Author: "Cédric Gaillard" / Topic: 0210 nano-technology - Searchworks@Jio Institute Digital Library Search Results

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51 results on '"Cédric Gaillard"'

1. Catanionic Coacervate Droplets as a Surfactant-Based Membrane-Free Protocell Model

Author: Cédric Gaillard, Stephen Mann, Nicolas Martin, Jean-Christophe Baret, Laure Béven, Jean Paul Douliez, Thomas Beneyton, Biologie du fruit et pathologie (BFP), Université Sciences et Technologies - Bordeaux 1-Université Bordeaux Segalen - Bordeaux 2-Institut National de la Recherche Agronomique (INRA), University of Bristol [Bristol], Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), Institut National de la Recherche Agronomique (INRA), Centre de Recherche Paul Pascal (CRPP), Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), MaxSynBio, Université Bordeaux Segalen - Bordeaux 2-Institut National de la Recherche Agronomique (INRA)-Université Sciences et Technologies - Bordeaux 1, UMR1332 Fruit Biology and Pathology, Centre for Organized Matter Chemistry and Centre for Protolife Research, School of Chemistry, and Université de Bordeaux (UB)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Protocell, food.ingredient, Catanionics · Coacervates · Microreactors · Protein crowding · Sequestration, 02 engineering and technology, Cetylpyridinium chloride, 010402 general chemistry, Gelatin, Micelle, 01 natural sciences, Catalysis, chemistry.chemical_compound, food, Pulmonary surfactant, Organic chemistry, [PHYS.COND]Physics [physics]/Condensed Matter [cond-mat], [PHYS]Physics [physics], Coacervate, Chemistry, 010405 organic chemistry, General Chemistry, General Medicine, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Membrane, Chemical engineering, Ionic strength, 0210 nano-technology
Abstract: UMR BFP - Equipe Mollicutes; International audience; We report on the formation of surfactant-based complex catanionic coacervate droplets in mixtures of decanoic acid and cetylpyridinium chloride or cetyltrimethylammonium bromide. We show that coacervation occurs over a broad range of composition, pH, and ionic strength. The catanionic coacervates consist of elongated micelles, sequester a wide range of solutes including water-soluble organic dyes, polysaccharides, proteins, enzymes, and DNA, and can be structurally stabilized by sodium alginate or gelatin-based hydrogelation. These results suggest that catanionic coacervates could be exploited as a novel surfactant-based membrane- free protocell model.
Published: 2017
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2. Data on characterization of nano- and micro-structures resulting from glycine betaine surfactant/kappa-carrageenan interactions by Laser Scanning Confocal Microscopy and Transmission Electron Microscopy

Author: Cédric Gaillard, Rudy Covis, Maud Benoit, Thierry Benvegnu, Yunhui Wang, Thomas Vives, Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), Institut National de la Recherche Agronomique (INRA), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS), Centre d׳étude et de Valorisation des Algues, ANR-10-BTBR-04, Agence Nationale de la Recherche, Unité de recherche sur les Biopolymères, Interactions Assemblages ( BIA ), Institut National de la Recherche Agronomique ( INRA ), Institut des Sciences Chimiques de Rennes ( ISCR ), Université de Rennes 1 ( UR1 ), Université de Rennes ( UNIV-RENNES ) -Université de Rennes ( UNIV-RENNES ) -Ecole Nationale Supérieure de Chimie de Rennes-Institut National des Sciences Appliquées ( INSA ) -Centre National de la Recherche Scientifique ( CNRS ), Centre National de la Recherche Scientifique ( CNRS ), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre d'études et de valorisation des algues (CEVA), ANR-10-BTBR-0004,IDEALG,Biotechnologies pour la valorisation des macroalgues(2010), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes-Centre National de la Recherche Scientifique (CNRS)
Subjects: [SDV]Life Sciences [q-bio], Analytical chemistry, 02 engineering and technology, 010402 general chemistry, lcsh:Computer applications to medicine. Medical informatics, 01 natural sciences, chemistry.chemical_compound, Betaine, Pulmonary surfactant, Amide, Nano, lcsh:Science (General), ComputingMilieux_MISCELLANEOUS, Data Article, chemistry.chemical_classification, Electrostatic interactions, Multidisciplinary, [ SDV ] Life Sciences [q-bio], Chemistry, Glycine betaine surfactant/kappa-carrageenan complexes, Cationic polymerization, Polymer, 021001 nanoscience & nanotechnology, Nano- and micro-structures, 0104 chemical sciences, Laser Scanning Confocal Microscopy and Transmission Electron Microscopy, Chemical engineering, Transmission electron microscopy, Glycine, lcsh:R858-859.7, 0210 nano-technology, lcsh:Q1-390
Abstract: This article contains data on the Laser Scanning Confocal Microscopy (LSCM) and Transmission Electron Microscopy (TEM) images related to multi-scaled self-assemblies resulting from 'green' cationic glycine betaine surfactant/anionic kappa-carrageenan interactions. These data gave clear evidence of the evolution of the micron-, nano-sized structures obtained at two surfactant/polymer molar ratios (3.5 and 0.8) and after the dilution of the aqueous dispersions with factors of 5 and 10 times. This data article is related to the research article entitled, "Monitoring the architecture of anionic ĸ-carrageenan/cationic glycine betaine amide surfactant assemblies by dilution: A multiscale approach" (Gaillard et al., 2017) [1].
Published: 2016
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3. Spontaneous formation of nanofilms under interaction of 4th generation pyrydylphenylene dendrimer with proteins

Author: Svetlana A. Sorokina, Zinaida B. Shifrina, Victor S. Stroylov, Cédric Gaillard, Aleksandra K. Melnikova, Vladimir I. Muronetz, Yulia Yu. Stroylova, Thomas Haertlé, Moscow State University, Institute of Molecular Medicine, St. James's Hospital and Trinity College, Russian Academy of Sciences [Moscow] (RAS), ND Zelinsky Institute of Organic Chemistry [Moscow, Russia], Faculty of Bioengineering and Bioinformatics, Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), Institut National de la Recherche Agronomique (INRA), Department of Animal Nutrition and Feed Management, University of Life Sciences in Poznan, Teheran University, Partenaires INRAE, RFBR grant [15-38-70034, 16-33-00593], and French Government
Subjects: Dendrimers, Dendrimer-protein composites, Polymers and Plastics, Molecular model, In silico, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Molecular dynamics, chemistry.chemical_compound, Dendrimer, [SDV.IDA]Life Sciences [q-bio]/Food engineering, Materials Chemistry, medicine, [SPI.GPROC]Engineering Sciences [physics]/Chemical and Process Engineering, Chymotrypsin, biology, Organic Chemistry, 021001 nanoscience & nanotechnology, Trypsin, 0104 chemical sciences, 3. Good health, Enzymes, chemistry, biology.protein, Biophysics, Lysozyme, 0210 nano-technology, Biosensor, medicine.drug
Abstract: The use of materials based on protein-polymer compositions is a promising method for solving a number of problems in biotechnology and medicine. In our work, we produced multilayer nanofilms based on 4th generation (G4) pyridylphenylene dendrimers with fully pyridine-based periphery containing a protein component. For dairy beta- and kappa-caseins, alpha-lactalbumin, recombinant sheep prion protein, lysozyme, trypsin, and alpha-chymotrypsin the ability to integrate into self-organizing structures about 230–710 nm thick, measured by atomic force microscopy, was found. The formation of nanofilms is dependent on the protein/dendrimer ratio in the initial solution. At the same time, the nanofilms are resistant to pH changes, and the action of detergents. We demonstrated that trypsin and chymotrypsin incorporated into the nanofilms still conserved proteolytic activities and were stable for at least 3 weeks. We have also conducted in silico molecular modeling of the G4 dendrimer interactions with lysozyme. Spatial structure of the dendrimer-protein complex was predicted and most probable variant remained almost intact under 100 ns molecular dynamics simulation conditions. We believe that dendrimer-protein systems are promising tools for possible applications in the development of new stable biomaterials and biosensors.
Published: 2018
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4. Molecular and structural changes in gelatin evidenced by Raman microspectroscopy

Author: Anne Duconseille, Cédric Gaillard, Véronique Santé-Lhoutellier, Thierry Astruc, Qualité des Produits Animaux (QuaPA), Institut National de la Recherche Agronomique (INRA), and Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA)
Subjects: food.ingredient, General Chemical Engineering, Analytical chemistry, 02 engineering and technology, cross-links, Gelatin, gelatin, 0404 agricultural biotechnology, food, raman spectroscopy, Denaturation (biochemistry), Food science, dissolution rate, Dissolution, Chemistry, aging, 04 agricultural and veterinary sciences, General Chemistry, 021001 nanoscience & nanotechnology, 040401 food science, Raman microspectroscopy, Lipid content, Digestive tract, 0210 nano-technology, [CHIM.OTHE]Chemical Sciences/Other, Food Science
Abstract: International audience; The gelatin used for the hard capsules manufacturing must meet strict dissolution specification to ensure the delivery of drugs at right time in the digestive tract. However, the environment of production and storage time affect the quality of gelatin dissolution. This study aimed to identify the mechanisms underlying the geographical environment of production and aging impact on the gelatin dissolution rate. Gelatins from 3 different origins of production (A, B & C), whose dissolution rate had been previously characterized, were analyzed by Raman microspectroscopy before and after aging. The principal component analysis (PCA) clearly separated the aged gelatins from non-aged ones. The spectra interpretation suggested the denaturation of gelatin triple-helices. In addition, the formation of cross-links such as dityrosine, glucosyl-galactosylhydroxylysinonorleucine and proteoglycan-like sugar adducts was strongly suspected. Whatever the gelatin aging state, PCA systematically separated the B-gelatins from A and C-gelatins. Pentosidine cross-link was likely to vary depending on the production origin. Finally, the quality of dissolution was discriminated for aged gelatins of A-origin: the non-compliant gelatins exhibited higher lipid content than the compliant ones.
Published: 2018
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5. Focused ultrasound influence on calcein-loaded thermosensitive stealth liposomes

