Combined supercritical-fluid chromatography/mass spectrometry in the analysis of diuron in plasma using on-line phase-system switching

On-line sample pretreatment by means of the phase-system switching approach is an interesting technique for the analysis of aqueous samples, e.g., plasma, by means of supercritical-fluid chromatography. In order to analyse plasma samples the following analytical procedure is used. The plasma sample is injected on to a short precolumn, which is washed with water and subsequently dried with nitrogen. Next, the solutes are desorbed with the supercritical mobile phase, analysed with packed-column supercritical-fluid chromatography and detected with either a UV detector or a mass spectrometer, equipped with a moving-belt interface. The herbicide diuron is selected as a test compound to study the feasibility of this approach. Using a selective detector the procedure is sufficiently sensitive to detect diuron in plasma, but not appropriate to detect the diuron metabolites in a post-mortem plasma sample. These have been identified with liquid chromatography/mass spectrometry. The detection limit of diuron in plasma using the procedure described is about 30 ng/mL.     

Three-dimensional structure of Saccharomyces cerevisiae inorganic pyrophosphatase complexed with cobalt and phosphate ions

Crystals of Saccharomyces cerevisiae inorganic pyrophosphatase suitable for X-ray diffraction study were grown by cocrystallization of the enzyme with cobalt chloride and imidodiphosphate. Saccharomyces cerevisiae is a metal-dependent enzyme which catalyzes hydrolysis of inorganic pyrophosphate to orthophosphate. The three-dimensional structure of this enzyme was solved by the molecular-replacement method and refined at 1.8 Å resolution to an R factor of 19.5%. Cobalt and phosphate ions were revealed in the active centers of both identical subunits (A and B) of the pyrophosphatase molecule. In subunit B, a water molecule was found between two cobalt ions. It is believed that this water molecule acts as an attacking nucleophile in the enzymatic cleavage of the pyrophosphate bond. It was demonstrated that cobalt ions and a phosphate group occupy only part of the potential binding sites (two chemically identical and crystallographically independent subunits have different binding sites). The arrangement of ligands and the structure of the nucleophile-binding site are discussed in relation to the mechanism of action of the enzyme and the nature of the metal activator.     

Numerical analysis of time-dependent Boussinesq models

In this paper we analyse numerical models for time-dependent Boussinesq equations. These equations arise when so-called Boussinesq terms are introduced into the shallow water equations. We use the Boussinesq terms proposed by Katapodes and Dingemans. These terms generalize the constant depth terms given by Broer. The shallow water equations are discretized by using fourth-order finite difference formulae for the space derivatives and a fourth-order explicit time integrator. The effect on the stability and accuracy of various discrete Boussinesq terms is investigated. Numerical experiments are presented in the case of a fourth-order Runge-Kutta time integrator.     

Synthesis and characterization of poly(vinyl alcohol)‐graft‐[poly(D,L‐lactide)/poly(D,L‐lactide‐co‐glycolide)] hydrogels

Poly(D ,L ‐lactide) and poly(D ,L ‐lactide‐co‐glycolide) with various composition and with one methacrylate and one carboxylate end group were synthesized and grafted onto poly(vinyl alcohol) (PVA) via the carboxylate group. The graft copolymers were crosslinked via the methacrylate groups using a free radical initiator. The polymer networks were characterized by means of NMR and studied qualitatively by means of IR spectroscopy. The influence of the glycolide content in the polyester grafts and of the number of ester units in the grafts on thermal properties and swellability were studied as well. The high swellability in water is characteristic of all hydrogels. Differential scanning calorimetry (DSC) showed a single glass transition temperature that occurs in the range between 51 and 69 °C. Thermogravimetric analysis (TGA) of the networks showed the main loss in weight in the temperature range between 290 and 370 °C. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4536–4544, 2007     

An anisotropic fibre-network model for mechano-sorptive creep in paper

In this paper a simplified network model for mechano-sorptive creep is presented, which is a further development of an earlier paper [Strömbro, J., Gudmundson, P., 2008. Mechano-sorptive creep under compressive loading – a micromechanical model. International Journal of Solids and Structures 45 (9), 2420–2450.]. It is assumed that the anisotropic hygroexpansion of the fibres leads to large stresses at the fibre bonds when the moisture content changes. The resulting stress state will accelerate creep if the fibre material obeys a constitutive law that is non-linear. Fibre kinks are included in order to capture experimental observations of larger mechano-sorptive effects in compression than in tension. Moisture dependent material parameters and anisotropy in the fibre distribution have been introduced. Theoretical predictions based on the model are compared to experimental results for an anisotropic paper both under tensile and compressive loading at varying moisture content and it is found that the important features in the experiments are captured by the model. Different kinds of drying conditions have also been examined.