Simple, common but functional: biocompatible and luminescent rare-earth doped magnesium and calcium hydroxides from miniemulsion.

Nanostructured (d∼ 20-35 nm) and highly luminescent Ca(OH):Ln and Mg(OH):Ln (Ln = Eu, Sm, Tb, Mg(Ca)/Ln = 20 : 1 atomic) nanostructures were obtained in inverse (water in oil - w/o) miniemulsion (ME), by exploiting the nanosized compartments of the droplets to spatially confine the hydroxide precipitation in basic environment (NaOH). The functional nanostructures were prepared using different surfactants (Span80 (span) and a mixture of Igepal co-630 and Brij 52 (mix)) to optimise ME stability and hydroxide biocompatibility as well as tune the droplet sizes. X-Ray diffraction (XRD) analyses testify the achievement of a pure brucite-Mg(OH)-phase and pure portlandite-Ca(OH)-phase with a high degree of crystallinity.

[Management strategies and choice of antithrombotic treatment in patients admitted with acute coronary syndrome--executive summary for clinical practice. Consensus Document of the Regional Chapters of the Italian National Association of Hospital Cardiologists (ANMCO) and of the Italian Society of Emergency Medicine (SIMEU)].

This document has been developed by the Lazio regional chapters of two scientific associations, the Italian National Association of Hospital Cardiologists (ANMCO) and the Italian Society of Emergency Medicine (SIMEU), whose members are actively involved in the everyday management of Acute Coronary Syndromes (ACS). The document is aimed at providing a specific, practical, evidence-based guideline for the effective management of antithrombotic treatment (antiplatelet and anticoagulant) in the complex and ever changing scenario of ACS. The document employs a synthetic approach which considers two main issues: the actual operative context of treatment delivery and the general management strategy.

From thioxo cluster to dithio cluster: exploring the chemistry of polynuclear zirconium complexes with S,O and S,S ligands.

Three different zirconium thio and oxothio clusters, characterized by different coordination modes of dithioacetate and/or monothioacetate ligands, were obtained by the reaction of monothioacetic acid with zirconium n-butoxide, Zr(O(n)Bu)4, in different experimental conditions. In particular, we isolated the three polynuclear Zr3(μ3-SSSCCH3)2(SSCCH3)6·2(n)BuOH (Zr3), Zr4(μ3-O)2(μ-η(1)-SOCCH3)2(SOCCH3)8(O(n)Bu)2 (Zr4), and Zr6(μ3-O)5(μ-SOCCH3)2(μ-OOCCH3)(SOCCH3)11((n)BuOH) (Zr6) derivatives, presenting some peculiar characteristics. Zr6 has an unusual star-shaped structure.

Tuning the functional properties of metal complexes containing polytopic heteroaromatic nitrogen ligands.

The preparation, characterization, and optimization of the functional properties of mono- and polynuclear coordination complexes containing heteroaromatic nitrogen ligands are discussed here, taking the advantage of numerous studies performed in our laboratories on exploring a variety of different metal ions and polytopic ligands. We highlight how very minor changes in connectivity, composition, and polarity of the molecular entities employed in the self-assembly steps may significantly affect the structural, thermal, sorptive, magnetic, and mesomorphic behavior of the resulting materials. Examples from three different classes are included: 1) pyrazolate-based polynuclear coordination compounds, 2) homoleptic and heteroleptic coordination polymers, and 3) 2,2'-bipyridine metal-based liquid crystals.

New coordination polymers based on the triangular [Cu3(mu3-OH)(mu-pz)3]2+ unit and unsaturated carboxylates.

By reacting copper(II) acrylate with pyrazole (Hpz), two trinuclear copper derivatives [Cu3(mu3-OH)(mu-pz)3(CH2CHCOO)2(H2O)2(Hpz)], 1, and [Cu3(mu3-OH)(mu-pz)3(CH2CHCOO)2(CH3OH)], 2, are obtained, in water and methanol respectively, while copper(II) methacrylate affords [Cu3(mu3-OH)(mu-pz)3(CH2C(CH3)COO)2], 3, independently from the solvent used. In 1 and 2 two triangular trinuclear units are connected through acrylate bridges forming hexanuclear clusters that, in the case of 2 are further connected through double syn-syn carboxylate bridges, generating a 1-D coordination polymer. In the case of 3 a different 1-D coordination polymer is obtained by alternating syn-syn and syn-anti double carboxylate bridges connecting the trinuclear clusters.

