References of "Debuigne, Antoine"
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See detailControlled synthesis of fluorinated copolymers via cobalt-mediated radical copolymerization of perfluorohexylethylene and vinyl acetate
Demarteau, Jérémy ULg; Améduri, Bruno; Ladmiral, Vincent et al

in Macromolecules (in press)

Designing novel polyfluoropolymer architectures is attractive for the development of new applications, such as advanced coatings, purification membranes, or materials for energy. Nevertheless, controlling ... [more ▼]

Designing novel polyfluoropolymer architectures is attractive for the development of new applications, such as advanced coatings, purification membranes, or materials for energy. Nevertheless, controlling the radical polymerization of fluoroalkenes is very challenging due to the high reactivity of the propagating fluorinated macroradicals. This study aims at exploring the controlled copolymerization of perfluoro- hexylethylene (PFHE) and vinyl acetate (VAc) in order to prepare a range of well-defined statistical poly(PFHE-stat-VAc) copolymers with different compositions. Cobalt-mediated radical polymerization demonstrated to be active at 40 °C starting from an alkylcobalt(III) initiator, and copolymers with a fluorinated monomer content as high as ca. 80 wt % were successfully prepared. Reactivity ratios were determined to be rVAc = 0.18 and rPFHE = 0 at 40 °C and emphasized a clear tendency for alternation. Unprecedented PFHE/VAc containing block copolymers were also prepared via a single-step approach or through sequential copolymerizations. Finally, hydrolysis of the pendant ester groups of these copolymers led to the corresponding fluorinated copolymers bearing vinyl alcohol (VOH). A preliminary solution behavior study, carried out by dynamic light scattering and transmission electron microscopy on block copolymers composed of PFHE and VAc or VOH units, evidenced a marked amphiphilicity of the copolymer composed of an extremely hydrophobic PFHE block associated with a highly hydrophilic PVOH segment. [less ▲]

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See detailFunctional emulsion-templated macroporous polymers via controlled radical polymerization
Mathieu, Kevin ULg; Jérôme, Christine ULg; Debuigne, Antoine ULg

Conference (2017, May 05)

Macroporous polymer monoliths with interconnected structures have attracted considerable interest in the fields of supported catalysis, chromatography, water purification, etc. A popular and ... [more ▼]

Macroporous polymer monoliths with interconnected structures have attracted considerable interest in the fields of supported catalysis, chromatography, water purification, etc. A popular and straightforward synthesis approach for such open-cell polymers is based on the emulsion-templated polymerization. In this strategy, a major phase is dispersed in a minor continuous phase containing monomers, cross-linker, initiator and surfactant. The curing of the continuous phase followed by the removal of the dispersed phase leads to a monolith with voids interconnected by pores. Size and number of the latters are influenced by several parameters and especially by the nature of the surfactant. Consequently, we prepared by controlled radical polymerization a series of well-defined amphiphilic copolymers having different hydrophilic-lipophilic balance (HLB) and chain-ends, used it as stabilizers for the emulsion-templated polymerizations and demonstrated the crucial effect of the macromolecular features as well as the concentration on the foam morphology. Secondly, the physical and the chemical anchoring of the macromolecular surfactants at the surface of the pores were also considered for tuning the surface properties of the porous monoliths in one step. This strategy was also implemented with alkyne-terminated copolymers in order to decorate the surface of the cavities with “clickable” moieties which broadens the scope of functional macroporous polymers. [less ▲]

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See detailSynthesis of well-defined polyvinylamine-containing copolymers via organometallic-mediated radical polymerization
Stiernet, Pierre ULg; Demarteau, Jérémy ULg; Jérôme, Christine ULg et al

Poster (2017, May 04)

Polyvinylamine (PVAm) is a useful polymer involved in a large range of applications including paper coating, surface engineering, membrane separation, etc. It is commonly produced via free radical ... [more ▼]

