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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 has several interesting ramifications – from mimicking the exquisite conformational control seen in biological macromolecules to understanding factors that govern the lamellar crystallite sizes in semi-crystalline polymers. During the past decade we have examined several aspects dealing with control of chain conformation in solution; and we have also attempted to translate this control towards regulating the morphological characteristics of the bulk polymer. The lamellar morphology that is often realized in these attempts leads to the layering of different types of immiscible domains; a closer examination of these layered structures prompted us to begin exploring the similarity between these systems and 2D polymers. 2D polymers have begun to attract the attention of several groups world-wide; although many early efforts have examined polymerization at air-water interfaces and 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

have recently demonstrated. However, these are not robust structures that can be prepared in bulk and exfoliated. It is with this challenge that we have just begun to examine alternate approaches to prepare 2D polymers; broadly, our strategy is to pre-organize multi-segmented monomers bearing at least two polymerizable units at the segment junctions. The pre-organization is designed to be driven by segment immiscibility and strengthened by the strong interactions, such as crystallization, within the domains; polymerization of the double bonds in the solid or semi-molten state it was expected would lead to the formation of a cross-linked and reasonably stiff sheet that would represent a 2D polymer. By suitable choice of the outer segments, it was felt that exfoliation could be made feasible. In the talk, I shall describe our efforts beginning with chain folding and I shall end with our recent foray into 2D polymers.

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).




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 polymersomes, are among the most attractive systems for drug delivery applications. Actually, vesicles obtained by self-assembly of block copolymers are expected to overcome some of the current limitations 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 copolymer structure would allow both controlling the self-assembled structure and the resultant biofunctionality. We report an overview on the self-assembly in water of amphiphilic block copolymers into polymersomes, and their applications in loading and controlled release of both hydrophilic and hydrophobic molecules and biomolecules. We pay special attention to polysaccharide and polypeptide-based block copolymer vesicles that we have studied these recent years in our group. These newly developed copolymers that mimic the structure and function of glycoproteins represent an example of the effectiveness of a biomimetic strategy in implementing materials design. In addition, magnetic polymersomes, including iron oxide -Fe2O3 nanoparticles are currently investigated, together with their potential applications as contrast agent for imaging and as therapeutic nanoparticles using hyperthermia (Figure 1). Exciting and very promising results about their therapeutic evaluation for tumor

targeting and in vivo tumor regression studies will be presented.

Fig. 1 : A Scheme of dual-loaded polymersomes with iron oxide nanoparticles and doxorubicin in their membrane

Finally our recent advances in using “biomimicry approaches” to design complex, compartmentalized materials will be proposed (Figure 2). We demonstrate the formation of compartmentalized polymersomes with an internal “gelly” cavity using an original and versatile emulsion-centrifugation process. Such a system constitutes a first step towards the challenge of structural cell mimicry with both “organelles” and “cytoplasm mimics”. This study constitutes major progress in the field of structural biomimicry and will certainly enable the rise of new, highly interesting properties in the field of high-added value soft matter, especially in controlled cascade (bio)reactions. Fig. 2 : “Plastic cells” as enzymatic reactor. (a) Graphical depiction of the applied system. (b) Plot profiles of the fluorescence cross-section for different time point showing the increase of fluorescence with time.

(a) (c) (b)

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.




Fig. 1: Quasibinary phase diagram of PD in methanol-water solution (1:1, v/v).

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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 grafted with a thermo-responsive polymer poly(diethylene glycol methyl ether methacrylate) (PMeO2MA) using a combined ATRC and ATRP technique with a very high conversion (69%) of the monomer to produce the graft copolymer (PD).1,2 Dynamic light scattering (DLS) study is used to study 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 temperature of the PD solution (0.2%, w/v) indicating a lower critical solution temperature (LCST) type phase transition (TPL) in aqueous medium. In isopropanol medium an upper critical solution temperature (UCST) type phase transition (TPU) is noticed but neither LCST nor UCST type phase transition is noticed for methanol larger sizes (400-750 nm), and exhibit neither any break in Z-average size-temperature plot nor any surprisingly at 40-60% both UCST and LCST type phase separation occurs simultaneously. Butin the mixture containing 70-90% methanol swelled state of the particles (size 250 -375 nm) are noticed. We have drawn a quasibinary phase diagram (Fig.1) for 50 vol% of methanol indicating presence of dispersed swelled 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-

0.2%,w/v) and it indicates an approximate inverted hourglass phase diagram where a swelled state exists between two single phase boundary produced from LCST and UCST type phase transitions. The phase separation process has been explained from temperature dependent 1H NMR spectroscopy along with transmission electron microscopy.

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.




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 electronics, polymeric semi-conductors (PSCs) have been the center of major research efforts in the last 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 still necessary to achieve proper growth control of PSCs and to detetmine their structure. This contribution will focus on recent advances in growth control and crystallization of some key PSCs such as regioregular poly(hexylthiophene). Particular emphasis will be given to the progress made in our group on oriented growth of PSCs using high-Temperature rubbing or epitaxy.

I. High temperature rubbing. Precise control of orientation and crystallinity is achieved in regioregular poly(3-hexylthiophene) (P3HT) thin films by using high-temperature rubbing, a fast and effective alignment method. Rubbing P3HT films at temperatures TR ≥ 144 °C generates highly oriented crystalline films with a periodic lamellar morphology with a dichroic ratio reaching 25. Uniquely, the inverse of the lamellar period l scales with the supercooling and can accordingly be controlled by the rubbing temperature TR. The exciton coupling in P3HT crystals is correlated to the length of the average planarized chain segments lc in the crystals. The high alignment and crystallinity observed for TR > 200 °C cannot translate to high hole mobilities parallel to the rubbing because of the adverse effect of amorphous zones interrupting charge transport between crystalline lamellae. Although tie chains bridge successive P3HT crystals through amorphous zones, their twisted conformation restrains interlamellar charge transport. The evolution of charge transport

anisotropy is correlated to the evolution of the dominant contact plane from mainly face-on (TR ≤ 100 °C) to edge-on (TR ≥ 170 °C).

Fig.1. Evolution of the dichroic ratio and order parameter in P3HT films oriented by high-temperature rubbing (left). Lamellar morphology observed by TEM.

