Transformation of the crystal structure of Ni0.5TiSe2 under in situ heating.

The crystal structure of the Ni0.5TiSe2 compound has been studied in situ in the temperature range of 25-1000 °C using synchrotron radiation X-ray diffraction. The previously known order-disorder transition in the Ni sublattice at ∼100 °C was found to be a second-order phase transition and belongs to the 3D Ising universality class. Reversible extraction of nickel selenides was observed in the temperature range of 275-975 °C. It was explained in terms of Ni extraction from Ni0.5TiSe2 due to the thermal widening of the Ni 3d/Ti 3d/Se 4p impurity band. The Ni-TiSe2 phase diagram follows the typical pattern of MxTiSe2 (M - transition metal) compounds.

F/OH ratio in a rare fluorine-poor blue topaz from Padre Paraíso (Minas Gerais, Brazil) to unravel topaz's ambient of formation.

Topaz [Al2SiO4(F,OH)2] is one of the main fluorine-bearing silicates occurring in environments where variably acidic (F)/aqueous (OH) fluids saturate the silicate system. In this work we fully characterized blue topaz from Padre Paraíso (Minas Gerais, Brazil) by means of in situ synchrotron X-Ray and neutron powder diffraction measurements (temperature range 298-1273 K) combined with EDS microanalyses. Understanding the role of OH/F substitution in topaz is important in order to determine the hydrophilicity and the exchange reactions of fluorine by hydroxyl groups, and ultimately to characterize the environmental redox conditions (H2O/F) required for mineral formation. The fluorine content estimated from neutron diffraction data is ~ 1.03 a.f.u (10.34 wt%), in agreement with the chemical data (on average 10.0 wt%). The XOH [OH/(OH + F)] (0.484) is close to the maximum XOH value (0.5), and represents the OH- richest topaz composition so far analysed in the Minas Gerais district. Topaz crystallinity and fluorine content sharply decrease at 1170 K, while mullite phase starts growing. On the basis of this behaviour, we suggest that this temperature may represent the potential initial topaz's crystallization temperature from supercritical fluids in a pegmatite system. The log(fH2O/fHF)fluid (1.27 (0.06)) is coherent with the fluorine activity calculated for hydrothermal fluids (pegmatitic stage) in equilibrium with the forming mineral (log(fH2O/fHF)fluid = 1.2-6.5) and clearly different from pure magmatic (granitic) residual melts [log(fH2O/fHF)fluid < 1]. The modelled H2O saturated fluids with the F content not exceeding 1 wt% may represent an anomalous water-dominant / fluorine-poor pegmatite lens of the Padre Paraíso Pegmatite Field.

The folding and aggregation properties of a single KH-domain protein: Ribosome binding factor A (RbfA) from Pseudomonas aeruginosa.

BACKGROUND: Ribosome-binding factor A from the pathogenic bacterium Pseudomonas aeruginosa (PaRbfA) is a small ribosome assembly factor, composed by a single KH domain, involved in the maturation of the 30S subunit. These domains are characterized by the ability to bind RNA or ssDNA and are often located in proteins involved in a variety of cellular functions. However, although the ability of proteins to fold properly, to misfold or to aggregate is of paramount importance for their cellular functions, limited information is available on these dynamic properties in the case of KH domains. METHODS: PaRbfA thermodynamic stability and folding mechanism: Far-UV CD and fluorescence spectroscopy, stopped-flow kinetics and chevron plot analysis, site-directed mutagenesis. Fibrils characterization: FT-IR spectroscopy, Thioflavin T fluorescence, Transmission Electron Microscopy (TEM) and X-ray fibrils diffraction. RESULTS: Quantitative analysis of the (un)folding kinetics of PaRbfA show that, in vitro, the protein folds via a 3-states mechanism involving a transiently populated folding intermediate. We also provide experimental evidences that PaRbfA can form ordered fibrils endowed with cross-ß structure even in mild conditions. CONCLUSION: These results lead to the hypothesis that the folding intermediate of PaRbfA may expose (some of) the predicted amyloidogenic regions, which could act as aggregation nuclei in the fibrillogenesis. GENERAL SIGNIFICANCE: The methodological approach presented herein could be readily adapted to verify the ability of other KH domain proteins to form cross-ß structured fibrils and to transiently populate a folding intermediate.

Modeling nanoribbon peeling.

The lifting, peeling and exfoliation of physisorbed ribbons (or flakes) of 2D material such as graphene off a solid surface are common and important manoeuvres in nanoscience. The feature that makes this case peculiar is the structural lubricity generally realized by stiff 2D material contacts. We model theoretically the mechanical peeling of a nanoribbon of graphene as realized by the tip-forced lifting of one of its extremes off a flat crystal surface. The evolution of shape, energy, local curvature and body advancement are ideally expected to follow a succession of regimes: (A) initial prying, (B) peeling with stretching but without sliding (stripping), (C) peeling with sliding, (D) liftoff. In the case where in addition the substrate surface corrugation is small or negligible, then (B) disappears, and we find that the (A)-(C) transition becomes universal, analytical and sharp, determined by the interplay between bending rigidity and adsorption energy. This general two-stage peeling transition is identified as a sharp crossover in published data of graphene nanoribbons pulled off an atomic-scale Au(111) substrate.

