Inter- and intramolecular enantioselective carbolithiation reactions

In this review we summarize recent developments in inter- and intramolecular enantioselective carbolithiation reactions carried out in the presence of a chiral ligand for lithium, such as (-)-sparteine, to promote facial selection on a C=C bond. This is an attractive approach for the construction of new carbon-carbon bonds in an asymmetric fashion, with the possibility of introducing further functionalization on the molecule by trapping the reactive organolithium intermediates with electrophiles.

Chiral gold(I) vs chiral silver complexes as catalysts for the enantioselective synthesis of the second generation GSK-hepatitis C virus inhibitor

The synthesis of a GSK 2(nd) generation inhibitor of the hepatitis C virus, by enantioselective 1,3-dipolar cycloaddition between a leucine derived iminoester and tert-butyl acrylate, was studied. The comparison between silver(I) and gold(I) catalysts in this reaction was established by working with chiral phosphoramidites or with chiral BINAP. The best reaction conditions were used for the total synthesis of the hepatitis C virus inhibitor by a four step procedure affording this product in 99% ee and in 63% overall yield. The origin of the enantioselectivity of the chiral gold(I) catalyst was justified according to DFT calculations, the stabilizing coulombic interaction between the nitrogen atom of the thiazole moiety and one of the gold atoms being crucial.

Evaluation of Fentanyl Disposition and Effects in Newborn Piglets as an Experimental Model for Human Neonates

Background: Fentanyl is widely used off-label in NICU. Our aim was to investigate its cerebral, cardiovascular and pulmonary effects as well as pharmacokinetics in an experimental model for neonates. Methods: Fentanyl (5 mu g/kg bolus immediately followed by a 90 minute infusion of 3 mu g/kg/h) was administered to six mechanically ventilated newborn piglets. Cardiovascular, ventilation, pulmonary and oxygenation indexes as well as brain activity were monitored from T = 0 up to the end of experiments (T = 225-300 min). Also plasma samples for quantification of fentanyl were drawn. Results: A "reliable degree of sedation" was observed up to T = 210-240 min, consistent with the selected dosing regimen and the observed fentanyl plasma levels. Unlike cardiovascular parameters, which were unmodified except for an increasing trend in heart rate, some of the ventilation and oxygenation indexes as well as brain activity were significantly altered. The pulmonary and brain effects of fentanyl were mostly recovered from T = 210 min to the end of experiment. Conclusion: The newborn piglet was shown to be a suitable experimental model for studying fentanyl disposition as well as respiratory and cardiovascular effects in human neonates. Therefore, it could be extremely useful for further investigating the drug behaviour under pathophysiological conditions.

Analysis of SUMOylated proteins using SUMO-traps

6 p. [+ 7 p. Supplementary Information]

Asymmetric organocatalytic cascade reactions

302 p. : gráf.

Petrarca y las primeras ediciones de Terencio

[ES] De entre las ediciones de Terencio publicadas en las primeras décadas de la imprenta, las de Vindelino de Espira son las que muestran una mayor voluntad filológica y, sin duda, las que ofrecen un texto más correcto. Estas ediciones dependen del texto terenciano reconstruido por Petrarca: concretamente, IGI 9408 desciende de una fase textual anterior a la que queda fijada en 1358 y responde además a algunos de los criterios propugnados por Petrarca en la Vita Terrentii; IGI 9409, por su parte, depende —parcialmente— del texto de 1358 y muestra indicios de haber sufrido la influencia de otro ejemplar de Petrarca. En fin, la presencia de la Vita Terrentii en la transmisión impresa de Terencio es una muestra más de la vigencia de la filología terencia de Petrarca durante aquellos años.

Euskal autore zaharren irakaskuntza Lehen Hezkuntzan: proiektu berritzaile baten proposamena

Euskara: Lan honek euskal autore zaharrak Lehen Hezkuntzako ikasleei hurbiltzea du helburu. Ezinbestekoa da neska-mutilek ikasgeletan klasikoen ondarea ezagutzeko aukera izatea, euskal autore zaharren irakaskuntza-ikaskuntza prozesua suspertzeko. Izan ere, idazle klasikoak oinarrizko hezkuntzan duten tokia ez da handia izan, hauek lantzeak zailtasunak dakartzalako. Beraz, zailtasun horiek aztertuta eta lekuko idazle ezberdinen lan hautatuen egokitze-lana aintzat hartuz, proiektu berritzaile baten proposamena eskaini nahi da, euskarazko literatura zaharra irakurtzeko eta lantzeko zaletasuna sustatzeko bidea erakusteko asmoz. Horrela izanik, ikasleek euren neurrira eta interesetara moldatutako egitasmoa eskura izango dute, egungo hezkuntza-sisteman beharrezkoak diren oinarrizko gaitasunak barneratuz, beti ere gaiarekiko motibazioa eta jakin-mina aintzat hartuta.

