Poster P1

Jean WOLFF Affiliation: Institut Charles Sadron - Strasbourg A theoretical approach to phase coexistence in ternary Cholesterol-phospholipid mixtures

Poster P2

Stéphane DUCHIRON Affiliation: ICPEES - ECPM Mixed systems to assist enzymatic ring opening polymerization of lactide stereoisomers

Poster P3

Franck SNIJKERS Affiliation: UMR 5268, CNRS/SOLVAY, LYON A rheological study of vitrimers

Poster P4 杨奇志 Qizhi YANG Affiliation: Institut de Science des Matériaux de Mulhouse (IS2M) Photocatalyzed Cu-based ATRP involving an Oxidative Quenching Mechanism under Visible Light

Poster P5

Uwe HAHN Affiliation: Laboratoire de Chimie des Matériaux Moléculaires - ECPM One-pot synthesis of sub-3 nm gold nanoparticle networks connected by thio-based multidentate fullerene adducts

Poster P6

Benjamin CABANNES-BOUÉ

Affiliation: Institut de Science des Matériaux de Mulhouse (IS2M) Polymers synthesized by RAFT as versatile macrophotoinitiators

Poster P7 陈静 Jing CHEN Affiliation: Physicochemistry of Glycopolymer Group CERMAV Grenoble Synthesis and properties of bottlebrush-like xyloglucan oligosaccharide-based glycopolymers with controlled composition

Poster P8 左晓玲 Xiaoling ZUO Affiliation: Institut de Science des Materiaux de Mulhouse IS2M Fluorescent brightener as photoinitiator for free radical photopolymerizations under visible LED

Poster P9

Federica FIORINI

Affiliation: Laboratoire de Chimie et des Biomatériaux Supramoléculaires ISIS Chemotaxis and Bioactivity in a New Class of Nanocomposite Hydrogel Systems

Poster P10

Michel RAWISO Affiliation: Institut Charles Sadron - Strasbourg Orientation order in polyelectrolyte solutions

Poster P11

Franck SCHILLINGER Affiliation: Laboratoire de Chimie des Matériaux Moléculaires – ECPM

Self-organisation of dodeca-dendronized fullerene into supramolecular discs and helical columns

Poster P12

Iwona NIERENGARTEN Affiliation: Laboratoire de Chimie des Matériaux Moléculaires - ECPM Langmuir and Langmuir-Blodgett films from amphiphilic pillar[5]arene-containing [2]rotaxanes

Poster P13

Haifaa MOKBEL Affiliation: Institut de Science des Matériaux de Mulhouse (IS2M) Iodonium-Polyoxometalate and Thianthrenium-Polyoxometalate as New One- Component UV Photoinitiators for Radical and Cationic Polymerization

Poster P14

Mariem BOUZRATI-ZERELLI Affiliation: Institut de Science des Matériaux de Mulhouse (IS2M) Towards new photoinitiating systems for visible light: high performances systems with unusual bleaching properties

Poster P15

Eric MEICHSNER Affiliation: Laboratoire de Chimie des Matériaux Moléculaires – ECPM Preparation of Pillar[5]arene-Based [2]Rotaxanes from Acyl Chlorides and Amines

Poster P16

Sofia TELITEL Affiliation: Institut Charles Sadron - Strasbourg Photoredox Catalysis using a new Iridium Complex As an Efficient Toolbox for Radical, Cationic and Controlled Polymerizations under Soft Blue Lights.

Poster P17

Chloé LAURE Affiliation: Institut Charles Sadron - Strasbourg Synthesis and sequencing of sequence-coded poly(alkoxyamine-amide)s

Poster P18

Guillaume FIERS Affiliation: Institut Charles Sadron - Strasbourg Synthesis of Peptide Triazole Nucleic Acids via a chemoselective process

Poster P19

Noémi FEILLÉE Affiliation: Laboratoire de Photochimie et d'Ingéniérie - ENSCMu -UHA Photoinduced Cross-linking of Polydisulfides Elastomer Film via Thiol Monomer Air Oxidation

Poster P20 Rémi ROUQUETTE Affiliation: UDS-ISIS Water-dispersive Pt complexes-polymer nanoparticles hybrids for bio-imaging

Poster P21 陳寶玉 Delphine CHAN-SENG Affiliation: Institut Charles Sadron - Strasbourg Amino Acids-Containing Polymers

Poster P22

Niklas Felix KÖNIG Affiliation: Institut Charles Sadron - Strasbourg Monodisperse Sequence-Encoded Polymers: Writing & Reading Information

Poster P23 Christoph HUSSAL Affiliation: IBG - Karlsruhe Institute of Technology Synthesis of new functionalized pyridinophane-based surface coatings via chemical vapour deposition (CVD) polymerization

Poster P24

Géraldine LAYRAC Affiliation: Institut Charles Gerhardt , Montpellier Highly Stable Colloids of Layered Double Hydroxide: A Direct Aqueous Synthesis Route using Double Hydrophilic Block Copolymers

Poster P25 Mathias DESTARAC Affiliation: U. Toulouse Aqueous RAFT/MADIX polymerization of poly(vinylphosphonic acid)-based double hydrophilic block copolymers and Hybrid Polyion Complex Micellization ability

Poster P26 林小锋 Xiaofeng LIN Affiliation: Institut Charles Sadron - Strasbourg Toward Layer-by-Layer assembled nanofiltration membranes with high retention and permeabilty

Poster P27

Vincent LEMAIRE Affiliation: Institut Charles Sadron - Strasbourg Large Area Layer-by-Layer Assembly of Aligned Silver Nanowires for Transparent Conductive Films

Poster P28 Ufuk Saim GÜNAY Affiliation: Institut Charles Sadron - Strasbourg Triple Click Reaction Strategy to Design Well-Defined Macromolecular Structures

Poster P29 Pierre MULLER Affiliation: Institut Charles Sadron - Strasbourg Influence of the membrane charge on the binding affinity constant of Cell Penetrating Peptides

Poster P30 赵静文 Jingwen ZHAO Affiliation: ESPCI Dynamics and mechanics of a dual cross-link gel

Poster P31 Artak SHAHNAS Affiliation: Karlsruhe Institute of Technology Bioorthogonal synthetic strategies for polyvalent materials

Poster P32 Sahar RAHMANI Affiliation: Karlsruhe Institute of Technology (Lahann Group) Multifunctional Nanoparticles with Tunable Properties for Biomedical Applications

Poster P33 傅 立 Li FU Affiliation: Institut Charles Sadron - Strasbourg Shearing experiments of confined phospholipid layers characterized by Fluorescence Recovery After Patterned Photobleaching (FRAPP)

Poster P34 Thitima LIMPANICHPAKDEE Affiliation: SIMM Lab, ESPCI Synthesis and structure of Novel cocontinuous double network elastomers

Poster P35 Christophe SERRA Affiliation: Institut Charles Sadron - Strasbourg Microreaction Technology: a Tool for the Intensification of Atom Transfer Radical Polymerization Process

Poster P36 Vladimir KARDELIS Affiliation: UMR 7509 / Laboratoire de Chimie des Matériaux Moléculaires Post-Polymerization Cycloaddition of a Cyclooctyne-Containing Polyimine

Poster P37 郭辉 Hui GUO Affiliation: ESPCI Design of thermoassociating copolymers for aqueous-based formulations: role of topology on the macroscopic properties

Poster P38 Catalina BORDEIANU Affiliation: DMO-IPCMS Dendrimer-nanoparticle conjugates as Nanomedicine tools

Poster P39 黄瞳瞳 Tongtong HUANG Affiliation: Institut de Science des Matériaux de Mulhouse (IS2M) Long term stability of proteins in contact with solid surfaces

Poster P40 Gowthamy VENKIDASUBRAMONIAN Affiliation: Karlsruhe Institute of Technology

Controlled Radical Polymerization of Zwitterionic Monomers for Biomedical Applications

A theoretical approach to phase coexistence in ternary Cholesterol-phospholipid mixtures

J. Wolff 1, C.M. Marques1, F. Thalmann1

1Institut Charles Sadron, Université de Strasbourg, CNRS UPR 22, 23 rue du Loess, Strasbourg Cedex, F-67037, France. jean.wolff@ics-cnrs.unistra.fr

We first introduce a simple and predictive model for describing the phase stability of ternary Choles\-terol-phospholipid mixtures. Assuming that competition between the liquid and the gel phase of the phospholipids is the main driving force behind lipid segregation, we derive a phenomenological Gibbs free-energy of mixing, based on the calorimetric properties of the lipids main transition. Gibbs phase diagrams are numerically obtained that reproduce the most important experimental features of DPPC-DOPC-Chol membranes and of other ternary mixtures. Regions of triple coexistence and liquid ordered-liquid disordered segregation as well as the temperature behavior of this diagram are well described by our model. We also developing a Ginzburg-Landau description of spatial heterogeneities seeking a quantitative explanation for the outer domains line tension and for phenomena such as microscope domains nucleation.

J.Wolff, C.M. Marques, F. Thalmann, PRL 2011,106,128104.

P1

P1

Mixed systems to assist enzymatic ring opening polymerization of lactide stereoisomers

Stéphane Duchirona, Eric Polleta, Sébastien Givryb, Luc Avérousa a BioTeam/ICPEES-ECPM, UMR 7515, University of Strasbourg, 25 Rue Becquerel, 67087 Strasbourg, Cedex 2, France b OSIRIS/J.SOUFFLET S.A. Quai du Général Sarail, 10300 Nogent sur Seine, France Nowadays, metallic-based catalysis is the main way to obtain well-controlled polyesters such as polylactide (PLA). However these chemicals may induce some toxicity (which could be detrimental for e.g., biomedical applications), environmental pollution (in the case of e.g., compostability) and also increase the polymer degradation kinetics (which could limit the material use). Currently, enzymatic catalysis shows a great potential to substitute metal-based catalysts and to limit final toxicity, environmental impacts and abiotic degradation, in perfect agreement with a sustainable development and concepts of green chemistry. Enzymatic Ring Opening Polymerization (eROP) of lactones has been studied since 1993 [1] but still shows some limitations: kinetics is usually slow and only some monomers can be polymerized by this way. Most of the studies concern ε-caprolactone and the few ones on lactide often show inconsistent results. Some methods to improve the polymerization kinetics have been used, such as microemulsion or continuous flow reaction [2] or by using ionic liquid as solvent. However, the main investigations concerned the immobilization of proteins onto various supports (e.g. nanoclays, silicones or acrylic resins) to increase the enzyme stability and catalytic activity for polyester synthesis [3]. Regarding the lactide enzymatic polymerization, among all existing lipases, only a few of them were tested so far. The aim of this work is to select and analyze the potential of new enzymes to polymerize lactones and lactides and to find the corresponding optimized conditions of polymerization. For that, some of the aforementioned methods, such as copolymerization or enzymes immobilization on nanoclay, have been previously investigated [3] to improve enzymes efficiency particularly for the ROP of lactide isomers. We also developed a new approach of solvent-assisted activation of the monomers and the prepolymers. Hence, we improved the reactions kinetics and modified the macromolecular architectures such as molar mass of the resulting PLA. This poster will focus on the different approaches we used to biosynthesize PLA by eROP with an improvement in the biocatalysts efficiency for different new enzymes and commercial lipases. Effects of these biocatalytic syntheses on the corresponding macromolecular architectures have been analyzed. [1] Uyama, H.; Kobayashi, S.; Chem. Lett. 1993; p.1149-1150 [2] Kundu S., Bhangale A.S., Wallace W.E., Flynn K. M., Guttman C.M., Gross R.A., Beers K. L.; J. Am. Chem. Soc.; 2011; p.6006-6011 [3] Öztürk Düşkünkorur, H., Pollet, E., Phalip, V., Güvenilir, Y., Avérous, L.; Polymer (United Kingdom); 2014; p.1648-1655

