聚吖啶黃素及 NDGA/Nafion 與 NDGA/FAD 複合薄膜修飾電極之製備及電催化性質之研究

Preparation and Electrocatalytic Properties of Polymerized Acriflavine and NDGA/Nafion and NDGA/FAD Hybrid Film Modified Electrodes

劉美英(Meei-Ing Liu)

指導教授 ： 陳生明

國立臺北科技大學/工程學院/化學工程所/碩士(2005年)

https://doi.org/10.6841/NTUT.2005.00279

摘要

本研究主要分為三部分來討論。第一部份，吖啶黃素是在酸性水溶液中經電聚合而製備成一細薄之電化學活性薄膜。藉由電化學石英晶體微天平 (EQCM)及循環伏安法來探討聚吖啶黃素薄膜即時成長之機制。此聚合物薄膜在酸性溶液下是較穩定的且具有pH 值效應。此薄膜亦可製備在玻璃碳電極、黃金電極及透明半導體氧化銦錫（ITO）電極上。
聚吖啶黃素薄膜修飾電極在酸性及中性水溶液下對NADH具有電催化氧化之活性，此乃經由薄膜之氧化還原對進行電催化氧化使陽極波峰電流成長。在酸性溶液下，薄膜對SO32- 進行電催化氧化及對NO2-、SO52- 與S2O82- 進行電催化還原，顯示出電催化反應之活性。本研究使用紫外/可見光吸收光譜儀及快速截止流動分光光譜法來探討SO52-電催化還原性質，同時亦使用循環伏安法及計時安培法來探討NADH電催化氧化性質。
第二部份，具有電化學活性之NDGA 薄膜，在NDGA 水溶液中可直接沉積在Nafion 修飾電極上。此沉積之NDGA / Nafion 薄膜是穩定的，可在不同的pH 值水溶液中表現出顯著的電化學活性。藉由電化學石英晶體微天平及循環伏安法探討NDGA / Nafion 薄膜即時成長之機制。薄膜亦具有pH 值效應。而對多巴胺、腎上腺素與正腎上腺素（即兒茶酚胺）則具有電催化氧化活性，此乃經由NDGA / Nafion薄膜之氧化態進而促使電催化氧化電流之成長。另外，薄膜也顯示出可逆之電催化性質，可電催化還原多巴胺、腎上腺素及正腎上腺素之氧化產物。
NDGA / Nafion 修飾薄膜對多巴胺及抗壞血酸之混合物亦有電催化氧化之效果。對於多巴胺醌與抗壞血酸之間的化學反應，本研究是藉由旋轉環-碟電極之測定方法來探討其電化學性質。
第三部份，NDGA 在中性水溶液中藉由循環伏安法製備成一細薄之電化學活性薄膜。並以電化學石英晶體微天平及循環伏安法來探討NDGA 薄膜即時成長情形。在中性水溶液中，此修飾薄膜電極對NADH、抗壞血酸、多巴胺及N2H4 具有電催化氧化之活性。
而NDGA 修飾電極，亦可利用方波伏安法成功地分離多巴胺與尿酸及抗壞血酸與尿酸，而得到伏安波峰。
在中性水溶液中，藉由循環伏安法製備而成的 NDGA/FAD 複合薄膜修飾電極，顯示出二對氧化還原對，當移至不同的酸性水溶液時，此二對氧化還原對及薄膜之形式電位會隨著pH 值而不同。在中性水溶液中，此薄膜對 NADH 電催化氧化及對 NAD+ 電催化還原分別具有反應活性，即其對NADH/NAD+ 具有可逆之電催化反應。

關鍵字

薄膜修飾電極 ； 吖啶黃素 ； 聚合作用 ； 電催化 ； 菸鹼醯胺腺嘌呤二核苷酸 ； 去甲二氫癒創木酸 ； 全氟磺酸聚合物 ； 兒茶酚胺 ； 抗壞血酸 ； 黃素腺嘌呤二核苷酸

