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基于异丁烯基双萘酰胺分子骨架构建具有聚集诱导发光性能的荧光和传感材料

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目录

声明

Abstract

摘要

CONTENTS

List of Tales

List of Figures

List of Abbreviations

1 Introduction

1.1 Organic Fluorescent Materials

1.1.1 Basic Principle of Fluorescence in Organic Materials

1.2 Aggregation caused quenching feature (ACQ)

1.3 Aggregation-induced emission feature (AIE)

1.3.1 AIE Working Mechanism

1.3.2 AIE-gen systems

1.3.3 Technological Applications

1.4 Stimuli Responsive Fluorescent Organic Gel

1.4.1 Metal Organic supramolecular Gel

1.4.2 Applications

1.5 Thesis Objectives

2 Development of Tunable Fluorophores via Isobutylene Bis-naphthylamide Cores:As a New AIE-Active Family

2.1 Introduction

2.2 Experimental Section

2.2.1 Material and instruments

2.2.2 Synthesis of fluorophore 1-AB

2.2.3 Synthesis of fluorophore 2-AN

2.2.4 Synthesis of fluorophore 2-AA

2.2.5 AIE experiments

2.3 Results and Discussion

2.3.1 Single crystal analysis and supramolecular interactions

2.3.2 Aggregation induced emission (AIE) property

2.3.3 Theoretical calculations (DFT/TD-DFT)

2.4 Summary

3 Two New Fluorescent Zn2+ Sensors Exhibiting Different Sensing Modes with Subtle Structural Changes

3.1 Introduction

3.2 Experimental Section

3.2.1 Instruments and reagents

3.2.2 Binding constants for receptors HL-1 and HL-2 towards Zn2+

3.2.3 Detection Limit of receptors HL-1 and HL-2 for Zn2+

3.2.4 Synthesis of compound HL-1

3.2.5 Preparation of HL-1-Zn

3.2.6 Synthesis of compound HL-2

3.2.7 Synthesis of compound HL

3.2.8 Preparation of sample solution for analysis

3.3 Results and Discussion

3.3.1 Fluorescence spectroscopic studies of HL-1 and HL-2 in the presence of various metal ions

3.3.2 Absorption spectroscopic studies

3.3.3 Partial 1H NMR of HL-1 and HL-2 with Zn2+

3.3.4 ESI-MS analysis

3.3.5 Signalling mechanisms of Zn2+ ion with HL-2 and HL-1

3.4 Summary

4 Aggregation-Induced Emission (AIE) Fluorophore Exhibits a Highly Ratiometric Fluorescent Response to Zn2+ in vitro and in Human Liver Cancer Cells

4.1 Introduction

4.2 Experimental section

4.2.1 Materials and instrumentation

4.2.2 UV-Vis and fluorescence measurements

4.2.5 Theoretical method (DFT and TD-DFT)

4.2.7 MTT assay

4.2.8 Synthesis of fluorophore 8AQ

4.2.9 Synthesis of compound 8WB

4.3 Results and Discussion

4.3.1 Single crystal structure and supramolecular interactions

4.3.2 Aggregation-induced emission (AIE) behavior of fluorophore 8AQ

4.3.3 Absorption spectroscopic smdies of 8AQ with various metal ions

4.3.4 Fluorescence response of fluorophore 8AQ with various metal ions

4.3.5 1H NMR titration of fluorophore 8AQ with Zn2+ to study the binding mode and composition of metal complex 8AQ-Zn

4.3.6 ESI-MS experiment

4.3.7 Theoretical calculation (DFT/TD-DFT) methods

4.3.8 Signaling mechanism of fluorophore 8AQ with Zn2+

4.3.9 Biological cell-permeability of 8AQ and intracellular ratiometic fluorescence response towards Zn2+

4.3.10 MTT assay

4.4 Summary

5 A Novel Smart Supramolecular Organic Gelator Exhibiting Dual-channel Responsive Sensing Behaviours towards Fluoride ion via Gel-Gel State

