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  • G. Mellot, J. - M. Guigner, J. Jestin, L. Bouteiller, F. Stoffelbach, et J. Rieger, « Unexpected thermo-responsiveness of bisurea-functionalized hydrophilic polymers in water », Journal of Colloid and Interface Science, vol. 581, p. 874-883, janv. 2021.
    Résumé : Hypothesis Thermoresponsive polymers are important materials for various applications. However, the number of polymers that exhibit this property in the temperature range of interest remains limited. The development of novel rational design strategies through the understanding of the thermal transition’s origin is therefore of utmost importance. Experiments Bisurea-functionalized water-soluble polymers were synthesized by RAFT polymerization. After direct dissolution in water, the supramolecular assemblies were analyzed by cryo-TEM and SANS. Their temperature-dependent water-solubility was characterized by various techniques, namely DLS, SANS, DSC, IR, to understand the origin of the temperature sensitivity. Findings The supramolecular assemblies exhibit an unexpected temperature-dependent solubility. For instance, a cloud point of only 39 °C was measured for poly(N,N-dimethylacrylamide) assemblies. This property is not restricted to one specific polymer but is rather a general feature of bisurea-functionalized polymers that form supramacromolecular bottlebrushes in water. The results highlight the existence of two distinct transitions; the first one is a visually perceptible cloud point due to the aggregation of individual micelles, presumably driven by the hydrophobic effect. The second transition is related to the dissociation of intermolecular bisurea hydrogen bonds. Finally, we show that it is possible to widely tune the cloud point temperature through the formation of co-assemblies.
    Mots-clés : Bisurea, Cloud point, Cylindrical micelles, Hydrogen bonding, LCST, nano-DSC, POLE 4, POLYMERES, Supramacromolecular assemblies, Supramolecular bottlebrushes, Thermoresponsive.


  • N. Audureau, F. Coumes, J. - M. Guigner, T. P. T. Nguyen, C. Ménager, F. Stoffelbach, et J. Rieger, « Thermoresponsive properties of poly(acrylamide-co-acrylonitrile)-based diblock copolymers synthesized (by PISA) in water », Polymer Chemistry, vol. 11, nᵒ 37, p. 5998-6008, sept. 2020.
    Résumé : In this present work, we report the synthesis of UCST-thermoresponsive diblock copolymers using reversible addition fragmentation chain transfer (RAFT) polymerization in aqueous media. A water-soluble poly(N,N-dimethylacrylamide) macromolecular chain transfer agent (PDMAc macroRAFT) is used to promote and control the copolymerization of acrylamide and acrylonitrile in water and obtain PDMAc-b-P(AAm-co-AN) diblock copolymers. The fAN,0 and the length of the thermosensitive block (DPn) are systematically varied, in order to study their influence on the thermoresponsiveness of the block copolymers. A good blocking efficiency is generally evidenced by size exclusion chromatography. Remarkably, amphiphilic copolymer nanoparticles are formed in situ for the highest fAN,0. This is indeed the first time that such particles are produced by a polymerization-induced self-assembly (PISA) process. The morphology of the in situ formed nanoparticles and their behavior with temperature are studied by means of dynamic light scattering (DLS), (cryogenic) transmission electron microscopy ((cryo-)TEM) and turbidimetry. Spherical and worm-like nanoparticles are formed which exhibit unexpected properties, such as an unprecedented heating-induced worm-to-sphere morphological transition in water.
    Mots-clés : POLE 4, POLYMERES.
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  • P. Biais, O. Colombani, L. Bouteiller, F. Stoffelbach, et J. Rieger, « Unravelling the formation of BAB block copolymer assemblies during PISA in water », Polymer Chemistry, vol. 11, nᵒ 28, p. 4568-4578, juill. 2020.
    Résumé : The mechanism of formation of associative BAB triblock copolymers through aqueous polymerization-induced self-assembly (PISA) is investigated for the first time, on copolymers constituted of a hydrophilic poly(N,N-dimethylacrylamide) block (PDMAc = block A) and a hydrophobic poly(diacetone acrylamide) block (PDAAm = block B). Such BAB copolymers tend to form bridged micelles/networks, which was expected to make the PISA process much more complex than for conventional diblock copolymers. Kinetic monitoring, light scattering analyses and macroscopic observations allowed identifying crucial parameters that influence the polymerization and the final dispersion properties, notably the stirring of the polymerization medium, the macroRAFT agent concentration, its ionization degree (related to the pH) and its Z group alkyl chain length.
    Mots-clés : POLE 4, POLYMERES.
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  • F. Coumes, M. Balarezo, J. Rieger, et F. Stoffelbach, « Biobased Amphiphilic Block Copolymers by RAFT-Mediated PISA in Green Solvent », Macromolecular Rapid Communications, vol. 41, nᵒ 9, p. 2000002, 2020.
    Résumé : Biobased amphiphilic diblock copolymers are prepared thanks to the combination of reversible addition–fragmentation transfer (RAFT) polymerization and polymerization-induced self-assembly (PISA) in an eco-friendly solvent mixture. First, the formation of a poly(acrylic acid) macroRAFT agent (PAA-TTC) is performed in water at 70 °C. Then, in a series of experiments, the PAA-TTC macroRAFT agent is used directly, without purification, as both chain transfer agent and stabilizing agent in the RAFT-PISA of menthyl acrylate (MnA) in dispersion in an ethanol/water mixture. The polymerizations of MnA are fast with high final conversions and well-controlled amphiphilic diblock copolymers are synthesized. Stable, sub-micrometric spherical particles composed of the diblock copolymers are formed. The influence of the monomer concentration and the length of the solvophobic block on the diameter of the self-assemblies is studied by means of dynamic light scattering and cryogenic transmission electron-microscopy.
    Mots-clés : amphiphilic copolymers, biobased monomers, dispersion polymerization, PISA, POLE 4, POLYMERES, RAFT.
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  • F. D'Agosto, J. Rieger, et M. Lansalot, « RAFT-Mediated Polymerization-Induced Self-Assembly », Angewandte Chemie International Edition, vol. 59, nᵒ 22, p. 8368-8392, 2020.
    Résumé : After a brief history that positions polymerization-induced self-assembly (PISA) in the field of polymer chemistry, this Review will cover the fundamentals of the PISA mechanism. Furthermore, this Review will also give an overview of some of the features and limitations of RAFT-mediated PISA in terms of the choice of the components involved, the nature of the nanoobjects that can be obtained and how the syntheses can be controlled, as well as some potential applications.
    Mots-clés : block copolymers, heterogeneous polymerization, morphology, PISA, POLE 4, POLYMERES, RAFT.
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  • H. Du, F. A. de Oliveira, L. J. C. Albuquerque, G. Tresset, E. Pavlova, C. Huin, P. Guégan, et F. C. Giacomelli, « Polyglycidol-Stabilized Nanoparticles as a Promising Alternative to Nanoparticle PEGylation: Polymer Synthesis and Protein Fouling Considerations », Langmuir, vol. 36, nᵒ 5, p. 1266-1278, févr. 2020.
    Résumé : We herein demonstrate the outstanding protein-repelling characteristic of star-like micelles and polymersomes manufactured from amphiphilic block copolymers made by poly(butylene oxide) (PBO) hydrophobic segments and polyglycidol (PGL) hydrophilic outer shells. Although positively charged proteins (herein modeled by lysozyme) may adsorb onto the surface of micelles and polymersomes where the assemblies are stabilized by short PGL chains (degree of polymerization smaller than 15), the protein adsorption vanishes when the degree of polymerization of the hydrophilic segment (PGL) is higher than ∼20, regardless the morphology. This has been probed by using three different model proteins which are remarkably different concerning molecular weight, size, and zeta potential (bovine serum albumin (BSA), lysozyme, and immunoglobulin G (IgG)). Indeed, the adsorption of the most abundant plasma protein (herein modeled as BSA) is circumvented even by using very short PGL shells due to the highly negative zeta potential of the produced assemblies which presumably promote protein–nanoparticle electrostatic repulsion. The negative zeta potential, on the other hand, enables lysozyme adsorption, and the phenomenon is governed by electrostatic forces as evidenced by isothermal titration calorimetry. Nevertheless, the protein coating can be circumvented by slightly increasing the degree of polymerization of the hydrophilic segment. Notably, the PGL length required to circumvent protein fouling is significantly smaller than the one required for PEO. This feature and the safety concerns regarding the synthetic procedures on the preparation of poly(ethylene oxide)-based amphiphilic copolymers might make polyglycidol a promising alternative toward the production of nonfouling spherical particles.
    Mots-clés : POLE 4, POLYMERES.
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  • G. Falco, L. Simonin, S. Pensec, F. Dalmas, J. - M. Chenal, L. Bouteiller, et L. Chazeau, « Linear and nonlinear viscoelastic properties of segmented silicone-urea copolymers: Influence of the hard segment structure », Polymer, vol. 186, p. 122041, janv. 2020.
    Résumé : The linear and non-linear viscoelastic behaviors of 5 segmented silicone copolymers - with low fraction of 1,6-hexamethylene diisocyanate (HDI), 4,4′-methylenebis (cyclohexyl isocyanate) (HMDI), 1,3-bis(1-isocyanato-1-methylethyl)benzene (TMXDI), 2,4-tolylene diisocyanate (TDI) or isophorone diisocyanate (IPDI) as hard segments (HS) - are compared, in relation with their microstructure. When the HS are non-symmetrical, the materials nanostructuration is weak and has a limited impact on the mechanical response: two mechanical relaxations occur after the α relaxation of the polydimethylsiloxane (PDMS), the first related to the “unfreezing” of the HS-HS bonds, and the second one to the sticky reptation of the polymer chains. Conversely, when the HS are symmetrical, their self-organization is favored and the long range ordering of the HS is possible. The materials are then semi-crystalline like, with a low crystallinity (due to the low weight percentage of HS) and their flow, possible above their melting temperature (Tm), depends also on the HS dynamics, which is the most rapid for HDI.
    Mots-clés : Mechanical relaxations, Nanostructure, POLE 4, POLYMERES, Segmented copolymers.

