設計合成以1,2,3-三唑為基礎的人工水解?用於水解有機磷農藥; Artificial Hydrolase Mimics, 1,2,3-Triazole-Based Metal Complexes, for Hydrolysis of Organophosphate Pesticides

Please use this identifier to cite or link to this item: http://ir.lib.ncu.edu.tw/handle/987654321/43747

Title:	設計合成以1,2,3-三唑為基礎的人工水解?用於水解有機磷農藥;Artificial Hydrolase Mimics, 1,2,3-Triazole-Based Metal Complexes, for Hydrolysis of Organophosphate Pesticides
Authors:	陳錫勳;Hsi-Hsun Chen
Contributors:	化學研究所
Keywords:	水解酶;人工酵素;有機磷農藥;胺基酸;金屬錯合物;1 2 3-三唑;雙金屬中心;artificial enzyme;amino acid;metal complex;binuclear metal center;1 2 3-triazole;hydrolase;organophosphate
Date:	2010-07-27
Issue Date:	2010-12-08 14:18:01 (UTC+8)
Publisher:	國立中央大學
Abstract:	雙金屬中心 ( Binuclear metal center) 的結構常見於磷酸酯水解酶 (Organophosphate hydrolase) 的活性中心。我們設計以1,2,3-三唑 (1,2,3-Triazole) 為中心，以此延伸出兩段碳鏈上分別帶有胺基與羧基結構，並與二價金屬離子進行螯合形成錯合物，進而使錯合物相似於雙金屬中心的結構。我們也透過形成醯胺鍵結連接不同種類的胺基酸，對金屬離子提供更多的配位鍵，使錯合物趨於穩定；同時，我們也可以藉由額外的胺基酸幫助配位基抓住更多的金屬離子，提升催化的活性。在合成方面，我們透過由K. B. Sharpless團隊研發出來的Click chemistry，亞銅催化Huisgen環化反應，形成1,2,3-三唑中心的分子，如化合物4。在這裡我們設計了引入一個L-天冬胺酸的化合物6。由於在選擇性去Boc 保護基時產率過低，因此我們還無法很有效率的得到於兩端引入L-天冬胺酸的化合物10。在催化活性測試方面，我們針對化合物4與化合物6，調整人工酵素的濃度、緩衝溶液的種類與pH值、金屬離子的濃度。結果並沒有增加Paraoxon 水解的速率。因此在這些條件的調整之下，化合物4與化合物6沒有催化的活性。接下來可以再引入其他的胺基酸，亦或是以化合物4的結構進行再改良，希望能具備更好的催化活性。 We can find the binuclear metal center structure in most organophosphate hydrolases. We design the 1,2,3-triazole core in our ligand, which can supply two different chelating directions. The amino group and carboxyl group in our ligand can help the compound to chelate metal ions tightly. This structure can be coupled with other amino acids via amide formation. That can make the ligand chelate metal ion tightly and catch many metal ions. We can synthesize the 1,2,3-triazole ring via Cu (I)-catalyzed Huisgen cycloaddition from the reserch of K. B. Sharpless group. We successfully synthesize the Compound 4 and Compound 6. We have very low yield in selectively Boc deprotection of Compound 5, so we can’t efficiently get the Compound 10, with two L-aspartic acids. In hydrolysis activity test, we change the concentration of artificial enzyme, the species and pH values of buffer, and concentration of metal ions. In these conditions, we can not observe the better hydrolysis activity than only metal ion in the experiment. We may add other amino acids in our ligand, or modify the structure of compound 4 for our next step.
Appears in Collections:	[Graduate Institute of Chemistry] Electronic Thesis & Dissertation

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