Magnetic Cross-Linked Enzyme Aggregates (mCLEAs) of Candida antarctica Lipase: An Efficient and Stable Biocatalyst for Biodiesel Synthesis

Enzyme-catalyzed production of biodiesel is the object of extensive research due to the global shortage of fossil fuels and increased environmental concerns. Herein we report the preparation and main characteristics of a novel biocatalyst consisting of Cross-Linked Enzyme Aggregates (CLEAs) of Candida antarctica lipase B (CALB) which are covalently bound to magnetic nanoparticles, and tackle its use for the synthesis of biodiesel from non-edible vegetable and waste frying oils. For this purpose, insolubilized CALB was covalently cross-linked to magnetic nanoparticles of magnetite which the surface was functionalized with –NH2 groups. The resulting biocatalyst combines the relevant catalytic properties of CLEAs (as great stability and feasibility for their reutilization) and the magnetic character, and thus the final product (mCLEAs) are superparamagnetic particles of a robust catalyst which is more stable than the free enzyme, easily recoverable from the reaction medium and reusable for new catalytic cycles. We have studied the main properties of this biocatalyst and we have assessed its utility to catalyze transesterification reactions to obtain biodiesel from non-edible vegetable oils including unrefined soybean, jatropha and cameline, as well as waste frying oil. Using 1% mCLEAs (w/w of oil) conversions near 80% were routinely obtained at 30°C after 24 h of reaction, this value rising to 92% after 72 h. Moreover, the magnetic biocatalyst can be easily recovered from the reaction mixture and reused for at least ten consecutive cycles of 24 h without apparent loss of activity. The obtained results suggest that mCLEAs prepared from CALB can become a powerful biocatalyst for application at industrial scale with better performance than those currently available.

Keep an "eye" on the text: The Use of Self-mention in the Academic Writing of Experts

One of the most controversial inquiries in academic writing is whether it is admissible to use first person pronouns in a scientific paper or not. Many professors discourage their students from using them, rather favoring a more passive tone, and thus causing novices to avoid inserting themselves into their texts in an expert-like manner. Abundant research, however, has recently attested that negotiation of identity is plausible in academic prose, and there is no need for a paper to be void of an authorial identity. Because in the course of the English Studies Degree we have received opposing prompts in the use of I, the aim of this dissertation is to throw some light upon this vexed issue. To this end, I compiled a corpus of 16 Research Articles (RAs) that comprises two sub-corpora, one featuring Linguistics RAs and the other one Literature RAs, and each, in turn, consists of articles written by American and British authors. I then searched for real occurrences of I, me, my, mine, we, us, our and ours, and studied their frequency, rhetorical functions and distribution along each paper. The results obtained certainly show that academic writing is no longer the faceless prose that it used to be, for I is highly used in both disciplines and varieties of English. Concerning functions, the most typically used roles were the use of I to take credit for the writer’s research process, and also those involving plural forms. With respect to the spatial disposition, all sections welcomed first person pronouns, but the Method and the Results/Discussion sections seem to stimulate their appearance. On the basis of these findings, I suggest that an L2 writing pedagogy that is mindful not only of the language proficiency, but also of the students’ own identity may have a beneficial effect on the composition of their texts.

Análisis de emplazamiento de un parque eólico en la parte peninsular española.

[ES]El objetivo de este trabajo fin de grado es analizar el recurso eólico presente en la parte peninsular español y diseñar un parque eólico en el que se considere el emplazamiento más óptimo. Para ello se analizan mapas de vientos, mapas de espacios protegidos, mapas de batimetría y de disposición del medio marino. Tras ello se concluye que ese punto óptimo se encuentra en la costa de Cádiz, cercana al Cabo de Trafalgar. En ese punto se diseña un parque eólico offshore. Adicionalmente, se calcula la generación de energía eléctrica anual en ese parque y se realiza su correspondiente planificación y análisis económico.