模擬DNA化學-雙降冰烯高分子

本篇論文的主旨在模擬並探討DNA的兩種生物性質：水溶性高分子以及高分子的複製反應。在高分子的複製方面，我們完成了文獻上第一個人造高分子的複製反應，此研究工作是利用一條刷子狀之單股降冰烯高分子，作為複製反應的模板，然後經由共價鍵的作用力，將單體銜接至模板，接著加入第一代Grubbs催化劑，將模板所懸掛之單體聚合。此一過程產生了不對稱結構之雙股高分子，即高分子之兩股分別具有不同之取代基，其二維結構經由掃瞄式穿隧電子顯微鏡證明為結構規整之梯狀雙股高分子。經由水解反應，此不對稱之雙股結構，轉變為二條互補的單股高分子，其中一股為酯溶性之高子，而另一股為水溶性高分子，這一對互補結構可以經由有機溶劑與鹼性水溶液的萃取而分離。在水溶性高分子的合成方面，我們考慮到降冰片烯高分子的骨架是由重覆性的反式雙鍵所構成，為不飽合結構，因此利用四氧化鋨結合硼酸的金屬催化反應，可以將高極性基團引進到降冰片烯高分子的骨架上，這項高分子的二羥化反應，為具有高度實用性之聚醇高分子的製備方法，可以被廣泛的應用到巨分子的官能基轉換上，特別是將疏水性的高分子轉換成親水性高分子。而雙股降冰片烯高分子本身結構的剛性以及對稱性，更使得鋨金屬催化的二羥化反應具有非常高的立體選擇性，這項工作也是文獻上第一個具有立體選擇性的高分子二羥化反應。

關鍵字

降冰片烯；複製；水溶性

並列摘要

The simulation of DNA chemistry by polybisnorbornenes is described. DNA molecules are double stranded polymers and the most important property for DNA molecules is replication. The purpose of this thesis is to mimic DNA replication and to functionalize double stranded polymers which could be used for further bioconjugation such as phosphorylation. Regarding the polymer replication, the single stranded polynorbornene acts as a template for norbornene monomer adhesion via ester linkage. This polymer is treated with Grubbs I catalyst to proceed the ring opening metathesis polymerization to afford the corresponding unsymmetric double stranded polymer that has been thoroughly characterized by spectroscopic means as well as by STM images. After hydrolysis, a complementary polynorbornenecarboxylic acid is produced and converted into the corresponding polyester. The overall process involves a pass of the information from the template polymer to the daughter polymer. In addition, we present a general and versatile preparation of polyols from polynorbornenes by catalytic dihydroxylation using a modified Naraska’s procedure. The polymers included single stranded and double stranded polynorbornenes were fully functionalized by OsO4. These polymers, are hydrophilic, double stranded and consist of a lot of reactive hydroxyl groups over the polymeric side chains, which could be applied for bioconjugations and bionanotechnology in the future.

並列關鍵字

polybisnorbornene ； replication ； water solubility

參考文獻

1. Watson, J. D.; Crick, F. H. C., Molecular Structure of Nucleic Acids - a Structure for Deoxyribose Nucleic Acid. Nature 1953, 171, 737-738.

2. Lehn, J. M.; Rigault, A.; Siegel, J.; Harrowfield, J.; Chevrier, B.; Moras, D., Spontaneous Assembly of Double-Stranded Helicates from Oligobipyridine Ligands and Copper(I) Cations - Structure of an Inorganic Double Helix. Proc. Natl. Acad. Sci. 1987, 84, 2565-2569.

3. An, D. L.; Nakano, T.; Orita, A.; Otera, J., Enantiopure double-helical alkynyl cyclophanes. Angew. Chem. Int. Ed. 2002, 41, 171-173.

4. Fink, H. W.; Schonenberger, C., Electrical conduction through DNA molecules. Nature 1999, 398, 407-410.

6. Zwolak, M.; Di Ventra, M., DNA spintronics. Appl. Phys. Lett. 2002, 81, 925-927.

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模擬DNA化學-雙降冰烯高分子

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