Alilación diastereoselectiva de N-terc-butilsulfinil iminas con bromuros alílicos: aplicación a la síntesis de heterociclos nitrogenados benzocondensados

En la presente Memoria se ha estudiado la adición estereoselectiva de diferentes bromuros alílicos mediada por indio a diferentes N-terc-butilsulfiniliminas (tBSiminas), pudiendo participar algunos de los derivados de aminas homoalílicas obtenidos en estos procesos en reacciones de ciclación intramolecular, a través de una N-arilación o una reacción de Heck, para acceder de manera estereoselectiva a estructuras más complejas. Finalmente, se ha demostrado la utilidad sintética de la metodología desarrollada aplicándola a la síntesis de algunos productos naturales y sus derivados. La Discusión de resultados aquí presentada se ha estructurado en las siguientes partes: - Alilación diastereoselectiva de tBS-cetiminas. La alilación de diferentes tBScetiminas con bromuro de alilo en presencia de indio a reflujo de THF dio lugar a los correspondientes derivados de homoalil aminas 5 con buenos rendimientos, en general, variando la diastereoselectividad encontrada con la naturaleza de las tBScetiminas de partida. Las relaciones diastereoméricas en el caso de las cetiminas aromáticas fueron moderadas (75:25-85:15 rd), teniendo lugar la alilación con total diastereoselectividad en el caso de las iminas alifáticas derivadas de metil cetonas (>98:2 rd). Por otro lado la diastereoselectividad fue baja en la alilación de iminas α,β-insaturadas no cíclicas y sorprendentemente muy elevada en los sistemas cíclicos de seis (5j) y siete (5k) eslabones (92:8 y 94:6 rd, respectivamente). - Alilación diastereoselectiva de tBS-iminas con bromuros alílicos sustituidos. La adición de reactivos de alilindio, generados a partir de bromuro de crotilo e indio, a tBS-aldiminas y –cetiminas se produjo con prácticamente total diastereoselectividad facial y buenas relaciones diastereoméricas anti/sin en el caso de tBS-iminas derivadas de benzaldehídos sustituidos y de cetonas. Sin embargo, la diastereoselectividad anti/sin fue prácticamente nula en el caso de los derivados de aldehídos alifáticos lineales. También se encontró que la adición mediada por indio de bromuro de ciclohexenilo a tBS-cetiminas tuvo lugar con alta diastereoselectividad. - Aplicaciones sintéticas de homoalilaminas con un grupo o-bromoarilo en su estructura. El tratamiento de diferentes derivados de homoalilamina 5 y 9 con un anillo aromático en su estructura, que porta a su vez en posición orto un átomo de bromo, bajo condiciones de reacción tipo Heck catalizadas por Pd, llevó a la formación de los compuestos cíclicos esperados de 5, 6 y 7 eslabones con buenos rendimientos. A su vez, también fue posible llevar a cabo la síntesis de diferentes compuestos heterocíclicos benzocondensados a través de reacciones de N-arilación intramolecular, catalizadas bien por compuestos de Cu o de Pd, en compuestos nitrogenados que portan anillos aromáticos orto-bromo sustituidos. - Síntesis estereoselectiva de alcaloides 2–alquiltetrahidroquinolínicos. Se llevó a cabo la síntesis de los productos naturales (–)-angustureína y (–)-cuspareína, siendo el primer paso de reacción en ambos casos la adición de reactivos organomagnesianos a las tBS-aldiminas 8p y ent-8p. Las síntesis se completaron tras 3 etapas adicionales: desulfinilación, N-arilación intramolecular y N-metilación, siendo los rendimientos globales del 49% y 17% respectivamente. También se preparó de manera alternativa la (–)-angustureína a partir de la N-metil-2-aliltetrahidroquinolina (23p) tras metátesis cruzada con (E)-3-hexeno e hidrogenación catalítica posterior del doble enlace olefínico. Por último y a partir del compuesto 23p, tras acoplamiento tipo Heck con 4-bromoveratrol, se llevó a cabo la síntesis de un derivado (24p) de la (–)-cuspareína.

