嗜甲烷菌內甲烷單氧化酵素中催化反應中心三核銅模擬分子之合成與光譜分析

以作者查詢圖書館館藏

、以作者查詢臺灣博碩士

、以作者查詢全國書目

、勘誤回報

、線上人數：28

、訪客IP：18.117.158.47

姓名

楊秉恭(Bing-Gong Yang) 查詢紙本館藏

畢業系所

化學學系

論文名稱

嗜甲烷菌內甲烷單氧化酵素中催化反應中心三核銅模擬分子之合成與光譜分析
(Models for the Trinuclear Copper Clusters of the Particulate Methane Monooxygenase from Methanotrophic Bacteria: Synthesis, Spectroscopic Characterization of Trinuclear Copper Complexes)

相關論文

★ 烷烴氧化菌及氧化酵素之純化與功能性探討	★ 以電腦模擬研究香蕉型液晶元的分子交互作用力
★ 利用時間相關的電子密度泛函理論研究反式-二苯乙烯胺的光化學行為	★ 以生物資訊法研究穩定Asparagine在左手螺旋形下的交互作用力
★ 葛蘭氏陰性菌脂質A之結構研究	★ 五苯荑衍生之苯乙炔寡聚物之合成與光物理性質研究
★ 紫質三元件系統的金屬化作用對遠端氫鍵調控的影響	★ 非鍵結作用力的理論研究： (1)質子化與氧化三元件系統遠端調控氫鍵的比較 (2)π- π與CH- π作用力的取代基效應
★ 利用時間相關的密度泛涵理論研究HBI分子及其衍生物在第一激發態的位能曲線	★ Replica-Exchange分子動態模擬法研究類澱粉胜肽25-35 嵌入膜與折疊的行為
★ 抗菌胜肽資料庫分析及利用分子動態模擬法探討抗菌胜肽Indolicidin於生物膜上的行為	★ 網頁圖形界面在分子模擬上的應用
★ 類澱粉胜肽Abeta(25-35) 序列影響該類胜肽在水-膜環境下的組態: 強調多樣性的神經毒性	★ 以分子動態模擬法研究陽離子-負電磷脂質雙層的配位網絡結構：延伸應用於膜融合機制
★ 染料敏化太陽能電池吸光性質的計算研究	★ Free Energy Landscape of Ca2+ Induced Lipid Micelle Fusion : Observation of a Dewetting Transition

檔案

[Endnote RIS 格式]

[Bibtex 格式]

[相關文章]

[文章引用]

[完整記錄]

[館藏目錄]

至系統瀏覽論文 ( 永不開放)

摘要(中)

在我們最近DFT計算的結果指出，三核銅簇合物bis(μ3-oxo)trinuclear copper(II, II, III) complex的結構能夠調控一個singlet “oxene”。它被用來模擬一個能輕易對甲烷，或是低碳數的碳氫化合物進行hydroxylation反應的重要膜蛋白酵素，—甲烷單氧化酵素(pMMO)—，其中的一個催化中心(C-cluster）。我們設計並合成了一系列能夠配位三個銅離子的配位基作為模擬分子來模仿這個反應。在質譜分析中，氧化[Cu3(I, I, I)L](X) complexes將形成相對應的[Cu3(II, II, II)L(O)](X)2 complexes。只有一個氧原子停留在trinuclear copper(II, II, II) complex上。當[Cu3(II, II, II)L(O)](X)2 complex在CH3CN中加入了三當量的benzoin和triethylamine並通入氧氣，benzoin氧化成為benzil後再進一步的被氧化並水解成為兩分子的benzoic acid。藉由18O2同位素標記以及GC-MS的分析，證實了bis
(μ3-oxo)trinuclear copper(II, II, III) complex有效率的調控對benzil的oxo-transfer。我們提出一個關於bis(μ3-oxo)Cu(II)Cu(II)Cu(III) trinuclear copper intermediate對benzil分子間進行碳—碳鍵oxo-insertion的反應機制。

摘要(英)

