Anisotropic hybridization probed by polarization dependent x-ray absorption spectroscopy in VI3van der Waals Mott ferromagnet.

Polarization dependent x-ray absorption spectroscopy was used to study the magnetic ground state and the orbital occupation in bulk-phase VI3van der Waals crystals below and above the ferromagnetic and structural transitions. X-ray natural linear dichroism and x-ray magnetic circular dichroism spectra acquired at the VL2,3edges are compared against multiplet cluster calculations within the frame of the ligand field theory to quantify the intra-atomic electronic interactions at play and evaluate the effects of symmetry reduction occurring in a trigonally distorted VI6unit. We observed a non zero linear dichroism proving the presence of an anisotropic charge density distribution around the V3+ion due to the unbalanced hybridization between the vanadium and the ligand states. Such hybridization acts as an effective trigonal crystal field, slightly lifting the degeneracy of thet2g2ground state. However, the energy splitting associated to the distortion underestimates the experimental band gap, suggesting that the insulating ground state is stabilized by Mott correlation effects rather than via a Jahn-Teller mechanism. Our results clarify the role of the distortion in VI3and establish a benchmark for the study of the spectroscopic properties of other van der Waals halides, including emerging 2D materials with mono and few-layers thickness, whose fundamental properties might be altered by reduced dimensions and interface proximity.

Diagnostic role of echocardiography in patients admitted to the emergency room with suspect no-ST-segment elevation acute myocardial infarction.

OBJECTIVE: We investigated whether echocardiography may help identify, among patients admitted with a suspect of non-ST-segment elevation acute myocardial infarction (NSTEMI), those with athero-thrombotic coronary artery disease (CAD). PATIENTS AND METHODS: We studied consecutive patients admitted with a clinical suspect of first NSTEMI. Echocardiography was assessed within 24 hours from admission. Patients were divided into two groups, according to the results of coronary angiography: 1) patients with obstructive stenosis (≥ 50%) and/or images of thrombosis in one or more coronary arteries (CAD group); 2) patients with no evidence of obstructive coronary arteries (NOCAD group). RESULTS: Of 101 patients enrolled in the study, 53 (52.5%) showed obstructive CAD and 48 (47.5%) NOCAD. At echocardiographic examination, regional wall motion abnormalities were found in 52.8% of patients in the CAD group and 43.7% in the NOCAD group (p=0.43). Left ventricle ejection fraction was 56.4±6.8 vs. 54.7±9.8% (p=0.30) and wall motion score index was 1.16±0.26 vs. 1.21±0.32 (p=0.39) in the two groups, respectively. A multivariable logistic regression independent predictors of obstructive CAD included age, male gender, typical angina, diabetes and hypertension. CONCLUSIONS: Our data showed that, in patients with acute chest pain and increased serum troponin T concentration, routine standard echocardiography does not significantly improve the diagnostic accuracy for the presence of obstructive CAD.

Microvascular ischemia in patients with successful percutaneous coronary intervention: effects of ranolazine and isosorbide-5-mononitrate.

OBJECTIVE: About one-third of patients undergoing percutaneous coronary interventions (PCIs) for flow-limiting coronary stenosis continue to develop signs of myocardial ischemia (MI) during exercise stress test [EST], despite successful coronary revascularization. Coronary microvascular dysfunction is a likely major cause of the persistence of EST-induced MI in these patients. PATIENTS AND METHODS: We studied 15 patients (14 men, age 67±5 years) fulfilling the following strict inclusion criteria: (1) recent PCI (<6 months), with drug-eluting stent, of coronary artery stenoses for stable angina, with evidence of full success (no residual stenosis >20% in any vessel); (2) persistence of ST-segment depression induction during EST. After a basal investigation, patients received either ranolazine (375 mg bid) or isosorbide-5-mononitrate (ISMN, 20 mg bid) for 3 weeks in a single-blind, randomized crossover study. Clinical assessment, symptom-limited EST, echocardiographic color-Doppler, with tissue-Doppler examination, and coronary microvascular dilator response to adenosine (CFR-ADO) and cold pressor test (CFR-CPT), assessed by transthoracic echo-Doppler, were obtained at baseline and the end of the 3-week therapy with each drug. RESULTS: Compared to both baseline and ISMN, ranolazine showed a longer time to 1 mm ST-segment depression (404±116 s vs. 317±98 and 322±70 s, respectively; p<0.01). No differences were observed in coronary microvascular function and diastolic left ventricular function between the 2 drugs and compared to baseline. CONCLUSIONS: Our data show that ranolazine, but not ISMN, improved time to ischemia during EST. This effect, however, was independent of any effects on coronary microvascular and diastolic function.

