動力學研究銅胺基酸活化過氧化氫中pH與有機酸效應

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研究生：	張皓
論文名稱：	動力學研究銅胺基酸活化過氧化氫中pH與有機酸效應 Kinetic study of the effects of pH and organic acid on the activation of hydrogen peroxide catalyzed by Copper(II) amino acid complexes
指導教授：	吳劍侯 Wu, Chien-Hou
口試委員:
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：	2009
畢業學年度：	97
語文別：	中文
論文頁數：	46
中文關鍵詞：	銅錯合物、過氧化氫、胺基酸、活性氧化物種、2-甲喹啉
外文關鍵詞：	Copper complex, Hydrogen peroxide, Amino acid, Reactive oxygen species, Quinaldine blue
相關次數：	點閱：3 下載：0
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本研究利用銅胺基酸錯合物，於25oC的磷酸緩衝溶液中活化過氧化氫，並偵測反應中的2-甲喹啉藍(QB)的初始氧化速率來探討銅錯合物活化過氧化氫效率。本實驗透過改變pH及活性氧化物種抑制劑的添加，了解過氧化氫活化系統的反應機制及其主要活性氧化物種。實驗結果發現，在以銅胺基酸錯合物活化過氧化氫的系統中，銅胺基酸錯合物可有效增加過氧化氫解離常數Ka，因此反應效率隨pH值上升而增加。此外，透過有機酸類抑制劑的添加，發現其抑制效果符合Non-competitive 的抑制模型，再藉由抑制劑與一價銅生成關係，推論LCu(I)OOH•為系統中主要的活性氧化物種，造成後續QB的氧化反應。

目錄

中文摘要………………………………………………………………...…………….I
英文摘要……………………………………………………………………………...II
誌謝…………………………………………………………………………………..III
目錄…………………………………………………………………………………..IV
圖目錄………………………………………………………………………………..VI
表目錄……………………………………………………………………….……...VII
附錄目錄………………………………………………………………….……......VIII
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     H2O2的金屬活化作用……………..………………………………………….3
  2.2 Fenton 反應/Fenton-like 反應…………..…………………………………….4
  2.3 銅的介紹………………………………….…………………………………....5
  2.4 銅離子╱銅錯合物的Fenton-like反應-工業製程與環境系統………………6
  2.5銅離子╱銅錯合物的Fenton-like反應-銅與胺基酸之相關研究…………….6
  2.6 胺基酸的介紹………………………………………………………………….7
  2.7 實驗原理介紹………………………………………………………………….9
    2.7.1銅胺基酸活化H2O2………………………………………………………..9
    2.7.2 分子吸收光譜法…………………………………………………………..9
    2.7.3 Quinaldine blue的介紹…………………………………………………...10
    2.7.4 銅胺基酸錯合物活化H2O2反應動力學………………………………...11
第三章    實驗方法……….………………………………………...……………..…13
  3.1實驗裝置…………..……………………………………...………………..…13
    3.1.1 紫外可見光譜儀(UV-Vis spectrometer)…….……….……………....….13
    3.1.2  pH meter………………………...………….………………..………….13
    3.1.3 離子層析儀(Ion chromatography)………...……………………..………13
  3.2 實驗藥品………………………...………………………...………..………...14
  3.3 實驗流程……………………………………………………………………...15
    3.3.1 母液配製…………………………………………………………………15
    3.3.2 樣品配製…………………………………………………………………15
    3.3.3 使用UV/Vis觀察反應速率……………………………………..………16
    3.3.4 初始速率決定方法…………………………..................………..………16
  3.4 一價銅的量測………………………………………………………………...19
  3.5 實驗計算軟體………………………………………………………………...20
    3.5.1 MINTEQ………………………………………………………………….20
    3.5.2 NIST46.4 熱力學資料庫………………………………………………...21
第四章  結果與討論…………………………...………..………………………….23
  4.1銅濃度之影響…..……...………..……………….……………………………23
  4.2 H2O2濃度之影響……………………………………………………………...24
  4.3 pH值的影響……………………………...………..………………………..…26
  4.4 有機酸分子與金屬螯合劑的影響………………...………..…………..……30
  4.5 NH4+的量測……...…………………………….……..……………………….37
  4.6 反應機制探討………………………..……...………..………………………37
第五章  結論....................……………………...………..………………………….40
第六張  未來展望…………………………………………………………………..40
參考文獻…………………………...………..……………………………………….41
附錄……………………...………..……………………………………………………i

