Catalytic tuning of phosphinoethane ligand. An improved catalyst for hydrocarbon

Report for the scientific sojourn carried out at the Department of Chemistry University of North Texas (USA) from September until November 2006. It includes the performance of two computational chemistry studies: an experimental and computational study toward the intra- and intermolecular hydroarylation of isonitriles and the development of an improved catalyst for hydrocarbon functionalization.

New Radicals and new applications of Dynamic Nuclear Polarization of biological systems

Dynamic Nuclear Polarization (DNP) is an emerging technique that could revolutionize the NMR study of small molecules at very low concentrations by the increase in sensitivity that results from transfer of polarization between electronic and nuclear spins. Although the underlying physics has been known for a long time, in the last few years there has been a lot of excitement on the chemistry and biology NMR community caused by the demonstration that the highly polarized nuclei that are prepared in solid state at very low temperatures (1-2 K) could be rapidly transferred to liquid samples at room temperature and studied in solution by conventional NMR techniques. In favorable cases several order of magnitude increases in sensitivity have been achieved. The technique is now mature enough that a commercial instrument is available. The efficiency of DNP depends on two crucial aspects: i) the efficiency of the nuclear polarization process and ii) the efficiency of the transfer from the initial solid state to the fluid state in which NMR is measured. The preferred areas of application (iii) will be dictated by situations in which the low concentration of the sample or its intrinsic low receptivity are the limiting factors .

Polychlorinated trityl radicals for dynamic nuclear polarization: the role of chlorine nuclei

Polychlorinated trityl radicals bearing carboxylate substituents are water soluble persistent radicals that can be used for dynamic nuclear polarization. In contrast to other trityl radicals, the polarization mechanism differs from the classical solid effect. DFT calculations performed to rationalize this behaviour support the hypothesis that polarization is transferred from the unpaired electron to chlorine nuclei and from these to carbon by spin diffusion. The marked differences observed between neutral and anionic forms of the radical will be discussed.

TGF-β dependent regulation of oxygen radicals during transdifferentiation of activated hepatic stellate cells to myofibroblastoid cells

Background: The activation of hepatic stellate cells (HSCs) plays a pivotal role during liver injury because the resulting myofibroblasts (MFBs) are mainly responsible for connective tissue re-assembly. MFBs represent therefore cellular targets for anti-fibrotic therapy. In this study, we employed activated HSCs, termed M1-4HSCs, whose transdifferentiation to myofibroblastoid cells (named M-HTs) depends on transforming growth factor (TGF)-β. We analyzed the oxidative stress induced by TGF-β and examined cellular defense mechanisms upon transdifferentiation of HSCs to M-HTs. Results: We found reactive oxygen species (ROS) significantly upregulated in M1-4HSCs within 72 hours of TGF-β administration. In contrast, M-HTs harbored lower intracellular ROS content than M1-4HSCs, despite of elevated NADPH oxidase activity. These observations indicated an upregulation of cellular defense mechanisms in order to protect cells from harmful consequences caused by oxidative stress. In line with this hypothesis, superoxide dismutase activation provided the resistance to augmented radical production in M-HTs, and glutathione rather than catalase was responsible for intracellular hydrogen peroxide removal. Finally, the TGF-β/NADPH oxidase mediated ROS production correlated with the upregulation of AP-1 as well as platelet-derived growth factor receptor subunits, which points to important contributions in establishing antioxidant defense. Conclusion: The data provide evidence that TGF-β induces NADPH oxidase activity which causes radical production upon the transdifferentiation of activated HSCs to M-HTs. Myofibroblastoid cells are equipped with high levels of superoxide dismutase activity as well as glutathione to counterbalance NADPH oxidase dependent oxidative stress and to avoid cellular damage.

(No)competition in the Spanish retailing gasoline market: a variance filter approach

Various methodologies in economic literature have been used to analyse the international hydrocarbon retail sector. Nevertheless at a Spanish level these studies are much more recent and most conclude that generally there is no effective competition present in this market, regardless of the approach used. In this paper, in order to analyse the price levels in the Spanish petrol market, our starting hypothesis is that in uncompetitive markets the prices are higher and the standard deviation is lower. We use weekly retail petrol price data from the ten biggest Spanish cities, and apply Markov chains to fill the missing values for petrol 95 and diesel, and we also employ a variance filter. We conclude that this market demonstrates reduced price dispersion, regardless of brand or city.

