Functional modification of biodegradable polyesters through a chemoselective approach: application to biomaterial surfaces

Abstract

This paper presents an overview of functional modifications of synthetic aliphatic polyesters and a new synthetic route to graft functional moieties onto the polyester backbone by a chemoselective approach. Aminooxy groups react efficiently and selectively with ketones or aldehydes to form oxime linkages under mild reaction conditions without catalysts, even in the presence of other functional groups. Chemoselective coupling of aminooxy‐terminated poly(ethylene oxide) (PEO) onto ketone‐bearing poly(ε‐caprolactone) (PCL) was exploited to prepare comb‐shaped copolymers that exhibit cell resistance when the PEO content is above 30 wt%. The free hydroxyl groups of PEO chain ends allowed further incorporation of cell signaling peptides including the sequence RGD. The results show chemoselective coupling to be a promising general route for introducing functional pendant groups onto most polyesters obtained by ring‐opening polymerization without backbone degradation. Copyright © 2006 Society of Chemical Industry

A functionalizable polyester with free hydroxyl groups and tunable physiochemical and biological properties

“…The synthetic strategy is versatile and can be used with other diacids and diepoxides to yield various linear functionalizable polyesters. Compared to other current approaches to functionalized polyester [8-10, 15, 16], it is simpler and more efficient.…”

“…The state of the art in the synthesis of functionalizable polyesters has been well presented in several recent reviews [8-10, 15, 16]. As mentioned in these reviews, chemical preparation of functionalizable polyesters is difficult because it usually involves a complex multistep synthetic route with a low overall yield.…”

PEGylated polymers for medicine: from conjugation to self-assembled systems

“…Recent examples of aliphatic polyesters with pendent reactive unsaturated groups, prepared by ring-opening polymerization of functionalized lactones, appear promising for subsequent grafting chemistry that proceeds cleanly, revealing little-to-no polyester degradation. [76][77][78][79][80][81][82] For example, pendent allyl groups serve as precursors to hydroxyl, halide, and silyl groups, and thiol-ene click chemistries, that alter the solubility, physical properties, and degradation rates of the polymers. 76,83 Pendent cyclopentene groups can be converted to 1,2-diols to give polyesters with good shelf-stability, and that can be PEGylated, for example, by esterification of the hydroxyl groups with PEG-succinic acid ester derivatives.…”

New promising biodegradable polyesters derived from poly((R,S)-3,3-dimethylmalic acid) for cardiovascular applications

“…It has the advantage of being metabolized in malic acid which is found in the Krebs cycle and is completely biodegraded in carbon and water [59]. The PMLA and benzyl derivative (PMLABn) are known since the late 1970s but their synthesis and applications are limited [59][60][61][62][63][64][65]. Since these years, all PMLA derivatives were obtained by ring-opening polymerization of various β-substituted β-lactones themselves synthesized from either malic acid or aspartic acid in several stages [60,[66][67][68].…”