2016 INDO-FRENCH CONFERENCE

Functional polymers and self-assembled systems

23-25 May 2019, Institut Charles Sadron, Strasbourg, France

Book of abstracts

INVITED LECTURES

2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2016, Strasbourg, France

From Chain Folding to 2D Polymers

S. RAMAKRISHNAN Department of Inorganic and Physical Chemistry Indian Institute of Science Bangalore, 560012

ABSTRACT: Control of chain conformation in solution have recently demonstrated. However, these are not has several interesting ramifications – from mimicking robust structures that can be prepared in bulk and the exquisite conformational control seen in biological exfoliated. It is with this challenge that we have just macromolecules to understanding factors that govern begun to examine alternate approaches to prepare 2D the lamellar crystallite sizes in semi-crystalline polymers; broadly, our strategy is to pre-organize polymers. During the past decade we have examined multi-segmented monomers bearing at least two several aspects dealing with control of chain polymerizable units at the segment junctions. The pre- conformation in solution; and we have also attempted organization is designed to be driven by segment to translate this control towards regulating the immiscibility and strengthened by the strong morphological characteristics of the bulk polymer. The interactions, such as crystallization, within the lamellar morphology that is often realized in these domains; polymerization of the double bonds in the attempts leads to the layering of different types of solid or semi-molten state it was expected would lead immiscible domains; a closer examination of these to the formation of a cross-linked and reasonably stiff layered structures prompted us to begin exploring the sheet that would represent a 2D polymer. By suitable similarity between these systems and 2D polymers. 2D choice of the outer segments, it was felt that exfoliation polymers have begun to attract the attention of several could be made feasible. In the talk, I shall describe our groups world-wide; although many early efforts have efforts beginning with chain folding and I shall end examined polymerization at air-water interfaces and with our recent foray into 2D polymers. also within vesicles, these do not typically constitute robust structures that would withstand exfoliation. One of the prime drivers of this field is graphene, which could be viewed as the archetypical 2D polymer – a robust and reasonably stiff system that can be readily exfoliated to generate single atom-thick carbon sheets. The remarkable properties of graphene amply justify the incredible attention that this class of materials has received during the past decade. As a polymer chemist one can ask – what are the possible design strategies to prepare 2-dimensional polymers? Evidently, folding of polymer chains does constitute one way to generate 2- D polymeric nanoobjects; the thickness of these sheets would be the height of a folded chain – something we

KEY WORDS: Polymer folding, crystallization, lamellae, 2D polymers

References 1. Raj Kumar Roy, E. Bhoje Gowd and S. Ramakrishnan, “Periodically Grafted Amphiphilic Copolymers: Nonionic Analogues of Ionenes” Macromolecules 45, 3063 (2012) 2. Joydeb Mandal, S. Krishna Prasad, D. S. Shankar Rao and S. Ramakrishnan, “Periodically clickable polyesters: Study of intra-chain self-segregation induced folding, crystallization and mesophase formation” J. Am. Chem. Soc. 136, 2538 (2014).

2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2016, Strasbourg, France

Bio-inspired polymersomes from controlled self-assembly of bio-hybrid copolymers

S. LECOMMANDOUX LCPO, UMR CNRS 5629, Université de Bordeaux, Bordeaux-INP, 33600 Pessac, France

ABSTRACT: Polymer vesicles, also coined targeting and in vivo tumor regression studies will be polymersomes, are among the most attractive systems presented. for drug delivery applications. Actually, vesicles Fig. 1 : A Scheme of dual-loaded polymersomes with obtained by self-assembly of block copolymers are iron oxide nanoparticles and doxorubicin in their expected to overcome some of the current limitations membrane in drug delivery, allowing the development of robust nanocontainers of either hydrophilic or hydrophobic species. In addition, the development of macromolecular nanodevices that can be used within the living body implies that sensors detecting chemical signals -such as ions, enzymes or pH changes- and generating internal signals or appropriate responses be integrated in the macromolecular system. The use of peptide and saccharide building blocks in the Finally our recent advances in using “biomimicry copolymer structure would allow both controlling the approaches” to design complex, compartmentalized self-assembled structure and the resultant materials will be proposed (Figure 2). We demonstrate biofunctionality. the formation of compartmentalized polymersomes We report an overview on the self-assembly in water of with an internal “gelly” cavity using an original and amphiphilic block copolymers into polymersomes, and versatile emulsion-centrifugation process. Such a their applications in loading and controlled release of system constitutes a first step towards the challenge of both hydrophilic and hydrophobic molecules and structural cell mimicry with both “organelles” and biomolecules. We pay special attention to “cytoplasm mimics”. This study constitutes major polysaccharide and polypeptide-based block copolymer progress in the field of structural biomimicry and will vesicles that we have studied these recent years in our certainly enable the rise of new, highly interesting group. These newly developed copolymers that mimic properties in the field of high-added value soft matter, especially in controlled cascade (bio)reactions. the structure and function of glycoproteins represent an example of the effectiveness of a biomimetic strategy Fig. 2 : “Plastic cells” as enzymatic reactor. (a) Graphical in implementing materials design. In addition, depiction of the applied system. (b) Plot profiles of the magnetic polymersomes, including iron oxide -Fe2O3 fluorescence cross-section for different time point showing nanoparticles are currently investigated, together with the increase of fluorescence with time. their potential applications as contrast agent for (c) (a) (b) imaging and as therapeutic nanoparticles using hyperthermia (Figure 1). Exciting and very promising results about their therapeutic evaluation for tumor

KEY WORDS: self-assembly, nanoparticles, biomimicry, controlled release, polypeptide, amphiphilic copolymers

References 1 (a) C. Bonduelle, S. Lecommandoux. Biomacromolecules 2013, 14, 2976-2983. (b) Huang, J. ; Bonduelle, C. ; Thévenot, J.; Lecommandoux, S. ; Heise, A. J. Am. Chem. Soc. 2012, 134, 119. (c) 8 Upadhyay, KK.; Bhatt, A.N.; Mishra, A.N.; Dwarakanath, B. S.; Jain, S.; Schatz, C.; Le Meins, JF.; Farooque, A.; Chandraiah, G.; Jain, AK.; Misra, AK.; Lecommandoux, S. Biomaterials 2010, 31, 2882. 2 (a) Sanson, C. ; Diou, O. ; Thevenot, J. ; Ibarboure, E. ; Soum, A. ; Brulet, A. ; Miraux, S. ; Thiaudiere, E. ;Tan, S. ; Brisson, A. ; Dupuis, V. ; Sandre, O. ; Lecommandoux, S. ACS Nano 2011, 5, 1122. (b) Oliveira, H. ; Pérez-Andrés, E. ; Thevenot, J. ; Sandre, O. ; Berra, E. ; Lecommandoux, S. J. Control. Release 2013, 169, 165. (c) Pourtau, L. ; Oliveira, H. ; Thevenot, J. ; Wan, Y. ; Brisson, A. ; Sandre, O. ; Miraux, S. ; Thiaudiere, E. ; Lecommandoux, S. Advanced Healthcare Materials 2013, 2, 1420-1424. 3 (a) Marguet, M.; Edembe, L.; Lecommandoux, S. Angew. Chem. Int. Ed. 2012, 51, 1173. (b) Marguet, M.; Sandre, O.; Lecommandoux, S. Langmuir 2012, 28, 2035. (c) Marguet, M. ; Bonduelle, C. ; Lecommandoux, S. Chem. Soc. Rev. 2013, 42, 512- 529. (d) R. J. R. W. Peters, M. Marguet, S. Marais, M. W. Fraaije, J. C. M. Van Hest, S. Lecommandoux. Angew. Chem. Int. Ed. 2014, 53, 146-150. 2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2016, Strasbourg, France

Co-existence of LCST and UCST Phases of a Poly(vinylidene fluoride) graft Copolymer in Alcohol-Water system ATANU KUILA, NABASMITA MAITY, DHRUBA P. CHATTERJEE$ AND ARUN K. NANDI*

Polymer Science Unit, Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700032, India, E-mail: [email protected]

ABSTRACT: Poly(vinylidene fluoride) (PVDF) is 0.2%,w/v) and it indicates an approximate inverted grafted with a thermo-responsive polymer hourglass phase diagram where a swelled state exists poly(diethylene glycol methyl ether methacrylate) between two single phase boundary produced from (PMeO2MA) using a combined ATRC and ATRP LCST and UCST type phase transitions. The phase technique with a very high conversion (69%) of the separation process has been explained from monomer to produce the graft copolymer (PD).1,2 temperature dependent 1H NMR spectroscopy along Dynamic light scattering (DLS) study is used to study with transmission electron microscopy. the solution property by varying polarity in pure solvents (water, methanol, isopropanol) and also in mixed solvents (water-methanol and water- isopropanol). The Z-average size varies with

C) temperature of the PD solution (0.2%, w/v) indicating a ) two phase two phase 0

C UCST LCST lower critical solution temperature (LCST) type phase 0 ( transition (TPL) in aqueous medium. In isopropanol medium an upper critical solution temperature (UCST) emp. type phase transition (TPU) is noticed but neither LCST t nor UCST type phase transition is noticed for methanol one phase

on one phase larger sizes (400-750 nm), and exhibit neither any iti break in Z-average size-temperature plot nor any

surprisingly at 40-60% both UCST and LCST type rans two phase Transition ( temp. T phase separation occurs simultaneously. Butin the Swelled state mixture containing 70-90% methanol swelled state of 0.08 0.10 0.18 0.20 the particles (size 250 -375 nm) are noticed. We have % of PD (w/v) drawn a quasibinary phase diagram (Fig.1) for 50 vol% Fig. 1: Quasibinary phase diagram of PD of methanol indicating presence of dispersed swelled in methanol-water solution (1:1, v/v). state in the medium. In the methanol + water mixture with methanol content of 0-30% TPL increases and solution. In the mixed solvent (water + isopropanol) at 0-20 % (v/v) isopropanol the TPL increases whereas the TPU decreases at 92-100 % with isopropanol content. However for the mixture having intermediate composition (20 – 90% isopropanol) PD particles have methanol by varying polymer concentration (0.07-

KEY WORDS: PVDF, Grafting, ATRC, ATRP, UCST, LCST, Phase diagram.

References 1. Kuila, A,. Chatterjee,, D. P., Layek , R. K., Nandi A. K. J.Polym. Science, Part A Polym. Chem Ed, 2014,52, 995 2. Kuila,A., Maity, N., Chatterjee, D. P., Nandi, A. K., J. Mater. Chem. A, 2015, 3, 13546 3. Kuila,A., Maity, N., Chatterjee, D. P., Nandi, A. K., communicated $ : Present address ;Presidency University, Kolkata.

2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2019, Strasbourg, France

Controlled crystallization and orientation of semi-conducting polymers

M. BRINKMANN1, A. HAMIDI-SAKR1, D. SCHIEFER2, L. BINIEK1, S. FALL3, M. SOMMER2

1 Institut Charles Sadron, CNRS-Université de Strasbourg, 23 rue du Loess, F-67034 STRASBOURG, France

2 Institut für Makromolekulare Chemie, Universität Freiburg, Stefan-Meier-Straße 31, 79104 Freiburg, Germany

3 ICUBE, MaCEPV, Université de Strasbourg, 23 rue du Loess, 67037, Strasbourg, France

ABSTRACT: Driven by the development of plastic anisotropy is correlated to the evolution of the electronics, polymeric semi-conductors (PSCs) have dominant contact plane from mainly face-on (TR ≤ 100 been the center of major research efforts in the last °C) to edge-on (TR ≥ 170 °C). decades. They are used as the active layers in devices such as Organic Field Effect Transistors, Organic Light Emitting Diodes and Organic solar cells. Before integrating new PSCs in devices, it is mandatory to draw proper correlations between their structural/morphological characteristics and their optical, electronic and opto-electronic properties. For this reason, the processing-structure-property nexus is of central importance in plastic electronics. Efforts are Fig.1. Evolution of the dichroic ratio and order still necessary to achieve proper growth control of parameter in P3HT films oriented by high- PSCs and to detetmine their structure. This temperature rubbing (left). Lamellar morphology contribution will focus on recent advances in growth observed by TEM. control and crystallization of some key PSCs such as regioregular poly(hexylthiophene). Particular emphasis II. Epitaxial crystallization. will be given to the progress made in our group on The large majority of semiconducting polymers based oriented growth of PSCs using high-Temperature on poly(alkylthiophene)s with linear or branched alkyl rubbing or epitaxy. side chains are reported to -stack in their crystalline I. High temperature rubbing. phases. In regioregular poly(3-(2,5- Precise control of orientation and crystallinity is dioctylphenyl)thiophene) (PDOPT), however,  achieved in regioregular poly(3-hexylthiophene) interactions are absent due to the presence of the bulky (P3HT) thin films by using high-temperature rubbing, a 2,5-dioctylphenyl side groups. High levels of fast and effective alignment method. Rubbing P3HT crystallinity and orientation are created in thin films of PDOPT aligned on substrates of naphthalene by slow films at temperatures TR ≥ 144 °C generates highly oriented crystalline films with a periodic lamellar directional epitaxial crystallization. Depending on morphology with a dichroic ratio reaching 25. molecular weight, both edge-on and flat-on lamellar crystals are obtained. Electron microscopy imaging Uniquely, the inverse of the lamellar period l scales reveals a transition from extended to folded chain with the supercooling and can accordingly be crystallization for M  12.7 kDa. The high orientation controlled by the rubbing temperature T . The exciton n R and crystallinity levels result in high anisotropy of UV- coupling in P3HT crystals is correlated to the length of vis absorption and photoluminescence. The single- the average planarized chain segments lc in the crystal-like electron diffraction patterns are used to crystals. The high alignment and crystallinity observed determine the structure of PDOPT. PDOPT features for TR > 200 °C cannot translate to high hole mobilities perfectly planarized chains despite the absence of - parallel to the rubbing because of the adverse effect of stacking. The octyl side chains are interdigitated and amorphous zones interrupting charge transport between crystallize in a dense subcell which is compared to that crystalline lamellae. Although tie chains bridge of other semiconducting polythiophenes. This successive P3HT crystals through amorphous zones, comparison allows to define some correlations between their twisted conformation restrains interlamellar side chain packing and overall crystallinity of the PSC. charge transport. The evolution of charge transport

KEY WORDS: conjugated polymers, Electron microscopy, crystallization

References 1. A. Hamidi Sakr et al., Adv. Funct. Mat. 2016, 26, 408. 2. M. Brinkmann et al., Macro. Rapid Comm. 2014, 35, 9

2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2016, Strasbourg, France

Semiconducting Polymers and Oligomers for Optoelectronic Applications: Facile Screening Using TRMC Technique

VIJAYAKUMAR C. NAIR Photosciences and Photonics Section, CSIR – National Institute for Interdisciplinary Science and Technology, Trivandrum, India. 695 019

ABSTRACT: Solution processable organic semiconducting materials is an area of immense scientific interest due to their potential for developing low-cost, flexible, light-weight electronic devices including photovoltaic cells, field-effect transistors and light emitting devices. At the molecular level, alternating the arrangement of electron donor and acceptor units in the conjugated backbone has been found to be a successful approach for developing reflects the material properties at the molecular level semiconducting polymers and oligomers for electronic but also their ordering in the film state. Fast and devices. The intra- and intermolecular charge transfer reliable measurement of such parameters helps speedy interactions could be effectively tuned by varying the screening of new materials and hence facilitates further electron donating and/or accepting strength of development in the area of organic electronics. In this individual building blocks, yielding suitable absorption context, flash-photolysis time-resolved microwave characteristics and optimum optical band gap for conductivity (TRMC) has attracted significant interest. device applications. Various techniques such as UV-vis TRMC is a unique electrodeless technique, which absorption and fluorescence spectroscopies, cyclic provides information about charge carrier generation voltammetry, and density functional theory and short-range (nanometer scale) intrinsic charge calculations give insight into the molecular level carrier transport properties of a material. This is an properties. However, predicting device performance by effective tool for predicting the device performances extrapolating the results obtained from these analyses (particularly photovoltaic and field-effect transistor is not possible in most cases. This is because the devices) without the fabrication of actual devices. structural ordering of the polymers/oligomers in the In this talk, a set of donor-acceptor type new film state plays a significant role in the device semiconducting polymers and oligomers will be performances. presented. Correlation of their structure, film state Charge carrier generation and transport properties organization, optoelectronic properties and device are the most important parameters which determine the performances with respect to TRMC results will be device efficiency of semiconducting materials. discussed in detail. Quantitative estimation of these parameters not only

KEY WORDS: Donor-acceptor systems, time-resolved microwave conductivity, structure-property correlation, photovoltaic, field-effect transistors

References 1. Vijayakumar, C.; Saeki, A.; Seki S. Chem. Asian J. 2012, 7, 1845. 2. Balan, B.; Vijayakumar, C.; Saeki, A.; Koizumi, Y.; Seki, S. Macromolecules 2012, 45, 2709. 3. Vijayakumar, C.; Balan, B.; Saeki, A.; Tsuda, T.; Kuwabata, S.; Seki, S. J. Phys. Chem. C 2012, 116, 17343. 4. Balan, B.; Vijayakumar, C.; Tsuji, M.; Saeki, A.; Seki S. J. Phys. Chem. B 2012, 116, 10371. 5. Saeki, A.; Yoshikawa, S.; Tsuji, M.; Koizumi, Y.; Ide, M.; Vijayakumar, C.; Seki, S. J. Am. Chem. Soc. 2012, 134, 19035. 6. Balan, B.; Vijayakumar, C.; Saeki, A.; Koizumi, Y.; Tsujia, M.; Seki S. Polym. Chem. 2013, 4, 2293. 7. Tsuji, M.; Saeki, A.; Koizumi, Y.; Matsuyama, N.; Vijayakumar, C.; Seki, S. Adv. Funct. Mater. 2014, 24, 28. 8. Ghosh, T.; Gopal, A.; Saeki, A.; Seki, S.; Vijayakumar, C. Phys.Chem.Chem.Phys. 2015, 17, 10630. 9. Ghosh, T.; Gopal, A.; Nila, T. M.; Saeki, A.; Vijayakumar, C. (submitted). 2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2016, Strasbourg, France

About Sequences, Codes and Polymers

J.-F. LUTZ Precision Macromolecular Chemistry, Institut Charles Sadron, UPR-22 CNRS, 23 rue du Loess 67034 Strasbourg, FRance

ABSTRACT: In this lecture, I will present recent achievements Information-containing macromolecules are polymers obtained in my laboratory for the synthesis of that contain a message encrypted in their comonomer information-containing macromolecules. Recent sequences. The archetypal example of such a polymer progress in the field of sequence-controlled polymers is DNA, which is used in biology to store genetic allows synthesis of unnatural macromolecules with information.[1] However, DNA is certainly not the precisely controlled primary and secondary only polymer that can contain molecular structures.[3-6] For instance, monodisperse sequence- information.[2] In principle, a string of information can defined polymers were prepared using chemoselective be created in any copolymer using two comonomers iterative strategies.[7] Furthermore, the readability of defined intentionally as 0-bit and 1-bit (Figure 1). these polymers will be presented. For instance the However, such polymers have to be monodisperse and sequencing of unnatural sequence-defined copolymers perfectly sequence-defined. In addition, the message by tandem mass spectrometry will be discussed.[7] encoded in their chains should be easily read

Figure 1. Schematic representation of an information-containing macromolecule containing a monomer-encoded binary code. Reprinted from reference 2. © Nature Publishing Group 2014.