Estudi de la desadsorció del pirè amb diferents surfactants en tres sòls artificials

Un dels problemes associats a la remeiació de contaminants hidròfobs és la seva poca disponibilitat. Es considera que un contaminant està disponible quan roman a la fase líquida del medi, ja sigui solubilitzat o en forma d’emulsió. Els surfactants són substàncies anfifíliques que promouen la transferència de compostos hidròfobs de la fase sòlida a la líquida. En aquest estudi s’escull el pirè com a representant dels hidrocarburs aromàtics policíclics i tres surfactants no iònics: un àmpliament citat a la bibliografia científica (Tween 80) i dos comercials (Gold Crew, BS-400). L’estudi es fa amb tres mescles d’argila i sorra amb diferents proporcions. La concentració micel·lar crítica (CMC) s’assoleix abans en sòls amb poc contingut en argila. L’eficiència dels surfactants està estretament relacionada amb la proporció d’argila i sorra. A concentracions molt per sobre de la CMC no s’observa una relació entre l’eficiència i la quantitat d’argila. El Tween 80 ha donat millors resultats que el Gold Crew i el BS-400, sense que aquest darrer no hagi presentat desadsorció de pirè.

Nacionalismo e identidad nacional en Corea, 1876-1945

Este trabajo de investigación tiene como objetivo el análisis de las circunstancias sociopolíticas que propiciaron la aparición y consolidación del nacionalismo como paradigma dominante en la creación de una nueva identidad colectiva coreana. El nacionalismo ha sido, en las últimas décadas, el discurso dominante dentro de la sociedad y la política coreana. De la derecha a la izquierda, pasando por los conservadores y los radicales, el pueblo coreano ha acogido de manera análoga el discurso nacionalista, siendo un instrumento utilizado abiertamente por las diferentes fuerzas gubernamentales para su propia legitimación política y moral tanto en el norte como en el sur.

El Paisatge

El paisatge de l’Alta Garrotxa ha sofert canvis radicals al llarg del temps i molt especial a les darreres dècades. Es proporcionen dades estadístiques sobre bosc, bosquina, pastura, conreu, vegetació de cinglera i zona estèril (roca nua, etc.)

S. P. Huntington : identitats i geopolítica

Aquest treball té com a propòsit esbrinar quina política internacional legitima S. P. Huntington, i quin paper hi adjudica als Estats Units. En aquest sentit, s'analitza el contingut de la teoria del "xoc de civilitzacions" i es treuen conclusions a partir de l'associació que realitza el politòleg nord-americà entre política internacional i les identitats cultural i religiosa en un món que ell considera marcadament hobbesià o d'esperit agonista.

El Paisatge

El concepce de paisatge ens permet una aproximació de síntesi al passat, present i a les tendències de futur dels territoris. En aquest sentit aquest concepte, entès com el conjunt de components de confereixen a un determinat espai unes característiques pròpies, és el reflex fidel d'evolució ambiental, econòmica, social, política i cultural que ha viscut un territori. En el cas concret de l'Alta Garrotxa el paisatge ha experinientat canvis radicals al llarg dels segles, i d'una manera molt especial en lesdarreres decades

Species resolved analysis of the expansion of hydroxyapatite laser ablation plumes

The plume generated by ablation of hydroxyapatite targets under ArF excimer laser irradiation has been investigated by means of fast intensified CCD-imaging and optical emission spectroscopy. Results have shown that the plume splits into two plasma clouds as it expands. Time and spatial resolved spectra have revealed that under the experiment conditions emission is mostly due to calcium neutral atoms and calcium oxide molecular radicals. Imaging of the plume with the aid of bandpass filters has demonstrated that the emissive species in the larger and faster plasma cloud are calcium neutral atoms, whereas in the smaller and slower one they are calcium oxide molecular radicals

Mineralization of the recalcitrant oxalic and oxamic acids by electrochemical advanced oxidation processes using a boron-doped diamond anode