Thermal stability of the layered modification of Cu0.5ZrTe2 in the temperature range 25-900†°C.

The thermal stability of the layered modification of the Cu0.5ZrTe2 polycrystalline intercalation compound, synthesized at room temperature, has been studied in the temperature range 25-900 °C. A change in the occupation of the octahedral and tetrahedral coordinated sites in the interlayer space of the zirconium ditelluride was observed using in-situ time-resolved synchrotron X-ray powder diffraction experiments. The formation of the rhombohedral CuZr2Te4 phase, which is stable in the temperature range 300-700 °C, has been observed. The copper intercalation at room temperature leads to the formation of a phase in which the Cu atoms occupy only octahedral sites in the interlayer space. At temperatures above the decay temperature of the rhombohedral CuZr2Te4, a layered phase with Cu atoms uniformly distributed between octahedral and tetrahedral sites in the interlayer space is stable. The changes in the crystal structure independent of temperature are in agreement with the previously proposed model, according to which the stability of the layered or the rhombohedral phase is determined by the entropy factor associated with the distribution of the intercalated atoms between the octahedral and tetrahedral sites in the interlayer space.

Updated clinical overview on cardiac laminopathies: an electrical and mechanical disease.

Cardiac laminopathies, associated with mutations in the LMNA gene, encompass a wide spectrum of clinical manifestations, involving electrical and mechanical alterations of cardiomyocytes. Thus, dilated cardiomyopathy, bradyarrhythmias and atrial or ventricular tachyarrhythmias may occur in a number of combined phenotypes. Nowadays, some attempt has been made to identify clinical predictors for the most life-threatening complications of LMNA-associated heart disease, i.e. sudden cardiac death and end-stage heart failure. The goal of this manuscript is to combine the most recent evidences in an updated review to show the state-of-the-art of such a complex disease group. This is supposed to be the starting point to collect more data and design new ad hoc studies to identify clinically useful predictors to stratify risk in mutation carriers, including probands and their asymptomatic relatives.

Lifted graphene nanoribbons on gold: from smooth sliding to multiple stick-slip regimes.

Graphene nanoribbons (GNRs) physisorbed on a Au(111) surface can be picked up, lifted at one end, and made to slide by means of the tip of an atomic-force microscope. The dynamic transition from smooth sliding to multiple stick-slip regimes, the pushing/pulling force asymmetry, the presence of pinning, and its origin are real frictional processes in a nutshell, in need of a theoretical description. To this purpose, we conduct classical simulations of frictional manipulations of a 30 nm-long GNR, one end of which is pushed or pulled horizontally while held at different heights above the Au surface. These simulations allow us to clarify theoretically the emergence of stick-slip originating from the short 1D edges rather than the 2D "bulk", the role of adhesion, of lifting, and of graphene bending elasticity in determining the GNR sliding friction. The understanding obtained in this simple context is of additional value for more general cases.

2D-3D transition in Cu-TiS2 system.

The phase diagram of the quasi-binary Cu-TiS2 system has been studied in situ in the temperature-concentration plane for the first time. Phase transitions between 2D (layered) and 3D (cubic) phases in CuxTiS2 (x = 0-0.5) intercalation compounds have been studied by the X-ray diffraction technique in the temperature range 20-1000 °C. It has been found that the stability of the layered phase is determined by the distribution of copper atoms between the octahedral and tetrahedral crystallographic sites. The occupation of octahedral sites dominates at low temperatures. Upon heating, tetrahedral site occupation is limited due to elastic lattice distortion and the layered phase becomes unstable and transforms to the spinel. Further heating allows the distribution of copper between octahedral and tetrahedral sites; the layered phase becomes stable again.

Pressure-induced penetration of guest molecules in high-silica zeolites: the case of mordenite.