KEY WORDS: sequence-controlled polymers, information-containing macromolecules, iterative synthesis, sequencing, data storage.

References 1. Lutz, J.-F., Ouchi, M., Liu, D. R.; Sawamoto, M. Science 2013, 341, 628 2. Colquhoun, H. M., Lutz, J.-F. Nature Chem. 2014, 6, 455-456 3. Giuseppone, N., Lutz, J.-F. Nature 2011, 473, 40-41 4. Lutz, J.-F. Nature Chem. 2010, 2, 84-85 5. Ouchi, M., Badi, N., Lutz, J.-F., Sawamoto M. Nature Chem. 2011, 3, 917-924 6. Zamfir, M., Lutz, J.-F. Nature Commun. 2012, 3, 1138 7. Roy, R. R., Meszynska, A., Laure, C., Charles, L., Verchin, C., Lutz, J.-F. et al. Nature Commun. 2015, 6, 7237 2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2016, Strasbourg, France

Supramolecular Triarylamine Self-Assemblies as Functional Nanomaterials

N. GIUSEPPONE University of Strasbourg, Institut Universitaire de France (IUF) Institut Charles Sadron - CNRS, 23 rue du Loess, BP 84047 67034 Strasbourg Cedex 2, France ABSTRACT Supramolecular organic electronics rests in the formation of supramolecular plasmonic on the use of bottom-up chemical self-assembly waveguides and interconnects.[9] processes in order to design conducting components at the 5–100 nm scale. Challenges in this field are both the construction of 1D-nanostructures displaying optimized transport properties and their precise connections to electrodes. By externally controlling light-responsive supramolecular polymerization processes of tailored triarylamine molecules, and by using appropriate methods of orientation, we have now demonstrated that it becomes possible to pre-determine the accurate positioning of organic interconnects within patterned nano-circuitry.[1-3] Along this main line, we will describe the detailed mechanism of this very original self-assembly process.[4] We will show that supramolecular polymerization can be extended to a number of advanced triarylamine derivatives for the production of various nanostructures.[5-7] We will also discuss the optical and electronic properties of these supramolecular polymers which reveal optical, magnetic, and electronic metallic signatures; the nature of their through-space conduction will be described. Furthermore, the supramolecular dynamics of these assemblies allows for the creation of novel soft materials not accessible with conducting conjugated polymers. In particular, we will show that some triarylamine-based nanofibers demonstrate a mechanism of defect repair driven by polaron diffusion through their supramolecular stacks.[5] We will finally highlight how the presence of such metallic electrons in these organic materials can be used for the first time

KEY WORDS: supramolecular polymers, responsive self-assemblies, conducting nanostructures, triarylamines

References [1] Moulin, E., Niess, F., Maaloum, M., Buhler, E., Nyrkova, I., Giuseppone, N., Angew. Chem. Int. Ed. 2010, 49, 6974. [2] Faramarzi, V., Niess, F., Moulin, E., Maaloum, M., Dayen, J.-F., Beaufrand, S. Zanettini, J.-B., Doudin, B., Giuseppone, N., Nat. Chem. 2012, 4, 485. [3] Moulin, E., Cid-Martin, J., Giuseppone N., Adv. Mat. 2013, 25, 477. [4] Nyrkova, I., Moulin, E., Armao, J. J., Maaloum, M., Heinrich, B., Rawiso, M., Niess, F., Cid J.-J., Jouault, N., Buhler, E., Semenov, A., Giuseppone N., ACS Nano 2014, 8, 10111. [5] Domoto, Y., Busseron, E., Maaloum, M., Moulin, E., Giuseppone, N. Chem. Eur. J. 2015, 21, 1938. [6] Wolf, A., Moulin, E., Cid, J.-J., Goujon, A., Du, G., Busseron, E., Fuks, G., Giuseppone, N. Chem. Commun. 2015, 51, 4212. [7] Busseron, E., Cid, J.-J., Wolf, A., Du, G., Moulin, E., Fuks, G., Maaloum, M., Polavarapu, P., Ruff, A., Saur, A.-K., Ludwigs, S., Giuseppone, N. ACS Nano 2015, 9, 2760. [8] Armao, J. J., Maaloum, M., Ellis, T., Fuks, G., Rawiso, M., Moulin, E., Giuseppone, N. J. Am. Chem. Soc. 2014, 136, 11382. [9] Armao, J.J., Domoto, Y., Umehara, T., Maaloum, M., Contal, C., Fuks, G., Moulin, E., Decher, G., Javahiraly, N., Giuseppone N., ACS Nano 2016, 10, DOI: 10.1021/acsnano.5b06294. 2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2016, Strasbourg, France

Engineered Amphiphiles by H-Bonding

Suhrit GHOSH Polymer Science Unit, Indian Association for the Cultivation of Science, Kolkata, India. 700032

ABSTRACT: Assembly of amphiphilic molecules and unsymmetrical π-amphiphiles, both having macromolecules has been an intense area of research in naphthalene-diimide chromophore connected to a non- interdisciplinary domain ranging from biology to ionic and anionic head groups in opposite arms, was materials science. Most of the amphiphilic molecules realized. They differ only in the location of a hydrazide are structurally identical in broad sense i.e. they consist group, placed either at the non-ionic or anionic arm of of a hydrophobic and a hydrophilic segments which the NDI chromophore. H-bonding among the differ in terms of their relative length, volume and hydrazides, compensating electrostatic and steric nature of covalent linking to each other. A natural next factors, promotes unidirectional alignment and step towards enriching their structural diversity would monolayer vesicles leading to contrasting surface be to make multiple directional forces such as H- functional group display and enzyme inhibition ability. bonding and π-stacking work in tandem. However, More recntly we have moved to a chromophore- examples of H-bonding-directed self-assembly of conjugated macromolecular amphiphilic system abiotic building blocks in aqueous medium are still rare consisting of a trialkoxy-benzhydrazide functionalized presumably because of the inherent difficulty naphthalene-diimide (NDI) building block at the chain associated with competitive H-bonding interaction with end of a water soluble non-ionic polymer. It shows the water molecules. vesicle and reverse vesicle assembly in water and oil, We have described recently spontaneous vesicular respectively, with bunch of interesting features such as assembly of a bis-hydrazide functionalized aggregation-induced enhanced emission, excellent naphthalene-diimide (NDI)-based non-ionic container property for both hydrophobic and bolaamphiphile in aqueous medium by synergistic hydrophilic dye, remarkable thermal and kinetic effect of π-stacking and hydrogen-bonding. Site stability. More importantly the assembly and isolation of the hydrogen bonding functionality morphology in such supramolecularly engineered (hydrazide), a strategy that has been adopted so polymers appear to be primarily driven by H-bonding elegantly in nature, has been executed with perfection functional group which can overcome the packing in the present system to protect them from bulk water parameters of classical immiscibility driven so that distinct role of hydrogen-bonding in self- aggregation of amphiphilic block copolymers. assembly could be realized even in aqueous solution. Further, we showed electron-deficient NDI- bolaamphiphile could be engaged in donor-acceptor (D-A) charge-transfer (CT) interaction with water- insoluble electron rich pyrene donor by perfect intercalation which eventually resulted in rupturing of the membrane to form 1D fiber leading to gelation. Effective pyrene intercalation was also exploited for spontaneous insitu multi-functionalization of the vesicular membrane. Based on similar supramolecular strategy, unidirectional assemblies of two bola-shape

KEY WORDS: Amphiphiles; H-Bonding; Polymersome; Enzyme inhibition

References 1. Pramanik, P., Ghosh, S., Unpublished work. 2. Sikder, A., Das, A., Ghosh, S., Angew. Chem. Int. Ed. 2015, 54, 6755-6760. 3. Rajdev, P., Molla, M. R., Ghosh, S., Langmuir 2014, 30, 1969-1976. 4. Das, A., Ghosh, S., Macromolecules 2013, 46, 3939-3949. 5. Molla, M. R., Ghosh, S., Chem. Eur. J. 2012, 18, 9849-9859.

2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2016, Strasbourg, France

Structural and thermodynamic studies of self-assembled diamides

D. COLLIN,1 C. BLANC,2 E. CHRIST,1 J.-L. BANTIGNIES,2 R. LEPARC,2 J.M. GUENET1 and P. MESINI1 1Institut Charles Sadron, CNRS, Université de Strasbourg, 23 rue du Loess, F-67034 STRASBOURG, France

Laboratoire Charles Coulomb, UMR 5221 CNRS Université de Montpellier, 34095 Montpellier, France

ABSTRACT: BHPB-n (Figure 1) is a series of bis- amides gelators that self-assemble in non-polar We will present the spectroscopic properties of these solvents. self-assemblies and the determination of their shape and size by two techniques: electron microscopy on freeze fractured samples and small angle scattering.The nanotubes have a high aspect ratio with a length of several micrometers and a diameter of a few tens of nm. The diameter is well-defined with a narrow distribution and is controlled by the length of the ester. The binary phase diagrams of BHPB10 in trans- decalin have been recently mapped out by micro differential calorimetry, by rheology, optical Fig. 1 : Chemical structure of BHPB-n microscopy and transmitted light intensity measurements. The structures of the different phases As shown by FTIR spectroscopy studies, the self- have been probed by FTIR and NMR. We will show assemblies are driven by H-bonds between amide; but that the different results provide new insights into the these studies reveal that the esters are also involved in interpretation of phase diagrams.3 the self-assembly. Their lengths governs the shape of BHPB-n compounds can be derivatized with a few the self-assemblies : flat ribbons, nanotubes or twisted 1,2 functional groups while their ability to form nanotubes ribbons. is preserved. We will show that the corresponding nanotubes can react with and remain self-assembled, as shown by cryo-fracture TEM and SAXS. We have also prepared aerogels from these reactive nanotube and we have studied their reactivity in water.4 Because they are both hydrophobic and alveolar, these aerogel do not react with hydrosoluble compounds, but trap every hydrophobic species and selectively react with it.

Fig. 2 : Freeze fracture TEM of self-assemblies of BHPB-n. A to E ; n= 8 to 12. F BHPB-6

KEY WORDS: organogelators, self-assembly, nanotubes, phase diagrams

References 1. Diaz N., Simon, F.X., Schmutz, M., Rawiso, M., Decher G., Jestin, J., Mésini, P., Angew. Chem. Int. Ed. Engl., 2005, 44, 3260 2. Simon, F.-X.; Nguyen, T. T. T.; Díaz, N.; Schmutz, M.; Demé, B.; Jestin, J.; Combet, J.; Mésini, P. J. Soft Matter, 2013, 9, 8483 3. Christ, E, Blanc, C., Al Ouahabi, A., Maurin, D.; Le Parc, R., Bantignies, J.L., Guenet, J.M.,Collin, D.; Mésini, P., submitted 4. T. T. T. Nguyen, F.-X. Simon, M. Schmutz, N. A. Khan, P. J. Mésini ; J. Mater. Chem., 2012, 22, 7712 2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2016, Strasbourg, France

Nano fibrillated cellulose aerogels with thermal superinsulating properties C. JIMENEZ1, Y. GROHENS1, B.CATHALA2, B. SEANTIER1

1LIMATB, UBS, Rue de Saint Maudé, 56100 Lorient - France 2Unité BIA, INRA, Rue Géraudière, 44000 Nantes - France

ABSTRACT: Bio aerogels are a new bio materials made . from polysaccharides. They have a very light weight and are highly porous. Due to its good thermal and mechanical properties, they have been extensively studied during the last decade1–4. Generally, aerogels are prepared by gelling and drying. To avoid the collapse of the pores during drying, techniques such as freeze drying or supercritical drying are used. However, during freeze drying, very large pores are produced. Due to the nucleation and growth of solvent crystals, the gel network may eventually be destroyed5. We propose a new drying technique derived from freeze drying, that allow an increase in the nano- structuration compared to conventional method. Nano fibrillated cellulose (NFC) aerogels are made by this new technique. Their structures and properties will be compared to aerogels prepared by normal freeze drying Fig. 1 : Thermal conductivity as a function of aerogel process. We found a drastic reduction in the pore size density for two different techniques of preparation and an increase in the specific surface area. In addition, the thermal properties have been improved considerably reaching values such as 18 mW/mK. Using this new freeze drying technique we designed a new material being thermal superinsulator 100% biobased.

KEY WORDS: Fibrilar cellulose, aerogels, porosity, super-insulation

References 1Gavillon, R.; Budtova, T. Biomacromolecules 2008, 9, 269–277. 2 Pääkkö, M.; Vapaavuori, J. et al. Soft Matter 2008, 4, 2492–2499. 3 Kobayashi, Y.; Saito, T. et al. Angew. Chem. Int. Ed. 2014, 53, 10394–10397. 4 Fischer, F.; Rigacci, A. et al. Polymer 2006, 47, 7636–7645. 5 Hamon, H.; Ishizaka, H. et al. Carbon 2000, 38, 1099–1105.