並列摘要

Part Ⅰ. Polymerization of acriflavine performed in acidic aqueous solution produced thin one redox couple electrochemically active film. The electrochemical quartz crystal microbalance and cyclic voltammetry were used to study the in situ growth of the poly(acriflavine) film. The polymer films were more stable in acidic solutions as their formal potentials being pH dependent with a slope close to –60 mV/pH.The film was produced on glassy carbon, gold, and transparent semiconductor tin(IV) oxide electrodes. The modified film was electrocatalytically oxidation active for NADH in acidic and neutral aqueous solutions, as the electrocatalytic oxidation current developed from the anodic peak of the redox couple. The electrocatalytic oxidation of SO32- and electrocatalytic reduction of NO2-, SO52- and S2O82- by the poly(acriflavine) film in acidic aqueous solutions also showed the electrocatalytic reaction activity. The electrocatalytic oxidation of SO52- was investigated using the UV–visible absorption spectroscopy and the stopped-flow kinetic method. While the electrocatalytic oxidation of NADH was investigated using the cyclic voltammetry and the Chronoamperometric method.
Part Ⅱ. The electrochemically active films of Nordihydroguaiaretic acid (NDGA,1,4-Bis(3,4-dihydroxyphenyl)2.3-dimethylbutane) film modified electrodes can produce by direct deposition on nafion modified electrodes from the Nordihydroguaiaretic acid. The deposition of NDGA/nafion films are stable and show obvious electrochemical activity in various pH aqueous solutions. An electrochemical quartz crystal microbalance and cyclic voltammetry were used to study the in situ growth of NDGA/nafion films. When NDGA/nafion films are prepared and transferred to aqueous solutions at various pH, the formal potential was found to be pH dependent. NDGA/nafion films were electrocatalytically oxidation active for dopamine, epinephrine, and norepinephrine in aqueous solutions, with the electrocatalytic oxidation current developing through the oxidized form of NDGA/nafion film. NDGA/nafion films also shows reversible electrocatalytic properties. Such films electrocatalytically reduce those oxidation products of dopamine, epinephrine, and norepinephrine that are produced from the electrocatalytic oxidation of these compounds by a NDGA/nafion film. NDGA/nafion modified films are also electrocatalytically oxidation active for the mixture of dopamine and ascorbic acid and their electrochemical properties show the reaction of dopamine quinone with ascorbic acid, This reaction was investigated using the rotating ring-disk electrode method.
Part Ⅲ. Preparation of nordihydroguaiaretic acid performed in neutral aqueous solution produced thin one redox couple electrochemically active film. The electrochemical quartz crystal microbalance and cyclic voltammetry were used to study the in situ growth of the nordihydroguaiaretic acid film. The modified film was electrocatalytically oxidation of NADH to NAD+ and the electrocatalytic oxidation of ascorbic acid, dopamine, and N2H4 by the nordihydroguaiaretic acid film in neutral aqueous solutions showed the electrocatalytic reaction activity. Well-separated voltammetric peaks were observed for dopamine with uric acid and ascorbic acid with uric acid using the NDGA/GC modified electrodes. Hybrid films composed of nordihydroguaiaretic acid- flavin adenine dinucleotide (FAD) adsorbed film modified electrodes have been prepared in neutral aqueous solutions. The hybrid NDGA/ FAD film showed two redox couples. When transferred to various aqueous acidic solutions, the two redox couples and the formal potentials of the hybrid films were observed to be pH-dependent. The electrocatalytic oxidation and reduction of NADH and NAD+ by a NDGA/ FAD hybrid film in neutral aqueous solutions was carried out. The electrocatalytic oxidation of NADH and the reversible electrocatalytic reactions of NADH / NAD+ using a NDGA/ FAD hybrid film were found active.

並列關鍵字

Film modified electrode ； Acriflavine ； Polymerization ； Electrocatalysis ； NADH ； Nordihydroguaiaretic acid ； Nafion ； Catecholamines ； Ascorbic acid ； FAD

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