Functionalization of Well-Defined Polyacrylates with TEMPO and PEG Moieties for the Modification of Hemoglobin-Based Oxygen Carriers
Term of Award
Master of Science in Applied Physical Science (M.S.)
Document Type and Release Option
Thesis (restricted to Georgia Southern)
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This work is licensed under a Creative Commons Attribution 4.0 License.
Department of Chemistry
Committee Member 1
Committee Member 2
The latest generation of Hemoglobin-Based Oxygen Carriers (HBOCs), Polynitroxyl Pegylated Hemoglobin (PNPH), containing 2,2,6,6-tetramethylpiperidine-1-oxidyl (TEMPO) and polyethylene glycol (PEG) has been approved by phase III clinical trials. The current synthesis involves a costly multistep procedure not conducive for large scale manufacturing of a potential treatment for Traumatic Brain Injuries. This thesis reports on the development of an affordable synthetic strategy of multifunctional copolymers that reduces the synthesis towards novel PNPH derivatives. Polyacrylates were synthesized with controlled molecular weight via Reversible-Addition Fragmentation Chain Transfer Agent (RAFT). By pre-determining the molar ratios of chain transfer agent (CTA) to the monomer acrylats, we calculated the theoretical molecular weight of the polymers to be 3000-15,000. The controlled poly-acrylates with ratios of 1:20 and 1:30 of the CTA to the monomer acrylates were characterized by MALDI-ToF MS and the molecular weights of each polymer was successfully determined. For the polymer, the monomer conversion of all the synthesized controlled polyacryaltes were determined by (1H NMR) Nuclear Magnetic Resonance. The polymers contain NMe2 side chains which were used for modification. PEG and TEMPO derivatives were synthesized with chloroacetate groups which allowed the attachment of these functionalities to the polymer Nme2 groups, hence introducing these functionalities via polymerization functionalization. The NMR data indicated that controlled polyacrylates were successfully quantitatively bonded to the NMe2 group of polyacryaltes with controlled molar ratios. Since TEMPO is a stable radical chemical, Electron Paramagnetic Resonance (EPR) was used to measure the presence of radical TEMPO in the controlled polyacrylate.
Alomainy, Omniya, "Functionalization of Well-Defined Polyacrylates with TEMPO and PEG Moieties for the Modification of Hemoglobin-Based Oxygen Carriers" (2017). Electronic Theses and Dissertations. 1580.
Research Data and Supplementary Material