臺灣博碩士論文加值系統

本研究為利用鈷青素(cobalt phthalocyanine, CoPC)修飾碳墨電極來發展兼具快速分析與高偵測靈敏度的二硫代胺基甲酸鹽(dithiocarbamate)類農藥的電化學感測器，並以鈉乃浦(Nabam)為研究對象。此一修飾電極的製備乃是利用鈷青素與碳墨均勻混合後，以環己酮稀釋(w/w=1/9)，再以dip-coating的方式修飾於旋轉玻璃碳電極上，並於電化學安培法來偵測Nabam分子。成功地利用CoPC催化Nabam的特性，將偵測電壓由+200mV降低至-200mV。由實驗結果顯示，本系統於0.1M磷酸緩衝溶液中(pH=7.5)，施加電位+0.2V(vs.Ag/AgCl)，電極轉速1600rpm下，測得Nabam的線性範圍0.1~3.0μM(R=0.9991)，偵測極限濃度為20nM(S/N=3)，系統反應時間(response time)為8.6秒，其靈敏度可達1.13μA/μM×cm2，此結果完全符合JMPR meeting (Joint FAO/WHO Meeting on Pesticide Residues)對此一系列農藥的偵測極限濃度要求。

This paper reports a sensitive electrochemical sensor for the detection of dithiocarbamate (Nabam) by using a cobalt phthalocyanine (CoPC) mocified carbon ink electrode. The modified electrode was prepared by mixing CoPC and cyclehexanone (w/w=1/9) diluted carbon ink. A portion of 1.0ml mixture was then dip-coated on a rotate disk glass carbon electrode and air dried for 15mins. The cyclic voltammetry indicates that CoPC catalysis the oxidation of Nabam at -200mV which is 400mV less than that of a bare glassy carbon electrode. A typical calibration plot of Nabam at +200mV(vs. Ag/AgCl), rotating speed=1600rpm, in 0.1M phosphate buffer pH 7.5, is linear over the concentration range of 0.1 to 3.0mM(R=0.9991). The detection limit was estimated about 20nM(S/N=3), and response time was 8.6 sec at the injection of 1.0mM Nabam . This sensitive scheme satisifies the sensitivity requirement of JMPR meeting (Joint FAO/WHO Meeting on Pesticide Residues).

目錄(Contents)
圖表目錄………………………………………………………….…VI
第一章 緒論……………………………………………………1
1-1 .農藥偵測之重要性 ………………………………………..1
1-2.農藥的分類…………………………………………………….2
1-3.偵測農藥的方法………………………………………………4
1-3-1 UV光譜法………………………………………………...5
1-3-2 螢光偵測法……………………………………………….5
1-3-3 電化學偵測法……………………………………………7
1-3-4 生化感測器………………………………………………9
1-4.化學修飾電極………………………………………………..10
1-4-1修飾方法…………………………………………………10
化學吸附單分子薄膜………………………………………10
共價鍵法……………………………………………………11
多層高分子薄膜……………………………………………13
非均相多分子薄膜…………………………………………15
1-4-2修飾功能……………………………………………….…16
電催化(electrocatalysis) ……………………………………16
預濃縮(preconcentration) ……………………………..……17
薄膜阻隔(membrane barriers) …………………………..…18
電釋放(electroreleasing) …………………………………...19
1-5. 二硫代胺基甲酸鹽的簡介……………………………...19
1-5-1 二硫代胺基甲酸鹽的用途及毒性…………………..20
1-5-2 二硫代胺基甲酸鹽的偵測……………………………20
1-6 鈷青素的特性…………………………………………….24
1-6-1 鈷青素的性質…………………………………..……24
1-6-2 鈷青素的應用………………………………………..24
1-7 本研究的目的………………………………………………..25
第二章 實驗部分……………………………...………………26
2-1 儀器……………………………………………………………..26
2-2 藥品……………………………………………………………..26
2-3 電極的製備…………………………………………………..27
第三章 結果與討論……………………………….…………28
3-1 鈷青素修飾電極的特性及催化鈉乃浦氧化的機
制探究…………………………… 28
(1) 鈷青素修飾電極催化鈉乃浦氧化的機制探究….28
(2) 電子傳遞速率κ值的計算……………………………..30
3-2 鈉乃浦感測器偵測條件之最適化……………………30
催化劑的組成…………………………………………………31
偵測電位的決定………………………………………………31
電極轉速的效應………………………………………………32
溶液氫離子濃度的影響……………………………………..33
電解質的效應…………………………………………………34
3-4 鈷青素之鈉乃浦感測器分析特性評估…………35
(1) 分析鈉乃浦之感測器的特性探討………………………35
(2) 干擾物的測定………………………………………………35
3-5結論……………………………………………………………..36
參考資料…………………………………………………………..48
符號對照表……………………………………………..………..54

1. Edwards, C. A. In World Directory of Pesticide Control Organisations; Ekstrom G., Ed.; Royal Society of Chemistry: Cambridge, 1994; pp. 1-24.
