聚亞甲基藍/FAD與聚發光胺/MWCNT修飾電極應用於測定H2O2和NADH生物感測器的電化學研究

A study of electrochemical biosensors using poly (methylene blue)/FAD and poly(luminol)/MWCNT modified electrodes for determining hydrogen peroxide and NADH

銀解語(Chien-Yu Yin)

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)

https://doi.org/10.6841/NTUT.2011.00180

摘要

本研究主要分為兩部分來討論，第一部分為使用循環伏安法在pH7溶液中將奈米結構聚亞甲基藍(PMB)/黃素腺嘌呤雙核甘酸(FAD)薄膜製備於玻璃碳電極上，重複掃描，電位範圍為-0.6~1.1V，黃素腺嘌呤雙核甘酸(FAD)因與亞甲基藍共聚合的靜電作用固定於玻璃碳電極上，而亞甲基藍則聚合在電極表面。此修飾電極表現出來的電化學特性，包含電極表面的受限制性和對於pH的依賴性。在中性環境下，它具有良好的電催化特性，以還原過氧化氫、溴酸鉀、碘酸鉀和次氯酸鈉以及電催化氧化還原酶。在pH 7無氧的磷酸鹽緩衝溶液中形式電位為-0.45 V vs. Ag/AgCl時偵測過氧化氫，顯示出迅速的線性反應，其線性範圍為80 μM 到 960 μM，偵測極限為0.1 μM ，靈敏度為1109 μA mM-1 cm-2，雜訊比為3，其在室溫下有優良的穩定性，放置超過30天時，其反應電流的變化不超過5 %。

第二部份為以電聚合發光胺和官能基化的多層奈米碳管複合薄膜，可以提高對NADH的電催化氧化反應。此複合薄膜為電聚合發光胺後將官能基化的多層奈米碳管吸附於電極表面，且此複合薄膜的製備過程是簡易的。該修飾電極表現出兩個氧化還原對以NADH氧化顯示出兩個峰電流值約為0.1和0.3 V（vs. Ag/AgCl）。kkin 為NADH電催化氧化的動力學常數，計時電流和伏安法使用RDE，提供的值接近105 M-1 s-1。應用電位在0.1 V時，NADH感測器的線性響應範圍為5×10-6 至 1.5×10-4 M，靈敏度為183.9μA mM−1 cm−2，偵測極限為0.6μM，定量偵測極限為5μM，雜訊比為3。

關鍵字

黃素腺嘌呤雙核甘酸 ； 菸鹼醯胺腺嘌呤二核苷酸 ； 過氧化氫 ； 亞甲基藍 ； 電催化 ； 聚發光胺 ； MWCNT ； 電化學感測器

並列摘要

Part Ⅰ： An electrochemical biosensor for determination of hydrogen peroxide (H2O2) has been developed by the hybrid film of poly(methylene blue) and FAD (PMB/FAD). The PMB/FAD hybrid film was performed in PBS (pH 7) containing methylene blue and FAD by cyclic voltammetry. Repeatedly scanning potential range of -0.6－1.1 V, FAD was immobilized on the electrode surface by electrostatic interaction while methylene blue was electropolymerized on electrode surface. This modified electrode was found surface confined and pH dependence. It showed good electrocatalytic reduction for H2O2, KBrO3, KIO3, and NaClO as well as electrocatalytic oxidation for NADH. At an applied potential of -0.45 V vs. Ag/AgCl, the sensor showed a rapid and linear response to H2O2 over the range from 80 μM to 960 μM, with a detection limit of 0.1 μM and a significant sensitivity of 1109 μA mM-1 cm-2 (S/N = 3). It presented excellent stability at room temperature, with a variation of response current less than 5 % over 30 days.
Part 2：This work presents that electrocatalytic oxidation of NADH can be enhanced by the hybrid composites of functionalized MWCNT and polyluminol. The hybrid composites can be easily prepared by the electropolymerization of luminol and the adsorption of functionalized MWCNT. The modified electrode exhibits two redox couples and shows two electrocatalytic peaks at about 0.1 and 0.3 V (vs. Ag/AgCl) to NADH oxidation. The kinetic constant, kkin, for the electrocatalytic oxidation of NADH, evaluated by chronoamperometry and voltammetry using RDE, provided values close to 105 M-1 s-1. Applied potential at 0.1 V, the sensor provides a linear response range for NADH from 5×10-6 up to 1.5×10-4 M with a sensitivity of 183.9 μA mM−1 cm−2, detection and quantification limits of 0.6 and 5 μM (S/N = 3), respectively.

並列關鍵字

Hydrogen peroxide ； FAD ； Methylene blue ； NADH ； Electrocatalysis ； Polyluminol ； MWCNT ； Electrochemical sensors

參考文獻

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