Author: "Fabienne Testard" / Topic: chemistry - Searchworks@Jio Institute Digital Library Search Results

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1. Making Mobile Nanotechnology Accessible: Is the Explicit Preparation of Janus Nanoparticle Necessary to Achieve Mobility?

Author: Vagisha Nidhi, Arthur Allaire, Zakariya Ait Athmane, Patrick Guenoun, Fabienne Testard, Jean-Philippe Renault, and Florent Malloggi
Subjects: self-propulsion, mobility, chemotaxism, Janus particles, gold–silica particles, DLS, Chemistry, QD1-999
Abstract: This study compares the mobility behaviour, in a H2O2 environment, of three different geometries of hybrid particle made of silica core functionalized by gold (nanoparticles or layer). It is known that the decomposition of H2O2 on gold surfaces drives mobility; however, the link between mobility orientation and the organization of gold on silica surfaces is still questionable. While conventional wisdom posits that asymmetric designs are crucial for generating phoretic forces or localized bubble propulsion, recent research suggests that symmetrical particles may also exhibit motility. To address this debate, we developed a robust workflow for synthesizing gold grafted silica nanoparticles with precise control over size and shape, enabling the direct comparison of their motile behaviour by dynamic light scattering and particle tracking velocimetry. Our results indicate, first, that a combination of techniques is necessary to overcome their intrinsic limitation and, second, that the inherent asymmetry generated by isotropic gold nanoparticle deposition onto silica surfaces may enable particle motility.
Published: 2024
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2. 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, Chemistry, QD1-999
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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3. Dimensional measurement of TiO$_2$ (Nano) particles by SAXS and SEM in powder form

Author: Najoua Bouzakher-Ghomrasni, Jocelyne Leroy, Fabienne Testard, Olivier Taché, Carine Chivas-Joly, Nicolas Feltin, Laboratoire National de Métrologie et d'Essais [Trappes] (LNE ), 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 Innovation en Chimie des Surfaces et NanoSciences (LICSEN), With the financial support from Agence Nationale Recherche Technologie (ANRT)under the contract CIFRE N°2018/0367., 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 Laboratoire Innovation en Chimie des Surfaces et NanoSciences (LICSEN UMR 3685)
Subjects: Small-angle X-ray scattering, Chemistry, 010401 analytical chemistry, Nanoparticle, 02 engineering and technology, SAXS, [CHIM.MATE]Chemical Sciences/Material chemistry, Raw material, 021001 nanoscience & nanotechnology, Metrology, 01 natural sciences, 0104 chemical sciences, Analytical Chemistry, Characterization (materials science), (Nano)particles, Manufactured products, Specific surface area, Nano, SEM, TiO2, Manufactured nanoparticles, Composite material, 0210 nano-technology
Abstract: International audience; The market for nano-additive materials has been growing exponentially since 2012, with almost 5040 consumer products containing nanoparticles in 2021. In parallel, the increasing recommendations, definitions and legislations underline the need for traceability of manufactured nanoparticles and for methods able to identify and quantify the “nano” dimensional character in manufactured product. From a multi-technic approach, this paper aims to compare the mesurands extracted from SAX/BET (specific surface area) and SEM (diameter equivalent to a projected surface area) on different TiO$_2$ powder issued from referenced, synthesized materials, raw materials (additives) and extracted materials from manufactured products. The influence of various parameters such as the anisotropic factor, the interaction between particles, the size distribution and the extraction steps are discussed to illustrate their impact on the diameter values issued from two different measurands. These results illustrate the difficulties in (nano)particles characterization. SEM and SAXS are complementary technics depending on the level of dimensional characterization required.
Published: 2021
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4. Morphology-controlled precipitation of cerium oxalate crystals: The effect of water in nanostructured solvents

Author: Renaud Podor, Sophie Charton, Irma Liascukiene, Fabienne Testard, Marie Jehannin, J. Lautru, 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), Department of Applied Mathematics (Canberra), Australian National University (ANU), Etude de la Matière en Mode Environnemental (L2ME), 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), 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), European Project: 654000,H2020,H2020-INFRADEV-1-2014-1,SINE2020(2015), 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 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)
Subjects: Morphology (linguistics), Precipitation (chemistry), Chemistry, 02 engineering and technology, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, chemistry.chemical_compound, General Energy, Chemical engineering, Physical and Theoretical Chemistry, 0210 nano-technology, Cerium oxalate
Abstract: International audience; The ability to control the morphology of precipitated cerium oxalate material results in determinate evidence to its final properties. In this study, we demonstrate that surfactant-free nanostructured low-water solvents have a huge potential for controlling the morphology of a cerium oxalate powder. To this aim, an in-depth investigation of the reaction between cerium nitrate and oxalic acid is carried out, by varying both the relative concentration of the two reagents (around the stoichiometric value) and the composition of the water/propanediol/octanol ternary solvent (especially in the low-water content nanostructured domain). Thanks to the complementary of observation methods: microscopy (confocal microscopy with fluorophores and environmental SEM) and X-ray scattering (SAXS and WAXS), we evidenced the role of the solvent in the growth kinetics and directional aggregation of the precipitates—the two major factors determining the final morphology of the particles. Besides the possible confinement effect in nanodroplets, compact “dense-branching” particles, achieved in low-water content solvents, unveil the strong role of the surface forces in the aggregation mechanisms. This is consistent with the prevailing capillary forces at water/oil/solid triple points in ternary solvents. These new results confirm the high potential of nanostructured solvents for controlling the size and shape of hydrated precipitated particles.
Published: 2021
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5. OSTE+ for in-situ SAXS Analysis with Droplet Microfluidic Devices

Author: Thomas Bizien, Tobias Lange, Fabienne Testard, Florent Malloggi, Sophie Charton, 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), 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), 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: chemistry.chemical_classification, Materials science, Small-angle X-ray scattering, Scattering, 010401 analytical chemistry, Microfluidics, Biomedical Engineering, Bioengineering, Nanotechnology, 02 engineering and technology, General Chemistry, Polymer, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Biochemistry, 0104 chemical sciences, chemistry, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Attenuation coefficient, Transmission coefficient, 0210 nano-technology, Polyimide, Microfabrication
Abstract: International audience; In recent years, microfluidic-based sample preparation techniques have emerged as a powerful tool for measurements at large scale X-ray facilities. Most often the microfluidic device was a form of hybrid system, i.e. an assembly of different materials, because a simple, versatile and inexpensive microfabrication method, on the one hand, and X-ray compatibility, on the other hand, cannot generally be achieved by the same material. The arrival of a new polymer family based on Off-Stoichiometric Thiol-Ene-epoxy (OSTE+) has recently redistributed the cards. In this context, we studied the relevance and the compatibility of OSTE+ for small-angle X-ray scattering (SAXS) studies. The material was characterized regarding its X-ray properties (transmission coefficient, attenuation coefficient, scattering pattern and polymer aging under X-ray light) and their comparison with those of the usual polymers used in microfluidics and/or for synchrotron radiation experiments. We show that OSTE+ has a better SAXS signal than polyimide, the polymer of reference in the SAXS community. Then a detailed protocol to manufacture a suitably thin full OSTE+ chip (total thickness
Published: 2020
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6. 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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7. 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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8. 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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9. Translation of nanomedicines from lab to industrial scale synthesis: The case of squalene-adenosine nanoparticles

