Dinámica de reacciones unimoleculares en fase gas: Desviaciones del comportamiento estadístico

The present review summarizes the most relevant results of our research group obtained recently in the field of unimolecular reaction dynamics. The following processes are specifically analyzed: the isomerization, dissociation and elimination in methyl nitrite, the fragmentation reactions of the mercaptomethyl cation, the C-CO dissociation in the acetyl and propionyl radicals, and the decomposition of vinyl fluoride. In all the cases, only state- or energy-selected systems are considered. Special emphasis is paid to the possibility of systems exhibiting non-statistical behavior.

Estudi i simulació aerodinàmica amb programari de dinàmica de fluids computacional (CFD) en un model bàsic de vehicle de competició de la categoria CM (curses de muntanya)

Aquest projecte té com a objectiu la simulació numérica de la carrosseria d’ un vehicle de curses de muntanya de categoria CM

Estudo da estrutura e da solvatação do HNP-3, um antibiótico natural, por dinâmica molecular

The structure and hydration of the HNP-3 have been derived from molecular dynamics data using root mean square deviation, radial and energy distributions. Three antiparallel beta sheets were found to be preserved. 15 intramolecular hydrogen bonds were identified together with 36 hydrogen bonds on the backbone and 35 on the side chain atoms. From the point of view of the hydration dynamics, the analysis shows a high solvent accessibility of the monomer and attractive interactions with water molecules.

Um modelo para a superfície líquida no estudo da dinâmica do espalhamento de Xe e Ne pelo esqualano

In this work we present a theoretical model to investigate the scattering of Xe and Ne by a liquid squalane surface. The liquid surface is modeled as a grid of harmonic oscillators with frequencies adjusted to experimental vibration as frequencies of the liquid squalane and the atom-surface interaction potential is modeled by a Lennard-Jones function. The three dimensional description of the dynamics of the process which occurs at the gas-liquid interface is obtained by the classical trajectory method. The general characteristics of the dynamics of the scattering process are in good agreement with experimental data.

Construção e avaliação de célula de fluxo para estudo da tensão interfacial dinâmica da interface fluxo líquido - sólido por despolarização da fluorescência

A simple low-cost flow cell was developed, built and optimized in order to observe dynamic interfacial tension of continuous flow systems. Distinct materials can be used in one of the cell walls in order to observe the intermolecular forces between the flowing liquid and the chemical constitution of the walls. The fluorescence depolarization was evaluated using Rhodamine B as fluorescent probe seeded in ethylene glycol. The effects of the positioning angles on the data acquired across the cell are reported. The reproducibility of the data was evaluated with a spectrometer assembled in-house and the relative standard deviation was below 3%.

Quantificação de fluxos de mercúrio gasoso na interface solo/atmosfera utilizando câmara de fluxo dinâmica: aplicação na bacia do Rio Negro

Gaseous mercury sampling conditions were optimized and a dynamic flux chamber was used to measure the air/surface exchange of mercury in some areas of the Negro river basin with different vegetal coverings. At the two forest sites (flooding and non-flooding), low mercury fluxes were observed: maximum of 3 pmol m-2 h-1 - day and minimum of -1 pmol m-2 h-1 - night. At the deforested site, the mercury fluxes were higher and always positive: maximum of 26 pmol m-2 h-1 - day and 17 pmol m-2 h-1 - night. Our results showed that deforestation could be responsible for significantly increasing soil Hg emissions, mainly because of the high soil temperatures reached at deforested sites.

Dinâmica complexa no sistema bromato/hipofosfito/acetona/manganês e ferroína

New chemical systems have been recently designed for the study of complex phenomena such as oscillatory dynamics in the temporal domain and spatiotemporal pattern formation. Systems derived from oscillators based on the chemistry of bromate are the most extensively studied, with the celebrated Belousov-Zhabotinsky (BZ) reaction being the most popular example. Problems such as the formation of bubbles (CO2) and solid precipitate in the course of the reaction and the occurrence of simply short-lived oscillations under batch conditions are very common and, in some cases, compromise the use of some of these systems. It is investigated in this paper the dynamic behavior of the bromate/hypophosphite/acetone/dual catalyst system, which has been sugested as an interesting alternative to circumvent those inconvenients. In this work, manganese and ferroin are employed as catalysts and the complete system (BrO3-/H2PO2-/acetone/Mn(II)-ferroin) is studied under batch conditions. Temporal symmetry breaking was studied in a reactor under agitation by means of simultaneous records of the potential changes of platinum and Ag/AgBr electrodes, both measured versus a reversible hydrogen electrode. Additionally, spatio-temporal formation of target patterns and spiral waves were obtained when the oscillating mixture was placed in a quasi two-dimensional reactor.