II. Epitaxial crystallization. The large majority of semiconducting polymers based on poly(alkylthiophene)s with linear or branched alkyl side chains are reported to -stack in their crystalline phases. In regioregular poly(3-(2,5-dioctylphenyl)thiophene) (PDOPT), however, interactions are absent due to the presence of the bulky 2,5-dioctylphenyl side groups. High levels of crystallinity and orientation are created in thin films of PDOPT aligned on substrates of naphthalene by slow directional epitaxial crystallization. Depending on molecular weight, both edge-on and flat-on lamellar crystals are obtained. Electron microscopy imaging reveals a transition from extended to folded chain crystallization for Mn 12.7 kDa. The high orientation and crystallinity levels result in high anisotropy of UV-vis absorption and photoluminescence. The single-crystal-like electron diffraction patterns are used to determine the structure of PDOPT. PDOPT features perfectly planarized chains despite the absence of -stacking. The octyl side chains are interdigitated and crystallize in a dense subcell which is compared to that of other semiconducting polythiophenes. This comparison allows to define some correlations between side chain packing and overall crystallinity of the PSC.

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




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 semiconducting polymers and oligomers for electronic devices. The intra- and intermolecular charge transfer interactions could be effectively tuned by varying the electron donating and/or accepting strength of individual building blocks, yielding suitable absorption characteristics and optimum optical band gap for device applications. Various techniques such as UV-vis absorption and fluorescence spectroscopies, cyclic voltammetry, and density functional theory calculations give insight into the molecular level properties. However, predicting device performance by extrapolating the results obtained from these analyses is not possible in most cases. This is because the structural ordering of the polymers/oligomers in the film state plays a significant role in the device performances.

Charge carrier generation and transport properties are the most important parameters which determine the device efficiency of semiconducting materials. Quantitative estimation of these parameters not only

reflects the material properties at the molecular level but also their ordering in the film state. Fast and reliable measurement of such parameters helps speedy screening of new materials and hence facilitates further development in the area of organic electronics. In this context, flash-photolysis time-resolved microwave conductivity (TRMC) has attracted significant interest. TRMC is a unique electrodeless technique, which provides information about charge carrier generation and short-range (nanometer scale) intrinsic charge carrier transport properties of a material. This is an effective tool for predicting the device performances (particularly photovoltaic and field-effect transistor devices) without the fabrication of actual devices.

In this talk, a set of donor-acceptor type new semiconducting polymers and oligomers will be presented. Correlation of their structure, film state organization, optoelectronic properties and device performances with respect to TRMC results will be discussed in detail.

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).




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: Information-containing macromolecules are polymers that contain a message encrypted in their comonomer sequences. The archetypal example of such a polymer is DNA, which is used in biology to store genetic information.[1] However, DNA is certainly not the only polymer that can contain molecular information.[2] In principle, a string of information can be created in any copolymer using two comonomers defined intentionally as 0-bit and 1-bit (Figure 1). However, such polymers have to be monodisperse and perfectly sequence-defined. In addition, the message encoded in their chains should be easily read

In this lecture, I will present recent achievements obtained in my laboratory for the synthesis of information-containing macromolecules. Recent progress in the field of sequence-controlled polymers allows synthesis of unnatural macromolecules with precisely controlled primary and secondary structures.[3-6] For instance, monodisperse sequence-defined polymers were prepared using chemoselective iterative strategies.[7] Furthermore, the readability of these polymers will be presented. For instance the sequencing of unnatural sequence-defined copolymers by tandem mass spectrometry will be discussed.[7]

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




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 on the use of bottom-up chemical self-assembly 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

in the formation of supramolecular plasmonic waveguides and interconnects.[9]

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.




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 macromolecules has been an intense area of research in interdisciplinary domain ranging from biology to materials science. Most of the amphiphilic molecules are structurally identical in broad sense i.e. they consist of a hydrophobic and a hydrophilic segments which differ in terms of their relative length, volume and nature of covalent linking to each other. A natural next step towards enriching their structural diversity would be to make multiple directional forces such as H-bonding and π-stacking work in tandem. However, examples of H-bonding-directed self-assembly of abiotic building blocks in aqueous medium are still rare presumably because of the inherent difficulty associated with competitive H-bonding interaction with the water molecules. We have described recently spontaneous vesicular assembly of a bis-hydrazide functionalized naphthalene-diimide (NDI)-based non-ionic bolaamphiphile in aqueous medium by synergistic effect of π-stacking and hydrogen-bonding. Site isolation of the hydrogen bonding functionality (hydrazide), a strategy that has been adopted so elegantly in nature, has been executed with perfection in the present system to protect them from bulk water so that distinct role of hydrogen-bonding in self-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

unsymmetrical π-amphiphiles, both having naphthalene-diimide chromophore connected to a non-ionic and anionic head groups in opposite arms, was realized. They differ only in the location of a hydrazide group, placed either at the non-ionic or anionic arm of the NDI chromophore. H-bonding among the hydrazides, compensating electrostatic and steric factors, promotes unidirectional alignment and monolayer vesicles leading to contrasting surface functional group display and enzyme inhibition ability. More recntly we have moved to a chromophore-conjugated macromolecular amphiphilic system consisting of a trialkoxy-benzhydrazide functionalized naphthalene-diimide (NDI) building block at the chain end of a water soluble non-ionic polymer. It shows vesicle and reverse vesicle assembly in water and oil, respectively, with bunch of interesting features such as aggregation-induced enhanced emission, excellent container property for both hydrophobic and hydrophilic dye, remarkable thermal and kinetic stability. More importantly the assembly and morphology in such supramolecularly engineered polymers appear to be primarily driven by H-bonding functional group which can overcome the packing parameters of classical immiscibility driven aggregation of amphiphilic block copolymers.

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.




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 solvents.

Fig. 1 : Chemical structure of BHPB-n As shown by FTIR spectroscopy studies, the self-assemblies are driven by H-bonds between amide; but these studies reveal that the esters are also involved in the self-assembly. Their lengths governs the shape of the self-assemblies : flat ribbons, nanotubes or twisted ribbons.1,2

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

We will present the spectroscopic properties of these 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 microscopy and transmitted light intensity measurements. The structures of the different phases have been probed by FTIR and NMR. We will show that the different results provide new insights into the interpretation of phase diagrams.3 BHPB-n compounds can be derivatized with a few functional groups while their ability to form nanotubes 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.

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




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 process. We found a drastic reduction in the pore size 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.

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Fig. 1 : Thermal conductivity as a function of aerogel density for two different techniques of preparation

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.




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 architectures in the crystalline phase are attracting considerable interest over the last two decades. For both design and analysis of molecular crystals, we have developed a strategy called molecular tectonics which is based on the formation of molecular networks through the design of complementary tectons or molecular construction units. The generation of molecular networks and subsequently of crystals is

achieved by self-assembly processes based on repetitive molecular recognition events. This approach, combining supramolecular synthesis and self-assembly processes in the solid state, is operational and versatile and allows the design and construct a variety of complex purely organic or hybrid architectures. The approach will be presented and illustrated by a variety of tectons and networks.

