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研究生： 梁以晴
Liang, Yi Ching
論文名稱： 硫化物奈米結構與多壁奈米碳管在葡萄糖生物感測器之應用
Applications of Multi-Wall Carbon Nanotubes and Sulfide Nanostructure on Sensing Glucose
指導教授： 呂世源
Lu, Shih Yuan
口試委員: 衛子健
蔡德豪
學位類別： 碩士
Master
系所名稱： 工學院 - 化學工程學系
Department of Chemical Engineering
論文出版年： 2015
畢業學年度： 103
語文別： 中文
論文頁數： 63
中文關鍵詞： 葡萄糖感測器 、二硫化錫
外文關鍵詞： glucose biosensor, SnS2
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    • 自1962年Clark提出第一代葡萄糖感測器開始，為了追求更高的靈敏度與專一性，目前已經發展至第三代感測器，其主要利用direct electron transfer方式，直接針對葡萄糖進行感測。做為一個理想的葡萄糖感測元件，除了需要具備良好的材料穩定性與專一性之外，其優異的親水性、電子傳遞能力與反應物接觸面積，亦為重要因素。良好的親水性可以促進glucose oxidase (GOD)與葡萄糖水溶液間的反應，優良的電子傳遞能力可以放大GOD中心的反應訊號，較大的反應物接觸面積可以增加GOD與葡萄糖接觸的機會。目前大部分的研究多以葡萄糖氧化酶做為感測酵素，雖然在適當操作條件下，有不錯的材料穩定性與專一性，但在親水性與電子傳遞能力上，仍有很大的進步空間。為了有效提升GOD在葡萄糖感測器上的偵測效能，本研究藉混和一低成本、無毒且高親水性之片狀二硫化錫於GOD薄膜中，除了能大幅改善GOD薄膜之整體親水性外，更可利用二硫化錫本身特殊的二維片狀結構，來加強電子傳遞能力與提升GOD與葡萄糖的接觸機會[1]。
    本研究使用水熱法，以SnCl4‧5H2O和C2H5NS做為反應前驅物，於160℃下持溫12小時，成功合成出一尺寸約934±804 nm之片狀二硫化錫奈米結構，並以超聲均質法，進行片狀二硫化錫之剝層程序。剝層後之片狀二硫化錫尺寸約24±8 nm，接觸角約8.71∘，進而將所剝層之片狀二硫化錫，混摻約0.1 mg至GOD薄膜，大幅降低GOD整體薄膜之接觸角，自26.9∘降低至4.06∘，同時也明顯提升葡萄糖感測效能，靈敏度自16.3 μA/mM cm2提升至28.9 μA/mM cm2，線性範圍從0.0625至1.5 mM提升0.0625至2.8 mM，偵測極限從0.0625 mM降至0.0125mM。這樣的增益表現，相較過去數年，進行第三代葡萄糖感測器研究的結果，發現使用剝層二硫化錫，所提升之整體感測效能，屬一具有相當競爭力的突破結果。

    There are more and more people getting diabetes all over the world and the patients suffer from bad life quality because of the fluctuating blood glucose concentration. To fabricate a good glucose biosensor, there are several criteria to be satisfied. The stability and specificity of the sensor itself, control of hydrophilicity for good electron transfer ability and larger surface areas are the key points to improve the sensing results. Glucose oxidase is an enzyme specifically binding with glucose and is usually used to sense blood glucose. This study aims to combine a cheap, stable and non-toxic SnS2 with multi-wall carbon nanotubes (MWCNT) to improve the sensitivity toward glucose. SnS2 is a layer structure material. The van der Waals force between the layers can be separated and thus the material exfoliated with ultrasonication. After centrifuguration in 13500 rpm, the size and thickness of the exfoliated SnS2 (E-SnS2) collected from the top portion become smaller so the surface area is much larger at the same concentration.
    X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) are used to characterize E-SnS2. TEM images show the same crystal lattice (001), (110) and (100), echoing the results in XRD. The binding energies of electrons match those of the database of SnS2. The atomic proportion of Sn and S is approximately 1:2 from scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDX). The thickness of SnS2 decreases from 36, 43 nm to 8.2 nm as measured by an atomic force microscope (AFM) and the size also decreases from 934±804 nm to 24±8 nm as estimated from SEM images.
    The current density in cyclic voltammetry of the redox reaction increases when the E-SnS2 is added. The current becomes larger when the scan rate increases which means that the electrochemical reaction is a surface control process. The most important goal in biosensor is sensitivity. This work achieved a high sensitivity of 28.9 μA/mM cm2, which shows a great improvement in sensing ability. The linear range is from 0.0625 to 2.8 mM and the detection limit is 0.0125 mM.

    摘要 I Abstract II 致謝 IV 總目錄 V 表目錄 VII 圖目錄 VIII 第一章 緒論 1 1-1生物感測器 1 1-1-1前言 1 1-1-2 生物感測器簡介 1 1-1-3糖尿病與葡萄糖感測器 3 1-2研究動機與方向 5 第二章 文獻回顧與理論說明 8 2-1 血糖感測器的發展 8 2-2 碳材表面性質 12 2-2-1多壁奈米碳管性質 13 2-2-2 奈米碳管應用於血糖感測器 14 2-2-3硫化物與奈米碳管應用於血糖感測器 18 2-3 二硫化錫的性質與應用 25 2-3-1 二硫化錫的結構與性質 25 第三章 實驗內容 33 3-1實驗藥品 33 3-2 實驗器材 35 3-3 分析儀器 36 3-4 實驗方法 40 3-4-1 二硫化錫製備 40 3-4-2 二硫化錫剝層 40 3-4-3 FTO清洗流程 40 3-4-4 配置葡萄糖氧化酶溶液 41 3-4-5 nafion配置 41 3-4-6 酵素電極製備 41 3-4-7 電化學反應條件 42 第四章 結果與討論 43 4-1 二硫化錫與多壁奈米碳管性質分析 43 4-1-1 XRD分析結果 43 4-1-2 SEM-EDX分析結果 44 4-1-3 TEM分析結果 44 4-1-4 HPXPS分析結果 45 4-1-5 AFM分析厚度結果 46 4-1-6 E-SnS2親水性檢測 46 4-1-7 UV-Vis與FTIR分析 47 4-1-8 E-SnS2與葡萄糖氧化酶親水性檢測 49 4-1-9 電極環境示意圖 49 4-1-10 SEM圖像分析結果 50 4-2 生物感測器分析結果 50 4-2-1 電極CV分析 50 4-2-2 葡萄糖與電化學反應關係 51 4-2-3 不同掃速分析 52 4-2-4 靈敏度與選擇性分析 53 4-2-5 不同pH值分析 54 4-2-6 文獻比較 55 4-2-7 近年來DET葡萄糖感測器之靈敏度比較 56 第五章 結論 57 第六章 文獻引用 58

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