Time-dependent pump-probe spectra of NeBr2

Time- and frequency-resolved pump-probe measurements on NeBr2 have been performed to better characterize its fragmentation dynamics on the B electronic state for vibrational levels in the energy region of the transition from direct vibrational predissociation to intramolecular vibrational relaxation dynamics. Above nu'=20 of the Br2 stretching mode, it was observed that the dependence of lifetime on the vibrational quantum number deviates from the energy-gap law by leveling off in the range of 10 psE transitions of the complex. These transitions are shifted 20 cm(-1) to lower energy from the free Br2 resonances, indicating an E state Ne-Br2 bond energy of 82 cm(-1). Measurements of NeBr2 vibrational predissociation via the delta nu=-2 channel were also performed for nu'=27, 28, and 29. The closing of the delta nu=-1 channel leads to an increase in the lifetimes of these vibrational levels. A new Nd:yttrium aluminum garnet pumped dual optical parametric oscillator/optical parametric amplifier system is described that allows us to conveniently record time-delayed pump-probe spectra with 2-cm(-1) spectral resolution and 15-ps time resolution.     

Ultrafast optics establishes metrological standards in high-frequency electronics

A measurement system is reported that allows for the complete characterization of high-speed oscilloscopes. The measurements are based on ultrafast optical methods, which are used to generate picosecond electrical pulses with photoconductive switches as test signals. The properties of the test pulses are determined by the electro-optic sampling method, which provides traceability to the unit of length and, hence, to the unit of time. The photoconductive switches combined with the electro-optic sampling system represent a primary standard in electrical pulse metrology. With the well-characterized pulses from this standard, the complex transfer function, the impulse and step response, as well as the intrinsic risetime of high-speed oscilloscopes are determined. Risetimes of 6–7 ps can be measured with an expanded uncertainty of 1.2 ps. PACS 84.40.Ua; 84.40.Az; 84.30.Ng     

Differential inhibition of postnatal brain,spinal cord and body growth by a growth hormone antagonist

Background  

Growth hormone (GH) plays an incompletely understood role in the development of the central nervous system (CNS). In this study, we use transgenic mice expressing a growth hormone antagonist (GHA) to explore the role of GH in regulating postnatal brain, spinal cord and body growth into adulthood. The GHA transgene encodes a protein that inhibits the binding of GH to its receptor, specifically antagonizing the trophic effects of endogenous GH.     

Assay Related Target Similarity (ARTS) - chemogenomics approach for quantitative comparison of biological targets

Computer-based chemogenomics approaches compare macromolecular drug targets based on their amino acid sequences or derived properties, by similarity of their ligands, or according to ligand-target interaction models. Here we present ARTS (Assay Related Target Similarity) as a quantitative index that estimates target similarity directly from measured affinities of a set of probe compounds. This approach reduces the risk of deducing artificial target relationships from mutually inactive compounds. ARTS implements a scoring scheme that matches intertarget similarity based on dose-response measurements. While all experimentally derived target similarities have a tendency to be data set-dependent, we demonstrate that ARTS depends less on the used data set than the commonly used Pearson correlation or Tanimoto index.     

Analysis of slip activity and heterogeneous deformation in tension and tension-creep of Ti–5Al–2.5Sn (wt %) using in-situ SEM experiments

The deformation behavior of a Ti–5Al–2.5Sn (wt %) near-α alloy was investigated during in-situ deformation inside a scanning electron microscope. Tensile experiments were performed at 296?K and 728?K (≈0.4?T _m), while tensile-creep experiments were performed at 728?K and 763?K. Active deformation systems were identified using electron backscattered diffraction-based slip trace analysis. Both basal and prismatic slip systems were active during the tensile experiments. Basal slip was observed for grains clustered around high Schmid factor orientations, while prismatic slip exhibited less dependence on the crystallographic orientation. The tension-creep experiments revealed less slip but more development of grain boundary ledges than in the higher strain rate tensile experiments. Some of the grain boundary ledges evolved into grain boundary cracks, and grain boundaries oriented nearly perpendicular to the tensile axis formed ledges earlier in the deformation process. Grain boundaries with high misorientations also tended to form ledges earlier than those with lower misorientations. Most of the grain boundary cracks formed in association with grains displaying hard orientations, where the c-axis was nearly perpendicular to the tensile direction. For the tension-creep experiments, pronounced basal slip was observed in the lower-stress creep regime and the activity of prismatic slip increased with increasing creep stress and temperature.     