2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2016, Strasbourg, France

Molecular tectonics: from molecules to crystal welding

M.W. HOSSEINI Laboratoire de Tectonique Moléculaire, UMR UDS-CNRS 7140, University of Strasbourg, Institut Le Bel, 4, rue Blaise Pascal, 67000 Strasbourg, France ([email protected])

ABSTRACT: The design and construction of periodic achieved by self-assembly processes based on architectures in the crystalline phase are attracting repetitive molecular recognition events. This approach, considerable interest over the last two decades. For combining supramolecular synthesis and self-assembly both design and analysis of molecular crystals, we have processes in the solid state, is operational and versatile developed a strategy called molecular tectonics which and allows the design and construct a variety of is based on the formation of molecular networks complex purely organic or hybrid architectures. The through the design of complementary tectons or approach will be presented and illustrated by a variety molecular construction units. The generation of of tectons and networks. molecular networks and subsequently of crystals is

Fig. 1 : Dependence of  form to  form transition temperature on glass transition temperature

KEY WORDS: Self-assembly, Crystal Engineering, Supramolecular Chemistry, Molecular Tectonics

References 1. M. W. Hosseini, Acc. Chem. Res., 38, 313 (2005). 2. M. W. Hosseini, Chem. Commun., Focus Article, 582 (2005). 3. M. W. Hosseini, CrytsEngComm., 6, 318 (2004). 4. G. Marinescu, S. Ferlay, N. Kyritsakas, M. W. Hosseini, Chem. Commun., 49, 11209 (2013). 5. M. El Garah, N. Marets, S. Bonacchi, M. Mauro, A. Ciesielski, V. Bulach, M. W. Hosseini, P. Samori, J. Amer. Chem. Soc. 137, 8450 (2015). 6. C. Adolf, S. Ferlay M. W. Hosseini, J. Amer. Chem. Soc., 137, 15390 (2015). 2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2016, Strasbourg, France

Functional Fullerenes: Optoelectronic and self-assembly aspects

SANDEEPA K. V. and JOSHY JOSEPH Photosciences and Photonics Section, CSIR-National Institute for Interdisciplinary Science and Technology (NIIST), Trivandrum 695019, India and Academy of Scientific and Innovative Research (AcSIR), New Delhi 110001, India; E-mail: [email protected]

ABSTRACT: Unique photophysical, electrochemical covalent grafting of fullerenes with polymer units, ii) and self-assembling properties of fullerene derivatives template based non-covalent functionalization using render them as an attractive class of materials with polymers and biomolecules as template and iii) small wide range of applications in nanotechnology and molecule self-assembly. Our morphological material science.1 Tuning the substitution of the well investigation reveals the self-assembly of fullerene studied acceptor [6,6]-phenyl-C61-butyric acid methyl monomers as nanoclusters while self-assembled ester (PCBM) to upshift the LUMO (lowest polyfullerenes result in the formation of one unoccupied molecular orbital) is a strategy used to dimensional nanostructures. Detailed photophysical enhance the electron acceptor properties of fullerene and morphological investigations of such polyfullerene derivatives.2 However, the rational design of fullerene systems will be discussed. materials which can organize in one dimensional fashion is challenging due to their higher aggregation/crystallization tendency in the solid state leading to changes in electronic and charge transport Self-assembly Polymerisation properties. Most of the polymeric materials exhibit intrinsic one dimensional, self-assembled nanostructures due to their directionality and order in Figure 1. The schematic representation of formation of the monomeric unit itself. Developing covalently nanoclusters and one dimensional nanostructures upon modified polyfullerenes and non-covalently traditional self-assembly and polymerization, functionalized supramolecular fullerene polymers are respectively. promising strategies to create one dimensional fullerene materials.3 The functional, monomeric fullerene derivatives are synthetically accessible, and exhibit comparable optoelectronic properties to that of the parent PCBM derivative which can be polymerized via covalent or supramolecular techniques. The polyfullerenes which retain the optoelectronic properties of the core moiety can be developed by i)

KEY WORDS: Fullerene, self assembly, organic photovoltaics, DNA

References 1. Takashi Nakanishi et al., Recent progress in morphology control of supramolecular fullerene assemblies and its applications, Chem. Soc. Rev., 2010, 39, 4021–4035. 2. Yongfang Li., Molecular design of photovoltaic materials for polymer solar cells: toward suitable electronic energy levels and broad absorption, Acc. Chem. Res. 2012, 45, 723-733. 3. Nazario Martín et al., Fullerene Polymers: Synthesis and Properties, Chem. Rev., 2006, 106 (12), 5136–5190.Gowd, E. B., Nair, S. S., Ramesh, C., Macromolecules 2002, 35, 8509 2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2016, Strasbourg, France

Electro-triggered self-construction of polymeric films: click and mussel inspired chemistry

G. RYDZEK, A. DOCHTER, C. MAERTEN, T.GARNIER, E. PARDIEU, N. T. T. CHAU, P. LUPATTELLI, P. SCHAAF, L. JIERRY and F. BOULMEDAIS Institut Charles Sadron Strasbourg, France

+ ABSTRACT: Surface functionalization allows Generated at the surface of the electrode, Cu ions controlling the interaction of materials with their (morphogens) diffuse from the surface to the solution surrounding environment. Catalysis, molecular and catalyze the click reaction between azide and recognition or cell adhesion are typical examples of alkyne functionalized polymers. As the reaction only such interactions. During the last decades, progress in takes place in the presence of the morphogens, all the surface science allowed modifying and tuning constituents can be mixed in a single solution and the material's surface properties in a highly controlled way film formation takes place by a simple application of by the development of new coating methods. Among an electrical stimulus. them, the use of an external stimulus, such as an Merging the fields of polyelectrolyte multilayers and electric signal or light, appears as a convenient way of morphogen-driven film buildup, we developed a inducing a film buildup in a one pot manner. strategy which allows the self-assembly of oppositely We introduced a new type of electro-construction of charged macromolecules on a surface. This strategy is polymeric film based on the formation of covalent relied on a charge-shifting polyanion that undergoes a bonds between polymers1-3 induced by an electro- hydrolysis at acidic pH, generated electrochemically generated gradient of morphogens. First introduced by (H+ = morphogen), leading to a polycation. In the Turing,4 morphogens are specific molecules to which presence of an enzyme, this electro-controlled cells respond in a concentration-dependent manner. We hydrolysis leads to the formation of complexes on the extended this definition to film buildup on a surface surface.5 The obtained film, assembly of where morphogens are molecules or ions that induce a polycation/enzyme complexes, is enzymatically active. chemical reaction or interaction in a confined space Inspired by the catechol numerous properties, a mussel near a surface. In a first study, Huisgens – Sharpless protein derived molecule, we designed a catechol based click reaction was used to induce a reticulation electrochemically triggered construction of films based between two polymers by electro-oxidation of Cu2+ on an organic morphogen: a synthesized ethylene into Cu+ (Fig. 1).1 glycol spacer bearing catechol groups on both sides, named bis-catechol. By application of a defined electrochemical potential, bis-catechol spacers undergo an oxidation in the close vicinity of the surface, leading to its “active” state (bis-quinone). In this active state, bis-quinone spacers can react with amino groups of a polymer through Michael addition and Schiff’s base condensation reaction forming a film exclusively on the electrode surface.6 The electro-triggerred self-construction of films is well Fig. 1 : Schematic representation of the one-pot self- suited for the functionalization of micro-electrodes by construction of polymeric film based on click- enzymes opening the route towards miniaturized chemistry triggered by the application of an electric biosensors. potential.

KEY WORDS: Self-assembly, polyelectrolytes, electrochemistry, catechol

References 1. Rydzek, G.; Jierry, L.; Parat, A.; Thomann, J. S.; Voegel, J. C.; Senger, B.; Hemmerle, J.; Ponche, A.; Frisch, B.; Schaaf, P.; Boulmedais, F., Angew. Chem. Int. Ed. 2011, 50, 4374. 2. Rydzek, G.; Garnier, T.; Schaaf, P.; Voegel, J. C.; Senger, B.; Frisch, B.; Haikel, Y.; Petit, C.; Schlatter, G.; Jierry, L.; Boulmedais, F., Langmuir 2013, 29, 10776. 3. Rydzek, G.; Parat, A.; Polavarapu, P.; Baehr, C.; Voegel, J. C.; Hemmerle, J.; Senger, B.; Frisch, B.; Schaaf, P.; Jierry, L.; Boulmedais, F., Soft Matter 2012, 8, 446. 4. Turing, A. M., Philos. Trans. R. Soc. Lond. 1952, 237, 37. 5. Dochter A., Garnier T., Pardieu E., Chau N.T.T., Maerten C., Senger B., Schaaf P., Jierry L. and Boulmedais F. Langmuir 2015, 31, 10208. 6. Maerten C., Garnier T., Lupattelli P., Chau N.T.T., Schaaf P., Jierry L. and Boulmedais F. Langmuir 2015, 31, 13385 2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2016, Strasbourg, France

Self-assembling Peptide Based Functional gels A. Banerjee Department of Biological Chemistry, Indian Association for the Cultivation of Science, Jadavpur,Kolkata-700032, India, e-mail: [email protected]

ABSTRACT: Molecular self-association plays a vital role in chemical, biological and material sciences. Peptides with suitable functionalities are good candidates for the assembly by using various non- covalent interactions including hydrogen bonding, pi-pi stacking, electrostatic, solvophobic and others. Under a suitable situation, a peptide can be self-assembled to form a micro/nano-fibrillar network structure occupied by a large amount of solvent molecules (water/organic solvent) and this forms a soft material called gel. It is interesting to control the assembly of designer oligopeptides to make useful gels and also to explore fascinating applications of these gels. These gels were applied to perform a variety of functions including carriers of drugs1 and other biologically active molecules2, removal of toxic organic dyes from waste-water3, oil spill recovery4, and semiconducting photo-switching materials5. Moreover, some of these peptide based hydrogels exhibit a remarkable self-healing property, that is usually very rare in non-living systems. The self-healing property can also be tuned by the incorporation of carbon based Fig. 1 : Various applications of self-assembling nanomaterials like carbon nanotubes and graphene peptide based gels. oxide.6 A gel based novel trihybrid system with nanofibers, nanosheets and nanoparticles has also been 7 . dicovered. Another interesting study demonstrates peptide based soft biomaterials for cancer drug release and modulation of stiffness, drug release capacity and proteolytic stability of these hydrogels by incorporating D-amino acid residue(s).8 A recent study demonstrates peptide based injectable gels with remarkable 9 antibacterial activity against Gram negative bacteria.

KEY WORDS: Peptides, hydrogels, drug carriers, self-assembly, waste water treatment, hybrid nanomaterials.

References 1. (a) Naskar, J., Palui, G., Banerjee, A., J. Phys. Chem. B 2009, 113, 11787; (b) Baral, A., Roy, S., Dehsorkhi, A., Hamley, I. W., Mohapatra, S., Ghosh, S., Banerjee, A. Langmuir 2014, 30, 929. 2. Nanda, J., Banerjee, A., Soft Matter 2012, 8, 3380. 3. Adhikari, B., Palui, G., Banerjee, A., Soft Matter 2009, 5, 3452. 4. Basak, S., Nanda, J., Banerjee, A., J. Mater. Chem. 2012, 22, 11658. 5. Roy, S., Maiti, D. K., Panigrahi, S., Basak, D., Banerjee, A., Phys.Chem. Chem. Phys. 2014, 16, 6041. 6. Roy, S., Baral, A., Banerjee, A., Chem.-Eur. J. 2013, 19, 14950. 7. Nanda, J., Biswas, A., Adhikari, B., Banerjee, A., Angew. Chem. 2013, 125, 5145; Angew. Chem. Int. Ed. 2013, 52, 5041. 8. Basu, K., Baral, A., Basak, S., Dehsorkhi, A., Nanda, J., Bhunia, D., Ghosh, S., Castelletto, V., Hamley, I. W., Banerjee, A., Chem. Commun. 2016, 52, 5045. 9. Baral, A., Roy, S., Ghosh, S., Merino, D. H.-, Hamley, I. W., Banerjee, A., Langmuir 2016, 32, 1836. 2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2016, Strasbourg, France

Soft-mechanochemistry – Mechanochemistry inspired by nature

P. SCHAAF1,2, F. BOULMEDAIS2, PH. LAVALLE1, L. JIERRY2 (1) Unité INSERM Biomaterials and Bioengineering, INSERM/University of Strasbourg, Starsbourg, France (2) Institut Charles Sadron (CNRS), Strasbourg, France

ABSTRACT: Mechano-transduction processes play a key role in nature and in particular in 1,2 cell adhesion. One general way that nature 1,1 found to transform a mechanical signal into a 1,0

0,9 chemical one is by making use of force . induced conformational changes. Such 0,8 0,7 changes can be at the origin of cryptic site exhibition but they can also affect enzymatic 0,6 0,5 activity. We have, over the last years, (mean+/- standard deviation) slope relative to that of the initial state of initial to that the relative slope 0,4 developed several chemo-mechano- 0,3 0-c 0-a 0-b 0-d 50-c 80-c 10-a 20-a 30-a 40-a 50-a 60-a 65-a 70-a 80-a 85-a 50-b 80-b 100-c 100-a responsive systems based on mimicking 100-b natural processes. We will present here stretching (%) several examples of such systems: We will Fig. 1 : Evolution of the enzymatic activity of a polymeric film containing β-galactosidase for various discuss systems where by stretching one can stretching degrees (upper evolution: enzymes not modulate the binding affinity of a ligand for covalently fixed to the polymeric matrix; lower receptors present on the substrate (1,2). We evolution: enzymes covalently fixed to the polymeric will also present systems where stretching matrix) (results taken from ref 5) allows modulating the enzymatic activity of the film. Such systems are either based on exhibiting enzymes through a barrier (3) or on modifying a protein (4) or an enzyme conformation (5) by stretching. In contrary to processes where the application of a mechanical force on a molecule affects its chemical bonds, mechano-transductive processes based on affecting macromolecular conformations require much less energy and new routes to develop such systems will be discussed.

KEY WORDS: mecano-transduction, soft-mechanochemistry, cell adhesion

References (1) Davila D. et al. J. Am. Chem. Soc. 134, 83 (2012) (2) Bacharouche J. et al. ACS Nano 7, 3457 (2013) (3) Mertz D. et al. Nature Mater. 8, 731 (2009) (4) Longo J. et al. Chem. Comm. 51, 5622 (2015) (5) Rios, C. et al. Chem. Comm. 51, 232 (2015)

2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2016, Strasbourg, France

Metallohydrogels from Bile Salts

T. GORAI, R. LAISHRAM, M. MAITY, UDAY MAITRA* Department of Organic Chemistry Indian Institute of Science Bangalore 560 012, India

ABSTRACT: Functional molecular gels are being increasingly investigated owing to their potential applications in various fields such as biomaterials, sensing, optoelectronics etc. Among many known gelators, bile acid derivatives are known to form self- assembled fibrillar networks (SAFINs), eventually leading to the immobilization of solvent molecules around them. We have recently developed a variety of metallo-hydrogels, predominantly derived from cholate salts. This lecture will highlight our current understanding of the structures of these gels, and the use of these novel soft materials for the design of nanostructured materials, luminescent hydrogels and enzyme sensors.

Fig 2: Nanostructured metal sulfide and metal nanoparticles embedded in the Ca-cholate gel matrix

Fig 1: Color tunable lanthanide gels

KEY WORDS: bile salts, hydrogels, lanthanides, photoluminescence, nanomaterials

References 1. Laishram, R., Bhowmik, S., Maitra, U. J. Mater. Chem. C, 2015, 3, 5885-5889. 2. Maity, M., Maitra, U. J. Mater. Chem. A, 2014, 2, 18952-18958. 3. Bhowmik, S., Gorai, T., Maitra, U. J. Mater. Chem. C. 2014, 2, 1597-1600. 4. Kandanelli, R., Sarkar, A., Maitra, U. Dalton Trans. 2013, 42, 15381-15386. 5. Bhowmik, S., Maitra, U. Chem. Commun., 2012, 48, 4624. 6. Banerjee, S., Kandanelli, R., Bhowmik, S., Maitra, U. Soft Matter 2011, 7, 8207. 7. Bhowmik, S., Banerjee, S., Maitra, U. Chem. Commun. 2010, 46, 8642

2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2016, Strasbourg, France

Polyaniline Nanotubes and Their Applications

SUDIP MALIK Polymer Science Unit, Indian Association for the Cultivation of Science, 2A & 2B Raja S. C. Mullick Road, Jadavpur, Kolkata, India. 700032

ABSTRACT: Conducting polymer nanostructures with the assembly of surfactants, polyelectrolytes and defined size, shape, architecture and chemical organic dopants to create network 1D structure is functionality have received more attention nowadays, promising as it uses the bottom-up approach of because they are the forefront of many next-generation supramolecular chemistry. Inspired by the easy organic optoelectronic technologies. Among preparation of PANI and the use of water as an conducting polymers such as polypyrrole, environment friendly solvent, we wonder if we could polythiophene, polyphenylenevinylene, and directly obtain nanoscale PANI based on soft templated polyacetylene, polyaniline (PANI) has been most method by self assembly of organic acids in aqueous extensively studied because it exhibits good medium. environmental stability and its electrical properties can Herein, we report a simple process of synthesis of be modified by both the oxidation state of the main nanostructure of PANI doped with several chain and protonation. However, the control of the size tetracarboxylic acid (aromatic and non-aromatic) in and morphology during the synthesis of nanostructured bulk quantity via in-situ polymerization. The PANI still remains a challenge. The reported methods architectures and properties of the formed PANI for the synthesis of PANI nanostructures include nanotube will be presented. This lecture will discuss interfacial polymerisation method, electrospinning, about the architectures and properties of the formed seeding polymerisation and template method (hard and PANI nanotube, particularly recent applications. soft). Among them, the soft-templated method utilizing

Aniline Aromatic Tetracarboxylic Acid

FIGURE1: Schematic view of formation of PANI nanotubes doped with aromatic acids.

KEY WORDS: Nanoscale morphology, Conducting polymers, Polyaniline, Applications.

References 1. Rana, U., Chakrabarty, K., Malik, S. , J. Mater. Chem. 2012, 22, 15665. 2. Rana, U., Mondal, S., Sannigrahi, J., Sukul, P.K., Amin, Md. A , Majumdar, S., Malik, S., J. Mater. Chem. C 2014, 2, 3382. 3. Mondal, S., Rana, U., Malik, S., Chem. Commun. 2015, 51, 12365. 4. Mondal, S., Rana, U., Malik, S., ACS Applied Materials and Interfaces 2015, 7, 10457.

