Nucleophile-Catalyzed Additions to Activated Triple Bonds. Protection of Lactams, Imides, and Nucleosides with MocVinyl and Related Groups

Additions of lactams, imides, (S)-4-benzyl-1,3-oxazolidin-2-one, 2-pyridone, pyrimidine-2,4-diones (AZT derivatives), or inosines to the electron-deficient triple bonds of methyl propynoate, tert-butyl propynoate, 3-butyn-2-one, N-propynoylmorpholine, or N-methoxy-N-methylpropynamide in the presence of many potential catalysts were examined. DABCO and, second, DMAP appeared to be the best (highest reaction rates and E/Z ratios), while RuCl3, RuClCp*(PPh3)2, AuCl, AuCl(PPh3), CuI, and Cu2(OTf)2 were incapable of catalyzing such additions. The groups incorporated (for example, the 2-(methoxycarbonyl)ethenyl group that we name MocVinyl) serve as protecting groups for the above-mentioned heterocyclic CONH or CONHCO moieties. Deprotections were accomplished via exchange with good nucleophiles: the 1-dodecanethiolate anion turned out to be the most general and efficient reagent, but in some particular cases other nucleophiles also worked (e.g., MocVinyl-inosines can be cleaved with succinimide anion). Some structural and mechanistic details have been accounted for with the help of DFT and MP2 calculations.

Orthogonal protection of peptides and peptoids for cyclization by the thiol-ene reaction and conjugation

Cyclic peptides and peptoids were prepared using the thiolene Michael-type reaction. The linear precursors were provided with additional functional groups allowing for subsequent conjugation: an orthogonally protected thiol, a protected maleimide, or an alkyne. The functional group for conjugation was placed either within the cycle or in an external position. The click reactions employed for conjugation with suitably derivatized nucleoside or oligonucleotides were either cycloadditions (Diels-Alder, Cu(I)-catalyzed azide-alkyne) or the same Michael-type reaction as for cyclization.

Nucleophile-Catalyzed Additions to Activated Triple Bonds. Protection of Lactams, Imides, and Nucleosides with MocVinyl and Related Groups

Additions of lactams, imides, (S)-4-benzyl-1,3-oxazolidin-2-one, 2-pyridone, pyrimidine-2,4-diones (AZT derivatives), or inosines to the electron-deficient triple bonds of methyl propynoate, tert-butyl propynoate, 3-butyn-2-one, N-propynoylmorpholine, or N-methoxy-N-methylpropynamide in the presence of many potential catalysts were examined. DABCO and, second, DMAP appeared to be the best (highest reaction rates and E/Z ratios), while RuCl3, RuClCp*(PPh3)2, AuCl, AuCl(PPh3), CuI, and Cu2(OTf)2 were incapable of catalyzing such additions. The groups incorporated (for example, the 2-(methoxycarbonyl)ethenyl group that we name MocVinyl) serve as protecting groups for the above-mentioned heterocyclic CONH or CONHCO moieties. Deprotections were accomplished via exchange with good nucleophiles: the 1-dodecanethiolate anion turned out to be the most general and efficient reagent, but in some particular cases other nucleophiles also worked (e.g., MocVinyl-inosines can be cleaved with succinimide anion). Some structural and mechanistic details have been accounted for with the help of DFT and MP2 calculations.

2010: balanç d'un any

L'any 2010 va iniciar-se com l'any internacional de la diversitat biològica, com a punt d'inflexió en el context del "Compte enrere 2010", amb l'objectiu de deturar la pèrdua de biodiversitat a escala mundial. Si bé s'han aconseguit progressos significatius, propiciats per l'efemèride, encara som lluny d'haver revertit la situació de manera satisfactòria.

2010: balanç d'un any

L'any 2010 va iniciar-se com l'any internacional de la diversitat biològica, com a punt d'inflexió en el context del "Compte enrere 2010", amb l'objectiu de deturar la pèrdua de biodiversitat a escala mundial. Si bé s'han aconseguit progressos significatius, propiciats per l'efemèride, encara som lluny d'haver revertit la situació de manera satisfactòria.

