Determination of (34)S:(32)S ratios by FTIR spectroscopy

A new method for determining (34)S:(32)S ratios using Fourier transform infrared spectroscopy has been developed. The four sulphur-containing gases SCO, H(2)S, SF(6) and SO(2) are assessed as possible compounds for the spectroscopic measurements, from which, after a consideration of available lines showing a clear isotopic shift and also of possible synthetic routes to the gas starting from a range of natural sample types, SO(2) was selected for further development of the instrumental method for the isotopic ratio determination. Sulphur in the samples present as the element, as metal sulphides or as organosulphur compounds, is converted by heating with V(2)O(5) into gaseous SO(2), and a part of the 518 cm(-1) band is recorded in the absorbance mode. The optimisation of instrumental parameters and of the chemical reaction conditions is described, and the results from the application of the method to the measurement of the level of enrichment of (34)S in a soil fungus are presented. The agreement between results at the natural abundances of 4.2% was better than 0.04% absolute for a sample size of 1.5 mg of sulphur.     

Information theory in analytical chemistry: basic terms, definitions and interpretations. Arbeitskreis "Automation in der Analyse"

The most important terms in information theory (information, character, code, message and signal) are defined and interpreted with reference to automation in analytical chemistry. The aim of this communication and the earlier one dealing with systems theory, is to facilitate communication and understanding between all specialists working on or with automated systems for analysis.     

The numerical integration of relative equilibrium solutions. The nonlinear Schrodinger equation

We analyse different error propagation mechanisms for conservativeand nonconservative time-integrators of nonlinear Schrödingerequations. We use a geometric approach based on interpretingwaves as relative equilibria.     

Using an Expert System to Monitor an Automatic Stock Control System

The theory of the control of stock is well understood, and a large number of firms use automatic stock control and ordering techniques as a major part of their inventory control systems. However, the effectiveness of such automatic stock control systems depends on the correct selection of system parameters for each item in the inventory and on the accurate reporting of information. It is not unusual for errors to be made in both the selection of parameters and the entry of data, and regular failures of either can cause severe problems in stock control. It is generally difficult for a human stock controller to discover errors quickly because of the large number of items that is usually found in a company inventory. This paper describes the use of an expert system to examine stock records and diagnose anomalies in the data provided or parameters applied to individual items in a stock control system. The expert system ‘reasons’ from symptoms such as reports from the forecasting system or high stock levels, to defects in the stock model used or data-collection processes, and from there to possible remedial action. Results are presented for runs of the expert system on a simulated stock control system.     

Genome mapping by random anchoring: A discrete theoretical analysis

As a part of the international human genome project, large-scale genomic maps of human and other model organisms are being generated. More recently, mapping using various anchoring (as opposed to the traditional fingerprinting) strategies have been proposed based largely on mathematical models. In all of the theoretical work dealing with anchoring, an anchor has been idealized as a point on a continuous, infinite-length genome. In general, it is not desirable to make these assumptions, since in practice they may be violated under a variety of actual biological situations. Here we analyze a discrete model that can be used to predict the expected progress made when mapping by random anchoring. By virtue of keeping all three length scales (genome length, clone length, and probe length) finite, our results for the random anchoring strategy are derived in full generality, which contain previous results as special cases and hence can have broad application for planning mapping experiments or assessing the accuracy of the continuum models. Finally, we pose a challenging nonrandom anchoring model corresponding to a more efficient mapping scheme.     

Separation of diarylethene-based photoswitchable isomeric compounds by high-performance liquid chromatography and supercritical fluid chromatography

Diarylethene-based photoswitches have become very popular over the last few decades for potential applications in chemistry, materials science, and biotechnology due to their unique physical and chemical properties. We report the isomeric separation of a diarylethene-based photoswitchable compound using high-performance liquid chromatography. The separated isomers were characterized by ultraviolet-visible spectroscopy and mass spectrometry confirmed the isomeric nature of the compounds. The isomers were purified by preparative high-performance liquid chromatography, providing fractionated samples to study the isomers individually. A total amount of 13 mg of an isomer of interest was fractionated from a solution of 0.4 mg/ml of the isomeric mixture. Because the preparative high-performance liquid chromatographic method required large quantities of solvent, we explored the use of supercritical fluid chromatography as an alternative separation mode which, to the best of our knowledge, is the first time this technique is used to separate diarylethene-based photoswitchable compounds. Supercritical fluid chromatography provided faster analysis times while maintaining sufficient baseline resolution for the separated compounds and consuming less organic solvent in the mobile phase compared to high-performance liquid chromatography. It is proposed that the supercritical fluid chromatographic method be upscaled and used in future fractionation of the diarylethene isomeric compounds, becoming a more environmentally benign approach for compound purification.     

Concerted and stepwise proton-coupled electron transfers in aquo/hydroxo complex couples in water: oxidative electrochemistry of [Os(II)(bpy)(2)(py)(OH(2))](2+)

Successive oxidation of transition metal(II) aqua complexes (M(II)OH(2) to M(III)OH) is a domain in which proton-coupled electron transfer reactions are extremely common. The mechanism of these PCET reactions-concerted or stepwise-is an important issue in the understanding and design of natural or artificial systems catalyzing the formation of dioxygen by four-electron oxidation of water. Concerted proton-coupled electron transfer from an aqua metal(II) to a hydroxo metal(III) complex requires the close proximity of a proton-accepting group with a pK value between those of the aqua complexes. Otherwise, stepwise electron-proton or proton-electron pathways involving high-energy intermediates are followed. Concerted proton-electron pathways involving water as proton-acceptor or proton-donor group are inefficient. Cyclic voltammetry of the title complex in buffered aqueous solution and re-examination of previous results for the same complex attached to an electrode surface are used to establish these conclusions, which provide a starting point on the route to higher degrees of oxidation, such as those involved in the catalysis of water oxidation.     

Determination of saccharides in atmospheric aerosol using anion-exchange high-performance liquid chromatography and pulsed-amperometric detection

An improved method is described for the quantification of primary sugars, sugar alcohols and anhydrosugars in atmospheric aerosols, making use of separation by high-performance anion-exchange chromatography (HPAEC) with pulsed amperometric detection (PAD). Quartz fibre filters from high-volume samplers were extracted with water and the extract injected directly. Repeatability is typically 4% RSD, for e.g. levoglucosan at 50 ng m(-3) in air, better for winter levels around 700 ng m(-3). Limits of detection for individual sugars are in the range 0.02-0.05 microg mL(-1) in solution, corresponding to 2-5 ng m(-3) from a 20 m(3) air sample. The overlap of arabitol and levogluocosan is overcome by using a Dionex PA-1 column, with appropriate control of eluent composition, and peak deconvolution software, allowing quantification of both sugars in difficult summer samples containing low-levels of levoglucosan. Analysis of a set of ambient aerosol samples by both GC-flame ionization detection and HPAEC-PAD shows good agreement. The new method has the advantage of requiring no sample pretreatment or derivatization and is thus well suited to handling large numbers of samples.