References of "Debuigne, Antoine"
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See detailOrganocobalt complexes as sources of carbon-centered radicals for organic and polymer chemistries
Demarteau, Jérémy; Debuigne, Antoine ULiege; Detrembleur, Christophe ULiege

in Chemical Reviews (in press)

Organocobalt(III) complexes (R-CoIII), defined as cobalt complexes featuring a carbon−cobalt bond, are largely used to produce carbon-centered radicals by homolytic cleavage of their C−Co bond under mild ... [more ▼]

Organocobalt(III) complexes (R-CoIII), defined as cobalt complexes featuring a carbon−cobalt bond, are largely used to produce carbon-centered radicals by homolytic cleavage of their C−Co bond under mild conditions. They are key compounds in cutting-edge developments in the fields of organic chemistry, biochemistry, medical research, radical reactions, and organometallic chemistry. This is the first Review of the use of R-CoIII in both organic and polymer chemistries. Although pioneering works in organic synthesis have largely contributed to the implementation of R-CoIII in polymer design, the two fields have evolved independently, with many breakthroughs on both sides. The main motivation of this Review is to confront both fields to stimulate cross-fertilization. It notably describes the most important synthetic pathways for R-CoIII, the influence of the ligand structure and the environment of the complex on the C−Co bond strength, the modes of formation of the radicals, and the most relevant R-CoIII-promoted radical reactions, with a focus on the main reaction mechanisms. [less ▲]

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See detailPrecision design of vinyl amine and vinyl alcohol-based copolymers via cobalt-mediated radical polymerization
Stiernet, Pierre ULiege; Jérôme, Christine ULiege; Debuigne, Antoine ULiege

in Polymer Chemistry (in press)

Poly(vinyl alcohol) (PVA) and poly(vinyl amine) (PVAm) are major industrial polymers involved in countless applications taking advantage of their ability to establish hydrogen bonds and, for the latter ... [more ▼]

Poly(vinyl alcohol) (PVA) and poly(vinyl amine) (PVAm) are major industrial polymers involved in countless applications taking advantage of their ability to establish hydrogen bonds and, for the latter, to create charges along the polymer’s backbone upon protonation. Although combining vinyl alcohol and vinyl amine units in specific proportions within copolymers should allow precise tuning of their properties and enlarge the scope of their use, the controlled synthesis of poly(VAm-co-VA)s has been completely dis- regarded so far. In this context, we report a straightforward strategy for preparing the aforementioned copolymers via cobalt-mediated radical copolymerization of vinyl acetate (VAc) and vinyl acetamide (NVA) followed by hydrolysis. Copolymerization conditions were optimized to produce poly(NVA-co-VAc) with predictable molar mass, low dispersity and precise composition. Reactivity ratios were also determined to gain insight into the distribution of the amine and alcohol moieties along the backbone. Depending on the hydrolysis treatment applied to poly(NVA-co-VAc), unprecedented well-defined poly(VAm-co-VA)s and poly(NVA-co-VA)s were achieved via full deprotection of the precursor and selective hydrolysis of its esters, respectively. [less ▲]

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See detailStraightforward synthesis of well-defined poly(vinylidene fluoride) and its block copolymers by cobalt-mediated radical polymerization
Falireas, Panagiotis G.; Ladmiral, Vincent; Debuigne, Antoine ULiege et al

in Macromolecules (2019), 52(3), 1266-1276

The organometallic-mediated radical polymeriza- tion (OMRP) of vinylidene fluoride (VDF) using an alkyl cobalt(III) compound as initiator was recently proven successful for the controlled synthesis ofPVDF ... [more ▼]

The organometallic-mediated radical polymeriza- tion (OMRP) of vinylidene fluoride (VDF) using an alkyl cobalt(III) compound as initiator was recently proven successful for the controlled synthesis ofPVDF (Angew. Chem., Int. Ed. 2018, 57, 2934−2937). However, the required synthesis of the organometallic initiator renders this method labor-intensive and time-consuming. This article reports the straightforward synthesis of well-defined poly(VDF) and its block copolymers via OMRP performed using a two-component initiating system from readily available compounds. First, PVDF was obtained by redox initiation using the combination of a peroxide initiator and bis(acetylacetonato)cobalt(II) (Co(acac)2). This step was optimized in terms of the initiator choice, polymerization temperature, and reactant molar ratio. The best results regarding the molar mass control and the dispersities were obtained using bis(tert-butylcyclohexyl) peroxydicarbonate as initiator at 60 °C. The polymerization followed first-order kinetics, and the molar masses ofPVDF increased linearly up to a 27% conversion to reach 11 800 g/mol with low dispersities (Đ = 1.35). Chain extension of the resulting PVDF-Co(acac)2 with vinyl acetate (VAc) led to three diblock copolymers of various chain lengths. [less ▲]

