Cymantrene–Triazole "Click" Products: Structural Characterization and Electrochemical Properties

We report the first known examples of triazole-derivatized cymantrene complexes (η5-[4-substituted triazol-1-yl]cyclopentadienyl)tricarbonylmanganese(I), obtained via a “click” chemical synthesis, bearing a phenyl, 3-aminophenyl, or 4-aminophenyl moiety at the 4-position of the triazole ring. Structural characterization data using multinuclear NMR, UV–vis, ATR-IR, and mass spectrometric methods are provided, as well as crystallographic data for (η5-[4-phenyltriazol-1-yl]cyclopentadienyl)tricarbonylmanganese(I) and (η5-[4-(3-aminophenyl)triazol-1-yl]cyclopentadienyl)tricarbonylmanganese(I). Cyclic voltammetric characterization of the redox behavior of each of the three cymantrene–triazole complexes is presented together with digital simulations, in situ infrared spectroelectrochemistry, and DFT calculations to extract the associated kinetic and thermodynamic parameters. The trypanocidal activity of each cymantrene–triazole complex is also examined, and these complexes are found to be more active than cymantrene alone

The bright optical afterglow of the long GRB 001007

We present optical follow up observations of the long GRB 001007 between 6.14 hours and ~468 days after the event. An unusually bright optical afterglow (OA) was seen to decline following a steep power law decay with index alpha = -2.03 +/- 0.11, possibly indicating a break in the light curve at t - to < 3.5 days, as found in other bursts. Upper limits imposed by the LOTIS alerting system 6.14 hours after the gamma ray event provide tentative (1.2 sigma) evidence for a break in the optical light curve. The spectral index beta of the OA yields -1.24 +/- 0.57. These values may be explained both by several fireball jet models and by the cannonball model. Fireball spherical expansion models are not favoured. Late epoch deep imaging revealed the presence of a complex host galaxy system, composed of at least two objects located 1.2" (1.7 sigma) and 1.9" (2.7 sigma) from the afterglow position.Comment: 7 pages, 5 figures, published in A&

Formação em psicologia comunitária e os seus contributos pedagógicos para a participação cívica

Neste trabalho procura-se documentar os processos através dos quais a formação académica avançada pode contribuir para o aprofundamento da formação cívica dos estudantes e para gerar novos polos de liderança e/ou mudança social em contextos sociais diversificados. Descreve-se o percurso do ensino da Psicologia Comunitária como formação especializada no âmbito da Psicologia e como curriculum formativo autónomo, bem como o debate sobre as competências profissionais neste domínio científico-pedagógico. Apresentam-se os resultados de um questionário sobre competências sociais e profissionais em Psicologia Comunitária e da Análise SWOT com estudantes de Mestrado e Doutoramento que serviram de base para a avaliação da formação pela Agência de Avaliação e Acreditação do Ensino Superior (http://www.a3es.pt/pt). A análise dos resultados permite concluir que os diplomados em Psicologia Comunitária escolheram causas cívicas diversificadas nos seus percursos profissionais e que utilizam as competências formativas adquiridas no seu percurso formativo na sua prática profissional. Através da análise qualitativa dos dados recolhidos através de análise SWOT, realça-se a relevância atribuída à liberdade de escolha durante o percurso formativo e as oportunidades de contacto com realidades sociais diversificadas. A participação em contextos comunitários tem permitindo compreender melhor a complexidade da aplicação prática dos princípios, bem como do papel que pode desempenhar a investigação com base em pressupostos de relevância e utilidade para o desenvolvimento dos indivíduos, grupos e/ou comunidades

Strategies for prompt searches for GRB afterglows: the discovery of the GRB 001011 optical/near-infrared counterpart using colour-colour selection

We report the discovery of the optical and near-infrared counterparts to GRB 001011. The GRB 001011 error box determined by Beppo-SAX was simultaneously imaged in the near-infrared by the 3.58-m New Technology Telescope and in the optical by the 1.54-m Danish Telescope ~8 hr after the gamma-ray event. Here we implement the colour-colour discrimination technique proposed by Rhoads (2001) and extend it using near-IR data as well. We present the results provided by an automatic colour-colour discrimination pipe-line developed to discern the different populations of objects present in the GRB 001011 error box. Our software revealed three candidates based on single-epoch images. Second-epoch observations carried out ~3.2 days after the burst revealed that the most likely candidate had faded, thus identifying it with the counterpart to the GRB. In deep R-band images obtained 7 months after the burst a faint (R=25.38+/-0.25) elongated object, presumably the host galaxy of GRB 001011, was detected at the position of the afterglow. The GRB 001011 afterglow is the first discovered with the assistance of colour-colour diagram techniques. We discuss the advantages of using this method and its application to error boxes determined by future missions.Comment: Accepted for publication in Astronomy and Astrophysics, 13 pages, 16 figure

