紫質衍生物之鋅離子感測劑暨大環紫質染料敏化太陽能電池之合成研究
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2014
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鋅是人體內細胞中不可或缺的礦物質，已知的含鋅的酵素超過300多種，鋅穩定酶蛋白質的立體結構，或位於催化中心，他們是人體中許多化學反應的催化劑，因此，開發一鋅離子感測分子是極為重要的。本實驗室於 2009年發表第一個於實驗室中發展的類紫質衍生物m-benziporphodimethene，簡稱 BPDM，在之後的研究顯示，三吡咯環酮類(tripyrrinone)有潛力成為新一代廣用的螢光感測分子。本研究合成出兩個新的tripyrrinone衍生物作為螢光鋅離子感測分子，將三吡咯環酮類之環上末端α碳原子苯醯基化得到兩個新的tripyrrinone衍生物14-mesitoyl-5,10-dimesityl-1-oxo-tripyrrinato(L1)和14-benzoyl-5,10-diphenyl-1-oxo-tripyrrinato(L2)，而將此兩化合物與鋅離子及各種金屬離子做選擇性的研究，可知化合物L2之鋅錯合物螢光強度優於化合物L1，故在偵測鋅離子時，可使用較低的濃度。比較化合物L1、L2與已發表的BPDM，鋅錯合物L1的吸收波長為594nm而鋅錯合物L2的吸收波長為608nm，相較於BPDM之吸收波長600nm，皆位於近紅外光的範圍。鋅錯合物L1的放射波長為659nm而鋅錯合物L2的放射波長為680nm，與BPDM之放射波長672nm做比較，鋅錯合物L2的放射波長在更長波長的位置，綜合比較得知，化合物L1及化合物L2在偵測鋅離子時有低能量的吸收及放射波長，顯示本研究化合物L1及化合物L2皆為優秀的近紅外光鋅離子感測分子。
在第二章的部份，本論文以合成22π電子的大環紫質pentaphyrin和sapphyrin作為合成目標。以[3+2]的合成策略，在適當路易士酸催化下將tripyrromethane和dipyrromethane組合成目標產物。將tripyrromethane(3)和dipyrromethane(15)合成，純化後可得pentaphyrin(16)，其UV-Vis吸收光譜在356、 421、 513 nm，經過高解析ESI-MS鑑定可在m/z = 839.3744找到與化合物(16)相符的碎裂峰，其產率為1.33%；將tripyrromethane(8)和dipyrromethane(14)合成，純化後可得pentaphyrin(19)，其UV-Vis吸收光譜在351、 424、 515 nm，經過高解析ESI-MS鑑定可在m/z = 971.3445找到與化合物(19)相符的碎裂峰；將tripyrromethane(8)和dipyrromethane(15)合成，其粗產物經過ESI-MS鑑定可在m/z = 927.3找到與pentaphyrin(17)相符的碎裂峰；將tripyrromethane(9)和dipyrromethane(15)合成，其粗產物經過ESI-MS鑑定可在m/z = 895.7找到與pentaphyrin (18)相符的碎裂峰；將tripyrromethane(9)和dipyrromethane(14)合成，純化後可得pentaphyrin(20)，經過高解析ESI-MS鑑定可在m/z = 939.4274找到與化合物(20)相符的碎裂峰。同樣地，以[3+2]的合成策略在適當路易士酸催化下將tripyrromethane(8)、p-tolyaldehyde和2,2’-bipyrrole組合成目標產物，其粗產物經過ESI-MS鑑定可在m/z = 825.1找到與sapphyrin(21)相符的碎裂峰。
Zinc is an essential metal ion in biology system. Over three hundred enzymes contain zinc in human body. Zinc locates in the catalytic center and stabilizes metalloenzymes. They play important roles in bio-relate catalytic reactions. Therefore, the development of a zinc sensing molecule is extremely important. In 2009, our lab published the first porphyrin derivative as zinc sensing molecule, m-benziporphodimethene (BPDM). The later study shows that tripyrrinone would be a new generation of effective zinc sensing molecules and even has potential to be developed into a new series of dye with diverse functionalities and applications. In this study, we synthesized two new types of tripyrrinone derivatives as zinc sensing molecules. By adding a acyl substitution to the end of the carbon atom in tripyrrinone ring, we obtained two new tripyrrinone derivatives 14-mesitoyl-5,10-dimesityl-1-oxo-tripyrrinato(L1)and 14-benzoyl-5,10-diphenyl-1-oxo-tripyrrinato(L2). Through studying the selectivity of metal ions in these two compounds, we observed that the fluorescence of compound L1 with zinc complex is stronger than compound L2. Thus, we can use lower concentrations of compound L1 than compound L2 to detect zinc molecules. Comparing compound L1 and L2 with known BPDM, complex L1 has absorption wavelength at 594 nm and the absorption wavelength of complex L2 is at 608 nm, while the absorption wavelength of BPDM is at 600 nm. The emission wavelength of compound L1 is 659 and of compound L2 is 680 nm. Compared with BPDM, we found compound L2 has the longer emission wavelength. In conclusion, because compound L1 and L2 have lower energy to detect the zinc molecules, we can say they are good near infrared zinc sensing dyes. In the second chapter, we chose 22πelectrons expanded porphyrins, pentaphyrin and sapphyrin, as synthetic targets. We used strategy of ”3+2” to synthesize pentaphyrin by adding Lewis acid catalyst tripyrromethane and dipyrromethane. Mixing of tripyrromethane(3) and dipyrromethane(15), we obtained pentaphyrin (16) after purifications. The absorption of compound 16 is at 356, 421, and 513 nm, and we observed a match molecular mass peak in high resolution ESI-MS spectrum. When combined with tripyrromethane(8) and dipyrromethane(14), we obtained pentaphyrin (19) after purifications. The absorption of compound 19 is at 351, 424, and 515 nm, and we observed an expected mass peak in high resolution ESI-MS spectrum. We combined tripyrromethane(8) and dipyrromethane(15) to