Author: Jean-Michel Escoffre, Anthony Novell, Nicolas Tsapis, Elias Fattal, Ayache Bouakaz, Chantal Al Sabbagh, Cédric Gaillard, Equipe 5 : imagerie et ultrasons, Imagerie et cerveau (iBrain - Inserm U1253 - UNIV Tours ), Université de Tours-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Tours-Institut National de la Santé et de la Recherche Médicale (INSERM), Institut Galien Paris-Sud (IGPS), Université Paris-Sud - Paris 11 (UP11)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Tours-Institut National de la Santé et de la Recherche Médicale (INSERM), Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), Institut National de la Recherche Agronomique (INRA), Physico-chimie, pharmacotechnie, biopharmacie (PCPB), Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS), Université de Tours (UT)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Tours (UT)-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 de Chimie du CNRS (INC), Université de Tours (UT)-Institut National de la Santé et de la Recherche Médicale (INSERM), Escoffre, Jean-Michel, Imagerie et cerveau, Institut de pharmacologie et de biologie structurale (IPBS), Université Toulouse III - Paul Sabatier (UT3), and Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)
Subjects: Cancer Research, medicine.medical_specialty, [SDV.BIO]Life Sciences [q-bio]/Biotechnology, Physiology, Ultrasonic Therapy, Calcein release, Thermosensitive liposomes, 02 engineering and technology, Focused ultrasound, 03 medical and health sciences, chemistry.chemical_compound, Drug Delivery Systems, 0302 clinical medicine, Physiology (medical), thermosensitive liposomes, polycyclic compounds, medicine, Thermosensing, Stealth liposomes, ComputingMilieux_MISCELLANEOUS, mild hyperthermia, Fluorescent Dyes, Liposome, Hydrophobic drug, Temperature, mechanical stress, technology, industry, and agriculture, [SDV.SP]Life Sciences [q-bio]/Pharmaceutical sciences, Fluoresceins, 021001 nanoscience & nanotechnology, [SDV.BIO] Life Sciences [q-bio]/Biotechnology, Surgery, [SDV.SP] Life Sciences [q-bio]/Pharmaceutical sciences, Calcein, Spectrometry, Fluorescence, chemistry, 030220 oncology & carcinogenesis, Liposomes, Drug delivery, Biophysics, focused ultrasound, lipids (amino acids, peptides, and proteins), Stress, Mechanical, 0210 nano-technology, Hydrophobic and Hydrophilic Interactions
Abstract: International audience; Focused ultrasound (FUS) is a versatile technology for non-invasive thermal therapies in oncology. Indeed, this technology has great potential for local heat-mediated drug delivery from thermosensitive liposomes (TSLs), thus improving therapeutic efficacy and reducing toxicity profiles. In the present study we evaluated the influence of FUS parameters on the release of calcein from TSLs used to model a hydrophilic drug. Quantitative calcein release from TSLs (DPPC/CHOL/DSPE-PEG2000: 90/5/5) and non-thermosensitive liposomes (NTSLs) (DPPC/CHOL/DSPE-PEG2000: 65/30/5) was measured by spectrofluorimetry after both water bath and FUS-induced in vitro heating. The heating of TSLs at 42 degrees C in a water bath resulted in a maximum calcein release of 45%. No additional calcein release was observed at temperatures above 42 degrees C. A similar percentage of calcein release was achieved when TSLs were exposed to 1 MHz sinusoidal waves at peak negative pressure of 1.5 MPa, 40% duty cycle, for 10 min (i.e. above 42 degrees C). No release was detected when NTSLs were heated in a water bath. For both TSLs and NTSLs, the calcein release was increased by more than 10% for acoustic pressures ranging from 1.5 MPa to 2 MPa. This additional release was attributed to the mechanical stress generated by FUS, which was sufficient to disrupt the liposomal membrane. Furthermore, analysis of cryo-TEM images showed a significant decrease in liposome size (14%) induced by the thermal effect, whereas the liposome diameter remained unaffected by the FUS-triggered non-thermal effects.
Published: 2015
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6. Structure and elasticity of composite nanoparticle/polymer nanoshells (hybridosomes®)

Author: Flavien Sciortino, Soizic Chevance, Cédric Gaillard, Mark L. Kahn, Fabienne Gauffre, M. Thivolle, Institut des Sciences Chimiques de Rennes (ISCR), Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Rennes-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES), Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Unité de Recherche sur les Biopolymères leurs Interactions et Assemblages (URBIA), Institut National de la Recherche Agronomique (INRA), French Ministry of Education and Research, CNRS, Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), 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)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes-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-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie de Toulouse (ICT), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), and Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Materials science, capsules, mechanical-properties, Composite number, Nanoparticle, Nanotechnology, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, polyelectrolyte multilayer microcapsules, chemistry.chemical_compound, Osmotic pressure, particles, chemistry.chemical_classification, vesicles, nanocapsules, General Chemistry, Polymer, [CHIM.MATE]Chemical Sciences/Material chemistry, stability, Nanoindentation, 021001 nanoscience & nanotechnology, Condensed Matter Physics, Nanoshell, 0104 chemical sciences, Chemical engineering, chemistry, membranes, molecular-weight, 0210 nano-technology, Ethylene glycol, [PHYS.COND.CM-SCM]Physics [physics]/Condensed Matter [cond-mat]/Soft Condensed Matter [cond-mat.soft], Iron oxide nanoparticles
Abstract: International audience; Our group recently introduced a new process to synthesize nanoparticle shells of about 100 nm, named "hybridosomess''. Here, the structure and mechanical properties of hybridosomes® made from iron oxide nanoparticles and poly(acrylic acid) are characterized using TEM, AFM and an osmotic compression technique. For the latter, the size distribution of the hybridosomes is monitored by nanoparticle tracking analysis (NTA) in the presence of poly(ethylene glycol)s of different molecular weights. It is found that the size of the hybridosomes® can be tuned from ca. 80 nm to over 110 nm by adjusting the amount of nanoparticles and that their shell consists of a single layer of nanoparticles, with a porous structure. The size of the pores is estimated from osmotic compression experiments at ca. 4000 g mol(-1). The mechanical properties are measured both at the ensemble level using size measurements under osmotic pressure and at the single nanoparticle level by atomic force microscopy nanoindentation. Both osmotic and AFM experiments are analyzed in the framework of the continuum elastic theory of thin shells and yield a value of Young's modulus of the order of MPa.
Published: 2017
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7. Study of the pseudo-polyrotaxane architecture as a route for mild surface functionalization by click-chemistry of poly(?-caprolactone)-based electrospun fibers

Author: Guy Schlatter, Anne Hébraud, Luc Avérous, Sébastien Gallet, Murielle Oster, Christophe Fajolles, Rachid Baati, Cédric Gaillard, Eric Pollet, Institut de chimie et procédés pour l'énergie, l'environnement et la santé (ICPEES), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et nanosciences d'Alsace, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), Institut National de la Recherche Agronomique (INRA), 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 Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Université de Strasbourg (UNISTRA)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), 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), French Agence Nationale de la Recherche (ANR), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), 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, Bioconjugation, Materials science, Cyclodextrin, Biomedical Engineering, technology, industry, and agriculture, 02 engineering and technology, General Chemistry, General Medicine, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Nanofiber, Polycaprolactone, Polymer chemistry, Click chemistry, Surface modification, General Materials Science, Fiber, 0210 nano-technology, Caprolactone
Abstract: International audience; Polycaprolactone (PCL) electrospun fibers are widely developed for biomedical applications. However, their hydrophobicity and passivity towards cell growth is an important limitation. An original method to functionalize PCL nanofibers, making them reactive for bioconjugation of proteins or other molecules of interests in water under mild conditions, is here reported. This method involves the preparation of pseudo-polyrotaxanes (pPR) of cyclodextrin (CD) and PCL. Core:shell PCL:pPR fibers were then prepared by coaxial electrospinning in order to bring available reactive hydroxyl groups from the CD, at the fiber surface. Different pPRs architectures (star, miktoarm and block-copolymer-like) were synthesized to study the effect of the pPR structure on the fiber morphology and surface reactivity by grafting fluorescein isothiocyanate (FITC). Finally, bicyclononyne groups were grafted onto the star-pPR based fibers allowing the conjugation of a fluorescent dye by click-chemistry in water without any copper catalyst proving the potential of the method for the biofunctionalization of PCL-based fibers.
Published: 2017
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8. Triazine-functionalized chitosan-encapsulated superparamagnetic nanoparticles as reusable and robust nanocarrier for glucoamylase immobilization

Author: Mahkameh Amirbandeh, Cédric Gaillard, Asieh Soozanipour, Asghar Taheri-Kafrani, University of Isfahan, Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), Institut National de la Recherche Agronomique (INRA), and Research Councils of University of Isfahan
Subjects: Environmental Engineering, Immobilized enzyme, Biomedical Engineering, Bioengineering, 02 engineering and technology, 01 natural sciences, Catalysis, Chitosan, chemistry.chemical_compound, Immobilization, [SDV.IDA]Life Sciences [q-bio]/Food engineering, Organic chemistry, Reactivity (chemistry), [SPI.GPROC]Engineering Sciences [physics]/Chemical and Process Engineering, Triazine, Reusability, Nanocomposite, Cyanuric chloride, biology, 010405 organic chemistry, Aspergillus niger, 021001 nanoscience & nanotechnology, biology.organism_classification, 0104 chemical sciences, Chemical engineering, chemistry, Glucoamylase, Magnetic nanoparticles, Nanocarriers, 0210 nano-technology, Biotechnology
Abstract: Aspergillus niger glucoamylase (GLA) was covalently immobilized on 1,3,5-triazine-functionalized chitosan coated superparamagnetic nanoparticles (MNPCh-CC). The morphology, structure and properties of functionalized nanocomposite were investigated, as well as GLA immobilization process, through different analytical tools. Different experimental parameters such as optimum temperature, pH, reaction time and enzyme concentration were studied for free and immobilized enzyme. The GLA immobilized on nanocarrier exhibited excellent catalytic activity at pH 4.5 and 60 °C. Notably, the immobilized GLA showed quite impressive stability, even after 10 reaction cycles, it could still retain about 70% of the initial activity. The results showed that immobilization process couldn’t significantly inhibit enzyme-substrate interaction and subsequently retained its effective catalytic activity. The substantial improvement of reactivity, reusability, and stability of this biocatalyst system may confer it a wider range of applications in industrial processes.
Published: 2017
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9. Mechanical properties of membranes composed of gel-phase or fluid-phase phospholipids probed on liposomes by atomic force spectroscopy

Author: Nicolas Delorme, Cédric Gaillard, Christelle Lopez, Franck Artzner, Oumaima Et-Thakafy, Fanny Guyomarc'H, Cristelle Mériadec, Science et Technologie du Lait et de l'Oeuf (STLO), Institut National de la Recherche Agronomique (INRA)-AGROCAMPUS OUEST, Institut national d'enseignement supérieur pour l'agriculture, l'alimentation et l'environnement (Institut Agro)-Institut national d'enseignement supérieur pour l'agriculture, l'alimentation et l'environnement (Institut Agro), Institut des Molécules et Matériaux du Mans (IMMM), Le Mans Université (UM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), Institut National de la Recherche Agronomique (INRA), Institut de Physique de Rennes (IPR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS), The Asylum Research MFP3D-BIO atomic force microscope was funded by the European Union (FEDER), the French Ministry of Education and Research, INRA, Conseil Général 35 and Rennes Métropole. The doctoral fellowship of author Et-Thakafy was funded by INRA CEPIA and Région Bretagne under the grant ARED 8806., Le Mans Université (UM)-Centre National de la Recherche Scientifique (CNRS), and Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS)
Subjects: phospholipide, x ray, rayon x, Lipid Bilayers, Analytical chemistry, diffraction, 02 engineering and technology, Microscopy, Atomic Force, 010402 general chemistry, vésicule phospholipidique, 01 natural sciences, Adsorption, membrane lipidique, lipid, Microscopy, Electrochemistry, General Materials Science, Lipid bilayer, Phospholipids, Spectroscopy, lipide, Mechanical Phenomena, [PHYS]Physics [physics], Liposome, Chemistry, Spectrum Analysis, Force spectroscopy, technology, industry, and agriculture, Surfaces and Interfaces, Penetration (firestop), [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 0104 chemical sciences, diffraction électronique, Membrane, [CHIM.POLY]Chemical Sciences/Polymers, Electron diffraction, Liposomes, liposome, Phosphatidylcholines, electron diffraction, lipids (amino acids, peptides, and proteins), spectroscopie à force atomique, 0210 nano-technology
Abstract: International audience; In many liposome applications, the nanomechanical properties of the membrane envelope are essential to ensure, e.g., physical stability, protection, or penetration into tissues. Of all factors, the lipid composition and its phase behavior are susceptible to tune the mechanical properties of membranes. To investigate this, small unilamellar vesicles (SUV; diameter < 200 nm), referred to as liposomes, were produced using either unsaturated 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) or saturated 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) in aqueous buffer at pH 6.7. The respective melting temperatures of these phospholipids were −20 and 41 °C. X-ray diffraction analysis confirmed that at 20 °C DOPC was in the fluid phase and DPPC was in the gel phase. After adsorption of the liposomes onto flat silicon substrates, atomic force microscopy (AFM) was used to image and probe the mechanical properties of the liposome membrane. The resulting force–distance curves were treated using an analytical model based on the shell theory to yield the Young’s modulus (E) and the bending rigidity (kC) of the curved membranes. The mechanical investigation showed that DPPC membranes were much stiffer (E = 116 ± 45 MPa) than those of DOPC (E = 13 ± 9 MPa) at 20 °C. The study demonstrates that the employed methodology allows discrimination of the respective properties of gel- or fluid-phase membranes when in the shape of liposomes. It opens perspectives to map the mechanical properties of liposomes containing both fluid and gel phases or of biological systems.
Published: 2017
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10. Self-Assembling Behavior of Glycerol Monoundecenoate in Water

