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40 results on '"Emilie Moulin"'

1. Light-Driven Molecular Whirligig

Author

Chuan Gao, Andreas Vargas Jentzsch, Emilie Moulin, Nicolas Giuseppone, Institut Charles Sadron (ICS), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), and Moulin, Emilie

Subjects
[CHIM.POLY] Chemical Sciences/Polymers, Polymers, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Molecular Motor Proteins, General Chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, Biochemistry, Catalysis, [CHIM.POLY]Chemical Sciences/Polymers, Colloid and Surface Chemistry, Torque, Humans, Child, Mechanical Phenomena
Abstract

International audience; An unidirectional light-driven rotary motor was looped in a figure-of-eight molecule by linking two polymer chains between its stator and rotor parts. By properly tuning the size of these linkers, clockwise rotation of the motor under UV light was shown to create conformationally strained twists between the polymer chains and, in this tensed conformation, the energy stored in the molecular object was sufficient to trigger the reverse rotation of the motor back to its fully relaxed state. The functioning principle of this motorized molecular device appears very similar to the one of macroscopic whirligig crafts used by children for fun. In addition, we found that in its out-of-equilibrium tensed state, the fluorescence emission of the molecular motor increased by 500% due to the mechanical constraints imposed by the polymer chains on its conjugated core. Finally, by calculating the apparent thermal energies of activation for the backward rotations at different levels of twisting, we quantitatively determined a lower estimate of the work generated by this rotary motor, from which a torque and a force were extracted, thus answering a long-term open question in this field of research.

Published
2022
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3. Design of Stimuli-Responsive Dynamic Covalent Delivery Systems for Volatile Compounds (Part 2): Fragrance-Releasing Cleavable Surfactants in Functional Perfumery Applications

Author

Andreas Herrmann, Nicolas Giuseppone, Vera Tchakalova, Serge Lamboley, Emilie Moulin, Daniel Benczedi, Eric Lutz, Firmenich S.A., Institut Charles Sadron (ICS), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Moulin, Emilie, Firmenich SA, Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, and Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)

Subjects
[CHIM.POLY] Chemical Sciences/Polymers, Imine, 010402 general chemistry, 01 natural sciences, Aldehyde, Micelle, Catalysis, Surface-Active Agents, chemistry.chemical_compound, Pulmonary surfactant, [CHIM] Chemical Sciences, Amphiphile, Organic chemistry, [CHIM]Chemical Sciences, Propylene oxide, Micelles, chemistry.chemical_classification, Ethylene oxide, 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, General Chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, Perfume, 0104 chemical sciences, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Odorants, Amine gas treating, Hydrophobic and Hydrophilic Interactions
Abstract

International audience; Amphiphilic imines prepared by condensation of a hydrophobic fragrance aldehyde with a hydrophilic amine derived from a hydrophilic poly(propylene oxide) and poly(ethylene oxide) diblock copolymer were investigated as cleavable surfactant profragrances in applications of functional perfumery. In water, the cleavable surfactants assemble into micelles that allow solubilization of perfume molecules that are not covalently attached to the surfactant. Dynamic headspace analysis on a glass surface showed that solubilized perfume molecules evaporated in a similar manner in the presence of the cleavable surfactant as compared with a noncleavable reference surfactant. Under application conditions, the cleavable surfactant imine hydrolysed to release the covalently linked fragrance aldehyde. The profragrances were stable during storage in aqueous media and upon dilution showed a blooming effect for the hydrolytical fragrance release and a more balanced performance of a solubilized perfume by retaining the more volatile fragrances and boosting the evaporation of the less volatile fragrances.

Published
2021
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4. Structural properties of contractile gels based on light-driven molecular motors: a small-angle neutron and X-ray study

Author

Eric Buhler, Emilie Moulin, Giacomo Mariani, Jean-Rémy Colard-Itté, Nicolas Giuseppone, Matière et Systèmes Complexes (MSC (UMR_7057)), Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP), Institut Charles Sadron (ICS), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Moulin, Emilie, Centre National de la Recherche Scientifique (CNRS)-Université Paris Cité (UPCité), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, and Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)

Subjects
chemistry.chemical_classification, [CHIM.POLY] Chemical Sciences/Polymers, Range (particle radiation), Materials science, 010405 organic chemistry, Scattering, General Chemistry, Polymer, 010402 general chemistry, Condensed Matter Physics, Rotation, 01 natural sciences, [PHYS.COND.CM-SCM] Physics [physics]/Condensed Matter [cond-mat]/Soft Condensed Matter [cond-mat.soft], 0104 chemical sciences, Condensed Matter::Soft Condensed Matter, Quantitative Biology::Subcellular Processes, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Chemical physics, Molecular motor, Neutron, Irradiation, [PHYS.COND.CM-SCM]Physics [physics]/Condensed Matter [cond-mat]/Soft Condensed Matter [cond-mat.soft], Contraction (operator theory)
Abstract

International audience; The detailed structure of active polymer gels built by integrating light-driven rotary molecular motors as reticulation units in polymer networks is discussed as a function of gel composition. Upon light-irradiation, the collective rotation of molecular motors is translated into the macroscopic contraction of the gels through polymer chains twisting. The major role of the characteristic ratio c/c* (c* being the overlap concentration of the polymer-motor conjugates before crosslinking) on the contraction efficiency is exploited. Combined small-angle neutron and X-ray scattering experiments reveal the importance of heterogeneities in the macroscopic contraction process: the mesh size of the network increases under irradiation in the whole range of c/c*, an increase that is maximal for c/c*=1; i.e. at higher contraction efficiency. Furthermore, the mesh size of the network reaches equilibrium within a short period of time, while the heterogeneiteis increase in size untill the end of the contraction process. Finally, the significant motorized twisting of polymer chains within the network allows to foresee the design of new storage energy systems.

Published
2020
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5. Supramolecular Polymerization of Triarylamine-Based Macrocycles into Electroactive Nanotubes

Author

Shoichi Tokunaga, Andreas Vargas Jentzsch, Mounir Maaloum, Odile Gavat, Emilie Moulin, Jean-Marc Strub, Susanne Schneider, Nicolas Giuseppone, Junjun Tan, Jean-Marie Lehn, Flavio Picini, Institut Charles Sadron (ICS), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Institut de Science et d'ingénierie supramoléculaires (ISIS), Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Laboratoire de Spectrométrie de Masse BioOrganique [Strasbourg] (LSMBO), Département Sciences Analytiques et Interactions Ioniques et Biomoléculaires (DSA-IPHC), Institut Pluridisciplinaire Hubert Curien (IPHC), Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Institut Pluridisciplinaire Hubert Curien (IPHC), and Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)

Subjects
chemistry.chemical_classification, Molecular model, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Supramolecular chemistry, Stacking, General Chemistry, 010402 general chemistry, 01 natural sciences, Biochemistry, Catalysis, 0104 chemical sciences, Supramolecular polymers, chemistry.chemical_compound, Delocalized electron, Crystallography, [CHIM.POLY]Chemical Sciences/Polymers, Colloid and Surface Chemistry, chemistry, Polymerization, Amide, [CHIM]Chemical Sciences, Spectroscopy
Abstract

International audience; A S6-symmetric triarylamine-based macrocycle (i.e. hexaaza[16]para-cyclophane), decorated with six lateral amide functions, is synthesized by a convergent and modular strategy. This macrocycle is shown to undergo supramolecular polymerization in o-dichlorobenzene, and its nanotubular structure is elucidated by a combination of spectroscopy and microscopy techniques, together with X-ray scattering and molecular modelling. Upon sequential oxidation, a spectroelectrochemical analysis of the supramolecular polymer suggests an extended electronic delocalization of charge carriers both within the macrocycles (through bond) and between macrocycles along the stacking direction (through space).