2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2016, Strasbourg, France

Organized or Self-organized Patterns on Plasma-exposed Polymer Surfaces

V. ROUCOULES Institut de Science des Matériaux de Mulhouse, 15 rue Jean Starcky, 68057 Mulhouse Cedex, France

ABSTRACT: A plasma typically produces a plethora of 100 nm different precursor species (molecules, atoms, and radicals), in a large number of different energetic states (ionized, excited, metastables, and ground states) compared with solid, liquid, or gaseous precursors. These plasma precursors are thus very likely to assemble into solid objects with different properties 1. This plasma-specific effect enables many interesting features in the synthesis, surface structuring, and processing of soft organic nanomaterials such as Fig. 1 : AFM images of the beads and branches structures during polymers. plasma polymerization Since few years our group works on the possibility to produce self-organized plasma polymer nanopatterns A second example is organization or « self »- without using any etching masks. This task stills organisation which result from the interplay between challenging and the main problem comes from the the plasma and solid components involved. Recently difficulty to identify the prevailing driving forces that our group has demonstrated the feasibility to design lead to the formation of the observed organized or self- super-structures under co-deposition of crystalline organized patterns on plasma-exposed polymer nanocellulose whiskers (CNW) during plasma surfaces. The other difficulty is the multi-scale nature polymerization of maleic anhydride 3, Figure 2. A of this system, where diverse chemical and physical close view over the superstructures provided some phenomena may take place at different spatial and information regarding its formation. temporal scales.

Very recently, we report for the first time the formation of unexpected beads and branched structures in the surface of plasma polymerized maleic anhydride 2, Figure 1. The formation of the structures was linked to the decoupling and competition between rate of deposition and rate of diffusion of plasma active species. While the beads could be formed even in moderate to high duty cycle (DC), the formation of the Fig. 2 : Phase AFM images of plasma polymer films deposited in branched and needle structures required long pulse-off presence of crystalline nanocellulose whiskers time (toff) and short pulse-on time (ton), provided by low DC, which afford enough time for the radicals to This work brought new important information that migrate and react with the nucleation sites. The goal of represent a step forward in the understanding of the this presentation is to get further insights of morphogenesis of complex structures induced by aforementioned mechanisms. plasma polymerization process.

KEY WORDS: Plasma Polymerization, Self-Organized Nanopatterns, Morphogenesis, Complex Structures

References 1. K. Ostrikov, K., Neyts, E. C., Meyyappan, M., Advances in Physics 2013, 62, 113 2. Brioude, M., Laborie, M.P., Airoudj, A. Haidara, H., Roucoules, V., Plasma processes and polymers 2014 11, 943 3. Brioude, M., Laborie, M.P., Haidara, H., Roucoules, V., ACS Applied Materials and Interfaces 2015, 7, 14079

2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2016, Strasbourg, France

Structure, Morphology and Functionality of Multiphase Polymer Systems Containing Poly(ʟ-lactide)

E. Bhoje Gowd Materials Science and Technology CSIR-National Institute for Interdisciplinary Science and Technology (CSIR-NIIST) Trivandrum, Kerala, India – 695019 [email protected]

ABSTRACT: Poly(ʟ-lactide) (PLLA), the most common block plays a significant role in the formation of stereoisomer of the poly(lactic acid), is a widely used mesophase of PLLA in block copolymer systems. Last biobased polymer in degradable plastics. It is also used part of the talk highlights the structural changes in as a degradable biomaterial in many medical devices PLLA/CPO co-crystals at multiple length scales using and tissue engineering. In this talk, three types of differential scanning calorimetry, small-angle neutron multiphase polymer systems containing poly(L-lactide) scattering, Fourier transform infrared spectroscopy, will be presented. In all cases, the crystallization of and temperature-dependent wide- and small-angle X- PLLA plays a significant role in the self-assembly of ray scattering. the multiphase systems. These kinds of materials have attracted considerable interest from many researchers because of their applications in the medical field and nanolithography.

The first system covers the synthesis and photophysical properties of star-shaped PLLA containing dipyridamole core. This study shows that the solid state emission properties of dipyridamole core are sensitive to the polymer chain conformation of PLLA in the multiphase system. The second system deals with the structure development in PLLA containing triblock copolymers (poly(ʟ-lactide-b-dimethylsiloxane-b-ʟ- lactide and poly(ʟ-lactide-b-ethylene glycol-b-ʟ- lactide) during the cold crystallization of the triblock copolymer films (Figure 1). The block copolymer PLLA-PDMS-PLLA was immiscible in the melt, and the melt morphology was preserved upon cooling the melt to  120 °C. On the other hand, PLLA-PEG- PLLA was miscible in the melt. The breakout and preservation of the nanostructure morphology of the triblock copolymers have been investigated by variable Fig. 1: Lorentz-corrected SAXS patterns of (a) PLLA- temperature small-angle and wide-angle X-ray b-PEG-b-PLLA and (b) PLLA-b-PDMS-b-PLLA in scattering (SAXS and WAXS) during heating. It was the melt-quenched (amorphous) state. observed that the segmental mobility of the PLLA

KEYWORDS: poly(L-lactide), self-assembly, crystallization, co-crystals, star polymers

References 1. Nagarajan, S., Gowd, E. B., Macromolecules 2015, 48, 5367 2. Shaiju. P., Murthy, N.S., Gowd, E. B., Macromolecules 2016, 49, 224 2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2016, Strasbourg, France

Towards New High Performance Radical and Cationic Photoinitiating Systems

F. DUMURa, D. GIGMESa, J.-P. FOUASSIERc, J. LALEVEEb* aAix-Marseille Université, CNRS, Institut de Chimie Radicalaire, UMR 7273, F-13397 Marseille, France; bInstitut de Science des Matériaux de Mulhouse IS2M, UMR CNRS 7361, UHA, 15, rue Jean Starcky, 68057 Mulhouse Cedex, France; cENSCMu-UHA, 3 rue Alfred Werner, 68093 Mulhouse Cedex, France Email of corresponding author: [email protected] highly versatile and high performance visible light ABSTRACT: The key point in the photopolymerization photoinitiating systems. area is the transformation of multifunctional monomers New radical chemistry (e.g. boryl, silyl, germyl (e.g. acrylates or epoxides) or prepolymers into highly …) can also be used for high performance radical crosslinked networks using a photochemical route initiating systems.[1-3] Some examples will be provided. where photoinitiating systems PISs generating radical, cation or radical cation initiating species play an . important role. Halogen lamps, laser diodes or LEDs are now cheap and readily available. Even though some systems, e.g. camphorquinone CQ, are already available and used in industrial applications in the 450- 470 nm range, the challenge still remains open to develop versatile PISs that can efficiently initiate various types of photopolymerizations, i.e. the radical polymerization of acrylates, the cationic polymerization of epoxide and vinylether monomers, the hybrid cure of acrylate/epoxide blends and the thiol-ene photopolymerization under blue light irradiations. In this presentation, new families of radical photoinitiators for visible light (e.g. cheap and safe LED) are presented.[1-3] Their abilities to photochemically produce radicals and cations were investigated by electron spin resonance spin trapping, fluorescence, cyclic voltammetry, laser flash photolysis, and steady state photolysis techniques. The photoinitiation upon visible light irradiation (halogen lamp, 405 and 457 nm laser diodes, 455, 462 or 470 nm LEDs) will be discussed. Compared to well known references, the new proposed combinations appear as

KEY WORDS: Photopolymerization, photoinitiating system, LED

References

1. P Xiao, F Dumur, B Graff, D Gigmes, JP Fouassier, J Lalevee, Blue Light Sensitive Dyes for Various Photopolymerization Reactions: Naphthalimide and Naphthalic Anhydride Derivatives Macromolecules, 47, 601-608 (2014). 2. P Xiao, M Frigoli, F Dumur, B Graff, D Gigmes, JP Fouassier, J Lalevee, Julolidine or Fluorenone Based Push–Pull Dyes for Polymerization upon Soft Polychromatic Visible Light or Green Light. Macromolecules, 47(1), 106-112 (2014). 3. P Xiao, F Dumur, B Graff, F Morlet-Savary, L Vidal, D Gigmes, JP Fouassier, J Lalevee, Structural Effects in the Indanedione Skeleton for the Design of Low Intensity 300–500 nm Light Sensitive Initiators. Macromolecules, 47(1), 26-34 (2014). 2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2016, Strasbourg, France

Stimuli-Responsive Poly(zwitterions) and Poly(ionic liquid)s

T. MAJI, Y. BISWAS and T. K. MANDAL Polymer Science Unit, Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700 032, India. E-mail: [email protected]

ABSTRACT: Stimuli‐responsive smart polymers are by discussing the aqueous solution behavior of PSA used as precursor of advanced polymer materials for solution in the pH range of 2.4‐3.4 where it forms sensing, biomedical application, device application etc. insoluble aggregates through the intra‐ and inter‐ Different functionalities of smart polymers make the molecular electrostatic interaction between the polymers responsive to different stimuli such as pendent ammonium and carboxylate groups of the temperature, pH, light, ionic strength, redox system neighboring zwitterionic PSA molecules. Furthermore, and host–guest interactions. the temperature dependent phase transition upon Zwitterionic polymers contains both cationic and heating of the biphasic PSA solution at that pH range, anionic moiety into the repeating unit which helps exhibiting distinct reversible upper critical solution them to respond to different external stimuli. temperature (UCST) will be discussed. The effect of Furthermore, the introduction of amino acid into molecular weights, the solution pH and the electrolyte those polymers makes them more bio‐friendly. The type on the UCST will also be discussed. Finally, the fictionalization of a vinyl monomer with amino acid synthesis of fluorescein isothiocyanate (FITC) tagged through the reaction between terminal chain PSA with dual‐responsiveness will also be discussed. functional group of amino acid with appropriate Furthermore, in the area of stimuli responsive PILs, functional groups [such as –COOH or –COX (X = Cl, Br)] the synthesis of a cationic phosphonium poly(ionic of vinyl monomer leads to zwitterionic monomers. liquid) of varying and controllable molecular weights Subsequent polymerizations of amino acid‐based via reversible addition‐fragmentation chain transfer monomers lead to the formation of the zwitterionic (RAFT) polymerization will be discussed. It is known polymers with pendent amine and carboxylic acid that water‐soluble poly(ionic liquid)s often exhibit a functional groups. lower critical solution temperature (LCST). In contrast, In recent time, poly(ionic liquid)s (PILs) have also in this case, it will be shown that the transparent gained considerable attention to the polymer and aqueous solution of this PIL turns into a turbid materials science community because of their wide solution in presence of halide ions, forming insoluble range of applications such as CO2 sorbents, porous microgel aggregates owing to intra‐ and/or inter‐chain materials, carbon precursors, catalytic materials and cross‐linking through halide ion bridges between PILs, specially as a stimuli‐responsive materials. which upon heating exhibits a distinct upper critical I will discuss several recent developments of different solution temperature (UCST)‐type phase transition synthetic routes of poly(zwitterions) and PILs in our due to disruption of ion bridges. A cross‐linked laboratory. In particular, the synthesis of ε‐L‐lysine‐/L‐ hydrogel system containing this PIL with both halide serine‐/L‐methionine‐based zwitterionic polymers of ion‐ and thermo‐responsiveness (UCST‐type) will be controllable molecular weights and low dispersities presented. The application of this PIL as a smart will be discussed. It will be shown that in alkaline pH, stabilizer to promote water borne double‐responsive poly(ε‐L‐lysinyl acrylamide) (PLAM) undergoes Cu(II) dispersion of multi‐walled carbon nanotubes ion‐induced aggregation through the complexation its (MWCNTs) towards halide ions and temperature will pendent amine and carboxylic groups with Cu(II) ion also be discussed. resulting in the formation of spherical nanogel aggregates, which dissociates at a pH <5.5 resulting in molecular dissolution of PLAM. This will be followed

KEY WORDS: Poly(zwitterions), Poly(ionic liquid)s, Thermo-responsive, pH-responsive, UCST, Amino acid, Aggregation,

References 1. Banerjee, S.; Maji, T.; Paira, T. K.; Mandal, T. K., Macromol. Rapid Commun. 2013, 34, 1480-1486. 2. Maji, T.; Banerjee, S.; Biswas, Y.; Mandal, T. K.,Macromolecules 2015, 48, 4957-4966. 3. Biswas, Y.; Maji, T.; Dule, M.; Mandal, T.K., Polym. Chem., 2016, 7, 867–877

2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2019, Strasbourg, France

Sheathing polymers fibrils with nanotube-forming molecules

A. BOULAOUED1, G. RAJ2, J. LACAVA1, J. FAURE-VINCENT2, F. CHANDEZON2, P. MESINI1, M. BRINKMANN1, J.M. GUENET1 1 Institut Charles Sadron, CNRS-Université de Strasbourg 23 rue du Loess, F-67034 STRASBOURG, France 2 CEA/SPrAM, UMR5819) 17, rue des Martyrs, F-38054 GRENOBLE Cedex 9, France

1 ABSTRACT: Recently, P. Mésini and coworkers have matching do show a difference between the scattering prepared nanotubular structures from diamide function of the nanotubes in the binary systems and molecules (3,5-Bis-(5-hexylcarbamoyl-pentyloxy)-ben- those in the hybrid system at very low angles (figure 1 zoic acid decyl ester, BHPB-10 for short) (Scheme 1). inset). The inner and outer diameter of the nanotubes are very We have extended this process to a semi-conducting well-defined with very little cross-section dispersity as polymer, Poly(3-butylthiophene-2,5-diyl) (P3BT). The ascertained by the scattering patterns (fig.1) . system has been studied by neutron scattering and by conducting AFM (C-AFM).

Scheme 1 : The 3,5-Bis-(5-hexylcarbamoyl-pentyl- oxy)-benzoic acid decyl ester molecule (BHPB-10).

Fig.2: left: the principle of the C-AFM measurement for P3BT fibrils sheathed by BHPB-10. Right the cross-section of the hybrid fibril.

The C-AFM experiments reveal that P3BT fibrils are Fig. 1: SANS curves for: () BHPB-10/trans-deca- covered with BHPB-10 thus forming a hybrid system. hydronaphthalene gels; ()BHPB-10/iPS/trans-deca- By means of the process shown in fig 2, gradual hydronaphthalene hybrid systems. Inset: the curves in -1 penetration of the conducting tip into presumably the low-angle domain q= 0 to q= 0.5 nm . (ref. 2). sheathed fibrils first reveals the behavior of an

2 insulator (BHPB-10), and then the behavior of a semi- We have recently shown that the sheathing of polymer conductor (P3BT). fibrils grown from an isotactic polystyrene SANS experiments give further confirmation to these thermoreversible gel can be achieved with these outcomes. Scattering curves can be fitted with nanotubes. Only a physical process is involved, namely concentric cylinders, which bears out the model where heterogeneous nucleation. The polymer fibrils act as P3BT fibrils are sheathed by BHPB-10 nanotubes. heterogeneous nuclei onto which the nanotubes form. Neutron scattering experiments using contrast

KEY WORDS: hybrid meterials, self-assembling, Thermoreversible gels, fibrils, sheathing

References 1. N. Diaz, F.-X. Simon, M. Schmutz, M. Rawiso, G. Decher, J. Jestin and P. Mésini, Angew. Chem., Int. Ed., 2005, 44, 3260 2. Dasgupta, D.; Kamar, Z.; Rochas, C.; Dahmani, M.; Mesini, P.; Guenet, J. M. Soft Matter 2010, 6, 3573 3. G. Raj, A. Boulaouedᵩ, J. Lacava, P.J. Mésini, M. Brinkmann, J. Faure-Vincent, J-M Guenet to be submitted

POSTERS 2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2016, Strasbourg, France

Piling up pillar[5]arenes to self-assemble nanotubes

I. NIERENGARTEN,a S. GUERRA,a,b H. BEN AZIZA,a M. HOLLER,a J. BARBERA,c R. DESCHENAUXb AND J.-F. NIERENGARTENa aLaboratoire de Chimie des Matériaux Moléculaires, Université de Strasbourg et CNRS, ECPM, 25 rue Becquerel, 67087 Strasbourg Cedex 2, France bInstitut de Chimie, Université de Neuchâtel, Avenue de Bellevaux 51, 2000 Neuchâtel, Switzerland cDepartamento de Química Orgánica, Instituto de Ciencia de Materiales de Arágon, Universidad de Zaragoza-CSIC, 50009 Zaragoza,Spain

ABSTRACT: Pillar[5]arenes are para-cyclophane derivatives composed of five 1,4-disubstituted hydroquinone subunits linked together by methylene bridges.1 Since the first report on their one-step synthesis in 2008,2 they have been already used for many applications in the field of supramolecular chemistry.3 Owing to their cylindrical structure, pillar[5]arenes appear as an attractive platform for the preparation of nanomaterials with a controlled distribution of functional groups on the macrocyclic framework. Following the first exemple of liquid- cristalline pillar[n]arenes reported by our group4, we decided to prepare new derivatives by grafting first- generation Percec-type poly(benzylether) dendrons onto the macrocyclic scaffold5. The molecules adopt a disc-shaped structure perfectly suited for the self- organization into a columnar liquid-crystalline phase. In this way, the pillar[5]arene cores are piled up thus Schematic representations of (A) pillar[5]arene forming a nanotubular wire encased within a shell of derivative (dark blue: pillar[5]arene core, pale blue: peripheral dendrons. The capability of pillar[5]arenes peripheral dendrons), (B) the columnar stacks of the to form inclusion complexes has been also exploited. compound, (C) the supramolecular arrangement of Specifically, detailed binding studies have been carried the compound into the hexagonal columnar phase, out in solution with 1,6-dicyanohexane as the guest. (D) the columnar stacks of the inclusion complex Inclusion complexes have also been prepared in the (dark red: 1,6-dicyanohexane guest). solid state. The supramolecular organization into their Colh mesophase has been deduced from XRD data and found to be similar to the one observed within the crystal lattice of a model inclusion complex prepared from 1,4-dimethoxypillar[5]arene and 1,6- dicyanohexane.