Magnetic properties and vapochromic reversible guest-induced transformation in a bispyrazolato copper(II) polymer: an experimental and dispersion-corrected density functional theory study.

Dispersion-corrected density functional theory (DFT-D) calculations, Electron Spin Resonance spectroscopy (EPR), and variable temperature magnetic moment measurements were used to investigate the structure and the electronic/magnetic properties of bispyrazolato-copper(II) coordination polymer and of its hydration product. The Cu(II) ions are antiferromagnetically coupled through the sigma system of the pyrazolate rings in both compounds. Theoretical electron density maps reveal that water molecules interact simultaneously and to a comparable extent with two Cu(II) centers (through the electronegative O end) and two pyrazolate rings (through the partly positively charged H atoms), which is compatible with the observed internuclear distances.

Carbonyl copper(I) complexes with hydrotris(1,2,4-triazolyl)borate, hydrotris(pyrazolyl)borate, and tris(pyrazolyl)methane ligands: a DFT study.

Theoretical evidence supporting the use of hydrotris(1,2,4-triazolyl)borate (ttz) ligands as a proper alternative to the hydrotris(pyrazolyl)borate (tp) ones is provided by density functional calculations.

Density functional theory study of the binding capability of tris(pyrazol-1-yl)methane toward Cu(I) and Ag(I) cations.

Density functional theory (DFT) has been used to look into the electronic structure of [M(tpm)]+ molecular ion conformers (M = Cu, Ag; tpm = tris(pyrazol-1-yl)methane) and to study the energetics of their interconversion. Theoretical data pertaining to the free tpm state the intrinsic instability of its kappa3-like conformation, thus indicating that, even though frequently observed, the kappa3-tripodal coordinative mode is unlikely to be directly achieved through the interaction of M(I) with the kappa3-like tpm conformer. It is also found that the energy barrier for the kappa2-[M(tpm)]+ --> kappa3-[M(tpm)]+ conversion is negligible.

Supramolecular assemblies of trinuclear triangular copper(II) secondary building units through hydrogen bonds. Generation of different metal-organic frameworks, valuable catalysts for peroxidative oxidation of alkanes.

Formation of the trinuclear triangular copper derivative [Cu3(mu3-OH)(mu-pz)3(EtCOO)2(H2O)] x H2O, 1b (Hpz = pyrazole), has been simply achieved by addition of Hpz to a water solution of Cu(EtCOO)2 x H2O and leaving the resulting solution to crystallize at ca. 12 degrees C. When the reaction and crystallization were carried out at a slightly higher temperature (18-22 degrees C), the compound [Cu3(mu3-OH)(mu-pz)3(EtCOO)2(H2O)], 1c, formed.

Synthesis, solid-state NMR, and X-ray powder diffraction characterization of group 12 coordination polymers, including the first example of a C-mercuriated pyrazole.

Cadmium and mercury acetates have been reacted with pyrazole (Hpz) and 3,5-dimethylpyrazole (Hdmpz), affording distinct mixed-ligand species, selectively prepared upon slightly modifying the reaction conditions. Two polymorphs of [{Cd(mu-ac)2(Hpz)2}n], as well as the [{Cd(mu-ac)2(Hdmpz)2}n] species (Hac = acetic acid), were obtained by solution chemistry, while the two-dimensional [{Cd3(mu3-ac)4(mu-pz)2(Hpz)2}n] and [{Cd(mu-ac)(mu-pz)}n] polymers were prepared upon controlled thermal treatment of one of the [{Cd(mu-ac)2(Hpz)2}n] forms. Two mercury derivatives, [{Hg3(mu-ac)3(mu-pz)3}n] and [{Hg(ac)(mu-dmpz)}n], were also prepared, the latter containing one-dimensional chains of Hg(II) ions bridged by C-mercuriated Hdmpz ligands.

The competition between acetate and pyrazolate in the formation of polynuclear Zn(II) coordination complexes.

Hydrated zinc(II) acetate reacts with pyrazole (Hpz) and, depending on the reaction conditions, forms different pyrazole-containing species, i.e. [[Zn(CH3COO)(mu-pz)(Hpz)]2] (1), [[Zn(CH3COO)2(Hpz)2.

One-dimensional and two-dimensional coordination polymers from self-assembling of trinuclear triangular Cu(II) secondary building units.

