染料結合奈米碳管複合膜測定過氧化氫和生化化合物之研究

Dye containing MWCNTs hybrid films for the determination of hydrogen peroxide and biochemical compound

彭雅鈺(Ya-Yu Peng)

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(2010年)

摘要

第一部份，主要是探討催化過氧化氫的一種新穎生物感測器。此感測器主要是由改質矽酸鹽(Ormosils)和尼羅藍(Nile Blue) 結合多層奈米碳管(MWCNTs)、Nafion(NAF)及過氧化酶(HRP)所構成的。而改質矽酸鹽(Ormosils)是指3-aminopropyltrimethoxysilane(APTMOS)2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane(EETMOS)和Phenyltrimethoxysilane(PHTMOS)所結合而成的。選用有著氧化還原反應的尼羅藍染料、過氧化酶及多層奈米碳管結合改質矽酸鹽修飾薄膜。而薄膜中的Nafion是提高改質矽酸鹽薄膜裡的電子轉移速率；EETMOS是改進改質矽酸鹽薄膜裡的機械強度；APTMOS是增加改質矽酸鹽薄膜裡的生物相容性。其表面型態為尼羅藍/多層奈米碳管/NAF/過氧化酶/改質矽酸鹽複合材料。由掃描式電子顯微鏡(SEM)、原子力顯微鏡(AFM)和循環伏安法測量來檢測此修飾膜的特性。本研究製備出的生物感測器在最適化的條件下催化過氧化氫有著從2x10-7到3.8x10-4 M極佳的線性濃度範圍，且偵測極限是1x10-7 M。同時，也有研究此生物感測器對pH濃度、酵素量以及在標準狀態下電位的影響。本研究所探討出的生物感測器方便使用且顯示出高選擇性及好的穩定性。
第二部份為探討催化過氧化氫的一種生物感測器。選擇一個陽離子染料亮甲酚藍、過氧化酶和多層奈米碳管結合改質矽酸鹽修飾在玻璃碳電極。利用改質矽酸鹽、亮甲酚藍和Nafion結合多層奈米碳管和過氧化酶製備出高靈敏度、快速偵測、高穩定性的過氧化氫生物感測器。修飾薄膜中的EETMOS是提高改質矽酸鹽薄膜裡的機械強度；APTMOS是提供固定過氧化酶在改質矽酸鹽薄膜裡的生物相容性；多層奈米碳管可改善薄膜裡的導電率。由掃描式電子顯微鏡(SEM)、原子力顯微鏡(AFM)和循環伏安法測量來檢測此修飾膜的特性。使其性能達到最佳化。同時，也會系統化地研究此生物感測器對不同pH值濃度、酵素量、和催化電位的影響而本研究所探討出的生物感測器方便使用且顯示出高選擇性及好的穩定性。且在最適化的條件下，此生物感測器可展現寬廣的線性範圍從3x10-7到1x10-4 M和極低的偵察極限為1x10-7 M。
第三部分主要探討新式的多層奈米碳管/NAF /阿蕊氏紅沉積薄膜，此薄膜由多層奈米碳管混合Nafion和阿蕊氏紅利用電化學方法修飾於玻璃碳電極及黃金電極上，而在電催化結果對於，如：血清素、退黑激素生化分子的氧化反應都具有催化的效果。透過循環伏安法方法就可以將阿蕊氏紅沉積薄膜修飾於黃金電極，提高多層奈米碳管/NAF /阿蕊氏紅修飾膜的實用性。此薄膜修飾玻璃碳電極經由計時安培法可偵測血清素濃度範圍為1.5×10–6到1.5×10–4 M，其偵側極限為1×10–6 M；偵測退黑激素濃度範圍為2.5×10–6 到1.5×10–4 M，其偵側極限為 1×10–7 M。