KEY WORDS: pillar[5]arenes, liquid crystals, self-assembly, supramolecular chemistry

References 1. Cao, D., Meier, H., Asian J. Org. Chem. 2014, 3, 244; Strutt, N. L., Zhang, H., Schneebeli, S. T., Stoddart, J. F., Acc. Chem. Res. 2014, 47, 2631 2. Ogoshi, T., Kanai, S., Fujinami, S., Yamagishi, T.-a., Nakamoto, Y., J. Am. Chem. Soc. 2008, 130, 5022 3. Ogoshi, T., Yamagishi, T.-a., Eur. J. Org. Chem. 2013, 2961; Zhang, H., Zhao, Y., Chem. Eur. J. 2013, 19, 16862 4. Nierengarten, I., Guerra, S., Holler, M., Nierengarten, J.-F., Deschenaux, R., Chem. Commun. 2012, 48, 8072; Nierengarten, I., Guerra, S., Holler, M., Karmazin-Brelot, L., Barbera, J., Deschenaux, R., Nierengarten, J.-F., Eur. J. Org. Chem. 2013, 3675 5. Nierengarten, I., Guerra, S., Ben Aziza, H., Holler, M., Abidi, R., Barbera, J., Deschenaux, R., Nierengarten, J.-F., Chem. Eur. J., DOI: 10.1002/chem.201600688.

2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2016, Strasbourg, France

Thio-based multidentate fullerene adducts for the one-pot synthesis of sub-3 nm gold nanoparticle networks

U. HAHN,a G. ROUSSEAU,b A. DEMESSENCEb and J.-F. NIERENGARTENa a Laboratoire de Chimie des Matériaux Moléculaires (ECPM), UMR 7509, Université de Strasbourg, France b Institut de Recherches sur la Catalyse et l’Environnement de Lyon (IRCELYON), UMR 5256, Université Lyon 1, Villeurbanne, France

ABSTRACT: One of the biggest challenges in nanotechnology is to control the self-assembly of interconnected nanoparticles at the microscopic scale [1]. 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 [2]. 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 Fig. 1 : Self-assembly of homogeneous ultra-small preparation of 3D-networks incorporating smaller gold nanoparticles thanks to the design of a new GNPs remains a challenge. This is particularly hexaadduct fullerene bearing 12 thiocyanate important for their future application in the field of functions. 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 [3]. 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.

KEY WORDS: gold nanoparticles, fullerene, hexa-adducts

References 1. Mann, S., Chem. Commun. 2004, 1, 1; Mann, S., Nat. Mater. 2009, 8, 781. 2. Urban, A. S., Pfeiffer, T., Fedoruk, M., Lutich, A. A., Feldmann, J., ACS Nano 2011, 5, 3585; Urban, A. S., Carretero-Palacios, S., Lutich, A. A., Lohmüller, T., Feldmann, J., Jäckel, F., Nanoscale 2014, 6, 4458; Jung, S. H., Jeon, J., Kim, H., Jaworski, J., Jung, J. H., J. Am. Chem. Soc. 2014, 136, 6446; Lee, S. S., Lee, L. P., Nanoscale 2014, 6, 3561; Phillips, R. L., Miranda, O. R., You, C.-C., Rotello, V. M., Bunz, U. H. F., Angew. Chem. Int. Ed. 2008, 47, 2590; M. Haruta, Angew. Chem. Int. Ed. 2014, 53, 52. 3. Rousseau, G., Lavenn, C., Cardenas, L., Loridant, S., Wang, Y., Hahn, U., Nierengarten, J.-F., Demessence, A., Chem. Commun. 2015, 6730. 2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2016, Strasbourg, France

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

E. MEICHSNER,1 R. MILEV,1 A. LOPEZ-PACHETO,1 I. NIERENGARTEN,1 T. M. N. TRINH,1,2 M. HOLLER,1 R. DESCHENAUX,2 and J-F. NIERENGARTEN.1 1 Laboratoire de Chimie Moléculaires, Université de Strasbourg et CNRS (France). 2 Institut de Chimie, Université de Neuchâtel (Switzerland).

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

KEY WORDS: Supramolecular chemistry / Inclusion complexes / Rotaxanes / Pillar[5]arenes / Amides

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

2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2016, Strasbourg, France

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

F. SCHILLINGER,1 S. GUERRA,2 J. IEHL,1 M. HOLLER,1 M. PETERCA,3 D. A. WILSON,3 B. E. PARTRIDGE,3 S. ZHANG,3 R. DESCHENAUX,2 V. PERCEC,3 J.-F. 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).

ABSTRACT: Dendronized fullerenes are an of the C60 core, the fullerodendrimers reported attractive synthetic target for fundamental herein self-organise into 2D columnar arrays, studies and practical applications.1 As part of due to the dominating self-assembling ability this research, we now report the first example of the peripheral dendrons.2 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

OC12H25 OC12H25 R R N N N N N N R R O O OC12H25 O OC12H25 N N O O N N 1a R = 1b R = (CH2)11 O N N O O O O N N N O O N OC12H25 N O O O O N R R OC12H25 OC12H25 O O O O O O O O OC12H25 O O O O O R 1c R = (CH2)11 O O R N O O O O N O O N N N N O O OC12H25 OC12H25 N N OC12H25 N N N N R R O O N O OC12H25 O OC12H25 N O O O N N N N 1d R = O 1e R = O R R O O O

OC12H25 OC12H25

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

2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2016, Strasbourg, France

Hybrid gels constructed from a Supramolecular Gel and copolymer: Enhancement of Conductivity, Mechanical Property, Fluorescence and Gelation Rate

P. CHAKRABORTY AND A.K. NANDI Polymer Science Unit, Indian Association for the Cultivation of Science, Jadavpur Kolkata-700 032, INDIA

ABSTRACT: Supramolecular gels are endowed with the fantastic property of stimuli-responsiveness which the F-PVPS5 gel shows a sigmoidal increase. The makes them appropriate candidates for applications in gelation rate constants manifests that PVPS enhances diverse fields. However, the practical applications of the gelation rate. The hybrid gel exhibit five orders supramolecular gels are limited as they are increase of dc-conductivity than that of F gel showing mechanically weak. One uncomplicated way to semiconducting nature in the current-voltage plot. The improve the mechanical and thermal stability of the Nyquist plot in impedance spectra of F-PVPS5 xerogel supramolecular gels is to prepare hybrid gels with depict a depressed semicircle with a spike at lower covalent polymers. frequency region and the equivalent circuit represent a In an endeavor to improve the mechanical complex combination of resistance–capacitance property of folic acid (F) gel, poly(4-vinylpyridine-co- circuits attributed to the hybrid morphology of the gel styrene)(PVPS) is elegantly incorporated as a fibers. polymeric additive as it possess tremendous potential to form H-bonding and π-stacking with F. The hybrid gels are designated as F-PVPSx gels where x denotes the amount of PVPS (mg) added in 2 ml of F gel Self (0.3%, w/v). PVPS assisted gel formation of F is Assembly obvious from the drop in critical gelation concentration Folic and increased fiber diameter and branching of F- acid PVPSx gels compared to that of F gel. PVPS confers . an outstanding improvement of mechanical properties. Co-Assembly The complex modulus increases with increasing PVPS concentration with a maximum in F-PVPS5 gel. Creep recovery experiments authenticate PVPS induced elasticity in the viscous F gel. The fluorescence intensity of F-PVPSx gels increases with increasing F-PVPSx gel PVPS concentration showing maxima at F-PVPS5 gel. F gel PVPS Gelation is examined by time dependent fluorescence spectroscopy and it is observed that F and F-PVPSx gels exhibit opposite trend; F gel shows a sigmoidal decrease in fluorescence intensity during gelation but

KEY WORDS: Supramolecular gel, rheolgy, gelation rate, dc conductivity, impedance spectra, creep recovery

References 1. Chen, L.; Revel, S.; Morris, K.; Spiller, D. G.; Serpell, L. C.; Adams, D. J. Chem. Commun., 2010, 46, 6738-6740. 2. Cornwell, D. J.; Okesola, B. O.; Smith, D. K. Angew. Chem. Int. Ed., 2014, 53, 12461-12465.

2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2016, Strasbourg, France

Amino acids as building blocks in comb polymers

R. TAVERNIER, J.-F. LUTZ and D. CHAN-SENG Institut Charles Sadron, UPR22/CNRS, 23 rue du Loess, 67034 Strasbourg Cedex 2, France

ABSTRACT: Recent developments in polymer iterative addition of amino acids and synthetic building chemistry have permitted the preparation of polymers blocks on a solid support to prepare oligomers with advanced properties by controlling their topology, containing amino acids that are inserted on their main functionality and microstructure providing access to chain.2,3 However, the synthetic strategy that will be more elaborated architectures1 such as star, comb and discussed here focused on the introduction of amino hyperbranched polymers that could be bearing a acids of the side chains of the polymer through the variety of functional groups at well-defined sites on the preparation of peptide-based macromonomers. These polymer chain. The ability to control the architecture of macromonomers have been synthesized by solid-phase polymers allows tuning their properties and adjusting peptide synthesis from a conventional peptide resin, i.e. their performances regarding targeted applications. 2-chlorotrityl chloride resin, involving the iterative Here the objective is to develop synthetic strategies addition of the desired amino acids on the support to prepare macromolecules containing amino acids. followed by the insertion of the polymerizable moiety These amino acids will be used either as elements of a of choice before cleavage from the resin. The peptide sequence relevant for biological applications or macromonomers were then polymerized under the to promote the introduction of further functionalities at relevant polymerization conditions according to the well-defined localizations on the macromolecule chain. polymerizable moiety to obtain peptide-based comb One approach that have been explored considered the polymers.

cleavage ( )n

piperidine

Macromonomers with pendent peptide grafts prepared by solid-phase synthesis and their polymerization to obtain peptide-based comb polymers.

KEY WORDS: graft polymers, solid-phase synthesis, peptide sequence

References 1. Matyjaszewski K., Gnanou Y., Leibler L. Macromolecular Engineering: Precise Synthesis, Materials Properties, Applications; Wiley: 2007 2. Chan-Seng D., Lutz J.-F. ACS Macro Letters 2014, 3, 291 3. Chan-Seng D., Lutz J.-F. In Sequence-Controlled Polymers: Synthesis, Self-Assembly, and Properties; American Chemical Society: 2014; Vol. 1170, p 103

2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2016, Strasbourg, France

Backbone-modified diphenylalnine self-assemblies in combination with carbon nanotubes

B. DINESH, C. MÉNARD-MOYON and A. BIANCO Institut de Biologie Moléculaire et Cellulaire, UPR 3572, CNRS, Immunopathologie et Chimie Thérapeutique, 67084 Strasbourg Cedex, France

ABSTRACT: The natural simple constituents of life - functionalized with the same peptide generated unique amino acids, sugars, lipids and nucleic acids are dendritic assemblies. This comparative study on self- intrinsically bioactive, biodegradable and assembly using diphenylalanine backbone homologues biocompatible which makes them as perfect building and of the co-assembly with CNT covalent conjugates blocks to generate new materials.1 In particular, the is the first example exploring the capacity of β and γ research on peptide-based materials has intensified peptides to adopt precise nanostructures, particularly in over the last few years, not only because of their combination with carbon nanotubes.5 synthetic versatility and their potential in biomedical applications, but also because they are promising bio- based alternatives to synthetic materials.1 The peptides composed of natural amino acids or in combination with other unnatural analogues are known to self- assemble or self-organise into complex architectures, such as peptide nanowires,2 nanotubes3 and nanofibers.4 Integrating such organized architectures with carbon nanotubes (CNTs) is of great interest in current research trend for applications in material science and biomedicine. Figure. Self-assembled nanostructures of  and  Herein, we studied the self-assembly of β and γ diphenylalanine homologues of diphenylalanine peptides under different solvent and pH conditions. We investigated the role of peptide backbone in tuning different types of nanostructures alone or in combination with carbon nanotubes. In spite of having the same side chain, β and γ peptides formed distinctively different nanofibers, a clear indication of the role played by the backbone homologation on self-assembly. The  peptide nanofibers bundled originating from a central nucleating point forming a dendritic like arrangements with the fiber diameters in the range 20 to 80 nm and several microns in lengths. The nanofibers of  peptide were rather shorter, more compact and aligned in parallel-like arrangement creating a sort of film. The variation of the pH allowed to transform the nanofibers into spherical structures. Moreover, the co-assembly of β and γ peptides with carbon nanotubes covalently

KEY WORDS: diphenylalanine, carbon nanotubes, co-assembly, nanofibers

References 1. Alemán, C; Bianco, A; Venanzi, M Peptide Materials: From Nanostuctures to Applications, John Wiley & Sons, 2013 2. Reches, M; Gazit, E Science 2003, 300, 625-627 3. Scanlon, S; Aggeli, A; Nano Today 2008, 3, 22-30. 4. Renliang, H; Rongxin, S; Wei, Q; Jun, Z; Zhimin, H Nanotechnology 2011, 22, 245609 5. Bhimareddy et.al. Nanoscale, 2015, 7, 15873.

2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2016, Strasbourg, France

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

S. TELITEL1, F. DUMUR2, S. TELITEL1, O. SOPPERA1, J. POLY1, F. MORLET-SAVARY1, J.P. FOUASSIER3, D. GIGMES2, J. LALEVEE1

1 Institut de Science des Matériaux de Mulhouse, UMR CNRS-UHA 7361, 15 rue Jean Starcky, 68057 Mulhouse Cedex, France ; 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.

1 ABSTRACT: Ir(ppy)3 was used as new catalyst for nIr; the polymer surfaces were analyzed by XPS. The controlled/living radical polymerization under light. In chemical mechanisms were examined through laser this subject a new iridium complex (nIr) was designed flash photolysis, NMR, ESR and size exclusion and investigated as a photoinitiator catalyst for radical chromatography experiments. and cationic polymerizations upon very soft irradiations (particularly visible light). A ring-opening polymerization (ROP) of an epox monomer was easily S promoted through the interaction between nIr and an N O iodonium salt (Iod) upon light. In radical Ir polymerization, a control of the methylmethacrylate O N polymerization (conducted under a 462 nm light) with S 1.4-1.6 polydispersity was displayed2. Surface modifications was also easily carried out through nIr Ir(ppy)3 surface re-initiation experiments i.e. the dormant species being reactivated by light in the presence of

KEY WORDS: visible-light, N-Vinylcarbazole, atom-transfer, photopolymerization, photocatalysis, organocatalysis, aldehydes, photoinitiators, methacrylates, alkylation

References 1. Fors, B. P., Hawker, C. J., Angew. Chem. Int. Ed. 2012, 51, 8850 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., Polym. Chem.. 2015, 6, 613

2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2016, Strasbourg, France

Synthesis of precision compatibilizers for composite materials

J. LOUWSMA,a,b S. JOLY,a J.-F. LUTZ,b D. CHAN-SENGb

aPSA Groupe, Site Vélizy, Chemin de Gisy, 78943 Vélizy-Villacoublay, France bInstitut Charles Sadron, UPR22/CNRS, 23 rue du Loess, 67034 Strasbourg Cedex 2, France

ABSTRACT: Mixing fibers in a polymer matrix to considered. The control of the sequence on the prepare composite materials can be challenging as their oligomer backbone was accessed by solid phase difference in chemical nature can result in their synthesis from a chlorotrityl chloride resin permitting incompatibility. However the homogeneity of the the iterative insertion of amino acids and synthetic composite materials is of high importance to reach building blocks.2 This technique allows for the materials with high performances. To overcome this synthesis of phenylalanine-based oligomers with a high difficulty one approach considers the use of additives, degree of precision in the design permitting to screen named compatibilizers, capable to enhance the some specific structural parameters in a controlled interfacial properties between the immiscible manner and thus identify the structural requirements components of the composite material.1 for the elaboration of efficient compatibilizers. In this context, the synthesis of sequence-controlled oligomers containing phenylalanine residues was

cleavage N HOOC 3

Fig. 1: Solid-phase synthesis of sequence-controlled oligomers containing phenylalanine residues.

KEY WORDS: compatibilizers, sequence-controlled oligomers, solid-phase synthesis

References 1. (a) Saheb D. N., Jog J. P., Adv. Polym. Technol. 1999, 18, 351-363; (b) Mukhopadhyay S., Deopura B. L., Alagiruswamy R., J. Thermoplast. Compos. Mater. 2003, 16, 479-495. 2. Chan-Seng D., Lutz J.-F., ACS Macro Lett. 2014, 3, 291-294.

2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2016, Strasbourg, France

Welding Molecular Crystals

C.R.R. ADOLF, S. FERLAY and M. W. HOSSEINI Molecular Tectonic Laboratory, University of Strasbourg, Institut Le Bel, 4, rue Blaise Pascal, F-67000 Strasbourg, France.

