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

(1)通过酰胺键（MPr、MPs和MPg）将金属卟啉（M-P）固定在离子交换树脂、硅胶和玻璃微珠上。以M-P为原料制备了金属-八溴卟啉（M-BrP）。(2)研究了Mn^<3+>-Pg对过氧化氢的类过氧化物酶催化活性。结果表明，部分Mn^<3+>-Pg具有过氧化物酶样活性和过氧化物酶样活性。该活性适用于过氧化氢的测定。(3)我尝试开发一种新的过氧化氢荧光流动分析方法。这是基于Mn^<3+>-卟啉修饰的载体的过氧化物酶样活性。因此，我们开发了过氧化氢的新方法。(4)研究了MPs和MPg对有机过氧化物的类过氧化物酶催化活性。结果表明，部分MPs和MPg表现出过氧化物酶样活性有机过氧化物。该活性适用于过氧化亚油酸的测定。(5)研究了Co^<3+>-四（巯基）卟啉（Co- tsppr）改性的离子交换树脂在空气中催化苯酚与氧的氧化反应。还发现Co-TSPPr在NADH与过氧化氢的氧化反应中表现出催化活性。(6)用钴卟啉（Co-Ps）固定硅胶可加速抗坏血酸氧化酶催化的氧化还原反应。利用这种活性以及Co-Ps的过氧化物酶样活性，建立了一种新的抗坏血酸流动分析方法。(7)为揭示改性载体类酶活性的机理，对改性载体的共振拉曼光谱进行了研究。此外，用金属卟啉修饰的硅胶填充的色谱柱可以作为基于π-π电子相互作用的固定相。

(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.