Constraints on Be-10 and Ca-41 distribution in the early solar system from Al-26 and Be-10 studies of Efremovka CAIs

Three refractory coarse grained CAIs from the Efremovka CV3 chondrite, one (E65) previously shown to have formed with live Ca-41, were studied by ion microprobe for their Al-26-Mg-26 and Be-10-B-10 systematic in order to better understand the origin of Be-10. The high precision Al-Mg data and the inferred Al-26/Al-27 values attest that the precursors of the three CAIs evolved in the solar nebula over a period of few hundred thousand years before last melting-crystallization events. The initial Be-10/Be-9 ratios and delta B-10 values defined by the Be-10 isochrons for the three Efremovka CAIs are similar within errors. The CAI Be-10 abundance in published data underscores the large range for initial Be-10/Be-9 ratios. This is contrary to the relatively small range of Al-26/Al-27 variations in CAIs around the canonical ratio. Two models that could explain the origin of this large Be-10/Be-9 range are assessed from the collateral variations predicted for the initial delta B-10 values: (i) closed system decay of Be-10 from a ``canonical'' Be-10/Be-9 ratio and (ii) formation of CAIs from a mixture of solid precursors and nebula gas irradiated during up to a few hundred thousand years. The second scenario is shown to be the most consistent with the data. This shows that the major fraction of Be-10 in CAIs was produced by irradiation of refractory grains, while contributions of galactic cosmic rays trapping and early solar wind irradiation are less dominant. The case for Be-10 production by solar cosmic rays irradiation of solid refractory precursors poses a conundrum for Ca-41 because the latter is easily produced by irradiation and should be more abundant than what is observed in CAIs. Be-10 production by irradiation from solar energetic particles requires high Ca-41 abundance in early solar system, however, this is not observed in CAIs. (C) 2013 Elsevier B.V. All rights reserved.

Component Selection in the Self-Assembly of Palladium(II) Nanocages and Cage-to-Cage Transformations

Dynamic supramolecular systems involving a tetratopic palladium(II) acceptor and three different pyridine-and imidazole-based donors have been used for self-selection by a synergistic effect of morphological information and coordination ability of ligands through specific coordination interactions. Three different cages were first synthesized by two-component self-assembly of individual donor and acceptor. When all four components were allowed to interact in a reaction mixture, only one out of three cages was isolated. The preferential binding affinity towards a particular partner was also established by transforming a non-preferred cage into a preferred cage by interaction with the appropriate ligand. Computational studies further supported the fact that coordination interaction of imidazole moiety to Pd-II is enthalpically more preferred compared to pyridine, which drives the selection process. Analysis of crystal packing of both complexes indicated the presence of strong hydrogen bonds between nitrate and water molecules and also H-bonded 3D networks of water. Both complexes exhibit promising proton conductivity (10(-5) to ca. 10(-3) Scm(-1)) at ambient temperature under a relative humidity of circa 98% with low activation energy.

Relaxor ferroelectricity and electric-field-driven structural transformation in the giant lead-free piezoelectric (Ba,Ca)(Ti, Zr)O-3

There is great interest in lead-free (Ba0.85Ca0.15)(Ti0.90Zr0.10)O-3 (15/10BCTZ) because of its exceptionally large piezoelectric response Liu and Ren, Phys. Rev. Lett. 103, 257602 (2009)]. In this paper, we have analyzed the nature of: (i) crystallographic phase coexistence at room temperature, (ii) temperature-and field-induced phase transformation to throw light on the atomistic mechanisms associated with the large piezoelectric response of this system. A detailed temperature-dependent dielectric and lattice thermal expansion study proved that the system exhibits a weak dielectric relaxation, characteristic of a relaxor ferroelectric material on the verge of exhibiting a normal ferroelectric-paraelectric transformation. Careful structural analysis revealed that a ferroelectric state at room temperature is composed of three phase coexistences, tetragonal (P4mm)+ orthorhombic (Amm2) + rhombohedral (R3m). We also demonstrate that the giant piezoresponse is associated with a significant fraction of the tetragonal phase transforming to rhombohedral. It is argued that the polar nanoregions associated with relaxor ferroelectricity amplify the piezoresponse by providing an additional degree of intrinsic structural inhomogeneity to the system.

