臺灣博碩士論文加值系統

有機磷類農藥是目前被廣泛使用的一種殺蟲劑，此類農藥具有高藥效及快速分解的優點，但是有機磷農藥的毒性很高，會破壞生物體的神經系統，嚴重者會導致中毒或死亡；本研究分析的大滅松是屬於有機磷殺蟲劑，常使用於核果類及柑橘類的農作物上，由於此殺蟲劑本身與其水解代謝後產物均具有很高的毒性，而且都有致癌的危險，因此希望發展出兼具及時與準確的偵測系統，以完成一個穩定且高靈敏度的農藥化學感測器。
本實驗主要是利用鈷酞青素(Cobalt Phthalocyanine)與印刷碳墨混和修飾於玻璃碳旋轉電極上，成功的在+100mV(vs. Ag/AgCl)低干擾電位下測定大滅松的水解產物，而得到氧化電流訊號，並以安培法定量大滅松之濃度。在最佳化的條件下，其可分析之線性範圍為0.15mM ~ 2.4mM (R=0.9997)，偵測極限可達20.93nM (S/N=3)，在連續二十次重複測定1.0mM大滅松的實驗中，相對標準偏差為1.02%，響應時間為2.1秒，於環境中常見之干擾物的存在下進行農藥分析，結果證實干擾程度皆小於3.3 %，由此可說明本系統具有很高的精確度，不容易受外界環境的影響，對於發展真實樣品之偵測有很大的貢獻。
以鈷酞青素修飾電極所發展出來的大滅松化學感測器具有迅速、穩定、靈敏及低干擾的優點，其分析特性符合美國環境保護署對大滅松殺蟲劑安全殘餘劑量的偵測要求，未來或可將此分析系統微小化就可發展成簡易而靈敏的農藥感測器。

Organophosphate insecticides are widely used in many agriculture applications. Organophosphates had the advantage of effectiveness and high decomposing rate. However, both of organophosphate and it metabolites possess high neurotoxin. In a severe case, organophosphate pesticides may result in cholinesterase inhibition and/or death. Dimethoate, one of the organopgosphorus pesticides, was used in citrus fruits and of many produce. Both of dimethoate and its metabolite possess high toxicity and carcinogens. The demand of developing a stable and sensitive scheme is, thus urgently needed.
The detection scheme was based on the basis of cobalt phthalocyanine (CoPC) can catalyze the oxidation of electrode. A suitable quantify of CoPC modified ink was pipetted onto a polished GC electrode and air-dried. An operational potential of +100mV (vs. Ag/AgCl) was used to detect dimethoate. In the optimum condition, the linearity is up to 2.4 M with correlation coefficient of 0.9997 and the detection limit of dimethoate is 20.93nM (S/N=3). Its relative standard deviation is 1.02% at a series of twenty repetitive measurements and the response time is 2.1 seconds. The scheme is very precise with low interference advantage. Other advantage includes stable and sensitive characteristics. These sensitive schemes meet the requirement of the residue of dimethoate of US EPA.

目錄……………………………………………………………………… I
圖表目錄……………………………………...………………………... V
第一章 緒論…………………………………………………….…... 1
前言………………………………….………………………………….. 1
1-1 農藥的簡介……………………………………………………….... 2
1-1-1 農藥的分類…………………………………………………. 2
1-1-2 農藥對環境的影響…………………………………………. 7
1-1-3 農藥對人類的影響…………………………………….…… 8
1-2 農藥的偵測………………………………..……………………… 11
1-2-1 吸收光譜偵測法……………………………………….….. 12
1-2-2 發光光譜偵測法…………………………………………... 14
1-2-3 原子光譜偵測法………………………………………...… 15
1-2-4 質譜偵測法………………………………………………... 16
1-2-5 電化學偵測法………………………………………...…… 17
1-2-6 生化感測器………………………………………………... 21
1-3 化學修飾電極…………………………………………………….. 23
1-3-1 化學鍵結法…………………………………….……...…... 24
1-3-2 化學吸附法………………………………………………... 25
1-3-3 高分子薄膜修飾法………………………………………... 28
1-3-4 非均相材料修飾法………………………………………... 31
1-4 修飾電極的功能………………………………………………….. 32
1-4-1 電催化…………………………….……………………….. 32
1-4-2 預濃縮……………………………………………..…….… 34
1-4-3 薄膜阻隔…………………………………….…………….. 35