Re-evaluating how charge transfer modifies the conformation of adsorbed molecules.

The archetypal electron acceptor molecule, TCNQ, is generally believed to become bent into an inverted bowl shape upon adsorption on the coinage metal surfaces on which it becomes negatively charged. New quantitative experimental structural measurements show that this is not the case for TCNQ on Ag(111). DFT calculations show that the inclusion of dispersion force corrections reduces not only the molecule-substrate layer spacing but also the degree of predicted molecular bonding. However, complete agreement between experimentally-determined and theoretically-predicted structural parameters is only achieved with the inclusion of Ag adatoms into the molecular layer, which is also the energetically favoured configuration. The results highlight the need for both experimental and theoretical quantitative structural methods to reliably understand similar metal-organic interfaces and highlight the need to re-evaluate some previously-investigated systems.

Correlation between benzene and testosterone in workers exposed to urban pollution.

AIM: Many studies have examined the effects of benzene on testosterone. The purpose of this study was to evaluate the possible correlation between the blood levels of benzene and the levels of testosterone. MATERIALS AND METHODS: The study involved a group of 148 subjects. For every worker have been made out a blood sample for the evaluation of benzene and testosterone levels and an urine analysis for the evaluation of the levels of trans, trans-muconic acid and S-phenylmercapturic acid. We estimated the Pearson correlation coefficient between the variables in the sample and the urinary metabolites, age, length of service, gender, BMI. For the analysis of the major confounding factors it was performed a multiple linear regression. RESULTS: The Pearson correlation coefficiet showed: 1. a significant inverse correlation between the S-phenyl mercapturic acid and free testosterone; 2. a significant direct correlation between trans-trans muconic acid and BMI. After dividing the sample according to the median of blood benzene (161.0 ng / L), Pearson correlation coefficient showed a significant inverse correlation between the S-phenyl mercapturic acid and free testosterone in the group with values below this median. CONCLUSIONS: Our results, to be considered preliminary, suggest that occupational exposure to low levels of benzene, present in urban pollution, affect the blood levels of testosterone. These results need to be confirmed in future studies, with the eventual possibility of including more specific fertility tests.

Two-dimensional core-shell donor-acceptor assemblies at metal-organic interfaces promoted by surface-mediated charge transfer.

Organic charge transfer (CT) complexes obtained by combining molecular electron donors and acceptors have attracted much interest due to their potential applications in organic opto-electronic devices. In order to work, these systems must have an electronic matching - the highest occupied molecular orbital (HOMO) of the donor must couple with the lowest unoccupied molecular orbital (LUMO) of the acceptor - and a structural matching, so as to allow direct intermolecular CT. Here it is shown that, when molecules are adsorbed on a metal surface, novel molecular organizations driven by surface-mediated CT can appear that have no counterpart in condensed phase non-covalent assemblies of donor and acceptor molecules. By means of scanning tunneling microscopy and spectroscopy it is demonstrated that the electronic and self-assembly properties of an electron acceptor molecule can change dramatically in the presence of an additional molecular species with marked electron donor character, leading to the formation of unprecedented core-shell assemblies. DFT and classical force-field simulations reveal that this is a consequence of charge transfer from the donor to the acceptor molecules mediated by the metallic substrate.

Biomimetic proteolipid vesicles for targeting inflamed tissues.

A multitude of micro- and nanoparticles have been developed to improve the delivery of systemically administered pharmaceuticals, which are subject to a number of biological barriers that limit their optimal biodistribution. Bioinspired drug-delivery carriers formulated by bottom-up or top-down strategies have emerged as an alternative approach to evade the mononuclear phagocytic system and facilitate transport across the endothelial vessel wall. Here, we describe a method that leverages the advantages of bottom-up and top-down strategies to incorporate proteins derived from the leukocyte plasma membrane into lipid nanoparticles. The resulting proteolipid vesicles-which we refer to as leukosomes-retained the versatility and physicochemical properties typical of liposomal formulations, preferentially targeted inflamed vasculature, enabled the selective and effective delivery of dexamethasone to inflamed tissues, and reduced phlogosis in a localized model of inflammation.

