References of "Debuigne, Antoine"
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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 (in press)

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 ▲]

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See detailOrganometallic mediated radical polymerization of vinylidene fluoride
Banerjee, Sanjib; Ladmiral, Vincent; Debuigne, Antoine ULiege et al

in Angewante Chemie Intenational Edition (in press)

An unprecedented level of control for the radical polymerization of vinylidene fluoride (VDF), yielding well-defined PVDF (up to 14,500 g/mol) with low dispersity (≤1.32), was achieved using ... [more ▼]

An unprecedented level of control for the radical polymerization of vinylidene fluoride (VDF), yielding well-defined PVDF (up to 14,500 g/mol) with low dispersity (≤1.32), was achieved using organometallic mediated radical polymerization (OMRP) with an organocobalt compound as initiator. The high chain-end fidelity was demonstrated by the synthesis of PVDF- and PVAc-containing di-and tri-block copolymers. DFT calculations rationalize the efficient reactivation of both head and tail chain end dormant species. [less ▲]

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See detailMacroporous poly(ionic liquid)/ionic liquid gels via CO2-based emulsion-templating polymerization
Mathieu, Kevin ULiege; Jérôme, Christine ULiege; Debuigne, Antoine ULiege

in Polymer Chemistry (2018), 9(4), 428-437

Structuring poly(ionic liquid)s (PILs) into porous materials or swelling PILs with free ionic liquids (ILs) has received specific attention recently and contributed to improve the performances of these ... [more ▼]

Structuring poly(ionic liquid)s (PILs) into porous materials or swelling PILs with free ionic liquids (ILs) has received specific attention recently and contributed to improve the performances of these materials used in a wide range of applications. The present work aims to take benefit of both approaches and produce macroporous PIL/IL gels in a single step through an innovative emulsion-templated polymerization method based on supercritical carbon dioxide (scCO2). More precisely, ILs vinyl monomers and crosslinkers were polymerized in the presence of non polymerizable ILs within the outer phase of a CO2-in-ILs high internal phase emulsion (HIPE). Specific macromolecular surfactants were synthesized by controlled radical polymerization techniques and tested for the stabilization of the CO2-in-ILs emulsions. While optimizing the polymerization conditions, we found that adding a limited amount of water in the medium was beneficial for the emulsion stability. Overall, this straightforward process gave access to macroporous polyHIPEs composed of poly(vinyl imidazolium) networks swollen by ‘free’ vinyl imidazolium-based ILs having interesting properties such as switchable polarity upon simple anion exchange reaction. [less ▲]

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See detailEthylene/vinyl acetate-based macrocycles via organometallic-mediated radical polymerization and CuAAC ‘click’ reaction
Demarteau, Jérémy ULiege; De Winter, Julien; Detrembleur, Christophe ULiege et al

in Polymer Chemistry (2018), 9(3), 273-278

Recent advances in organometallic-mediated radical polymerization led to unique α,ω-difunctional poly(vinyl acetate) (PVAc) and ethylene/vinyl acetate copolymers (EVA). A copper- catalyzed Huisgen dipolar ... [more ▼]

Recent advances in organometallic-mediated radical polymerization led to unique α,ω-difunctional poly(vinyl acetate) (PVAc) and ethylene/vinyl acetate copolymers (EVA). A copper- catalyzed Huisgen dipolar cycloaddition ring-closure reaction was applied to these difunctional precursors paving the way to unprecedented PVAc and/or EVA macrocycles, and to their PVOH- and EVOH-counterparts after hydrolysis. [less ▲]

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See detailBis(formylphenolato)cobalt(II)-mediated alternating radical copolymerization of tert-butyl 2-trifluoromethylacrylate with vinyl acetate
Banerjee, Sanjib; Bellan, Ekaterina V.; Gayet, Florence et al

in Polymers (2017), 9(12), 705

The organometallic-mediated radical polymerization (OMRP) of vinyl acetate (VAc) and its OMR copolymerization (OMRcoP) with tert-butyl 2-trifluoromethylacrylate (MAF-TBE) mediated by Co(SAL)2 (SAL = 2 ... [more ▼]

