Governance through the market and the state : postgraduate education in Argentina

Resumen tomado de la publicaci??n

Fer lectors en un context advers

Resumen basado en el de la publicaci??n

Els pedag??gics sons dels silencis : enll?? del silenci d???Auschwitz

Resumen basado en el de la publicaci??n

BIOrienta2: orientación a futuros farmacéuticos. La Investigación en biomedicina como carrera profesional

El Grado de Farmacia ofrece una formación idónea para personas que enfoquen su carrera profesional como investigadores en el área de Biomedicina. Ninguna otra formación de Pregrado aúna conocimientos tan amplios en Microbiología, Parasitología, Química, Biología Molecular y Biotecnología así como en aspectos relacionados con el mecanismo de acción de fármacos y con alteracions fisio/patológicas a nivel molecular. Por ello, nos hemos planteado realizar un Plan de Acción Tutorial enfocado a formar alumnos desde sus etapas iniciales en la investigación en Biomedicina: elección de su trayectoria curricular, requisitos para realizar una carrera científica y oportunidades de formación en esta área

Paper del nucli hidrofòbic principal de la RNasa A en el plegament i desplegament induïts per pressió i temperatura

Utilitzant temperatura i pressió com a agents desnaturalitzants s'ha explorat la contribució a l'estabilitat de diferents residus del principal nucli hidrofòbic de la RNasa A. Aquests resutats suggereixen que el principal nucli hidrofòbic d'aquest enzim, està fortament empaquetat i ha revelat l'existència de reordenacions en l'interior de la proteïna. El mètode dels valors , han permès estudiar el paper de les interaccions hidrofòbiques establertes pels residus del principal nucli hidrofòbic de la RNasa A en el seu estat de transició induït per pressió. En conjunt, aquests resultats suggereixen que l'estat de transició de la RNasa A, s'assemblaria a un glòbul col·lapsat amb una cadena estructurada però amb un debilitat nucli hidrofòbic. S'ha explorat també, el paisatge energètic del plegament/desplegament proteic de la variant Y115W de la RNasa A. L'estat de transició sembla interaccionar fortament amb la capa d'hidratació d'aquest estat, tal i com indiquen els resultats en presència de glicerol.

A consolidação da Educação e Formação Profissional na Escola Secundária nos últimos 50 anos em Portugal

Ao longo das últimas cinco décadas, temos assistido a uma presença, cada vez mais consistente, do ensino profissionalmente qualificante no sistema educativo português. A actual abertura das escolas secundárias da rede pública à educação e formação profissional tornou-se um facto incontornável, com a última revisão curricular do ensino secundário a permitir um arrojado salto no seu desenvolvimento, ao qual não é alheia a sua crescente valorização e consolidação no contexto da acção educativa. A procura da educação, nomeadamente de características técnico-profissionais, torna-se mais intensa a partir dos anos 1960 - é a fase em que a teoria do capital humano se torna o modelo dominante nos sistemas educativos internacionais, privilegiando a correlação entre investimento no ensino e a expansão da economia, com grandes reflexos em Portugal, e que se materializa, em 1973, Mas, a partir dos anos 1980, o discurso político volta a ser fortemente marcado pela ideologia dos recursos humanos, o que faz da qualificação profissional um elemento naturalmente integrante da política educativa portuguesa. Este traço, acentua-se ao longo das décadas que se seguem, repercutindo-se nas várias reformas das políticas educativas que, entretanto, vão surgindo, culminando na Reforma do Ensino Secundário, em 2004, cujos objectivos assumem plenamente a importância do ensino profissionalmente qualificante, com uma expressão no sistema educativo mais intensa que nunca.

