References of "Jérôme, Christine"
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See detailSynthesis of new biomimetic biodegradable materials for clinical use
Clement, Benoît ULg; Grignard, Bruno ULg; Lecomte, Philippe ULg et al

Poster (2012, May 10)

For recent decades, the most commonly biodegradable polymers used in clinical and therapeutic applications are aliphatic polyesters such as polyglycolide, polylactide, polycaprolactone and their ... [more ▼]

For recent decades, the most commonly biodegradable polymers used in clinical and therapeutic applications are aliphatic polyesters such as polyglycolide, polylactide, polycaprolactone and their copolymers, mainly due to their excellent biocompatibility and biodegradability properties. However, the lack of functional groups on the backbone of polyesters, which could otherwise be used for tuning physicochemical properties and for introducing bioactive units, limits their further biomedical applications. Polymers with repeating phosphoester bonds in the backbone are structurally versatile and biodegradable through hydrolysis and possibly enzymatic digestion of phosphates linkages under physiological conditions. An advantage of polyphosphoesters (PPEs) compared to aliphatic polyesters is the possible functionalization of side chains due to the patenvalency of the phosphorous atom, allowing the introduction of bioactive molecules and extensive modification of the physical and chemical properties of final material. The Ring-Opening Polymerization (ROP) of cyclic esters is a well-established process to provide linear polyesters with predictable molecular weight, narrow polydispersity and well-defined end-groups. Up to now, metallic compounds are particularly used as initiators or polymerization catalysts to synthetize these materials but metallic derivatives are cytotoxic and a lack of residual metal contaminants is strongly required in view of biomedical applications. To tackle these drawbacks, we developed synthetic approaches that are metal-free (i.e., organocatalytic) using organocatalysis based on supramolecular recognition. A variety of organocatalysts such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5,7-triazabicyclo[4.4.0]undec-5-ene (TBD) and a bicomponent thiourea-tertiary amine catalyst were studied. Each of these catalysts is efficient to produce linear polyphosphoesters (PPEs) from cyclic phosphate monomers (CPMs) but with different sensitivity towards transesterification side reactions. Compared with polymerizations carried out with Sn(Oct)2 as a metal catalyst, the control of polymerization is much better so that it is possible to prepare PPEs with molecular weight close to 70000 g.mol-1 and polydispersity index below 1.10. The chain extension experiments through the use of hydroxy end-capped PPEs as macro-initiators confirm the controlled/living nature of organo-catalyzed ROP of CPMs and pave the way to the synthesis of block copolymers based on polyphosphates. Finally, these polymerizations procedures are expected to facilitate the synthesis of well-defined PPEs with various architectures and free of potentially toxic metal remnants. The easy availability of catalysts, the mild conditions of polymerizations and the metal-free nature of the polymerizations makes these catalysts very attractive candidates for the synthesis of PPEs for biomedical applications such as drug and gene delivery, tissue engineering and dental applications. [less ▲]

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See detailDesign of sugar-based surface active agents for emulsion polymerization in supercritical carbon dioxide
Boyère, Cédric ULg; Favrelle, Audrey; Broze, Guy ULg et al

Conference (2012, May 10)

The use of aqueous dispersed media, such as emulsions, has many advantages over solution processes for chemical transformations and polymerization reactions, i.e. limited environmental impact, ease of ... [more ▼]

