Enzyme-like Activities of Resins Modified with Metalloporphyrins and their Analytical Applications as Artificial Solid-Enzymes

为了开发人工固体酶，我们研究了金属卟啉修饰的离子交换树脂（M-P_r）及其分析应用. M-TPPS_r的类过氧化物酶活性及其分析应用研究表明，Mn^<3+>-四（磺苯基）卟啉修饰的离子交换树脂（Mn-TPPS_r）可作为过氧化物酶的模拟物用于葡萄糖的测定。本文用Mn-TPPS_r代替固定化过氧化物酶，建立了流动注射分光光度法和荧光法测定过氧化氢的方法。此外，我们还发现钴卟啉修饰的离子交换树脂对有机过氧化物具有类似过氧化物酶的活性. M-P_r的类尿酸酶活性研究发现，Mn^<3+>-四（甲基吡啶-4-基）卟啉修饰的离子交换树脂具有类尿酸酶活性，可代替尿酸酶测定尿酸。共振拉曼光谱表明，钴卟啉的活性是由钴离子中Co^<3+>和Co^<2+>的氧化还原循环引起的. M-P_r的类抗坏血酸氧化酶活性及其分析应用研究表明，Co^<3+>-四（磺基苯基）卟啉修饰的离子交换树脂具有很强的类抗坏血酸氧化酶活性，可用于去除干扰过氧化氢测定的抗坏血酸。共振拉曼光谱表明，改性树脂的活性是由上述氧化还原循环引起的，因此，我们能够开发出酶的人工模拟树脂。

To develop artificial solid-enzymes, we investigated ion-exchange resins modified with metalloporphyrins (M-P_r) and their analytical applications as follows.1. Peroxidase-like Activities of M-P_r and Their Analytical Applications.It has been shown that the ion-exchange resin modified with Mn^<3+>-tetrakis(sulfophenyl)porphine (Mn-TPPS_r) can be used for the determination of glucose as a mimesis of peroxidase. Spectrophotometric and fluorometric flow injection methods of hydrogen peroxide has been developed by using Mn-TPPS_r in place of immobilized peroxidase. In addition, we have found that the ion-exchangeresin modified with cobalt-porphine shows the peroxidase-like activity for organic peroxides.2. Uricase-like Activities of M-P_r.It has been found that the ion-exchange resin modified with Mn^<3+>-tetrakis(methylpyridinium-4-yl)porphine shows the uricase-like activity and can be used for the determination of uric acid in place of uricase. The activity has been revealed to be caused from redox cycle of Co^<3+> and Co^<2+> in in cobalt-porphine on the basis of resonance Raman spectra.3. Ascorbate Oxidase-like Activities of M-P_r and Their Analytical Applications.It has been shown that the ion-exchange resin modified with Co^<3+>-tetrakis(sulfophenyl)porphine exhibits strong ascorbate oxidase-like activity and can be used for removal of ascorbate that interfers the determination of hydrogen peroxide. The resonance Raman spectra of the modified resins have been revealed that the activity is caused from the essential same redox cycle to be described above.In conclusion, we were able to develop the artificial mimetic resins of enzymes.