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研究生：	陳弘毅 Chen, Hong-Yi
論文名稱：	運用分子模板於三聚氰胺檢測之方法研發 Development of Molecular Imprinting Polymers for Analysis of Melamine and Related compounds
指導教授：	林達昌 Lin, Ta-Chang
學位類別：	碩士 Master
系所名稱：	工學院 - 環境工程學系 Department of Environmental Engineering
論文出版年：	2011
畢業學年度：	99
語文別：	中文
論文頁數：	81
中文關鍵詞：	三聚氰胺、分子模板、固相萃取、氣相層析儀
外文關鍵詞：	Melamine, molecular imprinting polymers, SPE, GC-MS
相關次數：	點閱：117 下載：1
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本研究主要是利用分子模板技術進行三聚氰胺萃取、濃縮、淨化之分析方法；以三聚氰胺為目標分子製成之分子模板對於環境樣品進行萃取，所得之樣品以氣相層析質譜儀（GC/MS）進行分析。三聚氰胺傳統分析方式以高效能液相層析儀（HPLC-UV與HPLC-DAD）為主，其分析方法偵測極限約為2.5 ppm（v/v），藉由分子模板的樣品前處理與技術希望能達到干擾減低、濃縮樣品和準確快速的效果，來提升檢測結果的可靠性與檢測過程的便利性，以及降低前處理所消耗的有機溶劑、時間、材料與人力。本研究依照不同官能基單體與交聯劑比例，配製4種具有目標分子之分子模板為實驗組與4種沒有添加目標分子之分子模板為控制組，在目標分子的移除之後，隨後進行容量測試、三聚氰胺固相萃取測試、電子顯微鏡表面觀察、回收率測試、選擇性測試、重複使用性測試、環境樣品測試等；實驗結果顯示A3M（Template : Monomer : Cross-Linker : Initiator = 1 : 8 : 20 : 0.66）對於三聚氰胺吸附效果最高，1 g模板可吸附16.09 μg的三聚氰胺，回收率可達93.1%左右，但選擇性效果不如A1M（Template : Monomer : Cross-Linker : Initiator = 1 : 4 : 20 : 0.66）來的明顯，A1M對於三聚氰胺回收率也高達86.4%，QMIP/QNIP （分子模板組/無分子模板組）為10.99，可推測A1具有較多對於三聚氰胺有專一性且特殊大小形狀之孔洞，並且對於三聚氰胺的偵測於0.1 ppm仍可精準的檢測。

This study aimed to develop a novel molecular imprinting polymer (MIP) for the analysis of melamine in environmental samples. Samples were extracted by using MIPs prepared with melamine as the template and the extracts were analyzed by GC-MS. Melamine is analyzed by HPLC-UV or HPLC-DAD practically and the detection limit is 2.5 ppm. By exploiting the specific interaction between molecular key and molecular lock, interferences in complex environment matrices, such as water, soil and air, can be greatly eliminated. It is anticipated that this developed molecular imprinting extraction technique of melamine may be applied to the sampling and analysis of liquid sample in general. It will not only provide a highly selective and effective method, but also decrease the consumption of time, human power and large quantities of solvents in sample pretreatment.
Four different ratios of template (melamine), monomer (methacrylic acid), cross-linker (ethylene glycol dimethacrylate) and initiator (2,2-Azobis(2-isobutyronitrile)) of MIPs as well as the corresponding molecular imprinting polymers without template (NIPs) were synthesized. The MIPs and NIPs were tested for the material characteristics of capacity, selectivity, recovery, and breakthrough evaluations.
The results showed that the MIP tagged as A3M (template: monomer: cross-linker: initiator = 1:8:20:0.33) provided the best adsorption capacity (16.09 μg/g). Recovery of melamine was about 93.1%. However, the selectivity of A1M(template: monomer: cross-linker: initiator = 1:4:20:0.33) was better than that of A3M. The ratio of QMIP/QNIP (with/without template) equaled to 10.99 for A1M, which revealed a significantly better adsorption effect of MIPs against the NIPs. Furthermore, the recovery of A1M achieved 86.4%. A1M was considered an ultimate formula of melamine MIP and it offered a high accuracy even at a trace concentration of 0.1 ppm in the tested sample.