Memorias montoneras: metáforas de la guerra en Argentina (Crítica)

La autora lee la novela de Sergio Pollastri desde la perspectiva crítica de las posibilidades e imposibilidades de la reconstrucción de una historia, a partir de este relato testimonial que se mueve en el territorio de la violencia y las armas (la militancia política) y en el de la subjetividad (la poesía, la ficción). Resalta los vínculos entre vida y literatura, que cruzan toda la novela, así, apela a la metáfora para referirse a dos tipos de silencios en las ficciones sobre la violencia revolucionaria: la opción por las armas y la delación bajo tortura. Resalta el rol de la metáfora en este texto que tensa hasta sus límites el género testimonial, y que cobra su mayor fuerza hacia el final: «La revolución es frágil y superficial como una violeta, aquello que la comparación desarrolla es al mismo tiempo lo que amortigua la caída del salto brutal al vacío con el que la novela cierra su enunciación».

De las cuotas a la paridad: avances y límites del derecho a la participación política de las mujeres en el Ecuador

La paridad, formulada como un derecho para que hombres y mujeres accedan en igualdad de condiciones a los distintos espacios de poder, es un principio consagrado constitucionalmente, que tiene su origen en la lucha de los distintos movimientos de mujeres por democratizar el escenario político, área tradicionalmente masculina, para que incluya equilibradamente, la presencia, intereses y necesidades de hombres y mujeres en el quehacer estatal. En el Ecuador, una mayor participación política electoral de las mujeres ha sido posible por la aplicación progresiva de las leyes de cuotas, instrumentos sustentados en la necesidad de acelerar, jurídicamente, la consecución de la igualdad real entre hombres y mujeres, con la ayuda de medidas de acción afirmativa de carácter temporal. La Constitución de 2008 es novedosa en tanto da un salto cualitativo, al pasar de la progresiva aplicación de cuotas de carácter temporal, a una medida definitiva como la paridad, que se aplica a las listas pluripersonales en procesos de elección popular y también a los altos cargos públicos de nominación, en las cinco funciones del Estado. El presente trabajo analiza desde la perspectiva de género instrumentos internacionales, normas constitucionales y legales; jurisprudencia constitucional y electoral, estudios académicos e históricos previos, notas periodísticas, información estadística y entrevistas a mujeres políticas; con el fin de establecer avances y límites del derecho a la participación política de las mujeres en el Ecuador, desde la superación de las cuotas como medidas de carácter temporal, con la declaración constitucional de paridad, vigente desde 2008.

Self-assembled biomimetic [2Fe2S]-hydrogenase-based photocatalyst for molecular hydrogen evolution

The large-scale production of clean energy is one of the major challenges society is currently facing. Molecular hydrogen is envisaged as a key green fuel for the future, but it becomes a sustainable alternative for classical fuels only if it is also produced in a clean fashion. Here, we report a supramolecular biomimetic approach to form a catalyst that produces molecular hydrogen using light as the energy source. It is composed of an assembly of chromophores to a bis(thiolate)-bridged diiron ([2Fe2S]) based hydrogenase catalyst. The supramolecular building block approach introduced in this article enabled the easy formation of a series of complexes, which are all thoroughly characterized, revealing that the photoactivity of the catalyst assembly strongly depends on its nature. The active species, formed from different complexes, appears to be the [Fe-2(mu-pdt)(CO)(4){PPh2(4-py)}(2)] (3) with 2 different types of porphyrins (5a and 5b) coordinated to it. The modular supramolecular approach was important in this study as with a limited number of building blocks several different complexes were generated.

DNA cleavage and antitumour activity of platinum(II) and copper(II) compounds derived from 4-methyl-2-N-(2-pyridylmethyl)aminophenol: spectroscopic, electrochemical and biological investigation

