References of "Jérôme, Christine"
     in
Bookmark and Share    
Full Text
See detailPreparation of living polymer microspheres by dispersion atom transfer radical polymerization in scCO2 using fluorinated macroligands
Grignard, Bruno ULg; Calberg, Cédric ULg; Jérôme, Christine ULg et al

Poster (2009, May 19)

Due to an increasing need for polymers with well-defined architecture (diblock-, graft-, star-shaped copolymers), molecular weight and/or functional end-groups, the use of controlled radical ... [more ▼]

Due to an increasing need for polymers with well-defined architecture (diblock-, graft-, star-shaped copolymers), molecular weight and/or functional end-groups, the use of controlled radical polymerization (CRP) in scCO2 has started to gain attention. Among all the controlled processes, Atom Transfer Radical Polymerization has emerged as a robust tool for the preparation of polymers with well-defined molecular weight, architecture and chain-end functionality. In a very recent paper, we reported the first efficient dispersion ATRP of methyl methacrylate (MMA) in scCO2 using a fluorinated polymeric ligand that had a dual role, i.e., the complexation of the copper salt and the stabilization of PMMA growing particles. In this contribution, we extended this new system to the dispersion ATRP of styrene, to the synthesis of diblock copolymers beads and the controlled synthesis of hyperbranched copolymers. Finally, because both ATRP and alkyne-azide Huisgen’s 1,3-dipolar cycloaddition relies on the use of a Cu(I) catalyst, synthesis of pyrene end-functionalized polymers by simultaneous dispersion ATRP and click reaction was also investigated in supercritical carbon dioxide. [less ▲]

Detailed reference viewed: 50 (7 ULg)
Full Text
See detailUse of the supercritical fluid technology to prepare efficient nanocomposite foams for environmental protection purpose
Urbanczyk, Laetitia ULg; Thomassin, Jean-Michel ULg; Huynen, Isabelle et al

Conference (2009, May 19)

This work reports on the preparation of novel nanocomposite foams that are efficient broadband microwave absorbers. Carbon nanotubes are first successfully dispersed into PCL and PMMA by melt blending ... [more ▼]

This work reports on the preparation of novel nanocomposite foams that are efficient broadband microwave absorbers. Carbon nanotubes are first successfully dispersed into PCL and PMMA by melt blending. Then, foaming is promoted by supercritical CO2 by depressurization. Regular cellular structures are obtained in both cases with cells size around 10-50µm. The electromagnetic interference (EMI) shielding efficiency of these materials are then evaluated and compared to the non-foamed nanocomposites. [less ▲]

Detailed reference viewed: 55 (7 ULg)
Full Text
See detailNovel Stealthy Gd(III)-DOTA/polymer Conjugates for Magnetic Resonance Imaging (MRI)
Grogna, Mathurin ULg; Bémelmans, Stéphanie ULg; Vanasschen, Christian ULg et al

Conference (2009, May 14)

Magnetic resonance imaging (MRI) is a routine diagnostic tool in modern clinical medicine. MRI has many advantages as a diagnostic imaging modality. It is noninvasive, delivers no radiation, and has ... [more ▼]

Magnetic resonance imaging (MRI) is a routine diagnostic tool in modern clinical medicine. MRI has many advantages as a diagnostic imaging modality. It is noninvasive, delivers no radiation, and has excellent (submillimeter) spatial resolution. Some Gadolinium(III) complexes are commonly used to enhance the contrast between adjacent tissues when the resolution/sensitivity of MRI is too low. Because free Gd3+ is very toxic in doses required for MRI, Gd(III) is chelated by poly(amino-carboxylate) such as diethylenetriamine pentaacetic acid (DTPA) or 1,4,7,10-Tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA). Although DTPA/Gd3+ and DOTA/Gd3+ are water soluble, they have a very short circulation lifetime in blood, a low molecular weight and a short rotational time that make the contrast poor. To enhance the contrast, the Gd3+/complex doses have to be increased. In order to increase the sensitivity of the technique, while not increasing the concentration of the contrast agent, we were investigating different strategies to improve (i) the circulation lifetime in blood, (ii) the relaxation rate of Gd(III) (and consequently, the contrasting efficiency) and (iii) the targeting of the contrast agent. This presentation aims at reporting how a multifunctional (co)polymer can be designed and exploited for improving the contrasting ability and bioavailability of gadolinium-based complexes. [less ▲]

