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研究生:李懿
研究生(外文):Li, Yi
論文名稱:網版印刷碳電極結合奈米複合碳材同時偵測 雙酚A、8-羥基-2'-脫氧鳥苷、對苯二酚 之方法開發及應用
論文名稱(外文):Development and Application of Simultaneous Determination of Bisphenol A, 8-Hydroxy-2'-Deoxyguanosine and Hydroquinone Base on Carbon Nanocomposite Materials Modified Screen-Printed Carbon Electrode
指導教授:李慧玲李慧玲引用關係
指導教授(外文):Lee, Hui-Ling
口試委員:李慧玲陳壽椿陳泊余
口試委員(外文):Lee, Hui-LingChen, Show-ChuenChen, Po-Yu
口試日期:2014-07-29
學位類別:碩士
校院名稱:輔仁大學
系所名稱:化學系
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:2014
畢業學年度:102
語文別:中文
論文頁數:122
中文關鍵詞:雙酚 A8-羥基-2'-脫氧鳥苷對苯二酚奈米複合碳材石墨烯氧化物電化學還原石墨烯奈米碳管羧酸化奈米碳管奈米碳黑網版印刷碳電極修飾電極電化學人體尿液
外文關鍵詞:bisphenol A8-hydroxy-2'-deoxyguanosinehydroquinonecarbon nanocomposite materialsgraphene oxideelectrochemical reduced-graphenecarbon nanotubescarboxylated carbon nanotubescarbon blackscreen-printed carbon electrodemodified electrodeelectrochemistryhuman urine
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  暴露於環境中的污染物日趨增加,並且已知這些環境污染物會對於人體的健康造成嚴重的危害,其中雙酚A (Bisphenol A)為一具有兩個苯酚官能基的有機化合物,廣泛地使用於食物、飲料包裝材料和嬰兒奶瓶製作,及美白藥品中的對苯二酚 (Hydroquinone),若過度使用則會危害人體的健康,而8-羥基-2'-脫氧鳥苷 (8-Hydroxy-2'-Deoxyguanosine) 為人體中一重要的氧化性傷害指標物。因此,本研究使用電化學還原石墨烯 (Electrochemical Reduced-Graphene)、奈米碳管 (Carbon Nanotubes)、羧酸化奈米碳管 (Carboxylated Carbon Nanotubes) 及奈米碳黑 (Carbon Black) 等奈米碳材修飾網版印刷碳電極 (Screen-Printed Carbon Electrode),製備一高靈敏度及高選擇性的電化學感測器,以發展一快速、簡便同時偵測人體尿液中雙酚A、8-羥基-2'-脫氧鳥苷與對苯二酚的方法。
  實驗結果在最佳化的條件下,經由差式脈波伏安法 (Differential Pulse Voltammetry) 與電化學交流阻抗分析 (Electrochemical Impedance Spectroscopy),證實電化學還原石墨烯/奈米碳管修飾電極對雙酚A、8-羥基-2'-脫氧鳥苷、對苯二酚具有良好的電子傳遞特性、減少電傳阻抗,及增加分析物氧化電流訊號的特性,並以場發射槍掃描式電子顯微鏡 (Field Emission Scanning Electron Microscope)、顯微拉曼光譜儀 (Micro-Raman Spectrometer) 及X光光電子能譜儀 (X-ray Photoelectron Spectroscopy) 對未修飾和修飾電極進行表面特徵、結構特性、化學組成等探討,證實此修飾方法可成功地製備電化學還原石墨烯/奈米碳管修飾電極。
  電化學還原石墨烯/奈米碳管修飾電極對於雙酚A、8-羥基-2'-脫氧鳥苷、對苯二酚的檢量線 (Calibration Curve) 範圍分別為0.5 - 20 μM、0.05 - 10 μM、0.5 - 100 μM,偵測極限 (Detection Limit,S/N = 3) 分別為14 nM、3 nM、28 nM。
  另外,探討電化學還原石墨烯/奈米碳管修飾電極的再現性 (Reproducibility) 以及穩定度 (Stability),其同日間 (Intra Day) 與異日間 (Inter Day) 的相對標準偏差 (Relative Standard Deviation) 分別小於4.11 % 與3.38 %,並且連續偵測一個月後的電流訊號與初始電流訊號相比,其電流訊號仍保89.91 % 以上,證實此修飾電極具有良好的再現性及穩定度。
  最後,此電化學還原石墨烯/奈米碳管修飾電極可成功地應用於同時檢測人體尿液 (Human Urine) 中的雙酚A、8-羥基-2'-脫氧鳥苷、對苯二酚,其回收率介於95.82 % 至106.85 % 之間,證實此修飾電極具有良好的準確性 (Accuracy)。