ABSTRACT: Both for fundamental and applied Taking advantage of the iso-structurality of this family sciences, the design of complex molecular systems in of crystals, welded crystals have been generated by the crystalline phase with strict control of order and epitaxial growth of crystalline region between two seed periodicity at both microscopic and macroscopic levels crystals (figure 2). is of prime importance for development of new solid- state materials and devices.1 The design and fabrication A of complex crystalline systems as networks of crystals A A (ii) displaying task-specific properties is a step toward A smart materials.2 Here we report on iso-structural, and A (i) almost iso-metric, molecular crystals of different A B colours, and their welding by 3D epitaxial growth into A (iii) 3 networks of crystals as single-crystalline entities. Upon combining the dicationic hydrogen bond (H- bond) donor tecton 1 (Fig. 1i), with H-bond acceptor II 4- anionic metallatectons [M L2] (M = Mn, Fe, Co, Ni, Cu or Zn) (Fig. 1ii), a series of iso-structural robust coloured crystals based on H-bonded 3D networks 12- (iv) ML has been obtained (Fig. 1iii) and characterized by 2 Fig. 2 : Schematic representation of homo- (ii) and XRD methods. hetero (iii) welding based on welding of preformed seed crystals (i). Photo of macroscopic homo-welded (Fe-Fe-Fe) (iv left) and hetero-welded (Fe-Zn-Fe) (iv right) crystals.

Welding of crystals by self-assembly processes into

(i) (ii) macroscopic networks of crystals is a powerful strategy for the design of hierarchically organized periodic complex architectures composed of different 1 -MnL 1 -FeL 2 2 2 2 12-CoL2 subdomains displaying targeted characteristics. Crystal welding may be regarded as a first step toward

1 -CuL 1 -ZnL the design of new hierarchically organized complex 12-NiL2 2 2 2 2 (iii) crystalline systems.

Fig. 1 : H-bond donor tecton 1 (i) and H-bond II 4- acceptor metallatecton [M L2] (ii). Iso-structural crystals formed by this tectons (iii).

KEY WORDS: H-bond network, epitaxial growth, iso-structurality, self-assembly crystal welding, molecular crystal, hierarchical organization.

References 1. Marinescu, G., Ferlay, S., Kyritsakas, N., Hosseini, M. W., Chem. Commun. 2013, 49, 11209. 2. Schmidt, G. M., J. Pure Appl. Chem. 1971, 27,647. Desiraju, G. D. Crystal Engineering: The Design of Organic Solids; Elsevier: New York, 1989. 3. Adolf, C. R. R., Ferlay, S., Kyritsakas, N., Hosseini, M. W., J. Am. Chem. Soc. 2015, 137, 15390.

2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2016, Strasbourg, France

Chiral Porous Coordination Networks

R. Corso, P. Larpent, A. Jouaiti, N. Kyritsakas an M. W. Hosseini Laboratoire de Chimie de Coordination Organique (UMR-CNRS 7140) Université de Strasbourg, Institut Le Bel, 4 tue Blaise Pascal, 67000 Strasbourg, France

ABSTRACT: Since several years, the interest for In all cases studied, the X-Ray diffraction coordination networks or metal-organic frameworks investigations revealed their isostructural nature. (MOFs) increases due to their structural features The porous crystals (figure 2) display two types of (dimension, geometry, topology) and their cavities differing by their volumes, one spherical properties.1, 2 These porous coordination networks (small cavity) and the other of the ovaloid type are composed of organic tectons and metallic (larger cavity). nodes. The design, formation and description of such periodic architectures may be explored by the 3, 4 approach called Molecular Tectonic. Ovaloïd cavity Combinations of a series of enantiomerically pure organic tectons bearing four carboxylate moieties (figure 1) with Zn(II) or Cu(II) cations lead to the formation of isostructural chiral porous crystals. The crystalline materials have been characterized by X-ray diffraction on single crystals as well as by powder X-ray diffraction. Spherical cavity

Fig.2: DRX structure of the networks

The stability of the different crystals generated has been studied by thermogravimetric analysis (TGA) which revealed that their decomposition starts at ca 300 °C. In all cases, the phase purity was checked by powder X-Ray Diffraction (XRPD) which revealed a good match between the simulated and observed diffraction patterns. Finally the gas adsorption propensity of porous crystalline materials was investigated by BET.

Fig.1: Lewis representation of the different tectons

KEY WORDS: MoFs, Chirality, Porous Materials

Refrences 1. M. W. Hosseini, L’actualité chimique, 2011, 36, 348-349. 2. M. W. Hosseini, L’actualité chimique, 2005, 51, 290-291. 3. Simard, M.; Su, D.; Wuest, J. D. J. Am. Chem. Soc. 1991, 113, 4696−4698. 4. Mann, S. Nature 1993, 365, 499−505. 2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2016, Strasbourg, France

Self-Assembly of Conducting Triarylamine Nanowires in Mesoporous Silica and Biocompatible Electrodes Thereof

S. SCHNEIDER,[1,2] E.-D. LICSANDRU,[3] S. TINGRY,[3] T. ELLIS,[1] E. MOULIN,[1] M. MAALOUM,[1] J.-M. LEHN,[2] M. BARBOIU,*[3] and N. GIUSEPPONE*[1] 1SAMS Research Group, Institut Charles Sadron (ICS), UPR 22-CNRS, icFRC, University of Strasbourg, 23 rue du Loess, BP 84047, 67034 Strasbourg, Cedex 2, France 2Institut de science et d'ingénierie supramoléculaires (ISIS), Universite de Strasbourg 8 rue Gaspard Monge - BP 70028 67083 Strasbourg Cedex, France 3 Adaptative Supramolecular Nanosystems Group, Institut Européen des Membranes, ENSCM/UMII/UMR-CNRS 5635, Pl. Eugène Bataillon, CC 047, 34095, Montpellier, Cedex 5, France

ABSTRACT: Biocompatible silica-based mesoporous oriented mesopores of a silica nanolayer covering a materials, which present high surface areas combined gold electrode.2 This addressable bottom-up with uniform distribution of nanopores, can be construction is triggered from solution by simple light organized in functional nanopatterns for a number of irradiation.3-5 The resulting self-assembled nanowires applications. However, silica is by essence an act as highly conducting electronic pathways crossing electrically insulating material which precludes the silica layer. They allow very efficient charge applications for electro-chemical devices. For instance, transfer from the redox species in solution to the gold the formation of hybrid electroactive silica surface. We demonstrate the potential of these hybrid nanostructures is expected of great interest for the constitutional materials by implementing them as design of biocompatible conducting materials such as biocathodes and by measuring Laccase activity that bioelectrodes.1 Here we show that we can grow reduces dioxygen to produce water. supramolecular stacks of triarylamine molecules inside

Ox + e‐ Red

5 nm Gold I

Fig. 1 : Left: Side view of the characteristic molecular packing between triarylamine molecules; Middle: Mesoporous Silica Electrode filled with Conducting Triarylamine Assemblies; Right: High resolution AFM image of single pore after the silica layer was filled with a single self-assembled fibril of TAA

KEY WORDS: mesoporous silica, triarylamines, self-assembly, bioelectrodes, molecular electrodes

References 1. Y. Le Duc, A. Gilles, S. Mihai, V. Rouessac, S. Tingry and M. Barboiu, Chem. Commun. 2013, 49, 3667. 2. E.-D. Licsandru, S. Schneider, S. Tingry, T. Ellis, E. Moulin, M. Maaloum, J.-M. Lehn, M. Barboiu, N. Giuseppone, Nanoscale 2016, 8, 5605– 5611. 3. Moulin, E.; Niess, F.; Maaloum, M.; Buhler, E.; Nyrkova, I.; Giuseppone, N. Angew. Chem. Int. Ed. 2010, 49, 6974. 4. Faramarzi, V.; Niess, F.; Moulin, E.; Maaloum, M.; Dayen, J.-F.; Beaufrand, J.-B.; Zanettini, S.; Doudin, B.; Giuseppone, N. Nature Chem. 2012, 4, 485. 5. Nyrkova, E. Moulin, J. J. Armao, M. Maaloum, B. Heinrich, M. Rawiso, F. Niess, J.-J. Cid, N. Jouault, E. Buhler, A. N. Semenov and N. Giuseppone, ACS Nano. 2014, 8, 10111.

2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2016, Strasbourg, France

Synthesis and Self-assembly of Triarylamine-Nucleobase Conjugates

Q. CAO, E. MOULIN and N. GIUSEPPONE SAMS Research Group, University of Strasbourg, Institut Charles Sadron, CNRS, 23, rue du Loess, BP 84087, 67034 Strasbourg Cedex 2, France

ABSTRACT: Nucleobases are important building blocks possibility to use this molecule as sensor for metal for the self-assembly of DNA and RNA. Over the last ions. years, chemists have used these recognition units to trigger the self-assembly of small molecules into 1 functional architectures. Recently, our group 2.4 discovered that properly modified triarylamine (TAA) FeCl3 molecules in chlorinated solvents can generate 2.0 HgCl2 supramolecular triarylamine nanowires (STANWs) and 1.6 MgCl2 be combined into packed bundles of fibers which ZnCl2 displayed extraordinary metal-like conductivity 1.2 2-4 properties thanks to a non-covalent polymerization. 0.8 Furthermore, we have shown that the triarylamine scaffold is a versatile motif to produce functional (a.u.) Absorbance 0.4 supramolecular systems which can exhibit a variety of 0.0 morphologies.5-6 250 500 750 1000 Wavelength (nm) Here, we will report on the synthesis and Fig. 1 : Chemical Structure of thymine-triarylamine characterization of a series of triarylamine-nucleobase conjugate and its use as selective sensor for metal conjugates. Using spectroscopic techniques such as ions. NMR, UV-Vis-NIR and fluorescence, we will show that these molecules retains their self-assembling properties. Finally, focusing on the thymine- triarylamine conjugate, we will also explore the

KEY WORDS: triarylamine, nucleobases, supramolecular polymers, spectroscopy

References 1. Sivakova, S.; Rowan, S. J., Chem. Soc. Rev. 2005, 34, 9. 2. Moulin, E.; Niess, F.; Maaloum, M.; Buhler, E.; Nyrkova, I.; Giuseppone, N., Angew. Chem. Int. Ed. 2010, 49, 6974-6978. 3. Nyrkova, I.; Moulin, E.; Armao, J. J.; Maaloum, M.; Heinrich, B.; Rawiso, M.; Niess, F.; Cid, J.-J.; Jouault, N.; Buhler, E.; Semenov, A. N.; Giuseppone, N., ACS Nano 2014, 8, 10111-10124. 4. Armao, J. J.; Maaloum, M.; Ellis, T.; Fuks, G.; Rawiso, M.; Moulin, E.; Giuseppone, N., J. Am. Chem. Soc. 2014, 136, 11382-11388 5. Domoto, Y.; Busseron, E.; Maaloum, M.; Moulin, E.; Giuseppone, N., Chem. Eur. J. 2015, 21, 1938-1948.. 6. Busseron, E., Cid, J. J., Wolf, A., Du, G. Y., Moulin, E., Fuks, G., Maaloum, M., Polavarapu, P., Ruff, A., Saur, A. K., Ludwigs, S., Giuseppone, N., ACS Nano 2015, 9, 2760-2772. 2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2016, Strasbourg, France

Temperature-Dependent Supramolecular Chirality in Triarylamine-Based Organogelators

A. OSYPENKO, E. MOULIN, O. GAVAT, G. FUKS, M. MAALOUM and N. GIUSEPPONE SAMS Research Group, Institut Charles Sadron, 23 rue du Loess, 67034 Strasbourg, France

ABSTRACT: Recently our group reported on the ability (TATAs) decorated with chiral and achiral alkyl of electron-donor triarylamines (TAAs) to self- substituents (Fig. 1, A). assemble into nano-fibers upon light irradiation in We found that these molecules assemble in non- chlorinated solvents. 1 These molecules were then chlorinated solvents, such as toluene, via a cooperative assembled between 80 nm lithographically defined (nucleation-and-growth) mechanism into long fibrillary electrodes and demonstrated high conductivity (higher structures (Fig. 1, B). Thermoresponsive organogels than 5×10 3 S m-1), which systematically decreases are formed at very low concentrations in various when the temperature is lowered to 1.5 K, revealing an organic solvents (CGC is 0.1% wt or 0.75 mM in intrinsic metallic behavior. 2 Finally, we have toluene). Temperature dependent CD measurements exemplified that these TAA units can act as were performed to study the aggregation process of supramolecular structuring synthons for more complex TATAs in detail (Fig. 1, C). structures, as they retain the general ability to self- Interestingly, we found that the shape and the sign of assemble upon light stimulation in chlorinated solvents CD depend on the cooling rate, which is explained by even when modified with various chemical units such different self-assembly pathways for two cooling as gallate or benzene-1,3,5-tricarboxamide for regimes. example. 3 In this work we study gelation, fluorescent and chiroptical properties of trisamidetriarylamine

100 Slow Cooling Fast Cooling 0

-100

-200 CD (mdeg)

-300

-400 2µm 300 320 340 360 380 A B C Wavelenght (nm)

Fig. 1 : (A) Structures of studied TATAs, decorated with chiral and achiral alkyl substituents; (B) Scanning Electron Microscopy image of TATA self-assemblies in toluene; (C) Temperature dependent CD-spectra of 0.5 mM toluene solution of TATA for different cooling regimes: slow cooling (1 K/min, blue lines); fast cooling (10 K/min, red lines)

KEY WORDS: supramolecular chirality, organogel, supramolecular polymers, chirality inversion

References 1. Moulin E., Niess F., Maaloum M., Buhler E., Nyrkova I., Giuseppone N., Angew. Chem. Int. Ed. 2010, 49, 6974–6978 2. Faramarzi V., Niess F., Moulin E., Maaloum M., Dayen J.-F., Beaufrand J.-B., Zanettini S., Doudin B., Giuseppone N., Nature Chem. 2012, 4, 485–490 3. (a) Armao IV J.J., Maaloum M., Ellis T., Fuks G., Rawiso M., Moulin E. and Giuseppone N., J. Am. Chem. Soc. 2014, 136, 11382–11388; (b) Domoto Y., Busseron E., Maaloum M., Moulin E., Giuseppone N., Chem. Eur. J., 2015, 21, 1938–1948; (c) Moulin E., Busseron E., Domoto Y., Ellis T., Osypenko A., Maaloum M., Giuseppone N., C. R. Chimie, 2016, 19, 117–122

2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2016, Strasbourg, France

Synthesis and Self-Assembly of Triarylamines in Water

T. LIANG, E. MOULIN, M. MAALOUM, G. FUKS and N. GIUSEPPONE SAMS Research Group, University of Strasbourg, Institut Charles Sadron, CNRS, 23, rue du Loess, BP 84087, 67034 Strasbourg Cedex 2, France

ABSTRACT: Over the last few years, our group has Here, we will report on new classes of water-soluble demonstrated that well-designed triarylamine triarylamine molecules decorated with either molecules can be used as building blocks to produce poly(ethylene glycol) (PEG), peptide or cyanine dyes functional supramolecular architectures exhibiting on the three amide positions (Fig. 1).5 First, we will various morphologies with excellent physical describe the synthesis of these complex molecules. properties in non-polar solvents such as chlorinated Using a large variety of characterizations going from solvents or toluene.1-4 However, their self-assembly in spectroscopy to microscopy and even scattering aqueous solution has, to the best of our knowledge, not techniques, we will show that these three amphiphilic yet been investigated. Within water environment, triarylamines can give rise to different self-assembled amphiphilic molecules are expected to self-organize objects both in water and in methanol. into hierarchical structures such as fibers, vesicles, ribbons and nanotubes, due to hydrophobic effect and hydrophilic interaction.

KEY WORDS: triarylamine amphiphiles, PEG, peptide, cyanine dye, supramolecular polymers

References 1. Moulin, E.; Niess, F.; Maaloum, M.; Buhler, E.; Nyrkova, I.; Giuseppone, N. Angew. Chem. Int. Ed. 2010, 49, 6974. 2. Faramarzi, V.; Niess, F.; Moulin, E.; Maaloum, M.; Dayen, J.-F.; Beaufrand, J.-B.; Zanettini, S.; Doudin, B.; Giuseppone, N. Nature Chem. 2012, 4, 485. 3. Armao, J. J., Maaloum, M., Ellis, T., Fuks, G., Rawiso, M., Moulin, E., Giuseppone, N., J. Am. Chem. Soc. 2014, 136, 11382. 4. Busseron, E., Cid, J. J., Wolf, A., Du, G. Y., Moulin, E., Fuks, G., Maaloum, M., Polavarapu, P., Ruff, A., Saur, A. K., Ludwigs, S., Giuseppone, N., ACS Nano 2015, 9, 2760. 5. Xiang Y. J., Moulin, E., Buhler, E., Maaloum, M., Fuks, G., Giuseppone, N., Langmuir 2015, 31, 7738.