A synthetic high-silica mordenite (HS-MOR) has been compressed in both non-penetrating (silicone oil, s.o.) and penetrating [methanol : ethanol : water (16 : 3 : 1) (m.e.w.), water : ethanol (3 : 1) (w.e.), and ethylene glycol (e.gl.)] pressure transmitting media (PTM). In situ high-pressure (HP) synchrotron X-ray powder diffraction (XRPD) experiments allowed the unit cell parameters to be followed up to 1.6, 1.8, 8.4, and 6.7 GPa in s.o., w.e., m.e.w., and e.gl., respectively. Moreover, e.gl. was also used as a PTM in in situ HP Raman and ex situ IR experiments. The structural refinement of HS-MOR compressed in e.gl. at 0.1 GPa - the lowest investigated pressure - revealed the presence of 3.5 ethylene glycol molecules per unit cell. The infrared spectrum of the recovered sample, after compression to 1 GPa, is consistent with the insertion of ethylene glycol molecules in the pores. XRPD and Raman spectroscopy experiments performed under pressure indicated the insertion of a small number of guest molecules. Ethylene glycol is partially retained inside mordenite upon pressure release. A symmetry lowering was observed in s.o. above 0.8 GPa, while above 1.6 GPa the patterns indicated a rapid loss of long range order. From ambient pressure (Pamb) to 1.6 GPa, a high cell volume contraction (ΔV = -9.5%) was determined. The patterns collected with penetrating PTM suggested the penetration of guest molecules into the porous host matrix, starting from a very low P regime. The entrapment of PTM molecules inside micropores contributes to the stiffening of the structure and, as a consequence, to the decrease of the compressibility with respect to that measured in s.o. From the structural point of view, HS-MOR reacts to compression and to the penetration of different guest species with appropriate framework deformations. Interestingly, ethylene glycol is partially retained inside mordenite upon pressure release, which is of importance for potential application of this composite material.

The implantable cardioverter defibrillator in primary prevention: a revision of monocentric study group.

AIMS: To evaluate the outcome of a population implanted with an implantable cardioverter defibrillator (ICD) for primary prevention in terms of mortality, morbidity and appropriate and inappropriate interventions. Secondly, to compare the performances of single-chamber vs. dual-chamber devices. METHODS: We examined all patients with CAD or CMD who received an ICD in primary prevention with at least 6 months of follow-up. For each patient were evaluated, primarily, survival, complications related to the implantation and performance of the device (antitachycardia pacing/shock). RESULTS: Of 193 patients, 163 were men (84.5). Mean age was 64.4 ± 10 years. One hundred and twenty patients (62%) were affected by CAD and 73 (38%) by CMD. The ejection fraction was 26 ± 6%. Fifty-three patients (27.5%) received a dual-chamber ICD, whereas 140 (72.5%) received a single-chamber ICD. There were periprocedural complications in 5.2% of the patients. At a mean follow-up of 49.9 months, 55 patients (28.5%) died. Appropriate interventions were documented in 40 patients (20.7%). In 36 patients (18%), inappropriate interventions occurred. Patients implanted with dual-chamber ICD had an overall mortality of 17% compared to 32.4% for those implanted with single-chamber ICD (P = 0.029). Mortality was higher in patients with CAD (33.9%) (P = 0.032). Among the fatalities, 69% occurred in patients who had an ejection fraction 25% or less at the time of implantation and 31% in patients with an ejection fraction greater than 25% (P = 0.013). CONCLUSIONS: The 4-year survival was 72%. The overall mortality was higher in patients with CAD. More than two-thirds of the deceased had an ejection fraction less than 25%. The dual-chamber ICD patients had a significantly lower mortality rate.

[Measles in the Local Health Unit Naples 4: vaccination coverage, epidemic 2001-2002 and prevention strategies]. / II morbillo nella ASL Napoli 4: coperture vaccinali, epidemia 2001-2002 e strategie per la prevenzione.

The authors have analysed vaccination coverage for measles. The active offer of the vaccine brought about an increase of the vaccination coverage but participation to vaccination proved unsatisfactory between 1995 and 2000. The measles epidemic reported 1367 cases, of which 125 were hospitalised (3 cases presented complications). The target for the next years is to reach a vaccination coverage of 95% or more and recuperate the non vaccinated, starting with the 1990 birth cohort.

[Role of transesophageal echocardiography in the evaluation of the potential embolic risk in left atrial thrombosis. Report of a clinical case]. / Ruolo dell'ecocardiografia transesofagea nella valutazione del potenziale rischio embolico della trombosi atriale sinistra. Descrizione di un caso clinico.

We describe the case of a 73-year-old man with cardiac failure due to hypertensive heart disease, chronic atrial fibrillation, prior ischemic stroke and acute ischemia of the left leg probably embolic in nature, in whom transthoracic echocardiography (TTE) detected a large left atrial mass compatible with thrombus. Transesophageal echocardiography (TEE) was performed to better evaluate the atrial mass. TTE showed a mass that was firmly attached to the wall of the left atrium, compact, homogeneous and stationary, indicating a relatively low embolic risk. On the other hand TEE clearly detected a marked motility and echographic unhomogeneity of the atrial mass, suggesting a poorer prognosis and urgent surgical referral due to high impending embolik risk. This case further supports the superiority of TEE to TTE in the assessment of intracardiac masses and, in particular, of embolik risk in a patient with left atrial thrombosis.

[Brucellosis in the Campania region]. / Brucellosi nella regione Campania.

The research describes the trend of brucellosis, in the period 1984-86, in the county of the "regione Campania". This trend, in contrast with the national one, is manifested as endemic, with frequent and localised outbreaks of epidemic levels. The research also describes, through the analysis of the illness registration forms of 762 cases of brucellosis in the period 1985-86, the seasonal trend, the ages of major risk of infection and the most frequent modes of infection. The paper concludes with suggestions for the effective prevention of brucellosis.