Nonideal thermoequilibrium calculations using a large product species data base

Thermochemical data fits for approximately 900 gaseous and 600 condensed species found in the JANAF tables (Chase et al. 1985) have been completed for use with the TIGER non-ideal thermoequilibrium code (Cowperthwaite and Zwisler 1973). The TIGER code has been modified to allow systems containing up to 400 gaseous and 100 condensed constituents composed of up to 50 elements. Gaseous covolumes have been estimated following the procedure outlined by Mader (1979) using estimates of van der Waals radii for 48 elements and three-dimensional molecular mechanics. Molecular structures for all gaseous components were explicitly defined in terms of atomic coordinates in Å (Hobbs and Baer 1992a). The Becker-Kistiakowsky-Wilson equation of state (BKW-EOS) has been calibrated near C-J states using detonation temperatures measured in liquid and solid explosives and a large product species data base. Detonation temperatures for liquid and solid explosives were predicted adequately with a single set of BKW parameters. Values for the empirical BKW constants ,, , and were 0.5, 0.174, 11.85, and 5160, respectively. Values for the covolume factors, _i, were assumed to be invariant. The liquid explosives included mixtures of hydrazine nitrate with hydrazine, hydrazine hydrate, and water; mixtures of tetranitromethane with nitromethane; liquid isomers ethylnitrate and 2-nitroethanol; and nitroglycerine. The solid explosives included HMX, RDX, PETN, Tetryl, and TNT. Color contour plots of HMX equilibrium products as well as thermodynamic variables are shown in pressure and temperature space. Similar plots for a pyrotechnic reaction composed of TiH₂ and KClO₄ are also reported. Calculations for a typical HMX-based propellant are also discussed.This article was processed using Springer-Verlag T_EX Shock Waves macro package 1.0 and the AMS fonts, developed by the American Mathematical Society.     

Understanding hERG inhibition with QSAR models based on a one-dimensional molecular representation

Blockage of the potassium channel encoded by the human ether-a-go-go related gene (hERG) is well understood to be the root cause of the cardio-toxicity of numerous approved and investigational drugs. As such, a cascade of in vitro and in vivo assays have been developed to filter compounds with hERG inhibitory activity. Quantitative structure activity relationship (QSAR) models are used at the very earliest part of this cascade to eliminate compounds that are likely to have this undesirable activity prior to synthesis. Here a new QSAR technique based on the one-dimensional representation is described in the context of the development of a model to predict hERG inhibition. The model is shown to perform close to the limits of the quality of the data used for model building. In order to make optimal use of the available data, a general robust mathematical scheme was developed and is described to simultaneously incorporate quantitative data, such as IC50 = 50 nM, and qualitative data, such as inactive or IC50 > 30 μM into QSAR models without discarding any experimental information.     

Experimentally determined temperature–concentration phase diagrams of monodisperse alkanes with chains containing between 100 and 200 carbons

The temperature–concentration phase (T–c) diagrams of the uniform n-alkanes C₁₀₂H₂₀₆, C₁₂₂H₂₄₆, C₁₆₂H₃₂₆, and C₁₉₈H₃₉₈ in toluene have been determined for solution concentrations in the range 0.1 to 6% (w/w). The shorter alkanes display a “classical” behavior with the expected, strong dependence of dissolution temperature on solution concentration. The longest alkane displays a very different, “polymeric” type behavior with a concentration independent dissolution temperature (for both extended and folded chain crystals). It is argued that no current theory of polymer dissolution is able to explain this behavior. It is suggested that a locally higher concentration occurs when molecules are partially attached to a crystal either during crystallization or dissolution, and that this increased local concentration accounts for the independence of dissolution temperature on the global concentration. There are some small variations in the dissolution temperature of crystals of the same thickness grown at the same concentration, but at different temperatures. These are ascribed to differences in the stacking of the separate layers. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 3188–3200, 1999     

Anionic N-heterocyclic carbenes with N,N'-bis(fluoroaryl) and N,N'-bis(perfluoroaryl) substituents

A series of rhodium complexes, [Rh(cod)(NHC-F(x))(OH(2))] (cod = 1,5-cyclooctadiene; NHC = N-heterocyclic carbene), incorporating anionic N-heterocyclic carbenes with 2-tert-butylmalonyl backbones and 2,6-dimethylphenyl (x = 0), 2,6-difluorophenyl (x = 4), 2,4,6-trifluorophenyl (x = 6), and pentafluorophenyl (x = 10) N,N'-substituents, respectively, has been prepared by deprotonation of the corresponding zwitterionic precursors with potassium hexamethyldisilazide, followed by immediate reaction of the resulting potassium salts with [{RhCl(cod)}(2)]. These complexes could be converted to the related carbonyl derivatives [Rh(CO)(2)(NHC-F(x))(OH(2))] by displacement of the COD ligand with CO. IR and NMR spectroscopy demonstrated that the degree of fluorination of the N-aryl substituents has a considerable influence on the σ-donating and π-accepting properties of the carbene ligands and could be effectively used to tune the electronic properties of the metal center. The carbonyl groups on the carbene ligand backbone provided a particularly sensitive probe for the assessment of the metal-to-ligand π donation. The ortho-fluorine substituents on the N-aryl groups in the carbene ligands interacted with the other ligands on rhodium, determining the conformation of the complexes and creating a pocket suitable for the coordination of water to the metal center. Computational studies were used to explain the influence of the fluorinated N-substituents on the electronic properties of the ligand and evaluate the relative contribution of the σ- and π-interactions to the ligand-metal interaction.     

