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1. Crystal Engineering of Conglomerates: Dilution of Racemate-Forming Fe(II) and Ni(II) Congeners into Conglomerate-Forming [Zn(bpy)3](PF6)2

Author

Ugo Serdan, Lucas Robin, Mathieu Marchivie, Mathieu Gonidec, Patrick Rosa, Elen Duverger-Nédellec, Emilie Pouget, Philippe Sainctavit, Marie-Anne Arrio, Amélie Juhin, Andrei Rogalev, Fabrice Wilhelm, and Elizabeth A. Hillard

Subjects
crystal engineering, chirality, conglomerate, molecular alloy, PXRD, Chemistry, QD1-999
Abstract

Conglomerate formation, where enantiomers within a racemic mixture self-segregate upon crystallization, is an advantageous property for obtaining chirally pure crystals and allows large-scale chiral resolution. However, the prevalence of conglomerates is low and difficult to predict. In this report, we describe our attempts to engineer conglomerates from racemate-forming compounds by integrating them into a conglomerate-forming matrix. In this regard, we found that Ni(II) and Fe(II) form molecular alloys with Zn(II) in [MxZn(1−x)(bpy)3](PF6)2 (where bpy = 2,2′-bipyridyl). Powder X-ray Diffraction (PXRD) and Energy-Dispersive X-ray spectroscopy (EDX) evidenced conglomerate crystallization with Ni(II) concentrations up to about 25%, while it was observed only for much lower concentrations of Fe(II). This can be attributed to the ability of [Ni(bpy)3](PF6)2 to access a metastable conglomerate phase, while no such phase has been detected in [Fe(bpy)3](PF6)2. Furthermore, the chiral phase appears to be favored in fast-growing precipitates, while the racemic phase is favored in slow re-crystallizations for both Ni(II) and Fe(II) molecular alloys. X-ray natural circular dichroism (XNCD) measurements on [Ni0.13Zn0.87(bpy)3](PF6)2 demonstrate the chirality of the nickel molecules within the zinc molecular matrix.

Published
2023
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2. Common mechanism for helical nanotube formation by anodic polymerization and by cathodic deposition using helical pores on silicon electrodes

Author

Yuki Maeda, Takumi Yasuda, Kenta Matsuzaki, Yutaka Okazaki, Emilie Pouget, Reiko Oda, Atsushi Kitada, Kuniaki Murase, Guillaume Raffy, Dario M. Bassani, and Kazuhiro Fukami

Subjects
Industrial electrochemistry, TP250-261, Chemistry, QD1-999
Abstract

We report that platinum-assisted chemical etching formed self-organized helical pores in silicon substrates can be utilized as platforms for the electrochemical production of nanohelices of conducting polymers (polypyrrole) and metals (gold). Surprisingly, the nanohelices thus created are tubes although the polymerization and deposition were carried out by anodic and cathodic reactions, respectively. Based on our results, we propose a common mechanism for the formation of tubular nanohelices by both anodic polymerization and cathodic deposition through the accumulation of reactants in microporous silicon which covers the wall surface of the helical pores. Keywords: Helical pore, Nanohelices, Conducting polymers, Metals, Tubes

Published
2020
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4. Effect of Solvent on Convectively Driven Silica Particle Assembly: Decoupling Surface Tension, Viscosity, and Evaporation Rate

Author

Lucien Roach, David Gonzalez-Rodriguez, Jie Gao, Eric Laurichesse, Alexander Castro-Grijalba, Reiko Oda, Véronique Schmitt, Emilie Pouget, Mona Tréguer-Delapierre, Glenna L. Drisko, Institut de Chimie de la Matière Condensée de Bordeaux (ICMCB), Université de Bordeaux (UB)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie et Physique - Approche Multi-échelle des Milieux Complexes (LCP-A2MC), Université de Lorraine (UL), Chimie et Biologie des Membranes et des Nanoobjets (CBMN), Université de Bordeaux (UB)-École Nationale d'Ingénieurs des Travaux Agricoles - Bordeaux (ENITAB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre de Recherche Paul Pascal (CRPP), Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Funding for this work from the European Research Council (ERC) under European Union′s Horizon 2020 Research and Innovation Program (Grant No. 948319). L.R., G.L.D., and M.T.-D. received financial support from the Conseil Régional d′Aquitaine and the LabEx AMADEus (Grant No. ANR-10-LABX-42) in the framework of IdEx Bordeaux (Grant No. ANR-10-IDEX-03-02) managed by the National Agency for Research., ANR-10-IDEX-0302,ANR-10-IDEX-03-02,Investments for the Future Programme IdEx Bordeaux-LAPHIA, and European Project: 948319-ERC-2020-STG,SCATTER

Subjects
Landau‑Levich flow, evaporative rate, stick‑slip, viscosity, Electrochemistry, General Materials Science, [CHIM.MATE]Chemical Sciences/Material chemistry, Surfaces and Interfaces, Convective flux, Condensed Matter Physics, Spectroscopy
Abstract

International audience; The process of convectively self-assembling particles in films suffers from low reproducibility due to its high dependency on particle concentration, as well as a variety of interactions and physical parameters. Inhomogeneities in flow rates and instabilities at the air–liquid interface are mostly responsible for reproducibility issues. These problems are aggravated by adding multiple components to the dispersion, such as binary solvent mixtures or surfactant/polymer additives, both common approaches to control stick-slip behavior. When an additive is used, not only does it change the surface tension, but also the viscosity and the evaporation rate. Worse yet, gradients in these three properties can form, which then lead to Marangoni currents. Here, we use a series of alcohols to study the role of viscosity independently of other solvent properties, to show its impact on stick-slip behavior and interband distances. We show that mixtures of glycerol and alcohol or poly(acrylic acid) and alcohol lead to more complex patterning. Marangoni currents are not always observed in co-solvent systems, being dependent on the rate of solvent evaporation. To produce homogeneous particle assemblies and control stick-slip behavior, gradients must be avoided, and the surface tension and viscosity need both be carefully controlled.

Published
2023
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7. Cooperative interaction between organic and inorganic moieties in hybrid silica nanohelices for enantioselective interaction

Author

Rahul Nag, Yutaka Okazaki, Antoine Scalabre, Zakaria Anfar, Sylvain Nlate, Thierry Buffeteau, Reiko Oda, and Emilie Pouget

Subjects
Materials Chemistry, Metals and Alloys, Ceramics and Composites, General Chemistry, Catalysis, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials
Abstract

Hybrid nanometric helical structures formed by the molecular assemblies of dicationic gemini surfactants with tartrate counterions covered with helical silica walls interact differently with matching or mismatching enantiomers of the tartrate. The difference of the interaction is based on the cooperativity between the chiral crystalline gemini surfactant molecular organization/conformation and the rigid chiral nanospace formed by the helical silica wall.

Published
2022

8. Chiral Anthranyl Trifluoromethyl Alcohols: Structures, Oxidative Dearomatization and Chiroptical Properties

Author

Dorian Sonet, Mattéo Cayla, Raphaël Méreau, Estelle Morvan, Aline Lacoudre, Nicolas Vanthuyne, Muriel Albalat, Dario M. Bassani, Antoine Scalabre, Emilie Pouget, Brigitte Bibal, Institut des Sciences Moléculaires (ISM), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Européen de Chimie et Biologie (IECB), Université de Bordeaux (UB)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chimie et Biologie des Membranes et des Nanoobjets (CBMN), and Université de Bordeaux (UB)-École Nationale d'Ingénieurs des Travaux Agricoles - Bordeaux (ENITAB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Organic Chemistry, [CHIM]Chemical Sciences, General Chemistry, Catalysis
Abstract

International audience; Chiral trifluoromethyl alcohol groups were introduced at the hindered ortho positions of 9,10-diphenylanthracenes to investigate their effects on the physical properties and reactivity towards oxidative dearomatization. In such compact structures, the position in different quadrants and the preferred orientation of the ÀCH(OH)CF 3 groups were determined by the relative and absolute configurations of each stereoisomer, respectively. As a consequence, the stereochemistry governs the organization of the H-bonded molecules in single crystals (homochiral dimers vs ribbon), whereas in chlorinated solvents, they all behave as discrete compounds. Concerning their reactivity, the stereospecific dearomative oxidation of these molecules leads to 9,10-bisspiro-isobenzofuran-anthracenes, when using organic singleelectron transfer oxidants. The chiroptical properties of the alcohols and the corresponding dearomatized products were compared and showed an important modulation of the intensity.

Published
2022
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9. Near perfect head-to-head selectivity on the supramolecular photocyclodimerisation of 2-anthracenecarboxylate with self-organised gemini surfactant bilayers

Author

Wijak Yospanya, Takehiko Wada, Masaki Nishijima, Thierry Buffeteau, Emilie Pouget, Yasuyuki Araki, Reiko Oda, Chimie et Biologie des Membranes et des Nanoobjets (CBMN), École Nationale d'Ingénieurs des Travaux Agricoles - Bordeaux (ENITAB)-Institut de Chimie du CNRS (INC)-Université de Bordeaux (UB)-Centre National de la Recherche Scientifique (CNRS), Tohoku University [Sendai], Institut des Sciences Moléculaires (ISM), and Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, 010405 organic chemistry, Head to head, Metals and Alloys, Supramolecular chemistry, Regioselectivity, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Crystallography, Template, Pulmonary surfactant, 13. Climate action, 2-anthracenecarboxylate, Materials Chemistry, Ceramics and Composites, [CHIM.OTHE]Chemical Sciences/Other, Selectivity
Abstract

International audience; Silicificated self-organised crystalline bilayers of gemini surfactants were used as reaction templates for supramolecular regioselective [4+4] photocyclodimerisation of 2-anthracenecarboxylate in water. Near perfect head-to-head cyclodimers selectivity, up to 97% at room temperature was achieved with accelerated dimerisation. Ever since the first report in 1867, 1-3 the [4+4] photocyclodimerisation of anthracene and its derivatives has attracted much attention due to the unique structure and properties of the photocyclodimers obtained, and has been employed indeed as a key motif in energy storage and photoreversible devices. 4-8 However, controlling regio-and enantioselectivities of the photocyclodimerisation of anthracene derivatives, such as 2anthracenecarboxylate (AC) (Scheme 1), is a challenge, which has driven researchers to the use of supramolecular approach, 9,10 using cyclodextrins, 11-14 proteins, 15,16 molecular templates, 17-21 molecular cages, 20-22 twisted self-associated templates, 18 organogels, 23 and helical metal nanostructures 24 as hosts and templates. Most of the reported systems, however, require the multi-step synthesis of host/template, the modification of guest substrate and/or the irradiation in organic media at low temperature. From the Sustainable Development Goals (SDGs) point of view, a readily accessible, spontaneously self-organisable, operative under ambient conditions, yet biodegradable host/template is advocated, while a three-dimensionally well-defined, appropriately functionalised, structurally robust host/template is essential for directing the stereochemical course of photoreaction to desired product(s). Upon photoirradiation in aqueous media, AC form antiand syn-isomeric head-to-tail (HT) cyclodimers (ACD1 and ACD 2) and head-to-head (HH) cyclodimers (ACD 3 and ACD 4) in a 4:1 ratio (Table 1, entry 1) for steric and electrostatic reasons. Possessing two functional groups on the same side of molecule, the HH cyclodimers are structurally attractive as building blocks for functional devices and materials. 25,26 Wolff et al. succeeded to increase the HH/HT ratio of the photo-cyclodimerisation of 9-substituted anthracenes by executing the reaction in cationic and anionic micelles to gain modestly enhanced HH/HT ratios of 0.62-0.76, 27,28 for which the flexible micelle shell would be responsible for the limited value of HH/HT ratios.