2. 王一雄 土壤環境污染與農藥; 國立編譯館編著; 明文書局股份有限公司: 台北市, 1997.
3. U.S. Environmental Protection Agency. Integrated Risk Information System; Washington, D.C., 1995.
4. Hennion, M.-C.; Pichon, V.; Chen, L. Anal. Chim. Acta 1995, 311, 429.
5. Lawrence, J. F.; Menard, C.; Hennion, M. -C.; Pichon, V.; Goffic, L.; Durand, N. Journal of Chromatography A 1996, 732, 277.
6. Walters, S. M.; Westerby, B. C.; Gilvydis D. M. J. Chromatog. 1984, 317, 533.
7. Gennaro, M. C.; Abrigo, C.; Giacosa, D.; Rigotti, L.; Liberatori, A. J. Chromatog. A 1995, 718, 81.
8. Schechter, I.; Hassoon, S. Anal. Chim. Acta 1998, 368, 77.
9. Aaron, J. -J.; Coly, A. Anal. Chim. Acta 1998, 360, 129.
10. Sojo, L. E. J. Chromatog. A 1997, 788, 87.
11. Okihashi, M.; Obana, H.; Hori, S. Analyst 1998, 123, 711.
12. Brett, A. M. O.; Delerue-Matos, C. M.; Garrido, E. M.; Lima, J. L. C. Talanta 1998, 46, 1131.
13. Valcarcel, M.; Luque, M.; Rios, A. Analyst 1998, 123, 2383.
14. Martinez, R. C.; Gonzalo, E. R.; Garcia, F. G.; Mendez, J. H. J. Chromatog. 1993, 644, 49.
15. Cordero, B. M.; Pinto, C. G.; Pavon, J. L. P. Anal. Chem. 1995, 67, 2606.
16. Kumaran, S.; Tran-Minh, C. Anal. Biochem. 1992, 200, 187.
17. Marty, J. L.; Mionetto, N.; Noguer, T.; Ortega, F.; Roux, C. Biosensors Bioelect. 1993, 8, 273.
18. Lorenzo, E.; Rosa, C. L.; Pariente, F.; Hernandez, L. Anal. Chim. Acta 1994, 295, 273.
19. Skladal, P.; Fiala, M.; Krejci, J. Intern. J. Environ. Anal. Chem. 1996, 65, 139.
20. Alegret, S.; Martorell, D.; Cespedes, F.; Martinez-Fabregas, E. Anal. Chim. Acta 1997, 337, 305.
21. Labbe, P.; Besombes, J. L.; Cosnier, S.; Reverdy, G. Anal. Chim. Acta 1995, 311, 255.
22. Wang, J.; Nascimento, V. B.; Kane, S. A.; Rogers, K.; Smyth, M. R.; Angnes, L. Talanta 1996, 43, 1903.
23. Rechnitz, G. A.; Everett, W. R. Anal. Chem. 1998, 70, 807.
24. Alegret, S.; Martorell, D.; Cespedes, F.; Martinez-Fabregas, E. Anal. Chim. Acta 1994, 290, 343.
25. Lorenzo, E.; Abad, J. M.; Pariente, F.; Herandez, L.; Abruna, H. D. Anal. Chem. 1998, 70, 2848.
26. Matsunaga, T.; Okochi, M. Electrochim. Acta 1997, 42, 3247.
