Full Exploration of the Diels–Alder Cycloaddition on Metallofullerenes M3N@C80 (M=Sc, Lu, Gd): The D5h versus Ih Isomer and the Influence of the Metal Cluster

In this work a detailed investigation of the exohedral reactivity of the most important and abundant endohedral metallofullerene (EMF) is provided, that is, Sc3N@Ih-C80 and its D5h counterpart Sc3N@D5h-C80, and the (bio)chemically relevant lutetium- and gadolinium-based M3N@Ih/D5h-C80 EMFs (M=Sc, Lu, Gd). In particular, we analyze the thermodynamics and kinetics of the Diels–Alder cycloaddition of s-cis-1,3-butadiene on all the different bonds of the Ih-C80 and D5h-C80 cages and their endohedral derivatives. First, we discuss the thermodynamic and kinetic aspects of the cycloaddition reaction on the hollow fullerenes and the two isomers of Sc3N@C80. Afterwards, the effect of the nature of the metal nitride is analyzed in detail. In general, our BP86/TZP//BP86/DZP calculations indicate that [5,6] bonds are more reactive than [6,6] bonds for the two isomers. The [5,6] bond D5h-b, which is the most similar to the unique [5,6] bond type in the icosahedral cage, Ih-a, is the most reactive bond in M3N@D5h-C80 regardless of M. Sc3N@C80 and Lu3N@C80 give similar results; the regioselectivity is, however, significantly reduced for the larger and more electropositive M=Gd, as previously found in similar metallofullerenes. Calculations also show that the D5h isomer is more reactive from the kinetic point of view than the Ih one in all cases which is in good agreement with experiments

Essential factors for control of the equilibrium in the reversible rearrangement of M3N@Ih-C80 fulleropyrrolidines: Exohedral functional groups versus endohedral metal clusters

The effects of exohedral moieties and endohedral metal clusters on the isomerization of M3N@Ih-C80 products from the Prato reaction through [1,5]-sigmatropic rearrangement were systematically investigated by using three types of fulleropyrrolidine derivatives and four different endohedral metal clusters. As a result, all types of derivatives provided the same ratios of the isomers for a given trimetallic nitride template (TNT) as the thermodynamic products, thus indicating that the size of the endohedral metal clusters inside C80 was the single essential factor in determining the equilibrium between the [6,6]-isomer (kinetic product) and the [5,6]-isomer. In all the derivatives, the [6,6]- and [5,6]-Prato adducts with larger metal clusters, such as Y3N and Gd3N, were equally stable, which is in good agreement with DFT calculations. The reaction rate of the rearrangement was dependent on both the substituent of exohedral functional groups and the endohedral metal-cluster size. Further DFT calculations and 13C NMR spectroscopic studies were employed to rationalize the equilibrium in the rearrangement between the [6,6]- and [5,6]-fulleropyrrolidines

Spectroscopic analysis of C80 doping with group III and group V elements using semiempirical PM3 molecular modelling technique

Semiempirical calculations at the level of PM3 of theory were carried out to study the structural and electronic properties of C80 and some of its doped derivatives with the elements of group III and V at the level of PM3 of theory. We have selected these elements to be substituted in the fullerene-C80 cage in order to show the effect of such structural change on the electronic properties of the molecules studied. The theoretical IR spectra, some of physical and chemical properties of the molecules studied are obtained and discussed.

Estudo químico e biológico do fungo endofítico C80 (Phaeosphaeriaceae) associado à alga marinha Bostrychia radicans

Pós-graduação em Química - IQ

Real-time tracking system using C80 DSPs and a binocular robotic head

[EN]An active vision system to perform tracking of moving objects in real time is described. The main goal is to obtain a system integrating off-the-self components. These components includes a stereoscopic robotic-head, as active perception hardware; a DSP based board SDB C80, as massive data processor and image acquisition board; and finally, a Pentium PC running Windows NT that interconnects and manages the whole system. Real-time is achieved taking advantage of the special architecture of DSP. An evaluation of the performance is included.

A C80 DSP-based active vision system for real-time tracking

[EN]Active Vision Systems can be considered as dynamical systems which close the loop around artificial visual perception, controlling camera parameters, motion and also controlling processing to simplify, accelerate and do more robust visual perception. Research and Development in Active Vision Systems [Aloi87], [Bajc88] is a main area of interest in Computer Vision, mainly by its potential application in different scenarios where real-time performance is needed such as robot navigation, surveillance, visual inspection, among many others. Several systems have been developed during last years using robotic-heads for this purpose...

