Periodically Grafted Amphiphilic Copolymers: Effects of Steric Crowding and Reversal of Amphiphilicity

Two series of periodically clickable polyesters were prepared; one of them carries alkylene segments along its backbone, whereas the other carries poly(ethylene glycol) (PEG) segments. These polyesters were clicked with either MPEG-350 azide or docosyl (C22) azide to yield periodically grafted amphiphilic copolymers (PGACs) carrying either flexible hydrophilic or crystallizable hydrophobic backbone segments. The immiscibility between hydrocarbon and PEG segments causes both of these systems to fold in either a zigzag or hairpin-like conformation; the hairpin-like conformation appears to be preferred when flexible PEG segments are present in the backbone. The folded chains further reorganize in the solid state to develop a lamellar morphology that permits the collocation of the PEG and hydrocarbon (HC) segments within alternate domains; evidence for the self-segregation was gained from DSC, SAXS, and AFM studies. SAXS studies revealed the formation of an extended lamellar structure, whereas AFM images showed uniform layered morphology with layer heights that matched reasonably well with the interlamellar spacing obtained from the SAXS study. Labeling One representative PGAC, carrying crystallizable long alkylene segments in the backbone and pendant PEG-350 side chains, with a small mole fraction of pyrene fluorophore permitted the examination of the conformational transition that occurs upon going from a good to a poor solvent; this single-chain folded conformation, we postulate, is the intermediate that organizes into the lamellar morphology.

Molecular structure of the discotic liquid crystalline phase of hexa-peri-hexabenzocoronene/oligothiophene hybrid and their charge transport properties

Using atomistic molecular dynamics simulation, we study the discotic columnar liquid crystalline (LC) phases formed by a new organic compound having hexa-peri-Hexabenzocoronene (HBC) core with six pendant oligothiophene units recently synthesized by Nan Hu et al. Adv. Mater. 26, 2066 (2014)]. This HBC core based LC phase was shown to have electric field responsive behavior and has important applications in organic electronics. Our simulation results confirm the hexagonal arrangement of columnar LC phase with a lattice spacing consistent with that obtained from small angle X-ray diffraction data. We have also calculated various positional and orientational correlation functions to characterize the ordering of the molecules in the columnar arrangement. The molecules in a column are arranged with an average twist of 25 degrees having an average inter-molecular separation of similar to 5 angstrom. Interestingly, we find an overall tilt angle of 43 degrees between the columnar axis and HBC core. We also simulate the charge transport through this columnar phase and report the numerical value of charge carrier mobility for this liquid crystal phase. The charge carrier mobility is strongly influenced by the twist angle and average spacing of the molecules in the column. (C) 2015 AIP Publishing LLC.

Iron(III) salicylates of dipicolylamine bases showing photo-induced anticancer activity and cytosolic localization

An iron(III) salicylate having a dipicolylamine base (andpa) with a photoactive anthracenyl moiety is prepared, characterized, and studied for its photo-induced anticancer activity and cellular localization in HeLa and MCF-7 cells. Its phenyl analogue is structurally characterized by X-ray crystallography. The complex has a ternary structure in which the dipicolylamine ligand and salicylic acid in dianionic form (sal) display respective tridentate and bidentate mode of coordination in Fe(sal)(phdpa)Cl] (1). Complex Fe(sal)(andpa)Cl] (2) having a pendant anthracenyl moiety shows significant photocytotoxicity in visible light (400-700 nm) giving IC50 values of 8.6 +/- 0.7 and 3.4 +/- 0.9 mu M in HeLa and MCF-7 cells, while being essentially nontoxic in the dark (IC50 > 100 mu M). The complex shows cytosolic localization in the cancer cells. Formation of hydroxyl radicals ((OH)-O-center dot) as the reactive oxygen species is evidenced from the pUC19 DNA photocleavage studies. (C) 2015 Elsevier Ltd. All rights reserved.

El mundo de las supersticiones y el paso de la hechicería a la brujomanía en Euskal-Herria (siglos XIII al XVI)

[ES]En este artículo se pretende dar una visión global, tanto en la exposición de los hechos como en la interpretación de los mismos, del mundo de la brujería (hechicería, adivinación, etc.) y de la superstición (curanderismo, exorcismo, conjuros, bendiciones)en el País Vasco y Navarra durante la Edad Media y primera Edad Moderna.

Développement des méthodes de stabilisation pour la conception des circuits hyperfréquences : application à l'optimisation d'un amplificateur de puissance spatial

209 p. : graf.