Published
2020
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10. Chiral optical scattering from helical and twisted silica nanoribbons

Author

Reiko Oda, Sylvain Nlate, Emilie Pouget, Yann Battie, Naoya Ryu, Takashi Sagawa, Yutaka Okazaki, and Peizhao Liu

Subjects
Quantitative Biology::Biomolecules, Morphology (linguistics), Materials science, Metals and Alloys, Physics::Optics, General Chemistry, Molecular physics, Catalysis, Quartz substrate, Light scattering, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Materials Chemistry, Ceramics and Composites, Physics::Chemical Physics, Boundary element method
Abstract

Helical and twisted silica nanoribbons, deposited in an in-plane direction and with a random orientation, on a quartz substrate showed chiral optical scattering, and the helical nanoribbons had a g-factor of the order of 10-2 below 250 nm. Their signs depend on the handedness of the nanohelices. The effect of the morphology and the orientation of the helices on the chiral optical scattering were investigated with simulations via the boundary element method.

Published
2021

11. Chirality Induction to CdSe Nanocrystals Self-Organized on Silica Nanohelices: Tuning Chiroptical Properties

Author

Reiko Oda, Sisareuth Tan, Emilie Pouget, Peizhao Liu, Marion Decossas, Yann Battie, Takashi Sagawa, Yutaka Okazaki, Chimie et Biologie des Membranes et des Nanoobjets (CBMN), École Nationale d'Ingénieurs des Travaux Agricoles - Bordeaux (ENITAB)-Institut de Chimie du CNRS (INC)-Université de Bordeaux (UB)-Centre National de la Recherche Scientifique (CNRS), Graduate School of Energy Science, Kyoto University [Kyoto], Laboratoire de Chimie et Physique - Approche Multi-échelle des Milieux Complexes (LCP-A2MC), and Université de Lorraine (UL)

Subjects
Morphology (linguistics), Materials science, General Physics and Astronomy, Physics::Optics, 02 engineering and technology, 010402 general chemistry, Curvature, 01 natural sciences, behavioral disciplines and activities, Spectral line, Rod, CdSe quantum dots, chiral organization, Computer Science::Systems and Control, Condensed Matter::Superconductivity, mental disorders, [CHIM]Chemical Sciences, General Materials Science, chiral silica ribbons, CdSe/CdS quantum rods, Quantitative Biology::Biomolecules, General Engineering, 021001 nanoscience & nanotechnology, Grafting, 0104 chemical sciences, Condensed Matter::Soft Condensed Matter, Crystallography, Template, Helix, optically active nanostructures, sense organs, 0210 nano-technology, Chirality (chemistry)
Abstract

International audience; CdSe nanocrystals (NCs) were grafted on chiral silica nanoribbons, and the mechanism of resulting chirality induction was investigated. Because of their chiral organization, these NCs show optically active properties that depend strongly on their grafting densities and sizes of the NCs. The effect of the morphology of the chiral silica templates between helical (cylindrical curvature) vs twisted (saddle like curvature) ribbons was investigated. The g-factor of NCs-silica helical ribbons is larger than that of the NCs-silica twisted ribbons. Finally, rod-like NCs (QR) with different lengths were grafted on the twisted silica ribbons. Interestingly, their grafting direction with respect to the helix surface changed from side-grafting for short QR to tip-grafting for long rods and the corresponding CD spectra switched signs.

Published
2021
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12. Chiral Generation of Hot Carriers for Polarization-Sensitive Plasmonic Photocatalysis with Hybrid Nanostructures

Author

Yoel Negrín-Montecelo, Alexander O. Govorov, Zhiming Wang, Miguel Comesaña-Hermo, Miguel A. Correa-Duarte, Emilie Pouget, Reiko Oda, Artur Movsesyan, Sven Burger, Sylvain Nlate, Jie Gao, CINBIO, University of Vigo [ Pontevedra], Ohio University, Chimie et Biologie des Membranes et des Nanoobjets (CBMN), École Nationale d'Ingénieurs des Travaux Agricoles - Bordeaux (ENITAB)-Institut de Chimie du CNRS (INC)-Université de Bordeaux (UB)-Centre National de la Recherche Scientifique (CNRS), Zuse Institute Berlin (ZIB), University of Electronic Science and Technology of China (UESTC), Interfaces, Traitements, Organisation et Dynamique des Systèmes (ITODYS (UMR_7086)), and Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP)

Subjects
Polarization sensitive, Nanostructure, Materials science, nanostructures, Photocatalysis, chirality, Physics::Optics, Nanotechnology, [CHIM.MATE]Chemical Sciences/Material chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, photocatalysis, plasmonics, Plasmon
Abstract

Mastering the manipulation of chirality at the nanoscale has long been a priority for chemists, physicists and materials scientists, given its importance in the biochemical processes of the natural world and in the development of novel technologies. In this vein, the formation of novel metamaterials and sensing platforms resulting from the synergic combination of chirality and plasmonics has opened new avenues in nano-optics. Recently, the implementation of chiral plasmonic nanostructures in photocatalysis has been proposed theoretically as a means to drive polarization-dependent photochemistry. Nevertheless, the lack of synthetic procedures leading to the formation of robust plasmonic photocatalysts with chiroptical features has hindered the advancement of this field. In the present work, we demonstrate that the use of inorganic nanometric chiral templates for the controlled assembly of Au and TiO2 nanoparticles leads to the formation of plasmon-based photocatalysts with polarization-dependent reactivity. The formation of plasmonic assemblies with chiroptical activities induces the asymmetric formation of hot electrons and holes generated via electromagnetic excitation, opening the door to novel photocatalytic and optoelectronic features. More precisely, we demonstrate that the reaction yield can be improved when the helicity of the circularly polarized light used to activate the plasmonic component matches the handedness of the chiral substrate. Our approach may enable new applications in the fields of chirality and photocatalysis, particularly toward plasmon-induced chiral photochemistry.

Published
2021
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13. Chirality induction to achiral molecules by silica-coated chiral molecular assemblies

Author

Antoine Scalabre, Gabriele Magna, Sylvain Nlate, Yutaka Okazaki, Manuela Stefanelli, Thierry Buffeteau, Reiko Oda, Balamurugan Kuppan, Fabrizio Caroleo, Dario M. Bassani, Hirotaka Ihara, Donato Monti, Roberto Paolesse, Emilie Pouget, Chimie et Biologie des Membranes et des Nanoobjets (CBMN), École Nationale d'Ingénieurs des Travaux Agricoles - Bordeaux (ENITAB)-Institut de Chimie du CNRS (INC)-Université de Bordeaux (UB)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Moléculaires (ISM), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Dipartimento di ingegneria elettronica, Università di Roma Tor Vergata, and Università di Roma Tor Vergata

Subjects
Pharmacology, Circular dichroism, silica nanohelice, 010405 organic chemistry, Chemistry, Organic Chemistry, Settore CHIM/07, circularly polarized luminescence, induced chirality, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, Analytical Chemistry, Organic molecules, circular dichroism, Crystallography, Drug Discovery, Molecule, [CHIM]Chemical Sciences, excimer emission, Chirality (chemistry), Luminescence, Spectroscopy
Abstract

International audience; Hybrid silica-organic nanohelices are used to organize a large variety of nonchiral small organic molecules or inorganic anions to nanometer-sized assemblies. Such chiral organization of achiral molecules induces chiroptical properties as detected by vibrational or electronic circular dichroism (CD), as well as from circularly polarized luminescence (CPL).

Published
2021
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15. Slow kinetic evolution of nanohelices based on gemini surfactant self-assemblies with various enantiomeric excess; chiral segregation towards a racemic mixture

Author

Emilie Pouget, Franck Artzner, Yutaka Okazaki, Thierry Buffeteau, Reiko Oda, Brice Kauffmann, Sylvain Nlate, Jie Gao, Chimie et Biologie des Membranes et des Nanoobjets (CBMN), Université de Bordeaux (UB)-École Nationale d'Ingénieurs des Travaux Agricoles - Bordeaux (ENITAB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Kyoto Institute of Technology, Soutien à la Recherche de l'Institut Européen de Chimie Biologique, Université Sciences et Technologies - Bordeaux 1 (UB)-Institut Européen de Chimie et de Biologie-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Physique de Rennes (IPR), Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Moléculaires (ISM), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), France-Japan International Associated Laboratory, Chiral Nanostructures for Photonic Applications (LIA-CNPA), Centre National de la Recherche Scientifique Centre National de la Recherche Scientifique (CNRS), Universite de Bordeaux, JSPS Overseas Research Fellowship, Chinese Scholarship Council Fellowship, LabEx AMADEus [ANR-10-LABX-42, ANR-10-IDEX-03-02], Rennes Metropoles, ANR-10-LABX-0042,AMADEus,Advanced Materials by Design(2010), ANR-10-IDEX-0003,IDEX BORDEAUX,Initiative d'excellence de l'Université de Bordeaux(2010), Jonchère, Laurent, Advanced Materials by Design - - AMADEus2010 - ANR-10-LABX-0042 - LABX - VALID, Initiative d'excellence de l'Université de Bordeaux - - IDEX BORDEAUX2010 - ANR-10-IDEX-0003 - IDEX - VALID, École Nationale d'Ingénieurs des Travaux Agricoles - Bordeaux (ENITAB)-Institut de Chimie du CNRS (INC)-Université de Bordeaux (UB)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut Européen de Chimie et de Biologie-Université Sciences et Technologies - Bordeaux 1-Institut de Chimie du CNRS (INC), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS), and Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
[PHYS]Physics [physics], 010405 organic chemistry, Chemistry, 010402 general chemistry, Kinetic energy, 01 natural sciences, 0104 chemical sciences, [PHYS] Physics [physics], Crystallography, Pulmonary surfactant, Amphiphile, Ribbon, Materials Chemistry, Racemic mixture, General Materials Science, Enantiomer, Enantiomeric excess
Abstract

International audience; Very slow kinetic evolution (days) of chiral nanoribbons based on amphiphilic molecular assemblies is investigated for various enantiomeric excess. In the early stage of ribbon formation, those formed for low enantiomeric excess (0

Published
2021
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16. Silica-Supported Phosphine-Gold Complexes as an Efficient Catalytic System for a Dearomative Spirocyclization

Author

Reiko Oda, Zhen Cao, Antoine Scalabre, Sonia Buffière, Sylvain Nlate, Brigitte Bibal, Emilie Pouget, Chimie et Biologie des Membranes et des Nanoobjets (CBMN), Université Sciences et Technologies - Bordeaux 1-École Nationale d'Ingénieurs des Travaux Agricoles - Bordeaux (ENITAB)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Moléculaires (ISM), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), École Nationale d'Ingénieurs des Travaux Agricoles - Bordeaux (ENITAB)-Institut de Chimie du CNRS (INC)-Université de Bordeaux (UB)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie de la Matière Condensée de Bordeaux (ICMCB), Université de Bordeaux (UB)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Financial support was provided by the China Scholarship Council (Z.C. fellowship), the Agence Nationale pour la Recherche (ANR‐CONACYT‐159884), the University of Bordeaux, and the Centre National de la Recherche Scientifique (CNRS). The authors thank Aline Lacoudre (CESAMO, Université de Bordeaux) for the structural resolution of ligand L2 by X‐ray crystallography, and the Placamat platform for TEM characterizations., and ANR-11-ISV7-0001,MALE-EFFECT,L'effet mâle chez les ongulés: applications agronomiques et mécanismes neuroendocriniens(2011)

Subjects
010405 organic chemistry, Aryl, Organic Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, 01 natural sciences, Chloride, Combinatorial chemistry, Catalysis, 0104 chemical sciences, Metal, chemistry.chemical_compound, chemistry, Covalent bond, visual_art, visual_art.visual_art_medium, medicine, Reactivity (chemistry), Trifluoromethanesulfonate, Phosphine, ComputingMilieux_MISCELLANEOUS, medicine.drug
Abstract

International audience; The combination of metal catalyst and inorganic silica frameworks provides a greener approach to recyclable catalysis. In this study, three phosphine–gold chloride complexes have been successfully covalently grafted onto chiral silica nanohelices. The resulting 3D ensembles showed chiroptical properties that allowed the monitoring of the supported ligands. The heterogeneous gold chloride catalysts in cooperation with silver triflate exhibited high reactivity in various reactions, especially in the spirocyclization of aryl alkynoate esters, for which a catalytic loading of 0.05 mol % could be employed. The heterogeneous catalysts could be easily recovered and recycled seven or eight times without any loss of efficiency. By adding more silver triflate, 25 cycles with full conversion were achieved owing to a complex catalytic system based on silica and metallic species.