27. Tomi, T. -T.; Liu, H. Y.; Weaver, M. J. J. Am. Chem. Soc. 1984, 106, 1233.
28. Chen, H. Y.; Ju, H. X.; Zhou, D. M. J. Electroanal. Chem. 1996, 408, 219.
29. Albery, W. J.; Eddowes, M. J.; Hill, H. A. O.; Hillman, A. R. J. Am. Chem. Soc. 1981, 103, 3904.
30. Uosaki, K.; Kondo, T.; Yanagida, M.; Nomura, S. I.; Ito, T. J. Electroanal. Chem. 1997, 438, 121.
31. Lenhard, J. R.; Murray, R. W. J. Am. Chem. Soc. 1978, 100, 7870.
32. Tse, D.C.-S.; Kuwana, T. Anal. Chem. 1978, 50, 1315.
33. Watkins, B. J.; Behling, J. R.; Kariv, E.; Miller, L. L. J. Am. Chem. Soc. 1975, 97, 3549.
34. Lau, A. N. K.; Miller, L. L. J. Am. Chem. Soc. 1983, 105, 5271.
35. Gao, Z.; Siow, K. S.; Ng, A.; Zhang, Y. Anal. Chim. Acta 1997, 343, 49.
36. Casella, I. G.; Guascito, M. R.; Salvi, A. M.; Desimoni, E. Anal. Chim. Acta 1997, 354, 333.
37. Kanazawa, K. K.; Diaz, A. F.; Geiss, R. H.; Gill, W. D.; Kwak, J. F.; Logan, J. A.; Rabolt, J. F.; Street, G. B. J. C. S. Chem. Comm. 1979, 854.
38. Ciszewski, A.; Milczarek, G. J. Electroanal. Chem. 1997, 426, 125.
39. Komori, T.; Nonaka, T. J. Am. Chem. Soc. 1983, 105, 5690.
40. Murray, R. W.; Reed, R. A.; Geng, L. J. Electroanal. Chem. 1986, 208, 185.
41. Baldwin, R. P.; Christensen, J. K.; Kryger, L. Anal. Chem. 1986, 58, 1790.
42. Ghosh, P. K.; Bard, A. J. J. Am. Chem. Soc. 1983, 105, 5691.
43. Zen, J. M.; Chen, P. J. Anal. Chem. 1997, 69, 5087.
44. Murray, C. G.; Nowak, R. J.; Rolison, D. R. J. Electroanal. Chem. 1984, 164, 205.
45. Chen, H. Y.; Yu, A. M.; Zhang, H. L. Analyst 1997, 122, 839.
46. Chen, H. Y.; Yu, A. M. Anal. Chim. Acta 1997, 344, 181.
47. Zen, J. M.; Ting, Y. S. Anal. Chim. Acta 1997, 342, 175.
48. Zen, J. M.; Wang, W. M.; Ilangovan, G. Anal. Chim. Acta 1998, 372, 315.
49. Kang, T. -F. Anal. Chim. Acta 1997, 354, 343.
50. Chen, H. Y.; Ni, J. A.; Ju, H. X.; Leech, D. Anal. Chim. Acta 1999, 378, 151.
51. Zinger, B.; Miller, L. L. J. Am. Chem. Soc. 1984, 106, 6861.
52. Vettorazzi, G.; Almeida, W. F.; Burin, G. J.; Jaeger, R. B.; Puga, F. R.; Rahde, A. F.; Reyes, F. G.; Schvartsman, S. Teratogenesis, Carcinogenesis, and Mutagenesis 1995, 15, 313.