The organometallic-mediated radical polymerization (OMRP) of vinyl acetate (VAc) and its OMR copolymerization (OMRcoP) with tert-butyl 2-trifluoromethylacrylate (MAF-TBE) mediated by Co(SAL)2 (SAL = 2-formylphenolato or deprotonated salicylaldehyde) produced relatively well-defined PVAc and poly(VAc-alt-MAF-TBE) copolymers at moderate temperature (<40 ◦C) in bulk. The resulting alternating copolymer was characterized by 1H-, 13C- and 19F-nuclear magnetic resonance (NMR) spectroscopies, and by size exclusion chromatography. The linear first-order kinetic plot, the linear evolutions of the molar mass with total monomer conversion, and the relatively low dispersity (Đ~1.55) of the resulting copolymers suggest that this cobalt complex provides some degree of control over the copolymerization of VAc and MAF-TBE. Compared to the previously investigated cobalt complex OMRP mediators having a fully oxygen-based first coordination sphere, this study emphasizes a few peculiarities of Co(SAL)2: a lower ability to trap radical chains as compared to Co(acac)2 and the absence of catalytic chain transfer reactions, which dominates polymerizations carried in the presence of 9-oxyphenalenone cobalt derivative. [less ▲]

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See detailUnique alternating peptide-peptoid copolymers from dipeptides via Ugi reaction in water
Al Samad, Assala ULiege; De Winter, Julien; Gergaux, Pascal et al

in Chemical Communications (2017), 53(90), 12240-12243

Herein, we developed a strainghtforward aqueous synthesis of unprecedented alternating peptide-peptoid copolymers via Ugi four-component reaction applied to dipeptides. Functional peptide-peptoid ... [more ▼]

Herein, we developed a strainghtforward aqueous synthesis of unprecedented alternating peptide-peptoid copolymers via Ugi four-component reaction applied to dipeptides. Functional peptide-peptoid copolymers as well as block copolymers were produced in a single step in the presence of acrylic acid and carboxylic acid-terminated poly(ethylene glycol). The thermoresponsiveness of these polymers is highlighted [less ▲]

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See detailEnhanced stabilization of water-scCO2 interface by block-like spontaneous gradient copolymers
Liu, Xuan; Wang, Mingxi; Harrisson, Simon et al

in ACS Sustainable Chemistry & Engineering (2017), 5(11), 9645-9650

There is an increasing interest in the specific physicochemical properties of gradient copolymers at interfaces. In this work, the phase behavior and interfacial properties of amphiphilic gradient ... [more ▼]

There is an increasing interest in the specific physicochemical properties of gradient copolymers at interfaces. In this work, the phase behavior and interfacial properties of amphiphilic gradient copolymers at the water/CO2 interface are explored and compared to that of diblock copolymer counterparts. It is observed that spontaneous amphiphilic block-like gradient copolymers made of N,N-dimethylacrylamide, vinyl pivalate, and vinyl acetate exhibit slightly lower cloud point pressures in supercritical carbon dioxide (scCO2) than the corresponding diblock copolymers. Much more pronounced differences are established at the water/scCO2 interface, with larger critical aggregation concentration (CAC), much faster adsorption kinetics and equilibration, and lower surface tension for gradient copolymers. RAFT/MADIX polymerization allows the control of molar mass, composition, and microstructure of the copolymers of the study. These findings shed light on how microstructural control in amphiphilic copolymers can give access to a new range of macromolecular emulsifiers for CO2 media with improved properties. [less ▲]

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See detailImprovement in or relating to organic material
Debuigne, Antoine ULiege; Dréan, Mathilde; Guégan, Philippe et al

Patent (2017)

The present invention provides polyplex comprising: (a) at least one polymer of formula (I) comprising at least one set of repeating units of formula: and wherein for each set of repeating units R 1 ... [more ▼]

The present invention provides polyplex comprising: (a) at least one polymer of formula (I) comprising at least one set of repeating units of formula: and wherein for each set of repeating units R 1 represents either a hydrogen atom or a straight or branched chain alkyl group having from 1 to 20 carbon atoms and R 2 represents a straight or branched chain alkyl group having from 1 to 20 carbon atoms, wherein n and m each represent an integer of from 1 to 5000, wherein the sum of n and m is from 10 to 250 when R 1 represents a hydrogen atom and when the polymer of formula (I) contains only one set of repeating units; and (b) at least one nucleic acid having improved transfection efficient and reduced cytotoxicity; a method for preparing a polyplex; a method for preparing the polymer of formula (I) for use in the polyplex; a method for transferring at least one nucleic acid into a cell and a pharmaceutical composition comprising the polyplex and an adjuvant; use of a polyplex or of a pharmaceutical composition according to the invention in transferring at least one nucleic acid into a cell; and use of a polymer of formula (I) as defined above in transferring of at least one nucleic acid into a cell.. To be accompanied when published by Figure 1 of the accompanying drawings. [less ▲]

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See detailPolyvinyl alcohol and method for producing same
Takayama, Takumi; Amano, Yusuke; Maekawa, Kazuko et al