The reaction of the redox-active ligand, Hpyramol (4-methyl-2-N-(2-pyridylmethyl)aminophenol) with K2PtCl4 yields monofunctional square-planar [Pt(pyrimol)Cl], PtL-Cl, which was structurally characterised by single-crystal X-ray diffraction and NMR spectroscopy. This compound unexpectedly cleaves supercoiled double-stranded DNA stoichiometrically and oxidatively, in a non-specific manner without any external reductant added, under physiological conditions. Spectro-electrochemical investigations of PtL-Cl were carried out in comparison with the analogue CuL-Cl as a reference compound. The results support a phenolate oxidation, generating a phenoxyl radical responsible for the ligand-based DNA cleavage property of the title compounds. Time-dependent in vitro cytotoxicity assays were performed with both PtL-Cl and CuL-Cl in various cancer cell lines. The compound CuL-Cl overcomes cisplatin-resistance in ovarian carcinoma and mouse leukaemia cell lines, with additional activity in some other cells. The platinum analogue, PtL-Cl also inhibits cell-proliferation selectively. Additionally, cellular-uptake studies performed for both compounds in ovarian carcinoma cell lines showed that significant amounts of Pt and Cu were accumulated in the A2780 and A2780R cancer cells. The conformational and structural changes induced by PtL-Cl and CuL-Cl on calf thymus DNA and phi X174 supercoiled phage DNA at ambient conditions were followed by electrophoretic mobility assay and circular dichroism spectroscopy. The compounds induce extensive DNA degradation and unwinding, along with formation of a monoadduct at the DNA minor groove. Thus, hybrid effects of metal-centre variation, multiple DNA-binding modes and ligand-based redox activity towards cancer cell-growth inhibition have been demonstrated. Finally, reactions of PtL-Cl with DNA model bases (9-Ethylguanine and 5'-GMP) followed by NMR and MS showed slow binding at Guanine-N7 and for the double stranded self complimentary oligonucleotide d(GTCGAC)(2) in the minor groove.

Redox chemistry and electronic properties of 2,3,5,6-tetrakis(2-pyridyl)pyrazine-bridged diruthenium complexes controlled by N,C,N '-biscyclometalated ligands

To investigate the consequences of cyclometalation for electronic communication in dinuclear ruthenium complexes, a series of 2,3,5,6-tetrakis(2-pyridyl)pyrazine (tppz) bridged diruthenium complexes was prepared and studied. These complexes have a central tppz ligand bridging via nitrogen-to-ruthenium coordination bonds, while each ruthenium atom also binds either a monoanionic, N,C,N'-terdentate 2,6-bis(2'-pyridyl)phenyl (R-N boolean AND C boolean AND N) ligand or a 2,2':6',2 ''-terpyridine (tpy) ligand. The N,C,N'-, that is, biscyclometalation, instead of the latter N,N', N ''-bonding motif significantly changes the electronic properties of the resulting complexes. Starting from well-known [{Ru(tpy)}(2)(mu-tppz)](4+) (tpy = 2,2':2 '',6-terpyridine) ([3](4+)) as a model compound, the complexes [{Ru(R-N boolean AND C boolean AND N)}(mu-tppz){Ru(tpy)}](3+) (R-N boolean AND C(H)boolean AND N = 4-R-1,3-dipyridylbenzene, R = H ([4a](3+)), CO2Me ([4b](3+))), and [{Ru(R-N boolean AND C boolean AND N)}(2)(mu-tppz)](2+), (R = H ([5a](2+)), CO2Me ([5b](2+))) were prepared with one or two N,C,N'-cyclometalated terminal ligands. The oxidation and reduction potentials of cyclometalated [4](3+) and [5](2+) are shifted negatively compared to non-cyclometalated [3](4+), the oxidation processes being affected more significantly. Compared to [3](4+), the electronic spectra of [5](2+) display large bathochromic shifts of the main MLCT transitions in the visible spectral region with low-energy absorptions tailing down to the NIR region. One-electron oxidation of [3](4+) and [5](2+) gives rise to low-energy absorption bands. The comproportionation constants and NIR band shape correspond to delocalized Robin-Day class III compounds. Complexes [4a](3+) (R = H) and [4b](3+) (R = CO2Me) also exhibit strong electronic communication, and notwithstanding the large redox-asymmetry the visible metal-to-ligand charge-transfer absorption is assigned to originate from both metal centers. The potential of the first, ruthenium-based, reversible oxidation process is strongly negatively shifted. On the contrary, the second oxidation is irreversible and cyclometalated ligand-based. Upon one-electron oxidation, a weak and low-energy absorption arises.

