Titanium-Based Tetrakis-2,3-[5,6-di(Substituted)pyrazino]porphyrazine: Synthesis and Characterization

Tetrapyrazinoporphyrazine (TPysPz) ligands and metal complexes find, generally, application as electronic materials and catalysts. Considering the limited application of Titanium (Ti), we prepared and characterized a family of ligands and Ti-based complexes of tetrakis-2,3-[5,6-di-R8-pyrazino]porphyrazine (R = H, 2-Py, Ph). UV/Vis measurements in different solvents confirm molecular aggregation, which results more pronounced in the presence of 2-pyridil and phenyl substituents on the macrocycle edge. Because of low solubility, solid state NMR was applied for structure characterization. Additional IR and MALDI-TOF were carried out to complete the characterization. Cyclic voltammetry in DMSO/Bu4NBF4 0.1 m unveiled that our Ti complexes can take part in up to five redox events. The first two quasi-reversible reductions involve Ti(IV), whereas the further to or three occur at the expense of the TPysPz macrocycle. To test the applicability of our compounds as catalytic materials, we performed a preliminary cyclic voltammetry investigation in the solid-state, which showed typical peaks of hydrogen redox reactions

Serum Biomarker Profile Including CCL1, CXCL10, VEGF, and Adenosine Deaminase Activity Distinguishes Active From Remotely Acquired Latent Tuberculosis

INTRODUCTION: There is an urgent medical need to differentiate active tuberculosis (ATB) from latent tuberculosis infection (LTBI) and prevent undertreatment and overtreatment. The aim of this study was to identify biomarker profiles that may support the differentiation between ATB and LTBI and to validate these signatures. MATERIALS AND METHODS: The discovery cohort included adult individuals classified in four groups: ATB (n = 20), LTBI without prophylaxis (untreated LTBI; n = 20), LTBI after completion of prophylaxis (treated LTBI; n = 20), and healthy controls (HC; n = 20). Their sera were analyzed for 40 cytokines/chemokines and activity of adenosine deaminase (ADA) isozymes. A prediction model was designed to differentiate ATB from untreated LTBI using sparse partial least squares (sPLS) and logistic regression analyses. Serum samples of two independent cohorts (national and international) were used for validation. RESULTS: sPLS regression analyses identified C-C motif chemokine ligand 1 (CCL1), C-reactive protein (CRP), C-X-C motif chemokine ligand 10 (CXCL10), and vascular endothelial growth factor (VEGF) as the most discriminating biomarkers. These markers and ADA(2) activity were significantly increased in ATB compared to untreated LTBI (p ≤ 0.007). Combining CCL1, CXCL10, VEGF, and ADA2 activity yielded a sensitivity and specificity of 95% and 90%, respectively, in differentiating ATB from untreated LTBI. These findings were confirmed in the validation cohort including remotely acquired untreated LTBI participants. CONCLUSION: The biomarker signature of CCL1, CXCL10, VEGF, and ADA2 activity provides a promising tool for differentiating patients with ATB from non-treated LTBI individuals

Accuracy of Immunodiagnostic Tests for Active Tuberculosis Using Single and Combined Results: A Multicenter TBNET-Study

The clinical application of IFN-gamma release assays (IGRAs) has recently improved the diagnosis of latent tuberculosis infection. In a multicenter study of the Tuberculosis Network European Trialsgroup (TBNET) we aimed to ascertain in routine clinical practice the accuracy of a novel assay using selected peptides encoded in the mycobacterial genomic region of difference (RD) 1 for the diagnosis of active tuberculosis in comparison with tuberculin skin test (TST), QuantiFERON-TB GOLD In-Tube (Cellestis Ltd., Carnegie, Australia) and T-SPOT.TB (Oxfordimmunotec, Abingdon, UK)

HIV incidence estimate combining HIV/AIDS surveillance, testing history information and HIV test to identify recent infections in Lazio, Italy