Comparison of the deformation behaviour of commercially pure titanium and Ti–5Al–2.5Sn(wt.%) at 296 and 728 K

The tension and tensile-creep deformation behaviours of a fully-α phase commercially pure (CP) Ti and a near-α Ti–5Al–2.5Sn(wt.%) alloy deformed in situ inside a scanning electron microscope were compared. Tensile tests were performed at 296 and 728?K, while tensile-creep tests were performed at 728?K. The yield stress of CP Ti decreased dramatically with increasing temperature. In contrast, temperature had much smaller effect on the yield stress of Ti–5Al–2.5Sn(wt.%). Electron backscattered diffraction was performed both before and after the deformation, and slip trace analysis was used to determine the active slip and twinning systems, as well as the associated global stress state Schmid factors. In tension tests of CP Ti, prismatic slip was the most likely slip system to be activated when the Schmid factor exceeded 0.4. Prismatic slip was observed over the largest Schmid factor range, indicating that the local stress tensor varies significantly from the global stress state of uniaxial tension. The basal slip activity in Ti–5Al–2.5Sn(wt.%) was observed in a larger faction of grains than in CP Ti. Pyramidal ?c?+?a? slip was more prevalent in CP Ti. Although twinning was an active deformation mode in tension tests of the CP Ti, it was rare in Ti–5Al–2.5Sn(wt.%). During creep, dislocation slip was the primary apparent deformation mechanism in CP Ti, while evidence for dislocation slip was much less apparent in Ti–5Al–2.5Sn(wt.%), where grain boundary sliding was dominant. A robust statistical analysis was carried out to assess the significance of the comparative activity of the different slip systems under the variety of experimental conditions examined.     

Effect of thermomechanical processing on the creep behaviour of Udimet alloy 188

Udimet alloy 188 was subjected to grain-boundary engineering involving thermomechanical processing in an attempt to improve the creep performance and determine the effects on creep deformation processes. The as-received sheet was cold-rolled to either 10, 25 or 35% reduction per pass followed by a solution treatment at 1191°C for 1 h plus air cooling. This sequence was repeated four times and the resultant microstructure and grain-boundary character distribution were described using electron backscatter diffraction. The fraction of general high-angle grain boundaries tended to increase with increased cold rolling. The 10 and 25% cold-rolled materials exhibited lower creep rates than the 35% cold-rolled material. The measured creep stress exponents and activation energies suggested that dislocation creep with lattice self-diffusion was dominant at 760°C for stresses ranging between 100 and 220 MPa. A transition in the creep exponent below the applied stresses of 100 MPa indicated that a different secondary creep mechanism was rate-controlling at low stresses. A significant amount of grain-boundary cracking was observed both on the surface and subsurface of deformed samples, but surface cracks were greater in number and size than those within the bulk. The cracking behaviour was similar in both vacuum and air environments, indicating that grain-boundary cracking was not caused by environment. To assess the mechanisms of crack nucleation, in situ scanning electron microscopy was performed during elevated-temperature (T ≤ 760°C) tensile-creep deformation. Sequential secondary electron imaging and electron backscatter diffraction orientation mapping were performed in situ to allow the evolution of crack nucleation and linkage to be followed. Cracking occurred preferentially along general high-angle grain boundaries and less than 15% of the cracks were found on low-angle grain boundaries and coincident site lattice boundaries. A fracture initiation parameter analysis was performed to identify the role of slip system interactions at the boundaries and their impact on crack nucleation. The parameter was successful in separating the population of intact and cracked general high-angle boundaries at lower levels of strain, but not after crack coalescence dominated the fracture process. The findings of this work have significant implications regarding grain-boundary engineering of this alloy and potentially for other alloy systems.     

Product state resolved excitation spectroscopy of He-, Ne-, and Ar-Br2 linear isomers: experiment and theory

Valence excitation spectra for the linear isomers of He-, Ne-, and Ar-Br2 are reported and compared to a two-dimensional simulation using the currently available potential energy surfaces. Excitation spectra from the ground electronic state to the region of the inner turning point of the Rg-Br2 (B,nu') stretching coordinate are recorded while probing the asymptotic Br2 (B,nu') state. Each spectrum is a broad continuum extending over hundreds of wavenumbers, becoming broader and more blueshifted as the rare gas atom is changed from He to Ne to Ar. In the case of Ne-Br2, the threshold for producing the asymptotic product state reveals the X-state linear isomer bond energy to be 71+/-3 cm(-1). The qualitative agreement between experiment and theory shows that the spectra can be correctly regarded as revealing the one-atom solvent shifts and also provides new insight into the one-atom cage effect on the halogen vibrational relaxation. The measured spectra provide data to test future ab initio potential energy surfaces in the interaction of rare gas atoms with the halogen valence excited state.     

The Norbornene Shuttle: Multicomponent Domino Synthesis of Tetrasubstituted Helical Alkenes through Multiple C?H Functionalization

Shall we dance? Within the proposed mechanism for the palladium‐catalyzed title reaction, the strained alkene norbornene (or norbornadiene) enters and exits the catalytic cycle in a catalytic “square dance”, acting as both a promoter and a coupling partner in the formation of four carbon–carbon bonds, two of them by challenging C? H activation processes.