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26 results on '"Fabienne Testard"'

1. UV-Visible photo-reactivity of permanently polarized inorganic nanotubes coupled to gold nanoparticles

Author

Sabyasachi Patra, Fabienne Testard, Frédéric Gobeaux, Lorette Sicard, Delphine Shaming, Sophie Le Caër, Antoine Thill, Laboratoire Interdisciplinaire sur l'Organisation Nanométrique et Supramoléculaire (LIONS), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Radiochemistry division, Bhabha Atomic Research Centre, 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 Paris Cité (UPCité)

Subjects
plasmon, imogolite, nanotube, [CHIM]Chemical Sciences, General Materials Science, photocatalysis, gold nanoparticle
Abstract

International audience; Hybrid aluminosilicate nanotubes (Imo-CH3) have the ability to trap small organic molecules inside their hydrophobic internal cavity while being dispersed in water owing to their hydrophilic external surface. They also display a curvature-induced polarization of their wall, which favors reduction outside the nanotubes and oxidation inside. Here, we coupled bare plasmonic gold nanoparticles (GNPs) with Imo-CH3 and analyzed for the first time the redox reactivity of these hybrid nano-reactors upon UV illumination. We show that the coupling between GNPs and Imo-CH3 significantly enhances the nanotube photocatalytic activity, with a large part of water reduction occurring directly on the gold surface. The coupling mechanism strongly influences the initial H2 production rate, which can go from ×10 to more than ×90 as compared to bare Imo-CH3 depending on the synthesis route of the GNPs. The present results show that this hybrid photocatalytic nano-reactor benefits from a synergy of polarization and confinement effects that facilitate efficient H2 production.

Published
2023
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2. Coexistence of Transient Liquid Droplets and Amorphous Solid Particles in Nonclassical Crystallization of Cerium Oxalate

Author

Maxime Durelle, Sophie Charton, Frédéric Gobeaux, Corinne Chevallard, Luc Belloni, Fabienne Testard, Sylvain Trépout, David Carriere, Laboratoire Interdisciplinaire sur l'Organisation Nanométrique et Supramoléculaire (LIONS), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Département de recherche sur les procédés pour la mine et le recyclage du combustible (DMRC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Multimodal Imaging Center (Centre d'Imagerie Multimodale) (MIC), and Institut Curie [Paris]-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)

Subjects
General Materials Science, [CHIM.MATE]Chemical Sciences/Material chemistry, Physical and Theoretical Chemistry
Abstract

International audience; Crystallization from solution often occurs via “nonclassical” routes; that is, it involves transient, non-crystalline states like reactant-rich liquid droplets and amorphous particles. However, in mineral crystals, the well-defined thermodynamic character of liquid droplets and whether they convert─or not─into amorphous phases have remained unassessed. Here, by combining cryo-transmission electron microscopy and X-ray scattering down to a 250 ms reaction time, we unveil that crystallization of cerium oxalate involves a metastable chemical equilibrium between transient liquid droplets and solid amorphous particles: contrary to the usual expectation, reactant-rich droplets do not evolve into amorphous solids. Instead, at concentrations above 2.5 to 10 mmol L–1, both amorphous and reactant-rich liquid phases coexist for several tens of seconds and their molar fractions remain constant and follow the lever rule in a multicomponent phase diagram. Such a metastable chemical equilibrium between solid and liquid precursors has been so far overlooked in multistep nucleation theories and highlights the interest of rationalizing phase transformations using multicomponent phase diagrams not only when designing and recycling rare earths materials but also more generally when describing nonclassical crystallization.

Published
2022
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3. Metrological Protocols for Reaching Reliable and SI-Traceable Size Results for Multi-Modal and Complexly Shaped Reference Nanoparticles

Author

Nicolas Feltin, Loïc Crouzier, Alexandra Delvallée, Francesco Pellegrino, Valter Maurino, Dorota Bartczak, Heidi Goenaga-Infante, Olivier Taché, Sylvie Marguet, Fabienne Testard, Sébastien Artous, François Saint-Antonin, Christoph Salzmann, Jérôme Deumer, Christian Gollwitzer, Richard Koops, Noham Sebaïhi, Richard Fontanges, Matthias Neuwirth, Detlef Bergmann, Dorothee Hüser, Tobias Klein, and Vasile-Dan Hodoroaba

Subjects
certified reference nanomaterials, traceable nanoparticle size measurements, hybrid metrology, scanning probe microscopy, small-angle X-ray scattering, electron microscopy, General Chemical Engineering, General Materials Science
Abstract

The study described in this paper was conducted in the framework of the European nPSize project (EMPIR program) with the main objective of proposing new reference certified nanomaterials for the market in order to improve the reliability and traceability of nanoparticle size measurements. For this purpose, bimodal populations as well as complexly shaped nanoparticles (bipyramids, cubes, and rods) were synthesized. An inter-laboratory comparison was organized for comparing the size measurements of the selected nanoparticle samples performed with electron microscopy (TEM, SEM, and TSEM), scanning probe microscopy (AFM), or small-angle X-ray scattering (SAXS). The results demonstrate good consistency of the measured size by the different techniques in cases where special care was taken for sample preparation, instrument calibration, and the clear definition of the measurand. For each characterization method, the calibration process is described and a semi-quantitative table grouping the main error sources is proposed for estimating the uncertainties associated with the measurements. Regarding microscopy-based techniques applied to complexly shaped nanoparticles, data dispersion can be observed when the size measurements are affected by the orientation of the nanoparticles on the substrate. For the most complex materials, hybrid approaches combining several complementary techniques were tested, with the outcome being that the reliability of the size results was improved.