El control de la producción histórica sobre Gipuzkoa en el siglo XVII. Un instrumento de defensa del régimen foral

[ES] Este trabajo pretende conocer las causas que explican la actividad censora y recopiladora de la Provincia, durante el siglo XVII, en el campo de la producción histórica referente a Gipuzkoa.

El mito de Safo en el relato decadente

[FR] La femme homosexuelle, reflet d’un désir mythique hermaphrodite, est, pendant la fin du siècle une figure littéraire paradoxale et en même temps obsédante. Sapho est, comme la femme fatale, une des protagonistes de la fin-du-siècle qui répond à une misogynie récurrente dans l’imaginaire créateur. Il s’agit d’un désir artificiel, éros intangible (Péladan 1910: 74), contre nature, un idéal impossible: Sexe initial,sexe définitif, absolu de l’amour, absolu de la forme, sexe qui nies le sexe, sexe d’éternité! Los à toi, Androgyne! (Péladan 1910: 76). Sapho, figure archétypique, androgyne, constitue en définitive le symbole de l’abolition des sexes, de la confusion des genres, de la crise du couple traditionnel. Elle met en évidence la solitude, la peur et un désir inassouvi.

Los determinantes de la rentabilidad primaria de los bonos de titulización hipotecaria: la influencia de las estructuras multitramo

[ES] Este artículo analiza los determinantes de la rentabilidad primaria de los bonos de titulización hipotecaria (conocidos en la literatura como mortgage backed securities, o MBS) emitidos en España durante el periodo 1993-2011, periodo en el que el mercado español llegó a convertirse en el más importante de Europa continental. Los resultados obtenidos sobre el análisis de la población completa de MBS emitidos (262 tramos configurados sobre 94 fondos de titulización) indican que la estructuración multitramo de los MBS ha ayudado a reducir el riesgo percibido global de las emisiones de MBS, mediante la generación de mercados más completos y la reducción de los problemas derivados de la existencia de asimetrías informativas implícitas en el proceso de selección de los activos transmitidos por parte de la entidad cedente. Esta reducción del riesgo percibido ha tenido un efecto directo sobre la rentabilidad ofrecida por los bonos de titulización emitidos. Además, no se encuentran evidencias de que la emisión de MBS persiga la transmisión efectiva de riesgos, más bien al contrario. Las Entidades de crédito, por lo general, han retenido los tramos de primeras pérdidas, lo que ha contribuido a mantener en niveles muy bajos (por debajo de la rentabilidad de la deuda soberana) la rentabilidad ofrecida por los MBS. Precisamente, el escaso diferencial ofrecido por los bonos de titulización se debe a que los tramos retenidos no han ofrecido primas de rentabilidad ajustadas al riesgo inherente.

Bimetallic olefin polymerization catalysis : mechanisms and applications of proximal effects

This dissertation covers progress with bimetallic polymerization catalysts. The complexes we have designed were aimed at expanding the capabilities of homogeneous polymerization catalysts by taking advantage of multimetallic effects. Such effects were examined in group 4 and group 10 bimetallic complexes; proximity and steric repulsion were determined to be major factors in the effects observed.

Chapters 2 and 3 introduce the rigid p-terphenyl dinucleating framework utilized in most of this thesis. The permethylation of the central arene allows for the separation of syn and anti atropisomers of the terphenyl compounds. Kinetic studies were carried out to examine the isomerization of the dinucleating bis(salicylaldimine) ligand precursors. Metallation of the syn and anti bis(salicylaldimine)s using Ni(Me)2(tmeda) and excess pyridine afforded dinickel bisphenoxyiminato complexes with a methyl and a pyridyl ligand on each nickel. The syn and anti atropisomers of the dinickel complexes were structurally characterized and utilized in ethylene and ethylene/α-olefin polymerizations. Monometallic analogues were also synthesized and tested for polymerization activity. Ethylene polymerizations were performed in the presence of primary, secondary, and tertiary amines – additives that generally deactivate nickel polymerization catalysts. Inhibition of this deactivation was observed with the syn atropisomer of the bimetallic species, but not with the anti or monometallic analogues. A mechanism was proposed wherein steric repulsion of the substituents on proximal nickel centers disfavors simultaneous ligation of base to both of the metal centers. The bimetallic effect has been explored with respect to size and binding ability of the added base.

