References of "Jérôme, Robert"
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See detailCathodic electrografting of acrylics: From fundamentals to functional coatings
Gabriel, Sabine ULg; Jérôme, Robert ULg; Jérôme, Christine ULg

in Progress in Polymer Science (2010), 35

Promoting permanent adhesion between so dissimilar materials as polymers and metals is a very challenging target and a severe brake to the implementation of many potential applications. However, synthetic ... [more ▼]

Promoting permanent adhesion between so dissimilar materials as polymers and metals is a very challenging target and a severe brake to the implementation of many potential applications. However, synthetic polymers can now be chemisorbed onto a variety of conducting surfaces by cathodic electrografting of acrylic monomers. The first part of this review will focus on the fundamental aspects of this emerging technology, thus from the historical discovery to experimental and theoretical developments, with the purpose to better comprehend the electrografting phenomenon. Once firmly established, this concept has been exploited in order to make polymeric coatings with specific functionality chemisorbed onto more diversified substrates in more convenient liquid media. This remarkable progress that largely relies on advanced controlled polymerization processes will be the topic of the second part of the review, with a special emphasis on the more recent development of smart coatings, particularly stimuli responsive coatings very well-suited to nanotechnologies. [less ▲]

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See detailMultifunctional coatings
Van de Weerdt, Cécile ULg; Detrembleur, Christophe ULg; Jérôme, Robert ULg et al

Patent (2009)

New polyelectrolyte copolymer, composite material, multilayer film and substrate carrying such polyelectrolyte copolymer, composite and multilayer film wherein the polyelectrolyte copolymer comprises a) a ... [more ▼]

New polyelectrolyte copolymer, composite material, multilayer film and substrate carrying such polyelectrolyte copolymer, composite and multilayer film wherein the polyelectrolyte copolymer comprises a) a first type of identical or different units (A) each comprising one or more dihydroxyphenyl groups such that sidechains are present along the backbone of the polyelectrolyte copolymer which contain at least one dihydroxyphenyl group each; and (b1) a second type of identical or different units (B1) each comprising a cationic moiety, or (b2) a second type of identical or different units (B2) each comprising an anionic moiety. [less ▲]

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See detailAll-in-one strategy for the fabrication of antimicrobial biomimetic films on stainless steel
Charlot, Aurélia; Sciannamea, Valérie; Lenoir, Sandrine et al

in Journal of Materials Chemistry (2009), 19

Here we report on an all-in-one approach to prepare robust antimicrobial films on stainless steel. The strategy is based on the layer-by-layer deposition of polyelectrolytes. A polycationic copolymer ... [more ▼]

Here we report on an all-in-one approach to prepare robust antimicrobial films on stainless steel. The strategy is based on the layer-by-layer deposition of polyelectrolytes. A polycationic copolymer bearing 3,4-dihydroxyphenylalanine units (DOPA, a major component of natural adhesives) was synthesized and co-deposited with precursors of silver nanoparticles as the first layer. The presence of DOPA units ensures a strong anchoring on the stainless steel substrate, and the silver nanoparticles are sources of biocidal Ag+, providing stainless steel with antimicrobial activity. We show that multilayered films, obtained by alternating this nanoparticle-loaded polycationic copolymer with polystyrene sulfonate, a commercial polyanion, results in stainless steel with high antibacterial activity against Gram-negative E. coli bacteria. The polycationic layers are a reservoir of Ag+ that can be reactivated after depletion. The whole process of film formation, including the synthesis of the copolymer, is conducted in aqueous media under very mild conditions, which makes it very attractive for industrial scale-up and sustainable applications. [less ▲]

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See detailFunctionlization and grafting of polylactide by click chemistry
Riva, Raphaël ULg; Croisier, Florence ULg; Jérôme, Christine ULg et al

Conference (2009, November 19)

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See detailElectrostatic hierarchical co-assembly in aqueous solutions of two oppositevely charged double hydrophilic diblock copolymers
Voets, Ilja K.; de Keizer, Arie; Leermakers, Frans A. M. et al

in European Polymer Journal (2009), 45(10), 2913-2925

The formation of spherical micelles in aqueous solutions of poly(N-methyl-2-vinyl pyridinium iodide)-block-poly(ethylene oxide), P2MVP-b-PEO and poly(acrylic acid)-block-poly(vinyl alcohol), PAA-b-PVOH ... [more ▼]