The use of aqueous dispersed media, such as emulsions, has many advantages over solution processes for chemical transformations and polymerization reactions, i.e. limited environmental impact, ease of products recovery and increased reaction rate. Emulsions are usually implemented from a water/organic solvent mixture in the presence of a surfactant. However, supercritical carbon dioxide (scCO2) (Pc =74 bars; Tc = 31°C) constitutes an interesting alternative to the traditional organic solvents in these heterogeneous systems because it is inexpensive, non-toxic, non-inflammable and environmentally friendlier. In this context, we developed a novel class of surfactants for the stabilization of H2O/scCO2 emulsions, i.e. fluorinated modified carbohydrates. The hydrophilic head of the surfactant consists in a sugar moiety whereas a fluorinated tail is specifically located in the scCO2 phase. The strategies for the synthesis of these carbohydrates esters rely on selective lipase-catalyzed modifications of sugars and on the versatile thiol-Michael addition reaction. The ability of these molecules to decrease the H2O/scCO2 interfacial tension and to stabilize such emulsions will be presented. Finally, high internal phase scCO2-in-water emulsion (HIPE) were prepared with these new surfactants and used as template for the acrylamide polymerization. The monomer is polymerized in the continuous aqueous phase before removing the CO2 droplets (at least 70 % of the total volume). The resulting permeable porous polymers, called polyHIPEs, exhibit highly interconnected voids (cfr SEM picture) and should be valuable in many applications including support for catalyst, filtration process, immobilization of proteins, etc. [less ▲]

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See detailAntibacterial polyelectrolyte micelles for coating stainless steel
Falentin, Céline ULg; Faure, Emilie ULg; Svaldo Lanero, Tiziana ULg et al

in Langmuir (2012), 28(18), 7233-7241

In this study, we report on the original synthesis and characterization of novel antimicrobial coatings for stainless steel by alternating the deposition of aqueous solutions of positively charged ... [more ▼]

In this study, we report on the original synthesis and characterization of novel antimicrobial coatings for stainless steel by alternating the deposition of aqueous solutions of positively charged polyelectrolytes micelles doped with silver based nanoparticles with a polyanion. The micelles are formed by electrostatic interaction between two oppositely charged polymers, a polycation bearing 3,4-dihydroxyphenylalanine units (DOPA, a major component of natural adhesives) and a polyanion (poly(styrene sulfonate), PSS) without using any block copolymer. DOPA units are exploited for their well-known ability to anchor to stainless steel and to form and stabilize biocidal silver nanoparticles (Ag0). The chlorine counter-anion of the polycation forms and stabilizes biocidal silver chloride nanoparticles (AgCl). We demonstrate that two layers of micelles (alternated by PSS) doped by silver particles are enough to impart to the surface a strong antibacterial activity against Gram-negative E. coli. Moreover, micelles that are reservoirs of biocidal Ag+ can be easily reactivated after depletion. This novel water-based approach is convenient, simple and attractive for industrial applications. [less ▲]

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See detailElectroinitiated polymerization
Jérôme, Christine ULg

in Matyjaszewski, Krzysztof; Möller, Martin (Eds.) Polymer Science: a comprehensive reference ; volume 4: Ring-Opening Polymerization and Special Polymerization Processes (2012)

Electroinitiated polymerization, a method particularly relevant in coating technology, offers the unique opportunity of imparting permanent functionality/reactivity to a variety of surfaces, provided that ... [more ▼]

Electroinitiated polymerization, a method particularly relevant in coating technology, offers the unique opportunity of imparting permanent functionality/reactivity to a variety of surfaces, provided that the solid substrate is (semi)conducting. By focusing on the electroinitiation of acrylic monomers, basic concepts and some tools dedicated to the analysis of this peculiar polymerization process are discussed in this chapter. The important role of this polymerization method in the field of conjugated polymers is also highlighted. Finally, this chapter concludes with the opportunities and future challenges of this technology. [less ▲]

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See detailPhysicochemical properties of pH-controlled polyion complex (PIC) micelles of poly(acrylic acid)-based double hydrophilic block copolymers and various polyamines
Warnant, Jérôme; Marcotte, N.; Reboul, J. et al

in Analytical and Bioanalytical Chemistry (2012), 403

The physicochemical properties of polyion complex (PIC) micelles were investigated in order to characterize the cores constituted of electrostatic complexes of two oppositely charged polyelectrolytes. The ... [more ▼]

