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See detailContribution of "click chemistry" to the macromolecular engineering of aliphatic polyesters
Riva, Raphaël ULg; Schmeits, Stephanie ULg; Croisier, Florence ULg et al

Poster (2010, July 13)

In this work, click chemistry was sucessfully applied to the chemical modification of aliphatic polyesters with the purpose to tailor their physical properties. The developped strategy was then applied to ... [more ▼]

In this work, click chemistry was sucessfully applied to the chemical modification of aliphatic polyesters with the purpose to tailor their physical properties. The developped strategy was then applied to the synthesis of materials, such as smart partially degradable hydrogels or antibacterial polyesters. Last, the synthesis of amphiphilic star-shaped copolyester was investigated. [less ▲]

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See detailFirst example of “click” copper(I) catalyzed azide-alkyne cycloaddition in supercritical carbon dioxide: Application to the functionalization of aliphatic polyesters
Grignard, Bruno ULg; Schmeits, Stephanie ULg; Riva, Raphaël ULg et al

in Green Chemistry (2009), 11

The modification of aliphatic polyesters by the copper(I) catalyzed azide-alkyne cycloaddition (CuAAC) was successfully implemented in supercritical carbon dioxide (scCO2). Due to the remarkable ... [more ▼]

The modification of aliphatic polyesters by the copper(I) catalyzed azide-alkyne cycloaddition (CuAAC) was successfully implemented in supercritical carbon dioxide (scCO2). Due to the remarkable properties of scCO2, the CuAAC reaction turned out to be quantitative even though the aliphatic polyesters used in this work were insoluble in scCO2. Interestingly enough, the conditions were mild enough to prevent polymer degradation from occurring and finally, efficient removal of the catalyst (>96%) was achieved by scCO2 extraction. [less ▲]

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See detailNew developments in the functionalization of aliphatic polyesters by "click" copper-catalyzed azide-alkyne cycloaddition
Lecomte, Philippe ULg; Riva, Raphaël ULg; Schmeits, Stephanie ULg et al

Conference (2009, June 03)

Nowadays, biodegradable and biocompatible aliphatic polyesters are widely used as environmentally friendly thermoplastics and biomaterials. Nevertheless, the absence of any pendant functional group is a ... [more ▼]

Nowadays, biodegradable and biocompatible aliphatic polyesters are widely used as environmentally friendly thermoplastics and biomaterials. Nevertheless, the absence of any pendant functional group is a severe limitation for the development of novel applications. Our strategy aiming at functionalizing aliphatic polyesters relies on the “click” copper-catalyzed cycloaddition (CuAAC) of alkynes duly substituted by functional groups or even chains onto PCL bearing pendant azides. The aliphatic polyesters bearing pendant azides have been very efficiently synthesized by a straightforward approach, which relies on the ring-opening copolymerization of αClεCL (or γBrεCL) and εCL (or lactide) followed by reaction with sodium azide to convert pendant chlorides or bromides into azides. The alternative reported by Emrick et al. is based on the CuAAC reaction of azides substituted by any functional group onto copolyesters of poly(ε-caprolactone) bearing pendant alkynes. Interestingly enough, Emrick et al. carried out the CuAAc reaction in water at 80°C. Unfortunately, it turned out, at least in our hands, that these conditions can not be extended to the derivatization of more sensitive aliphatic polyesters because degradation was then unavoidable. Nevertheless, we found out that degradation can be minimized whenever the CuAAC reaction is carried out in an organic solvent at lower temperature. Typically, the CuAAC reaction was carried out in DMF or THF at 35°C. Recently, it was shown that supercritical carbon dioxide can be used as a more environmentally friendly solvent than DMF or THF. The contamination by catalytic residues of aliphatic polyesters functionalized by the CuAAC reaction is a severe limitation in view of future applications, especially in the biomedical field. In the last part of this talk, a special attention will be paid on our current efforts to get rid of copper residues. [less ▲]

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See detailFunctionalization of aliphatic polyesters by “click chemistry” in supercritical carbon dioxide
Grignard, Bruno ULg; Schmeits, Stephanie ULg; Riva, Raphaël ULg et al

Poster (2009, May 14)

The combination of ring-opening polymerization of lactones and “click” copper-catalyzed Huisgen’s [3+2] cycloaddition is known to be a very efficient strategy for the functionalization of poly(ε ... [more ▼]

