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研究生： 彭兆珩
論文名稱： 水相中銅胺基酸錯合物活化過氧化氫之醛產物分析
Formation of aldehydes in the activation of hydrogen peroxide by Cu(II)/amino acid complexes
指導教授： 吳劍侯
口試委員: 林萬寅
鄧金培
吳劍侯
學位類別： 碩士
Master
系所名稱： 原子科學院 - 生醫工程與環境科學系
Department of Biomedical Engineering and Environmental Sciences
論文出版年： 2011
畢業學年度： 99
語文別： 中文
論文頁數： 50
中文關鍵詞： 銅錯合物 、過氧化氫 、丙酸 、亞硝基二甲基苯胺 、胺甘露醇 、3-甲硫基丙醛
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    • 本研究利用Cu(II)與α-Ala形成的錯合物，在磷酸鹽緩衝溶液中活化過氧化氫，以量測反應中所形成的乙醛，並由其產生速率來探討系統活化過氧化氫的反應途徑。實驗中探討包括pH、離子強度、Cu(II)、過氧化氫與Alanine濃度的影響，由於系統中會產生許多自由基，後續則使用亞硝基二甲基苯胺(p-Nitrosodimethylaniline, PNDA)來觀察系統中OH．的產率，與量測乙醛反應的變化，以及使用OH．抑制劑甘露醇(mannitol)觀察對反應的影響；另外也使用Cu(OOH)．抑制劑3-甲硫基丙醛(methional)發現後者對系統中產生乙醛速率有很明顯的抑制效果，因而推論Cu(I)OOH．為主要活性氧化物種，最後從實驗結果及文獻整理推測系統中可能產生乙醛的反應途徑。

    目錄 中文摘要.....................I 英文摘要.....................II 目錄.........................III 圖目錄.......................V 表目錄.......................VI 第一章 前言................1 1.1 簡介................1 1.2 研究目的及動機......1 第二章 文獻回顧............3 2.1 金屬活化H2O2的反應 2.2 活化H2O2的應用..............4 2.3 活化H2O2的反應機制.............4 2.4 銅的介紹.........5 2.5 氨基酸的介紹................6 2.6 銅與胺基酸的鍵結情況與物種分佈................8 2.7 銅胺基酸錯合物活化H2O2反應動力學......9 2.8 實驗原理介紹.....................11 2.8.1銅丙氨酸活化H2O2............11 2.8.2醛的測量方法................11 2.8.3 分子吸收光譜法.............13 第三章 實驗方法.................14 3.1 實驗裝置..................14 3.1.1. 高效率液相層析儀（HPLC）.....14 3.1.2. 紫外可見光譜儀(UV-Vis spectrometer).....................14 3.1.3. pH meter.................14 3.2 實驗計算軟體.............14 3.2.1 MINTEQ......................14 3.2.2 NIST46.4 熱力學資料庫.......16 3.3 實驗藥品..................17 3.4 分析流程..................18 3.4.1. 母液配製..................18 3.4.2. 樣品配製..................19 3.4.3. 醛的分析..................20 第四章 結果與討論................22 4.1乙醛的分析......................22 4.2活化H2O2要素的確定..............25 4.3離子強度的影響..................26 4.4 pH值的影響................27 4.5銅錯合物物種分布之影響..........28 4.6 Cu濃度之影響...................30 4.7 H2O2濃度的影響.................30 4.8 OH．清除劑對系統的影響.........32 4.9 Cu(I)OOH•清除劑的影響.........35 4.10反應機制探討...................37 第五章 結論......................39 第六章 未來展望..................39 參考文獻...........................40 附錄...............................47 附錄一 PNDA檢量線..................47 附錄二 DNPH檢量線..................47 附錄三pH =2~4乙醛衍生物長時間的分解....48 附錄四改變不同條件對乙醛產生速率的影響......48 圖目錄 圖2-1 銅胺基酸錯合物結構圖.................9 圖2-2 Michaelis-Menton equation曲線圖.....10 圖3-1 銅物種分佈.........................15 圖3-2 Nist46.4中Cu與Alanine之錯合常數..........17 圖3-3 醛分析的HPLC-UV/VIS之移動相梯度.....19 圖3-4 DNPH及其衍生物UV光譜圖.........20 圖3-5 乙醛標準品層析圖譜.............21 圖3-6 乙醛標準品檢量線................21 圖4-1 acetaldehyde-DNPH 標準品檢量線.............22 圖4-2 acetaldehyde-DNPH衍生物濃度在不同pH下的變化...23 圖4-3 DNPH濃度在不同pH下的增加.................23 圖4-4 乙醛衍生物在pH = 1.8分解濃度變化.........24 圖4-5 不同條件下乙醛產生速率變化圖...................25 圖4-6 乙醛加入H2O2的長時間變化圖...............26 圖4-7 離子強度對反應效率的影響................27 圖4-8 pH對反應效率的影響.........................28 圖4-9 銅胺基酸一二配位錯合物CuL及CuL2與H2O2活化效率比較..29 圖4-10 銅氨基酸濃度對產生乙醛速率的影響...............30 圖4-11 不同H2O2濃度對產生乙醛速率的比較.......31 圖4-12 利用式4-2計算銅氨基酸錯合物(Ala)之Kcat,Km......32 圖4-13 OH •抑制劑在不同濃度對OH •生成速率的影響.....34 圖4-14 OH •抑制劑在不同濃度對乙醛生成速率的影響.......35 圖4-15 methional在不同濃度對系統中產生乙醛的影響.......36 圖4-16 在不同濃度對系統中產生OH•的影響...............37 表目錄 表2-1 胺基酸基本性質介紹.........7 表3-1 藥品的機本物理性質................18 表4-1 各OH•清除劑的清除效率..............33

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