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標題: Application of Clay-modified Electrodes on Electroanalysis of Tea Soups and Investigation of Layer Charge
作者: Yu-Ju Liu
關鍵字: 黏土礦物
clay minerals
phenolic compounds
tea soup
layer charge
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摘要: 黏粒修飾電極 (CME) 具有預濃縮分析物的能力,在分析上可以有更高靈敏度與更低偵測極限,可用於農藥、重金屬及有機化合物等的偵測,且黏粒層中所具有的電子傳導特性也常被用於電化學分析、光催化性和生化感測器等用途。茶葉中含有多量酚類化合物,已有文獻證實其具有多種保健及預防疾病之生理功效,其也是茶湯味道、香氣及色澤的重要來源。由於近年來台灣出現食安問題,常有產品標示不實的情況,因此,引發想利用嶄新快速的電化學分析方法來偵測茶湯中的酚類化合物。本論文研究目的以黏粒修飾鈦還原後再氧化電極 [Ti-SWa-SPCE*(O)] 搭配循環伏安法偵測茶湯及市售茶品之酚類化合物。試驗結果指出由17個不同品種及發酵程度之茶湯所偵測之循環伏安圖中可看到酚類化合物的氧化還原波峰對,其中烏龍茶類茶湯有較明顯的兩個氧化波峰 (0.5 V, 0.57 V),而紅茶類茶湯則只有一明顯氧化波峰 (0.6 V)。此外,由各商店所買到的46個市售茶品所測到的循環伏安圖中也有類似各種茶葉茶湯所測到的氧化還原波峰對,顯示茶品中確實含有和茶湯相類似的酚類化合物。46個茶品涵蓋有各種綠茶、烏龍茶及紅茶等,其中以16種紅茶類茶品只有一個氧化波峰 (0.59 V),其餘30種茶品均有兩個氧化還原波峰 (0.5 V, 0.57 V),且由16種紅茶類茶品的氧化波峰電流量 (6.61 ~ 59.35 μA) 得知其所含酚類化合物的含量不同,此偵測方法期望能有助於對茶葉茶湯和茶品酚類化合物的快速測定。此外,黏粒修飾電極亦可作為一種研究電化物質通過帶負電荷黏粒膜層之傳輸過程的方法,以往的研究常使用 Fe(CN)63- 及 Ru(NH3)63+ 作為偵測物以進行電化學分析特性的探討,故本研究將六種標準黏土礦物及十二種台灣代表性的土壤黏粒結合洋菜膠修飾在三極式網版印刷電極上,是本論文研究研發出來的一種新型修飾電極 (NCME, novel clay modified electrode),以 Ru(NH3)63+ 及 Fe(CN)63- 作為探針化合物,進行層面電荷特性之探討。試驗結果指出,六種標準黏土礦物及十二種土壤黏粒修飾電極對 Ru(NH3)63+ 及 Fe(CN)63- 偵測到的氧化還原波峰電流量皆會隨掃描速率增加而上升,且皆符合 Randles-Sevcik 擴散方程式理論,其中以 Ru(NH3)63+ 測得之氧化還原電流量皆大於 Fe(CN)63-,顯示 Ru(NH3)63+ 較能表現出不同黏粒修飾電極中層面電荷的電化學特性。六種標準黏土礦物修飾電極對 Ru(NH3)63+ 電化學反應皆有明顯的氧化還原波峰,且具有良好的可逆性,以 SWy-1 及 VTx-1 的氧化還原波峰訊號最為明顯,明顯能展現出黏土礦物的層面電荷特性,六種標準黏土礦物的負電荷電場效應則對 Fe(CN)63- 具有排斥力,導致 Fe(CN)63- 不易通過黏粒膠體膜層到達電極表面進行電化學反應,因而使其偵測到的氧化還原波峰電流量較不明顯。試驗結果中也指出十二種土壤黏粒修飾電極對 Ru(NH3)63+ 的電化學反應中,以柳營、五魁寮(4)及中壇可測得較大的氧化還原波峰對,而在 Fe(CN)63- 的反應上以柳營和中萬甲有較明顯之氧化還原波峰訊號。由於土壤黏粒是由不同黏土礦物與有機質、游離氧化鐵等物質所組成,而呈現一複雜系統,層面電荷的電化學分析會受到有機質含量、游離氧化鐵含量和膨脹性黏土礦物等所影響。
Clay-modified electrodes (CME) can preconcentrate and analyze and that have higher sensitivity and lower detection limits. CME also have been applied for the determination of pesticides, heavy metals and organic compounds, and that also are used as electroanalysis, photocatalysis and biosensors due to the good conductivity of clay layer. Tea contain a great number of phenolic compounds, and many studies are demonstrated that these compounds have many a variety of health care and prevention of the physiological effects of disease, and that also are the main source of the taste, smell and color of tea soups. Recently, many food safety problems have been reported in Taiwan which often occurred the situations of mislabeling and adulteration or counterfeit, therefore, we decide to use a new and rapid electrochemical methods to analyze the phenolic compounds of tea soups. In this research, the phenolic compounds of tea soups and commercially available tea products are detected by clay-modified screen-printed carbon electrodes with the reduction of Ti4+ and oxidation again [Ti-SWa-SPCE*(O)] using