Synthesis of arylated highly congested indans using a domino sequence

A novel and efficient regioselective synthesis of various arylated highly congested 7-aryl-5-methylsulfanylindan-4-carbonitriles (3a-(), methyl 7-aryl-5-methylsulfanylindan-4-carboxylates (lOa-e) and 7-aryl-5-methylsulfanylindan-4-carboxylic acids (lla-e) through base-catalyzed reaction of 6-aryl-4-methylsulfanyl-2-oxo-2H-pyran-3-carbonitriles (la-() and methyl 6-aryl-4-methylsulfanyl-2-oxo-2Hpyran-3-carboxylates (9a-e) by cyclopentanone (2) has been delineated. The synthetic potential of 2-pyranone was explored further to generate mo'iecular diversity using 6-aryl-4-secamino- 2-oxo-2H-pyran-3-carbonitriles (7a-h), 5,6-diaryl-4-methylsulfanyl-2-oxo2H-pyran-3-carbonitriles (Sa,b) and methyl 5,6-diaryl-4- methylsulfanyl-2-oxo-2H-pyran-3-carboxylates (12a,b) as precursors for the ring transformation by cyclopentanone to assess the effects of substituents on the course of the reaction to obtain highly congested indans, 6,7diaryl-5-methylsulfanylindan-4-carbonitriles (6a,b), 7-aryl-5-(piperidin-I-yl)indancarbonitriles (8a-h) and methyl 6,7-4- diaryl-5-methylsulfanylindan-4-carboxylate 13a,b).

An efficient substituent dependent synthesis of congested pyridines and pyrimidines

An efficient and versatile synthesis of various congested pyridines 3a-h, 6a,b, 8a-n, lOa-g, and 16a,b, and (pyrimidin-4-yl)acetonitriles 13a-g has been delineated by base catalyzed ring transformation of suitably functionalized 2H-pyran-2-ones la-h, 5, 7, and 15 by formamidine acetate 2a,acetamidine hydrochloride 2b, S-methylisothiourea 9a, pyrazol-I-yl-carboxamidine 9b, and arylamidine hydrochloride 12 separately in the presence of powdered KOH in dry DMF.

Reliability of lithium dilution cardiac output in anaesthetized sheep

BACKGROUND: Cardiac output (CO) measurement with lithium dilution (COLD) has not been fully validated in sheep using precise ultrasonic flow probe technology (COUFP). Sheep generate important cardiovascular research models and the use of COLD has become more popular in experimental settings. METHODS: Ultrasonic transit-time perivascular flow probes were surgically implanted on the pulmonary artery of 13 sheep. Paired COLD readings were taken at six time points, before and after implantation of a left ventricular assist device (LVAD) and compared with COUFP recorded just after lithium injection. RESULTS: The mean COLD was 5.7 litre min(-1) (range 3.8-9.6 litre min(-1)) and mean COUFP 5.9 litre min(-1) (range 4.0-9.2 litre min(-1)). The bias (standard deviation) was 0.3 (1.0) litre min(-1) [5.1 (16.9)%] and limits of agreement (LOA) were -1.7 to 2.3 litre min(-1) (-28.8 to 39.0%) with a percentage error (PE) of 34.4%. Data to assess trending [rate (95% confidence intervals)] included a 78 (62-93)% concordance rate in the four-quadrant plot (n=27). In the half moon polar plot (n=19), the mean polar angle was +5°, the radial LOA were -49 to +35° and 68 (47-89)% of data points fell within 22.5° of the mean polar angle. Both tests indicated moderate to poor trending ability. CONCLUSION: COLD is not precise when evaluated against COUFP in sheep based on the statistical criteria set, but the results are comparable with previously published animal studies. KEYWORDS:

Dinoflagellate abundance and events of ODP Site 189-1172 sediments

Palynomorphs were studied in samples from Ocean Drilling Program (ODP) Leg 189, Holes 1172A and 1172D (East Tasman Plateau; 2620 m water depth). Besides organic walled dinoflagellate cysts (dinocysts), broad categories of other palynomorphs were quantified in terms of relative abundance. In this contribution, we provide an overview of the dinocyst distribution from the Maastrichtian to lowermost Oligocene and Quaternary intervals and illustrate main trends in palynomorph distribution. The uppermost Cretaceous-lowermost Oligocene succession of Site 1172 has a confident biomagnetostratigraphy, enabling us to tie early Paleogene Southern Hemisphere dinocyst events to the geomagnetic polarity timescale for the first time. Dinocyst species from the Maastrichtian to earliest Oligocene at Site 1172 are largely endemic ("Transantarctic Flora") or bipolar; cosmopolitan taxa are present in the background as well. The Maastrichtian-early late Eocene dinocyst assemblages are indicative of shallow-marine to restricted marine, pro-deltaic conditions, closely tied to a massive siliciclastic sequence. By middle late Eocene times (~35.5 Ma), the siliciclastic sequence gave way to a thin glauconitic unit, considered to reflect the deepening of the Tasmanian Gateway. This transition coincides with the most prominent change in dinocyst associations of the Paleogene. The turnover is inferred to reflect a change from marginal marine to more offshore conditions, with increased winnowing and oxidation. Overlying pelagic carbonate ooze of middle early Oligocene and younger age is virtually barren of organic microfossils, although Quaternary assemblages have been recovered. This aspect is taken to reflect average low sedimentation rates and well-oxygenated water masses during most of the Oligocene and Neogene. The few palynologically productive samples from the Oligocene-Quaternary interval have a stronger cosmopolitan to subtropical signature, with warm-water species being common to abundant.

Geochemistry of Pliocene-Pleistocene volcanic sands of ODP Site 136-842

Several distinct, thin (2-7 cm), volcanic sand layers ("ashes") were recovered in the upper portions of Holes 842A and 842B. These holes were drilled 320 km west of the island of Hawaii on the outer side of the arch that surrounds the southern end of the Hawaiian chain. These layers are Pliocene to Pleistocene in age, graded, and contain fresh glass and mineral fragments (mainly olivine, plagioclase, and clinopyroxene) and tests of Pleistocene to Eocene radiolarians. The glass fragments are weakly vesicular and blocky to platy in shape. The glass and olivine fragments from individual layers have large ranges in composition (i.e, larger than expected for a single eruption). These features are inconsistent with an explosive eruption origin for the sands. The only other viable mechanism for transporting these sands hundreds of kilometers from their probable source, the Hawaiian Islands, is turbidity currents. These currents were probably related to several of the giant debris slides that were identified from Gloria sidescan images around the islands. These currents would have run over the ~500-m-high Hawaiian Arch on their way to Site 842. This indicates that the turbidity currents were at least 325 m thick. Paleomagnetic and biostratigraphic data allow the ages of the sands to be constrained and, thus, related to particular Hawaiian debris flows. These correlations were checked by comparing the compositions of the glasses from the sands with those of glasses and rocks from islands with debris flows directed toward Site 842. Good correlations were found for the 110-ka slide from Mauna Loa and the ~1.4-Ma slide from Lanai. The correlation with Kauai is poor, probably because the data base for that volcano is small. The low to moderate sulfur content of the sand glasses indicates that they were derived from moderately to strongly degassed lavas (shallow marine or subaerially erupted), which correlates well with the location of the landslide scars on the flanks of the Hawaiian volcanoes. The glass sands may have been formed by brecciation during the landslide events or spallation and granulation as lava erupted into shallow water.

