Versatile Synthesis of Transition Metal Phosphides: Emerging Front-runners for Affordable Catalysis

Transition metal phosphide materials have found themselves at the forefront of research revolving around energy applications. Due to the vast range of properties possessed by marginally different phase compositions, binary and ternary metal phosphides are utilized as catalysts, semi-conductors and magnetocaloric materials along with many others. These attractive properties, which are highly phase dependent, call for a versatile and cost effective synthesis route for various phosphide materials without sacrificing properties important at the nanoscale such as particle size and morphology. The primary focus outlined in the work of this dissertation pertains to a versatile wet chemical synthesis capable of producing multiple phases of binary and ternary phosphides containing one or more of the transition metals cobalt, iron and nickel. These metals were of particular interest due to the proven catalytic activity of iron, cobalt or nickel binary phases and the lack of research conducted on the corresponding ternary phases. The challenge presented by wet chemical synthesis methods is the ability to separate different crystal phases of metal phosphide in a short amount of time, with less toxic and lower cost chemicals, and a simple synthetic process with the ability to produce products on a larger scale. Oleylamine was used as a solvent, capping agent and reducing agent along with trioctylphosphine or triphenylphosphine as a phosphorus source. Many binary phosphide phases were synthesized with the same method and purity of phase was controlled primarily with temperature or phosphorus to metal ratio (P:M). At lower temperatures (290-320°C) or lower P:M (4:1) Ni3P,Ni2P, Fe2P, and Co2P were synthesized while higher temperatures (330-360°C) or higher P:M (22:1) produced Ni5P4, Ni12P5, FeP and CoP. Ternary phosphides FeCoP and CoNiP were also successfully synthesized at temperatures of 300-330°C with small excesses of phosphorus (2-5 molar excess). Preliminary catalytic studies for the evolution of hydrogen gas were conducted to test the efficacy of phosphide materials produced via the simplistic oleylamine method. Ni2P was found to have the highest activity toward hydrogen evolution with an overpotential of 320 mV which is comparable and in some cases better than other unsupported phosphide catalysts of the same phase. The ability to control phase composition using a simple, cost effective wet chemical synthesis is promising for the future production of active metal phosphide materials

L’educazione dell’Indio. I gesuiti José de Acosta e Blas Valera su lingua e ingegni dei nativi peruviani

For the first Jesuits, the Peruvian Province has been a place of experimentation of educational practices and inculturation. The presence of a culture as complex as that of the Incas posed to the Society some crucial theological and political problems. To solve these problems, some of its members undertook grammatical, anthropological and historical studies that are still essential for understanding the peoples of the Andes. Among these studies, they are to be counted those of José de Acosta (1540-1600), who was provincial of Peru, and Blas Valera (1544-1597?/1619?), first Jesuit mestizo to be ordained a priest. Both were opposed to the policy of forced conversion of the Indios, but they proposed two different ways to educate the natives to Christianity. This paper aims at investigating the plots of these pathways, understanding them as two pedagogies strategically different, but not in opposition to each other

A Robust Filter for the BeppoSAX Gamma Ray Burst Monitor Triggers

The BeppoSAX Gamma Ray Burst Monitor (GRBM) is triggered any time a statistically significant counting excess is simultaneously revealed by at least two of its four independent detectors. Several spurious effects, including highly ionizing particles crossing two detectors, are recorded as onboard triggers. In fact, a large number of false triggers is detected, in the order of 10/day. A software code, based on an heuristic algorithm, was written to discriminate between real and false triggers. We present the results of the analysis on an homogeneous sample of GRBM triggers, thus providing an estimate of the efficiency of the GRB detection system consisting of the GRBM and the software.Comment: Proc. 5th Huntsville GRB Symposiu

Involvement of both sodium influx and potassium efflux in ciguatoxin-induced nodal swelling of frog myelinated axons

Ciguatoxins, mainly produced by benthic dinoflagellate Gambierdiscus species, are responsible for a complex human poisoning known as ciguatera. Previous pharmacological studies revealed that these toxins activate voltage-gated Na+ channels. In frog nodes of Ranvier, ciguatoxins induce spontaneous and repetitive action potentials (APs) and increase axonal volume that may explain alterations of nerve functioning in intoxicated humans. The present study aimed determining the ionic mechanisms involved in Pacific ciguatoxin-1B (P-CTX-1B)-induced membrane hyperexcitability and subsequent volume increase in frog nodes of Ranvier, using electrophysiology and confocal microscopy. The results reveal that P-CTX-1B action is not dependent on external Cl- ions since it was not affected by substituting Cl- by methylsulfate ions. In contrast, substitution of external Na+ by Li+ ions suppressed spontaneous APs and prevented nodal swelling. This suggests that P-CTX-1B-modified Na+ channels are not selective to Li+ ions and/or are blocked by these ions, and that Na+ influx through Na+ channels opened during spontaneous APs is required for axonal swelling. The fact that the K+ channel blocker tetraethylammonium modified, but did not suppress, spontaneous APs and greatly reduced nodal swelling induced by P-CTX-1B indicates that K+ efflux might also be involved. This is supported by the fact that P-CTX-1B, when tested in the presence of both tetraethylammonium and the K+ ionophore valinomycin, produced the characteristic nodal swelling. It is concluded that, during the action of P-CTX-1B, water movements responsible for axonal swelling depend on both Na+ influx and K+ efflux. These results pave the way for further studies regarding ciguatera treatment