  • F. Giusti, M. Casiraghi, E. Point, M. Damian, J. Rieger, C. L. Bon, A. Pozza, K. Moncoq, J. - L. Banères, et L. J. Catoire, « Structure of the agonist 12–HHT in its BLT2 receptor-bound state », Scientific Reports, vol. 10, nᵒ 1, p. 2630, févr. 2020.
    Résumé : G Protein-Coupled receptors represent the main communicating pathway for signals from the outside to the inside of most of eukaryotic cells. They define the largest family of integral membrane receptors at the surface of the cells and constitute the main target of the current drugs on the market. The low affinity leukotriene receptor BLT2 is a receptor involved in pro- and anti-inflammatory pathways and can be activated by various unsaturated fatty acid compounds. We present here the NMR structure of the agonist 12–HHT in its BLT2-bound state and a model of interaction of the ligand with the receptor based on a conformational homology modeling associated with docking simulations. Put into perspective with the data obtained with leukotriene B4, our results illuminate the ligand selectivity of BLT2 and may help define new molecules to modulate the activity of this receptor.
    Mots-clés : POLE 4, POLYMERES.
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  • Y. T. L. Guen, T. L. Gall, P. Midoux, P. Guégan, S. Braun, et T. Montier, « Gene transfer to skeletal muscle using hydrodynamic limb vein injection: current applications, hurdles and possible optimizations », The Journal of Gene Medicine, vol. 22, nᵒ 2, p. e3150, 2020.
    Résumé : Hydrodynamic limb vein injection is an in vivo locoregional gene delivery method. It consists of administrating a large volume of solution containing nucleic acid constructs in a limb with both blood inflow and outflow temporarily blocked using a tourniquet. The fast, high pressure delivery allows the musculature of the whole limb to be reached. The skeletal muscle is a tissue of choice for a variety of gene transfer applications, including gene therapy for Duchenne muscular dystrophy or other myopathies, as well as for the production of antibodies or other proteins with broad therapeutic effects. Hydrodynamic limb vein delivery has been evaluated with success in a large range of animal models. It has also proven to be safe and well-tolerated in muscular dystrophy patients, thus supporting its translation to the clinic. However, some possible limitations may occur at different steps of the delivery process. Here, we have highlighted the interests, bottlenecks and potential improvements that could further optimize non-viral gene transfer following hydrodynamic limb vein injection.
    Mots-clés : gene transfer, hydrodynamic delivery, locoregional, non-viral gene delivery, optimizations, POLE 4, POLYMERES, skeletal muscle.
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    Note Note
    <p>e3150 JGM-19-0364.R1</p>

  • H. Guo, D. Hourdet, A. Marcellan, F. Stoffelbach, J. Lyskawa, L. de Smet, A. Vebr, R. Hoogenboom, et P. Woisel, « Dual Responsive Regulation of Host–Guest Complexation in Aqueous Media to Control Partial Release of the Host », Chemistry – A European Journal, vol. 26, nᵒ 6, p. 1292-1297, janv. 2020.
    Résumé : Abstract The regulation of the concentration of a wide range of small molecules is ubiquitous in biological systems because it enables them to adapt to the continuous changes in the environmental conditions. Herein, we report an aqueous synthetic system that provides an orchestrated, temperature and pH controlled regulation of the complexation between the cyclobis(paraquat-p-phenylene) host (BBox) and a 1,5-dialkyloxynaphthalene (DNP) guest attached to a well-defined dual responsive copolymer composed of N-isopropylacrylamide as thermoresponsive monomer and acrylic acid as pH-responsive monomer. Controlled, partial release of the BBox, enabling control over its concentration, is based on the tunable partial collapse of the copolymer. This colored supramolecular assembly is one of the first synthetic systems providing control over the concentration of a small molecule, providing great potential as both T and pH chromic materials and as a basis to develop more complex systems with molecular communication.
    Mots-clés : host–guest systems, molecular recognition, POLE 4, POLYMERES, polymers, supramolecular chemistry.