Published
2021
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6. Design of Stimuli-Responsive Dynamic Covalent Delivery Systems for Volatile Compounds (Part 1): Controlled Hydrolysis of Micellar Amphiphilic Imines in Water

Author

Nicolas Giuseppone, Eric Lutz, Emilie Moulin, Andreas Herrmann, Vera Tchakalova, Daniel Benczedi, Institut Charles Sadron (ICS), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), and Firmenich S.A.

Subjects
010405 organic chemistry, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Hydrolysis, Organic Chemistry, Imine, Rational design, Dynamic covalent chemistry, Water, General Chemistry, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, Micelle, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, [CHIM.POLY]Chemical Sciences/Polymers, Covalent bond, Amphiphile, Self-assembly, Imines, Hydrophobic and Hydrophilic Interactions, Micelles
Abstract

International audience; Despite their intrinsic hydrolysable character, imine bonds can become remarkably stable in water when self-assembled in amphiphilic micellar structures. In the present article, we systematically study some of these structures and the influence of various parameters that can be used to take control over their hydrolysis, including pH, concentration, position of the imine function in the amphiphilic structure, relative lengths of the linked hydrophilic and hydrophobic moieties. Thermodynamic and kinetic data lead us to the rational design of stable imines in water, partly based on the location of the imine function within the hydrophobic part of the amphiphile and on a predictable quantitative term that we define as the total hydrophilic-lipophilic balance (HLB). In addition, we show that such stable systems are also stimuli-responsive and therefore, of potential interest in trapping and releasing micellar components on demand.

Published
2021
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7. Extraction of mechanical work from stimuli-responsive molecular systems and materials

Author

Nicolas Giuseppone, Emilie Moulin, Alexis Perrot, Moulin, Emilie, Institut Charles Sadron (ICS), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Matériaux et nanosciences d'Alsace (FMNGE), and Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)

Subjects
[CHIM.POLY] Chemical Sciences/Polymers, Work output, Computer science, 02 engineering and technology, Molecular systems, 010402 general chemistry, 01 natural sciences, [CHIM] Chemical Sciences, Molecular motor, Stimuli-responsive materials, [CHIM]Chemical Sciences, Molecular switch, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Work (physics), Soft actuators, Control engineering, Molecular motors, General Chemistry, 021001 nanoscience & nanotechnology, [CHIM.ORGA] Chemical Sciences/Organic chemistry, Molecular machine, 0104 chemical sciences, Molecular switches, [CHIM.POLY]Chemical Sciences/Polymers, Dissipative system, 0210 nano-technology, Actuator
Abstract

International audience; Molecular switches and advanced molecular motors, which are the elementary building blocks for the construction of molecular machines, have been recently integrated into soft materials in order to generate macroscopic actuation under various types of external stimulations. However, to produce a continuous work from these materials, and therefore to potentially achieve more advanced tasks, important structural and dynamic aspects should be considered at all length scales. Here we discuss the implementation of thermodynamic, photodynamic, and dissipative molecular switches and motors in such stimuli-responsive materials. We also highlight the different ratcheting strategies that can be implemented in these actuators to confer them with the capacity of achieving unidirectional cyclic motion, and in order to continuously and autonomously increase their work output.

Published
2021
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8. Homodyne dynamic light scattering in supramolecular polymer solutions: anomalous oscillations in intensity correlation function

Author

Eric Buhler, I. A. Nyrkova, Nicolas Giuseppone, Emilie Moulin, Alexander N. Semenov, Institut Charles Sadron (ICS), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Matière et Systèmes Complexes (MSC (UMR_7057)), Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP), Semenov, Alexander, Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), and Centre National de la Recherche Scientifique (CNRS)-Université Paris Cité (UPCité)

Subjects
Convection, chemistry.chemical_classification, [CHIM.POLY] Chemical Sciences/Polymers, Materials science, Scattering, Oscillation, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 01 natural sciences, Molecular physics, [PHYS.COND.CM-SCM] Physics [physics]/Condensed Matter [cond-mat]/Soft Condensed Matter [cond-mat.soft], 0104 chemical sciences, Supramolecular polymers, Correlation function (statistical mechanics), [CHIM.POLY]Chemical Sciences/Polymers, Dynamic light scattering, chemistry, Irradiation, Laser power scaling, 0210 nano-technology, [PHYS.COND.CM-SCM]Physics [physics]/Condensed Matter [cond-mat]/Soft Condensed Matter [cond-mat.soft]
Abstract

International audience; Dilute solutions of electronically active molecules capable of irradiation-driven supramolecular self-assembly are studied by dynamic light scattering. We detect unusual well-defined oscillations in the long time range of the homodyne intensity correlation function for all solutions that were irradiated with white light prior to the measurements. The oscillation effect is attributed to the local laser-induced heating of the samples due to strongly enhanced absorption manifested by the supramolecular filaments. It is found that the oscillation frequency depends on the irradiation time, solution concentration, and the incident laser power, but is independent of the scattering angle. These observations are explained with a semi-quantitative theory relating the oscillation effect to thermo-gravitational convection flows generated by laser beam. The results suggest that the presence of such homodyne oscillations could be a sensitive probe for aggregation in many complex systems.

Published
2020
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9. 3D supramolecular self-assembly of [60]fullerene hexaadducts decorated with triarylamine molecules

Author

Nicolas Giuseppone, Eric Buhler, Mounir Maaloum, Jean-François Nierengarten, Thi Minh Nguyet Trinh, Emilie Moulin, Odile Gavat, Thomas Ellis, Guillaume Fleith, Laboratoire de chimie moléculaire (LCM), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Substances naturelles/chimie moléculaire, Université Louis Pasteur - Strasbourg I-Ecole européenne de chimie, polymères et matériaux [Strasbourg]-Centre National de la Recherche Scientifique (CNRS), Institut Charles Sadron (ICS), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Animal et gestion intégrée des risques (UPR AGIRs), Centre de Coopération Internationale en Recherche Agronomique pour le Développement (Cirad), Laboratoire d'innovation moléculaire et applications (LIMA), and Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Fullerene, Materials science, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Metals and Alloys, Supramolecular chemistry, Nanowire, General Chemistry, 010402 general chemistry, Grafting, 01 natural sciences, Catalysis, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, chemistry.chemical_compound, Monomer, chemistry, Polymerization, Polymer chemistry, Materials Chemistry, Ceramics and Composites, Molecule, Self-assembly
Abstract

A clickable fullerene hexa-adduct scaffold has been functionalized with twelve triarylamine subunits. The light-triggered self-assembly of this molecular unit leads to 3D honeycomb-like structures with inner pores of around 10 nm diameter. Multiple grafting of triarylamine subunits onto a hard-core C60 unit increases the dimensionality of the self-assembly process by reticulating the 1D nanowires typically obtained from the supramolecular polymerization of triarylamine monomers.

