Further Applications of a Glutamate Oxidase Reactor for the Determination of the Neurotoxin P-Odap in a Flow Injection System

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1995-06

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Addis Ababa University

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A flow injection system involving immobilized GIOD reactor was employed to study the kinetics of the isomerization of ,8-0DAP to a-ODAP. The amino acid was oxidized by dissolved oxygen to produce hydrogen peroxide which subsequently reacted with T rinder chromogenic reagent (catalyzed by horseradish peroxidase in solution, HRP) to form red-coloured quinone imine dye for spectrophotometric detection at 512 nm. Injections of 20 III ,8-0DAP standards resulted in a linear range of 10 - 300 11M. Thermal treatment (at 80 DC) of ,8-0DAP standards and grass pea extracts reduced the FI response to 62 - 63 % of that before heating, because of the isomerization of the,8-isomer to the non-toxic a-isomer. This reconfirms the reported selectivity of GIOD to the toxin. The experimental convenience of the ,8-selective flow system has been exploited to study the effects of the neurotoxin concentration and temperature on the rates of ,8-a conversion. The results of these studies showed that the isomerization of the toxin to the nontoxic isomer followed zero order kinetics with an initial apparent rate constant equal to 15.26 lIM1min. The equilibrium time varied linearly with the initial concentration of ,8-0DAP. Values for the initial apparent rate constant of isomerization (at pH 7) were 3.56 lIM1min, 6.2811M1min, 15.2611M1min and 30.8911M1min at 60,70,80 and 90DC, respectively. Isomerization at pH 2 proceeded at a faster rate (24.5 lIM1min) than at pH 7. The complete flow injection set-up for the determination of ,8-0DAP in grass pea samples consisted of two packed-bed enzyme reactors in series, namely a mixture of GIOD (25 II\) and catalase (25 II\), and GIOD (250 III). The major interference from glutamate was destroyed by its quantitative oxidation in the pre-reactor. The product, hydrogen peroxide, was destroyed in the first reactor which contained GIOD and catalase. Most of the P-ODAP was oxidized in the big (250 III) reactor, because only a few percent of this compound is destroyed in the first reactor. The P-ODAP concentrations of five grass pea samples (0.599 - 0.749%) were determined from flow injection peaks of filtered extracts in phosphate buffer (pH 7). These results were found to be in good agreement with the values obtained using the OPT method

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Glutamate Oxidase

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