Published
2020
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17. Optically Active Perovskite CsPbBr

Author

Peizhao, Liu, Wei, Chen, Yutaka, Okazaki, Yann, Battie, Lysiane, Brocard, Marion, Decossas, Emilie, Pouget, Peter, Müller-Buschbaum, Brice, Kauffmann, Shaheen, Pathan, Takashi, Sagawa, and Reiko, Oda

Abstract

Perovskite nanocrystals (PNCs) exhibit excellent absorption and luminescent properties. Inorganic silica right (or left) handed nanohelices are used as chiral templates to induce optically active properties to CsPbBr

Published
2020

18. Common mechanism for helical nanotube formation by anodic polymerization and by cathodic deposition using helical pores on silicon electrodes

Author

Emilie Pouget, Kuniaki Murase, Guillaume Raffy, Kazuhiro Fukami, Takumi Yasuda, Yutaka Okazaki, Atsushi Kitada, Reiko Oda, Kenta Matsuzaki, Yuki Maeda, Dario M. Bassani, Chimie et Biologie des Membranes et des Nanoobjets (CBMN), École Nationale d'Ingénieurs des Travaux Agricoles - Bordeaux (ENITAB)-Institut de Chimie du CNRS (INC)-Université de Bordeaux (UB)-Centre National de la Recherche Scientifique (CNRS), Department of Materials Science and Engineering [Kyoto], Kyoto University [Kyoto], Institut des Sciences Moléculaires (ISM), and Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Nanotube, Materials science, Silicon, Helical pore, chemistry.chemical_element, Conducting polymers, 02 engineering and technology, 010402 general chemistry, Polypyrrole, Electrochemistry, 01 natural sciences, lcsh:Chemistry, chemistry.chemical_compound, [CHIM]Chemical Sciences, Nanohelices, ComputingMilieux_MISCELLANEOUS, Conductive polymer, Tubes, technology, industry, and agriculture, Microporous material, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Isotropic etching, 0104 chemical sciences, chemistry, Chemical engineering, Polymerization, lcsh:Industrial electrochemistry, lcsh:QD1-999, Metals, 0210 nano-technology, lcsh:TP250-261
Abstract

We report that platinum-assisted chemical etching formed self-organized helical pores in silicon substrates can be utilized as platforms for the electrochemical production of nanohelices of conducting polymers (polypyrrole) and metals (gold). Surprisingly, the nanohelices thus created are tubes although the polymerization and deposition were carried out by anodic and cathodic reactions, respectively. Based on our results, we propose a common mechanism for the formation of tubular nanohelices by both anodic polymerization and cathodic deposition through the accumulation of reactants in microporous silicon which covers the wall surface of the helical pores. Keywords: Helical pore, Nanohelices, Conducting polymers, Metals, Tubes

Published
2020
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19. Tuning the Chiroptical Properties of Elongated Nano-objects

Author

Jie, Gao, Wenbing, Wu, Vincent, Lemaire, Alain, Carvalho, Sylvain, Nlate, Thierry, Buffeteau, Reiko, Oda, Yann, Battie, Matthias, Pauly, and Emilie, Pouget

Abstract

Chiral materials appear as excellent candidates to control and manipulate the polarization of light in optical devices. In nanophotonics, the self-assembly of colloidal plasmonic nanoparticles gives rise to strong resonances in the visible range, and when such organizations are chiral, a strong chiroplasmonic effect can be observed. In the present work, we describe the optical properties of chiral artificial nanophotonic materials

Published
2020

20. Hierarchical chirality expression of gemini surfactant aggregates via equilibrium between chiral nucleotide and nonchiral mono-anions

Author

Reiko Oda, Emilie Pouget, Dmytro Dedovets, Thierry Buffeteau, Barbara Martin, Yutaka Okazaki, Chimie et Biologie des Membranes et des Nanoobjets (CBMN), École Nationale d'Ingénieurs des Travaux Agricoles - Bordeaux (ENITAB)-Institut de Chimie du CNRS (INC)-Université de Bordeaux (UB)-Centre National de la Recherche Scientifique (CNRS), Laboratoire du Futur (LOF), Université Sciences et Technologies - Bordeaux 1-RHODIA-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Kyoto University [Kyoto], Institut des Sciences Moléculaires (ISM), and Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
inorganic chemicals, Micrometer scale, micrometric helices, High Energy Physics::Lattice, chirality, nucleo amphiphiles, 010402 general chemistry, 01 natural sciences, Catalysis, Analytical Chemistry, Pulmonary surfactant, guanosine-5'-monophosphate, Drug Discovery, polycyclic compounds, Physics::Atomic and Molecular Clusters, heterocyclic compounds, Nucleotide, Physics::Chemical Physics, Spectroscopy, ComputingMilieux_MISCELLANEOUS, Pharmacology, chemistry.chemical_classification, gemini surfactant, Amphiphilic molecule, 010405 organic chemistry, organic chemicals, Organic Chemistry, High Energy Physics::Phenomenology, [CHIM.MATE]Chemical Sciences/Material chemistry, Self-assembly, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Crystallography, chemistry, health occupations, Chirality (chemistry)
Abstract

International audience; The assembling behaviors of non-chiral dicationic amphiphilic molecules (gemini) in the presence of the mixture of chiral anionic nucleotides and non-chiral anions are investigated. We demonstrate that subtle balance of various physico-chemical parameters and the competition between chiral and non-chiral anions at the interface of gemini assemblies influences the expression of molecular chirality at the micrometer scale through the hierarchical molecular assembly.

Published
2020
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21. Optically Active Perovskite CsPbBr 3 Nanocrystals Helically Arranged on Inorganic Silica Nanohelices

Author

Brice Kauffmann, Yutaka Okazaki, Shaheen Pathan, Reiko Oda, Peter Müller-Buschbaum, Yann Battie, Emilie Pouget, Peizhao Liu, Wei Chen, Marion Decossas, Takashi Sagawa, Lysiane Brocard, Chimie et Biologie des Membranes et des Nanoobjets (CBMN), and École Nationale d'Ingénieurs des Travaux Agricoles - Bordeaux (ENITAB)-Institut de Chimie du CNRS (INC)-Université de Bordeaux (UB)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Circular dichroism, Materials science, Mechanical Engineering, Bioengineering, 02 engineering and technology, General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, Optically active, 021001 nanoscience & nanotechnology, Condensed Matter Physics, Photochemistry, 3. Good health, Nanocrystal, General Materials Science, 0210 nano-technology, Luminescence, Absorption (electromagnetic radiation), ComputingMilieux_MISCELLANEOUS, Perovskite (structure)
Abstract

Perovskite nanocrystals (PNCs) exhibit excellent absorption and luminescent properties. Inorganic silica right (or left) handed nanohelices are used as chiral templates to induce optically active p...

Published
2020
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22. Tuning the Chiroptical Properties of Elongated Nano-objects via Hierarchical Organization

Author

Alain Carvalho, Vincent Lemaire, Wenbing Wu, Thierry Buffeteau, Reiko Oda, Jie Gao, Emilie Pouget, Sylvain Nlate, Matthias Pauly, Yann Battie, Chimie et Biologie des Membranes et des Nanoobjets (CBMN), Université de Bordeaux (UB)-École Nationale d'Ingénieurs des Travaux Agricoles - Bordeaux (ENITAB)-Institut de Chimie du CNRS (INC)-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, 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 des Sciences Moléculaires (ISM), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie et Physique - Approche Multi-échelle des Milieux Complexes (LCP-A2MC), Université de Lorraine (UL), Buffeteau, Thierry, École Nationale d'Ingénieurs des Travaux Agricoles - Bordeaux (ENITAB)-Institut de Chimie du CNRS (INC)-Université de Bordeaux (UB)-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), 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 Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Sciences et Technologies - Bordeaux 1-École Nationale d'Ingénieurs des Travaux Agricoles - Bordeaux (ENITAB)-Centre National de la Recherche Scientifique (CNRS), Univ Bordeaux, CNRS UMR 5248, Inst Chim & Biol Membranes & Nanoobjets, INP Bordeaux, Université de Bordeaux (UB)-Institut Polytechnique de Bordeaux (Bordeaux INP)-Centre National de la Recherche Scientifique (CNRS), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et nanosciences d'Alsace, Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Université de Strasbourg (UNISTRA)-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))-Université de Strasbourg (UNISTRA), and Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, Thin films, Aucun, General Physics and Astronomy, Nanoparticle, Physics::Optics, Nanotechnology, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Nano, General Materials Science, Mueller calculus, Thin film, [PHYS.COND]Physics [physics]/Condensed Matter [cond-mat], Chirality, ComputingMilieux_MISCELLANEOUS, Plasmonic nanoparticles, [CHIM.MATE] Chemical Sciences/Material chemistry, Optical properties, business.industry, General Engineering, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Template, Colloidal gold, Nanoparticles, Photonics, 0210 nano-technology, business, Layers
Abstract

International audience; Chiral materials appear as excellent candidates to control and manipulate the polarization of light in optical devices. In nano-photonics, the self-assembly of colloidal plasmonic nanoparticles gives rise to strong resonances in the visible range and, when such organizations are chiral, strong chiroplasmonic effect can be observed. In the present work, we describe the optical properties of chiral artificial nano-photonic materials, Goldhelices, which are hierarchically organized by Grazing Incidence Spraying. These Goldhelices are made by plasmonic nanoparticles (gold) grafted onto helical templates made from silica nanohelices. A comparison of oriented vs non-oriented surfaces has been performed by Mueller matrix polarimetry, showing the importance of the organization of the Goldhelices regarding their interaction with light. Moreover, mono-vs multi-layers photonic films are created and the measured optical properties are discussed and compared to simulations.