Published
2018
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10. Bistable [c2] Daisy Chain Rotaxanes as Reversible Muscle-like Actuators in Mechanically Active Gels

Author

Nicolas Giuseppone, Gad Fuks, Antoine Goujon, Thomas Lang, Emilie Moulin, Giacomo Mariani, Eric Buhler, Jésus Raya, Institut Charles Sadron (ICS), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Matière et Systèmes Complexes (MSC (UMR_7057)), Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP), Institut de Chimie de Strasbourg, and Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
chemistry.chemical_classification, Bistability, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Nanotechnology, General Chemistry, Polymer, Neutron scattering, 010402 general chemistry, 01 natural sciences, Biochemistry, Catalysis, Molecular machine, 0104 chemical sciences, [CHIM.POLY]Chemical Sciences/Polymers, Colloid and Surface Chemistry, chemistry, Polymerization, Click chemistry, Daisy chain, Topology (chemistry)
Abstract

International audience; The implementation of molecular machines in polymer science is of high interest to transfer mechanical motions from nanoscale to macroscale in order to access new kinds of active devices and materials. Toward this objective, thermodynamic and topological aspects need to be explored for reaching efficient systems capable of producing a useful work. In this paper we describe the branched polymerization of pH-sensitive bistable [c2] daisy chain rotaxanes by using copper(I)-catalyzed Huisgen 1,3-dipolar cycloaddition (“click chemistry”). With this cross-linked topology, the corresponding materials in the form of chemical gels can be contracted and expanded over a large variation of volume (∼50%) by changing the protonation state of the system. HR-MAS 1H NMR and neutron scattering experiments reveal that this macroscopic response of the gels results from the synchronized actuation of the mechanical bonds at the molecular level.

Published
2017
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11. Columnar Self-Assemblies of Triarylamines as Scaffolds for Artificial Biomimetic Channels for Ion and for Water Transport

Author

Nicolas Giuseppone, Mihail Barboiu, Emilie Moulin, Erol Licsandru, Istvan Kocsis, Susanne Schneider, Florina Dumitru, Junjun Tan, Arnaud Gilles, Jean-Marie Lehn, Universität Leipzig [Leipzig], Institut Européen des membranes (IEM), Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM), Institut Charles Sadron (ICS), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Institut de Science et d'ingénierie supramoléculaires (ISIS), Université Louis Pasteur - Strasbourg I-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), and Collège de France (CdF (institution))

Subjects
Water transport, Chemistry, Supramolecular chemistry, KcsA potassium channel, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Biochemistry, Catalysis, Light scattering, 0104 chemical sciences, Ion, Crystallography, Colloid and Surface Chemistry, Membrane, [CHIM]Chemical Sciences, Molecule, 0210 nano-technology, Lipid bilayer, ComputingMilieux_MISCELLANEOUS
Abstract

Triarylamine molecules appended with crown-ethers or carboxylic moieties form self-assembled supramolecular channels within lipid bilayers. Fluorescence assays and voltage clamp studies reveal that the self-assemblies incorporating the crown ethers work as single channels for the selective transport of K+ or Rb+. The X-ray crystallographic structures confirm the mutual columnar self-assembly of triarylamines and crown-ethers. The dimensional fit of K+ cations within the 18-crown-6 leads to a partial dehydration and to the formation of alternating K+ cation-water wires within the channel. This original type of organization may be regarded as a biomimetic alternative of columnar K+-water wires observed for the natural KcsA channel. Supramolecular columnar arrangement was also shown for the triarylamine-carboxylic acid conjugate. In this latter case, stopped-flow light scattering analysis reveals the transport of water across lipid bilayer membranes with a relative water permeability as high as 17 μm s–1.

Published
2017
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12. Design of Collective Motions from Synthetic Molecular Switches, Rotors, and Motors

Author

Nicolas Giuseppone, Xuyang Yao, Emilie Moulin, Joakim Heiser, Alexis Perrot, Damien Dattler, Gad Fuks, Institut Charles Sadron (ICS), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Moulin, Emilie, Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, and Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Molecular switch, [CHIM.POLY] Chemical Sciences/Polymers, 010405 organic chemistry, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Collective motion, Control engineering, General Chemistry, Molecular rotors, 010402 general chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, 01 natural sciences, Active devices, 0104 chemical sciences, [CHIM.POLY]Chemical Sciences/Polymers, Actuator
Abstract

International audience; Precise control over molecular movement is of fundamental and practical importance in physics, biology, and chemistry. At nanoscale, the peculiar functioning principles and the synthesis of individual molecular actuators and machines has been the subject of intense investigations and debates over the past 60 years. In this review, we focus on the design of collective motions that are achieved by integrating, in space and time, several or many of these individual mechanical units together. In particular, we provide an in-depth look at the intermolecular couplings used to physically connect a number of artificial mechanically active molecular units such as photochromic molecular switches, nanomachines based on mechanical bonds, molecular rotors, and light-powered rotary motors. We highlight the various functioning principles that can lead to their collective motion at various length scales. We also emphasize how their synchronized, or desynchronized, mechanical behavior can lead to emerging functional properties and to their implementation into new active devices and materials

Published
2020
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13. Covalently Trapped Triarylamine‐Based Supramolecular Polymers

Author

Andreas Vargas Jentzsch, Emilie Moulin, Ting Liang, Dominique Collin, Alain Carvalho, Melodie Galerne, Gad Fuks, Mounir Maaloum, Nicolas Giuseppone, Institut Charles Sadron (ICS), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Hétérochimie Fondamentale et Appliquée (LHFA), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD), Moulin, Emilie, Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, and Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)

Subjects
[CHIM.POLY] Chemical Sciences/Polymers, Supramolecular chemistry, Stacking, macromolecular substances, 010402 general chemistry, 01 natural sciences, Catalysis, chemistry.chemical_compound, [CHIM] Chemical Sciences, [CHIM]Chemical Sciences, Ring-opening metathesis polymerisation, ComputingMilieux_MISCELLANEOUS, Norbornene, chemistry.chemical_classification, 010405 organic chemistry, Hydrogen bond, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, technology, industry, and agriculture, General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, 0104 chemical sciences, Supramolecular polymers, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Polymerization, Chemical engineering, Covalent bond
Abstract

C3 -Symmetric triarylamine trisamides (TATAs), decorated with three norbornene end groups, undergo supramolecular polymerization and further gelation by π-π stacking and hydrogen bonding of their TATA cores. By using subsequent ring-opening metathesis polymerization, these physical gels are permanently crosslinked into chemical gels. Detailed comparisons of the supramolecular stacks in solution, in the physical gel, and in the chemical gel states, are performed by optical spectroscopies, electronic spectroscopies, atomic force microscopy, electronic paramagnetic resonance spectroscopy, X-ray scattering, electronic transport measurements, and rheology. The results presented here clearly evidence that the core structure of the functional supramolecular polymers can be precisely retained during the covalent capture whereas the mechanical properties of the gels are concomitantly improved, with an increase of their storage modulus by two orders of magnitude.

Published
2019
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14. Temperature Control of Sequential Nucleation-Growth Mechanisms in Hierarchical Supramolecular Polymers

Author

Mounir Maaloum, Artem Osypenko, Wybren Jan Buma, Odile Gavat, Nicolas Giuseppone, Mark A. J. Koenis, Emilie Moulin, Gad Fuks, Molecular Spectroscopy (HIMS, FNWI), Institut Charles Sadron (ICS), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Matériaux et nanosciences d'Alsace (FMNGE), and Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)

Subjects
chemistry.chemical_classification, FELIX Condensed Matter Physics, Circular dichroism, Quantitative Biology::Biomolecules, Temperature control, 010405 organic chemistry, Molecular and Biophysics, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Nucleation growth, Organic Chemistry, Stacking, Supramolecular chemistry, General Chemistry, 010402 general chemistry, Fibril, 01 natural sciences, Catalysis, 0104 chemical sciences, Supramolecular polymers, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Chemical physics, Vibrational circular dichroism, [CHIM]Chemical Sciences, ComputingMilieux_MISCELLANEOUS
Abstract

Upon cooling insolution, chiral triarylamine tris-amide unimers produce organogels by stacking into helical supramolecular polymers, which subsequently bundle into larger fibers. Interestingly, circular dichroism, vibrational circular dichroism, and AFM imaging of the chiral self-assemblies revealed that monocolumnar P-helical fibrils formed upon fast cooling, whereas bundled M-superhelical fibers formed upon slow cooling. The mechanistic study of this structural bifurcation reveals the presence of a strong memory effect, reminiscent of a complex stepwise combination of primary and secondary nucleation-growth processes. These results highlight the instrumental role of sequential self-assembly processes to control supramolecular architectures of multiple hierarchical order.