1-4-4 電釋放…………………………………...………………… 36
1-5 鈷酞青素的簡介………………………………………………….. 37
1-5-1 鈷酞青素的特性…………….…………………………….. 38
1-5-2 鈷酞青素的應用……......……………………………….… 38
1-6 大滅松的簡介………………………………………………..…… 40
1-6-1 大滅松的化學性質與毒性………………………….…….. 40
1-6-2 大滅松的偵測方法………………………………………... 42
1-7 本研究的目的…………………………………………………….. 44
第二章 實驗的部分……………………………………………….. 46
2-1 儀器與設備……………………………………………………….. 46
2-2 藥品……………………………………………………………….. 47
2-3 電極的製備……………………………………………………….. 48
2-3-1 電極的前處理……………………………………………... 48
2-3-2催化劑的修飾……………………………………………… 48
2-4 實驗的設計……………………………………………………….. 48
2-4-1 農藥水解條件的探討……………………………………... 49
2-4-1-1 酸鹼度對水解速率的影響………………….…… 49
2-4-2 操作條件探討……………………………………………... 49
2-4-2-1催化劑組成………………………………………... 49
2-4-2-2 操作電位…………………………………………. 49
2-4-2-3酸鹼值………………………….………………….. 49
2-4-2-4 緩衝溶液種類……………………………………. 50
2-4-2-5 緩衝溶液濃度……………………………………. 50
2-4-2-6 電極轉速…………………………………………. 50
2-4-3 動力學探討………………………………………………... 50
2-4-3-1 電子傳遞速率常數………………………………. 50
2-4-3-2 質傳行為模式的探討……………………………. 51
2-4-4 分析特性………………………………………………….. 51
第三章 結果與討論……………………………………………..… 52
3-1 鈷酞青素催化大滅松的機制與特性…………………………….. 52
3-1-1 鈷酞青素修飾電極催化大滅松的機制…………………... 52
3-1-2 電子傳遞速率k值的探討………………………………… 57
3-1-3 質傳行為模式的探討……………………………………... 59
3-2 大滅松化學感測器的偵測最佳化條件………………………….. 60
3-2-1 催化劑的組成……………………………………………... 60
3-2-2 系統的偵測電位……………………………………...…… 62
3-2-3 電極轉速效應………………………………………….….. 62
3-2-4 電解質酸鹼度的影響………………………...…………… 63
3-2-5 電解質的種類………………………………………….….. 64
3-2-6 電解質的濃度……………………………………………... 65
3-3 大滅松化學感測器的分析特性………………………………….. 66
3-3-1 大滅松化學感測器的分析特性探討……………………... 66
3-3-2 干擾物的測定……………………………………………... 67
3-4 結論……………………………………………………………….. 69
參考資料……………………………………………………….……… 88
符號對照表……………………………………………………………. 96

1.Charting the Progress of Populations, Department of Economic and Social Affairs Population Division, United Nations, New York, 2000.
2.The State of Food and Agriculture, Food and Agriculture Organization, United Nations, New York, 2000.
3.Office of Prevention, Pesticides and Toxic Substances (OPPTS), Environment Protection Agency, USA.
4.「農藥濫用影響國人健康及生態環境」專案調查報告，中華民國監察院，中華民國九十年二月十三日。
5.WHO Task Group on Environment Health Criteria for Pesticide, World Health Organization, WHO Publication Center USA.
6.陳家鐘，「世界農藥研究發展趨勢」，行政院農業委員會農業藥物毒物試驗所，第二十八期專題報導，中華民國八十二年一月。
7.Ware, George Whitaker. The Pesticide Book, Thomson Publisher, Inc., CA, 1989.
8.Frank C. Lu, Basic Toxicology, Yi Hsien Publishing Co. Ltd., Taipei, 1998.
9.Kamrin, Michael A, Pesticide Profiles: Toxicity, Environmental Impact, and Fate, Lewis Publisher, New York, 1997.
10.Rocha, Edson S.; Santos, Mariton D.; Albuquerque, Edson X., Toxicology and applied Pharmacology, 1999, 159, 31.
11.Rohl C.; Gulden M.: Seibert H., Cell Biology and Toxicology, 2001, 17, 23.
12.Ja-Liang Lin; Swei Hsueh, American Journal of Nephrology, 1993, 13, 124.
13.Rubin, C. D.; Pak, C. Y. C.; Adams-Huet, B.; Genant, H. K.; Li, J.; Rao, D. S., Archives of Internal Medicine, 2001, 161, 2325.