Published
2023
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4. Crystallization within Intermediate Amorphous Phases Determines the Polycrystallinity of Nanoparticles from Coprecipitation

Author

Alexy P. Freitas, Raj Kumar Ramamoorthy, Maxime Durelle, Eric Larquet, Isabelle Maurin, Fabienne Testard, Corinne Chevallard, Thierry Gacoin, David Carriere, Laboratoire Interdisciplinaire sur l'Organisation Nanométrique et Supramoléculaire (LIONS), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Laboratoire de physique de la matière condensée (LPMC), École polytechnique (X)-Centre National de la Recherche Scientifique (CNRS), Matériaux, Rayonnements, Structure (MRS), Institut Néel (NEEL), Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA), ANR-14-CE08-0003,DIAMONS,Phases denses intermédiaires liquides et amorphes comme modèle alternatif pour la synthèse de nanoparticules d'oxydes(2014), ANR-10-LABX-0035,Nano-Saclay,Paris-Saclay multidisciplinary Nano-Lab(2010), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Matériaux, Rayonnements, Structure (NEEL - MRS), Laboratoire de Physique de la Matière Condensée (LPMC), and Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Mechanical Engineering, Bioengineering, 02 engineering and technology, General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 01 natural sciences, 0104 chemical sciences, Nanoparticles, General Materials Science, 0210 nano-technology, Crystallization
Abstract

International audience; Intense research on nanocrystals synthesized in solution is motivated by their original physical properties, which are determined by their sizes and shapes on various scales. However, morphology control on the nanoscale is limited by our understanding of crystallization, which is challenged by the now well-established prevalence of noncrystalline intermediates. In particular, the impact of such intermediates on the final sizes and crystal quality remains unclear because the characterization of their evolution on the nanometer and millisecond scales with nonperturbative analyses has remained a challenge. Here we use in situ X-ray scattering to show that the nucleation and growth of YVO4:Eu nanocrystals is spatially restrained within amorphous, nanometer-scaled intermediates. The reactivity and size of these amorphous intermediates determine (i) the mono versus polycrystalline character of final crystals and (ii) the size of final crystals. This implies that designing amorphous intermediates themselves that form in

Published
2021
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5. Combining surface chemistry modification and in situ small-angle scattering characterization to understand and optimize the biological behavior of nanomedicines

Author

Marine Le Goas, Elodie Barruet, Maria Kalbazova, Tom Roussel, David Carriere, Jean Philippe Renault, Geraldine Carrot, Fabienne Testard, Valérie Geertsen, Giulia C Fadda, Laboratoire Innovation en Chimie des Surfaces et NanoSciences (LICSEN UMR 3685), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Interdisciplinaire sur l'Organisation Nanométrique et Supramoléculaire (LIONS), Laboratoire Léon Brillouin (LLB - UMR 12), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), UFR Santé, Médecine et Biologie Humaine (UFR SMBH), Université Sorbonne Paris Nord, ANR-11-IDEX-0003,IPS,Idex Paris-Saclay(2011), Laboratoire Innovation en Chimie des Surfaces et NanoSciences (LICSEN), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Université Paris-Saclay

Subjects
In situ, Cell Membrane Permeability, Surface Properties, Biomedical Engineering, Nanoparticle, Metal Nanoparticles, Nanotechnology, Antineoplastic Agents, Biocompatible Materials, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Small Molecule Libraries, Mice, Polymethacrylic Acids, Scattering, Small Angle, Animals, Humans, General Materials Science, Particle Size, Chemistry, General Chemistry, General Medicine, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Characterization (materials science), Cancer treatment, Nanomedicine, Colloidal gold, Gold, Small-angle scattering, 0210 nano-technology, Hydrophobic and Hydrophilic Interactions
Abstract

International audience; Nanomedicines are considered as promising therapeutics for cancer treatment. However, clinical translation is still scarce, partly because their biological behavior is not well understood. Extracting general guidelines from the great variety of nanoparticles and conditions studied is indeed difficult, and relevant techniques are lacking to obtain in situ information. Here, both issues are solved by combining versatile model nanoparticles with in situ tools based on small-angle scattering techniques (SAS). The strategy was to develop a library of nanoparticles and perform systematic study of their interactions with biological systems. Considering the promising properties of gold nanoparticles as cancer therapeutics, polymethacrylate-grafted gold nanoparticles were chosen as models. Modulation of polymer chemistry was shown to change the surface properties while keeping the same structure for all nanoparticles. This unity allowed reliable comparison to extract general principles, while the synthesis versatility enabled to fine-tune the nanoparticles surface properties, especially through copolymerization, and thus to optimize their biological behavior. Two specific aspects were particularly examined: colloidal stability and cell uptake. Positive charges and hydrophobicity were identified as key parameters influencing toxicity and internalization. In situ SAS gave valuable information about nanoparticles evolution in biologically relevant environments. Good colloidal stability was thereby shown in cell culture media, while intracellular transformation and quantity of nanoparticles were monitored, highlighting the potential of these techniques for nanomedicines studies.

Published
2020
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6. Albumin-driven disassembly of lipidic nanoparticles: the specific case of the squalene-adenosine nanodrug

Author

Marie Rouquette, Frédéric Gobeaux, Fabienne Testard, Semen O Yesylevsky, Didier Desmaële, Jean Philippe Renault, Joëlle Bizeau, Christophe Ramseyer, Frank Wien, Laurent Marichal, Isabelle Grillo, Sinda Lepetre-Mouelhi, Patrick Guenoun, Patrick Couvreur, Firmin Samson, Laboratoire Interdisciplinaire sur l'Organisation Nanométrique et Supramoléculaire (LIONS), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-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), Institut Laue-Langevin (ILL), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Department of Physics of Biological Systems, Institute of Metal Physics of the National Academy of Sciences of Ukraine, Laboratoire Chrono-environnement (UMR 6249) (LCE), Centre National de la Recherche Scientifique (CNRS)-Université de Franche-Comté (UFC), Université Bourgogne Franche-Comté [COMUE] (UBFC)-Université Bourgogne Franche-Comté [COMUE] (UBFC), Institut Galien Paris-Saclay (IGPS), Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), NATO grant SPS-G5291, ANR-11-IDEX-0003,IPS,Idex Paris-Saclay(2011), ANR-10-INBS-0005,FRISBI,Infrastructure Française pour la Biologie Structurale Intégrée(2010), European Project: 690853, European Project: 654000, Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), ILL, Laboratoire Chrono-environnement - CNRS - UBFC (UMR 6249) (LCE), Université de Franche-Comté (UFC), Université Bourgogne Franche-Comté [COMUE] (UBFC)-Université Bourgogne Franche-Comté [COMUE] (UBFC)-Centre National de la Recherche Scientifique (CNRS), and Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)