Published
2020
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23. J. Phys. Chem. B

Author

Jonnalagadda Raghava Rao, Gwénaëlle Le Bourdon, Emilie Pouget, Sathya Ramalingam, Antoine Scalabre, Adeline Perro, Institut des Sciences Moléculaires (ISM), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chimie et Biologie des Membranes et des Nanoobjets (CBMN), École Nationale d'Ingénieurs des Travaux Agricoles - Bordeaux (ENITAB)-Institut de Chimie du CNRS (INC)-Université de Bordeaux (UB)-Centre National de la Recherche Scientifique (CNRS), Centre de recherches Paul Pascal (CRPP), and Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010402 general chemistry, 01 natural sciences, Fluorescence spectroscopy, Nanocapsules, Adsorption, 0103 physical sciences, Nano, Materials Chemistry, Animals, Physical and Theoretical Chemistry, Bovine serum albumin, Nanoscopic scale, ComputingMilieux_MISCELLANEOUS, 010304 chemical physics, biology, Chemistry, Water, Serum Albumin, Bovine, [CHIM.MATE]Chemical Sciences/Material chemistry, Silicon Dioxide, 0104 chemical sciences, Surfaces, Coatings and Films, Chemical engineering, Oil droplet, biology.protein, Cattle, Emulsions, Muramidase, Nanocarriers, Hydrophobic and Hydrophilic Interactions, Oils
Abstract

The design of nanocarriers containing hydrophobic and hydrophilic compounds represents a powerful tool for cocktail delivery. Water-in-oil-in-water emulsions constitute an attractive approach, as they offer dual encapsulation and provide a template for the constitution of a capsule. A limitation in the preparation of nano double emulsions is their instability resulting from high curvature radii. In this work, silica nanocapsules (NCs) stable over several months were synthesized. This was achieved by exploiting a double emulsion in which the oil phase is constituted by a combination of oils presenting several volatilities. The decrease of oil droplet size by evaporation favored the deposition of a silica layer at the nanoscale interface. The release of the payload obtained by drying the capsules was investigated by fluorescence spectroscopy. Understanding the interactions between proteins and nanocapsules is a fundamental point for many biological applications. Nanocapsules were exposed to two model proteins, which were bovine serum albumin (BSA) and lysozyme (Ly). These proteins, presenting differences in charges and size, showed distinctive arrangements onto the nanocapsules. Moreover, we have studied changes in α-helix and β-sheet content, which divulged the interactions between the proteins and the nanocapsules.

Published
2019
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24. Cyclobishelicenes: Shape-Persistent Figure-Eight Aromatic Molecules with Promising Chiroptical Properties

Author

Michel Giorgi, Yoann Coquerel, Harald Bock, Emilie Pouget, Yannick Carissan, Christie Aroulanda, Antoine Scalabre, Antoine Robert, Fabien Durola, Nicolas Vanthuyne, Marion Jean, Guillaume Naulet, Centre de Recherche Paul Pascal (CRPP), Université de Bordeaux (UB)-Centre National de la Recherche Scientifique (CNRS), Chimie et Biologie des Membranes et des Nanoobjets (CBMN), Université Sciences et Technologies - Bordeaux 1-École Nationale d'Ingénieurs des Travaux Agricoles - Bordeaux (ENITAB)-Centre National de la Recherche Scientifique (CNRS), Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Fédération Sciences Chimiques Marseille (FSCM), Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Université Paris-Sud - Paris 11 (UP11)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Bordeaux (UB)-École Nationale d'Ingénieurs des Travaux Agricoles - Bordeaux (ENITAB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Aix Marseille University, Centrale Marseille, University of Bordeaux, Paris Saclay University, and the Centre National de la Recherche Scientifique (CNRS), ICMMO, Université Paris-Sud - Paris 11 (UP11), and École Nationale d'Ingénieurs des Travaux Agricoles - Bordeaux (ENITAB)-Institut de Chimie du CNRS (INC)-Université de Bordeaux (UB)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, Chemistry, aromatic compounds, Organic Chemistry, chirality, chiroptical properties, General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, Inherent chirality, 01 natural sciences, Catalysis, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Crystallography, chemistry.chemical_compound, Helicene, helical structures, conformation analysis, Molecule, Enantiomer, Chirality (chemistry), Conformational isomerism
Abstract

International audience; Cyclobis[n]helicenes (n = 3 or 5) are chiral D2-symmetric p-conjugated macrocycles with stable lemniscular, or figure-eight, shapes. The conformational analysis of five different cyclobis[n]helicenes revealed that these molecules can only exist as their lemniscular conformers with high barriers to enantiomerization (>200 kJ.mol-1). The enantiomers of a cyclobis[5]helicene were resolved by HPLC and their unusual chiroptical properties were attributed to the inherent chirality of their macrocyclic figure-eight.

Published
2019
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25. Direct Observation of Siloxane Chirality on Twisted and Helical Nanometric Amorphous Silica

Author

Ryohei Yagi, Thierry Buffeteau, Reiko Oda, Emilie Pouget, Hirotaka Ihara, Naoya Ryu, Elise Siurdyban, David Talaga, Yutaka Okazaki, and Makoto Takafuji

Subjects
Materials science, High Energy Physics::Lattice, Bioengineering, Nanotechnology, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Nanomaterials, law.invention, symbols.namesake, chemistry.chemical_compound, law, General Materials Science, Calcination, Mechanical Engineering, High Energy Physics::Phenomenology, General Chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 0104 chemical sciences, Crystallography, chemistry, Transmission electron microscopy, Siloxane, Vibrational circular dichroism, symbols, 0210 nano-technology, Raman spectroscopy, Chirality (chemistry), Cotton effect
Abstract

Synthesis of chiral inorganic or hybrid nanomaterials through sol–gel transcription of chiral organic templates has attracted a great deal of interest for more than a decade. However, the chiral nature of these inorganic matrices has never been directly observed. For the first time, we report a direct evaluation of chirality on noncrystalline silica chiral nanoribbons by vibrational circular dichroism (VCD) measurements. Strong Cotton effect around 1150–1000 cm–1 from Si—O—Si asymmetric stretching vibration was observed. Surprisingly, calcination of these hybrid nanoribbons doubled the intensity of Cotton effects. On the basis of transmission electron microscopy observations, IR, VCD, NMR, and Raman spectroscopies, we demonstrate that the silica chirality originates from twisted siloxane network composed of chiral arrangement of the Si—O—Si bonds. Our findings clearly prove the presence of chiral organization of amorphous silica network, making them very promising chiral platforms for chiral recognition, ...

Published
2016
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26. Memorized chiral arrangement of gemini surfactant assemblies in nanometric hybrid organic–silica helices

Author

Emilie Pouget, Naoya Ryu, Reiko Oda, Yutaka Okazaki, Makoto Takafuji, Hirotaka Ihara, Kana Hirai, and Shoji Nagaoka

Subjects
inorganic chemicals, 02 engineering and technology, Tartrate, 010402 general chemistry, 01 natural sciences, Catalysis, chemistry.chemical_compound, Pulmonary surfactant, Bromide, polycyclic compounds, Materials Chemistry, Methyl orange, Organic chemistry, heterocyclic compounds, chemistry.chemical_classification, organic chemicals, Metals and Alloys, General Chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, chemistry, Chemical engineering, Silica matrix, health occupations, Ceramics and Composites, Counterion, 0210 nano-technology
Abstract

Hybrid nanohelices were obtained from silicification of self-assemblies of gemini surfactants with tartrate counterions. The chiral arrangement of these non-chiral gemini surfactants was preserved in the silica matrix even after the counterion exchange for a non-chiral bromide, and was capable of inducing the chiral organisation of a non-chiral dye, methyl orange.

Published
2016
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27. Silica twisted and helical nanoribbons as chiral inducers for peroxophosphotungstate anions

Author

David Talaga, Emilie Pouget, Thierry Buffeteau, Reiko Oda, Mariam Attoui, Sylvain Nlate, Chimie et Biologie des Membranes et des Nanoobjets (CBMN), École Nationale d'Ingénieurs des Travaux Agricoles - Bordeaux (ENITAB)-Institut de Chimie du CNRS (INC)-Université de Bordeaux (UB)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Moléculaires (ISM), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de chimie organique et organométallique (LCOO), and Université Sciences et Technologies - Bordeaux 1-Centre National de la Recherche Scientifique (CNRS)

Subjects
Circular dichroism, 010405 organic chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Catalysis, Nanomaterials, Inorganic Chemistry, Crystallography, chemistry.chemical_compound, symbols.namesake, chemistry, Polyoxometalate, Triethoxysilane, Materials Chemistry, symbols, Phosphotungstic acid, Physical and Theoretical Chemistry, Raman spectroscopy, Chirality (chemistry), ComputingMilieux_MISCELLANEOUS
Abstract

As a part of our ongoing research towards the investigation of chiral polyoxometalate-based nanomaterials (NANOPOMs), new chiral POM-based silica twisted and helical ribbons were synthesized by the treatment of 3-aminopropyl triethoxysilane (APTES) functionalized left- and right-handed silica twisted and helical nanoribbons with phosphotungstic acid H3PW12O40 and excess of H2O2. The morphology and structural composition of the resulting NANOPOM hybrids as well as the presence of POM species were confirmed by various physicochemical techniques such as solid 31P NMR, UV–Vis, Raman, TEM, HR-TEM, and EDX. Solid 31P NMR studies indicate that the structures of these NANOPOM hybrids contain various phosphotungstate anions, with among them, the catalytically active Venturello peroxophosphotungstate trianion [PO4{WO(O2)2}4]3–. Interestingly, the optical activity of these twisted and helical NANOPOM hybrids has been confirmed by circular dichroism (CD) spectroscopy, highlighting the chirality induction from chiral nanoribbons to achiral POM clusters. The catalytic performances of these NANOPOM hybrids were evaluated in the heterogeneous oxidation of methyl phenyl sulfide as a model reaction, indicating NANOPOM hybrids built from twisted ribbons as the most efficient catalysts.

Published
2019
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28. Induced circular dichroism of monoatomic anions: silica-assisted the transfer of chiral environment from molecular assembled nanohelices to halide ions

Author

Shaheen Pathan, Reiko Oda, Emilie Pouget, Hirotaka Ihara, Sylvain Nlate, Thierry Buffeteau, Shoji Nagaoka, Yutaka Okazaki, Naoya Ryu, Department of Applied Chemistry and Biochemistry, Kumamoto University, Institut des Sciences Moléculaires (ISM), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de chimie organique et organométallique (LCOO), Université Sciences et Technologies - Bordeaux 1-Centre National de la Recherche Scientifique (CNRS), Chimie et Biologie des Membranes et des Nanoobjets (CBMN), and École Nationale d'Ingénieurs des Travaux Agricoles - Bordeaux (ENITAB)-Institut de Chimie du CNRS (INC)-Université de Bordeaux (UB)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Monatomic gas, Circular dichroism, Materials science, Metals and Alloys, Cationic polymerization, Halide, 02 engineering and technology, General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, Photochemistry, 01 natural sciences, Chemical reaction, Catalysis, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Materials Chemistry, Ceramics and Composites, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract

We demonstrate the first example of induced CD of monoatomic anions. This was detected using chirally-arranged molecular assemblies of non-chiral cationic gemini surfactants (16-2-16) with monoatomic anions stabilized with silica-coating. Furthermore, we have also achieved multi-step transfer of a chiral environment through an in situ chemical reaction via chiralized monoatomic anions.