La intensificación agrícola y la diversidad vegetal en los sistemas cerealistas de secano mediterráneos: implicaciones para la conservación

El trabajo analiza la importancia de la diversidad vegetal en los agroecosistemas y los efectos de la intensificación de las prácticas agrícolas y del paisaje sobre la diversidad vegetal. La revisión de diversos estudios llevados a cabo por el equipo de investigación permite destacar que la intensificación agrícola, tanto a escala de campo como de paisaje, afecta negativamente la abundancia y la riqueza específica de la flora. La comparación de la flora arvense de los cultivos cerealistas de secano mediterráneos entre los años 50 y la actualidad refleja la reducción de la flora arvense, especialmente de la flora propia de las mieses y la disminución de la abundancia de grupos funcionales como las leguminosas y las plantas entomófilas. El efecto de las prácticas agrícolas y de la complejidad del paisaje varía en función de la flora estudiada. Así, la complejidad del paisaje es el principal factor que afecta la configuración de la vegetación de los márgenes, mientras que la intensidad de las prácticas agrícolas es el principal factor para explicar las diferencias en la flora arvense en el centro de los campos. Por último, el artículo analiza diversas propuestas para la gestión de los agrosistemas con el objetivo de conciliar la producción agrícola y la conservación de la biodiversidad en la región mediterránea.

La intensificación agrícola y la diversidad vegetal en los sistemas cerealistas de secano mediterráneos: implicaciones para la conservación

El trabajo analiza la importancia de la diversidad vegetal en los agroecosistemas y los efectos de la intensificación de las prácticas agrícolas y del paisaje sobre la diversidad vegetal. La revisión de diversos estudios llevados a cabo por el equipo de investigación permite destacar que la intensificación agrícola, tanto a escala de campo como de paisaje, afecta negativamente la abundancia y la riqueza específica de la flora. La comparación de la flora arvense de los cultivos cerealistas de secano mediterráneos entre los años 50 y la actualidad refleja la reducción de la flora arvense, especialmente de la flora propia de las mieses y la disminución de la abundancia de grupos funcionales como las leguminosas y las plantas entomófilas. El efecto de las prácticas agrícolas y de la complejidad del paisaje varía en función de la flora estudiada. Así, la complejidad del paisaje es el principal factor que afecta la configuración de la vegetación de los márgenes, mientras que la intensidad de las prácticas agrícolas es el principal factor para explicar las diferencias en la flora arvense en el centro de los campos. Por último, el artículo analiza diversas propuestas para la gestión de los agrosistemas con el objetivo de conciliar la producción agrícola y la conservación de la biodiversidad en la región mediterránea.

Federalism and democracy. The case of minority nations: a federalist deficit

In this chapter, after pointing out the different logics that lie behind the familiar ideas of democracy and federalism, I have dealt with the case of plurinational federal democracies. Having put forward a double criterion of an empirical nature with which to differentiate between the existence of minority nations within plurinational democracies (section 2), I suggest three theoretical criteria for the political accommodation of these democracies. In the following section, I show the agonistic nature of the normative discussion of the political accommodation of this kind of democracies, which bring monist and pluralist versions of the demos of the polity into conflict (section 3.1), as well as a number of conclusions which are the result of a comparative study of 19 federal and regional democracies using four analytical axes: the uninational/plurinational axis; the unitarianism-federalism axis; the centralisation-decentralisation axis; and the symmetry-asymmetry axis (section 3.2). This analysis reveals shortcomings in the constitutional recognition of national pluralism in federal and regional cases with a large number of federated units/regions with political autonomy; a lower degree of constitutional federalism and a greater asymmetry in the federated entities or regions of plurinational democracies. It also reveals difficulties to establish clear formulas in these democracies in order to encourage a “federalism of trust” based on the participation and protection of national minorities in the shared government of plurinational federations/regional states. Actually, there is a federal deficit in this kind polities according to normative liberal-democratic patterns and to what comparative analysis show. Finally, this chapter advocates the need for a greater normative and institutional refinement in plurinational federal democracies. In order to achieve this, it is necessary to introduce a deeper form of “ethical” pluralism -which displays normative agonistic trends, as well as a more “confederal/asymmetrical” perspective, congruent with the national pluralism of these kind of polities.