P2

P2

A rheological study of vitrimers

Frank Snijkers1, Rossana Pasquino2, Alfonso Maffezzoli1

1 Department of Engineering for Innovation, Università degli Studi di Salento, Lecce, Italy 2 Department of Chemical, Materials and Industrial Engineering, Università degli Studi di Napoli Federico II, Napoli, Italy Epoxies and epoxy-based materials find applications as e.g. coatings, structural adhesives, and fiber-reinforced materials due to their combination of a high mechanical strength with a low density. Possible self-healing properties for such systems are of great technological interest. In a series of papers, prof. Leibler’s group1-3 presented an elegant method to modify epoxy materials based on mixtures of diglycidyl ether of bisphenol A and fatty acids by the addition of an appropriate catalyst for the reversible transesterification reaction between alcohol and ester groups. Strong, self-healing, and even more importantly, easy processable networks, termed “vitrimers”, were obtained, which can be readily prepared by mixing standard chemicals. In this work, a wider range of possible formulations of vitrimers is studied. They differ in their content of mono-, di- and tri-carboxyl fatty acids thereby controlling the number of links and hence strength of the final network. We present an experimental investigation of their curing behavior studied by rheometry and calorimetry to assess the activity of the catalyst at different cure temperatures. We further studied the linear dynamical properties of the cured vitrimers over a wide range of frequencies and temperatures. The terminal relaxation behavior could often not be reached in oscillatory tests and the frequency axis is extended by performing long-time creep and stress relaxation experiments. We observe strong, systematic variations of the relaxation time and moduli of the samples with formulation and we systematically observe a peculiar double relaxation. The variation of the moduli follows the expectations from standard rubber theory well, while the origin of the double relaxation remains elusive. 1 Montarnal et al., Science 2011, 334, 965 2 Capelot et al., ACS Macro Lett. 2012, 1, 789 3 Capelot et al., JACS 2012, 134, 7664

P3

P3

Photocatalyzed Cu-based ATRP involving an Oxidative Quenching

Mechanism under Visible Light

Qizhi Yang1, Frédéric Dumur2, Fabrice Morlet-Savary1, Julien Poly1*, Jacques Lalevée1

1 Institut de Science des Matériaux de Mulhouse (IS2M), UMR 7361 – CNRS/UHA, 15 rue Jean Starcky, 68057 Mulhouse, France, 2 Aix-Marseille Université, CNRS, ICR UMR7273, 13397 Marseille, Cedex 20, France.julien.poly@uha.fr) Cu-based catalyst (bis(1,10-phenanthroline) copper(I) (Cu(phen)2

+)) was used as a photocatalyst for ATRP due to its intense absorption in the visible domain (λmax., abs. = 440 nm). Under a very soft light irradiation (0.9 W household LED lamp, λmax., em. = 465 nm), the polymerization of methyl methacrylate (MMA) in dimethylformamide (DMF) was well controlled, using ethyl α-bromophenylacetate (EBPA) as the initiator. The PDI of the resulting polymers can be as low as 1.10, when 80 ppm of [Cu(phen)2]BF4 were used. The proposed mechanism implies light absorption by the activator Cu(I), resulting in the formation of an excited state Cu(I)* which can then react rapidly (Scheme 1). It is different from previous reports based on reductive quenching processes. Additionally, it was possible to complete the catalysis mechanism by adding triethylamine (TEA), which permitted a faster polymerization, thanks to a faster regeneration of the activator Cu(I). An excellent control over the polymerization was also observed in the presence of TEA, with PDI as low as 1.06. The addition of TEA allowed also using a catalyst loading as low as 20 ppm, while maintaining a good controllability1.

Scheme 1. Catalytic cycle proposed for the photocatalyzed ATRP of MMA involving Cu(phen)2+

(Cu(I)). The predominant quenching reaction occurs between dormant species PBr (initially EBPA) and the excited state Cu(phen)2

+* (Cu(I)*). A faster polymerization is observed in the presence of TEA as an additional amine permitting the faster regeneration of the activator (red part).

1. Yang, Q.; Dumur, F.; Morlet-Savary, F.; Poly, J.; Lalevée, J., Photocatalyzed Cu-Based ATRP Involving an Oxidative Quenching Mechanism under Visible Light. Macromolecules, 2015, 48, (7), 1972-1980.

Cu(I)

Cu(I)*

Cu(II)BrPBr P•

amine

amine•+

hν

P4

P4

One-pot synthesis of sub-3 nm gold nanoparticle networks connected

by thio-based multidentate fullerene adducts

Uwe Hahn1, Guillaume Rousseau2, Christophe Lavenn2, Luis Cardenas2, Stéphane

Loridant2, Y. Wang1, Aude Demessence2, Jean-François Nierengarten1

1 Laboratoire de Chimie des Matériaux Moléculaires (ECPM), UMR 7509, Université de Strasbourg, France. (u.hahn@unistra.fr; nierengarten@unistra.fr) 2 Institut de Recherches sur la Catalyse et l’Environnement de Lyon (IRCELYON), UMR 5256, Université Lyon 1, Villeurbanne (France). One of the biggest challenges in nanotechnology is to control the self-assembly of interconnected nanoparticles at the microscopic scale. Gold nanoparticles (GNPs) are among the most widely used nanomaterials due to their easy synthesis, great stability, low toxicity and promising applications in electronics, photonics, medicine and catalysis. Several studies have shown that fully organized GNPs with narrow size-dispersion can be obtained in self-assembled architectures incorporating macromolecules. All these studies reported so far involved large particles with a diameter above 5 nm. The assembly of GNPs with functionalized fullerene nodes through weak electrostatic interactions has also been done and led to particles larger than 8 nm. However, the preparation of 3D-networks incorporating smaller GNPs remains a challenge. This is particularly important for their future application in the field of catalysis. In this contribution, we will show that the use of a bulky organic 3D-linker, namely a C60-hexaadduct functionalized with twelve thiocyanate moieties is perfectly suited for the one-pot synthesis of hybrid materials where homogeneous sub-3 nm GNPs are connected through strong S-Au bonds 1. This association of ultra-small GNPs with a carbon-based organic linker in the network makes this kind of hybrid material promising as catalyst with potential synergetic effects between the two parts. By selecting well-designed organic linkers with the appropriated external functions and well-adapted synthesis, the formation of robust and organized 3D-networks of small nanoparticles should soon be possible. 1. G. Rousseau, C. Lavenn, L. Cardenas, S. Loridant, Y. Wang, U. Hahn, J.-F. Nierengarten, A. Demessence, One-pot synthesis of sub-3 nm gold nanoparticle networks connected by thio-based multidentate fullerene adducts, Chem. Commun. 2015, 6730-6733.

P5

P5

Polymers synthesized by RAFT as versatile macrophotoinitiators

Benjamin Cabannes-Boué, Fabrice Morlet-Savary, Jacques Lalevée, Julien Poly *

Institut des Sciences des Matériaux de Mulhouse (IS2M), UMR 7361 – CNRS/UHA, 15

rue Jean Starcky, 68057 Mulhouse, France. *julien.poly@uha.fr

An exploitation of the generally unwanted sensitivity to light of chain-end functions

in polymers synthesized by reversible addition-fragmentation chain transfer (RAFT)

is proposed. This reactivity can be purposely enhanced through the simple

introduction of a strongly absorbing chromophore on the terminal monomer unit. The

concept was validated on RAFT polymers with a xanthate chain-end function and a

terminal monomer unit derived from N-vinylcarbazole (NVC). 1

We demonstrate that

such compounds can be considered as efficient and versatile macrophotoinitiators,

being able to initiate both free radical and radical promoted cationic polymerizations

under UV irradiation (Scheme 1).

Beyond the purpose of this contribution, more directed towards potential applications,

RAFT polymers especially designed so as to enhance the photodissociation efficiency

of the chain-end functions appear very promising. This can be achieved by

introducing a chromophore, such as the carbazole group, either on the terminal

monomer unit or as the Z group in the thiocarbonylthio function. Both of them are

worth being deeply investigated regarding the new synthetic methodologies that they

can offer, especially for the synthesis of block copolymers.

Scheme 1. Photoinitiated radical and radical promoted polymerizations using RAFT polymers with a

terminal NVC monomer unit as macrophotoinitiators.

1. J. Poly, B. Cabannes-Boué, L. Hebinger, R. Mangin, A. Sauvage, P. Xiao, F. Morlet-Savary, J.

Lalevée, Polym. Chem., 2015, Vol 6, 5766-5772.

P6

P6

Synthesis and properties of bottlebrush-like xyloglucan

oligosaccharide-based glycopolymers with controlled composition

Jing Chen, Sami Halila

Centre de Recherchesur les MacromoléculesVégétales, CERMAV, CNRS UPR 5301,

CNRS and Joseph Fourier University, BP 53, 38041 Grenoble cedex 9, France (jing.chen@cermav.cnrs.fr)

We aim to develop a novel biosourced thermoswitchable material thanks to the

design of glycopolymers containing structurally well-defined xyloglucan oligosaccharide (XGO) side-chains. This material with tailored structures and tunable properties could be applied toward many advanced biomaterials, for example, the thermoswitchable surface with tunable wettability, permeability, adhesive, adsorptive, mechanical and optical properties.

The synthesis of XGO with tunable galactose residues is achived by controlled enzymatic depolymerization by cellulase and subsequentdegalactosylation by galactosidase. These modified XGOs are then modified as “clickable” azide-end groups (XGO-N3). Thanks to the CuAAC click reaction between XGO-N3 and alkyne-backbone polymer (poly(propargyl methacylate), PPMA), the bottlebrush-like glycopolymers are prepared. The structures and physicochemical properties are characterized.

General synthetic strategy adopted to obtain bottlebrush-like xyloglucan oligosaccharide-based

glycopolymers with controlled composition

The authors acknowledge the financial support from Institut Carnot PolyNat

P7

P7

Fluorescent brightener as photoinitiator for free radical

photopolymerizations under visible LED

Xiaoling Zuo1,2, Fabrice Morlet-Savary 1, Bernadette Graff 1, Nicolas Blanchard 3, Jean-phillipe Goddard 2, Jacques Lalevée 1

1 Institut de Science des Materiaux de Mulhouse IS2M, UMR CNRS 7361, UHA, Mulhouse. F. 2 Laboratory of Organic and Bioorganic Chemistry, University of Haute Alsace ENSCMu, Mulhouse .F. 3 Laboratoire de Chimie Moléculaire, Université de Strasbourg, UMR CNRS 7509, ECPM, Strasbourg, F.

The commercial fluorescent brightener, namely, triazinylstilbene fluorescent brighteners (TFB) appeared as an efficient high-performance photoinitiator with iodonium salt to form two-component photoinitiating system that could be employed for free radical polymerization FRP of acrylates (Ebecryl 605/TMPTA blend) under air applicable to visible LED at 420 nm. Remarkably, brightener/iodonium salt in the presence of the third additives (ethyl 4-(dimethylamino)benzoate or N-vinylcarbazole) behaved even higher efficiencies than this two-component system in some cased. The underlying photochemical mechanisms were investigated by electron spin resonance spin trapping techniques (ESR). The formations of aminoalkyl and phenyl radicals under near visible LED irradiation have been obtained using three photoreductive methods, which used fluorescent brightener as the photoreductant. Remarkably, the investigation of the photochemical mechanisms illustrated that the possibility of commercial fluorescent brightener for applications as efficient photosensitive systems upon visible LED. Especially the combination with the third additives, indeed, significantly improves the versatility of fluorescent brightener and the scope of free radical polymerizations.

