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CHEMISTRY TECHNIQUES a Dissertation Presented to the Graduate Faculty Of PREPARING POLYMERIC BIOMATERIALS USING “CLICK” CHEMISTRY TECHNIQUES A Dissertation Presented to The Graduate Faculty of The University of Akron In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy Fei Lin May, 2014 PREPARING POLYMERIC BIOMATERIALS USING “CLICK” CHEMISTRY TECHNIQUES Fei Lin Dissertation Approved: Accepted: ______________________ _______________________ Advisor Department Chair Dr. Matthew L. Becker Dr. Coleen Pugh ______________________ _______________________ Committee Member Dean of the College Dr. Abraham Joy Dr. Stephen Z. D. Cheng ______________________ _______________________ Committee Member Dean of the Graduate School Dr. Chrys Wesdemiotis Dr. George R. Newkome ______________________ _______________________ Committee Member Date Dr. Shi-Qing Wang ______________________ Committee Member Dr. Robert A. Weiss ii ABSTRACT Significant efforts have been focused on preparing degradable polymeric biomaterials with controllable properties, which have the potential to stimulate specific cellular responses at the molecular level. “Click” reactions provide a universal tool box to achieve that goal through molecular level design and modification. This dissertation demonstrates multiple methodologies and techniques to develop advanced biomaterials through combining degradable polymers and “click” chemistry. In my initial work, a novel class of amino acid-based poly(ester urea)s (PEU) materials was designed and prepared for potential applications in bone defect treatment. PEUs were synthesized via interfacial polycondensation, and showed degradability in vivo and possessed mechanical strength superior to conventionally used polyesters. Further mechanical enhancement was achieved after covalent crosslinking with a short peptide crosslinker derived from osteogenic growth peptide (OGP). The in vitro and in an in vivo subcutaneous rat model demonstrated that the OGP-based crosslinkers promoted proliferative activity of cells and accelerated degradation properties of PEUs. As a continuous study, extra efforts were focused on the development of PEUs with functional pendant groups, including alkyne, azide, alkene, tyrosine–phenol, and ketone groups. PEUs with Mw exceeding to 100K Da were obtained via interfacial polycondensation, and the concentration of pendent groups was varied using a copolymerization strategy. Electrospinning was used to fabricate PEU nanofiber matrices iii with mechanical strengths suitable for tissue engineering. A series of biomolecules were conjugated to nanofiber surface following electrospinning using “click” reactions in aqueous media. The ability to derivatize PEUs with biological motifs using high efficient chemical reactions will significantly expand their use in vitro and in vivo. Based on similar principles, a series of mono- and multifunctionalized polycaprolactone (PCL) bearing various “clickable” groups, including ketone, alkyne, azide, and methyl acrylate (MA), were synthesized via ring opening polymerization. A quartz crystal microbalance (QCM) was used to quantify the rate and extent of surface conjugation between RGD peptides and polymer thin films. The successful conjugation was further confirmed by static contact angle and NMR measurements. QCM results also verified and quantified the sequential immobilization of peptides onto polymer films. Besides polymer functionalization, “click” reactions were also utilized for hydrogel fabrication and post-gelation modification. Polyethylene glycol-based hydrogels were formed via oxime ligation. The gelation process and final mechanical strength of the hydrogels can be tuned using pH and the catalyst concentration. The time scale to reach the gel point and complete gelation, and the storage modulus of hydrogels can be tuned in two orders of magnitude. Azide- and alkene-functionalized hydrogels were also fabricated, and further post-gelation functionalization was achieved via alkyne-azide cycloaddition and thiol-ene radical addition for spatially defined peptide incorporation. These materials with tunable mechanical regimes and biomolecule patterns were attractive for soft tissue engineering. iv ACKNOWLEDGEMENTS This dissertation would not have been possible without the help of so many people in so many ways. It’s also a product of tremendous serendipity and encounters with people who have significant effect on my career. First of all, a very special thank you should be given to my advisor, Dr. Matthew L. Becker, for all his support during the past years. He was very suggestive and supportive during my researches and it was my great honor to work with him. I am also very grateful to Dr. Abraham Joy, Dr. Avraam I. Isayev, Dr. Chrys Wesdemiotis, Dr. Robert Weiss, and Dr. Shi-Qing