Analytical Applications of Carriers Immobilized with Analogues of Metal-Porphyrins as Artificial Solid Mimesis of Enzymes.

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(1) Metal-porphyrins (M-P) were immobilized to ion-exchange resins, silica gels and glass beads through amide-bonds (MPr, MPs and MPg). Metal-octabromoporphyrins (M-BrP) were also prepared from M-P.(2) Peroxidase-like catalytic activities of Mn^<3+>-Pg for hydrogen peroxide were investigated. Consequently, some of Mn^<3+>-Pg was revealed to exhibit the peroxidase-like activity as well as peroxidase. This activity is applicable to determination of hydrogen peroxide.(3) I have attempted to develop a new method for a new fluorescent flow analysis of hydrogen peroxide. which is based on peroxidase-like activity of a carrier modified with Mn^<3+>-porhyrin. As the result, we developed the new method for hydrogen peroxide.(4) Peroxidase-like catalytic activities of MPs and MPg for organic peroxides were investigated. Consequently, some of MPs and MPg was revealed to exhibit the peroxidase-like activity organic peroxides. This activity is applicable to determination of linoleate hydroperoxide.(5) It was revealed that an ion-exchange resin modified with Co^<3+>-tetrakis (sulfophenyl) porphine (Co-TSPPr) catalyzes oxidative reactions of phenol with oxygen in air. It was also found that Co-TSPPr exhibits a catalytic activity in the oxidative reaction of NADH with hydorogen peroxide.(6) Silica gels immobilized with cobalt-porphyrin (Co-Ps) was proved to accelerate the redox reaction catalyzed by ascorbate-oxidase. By using this activity as well as peroxidase-like activity of Co-Ps, a new flow analysis of ascorbate was developed.(7) To reveal the mechanism of the enzyme-like activities of the modified carriers, the resonance Raman spectra of the modified carriers were investigated. In addition, a column packed with silica gels modified with metal-porphyrins could be advantageous as a stationary phase based on the π-π electron interaction.