Author: Marie Rouquette, Arnaud Peramo, Clement Mahatsekake, Romain Brusini, Mariana Varna, Sinda Lepetre-Mouelhi, Flavio Dormont, Didier Desmaële, Serge Calet, Frédéric Gobeaux, Patrick Couvreur, Fabienne Testard, Institut Galien Paris-Sud (IGPS), Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS), HOLOCHEM, 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), 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)-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, Fondation pour la Recherche Médicale (FRM) grant number ECO20160736101, ANR-16-ENM2–0005-01,NanoHeart,NanoHeart, Institut Galien Paris-Saclay (IGPS), Institut de Chimie du CNRS (INC)-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)-Institut de Chimie du CNRS (INC), 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), ANR-16-ENM2-0005,NanoHeart,Squalene-Adenosine nanoparticles for heart ischemia/reperfusion injuries treatment(2016), Institut de Biologie et de Technologies de Saclay (IBITECS), Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), 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), Physico-chimie, pharmacotechnie, biopharmacie (PCPB), 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 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)
Subjects: Multiple stages, Male, Squalene, Adenosine, Cell Survival, Pharmaceutical Science, Nanoparticle, Nanotechnology, Context (language use), impurity profile, 02 engineering and technology, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, Cell Line, Rats, Sprague-Dawley, 03 medical and health sciences, chemistry.chemical_compound, Mice, Animals, scaling-up nanomedicines, ComputingMilieux_MISCELLANEOUS, 030304 developmental biology, 0303 health sciences, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Industrial scale, [CHIM.MATE]Chemical Sciences/Material chemistry, Blood Proteins, [SDV.SP]Life Sciences [q-bio]/Pharmaceutical sciences, 021001 nanoscience & nanotechnology, Biocompatible material, drug development, [SDV.SP.PG]Life Sciences [q-bio]/Pharmaceutical sciences/Galenic pharmacology, Nanomedicine, Drug development, Nanoparticles, Adsorption, Nanocarriers, 0210 nano-technology
Abstract: International audience; A large variety of nanoparticle-based delivery systems have become increasingly important for diagnostic and/or therapeutic applications. Yet, the numerous physical and chemical parameters that influence both the biological and colloidal properties of nanoparticles remain poorly understood. This complicates the ability to reliably produce and deliver well-defined nanocarriers which often leads to inconsistencies, conflicts in the published literature and, ultimately, poor translation to the clinics. A critical issue lies in the challenge of scaling-up nanomaterial synthesis and formulation from the lab to industrial scale while maintaining control over their diverse properties. Studying these phenomena early on in the development of a therapeutic agent often requires partnerships between the public and private sectors which are hard to establish. In this study, through the particular case of squalene-adenosine nanoparticles, we reported on the challenges encountered in the process of scaling-up nanomedicines synthesis. Here, squalene (the carrier) was functiona-lized and conjugated to adenosine (the active drug moiety) at an industrial scale in order to obtain large quantities of biocompatible and biodegradable nanoparticles. After assessing nanoparticle batch-to-batch consistency , we demonstrated that the presence of squalene analogs resulting from industrial scale-up may influence several features such as size, surface charge, protein adsorption, cytotoxicity and crystal structure. These analogs were isolated, characterized by multiple stage mass spectrometry, and their influence on nanoparticle properties further evaluated. We showed that slight variations in the chemical profile of the nanocarrier's constitutive material can have a tremendous impact on the reproducibility of nanoparticle properties. In a context where several generics of approved nanoformulated drugs are set to enter the market in the coming years, characterizing and solving these issues is an important step in the pharmaceutical development of nanomedicines.
Published: 2019
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10. Towards a clinical application of freeze-dried squalene-based nanomedicines

Author: Fabienne Testard, Mélanie Polrot, Frédéric Gobeaux, Marie Rouquette, Claudie Bourgaux, Karine Ser-Le Roux, Jean-Philippe Michel, Sinda Lepetre-Mouelhi, Institut Galien Paris-Sud (IGPS), Université Paris-Sud - Paris 11 (UP11)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Plateforme d’évaluation préclinique (PFEP), Analyse moléculaire, modélisation et imagerie de la maladie cancéreuse (AMMICa), Centre National de la Recherche Scientifique (CNRS)-Université Paris-Sud - Paris 11 (UP11)-Institut Gustave Roussy (IGR)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université Paris-Sud - Paris 11 (UP11)-Institut Gustave Roussy (IGR)-Institut National de la Santé et de la Recherche Médicale (INSERM), 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), Université Paris-Sud - Paris 11 (UP11)-Institut Gustave Roussy (IGR)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université Paris-Sud - Paris 11 (UP11)-Institut Gustave Roussy (IGR)-Institut National de la Santé et de la Recherche Médicale (INSERM)-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: Male, Squalene, Adenosine, Chemistry, Pharmaceutical, education, Pharmaceutical Science, Nanoparticle, 02 engineering and technology, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, 03 medical and health sciences, Freeze-drying, chemistry.chemical_compound, Mice, 0302 clinical medicine, Cryoprotective Agents, Drug Stability, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Animals, Humans, Particle Size, Chromatography, Chemistry, technology, industry, and agriculture, Trehalose, Biological activity, [CHIM.MATE]Chemical Sciences/Material chemistry, Hep G2 Cells, 021001 nanoscience & nanotechnology, Freeze Drying, Nanomedicine, 030220 oncology & carcinogenesis, Hepatocytes, Nanoparticles, 0210 nano-technology
Abstract: International audience; Squalene-adenosine (SQAd) nanoparticles (NPs) were found to display promising pharmacological activity similar to many other nanomedicines, but their long-term stability was still limited, and their preparation required specific know-how and material. These drawbacks represented important restrictions for their potential use in the clinic. Freeze-drying nanoparticles is commonly presented as a solution to allow colloidal stability, but this process needs to be adapted to each nanoformulation. Hence, we aimed at developing a specific protocol for freeze-drying SQAd NPs while preserving their structural features. NPs were lyophilised, resuspended and analysed by dynamic light scattering, atomic force microscopy and small-angle scattering. Among four different cryoprotectants, trehalose was found to be the most efficient in preserving NPs physico-chemical characteristics. Interestingly, we identified residual ethanol in NP suspensions as a key parameter which could severely affect the freeze-drying outcome, leading to NPs aggregation. Long-term stability was also assessed. No significant change in size distribution or zeta potential could be detected after three-month storage at 4?°C. Finally, freeze-dried NPs innocuity was checked in vitro on cultured hepatocytes and in vivo on mice. In conclusion, optimisation of freeze-drying conditions resulted in safe lyophilised SQAd NPs that can be easily stored, shipped and simply reconstituted into an injectable form.
Published: 2019
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11. Irradiation Effects on Polymer-Grafted Gold Nanoparticles for Cancer Therapy

