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1 SYNTHESIS OF HYPERBRANCHED POLYGLYCIDOL-STAR-POLY(N-ISOPROPYLACRYLAMIDE) USING NITROXIDE-MEDIATED POLYMERIZATION AS A THERMO-SENSITIVE DRUG DELIVERY SYSTEM 11
1.1 INTRODUCTION 11
1.2 EXPERIMENT DETAILS 16
1.2.1 Materials 16
1.2.2 Polymerization of HBP 17
1.2.3 Modification of Hydroxyl Group of the HBP to Chloro and Azide Groups. 17
1.2.4 Synthesis of 4-alkynyl TEMPO from 4-hydroxy TEMPO 18
1.2.5 Synthesis of HBP-TEMPO by Click Chemistry 19
1.2.6 Polymerization of NIPAM with HBP-TEMPO 19
1.2.7 Fabrication of the Polymeric Micelles 20
1.2.8 Preparation of the Dox Entrapped Micelles 21
1.2.9 Time-Dependent Release Test of Dox from Micelles 21
1.2.10 Cellular Cytotoxicity Studies on the Polymers 21
1.2.11 Characterizations 22
1.3 RESULTS AND DISCUSSION 23
1.3.1 Synthesis and Characterization of HBP-TEMPO for NMP Macroinitiation 23
1.3.2 Synthesis and Characterization of HBP-star-[p(NIPAM)n]6 (n=15, 25, 35 and 45) 24
1.3.3 Thermo-Responsive Phase Transition Behavior of Multiarm-Hyperbranched Copolymers 27
1.3.4 Preparation and Characterization of Polymeric Micelles 27
1.3.5 Thermo-Responsive Release of Dox 29
1.3.6 Cellular Cytotoxicity of The Polymeric Micelles 30
1.4 CONCLUSIONS 31
1.5 REFERENCES 33
2 SYNTHESIS OF HYPERBRANCHED POLYGLYCIDOL-BLOCK-POLY(L-LACTIDE) FOR PH SENSITIVE CONTROLLED DRUG DELIVERY SYSTEM 57
2.1 INTRODUCTION 57
2.2 EXPERIMENT DETAILS 61
2.2.1 Materials 61
2.2.2 Polymerization of HBP 61
2.2.3 Preparation of 1,3-Dicyclohexyl Benzimidazolium bromide 62
2.2.4 Synthesis of 1,3-Dicyclohexyl Benzimidazolium Hydrogen Carbonates ([DCBNHC(H)][HCO3]) 63
2.2.5 Ring Opening Polymerization of L-Lactide Using [DCBNHC(H)][HCO3] as the Organocatalyst 63
2.2.6 Fabrication of Polymer Micelles 64
2.2.7 Preparation of the Dox Entrapped Micelles 65
2.2.8 Time-Dependent Release Test of Dox from Micelles 65
2.2.9 Cellular Cytotoxicity Studies on the Synthesized Polymers 66
2.2.10 Characterizations 66
2.3 RESULTS AND DISCUSSION 67
2.3.1 Synthesis and Characterization of HBP 67
2.3.2 Synthesis and Characterization of 1,3-Dicyclohexyl-benzimidazolium Hydrogen Carbonates as the Organocatalyst for Ring Opening Polymerization of L-lactide 68
2.3.3 Synthesis and Characterization of HBP-b-p(L-lactide)n (n=10, 20, 30 and 40). 69
2.3.4 Preperation and Characterization of Polymeric Micelles 69
2.3.5 pH Responsive Release of Dox 71
2.3.6 Cellular Cytotoxicity of the Polymeric Micelles 71
2.4 CONCLUSIONS 72
2.5 REFERENCES 73