0000000000231070
AUTHOR
Kerstin Niederer
Catechol Acetonide Glycidyl Ether (CAGE): A Functional Epoxide Monomer for Linear and Hyperbranched Multi-Catechol Functional Polyether Architectures
A protected catechol-containing epoxide monomer, catechol acetonide glycidyl ether (CAGE), is introduced. CAGE is conveniently obtained in three steps and enables the incorporation of surface-active catechol moieties into a broad variety of hydrophilic and biocompatible polyether architectures by copolymerization. Via acidic cleavage of the acetal protecting groups, the polymer-attached catechol functionalities are liberated and available for surface attachment or metal complexation. CAGE has been copolymerized with ethylene oxide and glycidol to obtain both linear poly(ethylene glycol) and hyperbranched polyglycerol copolymers, respectively, with multiple surface-adhesive catechol moieties…
Combining oxyanionic polymerization and click-chemistry: a general strategy for the synthesis of polyether polyol macromonomers
We describe a synthetic pathway to tailor-made amphiphilic macromonomers by a combination of anionic ring-opening polymerization and copper-catalyzed azide–alkyne cycloaddition (CuAAC). Linear polyglycerol and poly(glyceryl glycerol) were synthesized in a controlled manner by anionic ring-opening polymerization of ethoxyethyl glycidyl ether or isopropylidene glyceryl glycidyl ether, respectively, with narrow and monomodal molecular weight distributions (Mw/Mn < 1.20) and molecular weights ranging from 850 g mol−1 to 2500 g mol−1. After end-capping with propargyl bromide and removal of the protecting groups, the hydrophilic precursors were quantitatively clicked to a series of hydrophobic az…
Tailoring Novel PTFE Surface Properties: Promoting Cell Adhesion and Antifouling Properties via a Wet Chemical Approach
Many biomaterials used for tissue engineering applications lack cell-adhesiveness and, in addition, are prone to nonspecific adsorption of proteins. This is especially important for blood-contacting devices such as vascular grafts and valves where appropriate surface properties should inhibit the initial attachment of platelets and promote endothelial cell colonization. As a consequence, the long-term outcome of the implants would be improved and the need for anticoagulation therapy could be reduced or even abolished. Polytetrafluoroethylene (PTFE), a frequently used polymer for various medical applications, was wet-chemically activated and subsequently modified by grafting the endothelial …
Wet Chemistry and Peptide Immobilization on Polytetrafluoroethylene for Improved Cell-adhesion
Endowing materials surface with cell-adhesive properties is a common strategy in biomaterial research and tissue engineering. This is particularly interesting for already approved polymers that have a long standing use in medicine because these materials are well characterized and legal issues associated with the introduction of newly synthesized polymers may be avoided. Polytetrafluoroethylene (PTFE) is one of the most frequently employed materials for the manufacturing of vascular grafts but the polymer lacks cell adhesion promoting features. Endothelialization, i.e., complete coverage of the grafts inner surface with a confluent layer of endothelial cells is regarded key to optimal perfo…
Conducting Polymer with Orthogonal Catechol and Disulfide Anchor Groups for the Assembly of Inorganic Nanostructures
To combine several inorganic components with organic material in a controlled special and permanent manner still remains a difficult issue. Two specifically functionalized block copolymers were synthesized separately and combined in a second step. A heterofunctional poly(ethylene glycol) (PEG) block copolymer bearing a single amino unit, a short PEG spacer, and multiple catechol functionalities was obtained via anionic ring-opening polymerization (AROP). Using the reversible addition–fragmentation chain transfer (RAFT) radical polymerization technique, a semiconducting block copolymer with carbazole side groups was obtained. The second polyacrylate block contained reactive ester groups and …
Polymerization of Ethylene Oxide, Propylene Oxide, and Other Alkylene Oxides: Synthesis, Novel Polymer Architectures, and Bioconjugation.
The review summarizes current trends and developments in the polymerization of alkylene oxides in the last two decades since 1995, with a particular focus on the most important epoxide monomers ethylene oxide (EO), propylene oxide (PO), and butylene oxide (BO). Classical synthetic pathways, i.e., anionic polymerization, coordination polymerization, and cationic polymerization of epoxides (oxiranes), are briefly reviewed. The main focus of the review lies on more recent and in some cases metal-free methods for epoxide polymerization, i.e., the activated monomer strategy, the use of organocatalysts, such as N-heterocyclic carbenes (NHCs) and N-heterocyclic olefins (NHOs) as well as phosphazen…