References of "Debuigne, Antoine"
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See detailSynthesis of degradable polyphosphoester copolymers for templating calcium carbonate drug delivery carriers
Ergül, Zeynep ULg; Debuigne, Antoine ULg; Calvignac, Brice et al

Conference (2014, July 09)

Degradable acid bearing polyphosphoester (PPE) copolymers were prepared by combination of organocatalyzed ring opening polymerization and click chemistry. Their solution behavior and ability to complex ... [more ▼]

Degradable acid bearing polyphosphoester (PPE) copolymers were prepared by combination of organocatalyzed ring opening polymerization and click chemistry. Their solution behavior and ability to complex calcium ions were studied as well as their capacity to template CaCO3 particles dedicated to drug delivery. [less ▲]

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See detailTemplating calcium carbonate drug delivery carriers based on polyphosphoester copolymers
Ergül, Zeynep ULg; Debuigne, Antoine ULg; Caalvignac, Brice et al

Poster (2014, May 27)

The design of drug delivery systems (DDS) often requires biodegradable and biocompatible materials that allow safe retention and controlled release of the drug. In this respect, CaCO3 particles are ... [more ▼]

The design of drug delivery systems (DDS) often requires biodegradable and biocompatible materials that allow safe retention and controlled release of the drug. In this respect, CaCO3 particles are appropriate drug carriers that have excellent properties such as low density, high specific surface areas and porosity for drugs and proteins encapsulation. Here, hyaluronic acid usually used for templating CaCO3 particles was substituted by a degradable synthetic copolymer based on PPE. The latter is a promising candidate due to its biocompatibility, biodegradability and the low toxicity of its degradation products such as phosphates. We also introduced acid functions on the PPE segment in order to enhance its calcium affinity and ability to tune the morphology of the CaCO3 particles. The butynyl phospholane (BYP) polymerization was initiated from poly(ethylene oxide) PEO-OH by organocatalyzed ring opening polymerization (ROP) [2] followed by UV catalyzed thiol-yne addition of 3-mercaptopropionoic acid onto the alkyne functions. CaCO3 particles were then generated in the presence of the copolymer following a procedure inspired from . Well-defined PPE copolymers bearing pendant alkynyl groups, i.e. PEO-b-PBYP (Ð <1.1), were obtained by organocatalyzed ROP of BYP initiated at 0°C from PEO-OH (Scheme 1). The copolymer was then reacted under UV with 3-mercaptopropionoic acid in order to introduce carboxylic acid functions along the PPE backbone by thiol-yne reaction. NMR analyses confirmed that full functionalization was reached after 2h. The high density of acid moieties in PEO-b-PBYP(COO-)2 is supposed to facilitate the Ca2+ complexation. The solution behavior and self-assembly of PEO-b-PBYP(COO-)2 in water was investigated by DLS with and without Ca+2 at different pH. Finally, stoichiometric amounts of CaCl2 and Na2CO3 were mixed in water containing the PEO-b-PBYP(COO-)2 which strongly influences the size of the CaCO3 particles (~1.5 µm). The acid-bearing PPE-based copolymers were successfully prepared and used as templating agents for the synthesis of CaCO3 particles. [less ▲]

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See detailSynthesis of a glucosamine labeled amphiphilic polymer for drug delivery application
Riva, Raphaël ULg; Boyère, Cédric; Debuigne, Antoine ULg et al

Poster (2014, May 27)

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See detailPrecision design of novel poly(ionic liquid) (co)polymers by cobalt-mediated radical polymerization (CMRP)
Cordella, Daniela ULg; Kermagoret, Anthony ULg; Debuigne, Antoine ULg et al

Poster (2014, May 20)

In recent years, poly(ionic liquid)s (PIL)s were found to take an enabling role in important fields of polymer chemistry and material science. PILs combine the unique properties of ionic liquids with the ... [more ▼]

