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研究生： 梁秉怡
Pin-i Liang
論文名稱： 化學修飾電極之光電性質研究
指導教授： 王忠茂
Wang, Chong-Mou
學位類別： 碩士
Master
系所名稱： 化學系
Department of Chemistry
論文出版年： 2002
畢業學年度： 90
語文別： 中文
論文頁數： 164
中文關鍵詞： 維生素B2 、修飾電極 、電化學發光
英文關鍵詞： Riboflavin, ECL, Ru(bpy)3 2+
論文種類： 學術論文
相關次數： 點閱：227  下載：0 
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    • 維生素B2是一具應用潛力的光催化劑，可於照光時氧化還原劑，如EDTA。為瞭解維生素B2之光電性質，本論文於是探討維生素B2在各種pH環境中的螢光光譜，並藉其螢光強度變化與電腦模擬進行分析比較，以推測維生素B2於光誘發反應中之主要反應形式。由於EDTA可有效還原激發態的維生素B2，致使其螢光強度趨於一穩定值，故於EDTA溶液中以光纖觀察維生素B2修飾電極之螢光光譜並研究其他電子傳遞媒介者，如Fe(III)、Cu(II)離子、Ruthenium Purple（簡稱RP）等，對還原態維生素B2之光電影響。
    此外，本論文也成功地利用黏土微粒製備得含Ru(bpy)32+修飾電極。實驗結果顯示：其光電性質與溶液態Ru(bpy)32+所測得的光電性質極為吻合。實驗結果亦顯示：此修飾電極與草酸(pH 10)共同被氧化時，可發生電化學發光反應。若於溶液中添加EDTA，不僅可有效增強發光度，更可穩定電極之發光效率。由於此一結果，我們成功藉以偵測水中的溶氧量。本論文也利用前述性質，製備得一含Ru(bpy)32+-草酸-EDTA的黏土白金修飾電極。此電極若再經葡萄糖酵素修飾，可藉以偵測葡萄糖，其線性範圍為：20μM – 5 mM；偵測極限為20μM (pH 10)。

    Vitamin B2 is a potential photocatalyst. When it is brought to its excited state, it can oxidize electron donors, like EDTA. In order to study the photoelectrochemical properties inherent to vitamin B2 and the influence from the third-party electron mediators, like Fe(III), Cu(II) and ruthenium purple, we monitored the emission spectra for vitamin B2 in the EDTA solutions.
    Besides, we also carried out studies on electrochemiluminescence (ECL) based on clay particles and Ru(bpy)32+. We successfully prepared a Ru(bpy)32+-containing clay modified electrode. This electrode showed a similar behavior as the solution counterpart. When this Ru(bpy)32+-containing clay modified electrode contacted with oxalic acid (pH 10), it emitted light at the potential near the formal potential of Ru(bpy)32+/3+. Furthermore, as the system was further added with EDTA, the ECL was greatly enhanced. Based on this result, we could use it to monitor the oxygen content in water. Merited by these properties, we also successfully prepared a Ru(bpy)32+-oxalate-EDTA-clay modified electrode for the detection of glucose after the resulting electrode was further incorporated with glucose oxidase. The resulting ECL showed a linear relationship with [glucose] in the range: 20 μM – 5 mM. The detection limit could reach 20 μM at this pH.

    目錄 圖目錄…………………………………………………………………………Ⅲ 表目錄……………………………………………………..………………ⅩⅡ 中文摘要………………………………………………………….……..ⅩⅣ 英文摘要…………………………………………………………………ⅩⅤ 第一章 緒論 1-1 維生素B2之簡介…………………………………………………….…………………..…1 1-2 Ru(bpy)32+之電化學發光………………………………………..…………..……...5 1-3 黏土與沸石…………………………………………………………………………………..8 1-4 酵素電極……………………………………………………………………………………..13 1-5 凝膠電極……………………………………………………………………………………..16 1-6 利用zero-zero bands計算激發態敏光劑之能階…………………..18 1-7 Stern-Volmer方程式……………………………………………………………….21 第二章 實驗 2-1 儀器設備…………………………………………………………………………………….23 2-2 化學藥品……………………………………………………………………………………25 2-3 儀器配置……………………………………………………………………………………28 2-4 黏土與沸石之前處理及製備………………………………………………….…30 2-5 修飾電極之製備與性質探討…………………………………………………….31 2-6 方波伏安法…………………………………………………………………………………41 第三章 B2的光電性質研究 3-1 B2的氧化還原機制探討…………………………………………………………….43 3-2 EDTA對B2修飾電極之螢光作用的探討…………………………………51 3-3 B2修飾電極之製備與研究………………………………………………………..57 3-4 B2-RP黏土凝膠薄層修飾電極之光電行為研究………………………77 3-5 維生素C對B2修飾電極之螢光作用的探討…………………………….82 第四章 Ru(bpy)32+的光電性質研究與應用 4-1 Ru(bpy)32+修飾電極之製備與研究…………………………………………..98 4-2 Ru(bpy)32+修飾電極之電化學發光研究……………………………..…108 4-3 最佳化條件………………………………………………………………………..…….132 4-4 Ru(bpy)32+修飾電極對溶液含氧量之偵測…………………………….141 4-5 Ru(bpy)32+電化學發光與過氧化氫偵測………………………………..143 4-6 Ru(bpy)32+複合修飾電極之電化學發光與葡萄糖偵測…………147 第五章 結論…………………………………………………………..154 第六章 參考文獻……………………………………………….….155

