在這篇文章中，將具有聚集誘導發光增強 (AIEE) 特性的螢光發光物質¬-四苯基噻吩 (TP) 離子單元，以離子鍵和親水性的聚(N-異丙基丙烯醯胺)-PNIPAM 形成鍵結之後，形成多重感測的微胞系統。金屬離子、酸和鹼對離子鍵 (氨基-磺酸根)的影響，引發AIEE的螢光發光體在螢光上有所改變。為了行使我們的想法，先將尾端帶有磺酸根的PNIPAM和具有氨基的TP衍生物鍵結，產生高分子綜合體 (TP-PNIPAM)。在水裡面時，TP-PNIPAM中，TP的疏水性在中心產生聚集，親水性的PNIPAM在外圍並且以離子鍵鍵結的方式形成微胞。微胞中心的AIEE物質，因為聚集，有螢光的顯現，但是一旦加入金屬離子、酸和鹼，離子鍵被破壞，導致微胞瓦解，造成螢光抑制。因此，多重感測的螢光偵測器就此產生。
由親水端的聚(N-異丙基丙烯醯胺)-PNIPAM和疏水端的四苯基噻吩 (TP) 組成的兩性微胞系統具有聚集誘導發光增強 (AIEE) 的螢光特性，在此研究中，離子鍵鍵結的聚合物利用螢光回應來探討臨界微胞濃度和低臨界溶解溫度。為了行使我們的想法，各別將具有氨基的TP衍生物和尾端帶有磺酸根的PNIPAM混合，產生兩性的高分子錯合物 (TP-PNIPAM)，有著不同的疏水TP和親水PNIPAM比 (x/y)。當在水裡面，TP-PNIPAMs會形成有著聚集的TP中心、PNIPAM包圍的微胞，因為TP聚集誘導發光增強的螢光特性，使得有強的螢光強度呈現。藉由調控疏水TP和親水PNIPAM的比例，可以改變臨界微胞濃度和低臨界溶解溫度，並且可以利用螢光回應來偵測此轉變。

In this article, a multiple-responsive polymer micelles system was constructed by using ionic bond to link the hydrophobic tetraphenylthiophene (TP) fluorophores, which possess the property of aggregation-induced emission enhancement (AIEE), with the hydrophilic poly(N-isopropyl acrylamide) (PNIPAM). The susceptibility of the ionic ammonium-sulfonate (Am-Sul) bonds towards metal ions, acid and base triggered the AIEE-operative fluorescence (FL) response. To exercise the idea, PNIPAM with sulfonate terminal was primarily prepared to react with TP-derivatives functionalized with ammonium groups to generate polymer complex of TP-PNIPAM. When in water, the polymer complex TP-PNIPAM formed micelles with the aggregated TP core interconnecting the hydrophilic PNIPAM shell by the ionic Am-Sul bonds. With the operative AIEE effect, the aggregated TP core of the micelles fluoresced but upon the additions of metal ions, acid and base, the ionic bonds dissociated to result in the collapse of the micelles and the FL quenching. A novel fluorogenic sensor capable to respond to multi-stimuli was therefore constructed.
Amphiphilic micelle systems with the hydrophilic poly(N-isopropyl amide) (PNIPAM) shell and the hydrophobic tetraphenylthiophene (TP), which has the novel aggregation-induced emission enhancement (AIEE) feature, core inter-connected by ionic bonds were prepared in this study to explore the AIEE-operative emission response towards critical micelle concentration (CMC) and lower critical solution temperature (LCST). To exercise the idea, TP functionalized ammonium cations and PNIPAM with terminal sulfonate group were individually prepared and mixed together to yield three amphiphilic TP-PNIPAM complexes with different hydrophobic TP to the hydrophilic PNIPAM (x/y) ratios. When in aqueous solution, TP-PNIPAMs form micelles with the aggregated TP core, which emits strongly due to the operative AIEE effect, encompassed by the PNIPAM shell. The resultant CMC and LCST of the TP-PNIPAM micelles can be varied by changing the hydrophobic to the hydrophilic x/y ratio and can be monitored by the AIEE-dominant fluorescence responses towards concentration and temperature variables.

OUTLINES OF CONTENTS
OUTLINES OF CONTENTS………………………………………….…………………i
LIST OF SCHEME……………...………………………………………….…………..iv
LIST OF FIGURE………………………………………………………………............v
LIST OF TABLE…………………………………………………………………..........ix
Abstract-1 (in Chinese)..……………………..…………………………………………..x
Abstract-1 (in English)..……………………..……………………………………….....xi
Abstract-2 (in Chinese)..……………………..…………………………………….......xii
Abstract-2 (in English)..……………………..…………………………………...…....xiii

Chapter 1 Aggregation-Induced Emission Enhancement, Fluorescence Responses
toward Acid, Base and Metal Ions………………………………….........1
1.1 Introduction……..……….………………………………………………....……......1
1.2 Experimental Sections........………………………………………..…………….......5
1.2.1 Materials........………………………………………..………………..…………...5
1.2.2 Instrumentation…….......………………………………………..………..……......6
1.2.3 Syntheses of small molecules and polymer…………………………………….….6
1.3 Results and Discussion...…………...………………………………………..…......12
1.3.1 Synthesis…………….…………...…………………………………….…..…......12
1.3.2 AIEE characterizations on the model compound TP2NH3+ and the polymer complex TP-PNIPAM…………...…………………………………………..…..……...14
1.3.3 TP-PNIPAM as fluorogenic metal-ion sensor……………………………..……..17
1.3.4 PH-driven emission variations………………………………………...…..……..20
1.4 Conclusions…………….………………………….…………………………….....23
1.5 References…………..…….……………………...…………….………………......24
Chapter 2 Critical Micelle Concentration (CMC) and Lower Critical Solution
Temperature (LCST)………………………………………………….…..28
2.1 Introduction….…..………………………………………………………....……....28
2.2 Experimental Sections.........………………………………………..……………....34
2.2.1 Syntheses of polymer.......………………………………………..…………….…34
2.2.2 Preparation of TP-PNIPAM complexes………...………………..……………….34
2.2.3 Instrumentation………...………………………………………..……….……….36
2.3 Results and Discussion..…………...…………………………………….............…37
2.3.1 Primary characterizations on TP-PNIPAM……………………………............…37
2.3.2 AIEE property of TP-PNIPAM…..……………………………………...........….40
2.3.3 CMC of TP-PNIPAMs in aqueous solution…...………………………..........…..44
2.3.4 LCST of TP-PNIPAMs..…...…………………………………….....….…......….49
2.4 Conclusions…………….………………………….……………………………….56
2.5 References..……….…….……………………...………………………………..…57
Supporting Information...…………………………...……………………………..…...60

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