In recent years, poly(ionic liquid)s (PIL)s were found to take an enabling role in important fields of polymer chemistry and material science. PILs combine the unique properties of ionic liquids with the flexibility and properties of macromolecular architectures giving rise to a new family of functional polymers that opens new area of applications such as polymer electrolytes in electrochemical devices, powerful dispersants and stabilizers, absorbing membranes, precursors for carbon materials, porous polymers, etc. In this communication, we will report on the implementation of organometallic-mediated radical polymerization (OMRP) technique for the precision synthesis of unprecedented PILS (co)polymers. We will discuss how an organocobalt complex can nicely control the growth of vinyl imidazolium chains and lead to PILS with predicted molar masses and low polydispersitiesunder mild experimental conditions. The huge potential of this system will be highlighted by describing the first one-pot synthesis of vinyl imidazolium-based block copolymers in heterogeneous conditions. This OMRP is unique for providing well-defined vinyl imidazolium based-copolymers that are not easily accessible by other controlled radical polymerization techniques, and opens therefore new rooms for advanced PILS applications. [less ▲]

Detailed reference viewed: 30 (2 ULg)
See detailSynthesis of degradable polyphosphoester copolymers for templating calcium carbonate drug delivery carriers
Ergül, Zeynep ULg; Debuigne, Antoine ULg; Calvignac, Brice et al

Poster (2014, May 20)

The design of drug delivery systems (DDS) often requires biodegradable and biocompatible materials that allow safe retention and controlled release of the drug. In this respect, CaCO3 particles are ... [more ▼]

The design of drug delivery systems (DDS) often requires biodegradable and biocompatible materials that allow safe retention and controlled release of the drug. In this respect, CaCO3 particles are appropriate drug carriers that have excellent properties such as low density, high specific surface areas and porosity for drugs and proteins encapsulation. Here, hyaluronic acid usually used for templating CaCO3 particles was substituted by a degradable synthetic copolymer based on PPE. The latter is a promising candidate due to its biocompatibility, biodegradability and the low toxicity of its degradation products such as phosphates. We also introduced acid functions on the PPE segment in order to enhance its calcium affinity and ability to tune the morphology of the CaCO3 particles. The butynyl phospholane (BYP) polymerization was initiated from poly(ethylene oxide) PEO-OH by organocatalyzed ring opening polymerization (ROP) [2] followed by UV catalyzed thiol-yne addition of 3-mercaptopropionoic acid onto the alkyne functions. CaCO3 particles were then generated in the presence of the copolymer following a procedure inspired from . Well-defined PPE copolymers bearing pendant alkynyl groups, i.e. PEO-b-PBYP (Ð <1.1), were obtained by organocatalyzed ROP of BYP initiated at 0°C from PEO-OH (Scheme 1). The copolymer was then reacted under UV with 3-mercaptopropionoic acid in order to introduce carboxylic acid functions along the PPE backbone by thiol-yne reaction. NMR analyses confirmed that full functionalization was reached after 2h. The high density of acid moieties in PEO-b-PBYP(COO-)2 is supposed to facilitate the Ca2+ complexation. The solution behavior and self-assembly of PEO-b-PBYP(COO-)2 in water was investigated by DLS with and without Ca+2 at different pH. Finally, stoichiometric amounts of CaCl2 and Na2CO3 were mixed in water containing the PEO-b-PBYP(COO-)2 which strongly influences the size of the CaCO3 particles (~1.5 µm). The acid-bearing PPE-based copolymers were successfully prepared and used as templating agents for the synthesis of CaCO3 particles. [less ▲]

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See detailMetal-free synthesis of a glucosamine labeled amphiphilic polymer for drug delivery applications
Riva, Raphaël ULg; Boyère, Cécric; Debuigne, Antoine ULg et al

Poster (2014, May 19)

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See detail(Co)Polymerization of vinyl levulinate by cobalt-mediated radical polymerization and functionalization by ketoxime click chemistry
Allaoua, Imène; Eleuterio, Beatriz; Obadia, Mona M. et al

in Polymer Chemistry (2014), 5(8), 2973-2979

Vinyl levulinate is synthesized from levulinic acid by palladium-catalyzed vinyl exchange and is characterized by NMR and ESI-HRMS techniques. Homopolymerization of vinyl levulinate and random ... [more ▼]