Macroscopic scattering of cracks initiated at single impurity atoms.

Brittle crystals, such as coloured gems, have long been known to cleave with atomically smooth fracture surfaces, despite being impurity laden, suggesting that isolated atomic impurities do not generally cause cracks to deflect. Whether cracks can ever deviate when hitting an atomic defect, and if so how they can go straight in real brittle crystals, which always contain many such defects, is still an open question. Here we carry out multiscale molecular dynamics simulations and high-resolution experiments on boron-doped silicon, revealing that cracks can be deflected by individual boron atoms. The process, however, requires a characteristic minimum time, which must be less than the time spent by the crack front at the impurity site. Deflection therefore occurs at low crack speeds, leading to surface ridges which intensify when the boron-dopage level is increased, whereas fast-moving cracks are dynamically steered away from being deflected, yielding smooth cleavage surfaces.

Neurotrophic factors and neurodegenerative diseases: a delivery issue.

Neurotrophic factors (NTFs) represent one of the most stimulating challenge in neurodegenerative diseases, due to their potential in neurorestoring and neuroprotection. Despite the large number of proofs-of-concept and evidences of their activity, most of the clinical trials, mainly regarding Parkinson's disease and Alzheimer's disease, demonstrated several failures of the therapeutic intervention. A large number of researches were conducted on this hot topic of neuroscience, clearly evidencing the advantages of NTF approach, but evidencing the major limitations in its application. The inability in crossing the blood-brain barrier and the lack of selectivity actually represent some of the most highlighted limits of NTFs-based therapy. In this review, beside an overview of NTF activity versus the main neuropathological disorders, a summary of the most relevant approaches, from invasive to noninvasive strategies, applied for improving NTF delivery to the central nervous systems is critically considered and evaluated.

Correlation between clinical presentation and delayed-enhancement MRI pattern in myocarditis.

PURPOSE: The exact incidence of myocarditis is unknown, as the diagnosis is frequently delayed or missed. Clinical presentation and disease course are extremely variable, as there may be acute onset with acute coronary syndrome, or cardiogenic shock, or progressive heart failure or arrhythmias. The purpose of this study was to identify prognostic factors on magnetic resonance imaging (MRI) performed in patients with bioptically proven myocarditis at presentation and after 6 months. MATERIALS AND METHODS: Fifty-six consecutive patients with different presentations of myocarditis (20 with acute coronary syndrome, 20 with heart failure, 16 with arrhythmias) were enrolled. All patients underwent B-mode echocardiography (echo) and tissue Doppler imaging, coronarography, ventriculography, endomyocardial biopsy and contrast-enhanced MRI examination, as well as clinical and echo follow-up at 6 months. RESULTS: At 6-month follow-up, patients were divided in two groups according to values of end-systolic volume and ejection fraction: patients with negative remodelling and those with positive remodelling. Late enhancement was found to be an independent predictor of negative remodelling. CONCLUSIONS: Contrast-enhanced MRI is useful both in the diagnosis and as a prognostic indicator in the clinical suspicion of myocarditis.

Disease management of type 2 diabetes: a follow-up analysis in a sanitary district of Sicily.

AIM: The aim of this paper was to analyze the Disease management of type 2 diabetes in a sanitary district of the Sicily Region (Italy). METHODS: In a population of 9 698 subjects, we selected patients with known type 2 diabetes: a cohort of 385 subjects, (206 women and 179 men) following up for one year. Prevalence of type 2 diabetes in the analyzed population was 3.97%. A great lot of cohort was on a diet. RESULTS: After one year, a per cent reduction of obese and overweight subjects was observed. No differences were observed for Body Mass Index (BMI) at the beginning and at the end of the study. After one year, through educational meetings with the doctor, a significant increase of knowledge on the patient's conditions and on the diabetes complications was verified, but our data showed persistent poor attention by doctors. The poor knowledge of patients led to a difficult disease management. After one year, a great lot of cohort used antistroke and cardiovascular disease therapy, reducing significantly the cardiovascular disease risk. However, our study also highlights a gap between the therapeutic guidelines and the actual treatment, with wide variability in the delivery of secondary prevention. CONCLUSION. Our study showed that a persevering warning and a constant adjournment of doctors improves the disease management, reducing complications risk in type 2 diabetes patients.

NIR-labeled nanoparticles engineered for brain targeting: in vivo optical imaging application and fluorescent microscopy evidences.