Published
2019
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15. Triarylamine-Based Supramolecular Polymers: Structures, Dynamics, and Functions

Author

Nicolas Giuseppone, Joseph J. Armao, Emilie Moulin, Moulin, Emilie, Institut Charles Sadron (ICS), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, and Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)

Subjects
chemistry.chemical_classification, [CHIM.POLY] Chemical Sciences/Polymers, Materials science, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Hydrogen bond, Supramolecular chemistry, Nanotechnology, General Medicine, General Chemistry, Polymer, [CHIM.ORGA] Chemical Sciences/Organic chemistry, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Supramolecular polymers, chemistry.chemical_compound, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Covalent bond, Amide, Molecule, Nanorod
Abstract

International audience; Triarylamine molecules and triarylamine-based covalent polymers have been extensively investigated for more than 60 years in academics and industry because of their intriguing electronic and optical characteristics. However, despite the profusion of studies made on these derivatives, only very recently have the first examples of supramolecular polymers based on the triarylamine motif been described in the literature. Specifically, our research group has shown that, by adding supplementary hydrogen bonding moieties such as amide functions in their periphery, it becomes possible to tightly pack triarylamine molecules in columnar supramolecular stacks presenting a collinear arrangement of their central nitrogen atoms. These supramolecular polymers can self-assemble into various soft hierarchical structures such as helical fibers, nanorods, nanospheres, and nanoribbons in the sol and in the gel states, into liquid-crystalline mesophases, and into highly organized supramolecular frameworks and single crystals thereof.Interestingly, the associated supramolecular polymerization mechanism involves a nucleation step of high activation energy, which requires the flattening of the triarylamine core. Because of this singularity and although dependent on the precise chemical nature of the building blocks, it has been demonstrated that their supramolecular polymerization can be triggered by original tools, such as light irradiation or electrochemistry, and that it can display autocatalytic growth behaviors, remarkably strong amplifications of chirality, and complex and competing thermodynamic and kinetic self-assembly pathways.Further, from a functional point of view, it has been highlighted that a partial oxidation of the triarylamine molecules results in an enhanced through-space delocalization of the charge carriers along the π–π stacked supramolecular polymers, a feature that confers to these nanowires exceptional transport properties. Upon increasing the charge carrier concentration, the electronic nature of these soft materials can be switched from semiconducting to metallic behavior, and the presence of highly delocalized unpaired electrons in supramolecular polaronic band structures has been further exploited to implement plasmonic properties within subwavelength organic interconnects and microscopic optical waveguides.Finally, by making use of the unusual dynamics and functions of triarylamine-based nanostructures, it becomes possible to precisely address their self-construction within confined environments or within nano- and micrometer scale devices. This has been demonstrated for instance between nanoparticles and between electrodes, inside inorganic nanopores, and inside phospholipid bilayers, as well as at the liquid–liquid interface. Such a meeting point between bottom-up and top-down technologies is of high interest to envision further developments and applications for this entirely new class of supramolecular polymers, which combine a unique relationship between their structures, their dynamics, and their subsequent emerging functional properties.

Published
2019
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16. [c2]Daisy Chain Rotaxanes as Molecular Muscles

Author

Nicolas Giuseppone, Gad Fuks, Antoine Goujon, and Emilie Moulin

Subjects
010405 organic chemistry, Chemistry, Biophysics, Supramolecular chemistry, General Chemistry, 010402 general chemistry, Daisy chain, 01 natural sciences, Molecular machine, 0104 chemical sciences
Abstract

Bistable [ c2]daisy chain rotaxanes represent a particularly intriguing class of interlocked molecules that can produce internal sliding movements with a net contraction or extension at the single-molecule level. These nanometric motions show some analogies with the sliding motions of actin and myosin filaments in sarcomeres, and this is why [ c2]daisy chain rotaxanes have been also named as “molecular muscles,” as their first synthesis in 2000. In this minireview, the authors discuss the recent history of these molecules, their modular chemical structures, and the various synthetic pathways described in the literature to access them. The authors also detail how their internal motions can be controlled and characterized by a number of chemical and physical tools. The authors finally show that their integration within polymers and materials can give access to synchronized motions and amplifications up to the macroscopic scale. Overall, the numerous examples that have been described in the literature to date demonstrate that this family of molecules has already strongly influenced the entire field of research on artificial molecular machines, and has the potential to be implemented as actuators working at all scales, from nanometric-switchable devices to mechanically active soft matter materials.

Published
2019
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17. Supramolecular Electropolymerization

Author

Thomas K. Ellis, Melodie Galerne, Joseph J. Armao, Artem Osypenko, David Martel, Mounir Maaloum, Gad Fuks, Odile Gavat, Emilie Moulin, Nicolas Giuseppone, Institut Charles Sadron (ICS), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), and Martel, David

Subjects
[CHIM.POLY] Chemical Sciences/Polymers, [CHIM.POLY]Chemical Sciences/Polymers, [CHIM]Chemical Sciences, General Chemistry, 02 engineering and technology, General Medicine, 010402 general chemistry, 021001 nanoscience & nanotechnology, 0210 nano-technology, 01 natural sciences, Catalysis, ComputingMilieux_MISCELLANEOUS, 0104 chemical sciences
Abstract

International audience; Gaining control over supramolecular polymerization mechanisms is of high fundamental interest to understand self-assembly and self-organization processes at the nanoscale. It is also expected to significantly impact the design and improve the efficiency of advanced materials and devices. Up to now, supramolecular polymerization has been shown to take place from unimers in solution, mainly by variations of temperature or of concentration. Reported here is that supramolecular nucleation-growth of triarylamine monomers can be triggered by electrochemistry in various solvents. The involved mechanism offers new opportunities to precisely address in space and time the nucleation of supramolecular polymers at an electrode. To illustrate the potential of this methodology, supramolecular nanowires are grown an oriented over several tens of micrometers between different types of commercially available electrodes submitted to a single DC electric field, reaching a precision unprecedented in the literature.

Published
2018
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18. Self-assembly of benzene-tris(bis(p-benzyloxy)triphenylamine)carboxamide

Author

Nicolas Giuseppone, Artem Osypenko, Mounir Maaloum, Yuya Domoto, Eric Busseron, Thomas Ellis, and Emilie Moulin

Subjects
Materials science, Chemistry(all), medicine.drug_class, General Chemical Engineering, Supramolecular chemistry, Carboxamide, 02 engineering and technology, 010402 general chemistry, Photochemistry, Triphenylamine, 01 natural sciences, chemistry.chemical_compound, Dendrimer, medicine, Benzene, Triarylamine, Supramolecular fibers, Self-assembly, General Chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, chemistry, Benzenetricarboxamide, Chemical Engineering(all), 0210 nano-technology, Derivative (chemistry), Visible spectrum
Abstract

A dendritic unit based on a benzenetricarboxamide core and three triarylamine arms has been synthesized and characterized. Self-assembled micrometric crystalline fibers can be formed in various organic solvents. This derivative has also been studied in chlorinated solvents upon visible light stimulation, giving rise to self-assembled fibers with triarylammonium cations trapped in their supramolecular structure. Overall, this work enlarges the scope of chemical modifications that can be made on triarylamine cores to produce doped supramolecular architectures with potential interests for optoelectronic materials.

