References of "Jérôme, Robert"
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See detailCoating of gold nanoparticles by thermosensitive poly(N-isopropylacrylamide) end-capped by biotin
Aqil, Abdelhafid ULg; Qiu, Hongjin; Greisch, Jean-François ULg et al

in Polymer (2008), 49(5), 1145-1153

Gold nanoparticles (NPs) were prepared by reduction of HAuCl4 in aqueous solution and stabilized by poly(N-isopropylacrylamide) (PNIPAM). PNIPAM was prepared by two distinct routes: (i) conventional free ... [more ▼]

Gold nanoparticles (NPs) were prepared by reduction of HAuCl4 in aqueous solution and stabilized by poly(N-isopropylacrylamide) (PNIPAM). PNIPAM was prepared by two distinct routes: (i) conventional free-radical polymerization leading to polymer without any reactive end-group, and (ii) Reversible Addition–Fragmentation chain Transfer (RAFT) polymerization with 2-dodecylsulfanylthiocarbonylsulfanyl-2-methyl propionic acid (DMP) as a RAFT agent. PNIPAM with low polydispersity was then end-capped by an α-carboxylic acid and an ω-trithiocarbonate that was converted into an ω-thiol upon hydrolysis. This hetero-telechelic polymer was analyzed by mass spectroscopy, size exclusion chromatography (SEC) and 1H NMR. Even without thiol end-group, known for chemisorption onto gold, PNIPAM was effective in stabilizing gold NPs (1–5 nm). The thermosensitivity of PNIPAM at the surface of gold NPs was, however, dependent on the molecular weight of the chains. Finally, the α-carboxyl end-group of PNIPAM was used to anchor biotin, which is indeed known for complexation with avidin, which is a possible strategy for the coated gold NPs to be involved as building blocks in supramolecular assemblies. TEM and UV–vis spectroscopy were used to characterize the gold nanoparticles. [less ▲]

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See detailMechanistic Insights into the Cobalt-Mediated Radical Polymerization (CMRP) of Vinyl Acetate with Cobalt(Iii) Adducts as Initiators
Debuigne, Antoine ULg; Champouret, Yohan; Jérôme, Robert ULg et al

in Chemistry : A European Journal (2008), 14(13), 4046-4059

Over the past few years, cobalt-mediated radical polymerization (CMRP) has proved efficient in controlling the radical polymerization of very reactive monomers, such as vinyl acetate (VAc). However, the ... [more ▼]

Over the past few years, cobalt-mediated radical polymerization (CMRP) has proved efficient in controlling the radical polymerization of very reactive monomers, such as vinyl acetate (VAc). However, the reason for this success and the intimate mechanism remained basically speculative. Herein, two mechanisms are shown to coexist: the reversible termination of the growing poly(vinyl acetate) chains by the Co(acac)(2) complex (acac: acetylacetonato), and a degenerative chain-transfer process. The importance of one contribution over the other strongly depends on the polymerization conditions, including complexation of cobalt by ligands, such as water and pyridine. This significant progress in the CMRP mechanism relies on the isolation and characterization of the very first cobalt adducts formed in the polymerization medium and their use as CMRP initiators. The structure proposed for these adducts was supported by DFT calculations. Beyond the control of the VAc polymerization, which is the best ever achieved by CMRP, extension to other monomers and substantial progress in macromolecular engineering are now realistic forecasts. [less ▲]

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See detailIn-Situ Nitroxide-Mediated Radical Polymerization (Nmp) Processes: Their Understanding and Optimization
Sciannamea, Valérie; Jérôme, Robert ULg; Detrembleur, Christophe ULg

in Chemical Reviews (2008), 108(3), 1104-26

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See detailAtom transfer radical polymerization of MMA with a macromolecular ligand in a fluorinated solvent and in supercritical carbon dioxide
Grignard, Bruno ULg; Jérôme, Christine ULg; Calberg, Cédric ULg et al

in European Polymer Journal (2008), 44(3), 861-871

Macromolecular fluorinated ligands were prepared according to a three-step strategy that consists of the random copolymerization of heptadecafluorodecyl acrylate and 2-hydroxyethylacrylate, followed by ... [more ▼]