Patent (2017)

According to the present invention a polyvinyl alcohol is produced by performing: a polymerization step wherein a polymer solution containing a polyvinyl ester is obtained by polymerizing a vinyl ester ... [more ▼]

According to the present invention a polyvinyl alcohol is produced by performing: a polymerization step wherein a polymer solution containing a polyvinyl ester is obtained by polymerizing a vinyl ester monomer by means of controlled radical polymerization in the presence of a radical initiator and an organic cobalt complex; an extraction step wherein a cobalt complex is extracted from the polymer solution by bringing the polymer solution into contact with an aqueous solution containing a water-soluble ligand; and a saponification step wherein a polyvinyl alcohol is obtained by saponifying the polyvinyl ester after the extraction step. Consequently, the present invention provides a method for producing a polyvinyl alcohol which has narrow molecular weight distribution, high number average molecular weight and good hue, while exhibiting good solubility in water. [less ▲]

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See detailVINYLIC COPOLYMERS FOR PH-SENSITIVE LIPID NANOCAPSULES
Pautu, Vincent ULiege; Lepeltier, Elise; Debuigne, Antoine ULiege et al

Poster (2017, September)

Detailed reference viewed: 14 (2 ULiège)
See detailWell-defined polyvinylamine-based copolymers: synthesis by organometallic-mediated radical polymerization and use in gene transfection
Debuigne, Antoine ULiege; Dréan, Mathilde; Detrembleur, Christophe ULiege et al

Conference (2017, August 22)

Polyvinylamine (PVAm) presents valuable properties like affinity for many supports, pH responsiveness, metal binding capacity, polyelectrolytes complexation, and is used in various applications including ... [more ▼]

Polyvinylamine (PVAm) presents valuable properties like affinity for many supports, pH responsiveness, metal binding capacity, polyelectrolytes complexation, and is used in various applications including coatings, water purification or gas membrane separation. PVAm is commonly prepared by free radical polymerization of N-vinyl monomers followed by deprotection and release of the masked amino functions. However, examples of controlled synthesis of polyvinylamine-based copolymers are scarce because of the high reactivity of the propagating radicals deriving from non-conjugated N-vinyl monomers due to the lack of resonance stabilization. The present communication aims at reporting an efficient platform for producing tailor-made PVAms via organometallic-mediated radical polymerization (OMRP) of N-vinylacetamides followed by hydrolysis of the pendent amide moieties. In this case, cobalt(II) acetylacetonate was successfully used as controlling agent. The synthesis of a series of well-defined homopolymers, statistical and block copolymers with pendent primary and/or secondary amines having low dispersities, predictable molar masses and precise compositions, will be described. Finally, we will discuss the possible use of these polyvinylamine-containing copolymers as gene transfection agents. Some of them demonstrated high DNA transfection level in combination with high cell viability. [less ▲]

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See detailOrganometallic-mediated alternating radical copolymerization of tert-butyl-2- trifluoromethacrylate with vinyl acetate and synthesis of block copolymers thereof
Banerjee, Sanjib; Ladmiral, Vincent; Debuigne, Antoine ULiege et al

in Macromolecular Rapid Communications (2017), 38(15), 1700203

Organometallic-mediated radical polymerization (OMRP) has given access to well-defined poly(vinyl acetate-alt-tert-butyl-2-trifluoromethacrylate)-b-poly(vinyl acetate) and poly (VAc- alt-MAF-TBE ... [more ▼]

Organometallic-mediated radical polymerization (OMRP) has given access to well-defined poly(vinyl acetate-alt-tert-butyl-2-trifluoromethacrylate)-b-poly(vinyl acetate) and poly (VAc- alt-MAF-TBE) copolymers composed of two electronically distinct monomers: vinyl acetate (VAc, donor, D) and tert-butyl-2-trifluoromethacrylate (MAF-TBE, acceptor, A), with low dispersity (≤1.24) and molar masses up to 57 000 g mol−1. These copolymers have a precise 1:1 alternating structure over a wide range of comonomer feed compositions. The reactivity ratios are determined as rVAc = 0.01 ± 0.01 and rMAF-TBE = 0 at 40 °C. Remarkably, from a feed containing >50% molar VAc content, poly(VAc-alt-MAF-TBE)-b- PVAc block copolymers are produced via a one- pot synthesis. Such diblock copolymers exhibit two glass transition temperatures attributed to the alternating and homopolymer sequences. The OMRP of this fluorine-containing alter- nating monomer system may provide access to a wide range of new polymer materials. [less ▲]