P8

P8

Chemotaxis and Bioactivity in a New Class of Nanocomposite Hydrogel Systems

Federica Fiorinia, Eko Adi Prasetyantoa, Francesca Taraballib, Laura Pandolfib, Iván

López-Monteroc,d, Francisco Monroyc,d, Ennio Tasciottib and Luisa De Colaa

a Institut de Science et d'Ingénierie Supramoléculaires, University of Strasbourg, 8 rue Gaspard Monge, 67000 Strasbourg, France. federica.fiorini@etu.unistra.fr bDepartment of Nanomedicine, Houston Methodist Research Institute, 6670 Bertner Avenue, 77030 Houston, TX, United States. cDepartamento de Química Física I, Universidad Complutense, Ciudad Universitaria s/n, 28040 Madrid, Spain. dInstituto de Investigacion Hospital 12 de Octubre (i+12), Avda. de Cordoba s/n, 28041 Madrid, Spain. Herein, we report the synthesis of a novel nanocomposite hydrogel network composed of chemically cross-linked biocompatible polymer chains, such as polyamidoamines, together with porous nanomaterials (e.i. mesoporous silica nanoparticles). By building a dual hydrogel system, Concentric Cylinder hydrogel (CCH), we tested the ability of Stromal-Cell Derived Factor-1α (SDF-1α) filled porous silica-hydrogel to induce chemotaxis in vitro and were able to follow the migration of the seeded mesenchymal stem cells from the edges of the scaffold towards the inner core, upon local release of SDF-1α from the hydrogel core. The scaffold was then implanted into a subcutaneous dorsal pocket of mice to assess the possibility of a reduced inflammatory and fibrotic reaction and a possible increase of the wound healing process.

G.F. Muschler, C. Nakamoto, L.G. Griffith, J. Bone Joint Surg. Am. 2004, 86-A, 1541-58. V. Barron, A. Pandit Top. Tissue Eng. (Ed.: Eds. N. Ashammakhi & P. Ferretti), 2003. D. Seliktar Science 2012, 336, 1124–8. I. B. Copland, S. Lord-Dufour, J. Cuerquis et al. Stem Cells, 2009, 27, 467–477. P. Thevenot, A. Nair, J. Shen et al. Biomaterials, 2010, 31, 3997–4008.

Acknowledgements: We thank the European Research Council (ERC), grant no. 2009247365 titled “MaGIC”, for financial support and Université de Strasbourg. F.F. thanks the Houston Methodist Research Institute, Texas (USA) for financial support and for the opportunity to develop part of the project in this research center.

P9

P9

Orientation order in polyelectrolyte solutions

Philippe Lorchat1, Iuliia Konko1, Jérôme Combet1, Jacques Jestin2, Albert Johner1, André

Laschewski3, Sergei Obukhov4, Michel Rawiso1 1 Institut Charles Sadron (CNRS-UdS), Strasbourg, France. 2 Laboratoire Léon Brillouin, CEA-Saclay, France. 3 Fraunhofer Institut für Angewandte Polymerforschung, Postam, Germany. 4 Department of physics, University of Florida, Gainesville, FL, USA. michel.rawiso@ics-cnrs.unistra.fr The question was raised if an orientation order could be observed in semi-flexible polyelectrolyte solutions [1-3]. Combined small angle X-ray and neutron scattering experiments recently performed on dense solutions of highly charged polyelectrolytes allow replying to this issue. Specifically, they reveal the existence of a nematic local order at high concentration [4] preceded by a new regime [5], both depending on the intrinsic stiffness of the macroion and the ionic strength of the solution. Three polyelectrolytes of distinct intrinsic stiffness will be considered: sodium poly(styrene sulfonate) (NaPSS); poly(diallyldimethyl ammonium chloride) (PDADMAC), and sodium hyaluronate (NaHA). Their related non electrostatic persistence length and effective charge fraction are, respectively: lp = 10, 30 and 90 Å; feff = 0.33, 0.66 and 1. [1] de Gennes P.-G.; Pincus P.; Velasco R. M.; Brochard F., Remarks on polyelectrolyte conformation. J. Phys. (France) 1976, 37, 1461. [2] Nyrkova I. A.; Shusharina N. P.; Khoklov A. R., Liquid-crystalline ordering in solutions of polyelectrolytes. Macromol. Theory Simul. 1997, 6, 965. [3] Carri G. A.; Muthukumar M., Attractive interactions and phase transitions in solutions of similarly charged rod-like polyelectrolytes. J. Chem. Phys. 1999, 111, 1765. Gosh K.; Carri G. A.; Muthukumar M., Phase transitions in solutions of semiflexible polyelectrolytes. J. Chem. Phys. 2002, 116, 5299. [4] Onsager L., Effects of shape on the interaction of colloidal particles. Ann. N.Y. Acad. Sci. 1949, 51, 627. [5] Lorchat P.; Konko I.; Combet J.; Jestin J.; Johner A.; Laschewski A.; Obukhov S.; Rawiso M., New regime in polyelectrolyte solutions. EPL 2014, 106, 28003.

P10

P10

Self-organisation of dodeca-dendronized fullerene into

supramolecular discs and helical columns

Franck Schillinger,1 Sebastiano Guerra,2 Julien Iehl,1 Michel Holler,1 Mihai Peterca,3 Daniela A. Wilson,3 Benjamin E. Partridge,3 Shaodong Zhang,3 Robert Deschenaux,1

Virgil Percec,3 Jean-François Nierengarten1

1 Laboratoire de Chimie Moléculaires, Université de Strasbourg et CNRS (France). 2

Institut de Chimie, Université de Neuchâtel (Switzerland). 3 Department of Chemistry, University of Pennsylvania, Philadelphia (United States). Dendronized fullerenes are an attractive synthetic target for fundamental studies and practical applications.1 As part of this research, we now report the first example of a hexakis-adduct of C60 with self-assembling dendrons at every possible position, i.e. 12 dendrons per fullerene (compounds 1a-e). Intuitively, the quasi-spherical hard core of these molecules and an isotropic distribution of dendrons around their surface were expected to force these molecules to adopt a globular shape suitable for self-organisation into various cubic, tetragonal or quasicrystalline periodic and quasiperiodic arrays. Unexpectedly, regardless of this high degree of substitution of the C60 core, the fullerodendrimers reported herein self-organise into 2D columnar arrays, due to the dominating self-assembling ability of the peripheral dendrons.2

1. Hahn, U.; Vögtle, F.; Nierengarten, J.-F. Polymers 2012, 4, 501-538. 2. Guerra, S. et al., Chem. Sci. 2015, 6, 3393-3401.

P11

P11

Langmuir and Langmuir-Blodgett films from amphiphilic

pillar[5]arene-containing [2]rotaxanes

Iwona Nierengarten,1 Thi Minh Nguyet Trinh,1 Michel Holler,1 Jean-Louis Gallani,2

Jean-François Nierengarten1

1 Laboratoire de Chimie des Matériaux Moléculaires, Université de Strasbourg et CNRS (France). 2 IPCMS, Université de Strasbourg et CNRS (France). Amphiphilic pillar[5]arene-containing [2]rotaxanes (1a-b) have been prepared and fully characterized.1 In the particular case of the [2]rotaxane incorporating a 1,4-diethoxypillar[5]arene subunit (1a), the structure of the compound was confirmed by X-ray crystal structure analysis. Owing to a good hydrophilic/hydrophobic balance, stable Langmuir films have been obtained for these rotaxanes and the size of the peripheral alkyl chains on the pillar[5]arene subunit has a dramatic influence on the reversibility during compression-decompression cycles. Indeed, when these are small enough, molecular reorganization of the rotaxane by gliding motions are capable of preventing strong π-π interactions between neighbouring macrocycles in the thin film.

1. T. M. N. Trinh, I. Nierengarten, M. Holler, J.-L. Gallani, J.-F. Nierengarten, Chem. Eur. J.

2015, 21, 8019-8022.

P12

P12

Iodonium-Polyoxometalate and Thianthrenium-Polyoxometalate as New One- Component UV Photoinitiators for Radical and Cationic

Polymerization

Haifaa Mokbel1,4, Pu Xiao1, Corine Simonnet-Jégat2, Frederic Dumur3, Didier Gigmes3, Joumana Toufaily4, Tayssir Hamieh4, Jean Pierre Fouassier5, Jacques Lalevée1

1Institut de Science des Matériaux de Mulhouse IS2M, UMR CNRS 7361, UHA, 15, rue Jean Starcky, 68057 Mulhouse Cedex, France; 2Institut Lavoisier de Versailles, UMR CNRS 8180,

Université de Versailles-St Quentin, 45,Avenue des Etats-Unis, 78035, Versailles, France; 3Aix-Marseille Université, CNRS, Institut de Chimie Radicalaire, UMR 7273, F-13397 Marseille, France; 4Laboratoire de Matériaux, Catalyse, Environnement et Méthodes

Analytiques (MCEMA-CHAMSI), EDST, Université Libanaise, Campus Hariri, Hadath, Beyrouth, Liban; 5ENSCMu-UHA, 3 rue Alfred Werner, 68093 Mulhouse Cedex, France.

Novel onium salts (onium-polyoxometalates) have been synthesized and characterized1. They contain a diphenyliodonium or a thianthrenium (TH) moiety and a polyoxomolybdate or a polyoxotungstate. Polyoxometalates (POMs) are a unique class of inorganic anionic transition-metal oxide species with a wide variety of topologies and compositions2. We would like to explore the role of polyoxometalates (POMs) as counter anions in new onium salt series. Outstandingly, these counter anions are photochemically active and can sensitive the decomposition of the iodonium or TH moiety through an intramolecular electron transfer (Fig 1). The newly synthesized iodonium-POM or TH-POM can be used as an efficient one-component photoinitiator (PI) for the radical polymerization of an acrylate TMPTA, the cationic polymerization of an epoxide EPOX (or an divinylether monomer) upon a Xe-Hg lamp exposure. Interpenetrating polymer networks (IPN) can also be obtained under air through a concomitant cationic/radical photopolymerization of an epoxy/acrylate blend. Remarkably, these novel iodonium and TH salts are characterized by a higher reactivity compared with that of the diphenyliodonium hexafluorophosphate and the commercial TH salt, respectively. The photochemical mechanisms are studied by steady-state photolysis, cyclic voltammetry, and electron spin resonnance (ESR) techniques.

1. Mokbel, H.; Xiao, P.; Simonnet-Jégat, C.; Dumur, F.; Gigmes, D.; Toufaily, J.; Hamieh, T.; Fouassier, J-P.; J. Lalevée, Iodonium-Polyoxometalate and Thianthrenium-Polyoxometalate as New One-Component UV Photoinitiators for Radical and Cationic Polymerization. Journal of Polymer Science Part A: Polymer Chemestry 2015,53,(8), 981-989.

2. Hill, C-L.; Special issue for polyoxometalate. Chemical Reviews 1998, 98, (1), 1–390.

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Towards new photoinitiating systems for visible light: high performances systems with unusual bleaching properties

Mariem Bouzrati-Zerelli 1, Jacques Lalevée 1*, Fabrice Morlet-Savary 1, Céline

Dietlin 1, Bernadette Graff 1, Frédéric Dumur 2, Didier Gigmes 2 et Jean Pierre

Fouassier 1

1Institut de Science des Matériaux de Mulhouse IS2M, UMR CNRS 7361, UHA, 15, rue Jean Starcky, 68057 Mulhouse Cedex, Franc ; 2Aix-Marseille Université, CNRS, Institut de Chimie Radicalaire, UMR 7273, F-13397 Marseille, France. (Jacques.lalevée@uha.fr)

Radical photopolymerization of methacrylic networks has been investigated in presence of a new functionalized thiophen diketopyrrolopyrrole : the (2,5-bis[3-(dimethylamino)propyl]-3,6-bis(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4-dione (TDP). Combined with various additives such as iodonium salt (Iod), amine (EDB) or chlorotriazine (R-Cl)], reactive radicals can be generated from TDP, and then free radical polymerization of acrylates can be initiated. Upon violet (405nm), blue (470nm), green (532 nm) or even yellow (565 nm) light irradiations, the polymerizations were successful, both in laminate and under air, in thin or thick samples. The TDP based PISs are outperformed than the well known camphoquinone and refered systems. Furthermore, TDP exhibited a rarely remarkable property compared with dyes that have been tried before. It was completely bleached after polymerization, and that led to a transparent polymer film. Also, radical polymerization of methacrylate (HEMA, HEA) can be efficiently initiated in aqueous environment in the presence of TDP. This opens a new door for the photoinitiating radical polymerization which can be cared out in water. The photochemical mechanisms of the investigated dye were studied by steady-state photolysis, cyclic voltammetry, and electron spin resonnance (ESR) techniques.

