在這個研究中，TP1PBLG及TP2PBLG是將具有聚集誘導放光增強 (AIEE)的四苯基噻吩(TP) 發光體，利用開環聚合反應(ROP)各別導入聚(γ-谷胺酸芐酯) (PBLG)的末端以及中心位置，用於偵測聚蛋白質的二級結構(α-螺旋)與AIEE螢光物質之間的關係。在TP2PBLG的系統中，在中心位置之發光體TP因受兩側較大的α-螺旋PBLG分子鏈阻隔，TP無法藉由分子間聚集而導致AIEE效應不顯著且發光效率降低。進而我們更合成了一系列TP發光體在PBLG末端的TP1PBLG與TP2PBLG做對照。在TP1PBLG系統中，末端的TP在分子鏈聚集時較容易靠近而導致其具有較強的放光。在此研究中，藉由調控PBLG之α-螺旋的比例(使用不同溶劑進行退火)進而改變其發光強度。TP1PBLG及TP2PBLG之構型我們藉由傅立葉紅外光譜、廣角X光繞射以及小角X光散射等光譜測得並得到其對AIEE發光行為的影響。

In this study, tetraphenylthiophenen (TP) with aggregation-induced emission enhancement (AIEE) property is served as terminal and central fluorophores of poly(γ-benzyl-L-glutamate) (PBLG)-based polymers of TP1PBLG and TP2PBLG, respectively, to probe for the relationship between the secondary structure (α-helix) of polypeptides and the ALEE-operative fluorescence (FL). Intermolecular aggregation of the central TP unit in the di-substituted TP2PBLG is sterically blocked by the large α-helical PBLG chains, which lead to the reduced AIEE-oriented FL. On the contrast, the terminal TP units in TP1PBLG can easily approach each other to form aggregates with strong FL. Factor (e.g. solvent annealing) controlling the fraction of α-helix chain also varies the corresponding emission intensity. Conformational difference between TP1PBLG and TP2PBLG evaluated from the infrared and the X-ray (wide- and small-angle) diffraction spectra is also used to verify its influence on the AIEE-operative FL behavior.

Outline of Contents..........................................................i
List of Chart....................................................................iii
List of Figure..................................................................iv
List of Scheme................................................................vi
List of Table...................................................................vii
English Abstract............................................................viii
Chinese Abstract............................................................ix
Chapter 1 Background....................................................1
Chapter 2 Experimental Sections....................................6
2-1 Materials...................................................................6
2-2 Instrumentations.....................................................10
Chapter 3 Results and discussion.................................12
3-1 Synthesis ofTP-2PBLG...........................................12
3-2 Solution PL emission study.....................................16
3-3 Study of cooling PL on TP-2PBLG solution.............23
3-4 Secondary structure in relation to the AIEE-effect in the solid state................................................................24
3-5 Comparison between TP1PBLG(n)s and TP2PBLG......................................................................37
Chapter 4 Conclusions..................................................38
Chapter 5 Reference and Notes...................................41
Supporting Information..................................................44

