Iloprost Attenuates Oxidative Stress-Dependent Activation of Collagen Synthesis Induced by Sera from Scleroderma Patients in Human Pulmonary Microvascular Endothelial Cells

Endothelial cell injury is an early event in systemic sclerosis (SSc) pathogenesis and several studies indicate oxidative stress as the trigger of SSc-associated vasculopathy. Here, we show that circulating factors present in sera of SSc patients increased reactive oxygen species (ROS) production and collagen synthesis in human pulmonary microvascular endothelial cells (HPMECs). In addition, the possibility that iloprost, a drug commonly used in SSc therapy, might modulate the above-mentioned biological phenomena has been also investigated. In this regard, as compared to sera of SSc patients, sera of iloprost-treated SSc patients failed to increased ROS levels and collagen synthesis in HPMEC, suggesting a potential antioxidant mechanism of this drug.     

Comparative two-dimensional mapping of prion protein isoforms in human cerebrospinal fluid and central nervous system

The cellular prion protein (PrP(C)) is a glycosylphosphatidylinositol (GPI)-anchored glycoprotein abundant in neurons. Although its precise function is unknown, PrP(C) represents the substrate for the generation of a conformational pathogenic isoform (PrP(Sc)) in human and animal transmissible spongiform encephalopathies, or prion diseases. By applying novel solubilization cocktails, we analyzed normal human brain and cerebrospinal fluid (CSF) PrP(C) by immunoblot of two-dimensional (2-D) gel electrophoresis preparations, using specific antibodies. Here, we show that PrP(C) from brain and CSF is composed of several charge isomers of differently glycosylated isoforms of the full-length PrP(C) and two N-terminally truncated fragments of 20 and 18 kDa. In the CSF, substantial amounts of the highly glycosylated PrP(C) isoforms and of the unglycosylated 18 kDa fragment are detected. Our study, for the first time, provides a detailed 2-D map of human PrP(C) both in brain and CSF, and establishes an innovative and sensitive method that might help in detecting the CSF pathological PrP(Sc) isoform in vivo. It also shows the incredible microheterogeneity of such isoforms (ca. 60 spots!), as revealed in 2-D mapping, as opposed to 3-4 main zones by mono-dimensional sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE).     

Optical properties of Cu nanoclusters supported on MgO(100)

The vertical transitions of Cu atoms, dimers, and tetramers deposited on the MgO surface have been investigated by means of ab initio calculations based either on complete active space second-order perturbation theory or on time-dependent density functional theory. Three adsorption sites have been considered as representative of the complexity of the MgO surface: regular sites at flat (100) terraces, extended defects such as monoatomic steps, and point defects such as neutral oxygen vacancies (F or color centers). The optical properties of the supported Cu clusters have been compared with those of the corresponding gas-phase units. Upon deposition a substantial modification of the energy levels of the supported cluster is induced by the Pauli repulsion with the substrate. This causes shifts in the optical transitions going from free to supported clusters. The changes in cluster geometry induced by the substrate have a much smaller effect on the optical absorption bands. On F centers the presence of filled impurity levels in the band gap of MgO results in a strong mixing with the empty levels of the Cu atoms and clusters with consequent deep changes in the optical properties of the color centers. The results allow to interpret electron energy loss spectra of Cu atoms deposited on MgO thin films.     

Gold atoms and dimers on amorphous SiO(2): calculation of optical properties and cavity ringdown spectroscopy measurements

We report on the optical absorption spectra of gold atoms and dimers deposited on amorphous silica in size-selected fashion. Experimental spectra were obtained by cavity ringdown spectroscopy. Issues on soft-landing, fragmentation, and thermal diffusion are discussed on the basis of the experimental results. In parallel, cluster and periodic supercell density functional theory (DFT) calculations were performed to model atoms and dimers trapped on various defect sites of amorphous silica. Optically allowed electronic transitions were calculated, and comparisons with the experimental spectra show that silicon dangling bonds [[triple bond]Si(.-)], nonbridging oxygen [[triple bond]Si-O(.-)], and the silanolate group [[triple bond]Si-O(-)] act as trapping centers for the gold particles. The results are not only important for understanding the chemical bonding of atoms and clusters on oxide surfaces, but they will also be of fundamental interest for photochemical studies of size-selected clusters on surfaces.     

