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Synthesis, Characterization and Amphiphilic Self-Assembly of Inorganic Nanoparticles Functionalized with Polymer Brushes of Variable Composition and Chain Length

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Synthesis, Characterization and Amphiphilic Self-Assembly of Inorganic Nanoparticles Functionalized with Polymer Brushes of Variable Composition and Chain Length Synthesis, Characterization and Amphiphilic Self-Assembly of Inorganic Nanoparticles Functionalized with Polymer Brushes of Variable Composition and Chain Length by Brian Coleman B.Sc., McMaster University, 2012 A Thesis Submitted in Partial Fulfillment of the Requirements for the Degree of MASTER OF SCIENCE in the Department of Chemistry Brian Coleman, 2016 University of Victoria All rights reserved. This thesis may not be reproduced in whole or in part, by photocopy or other means, without the permission of the author. i Synthesis, Characterization and Amphiphilic Self-Assembly of Inorganic Nanoparticles Functionalized with Polymer Brushes of Variable Composition and Chain Length by Brian Coleman B.Sc., McMaster University, 2012 Supervisory Committee Dr. Matthew Moffitt, Supervisor (Department of Chemistry) Dr. Irina Paci, Departmental Member (Department of Chemistry) ii Supervisory Committee Dr. Matthew Moffitt, Supervisor Department of Chemistry Dr. Irina Paci, Departmental Member Department of Chemistry ABSTRACT The synthesis, characterization and amphiphilic self-assembly of polymer brush functionalized nanoparticles (PBNPs) using a block copolymer template is described herein. To study the effect of polymer brush composition on self-assembly, four samples were created using a mixture of PS-b-PAA (polystyrene-block-polyacrylic acid) and PMMA-b-PAA (poly(methyl methacrylate)-block-polyacrylic acid) diblock copolymers to create PBNPs with a CdS quantum dot (QD) core and different ratios of PS and PMMA in the coronal brush. Static light scattering showed that despite differences in brush composition, the PBNPs formed nanoparticles of similar aggregation number and chain density but showed evidence of asymmetric structure in a common solvent for both blocks at higher PS contents. After subsequent hydrolysis of the hydrophobic PMMA to hydrophilic poly(methacrylic acid) (PMAA), these amphiphilic particles were then self-assembled in THF/H2O solution in which it was determined that increasing the hydrophobic content of the brush composition, the initial nanoparticle concentration (c0) or the added salt content (RNaCl), would cause the assembly of low curvature assemblies. Compilation of this data allowed for the construction of phase diagrams for PBNP systems based on brush composition and c0 at different salt contents. Lastly, PS-b-PAA-b-PMMA triblock copolymers with variable PMMA chain length were assembled into PBNPs around a CdS QD core using a iii block copolymer template approach. Light scattering showed these particles also had similar aggregation number and chain density despite the difference in PMMA chain length. After hydrolysis of PMMA to PMAA these particles were then self-assembled in THF/H2O mixtures to determine the role of PMAA block length on the produced morphological structures. The resulting assemblies suggest that chain length played a minimal role in their self-assembly iv TABLE OF CONTENTS Supervisory Committee……………………………………………………………………….….iii Abstract…………………………………………………………………………………………..iii Table of Contents…………………………………………………………………………………v List of Tables……………………………………………………………………………………..xi List of Figures……………………………………………………………………………………xii List of Abbreviations……………………………………………………………………………xiv Acknowledgment………………………………………………………………………………...xx CHAPTER 1……………………………………………………………………………………...1 General Introduction…………….……………………………………………………………....1 1.1 General Introduction…………………………………………………………………..2 1.2 Polymers and Block Copolymers……………………………………………………..4 1.2.1 Polymers…………………………………………………………………….4 1.2.2 Molecular Weight Distribution……………………………………………...5 1.3 Micellization of Diblock and Triblock Copolymers in Selective Solvents…………...7 1.3.1 Formation of Block Copolymer Micelles …………………………………..7 1.3.2 Thermodynamics of Block Copolymer Micellization………………………8 1.3.3 Micellization of Ionic Diblock Copolymers in Organic Solvents…………..9 1.4 Semiconducting Nanoparticles and the Quantum Confinement Effect……………...10 1.5 Synthesis of Polymer/Nanoparticle Composite Micelles……………………………15 1.6 Varieties of Mixed Brush Block Copolymer Nanoparticles…………………………17 1.7 Major Characterization Techniques………………………………………………….21 1.7.1 Gel Permeation Chromatography (GPC)…………………………………..21 1.7.2 Static and Dynamic Light Scattering (SLS and DLS)……………………..22 1.7.3 Transmission Electron Microscopy (TEM)………………………………..24 1.7.4 Laser Scanning Confocal Fluorescence Microscopy (LSCFM)…………...25 1.8 Content of this Thesis………………………………………………………………..26 v CHAPTER 2…………………………………………………………………………………….28 Synthesis and Characterization of PS/PMAA-(CdS) Nanoparticles