Discarge compilation from The Global River Discharge (RivDIS) Project

The Global River Discharge (RivDIS) data set contains monthly discharge measurements for 1018 stations located throughout the world. The period of record varies widely from station to station, with a mean of 21.5 years. These data were digitized from published UNESCO archives by Charles Voromarty, Balaze Fekete, and B.A. Tucker of the Complex Systems Research Center (CSRC) at the University of New Hampshire. River discharge is typically measured through the use of a rating curve that relates local water level height to discharge. This rating curve is used to estimate discharge from the observed water level. The rating curves are periodically rechecked and recalibrated through on-site measurement of discharge and river stage.

Velero de Competición IMOCA OPEN 60

TIPO DE BUQUE: velero de competición IMOCA OPEN 60 CONSTRUCCIÓN: materiales compuestos ESLORA: LOA mayor de 59’ (17.938 m) y menor de 60’ (18.288) CALADO: máximo de 4.5 m CLASIFICACIÓN Y COTA: 2007 IMOCA Open60 Rule. ABS guide for building and classing offshore yachts. ISAF Offshore Special Regulations, category 0 VELOCIDAD A MOTOR: 8 nudos al 90% MCR SISTEMA DE PROPULSIÓN: motor diesel de potencia 37 CV. Hélice de 3 palas OTROS REQUERIMIENTOS: sólo competición, estudio del comportamiento en la mar en condiciones oceánicas. Insumergibilidad. Sistema de orza pivotante. Vela spinnaker asimétrica para vientos portantes

Industrializacion de los cotos de Huelva. Su posible producción en celulosa.

Por la Dirección General del Patrimonio Forestal del Estado y la Escuela Especial de Ingenieros de Montes se me encargó la redacción del presente trabajo: Industrialización de los "Cotos de Huelva". Su producción en celulosa. Personado en aquel lugar y tomando en trabajos de campo loa datos necesarios se ha redactado la siguiente memoria, que tengo el honor de entregar a ambos organismos por si merece su aprobación.

Vacíos urbanos en la ciudad de Zaragoza (1975-2010). Oportunidades para la estructuración y continuidad urbana

