Damien Quemener

Porous membranes from acid decorated block copolymer nano-objects via RAFT alcoholic dispersion polymerization

The RAFT dispersion polymerization of methyl methacrylate (MMA) was conducted in ethanol at 70 °C using a poly(methacrylic acid) (PMAA) chain transfer agent. The poly(methacrylic acid) block is soluble in ethanol and acts as a steric stabilizer for the growing insoluble PMMA chains, resulting in the in situ formation of diblock copolymer nano-objects (Polymerization Induced Self-Assembly (PISA)) in the form of spheres, worms or vesicles, depending on the precise reaction conditions as judged by transmission electron microscopy and dynamic light scattering studies. Two detailed phase diagrams using PMAA27 and PMAA47 macro-CTAs were constructed as a road map for the synthesis of pure morphologies. It was observed that the pure phases could be obtained using the longer macro-CTA while the pure worm phase was not observed with the shorter PMAA. Spin-coated thin films of the prepared spherical particles exhibited a connected porous network as evaluated by electron microscopy (SEM, TEM). Finally, the prepared porous thin film was tested as an isoporous membrane for water filtration.

Hemocompatibility of Polyampholyte Copolymers with Well-Defined Charge Bias in Human Blood

In this work, the hemocompatibility of polyampholyte copolymers from the mixed-charge copolymerization of negatively charged 3-sulfopropyl methacrylate (SA) and positively charged [2-(methacryloyloxy)ethyl] trimethylammonium (TMA) was studied. Charge-bias variation of the prepared poly(SA-co-TMA) copolymers can be controlled using the regulated SA and TMA monomer ratio via homogeneous free radical copolymerization. A systematic study of how charge-bias variations in poly(SA-co-TMA) copolymers affect the hemocompatibility in human blood plasma was reported. The hydrodynamic size of prepared polymers and copolymers is determined to illustrate the correlations between intermolecular cationic/anionic associations and the blood compatibility of polySA, poly(SA-co-TMA), and polyTMA suspensions in human blood plasma. It was found that the protein resistance and hydration capability of prepared copolymers can be effectively controlled by regulating the charge balance of the SA/TMA compositions in poly(SA-co-TMA). The results suggest that polyampholyte copolymers of poly(SA-co-TMA) with overall charge neutrality have a high hydration capability and the best antifouling, anticoagulant, and antihemolytic activities as well as zwitterionic sulfobetaine-based homopolymers when in contact with blood plasma at human body temperature.

Stimuli responsive nanostructured porous network from triblock copolymer self-assemblies

An ABA triblock amphiphilic copolymer is synthesized using RAFT chemistry. The self-assembled micelles of this copolymer are then used to prepare nano-organized porous films that could be used as filtration membranes. In this work a novel strategy is developed to build the nanostructures and perform their self-assembly using reversible and non-covalent interactions to create free volume between the micelles, thus giving tuneable porosity to the film. The self-assembly of poly(styrene)-b-poly(phenylboronic acid)-b-poly(styrene) block copolymer, occurs at high concentration through solvent evaporation, which induces a progressive decrease of the inter-micellar distance, and results in the formation of an in situ network of micelles and the final porous film. Subsequent permeability tests were conducted under different stimuli (pH and UV), generating cross-linking and chemical exchange reactions, to ensure the best balance between permeability and mechanical strength. This work highlights an original strategy for pore size control, and provides new insights towards the design of stimuli-responsive materials.

Nano-structured magneto-responsive membranes from block copolymers and iron oxide nanoparticles

Mixed matrix membranes (MMMs) provide an exciting alternative to traditional membranes due to their favorable properties from both building blocks which are essential for certain separation applications. Block copolymer directed synthesis of MMMs is an innovative approach for the preparation of porous materials. In the current work the syntheses of mixed matrix membranes from a PMAA-b-PMMA block copolymer and functionalized iron oxide magnetic nanoparticles are demonstrated. The block copolymers were synthesized using a RAFT polymerization technique, along with three different types of magnetic nanoparticles with various surface properties. The thin film membranes were prepared by mixing different ratios of diblock copolymer in THF and iron oxide nanoparticles in water followed by tape casting or spin coating. The particles and the membranes were characterized using TEM, DLS, and SEM. The permeation behavior of the membranes was assessed using filtration tests in the presence and absence of a magnetic field.