圖目錄

圖2-1  QB化學結構圖…………………………………………………………….10
圖2-2  Michaelis-Menton equation曲線圖…...………..…………………………..12
圖3-1  QB分解光譜圖………...………..………………………………………….16
圖3-2  QB吸收值衰減圖……….………..………………………………………...17
圖3-3  QB衰減初始速率決定圖……...……..…………………………………….18
圖3-4　QB檢量線………...………..……………….………………………………18
圖3-5  Cu(I)加Bathocuproine於484 nm出現吸收峰..………………………........19
圖3-6  Minteq模擬不同pH值環境下改變Gly濃度對銅物種分布之影響...........20
圖3-7  Nist46.4中Cu與Alanine 之錯合常數..…………….………………........22
圖4-1  銅濃度對QB降解速率的影響……..…...……..……..................................23
圖4-2  H2O2濃度對QB降解速率的影響….……………………………………...24
圖4-3  利用4-1式計算銅胺基酸錯合物(Gly)之kcat, Km………………………...25
圖4-4  pH對反應效率影響圖.…....……………………………………..................26
圖4-5  利用4-7式計算銅胺基酸錯合物(Gly)之k’, Ka……..….…..…………….28
圖4-6  有機酸對反應速率的影響.………………………..…………………….....30
圖4-7  胺基酸與雙胺類對反應速率的影響……………………..………..………31
圖4-8(a) 乙二酸的抑制……………………………..……………...………..……...32
圖4-8(b) 丙二酸的抑制.…………………………………………………………....32
圖4-8(c) 檸檬酸的抑制.……..………………...……………………………….…...33
圖4-8(d) EDTA的抑制.……………………...…................................................…...33
圖4-8(e) Gly的抑制…………………………………………………………………34
圖4-8(f) 乙二胺的抑制…………………………………………………………..…34
圖4-9 non-competitive 反應機制示意圖..………………………………………….35
圖4-10 抑制劑對一價銅生成的影響..…….…..……….…………………………..36
表目錄

表2-1  胺基酸基本性質介紹………………….……..………..…………………….7
表3-1  離子層析儀儀器設定條件....…………………..………..………………....14
表4-1  銅胺基酸錯合物之k’與pKa值..………..…………………………………26
表4-2  抗氧化劑對QB分解速率影響……………...……………………………...36


附錄目錄

銅胺基酸錯合物活化反應之k’與Ka………………………………………………...i
1. Ala…………………………...................................................………………………i
2. Arg………………………………..................................................................………ii
3. Asp…………………………………………………………………………………iii
4. Glu………...................................................……………………………………......iv
5. His……………………………………………………..……………………….…...v
6. Ile…………...............................................................………………………….…...vi
7. Leu………………….....................................................…………………………..vii
8. Met………………………………………………………………………………..viii
9. Phe................................................................…………………………………….…ix
10. Pro…………………………………………………………………………………x
11. Ser……………....................................................................…………………..…..xi
12. Val…………………………………………………………………..……………xii
13. Asn……………………………………...................................................……….xiii
14. Gln………………………………...................................................................…..xiv
15. Lys…………..............................................................…………………………....xv
16. Thr…………………………....................................................……….................xvi
17. Trp…………………………...................................................................……….xvii
18. Tyr…………..............................................................………………………….xviii
19. Gly…………………………………....................................................………….xix

                                

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