Oxygen transport in nanostructured lanthanum manganites

Methods and models describing oxygen diffusion and desorption in oxides have been developed for slightly defective and well crystallised bulky materials. Does nanostructuring change the mechanism of oxygen mobility? In such a case, models should be properly checked and adapted to take into account new material properties. In order to do so, temperature programmed oxygen desorption and thermogravimetric analysis, either in isothermal or ramp mode, have been used to investigate some nanostructured La1\u2013xAxMnO3 d samples (A = Sr and Ce, 20\u201360 nm particle size) with perovskite-like structure. The experimental data have been elaborated by means of different models to define a set of kinetic parameters able to describe oxygen release properties and oxygen diffusion through the bulk. Different rate-determining steps have been identified, depending on the temperature range and oxygen depletion of the material. In particular, oxygen diffusion was shown to be rate-limiting at low temperature and at low defect concentration, whereas oxygen recombination at the surface seems to be the rate-controlling step at high temperature. However, the oxygen recombination step is characterised by an activation energy much lower than that for diffusion. In the present paper oxygen transport in nanosized materials is quantified by making use of widely diffused experimental techniques and by critically adapting to nanoparticles suitably chosen models developed for bulk materials

The developmental pathways of preschool children with acute lymphoblastic leukemia: communicative and social sequelae one year after treatment

Early childhood is considered to be a period of rapid development, with the acquisition of abilities predicting future positive school competences. Motor, cognitive, and social diculties related to cancer therapies heavily impact the development of children with cancer. This study focused on two main aims: To assess the developmental pathways of preschool children with acute lymphoblastic leukemia one year post-treatment and to compare these abilities both with those of a control group of healthy peers and with Italian norms. Forty-four children and their families, recruited through the Hematology-Oncologic Clinic of the Department of Child andWoman Health (University of Padua), agreed to participate in this study. The children\u2019s mean age was 4.52 years (SD = 0.94, range = 2.5\u20136 years), equally distributed by gender, all diagnosed with acute lymphoblastic leukemia. Matched healthy peers were recruited through pediatricians\u2019 ambulatories. Each family was interviewed adopting the Vineland adaptive behavior scales. Paired sampleWilcoxon tests revealed that children were reported to have significantly more developmental diculties than their healthy peers. When compared with Italian norms, they scored particularly low in verbal competence, social, and coping skills. No significant association was found between treatment variables and developmental abilities. These findings suggest that the creation of specialized interventions, both for parents and children, may fill the possible delays in children\u2019s development probably due to stress, lack of adequate stimulation, or dicult adaptation

The Overlooked Potential of Generalized Linear Models in Astronomy - I: Binomial Regression

Revealing hidden patterns in astronomical data is often the path to fundamental scientific breakthroughs; meanwhile the complexity of scientific inquiry increases as more subtle relationships are sought. Contemporary data analysis problems often elude the capabilities of classical statistical techniques, suggesting the use of cutting edge statistical methods. In this light, astronomers have overlooked a whole family of statistical techniques for exploratory data analysis and robust regression, the so-called Generalized Linear Models (GLMs). In this paper -- the first in a series aimed at illustrating the power of these methods in astronomical applications -- we elucidate the potential of a particular class of GLMs for handling binary/binomial data, the so-called logit and probit regression techniques, from both a maximum likelihood and a Bayesian perspective. As a case in point, we present the use of these GLMs to explore the conditions of star formation activity and metal enrichment in primordial minihaloes from cosmological hydro-simulations including detailed chemistry, gas physics, and stellar feedback. We predict that for a dark mini-halo with metallicity $\approx 1.3 \times 10^{-4} Z_{\bigodot}$, an increase of $1.2 \times 10^{-2}$ in the gas molecular fraction, increases the probability of star formation occurrence by a factor of 75%. Finally, we highlight the use of receiver operating characteristic curves as a diagnostic for binary classifiers, and ultimately we use these to demonstrate the competitive predictive performance of GLMs against the popular technique of artificial neural networks.Comment: 20 pages, 10 figures, 3 tables, accepted for publication in Astronomy and Computin

Phase Transformations in the CeO2-Sm2O3System : A Multiscale Powder Diffraction Investigation

The structure evolution in the CeO2-Sm2O3system is revisited by combining high resolution synchrotron powder diffraction with pair distribution function (PDF) to inquire about local, mesoscopic, and average structure. The CeO2fluorite structure undergoes two phase transformations by Sm doping, first to a cubic (C-type) and then to a monoclinic (B-type) phase. Whereas the C to B-phase separation occurs completely and on a long-range scale, no miscibility gap is detected between fluorite and C-type phases. The transformation rather occurs by growth of C-type nanodomains embedded in the fluorite matrix, without any long-range phase separation. A side effect of this mechanism is the ordering of the oxygen vacancies, which is detrimental for the application of doped ceria as an electrolyte in fuel cells. The results are discussed in the framework of other Y and Gd dopants, and the relationship between nanostructuring and the above equilibria is also investigated

