dimensions without staining. It is commonly implemented in two configurations, by either rotating the sample illumination keeping the specimen fixed, or by rotating the sample using a fixed illumination. Under the first-order Born approximation, the volume of the frequency domain that can be mapped with the rotating illumination method has the shape of a “doughnut”, which exhibits a so-called “missing cone” of non-captured frequencies, responsible for the strong resolution anisotropy characteristic of transmission microscopes. When rotating the sample, the resolution is almost isotropic, but the set of captured frequencies still exhibits a missing part, the shape of which resembles that of an apple core. Furthermore, its maximal extension is reduced compared to tomography with rotating illumination. We propose various configurations for tomographic diffractive microscopy, which combine both approaches, and aim at obtaining a high and isotropic resolution. We illustrate with simulations the expected imaging performances of these configurations.     

L1 Existence and Uniqueness of Entropy Solutions to Nonlinear Multivalued Elliptic Equations with Homogeneous Neumann Boundary Condition and Variable Exponent

In this work, we study the following nonlinear homogeneous Neumann boundary value problemβ （u） -diva （x, 7u） f in fΩ, a （x, u）. η= 0 on Ω, where Ω is a smooth bounded open domain in RN, N ≥ 3 with smooth boundary Ωand ηthe outer unit normal vector on Ω . We prove the existence and uniqueness of an entropy solution for L1-data f. The functional setting involves Lebesgue and Sobolev spaces with variable exponent.     

Dimerization by Hetero Diels-Alder Reaction of Methyl 4,6-O-Benzylidene-3-Deoxy-3-C-Methylene-α-D-Erythro-Hexopyranosid-2-Ulose

Abstract

The dimerization by hetero Diels-Alder reaction of methyl 4,6-O-benzylidene-3-deoxy-3-C-methylene-α-D-erythro-hexopyranosid-2-ulose was found to be regio and stereospecific. The structure of the cycloadduct was assigned from NMR spectrographic and X-ray crystallographic results. These results indicated that this cycloaddition occurred by a concerted hetero Diels-Alder reaction with inverse electron demand.     

The accuracy of tomographic particle image velocimetry for measurements of a turbulent boundary layer

To investigate the accuracy of tomographic particle image velocimetry (Tomo-PIV) for turbulent boundary layer measurements, a series of synthetic image-based simulations and practical experiments are performed on a high Reynolds number turbulent boundary layer at Re_θ = 7,800. Two different approaches to Tomo-PIV are examined using a full-volume slab measurement and a thin-volume “fat” light sheet approach. Tomographic reconstruction is performed using both the standard MART technique and the more efficient MLOS-SMART approach, showing a 10-time increase in processing speed. Random and bias errors are quantified under the influence of the near-wall velocity gradient, reconstruction method, ghost particles, seeding density and volume thickness, using synthetic images. Experimental Tomo-PIV results are compared with hot-wire measurements and errors are examined in terms of the measured mean and fluctuating profiles, probability density functions of the fluctuations, distributions of fluctuating divergence through the volume and velocity power spectra. Velocity gradients have a large effect on errors near the wall and also increase the errors associated with ghost particles, which convect at mean velocities through the volume thickness. Tomo-PIV provides accurate experimental measurements at low wave numbers; however, reconstruction introduces high noise levels that reduces the effective spatial resolution. A thinner volume is shown to provide a higher measurement accuracy at the expense of the measurement domain, albeit still at a lower effective spatial resolution than planar and Stereo-PIV.     

Nonlinear elliptic problem involving non-local boundary conditions and variable exponent

We study a nonlinear elliptic problem with non-local boundary conditions and variable exponent. We prove an existence and uniqueness result of weak solution to this problem with general maximal monotone graphs.