get pentaphyrin(17), we observed an expected mass in ESI-MS spectrum with crude compound. The reaction of tripyrromethane(9) and dipyrromethane(15) obtained pentaphyrin(18), confirmed by a mass peak in ESI-MS spectrum in crude compound. Finally, the reaction of tripyrromethane(9) and dipyrromethane(14) obtained pentaphyrin(20), confirmed by a mass peak in ESI-MS spectrum after purifications. In the other side, we also use strategy of ”3+2” to synthesize sapphyrin. Under appropriate Lewis acid catalysis, the condensation reaction of tripyrromethane(8), aldehyde, and 2,2’-bipyrrole gave sapphyrin(21). These compounds provided important precursors for the preparation of new expanded porphyrin based DSSC dyes with NIR absorption properties.
Zinc is an essential metal ion in biology system. Over three hundred enzymes contain zinc in human body. Zinc locates in the catalytic center and stabilizes metalloenzymes. They play important roles in bio-relate catalytic reactions. Therefore, the development of a zinc sensing molecule is extremely important. In 2009, our lab published the first porphyrin derivative as zinc sensing molecule, m-benziporphodimethene (BPDM). The later study shows that tripyrrinone would be a new generation of effective zinc sensing molecules and even has potential to be developed into a new series of dye with diverse functionalities and applications. In this study, we synthesized two new types of tripyrrinone derivatives as zinc sensing molecules. By adding a acyl substitution to the end of the carbon atom in tripyrrinone ring, we obtained two new tripyrrinone derivatives 14-mesitoyl-5,10-dimesityl-1-oxo-tripyrrinato(L1)and 14-benzoyl-5,10-diphenyl-1-oxo-tripyrrinato(L2). Through studying the selectivity of metal ions in these two compounds, we observed that the fluorescence of compound L1 with zinc complex is stronger than compound L2. Thus, we can use lower concentrations of compound L1 than compound L2 to detect zinc molecules. Comparing compound L1 and L2 with known BPDM, complex L1 has absorption wavelength at 594 nm and the absorption wavelength of complex L2 is at 608 nm, while the absorption wavelength of BPDM is at 600 nm. The emission wavelength of compound L1 is 659 and of compound L2 is 680 nm. Compared with BPDM, we found compound L2 has the longer emission wavelength. In conclusion, because compound L1 and L2 have lower energy to detect the zinc molecules, we can say they are good near infrared zinc sensing dyes. In the second chapter, we chose 22πelectrons expanded porphyrins, pentaphyrin and sapphyrin, as synthetic targets. We used strategy of ”3+2” to synthesize pentaphyrin by adding Lewis acid catalyst tripyrromethane and dipyrromethane. Mixing of tripyrromethane(3) and dipyrromethane(15), we obtained pentaphyrin (16) after purifications. The absorption of compound 16 is at 356, 421, and 513 nm, and we observed a match molecular mass peak in high resolution ESI-MS spectrum. When combined with tripyrromethane(8) and dipyrromethane(14), we obtained pentaphyrin (19) after purifications. The absorption of compound 19 is at 351, 424, and 515 nm, and we observed an expected mass peak in high resolution ESI-MS spectrum. We combined tripyrromethane(8) and dipyrromethane(15) to get pentaphyrin(17), we observed an expected mass in ESI-MS spectrum with crude compound. The reaction of tripyrromethane(9) and dipyrromethane(15) obtained pentaphyrin(18), confirmed by a mass peak in ESI-MS spectrum in crude compound. Finally, the reaction of tripyrromethane(9) and dipyrromethane(14) obtained pentaphyrin(20), confirmed by a mass peak in ESI-MS spectrum after purifications. In the other side, we also use strategy of ”3+2” to synthesize sapphyrin. Under appropriate Lewis acid catalysis, the condensation reaction of tripyrromethane(8), aldehyde, and 2,2’-bipyrrole gave sapphyrin(21). These compounds provided important precursors for the preparation of new expanded porphyrin based DSSC dyes with NIR absorption properties.
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紫質, 螢光, 感測劑, 大環紫質, 太陽能染料, porphyrin, fluorescence, sensor, expanded-porphyrin, dye