References of "Jérôme, Christine"
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See detailEfficient hydrogen-bond donor activators for the synthesis of bio-based cyclic carbonates from CO2 and vegetable oils: a combined in-situ FT-IR and DFT study
Alves, Margot ULg; Méreau, Raphaël; Grignard, Bruno ULg et al

Conference (2015, July 06)

The present research aims at developing new very efficient organocatalysts for the chemical fixation of carbon dioxide onto epoxides that are precursors of non-isocyanate polyurethanes (NIPUs). Although ... [more ▼]

The present research aims at developing new very efficient organocatalysts for the chemical fixation of carbon dioxide onto epoxides that are precursors of non-isocyanate polyurethanes (NIPUs). Although this area of research is the subject of many works, the catalytic performance must be further enhanced in particular for the carbonatation of vegetable-based precursors while respecting environmental standards. In this context, we developed a new organocatalytic platform based on the combination of ammonium salts with single or double hydrogen bond donor activators that showed unexpected catalytic activity for the fast addition of CO2 onto epoxidized oils under mild conditions. First of all, in situ kinetic studies of the cycloaddition of CO2 onto model epoxidized oils were monitored by FT-IR spectroscopy in order to evaluate the influence of the hydrogen bond structure and various parameters such as the pressure, the temperature, the catalyst loading, and the nature of the epoxide on the reaction kinetics. Thanks to this catalyst screening, we found that ammonium salt/fluorinated hydrogen bond donors bicomponent organocatalysts were by far more efficient than that proposed in the literature under mild conditions (60°C, 2MPa). Then, the reaction mechanism of the organocatalyzed cycloaddition of propylene oxide onto CO2 was elucidated by performing Density Functional Theory (DFT). Our theoretical results highlighted the key role of the hydrogen bond interaction between the epoxide and the activators for the enhancement of the catalytic platform’s efficiency. [less ▲]

Detailed reference viewed: 72 (5 ULg)
See detailPhoto- and thermo-reversible crosslinked recyclable shape memory materials
Defize, Thomas ULg; Riva, Raphaël ULg; Thomassin, Jean-Michel ULg et al

Poster (2015, July 02)

Shape memory polymers (SMPs) are remarkable materials able to switch from a stressed deformed state (temporary shape) to their initial relaxed state (permanent shape) by the application of a stimulus ... [more ▼]

Shape memory polymers (SMPs) are remarkable materials able to switch from a stressed deformed state (temporary shape) to their initial relaxed state (permanent shape) by the application of a stimulus; such as heat or light. Typically; the shape memory property is generally observed for chemically or physically cross-linked polymers that exhibit an elastomeric behavior above a phase transition; e.g. glass or melting transition. As an example; cross-linked semi-crystalline poly(ε-caprolactone) (PCL) is widely studied for the development of SMPs. As most of SMPs are irreversibly cross-linked material; their reprocessing is impossible preventing any recycling. Thereby; reversible reactions; allowing the formation/cleavage of the network; raise tremendous interest for the development of new SMPs. Recently, we reported the preparation reversibly cross-linked PCL-based SMP using the Diels-Alder (DA) reaction between furan and maleimide end-groups of 4-arm star-shaped PCL, well-known to create reversible bonds. After implementation, this shape memory material was demonstrated to be recyclable, and was characterized by excellent fixity and recovery before and after recycling experiments. However, the relatively low retro DA temperature of the furan-maleimide adducts led to an inelastic deformation during shape memory tensile cycles. In order to get rid of this drawback, an alternative approach was investigated. The substitution of the DA reaction by a photo-reversible reaction, typically the photo-induced (2+2) cycloaddition of coumarins, was proposed to prepare cross-linked PCL matrix presenting one-way and two-way memory properties, since photolabile adducts are supposed to be stable during shape memory tensile cycles. [less ▲]

Detailed reference viewed: 70 (6 ULg)
See detailDouble hydrophilic polyphosphoester containing copolymers as efficient templating agnets for calcium carbonate microparticles
Ergül, Zeynep ULg; Debuigne, Antoine ULg; Calvignac, Brice et al

Conference (2015, June 22)

The design of drug delivery systems (DDS) often requires biodegradable and biocompatible materials that allow safe retention and controlled drug release. In this respect, CaCO3 particles are appropriate ... [more ▼]