Published
2016
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19. Hierarchical Self-Assembly of Supramolecular Muscle-Like Fibers

Author

Eric Buhler, Nicolas Giuseppone, Guangyan Du, Mounir Maaloum, Gad Fuks, Antoine Goujon, and Emilie Moulin

Subjects
chemistry.chemical_classification, Mesoscopic physics, Materials science, Rotaxane, 010405 organic chemistry, Polymers, Proton Magnetic Resonance Spectroscopy, Supramolecular chemistry, Nanotechnology, General Chemistry, General Medicine, 010402 general chemistry, 01 natural sciences, Catalysis, Molecular machine, 0104 chemical sciences, Supramolecular polymers, symbols.namesake, chemistry, Microscopy, Electron, Transmission, symbols, Self-assembly, van der Waals force, Daisy chain, Muscle, Skeletal
Abstract

An acid-base switchable [c2]daisy chain rotaxane terminated with two 2,6-diacetylamino pyridine units has been self-assembled with a bis(uracil) linker. The complementary hydrogen-bond recognition patterns, together with lateral van der Waals aggregations, result in the hierarchical formation of unidimensional supramolecular polymers associated in bundles of muscle-like fibers. Microscopic and scattering techniques reveal that the mesoscopic structure of these bundles depends on the extended or contracted states that the rotaxanes show within individual polymer chains. The observed local dynamics span over several length scales because of a combination of supramolecular and mechanical bonds. This work illustrates the possibility to modify the hierarchical mesoscopic structuring of large polymeric systems by the integrated actuation of individual molecular machines.

Published
2015
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20. pH and light-controlled self-assembly of bistable [c2] daisy chain rotaxanes

Author

Emilie Moulin, Juan-José Cid, Adrian Wolf, Guangyan Du, Nicolas Giuseppone, Gad Fuks, Antoine Goujon, and Eric Busseron

Subjects
Rotaxane, Bistability, Chemistry, business.industry, Metals and Alloys, Supramolecular chemistry, General Chemistry, Photochemistry, Catalysis, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Logic gate, Materials Chemistry, Ceramics and Composites, Optoelectronics, Self-assembly, Daisy chain, business, Dual color
Abstract

A logic gate based on a bistable [c2] daisy chain rotaxane decorated with lateral triarylamine units is described, giving rise to an INHIBIT logic function using proton concentration and light as inputs, and producing dual color change and supramolecular self-assembly as outputs.

Published
2015
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21. Controlled Sol-Gel Transitions by Actuating Molecular Machine Based Supramolecular Polymers

Author

Emilie Moulin, Eric Buhler, Michel Rawiso, Nicolas Giuseppone, Antoine Goujon, Thomas Lang, Giacomo Mariani, Institut Charles Sadron (ICS), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Matière et Systèmes Complexes (MSC (UMR_7057)), and Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP)

Subjects
chemistry.chemical_classification, Rotaxane, Bistability, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Supramolecular chemistry, Nanotechnology, 02 engineering and technology, General Chemistry, Polymer, 010402 general chemistry, 021001 nanoscience & nanotechnology, Smart material, 01 natural sciences, Biochemistry, Catalysis, Molecular machine, 0104 chemical sciences, Supramolecular polymers, [CHIM.POLY]Chemical Sciences/Polymers, Colloid and Surface Chemistry, chemistry, 0210 nano-technology, Daisy chain
Abstract

International audience; The implementation of artificial molecular machines in polymer science is an important objective that challenges chemists and physicists in order to access an entirely new class of smart materials. To design such systems, the amplification of a mechanical actuation from the nanoscale up to a macroscopic response in the bulk material is a central issue. In this article we show that bistable [c2]daisy chain rotaxanes (i.e. molecular muscles) can be linked into mainchain Upy-based supramolecular polymers. We then reveal by an in depth quantitative study that the pH actuation of the mechanically active rotaxane at the nanoscale influences the physical reticulation of the polymer chains by changing the supramolecular behavior of the Upy units. This nano-actuation within the local structure of the main chain polymer results in a mechanically controlled sol-gel transition at the macroscopic level.

Published
2017
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22. Control over Nanostructures and Associated Mesomorphic Properties of Doped Self-Assembled Triarylamine Liquid Crystals

Author

Mounir Maaloum, Emilie Moulin, Nicolas Giuseppone, Yuya Domoto, and Eric Busseron

Subjects
Chemistry, Organic Chemistry, Supramolecular chemistry, Nanotechnology, General Chemistry, Triphenylamine, Catalysis, Crystallography, chemistry.chemical_compound, Differential scanning calorimetry, Liquid crystal, Molecule, Lamellar structure, Self-assembly, Spectroscopy
Abstract

We have synthesized a series of triarylamine-cored molecules equipped with an adjacent amide moiety and dendritic peripheral tails in a variety of modes. We show by (1) H NMR and UV/Vis spectroscopy that their supramolecular self-assembly can be promoted in solution upon light stimulation and radical initiation. In addition, we have probed their molecular arrangements and mesomorphic properties in the bulk by integrated studies on their film state by using differential scanning calorimetry (DSC), variable-temperature polarizing optical microscopy (VT-POM), variable-temperature X-ray diffraction (VT-XRD), and atomic force microscopy (AFM). Differences in the number and the disposition of the peripheral tails significantly affect their mesomorphic properties associated with their lamellar- or columnar-packed nanostructures, which are based on segregated stacks of the triphenylamine cores and the lipophilic/lipophobic periphery. Such structural tuning is of interest for implementation of these soft self-assemblies as electroactive materials from solution to mesophases.

Published
2014
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23. Experimental and theoretical methods for the analyses of dynamic combinatorial libraries

Author

Maria Cristina Misuraca, Yves Ruff, Emilie Moulin, and Nicolas Giuseppone

Subjects
Materials science, Theoretical methods, Materials Chemistry, General Chemistry, Biochemical engineering, Combinatorial chemistry, Data treatment, Catalysis, Selection (genetic algorithm)
Abstract

Because of their recent interest towards dynamic combinatorial systems, chemists have to challenge their capacity to analyse complex mixtures of components exchanging their molecular fragments over time. Here we present, by a selection of practical examples from the literature, how chromatographic, spectroscopic, and microscopic techniques, as well as theoretical modelling and statistical data treatment, are instrumental in this new research area which is of significance at the interfaces with molecular biology and materials science.

Published
2014
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24. Anisotropic Self-Assembly of Supramolecular Polymers and Plasmonic Nanoparticles at the Liquid-Liquid Interface

Author

Raul Arenal, Alexander N. Semenov, Joseph J. Armao, Nicolas Giuseppone, I. A. Nyrkova, Gad Fuks, Emilie Moulin, Odile Gavat, Mounir Maaloum, and Artem Osypenko

Subjects
chemistry.chemical_classification, Plasmonic nanoparticles, Supramolecular chemistry, Nanoparticle, Nanotechnology, 02 engineering and technology, General Chemistry, Polymer, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Biochemistry, Catalysis, Article, 0104 chemical sciences, Supramolecular polymers, Colloid and Surface Chemistry, Polymerization, chemistry, Liquid crystal, Self-assembly, 0210 nano-technology
Abstract

The study of supramolecular polymers in the bulk, in diluted solution, and at the solid–liquid interface has recently become a major topic of interest, going from fundamental aspects to applications in materials science. However, examples of supramolecular polymers at the liquid–liquid interface are mostly unexplored. Here, we describe the supramolecular polymerization of triarylamine molecules and their light-triggered organization at a chloroform–water interface. The resulting interfacial nematic layer of these 1D supramolecular polymers is further used as a template for the precise alignment of spherical gold nanoparticles coming from the water phase. These hybrid thin films are spontaneously formed in a single process, without chemical prefunctionalization of the metallic nanoparticles, and their ordering is improved by centrifugation. The resulting polymer chains and strings of nanoparticles can be co-aligned with high anisotropy over very large distances. By using a combination of experimental and theoretical investigations, we decipher the full sequence of this oriented self-assembly process. In such a highly anisotropic configuration, electron energy loss spectroscopy reveals that the self-assembled nanoparticles behave as plasmonic waveguides.

