Flavonoids and iridoids from Stachys corsica

Two flavonoid glycosides containing acetylated allose, and two iridoid glucosides were obtained from a EtOH extract of Stachys corsica, an endemic plant of Sardinia and Corsica. All the compounds have previously been isolated from other species of Stachys.     

Diffusion-controlled solid-state reactions of spherical particles, a general model for multiphase binary systems

The formal treatment of the diffusion-controlled growth of n binary compounds with narrow homogeneity range during the reaction of a sphere of reactant A immersed in reactant B is presented and discussed. Both constituents are assumed to be mobile. The reaction products are assumed to grow simultaneously as uniform and compact concentric layers with ideal contact at the interfaces as well as at the external surface of the sphere. The kinetic equations follow from the coupling between chemical reactions and partitioning of the diffusion flux at phase boundaries. The results for the formation of two and three compounds are presented. The influence of the initial radius of the sphere, of the relative magnitude of the kinetic constants, and of the volume variation is discussed in detail.     

LiI-doped N,N-dimethyl-pyrrolidinium iodide, an archetypal rotator-phase ionic conductor

N,N-Dimethyl-pyrrolidinium iodide, and the effect of doping with LiI, has been investigated using DSC, NMR, and impedance spectroscopy. It was found that the addition of a small amount of LiI enhances the ionic conductivity by up to 3 orders of magnitude for this ionic solid. Furthermore, a slight decrease in phase transition onset temperatures, as well as the appearance of a superimposed narrow line in the (1)H NMR spectra with dopant, suggest that the LiI facilitates the mobility of the matrix material, possibly by the introduction of vacancies within the lattice. (7)Li NMR line width measurements reveal a narrow Li line width, decreasing in width and increasing in intensity with temperature, indicating mobile Li ions.     

Aggregation behavior of tetrakis(4-sulfonatophenyl)porphyrin in AOT/water/decane microemulsions

AOT/water/decane microemulsions have been used to entrap the water-soluble 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (TPPS4). Quasi-elastic light scattering technique has confirmed the confinement of the porphyrin and its various aggregates into the inner water pool. Various species have been detected as function of the size of the microemulsions, concentration of the porphyrin, pH, and aging of the solutions by using a combination of UV-vis absorption, steady fluorescence emission, fluorescence lifetime measurements, and time-resolved fluorescence anisotropy. Under neutral pH conditions, the porphyrin is present as the free base monomer (S414) in the inner water compartment, and it is free to rotate when the size of the droplet is large enough and the porphyrin concentration is low. On increasing the concentration and/or decreasing the microemulsion size, a H-dimer of the free base (S406) is prevalently formed. Aging both the S414 and S406 species leads to the formation of a new species (S424), which has been postulated as a H-type dimer of the diacid porphyrin. On decreasing the pH, the species S414 and S406 almost instantaneously convert into the diacid porphyrin, which is monomeric (S434). This latter is an intermediate in the eventual formation of J-aggregated TPPS4 (S490). A marked stability has been observed for the S424 species, which do not interconvert on changing the pH of the bulk aqueous phase.     

Novel oxa-di-pi-methane and Norrish type I reactions in the S2 (pi,pi*) excited state of a series of beta,gamma-unsaturated ketones

[reaction: see text] Beta,gamma-unsaturated methyl ketones with electron-withdrawing groups at the gamma-position of the ene moiety undergo ODPM rearrangements and Norrish type I reactions on direct irradiation at 254 nm. The results are consistent with the involvement of alkene S(2) (pi,pi*) as reactive excited states in these processes.     

A Note on the analytic solutions of the Camassa–Holm equation

In this Note we are concerned with the well-posedness of the Camassa–Holm equation in analytic function spaces. Using the Abstract Cauchy–Kowalewski Theorem we prove that the Camassa–Holm equation admits, locally in time, a unique analytic solution. Moreover, if the initial data is real analytic, belongs to $H^s(\mathbb{R})$ with $s>3/2$, $6u_0{6}_{L^1}<\infty$ and $u_0?u_{0xx}$ does not change sign, we prove that the solution stays analytic globally in time. To cite this article: M.C. Lombardo et al., C. R. Acad. Sci. Paris, Ser. I 341 (2005).     

How the First Partial Transpose was Written

We tell the tale of the first writing of a partial transpose, without guaranteeing historical authenticity. Dedicated to Prof. Asher Peres, Haifa, on the occasion of his 70th birthday.     

Spontaneous emission in the near field of two-dimensional photonic crystals

We show theoretically that photonic crystal membranes cause large variations in the spontaneous emission rate of dipole emitters, not only inside but also in the near field above the membranes. Our three-dimensional finite-difference time-domain calculations reveal an inhibition of more than five times and an enhancement of more than ten times for the spontaneous emission rate of emitters with select dipole orientations and frequencies. Furthermore, we demonstrate theoretically the potential of a nanoscopic emitter attached to the end of a glass fiber tip as a local probe for mapping the large spatial variations of the photonic crystal local radiative density of states. This arrangement is promising for on-command modification of the coupling between an emitter and the photonic crystal in quantum optical experiments.     

Rheological properties of paraffin suspensions of surface-modified alumina powder for low-pressure injection moulding

Due to the hygroscopic nature of fine alumina powders, the presence of water may have a detrimental effect on the rheological properties of a suspension in melted paraffin for low-pressure injection moulding (LPIM). For this reason, a modification of the powder surface from hydrophilic to hydrophobic is essential for the production of high-quality moulded ceramics. In our paper, the efficiency of the application and the chemisorption of protective monomolecular layers of a long-chain carboxylic acid or its salts will be presented. The effect of the powder treatment on the shear viscosity and the viscoelastic properties of the suspensions for LPIM as well as on their stability in terms of the detrimental effect of water will be discussed.This paper was presented at the first Annual European Rheology Conference (AERC) held in Guimarães, Portugal, September 11-13, 2003.     

Folding and unfolding of an elastinlike oligopeptide: "inverse temperature transition," reentrance, and hydrogen-bond dynamics

The temperature-dependent behavior of a solvated oligopeptide, GVG(VPGVG), is investigated. Spectroscopic measurements, thermodynamic measurements, and molecular dynamics simulations find that this elastinlike octapeptide behaves as a two-state system that undergoes an "inverse temperature" folding transition and reentrant unfolding close to the boiling point of water. A molecular picture of these processes is presented, emphasizing changes in the dynamics of hydrogen bonding at the protein/water interface and peptide backbone librational entropy.