Kinetics and mechanism of gas-phase thermolysis using headspace-gas chromatographic analysis

Headspace gas chromatography is employed in order to study the thermal decomposition reaction of gaseous di-tert-butyl peroxide (DTBP) in the 130°C to 160°C temperature range and in the presence of n-hexane as the internal standard and nitrogen as the carrier gas. The reaction exclusively yields acetone and ethane as products. First-order kinetics are observed, including when the surface-to-volume ratio (S/V) of the Pyrex 20-mL vial employed as the reactor is increased by packing it with silanized glass wool. However, a small increase in the rate constant values is observed at each temperature, which supports a heterogeneous surface process in DTBP decomposition. The rate constant's dependence on the homogeneous unimolecular decomposition reaction corresponds to the O-O bond rupture of the DTBP molecule in a stepwise three-stage mechanism. Thus, the relevant question of the participation of a surface catalytic effect in the DTBP gas-phase thermolysis can easily be assessed through the procedure described in this work. In general, this is advantageous for the rapid investigation of the reaction kinetics of volatile compounds at different temperatures.Laboratorio de Estudio de Compuestos Orgánico

Co-evolutionnary network approach to cultural dynamics controlled by intolerance

Starting from Axelrod's model of cultural dissemination, we introduce a rewiring probability, enabling agents to cut the links with their unfriendly neighbors if their cultural similarity is below a tolerance parameter. For low values of tolerance, rewiring promotes the convergence to a frozen monocultural state. However, intermediate tolerance values prevent rewiring once the network is fragmented, resulting in a multicultural society even for values of initial cultural diversity in which the original Axelrod model reaches globalization

Kinetics and mechanism of gas-phase thermolysis using headspace-gas chromatographic analysis

Headspace gas chromatography is employed in order to study the thermal decomposition reaction of gaseous di-tert-butyl peroxide (DTBP) in the 130°C to 160°C temperature range and in the presence of n-hexane as the internal standard and nitrogen as the carrier gas. The reaction exclusively yields acetone and ethane as products. First-order kinetics are observed, including when the surface-to-volume ratio (S/V) of the Pyrex 20-mL vial employed as the reactor is increased by packing it with silanized glass wool. However, a small increase in the rate constant values is observed at each temperature, which supports a heterogeneous surface process in DTBP decomposition. The rate constant's dependence on the homogeneous unimolecular decomposition reaction corresponds to the O-O bond rupture of the DTBP molecule in a stepwise three-stage mechanism. Thus, the relevant question of the participation of a surface catalytic effect in the DTBP gas-phase thermolysis can easily be assessed through the procedure described in this work. In general, this is advantageous for the rapid investigation of the reaction kinetics of volatile compounds at different temperatures.Laboratorio de Estudio de Compuestos Orgánico

Gender differences in cooperation: experimental evidence on high school students

The emergence of cooperation among unrelated human subjects is a long-standing conundrum that has been amply studied both theoretically and experimentally. Within the question, a less explored issue relates to the gender dependence of cooperation, which can be traced back to Darwin, who stated that "women are less selfish but men are more competitive". Indeed, gender has been shown to be relevant in several game theoretical paradigms of social cooperativeness, including prisoner's dilemma, snowdrift and ultimatum/dictator games, but there is no consensus as to which gender is more cooperative. We here contribute to this literature by analyzing the role of gender in a repeated Prisoners' Dilemma played by Spanish high-school students in both a square lattice and a heterogeneous network. While the experiment was conducted to shed light on the influence of networks on the emergence of cooperation, we benefit from the availability of a large dataset of more 1200 participants. We applied different standard econometric techniques to this dataset, including Ordinary Least Squares and Linear Probability models including random effects. All our analyses indicate that being male is negatively associated with the level of cooperation, this association being statistically significant at standard levels. We also obtain a gender difference in the level of cooperation when we control for the unobserved heterogeneity of individuals, which indicates that the gender gap in cooperation favoring female students is present after netting out this effect from other socio-demographics factors not controlled for in the experiment, and from gender differences in risk, social and competitive preferences.This paper has benefited from the funding from the Spanish Ministry of Education and Science (Projects ECO2012-34828, RESINEE and PRODIEVO). The funders had no role in study design, data collection and analysis, decision to publish, or preparation of the manuscript