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See detailUgi three-component polymerization toward poly(α-amino amide)s
Stiernet, Pierre ULiege; Lecomte, Philippe ULiege; De Winter, Julien et al

in ACS Macro Letters (2019), 8

Due to their great modularity, ease of implementation, and atom economy, multicomponent reactions (MCRs) are becoming increasingly popular macromolecular engineering tools. In this context, MCRs suitable ... [more ▼]

Due to their great modularity, ease of implementation, and atom economy, multicomponent reactions (MCRs) are becoming increasingly popular macromolecular engineering tools. In this context, MCRs suitable in polymer synthesis are eagerly searched for. This work demonstrates the potential of the Ugi-three component reaction (Ugi-3CR) for the design of polymers and, in particular, of poly(α-amino amide)s. A series of polymers containing amino and amido groups within their backbone were obtained through a one-pot process by reacting aliphatic or aromatic diamines, diisocyanides, and aldehydes. The impact of temperature, concentration, catalyst loading, and substrates on polymerization efficiency is discussed. A preliminary study on the thermal properties and the solution behavior of these poly(α-amino amide)s was carried out. An aliphatic-rich derivative notably showed some pH-responsiveness in water via protonation−deprotonation of its amino groups. [less ▲]

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See detailDesign of monodisperse polystyrene/polyacrylonitrile core-shell particles used as templating agents and source of carbon
Thangaraj, Vidhyadevi ULiege; Schrijnemakers, Audrey ULiege; Dewalque, Jennifer ULiege et al

Poster (2018, October 03)

In the present work, we synthesized Polystyrene (PS) and Polystyrene/polyacrylonitrile (PS/PAN) core shell particles by surfactant-free emulsion polymerization and characterized them by DLS and TEM. After ... [more ▼]

In the present work, we synthesized Polystyrene (PS) and Polystyrene/polyacrylonitrile (PS/PAN) core shell particles by surfactant-free emulsion polymerization and characterized them by DLS and TEM. After deposition of the PS/PAN particles on a surface, a TiCl4 solution was infiltrated in the interstices before thermal treatment. The carbonization of the PS core and the PAN shell led to voids and carbon in the inorganic layer, respectively. This paved the way to well-organized carbon coated porous TiO2 layers of interest in the field of electronics. [less ▲]

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See detailTargeting melanoma tumor cells with pH-responsive lipid nanocapsules: in vitro and in vivo studies
Pautu, Vincent ULiege; Lepeltier, Elise; Debuigne, Antoine ULiege et al

Conference (2018, September)

Detailed reference viewed: 24 (6 ULiège)
See detailMultifunctional poly(ionic liquid)s: from precision synthesis to applications in energy
Detrembleur, Christophe ULiege; Cordella, Daniela; Patil, Nagaran et al

Conference (2018, August 29)

Detailed reference viewed: 19 (2 ULiège)
See detailAmélioration de l’internalisation cellulaire à l’aide de nanocapsules lipidiques pH-sensibles
Pautu, Vincent ULiege; Lepeltier, Elise; Debuigne, Antoine ULiege et al

Poster (2018, June)

Detailed reference viewed: 17 (0 ULiège)
See detailStealth and pH-sensitive lipid nanocapsules for increased internalization in melanoma cells
Pautu, Vincent ULiege; Lepeltier, Elise; Debuigne, Antoine ULiege et al

Conference (2018, June)

Detailed reference viewed: 17 (2 ULiège)
See detailControlled radical (co)polymerisation of allylic- and vinylic monomers originating from renewable resources
Scholten, Philip ULiege; Demarteau, Jérémy; Gennen, Sandro ULiege et al

Conference (2018, May 29)

In light of recent efforts of applying principles of green and sustainable chemistry within macromolecular engineering, a large number of novel bio-sourced monomers are available. Especially cyclic ... [more ▼]