  Environmental exposure to contaminants has increasingly been acknowledged to play a vital role in wide range of health problems. Bisphenol A (BPA), an organic compound with two phenol functional groups, is widely used in the food, beverage packaging materials and the production of baby bottles, Hydroquinone (HQ) was used to skin lightening cosmetics, if we overuse will cause harm to our health. 8-hydroxy-2'-deoxy-guanosine (8-OHdG) is an important oxidative damage indicator substance in the human body. Development of highly sensitive and selective electrochemical sensors using nanomaterial such as reduced-graphene (erGN), carbon nanotubes (CNT), carboxylated carbon nanotubes (CNT-COOH) and carbon black (CB) modified screen-printed carbon electrode (SPCE) is creating continual interest and also fast and simple method for simultaneous determination of bisphenol A, 8-hydroxy-2'-deoxyguanosine and hydroquinone in human urine .
  In this optimal conditions, the results shown the modified SPCE have properties of excellent electron transfer characteristics, low electron transfer resistance and increase the oxidation current by differential pulse voltammetry (DPV) and electrochemical impedance analysis (EIS). In the other hand the bare electrode and modified electrode were characterized by field emission scanning electron microscope (FEG-SEM), micro-raman spectrometer (Micro-Raman) and X-ray photoelectron spectroscopy (XPS), which confirmed that electrochemical reduced-graphene/carbon nanotubes modified electrode can be successfully prepared in this electrochemical reduced method.
  The electrochemical reduced-graphene/carbon nanotubes modified electrode shown a linear response for bisphenol A, 8-hydroxy-2'-deoxyguanosine and hydroquinone in the concentration range of 0.5 to 20 μM, 0.05 to 10 μM and 0.5 to 100 μM with detection limit of 14 nM, 3 nM and 28 nM at S/N = 3, respectively.
  In addition, the reproducibility and stability of this electrochemical reduced-graphene/carbon nanotubes modified electrode were discussed. Its relative standard deviation (RSD) of intra day and inter day were less than 4.11 % and 3.38 %, respectively. Stability still remanined above 89.91 % during one month. These results have confirmed that this modified electrode have satisfactory reproducbility and stability.
  Finally, this electrochemical reduced-graphene/carbon nanotubes modified electrode was successfully applied in the simulataneous determination of these analytes in human urine. The recovery was between 95.82 to 106.85 %. These results have confirmed that this modified electrode have good accuracy.