1 (a) Y. Bae, S. Fukushima, A. Harada and K. Kataoka, Angew. Chem. Int. Ed., 2003, 42, 4640–4643; (b) H. A. Klok and S. Lecommandoux, Adv. Mater., 2001, 13, 1217–1229; (c) H. Tang and D. Zhang, J. Polym. Sci., Polym. Chem., 2010, 48, 2340–2350; (d) G. J. M. Habraken, C. E. Koning and A. Heise, J. Polym. Sci., Polym. Chem., 2009, 47, 6883–6893; (e) P.J. Flory, Proc. R. Soc. London. Ser. A, 1956, 234, 73–89; (f) C. Robinson and J. C. Ward, Nature, 1957, 180, 1183–1184; (g) S. M. Yu, V. P. Conticello, G. Zhang, C. Kayser, M. J. Fournier, T. L. Mason and D. A. Tirrell, Nature, 1997, 389, 167–170; (h) K. Tohyama and W. G. Miller, Nature, 1981, 289, 813–814; (i) S. W. Kuo, H. F. Lee and F. C. Chang, J. Polym. Sci., Polym. Chem., 2008, 46, 3108–3119; (j) A. Gitsas, G. Floudas, M. Mondeshki, H. W. Spiess, T. Aliferis, H. Iatrou and N. Hadjichristidis, Macromolecules , 2008, 41, 8072–8080.
2 (a) T. Torii, T. Yamashita and K. Horie, Eur. Polym. J., 1993, 29, 1265-1270; (b) P. Doty, J. H. Bradbury and A. M. Holtzer, J. Am. Chem. Soc., 1956, 78, 947-954; (c) F. A. Bovey and G. V. D. Tiers, Adv. Polym. Sci., 1963, 3, 139-195; (d) R. H. Wieringa, E. A. Siesling, P. J. Werkman, H. J. Angerman, E. J. Vorenkamp, and A. J. Schouten, Langmuir 2001, 17, 6485 - 6490; (e) A. J. Wada, J. Polym. Sci., 1960, 45, 145-153; (f) M. Gregson, G. P. Jones and M. Davies, Chem. Phys. Lett., 1970, 6, 215-216 ; (g) A. K. Gupta, C. Dufour and E. Marchal, Biopolymers, 1974, 13, 1293-1308 ; (h) V. Pokorná, D. Výprachtický and J. Pecka, Macromol. Biosci., 2001, 1, 185–190; (i) K. T. Kim, C. Park, G. W. M. Vandermeulen, D. A. Rider, C. Kim, M. A. Winnik and I. Manners, Angew. Chem., 2005, 117, 8178 –8182; (j) L. Rubatat, X. Kong, S. A. Jenekhe, J. Ruokolainen, M. Hojeij and R. Mezzenga, Macromolecules, 2008, 41, 1846-1852; (k) P. Papadopoulous, G. Floudas, H. A. Klok, I. Schnell and T. Pakula, Biomacromolecules, 2004, 5, 81–91; (l) Y. C. Lin and S. W. Kuo J. Polym. Sci. Part A: polym. Chem., 2011, 49, 2127-2137; (n) A. Sanchez-Ferrer and R. Mezzenga, Macromolecules, 2010, 43, 1093-1100; (n) J. Lin, N. Liu, J. Chen and D. Zhou, polymer, 2000, 41, 6189-6194; (o) D. Voet and J. G. Voet, Biochemistry, Hoboken, NJ: Wiley, 2004; p 227.
3 (a) J. Z. Xie, J. W. Y. Lam, L. Cheng, H. Chen, C. Qiu, H. S. Kwok, X. Zhan, Y. Liu, D. Zhu and B. Z. Tang, Chem. Commun., 2001, 1740–1741; (b) C. X. Yuan, X. T. Tao, L. Wang, J. X. Yang and M. H. Jiang, J. Phys. Chem. C, 2009, 113, 6809–6814; (c) Z. Yang, Z. Chi, T. Yu, X. Zhang, M. Chen, B. Xu, S. Liu, Y. Zhang and J. Xu, J. Mater. Chem., 2009, 19, 5541–5546; (d) W. Z. Yuan, P. Lu, S. Chen, J. W. Y. Lam, Z. Wang, Y. Liu, H. S. Kwok, Y. Ma and B. Z. Tang, Adv. Mater., 2010, 22, 1–5; (e) B. Xu, Z. Chi, Z. Yang, J. Chen, S. Deng, H. Li, X. Li, Y. Zhang, N. Xu and J. Xu, J. Mater. Chem., 2010, 20, 4135–4141; (f) Z. Zhao, S. Chen, J. W. Y. Lam, P. Lu, Y. Zhong, K. S. Wong, H. S. Kwok and B. Z. Tang, Chem. Commun., 2010, 46, 2221–2223; (g) J. Liu, J. W. Y. Lam and B. Z. Tang, J. Inorg. Organomet. Polym., 2009, 19, 249–285; (h) J. Liu, Y. Zhong, J. W. Y. Lam, P. Lu, Y. Hong, Y. Yu, Y. Yue, M. Faisal, H. H. Y. Sung, I. D. Williams, K. S. Wong and B. Z. Tang, B. Z. Macromolecules, 2010, 43, 4921–4936; (i) R. H. Chien, C. T. Lai and J. L. Hong, J. Phys. Chem. C, 2011, 115, 5958–5965; (j) C. T. Lai and J. L. Hong, J. Phys. Chem. B, 2010, 114, 10302–10310; (k) C. T. Lai, R. H. Chien, S. W. Kuo and J. L. Hong, Macromolecules 2011, 44, 6546-6556. (l) R. H. Chien, C. T. Lai and J. L. Hong, Macrom. Chem. Phys. 2012, 213, 666-677.
4 W. H. Daly and D. Poche, Tetrahedron Lett. 1988, 29, 5859–5862.