Published
2018
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29. Gold Nanoparticle Chains: Synthesis, Characterization, and Modeling Using Spectroscopic Ellipsometry

Author

Aotmane En Naciri, Emilie Pouget, Julien Vieaud, Reiko Oda, Yann Battie, Katsuhiko Ariga, M. Stchakovsky, Jérémy Cane, Jie Gao, Chimie et Biologie des Membranes et des Nanoobjets (CBMN), École Nationale d'Ingénieurs des Travaux Agricoles - Bordeaux (ENITAB)-Institut de Chimie du CNRS (INC)-Université de Bordeaux (UB)-Centre National de la Recherche Scientifique (CNRS), HORIBA France SAS [Longjumeau], HORIBA Scientific [France], Laboratoire de Chimie et Physique - Approche Multi-échelle des Milieux Complexes (LCP-A2MC), Université de Lorraine (UL), International Center for Materials Nanoarchitectonics (MANA), and National Institute for Materials Science (NIMS)

Subjects
Materials science, Physics::Optics, Nanoparticle, [CHIM.MATE]Chemical Sciences/Material chemistry, 02 engineering and technology, Molar absorptivity, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Condensed Matter::Soft Condensed Matter, Solvent, Dipole, Colloid, General Energy, Chemical physics, Transmission electron microscopy, Ellipsometry, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS, Plasmon
Abstract

In this paper, we explore the ability of ellipsometry to characterize colloidal suspensions composed of gold nanoparticle (NP) chains. The complex effective index of these suspensions is deduced from ellipsometric measurement by using a wavelength-by-wavelength inversion without any dispersion law. We show that the effective refractive index of these colloids is defined by the nature of the solvent, whereas their effective extinction coefficient is mainly sensitive to the plasmonic properties of NP chains. The influence of the NP radius distribution and arrangement on the effective extinction coefficient of NP chain are investigated through simulations based on the coupled point dipole method (CDM). We clearly show that this coefficient is mainly sensitive to the interparticle distance and the number of NPs in the longest segment of chains. We demonstrate that the distribution of the number of NPs in the longest segment of chains and their volume fractions can be directly deduced from the ellipsometry by ...

Published
2018
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30. Chem

Author

Reiko Oda, Gwénaëlle Le Bourdon, Emilie Pouget, Thierry Buffeteau, Mariam Attoui, David Talaga, Sylvain Nlate, Chimie et Biologie des Membranes et des Nanoobjets (CBMN), École Nationale d'Ingénieurs des Travaux Agricoles - Bordeaux (ENITAB)-Institut de Chimie du CNRS (INC)-Université de Bordeaux (UB)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Moléculaires (ISM), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de chimie organique et organométallique (LCOO), and Université Sciences et Technologies - Bordeaux 1-Centre National de la Recherche Scientifique (CNRS)

Subjects
Circular dichroism, silica nanohelices, oxidation, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Catalysis, Spectral line, symbols.namesake, Adsorption, polyoxometalates, Spectroscopy, ComputingMilieux_MISCELLANEOUS, Chemistry, Organic Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, circular dichroism, Crystallography, Polyoxometalate, symbols, 0210 nano-technology, Chirality (chemistry), Raman spectroscopy, chirality induction
Abstract

In order to investigate the principle of chiral induction from nanometric silica helices to polyoxometalate (POM) clusters, a series of optically active silica POM-based nanohelices (NANOPOMs) have been prepared by electrostatic grafting and direct adsorption of α-Keggin polyoxometalate [α-PW12 O40 ]3- to well-defined left- and right-handed silica nanohelices. UV/Vis, Raman, DRIFT, TEM, HR-TEM, EDS and circular dichroism (CD) spectroscopy were used to characterize these NANOPOMs, and confirm the presence of POM clusters as well as their interactions with the helical support. The optical activity of the left-handed and right-handed NANOPOMs has been proven by CD spectroscopy. Their CD spectra are mirror images of one another, showing cotton effects at around 214 and 276 nm, this last contribution corresponding to the oxygen-to-tungsten charge-transfer bands of Keggin polyoxoanions. The CD signal of POM clusters is strongly enhanced for NANOPOMs built by adsorption of POM onto silica nanohelices, indicating a better induced optical activity to POM clusters. These nanohelices are stable, recoverable and active catalysts in the oxidation of sulfides. To the best of our knowledge, the present research represents the first examples of optically active POM-containing silica nanohelices in which achiral POM clusters have been grafted onto silica nanohelices, and display chiroptical effects.

Published
2018
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31. Structural and mechanical characterization of hybrid metallic-inorganic nanosprings

Author

Sabrina Habtoun, Said Houmadi, Dmytro Dedovets, Christian Bergaud, Reiko Oda, Benjamin Reig, Marie-Hélène Delville, Fuccio Cristiano, Emilie Pouget, Équipe Microsystèmes électromécaniques (LAAS-MEMS), Laboratoire d'analyse et d'architecture des systèmes (LAAS), Université Toulouse - Jean Jaurès (UT2J)-Université Toulouse 1 Capitole (UT1), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse - Jean Jaurès (UT2J)-Université Toulouse 1 Capitole (UT1), Université Fédérale Toulouse Midi-Pyrénées, Équipe NanoBioSystèmes (LAAS-NBS), Service Techniques et Équipements Appliqués à la Microélectronique (LAAS-TEAM), Chimie et Biologie des Membranes et des Nanoobjets (CBMN), Université de Bordeaux (UB)-École Nationale d'Ingénieurs des Travaux Agricoles - Bordeaux (ENITAB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie de la Matière Condensée de Bordeaux (ICMCB), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Université de Bordeaux (UB), Équipe Matériaux et Procédés pour la Nanoélectronique (LAAS-MPN), French RENATECH network, ANR-10-BLAN-0813,nanosprings,Nanohélices hybrides organiques–inorganiques fonctionnelles : étude de phénomènes exaltés à l'échelle nanométrique(2010), ANR-15-CE08-0041,NANOHELIFLEX,Assemblage de type ' bottom-up ' de Nanohélices fonctionnalisées: un pas de plus vers des dispositifs flexibles.(2015), Université Toulouse Capitole (UT Capitole), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université Toulouse - Jean Jaurès (UT2J), Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université Toulouse Capitole (UT Capitole), Université de Toulouse (UT), Université de Bordeaux (UB)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and École Nationale d'Ingénieurs des Travaux Agricoles - Bordeaux (ENITAB)-Institut de Chimie du CNRS (INC)-Université de Bordeaux (UB)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Nanostructure, Materials science, nanostructure, Polymers and Plastics, Silicon, Multiphysics, atomic force spectroscopy, chemistry.chemical_element, 02 engineering and technology, nanohelix, 010402 general chemistry, 01 natural sciences, Focused ion beam, Biomaterials, FIB, Composite material, High-resolution transmission electron microscopy, nanospring, Nanoelectromechanical systems, Metals and Alloys, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, nanomechanics, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, EBID, chemistry, Transmission electron microscopy, 0210 nano-technology, Nanomechanics
Abstract

International audience; Silica nanosprings (NS) are fabricated by a sol–gel deposition of silica precursors onto a template made of self-assembled organic chiral nanostructures. They are deposited and assembled on microstructured silicon substrates, and then metallized and clamped in a single lithography-free step using a focused ion beam (FIB). The resulting suspended hybrid metallic/inorganic NS are then characterized with high-resolution transmission electron microscopy (HRTEM) and scanning TEM/energy-dispersive X-ray spectroscopy (STEM/EDX), showing the atomic structure of the metallic layer. Three-point bending tests are also carried out using an atomic force microscope (AFM) and supported by finite element method (FEM) simulation with COMSOL Multiphysics allowing the characterization of the mechanical behavior and the estimation of the stiffness of the resulting NS. The information obtained on the structural and mechanical properties of the NS is discussed for future nano-electro-mechanical system (NEMS) applications.

Published
2017
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32. Fluorescence emission originated from the H-aggregated cyanine dye with chiral gemini surfactant assemblies having a narrow absorption band and a remarkably large Stokes shift

Author

Reiko Oda, Naoya Ryu, Shoji Nagaoka, Emilie Pouget, Yutaka Okazaki, Makoto Takafuji, and Hirotaka Ihara

Subjects
inorganic chemicals, 02 engineering and technology, Tartrate, 010402 general chemistry, Photochemistry, 01 natural sciences, Catalysis, chemistry.chemical_compound, symbols.namesake, Stokes shift, Materials Chemistry, Symmetry breaking, Cyanine, chemistry.chemical_classification, Metals and Alloys, Cationic polymerization, General Chemistry, 021001 nanoscience & nanotechnology, Fluorescence, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, chemistry, Absorption band, Ceramics and Composites, symbols, Counterion, 0210 nano-technology
Abstract

We demonstrate that the fluorescence emission that originated from a cyanine dye forming H-aggregates with a narrow absorption band and a remarkably large Stokes shift can be induced by symmetry breaking. The H-aggregate formation was successfully induced using chirally assembled cationic gemini surfactants with enantiomeric tartrate counterions as templates in water.

Published
2017

33. Self-assembled nanostructured metamaterials

Author

Reiko Oda, Virginie Ponsinet, Alexandre Baron, Emilie Pouget, Yutaka Okazaki, Philippe Barois, Centre de recherches Paul Pascal (CRPP), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Bordeaux (UB), Chimie et Biologie des Membranes et des Nanoobjets (CBMN), Université de Bordeaux (UB)-École Nationale d'Ingénieurs des Travaux Agricoles - Bordeaux (ENITAB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), ANR-10-IDEX-0003,IDEX BORDEAUX,Initiative d'excellence de l'Université de Bordeaux(2010), and École Nationale d'Ingénieurs des Travaux Agricoles - Bordeaux (ENITAB)-Institut de Chimie du CNRS (INC)-Université de Bordeaux (UB)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Fabrication, Materials science, Nanoscale materials and structures: fabrication and characterization, FOS: Physical sciences, Physics::Optics, General Physics and Astronomy, 02 engineering and technology, 01 natural sciences, Electromagnetic radiation, Resonator, Negative refraction, 0103 physical sciences, Multilayers superlattices, 010306 general physics, Lithography, [PHYS.PHYS.PHYS-OPTICS]Physics [physics]/Physics [physics]/Optics [physics.optics], business.industry, Metamaterial, photonic structures, 021001 nanoscience & nanotechnology, metamaterials, Optical materials, Optoelectronics, Nanometre, 0210 nano-technology, business, Physics - Optics, Optics (physics.optics), Visible spectrum
Abstract

The concept of metamaterials emerged in years 2000 with the achievement of artificial structures enabling non conventional propagation of electromagnetic waves, such as negative phase velocity of negative refraction. The electromagnetic response of metamaterials is generally based on the presence of optically-resonant elements (or meta-atoms) of sub-wavelength size and well designed morphology so as to provide the desired electric and magnetic optical properties. Top-down technologies based on lithography techniques have been intensively used to fabricate a variety of efficient electric and magnetic resonators operating from microwave to visible light frequencies. However, the technological limits of the top-down approach are reached in visible light where a huge number of nanometre sized elements is required. We show here that the bottom-up fabrication route based on the combination of nanochemistry and of the self-assembly methods of colloidal physics provide an excellent alternative for the large scale synthesis of complex meta-atoms, as well as for the fabrication of 2D and 3D samples exhibiting meta-properties in visible light., Comment: 8 pages, 7 figures