Subjects
Squalene, Adenosine, complexation, serum albumin, Serum albumin, 02 engineering and technology, Plasma protein binding, 010402 general chemistry, 01 natural sciences, Mice, Drug Stability, medicine, Animals, Humans, General Materials Science, Prodrugs, Colloids, Bovine serum albumin, ComputingMilieux_MISCELLANEOUS, Binding Sites, biology, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Chemistry, Albumin, Isothermal titration calorimetry, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Human serum albumin, disassembly, 0104 chemical sciences, nanodrug, biology.protein, Biophysics, Nanomedicine, Nanoparticles, 0210 nano-technology, Fetal bovine serum, medicine.drug, Protein Binding
Abstract

International audience; In the field of nanomedicine, nanostructured nanoparticles (NPs) made of self-assembling prodrugs emerged in the recent years with promising properties. In particular, squalene-based drug nanoparticles have already shown their efficiency through in vivo experiments. However, a complete pattern of their stability and interactions in the blood stream is still lacking. In this work we assess the behavior of squalene-adenosine (SQAd) nanoparticles-whose neuroprotective effect has already been demonstrated in murine models-in the presence of fetal bovine serum (FBS) and of bovine serum albumin (BSA), the main protein of blood plasma. Extensive physicochemical characterizations were performed using Small Angle Neutron Scattering (SANS), cryogenic transmission electron microscopy (Cryo-TEM), circular dichroism (CD), steady-state fluorescence spectroscopy (SSFS) and isothermal titration calorimetry (ITC) and in silico by means of ensemble docking simulations with human serum albumin (HSA). Significant changes in the colloidal stability of the nanoparticles in the presence of serum albumin were observed. SANS, CD and SSFS analyses demonstrated an interaction 2 between SQAd and BSA, with a partial disassembly of the nanoparticles in the presence of BSA and the formation of a complex between SQAd and BSA. The interaction free energy of SQAd nanoparticles with BSA derived from ITC experiments, is about-8 kcal/mol which is further supported in silico by ensemble docking simulations. Overall, our results show that serum albumin partially disassembles SQAd nanoparticles by extracting individual SQAd monomers from them. As a consequence, the SQAd nanoparticles would act as a circulating reservoir in the blood stream. The approach developed in this study could be extended to other soft organic nanoparticles.

Published
2020
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7. How do surface properties of nanoparticles influence their diffusion in the extracellular matrix? A model study in Matrigel using polymer-grafted nanoparticles

Author

Nabila Debou, Jean Philippe Renault, Béatrice Cambien, Fabienne Testard, Marine Le Goas, Geraldine Carrot, Olivier Taché, Laboratoire Innovation en Chimie des Surfaces et NanoSciences (LICSEN), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Laboratoire Interdisciplinaire sur l'Organisation Nanométrique et Supramoléculaire (LIONS), Transporteurs et Imagerie, Radiothérapie en Oncologie et Mécanismes biologiques des Altérations du Tissu Osseux (TIRO-MATOs - UMR E4320), UMR E4320 (TIRO-MATOs), Université Nice Sophia Antipolis (... - 2019) (UNS), COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Côte d'Azur (UCA)-Université Nice Sophia Antipolis (... - 2019) (UNS), COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Côte d'Azur (UCA)-Service Hospitalier Frédéric Joliot (SHFJ), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay, NSF award DMR-0520547, Laboratoire Innovation en Chimie des Surfaces et NanoSciences (LICSEN UMR 3685), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Service Hospitalier Frédéric Joliot (SHFJ), Université Paris-Saclay-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-UMR E4320 (TIRO-MATOs), Université Nice Sophia Antipolis (1965 - 2019) (UNS), COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Côte d'Azur (UCA)-Université Nice Sophia Antipolis (1965 - 2019) (UNS), and COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Côte d'Azur (UCA)

Subjects
Materials science, Polymers, Surface Properties, Diffusion, Metal Nanoparticles, Nanoparticle, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Homogeneous distribution, Extracellular matrix, Mice, X-Ray Diffraction, Scattering, Small Angle, Electrochemistry, Animals, General Materials Science, Spectroscopy, chemistry.chemical_classification, Matrigel, Small-angle X-ray scattering, Surfaces and Interfaces, Polymer, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, Extracellular Matrix, 0104 chemical sciences, Drug Combinations, chemistry, Colloidal gold, Biophysics, Nanoparticles, Proteoglycans, Collagen, Gold, Laminin, 0210 nano-technology
Abstract

Diffusion of nanomedicines inside the extracellular matrix (ECM) has been identified as a key factor to achieve homogeneous distribution and therefore therapeutic efficacy. Here, we sought to determine the impact of nanoparticles' (NPs) surface properties on their ability to diffuse in the ECM. As model nano-objects, we used a library of gold nanoparticles grafted with a versatile polymethacrylate corona, which enabled the surface properties to be modified. To accurately recreate the features of the native ECM, diffusion studies were carried out in a tumor-derived gel (Matrigel). We developed two methods to evaluate the diffusion ability of NPs inside this model gel: an easy-to-implement one based on optical monitoring and another one using small-angle X-ray scattering (SAXS) measurements. Both enabled the determination of the diffusion coefficients of NPs and comparison of the influence of their various surface properties, while the SAXS technique also allowed to monitor the NPs' structure as they diffused inside the gel. Positive charges and hydrophobicity were found to particularly hinder diffusion, and the different results suggested on the whole the presence of NPs-matrix interactions, therefore underlying the importance of the ECM model. The accuracy of the tumor-derived gels used in this study was evidenced by in vivo experiments involving intratumoral injections of NPs on mice, which showed that diffusion patterns in the peripheral tumor tissues were quite similar to the ones obtained within the chosen ECM model.