The formation of spherical micelles in aqueous solutions of poly(N-methyl-2-vinyl pyridinium iodide)-block-poly(ethylene oxide), P2MVP-b-PEO and poly(acrylic acid)-block-poly(vinyl alcohol), PAA-b-PVOH has been investigated with light scattering-titrations, dynamic and static light scattering, and 1H 2D Nuclear Overhauser Effect Spectroscopy. Complex coacervate core micelles, also called PIC micelles, block ionomer complexes, and interpolyelectrolyte complexes, are formed in thermodynamic equilibrium under charge neutral conditions (pH 8, 1 mM NaNO3, T = 25 °C) through electrostatic interaction between the core-forming P2MVP and PAA blocks. 2D 1H NOESY NMR experiments show no cross-correlations between PEO and PVOH blocks, indicating their segregation in the micellar corona. Self-consistent field calculations support the conclusion that these C3Ms are likely to resemble a ‘patched micelle’; that is, micelles featuring a ‘spheres-on-sphere’ morphology. [less ▲]

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See detailCobalt-mediated radical polymerization of vinyl monomers: investigation of cobalt-coordination
Debuigne, Antoine ULg; Piette, Yasmine ULg; Poli, Rinaldo et al

Poster (2009, September 17)

Controlled Radical Polymerization techniques have been developed to obtain well-defined architectures and to control polymer parameters. Among these systems is Cobalt-Mediated Radical Polymerization (CMRP ... [more ▼]

Controlled Radical Polymerization techniques have been developed to obtain well-defined architectures and to control polymer parameters. Among these systems is Cobalt-Mediated Radical Polymerization (CMRP), which is based on the reversible deactivation of the growing radical chains with a cobalt complex, the cobalt (II) bis(acetylacetonate). The interest of this system is not only due to its ability to control the polymerization of very reactive monomers such as vinyl acetate (VAc) and N-vinylpyrrolidone (NVP), but also its peculiar mechanism which exhibits two pathways depending on the polymerization conditions; a reversible termination process and a degenerative chain transfer mechanism. Furthermore, it has been showed that the Co-C bond strength and thus the polymerization are strongly influenced by the use of some additives, such as water, dimethylformamide, dimethylsulfoxide and pyridine, which coordinate the cobalt free site. In this presentation we report the use of a preformed alkyl-cobalt(III) adduct as initiator for the polymerization of various vinyl monomers of different reactivity (VAc, acrylonitrile,…) and on the effect of several ligands on their polymerization control. The preparation of novel block copolymers by CMRP will finally be presented. As a conclusion, cobalt-coordination appears today as a unique opportunity to adjust the Co-C bond strength and to push back the bounds of possibilities in terms of macromolecular engineering assisted by CMRP. [less ▲]

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See detailPolymer composite material structures comprising carbon based conductive loads
Jérôme, Robert ULg; Pagnoulle, Christophe; Detrembleur, Christophe ULg et al

Patent (2009)

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 ▲]

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See detailKey role of metal-coordination in cobalt-mediated radical polymerization of vinyl acetate
Debuigne, Antoine ULg; Poli, Rinaldo; Jérôme, Robert ULg et al

in Matyjaszewski, Krzysztof (Ed.) Controlled/living radical polymerization: progress in RAFT, DT, NMP & OMRP (2009)

Cobalt mediated radical polymerization (CMRP) of vinyl acetate (VAc) follows a reversible termination mechanism when initiated from a preformed alkyl-cobalt(III) complex. In these particular conditions ... [more ▼]

Cobalt mediated radical polymerization (CMRP) of vinyl acetate (VAc) follows a reversible termination mechanism when initiated from a preformed alkyl-cobalt(III) complex. In these particular conditions, CMRP functions as a stable free radical process and fine tuning of the Co-C bond strength becomes crucial. Increase of temperature and addition of molecules, such as water, dimethylformamide and dimethylsulfoxide, able to coordinate the cobalt complex appeared as efficient strategies to weaken the Co-C bond and thus to speed up the polymerization while maintaining a very good control of the VAc polymerization. The key role of metal-coordination was investigated by kinetic measurements combined with DFT calculations. [less ▲]

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See detailGold-loaded carbon nanoparticles from poly(vinyl alcohol)-b-poly(acrylonitrile) non-shell-cross-linked micelles
Bryaskova, Rayna; Willet, Nicolas ULg; Duwez, Anne-Sophie ULg et al

in Chemistry : An Asian Journal (2009), 4(8), 1338-1345

Herein we show that a new amphiphilic poly(vinyl alcohol)-b-poly(acrylonitrile) block copolymer dispersed in water can be easily loaded with gold nanoparticles by addition of chlorauric acid followed by ... [more ▼]

