Synthesis and Characterization of Silole Derivatives and Application as Chemosensors for the Detection of Chemical Explosives
- Issued Date
- 2023
- Abstract
- 니트로방향족 화합물(NAC)의 검출은 우리의 환경, 국가 안보 및 인간 건강에 매우 바람직합니다. 공액 형광 고분자는 형광 소광, 비색 감지, 실시간 감지 등 다양한 방법으로 NAC를 감지하는 데 매우 중요한 역할을 합니다. Silole은 silole 코어의 Si 원자와 부타디엔 부분 사이의 σ*-π* 접합으로 인해 헤테로시클로펜타디엔의 다른 모든 5원 고리 중에서 독특하고 특이한 광학 특성을 가지고 있습니다. 이 접합은 silole의 낮은 위치에 있는 LUMO를 발생시키고 전자 친화력을 증가시킵니다. 합성 과정, 분광 특성화에 대한 세부 사항 및 메카노크로믹, 솔브토크로믹, 압전크로믹과 같은 고유한 광물리 특성에 대해 설명하고 다양한 유형의 감지 방법도 보고되었습니다. 합성된 사일로는 열중량 분석(TGA)에 의해 확인된 고온에서 높은 열적 안정성을 보였다. silole core의 1,1-position에서 σ-π*, 2,5-position에서 π-π*, σ-σ*, σ-π*를 통해 이량체 및 고분자와 같은 결합 화합물. 우리는 그들의 광물리학적 특성을 조사했으며 THF/물 혼합물에서 방출 강도를 증가시켜 독특한 응집 유도 방출(AIE) 특성을 나타냅니다. 또한, 우리는 silole 유도체에 의한 폭발물 감지에 대한 우수한 감도를 관찰했습니다. 폭발물을 첨가할 때 광발광(PL) 강도의 소광 동안 높은 Stern-Volmer 상수가 관찰되었습니다. 또한 실제 적용을 위해 형광 회복 과정에 의한 실시간 센싱을 조사한 결과 NACS를 통해 2,5-페닐 치환 실롤 폴리머가 큰 반응을 보였다. 또한, 우리는 또한 비색 및 종이 스트립 조사를 조사했으며 폴리머는 NAC 검출을 위한 고체 상태의 유망한 후보가 될 수 있음을 보여줍니다.|Detection of nitroaromatic compounds (NACs) are highly desirable for our environment, national security, and human health. Conjugated fluorescent polymers play very important role for detecting NACs by various way such as fluorescence quenching, colorimetric sensing, real-time sensing and so on. Silole has unique and unusual optical properties among all others five-membered ring of heterocyclopentadienes, due to the σ*-π* conjugation between Si atom of silole core and butadiene moieties. This conjugation gives rises to the low-lying LUMO of silole and increases its electron affinity. Herein, a series of conjugated silole derivatives were successfully synthesized. The synthetic process, details of spectroscopic characterizations and some of unique photophysical property such as mehcanocromic, solvetocromic, pieozocromic will be address, and various type of sensing methods were also reported. Synthesized siloles showed high thermal stability at high temperature confirmed by thermogravimetric analysis (TGA). The obtained compounds such as dimer and polymers are conjugated through σ-σ*, and σ-π* in 1,1-position and π-π* in 2,5-position of silole core. We have investigated their photophysical properties and they exhibit unique aggregation-induced emission (AIE) properties by increasing the emission intensity in THF/water mixtures. Furthermore, we observed excellent sensitivity for sensing explosives by silole derivatives. High Stern-Volmer constant was observed during quenching of photoluminescence (PL) intensity upon adding explosives. In addition, for the practical application, we investigated the real-time sensing by fluorescence recovery process and 2,5-phenyl substituted silole polymer showed great respond through NACS. Moreover, we also examined the colorometric and paper strips investigation and the polymers reveal that it may be a promising candidate in solid state for NACs detection
- Alternative Title
- 실올 유도체의 합성과 특성 분석 및 폭발물 탐지를 위한 화학센서로의 응용
- Alternative Author(s)
- 앰디하산을 하퀴
- Affiliation
- 조선대학교 일반대학원
- Department
- 일반대학원 화학과
- Advisor
- 손홍래
- Awarded Date
- 2023-02
- Table Of Contents
- I. CHAPTER 1 - INTRODUCTION 1
Background 1
1.1 Silole 2
1.2 Conjugated Silole 3