  • S. Han, G. Mellot, S. Pensec, J. Rieger, F. Stoffelbach, E. Nicol, O. Colombani, J. Jestin, et L. Bouteiller, « Crucial Role of the Spacer in Tuning the Length of Self-Assembled Nanorods », Macromolecules, vol. 53, nᵒ 1, p. 427-433, janv. 2020.
    Résumé : Polymeric supramolecular nanorods were prepared in toluene by self-assembly of tris(urea) stickers connected on both sides through alkyl spacers of different lengths to short polystyrene (PS) arms. Several tris(urea) initiators or chain transfer agents were synthesized straightforwardly and used to grow well-defined PS arms via atom transfer radical polymerization (ATRP) or reversible addition fragmentation chain transfer (RAFT) polymerization. Self-assembly was investigated by means of Fourier-transform infrared (FTIR) spectroscopy and light/neutron scattering. A dramatic impact of the spacer separating the tris(urea) sticker from the PS arms on the extent of self-assembly was observed in toluene as long as the degree of polymerization of the PS arms (x) was kept short (x ∼ 10). Indeed, supramolecular nanorods several hundreds of nanometers in length for a few nanometers in radius were obtained with a spacer consisting of nine atoms, whereas five times shorter nanorods were obtained for a spacer of only five atoms, and spherical particles were found in the absence of any spacer, all other parameters remaining unchanged. These results reveal the possibility to tune the length of polymer-decorated supramolecular nanorods with minimal modification of the assembling sticker and without affecting the functionality of the rods.
    Mots-clés : POLE 4, POLYMERES.
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  • Y. Li, A. Hammoud, L. Bouteiller, et M. Raynal, « Emergence of Homochiral Benzene-1,3,5-tricarboxamide Helical Assemblies and Catalysts upon Addition of an Achiral Monomer », Journal of the American Chemical Society, vol. 142, nᵒ 12, p. 5676-5688, mars 2020.
    Résumé : Chirality amplification refers to the ability of a small chiral bias to fully control the main chain helicity of polymers and assemblies. Further implementation of functional chirally amplified helices as switchable asymmetric catalysts, chiral sensors, and circularly polarized light emitters will require a greater control of the energetics governing these chirality amplification effects. In this work, we report on the counterintuitive ability of an achiral molecule to suppress conformational defects in supramolecular helices, thus leading to the emergence of homochirality in a system containing a very small chiral bias. We focus our investigation on supramolecular helices composed of an achiral benzene-1,3,5-tricarboxamide (BTA) ligand, coordinated to copper, and an enantiopure BTA comonomer. Amplification of chirality as probed by varying the amount (sergeants and soldiers effect) or the optical purity (diluted majority-rules effect) of the enantiopure comonomer are modest in this initial system. However, both effects are hugely enhanced upon addition of a second achiral BTA monomer, leading to a perfect control of the helicity either by means of a remarkably low amount of sergeants (0.5%) or a small bias from a racemic mixture of enantiopure comonomers (10% ee). Such an enhancement in the amplification of chirality is only achieved by mixing the three components, i.e. the two achiral and the enantiopure comonomers, highlighting a synergistic effect upon coassembly of the three monomers. Investigation of the role of the achiral additive by multifarious analytical techniques supports its ability to stabilize the helical coassemblies and suppress helix reversals: i.e., conformational defects. Implementation of these helical copper precatalysts in the hydrosilylation of 1-(4-nitrophenyl)ethanone confirms that the effect of the achiral BTA additive is also operative under the conditions of the catalytic experiment. A highly enantioenriched product (90% ee) is produced by a supramolecular catalyst operating with ppm levels of chiral species.
    Mots-clés : POLE 4, POLYMERES.
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  • X. Liu, X. Su, C. Livache, L. - M. Chamoreau, S. Sanaur, L. Sosa-Vargas, J. - C. Ribierre, D. Kreher, E. Lhuillier, E. Lacaze, et F. Mathevet, « Investigation of charge transport properties of [1]Benzothieno[3,2-b][1]-benzothiophene single-crystals in field-effect transistor configuration », Organic Electronics, vol. 78, p. 105605, mars 2020.
    Résumé : Single-crystals of unsubstituted [1]Benzothieno[3,2-b][1]-benzothiophene (BTBT) were prepared by physical vapor transport deposition (VTP). The packing structure and morphology of the crystals were studied by X-ray diffraction (XRD), polarized optical microscopy (POM), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The charge transport properties of BTBT single-crystals were also investigated via bottom contact/bottom gate (BC/BG) organic field-effect transistors (OFETs) on both SiO2 and n-octadecyltrichlorosilane (OTS) treated surfaces. A maximum hole mobility value of 0.032 cm2V−1s−1 was measured on the OTS substrate. In addition, single-crystal OFETs with ion gel top gate (TG) configuration were also investigated for low voltage operation. This work represents the first investigation of charge carrier mobility of a simple BTBT in transistor configuration and highlights the essential role of the BTBT substitution in charge transport properties.
    Mots-clés : Organic field effect transistors, POLE 4, POLYMERES, Semiconducting materials, Single crystals, Thienoacene derivative.

  • L. Plet, G. Delecourt, M. Hanafi, N. Pantoustier, G. Pembouong, P. Midoux, V. Bennevault, et P. Guégan, « Controlled star poly(2-oxazoline)s: Synthesis, characterization », European Polymer Journal, vol. 122, p. 109323, janv. 2020.
    Résumé : Poly(2-methyl-2-oxazoline) and poly(2-ethyl-2-oxazoline) star polymers with 3, 4 and 6 arms are synthesized from pluritriflate initiators. Characterization of the topology was achieved by NMR, SEC and kinetic studies. The initiation step of 2-ethyl-2-oxazoline being slow, heterogeneous star polymers in arm molar masses are obtained for low molar mass polymers. However, for both monomers, high molar mass homogeneous star polymers are obtained. A fast initiation is observed for the polymerization of 2-methyl-2-oxazoline, providing a control of the topology even at low molar mass. In the studied molar mass range, linear kinetic first order plots and linear molar mass as a function of conversion are obtained for both monomers, suggesting living polymerizations.
    Mots-clés : 2oxazoline polymerization, Pluritriflate initiators, POLE 4, POLYMERES, Star polymers.

  • V. Puchelle, H. Du, N. Illy, et P. Guégan, « Polymerization of epoxide monomers promoted by tBuP4 phosphazene base: a comparative study of kinetic behavior », Polymer Chemistry, vol. 11, nᵒ 21, p. 3585-3592, juin 2020.
    Résumé : The kinetics of the anionic ring-opening polymerizations (AROP) of epoxide monomers, 1,2-epoxybutane (BO), 1,2-epoxypropane (PO), tert-butyl glycidyl ether (tBuGE), allyl glycidyl ether (AGE), benzyl glycidyl ether (BnGE), and ethoxyethyl glycidyl ether (EEGE), was investigated using benzyl alcohol/tBuP4 as the initiating system. All the polymerizations proceed in a controlled manner following a first order kinetics with respect to the monomer. The influence of the side chains borne by the oxirane ring was evidenced. Propagating centers derived from epoxide bearing heretoatom-containing side chains display higher reactivities and propagation rates. A reactivity scale has been established and is as follows, kp,BnGE > kp,AGE > kp,EEGE ≫ kp,tBuGE ≈ kp,PO > kp,BO. Using BO as the model monomer and different initiator concentrations, the nature of the propagating species has been identified as ion pairs. The influence of a Lewis acid addition on the monomer reactivities and on the control of the polymerization was also investigated. In the presence of triisobutylaluminum (iBu3Al), polymerization kinetics was faster but led to a broadening of the molar mass distributions. The monomer reactivity scale was also strongly modified with kp,PO > kp,BO > kp,EEGE ≈ kp,AGE > kp,BnGE ≈ kp,tBuGE. The polymerizations of PO, BO and tBuGE follow zero order kinetics which is not the case for the other oxirane monomers.
    Mots-clés : pole 4, POLYMERES.
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  • C. Qin, T. Matsushima, W. J. Potscavage, A. S. D. Sandanayaka, M. R. Leyden, F. Bencheikh, K. Goushi, F. Mathevet, B. Heinrich, G. Yumoto, Y. Kanemitsu, et C. Adachi, « Triplet management for efficient perovskite light-emitting diodes », Nature Photonics, vol. 14, nᵒ 2, p. 70-75, févr. 2020.
    Résumé : Perovskite light-emitting diodes are promising for next-generation lighting and displays because of their high colour purity and performance1. Although the management of singlet and triplet excitons is fundamental to the design of efficient organic light-emitting diodes, the nature of how excitons affect performance is still not clear in perovskite2–4 and quasi-two-dimensional (2D) perovskite-based devices5–9. Here, we show that triplet excitons are key to efficient emission in green quasi-2D perovskite devices and that quenching of triplets by the organic cation is a major loss path. Employing an organic cation with a high triplet energy level (phenylethylammonium) in a quasi-2D perovskite based on formamidinium lead bromide yields efficient harvesting of triplets. Furthermore, we show that upconversion of triplets to singlets can occur, making 100% harvesting of electrically generated excitons potentially possible. The external quantum and current efficiencies of our green (527 nm) devices reached 12.4% and 52.1 cd A−1, respectively.
    Mots-clés : POLE 4, POLYMERES.