Published
2020
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8. Partial Transformation of Imogolite by Decylphosphonic Acid Yields an Interface Active Composite Material

Author

Fabienne Testard, Tobias Lange, Frédéric Gobeaux, Sophie Charton, Antoine Thill, Thibault Charpentier, Laboratoire Interdisciplinaire sur l'Organisation Nanométrique et Supramoléculaire (LIONS), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Laboratoire Structure et Dynamique par Résonance Magnétique (LCF) (LSDRM), Département de recherche sur les procédés pour la mine et le recyclage du combustible (DMRC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), C'Nano-IdFAmont-Aval CEA program, ANR-11-IDEX-0003,IPS,Idex Paris-Saclay(2011), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Palacin, Serge, and Idex Paris-Saclay - - IPS2011 - ANR-11-IDEX-0003 - IDEX - VALID

Subjects
Materials science, Scanning electron microscope, Infrared spectroscopy, Imogolite, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Lamellar phase, Electrochemistry, General Materials Science, Reactivity (chemistry), Composite material, Spectroscopy, [CHIM.MATE] Chemical Sciences/Material chemistry, Surfaces and Interfaces, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 0104 chemical sciences, 3. Good health, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [CHIM.THEO] Chemical Sciences/Theoretical and/or physical chemistry, Transmission electron microscopy, Surface modification, 0210 nano-technology, Dispersion (chemistry)
Abstract

International audience; The phosphonic acid moiety is commonly used as an anchoring group for the surface modification of imogolite. However, the impact of the reaction on its structure has never been clearly analyzed before. We study the reaction of imogolite and decylphosphonic acid by combining infrared spectroscopy, X-ray scattering, scanning electron microscopy, transmission electron microscopy and solid-state nuclear magnetic resonance spectroscopy. Instead of a surface functionalization, we observe the formation of a lamellar phase interconnected with imogolite bundles. Although we find no evidence for grafted imogolite tubes, we observe the expected dispersion characteristics and stabilization of water in toluene emulsions described in literature. Based on the surface chemistry of imogolite we propose an explanation for the observed reactivity and link the structural features of the obtained composite material to its dispersibility in toluene and its observed properties at the toluene-water interface.

Published
2019
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9. Gold Nanoparticle Internal Structure and Symmetry Probed by Unified Small-Angle X-ray Scattering and X-ray Diffraction Coupled with Molecular Dynamics Analysis

Author

Fabienne Testard, Olivier Spalla, Nicolas Menguy, Blaise Fleury, Olivier Taché, and Robinson Cortes-Huerto

Subjects
Diffraction, Materials science, Small-angle X-ray scattering, Scattering, Mechanical Engineering, Nanoparticle, Bioengineering, General Chemistry, Condensed Matter Physics, Crystallography, Crystallinity, Chemical physics, Colloidal gold, X-ray crystallography, General Materials Science, Surface plasmon resonance
Abstract

Shape and size are known to determine a nanoparticle's properties. Hardly ever studied in synthesis, the internal crystal structure (i.e., particle defects, crystallinity, and symmetry) is just as critical as shape and size since it directly impacts catalytic efficiency, plasmon resonance, and orients anisotropic growth of metallic nanoparticles. Hence, its control cannot be ignored any longer in today's research and applications in nanotechnology. This study implemented an unprecedented reliable measurement combining these three structural aspects. The unified small-angle X-ray scattering and diffraction measurement (SAXS/XRD) was coupled with molecular dynamics to allow simultaneous determination of nanoparticles' shape, size, and crystallinity at the atomic scale. Symmetry distribution (icosahedra-Ih, decahedra-Dh, and truncated octahedra-TOh) of 2-6 nm colloidal gold nanoparticles synthesized in organic solvents was quantified. Nanoparticle number density showed the predominance of Ih, followed by Dh, and little, if any, TOh. This result contradicts some theoretical predictions and highlights the strong effect of the synthesis environment on structure stability. We foresee that this unified SAXS/XRD analysis, yielding both statistical and quantitative counts of nanoparticles' symmetry distribution, will provide new insights into nanoparticle formation, growth, and assembly.

Published
2015
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10. Nanostructure Changes upon Polymerization of Aqueous and Organic Phases in Organized Mixtures

Author

Odile Fichet, Cecile Noirjean, David Carriere, Sophie Bourcier, Frédéric Vidal, Cédric Vancaeyzeele, Fabienne Testard, Laboratoire Interdisciplinaire sur l'Organisation Nanométrique et Supramoléculaire (LIONS), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Laboratoire de Physico-chimie des Polymères et des Interfaces (LPPI), Fédération INSTITUT DES MATÉRIAUX DE CERGY-PONTOISE (I-MAT), Université de Cergy Pontoise (UCP), Université Paris-Seine-Université Paris-Seine-Université de Cergy Pontoise (UCP), Université Paris-Seine-Université Paris-Seine, Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Aqueous solution, Materials science, Nanostructure, Aqueous two-phase system, technology, industry, and agriculture, 02 engineering and technology, Surfaces and Interfaces, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 01 natural sciences, 0104 chemical sciences, Lamellar phase, Polymerization, Phase (matter), Polymer chemistry, Electrochemistry, Precipitation polymerization, General Materials Science, Microemulsion, 0210 nano-technology, Spectroscopy
Abstract

International audience; The nanostructure of a microemulsion can be strongly affected by the liquid-to-solid transition during polymerization. Here, we examined the evolution of nanostructures of different ternary mixtures, including two microemulsions and a single lamellar phase that upon polymerization are quantitatively studied by SAXS/WAXS and DSC experiments systematically performed before and after the polymerization of both aqueous and organic phases. Samples are mixtures of the poly(2-acrylamido-2-methylpropanesulfonic acid) network as the aqueous phase and poly(hexyl methacrylate) as the organic phase stabilized by Brij35 surfactant. Upon polymerization, the surfactant is excluded from the water/oil interface and crystallizes, strongly changing the nanostructure of samples where it is the main component. In samples where the aqueous phase is the main component, only a few changes in structure are observed upon polymerization. This study demonstrates quantitatively the possibility to preserve nanostructures during polymerization, thus inducing a templating effect.

Published
2016
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11. Growth and Overgrowth of Concentrated Gold Nanorods: Time Resolved SAXS and XANES

Author

Olivier Spalla, Fabien Hubert, Olivier Taché, Q. Kong, Fabienne Testard, and Antoine Thill

Subjects
Materials science, Number density, Aspect ratio, Small-angle X-ray scattering, Analytical chemistry, Nucleation, Nanoparticle, General Chemistry, Condensed Matter Physics, XANES, Crystallography, General Materials Science, Nanorod, Absorption (chemistry)
Abstract

The growth of gold nanorods has been followed by small angle X-ray scattering and X-ray absorption. The synthesis is performed at high concentration of 3.5 mM in gold using in situ generation of seeds. It is shown that the growth occurs at constant number density of nanoparticles after the initial nucleation of seeds and that the final step of reduction of Au(I) to Au(0) occurs only at the surface of the growing nanorods. Anisotropy is acquired during the growth with a ratio of longitudinal to basal growth rates measured at 12. The final aspect ratio is only limited by the available amount of material and the experiment of overgrowth was allowed to reach a final aspect ratio of 5 instead of the initial 3.6.