Peregrinajes tras la arquitectura sacra moderna

La presente comunicación pretende ofrecer una visión sintética de la vasta producción arquitectónica religiosa de orientación cristiana que se ha producido desde el periodo de entreguerras que traza, en todas las ciudades, nuevas sendas de peregrinación y constituye un interesante patrimonio arquitectónico y cultural que permanece algo olvidado en su presencia y potencialidad. Esta panorámica contempla un análisis simbólico de estas construcciones de lo sagrado en atención a las metáforas de la inestabilidad del alma, la intensidad de la luz y el paso del tiempo, aspectos que se calibran y perciben simultáneamente por las sensaciones de todos los sentidos y no solo por el hegemónico de la vista. Arquitecturas de lo sagrado que sirven a la sociedad, a la cultura y a la ciudad. Sendas modernas de peregrinación tras la arquitectura sacra moderna.

El aplacado de piedra trasventilado. Comportamiento mecánico, condicionantes constructivos y formales, su durabilidad y lesiones

La evolución en el uso de los materiales pétreos y sistemas constructivos de fachada ventilada influye y condiciona el concepto del diseño de los cerramientos de fachada de los edificios y del proyecto arquitectónico. El objetivo de esta comunicación es identificar, analizar y valorar de forma sintética los principales condicionantes técnicos que deben considerarse en los aspectos constructivos que influyen en el proyecto de fachadas ventiladas de aplacado pétreo, interpretando sus prestaciones y su comportamiento mecánico. Para garantizar su calidad y durabilidad, se propone la aplicación práctica de métodos de cálculo y control de calidad tanto de los materiales pétreos como del sistema constructivo. La metodología empleada se basa tanto en ensayos en laboratorio de la piedra empleada como ensayos in situ del sistema constructivo ya ejecutado en obra, analizando las características físicas y comportamiento mecánico del aplacado en relación con las acciones a las que se ve sometido en un edificio. Los resultados obtenidos permiten verificar las elevadas tensiones y solicitaciones a las que se ven sometidos los aplacados pétreos trasventilados, y la importancia del adecuado proyecto y ejecución del cerramiento, mediante un correcto dimensionado y control de calidad de la obra. En conclusión, la fachada trasventilada pétrea supone la transformación del tradicional carácter masivo del uso de la piedra natural en arquitectura en una delgada piel expuesta a sus máximas prestaciones dentro de un conjunto de capas especializadas funcionalmente. Por ello, entender mejor y de forma sintética el específico comportamiento mecánico del aplacado pétreo y sus sistemas de anclaje en las fachadas ventiladas, sus principales causas de lesión, las características constructivas más destacables y las metodologías de cálculo y ensayo para garantizar su durabilidad, contribuirá a mejorar la calidad constructiva de las fachadas ventiladas, manteniendo y potenciando el uso de la piedra natural en la arquitectura moderna.

Modelo e instrumentos de evaluación integrativa de competencias, objetivos mediante los temas de Teoría e Historia de la Educación

Se ofrece la sistemática para proceder al diseño integrado de nociones de Teoría e Historia de la Educación, para formar a aspirantes al magisterio infantil y primario, relacionando tales constructos con la realidad convivencial de las aulas, tomando como logros las competencias generales y específicas que se plantean y pretendiendo seguir las vías marcadas por los objetivos. El desarrollo coimplica las actividades de aprendizaje con los procesos de evaluación (sumativa, formativa, sintética…). Se sigue una metodología fenomenológica con análisis lingüístico y hermenéutico, con la incorporación de aportes empíricos. Esto se efectúa en la relación de fuentes legales y definiciones del programa, mediando el modelo de universidad interdisciplinar, e incorporando un modelo empleado en investigaciones previas. Tras pasar a integrar cada tema con una secuencia de competencias, se elaboran los niveles procedimentales, base para confeccionar ejercicios (aprendizaje-evaluación). Tras incardinar los objetivos específicos, se procede a mostrar ejemplos de actividades integradoras. Al final de muestra la valoración del modelo efectuada por los alumnos.

