在天然水環境中二價銅與多種有機配位基所形成錯合物的光化學反應對於光反應性之研究相當重要，一價銅量子產率的測定是評估銅錯合物的光反應性之指標。藉由改變除氧水溶液中的pH值、總多元羧酸濃度與總二價銅濃度等廣泛的實驗條件，於波長313 nm的光照射下，銅多元羧酸錯合物經由配位基-金屬電荷轉移 (LMCT)反應引發一價銅的生成，研究配位基結構對於銅多元羧酸錯合物系統中光生成一價銅的效應。利用多元線性回歸分析測定個別二價銅錯合物種於313 nm下的莫耳吸收係數與一價銅的量子產率，對於帶有胺基的銅多元羧酸錯合物而言，其CuL的一價銅量子產率 (ΦCu(I),CuL)遵循以下趨勢：天門冬胺酸 (0.081 ± 0.025) > 麩胺酸 (0.062 ± 0.032)，CuL2的一價銅量子產率 (ΦCu(I),CuL2)也依循相同趨勢：天門冬胺酸 (0.035 ± 0.010) > 麩胺酸 (0.031 ± 0.011)，結果顯示配位基上的碳鏈長度增加可能會降低光反應性，然而，CuL的一價銅量子產率 (ΦCu(I),CuL)會大於CuL2的一價銅量子產率 (ΦCu(I),CuL2)，此結果可透過銅與配位基之間的穩定效應說明。對於帶有α-羥基及帶有胺基的銅多元羧酸錯合物而言，其CuL的一價銅的量子產率 (ΦCu(I),CuL)遵循以下趨勢：蘋果酸 (0.161 ± 0.010) > 琥珀酸 (0.102 ± 0.018) > 天門冬胺酸 (0.081 ± 0.025)，這些結果表明α-羥基會增加光反應性，其可歸因於α-羥基會穩定錯合物的激發態，相反地，胺基會降低光反應性，顯示胺基可能會降低光活性狀態，阻礙胺基羧酸根自由基 (H2NRCO2•)的脫羧反應。對於帶有三個羧基的銅多元羧酸錯合物而言，其Cu(HL)的一價銅量子產率 (ΦCu(I),Cu(HL))遵循以下趨勢：三羧酸 (1.834 ± 0.868) > 檸檬酸 (0.157 ± 0.078)，結果顯示β-羥基可能會降低光反應性。此外，Cu(II)/Asp系統中的光產物乙醛及Cu(II)/Cit系統中的光產物丙酮的量子產率已被測定，Cu(I)與這些羰基產物的個別量子產率之比例約為2:1，於本研究中也提出其光化學反應機制模型假設。

The photochemical reaction of Cu(II) complex with various organic ligands in the natural water environment is crucial importance for the study of photoreactivity. Determination of Cu(I) quantum yield is the index for evaluating the photoreactivity of Cu(II) complex. Under irradiation at 313 nm, the effect of ligand structure to the Cu(I) photoformation of Cu(II)/multicarboxylic acid complex systems have been studied in the deaerated aqueous solutions over a widespread pH, total multicarboxylic acid concentration and total Cu(II) concentration. The Cu(I) photoformation is induced from Cu(II)/multicarboxylic acid complex through ligand-to-metal charge transfer (LMCT). Determination for molar absorptivities and Cu(I) quantum yields of individual Cu(II) complex species at 313 nm by using the multivariate linear regression analysis. For the Cu(II)/multicarboxylic acid complex with amino group, the Cu(I) quantum yields for CuL (ΦCu(I),CuL) follow the trend: aspartic acid (Asp) (0.081 ± 0.025) > glutamic acid (Glu) (0.062 ± 0.032) and those for CuL2 (ΦCu(I),CuL2) also follow the same trend: Asp (0.035 ± 0.010) > Glu (0.031 ± 0.011). The results demonstrate that the photoreactivity probably lowers since increasing the length of carbon chain of ligand. However, the result of ΦCu(I),CuL larger than ΦCu(I),CuL2 is explained from the stabilizing effect for Cu(II) and ligand. For the Cu(II)/multicarboxylic acid complex with amino group and the other with α-OH group, ΦCu(I),CuL follow the trend: malic acid (MA) (0.161 ± 0.010) > succinic acid (SA) (0.102 ± 0.018) > Asp (0.081 ± 0.025). These results indicate that α-OH group increase photoreactivity, which attributable to the stabilizing effect of α-OH group on the excited state of Cu(II) complex. Oppositely, the amino group lowers the photoreactiviy, which illustrates that the amino group decreases the photoreactive state and hinders the decarboxylation of aminocarboxylate radical. For the Cu(II)/multicarboxylic acid complex with three carboxylato group, the Cu(I) quantum yields for Cu(HL) (ΦCu(I),Cu(HL)) follow the trend: tricarballylic acid (Tca) (1.834 ± 0.868) > citric acid (Cit) (0.157 ± 0.078). The result indicates that β-OH group perhaps lowers the photoreactivity. Furthermore, the quantum yields of acetaldehyde and acetone photoproducts from Cu(II)/Asp and Cu(II)/Cit systems have been determined, respectively. The individual quantum yields of Cu(I) and carbonyl photoproducts are approximately in the ratio of 2:1. The photochemical reaction mechanism model assumption is proposed.

