在第一章裡，TP-PAA是將具有聚集增強放光(AEE) 特性的四苯基噻吩(TP)發光體，利用原子轉移自由基聚合法(ATRP)與水解反應導入聚丙烯酸(PAA) 的末端位置，用於偵測在不同酸鹼值下所造成AEE螢光物質的放光行為與牛血清蛋白 (BSA) 的檢測。當TP-PAA在中性水溶液下，聚丙烯酸鏈上的羧基具有氫鍵作用力，使得末端位置之發光體TP不易聚集,無法藉由分子間聚集而導致AEE效應不顯著；相對的，TP-PAA在鹼性水溶液下，聚丙烯酸鏈上的羧基被去質子化，而限制住其氫鍵作用力，TP則較容易靠近而導致其具有較強的放光。而因為疏水性作用的關係，使具有水溶性的TP-PAA與牛血清蛋白 (BSA)進行混摻而得到的錯合物，使得TP-PAA有較強的放光行為，可作為生物性螢光探測劑。
在第二章裡，非共平面芳香族發光體可藉由抑制分子內轉動(RIR)進而顯現聚集增強放光(AEE)特性。本研究的TP-PSS系統中，是將具有聚集增強放光(AEE) 特性的四苯基噻吩(TP)發光體，導入聚苯乙烯磺酸鈉(PSS) 的中心位置，利用巨大基團高分子材料以提升限制分子轉動(RIR)作用力，進而探討AEE發光性質。然後我們利用TP-PSS主鏈上的苯乙烯磺酸鈉其具有短程靜電相互作用力與離子(鈣離子)交換的性質，可作為酸鹼與金屬(鈣離子)螢光探測劑。

In chapter 1, tetraphenylthiophenen (TP) with aggregation-emission enhancement (AEE) property is served as terminal fluorophore of poly (acrylic acid) (PAA) based polymer of TP-PAA by atom transfer radical polymerization (ATRP) and hydrolysis reaction to probe the relationship between pH-induced conformation change and the AEE-related emission behavior, and the detection of the bovine serum albumin (BSA) model protein. Intermolecular aggregation of the terminal TP unit in TP-PAA is sterically blocked due to the carboxyl groups of the poly (acrylic acid) were involved in H-bonding, leading to the weak AEE-related fluorescence in the neutral aqueous solution. In contrast, the carboxyl group of the poly (acrylic acid) become deprotonated, leading to a strong electrostatic force limiting the hydrogen bonding and results in the terminal TP units in TP-PAA can easily approach each other to form aggregates with strong the emission intensity in the alkaline aqueous solution; The water-soluble TP-PAA were blended with BSA forming complexes due to hydrophobic interactions shows a sensitive and selective fluorescence enhancement property for protein detection.
In chapter 2, as restricted intramolecular rotation (RIR) is the key leading to the aggregation-enhanced emission (AEE) property. We propose that luminogenic unit connecting polymer chains is particularly clumsy in rotation in considering that the bulky polymer chains are effective in hampering the rotational freedom of the luminogenic unit connecting to them. To test this idea, we synthesized tetraphenylthiophenen (TP) with aggregation-emission enhancement (AEE) property is served as central fluorophores of sodium polystyrene sulfonate (PSS) based polymer of TP-PSS. We used PL spectroscopy to study AEE phenomena for TP-PSS in solution/solid state and solvent/nonsolvent pair, respectively; we can use the sulfonate side groups of TP-PSS characteristics containing short-range interactions and ion exchange to detect pH value and remove calcium to achieve water softing.

Outline of contents
Verification letter from the Oral Examination Committee.............................................i
Chinese Abstract.........................................................................................................…ii
English Abstract...................................................................................……………….iii
Outline of Contents…………………………………………………………………….v
List of Figure………………………………………………………………………..viii
List of Scheme.................................................................................................xi
Chapter 1 Tetraphenylthiophene-functionalized poly (acrylic acid): pH- and bio-sensor with aggregation-induced emission..........................................................1
1.1 Introduction................................................................................................1
1.2 Experimental Sections………………………………….…………………..……5
1.2.1 Materials……………………….…………………………………………….…..5
1.2.2 Syntheses of small molecules and polymers….....................................................6
1.2.3 Instrumentations...................................................................................................9
1.3 Results and discussion..................................................................................10
1.3.1 Synthesis of TP-PAA……………………………………………………….....10
1.3.2 AEE characterizations of TP-PAA………………………………………….....11
1.3.3 CMC of TP-PAA in Water……..……………………………….………………13
1.3.4 pH-Responsive Properties of TP-PAA………………..………………………17
1.3.4.1 The Study by the PL emission spectra of TP-PAA dissolve different pH value in water………………………...................................................................………….18
1.3.4.2 NMR in different pH value…………………...................…………………….19
1.3.4.3 TP-PAA at different pH value impact particle size variation by dynamic Light Scattering (DLS) ..........................………….20
1.3.5 Quantitation of BSA by TP-PAA………………..........………………………21
1.4 Conclusions….....................................................................................................24
1.5 References….....................................................................................................25
SupportingInformation…………….............................................................…………28
Chapter 2 Tetraphenylthiophene-Functionalized sodium polystyrene sulfonate:
pH responsive polymer with Aggregation-Enhanced Emission and Water softening………….....................................................................................…………37
2.1 Introduction................................................................................................37
2.2 Experimental Sections………………………………….…………………..……40
2.2.1 Materials……………………….……………………………………………...40
2.2.2 Instrumentations..................................................................................................41
2.2.3 Syntheses of small molecules and polymers….....................................................42
2.3 Results and discussion..................................................................................44
2.3.1 Synthesis of TP-PSS……………………………………………………….....44
2.3.2 AEE characterizations of TP-PSS………………………………………….....45
2.3.3 CAC of TP-PSS in Water……..……………………………….………………47
2.3.4 pH-Responsive Properties of TP-PSS………………..………………………49
2.3.5 Water softening. ………….............................................................…………52
2.4 Conclusions….....................................................................................................54
2.5 References….....................................................................................................55
SupportingInformation…………….............................................................…………58

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