Polyvinylamine (PVAm) is a useful polymer involved in a large range of applications including paper coating, surface engineering, membrane separation, etc. It is commonly produced via free radical polymerization of N-vinylformamide (NVF) or N-vinylacetamide (NVA) followed by hydrolysis of the pendent amides of the resulting polymers. Due to the lack of stabilizing group on the double bond of N-vinylamides, the controlled radical polymerization of these monomers remained a challenge for a long time, preventing the preparation of well-defined PVAms. Recently, our group reported the controlled polymerization of NVA via reversible deactivation of the growing radical chains with cobalt complexes. Moreover, the use of well-defined PVAms as efficient carriers for gene transfection was demonstrated. This communication aims at reporting the synthesis of novel well-defined polyvinylamine-based copolymers. First, we explored the organometallic-mediated radical copolymerization of NVA and vinyl acetate. The optimized polymerization conditions and the comonomer reactivity ratios will be presented. Further conversion of the pendent amides and esters moieties into amino and hydroxy groups, respectively, was also considered for the preparation of unprecedented hydrophilic polyvinylamine-based copolymers. [less ▲]

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See detailControlled synthesis of α-olefins-based copolymers by organocobalt(III) complexes
Demarteau, Jérémy ULg; Debuigne, Antoine ULg; Detrembleur, Christophe ULg

Conference (2017, May 04)

Polyolefins, and ethylene-vinyl acetate (EVA) copolymers in particular, are highly attractive materials that are industrially synthesized by a free radical process for large range of applications from ... [more ▼]

Polyolefins, and ethylene-vinyl acetate (EVA) copolymers in particular, are highly attractive materials that are industrially synthesized by a free radical process for large range of applications from food packaging to coatings. Their production requires drastic synthesis conditions (high pressure and high temperature) and the resulting polymers are generally ill-defined. Controlling the polymerization of these unconjugated monomers remains however extremely difficult because of the lack of stabilizing group on their double bond. Moreover, the preparation of chain-end functionalized polyolefins is actually impossible under these conditions. This communication aims at reporting an efficient platform for the precision design of alpha-olefin-based copolymers through a controlled radical polymerization technique called Cobalt-Mediated Radical Polymerization (CMRP). The latter is based on the reversible deactivation of the radical chains by a cobalt complex bearing acetylacetonate (acac) ligands, which is very efficient under mild experimental conditions. The presentation will focus on three main axes: (i) the synthesis of a novel organocobalt(III) complex useful for the functionalization of the polymer chains, (ii) the preparation of various EVA architectures, (iii) the controlled copolymerization of vinyl acetate with a perfluorinated alkene, i.e. perfluorohexylethylene. The hydrolysis of the pendent esters moieties of these fluorinated copolymers paved the way to their polyvinylalcohol counterparts with a marked amphiphilicity. [less ▲]

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See detailOrganometallic-mediated radical polymerization of 'less activated monomers': fundamentals, challenges and opportunities
Debuigne, Antoine ULg; Jérôme, Christine ULg; Detrembleur, Christophe ULg

in Polymer (2017), 115

Access to well-defined polymers made of the so-called ‘Less Activated Monomers’ (LAMs) via controlled radical polymerization has long been a challenge due to the lack of radical stabilizing group on the ... [more ▼]

Access to well-defined polymers made of the so-called ‘Less Activated Monomers’ (LAMs) via controlled radical polymerization has long been a challenge due to the lack of radical stabilizing group on the double bond of these monomers. This Feature Article summarizes substantial progress in the organometallic-mediated radical polymerization (OMRP) of this important class of monomers including vinyl esters, olefins, vinyl chloride, vinyl amides, or ionic-liquid vinyl monomers. It aims to provide a clear and comprehensive account of the fundamentals and challenges in the OMRP of LAMs as well as an overview of the resulting macromolecular engineering opportunities. The input of photochemistry, environmentally friendly solvents or flow reactors in OMRP is also presented. Finally, it emphasizes how some well-defined LAMs-based materials contributed to the development of specific applications notably in the fields of biomedicine or energy. [less ▲]

