臺灣博碩士論文加值系統

本論文量測水相中銅胺酸錯合物於313 nm照射下之一價銅量子產率。八種非極性胺酸配位基包括甘胺酸 (glycine, Gly)、α-丙胺酸 (alanine, Ala)、β-丙胺酸 (β-alanine, β-Ala)、2-胺基丁酸 (2-aminobutyric acid, 2-ABA)、2-胺基異丁酸 (2-aminoisobutyric acid, 2-AIBA)、4-胺基丁酸 (4-aminobutyric acid, 4-ABA)、纈胺酸 (valine, Val) 及正纈胺酸 (norvaline, Nor)。在不同條件（pH值與配位基濃度）下，利用bathocuproine之方法量測一價銅生成量並探討不同銅胺酸錯合物的一價銅量子產率關係。於313 nm光照下，一配位基的銅錯合物其一價銅量子產率 (ΦCu(I),CuL) 大小順序如下：2-AIBA ＞ β-Ala ＞ Ala，2-ABA，Nor ＞ Val ＞4-ABA ＞ Gly，範圍從0.279到0.06 (mol einstein-1)。不同實驗條件下，銅胺酸錯合物之光反應性，皆能以簡單之物種分佈模式預測。以碳為中心的自由基，其穩定性會對一價銅量子產率有重大的影響；形成六元螯合環的銅胺酸錯合物會比五元螯合環的銅胺酸錯合物有較大的一價銅量子產率，其可能原因為電子轉移效率增加。

Cu(I) quantum yields were measured at 313 nm for copper(II)-amino acid complexes with eight amino acids in aqueous solutions. Photochemical formation of copper(I) has been systematically studied for copper(II) complexes in different conditions (changing pH and ligand concentration). Bathocuproine method was used to determine copper(I) concentration. For the 1:1 Cu(II) complexes (CuL), the Cu(I) quantum yields at 313 nm (ΦCu(I),CuL) are in the sequence (25 0C, ionic strength = 0.10 M): 2-AIBA > β-ala > ala, 2-ABA, nor > val > 4-ABA > gly, ranging from 0.279 to 0.06 (mol einstein-1). Experimental data show that the photoreactivity of Cu(II)/amino-acid complexes can be predicted by Cu(II) speciation in a wide range of the solution conditions, varying in pH and the total concentration of ligand. The stability of the carbon-center radical plays an important role on the Cu(I) quantum yield. The six-membered chelate ring of Cu(II)/amino-acid complexes has larger Cu(I) quantum yields than five-membered chelate ring, probably owing to the increasing of the intra-molecular electron-transfer rate.

摘要 I
Abstract II
總目錄 III
圖目錄 V
表目錄 VI
謝誌 VII
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 相關胺酸的介紹 6
2.2 環境水體中銅錯合物的反應 8
2.3 不同配位基之銅錯合物的光化學反應 10
2.3.1 銅與各種配位基之光化學反應 11
2.3.2 銅與胺酸光化學反應 12
2.4 化學光度計 (Actinometer) 14
2.5 一價銅的測量 16
2.6 反應模式的假設 17
2.6.1 符號解說 19
2.6.2 理論計算—吸收值 19
2.6.3 理論計算—反應速率 20
2.6.4 理論計算—量子產率 21
第三章 研究方法 23
3.1 銅胺酸光反應系統 23
3.1.1 實驗儀器 23
3.1.2 實驗藥品 29
3.1.3 分析流程 30
3.1.5 光強度測量 31
3.1.4 光照反應：一價銅的測量 33
3.2 銅-胺酸系統中各物種所佔比例之計算 34
3.2.1 Visual MINTEQ v.3.1 35
3.2.2 NIST46.8 熱力學資料庫 37
3.2.3 離子強度之修正 38
3.3 數據處理方法 40
3.3.1 光強度方法與數據處理 40
3.3.2 量測一價銅之數據處理 42
3.3.3 計算量子產率之數據處理 43
第四章 結果與討論 45
4.1 2-NB的濃度選取實驗 45
4.2 銅胺酸錯合物光反應結果討論 47
4.2.2 改變條件下銅-胺酸的物種分佈趨勢 47
4.2.1 銅與不同胺酸之一價銅量子產率 54
4.2.3 不同胺酸的物種分布對光反應的影響 58
4.2.4 不同系列胺酸支鏈對光化學反應的影響 60
第五章 結論 68
第六章 未來計畫 69
參考文獻 70
附錄一 胺酸性質 76
附錄二 生成物種之熱力學常數表 77
附錄三 銅與胺酸照光反應之原始數據 78
附錄四 銅胺酸錯合物莫耳吸收係數之原始數據 84
附錄五 Visual MINTEQ v3.1使用說明 90
附錄六 NIST46.8使用說明 99
Acknowledgement 102

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