1,2]- or [2,3]-rearrangement of onium ylides of allyl and benzyl ethers and sulfides via in situ-generated iodonium ylides

Iodonium ylides, generated in situ with bisacetoxyiodobenzene, are converted to allyl- or benzyl-substituted oxonium or sulfonium ylides via rhodium- or copper-catalyzed carbene transfer. Except for the S-benzyl example, the resulting ylides undergo rearrangement to the corresponding 2-substituted heterocycles. This demonstrates the first use of iodonium ylides as diazoketone surrogates for the generation and rearrangement of onium ylide intermediates. This abbreviated one-step method proceeds in comparable yields relative to the corresponding two-step route employing diazoketone intermediates.     

Thermophysical Properties of High-Temperature Reacting Mixtures of Carbon and Water in the Range 400–30,000 K and 0.1–10 atm. Part 1: Equilibrium Composition and Thermodynamic Properties

This paper is devoted to the calculation of the chemical equilibrium composition and thermodynamic properties of reacting mixtures of carbon and water at high temperature. Equilibrium particle concentrations and thermodynamic properties including mass density, molar weight, entropy, enthalpy and specific heat at constant pressure, sonic velocity, and heat capacity ratio are determined by the method of Gibbs free energy minimization, using species data from standard thermodynamic tables. The calculations, which assume local thermodynamic equilibrium, are performed in the temperature range from 400 to 30,000 K for pressures of 0.10, 1.0, 3.0, 5.0 and 10.0 atm. The properties of the reacting mixture are affected by the possible occurrence of solid carbon formation at low temperature, and therefore attention is paid to the influence of the carbon phase transition by comparing the results obtained with and without considering solid carbon formation. The results presented here clarify some basic chemical process and are reliable reference data for use in the simulation of plasmas in reacting carbon and water mixtures together with the need of transport coefficients computation.     

Application of affinity selection-mass spectrometry assays to purification and affinity-based screening of the chemokine receptor CXCR4

Affinity selection-mass spectrometry (AS-MS) is a sensitive technology for identifying small molecules that bind to target proteins, and assays enabled by AS-MS can be used to delineate relative binding affinities of ligands for proteins. 'Indirect' AS-MS assays employ size-exclusion techniques to separate target-ligand complexes from unbound ligands, and target-associated ligands are then specifically detected by liquid chromatography mass spectrometry. We report how indirect AS-MS binding assays with known reference control compounds were used as guideposts for development of an optimized purification method for CXCR4, a G-protein coupled chemokine receptor, for which we sought novel antagonists. The CXCR4 purification method that was developed was amenable to scale-up and enabled the screening of purified recombinant human CXCR4 against a large combinatorial library of small molecules by high throughput indirect AS-MS. The screen resulted in the discovery of new ligands that competed off binding of reference compounds to CXCR4 in AS-MS binding assays and that antagonized SDF1α-triggered responses and CXCR4-mediated HIV1 viral uptake in cell-based assays. This report provides a methodological paradigm whereby indirect AS-MS-based ligand binding assays may be used to guide optimal integral membrane protein purification methods that enable downstream affinity selection-based applications such as high throughput AS-MS screens.     

Reduction of nitroarenes,azoarenes and hydrazine derivatives by an organic super electron donor

Reduction of nitrobenzene by excess organic electron donor, 12, affords diphenylhydrazine in a reaction where azobenzene oxide and azobenzene are likely intermediates. No cleavage of the N-N σ-bond is seen under photoactivation conditions, whereas traces are seen under thermal activation. Hydrazone derivatives were prepared to explore the cleavage of N-N σ-bonds; the results show that a low-lying LUMO assists the transition state for accepting an electron, and the stabilisation that the potential fragments from N-N bond cleavage afford to the fragments is important in determining whether cleavage is observed.     

Laser-induced surface migration via surface plasmons

A classical model coupling a charged adspecies to a laser-induced surface plasmon is presented. Such coupling can enhance the rate and specify the direction of surface migration. For the particular case of an atomic oxygen ion of charge ?1 adsorbed on aluminum which is exposed to CO₂ laser radiation of intensity 1 W/cm², the velocity of migration (61.3 μm/s) is five orders of magnitude greater than the usual thermal velocities observed at room temperature.     

PIV space-time resolution of flow behind blast waves

An ultra-high speed, time-resolved particle image velocimetry (PIV) system is developed to measure velocity fields created by explosive detonators. When initiated into a gas, the detonators generate blast waves that propagate outwards from the origin of initiation at supersonic speeds. The PIV system consists of a custom eight-pulse Nd:YAG laser system and an ultra-high speed camera system comprising four dual-frame CCD cameras optically combined to share a single optic axis. The system is capable of sampling the flow field four times at up to 333 MHz or eight times at up to 8 MHz. System development is discussed, and preliminary application to the complex flow behind the blast wave from an exploding bridge wire detonator is demonstrated.     

A rapid heating and high magnetic field thermal analysis technique

Journal of Thermal Analysis and Calorimetry - A new thermal analysis technique is described that allows measurements to be performed on bulk samples at extreme heating and cooling rates and in high...     

Author Index for Volume 14

Authors Index

Author Index for Volume 14     

Konzertierte nukleophile aromatische Substitutionen

Jüngste Entwicklungen in der experimentellen und theoretischen Chemie haben zur Identifizierung einer schnell wachsenden Klasse von nukleophilen aromatischen Substitutionsreaktionen geführt, die einem konzertierten Mechanismus (cS_NAr) folgen, und nicht dem klassischen, zweistufigen S_NAr‐Mechanismus. Während klassische S_NAr‐Reaktionen auf die substantielle Aktivierung des aromatischen Ringes durch elektronenziehende Substituenten angewiesen sind, ist eine solche Aktivierung für den konzertierten Reaktionsverlauf nicht zwingend nötig.