Asymptotic analysis and estimates of blow‐up time for the radial symmetric semilinear heat equation in the open‐spectrum case

We estimate the blow‐up time for the reaction diffusion equation u_t=Δu+ λf(u), for the radial symmetric case, where f is a positive, increasing and convex function growing fast enough at infinity. Here λ>λ^*, where λ^* is the ‘extremal’ (critical) value for λ, such that there exists an ‘extremal’ weak but not a classical steady‐state solution at λ=λ^* with ∥w(?, λ)∥_∞→∞ as 0<λ→λ^*?. Estimates of the blow‐up time are obtained by using comparison methods. Also an asymptotic analysis is applied when f(s)=e^s, for λ?λ^*?1, regarding the form of the solution during blow‐up and an asymptotic estimate of blow‐up time is obtained. Finally, some numerical results are also presented. Copyright © 2007 John Wiley & Sons, Ltd.     

Oriented immobilization of Desulfovibrio gigas hydrogenase onto carbon electrodes by covalent bonds for nonmediated oxidation of H2

The orientation of hydrogenase bound covalently to a pyrolytic graphite edge electrode modified with a 4-aminophenyl monolayer can be modulated via electrostatic interactions during the immobilization step. At low ionic strength and when the amino groups of the electrode surface are mostly protonated, the hydrogenase is immobilized with the negatively charged region that surrounds its 4Fe4S cluster nearer to the protein surface facing the electrode. This allows direct electron transfer between the immobilized hydrogenase and the electrode, which is observed by the strong catalytic currents measured in the presence of the H2 substrate. Therefore, a very stable enzymatic electrode is produced that catalyzes nonmediated H2 oxidation.     

Combined capillary gas chromatography/ion trap mass spectrometry quantitative methods using labeled or unlabeled internal standards

Three methods of operating an ion trap mass spectrometer (ITMS) were investigated for the determination of quantitative information by combined capillary GC/MS and GC/MS/MS. Separate regression Lines for a hexynone drug were examined by using bath unlabeled and stable-isotope-labeled internal standards. The ITMS modes of operation examined were (1) the full-scan, rf-voltage-only mode, useful on ion trap detectors as well as on the ITMS, (2) a scan using combined rf and dc voltages (rf/dc) for mass-selective storage analyses, and (3) rf/dc followed by collision-induced dissociation, Results of over 200 analyses in the 0.1–10 ng on-column range, with 5 ng of internal standard, showed that the unlabeled internal standard, separated by retention time on the capillary GC column, gave the best relative standard deviatiod (less than 5% over the range) and linear correlations (r ² typically > 0.9992).     

Assessment of silver and gold substrates for the detection of amphetamine sulfate by surface enhanced Raman scattering (SERS)

Methods of detection of amphetamine sulfate using surface enhanced Raman scattering (SERS) from colloidal suspensions and vapour deposited films of both silver and gold are compared. Different aggregating agents are required to produce effective SERS from silver and gold colloidal suspensions. Gold colloid and vapour deposited gold films give weaker scattering than the equivalent silver substrates when high concentrations of drug are analysed but they also give lower detection limits, suggesting a smaller surface enhancement but stronger surface adsorption. A 10(-5) mol dm(-3) solution (the final concentration after addition of colloid was 10(-6) mol dm(-3)) of amphetamine sulfate was detected from gold colloid with an RSD of 5.4%. 25 microl of the same solution could be detected on a roughened gold film. The intensities of the spectra varied across the film surface resulting in relatively high RSDs. The precision was improved by averaging the scattering from several points on the surface. An attempt to improve the detection limit and precision by concentrating a suspension of gold colloid and amphetamine sulfate in aluminium wells did not give effective quantitation. Thus, positive identification and semi-quantitative estimation of amphetamine sulfate can be made quickly and easily using SERS from suspended gold colloid with the appropriate aggregating agents.     

Graphical aids and scanning modes for tandem mass spectrometry

In tandem mass spectrometry, where typically one analyser is used to study the reactions of ions selected by another analyser from a mixture leaving the ion source, the output contains an additional dimension of information compared to that from conventional mass spectrometry. The increase in dimensionality tends to make the results less easy to assimilate and interpret, but the difficulties may be overcome in large measure by presenting the results in an appropriate graphical form. This review deals with the use of graphical representations of three-dimensional data to display the results of experiments in tandem mass spectrometry. Perspective diagrams or contour maps can be used to show the identity of the parent and daughter ions for all of the reactions occurring in a tandem mass spectrometer, including reactions of positive ions, reactions of negative ions and charge inversion reactions. A graphical approach is particularly valuable when double focusing mass spectrometers are used for tandem mass spectrometry, because it can make it much easier to establish the origin of the ions contributing to an observed peak and thus to determine whether interference is occurring. Factors bearing on the choice of a coordinate system are discussed. Relationships characterizing the more important simple and linked scanning modes are listed and the features to which they correspond in two selected coordinate systems are shown. Factors that influence the resolution of neighbouring peaks by sector field tandem mass spectrometers are discussed.     