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).




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 and self-assembling properties of fullerene derivatives render them as an attractive class of materials with wide range of applications in nanotechnology and material science.1 Tuning the substitution of the well studied acceptor [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) to upshift the LUMO (lowest unoccupied molecular orbital) is a strategy used to enhance the electron acceptor properties of fullerene derivatives.2 However, the rational design of fullerene 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 properties. Most of the polymeric materials exhibit intrinsic one dimensional, self-assembled nanostructures due to their directionality and order in the monomeric unit itself. Developing covalently modified polyfullerenes and non-covalently functionalized supramolecular fullerene polymers are 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)

covalent grafting of fullerenes with polymer units, ii) template based non-covalent functionalization using polymers and biomolecules as template and iii) small molecule self-assembly. Our morphological investigation reveals the self-assembly of fullerene monomers as nanoclusters while self-assembled polyfullerenes result in the formation of one dimensional nanostructures. Detailed photophysical and morphological investigations of such polyfullerene systems will be discussed.

Self-assembly Polymerisation

Figure 1. The schematic representation of formation of nanoclusters and one dimensional nanostructures upon traditional self-assembly and polymerization, respectively.

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




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 controlling the interaction of materials with their surrounding environment. Catalysis, molecular recognition or cell adhesion are typical examples of such interactions. During the last decades, progress in surface science allowed modifying and tuning material's surface properties in a highly controlled way by the development of new coating methods. Among them, the use of an external stimulus, such as an electric signal or light, appears as a convenient way of inducing a film buildup in a one pot manner. We introduced a new type of electro-construction of polymeric film based on the formation of covalent bonds between polymers1-3 induced by an electro-generated gradient of morphogens. First introduced by Turing,4 morphogens are specific molecules to which cells respond in a concentration-dependent manner. We extended this definition to film buildup on a surface where morphogens are molecules or ions that induce a chemical reaction or interaction in a confined space near a surface. In a first study, Huisgens – Sharpless click reaction was used to induce a reticulation between two polymers by electro-oxidation of Cu2+ into Cu+ (Fig. 1).1

Fig. 1 : Schematic representation of the one-pot self-construction of polymeric film based on click-chemistry triggered by the application of an electric potential.

Generated at the surface of the electrode, Cu+ ions (morphogens) diffuse from the surface to the solution and catalyze the click reaction between azide and alkyne functionalized polymers. As the reaction only takes place in the presence of the morphogens, all the constituents can be mixed in a single solution and the film formation takes place by a simple application of an electrical stimulus. Merging the fields of polyelectrolyte multilayers and morphogen-driven film buildup, we developed a strategy which allows the self-assembly of oppositely charged macromolecules on a surface. This strategy is relied on a charge-shifting polyanion that undergoes a hydrolysis at acidic pH, generated electrochemically (H+ = morphogen), leading to a polycation. In the presence of an enzyme, this electro-controlled hydrolysis leads to the formation of complexes on the surface.5 The obtained film, assembly of polycation/enzyme complexes, is enzymatically active. Inspired by the catechol numerous properties, a mussel protein derived molecule, we designed a catechol based electrochemically triggered construction of films based on an organic morphogen: a synthesized ethylene 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 suited for the functionalization of micro-electrodes by enzymes opening the route towards miniaturized biosensors.

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




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 nanomaterials like carbon nanotubes and graphene oxide.6 A gel based novel trihybrid system with nanofibers, nanosheets and nanoparticles has also been dicovered.7 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 antibacterial activity against Gram negative bacteria.9

Fig. 1 : Various applications of self-assembling peptide based gels.

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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.




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 cell adhesion. One general way that nature found to transform a mechanical signal into a chemical one is by making use of force induced conformational changes. Such changes can be at the origin of cryptic site exhibition but they can also affect enzymatic activity. We have, over the last years, developed several chemo-mechano-responsive systems based on mimicking natural processes. We will present here several examples of such systems: We will discuss systems where by stretching one can modulate the binding affinity of a ligand for receptors present on the substrate (1,2). We will also present systems where stretching 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.

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Fig. 1 : Evolution of the enzymatic activity of a polymeric film containing β-galactosidase for various stretching degrees (upper evolution: enzymes not covalently fixed to the polymeric matrix; lower evolution: enzymes covalently fixed to the polymeric matrix) (results taken from ref 5)

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)

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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 1: Color tunable lanthanide gels

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

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




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 defined size, shape, architecture and chemical functionality have received more attention nowadays, because they are the forefront of many next-generation organic optoelectronic technologies. Among conducting polymers such as polypyrrole, polythiophene, polyphenylenevinylene, and polyacetylene, polyaniline (PANI) has been most extensively studied because it exhibits good environmental stability and its electrical properties can be modified by both the oxidation state of the main chain and protonation. However, the control of the size and morphology during the synthesis of nanostructured PANI still remains a challenge. The reported methods for the synthesis of PANI nanostructures include interfacial polymerisation method, electrospinning, seeding polymerisation and template method (hard and soft). Among them, the soft-templated method utilizing

the assembly of surfactants, polyelectrolytes and organic dopants to create network 1D structure is promising as it uses the bottom-up approach of supramolecular chemistry. Inspired by the easy preparation of PANI and the use of water as an environment friendly solvent, we wonder if we could directly obtain nanoscale PANI based on soft templated method by self assembly of organic acids in aqueous medium. Herein, we report a simple process of synthesis of nanostructure of PANI doped with several tetracarboxylic acid (aromatic and non-aromatic) in bulk quantity via in-situ polymerization. The architectures and properties of the formed PANI nanotube will be presented. This lecture will discuss about the architectures and properties of the formed PANI nanotube, particularly recent applications.

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.

Aniline Aromatic Tetracarboxylic Acid




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 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 polymers. Since few years our group works on the possibility to produce self-organized plasma polymer nanopatterns without using any etching masks. This task stills challenging and the main problem comes from the difficulty to identify the prevailing driving forces that lead to the formation of the observed organized or self-organized patterns on plasma-exposed polymer surfaces. The other difficulty is the multi-scale nature of this system, where diverse chemical and physical phenomena may take place at different spatial and 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 branched and needle structures required long pulse-off time (toff) and short pulse-on time (ton), provided by low DC, which afford enough time for the radicals to migrate and react with the nucleation sites. The goal of this presentation is to get further insights of aforementioned mechanisms.

100 nm

Fig. 1 : AFM images of the beads and branches structures during plasma polymerization

A second example is organization or « self »-organisation which result from the interplay between the plasma and solid components involved. Recently our group has demonstrated the feasibility to design super-structures under co-deposition of crystalline nanocellulose whiskers (CNW) during plasma

polymerization of maleic anhydride 3, Figure 2. A close view over the superstructures provided some information regarding its formation.

