A powerful route to C-functionalised tetraazamacrocycles

The bisaminal template approach represents a powerful synthetic tool for the preparation of various C-functionalised tetraazacycloalkanes which are efficient precursors of bifunctional chelating agents.     

Complex formation of peroxouranyl (and uranyl) with polyaminocarboxylate ligands

Complexation of the uranyl ion (UO₂²⁺) and of the peroxouranyl species (UO₄) by some polyaminocarboxylate ligands has been investigated in solution (3M NaClO₄) at 25°C. The logarithms of the cumulative formation constants of the UO₂²⁺ chelates formed are: UO₂edta^2? (15.65), UO₂Hedta^? (18.59), (UO₂)₂edta (20.24); UO₂edda (16.02); UO₂Hnta (12.19); UO₂ida (9.63), UO₂H₂(ida)₂ (23.80). The equilibrium UO₂²⁺ + H₂O₂ ? UO₄ + 2H⁺ has a stability log K = ?3.99. The peroxocomplexes formed are UO₄Hedda^? (14.81, expressed from UO₂²⁺ and H₂O₂) and UO₄Hnta^2? (8.50). Solution structures of the chelates are proposed.     

Synthese et caracterisation par RMN 1H d'alkyl(aryl)ferriporphyrines a liaison σ metalcarbone

A series of alkyl(aryl)iron(III) porphyrins with a metalcarbon σ bond has been prepared either by action of an organomagnesium compound on iron(III) chloride porphyrins or by oxidative addition of alkyl halides to iron(I) porphyrins. ¹H NMR data have been used to characterize the products obtained.     

Experimental evidence of s-wave superconductivity in bulk CaC6

The temperature dependence of the in-plane magnetic penetration depth, lambda(ab)(T), has been measured in a c-axis oriented polycrystalline CaC(6) bulk sample using a high-resolution mutual inductance technique. A clear exponential behavior of lambda(ab)(T) has been observed at low temperatures, strongly suggesting isotropic s-wave pairing. Data fit using the standard BCS theory yields lambda(ab)(0) = (720 +/- 80) A and delta(0) = (1.79 +/- 0.08) meV. The ratio 2delta(0)/k(B)T(c) = (3.6 +/- 0.2) gives indication for a weakly coupled superconductor.     

Braiding minimal sets of vector fields

We extend a classical but fundamental theorem of knot and braid theories to describe the geometry of nonsingular minimal sets of 3-dimensional flows.

     

Enhancement of superconductivity and evidence of structural instability in intercalated graphite CaC6 under high pressure

We measured the temperature dependent resistivity, varrho(T), of the intercalated graphite superconductor CaC6 as a function of pressure up to 16 GPa. We found a large linear increase of critical temperature, Tc, from the ambient pressure value 11.5 K up to 15.1 K, the largest value for intercalated graphite, at 7.5 GPa. At approximately 8 GPa, a jump of varrho and a sudden drop of Tc down to approximately 5 K indicates the occurrence of a phase transition. Our data analysis suggests that a pressure-induced phonon softening related to an in-plane Ca phonon mode is responsible for the Tc increase and that higher pressures greater, similar8 GPa lead to a structural transition into a new phase with a low Tc less, similar3 K.     

Development of an analytical procedure for quantifying the underivatized neurotoxin β-N-methylamino-l-alanine in brain tissues

The cyanotoxin β-methylamino-l-alanine (BMAA) has received renewed attention as an environmental risk factor for sporadic cases of amyotrophic lateral sclerosis (ALS) (Nunn et al., Brain Res 410:375–379, 1987). The aim of the present study was to develop and to validate an analytical procedure that allows the quantification of native BMAA and of its natural isomer, 2,4 diaminobutyric acid (DAB), in brain tissues. An analytical procedure was previously reported by our group for the determination of underivatized BMAA in environmental samples. It included a step of sample clean-up by solid phase extraction (SPE) with a mixed-mode sorbent and the analyses were performed by LC/MS-MS using hydrophilic interaction chromatography and multiple reactions monitoring scan mode. As brain tissues have a higher lipid content, the crucial step of sample clean-up had been optimized by evaluating the efficiency of the addition of a liquid/liquid extraction step prior to the SPE procedure or alternatively, of washing steps to the SPE extraction procedure. The efficiency was checked by visualizing the complexity of the resulting chromatograms in LC/MS and their performance by using spiked brain samples. The optimized analytical procedure, including a washing step with cyclohexane to the SPE with a recovery yield close to 100 %, was validated using the total error approach and allowed the quantification of BMAA in a concentration level ranging from 20 to 1,500 ng/g in brain samples. Finally, the feasibility of implementation of this procedure was verified in human brain samples from two patients who died of ALS.