Papers by Vincent Ladmiral
Polym. Chem., 2017
Fluorinated polyacrylates with tunable surface hydrophobicity are prepared via radical copolymeri... more Fluorinated polyacrylates with tunable surface hydrophobicity are prepared via radical copolymerization of an α-fluoroacrylate and 2-(trifluoromethyl)acrylic acid.
Bookmarks Related papers MentionsView impact
We report the controlled polymerization of methyl acrylate in the presence of elemental copper at... more We report the controlled polymerization of methyl acrylate in the presence of elemental copper at room temperature in a nonpolar solvent. As in single electron transfer (SET) living radical polymerization with nonactivated Cu (0), uncontrolled polymerization is observed ...
Bookmarks Related papers MentionsView impact
Macromolecules, 2015
Bookmarks Related papers MentionsView impact
Journal of Fluorine Chemistry, 2016
Bookmarks Related papers MentionsView impact
Methods in molecular biology (Clifton, N.J.), 2016
Glycopolymer-based nanostructures are invaluable tools to both study biological phenomena and to ... more Glycopolymer-based nanostructures are invaluable tools to both study biological phenomena and to design future targeted drug delivery systems. Polymerization-induced self-assembly, especially RAFT aqueous dispersion polymerization is a unique method to prepare such polymer nanostructures, as it enables the preparation of very-well-defined morphologies at very high concentrations. Here we describe the implementation of PISA to the synthesis of galactosylated spheres, wormlike micelles and vesicles, and the preliminary results of cell toxicity, cell uptake, and cargo delivering capacity of galactose-decorated vesicles.
Bookmarks Related papers MentionsView impact
Macromolecules, 2015
Bookmarks Related papers MentionsView impact
European Polymer Journal, Oct 1, 2009
Monodisperse zinc sulfide (ZnS) particles of diameters ranging from 120 to 400nm were prepared an... more Monodisperse zinc sulfide (ZnS) particles of diameters ranging from 120 to 400nm were prepared and then coated with a thin layer of silica (SiO2). After the surface modification with an alkoxyamine derivative, polystyrene (PS) brushes of chain lengths ranging from 30,000 to 114,000 in Mn with relatively low polydispersities less than 1.5 in Mw/Mn were successfully grafted by surface-initiated nitroxide-mediated
Bookmarks Related papers MentionsView impact
Bookmarks Related papers MentionsView impact
Polym. Chem., 2015
Bookmarks Related papers MentionsView impact
RSC Adv., 2015
ABSTRACT The radical copolymerisation of electron-acceptor chlorotrifluoroethylene (CTFE) with el... more ABSTRACT The radical copolymerisation of electron-acceptor chlorotrifluoroethylene (CTFE) with electron-donor vinyl ethers (VEs) produced poly(CTFE-alt-VE) alternating fluorinated copolymers with a high content of functional groups. This article describes methods to synthesise poly(CTFE-alt-VE) copolymers that bear ammonium-groups insensitive to Hofmann degradation. Direct preparation and post-polymerisation functionalisation methods are presented. First, the radical copolymerisation of CTFE with a tertiary amine-carrying vinyl ether led to low molecular weight-copolymers with an imperfect structure. That copolymerisation and the quaternisation of the amino groups using methyl iodide were however accompanied by side reactions, including transfer reactions and significant loss of functionality. In contrast, the second strategy dealt with the post functionalisation of an alternated poly(CTFE-alt-2-chloroethyl vinyl ether) copolymer. Halogen exchange of poly(CTFE-alt-CEVE) copolymers was carried out using the efficient Finkelstein reaction. Then, the nucleophilic substitution of the iodine atoms on the obtained poly(CTFE-alt-IEVE) copolymer led to a poor yield of functionalisation and was accompanied by a substantial amount of side reactions. Then, the iodine atoms in poly(CTFE-alt-IEVE) copolymers were chemically changed quantitatively into azides (especially from microwave activation) and the resulting azido-containing copolymer was reacted with 1-dimethylamino-2-propyne. An optimisation of this Huisgen's or thermal cycloaddition showed that (i) a copper catalyst led to cross-linked copolymers, (ii) whereas in the absence of the copper catalyst, the cycloaddition was slow and only converted ca. 60% of the azides; (iii) then, microwave activation led to high yield in a few minutes. Dimethylamino groups were inserted onto the copolymeric backbone and subsequently quaternised using iodomethane efficiently. Such copolymers, potentially resistant to alkaline media and able to promote hydroxide anion conduction, may exhibit interesting properties as a component of solid alkaline fuel cell membranes.
Bookmarks Related papers MentionsView impact
Journal of Fluorine Chemistry, 2015
ABSTRACT The synthesis of functional fluoropolymers is a challenging and highly sought-after obje... more ABSTRACT The synthesis of functional fluoropolymers is a challenging and highly sought-after objective. Fluoroolefins are indeed in their vast majority non-functional. Their specific reactivity however, can be turned into an advantage. Alternating copolymerisation of electron-acceptor chlorotrifluoroethylene (CTFE) and electron-donor vinyl ethers (VEs) is indeed efficient to prepare poly(CTFE-alt-VE) fluoropolymers with a very high density of functional groups. This article deals with the synthesis of two original functional vinyl ethers (oxirane and cyclocarbonate), and describes two methods to synthesise ammonium-containing Hofmannn degradation-insensitive fluoro-copolymers, that may display interesting properties as component of solid alkaline fuel cell membranes. Both functional vinyl ethers copolymerised to high yield with CTFE. The oxirane-based monomers led to better defined alternating copolymers compared to the cyclocarbonate-containing vinyl ether. The post-polymerisation functionalisation of the copolymers using amines afforded well-defined ammonium-functionalised fluoro-copolymers.