中文摘要………………………………………………………………I
英文摘要………………………………………………………………III
誌謝……………………………………………………………………V
總目錄…………………………………………………………………VII
表目錄…………………………………………………………………XI
圖目錄…………………………………………………………………XII
第一章 前言……………………………………………………………1
1-1 研究動機…………………………………………………………1
1-2 研究目的…………………………………………………………2
第二章 文獻回顧………………………………………………………3
2-1 微量分析之概念與應用…………………………………………3
2-2 固相萃取之概念與應用…………………………………………6
2-2-1 固相萃取原理與流程…………………………………………6
2-2-2 固相萃取與微量物質分析……………………………………7
2-3 分子模版之概念與應用…………………………………………8
2-3-1 分子模版發展歷史……………………………………………8
2-3-2 分子模版概念	…………………………………………………9
2-3-3 分子模版製備	…………………………………………………10
2-3-4 分子模版應用	…………………………………………………14
2-3-5 分子模版萃取與傳統萃取比較………………………………15
2-4 三聚氰胺之特性與危害…………………………………………17
2-4-1 三聚氰胺之簡介與環境流佈…………………………………17
2-4-2 三聚氰胺之毒性與法規………………………………………19
2-4-3 三聚氰胺與賽滅淨之特性比較………………………………20
2-4-4 目前三聚氰胺在微量分析之方法……………………………22
第三章 實驗方法與步驟………………………………………………26
3-1 實驗藥品與器材…………………………………………………26
3-1-1 藥品與試劑……………………………………………………26
3-1-2 實驗設備………………………………………………………28
3-2 實驗設計與規劃	…………………………………………………29
3-3 分子模版製備……………………………………………………30
3-4 模板性質…………………………………………………………35
3-4-1 洩漏測試………………………………………………………35
3-4-2 吸附容量測試	…………………………………………………35
3-4-3 掃描式電子顯微鏡（SEM）觀察……………………………38
3-5 MISPE最佳化測試………………………………………………39
3-5-1 模板添加量……………………………………………………39
3-5-2 選擇性測試……………………………………………………40
3-5-3 重複使用測試…………………………………………………40
3-5-4 三聚氰胺回收率測試…………………………………………41
3-6 樣品測試…………………………………………………………42
3-6-1 市售奶粉前處理………………………………………………42
3-6-2 分子模板萃取管萃取…………………………………………42
3-6-3 樣品衍生化……………………………………………………43
3-7 三聚氰胺之分析方法……………………………………………45
第四章 數據分析之品質保證與控制…………………………………46
4-1 空白試驗…………………………………………………………46
4-1-1 溶劑空白試驗…………………………………………………46
4-1-2 程序空白試驗…………………………………………………46
4-2 分析程序之QA/QC................................47
4-2-1 方法偵測極限…………………………………………………47
4-2-2 準確度及精密度建立…………………………………………47
4-2-3 滯留時間測試…………………………………………………48
4-2-4 標準品檢量線之建立…………………………………………49
第五章 結果與討論……………………………………………………51
5-1 模板性質…………………………………………………………51
5-1-1 洩漏測試結果…………………………………………………51
5-1-2 模板吸附容量測試結果………………………………………52
5-1-3 SEM觀察結果…………………………………………………56
5-2 MISPE最佳化結果………………………………………………59
5-2-1 模板添加量……………………………………………………59
5-2-2 選擇性測試結果………………………………………………63
5-2-3 重複使用測試結果……………………………………………65
5-2-4 三聚氰胺回收率………………………………………………67
5-3 市售奶粉分析結果………………………………………………68
5-3-1 人為添加三聚氰胺至奶粉之檢測……………………………68
5-3-2 添加三聚氰胺與賽滅淨至奶粉之檢測………………………70
第六章 結論與建議……………………………………………………72
6-1 結論………………………………………………………………72
6-2 建議………………………………………………………………74
參考文獻…………………………………………………………………75
附錄………………………………………………………………………79
自述………………………………………………………………………81


                                    

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校內：2012-07-11公開
校外：2012-07-11公開

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