Preparation of propargyl 1,2-orthoesters of carbohydrates: From side reactions in dichloromethane to optimized reaction conditions in acetonitrile.

In this note, supercritical fluid chromatography coupled to high-resolution mass spectrometry (SFC-HRMS) has been used to identify a chloro glycoside formed during the preparation of propargyl 1,2-orthoesters in dichloromethane. Additional studies revealed that 20-40% of this side-product was obtained depending on the source of anhydrous solvent, and that tetrabutylammonium iodide amplifies this side-reaction. Finally, a reliable procedure was developed in acetonitrile to prepare these glycosyl donors from perbenzoylated bromo glycosides in manno, gluco and galacto series in 63-74% yield.

Organocatalytic enantioselective synthesis of ß-amino sulfonic acid derivatives.

An unprecedented enantioselective conjugate addition reaction of sodium bisulfite to various nitrostyrenes occurred upon the influence of a bifunctional amino-thiourea organocatalyst; a strategy that opens a straightforward route to unprotected chiral taurine derivatives thanks to the reduction of the obtained ß-nitroethanesulfonic acids into the corresponding amino derivatives.

Hydrozirconation/bromination, followed by a Michaelis-Arbuzov reaction, as a convenient approach towards polyfunctional glycosylphosphonates.

In this note, an hydrozirconation/bromination/Michaelis-Arbuzov sequence was developped to introduce a trimethylene phosphonate unit on ketopyranosides. Performed on polyfunctional substrates bearing orthogonal protecting groups, this new approach provided a straightforward entry towards a large diversity of glycophosphomimetics having a quaternary anomeric position.

Desempenho técnico-tático no basquetebol feminino: associação com as posições específicas das atletas / Technical-tactical performance in feminine basketball: association with the athletes' specific positions

O objetivo deste estudo empírico, descritivo e associativo foi analisar a associação entre o nível de desempenho técnico-tático de atletas de categorias de base de basquetebol feminino e suas posições específicas. As participantes foram 49 atletas de equipes de base pertencentes a um clube de basquetebol catarinense, envolvido em diferentes categorias do campeonato estadual de Santa Catarina/Brasil. Realizou-se a coleta de dados por meio de observação estruturada do desempenho técnico-tático das atletas, resultando na análise de 27.420 ações de jogo. Os dados foram transcritos em fichas sistemáticas de registro, com base no Instrumento de Avaliação do Desempenho Técnico-Tático Individual no Basquetebol (IAD-BB), e analisados a partir das componentes adaptação, tomada de decisão e eficácia. O tratamento estatístico envolveu a utilização de recursos descritivos (frequência simples e percentual) e inferenciais (teste Qui-quadrado) no programa SPSS 23, adotando-se o nível de 5% de significância para a interpretação dos resultados. A avaliação geral e por categorias competitivas evidenciaram que as atletas, independentemente da posição, apresentaram os percentuais mais elevados de desempenho adequado na componente eficácia e os mais baixos na adaptação. Evidenciou-se, ainda, que as armadoras apresentaram desempenhos superiores nas três componentes, enquanto o desempenho das pivôs chamou a atenção pelos percentuais mais elevados de desempenho inadequado na componente eficácia, em comparação às alas e às armadoras. Para o avanço da área de análise de jogo no basquetebol, recomenda-se a realização de estudos que investiguem a relação entre os fundamentos de jogo e as posições específicas em que os atletas atuam, assim como outros fatores que podem estar associados à eficácia, além da tomada de decisão e da adaptação...(AU)

The purpose of this empirical, descriptive and associative study was to analyze the association between the level of technical-tactical performance of youth female basketball athletes and their specific positions. Participants were 49 athletes of youth basketball teams belonging to a basketball club from Santa Catarina state/Brazil enrolled in u-13, u-14, u-16 and u-18 categories of the Santa Catarina state championship. Data were collected through a structured observation of the athletes' technical-tactical performance, resulting in 27,420 game actions. Data were transcribed in systematic record sheets, based on the Instrument for Assessment of Individual Technical-Tactical Performance in Basketball (IAD-BB), and analyzed from the components adaptation, decision making, and efficacy. Statistical treatment involved the use of descriptive (simple frequency and percentage) and inferential (Chi-square test) resources in the SPSS 23 program, adopting the level of significance of 5% for results interpretation. General and specific evaluation by competitive categories showed that, regardless of their position, athletes presented the highest percentages of adequate performance in efficacy, and the lowest in adaptation. It was also evidenced that the point guards presented superior performances in the three components, while the centers' performance caught attention by the higher percentages of efficacy's inadequate performance, in comparison to the point guards and small forwards. In order to advance the field of game analysis in basketball, it is recommended to carry out studies that investigate the relationship between the basketball technical-tactical skills and the specific positions in which athletes play, as well as other factors that may be associated with efficacy, besides decision-making and adaptation...(AU)

Differences and Similarities in TRAIL- and Tumor Necrosis Factor-Mediated Necroptotic Signaling in Cancer Cells.

Recently, a type of regulated necrosis (RN) called necroptosis was identified to be involved in many pathophysiological processes and emerged as an alternative method to eliminate cancer cells. However, only a few studies have elucidated components of TRAIL-mediated necroptosis useful for anticancer therapy. Therefore, we have compared this type of cell death to tumor necrosis factor (TNF)-mediated necroptosis and found similar signaling through acid and neutral sphingomyelinases, the mitochondrial serine protease HtrA2/Omi, Atg5, and vacuolar H(+)-ATPase. Notably, executive mechanisms of both TRAIL- and TNF-mediated necroptosis are independent of poly(ADP-ribose) polymerase 1 (PARP-1), and depletion of p38α increases the levels of both types of cell death. Moreover, we found differences in signaling between TNF- and TRAIL-mediated necroptosis, e.g., a lack of involvement of ubiquitin carboxyl hydrolase L1 (UCH-L1) and Atg16L1 in executive mechanisms of TRAIL-mediated necroptosis. Furthermore, we discovered indications of an altered involvement of mitochondrial components, since overexpression of the mitochondrial protein Bcl-2 protected Jurkat cells from TRAIL- and TNF-mediated necroptosis, and overexpression of Bcl-XL diminished only TRAIL-induced necroptosis in Colo357 cells. Furthermore, TRAIL does not require receptor internalization and endosome-lysosome acidification to mediate necroptosis. Taken together, pathways described for TRAIL-mediated necroptosis and differences from those for TNF-mediated necroptosis might be unique targets to increase or modify necroptotic signaling and eliminate tumor cells more specifically in future anticancer approaches.