Complexidade textual e progressão escolar em dois registos : um estudo de correlação baseado em um corpus quasi-longitudinal

Tese de doutoramento, Linguística (Linguística Educacional), Universidade de Lisboa, Faculdade de Letras, 2016

Insight into the evolution of the Solanaceae from the parental genomes of Petunia hybrida

Petunia hybrida is a popular bedding plant that has a long history as a genetic model system. We report the whole-genome sequencing and assembly of inbred derivatives of its two wild parents, P. axillaris N and P. inflata S6. The assemblies include 91.3% and 90.2% coverage of their diploid genomes (1.4 Gb; 2n = 14) containing 32,928 and 36,697 protein-coding genes, respectively. The genomes reveal that the Petunia lineage has experienced at least two rounds of hexaploidization: the older gamma event, which is shared with most Eudicots, and a more recent Solanaceae event that is shared with tomato and other solanaceous species. Transcription factors involved in the shift from bee to moth pollination reside in particularly dynamic regions of the genome, which may have been key to the remarkable diversity of floral colour patterns and pollination systems. The high-quality genome sequences will enhance the value of Petunia as a model system for research on unique biological phenomena such as small RNAs, symbiosis, self-incompatibility and circadian rhythms.

Tab. 2,3,4 Specific resistivity of calculated models for the soundings in Lapland

Geoelectrical soundings were carried out in 29 different places in order to find permafrost and to measure its thickness. In most places above timber Iine a permafrost thickness of 10-50 m was recorded. Permafrost was found at sites with thin snow cover during winter. Here, deflation phenomena on the summits of fjells indicate the occurence of permafrost, Vegetation type might be a good indicator of permafrost, too. It seems obvious that permafrost exists extensively on fjell summits of northern Finland.

Ragguaglio della vita, virtú e miracoli del B. Gregorio Barbarigo, Vescovo di Padova ... : e diviso in tre parti ...

Mode of access: Internet.

Uso de água produzida na formulação de fluidos de perfuração

Drilling fluids have fundamental importance in the petroleum activities, since they are responsible for remove the cuttings, maintain pressure and well stability, preventing collapse and inflow of fluid into the rock formation and maintain lubrication and cooling the drill. There are basically three types of drilling fluids: water-based, non-aqueous and aerated based. The water-based drilling fluid is widely used because it is less aggressive to the environment and provide excellent stability and inhibition (when the water based drilling fluid is a inhibition fluid), among other qualities. Produced water is generated simultaneously with oil during production and has high concentrations of metals and contaminants, so it’s necessary to treat for disposal this water. The produced water from the fields of Urucu-AM and Riacho da forquilha-RN have high concentrations of contaminants, metals and salts such as calcium and magnesium, complicating their treatment and disposal. Thus, the objective was to analyze the use of synthetic produced water with similar characteristics of produced water from Urucu-AM and Riacho da Forquilha-RN for formulate a water-based drilling mud, noting the influence of varying the concentration of calcium and magnesium into filtered and rheology tests. We conducted a simple 32 factorial experimental design for statistical modeling of data. The results showed that the varying concentrations of calcium and magnesium did not influence the rheology of the fluid, where in the plastic viscosity, apparent viscosity and the initial and final gels does not varied significantly. For the filtrate tests, calcium concentration in a linear fashion influenced chloride concentration, where when we have a higher concentration of calcium we have a higher the concentration of chloride in the filtrate. For the Urucu’s produced water based fluids, volume of filtrate was observed that the calcium concentration influences quadratically, this means that high calcium concentrations interfere with the power of the inhibitors used in the formulation of the filtered fluid. For Riacho’s produced water based fluid, Calcium’s influences is linear for volume of filtrate. The magnesium concentration was significant only for chloride concentration in a quadratic way just for Urucu’s produced water based fluids. The mud with maximum concentration of magnesium (9,411g/L), but minimal concentration of calcium (0,733g/L) showed good results. Therefore, a maximum water produced by magnesium concentration of 9,411g/L and the maximum calcium concentration of 0,733g/L can be used for formulating water-based drilling fluids, providing appropriate properties for this kind of fluid.