14.Jaga, K.; Duvvi, H., Journal- Royal Society for the Promotion of Health, 2001, 121, 107.
15.李國欽、林浩潭，「農藥與土壤」，行政院農業委員會農業藥物毒物試驗所，第十三期專題報導，中華民國七十八年六月。
16.Gopal, M.; Mukherjee, I.; Yaduraju, N. T., Bulletin of Environmental Contamination and Toxicology, 2000, 64, 40.
17.Opperman, C. H.; Chang, S., Journal of nematology, 1990, 22, 481.
18.Goos, R. J.; Ahrens, W. H., Agronomy Journal, 1992, 84, 459.
19.Tixer, C.; Sancelme, M.; Bonnemoy, F.; Cuer, A.; Veschambre, H., Environmental Toxicology and Chemistry, 2001, 20, 1381.
20.Pothuluri, Jairaj V.; Hinson, Jack A.; Cerniglia, Carl E., Journal of Environmental Quality, 1991, 20, 330.
21.Ozeki, Y.; Komamine, A.; Tanaka, Y., Physiologia Plantarum, 1990, 78, 400.
22.Riggle, B., Bulletin of Environmental Contamination and Toxicology, 1991, 46, 404.
23.Guenzi, W. D., Pesticides in Soil and Water, Soil Science Society of America, Wisconsin, 1974.
24.Jury, W. A.; Ware, G. W., Reviews of Environmental Contamination and Toxicology, Springer-Verlag Inc., New York, 1987.
25.Crane, M.; Newman, M.C., Environmental toxicology and chemistry, 2000, 19, 516.
26.Walton, K.; Walker, R.; Schilter, B., Food and chemical toxicology, 1999, 37, 1175.
27.Ellenhorn M. J.; Barceloux D.G., Medical Toxicology, Elsevier, New York, 1988.
28.Hoffman, R.S.; Morasco, R.; Goldfrank, L.R., Journal of toxicology. clinical toxicology, 1996, 34, 259.
29.Liu, W.; Kumar, A.; Alraja, M., Brain research, 1998, 805, 220.
30.Kiss, J. P.; Windisch, K.; De Oliveira, K.; Hennings, E. C. P.; Mike, A.; Szasz, B. K., Neurochemical Research, 2001, 26, 943.
31.Nanda Kumar, N. V.; Udaya Bhaskar, S., Journal of Food Science and Technology, 1980, 17, 153.
32.Jongen, M. J.; Engel, R.; Leenheers, L H., Journal of Analytical Toxicology, 1991, 15, 30.
33.Valenzuela, A. I.; Lorenzin, R.; Font, G., Journal of Chromatography. A, 1999, 839, 101.
34.Collinge, A.; Noirfalise, A., Journal of Chromatography, 1983, 257, 416.
35.Walters, S. M.; Westerby, B. C.; Gilvydis, D. M., Journal of Chromatography, 1984, 317, 533.
36.Conceicao, M.; Mateus, D. A.; da Silva, Abilio M.; Burrows, Hugh D., Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 1997, 53, 2679.
37.Aaron, J. —J.; Coly, A., Analusis, 2000, 28, 699.
38.Timo Hamers; Mathijis G. D. Smit; Albertinka J. Murk; Jan H. Koeman, Chemosphere, 2001, 45, 609.
39.Weins, Christel; Jork, Hellmut, Journal of Chromatography. A, 1996, 750, 403.
40.Terreni, M.; Benfenati, E.; Natangelo, M.; Facchini, G.; Pagani, G., Journal of Chromatography. A, 1994. 668, 243.
41.中華民國八十九年三月二十日(89)環署檢字第14669號公告，NIEA W656.51B
42.Ling, Y. C.; Huang, I. P., Journal of Chromatography. A, 1995. 695, 75.
43.Crespo, C.; Marce, R. M.; Borrull, F.; Journal of Chromatography. A, 1994. 670, 135.
44.Wigfield, Y. Y.; Grant, R.; Sinder, N., Journal of Chromatography. A, 1993. 657, 219.
45.中華民國八十九年十月九日(89)環署檢字第58881號公告，NIEA D910.00B
46.Stephanou, E. G.; Manoussaridou, E.; Psathaki, M., Journal of Chromatography. A, 1994. 667, 241.
47.Levsen, K.; Schafer, K. H., Journal of Chromatography. A, 1983. 271, 51.
48.Steven J. Lehotay; Alan R. Lightfield; Jennifer A. Harman-Fetcho; Dan J. Donoghue, Journal of Agricultural and Food Chemistry, 2001, 49, 4589.