La expansión de las ciudades hacia la periferia en las últimas décadas ha generado una serie de tejidos en colisión, donde los intersticios y los espacios residuales muestran la realidad de una ciudad dispersa. A esta serie de espacios intermedios los denominaremos “vacíos urbanos” y determinaremos una serie de factores que hagan posible su identificación Los vacíos urbanos son el objeto de la Tesis. El concepto “vacío urbano” adquiere un determinado significado para la investigación y se acota formulando una serie de parámetros para su definición. Definiremos los “vacíos urbanos” como espacios que han aparecido en el extrarradio de las ciudades, fruto de una expansión sin precedentes de las áreas urbanas. Han surgido como lugares residuales condicionados por elementos naturales o por infraestructuras, ligados a una temporalidad incierta, no inmersos en la dinámicas urbanas o habiendo perdido su funcionalidad. El objetivo de esta investigación es localizar y clasificar los vacíos existentes en la ciudad partiendo de la hipótesis de que es posible establecer una metodología para su reconocimiento y comprobación de los parámetros que los definen. La investigación centra su estudio en la ciudad de Zaragoza, como un ejemplo paradigmático, confirmando que la nueva fenomenología territorial, no sólo se manifiesta en dicha ciudad y en las áreas en concreto donde se ha estudiado, sino que más bien se trata de observarla como una serie de modelos tipológicos que respondan a un proceso de análisis. La propuesta metodológica de loa tesis pasa por reconocerlos, mostrarlos y darles una visibilidad que permita su clasificación, el desarrollo de un estudio de Áreas de la ciudad donde se localizan y un análisis de cada tipología de vacío urbano. Como instrumento metodológico se ha elaborado una detallada cartografía a diferentes escalas. La realización de los planos ha sido el medio de análisis que ha permitido localizar e interpretar los vacíos, complementado con unas escogidas fotografías de estos entornos. La metodología se convierte en un modo de descubrir y analizar los vacíos, el proceso conlleva la comprobación y la clasificación en una tipología. Según se han ido analizando nuevas áreas, se confirma como un hecho repetitivo exitoso y se observa que es aplicable a otras áreas urbanas de similares características, donde se den las condiciones principales de cada tipo. En general, deberán ser espacios localizados en la periferia de núcleos urbanos donde aparezcan fenómenos ligados a una expansión discontinua. Parece probable que el futuro de la ciudad se tenga que resolver en las próximas décadas sobre su actual extensión; bajo este supuesto, es trascendente la función que los vacíos puedan desempeñar en el futuro desarrollo urbano. Toda posibilidad de intervención precisará de una necesaria reinterpretación, puestas las miras en su potencial como elementos capaces de generar una rehabilitación urbana. A su vez se hace conveniente plantear una reflexión sobre estos espacios cargados de una dimensión social y cultural, como lugares capaces de articular y dotar de identidad al medio urbano. Los vacíos deberían protagonizar un papel relevante en la estructuración urbana, abriendo posibilidades para el tramado de la ciudad desde nuevas perspectivas. Una apuesta para que estos espacios libres pasen de ser el objetivo de procesos urbanizadores tradicionales, a ser considerados como oportunos elementos vertebradores de los entornos periurbanos, colaborando en el objetivo de una ciudad contemporánea sostenible. ABSTRACT In the last decades the city periphary expansion has provoked a series of matters to collide, where interstices and waste lands show the reality of a divided city. We shall determine a number of factors allowing us to treat these “in between” spaces, also called "urban voids" as identifiable elements. We will consider them the subject of the thesis and establish them as a "concept", delimiting the meaning of the research specifically acquired, defining, and formulating a set of parameters. "Urban voids" are defined as spaces that have appeared on the outskirts of cities, the result of an unprecedented expansion of urban areas. They have emerged as waste lands, conditioned by natural elements or infrastructure, related to uncertain temporality, not immersed in the urban dynamics, or having lost their functionality. It seems likely that in the upcoming decades, the future of the city will have to resolve its current way of expanding . It is under this assumption that urban voids, as intermediate spaces, will play an important role in future urban developments. Any possible intervention will require a necessary reinterpretation, closely watching their potential as elements capable of generating an urban rehabilitation. At the same time, we wish to reflect on these spaces, in many cases loaded with a social and cultural dimension, as places able to articulate and give identity to the urban environment. Based on the hypothesis that it is possible to establish a methodology for recognition and verification, the purpose of this research is to locate and classify the existing urban voids in the city. The research focuses its study on the city of Saragossa which can be seen as a paradigmatic example. The objective is to confirm that this new territorial phenomenology, not only manifests itself in Saragossa and specific areas under study, but also, can be observed as a series of typological models that respond to a review process. The methodological proposal will recognize, demonstrate, and exhibit these urban voids, in a light that will allow us to classify them, examine the different areas where they can be found, and develop a tipology analysis of each type of urban void found. The technical tool used in this research is a detailed mapping at different scales. A realization of plans, as a mean of analysis, supplemented with a few selected pictures of these environments, will facilitate the location and interpretation of these voids. This scholarly approach to discover and analyze urban voids will involve checking and classifying them in a typology. It has been confirmed as a successful constant regulator while exploring new areas. It will be apply to other urban areas with similar characteristics, that is, spaces located on the periphery of urban areas where expansion is linked to the appearence of discontinuous phenomena. The urban voids play a fundamental role within the urban structure, providing the city a weaving scheme with opportunities of fresh perspectives. The challenge for these free spaces is to move from being the consequence of traditional urban development processes, to being considered opportune backbone elements of peri-urban environments, and to finally contribute to the objectives of a sustainable contemporary city.

