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研究生: 吳肇洋
Wu, Jhao-Yang
論文名稱: 非血基質鐵三價超氧化物與過氧化物之合成與反應性探討
Synthesis and Reactivity of Non-Heme Iron(III) Superoxo and Hydroperoxo Complexes
指導教授: 李位仁
Lee, Way-Zen
學位類別: 碩士
Master
系所名稱: 化學系
Department of Chemistry
論文出版年: 2018
畢業學年度: 106
語文別: 中文
論文頁數: 69
中文關鍵詞: 鐵過氧氫化物鐵過氧化物
英文關鍵詞: iron hydroperoxo, iron peroxo
DOI URL: http://doi.org/10.6345/THE.NTNU.DC.044.2018.B05
論文種類: 學術論文
相關次數: 點閱:70下載:0
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  • 在生物體中,細胞色素P450催化過程中推測有鐵超氧化物、鐵過氧化物和鐵過氧氫化物之中間體生成,其中鐵超氧化物為重要的中間體。實驗室先前的研究,利用FeII(BDPP) 於193 K下與氧氣反應生成鐵超氧化物,再經奪氫反應生成鐵過氧氫化物。在本次研究中,我們使用較穩定的FeIII(BDPBrP)(OO˙)重複先前的實驗,也利用鐵過氧氫化物與酸性受質反應,由紫外光可見光光譜我們推測生成鐵三價物質與過氧化氫。另外,我們也嘗試於193 K下加入超氧化鉀反應,生成之產物其紫外光可見光光譜得到與鐵過氧氫化物之光譜類似的樣式,此產物與酸性受質反應也與鐵過氧氫化物有類似的反應性。

    The catalytic process of cytochrome P450 in organism is presumed to produce iron superoxo and iron peroxo intermediates, and iron superoxo species is the first intermediate. Previously, we have developed FeII(BDPP) which can activate oxygen at 193 K to generate iron superoxo complex. The iron superoxo complex reacted to form iron hydroperoxo species. In this study, we not only repeat previous experiments by using a more stable complex of FeIII(BDPBrP)(OO˙) species, and allow iron hydroperoxo species to react with acidic substrates. From UV-vis spectra, we propose that the formation of iron(III) species and hydrogen peroxide. In addition, we attempt to add potassium superoxide with cryptand at 193 K. The UV-vis spectrum of the resulting solution was similar to that of the iron hydroperoxo spcies. The reaction of the product with the acidic substrate was also similar to the iron hydroperoxo species.

    中文摘要 iii Abstract iv 圖索引 v 第一章 緒論 1 1-1 大自然中含鐵金屬的酶 2 1-2 血基質模擬鐵錯合物 11 1-3 非血基質模擬鐵過氧化物 15 1-4 非血基質模擬鐵超氧化物 21 1-5 研究方向 22 第二章 實驗部分 24 2-1 實驗藥品 24 2-2 實驗儀器及條件 25 2-3 鐵錯合物的製備 29 第三章 結果與討論 31 3-1 鐵超氧化物的性質與反應性 31 3-1.1 鐵超氧化物穩定性探討 31 3-1.2 鐵超氧化物反應性探討 36 3-2 鐵過氧化物的性質探討 50 3-2.1 鐵過氧化物光譜探討 50 3-2.2 鐵過氧化物反應性探討 54 3-3 三價鐵錯合物的性質探討 59 3-3.1 三價鐵錯合物光譜探討 59 3-3.2 三價鐵錯合物反應性 61 第四章 結論與展望 64 4-1 結論 64 4-2 展望 66 鐵超氧化物 66 鐵過氧化物 67 第五章 參考資料 68