In light of recent efforts of applying principles of green and sustainable chemistry within macromolecular engineering, a large number of novel bio-sourced monomers are available. Especially cyclic carbonates (CCs), because of their effective ring-opening polymerisation to yield polymers such as non-isocyanate poly(urethane)s, has seen rapid progress during the past decade. Yet, very few examples exist of controlled radical polymerisations (CRP) of CCs bearing a double bond, part of the reason being that (i) up to now only some sustainable synthetic routes to such molecules are known and (ii) some interesting monomers contain an allylic-double bond that is challenging to control by most radical polymerization techniques. In this communication, we report on the synthesis of new bio-sourced polymers by the preparation of novel cyclic carbonate monomers from renewable resources followed by their controlled radical polymerization. Mainly bio-sourced allyl- or unconjugated vinyl-type cyclic carbonates are investigated. Cobalt-mediated radical polymerisation (CMRP) is used as a powerful CRP technique that is active for the polymerization of highly unreactive non-conjugated monomers under mild experimental conditions. [less ▲]

Detailed reference viewed: 39 (7 ULiège)
See detailControlled radical (co)polymerisation of vinylic monomers originating from renewable resources
Scholten, Philip ULiege; Demarteau, Jérémy; Gennen, Sandro ULiege et al

Poster (2018, May 29)

In light of recent efforts of applying principles of green and sustainable chemistry within macromolecular engineering, a large number of novel bio-sourced monomers are available. Especially cyclic ... [more ▼]

In light of recent efforts of applying principles of green and sustainable chemistry within macromolecular engineering, a large number of novel bio-sourced monomers are available. Especially cyclic carbonates (CCs), because of their effective ring-opening polymerisation to yield polymers such as non-isocyanate poly(urethane)s, has seen rapid progress during the past decade. Yet, very few examples exist of controlled radical polymerisations (CRP) of CCs bearing a double bond, part of the reason being that (i) up to now only some sustainable synthetic routes to such molecules are known and (ii) some interesting monomers contain an allylic-double bond that is challenging to control by most radical polymerization techniques. In this communication, we report on the synthesis of new bio-sourced polymers by the preparation of novel cyclic carbonate monomers from renewable resources followed by their controlled radical polymerization. Mainly bio-sourced allyl- or unconjugated vinyl-type cyclic carbonates are investigated. Cobalt-mediated radical polymerisation (CMRP) is used as a powerful CRP technique that is active for the polymerization of highly unreactive non-conjugated monomers under mild experimental conditions. [less ▲]

Detailed reference viewed: 13 (5 ULiège)
See detailAdvanced emulsion templated porous polymers via reversible deactivation radical polymerization
Debuigne, Antoine ULiege

Conference (2018, May 28)

Macroporous polymer monoliths are remarkable materials used in several applications such as supported catalysis, chromatography, water purification, gas capture, to name but a few. The emulsion-templated ... [more ▼]

Macroporous polymer monoliths are remarkable materials used in several applications such as supported catalysis, chromatography, water purification, gas capture, to name but a few. The emulsion-templated polymerization method, often based on conventional radical polymerization, is a very popular and straightforward approach for preparing such porous polymers. Nevertheless, the demand for more and more sophisticated porous supports with controlled porosity, good mechanical properties and specific surface properties, is increasing and requires the development of innovative synthesis strategies. This communication reports the possible benefits of the reversible deactivation radical polymerization (RDRP) methods for the design of advanced macroporous monoliths via emulsion templated polymerization. For example, copolymers with precise architecture, composition and chain-end functionality, synthesized by RDRP, can be used as macromolecular surfactants for stabilizing various types of high and medium internal phase emulsion polymerizations leading to porous materials with tunable morphologies. Moreover, the physical and chemical anchoring of the macromolecular surfactants at the surface of the porous monoliths allows the functionalization of the porous supports while preserving their openness. Finally, RDRP gives access to specific surfactants able to stabilize CO2 in-ionic liquid (IL) emulsions leading to the single step synthesis of unique and valuable macroporous poly(ionic liquid)s/ILs gels. Overall, this presentation will emphasize the potential of RDRP for the emulsion-templated polymerization and the production of advanced functional macroporous monoliths. [less ▲]

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See detailMerging CO2‑based building blocks with cobalt-mediated radical polymerization for the synthesis of functional poly(vinyl alcohol)s
Scholten, Philip ULiege; Demarteau, Jérémy ULiege; Gennen, Sandro ULiege et al

in Macromolecules (2018), 51(9), 3379-3393

The use of CO2-based α-alkylidene cyclic carbonates in controlled radical polymerization has so far not been exploited, despite the fact that the cyclic carbonate ring offers a multitude of possible ... [more ▼]

