臺灣博碩士論文加值系統

Mn(4-TMPyP)在pH 7，EtOH/H2O=4/6的混合溶液中，對geraniol及nerol進行多步驟選擇性電催化氧化反應，第一步的產物為其相對應的醛類(geranial及neral)。第二步則再對此醛類混合物(citral)，進行位置選擇性環氧化反應，形成6,7-epoxycitral。動力學研究也證實Mn(4-TMPyP)與烯醇類(geraniol)的反應速率確實明顯高於與烯醛類(citral)的反應速率。然而Mn(4-TMPyP)卻無法對citral的衍生物geranyl acetate進行氧化催化反應。另外與Mn(4-TMPyP)紫質環帶相反電荷的MnTSPP進行同樣的電催化氧化反應研究，反應速率極低。
為對紫質氧化過程中去活性機制更了解，以帶有dinitrophenyl group的二級醯胺取代基鋅紫質(ZnPH)進行氧化機制的探討，ZnPH在氧化部分具三個可逆的氧化波，分別是形成porphyrin cation radical (ZnPH+), porphyrin dication (ZnPH2+)及isoporphyrin dication radical (ZnIP2+)。ZnPH在氧化過程中經由分子內親核反應而生成分子內類紫質，而此分子內isoporphyrin可再被氧化，氧化態可穩定存在十秒鐘以上，但長時間定電位電解得到藍綠色的產物，推測是紫質環進行開環反應。在鹼性溶液中，ZnPH+失去一個質子形成ZnIP，室溫下可穩定存在數小時以上，EPR測量其g值為2.0025，這是第一個可穩定存在的isoporphyrin radical。

Manganese Tetrakis(N-methyl-4-pyridyl)porphine ( Mn(4-TMPyP) ) selectively catalyzes the oxidation of nerol and geraniol at the hydroxyl group to form aldehydes, neral and geranial, respectively. The products keep the original stereostructure of substrates. Manganese porphyrin plays a role of hydrogen atom abstractor in this catalysis. Citral, the mixture of neral and geranial, can be further oxidized by Mn(4-TMPyP) to give epoxides. The epoxidation selectively takes place at the 6,7 double bond of citral. It is the very especial thing that olefin catalyzed by Mn(4-TMPyP) in pH 7 buffer mixed solution undergoes a stepwise catalytic oxidation. First, alcohol was oxidized to aldehyde. Then, epoxidation takes place at the 6,7 double bond of the diolefin. However, the manganese porphyrin lost its catalytical capability as the pH of the solution increased to 10.0. Moreover, the manganese porphyrin showed no appreciable catalytic ability toward geranyl acetate. Semi-empirical calculation suggests that the spatial orientation may play an important role. Besides, kinetic study supports the reaction rate between geraniol and O=MnIV(4-TMPyP) is faster than other substrates. MnTSPP was alao used to be the catalyst in the same pH 10 buffer mixed solution at +1.0 V. There is no remarkable catalyical ability toward geraniol, citral, and geranyl acetate.
Porphyrin ring cleavage is the major deactivation reaction in the process of heme catabolism. The process of porphyrin ring cleavage is thought to involve the formation of isoporphyrin. Endogenous isoporphyrin was formed in oxidation of amide linked zinc meso-tetraphenyl porphyrin (ZnPH). It exhibited three unusual reversible oxidative couples on cyclic voltammetry. The half-wave potentials are at +0.74, +1.07 and +1.38 V, respectively. Observation by UV-vis-near IR spectroelecrochemistry indicated that ZnPH was first oxidized to ZnPH+ and that the second oxidation renders rapid intramolecular chemical reaction to form isoporphyrin, ZnIP. FT-IR spectroelecrochemical study revealed the stepwise intramolecular attack by the oxygen of the amide group to the meso carbon of the porphyrin dication and the formation of the endogenous isoporphyrin. Further oxidation of the isoporphyrin probably resulted in slow ring-opening and decomposition. Addition of a sterically hindered organic base, 2,6-lutidine, rapidly caused ZnPH+ deprotonation to form ZnIP. EPR spectrum of ZnIP was observed and shown a free radical formation. ZnIP could be oxidized to ZnIP+ at the formal potential of +0.96 V. This is the first time that an isoporphyrin radical is observed.

封面
目錄
中文摘要
英文摘要
縮寫表
圖目錄
第一章 錳紫質多步驟選擇性電催化氧化烯醇類
簡介
一、 細胞色素P450 (Cytochrome P450) 　　　
二、 金屬紫質催化烯類環氧化的位置選擇性
三、 金屬紫質催化烯類環氧化的立體選擇性　
四、 金屬紫質催化烯類環氧化的反應機構探討　
五、 錳紫質的氧化催化反應　
六、 Geraniol 與 Nerol 的氧化反應 　　　　
實驗部分
一、紫質的合成　
二、藥品　
三、實驗儀器
結果與討論
一、 Mn(4-TMPyP)在中性混合溶液中的氧化催化反應
二、 Mn(4-TMPyP) 在鹼性溶液中的氧化催化反應　　
三、 錳紫質氧化受質的動力學探討　　　
四、 紫質與受質間的相互吸引力
五、 Mn TSPP在鹼性溶液中的氧化催化反應 　　
結論　
參考文獻　
第二章 由醯胺取代基在氧化過程中形成分子內類紫質探討金屬紫質去活性的反應機制簡介
一、血基質(heme)代謝的反應機構探討　
二、Isoporphyrin的研究
實驗部分
一、藥品　
二、紫質的合成　
三、實驗儀器　
結果與討論
一、 H2PH之電化學與光譜電化學性質
二、 ZnPH之電化學與光譜電化學性質
三、 CuPH之電化學與光譜電化學性質　
結論　
參考文獻　

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