Macromolecular fluorinated ligands were prepared according to a three-step strategy that consists of the random copolymerization of heptadecafluorodecyl acrylate and 2-hydroxyethylacrylate, followed by the esterification of the pendant hydroxyl groups with acryloyl chloride and the Michael-type addition of tetraethyldiethylenetriamine onto the acrylic double bonds of the polymeric chains. These fluorinated macroligands were successfully used in the atom transfer radical polymerization of MMA catalyzed by a copper salt in a fluorinated solvent. The polymerization control was analyzed in relation to the copper salt, the initiator and the molecular weight and composition of the macroligand before being extended to the heterogeneous ATRP of MMA in scCO2. [less ▲]

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See detailAmphiphilic sun-shaped polymers by grafting macrocyclic copolyesters with PEO
Li, Haiying; Jérôme, Robert ULg; Lecomte, Philippe ULg

in Macromolecules (2008), 41(3), 650-654

An amphiphilic sun-shaped copolymer was successfully prepared by esterification of carboxylic acid terminated PEO with the pendent hydroxyl groups of high molecular weight (M-n = 28 000) cyclic PCL. The ... [more ▼]

An amphiphilic sun-shaped copolymer was successfully prepared by esterification of carboxylic acid terminated PEO with the pendent hydroxyl groups of high molecular weight (M-n = 28 000) cyclic PCL. The cyclic structure of the copolyester originally resulted from the polymerization initiation by a cyclic tin dialkoxide and was ultimately stabilized by the intramolecular cross-linking of a few unsaturated groups. [less ▲]

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See detailPH-responsive biodegradable amphiphilic networks
Zednik, Jiri; Riva, Raphaël ULg; Lussis, Perrine ULg et al

in Polymer (2008), 49(3), 697-702

Copper-mediated azide - alkyne Huisgen's 1,3-dipolar cycloaddition is a "click" reaction that was successfully used to prepare pH-responsive, amphiphilic and biodegradable networks. Indeed, this reaction ... [more ▼]

Copper-mediated azide - alkyne Huisgen's 1,3-dipolar cycloaddition is a "click" reaction that was successfully used to prepare pH-responsive, amphiphilic and biodegradable networks. Indeed, this reaction proved to be very efficient in the "one pot" grafting of amino alkyne onto azide containing poly(epsilon-caprolactone) and the cross-linking of these chains by alpha,omega-dialkynyl poly(ethylene oxide). The pH-controlled release of guests hosted during the cross-linking step was illustrated with an entrapped model dye. [less ▲]

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See detailSynthesis of eight-shaped and star-shaped poly(ε-caprolactone) and their amphiphilic derivatives
Li, Haiying; Riva, Raphaël ULg; Kricheldorf, Hans R. et al

in Chemistry : A European Journal (2008), 14(1), 358-368

Spirocyclic tin dialkoxides are unique initiators for the ring-expansion polymerization of lactones leading to complex, but well-defined macromolecular architectures. In a first example, -caprolactone (CL ... [more ▼]

Spirocyclic tin dialkoxides are unique initiators for the ring-expansion polymerization of lactones leading to complex, but well-defined macromolecular architectures. In a first example, -caprolactone (CL) was polymerized, followed by the resumption of polymerization of a mixture of CL and CL -substituted by a chloride (ClCL), so leading to living eight-shaped chains. Upon hydrolysis of the alkoxides, a four-arm star-shaped copolyester was formed, whose each arm was grafted by conversion of the chloride units into azides, followed by the Huisgen's [3+2] cycloaddition of alkyne end-capped poly(ethylene oxide) (PEO) onto the azide substituents. The complexity of this novel amphiphilic architecture was increased further by substituting the four-arm interconnecting PCL by an eight-shaped PCL. In a preliminary step, CL was polymerized followed by a few units of CL -substituted by an acrylate. The intramolecular photo-crosslinking of the acrylates adjacent to the tin dialkoxides was effective in stabilizing the eight-shaped polyester while preserving the chain growth sites. This quite unusual tetrafunctional macroinitiator was used to copolymerize CL and ClCL, followed by hydrolysis of the alkoxides, conversion of the chloride units into azides and grafting of the four arms by PEO (see above). This architecture reported for the very first time is nothing but a symmetrical four-tail eight-shaped copolyester macromolecule. [less ▲]

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See detailMagnetic nanoparticles coated by temperature responsive copolymers for hyperthermia
Aqil, Abdelhafid ULg; Vasseur, Sébastien; Duguet, Etienne et al

in Journal of Materials Chemistry (2008), 18(28), 3352-3360

Various temperature-responsive N-isopropylacrylamide-based functional copolymers were prepared and used for the stabilization of iron oxide nanoparticles. The copolymers investigated are poly(acrylic acid ... [more ▼]