Detailed reference viewed: 94 (20 ULg)
Full Text
See detailDispersion nitroxide mediated polymerization of MMA in supercritical carbon dioxide
Grignard, Bruno ULg; Gigmes, Didier; Jérôme, Christine ULg et al

Poster (2009, May 14)

Controlled dispersion Nitroxide Mediated Polymerization (NMP) of methyl methacrylate (MMA) was successfully carried out for the first time in supercritical carbon dioxide (scCO2) in the presence of CO2 ... [more ▼]

Controlled dispersion Nitroxide Mediated Polymerization (NMP) of methyl methacrylate (MMA) was successfully carried out for the first time in supercritical carbon dioxide (scCO2) in the presence of CO2-philic perfluorinated surfactant that was generated “in situ”. The control of the MMA polymerization relies on the strategy developed by Charleux et al. that consists of using a SG1-based alkoxyamine, i.e. the block-builder, in the presence of small amount of styrene. In a first step, CO2 soluble polyheptadecafluorodecylacrylate was prepared in scCO2 using block-builder as an alkoxyamine. In a second step, nitroxide SG1 mediated dispersion polymerization of MMA was conducted at 70°C and 300 bar in the presence of 5 w% of SG1 terminated surfactant compared to the monomer. Different monomer to alkoxyamine molar ratios were investigated in order to target different molecular weights. In each case, the monomer conversion was high (>90 %), the experimental molecular weight was in good agreement with the theoretical value and the polydispersity was narrow (Mw/Mn ~1.2). Moreover, after depressurisation of the cell, PMMA was collected as a free flowing powder consisting of small sized microspheres. [less ▲]

Detailed reference viewed: 64 (8 ULg)
Full Text
See detailMannosylated amphiphilic and degradable PEO-b-PCL copolymers for drug delivery systems: preparation and sugar availability characterizations
Freichels, Hélène ULg; Imberty, Anne; Auezély-Velty, Rachel et al

Poster (2009, May 14)

Over the last decade, polymer micelles and nanoparticles attracted an increasing interest in pharmaceutical research because they can be used as efficient drug delivery systems. In this field, amphiphilic ... [more ▼]

Over the last decade, polymer micelles and nanoparticles attracted an increasing interest in pharmaceutical research because they can be used as efficient drug delivery systems. In this field, amphiphilic copolymers combining poly(ethylene oxide) and aliphatic polyester (such as poly(ε-caprolactone) (PCL) or polylactide (PLA)) are particularly of interest because (i) PEO has unique protein- repellent properties and thus provides a stealth behaviour to the drug carriers and (ii) aliphatic polyesters are biocompatible and biodegradable hydrophobic matrices well-suited for the incorporation of an hydrophobic drug. By end-capping the hydrophilic segment by a targeting moiety so that they may interact with membrane receptors, the biodistribution of polymeric micelles and nanoparticles stabilized with this copolymer can be modulated and can induce specific cellular uptake by receptor-mediated endocytosis. One class of interesting targeting agent is the saccharides, in particular the mannose, because of its specific interaction with mannose receptor, which are found on peripheral and bone marrow macrophages, dendritic cells and sinusoidal liver cells. In this study, the reductive amination reaction is use to attach this targeting agent. After optimisation of the reaction with amino fluorescein, a model amine, mannosylated copolymer of PEO and PCL has been prepared. The surface availability of the saccharide upon the micelles in aqueous phosphate buffer was then assessed by DLS through binding with the protein Concanavalin A (ConA), a known mannose receptor. The interactions between the Bcla lectin and the mannosylated micelles have then been studied by Isothermal Titration Calorimetry (ITC) and the thermodynamic parameters have been obtained. This polymer is particularly useful for the stabilization of PLGA nanoparticles with the goal to target M cells for oral vaccination. [less ▲]