Bookmarks Related papers MentionsView impact
Bookmarks Related papers MentionsView impact
Self-assembly in polymer films containing nanoparticles (NPs) can result in novel structures with... more Self-assembly in polymer films containing nanoparticles (NPs) can result in novel structures with attractive properties that depend on NP functionality. Here, magnetic iron oxide NPs (5nm) are dispersed in both poly(methyl methacrylate) (PMMA) and lamella forming poly(styrene-b-methyl methacrylate) (PS-b-PMMA) films. The NPs are grafted with PMMA brushes ranging from 3k to 37k Da. Increasing brush length improves dispersion in PMMA in agreement with trends observed for potential of mean force between two nanoparticles as obtained from coarse-grained molecular dynamics simulations of equivalent systems. For the 3k brush, NPs disperse uniformly in PS-b-PMMA only at low loadings (1wt%), locate in the PMMA domains, and slow down the perpendicular to parallel morphology transition. At 10 wt%, the NPs form uniform sized aggregates (˜22nm) and perturb the lamellar morphology. Increasing brush length leads to aggregation in the solution state and as a result large aggregates in the spin cas...
Bookmarks Related papers MentionsView impact
Polym. Chem., 2015
ABSTRACT Amino acids constitute one of Nature’s most important building blocks. Their remarkably ... more ABSTRACT Amino acids constitute one of Nature’s most important building blocks. Their remarkably diverse properties (hydrophobic/hydrophilic character, charge density, chirality, reversible cross-linking etc.) dictate the structure and function of proteins. The synthesis of artificial peptides and proteins comprising main chain amino acids is of particular importance for nanomedicine. However, synthetic polymers bearing amino acid side-chains are more readily prepared and may offer desirable properties for various biomedical applications. Herein we describe an efficient route for the synthesis of poly(amino acid)stabilized diblock copolymer nano-objects. First, either cysteine or glutathione is reacted with a commercially available methacrylate-acrylate adduct to produce the corresponding amino acid-based methacrylic monomer (CysMA or GSHMA). Well-defined water-soluble macromolecular chain transfer agents (PCysMA or PGSHMA macro-CTAs) are then prepared via RAFT polymerization, which are then chain-extended via aqueous RAFT dispersion polymerization of 2-hydroxypropyl methacrylate. In situ polymerization-induced self-assembly (PISA) occurs to produce sterically-stabilized diblock copolymer nano-objects. Although only spherical nanoparticles could be obtained when PGSHMA was used as the sole macro-CTA, either spheres, worms or vesicles can be prepared using either PCysMA macro-CTA alone or binary mixtures of poly(glycerol monomethacrylate) (PGMA) with either PCysMA or PGSHMA macro-CTAs. The worms formed soft free-standing thermo-responsive gels that undergo degelation on cooling as a result of a worm-to-sphere transition. Aqueous electrophoresis studies indicate that all three copolymer morphologies exhibit cationic character below pH 3.5 and anionic character above pH 3.5. This pH sensitivity corresponds to the known behavior of the poly(amino acid) steric stabilizer chains.
Bookmarks Related papers MentionsView impact
ACS Symposium Series, 2009
In Controlled/Living Radical Polymerization: Progress in RAFT, DT, NMP & OMRP... more In Controlled/Living Radical Polymerization: Progress in RAFT, DT, NMP & OMRP; Matyjaszewski, K.; ACS Symposium Series; American Chemical Society: Washington, DC, 2009. ... Diblock copolymers are wellknown for their abilities to spontaneously ...
Bookmarks Related papers MentionsView impact
Bookmarks Related papers MentionsView impact
Chemical Science, 2013
ABSTRACT Well-defined poly(lauryl methacrylate-benzyl methacrylate) (PLMA-PBzMA) diblock copolyme... more ABSTRACT Well-defined poly(lauryl methacrylate-benzyl methacrylate) (PLMA-PBzMA) diblock copolymer nanoparticles are prepared in n-heptane at 90 °C via reversible addition–fragmentation chain transfer (RAFT) polymerization. Under these conditions, the PLMA macromolecular chain transfer agent (macro-CTA) is soluble in n-heptane, whereas the growing PBzMA block quickly becomes insoluble. Thus this dispersion polymerization formulation leads to polymerization-induced self-assembly (PISA). Using a relatively long PLMA macro-CTA with a mean degree of polymerization (DP) of 37 or higher leads to the formation of well-defined spherical nanoparticles of 41 to 139 nm diameter, depending on the DP targeted for the PBzMA block. In contrast, TEM studies confirm that using a relatively short PLMA macro-CTA (DP = 17) enables both worm-like and vesicular morphologies to be produced, in addition to the spherical phase. A detailed phase diagram has been elucidated for this more asymmetric diblock copolymer formulation, which ensures that each pure phase can be targeted reproducibly. 1H NMR spectroscopy confirmed that high BzMA monomer conversions (>97%) were achieved within 5 h, while GPC studies indicated that reasonably good blocking efficiencies and relatively low diblock copolymer polydispersities (Mw/Mn < 1.30) were obtained in most cases. Compared to prior literature reports, this all-methacrylic PISA formulation is particularly novel because: (i) it is the first time that higher order morphologies (e.g. worms and vesicles) have been accessed in non-polar solvents and (ii) such diblock copolymer nano-objects are expected to have potential boundary lubrication applications for engine oils.
Bookmarks Related papers MentionsView impact
Polym. Chem., 2014
Bookmarks Related papers MentionsView impact
Journal of the American Chemical Society, 2014
Bookmarks Related papers MentionsView impact
ChemInform, 2010
Bookmarks Related papers MentionsView impact
Uploads
Papers by Vincent Ladmiral