The use of CO2-based α-alkylidene cyclic carbonates in controlled radical polymerization has so far not been exploited, despite the fact that the cyclic carbonate ring offers a multitude of possible modifications. Herein, the synthesis of well-defined copolymers of vinyl acetate (VAc) and 4,4-dimethyl-5-methylene-1,3-dioxolan-2-one (DMMDO) using cobalt-mediated radical polymerization (CMRP) at 40 °C is reported. The controlled nature of the polymerization was confirmed while molecular weights of up to 25 000 g mol−1 and narrow dispersities (<1.4) were obtained. The copolymer structure was elucidated combining NMR, FT-IR, and MALDI-TOF analyses and consists of a polymer backbone with pendant carbonate rings. Further insights into the copolymer structure were gained through the monomers’ reactivity ratios, and a homogeneous distribution of the DMMDO monomer along the polymer chain was observed. A highly water-soluble poly(vinyl alcohol)-based copolymer was obtained by basic hydrolysis, whereas the chemoselective acidic hydrolysis of the acetate groups left the cyclic carbonate rings untouched, which were then exploited for further postmodification with amines. The precise copolymerization of VAc with CO2-sourced five-membered cyclic carbonates bearing an exomethylene moiety is therefore a powerful tool for the synthesis of new variants of poly(vinyl alcohol)-based copolymers. [less ▲]

Detailed reference viewed: 74 (12 ULiège)
See detailpH-responsive lipid nanocapsules for enhanced cellular uptake
Pautu, Vincent ULiege; Lepeltier, Elise; Debuigne, Antoine ULiege et al

Poster (2018, May)

Detailed reference viewed: 18 (2 ULiège)
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See detailPoly(N-methylvinylamine)-based copolymers for improved gene transfection
Dréan, Mathilde; Debuigne, Antoine ULiege; Jérôme, Christine ULiege et al

in Macromolecular Bioscience (2018), 18(4), 1700353

Poly(N-methylvinylamines) with secondary amines can form complexes with plasmid DNA (pDNA) and provide transfection efficiency in HeLa cells in the same order as linear polyethyleneimine but with higher ... [more ▼]

Poly(N-methylvinylamines) with secondary amines can form complexes with plasmid DNA (pDNA) and provide transfection efficiency in HeLa cells in the same order as linear polyethyleneimine but with higher cell viability. Chemical modifications of poly(N-methylvinylamine) backbones are performed to further improve transfection efficiency while maintaining low degree of cytotoxicity. In a first type of polymer, primary amino groups are incorporated via a copolymerization strategy. In a second one, primary amino and imidazole groups are incorporated also via a copolymerization strategy. In a third one, secondary amino groups are substituted with methylguanidine functions through a postpolymerization reaction. Thus, novel polymers of various molecular masses are synthesized, characterized, and their interaction with pDNA studied. Then, their transfection efficiency and cytotoxicity are tested in HeLa cells. Two polymethylvinylamine-based copolymers, one containing 20% of imidazole moieties and another one composed of 12% of guanidinyl units allow remarkable transfection efficiency of HeLa, pulmonary (16HBE), skeletal muscle (C2C12), and dendritic (DC2.4) cells. Overall, this work thus identifies new promising DNA carriers and chemical modifications that improve the transfection efficiency while maintaining low degree of cytotoxicity. [less ▲]

Detailed reference viewed: 51 (11 ULiège)
See detailControlled radical (co)polymerisation of allylic and vinylic monomers originating from renewable resources
Scholten, Philip ULiege; Demarteau, Jérémy ULiege; Gennen, Sandro ULiege et al

Conference (2018, March 22)

In light of recent efforts of applying principles of green and sustainable chemistry within macromolecular engineering, a large number of novel bio-sourced monomers are available. Especially cyclic ... [more ▼]

In light of recent efforts of applying principles of green and sustainable chemistry within macromolecular engineering, a large number of novel bio-sourced monomers are available. Especially cyclic carbonates (CCs), because of their effective polyaddition with polyamines to yield polymers such as non-isocyanate poly(urethane)s, have seen rapid progress during the past decade. Yet, very few examples exist of controlled radical polymerisations (CRP) of CCs bearing a double bond, part of the reason being that (i) up to now only some sustainable synthetic routes to such molecules are known and (ii) some interesting monomers contain reactive double bonds which are challenging to control by most radical polymerisation techniques. Herein we report on how cobalt-mediated radical polymerisation (CMRP) proves a powerful method for the (co)polymerisation of such monomers. Furthermore, the unique characteristics of the resulting (co)polymers and their value for applications in composites are highlighted. [less ▲]

Detailed reference viewed: 31 (2 ULiège)