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See detailMultifunctional poly(ionic liquid)s: from synthesis to applications in energy and environment
Detrembleur, Christophe ULiege; Patil, Nagaraj ULiege; Debuigne, Antoine ULiege et al

Conference (2017, May 24)

Poly(ionic liquid)s (PILs) are a subclass of polyelectrolytes that gained an enabling role in many fields of polymer chemistry and material science. PILs combine the unique properties of ionic liquids ... [more ▼]

Poly(ionic liquid)s (PILs) are a subclass of polyelectrolytes that gained an enabling role in many fields of polymer chemistry and material science. PILs combine the unique properties of ionic liquids with the flexibility and properties of macromolecules, and provide novel attractive functions. Recently, the precision design of novel PILs by controlled/living polymerization (CLP) techniques was intensively searched for developing emerging applications. This talk will first discuss recent routes for the precision synthesis of all vinyl-imidazolium based (co)polymers in water or in organic media under non-demanding experimental conditions. We will then describe the preparation of innovative redox and surface active PILs, and show the potential of these PILs in battery applications and for multifunctional coatings. More specifically, we will show how macromolecular engineering can be exploited for designing innovative polymer cathodes for ultra-high performance Li storage with unprecedented performances (high capacities and ultra-long life-span over more than 3000 cycles at an extreme current-rate). This innovative and effective molecular design for polymer cathodes opens up new horizons in developing an economical and environmentally benign platform for large-scalable fabrication of high performance batteries. [less ▲]

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See detailControlled synthesis of fluorinated copolymers via cobalt-mediated radical copolymerization of perfluorohexylethylene and vinyl acetate
Demarteau, Jérémy ULiege; Améduri, Bruno; Ladmiral, Vincent et al

in Macromolecules (2017), 50(10), 3750-3760

Designing novel polyfluoropolymer architectures is attractive for the development of new applications, such as advanced coatings, purification membranes, or materials for energy. Nevertheless, controlling ... [more ▼]

Designing novel polyfluoropolymer architectures is attractive for the development of new applications, such as advanced coatings, purification membranes, or materials for energy. Nevertheless, controlling the radical polymerization of fluoroalkenes is very challenging due to the high reactivity of the propagating fluorinated macroradicals. This study aims at exploring the controlled copolymerization of perfluoro- hexylethylene (PFHE) and vinyl acetate (VAc) in order to prepare a range of well-defined statistical poly(PFHE-stat-VAc) copolymers with different compositions. Cobalt-mediated radical polymerization demonstrated to be active at 40 °C starting from an alkylcobalt(III) initiator, and copolymers with a fluorinated monomer content as high as ca. 80 wt % were successfully prepared. Reactivity ratios were determined to be rVAc = 0.18 and rPFHE = 0 at 40 °C and emphasized a clear tendency for alternation. Unprecedented PFHE/VAc containing block copolymers were also prepared via a single-step approach or through sequential copolymerizations. Finally, hydrolysis of the pendant ester groups of these copolymers led to the corresponding fluorinated copolymers bearing vinyl alcohol (VOH). A preliminary solution behavior study, carried out by dynamic light scattering and transmission electron microscopy on block copolymers composed of PFHE and VAc or VOH units, evidenced a marked amphiphilicity of the copolymer composed of an extremely hydrophobic PFHE block associated with a highly hydrophilic PVOH segment. [less ▲]

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See detailPrecision synthesis and characterization of novel functional polymers
Scholten, Philip ULiege; Debuigne, Antoine ULiege; Demarteau, Jérémy ULiege et al

Poster (2017, May 23)

Among controlled radical polymerisation techniques, cobalt-mediated radical polymerisation (CMRP) has proven to be a valuable alternative in polymerising unreactive and unconjugated monomers of many ... [more ▼]

Among controlled radical polymerisation techniques, cobalt-mediated radical polymerisation (CMRP) has proven to be a valuable alternative in polymerising unreactive and unconjugated monomers of many different monomer classes under mild conditions, including α-olefins. In a reversible deactivation mechanism, a cobalt complex reversibly traps the active growing chains and converts them into dormant species, avoiding side reactions and allowing for a controlled polymerisation. A fine control over the architecture is possible and allows to synthesise a large diversity of unprecedented block and alternating copolymers. Furthermore, functionalisation of the α- and ω-chain ends is now also possible. In this poster, the polymerization of different vinyl monomers using CMRP has been investigated to design highly functional materials under mild experimental conditions. The copolymerisation behaviour of these novel monomers was examined, and the structure and thermal properties of the new copolymers were investigated. [less ▲]