The physicochemical properties of polyion complex (PIC) micelles were investigated in order to characterize the cores constituted of electrostatic complexes of two oppositely charged polyelectrolytes. The pH-sensitive micelles were obtained with double hydrophilic block copolymers containing a poly(acrylic acid) block linked to a modified poly(ethylene oxide) block and various polyamines (polylysine, linear and branched polyethyleneimine, polyvinylpyridine, and polyallylamine). The pH range of micellization in which both components are ionized was determined for each polyamine. The resulting PIC micelles were characterized using dynamic light scattering and smallangle X-ray scattering experiments (SAXS). The PIC micelles presented a core–corona nanostructure with variable polymer density contrasts between the core and the corona, as revealed by the analysis of the SAXS curves. It was shown that PIC micelle cores constituted by polyacrylate chains and polyamines were more or less dense depending on the nature of the polyamine. It was also determined that the density of the cores of the PIC micelles depended strongly on the nature of the polyamine. These homogeneous cores were surrounded by a large hairy corona of hydrated polyethylene oxide block chains. Auramine O (AO) was successfully entrapped in the PIC micelles, and its fluorescence properties were used to get more insight on the core properties. Fluorescence data confirmed that the cores of such micelles are quite compact and that their microviscosity depended on the nature of the polyamine. The results obtained on these core–shell micelles allow contemplating a wide range of applications in which the AO probe would be replaced by various cationic drugs or other similarly charged species to form drug nanocarriers or new functional nanodevices. [less ▲]

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See detailInnovative multilayered nanofibers for wound dressing application
Croisier, Florence ULg; Detrembleur, Christophe ULg; Jérôme, Christine ULg

Poster (2012, April 18)

Chitosan is a natural polymer derived from the chitin of crustacean or mushroom shells, that intrinsically presents haemostatic, mucoadhesive, antimicrobial and immunostimulant properties. This ... [more ▼]

Chitosan is a natural polymer derived from the chitin of crustacean or mushroom shells, that intrinsically presents haemostatic, mucoadhesive, antimicrobial and immunostimulant properties. This polysaccharide has shown a great potential for biomedical and pharmaceutical applications, on account of its remarkable compatibility with physiological medium. Besides, it is degraded in a physiological environment into non-toxic products, which make chitosan an outstanding candidate for short- to medium-term applications. In this respect, nanometric fibers are highly interesting as their assembly mimics the skin extracellular matrix structure. Such nanofibrous materials can be prepared by electrospinning (ESP). This technique uses a high voltage to create an electrically charged jet of polymer solution or melt which leads to fibers formation. Depending on the polymer characteristics (a.o. molecular weight, solution viscosity and conductivity) and processing conditions (electric potential, distance between syringe-capillary and collection plate, concentration, flow rate), polymer fibers ranging from nanometers to a few microns in diameter can be obtained and subsequently used as potential scaffolds, a.o. to form a temporary, artificial extracellular matrix. In the present study, electrospinning technique was combined with layer-by-layer deposition method (LBL) - a well-known method for surface coating, based on electrostatic interactions - in order to prepare multilayered chitosan-based nanofibers. The antibacterial properties of the obtained material were then assessed, and the presence of a multilayered deposit was confirmed by several techniques. (Future) possibilities for valorization: These multilayered chitosan-based nanofibers present great prospects for the preparation of new biomedical scaffolds - such as wound dressings that could improve skin regeneration. [less ▲]

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See detailUse of ionic liquids for biocatalytic synthesis of sugar derivatives
Galonde, Nadine ULg; Nott, Katherine ULg; Debuigne, Antoine ULg et al

in Journal of Chemical Technology & Biotechnology (2012), 87(4), 451-471

Sugar-based compounds are widely used in pharmaceuticals, cosmetics, detergents and food. They are mainly produced by chemical methods, but the use of enzymes as ‘a greener alternative’ to organic ... [more ▼]

