| 摘要: | 鋅是人體內所有細胞中不可或缺的礦物質，人體內超過兩百種酵素都含有鋅，它們是人體中許多化學反應的催化劑。合成一系列類紫質衍生物─間位苯卟啉分子(m-Benziporphodimethene，BPDM)，做為對鋅離子具高度選擇性的螢光感測分子；當BPDM分子和Zn2+形成配位化合物後，利用長波長的激發，可使鋅錯合物由CHEF (chelation-enhanced fluorescence)效應，放射出長波長的螢光。本研究以高效能共軛焦顯微鏡(confocal microscope)進行間位苯卟啉鋅錯合物在HeLa細胞內染色和間位苯卟啉分子對HeLa細胞內鋅離子的感測觀察；另外，藉由MTT細胞活性染色法(MTT assay)配合ELISA reader測量24小時中極性非質子溶劑DMSO和BPDM-COOH分子對HeLa細胞株毒性測試，也以etoposide為誘導分子利用BPDM-COOH分子進行凋亡細胞的感測實驗。 在本論文第二章中，合成含四氮四硫的紫質大環化合物[38]octaphyrin(1,1,1,1,1,1,1,1)，並以一維1H NMR及二維1H−1H COSY、1H−13C HSQC、1H−13C HMBC NMR光譜以及單晶X-ray結構進行鑑定；並且利用變溫1H NMR光譜研究溫度對分子結構及環電流的影響。另外，藉由UV-Vis光譜和1H NMR光譜可知以過氯酸(HClO4)進行質子化反應造成[38]N4S4-octaphyrin構型的變化及芳香性提高。 Zinc is an essential metal ion in biology system. Over two hundred enzymes contain zinc in their active site in human body. They play important roles in bio-relate catalytic reactions. In this thesis, we demonstrate a new porphyrin analogue, m-benziporphodimethene (BPDM), as a highly selective fluorescence sensor for zinc ion. When zinc(2+) coordinated with BPDM to form a stable metal complex, the excitation by long wavelength light emits long wavelength fluorescence through chelation-enchanced fluorescence effect. To confirm the penetration of compounds into cells, we treat BPDM-Zn into medium of HeLa cell before incubation and detect the fluorescence by a high performance confocal microscope. In addition, we study the 24 hours cell toxicity of DMSO and BPDM-COOH in HeLa cell measured by MTT assay and ELISA reader. Finally, we also utilized BPDM-COOH as a sensor to trace the apoptotic process in HeLa cell. In the second chapter, we successfully synthesize a heteroatom substituted expanded porphyrin, [38]octaphyrin(1,1,1,1,1,1,1,1), embeding four nitrogen atoms and four sulfur atoms in the central core, which confirmed by one dimension 1H NMR, two dimensions 1H−1H COSY, 1H−13C HSQC, 1H−13C HMBC NMR spectra and single crystal structure. Interestingly, variable temperature 1H NMR experiment demonstrated a temperature dependent molecular structure ring current changes. Additionally, protonation by HClO4 also affects the structure and aromaticity of [38]N4S4-octaphyrin according to UV-vis and 1H−NMR spectroscopic data. |
