鑭系金屬錯合物之熱力學與水解磷酸酯鍵之動力學研究

Abstract

合成設計能促進磷酸酯鍵水解的金屬錯合物，一直是我們實驗室很感興趣的研究領域，尤其是以鑭系金屬離子大環配位子錯合物這方面的研究，因其具有高度的熱力學穩定、動力學穩定、高配位數及電子密度等特性，使得鑭系金屬大環錯合物非常適合作為人造水解酶。 之前實驗室已合成一系列配位子，並且經由實驗證實 EuDO2A+ 具有極高水解 BNPP 的效力，除此之外，我們亦由實驗驗證配位水及錯合物之電性能影響磷酸酯鍵水解。 本篇論文將以三氮九元環為主體，合成一系列相關的配位子，包含 NO2A 、PhNO2A 及三氮九元環雙體配位子。由前人的研究可得知，改變配位子的特性，或許可提高金屬錯合物對於磷酸酯鍵的水解效力，因此我們將比較NO2A 及 PhNO2A 對於鑭系金屬穩定常數，及其鑭系金屬錯合物水解磷酸酯鍵的影響。除此之外，雙體錯合物也是我們一直感興趣的研究，近年來也有很多文獻指出雙核金屬錯合物對於水解磷酸酯鍵更具效力，而我們也將朝這方面的研究努力邁進。

We have been interested in design and synthesis of macrocyclic lanthanide complexes which are capable of catalytically hydrolyzing phosphodiester bonds. Because of their high thermodynamics stability, low kinetics lability, high coordination numbers, and charge density, macrocyclic lanthanide complexes will be suitable as artificial nucleases. We had synthesized a few ligands and verified EuDO2A+ would promote effectively hydrolysis of BNPP by experiment. We also verified more coordinated water would make metal complexes more effectively in hydrolyzing phosphodiester bonds. And metal complexes carry positive charge would enhance its ability in hydrolyzing BNPP. According to previous researches, we would improve efficiency in hydrolyzing phosphodiester bonds by changing characters of metal complexes. We will synthesize NO2A, PhNO2A and its dimer structure, and study the stability constants for lanthanides complexes and kinetics in hydrolyzing BNPP. And we also want to understand their differences in catalytic mechanism. Additionally, we are interesting in dinuclear metal complexes. Many researches indicate dinuclear metal complexes have more effective than monomer.