Sugar-based compounds are widely used in pharmaceuticals, cosmetics, detergents and food. They are mainly produced by chemical methods, but the use of enzymes as ‘a greener alternative’ to organic synthesis has been investigated for more than 20 years. Due to the low polar substrate solubility in organic solvents compatible with enzymes, research has focused on the application of substitutes for biocatalysis, especially ionic liquids (ILs). After introducing the main properties of ILs and especially their ability to solubilize sugars, this review focuses on one of their applications, the biocatalytic synthesis of carbohydrate derivatives. In this context, they can be used in pure IL systems, in IL/IL systems or in IL/organic solvent systems. Finally, this review provides an update on the environmental fate of ILs. Their exploitation in ‘green’ processes is still limited due to their low degradability but research is currently under way to design new more ‘eco-friendly’ ILs. [less ▲]

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See detailDevelopment of a biomechanical model of deer antler cancellous bone based on X-ray microtomographic images
de Bien, Charlotte ULg; Mengoni, Marlène ULg; D'Otreppe, Vinciane ULg et al

in Micro-CT User Meeting 2012 - Abstract Book (2012, April)

Finite element models accurately compute the mechanical response of bone and bone-like materials when the models include their detailed microstructure. The aim of this paper is to develop and validate a ... [more ▼]

Finite element models accurately compute the mechanical response of bone and bone-like materials when the models include their detailed microstructure. The aim of this paper is to develop and validate a biomechanical model for deer antler cancellous bone tissue based on X-ray microtomographic images. In order to simulate the mechanical behavior under compressive load using a finite element model, images obtained by X-ray microtomography were exported into Metafor, which is an non-linear finite element software initially developed at University of Liège for metal forming processes. This software has recently found biomedical applications. The ultimate goal is to compare model predictions with the mechanical behavior observed experimentally using the Skyscan material testing stage under compression mode. The creation of the biomechanical model mesh from segmented μCT images, its integration into the software Metafor and the simulation of a compression test are described in this paper. [less ▲]

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See detailMagnetic hybrid materials for triggered drug delivery and optical properties of intraocular lens
Liu, Ji ULg; Hurtgen, Marie ULg; Mornet, Stephan et al

Poster (2012, March 30)

Stimuli-responsive nano-materials have been playing increasingly important roles in the biomedical field due to their ability to alter the physico-chemical properties in response to external stimuli, such ... [more ▼]

Stimuli-responsive nano-materials have been playing increasingly important roles in the biomedical field due to their ability to alter the physico-chemical properties in response to external stimuli, such as temperature, pH, ionic strength, magnetic field, etc. Nanohybrids bearing an inorganic core and thermo-responsive polymer shell are particularly applicable in target delivery and controlled drug release. Poly (N-vinylcaprolactam) (PNVCL) and its copolymers, exhibiting lower critical solution temperature (LCST) where the transition between hydrophilic and hydrophobic state happens, is one of the optimal choices for this core/shell structure. Here we present the in-situ fabrication of thermo-responsive gold nanohybrids coated with a novel poly (vinyl alcohol)-b-poly (N-vinylcaprolactam) (PVOH-b-PNVCL) block copolymers, which were prepared by the cobalt-mediated radical polymerization (CMRP). The interaction between both PVOH and PNVCL segments and gold nanoparticles was confirmed by FT-IR spectra. A sharp thermo-induced phase transition with a good reversibility upon change in temperature was detected by DLS and UV/vis spectrometer. Furthermore, the presence of hydrophilic PVOH moieties endows the gold nanohybrids with improved colloidal stability above LCST without any flocculation detected. This kind of gold nanohybrids can be envisaged as a new drug delivery vehicle. [less ▲]

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See detailPreparation of drug-loaded scaffolds for biomedical applications using supercritical carbon dioxide technology
Champeau, Mathilde; Jérôme, Christine ULg; Tassaing, Thierry

Conference (2012, March 25)

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See detailRadical coupling of polymers formed by cobalt-mediated radical polymerization
Debuigne, Antoine ULg; Hurtgen, Marie ULg; Jérôme, Christine ULg et al

in Matyjaszewski, Krzysztof; Sumerlin, Brent; Tsarevsky, Nicolas V. (Eds.) Progress in controlled radical polymerization: mechanisms and techniques (2012)