Author: Cédric Gaillard, Frédéric Nallet, Romain Valentin, Zéphirin Mouloungui, Laurence Navailles, Gildas Nyame Mendendy Boussambe, Jean-François Fabre, Chimie Agro-Industrielle (CAI), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole nationale supérieure des ingénieurs en arts chimiques et technologiques-Institut National de la Recherche Agronomique (INRA), Centre de Recherche Paul Pascal (CRPP), Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), Institut National de la Recherche Agronomique (INRA), French government and the Midi-Pyrénées Region Fond Unique Interministériel (FUI) and the CEPIA Department of INRA for support of the ANS program., Centre National de la Recherche Scientifique - CNRS (FRANCE), Institut National Polytechnique de Toulouse - Toulouse INP (FRANCE), Institut National de la Recherche Agronomique - INRA (FRANCE), Université de Bordeaux (FRANCE), Institut National Polytechnique de Toulouse - INPT (FRANCE), Institut National de la Recherche Agronomique (INRA)-Ecole nationale supérieure des ingénieurs en arts chimiques et technologiques-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées, Laboratoire de Chimie Agro-Industrielle (LCA), Institut National de la Recherche Agronomique (INRA)-Ecole Nationale Supérieure de Chimie de Toulouse, and Université de Bordeaux (UB)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Glycerol, [SDV.SA]Life Sciences [q-bio]/Agricultural sciences, Lamellar phases, 02 engineering and technology, Water retention, 010402 general chemistry, 01 natural sciences, Surface tension, Fatty Acids, Monounsaturated, chemistry.chemical_compound, Differential scanning calorimetry, [CHIM.GENI]Chemical Sciences/Chemical engineering, Electrochemistry, medicine, Génie chimique, General Materials Science, Cryogenic transmission electron microscopy, Vesicles, Spectroscopy, Polarized light microscopy, Molecular Structure, Small-angle X-ray scattering, Water, Surfaces and Interfaces, Self-assembly, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 0104 chemical sciences, Crystallography, chemistry, Chemical engineering, Transmission electron microscopy, Undecylenic acid, Surface tension experiments, 0210 nano-technology, Sciences agricoles, medicine.drug
Abstract: International audience; The self-assembling properties of glycerol esters in water are well known. Still, few data on glycerol monoesters of undecylenic acid are available. The aim of this study was to highlight the behavior of glycerol monoundecenoate (GM-C11:1) in different diluted and concentrated states. Its self-assembling properties in water and upon solid inorganic surfaces were investigated in the diluted state using surface tension experiments, atomic force microscopy, and cryogenic transmission electron microscopy studies. In the concentrated state, the gelling properties in the presence of water were investigated using polarized light microscopy, differential scanning calorimetry (DSC), and small-angle X-ray scattering (SAXS) experiments. GM-C11:1 at 100 mg/L self-assembles at the liquid/air interfaces as aggregates of approximately 20 nm in diameter, organized into concentric forms. These aggregates are spherical globules composed of several molecules of GM-C11:1. At higher concentrations (1000 and 104 mg/L), GM-C11:1 is able to uniformly coat liquid/air and liquid/solid interfaces. In bulk, GM-C11:1 forms spontaneously aggregates and vesicles. In a more concentrated state, GM-C11:1 assembles into lamellar Lβ and Lα forms in water. By cross-referencing SAXS and DSC findings, we were able to distinguish between interlamellar water molecules strongly bound to GM-C11:1 and other molecules remaining unbound and considered to be “mobile” water. The percentage of water strongly bound was proportional to the percentage of GM-C11:1 in the system. In this case, GM-C11:1 appears to be an effective molecule for surface treatments for which water retention is important.
Published: 2017
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11. Synthesis of Flower-Like Polybutadiene

Author: Erwan Nicol, Stéphane Carlotti, Cédric Gaillard, René-Ponce Nzé, Suwat Kaewbuddee, Institut des Molécules et Matériaux du Mans (IMMM), Le Mans Université (UM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Bretagne Loire (UBL), Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), Institut National de la Recherche Agronomique (INRA), Laboratoire de Chimie des Polymères Organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Team 1 LCPO : Polymerization Catalyses & Engineering, Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Region des Pays de la Loire (Nanofleurs Project), Institut des Molécules et Matériaux du Mans, Le Mans Université (UM), Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Centre National de la Recherche Scientifique (CNRS), TEAM 1 LCPO, and Université de Bordeaux (UB)-Institut Polytechnique de Bordeaux-Centre National de la Recherche Scientifique (CNRS)
Subjects: Polymers and Plastics, [SDV]Life Sciences [q-bio], block copolymer, 02 engineering and technology, SARA-ATRP, 010402 general chemistry, 01 natural sciences, Micelle, anionic polymerization, Polybutadiene, Dynamic light scattering, Polymer chemistry, Materials Chemistry, Copolymer, Physical and Theoretical Chemistry, Reversible-deactivation radical polymerization, chemistry.chemical_classification, Chemistry, Organic Chemistry, Polymer, self-assembly, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 0104 chemical sciences, photo-crosslinking, Anionic addition polymerization, Living polymerization, 0210 nano-technology
Abstract: Synthesis of complex macromolecular architectures exhibiting no chain ends such as flower-like polymers is still of interest in the aim of investigating their physicochemical properties. For this purpose, poly(3,4-dimethyl maleic imidoethyl acrylate)-block-polybutadiene-block-poly(3,4-dimethyl maleic imidoethyl acrylate) triblock copolymer is synthesized in a convergent manner using a combination of living polymerization (anionic polymerization), reversible deactivation radical polymerization, and click chemistry. This copolymer is self-assembled in a selective solvent (heptane/THF mixture) of the polybutadiene block leading to the formation of flower-like micelles in thermodynamic equilibrium in dilute solution. These resulting transient architectures are fixed by covalently crosslinking the micelles core by inducing [2+2] cyclodimerization of the 3,4-dimethyl maleic imidoethyl groups borne by the short solvophobic blocks under UV irradiation. Single flowers are isolated from residual non-crosslinked chains by semipreparative size exclusion chromatography (SEC) and characterized by H-1 NMR, SEC, dynamic light scattering (DLS), and transmission electron microscopy (TEM).
Published: 2017
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12. Structural, Viscoelastic, and Electrochemical Characteristics of Self-Assembled Amphiphilic Comblike Copolymers in Aqueous Solutions

Author: Claude Deslouis, Cédric Gaillard, Boualem Saidani, Lila Chaal, Lazhar Benyahia, Malika Talantikite, Kahina Aoudia, Christophe Chassenieux, Institut des Molécules et Matériaux du Mans (IMMM), Le Mans Université (UM)-Centre National de la Recherche Scientifique (CNRS), Laboratoire d'Electrochimie, Corrosion et de Valorisation Energétique (LECVE), Université A. Mira, Laboratoire Interfaces et Systèmes Electrochimiques (LISE), Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC), Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), Institut National de la Recherche Agronomique (INRA), Le Mans Université (UM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire d'Electrochimie, Corrosion et de Valorisation Energétique [Université de Béjaïa] (LECVE), Université Abderrahmane Mira [Béjaïa], Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), 'TASSILI' program [13MDU 893], and University of Bejaia
Subjects: Materials science, 02 engineering and technology, 01 natural sciences, Micelle, 010305 fluids & plasmas, chemistry.chemical_compound, Electrochemical characteristic, 0103 physical sciences, Amphiphile, Polymer chemistry, Materials Chemistry, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Rotating disk electrode, chemistry.chemical_classification, Viscoelastic, Aqueous solution, Polymer, Polyelectrolyte, 021001 nanoscience & nanotechnology, Surfaces, Coatings and Films, Dication, Chemical engineering, chemistry, Polystyrene, 0210 nano-technology, [CHIM.OTHE]Chemical Sciences/Other
Abstract: International audience; Self-assembly in aqueous solutions of an amphiphilic comblike polyelectrolyte (80C12) that consists of a polystyrene (PS) backbone onto which quaternary ammonium pendant moieties have been grafted has been investigated by light scattering and cryo-transmission electron microscopy measurements in the presence of KCl and methylviologen dication (MV2+) under conditions mimicking those for electrochemical measurements. Polymer chains self-assemble within branched cylindrical micelles that display viscoelastic properties, characterized by a relaxation time of 4 s. To tune this time, 80C12 was mixed with a polyoxyethylene nonionic surfactant (Brij C12E10). Relatively increasing the amount of the latter leads to a decrease in the relaxation time of the 80C12 solution. Correlatively, electrochemical experiments with a rotating disk electrode show a transition of the mass transport rate, which deviates from the classical Newtonian behavior in the same velocity domain. This result generalizes what has been already observed with solutions of linear polymers of high molecular weight and wormlike micelles based on surfactants subjected to elongational deformations. Moreover, the critical times derived from rheological and electrochemical experiments display the same trend.
Published: 2017
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13. Fast and effective quantum-dots encapsulation and protection in PEO based photo-cross-linked micelles

Author: Erwan Nicol, Benoit Dubertret, Christophe Chassenieux, Khalid Ferji, Cédric Gaillard, Ines Hamouda, Brice Nadal, Institut des Molécules et Matériaux du Mans (IMMM), Le Mans Université (UM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), NEXDOT, Laboratoire de Physique et d'Etude des Matériaux (UMR 8213) (LPEM), 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)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), Institut National de la Recherche Agronomique (INRA), project Nanofleurs, Centre National de la Recherche Scientifique (CNRS)-Le Mans Université (UM), Laboratoire de Physique et d'Etude des Matériaux (LPEM), Centre National de la Recherche Scientifique (CNRS)-ESPCI ParisTech-Université Pierre et Marie Curie - Paris 6 (UPMC), laboratoire d'optique physique, and Centre National de la Recherche Scientifique (CNRS)
Subjects: Materials science, Block copolymer, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Micelle, Biomaterials, Colloid, chemistry.chemical_compound, Colloid and Surface Chemistry, Amphiphile, Polymer chemistry, Copolymer, [CHIM]Chemical Sciences, ComputingMilieux_MISCELLANEOUS, Acrylate, Ethylene oxide, Photo-cross-linking, technology, industry, and agriculture, Quantum dot, 021001 nanoscience & nanotechnology, equipment and supplies, Fluorescence photoenhancement, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Chemical engineering, Emulsion, Encapsulation, 0210 nano-technology
Abstract: International audience; Cadmium-based quantum dots (QDs) were easily, quickly and efficiently transferred from an organic medium to water without modification of their surface chemistry by the simple emulsion/solvent evaporation technique using micelles of amphiphilic diblock copolymers based on poly(ethylene oxide) and poly(2-methacryloyloxyethyl acrylate) (PEO-b-PMEA) as hosts. The resulting hybrid micelles were stabilized very rapidly by photo-cross-linking the hydrophobic core around the QDs. The encapsulation and photo-cross-linking process were shown to barely affect the photoluminescence properties. Grafting a short octyl chain at the end of the hydrophobic block enhanced both the colloidal stability of the QDs dispersed in water and prevented the quenching of their fluorescence by copper ions. Grafting a longer hexadecyl chain at the end of the PMEA block decreased the efficiency of the corona cross-linking and led to poorer stabilization and protection.
Published: 2016
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14. On the interaction of alginate-based core-shell nanocarriers with keratinocytes in vitro

