Electronic and vibrational contributions to first hyperpolarizability of donor-acceptor-substituted azobenzene

In this study we report on the electronic and vibrational (hyper)polarizabilities of donor–acceptorsubstituted azobenzene. It is observed that both electronic and vibrational contributions to the electricdipole first hyperpolarizability of investigated photoactive molecule substantially depend on the conformation. The contributions to the nuclear relaxation first hyperpolarizability are found to be quite important in the case of two considered isomers (cis and trans). Although the double-harmonic term is found to be the largest in terms of magnitude, it is shown that the total value of the nuclear relaxation contribution to vibrational first hyperpolarizability is a result of subtle interplay of higher-order contributions. As a part of the study, we also assess the performance of long-range-corrected densityfunctional theory in determining vibrational contributions to electric dipole (hyper)polarizabilities. In most cases, the applied long-range-corrected exchange correlation potentials amend the drawbacks of their conventional counterparts

Kinetic resolution: a powerful tool for the synthesis of planar-chiral ferrocenes

Since the serendipitous discovery of ferrocene by Pauson and Kealy in 1951, it has become one of the most important structures in Organic Chemistry. Lately, kinetic resolution has emerged as a useful tool for the synthesis of planar chiral ferrocenes. This review aims to cover and discuss the development of this topic.

Simulació d'arquitectures VLIW

L'objectiu d'aquest projecte es dissenyar i implementar en Java una interfície gràfica que permeti simular l'arquitectura VLIW. Ha d'interactuar amb un simulador ja existent, VEX, i amb l'usuari. VEX permet analitzar, desenvolupar i depurar codi escrit en C sobre un processador VLIW configurable, des dels recursos hardware fíns al comportament de la "caché". L'interfície gràfica desenvolupada es diu JavaVEX. Té el gran avantatge d'evitar la introducció de les comandes de text que necesita VEX perquè son substituïdes per elements. És una eina més intuïtiva, ràpida i eficient. JavaVEX mostra informació sobre el codi C traduït a instruccions VLIW de fins a 4 operacions. També mostra els resultats de les instrucciones VLIW simulades. JavaVEX s'ha incorporat a un LiveCD. Així es pot executar l'aplicació sobre qualsevol ordinador. La finalitat docent de JavaVEX és ser utilitzada en les pràctiques de l'assignatura Arquitectura per a Computadors 2.

El parlar salat: descripció, àmbit geogràfic i ús

La recerca, que ha durat quatre anys (2004-2008), s’ha centrat en l’estudi del parlar salat, un subdialecte del català oriental que es caracteritza per una sola isoglossa: l’ús de l’article salat (es, sa), és a dir, l’element derivat del demostratiu llatí “ipse”. Aquesta varietat ―poc estudiada― no té un abast gaire definit. Se sol situar en una estreta franja del litoral de Girona, entre Blanes i Begur, i que, després, isoladament, reapareix a Cadaqués, on es manté amb més vigència. A banda que els estudis no estableixen els límits geogràfics del fenomen de manera precisa, es tenen indicis que el tret que defineix i dóna nom a la varietat es troba en un acusat procés de recessió i de pèrdua, ja que només l’empren persones d’edat avançada (en general, pescadors). La tesi concreta l’estat actual del parlar salat. També fixa la cronologia del canvi de l’article salat (és a dir, en quin moment s’ha substituït per l’article literari, el, la) i es decriuen els factors que l’han propiciat (migració, turisme, la pressió de l’estàndard, etc.). El parlar salat és un exemple de desdialectalització del català, atès que es verifica que el tret que el caracteritza va començar a caure en desús en dels anys cinquanta del segle passat i que, avui dia, pràcticament ja s’ha extingit (només es manté en parlants de Cadaqués nascuts després de 1983). Per tant, s’evidencia que cal replantejar-se l’actual divisió dialectal de la llengua catalana ja que el subdialecte estudiat no existeix.