1. Mariem Bouzrati-Zerelli, Jacques Lalevée, Fabrice Morlet-Savary, Céline Dietlin, Bernadette

Graff, Frédéric Dumur, Didier Gigmes et Jean Pierre Fouassier. A New Diketo Pyrrolo-Pyrrole

Photoinitiator for visible light: High performance system with unusual bleaching properties (under

preparation).

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Preparation of Pillar[5]arene-Based [2]Rotaxanes from Acyl

Chlorides and Amines

Eric Meichsner,1 Radian Milev,1 Alberto Lopez-Pacheco,1 Iwona Nierengarten,1 Thi

Minh Nguyet Trinh,1,2 Michel Holler,1 Robert Deschenaux,2 and Jean-François Nierengarten1

1 Laboratoire de Chimie Moléculaires, Université de Strasbourg et CNRS (France). 2

Institut de Chimie, Université de Neuchâtel (Switzerland). Pillar[n]arenes are readily available macrocyclic compounds recently discovered.1 Their host-guest chemistry has been already intensively investigated. Owing to the electron-rich nature of their constitutive aromatic subunits, pillar[5]arenes exhibit interesting host-guest properties with π-electron-poor aromatic guests such as viologen and imidazolium cations. Along with charge-transfer interactions occurring between the electron-rich cavity of pillar[5]arenes and π-electron-poor guest molecules, C-H⋅⋅⋅π interaction is also a driving force in the formation of inclusion complexes. Actually, simple alkyl-substituted guests are efficiently encapsulated in the cavity of pillar[5]arenes to generate pseudo-rotaxanes. Such host-guest complexes are indeed perfectly suited for the synthesis of [2]rotaxanes. As part of this research, we have shown that pillar[5]arene-based [2]rotaxanes can be prepared from the reaction of diacyl chloride reagents with various amine stoppers.2 The yield in [2]rotaxane is sensitive to the reaction conditions (solvent, stoichiometry) but also to structural and electronic factors. In particular, the nature of the starting amine reagent has a dramatic influence on the yields of [2]rotaxanes thus showing that the outcome of the reaction is not simply related to the binding constant of the diacyl chloride reagent with the pillar[5]arene. Indeed, the difference in yields must be related to the difference in affinity for the various mono-acylated intermediates. The yields of [2]rotaxane are also influenced by several structural factors such as the chain length of the bis-acyl chloride reagent or the size of the peripheral substituents of the pillar[5]arene building block. Finally, the preparation of [2]rotaxanes has been also investigated under our conditions starting from alkyldiamine reagents and acyl chloride stoppers.

1. T. Ogoshi et al., Chem. Commun. 2014, 50, 4776-4787. 2. R. Milev et al., Eur. J. Org. Chem. 2015, 479-485.

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Photoredox Catalysis using a new Iridium Complex As an Efficient Toolbox for Radical, Cationic and Controlled Polymerizations under Soft Blue

Lights.

Sofia Telitel 1, Frederic Dumur 2, Didier Gigmes 2, Bernadette Graff 1, Julien Poly 1, Fabrice

Morlet-Savary 1, Philippe Fioux,1 Jean-Pierre Fouassier3, Jacques Lalevée 1 1 Institut de Science des Matériaux de Mulhouse, UMR CNRS-UHA 7361, 15 rue Jean Starcky, 68057 Mulhouse Cedex, France (jacques.lalevee@uha.fr); 2 Aix-Marseille Université, CNRS, Institut de Chimie Radicalaire, UMR 7273, F-13397 Marseille, France ; 3

ENSCMu-UHA, 3 rue Alfred Werner, 68200 Mulhouse, France.

Ir(ppy)3

1 was used as new catalyst for controlled/living radical polymerization under light. In this subject a new iridium complex (nIr) was designed and investigated as a photoinitiator catalyst for radical and cationic polymerizations upon very soft irradiations (particularly visible light). A ring-opening polymerization (ROP) of an epox monomer was easily promoted through the interaction between nIr and an iodonium salt (Iod) upon light. In radical polymerization, a control of the methylmethacrylate polymerization (conducted under a 462 nm light) with 1.4-1.6 polydispersity was displayed2. Surface modifications was also easily carried out through surface re-initiation experiments i.e. the dormant species being reactivated by light in the presence of nIr; the polymer surfaces were analyzed by XPS. The chemical mechanisms were examined through laser flash photolysis, NMR, ESR and size exclusion chromatography experiments.

1. Fors, B. P.; Hawker, C. J.; Control of a Living Radical Polymerization of Methacrylates by Light.

Angewandte Chemie International Edition, 2012, 51, 8850-8853. 2. Telitel, S.; Dumur, F.; Telitel, S.; Soppera, O.; Lepeltier, M.; Guillaneuf, Y.; Poly, J.; Morlet-Savary,

F.; Fioux, P.; Fouassier, J.P.; Gigmes, D.; Lalevee, J.; Photoredox Catalysis using a new Iridium Complex As an Efficient Toolbox for Radical, Cationic and Controlled Polymerizations under Soft Blue Lights. Polymer Chemistry. 2015, 6, 613-624.

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Synthesis and sequencing of sequence-coded

poly(alkoxyamine-amide)s

Chloé Laure1, Raj Kumar Roy1, Laurence Charles2, Jean-François Lutz1

1 Precision Macromolecular Chemistry, Institut Charles Sadron, CNRS UPR 22, 23 rue du Loess, 67034 Strasbourg Cedex, France 2 SACS, Laboratoire Chimie de Provence, Avenue Escadrille Normandie Niémen, 13397 Marseille Cedex 20, France

Biopolymers such as DNA are able to store information. Using a control sequence of monomers, synthetic polymers can also potentially store information. In order to do so, two monomers can be intentionally defined as 0 and 1 bit.1 Theses monomers can be assembled into a coded sequence through a protecting group free approach on a solid support.2 In the present case, the synthesis of poly(alkoxyamine-amide)s is based on a chemoselective process, involving two building blocks that cannot react with themselves.3 One of the building blocks is a nitroxide which is used as a spacer. The other one is an anhydride, which is used as a coding unit, depending on it substituent. Finally, the decoding is performed by ESI-MS/MS.4 The C-ON bond is indeed thermolabile and allows the fragmentation of the polymer. Then, knowing the length of each segment, and thanks to specific lengths of chain ends, it is possible to decipher the code along the oligomer.

Furthermore, in order to accelerate the synthesis and to prepare longer sequences, the convergent synthesis of the poly(alkoxyamide amide)s was studied.5 Binary encoded oligomers were prepared by oligomer ligation. A library of oligomers containing all possible dyads 00, 01, 10 and 11 was prepared on Wang resin and used to construct longer oligomers, until 19 units.

1- H. Colquhoun, J.-F. Lutz, Nat Chem, 6, 455-456 (2014) 2- T.T. Trinh, C. Laure, J.-F. Lutz, Macromol. Chem. Phys., 216, 1498-1506 (2015) 3- R.K. Roy, A. Meszynska, C. Laure, L. Charles, C. Verchin, J.-F. Lutz, Nat. Commun., 6,7237 (2015) 4- L.Charles, C.Laure, J.-F. Lutz, and R.K. Roy, Macromolecules, 48, 4319–4328 (2015) 5- R. K. Roy, C. Laure, D. Fischer-Krauser, L. Charles, J.-F.Lutz, Chem.Commun. DOI : 10.1039/C5CC06646H (2015)

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Synthesis of Peptide Triazole Nucleic Acids via a chemoselective process

Guillaume Fiers1, Dalila Chouikhi1, Laurence Oswald1, Laurence Charles2, Jean-François Lutz1

1 Precision Macromolecular Chemistry, Institut Charles Sadron, CNRS UPR 22, 23 rue du Loess, 67034 Strasbourg Cedex, France 2 SACS, Laboratoire Chimie de Provence, Avenue Escadrille Normandie Niémen, 13397 Marseille Cedex 20, France

Control of monomers sequences in macromolecular chains plays a crucial role in biology.1,2 For example, the hereditary message is coded on DNA chains thanks to only four monomer units. For decades, several research groups have developed chemical methods to synthesize non-natural nucleic acids. In particular, peptide nucleic acids (PNA)3 and more generally xeno nucleic acids (XNA) have been highly investigated and exhibit great potential for many biological applications. However, the synthesis of such polymers is still difficult, due to the need for many coupling and deprotection steps.

In this context, a new orthogonal approach for the synthesis of XNA chains is studied. Promising results have already been published during the last few years in the domain of sequence-controlled polymers.1 In particular, chemoselective iterative approaches that allow to synthesize perfectly monodisperse polymers without the use of protecting groups have been developed.4

In the present study, the synthesis of peptide triazole nucleic acids (PTzNA) is based on an AB+CD chemoselective iterative process on a solid support5 involving two different building blocks (AB and CD) that are not able to react with themselves. One of the building blocks carries an amine (A) and an alkyne (B) function whereas the other one carries a carboxylic acid (C) and an azide (D) function, resulting in two different coupling reactions that lead to the formation of an amide and a triazole. 1. Lutz, J.-F.; Ouchi, M.; Liu, D. R.; Sawamoto, M. Science 2013, 341 (6146), 1238149–1238149. 2. Lutz, J.-F. Nat Chem 2010, 2 (2), 84–85. 3. Nielsen, P. E.; Egholm, M.; Berg, R. H.; Buchardt, O. Science 1991, 254 (5037), 1497–1500. 4. Trinh, T. T.; Laure, C.; Lutz, J.-F. Macromol. Chem. Phys. 2015, 216 (14), 1498–1506. 5. Merrifield, R. B. Angew. Chem. Int. Ed. Engl. 1985, 24 (10), 799–810.

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Photoinduced Cross-linking of Polydisulfides Elastomer Film

via Thiol Monomer Air Oxidation

Noémi Feillée1, Abraham Chemtob1, Christian Ley1,

Céline Croutxé-Barghorn1, Xavier Allonas1

1Laboratory of Macromolecular Photochemistry and Engineering, University of Haute-Alsace, Mulhouse, F. (noemi.feillee@uha.fr) Containing repeated reversible covalent bond, dynamic polymers are able to reorganize structure and constitution on demand and thus have gain high interest in the last decades. One of the most intriguing and versatile examples of dynamic covalent bonds is the disulfide bond. Its bond reversibility can be activated by different stimuli, like redox species, thiol nucleophiles or UV light, making this polymer a very good candidate for adaptability and degradability1. While many studies address disulfides as monomeric compounds, there are few studies on the synthesis of poly(disulfide)s2. Recently, we have developed a novel photobase-catalyzed oxidative polymerization of multifunctional thiols to poly(disulfide) network3. This single-step UV process relies on air oxidation at ambient temperature, thus obviating the need for an external chemical oxidant to be incorporated in the resin.