Detailed reference viewed: 82 (10 ULg)
Full Text
See detailpH-sensitive micellar systems for controlled drug delivery: synthesis and structural characterization by small-angle neutron scattering
Joset, Arnaud ULg; Jérôme, Christine ULg; Brulet, Annie et al

Poster (2009, May 14)

The aim of the project is the preparation of micellar nanocarriers made of biocompatibles copolymers and their structural analysis by Small Angle Neutron Scattering (SANS). These micelles could be used in ... [more ▼]

The aim of the project is the preparation of micellar nanocarriers made of biocompatibles copolymers and their structural analysis by Small Angle Neutron Scattering (SANS). These micelles could be used in drug delivery applications to fight cancer1. The hydrophobic polycaprolactone (PCL) core is intended to incorporate the drug. The corona of hydrophilic polyethylene oxide (PEO) stabilizes the nanocarriers with respect to the plasma proteins. The pH in the neighborhood of the tumoral cells is lower than in the healthy cells. We incorporated a pH-sensitive sequence of poly(2-vinylpyridine) (P2VP). As a result, these micelles are expected to deliver their drug near the cancerous cells without affecting the healthy cells. When the pH is acidic, the P2VP is protonated and the chains are repulsive. The micellar size is then larger than in basic pH, when the P2VP is precipitated on the PCL core. We prepared PCL65-b-P2VP31 / PCL65-b-PEO114 and PCL32-b-P2VP52 / PCL36-b-PEO114 50:50 mixtures of diblocks copolymers. The resulting mixed micelles are analyzed by SANS. We developed a theoretical model with a spherical water-free PCL core. The PEO corona is described as consisting of gaussian chains with a thickness estimated as twice the chain gyration radius, Rg. We propose two alternatives for handling the P2VP zone. The P2VP molecules are either assumed to be Gaussian chains or they fill a shell of thickness L with possible water penetration.The fitting of the models to the experimental scattering cross sections leads to important structural parameters like the aggregation number, the core radius, the gyration radius and the thickness of the P2VP shell. [less ▲]

Detailed reference viewed: 87 (16 ULg)
Full Text
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 ▲]

Detailed reference viewed: 141 (16 ULg)
Full Text
Peer Reviewed
See detailpH-responsive flower-type micelles formed by a biotinylated poly(2-vinylpyridine)-block-poly(ethylene-oxide)-block-poly(ε-caprolactone) triblock copolymer
Van Butsele, Kathy ULg; Cajot, Sébastien ULg; Van Vlierberghe, Sandra et al

in Advanced Functional Materials (2009), 19(9), 1416-1425

In the present work, a method is proposed to assemble pH-responsive, flower-like micelles that can expose a targeting unit at their periphery upon a decrease in pH. The micelles are composed of a novel ... [more ▼]

In the present work, a method is proposed to assemble pH-responsive, flower-like micelles that can expose a targeting unit at their periphery upon a decrease in pH. The micelles are composed of a novel biotinylated triblock copolymer of poly(-caprolactone)-block-poly(ethylene oxide)-block-poly(2-vinylpyridine) (PCL-b-PEO-b-P2VP) and the non-biotinylated analogue. The block copolymers are synthesized by sequential anionic and ring-opening polymerization. The pH-dependent micellization behaviour in aqueous solution of the triblock copolymers developed is studied using dynamic light scattering, zeta potential, transmission electron microscopy (TEM), and fluorimetric measurements. The shielding of the biotin at neutral pH and their availability at the micelle surface upon protonation is established by TEM and surface plasmon resonance with avidin and streptavidin-coated gold surfaces. The preliminary stealthy behavior of these pH-responsive micelles is examined using the complement activation (CH50) test. [less ▲]

Detailed reference viewed: 115 (37 ULg)
See detailBiodegradable polymers-based nanofibers by electrospinning
Jérôme, Christine ULg