Published
2017
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34. GoldHelix: Gold Nanoparticles Forming 3D Helical Superstructures with Controlled Morphology and Strong Chiroptical Property

Author

Jie Gao, Guillaume Le Saux, P. Barois, Virginie Ponsinet, Ovidiu Ersen, Jiaji Cheng, Thierry Buffeteau, Reiko Oda, Yann Battie, Marie-Hélène Delville, Emilie Pouget, Chimie et Biologie des Membranes et des Nanoobjets (CBMN), Université de Bordeaux (UB)-École Nationale d'Ingénieurs des Travaux Agricoles - Bordeaux (ENITAB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Moléculaires (ISM), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie et Physique - Approche Multi-échelle des Milieux Complexes (LCP-A2MC), Université de Lorraine (UL), Centre de Recherche Paul Pascal (CRPP), Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie de la Matière Condensée de Bordeaux (ICMCB), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Université de Bordeaux (UB), Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université de Strasbourg (UNISTRA)-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)-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)-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), CNRS and CEA METSA (Microscopie Electronique et Sonde Atomique) network (FR3507)., ANR-10-IDEX-0003,IDEX BORDEAUX,Initiative d'excellence de l'Université de Bordeaux(2010), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Bordeaux (UB)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), 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), Teulet, Nadine, Initiative d'excellence de l'Université de Bordeaux - - IDEX BORDEAUX2010 - ANR-10-IDEX-0003 - IDEX - VALID, École Nationale d'Ingénieurs des Travaux Agricoles - Bordeaux (ENITAB)-Institut de Chimie du CNRS (INC)-Université de Bordeaux (UB)-Centre National de la Recherche Scientifique (CNRS), and Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Université Sciences et Technologies - Bordeaux 1-Université Montesquieu - Bordeaux 4-Institut de Chimie du CNRS (INC)

Subjects
Circular dichroism, Chiral nanostructures, Materials science, Morphology (linguistics), General Physics and Astronomy, Nanotechnology, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Circular dichroism of plasmon, Nanomaterials, Gold nanoparticles, [PHYS.PHYS] Physics [physics]/Physics [physics], General Materials Science, Surface plasmon resonance, Spectroscopy, Plasmonic nanoparticles, Nanoscopic scale, [CHIM.MATE] Chemical Sciences/Material chemistry, [PHYS.PHYS]Physics [physics]/Physics [physics], General Engineering, Silica, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Chiroptical properties, Colloidal gold, 0210 nano-technology
Abstract

International audience; Plasmonic nanoparticles, particularly gold nanoparticles (GNPs) hold a great potential as structural and functional building blocks for three-dimensional (3D) nanoarchitectures with specific optical applications. However, a rational control of their assembly into nanoscale superstructures with defined positioning and overall arrangement still remains challenging. Herein, we propose a solution to this challenge by using as building blocks: (1) nanometric silica helices with tunable handedness and sizes as a matrix and (2) GNPs with diameter varying from 4 to 10 nm to prepare a collection of helical GNPs superstructures (called Goldhelices hereafter). These nanomaterials exhibit well-defined arrangement of GNPs following the helicity of the silica template. Strong chiroptical activity is evidenced by circular dichroism (CD) spectroscopy at the wavelength of the surface plasmon resonance (SPR) of the GNPs with a anisotropy factor (g-factor) of the order of 1 × 10−4, i.e., 10-fold larger than what is typically reported in the literature. Such CD signals were simulated using a coupled dipole method which fit very well the experimental data. The measured signals are 1−2 orders of magnitude lower than the simulated signals, which is explained by the disordered GNPs grafting, the polydispersity of the GNPs, and the dimension of the nanohelices.....

Published
2017
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35. Kinetics of avidin-induced clearance of biotinylated bimodal liposomes for improved MR molecular imaging

Author

Klaas Nicolay, Geralda A. F. van Tilborg, Gustav J. Strijkers, Nico A. J. M. Sommerdijk, Emilie Pouget, Willem J. M. Mulder, and Chris P. M. Reutelingsperger

Subjects
Liposome, Pathology, medicine.medical_specialty, biology, chemistry.chemical_compound, Biotin, chemistry, In vivo, Biotinylation, PEG ratio, Biophysics, medicine, biology.protein, Radiology, Nuclear Medicine and imaging, Molecular imaging, Ex vivo, Avidin
Abstract

Dual labeled liposomes, carrying both paramagnetic and fluorescent lipids, were recently proposed as potent contrast agents for MR molecular imaging. These nanoparticles are coated with poly(ethylene glycol) (PEG) to increase their blood circulation half-life, which should allow extensive accumulation at the targeted site. To eliminate nonspecific blood pool signal from the MR images, the circulating liposomes should ideally be cleared from the circulation when sufficient target-specific contrast enhancement is obtained. To that aim, we designed an avidin chase that allowed controlled and rapid clearance of paramagnetic biotinylated liposomes from the blood circulation in C57BL/6 mice. Avidin-induced alterations in blood clearance kinetics and tissue distribution were studied quantitatively by determination of the Gd content in blood and tissue samples ex vivo. Intrinsic liposomal blood clearance showed bi-exponential behavior with half-lives t1/2α = 2.1 ± 1.1 and t1/2β = 15.1 ± 5.4 hours, respectively. In contrast, the contrast agent was cleared from the blood by the avidin infusion to

Published
2008
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36. Noncovalent triblock copolymers based on coiled-coil peptide motif

Author

Hana Robson Marsden, Nico A. J. M. Sommerdijk, Alexander Kros, Emilie Pouget, Sandra J. Veen, Ellen N. M. van Leeuwen, Alexander V. Korobko, Materials and Interface Chemistry, and Chemical Engineering and Chemistry

Subjects
Models, Molecular, Circular dichroism, Light, Molecular Conformation, Biochemistry, Micelle, Protein Structure, Secondary, Catalysis, Polyethylene Glycols, chemistry.chemical_compound, Colloid and Surface Chemistry, Dynamic light scattering, Biomimetic Materials, Polymer chemistry, Amphiphile, Copolymer, Scattering, Radiation, Protein Structure, Quaternary, Micelles, Coiled coil, Chemistry, Circular Dichroism, Temperature, technology, industry, and agriculture, General Chemistry, Polystyrenes, Polystyrene, Peptides, Ethylene glycol
Abstract

The formation of a noncovalent triblock copolymer based on a coiled-coil peptide motif is demonstrated in solution. A specific peptide pair (E and K) able to assemble into heterocoiled coils was chosen as the middle block of the polymer and conjugated to poly(ethylene glycol) (PEG) and polystyrene (PS) as the outer blocks. Mixing equimolar amounts of the polymer-peptide block copolymers PS-E and K-PEG resulted in the formation of coiled-coil complexes between the peptides and subsequently in the formation of the amphiphilic triblock copolymer PS-E/K-PEG. Aqueous self-assembly of the separate peptides (E and K), the block copolymers (PS-E and K-PEG), and equimolar mixtures thereof was studied by circular dichroism, dynamic light scattering, and cryogenic transmission electron microscopy. It was found that the noncovalent PS-E/K-PEG copolymer assembled into rodlike micelles, while in all other cases, spherical micelles were observed. Temperature-dependent studies revealed the reversible nature of the coiled-coil complex and the influence of this on the morphology of the aggregate. A possible mechanism for these transitions based on the interfacial free energy and the free energy of the hydrophobic blocks is discussed. The self-assembly of the polymer-peptide conjugates is compared to that of polystyrene-b-poly(ethylene glycol), emphasizing the importance of the coiled-coil peptide block in determining micellar structure and dynamic behavior.

Published
2008
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37. Hierarchical architectures by synergy between dynamical template self-assembly and biomineralization

Author

Maïté Paternostre, Thomas M. Weiss, Emilie Pouget, Alain Moréac, Annie Cavalier, Erik Dujardin, Franck Artzner, Anne Renault, Valérie Marchi-Artzner, Céline Valéry, Groupe matière condensée et matériaux (GMCM), Centre National de la Recherche Scientifique (CNRS)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES), Centre d'élaboration de matériaux et d'études structurales (CEMES), 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 de Toulouse (ICT-FR 2599), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA), Interactions cellulaires et moléculaires (ICM), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), European Synchrotron Radiation Facility (ESRF), Protéines membranaires transductrices d'énergie (PMTE), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Nanostructure, Materials science, Static Electricity, Supramolecular chemistry, Nanotechnology, 02 engineering and technology, Spectrum Analysis, Raman, 010402 general chemistry, Peptides, Cyclic, 01 natural sciences, Microscopy, Electron, Transmission, Biomimetics, Phase (matter), Scattering, Radiation, General Materials Science, Nanotubes, X-Rays, Mechanical Engineering, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, Silicon Dioxide, 021001 nanoscience & nanotechnology, Condensed Matter Physics, Nanostructures, 0104 chemical sciences, Kinetics, Template, Models, Chemical, Mechanics of Materials, Nanometre, Self-assembly, Crystallization, Somatostatin, 0210 nano-technology, Biomineralization
Abstract

International audience; Diatoms, shells, bones and teeth are exquisite examples of well-defined structures, arranged from nanometre to macroscopic length scale, produced by natural biomineralization using organic templates to control the growth of the inorganic phase. Although strategies mimicking Nature have partially succeeded in synthesizing human-designed bio-inorganic composite materials, our limited understanding of fundamental mechanisms has so far kept the level of hierarchical complexity found in biological organisms out of the chemists' reach. In this letter, we report on the synthesis of unprecedented double-walled silica nanotubes with monodisperse diameters that self-organize into highly ordered centimetre-sized fibres. A unique synergistic growth mechanism is elucidated by the combination of light and electron microscopy, synchrotron X-ray diffuse scattering and Raman spectroscopy. Following this growth mechanism, macroscopic bundles of nanotubules result from the kinetic cross-coupling of two molecular processes: a dynamical supramolecular self-assembly and a stabilizing silica mineralization. The feedback actions between the template growth and the inorganic deposition are driven by a mutual electrostatic neutralization. This 'dynamical template' concept can be further generalized as a rational preparation scheme for materials with well-defined multiscale architectures and also as a fundamental mechanism for growth processes in biological systems.

Published
2007
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38. On the Crystalline Structures of Poly(tetramethylene adipate)

Author

Emilie Pouget, Ahmed Almontassir, María Teresa Casas, and Jordi Puiggalí

Subjects
Diffraction, Materials science, Polymers and Plastics, Organic Chemistry, Epitaxy, Inorganic Chemistry, Polyester, Crystallography, Electron diffraction, Adipate, Polymer chemistry, Materials Chemistry, Orthorhombic crystal system, Lamellar structure, Monoclinic crystal system
Abstract

Structural analyses have been undertaken with the monoclinic and orthorhombic crystalline structures of polyester 4 6. X-ray diffraction patterns performed at 50 °C and electron diffraction patterns from single crystals, solution-grown films, and epitaxial crystallizations have been considered. Skew CH2CH2−OC(O) bonds and a P121/n1 space group were postulated for the monoclinic structure (α-form). Molecular packing was optimized from electron diffraction data and a final R factor of 0.19 was obtained. The orthorhombic structure (β-form) is characterized by an extended conformation and a molecular packing similar to polyethylene. Thus, an R factor of 0.11 is calculated for a setting angle of 40°, taking into account the electron diffraction data. A regular folding habit is found in the lamellar surfaces of crystals belonging to the β-form, whereas an irregular folding habit is characteristic of the α-form.

