超氧陰離子（superoxide redical, O2-）在生物體內具有殺菌的功能，但在超氧陰離子的濃度過高時，就會對身體的組織造成傷害。在環境上，超氧陰離子也被懷疑為海洋鞭毛藻類造成魚類大量死亡的原因。因此對超氧陰離子的濃度的感測便顯得重要。
本研究以開發非破壞性及高感度的超氧陰離子感測電極為目的。利用循環伏安法將混合價錯合物（mixed-valence complex）普魯士藍（Prussian Blue, PB）及ruthenium(II) hexacyanoferrate（RuHCF）修飾於玻璃化碳電極（GC）的表面，以感測超氧陰離子濃度。為了阻隔干擾物如維他命C（Ascoribic acid, AA）及尿酸（Uric acid, UA）等物質對感測訊號的影響，再以適當的電解聚合條件形成一層poly(o-phenylenediamine)（PPD）於電極修飾層之外。由此兩種修飾電極分別感測xanthine-xanthine oxidase（XOD）的超氧陰離子產生系統。結果發現PPD/PB/GC電極在感測電位定為370mV（vs. Ag/AgCl）時，雖然能除去UA的干擾，但是AA的干擾卻無法去除。而PPD/RuHCF/GC電極，在感測電位定在350mV（vs. Ag/AgCl）時，能夠避免UA及AA的干擾。這可能是PPD/PB/GC電極以high spin的鐵為反應中心，因具有較高的反應性，使得感測過程中易與AA起反應，而PPD/RuHCF/GC的反應中心為low spin的鐵，反應性較低，因此較能避免AA所造成的干擾。PPD/RuHCF/GC電極在xanthine濃度範圍為5*10-5M～9.5*10-4M之間有良好的線性（R2=0.9989），相對於超氧陰離子的濃度為2.9*10-7M～5.5*10-6M。

Superoxide anion radical (O2-) has received a great deal attention in the fields of biochemistry, medicine and environment. Mixed-valence complex (Prussian Blue and ruthenium(II) hexacyanoferrate ) modified electrodes are investigated for the detection of superoxide anion radical in this study. The superoxide anion radical amperometric sensors were made by poly(o-phenylenediamine) (PPD) electrodeposition onto Prussian Blue (PB) modified electrode and ruthenium(II) hexacyanoferrate (RuHCF) modified electrode. O2- was generated by Xanthine-Xanthine Oxidase system. The interference of ascoribic acid can be avoided with PPD/RuHCF/GC but PPD/PB/GC. The PPD/RuHCF/GC response exhibited a linear dependence on analytic concentration of xanthine in the range 5*10-5~9.5*10-4 M (O2- concentration 2.9*10-7~5.5*10-6 M).

Neuman, E. W. J. Chem. Phys. 1934, 2, 31
Sawyer, D. T.; Valentine J. S. Acc. Chem. Res. 1981, 14, 393
Bielski, B. H. J.; Allen, A. O. J. Phys. Chem. 1977, 81, 1048
Fulbert, J. C.; Succari, M.; Cals, M. J. Clin. Biochem. 1992, 25, 115
大坂武男、松本太，表面 1996, 34, 565
Grisham, M. B.; Hernandez, A. K.; Granger, D.N. Am. J. Physiol.
1986, 251, G567
Willian, A. P. Eds., Free Radicals in Biology ( Academic press, Inc., Landon ) 1984, 6, 47
施益民、呂鋒洲，當代醫學 1987, 16, 399
Carloni, P.; Blochl, P. E. Parrinello, M. J. Phys. Chem. 1995, 99, 1338
Fridovich I. Annu. Rev. Biochem. 1995, 64, 97
Song, M. I.; Bier, F. F.; Scheller, F. W. Bioelectrochem. Bioenerg. 1995, 38, 419
Lvovich, V.; Scheeline, A. Anal. Chem. 1997, 69, 454
Tatsuma, T.; Watanabe, T.; Tatsuma, S. Watanabe, T. Anal. Chem. 1994, 66, 190
Cooper, J. M.; Greenough, K. R.; McNeil C. J. J. Electroanal. Chem. 1993, 347, 267
Itaya, K.; Uchida, I.; Neff, V. D. Acc. Chem. Res. 1986, 19, 162
Robin, M. B.; Day, P. Adv. Inorg. Chem. Radiochem. 1967, 10, 247
Itaya, K.; Uchida, I. Inorg. Chem. 1986, 25, 389
Itaya, K.; Ataka, T.; Toshima, S. J. Am. Chem. Soc. 1982, 104, 4767
Itaya, K.; Akahoshi, H.; Toshima, S. J. Electrochem. Soc. 1982, 129, 1498
Holtzman, H. I. Eng. Chem. 1945, 37, 855
Itaya, K.; Shoji, N.; Uchida, I. J. Am. Chem. Soc. 1984, 106, 3423
Kaneko, M.; Okada, T. J. Electroanal. Chem. 1988, 255, 45
Krishnsn, V.; Xidis, A. L.; Neff,V. D. Analytica Chemica Acta 1990, 239, 7
Karyakin, A. A.; Gitelmacher, O. V.; Karyakin, E. E. Anal. Chem. 1995, 67, 2419
Gao, Z.; Zhou, X.; Wang, G.; Li, P.; Zhao, Z. Analytica Chemica Acta 1991, 244, 39
Pournaghi-Azar, M. H.; Razmi-Nerbin, H. J. Electroanal. Chem. 1998, 456, 83
Kulesza, P. J. J. Electroanal. Chem. 1990, 289, 103
Hadjur, C.; Jardon, P. J. Photochem. Photobio. B: Biology. 1995, 29, 147
Sanders, S. P.; Harrison, J. S.; Kuppusamy, P.; Sylvester, J. T.; Zweier, J. L. Free Radic. Biol. Med. 1994, 16, 753
Liu, D.; Sybert, T. E.; Qian, H.; Liu, J. Free Radic. Biol. Med. 1998, 25, 298
Stefan, M. J. Biolog. Chem. 1976, 251, 7504
Dong, S.; Deng, Q.; Cheng, G.; Analytica Chemica Acta 1993, 279, 235
Wang, J.; Wu, H. J. Electroanal Chem. 1995, 395, 287
Itaka, K,; Ataka, T.; Toshima, S. J. Am. Chem. Soc. 1982, 104, 3751