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See detailSimultaneous synthesis and chemical functionalization of emulsion-templated porous polymers using nitroxide-terminated macromolecular surfactants
Mathieu, Kevin ULg; De Winter, Julien; Jérôme, Christine ULg et al

in Polymer Chemistry (2017), 8(11), 1850-1861

The design of functional 3D macroporous monoliths has become a necessity for a wide range of applications. Traditional post-modification strategies of porous materials are efficient but often consist in ... [more ▼]

The design of functional 3D macroporous monoliths has become a necessity for a wide range of applications. Traditional post-modification strategies of porous materials are efficient but often consist in tedious multi-steps processes. This work describes a straightforward macromolecular surfactant-assisted method for producing chemically functionalized macroporous polyHIPEs with interconnected structures. Accordingly, high internal phase emulsion-templated polymerizations were implemented in the presence of SG1-terminated amphiphilic copolymers prepared by nitroxide- mediated radical polymerization (NMP). The latter served as both stabilizers and functionalizing agents upon thermal activation of its terminal alkoxyamine and covalent anchoring of the released radical copolymer onto the walls of the scaffold. The effect of the polymerization temperature on the functionalization and openness of the final porous materials was explored. As a result, a range of open-cell styrene and acrylate-based polyHIPEs chemically grafted with PEO were obtained. Moreover, polyHIPEs were also decorated with alkyne-bearing PEO and subsequently modified via CuAAc click chemistry in order to demonstrate the potential of this macromolecular surfactants-assisted functionalization method. [less ▲]

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See detailUse of primary and secondary polyvinylamines for efficient gene transfection
Dréan, Mathilde; Debuigne, Antoine ULg; Gonçalves, Christine et al

in Biomacromolecules (2017), 18(2), 440-441

Gene transfection with polymeric carrier remains a challenge, particularly high transfection levels combined with low toxicity are hard to achieve. We herein revisit polyvinylamines, an old and neglected ... [more ▼]

Gene transfection with polymeric carrier remains a challenge, particularly high transfection levels combined with low toxicity are hard to achieve. We herein revisit polyvinylamines, an old and neglected family of cationic polymers. They can be readily obtained by controlled hydrolysis of polyvinylamides prepared through (controlled) radical polymerization. A series of tailor-made and well-defined polyvinylamines bearing primary amino groups, and poly(N- methylvinylamine) bearing secondary amines, were evaluated for the transfection of cells with pDNA as a function of their molar mass, molar mass distribution and degree of deacetylation. Unexpected high transfection levels, in combination with low cytotoxicity were recorded for both series. Surprisingly, a great impact of the molar mass was observed for the primary amine polyvinylamine series, whereas the results were mostly independent on molar mass or dispersity for the polymer bearing secondary amine. It was further established that a certain percentage of acetamide groups increased the transfection level, while maintaining low cytotoxicity. These results highlight for the first time the real potential of polyvinylamines as gene carriers, and make these polymers very attractive for further development in gene therapy. [less ▲]

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See detailProtein encapsulation and release from PEO-b-polyphosphoester templated calcium carbonate particles
Ergül, Zeynep ULg; Cordonnier, Thomas; Debuigne, Antoine ULg et al

in International Journal of Pharmaceutics (2016), 513

Calcium carbonate particles are promising candidates as proteins carriers for their controlled delivery in the body. The present paper aims at investigating the protein encapsulation by in situ ... [more ▼]

Calcium carbonate particles are promising candidates as proteins carriers for their controlled delivery in the body. The present paper aims at investigating the protein encapsulation by in situ precipitation of calcium carbonate particles prepared by a process based on supercritical CO2 and using a new type of degradable well-defined double hydrophilic block copolymers composed of poly(ethylene oxide) and polyphosphoester blocks acting as templating agent for the calcium carbonate. For this study, lysozyme was chosen as a model for therapeutic protein for its availability and ease of detection. It was found that by this green process, loading into the CaCO3 microparticles with a diameter about 2 mm can be obtained as determined by scanning electron microscopy. A protein loading up to 6.5% active lysozyme was measured by a specific bioassay (Micrococcus lysodeikticus). By encapsulating fluorescent-labelled lysozyme (lysozyme-FITC), the confocal microscopy images confirmed its encapsulation and suggested a core–shell distribution of lysozyme into CaCO3, leading to a release profile reaching a steady state at 59% of release after 90 min. [less ▲]