Dinámica del heleoplancton en relación a las fluctuaciones hidrológicas en aiguamolls de l’Empordà (NE de la península Ibérica). Propuesta de un método sencillo de monitorización basado en la abundancia de grupos taxonómicos

Monitoring of the 'ecological water quality' in 'Aiguamolls de l’Empordà' Natural Park was carried out between September 1996 and August 1997 . The aim of this sampling programme was to design a simple method for rapid detect changes in water quality due to human activity. These include flow regulation by the Park management, nutrient entries from effluents of a nearby wastewater treatment plant or agricultural fertilising. The proposed method is based on the analysis of the abundance of characteristic taxonomic groups of aquatic invertebrates (heleoplankton). The simplicity of the method is ensured by the use of large taxa which are easier to recognise than species. The functioning of aquatic systems has been modelled by means of correspondence analysis between samples and taxa. Results can be summerized in five environmental conditions with a regular community structure. Dominated by one taxon: cladocerans, ostracods, calanoids, cyclopoids and harpacticoids. The dynamics of both freshwater and brackish lagoons can be modelled as displacements between these five groups of environmental conditions. Nevertheless, the “calanoids situation” and the “harpacticoids situation” occur mainly in brackish lagoons, whereas the “cladocerans situation” occurs mainly in freshwater. The four principal axes of data variation have been respectively identified as nutrient turnover rate, hypertrophy, degree of mineralization of the organic matter and eutrophy. The use of these taxa has been validated by comparison with a model obtained from the species. We conclude that in a highly fluctuating system such as the one here, only persistent situations of eutrophy or hypertrophy must be equated to low 'ecological water quality'

La convergència lingüística: possible retardador del procés de gramaticalització?

En diferents zones d"Hispanoamèrica, la substitució del futur sintètic en -rá (cantaré, lloverá) per la construcció Ir a + Infinitiu (voy a cantar, va a llover) resulta cada vegada més evident (Bauhr, 1989; Troya, 1998; Almeida y Díaz, 1998; Blas Arroyo, 2005; Sedano, 2006). Si bé en les zones peninsulars monolingües aquesta substitució també es percep, sembla que en les zones bilingües on el castellà està en contacte amb el català la tendència és justament la contrària. En aquest article es pretén verificar aquesta tendència tot partint de la hipòtesi que la construcció Ir a + Infinitiu per expressar valors temporals prospectius es fa servir en menor grau, sobretot en els parlants amb el català como a L1. La justificació cal trobar-la en la influència del català sobre el castellà; concretament, en el paradigma verbal particular del català confusió amb el pretèrit perfet perifràstic (vaig cantar) i esforç articulatori i en el fet que Anar a + Infinitiu no ha gramaticalitzat els mateixos valors que el castellà a Ir a + Infinitiu manté els valors etimològics. Per comprovar-ho, ens valdrem del corpus RESOL; un corpus de dades orals constituït per 94 entrevistes semidirigides realitzades a nens de 6º de primària, i novament quan cursaven 1º de la ESO, a escoles de Mataró i de Manlleu. Un cop analitzat el corpus, les dades revelen que, efectivament, en les zones bilingües, els informants amb el català com a L1 tendeixen a utilitzar la forma sintètica en major grau que la forma analítica. En canvi, els parlants que tenen el castellà com a L1 fan servir majoritàriament la perífrasi Ir a + Infinitiu, tot i que aquest ús no es tan profús como en la resta de zones monolingües peninsulars. En definitiva, el fet de tenir el català como a L1 sembla ser un dels factor que condiciona o determina la proliferació de la construcció Ir a + Infinitiu en el castellà parlat a Catalunya, però, alhora, la convergència de diferents factors lingüístics és el que condiciona l"ús particular d"aquesta perífrasi verbal en la zona analitzada.