Oxalic and oxamic acids are the ultimate and more persistent by-products of the degradation of N-aromatics by electrochemical advanced oxidation processes (EAOPs). In this paper, the kinetics and oxidative paths of these acids have been studied for several EAOPs using a boron-doped diamond (BDD) anode and a stainless steel or an air-diffusion cathode. Anodic oxidation (AO-BDD) in the presence of Fe2+ (AO-BDD-Fe2+) and under UVA irradiation (AO-BDD-Fe2+-UVA), along with electro-Fenton (EF-BDD), was tested. The oxidation of both acids and their iron complexes on BDD was clarified by cyclic voltammetry. AO-BDD allowed the overall mineralization of oxalic acid, but oxamic acid was removed much more slowly. Each acid underwent a similar decay in AO-BDD-Fe2+ and EFBDD, as expected if its iron complexes were not attacked by hydroxyl radicals in the bulk. The faster and total mineralization of both acids was achieved in AO-BDD-Fe2+-UVA due to the high photoactivity of their Fe(III) complexes that were continuously regenerated by oxidation of their Fe(II) complexes. Oxamic acid always released a larger proportion of NH4 + than NO3- ion, as well as volatile NOx species. Both acids were independently oxidized at the anode in AO-BDD, but in AO-BDD-Fe2+-UVA oxamic acid was more slowlydegraded as its content decreased, without significant effect on oxalic acid decay. The increase in current density enhanced the oxidation power of the latter method, with loss of efficiency. High Fe2+ contents inhibited the oxidation of Fe(II) complexes by the competitive oxidation of Fe2+ to Fe3+. Low current densities and Fe2+ contents are preferable to remove more efficiently these acids by the most potent AO-BDD-Fe2+-UVA method.

Nanoparticles in SiH4-Ar plasma: Modelling and comparison with experimental data

Experimental and theoretical investigations for growth of silicon nanoparticles (4 to 14 nm) in radio frequency discharge were carried out. Growth processes were performed with gas mixtures of SiH4 and Ar in a plasma chemical reactor at low pressure. A distinctive feature of presented kinetic model of generation and growth of nanoparticles (compared to our earlier model) is its ability to investigate small"critical" dimensions of clusters, determining the rate of particle production and taking into account the influence of SiH2 and Si2Hm dimer radicals. The experiments in the present study were extended to high pressure (≥20 Pa) and discharge power (≥40 W). Model calculations were compared to experimental measurements, investigating the dimension of silicon nanoparticles as a function of time, discharge power, gas mixture, total pressure, and gas flow.

Barnbyn Skå (Skå, la vila dels infants) 1947-1972: L’experiència terapèutica de Gustav Jonsson amb infants «irrecuperables»

The article presents the trajectory of the Swedish psychiatrist Gustav Jonsson (1907-1994) who, in the 1940s, revolutionised the therapeutic and educational treatment of children and young people, considered irreclaimable from the social point of view, who were committed to educational institutions. It analyses the social development of the Welfare State in Sweden, the legal framework of child protection, as well as the context of Swedish residential care centres for children and young people in the first half of the 20th century in order to go further into the psychological and educational work conducted with the Barnbyn Skå group. Jonsson redirected the analysis of violent behaviours that were manifest in these children and young people which made them intractable from the educational point of view and established elements of psychoanalytical understanding, based on a systemic approach in which the family context became essential in order to understand the children’s difficulties. Barnbyn Skå was the centre which, under the guidance of Jonsson, developed this new therapeutic and pedagogic approach. The educational work carried out there exceeded the traditional model in terms of control and surveillance. The methods were considered radical from within pedagogy and caused great controversy which led the centre to continuous investigations on behalf of the Social Services of Stockholm between 1960 and 1970. For several decades Barnbyn Skå has been considered a pioneering experience in the field of Scandinavian child psychiatry.

Manuel Ballester

Biografia de Manuel Ballester Boix (1919 – 2005), un dels científics catalans de major prestigi internacional. Les seves aportacions principals dins de l'àmbit de la química van ser el desenvolupament de la química percloorgànica i el descobriment dels Radicals Lliures Inerts.