Search results for "Bioengineering"
showing 10 items of 1963 documents
Poly(carbonate) copolymers with a tailored number of hydroxyl groups from glycidyl ethers and CO2
2014
Functional poly(carbonate)s with multiple hydroxyl functionalities have been prepared by copolymerization of carbon dioxide (CO2) with glycidyl methyl ether (GME) and benzyl glycidyl ether (BGE) in various ratios, using a diethylzinc–pyrogallol catalyst system. Subsequent catalytic hydrogenation was employed for removal of the benzyl protecting groups at the polymer backbone. A series of copolymers with varying comonomer fractions from 0 to 100% was obtained. The copolymers possessed a broad range of molecular weights from 9000 to 30 000 g mol−1 and showed polydispersities Mw/Mn between 2.4 and 3.6. The materials were characterized via1H and 13C NMR, SEC and differential scanning calorimetr…
New Perspectives of HPMA-based Copolymers Derived by Post-Polymerization Modification
2014
Poly[N-(2-hydroxypropyl) methacrylamide] (HPMA) was one of the first polymers applied as polymer drug conjugate in the clinics. Since then many attempts have been made to expand the functionality of HPMA-based copolymers from advanced synthetic pathways to multiple biomedical applications. This Feature Article highlights multifunctional HPMA based copolymers prepared by controlled radical polymerization and subsequent post-polymerization modification of activated ester precursor polymers via aminolysis. This approach combines precise control of the polymer's microstructure (molecular weight, dispersity, block copolymer formation, end group functionalization) with an easy introduction of var…
“Clickable PEG” via anionic copolymerization of ethylene oxide and glycidyl propargyl ether
2017
A straight forward synthesis of poly(ethylene glycol) (PEG) with multiple alkyne groups distributed along the polymer chain is introduced. Direct access to clickable PEG is achieved by the monomer-activated anionic ring-opening copolymerization (AROP) of ethylene oxide (EO) with glycidyl propargyl ether (GPgE). Notably for successful polymerization no protection of the alkyne unit is required owing to the mild reaction conditions. Defined PEG-co-PGPgE and PGPgE (co)polymers with PDIs of 1.18–1.60 and molecular weights of Mn = 3000–9500 g mol−1 were prepared. In situ1H NMR kinetic studies revealed remarkably disparate reactivity ratios of rEO = 14.8 and rGPgE = 0.076, representing a pronounc…
Microstructure analysis of biocompatible phosphoester copolymers
2013
Copolymers with varying compositions of 2-ethoxy-2-oxo-1,3,2-dioxaphospholane (EEP) and 2-ethoxy-4-methyl-2-oxo-1,3,2-dioxaphospholane (EMEP) have been synthesized via 1,5,7-triazabicyclo[4.4.0]dec-5-ene-catalyzed anionic ring-opening polymerization. The molecular weights and comonomer ratios were well controlled and polymers with reasonable molecular weight distributions (<1.5) were obtained in all cases. The copolymers were investigated by 1H and 31P NMR spectroscopies to determine the underlying microstructure via detailed dyad analysis. The copolymers were found to be nontoxic to HeLa cells. Furthermore, the obtained copolymers of EEP and EMEP show thermoresponsive properties, i.e., exh…
Poly(phosphonate)-mediated Horner–Wadsworth–Emmons reactions
2015
A novel, general protocol for a polymer-mediated Horner–Wadsworth–Emmons (HWE) reaction is reported. The polyvalent polymeric reagent was prepared via acyclic diene metathesis (ADMET) polymerization. Homo- and copolymers of reactive poly(phosphonate)s with molecular weights up to 40 000 g·mol−1 and molecular weight dispersities Đ < 2 were successfully synthesized. Subsequent application of these polymers in the HWE reaction to prepare a library of aromatic α,β-unsaturated ketones (chalcons) has proven to be an efficient synthetic pathway to minimize purification efforts, as the polymeric side-product can be removed by simple precipitation. In this paper we also demonstrate for the first tim…