Els primers llums del Delta

Treball de recerca realitzat per un alumne d'ensenyament secundari i guardonat amb un Premi CIRIT per fomentar l'esperit científic del Jovent l'any 2009. El treball és un estudi de l’evolució, tan tècnica com estètica dels fars paral•lela als avenços tecnològics i prenent com a protagonistes els singulars fars de ferro que es varen construir durant la segona meitat del segle XIX i varen funcionar durant un llarguíssim període en el delta de l’Ebre. L’estructura de ferro, ancorada directament sobre les sorres del delta va donar un caràcter especial a aquestes construccions que, d’altra banda, constituïen una tipologia única a Catalunya i a Espanya. Aquests fars van rebre el nom del lloc on foren ubicats estratègicament. De sud a nord: far de la Banya, far de Buda i far del Fangar. Els van projectar conjuntament, es van encendre per primera vegada el mateix dia, van ser l’habitatge dels seus faroners, van anar evolucionant tècnicament tots tres però el final de cadascun d’ells va ser molt diferent. La història dels fars de ferro ha anat lligada al paisatge i la vida d’aquestes singulars terres del Delta i després de més d’un segle de servei foren substituïts per altres que estèticament i tècnicament res tenen a veure amb els seus antecessors.

The nature of the Cr-C bond: direct estimation of aromaticity in Fischer carbenes

Report for the scientific sojourn at the the Philipps-Universität Marburg, Germany, from september to december 2007. For the first, we employed the Energy-Decomposition Analysis (EDA) to investigate aromaticity on Fischer carbenes as it is related through all the reaction mechanisms studied in my PhD thesis. This powerful tool, compared with other well-known aromaticity indices in the literature like NICS, is useful not only for quantitative results but also to measure the degree of conjugation or hyperconjugation in molecules. Our results showed for the annelated benzenoid systems studied here, that electron density is more concentrated on the outer rings than in the central one. The strain-induced bond localization plays a major role as a driven force to keep the more substituted ring as the less aromatic. The discussion presented in this work was contrasted at different levels of theory to calibrate the method and ensure the consistency of our results. We think these conclusions can also be extended to arene chemistry for explaining aromaticity and regioselectivity reactions found in those systems.In the second work, we have employed the Turbomole program package and density-functionals of the best performance in the state of art, to explore reaction mechanisms in the noble gas chemistry. Particularly, we were interested in compounds of the form H--Ng--Ng--F (where Ng (Noble Gas) = Ar, Kr and Xe) and we investigated the relative stability of these species. Our quantum chemical calculations predict that the dixenon compound HXeXeF has an activation barrier for decomposition of 11 kcal/mol which should be large enough to identify the molecule in a low-temperature matrix. The other noble gases present lower activation barriers and therefore are more labile and difficult to be observable systems experimentally.

A system to evaluate the accuracy of a visual mosaicking methodology

When underwater vehicles navigate close to the ocean floor, computer vision techniques can be applied to obtain motion estimates. A complete system to create visual mosaics of the seabed is described in this paper. Unfortunately, the accuracy of the constructed mosaic is difficult to evaluate. The use of a laboratory setup to obtain an accurate error measurement is proposed. The system consists on a robot arm carrying a downward looking camera. A pattern formed by a white background and a matrix of black dots uniformly distributed along the surveyed scene is used to find the exact image registration parameters. When the robot executes a trajectory (simulating the motion of a submersible), an image sequence is acquired by the camera. The estimated motion computed from the encoders of the robot is refined by detecting, to subpixel accuracy, the black dots of the image sequence, and computing the 2D projective transform which relates two consecutive images. The pattern is then substituted by a poster of the sea floor and the trajectory is executed again, acquiring the image sequence used to test the accuracy of the mosaicking system

Counterexamples to some pointwise estimates of the maximal Cauchy transform in terms of the Cauchy transform

Motivated by the work of Mateu, Orobitg, Pérez and Verdera, who proved inequalities of the form $T_*f\lesssim M(Tf)$ or $T_*f\lesssim M^2(Tf)$ for certain singular integral operators $T$, such as the Hilbert or the Beurling transforms, we study the possibility of establishing this type of control for the Cauchy transform along a Lipschitz graph. We show that this is not possible in general, and we give a partial positive result when the graph is substituted by a Jordan curve.