  • B. Rasolonjatovo, N. Illy, V. Bennevault, J. Mathé, P. Midoux, T. L. Gall, T. Haudebourg, T. Montier, P. Lehn, B. Pitard, H. Cheradame, C. Huin, et P. Guégan, « Temperature-Sensitive Amphiphilic Non-Ionic Triblock Copolymers for Enhanced In Vivo Skeletal Muscle Transfection », Macromolecular Bioscience, vol. 20, nᵒ 3, p. 1900276, 2020.
    Résumé : It is reported that low concentration of amphiphilic triblock copolymers of pMeOx-b-pTHF-b-pMeOx structure (TBCPs) improves gene expression in skeletal muscle upon intramuscular co-injection with plasmid DNA. Physicochemical studies carried out to understand the involved mechanism show that a phase transition of TBCPs under their unimer state is induced when the temperature is elevated from 25 to 37 °C, the body temperature. Several lines of evidences suggest that TBCP insertion in a lipid bilayer causes enough lipid bilayer destabilization and even pore formation, a phenomenon heightened during the phase transition of TBCPs. Interestingly, this property allows DNA translocation across the lipid bilayer model. Overall, the results indicate that TBCPs exhibiting a phase transition at the body temperature is promising to favor in vivo pDNA translocation in skeletal muscle cells for gene therapy applications.
    Mots-clés : amphiphilic copolymers, in vivo transfection, LCST, POLE 4, poly(2-methyl-2-oxazoline), POLYMERES, skeletal muscle.
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  • Y. Si, C. Grazon, G. Clavier, J. Rieger, Y. Tian, J. - F. Audibert, B. Sclavi, et R. Méallet-Renault, « Fluorescent Copolymers for Bacterial Bioimaging and Viability Detection », ACS Sensors, vol. 5, nᵒ 9, p. 2843-2851, sept. 2020.
    Résumé : Novel fluorescent labels with high photostability and high biocompatibility are required for microbiological imaging and detection. Here, we present a green fluorescent polymer chain (GFPC), designed to be nontoxic and water-soluble, for multicolor bioimaging and real-time bacterial viability determination. The copolymer is synthesized using a straightforward one-pot reversible addition–fragmentation chain-transfer (RAFT) polymerization technique. We show that GFPC does not influence bacterial growth and is stable for several hours in a complex growth medium and in the presence of bacteria. GFPC allows the labeling of the bacterial cytoplasm for multicolor bacterial bioimaging applications. It can be used in combination with propidium iodide (PI) to develop a rapid and reliable protocol to distinguish and quantify, in real time, by flow cytometry, live and dead bacteria.
    Mots-clés : POLE 4, POLYMERES.
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  • F. Abbassi, M. Mbarek, D. Kreher, et K. Alimi, « Cross linking-dependent properties of PVK-MEH-PPV bi-block copolymer: Vibrational, thermal and optical properties », Journal of Physics and Chemistry of Solids, vol. 126, p. 274-279, mars 2019.
    Résumé : Despite its interesting optoelectronic properties, the insolubility of poly (N-vinylcarbazole-poly [2-methoxy-5-2 (ethylhexyloxy)-1,4-phenylenevinylene] (PVK-MEH-PPV) bi-block copolymer has caused some difficulties especially for the elaboration of new composites based on this copolymer and [6,6]-phenyl-C61-butanoate of methyl (PCBM). To solve the problem of insolubility, we first modify quantitatively a main parameter in the chemical synthesis, namely the oxidant agent and then replaced with a new one. Dramatic changes in the vibrational and optical properties are founded by varying the FeCl3 amount in the synthesis way due to the cross-linking of PVK units. This is induces the modulation of copolymers properties particularly theirs emissive proprieties due to the modulation of PVK and MEH-PPV contribution. A red shifting of the maximum of photoluminescence and a quenching was observed with increasing of the oxidation yields. Composite based PCBM and copolymer was elaborated due the solubility of one of copolymer by changing the oxidant agent.
    Mots-clés : Chemical synthesis, Infrared spectroscopy, Optical properties, POLYMERES, Polymers, Thermogravimetric analysis (TGA).

  • M. Auffray, D. H. Kim, J. U. Kim, F. Bencheikh, D. Kreher, Q. Zhang, A. D'Aléo, J. - C. Ribierre, F. Mathevet, et C. Adachi, « Dithia[3.3]paracyclophane Core: A Versatile Platform for Triplet State Fine-Tuning and Through-Space TADF Emission », Chemistry – An Asian Journal, vol. 14, nᵒ 11, p. 1921-1925, 2019.
    Résumé : Thermally activated delayed fluorescence (TADF) based on through-space donor and acceptor interactions constitute a recent and promising approach to develop efficient TADF emitters. Novel TADF isomers using a dithia[3.3]-paracyclophane building block as a versatile 3D platform to promote through-space interactions are presented. Such a 3D platform allows to bring together the D and A units into close proximity and to probe the effect of their orientation, contact site and distance on their TADF emission properties. This study provides evidence that the dithia[3.3]paracyclophane core is a promising platform to control intramolecular through-space interactions and obtain an efficient TADF emission with short reverse-intersystem crossing (RISC) lifetimes. In addition, this study demonstrates that this design can tune the energy levels of the triplet states and leads to an upconversion from 3CT to 3LE that promotes faster and more efficient RISC to the 1CT singlet state.
    Mots-clés : cyclophanes, donor-acceptor molecules, POLYMERES, TADF lifetime, thermally activated delayed fluorescence, through-space interactions.
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  • V. Ayzac, Q. Sallembien, M. Raynal, B. Isare, J. Jestin, et L. Bouteiller, « A Competing Hydrogen Bonding Pattern to Yield a Thermo-Thickening Supramolecular Polymer », Angewandte Chemie International Edition, vol. 58, nᵒ 39, p. 13849-13853, 2019.
    Résumé : Introduction of competing interactions in the design of a supramolecular polymer (SP) creates pathway complexity. Ester–bis-ureas contain both a strong bis-urea sticker that is responsible for the build-up of long rod-like objects by hydrogen bonding and ester groups that can interfere with this main pattern in a subtle way. Spectroscopic (FTIR and CD), calorimetric (DSC), and scattering (SANS) techniques show that such ester–bis-ureas self-assemble into three competing rod-like SPs. The previously unreported low-temperature SP is stabilized by hydrogen bonds between the interfering ester groups and the urea moieties. It also features a weak macroscopic alignment of the rods. The other structures form isotropic dispersions of rods stabilized by the more classical urea-urea hydrogen bonding pattern. The transition from the low-temperature structure to the next occurs reversibly by heating and is accompanied by an increase in viscosity, a rare feature for solutions in hydrocarbons.
    Mots-clés : hydrogen bonds, pathway complexity, POLYMERES, self-assembly, supramolecular polymers, urea.

  • K. Baatout, F. Saad, A. Baffoun, B. Mahltig, D. Kreher, N. Jaballah, et M. Majdoub, « Luminescent cotton fibers coated with fluorescein dye for anti-counterfeiting applications », Materials Chemistry and Physics, vol. 234, p. 304-310, août 2019.
    Résumé : A simple, rapid and green method to develop fluorescent cotton yarns was established. We report the application of fluorescein (FL) into textile support by impregnation method while keeping the original cotton yarn properties for anti-counterfeiting applications. The FL-coated yarns were characterized by Scanning Electron Microscopy, reflectance and fluorescence spectroscopy. The CIE chromaticity diagram showed a yellowish green emission with a weak yellow coloration of cotton fiber. Mechanical characterization of samples shows that the application of fluorescein did not alter significantly the breaking strength and elongation at break of the fibers, even when using resins. In contrast, to resin-free impregnation process the color fastness test demonstrates that the use of resins as binder is required. The obtained results showed that cotton samples release slowly its contents and fluorescein remains more than five washing cycles.
    Mots-clés : Anti-counterfeiting, Cotton fiber, Fluorescein dye, Fluorescence, POLYMERES, Resin, Washing fastness.

  • G. Basuyaux, A. Desmarchelier, G. Gontard, N. Vanthuyne, J. Moussa, H. Amouri, M. Raynal, et L. Bouteiller, « Extra hydrogen bonding interactions by peripheral indole groups stabilize benzene-1,3,5-tricarboxamide helical assemblies », Chemical Communications, vol. 55, nᵒ 59, p. 8548-8551, juill. 2019.
    Résumé : Benzene-1,3,5-tricarboxamide monomers derived from alkyl esters of tryptophan (BTA Trp) self-assemble into helices with an inner threefold hydrogen bond network surrounded by a second network involving the indole N–H groups. As a consequence of this extra stabilization of its helical assemblies, BTA Trp forms more viscous solutions than a range of ester and alkyl BTAs.
    Mots-clés : ARC, POLE 1, POLYMERES.
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  • K. Bernardino, J. Świergiel, J. Jadżyn, L. Bouteiller, et A. F. de Moura, « Bulkiness as a design element to increase the rigidity and macrodipole of supramolecular polymers », Journal of Molecular Liquids, vol. 286, p. 110937, juill. 2019.
    Résumé : N,N′-dialkyl ureas in non-polar solvents self-assemble as hydrogen bonded chains. Infrared and dielectric spectroscopy show that more sterically crowded monomers form shorter chains but also larger macrodipoles. This unexpected effect is due to the enhanced rigidity of the bulky assemblies, as confirmed by molecular dynamics simulations.
    Mots-clés : POLYMERES.