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See detailSurface- and redox-active multifunctional polyphenol-derived poly(ionic liquid)s: controlled synthesis and characterization
Patil, Nagaraj ULg; Cordella, Daniela; Aqil, Abdelhafid ULg et al

in Macromolecules (2016), 49(20), 7676-7691

Combining the redox activity and remarkable adhesion propensity of polyphenols (such as catechol or pyrogallol) with the numerous tunable properties of poly(ionic liquid)s (PILs) is an attractive route to ... [more ▼]

Combining the redox activity and remarkable adhesion propensity of polyphenols (such as catechol or pyrogallol) with the numerous tunable properties of poly(ionic liquid)s (PILs) is an attractive route to design inventive multifunctional macro-molecular platforms. In this contribution, we describe the first synthesis of a novel family of structurally well-defined PILs functionalized with catechol/pyrogallol/phenol pendants by organometallic-mediated radical polymerization (OMRP) using an alkyl−cobalt(III) complex as initiator and mediating agent. The living character of the chains is also exploited to produce di-and triblock PILs, and the facile counteranion exchange reactions afforded a library of PILs-bearing free phenol/catechol/pyrogallol moieties. Electrochemical investigations of catechol/pyrogallol-derived PILs in aqueous medium demonstrated the characteristic catechol to o-quinone transformations, whereas, quasi-reversible doping/undoping with supporting electrolyte cations (Li + /tetrabutylammonium +) has been observed in organic media, suggesting a bright future for this new family of redox-active PILs as cathode material for secondary energy storage devices. Also, pendant catechol/pyrogallol groups mediated sustained anchoring onto the gold surface conferred PILs properties to the interface. As a proof-of-concept, both the adsorption and inhibition of proteins on polymer modified surfaces have been demonstrated in real time using the quartz crystal microbalance with dissipation technique. The exquisite physicochemical tunability of these innovative surface-and redox-active PILs makes them excellent candidates for a broad range of potential applications, including " smart surfaces " and electrochemical energy storage devices. [less ▲]

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See detailAlkylcobalt as source of radicals for the controlled polymerization of less activated vinyl monomer
Demarteau, Jérémy ULg; Cordella, Daniela ULg; Kermagoret, Anthony et al

Poster (2016, October 13)

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See detailExpanding the scope of cobalt-mediated radical polymerization towards the synthesis of novel poly(vinyl acetate-alt-tert-butyl-2-trifluoromethacrylate) alternating fluorocopolymers
Banerjee; Ladmiral, Vincent; Debuigne, Antoine ULg et al

Conference (2016, October 04)

Cobalt mediated radical polymerization (CMRP) is a nice technique to control the radical polymerization of vinyl acetate, VAc, but has never been reported on fluoromonomers. This presentation aims at ... [more ▼]