謝誌 I
摘要 IV
Abstract VII
目錄 IX
圖目錄 XIII
表目錄 XVII
第一章、緒論 1
1-1研究背景與目的 1
1-2分析物簡介 5
1-2-1雙酚A 5
1-2-2對苯二酚 6
1-2-3 8-羥基-2'-脫氧鳥苷 7
1-3分析物之偵測方法 8
1-3-1免疫分析 9
1-3-2質譜儀 11
1-3-3紫外可見光或光二極體陣列偵測器 14
1-3-4化學放光偵測器 15
1-3-5螢光偵測器 16
1-3-6電化學偵測器 17
1-4修飾電極簡介 20
1-4-1修飾電極的方式 20
1-4-1-1化學吸附法 20
1-4-1-2共價鍵結法 21
1-4-1-3高分子薄膜塗佈法 22
1-4-1-4非均勻相材料混合塗佈法 22
1-4-2修飾電極的特性與應用 23
1-4-2-1電催化 24
1-4-2-2預濃縮 26
1-4-2-3薄膜阻隔 27
1-5碳材簡介 28
1-5-1石墨烯 28
1-5-2奈米碳管 31
1-5-2奈米碳黑 32
1-6 網版印刷碳電極 34
第二章、研究方法 35
2-1實驗架構 35
2-2實驗藥品 36
2-3實驗儀器與設備 37
2-4實驗步驟 38
2-4-1修飾電極之製備 38
2-4-2循環伏安法 40
2-4-3電化學交流阻抗分析 40
2-4-4差式脈波伏安法 40
2-4-5場發射槍掃描式電子顯微鏡分析 41
2-4-6顯微拉曼光譜儀分析 42
2-4-7 X光光電子能譜儀分析 43
第三章、結果與討論 45
3-1分析物的電化學特性 45
3-2修飾電極最佳化的探討 48
3-2-1探討以電化學還原石墨烯的最佳還原時間 48
3-2-2探討以電化學還原石墨烯的最佳還原電位 50
3-2-3探討奈米複合碳材的選擇 52
3-2-4探討奈米碳管之最佳比例 55
3-2-5探討石墨烯氧化物與奈米碳管之修飾劑的最佳化劑量 57
3-2-6探討緩衝溶液之最佳化pH值 58

3-3電化學還原石墨烯/奈米碳管修飾電極之電化學特性探討 62
3-3-1掃描速率 62
3-3-2電化學交流阻抗分析 65
3-3-3修飾電極之電化學特性 68
3-4電化學還原石墨烯/奈米碳管修飾電極之物理特性探討 71
3-4-1場發射槍掃描式電子顯微鏡 71
3-4-2顯微拉曼光譜儀 73
3-4-3 X光光電子能譜儀 75
3-5分析方法的建立與確效 78
3-5-1 檢量線的建立 78
3-5-2干擾物的探討 83
3-5-3 修飾電極的再現性與穩定度探討 85
3-6真實樣品的偵測 89
3-6-1 尿液樣品的稀釋倍率比較 89
3-6-2 修飾電極於尿液樣品中的修飾效果 91
3-6-3 於尿液樣品中進行標準添加法 94
第四章、結論 95
第五章、參考文獻 98
(1) http://bjycjy.bjedu.gov.cn/2011bjamweb/bjjsxx/html/home.html.
(2) Choi, C. H.; Chung, M. W.; Kwon, H. C.; Chung, J. H.; Woo, S. I. Applied Catalysis B: Environmental 2014, 144, 760-766.
(3) 黃壬瑰,環境檢驗所。
(4) 吳幸娟、楊文都,行政院勞工委員會勞工安全衛生研究所,101年3月。
(5) 吳碩文,美白相關藥物介紹,亞東紀念醫院,藥劑部。
(6) 王千豪,輔仁大學化學研究所,碩士論文,100年7月。
(7) Zhao, M.-P.; Li, Y.-Z.; Guo, Z.-Q.; Zhang, X.-X.; Chang, W.-B. Talanta 2002, 57, 1205-1210.
(8) Zhang, J.; Zhao, S.-Q.; Zhang, K.; Zhou, J.-Q. Chemosphere 2014, 95, 105-110.
(9) Kaneko, K.; Kimata, T.; Tsuji, S.; Ohashi, A.; Imai, Y.; Sudo, H.; Kitamura, N. Clinica Chimica Acta 2012, 413, 1822-1826.
(10) Darwish, I. A.; Wani, T. A.; Alanazi, A. M.; Hamidaddin, M. A.; Zargar, S. Talanta 2013, 111, 13-19.
(11) Della Ciana, L.; Bernacca, G.; De Nitti, C.; Massaglia, A. Journal of Immunological Methods 1996, 193, 51-62.
(12) Selvaraj, K. K.; Shanmugam, G.; Sampath, S.; Joakim Larsson, D. G.; Ramaswamy, B. R. Ecotoxicology and Environmental Safety 2014, 99, 13-20.
(13) Mei, S.; Yao, Q.; Wu, C.; Xu, G. Journal of Chromatography B 2005, 827, 83-87.