The UV-mediated oxidation of a 1-µm thick film occurs in a matter of minutes both selectively, i.e. without over-oxidation, and quantitatively as assessed by a range of spectroscopic techniques. It also enables spatial and temporal control of the crosslinking, which can be exploited in photolithography applications and protein micro-patterning. These polymers also open great prospect toward recycling because the reductive cleavage of S-S bridges allows the recovery of the initial thiol groups. 1. Bang, E.; Lista, M.; Sforazzini, G.; Sakai, N.; Matile, S., Poly(disulfide)s. Chemical Science 2012, 3. (6), 1752-1763. 2. Rosenthal E.; Puskas J.; Wesdemiotis C., Green Polymer Chemistry: Living Dithiol Polymerization via Cyclic Intermediates. Biomacromolecules 2011, 13, (1), 154-164. 3. Feillée N.; Chemtob A.; Ley C.; Croutxé-Barghorn C.; Allonas X.; Ponche A.; Le Nouen D.; Majjad H.; Jacomine L., Photoinduced Cross-linking of Dynamic Poly(disulfide) Films via Thiol Oxidative Coupling. Macromolecular Rapid Communications (Accepted)

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Water-dispersive Pt complexes-polymer nanoparticles hybrids for bio-imaging

Rémi Rouquette1, Matteo Mauro1, Luisa De Cola1,2 The encapsulation of luminescent Pt complexes using poly (methylmethacrylate)-co-poly(methylacrylic acid) (pMMA-co-pMAA), poly(ethylene glycol) methyl ether-block-poly(D,L lactide) (PEG-b-pDLLA) by simple “flash-injection” technique is described and the resulting hybrids characterized by means of different techniques. The preparation and purification of two hydrophobic Pt complexes, followed by formation of nanoparticles of polymers in water has also been achieved. The resulting water-dispersible polymeric nanoparticles with either entrapped Pt complexes or self-aggregated Pt complexes showed emission wavelength, photoluminescence quantum yield (PLQY) and excited state lifetimes which depends on the Pt/polymer ratio and the concentration of Pt complexes. Controlling the different parameters of the flash-injection technique allows a full control of the photophysical properties of the different solutions. The size and morphology of these loaded nanoparticles have been studied by scanning electron microscopy (SEM), scanning transmission electron microscopy (STEM) and dynamic light scattering (DLS). The preliminary experiments of the separations of loaded nanoparticles from empty nanoparticles have been performed by analytical ultracentrifugation and density gradient centrifugation. These luminescent polymeric nanoparticles made by the biocompatible polymers pMMA-co-pMAA and PEG-b-pDLLA encapsulating the platinum complexes showed particle size in the range 30–2125 nm in diameter and they have been preliminarily applied in luminescence bio-imaging upon cellular uptake. 1. Laboratoire de chimie et des biomatériaux supramoléculaires, 8 rue Gaspard Monge, 67000 Strasbourg, France. 2. Institute of Nanotechnology and Karlsruhe Nano Micro Facility, Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz Platz 1, 76344, Eggenstein-Leopoldshafen, Germany

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Amino Acids-Containing Polymers

Romain Tavernier, Pauline Ernst, Jean-François Lutz, Delphine Chan-Seng

Institut Charles Sadron, CNRS-UPR22, 23 rue du Loess, 67034 Strasbourg, France. (delphine.chan-seng@ics-cnrs.unistra.fr) The development of synthetic macromolecules adapted to the specific needs of targeted applications is necessary to obtain materials with higher performances. In this perspective the progresses in the control of the topology, functionality and microstructure of polymers offer the ability to tune their structure according to the requirements of the desired materials. We propose here the use of amino acids as a tool to control the architecture of polymers employing them either as elements of a peptide sequence relevant for a specific biomedical application or as an element permitting to insert further functionalities on the polymer in a controlled manner. Synthetic strategies have been identified to introduce amino acids either on the main chain1 or on the side chains of the backbone of polymers. These strategies mostly rely on solid-phase synthesis through an iterative approach from a chlorotrityl chloride resin as depicted below for the iterative synthesis of oligomers based on amino acids and synthetic building blocks allowing the insertion of amino acids along the main chain of the polymer backbone. These strategies will be described and illustrated by examples in this presentation.

1. (a) D. Chan-Seng, J.-F. Lutz. “Primary structure control of oligomers based on natural and synthetic building blocks” ACS Macro Lett. 2014, 3, 291; (b) D. Chan-Seng, J.-F. Lutz. “Solid-phase synthesis as a tool for the preparation of sequence-defined oligomers based on natural amino acids and synthetic building blocks” ACS Symp. Ser. 2014, 1170, 103

cleavage N3HOOCClCl

HO RS

ON3RN

NH(Fmoc)HO

O

NH2

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Monodisperse Sequence-Encoded Polymers:

Writing & Reading Information

Abdelaziz Al Ouahabi1, Niklas Felix König1, Mitsuharu Kotera2, Laurence Charles3, and Jean-François Lutz1

1 Precision Macromolecular Chemistry, Institut Charles Sadron, CNRS UPR-22, 23 rue du Loess, 67034 Strasbourg Cedex 2, France jflutz@unistra.fr 2 Laboratoire de Conception et Application de Molécules Bioactives, V-SAT Group, UMR 7199 CNRS, Université de Strasbourg, Faculté de Pharmacie, 74 route du Rhin, 67401 Illkirch Cedex, France 3 Aix-Marseille Université – CNRS, UMR 7273, Institute of Radical Chemistry, 13397 Marseille Cedex 20, France Information storage capacity will be a new application for sequence-controlled polymers.1,2,3 In this concept, monomers defined as 0-bits and 1-bits are the building blocks for ‘writing’ binary codes. Molecular storage of information requires fast and precise synthesis of defined sequences in the writing-step as solely a complete decoding meets the demands for enabling afterward ‘reading’ the information. A protocol for automated synthesis has been developed paving the way for obtaining monodisperse copolymers with chain length above DP100 within a few hours. During the synthesis on a commercial DNA synthesizer controlled pore glass (CPG) serves as the solid support. Iterative phosphoramidite coupling steps with two different monomers allow us to store a 13-byte package of information in a defined polyphosphate sequence.4 Tandem mass spectrometry (MS/MS) can be applied as a sequencing technology, thus providing a convenient read-out to complete the inspiring proof-of-concept.5 Moreover, designing suitable monomers enables post-modification of the sequence-encoded polyphosphate. Hence, alkyne-azide coupling is employed to bypass complex functional monomers. Following this concept can dramatically facilitate the tuning of diverse polymer properties that will be desired in potential future aplications.6 1) J.-F. Lutz, Macromolecules 2015, 48, 4759. 2) H. Colquhoun, J.-F. Lutz, Nat. Chem. 2014, 6, 455. 3) R. K. Roy, A. Meszynska1, C. Laure, L. Charles, C. Verchin, J.-F. Lutz, Nat Commun 2015, 6. 4) A. Al Ouahabi, M. Kotera, L. Charles, J.-F. Lutz, ACS Macro Lett. 2015, 4, 1077. 5) L. Charles et al., manuscript in preparation. 6) A. Al Ouahabi, L. Charles, J.-F. Lutz, J. Am. Chem. Soc. 2015, 137, 5629.

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Synthesis of new functionalized pyridinophane-based surface coatings via chemical vapour deposition (CVD) polymerization

Christoph Hussal1, Florence Bally-Le Gall1, Joshua Kramer2, Stefan Braese2 and

Joerg Lahann1

1Institute of Functional Interfaces, Karlsruhe Institute of Technology, Germany. 2Institute of Organic Chemistry, Karlsruhe Institute of Technology, Germany.

Reactive polymer coatings are of major interest for many applications, including fields like biotechnology and catalysis.1 However, strategies taking advantage of Chemical Vapor Deposition (CVD) of reactive coatings is almost completely limited to entirely carbon-based polymer backbone (p-xylylene units)2 and only few examples of surface polymers of these heterophanes, first synthesized around 40 years ago,3 are known (Scheme 1).4 The presence of an electron donor heteroatom and appropriate substituents drastically increases potential applications of the coatings.

FG

CVD

Pyrolyse: 500- 800 °C Depostion: r.t. Pressure: < 0.2 mbar

FGm

n

FG (functional groups) = Hal, COR, CHO, CH2OH, CH2NH2

Scheme 1: Synthesis of functional poly(p-xylylene) coatings via CVD polymerization.

One reason for the very few examples of pyridinophane derivatives is the demanding synthesis of the scaffold. Therefore, a modified synthesis route for the pyridinophane scaffold from BRAESE et. al. was used starting from commercially available pyridine-2,5-dicarboxylic acid.5

Herein, we show new synthesis approaches for functionalized pyridinophanes, like aldehydes or halogens, as well as polymerization of un- and functionalized pyridinophane derivatives via CVD process to fabricate new reactive hetero-copolymer-based coatings.

The synthesis of halogen-substituted pyridinophane and its polymerization enables the production of a polymer that can undergo subsequent post-functionalization reactions, e.g. transition-metal cross-coupling reactions. IRRAS and XPS are used to characterize the functional coatings. 1. J. H. Scofield, J. Electron Spectr. Relat. Phen., 1976, 8, 129. 2. H. Y. Chen, J. Lahann, Langmuir, 2011, 27, 34. 3. J. Bruhin, W. Jenny, Chimia, 1972, 26, 420. 4. T. Itoh, T. Iwasaki, M. Kubo, S. Iwatsuki, Polymer Bulletin, 1995, 35, 307. 5. J. Kramer, M. Nieger, S. Bräse, Eur. J. Org. Chem., 2013, 3, 541.

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Highly Stable Colloids of Layered Double Hydroxide: A Direct

Aqueous Synthesis Route using Double Hydrophilic Block

Copolymers

Géraldine Layrac1, Simon Harrisson2, Mathias Destarac2, Corine Gérardin1, Didier Tichit1 , ,

1 “ Matériaux Avancés pour la Catalyse et la Santé “, Institut Charles Gerhardt UMR 5253, Montpellier, France. geraldine.layrac@enscm.fr 2 “ Polymères de Précision par Procédés Radicalaires ”, Laboratoire IMRCP UMR 5623, Toulouse, France. Aqueous suspensions of highly stable Mg/Al layered double hydroxide (LDH) nanoparticles were obtained via a direct and fully colloidal route using asymmetric poly(acrylic acid)-b-poly(acrylamide) (PAA-b-PAM) double hydrophilic block copolymers (DHBCs) as growth and stabilizing agents1. This DHBC was prepared according to a well-established sequential polymerization of acrylic acid and acrylamide performed in aqueous medium in the presence of a xanthate RAFT/ MADIX transfer agent. We showed that hybrid polyion complex (HPIC) micelles constituted almost entirely of Al3+ were first formed when mixing solutions of Mg2+ and Al3+ cations and PAA3000-b-PAM10000 due to the preferential complexation of the trivalent cations. Then mineralization performed by progressive hydroxylation with NaOH transformed the simple DHBC/Al3+ HPIC micelles into DHBC/aluminum hydroxide colloids, in which Mg2+ ions were progressively introduced upon further hydroxylation leading to the Mg−Al LDH phase. The whole process of LDH formation occurred then within the confined environment of the aqueous complex colloids. The complexation degree (R) (R = AA/(Mg + Al)) is a major parameter controlling the colloidal stability of the suspension. It also controlled the hydrodynamic diameter of the DHBC/LDH colloids which decreased from 530 nm down to 60 nm and the growth of the LDH phase with mean size of the particles in the range of 20-50 nm when R increased. Moreover, the asymmetry degree of the DHBC has been varied contributing to tailor the size and the stability of the colloids. LDH colloids have interesting properties for biomedical applications and they could be used as colloidal drug delivery systems, especially for water-soluble negatively charged drugs. 1. Géraldine Layrac, Mathias Destarac, Corine Gérardin and Didier Tichit, Highly Stable Layered Double Hydroxide Colloids: A Direct Aqueous Synthesis Route from Hybrid Polyion Complex Micelles., Langmuir 2014, 30, 9663.