Herein we show that a new amphiphilic poly(vinyl alcohol)-b-poly(acrylonitrile) block copolymer dispersed in water can be easily loaded with gold nanoparticles by addition of chlorauric acid followed by reduction by sodium borohydride. After deposition of the so-loaded micelles onto a silicon wafer, followed by an appropriate thermal treatment, the poly(acrylonitrile) core of the micelles is carbonized, while the poly(vinyl alcohol) shell is completely decomposed and volatilized, leading to gold encapsulated in carbon nanoparticles. The morphology of the micelles is maintained during thermal treatment without requiring shell-cross-linking of the micelles prior to pyrolysis. [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 et al

Patent (2009)

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 detailNew developments in the functionalization of aliphatic polyesters by "click" copper-catalyzed azide-alkyne cycloaddition
Lecomte, Philippe ULg; Riva, Raphaël ULg; Schmeits, Stephanie ULg et al

Conference (2009, June 03)

Nowadays, biodegradable and biocompatible aliphatic polyesters are widely used as environmentally friendly thermoplastics and biomaterials. Nevertheless, the absence of any pendant functional group is a ... [more ▼]

Nowadays, biodegradable and biocompatible aliphatic polyesters are widely used as environmentally friendly thermoplastics and biomaterials. Nevertheless, the absence of any pendant functional group is a severe limitation for the development of novel applications. Our strategy aiming at functionalizing aliphatic polyesters relies on the “click” copper-catalyzed cycloaddition (CuAAC) of alkynes duly substituted by functional groups or even chains onto PCL bearing pendant azides. The aliphatic polyesters bearing pendant azides have been very efficiently synthesized by a straightforward approach, which relies on the ring-opening copolymerization of αClεCL (or γBrεCL) and εCL (or lactide) followed by reaction with sodium azide to convert pendant chlorides or bromides into azides. The alternative reported by Emrick et al. is based on the CuAAC reaction of azides substituted by any functional group onto copolyesters of poly(ε-caprolactone) bearing pendant alkynes. Interestingly enough, Emrick et al. carried out the CuAAc reaction in water at 80°C. Unfortunately, it turned out, at least in our hands, that these conditions can not be extended to the derivatization of more sensitive aliphatic polyesters because degradation was then unavoidable. Nevertheless, we found out that degradation can be minimized whenever the CuAAC reaction is carried out in an organic solvent at lower temperature. Typically, the CuAAC reaction was carried out in DMF or THF at 35°C. Recently, it was shown that supercritical carbon dioxide can be used as a more environmentally friendly solvent than DMF or THF. The contamination by catalytic residues of aliphatic polyesters functionalized by the CuAAC reaction is a severe limitation in view of future applications, especially in the biomedical field. In the last part of this talk, a special attention will be paid on our current efforts to get rid of copper residues. [less ▲]

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See detailStabilized mixed micelles with a temperature-responsive core and a functional shell
Petrov, Petar; Tsvetanov, Christo B.; Jérôme, Robert ULg

in Journal of Physical Chemistry B (2009), 113(21), 7527-7533

Formation and stabilization of multiresponsive micelles with a mixed poly(ethylene oxide)/polyelectrolyte shell and a temperature-responsive poly(propylene oxide) core were studied. Various poly(ethylene ... [more ▼]

Formation and stabilization of multiresponsive micelles with a mixed poly(ethylene oxide)/polyelectrolyte shell and a temperature-responsive poly(propylene oxide) core were studied. Various poly(ethylene oxide)block-poly(propylene oxide)-block-poly(ethylene oxide) (PEO-PPO-PEO) triblock copolymers were mixed with poly(acrylic acid)-block-poly(propylene oxide)-block-poly(acrylic acid) (PAA-PPO-PAA) or poly(dimethylaminoethyl methacrylate)-block-poly(propylene oxide)-block-poly(dimethylaminoethyl methacrylate) (PD-MAEMA-PPO-PDMAEMA) triblock copolymers. The micelles formed by binary mixtures of well-defined compositions at a specific pH were additionally stabilized by loading with pentaerythritol tetraacrylate (PETA), that was polymerized and cross-linked "in situ" with UV assistance. Depending on both the composition of the copolymers and the experimental conditions, either spherical or wormlike "stabilized polymeric micelles with a mixed shell" (SPMMS) were observed by dynamic light scattering (DLS) and transmission electron microscopy (TEM). The SPMMS that contained PAA blocks in the shell were pH-sensitive, such that a reversible transition from well-dispersed SPMMS to precipitate could be promoted. In contrast, the SPMMS with a PEO/PDMAEMA mixed shell remained well-dispersed in the 2-11 pH range. Finally, SPMMS were successfully exploited as templates for the preparation of Ag nanoparticles (Ag NPs). [less ▲]