2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2016, Strasbourg, France

Paving the way for Single-molecule Sequencing of non-natural information-containing Polymers

N. F. KÖNIG1, L. CHARLES2 and J.-F. LUTZ1 1 Precision Macromolecular Chemistry, Institut Charles Sadron, CNRS UPR-22, 23 rue du Loess, 67034 Strasbourg Cedex 2, France 2 Aix-Marseille Université – CNRS, UMR 7273, Institute of Radical Chemistry, 13397 Marseille Cedex 20, France

ABSTRACT: Storing information on the molecular level has become a flourishing discipline in recent years. Attaining an immense information density, and energy efficient storage compared to conventional storage devices, stimulates research in the field.

Artificial biopolymers like DNA set, until now, the yardstick for molecular storage systems due to already established coding and decoding methodologies.1,2

However, restriction to biological building blocks is clearly setting limits to future (commercial) applicability. There is a need for diversely tunable systems. Methodologies for obtaining sequence- defined non-natural polymers have recently been developed.3,4,5 Sequencing can be achieved by tandem mass spectrometry, yet crucial for efficient storage systems, the next objective is the development of a new single-molecule sequencing technique for non-natural polymers.

The new approach employs polyphosphodiesters that comprise two different monomer units defining a 0 and a 1 bit, respectively. Polymers of that kind incorporate information as a binary code. The copolymers are accessible through the fast and convenient phosphoramidite method. To respond with information readout, every sequencing technique demands specified features within the polymer. Libraries of fine-tuned polymers are thus demanded. The approach to cope with these requirements is presented to pave the way for single-molecule sequencing of non-natural information-containing polymers.

KEY WORDS: sequence-controlled polymers, polyphosphodiester, phosphoramidite strategy, single-molecule sequencing

References 1. Zhirnov, V., Zadegan, R. M., Sandhu, G. S., Church, G. M., Hughes, W. L., Nature Mater. 2016, 15, 366. 2. Goldman, N., Bertone, P., Chen, S., Dessimoz, C., LeProust, E. M., Sipos, B., Birney, E., Nature 2013, 494, 77. 3. Lutz, J.-F., Macromolecules 2015, 48, 4759. 4. Al Ouahabi, A., Charles, L., Lutz, J.-F., J. Am. Chem. Soc. 2015, 137, 5629. 5. Al Ouahabi, A., Kotera, M., Charles, L., Lutz, J.-F., ACS Macro Lett. 2015, 4, 1077.

2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2016, Strasbourg, France

Reversible NCL of Specific Peptides for Affinity-based Receptor Binding

M. SAMIAPPAN,1 C.-V. REȚE,1 J.-M. STRUB,2 D. FUNERIU1 and N. GIUSEPPONE1

1 Institut Charles Sadron – UPR 22, University of Strasbourg, SAMS Research Group- icFRC, 23 Rue du Loess, BP84047, 67034 Strasbourg Cedex 2 2 Laboratoire de Spectrométrie de Masse BioOrganique (UMR 7178), Institut Pluridisciplinaire Hubert Curien, University of Strasbourg, 25 rue Becquerel, 67087 Strasbourg, France

ABSTRACT: Dynamic combinatorial chemistry has been introduced as a supramolecular approach to the screening of chemical libraries and the acceleration of receptor/ligand identification for affinity-based drug discovery.1

Recently, we have reported the activation of a specific peptide bond for exchange reactions, i.e. reversible native chemical ligation (revNCL), in physiological conditions.2 (Figure 1) Fig. 1 : Schematic representation of the exchange reaction performed between two peptides containing A first proof of concept has been the design of dynamic an internal dynamic unit Affibody® peptides which can interconvert, self- assemble and amplify using revNCL in the presence of particular receptors. Specific binding properties of the designed peptides have been measured by SPR, QCM and ITC techniques.

KEY WORDS: peptides, dynamic combinatorial libraries, exchange reaction, native chemical ligation

References 1. Mondal, M., Hirsch, A. K. H., Chem. Soc. Rev. 2015, 44, 2455 2. Ruff, Y., Garavini, V., Giuseppone, N., J. Am. Chem. Soc. 2014, 136, 6333

2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2016, Strasbourg, France

Muscle-like Supramolecular Polymers: Integrated Motion from Thousands of Molecular Machines

A. GOUJON,1 G. DU,1 T. LANG,1 E. MOULIN,1 G. FUKS,1 M. MAALOUM,1 M. RAWISO,1 G. MARIANI,2 E. BUHLER2 and N. GIUSEPPONE1

1 Institut Charles Sadron – UPR 22, University of Strasbourg, SAMS Research Group- icFRC, 23 Rue du Loess, BP84047, 67034 Strasbourg Cedex 2 2 Matière et Systèmes Complexes (MSC) Laboratory, University of Paris Diderot – Paris VII, UMR 7057, Bâtiment Condorcet, 75205 Paris Cedex 13, France.

ABSTRACT: One of the targeted challenges in This work represents the first example showing this nanotechnologies consists in coupling together defined synchronization of thousands of molecular machines to individual molecular motions for the production of cross several length scales thanks to a combination of macroscopic response.1 In 2012, we reported the first molecular synthesis, supramolecular engineering, and example of micrometric contraction and extension of polymerization processes. telescopic [c2]daisy chains based coordination supramolecular polymers.2 Characterizations by scattering techniques in solution reveal the formation of single-strand supramolecular polymer chains with very high molecular weight (up to 6*108 g.mol-1). The subsequent pH modulation triggers cooperative nano- contractions / extensions of the individual rotaxanes resulting in an amplified motion of the muscle-like supramolecular chains with changes of their contour lengths by several micrometers. Here we will show how different H-bonding groups allowed us to go from the previously described single chains to larger architectures. A H-bonding supramolecular polymer relying on a 2,6- diaminopyridine/uracil recognition pattern was used to create aggregating chains, forming microscopic 3 stimuli-responsive bundles of fibers (Fig. 1). On the Fig. 1 : Muscle-like behavior of an hydrogen-bonding other hand, [c2]daisy chains substituted with muscle-like supramolecular polymer. ureidopyrimidinone moieties protected with a photolabile group were shown to polymerize and form gel upon UV irradiation. The resulting material displayed a reversible gel-sol transition. In both cases, the nanoscopic contraction / extension of the cooperating molecular machines were responsible of the changes of structural / physical properties observed at the microscopic / macroscopic scale.

KEY WORDS: rotaxanes, supramolecular polymers, microscopy, scattering techniques

References 1. Coskun, A., Banaszak, M., Atsumian, R. D., Stoddart, J. F., Grzybowski, B. A., Chem. Soc.Rev. 2012, 41,19. 2. Du, G., Moulin, E., Jouault, N., Buhler, E., Giuseppone, N., Angew.Chem. Int. Ed. 2012, 124, 12672. 3. Goujon, A., Du, G., Moulin, E., Fuks, G., Maaloum, M., Buhler, E., Giuseppone, N., Angew.Chem. Int. Ed. 2016, 55,703.

2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2016, Strasbourg, France

Synthesis and physico-chemical characterization of supramolecular Lysine-based gels; a novel and tunable gelation platform

M. M. ABDELLATIF, M-C AVERLANT-PETIT and G. PICKAERT* Laboratoire de Chimie Physique Macromoléculaire, Université de Lorraine Nancy, France. 54001

ABSTRACT: Low molecular weight gelators (LMWGs) critical gelation concentration (CGC), the sol-gel -1 1 are small molecules (< 2000 g. mol ), able to transition temperature (Tgel) and their melting immobilize fluid phases (i.e. water, organic solvents, enthalpies (ΔH). Moreover, the gelation behaviour has oils, liquid crystals, ionic liquids, etc.). The gelation been analyzed as a function of Kamlet–Taft process is achieved via formation of a self-assembled parameters. Scanning electron microscopy was also three dimensional fibrillar network. Amide containing performed on aerogels, obtained from supercritical CO2 molecules, such as L-amino acids derivatives, are used drying of corresponding organogels. A strong as platforms for molecular gels elaboration. Indeed, difference in the fibrillar nanostructures (shape and because of their specifically oriented hydrogen bond size) could be observed by changing the functional donor and acceptor sites, unidirectional primary group grafted on lysine platform (Fig. 2). supramolecular structures can be obtained. Then, fibers found within molecular gels are due to further self- 2 assembly processes of those primary columns. In addition, the gelation process can be finely tuned depending on the nature of lateral side chain of the amino acids (polar, non-polar, acidic or basic). In this work, tunable building block platform α based on L-Lysin dervatives (N - and C- terminal substituted) with various peripheral groups such as carboxybenzyl (G1), naphthalimide moiety (G2) or ε 3,4,5-tris-hexadecyloxy benzoyl (G3) at N -position have been designed (Fig. 1). Strong molecular gels, with high gelation efficiency, were obtained mainly in aromatic and alkane solvents. Those molecular gels Fig. 1 : The synthesized LMWGs [G1, G2 and G3] have been macroscopically characterized through their

Fig. 2: SEM pictures of aerogels of G1-G3 obtained from 2 wt% toluene organogel (x 20 000)

KEY WORDS: low molecular weight organogelators, lysine, supramolecular chemistry, fibrillar networks, gels, scanning electron microscopy

References 1. Zweep, N., Esch, J. H. V.,“Functional Molecular Gels”, Royal Society of Chemistry 2013 2. Curcio, P., Allix, F., Pickaert, G., Jamart-Grégoire, B., Chemistry - A European Journal 2011, 17, 13603

2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2016, Strasbourg, France

Molecular scale spectroscopic characterization of Lysine-based supramolecular gels M. M. ABDELLATIF, M-C AVERLANT-PETIT and G. PICKAERT* Laboratoire de Chimie Physique Macromoléculaire, Lorraine Université, Nancy, France. 54001

ε ABSTRACT: The gelation process of Lysine-based low backbone, N -position), has also been investigated. molecular weight gelators (LMWGs) has been studied Molecular scale spectroscopic characterization of the by molecular spectroscopy. NMR and FT-IR spectra LMWGs afford a valuable observations regarding 1-D were recorded for Nα- and C- terminal substituted self-assembly process (stacking-up) which is necessary lysine with various peripheral groups such as for formation of a three dimensional fibrillar network carboxybenzyl (G1), naphthalimide moiety (G2) or responsible for immobilizing fluid phases (i.e. water, 3,4,5-tris-hexadecyloxy benzoyl (G3) at Nε-position organic solvents, oils, liquid crystals, ionic liquids, (Fig.1). The influence of side chain nature on self- etc.). 1-5 assembly process was evaluated. Moreover, the gelation behavior of the LMWGs has been studied using temperature-dependent NMR (Fig.2) and FT-IR (Fig.3) experiments; that enable us to study the different phase transitions from gel state to solution.

The involvement of N-H and C=O groups in the hydrogen-bonding, needed for supramolecular self- assembly at different positions of the LMWG (i.e. main Fig. 1: structures of G1, G2, G3

Fig. 2 : Plot of temperature-dependent Fig. 3 : Temperature-dependent direct FT- mobility of G1 protons. NHa, NHb NHc IR spectra of G3 in d8-toluene gel state α and H-C .(1.0 wt% in d8-toluene) (1wt %). (10 to 60 °C)

KEY WORDS: low molecular weight organogelators, lysine, supramolecular chemistry, gels, NMR, FT-IR

References 1. Allix, F., Curcio, P., Pham, Q. N., Pickaert, G., Jamart-Grégoire, B., Langmuir 2010, 26(22), 16818 2. Weiss, R. G., Terech, P., Molecular Gels: Materials with Self-Assembled Fibrillar Networks; Kluwer Academic: Norwell, MA, 2005 3. Estroff, L. A., Hamilton, A. D., Chem. Rev. 2004, 104, 1201 4. Chen, Y., Lv, Y., Han, Y., Zhu, B., Zhang, F., Bo, Z., Liu, C.-Y., Langmuir 2009, 25, 8548 5. Samanta, S. K., Pal, A., Bhattacharya, S., Langmuir 2009, 25, 8567 2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2016, Strasbourg, France

Light-triggered Supramolecular Assembly of a Hexaazaparacyclophane

S. SCHNEIDER,[1,2] J. TAN,[1] E. MOULIN,[1] G. FUKS,[1] M. MAALOUM,[1] O. GAVAT,[1] T. ELLIS,[1] J.-M. LEHN,[2] and N. GIUSEPPONE*[1] 1SAMS Research Group, Institut Charles Sadron (ICS), UPR 22-CNRS, icFRC, University of Strasbourg, 23 rue du Loess, BP 84047, 67034 Strasbourg, Cedex 2, France 2Institut de science et d'ingénierie supramoléculaires (ISIS), Universite de Strasbourg 8 rue Gaspard Monge - BP 70028 67083 Strasbourg Cedex.

ABSTRACT: Our group has recently discovered the ability of appropriately substituted triarylamines1 to self-assemble upon light activation into various1 supramolecular structures going from fibers to spheres.1,2 We have also3 measured their exceptional conduction efficiency and, more recently, explained their metallic characteristics.3,4 Based on these findings, we are interested in studying a well-designed hexaazaparacyclophane which should present unusual electromagnetic properties due to the combination of charge delocalization within the macrocycle and along the self-assembled architecture. Here, we will report on a robust and efficient eleven- step synthesis of this advanced macrocyclic derivative. Similarly to our light-responsive triarylamines, 1H-

NMR and UV-vis studies prove that the molecule is able to self-assemble under the influence of light in chlorinated solvents. Using a combination of UV and Fig. 1 : Macrocyclic Hexaazaparacyclophane and EPR experiments, we will show the long term stability Schematic Representation of the Dual Charge of the light-induced radical cations and their electronic Delocalization. delocalization.

KEY WORDS: triarylamines, self-assembly, hexaazaparacyclophanes

References

1. Moulin, E.; Niess, F.; Maaloum, M.; Buhler, E.; Nyrkova, I.; Giuseppone, N. Angew. Chem. Int. Ed. 2010, 49, 6974-6978. 2. Moulin, E.; Niess, F.; Fuks, G.; Jouault, N.; Buhler, E.; Giuseppone, N. Nanoscale 2012, 4, 6748-6751. 3. Faramarzi, V.; Niess, F.; Moulin, E.; Maaloum, M.; Dayen, J.-F.; Beaufrand, J.-B.; Zanettini, S.; Doudin, B.; Giuseppone, N. Nature Chem. 2012, 4, 485-490. 4. Armao IV, J. J.; Maaloum, M.; Ellis, T.; Fuks, G.; Rawiso, M.; Moulin, E.; Giuseppone, N. J. Am. Chem. Soc. 2014, 136 , 11382–11388.

2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2016, Strasbourg, France

Rheological and Spectroscopic Studies for the Supramolecular Self-Assembly of Heterochiral Cyclohexamer [-(Phe-azaPhe-Ala)2-] in Gel state M. I. ABDELMONEIM, J. BODIGUEL, Z. ZHOU, B. JAMART, M.-C. AVERLANT-PETIT Laboratoire de Chimie-Physique Macromoléculaire, UMR 7375, Université de Lorraine, 1 rue Grandville, BP 20451, 54001 Nancy cedex, France

ABSTRACT: Molecular self-assembly is a fascinating low molecular weight organogelators (LMWGs). process for the synthesis of many new supramolecular Rheological results for gels in toluene at different hierarchical structures. In certain cases, the self- concentrations revealed good thermal stabilities. SEM assembly process leads to molecular gels, which has analysis of the aerogel demonstrated non-twisted fibers, become an area of great interest in the field of thus confirming the presence of self-organization. supramolecular chemistry. Gels are composed of a 3D Subsequent FTIR and NMR studies have shown network where organic solvents (organogel) or water the presence of equilibrium between monomeric (hydrogel) are trapped. First gels were obtained from (intramolecular H-bonds) and nanotubular polymers and last two decades authors have report (intermolecular H-bonds) forms in solution. Finally, we molecular gels obtained from low molecular weight found that our organogelator is suitable for selective gelators (LMWGs). LMWGs have attracted much gelation of an organic solvent(s) from (water/organic) interest due to their practical implications as new soft mixture with good recovery percents ranging from 73- materials [1]. Recently, LMWGs form peptides, 96% which could lead to potential applications in water pseudopeptides or their cyclic analogues have had cleaning. greater advantages as they can be easily synthesized, multiple responsive, control over their physical and

chemical properties. Most of the LMWGs are driven by various non-covalent forces such as π–π stacking, hydrogen bonding, van der Waals, charge-transfer and electrostatic interactions [2,3]. We have synthesized homo- and hetero- cyclohexamer pseudopeptides based on the proteinogenic amino acid phenylalanine and alanine. Previous studies[4] have shown that the alternatingD,L-cyclohexamer [-(Phe-azaPhe- Ala)2-] . could self-assembly in some aromatic solvents to for

KEY WORDS: Self-assembly, organogel, LMWGs, non-covalent interactions, cyclo-pseudopeptides, biphasic separation

References 1. Reddy, S.M.M., et al.,. Soft Matter, 2015. 11(41):p. 8126-8140. 2. Kar, T., S. Mukherjee, and P.K. Das,. New Journal of Chemistry, 2014. 38(3): p. 1158-1167. 3. Seabra, A.B. and N. Duran,. Peptides, 2013. 39: p. 47-54. 4. Zhou, Z., Deng, C., Abbas, C., et al. European Journal of Organic Chemistry, 2014(34): p. 7643-7650. 2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2016, Strasbourg, France

Dynamical arrest in solutions containing organogelator molecules of amino-acid type

P. MARTINOTY a, D. COLLIN a, R. COVISa, F. ALLIXb, and B. JAMART-GREGOIREb

a Institut Charles Sadron, UPR 22, CNRS/UDS, 23 rue du Loess, BP 84047, 67034 Strasbourg, France. b Laboratoire de Chimie Physique Macromoléculaire, UMR7568, CNRS/INPL, 1 rue Granville, BP 20451, 54001 Nancy, France.