Further insights on predictors of environmental tobacco smoke exposure during the pediatric age

Background: The smoking ban in public places has reduced Environmental Tobacco Smoke (ETS) exposure for non-smokers, but despite this, domestic environments still remain places at high risk of exposure, and, today, about 40% of children worldwide are exposed to ETS at home. The aims of the study are to investigate the contribution of several factors on ETS exposure among a group of Italian children and to evaluate the changes in smoking precautions adopted at home when the smoker is the mother, the father, or both parents, respectively. Methods: A cross-sectional study was performed on a sample of 519 Italian schoolchildren. Information was collected via a questionnaire. Results: 41.4% of the participants lived with at least one smoker. Almost half of the children exposed to ETS lived with one or more smokers who do not observe any home smoking ban. Lower maternal or paternal educational levels significantly increase the risk of ETS exposure at home and the “worst case” is represented by both parents who smoke. Conclusions: More effective preventive interventions are needed to protect children from ETS exposure. Some interventions should be specifically dedicated to smokers with a low educational level and to mothers that smoke

Loss of correlation between HIV viral load and CD4+ T-cell counts in HIV/HTLV-1 co-infection in treatment naive Mozambican patients

Seven hundred and four HIV-1/2-positive, antiretroviral therapy (ART) naïve patients were screened for HTLV-1 infection. Antibodies to HTLV-1 were found in 32/704 (4.5%) of the patients. Each co-infected individual was matched with two HIV mono-infected patients according to World Health Organization clinical stage, age +/-5 years and gender. Key clinical and laboratory characteristics were compared between the two groups. Mono-infected and co-infected patients displayed similar clinical characteristics. However, co-infected patients had higher absolute CD4+ T-cell counts (P = 0.001), higher percentage CD4+ T-cell counts (P < 0.001) and higher CD4/CD8 ratios (P < 0.001). Although HIV plasma RNA viral loads were inversely correlated with CD4+ T-cell-counts in mono-infected patients (P < 0.0001), a correlation was not found in co-infected individuals (P = 0.11). Patients with untreated HIV and HTLV-1 co-infection show a dissociation between immunological and HIV virological markers. Current recommendations for initiating ART and chemoprophylaxis against opportunistic infections in resource-poor settings rely on more readily available CD4+ T-cell counts without viral load parameters. These guidelines are not appropriate for co-infected individuals in whom high CD4+ T-cell counts persist despite high HIV viral load states. Thus, for co-infected patients, even in resource-poor settings, HIV viral loads are likely to contribute information crucial for the appropriate timing of ART introduction

Dual action of a dinoflagellate-derived precursor of Pacific ciguatoxins (P-CTX-4B) on voltage-dependent K(+) and Na(+) channels of single myelinated axons

The effects of Pacific ciguatoxin-4B (P-CTX-4B, also named gambiertoxin), extracted from toxic Gambierdiscus dinoflagellates, were assessed on nodal K(+) and Na(+) currents of frog myelinated axons, using a conventional voltage-clamp technique. P-CTX-4B decreased, within a few minutes, both K(+) and Na(+) currents in a dose-dependent manner, without inducing any marked change in current kinetics. The toxin was more effective in blocking K(+) than Na(+) channels. P-CTX-4B shifted the voltage-dependence of Na(+) conductance by about 14 mV towards more negative membrane potentials. This effect was reversed by increasing Ca(2+) in the external solution. A negative shift of about 16 mV in the steady-state Na(+) inactivation-voltage curve was also observed in the presence of the toxin. Unmodified and P-CTX-4B-modified Na(+) currents were similarly affected by the local anaesthetic lidocaine. The decrease of the two currents by lidocaine was dependent on both the concentration and the membrane potential during pre-pulses. In conclusion, P-CTX-4B appears about four times more effective than P-CTX-1B to affect K(+) channels, whereas it is about 50 times less efficient to affect Na(+) channels of axonal membranes. These actions may be related to subtle differences between the two chemical structures of molecules