Evaluación de semilla sexual hibrida de papa (Solanum tuberosum L.) provenientes del Centro Internacional de la Papa e India en la zona de Miraflor, Esteli

Con el objetivo de seleccionar progenies promisorias de semilla sexual de papa, procedentes del CIP (11) y Programa de la India (3) se estableció este ensayo el 21 de septiembre de 1994, utilizando un diseño de Bloques Completos al Azar (BCA) con cuatro repeticiones, en la estación experimental del Instituto Nicaragüense de Tecnología Agropecuaria (INTA-RB-3), ubicada a 1 350 msnm, humedad relativa del 91 por ciento, temperatura promedio mínima 15 °C/máx 26 °C, cuyos suelos son de textura franca bien drenada, medianamente profundo a profundo, con una precipitación durante el ensayo de 622 mm. Los resultados obtenidos muestran que todas las progenies híbridas enviadas por el CIP mostraron buena velocidad de emergencia en especial SERRANA x LT-7, con respecto a los lubridos de la India. En general el porcentaje de sobrevivencia fue mayor del 80 por ciento para la mayoría de las progenies el cual es un índice aceptable, a excepción de 104.12 LB x TS-4.En la altura final de la planta no hubieron diferencias significativas entre híbridos, solo fueron superiores a KATADIN x TS-10. En cuanto al rendimiento, la progenie HPS­ II/67 mostró ser superior a las demás con 6.2 kg/m2. El número total de tubérculos por metro cuadrado {740) y tubérculos por planta (7) fue superior en la progenie TS-6 x TPS-67. Las progenies de ambos programas mostraron rendimientos por metro cuadrado de más del 50 por ciento con tubérculos mayores de 5 gramos. No se presentó incidencia de virus para ambas progenies, las tres progenies provenientes del Programa de la India presentaron mayor resistencia a tizón tardío (Phytophthora infestans, Mont. D.bary).

El Concilio Vaticano II : remembranza y actualización

Resumen: Retomando la propuesta de su libro del año 2002, Vaticano II: Remembranza y Actualización y poniendo la mirada sobre el tema del Congreso del Centenario, que es abordar la cuestión del Concilio desde la memoria, el presente y las perspectivas que se abren para el futuro de la Iglesia, el profesor Madrigal nos propone en esta conferencia un ejercicio de memoria, un intento de respuesta a los temas que se deben actualizar y, a la vez, una mirada sobre el desafío a la pregunta del papa Francisco “¿cómo seguir adelante?”. En cuatro momentos desplegará esas cuestiones: 1) la realidad teológica de la institución conciliar; 2) una sistematización o lectura esencial de la doctrina conciliar; 3) el significado histórico del Vaticano II como movimiento de renovación; 4) líneas de actualización para un relanzamiento de la recepción del Vaticano II

Teología, 1965, Tomo II/2 nº 5 (número completo)

Los pobres en la Iglesia / Norman Horacio Pipo -- La ordenación final del hombre a la gloria en el comentario a las Sentencias de Santo Tomás de Aquino / Juan C De Zan -- Exposición de la doctrina de la fe en el Nuevo Mundo / Eduardo Pérez Bravo -- Boletín de teología de la historia / Pedro Geltman -- Se suprime en Buenos Aires (1824) el nombre del Papa en la liturgia / Américo Tonda -- Crónica de la Facultad -- Índice del Tomo II (1964)

Escritura y tradición : Karl Rahner en el “primer conflicto doctrinal” del Vaticano II

Resumen: En 2012 se cumplen 50 años del inicio del Concilio Vaticano II, inaugurado por el Papa Juan XXIII el 11 de octubre de 1962. Es un dato reconocido el importante papel que desarrollaron muchos teólogos a lo largo de los diversos debates conciliares. Entre ellos destaca la figura de K. Rahner. Su principal contribución se dirigió a los asuntos eclesiológicos. Menos conocido es su aporte a los debates que, iniciados en octubre de 1962, conducirían, recién en 1965, a la aprobación de la Constitución Dei Verbum. Luego de una breve introducción, me detengo, en primer lugar, en el informe que Rahner preparó en noviembre de 1962 en contra del Esquema preparatorio, De fontibus revelationis. En un segundo momento, describo otro texto, el llamado “Esquema Rahner – Ratzinger”, elaborado en la misma época, pensado como un texto alternativo al oficial. En tercer lugar, destaco algunas ideas centrales de una conferencia de Rahner de 1963, titulada “Escritura y Tradición”. Finalmente, analizo el número noveno de Dei Verbum que, como se advertirá, muestra que las posiciones bíblico-sistemáticas de Rahner se direccionaban en el sentido de la llamada mayoría conciliar.

