References of "Debuigne, Antoine"
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See detailAntibacterial activity of poly(vinyl alcohol)-b-poly(acrylonitrile) based micelles loaded with silver nanoparticles
Bryaskova, Rayna; Pencheva, Daniela; Kyulavska, Mariya et al

in Journal of Colloid & Interface Science (2010), 344(2), 424-448

A new amphiphilic poly(vinyl alcohol)-b-poly(acrylonitrile) (PVOH-b-PAN) copolymer obtained by selective hydrolysis of well-defined poly(vinyl acetate)-b-poly(acrylonitrile) copolymer synthesized by ... [more ▼]

A new amphiphilic poly(vinyl alcohol)-b-poly(acrylonitrile) (PVOH-b-PAN) copolymer obtained by selective hydrolysis of well-defined poly(vinyl acetate)-b-poly(acrylonitrile) copolymer synthesized by cobalt mediated radical polymerization was used for the preparation of PVOH-b-PAN based micelles with embedded silver nanoparticles. The successful formation of silver loaded micelles has been confirmed by UV–vis, DLS and TEM analysis and their antibacterial activity against Escherichia coli (E. coli), Staphylococcus aureus (S. aureus), Pseudomonas aeruginosa (P. aeruginosa) and spore solution of Bacillus subtilis (B. subtilis) has been studied. PVOH-b-PAN based micelles with embedded silver nanoparticles showed a strong bactericidal effect against E. coli, S. aureus and P. aeruginosa and the minimum bactericidal concentration for each system (MBC) has been determined. [less ▲]

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See detailLocating carbon nanotubes (CNTs) at the surface of polymer microspheres using poly(vinyl alcohol) grafted CNTs as dispersion co-stabilizers
Thomassin, Jean-Michel ULg; Molenberg, Isabel; Huynen, Isabelle et al

in Chemical Communications (2010), 46(3330), 3332

In this communication, we prepared carbon nanotubes (CNTs) modified by poly(vinyl alcohol) that are used as co-stabilizers for the dispersion polymerization of methyl methacrylate. Poly(methyl ... [more ▼]

In this communication, we prepared carbon nanotubes (CNTs) modified by poly(vinyl alcohol) that are used as co-stabilizers for the dispersion polymerization of methyl methacrylate. Poly(methyl methacrylate) microspheres with CNTs selectively located at their surface are formed. This specific localization is a way to enhance the electrical conductivity of the nanocomposite. [less ▲]

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See detailSynthesis of poly(vinyl alcohol)/C60 and poly(N-vinylpyrrolidone)/C60 nanohybrids as potential photodynamic cancer therapy agents
Hurtgen, Marie ULg; Debuigne, Antoine ULg; Mouithys-Mickalad, Ange ULg et al

in Chemistry : An Asian Journal (2010), 5(4), 859-868

Well-defined poly(vinyl acetate) (PVAc) and poly(N-vinylpyrrolidone)-co-poly(vinyl acetate) (PNVPco-PVAc) chains end-capped by Co-(acac)2 (acac=acetylacetonate) and prepared by cobalt-mediated radical ... [more ▼]

Well-defined poly(vinyl acetate) (PVAc) and poly(N-vinylpyrrolidone)-co-poly(vinyl acetate) (PNVPco-PVAc) chains end-capped by Co-(acac)2 (acac=acetylacetonate) and prepared by cobalt-mediated radical polymerization (CMRP) are grafted onto a fullerene. Homolytic Co-C bond cleavage of the polymer chain ends at 30°C releases the polymeric radicals that add onto C60, thereby leading to the corresponding PVAc/C60 and PNVP-co-PVAc/C60 nanohybrids. The [polymer–Co(acac)2]/[C60] molar ratio was varied to adjust the structure of the nanohybrids, and more particularly the number of grafted arms. Finally, the potential of the hydrosoluble PVOH/C60 nanohybrids, which result from the methanolysis of the ester groups of PVAc/C60, and of the PNVP-co-PVAc/C60 nanohybrids as photosensitizers for photodynamic therapy (PDT), was approached. First, photobleaching tests demonstrated the ability of these nanohybrids to produce singlet oxygen upon irradiation, which can play a role in cell damage. Second, cell viability assays demonstrated that both types of nanohybrids are deprived of intrinsic cytotoxicity in the dark, whereas they promoted significant cell mortality when subjected to light treatment. The selective response of these materials to irradiation makes them promising compounds for PDT. [less ▲]