5.1 Introduction

5.2 Experimental Section

5.2.1 Materials and reagents

5.2.2 Gelation test

5.2.4 Detection limit of supramolecular metal organic gel OG-Zn for F-

5.2.5 Synthesis of gelator G-16

5.3 Results and Discussion

5.3.2 Fluorescence response of OG towards metal ions

5.3.3 Fluorescence response of OG and OG-Zn towards anions

5.3.4 Self-assembly mechanism in OG and OG-Zn

5.3.5 Stimuli responsive mechanism of OG and OG-Zn towards fluoride ion

5.3.6 Morphological studies of OG,OG-Zn,OG-Zn-F and OG-F

5.3.7 Rheological studies

5.4 Summary

6 Conclusion

Innovation Points and Future Horizons

Innovation Points

References

Published Academic Articles during PhD Period

Supplementary Materials

Acknowledgement

About the Author

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摘要

具有聚集诱导发光性质的荧光材料近年来吸引了广泛的关注,而开发具有高灵敏性和选择性的荧光传感材料也是当前的研究热点。但是将聚集诱导发光性质与荧光传感相结合仍是该领域的一大挑战。本论文在上述研究思路的指导下,设计了一种以异丁烯双萘酰胺为核心的的新型分子骨架,在此基础上构建了一系列具有可调荧光的新型聚集诱导发光材料。进一步通过改变取代基团的性质,设计合成了同时具有聚集诱导发光性质和传感功能的新颖分子体系,全文的研究内容和结果如下:(1)荧光可调的新型聚集诱导发光材料的设计与合成。以异丁烯双萘酰胺为核心骨架,设计合成了具有荧光颜色可调性的新聚集诱导发光分子1-AB,2-AN和2AA。其分子结构通过1 HNMR,13 CNMR,ESI-MS和单晶结构等表征手段得到确认,进而通过荧光光谱,UV-vis光谱,量子产率计算,单晶结构分析和DFT理论计算研究了其发光性质及可能的发光机理。结果表明:通过改变官能团的共轭结构可以调控其荧光性能,而其聚集诱导发光性能是通过限制分子内旋转机理实现的。(2)具有高选择性锌离子传感功能的新型传感分子的设计合成与传感性能研究。在上一章的研究基础上,通过改变荧光基团为金属配位基团,同样以异丁烯双萘酰胺为核心骨架,设计合成了两种新型受体HL-1和HL-2。研究结果表明:两种受体分子由于其结构的微小差异对锌离子显示出不同的传感行为,但都在水溶液中显示出对锌离子优异的选择性。HL-1对Zn2+表现出单一的“turn-on”型传感,而HL-2显示出灵敏的“turn-on”和比率型传感特征.(3)具有聚集诱导荧光增强的高选择锌离子荧光探针的设计合成以及细胞成像研究。为提高锌离子的选择性,本章以喹啉基团代替上一章的吡啶基团,同样以异丁烯双萘酰胺为核心骨架,设计合成了两种新型受体8AQ和8WB。研究结果表明:含有异丁烯单元核心骨架的8AQ对水溶液以及人类肝癌细胞中的锌离子展现出极高的选择性和灵敏度,并伴有优异的聚集诱导发光性能。作为对比,缺乏异丁烯核心骨架的控制分子8WB由于其更柔性的分子结构而没有显示出显著的聚集诱导发光性质和传感功能,进一步证实了我们所选择的核心骨架的重要性(4)具有聚集诱导发光性质与传感功能的刺激-响应型有机超分子凝胶的设计合成与性能研究。为了进一步拓展该核心分子骨架的应用范围,本章,我们通过在骨架中引入具有氢键和范德华力的功能基团,设计合成了一种新型的有机凝胶剂G-16。研究结果表明:该有机凝胶剂分子在DMF中展现出优异的成胶能力,而加入锌离子后原位形成金属有机凝胶,且形成的有机凝胶和金属有机凝胶均对氟离子展现出选择性传感,但具有不同的响应模式。证明该有机小分子凝胶剂具有良好的多重刺激响应功能。

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