多壁奈米碳管-聚二烯丙基二甲基氯化銨-石墨烯複合材料修飾於網版印刷碳電極對酚類抗氧化劑的電化學分析

Multi-walled Carbon Nanotubes-Poly(diallyldimethylammonium chloride)-Graphene Composite Materials for Electrochemical Analysis of Phenolic Antioxidantsmaterials for electrochemical analysis of phenolic antioxidants

張仲崑(Jhong-Kun Jhang)

指導教授 ： 鄭淑華

國立暨南國際大學/科技學院/應用化學學系/碩士(2017年)

摘要

酚類抗氧化劑如第三丁基氫醌(tert-butylhydroquinone, TBHQ)與丁基羥基茴香醚(butylated hydroxyanisole, BHA)是被廣泛用於食品、化妝品與石油產品中來避免產品劣化、變質氧化的食品添加劑，因研究發現這類抗氧化劑會產生有毒物質危害到人體健康，因此在美國食品和藥物管理局（FDA）和歐盟（EU）對於特定食品如食用油、乳酪及奶油中，明定可容許TBHQ與 BHA的使用濃度的最大劑量的添加規範。本研究以奈米碳材複合材料來開發TBHQ 與 BHA的電化學偵測方法。
本研究藉由加入聚二烯丙基二甲基氯化銨(PDDA)幫助MWCNT-COOH和GR兩種碳材均勻分散在二次水中，並利用MWCNT-COOH、GR與PDDA相互摻雜形成導電網絡狀結構，再以滴覆後乾燥的方式將複合碳材修飾於網版印刷碳電極(Screen-Printed Carbon Electrode, SPCE)，製備出多壁奈米碳管-聚二烯丙基二甲基氯化銨-石墨烯修飾電極(MWCNT-COOH_PDDA_GR/SPCE)。運用此修飾電極以循環伏安法(cyclic voltammetry, CV)來偵測TBHQ與BHA，發現bare SPCE上TBHQ和BHA的氧化電位分別為0.5 V與0.7 V，而修飾上複合材料後能使訊號分別降低至0.3 V與0.6V，因此由實驗結果發現複合碳材優良的韌性、比表面積與電子傳導速率不僅提升偵測TBHQ和BHA的靈敏度，並能讓兩者分析物的氧化電位降低，最後利用浸泡的方式將修飾電極透過差式脈衝伏安法(Differential Pulse Voltammetry, DPV)來同時偵測TBHQ與BHA。本分析方法對TBHQ的靈敏度為4.32 μA/μM，BHA的靈敏度為0.90 μA/μM，TBHQ線性範圍為0.8-10 μM與10-100 μM，BHA線性範圍為 4-180 μM，而TBHQ與BHA的偵測極限分別為0.04 μM與0.21 μM (S/N=3)。

關鍵字

電化學感測器 ； 酚類抗氧化劑 ； 多壁奈米碳管 ； 石墨烯 ； 聚電解質

並列摘要

Antioxidants such as TBHQ and BHA, are widely used in products such as edible oils and creams to prevent oxidation. However, antioxidants have been reported to cause damage to human health. Therefore, The U.S. Food and Drug Administration (FDA) and European Union enacted guidelines on inclusion antioxidants in these products .Therefore, we develop simple and sensitive analytical methods to detect TBHQ and BHA simultaneously.
In this study, we used MWCNT-COOH, GR and PDDA to form a conductive network structure of nano-composite, which was dropped onto screen-printed carbon electrode(SPCE), to obtain an electrochemical sensor for TBHQ and BHA. The increased sensitivity and the reduced oxidation potential for TBHQ and BHA were due to the excellent mechanical properties, specific surface area and good electron transfer rate of composite carbon materials. The proposed sensor was observed to adsorb TBHQ and BHA at SPCE/MWCNT-COOH_PDDA_GR in pH 2.0 PBS. Under optimal differential pulse voltammetry (DPV), the linear response range of 0.8-10 and 10-100 μM for TBHQ and 4-180 μM for BHA were obtained the method sensitivity were 4.32 μA/μM and 1.87 μA/μM for TBHQ and 0.90 μA/μM for BHA, and the detection limit was 0.04 μM and 0.21 μM (S/N=3),respectively.

並列關鍵字

Electrochemical sensor ； Antioxidant ； MWCNT-COOH ； Graphene ； PDDA

參考文獻

[1] M.M. Delgado-Zamarreño, I. González-Maza, A. Sánchez-Pérez, R. Carabias Martínez, Analysis of synthetic phenolic antioxidants in edible oils by micellar electrokinetic capillary chromatography, Food Chemistry, 100 (2007) 1722-1727.

[2] T. Galeano Diaz, A. Guiberteau Cabanillas, M.F. Alexandre Franco, F. Salinas, J.C. Viré, Voltammetric Behavior and Simultaneous Determination of the Antioxidants Propyl Gallate, Butylated Hydroxyanisole, and Butylated Hydroxytoluene in Acidic Acetonitrile-Water Medium Using PLS Calibration, Electroanalysis, 10 (1998) 497-505.

[3] S. Michalkiewicz, M. Mechanik, J. Malyszko, Voltammetric Study of Some Synthetic Antioxidants on Platinum Microelectrodes in Acetic Acid Medium, Electroanalysis, 16 (2004) 588-595.

[4] P. Zhao, J. Hao, Tert-butylhydroquinone recognition of molecular imprinting electrochemical sensor based on core–shell nanoparticles, Food Chemistry, 139 (2013) 1001-1007.

[5] R.A. Medeiros, B.C. Lourenção, R.C. Rocha-Filho, O. Fatibello-Filho, Simple Flow Injection Analysis System for Simultaneous Determination of Phenolic Antioxidants with Multiple Pulse Amperometric Detection at a Boron-Doped Diamond Electrode, Analytical Chemistry, 82 (2010) 8658-8663.