cyclic voltammetry method. The results indicated that the oxidation-reduction peak pairs of phenolic compounds can be seen from the cyclic voltammograms of seventeen teas with different varieties and degrees of fermentation. Oolong tea has two obvious oxidation peaks (0.5 V, 0.57 V), while black tea only observes one obvious oxidation peak. Furthermore, the cyclic voltammograms of forty-six commercially available tea products bought from different stores also appear the similar oxidation-reduction peak pairs to the results of tea soups, the results indicated tea products indeed contain phenolic compounds which are similar to tea soups. Forty-six commercial tea products having a variety of green tea, oolong tea and black tea. Sixteen black tea products have only one oxidative peak (0.59 V), and else thirty tea products all have two oxidative peaks (0.5 V, 0.57 V). Moreover, it can identify the different contents of phenolic compounds with the oxidative currents of sixteen kinds of black tea products (6.61 ~ 59.35 μA). This electrochemical method is expected to contribute to the rapid determination of phenolic compounds in tea soups and tea products. In addition, CME can be used as a method of studying the transport process of an electrochemical material [Fe(CN)63- and Ru(NH3)63+] through a negatively charged clay layer, and that were used to investigate layer charge characters of six standard clay minerals and twelve Taiwan representative soil clays with a new clay-modified electrode combining agar (novel clay modified electrode, NCME). The results showed that the oxidative-reductive currents of Ru(NH3)63+ and Fe(CN)63- for six standard clay minerals and twelve Taiwan representative soil clays increased with increasing scan rate and the currents and diffusive rate would fit Randles-Sevcik equation. The currents of Ru(NH3)63+ are larger than Fe(CN)63- that indicate Ru(NH3)63+ is a good probe for the character of layer charge of clay minerals in NCME. Ru(NH3)63+ have obvious oxidative-reductive peaks and great reversibilities in NCME of six standard clay minerals, especially as SWy-1 and VTx-1, while Fe(CN)63- is excluded by the negative charges of six standard clay minerals, leading little currents due to hardly pass the film of NCME. In twelve Taiwan representative soil clays, NCME of Liuying, Wukueiliao (4) and Chungtann get obvious redox peaks of Ru(NH3)63+, while NCME of Liuying and Chungwanchia have more peak current of Fe(CN)63-. Soil Clays have mixed compontents of clay minerals, organic matter and free iron oxides, and that will affect the current of Ru(NH3)63+ through the film of NCME. The character of layer charge of clay minerals are affected by organic matter and free iron oxides.
文章公開時間: 2020-08-16
Appears in Collections:土壤環境科學系



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