Published
2003
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39. The binding of CNA35 contrast agents to collagen fibrils

Author

Emilie Pouget, Nico A. J. M. Sommerdijk, Giuseppe Falini, Honorius M. H. F. Sanders, Michele Iafisco, Klaas Nicolay, Maarten Merkx, Paul H. H. Bomans, Gustav J. Strijkers, Fabio Nudelman, H.M.H.F. Sander, M. Iafisco, E.M. Pouget, G. Falini, K. Nicolay, N.A.J.M. Sommerdijk, Materials and Interface Chemistry, Protein Engineering, Macro-Organic Chemistry, Adult Psychiatry, ACS - Amsterdam Cardiovascular Sciences, CCA -Cancer Center Amsterdam, and Radiology and Nuclear Medicine

Subjects
collagen, MRI contrast agent, Contrast Media, macromolecular substances, Micelle, bacterial protein, Catalysis, Collagen fibril, Bacterial protein, chemistry.chemical_compound, Microscopy, Electron, Transmission, Materials Chemistry, Animals, Horses, Binding site, Micelles, Collagen type, Liposome, Binding Sites, Cryoelectron Microscopy, Metals and Alloys, General Chemistry, Magnetic Resonance Imaging, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Monomer, Biochemistry, chemistry, Liposomes, liposome, Ceramics and Composites, Biophysics
Abstract

CryoTEM demonstrates that a CNA35-bearing liposomal MRI contrast agent selectively binds to poorly assembled collagen type I as opposed to well-assembled collagen fibrils, whereas monomeric CNA35 binds to all forms of collagen. It is shown that upon conjugation to liposomes and micelles CNA35 loses its ability to dissociate ordered collagen fibrils and thereby to create its own binding sites.

Published
2011
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40. Chiral colloids: homogeneous suspension of individualized SiO2 helical and twisted nanoribbons

Author

Reiko Oda, Emilie Pouget, Marie-Hélène Delville, Marie-Christine Durrieu, Dmytro Dedovets, Gregor Kemper, Jiaji Cheng, Makoto Takafuji, Hirotaka Ihara, Yutaka Okazaki, Department of Applied Chemistry and Biochemistry, Kumamoto University, Chimie et Biologie des Membranes et des Nanoobjets (CBMN), Université de Bordeaux (UB)-École Nationale d'Ingénieurs des Travaux Agricoles - Bordeaux (ENITAB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie de la Matière Condensée de Bordeaux (ICMCB), and Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Université de Bordeaux (UB)

Subjects
Materials science, Sonication, General Engineering, General Physics and Astronomy, Nanotechnology, [CHIM.MATE]Chemical Sciences/Material chemistry, 02 engineering and technology, Carbon nanotube, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, law.invention, Solvent, Colloid, Homogeneous, law, General Materials Science, Nanometre, 0210 nano-technology
Abstract

International audience; Finely tuned chiral nanometric silica fibers were synthesized based on sol-gel chemistry using organic self-assembly as a template. The optimization of the sol-gel process in acidic conditions allowed us to reduce the transcription time by a factor of 10. These nanohelices were successfully fragmented while preserving the fine internal structures from several micrometers to several hundreds of nanometers in length by a sonication method previously reported for carbon nanotubes. By carefully choosing the nature of the solvent, the sonication power, pH in the case of water, and densification of the silica walls by freeze-drying, the homogeneous and stable colloidal suspensions of individualized chiral nanometric silica ribbons with controlled length were obtained.

Published
2014
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42. Dispersions of Monodisperse Hybrid Rod-Like Particles by Mineralization of Filamentous Viruses

Author

Emilie Pouget, Eric Grelet, Centre de recherches Paul Pascal (CRPP), and Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Steric effects, Materials science, Dispersity, Nanotechnology, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Mineralization (biology), Colloid, Hydrophilic polymers, Microscopy, Electron, Transmission, Polymer functionalization, Electrochemistry, General Materials Science, Particle Size, Spectroscopy, Titanium, Aqueous solution, Surfaces and Interfaces, Silicon Dioxide, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 0104 chemical sciences, Chemical engineering, Viruses, Inorganic materials, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], 0210 nano-technology
Abstract

International audience; In this work, we report on the synthesis through a direct chemical approach of hybrid organic/inorganic rod-like particles with a very high aspect ratio (length/diameter) by the use of a biotemplate, the fd virus. A synthetic route is proposed based on an initial step of steric stabilization of the colloidal template by hydrophilic polymer grafting. Thanks to this polymer functionalization, the filamentous viruses are well-dispersed in solution during their mineralization by different inorganic salts, leading to suspensions of individual hybrid rod-like particles such as virus/SiO2 and virus/TiO2. This aqueous solution based approach is shown to be highly reproducible, scalable for large production synthesis, and versatile to different inorganic materials.

Published
2013
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43. Fractional Hoppinglike Motion in Columnar Mesophases of Semiflexible Rodlike Particles

Author

Emilie Pouget, Paul van der Schoot, M. Paul Lettinga, Pierre Ballesta, Eric Grelet, M. Saber Naderi, Soft Matter and Biological Physics, Faculteit Technische Natuurkunde, Faculteit Technische Naturkunde, Laboratory for Acoustics and Thermal Physics [Leuven], Catholic University of Leuven - Katholieke Universiteit Leuven (KU Leuven), Centre de recherches Paul Pascal (CRPP), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Weiche Materie (ICS-3), Institut Weiche Materie, Instituut voor Theoretische Fysica, Universiteit Utrecht, Theoretical Physics, and Afd Theoretical Physics (ITF)

Subjects
Materials science, Condensed matter physics, 61.30.Hn, 61.30.Dk, 82.70.Dd, Dynamics (mechanics), General Physics and Astronomy, Motion (geometry), 01 natural sciences, 010305 fluids & plasmas, Condensed Matter::Soft Condensed Matter, Colloid, Classical mechanics, 0103 physical sciences, Brownian dynamics, Jump, ddc:550, Length distribution, Collective dynamics, 010306 general physics, Columnar phase
Abstract

International audience; We report on single-particle dynamics of strongly interacting filamentous fd virus particles in the liquidcrystalline columnar state in aqueous solution. From fluorescence microscopy, we find that rare, discrete events take place, in which individual particles engage in sudden, jumplike motion along the main rod axis. The jump length distribution is bimodal and centered at half- and full-particle lengths. Our Brownian dynamics simulations of hard semiflexible particles mimic our experiments and indicate that full-length jumps must be due to collective dynamics in which particles move in stringlike fashion in and between neighboring columns, while half jumps arise as a result of particles moving into defects. We find that the finite domain structure of the columnar phase strongly influences the observed dynamics.

Published
2013
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44. Control of peptide nanotube diameter by chemical modifications of an aromatic residue involved in a single close contact

Author

Christophe Tarabout, Franck Artzner, Frédéric Gobeaux, François Besselievre, Emilie Pouget, Cristelle Mériadec, Céline Valéry, Daryl Thomas, Michel Petitjean, Maarten IJsselstijn, Maïté Paternostre, Jean-Marc Verbavatz, Luc Perrin, David-Alexandre Buisson, Jean-Christophe Cintrat, Stéphane Roux, Nicolas Fay, Melinda Ligeti, Bernard Rousseau, Institut de Physique de Rennes (IPR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS), Institut de Biologie et de Technologies de Saclay (IBITECS), Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Système membranaires, photobiologie, stress et détoxication (SMPSD), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS), Interactions cellulaires et moléculaires (ICM), Ipsen-Pharman, Ipsen-Pharma, De Villemeur, Hervé, Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay

Subjects
Models, Molecular, Nanotubes, Peptide, Nanotube, Materials science, Silicon dioxide, Chemical structure, MESH: Somatostatin, Dispersity, MESH: Molecular Structure, Supramolecular chemistry, [SDV.BBM.BP] Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biophysics, Nanotechnology, 02 engineering and technology, MESH: Microscopy, Electron, 010402 general chemistry, Peptides, Cyclic, 01 natural sciences, MESH: Silicon Dioxide, Nanomaterials, Amino Acids, Aromatic, chemistry.chemical_compound, X-Ray Diffraction, Scattering, Small Angle, [SDV.BBM] Life Sciences [q-bio]/Biochemistry, Molecular Biology, Molecule, [SDV.BBM]Life Sciences [q-bio]/Biochemistry, Molecular Biology, MESH: Nanotubes, Peptide, MESH: Nanotechnology, MESH: Peptides, Cyclic, MESH: Scattering, Small Angle, Multidisciplinary, Molecular Structure, MESH: X-Ray Diffraction, Chemical modification, Silicon Dioxide, 021001 nanoscience & nanotechnology, 0104 chemical sciences, MESH: Amino Acids, Aromatic, [SDV.BBM.BP]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biophysics, Microscopy, Electron, chemistry, Physical Sciences, Somatostatin, 0210 nano-technology, MESH: Models, Molecular
Abstract

International audience; Supramolecular self-assembly is an attractive pathway for bottom-up synthesis of novel nanomaterials. In particular, this approach allows the spontaneous formation of structures of well-defined shapes and monodisperse characteristic sizes. Because nanotechnology mainly relies on size-dependent physical phenomena, the control of monodispersity is required, but the possibility of tuning the size is also essential. For self-assembling systems, shape, size, and monodispersity are mainly settled by the chemical structure of the building block. Attempts to change the size notably by chemical modification usually end up with the loss of self-assembly. Here, we generated a library of 17 peptides forming nanotubes of monodisperse diameter ranging from 10 to 36 nm. A structural model taking into account close contacts explains how a modification of a few Å of a single aromatic residue induces a fourfold increase in nanotube diameter. The application of such a strategy is demonstrated by the formation of silica nanotubes of various diameters.