Author: Lynda Miloudi, Igor Chourpa, Cédric Gaillard, Emilie Munnier, Imane Eddaoudi, Martin Soucé, Hoang Truc Phuong Nguyen, Emilie Allard-Vannier, Nanomédicaments et Nanosondes, EA 6295 (NMNS), Université de Tours (UT), Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), Institut National de la Recherche Agronomique (INRA), NANO'derm project Region (Centre Val de Loire Bioeurope (Solabia Group), Carlina Technologies and Spincontrol, for financial support), and Université de Tours
Subjects: Keratinocytes, Calcium alginate, 02 engineering and technology, 01 natural sciences, chemistry.chemical_compound, Colloid and Surface Chemistry, Glucuronic Acid, Fluorescence Resonance Energy Transfer, Internalization, media_common, Drug Carriers, Hexuronic Acids, Surfaces and Interfaces, General Medicine, Carbocyanines, 021001 nanoscience & nanotechnology, Endocytosis, medicine.anatomical_structure, Drug delivery, 0210 nano-technology, Drug carrier, Keratinocyte, Hydrophobic and Hydrophilic Interactions, Core-shell nanocarrier, Biotechnology, Alginates, Cell Survival, Drug Compounding, media_common.quotation_subject, Nanotechnology, Caveolae, 010402 general chemistry, Cell Line, Microscopy, Electron, Transmission, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, medicine, Humans, Particle Size, Physical and Theoretical Chemistry, [SDV.IB.BIO]Life Sciences [q-bio]/Bioengineering/Biomaterials, Fluorescent Dyes, Alginate, Förster resonance energy transfer (FRET), 0104 chemical sciences, Drug Liberation, Kinetics, Förster resonance energy transfer, [SDV.SP.PG]Life Sciences [q-bio]/Pharmaceutical sciences/Galenic pharmacology, chemistry, Biophysics, Nanoparticles, Nanocarriers, [SDV.MHEP.DERM]Life Sciences [q-bio]/Human health and pathology/Dermatology
Abstract: International audience; Calcium alginate nanocarriers (CaANCs) were developed as a potential tool for delivery of hydrophobic active molecules such as pharmaceutical and cosmetic active ingredients. In this study, we focused on interactions between CaANCs and keratinocytes in culture and examined toxicity, internalization and drug release. Prior to cellular interactions, cryogenic transmission electron microscopy images showed that CaANCs appear as regular, spherical and dense particles, giving evidence of the surface gelation of CaANCs. Their size, around 200 nm, was stable under tested conditions (temperature, culture media, presence of serum and presence of encapsulated dye), and their toxicity on keratinocytes was very low. Flow cytometry assays showed that CaANCs are internalized into keratinocytes by endocytosis with a predominant implication of the caveolae-mediated route. Förster resonance energy transfer (FRET) demonstrated that after a 2 h contact, the release of CaANC contents in the cytoplasm of keratinocytes was almost complete. The endocytosis of CaANCs by a lysosome-free pathway, and the rapid release of their contents inside keratinocytes, will allow vectorized molecules to fully exhibit their pharmacological or cosmetic activity.
Published: 2016
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15. Synthesis of Flower-Like Poly(Ethylene Oxide) Based Macromolecular Architectures by Photo-Cross-Linking of Block Copolymers Self-Assemblies

Author: Erwan Nicol, Vijay S. Kadam, Cédric Gaillard, Université du Maine [Le Mans - Laval], Polymères, colloïdes, interfaces (PCI), Le Mans Université (UM), Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), and Institut National de la Recherche Agronomique (INRA)
Subjects: Acrylate, Materials science, Polymers and Plastics, Ethylene oxide, Organic Chemistry, Flower like, Oxide, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Polymer chemistry, Materials Chemistry, Copolymer, 0210 nano-technology, Poly ethylene, Macromolecule
Abstract: Article Nicol, E (reprint author), Univ Maine, CNRS, UMR 6120, *F*-72085 Le Mans, France erwan.nicol@univ-lemans.fr Funding Acknowledgement: National Research Agency (ANR); International audience; A triblock poly(2-methacryloyloxyethyl acrylate)-b-poly(ethylene oxide)-b-poly(2-methacryloyloxyethyl acrylate) (PMEA-b-PEO-b-PMEA) copolymer bearing polymerizable groups on the hydrophobic blocks synthesized and self-assembled in water. The transient micellar structures formed in selective solvent were permanently fixed by cross-linking the methacrylate moieties in micelles cores under UV light. The structures obtained after cross-linking were characterized by static and dynamic light scattering (SLS and DLS), size exclusion chromatography (SEC), and electron microscopy (TEM and cryoTEM). SLS measurements showed an increase of the aggregation number of the micelles during the photo-cross-linking process. This result was discussed in terms of competition between the micelles polymerization rate and the unimers exchange rate. At low concentration, mainly flower-like architectures were obtained. As the concentration of the cross-linked solutions increased, more complex aggrega! tes, in which the "flower" is the basic unit, were obtained.
Published: 2011
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16. Core Cross-Linking of Dynamic Diblock Copolymer Micelles: Quantitative Study of Photopolymerization Efficiency and Micelle Structure

Author: Laurent Fontaine, Erwan Nicol, Alla Nesterenko, Guillaume Brotons, Cédric Gaillard, Sagrario Pascual, Sandie Piogé, Institut des Molécules et Matériaux du Mans (IMMM), Le Mans Université (UM)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie Agro-Industrielle (LCA), Institut National de la Recherche Agronomique (INRA)-Ecole Nationale Supérieure de Chimie de Toulouse, Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), Institut National de la Recherche Agronomique (INRA), Le Mans Université (UM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chimie Agro-Industrielle (CAI), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole nationale supérieure des ingénieurs en arts chimiques et technologiques-Institut National de la Recherche Agronomique (INRA), Region des Pays de la Loire, and National Research Agency (ANR)
Subjects: WORMLIKE MICELLES, Materials science, Polymers and Plastics, BLOCK POLY(2-CINNAMOYLETHYL METHACRYLATE), 02 engineering and technology, 010402 general chemistry, Photochemistry, 01 natural sciences, Micelle, Light scattering, Inorganic Chemistry, chemistry.chemical_compound, POROGEN RELEASE, Dynamic light scattering, Materials Chemistry, POLY(ETHYLENE OXIDE), Static light scattering, ComputingMilieux_MISCELLANEOUS, Acrylate, Aggregation number, LINKED STAR POLYMERS, FORMING MONOMERS, JANUS MICELLES, Organic Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, REACTIVE MICELLES, 0104 chemical sciences, [CHIM.POLY]Chemical Sciences/Polymers, Photopolymer, chemistry, POLYSTYRENE, Ethyl acrylate, 0210 nano-technology, HOLLOW NANOSPHERES
Abstract: International audience; Asymmetric poly(ethylene oxide)-b-poly(ethyl acrylate) block copolymers bearing polymerizable (meth)acrylate groups at the end of the hydrophobic block were synthesized and self-assembled in water. The micellar structures were studied by static light scattering (SLS), dynamic light scattering (DLS) and small angle neutrons scattering (SANS). The micelles were checked to be dynamical and in a thermodynamic equilibrium. In order to stabilize the micelles, a photoinitiator was added and UV light was applied to initiate the cross-linking of micelles cores. Light scattering and SANS showed a very weak influence of the addition of the photoinitiator on the size and aggregation number of micelles. The photopolymerization takes place within a few seconds and the cross-linking process barely modifies the structural properties of the micelles. The efficiency of the core cross-linking was estimated in terms of (meth)acrylate double bonds conversion and rate of incorporation of unimers into the cross-linked structures. (1)H NMR showed a complete conversion of double bonds. Transmission electron microscopy (TEM), light and neutron scattering studies showed almost no modification of the structures, indicating that the exchange dynamics of unimers barely affects the structure during the cross-linking process. Size exclusion chromatography (SEC) analyses in DMF revealed a non-negligible amount of nonstabilized unimers. The crosslinked stars can be easily isolated from the remaining unimers by flash chromatography using hydrophobically modified silica gel.
Published: 2011
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17. Rheological characterization of microfibrillated cellulose suspensions after freezing

Author: Sylvie Durand, Jean-Louis Doublier, Cédric Gaillard, Catherine Garnier, C. Blassel, G. Agoda-Tandjawa, S. Berot, Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), and Institut National de la Recherche Agronomique (INRA)
Subjects: Polymers and Plastics, Concentration effect, 02 engineering and technology, engineering.material, 010402 general chemistry, 01 natural sciences, chemistry.chemical_compound, Crystallinity, RHEOLOGY, Rheology, Materials Chemistry, Cellulose, Composite material, SUGAR-BEET PULP, MICROFIBRILS, Pulp (paper), Organic Chemistry, FREEZING, Dynamic mechanical analysis, 021001 nanoscience & nanotechnology, 0104 chemical sciences, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Ionic strength, engineering, CATIONS, Microfibril, 0210 nano-technology, CELLULOSE SUSPENSION, CRYSTALLINITY
Abstract: International audience; This work aims to investigate the theological properties of microfibrillated cellulose (MFC) suspensions. The effect of some experimental parameters, such as cellulose concentration, temperature, ionic strength and pH has been studied. For that purpose, suspensions of microfibrillated cellulose have been prepared by strong mechanical treatments of a purified sugar-beet pulp cellulose-based residue in aqueous medium. Cellulose suspensions at different concentrations (from 0.25 to 3 w/w%.) have been found to display a viscoelastic solid-like behaviour, even for the lowest concentration tested. The storage modulus at 0.1 rad s(-1) increased strongly upon increasing concentration from 0.25 to 3 w/w%, following a power law with an exponent of 2.58. All suspensions exhibited a shear-thinning behaviour. It was also found that viscoelastic properties of the suspensions of cellulose are not affected by temperature or by varying pH from 4.5 to 9 while the G' and G '' moduli increased as salt concentration of the suspensions increased. This reinforcement of the viscoelastic properties by increasing ionic strength can be related to a screening of the electrostatic repulsions between the microfibrils, due to the presence of uronic acid groups, enhancing the fiber-fiber interactions. Mechanical treatment did not affect cellulose crystallinity. The effect of freezing was investigated as an alternative way to the most conventional cellulose preparation that consists to freeze-dry the suspensions for their conservation. It was shown that freezing preserved the rheological properties of the suspensions, contrary to freeze drying
Published: 2010
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18. 'Green labelled' pectins with gelling and emulsifying properties can be extracted by enzymatic way from unexploited sources