Author: Fabienne Testard, G. C. Fadda, Serge Palacin, Aurélie Paquirissamy, Marine Le Goas, Caroline Aymes-Chodur, Geraldine Carrot, Thierry Pourcher, Jean Philippe Renault, Béatrice Cambien, Emile Jubeli, Dorra Gargouri, 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), Groupe matériaux et santé, Université Paris-Sud - Paris 11 (UP11), Transporteurs et Imagerie, Radiothérapie en Oncologie et Mécanismes biologiques des Altérations du Tissu Osseux (TIRO-MATOs - UMR E4320), 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)-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), 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), Immunite anti-tumorale et chimiotactisme. Adenocarcinomes et métastases, COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-IFR50-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université Côte d'Azur (UCA), ANR-10-LABX-0035,Nano-Saclay,Paris-Saclay multidisciplinary Nano-Lab(2010), 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), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Université Paris-Saclay, 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, Institut National de la Santé et de la Recherche Médicale (INSERM)-IFR50-Université Nice Sophia Antipolis (... - 2019) (UNS), COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-Université Côte d'Azur (UCA), Palacin, Serge, and Paris-Saclay multidisciplinary Nano-Lab - - Nano-Saclay2010 - ANR-10-LABX-0035 - LABX - VALID
Subjects: chemistry.chemical_classification, [CHIM.MATE] Chemical Sciences/Material chemistry, Atom-transfer radical-polymerization, Small-angle X-ray scattering, Chemistry, Biochemistry (medical), Size-exclusion chromatography, Biomedical Engineering, Nanoparticle, Context (language use), 02 engineering and technology, General Chemistry, Polymer, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, Photochemistry, 01 natural sciences, 3. Good health, 0104 chemical sciences, Biomaterials, Colloidal gold, Irradiation, 0210 nano-technology
Abstract: In the context of cancer treatment, gold nanoparticles (AuNPs) are considered as very promising radiosensitizers. Here, well-defined polymer-grafted AuNPs were synthesized and studied under gamma irradiation to better understand the involved radiosensitizing mechanisms. First, various water-soluble and well-defined thiol-functionalized homopolymers and copolymers were obtained through atom transfer radical polymerization. They were then used as ligands in the one-step synthesis of AuNPs, which resulted in stable hybrid metal-polymer nanoparticles. Second, these nano-objects were irradiated in solution by γ rays at different doses. Structures were fully characterized through size exclusion chromatography, small-angle X-ray scattering, and small-angle neutron scattering measurements, prior to and after irradiation. We were thus able to quantify and to localize radiation impacts onto the grafted polymers, revealing the production sites of reactive species around AuNPs. Both external and near-surface scissions were observed. Interestingly, the ratio between these two effects was found to vary according to the nature of polymer ligands. Medium-range and long-distance dose enhancements could not be identified from the calculated scission yields, but several mechanisms were considered to explain high yields found for near-surface scissions. Then cytotoxicity was shown to be equivalent for both nonirradiated and irradiated polymer-grafted NPs, which suggested that released polymer fragments were nontoxic. Finally, the potential to add bioactive molecules such as anticancer drugs has been explored by grafting doxorubicin onto the polymer corona. This may lead to nano-objects combining both radiosensitization and chemotherapy effects. This work is the first one to study in details the impact of radiation on radiosensitizing nano-objects combining physical, chemical, and biological analyses.
Published: 2018
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12. Towards Accurate Analysis of Particle Size Distribution for Non-Spherically Shaped Nanoparticles as Quality Control Materials

Author: Valter Maurino, Francesco Pellegrino, Vasile-Dan Hodoroaba, Sylvie Marguet, Olivier Taché, Ulrich Mansfeld, Fabienne Testard, BAM Federal Institute for Materials Research and Testing, Federal Institute for Materials Research and Testing - Bundesanstalt für Materialforschung und -prüfung (BAM), Dipartimento di Chimica [Torino], Università degli studi di Torino (UNITO), Laboratoire Edifices Nanométriques (LEDNA), 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), Università degli studi di Torino = University of Turin (UNITO), 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: 010302 applied physics, [PHYS.PHYS.PHYS-OPTICS]Physics [physics]/Physics [physics]/Optics [physics.optics], Acicular, Materials science, Analytical chemistry, Nanoparticle, 02 engineering and technology, 021001 nanoscience & nanotechnology, 01 natural sciences, Nanomaterials, chemistry.chemical_compound, chemistry, 0103 physical sciences, Titanium dioxide, Particle-size distribution, Nano, Nanorod, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Particle size, 0210 nano-technology, Instrumentation, ComputingMilieux_MISCELLANEOUS
Abstract: Measurement of nanoparticle size (distribution) becomes a challenging analytical problem when non-spherical nanoparticles must be accurately measured. Most industrial nanoparticles have not only non-spherical shapes but also possess polydisperse size distributions, and due to their agglomeration/aggregation state are difficult (or even impossible) to be addressed individually. Moreover, driven by regulatory purposes related to the identification of a material as a nanomaterial, the accurate measurement of the smallest dimension of a (nano)particulate material makes the analysis even more complex. In the first phase of the EU Project nPSize - Improved traceability chain of nanoparticle size measurements (https://www.bam.de/Content/DE/Projekte/laufend/nPSize/npsize.html), the efforts are focused on synthesis of nanoparticles of well-defined, non-spherical shape. Following candidates of reference materials (CRM) with certifiable particle size (distribution) are under characterization with respect to their homogeneity and stability: (i) titania nanoplatelets (10-15 nm thickness x 50-60 nm lateral), (ii) titania bipyramides (~60 nm length x 40 nm width), (iii) titania acicular particles (100 nm length x 15-20 nm width; aspect ratio 5.5/6), (iv) gold nanorods (~10 nm width x 30 nm length), and (v) gold nanocubes (~55 nm x 55 nm x 55 nm).
Published: 2019
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13. Molten fatty acid based microemulsions †

Author: Christophe Déjugnat, Fabienne Testard, Cecile Noirjean, Jacques Jestin, 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), Interactions moléculaires et réactivité chimique et photochimique (IMRCP), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD), Laboratoire Léon Brillouin (LLB - UMR 12), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Université Paris-Saclay, 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 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 Ecologie et Environnement (INEE), Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Fédération de Recherche Fluides, Energie, Réacteurs, Matériaux et Transferts (FERMAT), 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)-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)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), SMODD - Systèmes Moléculaires Organisés et Développement Durable (SMODD), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie de Toulouse (ICT), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)
Subjects: Ternary numeral system, Chemistry, General Physics and Astronomy, Myristic acid, 02 engineering and technology, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, chemistry.chemical_compound, Chemical engineering, Pulmonary surfactant, Phase (matter), Organic chemistry, Lamellar structure, Microemulsion, Physical and Theoretical Chemistry, Long chain fatty acid, 0210 nano-technology, Ternary operation
Abstract: International audience; a We show that ternary mixtures of water (polar phase), myristic acid (MA, apolar phase) and cetyltrimethyl-ammonium bromide (CTAB, cationic surfactant) studied above the melting point of myristic acid allow the preparation of microemulsions without adding a salt or a co-surfactant. The combination of SANS, SAXS/ WAXS, DSC, and phase diagram determination allows a complete characterization of the structures and interactions between components in the molten fatty acid based microemulsions. For the different structures characterized (microemulsion, lamellar or hexagonal phases), a similar thermal behaviour is observed for all ternary MA/CTAB/water monophasic samples and for binary MA/CTAB mixtures without water: crystalline myristic acid melts at 52 1C, and a thermal transition at 70 1C is assigned to the breaking of hydrogen bounds inside the mixed myristic acid/CTAB complex (being the surfactant film in the ternary system). Water determines the film curvature, hence the structures observed at high temperature, but does not influence the thermal behaviour of the ternary system. Myristic acid is partitioned in two ''species'' that behave independently: pure myristic acid and myristic acid associated with CTAB to form an equimolar complex that plays the role of the surfactant film. We therefore show that myristic acid plays the role of a solvent (oil) and a co-surfactant allowing the fine tuning of the structure of oil and water mixtures. This solvosurfactant behaviour of long chain fatty acid opens the way for new formulations with a complex structure without the addition of any extra compound.
Published: 2016
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14. Uranium Extraction by a Bifunctional Amido-Phosphonic Acid: Coordination Structure and Aggregation