<p>Abstract</p> <p>Background</p> <p>The application of serological methods in HIV/AIDS routine surveillance systems to identify persons with recently acquired HIV infection has been proposed as a tool which may provide an accurate description of the current transmission patterns of HIV. Using the information about recent infection it is possible to estimate HIV incidence, according to the model proposed by Karon et al. in 2008, that accounts for the effect of testing practices on the number of persons detected as recently infected.</p> <p>Methods</p> <p>We used data from HIV/AIDS surveillance in the period 2004-2008 to identify newly diagnosed persons. These were classified with recent/non-recent infection on the basis of an avidity index result, or laboratory evidence of recently acquired infection (i.e., previous documented negative HIV test within 6 months; or presence of HIV RNA or p24 antigen with simultaneous negative/indeterminate HIV antibody test). Multiple imputation was used to impute missing information. The incidence estimate was obtained as the number of persons detected as recently infected divided by the estimated probability of detection. Estimates were stratified by calendar year, transmission category, gender and nationality.</p> <p>Results</p> <p>During the period considered 3,633 new HIV diagnoses were reported to the regional surveillance system. Applying the model, we estimated that in 2004-2008 there were 5,465 new infections (95%CI: 4,538-6,461); stratifying by transmission category, the estimated number of infections was 2,599 among heterosexual contacts, 2,208 among men-who-have-sex-with-men, and 763 among injecting-drug-users. In 2008 there were 952 (625-1,229) new HIV infections (incidence of 19.9 per 100,000 person-years). In 2008, for men-who-have-sex-with-men (691 per 100,000 person-years) and injecting drug users (577 per 100,000 person-years) the incidence remained comparatively high with respect to the general population, although a decreasing pattern during 2004-2008 was observed for injecting-drug-users.</p> <p>Conclusions</p> <p>These estimates suggest that the transmission of HIV infection in Lazio remains frequent and men-who-have-sex-with men and injecting-drug-users are still greatly affected although the majority of new infections occurs among heterosexual individuals.</p

Preparation and characterization of phosphotungstic acid-derived salt/Nafion nanocomposite membranes for proton exchange membrane fuel cells

Nafion/Cs2.5H0.5PW12O40 nanocomposite membranes are prepared and characterized as alternate materials of PEMFC operation at high temperature/low humidity. The Cs2.5H0.5PW12O40 solid acid particles (hereafter CsPWA) have the high surface area, the high hygroscopic property and the ability to generate proton in the presence of water molecules. The results of prepared membranes at three levels (0, 10 and 15%) indicate that the CsPWA particles have influence on the water content, ion exchange capacity, thermal properties (TGA and DSC), proton conductivity and PEM fuel cell performance. Particles agglomeration and Nafion active sites (sulfonic groups) covering are seen in the nanocomposite membranes. The conductivity of nanocomposite membranes at high temperatures (110 and 120 degrees C) is higher than plain Nafion and may be related to the additional water within the nanocomposite membrane and/or the additional surface functional site provide by CsPWA. The fuel cell responses show that in the fully hydrated state and at the higher current densities, the prepared MEAs with nanocomposite membranes possess better response compared with the plain Nafion. In partially hydrated cell, at both low and high current densities, the superior performance of the MEA prepared by nanocomposite membranes is observed. (C) 2010 Elsevier B.V. All rights reserved

Solvent-free nanocomposite proton-conducting membranes composed of cesium salt of phosphotungstic acid doped PVDF-CTFE/PEO blend

