Dosage par spectrophotometrie dans l'ultraviolet de l'lon fluorure a l'aide des chelates : Cerium(iii)-alizarine complexon ou lanthane(iii)-alizarine complexon,en presence de dimethylsulfoxyde

A comparative study of the absorption spectra, in the visible and the ultraviolet regions, of the ternary complex cerium(III)-alizarin fluorine blue-fluoride and lanthanum-alizarin fluorine blue-fluoride has been made both in aqueous medium and in media containing 25% dimethylsulfoxide. This solvent very greatly enhances the sensitivity of the reaction in every case; moreover, since it has no important absorption band in the ultraviolet region, it can be used advantageously in exploring the spectra of the above-mentioned fluoride chelates in that region. Determinations of fluorides, with a final spectrophotometric measurement at 625 or 283 nm are described. The interference of 8 ions was studied.     

A study of the direct spectrophotometric determination of fluoride ion with the cerium(3)-alizarin fluorine blue complex

Several workers have observed that the sensitivity of the cerium (ItII)-alizarin fluorine blue method for the spectrophotometric determination of microgram amounts of fluoride may be enhanced by addition of certain solvents. The present study proves that the use of an aqueous 25% v/v solution of dimethylsulfoxide, the most polar aprotic solvent, enhances to a maximum the sensitivity of the reaction and increases its speed. Two procedures, allowing the determination of 1–25 μg fluoride ion, are described: the best pH value is 4.1 and the spectrophtotometric measurements are carried out at 625 or 630 nm. The interferences of 12 ions were studied.     

Optical pump-terahertz probe spectroscopy of dyes in solutions: probing the dynamics of liquid solvent or solid precipitate?

The optical pump-terahertz probe spectroscopy was used together with ab initio calculations and molecular dynamics simulations to investigate ultrafast dynamics following electronic excitation of Coumarin 153 and TBNC (2,11,20,29-tetra-tert-butyl-2,3-naphtalocyanine) dyes in polar solvents. By scanning the terahertz waveform for different pump-probe delays this experimental technique allows us to obtain two dimensional spectra directly reflecting the temporal response of the system. A distinct signal was obtained for TBNC in chloroform, 2-propanol, and n-butanol, while no signal was recorded for Coumarin 153 in either of these solvents. We explain the nonequilibrium signal detected in TBNC solutions by the presence of a solid, polycrystalline phase of the dye resulting from irradiating the solution by intense optical pulses.     

Self-organized formation of rhomboidal nanopyramids on fcc(110) metal surfaces

We report on the far from equilibrium self-organized morphologies obtained after Xe ion irradiation of the Rh(110) and Cu(110) surfaces. Here we experimentally identify by means of high resolution LEED a novel interfacial state characterized by a rhomboidal pyramid islanding with majority steps oriented along nonequilibrium low-symmetry directions. The formation of the novel rhomboidal pyramid state and the transition to the well-known rippled phases results from a delicate interplay of kinetic processes which are controlled by acting on temperature, ion flux, and impact energy.     

Poly(ethylene glycol) Surface Coated Magnetic Particles

Summary: A methacrylate‐functionalized poly(ethylene glycol) macromonomer was copolymerized at the surface of methacrylate‐derivatized maghemite nanoparticles. After silylation of the magnetic core with methacryloxypropyltrimethoxysilane, two grafting procedures based on either a direct copolymerization reaction in water or an inverse emulsion polymerization were compared. A direct copolymerization led to low polymer surface amounts, whereas an inverse emulsion process allowed nanocomposite particles containing up to 90 wt.‐% polymer to be obtained.

TEM picture of maghemite‐PEG hybrid particles.     

Measuring local and global vibration modes in model plants

Model plants are extensively used in biological studies, and their mechanical behaviour needs to be better understood, in relation to studies in mechanoperception for instance. We present here the first approach to derive experimentally the modal parameters of two of these plants, Arabidopsis thaliana and Populus tremula × alba. A classical sinusoidal sweep excitation is used, with a measurement of displacements based on LKT optical flow tracking, followed by a bi-orthogonal decomposition (BOD). This allows us to estimate several modal frequencies for each plant, as well as the corresponding spatial localizations of deformation. Analyzing the modal frequencies, we show that global and local modes correspond to distinct ranges of frequencies and depend differently on plant size. Possible phenotyping applications are then discussed.     

The status of strontium in biological apatites: an XANES/EXAFS investigation

Osteoporosis represents a major public health problem through its association with fragility fractures. The public health burden of osteoporotic fractures will rise in future generations, due in part to an increase in life expectancy. Strontium‐based drugs have been shown to increase bone mass in postmenopausal osteoporosis patients and to reduce fracture risk but the molecular mechanisms of the action of these Sr‐based drugs are not totally elucidated. The local environment of Sr²⁺ cations in biological apatites present in pathological and physiological calcifications in patients without such Sr‐based drugs has been assessed. In this investigation, X‐ray absorption spectra have been collected for 17 pathological and physiological calcifications. These experimental data have been combined with a set of numerical simulations using the ab initioFEFF9 X‐ray spectroscopy program which takes into account possible distortion and Ca/Sr substitution in the environment of the Sr²⁺ cations. For selected samples, Fourier transforms of the EXAFS modulations have been performed. The complete set of experimental data collected on 17 samples indicates that there is no relationship between the nature of the calcification (physiological and pathological) and the adsorption mode of Sr²⁺ cations (simple adsorption or insertion). Such structural considerations have medical implications. Pathological and physiological calcifications correspond to two very different preparation procedures but are associated with the same localization of Sr²⁺versus apatite crystals. Based on this study, it seems that for supplementation of Sr at low concentration, Sr²⁺ cations will be localized into the apatite network.     

Rational design of lanthanide binding peptides

Lanthanide-binding peptides are very attractive for the design of bioprobes. Indeed, they combine the amazing properties of lanthanide ions, such as their time-resolved luminescence (Eu, Tb) or electronic relaxation (Gd) to the characteristics of the peptide scaffold, such as large solubility in water and ability to recognize biological substrates. Peptides derived from natural amino acids are reviewed in a first section. Some of their lanthanide complexes have already demonstrated their efficiency in determining protein structures and functions. Then, we will show how insertion of chelating unnatural amino acids modulates peptide-lanthanide complexes properties, such as luminescence and stability.