關鍵字

尼羅藍 ； 多層奈米碳管 ； 過氧化氫 ； 過氧化酶亮甲酚藍 ； 改質矽酸鹽 ； 阿蕊氏紅 ； 血清素 ； 退黑激素

並列摘要

Part I：I：A novel amperometric biosensor for the analytical determination of hydrogen peroxide was developed. The fabrication of the biosensor was based on the coimmobilization of horseradish peroxidase (HRP), nile blue and multiwalled carbon nanotubes with in ormosils; 3-aminopropyltrimethoxysilane (APTMOS), 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (ETMOS) and phenyltrimethoxysilane (PHTMOS).The classical redox dye Nile blue and Peroxidase (HRP) were coimmobilized into the multi wall carbon nanotoubes (MWCNTs) modified ormosil matrix. Nafion was dispersed into the ormosil film to enhance the rate of the electron transfer. EETMOS group in ormosil film improves the mechanical strength. APTMOS group provides biocompatible for theimmobilization of enzymes. The surface morphology of MWCNTs/NB/NAF/HRP composite. The ormosil modified electrodes were characterized with Scanning electron microscopy(SEM), Atomic force microscopy (AFM) and Cyclic voltammetry demonstrated the NB coimmobilized with HRP in this way, displayed good stability and could efficiently shuttle electrons between immobilized enzyme and electrode.The facile procedure of immobilizing HRP and MWCNTs into the ormosils film . The optrmun biosensor had a fast response of H2O2 , and excellent linear range of concentration from 2x10-7 to 3.8x10-4 M with the detection limit of 1x10-7 M under the optimum conditions. At the same time, the influence of solution pH, effect of enzyme amount, steady-state applied potential on the biosensor was investigated. The preparation of the developed biosensor was convenient and showed high sensitivity with good stability.
Part II：A biosensor for the detection of hydrogen peroxide has been developed. A cationic dye brilliant Cresy Blue (BCB) and horseradish peroxidase (HRP) were coimmobilzed within ormosils on multiwalled carbon nanotabes modified glassy carbon electrode. The feature of biosensor is highly sensitive, fast responding and stable.EETMOS group in ormosils dispersed the mechanical strength of the flim . APTMOS group provides biocompatible for the immobilization of horseradish peroxidase (HRP).The presence of MWCNTs improved the conductivity of the film. The ormosil modified electrodes .The Scanning electron microscopy (SEM), Atomic force microscopy (AFM) and Cyclic voltammetry demonstrated the BCB coimmobilized with HRP in this way, displayed good stability and could efficiently shuttle electrons between immobilized enzyme and electrode. the influence of solution pH, effect of enzyme amount, steady-state applied potential on the biosensor was investigated. The preparation of the developed biosensor was convenient and showed high sensitivity with good stability.The proposed H2O2 biosensor exhibited wide linear range form 3x10-7 to 1x10-4 M and low detection limit of 1x10-7 M.

Part III：A novel biocomposite film MWCNTs/NAF /AR was investigated. This Multi-wall carbon nanotubes (MWCNTs) aling with the incorporation of Nafion and Alizarin Red has been synthesized on glassy carbon electrode and gold electrode by potentiostatic methods. The biocomposite film also exhibits a promising enhanced electrocatalytic activity towards the oxidation of biochemical compounds as serotonin and melatonin.The cyclic voltammetry has been used for the measurement of electroanalytical properties of analytes by means of biocomposite film modified gold electrodes.The chronoamperometry has been used for the amperomtric detection of analytes at MWCNTs/NAF/AR modified film electrocatalytic behavior towards reduction of serotonin in the linear range of 1.5×10–6 to 1.5×10–4 M and the detection limit is 1 ×10–4 M, and melatonin in the linear range of 2.5×10–6 to the 1.5×10–4 M and detection limit is 1 ×10–7 M.

並列關鍵字

Nile Blue（NB) ； MWCNTs ； Hydrogen peroxide (H2O2) ； horseradish peroxidase（HRP) ； Brilliant Cresy Blue(BCB) ； Ormosils ； Alizarin Red（AR) ； Serotonin, ； Melatonin.

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