The design of drug delivery systems (DDS) often requires biodegradable and biocompatible materials that allow safe retention and controlled drug release. In this respect, CaCO3 particles are appropriate drug carriers that have excellent properties such as low density, high specific surface areas and porosity for drugs and proteins encapsulation. Here, degradable synthetic copolymers based on polyphosphoester (PPE) were used to template CaCO3 particles. PPE is a promising candidate due to its biocompatibility, biodegradability and low toxicity of its degradation products such as phosphates. In particular, PPE copolymers with carboxylic acid pendant groups and negatively charged polyphosphodiester-based copolymers were prepared by organocatalyzed ring opening polymerization (ROP) initiated from poly(ethylene oxide). The moieties introduced along the polymer chains enhance the calcium affinity and so the ability of the copolymers to tune the morphology of the CaCO3 particles. The copolymers were tested as templating agents for the preparation of CaCO3 particles by the classical chemical pathway and the supercritical CO2 (Sc-CO2) route. The morphology of the resulting particles was then compared to the one of particles obtained using hyaluronic acid (HA) as a templating agent. The synthesis involving Sc-CO2 and the copolymer with pendant carboxylic groups was particularly interesting and led to smaller (~1.5 µm) and non-aggregated particles. In the future, the impact of the copolymer structure and of the particle size on the encapsulation and release processes will be investigated. [less ▲]

Detailed reference viewed: 49 (11 ULg)
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See detailFluorinated alcohols as activators for the solvent-free chemical fixation of carbon dioxide onto epoxides
Gennen, Sandro ULg; Alves, Margot ULg; Méreau, Raphaël et al

in ChemSusChem (2015), 8(11), 1845-1849

The addition of fluorinated alcohols to onium salts provides highly efficient organocatalysts for the chemical fixation of CO2 onto epoxides under mild experimental conditions. The combination of online ... [more ▼]

The addition of fluorinated alcohols to onium salts provides highly efficient organocatalysts for the chemical fixation of CO2 onto epoxides under mild experimental conditions. The combination of online kinetic studies, NMR titrations and DFT calculations allows understanding this synergistic effect that provides an active organocatalyst for CO2/epoxides coupling. [less ▲]

Detailed reference viewed: 61 (20 ULg)
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See detailA new design of organic radical batteries (ORBs): carbon nanotube buckypaper electrode functionalized by electrografting
Aqil, Abdelhafid ULg; Vlad, Alexandru; Piedboeuf, Marie-Laure ULg et al

in Chemical Communications (2015), 51(45), 9301-9304

A novel hybridmaterial displaying a fast and reversible charge storage capability is prepared by electrografting of an alkoxyamine-bearing acrylate onto a carbon nanotube buckypaper, followed by the quan ... [more ▼]

A novel hybridmaterial displaying a fast and reversible charge storage capability is prepared by electrografting of an alkoxyamine-bearing acrylate onto a carbon nanotube buckypaper, followed by the quan- titative generation of an electroactive polynitroxide. [less ▲]

Detailed reference viewed: 68 (14 ULg)
See detailAliphatic polyphosphates, a promising class of polymers for drug delivery
Vanslambrouck, Stéphanie ULg; Clément, Benoit; Molin, Daniel G. et al

Conference (2015, June 02)

Detailed reference viewed: 19 (7 ULg)
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See detailDrug loading of sutures by supercritical CO2 impregnation: effect of polymer/drug interactions and thermal transitions
Champeau, Mathilde; Thomassin, Jean-Michel ULg; Tassaing, Thierry et al

in Macromolecular Materials and Engineering (2015), 300(6), 596-610

This paper aims at exploring the scCO2 impregnation of three commonly implanted polymer sutures made of poly-l-lactide (PLLA), poly(ethylene terephthalate) (PET) and polypropylene (PP) with two anti ... [more ▼]

This paper aims at exploring the scCO2 impregnation of three commonly implanted polymer sutures made of poly-l-lactide (PLLA), poly(ethylene terephthalate) (PET) and polypropylene (PP) with two anti-inflammatory drugs namely ketoprofen and aspirin. For all the investigated polymer/drug systems, the drug loading increases with temperature and pressure. It appears that two main criteria must be fulfilled by the polymer to achieve high drug loading: (i) a good affinity between the polymer and the drug and (ii) a high chain mobility to favor the diffusion of the drug into the matrix. As the investigated PLLA fulfills these two requirements, drug loading up to 32.5% with ketoprofen and 8.1% with aspirin has been achieved. [less ▲]