Author: Marie-Hélène Boiffard, Jean-François Thibault, Cédric Gaillard, Estelle Bonnin, Agata Zykwinska, Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), and Institut National de la Recherche Agronomique (INRA)
Subjects: animal structures, food.ingredient, Sucrose, Pectin, General Chemical Engineering, By-product valorization, macromolecular substances, 02 engineering and technology, Polysaccharide, complex mixtures, chemistry.chemical_compound, 0404 agricultural biotechnology, food, [SDV.IDA]Life Sciences [q-bio]/Food engineering, By-product, [SPI.GPROC]Engineering Sciences [physics]/Chemical and Process Engineering, Food science, Functional properties, chemistry.chemical_classification, Ecofriendly extraction, Chemistry, Atomic force microscopy, Food additive, digestive, oral, and skin physiology, Extraction (chemistry), food and beverages, 04 agricultural and veterinary sciences, General Chemistry, 021001 nanoscience & nanotechnology, 040401 food science, Enzyme, Biochemistry, AFM, Rheology, 0210 nano-technology, Food Science
Abstract: International audience; Functional properties of “green labelled” pectins extracted with enzymes from chicory root, citrus peel and cauliflower by-products were assessed. Chicory and citrus pectins were selected to study their gelling properties, while cauliflower pectin was chosen to investigate its emulsifying ability. High methoxy chicory and citrus pectins were shown to gel in the presence of sucrose at acidic pH, whereas their corresponding low methoxy pectins were able to gel in the presence of calcium. Additionally, HM cauliflower pectin exhibited emulsifying ability. Atomic Force Microscopy was used to better understand the gelling mechanism of pectins and particularly the first steps of gel setting. The present work demonstrates that “green labelled” enzyme-extracted pectins can be successfully used as gelling or emulsifying agents. The present study allows enhancing the value of “green” extraction of pectins, since such extraction leads to products with good functional properties that can directly be used for food and non-food purposes.
Published: 2009
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19. Aqueous-Core Lipid Nanocapsules for Encapsulating Fragile Hydrophilic and/or Lipophilic Molecules

Author: Cédric Gaillard, Sandy Vrignaud, Jean-Pierre Benoit, Nicolas Anton, Patrick Saulnier, Emilien Porcher, Ingénierie de la vectorisation particulaire, Université d'Angers (UA)-Institut National de la Santé et de la Recherche Médicale (INSERM), Micro et Nanomédecines Biomimétiques (MINT), Université d'Angers (UA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université Bretagne Loire (UBL), Unité de Biostatistique et de Recherche Clinique (UBRC), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-CHU Caen, Normandie Université (NU)-Tumorothèque de Caen Basse-Normandie (TCBN)-Tumorothèque de Caen Basse-Normandie (TCBN), Centre d'Ecologie et des Sciences de la COnservation (CESCO), Muséum national d'Histoire naturelle (MNHN)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Centre Hospitalier Universitaire d'Angers (CHU Angers), and PRES Université Nantes Angers Le Mans (UNAM)
Subjects: Lipid nanocapsules, cryo-TEM, [SDV]Life Sciences [q-bio], Static Electricity, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Proof of concept, Nanocapsules, Electrochemistry, Animals, Chemotherapy, Molecule, molecules, General Materials Science, Anti-cancer therapies, Hydrophilicity, Spectroscopy, Aqueous solution, Chemistry, Water, Serum Albumin, Bovine, Hydrophilic species, Surfaces and Interfaces, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 0104 chemical sciences, Methylene Blue, Chemical engineering, Soft particle analysis, TEM, Cattle, Emulsions, Encapsulation, 0210 nano-technology, Azo Compounds, Hydrophobic and Hydrophilic Interactions, Oils, Fluorescein-5-isothiocyanate
Abstract: International audience; This paper presents the original method of producing aqueous-core lipid nanocapsule, able to encapsulate both hydrophilic and lipophilic species with relevant yields. The scope offered by the integration of both hydrophilic and lipophilic molecules within the same colloidal objects make this method a prime candidate for the numerous anticancer therapies for which chemotherapy frequently requires the association of several molecules. The proof of concept study is proposed here (i) describing in detail the formulation of such objects and their characterization (TEM, cryo-TEM, soft particle analysis), (ii) showing the encapsulation of hydrophilic species alone, using examples of very different molecular weights, such as a dye (methylene blue) and a protein (BSA-isothycianate fluorecein labeled), and (iii) showing the simultaneous encapsulation of hydrophilic (methylene blue) and lipophilic (also a dye, red Sudan III) species.
Published: 2009
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20. Nanostructured polymer composite nanoparticles synthesized in a single step via simultaneous ROMP and ATRP under microemulsion conditions

Author: Valérie Héroguez, Emmanuel Ibarboure, Cédric Airaud, and Cédric Gaillard
Subjects: Materials science, Polymers and Plastics, Atom-transfer radical-polymerization, Organic Chemistry, Radical polymerization, Emulsion polymerization, 02 engineering and technology, ROMP, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Ring-opening polymerization, 0104 chemical sciences, Grubbs' catalyst, chemistry.chemical_compound, Polymerization, chemistry, Polymer chemistry, Materials Chemistry, Ring-opening metathesis polymerisation, 0210 nano-technology
Abstract: Ring-Opening Metathesis Polymerization (ROMP) and Atom-Transfer Radical Polymerization (ATRP) were carried out simultaneously under microemulsion conditions with 1st generation Grubbs catalyst playing a double role: ROMP initiator and ATRP controlling agent. Starting from two distinct microemulsions—one containing the monomers and the other the catalyst—well-defined composite nanoparticles with z-average hydrodynamic diameter smaller than 50 nm were prepared. Depending on the monomers droplet composition, homopolymers blends or graft-copolymers were synthesized in a one-pot, one-step, one-catalyst approach. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4014–4027, 2009
Published: 2009
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21. Simple Engineering of Polymer-Nanoparticle Hybrid Nanocapsules

Author: Flavien Sciortino, Cédric Gaillard, Gérald Casterou, Fabienne Gauffre, Myrtil L. Kahn, Marie-Bérengère Troadec, Soizic Chevance, Pierre-Antoine Eliat, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes-Centre National de la Recherche Scientifique (CNRS), Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Plate-forme Rennaise d'Imagerie et Spectroscopie Structurale et Métabolique (PRISM), Institut National de la Recherche Agronomique (INRA)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA)-Structure Fédérative de Recherche en Biologie et Santé de Rennes ( Biosit : Biologie - Santé - Innovation Technologique ), Institut de Génétique et Développement de Rennes (IGDR), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS)-Structure Fédérative de Recherche en Biologie et Santé de Rennes ( Biosit : Biologie - Santé - Innovation Technologique ), Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), Institut National de la Recherche Agronomique (INRA), BIOSIT-University of Rennes 1, CNRS UMS, Inserm US, Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Rennes-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), 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)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Structure Fédérative de Recherche en Biologie et Santé de Rennes ( Biosit : Biologie - Santé - Innovation Technologique )-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Structure Fédérative de Recherche en Biologie et Santé de Rennes ( Biosit : Biologie - Santé - Innovation Technologique )-Centre National de la Recherche Scientifique (CNRS)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES), Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie de Toulouse (ICT), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Structure Fédérative de Recherche en Biologie et Santé de Rennes ( Biosit : Biologie - Santé - Innovation Technologique )-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), and Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS)-Structure Fédérative de Recherche en Biologie et Santé de Rennes ( Biosit : Biologie - Santé - Innovation Technologique )
Subjects: Materials science, water, Energy Engineering and Power Technology, Nanoparticle, Nanotechnology, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Nanocapsules, Biomaterials, chemistry.chemical_compound, Materials Chemistry, copolymers, [CHIM]Chemical Sciences, chemistry.chemical_classification, vesicles, Renewable Energy, Sustainability and the Environment, [CHIM.MATE]Chemical Sciences/Material chemistry, Polymer, 021001 nanoscience & nanotechnology, 0104 chemical sciences, stabilization, agents, Solvent, solvents, mixtures, chemistry, Colloidal gold, Polymersome, Self-assembly, iron-oxide nanoparticles, 0210 nano-technology, Iron oxide nanoparticles, supramolecular structures, nanobubbles
Abstract: International audience; A general method to generate hybrid hollow capsules is reported. The process is based on the stabilization of solvent droplets by nanoparticles, in macroscopically miscible mixtures of tetrahydrofuran (THF) and water. After addition of a crosslinking polymer and removal of the solvent core, capsules of diameter ca 100 nm are obtained. This novel strategy does not require the use of block copolymers. In contrast, most methods reporting the formation of hybrid nanocapsules incorporate nanoparticles into block-copolymer polymersomes or use nanoparticles tethered with block-copolymers. The nanocapsules were characterized using a full set of techniques including nanoparticle tracking analysis, electron microscopy and liquid phase atomic force microscopy. Our results show that the vesicular shape of the nanocapsules is templated by the liquid droplets. Nanocapsules were prepared from quantum dots, gold nanoparticles, superparamagnetic iron oxide nanoparticles and mixtures of particles. The entrapment of a fluorescent dye was also demonstrated. Thus, nanocapsules with dual properties (e.g., magnetic and fluorescent) are easily obtained. Interestingly, the magnetic nanocapsules enable magnetic resonance imaging contrast enhancement of tumors in vivo.
Published: 2016
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22. Electrostatically driven modulation of the reinforcement of agarose hydrogels by cellulose nanowhiskers

Author: Cédric Gaillard, Kévin Jacques Le Goff, Thierry Aubry, Catherine Garnier, Université de Bretagne Occidentale, Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), Institut National de la Recherche Agronomique (INRA), and Region Bretagne
Subjects: Materials science, Polymers and Plastics, polysaccharides, Nanoparticle, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, chemistry.chemical_compound, nanowires and nanocrystals, Polymer chemistry, Materials Chemistry, Surface charge, Cellulose, structure-property relations, General Chemistry, 021001 nanoscience & nanotechnology, gels, 0104 chemical sciences, Surfaces, Coatings and Films, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Chemical engineering, Transmission electron microscopy, Self-healing hydrogels, Volume fraction, Agarose, nanoparticles, rheology, 0210 nano-technology, Dispersion (chemistry)
Abstract: The modulation of the reinforcement effect brought by the addition of tunicate cellulose nanowhiskers with different surface charge densities to an agarose hydrogel matrix has been studied using linear viscoelastic measurements. The cellulose nanowhiskers were characterized using transmission electron microscopy, and their surface charge was determined by a titration method. The results show that increasing the charge at the surface of nanowhiskers tends to enhance the reinforcement effect, because of a better dispersion of nanowhiskers. However, the results also suggest the existence of an optimum surface charge, corresponding to a maximum reinforcement effect at a given volume fraction. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43063.
Published: 2016
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23. Smart Nonaqueous Foams from Lipid-Based Oleogel

