Mild and general methods for the palladium-catalyzed cyanation of aryl and heteroaryl chlorides

[reaction: see text] New methods for the palladium-catalyzed cyanation of aryl and heteroaryl chlorides have been developed, featuring sterically demanding, electron-rich phosphines. Highly challenging electron-rich aryl chlorides, in addition to electron-neutral and electron-deficient substrates, as well as nitrogen- and sulfur-containing heteroaryl chlorides can all undergo efficient cyanation under relatively mild conditions using readily available materials. In terms of substrate scope and temperature, these methods compare very favorably with the state-of-the-art cyanations of aryl chlorides.     

Protein dynamics and function: Making new strides with an old warhorse,the alkaline conformational transition of cytochrome c

Protein dynamics is intimately linked to function. In metalloproteins, dynamics are often coupled to redox activity, ligand binding and enzyme function. We provide a concise overview of the field and then focus on the use of the alkaline conformer of cytochrome c as a model system to probe the factors that control the conformational dynamics of proteins in general and metalloproteins in particular. We consider the effects of ligands on metal-mediated dynamics, the interplay between intrinsic metal-ligand dynamics and barriers imposed by the protein scaffold itself, and the effects of local and overall protein stability on dynamics. Discussed within are the collected results from equilibrium thermodynamic methods, pH jump kinetics and conformationally gated redox reactions between small inorganic reagents and metalloproteins used as a means to probe conformational switching in metalloproteins.     

Disappearance of back-to-back high-pT hadron correlations in central Au+Au collisions at sqrt[s NN ] =200 GeV

Azimuthal correlations for large transverse momentum charged hadrons have been measured over a wide pseudorapidity range and full azimuth in Au+Au and p+p collisions at sqrt[s(NN)]=200 GeV. The small-angle correlations observed in p+p collisions and at all centralities of Au+Au collisions are characteristic of hard-scattering processes previously observed in high-energy collisions. A strong back-to-back correlation exists for p+p and peripheral Au+Au. In contrast, the back-to-back correlations are reduced considerably in the most central Au+Au collisions, indicating substantial interaction as the hard-scattered partons or their fragmentation products traverse the medium.     

Identification of a selectivity determinant for inhibition of tumor necrosis factor-alpha converting enzyme by comparative modeling

Inhibition of tumor necrosis factor-alpha converting enzyme (TACE) is a widespread objective in the search for disease modifying agents to combat rheumatoid arthritis and other autoimmune diseases. Until recently, most of the inhibitors in the literature have shown concomitant activity against the related matrix metalloproteinases (MMPs), producing undesired side effects. Here we describe the successful search for a TACE selectivity mechanism. We built a homology model based on the crystal structure of the related snake venom protein atrolysin. Comparison of the model with crystal structures of MMPs suggested a uniquely shaped S1' pocket that might be exploited for selectivity. A novel gamma-lactam scaffold was used to explore the activity profile of P1' sidechains, resulting in highly selective compounds consistent with this hypothesis. Transferability of the hypothesis was then demonstrated with five other distinct scaffolds.     

Space charge analysis in enamelled wires by using thermally stimulated depolarization current (TSDC)

This paper reports on measurements of thermally stimulated depolarization current (TSDC) that is applied to characterize changes in the large motors and generators enamelled wires that have been exposed to aging under steep-front pulse voltage waveforms. The thermoelectrets are prepared at various polarizing fields, E_P, and measurements of TSDC are carried out both as a function of time and temperature over the range of 23–200 °C. In addition, various TSDC parameters such as activation energy, ?_a, characteristic relaxation time, τ and the released charge, Q during the relaxation process have been determined by applying initial rise method. The experimental results for TSDC spectra of wire specimens have shown that the total stored charge in the insulation bulk increases significantly, as the number of insulation layers increases on the wire. The reason for such a higher concentration of trapped charges is more likely due to the presence of a broad distribution of the traps, which are occupied by the injected charges.     

Measurement of the bottom quark contribution to nonphotonic electron production in p + p collisions at √s=200 GeV

The contribution of B meson decays to nonphotonic electrons, which are mainly produced by the semileptonic decays of heavy-flavor mesons, in p + p collisions at √s=200 GeV has been measured using azimuthal correlations between nonphotonic electrons and hadrons. The extracted B decay contribution is approximately 50% at a transverse momentum of pT≥5 GeV/c. These measurements constrain the nuclear modification factor for electrons from B and D meson decays. The result indicates that B meson production in heavy ion collisions is also suppressed at high pT.     

Particle-type dependence of azimuthal anisotropy and nuclear modification of particle production in Au+Au collisions at square root of sNN=200 GeV

We present STAR measurements of the azimuthal anisotropy parameter v(2) and the binary-collision scaled centrality ratio R(CP) for kaons and lambdas (Lambda+Lambda) at midrapidity in Au+Au collisions at square root of s(NN)=200 GeV. In combination, the v(2) and R(CP) particle-type dependencies contradict expectations from partonic energy loss followed by standard fragmentation in vacuum. We establish p(T) approximately 5 GeV/c as the value where the centrality dependent baryon enhancement ends. The K(0)(S) and Lambda+Lambda v(2) values are consistent with expectations of constituent-quark-number scaling from models of hadron formation by parton coalescence or recombination.     

Coherent rho(0) production in ultraperipheral heavy-ion collisions

The STAR Collaboration reports the first observation of exclusive rho(0) photoproduction, AuAu-->AuAurho(0), and rho(0) production accompanied by mutual nuclear Coulomb excitation, AuAu-->Au*Au*rho(0), in ultraperipheral heavy-ion collisions. The rho(0) have low transverse momenta, consistent with coherent coupling to both nuclei. The cross sections at sqrt[s(NN)]=130 GeV agree with theoretical predictions treating rho(0) production and Coulomb excitation as independent processes.     

Azimuthal anisotropy of K(0)(S) and Lambda+Lambda production at midrapidity from Au+Au collisions at sqrt[s(NN)]=130 GeV

We report STAR results on the azimuthal anisotropy parameter v(2) for strange particles K(0)(S), Lambda, and Lambda at midrapidity in Au+Au collisions at sqrt[s(NN)]=130 GeV at the Relativistic Heavy Ion Collider. The value of v(2) as a function of transverse momentum, p(t), of the produced particle and collision centrality is presented for both particles up to p(t) approximately 3.0 GeV/c. A strong p(t) dependence in v(2) is observed up to 2.0 GeV/c. The v(2) measurement is compared with hydrodynamic model calculations. The physics implications of the p(t) integrated v(2) magnitude as a function of particle mass are also discussed.     

Midrapidity Lambda and Lambda(macro) production in Au+Au collisions at the square root of [s(NN)]=130 GeV

We report the first measurement of strange (Lambda) and antistrange (Lambda macro) baryon production from square root of [s(NN)]=130 GeV Au+Au collisions at the Relativistic Heavy Ion Collider (RHIC). Rapidity density and transverse mass distributions at midrapidity are presented as a function of centrality. The yield of Lambda and Lambda; hyperons is found to be approximately proportional to the number of negative hadrons. The production of Lambda; hyperons relative to negative hadrons increases very rapidly with transverse momentum. The magnitude of the increase cannot be described by existing hadronic string fragmentation models alone.