Considerable progress has been recently made in cobalt-mediated radical polymerization (CMRP), a controlled radical polymerization system based on the temporary deactivation of the polymer chains by a ... [more ▼]

Considerable progress has been recently made in cobalt-mediated radical polymerization (CMRP), a controlled radical polymerization system based on the temporary deactivation of the polymer chains by a cobalt complex, like the improvement of the mechanistic understanding, the extension to a range of monomers and the preparation of novel architectures. However, the real breakthrough in this field concerns the development of efficient radical coupling methods for polymer precursors preformed by CMRP. This book chapter aims to describe the general principle and main characteristics of such radical coupling techniques involving dienes, nitrones, fullerenes or carbon nanotubes. Well-defined and complex architectures obtained by these techniques are provided in order to illustrate their potential for macromolecular engineering. [less ▲]

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See detailSynthesis of poly(lactide-co-glycolide-co-ε-caprolactone)-graft-mannosylated poly(ethylene oxide) copolymers by combination of “clip” and “click” chemistries
Freichels, Hélène; Pourcelle, Vincent; Auzély-Velty, Rachel et al

in Biomacromolecules (2012), 13(3), 760-768

Poly(lactide-co-glycolide) (PLGA) is extensively used in pharmaceutical applications, for example, in targeted drug delivery, because of biocompatibility and degradation rate, which is easily tuned by the ... [more ▼]

Poly(lactide-co-glycolide) (PLGA) is extensively used in pharmaceutical applications, for example, in targeted drug delivery, because of biocompatibility and degradation rate, which is easily tuned by the copolymer composition. Nevertheless, synthesis of sugar-labeled amphiphilic copolymers with a PLGA backbone is quite a challenge because of high sensitivity to hydrolytic degradation. This Article reports on the synthesis of a new amphiphilic copolymer of PLGA grafted by mannosylated poly(ethylene oxide) (PEO). A novel building block, that is, α-methoxy-ω-alkyne PEO-clip-N-hydroxysuccinimide (NHS) ester, was prepared on purpose by photoreaction of a diazirine containing molecular clip. This PEO block was mannosylated by reaction of the NHS ester groups with an aminated sugar, that is, 2-aminoethyl-α-d-mannopyroside. Then, the alkyne ω-end-group of PEO was involved in a copper alkyne- azide coupling (CuAAC) with the pendent azides of the aliphatic copolyester. The targeted mannose-labeled poly(lactide-co-glycolide-co-ε-caprolactone)-graft-poly(ethylene oxide) copolymer was accordingly formed. Copolymerization of d,l-lactide and glycolide with α-chloro-ε-caprolactone, followed by substitution of chlorides by azides provided the azido-functional PLGA backbone. Finally, micelles of the amphiphilic mannosylated graft copolymer were prepared in water, and their interaction with Concanavalin A (ConA), a glyco-receptor protein, was studied by quartz crystal microbalance. This study concluded to the prospect of using this novel bioconjugate in targeted drug delivery. [less ▲]

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See detailProcess for preparing electromagnetic interference shileding materials
Thomassin, Jean-Michel ULg; Jérôme, Christine ULg; Detrembleur, Christophe ULg et al

Patent (2012)

The present invention relates to a process for preparing an electromagnetic interference shielding material, or a precursor thereof, comprising a first polymer matrix and carbon conductive loads, said ... [more ▼]

The present invention relates to a process for preparing an electromagnetic interference shielding material, or a precursor thereof, comprising a first polymer matrix and carbon conductive loads, said process comprises the steps of: (a) Forming a reaction mixture comprising carbon conductive loads and a polymerizable medium said polymerizable medium comprising one or more monomers dissolved in a solvent, (b) Exposing the reaction mixture to polymerization conditions to polymerize said polymerizable medium and thus form a polymer, and (c) Forming a precipitate or an agglomerate of an electromagnetic interference shielding material made of less than 50 wt.% carbon conductive loads dispersed in the first polymer matrix formed in step (b), characterized in that, said polymer is insoluble in said solvent and in that a fraction of the polymer chains thus formed are grafted on part of the surface of the carbon conductive loads. [less ▲]