Fig. 2 : Phase AFM images of plasma polymer films deposited in

presence of crystalline nanocellulose whiskers

This work brought new important information that represent a step forward in the understanding of the morphogenesis of complex structures induced by

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




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 stereoisomer of the poly(lactic acid), is a widely used biobased polymer in degradable plastics. It is also used as a degradable biomaterial in many medical devices and tissue engineering. In this talk, three types of multiphase polymer systems containing poly(L-lactide) will be presented. In all cases, the crystallization of PLLA plays a significant role in the self-assembly of 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 temperature small-angle and wide-angle X-ray scattering (SAXS and WAXS) during heating. It was observed that the segmental mobility of the PLLA

block plays a significant role in the formation of mesophase of PLLA in block copolymer systems. Last part of the talk highlights the structural changes in PLLA/CPO co-crystals at multiple length scales using differential scanning calorimetry, small-angle neutron scattering, Fourier transform infrared spectroscopy, and temperature-dependent wide- and small-angle X-ray scattering.

Fig. 1: Lorentz-corrected SAXS patterns of (a) PLLA-b-PEG-b-PLLA and (b) PLLA-b-PDMS-b-PLLA in the melt-quenched (amorphous) state.

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




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]

ABSTRACT: The key point in the photopolymerization area is the transformation of multifunctional monomers (e.g. acrylates or epoxides) or prepolymers into highly crosslinked networks using a photochemical route 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

highly versatile and high performance visible light photoinitiating systems.

New radical chemistry (e.g. boryl, silyl, germyl …) can also be used for high performance radical initiating systems.[1-3] Some examples will be provided.

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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).




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 used as precursor of advanced polymer materials for sensing, biomedical application, device application etc. Different functionalities of smart polymers make the polymers responsive to different stimuli such as temperature, pH, light, ionic strength, redox system and host–guest interactions. Zwitterionic polymers contains both cationic and anionic moiety into the repeating unit which helps them to respond to different external stimuli. Furthermore, the introduction of amino acid into those polymers makes them more bio‐friendly. The fictionalization of a vinyl monomer with amino acid through the reaction between terminal chain functional group of amino acid with appropriate functional groups [such as –COOH or –COX (X = Cl, Br)] of vinyl monomer leads to zwitterionic monomers. Subsequent polymerizations of amino acid‐based monomers lead to the formation of the zwitterionic polymers with pendent amine and carboxylic acid functional groups. In recent time, poly(ionic liquid)s (PILs) have also gained considerable attention to the polymer and materials science community because of their wide range of applications such as CO2 sorbents, porous materials, carbon precursors, catalytic materials and specially as a stimuli‐responsive materials. I will discuss several recent developments of different synthetic routes of poly(zwitterions) and PILs in our laboratory. In particular, the synthesis of ε‐L‐lysine‐/L‐serine‐/L‐methionine‐based zwitterionic polymers of controllable molecular weights and low dispersities will be discussed. It will be shown that in alkaline pH, poly(ε‐L‐lysinyl acrylamide) (PLAM) undergoes Cu(II) ion‐induced aggregation through the complexation its pendent amine and carboxylic groups with Cu(II) ion 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

by discussing the aqueous solution behavior of PSA solution in the pH range of 2.4‐3.4 where it forms insoluble aggregates through the intra‐ and inter‐molecular electrostatic interaction between the pendent ammonium and carboxylate groups of the neighboring zwitterionic PSA molecules. Furthermore, the temperature dependent phase transition upon heating of the biphasic PSA solution at that pH range, exhibiting distinct reversible upper critical solution temperature (UCST) will be discussed. The effect of molecular weights, the solution pH and the electrolyte type on the UCST will also be discussed. Finally, the synthesis of fluorescein isothiocyanate (FITC) tagged PSA with dual‐responsiveness will also be discussed. Furthermore, in the area of stimuli responsive PILs, the synthesis of a cationic phosphonium poly(ionic liquid) of varying and controllable molecular weights via reversible addition‐fragmentation chain transfer (RAFT) polymerization will be discussed. It is known that water‐soluble poly(ionic liquid)s often exhibit a lower critical solution temperature (LCST). In contrast, in this case, it will be shown that the transparent aqueous solution of this PIL turns into a turbid solution in presence of halide ions, forming insoluble microgel aggregates owing to intra‐ and/or inter‐chain cross‐linking through halide ion bridges between PILs, which upon heating exhibits a distinct upper critical solution temperature (UCST)‐type phase transition due to disruption of ion bridges. A cross‐linked hydrogel system containing this PIL with both halide ion‐ and thermo‐responsiveness (UCST‐type) will be presented. The application of this PIL as a smart stabilizer to promote water borne double‐responsive dispersion of multi‐walled carbon nanotubes (MWCNTs) towards halide ions and temperature will also be discussed.

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




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

ABSTRACT: Recently, P. Mésini and coworkers1 have prepared nanotubular structures from diamide molecules (3,5-Bis-(5-hexylcarbamoyl-pentyloxy)-ben-zoic acid decyl ester, BHPB-10 for short) (Scheme 1). The inner and outer diameter of the nanotubes are very well-defined with very little cross-section dispersity as ascertained by the scattering patterns (fig.1) .

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

Fig. 1: SANS curves for: () BHPB-10/trans-deca-hydronaphthalene gels; ()BHPB-10/iPS/trans-deca-hydronaphthalene hybrid systems. Inset: the curves in the low-angle domain q= 0 to q= 0.5 nm-1. (ref. 2).

We have recently shown2 that the sheathing of polymer fibrils grown from an isotactic polystyrene thermoreversible gel can be achieved with these nanotubes. Only a physical process is involved, namely heterogeneous nucleation. The polymer fibrils act as heterogeneous nuclei onto which the nanotubes form. Neutron scattering experiments using contrast

matching do show a difference between the scattering function of the nanotubes in the binary systems and those in the hybrid system at very low angles (figure 1 inset). We have extended this process to a semi-conducting polymer, Poly(3-butylthiophene-2,5-diyl) (P3BT). The system has been studied by neutron scattering and by conducting AFM (C-AFM).

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 covered with BHPB-10 thus forming a hybrid system. By means of the process shown in fig 2, gradual penetration of the conducting tip into presumably sheathed fibrils first reveals the behavior of an insulator (BHPB-10), and then the behavior of a semi-conductor (P3BT). SANS experiments give further confirmation to these outcomes. Scattering curves can be fitted with concentric cylinders, which bears out the model where P3BT fibrils are sheathed by BHPB-10 nanotubes.