Detailed reference viewed: 25 (2 ULg)
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See detailGold nanorods coated with mesoporous silica shell as drug delivery system for remote near infrared light-activated release and potential phototherapy
Liu, Ji; Detrembleur, Christophe ULg; De Pauw-Gillet, Marie-Claire ULg et al

in Small (Weinheim an der Bergstrasse, Germany) (2015), 11(19), 2323-2332

In this study, we report the synthesis of a nanoscaled drug delivery system, which is composed of a gold nanorod-like core and a mesoporous silica shell (GNR@MSNP) and partially uploaded with phase ... [more ▼]

In this study, we report the synthesis of a nanoscaled drug delivery system, which is composed of a gold nanorod-like core and a mesoporous silica shell (GNR@MSNP) and partially uploaded with phase-changing molecules (1-tetradecanol, TD, Tm 39 degrees C) as gatekeepers, as well as its ability to regulate the release of doxorubicin (DOX). Indeed, a nearly zero premature release is evidenced at physiological temperature (37 degrees C), whereas the DOX release is efficiently achieved at higher temperature not only upon external heating, but also via internal heating generated by the GNR core under near infrared irradiation. When tagged with folate moieties, GNR@MSNPs target specifically to KB cells, which are known to overexpress the folate receptors. Such a precise control over drug release, combining with the photothermal effect of GNR cores, provides promising opportunity for localized synergistic photothermal ablation and chemotherapy. Moreover, the performance in killing the targeted cancer cells is more efficient compared with the single phototherapeutic modality of GNR@MSNPs. This versatile combination of local heating, phototherapeutics, chemotherapeutics and gating components opens up the possibilities for designing multifunctional drug delivery systems. [less ▲]

Detailed reference viewed: 94 (19 ULg)
See detailOrganometallic-mediated radical synthesis of well-defined ethylene-vinyl acetate statistical and block copolymers
Demarteau, Jérémy ULg; Kermagoret, Anthony; Jérôme, Christine ULg et al

Poster (2015, May 18)

The copolymerization of ethylene (E) and vinyl acetate (VAc) is of high interest for polymer industry. Nevertheless, the control of the macromolecular parameters of ethylene-vinyl acetate copolymers (EVAs ... [more ▼]

The copolymerization of ethylene (E) and vinyl acetate (VAc) is of high interest for polymer industry. Nevertheless, the control of the macromolecular parameters of ethylene-vinyl acetate copolymers (EVAs) is difficult to achieve. Herein, we report the controlled radical copolymerization of these monomers by organometallic-mediated radical polymerization (OMRP) using Co(acac)2 as controlling agent. The ethylene pressure is varied from 10 to 100 bar and we discuss the effect of this parameter on kinetics, level of control and copolymer composition. EVAs are synthetized accordingly with low dispersities and ethylene content reaches up to 57 mol%. The precision design of EVA-containing block copolymers, i.e. PVAc-block-EVA, is also addressed. [less ▲]

Detailed reference viewed: 39 (7 ULg)
See detailAliphatic polyphosphates: a promising family of polymers for drug delivery
Vanslambrouck, Stéphanie ULg; Clément, Benoit; Riva, Raphaël ULg et al

Poster (2015, May 18)

Thanks to their biocompatibility and biodegradability, polyphosphates are appealing polymers for biomedical applications. In contrast to polyesters, polyphosphate properties and functionality are easily ... [more ▼]

Thanks to their biocompatibility and biodegradability, polyphosphates are appealing polymers for biomedical applications. In contrast to polyesters, polyphosphate properties and functionality are easily tuned via the chemical nature of the lateral chains. In this work, a series of amphiphilic PEO-block-polyphosphate copolymers were synthesized by organo-catalyzed ring-opening polymerization of cyclic phosphates. These polymers are directly dissolved in water in the absence of any organic solvent and they self-assemble to form nanoparticles Our work aims at changing the lateral chain of polyphosphates to investigate the influence of this structural modification on (i) the size of the nanoparticles, (ii) the critical aggregation concentration, (iii) the encapsulation of an hydrophobic drug in the core of the nanoparticles and, finally, (iv) the release of the drug. [less ▲]