Colecciones, correctores y generadores automáticos de ejercicios de programación

Este artículo pretende analizar algunos de los logros conseguidos en el ámbito de las colecciones, correctores y generadores automáticos de ejercicios. Se presta particular atención a problemas de programación, pero se consideran metodologías y temáticas comunes a otras disciplinas. Recientemente se han desarrollado múltiples herramientas pero falta una sistematización de las mismas. El objetivo del artículo es consolidar el conocimiento de estos sistemas, lo que puede ser la base para un uso más racional de ellos y para identificar mejoras.El trabajo se ha financiado con el proyecto TIC2000-1413 de la CICYT

Modeling nonlinear power amplifiers in OFDM systems from subsampled data: a comparative study using real measurements

A comparative study among several nonlinear high-power amplifier (HPA) models using real measurements is carried out. The analysis is focused on specific models for wideband OFDM signals, which are known to be very sensitive to nonlinear distortion. Moreover, unlike conventional techniques, which typically use a single-tone test signal and power measurements, in this study the models are fitted using subsampled time-domain data. The in-band and out-of-band (spectral regrowth) performances of the following models are evaluated and compared: Saleh’s model, envelope polynomial model (EPM), Volterra model, the multilayer perceptron (MLP) model, and the smoothed piecewise-linear (SPWL) model. The study shows that the SPWL model provides the best in-band characterization of the HPA. On the other hand, the Volterra model provides a good trade-off between model complexity (number of parameters) and performance

Formation Mechanism of Maghemite Nanoflowers Synthesized by a Polyol-Mediated Process

Magnetic nanoparticles are being developed as structural and functional materials for use in diverse areas, including biomedical applications. Here, we report the synthesis of maghemite (γ-Fe₂O₃) nanoparticles with distinct morphologies: single-core and multicore, including hollow spheres and nanoflowers, prepared by the polyol process. We have used sodium acetate to control the nucleation and assembly process to obtain the different particle morphologies. Moreover, from samples obtained at different time steps during the synthesis, we have elucidated the formation mechanism of the nanoflowers: the initial phases of the reaction present a lepidocrocite (γ-FeOOH) structure, which suffers a fast dehydroxylation, transforming to an intermediate “undescribed” phase, possibly a partly dehydroxylated lepidocrocite, which after some incubation time evolves to maghemite nanoflowers. Once the nanoflowers have been formed, a crystallization process takes place, where the γ-Fe₂O₃ crystallites within the nanoflowers grow in size (from ∼11 to 23 nm), but the particle size of the flower remains essentially unchanged (∼60 nm). Samples with different morphologies were coated with citric acid and their heating capacity in an alternating magnetic field was evaluated. We observe that nanoflowers with large cores (23 nm, controlled by annealing) densely packed (tuned by low NaAc concentration) offer 5 times enhanced heating capacity compared to that of the nanoflowers with smaller core sizes (15 nm), 4 times enhanced heating effect compared to that of the hollow spheres, and 1.5 times enhanced heating effect compared to that of single-core nanoparticles (36 nm) used in this work

Analysis of the alteration in the optical configuration of Raman spectrometer: Optimization of signal-to-noise ratio (SNR) in a specific wavelength range of clinical interest

Abstract. The present article is focused on the optimization of the optical parameters of a Raman spectrometer in order to obtain a minimum width of its spectral lines. In this way, using as reference the width of a fingerprint band of a calcified biological tissue, a spectral line without distortion or any loss of resolution was identified. This optimization is employed with the aim of improvement of the signal-to-noise ratio (SNR). A great improvement in the efficiency of the spectral collect was obtained, which can reduce significantly the time of diagnosis of target tissues, such as the calcified coronarian tissue. Therefore, the potential application of this new spectroscopic system increases the efficiency and precision, favoring the security of this technique to future in vivo applications. The excellent results obtained in this work become this spectroscopic system a powerful tool to the clinical diagnosis of several diseases