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




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 forming a nanotubular wire encased within a shell of peripheral dendrons. The capability of pillar[5]arenes to form inclusion complexes has been also exploited. Specifically, detailed binding studies have been carried out in solution with 1,6-dicyanohexane as the guest. Inclusion complexes have also been prepared in the 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.

Schematic representations of (A) pillar[5]arene derivative (dark blue: pillar[5]arene core, pale blue: peripheral dendrons), (B) the columnar stacks of the compound, (C) the supramolecular arrangement of the compound into the hexagonal columnar phase, (D) the columnar stacks of the inclusion complex (dark red: 1,6-dicyanohexane guest).

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.




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 preparation of 3D-networks incorporating smaller GNPs remains a challenge. This is particularly important for their future application in the field of catalysis. In this contribution, we will show that the use of a bulky organic 3D-linker, namely a C60-hexaadduct functionalized with twelve thiocyanate moieties is perfectly suited for the one-pot synthesis of hybrid materials where homogeneous sub-3 nm GNPs are connected through strong S-Au bonds [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.

Fig. 1 : Self-assembly of homogeneous ultra-small gold nanoparticles thanks to the design of a new

hexaadduct fullerene bearing 12 thiocyanate functions.

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.




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).

ABSTRACT: Pillar[n]arenes are readily available

macrocyclic compounds recently discovered.1 Their host-guest chemistry has been already intensively investigated. Owing to the electron-rich nature of their constitutive aromatic subunits, pillar[5]arenes exhibit interesting host-guest properties with -electron-poor aromatic guests such as viologen and imidazolium cations. Along with charge-transfer interactions occurring between the electron-rich cavity of pillar[5]arenes and -electron-poor guest molecules, C-Hπ interaction is also a driving force in the formation of inclusion complexes. Actually, simple alkyl-substituted guests are efficiently encapsulated in the cavity of pillar[5]arenes to generate pseudo-rotaxanes. Such host-guest complexes are indeed perfectly suited for the synthesis of [2]rotaxanes. As part of this research, we have shown that pillar[5]arene-based [2]rotaxanes can be prepared from the reaction of

diacyl chloride reagents with various amine stoppers.2 The yield in [2]rotaxane is sensitive to the reaction conditions (solvent, stoichiometry) but also to structural and electronic factors. In particular, the nature of the starting amine reagent has a dramatic influence on the yields of [2]rotaxanes thus showing that the outcome of the reaction is not simply related to the binding constant of the diacyl chloride reagent with the pillar[5]arene. Indeed, the difference in yields must be related to the difference in affinity for the various mono-acylated intermediates. The yields of [2]rotaxane are also influenced by several structural factors such as the chain length of the bis-acyl chloride reagent or the size of the peripheral substituents of the pillar[5]arene building block. Finally, the preparation of [2]rotaxanes has been also investigated under our conditions starting from alkyldiamine reagents and acyl chloride stoppers.

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.




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 attractive synthetic target for fundamental studies and practical applications.1 As part of this research, we now report the first example of a hexakis-adduct of C60 with self-assembling dendrons at every possible position, i.e. 12 dendrons per fullerene (compounds 1a-e). Intuitively, the quasi-spherical hard core of these molecules and an isotropic distribution of dendrons around their surface were expected to force these molecules to adopt a globular shape suitable for self-organisation into various cubic, tetragonal or quasicrystalline periodic and quasiperiodic arrays. Unexpectedly, regardless of this high degree of substitution

of the C60 core, the fullerodendrimers reported herein self-organise into 2D columnar arrays, due to the dominating self-assembling ability of the peripheral dendrons.2

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.

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Self

Assembly Folic acid

F gel

PVPS

Co-Assembly

F-PVPSx gel

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 makes them appropriate candidates for applications in diverse fields. However, the practical applications of supramolecular gels are limited as they are mechanically weak. One uncomplicated way to improve the mechanical and thermal stability of the supramolecular gels is to prepare hybrid gels with covalent polymers.

In an endeavor to improve the mechanical property of folic acid (F) gel, poly(4-vinylpyridine-co-styrene)(PVPS) is elegantly incorporated as a 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 (0.3%, w/v). PVPS assisted gel formation of F is obvious from the drop in critical gelation concentration and increased fiber diameter and branching of F-PVPSx gels compared to that of F gel. PVPS confers an outstanding improvement of mechanical properties. 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 PVPS concentration showing maxima at F-PVPS5 gel. 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

the F-PVPS5 gel shows a sigmoidal increase. The gelation rate constants manifests that PVPS enhances the gelation rate. The hybrid gel exhibit five orders increase of dc-conductivity than that of F gel showing semiconducting nature in the current-voltage plot. The Nyquist plot in impedance spectra of F-PVPS5 xerogel depict a depressed semicircle with a spike at lower frequency region and the equivalent circuit represent a complex combination of resistance–capacitance circuits attributed to the hybrid morphology of the gel fibers.

.

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.




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

chemistry have permitted the preparation of polymers

with advanced properties by controlling their topology,

functionality and microstructure providing access to

more elaborated architectures1 such as star, comb and

hyperbranched polymers that could be bearing a

variety of functional groups at well-defined sites on the

polymer chain. The ability to control the architecture of

polymers allows tuning their properties and adjusting

their performances regarding targeted applications.

Here the objective is to develop synthetic strategies

to prepare macromolecules containing amino acids.

These amino acids will be used either as elements of a

peptide sequence relevant for biological applications or

to promote the introduction of further functionalities at

well-defined localizations on the macromolecule chain.

One approach that have been explored considered the

iterative addition of amino acids and synthetic building

blocks on a solid support to prepare oligomers

containing amino acids that are inserted on their main

chain.2,3 However, the synthetic strategy that will be

discussed here focused on the introduction of amino

acids of the side chains of the polymer through the

preparation of peptide-based macromonomers. These

macromonomers have been synthesized by solid-phase

peptide synthesis from a conventional peptide resin, i.e.

2-chlorotrityl chloride resin, involving the iterative

addition of the desired amino acids on the support

followed by the insertion of the polymerizable moiety

of choice before cleavage from the resin. The

macromonomers were then polymerized under the

relevant polymerization conditions according to the

polymerizable moiety to obtain peptide-based comb

polymers.

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

n)cleavage

piperidine

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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 - amino acids, sugars, lipids and nucleic acids are intrinsically bioactive, biodegradable and biocompatible which makes them as perfect building blocks to generate new materials.1 In particular, the research on peptide-based materials has intensified over the last few years, not only because of their 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. Herein, we studied the self-assembly of β and γ 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

functionalized with the same peptide generated unique dendritic assemblies. This comparative study on self-assembly using diphenylalanine backbone homologues and of the co-assembly with CNT covalent conjugates is the first example exploring the capacity of β and γ peptides to adopt precise nanostructures, particularly in combination with carbon nanotubes.5

Figure. Self-assembled nanostructures of and diphenylalanine

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.




