Activación de aldehídos a,b-insaturados mediante aminocatálisis en procesos enantioselectivos. Cicloadiciones (3+2) y reacciones en cascada Michael/Henry

During the research that it is summarized in the present memory, the activation of enals via iminium ion catalysis in different transformations has been studied. Firstly, a 1,3-dipolar cycloaddition between stable azomethine ylides and a,b-unsaturated aldehydes catalyzed by a chiral imidazolidinone derivative has been optimized. Employing this methodology we have synthesized a large range of densely substituted pyrroloisoquinolines and pyrrolophthalazines with good yields and high values of diastereo- and enantioselectivity. Moreover, a mechanistic study has been carried out based on DFT calculations and experimental data which have allowed us to propose that the (3+2) cycloaddition reaction follows a sequential Michael addition/Mannich cyclization pathway. The formation of the iminium ion as a result of the condensation between the a,b-unsaturated aldehyde and the catalyst plays an essential role, regarding both reactivity and stereoselectivity. On the other hand we have developed a methodology to carry out a cascade Michael/Henry reaction followed by a sequential dehydration. Starting from simple substrates (2-nitromethylacrilates and a,b-unsaturated aldehydes) and employing a prolinol-derivative catalyst a series of quiral nitrocyclohexadienes have been synthesized.

Diário da Constituinte [gravação de vídeo] : [programa n. 706 B]

A Constituinte manteve a vitaliciedade dos juízes do Tribunal de Contas e considerou que as Forças Armadas são responsáveis pela defesa da lei e da ordem. A emenda que suprimia os blocos parlamentares do textoconstitucional, impedindo que eles participassem, proporcionalmente, da formação de de mesas e comissões do Congresso foi rejeitada.

Surface Expression and Subunit Specific Control of Steady Protein Levels by the Kv7.2 Helix A-B Linker

12 p.

Monthly charts of surface salinity in the Eastern Tropical Pacific Ocean

ENGLISH: Mean monthly maps of surface salinity of the eastern Pacific Ocean were prepared using all available data. Charts were also made of the distribution by one-degree quadrangles of the number of surface salinity observations for each month. Features of interest in the surface salinity distribution are discussed briefly, especially with reference to temporal changes. SPANISH: Se prepararon mapas mensuales sobre la salinidad media de superficie del Océano Pacifico oriental tropical, usando todos los datos disponibles. También se ejecutaron cartas por cuadrángulos de un grado, según el número de las observaciones mensuales de la distribución de la salinidad superficial. Las caracteristicas de interés de las distribuciones de la salinidad superficial se discuten brevemente, especialmente con referencia a los cambios estacionales. (PDF contains 44 pages.)

Surface drift charts for the Eastern Tropical Pacific Ocean

ENGLISH: For the region of the Eastern Tropical Pacific Ocean between 0° and 300 N, and between 1200 W and the coastline of the Americas, charts of surface drift have been prepared for each month of the year. These should be of interest to both mariners and oceanographers. SPANISH: Cartas de la deriva de superficie para la región del Océano Pacífico Oriental Tropical, comprendida entre 0° y 30° N., Y 120° O. y la línea de la costa de las Américas fueron preparadas por cada mes del año. Estas pueden interesar tanto a los marinos como a los oceanógrafos. (PDF contains 23 pages.)

An oceanographic atlas of the Eastern Tropical Pacific Ocean, based on data from EASTROPIC Expedition, October-December 1955.