Proteomic analysis of simulated occupational jet fuel exposure in the lung

We analyzed protein expression in the cytosolic fraction prepared from whole lung tissue in male Swiss-Webster mice exposed 1 h/day for seven days to aerosolized JP-8 jet fuel at concentrations of 1000 and 2500 mg/m3, simulating military occupational exposure. Lung cytosol samples were solubilized and separated via large scale, high resolution two-dimensional electrophoresis (2-DE) and gel patterns scanned, digitized and processed for statistical analysis. Significant quantitative and qualitative changes in tissue cytosol proteins resulted from jet fuel exposure. Several of the altered proteins were identified by peptide mass fingerprinting, confirmed by sequence tag analysis, and related to impaired protein synthetic machinery, toxic/metabolic stress and detoxification systems, ultrastructural damage, and functional responses to CO2 handling, acid-base homeostasis and fluid secretion. These results demonstrate a significant but comparatively moderate JP-8 effect on protein expression and corroborate previous morphological and biochemical evidence. Further molecular marker development and mechanistic inferences from these observations await proteomic analysis of whole tissue homogenates and other cell compartment, i.e., mitochondria, microsomes, and nuclei of lung and other targets.     

Esmodil: an acetylcholine mimetic resurfaces in a Southern Australian marine sponge Raspailia (Raspailia) sp

Bioassay directed fractionation of a Raspailia (Raspailia) sp. (Order Poecilosclerida; Family Raspailiidae) collected during scientific trawling operations off the Northern Rottnest Shelf yielded as nematocidal agents the known metabolites, phorboxazoles A (1) and B (2). Further examination revealed the new natural product but known synthetic compound, esmodil (3). The structure for 3 was confirmed by spectroscopic analysis and total synthesis.     

Sequencing of sulfonic acid derivatized peptides by electrospray mass spectrometry

We report the application of nanoelectrospray ionization tandem mass spectrometry (nES-MS/MS) and capillary LC/microelectrospray MS/MS (cLC/&mgr;ES-MS/MS) for sequencing sulfonic acid derivatized tryptic peptides. These derivatives were specifically prepared to facilitate low-energy charge-site-initiated fragmentation of C-terminal arginine-containing peptides, and to enhance the selective detection of a single series of y-type fragment ions. Both singly and doubly protonated peptides were analyzed by MS/MS and the results were compared with those from their derivatized counterparts. Model peptides and peptides from tryptic digests of gel-isolated proteins were analyzed. Derivatized singly protonated peptides fragment in the same way by nES-MS/MS as they do by post-source decay matrix-assisted laser desorption/ionization mass spectrometry (PSD-MALDI-MS). They produce fragment ion spectra dominated by y-ions, and the simplified spectra are readily interpreted de novo. Doubly protonated peptides fragment in much the same way as their non-derivatized doubly protonated counterparts. The fragmentation of doubly protonated derivatives is especially useful for sequencing peptides that possess a proline residue near the N-terminus of the molecule. The singly protonated forms of these proline-containing derivatives often show enhanced fragmentation on the N-terminal side of the proline and considerably reduced fragmentation on the C-terminal side. In addition, sulfonic acid derivatization increases the in-source fragmentation of arginine-containing peptides. This could be useful for sequence verification and sequence tagging for use in single stage mass spectrometry. Copyright 2000 John Wiley & Sons, Ltd.     

The Synthesis and Liquid Crystal Properties of Some 2,5-Disubstituted Pyridines

Abstract

The synthesis is reported of fifteen three-ring 2,5-disubstituted pyridines and two pyridine-N-oxides where the pyridine rings carry a variety of alkyl, aryl, cyclohexyl, cyclohexylethyl and fluorinated-aryl substituents. The mesomorphic transition temperatures for these compounds have been measured; all the compounds show enantiotropic phases. The different substituent effects are discussed and comparisons are made with previous work on analogous systems where the hetero-function is replaced by C-F.