References of "Jérôme, Robert"
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See detailSynthesis and pH-dependent micellization of diblock copolymer mixtures
Van Butsele, Kathy ULg; Sibret, Pierre ULg; Fustin, Charles-André et al

in Journal of Colloid & Interface Science (2009), 329(2), 235-243

This work focused on the preparation and the aqueous solution properties of hybrid polymeric micelles consisting of a hydrophobic poly(ε-caprolactone) (PCL) core and a mixed shell of hydrophilic poly ... [more ▼]

This work focused on the preparation and the aqueous solution properties of hybrid polymeric micelles consisting of a hydrophobic poly(ε-caprolactone) (PCL) core and a mixed shell of hydrophilic poly(ethylene oxide) (PEO) and pH-sensitive poly(2-vinylpyridine) (P2VP). The hybrid micelles were successfully prepared by the rapid addition of acidic water to a binary solution of PCL34-b-PEO114 and PCL32-b-P2VP52 diblock copolymers in N,N-dimethylformamide. These micelles were pH-responsive as result of the pH-dependent ionization of the P2VP block. The impact of pH on the self-assembly of the binary mixture of diblocks—thus on the composition, shape, size and surface properties of the micelles—was studied by a variety of experimental techniques, i.e., dynamic and static light scattering, transmission electron microscopy, Zeta potential, fluorescence spectroscopy and complement hemolytic 50 test. [less ▲]

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See detailSelf-assembly and pH-responsiveness of ABC miktoarm star terpolymers
Van Butsele, Kathy ULg; Fustin, Charles-André; Gohy, Jean-François et al

in Langmuir (2009), 25(1), 107-111

This work deals with the self-assembly in water of ABC miktoarm star terpolymers consisting of hydrophobic poly(-caprolactone), hydrophilic poly(ethylene oxide) (PEO), and pH-sensitive poly(2 ... [more ▼]

This work deals with the self-assembly in water of ABC miktoarm star terpolymers consisting of hydrophobic poly(-caprolactone), hydrophilic poly(ethylene oxide) (PEO), and pH-sensitive poly(2-vinylpyridine) (P2VP). A variety of experimental techniques were used, including dynamic light scattering, transmission electron microscopy, and zeta potential. Special attention was paid to the pH dependency of the supramolecular self-assemblies. A key observation is the capability of the miktoarm terpolymers to form micelles stable over the whole range of pH, although a transition was observed from neutral to highly positively charged nanoobjects upon decreasing pH. [less ▲]

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See detailMetal enolates in polymer science and technology
Lecomte, Philippe ULg; Jérôme, Robert ULg

in Zabicky, Jacob (Ed.) The Chemistry of Metal Enolates (2009)

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See detailElectrografting of thermo-responsive polymer films on conducting surfaces
Gabriel, Sabine; Stach, M.; Confortini, O. et al

Poster (2008, November 28)

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See detailDesign of perfluorinated macroligand for the implementation of atom transfer radical polymerization in supercritical carbon dioxide
Grignard, Bruno ULg; Jérôme, Christine ULg; Calberg, Cédric ULg et al

Conference (2008, November 28)

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. The goal of the research relies on the development of ATRP of vinyl monomers in scCO2. Perfluorinated polymethacrylate, i.e. poly2,2,2-trifluoroethyl methacrylate (PFMA), was successfully prepared by homogenous ATRP using a polymeric ligand in order to complex the copper catalyst. CO2-soluble poly(2,2,2-trifluoroethylmethacrylate) was also prepared in supercritical CO2 by supported ATRP using a “pseudo-homogeneous” catalyst consisting of copper (I) ligated by macroligand immobilized onto an inorganic support, that results in polymers with well defined molecular weight and low polydispersity. 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 was also reported and the concept of dispersion ATRP was extended to the dispersion ATRP of styrene, to the synthesis of diblock copolymers beads using PMMA beads as macroinitiators, leading to (co)polymers with predictable molecular weight and narrow polydispersity. 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, leading to the formation of PMMA of well defined characteristics that was collected as fluorescent micropheres. [less ▲]