49.Valcarcel, M.; Luque, M.;Rois, A., Analyst, 1998, 123, 2383.
50.Brett, A. M. O.; Delerue-Matos, C. M.; Garrido, E. M.; Lima, J. L. C., Talata, 1998, 46, 1131.
51.Teresa, G. D.; Agustina, G. C.; Nielene, M. D.; Piedad, P. V.; Francisco, S. L., Journal of Agricultural and Food Chemistry, 2000, 48, 4508.
52.Martinez, R. C.; Gonzalo, E. R.; Garcia, F. G.; Mendez, J. H., Journal of Chromatography, 1993. 644, 49.
53.Pomerantz, I. H.; Miller, L. J.; Kava, G., Journal of the Association of Official Analytical Chemists, 1970, 53, 154.
54.Baker, P. B.; Flaherty, B., Analyst, 1972, 97, 713.
55.Heyrovsky, Jaroslav, Chem. Listy, 1922, 16, 256.
56.Miquel, A. S.; Arben, M.; Salvador, A., Analytica Chimica Acta, 2001, 442, 35.
57.Lorenzo, E.; Abad, J. M.; Pariente, F.; Heandez, L.; Abruna, H. D., Analytical Chemistry, 1998, 70, 2848.
58.Rekha, K.; Gouda, M. D.; Thakur, M. S.; Karanth, N. G., Biosensors and Bioelectronics, 2000, 15, 499.
59.Mulchandani, A.; Mulchandani, P.; Chen, L., Analytical Chemistry, 1999, 71, 2246
60.Husain, Q.; Saleemuddin, M., Enzyme and Microbial Technology, 1986, 8, 886.
61.Mulchandani, A.; Pan, S. Analytical Biochemistry, 1999, 267, 141.
62.Xu, J. J.; Chen, H. Y., Analytical Biochemistry, 2000, 280, 221.
63.Katz, E.; Lion-Dagan, M.; Willner, I., Journal of Electroanalytical Chemistry, 1996, 408, 107.
64.Rover, L.; Kubota, L. T.; Hoehr, N. F., Clinica Chimica Acta, 2001, 308, 55.
65.Vreeke, M. S.; Rocca, P., Electroanalysis, 1996, 8, 55.
66.Narasimhan, K.; Wingard, L. B., Analytical Chemistry, 1986, 58, 2984.
67.Chi, S. Kim; Seung, M. Oh, Electrochimica Acta, 1996, 41, 2433.
68.Cheng, Y. S.; Yeung, K. L., Journal of Membrane Science, 1999, 158, 127.
69.Dong, S.; Deng, Q.; Cheng, G., Analytica Chimica Actd, 1993, 279, 235.
70.Chi, Q.; Dong, S., Analytica Chimica Actd, 1993, 278, 17.
71.Okochi, M.; Matsunaga, T., Electrochimica Acta, 1997, 42, 3247.
72.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.
73.Lobo, M. J.; Miranda, A. J.; Lopez-Fonseca, J. M.; Tunon, P., Analytica Chimica Actd, 1996, 325, 33.
74.Pandey, P. C., Journal of Chemical Society Faraday Transactions. 1, 1988, 84, 2259.
75.Inoue, T.; Kirchhoff, J. R., Analytical Chemistry, 2000, 72, 5755.
76.Zhao, H.; Chang, Y.; Yuan, Z., Analyst, 2001, 126, 358.
77.Pandy, P. C., Sensors and Actuators. Part B, Chemical, 1999, 54, 210.
78.Gregg, B. A.; Heller, A., Analytical Chemistry, 1990, 62, 258.
79.Ohara, T. J.; Rajagopalan, R.; Heller, A., Analytical Chemistry, 1993, 65, 3512
80.He, X. C.; Mo, J. Y., Analyst, 2000, 125, 793.
81.Ttangestaninejad, S.; Mirkhani, V.; Shahrokhian, S.; Amini, M. K., Analytical Biochemistry, 1998, 260, 195.
82.Pandey, P. C.; Upadhyay, S.; Upadhyay, B. C.; Pathak, H. C., Analytical Biochemistry, 2001, 290, 277
83.Nowak, R. J.; Rolison, D. R., Journal of Electroanalytical Chemistry, 1995, 67, 101.
84.Tommaso, R.; Cataldi, I.; Centonze, D.; Guerrieri, A., Analytical Chemistry, 1990, 62, 258.