Caracterização da qualidade acústica da Catedral Metropolitana de Campinas - Brasil

Dissertação para obtenção do Grau de Mestre em Engenharia Civil - Perfil Construção

Adição simultânea de sulfato de amônio e ureia à calda de pulverização do herbicida glyphosate

Dois experimentos foram desenvolvidos em casa de vegetação, com o objetivo de avaliar a eficácia do herbicida glyphosate sobre plantas de Digitaria insularis quando soluções de ureia (U; 5 g L-1), sulfato de amônio (SA; 15 g L-1) ou U+SA (2,5 + 7,5 g L-1) foram utilizadas como veículo de pulverização. Aos 28 dias após aplicação, de acordo com as curvas de dose-resposta (primeiro experimento), foram necessários 409 g ha-1 de glyphosate para atingir 50% de controle da planta daninha (C50) quando água sem adjuvantes foi usada como veículo de pulverização. Para obtenção dos mesmos 50% de controle, as doses de glyphosate foram reduzidas para 373, 208 e 189 g ha-1; quando o herbicida foi pulverizado utilizando solução de U, SA ou U+SA, respectivamente. A redução na dose oriunda da combinação de glyphosate e U+SA também foi observada para controles de 80% (C80). No segundo experimento, a adição de U+SA à calda elevou o controle obtido com a menor dose de glyphosate (360 g ha-1), igualando-o à aplicação da maior dose (720 g ha-1) sem adjuvantes. Esses resultados evidenciam efeito complementar de U e SA em elevar a eficácia do glyphosate para controle de D. insularis.

Dose-response curve to soil applied herbicides and susceptibility evaluation of different amaranthus species using model identity

Greenhouse studies were conducted in 2008-2009 with the objective of adjusting dose-response curves of the main soil-applied herbicides currently used in cotton for the control of Amaranthus viridis, A. hybridus, A. spinosus, A. lividus, as well as comparing susceptibility among different species, using the identity test models. Thirty six individual experiments were simultaneously carried out in greenhouse, in a sandy clay loam soil (21% clay, 2.36% OM) combining increasing doses of the herbicides alachlor, clomazone, diuron, oxyfluorfen, pendimethalin, prometryn, S-metolachlor, and trifluralin applied to each species. Dose-response curves were adjusted for visual weed control at 28 days after herbicide application and doses required for 80% (C80) and 95% (C95) control were calculated. All herbicides, except clomazone and trifluralin, provided efficient control of most Amaranthus species, but substantial differences in susceptibility to herbicides were found. In general, A. lividus was the least sensitive species, whereas A. spinosus demonstrated the highest sensitivity to herbicides. Alachlor, diuron, oxyfluorfen, pendimethalin, S-metolachlor, and prometryn are efficient alternatives to control Amaranthus spp. in a range of doses that are currently lower than those recommended to cotton.

La acústica de los auditorios en centros de enseñanza musical. El conservatorio de Palencia.

Resumen en inglés

Quantificação molecular de bactérias ruminais, parâmetros ruminais e digestibilidade de dietas de novilhos alimentados com diferentes relações de volumoso: concentrado na dieta

Pós-graduação em Zootecnia - FCAV

Assessing the effectiveness of ISO 3382 for evaluating the acoustical quality of italian historical theatres: the case study of the Bonci Theatre

The present study concerns the acoustical characterisation of Italian historical theatres. It moved from the ISO 3382 which provides the guidelines for the measurement of a well established set of room acoustic parameters inside performance spaces. Nevertheless, the peculiarity of Italian historical theatres needs a more specific approach. The Charter of Ferrara goes in this direction, aiming at qualifying the sound field in this kind of halls and the present work pursues the way forward. Trying to understand how the acoustical qualification should be done, the Bonci Theatre in Cesena has been taken as a case study. In September 2012 acoustical measurements were carried out in the theatre, recording monaural e binaural impulse responses at each seat in the hall. The values of the time criteria, energy criteria and psycho-acoustical and spatial criteria have been extracted according to ISO 3382. Statistics were performed and a 3D model of the theatre was realised and tuned. Statistical investigations were carried out on the whole set of measurement positions and on carefully chosen reduced subsets; it turned out that these subsets are representative only of the “average” acoustics of the hall. Normality tests were carried out to verify whether EDT, T30 and C80 could be described with some degree of reliability with a theoretical distribution. Different results, according to the varying assumptions underlying each test, were found. Finally, an attempt was made to correlate the numerical results emerged from the statistical analysis to the perceptual sphere. Looking for “acoustical equivalent areas”, relative difference limens were considered as threshold values. No rule of thumb emerged. Finally, the significance of the usual representation through mean values and standard deviation, which may be meaningful for normal distributed data, was investigated.

Abundance of mesozooplankton in the Mediterranean Sea during PELMED 1995 and PELMED 1996

The PELMED-ECOPEL dataset contains mesozooplankton data collected in 1995-1996 in the Gulf of Lion (North Western Mediterranean Sea) between 43°35' N, 2°50' E and 42°15' N, 6°15' E. Zooplankton taxonomy-related abundance per unit volume of the water column.