Consequences of N,C,N '- and C,N,N '-coordination modes on electronic and photophysical properties of cyclometalated aryl ruthenium(II) complexes

The effects of isoelectronic replacement of a neutral nitrogen donor atom by an anionic carbon atom in terpyridine ruthenium(II) complexes on the electronic and photophysical properties of the resulting N,C,N'- and C,N,N'-cyclometalated aryl ruthenium(II) complexes were investigated. To this end, a series of complexes was prepared either with ligands containing exclusively nitrogen donor atoms, that is, [Ru(R-1-tpy)(R-2-tpy)](2+) (R-1, R-2 = H, CO2Et), or bearing either one N,C,N'- or C,N,N'-cyclometalated ligand and one tpy ligand, that is, [Ru(R-1-(NCN)-C-Lambda-N-Lambda)(R-2-tpy)](+) and [Ru(R-1-(CNN)-N-Lambda-N-Lambda)(R-2-tpy)](+), respectively. Single-crystal X-ray structure determinations showed that cyclometalation does not significantly alter the overall geometry of the complexes but does change the bond lengths around the ruthenium(II) center, especially the nitrogen-to-ruthenium bond length trans to the carbanion. Substitution of either of the ligands with electron-withdrawing ester functionalities fine-tuned the electronic properties and resulted in the presence of an IR probe. Using trends obtained from redox potentials, emission energies, IR spectroelectrochemical responses, and the character of the lowest unoccupied molecular orbitals from DFT studies, it is shown that the first reduction process and luminescence are associated with the ester-substituted C,N,N'-cyclometalated ligand in [Ru(EtO2C-(CNN)-N-Lambda-N-Lambda)(tpy)](+). Cyclometalation in an N,C,N'-bonding motif changed the energetic order of the ruthenium d(zx), d(yz), and d(xy) orbitals. The red-shifted absorption in the N,C,N'-cyclometalated complexes is assigned to MLCT transitions to the tpy ligand. The red shift observed upon introduction of the ester moiety is associated with an increase in intensity of low-energy transitions, rather than a red shift of the main transition. Cyclometalation in the C,N,N'-binding motif also red-shifts the absorption, but the corresponding transition is associated with both ligand types. Luminescence of the cyclometalated complexes is relatively independent of the mode of cyclometalation, obeying the energy gap law within each individual series.

A phosphorus analogue of Bis(eta(4)-cyclobutadiene)iron(0)

P makes it possible: The convenient oxidative synthesis of the 16-electron organophosphorus iron sandwich complex [Fe(4-P2C2tBu2)2] suggests that the elusive all-carbon complex [Fe(4-C4H4)2] is a viable synthetic target.

Regulation of the neural circuitry of emotion by compassion meditation: effects of meditative expertise

Recent brain imaging studies using functional magnetic resonance imaging (fMRI) have implicated insula and anterior cingulate cortices in the empathic response to another's pain. However, virtually nothing is known about the impact of the voluntary generation of compassion on this network. To investigate these questions we assessed brain activity using fMRI while novice and expert meditation practitioners generated a loving-kindness-compassion meditation state. To probe affective reactivity, we presented emotional and neutral sounds during the meditation and comparison periods. Our main hypothesis was that the concern for others cultivated during this form of meditation enhances affective processing, in particular in response to sounds of distress, and that this response to emotional sounds is modulated by the degree of meditation training. The presentation of the emotional sounds was associated with increased pupil diameter and activation of limbic regions (insula and cingulate cortices) during meditation (versus rest). During meditation, activation in insula was greater during presentation of negative sounds than positive or neutral sounds in expert than it was in novice meditators. The strength of activation in insula was also associated with self-reported intensity of the meditation for both groups. These results support the role of the limbic circuitry in emotion sharing. The comparison between meditation vs. rest states between experts and novices also showed increased activation in amygdala, right temporo-parietal junction (TPJ), and right posterior superior temporal sulcus (pSTS) in response to all sounds, suggesting, greater detection of the emotional sounds, and enhanced mentation in response to emotional human vocalizations for experts than novices during meditation. Together these data indicate that the mental expertise to cultivate positive emotion alters the activation of circuitries previously linked to empathy and theory of mind in response to emotional stimuli.