Studies in stoichiometry with compositional data

Geochemical data that is derived from the whole or partial analysis of various geologic materialsrepresent a composition of mineralogies or solute species. Minerals are composed of structuredrelationships between cations and anions which, through atomic and molecular forces, keep the elementsbound in specific configurations. The chemical compositions of minerals have specific relationships thatare governed by these molecular controls. In the case of olivine, there is a well-defined relationshipbetween Mn-Fe-Mg with Si. Balances between the principal elements defining olivine composition andother significant constituents in the composition (Al, Ti) have been defined, resulting in a near-linearrelationship between the logarithmic relative proportion of Si versus (MgMnFe) and Mg versus (MnFe),which is typically described but poorly illustrated in the simplex.The present contribution corresponds to ongoing research, which attempts to relate stoichiometry andgeochemical data using compositional geometry. We describe here the approach by which stoichiometricrelationships based on mineralogical constraints can be accounted for in the space of simplicialcoordinates using olivines as an example. Further examples for other mineral types (plagioclases andmore complex minerals such as clays) are needed. Issues that remain to be dealt with include thereduction of a bulk chemical composition of a rock comprised of several minerals from which appropriatebalances can be used to describe the composition in a realistic mineralogical framework. The overallobjective of our research is to answer the question: In the cases where the mineralogy is unknown, arethere suitable proxies that can be substituted?Kew words: Aitchison geometry, balances, mineral composition, oxides

Asymptotic robustness in multi-sample analysis of multivariate linear relations

Standard methods for the analysis of linear latent variable models oftenrely on the assumption that the vector of observed variables is normallydistributed. This normality assumption (NA) plays a crucial role inassessingoptimality of estimates, in computing standard errors, and in designinganasymptotic chi-square goodness-of-fit test. The asymptotic validity of NAinferences when the data deviates from normality has been calledasymptoticrobustness. In the present paper we extend previous work on asymptoticrobustnessto a general context of multi-sample analysis of linear latent variablemodels,with a latent component of the model allowed to be fixed across(hypothetical)sample replications, and with the asymptotic covariance matrix of thesamplemoments not necessarily finite. We will show that, under certainconditions,the matrix $\Gamma$ of asymptotic variances of the analyzed samplemomentscan be substituted by a matrix $\Omega$ that is a function only of thecross-product moments of the observed variables. The main advantage of thisis thatinferences based on $\Omega$ are readily available in standard softwareforcovariance structure analysis, and do not require to compute samplefourth-order moments. An illustration with simulated data in the context ofregressionwith errors in variables will be presented.

The electric revolution in Latin America

Latin America participated in the electric revolution which profoundly transformed the most developed Western economies between 1880 and 1930. The electrification of Latin America began relatively soon after these economies, but it was incapable of keeping up with them. Public electric lighting was introduced early in the big Latin American cities, where electric trams started running at almost the same time as in Europe, and electricity spread rapidly in the mining sector. In the most advanced countries or areas in the region, the manufacturing industry substituted the steam engine with the electric motor, following the example of industry in the United States and Europe. Nevertheless, towards 1930 electricity consumption per inhabitant for Latin America was far below that of the more advanced economies, and only the Latin American countries which lead the process of electrification had reached levels of electric consumption that were similar to those of the late industrialised European countries. One of the most striking features of the electric revolution in Latin America is rooted precisely in the enormous national differences. These differences are indicative of the great economic inequalities existing in the heart of the region and these nations highly diverse capacity for economic modernisation.