A Zwitterionic-Shielded Carrier with pH-Modulated Reversible Self-Assembly for Gene Transfection

Cationic vectors are ideal candidates for gene delivery thanks to their capability to carry large gene inserts and their scalable production. However, their cationic density gives rise to high cytotoxicity. We present the proper designed core-shell polyplexes made of either poly(ethylene imine) (PEI) or poly(2-dimethylamino ethyl methacrylate) (PDMAEMA) as the core and zwitterionic poly(acrylic acid)-block-poly(sulfobetaine methacrylate) (PAA-b-PSBMA) diblock copolymer as the shell. Gel retardation and ethidium bromide displacement assays were used to determine the PEI/DNA or PDMAEMA/DNA complexation. At neutral pH, the copolymer serves as a protective shell of the complex. As PSBMA is a nonfouling block, the shell reduced the cytotoxicity and enhanced the hemocompatibility (lower hemolysis activity, longer plasma clotting time) of the gene carriers. PAA segments in the copolymer impart pH sensitivity by allowing deshielding of the core in acidic solution. Therefore, the transfection efficiency of polyplexes at pH 6.5 was better than at pH 7.0, from β-galactosidase assay, and for all PAA-b-PSBMA tested. These results were supported by more favorable physicochemical properties in acidic solution (zeta potential, particle size, and interactions between the polymer and DNA). Thus, the results of this study offer a potential route to the development of efficient and nontoxic pH-sensitive gene carriers.

Reversible 2D/3D Coatings from Zipper‐Assembly of Block Copolymer Micelles

A zipper-assembly of micelles into 2D/3D coatings is reported. Block copolymer micelles that incorporate a poly(n-octadecyl methacrylate) block are zipped and unzipped on demand onto a PMMA surface. The mechanism implies an interdigitation of molecular brushes enabling 15 nm micelles to be assembled into monolayers or multilayers.

Self-assembly of PS-PNaSS-PS triblock copolymers from solution to the solid state

Block copolymer assemblies are fascinating objects that have been studied for years. In this work, the PS-PNaSS-PS ABA triblock copolymer was synthesized by RAFT polymerization and self-assembled in a selective medium (THF/water). Various morphologies of aggregates were identified (spheres, cylinders, and vesicles) but we focused on large compound vesicles which gave birth to porous materials after solvent evaporation. The change in solvent composition upon drying was modeled and correlated to the change in morphology observed using microscopy techniques such as AFM, TEM and cryo-TEM. The large compound vesicles were found to partially fuse to form a bulk material before the vesicular compartments were opened to yield pores of about 30 nm.

First multi-reactive dextran-based inisurf for atom transfer radical polymerization in miniemulsion

A multi-reactive polysaccharide-based inisurf (acting both as initiator and stabilizer) has been designed for the first time from dextran with the aim of preparing dextran-covered nanoparticles with covalent linkage between core and coverage. This inisurf was used for polymerizing butyl acrylate in miniemulsion by AGET-ATRP. Both hydrophobic phenoxy groups and initiator groups (bromoisobutyryl ester) were introduced within hydrophilic dextran chain, conferring it amphiphilic and macroinitiator characters. Amphiphilic properties of dextran inisurfs have been evidenced as well as their ability to stabilize the direct miniemulsion of n-butyl acrylate. After optimization of polymerization conditions with model studies, assays were successfully realized with dextran-based inisurfs. Because of their amphiphilic character, inisurfs migrated at oil/water interface and initiated polymerization from bromoisobutyryl ester groups. Therefore graft copolymers were produced at oil/water interface, due to the multifunctional character of these inisurfs and constituted the particle inner core with covalent links to the dextran coverage.

Anti-Bioadhesive Coating Based on Easy to Make Pseudozwitterionic RAFT Block Copolymers for Blood-Contacting Applications.

Amphiphilic diblock copolymer containing randomly distributed positive and negative charged monomers are synthesized using RAFT polymerization technique to be used as anti-bioadhesion coatings for hydrophobic surfaces. Quaternized 2-(dimethylamino) ethyl methacrylate and potassium 3-sulfopropyl methacrylate (P[qDMAEMA-co-KSPMA]) are randomly polymerized to yield an anti-bioadhesion block which is, in one pot, copolymerized with styrene as an anchoring block. This copolymer has demonstrated high anti-bioadhesion properties to avoid the blood clotting in medical devices through a simple and facile approach to preparation of pseudozwitterionic copolymers.

Negatively Charged Porous Thin Film from ABA Triblock Copolymer Assembly

The preparation of well-arranged nano-porous thin films from an ABA triblock copolymer of polystyrene-block-poly(sodium 4-styrenesulfonate)-block-polystyrene (PS-PNaSS-PS) is reported. This copolymer was self-assembled in a N,N-dimethylformamide (DMF)/water mixture and the resulting micellar solution was used to prepare thin films via the compact packing of the flower-like micelles using spin coating method. The films were characterized by several microscopy techniques such as TEM, AFM, and SEM. Permeation test was performed to highlight the interconnected porous nature of the polymeric network obtained. Under applied water pressure, the micellar morphology was altered and a partial fusion of the micelles was observed that resulted in a change in the water permeability. Such hydrophilic nanoporous thin films with negatively charged interface could find applications in membrane filtration.