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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 ▲]

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See detailThe influence of cobalt-coordination on cobalt-mediated radical polymerization of vinyl monomers
Debuigne, Antoine ULg; Piette, Yasmine ULg; Poli, Rinaldo et al

Poster (2009, March 19)

Nowadays, polymers are a part of everyday life. Researchers encouraged by growing need in high performance polymers develop new synthesis tools to manage the molecular architecture and thus the polymer ... [more ▼]

Nowadays, polymers are a part of everyday life. Researchers encouraged by growing need in high performance polymers develop new synthesis tools to manage the molecular architecture and thus the polymer properties. In this context, CRP (Controlled Radical Polymerization) techniques have been developed to obtain well-defined architectures and to control polymer parameters. Among these systems is Cobalt-Mediated Radical Polymerization (CMRP), which is based on the reversible deactivation of the growing radical chains with a cobalt complex, the cobalt (II) bis-acetylacetonate. The interest of this system is not only due to its ability to control the polymerization of very reactive monomers such as vinyl acetate (VAc) and N-vinylpyrrolidone (NVP), but also its peculiar mechanism which exhibits two pathways depending on the polymerization conditions; a reversible termination process and a degenerative chain transfer mechanism. Furthermore, it has been showed that the Co-C strength and thus the polymerization are strongly influenced by the use of some additives, such as water, dimethylformamide, dimethylsulfoxide and pyridine, which coordinate the cobalt free site. In this presentation we report the use of a preformed alkyl-cobalt(III) adduct as initiator for the polymerization of acrylonitrile (AN) and the use of these ligands in the CMRP system to synthesize well-defined poly(vinyl acetate)-b-poly(acrylonitrile) block copolymers. As a conclusion, cobalt-coordination appears today as a unique opportunity to adjust the Co-C bond strength and to push back the bounds of possibilities in terms of macromolecular engineering assisted by CMRP. [less ▲]

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See detailHow can cobalt complexes help synthetic polymer chemists?
Debuigne, Antoine ULg; Jérôme, Robert ULg; Jérôme, Christine ULg et al

Conference (2009, March 19)

Nowadays, progresses in medicine, biotechnology, microelectronic and many other fields are more and more sustained by the development of novel polymer materials with constantly improved properties and ... [more ▼]

Nowadays, progresses in medicine, biotechnology, microelectronic and many other fields are more and more sustained by the development of novel polymer materials with constantly improved properties and well-defined molecular parameters. In this context, we designed a controlled radical polymerization (CRP) technique based on cobalt complexes which is able to efficiently control the radical polymerization of challenging monomers such as vinyl acetate (VAc), N-vinyl pyrrolidone (NVP) and acrylonitrile (AN). This so-called Cobalt-Mediated Radical Polymerization (CMRP) also gave access to unique diblock copolymers by sequential polymerization of the above mentioned monomers. However, addition of isoprene to polymer chains preformed by CMRP did not lead to the expected poly(isoprene) containing copolymers. Instead, the quantitative coupling reaction of the polymer chains was observed, as assessed by the perfect doubling of the molar mass of the initial macromolecules. This result is very exciting because this so-called Isoprene-Assisted Radical Coupling (I-ARC) reaction is not limited to polymers with low molar masses and homopolymers, contrary to the existing radical chains coupling methods. Indeed, when applied to diblock copolymers, IARC constitutes a straightforward approach for the synthesis of telechelic symmetrical ABA triblock copolymers and is thus a very promising tool for macromolecular engineering. [less ▲]

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See detailOverview of cobalt-mediated radical polymerization: roots, state of the art and future prospects
Debuigne, Antoine ULg; Poli, Rinaldo; Jérôme, Christine ULg et al

in Progress in Polymer Science (2009), 34(3), 211-239

Controlled radical polymerization (CRP) techniques offer the opportunity to properly design polymer chains and adjust their chemical and physical properties. Among these techniques, cobalt-mediated ... [more ▼]