ABSTRACT: Organogels are soft solids made of physical gelation comes from a fractal growth of organic molecules of low molecular weight called clusters, while the gelation induced by a dynamical organogelators. They are currently described as arrest is associated with a crowding of clusters (or thermoreversible gels, and their formation as a physical particles), which leads to the formation of a purely gelation1. The question we ask is to know whether this elastic network in a carrier fluid that is the solvent2. We description is valid or not. also show that the difference between organogels and In this communication, we present a rheological study gels appears in the elastic and volume properties of the of the formation and characterization of amino-acid aerogels derived from organogels and gels. organogels in solvents such as toluene or tetralin. The This study shows for the first time that an organogel is rheology experiments were carried out as a function of not a physical gel, as is currently believed, but a temperature for different concentrations of the dynamically arrested suspension. The transition from organogelator molecules, of the frequency, of the liquid to organogel cannot therefore be associated with thermal history and of aging. The results show all the the existence of a new phase, but merely to a change in characteristics of a dynamically arrested suspension: no the mechanical response of the solution, from a liquid critical gel, no rubber elasticity and presence of state to a solid state. thixotropic effects. Compared to the behavior expected for a gel, this behavior results from the fact that the 2 0.2% tetralin-based solution 103

2 G’ 0.2% tetralin-based 10 solution 1 1 10 cooling rate 0 T 10 G’’ organogel 0.2 K/min

10-1 DSC peak G' G', G'' (Pa) 10-2 G'' G’’ G', G'' (Pa) G'' G', T=18.2°C 10-3 T=17.4°C G’ T=16.8°C 0.2 -4 III II I 10 0.1 1 3 0 1020304050 f (Hz) T(°C) Fig. 1: Typical experiment showing the formation of Fig. 2: Behavior of G’ (filled symbols) and G’’ (open the organogel at a frequency of 1 Hz. Three regions: symbols) around the liquid to organogel transition, I) classical fluid; II) formation of clusters, liquid showing that G’ and G’’ do not exhibit the power law behavior (critical gel) expected for a gel at the liquid state; III) organogel, solid state. Torganogel depends on frequency, concentration and cooling rate. to solid transition. The transition is not a percolation transition and the organogel is not a physical gel. KEY WORDS: organogel, gel, critical gel, jamming transition, dynamical arrested suspension.

References 1. Abdallah, D.J., Weiss, R.G., Adv. Mater. 2000, 12, 1237. Terech, P., Weiss, R.G., Chem. Rev., 1997, 97, 3133. Estroff, L.A. and A. D. Hamilton, A.D., Chem. Rev., 2004, 104, 1201 2. Collin, D., Covis, R., Allix, F., Jamart-Grégoire, B., Martinoty.P. Soft Matter 2013, 9, 2947

2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2016, Strasbourg, France

Chemoselective Synthesis of Uniform Sequence-coded Polyurethanes B. PETIT, U. GUNAY, L. CHARLES and J.-F. LUTZ Institut Charles Sadron, CNRS-Université de Strasbour 23 rue du Loess 67034 STRASBOURG Cedex02

ABSTRACT: Provisionally confidential Patenting pending. The abstract will be available just before the onset of the conference

KEY WORDS: polyurethanes, sequence controlled synthesis, tandem MS/MS

References

Lutz, J.-F., Ouchi, M., Liu, D. R., Sawamoto, M., Science 2013, 341,1238149 Ghosh, A. K., Doung, T. T., McKee, S. P., Thompson, W. J., Tetrahedron Lett. 1992, 33, 2781 Warrass, R., Walden, P., Wiesmüller, K.-H., Jung, G., Lett. Pept. Sci 1989, 5, 125

2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2016, Strasbourg, France

Synthesis and utilization of sequence-coded barcodes

D. KARAMESSINIa, U. S. GUNAYa, B. E. PETITa, M. BOUQUEYa L.CHARLESb, J.-F. LUTZa a Precision Macromolecular Chemistry, Institut Charles Sadron, UPR-22 CNRS, 23 rue du Loess 67034 Strasbourg, France b Aix-Marseille Université, CNRS, UMR 7273, Institute of Radical Chemistry, 13397, Marseille Cedex 20, France

ABSTRACT: Our proposal to this challenge focuses on the labeling of materials at the molecular level2. A homogeneous Anti-counterfeit technologies have become highly dispersion of a small amount of a coded polymer important during the last decades and have found containing information in an organic or inorganic applications in the domain of food and pharmaceutical matrix gives a solution to the imitation problem. packaging, paper currency, high values products and Finding readable information in the matrix of a treasured artworks.1 These technologies require novel product, such as the production date and the lot techniques for tracing commercial products that are number, and not only on the packaging will help the extremely difficult to be copied but very efficient for consumer come up against troubles that occur after a the discrimination of the original product from fraud period of using. In the current work, sequence-defined ones. In this context, molecular barcodes would offer oligomers synthesized by solid-phase synthesis and to the consumers the safety of buying the original bearing a monomer-sequenced binary message were product but also to the manufacturer the ability of used as molecular barcodes.3 The inclusion of a guaranteeing its value by increasing his responsibility sequence-coded label into commodity plastics was and liability. studied and its extraction was followed by tandem mass spectrometry sequencing.

KEY WORDS: sequence-coded polymers, molecular barcode, anti-counterfeiting

References 1. (a) Ecker, M.; Pretsch, T. RSC Adv. 2014, 4, 286; (b) Hou, X.; Ke, C.; Bruns, C. J.; McGonigal, P. R.; Pettman, R. B.; Stoddart, J. F. Nat Commun 2015, 6, 6884. 2. J.-F Lutz,. Macromolecules 2015, 48, 4759. 3. R. K. Roy, A. Meszynska,C. Laure, L. Charles, C. Verchin, J.-F. Lutz, Nat. Commun. 2015, 6, 7237

2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2016, Strasbourg, France

Synthesis of monodisperse sequence encoded copolymers using fast orthogonal chemistry

1 G. CAVALLO1, A. AL OUAHABI1, L. OSWALD1, L. CHARLES2, J.-F. LUTZ

1 Precision Macromolecular Chemistry, Institut Charles Sadron, UPR-22 CNRS, BP 84047, 23 rue du Loess 67034 Strasbourg Cedex 2, France, 2 Aix-Marseille Universitė, CNRS, Institute of Radical Chemistry UMR 7273, Marseille, France

ABSTRACT: Information containing polymers coupling and a radical-radical coupling. This constitute a new class of molecules that enables data orthogonal strategy does not employ protecting groups storage at the molecular level.1 These linear and utilizes two different types of building blocks: a macromolecules are built up using two comonomers, spacer which contain nitroxide and hydroxy functions representing bit 0 and 1 respectively, thus allowing and a coded monomer, defining the bits (0 and 1), that binary coding. Several strategies for the efficient exhibit phosphoramidite and alkyl bromide functional synthesis of information containing polymers have groups. The synthesis of digitally-encoded polymers been developed by J.-F. Lutz and coworkers.2. For using this simple approach will be shown in this poster instance, polymers synthesized by phosphoramidite presentation. Moreover, the encoded sequences can be protocols3 as well as the new class of poly(alkoxy easily analyzed by tandem mass spectrometry. Hence, amine amide)s4 show interesting features. Here we sequence-coded poly(alkoxyamine phosphodiester)s present a new strategy for the iterative synthesis of represent a promising new class of information information-containing polymers based on two containing macromolecules. chemoselective steps, namely the phosphoramidite

KEY WORDS: chemoselective sequence controlled synthesis, information-containing macromolecules, MS/MS sequencing.

References 1. Jean-François Lutz, Jean-Marie Lehn, E.W. Meijer and Krzysztof Matyjaszewski, Nat. Rev. Mat. 24, 16024 (2016) 2. Jean-François Lutz, Macromolecules, 48, 4759-4767 (2015) 3. Abdelaziz Al Ouahabi, Laurence Charles, and Jean-François Lutz, J. Am. Chem. Soc. 137, 5629-5635 (2015) 4. Raj Kumar Roy, Anna Meszynska, Chloė Laure, Laurence Charles, Claire Verchin & Jean-François Lutz, Nat. Commun.6:7237 (2015) 2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2016, Strasbourg, France

Complete multitechnique study of the sol-to-organogel transition reveals different thermodynamical pathways of gelation

E. CHRIST, D. COLLIN, C. BLANC, R. LE PARC, J.L. BANTIGNIES, J.M. GUENET, P. J. MESINI Institut Charles Sadron, UPR22/CNRS 23 rue du Loess, 67034 Strasbourg Cedex 2, France

ABSTRACT: Although the field of organogelators has expanded, few papers describe the thermodynamic pathways of gelation. The phase diagrams are seldom mapped out and they are always simplified in two domain gel and sol. In the present study,1 we have investigated in details the sol-to-organogel transition of a diamide organogelator : BHPB10. This compound forms organogels in a large concentration range2. We have investigated this transition by mechanical measurements, microcalorimetry, optical microscopy, and light intensity transmission. We have carefully adapted the different technics to follow the transition over 2 decades of concentrations (from 0.05% up to 15%). All the experiments were performed at the same Fig. 1 : Optical micrographs of BHPB10/trans- cooling rate (–0.25°C/min). decalin (c = 10wt%) showing the transition between From these measurements we have mapped out the biphasic liquid phases and gel fibers phase diagram. Tgel follows two regimes: it increases gradually with concentration below a given concentration cL  0.6% and remains constant above. Above cL, the system exhibits a liquid-liquid phase separation, as revealed by optical microscopy. Before the gel forms, it comprises droplets of liquid in a continuous phase. The two regimes in the phase diagram correspond to two gelation pathways. Below cL, the system transits directly from solution to a gel and it transition temperature varies with c. Above cL, the gelation is a monotectic transformation that takes place at constant temperature. The two liquid phases comprise the organogelator and the solvent but in different concentration. The concentration is high in the droplets and low in the continuous phase, as shown by FTIR and NMR. These techniques also provide insight into the different state Fig. 2 : c-T phase diagram of BHPB10/trans-decalin of H-bonding in the different phases. (established at cooling rate of -0.25°C/min)

KEY WORDS: Organogelators, self-assembly, Phase Diagram

References 1. Christ, E.; Blanc, C.; Al Ouahabi, A.; Maurin, D. ; Le Parc, R. ; Bantignies, J.L. ; Guenet, J.M. ; Collin, D. ; Mésini, P.J. Origin of Invariant Gel Melting Temperatures in the c-T Phase Diagram of an Organogel. Langmuir 2016 DOI: 10.1021 (in Press) 2. - , P. J. Self-Assembling Properties of a Series of Homologous Ester- d − fr R Soft Matter 2013, 9 8483−8493

2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2016, Strasbourg, France

Aggregation of thermoresponsive polymers and “click chemistry” as tools for well- defined nanoparticles of pH-controlled stability

R. SZWEDA1,2, D. LIPOWSKA1, D. SZWEDA1, B. TRZEBICKA1, A. DWORAK1

1Centre of Polymer and Carbon Materials, Polish Academy of Sciences, M. Curie-Sklodowskiej 34, 41-819 Zabrze, Poland

2Institut Charles Sadron, 23 rue du Loess, 67034 Strasbourg, France

ABSTRACT: In this work the way leading to polymeric nanoparticles of pH-depended stability is presented. Thermoresponsive copolymers of di(ethylene glycol) methyl ether methacrylate (D) and (2-aminoethyl) methacrylate (A) were obtained by ATRP. Amine groups of A were transformed to azides or to prop-2- ynyl carbamate groups by post-polymerization modification what led to P(D-co-A_Az) and P(D-co- A_Pr) copolymers, with azide and amine functional groups. Strcture of obtained copolymers was confirmed by NMR, FTIR and GPC. The obtained copolymers exhibited thermoresponsive properties. In aqueous solutions at temperature above their phase transition temperature (TCP) they aggregated to nanoparticles and below they disintergated into individual chains. The sizes of obtained nanoparticles were easily controlled by changes of copolymer concentration and heating rate. By abrupt heating of copolymers solution it was posible to obtained mixed nanoparticles consisting of copolymers with azide and alkyne functions ( P(D-co- A_Az) and P(D-co-A_Pr)) (Fig. 1). Mixed nanoparticles were covalently stabilized by Cu (I) Huisgen 1,3-dipolar cycloaddition of azides and alkynes gropup present in copolymers chains. The Fig. 1 : Stabilization and degradation of crosslinked particles were stable below T . CP nanoparticles. Due to the presence of carbamate bonds in polymer chains the mesoglobules undergo degradation above pH 7 what made them suitable for delivery of . biological compounds.

KEY WORDS: thermoresponsive polymers, aggregation, nanoparticles, click chemistry, degradation

References 1. A Dworak, D Lipowska, D Szweda, J Suwinski, B Trzebicka, R Szweda Nanoscale 2015, 7, 16823

2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2016, Strasbourg, France

Synthesis and sequencing of sequence-coded poly(alkoxyamine-amide)s

1 1 1 2 1 C. LAURE , R. KUMAR ROY , D. SARENTI-KARAMESINI , L. CHARLES , J.-F. LUTZ

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

ABSTRACT: Sequence-defined synthetic polymers can studied. In a first approach, long sequence-coded be used to store digital information. In order to do so, poly(alkoxyamide amide)s (i.e. up to 19 units) were two monomers are intentionally defined as 0 and 1 bit1 prepared by convergent synthesis.5 These polymers and assembled into a coded sequence through an were obtained by stepwise ligation of oligomers iterative approach on a solid support.2 In the present containing information dyads, i.e. 00, 01, 10 and 11. In work, sequence-coded poly(alkoxyamine-amide)s were a second approach, uniform poly(alkoxyamide amide)s synthesized by a chemoselective process involving two with different chain-lengths were physically mixed. building blocks that cannot react with themselves.3 The This intentionally polydisperse mixture was analyzed first building blocks is a nitroxide, which is used as a by electrospray mass spectrometry and fully decoded 6 spacer, whereas the other one is an anhydride used as a by MS/MS using simple predefined reading rules. coding unit. The decoding of these polymers was performed by ESI-MS/MS.4 It was found that they are particularly easy to read by MS/MS due to the fragility of their alkoxyamine bonds that lead to predictable fragmentation patterns. Besides data storage applications, sequence-coded poly(alkoxyamine-amide)s could also be used as molecular barcodes in anti-counterfeit technologies. However, such an application requires synthesis of polymers containing a certain amount of digital information. In order to so, two routes were recently

KEY WORDS: sequenced-coded polymers, solid-phase synthesis, MS/MS sequencing, information-containing macromolecules.

References 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, R.K. Roy, Macromolecules, 48, 4319–4328 (2015) 5- R. K. Roy, C. Laure, D. Fischer-Krauser, L. Charles, J.-F.Lutz, Chem.Commun., 51, 15677-15680 (2015) 6- C. Laure, D. Saranti-Karamesini, L. Charles, J.-F.Lutz, submitted. 2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems 23-25 May 2016, Strasbourg, France

Fluorescent brighteners as visible LED-light sensitive photoinitiators for free radical photopolymerizations

X. ZUO1,2, F. MORLET-SAVARY1, B. GRAFF1, N. BLANCHARD3, J.-P. GODDARD2, J. LALEVEE1

1 Institut de Science des Materiaux de Mulhouse IS2M, UMR CNRS 7361, UHA, 15, Rue Jean Starcky, 68057 Mulhouse, Cedex, France 2 Laboratoire de Chimie Organique et Bioorganique, EA4566, UHA, ENSCMu, 3 rue Alfred Werner, 68093 Mulhouse Cedex, France 3 Laboratoire de Chimie Moléculaire, Université de Strasbourg, UMR CNRS 7509, ECPM, 25 rue Becquerel, 67087 Strasbourg, France

ABSTRACT: The photochemical and electrochemical inhibition even upon irradiation with low LED light investigations of commercially available, safe and intensity. cheap fluorescent brighteners, namely, triazinylstilbene (fluorescent brightener 28) and 2,5-Bis(5-tert-butyl- benzoxazol-2-yl)thiophene as well as their original use as photoinitiators of polymerization upon LED irradiation are reported. Remarkably, their excellent near-UV/visible absorption properties combined with outstanding fluorescent properties allow them to act as high-performance photoinitiators when used in combination with diaryliodonium salt. These two- component photoinitiating systems could be employed for efficient free radical polymerizations (FRP) of acrylate. In addition, this brightener-initiated photopolymerization is able to overcome oxygen

KEY WORDS: Photoinitiator; free radical photopolymerization; fluorescent brighteners; Light Emitting Diode (LED).