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See detailProcess for preparing electromagnetic interference shileding materials
Thomassin, Jean-Michel ULg; Jérôme, Christine ULg; Detrembleur, Christophe ULg et al

Patent (2012)

The present invention relates to a process for preparing an electromagnetic interference shielding material, or a precursor thereof, comprising a first polymer matrix and carbon conductive loads, said ... [more ▼]

The present invention relates to a process for preparing an electromagnetic interference shielding material, or a precursor thereof, comprising a first polymer matrix and carbon conductive loads, said process comprises the steps of: (a) Forming a reaction mixture comprising carbon conductive loads and a polymerizable medium said polymerizable medium comprising one or more monomers dissolved in a solvent, (b) Exposing the reaction mixture to polymerization conditions to polymerize said polymerizable medium and thus form a polymer, and (c) Forming a precipitate or an agglomerate of an electromagnetic interference shielding material made of less than 50 wt.% carbon conductive loads dispersed in the first polymer matrix formed in step (b), characterized in that, said polymer is insoluble in said solvent and in that a fraction of the polymer chains thus formed are grafted on part of the surface of the carbon conductive loads. [less ▲]

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See detailTocol modified glycol chitosan for the oral delivery of poorly soluble drugs
Duhem, Nicolas; Rolland, Julien; Riva, Raphaël ULg et al

in International Journal of Pharmaceutics (2012), 423(2), 452-460

The aim of this study was to develop tocol derivatives of chitosan able (i) to self-assemble in the gastrointestinal tract and (ii) to enhance the solubility of poorly soluble drugs. Among the derivatives ... [more ▼]

The aim of this study was to develop tocol derivatives of chitosan able (i) to self-assemble in the gastrointestinal tract and (ii) to enhance the solubility of poorly soluble drugs. Among the derivatives synthesized, tocopherol succinate glycol chitosan (GC-TOS) conjugates spontaneously formed micelles in aqueous solution with a critical micelle concentration of 2 μg mL−1. AFM and TEM analysis showed that spherical micelles were formed. The GC-TOS increased water solubility of 2 model class II drugs. GC-TOS loading efficiency was 2.4% (w/w) for ketoconazole and 0.14% (w/w) for itraconazole, respectively. GC-TOS was non-cytotoxic at concentrations up to 10 mg mL−1. A 3.4-fold increase of the apparent permeation coefficient of ketoconazole across a Caco-2 cell monolayer was demonstrated. Tocol polymer conjugates may be promising vehicles for the oral delivery of poorly soluble drugs. [less ▲]

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See detailSmart coatings by electrografting
Jérôme, Christine ULg

Conference (2012, February 22)

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See detailClay and DOPA containing polyelectrolyte multilayer film for imparting anticorrosion properties to galvanized steel
Faure, Emilie ULg; Halusiak, Emilie; Farina, Fabrice et al

in Langmuir (2012), 28(5), 2971-2978

A facile and green approach is developed to impart remarkable protection against corrosion to galvanized steel. A protecting multilayer film is formed by alternating the deposition of a polycation bearing ... [more ▼]

A facile and green approach is developed to impart remarkable protection against corrosion to galvanized steel. A protecting multilayer film is formed by alternating the deposition of a polycation bearing catechol groups, used as corrosion inhibitors, with clay that induces barrier properties. This coating does not affect the esthetical aspect of the surface and does not release any toxic molecules in the environment. [less ▲]

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See detailA non-linear homogeneous model for bone-like materials under compressive load.
Mengoni, Marlène ULg; Voide, Romain; de Bien, Charlotte ULg et al

in International Journal for Numerical Methods in Biomedical Engineering (2012), 28(2), 334-348

Finite element (FE) models accurately compute the mechanical response of bone and bone-like materials when the models include their detailed microstructure. In order to simulate non-linear behavior, which ... [more ▼]

