RESUMO
Atom probe tomography (APT) analysis conditions play a major role in the composition measurement accuracy. Preferential evaporation (PE), which significantly biases the apparent composition, more than other well-known phenomena in APT, is strongly connected to those analysis conditions. One way to optimize them, in order to have the most accurate measurement, is therefore to be able to predict and then to estimate their influence on the apparent composition. An analytical model is proposed to quantify the PE. This model is applied to three different alloys such as NiCu, FeCrNi, and FeCu. The model explains not only the analysis temperature dependence, as in an already existing model, but also the dependence to the pulse fraction and the pulse frequency. Moreover, the model can also provide an energetic constant directly linked to the energy barrier required to field evaporate atom from the sample surface.
RESUMO
The tandem catalysis of ring-closing metathesis/atom transfer radical reactions was investigated with the homobimetallic ruthenium-indenylidene complex [(p-cymene)Ru(µ-Cl)3RuCl(3-phenyl-1-indenylidene)(PCy3)] (1) to generate active species in situ. The two catalytic processes were first carried out independently in a case study before the whole sequence was optimized and applied to the synthesis of several polyhalogenated bicyclic γ-lactams and lactones from α,ω-diene substrates bearing trihaloacetamide or trichloroacetate functionalities. The individual steps were carefully monitored by ¹H and ³¹P NMR spectroscopies in order to understand the intimate details of the catalytic cycles. Polyhalogenated substrates and the ethylene released upon metathesis induced the clean transformation of catalyst precursor 1 into the Ru(II)-Ru(III) mixed-valence compound [(p-cymene)Ru(µ-Cl)3RuCl(2)(PCy3)], which was found to be an efficient promoter for atom transfer radical reactions under the adopted experimental conditions.
RESUMO
Superplasticity, a phenomenon of high tensile elongation in polycrystalline materials, is highly effective in fabrication of complex parts by metal forming without any machining. Superplasticity typically occurs only at elevated homologous temperatures, where thermally-activated deformation mechanisms dominate. Here, we report the first observation of room-temperature superplasticity in a magnesium alloy, which challenges the commonly-held view of the poor room-temperature plasticity of magnesium alloys. An ultrafine-grained magnesium-lithium (Mg-8 wt.%Li) alloy produced by severe plastic deformation demonstrated 440% elongation at room temperature (0.35 T m) with a strain-rate sensitivity of 0.37. These unique properties were associated with enhanced grain-boundary sliding, which was approximately 60% of the total elongation. This enhancement originates from fast grain-boundary diffusion caused by the Li segregation along the grain boundaries and the formation of Li-rich interphases. This discovery introduces a new approach for controlling the room-temperature superplasticity by engineering grain-boundary composition and diffusion, which is of importance in metal forming technology without heating.
RESUMO
The role of the synaptic vesicle protein 2A (SV2A) protein, target of the antiepileptic drug levetiracetam, is still mostly unknown. Considering its potential to provide in vivo functional insights into the role of SV2A in epileptic patients, the development of an SV2A positron emission tomography (PET) tracer has been undertaken. Using a 3D pharmacophore model based on close analogues of levetiracetam, we report the rationale design of three heterocyclic non-acetamide lead compounds, UCB-A, UCB-H and UCB-J, the first single-digit nanomolar SV2A ligands with suitable properties for development as PET tracers.