功能化有機分子/聚合物/奈米材料之生物辨識或太陽能運用

Functionalizing Organic Molecules/Polymer/Nanomaterials for Bio-recognition or Harnessing Solar Energy

吳以哲(I-Che Wu)

指導教授 ： 周必泰

國立臺灣大學/理學院/化學研究所/博士(2008年)

https://doi.org/10.6342/NTU.2008.10690

摘要

第一章中，我們利用分子辨識的觀念設計合成3,4,5,6-tetrahydrobis-[6-carboxy-
pyrido-[3,2-g]-indolo][2,3-a;3',2'-j]-acridine (TCIA)，使它可以在水溶液中選擇性辨認尿素，同時形成一個六重氫鍵狀態，這個狀態可產生高強度及高靈敏度的熒光信號。
在第二章，我們發現Cu+ 離子在polyalkoxythiophene （ P3MEET ）中能提高P3HT/PCBM系統的太陽能電池效率。相較於一般的P3HT/PCBM系統，約可以增加0.9 %效率。除此之外，也發現系統最佳化的比例為P3MEET/Cu + ： P3HT ： PCBM = 1 : 9 : 6。其中P3MEET/Cu +系統參雜7.5 mol%的CuBr為最好的條件。我們的認為增強電池效率有兩個關鍵作用：第一、P3MEET/Cu +氧化還原電位和P3HT/PCBM系統配對的比較相符，第二、P3MEET/Cu +具有較好的基材表面排列性。
在第三章中，我們合成了皇冠醚、矽粒子和金奈米粒子。利用矽微粒的體積優勢，以矽粒子來合成一組金奈米粒子對，同時我們利用穿透式電子顯微鏡對每一步的產物進行監測，以確定合成需要的產物。同時，也可以很簡單的利用鉀離子形成金奈米粒子對，而不會有嚴重聚集的現象發生。
在第四章，我們將EDOT或BMEET基團運用在小分子太陽能電池合成設計中，發現最後可以在太陽能電池上有顯著的效率提升。採用EDOT分子的LJ1和BMEET分子的LJ4在效能上都有不錯的表現，最高的轉換效率可高達7.3 ％

關鍵字

分子辨識 ； 尿素 ； 太陽能電池 ； 銅離子 ； 皇冠醚 ； 金奈米粒子

並列摘要

In Chapter 1, based on synthesis of 3,4,5,6-tetrahydrobis-[6-carboxypyrido-[3,2-g]-
indolo][2,3-a;3',2'-j]-acridine (TCIA) we convey a generic approach to attain urea recognition via forming a 1:1 TCIA/urea hextuple hydrogen bonded complex in aqueous solution.
Highly sensitive signal transduction is achieved via the ratiometric fluorescence for excited-state proton transfer (TCIA) versus non proton transfer (TCIA/urea complex)
In Chapter 2, we report the Cu+ chelated poly-alkoxythiophene (P3MEET) enhancement of a solar cell device consisting of a P3HT/PCBM heterojunction system. Compared to the reference P3HT/PCBM system, a consistent increase of conversion efficiency of 0.9% via apparent increase of IPCE is achieved upon optimizing the ratio of P3MEET/Cu+ : P3HT : PCBM to 1 : 9 : 6 by weight, in which 7.5 mol% of CuBr is added upon synthesizing P3MEET/Cu+. The results, in combination with relevant data gathered from atomic force microscopy, cyclic voltammetry, and electrochemical impedance spectra, lead us to conclude that the match in redox potential and increase of ordering of the film upon doping P3MEET/Cu+ plays two key roles in enhancing the performance
In Chapter 3, the single 15-crown-5 functionalized Au nanoparticles (NPs) were synthesized with the assistance of silica particles. The use of silica particles renders intrinsic advantages in that each step along the product formation can be monitored by e.g. transmission electron microscope, and the large surface to volume ratio of silica particles leads to a good yield of Au NPs attachment. The as prepared Au NPs, providing access to the fundamental analysis, were readily applied in K+ recognition and proved to be free from aggregation. Accordingly, a sandwich type of complexation is resolved with an association constant of Ka = 32

並列關鍵字

acridine ； urea ； hydrogen bond ； P3HT ； PCBM ； solar cells ； EDOT.

參考文獻

S4. Marzi, E.; Bobbio, C.; Cottet, F.; Schlosser, M. Eur. J. Org. Chem. 2005, 2116-2123.

S8. Gaussian 03, Revision C.02, Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, Jr.; J. A.; Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian, Inc., Wallingford CT, 2004.

S10. Petersson, G. A.; Al-Laham, M. A. J. Chem. Phys. 1991, 94, 6081-6090.

1 F. C. Krebs, H. Spanggaard, Chem. Mater. 2005, 17, 5235.

3 a) W. Ma, C. Yang, X. Gong, K. Lee, A. J. Heeger, Adv. Funct. Mater. 2005, 15, 1617.