Published
2012
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12. Nanorods versus Nanospheres: A Bifurcation Mechanism Revealed by Principal Component TEM Analysis

Author

Fabienne Testard, Giancarlo Rizza, Fabien Hubert, and Olivier Spalla

Subjects
Nanotubes, Materials science, Aqueous solution, Surface Properties, Analytical chemistry, Nanoparticle, Surfaces and Interfaces, Condensed Matter Physics, Borohydride, Rod, chemistry.chemical_compound, Microscopy, Electron, Transmission, chemistry, Chemical physics, Principal component analysis, Electrochemistry, General Materials Science, SPHERES, Nanorod, Particle Size, Nanospheres, Spectroscopy, Bifurcation
Abstract

A quantitative analysis of object populations obtained by TEM images is performed for the classical scheme of aqueous seedless synthesis of nanorods. Using an effective way to represent nanoparticle size distributions, we unravel that spheres, usually considered to be a side-product, are in fact coming from a competing route during nanorod formation. The differentiation between spheres and rods appears above a critical size of 5 nm and is due to different growth rates between faces. The initial repartition of faces on nuclei or on the nanoparticles at the critical size can be the source for the final differentiation between globules and rods. The efficiency of the selection is strongly influenced by the production of the initial seeds and, in particular, by the amount of borohydride added in the present scheme.

Published
2010
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13. Probing in situ the Nucleation and Growth of Gold Nanoparticles by Small-Angle X-ray Scattering

Author

Philippe Barboux, Fabienne Testard, Benjamin Abécassis, Olivier Spalla, Laboratoire Interdisciplinaire sur l'Organisation Nanométrique et Supramoléculaire (LIONS), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Université Paris sciences et lettres (PSL)

Subjects
Macromolecular Substances, Surface Properties, Annealing (metallurgy), Molecular Conformation, Analytical chemistry, Nucleation, Bioengineering, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, law.invention, X-Ray Diffraction, law, Materials Testing, Scattering, Small Angle, Nanotechnology, General Materials Science, [PHYS.COND]Physics [physics]/Condensed Matter [cond-mat], Particle Size, Spectroscopy, ComputingMilieux_MISCELLANEOUS, Small-angle X-ray scattering, Chemistry, Mechanical Engineering, General Chemistry, Hydrogen-Ion Concentration, 021001 nanoscience & nanotechnology, Condensed Matter Physics, Synchrotron, Nanostructures, 0104 chemical sciences, Colloidal gold, Particle-size distribution, Gold, Crystallization, 0210 nano-technology, Order of magnitude
Abstract

We probe in situ by synchrotron SAXS/WAXS and UV−visible spectroscopy the nucleation and growth of gold nanoparticles. The use of a fast-mixing stopped-flow device enables the assesment of the whole particle formation process with a 200 ms time resolution. The number of particles, their size distribution, and the yield of the reaction is determined in real time through the quantitative analysis of the SAXS data on an absolute scale. Two ligands exhibit drastically different behaviors: when an alkanoic acid is used, a nucleation phase of 1 s is followed by a growth step whose rate is limited by the reaction of the monomers at the interface; on the other hand, when an alkylamine is used, the nucleation rate is increased by an order of magnitude, thus annealing growth by a lack of monomer and yielding R = 1 nm particles in 2 s, as compared with R = 3.7 nm in 12 s for the acid case.

Published
2007
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14. How Does ZrO2/Surfactant Mesophase Nucleate? Formation Mechanism

Author

F. Ne, I. Grillo, Fabienne Testard, and Th. Zemb

Subjects
Zirconium, Materials science, genetic structures, Precipitation (chemistry), Nucleation, chemistry.chemical_element, Mesophase, Surfaces and Interfaces, Neutron scattering, Condensed Matter Physics, Micelle, Crystallography, chemistry.chemical_compound, Monomer, chemistry, Pulmonary surfactant, Electrochemistry, General Materials Science, Spectroscopy
Abstract

In situ time-resolved small-angle X-ray and neutron scattering have been used to investigate the mechanism of a bulk precipitation of a hexagonally ordered ZrO 2 /surfactant mesophase. Using hexadecyltrimethylammonium bromide (CTAB) as a structure-directing agent, the precipitation results from the addition of sulfate to an oxychloride zirconium/CTAB water solution. The precipitate obtained after a few seconds is organized in a 2D hexagonal network. There is no preexisting cylindrical micelle in the precursor solution, and the micelles act as a reservoir for monomer to feed the building grain. The precipitation occurs through a two-step mechanism: a random nucleation/growing process and a first-order reorganization from locally ordered cylinders to a hexagonal lattice in the grain at its final size.

Published
2003
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15. Twinned gold nanoparticles under growth: bipyramids shape controlled by environment

Author

Robinson Cortes-Huerto, Guillaume Wang, Fabienne Testard, Jacek Goniakowski, Olivier Spalla, Nicolas Menguy, Ovidiu Ersen, Z. Cansu Canbek, Simona Moldovan, Claudine Noguera, Andreas Wisnet, Laboratoire Interdisciplinaire sur l'Organisation Nanométrique et Supramoléculaire (LIONS), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Nanosciences de Paris (INSP), Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Ludwig-Maximilians-Universität München (LMU), Laboratoire Matériaux et Phénomènes Quantiques (MPQ (UMR_7162)), Centre National de la Recherche Scientifique (CNRS)-Université Paris Cité (UPCité), Institut de minéralogie, de physique des matériaux et de cosmochimie (IMPMC), Muséum national d'Histoire naturelle (MNHN)-Institut de recherche pour le développement [IRD] : UR206-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-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)-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), Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP), Palacin, Serge, Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et nanosciences d'Alsace, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Université Paris Diderot - Paris 7 (UPD7)-Centre National de la Recherche Scientifique (CNRS), Université de Strasbourg (UNISTRA)-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)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, and 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)

Subjects
Diffraction, [PHYS]Physics [physics], [CHIM.MATE] Chemical Sciences/Material chemistry, Materials science, Nanoparticle, Transmission electronic microscopy, 02 engineering and technology, General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 01 natural sciences, 0104 chemical sciences, Crystallography, Colloidal gold, [CHIM]Chemical Sciences, General Materials Science, Nanorod, Selected area diffraction, 0210 nano-technology, High-resolution transmission electron microscopy, Plasmon
Abstract