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See detailEffective cobalt-mediated radical coupling (CMRC) of poly(vinylacetate) and poly(N-vinylpyrrolidone) (co)polymer precursors
Debuigne, Antoine ULg; Poli, Rinaldo; De Winter, Julien et al

in Macromolecules (2010), 43(6), 2801-2813

Cobalt-mediated radical coupling (CMRC) is successfully applied to poly(vinyl acetate) (PVAc) and poly(N-vinylpyrrolidone) (PNVP) precursors for the first time. The coupling process is based on addition ... [more ▼]

Cobalt-mediated radical coupling (CMRC) is successfully applied to poly(vinyl acetate) (PVAc) and poly(N-vinylpyrrolidone) (PNVP) precursors for the first time. The coupling process is based on addition of isoprene onto polymer chains preformed by controlled radical polymerization with cobalt complexes (CMRP). The extents of coupling were high (>90%) to moderate (75-80%) for PVAc and PNVP precursors, respectively. Effects of the length of the polymer precursors and conditions used in the polymerization step on the coupling efficiency are discussed. Mass spectrometry (MS) and nuclear magnetic resonance (NMR) analyses conducted on the coupling products demonstrate the preferential insertion of two isoprene units in the final polymers. The CMRC mechanistic proposal, supported by DFT calculations, is based on this microstructure feature. Finally, illustration of the macromolecular engineering potential of this technique is given by the preparation of symmetrical PVAc-b-PNVP-b-PVAc triblock copolymers starting from the corresponding PVAc-b-PNVP-[Co] diblock copolymer. [less ▲]

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See detailCobalt mediated radical coupling (CMRC) : an unusual route to midchain-functionalized symmetrical macromolecules
Debuigne, Antoine ULg; Poli, Rinaldo; De Winter, Julien et al

in Chemistry : A European Journal (2010), 16(5), 1799-1811

Cobalt-mediated radical coupling (CMRC) is a straightforward approach to the synthesis of symmetrical macromolecules that relies on the addition of 1,3-diene compounds onto polymer precursors preformed by ... [more ▼]

Cobalt-mediated radical coupling (CMRC) is a straightforward approach to the synthesis of symmetrical macromolecules that relies on the addition of 1,3-diene compounds onto polymer precursors preformed by cobalt-mediated radical polymerization (CMRP). Mechanistic features that make this process so efficient for radical polymer coupling are reported here. The mechanism was established on the basis of NMR spectroscopy and MALDI-MS analyses of the coupling product and corroborated by DFT calculations. A key feature of CMRC is the preferential insertion of two diene units in the middle of the chain of the coupling product mainly according to a trans-1,4-addition pathway. The large tolerance of CMRC towards the diene structure is demonstrated and the impact of this new coupling method on macromolecular engineering is discussed, especially for midchain functionalization of polymers. It is worth noting that the interest in CMRC goes beyond the field of polymer chemistry, since it constitutes a novel carbon-carbon bond formation method that could be applied to small organic molecules. [less ▲]

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See detailSolving the problem of bis(acetylacetonato)cobalt(II)-mediated radical polymerization (CMRP) of acrylic esters
Hurtgen, Marie ULg; Debuigne, Antoine ULg; Jérôme, Christine ULg et al

in Macromolecules (2010), 43(2), 886-894

Recent developments in cobalt-mediated radical polymerization (CMRP) and progress in the mechanistic understanding enabled to optimize the copolymerization of n-butyl acrylate (nBA) with vinyl acetate ... [more ▼]

Recent developments in cobalt-mediated radical polymerization (CMRP) and progress in the mechanistic understanding enabled to optimize the copolymerization of n-butyl acrylate (nBA) with vinyl acetate (VAc), as well as to control the homopolymerization of nBA by means of bis(acetylacetonato)cobalt-(II) (Co(acac)2). Critical experimental parameters such as the initiating system, the temperature, and the presence of additives were varied and discussed. Under optimized conditions, an alkylcobalt(III) adduct R0-(CH2-CHOAc)<4-Co(acac)2 (R0=primary radical from the V-70 decomposition) allowed a better control of the nBA/VAc copolymerization than the previously studied V-70/Co(acac)2 pair regarding the molecular weight control and the polydispersities. Importantly, the homopolymerization of nBA was controlled by Co(acac)2 for the first time using the alkylcobalt(III) adduct or the lauroyl peroxide (LPO)/ Co(acac)2 redox pair as initiating system. Typically, poly(n-butyl acrylate) with polydispersity around 1.2 and molar mass as high as 200 000 g/mol was achieved with this cobalt complex. [less ▲]