The presence of the blood-brain barrier (BBB) makes extremely difficult to develop efficacious strategies for targeting contrast agents and delivering drugs inside the Central Nervous System (CNS). To overcome this drawback, several kinds of CNS-targeted nanoparticles (NPs) have been developed. In particular, we proposed poly-lactide-co-glycolide (PLGA) NPs engineered with a simil-opioid glycopeptide (g7), which have already proved to be a promising tool for achieving a successful brain targeting after i.v. administration in rats. In order to obtain CNS-targeted NPs to use for in vivo imaging, we synthesized and administrated in mice PLGA NPs with double coverage: near-infrared (NIR) probe (DY-675) and g7. The optical imaging clearly showed a brain localization of these novel NPs. Thus, a novel kind of NIR-labeled NPs were obtained, providing a new, in vivo detectable nanotechnology tool. Besides, the confocal and fluorescence microscopy evidences allowed to further confirm the ability of g7 to promote not only the rat, but also the mouse BBB crossing.

[A pilot study on adolescents of both sexes. Correlation between phenotype, athletic performances and family history to type 2 diabetes]. / Uno studio pilota su adolescenti di entrambi i sessi: correlazione tra fenotipo, prestazioni fisiche e familiarità al diabete di tipo 2.

The authors have studied the influence of family history of type 2 diabetes on the physical phenotype of 47 health adolescents. In both sexes groups with positive family history (FH+) had the highest values of stature and body weight (P<0.05 for males, not significant for females), waist circumference (P<0.05 for males, not significant for females), and wrist circumference (P=0.05 for males, not significant for females). Considering athletic performance, FH+ males showed a significant higher performance in power exercises than FH- males; no significant differences were found between FH+ and FH- female groups. The study confirms that family history of type 2 diabetes can induce in both sexes precocious phenotype and athletic performances linked-related variations; larger studies are necessary to confirm these data and to verify preventive interventions promoting significant life-style changes.

A first principles based polarizable O(N) interatomic force field for bulk silica.

We present a reformulation of the Tangney-Scandolo interatomic force field for silica [J. Chem. Phys. 117, 8898 (2002)], which removes the requirement to perform an Ewald summation. We use a Yukawa factor to screen electrostatic interactions and a cutoff distance to limit the interatomic potential range to around 10 Å. A reparametrization of the potential is carried out, fitting to data from density functional theory calculations. These calculations were performed within the local density approximation since we find that this choice of functional leads to a better match to the experimental structural and elastic properties of quartz and amorphous silica than the generalized gradient approximation approach used to parametrize the original Tangney-Scandolo force field. The resulting O(N) scheme makes it possible to model hundreds of thousands of atoms with modest computational resources, without compromising the force field accuracy. The new potential is validated by calculating structural, elastic, vibrational, and thermodynamic properties of α-quartz and amorphous silica.

Molecular dynamics studies of the dissociated screw dislocation in silicon.

Characterizing the motion of dislocations through covalent, high Peierls barrier materials is a key problem in materials science, while despite the progress in experimental studies the actual observation of the atomistic behaviour involved in core migration remains limited. We have applied a hybrid embedding scheme to investigate the dissociated screw dislocation in silicon, consisting of two 30° partials separated by a stacking fault ribbon, under the influence of a constant external strain. Our 'learn on the fly' hybrid technique allows us to calculate the forces on atoms in the vicinity of the core region using the tight binding Kwon potential, whilst the remainder of the bulk matrix is treated within a classical approximation. Applying a 5% strain to the dissociated screw dislocation, for a simulation time of 100 ps at a temperature of 600 K, we observe movement of the partials through two different mechanisms: double kink formation and square ring diffusion at the core. Our results suggest that in these conditions, the role of solitons or anti-phase defects in seeding kink formation and subsequent migration is an important one, which should be taken into account in future studies.

Investigating genetic diversity and habitat dynamics in Plantago brutia (Plantaginaceae), implications for the management of narrow endemics in Mediterranean mountain pastures.

