Multiblock Copolymers Based on Highly Crystalline Polyethylene and Soft Poly(ethylene-co-butadiene) Segments: Towards Polyolefin Thermoplastic Elastomers

Block copolymers based on polyethylene (PE) and ethylene butadiene rubber (EBR) were obtained by successive controlled coordinative chain transfer polymerization (CCTP) of a mixture of ethylene and butadiene (80/20) and pure ethylene. EBR-b-PE diblock copolymers were synthesized using the {Me₂Si(C₁₃H₈)₂Nd(BH₄)₂Li(THF)}₂ complex in combination with n-butyl,n-octyl magnesium (BOMAG) used as both the alkylating and chain transfer agent (CTA). Triblock and multiblock copolymers featuring highly semi-crystalline PE hard segments and soft EBR segments were further obtained by the development of a bimetallic CTA, the pentanediyl-1,5-di(magnesium bromide) (PDMB). These new block copolymers undergo crystallization-driven organization into lamellar structures and exhibit a variety of mechanical properties, including excellent extensibility and elastic recovery in the case of triblock and multiblock copolymers.     

PHOTOOXIDATION PRODUCTS OF MEROCYANINE 540 FORMED UNDER PREACTIVATION CONDITIONS FOR TUMOR THERAPY

In order to gain insight into the preactivation of merocyanine 540 (MC540) 1 for the photodynamic therapy (Gulliya et al., 1990a, Photochem. Photobiol. 52, 831-838) its photo-oxidation was investigated. After irradiation of MC540 1 on a preparative scale three main photodegradation products were isolated with 16-20% yields. They turned out to be derivatives of benzoxazole, thiouracil and thiohydantoin with the structures 4, 5 and 6, respectively. It may be possible that they contribute to the cytostatic and antiviral activity of preactivated MC540 1.     

Multiple resonance heteronuclear decoupling under MAS: dramatic increase of spectral resolution at moderate magnetic field and MAS frequencies

The effects of multiple-resonance heteronuclear decoupling under magic angle spinning (MAS) on the resolution of one-dimensional ¹⁹F and ³¹P and various two-dimensional MAS NMR spectra and on the residual non-refocusable coherence lifetimes in fluorinated aluminophosphate AlPO₄-CJ2, i.e. a compound that contains numerous highly abundant nuclei but no homonuclear spin bath, has been investigated. The design of the four-channel (¹H, ¹⁹F, ²⁷Al, ³¹P) MAS probe used for this study is first described. ¹H and ¹H–²⁷Al double-resonance decouplings allows lengthening the optimized transverse relaxation and increasing the resolution in the ¹⁹F and ³¹P dimensions. Under the application of multi-nuclear decoupling, a two-dimensional ¹⁹F–³¹P CP-HETCOR correlation spectrum for AlPO₄-CJ2 is recorded with unprecedented high-resolution in the two dimensions. Moreover, because ¹H-decoupling increases the ¹⁹F , it has been applied during the entire duration of the 2D NMR experiments, allowing the direct use of residual small interactions to generate ¹⁹F–¹⁹F and ¹⁹F–²⁷Al 2D NMR correlation spectra in AlPO₄-CJ2.     

The cycloaddition way to novel deoxy disaccharide analogs

A novel heterocycloaddition merges 2-thiono-3-ketolactones with carbohydrate glycals to afford materials which resemble disaccharides with an O-glycosidic linkage at the anomeric center and a thioether linking both C-2 and C-2′, thus creating a third heterocyclic ring. Upon desulfurization, these novel cycloadducts afford materials which are models for 2-deoxydisaccharides. Studies with two keto lactones and seven glycals are described.     

Towards two-dimensional electrophoresis mapping of the cerebrospinal fluid proteome from a single individual

We test the ability of state-of-the-art two-dimensional electrophoresis (2-DE) technology to enable the proteome mapping of ante mortem cerebrospinal fluid (CSF) from a single individual. Using the sensitive technologies of a fluorescent protein stain and fluorescence laser scanning of 2-DE gels, combined with matrix-assisted laser desorption/ionization-time of flight/time of flight-mass spectrometry (MALDI-TOF/TOF-MS) for protein identification, a highly detailed 2-DE map of the CSF proteome was created. The 2-DE map contains 600 identified spots representing 82 different proteins. Of the 82 proteins identified, 25 have not appeared in any previously published 2-DE map of CSF, and 11 have not been previously reported to exist in CSF. Most of the identifications originate from an ante mortem CSF sample collected from a single hydrocephalus patient. A supplemental map created from neurologically normal patients is also presented. A webpage with protein identification and scoring information from both maps is available at http://www.leelab.org/csfmap.     

Synthesis and biomimetic rearrangement of a chiral diterpene dioxide

As pan of a biomimetic approach towards me marine triterpene teurilene (2), the synthesis of the chiral diepoxide 3 is described. Aiming at the synthesis of the squalene tetraepoxide 1, double Sharpless epoxidation led to the intermediate bisglycidic alcohol 7 being subject to a stereochemical analysis.     

Une méthode inverse d'ordre un pour les problèmes de complétion de données

An iterative resolution method for inverse Cauchy problems is presented. The successive iterations satisfy the equilibrium equations exactly. Numerical simulations prove the accuracy of the method and its ability to solve Cauchy problems when the domain boundary is not regular. To cite this article: A. Cimetière et al., C. R. Mecanique 333 (2005).