Mono- and dicarbonyl-bridged tricyclic heterocyclic acceptors: synthesis and electronic properties

A series of trialkylsilyl-substituted 2,2'-dithiophene, 4,4'-di-n-hexyl-2,2'-dithiophene, 5,5'-dithiazole, and 2,2'-diselenophene with carbonyl (2a-d) and α-dicarbonyl bridges (3a-d) were prepared from readily available dihalides, using double lithiation followed by trapping with N,N-dimethylcarbamoyl chloride or diethyl oxalate (or N,N-dimethylpiperazine-2,3-dione), respectively. Cyclic voltammetry reveals that the first half-wave reduction potentials for this series of compounds span a wide range, from -1.87 to -0.97 V vs the ferrocene/ferrocenium couple at 0 V (0.1 M (n)Bu(4)NPF(6) in THF). A significant increase of the first half-wave reduction potential (by 0.50-0.67 V) was observed on substitution of the monocarbonyl bridge with α-dicarbonyl. Adiabatic electron affinity (AEA, gas phase) trends determined via density functional theory (DFT) calculations are in good agreement with the electrochemical reduction potentials. UV-vis absorption spectra across the series show a weak absorption band in the visible range, corresponding to the HOMO→LUMO transition within a one-electron picture, followed by a more intense, high-energy transition(s). Single-crystal X-ray structural analyses reveal molecular packing features that balance the interplay of the presence of the bulky substituents, intermolecular π-stacking interactions, and S···O intermolecular contacts, all of which affect the DFT-evaluated intermolecular electronic couplings and effective charge-carrier masses for the crystals of the tricyclic cores.     

Isolation of C-glycosyl xanthones from Coffea pseudozanguebariae and their location

The biochemical composition of leaves from Coffea pseudozanguebariae, a wild caffeine-free coffee species, was determined. Two phenolic compounds were extracted from leaves, separated and characterized. Their structures were elucidated by mass spectrometry, and 1D and 2D NMR spectroscopy and were shown to be mangiferin (1) and isomangiferin (2), which were the main polyphenol products. Multiphoton fluorescence imaging was performed to visualize polyphenol distribution in leaf cross sections. Consistent biochemical analysis cell imaging techniques on leaves revealed yellow fluorescence in the epidermis and parenchyma cells corresponding to xanthone compounds.     

Determination of the enantiomeric excess of α-hydroxy acids

This work describes a convenient and accurate method for optical purity determination of α-hydroxy acids. Their derivatization with commercially available valine methyl ester affords diastereoisomers easily separable by HPLC using achiral C₁₈ columns.     

La détection infrarouge avec les plans focaux non refroidis : état de l'artUncooled focal plane infrared detectors: the state of the art

The emergence of uncooled detectors has opened new opportunities for IR detection for both military and commercial applications. Development of such devices involves a lot of trade-offs between the different parameters that define the technological stack. These trade-offs explain the number of different architectures that are under worldwide development. The key factor is to find a high sensitivity and low noise thermometer material compatible with silicon technology in order to achieve high thermal isolation in the smallest area as possible. Ferroelectric thermometer based hybrid technology and electrical resistive thermometer based (microbolometer) technology are under development. LETI and ULIS have chosen from the very beginning to develop first a monolithic microbolometer technology fully compatible with commercially available CMOS technology and secondly amorphous silicon based thermometer. This silicon approach has the greatest potential for reducing infrared detector manufacturing cost. After the development of the technology, the transfer to industrial facilities has been performed in a short period of time and the production is now ramping up with ULIS team in new facilities. LETI and ULIS are now working to facilitate the IRFPA integration into equipment in order to address a very large market. Achievement of this goal needs the development of smart sensors with on-chip advanced functions and the decrease of manufacturing cost of IRFPA by decreasing the pixel pitch and simplifying the vacuum package. We present in this paper the technology developed by CEA/LETI and its improvement for being able to designs 384×288 and 160×120 arrays with a pitch of 35 μm. Thermographic application needs high stability infrared detector with a precise determination of the amount of absorbed infrared flux. Hence, infrared detector with internal temperature stabilized shield has been developed and characterized. These results will be presented. To cite this article: J.-L. Tissot, C. R. Physique 4 (2003).     