O orçamento como instrumento de intervenção no domínio econômico

Este trabalho versa sobre a utilização do orçamento público como instrumento de intervenção no domínio econômico, demonstrando, em síntese, de que forma o Estado utiliza, ou ao menos deveria utilizar, o orçamento público como instrumento de planejamento de suas ações e de intervenção na atividade desempenhada pela iniciativa privada. Tem-se por objetivo contribuir para a compreensão jurídica de diversas questões atinentes à elaboração e execução da peça orçamentária federal, aos reflexos causados na economia e na atividade desempenhada pela iniciativa privada, especialmente no que toca à realização das receitas e despesas públicas, à elaboração das leis orçamentárias Plano Plurianual (PPA), Lei Orçamentária Anual (LOA) e Lei de Diretrizes Orçamentárias (LDO) e, também, aos interesses, às paixões e ideologias envolvidas em todo o processo financeiro. Para tanto, inicialmente, estuda o papel do Estado, distinguindo os campos de atuação privada e aquele reservado à Administração Pública, os modos de intervenção e aqueles aplicados à hipótese analisada, para, em seguida, proceder à análise da peça orçamentária, sua concepção atual e relevância para a iniciativa privada, o que possibilita, então, tratar de questões que envolvam as receitas públicas, em específico as tributárias e as despesas públicas. Por fim, trata do crédito público e, com isso, procura evidenciar de que forma, sob a ótica do orçamento público e nos limites legais de atuação do Estado, as previsões constantes do orçamento podem funcionar como instrumento de promoção, incentivo e estímulo, ou, em sentido contrário, limitar, frear ou desestimular o crescimento econômico e a atividade desenvolvida pela iniciativa privada.

Clinical Validation of Adjusted Corneal Power in Patients with Previous Myopic Lasik Surgery

Purpose. To validate clinically a new method for estimating the corneal power (P,) using a variable keratometric index (nkadj) in eyes with previous laser refractive surgery. Setting. University of Alicante and Medimar International Hospital (Oftalmar), Alicante, (Spain). Design. Retrospective case series. Methods. This retrospective study comprised 62 eyes of 62 patients that had undergone myopic LASIK surgery. An algorithm for the calculation of 11kadj was used for the estimation of the adjusted keratometric corneal power (Pkadj). This value was compared with the classical keratometric corneal power (Pk), the True Net Power (TNP), and the Gaussian corneal power (PcGauss). Likewise, Pkadj was compared with other previously described methods. Results. Differences between PcGauss and P, values obtained with all methods evaluated were statistically significant (p < 0.01). Differences between Pkadj and PcGauss were in the limit of clinical significance (p < 0.01, loA [ - 0.33,0.60] D). Differences between Pkadj and TNP were not statistically and clinically significant (p = 0.319, loA [- 0.50,0.44] D). Differences between Pkadj and previously described methods were statistically significant (p < 0.01), except with PcHaigisL (p = 0.09, loA [ - 0.37,0.29] D). Conclusion. The use of the adjusted keratometric index (nkadj) is a valid method to estimate the central corneal power in corneas with previous myopic laser refractive surgery, providing results comparable to PcHaigisL.