Vinyl levulinate is synthesized from levulinic acid by palladium-catalyzed vinyl exchange and is characterized by NMR and ESI-HRMS techniques. Homopolymerization of vinyl levulinate and random copolymerization with vinyl acetate by cobalt-mediated radical polymerization affords well-defined ketone functionalized poly(vinyl ester)s. The impact of temperature, solvent and theoretical degree of polymerization on monomer conversion and control of the polymerization is studied by 1H NMR and size exclusion chromatography techniques. The ketoxime conjugation of O-benzylhydroxylamine with the pendant ketone functionality of poly(vinyl levulinate-co-vinyl acetate) is demonstrated. [less ▲]

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See detailElaboration of drug nanocarriers based on a glucosamine labeled amphiphilic polymer
Boyère, Cédric; Duhem, N; Debuigne, Antoine ULg et al

in Polymer Chemistry (2014), 5(8), 3030-3037

A new functional polymer micelle with high loading efficiency of a poorly soluble drug was made of biocompatible and/or biosourced compounds, i.e. cholesterol-poly(ethylene glycol)-glucosamine (Chol-PEG ... [more ▼]

A new functional polymer micelle with high loading efficiency of a poorly soluble drug was made of biocompatible and/or biosourced compounds, i.e. cholesterol-poly(ethylene glycol)-glucosamine (Chol-PEG-GlcNH2). A synthesis strategy combining enzymatic and metal-free click chemistry was developed in order to meet the increasingly stringent requirements of biomedical applications. After the self-assembly of the Chol-PEG-GlcNH2 amphiphilic polymer in water, the presence of glucosamine at the micelle surface confers an active targeting moiety to the nanocarriers whereas protonation of the peripheral primary amine delay their aggregation. The complete characterization of this novel functional amphiphilic bioconjugate is presented as well as its aqueous solution behaviour and encapsulation efficiency using ketoconazole as a model hydrophobic drug. [less ▲]

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See detailPrecision polymer design by organometallic-mediated radical polymerization
Debuigne, Antoine ULg

Scientific conference (2014, March 13)

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See detailPrecision design of ethylene- and polar-monomer-based copolymers by organometallic-mediated radical polymerization
Kermagoret, Anthony ULg; Debuigne, Antoine ULg; Jérôme, Christine ULg et al

in Nature Chemistry (2014), 6(3), 179-187

The copolymerization of ethylene with polar monomers is a major challenge when it comes to the manufacture of materials with potential for a wide range of commercial applications. In the chemical industry ... [more ▼]

The copolymerization of ethylene with polar monomers is a major challenge when it comes to the manufacture of materials with potential for a wide range of commercial applications. In the chemical industry, free-radical polymerization is used to make a large proportion of such copolymers, but the forcing conditions result in a lack of fine control over the architecture of the products. Herein we introduce a synthetic tool, effective under mild experimental conditions, for the precision design of unprecedented ethylene- and polar-monomer-based copolymers. We demonstrate how an organocobalt species can control the growth of the copolymer chains, their composition and the monomer distribution throughout the chain. By fine tuning the ethylene pressure during polymerization and by exploiting a unique reactive mode of the end of the organometallic chain, novel block-like copolymer structures can be prepared. This highly versatile synthetic platform provides access to a diverse range of polymer materials. [less ▲]

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See detailGlucose-, pH- and thermo-responsive nanogels crosslinked by functional superparamagnetic maghemite nanoparticles as innovative drug delivery systems
Liu, Ji ULg; Detrembleur, Christophe ULg; Debuigne, Antoine ULg et al

in Journal of Materials Chemistry B (2014), 2(8), 1009-1023

Reversibly crosslinked (RCL) nanogels made of thermo-responsive poly(vinyl alcohol)-b-poly(Nvinylcaprolactam) copolymers were combined with maghemite nanoparticles and developed as new drug delivery ... [more ▼]

