Recuperación de estructuras latentes y estimación de parámetros en test multidimensionales ordinales: análisis comparado entre la TRI la TCT y el análisis factorial

A través de la realización de cuatro estudios basados en datos simulados y unidos por una preocupación común, aunque parcialmente independientes en su metodología y foco específico, esta tesis se plantea como objetivo general poner a prueba algunas de las ventajas que podría obtener un investigador aplicado al utilizar modelos clásicos de TRI frente a otras opciones, para de esta forma evaluar la posibilidad de obtener resultados relativamente equivalentes utilizando procedimientos alternativos. Específicamente, en esta tesis se pone a prueba: a) la calidad diferencial de las estimaciones de las propiedades de los ítems obtenidas por los procedimientos TRI frente a los factoriales; b) la validez de los procedimientos de escalamiento TRI frente a los de la TCT; y c) los límites de la propiedad de invarianza de las estimaciones de sujetos e ítems obtenidas con procedimientos TRI. La hipótesis general de esta tesis es que, en el tipo de condiciones en que se ha enfocado el estudio, las ventajas de utilizar modelos clásicos de TRI no serán demasiado amplias, con lo que existirán condiciones en las que emplear procedimientos alternativos será recomendable, dada su simplicidad relativa y su equivalencia de resultados. La primera investigación utiliza datos simulados para comparar las estimaciones de discriminación de ítems politómicos provenientes del AFI, frente a las posibles de obtener con distintas estrategias relacionadas con el análisis factorial clásico. La segunda investigación, también utiliza datos simulados para poner a prueba la equivalencia de las estimaciones de discriminación de los ítems obtenidas con los procedimientos TRI y AFI. La tercera investigación, utiliza dos estudios basados en datos simulados tanto para comparar los escalamientos de los sujetos obtenidos por la TRI y la TCT, como para aclarar las condiciones en que es posible esperar la presencia similitudes o diferencias entre ambos...

Una clave humanista de mediados del siglo XV para el Humanismo de la Corona de Aragón desde fines del siglo XIV: Ferran Valentí y el Prólogo a su traducción de las Paradoxa de Cicerón

In this article I study the Preface by Ferran Valentí to his own translation into Catalan of Cicero’s Paradoxa. Ferran Valentí was a humanist from Majorca, author in Catalan language who earned a Low Degree at the University of Bologna and who declared himself a devoted “son and pupil” of humanist Leonardo Bruni. Valentí made an analysis of the humanistic Canon in mid-15th century, including troubadours, Dante, Lullius, Latin literature classics and several Catalan authors, such as Bernat Metge. This proves that humanism was a true trend in the Crown of Aragon from the 2nd half of the 14th Century on.

Sol–gel copper chromium delafossite thin films as stable oxide photocathodes for water splitting

Significant effort is being devoted to the study of photoactive electrode materials for artificial photosynthesis devices. In this context, photocathodes promoting water reduction, based on earth-abundant elements and possessing stability under illumination, should be developed. Here, the photoelectrochemical behavior of CuCrO2 sol–gel thin film electrodes prepared on conducting glass is presented. The material, whose direct band gap is 3.15 eV, apparently presents a remarkable stability in both alkaline and acidic media. In 0.1 M HClO4 the material is significantly photoactive, with IPCE values at 350 nm and 0.36 V vs. RHE of over 6% for proton reduction and 23% for oxygen reduction. This response was obtained in the absence of charge extraction layers or co-catalysts, suggesting substantial room for optimization. The photocurrent onset potential is equal to 1.06 V vs. RHE in both alkaline and acidic media, which guarantees the combination of the material with different photoanodes such as Fe2O3 or WO3, potentially yielding bias-free water splitting devices.

Tungsten coil atomic emission spectrometry combined with dispersive liquid–liquid microextraction: A synergistic association for chromium determination in water samples

A novel and environment friendly analytical method is reported for total chromium determination and chromium speciation in water samples, whereby tungsten coil atomic emission spectrometry (WCAES) is combined with in situ ionic liquid formation dispersive liquid–liquid microextraction (in situ IL-DLLME). A two stage multivariate optimization approach has been developed employing a Plackett–Burman design for screening and selection of the significant factor involved in the in situ IL-DLLME procedure, which was later optimized by means of a circumscribed central composite design. The optimum conditions were complexant concentration: 0.5% (or 0.1%); complexant type: DDTC; IL anion: View the MathML sourcePF6−; [Hmim][Cl] IL amount: 60 mg; ionic strength: 0% NaCl; pH: 5 (or 2); centrifugation time: 10 min; and centrifugation speed: 1000 rpm. Under the optimized experimental conditions the method was evaluated and proper linearity was obtained with a correlation coefficient of 0.991 (5 calibration standards). Limits of detection and quantification for both chromium species were 3 and 10 µg L−1, respectively. This is a 233-fold improvement when compared with chromium determination by WCAES without using preconcentration. The repeatability of the proposed method was evaluated at two different spiking levels (10 and 50 µg L−1) obtaining coefficients of variation of 11.4% and 3.6% (n=3), respectively. A certified reference material (SRM-1643e NIST) was analyzed in order to determine the accuracy of the method for total chromium determination and 112.3% and 2.5 µg L−1 were the recovery (trueness) and standard deviation values, respectively. Tap, bottled mineral and natural mineral water samples were analyzed at 60 µg L−1 spiking level of total Cr content at two Cr(VI)/Cr(III) ratios, and relative recovery values ranged between 88% and 112% showing that the matrix has a negligible effect. To our knowledge, this is the first time that combines in situ IL-DLLME and WCAES.

Complaint against the keeper of the bath, 1828 July 28

One draft of a letter.

Contributions for a bath in Charles' River, 1799 & 1800, 1800

Includes contribution totals from personal subscribers, individual donors, the Harvard Corporation, and the Humane Society for the construction of a bath on the Charles River. Also contains estimated costs for materials and labor.