Chapter 4 presents the optimization of the bisphenoxyimine ligand synthesis and synthesis of syn and anti m-terphenyl analogues. Metallation with NiClMe(PMe₃)₂ yielded phosphine-ligated dinickel complexes, which have been structurally characterized. Ethylene/1-hexene copolymerizations in the presence of amines using Ni(COD)₂ as a phosphine scavenger showed significantly improved activity relative to the pyridine-ligated analogues. Incorporation of amino olefins in copolymerizations with ethylene was accomplished, and a mechanism was proposed based on proximal effects. Copolymerization trials with a variety of amino olefins and ethylene/1-hexene/amino olefin terpolymerizations were completed.

Early transition metal complexes based on the rigid p-terphenyl framework were designed with a variety of donor sets (Chapter 5 and Appendix B). Chapter 5 details the use of syn dizirconium di[amine bis(phenolate)] complexes for isoselective 1-hexene and propylene homopolymerizations. Ligand variation and monometallic complexes were studied to determine the origin of tacticity control. A mechanistic proposal was presented based on the symmetry at zirconium and the steric effects of the proximal metal center. Appendix B covers additional studies of bimetallic early transition metal complexes based on the p-terphenyl. Dititanium, dizirconium, and asymmetric complexes with bisphenoxyiminato ligands and derivatives thereof were targeted. Progress toward the synthesis of these complexes is described along with preliminary polymerization data. 1-hexene/diene copolymerizations and attempted polymerizations in the presence of ethers and esters with the syn dizirconium di[amine bis(phenolate)] complexes demonstrate the potential for further applications of this system in catalysis.

Appendix A includes work toward palladium catalysts for insertion polymerization of polar monomers. These complexes were based on dioxime and diimine frameworks with the intent of binding Lewis acidic metals at the oxime oxygens, at pendant phenolic donors, or at pendant aminediol moieties. The synthesis and structural characterization of a number of palladium and Lewis acid complexes is presented. Due to the instability of the desired species, efforts toward isolation of the desired complexes proved unsuccessful, though preliminary ethylene/methyl acrylate copolymerizations using in situ activation of the palladium species were attempted.

Synthesis, Oxidation and Photophysics of Perfluoroborated Tetrakis(pyrophosphito)diplatinate (II) and Density Functional Theory (DFT) Study of Electrochemical CO2 Reduction by Mn Catalysts

In the first part of this thesis (Chapters I and II), the synthesis, characterization, reactivity and photophysics of per(difluoroborated) tetrakis(pyrophosphito)diplatinate(II) (Pt(POPBF₂)) are discussed. Pt(POP-BF₂) was obtained by reaction of [Pt₂(POP)₄]^4- with neat boron trifluoride diethyl etherate (BF₃·Et₂O). While Pt(POP-BF₂) and [Pt₂(POP)₄]^4- have similar structures and absorption spectra, they differ in significant ways. Firstly, as discussed in Chapter I, the former is less susceptible to oxidation, as evidenced by the reversibility of its oxidation by I2. Secondly, while the first excited triplet states (T₁) of both Pt(POP-BF₂) and [Pt₂(POP)₄]^4- exhibit long lifetimes (ca. 0.01 ms at room temperature) and substantial zero-field splitting (40 cm^-1), Pt(POP-BF₂) also has a remarkably long-lived (1.6 ns at room temperature) singlet excited state (S₁), indicating slow intersystem crossing (ISC). Fluorescence lifetime and quantum yield (QY) of Pt(POP-BF₂) were measured over a range of temperatures, providing insight into the slow ISC process. The remarkable spectroscopic and photophysical properties of Pt(POP-BF₂), both in solution and as a microcrystalline powder, form the theme of Chapter II.

In the second part of the thesis (Chapters III and IV), the electrochemical reduction of CO₂ to CO by [(L)Mn(CO)₃]^- catalysts is investigated using density functional theory (DFT). As discussed in Chapter III, the turnover frequency (TOF)-limiting step is the dehydroxylation of [(bpy)Mn(CO)₃(CO₂H)]^0/- (bpy = bipyridine) by trifluoroethanol (TFEH) to form [(bpy)Mn(CO)₄]^+/0. Because the dehydroxylation of [(bpy)Mn(CO)₃(CO₂H)]^- is faster, maximum TOF (TOF_max) is achieved at potentials sufficient to completely reduce [(bpy)Mn(CO)₃(CO₂H)]⁰ to [(bpy)Mn(CO)₃(CO₂H)]^-. Substitution of bipyridine with bipyrimidine reduces the overpotential needed, but at the expense of TOF_max. In Chapter IV, the decoration of the bipyrimidine ligand with a pendant alcohol is discussed as a strategy to increase CO₂ reduction activity. Our calculations predict that the pendant alcohol acts in concert with an external TFEH molecule, the latter acidifying the former, resulting in a ~ 80,000-fold improvement in the rate of TOF-limiting dehydroxylation of [(L)Mn(CO)₃(CO₂H)]^-.

