Gold Difluorocarbenoid Complexes: Spectroscopic and Chemical Profiling

Gold carbenes of the general type [LAu=CR2]+ are sufficiently long‐lived for spectroscopic inspection only if the substituents compensate for the largely missing stabilization of the carbene center by the [LAu]+ fragment. π‐Donation by two fluorine substituents (R=F) is insufficient; rather, difluorocarbene complexes are so deprived in electron density that they sequester even “weakly coordinating” anions such as triflate or triflimide. This particular bonding situation translates into unmistakable carbenium ion chemistry upon reaction with stilbene as a model substrate

(Un-) Coupling gaze and attention outside central vision

In normal vision, shifts of attention and gaze are tightly coupled. Here we ask if this coupling affects performance also when central vision is not available. To this aim, we trained normal-sighted participants to perform a visual search task while vision was restricted to a gaze-contingent viewing window ("forced field location") either in the left, right, upper, or lower visual field. Gaze direction was manipulated within a continuous visual search task that required leftward, rightward, upward, or downward eye movements. We found no general performance advantage for a particular part of the visual field or for a specific gaze direction. Rather, performance depended on the coordination of visual attention and eye movements, with impaired performance when sustainedattention and gaze have to be moved in oppositedirections. Our results suggest that during early stages of central visual field loss, the optimal location for the substitution of foveal vision does not depend on the particular retinal location alone, as has previously been thought, but also on the gaze direction required by the task the patient wishes to perform

Polyunsaturated C-Glycosidic 4-Hydroxy-2-pyrone Derivatives: Total Synthesis Shows that Putative Orevactaene Is Likely Identical with Epipyrone A

Orevactaene and epipyrone A were previously thought to comprise the same polyunsaturated tail but notably different C-glycosylated 4-hydroxy-2-pyrone head groups. Total synthesis now shows that the signature bicyclic framework assigned to orevactaene is a chimera; the compound is almost certainly identical with epipyrone A, whose previously unknown stereochemistry has also been established during this study. Key to success was the ready formation of the bicyclic core of putative orevactaene by a sequence of two alkyne cycloisomerization reactions using tungsten and gold catalysis. Equally important was the flexibility in the assembly process gained by the use of heterobimetallic polyunsaturated modules whose termini could be selectively and consecutively addressed in a practical one-pot cross-coupling sequence

Simulação do impacto das atividades florestais na fragilidade potencial em plantios de pinus.

Este trabalho, realizado em uma área com povoamento de Pinus taeda, teve por objetivo simular e mapear a influência do valor de impacto das atividades florestais na fragilidade potencial. Variáveis do solo, de declividade do terreno, valor de impacto e de cobertura vegetal foram utilizadas para gerar os mapas. Os resultados expressos pelo modelo adotado mostraram que as áreas mais frágeis apresentam em sua maioria declividades superiores a 75 % e textura que variam de arenosa a média, e as áreas menos frágeis apresentam predominantemente relevo plano (até 3 %) e textura argilosa. Quando simulado o impacto das atividades florestais sobre esse ambiente, verificou-se que na maior parte da área (78 %) todas as atividades florestais podem ser realizadas sem influência na degradação do meio ambiente e para algumas áreas (11 %) o ambiente foi considerado menos frágil, em razão da presença de cobertura vegetal

The Catalytic Asymmetric Mukaiyama–Michael Reaction of Silyl Ketene Acetals with α,β-Unsaturated Methyl Esters

α,β-Unsaturated esters are readily available but challenging substrates to activate in asymmetric catalysis. We now describe an efficient, general, and highly enantioselective Mukaiyama–Michael reaction of silyl ketene acetals with α,β-unsaturated methyl esters that is catalyzed by a silylium imidodiphosphorimidate (IDPi) Lewis acid

MHC class II antigen presentation pathway in murine tumours: tumour evasion from immunosurveillance?

Qualitative differences in the MHC class II antigen processing and presentation pathway may be instrumental in shaping the CD4+ T cell response directed against tumour cells. Efficient loading of many MHC class II alleles with peptides requires the assistance of H2-M, a heterodimeric MHC class II-like molecule. In contrast to the HLA-DM region in humans, the β-chain locus is duplicated in mouse, with the H2-Mb1 (Mb1β-chain distal to H2-Mb2 (Mb2) and the H2-Ma (Ma) α-chain gene). Here, we show that murine MHC class II and H2-M genes are coordinately regulated in murine tumour cell lines by T helper cell 1 (IFN-γ) and T helper cell 2 (IL-4 or IL-10) cytokines in the presence of the MHC class II-specific transactivator CIITA as determined by mRNA expression and Western blot analysis. Furthermore, Mαβ1 and Mαβ2 heterodimers are differentially expressed in murine tumour cell lines of different histology. Both H2-M isoforms promote equally processing and presentation of native protein antigens to H2-Ad- and H2-Ed-restricted CD4+ T cells. Murine tumour cell lines could be divided into three groups: constitutive MHC class II and CIITA expression; inducible MHC class II and CIITA expression upon IFN-γ-treatment; and lack of constitutive and IFN-γ-inducible MHC class II and CIITA expression. These differences may impact on CD4+ T cell recognition of cancer cells in murine tumour models. © 2000 Cancer Research Campaig

Controlling suction by vapour equilibrium technique at different temperatures, application to the determination of the water retention properties of MX80 clay

Problems related to unsaturated soils are frequently encountered in geotechnical or environmental engineering works. In most cases, for the purpose of simplicity, the problems are studied by considering the suction effects on volume change or shear strength under isothermal conditions. Under isothermal condition, very often, a temperature independent water retention curve is considered in the analysis, which is obviously a simplification. When the temperature changes are too significant to be neglected, it is necessary to account for the thermal effects. In this paper, a method for controlling suction using the vapour equilibrium technique at different temperatures is presented. First, calibration of various saturated saline solutions was carried out from temperature of 20 degrees C to 60 degrees C. A mirror psychrometer was used for the measurement of relative humidity generated by saturated saline solutions at different temperatures. The results obtained are in good agreement with the data from the literature. This information was then used to determine the water retention properties of MX80 clay, which showed that the retention curve is shifting down with increasing of temperature