Cool Core Clusters from Cosmological Simulations

We present results obtained from a set of cosmological hydrodynamic simulations of galaxy clusters, aimed at comparing predictions with observational data on the diversity between cool-core (CC) and non-cool-core (NCC) clusters. Our simulations include the effects of stellar and AGN feedback and are based on an improved version of the smoothed particle hydrodynamics code GADGET-3, which ameliorates gas mixing and better captures gas-dynamical instabilities by including a suitable artificial thermal diffusion. In this Letter, we focus our analysis on the entropy profiles, the primary diagnostic we used to classify the degree of cool-coreness of clusters, and on the iron profiles. In keeping with observations, our simulated clusters display a variety of behaviors in entropy profiles: they range from steadily decreasing profiles at small radii, characteristic of cool-core systems, to nearly flat core isentropic profiles, characteristic of non-cool-core systems. Using observational criteria to distinguish between the two classes of objects, we find that they occur in similar proportions in both simulations and in observations. Furthermore, we also find that simulated cool-core clusters have profiles of iron abundance that are steeper than those of NCC clusters, which is also in agreement with observational results. We show that the capability of our simulations to generate a realistic cool-core structure in the cluster population is due to AGN feedback and artificial thermal diffusion: their combined action allows us to naturally distribute the energy extracted from super-massive black holes and to compensate for the radiative losses of low-entropy gas with short cooling time residing in the cluster core.Comment: 6 pages, 4 figures, accepted in ApJL, v2 contains some modifications on the text (results unchanged

5kWe+5kWt reformer-PEMFC energy generator from bioethanol first data on the fuel processor from a demonstrative project

A power unit constituted by a reformer section, a H 2 purification section and a fuel cell stack is being tested c/o the Dept. of Physical Chemistry and Electrochemistry of Universit\ue0 degli Studi di Milano, on the basis of a collaboration with HELBIO S.A. Hydrogen and Energy Production Systems, Patras (Greece), supplier of the unit, and some sponsors (Linea Energia S.p.A., Parco Tecnologico Padano and Provincia di Lodi, Italy). The system size allows to co-generate 5 kW e (220 V, 50 Hz a.c.) + 5 kW t (hot water at 65\ub0C) as peak output. Bioethanol, obtainable by different non-food-competitive biomass, is transformed into syngas by a pre-reforming and reforming reactors couple and the reformate is purified from CO to a concentration below 20 ppmv, suitable to feed a proton exchange membrane fuel cell (PEMFC) stack that will be integrated in the fuel processor in a second step of the experimentation. This result is achieved by feeding the reformate to two water gas shift reactors, connected in series and operating at high and low temperature, respectively. CO concentration in the outcoming gas is ca. 0.4 vol% and the final CO removal to meet the specifications is accomplished by two methanation reactors in series. The second methanation step acts merely as a guard, since ca. 15 ppmv of CO are obtained already after the first reactor. The goals of the present project are to test the integrated fuel processor, to check the effectiveness of the proposed technology and to suggest possible adequate improvements

Beta-blocker treatment guided by head-up tilt test in neurally mediated syncope

This study was an open-label, uncontrolled, dose-escalation trial of beta-blockers in patients with a history of syncope without warning or syncope resulting in trauma (malignant vasovagal syncope) who had positive head-up tilt test (HUT) responses, with or without isoproterenol infusion. Thirty patients (mean age, 37 +/- 21 years) with recurrent syncopal and near-syncopal episodes of unexplained origin in the previous year (6 +/- 14 syncopal episodes and 17 +/- 3 near-syncopes) underwent HUT for diagnostic purposes and for guiding prophylactic treatment. After patients were given a 10-minute rest in a recumbent position, rye performed an WT at 70 degrees for 25 minutes; if indicated, isoproterenol testing was performed at incremental dosages (dye steps at 10-minute intervals at 80 degrees), AU patients experienced syncope during HUT, 15 (50%) at baseline HUT and 15 (50%) during isoproterenol infusion (1 to 3 mu g/min; mean, 1.6 mu g/min). Sixteen syncopes were of vasodepressor type, 10 were mixed, and 4 were of cardioinhibitory type. After baseline HUT, betablocking drugs were prescribed to all patients as follows: 1 patient was given propranolol (160 mg daily), and 29 patients were given metoprolol (246 +/- 49 mg daily), with a dose titration period of 14 days. HUT was repeated after 3 weeks, and 24 patients (80%) had negative results (no syncope or anomalous responses). After further dosage adjustment of beta-blockers in nonresponders, a negative HUT was obtained in 28 patients (93%). Overall mean metoprolol daily dose was 262 +/- 60 mg (29 patients), and propranolol was administered at 160 mg daily in 1 patient. Thirteen patients (43%) reported side effects, none of which required drug withdrawal. At an average follow-up of 16 +/- 4 months, none of the patients experienced syncope, a statistically significant reduction. Moreover, a statistically significant reduction in the number of near-syncopal episodes was observed in comparison to the previous year. None of the patients discontinued treatment because of long-term side effects. Beta-blockers were well tolerated and achieved a high rate of efficacy, even in cardioinhibitory syncopes. In conclusion, in selected patients with malignant vasovagal syncope, treatment with metoprolol or propranolol at relatively high doses is feasible and, if guided by HUT results, is associated with a favorable outcome in terms of freedom from syncopal recurrences. Appropriate titration to achieve the full beta-blocking effect appears to be advisable