Author: Laurence Berthon, Dominique Guillaumont, Olivia Pecheur, Raphaël Turgis, Sandrine Dourdain, Fabienne Testard, Guilhem Arrachart, Clara Fillaux, Tri ionique par les Systèmes Moléculaires auto-assemblés (LTSM), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), 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), Département RadioChimie et Procédés (DRCP), 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), 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 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)
Subjects: Aggregation number, Extended X-ray absorption fine structure, 010405 organic chemistry, Ligand, General Chemical Engineering, Inorganic chemistry, Extraction (chemistry), chemistry.chemical_element, General Chemistry, Actinide, Uranium, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, chemistry.chemical_compound, chemistry, [CHIM]Chemical Sciences, Bifunctional, Phosphoric acid, ComputingMilieux_MISCELLANEOUS
Abstract: Butyl-N,N-di(2-ethylhexyl)carbamoyl-nonylphosphonate (DEHCNPB) is a new amido-phosphonic acid bifunctional ligand with a high uranium extraction efficiency from wet phosphoric acid. In the present work, the DEHCNPB coordination structure toward uranium and its aggregation properties have been fully characterized using experimental and theoretical approaches. DEHCNPB forms associated species, and its aggregation properties such as aggregation number or CAC have been determined from SAXS and SANS measurements. The preferred site for bonding of DEHCNPB toward U(VI) has been determined from IR, EXAFS, and DFT calculations.
Published: 2016
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15. Synergism in a HDEHP/TOPO Liquid−Liquid Extraction System: An Intrinsic Ligands Property?

Author: Sandrine Dourdain, J. Rey, Stéphane Pellet-Rostaing, Marie-Christine Charbonnel, O. Pecheur, Philippe Guilbaud, Dominique Guillaumont, Fabienne Testard, Laurence Berthon, Département RadioChimie et Procédés (DRCP), 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), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), 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), Tri ionique par les Systèmes Moléculaires auto-assemblés (LTSM), 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), 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), 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), and 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)
Subjects: inorganic chemicals, Chemistry, Vapor pressure osmometry, Supramolecular chemistry, Infrared spectroscopy, Nanotechnology, 02 engineering and technology, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, Mass spectrometry, 01 natural sciences, Micelle, 0104 chemical sciences, Surfaces, Coatings and Films, Molecular dynamics, Liquid–liquid extraction, Materials Chemistry, Molecule, Physical chemistry, Physical and Theoretical Chemistry, 0210 nano-technology
Abstract: International audience; Among the proposed mechanisms to predict and understand synergism in solvent extraction, the possibility of a preorganization of the mixture of extractant molecules has never been considered. Whether involving synergistic aggregation as for solubilization enhancement with reverse micelles or favored molecular interaction between the extractant molecules, evaluation of this hypothesis requires characterization of the aggregates formed by the extractant molecules at different scales. We investigate here the HDEHP/ TOPO couple of extractant with methods ranging from vibrational spectroscopy and ESI-MS spectrometry to vapor pressure osmometry and neutron and X-ray scattering to cover both molecular and supramolecular scales. These experimental methods are subjected to DFT calculations and molecular dynamics calculations, allowing a rationalization of the results through the different scales. Performed in the absence of any cation, this original study allows a decorrelation of the mechanisms at the origin of synergy: it appears that no clear preorganization of the extractants can explain the synergy and therefore that the synergistic aggregation observed in the presence of cations is rather due to the chelation mechanisms than to intrinsic properties of the extractant molecules.
Published: 2016
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16. A Comprehensive Study of the Mechanism of Formation of Polyol-Made Hausmannite Nanoparticles: From Molecular Species to Solid Precipitation

Author: Jean-Yves Piquemal, Olivier Taché, L. Sicard, Tarik Rhadfi, Yann Le Du, Laurent Binet, Ahmed Atlamsani, Elodie Anxolabéhère-Mallart, and Fabienne Testard
Subjects: chemistry.chemical_classification, Precipitation (chemistry), Nanoparticle, Nanotechnology, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, chemistry.chemical_compound, General Energy, chemistry, Polyol, Chemical engineering, Mechanism (philosophy), Physical and Theoretical Chemistry, Hausmannite
Abstract: This study aims at achieving a better understanding of the mechanisms of formation of Mn3O4 nanoparticles prepared by the polyol process. The role of each reactant is studied, and a possible scheme...
Published: 2012
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17. Influence of the extracted solute on the aggregation of malonamide extractant in organic phases: Consequences for phase stability

Author: Laurence Martinet, Charles Madic, Laurence Berthon, Fabienne Testard, and Thomas Zemb
Subjects: chemistry.chemical_classification, Aggregation number, Chemistry, General Chemical Engineering, Inorganic chemistry, General Chemistry, Uranyl, Micelle, chemistry.chemical_compound, Third phase, Uranyl nitrate, Liquid–liquid extraction, Phase (matter), Alkyl
Abstract: Due to their amphiphilic properties, malonamide molecules in alkane are organized in reverse micelle type aggregates, composed of a polar core formed by the malonamide polar heads and the extracted solutes, and surrounded by a hydrophobic shell made up of the extractant alkyl chains. The aggregates interact with one another through an attractive potential, leading to the formation of a third phase. This occurs with the splitting of the organic phase into a light phase composed mostly of diluent, and a heavy third phase containing highly concentrated extractant and solutes. In this article, we show that the aggregation (monomer concentration, domain of stability, and attractive potential between micelles) greatly depends on the nature of the extracted solute, whereas the size of aggregate (aggregation number) is only slightly influenced by this. We describe the extraction of water, nitric acid, neodymium nitrate and uranyl nitrate. Strongly polarizable species induce consistently large attraction potentials and a small stability domain for the dispersion of nanodroplets in the solvent. Highly polarizable ions such as lanthanides or uranyl induce more long-range attractive interactions than do protons.
Published: 2010
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18. 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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19. Solubilization and interfacial curvature in microemulsions

Author: Alan Parker, Fabienne Testard, Daniel Benczédi, Thomas Zemb, Vera Tchakalova, and Kenneth Wong
Subjects: Chemistry, Co extraction, Analytical chemistry, Thermodynamics, Curvature, Crystallography, Colloid and Surface Chemistry, Adsorption, Chemical engineering, Pulmonary surfactant, Solubilization, Phase (matter), Molecule, Microemulsion, Absorption (chemistry), Phase diagram, Co solvent
Abstract: We show that solubilization in microemulsion droplets is best described as a combination of interfacial adsorption and internal absorption. We progressively add solute to a Winsor type I system, and simultaneously measure the amount of solute at the oil–water interface and its effect on the interfacial curvature. We determine the relationship between the effective packing parameter and the amount of solute adsorbed at the oil–water interface. For four solutes, a significant amount of oil is co-extracted with solute into the interfacial film. Moreover, we show that solubilization in microemulsions can be characterized by two physical quantities with precise meaning: (1) the increase in interfacial area per molecule of adsorbed solute and (2) the number of oil molecules co-extracted with each solute molecule into the interfacial film. To quantify these effects, we introduce the constant interfacial thickness (CIT) model. It provides a general relationship between curvature, packing and interfacial composition in oil/water/surfactant/solute mixtures. Finally, we show that these results can be used to calculate the free energy of transfer of solute and oil from the droplet core to the interface.
Published: 2008
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20. Self-assembling properties of malonamide extractants used in separation processes