EWS-FLI1-mediated suppression of the RAS-antagonist Sprouty 1 (SPRY1) confers aggressiveness to Ewing sarcoma

Ewing sarcoma is characterized by chromosomal translocations fusing the EWS gene with various members of the ETS family of transcription factors, most commonly FLI1. EWS-FLI1 is an aberrant transcription factor driving Ewing sarcoma tumorigenesis by either transcriptionally inducing or repressing specific target genes. Herein, we showed that Sprouty 1 (SPRY1), which is a physiological negative feedback inhibitor downstream of fibroblast growth factor (FGF) receptors (FGFRs) and other RAS-activating receptors, is an EWS-FLI1 repressed gene. EWS-FLI1 knockdown specifically increased the expression of SPRY1, while other Sprouty family members remained unaffected. Analysis of SPRY1 expression in a panel of Ewing sarcoma cells showed that SPRY1 was not expressed in Ewing sarcoma cell lines, suggesting that it could act as a tumor suppressor gene in these cells. In agreement, induction of SPRY1 in three different Ewing sarcoma cell lines functionally impaired proliferation, clonogenic growth and migration. In addition, SPRY1 expression inhibited extracellular signal-related kinase/mitogen-activated protein kinase (MAPK) signaling induced by serum and basic FGF (bFGF). Moreover, treatment of Ewing sarcoma cells with the potent FGFR inhibitor PD-173074 reduced bFGF-induced proliferation, colony formation and in vivo tumor growth in a dose-dependent manner, thus mimicking SPRY1 activity in Ewing sarcoma cells. Although the expression of SPRY1 was low when compared with other tumors, SPRY1 was variably expressed in primary Ewing sarcoma tumors and higher expression levels were significantly associated with improved outcome in a large patient cohort. Taken together, our data indicate that EWS-FLI1-mediated repression of SPRY1 leads to unrestrained bFGF-induced cell proliferation, suggesting that targeting the FGFR/MAPK pathway can constitute a promising therapeutic approach for this devastating disease.FC-A, LG-G, JCL, AS, PG-M, SEL-P, SM and JA are supported by Asociación Pablo Ugarte and Miguelañez SA, ASION-La Hucha de Tomás, Fundación La Sonrisa de Alex and Instituto de Salud Carlos III (PI12/00816 and Spanish Cancer Network RTICC RD12/0036/0027). TGPG is supported by a grant from ‘Verein zur Förderung von Wissenschaft und Forschung an der Medizinischen Fakultät der LMU München (WiFoMed)’, the Daimler and Benz Foundation in cooperation with the Reinhard Frank Foundation, by LMU Munich’s Institutional Strategy LMUexcellent within the framework of the German Excellence Initiative, the ‘Mehr LEBEN für krebskranke Kinder—Bettina-Bräu-Stiftung’, the Walter Schulz Foundation, the Fritz Thyssen Foundation (FTH-40.15.0.030MN) and by the German Cancer Aid (DKH-111886 and DKH-70112257). The ‘Genetics and Biology of Cancers’ team (TGPG, DS and OD) is supported by grants from the Ligue Nationale Contre Le Cancer (Equipe labellisée). This work was also supported by the European PROVABES, ASSET and EEC FP7 grants. We also thank the following associations for their invaluable support: the Société Française des Cancers de l’Enfant, Courir pour Mathieu, Dans les pas du Géant, Olivier Chape, Les Bagouzamanon, Enfants et Santé and les Amis de Claire. We thank Dr S Navarro (University of Valencia, Valencia, Spain) and Dr TJ Triche (Children’s Hospital Los Angeles, Los Angeles, USA) for providing us with Ewing sarcoma cell lines A4573 and TTC-466, respectively.S