  • Y. El Mendili, A. Vaitkus, A. Merkys, S. Gražulis, D. Chateigner, F. Mathevet, S. Gascoin, S. Petit, J. - F. Bardeau, M. Zanatta, M. Secchi, G. Mariotto, A. Kumar, M. Cassetta, L. Lutterotti, E. Borovin, B. Orberger, P. Simon, B. Hehlen, et M. Le Guen, « Raman Open Database: first interconnected Raman–X-ray diffraction open-access resource for material identification », Journal of Applied Crystallography, vol. 52, nᵒ 3, p. 618-625, juin 2019.
    Résumé : The fully open character of the Raman Open Database makes this novel database freely and completely usable by anybody worldwide: academics, those working in industry and the general public.
    Mots-clés : POLYMERES.
    Pièce jointe Full Text PDF 428.1 ko (source)

  • C. Grazon, Y. Si, J. - P. Placial, J. Rieger, R. Méallet-Renault, et G. Clavier, « Core–shell polymeric nanoparticles comprising BODIPY and fluorescein as ultra-bright ratiometric fluorescent pH sensors », Photochemical & Photobiological Sciences, vol. 18, nᵒ 5, p. 1156-1165, 2019.

  • J. Hendricks, A. Louhichi, V. Metri, R. Fournier, N. Reddy, L. Bouteiller, M. Cloitre, C. Clasen, D. Vlassopoulos, et W.  J. Briels, « Nonmonotonic Stress Relaxation after Cessation of Steady Shear Flow in Supramolecular Assemblies », Physical Review Letters, vol. 123, nᵒ 21, p. 218003, nov. 2019.
    Résumé : Stress relaxation upon cessation of shear flow is known to be described by single-mode or multimode monotonic exponential decays. This is considered to be ubiquitous in nature. However, we found that, in some cases, the relaxation becomes anomalous in that an increase in the relaxing stress is observed. Those observations were made for physicochemically very different systems, having in common, however, the presence of self-associating units generating structures at large length scales. The nonmonotonic stress relaxation can be described phenomenologically by a generic model based on a redistribution of energy after the flow has stopped. When broken bonds are reestablished after flow cessation, the released energy is partly used to locally increase the elastic energy by the formation of deformed domains. If shear has induced order such that these elastic domains are partly aligned, the reestablishing of bonds gives rise to an increase of the overall stress.
    Mots-clés : POLYMERES.
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  • N. Illy, V. Corcé, J. Zimbron, V. Molinié, M. Labourel, G. Tresset, J. Degrouard, M. Salmain, et P. Guégan, « pH-Sensitive Poly(ethylene glycol)/Poly(ethoxyethyl glycidyl ether) Block Copolymers: Synthesis, Characterization, Encapsulation, and Delivery of a Hydrophobic Drug », Macromolecular Chemistry and Physics, vol. 220, nᵒ 16, p. 1900210, 2019.
    Résumé : Abstract Curcumin is a natural polyphenolic compound known for its numerous pharmacological properties. However, its low water solubility and instability at neutral pH are serious drawbacks preventing its use as an oral drug. Well-defined amphiphilic poly(ethylene glycol)-block-poly(ethoxyethyl glycidyl ether) (PEG-b-PEEGE) block copolymers carrying acid-labile acetal groups are synthesized by anionic ring-opening polymerization and investigated as potential pH-sensitive nano-carriers for delivery of curcumin to cancer cells. The nanoparticles, resulting from copolymer self-assembly in aqueous media, are characterized by dynamic light scattering and cryo-transmission electron microscopy. The nanoparticles? stabilities are evaluated in three different phosphate buffers (pH = 7.2, 6.4, and 5.3). The stability decreases at lower pH and a complete disappearance of the nanoparticles is noticed after 4 days at pH 5.3. Curcumin is encapsulated in hydrophobic core of mPEG40-b-PEEGE25 nanoparticles allowing significant enhancements of curcumin solubility in water and lifetime at neutral pH. In vitro curcumin release is studied at different pH by UV-spectroscopy and high-performance liquid chromatography (HPLC). The cytotoxicity of curcumin and curcumin encapsulated in micelles is evaluated by cell viability 3-(4,5-Dimethyl-2-thiazolyl)-2,5-diphenyl-2H-tetrazolium bromide (MTT) assay on MDA-MB-231 human breast cancer cells.
    Mots-clés : amphiphilic polyethers, anionic-ring opening polymerization, CHEMBIO, curcumin encapsulation, pH-sensitive copolymers, POLE 3, POLE 4, POLYMERES, self-assembly.
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    Note Note
    <p>doi: 10.1002/macp.201900210</p>

  • N. Illy, D. Urayeneza, A. V. Maryasevskaya, L. Michely, S. Boileau, B. Brissault, E. A. Bersenev, D. V. Anokhin, D. A. Ivanov, et J. Penelle, « Synthesis and Solid-State Properties of PolyC3 (Co)polymers Containing (CH2–CH2–C(COOR)2) Repeat Units with Densely Packed Fluorocarbon Lateral Chains », Macromolecules, vol. 52, nᵒ 23, p. 9199-9207, déc. 2019.
    Résumé : The synthesis and structural characterization of linear PolyC3 polymers containing trimethylene-1,1-dicarboxylate structural repeat units with C6F13 and C8F17 fluorinated side chains is described for the first time, and their properties were compared with the traditional polyvinyl structures that display the fluorinated chain on every second rather than on every third carbon alongside the backbone. Homopolymers as well as statistical and block copolymers with n-propyl and/or allyl trimethylene-1,1-dicarboxylate blocks have been obtained from PolyC3 precursors containing diallyl trimethylene-1,1-dicarboxylate units, by reacting C6F13–C2H4–SH and C8F17–C2H4–SH thiols with the allyl groups using a thiol–ene post-polymerization modification reaction. Solid-state properties have been investigated by differential scanning calorimetry for all of the (co)polymers and by small-angle X-ray scattering/wide-angle X-ray scattering for the C8F17 homopolymer at several temperatures. The structure of the homopolymer consistently shows a coexistence of two smectic phases at room temperature, which can be identified as SmB and SmC. This coexistence is assumed to arise from the fact that the distances between carboxylic oxygens bonded to the same carbon are very close to the ones between the neighboring carboxylic oxygens alongside the backbone, resulting in two possible ways of packing the pendent fluoroalkyl chains arranged in a hexatic order.
    Mots-clés : POLE 4, POLYMERES.
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  • M. Lansalot et J. Rieger, « Polymerization-Induced Self-Assembly », Macromolecular Rapid Communications, vol. 40, nᵒ 2, p. 1800885, 2019.