Author: Benjamin Abécassis, Laurence Berthon, Charles Madic, Fabienne Testard, Th. Zemb, L. Martinet, and Pierre Bauduin
Subjects: Octanol, Extraction (chemistry), Analytical chemistry, Micelle, symbols.namesake, chemistry.chemical_compound, chemistry, Chemical engineering, Third phase, Liquid–liquid extraction, Phase (matter), symbols, Microemulsion, Physical and Theoretical Chemistry, van der Waals force
Abstract: A review of the four microstructures present in oil phases of malonamide extractants used for nuclear fuel reprocessing is presented in relation with the extraction properties and the third phase formation. Due to their surface active properties, extractants can be considered as a weak surfactants and are organised into reverse micelles interacting through an attractive potential. The Van der Waals attractions between the cores of reverse micelles are the key parameters for understanding “third phase” formation. Extractant solutions are similar to reverse microemulsions and the stability rules known in the field of microemulsions can be applied. In some cases, micelles are transformed into a regular molecular solution by modest heating. Apart from micellar and regular solutions, two new modes of association of extractant molecules have been identified. Networks of H-bounds are obtained when “modifiers” such as octanol are added by formulators in order to improve stability range. Microphase separation in a more crystalline phase may be obtained by increasing extractant and/or ion concentrations.
Published: 2008
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21. Futuristic back-end of the nuclear fuel cycle with the partitioning of minor actinides

Author: Charles Madic, Jan-Olov Liljenzin, M. Ferrando, A. Facchini, Birgit Christiansen, Fabienne Testard, Giuseppe Modolo, Pascal Baron, Michael J. Hudson, Andreas Geist, J. De Mendoza, B. Boullis, and A.G. Espartero
Subjects: Nuclear fuel cycle, Nuclear transmutation, Hydrometallurgy, Mechanics of Materials, Chemistry, Mechanical Engineering, Radiochemistry, Materials Chemistry, Metals and Alloys, Radioactive waste, Actinide, PUREX, Solvent extraction
Abstract: For future back-end of the nuclear fuel cycle, the partitioning of minor actinides: Np, Am and Cm, followed by their transmutation will minimize importantly the radiotoxicity of nuclear glass waste. In this paper, the research done in France and in Europe will be presented: (i) partitioning of Np by modified PUREX process, (ii) partitioning of Am and Cm by the DIAMEX and SANEX hydrometallurgical processes. (c) 2007 Published by Elsevier B.V.
Published: 2007
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22. Liquid–liquid extraction: An adsorption isotherm at divided interface?

Author: Laurence Berthon, Fabienne Testard, and Thomas Zemb
Subjects: Langmuir, Aggregation number, Chromatography, Chemistry, General Chemical Engineering, Extraction (chemistry), Solvation, Analytical chemistry, Langmuir adsorption model, General Chemistry, Condensed Matter::Soft Condensed Matter, symbols.namesake, Adsorption, Liquid–liquid extraction, symbols, Physics::Chemical Physics, Solubility
Abstract: We show that liquid–liquid extraction can be described as the equilibrium between two pseudophases of ions: the hydrated state in the water phase and the solvation state when the ions are adsorbed on an organized interface. The extractant is considered as a potential surface where the ions can adsorb. Unlike phenomenological binding “constants”, ion extraction/stripping can be seen as the sum of Langmuir isotherms. The number of aggregated extractants in one reverse micelle in the solvent is at least equal to or higher than the number of extracting molecules complexed at a given instant to the ion to be extracted. Considering extraction equilibrium as a sum of isotherms corresponding to the different states of aggregation of extractant molecule in the solvent, the resulting constant is representative of both the efficiency of the extraction and the structure of the solution. This is a first step toward the development of predictive models for the apparent distribution coefficients.
Published: 2007
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23. Solvent Penetration and Sterical Stabilization of Reverse Aggregates based on the DIAMEX Process Extracting Molecules: Consequences for the Third Phase Formation

Author: Fabienne Testard, Laurence Berthon, Th. Zemb, Charles Madic, and L. Martinet
Subjects: Phase transition, Aggregation number, Chemistry, Vapor pressure osmometry, General Chemical Engineering, Supramolecular chemistry, General Chemistry, Micelle, chemistry.chemical_compound, Third phase, Nitric acid, Physical chemistry, Organic chemistry, Phase diagram
Abstract: Studies on third phase formation during the extraction of nitric acid by malonamide extractants in various diluents are investigated. This “third phase transition” is studied from a fundamental point of view, combining vapor pressure osmometry, phase diagram, and scattering studies. The organization of the organic phases of the “malonamides/alkane/water/nitric acid” systems was studied at three “scales”: 1/at a molecular scale by determining the compositions of the extracted complexes; 2/at a macroscopic scale by determining the phase transition boundaries quantified by the limiting organic concentration (LOC) of solutes; and 3/at a supramolecular scale by analyzing the organization of the species in the organic phases (i.e. measuring the critical micellization concentration, the aggregation number, and the interactions between the aggregates). The instability (third phase apparition) has a supramolecular origin: it is a “long range” attraction between polar cores of the reverse micelles formed b...
Published: 2007
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24. 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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25. The role of solvent swelling in the self-assembly of squalene based nanomedicines

Author: Patrick Couvreur, Aurel Radulescu, Fatima Zouhiri, Annie Brûlet, Didier Desmaële, Isabelle Grillo, Olivier Spalla, Debasish Saha, Fabienne Testard, Sylvain Desert, 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), Institut Galien Paris-Sud (IGPS), Université Paris-Sud - Paris 11 (UP11)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), 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), 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, Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Université Paris-Saclay, Jülich Centre for Neutron Science (JCNS), Forschungszentrum Jülich GmbH | Centre de recherche de Juliers, Helmholtz-Gemeinschaft = Helmholtz Association-Helmholtz-Gemeinschaft = Helmholtz Association, and Palacin, Serge
Subjects: Squalene, Nanoparticle, Antineoplastic Agents, chemistry.chemical_compound, Scattering, Small Angle, medicine, Organic chemistry, Particle Size, ComputingMilieux_MISCELLANEOUS, Coalescence (physics), [CHIM.MATE] Chemical Sciences/Material chemistry, Ethanol, Water, General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, Condensed Matter Physics, Small-angle neutron scattering, Solvent, Neutron Diffraction, Nanomedicine, chemistry, Chemical engineering, Solvents, Nanoparticles, Particle size, Swelling, medicine.symptom
Abstract: International audience; Squalene based nanoparticles obtained via nanoprecipitation are promising candidates as efficient anti-cancer drugs. In order to highlight their preparation process and to facilitate further clinical translation, the present study enlightens the paramount role of the solvent in the formation of these nanomedicines. Three different squalene-based nanoparticles, i.e. squalenic acid, deoxycytidine squalene and gemcitabine squalene, have been investigated before and after organic solvent evaporation. Size and structural analysis by Small Angle Neutron Scattering revealed that droplets' size was uniquely controlled by the solvent composition (ethanol–water), which evolved during their gradual formation. The particles were preferably swollen by water and the swelling increased when less ethanol was present. Either coalescence or fragmentation was observed depending on the increase or decrease of the ethanol content, supporting an equilibrium control of the size. Moreover, a high water swelling was observed for the three local organization of the nanodroplets (hexagonal for gemcitabine squalene, cubic for deoxycytidine and not structured for squalenic acid) and could be the source of the previously reported efficiency of related anti-cancer squalene based nanomedicines.
Published: 2015
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26. Aggregation Properties ofN,N,N′,N′‐Tetraoctyl‐3‐oxapentanediamide (TODGA) inn‐Dodecane