Author: Anne-Laure Fameau, Cédric Gaillard, Arnaud Saint-Jalmes, Orlin D. Velev, Audrey Arnould, Stephanie Lam, Unité de Recherches Biopolymères, Interactions, Assemblages, Institut National de la Recherche Agronomique (INRA), department of chemical and biochemical engineering, North Carolina State University [Raleigh] (NC State), University of North Carolina System (UNC)-University of North Carolina System (UNC), UR1268 Biopolymeres Interactions Assemblages, Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), Institut de Physique de Rennes (IPR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS), Institut National de la Recherche Agronomique, W911NF-15-1-0115, Army Research Office, MP 1106, European Cooperation in Science and Technology, DMR-1121107, Division of Materials Research, Région Pays de la Loire, INRA (UR 1268), and Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Materials science, food.ingredient, Surface Properties, Fatty alcohol, Nanotechnology, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, law.invention, Crystal, chemistry.chemical_compound, Adsorption, food, Pulmonary surfactant, law, Electrochemistry, Plant Oils, Sunflower Oil, General Materials Science, cardiovascular diseases, Organic Chemicals, Particle Size, Crystallization, Spectroscopy, Aqueous solution, Sunflower oil, Temperature, Foams, Surfaces and Interfaces, Interface, 021001 nanoscience & nanotechnology, Condensed Matter Physics, Lipids, 0104 chemical sciences, chemistry, Chemical engineering, lipids (amino acids, peptides, and proteins), Particle size, Fatty Alcohols, 0210 nano-technology, [PHYS.COND.CM-SCM]Physics [physics]/Condensed Matter [cond-mat]/Soft Condensed Matter [cond-mat.soft]
Abstract: COST [MP 1106]; INRA; Region Pays de la Loire; U.S. Army Research Office [W911NF-15-1-0115]; NSF Research Triangle MRSEC on Programmable Soft Matter [DMR-1121107]; International audience; Oil foams are composed of gas bubbles dispersedin an oil phase. These systems are scarcely studied despite theirgreat potential in diverse fields such as the food and cosmeticindustries. Contrary to aqueous foams, the production of oilfoams is difficult to achieve due to the inefficiency of surfactantadsorption at oil−air interfaces. Herein, we report a simple way toproduce oil foams from oleogels, whose liquid phase is a mixtureof sunflower oil and fatty alcohols. The temperature at which theoleogel formed was found to depend on both fatty alcohol chainlength and concentration. The air bubbles in the oleogel foamwere stabilized by fatty alcohol crystals. Below the meltingtemperature of the crystals, oleogel foams were stable for months.Upon heating, these ultrastable foams collapsed within a few minutes due to the melting of the crystal particles. The transitionbetween crystal formation and melting was reversible, leading to thermoresponsive nonaqueous foams. The reversible switchingbetween ultrastable and unstable foam depended solely on the temperature of the system. We demonstrate that these oleogelfoams can be made to be photoresponsive by using internal heat sources such as carbon black particles, which can absorb UVlight and dissipate the absorbed energy as heat. This simple approach for the formulation of responsive oil foams could be easilyextended to other oleogel systems and could find a broad range of applications due to the availability of the components in largequantities and at low cost.
Published: 2015
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24. pH-responsive fatty acid self-assembly transition induced by UV light

Author: Anne-Laure Fameau, Audrey Arnould, Cédric Gaillard, Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), and Institut National de la Recherche Agronomique (INRA)
Subjects: Light, Ultraviolet Rays, Infrared spectroscopy, 02 engineering and technology, 010402 general chemistry, Photochemistry, 01 natural sciences, Micelle, Biomaterials, Surface-Active Agents, Colloid and Surface Chemistry, Lamellar structure, Irradiation, chemistry.chemical_classification, Aqueous solution, Vesicle, Photodissociation, Fatty Acids, Fatty acid, Self-assembly, Hydrogen-Ion Concentration, 021001 nanoscience & nanotechnology, Photoacid generator, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Responsive surfactant, chemistry, 13. Climate action, 0210 nano-technology, [CHIM.OTHE]Chemical Sciences/Other
Abstract: International audience; Fatty acids are natural, pH-responsive surfactants. Their properties can be tuned by adding CO2 or by applying light which modify solution pH. We investigated photoresponsive systems based on fatty acids with different chain lengths in the presence of a photoacid generator (PAG). Under UV irradiation, photolysis of the PAG in aqueous solution resulted in a decrease in pH, triggering a change in fatty acid assembly. Using a multi-scale approach before and after UV irradiation, we characterized the effect of this pH decrease on the nature of the fatty acid self-assemblies. At the molecular scale, pH and infrared spectroscopy measurements were used to determine the fatty acid ionization state. At the microscopic scale, the self-assembled structure was characterized using small-angle neutron scattering and microscopy. We showed that UV irradiation tuned the ionization state of the fatty acid molecules which in turn triggered a transition from spherical micelles to vesicles or lamellar phases, depending on fatty acid chain length. We studied the foaming properties of these systems before and after UV irradiation. We showed that after uv irradiation, foam stability was drastically enhanced as a result of a change in self-assembly. Our approach can be easily extended to various pH-responsive surfactants.
Published: 2015
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25. Self-assembly of myristic acid in the presence of choline hydroxide: Effect of molar ratio and temperature

Author: Audrey Arnould, Cédric Gaillard, Liliana G. Santiago, Anne-Laure Fameau, Thomas Zemb, Adrián A. Perez, Marc Anton, Jean-Paul Douliez, Fabrice Cousin, Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), Institut National de la Recherche Agronomique (INRA), Grupo Biocoloides y nanotecnologías (GBN), Universidad Nacional del Litoral [Santa Fe] (UNL), Biologie du fruit et pathologie (BFP), Université Bordeaux Segalen - Bordeaux 2-Institut National de la Recherche Agronomique (INRA)-Université Sciences et Technologies - Bordeaux 1, 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, 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)-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)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Université Bordeaux Segalen - Bordeaux 2-Institut National de la Recherche Agronomique (INRA)-Université Sciences et Technologies - Bordeaux 1 (UB), 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)-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), 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: Molar ratio, Inorganic chemistry, Lipid Bilayers, Myristic acid, molar ratio, 02 engineering and technology, INGENIERÍAS Y TECNOLOGÍAS, Conductivity, 010402 general chemistry, 01 natural sciences, Micelle, Myristic Acid, catanionic, Phase Transition, Choline, Biomaterials, chemistry.chemical_compound, Colloid and Surface Chemistry, Differential scanning calorimetry, Counter-ion, [CHIM]Chemical Sciences, counter-ion, chemistry.chemical_classification, Ions, Nanotecnología, Temperature, Fatty acid, Self-assembly, self-assembly, 021001 nanoscience & nanotechnology, Nano-materiales, Small-angle neutron scattering, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, chemistry, Hydroxide, fatty acid, Counterion, 0210 nano-technology, Catanionic
Abstract: Salt-free catanionic systems based on fatty acids and cationic surfactants are known to exhibit a broad polymorphism by simply tuning the molar ratio between the two components. In the case of fatty acid combined with organic amino counter-ions, very few data are available on the phase behavior obtained as a function of the molar ratio between the counter-ion and the fatty acid. In this study, we investigated the choline hydroxide/myristic acid system as a function of the molar ratio, R= n choline hydroxide/n myristic acid, and the temperature. At molecular scale, the ionization state of myristic acid was determined as a function of R by coupling pH, conductivity and infra-red spectroscopy measurements. At microscopic scale, the self-assemblies were characterized by small angle neutron scattering and microscopy experiments.For R1, all the myristic acid molecules were under their ionized form and only spherical micelles were present in solution. As in the case of catanionic systems, our study highlights that both R and temperature are two key parameters to finely control the self-assembly structure formed by myristic acid in the presence of choline hydroxide. Fil: Arnould, Audrey. Institut National de la Recherche Agronomique; Francia Fil: Perez, Adrián Alejandro. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Instituto de Tecnología de los Alimentos; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; Argentina Fil: Gaillard, Cédric. Institut National de la Recherche Agronomique; Francia Fil: Douliez, Jean Paul. Institut National de la Recherche Agronomique; Francia Fil: Cousin, Fabrice. Centre National de la Recherche Scientifique; Francia Fil: Santiago, Liliana Gabriela. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Instituto de Tecnología de los Alimentos; Argentina Fil: Zemb, Thomas. Centre National de la Recherche Scientifique; Francia Fil: Anton, Marc. Institut National de la Recherche Agronomique; Francia Fil: Fameau, Anne Laure. Institut National de la Recherche Agronomique; Francia
Published: 2015
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26. Rheological study of reinforcement of agarose hydrogels by cellulose nanowhiskers

Author: Cédric Gaillard, Thierry Aubry, William Helbert, Catherine Garnier, Kévin Jacques Le Goff, ONERA - The French Aerospace Lab [Salon], ONERA, Marchés, Organisations, Institutions et Stratégies d'Acteurs (UMR MOISA), Centre de Coopération Internationale en Recherche Agronomique pour le Développement (Cirad)-Institut National de la Recherche Agronomique (INRA)-Centre international d'études supérieures en sciences agronomiques (Montpellier SupAgro)-Centre International de Hautes Etudes Agronomiques Méditerranéennes - Institut Agronomique Méditerranéen de Montpellier (CIHEAM-IAMM), Centre International de Hautes Études Agronomiques Méditerranéennes (CIHEAM)-Centre International de Hautes Études Agronomiques Méditerranéennes (CIHEAM)-Institut national d’études supérieures agronomiques de Montpellier (Montpellier SupAgro), Centre National de la Recherche Scientifique (CNRS), Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), Institut National de la Recherche Agronomique (INRA), Laboratoire d'Ingénierie des Matériaux de Bretagne (LIMATB), Université de Bretagne Sud (UBS)-Institut Brestois du Numérique et des Mathématiques (IBNM), Université de Brest (UBO)-Université de Brest (UBO)-Université de Brest (UBO), Centre de Recherches sur les Macromolécules Végétales (CERMAV), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Joseph Fourier - Grenoble 1 (UJF), 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), Region Bretagne, Region Pays de Loire, GlycoOuest Network, Institut national d’études supérieures agronomiques de Montpellier (Montpellier SupAgro), Institut national d'enseignement supérieur pour l'agriculture, l'alimentation et l'environnement (Institut Agro)-Institut national d'enseignement supérieur pour l'agriculture, l'alimentation et l'environnement (Institut Agro)-Centre International de Hautes Etudes Agronomiques Méditerranéennes - Institut Agronomique Méditerranéen de Montpellier (CIHEAM-IAMM), and Centre International de Hautes Études Agronomiques Méditerranéennes (CIHEAM)-Centre International de Hautes Études Agronomiques Méditerranéennes (CIHEAM)-Institut National de la Recherche Agronomique (INRA)-Centre de Coopération Internationale en Recherche Agronomique pour le Développement (Cirad)-Centre international d'études supérieures en sciences agronomiques (Montpellier SupAgro)
Subjects: Materials science, Polymers and Plastics, Nanoparticle, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Matrix (chemical analysis), chemistry.chemical_compound, Rheology, Materials Chemistry, Stress relaxation, Cellulose nanowhiskers, [CHIM]Chemical Sciences, Composite material, Cellulose, Agarose hydrogels, ComputingMilieux_MISCELLANEOUS, Organic Chemistry, Structure, Rheological behavior, 021001 nanoscience & nanotechnology, 0104 chemical sciences, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Transmission electron microscopy, Self-healing hydrogels, Agarose, 0210 nano-technology
Abstract: International audience; The influence of the addition of tunicate cellulose nanowhiskers on the structural and rheological properties of an agarose hydrogel matrix has been studied, with the objective to design innovative green material, with good mechanical properties. The cellulose nanowhiskers were characterized using transmission electron microscopy, and their charge surface density was determined by a titration method. Oscillatory shear and stress relaxation tests were performed in order to characterize the rheological properties of the agarose matrix, and of the agarose hydrogels filled by nanowhiskers at volume fractions below 0.2%. The results show a significant reinforcement effect due to the addition of nanowhiskers, and suggest changes in the matrix network structure induced by the cellulose nanoparticles.
Published: 2015
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27. In vitro digestion of emulsions: high spatiotemporal resolution using synchrotron SAXS

