臺灣博碩士論文加值系統

　　近年來隨著有機共軛高分子的蓬勃發展，高分子材料的應用越來越受到研究單位與工業界的重視，尤其是應用於高分子感測器的部分。在本論文中，主要合成了應用在高分子化學感測器的雙吡啶和對苯乙烯之交替共聚物。其雙吡啶單元具有兩個氮原子可和重金屬離子進行配位螯合機制，連接雙吡啶的單鍵因螯合而扭轉進而改變高分子共聚物之結構，接連改變了高分子光學性質，是為利用螢光變化所設計的高分子感測器。待測物如：汞、鉛、鎘、鎳、鋅、銅等重金屬離子，和高分子共聚物感測器之感測單元螯合時，會產生程度不一的螢光強度減弱和吸收波長紅位移。該高分子在溶液狀態和固體狀態下和待測物重金屬之螯合後的光學性質改變和敏銳度有不同的呈現，可更進一步探討其光學性質變化之敏感度，設計成可攜式薄膜元件，用來檢測環境過渡重金屬的存在與否。

The organic conjugated polymer has been rapidly developed in the past decade, and the application of conjugated polymer to the chemosensor has attracted considerable attention. Fluorescence conjugated polymer chemosensors for metal ions sensing which containing bipyridine units and phenylenevinylene moieties were prepared in this thesis. Nitrogen-based ligands such as 2-2’-bipyridine can effectively coordinate a variety of metal ions. The polymer conformation changed due to the coordination with metal ions, and the optical properties present something different subsequently. Addition of heavy metal ions to the fluorescent polymer solution and dipping the polymer films to heavy metal ions solution generated a different extent of fluorescent quenching and absorbance red-shift, and these could be applied to the detection of the presence of transition metal in our environment.

Abstract 1
中文摘要 2
Acknowledgements 3
List of content 4
Chapter 1. Introduction and Aims 6
1.1 Introduction 7
1.2 Introduction to conducting polymers 8
1.2.1 Conducting polymers 8
1.2.2 Charge transport in conjugated polymers 10
1.2.3 Photoluminescence in conjugated polymers 13
1.3 Introduction to chemosensor and its applications 15
1.3.1 Chemosensors 15
1.3.2 Fluorescent conjugated polymer chemosensors [18] 16
1.3.3 The mechanism of analytes detection 17
1.4 Introduction to bipyridyl-containing fluorescence conjugated polymers 18
1.4.1 Bipyridyl-containing conjugated polymers for metal-ion sensing 18
1.4.2 Bipyridyl-phenylenevinylene based polymers 20
1.5 Aims of this project 21
Chapter 2. Results and Discussion 22
2.1. Synthesis and characterization of monomers 23
2.1.1. Synthesis of 5,5’-bis(triphenylphosphonium methyl)-2,2’-bipyridine dibromide 24
2.1.2. Synthesis of 2,5-bis(octyloxy)benzene-1,4-dialdehyde 26
2.1.3. Synthesis of 2,5-Bis(octyloxy)-1,4-bis[(2,5-dioctyloxy-4-formyl) phenylenevinylene]benzene 28
2.2. Synthesis and characterization of polymers 31
2.2.1 Synthesis of alternating polymers 32
2.2.2 Molecular weight and structure characterization 33
2.3. Properties of polymers 39
2.3.1 Thermal properties 39
2.3.2. Optical properties 42
2.4 Responsive properties of polymers on metal ions 49
2.4.1 Polymers in solution state 49
2.4.2 Polymers in solid state 67
Chapter 3. Conclusions 81
Chapter 4 Experimental Section 83
4.1 General Information 84
4.2 Synthesis of monomers 85
4.2.1 Synthesis of 5,5’-bis(bromomethyl)-2,2’-bipyridine (1) 85
4.2.2 Synthesis of 5,5’-bis(triphenylphosphonium methyl)-2,2’bipyridine dibromide (2) 85
4.2.3 Synthesis of 1,4-bis(octyloxy)benzene (3) 86
4.2.4 Synthesis of 1,4-dibromo-2,5-bis(octyloxy)benzene (4) 87
4.2.5 Synthesis of 2,5-bis(octyloxy)benzene-1,4-dialdehyde (5) 87
4.2.6 Synthesis of 1,4-bis(bromomethyl)-2,5-bis(octyloxy)benzene (6) 88
4.2.7 Synthesis of 2,5-dioctyloxy-1,4-xylene-bis(triphenylphosphonium)dibromide (7) 89
4.2.8 Synthesis of 2,5-Bis(octyloxy)-1,4-bis[(2,5-dioctyloxy-4-formyl)phenylenevinylene]benzene (8) 90
4.3 Synthesis of alternating copolymers 91
4.3.1 Synthesis of alternating copolymers (P1a and P1b) 91
4.3.2 Synthesis of alternating copolymers (P2a and P2b) 92
4.3.3 Synthesis of alternating copolymers (P3) 93
Reference 94
Appendix 98

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