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Thesis M Ten Breteler Stereoselective Polymerization of Lactones. Properties of Stereocomplexed PLA Building Blocks M.R. ten Breteler 2010 Stereoselective Polymerization of Lactones. Properties of Stereocomplexed PLA Building Blocks ISBN: 978-90-365-3045-3 M.R. ten Breteler STEREOSELECTIVE POLYMERIZATION OF LACTONES. PROPERTIES OF STEREOCOMPLEXED PLA BUILDING BLOCKS PROEFSCHRIFT ter verkrijging van de graad van doctor aan de Universiteit Twente, op gezag van de rector magnificus, prof. dr. H. Brinksma, volgens besluit van het College voor Promoties in het openbaar te verdedigen op donderdag 10 juni 2010 om 16:45 uur door Mark Randolf ten Breteler geboren op 15 september 1979 te Haaksbergen Dit proefschrift is goedgekeurd door: Promotor: Prof. dr. J. Feijen Assistant promotor: Dr. P.J. Dijkstra Committee Chairman: prof. dr. G. van der Steenhoven University of Twente Promotor: prof. dr. J. Feijen University of Twente Assistant Promotor: dr. P.J. Dijkstra University of Twente Members: prof. dr. J.J.L.M. Cornelissen University of Twente prof. dr. D.W. Grijpma University of Twente prof. dr. W.E. Hennink University of Utrecht prof. dr. ir. J.C.M. van Hest Radboud University prof. dr. Ch. Jérôme University of Liège prof. dr. G. van Koten University of Utrecht prof. dr. A.-J. Schouten University of Groningen The research described in this thesis was financially supported by Technologiestichting STW. Stereoselective Polymerization of Lactones. Properties of Stereocomplexed PLA Building Blocks Ph.D.Thesis with references; summary in English and Dutch University of Twente, the Netherlands ISBN: 978-90-365-3045-3. Copyright © 2010 by M.R. ten Breteler All rights reserved. Printed by Ipskamp Drukkers B.V., Enschede, the Netherlands, 2010. Preface P| In all these years in which I’ve been working towards finishing this thesis, I’ve always had in mind to write a limited preface, without elaborations on how I’ve spend my day- breaks, enjoyed all kinds of parties, or dragged myself trough ‘desperate’ moments. And thus, a short preface it will be, in which I’d nevertheless would like to thank a number of people, whose help was invaluable in creating this thesis.. I’d like to thank my promotor, Jan Feijen, and assistant promotor, Piet Dijkstra, for the opportunity of doing my promotion within their group, for their endless time and help in corrections (especially Piet) and their supervision throughout the years. A great part of the ‘tutoring’ was in the capable hands of Zhiyuan, for which I’d like to thank him. During my promotion I’ve had the pleasure of working with collegues from other universities, and some results are mentioned in this thesis. I’d like to express my thanks to prof. Gerard van Koten, Johann Jastrzebski, Henk Kleijn and Rainer Wechselberger for their contributions to chapter 3 and 4, Anja Palmans and Joris Peeters for their contribution to chapter 5 and Linda Havermans-van Beek for her contribution to chapter 8. I enjoyed working with Rainer Kränzle and Mark Leemhuis, and was fortunate to walk along the ‘educational highway’ with a number of students. Dimitri, Erwin, Roel, Martha, Marloes, Kicki and Lucas: thanks for your contributions. Much obliged to the ‘labmates’ – in particular Priscilla (who ‘lured’ me into the group), Ingrid and Christine, who were essential discussion partners, and Marc, for his assistance in numerous experiments. A special thanks is in place for Zlata and Karin, who have helped out in many ways. And of course many thanks to all my PBM and other collegues at the university; I will not mentioned names here, because I’m bound to forget some. Last but not least, I’d like to thank my friends, family - especially my parents, Bart and Phoebe, for all their love and support. My greatest thanks go to my wife Kim, whose endless patience and gentle encouragements turned out to be the most important as well as most successful ingredient in finishing this thesis. Mark Contents C| Chapter 1 General Introduction 1 Chapter 2 The Synthesis of Polyesters by Controlled Ring-Opening Polymerization and Their Use in Biomedical Applications 9 Chapter 3 NO-Bidentate and NON-Tridentate Zinc Alkoxides for the Controlled Ring-Opening Polymerization of Lactides 43 Chapter 4 Controlled Ring-Opening Polymerization of Lactides by Thiophenolate-Based Zinc Catalysts 65 Chapter 5 Ring-Opening Polymerization of Substituted ε-Caprolactones Using a Chiral (Salen) AlOiPr-Complex 85 Chapter 6 Synthesis and Ring-Opening of γ-Boc-Amino-ε-Caprolactone 103 Chapter 7 Synthesis and Thermal Properties of Heterobifunctional PLA Oligomers and Their Stereocomplexes 125 Chapter 8 Stereocomplexed Hydrogels from Dextrans Grafted with PLA Amines 149 Summary 175 Samenvatting 179 Curriculum Vitae 183 General Introduction 1| Hydrogels have found numerous