Wang for their cooperation, help, discussion, advice and comment during my research. I also want to say thanks to students in the College of Polymer Science and Engineering, in particular Jing Zhou, Xueyuan Wang, Yiwen Li, Kai Guo, Shiwang Cheng, Tian Liang, Hao Su, Kan Yue, Yin Xu, Panpan Lin, all my group members and friends. They have been a critical source of support and encouragement. I can’t thank them enough for their kind friendship, trust, and support. I am also very grateful for my parents and grandparents, who give me all the love and encouragement for ever. They have instilled in me the importance of education, working hard, and caring for others. v TABLE OF CONTENTS Page LIST OF TABLES………………………………………………………………………ix LIST OF FIGURES……………………………………………………………………..x LIST OF SCHEMES………………………………………………………………….xxii CHAPTER I. INTRODUCION………………………………………………………………………..1 1.1 Degradable Polymers……………………………………………………..………..3 1.2 “Click” Chemistry and Its Applications in Biopolymers………………………….42 1.3 Conclusion………………………………………………………………………...72 II. EXPERIMENTAL SECTION………………………………………………………...73 2.1 Materials…………………………………………………………………………..73 2.2 Instruments………………………………………………………………………..75 III. RESORBABLE, AMINO ACID-BASED POLY (ESTER UREA)S CROSSLINKED WITH OGP PEPTIDE WITH ENHANCED MEAHCNICAL PROPERTIES AND BIOACTIVITY…………………………………………………………………………..81 3.1 Outline..……………………………………………………………………………81 3.2 Introduction…………………………………………………………………….….82 3.3 Experimental Section…………………………………………………………..….85 3.4 Results……………………………………………………………………………..96 vi 3.5 Discussion…………………………………………………………………..……105 3.6 Conclusion……………………………………………………………………….108 3.7 Acknowledgement……………………………………………………………….109 IV. POST-ELECTROSPINNING “CLICK” MODIFICATION OF DEGRADABLE AMINO ACID-BASED POLY(ESTER UREA) NANOFIBERS…………………...…110 4.1 Outline..…………………………………………………………………………. 110 4.2 Introduction………………………………………………………………………111 4.3 Experimental Section………………………………………………………...…..114 4.4 Results and Discussion…………………………………………………………..135 4.5 Conclusion……………………………………………………………………….152 4.6 Acknowledgment…………………………………………………………….…..153 V. PEPTIDE-FUNCTIONALIZED OXIME HYDROGELS WITH TUNABLE MECHANICAL PROPERTIES AND GELATION BEHAVIOR……………………...154 5.1 Outline..…………………………………………………………………………. 154 5.2 Introduction………………………………………………………………………155 5.3 Experimental Section………………………………………………………...…..158 5.4 Results and Discussion…………………………………………………………..168 5.5 Conclusion……………………………………………………………………….181 5.6 Acknowledgment…………………………………………………………….…..182 VI. CASCADING “TRI-CLICK”FUNCTIONALIZATION OF POLYCAPROLACTONE THIN FILMS QUANTIFIED VIA QCM……………………………………………....183 6.1 Outline..…………………………………………………………………………. 183 6.2 Introduction………………………………………………………………………184 6.3 Experimental Section………………………………………………………...…..186 vii 6.4 Results and Discussion…………………………………………………………..201 6.5 Conclusion……………………………………………………………………….215 6.6 Acknowledgment…………………………………………………………….…..216 REFERENCES…………………………………………………….…………………...238 APPENDIX…………………………………………………………………………….271 viii LIST OF TABLES Table Page 1.1. Structure of cyclic lactones and corresponding polymers…………………………….5 3.1. Characterization data summary for the amino acid-based poly(ester ureas)…………88 3.2. Summary of the mechanical properties of peptide-crosslinked PEU………………..99 4.1. Reaction formulation summary of experiment groups and control groups for nanofiber surface modification. …………………………………………………………...….133 4.2. Molecular mass data of PEUs. aMass average molecular weight (g/mol); bDistribution of molecular mass (Dm, Mw/Mn) of polymers after precipitation in water, which significantly narrows the molecular mass distribution from what is expected in a step growth polymerization……………………………………………………..………139 4.3. Comparison of tensile properties of nanofiber matrices: PEU, PCL, PLGA, gelatin, cartilage and skin. Nanofibers of PEU, PCL, PLGA, and gelatin are randomly oriented. PEU fibers’ diameter: 350-500 nm; PCL and gelatin fibers’ diameter: 10-1000 nm; PLGA fibers’ diameter: 500-800 nm………………………………………………148 5.1. Molecular mass data of polymers. Mn: number average molecular weight; PDI: polydispersity index. Mn and PDI were calculated from polystyrene standards………………………………………………………………………..…170 6.1. Thickness of Spinning coated polyester films…………………………………….199 6.2. Summary of (a) QCM frequency shift (△f) after peptide conjugation to mono- functionalized polymers surface, (b) Amount of covalently bound RGD calculated from △f based on Sauerbrey model, (c) reaction efficiency was calculated by the ratio between reacted functional groups and the whole amount in entire film; (d) change of contact angle (△θ) after peptide conjugation……………………………………..206 ix LIST OF FIGURES Figure Page 1.1. Shear strength of SR-PGA rods after implantation in subcutis of rabbits. Rod sizes: (○) 1.5 x
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