k-intolerant capacities and Choquet integrals

We define an aggregation function to be (at most) k-intolerant if it is bounded from above by its kth lowest input value. Applying this definition to the discrete Choquet integral and its underlying capacity, we introduce the concept of k-intolerant capacities which, when varying k from 1 to n, cover all the possible capacities on n objects. Just as the concepts of k-additive capacities and p-symmetric capacities have been previously introduced essentially to overcome the problem of computational complexity of capacities, k-intolerant capacities are proposed here for the same purpose but also for dealing with intolerant or tolerant behaviors of aggregation. We also introduce axiomatically indices to appraise the extent to which a given capacity is k-intolerant and we apply them on a particular recruiting problem.     

Synthesis and characterization of polyethylene film grafted with acrylic acid and diethyleneglycol-dimethacrylate

Acrylic acid (AA) and diethyleneglycol-dimethacrylate (DEGDM) are grafted onto 25 μm low-density radio-peroxided polyethylene. Monomer content is determined by exchange capacity measurements. Studies of electrical resistance and zero-current membrane potential allow for the determination of the influence of DEGDM on both the dissociation of grafted AA and the permselectivity of these so-obtained cation-exchange membranes. DEGDM, acting as a crosslinking agent, limits the AA degree of grafting, slightly increases the electrical resistance, but contributes to enhance the permselectivity. For example, when these grafted films are immersed in 3M NaCl aqueous solutions, the addition of DEGDM leads to an increase of the transport number of Na⁺ close to 20%. © 1993 John Wiley & Sons, Inc.     

A propos de la structure de pyrimidines obtenues par condensation de l'acide cyanacétique et de monoalkylurées

Classically, the condensation of cyanoacetic acid and monoalkylurea gives 1-alkyl-6-amino-1,2,3,4-tetrahydropyrimidine-2,4-dione. However, this was verified only in two instances involving a long and delicate synthesis. The structure of the N′-cyanoacetyl-N-isobutylurea, an intermediate in the preparation of this type of pyrimidine, was confirmed by nmr. This method is capable of extension.     

Corniculoside,a New Biosidic Ester Secoiridoid from Halenia corniculata

Chemical screening of the secondary metabolites from Halenia corniculata L. (CORNAZ ), by LC/UV,LC/TSP-MS (thermospray), and LC/ES-MS (electrospray) was used for the targeted isolation of corniculoside ( 1 ), a new biosidic ester secoiridoid. The structure was established as 7-β-[(E)-4′-O-(β-D -glucopyranosyl)caffeoyloxy]-sweroside by 1D- and 2D-NMR, LC/UV, LC/MS, and FAB-MS data, in combination with chemical reactions.     

Über enolisierte Derivate der Chlorophyllreihe. 132-Desmethoxycarbonyl-173-desoxy-132,173-cyclochlorophyllid a-enol und eine Methode zur Einführung von Magnesium in porphinoide Ligandsysteme unter milden Bedingungen. (Vorläufige Mitteilung)

Enol derivatives in the chlorophyll series. 13²-Desmethoxycarbonyl-17³-desoxy-13²,17³-cyclochlorophyllide a-enol and a method for the introduction of magnesium into porphinoid ligands under mild conditions Magnesium transfer from the iodo-magnesium salt of 3,5-di-t-butyl-4-hydroxy-toluene (BHT) into methyl pheophorbide a is a fast process in methylenechloride/ether solution at ambient temperature. This procedure for the introduction of magnesium into labile chlorin ligands has made possible the preparation of a crystalline 13², 17³-cyclochlorophyllide a-enol. Concomitant use of the lithium salt of BHT facilitates the more critical insertion of magnesium into methyl bacteriopheophorbide a. The preparative success of these magnesium transfers depends crucially upon the solvent system used. Under conditions where the complexation of methyl pheophorbide a with iodo-magnesium-BHT is essentially complete within 2 minutes at 12° in methylenechloride/ether solution, strong inhibition of the magnesium transfer is observed by cosolvents such as pyridine, dimethylacetamide, dioxan or tetrahydrofuran.