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See detailDispersion Atom Transfer Radical Polymerization of vinyl monomers in supercritical carbon dioxide
Grignard, Bruno ULg; Jérôme, Christine ULg; Calberg, Cédric ULg et al

in Macromolecules (2008), 41(22), 8575-8563

Controlled dispersion atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) was successfully carried out in supercritical carbon dioxide in the presence of aminated fluoropolymers ... [more ▼]

Controlled dispersion atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) was successfully carried out in supercritical carbon dioxide in the presence of aminated fluoropolymers. These materials played the dual role of macroligand for the copper bromide and also steric stabilizer to support formation of polymer microspheres. The livingness of the PMMA beads was confirmed by the one-pot two-step PMMA chain extension and the synthesis of poly(methyl methacrylate)-b-poly(2,2,2-trifluoroethyl methacrylate) (PMMA-b-PFMA) diblock copolymer in scCO2. Successful activator generated by electron transfer (AGET) for ATRP of MMA, using tin ethylhexanoate as a reducing agent, is also discussed, and the concept of dispersion ATRP of MMA was successfully extended to the controlled dispersion polymerization of styrene by ATRP leading to the formation of PS microparticles. Finally, due to the high solubility of the catalyst in scCO2, the purification of PMMA was investigated by supercritical fluid extraction, leading to the preparation of PMMA beads with low residual catalyst traces. [less ▲]

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See detailSynthesis of biodegradable poly-epsilon-caprolactone microspheres by dispersion ring-opening polymerization in supercritical carbon dioxide
Grignard, Bruno ULg; Stassin, Fabrice; Calberg, Cédric ULg et al

in Biomacromolecules (2008), 9(11), 3141-3149

A series of fluorinated diblock and triblock copolymers of poly(ε-caprolactone) and poly(heptadecafluorodecylacrylate) were prepared by combining ring-opening polymerization of ε-CL and atom transfer ... [more ▼]

A series of fluorinated diblock and triblock copolymers of poly(ε-caprolactone) and poly(heptadecafluorodecylacrylate) were prepared by combining ring-opening polymerization of ε-CL and atom transfer radical polymerization of the acrylate. These copolymers with well-controlled molecular weight and composition were characterized by 1H NMR spectroscopy and used as stabilizers for the dispersion ring-opening polymerization of ε-CL in supercritical carbon dioxide. The effect of composition and architecture of the polymeric stabilizers on the stabilization of PCL microspheres was investigated. Finally, purification of PCL was successfully implemented by reactive supercritical fluid extraction of the tin catalyst. [less ▲]

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See detailTwo-component "onionlike" micelles with a PPO core, a PDMAEMA shell and a PEO corona : formation and crosslinking
Petrov, Petar; Tsvetanov, Christo B.; Jérôme, Robert ULg

in Polymer International (2008), 57(11), 1258-1264

Chemical or physical crosslinking of supramolecular assemblies gives them stability in a wide range of environments. Much attention is paid to multilayer (onion-like) polymeric micelles because their ... [more ▼]

Chemical or physical crosslinking of supramolecular assemblies gives them stability in a wide range of environments. Much attention is paid to multilayer (onion-like) polymeric micelles because their functionality is higher than classic core-shell micelles. This work reports on the formation and crosslinking of onion-like micelles prepared by mixing two different block copolymers containing a crosslinkable poly(dimethylaminoethyl methacrylate) (PDMAEMA) block. [less ▲]

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See detailControlled release of drugs from multi-component biomaterials
Zalfen, Alina ULg; Nizet, D.; Jérôme, Christine ULg et al

in Acta Biomaterialia (2008), 4(6), 1788-1796

In order to control their release, drugs are encapsulated into systems which are expected to provide a certain site with a predetermined amount of drug over a well-defined period of time. Here we report ... [more ▼]

