臺灣博碩士論文加值系統

糖尿病是一種常見的致命疾病，當血糖過高時，其併發症會導致死亡及殘疾，而這些併發症往往是不可逆的，故糖尿病的預防是一大課題。為了解決這個問題，即時感測血糖技術可提供連續、穩定的監測平台，藉此提醒糖尿病患者血糖控制，以避免併發症的發生。其中，因葡萄糖電化學生物感測器之諸多優點，針對糖尿病醫學檢測技術不但具備潛力，更可發展為即時感測血糖監測平台，而利用電化學感測葡萄糖的方法主要可分為兩種：第一種方法是透過電極直接對葡萄糖進行電化學氧化反應，第二種方法是則是先利用葡萄糖氧化酶將葡萄糖轉換成過氧化氫，並利用電化學法對其進行電化學還原反應。
本研究主要是利用四種材料作為電極，開發簡單、快速、準確的方法檢測過氧化氫及葡萄糖，選用材料分別為玻璃碳電極 (GCE)、白金線 (Pt wire)、銅線 (Cu wire)、以及利用電化學沉積法修飾銅於白金線 (Cu/Pt wire)。由於白金與銅針對過氧化氫和葡萄糖具有良好的電催化活性，而結合白金與銅製備的生物傳感器，並透過施加不同電壓沉積銅粒子，可藉由協同作用，進而增強其感測之靈敏性。實驗結果顯示，藉由FE-SEM觀察經修飾後白金線的表面型態，可發現銅粒子可均勻的附著於白金線表面上，當施加高電壓時 (-0.4V) 進行電化學沉積，可觀察銅修飾形狀為樹枝狀。
於電化學循環伏安法分析結果，顯示於PBS pH 7.4溶液與0.1 M 氫氧化鈉溶液，發現利用經電化學沉積銅的材料電極可增強氧化及還原峰，因此可測試其對過氧化氫與葡萄糖之電化學特性。循環伏安法結果顯示，在PBS pH 7.4溶液中施加電壓-0.3 V及-0.4 V，對過氧化氫進行安培測試，可發現施加電壓-0.4 V時沉積銅之白金線，其靈敏度可從0.19 mA.mM-1.cm-2 上升至3.17 mA.mM-1.cm-2。另外，在0.1 M氫氧化鈉溶液中施加電壓0.6 V時感測葡萄糖，於施加電壓-0.4 V沉積銅之白金線，其感測靈敏度可從0.004 mA.mM-1.cm-2 上升至1.37 mA.mM-1.cm-2，靈敏度上升之結果與過氧化氫具有相同的趨勢。

Diabetes mellitus was known as one of the important diseases which is difficult to deal with. Monitoring the blood glucose level for diabetes mellitus patients would be the solution to treat and prevent the patients from the complications that may occur. Glucose electrochemical biosensor is one of devices that were applied to monitor blood glucose level. Glucose detection using electrochemical analyses usually involved two methods. The first method is based on the direct electrooxidation ability of glucose by electrode and the other is based on the electroreduction ability of hydrogen peroxide that was produced from the oxidation of glucose by enzymes, e.g. glucose oxidase. In this study, the bare glassy carbon electrode, platinum wire, copper wire, and copper electrodeposited on platinum wire were developed to prepare simple, fast, and accurate platform for the detection of hydrogen peroxide and glucose.
Because platinum and copper both show good electrocatalytic character toward hydrogen peroxide and glucose, the combination of platinum and copper as a biosensor is supposed to provide the synergetic effects to enhance the sensitivity for the sensing. In this study, copper particles were coated on platinum wire (Pt wire) using electrodeposition technique under different applied voltages. The surface morphology of the copper decorated Pt wire was observed by FE-SEM, which revealed that the copper particles were uniformly attached on the surface of Pt wire. Moreover, at the higher applied potential (-0.4 V), dendrites structure of copper was observed. The electrochemical characteristics against hydrogen peroxide and glucose were investigated using cyclic voltammetry in PBS with pH 7.4 and 0.1 M NaOH solution for different working electrodes, respectively. The results of cyclic voltammograms showed that both the reduction and the oxidation peaks increased by the incorporation of copper as a result of electrodeposition. The amperometric tests against hydrogen peroxide were conducted at around -0.3 V and -0.4 V in PBS with pH 7.4 and the results showed that the sensitivity increased significantly from 0.19 to 3.17 mA.mM-1.cm-2 for the bare Pt wire and the copper electrodeposited Pt wire at -0.4 V when the copper precursor solution was consisted of 50 mM CuSO4 in 0.5 M H2SO4 ((-0.4V)S-Cu/Pt wire). Furthermore, the amperometric test against glucose was performed in 0.1 M NaOH solution at 0.6 V. The sensitivity increased significantly, from 0.004 to 1.37 mA.mM-1.cm-2, by the incorporation of copper on Pt wire at -0.4 V.
The highest sensitivity of (-0.4V)S-Cu/Pt wire was attributed to the increasing specific surface area after deposition of copper particles on the surface of Pt wire, followed by generation of higher electrocatalytic active sites on the surface. In addition, the sensitivity of (-0.4V)S-Cu/Pt wire was compared at the same applied voltage (0.6 V) and electrolyte solution (0.1 M NaOH) with other modified electrodes. The proposed sensor based on (-0.4V)S-Cu/Pt showed superior electrochemical performance with high sensitivity and simple and low-cost fabrication process. Moreover, Cu particles successfully overcome the disadvantages of Pt wire associated with lack of sensitivity and surface poisoning.

Abstract i
Acknowledgement iv
Contents v
List of figures vi
List of tables ix
Abbreviations x
Chapter 1. Introduction 1
Chapter 2. Literature review 3
2-1. Importance of hydrogen peroxide and glucose detection 3
2-1-1. Hydrogen peroxide 3
2-1-2. Glucose 4
2-1-3. Diabetes mellitus 4
2-2. Common methods for glucose detection 6
2-3. Electrochemical biosensor 10
2-4. Metal-based electrochemical glucose and hydrogen peroxide sensor 12
2-4-1. Platinum-based electrochemical biosensor 12
2-4-2. Copper-based electrochemical biosensor 14
2-5. Electrochemical deposition of copper 16
Chapter 3. Experimental 19
3-1. Chemicals 19
3-1-1. Electrodeposition of Cu on Pt wire 19
3-1-2. Electrochemical measurements 19
3-2. Equipment and instruments 19
3-3. Experimental procedures 20
3-3-1. Preparation of Cu/Pt wire 20
3-3-2. Electrochemical Analyses 21
3-4. Material Characterizations 26
3-5. Experimental flow chart 26
Chapter 4. Results and Discussion 27
4-1. Electrodeposition of copper on platinum wire 27
4-2. sSurface morphology of modified platinum wire by FE-SEM 28
4-3. Electrochemical characterization of modified platinum wire 30
4-4. Hydrogen peroxide detection 31
4-4-1. Electrocatalytic ability of hydrogen peroxide at the modified platinum wire 31
4-4-2. Amperometric response of modified Pt wire toward hydrogen peroxide 36
4-5. Glucose detection 43
4-5-1. Electrocatalytic oxidation of glucose at the Cu-modified Pt wires 43
4-5-2. Amperometric response of modified Pt wire toward glucose 46
4-5-3. Comparison of the electrode performance for glucose sensing 50
Chapter 5. Conclusions 52
References 53
Appendix 65

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