53. Kumar, U.; Agarwal, H. C. Pestic. Sci. 1992, 36, 121
54. Marshall, W. D. J. Agric. Food Chem. 1972, 25, 357.
55. Bottomley, P.; Hoodless, R. A.; Smart, N. A. Residue Rev. 1985, 95, 5.
56. Graham, S. L.; Hansen, W. H. Bull. Environ. Contam. Toxicol. 1972, 7, 19.
57. Cullen, T. E. Anal. Chem. 1964, 36, 221.
58. Rangaswamy, J. R.; Vijayashankar, Y. N. J. Assoc. Off. Anal. Chem. 1975, 58, 1232.
59. Rangaswamy, J. R.; Poornima, P.; Majumder, S. K. J. Assoc. Off. Anal. Chem. 1970, 53, 519.
60. Rao, T. P.; Mathew, L.; Reddy, M. L. P.; Iyer, C. S. P.; Damodaran, A. D. Talanta 1996, 43, 73.
61. Lin, M. S.; Jan, B. I.; Leu, H. J.; Lin, J. S. Anal. Chim. Acta 1999, 388, 111.
62. Pingarron, J. M.; Fernandez, C.; Reviejo, A. J.; Polo, L. M. Talanta 1996, 43, 1341.
63. Perez-Ruiz, T.; Martinez-Lozano, C.; Tomas, V.; Casajus, R. Talanta 1996, 43, 193.
64. Verma, B. C.; Sood, R. K.; Sidhu, H. S. Talanta 1983, 30, 787.
65. Gupta, V. K.; Agrawal, V.; Shivhare, P. Fresenius J. Anal. Chem. 1992, 344, 350.
66. Gupta, V. K.; Kesari, R. Talanta 1998, 45, 1097.
67. Rao, T. P.; Mathew, L.; Iyer, C. S. P.; Damodaran A. D. Talanta 1995, 42, 41.
68. Rao, A. L. J.; Malik, A. K. Talanta 1997, 44, 177.
69. Gustafsson, K. H.; Thompson, R. A. J. Agric. Food Chem. 1981, 29, 729.
70. Sedlak, D. L.; Weissmahr, K. W.; Houghton, C. L. Anal. Chem. 1998, 70, 4800.
71. Lo, C. -C.; Ho, M. -H.; Hung, M. -D. J. Agric. Food Chem. 1996, 44, 2720.
72. Schwack, W.; Bruger, B.; Nyanzi, S. Fresenius J. Anal. Chem. 1995, 351, 297.
73. Chan, W. H.; Lee, A. W. M.; Ng, S. L.; Liu, W. L. Analyst 1992, 117, 1909.
74. Wang, J.; Golden, T.; Li, R. Anal Chem. 1998, 60, 1642.
75. Nyokong, T.; Mafatle, T. Anal. Chim. Acta 1997, 354, 307.
76. Zagal, J. H.; Retamal, B. A.; Vaschetto, M. E. J. Electroanal. Chem. 1997, 431, 1.
77. Lever, A. B. P.; Janda, P.; Tse, Y. H. Anal Chem. 1994, 66, 384.
78. Baldwin, R. P.; Qi, X. J. Electrochem. Soc. 1996, 143, 1283.
79. Hart, J. P.; Wring, S. A. Analyst 1989, 114, 1563.
80. Hart, J. P.; Wring, S. A.; Bracey, L.; Birch, B. J. Anal. Chim. Acta 1997, 354, 307.
81. Hart, J. P.; Abass, A. K. Sensors and Actrators 1997, B41, 169.
82. Hart, J. P.; Hartley, I. C. Analyst 1994, 119, 259.
83. Yeager, E.; Bindra, P.; Zagal, J. J. Electrochem. Soc. 1980, 127, 1506.
84. Leung, T. W.; Dombek, B. D. J. Chem. Soc. Chem. Comm. 1992, N3, 205.
85. Nyokong, T.; Chebotareva, N. J. Appl. Electrochem. 1997, 27, 975.
86. Efstathiou, C. E.; Cookeas, E. G. Analyst 1994, 119, 1607.
87. 廖佳儀 淡江大學化學研究所碩士論文 1998, pp. 42-45.
88. Lesage, S. J. Agric. Food Chem. 1980, 28, 787.
89. Karyakin, A. A.; Gitelmacher, O. V.; Karyakina, E. E. Anal Chem. 1995, 67, 2419.
90. Bard, A. J.; Faulkner, L. R. ELECTROCHEMICAL METHODS Fundamentals and Applications; John Wiley & Sons:New York, 1980.