奈米碳管結合酵素和染料薄膜修飾電極之電化學性質研究

Preparation, Characterization and Electroanalytical Application of Multi-walled Carbon Nanotubes with Enzyme and Dye Film Modified Electrodes

楊欣穎(Sing-Ying Yang)

指導教授 ： 陳生明

國立臺北科技大學/工程學院/化學工程研究所/碩士(2011年)

摘要

本研究第一部份是將此複合薄膜結合多層奈米碳管(multi-walled carbon nanotube ，簡稱MWCNTs)及穀胱甘肽還原酶(glutathione reductase，簡稱 GR)製備在黃金電極上。MWCNTs的存在增加了表面覆蓋率(Γ)和穩定性。此修飾電極對於還原穀胱甘肽(glutathione，簡稱GSH)增加其電催化的活性。透過循環伏安圖法測量此修飾電極分析物的電化學性質。此MWCNTs/GR薄膜修飾電極其靈敏度值，高於只有單一穀胱甘肽還原酶的修飾電極。我們使用掃描電子顯微鏡(SEM)和原子力顯微鏡(AFM)去觀察此薄膜的表面型態，可以觀察到GR確實製備在多層奈米碳管上。
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第二部份為官能化的多層奈米碳管(f-MWCNTs)結合鹼性紅9(BR9)，製備在玻璃碳電極(GCE)及銦錫氧化玻璃上(ITO)。f-MWCNTs的存在增加了電極的表面覆蓋率及穩定性。此修飾電極也表現出對神經傳遞物質血清素及腎上腺素的氧化有電催化活性的作用。修飾過的電極經由循環伏安法，可用於測量分析物的電化學性質。f-MWCNTs/BR9複合薄膜修飾電極的靈敏度值，相較於只有鹼性紅9及f-MWCNTs修飾電極都來的較佳。本研究利用掃描電子顯微鏡(SEM)及原子力顯微鏡(AFM)觀察，其修飾電極的表面型態，從圖中也可以清楚的看到鹼性紅9，確實製備在f-MWCNTs上。最後，使用微分脈衝伏安法，對f-MWCNTs/BR9複合薄膜修飾電極，對含有分析物的混合物做偵測。
第三部份是製備辣跟過氧化酶(HRP) /氧化鉍(Bi2O3) /多層奈米碳管複合薄膜修飾電極研究其電化學性質。為了提高此修飾電極的穩定性及避免干擾物的影響，所以在此薄膜修飾電極製備上一層nafion。接著利用掃描電子顯微鏡(SEM)、X光能譜分析儀(EDX)、原子力顯微鏡(AFM)及X-射線繞射光譜儀(XRD)研究氧化鉍粒子、氧化鉍結合多層奈米碳管及NF/HRP/Bi2O3-MWCN薄膜的電化學性質。也經由電化學阻抗頻譜圖(EIS)，探討不同膜修飾電極的電化學行為。此NF/HRP/Bi2O3-MWCNT複合薄膜修飾電極，在生理條件下(pH7)偵測過氧化氫。計時安培法在線性範圍13.12mM至 36.95 mM之間，對過氧化氫顯示優秀的反應。此NF/HRP/Bi2O3-MWCNT生物感測器，對於偵測過氧化氫有很高的選擇性，即便是存在於隱型眼鏡清洗液中的過氧化氫也能有效偵測。

關鍵字

多層奈米碳管 ； 穀胱甘肽還原酶穀胱甘肽鹼性紅9 ； 血清素 ； 腎上腺素 ； 辣根過氧化酶過氧化氫 ； 氧化鉍奈米粒子 ； 修飾電極 ； 電催化 ； 直接電化學

並列摘要

Part I：MWCNTs/GR modified electrode which contains multi-walled carbon nanotubes (MWCNTs) and glutathione reductase (GR) has been synthesized on gold electrode. The presence of MWCNTs enhances the surface coverage concentration (Γ) and stability. The modified electrode also exhibits a promising enhanced electrocatalytic activity towards the reduction of glutathione disulfide (GSSG). The cyclic voltammetry has been used for the measurement of electroanalytical properties of analytes by means of modified electrodes. The sensitivity values of MWCNTs/GR modified gold electrode are higher than the values which are obtained for only GR modified electrode. We have studied the surface morphology of the modified electrode using scanning electron microscopy (SEM) and atomic force microscopy (AFM), which revealed that GR is coated on MWCNTs. Finally, the flow injection analysis (FIA) has been used for the amperometric detection of analytes at MWCNTs/GR film modified SPCE.

Part II： In this work, we report the direct electrochemistry of horseradish peroxidase (HRP) at bismuth oxide (Bi2O3) nanoparticles coated multiwalled carbon nanotubes (MWCNTs) film modified glassy carbon electrode (GCE). In order to improve the stability of the modified electrode and to avoid the interference effect a thin layer of nafion was formed over the modified electrode. The prepared Bi2O3 nanoparticles, Bi2O3 nanoparticles coated MWCNT (Bi2O3-MWCNT), and NF/HRP/Bi2O3-MWCNT films have been characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), atomic force microscopy (AFM), and powder X-ray diffraction (XRD) studies. The electrochemical behavior of the various film modified electrodes has also been probed via electrochemical impedance spectroscopy (EIS) technique. The prepared NF/HRP/Bi2O3-MWCNT film modified GCE has been employed for H2O2 quantification at physiological pH conditions. The NF/HRP/Bi2O3-MWCNT film showed excellent amperometric i–t response towards H2O2 in the linear concentration range between 13.12 mM-36.95 mM. The developed NF/HRP/Bi2O3-MWCNT biosensor was highly selective towards H2O2 and it detects H2O2 present in the contact lens cleaning solution.

Part III： f-MWCNTs/BR9 modified electrode which contains functionalized multi-walled carbon nanotubes (f-MWCNTs) and Basic Red 9 (BR9) has been synthesized on glassy carbon electrode (GCE) and indium tin oxide (ITO). The presence of f-MWCNTs enhances the surface coverage (Γ) and stability. The modified electrode also exhibits a promising enhanced electrocatalytic activity towards the oxidation of neurotransmitters, serotonin and epinephrine (EP). The cyclic voltammetry has been used for the measurement of electroanalytical properties of analytes by means of modified electrodes. The sensitivity values of f-MWCNTs/BR9 modified glassy carbon electrode are higher than the values which are obtained for only BR9 and f-MWCNTs modified electrode. We have studied the surface morphology of the modified electrode using scanning electron microscopy (SEM) and atomic force microscopy (AFM), which revealed that BR9 is coated on f-MWCNTs. Finally, the Differential pulse voltammetry (DPV) has been used for the detection of mixture analytes at f-MWCNTs/BR9 modified electrode.

並列關鍵字

Multi-walled carbon nanotubes ； Glutathione reductase ； Modifiedelectrodes ； Electrocatalysis ； Glutathione ； Basic Red 9 ； Epinephrine ； Serotonin ； Direct electrochemistry ； Horseradish peroxidase ； Bi2O3 ； Hydrogen peroxide

參考文獻

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