多種有機配位基與二價銅所形成錯合物的光化學氧化還原反應，在環境、工業與生物作用過程中的潛在應用是相當重要的。本文探討配位基中羥基對水溶液中二價銅錯合物之光反應性的效應。於波長313 nm的單光照射下，在廣泛的pH值、二價銅濃度以及配位基濃度範圍中，觀察由二價銅錯合物光致生成一價銅的動力學。對於一配位的銅胺基酸錯合物而言，其一價銅的量子產率(ΦCu(I),CuL)的大小依循以下趨勢：alanine (0.096 ± 0.014) > serine (0.065 ± 0.004) > threonine (0.033 ± 0.003)。對於二配位的銅胺基酸錯合物而言，其一價銅的量子產率(ΦCu(I),CuL2)遵循相同的趨勢：alanine (0.068 ± 0.013) > serine (0.058 ± 0.006) > threonine (0.055 ± 0.006)。此趨勢可能是由於胺基酸中的β-羥基使一價銅再被氧化為二價銅。對於一配位帶有α-羥基的銅羧酸鹽錯合物而言，其一價銅的量子產率(ΦCu(I),CuL)依循以下趨勢：malate (0.16 ± 0.01) > succinate (0.11 ± 0.02)，推測α-羥基可穩定由光反應形成的自由基。然而，在不同羧基數的錯合物系統中，其一價銅的量子產率(ΦCu(I),CuL)的大小依循下列趨勢：lactate (0.28 ± 0.03) > malate (0.16 ± 0.01) > citrate (0.010 ± 0.003‒0.048 ± 0.003)，表示越多的羧基並非能增強錯合物的光反應性。本研究中，羥基的位置顯著影響其錯合物的光反應性，α-羥基能增強光反應性，但β-羥基卻會使光反應生成的自由基不穩定。

The photochemical redox reactions of copper(II) complexes with various organic ligands are of crucial important for their potential uses in environmental, industrial, and biological processes. This study investigated the effect of hydroxyl groups of the organic ligands on the photoreactivity of Cu(II) complexes in aqueous solution. Under monochromatic light irradiation at 313 nm, the kinetics of Cu(I) photoformation from Cu(II) complexes were observed over an extensive range of pH, Cu(II) concentration, and ligand concentration. For Cu(amino acid), the Cu(I) quantum yields (ΦCu(I),CuL) follow the trend: alanine (0.096 ± 0.014) > serine (0.065 ± 0.004) > threonine (0.033 ± 0.003). For Cu(amino acid)2, the Cu(I) quantum yields (ΦCu(I),CuL2) follow the same trend: alanine (0.068 ± 0.013) > serine (0.058 ± 0.006) > threonine (0.055 ± 0.006). This trend may be ascribed to the β-hydroxyl group of the amino acid leading the Cu(I) to be reoxidized to Cu(II). For Cu(carboxylate), the Cu(I) quantum yields (ΦCu(I),CuL) by the α-hydroxyl group in the acid system: malate (0.16 ± 0.01) > succinate (0.11 ± 0.02), it may be inferred that the α-hydroxy group stabilizes the radical from photoreaction. While in different numbers of carboxyl systems, the Cu(I) quantum yields (ΦCu(I),CuL) follows the trend: lactate (0.28 ± 0.03) > malate (0.16 ± 0.01) > citrate (0.010 ± 0.003‒0.048 ± 0.003), the more carboxyl groups do not increase the photoreactivity of the complexes. In the study, the position of the hydroxyl group greatly affects its photoreactivity, the α‒hydroxy group enhances the photoreactivity, but the β‒hydroxy group makes the free radical from photoreaction unstable.

摘要...................................I
ABSTRACT..............................II
謝誌.................................III
目錄..................................IV
圖目錄................................VI
表目錄...............................VII
第一章 前言............................1
1.1簡介................................1
1.2研究動機............................2
1.3研究目的............................2
第二章 文獻回顧.........................3
2.1銅..................................3
2.2配位基..............................3
2.3銅錯合物光反應.......................6
2.3光化學反應機制.......................8
2.4化學光度計..........................11
2.5銅錯合物循環........................13
2.6量測一價銅試劑......................14
2.7反應模型假設........................15
2.7.1符號解說..........................16
2.7.2 溶液中個別二價銅錯合物的吸收度.....16
2.7.3銅物種光反應......................17
第三章 研究方法........................19
3.1 實驗裝置..........................19
3.1.1銅錯合物光反應系統的各項實驗器材...19
3.1.2 其他儀器........................22
3.1.3 實驗藥品........................22
3.1.4母液配製.........................23
3.2實驗分析流程.......................24
3.2.1莫耳吸收係數.....................24
3.2.2光化學反應步驟...................25
3.2.3 MINTEQ.........................26
3.2.4 NIST46.8熱力學資料庫............27
3.2.5離子強度之修正....................28
第四章 結果與討論.......................30
4.1數據處理方法.........................30
4.1.1量測各金屬物種的莫耳吸收係數.........30
4.1.2量測一價銅.........................30
4.1.3光強度量測.........................32
4.1.4計算一價銅的量子產率................33
4.2莫耳吸收係數.........................34
4.3不同配位基光反應.....................38
4.3.1銅絲胺酸..........................39
4.3.2銅蘇胺酸..........................41
4.3.3銅乳酸............................43
4.3.4銅蘋果酸..........................45
4.3.5銅檸檬酸..........................46
4.4光反應性比較........................56
第五章 結論............................59
第六章 未來展望.........................59
參考文獻...............................60
附錄一 配位基性質.......................64
附錄二 金屬錯合物物種之熱力學常數表.......65
附錄三 電子轉移方式......................66
附錄四 錯合物結構........................67
附錄五　銅錯合物莫耳吸收係數原始數據.......68
附錄六 銅錯合物光化學反應之原始數據........71
附錄七 NIST46.8使用說明..................74
附錄八 VISUAL MINTEQ3.1.................79

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