International audience; The structure of (Au) bipyramids, very promising for their specific plasmonic properties, is fully analyzed for gradual stages of growth. From combined use of HRTEM (High resolution transmission electronic microscopy) in specific conditions and SAED (selected area electronic diffraction) analysis, the atomic structure of these elongated objects of different sizes is extracted (from 2 to 60 nm). In the case of silver(I)-assisted growth from citrate capped seeds, a clear penta-twinned structure, made by the superimposition of specific pairs of crystallographic zones is found for the different size nanoparticles representing the different steps of the growing bipyramids. The experimental results were analyzed in the framework of a recent atomistic approach developed for metal-environment interactions to account for the stability of multi-twinned nanorods or bipyramids in a complex environment. Efficient in describing the multi-twinned nanoparticles and the drastic effects of environment on the stabilization of elongated multi-twinned shapes, this model supports the experimental features of bipyramids and nanorods formation from citrate seeds in function of the nature of the surface chemical ligands: citrate seeds in a growth solution prepared without silver(I) yields the formation of a few penta-twinned nanorods, while the silver(I)-assisted growth process mainly leads to penta-twinned bipyramids. The conservation of a bulk penta-twinned structure inherited from isotropic decahedral (i-Dh) seeds all along the growth is retrieved by this approach for two different environments.

Published
2015
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17. Excess of Solubilization of Lindane in Nonionic Surfactant Micelles and Microemulsions

Author

Fabienne Testard and Th. Zemb

Subjects
Chromatography, Analytical chemistry, Surfaces and Interfaces, Condensed Matter Physics, Micelle, chemistry.chemical_compound, Reduced properties, Pulmonary surfactant, chemistry, Volume (thermodynamics), Volume fraction, Electrochemistry, General Materials Science, Microemulsion, Ternary operation, Lindane, Spectroscopy
Abstract

The solubilization oflindane by nonionic polyoxyethylene glycol surfactants has been studied in micellar solution, as well as in Winsor I and Winsor III microemulsions. The maximum of solubilization was determined when a saturated lindane solution was in equilibrium with solid lindane. At this saturation point, the interfacial molar ratio λ max of the solute to the surfactant was determined, taking into account the amount of lindane solubilized in oil. We first studied the evolution of the maximum excess solubilization λ max as a function of surfactant volume fraction in water-C 8 E 6 binary solutions. The excess solubilization was found to be constant between 0 and 50% in surfactant volume fraction. For higher volume fractions, λ max increased with the surfactant concentration. This behavior is the result of a competition between water and lindane to be solubilized by the surfactant film. We also observed a decrease of the clouding temperature for the water-C 8 E 6 system when lindane is solubilized. We have evidenced a linear decreasing of λ max with the reduced temperature (T L C - T)/T C L , where T C L is the cloud temperature for the saturated system. By comparison with results obtained with ternary microemulsions for two different curvatures, we have observed a strong dependence of i max on the average curvature of the surfactant film. The excess solubilization is maximum for the bicontinuous balanced structure obtained in the Winsor III case, where fluctuations produce the most stable structure versus the amount of added solute located in the surfactant film. When only excess oil is present (Winsor I), the o/w droplets at the emulsification failure boundary show an intermediate value of the maximum solubilization power.

Published
1998
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18. Synergism by Coassembly at the Origin of Ion Selectivity in Liquid–Liquid Extraction

Author

Thomas Zemb, Sandrine Dourdain, Jacques Jestin, Jean-François Dufrêche, Antoine Leydier, O. Pecheur, Raphaël Turgis, I. Hofmeister, Stéphane Pellet-Rostaing, Fabienne Testard, Tri ionique par les Systèmes Moléculaires auto-assemblés (LTSM), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Modélisation Mésoscopique et Chimie Théorique (LMCT), Laboratoire d'Ingénierie des Matériaux de Bretagne (LIMATB), Université de Bretagne Sud (UBS)-Université de Brest (UBO)-Institut Brestois du Numérique et des Mathématiques (IBNM), Université de Brest (UBO)-Université de Brest (UBO), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Université de Bretagne Sud (UBS)-Institut Brestois du Numérique et des Mathématiques (IBNM), and Université de Brest (UBO)-Université de Brest (UBO)-Université de Brest (UBO)

Subjects
Chemistry, Dodecane, Small-angle X-ray scattering, 02 engineering and technology, Surfaces and Interfaces, 010402 general chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 01 natural sciences, 0104 chemical sciences, Ion, Solvent, chemistry.chemical_compound, Chemical engineering, Liquid–liquid extraction, Phase (matter), Electrochemistry, Organic chemistry, [CHIM]Chemical Sciences, General Materials Science, 0210 nano-technology, Selectivity, Spectroscopy, ComputingMilieux_MISCELLANEOUS, Phase diagram
Abstract

In liquid-liquid extraction, synergism emerges when for a defined formulation of the solvent phase, there is an increase of distribution coefficients for some cations in a mixture. To characterize the synergistic mechanisms, we determine the free energy of mixed coassembly in aggregates. Aggregation in any point of a phase diagram can be followed not only structurally by SANS, SAXS, and SLS, but also thermodynamically by determining the concentration of monomers coexisting with reverse aggregates. Using the industrially used couple HDEHP/TOPO forming mixed reverse aggregates, and the representative couple U/Fe, we show that there is no peculiarity in the aggregates microstructure at the maximum of synergism. Nevertheless, the free energy of aggregation necessary to form mixed aggregates containing extracted ions in their polar core is comparable to the transfer free energy difference between target and nontarget ions, as deduced from the synergistic selectivity peak.