El Vaticano II : intención, recepción, futuro

Resumen: En esta presentación, escrita para el Congreso del centenario de la Facultad de Teología, el autor, a partir de recuerdos personales, se refiere al contexto histórico de grandes transformaciones en que tiene lugar el Concilio Vaticano II, y el triunfo de la renovación inspirada en las fuentes y reflejada en los documentos conciliares. La recepción de estos resultados en el posconcilio fue difícil: en Latinoamérica, por las discusiones en torno a la teología de la liberación, y en Europa por el enfrentamiento con diferentes expresiones de la modernidad, el marxismo y el individualismo liberal. Desde los años ’80 se acentúan los debates sobre la interpretación del Concilio, con fuertes tendencias dirigidas a neutralizar su implementación. El Papa Francisco afronta hoy este desafío proponiendo un camino de radicalidad evangélica, centrada en la misericordia y la opción preferencial por los pobres

Crystal structure and phase transition studies in perovskite-type oxides using powder-diffraction techniques and symmetry-mode analysis : SrLnMRuO6 (Ln=La,Pr,Nd; M=Zn,Co,Mg,Ni,Fe) and ALn2CuTi2O9 (A=Ca,Ba; Ln=La,Pr,Nd,Sm)

La tesis se ha centrado en la síntesis y caracterización estructural de materiales tipo perovskita: SrLnMRuO6 (Ln=La,Pr,Nd; M=Zn,Co,Mg,Ni,Fe) y ALn2CuTi2O9 (A=Ca,Ba; Ln=La,Pr,Nd,Sm). El estudio de las estructuras de los materiales se ha realizado mediante el análisis de los patrones de difracción en polvo de rayos-X, sincrotrón y/o neutrones. En el refinamiento por el método de Rietveld de las estructuras se han sustituido las coordenadas atómicas (el método más común), por coordenadas colectivas: las amplitudes de los modos que describen la distorsión de la fase prototipo. Los resultados generales para la serie SrLnMRuO6 (Ln=La,Pr,Nd; M=Zn,Co,Mg,Ni) a temperatura ambiente se ha recogido en un diagrama en el que se han indicado las amplitudes de los modos que transforman de acuerdo a las irreps en función del factor de tolerancia, ya que todos ellos cristalizan en la misma fase monoclínica (P21/n); y a temperaturas altas se ha construido un diagrama de fase. Los materiales SrLnFeRuO6 ( Ln=La,Pr,Nd) y CaLn2CuTi2O9 cristalizan en la fase ortorrómbica Pbnm a temperatura ambiente; mientras que BaLn2CuTi2O9 tienen una estructura más simétrica, I4/mcm. A altas temperaturas se han identificado las transiciones de fase inducidas por el cambio de temperatura.A temperaturas bajas se han analizado las estructuras magnéticas de algunos de los compuestos mediante difracción de neutrones.

Análisis dieléctrico del compuesto La(1-x)Ca(x)MnO3 [x=0.2]

Lan honen helburua La1-x Cax MnO3 [x ~ 0.2] (perovskiten familiakoa) laginaren azterketan oinarritzen da. "High resolution dielectric analyzer" tresnari esker permitibitate dielektrikoa neurtuko da eta honen bitartez erresistentzia eta eroankortasun elektrikoa. Azterketa hau [10-2, 107] Hz maiztasun-tarte batean eta tenperatura desberdinetan (150K, 170K, 190K, 210K, 230K, 300K) burutuko da, ondoren materialak magnitude hauen bariazioekiko duen erantzuna aztertuz.

Oceanographic observations in the Gulf of Guayaquil, 1962-1964. Part II. Biological, chemical and physical.

ENGLISH: During 1961 the government of Ecuador, with the financial assistance of the Special Fund of the United Nations and the technical assistance of FAO experts, initiated an extensive program of fisheries research centered in a fisheries institute established in Guayaquil. In cooperation with this program, and in connection with Ecuador's adherence in 1961 to the Convention for the Establishment of an Inter-American Tropical Tuna Commission, a two-and-a-half year investigation of the ecology of the Gulf of Guayaquil and adjacent waters was started by the Inter-American Tropical Tuna Commission. SPANISH: Durante 1961 el gobierno ecuatoriano con el apoyo financiero del Fondo Especial de las Naciones Unidas y la ayuda técnica de los expertos de la FAO, inició un programa extensivo de investigación pesquera, centralizado en el instituto pesquero establecido en Guayaquil. En cooperación con este programa y en conexión a la afiliaci6n del Ecuador a la Convención, en 1961, para el establecimiento de una Comisión Interamericana del Atún Tropical, Cue iniciada por la Comisión una investigación de dos aftos y medio sobre la ecología del Golfo de Guayaquil y de las aguas adyacentes. (PDF contains 501 pages.)

