Novel Synthesis, Characterization, and Versatile Applications of Multifunctional Nanomaterials by Control Radical Polymerization and/or Click Chemistry
- Alternative Title
- 이용한 나노물질 합성 및 특성분석, 그리고 다양한 응용에 관한 연구
- Abstract
- 물질 구성, 설계, 기능을 정밀하게 제어할 수 있는 나노 재료의 설계 및 합성은 많은 산업 분야에 필수적이다. 최근 라디칼 제어 중합(CRP)과 click chemistry와 같은 중합법으로 다양한 하이브리드 물질개발이 많이 연구되고 있다. CRP중 특히 atom transfer radical polymerization (ATRP) 및 reversible addition-fragmentation chain transfer (RAFT)중합은 분자량 제어도가 높은 고분자 합성을 위한 강력한 방법이다. 게다가, 이 중합은 뛰어난 물성 및 우수한 functional 그룹 허용, 고수율, 구리 (I) 촉매 아지드-알킨의 사이클로 및 thiol-ene chemistry으로 기능성 고분자 합성에 있어 매우 유망한 미래를 가지고 있다.
이 논문의 주요 목표는 다양한 제품에 사용되기 위해 CRP법 혹은 CRP법과 Click chemistry를 같이 사용하여 나노물질에 기능성 고분자를 접합시키는 것으로 이를 새롭고 간단한 공정이 되도록 연구하였다. 철과 금(코어-쉘), 실리카 나노파티클, polyhedral oligomeric silsesquioxanes, 마그네슘/알루미늄 layered double hydroxides, halloysite clay 나노튜브, 카본 나노튜브, hydroxyapatite 나노결정체와 같은 여러개의 나노물질을 표면개조하여 다양한 제품에 사용할 수 있도록 특히 바이오제품등에 쓸 수 있도록 표면 성질을 바꾸는 연구를 수행하였다. 또한 이 논문에서, thiol-lactam initiated radical polymerization(TLIRP)를 이용하여 Fe3O4 자성 나노 입자 표면에 폴리머를 쉽게 붙일 수 있다는 것도 증명하였다.
하이브리드 나노물질의 형태와 화학적 구조는 다양한 분석기기를 통해 관찰하였다. 그리고 이 논문에 나온 유기-무기 하이브리드 나노 구조는 기계, 전기, 광학, 영상, 생물의학 및 구동 기기등에 사용될 수 있는 큰 잠재력을 보여주었다. 무엇보다도, 나노물질의 표면에 고분자 코팅시키는 기술은 앞으로 물질 구조응용 및 개발에 필수적으로 사용될 것으로 기대된다.
The design and synthesis of nano-engineered materials with precise control over material composition, architecture and functionality is integral to advances in diverse fields. Recent development in the techniques of functional polymeric nanomaterials such as controlled radical polymerization (CRP) and click chemistry has opened up a new horizon to provide cascades of novel hybrid nanomaterials for versatile applications. CRP, especially atom transfer radical polymerization (ATRP) and reversible addition-fragmentation chain transfer (RAFT) polymerization, has been demonstrated as a powerful strategy for synthesizing well-controlled macromolecules. Meanwhile, because of the high specificity, excellent functional group tolerance, and quantitative yields, Cu(I)-catalyzed azide-alkyne cycloaddition and thiol-ene chemistry is emerging as a promising protocol to synthesize a range of functional polymers.
The main goal of this thesis is to develop new and simple approaches for immobilization of functional polymers onto nanomaterials by either CRP alone or the combination of click chemistry and CRP techniques for various applications. The surface chemical modification of several nanomaterials including Fe-Au NPs, polyhedral oligomeric silsesquioxanes, Mg/Al layered double hydroxides, halloysite clay nanotubes, carbon nanotubes, hydroxyapatite nanocrystals has been carried out to tune the surface properties for wide applications especially bio-applications. In this thesis, a facile surface functionalization of Fe3O4 magnetic nanoparticles by polymer brushes via surface functionalized thiol-lactam initiated radical polymerization (TLIRP) employing grafting from approach are also demonstrated.
The resulting chemical structure and morphologies of hybrid nanostructures were investigated by a wide variety of spectroscopic and microscopic techniques. Furthermore, the resulted organic-inorganic hybrid nanostructures encompassed in this dissertation show their huge promise towards mechanical, electrical, optical, imaging, biomedical and actuating applications. Above all, these versatile techniques for surface functionalization of nanomaterials by polymers offer indispensible tools for the future development and application of these materials and structures.