(14) Chisvert, A.; Sisternes, J.; Balaguer, Á.; Salvador, A. Talanta 2010, 81, 530-536.
(15) Chen, M.; Tao, L.; Collins, E. M.; Austin, C.; Lu, C. Journal of Chromatography B 2012, 904, 73-80.
(16) Wang, C.-J.; Yang, N.-H.; Chang, C.-C.; Liou, S.-H.; Lee, H.-L. Journal of Chromatography B 2011, 879, 3538-3543.

(17) Desmedt, B.; Van Hoeck, E.; Rogiers, V.; Courselle, P.; De Beer, J. O.; De Paepe, K.; Deconinck, E. Journal of Pharmaceutical and Biomedical Analysis 2014, 90, 85-91.
(18) Rezaee, M.; Yamini, Y.; Shariati, S.; Esrafili, A.; Shamsipur, M. Journal of Chromatography A 2009, 1216, 1511-1514.
(19) Kvasnicová, V. r.; Samcová, E.; Jursová, A.; Jelı́nek, I. Journal of Chromatography A 2003, 985, 513-517.
(20) Gao, W.; Legido-Quigley, C. Journal of Chromatography A 2011, 1218, 4307-4311.
(21) Chen, X.; Wang, C.; Tan, X.; Wang, J. Analytica Chimica Acta 2011, 689, 92-96.
(22) Nair, U. J.; Floyd, R. A.; Nair, J.; Bussachini, V.; Friesen, M.; Bartsch, H. Chemico-Biological Interactions 1987, 63, 157-169.
(23) Du, J.; Li, Y.; Lu, J. Talanta 2001, 55, 1055-1058.
(24) Zhou, Q.; Gao, Y.; Xie, G. Talanta 2011, 85, 1598-1602.
(25) Lisboa, N. S.; Fahning, C. S.; Cotrim, G.; dos Anjos, J. P.; de Andrade, J. B.; Hatje, V.; da Rocha, G. O. Talanta 2013, 117, 168-175.
(26) Svoboda, P.; Ko, S.-H.; Cho, B.; Yoo, S.-H.; Choi, S.-W.; Ye, S.-K.; Kasai, H.; Chung, M.-H. Analytical Biochemistry 2008, 383, 236-242.
(27) Zhang, L.; Zhang, L.; Zhang, W.; Zhang, Y. Analytica Chimica Acta 2005, 543, 52-57.
(28) Inoue, K.; Kato, K.; Yoshimura, Y.; Makino, T.; Nakazawa, H. Journal of Chromatography B: Biomedical Sciences and Applications 2000, 749, 17-23.
(29) Sajiki, J. Journal of Chromatography B: Biomedical Sciences and Applications 2001, 755, 9-15.
(30) Koide, S.; Kinoshita, Y.; Ito, N.; Kimura, J.; Yokoyama, K.; Karube, I. Journal of Chromatography B 2010, 878, 2163-2167.
(31) Rueda, M. E.; Sarabia, L. A.; Herrero, A.; Ortiz, M. C. Analytica Chimica Acta 2003, 479, 173-184.
(32) Crevillén, A. G.; Barrigas, I.; Blasco, A. J.; González, M. C.; Escarpa, A. Analytica Chimica Acta 2006, 562, 137-144.
(33) Murray, R. W.; Ewing, A. G.; Durst, R. A. Analytical Chemistry 1987, 59, 379A-390A.
(34) Baldwin, R. P.; Thomsen, K. N. Talanta 1991, 38, 1-16.

(35) Cox, J. A.; Jaworski, R.; Kulesza, P. J. Electroanalysis 1991, 3, 869-877.
(36) Zotti, G.; Schiavon, G.; Zecchin, S.; Berlin, A.; Pagani, G. Langmuir 1998, 14, 1728-1733.
(37) Fang, A.; Ng, H.; Su, X.; Li, S. F. Y. Langmuir 2000, 16, 5221-5226.
(38) Shi, G.; Lu, J.; Xu, F.; Sun, W.; Jin, L.; Yamamoto, K.; Tao, S.; Jin, J. Analytica Chimica Acta 1999, 391, 307-313.
