Total synthesis of (-)-isoavenaciolide

An enantioselective approach to (-)-isoavenaciolide was achieved starting from 1- undecyn-3-ol. The synthesis relied upon the preparation of a chiral 4-silyloxy-2-alkenylborane by hydroboration of a protected 2,3-allenol and subsequent stereoselective addition to 2- thiophenecarboxaldehyde

The long run development of Chile and the Natural Resources curse. Linkages, policy and growth, 1850-1950

This chapter analyses the effects of Natural Resources on the Chilean economy in the long run -1850-1950-. Specifically, the authors focus their attention on the mining cycles -nitrates and copper- and their impact on the mining activity. We also compare it with the evolution of the industry and whole economy, and how this has affected the economic growth of the country. In that sense, the industrial performance in Chile at the end of the 19th century until the Great Depression is still under debate. The optimistic view of Kirsch -1977- forehead the pessimistic view of Lagos -1966- and Palma -1979-. The new data and its analyses shows a neutral effect of the Natural Resources in the industrial development.

Identidad y diversidad en el conocimiento del medio natural, social y cultural en la educación infantil y primaria

El actual proceso de globalización de la sociedad ha supuesto, entre otros aspectos, la llegada de fuertes corrientes migratorias y la presencia en la escuela de niños y niñas de todo el mundo. Esta realidad implica una nueva orientación del currículo de conocimiento del medio que posibilite la comprensión de la diversidad y la pluriidentidad presente en todas las aulas de las escuelas de Cataluña y así conseguir educar para una nueva ciudadanía. Este artículo presenta los resultados de un proceso de investigación-acción que ha tenido como objetivo la innovación curricular en el conocimiento del medio natural, social y cultural en seis centros de educación infantil y primaria de las comarcas gerundenses. Se pretende describir y explicar una innovación o cambio curricular fundamentado teóricamente, del que se ha derivado una nueva forma de trabajo en el aula; y mostrar el proceso metodológico de elaboración e implementación con las resistencias y los cambios reales en el currículo

Synthesis and structure - Activity relationship study of potent cytotoxic analogues of the marine alkaloid Lamellarin D

The marine alkaloid, Lamellarin D (Lam-D), has shown potent cytotoxicity in numerous cancer cell lines, and was recently identified as a potent topoisomerase I inhibitor. A library of open lactone analogs of Lam-D was prepared from a methyl 5,6-dihydropyrrolo[2,1-a]isoquinoline-3- carboxylate scaffold (1) by introducing various aryl groups through sequential and regioselective bromination, followed by Pd(0)-catalyzed Suzuki cross-coupling chemistry. The compounds were obtained in a 24-44% overall yield, and tested in a panel of three human tumor cell lines, MDA-MB- 231 (breast), A-549 (lung), and HT-29 (colon), to evaluate their cytotoxic potential. From these data the SAR study concluded that more than 75% of the open-chain Lam-D analogs tested showed cytotoxicity in a low micromolar GI50 range.

Convergent Approaches for the Synthesis of the Anti-tumoral Peptide, Kahalalide F. Study of Orthogonal Protecting Groups

Kahalalide compounds are peptides that are isolated from a Hawaiian herbivorous marine species of mollusc, Elysia rufescens, and its diet, the green alga Bryopsis sp. Kahalalide F and its synthetic analogues are the most promising compounds of the Kahalalide family because they show anti-tumoral activity. Linear solid-phase syntheses of Kahalalide F have been reported. Here we describe several new improved synthetic routes based on convergent approaches with distinct orthogonal protection schemes for the preparation of Kahaladide analogues. These strategies allow a better control and characterization of the intermediates because more reactions are performed in solution. Five derivatives of Kahalalide F were synthesized using several convergent approaches.

Preparation of penta-azole containing cyclopeptides: challenges in macrocyclization

Herein is described the synthesis of several analogs of the natural product IB-01211 from concatenated azoles, via a biomimetic pathway based on cyclization-oxidation of serine containing peptides combined with the Hantzsch synthesis. The macrocyclization of rigid peptide compounds 1 and 2 to give IB-01211 and its epimer 12b was explored, and the results are compared here to those previously obtained for the macrocyclization of more flexible structures in the syntheses of YM-216391, telomestatin, and IB-01211. Lastly, the preliminary results of anti-tumor activity screening of the synthesized analogs are discussed.

Lamellarin D bioconjugates II: synthesis and cellular internalization of dendrimer and nuclear location signal derivatives

The design and synthesis of Lamellarin D conjugates with a nuclear localization signal peptide and a poly(ethylene glycol)-based dendrimer are described. Conjugates 1-4 were obtained in 8-84% overall yields from the corresponding protected Lamellarin D. Conjugates 1 and 4 are 1.4 to 3.3-fold more cytotoxic than the parent compound against three human tumor cell lines(MDA-MB-231 breast, A-549 lung, and HT-29 colon). Besides, conjugates 3, 4 showed a decrease in activity potency in BJ skin fibroblasts, a normal cell culture. Cellular internalization was analyzed and nuclear distribution pattern was observed for 4, which contains a nuclear localization signalling sequence.

Synthesis and structure - Activity relationship study of potent cytotoxic analogues of the marine alkaloid Lamellarin D

The marine alkaloid, Lamellarin D (Lam-D), has shown potent cytotoxicity in numerous cancer cell lines, and was recently identified as a potent topoisomerase I inhibitor. A library of open lactone analogs of Lam-D was prepared from a methyl 5,6-dihydropyrrolo[2,1-a]isoquinoline-3- carboxylate scaffold (1) by introducing various aryl groups through sequential and regioselective bromination, followed by Pd(0)-catalyzed Suzuki cross-coupling chemistry. The compounds were obtained in a 24-44% overall yield, and tested in a panel of three human tumor cell lines, MDA-MB- 231 (breast), A-549 (lung), and HT-29 (colon), to evaluate their cytotoxic potential. From these data the SAR study concluded that more than 75% of the open-chain Lam-D analogs tested showed cytotoxicity in a low micromolar GI50 range.