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See detailCobalt-mediated radical polymerization (CMRP) and coupling reaction (CMRC): mechanistic advances ans synthetic opportunities
Debuigne, Antoine ULg; Poli, Rinaldo; De Winter, Julien et al

Poster (2009, December 14)

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See detailSynthèse enzymatique de surfactants sucrés dans le CO2 supercritique
Favrelle, Audrey ULg; Brognaux, Alison ULg; Debuigne, Antoine ULg et al

Poster (2009, October 15)

Les esters de carbohydrates sont des surfactants non ioniques ayant un vaste éventail d’applications commerciales en particulier dans l’industrie cosmétique, alimentaire et pharmaceutique. Ils sont ... [more ▼]

Les esters de carbohydrates sont des surfactants non ioniques ayant un vaste éventail d’applications commerciales en particulier dans l’industrie cosmétique, alimentaire et pharmaceutique. Ils sont produits à partir de matières premières renouvelables et peu coûteuses, et sont biodégradables et non toxiques. De manière générale, la synthèse d’esters de sucre nécessite de nombreuses étapes de protection/déprotection des groupements hydroxyles, le nombre et la position exacte des substituants greffés sur un squelette osidique étant des paramètres difficiles à contrôler lors des réactions chimiques. En revanche, la spécificité de certaines enzymes, et en particulier des lipases, peut être mise à profit pour modifier les sucres en milieux organiques. L’utilisation des lipases permet ainsi un meilleure sélectivité et énantiosélectivité des réactions d’estérification et de transestérification. D’autre part, la voie enzymatique permet d’effectuer ces réactions dans des conditions expérimentales beaucoup plus douces de température, de pH et de pression, par rapport aux synthèses réalisées à l’aide de catalyseurs chimiques. Le dioxyde de carbone supercritique (Sc-CO2), quant à lui, constitue une alternative intéressante aux solvants organiques couramment utilisés dans ce domaine car il est non toxique, chimiquement inerte, non inflammable…. Par exemple, son utilisation réduit la contamination des produits finaux avec des solvants résiduels. Ces avantages lui confèrent un large potentiel d’applications notamment dans l’industrie alimentaire, cosmétique, pharmaceutique mais également des matériaux. Notre travail consiste donc à développer la synthèse enzymatique de surfactants sucrés en milieu Sc-CO2 et d’étudier l’influence de divers paramètres sur la réaction biocatalysée. L’activité enzymatique et les rendements observés lors de nos expériences préliminaires dans le Sc-CO2 seront présentés ici et comparés avec ceux obtenus dans des solvants organiques traditionnels. [less ▲]

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See detailOptimisation de l'acylation enzymatique du mannose par l'utilisation de co-solvants
Brognaux, Alison ULg; Favrelle, Audrey ULg; Deleu, Magali ULg et al

Poster (2009, October 15)

Les esters de sucres sont des surfactants non-ioniques avec de nombreuses applications dans l’industrie alimentaire et pharmaceutique. La synthèse enzymatique est généralement préférée à la synthèse ... [more ▼]

