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研究生: 林暐智
Wei-Chih Lin
論文名稱: 阿達瑪轉換法在液相層析/拉曼光譜法之應用
Applications of Hadamard Transform-Liquid Chromatography based on Raman spectrometry
指導教授: 林震煌
Lin, Cheng-Huang
學位類別: 碩士
Master
系所名稱: 化學系
Department of Chemistry
論文出版年: 2011
畢業學年度: 99
語文別: 中文
論文頁數: 122
中文關鍵詞: 阿達瑪轉換拉曼光譜法液相層析法
英文關鍵詞: Hadamard Transform, Raman spectrometry, Liquid Chromatography
論文種類: 學術論文
相關次數: 點閱:159下載:2
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  • 本研究首次將阿達碼轉換(Hadamard transform)技術應用在液相層析/拉曼光譜法(liquid chromatography/Raman spectrometry, LC/RS)上。分析物溶液置於精密注射針內,配合注射泵(syringe pump)推擠進樣,在三向連接頭(Tee connector)中,與來自液相層析泵的流析溶劑匯流以後,共同經過層析分離管柱。經分離之分析物的拉曼訊號則由市售拉曼光譜儀(Renishaw Invia Raman spectroscope)收集。配合阿達瑪序碼(Hadamard code)的使用,由電腦可以控制注射泵的進樣順序,因此可以得到阿達碼-層析圖碼。此編碼之層析圖經過阿達碼轉換以後,可還原得到解碼之液相層析/拉曼光譜圖。實驗結果發現,此方法非常有助於提高雜訊比值,亦有助於提高偵測靈敏度。當以結晶紫(crystal violet, CV)作為測試樣品,編碼後的層析圖譜經由阿達瑪轉換後,訊號/雜訊比提高了7.29倍。這數值與理論值8.02 相當接近。再者,本研究同時發現,經過層析分離管柱後的分析物若能與奈米銀溶液再次匯流混合的話,藉由表面增強拉曼光現象,可提升拉曼散射光的強度,使分析物的的偵測極限下降。即使分析物的濃度為 500 ppb,依舊可觀察到清楚的拉曼光譜圖。

    The technique of Hadamard transform (HT) was successfully coupled with liquid chromatography/Raman spectrometry (LC/RS), for the first time. Crystal violet (CV) and a commercial Raman system (Renishaw Invia Raman Spectroscope) were employed as a model sample and detection instrument, respectively. Sample injection device was aslo developed to achieve multiple sample injections for the use of Hadamard
    transformation. The sample solution was placed in a reservoir and was pushed out by a commercial syringe pump, which was controlled by a personal computer. Compared with a conventional single injection method in LC, the S/N ratios were substantially improved after inverse Hadamard transformation of the encoded chromatogram. Under optimized conditions, when Hadamard matrix of 255 was used, the S/N
    ratio of the signals for crystal violet (concentration level, 0.5 ppm) was substantially improved to 7.29-fold, and the improvements are in good agreement with those obtained by theory (8.0-fold). The limit of detect was further improved when the method of surface enhanced Raman
    scattering (SERS) was applied.

    中文摘要…………………………………………………………………………… I 英文摘要……………………………………………………………………………II 目錄……………………………………………………………………………… III 圖目錄……………………………………………………………………………… V 表目錄…………………………………………………………………………… VII 第一章 緒論…………………………………………………………………………1 1-1 研究目的………………………………………………………………………1 1-2 分析物簡介……………………………………………………………………2 結晶紫(Cryatal violet)………………………………………………………2 1-3 阿達瑪轉換法...…………………………………………………………… 3 第二章 分析方法及原理……………………………………………………………4 2-1 拉曼散射………………………………………………………………………4 2-1-1 拉曼散射歷史簡介…………………………………………………………4 2-1-2 拉曼散射原理介紹…………………………………………………………6 2-2 表面增強拉曼……………………………………………………………… 10 2-2-1 表面增強拉曼歷史簡介………………………………………………… 10 2-2-2 表面增強拉曼原理介紹………………………………………………… 11 2-3 奈米粒子的特性…………………………………………………………… 15 2-4 高效能液相層析法簡介…………………………………………………… 17 2-5 阿達瑪矩陣原理…………………………………………………………… 19 2-5-1 矩陣起源………………………………………………………………… 20 2-5-2 阿達瑪轉換法…………………………………………………………… 21 2-5-3 阿達瑪轉換提高S/N 比的理論值………………………………………28 第三章 儀器、藥品與實驗方法………………………………………………… 32 3-1 高解析拉曼光譜分析儀…………………………………………………… 32 3-2 阿達瑪進樣裝置…………………………………………………………… 35 3-2-1 阿達瑪進樣裝置………………………………………………………… 35 3-2-2 阿達瑪進樣步驟與實驗方法…………………………………………… 38 3-2-3 液相層析/拉曼光譜分析儀………………………………………………40 3-3 奈米銀膠體溶液的配置與玻璃容器清洗………………………………… 42 3-3-1 奈米銀膠體溶液的配置………………………………………………… 42 3-3-2 玻璃容器清洗…………………………………………………………… 43 3-4 儀器及周邊設備列表……………………………………………………… 44 3-5 實驗藥品列表……………………………………………………………… 49 第四章 研究過程與結果討論…………………………………………………… 50 4-1 注射式幫浦進樣器穩定度測試…………………………………………… 50 4-1-1 以UV-Vis 偵測器測試注射式幫浦進樣器穩定度 ……………………50 4-2 利用液相層析/拉曼光譜分析法對分析物進行分析………………………53 4-2-1 液相層析/拉曼光譜法對不同進樣體積測試……………………………54 4-2-2 液相層析/拉曼光譜法對不同進樣濃度測試……………………………59 4-2-3 阿達瑪進樣與阿達瑪序列比較………………………………………… 64 4-2-4 阿達瑪轉換與單點進樣結果比較……………………………………… 66 4-3 利用液相層析/表面增強拉曼法對分析物進行偵測………………………68 4-3-1 奈米銀溶液製配結果.……………………………………………………69 4-3-2 液相層析/表面增強拉曼法對不同進樣濃度測試………………………72 4-3-3 LC-SERS 之阿達瑪轉換與單點進樣結果比較…………………………79 第五章 結論……………………………………………………………………… 81 參考文獻……………………………………………………………………………82 附錄一………………………………………………………………………………88 附錄二…………………………………………………………………………… 103

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