  • K. J. Lee, Y. Xiao, E. S. Kim, F. Mathevet, L. Mager, O. Cregut, Frédéric Fages, J. - C. Ribierre, J. W. Wu, et A. D’Aléo, « Donor–Acceptor Distance-Dependent Charge Transfer Dynamics Controlled by Metamaterial Structures », ACS Photonics, vol. 6, nᵒ 11, p. 2649-2654, nov. 2019.
    Résumé : The capability to control charge transfer dynamics in a donor–acceptor molecule is important for efficient optoelectronic devices. Charge transfer dynamics is governed by thermodynamics of donor–acceptor charges in a given dielectric environment. Metamaterial structure has been shown to be able to control charge separation and charge recombination processes via nonlocal effect on dielectric permittivity for a fixed donor–acceptor distance organic film. Here, we report the influence of the metamaterial structure on the donor–acceptor distance dependence of the electron transfer process occurring in liquid crystalline organic semiconductor thin films. By examining the charge recombination rate in three different donor–acceptor distances, it is found that the barrier height β increases from 0.084 to 0.137 Å–1 by 63% in the presence of metal-dielectric multilayered metamaterial structures. Based on the Marcus theory on the charge transfer process, we show that a further increase in the driving force for a larger donor–acceptor distance is mainly responsible for the barrier height increase in the presence of a multilayered metamaterial substrate when compared with a glass substrate. This study will provide a significant step forward in enabling more efficient hybrid organic-optoelectronic devices associated with the charge tran

    sfer process.
    Mots-clés : POLYMERES.
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  • Y. U. Lee, O. P. M. Gaudin, K. J. Lee, E. Choi, V. Placide, K. Takaishi, T. Muto, P. André, A. Muranaka, M. Uchiyama, F. Mathevet, T. Aoyama, J. W. Wu, A. D’Aléo, et J. - C. Ribierre, « Organic Monolithic Natural Hyperbolic Material », ACS Photonics, vol. 6, nᵒ 7, p. 1681-1689, juill. 2019.
    Résumé : Materials with hyperbolic dispersion are the key to a variety of photonic applications involving nanoimaging, hyper-lensing, and spontaneous emission engineering, due to the availability of high k modes. Here we demonstrate that spin-coated polycrystalline organic semiconducting films with a layered molecular packing structure can exhibit a hyperbolic dispersion over a wide spectral range and support the presence of surface excitonic polaritons. This was evidenced from 670 to 920 nm and is related to the negative real part of the dielectric permittivity of the selected quinoidal organic semiconductor. In addition, the accessible high k modes lead to changes in the spontaneous emission decay rate and photoluminescence quantum yield of emitters placed nearby the organic monolithic (composed of only one molecule and not necessitating an alternating multilayer structure) natural hyperbolic material. This study opens a new route toward single-step solution manufacturing of large-area, low-cost, and flexible organic photonic metadevices with hyperbolic dispersion.
    Mots-clés : POLYMERES.
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  • Y. Li, L. Bouteiller, et M. Raynal, « Catalysts Supported by Homochiral Molecular Helices: A New Concept to Implement Asymmetric Amplification in Catalytic Science », ChemCatChem, vol. 11, nᵒ 21, p. 5212-5226, 2019.
    Résumé : Connecting intrinsically achiral catalytic centers to helical polymers provides a new class of asymmetric catalysts whose selectivity exclusively stems from the chiral environment provided by the helical polymer. Chirality amplification phenomena allow to control the handedness and the helical sense excess of these polymers which in turn dictate the stereochemical direction and the extent of enantioinduction, respectively, obtained in the course of the asymmetric reaction. This minireview is focused on such helical catalysts built either on a covalent or a non-covalent scaffold and for which the handedness is controlled by an asymmetric polymerization reaction, by enantiopure monomers or by chiral additives. The selectivity of catalysts based on a dynamic helical backbone can be tuned by changing the solvent or with additives. The fact that the enantiomeric state of such asymmetric catalysts can be switched in a predictable way is particularly emphasized.
    Mots-clés : asymmetric catalysis, chirality amplification, macromolecular helices, POLYMERES, supramolecular helices, switchable catalysis.
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  • Y. Li, X. Caumes, M. Raynal, et L. Bouteiller, « Modulation of catalyst enantioselectivity through reversible assembly of supramolecular helices », Chemical Communications, vol. 55, nᵒ 15, p. 2162-2165, févr. 2019.
    Résumé : A multi-configurable catalyst, for which the degree of enantioinduction in successive reactions is varied between 6% ee and 52% ee, is achieved by supporting copper centres at the periphery of supramolecular helices. Precise characterization of the co-assemblies corroborates the relation between helix length and catalyst selectivity.
    Mots-clés : POLYMERES.
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  • Y. Li, L. Dubreucq, B. G. Alvarenga, M. Raynal, et L. Bouteiller, « N-Substituted Benzene-1-Urea-3,5-Biscarboxamide (BUBA): Easily Accessible C2-Symmetric Monomers for the Construction of Reversible and Chirally Amplified Helical Assemblies », Chemistry – A European Journal, vol. 25, nᵒ 45, p. 10650-10661, 2019.
    Résumé : Non-C3-symmetric supramolecular helices are gaining interest for the design of hierarchical assemblies, for the compartmentalisation or the self-assembly of polymer chains and for application in asymmetric catalysis. Herein, N-substituted benzene-1-urea-3,5-biscarboxamide (BUBA) monomers, which consist of one urea and two carbon-connected amide functions linked to an aromatic ring, are introduced as an easily accessible class of C2-symmetric supramolecular synthons. In apolar solvents, BUBA monomers assemble into long helical assemblies by means of hydrogen-bonding and aromatic interactions, as assessed by several analytical techniques. To probe the influence of the urea function, BUBA and related benzene-1,3,5-tricarboxamide (BTA) helical polymers have been compared, in terms of their thermodynamics of formation, stability, reversibility and chiral amplification properties. Similar to BTA, BUBA monomers form long helices reversibly through a highly cooperative mechanism and the helicity of their assemblies is governed by chiral amplification effects. However, precise quantification of their properties reveals that BUBA monomers assemble in a more cooperative manner. Also, chiral amplification operates to a higher extent in BUBA helices, as probed by both sergeants-and-soldiers and majority-rules experiments. Compatibility between urea and amide functions also allows the formation of co-assemblies that incorporate both BUBA and BTA monomers. Importantly, a small amount of chiral BUBA monomers in these co-assemblies is sufficient to obtain single-handed helices; thus paving the way towards the development of functional supramolecular helices.
    Mots-clés : chirality, cooperative effects, helical structures, noncovalent interactions, POLYMERES, self-assembly.
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  • T. H. N. Nguyen, F. Balligand, A. Bormann, V. Bennevault, et P. Guégan, « Synthesis of new biobased linear poly(ester amide)s », European Polymer Journal, vol. 121, p. 109314, déc. 2019.
    Résumé : In the present work, we investigated the synthesis of new biobased linear aliphatic PEAs with a controlled regicity, in a two steps procedure. First, dioldiamide derivatives were successfully synthesized, then polycondensation reaction using the usual alcohol plus acid reaction was performed. NMR analyses demonstrate that dioldiamide can be synthesized in one step from diacid and ethanolamine condensation with high conversion. A new library of polymers was then synthesized, and characterized. Overall, the reactivity of amine or alcohol or acid functions is investigated by in-depth 1H and 13C NMR versus HSQC NMR analysis. These results can be used to follow the complex evolution of monoesterification or diesterification reactions, monoamidation or diamidation reactions when dicarboxylic acids versus alcohol or amine are reacted. Thermal degradation was examined, and a good stability of all the polymers was evidenced. The thermal properties of the polymers were also analyzed, and high melting temperatures were measured, thanks to the control of the regicity. Comparing the melting and crystallization temperature revealed a fast rate of crystallization, an important feature for polymer melt processing. The solubility behavior of these polymers was found to be close to the one of polyamides, suggesting the use of this new polymers library to replace polyamides in applications where biodegradability of the materials is required.
    Mots-clés : Biomass, Dicarboxylic acid, Dioldiamide monomer, Poly(ester amide)s, POLYMERES, Thermal behaviors.