Published
2017

25. Long-Range Energy Transport via Plasmonic Propagation in a Supramolecular Organic Waveguide

Author

Pierre Rabu, Nicolas Giuseppone, Joseph J. Armao, and Emilie Moulin

Subjects
Materials science, Exciton, Nanophotonics, Physics::Optics, Bioengineering, 02 engineering and technology, 010402 general chemistry, 7. Clean energy, 01 natural sciences, law.invention, Delocalized electron, law, General Materials Science, Plasmon, Range (particle radiation), business.industry, Mechanical Engineering, General Chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, Ray, 0104 chemical sciences, Excited state, Optoelectronics, 0210 nano-technology, business, Waveguide
Abstract

Energy transport in organic materials is dependent on the coherent migration of optically induced excited states. For instance, in active organic waveguides, the tight packing of dye molecules allows delocalization of excitons over a distance generally limited to at most several hundred nanometers. Here, we demonstrate an alternative mechanism of energy transport in a triarylamine-based supramolecular organic waveguide that is plasmonic in nature and results in coherent energy propagation superior to 10 μm. The optical, electric, and magnetic properties of the doped material support the presence of metallic electrons that couple with and transport incident light. These results show that organic metals constitute a novel class of materials with efficient energy transport and are of potential interest for optoelectronics, plasmonics, and artificial light-energy harvesting systems.

Published
2016

26. Dynamic combinatorial chemistry as a tool for the design of functional materials and devices

Author

Nicolas Giuseppone, Gabriela Cormos, and Emilie Moulin

Subjects
010405 organic chemistry, business.industry, Computer science, Information processing, Nanotechnology, General Chemistry, Modular design, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Variety (cybernetics), Key (cryptography), Dynamic combinatorial chemistry, Biochemical engineering, Sensitivity (control systems), business
Abstract

This tutorial review presents emerging lines of investigations directed towards the development of dynamic combinatorial materials and devices. These can be defined as multi-component chemical systems which, thanks to the reversibility of their interconnections within networks of competing reactions, and thanks to their sensitivity to environmental parameters, aim at performing modular functional tasks by responding to external stimuli. The behaviour of such dynamic materials is by essence more complex than the one produced by their static or single-component counterparts and as such, they hold higher potentialities in terms of information processing and functionality tuning. Key examples are selected here to illustrate the variety of their chemical nature and physical properties which can be implemented for the fabrication of devices as diverse as sensors, ion channels, self-healable materials, mesophases for the controlled release of bioactive compounds, or dynamic functional nanostructures.

Published
2012
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27. Total Synthesis and Biological Evaluation of the Cytotoxic Resin Glycosides Ipomoeassin A-F and Analogues

Author

Guillaume Chollet, Volker Hickmann, Jennifer Herrmann, Saskia Schulthoff, Takashi Nagano, Emilie Moulin, Alois Fürstner, Rolf Müller, and Jiří Pospíšil

Subjects
Stereochemistry, Sulfonium, Organic Chemistry, Molecular Conformation, Substituent, Total synthesis, Antineoplastic Agents, Stereoisomerism, General Chemistry, Crystallography, X-Ray, Metathesis, Ruthenium, Catalysis, Cinnamic acid, Acylation, chemistry.chemical_compound, chemistry, Cell Line, Tumor, Humans, Protecting group, Glycoconjugates, Cycloalkene
Abstract

A multitasking C-silylation strategy using the readily available compound 26 as a surrogate for cinnamic acid represents the key design element of a total synthesis of all known members of the ipomoeassin family of resin glyosides. This protecting group maneuver allows the unsaturated acids decorating the glucose subunit of the targets to be attached at an early phase of the synthesis, prevents their participation in the ruthenium-catalyzed ring-closing metathesis (RCM) used to form the macrocyclic ring, and protects them against reduction during the hydrogenation of the resulting cycloalkene over Wilkinson's catalyst. As the C-silyl group can be concomitantly removed with the O-TBS substituent using tris(dimethylamino)sulfonium difluorotrimethylsilicate (TASF) in acetonitrile, no separate protecting group manipulations were necessary in the final stages, thus contributing to a favorable overall "economy of steps". In addition to the naturally occurring ipomoeassins, a small set of synthetic analogues has also been prepared by "diverted total synthesis". The cytotoxicity of these compounds was assayed with two different cancer cell lines. The recorded data confirm previous findings that the acylation- and oxygenation pattern of these amphiphilic glycoconjugates is highly correlated with their biological activity profile. Ipomoeassin F turned out to be the most promising member of the series, showing IC(50) values in the low nanomolar range.

Published
2009
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28. Total Synthesis of Iejimalide A−D and Assessment of the Remarkable Actin-Depolymerizing Capacity of These Polyene Macrolides

Author

Alois Fürstner, Mario Waser, Carine Chevrier, Oliver Müller, Christophe Aïssa, Filip Teplý, Cristina Nevado, Martin R. Tremblay, and Emilie Moulin

Subjects
Double bond, Polymers, Stereochemistry, Acylation, Polyenes, Metathesis, Biochemistry, Catalysis, Lactones, Mice, chemistry.chemical_compound, Colloid and Surface Chemistry, Animals, Actin, chemistry.chemical_classification, Caspase 3, Chemistry, Total synthesis, General Chemistry, Polyene, Actins, Up-Regulation, Stille reaction, NIH 3T3 Cells, Indicators and Reagents, Carbamates, Macrolides
Abstract

A concise and convergent total synthesis of the highly cytotoxic marine natural products iejimalide A-D (1-4) is reported, which relies on an effective ring-closing metathesis (RCM) reaction of a cyclization precursor containing no less than 10 double bonds. Because of the exceptional sensitivity of this polyunsaturated intermediate and its immediate precursors toward acid, base, and even gentle warming, the assembly process hinged upon the judicious choice of protecting groups and the careful optimization of all individual transformations. As a consequence, particularly mild protocols for Stille as well as Suzuki reactions of elaborate coupling partners have been developed that hold considerable promise for applications in other complex settings. Moreover, a series of non-natural "iejimalide-like" compounds has been prepared, differing from the natural lead in the polar head groups linked to the macrolide's N-terminus. With the aid of these compounds it was possible to uncover the hitherto unknown effect of iejimalide and analogues on the actin cytoskeleton. Their capacity to depolymerize this microfilament network rivals that of the latrunculins which constitute the standard in the field. Structural modifications of the peptidic terminus in 2 are thereby well accommodated, without compromising the biological effects. The iejimalides hence constitute an important new class of probe molecules for chemical biology in addition to their role as promising lead structures for the development of novel anticancer agents.