In order to control their release, drugs are encapsulated into systems which are expected to provide a certain site with a predetermined amount of drug over a well-defined period of time. Here we report on a multi-component drug delivery biomaterial that consists of a hydrogel matrix in which drug-loaded biodegradable microcarriers are dispersed, and whose potential applications could be found in the design of implantable devices with long-term activity, as required by contraceptive and hormone replacement treatments. The release profile of the drug can actually be tuned by the complex interplay of several release mechanisms, including the permeability and eventually the degradation rate of the microcarriers and the diffusion through the hydrogel. The hydrogel consisted of 2-hydroxyethyl methacrylate cross-linked by ethylene glycol dimethacrylate. The microcarriers were biodegradable poly-ε-caprolactone (PCL) microspheres in which active molecules, such as levonorgestrel (LNG), were encapsulated. The hydrogels were characterized by water swelling, thermal properties, LNG diffusion through drug-free and drug-depleted hydrogel membranes and LNG release from devices with drug dispersed in the hydrogel. The PCL microspheres were observed by scanning electron microscopy; their size distribution, LNG loading and release were also investigated. The hydrogel-microsphere assemblies were characterized in terms of the distribution of the microspheres within the hydrogel, water swelling and the release of the encapsulated molecules. The developed device, due to its composite structure, has the ability to combine several release mechanisms, leading to drug release obeying zero-order kinetics for most of the time. [less ▲]

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See detailElectrografting method for forming and regulating a strong adherent nanostructured polymer coating
Jérôme, Robert ULg; Jérôme, Christine ULg; Serwas, Harry ULg et al

Patent (2008)

Electrografting method for forming and regulating a strongly adherent nanostructured polymer coating onto an electro-conductive surface profile characterized in that the surface profile is regulated by ... [more ▼]

Electrografting method for forming and regulating a strongly adherent nanostructured polymer coating onto an electro-conductive surface profile characterized in that the surface profile is regulated by electrodeposition of nanometre- and/or micrometre-scale nuclei onto the surface profile prior to or simultaneously to the formation of the polymer coating. [less ▲]

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See detailPEO coated magnetic nanoparticles for biomedical application
Aqil, Abdelhafid ULg; Vasseur, S.; Duguet, E. et al

in European Polymer Journal (2008), 44(10), 3191-3199

This paper reports on the preparation, characterization and stealthiness of superparamagnetic nanoparticles (magnetite Fe3O4) with a 5 nm diameter and stabilized in water (pH 6.5) by a shell of water ... [more ▼]

This paper reports on the preparation, characterization and stealthiness of superparamagnetic nanoparticles (magnetite Fe3O4) with a 5 nm diameter and stabilized in water (pH 6.5) by a shell of water-soluble poly(ethylene oxide) (PEO) chains. Two types of diblock copolymers, i.e., poly(acrylic acid)-b-poly(ethylene oxide), PAA–PEO, and poly(acrylic acid)-b-poly(acrylate methoxy poly(ethyleneoxide)), PAA–PAMPEO, were prepared as stabilizers with different compositions and molecular weights. At pH 6.5, the negatively ionized PAA block interacts strongly with the positively-charged nanoparticles, thus playing the role of an anchoring block. Aggregates of coated nanoparticles were actually observed by dynamic light scattering (DLS) and transmission electron microscopy (TEM). The hydrodynamic diameter was in the 50–100 nm range and the aggregation number (number of nanoparticles per aggregate) was lying between several tens and hundred. Moreover, the stealthiness of these aggregates was assessed “in vitro” by the hemolytic CH50 test. No response of the complement system was observed, such that biomedical applications can be envisioned for these magnetic nanoparticles. Preliminary experiments of magnetic heating (10 kA/m; 108 kHz) were performed and specific absorption rate varied from 2 to 13 W/g(Fe). [less ▲]

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See detailRecent advances in the synthesis of aliphatic polyesters by “click” chemistry
Riva, Raphaël ULg; Jérôme, Christine ULg; Jérôme, Robert ULg et al

Conference (2008, September 11)

Since the discovery of Sharpless and Meldal, the copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) is more and more popular in the field of macromolecular engineering owing to its robustness, its ... [more ▼]

