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研究生： 黎育蕙
Li, Yu-Huei
論文名稱： 奈米複合材料局部表面電漿共振光纖毛細管偵測器的發展與應用
The Development and Application of Fiber Optic Capillary Detector Employing the Localized Surface Plasmon Resonance of Nanocomposite Materials
指導教授： 呂家榮
Lu, Chia-Jung
學位類別： 碩士
Master
系所名稱： 化學系
Department of Chemistry
論文出版年： 2017
畢業學年度： 105
語文別： 中文
論文頁數： 101
中文關鍵詞： 有機揮發性化合物 、奈米複合材料 、二氧化矽 、局部表面電漿共振 、光纖毛細管 、鎖相放大器
英文關鍵詞： voltaic organic compounds, nanocomposites, SiO2, localized surface plasmon resonance, fiber-optic capillary, lock-in amplifier
DOI URL： https://doi.org/10.6345/NTNU202202650
論文種類： 學術論文
相關次數： 點閱：108  下載：3 
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    • 在光纖毛細管（FOCap）內塗佈奈米複合材料，透過局部表面電漿共振（LSPR）量測揮發性有機化合物（VOCs）之含量，並成功串聯氣相層析儀（GC）做為氣相層析偵測器。為了使偵測器能夠應用於微小化氣相層析系統，本研究使用低功率的發光二極體（LED）搭配鎖相放大器（LIA）增強光電二極體之訊號。在FOCap中分別塗佈受中孔洞二氧化矽保護的奈米金粒子複合材料（SiO2@AuNPs）和受碳鏈保護的奈米金粒子於多孔聚合物內（C12-AuNPs@poly(GMA-EDMA)）作為感測材料，使用光譜儀測量LSPR吸收光譜，光譜的變化量足以偵測VOCs且吸脫附時間不會過長，兩種材料皆有當作GC偵測器的潛力。SiO2@AuNPs光纖毛細管偵測器對於常見的VOCs皆有良好的靈敏度，尤其對於極性較高之化合物偵測感度更佳。分析物極性不同，SiO2@AuNPs毛細管偵測器對其吸附作用力亦不相同，因此每個化合物都有不同的偵測下限（LOD），範圍介於2.56-274.4 ng，雖然對極性化合物有良好的偵測下限，但在再現性測試的實驗中發現回收率及再現性表現不如預期。為了使光纖毛細管偵測器能夠應用於微小化GC系統，使用放光範圍落在奈米複合材料LSPR範圍的LED作為光源並以光電二極體擷取訊號。在LED光徑上放置光束斷續器改善雜散光的干擾，搭配LIA以增強光電二極體的訊號，C12-AuNPs@poly(GMA-EDMA)光纖毛細管偵測器在此實驗裝置下有更好的偵測表現，最低的偵測下限為4.2 ng （左旋檸烯），本研究成功開發具低功率、高表現性等優點的微小化GC偵測器。

    The fiber-optic capillary (FOCap) detector was developed as gas chromatography (GC) detector for voltaic organic compounds (VOCs) using the nanocomposite materials localized surface plasmon resonance (LSPR) intensity variance. These nanocomposites coated FOCap detector was designed to integrate micro GC system by using low power selected wavelength LED and photodiode amplified by a lock-in amplifier (LIA). Two nanocomposites materials (mesoporous silica coated gold nanoparticles (SiO2@AuNPs) and thiolate protected gold nanocomposited porous polymer (C12-AuNPs@poly(GMA-EDMA)) were selected to be immobilized on the FOCap as sensing materials. The LSPR intensity was enhanced by eluting VOCs for both nano materials. With CCD measurements, the light intensity in the LSPR range can be used as GC signals for VOCs eluents measurement. The SiO2@AuNPs coated FOCap detector has been demonstrated high sensitivity for common VOCs detection, especially for polar targets. The limits of detection (LOD) were range from 2.56 to 274.4 ng because of different volatility and affinity between target VOCs and SiO2@AuNPs. The SiO2@AuNPs coated FOCap detector was effected by polar target compounds in signal recovery and performance. For future integration in a micro GC system, the light intensity over LSPR range was evaluated by a photodiode with wavelength selected LED as light source and a LIA. The emitting range range of LED was laid in the LSPR range. The photodiode signals were amplified by a LIA and LED was modulated by an optical chopper. A thiolate protected gold nanocomposites porous polymer coated FOCap detector was obtained by a LIA system and the performance of FOCap detector was improved. The best LOD can be down to 4.2 ng ((R)-(+)-limonene). With low power consumption and good performance, the nanocomposites coated FOCap detector can be used as micro GC detector.

    謝誌 i 摘要 ii Abstract iv 目錄 vi 圖目錄 x 表目錄 xvi 第一章 緒論 1 1.1 前言 1 1.2 揮發性有機化合物 3 1.3 局部表面電漿共振偵測器 5 1.3.1 漸逝波原理 5 1.3.2 表面電漿共振 6 1.3.3 局部表面電漿共振 9 1.3.4 LSPR的應用 13 1.4 二氧化矽 15 1.4.1 SiO2的備製25 15 1.4.2 SiO2的應用 17 1.5 光纖式偵測器 19 1.5.1 光纖的介紹 19 1.5.2 LSPR光纖式偵測器的應用 20 1.6 鎖相放大的原理 22 第二章 實驗部分 25 2.1 實驗藥品與儀器設備 25 2.1.1 實驗藥品 25 2.1.2 儀器設備 28 2.2 材料合成與光纖毛細管修飾 31 2.2.1 合成水相AuNPs50 31 2.2.2 AuNPs自組裝於光纖毛細管 31 2.2.3 SiO2修飾於AuNPs51 31 2.3 系統架設 32 2.3.1 流動注射系統架設 32 2.3.2 光纖毛細管偵測器量測系統 33 2.3.3 光纖毛細管偵測器搭配LIA 34 第三章 結果與討論 35 3.1 AuNPs水溶液合成 35 3.2 SiO2@AuNPs的鑑定與分析 36 3.2.1 AuNPs自組裝於玻璃基材 36 3.2.2 SiO2修飾於AuNPs 37 3.3 SiO2薄膜生長時間探討 39 3.4 多層SiO2@AuNPs探討 41 3.5 SiO2@AuNPs光纖毛細管偵測器特性 42 3.5.1 通入VOCs的LSPR吸收光譜變化 42 3.5.2 VOCs的濃度換算55 44 3.5.3 在FIA系統的再現性測試 45 3.5.4 在FIA系統的校正曲線 46 3.5.5 SiO2@AuNPs層數的選擇 49 3.6 SiO2修飾時間的選擇 51 3.7 SiO2@AuNPs光纖毛細管偵測器的條件探討 52 3.7.1 流速的探討 52 3.7.2 溫度的探討 54 3.7.3 偵測器的長度比較 56 3.8 SiO2@AuNPs光纖毛細管偵測器的感測 59 3.8.1 非極性混合樣品測試 59 3.8.2 極性混合樣品測試 64 3.8.3 混合樣品的極性對偵測器的影響 66 3.9 SiO2@AuNPs光纖毛細管偵測器再現性測試 68 3.10 鎖相放大器系統的條件探討 70 3.10.1 光源的選擇 74 3.10.2 參考頻率的探討 76 3.10.3 鎖相放大器的放大選擇 78 3.10.4 光電二極體的放大選擇 80 3.10.5 時間常數的探討 82 3.11 C12-AuNPs@poly(GMA-EDMA)光纖毛細管偵測器再現性測試 84 3.12 鎖相放大器系統下混合樣品測量 85 第四章 結論 91 文獻資料 93

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