Automatització d'una planta de processos químics

Resum L’any 1969 es van començar a comercialitzar els sistemes digitals programables coneguts com autòmats programables o PLC’s, utilitzats per controlar qualsevol tipus de procés industrial. Al llarg de tots aquests anys, aquests sistemes i tota la tecnologia en general han evolucionat molt, i només és qüestió de temps que la tecnologia que utilitzem avui en dia quedi obsoleta i substituïda per una de millors característiques i amb més avantatges. Aquest és el motiu de l’elaboració d’aquest treball, que com a objectiu pretén modernitzar un procés de fabricació d’una industria química que ha quedat molt limitat a causa de l’antiguitat de la instal•lació. Per dur a terme aquesta modernització, s’introdueixen sistemes de control amb majors prestacions, s’utilitzen xarxes de comunicacions per facilitar el muntatge elèctric de la instal•lació i un sistema de supervisió i adquisició de dades per poder obtenir un control més estricte del procés de fabricació i de tots els factors que intervenen. El funcionament del procés de fabricació és que a partir d’unes matèries primeres líquides emmagatzemades en dipòsits, es dosifiquin aquestes matèries en l’ordre i la quantitat desitjada dins un o diversos recipients per barrejar-les i aplicar els tractaments que siguin necessaris. Tot aquest procés està controlat per un autòmat programable, i disposa de diferents terminals operadors per poder interactuar amb el sistema. També té implementat un sistema SCADA en diversos ordinadors per aportar una visió general de la planta en temps real, un registre de dades dels paràmetres que es controlen i alhora serveix per enllaçar amb la xarxa d’ordinadors existent. Com annex d’aquest treball, es presenten els esquemes elèctrics i el programa de l’autòmat programable per veure totes les característiques elèctriques dels dispositius i el mètode de funcionament del procés. S’ha aconseguit donar un salt tecnològic i poder gaudir de tots els avantatges que ofereixen les noves tecnologies, que com a resultat s’ha optimitzat i millorat el procés de fabricació. De totes les conclusions, la més destacada és la d’haver dissenyat un sistema de control basat en una estructura descentralitzada molt flexible, que es pot expandir i adaptar fàcilment als possibles canvis.

PCAF regulates the stability of the transcriptional regulator and cyclin-dependent kinase inhibitor p27Kip1

P27(Kip1) (p27) is a member of the Cip/Kip family of cyclin-dependent kinase inhibitors. Recently, a new function of p27 as transcriptional regulator has been reported. It has been shown that p27 regulates the expression of target genes mostly involved in splicing, cell cycle, respiration and translation. We report here that p27 directly binds to the transcriptional coactivator PCAF by a region including amino acids 91-120. PCAF associates with p27 through its catalytic domain and acetylates p27 at lysine 100. Our data showed that overexpression of PCAF induces the degradation of p27 whereas in contrast, the knockdown of PCAF stabilizes the protein. A p27 mutant in which K100 was substituted by arginine (p27-K100R) cannot be acetylated by PCAF and has a half-life much higher than that of p27WT. Moreover, p27-K100R remains stable along cell-cycle progression. Ubiquitylation assays and the use of proteasome inhibitors indicate that PCAF induces p27 degradation via proteasome. We also observed that knockdown of skp2 did not affect the PCAF induced degradation of p27. In conclusion, our data suggest that the p27 acetylation by PCAF regulates its stability.

Nanocrystalline M-type hexaferrite powders: preparation, geometric and magnetic propertiess

Co-Ti-Sn-Ge substituted M-type bariumhexaferrite powders with mean grain sizes between about 10 nm and about 1 ¿m and a narrow size distribution were prepared reproducibly by means of a modified glass crystallization method. At annealing temperatures between 560 and 580°C of the amorphous flakes nanocrystalline particles grow. They behave superparamagnetically at room temperature and change into stable magnetic single domains at lower temperatures. The magnetic volume of the powders is considerably less than the geometric one. However, the effective anisotropy fields are larger by a Factor of two to three.