Avaliação do efeito da inibição do reparo de sítios abásicos na resposta inflamatória celular

Base excision repair (BER) proteins has been associated with functions beyond DNA repair. Apurynic/apyrimidinic endonuclease 1 (APE1) is a multifunctional protein involved in a plethora of cellular activities, such as redox activation of transcription factors, RNA processing and DNA repair. Some studies have described the action of the protein 8-oxoguanine (OGG1) in correcting oxidized lesions in promoters as a step in the transcription of pro-inflammatory cytokines. Despite being especially important in redox activation of transcription factors such as nuclear factor κB (NF-κB) and AP- 1, the repair activity of APE1 has not yet been associated with the inflammatory response. In this study, experimental and bioinformatic analysis approaches have been used to investigate the relationship between inhibition of the repair of abasic sites in DNA by MX, a synthetic molecule designed to inhibt the repair activity of APE1, and the modulation of the inflammatory response. The results showed that treatment of monocytes with lipopolysaccharide (LPS) and MX reduced the expression of cytokines, chemokines and toll-like receptors, and negatively regulated biological immune processes, as macrophages activation, and NF-κB and tumor necrosis factor (TNF-α) and interferon pathways, without inducing cell death. The transcriptomic analysis suggests that LPS/MX treatment induces mitochondrial dysfunction, endoplasmic reticulum stress and activation of autophagy pathways, probably activated by impairment of cellular energy and/or the accumulation of nuclear and mitochondria DNA damage. Additionally, it is proposed that the repair activity of APE1 is required for transcription of inflammatory genes by interaction with abasic sites at specific promoters and recruitment of transcriptional complexes during inflammatory signaling. This work presents a new perspective on the interactions between the BER activity and the modulation of inflammatory response, and suggests a new activity for APE1 protein as modulator of the immune response in a redox-independent manner.

Aplicação de géis de goma guar no processo de clarificação de salmouras e águas produzidas

Produced water is considered the main effluent of the oil industry, due to their increased volume in mature fields and its varied composition. The oil and grease content (TOG) is the main parameter for the final disposal of produced water. In this context, it is of great significance to develop an alternative method based on guar gum gel for the treatment of synthetic produced water, and using as the differential a polymer having high hydrophilicity for clarifying waters contaminated with oil. Thus, this study aims to evaluate the efficiency of guar gum gels in the remotion of oil from produced water. Guar gum is a natural polymer that, under specific conditions, forms three-dimensional structures, with important physical and chemical properties. By crosslinking the polymer chains by borate ions in the presence of salts, the effect salting out occurs, reducing the solubility of the polymer gel in water. As a result, there is phase separation with the oil trapped in the collapsed gel. The TOG was quantified from the spectroscopy in the ultraviolet and visible region. The system was proven to be highly efficient in the removal of dispersed oil from water produced synthetically, reaching removal percentages above 90%.

Posicionamento estratégico de destinos: uma análise através da percepção dos operadores de Turismo da cidade de São Paulo sobre o destino Natal, Brasil