85.Ohsaka, T.; Yamagughi, Y.; Oyama, N., Bulletin of the Chemical Society of Japan, 1990, 63, 2646.
86.Chen, H. Y.; Yu, A. M.; Zhang, H. L., Analyst, 1997, 122, 839.
87.Cha, S. K.; Ahn, B. K.; Hwang, J. U.; Abruna, H. D., Analytical Chemistry, 1993, 65, 1564.
88.Kolodsick, K.; Ramstad, T., Analytica Chimica Acta, 1995, 313, 75.
89.Wang, J.; Tuzhi, P., Analytical Chemistry, 1987, 59, 740.
90.Sandifer, J. S., Analytical Chemistry, 1981, 53, 1164.
91.Zen, J. M.; Chen, I. L.; Shih, Y., Analytica Chimica Acta, 1998, 369, 103.
92.Miller, L. L.; Zinger, B., Journal of the American Chemical Society, 1984, 106, 6861.
93.Hondneland, C. D.; Mrksich, M., Journal of the American Chemical Society, 2000, 122, 4235.
94.Takase, S.; Shimizu, Y., Chem. Sens., 2001, 17, 73.
95.Amini, M. K.; Shahrokhian, S.; Tangestaninejad, S., J. Sci., Islamic Repub. Iran, 1999, 10, 218.
96.Shahrokhian, S.; Amini, M. K.; Mohammadpoor-Baltork, I.; Tangestaninejad, S. Electroanalysis, 2000, 12, 863.
97.Chen, J. C.; Ju, Y. H.; Liu, C. J., Sens. Actuators, B, 1999, B60, 168.
98.Shekar, B. C.; Sakthivel, S.; Mangalraj, D.; Narayandass, S. A. K.; Venkatachalam, S., Bull. Electrochem., 1998, 14, 422.
99.Gilmartin, M. A. T.; Hart, J. P., Analystical, 1994, 119, 833.
100.Brady, U. E.; Jr; Arthur, B. W., Journal of Economic Entomology, 1963, 56, 477.
101.Sanderson, D. M.; Edson, E. F., British Journal of Industrial Medicine, 1964, 21, 52.
102.Andreozzi, R.; Ialongo, G.; Marotta, R.; Sanchirico, R., Journal of Hazardous Materials, 1999, 64, 283.
103.Environmental Health Criteria for Dimethoate, World Health Organization, WHO Publication Center USA. 1989.
104.Hewitt, R.; Emro, J.; Entwistle, J.; Pankavich, J.; Thorson, R.; Wallace, W.; Waletzky, E., Journal of Economic Entomology, 1958, 51, 445.
105.Casida, J. E.; Sanderson, D. M., Nature (Lond.), 1961, 189, 507.
106. Lee, Y. W.; Westcott, N. D., Journal of Agricultural and Food Chemistry, 1981, 29, 860.
107.Szeto, S. T.; Vernon, R. S.; Brown, M. J., Journal of Agricultural and Food Chemistry, 1985, 33, 763.
108.Van Middelem, C. H.; Waites, R. E., Journal of Agricultural and Food Chemistry, 1964, 12, 178.
109.Girenko, D. B.; Klisenko, M. A.; Pismennaya, M. B., Methods of Determination of Microquantites of Pesticide in Foods, Feed, and the Enviroment, 1978, 57.
110.Petukhov, R. D., Methods of Determination of Microquantites of Pesticide in Foods, Feed, and the Enviroment, 1975, 63.
111.Girenko, D. B.; Klisenko, M. A.; Pismennaya, M. B., Methods of Determination of Microquantites of Pesticide in Foods, Feed, and the Enviroment, 1977, 117.
112.Cabras, P.; Meloni, M.; Pirisi, F. M., Journal of Chromatography, 1979. 176, 473.
113.Nanda Kumar, N. V.; Udaya Bhaskar, S., Journal of Analytical Toxicology, 1980, 18, 139.
114.Chilwell, E. D.; Beechan, P. T., Journal of Analytical Toxicology, 1960, 11, 400.
115.Thomas, M. B.; Sturrock, P. E., Journal of Chromatography. 1986, 57, 318.
116.Hart, A. L.; Collier, W. A.; Janssen, D., Biosensors & Bioelectronics, 1997, 12, 645.
117.中華民國八十九年三月二十日(89)環署檢字第14669號公告，NIEA W656.51B
118.Clive Tomlin, The Pesticide Manual, The Royal Society of Chemistry, Cambridge, 1994.