ENGLISH: EASTROPIC Expedition was a cooperative oceanographic study of the eastern tropical Pacific Ocean conducted during the period 2 October through 16 December 1955. The five participating agencies and the ships they operated were: Scripps Institution of Oceanography (SIO), Spencer F. Baird and Horizon; Pacific Oceanic Fisheries Investigations (POFI) of the U. S. Fish and Wildlife Service, now Honolulu Biological Laboratory (HBL) of the U. S. Bureau of Commercial Fisheries, Hugh M. Smith; California Department of Fish and Game, N. B. Scofield; the Peruvian Navy, Bondu; and the Inter-American Tropical Tuna Commission which operated no vessels but supplied equipment and personnel. In addition to these planned participations in EASTROPIC Expedition, valuable information was provided by CCOFI Cruise 5512 of the California Cooperative Oceanic Fisheries Investigations, conducted during the period 29 November -16 December 1955 with the two vessels Stranger and Black Douglas. While the observational programs of most of the agencies involved, in part, special hydrographic-biological studies of known features and processes in the region (see reports listed under Data Sources) the deployment of ships and therefore of observations was sufficient that EASTROPIC Expedition could be considered a survey of the eastern tropical Pacific. This report is concerned with that aspect of the Expedition and is a presentation in atlas form of most of the hydrographic data collected. For reasons given below, emphasis has been placed on the upper 300 m of the water column. SPANISH: La Expedición EASTROPIC es un estudio oceanográfico cooperativo del Océano Pacífico Oriental Tropical llevado a cabo durante el período del 2 de octubre al 16 de dícíembre de 1955. Las cinco agencias participantes y los barcos operados por ellas son los siguientes: Scrípps Instítutíon of Oceanography (SIO) , Spencer F. Baird y Horizon; Pacific Oceanic Fisheries Investigatíons (PO'FI) del U. S. Fish and Wildlife Service, ahora Honolulu Biological Laboratory (BHL) del U. S. Bureau of Commercial Fisheries, Hugh M. Smith; California Department of Fish and Game, N. B. Scofield; la Marina Peruana, Bondu; y la Comisión Interamericana del Atún Tropical que no dirigió ningún barco pero proporcionó equipo y personal. Además de estas participaciones planeadas en la Expedición EASTROPIC, fué suministrada información de valor por el Crucero CCOFI 5512 del California Cooperative Fisheries Investigatíons, llevado a cabo durante el período del 29 de noviembre al 16 de diciembre de 1955 con los barcos Stranger y Black Douglas. Aunque los programas de observación de la mayoría de las agencias, comprendieron en parte estudios especiales hidrográficos y biológicos de las características y de los procesos conocidos de la región (véase los informes indicados bajo Fuente de Datos), el despliegue de los barcos, y por lo tanto, de las observaciones, fué suficiente para que la Expedición EASTROPIC pudiera ser considerada como una encuesta del Pacífico Oriental Tropical. Este informe se refiere a este aspecto de la Expedición y es una presentación, en forma de un atlas, de la mayoría de los datos hidrográficos recolectados. Por las razones que se dan a continuación, se le dió énfasis a los 300 m., superiores de la columna de agua. (PDF contains 136 pages.)

Influence of the Azores high on sea level pressure and wind, and on precipitation, in the Eastern Tropical Pacific Ocean

ENGLISH: Intensification of the Azores high pressure cell in mid-year, with concomitant air flow from the Caribbean into the Pacific, is shown to be responsible for a secondary minimum of precipitation observed along the tropical Pacific coast of the Americas, and to have a measurable effect on wind and precipitation several hundred kilometers offshore. SPANISH: La intensificación de la célula de alta presión de las Azores a mediados del año, y la corriente de aire concomitante que entra al Pacífico procedente del Caribe, se demuestra que es la causante de un mínimo secundario de precipitación observado a lo largo de la costa tropical de las Américas en el Pacífico y que tiene un efecto mensurable sobre el viento y la precipitación varios cientos de kilómetros mar afuera. (PDF contains 23 pages.)

Detection of hepatitis B virus markers using a biosensor based on imaging ellipsometry

A biosensor based on imaging ellipsometry (BIE) has been developed and validated in 169 patients for detecting five markers of hepatitis B virus (HBV) infection. The methodology has been established to pave the way for clinical diagnosis, including ligand screening, determination of the sensitivity, set-up of cut-off values (CoVs) and comparison with other clinical methods. A matrix assay method was established for ligand screening. The CoVs of HBV markers were derived with the help of receiver operating characteristic curves. Enzyme-linked immunosorbent assay (ELISA) was the reference method. Ligands with high bioactivity were selected and sensitivities of 1 ng/mL and 1 IU/mL for hepatitis B surface antigen (HBsAg) and surface antibody (anti-HBs) were obtained respectively. The CoVs of HBsAg, anti-HBs, hepatitis B e antigen, hepatitis B e antibody and core antibody were as follows: 15%, 18%, 15%, 20% and 15%, respectively, which were the percentages over the values of corresponding ligand controls. BIE can simultaneously detect up to five markers within 1 h with results in acceptable agreement with ELISA, and thus shows a potential for diagnosing hepatitis B with high throughput.

Comparative growth and survival of fry of Clarias gariepinus (B), Clarias anguillaris (L), Heterobranchus bidorsalis (G), Heteroclarias, Clariabranchus and Clarias hybrids under outdoor nursery management system

Hybrids of Clariid catfishes; C. gariepinus (Netherlands), C. anguillaris, H. bidorsalis and their parental species were monitored for 8 weeks in 2 x 2 x 1m outdoor concrete tanks. The fry were fed NIFFR diet (40% crude protein) twice daily, 7 days of the week. Growth and survival records were taken weekly. The male HEB X female CLG hybrid showed an overall highest performance in growth rate while the lowest was recorded in male CLA X female CLG hybrid. The male HEB X female CLG hybrid grew at a faster rate than its reciprocal hybrid. In view or their growth rate, it is possible that the growth and survival rates or H. bidorsalis especially at the fry to fingerling stage could be improved through hybridization. The hybrid have potential as commercial food fish

Alaves B taldearen lesioak 2012-2013 denboraldian: azterketa eta hobetzeko ardatzak

Futbolean iskiotibialetan ematen diren lesioen errebisioa eta hauek ekiditeko proposamena.