RAFT-polymerized poly(hexafluoroisopropyl methacrylate)s as precursors for functional water-soluble polymers
2014
Post-polymerization modification of well-defined precursor polymers is a versatile tool to obtain multifunctional water-soluble polymers that cannot be synthesized by common polymerization techniques. For the first time, 1,1,1,3,3,3-hexafluoroisopropyl methacrylate (HFIPMA) based homo and block copolymers were synthesized via RAFT polymerization to provide precise precursors for the post-polymerization modification of the 1,1,1,3,3,3-hexafluoroisopropyl ester side chains with water-soluble amines (methoxy tri(ethylene glycol) amine, 2-hydroxypropyl amine and 3-(dimethylamino)-1-propylamine). Sequential aminolysis using Oregon Green cadaverine first followed by 2-hydroxypropyl amine enables …
Evaluating chemical ligation techniques for the synthesis of block copolypeptides, polypeptoids and block copolypept(o)ides: a comparative study
2015
In this work, we describe the synthesis of block copolypeptides, polypeptoids and block copolypept(o)ides by chemical ligation techniques. Polysarcosine (PSar), poly(N-e-trifluoroacetyl-L-lysine) (PLys(TFA)) and poly(γ-benzyl-L-glutamate) (PGlu(OBzl)) homopolymers of different polarities and end group functionalities but with similar average degrees of polymerization (Xn = 50 and 100) could be obtained by ring opening polymerization (ROP) of α-amino acid N-carboxyanhydrides (NCA) and postpolymerization modification reactions. In the next step, these polymers were applied to copper(I)-catalyzed azide–alkyne coupling (CuAAC), strain-promoted azide–alkyne coupling (SPAAC) and native chemical l…
Polymerization of long chain alkyl glycidyl ethers: a platform for micellar gels with tailor-made melting points
2018
Controlled polymerization of long-chain alkyl glycidyl ethers (AlkGE) under anionic ring opening polymerization conditions is enabled by the addition of a crown ether (18-crown-6, K+). Homopolymers with molecular weights in the range of 4000 to 9000 g mol−1 and side chain melting temperatures of 14 °C (C12-AlkGE) and 43 °C (C16-AlkGE), respectively were synthesized. Furthermore, a series of amphiphilic ABA polyether triblock copolymers with polyethylene glycol (PEG) as the hydrophilic central block (Mn = 6k, 10k, and 20k g mol−1) with total molecular weights in the range of 7000 to 28 000 g mol−1 and narrow dispersity (1.12 to 1.34) were prepared. Separate melting endotherms of the triblock…
Functional PEG-based polymers with reactive groups via anionic ROP of tailor-made epoxides
2012
In this review article functional epoxide monomers that are suitable for controlled ring-opening polymerization (ROP) are discussed. Functional epoxides possess reactive groups, which either are directly accessible or carry suitable protective groups that can be removed in a facile one-step reaction after polymerization. The methods used to obtain linear, functional aliphatic polyethers rely on living polymerization techniques for the synthesis of well-defined structures. Materials properties, such as thermo-responsive behavior in combination with different functional groups that can be addressed selectively, render these novel materials interesting for a variety of applications.
One-step synthesis of multi-alkyne functional hyperbranched polyglycerols by copolymerization of glycidyl propargyl ether and glycidol
2013
By copolymerization of glycidol with the alkyne-containing oxirane monomer glycidyl propargyl ether (GPE), hyperbranched polyglycerol (hbPG) with a defined number of alkyne functionalities (up to 38%) can be obtained in a one-step procedure. The number of alkynes can be adjusted by the glycidol/GPE ratio to provide multi-alkyne functional hbPGs, maintaining the highly branched polyether structure. Interestingly, the acidic proton of the alkyne moiety does not interfere with the proton exchange mechanism during the polymerization of glycidol. By specific modification of the synthesis procedure, crosslinking reactions can be suppressed. The polymers exhibit molecular weights ranging from 1800…