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.

ABSTRACT: Ir(ppy)31 was used as new catalyst for

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

nIr; the polymer surfaces were analyzed by XPS. The chemical mechanisms were examined through laser flash photolysis, NMR, ESR and size exclusion chromatography experiments.

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N

IrO

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S

nIr Ir(ppy)3

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




Synthesis of precision compatibilizers for composite materials

J. LOUWSMA,a,b

S. JOLY,a J.-F. LUTZ,

b D. CHAN-SENG

b

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

prepare composite materials can be challenging as their

difference in chemical nature can result in their

incompatibility. However the homogeneity of the

composite materials is of high importance to reach

materials with high performances. To overcome this

difficulty one approach considers the use of additives,

named compatibilizers, capable to enhance the

interfacial properties between the immiscible

components of the composite material.1

In this context, the synthesis of sequence-controlled

oligomers containing phenylalanine residues was

considered. The control of the sequence on the

oligomer backbone was accessed by solid phase

synthesis from a chlorotrityl chloride resin permitting

the iterative insertion of amino acids and synthetic

building blocks.2 This technique allows for the

synthesis of phenylalanine-based oligomers with a high

degree of precision in the design permitting to screen

some specific structural parameters in a controlled

manner and thus identify the structural requirements

for the elaboration of efficient compatibilizers.

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.

cleavage N3HOOC

2016 INDO-FRENCH CONFERENCE Functional polymers and self-assembled systems


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 sciences, the design of complex molecular systems in the crystalline phase with strict control of order and periodicity at both microscopic and macroscopic levels is of prime importance for development of new solid-state materials and devices.1 The design and fabrication of complex crystalline systems as networks of crystals displaying task-specific properties is a step toward smart materials.2 Here we report on iso-structural, and almost iso-metric, molecular crystals of different colours, and their welding by 3D epitaxial growth into networks of crystals as single-crystalline entities.3 Upon combining the dicationic hydrogen bond (H-bond) donor tecton 1 (Fig. 1i), with H-bond acceptor anionic metallatectons [MIIL2]4- (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-ML2 has been obtained (Fig. 1iii) and characterized by XRD methods.

(i) (ii)

12-NiL2

12-CoL212-MnL2 12-FeL2

12-CuL2 12-ZnL2 (iii)

Fig. 1 : H-bond donor tecton 1 (i) and H-bond acceptor metallatecton [MIIL2]4- (ii). Iso-structural crystals formed by this tectons (iii).

Taking advantage of the iso-structurality of this family of crystals, welded crystals have been generated by epitaxial growth of crystalline region between two seed crystals (figure 2).

B

AAA

AA

AA

(i)

(ii)

(iii)

(iv)

Fig. 2 : Schematic representation of homo- (ii) and 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 macroscopic networks of crystals is a powerful strategy for the design of hierarchically organized periodic complex architectures composed of different subdomains displaying targeted characteristics. Crystal welding may be regarded as a first step toward the design of new hierarchically organized complex crystalline systems.

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.




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

coordination networks or metal-organic frameworks

(MOFs) increases due to their structural features

(dimension, geometry, topology) and their

properties.1, 2 These porous coordination networks

are composed of organic tectons and metallic

nodes. The design, formation and description of

such periodic architectures may be explored by the

approach called Molecular Tectonic.3, 4

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.

Fig.1: Lewis representation of the different

tectons

In all cases studied, the X-Ray diffraction

investigations revealed their isostructural nature.

The porous crystals (figure 2) display two types of

cavities differing by their volumes, one spherical

(small cavity) and the other of the ovaloid type

(larger 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.

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.

Ovaloïd cavity

Spherical

cavity




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

3Adaptative 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 materials, which present high surface areas combined with uniform distribution of nanopores, can be organized in functional nanopatterns for a number of applications. However, silica is by essence an electrically insulating material which precludes applications for electro-chemical devices. For instance, the formation of hybrid electroactive silica nanostructures is expected of great interest for the design of biocompatible conducting materials such as bioelectrodes.1 Here we show that we can grow supramolecular stacks of triarylamine molecules inside

oriented mesopores of a silica nanolayer covering a gold electrode.2 This addressable bottom-up construction is triggered from solution by simple light irradiation.3-5 The resulting self-assembled nanowires act as highly conducting electronic pathways crossing the silica layer. They allow very efficient charge transfer from the redox species in solution to the gold surface. We demonstrate the potential of these hybrid constitutional materials by implementing them as biocathodes and by measuring Laccase activity that reduces dioxygen to produce water.

I

Ox + e‐ Red

5 nm

Gold

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.




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 for the self-assembly of DNA and RNA. Over the last years, chemists have used these recognition units to trigger the self-assembly of small molecules into functional architectures.1 Recently, our group discovered that properly modified triarylamine (TAA) molecules in chlorinated solvents can generate supramolecular triarylamine nanowires (STANWs) and be combined into packed bundles of fibers which displayed extraordinary metal-like conductivity properties thanks to a non-covalent polymerization.2-4 Furthermore, we have shown that the triarylamine scaffold is a versatile motif to produce functional supramolecular systems which can exhibit a variety of morphologies.5-6 Here, we will report on the synthesis and characterization of a series of triarylamine-nucleobase conjugates. Using spectroscopic techniques such as 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

possibility to use this molecule as sensor for metal ions.

250 500 750 10000.0

0.4

0.8

1.2

1.6

2.0

2.4

Abs

orba

nce

(a.u

.)

Wavelength (nm)

FeCl3

HgCl2

MgCl2

ZnCl2

Fig. 1 : Chemical Structure of thymine-triarylamine conjugate and its use as selective sensor for metal ions.

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.




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 of electron-donor triarylamines (TAAs) to self-assemble into nano-fibers upon light irradiation in chlorinated solvents. 1 These molecules were then assembled between 80 nm lithographically defined electrodes and demonstrated high conductivity (higher than 5×103 S m-1), which systematically decreases when the temperature is lowered to 1.5 K, revealing an intrinsic metallic behavior. 2 Finally, we have exemplified that these TAA units can act as supramolecular structuring synthons for more complex structures, as they retain the general ability to self-assemble upon light stimulation in chlorinated solvents even when modified with various chemical units such as gallate or benzene-1,3,5-tricarboxamide for example. 3 In this work we study gelation, fluorescent and chiroptical properties of trisamidetriarylamine

(TATAs) decorated with chiral and achiral alkyl substituents (Fig. 1, A). We found that these molecules assemble in non-chlorinated solvents, such as toluene, via a cooperative (nucleation-and-growth) mechanism into long fibrillary structures (Fig. 1, B). Thermoresponsive organogels are formed at very low concentrations in various organic solvents (CGC is 0.1% wt or 0.75 mM in toluene). Temperature dependent CD measurements were performed to study the aggregation process of TATAs in detail (Fig. 1, C). Interestingly, we found that the shape and the sign of CD depend on the cooling rate, which is explained by different self-assembly pathways for two cooling regimes.