In this research, novel nanocomposite membranes were prepared using polymer blend of polyethylene oxide (PEO) and polyvinylidene fluoride-chloro tetrafluoro ethylene (PVDF-CTFE) copolymer with cesium salt of phosphotungstic acid (Cs2.5H0.5PWO40) as proton conductor. Nanocomposite membranes were prepared by solvent-free procedure. The DSC studies show a decrease in crystalinity of polymer matrix with increasing PEO to PVDF-CTFE proportional ratio and the filler. The TGA studies show that membranes are stable up to 180 °C. The TGA also indicates that addition of cesium salt of phosphotungstic acid increases the thermal stability of membranes. The SEMs exhibit that membranes are non-porous and the additive components are homogenously dispersed. Conductivity tests for membranes were carried out in the range of 25-100 °C in dry and hydrated states. Results show that by increasing the temperature, membranes conductivities are increased. In dry state, except at the temperature of 45 °C, membranes which have the highest crystalinity, have the highest conductivity. The alteration of the conductivity in the range of temperatures in dry condition may be attributed to segmental motion of polymer which resulted in proton hopping from one site to another or increasing free volume for proton motion. In fully hydrated state, dynamic equilibrium between different proton moieties determines the mode of proton conductivity which can be described by Grothuss mechanism. In the presence of water molecule, the free proton may be formed. The conductivity for the membrane in hydrated state with the blend ratio of PVDF:PEO = 95:5 w/w and 10% addition of cesium salt of phosphotungstic acid at the temperature of 90 °C is 1.05 × 10-4 S cm-1. © 2010 Springer-Verlag

Adaptive neuro-fuzzy inference system and artificial neural network modeling of proton exchange membrane fuel cells based on nanocomposite and recast Nafion membranes

In this study, a proton exchange membrane fuel cell (PEMFC) is modeled by multilayer perceptron neural network (MLPNN), RBF neural network (RBFNN), and adaptive neuro-fuzzy inference system (ANFIS). Experimental data are obtained on the basis of the fabricated membrane-electrode assembly (MEA) responses using prepared nanocomposite and recast Nafion membranes in the PEMFC. Four parameters including cell temperature, inlet gas temperature, current density, and inorganic additive percent are used as inputs, and the cell voltage is considered as the output. The results show that there is no considerable discrepancy between the RBFNN accuracy (R=0.99554) and the MLPNN accuracy (R=0.99609) for the performance prediction. The required time for developing the RBFNN model is significantly lower than the MLPNN model. A variety of ANFIS structure is explored to approximate the behavior of the system. The effect of cell and inlet gas temperatures on the PEMFC performance is investigated by the ANFIS developed model. Predicted polarization and powercurrent behavior by the ANFIS for the MEA prepared by the recast Nafion and the nanocomposite membranes at the cell temperatures 50 degrees C to110 degrees C are in high agreement with the experimental data. Predicted data by the ANFIS show that because of the property of Cs2.5H0.5PW12O40 additive for retaining water, much higher current density and power density at the same voltage are achieved for the nanocomposite membrane compared with the recast Nafion membrane in the PEMFC. Copyright (c) 2011 John Wiley & Sons, Ltd

Low-Temperature Phase Transitions of 1-Butyl-1-methylpyrrolidinium Bis(trifluoromethanesulfonyl)imide Swelling a Polyvinylidenefluoride Electrospun Membrane

We studied the temperature behavior of 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR14TFSI) swelling a polyvinylidenefluoride (PVdF) electrospun membrane by means of differential scanning calorimetry and dynamic mechanical analysis. The pure ionic liquid undergoes a glass transition around -85 degrees C independently of the cooling rate (4 or 0.5 degrees C/min). However, when PYR14TFSI swells the polymer membrane crystallization can be induced, either by cooling with a slow temperature rate (0.5 degrees C/min) around -52 degrees C or by prolonged isothermal treatments at -40 degrees C. The kinetics of the crystallization can be described by the usual Johnson-Mehl-Avrami-Kolmogorov equation, for both the isothermal and nonisothermal process. An Avrami index n = 3.78 +/- 0.09 and an activation energy for the crystallization on cooling of the ionic liquid (IL) in the PVdF membrane of 16.0 +/- 0.4 kJ/mol (37.9 +/- 0.1 J/g) are obtained from our experimental data

Hybrid membranes based on sulfated titania nanoparticles as low-cost proton conductors

This work reports on a novel, hybrid solid-state membrane based on sulfated titania nanoparticles stabilized by a polyvinylidene fluoride-hexafluoropropylene copolymer. A fast solvent-casting technique was adopted as a valid alternative to a fully dry, hot-pressing preparation procedure. Self-standing, flexible membranes with high proton conductivity were obtained