Controlled radical polymerization (CRP) techniques offer the opportunity to properly design polymer chains and adjust their chemical and physical properties. Among these techniques, cobalt-mediated radical polymerization (CMRP) distinguished itself by the high level of control imparted to the polymerization of acrylic and vinyl ester monomers, even for high molar masses. This article summarizes for the first time the advances in understanding and synthetic scope of CMRP since its discovery. Notably, the cobalt–carbon bond formation by dual contribution of reversible termination and degenerative chain transfer is discussed, as well as the impact of additives able to coordinate the metal. The potential of computational chemistry in the field of CMRP as a rationalization and predicting tool is also presented. These mechanistic considerations and achievements in macromolecular engineering will be discussed along with challenges and future prospects in order to assess the CMRP system as a whole. [less ▲]

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See detailRelevance of a prereaction for the in situ NMP of styrene using the C-phenyl-N-tert-butylnitrone/2,2’-azobis(isobutyronitrile) pair
Sciannamea, Valérie; Catala, Jean-Marie; Jérôme, Robert ULg et al

in Journal of Polymer Science. Part A, Polymer Chemistry (2009), 47(4), 1085-1097

In this article, we compare two routes for carrying out in situ nitroxide-mediated polymerization of styrene using the C-phenyl-N-tert-butylnitrone (PBN)/2,2-azobis(isobutyronitrile) (AIBN) pair to ... [more ▼]

In this article, we compare two routes for carrying out in situ nitroxide-mediated polymerization of styrene using the C-phenyl-N-tert-butylnitrone (PBN)/2,2-azobis(isobutyronitrile) (AIBN) pair to identify the best one for an optimal control. One route consists in adding PBN to the radical polymerization of styrene, while the other approach deals with a prereaction between the nitrone and the free radical initiator prior to the addition of the monomer and the polymerization. The combination of ESR and kinetics studies allowed demonstrating that when the polymerization of styrene is initiated by AIBN in the presence of enough PBN at 110 °C, fast decomposition of AIBN is responsible for the accumulation of dead polymer chains at the early stages of the polymerization, in combination with controlled polystyrene chains. On the other hand, PBN acts as a terminating agent at 70 °C with the formation of a polystyrene end-capped by an alkoxyamine, which is not labile at this temperature but that can be reactivated and chain-extended by increasing the temperature. Finally, the radical polymerization of styrene is better controlled when the nitrone/initiator pair is prereacted at 85 °C for 4 h in toluene before styrene is added and polymerized at 110 °C. [less ▲]

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

Patent (2009)

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 detailStainless steel grafting of hyperbranched polymer brushes with an antibacterial activity: synthesis, characterization and properties
Ignatova, Milena; Voccia, Samuel; Gabriel, Sabine et al

in Langmuir (2009), 25(2), 891-902

Two strategies were used for the preparation of hyperbranched polymer brushes with a high density of functional groups: (a) the cathodic electrografting of stainless steel by poly[2-(2-chloropropionate ... [more ▼]

Two strategies were used for the preparation of hyperbranched polymer brushes with a high density of functional groups: (a) the cathodic electrografting of stainless steel by poly[2-(2-chloropropionate)ethyl acrylate] [poly(cPEA)], which was used as a macroinitiator for the atom transfer radical polymerization of an inimer, 2-(2-bromopropionate)ethyl acrylate in the presence or absence of heptadecafluorodecyl acrylate, (b) the grafting of preformed hyperbranched poly(ethyleneimine) onto poly(N-succinimidyl acrylate) previously electrografted onto stainless steel. The hyperbranched polymer, which contained either bromides or amines, was quaternized because the accordingly formed quaternary ammonium or pyridinium groups are known for antibacterial properties. The structure, chemical composition, and morphology of the quaternized and nonquaternized hyperbranched polymer brushes were characterized by ATR-FTIR reflectance, Raman spectroscopy, X-ray photoelectron spectroscopy, and atomic force microscopy. The peeling test confirmed that the grafted hyperbranched polymer films adhered much more strongly to stainless steel than the nongrafted solvent-cast films. The quaternized hyperbranched polymer brushes were more effective in preventing both protein adsorption and bacterial adhesion than quaternary ammonium containing poly(cPEA) primary films, more likely because of the higher hydrophilicity and density of cationic groups. [less ▲]

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