摘要 Ⅰ
Abstract Ⅱ
謝誌 IV
目錄 V
圖目錄 ⅤII
表目錄 XX
第一章 緒論 1
1.1 簡介 1
1.2 研究動機 2
1.3 研究目的 3
第二章 文獻回顧 4
2.1 環境中的銅 (Copper)分布 4
2.2 配位基 5
2.2.1 胺基酸 (Amino acid) 5
2.2.2 多元羧酸 (Multicarboxylic acid) 5
2.3 環境水體中銅錯合物的光化學反應 6
2.3.1 Cu(II)/多元羧錯合物 (Cu(II)/multicarboxylic acid complex) 7
2.3.2 Cu(II)/α-胺基酸錯合物 (Cu(II)/α-amino acid complex) 8
2.4 一價銅的量測 10
2.5 醛酮類的量測 12
2.6 化學光度計 (Chemical Actinometer) 12
第三章 實驗方法 15
3.1 實驗理論與反應模型 15
3.1.1 反應模型假設與條件 15
3.1.2 水溶液中個別Cu(II)/多元羧酸錯合物的莫耳吸收係數 16
3.1.3 水溶液中個別Cu(II)/多元羧酸錯合物的一價銅量子產率 18
3.1.4 水溶液中個別Cu(II)/多元羧酸錯合物的醛酮光產物量子產率 21
3.2 銅錯合物系統中各物種比例之計算 24
3.3 實驗藥品 26
3.3.1 藥品 26
3.3.2 溶液配製 27
3.4 實驗儀器裝置 32
3.4.1 紫外可見光譜儀 (UV-Vis spectrophotometer) 32
3.4.2 單光照射系統 (Monochromatic irradiation system) 32
3.4.3 除氧系統 (Deaerated system) 33
3.4.4 高效能液相層析儀 (High-Performance Liquid Chromatography) 34
3.4.5 其他儀器 35
3.5 實驗分析流程 35
3.5.1 銅錯合物之莫耳吸收係數的量測 35
3.5.2 量測一價銅的光反應步驟 36
3.5.3 光強度的量測 39
3.5.4 銅錯合物之光產物乙醛的量測 42
3.5.5 銅錯合物之光產物丙酮的量測 44
第四章 結果與討論 48
4.1 銅物種分布 48
4.2 個別二價銅錯合物種的莫耳吸收係數 48
4.3 Cu(II)/多元羧酸系統中一價銅生成之動力學 61
4.4 Cu(II)/多元羧酸系統中一價銅的量子產率 70
4.5 Cu(II)/多元羧酸系統中醛酮光產物生成之動力學 82
4.6 Cu(II)/多元羧酸系統中醛酮光產物的量子產率 87
4.7 配位基結構的光反應性之比較 101
第五章 結論 105
第六章 未來展望 105
參考文獻 107
附錄一Cu(II)/多元羧酸系統中光產物氨之測定 116
附錄二Cu(II)/多元羧酸錯合物之莫耳吸收係數原始數據 117
附錄三Cu(II)/多元羧酸錯合物光反應之原始數據 128
附錄四NIST 46.8操作步驟說明 134
附錄五Visual MINTEQ 3.1使用說明 139

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