Poly(3-hydroxyalkanoate)-derived amphiphilic graft copolymers for the design of polymersomes

Institut de Chimie et des Matériaux Paris-Est (ICMPE), Systèmes Polymères Complexes, UMR CNRS 7182, 2-8 rue Henri Dunant, 94320 Thiais, France.
Chemical Communications (Impact Factor: 6.83). 04/2012; 48(43):5364-6. DOI: 10.1039/c2cc30482a
Source: PubMed


Amphiphilic graft copolymers composed of biocompatible bacterial poly(3-hydroxyalkanoate) and poly(ethylene glycol) have been synthesized by thiol-ene addition. They were demonstrated to form well-defined nanoscale vesicles in water by cryo-transmission electron microscopy.

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    • "We recently reported their chloride derivatives [39] and some graft copolymers with poly (methyl methacrylate) and polystyrene [40] [41]. Cross-linking of the unsaturated PHAs was also successfully achived [42e44].The well-known thiol-ene click reaction [45e52] was also used to prepare PHOU-g-polyethylene glycol amphiphilic graft copolymers in order to synthesis multi compartment micelles [53] [54]. In this manner, the modified PHAs with pendant grafts via thiol-ene click reactions by using 2-perfluorooctyl-1- ethanethiol and PEG 550eSH in the presence of 2, 2'-azo-bis isobutyronitrile was accomplished. "
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    ABSTRACT: Biodegradable polymers gained worldwide attention among researchers because of environmental and petroleum reserve limitation issues. In this manner, poly (3-hydroxyalkanoate)s, PHAs, are very useful materials from the point of this view. They can be easily obtained by using several bacteria from renewable substrate such as sugar, plant oils and as well as synthetic chemicals. The improvement of their mechanical properties and enhance hydrophilic character are still main challenge of the polymer scientists. Herein we report the thiol-ene photo click reactions of the unsaturated medium chain length PHAs produced by using Pseudomonas oleovorans from 10-undecenoic acid, octanoic acid and/or soybean oily acids that are coded as poly(3-hydroxy undecenoate) (PHU), poly(3-hydroxy octanoate-co-undecenoate) (PHOU) and poly(3-hydroxy octanoate-co-soybean oil polymer) (PHOSy), respectively, in order to obtain their hydroxyl and carboxyl derivatives. The molecular weights of the modified PHAs obtained in this work were the same as those of the starting PHAs. Structural analysis of the PHA derivatives was performed by using 1H-, 13C, HMBC and HSQC NMR techniques. Melting and glass transitions of the hydroxyl and carboxyl derivatives of the microbial polyesters were found to be relatively higher than that of the starting unsaturated PHAs.
    Polymer Degradation and Stability 05/2015; 119. DOI:10.1016/j.polymdegradstab.2015.04.024 · 3.16 Impact Factor
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    ABSTRACT: This contribution critically reviews some recent developments on the chemical modification and macromolecular engineering of poly(3-hydroxyalkanoate)s (PHAs) with a specific focus on typical examples from our group. Unsaturated PHAs were chemically modified via the transformation of pendant double bonds into carboxylic acid, hydroxyl or alkyne groups. Moreover, these reactive side functions could be used for further grafting biocompatible oligomers based on hydrolyzable polylactide (PLA) or poly(ε-caprolactone) (PCL) and hydrophilic poly(ethylene glycol) (PEG). Additionally, PHA-based block copolymers with a PLA, PCL or PEG segment were synthesized by ring-opening polymerization or ?click? chemistry using a suitably functionalized PHA building block.
    11/2012: chapter 12: pages 187-199; American Chemical Society., ISBN: 0841228221
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    ABSTRACT: Poly (3-hydroxyalkanoates) are natural aliphatic polyesters produced and accumulated by many bacteria as carbon and energy supply. They consist of β-hydroxy ester units, with pendant side chains of different lengths that can be functionalized. Thanks to their biodegradability and biocompatibility, they are promising polymers for biomedical applications, especially for controlled drug delivery systems. In this context, we aimed to synthesize PHA-based amphiphilic copolymers with different molecular architectures, and to study their self-assembly in water. First, a simple and straightforward method using click chemistry has been used to graft poly(ethylene glycol) (PEG) oligomers. A series of well-defined diblock copolymers PHA-b-PEG has thus been synthesized using copper-catalyzed azide-alkyne cycloaddition (CuAAC). Medium chain length PHA-based diblock copolymers have shown their ability to self-assemble into stable micelles having very low critical micelle concentrations. Afterwards, amphiphilic graft copolymers PHOU-g-PEG have been synthesized using thiol-ene addition. In this case, cryo-electron microscopy (cryo-TEM) analysis revealed that graft copolymers self-assembled into vesicular morphologies, i.e. in polymersomes. Finally, the synthesis of amphiphilic graft copolymers bearing perfluorinated chains PHOU-g-(F;PEG) was performed. After aqueous self-assembly, cryo-TEM shown the formation of multicompartment micelles, i.e. with a core displaying segregated hydrophobic and fluorophilic domains. Moreover, these multicompartment micelles have shown their cytocompatibility
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