Author: Charles Madic, Fabienne Testard, Giuseppe Modolo, and S. Nave
Subjects: Chemistry, Small-angle X-ray scattering, General Chemical Engineering, General Chemistry, Neutron scattering, Diluent, Micelle, Ion, Crystallography, chemistry.chemical_compound, Nitric acid, Molecule, Polar, Physical chemistry
Abstract: N,N,N′,N′‐Tetraoctyl‐3‐oxapentanediamide (TODGA) in n‐dodecane was studied to characterize the aggregation properties of the extractant and the formation of a third‐phase when nitric acid is extracted. Tensiometry and small‐angle x‐ray and neutron scattering (SAXS and SANS) revealed the presence of small aggregates dispersed in the diluent. The aggregates are spherical reverse micelles consisting of a polar core containing water and the extracted ions and surrounded by approximately four extractant molecules. When the initial nitric acid content is increased, the aggregates remain spherical, their size increases as more water and ions are extracted and inter‐particle attraction increases. The sticky hard‐sphere model proposed by Baxter was used successfully to describe the small reverse micelles of the organic TODGA phases and quantify their interactions. These attractive interactions were found responsible for the formation of the third‐phase.
Published: 2004
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27. 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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28. Recycling metals by controlled transfer of ionic species between complex fluids: en route to 'ienaics'

Author: Jean-François Dufrêche, Thomas Zemb, Caroline Bauer, Fabienne Testard, Sandrine Dourdain, Christophe Déjugnat, Olivier Diat, Magali Duvail, Luc Belloni, Chantal Larpent, Stéphane Pellet-Rostaing, Pierre Bauduin, Véronique Dubois, Tri ionique par les Systèmes Moléculaires auto-assemblés (LTSM), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), 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), Ions aux Interfaces Actives (L2IA), 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), Modélisation Mésoscopique et Chimie Théorique (LMCT), Institut Lavoisier de Versailles (ILV), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and 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)
Subjects: Polymers and Plastics, Chemistry, Free energy of transfer, Thermodynamics, Ionic bonding, Self-assembly, Liquid-liquid extraction, Ion, Physics::Fluid Dynamics, Condensed Matter::Soft Condensed Matter, Colloid, Colloid and Surface Chemistry, Ion selectivity, Materials Chemistry, Physical chemistry, [CHIM]Chemical Sciences, Microemulsion, Physical and Theoretical Chemistry, Chemical equilibrium, Ieanics, Dissolution, ComputingMilieux_MISCELLANEOUS, Phase diagram, Complex fluid, Adsoprtion isotherm
Abstract: Recycling chemistry of metals and oxides relies on three steps: dissolution, separation and material reformation. We review in this work the colloidal approach of the transfer of ions between two complex fluids, i.e. the mechanism at the basis of the liquid-liquid extraction technology. This approach allows for rationalizing in a unified model transformation such as accidently splitting from two to three phases, or uncontrolled viscosity variations, as linked to the transformation in the phase diagram due to ion transfer. Moreover, differences in free energies associated to ion transfer between phases that are the origin of the selectivity need to be considered at the meso-scale beyond parameterization of an arbitrary number of competing “complexes”. Entropy and electrostatics are taken into account in relation to solvent formulation. By analogy with electronics dealing about electrons transported in conductors and semi-conductors, this “ienaic” approach deals with ions transported between nanostructures present in colloidal fluids under the influence of chemical potential gradients between nanostructures coexisting in colloidal fluids. We show in this review how this colloidal approach generalizes the multiple chemical equilibrium models used in supra-molecular chemistry. Statistical thermodynamics applied to self-assembled fluids requires only a few measurable parameters to predict liquid-liquid extraction isotherms and selectivity in multi-phase chemical systems containing at least one concentrated emulsified water in oil (w/o) or oil in water (o/w) microemulsion.
Published: 2015
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29. Interpretation of phase diagrams: topological and thermodynamical constraints

Author: Fabienne Testard and Thomas Zemb
Subjects: Surface (mathematics), Theoretical physics, Colloid and Surface Chemistry, Chemistry, Thermodynamics, Binary number, Order (ring theory), Curvature, Ternary operation, Interpretation (model theory), Phase diagram
Abstract: Some general principles of surfactant self-assembly are rationalised in order to give a short introduction to the use of phase diagrams for binary (two components) and ternary (three components) systems. Finally models for solubilisation are considered to be understood within the frame of those general packing principles: volume, surface and curvature conservation.
Published: 2002
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30. 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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31. Quenched microemulsions: a new route to proton conductors

Author: Olivier Taché, Cecile Noirjean, Fabienne Testard, David Carriere, Jacques Jestin, Christophe Déjugnat, 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 Léon Brillouin (LLB - UMR 12), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Université Paris-Saclay, Interactions moléculaires et réactivité chimique et photochimique (IMRCP), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD), 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), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), 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 Ecologie et Environnement (INEE), Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Fédération de Recherche Fluides, Energie, Réacteurs, Matériaux et Transferts (FERMAT), 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)-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)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), and Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)
Subjects: chemistry.chemical_classification, Ammonium bromide, Materials science, General Chemistry, Polymer, [CHIM.MATE]Chemical Sciences/Material chemistry, Condensed Matter Physics, chemistry.chemical_compound, Membrane, chemistry, Chemical engineering, Lamellar phase, Phase (matter), Melting point, Organic chemistry, [CHIM]Chemical Sciences, Microemulsion, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Phase diagram
Abstract: International audience; Solid-state proton conductors operating under mild temperature conditions (T < 150 [degree]C) would promote the use of electrochemical devices as fuel cells. Alternatives to the water-sensitive membranes made of perfluorinated sulfonated polymers require the use of protogenic moieties bearing phosphates/phosphonates or imidazole groups. Here, we formulate microemulsions using water, a cationic surfactant (cetyltrimethyl ammonium bromide, CTAB) and a fatty acid (myristic acid, MA). The fatty acid acts both as an oil phase above its melting point (52 [degree]C) and as a protogenic moiety. We demonstrate that the mixed MA-CTA film presents significant proton conductivity. Furthermore, bicontinuous microemulsions are found in the water-CTAB-MA phase diagram above 52 [degree]C, where molten MA plays both the role of the oil phase and the co-surfactant. This indicates that the hydrogen-bond rich MA-CTA film can be formulated in the molten phase. The microemulsion converts into a lamellar phase upon solidification at room temperature. Our results demonstrate the potential of such self-assembled materials for the design of bulk proton conductors, but also highlight the necessity to control the evolution of the nanostructure upon solidification of the oil phase.
Published: 2014
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32. Micellization of dodecyltrimethylammonium bromide in water–dimethylsulfoxide mixtures: A multi-length scale approach in a model system