Published
2012
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19. Surfactant (bi)layers on gold nanorods

Author

Andrés Guerrero-Martínez, Sergio Gómez-Graña, Isabelle Grillo, Olivier Spalla, Fabien Hubert, Fabienne Testard, and Luis M. Liz-Marzán

Subjects
Materials science, Aqueous solution, Small-angle X-ray scattering, Bilayer, Analytical chemistry, 02 engineering and technology, Surfaces and Interfaces, 010402 general chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 01 natural sciences, Micelle, 0104 chemical sciences, Direct measure, Pulmonary surfactant, Electrochemistry, General Materials Science, Nanorod, 0210 nano-technology, Layer (electronics), Spectroscopy
Abstract

Gold nanorods in aqueous solution are generally surrounded by surfactants or capping agents. This is crucial for anisotropic growth during synthesis and for their final stability in solution. When CTAB is used, a bilayer has been evidenced from analytical methods even though no direct morphological characterization of the precise thickness and compactness has been reported. The type of surfactant layer is also relevant to understand the marked difference in further self-assembling properties of gold nanorods as experienced using 16-EO(1)-16 gemini surfactant instead of CTAB. To obtain a direct measure of the thickness of the surfactant layer on gold nanorods synthesized by the seeded growth method, we coupled TEM, SAXS, and SANS experiments for the two different cases, CTAB and gemini 16-EO(1)-16. Despite the strong residual signal from micelles in excess, it can be concluded that the thickness is imposed by the chain length of the surfactant and corresponds to a bilayer with partial interdigitation.

Published
2011

20. Influence of Monomer Feeding on a Fast Gold Nanoparticles Synthesis: Time-Resolved XANES and SAXS Experiments

Author

Oliver Spalla, Baudelet Francois, Quingyu Kong, Fabienne Testard, Benjamin Abécassis, Laboratoire Interdisciplinaire sur l'Organisation Nanométrique et Supramoléculaire (LIONS), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Time Factors, Nucleation, Analytical chemistry, Nanoparticle, Metal Nanoparticles, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, X-Ray Diffraction, Scattering, Small Angle, Electrochemistry, General Materials Science, [PHYS.COND]Physics [physics]/Condensed Matter [cond-mat], Spectroscopy, ComputingMilieux_MISCELLANEOUS, X-ray absorption spectroscopy, Small-angle X-ray scattering, Chemistry, Surfaces and Interfaces, 021001 nanoscience & nanotechnology, Condensed Matter Physics, XANES, 0104 chemical sciences, X-Ray Absorption Spectroscopy, Colloidal gold, Particle, Gold, Absorption (chemistry), 0210 nano-technology
Abstract

A comprehensive study of the mechanism of gold nanoparticle formation has been conducted using third-generation synchrotrons. The particles were obained by reduction of AuCl(3) by BH(4)(-) in toluene. Gold oxidation state was monitored by X-ray absorption near edge spectroscopy (XANES), while the size and concentration of the nanoparticles were assessed by small-angle X-ray scattering (SAXS). A time-resolution of 100 ms has been achieved for a total formation time of a few seconds. The change with time of the total amount of Au(0) present in the solution is obtained by XANES. The change of the amount of Au(0) inside the nanoparticles is obtained from the SAXS signal. The comparison between these two quantities shows that a measurable amount of Au(0) exists transiently as monomers (or very small entities) in solution and this quantity is linked to an observed burst of nucleation of nanoparticles. The reduction kinetics is strongly influenced by the presence of ligands and a change in temperature. A model coupling the observed reduction kinetics and nucleation and growth laws is able to recover the final size and number densities of the explored experimental conditions.

Published
2010
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21. Correspondence between curvature, packing parameter, and hydrophilic-lipophilic deviation scales around the phase-inversion temperature

Author

Werner Kunz, Fabienne Testard, and Thomas Zemb

Subjects
Quantitative Biology::Biomolecules, Chemistry, Mathematical analysis, Thermodynamics, Single parameter, Surfaces and Interfaces, Bending, Condensed Matter Physics, Curvature, Surface energy, Condensed Matter::Soft Condensed Matter, Solubilization, Electrochemistry, Compressibility, General Materials Science, Equivalence (measure theory), Spectroscopy, Phase inversion
Abstract

We show in this paper that three ways of characterizing “spontaneous” lateral packing of amphiphiles are equivalent: the spontaneous curvature, the molecular packing parameter, and the refined hydrophilic−lipophilic balance known as HLD (hydrophilic−lipophilic deviation). Recognition of this equivalence, with its underlying hypothesis of incompressible fluid with lowest surface energy, reinforces the single parameter bending energy expression implicit in the classical papers by Ninham and Israelachvili, as well as all the predictive models of solubilization developed as yet.

Published
2008

22. Cetyltrimethylammonium Bromide Silver Bromide Complex as the Capping Agent of Gold Nanorods

Author

Fabienne Testard, Fabien Hubert, Olivier Spalla, Laboratoire Interdisciplinaire sur l'Organisation Nanométrique et Supramoléculaire (LIONS), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Stereochemistry, 02 engineering and technology, Surfaces and Interfaces, Quartz crystal microbalance, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, Silver bromide, 01 natural sciences, 0104 chemical sciences, chemistry.chemical_compound, Adsorption, Pulmonary surfactant, chemistry, Transition metal, X-ray photoelectron spectroscopy, Chemical engineering, Bromide, Electrochemistry, General Materials Science, Nanorod, 0210 nano-technology, Spectroscopy
Abstract

International audience; A complex between cetyltrimethylammonium bromide (CTAB) surfactant and silver bromide (CTASB) is recognized by NMR and X-ray photoelectron spectroscopy (XPS) to be the entity at the surface of gold nanorods, resulting from an in situ formation in the classical scheme of synthesis. It can thus be introduced directly along with the initial reactants in place of silver(I) salt to produce a new effective synthesis of these objects. Complementary XPS and quartz crystal microbalance (QCM) measurements on macroscopic gold surfaces confirm a strong adsorption of CTASB that is higher than that of CTAB and any other CTAX surfactants. The role of CTASB as a rod inducing agent by surface complexation is stressed.