Various temperature-responsive N-isopropylacrylamide-based functional copolymers were prepared and used for the stabilization of iron oxide nanoparticles. The copolymers investigated are poly(acrylic acid)-b-poly(N-isopropylacrylamide) (PAA-PNIPAM) and poly(acrylic acid)-b-poly(N-isopropylacrylamide)-b-poly(acrylate methoxy poly(ethylene oxide)) (PAA-PNIPAM-PAMPEO), with different molecular weights. The coated nanoparticles were characterized in terms of size by a combination of dynamic light scattering (DLS) and transmission electron microscopy (TEM). A sharp temperature transition was confirmed by particle size measurements vs. temperature. In addition, the stealthiness of the coated nanoparticles has been assessed in vitro by the haemolytic CH50 test. These measurements evidenced the crucial role of the PEO segments on the stealthiness of the nanoparticles and thus that such copolymers are particularly suitable for biomedical applications. Preliminary experiments of alternating magnetic field induced heating were performed and specific absorption rates of the various samples were recorded. [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 detailMetal-coordination: an effective lever for cobalt-mediated radical polymerization
Debuigne, Antoine ULg; Jérôme, Christine ULg; Jérôme, Robert ULg et al

in Polymer Preprints (2008), 49(27), 193-194

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

in Journal of Materials Chemistry (2008), 18(7), 792-796

Nanocomposites of polycaprolactone (PCL) filled with multi-walled carbon nanotubes (MWNTs) were foamed by supercritical CO2 in order to prepare materials with reduced electromagnetic interference (EMI ... [more ▼]

Nanocomposites of polycaprolactone (PCL) filled with multi-walled carbon nanotubes (MWNTs) were foamed by supercritical CO2 in order to prepare materials with reduced electromagnetic interference (EMI). Two mixing techniques were used, i.e., melt blending and co-precipitation. Shielding efficiency as high as 60 to 80 dB together with a low reflectivity was observed at a very low vol% of MWNTs (0.25 vol%). The reflectivity of the nanocomposites was advantageously decreased upon foaming. The uniformity of the open-cell structure was assessed by scanning electron microscopy. These foamed PCL/MWNT nanocomposites are very promising EMI shielding materials because their performances result from absorption at low filler content and not from reflection at relatively high filler content as was previously the case. [less ▲]

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See detailXRD and NMR characterization of synthetic hectorites and the corresponding surfactant-exchanged clays
Gertsmans, André; Urbanczyk, Laetitia ULg; Jérôme, Robert ULg et al

in Clay Minerals (2008), 43

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See detailCopper bromide complexed by fluorinated macroligands: towards microspheres by ATRP of vinyl monomers in scCO2
Grignard, Bruno ULg; Jérôme, Christine ULg; Calberg, Cédric ULg et al

in Chemical Communications (2008), (3), 314-316

We report the successful synthesis of poly(methyl methacrylate) (PMMA) by atom transfer radical polymerization using a catalyst ligated to a polymeric ligand having a dual role, i.e., the complexation of ... [more ▼]

We report the successful synthesis of poly(methyl methacrylate) (PMMA) by atom transfer radical polymerization using a catalyst ligated to a polymeric ligand having a dual role, i.e., the complexation of the copper salt and the stabilization of the growing PMMA particles; at the end of the polymerization, the catalyst is removed by supercritical fluid extraction leading to PMMA microspheres with low residual catalyst content. [less ▲]

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See detailFunctional amphiphilic and biodegradable copolymers for intravenous vectorization
Van Butsele, Kathy ULg; Jérôme, Robert ULg; Jérôme, Christine ULg

in Polymer (2007), 48

This paper aims at reporting on the design of polymeric drug nanocarriers used in cancer therapy, with a special emphasis on the control of their biodistribution. First, the prominent role of poly ... [more ▼]

This paper aims at reporting on the design of polymeric drug nanocarriers used in cancer therapy, with a special emphasis on the control of their biodistribution. First, the prominent role of poly(ethylene oxide) in the lifetime of nanocarriers circulating in the blood stream is highlighted, and the origin of a passive targeting based on a difference in the anatomy of tumors and normal tissues is discussed. The main body of the review is devoted to the targeting of nanocarriers towards tumors and the underlying concepts. As a rule, either the constitutive polymer is stimuli-responsive and the locus of drug release is where the stimulation occurs, or a ligand endowed with specific recognition is grafted onto the nanocarrier. Finally, the fate of the nanocarrier after drug delivery and the bioelimination of the polymer(s) involved are briefly considered. [less ▲]