Author: Fabienne Testard, Véronique Peyre, Sabah Bouguerra, Physicochimie des Electrolytes, Colloïdes et Sciences Analytiques (PECSA), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Préparatoire aux Etudes d'Ingénieur de Tunis (IPEIT), Université de Tunis, 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: Molar volume, Thermodynamics of micellization, Thermodynamics, Dodecyltrimethylammonium bromide, Solvation, 02 engineering and technology, 010402 general chemistry, Mole fraction, 01 natural sciences, Micelle, Biomaterials, Colloid and Surface Chemistry, Organic chemistry, Conductimetry, Water–DMSO mixtures, Aggregation number, Chemistry, SANS, Micellization, 021001 nanoscience & nanotechnology, Small-angle neutron scattering, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Critical micelle concentration, 0210 nano-technology
Abstract: International audience; The micellization in mixed solvent was studied using conductimetry, density measurements (molar volumes), and small angle neutron scattering (SANS) to explore dodecyltrimethylammonium bromide (DTABr) micelle formation throughout the entire composition range of water–dimethylsulfoxide (DMSO) mixtures. As the concentration of DMSO was increased in the mixture, the critical micelle concentration (CMC) increased, the aggregation number decreased and the ionization degree increased, until no aggregates could be detected any more for DMSO molar fraction higher than 0.51. The results were consistent with the presence of globular micelles interacting via a coulombic potential. The experimental CMC values and aggregation numbers were successfully reconciled with a molecular thermodynamic model describing the micellization process in solvent mixtures (R. Nagarajan and C.-C. Wang, Langmuir 16 (2000) 5242). The structural and thermodynamic characterization of the micelles agreed with the prediction of a dissymmetric solvation of the surfactant entity: the hydrocarbon chain was surrounded only by DMSO while the polar head was surrounded only by water. The decrease in the ionization degree was due to the condensation of the counterions and was definitely linked to the geometrical characteristics of the aggregates and by no means to the CMC or salinity. This multi-technique study provides new insight into the role of solvation in micellization and the reason for the decrease in ionization degree, emphasizing the dissymmetric solvation of the chain by DMSO and the head by water. This is the first time that, for a given surfactant in solvent mixtures, micellization is described using combined analysis from molecular to macroscopic scale.
Published: 2013
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33. 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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34. 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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35. ChemInform Abstract: Third-Phase Formation in LiquidâLiquid Extraction: A Colloidal Approach

Author: Laurence Berthon, Th. Zemb, Pierre Bauduin, and Fabienne Testard
Subjects: Colloid, Chemical engineering, Third phase, Chemistry, Extraction (chemistry), General Medicine
Published: 2010
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36. Ternary phase diagrams of a thermoreversible chelating non-ionic surfactant

Author: H . Coulombeau, K . Baczko, Fabienne Testard, Th. Zemb, S. Nave, and C . Larpent
Subjects: Ternary numeral system, Chromatography, Chemical engineering, Pulmonary surfactant, Lyotropic liquid crystal, Chemistry, Liquid crystal, Liquid–liquid extraction, Phase (matter), General Physics and Astronomy, Microemulsion, Physical and Theoretical Chemistry, Ternary operation
Abstract: The behaviour of a di-block molecule associating a diamide group and a non-ionic surfactant (C(i)E(j)) is determined in a ternary surfactant/water/oil/system. Its properties are compared to the ones of a parent non-ionic surfactant C(i)E(j) through the limits of boundaries in the phase prisms. The existence of a stable microemulsion single phase in a defined temperature and concentration range is demonstrated. The extension of the microemulsion domain is limited by the presence of a gel, containing lyotropic liquid crystals as gelling agents. Temperature dependence is observed for the curvature below the temperature of zero spontaneous curvature, but the ternary system cannot produce reverse microemulsion as observed with classical C(i)E(j). The decrease of the mean curvature with temperature is inhibited by the presence of the diamide as a grafted complexing group. Liquid-liquid extraction processes with this type of surfactant are possible, but will require the presence of at least a fourth component to enlarge the water in an oil microemulsion domain.
Published: 2009

37. 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

38. Solubilization in alkanes by alcohols as reverse hydrotropes or 'lipotropes'

Author: Fabienne Testard, Th. Zemb, and Pierre Bauduin
Subjects: Alkane, chemistry.chemical_classification, chemistry.chemical_compound, Aqueous solution, chemistry, Solubilization, Dodecane, Materials Chemistry, Organic chemistry, Molecule, Physical and Theoretical Chemistry, Micelle, Surfaces, Coatings and Films
Abstract: Hydrotropes in aqueous systems do not aggregate in micelles, inhibit presence of mesophases and allow significant and progressive solubilization of "insoluble" molecules in water. It was shown that n-alcohols in alkanes develop the same properties, including the power-law for maximum solubilization of "hydrophilic" molecules. The aim of this paper is to highlight properties of reverse hydrotropes or "lipotropes" by taking n-alcohol/alkane mixtures as model systems. So as to establish a clear parallel between lipotropes and hydrotropes the same methodology used to characterize hydrotropes was applied to these systems. The solubilization of solutes insoluble in alkane, i.e. water and a hydrophilic dye in dodecane, enabled by the addition of n-alcohols ( n = 2, 3, 4 and 7) was studied. In parallel, the nonmicellar aggregation state of butan-1-ol and heptan-1-ol in dodecane was investigated by small-angle X-ray scattering. By applying the Porod's treatment the specific area of the H-bond network formed by heptan-1-ol and the area occupied by hydroxyl group in this network were determined as a function of concentration. A correlation between the aggregation of alcohols in dodecane and the solubilization was made. The disrupting of concentrated mesophases by a lipotrope was illustrated by studying the effect of adding n-alcohols to water/oil/extractant ternary systems used in liquid/liquid extraction. Under some conditions the organic phase splits up into two phases: an extractant mesophase and nearly pure oil. The amount of n-alcohols required to make the extractant mesophase disappear was determined for water/alkane/malonamide extractant systems. The influence of the chain length of the n-alcohol on the efficiency as lipotrope was also experimentally studied. The trend obtained was similar to the one observed with the solubilization experiments.
Published: 2008

39. 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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40. Excess solubilization of lindane in bicontinuous microemulsions

Author: Reinhard Strey, Fabienne Testard, and Th. Zemb
Subjects: chemistry.chemical_compound, Ternary numeral system, Adsorption, Chromatography, Pulmonary surfactant, Chemistry, Amphiphile, Analytical chemistry, Microemulsion, Penetration (firestop), Solubility, Lindane
Abstract: We examine the solubilization of a lipophilic molecule (lindane) in the nonionic system water-oil-CiEj, particularly in the microemulsion domain. Solubilization of lindane in this ternary system induces a variation of the HLB temperature and of the efficiency of the surfactant. The temperature of hydrophilic-lipophilic balance (HLB), or better, the temperature of zero spontaneous curvature T of the film, increases or decreases depending on the relative penetration power of oil and solute (lindane) in the amphiphilic film. We observe an excess solubility of lindane in the microemulsion regime, compared to bulk oil at the same temperature. This allows direct determination of the lindane excess adsorbed in the interfacial film referring to a temperature of the zero average curvature. No area per molecule variation associated to lindane penetration could be detected.
Published: 2007
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41. 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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42. Relation between the hydrophile/hydrophobe ratio of malonamide extractants and the stability of the organic phase: investigation at high extractant concentrations