Finite element (FE) models accurately compute the mechanical response of bone and bone-like materials when the models include their detailed microstructure. In order to simulate non-linear behavior, which currently is only feasible at the expense of extremely high computational costs, coarser models can be used if the local morphology has been linked to the apparent mechanical behavior. The aim of this paper is to implement and validate such a constitutive law. This law is able to capture the non-linear structural behavior of bone-like materials through the use of fabric tensors. It also allows for irreversible strains using an elastoplastic material model incorporating hardening. These features are expressed in a constitutive law based on the anisotropic continuum damage theory coupled with isotropic elastoplasticity in a finite strains framework. This material model was implemented into Metafor, a non-linear FE software. The implementation was validated against experimental data of cylindrical samples subjected to compression. Three materials with bone-like microstructure were tested : aluminum foams of variable density (ERG, Oakland, CA), PLA (polylactic acid) foam (CERM, University of Liège) and cancellous bone tissue of a deer antler (Faculty of Veterinary Medicine, University of Liège). [less ▲]

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See detailMultifunctional poly( ε-caprolactone)-forming networks by Diels–Alder cycloaddition: effect of the adduct on the shape-memory properties
Defize, Thomas ULg; Riva, Raphaël ULg; Jérôme, Christine ULg et al

in Macromolecular Chemistry and Physics (2012), 213(2), 187-197

Star-shaped poly(e-caprolactone)s are functionalized by various dienes (furan and anthracene) and a dienophile (maleimide), and the kinetics of network formation by melt-blending is compared for both ... [more ▼]

Star-shaped poly(e-caprolactone)s are functionalized by various dienes (furan and anthracene) and a dienophile (maleimide), and the kinetics of network formation by melt-blending is compared for both Diels–Alder adducts. When curing at 60 °C, the anthracene–maleimide network forms more rapidly and gives rise to a more crosslinked material than with the furan–maleimide adduct. Shape-memory properties of the networks are compared in terms of Diels–Alder adduct stability. Both materials exhibit excellent fixity and recovery ratios, but the relatively low retro Diels–Alder temperature of the furan–maleimide adduct perturbs the mechanical stability of the network during cyclic tensile testing between 0 and 60 °C, whereas the anthracene–maleimide adduct is shown to be stable up to 150 °C. [less ▲]

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See detailSynthesis of thermo-responsive poly(N-vinylcaprolactam)-containing block copolymers by cobalt-mediated radical polymerization
Hurtgen, Marie ULg; Liu, Ji ULg; Debuigne, Antoine ULg et al

in Journal of Polymer Science. Part A, Polymer Chemistry (2012), 50(2), 400-408

Thermo-responsive block copolymers based on poly(N-vinylcaprolactam) (PNVCL) have been prepared by cobalt-mediated radical polymerization (CMRP) for the first time. The homopolymerization of NVCL was ... [more ▼]

Thermo-responsive block copolymers based on poly(N-vinylcaprolactam) (PNVCL) have been prepared by cobalt-mediated radical polymerization (CMRP) for the first time. The homopolymerization of NVCL was controlled by bis(acetylacetonato)cobalt(II) and a molecular weight as high as 46,000 g/mol could be reached with a low polydispersity. The polymerization of NVCL was also initiated from a poly(vinyl acetate)-Co(acac)2 (PVAc-Co(acac)2) macroinitiator to yield well-defined PVAc-b-PNVCL block copolymers with a low polydispersity (Mw/Mn = 1.1) up to high molecular weights (Mn = 87,000 g/mol), which constitutes a significant improvement over other techniques. The amphiphilic PVAc-b-PNVCL copolymers were hydrolyzed into unprecedented double hydrophilic poly(vinyl alcohol)-b-PNVCL (PVOH-b-PNVCL) copolymers and their temperature-dependent solution behavior was studied by turbidimetry and dynamic light scattering. Finally, the so-called cobalt-mediated radical coupling (CMRC) reaction was implemented to PVAc-b-PNVCL-Co(acac)2 precursors to yield novel PVAc-b-PNVCL-b-PVAc symmetrical triblock copolymers. [less ▲]

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