Giant and Reversible Barocaloric Effect in Trinuclear Spin-Crossover Complex Fe3(bntrz)6(tcnset)6

A giant barocaloric effect (BCE) in a molecular material Fe3(bntrz)6(tcnset)6 (FBT) is reported, where bntrz = 4-(benzyl)-1,2,4-triazole and tcnset = 1,1,3,3-tetracyano-2-thioethylepropenide. The crystal structure of FBT contains a trinuclear transition metal complex that undergoes an abrupt spin-state switching between the state in which all three FeII centers are in the high-spin (S = 2) electronic configuration and the state in which all of them are in the low-spin (S = 0) configuration. Despite the strongly cooperative nature of the spin transition, it proceeds with a negligible hysteresis and a large volumetric change, suggesting that FBT should be a good candidate for producing a large BCE. Powder X-ray diffraction and calorimetry reveal that the material is highly susceptible to applied pressure, as the transition temperature spans the range from 318 at ambient pressure to 383 K at 2.6 kbar. Despite the large shift in the spin-transition temperature, its nonhysteretic character is maintained under applied pressure. Such behavior leads to a remarkably large and reversible BCE, characterized by an isothermal entropy change of 120 J kg−1 K−1 and an adiabatic temperature change of 35 K, which are among the highest reversible values reported for any caloric material thus far

E46K-like α-synuclein mutants increase lipid interactions and disrupt membrane selectivity

Parkinson's disease (PD) is one of the most common neurodegenerative disorders and both genetic and histopathological evidence have implicated the ubiquitous presynaptic protein α-synuclein (αSyn) in its pathogenesis. Recent work has investigated how disrupting αSyn's interaction with membranes triggers trafficking defects, cellular stress, and apoptosis. Special interest has been devoted to a series of mutants exacerbating the effects of the E46K mutation (associated with autosomal dominant PD) through homologous E-to-K substitutions in αSyn's N-terminal region (i.e. E35K, E61K). Such E46K-like mutants have been shown to cause dopaminergic neuron loss and severe, yet L-DOPA-responsive, motor defects in mouse overexpression models, presenting enormous translational potential for PD and other "synucleinopathies". In this work, using a variety of biophysical techniques, we characterize the molecular pathology of E46K-like αSyn mutants by studying their structure and membrane-binding and remodeling abilities. We find that, although a slight increase in the mutants' avidity for synaptic vesicle-like membranes can be detected, most of their deleterious effects are connected to their complete disruption of αSyn's curvature selectivity. Indiscriminate binding can shift αSyn's subcellular localization away from its physiological interactants at the synaptic bouton toward trafficking vesicles and organelles, as observed in E46K-like cellular and murine models, as well as in human pathology. In conclusion, our findings suggest that a loss of curvature selectivity, rather than increased membrane affinity, could be the critical dyshomeostasis in synucleinopathies

The optimal number of lymph nodes examined in stage II colorectal cancer and its impact of on outcomes

Background: Lymph node status is the most important prognostic factor for colorectal cancer. The number of lymph nodes that should be histologically examined has been controversial. The aims of this study were to assess the impact of the number of lymph nodes examined on survival of patients with stage II colorectal cancer and to determine the optimal number of lymph nodes that should be examined.Methods: The study included 664 patients who underwent resection for stage II colorectal cancer. The clinical and histopathologic data of the patients were prospectively collected and analyzed.Results: The median number of lymph nodes examined was 12 (range: 1 to 58). The 5-year disease free survival rate was significantly higher for patients with 12 or more lymph nodes examined compared to those with less than 12 lymph nodes examined. The significant difference in 5-year disease free survival persisted if the dividing number increased progressively from 12 to 23. However, the difference in survival was most significant (lowest p value and highest hazard ratio) for the number 21. The 5-year disease free survival of patients with 21 or more lymph nodes examined was 80% whereas that of patients with less than 21 lymph nodes examined was 60% (p = 0.001, hazard ratio 2.08). Multivariate analysis showed that 21 or more lymph nodes examined was a factor that independently influenced survival. The 5-year disease free survival also increased progressively with the number of lymph node examined up to the number 21. After the number 21, the survival rate did not increase further. It was likely that 21 was the optimal number, at and above which the chance of lymph node metastasis was minimal.Conclusions: The number of lymph nodes examined in colorectal cancer specimen significantly influences survival. It is recommended that at least 21 lymph nodes should be examined for accurate diagnosis of stage II colorectal cancer. © 2010 Choi et al; licensee BioMed Central Ltd.published_or_final_versio