Published
2008
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23. Electrostastic Control of Spontaneous Curvature in Catanionic Reverse Micelles

Author

Steen Hansen, Isabelle Grillo, Fabienne Testard, Lise Arleth, Thomas Zemb, Benjamin Abécassis, Laboratoire Interdisciplinaire sur l'Organisation Nanométrique et Supramoléculaire (LIONS), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Laue-Langevin (ILL), and ILL

Subjects
Phase transition, Chemistry, Stereochemistry, 02 engineering and technology, Surfaces and Interfaces, Neutron scattering, 010402 general chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, Curvature, 01 natural sciences, Micelle, Small-angle neutron scattering, 0104 chemical sciences, Pulmonary surfactant, Chemical physics, Electrochemistry, General Materials Science, Microemulsion, Surface charge, [PHYS.COND]Physics [physics]/Condensed Matter [cond-mat], 0210 nano-technology, Spectroscopy, ComputingMilieux_MISCELLANEOUS
Abstract

By means of small-angle neutron scattering and conductivity measurements, we study the microstructure of octylammoniumoctanoate/octane/water catanionic reverse microemulsions with an excess of anionic or cationic surfactant. Increasing the surface charge makes the microemulsion able to incorporate much more water than in the neutral case, up to 10 water molecules per surfactant. Even with charges in the surfactant film, wormlike micelles are present in the microemulsion domain. Along water dilution lines, the classical rod-to-sphere transition due to the minimization of the curvature energy of the rigid surfactant film is observed. When temperature is decreased, a re-entrant phase transition associated with the liquid-gas equilibrium of attractive cylinders is observed. Using the framework of the Tlusty-Safran theory, attraction could originate from junctions between wormlike reverse micelles. In any case, the spontaneous curvature of the catanionic surfactant film depends on both the temperature and the net charge, whatever the sign of the latter.

Published
2007
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24. Phase Behavior, Topology, and Growth of Neutral Catanionic Reverse Micelles

Author

Benjamin Abécassis, Fabienne Testard, Thomas Zemb, Lise Arleth, Steen Hansen, Isabelle Grillo, Laboratoire Interdisciplinaire sur l'Organisation Nanométrique et Supramoléculaire (LIONS), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Institut Laue-Langevin (ILL), ILL, Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Anions, Stereochemistry, 02 engineering and technology, 010402 general chemistry, Branching (polymer chemistry), 01 natural sciences, Micelle, Phase Transition, Surface-Active Agents, chemistry.chemical_compound, Pulmonary surfactant, Cations, Electrochemistry, General Materials Science, Microemulsion, [PHYS.COND]Physics [physics]/Condensed Matter [cond-mat], Micelles, Spectroscopy, ComputingMilieux_MISCELLANEOUS, Octane, Phase diagram, Ternary numeral system, Microchemistry, Temperature, Water, Surfaces and Interfaces, Octanes, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 0104 chemical sciences, Quaternary Ammonium Compounds, chemistry, Chemical physics, Emulsions, 0210 nano-technology, Ternary operation
Abstract

The ternary catanionic system octylammoniumoctanoate/octane/water is studied by combined SANS, light scattering, conductivity, and phase diagram approach in the water-poor microemulsion region. The sphere-to-cylinder growth and branching depends on the concentration, the water-to-surfactant ratio, and the temperature. The unidimensional growth leads to a network of interconnected wormlike micelles. Like most studied linear nonionic surfactants, in this true catanionic system at equimolarity of anionic and cationic surfactant, the curvature toward water increases with temperature, making connections between cylinders less frequent.

Published
2006
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25. Effect of recognized and unrecognized salt on the self-assembly of new thermosensitive metal-chelating surfactants

Author

Thomas Zemb, Helene Coulombeau, Chantal Larpent, and Fabienne Testard

Subjects
Models, Molecular, Metal ions in aqueous solution, Micelle, Polyethylene Glycols, Metal, Surface-Active Agents, Amphiphile, Polymer chemistry, Electrochemistry, Organic chemistry, General Materials Science, Chelation, Spectroscopy, Alkyl, Micelles, chemistry.chemical_classification, Ligand, Chemistry, Lysine, Surfaces and Interfaces, Condensed Matter Physics, Covalent bond, visual_art, Uranyl Nitrate, visual_art.visual_art_medium, Lithium Compounds, Thermodynamics
Abstract

New functional thermoreversible metal complexing surfactants consisting of a chelating amino acid residue grafted to the tip of a nonionic surfactant [alkyl poly(oxyethylene) CiEj] or in a branched position are studied. Nonionic surfactants are thermoreversible and exhibit a clouding phenomenon associated with phase separation of micelles. The functional molecules retain both the surface-active properties and the characteristic thermoreversible behavior. Because of the hydrophilic contribution of the chelating group (acetyl lysine), the cloud point and the area at the air-water interface are higher for functional surfactants than for nonionic precursors. These new surfactants have efficient complexing properties toward metal ions and are more efficient than the mixture of the corresponding nonionic surfactant and the acetyl lysine ligand solubilized in micelles. This reveals the synergistic effect obtained by the covalent link between the two functions. Addition of a bulky group on classical amphiphilic structures modifies markedly the packing constraints at the origin ofmicellar structures. Small-angle X-ray or neutron scattering results, modeled jointly on the absolute scale, demonstrate the influence of unrecognized lithium nitrate (LiNO3) as well as specifically recognized uranyl nitrate [UO2(NO3)2] salts on micellar structure and phase boundaries. The determination of the micellar shape variations induced by a recognized salt, that is, a decrease of the polar headgroup, allows the rationalization of uncommon synergistic effects on the cloud point variation: increase with lithium nitrate, no decrease in the presence of uranyl nitrate, and a very large decrease when these two salts are present together.

Published
2005

26. Effect of n -Octanol on the Structure at the Supramolecular Scale of Concentrated Dimethyldioctylhexylethoxymalonamide Extractant Solutions

Author

Charles Madic, Th. Zemb, Laurence Berthon, Fabienne Testard, Benjamin Abécassis, Laboratoire Interdisciplinaire sur l'Organisation Nanométrique et Supramoléculaire (LIONS), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Service de Chimie des Procédés de Séparation (SCPS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut Rayonnement Matière de Saclay (IRAMIS), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
Octanol, Dodecane, Scattering, Small-angle X-ray scattering, Supramolecular chemistry, Analytical chemistry, 02 engineering and technology, Surfaces and Interfaces, 010402 general chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 01 natural sciences, 3. Good health, 0104 chemical sciences, Surface tension, chemistry.chemical_compound, chemistry, Electrochemistry, General Materials Science, [PHYS.COND]Physics [physics]/Condensed Matter [cond-mat], 0210 nano-technology, Spectroscopy, ComputingMilieux_MISCELLANEOUS
Abstract

Using small-angle X-ray scattering (SAXS) and interfacial tension measurements, we show that concentrated solutions of dimethyldioctylhexylethoxymalonamide diluted in dodecane are organized in reve...

Published
2003
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