- 學位論文
聚合中性紅/FAD複合薄膜與電沉積銅/鎳/MWCNT奈米薄膜分別對H2O2、O2、NaClO以及葡萄糖之電化學感測研究
Electrochemical determination of hydrogen peroxide, dissolved oxygen, hypochlorite, and glucose using poly(Neutral Red)/FAD and Cu/Ni/MWCNT hybrid composite films
摘要
第一部份：主要是描述中性紅(neutral red)和FAD混合膜是一種多功能電化學傳感器；這種混合膜的製備是利用FAD和中性紅間的靜電作用以電聚合方式所製成；該材料具有良好的表面密閉、pH-相關性、相容性及穩定性；對於過氧化氫、氧氣、次氯酸鈉、溴酸鉀、碘酸鉀及NADH具有良好的電催化性，是一種多功能的電化學傳感器；對於過氧化氫的檢測，該電極具有一快速，且明顯的線性反應，其靈敏度為12.3 μA mM-1 cm-2，線性範圍為10－551.7 mM，偵測極限為0.1 μM (S/N = 3)；對O2的檢測，靈敏度為122.9 μA mM-1 cm-2，線性範圍2.2－9.4 mg L-1，偵測極限為0.1 μM (S/N = 3)；該電極比較特別的是，對於次氯酸鈉的檢測有兩個特徵電位可供選擇，分別是電位在-0.1 V，靈敏度為8.1 μA mM-1 cm-2，線性範圍1.5－141.6 mM,，偵測極限為0.1 μM (S/N = 3)；與另一電位在-0.45 V，靈敏度為9.9 μA mM-1 cm-2，線性範圍1.5－128.8 mM,，偵測極限為0.1 μM (S/N = 3)。該電極在4 °C時具有良好的穩定性，保存超過30天後再進行測試，其反應電流靈敏度變化差異小於5 %。 第二部份：成功製備了一種新類型的鎳和銅奈米粒子修飾多層奈米碳管電極，該電極對葡萄糖的非酶檢測具有靈敏性。Ni和Cu以連續兩個電化學程序電沉積在含有MWCNT修飾的電極上，形成Ni/Cu/MWCNT電極。可經由X-ray繞射和原子力顯微鏡來了解它的表面特徵。由電化學反應可發現其對葡萄糖具有高電流反應和低的過電位。其伏安反應比其他修飾電極包括Ni / GCE、Cu / GCE、Ni /Cu / GCE、Ni / MWCNT / GCE、Cu / MWCNT / GCE和Ni /Cu / MWCNT / GCE 高出2.5-20倍的電流。該應用電位在+0.575 V，對葡萄糖具有2632.9 μA mM-1 cm-2的高靈敏度。線性濃度範圍在0.025 – 800 μM，偵側極限為0.025 μM (S/N = 3)。與添加0.1 mM葡萄糖溶液反應時間約為 1秒。該膜可有效地避免共同性干涉物種的氧化作用干擾，如抗壞血酸、多巴胺、尿酸和碳水化合物。特別是，它也可以有效地分析人體血清樣品中的葡萄糖的濃度。作為非酶葡萄糖傳感器它具有低電位、高靈敏度、高選擇性、穩定性好、反應速度快和低成本的優點。
並列摘要
Part Ⅰ： An multifunctional electrochemical sensor for determination of hydrogen peroxide, oxygen, and hypochlorite has been developed by the hybrid film of poly(neutral red) and FAD. This hybrid film was prepared by electro-codeposition involving electrostatic interaction between FAD and PNR. It was known for a good material with surface hermetic sealing, pH-dependence, compatiblity, and stability. It can be a multifunctional electrochemical sensor due to good electrocatalytic properties for H2O2, O2, NaClO, KBrO3, KIO3, and NADH. For H2O2 detection, this electrode has a rapid and linear response to H2O2 with a significant sensitivity of 12.3 μA mM-1 cm-2, a linear range of 10－551.7 mM, and a detection limit of 0.1 μM (S/N = 3). For O2 detection, it has a sensitivity of 122.9 μA mM-1 cm-2, a linear range of 2.2－9.4 mg L-1, and a detection limit of 0.1 μM (S/N = 3). Particularly, this electrode has two characteristic potentials can be selected for NaClO detection. At an applied potential of -0.1 V, it has a sensitivity of 8.1 μA mM-1 cm-2, a linear range of 1.5－141.6 mM, and a detection limit of 0.1 μM (S/N = 3). At an applied potential of -0.45 V, it shows a sensitivity of 9.9 μA mM-1 cm-2, a linear range of 1.5－128.8 mM, and a detection limit of 0.1 μM (S/N = 3). It presents excellent stability at 4 °C, with a variation of response current less than 5 % over 30 days. Part Ⅱ：A novel type of nickel and copper nanoparticles-modified multi-walled carbon nanotubes electrode has been successfully fabricated for sensitive nonenzymatic glucose detection. Nickel and copper can be sequentially electro-deposited on the MWCNT-modified electrode to form Ni/Cu/MWCNT electrode by two electrochemical procedures. It was characterized by X-ray diffraction and atomic force microscopy. Electrocatalytic reaction was found with high current response and low over-potential to glucose. Voltammetric response presented 2.5–20 times of electrocatalytic current better than other modified electrodes including Ni/GCE, Cu/GCE, Ni/Cu/GCE, Ni/MWCNT/GCE, Cu/MWCNT/GCE, and Ni/Cu/MWCNT/GCE. Applied potential at +0.575 V, it showed a high sensitivity of 2632.9 μA mM-1 cm-2 to glucose. Linearity was obtained over a concentration range of 0.025–800 μM with a detection limit of 0.025 μM (S/N = 3). The response time is about 1 s with addition of 0.1 mM glucose. It can effectively avoid the interference from the oxidation of common interfering species such as ascorbic acid, dopamine, uric acid, and carbohydrate compounds. Particularly, it also can effectively analyze glucose concentration in human serum samples. It has superior advantages of low over-potential, high sensitivity, excellent selectivity, good stability, fast response, and low cost, promising for the development of nonenzymatic glucose sensors.