La expresión de futuro en el español de Cataluña. Un posible caso de confluencia lingüística

La incursión de nuevas disciplinas en la lingüística, tales como la sociología, el cognitivismo, la antropología, etc., han permitido encontrar diversos puntos de unión entre las investigaciones realizadas desde cada una de estas disciplinas. Ello resulta de gran interés para los estudios de variación y contacto de lenguas en los que, aparte de los factores lingüísticos tradicionales, intervienen significativamente otros de índole cognitiva, sociocultural y pragmático-discursiva.Partiendo de este marco teórico plural, y desde la perspectiva del contacto de lenguas, en las siguientes páginas se analizan las expresiones prospectivas del español. Concretamente, se pretende aseverar la hipótesis de la influencia del catalán sobre el español en la expresión formal del futuro,1 pues parece que en las zonas catalanohablantes la frecuencia de uso del futuro sintético (FS) y del futuro analítico (FA) para hablar de eventos venideros es opuesta al empleo que de estas mismas formas suele hacerse en el resto de zonas hispanohablantes.2 La idea parte del hecho de que, pese a que en catalán también alternan las dos estructuras —el FS y la perífrasis prospectiva «ANAR A+Infinitivo»—, el menor rendimiento de la perífrasis en catalán y, por tanto, su menor grado de gramaticalización, parece incidir en la frecuencia de uso de la perífrasis en español «IR A+Infinitivo».

Repensando la formación inicial del profesorado para abordar el tratamiento a la diversidad cultural y lingüística en el aula = Rethinking initial teacher education for linguistic and cvltural diversity in the classroom

In recent decades, European educational systems are facing many challenges related to the treatment of cultural and linguistic diversity. The need to address this diversity requires new approaches to education; this in turn requires changes in the way we prepare teachers for the new reality they face in their classrooms. In this article we highlight some of the major problems that initial teacher training has to address in order to enable teachers to deal effectively, respectfully, and fairly with students whose linguistic and cultural background is different from their own. We also present several models for teacher education from Europe and North America based on clearly identified teacher competences for linguistic and cultural diversity

Cardiotocógrafo: monitor para el control de la frecuencia cardiaca fetal y la dinámica uterina

Controlar la frecuencia cardiaca fetal y la dinámica uterina durante el proceso del embarazo y el parto resulta de particular importancia para conocer el estado de salud de la madre y el niño. Hoy en día existen aparatos muy novedosos para este fin de uso generalizado en los hospitales españoles. De este tema se ocupa la Ficha de Utillaje de este mes analizando en qué consiste este monitor; cómo se utiliza, los pasos a seguir; etc.

Cardiotocógrafo: monitor para el control de la frecuencia cardiaca fetal y la dinámica uterina

Controlar la frecuencia cardiaca fetal y la dinámica uterina durante el proceso del embarazo y el parto resulta de particular importancia para conocer el estado de salud de la madre y el niño. Hoy en día existen aparatos muy novedosos para este fin de uso generalizado en los hospitales españoles. De este tema se ocupa la Ficha de Utillaje de este mes analizando en qué consiste este monitor; cómo se utiliza, los pasos a seguir; etc.

Cardiotocógrafo: monitor para el control de la frecuencia cardiaca fetal y la dinámica uterina

Controlar la frecuencia cardiaca fetal y la dinámica uterina durante el proceso del embarazo y el parto resulta de particular importancia para conocer el estado de salud de la madre y el niño. Hoy en día existen aparatos muy novedosos para este fin de uso generalizado en los hospitales españoles. De este tema se ocupa la Ficha de Utillaje de este mes analizando en qué consiste este monitor; cómo se utiliza, los pasos a seguir; etc.

Bases moleculares da ação anti-inflamatória dos ácidos oleanólico e ursólico sobre as isoformas da ciclo-oxigenase por docking e dinâmica molecular

The triterpenoids oleanolic (OA) and ursolic (UA) acids show non-selective antiinflamatory activity in vitro for cyclooxygenase (COX) isoforms. 3D conformations of OA and UA, with three possible orientations (1, 1' and 2) in the active site of isoforms COX, obtained by docking, were submitted to molecular dynamics. The results show that orientation 2 of the OA in COX-2 is more favorable because orientation 1 moved away from the active site. The carboxylate group of OA interact by hydrogen bonds with Ser353 and with Phe357 and Leu359, mediated by water, while hydroxyl in C-3 interact by hydrogen bond, mediated by water, with Tyr385.