Recent DFT electronic calculations of a trinuclear copper cluster bis(?3-oxo)trinuclear copper(II, II, III) complex have showed that this structure harnesses a singlet “oxene”, mimicking one of the C-clusters in the particulate methane monooxygenase (pMMO), an important membrane enzyme that mediate the facile hydroxylation of methane and other small hydrocarbons. A series of supporting ligands that are capable to trap three copper ions toward developing a model compound to mimic this chemistry, we have designed and synthesized. Oxygenation of their corresponding [Cu3(I, I, I)L](X) complexes of these ligands leads to the formation of [Cu3(II, II, II)L(O)](X)2 (L = 7-Et, 7-Me, 6-Et, 6-Me; X = ClO4- and BF4-) through mass spectrometry analysis. Only one oxygen atom is locked in the trinuclear copper(II, II, II) complex. When the [Cu3(II, II, II)L(O)](X)2 complex is treated with three equivalent amounts of benzoin and triethylamine in CH3CN, and the solution purged by dioxygen, the benzoin is oxidized to benzil, which in turn is cleaved by further oxidation and hydrolyzes to 2 benzoic acid molecules. This chemistry is mediated by efficient oxo-transfer from the bis(μ3-oxo)trinuclear copper(II, II, III) complex to the benzil, as verified by 18O2 isotope labeling experiments and subsequent GC-MS analysis. We propose a mechanism involving intermolecular oxo-insertion across the C-C bond of the benzil by the bis(μ3-oxo)Cu(II)Cu(II)Cu(III) trinuclear copper intermediate.

關鍵字(中)

★ 甲烷單氧化酵素
★ 三核銅簇合物

關鍵字(英)

★ Trinuclear Copper Clusters
★ pMMO

論文目次

Chapter 1 Introduction... 1
Chapter 2 Experimental Section... 9
2.1 Materials... 9
2.2 Instrumentation... 10
2.3 Sample Preparation... 11
(A) Ligand synthesis... 11
a) Synthesis of 3,3’-(1,4-diazepane-1,4-diyl)bis(1- ((2- (diethylamino) ethyl)(ethyl)amino)propan-2-ol) (7-Et)... 11
b) Synthesis of 3,3’-(1,4-diazepane-1,4-diyl)bis(1-((2- (dimethylamino) ethyl) (methyl)amino)propan-2-ol) (7-Me)... 12
c) Synthesis of 3,3’-(piperazine-1,4-diyl)bis(1-((2- (diethylamino)ethyl) (ethyl)amino)propan-2-ol) (6-Et)... 13
d) Synthesis of 3,3’-(piperazine-1,4-diyl)bis(1-((2- (dimethylamino) ethyl) (methyl)amino)propan-2-ol) (6-Me)... 14
a) Synthesis of 3,3’-(1,4-diazepane-1,4-diyl)bis(1-((2- (diethylamino) ethyl) (ethyl)amino)propan-2-ol) (7-Et)... 15
b) Synthesis of 3,3’-(1,4-diazepane-1,4-diyl)bis(1-((2- (dimethylamino) ethyl)(methyl)amino)propan-2-ol) (7-Me)... 16
c) Synthesis of 3,3’-(piperazine-1,4-diyl)bis(1-((2-(diethylamino)ethyl) (ethyl)amino)propan-2-ol) (6-Et)... 17
d) Synthesis of 3,3’-(piperazine-1,4-diyl)bis(1-((2- (dimethylamino) ethyl) (methyl)amino)propan-2-ol) (6-Me)... 18
(B) Preparation of the Cu(I) complexes... 20
a) Cu(I)[(CH3CN)4]BF4... 20
b) Cu(I)[(CH3CN)4]ClO4... 20
(C) Preparation of tricopper(I, I, I) complex: Method (a)... 21
7-Et.. 21
[7-Et]2-[Na2]2+... 22
7-Me... 23
[7-Me]2-[Na2]2+... 24
6-Et... 25
[6-Et]2-[Na2]2+... 26
6-Me... 27
[6-Me]2-[Na2]2+... 28
(D) Preparation of tricopper(I, I, I) complex: Method (b)... 29
7-Et... 29
7-Me... 31
6-Et... 33
6-Me... 35
(E) Dioxygen Activation... 37
Chapter 3 Results and Discussion... 38
Synthesis of tricopper(I, I, I) complex... 38
Dioxygen reactivity of [Cu3(I, I, I)(L)](X) (L = 7-Et, 7-Me, 6-Et, and 6-Me; X = BF4, ClO4)... 40
Mass spectrometry analysis... 41
a) 7-Et... 41
1. ( X = ClO4-)... 41
2. ( X = BF4-)... 43
b) 7-Me... 45
1. ( X = ClO4-)... 45
Reaction of [Cu3(II, II, II)(L)(O)](X)2 (L = 7-Et, 7-Me, 6-Et, and 6-Me; X = BF4, ClO4) with benzoin (16O and 18O experiments)... 49
Oxene Insertion Across the C-C Bond of Benzil and C-C Bond Cleavage to Produce Benzoic Acid... 54
Chapter 4 Conclusions... 56
Reference ...58
Appendix... 65