Author: Pierre Bauduin, Laurence Berthon, Fabienne Testard, and Th. Zemb
Subjects: chemistry.chemical_classification, Dodecane, General Physics and Astronomy, Water, Micelle, Malonates, chemistry.chemical_compound, symbols.namesake, chemistry, Phase (matter), Critical micelle concentration, Radioactive Waste, Alkanes, symbols, Solvents, Physical chemistry, Organic chemistry, Microemulsion, Physical and Theoretical Chemistry, van der Waals force, Hydrophobic and Hydrophilic Interactions, Alkyl, Micelles, Hydrophile
Abstract: In the present paper, it is shown that in malonamide extractant/dodecane mixtures, change in the shape of the extractant aggregate may promote phase demixion. This phenomenon is known as the 3rd phase formation in extractant systems. The shape of the aggregates is dictated by the length of the alkyl chains stabilizing the reverse microemulsion by steric repulsion. Small angle scattering experiments are used to investigate the aggregation states of diamide extractant molecules, namely N,N'dimethyl-N,N'dibutyl-tetradecyl malonamide (DMDBTDMA) and N,N'dimethyl-N,N'dibutyl-pentyl malonamide (DMDBPMA), in dodecane. The results are described in a consistent way by the packing parameter concept and by expressing steric repulsion versus Van der Waals inter-aggregate interactions, both curvature dependants. Non-monotonous change in the extractant Critical Micellar Concentration (CMC) as a function of the extractant alkyl chain length is rationalized by comparing Van der Waals attraction between the alkyl chains of both the extractant and the solvent.
Published: 2007

43. 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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44. 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

45. 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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46. Excess of Solubilization and Curvature in Nonionic Microemulsions

Author: Fabienne Testard and Th. Zemb
Subjects: Aqueous solution, Chromatography, Ternary numeral system, Ethylene oxide, Thermodynamics, Curvature, Micelle, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Biomaterials, chemistry.chemical_compound, Colloid and Surface Chemistry, Adsorption, chemistry, Pulmonary surfactant, Microemulsion
Abstract: We measure separately the amount of solute dissolved in a surfactant monolayer and the average curvature of the relevant sample to establish a link between these two quantities. The model system chosen involves the common hydrophobic pesticide lindane (gamma-C(6)H(6)Cl(6)) in a nonionic surfactant solution of the ethylene oxide type. Excess solubilization, defined as the solubilization in the surfactant film by comparison with bulk oil, is quantified by the interfacial composition lambda (molar ratio solute/surfactant) within the interfacial film. A linear relationship between the amount of solute adsorbed on the film and the induced variation in curvature of the surfactant film is deduced from the phase diagram, dosage, and small-angle scattering experiments in the case of micellar, Winsor I, and several Winsor III domains at equilibrium in the same ternary system. We discuss the linear relationship obtained with constraints set by molecular packing. Copyright 1999 Academic Press.
Published: 1999

47. Nonionic metal-chelating surfactants mediated solvent-free thermo-induced separation of uranyl

Author: Thomas Zemb, Sylvain Prévost, Fabienne Testard, Laurence Berthon, and Chantal Larpent
Subjects: Cloud point, Solvent free, Extraction (chemistry), Inorganic chemistry, General Chemistry, Uranyl, Catalysis, Metal, chemistry.chemical_compound, Uranyl nitrate, chemistry, visual_art, Materials Chemistry, visual_art.visual_art_medium, Chelation
Abstract: Thermo-responsive metal-chelating surfactants permit the solvent-free, cloud point extraction of uranyl nitrate and afford a real molecular economy compared to conventional separation techniques.
Published: 2007
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48. Supramolecular organisation of tri-n-butyl phosphate in organic diluent on approaching third phase transition

Author: Fabienne Testard, L. Martinet, S. Nave, Th. Zemb, C. Mandin, Charles Madic, and Laurence Berthon
Subjects: Alkane, chemistry.chemical_classification, Chromatography, Supramolecular chemistry, Tri-N-butyl Phosphate, General Physics and Astronomy, Micelle, chemistry.chemical_compound, chemistry, Third phase, Chemical engineering, Liquid–liquid extraction, Nitric acid, Phase (matter), Physical and Theoretical Chemistry
Abstract: The supramolecular organisation of organic phases of the extractant tri-n-butyl phosphate (TBP) in alkane diluents is studied. Effects of extractant and nitric acid concentration, temperature and acid nature on third phase formation are presented. The aim is to gain information on the structural aspect of the organic phase just before phase splitting in liquid–liquid extraction. Small-angle X-ray and neutron scattering combined to vapour pressure osmometry, tensiometry and conductivity are used to characterise these systems. It is shown that organic phases of TBP in equilibrium with acid solutions are organised in reverse interacting aggregates and that these interactions govern the formation of the third phase. These aggregates disappear at high temperatures, even in the presence of HNO3, to form regular molecular solutions. The shape and size of the aggregates are not modified by varying the acid nature, HNO3 or TBP concentrations, whereas low temperatures and polarisability of the aqueous micellar core affect the strength of the interactions. The sticky sphere model proposed by Baxter is used successfully to model the small reverse micelles of the organic TBP phases and quantify their interactions.
Published: 2004
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49. Thermo-responsive Metal-chelating Surfactants: Properties and Use in Cloud Point Extraction of Uranyl Nitrate

Author: Sylvain Prévost, Nicole Zorz, Th. Zemb, Laurence Berthon, Hervé Desvaux, Chantal Larpent, Helene Coulombeau, Fabienne Testard, and Krystyna Baczko
Subjects: Cloud point, General Chemical Engineering, Inorganic chemistry, General Chemistry, Condensed Matter Physics, Uranyl, Metal, chemistry.chemical_compound, Residue (chemistry), Uranyl nitrate, chemistry, visual_art, Micellar solutions, visual_art.visual_art_medium, Chelation, Thermo responsive
Abstract: The properties of new thermo-responsive functional surfactants, capable of forming a metal chelate, synthesized by grafting a diamide group (amino-acid residue) to the tip hydrophilic endgroup or in a branched position to polyoxyethylene nonionic surfactants [CiEj: CiH2i+1(OCH2CH2)jOH)], are studied. Their use in cloud point extraction of uranyl nitrate is tested. The reversible temperature-dependent behavior of classical non-ionic surfactants associated to phase separation of micellar solutions known as clouding behavior is exploited for separation based on cation specific binding to the chelating group. The functional surfactants under investigation combine surface-active properties and characteristic thermoreversible behavior with a capacity to bind uranyl cation. The influence of the complexation on the cloud points of functional surfactants is determined. The chelating surfactants are found efficient for the cloud point extraction of uranyl nitrate at low surfactant-to-uranyl ratio. These new thermoresponsive surfactants with chelating properties hold most promise for the development of new solvent free extraction processes.

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