Published
2011
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45. Dynamics in the smectic phase of stiff viral rods

Author

Eric Grelet, Emilie Pouget, and M. Paul Lettinga

Subjects
Persistence length, Phase transition, Materials science, genetic structures, Diffusion, Dispersity, FOS: Physical sciences, Nanotechnology, Condensed Matter - Soft Condensed Matter, Rod, Colloid, Chemical physics, Phase (matter), Particle, Soft Condensed Matter (cond-mat.soft), ddc:530, sense organs
Abstract

We report on the dynamics in colloidal suspensions of stiff viral rods, called fd-Y21M. This mutant filamentous virus exhibits a persistence length 3.5 times larger than the wild-type fd-wt. Such a virus system can be used as a model system of rodlike particles for studying their self-diffusion. In this paper, the physical features, such as rod contour length and polydispersity have been determined for both viruses. The effect of viral rod flexibility on the location of the nematic-smectic phase transition has been investigated, with a focus on the underlying dynamics studied more specifically in the smectic phase. Direct visualization of the stiff fd-Y21M at the scale of a single particle has shown the mass transport between adjacent smectic layers, as found earlier for the more flexible rods. We could relate this hindered diffusion with the smectic ordering potentials for varying rod concentrations. The self-diffusion within the layers is far more pronounced for the stiff rods as compared to the more flexible fd-wt viral rod., Comment: 6 pages, 5 figures

Published
2011
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46. Elucidation of the self-assembly pathway of lanreotide octapeptide into beta-sheet nanotubes: role of two stable intermediates

Author

Emilie Pouget, Franck Artzner, Maïté Paternostre, Nicolas Fay, Patrick Berthault, Céline Valéry, Erik Dujardin, Nadège Jamin, Thierry Rose, Lionel Perrin, Daniel Thomas, Anjali Pandit, Institut de Physique de Rennes (IPR), Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS), Institut de Biologie et de Technologies de Saclay (IBITECS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay, Centre d'élaboration de matériaux et d'études structurales (CEMES), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), Institut Rayonnement Matière de Saclay (IRAMIS), Biophysique des Macromolécules et de leurs Interactions, Institut Pasteur [Paris] (IP)-Centre National de la Recherche Scientifique (CNRS), Interactions cellulaires et moléculaires (ICM), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS), Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), 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 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)-Institut de Chimie du CNRS (INC)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA), and Institut Pasteur [Paris]-Centre National de la Recherche Scientifique (CNRS)

Subjects
Nanotube, Magnetic Resonance Spectroscopy, Surface Properties, Dimer, Molecular Sequence Data, Supramolecular chemistry, Beta sheet, Nanotechnology, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Biochemistry, Peptides, Cyclic, Catalysis, Protein Structure, Secondary, chemistry.chemical_compound, Colloid and Surface Chemistry, Molecule, Amino Acid Sequence, Mesoscopic physics, Nanotubes, Molecular Structure, [SDV.BBM.BS]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Structural Biology [q-bio.BM], Rational design, General Chemistry, 021001 nanoscience & nanotechnology, Silicon Dioxide, Transition state, 0104 chemical sciences, chemistry, 0210 nano-technology, Peptides, Somatostatin
Abstract

International audience; Nanofabrication by molecular self-assembly involves the design of molecules and self-assembly strategies so that shape and chemical complementarities drive the units to organize spontaneously into the desired structures. The power of self-assembly makes it the ubiquitous strategy of living organized matter and provides a powerful tool to chemists. However, a challenging issue in the self-assembly of complex supramolecular structures is to understand how kinetically efficient pathways emerge from the multitude of possible transition states and routes. Unfortunately, very few systems provide an intelligible structure and formation mechanism on which new models can be developed. Here, we elucidate the molecular and supramolecular self-assembly mechanism of synthetic octapeptide into nanotubes in equilibrium conditions. Their complex hierarchical self-assembly has recently been described at the mesoscopic level, and we show now that this system uniquely exhibits three assembly stages and three intermediates: (i) a peptide dimer is evidenced by both analytical centrifugation and NMR translational diffusion experiments; (ii) an open ribbon and (iii) an unstable helical ribbon are both visualized by transmission electron microscopy and characterized by small angle X-ray scattering. Interestingly, the structural features of two stable intermediates are related to the final nanotube organization as they set, respectively, the nanotube wall thickness and the final wall curvature radius. We propose that a specific self-assembly pathway is selected by the existence of such preorganized and stable intermediates so that a unique final molecular organization is kinetically favored. Our findings suggests that the rational design of oligopeptides can encode both molecular- and macro-scale morphological characteristics of their higher-order assemblies, thus opening the way to ultrahigh resolution peptide scaffold engineering.

Published
2010
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47. Un échafaudage de peptides pour fabriquer des nanotubes de silice : Une organisation très hiérarchique

Author

Emilie Pouget, Christophe Tarabout, Daphné Duval, Bruno Bêche, Pascal Panizza, Maite Paternostre, Franck Artzner, Institut de Physique de Rennes (IPR), Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS), Biophysique, Groupe matière condensée et matériaux (GMCM), Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS)-Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS)-Institut de Physique de Rennes (IPR), Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Institut de Biologie et de Technologies de Saclay (IBITECS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay, Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS)-Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut de Physique de Rennes (IPR), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), and Destouches, Dorothée

Published
2009

48. Biominéralisation : de la compréhension d'architectures naturelles aux nanomatériaux bio-inspirés

Author

Emilie Pouget, Franck Artzner, and Erik Dujardin

Abstract

La biomineralisation regroupe les processus de mineralisation naturels qui fournissent une grande variete de structures inorganiques telles que les dents, les os, les coquilles et les carapaces. Ces proprietes ont ete optimisees par selection naturelle pour une fonction donnee et elles atteignent des performances remarquables, qui fascinent les chimistes des materiaux. Inspiree par ces procedes, il s'est developpe durant les deux dernieres decennies une chimie s'exercant dans des conditions environnementales physiologiques appelee « chimie douce ». Le domaine de la biomineralisation s'est alors etendu a de nouvelles strategies de synthese des materiaux inspirees des procedes observes chez les organismes vivants.

Published
2009
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49. New practical approach of integrated photonic based on biomimetic peptidic/silica self-assembled nanotubes

Author

Emilie Pouget, Franck Artzner, Anne Renault, Bruno Bêche, Nolwenn Huby, Christophe Tarabout, Joseph Zyss, Daphné Duval, Etienne Gaviot, Institut de Physique de Rennes (IPR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS), Biophysique, Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS)-Université de Rennes 1 (UR1), Laboratoire d'Acoustique de l'Université du Mans (LAUM), Centre National de la Recherche Scientifique (CNRS)-Le Mans Université (UM), Laboratoire de Photonique Quantique et Moléculaire (LPQM), École normale supérieure - Cachan (ENS Cachan)-CentraleSupélec-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS)-Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS), and Le Mans Université (UM)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Coupling, Photon, Materials science, business.industry, 010401 analytical chemistry, Physics::Optics, Nanotechnology, Heterojunction, 02 engineering and technology, Condensed Matter::Mesoscopic Systems and Quantum Hall Effect, 021001 nanoscience & nanotechnology, Chip, 01 natural sciences, 0104 chemical sciences, Optical properties of carbon nanotubes, Condensed Matter::Materials Science, Molecular self-assembly, Self-assembly, Photonics, 0210 nano-technology, business
Abstract

International audience; We report on the first developments for a new approach of integrated photonic using optical evanescent coupling from organic microstructures to bundles of hybrid nanotubes (NT). Microstructures are organic disks acting as photon reservoirs, integrated on a photonic chip fabricated by micro-technologic processes. Biomimetic peptidic/ silica nanotubes are realized by molecular self-assembly allowing high aspect ratio. Such heterostructures have been included directly on the organic chip as an innovative solution based on nanotubes in situ chipapproach. The latter allowed us to obtain an adequate evanescent coupling localized between micronic-disks and bundles of nanotubes. As a result, we highlight a specific photonic propagation along various heterostructured- NT-bundles featuring distances beyond the centimeter and losses from 1.2 to 6.6 dB/cm. It presents an advantageous confinement of the optical mode marked with strong energy localizations between nanotubes.

Published
2009
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50. Molecular origin of the self-assembly of lanreotide into nanotubes : a mutational approach

Author

Maïté Paternostre, Jean-Marc Verbavatz, Franck Artzner, Anjali Pandit, Laurent Bordes, Céline Valéry, Isabelle Boisdé, Roland Cherif-Cheikh, Emilie Pouget, Groupe matière condensée et matériaux ( GMCM ), Université de Rennes 1 ( UR1 ), Université de Rennes ( UNIV-RENNES ) -Université de Rennes ( UNIV-RENNES ) -Centre National de la Recherche Scientifique ( CNRS ), Système membranaires, photobiologie, stress et détoxication ( SMPSD ), Commissariat à l'énergie atomique et aux énergies alternatives ( CEA ) -Centre National de la Recherche Scientifique ( CNRS ), Institut de Biologie et de Technologies de Saclay ( IBITECS ), Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives ( CEA ), Service de Bioénergétique, Biologie Stucturale, et Mécanismes ( SB2SM ), Centre National de la Recherche Scientifique ( CNRS ) -Institut de Biologie Intégrative de la Cellule ( I2BC ), Université Paris-Sud - Paris 11 ( UP11 ) -Commissariat à l'énergie atomique et aux énergies alternatives ( CEA ) -Université Paris-Saclay-Centre National de la Recherche Scientifique ( CNRS ) -Université Paris-Sud - Paris 11 ( UP11 ) -Commissariat à l'énergie atomique et aux énergies alternatives ( CEA ) -Université Paris-Saclay-Centre National de la Recherche Scientifique ( CNRS ), Institut des Sciences Chimiques de Rennes ( ISCR ), Université de Rennes ( UNIV-RENNES ) -Université de Rennes ( UNIV-RENNES ) -Ecole Nationale Supérieure de Chimie de Rennes-Institut National des Sciences Appliquées ( INSA ) -Centre National de la Recherche Scientifique ( CNRS ), Groupe matière condensée et matériaux (GMCM), Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS), Système membranaires, photobiologie, stress et détoxication (SMPSD), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS), Institut de Biologie et de Technologies de Saclay (IBITECS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay, Service de Bioénergétique, Biologie Stucturale, et Mécanismes (SB2SM), Institut de Biologie Intégrative de la Cellule (I2BC), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Lentz, Celine, Centre National de la Recherche Scientifique (CNRS)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES), Centre National de la Recherche Scientifique (CNRS)-Institut de Biologie Intégrative de la Cellule (I2BC), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)

Subjects
Halobacterium salinarum, Nanotubes, Peptide, Nanotube, Amyloid, [ SDV.BBM.BP ] Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biophysics, Stereochemistry, Protein Conformation, Dispersity, Molecular Sequence Data, Biophysics, Supramolecular Assemblies, [SDV.BBM.BP] Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biophysics, Peptide, 02 engineering and technology, Lanreotide, Spectrum Analysis, Raman, Peptides, Cyclic, 03 medical and health sciences, chemistry.chemical_compound, Residue (chemistry), Amino Acids, Aromatic, Spectroscopy, Fourier Transform Infrared, Side chain, Molecule, Amino Acid Sequence, 030304 developmental biology, chemistry.chemical_classification, 0303 health sciences, Microscopy, Binding Sites, Lysine, Water, 021001 nanoscience & nanotechnology, Solutions, [SDV.BBM.BP]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biophysics, Directed mutagenesis, chemistry, Mutation, 0210 nano-technology, Somatostatin, Hydrophobic and Hydrophilic Interactions
Abstract

Lanreotide, a synthetic, therapeutic octapeptide analog of somatostatin, self-assembles in water into perfectly hollow and monodisperse (24-nm wide) nanotubes. Lanreotide is a cyclic octapeptide that contains three aromatic residues. The molecular packing of the peptide in the walls of a nanotube has recently been characterized, indicating four hierarchical levels of organization. This is a fascinating example of spontaneous self-organization, very similar to the formation of the gas vesicle walls of Halobacterium halobium. However, this unique peptide self-assembly raises important questions about its molecular origin. We adopted a directed mutation approach to determine the molecular parameters driving the formation of such a remarkable peptide architecture. We have modified the conformation by opening the cycle and by changing the conformation of a Lys residue, and we have also mutated the aromatic side chains of the peptide. We show that three parameters are essential for the formation of lanreotide nanotubes: i), the specificity of two of the three aromatic side chains, ii), the spatial arrangement of the hydrophilic and hydrophobic residues, and iii), the aromatic side chain in the β-turn of the molecule. When these molecular characteristics are modified, either the peptides lose their self-assembling capability or they form less-ordered architectures, such as amyloid fibers and curved lamellae. Thus we have determined key elements of the molecular origins of lanreotide nanotube formation.

Published
2008

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