Created Using a Novel Diblock Copolymer Template Approach……………………………………………………...28 2.1 Introduction…………………………………………………………………………..29 2.2 Experimental…………………………………………………………………………32 2.2.1 Hydrolysis of Polystyrene-block-poly(tert-butyl acrylate) (PS-b-tBA) and Poly(methyl methacrylate)-block-(tert-butyl acrylate) (PMMA-b-tBA) Diblock Copolymers…32 2.2.2 Preparation of Amphiphilic CdS Quantum Dots with Polystyrene/Poly (methacrylic acid) (PS/PMAA) Mixed Brushes of Varying Composition………………………33 2.2.2.1 Preparation of Polystyrene-block-poly(cadmium acrylate) / Poly(methyl methacrylate)-block-poly(cadmium acrylate) Mixed Reverse Micelles (PS/PMMA- b-PACd) …………………………………………………………………………………………33 2.2.2.2 Preparation of CdS Quantum Dots in Reverse Micelle Cores...…35 2.2.2.3 Core Cross-linking Reverse Micelles Containing CdS QDs………………………………………………………………………………………………36 2.2.2.4 Hydrolysis of PMMA Brush Chains to PMAA………………….37 2.2.6 Gel Permeation Chromatography (GPC)…………………………………..38 2.2.7 Nuclear Magnetic Resonance (NMR)……………………………………..38 2.2.8 UV-Vis Absorption Measurements………………………………………..38 2.2.9 Transmission Electron Microscopy (TEM)………………………………..39 2.2.10 Dynamic Light Scattering (DLS)………………………………………...39 2.2.11 Static Light Scattering (SLS)…………………………………………….40 2.2.12. Fourier Transform Infrared (FTIR) Spectroscopy………………………41 2.2.13. Powder X-Ray Diffraction (XRD)……………………………………....42 2.3 Results and Discussion………………………………………………………………42 2.3.1 Hydrolysis of Polystyrene-block-poly(tert-butyl acrylate) (PS-b-PtBA) to Polystyrene-block-poly(acrylic acid) (PS-b-PAA)………………………………………42 vi 2.3.2 Micellization and Fractionation of Polystyrene-block-poly(cadmium acrylate) / Poly(methyl methacrylate)-block-poly(cadmium acrylate) Blends ………………….44 2.3.3 Characterization of Polystyrene-block-poly(cadmium acrylate) / Poly(methyl methacrylate)-block-poly(cadmium acrylate) Mixed Reverse Micelles, PS/PMMA- b-PACd…………………………………………………………………………………………..47 2.3.4 Characterization of Crosslinked PS/PMMA Mixed Brush Coated CdS QDs Before Hydrolysis of PMMA Chains, PS/PMMAXL(CdS)………………………………..…….54 2.3.4.1 Gel Permeation Chromatography and Dispersability Tests…..…54 2.3.4.2 UV-Vis Spectroscopy and Transmission Electron Microscopy....58 2.3.4.3 Static and Dynamic Light Scattering…………………………….63 2.3.4.4 NOESY NMR Investigation of Mixed Brush Structure…………72 2.3.4 Hydrolysis of PMMA Brush Chains to PMAA: Converting PS/PMMAXL(CdS) to PS/PMAA-(CdS)………………………………………………………..75 2.3.5 Characterization of Crosslinked PS/PMAA Mixed Brush Coated CdS QDs After Hydrolysis of PMAA Chains, PS/PMAA-(CdS)………………………………………….79 2.3.5.1 Dynamic Light Scattering (DLS)………………………………..79 2.3.5.2 Transmission Electron Microscopy (TEM)……………………...82 2.3.5.3 Powder X-Ray Diffraction (XRD)……………………………….85 2.4 Conclusions…………………………………………………………………………..86 CHAPTER 3 The Effect of Brush Composition on the Self-Assembly of PS/PMMA-(CdS) Polymer Brush Functionalized Nanoparticles………………………………………………………………….88 3.1 Introduction………………………………………………………………………….89 3.2 Experimental…………………………………………………………………………92 vii 3.2.1 Self-Assembly of PS/PMAA-(CdS) NPs in Mixtures of THF and Water…92 3.2.2 Transmission Electron Microscopy………………………………………..93 3.2.3 Dynamic Light Scattering………………………………………………….94 3.2.4 Laser Scanning Confocal Fluorescence Microscopy………………………94 3.3 Results and Discussion………………………………………………………………95 3.3.1 Overview of PS/PMAA-CdS Self-Assembled Morphologies……………..95 3.3.1.1 Spheres…………………………………………………………..97 3.3.1.2 Cylinders…………………………………………………………98 3.3.1.3 Vesicles…………………………………………………………..99 3.3.1.4 Compound Vesicles ..…………………………………………..100 3.3.1.5 Large Compound Supermicelles……………………………..…101 3.3.1.6 Unimicellar Dots………………………………………………102 3.3.2 Mixed Morphologies and Annealing Experiments.....................................103 3.3.3 Determination of the Critical Water Concentration (CWC)…………...…106 3.3.4 Effect of Brush Composition (fPS) on Amphiphilic Self-Assembly of NPs……………………………………………………………………………………………..107 3.3.5 Effect of Initial PS/PMAA-CdS Concentration (c0) on Amphiphilic Self……………………………………………………………………………………………..112 3.3.6 Effect of Salt Addition on Amphiphilic Self-Assembly of NPs…………114 3.3.7 Phase Diagrams of PS/PMAA-CdS in THF/Water……………………...117 3.3.8 Measurement of the Characteristic Dimension of each Assembly by TEM……………………………………………………………………………………………125 3.3.9 Dynamic Light Scattering (DLS)………………………………………..128 viii 3.3.10 Imaging of PS/PMMA-CdS Assemblies by Laser Scanning Confocal Fluorescence Microscopy (LSFCM)………………………………………………………….129 3.4 Conclusion………………………………………………………………………...131 CHAPTER 4 The Effect of Brush Composition on the Self-Assembly of PS/PMMA-(CdS) Polymer Brush Functionalized Nanoparticles Synthesized Using a Triblock Copolymer Template…….132 4.1 Introduction……………………………………………………………………….133 4.2 Experimental………………………………………………………………………135 4.2.1 Preparation of Polystyrene-block-Poly(acrylic acid)-block-Poly(methyl methacrylate)(PS-b-PAA-b-PMMA)
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