Cooperative Metal Binding and Helical Folding in Model Peptides of Treble‐Clef Zinc Fingers

Synergy in zinc fingers : The comparison between peptide folding and metal binding properties of two model peptides of treble‐clef zinc fingers presenting high affinities for zinc and cobalt reveals a cooperative effect: the metal folds the peptide into a α‐helix, which in turn strengthens the metal core.

     

Comparison of surface properties between kaolin and metakaolin in concentrated lime solutions

The surface adsorption of calcium hydroxide onto kaolin and metakaolin was investigated by monitoring with atomic emission spectroscopy and pH measurements the amounts of ions left in solution after exposing clays to calcium hydroxide solutions of various concentrations. Both clays adsorb calcium and hydroxyl ions but differently. Kaolin adsorbs calcium hydroxide not only at the edges of the clay particles but also onto the basal faces. The adsorbed hydrated calcium ions form a layer on the clay particle surfaces, preventing further dissolution of the clay mineral platelet. Metakaolin shows high pozzolanic activity, which provides the quick formation of hydrated phases at the interfaces between metakaolin and lime solutions. The nature of the hydration products has been investigated using X-ray diffraction (XRD) and differential thermal analysis (DTA). The most important hydrated phases like CSH (hydrated calcium silicate) and C₂ASH₈ (gehlenite) have been identified.     

Probing helium interfaces with light scattering: From fluid mechanics to statistical physics

We have investigated the formation of helium droplets in two physical situations. In the first one, droplets are atomised from superfluid or normal liquid by a fast helium vapour flow. In the second, droplets of normal liquid are formed inside porous glasses during the process of helium condensation. The context, aims, and results of these experiments are reviewed, with focus on the specificity of light scattering by helium. In particular, we discuss how, for different reasons, the closeness to unity of the index of refraction of helium allows in both cases to minimise the problem of multiple scattering and obtain results which it would not be possible to get using other fluids.     

Stabilization of the Low‐Spin State in a Mononuclear Iron(II) Complex and High‐Temperature Cooperative Spin Crossover Mediated by Hydrogen Bonding

The tetrapyridyl ligand bbpya (bbpya=N,N‐bis(2,2′‐bipyrid‐6‐yl)amine) and its mononuclear coordination compound [Fe(bbpya)(NCS)₂] ( 1 ) were prepared. According to magnetic susceptibility, differential scanning calorimetry fitted to Sorai’s domain model, and powder X‐ray diffraction measurements, 1 is low‐spin at room temperature, and it exhibits spin crossover (SCO) at an exceptionally high transition temperature of T_1/2=418 K. Although the SCO of compound 1 spans a temperature range of more than 150 K, it is characterized by a wide (21 K) and dissymmetric hysteresis cycle, which suggests cooperativity. The crystal structure of the LS phase of compound 1 shows strong N?H???S intermolecular H‐bonding interactions that explain, at least in part, the cooperative SCO behavior observed for complex 1 . DFT and CASPT2 calculations under vacuum demonstrate that the bbpya ligand generates a stronger ligand field around the iron(II) core than its analogue bapbpy (N,N′‐di(pyrid‐2‐yl)‐2,2′‐bipyridine‐6,6′‐diamine); this stabilizes the LS state and destabilizes the HS state in 1 compared with [Fe(bapbpy)(NCS)₂] ( 2 ). Periodic DFT calculations suggest that crystal‐packing effects are significant for compound 2 , in which they destabilize the HS state by about 1500 cm^?1. The much lower transition temperature found for the SCO of 2 compared to 1 appears to be due to the combined effects of the different ligand field strengths and crystal packing.     

Étude des propriétés électriques des surfaces réelles d'antimoniure de gallium

Light effects on real surfaces of gallium antimonide are studied by the classical Kelvin method. After having made obvious the presence of slow states detectable for light energy higher than 2 eV, contact potential variations are studied during illumination and on their coming back to equilibrium in darkness. To explain the observed phenomenon we propose a simple model, and then a more sophisticated one based on the existence of a surface trap continuum with different time constants.     

The use of Gd-DOTA in magnetic resonance imaging of experimentally induced mammary tumors

Gd-DOTA contrast enhancement of MR images was evaluated on induced mammary tumors in female rats. A single intravenous injection of the carcinogenic N-nitrosourea ENU was administered to Wistar rats; this simple treatment led to a high percentage of mammary tumors without causing death. All the induced tumors were adenocarcinoma and their heterogeneousness depended on their size. The induced tumors did not have intra- or extravascular inflammatory spaces caused by heterotopic lesions, as is the case with implanted tumors. Before injection of Gd-DOTA, appearance of the patchy internal structure was clearly demonstrated on spin-echo images performed with long repetition times. Three doses of the paramagnetic contrast agent (0.1, 0.2, and 0.5 mmol/kg) were evaluated on two different T1-weighted MR sequences. Images were recorded before and repeatedly after intravenous injection of Gd-DOTA, and signal intensities and relaxation times were measured. On images acquired with the spin-echo 500/28 as well as the inversion-recovery 928/26/300 sequences, the results showed that 0.2 mmol/kg Gd-DOTA was the optimal dose for contrast enhancement and for clear visualization of the heterogeneousness of the mammary tumor.     

Radiative Auger emission in Ne K X-ray spectra

Radiative Auger emission intensity in K X-rays from neon was measured following electron bombardment by 1 to 2 keV electrons. The measured relative intensities of this process are in good agreement with calculations of Dyall using correlated final-state wavefunctions.