Cobalt mediated radical polymerization (CMRP) is a nice technique to control the radical polymerization of vinyl acetate, VAc, but has never been reported on fluoromonomers. This presentation aims at showing recent works on the use of CRMP to prepare well-defined unprecedented 1:1 alternating fluorocopolymers with narrow dispersity (≤1.3) comprised of a polar monomer (VAc) and a non-homopolymerizable fluoromonomer (tert-butyl-2-trifluoromethacrylate, MAF-TBE), under mild conditions.[1] The resulting poly(VAc-alt-MAF-TBE) copolymers have a precise 1:1 alternating structure over a wide range of the comonomer feed compositions in CMRP conditions as well as under free radical polymerization conditions,[2] as confirmed by NMR spectroscopies. Kinetics of radical copolymerization led to their reactivity ratios: rVAc = 0.014; rMAF-TBE = 0 at 40 °C). Simple adjustments of the monomer feed ratio and of the polymerization time, allow the synthesis of well-defined alternating copolymer or of novel poly(VAc- alt- MAF-TBE)-b-PVAc block copolymer composed of an alternating block and of a PVAc block. The block copolymer exhibited two glass transition temperatures (Tg) at 43 and 67 °C, which correspond to those of PVAc segment and poly(VAc-alt-MAF-TBE) alternating sequences, respectively. In contrast, the poly(VAc-alt-MAF-TBE) alternating copolymer displayed only one Tg at 40 °C. For the first time, CMRP of fluorinated monomer was achieved and this fluorine-containing alternating monomer system provides access to a wide range of new polymer materials, under progress. [less ▲]

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See detailOrganocobalt complexes as source of radicals for the controlled polymerization of unconjugated monomers
Demarteau, Jérémy ULg; Cordella, Daniela ULg; Kermagoret, Anthony et al

Poster (2016, September 12)

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See detailPolyphosphoester containing amphiphilic block copolymers as drug nanocarriers
Ergül, Zeynep ULg; Vanslambrouck, Stéphanie; Thiry, Justine ULg et al

Poster (2016, September 12)

The design of drug delivery systems often requires biodegradable and biocompatible materials that allow safe retention and controlled release of the drug. In this respect, supramolecularly self-assembled ... [more ▼]

The design of drug delivery systems often requires biodegradable and biocompatible materials that allow safe retention and controlled release of the drug. In this respect, supramolecularly self-assembled amphiphilic block copolymers into spherical micelles are appropriate carriers for poorly soluble drugs. In that framework, we have designed novel functional poly(ethylene oxide)-b-polyphosphoester amphiphilic block copolymers able to cross-linked under UV and degrade in response to a reduction of the pH from neutral conditions. Therefore, an unsaturated alkene side-chain was introduced on the cyclic phosphate monomer according to a one-step reaction followed by its organocatalyzed polymerization initiated by a poly(ethylene oxide) macroinitiator. After self-assembly into water, the micelles were cross-linked by UV irradiation. Then, these cross-linked micelles have been loaded by doxorubicin, i.e. a drug used in cancer therapy. We observed that the doxorubicin loading increased with the number of double bonds on the polyphosphate block of non-cross-linked micelles. This diblock amphiphilic copolymer bearing pendant unsaturations appears thus particularly promising candidate to build micellar drug delivery systems for intravenous injection. [less ▲]

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See detailMacro- and near-mesoporous monoliths by medium internal phase emulsion polymerization: a systematic study
Mathieu, Kevin ULg; Jérôme, Christine ULg; Debuigne, Antoine ULg

in Polymer (2016), 99

The synthesis of a series of poly(ethylene oxide)-b-polystyrene copolymers with different block lengths was performed by radical addition fragmentation chain transfer. These amphiphilic copolymers were ... [more ▼]

The synthesis of a series of poly(ethylene oxide)-b-polystyrene copolymers with different block lengths was performed by radical addition fragmentation chain transfer. These amphiphilic copolymers were tested as stabilizers for water-in-oil medium internal phase emulsion (MIPE) templating polymerization and the formation of polyMIPEs with controlled morphology. Aside from the structure of the emulsion stabilizer, several parameters susceptible to influence the size of the cavities and the interconnectivity of the porous monoliths were probed including the choice of the comonomers, treatment of the emulsion by ultrasound, the use of controlled radical polymerization method for the network formation as well as interfacial initiation. Interconnected cellular monoliths were produced. The polymerization of the ultrasonicated water-in-ethylhexylacrylate/divinylbenzene MIPE notably led to near-mesoporous open-cell material. Mechanical properties and specific surface areas of the polyMIPEs were also investigated and discussed. [less ▲]

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