Le rêve, le sommeil et la mort dans “Nocturne Vulgaire” de Rimbaud

A fin de recrear paródicamente el espacio romántico de la ensoñación y de la noche, “Nocturne Vulgaire” instaura una lógica onírica que manifiesta, indirectamente, la relación traumática entre muerte y sueño

Significado y dimensiones actuales de los tumores estromales gastro-intestinales (GIST)

Desde que en 1983 se utilizara por primera vez el término GISTs hasta hoy, se ha profundizado mucho en su conocimiento, comentándose aquí tres aspectos de actualidad: -Heterogenidad molecular: hasta hace poco se consideraba que los GISTs podían presentar dos tipos de mutaciones excluyentes, en KIT (75%) y PDGFR (10%). Hoy sabemos que existen también mutaciones en SDH, en KRAS/BRAF y en NF1, además de casos con fusiones génicas (s.t. de FGFR-1) y mutaciones puntuales en MAX, BCOR y APe. -Origen de los GISTs y progresión tumoral: Hirota et al (1998) señaló su origen en las células intersticiales de Cajal, aunque las que tienen potencial oncogénico son las sensibles a la transformación por CKIT y expresan el factor de transformación ETV1, cuya trasncripción se regula por KIT activado. Además, en la promoción tumoral es necesario la colaboración de otros factores. El acontecimiento inicial es la activación del oncogen KIT en el subtipo de CIC-ETV1 que conduce solo a una hiperplasia; para que progrese el crecimiento son necesarios cambios adicionales como deleciones del 14q, o del 22q. En la evolución se presentan otras deleciones adicionales en los genes lp,9p 15q Y Xplp 9p y 15q. Entre los genes implicados están MAX que interactúa con el gen MYC y causa desregulación de la expresión de p16 asociándose a progresión a tumor de riesgo intermedio y alto. Otro gen es lNll que regula negativamente el celular. En el segmento del XP está la distrofina que se asocia en el 90% con el desarrollo de metástasis. -GISTs de tipo pediátrico: se caracterizan por malfuncionamiento del complejo SDH y tienen características bioevolutivas diferentes. Afectan a jóvenes, sobre todo mujeres, en estómago, multifocales, con frecuentes metástasis linfáticas, exhiben mutaciones en SDH, expresan CD117 y DOGl, tienen un curso clínico indolente y no responden al imatinib. La mayoría de los casos se asociación a dos síndromes definidos: triada de Carney y síndrome de Carney-Stratakis.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

La metamorfosis lingüística de "Bottom"

"Bottom" (Arthur Rimbaud, Illuminations) narra una metamorfosis. Una de las convenciones del motivo es la enunciación de la zona intermedia donde acontece el cambio, causado por figuras supranaturales o por intervenciones externas. Pero "Bottom" presenta resultados e imágenes inmotivadas que se superponen como en sueños. ¿Cómo logra transmitir procesos sin nunca describir el cambio en sí o entregar sus causas? Una respuesta posible está en las unidades léxicas que constituyen el texto: la transformación sucede en valores de lengua precisos que llevan en sus núcleos sémicos el resultado del cambio sin hacer referencia al proceso ni a sus causas. Todo proceso de traducción deberá contemplar este sistema cerrado que se manifiesta mediante mecanismos como la solidaridad léxica, la implicación sintagmática, la alternancia de verbos de movimiento y una estructura retórica que desarrolla, en toda la prosa, la premisa expuesta en la primera frase ('la réalité étant trop épineuse pour mon grand caractère'). "Bottom" (Arthur Rimbaud, Illuminations) is the story of a metamorphosis. One of thge conventions of the genre is the description of the transitional space where change is operated either by supernatural figures or by the intervention of exterior forces. But "Bottom" presents only results and unmotivated images which evolve as in dreams. How does then “Bottom”, a story of transformations, manage to convey processes without ever describing change or disclosing its causes? A possible answer can be found in the lexical units whic build the text: transformation occurs in particular language values which carry in their semic nuecleus the results of change without actually referring to the process or its causes. Any translation process should take in account this closed system involving textual mecanism such as lexical solidarity, syntagmatic implication, alternance of verbs of motion and a rhetorical structure which develops throughout the text the premiss exposes in the first sentence ('la réalité étant trop épineuse pour mon grand caractère')

Mechanism of Alkyl Migration in Diorganomagnesium 2,6-Bis(imino)pyridine Complexes: Formation of Grignard-Type Complexes with Square-Planar Mg(II) Centers

Dialkylmagnesium compounds [MgR2L2] (R = n-Bu, L = none or R = Bn, L = THF) react with 2,6-bis(imino)pyridines (BIP) to afford different types of Mg(II) alkyl complexes, depending on the nature of R. For R = n-Bu, thermally stable products resulting from selective alkyl transfer to the pyridine nitrogen (N1) atom are obtained. However, NMR studies showed that the reaction of [Mg(Bn)2THF2] with iPrBIP at −65 °C leads to a thermally unstable product arising from benzyl migration to position C2 in the pyridine ring. Above +5 °C, this compound rearranges, cleanly yielding a mixture of two isomeric complexes, in which the benzyl group has migrated to positions C3 or C4 of the central ring, respectively. Similar isomeric mixtures were obtained when [Mg(Bn)2THF2] was reacted with iPrBIP or MesBIP at room temperature. Such mixtures are thermally stable below 80 °C, but at this temperature, the 3-benzyl isomer converts into the thermodynamically favored 4-benzyl product, albeit not quantitatively. An alternate route was devised for the selective syntheses of the latter type of compounds. The X-ray diffraction structure of one of them provided an unusual example of a square-planar alkylmagnesium(II) center.Ministerio de Economía e Innovación CTQ2015-68978-