Many factors have contributed to the richness of narrow endemics in the Mediterranean, including long-lasting human impact on pristine landscapes. The abandonment of traditional land-use practices is causing forest recovery throughout the Mediterranean mountains, by increasing reduction and fragmentation of open habitats. We investigated the population genetic structure and habitat dynamics of Plantago brutia Ten., a narrow endemic in mountain pastures of S Italy. Some plants were cultivated in the botanical garden to explore the species' breeding system. Genetic diversity was evaluated based on inter-simple sequence repeat (ISSR) polymorphisms in 150 individuals from most of known stands. Recent dynamics in the species habitat were checked over a 14-year period. Flower phenology, stigma receptivity and experimental pollinations revealed protogyny and self-incompatibility. With the exception of very small and isolated populations, high genetic diversity was found at the species and population level. amova revealed weak differentiation among populations, and the Mantel test suggested absence of isolation-by-distance. Multivariate analysis of population and genetic data distinguished the populations based on genetic richness, size and isolation. Landscape analyses confirmed recent reduction and isolation of potentially suitable habitats. Low selfing, recent isolation and probable seed exchange may have preserved P. brutia populations from higher loss of genetic diversity. Nonetheless, data related to very small populations suggest that this species may suffer further fragmentation and isolation. To preserve most of the species' genetic richness, future management efforts should consider the large and isolated populations recognised in our analyses.

Exposure setup to study potential adverse effects at GSM 1800 and UMTS frequencies on the auditory systems of rats.

To investigate possible biological effects of exposure to electromagnetic (EM) fields at the frequencies of global system for mobile communication (GSM) 1800 system and universal mobile telecommunication system (UMTS) on the auditory system of rats, an exposure setup for in vivo experiments is presented. The study was carried out in the framework of two European research projects. The target of the investigation was the cochlea. A dosimetric study was performed, both numerically and through direct measurements, to assess the interaction of the radiated fields and the dose distribution in the biological target. For the local exposure of rats, a loop antenna operating at the frequency bands of interest was designed, realised and characterised through numerical and experimental dosimetric procedures. Moreover, an exposure apparatus was set up, consisting of three arrays of four loop antennas, placed on three levels, thus allowing simultaneous exposure of 12 rats to give statistical power to the experiments. To isolate the exposure arrays, the setup was assembled by a wooden rack with EM field absorbing panels, inserted among the levels and at the four sides of the rack. Isolation was verified by direct measurements. Two exposure arrays were simultaneously supplied, whereas the third one was used for sham exposure. Blind exposure was achieved through a black box, hiding physical connections to the microwave power supply. During exposure sessions, rats were restrained in special plastic jigs for repeatable positioning, thus assuring the fixed level of dose in the target.

"Learn on the fly": a hybrid classical and quantum-mechanical molecular dynamics simulation.

We describe and test a novel molecular dynamics method which combines quantum-mechanical embedding and classical force model optimization into a unified scheme free of the boundary region, and the transferability problems which these techniques, taken separately, involve. The scheme is based on the idea of augmenting a unique, simple parametrized force model by incorporating in it, at run time, the quantum-mechanical information necessary to ensure accurate trajectories. The scheme is tested on a number of silicon systems composed of up to approximately 200 000 atoms.

Mesoscopic chiral reshaping of the Ag(110) surface induced by the organic molecule PVBA.

We report scanning tunneling microscopy observations on the restructuring of a Ag(110) surface induced by the molecule 4-[trans-2-(pyrid-4-yl-vinyl)]benzoic acid (PVBA). Our data reveal that the surface undergoes a mesoscopic step faceting following exposure to submonolayer coverages and thermal activation. A sawtooth arrangement evolves implying long-range mass transport of substrate atoms and forming a regular arrangement of kink sites. Its formation is associated with the molecules' functional headgroups forming carboxylates with [100] Ag microfacets at step edges, and eventually operating to reshape the surface morphology. Interestingly, the resulting microfacets act as chiral templates for the growth of supramolecular PVBA structures. Theoretical modeling based on ab initio results indicates that chiral recognition processes discriminating between the two enantiomers of adsorbed PVBA molecules occur in this process.

Mesoscopic correlation of supramolecular chirality in one-dimensional hydrogen-bonded assemblies.

The ordering of 4-[trans-2-(pyrid-4-yl-vinyl)] benzoic acid, a two-dimensional chiral species, was studied by scanning tunneling microscopy at noble metal surfaces. Homochiral molecules self-assemble in supramolecular chiral hydrogen-bonded twin chains, which order in nanogratings where the supramolecular chirality is strictly correlated over the entire microm domains without intimate molecular contact. Model simulations indicate that the underlying mesoscopic chiral resolution is associated with twin chains acting as chiroselective templates for transient molecular attachment, which process mediates the gratings' evolution.