Conference (2009, May 07)

Detailed reference viewed: 10 (1 ULg)
Full Text
Peer Reviewed
See detailPegylated thermally responsive block copolymer micelles and nanogels via in situ RAFT aqueous dispersion polymerization
Rieger, Jutta ULg; Grazon, Chloé; Charleux, Bernadette et al

in Journal of Polymer Science. Part A, Polymer Chemistry (2009), 47(9), 2373-2390

A very straightforward approach was developed to synthesize pegylated thermoresponsive core-shell nanoparticles in a minimum of steps, directly in water. It is based on RAFT-controlled radical ... [more ▼]

A very straightforward approach was developed to synthesize pegylated thermoresponsive core-shell nanoparticles in a minimum of steps, directly in water. It is based on RAFT-controlled radical crosslinking copolymerization of N,N-diethylacrylamide (DEAAm) and N,N-methylene bisacrylamide (MBA) in aqueous dispersion polymerization. Because DEAAm is water-soluble and poly(N,N-diethylacrylamide) (PDEAAm) exhibits a lower critical solution temperature at 32 °C, the initial medium was homogeneous, whereas the polymer formed a separate phase at the reaction temperature. The first macroRAFT agent was a surface-active trithiocarbonate based on a hydrophilic poly(ethylene oxide) block and a hydrophobic dodecyl chain. It was further extented with N,N-dimethylacrylamide (DMAAm) to target macroRAFT agents with increasing chain length. All macroRAFT agents provided excellent control over the aqueous dispersion homopolymerization of DEAAm. When they were used in the radical crosslinking copolymerization of DEAAm and MBA, the stability and size of the resulting gel particles were found to depend strongly on the chain length of the macroRAFT agent, on the concentrations of both the monomer and the crosslinker, and on the process (one step or two steps). The best-suited experimental conditions to reach thermosensitive hydrogels with nanometric size and well-defined surface properties were determined. [less ▲]

Detailed reference viewed: 77 (12 ULg)
Full Text
See detailNovel (co)polymers by cobalt-mediated radical polymerization
Debuigne, Antoine ULg; Piette, Yasmine ULg; Poli, Rinaldo et al

Poster (2009, April 24)

Detailed reference viewed: 17 (8 ULg)
Full Text
Peer Reviewed
See detailLight induced functionalization of PCL-PEG block copolymers for the covalent immobilization of biomolecules
Pourcelle, Vincent; Freichels, Hélène ULg; Stoffelbach, François et al

in Biomacromolecules (2009), 10(4), 966-974

Functionalized poly-ε-caprolactone-block-polyethyleneglycol (PCL-PEG) amphiphilic copolymers were prepared to be constituents of nanocarriers used for the targeting of specific cells. Hence, we conceived ... [more ▼]

Functionalized poly-ε-caprolactone-block-polyethyleneglycol (PCL-PEG) amphiphilic copolymers were prepared to be constituents of nanocarriers used for the targeting of specific cells. Hence, we conceived a smooth and simple photografting methodology on these copolymers using a bifunctional molecular clip (O-succinimidyl-4-(p-azido-phenyl)butanoate). We prepared PCL-PEGs with pendent N-hydroxysuccinimide esters and studied the grafting with 3H-lysine, which radioactivity was counted by LSC. Several parameters were investigated, such as behavior of homopolymers, initial concentrations, irradiation, and incubation durations. Evidences of a “PEG directed photografting” are discussed and this selectivity could be improved by a selective solvent technique. The photografting on different PCL-PEGs revealed a dependency of the rates to the crystallinity of the copolymers. Several controls by SEC, DLS, and TEM of the treated copolymers were realized. Lastly, the coupling of α-d-mannopyranoside ligand was performed, reaching amounts of 5400 nmol/g of PCL-PEG. This derivatized PCL-PEG enters in the preparation of nanocarriers used for the targeting of antigen presenting cells. [less ▲]

Detailed reference viewed: 42 (4 ULg)