Application of proton radiography in experiments of relevance to inertial confinement fusion

Multi-Mev proton beams generated by target normal sheath acceleration (TNSA) during the interaction of an ultra intense laser beam (I≥10¹⁹ W/cm²) with a thin metallic foil (thickness of the order of a few tens of microns) are particularly suited as a particle probe for laser plasma experiments. The proton imaging technique employs a laser-driven proton beam in a point-projection imaging scheme as a diagnostic tool for the detection of electric fields in such experiments. The proton probing technique has been applied in experiments of relevance to inertial confinement fusion (ICF) such as laser heated gasbags and laser-hohlraum experiments. The data provides direct information on the onset of laser beam filamentation and on the plasma expansion in the hohlraum’s interior, and confirms the suitability and usefulness of this technique as an ICF diagnostic.     

Modulational instability in a silicon-on-insulator directional coupler: role of the coupling-induced group velocity dispersion

We report frequency conversion experiments in silicon-on-insulator (SOI) directional couplers. We demonstrate that the evanescent coupling between two subwavelength SOI waveguides is strongly dispersive and significantly modifies modulational instability (MI) spectra through the coupling induced group velocity dispersion (GVD). As the separation between two 380-nm-wide silicon photonic wires decreases, the increasing dispersion of the coupling makes the GVD in the symmetric supermode more normal and suppresses the bandwidth of the MI gain observed for larger separations.     

Nanostructured biosensors built by layer-by-layer electrostatic assembly of enzyme-coated single-walled carbon nanotubes and redox polymers

In this study, we describe the construction of glucose biosensors based on an electrostatic layer-by-layer (LBL) technique. Gold electrodes were initially functionalized with negatively charged 11-mercaptoundecanoic acid followed by alternate immersion in solutions of a positively charged redox polymer, poly[(vinylpyridine)Os(bipyridyl)2Cl(2+/3+)], and a negatively charged enzyme, glucose oxidase (GOX), or a GOX solution containing single-walled carbon nanotubes (SWNTs). The LBL assembly of the multilayer films were characterized by UV-vis spectroscopy, ellipsometry, and cyclic voltammetry, while characterization of the single-walled nanotubes was performed with transmission electron microscopy, Raman spectroscopy, thermogravimetric analysis, and X-ray photoelectron spectroscopy. When the GOX solution contained single-walled carbon nanotubes (GOX-SWNTs), the oxidation peak currents during cyclic voltammetry increased 1.4-4.0 times, as compared to films without SWNTs. Similarly the glucose electro-oxidation current also increased (6-17 times) when SWNTs were present. By varying the number of multilayers, the sensitivity of the sensors could be controlled.     

Characterizing the radiation response of Cherenkov glass detectors with isotopic sources

Cherenkov detectors are widely used for particle identification and threshold detectors in high-energy physics. Glass Cherenkov detectors that are sensitive to beta emissions originating from neutron activation have been demonstrated recently as a potential replacement for activation foils. In this work, we set the groundwork to evaluate large Cherenkov glass detectors for sensitivity to MeV photons through first understanding the measured response of small Cherenkov glass detectors to isotopic gamma-ray sources. Counting and pulse height measurements are acquired with reflected glass Cherenkov detectors read out with a photomultiplier tube. Simulation was used to inform our understanding of the measured results. This simulation included radioactive source decay, radiation interaction, Cherenkov light generation, optical ray tracing, and photoelectron production. Implications for the use of Cherenkov glass detectors to measure low energy gamma-ray response are discussed.     

Simulated response of Cherenkov glass detectors to MeV photons

Cherenkov detectors are widely used for particle identification in high-energy physics and for track imaging in astrophysics. Glass Cherenkov detectors that are sensitive to beta emissions originating from neutron activation have been demonstrated recently as a potential replacement for activation foils. In this work, we evaluate Cherenkov glass detectors for sensitivity and specificity to MeV photons through simulations using Geant4. The model has been previously compared with measurements of isotopic gamma sources. It includes Cherenkov generation, light transport, light collection, photoelectron production and time response in photomultiplier tubes. The model incorporates measured, wavelength-dependent absorption and refractive index data. Simulations are conducted for glasses the size of fabricated samples and also for the same glasses in monolithic, square-meter-size. Implications for selective detection of MeV photons are discussed.