Author: Sébastien Marze, Cédric Gaillard, Pierre Roblin, Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), Institut National de la Recherche Agronomique (INRA), and Synchrotron SOLEIL
Subjects: Nanotechnology, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Models, Biological, law.invention, Digestion (alchemy), Spatio-Temporal Analysis, X-Ray Diffraction, law, Scattering, Small Angle, [SDV.IDA]Life Sciences [q-bio]/Food engineering, [SPI.GPROC]Engineering Sciences [physics]/Chemical and Process Engineering, Intestinal Mucosa, Triglycerides, Chemistry, Small-angle X-ray scattering, Vesicle, General Chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, In vitro digestion, Synchrotron, 0104 chemical sciences, Kinetics, Chemical engineering, Emulsion, Digestion, Emulsions, Absorption (chemistry), 0210 nano-technology, Lipid digestion, Synchrotrons
Abstract: International audience; Although the biochemical processes of lipid digestion are well-known, the biophysical ones, responsible for the assembly of molecules into functional structures, lack studies resolving both time and space scales. About 35 years ago, the seminal microscopy study of Patton and Carey constituted a major advance to reach this goal. Nowadays, new perspectives arise from the availability of large facilities scattering techniques, able to monitor the dynamics of multi-scale assemblies with unprecedented resolutions. The present small angle X-ray scattering (SAXS) study focused on the roles of the emulsifier and triglyceride in the formation of lipid assemblies during emulsion digestion in vitro. By developing several interpretations of the data in the whole space range (qualitative, shape-dependent and shape-independent models), the characteristic size of the assemblies and their transition times were obtained, which depended on the triglyceride, but not on the emulsifier. The major assembly formed was found to be a spherical mixed micelle, but vesicle was also found to coexist throughout the digestion, although in a lower proportion. The quantitative determination of the sizes and proportions of these assemblies, as well as the evolution of these characteristics during digestion are precious information for nutritional sciences, as these assemblies are the vehicles of lipophilic nutrients and micronutrients towards their absorption site.
Published: 2015
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28. Efficient in vitro gene therapy with PEG siRNA lipid nanocapsules for passive targeting strategy in melanoma

Author: Emilie André, Pauline Resnier, Nolwenn Lautram, Cédric Gaillard, Jean-Pierre Benoit, Catherine Passirani, Pierre LeQuinio, Guillaume Bastiat, Université d'Angers (UA), Micro et Nanomédecines Translationnelles (MINT), Université d'Angers (UA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), Institut National de la Recherche Agronomique (INRA), and ProdInra, Migration
Subjects: Small interfering RNA, NANOCARRIERS, Genetic enhancement, siRNA lipid nanocapsules, 02 engineering and technology, Applied Microbiology and Biotechnology, Polyethylene Glycols, Drug Delivery Systems, TUMOR, [SDV.IDA]Life Sciences [q-bio]/Food engineering, NANOPARTICLES, Nanotechnology, RNA, Small Interfering, Cytotoxicity, Melanoma, INTERFERENCE, 0303 health sciences, Liposome, General Medicine, Transfection, [SDV.IDA] Life Sciences [q-bio]/Food engineering, 021001 nanoscience & nanotechnology, Lipids, CANCER, Molecular Medicine, lipids (amino acids, peptides, and proteins), 0210 nano-technology, Cell Survival, [SPI.GPROC] Engineering Sciences [physics]/Chemical and Process Engineering, CH50 assay, Cryo-TEM imaging, Biology, 03 medical and health sciences, DELIVERY, Gene therapy, Nanocapsules, In vivo, Cell Line, Tumor, Humans, Gene silencing, [SPI.GPROC]Engineering Sciences [physics]/Chemical and Process Engineering, Gene Silencing, PERMEABILITY, 030304 developmental biology, Genetic Therapy, DNA, EFFICACY, Molecular biology, Cancer research, PEGylation, RNA
Abstract: International audience; Small interfering RNA (siRNA)-mediated gene therapy is a promising strategy to temporarily inhibit the expression of proteins implicated in carcinogenesis or chemotherapy resistance. Although intra-tumoral administration can be envisaged, studies currently focus on formulating nanomedicines for intravenous injection to target tumor sites as well as metastases. The development of synthetic nanoparticles and liposomes has advanced greatly during the last decade. The objective of this work consists in formulating and optimizing the encapsulation of siRNA into lipid nanocapsules (LNCs) for efficient gene therapy to target melanoma cells. SiRNA LNCs were prepared from DOTAP/DOPE lipoplexes, and the siRNA amount and lipid/siRNA charge ratio were assayed to improve the stability and the encapsulation yield. Cryo-TEM imaging of the siRNA lipoplexes and LNC morphology revealed specific organization of the siRNA DOTAP/DOPE lipoplexes as well as specific lipid microstructures that can be eliminated by purification. No cytotoxicity of the siRNA LNCs against the melanoma SK-Mel28 cell line was observed at concentrations of up to 500 ng/mL siRNA. In vitro siRNA transfection experiments, compared to Oligofectamine (TM), demonstrated interesting targeted gene silencing effects. Finally, complement activation assays confirmed the feasibility of the PEGylation of siRNA LNCs as part of a passive targeting strategy for future in vivo melanoma-and metastasis-targeting experiments.
Published: 2014
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29. Amino Acid−Nucleotide−Lipids: Effect of Amino Acid on the Self- Assembly Properties

Author: Philippe Barthélémy, Cédric Gaillard, Frédéric Nallet, Laurence Navailles, Giovanni Tonelli, Khalid Oumzil, Université de Bordeaux, ARNA Laboratory (U869), Université de Bordeaux (UB), Centre de recherches Paul Pascal (CRPP), Centre National de la Recherche Scientifique (CNRS), INRA (UR 1268), Institut National de la Recherche Agronomique (INRA), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), Region d'Aquitaine, and Army Research Office (U.S.A.)
Subjects: Surface Properties, Stereochemistry, [PHYS.PHYS.PHYS-BIO-PH]Physics [physics]/Physics [physics]/Biological Physics [physics.bio-ph], Phenylalanine, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Amphiphile, Electrochemistry, General Materials Science, Nucleotide, Amino Acids, Particle Size, Spectroscopy, chemistry.chemical_classification, Molecular Structure, Nucleotides, Biomolecule, Vesicle, technology, industry, and agriculture, RNA, Isothermal titration calorimetry, Surfaces and Interfaces, 021001 nanoscience & nanotechnology, Condensed Matter Physics, Lipids, 0104 chemical sciences, Amino acid, chemistry, lipids (amino acids, peptides, and proteins), 0210 nano-technology
Abstract: 9 pages; International audience; Hybrid amphiphiles composed of a lipid covalently linked to biomolecules are attracting considerable attention, owing to their unique physicochemical and biological properties. Herein, we have synthesized novel amino acid−nucleotide−lipids (ANLs), presenting phenylalanine and thymidine residues and saturated or unsaturated diacyl glycerol lipid moieties to investigate the effect of the specific aminoacid moieties on both aggregation properties and interactions of ANLs with single strand polyA RNA. Physicochemical studies (DLS, cryo-TEM, and small angle X-ray scattering) indicate that phenylanaline amino acids inserted at the 5′ position of the nucleotide-lipids stabilize multilamellar systems, whereas unilamellar vesicles are formed preferentially in the case of nucleotide−lipids (NLs). Both NLs and ANLs exhibit weak interactions with complementary polyA RNA as revealed by isothermal titration calorimetry investigations. The multilamellar vesicles obtained with ANLs could be used as a versatile carrier, suitable for both hydrophobic and hydrophilic therapeutic molecules.
Published: 2013
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30. One and two dimensional self-assembly of comb-like amphiphilic copolyelectrolytes in aqueous solution

Author: Wissam Moussa, Christophe Chassenieux, C. Limouzin-Morel, I. Iliopoulos, Cédric Gaillard, Fabien Dutertre, Denis Bendejacq, Taco Nicolai, Sciences et Ingénierie de la Matière Molle (SIMM), ESPCI ParisTech-PSL Research University (PSL)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut des Molécules et Matériaux du Mans (IMMM), Le Mans Université (UM)-Centre National de la Recherche Scientifique (CNRS), Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), Institut National de la Recherche Agronomique (INRA), Laboratoire Matière Molle et Chimie (MMC), ESPCI ParisTech-Centre National de la Recherche Scientifique (CNRS), RHODIA RECHERCHES ET TECHNOLOGIES CENTRE DE RECHERCHES ET TECHNOLOGIES D'AUBERVILLIERS, RHODIA RECHERCHES ET TECHNOLOGIES, Sciences et Ingénierie de la Matière Molle (UMR 7615) (SIMM), 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)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Le Mans Université (UM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS), French Research Ministry (MNRT grant), and Region Pays de la Loire
Subjects: Materials science, STYRENE, CATIONIC SURFACTANT PHASES, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, LAMELLAR PHASES, SYSTEMS, Amphiphile, Copolymer, WATER, ComputingMilieux_MISCELLANEOUS, chemistry.chemical_classification, Aqueous solution, General Chemistry, Polymer, 021001 nanoscience & nanotechnology, Condensed Matter Physics, Grafting, Small-angle neutron scattering, COPOLYMERS, 0104 chemical sciences, Crystallography, POLYMERIZATION, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Self-healing hydrogels, X-RAY, SHEAR, Self-assembly, 0210 nano-technology, OLIGOMERIC SURFACTANTS
Abstract: International audience; The spontaneous self-assembly of a novel comb-like amphiphilic copolyelectrolyte in water was studied by small angle neutron scattering and freeze fracture transmission electron microscopy. The copolymer was synthesized by randomly grafting pendant quaternized alkylamine moieties to a poly(styrene) chain. The effects of the grafting density and the length of the alkyls (C12-C18) on the structure were investigated systematically. The polymers were soluble over a broad range of grafting densities (35-80 mol%) where they assembled either into lamellae (35-55 mol%) consisting of a double layer of polymers or cylinders (65-80 mol%) formed by bundling of several chains. At higher concentrations, electrostatic repulsion drove smectic and hexagonal ordering of, respectively, the lamellae and the rods. TEM images showed micro-domains of stacked lamellae that were in some cases closed upon themselves to form onion-like particles. Exposure of hydrophobic patches at the surface due to defects of the self-assembly led to the formation of bonds between lamellae or cylinders. As a consequence visco-elastic solutions or hydrogels were formed at higher concentrations.
Published: 2013
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31. Rheological behaviour and microstructure of microfibrillated cellulose suspensions/low-methoxyl pectin mixed systems. Effect of calcium ions

Author: Cédric Gaillard, Catherine Garnier, Jean-Louis Doublier, Sylvie Durand, G. Agoda-Tandjawa, Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), and Institut National de la Recherche Agronomique (INRA)
Subjects: polysaccharide mixture, Thixotropy, food.ingredient, LM pectin, Polymers and Plastics, Pectin, Sodium, Composite number, microstructure, chemistry.chemical_element, 02 engineering and technology, Calcium, 010402 general chemistry, 01 natural sciences, chemistry.chemical_compound, food, Rheology, cellulose / LM pectin composite, [SDV.IDA]Life Sciences [q-bio]/Food engineering, Materials Chemistry, microfibrillated cellulose suspensions, Cellulose, Composite material, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, food and beverages, 021001 nanoscience & nanotechnology, Microstructure, cations, 0104 chemical sciences, chemistry, Chemical engineering, microscopy, rheology, 0210 nano-technology
Abstract: International audience; In this study, the influence of the presence of low-methoxyl pectin (LM pectin) on the rheological and microstructural properties of microfibrillated cellulose suspensions was elucidated in order to create new structures with new and interesting textures. For that purpose, the rheological properties of the cellulose/LM pectin mixtures in variable proportions were compared with those of the individual biopolymers. The influence of the presence of calcium and/or sodium ions on the properties of the mixed systems was studied. The microstructure of the resulting system was studied by transmission electron microscopy and confocal laser scanning microscopy. It was found that, in the presence of LM pectin, a synergistic effect was observed when calcium ions were also present, leading to increased rheological properties of the composites. Indeed, addition of calcium to the mixtures induced LM pectin gelation, which was favoured in the presence of sodium, the pectin network contributing to the formation of a stronger cellulose/LM pectin composite gel. The presence of LM pectin alone in the microfibrillated cellulose suspensions does not significantly modify the viscoelastic and microstructural properties of microfibrillated cellulose suspensions. Whether calcium was added to the mixtures or not in water, the viscoelastic properties of the mixtures are mainly controlled by cellulose. The same behaviour was observed for the mixtures in NaCl without added calcium. Contrary to this observation, it was noticed that in presence of both sodium and calcium ions, the viscoelastic properties of the mixtures are largely governed by LM pectin. On the other hand, it was showed that the flow behaviour of microfibrillated cellulose suspensions is modified in the presence of LM pectin with an increase in thixotropic character shear-thinning behaviour, which was more pronounced in the presence of NaCl. It was also shown, from TEM observations, that an interpenetrating network formed in cellulose/LM pectin composites gel in the presence of calcium ions. In the same way, the CLSM observations allowed the separate localization of cellulose and LM pectin within the composite systems to be highlighted. The results obtained suggests that it is possible to thus create new structures with new interesting textures, by mixing microfibrillated cellulose suspensions and LM pectin in suitable proportions in the simultaneous presence of both sodium and calcium ions.
Published: 2012
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32. Properties of cellulose/pectins composites. Implication for structural and mechanical properties of cell wall