Since the discovery of Sharpless and Meldal, the copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) is more and more popular in the field of macromolecular engineering owing to its robustness, its high tolerance to a wide range of functional groups without any need of protecting groups and the absence of side-products. This reaction is known to be a very efficient “click” reaction as defined by Sharpless. The chemical modification of aliphatic polyesters remains, at the time being, a very difficult task to achieve because of the very limited number of efficient chemical reactions, which can be implemented in the absence of chain degradation. The main purpose of this contribution is to report on the most recent advances on the use of CuAAC to derivatize aliphatic polyesters (Scheme 1). Interestingly enough, it was recently shown that CuAAC carried out onto aliphatic polyesters attached with either azides or alkynes is very efficient under mild conditions, which limit undesirable degradation. Several functional groups were grafted onto aliphatic polyesters by CuAAC without using any protection/deprotection reactions. The CuAAC is also very efficient to prepare aliphatic polyesters with various architectures as highlighted by the synthesis of graft copolymers, star-shaped copolymers and networks. This “click” chemistry has been combined with other polymerization mechanism such as ATRP in order to extend further the range of available polymers. [less ▲]

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See detailMacromolecular engineering of aliphatic polyesters by ring-opening polymerization
Lecomte, Philippe ULg; Jérôme, Christine ULg; Jérôme, Robert ULg

Conference (2008, September 09)

During the past few years, a steadily increasing attention was paid to the synthesis of biodegradable and biocompatible aliphatic polyesters because of potential applications as biomaterials or as ... [more ▼]

During the past few years, a steadily increasing attention was paid to the synthesis of biodegradable and biocompatible aliphatic polyesters because of potential applications as biomaterials or as environmentally friendly thermoplastics. The first purpose of this work is to show that the modification of these aliphatic polyesters by pendant functional groups is an efficient tool to tailor the main properties, including biodegradation rate, bioadhesion, hydrophilicity, degree of crystallinity. The strategies implemented for the synthesis of aliphatic polyesters bearing pendant functional groups rely on the synthesis of g-substituted e-caprolactones followed by their ring-opening polymerization and on the chemical modification of duly functionalized aliphatic polyesters.The second part of the lecture will be dedicated to some recent examples dealing with the use of functional caprolactones to prepare various architectures such as star-shaped copolymers, graft copolymers, macrocycles and networks. [less ▲]

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See detailFoams of polycaprolactone/MWNT nanocomposites for efficient EMI shielding
Thomassin, Jean-Michel ULg; Pagnoulle, Christophe; Bednarz, Lukasz et al

Conference (2008, September 09)

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See detailPreparation of stable suspensions of gold nanoparticles in water by sonoelectrochemistry
Aqil, Abdelhafid ULg; Serwas, Harry; Delplancke, J. L. et al

in Ultrasonics Sonochemistry (2008), 15(6), 1055-1061

Stable suspensions of gold nanoparticles in water were prepared with high yield by a novel one-step ultrasound assisted electrochemical process. Various strategies based on the addition of either tailor ... [more ▼]

Stable suspensions of gold nanoparticles in water were prepared with high yield by a novel one-step ultrasound assisted electrochemical process. Various strategies based on the addition of either tailor-made polymers or mixtures of commercially available polymers, in the electrochemical bath have been found successful to avoid nanoparticles aggregation commonly observed by sonoelectrochemistry. α-Methoxy-ω-mercapto-poly(ethylene oxide) or poly(vinyl pyrrolidone)/polyethylene oxide mixtures were able to build up a coalescence barrier around the gold nanoparticles. The results showed that the size of the gold nanoparticles could be easily tuned between 5 nm and 35 nm by simple control of the electrochemical parameters, i.e. the deposition time (TON) from 10 ms to 20 ms. The properties of as-prepared gold nanoparticles were compared to the ones of gold colloids prepared by the more conventional wet nanoprecipitation method using chemical reductive agents. [less ▲]

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See detailCobalt-mediated radical polymerization of acrylonitrile: Kinetics investigations and DFT calculations
Debuigne, Antoine ULg; Michaux, Catherine; Jérôme, Christine ULg et al

in Chemistry : A European Journal (2008), 14(25), 7623-7637

The successful controlled homopolymerization of acrylonitrile (AN) by cobalt-mediated radical polymerization (CMRP) is reported for the first time. As a rule, initiation of the polymerization was carried ... [more ▼]