Oxygen-Induced Dimerization of Alkyl-Manganese(II) 2,6-Bisiminopyridine Complexes: Selective Synthesis of a New Ditopic NNN-Pincer Ligand

The outcome of the reaction of manganese(II) dialkyls with 2,6-bisiminopyridine (BIP) ligands is dramatically altered by the presence of very small amounts of oxygen (< 0.5 mol %), leading to binuclear species. These arise from the dimerization of the initial product, a Mn(II) 4-alkyl-2,6-bisiminodihydropyridinate alkyl complex. Cleavage of the binuclear Mn products with methanol affords the free dimeric bases, which can be regarded as a special type of ditopic NNN pincer ligand with an unusual tricyclic framework. The coordinative ability of the new ligands has been probed with the syntheses of Zn and Pd organometallic derivativesMinisterio de Economía e Innovación TQ2015- 68978-

Migratory insertion reactions of nickel and palladium σ-alkyl complexes with a phosphinito-imine ligand†‡

Ligand exchange reactions have been used for the synthesis of metallacyclic complexes of Ni and Pd of the type [M[upper bond 1 start](CH2CMe2-o-C6[upper bond 1 end]H4)(P–N)], where P–N is the phosphinito-imine ligand P(iPr)2OC(Me)[double bond, length as m-dash]N(2,6-C6H3(iPr)2. The protic acid [H(OEt2)(BAr′4)] (Ar′ = 3,5-C6H3(CF3)2) selectively cleaves one of the two σ metal–carbon bonds, affording cationic monoalkyl complexes. Nickel monoalkyls stabilized with Et2O or MeCN ligands are thermally unstable and spontaneously undergo a decomposition process that ultimately leads to the breakdown of the phosphinito-imine ligand. In contrast, cationic alkylpalladium derivatives are thermally very stable, allowing the isolation of a formally unsaturated monoalkyl complex stabilized by an intramolecular π-arene interaction. Although monoalkynickel and -palladium phosphinito-imine derivatives are inactive as ethylene polymerization or copolymerization catalysts, they readily experience migratory insertion reactions. A palladium chelate arising from the successive insertion of CO and ethylene has been isolated and characterized.Ministerio de Ciencia y Tecnología CTQ2009-11721Junta de Andalucía P09-FQM507

Electron-rich metal complexes for C02 and CS2 incorporation

The dihapto coordination of two molecules of carbon dioxide to a square-planar MoP2(P-P) fragment (P=monodentate-, P-P=bidentate phosphi- ne ligands) can occur in several ways giving rise to different conformers. Compounds of this type have been prepared and their spectroscopic proper- ties investigated by variable temperature 'H and 31P NMR studies. The for- mation of ethylene complexes related to Mo(C2H4)2(PMe3)4, 6, and the study of their reactivity towards carbon dioxide and carbon disulphide is also described. In particular, compound 6 induces a head-to-tail dimerization of carbon disulphide with formation of a Mo(II)-C$4 linkage, which, in the presence of carbon monoxide, undergoes a symmetric, oxidative rupture, which produces a Mo(0) complex and two molecules of carbon disulphide. The insertion reactions of carbon dioxide and other unsaturated molecules into the nickel-carbon bonds of the nickelacyclopentene complexes 9 have been investigated and different organic products isolated by means of simple or sequential insertion reactions.Ministerio de Educación y CienciaAgencia Nacional de Evaluación y Prospectiv

Well-defined alkylpalladium complexes with pyridine-carboxylate ligands as catalysts for the aerobic oxidation of alcohols

Neophylpalladium complexes of the type [Pd(CH(2)CMe(2)Ph)(N-O)(L)], where N-O is picolinate or a related bidentate, monoanionic ligand (6-methylpyridine-2-carboxylate, quinoline-2-carboxylate, 2-pyridylacetate or pyridine-2-sulfonate) and L is pyridine or a pyridine derivative, efficiently catalyze the oxidation of a range of aliphatic, benzylic and allylic alcohols with oxygen, without requiring any additives. A versatile method is described which allows the synthesis of the above-mentioned complexes with a minimum synthetic effort from readily available materials. Comparison of the rates of oxidation of 1-phenylethanol with different catalysts reveals the influence of the structure of the bidentate N-O chelate and the monodentate ligand L on the catalytic performance of these complexesGobierno de España CTQ2009-11721Junta de Andalucía FQM627

Protonolysis of Fe-C bonds of a diiminopyridineiron(II) dialkyl complex by acids of different strengths: Influence of monoanionic ligands on the spectroscopic properties of diiminopyiridine-FeY2 complexes

The reaction of the dialkyliron complex [Fe(CH2SiMe 3)2(MesBIP)] (MesBIP = 2,6-bis((N-mesityl)acetimidoyl)pyridine) with protic acids (HY) of different strengths (Y = C6F5O, CF3CO2, Cl, CF3SO3) invariably leads to the cleavage of both Fe-C bonds, independent of the Fe/HY ratio used (either 1:2 or 1:1), affording the corresponding complexes [FeY2(MesBIP)]. Relevant spectroscopic features of these compounds, such as paramagnetic 1H NMR shifts and UV-Vis absorption bands, exhibit a marked dependence on the nature of YGobierno de España CTQ2012-30962Junta de Andalucía FQM507