- 學位論文
新型近紅外光響應分子的設計、合成、鑑定與生醫應用
Design, Synthesis and Characterization of New Near-Infrared Response Materials and Their Biomedical Applications
摘要
近年來，近紅外光波段的材料逐漸受到矚目。因此波段對於組織具有較深的穿透度，利用此特性，使它在生物顯影以及癌細胞的治療上具有相當重要的地位。在本篇論文中，主要以推電子基－拉電子基核心－推電子基 (D-A-D) 為架構設計分子，利用其剛硬性與平面性來提升螢光量子產率，再進一步使用具有強拉電子性、雙自由基特性的核心結構來使分子吸收波長達到較紅的波段。 第一章中，以二苯並[f,h]噻吩並[3,4-b]喹喔啉 (Dibenzo[f,h]thieno[3,4-b] quinoxaline, DBTQ) 和噻吩並[3,4-b]喹喔啉 (thieno[3,4-b]quinoxaline, TQ) 為核心，分別接上相同推電子基團，設計出吸收在近紅外光區的分子，進一步比較核心結構的拉電子性質不同對吸收所造成的差異，再將此系列分子做成奈米粒子，運用於光熱療法或光動力療法上，並討論其效率的差異。而在第二章則分成兩部分，第一部分以噻吩噻二唑 (thienothiadiazole, TTD) 為核心，設計出一系列的螢光材料，由於放光在近紅外光區 (>700 nm)，且具有優異的螢光量子產率，故將它使用於有機發光二極體中的放光客體。另外則是以苯并雙噻二唑 (benzobisthiadiazole, BBT) 為核心，利用其具有強的雙自由基特性，並進一步接上具有水溶性的基團，除了使放光達到近紅外光波段之外，同時也能提升生物相容性，增加在生物顯影上的應用價值。第三章，為菲咯啉[9,8-bc:10,1-b'c']二噻吩 (phenanthro[9,8-bc:10,1-b’c’]dithiophene, PHDT) 新核心的設計及合成，利用此核心本身結構的剛硬性及雙自由基特性，進一步設計出具有近紅外光區的螢光分子。
並列摘要
In the past few years, many molecular materials with good near-infrared (NIR) response for biomedical applications with deeper tissue penetration and minimized damage to healthy tissue have been developed. Taking advantage of NIR response, the molecular materials have made very important contribution in bioimaging and cancer treatment. In this thesis, new NIR response molecules were designed with the donor-acceptor-donor (D-A-D) architecture, which utilizes rigid and planar molecular structure to give good fluorescence quantum yield for NIR emission. In which, the core structures with strong electron-withdrawing property and quinoidal character are used to make the molecules the red-shifted absorption and NIR emission. In the first chapter, the cores of Dibenzo[f,h]thieno[3,4-b] quinoxaline (DBTQ) and thieno[3,4-b]quinoxaline (TQ) were selected to connect the electron-donating groups for giving D-A-D-configured molecules with NIR absorption. The structure and property relationship has been studied for screening candidate molecules for biomedical applications. Biocompatible polymer wrapped nanoparticles of DTPTTQ, DTPTTTQ, DTPTDBTQ and DTPTTDBTQ were examined for the possibility of photothermal therapy and/or photodynamic therapy. The preliminary results are discussed. In the second chapter, it is divided into two parts. The first part uses thienothiadiazole (TTD) as the core to make a series of fluorescent materials with emissions in NIR region (>700 nm) and superior fluorescent quantum yield. These new molecules were used as emitters in the organic light-emitting diode. In addition, benzobisthiadiazole (BBT), a strong electron-withdrawing core, was connected to water-soluble electron-donating groups. The new molecule exhibits NIR emission and improves its biocompatibility that may thereby promote the multifunctional application in bioimaging. The third chapter is about the design and synthesis of a new phenanthro[9,8-bc:10,1-b’c’]dithiophene (PHDT) core. The rigidity and quinoidal property of the core structure is beneficial for the new fluorescent molecules with NIR emission.