(39) Zen, J.-M.; Kumar, A. S.; Chen, J.-C. Analytical Chemistry 2001, 73, 1169-1175.
(40) Baldwin, R. P.; Christensen, J. K.; Kryger, L. Analytical Chemistry 1986, 58, 1790-1798.
(41) Kang, X.; Wang, J.; Wu, H.; Aksay, I. A.; Liu, J.; Lin, Y. Biosensors and Bioelectronics 2009, 25, 901-905.
(42) Kim, Y.-R.; Bong, S.; Kang, Y.-J.; Yang, Y.; Mahajan, R. K.; Kim, J. S.; Kim, H. Biosensors and Bioelectronics 2010, 25, 2366-2369.
(43) Wu, Z.; Wang, B.; Dong, S.; Wang, E. Biosensors and Bioelectronics 2000, 15, 143-147.
(44) Liu, H.; Ying, T.; Sun, K.; Li, H.; Qi, D. Analytica Chimica Acta 1997, 344, 187-199.
(45) Sun, C.; Song, W.; Zhao, D.; Gao, Q.; Xu, H. Microchemical Journal 1996, 53, 296-302.
(46) Wang, J.; Golden, T.; Li, R. Analytical Chemistry 1988, 60, 1642-1645.
(47) Liu, H.; Li, H.; Ying, T.; Sun, K.; Qin, Y.; Qi, D. Analytica Chimica Acta 1998, 358, 137-144.
(48) Ciszewski, A.; Milczarek, G. Journal of Electroanalytical Chemistry 1996, 413, 137-142.
(49) Raj, C. R.; Gobi, K. V.; Ohsaka, T. Bioelectrochemistry 2000, 51, 181-186.
(50) Moraes, F. C.; Mascaro, L. H.; Machado, S. A. S.; Brett, C. M. A. Talanta 2009, 79, 1406-1411.
(51) Ogorevc, B.; Cai, X.; Grabec, I. Analytica Chimica Acta 1995, 305, 176-182.
(52) Conesa, A. J.; Pinilla, J. M.; Hernández, L. Analytica Chimica Acta 1996, 331, 111-116.
(53) Zen, J.-M.; Chen, I. L.; Shih, Y. Analytica Chimica Acta 1998, 369, 103-108.
(54) Pumera, M.; Ambrosi, A.; Bonanni, A.; Chng, E. L. K.; Poh, H. L. TrAC Trends in Analytical Chemistry 2010, 29, 954-965.
(55) http://en.wikipedia.org/wiki/Graphene.
(56) Pumera, M, Chem Soc Rev 2010, 39, 4146-4157.
(57) Novoselov, K. S.; Geim, A. K.; Morozov, S. V.; Jiang, D.; Zhang, Y.; Dubonos, S. V.; IV, G.; Firsov, A. A. Science 2004, 306, 666-669.
(58) de Heer, W. A.; Berger, C.; Song, Z. M.: Li, T. B.; Li, X. B.; Ogbazghi, A. Y.; Feng, R.; Dai, Z. T.; Marchenkov, A. N.; Conrad, E. H.; First, P. N. J Phy Chem B 2004, 108, 19912-19916.
(59) Shang, N. G.; Papakonstantinou, P.; McMullan, M.; Chu, M.; Stamboulis, A.; Potenza, A.; Dhesi, S. S.; Marchetto, H. Adv Funct Mater 2008, 18, 3506-3514.
(60) Dai, H. J.; Jiao, L. J.; L. Y.; Zhang, L.; Wang, X. R.; Diankov, G. Nature 2009, 458, 877-880.
(61) Haddon, R. C.; Yu, A. P.; Ramesh, P.; Itkis, M. E.; Bekyarova, E. J Phys Chem C 2007, 111, 7565-7569.
(62) Loh, K. P.; Ang, P. K.; Wang, S.; Bao Q. L.; Thong, J. T. L. ACS Nano 2009, 3, 3587-3594.
(63) Sheng, Z.-H.; Zheng, X.-Q.; Xu, J.-Y.; Bao, W.-J.; Wang, F.-B.; Xia, X.-H. Biosensors and Bioelectronics 2012, 34, 125-131.