Reversibly crosslinked (RCL) nanogels made of thermo-responsive poly(vinyl alcohol)-b-poly(Nvinylcaprolactam) copolymers were combined with maghemite nanoparticles and developed as new drug delivery systems (DDS). The crosslinking was formed via boronate/diol bonding from the surfacefunctionalized superparamagnetic maghemite nanoparticles, endowing the DDS with thermo-, pH- and glucose-responsiveness. The capability to load a hydrophobic drug model Nile red (NR) within the RCL nanogels was evaluated, and stimuli-triggered drug release behaviours under different conditions were tested. Zero premature release behaviour was detected at physiological pH in the absence of glucose, whereas triggered release was observed upon exposure to acidic pH (5.0) and/or in the presence of glucose. In light of the superparamagnetic properties of the maghemite nanoparticles and RCL nanogels, magnetically-induced heating, MR imaging performance, as well as remotely magnetically-triggered drug release under alternating magnetic field (AMF), were investigated. Cytotoxicity against fibroblast-like L929 and human melanoma MEL-5 cell lines was assessed via the MTS assay. In vitro stimuli-triggered release of tamoxifen, a chemotherapeutic drug, was also studied within MEL-5 cell cultures under different conditions. These innovative RCL nanogels, integrating different stimuli-responsive components, hydrophobic chemotherapeutic moieties and also diagnostic agents together via reversible crosslinking, are promising new theranostic platforms. [less ▲]

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See detailPrecision synthesis of poly(ionic liquid)-based block copolymers by cobalt-mediated radical polymerization and preliminary study of their self-assembling properties
Coupillaud, Paul; Fèvre, Maréva; Wirotius, Anne-Laure et al

in Macromolecular Rapid Communications (2014), 35(4), 422-430

A poly(ionic liquid)-based block copolymer (PIL BCP), namely, poly(vinyl acetate)-b-poly(N-vinyl-3-butylimidazolium bromide), PVAc-b-PVBuImBr, is synthesized by sequential cobalt-mediated radical ... [more ▼]

A poly(ionic liquid)-based block copolymer (PIL BCP), namely, poly(vinyl acetate)-b-poly(N-vinyl-3-butylimidazolium bromide), PVAc-b-PVBuImBr, is synthesized by sequential cobalt-mediated radical polymerization (CMRP). A PVAc precursor is first prepared at 30 °C in bulk by CMRP of VAc, using bis(acetylacetonato)cobalt(II), Co(acac)2, and a radical source (V-70). Growth of PVBuImBr from PVAc-Co(acac)2 is accomplished by CMRP in DMF/MeOH (2:1, v/v). This PIL BCP self-assembles in the sub-micron size range into aggregated core–shell micelles in THF, whereas polymeric vesicles are observed in water, as evidenced by dynamic light scattering (DLS) and transmission electron microscopy (TEM). Thin-solid sample cut from raw materials analyzed by TEM shows an ordered lamellar organization by temperature-dependent synchrotron small-angle X-ray scattering (SAXS). Anion exchange can be accomplished to achieve the corresponding PIL BCP with bis(trifluorosulfonyl)imide (Tf2N−) anions, which also gives rise to an ordered lamellar phase in bulk samples. A complete suppression of SAXS second-order reflection suggests that this compound has a symmetric volume fraction (f ≈ 0.5). SAXS characterization of both di- and triblock PIL BCP analogues previously reported also shows a lamellar phase of very similar behavior, with only an increase of the period by about 8% at 60 °C. [less ▲]

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See detailReversibly crosslinked thermo- and redox-responsive nanogels for controlled drug release
Liu, Ji ULg; Detrembleur, Christophe ULg; Hurtgen, Marie ULg et al

in Polymer Chemistry (2014), 5(1), 77-88

Reversibly crosslinked poly(vinyl alcohol)-b-poly(N-vinylcaprolactam) PVOH-b-PNVCL nanogels were prepared by using a redox-responsive crosslinking agent, 3,30-dithiodipropionic acid (DPA), to crosslink ... [more ▼]

