Synthetic and mechanistic insights in cobalt mediated radical polymerization (CMRP) of vinyl acetate and acrylonitrileDebuigne, Antoine ; ; Jérôme, Robert et alConference (2008, July 03) Detailed reference viewed: 4 (1 ULg) Imparting antifouling properties of poly(2-hydroxyethyl methacrylate) hydrogels by grafting poly(oligoethylene glycol methyl ether acrylate)Bozukova, Dimitriya ; ; Gillet, Marie-Claire et alin Langmuir (2008), 24(13), 6649-6658 The antifouling properties of poly(2-hydroxyethyl methacrylate-co-methyl methacrylate) hydrogels were improved by the surface grafting of a brush of poly(oligoethylene glycol methyl ether acrylate) [poly ... [more ▼] The antifouling properties of poly(2-hydroxyethyl methacrylate-co-methyl methacrylate) hydrogels were improved by the surface grafting of a brush of poly(oligoethylene glycol methyl ether acrylate) [poly(OEGA)]. The atom-transfer radical polymerization (ATRP) of OEGA (degree of polymerization = 8) was initiated from the preactivated surface of the hydrogel under mild conditions, thus in water at 25 °C. The catalytic system was optimized on the basis of two ligands [1,1,4,7,10,10-hexamethyl-triethylenetetramine (HMTETA) or tris[2-(dimethylamino)ethyl]amine (Me6TREN)] and two copper salts (CuIBr or CuICl). Faster polymerization was observed for the Me6TREN/CuIBr combination. The chemical composition and morphology of the coated surface were analyzed by X-ray photoelectron spectroscopy, attenuated total reflectance Fourier transform infrared spectroscopy, contact angle measurements by the water droplet and captive bubble methods, scanning electron microscopy, and environmental scanning electron microscopy. The hydrophilicity of the surface increased with the molar mass of the grafted poly(OEGA) chains, and the surface modifications were reported in parallel. The antifouling properties of the coatings were tested by in vitro protein adsorption and cell adhesion tests, with green fluorescent protein, β-lactamase, and lens epithelial cells, as model proteins and model cells, respectively. The grafted poly(OEGA) brush decreased the nonspecific protein adsorption and imparted high cell repellency to the hydrogel surface. [less ▲] Detailed reference viewed: 67 (13 ULg) Macromolecular engineering of biodegradable polyesters by ring-opening polymerization and 'Click' chemistryLecomte, Philippe ; Riva, Raphaël ; Jérôme, Christine et alin Macromolecular Rapid Communications (2008), 29(12-13), 982-997 Biodegradability makes aliphatic polyesters valuable candidates for biomaterials and environmentally friendly thermoplastics. Nevertheless, their chemical modification, which is mandatory for a series of ... [more ▼] Biodegradability makes aliphatic polyesters valuable candidates for biomaterials and environmentally friendly thermoplastics. Nevertheless, their chemical modification, which is mandatory for a series of potential applications, is usually a problem because it must be carried out under very mild conditions in order to prevent degradation by hydrolysis and/or transesterification from occurring. In this review, the copper(i) -catalyzed azide-alkyne cycloaddition, which is a click reaction, is shown to be very efficient to bypass these problems and to tailor the macromolecular architecture and functionality of those polyesters without facing undesired degradation reactions. [less ▲] Detailed reference viewed: 43 (22 ULg) Toward protein and cell repellent properties by surface modification of intraocular lenses; ; De Pauw, Marie-Claire et alPoster (2008, June 23) Detailed reference viewed: 12 (1 ULg) Polymer composite material structures comprising carbon based conductive loadsJérôme, Robert ; ; Detrembleur, Christophe et alPatent (2008) The present invention provides a polymer composite material structure comprising at least one layer of a foamed polymer composite material comprising a foamed polymer matrix and 0.1 wt% to 6 wt% carbon ... [more ▼] The present invention provides a polymer composite material structure comprising at least one layer of a foamed polymer composite material comprising a foamed polymer matrix and 0.1 wt% to 6 wt% carbon based conductive loads, such as e.g. carbon nanotubes, dispersed in the foamed polymer matrix. The polymer composite material structure according to embodiments of the present invention shows good shielding and absorbing properties notwithstanding the low amount of carbon based conductive loads. The present invention furthermore provides a method for forming a polymer composite material structure comprising carbon based conductive loads. [less ▲] Detailed reference viewed: 7 (2 ULg) Polymer composite material structures comprising carbon based conductive loadsJérôme, Robert ; ; Detrembleur, Christophe et alPatent (2008) The present invention provides a polymer composite material structure comprising at least one layer of a foamed polymer composite material comprising a foamed polymer matrix and 0.1 to 6 wt% carbon based ... [more ▼] The present invention provides a polymer composite material structure comprising at least one layer of a foamed polymer composite material comprising a foamed polymer matrix and 0.1 to 6 wt% carbon based conductive loads, such as e.g. carbon nanotubes, dispersed in the foamed polymer matrix. The polymer composite material structure according to embodiments of the present invention shows good shielding and absorbing properties notwithstanding the low amount of carbon based conductive loads. The present invention furthermore provides a method for forming a polymer composite material structure comprising carbon based conductive loads. [less ▲] Detailed reference viewed: 11 (2 ULg) New developments on the macromolecular engineering of ring-shaped aliphatic polyestersLecomte, Philippe ; ; Jérôme, Robert ![]() Scientific conference (2008, May 30) Detailed reference viewed: 4 (1 ULg) Surface coating of hydrogel intraocular lenses toward resistance to posterior capsular opacification; ; Gillet, Marie-Claire et alConference (2008, May 23) Detailed reference viewed: 23 (8 ULg) Dispersion of platinum modified carbon nanotubes within fuel cell membranesThomassin, Jean-Michel ; Caldarella, Giuseppe ; Germain, Albert et alPoster (2008, May 22) Detailed reference viewed: 11 (4 ULg) Polyolefin matrixes with permanent antibacterial activity: preparation, antibacterial activity, and action mode of the active species; ; Galleni, Moreno et alPoster (2008, May 22) Detailed reference viewed: 26 (12 ULg) Key role of metal-coordination in cobalt mediated radical polymerizationDebuigne, Antoine ; ; Jérôme, Christine et alPoster (2008, May 22) Detailed reference viewed: 5 (1 ULg) Effect of the addition of nanoclay on the extrusion foaming of poly(styrene-co-acrylonitrile) with supercritical carbon dioxideUrbanczyk, Laetitia ; Calberg, Cédric ; et alConference (2008, May 22) Detailed reference viewed: 12 (5 ULg) New perfluorinated macroligand for the implementation of Atom Transfer Radical Polymerization in supercritical carbon dioxideGrignard, Bruno ; Jérôme, Christine ; Calberg, Cédric et alConference (2008, May 05) Detailed reference viewed: 11 (3 ULg) Active Substance Delivery System Comprising A Hydrogel Matrix And Microcarriers; ; Evrard, Brigitte et alPatent (2008) Detailed reference viewed: 17 (1 ULg) Contribution of "click chemistry" to the synthesis of antimicrobial aliphatic copolyesterRiva, Raphaël ; Lussis, Perrine ; Lenoir, Sandrine et alin Polymer (2008), 49(8), 2023-2028 A straightforward strategy is proposed to impart antimicrobial properties to biodegradable poly(oxepan-2-one) (poly(epsilon-caprolactone) or PCL), which is based on the grafting of pendant ammonium salts ... [more ▼] A straightforward strategy is proposed to impart antimicrobial properties to biodegradable poly(oxepan-2-one) (poly(epsilon-caprolactone) or PCL), which is based on the grafting of pendant ammonium salts by "click" chemistry. First, statistical copolymerization of 3-chlorooxepan-2-one (alpha-chloro-epsilon-caprolactone or alpha Cl epsilon CL) with oxepan-2-one (epsilon-caprolactone or epsilon CL) was initiated by 2,2-dibutyl-2-stanna-1,3-dioxepane (DSDOP). In a second step, pendant chlorides were converted into azides by reaction with sodium azide (NaN3). Finally, quaternary ammonium containing alkynes were quantitatively added to the pendant azide groups of PCL by the copper-catalyzed Huisgen's 1,3-dipolar cycloaddition, which is a typical "click" reaction. An alternative two-step strategy based on the cycloaddition of the amine containing alkyne onto the pendant azides, followed by quaternization turned out to be less efficient. The antimicrobial activity was analyzed by the "shaking flask method" in the presence of Escherichia coli [less ▲] Detailed reference viewed: 73 (15 ULg) Synthesis of novel functional aliphatic polyesters by association of ring-opening polymerization and click chemistryLecomte, Philippe ; Schmeits, Stephanie ; Riva, Raphaël et alConference (2008, April 09) Nowadays, biodegradable and biocompatible aliphatic polyesters are widely used as environmentally friendly thermoplastics and biomaterials. Nevertheless, the absence of any functional group along the ... [more ▼] Nowadays, biodegradable and biocompatible aliphatic polyesters are widely used as environmentally friendly thermoplastics and biomaterials. Nevertheless, the absence of any functional group along the chain is a severe limitation for the development of new applications. Very recently, it was reported by Emrick et al. and by us that copper(I)-mediated 1,3-dipolar Huisgen's cycloaddition of alkynes and azides, the most widely used “click” reaction in the frame of macromolecular engineering, is very efficient to derivatize aliphatic polyesters. Due to the tolerance for many functional groups, cumbersome protection and deprotection steps are not needed. One main advantage of copper(I)-mediated Huisgen's cycloaddition compared to other reactions previously used to derivatize aliphatic polyesters relies on the mildness of the experimental conditions, which results in limited degradation. Our most recent results dealing with the combination of “click” chemistry and ring-opening polymerization towards functional PCL and PLA, networks, graft and hyperbranched copolymers will be highlighted. [less ▲] Detailed reference viewed: 27 (9 ULg) Synthesis of novel well-defined poly(vinyl acetate)-b-poly(acrylonitrile) and derivatized water-soluble poly(vinyl alcohol)-b-poly(acrylic acid) block copolymers by cobalt-mediated radical polymerizationDebuigne, Antoine ; ; Jérôme, Robert et alin Macromolecules (2008), 41(7), 2353-2360 Poly(vinyl acetate)−Co(acac)2 macroinitiators, prepared by cobalt-mediated radical polymerization of vinyl acetate (VAc), were used to synthesize well-defined poly(vinyl acetate)-b-poly(acrylonitrile ... [more ▼] Poly(vinyl acetate)−Co(acac)2 macroinitiators, prepared by cobalt-mediated radical polymerization of vinyl acetate (VAc), were used to synthesize well-defined poly(vinyl acetate)-b-poly(acrylonitrile) (PVAc-b-PAN) block copolymers. Different solvents and temperatures were tested for the polymerization of the acrylonitrile segment by cobalt-mediated radical polymerization (CMRP), and copolymers with low polydispersity were obtained provided that dimethylformamide was used as solvent at 0 °C. The mechanism of control was assumed to change from a degenerative chain transfer mechanism for the VAc polymerization to a reversible-termination process for the AN polymerization. The hydrolysis of the ester groups of the PVAc block and the nitrile groups of the PAN sequence of the copolymer by potassium hydroxide in an ethanol/water mixture provided the double hydrophilic and pH-responsive poly(vinyl alcohol)-b-poly(acrylic acid) block copolymer. Finally, the pH responsiveness of these copolymers was demonstrated by DLS pH titration with formation of aggregates at pH < 3. [less ▲] Detailed reference viewed: 31 (7 ULg) Core-Shell-Corona Micelles by PS-b-P2VP-b-PEO Copolymers: Focus on the Water-Induced Micellization ProcessWillet, Nicolas ; ; et alin Langmuir (2008), 24(7), 3009-3015 It is now well established that amphiphilic PS-b-P2VP-b-PEO linear triblock copolymers can form multilayered assemblies, thus core-shell-corona (CSC) micelles, in water. Micellization is triggered by ... [more ▼] It is now well established that amphiphilic PS-b-P2VP-b-PEO linear triblock copolymers can form multilayered assemblies, thus core-shell-corona (CSC) micelles, in water. Micellization is triggered by addition of a small amount of water into a dilute solution of the PS-b-P2VP-b-PEO copolymer in a non-selective organic solvent. However, the phenomena that take place at the very beginning of this process are poorly documented. How these copolymer chains are perturbed by addition of water was investigated in this work by light and neutron scattering techniques and transmission electron microscopy. It was accordingly possible to determine the critical water concentration (CWC), the compactness of the nano-objects in solution, their number of aggregation, and their hydrodynamic diameter at each step of the micellization process. [less ▲] Detailed reference viewed: 69 (17 ULg) Coating of gold nanoparticles by thermosensitive poly(N-isopropylacrylamide) end-capped by biotinAqil, Abdelhafid ; ; Greisch, Jean-François et alin 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 ▲] Detailed reference viewed: 96 (13 ULg) Mechanistic Insights into the Cobalt-Mediated Radical Polymerization (CMRP) of Vinyl Acetate with Cobalt(Iii) Adducts as InitiatorsDebuigne, Antoine ; ; Jérôme, Robert et alin 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 ▲] Detailed reference viewed: 25 (15 ULg) |
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