    1. Sliva E.; Edwards A. M.; Pacheco D., J. Nutr. Biochem., 1999, 10, 181.
    2. Szen-Gyorgyl, A. Introduction to a Submolecular Biology, Academic Press, New Yourk, 1960.
    3. Wang, X. M.; Chen, H. Y. Spectrochimica. Acta A. 1996, 51, 599.
    4. Birss. V. I.; Elzanowaska, H.; Turner, R. A. Can. J. Chem. 1988, 66, 86.
    5. Wang, X. M.; Chen, H. Y. J. Electroanal. Chem. 1998, 451, 187.
    6. Wingard, J.; Trends, L. B. Anal. Chem. 1984, 3, 235.
    7. Breyer, B.；Biegler, T. J. Electroanal. Chem. 1960, 1, 453.
    8. Breyer, B.；Biegier, T. Czecch. Chem. Commun. 1960, 25, 3348.
    9. Tatwawadi, S. V.；Bard, A. J. Anal. Chem. 1964, 36, 2.
    10. Foresti, M. L.；Pergola, F.；Aloisi, G.；Guidelli, R. J. Electroanal. Chem. 1982, 137, 341.
    11. Foresti, M. L.；Pergola, F.；Aloisi, G.；Guidelli, R. J. Electroanal. Chem. 1982, 137, 355.
    12. Senda, M.；Tachi, I. Rev. Polarog. 1962, 10, 142.
    13. Ksenzhek, O. S.；Petrova, S. A. Bioelectrochem, Bioenerg. 1983, 11, 105.
    14. Oster, G. K.；Prati, G. J. Am. Chem. Soc. 1957, 79, 595.
    15. Chirasree, S.-V.；Sukanta, G.；Bhowmik, B. Benoy.Chem. and Phy. of lipids. 1995, 76, 49.
    16. Parjuntaboribal, K.；Chaikum, N. Solar Energy. 1987, 38, 3, 149.
    17. Fujio, T.；Tetuo, K. Bull. Chem. Soc. Jpn. 1981, 54, 1305.
    18. Nadir A. W. J. Indian. Chem. Soc. 1998, 75(1), 18.
    19. Nobuyuki, K.；Makoto, O. J. Electrochem. Soc. Jap. 1969, 37(2), 81.
    20. Kraljic, I. Energy Storage, Trans. Int. Assem., 1st, 1979, 436.
    21. Dressick, W. J.；Meyer, T. J.；Durham, B. Isr. J. Chem. 1982, 22, 153.
    22. Gorner, H.；Kuhm, H. J. EPA Newslett. 1987, 31, 13.
    23. Konig B.; Pelka M.; Zieg M.; Ritter T.;Bouas-Laurent H.; Bonneau R.; and Desvergne J.P., J. Am. Chem. Soc. 1999, 121, 1681.
