臺灣博碩士論文加值系統

本研究以氧化亞銅奈米立方體做為非酵素型葡萄糖感測器的電化學觸媒，在氧化亞銅奈米立方體的製備方面，藉由合成時調控不同濃度之陽離子界面活性劑cetyltrimethylammonium bromide (CTAB)，控制氧化亞銅顆粒的形狀及大小，再利用電化學的分析方法探討其催化葡萄糖的能力，並以材料的物理化學特性分析佐證電化學分析結果。此外，修飾於電極表面之金屬觸媒於感測時對許多電活性物質皆有催化能力，因此本研究以Nafion以及cellulose acetate (CA) 混合作為抗干擾層，修飾於電極表面，以增加感測器的選擇性，同時也對待測溶液pH值以及施加電位進行研究。
電化學分析主要是以循環伏安法以及計時安培法研究氧化亞銅奈米立方體催化葡萄糖的性能，並且以TEM、SEM、XRD、ESCA探討其顆粒大小、晶體結構以及表面化學組態。實驗結果發現，以CTAB濃度為0.04 M合成之氧化亞銅奈米立方體為最佳活性觸媒，並以Nafion:CA混合比例為0.5:0.5 (wt.%) 之配比為最適化之抗干擾層修飾電極。
本研究所製備之葡萄糖感測器於0.6 V vs. Ag/AgCl之施加電位下，具有感測葡萄糖線性範圍為0.5 - 9 mM (R2=0.997)，此感測線性範圍下，偵測靈敏度可高達 202.36 μA mM-1 cm-2，且應答時間快 (＜6 s)，並同時具有高選擇性。本論文成功製備氧化亞銅奈米立方體之電化學觸媒，並應用於生物感測器之製程，成功製備具良好再現性及量測準確度、穩定性佳之高靈敏度非酵素型葡萄糖感測器。

Cuprous oxide (Cu2O) nanocubes were synthesized in this study as electrocatalysts for the non-enzymatic glucose sensing. The particles size and shape of Cu2O was controlled through adjusting the concentration of CTAB (cetyltrimethylammonium bromide) which is a cationic surfactant. The capability of catalyzing glucose was investigated by electrochemical analyses and physical-chemcial characterizations. Due to the problem of interference might be resulted from the metal catalysts which can react with electroactive substrates, this work mixed Nafion and cellulose acetate (CA) to serve as an anti-interference layer for the modification of the surface of electrodes and to increase the selectivity. Moreover, the pH value of the analytes and the applied potential were further studied.
The electrochemical analysis, mainly based on cyclic voltammetry and chronoamperometry method, investigated the performance of glucose catalyzing. The physical characteristics of the Cu2O nanocubes were studied by Transmission Electron Microscopy (TEM), Scanning Electron Microscope (SEM), X-Ray Diffraction (XRD), and Electron Spectroscopy for Chemical Analysis (ESCA). Finally, it was found that Cu2O nanocubes synthesized by using 0.04 M CTAB was the optimized concentration for catalyzing glucose, and the optimal ratio of Nafion:CA is 0.5:0.5 (wt.%) for the surface protection layer on the electrode.
The optimized amperometric biosensor covered a wide linear detection range of glucose, from 0.5 to 9 mM (R2=0.997), at 0.6 V vs. Ag/AgCl of applied potential. Moreover, a sensitivity of 202.36 μA mM-1 cm-2 and a rapid response time (＜6 s) were obtained for the as-prepared non-enzymatic glucose sensor. We herein reported a glucose biosensor with surface decorated with Cu2O nanocubes for promising detection performance with good repeatability and high sensitivity.