The reactions of pyrazole (Hpz) with some copper(II) carboxylates in the presence of water yield trinuclear copper derivatives characterized by the triangular core [Cu3mu3-OH)(mu-pz)3(RCOO)2] (R = H, C2H5, C3H7). Copper(II) formate gives [Cu3(mu3-OH)(mu-pz)3(HCOO)2(Hpz)2] (1), whereas copper propionate and butyrate afford [Cu3(mu3-OH)(mu-pz)3(C2H5COO)2(EtOH)] (2) and [Cu3(mu3-OH)(mu-pz)3(C3H7COO)2(MeOH)(H2O)] (3), respectively, both containing solvent molecules coordinated to copper atoms. Magnetic susceptibilities are consistent with a single unpaired electron for each trinuclear unit of 1-3, and EPR measurements indicate that higher spin states, generated by exchange coupling between copper atoms, may be populated at room temperature.

Sorption-desorption behavior of bispyrazolato-copper(II) 1D coordination polymers.

A new polycrystalline vapochromic polymorph of the one-dimensional copper bispyrazolate polymer reversibly and selectively absorbs a number of small molecules; the crystal structures of the anhydrous and fully hydrated species, determined by powder diffraction methods, are markedly different despite their simple, fast, and reversible interconversion.

Spontaneous self-assembly of an unsymmetric trinuclear triangular copper(II) pyrazolate complex, [Cu3(micro3-OH)(micro-pz)3(MeCOO)2(Hpz)] (Hpz = pyrazole). synthesis, experimental and theoretical characterization, reactivity, and catalytic activity.

The almost quantitative formation of the triangular trinuclear copper derivative [Cu3(3-OH)(-pz)3(MeCOO)2(Hpz)] (1) (Hpz = pyrazole), has been simply achieved by adding Hpz to an ethanol solution of Cu(MeCOO)2 x H2O. An X-ray molecular structure determination shows that 1 is completely unsymmetric and that trinuclear units result assembled in an extended bidimensional network formed through acetate bridges and hydrogen bonds. EPR and magnetic measurements are consistent with the presence of a single unpaired electron.

[Electrical cardioversion for atrial fibrillation: advantages of the transthoracic biphasic method].

Background: The purpose of this study was to evaluate efficacy and safety of biphasic shock for atrial fibrillation cardioversion to sinus rhythm. A second endpoint was to evaluate myocardial damage by means of cardiac troponin I dosage.

Methods: We studied 164 patients, with drug-resistant atrial fibrillation (208 episodes).

Experimental and Theoretical Investigation of the Molecular and Electronic Structure of [Zn(4)(&mgr;(4)-S){&mgr;-S(2)As(CH(3))(2)}(6)] and [Cd(4)(&mgr;(4)-S){&mgr;-S(2)As(CH(3))(2)}(6)]: Two Possible Molecular Models of Extended Metal Chalcogenide Semiconductors.

The molecular and electronic structure of hexakis[&mgr;-(dimethylarsinodithioate-S:S')]-&mgr;(4)-thioxotetrazinc has been investigated by combining X-ray diffraction measurements, electrospray mass spectrometry (ESI), UV absorption spectroscopy, and density functional calculations. The polynuclear zinc complex consists of discrete "tetrazinc sulfide" moieties held together by van der Waals interactions. The unit cell contains four independent molecules and four solvent molecules.

An Experimental and Theoretical Study of the Electronic Structure of Zinc Thiophenolate-Capped Clusters.

The electronic structure of a series of thiophenolate-capped ionic/neutral clusters ([Zn(SPh)(4)](2)(-) (1); [Zn(4)(&mgr;(2)-SPh)(6)(SPh)(4)](2)(-) (2); Zn(10)(&mgr;(3)-S)(4)(&mgr;(2)-SPh)(12) (3); and [Zn(10)(&mgr;(3)-S)(4)(&mgr;(2)-SPh)(12)(SPh)(4)](4)(-) (4), Ph = phenyl), indicated as supertetrahedral fragments and possible molecular models of cubic ZnS, has been investigated by coupling density functional calculations to UV electronic and X-ray photoelectron (XP) spectroscopy. Theoretical outcomes indicate that, on passing from the tetrametallic to the decametallic clusters, there is a modification in the nature of the outermost occupied and lowermost unoccupied molecular orbitals. Actually, both in 1 and in 2 the frontier orbitals are delocalized and mainly composed of the S 3p pairs strongly mixed with the Ph pi levels (the HOMOs) and of the linear combinations of Ph pi orbitals, the LUMOs.