    24. Sliva E., Risi S. and Dose K., Radiat. Environ. Biophys., 1974, 11, 111.
    25. Yoshimura A.and Ohno T., Photochem. Photobiol., 1988, 48, 561.
    26. Sliva E., Gaule J., Radiat. Environ. Biophys., 1977, 14, 303.
    27. Ferrer I.and Sliva E., Environ. Biophys., 1985, 24, 63.
    28. Duran N., Haun M., Toledo S. M De., Cilento G.and Silva E., Photochem. Photobiol., 1983, 37, 247.
    29. Rojas J.and Silva E., Photochem. Photobiol., 1988, 47, 467.
    30. Silva E.; Ugarte R.; Andrade A. and Edwards A. M., Photochem. Photobiol. B: Biol., 1994, 23, 43.
    31. Garcia J.; Silva E., J. Nutr. Biochem. 1997,8, 341.
    32. Silva E.; Edwards A. M.; Pacheco D., J. Nutr. Biochem. 1999,10, 181.
    33. Cosnior S.; Nivibre V., Anal. Chem. 1997, 69, 3095.
    34. 傅雲珍、王忠茂，維他命B2之光電性質研究（2000）。
    35. Faulkner, L. R.; Bard, A. J. In Electroanalytical Chemistry, 1977, 10, 1.
    36. Lee, W. Y. Mikrochim. Acta 1997, 127, 19.
    37. Gerardi, R. D.; Barnett, N. W.; Lewis, S. W. Anal. Chim. Acta 1999, 378, 1.
    38. Ritchie, E. L.; Pastore, P. ; Wightman, R. M. J. Am. Chem. Soc. 1997, 119, 11920.
    39. Kapturkiewicz, A.; Graboeski, Z. R.; Jasny, J. J. Electroanal. Chem. 1990, 279, 55.
    40. Mussell, R. D.; Nocera, D. G. J. Am. Chem. Soc. 1988, 110, 2764.
    41. Kozlov, V. G.; Bulovic, V.; Burrows, P. E.; Forrest, S. R. Nuture 1997,389, 362.
    42. Engstorm, R. C.; Petersen, S. L. Anal. Chem. 1988, 60, 2385.
    43. Wightman, R. M.; Curtis, C. L.; McDonald, E. M. J. Phys. Chem. B. 1988, 102, 9991.
    44. Fan, F. R. F. ; Cliffel, D.; Bard, A. J. Anal. Chem. 1998, 70, 2941.
    45. Forrest, S. R.; Burrows, P. E.; Thompson, M. E. Chem. Ind. 1988, 70, 2941.
    46. Wallace, W. L.; Bard, A. J. J. Phys. Chem. 1979, 83, 1350.
    47. Abruna, H. D.; Bard, A. J. J. Am. Chem. Soc. 1982, 104, 2641.
    48. Maness, K. M.; Terrill, R. H.; Meyer, T. J.; Wightman, R. M. J. Am. Chem. Soc. 1996, 118, 10609.
    49. Elliott C. M.; Pichot F., J. Am. Chem. Soc. 1998, 120, 6781.Lyons, C. H.; Abbas, E. D.; Lee, J. K.;Rubner, M. F. J. Am. Chem. Soc. 1998, 120, 12100.Rubinstein, I.; Bard, A. J. J. Am. Chem. Soc. 1981, 103, 512.
    52. Faulker, L. R.; Bard, A. J.; Electroanalytical Chemistry 1977, 10, 1.
    53. Lee, W. Y.; Nieman, T. A. Anal. Chem. 1995, 67, 1789.
    54. White, H. S.; Bard, A. J.; J. Am. Chem. Soc. 1982, 104, 6891. Gerardi, R. D.; Barnett, N. W.; Lewis, S. W. Anal. Chim. Acta 1999, 378, 1.
    56. Zu, Y. B.; Bard, A. J. Anal. Chem. 2000, 72, 3223.
    57. Zu Y.; Bard A. J., Anal. Chem. E, PAGE EST: 3,4,5.
    58. Alexander, C. J.; Richter, M. M. Anal. Chim. Acta 1999, 402, 105.
    59. Wang, H.; Richter, Xu G., Dong S. Talanta. 2001, 55, 61.
    60. Collinson M. M.; Taussig J.; and Martin S. A., Chem. Mater., 1999, 11, 2594.
    61. Chen, X.; Sato, M.; Anal. Sci. 1995, 2, 749.
    62. Zorzi M.; Pastore P.; Magno F., Anal. Chem., 2000, 72, 4934.
    63. . Cheng S. F, J. Chin. Chem. Soc., 1989, 45, 127.
    64. Ghosh P. K.; Bard A. J., J. Am. Chem. Soc., 1983, 105, 5691.
    65. Zen J. M.; Lo C. W., Anal. Chem., 1995, 68, 2635.
    66. Lei C.and Deng J., Anal. Chem., 1996, 68, 3344.
    67. Lee S. A.; Futch A., J. Phys. Chem., 1990, 94, 4998.
    68. Futch A.; Subramanian P., J. Electrroanal. Chem., 1993, 362, 177.
    69. Kaviratna P. D.and Pinnavaia T. J., J. Electroanal. Chem., 1995, 385, 163.
    70. Thomas J. K., Chem. Rev., 1993, 93, 301.
    71. Oyama N.; Anson F. C., J. Electroanal. Chem., 1986, 199, 467.
    72. Walcarius A., Electroanalysis, 1996, 11, 971.
    73. Yoon K. B. Chem. Rev., 1993, 93, 321.
    74. Parton R. F., Vankelecom I. F. J., Casselmam M. J. A., Bezoukhanova C. P., Uytterhoeven J. B.and Jacobs P. A., Nature, 1994, 370, 541.