The combination of ring-opening polymerization of lactones and “click” copper-catalyzed Huisgen’s [3+2] cycloaddition is known to be a very efficient strategy for the functionalization of poly(ε-caprolactone) (PCL) and poly(lactic acid) (PLA). Whenever the “click” reaction occurs in an organic solvent (THF or DMF), at relatively low temperature (35°C) and within short reaction time (2 hours), no significant degradation of polyester chains is detected. This strategy was implemented in previous works to graft alkynes substituted by different functional groups, such as hydroxyl, tertiary amines, acrylates or ammonium salts onto azide-functionalized PCL. Moreover, this approach was previously extended to the synthesis of grafted copolymers, either by the grafting of omega-alkyne-PEO onto azide-functionalized aliphatic PLA or PCL (“grafting onto” technique) either by grafting of an ATRP initiator followed by the polymerization of vinyl monomers, such as styrene (“grafting from” technique). These functionalized aliphatic polyesters are promising materials for the development of new biomedical devices. In this work, novel conditions were implemented for the “click” reaction in order to avoid the use of organic solvents and to limit the amount of catalyst remnants in functionalized aliphatic polyesters. Toward this end, if was found that the functionalization by “click” chemistry can be efficiently carried out in supercritical carbon dioxide rather than in THF or DMF. For that sake, it turned out necessary to synthesize a perfluorinated polyamine in order to solubilize the catalyst in supercritical carbon dioxide. Aliphatic polyesters are not soluble in supercritical carbon dioxide. Nevertheless, even under heterogeneous conditions, the functionalization of aliphatic polyesters by “click” chemistry is quantitative. Interestingly enough, no degradation was observed. Last but not least, the copper catalyst was easily removed by supercritical fluid extraction leading to a very low content of residual copper in the final copolyester. [less ▲]

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See detailSynthesis of novel functional aliphatic polyesters by association of ring-opening polymerization and click chemistry
Lecomte, Philippe ULg; Schmeits, Stephanie ULg; Riva, Raphaël ULg et al

Conference (2008, April 09)

Nowadays, biodegradable and biocompatible aliphatic polyesters are widely used as environmentally friendly thermoplastics and biomaterials. Nevertheless, the absence of any functional group along the ... [more ▼]

Nowadays, biodegradable and biocompatible aliphatic polyesters are widely used as environmentally friendly thermoplastics and biomaterials. Nevertheless, the absence of any functional group along the chain is a severe limitation for the development of new applications. Very recently, it was reported by Emrick et al. and by us that copper(I)-mediated 1,3-dipolar Huisgen's cycloaddition of alkynes and azides, the most widely used “click” reaction in the frame of macromolecular engineering, is very efficient to derivatize aliphatic polyesters. Due to the tolerance for many functional groups, cumbersome protection and deprotection steps are not needed. One main advantage of copper(I)-mediated Huisgen's cycloaddition compared to other reactions previously used to derivatize aliphatic polyesters relies on the mildness of the experimental conditions, which results in limited degradation. Our most recent results dealing with the combination of “click” chemistry and ring-opening polymerization towards functional PCL and PLA, networks, graft and hyperbranched copolymers will be highlighted. [less ▲]

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See detailSynthesis of novel functional aliphatic polyesters
Schmeits, Stephanie ULg; Riva, Raphaël ULg; Jérôme, Christine ULg et al

in Polymer Preprints (2008), 49(1), 222-223

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See detailMacromolecular engineering of cyclic aliphatic polyesters by ring-opening polymerization and "click" chemistry
Lecomte, Philippe ULg; Li, Haiying; Riva, Raphaël ULg et al

Conference (2007, September 04)

The last decades have witnessed a steadily increasing progress in the macromolecular engineering of the main families of synthetic polymers. Ring-shaped copolymers show a unique topology due to the ... [more ▼]

The last decades have witnessed a steadily increasing progress in the macromolecular engineering of the main families of synthetic polymers. Ring-shaped copolymers show a unique topology due to the absence of any chain-end and exhibit distinct properties from their linear counterparts, such as glass transition temperature, order-disorder transition, reduced viscosity, lower hydrodynamic volumes. This communication aims at reporting on a novel route to biodegradable cyclic polyesters. Our strategy is based on the work of Prof. Kricheldorf who initiated the ring-opening polymerization of ε-caprolactone by cyclic tin dialkoxides, e.g., 2,2-dibutyl-2-stanna-1,3-dioxepane (DSDOP) in order to obtain “living” macrocyclic PCL, still containing two endocyclic tin-oxygen bonds. In this work, the resumption of polymerization by a few units of ε-caprolactone substituted by an acrylic unit, e.g., 1-(2-oxooxepan-3-yl)ethyl prop- 2-enoate, followed by intramolecular photo-crosslinking of pendant unsaturations and finally by hydrolysis gave rise to macrocyclic PCL. As a rule, this strategy is very well-suited for the synthesis of high molecular weight PCL. Moreover, tin alkoxides were kept untouched after the cross-linking step and remained thus available for further macromolecular engineering. The process was extended to the synthesis of other architectures such as sun-shaped, two-tail tadpoleshaped, and eight-shaped copolyesters. The second part of the lecture, it will be shown that the copper(I)-catalyzed Huisgen’s [3+2] cycloaddition, which is the most popular “Click" reaction, is very efficient to graft alkynes, duly substituted by functional groups or chains, onto aliphatic copolyesters bearing pendant azides. Interestingly enough, mild conditions were found and no degradation was observed during the “click” derivatization of copolyesters of PCL. The “click” reactions of alkynes onto pendant azides of copolyesters of PLA, by far more sensitive than PCL, was also successfully carried out without any detectable degradation. ”Click” chemistry is very versatile because this reaction was successfully implemented to graft functional groups or chains directly onto ω-azido-ε-caprolactone, without any ring-opening of the lactone, in order to make available a new range of functional caprolactones. Finally, the “click” grafting of PEO onto the tails of tadpole-shaped copolymers will be shown to be a route to amphiphilic copolymers with an original architecture. [less ▲]