Detailed reference viewed: 46 (13 ULg)
See detailPrerparation of graphene oxide-poly(methyl methacrylate) nanocompposites by a precipitation polymerization process and their dielectric and rheological characterization
Alkarmo, Walid ULg; Thomassin, Jean-Michel ULg; Macosko, Christopher et al

Poster (2015, May 18)

The graphene sheet, a flat monolayer composed of sp2-bonded carbon atoms packed into a two-dimensional honeycomb structure, has attracted a tremendous attention due to its extraordinary electrical ... [more ▼]

The graphene sheet, a flat monolayer composed of sp2-bonded carbon atoms packed into a two-dimensional honeycomb structure, has attracted a tremendous attention due to its extraordinary electrical, thermal, and mechanical properties. Graphene nanosheets–poly(methyl methacrylate) GN/PMMA nanocomposites were prepared via a precipitation polymerization process in a water/methanol mixture and thermal or chemical reduction of graphene oxide (GO). Scanning electron and transmission electron microscopies confirmed that the precipitate consists of polymer particles (<1μm) surrounded by the GO sheets. The GO sheets acts as a surfactant and adsorbs on the interface between polymerized PMMA particles and solvent mixture. Parallel dielectric and rheological characterization demonstrated that the thermal reduction is a quite fast process without significant degradation of the polymer. In addition, the main increase in electrical conductivity occurred during the first minutes of the thermal treatment but continued for about 30 min. The absence of dramatic change in the storage modulus confirmed that the increase in conductivity was not due to alteration of the particle dispersion. The addition of GO sheets had a dramatic influence on the glass transition (Tg) temperature of PMMA with an increase of 8 °C at only 0.2 wt %. This Tg increase has been attributed to the restricted mobility of PMMA chains which have been grafted onto the graphene surfaces during the in-situ polymerization. However, at GO content higher than 0.7 wt %, the glass transition decreases. This drop may be attributed to the increase in the number of stacked graphene layers. The obtained GN/PMMA composites not only have enhanced mechanical properties but also achieved electrical conductivity higher than 10 −2 S/m at 0.4 wt % of GO. The study should open up new opportunities in the design of GN-based polymer nanocomposites. [less ▲]

Detailed reference viewed: 184 (13 ULg)
See detailNon-isocyanate polyurethane: from the monomer synthesis to foamed materials
Gennen, Sandro ULg; Alves, Margot ULg; Tassaing, Thierry et al

Poster (2015, May 18)

Polyurethane (PU) is one of the most important polymers in our everyday life with numerous applications such as thermosets, thermoplastics, elastomers, adhesives, sealants, coatings, rigid and flexible ... [more ▼]

Polyurethane (PU) is one of the most important polymers in our everyday life with numerous applications such as thermosets, thermoplastics, elastomers, adhesives, sealants, coatings, rigid and flexible foams... Classically, PUs are produced by a step-growth polymerization between diols and diisocyanates. However, isocyanates are harmful upon prolonged exposure to vapours which can lead to health issues such as asthma and skin irritation. In addition, isocyanates are produced from even more toxic and explosive phosgene. Due to these problems in combination with increasing regulatory scrutiny, there is today a need to develop isocyanate- and phosgene free- PU synthesis, also called non-isocyanate polyurethane or NIPUs. One of the most promising alternatives to the conventional synthesis of PU relies on the step-growth polymerization between bicyclic carbonate monomers and diamines, but until now, obtaining high molar mass NIPUs in a short time still remains a challenge. This study will be focused on three objectives: 1) The synthesis of CO2-sourced biscyclic carbonates by CO2/epoxide coupling using new highly efficient bicomponent organocatalysts allowing the fast conversion of epoxides into the corresponding cyclic carbonates under mild and solvent-free conditions. 2) The synthesis of high molar mass NIPUs from CO2-sourced monomers and diamines thanks to the use of efficient organocatalysts. A series of organic compounds interacting with cyclic carbonates by hydrogen bonding were first identified and their catalytic activity was highlighted by a model reaction between ethylene carbonate and a primary amine before extrapolation to NIPU synthesis. 3) The scCO2-assisted foaming of CO2-sourced NIPUs with production of potential carbon zero-emission materials with low thermal conductivity [less ▲]

Detailed reference viewed: 210 (4 ULg)
See detailIntercalation of cationic aliphatic polyphosphates between montmorillonite nanosheets towards flame-retardant polymer materials
Carion, Stéphan ULg; Lecomte, Philippe ULg; Thomassin, Jean-Michel ULg et al