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

2 µmB300 320 340 360 380

-400

-300

-200

-100

0

100 Slow Cooling Fast Cooling

CD

(m

deg

)

Wavelenght (nm)A C




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 demonstrated that well-designed triarylamine molecules can be used as building blocks to produce functional supramolecular architectures exhibiting various morphologies with excellent physical properties in non-polar solvents such as chlorinated solvents or toluene.1-4 However, their self-assembly in aqueous solution has, to the best of our knowledge, not yet been investigated. Within water environment, amphiphilic molecules are expected to self-organize into hierarchical structures such as fibers, vesicles, ribbons and nanotubes, due to hydrophobic effect and hydrophilic interaction.

Here, we will report on new classes of water-soluble triarylamine molecules decorated with either poly(ethylene glycol) (PEG), peptide or cyanine dyes on the three amide positions (Fig. 1).5 First, we will describe the synthesis of these complex molecules. Using a large variety of characterizations going from spectroscopy to microscopy and even scattering techniques, we will show that these three amphiphilic triarylamines can give rise to different self-assembled objects both in water and in methanol.

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.




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.




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) A first proof of concept has been the design of dynamic 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.

Fig. 1 : Schematic representation of the exchange reaction performed between two peptides containing

an internal dynamic unit

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




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 nanotechnologies consists in coupling together defined individual molecular motions for the production of macroscopic response.1 In 2012, we reported the first example of micrometric contraction and extension of 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 stimuli-responsive bundles of fibers (Fig. 1).3 On the other hand, [c2]daisy chains substituted with 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.

This work represents the first example showing this synchronization of thousands of molecular machines to cross several length scales thanks to a combination of molecular synthesis, supramolecular engineering, and polymerization processes.

Fig. 1 : Muscle-like behavior of an hydrogen-bonding muscle-like supramolecular polymer.

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.




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)

are small molecules (< 2000 g. mol-1

),1 able to

immobilize fluid phases (i.e. water, organic solvents,

oils, liquid crystals, ionic liquids, etc.). The gelation

process is achieved via formation of a self-assembled

three dimensional fibrillar network. Amide containing

molecules, such as L-amino acids derivatives, are used

as platforms for molecular gels elaboration. Indeed,

because of their specifically oriented hydrogen bond

donor and acceptor sites, unidirectional primary

supramolecular structures can be obtained. Then, fibers

found within molecular gels are due to further self-

assembly processes of those primary columns.2 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

based on L-Lysin dervatives (Nα- and C- terminal

substituted) with various peripheral groups such as

carboxybenzyl (G1), naphthalimide moiety (G2) or

3,4,5-tris-hexadecyloxy benzoyl (G3) at Nε-position

have been designed (Fig. 1). Strong molecular gels,

with high gelation efficiency, were obtained mainly in

aromatic and alkane solvents. Those molecular gels

have been macroscopically characterized through their

critical gelation concentration (CGC), the sol-gel

transition temperature (Tgel) and their melting

enthalpies (ΔH). Moreover, the gelation behaviour has

been analyzed as a function of Kamlet–Taft

parameters. Scanning electron microscopy was also

performed on aerogels, obtained from supercritical CO2

drying of corresponding organogels. A strong

difference in the fibrillar nanostructures (shape and

size) could be observed by changing the functional

group grafted on lysine platform (Fig. 2).

Fig. 1 : The synthesized LMWGs [G1, G2 and G3]

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




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

ABSTRACT: The gelation process of Lysine-based low

molecular weight gelators (LMWGs) has been studied

by molecular spectroscopy. NMR and FT-IR spectra

were recorded for Nα- and C- terminal substituted

lysine with various peripheral groups such as

carboxybenzyl (G1), naphthalimide moiety (G2) or

3,4,5-tris-hexadecyloxy benzoyl (G3) at Nε-position

(Fig.1). The influence of side chain nature on self-

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

backbone, Nε-position), has also been investigated.

Molecular scale spectroscopic characterization of the

LMWGs afford a valuable observations regarding 1-D

self-assembly process (stacking-up) which is necessary

for formation of a three dimensional fibrillar network

responsible for immobilizing fluid phases (i.e. water,

organic solvents, oils, liquid crystals, ionic liquids,

etc.). 1-5

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

Fig. 3 : Temperature-dependent direct FT-

IR spectra of G3 in d8-toluene gel state

(1wt %). (10 to 60 °C)

Fig. 2 : Plot of temperature-dependent

mobility of G1 protons. NHa, NHb NHc

and H-Cα.(1.0 wt% in d8-toluene)

Fig. 1: structures of G1, G2, G3




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 triarylamines to self-assemble upon light activation

1

into various supramolecular structures going from fibers

1

to spheres.1,2 We have also measured their exceptional conduction efficiency

3

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 EPR experiments, we will show the long term stability of the light-induced radical cations and their electronic delocalization.

Fig. 1 : Macrocyclic Hexaazaparacyclophane and Schematic Representation of the Dual Charge 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.




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 process for the synthesis of many new supramolecular hierarchical structures. In certain cases, the self-assembly process leads to molecular gels, which has become an area of great interest in the field of supramolecular chemistry. Gels are composed of a 3D network where organic solvents (organogel) or water (hydrogel) are trapped. First gels were obtained from polymers and last two decades authors have report molecular gels obtained from low molecular weight gelators (LMWGs). LMWGs have attracted much interest due to their practical implications as new soft materials [1]. Recently, LMWGs form peptides, pseudopeptides or their cyclic analogues have had 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

low molecular weight organogelators (LMWGs). Rheological results for gels in toluene at different concentrations revealed good thermal stabilities. SEM analysis of the aerogel demonstrated non-twisted fibers, thus confirming the presence of self-organization.

Subsequent FTIR and NMR studies have shown the presence of equilibrium between monomeric (intramolecular H-bonds) and nanotubular (intermolecular H-bonds) forms in solution. Finally, we found that our organogelator is suitable for selective gelation of an organic solvent(s) from (water/organic) mixture with good recovery percents ranging from 73-96% which could lead to potential applications in water cleaning.