An interesting strategy for the co-upgrading of light olefins and alkanes into heavier alkanes is the subject of Appendix B. The proposed scheme involves dimerization of the light olefin, operating in tandem with transfer hydrogenation between the olefin dimer and the light alkane. The work presented therein involved a Ta olefin dimerization catalyst and a silica-supported Ir transfer hydrogenation catalyst. Olefin dimer was formed under reaction conditions; however, this did not undergo transfer hydrogenation with the light alkane. A significant challenge is that the Ta catalyst selectively produces highly branched dimers, which are unable to undergo transfer hydrogenation.

Dependência de álcool e outras drogas: debate conceitual, políticas públicas e a inserção do serviço social nessa área

Este estudo buscou identificar a inserção do Serviço Social na intervenção profissional junto à dependência de álcool e outras drogas na década de 1980, no Rio de Janeiro, a partir do debate conceitual acerca dessa temática e da análise das políticas públicas formuladas pelo Estado brasileiro para o seu enfrentamento. Caracteriza-se como uma pesquisa de natureza exploratória face à parca existência de produções científicas no Serviço Social sobre tal questão. Assim, constituindo-se como uma contribuição em termos de subsídios à ação profissional dos assistentes sociais. Os dados coletados junto aos representantes e assistentes sociais de instituições em funcionamento na década de 1980 permitiram delinear um perfil sobre a implantação do Serviço Social na intervenção profissional junto a essa problemática. Inicialmente, as entidades sem fins lucrativos e os programas de dependência química de empresa foram os principais espaços ocupados pelos profissionais de Serviço Social, havendo uma inexpressiva presença nos órgãos estatais. A partir dos anos noventa, com as políticas públicas de atenção ao consumo de drogas, amplia-se o número de assistentes sociais com atuação nessa área, cabendo, portanto, ao Serviço Social contribuir mais intensamente com estudos científicos, visando melhor instrumentalizá-los de forma teórico-metodológica e técnico-operativa.

Design, Synthesis, and Study of Novel Platforms for Iron-N2 Chemistry and Photoinduced, Copper-mediated C-N Bond Formation

Several new ligand platforms designed to support iron dinitrogen chemistry have been developed. First, we report Fe complexes of a tris(phosphino)alkyl (CP^iPr₃) ligand featuring an axial carbon donor intended to conceptually model the interstitial carbide atom of the nitrogenase iron-molybdenum cofactor (FeMoco). It is established that in this scaffold, the iron center binds dinitrogen trans to the C_alkyl anchor in three structurally characterized oxidation states. Fe-C_alkyl lengthening is observed upon reduction, reflective of significant ionic character in the Fe-C_alkyl interaction. The anionic (CP^iPr₃)FeN₂^- species can be functionalized by a silyl electrophile to generate (CP^iPr₃)Fe-N₂SiR₃. This species also functions as a modest catalyst for the reduction of N₂ to NH₃. Next, we introduce a new binucleating ligand scaffold that supports an Fe(μ-SAr)Fe diiron subunit that coordinates dinitrogen (N₂-Fe(μ-SAr)Fe-N₂) across at least three oxidation states (Fe^IIFe^II, Fe^IIFe^I, and Fe^IFe^I). Despite the sulfur-rich coordination environment of iron in FeMoco, synthetic examples of transition metal model complexes that bind N₂ and also feature sulfur donor ligands remain scarce; these complexes thus represent an unusual series of low-valent diiron complexes featuring thiolate and dinitrogen ligands. The (N₂-Fe(μ-SAr)Fe-N₂) system undergoes reduction of the bound N₂ to produce NH₃ (~50% yield) and can efficiently catalyze the disproportionation of N₂H₄ to NH₃ and N₂. The present scaffold also supports dinitrogen binding concomitant with hydride as a co-ligand. Next, inspired by the importance of secondary-sphere interactions in many metalloenzymes, we present complexes of iron in two new ligand scaffolds ([SiP^NMe₃] and [SiP^iPr₂P^NMe]) that incorporate hydrogen-bond acceptors (tertiary amines) which engage in interactions with nitrogenous substrates bound to the iron center (NH₃ and N₂H₄). Cation binding is also facilitated in anionic Fe(0)-N₂ complexes. While Fe-N₂ complexes of a related ligand ([SiP^iPr₃]) lacking hydrogen-bond acceptors produce a substantial amount of ammonia when treated with acid and reductant, the presence of the pendant amines instead facilitates the formation of metal hydride species.