Published
2007
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29. Diversity-Oriented Synthesis of Pochonins and Biological Evaluation against a Panel of Kinases

Author

Emilie Moulin, Sofia Barluenga, Nicolas Winssinger, and Frank Totzke

Subjects
ATPase, Catalysis, Lactones, Structure-Activity Relationship, chemistry.chemical_compound, pochonin, kinase inhibitors, Enzyme Inhibitors, Biological evaluation, Adenosine Triphosphatases, biology, Kinase, Phosphotransferases, Organic Chemistry, Bergerat fold, Resorcinols, General Medicine, General Chemistry, organic synthesis, chemistry, Biochemistry, Drug Design, biology.protein, Organic synthesis, Macrolides, combinatorial chemistry
Abstract

Pochonins A-F were recently characterized as six new members of the naturally occurring family of 14-membered resorcylic acid lactones. As there are a high number of ATPase and kinase inhibitors among natural resorcylic lactones, a library based on the pochonin scaffold, with five points of diversity, was prepared which includes diversity beyond that of the natural analogues. The library was synthesized by using solid-supported reagents amenable to automation. Testing the library for its inhibition against a panel of 24 kinases at 10 microM afforded a14 % hit rate. These results demonstrate the potential of the resorcylides towards the inhibition of therapeutically relevant kinases.

Published
2006
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30. Solution- and Solid-Phase Synthesis of Radicicol (Monorden) and Pochonin C

Author

Pilar Lopez, Sofia Barluenga, Nicolas Winssinger, and Emilie Moulin

Subjects
Spectrometry, Mass, Electrospray Ionization, Magnetic Resonance Spectroscopy, solid-phase synthesis, natural products, Organic Chemistry, Total synthesis, Pochonin C, General Chemistry, Metathesis, Combinatorial chemistry, Catalysis, Radicicol, Lactones, chemistry.chemical_compound, Solid-phase synthesis, chemistry, Reagent, Macrolides, metathesis, total synthesis, Spectroscopy, Two-dimensional nuclear magnetic resonance spectroscopy
Abstract

A modular synthesis for pochonin C and radicicol is reported. The two natural products were prepared in seven and eight steps, respectively, from three readily available fragments. Alternative syntheses of these compounds were achieved using a combination of polymer-bound reagents and solid phase reactions. The conformation of the two natural products was studied and compared by using 2D NMR spectroscopy.

Published
2005
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31. Modular Asymmetric Synthesis of Pochonin C

Author

Sofia Barluenga, Emilie Moulin, Nicolas Winssinger, and Pilar Lopez

Subjects
natural products, Stereochemistry, asymmetric synthesis, Pochonin C, Nanotechnology, Metathesis, Antiviral Agents, Catalysis, Lactones, chemistry.chemical_compound, conformation analysis, total synthesis, Protecting group, business.industry, Enantioselective synthesis, Center (category theory), Total synthesis, Stereoisomerism, General Medicine, General Chemistry, Modular design, Radicicol, chemistry, metathesis, Macrolides, business
Abstract

Back to its origins: Pochonin C was synthesized in 11 steps from the four fragments shown in the scheme. This asymmetric synthesis and the conversion of pochonin C into radicicol defines the configuration at the center bearing the chlorine atom as S. Ipc=isopenocampheyl, PG=protecting group.

Published
2004
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32. Healable supramolecular polymers as organic metals

Author

Gad Fuks, Michel Rawiso, Mounir Maaloum, Joseph J. Armao, Nicolas Giuseppone, Thomas Ellis, and Emilie Moulin

Subjects
chemistry.chemical_classification, Organic electronics, Nanowire, Supramolecular chemistry, Nanotechnology, 02 engineering and technology, General Chemistry, Polymer, Conjugated system, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Biochemistry, Catalysis, 0104 chemical sciences, Supramolecular polymers, Crystallinity, Delocalized electron, Colloid and Surface Chemistry, chemistry, 0210 nano-technology
Abstract

Organic materials exhibiting metallic behavior are promising for numerous applications ranging from printed nanocircuits to large area electronics. However, the optimization of electronic conduction in organic metals such as charge-transfer salts or doped conjugated polymers requires high crystallinity, which is detrimental to their processability. To overcome this problem, the combination of the electronic properties of metal-like materials with the mechanical properties of soft self-assembled systems is attractive but necessitates the absence of structural defects in a regular lattice. Here we describe a one-dimensional supramolecular polymer in which photoinduced through-space charge-transfer complexes lead to highly coherent domains with delocalized electronic states displaying metallic behavior. We also reveal that diffusion of supramolecular polarons in the nanowires repairs structural defects thereby improving their conduction. The ability to access metallic properties from mendable self-assemblies extends the current understanding of both fields and opens a wide range of processing techniques for applications in organic electronics.

Published
2014

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

Author

Nicolas Giuseppone, Eric Buhler, Emilie Moulin, Guangyan Du, Nicolas Jouault, Institut Charles Sadron (ICS), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Matière et Systèmes Complexes (MSC (UMR_7057)), Centre National de la Recherche Scientifique (CNRS)-Université Paris Cité (UPCité), and Moulin, Emilie

Subjects
[CHIM.POLY] Chemical Sciences/Polymers, Rotaxane, Materials science, genetic structures, Supramolecular chemistry, macromolecular substances, 010402 general chemistry, 01 natural sciences, Catalysis, Polymer chemistry, [CHIM] Chemical Sciences, [CHIM]Chemical Sciences, ComputingMilieux_MISCELLANEOUS, chemistry.chemical_classification, 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Zinc ion, General Medicine, General Chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, Molecular machine, 0104 chemical sciences, Supramolecular polymers, [CHIM.POLY]Chemical Sciences/Polymers, Polymerization, chemistry, Chemical physics
Abstract

Pumping iron: Double-threaded rotaxanes can be linked to coordination units and polymerized in the presence of iron or zinc ions. pH modulation triggers cooperative contractions (or extensions) of the individual rotaxanes, thus resulting in an amplified motion of the muscle-like supramolecular chains with changes of their contour lengths of several micrometers (see picture).

Published
2012
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34. Light-triggered self-construction of supramolecular organic nanowires as metallic interconnects

Author

Mounir Maaloum, Emilie Moulin, Frédéric Niess, Bernard Doudin, Jean Baptiste Beaufrand, Nicolas Giuseppone, Silvia Zanettini, Vina Faramarzi, Jean-Francois Dayen, Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Sadron (ICS), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, and Moulin, Emilie

Subjects
Solid-state chemistry, Light, Polymers, General Chemical Engineering, Inorganic chemistry, Nanowire, Carbon nanotube, Conductivity, Microscopy, Atomic Force, law.invention, Electricity, law, Electric field, chemistry.chemical_classification, [CHIM.MATE] Chemical Sciences/Material chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, business.industry, Chemistry, Nanowires, Doping, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, Semiconductor device, Polymer, [CHIM.ORGA] Chemical Sciences/Organic chemistry, Metals, Optoelectronics, business
Abstract

International audience; The construction of soft and processable organic material able to display metallic conduction properties—a large density of freely moving charges—is a major challenge for electronics. Films of doped conjugated polymers are widely used as semiconductor devices, but metallic-type transport in the bulk of such materials remains extremely rare. On the other hand, single-walled carbon nanotubes can exhibit remarkably low contact resistances with related large currents, but are intrinsically very difficult to isolate and process. Here, we describe the self-assembly of supramolecular organic nanowires between two metallic electrodes, from a solution of triarylamine derivative, under the simultaneous action of light and electric field triggers. They exhibit a combination of large conductivity values (>5 × 103 S m−1) and a low interface resistance (

Published
2011
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35. Gram-scale synthesis of iejimalide B

Author

Alois Fürstner, Emilie Moulin, and Julien Gagnepain

Subjects
Macrocyclic Compounds, Molecular Structure, Chemistry, Stereochemistry, Organic Chemistry, Enantioselective synthesis, Total synthesis, Stereoisomerism, General Chemistry, Polyenes, Polyene, Transfer hydrogenation, Catalysis, Stille reaction, Grubbs' catalyst, chemistry.chemical_compound, Suzuki reaction, Cyclization, Cell Line, Tumor, Salt metathesis reaction, Humans, Carbamates, Macrolides
Abstract