    75. Marko-Varga G., Burestedt E., Svensson C. J., Emneus J., Gorton L., Ruzgas T., Electroanalysis, 1996, 8, 1121.
    76. Boewrs L. D.; Carr P. W., Anal. Chem. , 1976, 48, 544A.
    77. Weetall H. H., Anal. Chem. ,1974, 46, 602A.
    78. lane R. F.and Hubbard T., J. Electroanal. Chem. , 1973, 91, 1285.
    79. Degani Y.and Heller A., J. Phys. Chem., 1987, 91, 1285.
    80. Foulds N. C. and Lowe C. R., Anal. Chem., 1988, 60, 2473.
    81. Ghobadi S.; Csoregi E.; Marko-VarGa G.; Gorton L., Current Separation, 1996, 14, 94.
    82. Cox J. A.; Jawoeski R. K., Anal. Chem., 1989, 61, 2176.
    83. Shyu S. C.and Lo C. W., Anal. Chem. 1997, 144, 3419.
    84. Ouyang C. S., Wang C. M., J. Electrochem. Soc., 1998, 145, 2657.
    85. Wang, J.; Pamidi V. A. Anal Chem. 1997, 69, 4490.
    86. Wang, B.; Li, B.; Wang, Z.; Xu, G.; Wang, Q.; Dong, S. Anal. Chem. 1999, 71, 1935.
    87. Makote, R.; Collinson, M. M. Anal. Chim. Acta 1999, 394, 195.
    88. Tadanaga, K.; Morinaga, J.; Matsuda, A.; Minami, T. Chem. Mater. 2000, 12, 590.
    89. Ichinose, I.; Senzu, H.; Kunitake, T. Chem. Mater. 1997, 9, 1296.
    90. Obert, R.; Dave, R. C. J. Am. Chem. Soc. 1999, 121, 12192.
    91. Ha, S. Y.; Kim, S. J. Electroanal. Chem. 1999, 468, 131.
    92. Oskam, G.; Searson, P. C. J. Phys. Chem. B 1998, 102, 2464.
    93. Hattori, A.; Shimoda, K.; Tada, H.; Ito, S. Langmuir 1999, 15, 5422.
    94. Mayo, E. I.; Lochner, E. J.; Stiegman, A. E. J. Phys. Chem. B 1999, 130, 9383.
    95. Mann, S.; Burkett, S. L.; Davis, S. A.; Fowler, C. E.; Mendelson, N. H.; Sim, S. D.; Walsh, D.; Whilton, N. T. Chem. Mater. 1997, 9, 2300.
    96. Bertolotti, B. G. ; Previtali, C. M. Photochem. Photobiol. A : Chem. 1997, 103, 115.
    97. Eriksen, J. ; Foote, C. S. J. Phys. Chem. 1978, 82, 2659.
    98. Eriksen, J. ; Foote, C. S. J. Am. Chem. Soc. 1980, 102, 6083.
    99. Vauthey, E. J. Phys. Chem. A 1997, 101, 1635.
    100. Lanzalunga, O. ; Crescenzi, C. ; Baciocchi, E. Tetrahedron 1997, 101, 1635.
    101. Shiraishi, Y. ; Taki, Y. ; Hirai, T. Chem. Commun. 1998, 2601.
    102. Bindra, D. S. ; Zhang, Y. ; Wilson, G. S. ; Sternberg, R. ; Thevenot, D. R. ; Moatti, D. ; Reach. G. Anal. Chem. 1991, 633, 1692.
    103. Barker, G. C. ; Jenkins, I. L. Analyst 1952, 77, 685.
    104. Ramaley, L. ; Krause, S., Anal. Chem. 1969, 41, 1362.
    105. Osteryoung, J. G. ; Osteryoung, R. A. Anal. Chem. 1985, 57, 101A.
    106. Brett, M. A.; Brett, A. M. O. Electrochemistry principles, methods, and applications, Oxford science publications, 1993, 219.
    107. Mlakar, M. Anal. Chim. Acta 1993, 276, 367.
    108. Buchanan, E. B.; Soleeta, H. D. Talanta 1983, 30, 459.
    109. Alsdtadt, J. H.; Dewald, H. D. Anal. Chem. 1992, 64, 3176.
    110. Draper R. D.; Ingraham L. L., Arch. Bioichem. Biophys., 1968, 125, 802.
    111. Konig B., Pelka M., Zieg H., Ritter T., Bouas-Laurent H., Bonneau R., Desvergne J. P., J. Am. Chem. Soc., 1999, 121, 1681.
    112. 徐素卿、王忠茂，多鐵黏土修飾電極之應用與研究（1996）。
    113. Ghosh P. K.; Bard A. J., J. Am. Chem. Soc., 1983, 105, 5691.
    114. Shichi T., Takagi K., Journal of Photochemistry and Photobiology C: Photochemistry Reviews, 2000, 1 , 113.

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