.

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.




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 organic molecules of low molecular weight called organogelators. They are currently described as thermoreversible gels, and their formation as a physical gelation1. The question we ask is to know whether this description is valid or not. In this communication, we present a rheological study of the formation and characterization of amino-acid organogels in solvents such as toluene or tetralin. The rheology experiments were carried out as a function of temperature for different concentrations of the organogelator molecules, of the frequency, of the thermal history and of aging. The results show all the characteristics of a dynamically arrested suspension: no critical gel, no rubber elasticity and presence of thixotropic effects. Compared to the behavior expected for a gel, this behavior results from the fact that the

G',

G''

(Pa

)

T(°C)0 10 20 30 40 50

0.2% tetralin-based solution

G' G''

10-4

102

10-2

10-1

100

103

101

10-3

Torganogel

IIIIII

cooling rate 0.2 K/min

DSC peak

G’’

G’

G’

G’’

Fig. 1: Typical experiment showing the formation of the organogel at a frequency of 1 Hz. Three regions: I) classical fluid; II) formation of clusters, liquid state; III) organogel, solid state. Torganogel depends on frequency, concentration and cooling rate.

physical gelation comes from a fractal growth of clusters, while the gelation induced by a dynamical arrest is associated with a crowding of clusters (or particles), which leads to the formation of a purely elastic network in a carrier fluid that is the solvent2. We also show that the difference between organogels and gels appears in the elastic and volume properties of the aerogels derived from organogels and gels. This study shows for the first time that an organogel is not a physical gel, as is currently believed, but a dynamically arrested suspension. The transition from liquid to organogel cannot therefore be associated with the existence of a new phase, but merely to a change in the mechanical response of the solution, from a liquid state to a solid state.

G',

G''

(Pa)

f (Hz)0.1 1

1

T=18.2°CT=17.4°CT=16.8°C

0.2% tetralin-based solution

3

2

0.2

Fig. 2: Behavior of G’ (filled symbols) and G’’ (open symbols) around the liquid to organogel transition, showing that G’ and G’’ do not exhibit the power law behavior (critical gel) expected for a gel at the liquid 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




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


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: Anti-counterfeit technologies have become highly important during the last decades and have found applications in the domain of food and pharmaceutical packaging, paper currency, high values products and treasured artworks.1 These technologies require novel techniques for tracing commercial products that are extremely difficult to be copied but very efficient for the discrimination of the original product from fraud ones. In this context, molecular barcodes would offer to the consumers the safety of buying the original product but also to the manufacturer the ability of guaranteeing its value by increasing his responsibility and liability.

Our proposal to this challenge focuses on the labeling of materials at the molecular level2. A homogeneous dispersion of a small amount of a coded polymer containing information in an organic or inorganic matrix gives a solution to the imitation problem. Finding readable information in the matrix of a product, such as the production date and the lot number, and not only on the packaging will help the consumer come up against troubles that occur after a period of using. In the current work, sequence-defined oligomers synthesized by solid-phase synthesis and bearing a monomer-sequenced binary message were used as molecular barcodes.3 The inclusion of a sequence-coded label into commodity plastics was 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

http://www.nature.com/ncomms/2015/150526/ncomms8237/full/ncomms8237.html#auth-1









Synthesis of monodisperse sequence encoded copolymers using fast orthogonal

chemistry

G. CAVALLO1, A. AL OUAHABI1, L. OSWALD1, L. CHARLES2, J.-F. LUTZ1

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 constitute a new class of molecules that enables data storage at the molecular level.1 These linear macromolecules are built up using two comonomers, representing bit 0 and 1 respectively, thus allowing binary coding. Several strategies for the efficient synthesis of information containing polymers have been developed by J.-F. Lutz and coworkers.2. For instance, polymers synthesized by phosphoramidite protocols3 as well as the new class of poly(alkoxy amine amide)s4 show interesting features. Here we present a new strategy for the iterative synthesis of information-containing polymers based on two chemoselective steps, namely the phosphoramidite

coupling and a radical-radical coupling. This orthogonal strategy does not employ protecting groups and utilizes two different types of building blocks: a spacer which contain nitroxide and hydroxy functions and a coded monomer, defining the bits (0 and 1), that exhibit phosphoramidite and alkyl bromide functional groups. The synthesis of digitally-encoded polymers using this simple approach will be shown in this poster presentation. Moreover, the encoded sequences can be easily analyzed by tandem mass spectrometry. Hence, sequence-coded poly(alkoxyamine phosphodiester)s represent a promising new class of information containing macromolecules.

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)




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

cooling rate (–0.25°C/min).

From these measurements we have mapped out the

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

of H-bonding in the different phases.

Fig. 1 : Optical micrographs of BHPB10/trans-

decalin (c = 10wt%) showing the transition between

biphasic liquid phases and gel fibers

Fig. 2 : c-T phase diagram of BHPB10/trans-decalin

(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




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 crosslinked particles were stable below TCP. 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.

Fig. 1 : Stabilization and degradation of nanoparticles.

.

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




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

C. LAURE1, R. KUMAR ROY1, D. SARENTI-KARAMESINI1, L. CHARLES2, J.-F. LUTZ1

1 Precision Macromolecular Chemistry, Institut Charles Sadron, CNRS UPR 22, 23 rue du Loess, 67034 Strasbourg Cedex, France

2 SACS, Laboratoire Chimie de Provence, Avenue Escadrille Normandie Niémen, 13397 Marseille Cedex 20, France

ABSTRACT: Sequence-defined synthetic polymers can be used to store digital information. In order to do so, two monomers are intentionally defined as 0 and 1 bit1

and assembled into a coded sequence through an iterative approach on a solid support.2 In the present work, sequence-coded poly(alkoxyamine-amide)s were synthesized by a chemoselective process involving two building blocks that cannot react with themselves.3 The first building blocks is a nitroxide, which is used as a spacer, whereas the other one is an anhydride used as a 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

studied. In a first approach, long sequence-coded poly(alkoxyamide amide)s (i.e. up to 19 units) were prepared by convergent synthesis.5 These polymers were obtained by stepwise ligation of oligomers containing information dyads, i.e. 00, 01, 10 and 11. In a second approach, uniform poly(alkoxyamide amide)s with different chain-lengths were physically mixed. This intentionally polydisperse mixture was analyzed by electrospray mass spectrometry and fully decoded by MS/MS using simple predefined reading rules.6

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.




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 investigations of commercially available, safe and 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

inhibition even upon irradiation with low LED light intensity.

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

2016 indo -fre nch conference - institut …...2016 indo-french conference functional polymers and...

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