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See detailFunctional emulsion-templated porous polymers by macromolecular surfactant anchoring strategies
Mathieu, Kevin ULiege; Jérôme, Christine ULiege; Debuigne, Antoine ULiege

Poster (2017, May 22)

Macroporous polymer monoliths with interconnected structures have attracted considerable interest in the fields of supported catalysis, chromatography, water purification, etc. A popular and ... [more ▼]

Macroporous polymer monoliths with interconnected structures have attracted considerable interest in the fields of supported catalysis, chromatography, water purification, etc. A popular and straightforward synthesis approach for such open-cell polymers is based on the polymerization of high internal phase emulsion (HIPE). Advanced functional polyHIPEs were also produced via different post-modification strategies but the latter often consists in tedious multi-step processes. This communication aims at reporting an efficient one-pot macromolecular surfactant-assisted method for the simultaneous synthesis and chemical functionalization of macroporous polyHIPEs. Briefly, amphiphilic block copolymers prepared by nitroxide-mediated radical polymerization (NMP) or reversible addition-fragmentation chain transfer (RAFT) were used as HIPE stabilizers and grafted at the surface of the walls of polyHIPE during the polymerization process. The impact of the controlled radical polymerization mechanism on the porous structure, openness and functionalization of the monoliths will be discussed. This strategy was also implemented with alkyne-terminated copolymers in order to decorate the surface of the polyHIPE’s cavities with “clickable” moieties which broadens the scope of functional macroporous polymers. [less ▲]

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See detailProtein encapsulation into nanostructured CaCO3 microparticles templated by PEO-b-polyphosphoester using a supercritical CO2 process
Ergül, Zeynep ULiege; Debuigne, Antoine ULiege; Calvignac, Brice et al

Poster (2017, May 22)

The use of calcium carbonate microparticles is becoming more and more attractive in biomedical applications as proteins carriers for their controlled delivery in the body. We investigate the protein ... [more ▼]

The use of calcium carbonate microparticles is becoming more and more attractive in biomedical applications as proteins carriers for their controlled delivery in the body. We investigate the protein encapsulation by in situ precipitation of CaCO3 particles prepared by a process based on supercritical CO2 and using a new type of degradable well-defined double hydrophilic block copolymer composed of poly(ethylene oxide) and polyphosphoester block with an affinity for calcium like poly(phosphotriester)s bearing pendent carboxylic acids on each repeating monomer unit which evidenced an efficient structure for templating the formation of CaCO3 leading to unprecedented small-sized particles. Lysozyme was chosen as a model for therapeutic protein for its availability and ease of detection. It was found that by this green process, loading into the CaCO3 microparticles with a diameter about 2 μm can be obtained as determined by scanning electron microscopy. A protein loading up to 6.5% active lysozyme was measured by a specific bioassay (Micrococcus lysodeikticus). By encapsulating fluorescent-labelled lysozyme (lysozyme-FITC), the confocal microscopy images confirmed its encapsulation and suggested a core–shell distribution of lysozyme into CaCO3. [less ▲]

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See detailUnprecendeted fluoroalkene-based copolymers through cobalt-mediated radical polymerization
Demarteau, Jérémy ULiege; Ameduri, Bruno; Ladmiral, Vincent et al

Poster (2017, May 22)

The precision design of fluorinated copolymers is challenging but also attractive for future developments in a wide range of applications involving fluoropolymers, such as advanced coatings or ... [more ▼]

The precision design of fluorinated copolymers is challenging but also attractive for future developments in a wide range of applications involving fluoropolymers, such as advanced coatings or purification membranes. In particular, controlling the radical polymerization of fluoroalkenes remains extremely difficult because of the high reactivity of these monomers due to the lack of resonance stabilizing group on their double bond. Herein, Cobalt-Mediated Radical Polymerization (CMRP) was used to efficiently control the bulk copolymerization of perfluorohexylethylene (PFHE) and vinyl acetate (VAc). Well-defined statistical poly(PFHE-stat-VAc) copolymers with different compositions (0 < FPFHE < 0.5) were obtained accordingly. In some cases, fluorinated monomer content as high as 80 % by weight were achieved. Reactivity ratios were determined (rVAc = 0.18 and rPFHE = 0) and emphasized a clear tendency for alternation. Single step approach and sequential polymerization were assessed for the synthesis of novel PFHE/VAc block copolymers. Finally, the acidic hydrolysis of the pendant ester groups of these block copolymers led to the formation of novel highly amphiphilic macromolecules bearing a PVOH hydrophilic segment and a hydrophobic PFHE-based block. [less ▲]

Detailed reference viewed: 44 (4 ULiège)