參考文獻

1. Periana, R. A.; Taube, D. J.; Gamble, S.; Taube, H.; Satoh, T.; Fujii, H., Platinum catalysts for the high-yield oxidation of methane to a methanol derivative. Science 1998, 280, (5363), 560-564.
2. Henriciolive, G.; Olive, S., Fischer-Tropsch Synthesis - Molecular-Weight Distribution of Primary Products and Reaction-Mechanism. Angewandte Chemie-International Edition in English 1976, 15, (3), 136-141.
3. Ashcroft, A. T.; Cheetham, A. K.; Foord, J. S.; Green, M. L. H.; Grey, C. P.; Murrell, A. J.; Vernon, P. D. F., Selective oxidation of methane to synthesis gas using transition metal catalysts. Nature 1990, 344, (6264), 319-321.
4. Hickman, D. A.; Schmidt, L. D., Production of Syngas by Direct Catalytic-Oxidation of Methane. Science 1993, 259, (5093), 343-346.
5. Hanson, R. S.; Hanson, T. E., Methanotrophic bacteria. Microbiological Reviews 1996, 60, (2), 439-&.
6. Chan, S. I.; Chen, K. H. C.; Yu, S. S. F.; Chen, C. L.; Kuo, S. S. J., Toward delineating the structure and function of the particulate methane monooxygenase from methanotrophic bacteria. Biochemistry 2004, 43, (15), 4421-4430.
7. Feig, A. L.; Lippard, S. J., Reactions of Nonheme Iron(Ii) Centers with Dioxygen in Biology and Chemistry. Chemical Reviews 1994, 94, (3), 759-805.
8. Lipscomb, J. D., Biochemistry of the Soluble Methane Monooxygenase. Annual Review of Microbiology 1994, 48, 371-399.
9. Yoshizawa, K.; Suzuki, A.; Shiota, Y.; Yamabe, T., Conversion of methane to methanol on diiron and dicopper enzyme models of methane monooxygenase: A theoretical study on a concerted reaction pathway. Bulletin of the Chemical Society of Japan 2000, 73, (4), 815-827.
10. Yoshizawa, K., Two-step concerted mechanism for methane hydroxylation on the diiron active site of soluble methane monooxygenase. Journal of Inorganic Biochemistry 2000, 78, (1), 23-34.
11. Wilkinson, B.; Zhu, M.; Priestley, N. D.; Nguyen, H. H. T.; Morimoto, H.; Williams, P. G.; Chan, S. I.; Floss, H. G., A concerted mechanism for ethane hydroxylation by the particulate methane monooxygenase from Methylococcus capsulatus (Bath). Journal of the American Chemical Society 1996, 118, (4), 921-922.
12. Valentine, A. M.; Wilkinson, B.; Liu, K. E.; KomarPanicucci, S.; Priestley, N. D.; Williams, P. G.; Morimoto, H.; Floss, H. G.; Lippard, S. J., Tritiated chiral alkanes as substrates for soluble methane monooxygenase from Methylococcus capsulatus (Bath): Probes for the mechanism of hydroxylation. Journal of the American Chemical Society 1997, 119, (8), 1818-1827.
13. Valentine, A. M.; LeTadic-Biadatti, M. H.; Toy, P. H.; Newcomb, M.; Lippard, S. J., Oxidation of ultrafast radical clock substrate probes by the soluble methane monooxygenase from Methylococcus capsulatus (Bath). Journal of Biological Chemistry 1999, 274, (16), 10771-10776.
14. Elliott, S. J.; Zhu, M.; Tso, L.; Nguyen, H. H. T.; Yip, J. H. K.; Chan, S. I., Regio- and stereoselectivity of particulate methane monooxygenase from Methylococcus capsulatus (Bath). Journal of the American Chemical Society 1997, 119, (42), 9949-9955.
15. Huang, D. S.; Wu, S. H.; Wang, Y. S.; Yu, S. S. F.; Chan, S. I., Determination of the carbon kinetic isotope effects on propane hydroxylation mediated by the methane monooxygenases from Methylococcus capsulatus (Bath) by using stable carbon isotopic analysis. Chembiochem 2002, 3, (8), 760-765.
16. Yu, S. S. F.; Wu, L. Y.; Chen, K. H. C.; Luo, W. I.; Huang, D. S.; Chan, S. I., The stereospecific hydroxylation of 2,2-H-2(2) butane and chiral dideuteriobutanes by the particulate methane monooxygenase from Methylococcus capsulatus (bath). Journal of Biological Chemistry 2003, 278, (42), 40658-40669.