摘要 I
ABSTRACT II
誌謝 III
目錄 V
圖索引 VIII
表索引 X
第一章、緒論 1
1-1、前言 1
1-2、葡萄糖生物感測器發展簡史 2
1-3、研究動機 4
第二章、文獻回顧 7
2-1、感測器簡介 7
2-2、化學感測器簡介 8
2-3、生物感測器簡介 9
2-3-1、生物感測器定義 9
2-3-2、生物感測器之基本結構與原理 9
2-3-3、生物感測器種類 11
2-3-3-1、依據固定化的生物分子分類 11
2-3-3-2、依據固定化的生物分子與待測生物樣本的結合方式分類 12
2-3-4、訊號換能器分類 14
2-4、電化學式生物感測器 16
2-4-1、電位式 (Potentiometric) 生物感測器 16
2-4-2、電流式 (Amperometric) 生物感測器 17
2-4-3、電導式 (Conductometric) 生物感測器 18
2-5、葡萄糖生物感測器 20
2-5-1、酵素型葡萄糖生物感測器 20
2-5-2、非酵素型葡萄糖感測器 26
2-6、奈米金屬顆粒 29
2-6-1、奈米材料之簡介 29
2-6-2、奈米顆粒之製備方法 30
2-6-3、奈米材料於葡萄糖生物感測器之應用 32
2-7、離子選擇膜 34
2-7-1、Nafion 35
2-7-2、Cellulose acetate 35
第三章、實驗方法 37
3-1、實驗設備 37
3-2、實驗藥品與溶液配製 38
3-2-1、實驗藥品 38
3-2-2、溶液配製 39
3-2-2-1、合成溶液配製 39
3-2-2-2、樣品溶液配製 39
3-3、實驗方法 40
3-3-1、氧化亞銅奈米立方體觸媒之合成方法 40
3-3-2、非酵素型葡萄糖感測器之製備 41
3-3-3、實驗架構 42
3-4、分析儀器與方法 43
3-4-1、感應偶合電漿放射光譜儀分析 (ICP-AES) 43
3-4-2、掃描式電子顯微鏡分析 (SEM) 43
3-4-3、穿透式電子顯微鏡分析 (TEM) 43
3-4-4、化學分析電子能譜 (ESCA) 43
3-4-5、X光繞射分析 (XRD) 44
3-4-6、紫外線/可見光分光光譜儀 (UV-vis) 45
3-5、電化學分析原理 46
3-5-1、電化學分析裝置 46
3-5-2、循環伏安法 (Cyclic Voltammetric method) 47
3-5-3、計時安培法 (Amperometric Method) 49
3-5-4、電化學阻抗分析法 49
第四章、結果與討論 53
4-1、奈米金屬觸媒之材料結構分析與電化學特性分析 53
4-1-1、ICP-AES 感應耦合電漿放射光譜分析 53
4-1-2、XRD晶體結構分析 54
4-1-3、奈米觸媒表面形態分析 (TEM, SEM) 55
4-1-4、UV-vis光譜分析 60
4-1-5、奈米觸媒表面化學組態分析 (ESCA) 62
4-1-6、觸媒之電化學特性分析 65
4-1-6-1、循環伏安法分析 65
4-1-6-2、葡萄糖滴定測試分析 72
4-2、抗干擾層修飾於葡萄糖感測器上之製程參數與電化學特性分析 74
4-2-1、掃描式電子顯微鏡分析 74
4-2-2、循環伏安法分析 76
4-2-3、電化學交流阻抗分析法 77
4-2-4、電活性物質干擾測試 79
4-3、施加電位之探討 83
4-3-1、電活性物質干擾測試 83
4-3-2、葡萄糖滴定測試分析 85
4-4、待測溶液PH值之探討 87
4-4-1、循環伏安法分析 87
4-4-2、葡萄糖滴定測試分析 88
4-5、非酵素型葡萄糖感測器之電化學性能分析 90
4-5-1、葡萄糖之偵測極限 90
4-5-2、電流之應答時間 90
4-5-3、葡萄糖滴定測試分析 92
4-5-4、穩定性測試 95
4-5-5、模擬血液測試 97
第五章、結論與未來方向 99
第六章、參考文獻 101

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