聚(黃尿酸)、FAD、CNTs及聚(牛磺酸)/ZrO2複合薄膜電極偵測NADH、H2O2、AA、多巴胺、尿酸、沙丁胺醇及萊克多巴胺的研究

Electrochemical determination of NADH, H2O2, AA, DA, UA, Salbutamol and Ractopamine using poly(xanthurenic acid), FAD, CNTs, and poly(taurine)/zirconia nanocomposites

李穎昇(Ying-Sheng Li)

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(2012年)

摘要

本研究主要分為三部分討論
第一部份把黃尿酸，黃素腺嘌呤二核苷酸及官能基化多層奈米碳管製備在電極表面，並針對不同的製備方法和步驟加以討論。先以黃尿酸和黃素腺嘌呤二核苷酸電沉積在電極表面上，再把官能基化多層奈米碳管沉積於未修飾完成的電極表面，成為聚(黃尿酸)-黃素腺嘌呤二核苷酸/官能基化多層奈米碳管修飾薄膜電極。在示性表現上，以不同掃描速率和不同pH環境測試都得到穩定的電化學結果。特別的是，此修飾薄膜對於菸鹼醯胺腺嘌呤二核苷酸及雙氧水的電催化效果極佳，僅需低過電位便完成催化且能有效增大電流訊號。總結偵測菸鹼醯胺腺嘌呤二核苷酸及雙氧水的結果，線性範圍依序是5×10-6–1.7×10-4 M 及1×10-4–2.9×10-3 M，靈敏度依序是155 μA mM−1 cm−2 及60 μA mM−1 cm−2，偵測極限依序是10-6 M 及10-4 M (S/N = 3)。另外，實驗過程中除了抗壞血酸，沒有其餘干擾物可影響菸鹼醯胺腺嘌呤二核苷酸的檢測。但使用線性掃描伏安法技術，可進一步成功鑑別出菸鹼醯胺腺嘌呤二核苷酸與抗壞血酸的差異。

第二部分以黃尿酸複合單層奈米碳管或多層奈米碳管對抗壞血酸、多巴胺、尿酸同時進行檢測。官能基化(酸處理)後的奈米碳管更具有親水性，能增加固定於電極表面的可能。在各種不同排列組合的複合薄膜中，發現先聚合黃尿酸單體再行沉積奈米碳管，所得電化學結果不僅放大的電流訊號且有更可逆的氧化還原對出現。於各種示性展示(不同掃描速率及不同酸鹼條件下)也都呈現穩定的結果。比起其他修飾材質聚(黃尿酸)，聚(黃尿酸)/單層奈米碳管，單層奈米碳管/聚(黃尿酸)及多層奈米碳管/聚(黃尿酸)，我們設計的聚(黃尿酸)/官能基化多層奈米碳管修飾薄膜對抗壞血酸，多巴胺及尿酸皆有能力展現高電流訊號及低過電位的電化學結果。經實驗計算出對抗壞血酸，多巴胺及尿酸的偵測區間依序是2×10-4–1×10-3 M，4×10-5–3.2×10-4 M及2×10-4–1×10-3 M；靈敏度依序是86，5814及1429 μA mM−1 cm−2；最低偵測極限依序是10 μM，1 μM及5 μM (S/N = 3)。

第三部分為製備聚(牛磺酸)/二氧化鋯修飾薄膜於玻璃碳電極上，並應用於偵測沙丁胺醇以及萊克多巴胺。運用循環伏安法及掃描線性伏安法兩種技術檢視此修飾薄膜對於待測物質的檢測能力。此修飾薄膜偵測沙丁胺醇以及萊克多巴胺的結果分別於電位+0.71 V和+0.65 V得到良好的氧化波峰訊號。除此之外運用電化學阻抗光譜及掃描式電子顯微鏡徹底檢視此修飾薄膜的各項表現。經實驗驗證，偵測沙丁胺醇得到靈敏度為456.1 μA mM-1 cm-2 ; 而偵測萊克多巴胺則得到靈敏度4889.1 μA mM-1 cm-2。且在真實樣本來自豬肉及人體尿液的實驗結果中，也成功偵測了兩種目標待測物，並得到可接受的數值成果。