Iejimalide B (2) is the most promising member of a small family of marine polyene macrolides endowed with remarkably selective activity against human cancer cell lines. As this product, however, is hardly available from the natural sources, a detailed evaluation requires the development of an efficient and practical synthetic approach. This challenge has now been met by adapting the first total synthesis of 2 previously reported by our group to the needs of high material throughput. Redesigning the access routes to the five required building blocks in combination with a careful optimization of the fragment coupling processes provided gram amounts of this valuable compound in a sequence of no more than 16 linear steps with an overall yield of about 7%. Key elements of the successful strategy include: i) three hydrostannylation processes of elaborate terminal alkynes with "lower order" stannyl cuprates, ii) a Brown allylation, a Noyori transfer hydrogenation, and a Marshall propargylation to set the chiral centers at C9, C17, C22 and C23, and iii) a modified Takai-Utimoto olefination for the preparation of the very labile skipped 1,4-diene flanking the ester group. The assembly process benefited from a particularly mild protocol for the Stille cross-coupling previously developed in this laboratory, which clearly outperformed the alternative Suzuki reaction in terms of yield and scalability. The 24-membered macrocyclic frame was forged by a remarkably selective ring-closing metathesis reaction (RCM), in which two out of the ten double bonds present in the cyclization precursor were selectively activated with the aid of a second-generation Grubbs catalyst.

Published
2011

36. Molecular editing and assessment of the cytotoxic properties of iejimalide and progeny

Author

Armin Maier, Julien Gagnepain, Emilie Moulin, Alois Fürstner, Mario Waser, Cristina Nevado, Heinz-Herbert Fiebig, and Gerhard Kelter

Subjects
Male, Models, Molecular, Stereochemistry, Antineoplastic Agents, Apoptosis, Catalysis, Prostate cancer, chemistry.chemical_compound, Inhibitory Concentration 50, Mice, In vivo, Cell Line, Tumor, medicine, Cytotoxic T cell, Animals, Humans, Cytotoxicity, Biological Products, Molecular Structure, Organic Chemistry, Prostatic Neoplasms, General Chemistry, medicine.disease, In vitro, chemistry, Cell culture, Cancer research, Carbamates, Macrolides, Lead compound, Ex vivo
Abstract

Systematic variation of all substructures embedded into the framework of iejimalide B (2) led to a panel of synthetic analogues of this polyunsaturated macrolide, featuring structural modifications that are not accessible by derivatization of the natural lead compound itself. The assessment of the cytotoxicity of these compounds with the aid of a monolayer proliferation assay (12 human tumor cell lines in vitro) as well as a colony formation assay (24 human tumor xenografts ex vivo) revealed the exceptional potency of 2 and several of its synthetic congeners, with IC(50) values in the picomolar range for the most sensitive cell lines. Whereas structural modifications of the macrocycle or of the side chain generally lead to a decrease in activity, changes of the peptidic terminus are not only well accommodated but engender increased tumor selectivity as well. 2 and two of the most promising analogues were selected for in vivo studies in mice, in which their activity against human tumor xenografts of breast cancer (MAXF 401) and prostate cancer (PRXF PC-3M) was tested. In contrast to a previous report in the literature however, which had claimed in vivo activity for the parent iejimalides, these tests did not show a significant therapeutic effect against the chosen solid tumors upon intraperitoneal administration.

Published
2011

37. The Hierarchical Self-Assembly of Charge Nanocarriers: A Highly Cooperative Process Promoted by Visible Light

Author

Emilie Moulin, I. A. Nyrkova, Mounir Maaloum, Eric Buhler, Nicolas Giuseppone, Frédéric Niess, Institut Charles Sadron (ICS), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Matière et Systèmes Complexes (MSC (UMR_7057)), Centre National de la Recherche Scientifique (CNRS)-Université Paris Diderot - Paris 7 (UPD7), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et nanosciences d'Alsace, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), and Université Paris Diderot - Paris 7 (UPD7)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Nanostructure, Quenching (fluorescence), Chemistry, 010405 organic chemistry, Supramolecular chemistry, Cationic polymerization, Nanotechnology, 02 engineering and technology, General Chemistry, General Medicine, 021001 nanoscience & nanotechnology, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, Molecular wire, Self-assembly, Nanocarriers, 0210 nano-technology, [PHYS.COND.CM-SCM]Physics [physics]/Condensed Matter [cond-mat]/Soft Condensed Matter [cond-mat.soft], Visible spectrum
Abstract

International audience; Let there be more light: Triarylamine-based building blocks respond to visible-light exposure by the formation of cationic radicals that hierarchically self-assemble into molecular wires, which in turn combine within larger fibers (see picture). The stimuli-responsive supramolecular scaffold, which is created by charge transfer and reversibly broken up by heating, prevents the quenching of holes within the wires.

Published
2010
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38. Resorcylic acid lactones: A pluripotent scaffold with therapeutic potential

Author

Pierre-Yves Dakas, Mehdi Boulifa, Sofia Barluenga, Emilie Moulin, and Nicolas Winssinger

Subjects
chemistry.chemical_classification, Scaffold, animal structures, biology, Solid-phase synthesis, Kinase, General Chemical Engineering, Natural compound, Total synthesis, Combinatorial synthesis, General Chemistry, chemistry, Biochemistry, Kinase inhibitors, Mitogen-activated protein kinase, biology.protein, polycyclic compounds, Resorcylic acid lactones (RALs), HSP90, Signal transduction, Polymer supported reagents, Lactone
Abstract

The recent discoveries of potent HSP90 and MAP kinase inhibitors amongst the resorcylic acid lactones (RALs) have revived interest in this family of natural products. Both HSP90 and MAP kinase inhibition hold tremendous therapeutic potential, particularly in the treatment of cancer. Our synthetic efforts towards the RALs and, in particular, selective inhibitors of HSP90 and kinases are reviewed.

Published
2008

39. Design, synthesis, and biological evaluation of HSP90 inhibitors based on conformational analysis of radicicol and its analogues

Author

Sofia Barluenga, Vincent Zoete, Martin Karplus, Emilie Moulin, and Nicolas Winssinger

Subjects
Models, Molecular, biology, Stereochemistry, Chemistry, Molecular Conformation, General Chemistry, Secondary metabolite, Biochemistry, Cocrystal, Hsp90, Catalysis, Hsp90 inhibitor, Radicicol, chemistry.chemical_compound, Molecular dynamics, Lactones, Colloid and Surface Chemistry, Heat shock protein, Drug Design, medicine, biology.protein, HSP90 Heat-Shock Proteins, Macrolides, Conformational isomerism, medicine.drug
Abstract

The molecular chaperone HSP90 is an attractive target for chemotherapy because its activity is required for the functional maturation of a number of oncogenes. Among the known inhibitors, radicicol, a 14-member macrolide, stands out as the most potent. A molecular dynamics/minimization of radicicol showed that there were three low energy conformers of the macrocycle. The lowest of these is the bioactive conformation observed in the cocrystal structure of radicicol with HSP90. Corresponding conformational analyses of several known analogues gave a good correlation between the bioactivity and the energy of the bioactive conformer, relative to other conformers. Based on this observation, a number of proposed analogues were analyzed for their propensity to adopt the bioactive conformation prior to synthesis. This led to the identification of pochonin D, a recently isolated secondary metabolite of Pochonia chlamydosporia, as a potential inhibitor of HSP90. Pochonin D was synthesized using polymer-bound reagents and shown to be nearly as potent an HSP90 inhibitor as radicicol.

Published
2005

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