applications in biomedical technology such as tissue engineering and drug delivery systems.1-5 Hydrogels resemble natural living soft tissues and in general their high water content renders them highly biocompatible. When used as implant materials hydrogels have to be preferably biodegradable, thus allowing the replacement of the material in time by a new extracellular matrix produced by surrounding or in the hydrogel incorporated cells. Hydrogels that are biofunctional, e.g. by the incorporation of growth factors to guide cellular behavior, receive a lot of attention in current research. In biomedical technology either preformed or in situ generated hydrogels may be used. Injectable, in situ-forming hydrogels offer the advantage of ease of cell seeding or incorporating drugs and the ability to readily fill irregularly shaped defects.6-8 Moreover, this method, which involves a simple injection of hydrogel precursor solutions that crosslink into a hydrogel, makes invasive surgery unnecessary. Hydrogel networks are insoluble in water, due to the presence of chemical crosslinks or physical crosslinks, such as hydrogen bonds, hydrophobic interactions, or ionic interactions.9 Physical crosslinking generally proceeds under mild conditions, which allows an easy immobilization of e.g. therapeutic proteins and cells. However, in general physically crosslinked hydrogels are mechanically weak and degrade faster than chemically crosslinked hydrogels. Well known biodegradable hydrogels are amphiphilic block copolymers of hydrophobic aliphatic polyesters and hydrophilic polymers like poly(ethylene oxide) or polysaccharides.10-12 Aliphatic polyesters like poly(lactide)s (PLA) and lactide copolymers are nontoxic to the human body and widely applied as biomedical materials. In recent years stereocomplexation or stereocomplex formation between enantiomeric PLAs (poly(L-lactide) and poly(D-lactide)) in amphiphilic block or graft copolymers has been developed as a method to prepare physically crosslinked injectable hydrogels.8, 11-14 1 cell Proteoglycan Hyaluronic acid collagen Glycosaminoglycans Figure 1. Schematic representation of the extracellular matrix in articular cartilage (middle), containing the typical ‘brushed brush’ structure of proteoglycans attached to a hyaluronic acid backbone. Tissue regeneration is a promising methodology for the repair of tissues like cartilage.15 The ECM of natural cartilage contains approximately 25% of proteoglycans.16 These proteoglycans are brush-like structures, composed of several different glycosaminoglycans (GAGs) (polysaccharides), and covalently attached to a single polypeptide chain. In the presence of hyaluronic acid, higher aggregates of aggrecans can be formed, resulting in ‘brushed brushes’ (Figure 1). In general, the GAGs are highly negatively charged, and therefore able to bind large amounts of water. In combination with collagen, which provides mechanical strength, these extracellular matrix (ECM) components provide the characteristic viscoelastic properties of cartilage tissue. In designing hydrogels for tissue engineering, the structure and properties of the natural ECM can be used as guidance. Aim of the Study and Hydrogel Design In this study, we have focused on different aspects of biodegradable polymers that may be used in the development of hydrogels for tissue engineering. Building blocks with a predetermined structure, that could be combined to give temporal in situ-forming hydrogels, were designed and finally applied in graft copolymers. We based our design on the structure of the aggrecans as found in the natural ECM of cartilage. 2 The brush-like structures should form upon self-assembly after mixing of the individual components, and gelation times should be tunable. By applying biodegradable and water soluble components that can be removed from the body by natural pathways biocompatible hydrogels are expected. injectable hydrogel cartilage defect gel filled defect . Figure 2. Schematic representation of the filling of cavities by injectable, in-situ forming hydrogels, based on complex formation between complementary segments attached to a polymer backbone. The aims of the research described in this thesis are to study (1) potential biocompatible catalyst systems that can induce stereoselective polymerization of lactides and substituted caprolactones and (2) to apply these systems in the preparation of new polyesters bearing functional groups. Such polyesters can be studied in the preparation of self-assembling moieties, for application in tissue engineering. The self-assembly of the individual components into hydrogels is based on the concept of stereocomplex formation between 3 poly(lactic acid) (PLA) segments of opposing chirality (Figure 2). Thus, applying biodegradable
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