Régulation de l'expression de PPARγ dans l'arthrose

L’arthrose (OA) est une maladie dégénérative très répondue touchant les articulations. Elle est caractérisée par la destruction progressive du cartilage articulaire, l’inflammation de la membrane synoviale et le remodelage de l’os sous chondral. L’étiologie de cette maladie n’est pas encore bien définie. Plusieurs études ont été menées pour élucider les mécanismes moléculaires et cellulaires impliqués dans le développement de l’OA. Les effets protecteurs du récepteur activé par les proliférateurs de peroxysomes gamma (PPARγ) dans l'OA sont bien documentés. Il a été démontré que PPARγ possède des propriétés anti-inflammatoires et anti-cataboliques. Aussi, plusieurs stimuli ont été impliqués dans la régulation de l’expression de PPARγ dans différents types cellulaires. Cependant, les mécanismes exacts responsables de cette régulation ainsi que le profil de l’expression de ce récepteur au cours de la progression de l’OA ne sont pas bien connus. Dans la première partie de nos travaux, nous avons essayé d’élucider les mécanismes impliqués dans l’altération de l’expression de PPARγ dans cette maladie. Nos résultats ont confirmé l’implication de l’interleukine-1β (IL-1β), une cytokine pro-inflammatoire, dans la réduction de l’expression de PPARγ au niveau des chondrocytes du cartilage articulaire. Cet effet coïncide avec l'induction de l’expression du facteur de transcription à réponse précoce de type 1 (Egr-1). En plus, la diminution de l'expression de PPARγ a été associée au recrutement d'Egr-1 et la réduction concomitante de la liaison de Sp1 au niveau du promoteur de PPARγ. Dans la deuxième partie de nos travaux, nous avons évalué le profil d’expression de ce récepteur dans le cartilage au cours de la progression de cette maladie. Le cochon d’inde avec OA spontanée et le chien avec OA induite par rupture du ligament croisé antérieur (ACLT) deux modèles animaux d’OA ont été utilisés pour suivre l’expression des trois isoformes de PPARs : PPAR alpha (α), PPAR béta (β) et PPAR gamma (γ) ainsi que la prostaglandine D synthase hématopoïétique (H-PGDS) et la prostaglandine D synthase de type lipocaline (L-PGDS) deux enzymes impliquées dans la production de l’agoniste naturel de PPARγ, la 15-Deoxy-delta(12,14)-prostaglandine J(2) (15d-PGJ2). Nos résultats ont démontré des changements dans l’expression de PPARγ et la L-PGDS. En revanche, l’expression de PPARα, PPARβ et H-PGDS est restée stable au fil du temps. La diminution de l’expression de PPARγ dans le cartilage articulaire semble contribuer au développement de l’OA dans les deux modèles animaux. En effet, le traitement des chondrocytes par de siRNA dirigé contre PPARγ a favorisé la production des médiateurs arthrosiques tels que l'oxyde nitrique (NO) et la métalloprotéase matricielle de type 13 (MMP-13), confirmant ainsi le rôle anti-arthrosique de ce récepteur. Contrairement à ce dernier, le niveau d'expression de la L-PGDS a augmenté au cours de la progression de cette maladie. La surexpression de la L-PGDS au niveau des chondrocytes humains a été associée à la diminution de la production de ces médiateurs arthrosiques, suggérant son implication dans un processus de tentative de réparation. En conclusion, l’ensemble de nos résultats suggèrent que la modulation du niveau d’expression de PPARγ, de la L-PGDS et d’Egr-1 au niveau du cartilage articulaire pourrait constituer une voie thérapeutique potentielle dans le traitement de l’OA et probablement d’autres formes d'arthrite.

Hora de fazer as contas

Dos R$ 144,4 bilhões previstos na Lei Orçamentária Anual (LOA) 2016 para uso discricionário, ou seja, sem comprometimento com rubricas específicas, aproximadamente R$ 49,4 bilhões (34,2%) já foram empenhados pelo governo da presidente Dilma Rousseff (PT) – afastada na última quinta-feira pelos senadores para que seja julgada por crime de responsabilidade. Desse total, 15,2% já foram liquidados e 14,1% pagos. Por isso, Temer tem a autorização da LOA 2016 para investir o valor de R$ 95 bilhões em verbas discricionárias. A conta é do pesquisador da Diretoria de Análise de Políticas Públicas da Fundação Getúlio Vargas (DAPP/FGV), Wagner Oliveira, com base em dados do Siga Brasil, do Senado Federal.

Vencer a Marte sin Marte. Fiesta real que para celebrar la memoria de la entrada de ... María Luisa de Borbón y sus felices bodas con ... Carlos Segundo, representaron en presencia de sus magestades ... los estudiantes del Colegio Imperial ... martes once de febrero de 1681.

Contiene: "Pensamiento de la comedia" y "Loa".