Habilitation of a city in case with multiple victims = Habilitación de una ciudad en sucesos con múltiples víctimas

Debido a que en España se han dado diferentes accidentes con múltiples víctimas en diferentes puntos del país, se cree conveniente que cada ciudad tenga un plan de gestión de catástrofes con una serie de espacios habilitados para poder responder en caso de un accidente de estas características. El presente artículo tiene como objetivo presentar la habilitación de espacios aplicable en cualquier capital de provincia de España, tomando como ejemplo la ciudad de Girona. Se ha tomado la ciudad de Girona como modelo por presentar infraestructuras viarias, ferroviarias, portuarias y aeroportuarias cada vez más concurridas

Resposta a les al·legacions al projecte de restauració de la Pedrera Berta (Sant Cugat del Vallès i el Papiol)

Postprint (published version)

Temps, guerra i política en la reivindicació de territoris indígenes i nacionals: un relat gràfic de la guerra del Chaco

[cat]L'estudi vol aprofundir en les conseqüències del conflicte bèlic que enfrontà a Bolivia i Paragüai a la guerra del Chaco (1923-1935), de manera especial per a les poblacions indígenas, les quals, en els darrers anys, han començat a dur a terme una clara reivindicació per al reconeixement oficial dels seus drets territorials a partir de la revaloració de la participació dels indígenes del Chaco en aquesta guerra com també de la utilització dels recursos naturals i de les comunitats autòctones pels exèrcits enfrontats, tot tenint com a eina d'estudi el registre fotogràfic del conflicte.

Total synthesis of lamellarin D and analogs library

Larnellarins are a group of marine natural products isolated from the prosobranch mollusc Lamellaria sp., the ascidian Didemnum sp., and the sponge Dendrilla Cactos. Several of them exhibit interesting biological activities. Natural as well as synthetic lamellarins should be excellent candidates for the development of new drugs due to their unique skeletal structure and their important biological activities especially as antitumor agents. Lamelarin O has been recently characterized as a topoisomerase 1-targeted anti tumor agent. A variety of synthetic approaches have been developed for this family of alkaloids. Herein we describe a new route to the synthesis of Lamellarin D, from a methyl 2-pyrrolecarboxylate. Transformation of the starting material into the scaffold, a substituted 5,6-dihydropyrrolo (2,l ­a)isoquinoline (5,6-DHPl), was afforded by N-alkylation followed by intramolecular Heck cyclization. From this scaffold the synthetic strategy is based on two sequential regioselective bromination!Suzuki cross-coupling reactions which permitted the introduction of differently substituted aryl groups on positions 1 and 2 followed by oxidation, deprotection, and lactonization.

Organic chicken product authentication: state-of-the-art and future perspectives

Organic food products are highly susceptible to fraud. Currently, administrative controls are conducted to detect fraud, but having an analytical tool able to verify the organic identity of food would be very supportive. The state-of-the-art in food authentication relies on fingerprinting approaches that find characteristic analytical patterns to unequivocally identify authentic products. While wide research on authentication has been conducted for other commodities, the authentication of organic chicken products is still in its infancy. Challenges include finding fingerprints to discriminate organic from conventional products, and recruiting sample sets that cover natural variability. Future research might be oriented towards developing new authentication models for organic feed, eggs and chicken meat, keeping models updated and implementing them into regulations. Meanwhile, these models might be very supportive to the administrative controls directing inspections towards suspicious fraudulent samples.

L'Impacte ecològic dels peixos introduïts a Catalunya

We review the invasive fish species introduced to Catalonia (Spain) and their mechanisms of ecological impact. Catalonia has about 15 established foreign fish species along with many others that have been translocated. These fish species, which are identical to those that have been introduced worldwide (thereby contributing to biotic homogenization), include: common carp (Cyprinus carpio), largemouth bass (Micropterus salmoides), eastern mosquitofish (Gambusia holbrooki) and many European cyprinids that are not native to the Iberian Peninsula. There are some well-documented repercussions to the native fauna, such as the impact of mosquitofish on endangered, endemic cyprinodonts. The illegal introduction by anglers continues to be one of the main culprits of this environmental problem, one that has been barely addressed by local and state authorities

La promoció de vendes de les marques d'aigües minerals en la distribució organitzada: el cas de Mercadona

La popularització de productes naturals i d’hàbits de vida saludables, ha contribuït a estimular la demanda de tota mena de d’articles vinculats a la salut com l’aigua mineral natural, que els últims anys, ha passat de ser una “commodity" a un producte de valor afegit. La conjuntura social i econòmica dels últims anys, també ha condicionat els hàbits de consum de les famílies. En alguns casos, la reducció del poder adquisitiu ha motivat l’estalvi en tota mena de productes i serveis fet que ha beneficiat les marques privades o de distribuïdor, sovint considerades inferiors en qualitat però també en preu, i que d’ara en endavant anomenarem (MDD). Els distribuïdors han recolzat els productes MDD millorant-ne la qualitat, la presentació i han invertit en estratègies de comunicació, fet que, ha suposat un increment de la quota de mercat en totes les categories de bens de consum favorable a les MDD. El present treball, pretén dur a terme un anàlisi comparatiu dels preus de venda al públic de les aigües minerals naturals a la cadena Mercadona, i de les estratègies promocionals seguides per tal d’afavorir la MDD vers les marques de fabricant (MDF).