  • J. - C. Ribierre, Z. Li, X. Liu, E. Lacaze, B. Heinrich, S. Méry, P. Sleczkowski, Y. Xiao, F. Lafolet, D. Hashizume, T. Aoyama, M. Uchiyama, J. W. Wu, E. Zaborova, F. Fages, A. D’Aléo, F. Mathevet, et C. Adachi, « A solvent-free and vacuum-free melt-processing method to fabricate organic semiconducting layers with large crystal size for organic electronic applications », Journal of Materials Chemistry C, vol. 7, nᵒ 11, p. 3190-3198, mars 2019.
    Résumé : We report on an improved melt-processing method to prepare organic semiconducting layers with large crystal size and enhanced charge carrier mobilities. The organic compound used in this work is a solution-processable oligo(p-phenylene vinylene) derivative substituted at both ends with pyrene moieties. Accurate control of the temperature during the recrystallization of this compound from the melt enables the formation of large single crystal monodomains in thin films. The melt-processed organic layer shows higher mobilities in transistor configuration than in spin-coated films, which can be attributed to the presence of large-size crystalline monodomains as evidenced by X-ray diffraction measurements. We also investigated the photophysical properties of this material in spin-coated and melted films and found an increase of the photoluminescence quantum yield with the size of the crystals in the organic layer. The advantage of this method over the spin coating also allowed observation of amplified spontaneous emission that was only achieved in the melted film due to its improved luminescence efficiency. Overall, this study demonstrates a simple and versatile method, which does not require the use of any solvent and vacuum, to fabricate organic layers with large crystal size, suitable for the realization of organic electronic and light-emitting devices.
    Mots-clés : POLYMERES.

  • D. Rosa Nunes, M. Reche-Tamayo, E. Ressouche, M. Raynal, B. Isare, P. Foury-Leylekian, P. - A. Albouy, P. Brocorens, R. Lazzaroni, et L. Bouteiller, « Organogel Formation Rationalized by Hansen Solubility Parameters: Shift of the Gelation Sphere with the Gelator Structure », Langmuir, vol. 35, nᵒ 24, p. 7970-7977, juin 2019.
    Résumé : To rationalize how the gelation ability of a low molecular weight gelator is influenced by its molecular structure, we performed extensive solubility tests of a group of thiazole-based gelators and made use of Hansen solubility parameter formalism. We observe that the increase of a linear alkyl chain in these gelators promotes an increase of the radius of the gelation sphere as well as a gradual shift of its center to lower values of the polar (δP) and hydrogen bonding (δH) components. The molecular packing within the fibers and the crystal habit were determined by a combination of X-ray diffraction and molecular modeling. We attribute the gradual and linear shift of the gelation sphere to the fact that all of the studied gelators share the same molecular packing, so that an increasing length of the alkyl chain reduces the proportion of polar groups at the surface, resulting in a gradual increase in the contact between apolar parts of the fiber and the solvent.
    Mots-clés : POLYMERES.
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  • Ö. Tezgel, S. Noinville, V. Bennevault, N. Illy, et P. Guégan, « An alternative approach to create N-substituted cyclic dipeptides », Polymer Chemistry, vol. 10, nᵒ 6, p. 776-785, févr. 2019.
    Résumé : N-Modified peptide backbones are promising peptidomimetics which offer several advantages in terms of improved biological activity and stability. They further allow the development of novel functional materials. However, the synthesis of N-substituted peptides is very challenging with the existing methods, particularly the synthesis of peptides with larger N-substituents. In this work, we are introducing a new method to create N-polyether substituted cyclic dipeptides via anionic ring-opening polymerization (AROP). Four different cyclic dipeptides with different hydrophobic functional groups were selected to create N-substituted cyclic dipeptides. Backbone amides –NH– were deprotonated with phosphazene bases to form nucleophilic initiators. Furthermore, the effect of different phosphazene bases (tBuP4 and tBuP2) and of the addition of a Lewis acid (i-Bu3Al) was studied in detail towards creating N-polyether-cyclic dipeptides bearing either hydrophobic poly(butylene oxide) chains, or hydrophilic linear polyglycidol chains, thanks to the polymerization of 1,2-epoxybutane and the polymerization followed by the deprotection of t-butyl glycidyl ether monomers, respectively. Moreover, we have demonstrated the possibility of avoiding the isomerization of cyclic dipeptides during the synthesis of N-substituted analogues depending on the synthetic approach.
    Mots-clés : POLYMERES.
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  • Ö. Tezgel, V. Puchelle, H. Du, N. Illy, et P. Guégan, « Modification of proline-based 2,5-diketopiperazines by anionic ring-opening polymerization », Journal of Polymer Science Part A: Polymer Chemistry, vol. 57, nᵒ 9, p. 1008-1016, 2019.
    Résumé : 2,5-Diketopiperazines (DKPs) are the smallest cyclic dipeptides found in nature with various attractive properties. In this study, we have demonstrated the successful modification of proline-based DKPs using anionic ring-opening polymerization (AROP) as a direct approach. Four different proline-based DKPs with various side chains and increasing steric hindrance were used as initiating species for the polymerization of 1,2-epoxybutane or ethoxyethyl glycidyl ether in the presence of t-BuP4 phosphazene base. The addition of a Lewis acid, tri-isobutyl aluminum, to the reaction mixture strongly decreased the occurrence of side reactions. Impact of the DKP side-chain functionalities on molar mass control and dispersity was successfully evidenced. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1008–1016
    Mots-clés : anionic polymerization, peptides, POLE 4, polyethers, POLYMERES, ring-opening polymerization.
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  • K. Wang, L. Trichet, C. Rieu, C. Peccate, G. Pembouong, L. Bouteiller, et T. Coradin, « Interactions of Organosilanes with Fibrinogen and Their Influence on Muscle Cell Proliferation in 3D Fibrin Hydrogels », Biomacromolecules, vol. 20, nᵒ 10, p. 3684-3695, oct. 2019.
    Résumé : Silanization of biomacromolecules has emerged as a fruitful approach to prepare hybrid biohydrogels. However, very little is known about interactions between organosilanes and biopolymers in solution. Here we focused on fibrin, a protein of interest in the biomedical field, whose self-assembly process and resulting gel structure are highly sensitive to experimental conditions. Three main silanes were selected to decipher the relative influence of the silanol groups and organic functions. Whereas no protein denaturation was observed, silanes bearing hydrophobic groups had a surfactant-like behavior and could improve the dispersion of fibrinogen molecules, impacting gel formation kinetics and rheological properties. 3D cultures of myoblasts evidenced that organosilanes could promote or impede cell proliferation, suggesting interactions of silanols with fibrin. These results demonstrate that the two sides of the coin of organosilane reactivity are relevant at different stages of fibrin gel formation and must be considered for future development of hybrid biomaterials.
    Mots-clés : POLE 4, POLYMERES.
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  • D. Zhang, Y. Zhang, Y. Fan, M. - N. Rager, V. Guérineau, L. Bouteiller, M. - H. Li, et C. M. Thomas, « Polymerization of Cyclic Carbamates: A Practical Route to Aliphatic Polyurethanes », Macromolecules, vol. 52, nᵒ 7, p. 2719-2724, avr. 2019.
    Résumé : A new polymerization system is reported that provides aliphatic polyurethanes with novel structures from the anionic ring-opening polymerization of five-membered carbamates. By use of a bifunctional initiating system, the anionic ring-opening polymerization of cyclic carbamates gives unimodal polymers with Đ values generally narrow. A series of PUs with controlled molecular weights were synthesized by changing the reaction conditions. Detailed analysis of the reaction demonstrates that repeated acylations of in situ formed urethane anions lead to the formation of the polyurethane.
    Mots-clés : POLYMERES.
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  • P. Biais, P. Beaunier, F. Stoffelbach, et J. Rieger, « Loop-stabilized BAB triblock copolymer morphologies by PISA in water », Polymer Chemistry, vol. 9, nᵒ 35, p. 4483-4491, sept. 2018.
    Résumé : A straightforward strategy to synthesize loop-stabilized particles in water via PISA is developed. These particular structures can in theory be obtained through the synthesis of amphiphilic BAB triblock copolymers, starting from a hydrophilic middle block A, which is chain extended in an aqueous PISA process with two hydrophobic external blocks B. For this purpose, symmetrical bifunctional poly(N,N-dimethylacrylamide) macroRAFT agents with a central benzoic acid group and an alkyl chain as the Z group are used in the aqueous dispersion polymerization of diacetone acrylamide. For the first time, stable BAB flower-like particles are formed via PISA in pure water. It is shown that the colloidal stability and the resulting particle morphology (spheres, worms, vesicles) strongly depend on the degree of ionization of the central charge in the stabilizer loop, and thus on the pH at which PISA is performed. Moreover, the influence of the length of the alkyl Z group (dodecyl and butyl alkyl chains) on the colloidal stability is studied.
    Mots-clés : POLE 4, POLYMERES.
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  • R. Brisse, D. Guianvarc'h, C. Mansuy, S. Sagan, D. Kreher, L. Sosa-Vargas, L. Hamitouche, V. Humblot, I. Arfaoui, V. Labet, C. Paris, C. Petit, et A. - J. Attias, « Probing the in-air growth of large area of 3D functional structures into a 2D supramolecular nanoporous network », Chemical Communications, vol. 54, nᵒ 72, p. 10068-10071, 2018.
    Mots-clés : POLE 4, POLYMERES.