Brain type II calcium and calmodulin-dependent protein kinase: characterization of a brain-region specific isozyme and regulation by autophosphorylation

A variety of molecular approaches have been used to investigate the structural and enzymatic properties of rat brain type ll Ca^(2+) and calmodulin-dependent protein kinase (type ll CaM kinase). This thesis describes the isolation and biochemical characterization of a brain-region specific isozyme of the kinase and also the regulation the kinase activity by autophosphorylation.

The cerebellar isozyme of the type ll CaM kinase was purified and its biochemical properties were compared to the forebrain isozyme. The cerebellar isozyme is a large (500-kDa) multimeric enzyme composed of multiple copies of 50-kDa α subunits and 60/58-kDa β/β’ subunits. The holoenzyme contains approximately 2 α subunits and 8 β subunits. This contrasts to the forebrain isozyme, which is also composed of and β/β'subunits, but they are assembled into a holoenzyme of approximately 9 α subunits and 3 β/β ' subunits. The biochemical and enzymatic properties of the two isozymes are similar. The two isozymes differ in their association with subcellular structures. Approximately 85% of the cerebellar isozyme, but only 50% of the forebrain isozyme, remains associated with the particulate fraction after homogenization under standard conditions. Postsynaptic densities purified from forebrain contain the forebrain isozyme, and the kinase subunits make up about 16% of their total protein. Postsynaptic densities purified from cerebellum contain the cerebellar isozyme, but the kinase subunits make up only 1-2% of their total protein.

The enzymatic activity of both isozymes of the type II CaM kinase is regulated by autophosphorylation in a complex manner. The kinase is initially completely dependent on Ca^(2+)/calmodulin for phosphorylation of exogenous substrates as well as for autophosphorylation. Kinase activity becomes partially Ca^(2+) independent after autophosphorylation in the presence of Ca^(2+)/calmodulin. Phosphorylation of only a few subunits in the dodecameric holoenzyme is sufficient to cause this change, suggesting an allosteric interaction between subunits. At the same time, autophosphorylation itself becomes independent of Ca^(2+) These observations suggest that the kinase may be able to exist in at least two stable states, which differ in their requirements for Ca^(2+)/calmodulin.

The autophosphorylation sites that are involved in the regulation of kinase activity have been identified within the primary structure of the α and β subunits. We used the method of reverse phase-HPLC tryptic phosphopeptide mapping to isolate individual phosphorylation sites. The phosphopeptides were then sequenced by gas phase microsequencing. Phosphorylation of a single homologous threonine residue in the α and β subunits is correlated with the production of the Ca^(2+) -independent activity state of the kinase. In addition we have identified several sites that are phosphorylated only during autophosphorylation in the absence of Ca^(2+)/ calmodulin.

Adsorption of Pb(II) and Cu(II) on α-quartz from aqueous solutions: influence of pH, ionic strength, and complexing ligands

Adsorption of aqueous Pb(II) and Cu(II) on α-quartz was studied as a function of time, system surface area, and chemical speciation. Experimental systems contained sodium as a major cation, hydroxide, carbonate, and chloride as major anions, and covered the pH range 4 to 8. In some cases citrate and EDTA were added as representative organic complexing agents. The adsorption equilibria were reached quickly, regardless of the system surface area. The positions of the adsorption equilibria were found to be strongly dependent on pH, ionic strength and concentration of citrate and EDTA. The addition of these non-adsorbing ligands resulted in a competition between chelation and adsorption. The experimental work also included the examination of the adsorption behavior of the doubly charged major cations Ca(II) and Mg(II) as a function of pH.

The theoretical description of the experimental systems was obtained by means of chemical equilibrium-plus-adsorption computations using two adsorption models: one mainly electrostatic (the James-Healy Model), and the other mainly chemical (the Ion Exchange-Surface Complex Formation Model). Comparisons were made between these two models.

The main difficulty in the theoretical predictions of the adsorption behavior of Cu(II) was the lack of the reliable data for the second hydrolysis constant(*β_2) The choice of the constant was made on the basis of potentiometric titratlons of Cu^(2+)

The experimental data obtained and the resulting theoretical observations were applied in models of the chemical behavior of trace metals in fresh oxic waters, with emphasis on Pb(II) and Cu(II).

