Stable windings on hyperbolic surfaces

Let ℳ be a geometrically finite hyperbolic surface with infinite volume, having at least one cusp. We obtain the limit law under the Patterson-Sullivan measure on T ¹ℳ of the windings of the geodesics of ℳ around the cusps. This limit law is stable with parameter 2δ− 1, where δ is the Hausdorff dimension of the limit set of the subgroup Γ of M?bius isometries associated with ℳ. The normalization is t ^{−1/(2δ−1)}, for geodesics of length t. Our method relies on a precise comparison between geodesics and diffusion paths, for which we need to approach the Patterson-Sullivan measure mentioned above by measures that are regular along the stable leaves. Received: 8 October 1999 / Revised version: 2 June 2000 / Published online: 21 December 2000     

EPR study of dialkyl nitroxides as probes to investigate the exchange of solutes between the ligand shell of monolayers of protected gold nanoparticles and aqueous solutions

EPR spectroscopy has been used to study the interaction of para-substituted benzyl hydroxyalkyl nitroxides with the monolayer of water-soluble protected gold cluster made by a short alkyl chain and a triethylene glycol monomethyl ether unit. The inclusion of nitroxide probes in the more hydrophobic environment of the monolayer gave rise to a reduction of the value of both nitrogen and beta-proton hyperfine splittings. The spectra also showed selective line broadening attributed to modulation of the spectroscopic parameters as the result of exchange between free and complexed nitroxide. The rate constants were obtained by analyzing the EPR line shape variations as functions of nanoparticle concentration and temperature. This represents, to the best of our knowledge, the first determination of rate constants for the solubilization of organic substrates in a monolayer-protected cluster.     

Trifluoroethanol: key solvent for palladium-catalyzed polymerization reactions

A series of cationic palladium complexes of general formula [Pd(CH₃)(NCCH₃)(N-N)][X] (N-N = phen 1, 3-sec-butyl-1,10-phenanthroline (3-sBu-phen) 2, bpy 3, (−)-(S,S)-3,3′-(1,2-dimethylethylenedioxy)-2,2′-bipyridine (bbpy) 4, (+)-(R)-3,3′-(1-methylethylenedioxy)-2,2′-bipyridine (pbpy) 5, N,N′-bis(2,6-diisopropylphenyl)-2,3-butanediimine (iso-DAB) 6; , OTf (OTf = triflate) b) containing different nitrogen-donor ligands were prepared from the corresponding neutral chloro derivatives [Pd(CH₃)(Cl)(N-N)] (1c-6c). They were characterized by ¹H NMR spectroscopy and elemental analysis. Single crystals suitable for X-ray determination were obtained for complexes [Pd(CH₃)(NCCH₃)(bbpy)][PF₆] (4a), [Pd(CH₃)(NCCH₃)(iso-DAB)][PF₆] (6a) and [Pd(Cl)₂(bbpy)] (4c′). The latter is the result of an exchange reaction of the methyl group, present in complex 4c, with a chloride, that occurred after dissolution of 4c in CDCl₃, for 1 week at 0 °C. The catalytic behavior of complexes 1a-5a and 1b-5b in the CO/styrene copolymerization was studied in CH₂Cl₂ and 2,2,2-trifluoroethanol (TFE) evidencing the positive effect of the fluorinated alcohol both in terms of productivity and molecular weight values of the polymers obtained. Influence of the nitrogen ligand, the anion and the reaction time in both solvents were investigated and is discussed in detail. Encouraging preliminary results were also obtained in the synthesis of polyethylene, in TFE, catalyzed by [Pd(CH₃)(NCCH₃)(iso-DAB)][PF₆] (6a).     

IR and FIR Spectroscopy of 13CH3I

We have investigated the ¹³CH₃I isotopomer of methyl iodide as a source of Far Infrared (FIR) laser radiation using the optical pumping technique. The molecule is pumped by using a pulsed waveguided CO₂ laser, driven by a novel all solid state power supply that lases on the 10HP band as well as the regular bands. We discovered and assigned two new FIR laser emissions and we give further spectroscopic information about polarization and pump frequency offset for five already known lines.     

The influence of the DX center on the capacitance of schottky barriers in n-type AlGaAs

The significance of both the density N, and the apparent built-in voltage V_a, as usually obtained from C-V measurements on Schottky barriers containing DX centers, is clarified. It is also shown that, owing to the non-equilibrium occupancy of the DX center, at low temperature the electron density in the flat-band region depends on the cooling rate of the sample.     

Peri-implant osteogenesis in health and osteoporosis

Long-term clinical success of endosseous dental implants is critically related to a wide bone-to-implant direct contact. This condition is called osseointegration and is achieved ensuring a mechanical primary stability to the implant immediately after implantation. Both primary stability and osseointegration are favoured by micro-rough implant surfaces which are obtained by different techniques from titanium implants or coating the titanium with different materials. Host bone drilled cavity is comparable to a common bone wound. In the early bone response to the implant, the first tissue which comes into contact with the implant surface is the blood clot, with particular attention to platelets and fibrin. Peri-implant tissue healing starts with an inflammatory response as the implant is inserted in the bone cavity, but an early afibrillar calcified layer comparable to the lamina limitans or incremental lines in bone is just observable at the implant surface both in vitro than in vivo conditions. Just within the first day from implantation, mesenchymal cells, pre-osteoblasts and osteoblasts adhere to the implant surface covered by the afibrillar calcified layer to produce collagen fibrils of osteoid tissue. Within few days from implantation a woven bone and then a reparative trabecular bone with bone trabeculae delimiting large marrow spaces rich in blood vessels and mesenchymal cells are present at the gap between the implant and the host bone. The peri-implant osteogenesis can proceed from the host bone to the implant surface (distant osteogenesis) and from the implant surface to the host bone (contact osteogenesis) in the so called de novo bone formation. This early bone response to the implant gradually develops into a biological fixation of the device and consists in an early deposition of a newly formed reparative bone just in direct contact with the implant surface. Nowadays, senile and post-menopausal osteoporosis are extremely diffuse in the population and have important consequences on the clinical success of endosseous dental implants. In particular the systemic methabolic and site morphological conditions are not favorable to primary stability, biological fixation and final osseointegration.

An early good biological fixation may allow the shortening of time before loading the implant, favouring the clinical procedure of early or immediate implant loading. Trabecular bone in implant biological fixation is gradually substituted by a mature lamellar bone which characterizes the implant ossoeintegration. As a final consideration, the mature lamellar bone observed in osseointegrated implants is not always the same as a biological turnover occurs in the peri-implant bone up to 1 mm from the implant surface, with both osteogenesis and bone reabsorption processes.