Zinc(II)-methimazole complexes: synthesis and reactivity

The tetrahedral S-coordinated complex [Zn(MeImHS)(4)](ClO4)(2), synthesised from the reaction of [Zn(ClO4)(2)] with methimazole (1-methyl-3H-imidazole-2-thione, MeImHS), reacts with triethylamine to yield the homoleptic complex [Zn(MeImS)(2)] (MeImS = anion methimazole). ESI-MS and MAS C-13-NMR experiments supported MeImS acting as a (N, S)-chelating ligand. The DFT-optimised structure of [Zn(MeImS)(2)] is also reported and the main bond lengths compared to those of related Zn-methimazole complexes. The complex [Zn(MeImS)(2)] reacts under mild conditions with methyl iodide and separates the novel complex [Zn(MeImSMe)(2)I-2] (MeImSMe = S-methylmethimazole). X-ray diffraction analysis of the complex shows a ZnI2N2 core, with the methyl thioethers uncoordinated to zinc. Conversely, the reaction of [Zn( MeImS)(2)] with hydroiodic acid led to the formation of the complex [Zn(MeImHS)(2)I-2] having a ZnI2S2 core with the neutral methimazole units S-coordinating the metal centre. The Zn-coordinated methimazole can markedly modify the coordination environment when changing from its thione to thionate form and vice versa. The study of the interaction of the drug methimazole with the complex [Zn(MeIm)(4)](2+) (MeIm = 1-methylimidazole) - as a model for Zn-enzymes containing a N-4 donor set from histidine residues shows that methimazole displaces only one of the coordinated MeIm molecules; the formation constant of the mixed complex [Zn(MeIm)(3)(MeImHS)](2+) was determined

Palladium(ii) complexes with chiral organoantimony(iii) ligands. Solution behaviour and solid state structures

The chiral compound (2-Me2NCH2C6H 4)PhSbCl (1) was obtained from (2-Me2NCH2C 6H4)Li and PhSbCl2 in 1:1 molar ratio, while (2-Me2NCH2C6H4)Mes2Sb (2) was prepared from (2-Me2NCH2C6H 4)SbCl2 and MesMgBr in 1:2 molar ratio. The compounds 1 and 2 were used to obtain the Pd(ii)/stibine complexes: [Me2NHCH 2C6H5]+[PdCl3SbCl(Ph) (C6H4CH2NMe2-2)-Sb]- (3) and [PdCl2SbMes2(C6H4CH 2NMe2-2)-N,Sb] (4). All the compounds were characterized by multinuclear NMR spectroscopy in solution, elemental analysis, mass spectrometry and single-crystal X-ray diffraction studies. In compounds 1-3 the coordination geometry around the antimony atom is pseudo-trigonal bipyramidal, while in compound 4 a tetrahedral geometry around the antimony atom is observed. Theoretical calculations at the DFT level on compounds 1-4 were used in order to gain insight into the nature of the coordinative bonds

Nitinol Carbofilm coated stents for peripheral applications: Study in the porcine model

Purpose: Testing the safety and foreign body reaction (FBR) of a nitinol self-expandable carbon-coated stent system in the porcine animal model at different follow-up (FU) periods. Methods: Fifteen minipigs received 30 carbon-coated self-expandable nitinol stents in iliac arteries. Explants were carried out at 7 (3 animals), 30 (4 animals), 90 (4 animals) and 180 (4 animals) day FU, for evaluation of acute, sub-acute and chronic biological response to the implanted devices. Histological, immunohistochemical, histomorphometric and scanning electron microscopy (SEM) analyses were performed to assess inflammatory reaction, endothelialization process, neointimal growth and cellular composition. Results: Thirty stents were successfully implanted. No mural thrombi were observed at gross examination or by angiography. Histologically no significant inflammatory reaction was detected: the stents appeared covered by a thin monolayer of endothelial cells even at 7 day FU. The neointima presented homogeneous growth and moderate thickness after 30, 90 and 180 days explants (0.38± 0.36 mm, 0.33± 0.30 mm, 0.27± 0.25 mm respectively). Internal and external elastic laminae were intact in 95% of stented arteries. Histological data validations of vessel endothelialization was obtained with SEM for the seven day follow-up group. Conclusions: This study showed good remarkable technical performances, minimal FBR and biocompatibility comparable with other available pre-clinical experimentation

Insights into the explosive eruption history of the Campanian volcanoes prior to the Campanian Ignimbrite eruption

The Campanian Volcanic Zone (CVZ) comprises multiple active volcanoes and includes the highly productive Campi Flegrei and Ischia caldera systems. These caldera volcanoes have produced probably the largest eruptions in Europe in the past 200 ka, such as the Monte Epomeo Green Tuff (MEGT; Ischia) at ca. 56 ka and the Campanian Ignimbrite (CI; Campi Flegrei) at ca. 40 ka, which form widespread isochrons across the Mediterranean region. These closely-spaced volcanic centres erupt phonolitic to trachytic glass compositions that are similar, and thus it can be challenging to correlate tephra deposits to specific volcanic sources. Here we present a detailed tephrostratigraphy for pre-CI eruption activity using the units preserved within a sequence at the coastal Acquamorta outcrop, on the western side of the CI caldera rim. Both the MEGT and CI units are present in the section, and they bracket twelve eruption units that were logged and sampled. New major and trace element glass chemistry data have been acquired for these Acquamorta tephra deposits. Three eruption deposits from Ischia and nine from Campi Flegrei are identified, which helps constrain the tempo of volcanic activity of these centres between the large caldera-forming eruptions. The three Ischia tephra deposits between the MEGT and the CI are indistinguishable based on both major and trace element glass chemistry and cannot be correlated to a specific or known eruption in this interval, such as the Schiappone tephra. The compositional variations between the Campi Flegrei eruptions reveal temporal shifts in the composition of the tephra deposits that reflect changes in the magmatic system prior to the CI eruption. These deposits indicate that there were at least nine eruptions at Campi Flegrei within 16 ka of the enormous CI eruption, and suggest that there was no significant period of repose before the caldera generating eruption

Strontium ranelate reduces the risk of vertebral fracture in young postmenopausal women with severe osteoporosis

Early osteoporotic fractures have a great impact on disease progression, the first fracture being a major risk factor for further fractures. Strontium ranelate efficacy against vertebral fractures is presently assessed in a subset of women aged 50-65 years

An elementary approach to rigorous approximation of invariant measures

We describe a framework in which is possible to develop and implement algorithms for the approximation of invariant measures of dynamical systems with a given bound on the error of the approximation. Our approach is based on a general statement on the approximation of fixed points for operators between normed vector spaces, allowing an explicit estimation of the error. We show the flexibility of our approach by applying it to piecewise expanding maps and to maps with indifferent fixed points. We show how the required estimations can be implemented to compute invariant densities up to a given error in the $L^{1}$ or $L^\infty$ distance. We also show how to use this to compute an estimation with certified error for the entropy of those systems. We show how several related computational and numerical issues can be solved to obtain working implementations, and experimental results on some one dimensional maps.Comment: 27 pages, 10 figures. Main changes: added a new section in which we apply our method to Manneville-Pomeau map