Water scarcity, social power and the production of an elite suburb: the political ecology of water in Matadepera, Catalonia

This article investigates the history of land and water transformations in Matadepera, a wealthy suburb of metropolitan Barcelona. Analysis is informed by theories of political ecology and methods of environmental history; although very relevant, these have received relatively little attention within ecological economics. Empirical material includes communications from the City Archives of Matadepera (1919-1979), 17 interviews with locals born between 1913 and 1958, and an exhaustive review of grey historical literature. Existing water histories of Barcelona and its outskirts portray a battle against natural water scarcity, hard won by heroic engineers and politicians acting for the good of the community. Our research in Matadepera tells a very different story. We reveal the production of a highly uneven landscape and waterscape through fierce political and power struggles. The evolution of Matadepera from a small rural village to an elite suburb was anything but spontaneous or peaceful. It was a socio-environmental project well intended by landowning elites and heavily fought by others. The struggle for the control of water went hand in hand with the land and political struggles that culminated – and were violently resolved - in the Spanish Civil War. The displacement of the economic and environmental costs of water use from few to many continues to this day and is constitutive of Matadepera’s uneven and unsustainable landscape. By unravelling the relations of power that are inscribed in the urbanization of nature (Swyngedouw, 2004), we question the perceived wisdoms of contemporary water policy debates, particularly the notion of a natural scarcity that merits a technical or economic response. We argue that the water question is fundamentally a political question of environmental justice; it is about negotiating alternative visions of the future and deciding whose visions will be produced.

Estudio comparativo de conocimientos y percepciones ambientales sobre la Reserva de la Biosfera de Sian Ka'an entre estudiantes de primaria de comunidades maya, México

El estudio analiza y compara las percepciones y conocimientos ambientales que estudiantes de primaria del municipio maya de Felipe Carrillo Puerto tienen sobre la vecina Reserva de la Biósfera de Sian Ka’an (RBSK) en términos de biodiversidad, con el fin de evaluar y elaborar programas de Educación Ambiental (EA) dirigidos a promover la protección de este espacio natural. Se analizan dibujos, cuestionarios y encuestas recogidos en tres comunidades maya que difieren en su proximidad a la RBSK y en su nivel de urbanización. Los resultados indican que los niños en general desconocen la RBSK y la biodiversidad de la zona. Para aumentar el conocimiento ambiental de los alumnos se propone potenciar el conocimiento vivencial, mantener la lengua y cultura maya y el contacto de ésta con la naturaleza y potenciar la afinidad del maestro por la temática ambiental y por la RBSK.

The European Union Perception of Cuba: From Frustation to Irritation

On Friday May 16, the Ministry of Foreign Affairs of Cuba summoned the newly-appointed charged’affairs of the European Commission in Havana and announced the withdrawal of the application procedure for membership in the Cotonou Agreement of the Africa, Caribbean, and Pacific (ACP) countries, and in fact renouncing to benefit from European development aid.1 In a blistering note published in the Granma official newspaper of the Cuban Communist Party, the government blamed the EU Commission for exerting undue pressure, its alleged alignment with the policies of the United States, and censure for the measures taken by Cuba during the previous weeks.2 In reality, Cuba avoided an embarrasin flat rejection for its application. This was the anti-climatic ending for a long process that can be traced back to the end of the Cold War, in a context where Cuba has been testing alternative grounds to substitute for the overwhelming protection of the Soviet Union

The externalisation of the asylum function in the European Union

This paper aims to identify and assess the main items in the strategy followed by the EU and its member states on the externalisation of their asylum function. First, it analyses the European harmonisation of the return to safe third countries and to countries of first asylum, which is carried out by means of readmission agreements. Second, it refers to the strategies defined by the Hague and the Stockholm programs concerning the External Aspects of the European Union Asylum Policy, on the detention centres for illegal immigrants abroad, and on the proposals for delocalisation of asylum applications processing centres beyond the EU borders. Finally, this paper considers whether the strategy of externalisation of the function of asylum sometimes lacks legitimacy, and to what extent there is a fair balance between the interests of the states and the protection of the human rights of refugees and asylum seekers.

Quotient spaces of boundedly rational types

By identifying types whose low-order beliefs up to level li about the state of nature coincide, weobtain quotient type spaces that are typically smaller than the original ones, preserve basic topologicalproperties, and allow standard equilibrium analysis even under bounded reasoning. Our Bayesian Nash(li; l-i)-equilibria capture players inability to distinguish types belonging to the same equivalence class.The case with uncertainty about the vector of levels (li; l-i) is also analyzed. Two examples illustratethe constructions.