Reversibly crosslinked poly(vinyl alcohol)-b-poly(N-vinylcaprolactam) PVOH-b-PNVCL nanogels were prepared by using a redox-responsive crosslinking agent, 3,30-dithiodipropionic acid (DPA), to crosslink the PVOH corona, above the lower critical solution temperature (LCST) of the PNVCL block. The stability of the as-prepared nanogels against heating and diluting with water was studied by dynamic light scattering (DLS) to follow the evolution of the hydrodynamic diameter and size distribution. Stability under reductive conditions was also studied by DLS and transmission electron microscopy (TEM) after exposure to dithiothreitol (DTT) buffer solutions at different pH. The reversibility of the crosslinking was evaluated by treating the de-crosslinked nanogels with hydrogen peroxide (H2O2) above the LCST. As a hydrophobic drug model, Nile red (NR) was loaded into the nanogels, and triggered release behaviours were studied after exposure to the same DTT buffer solutions. Moreover, two PVOH-b-PNVCL copolymers with different compositions and LCST were used to evaluate the effect of the LCST on the release behaviours of the nanogels. The cytotoxicity of the nanogels against a mouse fibroblast-like L929 cell line was assessed via the MTS assay, and preliminary studies on cellular uptake of the nanogels within human melanoma MEL-5 cells were also carried out by fluorescence microscopy and fluorescence-activated cell sorting. [less ▲]

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See detailExpanding the scope of controlled radical polymerization via cobalt–tellurium radical exchange reaction
Kermagoret, Anthony ULg; Nakamura, Yasuyuki; Bourguignon, Maxime et al

in ACS Macro Letters (2014), 3(1), 114-118

Cobalt-mediated radical polymerization (CMRP) and tellurium-mediated radical polymerization (TERP) were combined for the first time, offering new perspectives in the precision design of macromolecular ... [more ▼]

Cobalt-mediated radical polymerization (CMRP) and tellurium-mediated radical polymerization (TERP) were combined for the first time, offering new perspectives in the precision design of macromolecular structures. In particular, the present work highlights the benefits of this strategy for the synthesis of novel poly(vinyl acetate)-based block copolymers. A range of well-defined poly(vinyl acetate)s (PVAc) were first produced via CMRP using the bis(acetylacetonato)cobalt(II) complex (Co(acac)2) as a regulating agent. Substitution of a methyltellanyl moiety for Co(acac)2 at the ω-chain end of the precursor was then achieved upon treatment with dimethylditelluride. In contrast to the PVAc prepared by TERP, the ones produced by sequential CMRP and Co/Te exchange reaction almost exclusively consist of regular head-to-tail-TeMe chain-end species that can be activated by TERP. Ultimately, a series of monomers problematic in Co(acac)2-mediated radical polymerization including N-isopropylacrylamide (NIPAM), 2-(dimethylamino)ethyl acrylate (ADAME), n-butyl acrylate (BA), isoprene (IP), and vinylimidazole (NVIm) were polymerized by TERP from the PVAc–TeMe macroinitiators leading to novel diblock copolymers that cannot be made by each technique used separately. [less ▲]

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See detailPoly(acrylic acid)-block-poly(vinyl alcohol) anchored maghemite nanoparticles designed for multi-stimuli triggered drug release
Liu, Ji ULg; Detrembleur, Christophe ULg; Debuigne, Antoine ULg et al

in Nanoscale (2013), 5(23), 11464-11477

Original core/corona nanoparticles composed of amaghemite core and a stimuli-responsive polymer coating made of poly(acrylic acid)-block-poly(vinyl alcohol) macromolecules were fabricated for drug ... [more ▼]

Original core/corona nanoparticles composed of amaghemite core and a stimuli-responsive polymer coating made of poly(acrylic acid)-block-poly(vinyl alcohol) macromolecules were fabricated for drug delivery system (DDS) application. This kind of DDS aims to combine the advantage of stimuli-responsive polymer coating, in order to regulate the drug release behaviours under different conditions and furthermore, improve the biocompatibility and in vivo circulation half-time of the maghemite nanoparticles. Drug loading capacity was evaluated with methylene blue (MB), a cationic model drug. The triggered release of MB was studied under various stimuli such as pH, ionic strength and temperature. Local heating generated under alternating magnetic field (AMF) application was studied, and remotely AMF-triggered release was also confirmed, while a mild heating-up of the release medium was observed. Furthermore, their potential application as magnetic resonance imaging (MRI) contrast agents was explored via relaxivity measurements and acquisition of T2-weighted images. Preliminary studies on the cytotoxicity against mouse fibroblast-like L929 cell line and also their cellular uptake within human melanoma MEL-5 cell line were carried out. In conclusion, this kind of stimuli-responsive nanoparticles appears to be promising carriers for delivering drugs to some tumour sites or into cellular compartments with an acidic environment. [less ▲]

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