El turismo constituye una actividad propulsora de mejorías económicas y sociales en incontables lugares alrededor del mundo, y la ciudad de Natal se posiciona como uno de los principales destinos turísticos del Nordeste brasileño. De ese modo, el objetivo del presente estudio consistió en analizar el posicionamiento estratégico del destino Natal por medio de la percepción de los operadores de turismo de la ciudad de São Paulo, principal mercado emisor de turistas del país. El estudio de carácter descriptivo-exploratorio utilizó un abordaje cualitativo y tuvo, como universo de investigación, operadoras de turismo de la capital paulista que comercializan el destino Natal. En la colecta de datos, se utilizaron la investigación bibliográfica y el estudio de campo, siendo este último efetivado por medio de un guión de entrevista semiestruturado. Ya la técnica utilizada para el análisis de los datos fue el análisis de contenido, iniciada mediante selección del material recolectado y concluida con el proceso de categorización. Cuanto a los resultados del estudio, se percibió que el paulistano que viaja al destino Natal tiene un perfil demográfico que sugiere a la práctica del turismo sustentable, está a la busca del turismo de sol y playa, y valora las bellezas naturales del lugar. Los operadores de turismo entrevistados evaluaron, positivamente, la ciudad de Natal, y destacaron los siguientes atributos del destino: playas, bellezas naturales, hostelería, receptividad de los autóctonas, gastronomía, de entre otros. Además, los respondentes demostraron tener un fuerte encariño al destino. En lo que se refiere a los aspectos negativos, prevaleció la observancia de la ineficacia de los gobiernos locales, donde el deterioro de la malla aérea y la incipiente promoción del destino fueron apuntados como los dos principales gargalos. Al analizar la competencia, se identificó que Fortaleza, Porto de Galinhas y Maceió son los tres principales concurrentes de Natal, siendo el destino pernambucano lo que presenta mejor evaluación. Por fin, se observó que no existe una diferenciación relevante en el destino Natal.

Padrões de ordenação de constituintes das construções V2/V3 superficiais em cartas pessoais brasileiras dos séculos 19 e 20

In line with the model of grammar competition (Kroch, 1989; 2001), according to which the change in the syntactic domains is a process that develops via competition between different grammars, we describe and analyze the superficial constructions V2 / V3 in matrices / roots sentences of brazilian personal letters of the 19th and 20th centuries. The corpus, composed by 154 personal letters of Rio de Janeiro and Rio Grande do Norte, is divided into three century halves: (i) latter half of the 19th century; (ii) first half of the 20th century; and (iii) latter half of the 20th century. Our focus was the observation of the nature of preverbal constituents in superficial constructions V2 (verb in second position in the sentence) and V3 (verb in third position in the sentence), with a special attention on the position of the subject. Based on the various diachronical studies about the Portuguese ordination standards (Ambar (1992); Ribeiro (1995, 2001); Paixão de Sousa (2004); Paiva (2011), Coelho and Martins (2009, 2012)), our study sought to realize what are empirical ordination standards that involve superficial constructions V2 / V3 and how these patterns structure syntactically within a formal theoretical perspective (Chomsky, 1981; 1986), more specifically, in accordance with studies of Antonelli (2011), and Costa & Galves (2002). The survey results show that the data from the second half of the 19th century – unlike the first and second half of the 20th century data – have a greater balance in relation to the syntactic nature of preverbal constituent (contiguous or not), so that, in this period, the occurrence of orders with the subject in a preverbal position arrives at, at most, 52% (231/444 data); while in the 48% (213/444 data) remaining, the preverbal constituents are represented by a non-subject constituent, almost always an adverbial adjunct. Seen the results, we advocate that the brazilian personal letters of the 19th century have ordination patterns associated with a V2 system and an SV system, configuring, therefore, a possible competition process between different grammars that instantiate or a V2 system or an SV system. In other words, the brazilian letters of the 19th century instantiate a competition between the grammar of Classic Portuguese (a V2 system) and the grammars of Brazilian Portuguese and European Portuguese (an SV system). Therefore, that period is subject to the completion of two distinct parametric markings: (i) verb moved to the Fin core (grammar of Classic Portuguese) and (ii) verb moved to the T core (grammar of Brazilian Portuguese /European Portuguese). On the other hand, in the personal letters of the 20th century (first and second halves), there is a clear increase in ordenation patterns associated with the SV system, which shows more stable.