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  • X. Callies, E. Ressouche, C. Fonteneau, G. Ducouret, S. Pensec, L. Bouteiller, et C. Creton, « Effect of the Strength of Stickers on Rheology and Adhesion of Supramolecular Center-Functionalized Polyisobutenes », Langmuir, vol. 34, nᵒ 42, p. 12625-12634, oct. 2018.
    Résumé : In order to systematically investigate the effect of the strength of the supramolecular interactions on the debonding properties of associative polymers, a series of model systems have been characterized by probe-tack tests. These model materials, composed of linear and low dispersity poly(isobutylene) chains (Mn ≈ 3 kg/mol) center-functionalized by a single bis-urea sticker, are able to self-assemble by four hydrogen bonds. Three types of stickers are used in the present study: a bis-urea with a methylene diphenyl (MDI) spacer, a bis-urea with a tolyl (TOL) spacer, and a bis-urea with a xylyl (XYL) spacer. In order to investigate the influence of stickers in depth, both the nanostructure of the materials and the linear rheology were investigated by small-angle X-ray scattering (SAXS) and oscillatory shear, respectively. For two types of stickers (TOL and XYL), the association of polymers via hydrogen bonds induces the formation of bundles of rodlike aggregates at room temperature and the behavior of a soft elastic material was observed. For bis-urea MDI, no structure is detected by SAXS and a Newtonian behavior is observed at room temperature. In probe-tack experiments, all these materials show a cohesive mode of failure, a signature of flowing materials as previously observed for tri-urea center-functionalized poly(butylacrylate) (PnBA3U). However, XYL center-functionalized polyisobutene shows much higher debonding energies than PnBA3U, revealing the importance of the strength of noncovalent bonds in the scission/recombination dynamics. On the basis of the analysis of the debonding images, this effect is discussed via the mechanical behavior at large deformation.
    Mots-clés : POLE 4, POLYMERES.

  • M. Dréan, A. Debuigne, C. Jérôme, C. Goncalves, P. Midoux, J. Rieger, et P. Guégan, « Poly(N-methylvinylamine)-Based Copolymers for Improved Gene Transfection », Macromolecular Bioscience, vol. 18, nᵒ 4, p. 1700353, avr. 2018.
    Résumé : 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.
    Mots-clés : gene delivery, nanoparticles, POLE 4, POLYMERES, polyvinylamine.
    Pièce jointe Full Text PDF 3.2 Mo (source)

  • B. Ebeling, K. Belal, F. Stoffelbach, P. Woisel, M. Lansalot, et F. D'Agosto, « Polymer Nanospheres with Hydrophobic Surface Groups as Supramolecular Building Blocks Produced by Aqueous PISA », Macromolecular Rapid Communications, p. 1800455, 2018.
    Résumé : A robust and straightforward synthesis of waterborne polymer nanospheres bearing the supramolecular association unit dialkoxynapthalene at their surface is presented using polymerization-induced self-assembly (PISA). A RAFT agent bearing this unit is first employed to produce poly(acrylic acid) chains, which are then chain-extended with styrene (S) to spontaneously form the nano-objects via RAFT aqueous emulsion polymerization. The particular challenge posed by the dialkoxynapthalene hydrophobicity can be overcome by the use of PISA and the deprotonation of the poly(acrylic acid). At pH = 7, very homogeneous latexes are obtained. The particle diameters can be tuned from 36 to 105 nm (with a narrow particle size distribution) by varying the molar mass of the PS block. The surface accessibility of the dialkoxynapthalene moieties is demonstrated by complexation with the complementary host cyclobis(paraquat-p-phenylene) (CBPQT4+ · Cl−), highlighting the potential of the nanospheres to act as building blocks for responsive supramolecular structures.
    Mots-clés : emulsion polymerization, POLE 4, polymer nanoparticles, POLYMERES, polymerization-induced self-assembly, RAFT polymerization, supramolecular assembly.

  • Z. Eskandani, T. Le Gall, T. Montier, P. Lehn, F. Montel, L. Auvray, C. Huin, et P. Guégan, « Polynucleotide transport through lipid membrane in the presence of starburst cyclodextrin-based poly(ethylene glycol)s », The European Physical Journal E, vol. 41, nᵒ 11, p. 132, nov. 2018.
    Résumé : .Symmetrical cyclodextrin-based 14-arm star polymers with poly(ethylene glycol) PEG branches were synthesized and characterized. Interactions of the star polymers with lipid bilayers were studied by the “black lipid membrane” technique in order to demonstrate the formation of monomolecular artificial channels. The conditions for the insertion are mainly based on dimensions and amphiphilic properties of the star polymers, in particular the molar mass of the water-soluble polymer branches. Translocation of single-strand DNA (ssDNA) through those synthetic nanopores was investigated, and the close dimension between the cross-section of ssDNA and the cyclodextrin cavity led to an energy barrier that slowed down the translocation process.Graphical abstract Open image in new window
    Mots-clés : POLE 4, POLYMERES, Polymers: From Adsorption to Translocation - Topical Issue in Memoriam Loïc Auvray (1956-2016).

  • P. Evenou, J. Rossignol, G. Pembouong, A. Gothland, D. Colesnic, R. Barbeyron, S. Rudiuk, A. - G. Marcelin, M. Ménand, D. Baigl, V. Calvez, L. Bouteiller, et M. Sollogoub, « Bridging beta-Cyclodextrin prevents self-inclusion and allows formation of supramolecular polymers: self-assembly and cooperative interaction with nucleic acids », Angewandte Chemie International Edition, avr. 2018.
    Mots-clés : cyclodextrin, GOBS, inclusion complexes, nucleic acids, POLE 3, POLE 4, POLYMERES, supramolecular polymers.
    Pièce jointe Full Text PDF 3.2 Mo (source)

  • I. Faye, C. Huin, N. Illy, V. Bennevault, et P. Guégan, « β-Cyclodextrin-Based Star Amphiphilic Copolymers: Synthesis, Characterization, and Evaluation as Artificial Channels », Macromolecular Chemistry and Physics, p. 1800308, oct. 2018.
    Résumé : Abstract 14-arm amphiphilic star copolymers are synthesized according to different strategies. First, the anionic ring polymerization of 1,2-butylene oxide (BO) initiated by per(2-O-methyl-3,6-di-O-(3-hydroxypropyl))-?-CD (?-CD?OH14) and catalyzed by t-BuP4 in DMF is investigated. Analyses by NMR and SEC show the well-defined structure of the star ?-CD?-PBO14. To obtain a 14-arm poly(butylene oxide-b-ethylene oxide) star, a Huisgen cycloaddition between an α-methoxy-?-azidopoly(ethylene oxide) and the ?-CD?-PBO14,whose end-chains are beforehand alkyne-functionalized, is performed. In parallel, 14-arm star copolymers composed of butylene oxide-b-glycidol arms are successfully synthesized by the anionic polymerization of ethoxyethylglycidyl ether (EEGE) initiated by ?-CD?-PBO14 with t-BuP4. The deprotection of EEGE units is then performed to provide the polyglycidol blocks. These amphiphilic star polymers are evaluated as artificial channels in lipid bilayers. The effect of changing a PEO block by a polyglycidol block on the insertion properties of these artificial channels is discussed.
    Mots-clés : amphiphilic star copolymers, anionic polymerization, artificial channels, phosphazene base, POLE 4, POLYMERES, β-cyclodextrin.
    Pièce jointe Full Text PDF 4.4 Mo (source)
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