Magnetic properties and specific heat of garnet Ca3Fe2Ge3O12

Owing to a four-sublattice molecular field model we have found a good agreement between various experimental results of susceptibility, magnetization and magnetic specific heat obtained on the garnet Ca₃Fe₂Ge₃O₁₂.     

Production of high power tunable UV laser emission by second-harmonic generation fro, a rhodamine 6G dye laser

The generation of tunable UV radiation in the 280–310 nm range by doubling the output frequency of a flashlamp-excited Rhodamine 6 G dye laser is described. By using KDP and ADP crystals, conversion efficiencies of respectively 9.4% and 8.4% are obtained with UV output energies up to 50 mJ.     

Direct investigation of spin Hamiltonians DS2z by measuring magnetization during intense pulsed fields

We describe a new method for investigating the DS²_z spin Hamiltonians (D > 0) using intense pulsed magnetic fields at low temperature: the level crossings occuring during the pulse result in sharp increases in the magnetization. By this method, we measured D = 12.2 ± 0.2 cm^-1 in ferrous fluosilicate.     

Capillary electrophoresis analysis of glucooligosaccharide regioisomers

Complex gluco-oligosaccharide mixtures of two regioisomer series were successfully separated by CE. The gluco-oligosaccharide series were synthesized, employing a dextransucrase from Leuconostoc mesenteroides NRRL B-512F, by successive glucopyranosyl transfers from sucrose to the acceptor glucose or maltose. The glucosyl transfer to both acceptors, occurring through the formation of alpha1-->6 linkages, differed for the two series only in the glucosidic bond to the reducing end namely alpha1-->6 or alpha1-->4 bond for glucose or maltose acceptor, respectively. Thus, the combination of the two series results in mixed pairs of gluco-oligosaccharide regioisomers with different degrees of polymerization (DP). These regioisomer series were first derivatized by reductive amination with 9-aminopyrene-1,4,6-trisulfonate (APTS). Under acidic conditions using triethyl ammonium acetate as electrolyte, the APTS-gluco-oligosaccharides of each series were separated enabling unambiguous size determination by coupling CE to electrospray-mass spectrometry. However, neither these acidic conditions nor alkaline buffer systems could be adapted for the separation of the gluco-oligosaccharide regioisomers arising from the two combined series. By contrast, increased resolution was observed in an alkaline borate buffer, using differential complexation of the regioisomers with the borate anions. Such conditions were also successfully applied to the separation of glucodisaccharide regioisomers composed of alpha1-->2, alpha1-->3, alpha1-->4, and alpha1-->6 linkages commonly synthesized by glucansucrase enzymes.     

Fission of a multiphase membrane tube

A common mechanism for intracellular transport is the use of controlled deformations of the membrane to create spherical or tubular buds. While the basic physical properties of homogeneous membranes are relatively well known, the effects of inhomogeneities within membranes are very much an active field of study. Membrane domains enriched in certain lipids, in particular, are attracting much attention, and in this Letter we investigate the effect of such domains on the shape and fate of membrane tubes. Recent experiments have demonstrated that forced lipid phase separation can trigger tube fission, and we demonstrate how this can be understood purely from the difference in elastic constants between the domains. Moreover, the proposed model predicts time scales for fission that agree well with experimental findings.     

Theoretical investigation of substituted anthraquinone dyes

We have investigated with computational chemistry techniques the visible spectra of substituted anthraquinones. A wide panel of theoretical methods has been used, with various basis sets and density functional theory (DFT) functionals, in order to assess a level of theory that would lead to converged excitation energies. It turns out that the hybrid Becke-Lee-Yang-Parr and Perdew-Burke-Erzenrhof functionals with the 6-31G (d,p) atomic basis set provide reliable lambda(max) when the solvent effects are included in the model. Combining the results of both DFT schemes allows the prediction of lambda(max) with a standard deviation limited to 13 nm.     

Reassigning hydrogen-bond centering in dense ice

Hydrogen bonds in H2O ice change dramatically upon compression. Thereby a hydrogen-bonded molecular crystal, ice VII, is transformed to an atomic crystal, ice X. Car-Parrinello simulations reproduce the features of the x-ray diffraction spectra up to about 170 GPa but allow for analysis in real space. Starting from molecular ice VII with static orientational disorder, dynamical translational disordering occurs first via creation of ionic defects, which results in a systematic violation of the ice rules. As a second step, the transformation to an atomic solid and thus hydrogen-bond centering occurs around 110 GPa at 300 K and no novel phase is found up to at least 170 GPa.     

Aggregation of particles settling in shear-thinning fluids

We have experimentally studied the coaxial settling of three identical non-Brownian spheres in a shear-thinning fluid at small Reynolds numbers. While settling, the particles create corridors of reduced viscosity in their wake and, if they are initially close enough to one another, they can form stable clusters. By analogy with previous results obtained on two-particle interaction in the first part of this work, we show that the particle velocities can be satisfactorily described using a first-order expression and assuming that the reduced viscosity remains constant. We report systematic experiments performed at different initial separation distances between particles and the use of our simple model allows the prediction of the settling behaviour and in particular the conditions for clusters formation. We thus show that particle aggregation can occur even for large initial distances between particles and within times that are small compared to the time scales in Newtonian fluids. Received 10 July 2002 RID="a" ID="a"e-mail: talini@fast.u-psud.fr     

A Bioinspired Synthesis of Polyfunctional Indoles

Polyfunctional indoles bearing substituents at C5 and C6 are prevalent in natural products, pharmaceuticals, agrochemicals, and materials. Owing to the remoteness of the C5 and C6 positions, indoles of this family can be difficult to prepare, and often require multistep syntheses. Herein, we describe a concise process that converts simple derivatives of tyrosine into 5,6‐difunctionalized indoles by direct oxidation of C?H, N?H, and O?H bonds. Our work draws inspiration from the biosynthetic polymerization of tyrosine to make melanin pigments, but makes an important departure to provide well‐defined indole heterocycles.