Models of the Oxygen-Evolving Complex of Photosystem II

In the five chapters that follow, I delineate my efforts over the last five years to synthesize structurally and chemically relevant models of the Oxygen Evolving Complex (OEC) of Photosystem II. The OEC is nature’s only water oxidation catalyst, in that it forms the dioxygen in our atmosphere necessary for oxygenic life. Therefore understanding its structure and function is of deep fundamental interest and could provide design elements for artificial photosynthesis and manmade water oxidation catalysts. Synthetic endeavors towards OEC mimics have been an active area of research since the mid 1970s and have mutually evolved alongside biochemical and spectroscopic studies, affording ever-refined proposals for the structure of the OEC and the mechanism of water oxidation. This research has culminated in the most recent proposal: a low symmetry Mn₄CaO₅ cluster with a distorted Mn₃CaO₄ cubane bridged to a fourth, dangling Mn. To give context for how my graduate work fits into this rich history of OEC research, Chapter 1 provides a historical timeline of proposals for OEC structure, emphasizing the role that synthetic Mn and MnCa clusters have played, and ending with our Mn₃CaO₄ heterometallic cubane complexes.

In Chapter 2, the triarylbenzene ligand framework used throughout my work is introduced, and trinuclear clusters of Mn, Co, and Ni are discussed. The ligand scaffold consistently coordinates three metals in close proximity while leaving coordination sites open for further modification through ancillary ligand binding. The ligands coordinated could be varied, with a range of carboxylates and some less coordinating anions studied. These complexes’ structures, magnetic behavior, and redox properties are discussed.

Chapter 3 explores the redox chemistry of the trimanganese system more thoroughly in the presence of a fourth Mn equivalent, finding a range of oxidation states and oxide incorporation dependent on oxidant, solvent, and Mn salt. Oxidation states from Mn^II₄ to Mn^IIIMn^IV₃ were observed, with 1-4 O^2– ligands incorporated, modeling the photoactivation of the OEC. These complexes were studied by X-ray diffraction, EPR, XAS, magnetometry, and CV.

As Ca<sup>2+ is a necessary component of the OEC, Chapter 4 discusses synthetic strategies for making highly structurally accurate models of the OEC containing both Mn and Ca in the Mn₃CaO₄ cubane + dangling Mn geometry. Structural and electrochemical characterization of the first Mn₃CaO₄ heterometallic cubane complex— and comparison to an all-Mn Mn₄O₄ analog—suggests a role for Ca<sup>2+ in the OEC. Modification of the Mn₃CaO₄ system by ligand substitution affords low symmetry Mn₃CaO₄ complexes that are the most accurate models of the OEC to date.

Finally, in Chapter 5 the reactivity of the Mn₃CaO₄ cubane complexes toward O- atom transfer is discussed. The metal M strongly affects the reactivity. The mechanisms of O-atom transfer and water incorporation from and into Mn₄O₄ and Mn₄O₃ clusters, respectively, are studied through computation and ¹⁸O-labeling studies. The μ3-oxos of the Mn₄O₄ system prove fluxional, lending support for proposals of O^2– fluxionality within the OEC.

Avaliação da sorção de Cu (II) e Hg (II) pela Sargassum sp modificado com epicloridrina

É crescente o aumento da preocupação do homem com a contaminação de ambientes aquáticos uma vez que da subsistência dos mesmos depende o bem estar de todos. Ao mesmo tempo em que cresce a preocupação tem aumentado a quantidade de pesquisas em busca de tecnologias alternativas ao tratamento e remediação de efluentes aquosos contaminados pelas mais diversas substâncias incluindo os metais pesados. Nas últimas décadas, tem crescido o número de trabalhos avaliando a capacidade de sorção e a viabilidade da utilização de biossorventes de baixo custo na captação de íons metálicos e um desses materiais são as biomassas de algas pardas. Dentre os vários gêneros existentes no planeta o território brasileiro é rico na macroalga do gênero Sargassum. Muito embora a composição dessas biomassas varie o principal constituinte das mesmas é o ácido algínico e seus sais alcalinos na forma de um copolímero linear, homopolimérico, com unidades do ácido manurônico, (M), (1-4)-β-D- ligado e seu epímero em C-5 nos resíduos α-L-gulurônicos, (G), respectivamente, covalentemente ligados entre si em sequencias diferenciadas ou em blocos. Os monômeros podem aparecer em blocos homopoliméricos consecutivos, resíduos G (unidades G), resíduos consecutivos M (unidades M), pequenas unidades alternadas M e G (blocos MG), ou em blocos aleatoriamente organizados. A proposta dessa dissertação é realizar a modifica��ão do copolímero existente na biomassa com epicloridrina, avaliar e comparar a captação de íons Cu (II) e Hg (II) pela biomassa da alga Sargassum sp., com a biomassa não modificada e resultados publicados na literatura