Ni(II), Cu(II), and Zn(II) dinuclear metal complexes with an aza-phenolic ligand: crystal structures,magnetic properties,and solution studies

The basicity behavior and ligational properties of the ligand 2-((bis(aminoethyl)amino)methyl)phenol (L) toward Ni(II), Cu(II), and Zn(II) ions were studied by means of potentiometric measurements in aqueous solution (298.1 +/- 0.1 K, l = 0.15 mol dm-3). The anionic L-H- species can be obtained in strong alkaline solution; this species behaves as tetraprotic base (log K1 = 11.06, log K2 = 9.85, log K3 = 8.46, log K4 = 2.38). L forms mono- and dinuclear complexes in aqueous solution with all the transition metal ions examined; the dinuclear species show a [M2(L-H)2]2+ stoichiometry in which the ligand/metal ratio is 2:2. The studies revealed that two mononuclear [ML-H]+ species self-assemble, giving the dinuclear complexes, which can be easily isolated from the aqueous solution due to their low solubility. This behavior is ascribed to the fact that L does not fulfill the coordination requirement of the ion in the mononuclear species and to the capacity of the phenolic oxygen, as phenolate, to bridge two metal ions. All three dinuclear species were characterized by determining their crystal structures, which showed similar coordination patterns, where all the single metal ions are substantially coordinated by three amine functions and two oxygen atoms of the phenolate moieties. The two metals in the dinuclear complexes are at short distance interacting together as shown by magnetic measurements performed with Ni(II) and Cu(II) complexes, which revealed an antiferromagnetic coupling between the two metal ions. The [Cu2(L-H)2]2+ cation shows a phase transition occurring by the temperature between 100 and 90 K; the characterization of the compounds existing at different temperatures was investigated using X-ray single-crystal diffraction, EPR, and magnetic measurements.     

Study of the phenolic composition of spanish and italian monocultivar extra virgin olive oils: Distribution of lignans, secoiridoidic, simple phenols and flavonoids

The aim of the present study was to compare the phenolic content in selected monocultivar extra virgin olive oils. Analyses were carried out by HPLC/DAD/MS on Picual, Picuda, Arbequina and Hojiblanca oils from Spain and Seggianese and Taggiasca oils from Italy. Oils from cultivar Picual showed similar characteristics to those of Seggianese oils, with total amounts of secoiridoids of 498.7 and 619.2 mg/L, respectively. The phenolic composition of Arbequina oils is close to that of the Taggiasca variety with lignans among the main compounds. The determination of free and linked OH-Tyr, by way of an acid hydrolysis, represents a rapid and suitable method, especially when standards are not available, to determine antioxidant potentialities in terms of MPC, particularly for fresh extra virgin olive oils rich in secoiridoidic derivatives.     

Quality control in hair analysis: A systematic study on washing procedures for trace element determinations

Trace element analysis of human hair is widely used to provide an indicator of body burden, but there is a major problem associated with preparation. The washing procedure adopted before analysis represents still a critical point which deserves particular attention. This study aimed at comparing the efficiency of the most commonly used washing methods to identify the procedure which allows for satisfactory removal of external contamination alone. As results depend strongly on the element, toxic (Cd and Pb), essential trace (Cr, Cu, Se and Zn) and major (Ca, K and Mg) elements were tested. The comparison was carried out with six different methods which include use of ionic and non-ionic detergents, organic solvents, chelating agents and sonication. Removal efficiency varied according to the element and pretreatment, the highest being observed for EDTA and the lowest for sonication. Unsatisfactory results were found using an acetone/methanol mixture for the potential contamination caused by it. Organic solvents showed the highest removal efficiency for K and toxic elements, and seemed to be effective in removing a limited but significant fraction of element incorporated in the lipid matter of hair. The ionic detergent Na lauryl sulphate, instead, was more effective for essential elements, but also triggered a higher analytic variability. As detergents appear to remove only external contamination, a non-ionic detergent such as Triton X-100 is proposed as a reliable alternative to the acetone method recommended by IAEA. Practical advantages are safe working conditions, rapidity of application and reduction in costs.     

Gagliardo-Nirenberg inequalities for differential forms in Heisenberg groups

The \(L^1\)-Sobolev inequality states that for compactly supported functions u on the Euclidean n-space, the \(L^{n/(n-1)}\)-norm of a compactly supported function is controlled by the \(L^1\)-norm of its gradient. The generalization to differential forms (due to Lanzani and Stein and Bourgain and Brezis) is recent, and states that a the \(L^{n/(n-1)}\)-norm of a compactly supported differential h-form is controlled by the \(L^1\)-norm of its exterior differential du and its exterior codifferential \(\delta u\) (in special cases the \(L^1\)-norm must be replaced by the \(\mathcal H^1\)-Hardy norm). We shall extend this result to Heisenberg groups in the framework of an appropriate complex of differential forms.