Propagación del sonido en las iglesias prerrománicas

El presente proyecto tiene como objetivo el estudio de la propagación del sonido en las iglesias prerrománicas. Para ello, se analizarán y aplicarán algunas de las teorías más relevantes de propagación del sonido, con el fin de concluir si, alguna de ellas, se puede establecer como modelo de propagación en estos espacios. Se partirá de valores medidos in situ en diversas iglesias prerrománicas de la geografía española, siendo este un número considerado suficiente para poder valorar los resultados como significativos. Estas iglesias son: - San Cebrián - San Juan de Baños - San Pedro de la Nave - Santa María de Melque - Santa Lucía del Trampal El proyecto se valdrá de los siguientes parámetros acústicos para llevar a cabo el estudio: la Claridad Musical, C80, y la Sonoridad, G. El trabajo se centrará en tres teorías de propagación del sonido en el interior de recintos: • “La Teoría Clásica” • “Modelo de Barron y Lee” • “Método μ “ A partir de estas teorías, se obtendrán los valores, de forma teórica, para de C80 y G y se llevará a cabo una comparativa con los valores empíricos. ABSTRACT The aim of this project is to study the sound propagation in Pre-Romanesque churches. Hence, some of the most relevant sound propagation theories will be analyzed and applied, in order to conclude whether, any of them, can be set as a propagation model in this typology of spaces. On site measured values will be taken in different Pre-Romanesque churches in the Spanish geography, being the number of churches enough to evaluate if the results are significant. These churches are: - San Cebrián - San Juan de Baños - San Pedro de la Nave - Santa María de Melque - Santa Lucía del Trampal The following acoustic parameters will be used to perform the study: the musical clarity, C80, and the sound strength. G. The research will focus on three sound propagation theories in closed spaces: • “Classic Theory” • “Barron & Lee model” • μ Method Trough these theories, theoretical values will be derived, for C80 and G, being compared to the empirical values obtained on site.

Análisis de la distribución espacial de los parámetros acústicos en recintos

El principal objetivo de este estudio es la evaluación de la distribución espacial de los parámetros acústicos en un recinto a través de la aplicación de técnicas geoestadísticas como el método Kriging. Mediante el uso de la herramienta de análisis espacial ArcMap, perteneciente a la plataforma ArcGIS, se ha analizado el comportamiento acústico del Salón de Actos común a la Escuela Técnica Superior de Ingeniería y Sistemas de Telecomunicación (ETSIST) y la Escuela Técnica Superior de Ingeniería de Sistemas Informáticos (ETSISI), ambas situadas en el Campus Sur de la Universidad Politécnica de Madrid. Se han realizado mediciones in-situ del recinto no ocupado utilizando la herramienta de medición DIRAC Room Acoustics y el método de la respuesta impulsiva integrada, extrayéndose los parámetros acústicos de tiempo de reverberación (RT), tiempo de reverberación inicial (EDT), fuerza sonora relativa (Grel), claridad (C80), tiempo central (Ts), definición (D50) e Índice de Transmisión Rápida de la Palabra (RASTI). Se ha analizado la adecuación de los valores observados de Grel, C80 y Ts al modelo teórico de Barron y estimado, mediante el método Kriging Ordinario, el conjunto de parámetros medidos en el recinto, obteniéndose los semivariograma y mapas de estimación correspondientes. Además, se ha evaluado la calidad de la estimación en base a un número de puntos de medición reducido. A la vista de los resultados obtenidos, en general, el método Kriging puede considerarse un buen interpolador de los parámetros acústicos en un recinto, observándose que los parámetros que evalúan relaciones energéticas, especialmente la fuerza sonora relativa (Grel) proporcionan mejores estimaciones en comparación con aquellos relacionados con la reverberación y la inteligibilidad del habla. El coeficiente de determinación (R2) constituye una medida útil para evaluar la precisión de la estimación. Además, la entropía de los datos observados puede ser un buen indicador a priori de la precisión de la estimación. Asimismo, se ha demostrado que, basándose en un reducido número de puntos de medición, es posible obtener una estimación precisa de los parámetros acústicos de fuerza sonora relativa (Grel) y tiempo central (Ts). ABSTRACT. This project aims to evaluate the feasibility of using geostatistical techniques such as Kriging on the analysis of the spatial distribution of the acoustic parameters in rooms. The acoustic behaviour of the Assembly Hall of the ETSIST and ETSISI (Universidad Politécnica de Madrid) is investigated using ArcMap, which is the main component of ArcGIS suite of geospatial processing programs. For this purpose, in-situ acoustic measurements are carried out in the unoccupied room using DIRAC Room Acoustics software. The following acoustic parameters are measured by means of the integrated impulse response method for further examination: Reverberation Time (RT), Early Decay Time (EDT), Relative Strength (Grel), Clarity (C80), Centre Time (Ts), Definition (D50) and Rapid Speech Transmission Index (RASTI). Goodness-of-fit of measured Grel, C80 and Ts values to Barron’s theory is determined and Ordinary Kriging is applied to all the measured parameters in order to calculate the semivariogram and prediction surfaces. The prediction performance is also analysed when significantly fewer receiver positions are used for the prediction. The experimental results obtained lead to conclude that Kriging can be successfully applied to room acoustics. Energy\based acoustic parameters can be estimated with higher accuracy compared to those related to reverberation and speech intelligibility. Coefficient of determination (R2) is a reliable statistic for assessing the prediction accuracy, for which measured data entropy can also be a good a priori indicator. Furthermore, based on fewer receiver positions, it is demonstrated that accurate predictions of Grel and Ts can be achieved.