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研究生: 陳若玫
Chen, Ruo-mei
論文名稱: 研製奈米碳電極應用於活性氧化物之檢測
Fabrication of Carbon Nanopipette Electrodes for the Detection of Reactive Oxidative Species
指導教授: 陳巧貞
Chen, Chiao-Chen
學位類別: 碩士
Master
系所名稱: 理學院 - 化學系
Department of Chemistry
論文出版年: 2021
畢業學年度: 109
語文別: 中文
論文頁數: 87
中文關鍵詞: 奈米滴管奈米碳滴管普魯士藍聚苯胺
外文關鍵詞: Nanopipette, Carbon nanopipeete, Prussian blue, Polyaniline
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  • 細胞中過氧化氫的濃度與有機體的生理狀況及病理息息相關,由於細胞內的過氧化氫濃度極低,若電極尺寸過大對細胞內過氧化氫的靈敏度會很低,所以本研究所使用奈米滴管(Nanopipette)透過雷射拉針器控制尖端開口大小為臨界尺寸,奈米滴管常用來進行電化學分析或掃描探針顯微術(Scanning probe microscopy technique),透過奈米滴管製備奈米碳滴管(Carbon nanopipette),由於過氧化氫的氧化還原電位分別為+1.47 V以及-1.0 V vs. Ag/AgCl,偵測的電位範圍不僅很大,並且涉及水的氧化還原電位,因此本實驗透過電催化劑--普魯士藍(Prussian blue)對過氧化氫進行電催 化,使其氧化還原電位提早至-0.4~ 1.2 V vs. Ag/AgCl的範圍中,在製備普魯士藍膜時,觀察到掃速越快,普魯士藍顆粒會越小,而且膜厚也會越薄,不僅掃速會影響普魯士藍顆粒,濃度也會影響,濃度越小,顆粒也越小,由於實驗中所使用的電極尺寸在100 nm左右,因此選用濃度小,掃速快的方式進行修飾,以達所需的普魯士藍顆粒大小能夠沉積在奈米碳電極中。普魯士藍的優點是可以催化過氧化氫,不過它單獨存在於電極表面是不穩定的,特別是在鹼性溶液中,因為氫氧根離子會與鐵離子很容易結合,導致普魯士藍被分解,所以再將普魯士藍外修飾一層導電高分子--聚苯胺進行保護,聚苯胺為長條絲狀,具有通透性,可以使分子進入,但又可以有效保護普魯士藍,並將奈米碳電極、奈米普魯士藍碳電極以及奈米聚苯胺/普魯士藍碳電極對過氧化氫進行偵測,結果顯示被普魯士藍修飾的電極皆可以偵測到過氧化氫的訊號,而且也具有與濃度變化的線性關係。

    The concentration of hydrogen peroxide in the cell is related to physiological condition and pathology for organism. Due to the extremely low concentration of hydrogen peroxide in the cell, if the electrode size is so large that the sensitivity to the hydrogen peroxide in the cell is low. In this research, the nanopipette is used to control the size of the tip opening to a critical size through a laser puller. Nanopipettes are commonly used for electrochemical analysis or scanning probe microscopy. Since the standard redox potential of the couple H2O2/H2O in neutral medium is rather high (+1.47 to -1.0 V vs. Ag/AgCl), and involves the oxidation-reduction potential of water. Therefore, this experiment uses the electrocatalyst--Prussian blue to electrocatalyze hydrogen peroxide, so that its redox potential is advanced to the range of -0.4~1.2 V vs. Ag/AgCl. The advantage of Prussian blue is that it can catalyze hydrogen peroxide. However, Prussian blue alone on the electrode surface is unstable, especially in alkaline solutions, because hydroxide ions can easily combine with iron ions, causing Prussian blue to be decomposed. In order to improve the unstable problem, the Prussian blue carbon nanopipettes (PB CNP) are modified with polyaniline (PANI). The form of polyaniline is long filaments with permeability, which allows molecules to enter and effectively protecting Prussian blue film. Hydrogen peroxide was detected with CNP, PB CNP and PANI/PB CNP. The results showed that electrodes modified with Prussian blue can detect the signal of H2O2, and It also has a linear relationship with changes in concentration.

    中文摘要 I Extened Abstracts II 誌謝 X 目錄 XI 表目錄 XIII 圖目錄 XIII 第1章 緒論與動機 1 第2章 文獻回顧 2 2.1 過氧化氫鑑定之重要性 2 2.2 過氧化氫之檢測方法 3 2.2.1 光譜法(螢光、吸收光譜) 4 2.2.2 Electron Spin Resonance Spectroscopy 5 2.2.3 電化學法 7 2.3 超微電極於過氧化氫量測的應用 10 第3章 實驗方法與材料 17 3.1 奈米滴管的製備與鑑定 17 3.1.1 毛細管前處理 17 3.1.2 奈米滴管拉製 17 3.1.3 奈米滴管的鑑定 20 3.2 奈米碳電極(CNP)的製備與鑑定 22 3.2.1 奈米碳電極製備流程 22 3.2.2 奈米碳電極之形貌鑑定 24 3.2.3 奈米碳電極之電化學性質鑑定 24 3.3 奈米普魯士藍碳電極之製備(PB CNP) 27 3.3.1 奈米普魯士藍碳電極製備流程 27 3.3.2 奈米普魯士藍碳電極之電化學性質鑑定 29 3.4 奈米聚苯胺(石墨烯)/普魯士藍碳電極之製備(PANI/PB CNP) 30 3.4.1 奈米聚苯胺(石墨烯)/普魯士藍碳電極製備流程 30 3.4.2 奈米聚苯胺/普魯士藍碳電極之電化學性質鑑定 36 3.5 普魯士藍膜及聚苯胺膜之鑑定 36 3.6 樣品的製備 37 3.6.1 磷酸鹽緩衝液的製備 37 3.6.2 過氧化氫溶液製備及檢測 38 第4章 結果與討論 40 4.1 奈米碳電極製備 40 4.1.1 拉針參數的影響 40 4.1.2 碳沉積時間與不同掃速的影響 43 4.1.3 氧化還原物質濃度變化 51 4.2 奈米普魯士藍碳電極製備 53 4.2.1 奈米碳電極空白測試 53 4.2.2 奈米碳電極沉積普魯士藍及檢測 54 4.2.3 普魯士藍膜的形貌鑑定 58 4.3 奈米聚苯胺/普魯士藍碳電極製備 66 4.4 三種電極對於偵測過氧化氫樣品的比較 71 4.5 過氧化氫與干擾物的偵測 74 第5章 結論與未來展望 76 第6章 參考文獻 78 第7章 附錄 87

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