The successful controlled homopolymerization of acrylonitrile (AN) by cobalt-mediated radical polymerization (CMRP) is reported for the first time. As a rule, initiation of the polymerization was carried out starting from a conventional azo-initiator (V-70) in the presence of bis(acetylacetonato)cobalt(II) ([Co(acac)2]) but also by using organocobalt(III) adducts. Molar concentration ratios of the reactants, the temperature, and the solvent were tuned, and the effect of these parameters on the course of the polymerization is discussed in detail. The best level of control was observed when the AN polymerization was initiated by an organocobalt(III) adduct at 0 °C in dimethyl sulfoxide. Under these conditions, poly(acrylonitrile) with a predictable molar mass and molar mass distribution as low as 1.1 was prepared. A combination of kinetic data, X-ray analyses, and DFT calculations were used to rationalize the results and to draw conclusions on the key role played by the solvent molecules in the process. These important mechanistic insights also permit an explanation of the unexpected solvent effect that allows the preparation of well-defined poly(vinyl acetate)-b-poly(acrylonitrile) by CMRP. [less ▲]

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See detailSynthesis of PCL/clay masterbatches in supercritical carbon dioxide
Urbanczyk, Laetitia ULg; Calberg, Cédric ULg; Stassin, Fabrice et al

in Polymer (2008), 49(18), 3979-3986

Pre-exfoliated nanoclays were prepared through a masterbatch process using supercritical carbon dioxide as solvent and poly(epsilon-caprolactone) as organic matrix. In situ polymerization of epsilon ... [more ▼]

Pre-exfoliated nanoclays were prepared through a masterbatch process using supercritical carbon dioxide as solvent and poly(epsilon-caprolactone) as organic matrix. In situ polymerization of epsilon-caprolactone in the presence of large amount of clay was conducted to obtain these easily dispersible nanoclays, collected as a dry and fine powder after reaction. Dispersion of these pre-exfoliated nanoclays in chlorinated polyethylene was also investigated. All the results confirm the specific advantages of supercritical CO2 towards conventional solvents for filler modification. [less ▲]

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See detailNormal and frictional forces between surfaces bearing polyelectrolyte brushes
Raviv, Uri; Giasson, Suzanne; Kampf, Nir et al

in Langmuir (2008), 24(16), 8678-8687

Normal and shear forces were measured as a function of surface separation, D, between hydrophobized mica surfaces bearing layers of a hydrophobic−polyelectrolytic diblock copolymer, poly(methyl ... [more ▼]

Normal and shear forces were measured as a function of surface separation, D, between hydrophobized mica surfaces bearing layers of a hydrophobic−polyelectrolytic diblock copolymer, poly(methyl methacrylate)-block-poly(sodium sulfonated glycidyl methacrylate) copolymer (PMMA-b-PSGMA). The copolymers were attached to each hydrophobized surface by their hydrophobic PMMA moieties with the nonadsorbing polyelectrolytic PSGMA tails extending into the aqueous medium to form a polyelectrolyte brush. Following overnight incubation in 10−4 w/v aqueous solution of the copolymer, the strong hydrophobic attraction between the hydrophobized mica surfaces across water was replaced by strongly repulsive normal forces between them. These were attributed to the osmotic repulsion arising from the confined counterions at long-range, together with steric repulsion between the compressed brush layers at shorter range. The corresponding shear forces on sliding the surfaces were extremely low and below our detection limit (±20−30 nN), even when compressed down to a volume fraction close to unity. On further compression, very weak shear forces (130 ± 30 nN) were measured due to the increase in the effective viscous drag experienced by the compressed, sliding layers. At separations corresponding to pressures of a few atmospheres, the shearing motion led to abrupt removal of most of the chains out of the gap, and the surfaces jumped into adhesive contact. The extremely low frictional forces between the charged brushes (prior to their removal) is attributed to the exceptional resistance to mutual interpenetration displayed by the compressed, counterion-swollen brushes, together with the fluidity of the hydration layers surrounding the charged, rubbing polymer segments. [less ▲]

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