Estudo de métodos de tratamento de efluentes (troca iônica e eletroquímico) separados e sequenciais para eliminação de derivados de petróleo

The produce of waste and the amount of the water produced coming from activities of petroleum production and extraction has been a biggest challenge for oil companies with respect to environmental compliance due to toxicity. The discard or the reuse this effluent containing organic compounds as BTEX (benzene, toluene, ethylbenzene and xylene) can cause serious environmental and human health problems. Thus, the objective this paper was study the performance of two process (separately and sequential) in one synthetic effluent for the benzene, toluene and xylene removal (volatile hydrocarbons presents in the produced water) through of electrochemical treatment using Ti/Pt electrode and exchange resin ionic used in the adsorption process. The synthetic solution of BTX was prepared with concentration of 22,8 mg L-1, 9,7 mg L-1 e 9,0 mg L-1, respectively, in Na2SO4 0,1 mol L-1. The experiments was developed in batch with 0.3 L of solution at 25ºC. The electrochemical oxidation process was accomplished with a Ti/Pt electrode with different current density (J = 10, 20 e 30 mA.cm-2). In the adsorption process, we used an ionic exchange resin (Purolite MB 478), using different amounts of mass (2,5, 5 and 10 g). To verify the process of technics in the sequential treatment, was fixed the current density at 10 mA cm-2 and the resin weight was 2.5 g. Analysis of UV-VIS spectrophotometry, chemical oxygen demand (COD) and gas chromatography with selective photoionization detector (PID) and flame ionization (FID), confirmed the high efficiency in the removal of organic compounds after treatment. It was found that the electrochemical process (separate and sequential) is more efficient than absorption, reaching values of COD removal exceeding 70%, confirmed by the study of the cyclic voltammetry and polarization curves. While the adsorption (separately), the COD removal did not exceed 25,8%, due to interactions resin. However, the sequential process (electrochemical oxidation and adsorption) proved to be a suitable alternative, efficient and cost-effectiveness for the treatment of effluents petrochemical.

Síntese, estrutura e propriedades de polímeros de coordenação à base de íons lantanídeos e ácidos benzenodicarboxílicos

Metal Organic Frameworks (MOFs) are hybrids materials, often crystalline, consisting of metal or metal clusters, connected by polytopic organic ligands repetitively, leading to structures, usually porous. In this work, MOFs based on lanthanide ions (La3+ and Gd3+) and dicarboxylate type of ligands (isophthalic and terephthalic acids), were synthesized by hydrothermal, solvothermal and hydro(solvo)thermal methods. The effects of the synthetic route as well as the type of heating, conventional or by microwave, on the structure and properties of MOFs were studied. The powder samples obtained were characterized by X-ray diffraction, infrared spectroscopy, thermal analysis and scanning electron microscopy. The results suggest that the addition of an organic or inorganic base is needed to promote the deprotonation of the ligand, since in the samples prepared by the hydrothermal method, without the use of a base, no formation of the metalorganic framework was observed. On the other hand, the presence of DMF as solvent or cosolvent, afforded the deprotonation of the ligand with the consequent formation of MOFs. At least two different crystalline structures were identified for the samples prepared with terephthalic acid. These samples are isostructural with those reported for phases Eu(1,3-BDC)DMF, Eu2(1,4-BDC)3 (DMF)2 and Tb(1,4-BDC)H2O. The presence of water in the reaction medium in the hydro(solvo)thermal method, provoked the growth of the structure different from that observed in the absence of water. This can be explained by the difference in the coordination mode of water and DMF to lanthanide ions. Although not identified by XRD, the samples prepared with isophthalic acid, also present metalorganic structures, which was confirmed by the presence of the characteristic displacement of the carbonyl group band in their infrared spectra, compared to the spectrum of the pure ligand. This shift was also observed in the samples prepared with terephthalic acid. Thermal analisys shows that the metal organic frameworks do not collapse occurs at a temperature below 430°C.The analysis of scanning electron microscopy suggests that the morphology of powders is highly dependent on the type of heating used, conventional or by microwave.