1.3 Optical Properties of Conjugated Silole 5
1.4 Application of Conjugated Silole 6
1.4.1 Introduction of silole as Chemosensors 6
1.4.2 Sensing Mechanism 7
II. CHAPTER 2 9
Comparison of Aggregation-Induced Emission Enhancement Effect between π-σ* and σ-σ*Conjugation on Silole and Application in Explosives Detection 9
1. Introduction 10
2. Results and discussion 12
2.1. Synthesis and Characterization 12
2.2. Photophysical Properties. 14
2.3. Theoretical calculations and analysis. 16
2.4. AIEE properties of bissilole-benzene and bissilole 18
2.5. Detection of nitro-explosives in aqueous solution 22
3. Conclusion 27
III. CHAPTER 3 28
Detection of TNT Vapors by Real-time fluorescence Quenching with New Fluorescent Conjugated Silole Polymers 28
1. Introduction 29
2. Results and discussion 32
2.1. Synthesis and Mechanism 32
2.2. AIE and ICT properties. 36
2.3. Solvatocromic effect of Polymers. 41
2.4. Fluorescence Quenching and Recovery Cycles at Real-time sensing 45
2.5. Detection of nitro-explosives in aqueous solution and Aggregate states 47
2.6. Studies of Electron transfer Quenching 51
2.7. XRD Analysis 53
2.8. Thermal Properties 54
3. Conclusion 55
IV. CHAPTER 4 56
AIE-active Conjugated Polyphenylsilole for Higher Sensitivity of Explosives Detection 56
1. Introduction 57
2. Results and discussion 59
2.1. AIE Properties 62
2.2. Sensing Mechanism of Nitro-explosives 65
2.3. Detection of Nitro-explosives in Aqueous Solution 66
3. Conclusion 71
V. CHAPTER 5 72
Dual Mode Colorimetric and Fluorescent Sensing of TNT by Conjugated Fluorenone-Substituted 2,5-Silole Polymer 72
1. Introduction 73
2. Results and discussion 75
2.1. Synthesis and Characterization 75
2.2. Vapochromic Behavior in Solvent and Detection of TNT 78
2.3. Theoretical calculations and analysis 80
2.4. Photophysical properties. 81
2.5. Physical Property properties. 85
3. Conclusion 87
VII. CHAPTER 6 88
Experimental section 88
6.1. Measurements and Instruments 88
6.2. Synthesis of materials 89
6.2.1. Synthesis of 1,4-bis(1-methyl-2,3,4,5-tetraphenyl-1-silacyclopentadien), bissilole 89
6.2.2. Synthesis of 1,4-bis(1-methyl-2,3,4,5-tetraphenyl-1-silacyclopentadienyl) benzene, bissilole-benzene 90
6.2.3 Synthesis of bis(phenylethynyl)dibutylsilane 90
6.2.4. Synthesis of 1,4-diioodo-2,5-bis(octyloxy)benzene 91
6.2.5. Synthesis of Polymer 1&2 (Chapter-3) 91
6.2.6. Synthesis of Dimethyl bis(phenylethynyl) Silane 92
6.2.7. Synthesis of Hyperbranched Polymer 92
6.2.8. Synthesis 2,7-Dibromo-9-fluorenone 93
6.2.9. Synthesis of Polymer 1 (Chapter-5) 93
6.3. Experimental Spectra. 95
6.3.1. NMR Spectra 95
6.3.2. High-resolution Mass Spectroscopy (HRMS). 98
6.3.3. Gel Permutation Chromatography (GPC) 102
VI. CHAPTER 7 106
Conclusion of Study 106
References 108
Appendices 122
- Degree
- Doctor
- Publisher
- 조선대학교 대학원
- Citation
- Md Hasanul Haque. (2023). Synthesis and Characterization of Silole Derivatives and Application as Chemosensors for the Detection of Chemical Explosives.
- Type
- Dissertation
- URI
- https://oak.chosun.ac.kr/handle/2020.oak/17547
http://chosun.dcollection.net/common/orgView/200000656539
- Appears in Collections:
- General Graduate School > 4. Theses(Ph.D)
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