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See detailContribution of "click" chemistry to the functionalization of aliphatic polyesters
Schmeits, Stephanie ULg; Riva, Raphaël ULg; Zednik, Jiri et al

Poster (2007, August 31)

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See detailMacromolecular engineering of cyclic aliphatic polyesters by ring-opening polymerization
Lecomte, Philippe ULg; Riva, Raphaël ULg; Li, Haiying et al

Conference (2006, September 24)

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See detailNew prospects for the grafting of functional groups onto aliphatic polyesters. Ring-opening polymerization of alpha- or gamma-substituted epsilon-caprolactone followed by chemical derivatization of the substituents
Lecomte, Philippe ULg; Riva, Raphaël ULg; Schmeits, Stephanie ULg et al

in Macromolecular Symposia (2006), 240

Recent progress in the synthesis of aliphatic polyesters, substituted by pendent functional groups, has been reviewed. Two main strategies have to be distinguished. The first route consists of the ring ... [more ▼]

Recent progress in the synthesis of aliphatic polyesters, substituted by pendent functional groups, has been reviewed. Two main strategies have to be distinguished. The first route consists of the ring-opening polymerization of F,caprolactone substituted by various functional groups, protected if needed, in alpha- or gamma-position. In a second strategy, the functional groups are grafted onto preformed polyesters chains in alpha-position of the carbonyl groups. alpha-chloro-epsilon-caprolactone is quite an interesting monomer because, after polymerization, the activated chloride can be easily derivatized by atom transfer radical addition and "click" chemistry, respectively. Similarly, gamma-acrylic-epsilon-caprolactone is precursor of (co)polyesters wellsuited to derivatization of the pendent double bonds by Michael addition. [less ▲]

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See detailCombination of ring-opening polymerization and "click" chemistry towards functionalization of aliphatic polyesters
Riva, Raphaël ULg; Schmeits, Stephanie ULg; Stoffelbach, François et al

in Chemical Communications (2005), (42), 5334-5336

Azide pendent groups of aliphatic polyesters have been derivatized into tertiary amines, ammonium salts and poly(ethylene oxide) grafts. The experimental conditions have been optimized (organic solvent ... [more ▼]

Azide pendent groups of aliphatic polyesters have been derivatized into tertiary amines, ammonium salts and poly(ethylene oxide) grafts. The experimental conditions have been optimized (organic solvent, 35 degrees C), such that the aliphatic polyesters are not degraded, including even poly(lactide) which is very sensitive to attack by weak nucleophiles. [less ▲]

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See detailSynthesis of new substituted poly(ε-caprolactone)s by comination of ring-opening polymerization, atom transfer radical addition and click reaction
Lecomte, Philippe ULg; Riva, Raphaël ULg; Schmeits, Stephanie ULg et al

Poster (2005, May 19)

During the last few years, a great research effort has been devoted to the synthesis of aliphatic polyesters, e.g. poly(ε-caprolactone) and polylactides. Indeed, their remarkable properties of ... [more ▼]

During the last few years, a great research effort has been devoted to the synthesis of aliphatic polyesters, e.g. poly(ε-caprolactone) and polylactides. Indeed, their remarkable properties of biodegradability and biocompatibility pave the way to many new applications in the biomedical field and as substitutes for non degradable polymers. In order to tailor the polyester properties, the grafting of functional groups along the polymer backbone is highly desirable. For the last few years, CERM has reported on the synthesis and the (co)polymerization of novel ε-caprolactones γ-substituted by various functional groups, e.g., ketal, ketone, olefin, protected alcohol and carboxylic acid. Nevertheless, the grafting of a specific functional group onto the aliphatic polyester backbone requires the synthesis of the parent substituted ε-caprolactone. There is accordingly a need for a strategy that would use a unique substituted ε-caprolactone, followed by derivatization by well-established reactions, so making available a wide range of pendent functional groups, polymeric or not. The derivatization reactions have however to be quantitative under mild conditions to prevent the aliphatic polyester from degrading. Moreover, these reactions must be compatible with the functional groups of interest, e.g., hydroxyl and carboxylic acid, in order to avoid the use of cumbersome protection/deprotection reactions. This communication aims at reporting that a-chloro-e caprolactone (αCLεCL) can be easily copolymerized with εCL into poly(αCLεCL-co-εCL) copolymers, which are precursors for various aliphatic polyesters, by using either Atom Transfer Radical Addition (ATRA) or Click reactions. The number of steps is limited whatever the "Click" or the "ATRA" strategy under consideration. In both cases, mild conditions have been found, such that degradation is minimized. Pendent hydroxyl, carboxylic acid and epoxide groups have been attached without using any protection/deprotection reaction. This strategy has been implemented for the synthesis of amphiphilic poly(εCL-g-ethylene oxide) graft copolymers, that have been used to prepare poly(D,L-lactide) nanoparticles for drug delivery applications. [less ▲]

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