- Issued Date
- 2013
- Awarded Date
- 2013. 8
- Type
- Dissertation
- Publisher
- 부경대학교
- Affiliation
- 대학원
- Department
- 대학원 이미지시스템공학과
- Advisor
- 임권택
- Table Of Contents
- Abstract i
Abstract (In Korean Language) ii
Acknowledgement iii
Table of contents v
List of Fig.s xii
CHAPTER 1. General Introduction 1
1.1. Introduction to polymer and nanomaterials in nanotechnology 1
1.2. Synthesis of polymer brushes via surface grafted strategies 4
1.3. Atom transfer radical polymerization in designing advanced materials 5
1.4. Hybrid nanomaterials via reversible addition fragment chain transfer (RAFT) polymerization 8
1.5. Ring-opening polymerization (ROP) for nanomaterials having controlled architectures 10
1.6. Surface engineering of nanomaterials using click chemistry 11
1.7. Aim and outline of this thesis 13
1.8. References 15
CHAPTER 2. Immobilization of Proteins onto Poly(2-hydroxyethyl methacrylate) Functionalized Fe-Au/Core-Shell Nanoparticles via Adsorption Strategy 18
2.1. Introduction 18
2.2. Experimental section 22
2.2.1. Materials 22
2.2.2. Synthesis of Fe-AuNPs by a reverse micelle method 22
2.2.3. Synthesis of disulfide-carrying ATRP initiator 23
2.2.4. Preparation of disulfide-carrying PHEMA by ATRP technique 23
2.2.5. Grafting of DT-PHEMA onto Fe-AuNPs 24
2.2.6. Characterization and measurements 24
2.3. Results and discussion 25
2.3.1. Characterization of the Fe-AuNPs 25
2.3.2. Characterization of DT-PHEMA 28
2.3.3. Characterization of PHEMA-g-Fe-AuNPs 29
2.3.4. Optical and magnetic properties of PHEMA grafted Fe-AuNPs 34
2.3.5. Dispersion stability of the PHEMA grafted Fe-AuNPs 35
2.3.6. Immobilization of protein onto PHEMA functionalized Fe-Au NPs 37
2.4. Conclusions 38
2.5. References 39
CHAPTER 3. Surface Functionalization of Halloysite Nanotubes by Grafting of Poly(poly(ethylene glycol) methacrylate) for Bioactive Interface with Covalently Immobilized Penicillin 42
3.1. Introduction 43
3.2. Experimental section 44
3.2.1. Materials 44
3.2.2. Synthesis of ATRP initiator (GPTS-BMPA) 45
3.2.3. Immobilization of ATRP initiator (GPTS-BMPA) onto HNTs 45
3.2.4. Synthesis of HNTs-g-PPEGMA nanohybrids via SI-ATRP 45
3.2.5. Conjugation penicillin with HNTs-g-PPEGMA via covalent linkage 46
3.2.6. Determination of antibacterial activity of the penicillin anchored HNTs surfaces 46
3.2.7. Instrumentation 48
3.3. Results and discussion 49
3.3.1. Synthesis of HNTs-g-PPEGMA via SI-ATRP technique 50
3.3.2. Covalent immobilization of pencillin on the HNTs-g-PPEGMA surfaces and its antibacterial assay 54
3.4. Conclusion 59
3.5. References 59
CHAPTER 4. Poly(2-hydroxyethyl methacrylate) Grafted Halloysite Nanotubes as A Molecular Host Matrix for Luminescent Ions Prepared by Surface-Initiated RAFT Polymerization and Coordination Chemistry 62
4.1. Introduction 63
4.2. Experimental section 65
4.2.1. Materials 65
4.2.2. Immobilization of RAFT agent onto HNTs 65
4.2.3. Synthesis of HNTs-g-PHEMA via SI-RAFT polymerization 65
4.2.4. Cleavage of the grafted PHEMA from HNTs-g-PHEMA 66
4.2.5. Coordination of Eu3+ with HNTs-g-PHEMA-COOH macromolecular ligands 66
4.2.6. Characterization techniques 66
4.3. Results and discussion 67
4.3.1. Grafting of PHEMA from HNTs by SI-RAFT technique 68
4.3.2. Characterization and optical properties of Eu3+ capped HNTs-g-PHEMA nanohybrid complexes 73
4.4. Conclusions 77
4.5. References 78
CHAPTER 5. Nondestructive Covalent Functionalization of MWNTs by Biocompatible Polymer and Their Conjugation with CdSe Quantum dots: Synthesis, Properties, and Cytotoxicity Studies 80
5.1. Introduction 81
5.2. Experimental section 84
5.2.1. Materials 84
5.2.2. Synthesis of S-1-ethyl-S’-(α,α’-dimethyl-α”-acetic acid) trithiocarbonate (EDAT), a RAFT agent 84
5.2.3. Synthesis of benzophenonyl containing EDAT 85
5.2.4. Immobilization of photoactive RAFT agent (BP-EDAT) onto MWNTs surface 85
5.2.5. Encapsulation of MWNTs by PDMEAMA polymer using surface-initiated RAFT polymerization 85
5.2.6. Synthesis and conjugation of CdSe QDs with MWNT-g-PDMAEMA 86
5.2.7. In vitro cytotoxicity assay of modified MWNT by MTT-dye reduction method 87
5.2.8. Characterization techniques 88