Poster (2015, May 18)

Among the strategies used to impart flame-retardant properties to polymer materials, the most effective ones include the addition of phosphorous compounds such as organic polyphosphates and the dispersion ... [more ▼]

Among the strategies used to impart flame-retardant properties to polymer materials, the most effective ones include the addition of phosphorous compounds such as organic polyphosphates and the dispersion of layered silicates (nanoclays). The aim of this work is to combine both approaches by the dispersion of nanoclays, organomodified by cationic aliphatic polyphosphates, into a polymer matrix. In this work, the synthesis of an aliphatic polyphosphate end-capped by an imidazolium cation followed by its intercalation between montmorillonite nanoclays sheets is reported. In a first step, the polyphosphate was synthesized by ring-opening polymerization of the corresponding cyclic phosphate using 1-(11-hydroxy-undecyl)-3-methylimidazolium bromide as initiator. This polymerization was catalyzed by DBU and a thiourea derivative. This polymer was characterized by different techniques (31P and 1H NMR, SEC, TGA, DSC). Finally, the cationic end-functionalized polymer was exchanged with sodium cations present in montmorillonite. The intercalation of the polyphosphate between the clay nanosheets was proved by X-Ray Diffraction (XRD) and thermogravimetric analysis (TGA). This last technique was also used to determine the influence of the intercalation on the thermal stability of the polyphosphate.polyphosphates, into a polymer matrix. In this work, the synthesis of an aliphatic polyphosphate end-capped by an imidazolium cation followed by its intercalation between montmorillonite nanoclays sheets is reported. In a first step, the polyphosphate was synthesized by ring-opening polymerization of the corresponding cyclic phosphate using 1-(11-hydroxy-undecyl)-3-methylimidazolium bromide as initiator. This polymerization was catalyzed by DBU and a thiourea derivative. This polymer was characterized by different techniques (31P and 1H NMR, SEC, TGA, DSC). Finally, the cationic end-functionalized polymer was exchanged with sodium cations present in montmorillonite. The intercalation of the polyphosphate between the clay nanosheets was proved by X-Ray Diffraction (XRD) and thermogravimetric analysis (TGA). This last technique was also used to determine the influence of the intercalation on the thermal stability of the polyphosphate. [less ▲]

Detailed reference viewed: 82 (5 ULg)
See detailNew efficient bicomponent organocatalysts for the chemical fixation of CO2 onto epoxides: a theoretical study
Alves, Margot ULg; Méreau, Raphaël; Grignard, Bruno ULg et al

Poster (2015, May 18)

Regarding the economic and environmental issues, valorising CO2 as a C1 feedstock for producing useful building blocks is seducing as it is a free and abundant waste resulting from the human activity ... [more ▼]

Regarding the economic and environmental issues, valorising CO2 as a C1 feedstock for producing useful building blocks is seducing as it is a free and abundant waste resulting from the human activity. Cyclic carbonates are useful compounds that found application as green solvents, electrolytes for lithium battery or monomers for polycarbonates or polyurethanes synthesis. These cyclocarbonates can be synthesized with a total atom economy by chemical fixation of CO2 onto epoxides using organometallic complexes or organocatalysts. To date, although this area of research has been the subject of many studies, the identification and development of (organo)catalysts highly efficient under mild experimental conditions still remains challenging. In this context, we developed a new organocatalytic platform based on the use of ammonium salts in combination with single or double hydrogen bond donor activators derived from fluorinated alcohols that showed unexpected booster effect. In this contribution, the ammonium/fluoroalcohol promoted CO2/propylene oxide coupling was investigated through detailed kinetic studies by IR spectroscopy under pressure and results were compared to the most efficient organocatalysts based on ammonium salts and (multi)phenolic derivatives that were reported in the literature. In order to finely understand the reaction mechanism, this study was completed by molecular modeling. DFT calculations showed that the addition of H-bond donors (HBD) with hexafluoroisopropanol functionalities modified the mechanism of the ammonium promoted coupling of CO2 with epoxides. HBDs dramatically decreased the epoxide ring-opening step barrier which highlights the key role of the fluorinated activators in stabilizing the intermediates and transitions states by inter- and intra-molecular hydrogen bonds. [less ▲]

Detailed reference viewed: 98 (3 ULg)