Function of microRNA-146a and NF-κB in physiologic and pathologic hematopoiesis

During inflammation and infection, hematopoietic stem and progenitor cells (HSPCs) are stimulated to proliferate and differentiate into mature immune cells, especially of the myeloid lineage. MicroRNA-146a (miR-146a) is a critical negative regulator of inflammation. Deletion of the gene encoding miR-146a—expressed in all blood cell types—produces effects that appear as dysregulated inflammatory hematopoiesis, leading to a decline in the number and quality of hematopoietic stem cells (HSCs), excessive myeloproliferation, and, ultimately, to exhaustion of the HSCs and hematopoietic neoplasms. Six-week-old deleted mice are normal, with no effect on cell numbers, but by 4 months bone marrow hypercellularity can be seen, and by 8 months marrow exhaustion is becoming evident. The ability of HSCs to replenish the entire hematopoietic repertoire in a myelo-ablated mouse also declines precipitously as miR-146a-deficient mice age. In the absence of miR-146a, LPS-mediated serial inflammatory stimulation accelerates the effects of aging. This chronic inflammatory stress on HSCs in deleted mice involves a molecular axis consisting of upregulation of the signaling protein TRAF6 leading to excessive activity of the transcription factor NF-κB and overproduction of the cytokine IL-6. At the cellular level, transplant studies show that the defects are attributable to both an intrinsic problem in the miR-146a-deficient HSCs and extrinsic effects of miR-146a-deficient lymphocytes and non-hematopoietic cells. This study has identified a microRNA, miR-146a, to be a critical regulator of HSC homeostasis during chronic inflammatory challenge in mice and has provided a molecular connection between chronic inflammation and the development of bone marrow failure and myeloproliferative neoplasms. This may have implications for human hematopoietic malignancies, such as myelodysplastic syndrome, which frequently displays downregulated miR-146a expression.

Measurement of the direct CP asymmetry in b-->s+gamma via sum of exclusive B Meson decays using the BABAR detector

We perform a measurement of direct CP violation in b to s+gamma Acp, and the measurement of a difference between Acp for neutral B and charged B mesons, Delta A_{X_s\gamma}, using 429 inverse femtobarn of data recorded at the Upsilon(4S) resonance with the BABAR detector. B mesons are reconstructed from 16 exclusive final states. Particle identification is done using an algorithm based on Error Correcting Output Code with an exhaustive matrix. Background rejection and best candidate selection are done using two decision tree-based classifiers. We found $\acp = 1.73%+-1.93%+-1.02% and Delta A_X_sgamma = 4.97%+-3.90%+-1.45% where the uncertainties are statistical and systematic respectively. Based on the measured value of Delta A_X_sgamma, we determine a 90% confidence interval for Im C_8g/C_7gamma, where C_7gamma and C_8g are Wilson coefficients for New Physics amplitudes, at -1.64 < Im C_8g/C_7gamma < 6.52.

The intramolecular Buchner reaction of α-diazo-β-ketonitriles : development and application to the total synthesis of (+)-Salvileucalin B

Since its discovery in 1896, the Buchner reaction has fascinated chemists for more than a century. The highly reactive nature of the carbene intermediates allows for facile dearomatization of stable aromatic rings, and provides access to a diverse array of cyclopropane and seven-membered ring architectures. The power inherent in this transformation has been exploited in the context of a natural product total synthesis and methodology studies.

The total synthesis work details efforts employed in the enantioselective total synthesis of (+)-salvileucalin B. The fully-substituted cyclopropane within the core of the molecule arises from an unprecedented intramolecular Buchner reaction involving a highly functionalized arene and an α-diazo-β-ketonitrile. An unusual retro-Claisen rearrangement of a complex late-stage intermediate was discovered on route to the natural product.

The unique reactivity of α-diazo-β-ketonitriles toward arene cyclopropanation was then investigated in a broader methodological study. This specific di-substituted diazo moiety possesses hitherto unreported selectivity in intramolecular Buchner reactions. This technology was enables the preparation of highly functionalized norcaradienes and cyclopropanes, which themselves undergo various ring opening transformations to afford complex polycyclic structures.

Finally, an enantioselective variant of the intramolecular Buchner reaction is described. Various chiral copper and dirhodium catalysts afforded moderate stereoinduction in the cyclization event.