(64) Li, S.-J.; Xing, Y.; Wang, G.-F. Microchim Acta 2012, 176, 163-168.
(65) Iijima,S. Nature 1991, 354, 56-58.
(66) http://elearning.stut.edu.tw/m_facture/Nanotech/Web/ch8.htm.
(67) http://www.carbon-black.com/products.html.
(68) 韓文騰,逢甲大學材料科學與工程研究所,碩士論文,92年7月。
(69) 藍胄偉,高木榮,陳信銓,曾偉程,陳韋安,張合,國立臺北科技大學機械工程系,96年2月。
(70) Hu, X.; Dou, W.; Fu, L.; Zhao, G. Analytical Biochemistry 2013, 434, 218-220.
(71) Huang, S.-H.; Liao, H.-H.; Chen, D.-H. Biosensors and Bioelectronics 2010, 25, 2351-2355.
(72) Ku, S.; Palanisamy, S.; Chen, S.-M. Journal of Colloid and Interface Science 2013, 411, 182-186.
(73) Kit-Anan, W.; Olarnwanich, A.; Sriprachuabwong, C.; Karuwan, C.; Tuantranont, A.; Wisitsoraat, A.; Srituravanich, W.; Pimpin, A. Journal of Electroanalytical Chemistry 2012, 685, 72-78.
(74) Moreno, M.; Arribas, A. S.; Bermejo, E.; Chicharro, M.; Zapardiel, A.; Rodríguez, M. C.; Jalit, Y.; Rivas, G. A. Talanta 2010, 80, 2149-2156.
(75) Bergamini, M. F.; Santos, A. L.; Stradiotto, N. R.; Zanoni, M. V. B. Journal of Pharmaceutical and Biomedical Analysis 2007, 43, 315-319.
(76) Oliveira, P. R. d.; Oliveira, M. M.; Zarbin, A. J. G.; Marcolino-Junior, L. H.; Bergamini, M. F. Sensors and Actuators B: Chemical 2012, 171-172, 795-802.
(77) Wang, J.; Tian, B.; Sahlin, E. Analytical Chemistry 1999, 71, 5436-5440.
(78) Chiu, M.-H.; Yang, H.-H.; Liu, C.-H.; Zen, J.-M. Journal of Chromatography B 2009, 877, 991-994.
(79) 林信全,逢甲大學材料科學與工程研究所,碩士論文,94年6月。
(80) 紀東煒,國立中山大學物理研究所,碩士論文,93年1月。
(81) 姚潔宜,國立臺北科技大學製造科技研究所,碩士論文,95年7月。
(82) Li, Y.; Gao, Y.; Cao, Y.; Li, H. Sensors and Actuators B: Chemical 2012, 171-172, 726-733.
(83) Li, T.-H.; Jia, W.-L.; Wang, H.-S.; Liu, R.-M. Biosensors and Bioelectronics 2007, 22, 1245-1250.
(84) Xie, H.; Zhu, Y.; Wu, Y.; Wu, Z.; Liu, E. Materials Research Bulletin 2014, 50, 303-306.
(85) Joseph, L.; Zaib, Q.; Khan, I. A.; Berge, N. D.; Park, Y.-G.; Saleh, N. B.; Yoon, Y. Water Research 2011, 45, 4056-4068.
(86) Bing-zhi, D.; Hua-qiang, C.; Lin, W.; Sheng-ji, X.; Nai-yun, G. Desalination 2010, 250, 693-697.
(87) Su-Hua, W.; Bing-zhi, D.; Yu, H. Desalination 2010, 253, 22-29.
(88) Guo, H.; Xue, K.; Yan, L. Sensors and Actuators B: Chemical 2012, 171-172, 1038-1045.
(89) Jia, L.; Wang, H. Journal of Electroanalytical Chemistry 2013, 705, 37-43.
(90) Li, L.; Fan, L.; Sun, M.; Qiu, H.; Li, X.; Duan, H.; Luo, C. International Journal of Biological Macromolecules 2013, 58, 169-175.
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