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Aqueous RAFT/MADIX polymerization of poly(vinylphosphonic

acid)-based double hydrophilic block copolymers and

Hybrid Polyion Complex Micellization ability

Géraldine Layrac1, Corine Gérardin1, Didier Tichit1, Simon Harrisson2, Mathias Destarac2

1 “ Matériaux Avancés pour la Catalyse et la Santé “, Institut Charles Gerhardt UMR 5253, Montpellier, France. geraldine.layrac@enscm.fr 2 “ Polymères de Précision par Procédés Radicalaires ”, Laboratoire IMRCP UMR 5623, Toulouse, France. Double-hydrophilic block copolymers (DHBC) containing neutral polyacrylamide (Pam) and ionizable poly(vinylphosphonic acid) (PVPA) blocks were directly synthesized by quantitative chain extension of a polyacrylamide macroxanthate with vinyl phosphonic acid. PAm-b-PVPA block copolymers of different molecular weights from about 5500 to 11400 g.mol-1 were prepared1. The final conversion is about 40 % which leads to an additional purification step. We have shown by 31P NMR and SEC that the purification by precipitation in methanol was successfully performed and therefore the VPA residual monomer is less than of 1%wt. Additionally, the formation of hybrid polyion complex (HPIC) micelles was investigated at low pH with divalent transition metal ions with an emphasis on the comparison with poly(acrylic acid)-based DHBC1. The tendency to form HPIC micelles as a function of the poly(vinylphosphonic acid) block length was as follows Ni2+, Co2+ < Mn2+ < Cu2+ > Zn2+; it did not follow the charge to size ratio of cations or the Irving-Williams series, but was similar to the order obtained with phosphonate-bearing nucleotides and nucleic acids. The ability to form HPIC micelles was higher with poly(vinylphosphonic acid)-based than poly(acrylic acid)-based polymers in accordance with the higher basicity of the phosphonate group. 1. Géraldine Layrac, Corine Gérardin, Didier Tichit, Simon Harrisson and Mathias Destarac ,Hybrid polyion complex micelles from poly(vinylphosphonic acid)-based double hydrophilic block copolymers and divalent transition metal ions., Polymer, 2015, 72, 292-300

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Toward Layer-by-Layer assembled nanofiltration membranes with high retention and permeabilty

Xiaofeng LIN1,2, Paul ROUSTER1,2, Remi MERINDOL1,2, Oliver FELIX1, Christian GAUTHIER1,2, Gero DECHER1,2

1 Institut Charles Sadron, Strasbourg, France 2Université de Strasbourg, Strasbourg, France The development of novel and efficient membrane-based separation technologies requires new membrane designs based on new materials with improved performance. In conventional thin-film composite membranes a porous polymeric layer for high permeability and a very thin selective polymeric top layer are combined for optimum membrane performance. However, a major problem in membrane research is that selectivity and throughput are inversely proportional: separation membranes with high selectivity generally show low flux. Twenty-five years ago, our group has developed the Layer-by-Layer (LbL) technique,1 which is a powerful method for surface modification and preparation of composite membranes with nanoscale precision.2,3

Figure 1. (left) Representation of a nanofiltration membrane made of dense separation layer deposited on top of an intermediate layer composed of CNT. (middle) Typical stress-strain curve of a MFC-based LbL film. (right) Permeability and retention of LbL assembled nanofiltration membranes with (red and blue points) and without a CNT-based intermediate layer as function of number of layer pairs. Here, the LbL technique was used to develop nanofiltration membranes where a dense separation layer has been deposited on an intermediate layer to provide membrane reinforcement and high flux and not directly on the porous polymeric membrane (Figure 1, left). The fabrication of the intermediate layer containing carbon nanotubes (CNT) and/or micro-fibrillated cellulose (MFC) as reinforcing agent using various deposition methods (dipping and spin-assisted assembly) is presented. It is shown that this intermediate LbL films have extremely high mechanical strength (up to 450 MPa) comparable to steel (Figure 1, middle). In addition, nanofiltration membrane made with this intermediate layer showed much higher permeability while keeping similar retention compared to the membrane with only polyelectrolyte multilayers (Figure 1, right). 1. Decher G. et al., Science 277 (1997), p. 1232. 2. M. L. Bruening, Polymeric Materials: Science and Engineering 85 (2001), p. 525. 3. B. Tieke, Advanced Materials 3 (1991), p. 532.

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Large Area Layer-by-Layer Assembly of Aligned Silver Nanowires

for Transparent Conductive Films

Vincent Lemaire1, Matthias Pauly1, Gero Decher1 1 Institut Charles Sadron Strasbourg, France.

Thin films that combine high electrical conductivity and high optical transparency are

crucial for the development of many devices such as touch panels, e-papers, organic light-emitting diodes (OLEDs), liquid-crystal displays (LCDs), and solar cells. Most transparent conductive thin films nowadays rely on vacuum processes and transparent conductive oxides (TCOs) such as indium tin oxide (ITO). The next generation of optoelectronic devices will require conductive electrodes that are flexible, cheap and compatible with large-scale manufacturing methods, and silver nanowire thin films appear as a promising candidate. Furthermore, it has been recently demonstrated that aligned single nanowire mesh-like nanostructured films had superior performances compared to a random network of nanowires1. Several methods have been designed to control the orientation of silver nanowires2 in order to fabricate well-defined nanostructures with controlled architecture, which is a key requirement for thin films with versatile and tunable optoelectronic properties.

Scheme of grazing incidence spraying technique (on the left), Scanning Electron Microscopy pictures of six layers of silver nanowires oriented on the same direction.

In this report, a novel technique recently developed for the oriented self-assembly of silver nanowires will be presented3. Indeed, grazing incidence spraying, which consists in the low-angle spray deposition of a stable suspension of anisotropic nanoparticles, leads to the formation of a monolayer thin film homogeneous over large areas with all rod-like particles pointing in-plane towards the same direction (see Figure). Furthermore, the Layer-by-Layer technique4 is used to build multilayer thin films in which each layer’s architecture and orientation can be controlled independently. Based on optical spectroscopy and conductivity measurements, physical properties will be detailed depending on the thin film architecture and on the nanowire length, density and orientation within each layer. 1 O. Trotsenko, A. Tokarev, A. Gruzd, T. Enright, S. Minko, Nanoscale 2015, 7, 7155-7161. 2 L. Daniel, G. Gaël, M. Céline, C. Caroline,S. Jean-Pierre, Nanotechnol. 2013, 24, 452001. 3 H. Hu, M. Pauly, O. Felix, G. Decher, submitted 2015. 4 G. Decher, Science 1997, 277, 1232-1237

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Triple Click Reaction Strategy to Design Well-Defined

Macromolecular Structures

Ufuk Saim Gunay1,2, Hakan Durmaz1, Gurkan Hizal1, Umit Tunca1

1 Department of Chemistry, Istanbul Technical University, Istanbul, Turkey 2 Precision Macromolecular Chemistry Group, Institut Charles Sadron, Strasbourg, France gunayuf@itu.edu.tr The term `Triple Click Reaction` has been discussed in a recent article1. The concept is based on the utilization of three chemically and mechanistically different click reactions to design and synthesis of macromolecules with well-defined topology and chemical composition, and also precise molecular weight and narrow molecular weight distribution. In parallel with this strategy, a combination of triple click reactions, Copper-Catalyzed Azide-Alkyne Cycloaddition, Diels-Alder and Nitroxide Radical Coupling (NRC) was used to design and synthesis of well-defined macromolecular structures. A multifunctional organic structure, containing bromide, anthracene and alkyne functionalities was used as a core and this core was modified by triple click reactions to obtain 3-miktoarm star terpolymers2, V-shaped graft copolymers3 and H-shaped terpolymers. The precursors and the resultant polymers were characterized by 1H-NMR and GPC. 1. Tunca, U., Triple Click Reaction Strategy for Macromolecular Diversity. Macromolecular Rapid Communications 2013, 34, 38-46. 2. Gunay, U. S.; Durmaz, H.; Gungor, E.; Dag, A.; Hizal, G.; Tunca, U., 3-Miktoarm Star Terpolymers Using Triple Click Reactions: Diels–Alder, Copper-Catalyzed Azide-Alkyne Cycloaddition, and Nitroxide Radical Coupling Reactions. J. Polym. Sci. Part:A Polym. Chem. 2012, 50, 729-735. 3. Gunay, U. S.; Ozsoy, B.; Durmaz, H.; Hizal, G.; Tunca, U., V-Shaped Graft Copolymers via Triple Click Reactions: Diels–Alder, Copper-Catalyzed Azide–Alkyne Cycloaddition, and Nitroxide Radical Coupling. J. Polym. Sci. Part:A Polym. Chem. 2013, 51, 4667-4674.

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Influence of the membrane charge on the binding affinity constant

of Cell Penetrating Peptides

Vivien Walter, Andreas Weinberger, Pierre Muller, Andre Schroder, Tatiana Schmatko and Carlos Marques

Institut Charles Sadron, CNRS UPR 22 et Université de Strasbourg, 23 rue du loess, BP 84047, 67034 Strasbourg cedex2. Cell-penetrating peptide (CPP) sequences, such as oligo-arginine (ArgX) or TAT (a characteristic sequence of HIV virus), are most valuable tools for cellular delivery of cargo molecules. CPPs bind to plasma membranes, as a first step that leads to further stages of energy-driven processes, enhancing penetration through the cell natural barrier. However, attachment of a cargo to the CPPs invariably reduces or suppresses both cell penetration and membrane adhesion efficiency. We have recently shown that CPP binding to giant unilamellar vesicles, a simple model of the cell membrane, can be recovered by designing cargo molecules made of diblock Elastin-like Polypeptides (ELP) which self-assemble into spherical micelles at a well defined critical micellization temperature (CMT). In this work, based on a careful quantitative fluorescence analysis of the CPP adhesion to the membrane, we investigate the role of the membrane charge, temperature and peptide concentration on the binding efficiency of various ELP-based CPPs and show how they influence the affinity constant of peptides for the membrane.

Images of giant unilamellar vesicles in a solution containing fluorescently labeled ELPs. (A) at 25°C, below the CMT, ELP-based CPPs do not bind. (B) at 40°C, above the CMT, analysis of intensity profile enables quantitative measurement of adsorption amount per unit area.

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Dynamics and mechanics of a dual cross-link gel

Jingwen Zhao, Tetsuharu Narita, Costantino Creton

Laboratory of Soft Matter Science and Engineering, ESPCI ParisTech, Paris, F. (Jingwen.zhao@espci.fr) Self-healing dual cross-link poly(vinyl alcohol) (PVA) hydrogels can be synthesized by incorporating transient physical cross-links (borate ion) in a chemically crosslinked gel network. Previously the stress-strain relationship of their linear tensile properties was studied over a wide range of extension ratios and strain rates1, based on which we proposed a new analysis method to separate the stress into strain- and time- dependent terms. The connection between rate dependent mechanical behavior and kinetics of breaking and reattachment of temporary cross-links was quantified using a three-dimensional finite strain constitutive model. Reattachment of the chains contributes significantly to the overall stress of the dual cross-link gel and was described accurately in our model: the rate of healing is much faster than the rate of breaking. Here we report the linear viscoelastic properties of the hydrogels by oscillatory shear measurements in order to study quantitatively the breaking and healing dynamics experimentally. The storage and loss modulus obey the time temperature superposition principle, and the apparent activation energy and cross-linking enthalphy were calculated. The value of the breaking time is 20 times larger than the healing time, confirming the prediction by the constitutive model analysis. 1. Mayumi, K.; Marcellan, A.; Ducouret, G.; Creton, C.; Narita, T. ACS Macro Letters (2013) 2, 1065.