關鍵字

菸鹼醯胺腺嘌呤二核苷酸 ； 過氧化氫 ； 抗壞血酸 ； 多巴胺 ； 尿酸 ； 黃素腺嘌呤二核苷酸 ； 奈米碳管 ； 聚(黃尿酸) ； 聚(牛磺酸) ； 二氧化鋯 ； 沙丁胺醇 ； 萊克多巴胺 ； 微分脈衝伏安法 ； 電化學阻抗光譜 ； 掃描線性伏安法 ； 安培法 ； 修飾電極

並列摘要

Part Ⅰ：The hybrid composites of xanthurenic acid (Xa), flavin adenine dinucleotide (FAD), and carbon nanotubes (CNTs) have been successfully prepared on electrode surface and discussed with different prepared procedures. The polyXa-FAD/f-MWCNT formed with the firstly polyXa and FAD electro-codeposition and the secondly CNTs adsorption shows much higher current response than those hybrid composites made by inverted procedures. It is surface-confined and stable in various scan rates and different pH conditions. Particularly, the polyXa-FAD/f-MWCNT composite shows higher current response and lower over-potential to reduced β-nicotinamide adenine dinucleotide (NADH) and hydrogen peroxide (H2O2). Amperometric response provides a linear response range of 5×10-6–1.7×10-4 M and 1×10-4–2.9×10-3 M with a sensitivity of 155 μA mM−1 cm−2 and 60 μA mM−1 cm−2, and detection limit of 10-6 M and 10-4 M (S/N = 3) for NADH and H2O2, respectively. No interference occurred in the amperograms except of the case for NADH determination in the presence of AA. Linear sweep voltammetry (LSV) technique can help to distinguish NADH and AA response using this bifunctional sensor for NADH and H2O2 determination in the biosystem.

Part II：The simultaneous determination of ascorbic acid (AA), dopamine (DA), and uric acid (UA) is investigated with polymers/carbon nanotubes (CNTs) hybrid composites including xanthurenic acid (Xa), single-walled carbon nanotubes (SWCNT), and multi-walled carbon nanotubes (MWCNT). The functionalized CNTs with acidic treatment can be more hydrophilic to adsorb on electrode surface. The film type of CNTs covered polyXa on electrode surface is found with higher current response and more reversible redox couple in neutral solution. The polyXa/ f-MWCNT of this film type is stable in different scan rates and pH conditions. It shows higher current response and lower over-potential to AA, DA, and UA species when compared with other modifiers including polyXa, polyXa/SWCNT, SWCNT/polyXa, f-MWCNT/polyXa, and polyXa/f-MWCNT. It provides a linear response range of 2×10-4–1×10-3 M, 4×10-5–3.2×10-4 M, and 2×10-4–1×10-3 M with a sensitivity of 86, 5814, and 1429 μA mM−1 cm−2 and detection limit of 10 μM, 1 μM, and 5 μM (S/N = 3) for AA, DA, UA, respectively.

Part III：Herein we report the facile synthesis of poly taurine/zirconia nanoparticles (ZrO2) modified film glassy carbon electrode and its application for the detection of salbutamol and ractopamine. The poly taurine/ZrO2 nanoparticles was directly employed for the detection of salbutamol and ractopamine using linear sweep voltammetry(LSV).The modified film shows a well oxidation peak for salbutamol at 0.71V and ractopamine at 0.65V. Furthermore, the electrochemical measurements and surface morphology were studied using CV, EIS and SEM analysis. The film exhibits rapid and linear electrocatalytic response of salbutamol with the sensitivity of 456.1 μA mM-1 cm-2 and 4889.1 μA mM-1 cm-2 for ractopamine. The proposed electrode also successfully detects the salbutamol and ractopamine in pig meat and human urine samples.

並列關鍵字

NADH ； H2O2 ； AA ； DA ； UA ； FAD ； CNTs ； polyXa ； poly taurine ； ZrO2 ； salbutamol ； ractopamine ； DPV ； EIS ； LSV ； IT curve ； modified electrode

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