Les esters de sucres sont des surfactants non-ioniques avec de nombreuses applications dans l’industrie alimentaire et pharmaceutique. La synthèse enzymatique est généralement préférée à la synthèse chimique. En effet, cette dernière consomme beaucoup d’énergie, est moins sélective envers les différents groupes hydroxyle du sucre et conduit à des produits de caramélisation. Le type de solvant, le ratio sucre / lipide, la température et le type de lipase immobilisée peuvent être modifiés afin d’optimiser la vitesse initiale et le rendement de réaction. Les travaux décrits rapportent l’optimisation de la synthèse enzymatique de myristate de mannosyle à partir de mannose et d’acide myristique en présence de la lipase de Candida antarctica B (Novozyme 435). Les concentrations optimales en mannose et en acide myristique sont respectivement de 0,1 et 0,6 M dans du tert-butanol pur à 60°C. Ces conditions conduisent à une vitesse initiale de 1,3 g/l.h pour 2 g/l d’enzyme et à un rendement molaire de 55%. Afin d’améliorer cette vitesse initiale de réaction, différents mélanges de tert-butanol et de co-solvants polaires ont été testés. Les solvants polaires (log P faibles) augmentent la solubilité des sucres mais provoquent l’inactivation partielle des lipases. Lorsque le log P est supérieur à 3, l’enzyme reste active mais ce type de milieu n’est pas approprié si les deux substrats diffèrent grandement en terme de polarité. Le but de cette étude est donc de trouver un compromis entre la solubilité du sucre et le maintient de l’activité enzymatique. Les quatre co-solvants testés sont le DMSO, le DMF, le formamide et la pyridine. Au terme de ce travail, le DMSO, à raison de 10 % dans le milieu réactionnel, s’est avéré être le meilleur co-solvant parmi ceux testés. Dans ces conditions, la vitesse initiale de réaction est accrue de 130 %. [less ▲]

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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 (CMRP) using bis(acetylacetonato)cobalt(II): a unique tool for controlling the radical polymerization of conjugated and unconjugated vinyl monomers
Hurtgen, Marie ULg; Debuigne, Antoine ULg; Jérôme, Christine ULg et al

Poster (2009, September 17)

Cobalt-Mediated Radical Polymerization (CMRP) imparts a high level of control on the polymerization of acrylic and vinylic esters, acrylic acid and acrylonitrile. However, each class of monomers appears ... [more ▼]

Cobalt-Mediated Radical Polymerization (CMRP) imparts a high level of control on the polymerization of acrylic and vinylic esters, acrylic acid and acrylonitrile. However, each class of monomers appears to be controlled by one class of cobalt complexes. For example, the polymerization of acrylates and acrylic acid is mediated by cobalt porphyrin complexes while vinyl acetate (VAc) and acrylonitrile are efficiently controlled by bis(acetylacetonato)cobalt(II) (Co(acac)2). Therefore, a challenging issue in CMRP remains to broaden the range of monomers that can be controlled by the same cobalt complex. Recently, the controlled random copolymerization of butyl acrylate (BuA) with VAc was performed using the conventional V-70/Co(acac)2 CMRP system, but the homopolymerization of BuA remained uncontrolled. In this work, we used a new alkylcobalt(III) adduct to initiate and control the copolymerization of BuA with VAc. This achievement resulted in a significant improvement over the V-70/Co(acac)2 pair regarding the molecular weight control and the polydispersity indexes. Moreover, for the first time, the alkylcobalt(III) adduct was also efficient in controlling the homopolymerization of BuA and yielded low polydispersity PBuA even in the absence of VAc. These results indicate that Co(acac)2 is a versatile mediator for the CMRP of both unconjugated vinyl monomers (VAc, N-vinylpyrrolidone) and conjugated monomers such as acrylates. It gives access to copolymers that cannot be prepared by other controlled radical polymerization techniques. [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 detailSynthesis of novel block copolymers by cobalt-mediated radical polymerization (CMRP) and isoprene-assisted radical coupling reaction (I-ARC)
Debuigne, Antoine ULg; Jérôme, Christine ULg; Detrembleur, Christophe ULg

Conference (2009, September 17)

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 an innovative and very promising tool for macromolecular engineering. This technique, called Isoprene-Assisted Radical Coupling (I-ARC), allows to couple quantitatively polymer chains preformed by Cobalt-Mediated Radical Polymerization (CMRP), an efficient controlled radical polymerization system for vinyl acetate (VAc) and acrylonitrile (AN). Typically, addition of isoprene to well-defined polymers prepared by CMRP invariably leads to the quantitative coupling reaction of the chains, as assessed by the perfect doubling of the molar mass of the polymer. Importantly, the I-ARC reaction is not limited to macromolecules with low molar masses and homopolymers, contrary to the previously reported radical chains coupling methods. Indeed, when applied to diblock copolymers, I-ARC constitutes a straightforward approach for the synthesis of telechelic symmetrical ABA triblock copolymers, as illustrated by the preparation of poly(vinyl acetate)-b-poly(acrylonitrile)-b-poly(vinyl acetate) triblock copolymers and their derivatives. [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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