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Bioorthogonal synthetic strategies for polyvalent materials Artak Shahnas, Sahar Rahmani, Manuel Tsotsalas, Christof Woell, and Joerg Lahann

Institute of Functional Interfaces, Karlsruhe Institute of Technology, Germany. The production of materials with well-defined composition and reactive anchor groups is an important requirement of modern biotechnology, especially in the area of materials science.1 The number of functional groups, or the related ligations, are often limited in the biological field due to their required adherence to physiological and/or biological conditions in which the reactions can take place.2 As a result, only the most efficient chemical methods, usually "click chemistries", may be considered as ideal systems. Additionally, in many cases the selective immobilization of more than one active agent to the material should be carried out, where two or more orthogonal reactions are necessary, which further restricts the number of possible conjugation routes. In terms of materials, the anchor groups need to be conjugated to biocompatible/biodegradable polymers (such as polyethylene glycols (PEG) or polylactide-co-glycolide (PLGA)) because they generate little immune response and thus are optimal structures for biological applications (such as drug delivery, tissue engineering, and coatings). Previously, the Lahann Lab has developed the fabrication of multicompartmental, biodegradable nanoparticles that can be used for biomedical applications using electrohydrodynamic co-jetting.3 While this technique allows for the optimization of the shape, size, surface patches, and drug loading of these nanoparticles, the addition of reactive anchor groups that allow for the precise immobilization of multiple targeting, stealth, and therapeutic ligands on the same surface can be improved upon.4-5 Herein, we demonstrate several approaches for the functionalization of materials through the use of different heteromultifunctional linkers based on 2,2-Bis(hydroxymethyl) propionic acids. These linkers contain various bioorthogonal groups, such as azides (CuAAC), aldehydes (hydrazide coupling), and alkenes (thiol-en), allowing for multiple, yet orthogonal immobilization of ligands to the same surface, which can enhance our ability to fabricate materials that better interact with biological systems. References: 1. Zou, H.; Wang, Z.; Feng, M., Nanocarriers with tunable surface properties to unblock bottlenecks in systemic drug and gene delivery. J Control Release 2015, 214, 121-33. 2. Sun, T.; Zhang, Y. S.; Pang, B.; Hyun, D. C.; Yang, M.; Xia, Y., Engineered nanoparticles for drug delivery in cancer therapy. Angew Chem Int Ed Engl 2014, 53 (46), 12320-64. 3. Roh, K. H.; Martin, D. C.; Lahann, J., Biphasic Janus particles with nanoscale anisotropy. Nat Mater 2005, 4 (10), 759-63. 4. Bhaskar, S.; Pollock, K. M.; Yoshida, M.; Lahann, J., Towards designer microparticles: simultaneous control of anisotropy, shape, and size. Small 2010, 6 (3), 404-11. 5. Rahmani, S.; Saha, S.; Durmaz, H.; Donini, A.; Misra, A. C.; Yoon, J.; Lahann, J., Chemically orthogonal three-patch microparticles. Angew Chem Int Ed Engl 2014, 53 (9), 2332-8.

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Multifunctional Nanoparticles with Tunable Properties for Biomedical Applications

Sahar Rahmani1-2, Artak Shahnas1, Carlos Villa3, Chris Yu2, Sampa Saha4, Hakan Durmaz4,

Acacia Dishman5, Vladimir Muzykantov3, and Joerg Lahann1-2, 4 1Institute of Functional Interfaces, Karlsruhe Institute of Technology, Karlsruhe, Germany 2Biomedical Engineering Department, University of Michigan, Ann Arbor, MI, USA 3Department of Pharmacology, University of Pennsylvania, Philadelphia, PA, USA 4Chemical Engineering Department, University of Michigan, Ann Arbor, MI, USA 5Biophysics Department, University of Michigan, Ann Arbor, MI, USA Contact Information of Presenter: sahar.rahmani@kit.edu In nature, the hierarchical organization of material has led to the creation of unique entities that range from individual cellular components to entire organisms. Within a single mammalian cell, for example, the distinctive compartmentalization of chemical and biological functions in separate organelles has resulted in the evolution and development of eukaryotic cells in comparison to less advanced prokaryotic life forms.1 Inspired by this organization and resultant complexity, our lab has been able to fabricate multicompartmental colloids using the electrohydrodynamic co-jetting technique.2 In these colloids, the internal and external architecture can be precisely controlled to incorporate different materials and unique properties. To date, our lab has focused on the design and engineering of the internal structure to include stimuli responsive polymers, therapeutics, imaging agents, catalyzer, as well as other functional materials.3 Herein, we demonstrate the incorporation of a number of physical (size and shape) and chemical (surface patches and degradation rates) properties in our particles and the use of such multifunctional nanoparticles for drug delivery applications.4-5 References: 1. Mitragotri, S.; Lahann, J., Physical approaches to biomaterial design. Nat Mater 2009, 8 (1), 15-23. 2. Roh, K. H.; Martin, D. C.; Lahann, J., Biphasic Janus particles with nanoscale anisotropy. Nat Mater 2005, 4 (10), 759-763. 3. Rahmani, S.; Lahann, J., Recent progress with multicompartmental nanoparticles. Mrs Bull 2014, 39 (3), 251-257. 4. Rahmani, S.; Saha, S.; Durmaz, H.; Donini, A.; Misra, A. C.; Yoon, J.; Lahann, J., Chemically Orthogonal Three-Patch Microparticles. Angew Chem Int Edit 2014, 53 (9), 2332-2338. 5. Sokolovskaya, E.; Rahmani, S.; Misra, A. C.; Brase, S.; Lahann, J., Dual-Stimuli- Responsive Microparticles. Acs Applied Materials & Interfaces 2015, 7 (18), 9744-9751.

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Shearing experiments of confined phospholipid layers characterized by Fluorescence Recovery After Patterned Photobleaching (FRAPP)

L. Fu1, A. Rubin1* , D. Favier1, T. Charitat1, C. Gauthier1

1 Strasbourg University, Institut Charles Sadron, CNRS-UPR 22, 23 rue du Loess, BP84047, 67034 Strasbourg, France.

Introduction Shear experiments on confined ultrathin films have been widely performed in the nineties to study the viscoelasticity of molecular thin layers [1,2]. Such interfacial rheology measurements were mainly studied with SFA apparatus and are now better understood. Yet, there is a lack of information on shearing mechanisms at the meso-scale. This work propose a step further in experimental investigation of confined ultrathin films on larger surface (~0.03mm²) at a controlled mean contact pressure. In that matter a coupling of two set-up was performed: a nanosclerometer with in situ observation of the contact which monitor the confinement [3]; a FRAPP setup (Fluorescence Recovery After Patterned Photobleaching) which record molecular diffusion [4]. The final aim is to estimate both the strain rate and the shear rate of the confined layer.

Results Tests are performed on model layers formed with DSPC (1% fluorescently labelled) on a Langmuir-Blodgett trough and transferred on a microscope glass slide. Confinement of the DSPC layers between a spherical rigid tip (51 mm radius) and the supporting glass slide is controlled by the nanosclerometer (Fig1a). In parallel a laser beam from the FRAPP set-up is split and the two equivalent beams crossed on the sample, providing an interference fringe pattern. A photobleaching step ensures a set of unbleached dye on the patterned sample, and a reading step gives the signal recovery of fluorescence intensity. The sensitivity of the setup was checked without any contact between DSPC tri-layers and DSPC monolayer (instead of the spherical tip). Two signals were compared: one without displacement of the tip (Fig 1b, grey line) and one with displacement of the tip at v = 1.8 µm/s (Fig 1b, black line). For the latter the peak at f = 0.2 Hz gives the sliding velocity Vs = f.i≈ 1.76 µm/s from the interfringe i = 8.8 µm. This result confirm that the coupling of our setup can give valuable measurements. Experiments are currently performed with a spherical tip shearing DSPC trilayers including one labeled layer only. These experiments shows the kinetics of each layers separately depending on the imposed shearing speed. As a perspective it will lead to a discussion towards the choice of characteristics lengths during shearing and it will help us to gain knowledge in frictional response of membranes in a second step.

a b Fig. 1: Scheme of the experimental coupling MVS/FRAPP (a), FFT of the FRAPP signal from a DSPC trilayers obtained (--) without displacement (--) for a moving speed v = 1.8µm/s (b).

References [1] Briscoe BJ et al. Proc. R. Soc. Lond. A 380:389-407, 1982. [2] Granick S. et al. Langmuir 10:3857-3866, 1994. [3] Gauthier C. et al. Tribology International 34:469–479, 2001. [4] Davoust J. et al. EMBP Journal 1:1233-1238, 1982.

*corresponding author: anne.rubin@ics-cnrs.unistra.fr

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Synthesis and structure of Novel cocontinuous double network elastomers Thitima Limpanichpakdeea, Laurent Bouteillerb, Costantino Cretona

aLaboratory of Soft Matter Science and Engineering, ESPCI-ParisTech-UPMC-CNRS, 10 rue Vauquelin 75231 Paris Cedex 05 b UPMC Univ Paris 06, UMR 7610, Chimie des Polymères, 75005 Paris, France

Recently, a new technique to reinforce unfilled acrylic elastomers has been established. The elastomer was prepared by sequential free radical polymerization and swelling of acrylic monomers making interpenetrated networks. By using this new method, the elastomer had a significantly enhanced initial modulus, stress at break and fracture resistance compared with the simple network. It is now interesting to extend this method to a different elastomeric system to probe its generality. Thus, in this study a Silicone elastomer will be synthesized by using polycondensation polymerization method which is significantly different from polymerization used for acrylic networks. We will show preliminary results on network synthesis, stoichiometric selection and mechanical properties.

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Microreaction Technology: a Tool for the Intensification of Atom Transfer Radical Polymerization Process

Dambarudhar Parida1, Christophe A. Serra1,2,4, K. Garg3 and Yannick Hoarau3,4

1Groupe d’Intensification et d’Intégration des Procédés Polymères (G2IP), Institut de Chimie et Procédés pour l’Énergie,

l’Environnement et la Santé (ICPEES) - UMR 7515 CNRS 2Institut Charles Sadron (ICS) - UPR 22 CNRS

3Laboratoire des Sciences de l'Ingénieur, de l'Informatique et de l'Imagerie (ICUBE) 4Université de Strasbourg, France

This work aims at the intensification of controlled/”living” radical polymerization processes for the

production of architecture-controlled copolymers. Intensification method relies on the use of a coil

flow inverter (CFI) microreactor which was recently found to be extremely efficient mixers/heat

exchangers. Initially linear statistical copolymers of 2-Dimethylamino ethyl methacrylate and Benzyl

methacrylate were synthesized by Atom Transfer Radical Polymerization (ATRP) in batch and

continuous-microscale reactors (CT & CFI). From the kinetics of the polymerization it was observed

that even a slow polymerization reaction like ATRP can be accelerated by using microreaction

technology. Moreover, higher molecular weight (+8,000 g/mol) and lower polydispersity index (PDI)

can be achieved compared to batch mode. It is attributed to the synergy of efficient heat transfer and

enhanced diffusion in microscale even at high viscosities. In case of branched poly(DMAEMA),

highest molecular weight and lowest PDI were obtained with the CFI. These results may be attributed

to the redistribution of streams at each 90° bend which enhances the diffusion of chemical species

from centre to wall as well as narrower residence time distribution (RTD) observed in such kind of

geometry.

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Post-Polymerization Cycloaddition of a Cyclooctyne-Containing Polyimine

Vladimir Kardelis, Ryan C. Chadwick, Alex Adronov*

*Department of Chemistry and Chemical Biology, McMaster University, Hamilton,CA. kardelv@mcmaster.ca

A conjugated polyphenyl-co-dibenzocyclooctyne Schiff-base polymer was synthesized via condensation of dibenzocyclooctyne bisamine (DIBO-(NH2)2) and bis(hexadecyloxy)dialdehyde. The resulting polymer exhibited high molecular weight (Mn > 30 kDa, Mw > 60 kDa), good solubility, and good stability. Strain-promoted alkyne-azide cycloaddition reactions with a series of aryl azides allowed efficient functionalization of triazole units at the polymer backbone and the rapid synthesis of a small polymer library with a consistent degree of polymerization (DP). GPC and density functional calculations suggest a substantial change in polymer conformation after cycloaddition. Kinetic studies show second order reaction rate constants consistent with rate constants for monomeric dibenzocyclooctynes. Grafting with polystyrene and polyethylene glycol monomethyl ether azide-terminated polymers allowed the efficient syntheses of a series of graft-co-polymers with Mn values up to 800 kDa.