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See detailCombination of electrografting and layer-by-layer deposition: an efficient way to tailor polymer coatings of (semi)-conductors
Charlot, Aurélia; Gabriel, Sabine ULg; Detrembleur, Christophe ULg et al

in Chemical Communications (2007), (44), 4656-4658

This communication reports on a novel, simple and highly versatile concept, which consists in combining the advantages of two complementary and relevant techniques (i) electrografting and (ii) layer-by ... [more ▼]

This communication reports on a novel, simple and highly versatile concept, which consists in combining the advantages of two complementary and relevant techniques (i) electrografting and (ii) layer-by-layer deposition process with the goal to tailor strongly adhering coatings to (semi)-conducting surfaces imparting them with tunable specific properties. [less ▲]

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See detailPEGylated quaternized copolymer/DNA complexes for gene delivery
Vroman, Benoît; Ferreira, Isabel; Jérôme, Christine ULg et al

in International Journal of Pharmaceutics (2007), 344(1-2), 88-95

The aim of this study was to improve the colloidal stability, decrease unspecific interactions with cells and blood components of a novel gene delivery system composed of epsilon-caprolactone and ... [more ▼]

The aim of this study was to improve the colloidal stability, decrease unspecific interactions with cells and blood components of a novel gene delivery system composed of epsilon-caprolactone and quaternized epsilon-caprolactone. For this purpose, diblock 50/50 copolymer was used to generate complexes-with DNA by either the solvent evaporation technique and by dialysis. The size, surface charge and degree of interaction of the plasmid-loaded formulations were measured. Then, polyplexes were combined with a poly(CL)-b-PEG copolymer to create a hydrophilic corona on the surface of the complexes. The cytotoxicity, transfection efficiency and cellular uptake of polyplexes and their association with PEG were evaluated on HeLa cells. The dialysis method did not allow to reduce the size of complexes as compared to the solvent evaporation method. The zeta potential of polyplexes became positive from a charge ratio of 4. The degree of interaction of copolymer with plasmid DNA was very high. Cytotoxicity and transfection efficiency were found to be comparable to polyethylenimine 50 kDa. Association of polyplexes with poly(CL)-b-PEG copolymer led to a small increase in particle size and a sharp decrease of charge surface. Cytotoxicity, transfection efficiency and cellular uptake were significantly reduced relative to unshielded copolymer/DNA complexes. The PEGylated formulations may be an attractive approach for an in vivo application. [less ▲]

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See detailFast multiresponsive micellar gels from a smart ABC triblock copolymer
Willet, Nicolas ULg; Gohy, Jean-François; Lei, Liangcai et al

in Angewandte Chemie (International ed. in English) (2007), 46(42), 7988-7992

The triblock copolymer PS-b-P2VP-b-PEO undergoes simultaneous micellization and gelation, leading to high-storage-modulus materials that have fast responses to pH value, temperature, ionic strength, and ... [more ▼]

The triblock copolymer PS-b-P2VP-b-PEO undergoes simultaneous micellization and gelation, leading to high-storage-modulus materials that have fast responses to pH value, temperature, ionic strength, and shearing. The gel has a hierarchical structure with spherical core-shell-corona micelles, which, in turn, pack closely into an ordered cubic structure. [less ▲]

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See detailBeneficial effect of carbon nanotubes on the performances of Nafion membranes in fuel cell applications
Thomassin, Jean-Michel ULg; Kollar, Jozef; Caldarella, Giuseppe ULg et al

in Journal of Membrane Science (2007), 303(1-2), 252-257

Multi-walled carbon nanotubes (MWCNTs) were dispersed by melt-extrusion within Nafion(R) membranes in order to decrease the methanol permeability without deleterious effect on the ionic conductivity. The ... [more ▼]

Multi-walled carbon nanotubes (MWCNTs) were dispersed by melt-extrusion within Nafion(R) membranes in order to decrease the methanol permeability without deleterious effect on the ionic conductivity. The risk of short-circuits was minimized by keeping the carbon nanotubes content lower than the percolation threshold. Two series of carbon nanotubes grafted by carboxylic acid groups were used, i.e., commercially available carbon nanotubes and MWCNTs home-grafted by carboxylic acid containing alkyl radicals. The second series of nanotubes were more resistant to break-up during melt-processing. Methanol permeability was decreased by approximately 60% without any decrease in the ionic conductivity. In parallel, the Young's modulus was increased by 140% and 160% as compared to pure Nafion(R) at MWCNT contents of 1 and 2 wt%, respectively. [less ▲]

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