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

(1)金属卟啉（MPr，MPs，MPg）通过酰胺键固定在离子交换树脂、硅胶和玻璃微珠上。以八溴卟啉为原料合成了金属八溴卟啉（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。因此，部分Mn^<3+>-Pg显示出过氧化物酶样活性以及过氧化物酶活性。本活度适用于过氧化氢的测定。(3)本文尝试建立一种新的过氧化氢荧光流动分析方法。其基于用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。因此，一些MP和MPg显示出过氧化物酶样活性的有机过氧化物。该活性适用于亚油酸氢过氧化物的测定。(5)研究了Co^<3+>-四（磺基苯基）卟啉（Co-TSPPr）改性的离子交换树脂对苯酚氧化反应的催化作用。研究还发现Co-TSPPr在NADH与过氧化氢的氧化反应中表现出催化活性。(6)研究了钴卟啉（Co-Ps）固定化硅胶对抗坏血酸氧化酶催化氧化还原反应的促进作用。利用这种活性以及过氧化物酶样活性的钴-磷，一种新的流动分析抗坏血酸。(7)为了揭示修饰载体的类酶活性机理，研究了修饰载体的共振拉曼光谱。此外，填充有用金属卟啉改性的硅胶的柱可以有利地作为基于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.