臺灣博碩士論文加值系統

本論文已量測諸多銅胺基酸錯合物之一價銅量子產率。利用丙胺酸（NH2CHCH3COOH）為模型，在不同條件（pH、銅與配位基濃度、離子強度等）下，討論對一價銅量子產率之影響。實驗同時測量銅與丙胺酸錯合物CuL與CuL2之一價銅量子產率；另外，也一併討論其他八種不帶極性旁鏈之胺基酸，其光反應性趨勢為何。實驗利用Bathocuproine方法量測一價銅產率。對於銅錯合物1：1配位而言，於313 nm下之一價銅量子產率（ΦCu(I),CuL）大小順序如下：β-alanine＞ α-alanine＞ leucine, isoleucine, phenylalanine, valine＞ glycine＞ methionine＞ proline。其中1：1配位物種（CuL）一價銅量子產率變化約6倍而1:2配位物種（CuL2）約10倍左右。不同胺基酸錯合之下的量子產率，其1:1配位皆較1:2配位為大。實驗數據顯示改變pH、配位基濃度或銅濃度條件下，銅胺基酸錯合物之光反應性，均可以簡單之物種分佈模式預測。

The Cu(I) quantum yields of copper(II)-amino acid complexes in aqueous solutions have been measured at 313nm in this study. For Alanine (NH2CHCH3COOH) as a model ligand, the effects of Cu(I) quantum yields in different conditions (changing pH, copper and ligand concentration, and ionic strength) were discussed. In order to know the trend of photoreactivity of copper-amino acid complexes, the rest eight amino acids with non-polar side chains have also studied. Bathocuproine method is used to determine the copper(I) quantum yield. For the 1:1 Cu(II) complexes (CuL), the Cu(I) quantum yields at 313 nm (ΦCu(I),CuL) are in the sequence (25℃, ionic strength＝0.10 M)：β-alanine＞ α-alanine＞ leucine, isoleucine, phenylalanine, valine＞ glycine＞ methionine＞ proline. Among these amino acids, the Cu(I) quantum yields of 1:1 Cu(II) complexes vary by 6-folds and 10-folds for 1:2 Cu(II) complexes. Besides, the former are larger than the latter, probably owing to the stabilizing effect of the second ligand. The experimental data shows that the photoreactivity of copper-amino acid can be predicted by Cu(II) speciation in a wide range of the solution conditions, varying in pH, total concentration of copper(II) , and the total concentration of ligand.

第一章 引言-------------------------------------------------- 1
1-1 簡介----------------------------------------------------- 1
1-2 研究動機------------------------------------------------- 3
1-3 研究目的------------------------------------------------- 3
1-4 流程規劃------------------------------------------------- 4
第二章 文獻回顧---------------------------------------------- 5
2-1 環境水體中銅錯合物的反應--------------------------------- 5
2-2 不同配位基之銅錯合物的光化學反應------------------------- 8
2-2-1 銅與各種配位基之光化學反應----------------------------- 9
2-2-2 銅與胺基酸光化學反應---------------------------------- 10
2-3 一價銅的測量-------------------------------------------- 12
2-4 光強度量測-利用化學光度計（Actinometer）-----------------14
2-5 不同銅錯合物之量子產率的比較---------------------------- 15
2-6 反應模式的假設------------------------------------------ 17
第三章 研究方法--------------------------------------------- 21
3-1 銅胺基酸光反應系統---------------------------------------21
3-1-1 實驗儀器---------------------------------------------- 21
A.單光系統-------------------------------------------------- 21
B.紫外可見光譜儀-------------------------------------------- 22
C.高效能液相層析儀------------------------------------------ 23
D.除氧系統-------------------------------------------------- 24
3-1-2 實驗藥品---------------------------------------------- 25
3-1-3 分析流程---------------------------------------------- 26
3-1-4 一價銅的測量------------------------------------------ 27
3-1-5 光強度測量-------------------------------------------- 27
3-2 銅-胺基酸系統中各物種所佔比例之計算--------------------- 29
3-2-1 MINTEQ------------------------------------------------ 30
3-2-2 NIST46.4 熱力學資料庫--------------------------------- 32
3-2-3 離子強度之修正---------------------------------------- 33
3-3 數據處理方法-------------------------------------------- 35
3-3-1 光強度方法與數據處理---------------------------------- 35
3-3-2 量測一價銅之數據處理---------------------------------- 37
3-3-3 量子產率之計算方程式---------------------------------- 38
第四章 結果與討論------------------------------------------ 41
4-1 光照系統最佳化------------------------------------------ 41
4-1-1 除氧時間選取實驗-------------------------------------- 41
4-1-2 平衡時間選取實驗-------------------------------------- 42
4-2 品保品管（QA/QC）--------------------------------------- 44
4-2-1 實驗再現性 ------------------------------------------- 44
4-2-2 光源穩定性 ------------------------------------------- 45
4-2-3 方法適用性 ------------------------------------------- 46
4-3 銅胺基酸錯合物光反應結果討論---------------------------- 48
4-3-1 銅與不同胺基酸之一價銅量子產率------------------------ 48
4-3-2 利用銅-丙胺酸錯合物於改變條件下探討光反應性----------- 51
4-3-2-1 改變pH值-------------------------------------------- 52
4-3-2-2 改變配位基濃度-------------------------------------- 53
4-3-2-3 改變銅濃度------------------------------------------ 54
4-3-2-4 改變離子強度---------------------------------------- 56
第五章 結論------------------------------------------------- 58
第六章 未來計畫--------------------------------------------- 59
參考文獻---------------------------------------------------- 60
附錄一 胺基酸性質------------------------------------------- 66
附錄二 生成物種之熱力學常數表------------------------------- 67
附錄三 銅與胺基酸照光反應之原始數據------------------------- 68
附錄四 VMINTEQ使用說明 ------------------------------------- 80

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