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  • 學位論文

具親水及雙光子吸收性質之新穎有機材料合成

Synthesis of novel organic materials with hydrophilic and two photon absorption property

指導教授 : 趙啟民

摘要


本論文合成出兩個以dibenzo[a,c]-phenazine為電子受體中心(acceptor),以arylamine為電子予體,具D-A-D (D = donor,A = acceptor) 骨架之quadrupolar形式且具有親水性的雙光子吸收材料,針對其合成路徑及光物理性質研究和探討。利用可生成碳-碳鍵之Suzuki偶合反應或Stille 偶合反應,或是可生成碳-氮鍵的Buchwald- Hartwig 偶合反應,可得到新的化合物。選用已知雙光子吸收的係數(cross section)較大的結構,並引入具有親水性的官能基,以提高其在水中的溶解度,以利於在生醫領域上之應用,如生物細胞的標的螢光染料、生物分析、光動力療法(photodynamic therapy, PDT) 等。結構上兩個化合物皆以dibenzo[a,c]-phenazine為中心骨架,在骨架上面接上兩條triethylene glycol鏈段,而2和7位置則接上兩種不同共軛片段,末端則為diphenylamino推電子基團,其兩個苯環對位羥基各接上兩條triethylene glycol鏈段。其一化合物之spacer由thiophene與苯環構成(thiophene連結中心骨架),另一化合物之spacer則是由thiophene與fluorene構成(thiophene連結中心骨架),而fluorene之9號碳原子並接上兩條triethylene glycol鏈段。兩化合物在不同溶劑中最大吸收波長都在350 nm至480 nm範圍,且消光係數約在56,900至1,42,400 M-1cm-1之間,而螢光波長約在500到650 nm範圍。在電化學性質上,從循環伏安法(cyclic voltammetry,CV) 可得知其氧化還原電位。

關鍵字

親水性 雙光子吸收

並列摘要


Hydrophilic compounds of quadrupolar-type two photon absortion chromophores containing a D-A-D motif ( D = donor; A = acceptor) with dibenzo[a,c]-phenazine entity as the acceptor and arylamine as the donor have been synthesized, and their photophyscial properties were also investigated. Suzuki coupling and Stille coupling reactions were used for construction of C-C bonds, and Buchwald- Hartwig coupling reaction was used for construction of C-N bonds. Previously developed entity possessing large two-photon absorption cross sections were modified by incorporation of water soluble groups to improve water solubility of the chromophores, so as to be used as nonradiative labels in biological analysis, biomarkers in biomedical applications including imaging diagnosis and photodynamic therapy (PDT). The dibenzo[a,c]-phenazine core is tethered with two triethylene glycol chains, and the 2 and 7 postions of the core are connected to the conjugated spacers, and each peripheral diphenylamino entity has a triethylene glycol chain at the para position of the phenyl rings. The spacer in one of the compound is composed of a thiophene and phenyl with the thiophene ring connected to the core. The other compound uses a thiophene ring and fluorene ring as the spacer, and the thiophene ring is connected to the core. Moreover, the fluorene ring is also tethered with two triethylene glycol chains at the 9 position. Both compounds absorb in the region of 500–650 nm with fairly high molar absorption coefficients (56,900–1,42,400M-1cm-1), and emit in the region of 500–650 nm. The electrochemical properties of the compounds were also investigated with cyclic voltammetry.

參考文獻


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