Additionally, we present the development and mechanistic study of copper-mediated and copper-catalyzed photoinduced C-N bond forming reactions. Irradiation of a copper-amido complex, ((m-tol)₃P)₂Cu(carbazolide), in the presence of aryl halides furnishes N-phenylcarbazole under mild conditions. The mechanism likely proceeds via single-electron transfer from an excited state of the copper complex to the aryl halide, generating an aryl radical. An array of experimental data are consistent with a radical intermediate, including a cyclization/stereochemical investigation and a reactivity study, providing the first substantial experimental support for the viability of a radical pathway for Ullmann C-N bond formation. The copper complex can also be used as a precatalyst for Ullmann C-N couplings. We also disclose further study of catalytic C_alkyl-N couplings using a CuI precatalyst, and discuss the likely role of [Cu(carbazolide)₂]^- and [Cu(carbazolide)₃]^- species as intermediates in these reactions.

Finally, we report a series of four-coordinate, pseudotetrahedral P₃Fe^II-X complexes supported by tris(phosphine)borate ([PhBP₃Fe^R]^-) and phosphiniminato X-type ligands (-N=PR'₃) that in combination tune the spin-crossover behavior of the system. Low-coordinate transition metal complexes such as these that undergo reversible spin-crossover remain rare, and the spin equilibria of these systems have been studied in detail by a suite of spectroscopic techniques.

La Tipología Analítica aplicada al estudio de materiales líticos de época histórica

Homenaje a Georges Laplace, realizado en Vitoria-Gasteiz el 13, 14 y 15 de noviembre de 2012. Edición a cargo de Aitor Calvo, Aitor Sánchez, Maite García-Rojas y Mónica Alonso-Eguíluz.

Entre o exotismo e o progresso: a construção do Brasil pela fotografia de Marc Ferrez

Marc Ferrez (1843-1923), filho de franceses nascido no Brasil, exerceu por mais de cinqüenta anos a atividade de fotógrafo e comerciante de materiais afins. Para o presente estudo foi selecionada da imensa produção de Ferrez uma série de fotografias que pudesse abranger a diversidade de temas, regiões e períodos nos quais o fotógrafo atuou. A partir desta seleção foi estudada a contribuição da fotografia para a formação de uma identidade nacional brasileira, levando-se em conta os meios de circulação e recepção das fotografias e suas diversas formas de reprodução. Neste circuito visual travou-se um combate de imagens: de um lado o público que encomendava trabalhos de documentação fotográfica procurava apresentar uma nação n a marcha do progresso, de outro lado a comercialização de fotografias ou reproduções delas com grande aceitação em um mercado de imagens trazia especialmente temas como a natureza ou os tipos humanos exóticos. Na fotografia de Ferrez podemos apreender imagens de um país cujas elites sonhavam em mostrar civilizado, mas onde, a o mesmo tempo, predominava o elemento natural exuberante e os tipos exóticos. Elementos e temas essenciais para se discutir pertencimento, imaginário, identidade, enfim, para avaliar as construções da nação brasileira.

O ethos discursivo nas redações de vestibular

O presente trabalho tem o objetivo de estudar o ethos constituído nas redações argumentativas de vestibular, verificando, a partir das escolhas linguísticas dos estudantes, a representação discursiva que eles constroem de si para defender sua tese. O corpus se constitui de cem redações, que integraram a segunda fase dos vestibulares 2006 e 2007, da Universidade do Estado do Rio de Janeiro. Para alcançarmos essa imagem coletiva, utilizamos, prioritariamente, a noção de ethos discursivo proposta por Dominique Maingueneau. Optamos por realizar uma análise quantitativa e qualitativa do corpus. A primeira abordagem nos proporcionou uma visão panorâmica das redações ao passo que a segunda revelou os casos mais representativos de cada fenômeno observado. No decorrer da análise, verificamos nas redações práticas que incidiam no risco de configurar ethé indesejados e mesmo censuráveis, causando prejuízo à argumentação dos vestibulandos. Por essa razão, finalizamos a pesquisa com sugestões de atividades didáticas, que focam o aprimoramento das habilidades de escrita e leitura, na tentativa de apresentar uma contribuição ao processo de ensino-aprendizagem de Produção Textual