5.3. Results and discussion 88
5.3.1. Synthesis and characterization of MWNTs-g-PDMAEMA via surface-initiated RAFT Polymerization 89
5.3.2. Anchoring of CdSe QDs with MWNTs-g-PDMAEMA 95
5.3.3. In vitro cytotoxicity assessments of the modified MWNTs 98
5.4. Conclusions 99
5.5. References 100
CHAPTER 6. Chemical Modification of Polyhedral Oligomeric Silsesquioxanes by Functional Polymer via Combination of RAFT Polymerization and Azide-Alkyne Click Reaction 103
6.1. Introduction 104
6.2. Experimental section 106
6.2.1. Materials 106
6.2.2. Azidation of chloropropyl-heptaisobutyl-substituted POSS 107
6.2.3. Synthesis of random copolymer poly(HEMA-co-MMA) via RAFT technique 107
6.2.4. Synthesis of alkyne-functionalized poly(HEMA-co-MMA) 107
6.2.5. Synthesis of poly(HEMA-co-MMA)-g-POSS by click reaction 108
6.2.6. Characterization and measurements 108
6.3. Results and discussion 109
6.3.1. 1H-NMR analysis of poly(HEMA-co-MMA)-g-POSS nanohybrids 110
6.3.2. FT-IR analysis of poly(HEMA-co-MMA)-g-POSS nanohybrids 112
6.3.3. The chemical composition of the nanohybrids 114
6.3.4. Thermal stability of hybrid material 116
6.3.5. Morphology and crystalline of hybrid material 117
6.3.6. The number average molecular weight of hybrid material 119
6.4. Conclusions 120
6.5. References 121
CHAPTER 7. Poly(allyl methacrylate) Functionalized Hydroxyapatite Nanocrystals via the Combination of Surface-Initiated RAFT Polymerization and Thiol-Ene Protocol: A Potential Anticancer Drug Nanocarrier 124
7.1. Introduction 125
7.2. Experimental section 127
7.2.1. Materials 127
7.2.2. Functionalization of HAP NCs by 3-(chloropropyl)triethoxy silane 128
7.2.3 Anchoring of RAFT agent to HAP NCs 128
7.2.4. Synthesis of HAP-PolyAMA nanohybrids by SI-RAFT technique 128
7.2.5. Synthesis of multicarboxyl groups containing HAP-PolyAMA via thiol-ene click chemistry 128
7.2.6. Incorporation of cisplatin in the HAP-Poly(AMA-COOH) 129
7.2.7. Release of drug from HAP-Poly(AMA-COOH)/Pt complex 129
7.2.8. Cell culture and in vitro cytotoxicity assay of HAP-Poly(AMA-COOH)/Pt complex 130
7.2.9. Instrumentation 131
7.3. Results and discussion 131
7.3.1. Immobilization of RAFT agent onto the HAP NCs surface 132
7.3.2. Preparation of HAP-PolyAMA nanohybrids via surface-initiated RAFT polymerization 135
7.3.3. Preparation, characterization and drug release from HAP-Poly(AMA-COOH)/Pt complex 139
7.4. Conclusions 145
7.5. References 146
CHAPTER 8. A Novel Photoluminescent Nanohybrid of Poly(ε-Caprolactone) grafted Mg/Al Layered Double Hydroxides and Tb3+ ions: Synthesis, Characterization, and Cytotoxicity Studies 149
8.1. Introduction 150
8.2. Experimental section 151
8.2.1. Materials 151
8.2.2. Synthesis of azide-functionalized Mg/Al LDHs 151
8.2.3. Synthesis of α-carboxyl-ω-propargyl PCL (alkyene-PCL-COOH) 152
8.2.4. Grafting of PCL onto LDH via Click chemistry 153
8.2.5. Coordination of Tb3+ ions with LDH-g-PCL-COOH 153
8.2.6. In vitro cytotoxicity assay of hybrids (MTT-dye reduction assay) 154
8.2.7. Characterization techniques 154
8.3. Results and Discussion 155
8.3.1. Characterization of LDH-g-PCL-COOH nanohybrids. 155
8.3.2. Characterization of LDH-g-PCL-Tb3+ nanohybrids 160
8.4. Conclusions 164
8.5. References 165
CHAPTER 9. Encapsulation of Fe3O4 Magnetic Nanoparticles with Poly(methyl methacrylate) via Surface Functionalized Thiol-Lactam Initiated Radical Polymerization 168
9.1. Introduction 169
9.2. Experimental section 171
9.2.1. Materials 171
9.2.2. Synthesis of MNPs 171
9.2.3. Anchoring of thiol groups onto MNPs 172
9.2.4. Synthesis of PMMA-g-MNPs by TLIRP 172
9.2.5. Instrumentation 173
9.3. Results and discussion 174
9.3.1. Synthesis of MNPs-SH 174
9.3.2. Surface-Initiated TLIRP from MPTMS anchored MNPs 177
9.3.3. Control of MMA polymerization on MNPs-SH by TLIRP 180
9.3.4. Thermogravimetric analysis of MNPs, MNPs-SH, PMMA-g-MNPs 181
9.3.5. Magnetic property of MNPs, MNPs-SH and PMMA-g-MNPs 182
9.3.6. Dispersion stability of the PMMA-g-MNPs 184
9.4. Conclusions 185
9.5. References 186
SUMMARY 188
PUBLICATION 191
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- Doctor
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