Determination of neurotransmitter systems in human cerebrospinal fluid and rat nervous tissue by high-performance liquid chromatography with on-line data evaluation

We describe an improved high-performance liquid chromatographic method for the determination of tyrosine, 5-hydroxytryptamine, 5-hydroxyindoleacetic acid, tryptophan and homovanillic acid in cerebrospinal fluid and nerve tissue, using the new microbore cartridges with 5 micron average particle size. The first four substances are quantified fluorometrically and the last two electrochemically. Both detectors are connected to the same integrator through a relay which can be switched as required. Data are collected in an on-line personal computer and evaluated statistically. An improvement in the method for extraction and separation of catecholamines is also reported.     

Off-resonance TROSY (R1 rho - R1) for quantitation of fast exchange processes in large proteins

Current solution NMR experiments for characterizing conformational exchange processes in large proteins are limited to exchange rates ca. 500-3000 s-1. A TROSY-based constant relaxation time (R1rho - R1) experiment is designed to extend this capability to measure motion with rates up to 105 s-1 in large macromolecules. The experiment combines off-resonance spin-lock rf fields, which provide access to the faster time-scale dynamics, with TROSY coherence selection, which extends the molecular-weight range available for study. When implemented on the 53-kDa dimeric enzyme triosephosphate isomerase, the experiment yielded substantial gains in signal-to-noise (up to 60%) over current experiments at modest static magnetic fields (14.1 T). The TROSY (R1rho - R1) experiment should therefore be of general utility for investigation of fast conformational exchange events in large proteins.     

Mechanism of Iron Oxide Formation from Iron Pentacarbonyl‐Doped Low‐Pressure Hydrogen/Oxygen Flames

A chemical reaction mechanism was developed for the formation of iron oxide (Fe₂O₃) from iron pentacarbonyl (Fe(CO)₅) in a low‐pressure hydrogen–oxygen flame reactor. In this paper, we describe an extensive approach for the flame‐precursor chemistry and the development of a novel model for the formation of Fe₂O₃ from the gas phase. The detailed reaction mechanism is reduced for the implementation in two‐dimensional, reacting flow simulations. The comprehensive simulation approach is completed by a model for the formation and growth of the iron oxide nanoparticles. The exhaustive and compact reaction mechanism is validated using experimental data from iron‐atom laser‐induced fluorescence imaging. The particle formation and growth model are verified with new measurements from particle mass spectrometry.     

Relationships between strain,microstructure and oxide growth at the nano‐ and microscale

In the present article, the relationships between oxidation processes, surface strains and the microstructure of duplex stainless steels were investigated. Specimens were oxidized at 500 °C under secondary vacuum for 1 h to form a thin oxide film (thickness in the range of 20–50 nm). Such specimens were considered as the model system for developing novel methods of analysis in understanding the behavior of passive films. The interfacial strain field after oxidation was measured experimentally at the microscale using the point grid method. On the other hand, the chemical composition of the oxide film was determined at the submicroscopic scale by means of local scanning Auger spectroscopy (with a spot diameter of 50 nm). Local variations of the chemical composition of the oxide film were analyzed according to the specimen microstructure and the strain field. Copyright © 2008 John Wiley & Sons, Ltd.     

Geometric modeling and analysis of detonation cellular stability

A geometric model with a low computational complexity capable of simulating detonation behavior in physical systems is proposed. In support of the geometric model development, a series of cylindrical 1D simulations with a variable size initiation kernel are performed in hydrogen-oxygen mixtures. From these 1D simulations a detonation cell stabilization mechanism is identified. The stabilization mechanism is predicated on the size of the gap between the pressure and temperature fronts at the point where the average pressure front velocity along one cell length is equal to the CJ velocity. This gap, in a multidimensional detonation, is the ignition kernel of a subsequent blast, and dictates the formation of the subsequent cell. Serial analysis of blasts in this context leads to a unique stable blast kernel size for any mixture, which, within the uncertainty of the initial kernel state, can predict the experimental cell length for mixtures considered in this study. Using a tabulation of the 1D simulations as an input, a formulation and sample results of the geometric model are shown. The geometric model can reproduce both qualitative and quantitative features of experimental detonation cellular structure.     

Investigation of lengthscales, scalar dissipation, and flame orientation in a piloted diffusion flame by LES

This work investigates the structure of a diffusion flame in terms of lengthscales, scalar dissipation, and flame orientation by using large eddy simulation. This has been performed for a turbulent, non-premixed, piloted methane/air jet flame (Flame D) at a Reynolds-number of 22,400. A steady flamelet model, which was represented by artificial neural networks, yields species mass fractions, density, and viscosity as a function of the mixture fraction. This will be shown to suffice to simulate such flames. To allow to examine scalar dissipation, a grid of 1.97 × 10⁶ nodes was applied that resolves more than 75% of the turbulent kinetic energy. The accuracy of the results is assessed by varying the grid-resolution and by comparison to experimental data by Barlow, Frank, Karpetis, Schneider (Sandia, Darmstadt), and others. The numerical procedure solves the filtered, incompressible transport equations for mass, momentum, and mixture fraction. For subgrid closure, an eddy viscosity/diffusivity approach is applied, relying on the dynamic Germano model. Artificial turbulent inflow velocities were generated to feature proper one- and two-point statistics. The results obtained for both the one- and two-point statistics were found in good agreement to the experimental data. The PDF of the flame orientation shows the tilting of the flame fronts towards the centerline. Finally, the steady flamelet approach was found to be sufficient for this type of flame unless slowly reacting species are of interest.     

AES investigations of Ar+ ion retention in Si during Ar sputtering

Argon retention in silicon has been studied by AES in the energy range between 1 and 15 keV at bombardment fluences up to ∼10¹⁸ ions/cm². AES data of implanted argon in silicon near the surface region, as obtained during sputtering, can be interpreted qualitatively by a simple model of ion collection. Discrepancies between calculated and measured saturation values of collected argon ions indicate that during implantation at high fluences addition surface effects become important and that the simple model of ion collection has to account for this. Quantitative AES correlated with RBS indicates pronounced concentration gradients of argon in silicon near surface regions.     

Thin film characterization by laser interferometry combined with SIMS

Thin film properties of technologically important materials (Si, GaAs, SiO₂, WSi_x) have been measured by using a novel technique that combines secondary ion mass spectrometry (SIMS) and laser interferometry.The simultaneous measurement of optical phase and reflectance as well as SIMS species during ion sputtering yielded optical constants, sputtering rates and composition of thin films with high depth resolution. A model based on the principle of multiple reflection within a multilayer structure, which considered also transformation of the film composition in depth and time during sputtering, was fitted to the reflectance and phase data. This model was applied to reveal the transformation of silicon by sputtering with O ₂ ⁺ ions. Special attention was paid to the preequilibrium phase of the sputter process (amorphization, oxidation, and volume expansion). To demonstrate the analytical potential of our method the multilayer system WSi_x/poly-Si/SiO₂/Si was investigated. The physical parameters and the stoichiometry of tungsten suicide were determined for annealed as well as deposited films. A highly sensitive technique that makes use of a Fabry-Perot etalon integrated with a Michelson type interferometer is proposed. This two-stage interferometer has the potential to profile a sample surface with subangstroem resolution.