No abstract

The utility of electrospray and tandem mass spectroscopy (ES-MS and MS-MS) in anthocyanin characterization was tested using different anthocyanin extracts. Anthocyanins were semipurified by using a C-18 resin, washed with acidified water followed by ethyl acetate, and recovered with acidified methanol. Samples were directly injected into a mass spectrometer in either aqueous or methanolic solutions. The positive charge of anthocyanins favored fast and effective ES-MS detection of intact molecular ions. Little interference from other compounds was observed when the ethyl acetate cleaning procedure was used. Tandem mass spectroscopy provided clear and characteristic fragmentation patterns. The voltage used affected only the proportions at which these fragments were present. ES-MS may be used as a fast procedure for identification of anthocyanins, requiring minimal sample preparation. In combination with HPLC, ES-MS and MS-MS could be very powerful tools for anthocyanin characterization and monitoring the authenticity of anthocyanin-containing fruit juices and vegetable extracts.

Abstract. The paper presents an integrated view of the population structure and its role in establishing the ionisation state of light elements in dynamic, finite density, laboratory and astrophysical plasmas. There are four main issues, the generalised collisional-radiative picture for metastables in dynamic plasmas with Maxwellian free electrons and its particularising to light elements, the methods of bundling and projection for manipulating the population equations, the systematic production/use of state selective fundamental collision data in the metastable resolved picture to all levels for collisonal-radiative modelling and the delivery of appropriate derived coefficients for experiment analysis. The ions of carbon, oxygen and neon are used in illustration. The practical implementation of the methods described here is part of the ADAS Project.

A widely used alternative to a full Breit-Pauli R-matrix calculation of electronimpact excitation is the transformation of S-or K-matrices, calculated in pure LS coupling, to intermediate coupling. Here we present a transformation method, based on multichannel quantum defect theory (MQDT), that eliminates the problems associated with standard transformation methods and leads to accurate level-to-level electron-impact excitation cross sections. Instead of transforming the physical S-or K-matrices, we employ MQDT to generate unphysical K-matrices in pure LS coupling; we then treat all channels as open and transform these matrices to intermediate coupling. Finally, we generate the physical Kmatrices from the intermediate-coupled unphysical K-matrices. To illustrate the accuracy of this method, we compare cross sections for several transitions in Fe 14+ determined using: (i) the standard transformation method in which the LS-coupled physical S-matrices are transformed to intermediate coupling; (ii) an MQDT transformation method, used by others, in which the unphysical LS-coupled K-matrices are transformed to pure jK coupling; (iii) our intermediate coupling frame transformation (ICFT) method and (iv) a full Breit-Pauli R-matrix calculation. It is shown that our ICFT method eliminates the problems associated with the other two transformation methods and leads to cross sections that agree very well with those determined from a full Breit-Pauli R-matrix calculation. Furthermore, the ICFT method can be applied to complex atomic systems which are intractable to a full Breit-Pauli calculation.

We review the development of the time-dependent close-coupling method to study atomic and molecular few body dynamics. Applications include electron and photon collisions with atoms, molecules, and their ions.

Fluorescein was covalently attached through a cystamine linker group to carboxy-derivatized polyacrylamide microspheres to generate phagocytosable particles containing fluorescent reporter groups. A unique feature of these beads is that the dye was recoverable in near-quantitative yield from intracellular environments by thiol reduction of the cystamine disulfide bond. Fluorescence microscopy indicated that individual neutrophils could bind as many as approximately 20 serum-opsonized beads, although no appreciable cellular association was observed for unopsonized beads. By using methyl viologen to quench external fluorescence, it was demonstrated that 70-90% of the neutrophil-associated fluorescein on opsonized beads was inaccessible to the medium. The particle-bound fluorescein underwent near-stoichiometric conversion to chlorinated derivatives when reacted with HOCl or the cell-free myeloperoxidase (MPO)-H2O2-Cl- system; products were identified by HPLC separation and electrospray ionization mass spectrometry of the recovered dye. Fluorescence changes accompanying phagocytosis were consistent with chlorination of the dye; fluorescence spectrometric and chemical trapping measurements indicated that intraphagosomal chlorination was far more extensive than extracellular chlorination. Yields of recovered chlorofluoresceins determined by HPLC indicated that sufficient HOCl had been produced intracellularly to kill entrapped bacteria. Fluorescein chlorination coincided approximately with phagocytosis and stimulated uptake of O2 by the cells. Demonstration that HOCl is produced within phagosomes in sufficient concentrations to kill bacteria on a time scale associated with death constitutes strong evidence in support of a primary role for HOCl in the microbicidal action of neutrophils.

No abstract

We present complete collisional-radiative modelling results for the soft x-ray emission lines of Fe16+ in the 15 Å–17 Å range. These lines have been the subject of much controversy in the astrophysical and laboratory plasma community. Radiative transition rates are generated from fully relativistic atomic structure calculations. Electron-impact excitation cross sections are determined using a fully relativistic R-matrix method employing 139 coupled atomic levels through n = 5. We find that, in all cases, using a simple ratio of the collisional rate coefficient times a radiative branching factor is not sufficient to model the widely used diagnostic line ratios. One has to include the effects of collisional-radiative cascades in a population model to achieve accurate line ratios. Our line ratio results agree well with several previous calculations and reasonably well with tokamak experimental measurements, assuming a Maxwellian electron-energy distribution. Our modelling results for four EBIT line ratios, assuming a narrow Gaussian electron-energy distribution, are in generally poor agreement with all four NIST measurements but are in better agreement with the two LLNL measurements. These results suggest the need for an investigation of the theoretical polarization calculations that are required to interpret the EBIT line ratio measurements.