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Design of thermoassociating copolymers for aqueous-based formulations: role of topology on the macroscopic properties

Hui GuoESPCI ParisTech / Sorbonne Universités, UPMC Univ Paris 06 / CNRS

, Dominique Hourdet, Alba Marcellan and Nicolas Sanson

UMR 7615, SIMM, 10 rue Vauquelin, F-75005, Paris, France

Thermoassociating copolymers are of great interest when improved viscoelastic properties are required above a given temperature. This is the case for a wide range of industrial water-based formulations like suspensions, coatings, cosmetics, drilling fluids, but also for biomedical applications such as drug release, visco-supplementation of biological fluids and tissue engineering. These thermothickeners are generally designed with a macromolecular architecture (mainly block or grafted) involving two antagonistic contributions: water-solubility and responsive phase separation. For that purpose, polymers exhibiting a lower critical solution temperature (LCST) in water are often used to trigger the association process. In this framework, the extent of the phase separation (from nano to macro) and then the primary structure of the copolymer is the key issue controlling the macroscopic properties. In the present work, we aim at investigating the impact of the copolymer topology on the macroscopic properties by comparing two opposite grafted structures prepared from water-soluble poly(N,N-dimethylacrylamide) [PDMA] and thermoresponsive poly(N-isopropylacrylamide) [PNIPA]. The properties of the two copolymers, possessing similar weight fraction of PDMA and PNIPA but inverted grafted structures (Figure 1a), are studied in dilute and semi-dilute aqueous solutions using calorimetry, rheology and scattering experiments (light and neutron). Although these reversed macromolecules exhibit very similar viscoelastic properties in pure water (Figure 1b), their behavior start to diverge when additives are added into the solution. The structure/properties relationships will be discussed in this presentation.

a

20 30 40 50 600.01

0.1

1

10

100

1000

G', G

'' (P

a)

temperature (oC)

G' PDMA-g-PNIPAG" PDMA-g-PNIPAG' PNIPA-g-PDMAG" PNIPA-g-PDMA

b

Figure 1. (a) Schematic representation of PDMA-g-PNIPA and PNIPA-g-PDMA copolymers (PDMA (▬) and PNIPA (▬)) and (b) comparison of their thermothickening behaviors in water (Cp=3 wt%).

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Dendrimer-nanoparticle conjugates as Nanomedicine tools

Catalina Bordeianu,a Aurélie Walter, a Claire Billotey, b Sophie Laurent, c Robert Muller, c Sylvie Begin-Colin, a Delphine Felder-Flesch a

a Institut de Physique et Chimie des Matériaux de Strasbourg IPCMS UMR CNRS-UdS-ECPM 7504 23 rue du loess BP 43 67034 Strasbourg cedex 2

Catalina.Bordeianu@ipcms.unistra.fr, Sylvie.Begin@ipcms.unistra.fr, Delphine.Felder@ipcms.unistra.fr b Laboratoire de Physico-chimie des Matériaux Luminescents LPCML-UCBL UMR 5620 5 place d’Arsonval F-

69437 Lyon, France. c Service de Chimie Générale, Organique et Biomédicale, Laboratoire de RMN et d'Imagerie Moléculaire,

Université de Mons, 19, Avenue Maistriau, B-7000 Mons, Belgique

As one of the newest areas of science, nano-scale science and technology are seen by many as the key technology of the 21st century, which of course raises the question as to what role this technology will play in medicine. An important area of nano-scale science is the development of nano-structured carriers for medical applications. Various colloidal inorganic nanoparticles that exhibit unique inherent properties such as fluorescence properties (e.g. semiconductor quantum dots (QDs) up-/down-conversion nanoparticles), magnetic properties (e.g. metal oxide nanoparticles) and plasmonic properties (e.g. noble metallic nanoparticles) have been widely explored, particularly for biological and medical applications. For instance, various types of magnetic nanoparticles have a widespread range of applications such as in magnetic resonance imaging (MRI) as T1 and T2 contrast agent, magnetically guided drug/gene delivery, magnetic hyperthermia and magnetic biosensors; up-/down-conversion nanoparticles and QDs and their niche in biological and medical imaging; noble metallic nanoparticles can be used for photothermal therapy and bio-sensing. Designing nanoparticles for molecular diagnosis and targeted therapy is of the utmost importance. The wish list of such systems is long: they should selectively home in on the cells and organs of the body that are involved in the disease process, specifically targeting their potent healing effects on these cells and organs, while sparing cells not involved in the disease process. They should be completely non-toxic, biodegradable or capable of natural excretion, not be recognized or eliminated by the body’s own immune system before they have reached their target, and not induce any allergic reactions. Ideally, they are generic, i.e. they can be “programmed” to combat a wide variety of diseases by docking onto any target structures one chooses and being capable of carrying any medicines.

A proper surface coating can stabilize particles and avoid agglomeration, which hence may increase the sensitivity of NPs based sensor. In addition, a proper surface coating enables the nanoparticles in response specifically to biological species and avoids non-specific interactions with components in the complex matrix. Coating is also an effective manner of preventing the dissolution and release of core materials that may cause toxicity to biological system. Furthermore, the steric hindrance of coating can affect the fate of NPs in biological system, such as cellular uptake and accumulation, circulation and clearance from body. In addition, the surface can affect the maintenance of the intrinsic nanocrystal properties such as fluorescence and magnetic behaviour. Moreover, appropriate surface functionality is the perquisite for conjugating biomolecules to NPs for biomedical applications.

A dendritic approach as a coating strategy for the design of functional nanoparticles is particularly interesting in the field of cancer diagnostics (Figure 1). The appeal of such strategy is due to the unique properties of the dendritic structures which can be chemically tuned to reach ideal biodistribution or highly and efficient targeting efficacies. Indeed, dendrimers are macromolecules consisting of multiple perfectly branched monomers and this architecture makes them versatile constructs for the simultaneous presentation of receptor binding ligands and other biologically relevant molecules. Additionally, dendrimers might serve as promising molecular scaffolds containing a number of ligands thereby inducing an apparent increase of ligand concentration and increasing the probability of statistical rebinding. Alternatively, dendrimers may align these ligands and induce multivalency when receptor clustering occurs or is initiated after initial monovalent binding. To improve tumour targeting efficacy and to obtain better in vivo imaging properties, several studies explored the multivalency effect of dendrimers or of a dendritic surface functionalization of nanomaterials.

We thus propose a concept combining a dendritic coating with phosphonate anchors. Indeed, phosphonates ensure a strong anchoring at the NPs surface while preserving their magnetic properties, and dendritic shells, in addition to their small and easily controllable size (as a function of their generation), are promising building blocks simultaneously solving the problems of biocompatibility, large in vivo stability and specificity. Iron oxide NPs synthesized by co-precipitation and thermal decomposition were coated with functional oligoethyleneglycol or poly(amido)amine (PAMAM) dendrons to improve colloidal stability, graft fluorophores and investigate cell interactions. Different grafting strategies were optimized as a function of the NPs synthesis and dendron nature. The size distribution, colloidal stability in isoosmolar media, nature of surface complex, biodistribution and contrast enhancement properties evaluated through in vitro and in vivo MRI experiments were compared as a function of the nature of both dendrons and nanoparticles. All functionalized nanoparticles (whatever the synthesis method) display good colloidal stability in water but, in isoosmolar media, best results were observed with functional dendronized NPs bearing carboxylates at their periphery. The contrast enhancement properties of all dendronized nanoparticles were found higher than those of commercial products (polymer-decorated) and the best values were recorded for the nanoparticles synthesized by coprecipitation due to their higher saturation magnetization. Moreover, no evident adverse effect was observed in rat after injection, even at high concentrations and a long time after injection. The biodistribution of such nanohybrids was also studied by optical imaging thanks to Alexa labelling at the dendron periphery. In this case, a fast hepatobiliary, together with a low urinary, elimination was observed. Luckily, no RES uptake could be highlighted. Such study confirmed the interest of the dendritic approach to develop new, smart and multimodal contrast agents.

Chem. Comm. 2010, 46, 985-987; Contrast Med. and Mol. Imaging, 2011, 6, 132-138; Biomaterials, 2011, 32, 8562-8573; New J. Chem., invited Perspective review in DENDRIMER 2, 2012, 36 (2), 310-323; Eur. J. Inorg. Chem., invited Microreview in a special edition on Contrast Agents, 2012, 1987-2005; Nanomedicine 2014, accepted.

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Long term stability of proteins in contact with solid surfaces

Tongtong Huang1,2, Karine Anselme1, Segolene Sarrailh2 and Arnaud Ponche1 1Institut de Science des Matériaux de Mulhouse (IS2M),

Université de Haute Alsace, France. 2Aptar pharma – Route Des Falaises, 27100 Le Vaudreuil, France.

tongtong9696@gmail.com

Proteins are widely used in formulation in the pharmaceutical field and play a major role in biological functions. However, as a widespread phenomenon, the adsorption of proteins on solid surface is always observed for a long-term storage, which will result in a reduced dose of active compound or a loss of biological activity1. For instance, insulin losses 52% of its biological activity after 5 minutes contacting with glass surface2. The interfacial behavior is also known to trigger aggregation phenomena leading to drastic biological inactivation of proteins during long term storage. In this study, several model proteins have been contacted with multiple types of substrates. Parameters including temperature, concentration, adsorption time, rinsing steps and their influence on amount and conformation of adsorbed proteins have been systematically evaluated. Three model proteins were chosen for this study: bovine serum albumin (BSA), lysozyme (LSZ) and myoglobin (MGB). High performance liquid chromatography (HPLC) was used to quantify protein in solution (phosphate buffer saline, pH 7.4) after contact with glass and polydimethylsiloxane (PDMS) surfaces. Attenuated total reflection infrared (ATR-IR) spectroscopy has been adopted for proteins’ structure determination. The three proteins which have different intrinsic properties (like conformation stability for instance) show characteristic kinetic curves. These curves can be mathematically fitted with Langmuir model. As a more hydrophobic surface, the amount of BSA adsorbed on PDMS after 3 hours is five time more important. By peak fitting of amide I band, ATR-FTIR is able to give insight on secondary structures of the adsorbed protein. After a short contact time, adsorbed protein lost about half of the α-helix structures compared to native protein in solution. By increasing protein concentration, the fraction of α-helix is maintained close to the solution structure, confirming the protective effect of the concentration over denaturation. But this effect cannot be effective over a long time: after 2 hrs of contact, the adsorbed proteins at all concentrations showed similar secondary structures. After having reviewed the relevant parameters for adsorption of proteins, long term adsorption experiments (over 3 months) are currently under investigation. The first results show that initial adsorption process and nature of the surfaces drive the long term behavior of the protein in the formulation and play a role in initiation of aggregation process.

1. C. J. Burke et al., Int. J. Pharm., 86 : 89–93, 1992.2. C. PETTY and N. Cunningham, Anesthesiology, 40, 1974.

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Controlled Radical Polymerization of Zwitterionic Monomers for Biomedical Applications

Venkidasubramonian Gowthamy IBG - Karlsruhe Institute of Technology - Germany

Well-defined culture conditions are essential for realizing the full potential of human embryonic stem cells (hESCs) in regenerative medicine where large numbers of cells are required. Poly[2-(methacryloyloxy) ethyl dimethyl-(3-sulfopropyl) ammonium hydroxide] (PMEDSAH) substrates offer multiple advantages over mouse embryonic fibroblasts (MEFs) and Matrigel™ for hESC culture and expansion such as well-defined chemical composition, storage stability, reproducibility, cost-effectiveness and compatibility with standard sterilization techniques1. To study the impact of physico-chemical properties on hESC growth, we synthesized a library of new sulfobetaine methacrylates with varying inner charge distances2. Surface-initiated atom transfer radical polymerization (ATRP)3,4 of a selection of these monomers were carried out to produce well-defined polymer brushes showing a gradual augmentation in film thickness with increasing reaction time. Other material properties such as wettability, surface roughness and UCST phase transitions were also studied.

References:

1. Villa-Diaz LG, Nandivada H, Ding J, Nogueira-de-Souza NC, Krebsbach PH, O‘SheaKS, Lahann J; Nat. Biotechnol 2010;28:581 – 3

2. Kratzer D, Barner L, Friedmann C, Bräse S, Lahann J; Eur. J. Org. Chem.; 2014;8064-8071.

3. Qian X, Villa-Diaz LG, Kumar R, Lahann J; Biomaterials; 2014; 35, 9581-9590

4. Matyjaszweski K; Macromolecules 1995; 28: 7901-10.

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