17. Baik, M. H.; Gherman, B. F.; Friesner, R. A.; Lippard, S. J., Hydroxylation of methane by non-heme diiron enzymes: Molecular orbital analysis of C-H bond activation by reactive intermediate Q. Journal of the American Chemical Society 2002, 124, (49), 14608-14615.
18. Baik, M. H.; Newcomb, M.; Friesner, R. A.; Lippard, S. J., Mechanistic studies on the hydroxylation of methane by methane monooxygenase. Chemical Reviews 2003, 103, (6), 2385-2419.
19. Chen, K. H. C.; Chen, C. L.; Tseng, C. F.; Yu, S. S. F.; Ke, S. C.; Lee, J. F.; Nguyen, H. T.; Elliott, S. J.; Alben, J. O.; Chan, S. I., The copper clusters in the particulate methane monooxygenase (pMMO) from Methylococcus capsulatus (Bath). Journal of the Chinese Chemical Society 2004, 51, (5B), 1081-1098.
20. Lieberman, R. L.; Rosenzweig, A. C., Crystal structure of a membrane-bound metalloenzyme that catalyses the biological oxidation of methane. Nature 2005, 434, (7030), 177-182.
21. Chen, P. P.-Y.; Chan, S. I., Theoretical modeling of the hydroxylation of methane as mediated by the particulate methane monooxygenase. Journal of Inorganic Biochemistry High-valent iron intermediates in biology 2006, 100, (4), 801-809.
22. Burness, D. M.; Bayer, H. O., Synthesis and Reactions of Quaternary Salts of Glycidyl Amines. Journal of Organic Chemistry 1963, 28, (9), 2283-&.
23. Andreyanova, T. A.; Minakova, S. M.; Linberg, L. F.; Alekseeva, L. M.; Turchin, K. F.; Chernov, V. A.; Sheinker, Y. N.; Safonova, T. S., Synthesis and Anti-Tumor Activity of Diamine Derivatives Containing Gamma-Chloro-Beta-Hydroxy-Propyl Groups. Khimiko-Farmatsevticheskii Zhurnal 1982, 16, (12), 1460-1463.
24. Hayashi, S.; Furukawa, M.; Fujino, Y.; Sugita, M.; Nakao, T., Studies on Antitumor Substances .12. Synthesis of Bis(2,3-Epoxypropyl)Amine Derivatives and Reaction with Some Nucleophiles. Chemical & Pharmaceutical Bulletin 1971, 19, (10), 2003-&.
25. Knapp, S.; Trope, A. F.; Theodore, M. S.; Hirata, N.; Barchi, J. J., Ring Expansion of Ketones to 1,2-Keto Thioketals - Control of Bond Migration. Journal of Organic Chemistry 1984, 49, (4), 608-614.
26. Blain, I.; Bruno, P.; Giorgi, M.; Lojou, E.; Lexa, D.; Reglier, M., Aminoindanes in oxygen transfer reactions, 2 - Copper complexes as functional models for dopamine beta-hydroxylase stereospecific oxygen atom transfer. European Journal of Inorganic Chemistry 1998, (9), 1297-1304.
27. Blain, I.; Giorgi, M.; De Riggi, I.; Reglier, M., Aminoindanes in oxygen transfer reactions, part 3. Copper complexes as functional models for dopamine beta-hydroxylase mechanistic study of oxygen atom transfer from Cu/O species to benzylic C-H bonds. European Journal of Inorganic Chemistry 2001, (1), 205-211.
28. Blain, I.; Pierrot, M.; Giorgi, M.; Reglier, M., Dopamine beta-hydroxylase, a fascinating mammalian copper-containing monooxygenase: enzymatic and biomimetic studies of the O-atom transfer catalysis. Comptes Rendus De L Academie Des Sciences Serie Ii Fascicule C-Chimie 2001, 4, (1), 1-10.
29. Gelling, O. J.; Meetsma, A.; Feringa, B. L., Bimetallic Oxidation Catalysts - Synthesis, X-Ray-Analysis, and Reactivity of a Binuclear Para-Hydroquinone-Containing Copper(Ii) Complex. Inorganic Chemistry 1990, 29, (15), 2816-2822.
30. Gelling, O. J.; Vanbolhuis, F.; Meetsma, A.; Feringa, B. L., Bimetallic Oxidation Catalysts - Oxygen Insertion into an Aryl-Hydrogen Bond of a Binuclear Copper(I) Complex. Journal of the Chemical Society-Chemical Communications 1988, (8), 552-554.

指導教授

蔡惠旭、陳長謙
(Hui-Hsu Gavin Tsai、Sunney I. Chan)

審核日期

2006-7-24

推文