    1.Douglas A. Whittington and Stephen J. Lippard J. Am. Chem. Soc., 2001, 123 (5), pp 827–838
    2.Harold Basch, Djamaladdin G. Musaev, and Keiji Morokuma J. Am. Chem. Soc., 1999, 121, 7249–7256
    3.Pamela A. Williams, Jose Cosme, Dijana Matak Vinkovic, Alison Ward, Hayley C. Angove, Philip J. Day, Clemens Vonrhein, Ian J. Tickle, Harren Jhoti1 Science, 2004, 305, 683–686
    4.Sussan Ghassabian, Tristan Rawling, Fanfan Zhou, Munikumar R. Doddareddy, Bruce N. Tattam, David E. Hibbs, Robert J. Edwards, Pei H. Cui, Michael Murray Biochemical Pharmacology, 2012, 84, 215–223
    5.James Belcher, Kirsty J. McLean, Sarah Matthews, Laura S. Woodward, Karl Fisher, Stephen E. J. Rigby, David R. Nelson, Donna Potts, Michael T. Baynham, David A. Parker, David Leys, and Andrew W. Munro J Biol Chem. 2014, 289, 6535–6550.
    6.Peter L. Roach, Ian J. Clifton, Charles M. H.Hensgens, Norio Shibata, Christopher J. Schofield, Janos Hajdu, and Jack E. Baldwin Nature 1997, 387, 827–830
    7.Esta Tamanaha, Bo Zhang, Yisong Guo, Wei-chen Chang, Eric W. Barr, Gang Xing, Jennifer St. Clair, Shengfa Ye, Frank Neese, J. Martin Bollinger, Jr., and Carsten Krebs J. Am. Chem. Soc. 2016, 138, 8862−8874
    8.E. McCandlish, A.R. Miksztal, M. Nappa, A.Q. Sprenger, J.S. Valentine, J.D. Stong, T.G. Spiro. J. Am. Chem. Soc. 1980, 102, 4268–4271.
    9.Jin-Gang Liu, Takehiro Ohta, Satoru Yamaguchi, Takashi Ogura, Satoshi Sakamoto, Yonezo Maeda, and Yoshinori Naruta Angew. Chem. Int. Ed. 2009, 48, 9262–9267
    10.Marcel Lubben, Auke Meetsma, Elizabeth C. Wilkinson, Ben Feringa, and Lawrence Que, Jr. Angew. Chern. Int. Ed. 1995, 34, 1512–1514
    11.Raymond Y. N. Ho, Gerard Roelfes, Ben L. Feringa, and Lawrence Que, Jr. J. Am. Chem. Soc. 1999, 121, 264–265
    12.Gerard Roelfes, Vladislav Vrajmasu, Kui Chen, Raymond Y. N. Ho, Jan-Uwe Rohde, Charon Zondervan, Rene M. la Crois, Ebe P. Schudde, Martin Lutz, Anthony L. Spek, Ronald Hage, Ben L. Feringa, Eckard Mu1nck, and Lawrence Que, Jr. Inorg. Chem. 2003, 42, 2639−2653
    13.Jaeheung Cho, Sujin Jeon, Samuel A. Wilson, Lei V. Liu, Eun A. Kang, Joseph J. Braymer, Mi Hee Lim, Britt Hedman, Keith O. Hodgson, Joan Selverstone Valentine, Edward I. Solomon, Wonwoo Nam Nature, 2011, 478, 502–505
    14.Chien-Wei Chiang, Scott T. Kleespies, Heather D. Stout, Katlyn K. Meier, Po-Yi Li, Emile L. Bominaar, Lawrence Que, Jr., Eckard Münck, and Way-Zen Lee J .Am. Chem. Soc. 2014, 136, 10846−10849
    15.Heather D. Stout, Scott T. Kleespies, Chien-Wei Chiang, Way-Zen Lee, Lawrence Que, Jr., Eckard Münck, and Emile L. Bominaar Inorg. Chem. 2016, 55, 5215−5226
    16.Ruixi Fan, Joan Serrano-Plana, Williamson N. Oloo, Apparao Draksharapu, Estefanía Delgado-Pinar, Anna Company, Vlad Martin-Diaconescu, Margarida Borrell, Julio Lloret-Fillol, Enrique García-España, Yisong Guo, Emile L. Bominaar, Lawrence Que, Jr., Miquel Costas, and Eckard Münck J. Am. Chem. Soc. 2018, 140, 3916−3928

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