Author: Jean-Louis Doublier, Catherine Garnier, Cédric Gaillard, G. Agoda-Tandjawa, Sylvie Durand, Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), Institut National de la Recherche Agronomique (INRA), and French Research Ministry
Subjects: Polymers and Plastics, Surface Properties, microstructure, Viscoelastic Substances, 02 engineering and technology, engineering.material, mechanical properties, Polysaccharide, Viscoelasticity, Nanocomposites, Cell wall, 03 medical and health sciences, chemistry.chemical_compound, pectins, Biopolymers, Rheology, Cell Wall, Materials Chemistry, Side chain, [SDV.BV]Life Sciences [q-bio]/Vegetal Biology, Cellulose, Composite material, 030304 developmental biology, chemistry.chemical_classification, 0303 health sciences, Viscosity, Osmolar Concentration, Organic Chemistry, food and beverages, Polymer, 021001 nanoscience & nanotechnology, cations, Elasticity, cellulose, Biomechanical Phenomena, primary plant cell wall, chemistry, engineering, microscopy, Calcium, rheology, Biopolymer, Beta vulgaris, 0210 nano-technology
Abstract: International audience; The primary cell wall of dicotyledonous plants can be considered as a concentrated polymer assembly, containing in particular polysaccharides among which cellulose and pectins are known to be the major components. In order to understand and control the textural quality of plant-derived foods, it is highly important to elucidate the rheological and microstructural properties of these components, individually and in mixture, in order to define their implication for structural and mechanical properties of primary plant cell wall. In this study, the rheological and microstructural properties of model systems composed of sugar-beet microfibrillated cellulose and HM pectins from various sources, with varied degrees of methylation and containing different amounts of neutral sugar side chains, were investigated. The influence of the presence of calcium and/or sodium ions and the biopolymer concentrations on the properties of the mixed systems were also studied. The characterizations of the mixed system, considered as a simplified model of primary plant cell wall, showed that whatever the structural characteristics of the pectins, the ionic conditions of the medium and the biopolymer concentrations, the gelation of the composite was mainly controlled by cellulose. Thus, the cellulose network would be the principal component governing the mechanical properties of the cell walls. However, the neutral sugar side chains of the pectins seem to play a part in the interactions with cellulose, as shown by the interesting viscoelastic properties of cellulose/apple HM pectins systems. The rigidity of cellulose/pectins composite was strongly influenced by the structural characteristics of pectins. The particular properties of primary plant cell walls would thus result from the solid viscoelastic properties of cellulose, its interactions with pectins according to their structural characteristics (implication of the neutral sugar side chains and the specific potential calcic interactions) and of the distribution of the components in separate phases.
Published: 2012
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33. Smart Foams: Switching Reversibly between Ultrastable and Unstable Foams

Author: Anne-Laure, Fameau, Arnaud, Saint-Jalmes, Fabrice, Cousin, Bérénice, Houinsou Houssou, Bruno, Novales, Laurence, Navailles, Janine, Emile, Frédéric, Nallet, Cédric, Gaillard, François, Boué, Jean-Paul, Douliez, Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), Institut National de la Recherche Agronomique (INRA), 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, Institut de Physique de Rennes (IPR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS), Centre de recherches Paul Pascal (CRPP), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), 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), and Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Materials science, Interfaces, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Micelle, Catalysis, chemistry.chemical_compound, Adsorption, Scattering, Small Angle, Fatty acids, Coalescence (physics), Microscopy, Confocal, Tubes, Air, Temperature, Water, Foams, General Medicine, General Chemistry, Limiting, Self-assembly, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Neutron Diffraction, Monomer, [CHIM.POLY]Chemical Sciences/Polymers, Chemical engineering, chemistry, lipids (amino acids, peptides, and proteins), 0210 nano-technology, [PHYS.COND.CM-SCM]Physics [physics]/Condensed Matter [cond-mat]/Soft Condensed Matter [cond-mat.soft], Stearic Acids
Abstract: 6 pages; International audience; Ultrastable foams with an optimal foamability have been obtained using hydroxyl fatty acids tubes. The stabilization results from the adsorption of monomers at the air-water interface preventing coalescence and coarsening and from the presence of tubes in the Plateau borders limiting the drainage. Upon heating, tubes transit to micelles, which induces foam destabilization. Such foams are thus the first to have a temperature tunable stability.
Published: 2011
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34. DNA-Polymer micelles as nanoparticles with recognition ability

Author: Renée Mayap Talom, Christel Cerclier, Cédric Gaillard, Fabienne Gauffre, Julian Oberdisse, Leonard Kaps, Gad Fuks, Christophe Mingotaud, 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), Université Fédérale Toulouse Midi-Pyrénées, Laboratoire Charles Coulomb (L2C), Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), 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), Institut des Technologies Avancées en sciences du Vivant (ITAV), Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées, Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), Institut National de la Recherche Agronomique (INRA), The authors thank all the present and former collaborators of the project 'DNATOOL'. We acknowledge the Agence Nationale de la Recherche for funding (program ANR PNANO-07) and the Laboratoire d'Analyse et d'Architecture des Systemes (LAAS-CNRS) for access to Nanoscope 3., 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), Université de Toulouse (UT), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), and Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Polymers, micelles, Polyesters, Oligonucleotides, Nanoparticle, surface patterning, Nanotechnology, 02 engineering and technology, macromolecular substances, 010402 general chemistry, chemistry, 01 natural sciences, Micelle, Catalysis, chemistry.chemical_compound, Molecular recognition, [SDV.IDA]Life Sciences [q-bio]/Food engineering, Copolymer, [SPI.GPROC]Engineering Sciences [physics]/Chemical and Process Engineering, Particle Size, chemistry.chemical_classification, Oligonucleotide, Organic Chemistry, technology, industry, and agriculture, General Chemistry, Polymer, Quartz crystal microbalance, DNA, 021001 nanoscience & nanotechnology, 0104 chemical sciences, block copolymers, Chemical engineering, Nanoparticles, molecular recognition, 0210 nano-technology, Caprolactone, oligonucleotides, multidisciplinary
Abstract: International audience; The Watson-Crick binding of DNA single strands is a powerful tool for the assembly of nanostructures. Our objective is to develop polymer nanoparticles equipped with DNA strands for surface-patterning applications, taking advantage of the DNA technology, in particular, recognition and reversibility. A hybrid DNA copolymer is synthesized through the conjugation of a ssDNA (22-mer) with a poly(ethylene oxide)-poly(caprolactone) diblock copolymer (PEO-b-PCl). It is shown that, in water, the PEO-b-PCl-ssDNA(22) polymer forms micelles with a PCl hydrophobic core and a hydrophilic corona made of PEO and DNA. The micelles are thoroughly characterized using electron microscopy (TEM and cryoTEM) and small-angle neutron scattering. The binding of these DNA micelles to a surface through DNA recognition is monitored using a quartz crystal microbalance and imaged by atomic force microscopy. The micelles can be released from the surface by a competitive displacement event.
Published: 2011
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35. Self-similar assemblies of globular whey proteins at the air-water interface: Effect of the structure

Author: Alain Riaublanc, François Boué, Cédric Gaillard, Najet Mahmoudi, Monique A.V. Axelos, Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), Institut National de la Recherche Agronomique (INRA), 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), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Université Paris-Saclay
Subjects: Whey protein, Globular protein, Surface Properties, Static Electricity, 02 engineering and technology, Surface pressure, 01 natural sciences, Light scattering, Biomaterials, Colloid and Surface Chemistry, Adsorption, Dynamic light scattering, 0103 physical sciences, Monolayer, Scattering, Small Angle, Pressure, Surface Tension, chemistry.chemical_classification, 010304 chemical physics, Chemistry, Protein Stability, Air, Cryoelectron Microscopy, Osmolar Concentration, Water, 021001 nanoscience & nanotechnology, Milk Proteins, Small-angle neutron scattering, Elasticity, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Crystallography, Neutron Diffraction, Whey Proteins, Chemical physics, Emulsifying Agents, Protein Multimerization, 0210 nano-technology, Rheology, [CHIM.OTHE]Chemical Sciences/Other
Abstract: International audience; We investigated the structure of heat-induced assemblies of whey globular proteins using small angle neutron scattering (SANS), static and dynamic light scattering (SLS and DLS), and cryogenic transmission electron microscopy (Cryo-TEM). Whey protein molecules self-assemble in fractal aggregates with a structure density depending on the electrostatic interactions. We determined the static and dynamic properties of interfacial layer formed by the protein assemblies, upon adsorption and spreading at the air-water interface using surface film balance and interfacial dilatational rheology. Upon spreading, all whey protein systems show a power-law scaling behavior of the surface pressure versus concentration in the semi-dilute surface concentration regime, with an exponent ranging from 5.5 to 9 depending on the electrostatic interactions and the aggregation state. The dilatational modulus derived from surface pressure isotherms shows a main peak at 6-8 mN/m, generally considered to be the onset of a conformational change in the monolayer, and a second peak or a shoulder at 15 mN/m. Long-time adsorption kinetics give similar results for both the native whey proteins and the corresponding self-similar assemblies, with a systematic effect of the ionic strength
Published: 2010
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36. Self-Assembly and Foaming Properties of Fatty Acid-Lysine Aqueous Dispersions

Author: Alain Riaublanc, Cédric Gaillard, Frédéric Nallet, Bruno Novales, Jean-Paul Douliez, Laurence Navailles, Bérénice Houinsou Houssou, Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), Institut National de la Recherche Agronomique (INRA), Centre de recherches Paul Pascal (CRPP), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Sciences et Technologies - Bordeaux 1, and Centre National de la Recherche Scientifique (CNRS)
Subjects: Magnetic Resonance Spectroscopy, Carboxylic acid, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Micelle, Microscopy, Electron, Transmission, Electrochemistry, Organic chemistry, Aerosols and foams, General Materials Science, Spectroscopy, Alkyl, Micelles, Unilamellar Liposomes, chemistry.chemical_classification, Aqueous solution, Calorimetry, Differential Scanning, Chemistry, Vesicle, Lysine, Fatty Acids, Temperature, Fatty acid, Surfaces and Interfaces, 021001 nanoscience & nanotechnology, Condensed Matter Physics, Small-angle neutron scattering, Liquid-liquid interfaces, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Chemical engineering, Saturated fatty acid, lipids (amino acids, peptides, and proteins), Lyotropic phases, 0210 nano-technology, 61.30.St, 68.05.-n, 82.70.Rr, [PHYS.COND.CM-SCM]Physics [physics]/Condensed Matter [cond-mat]/Soft Condensed Matter [cond-mat.soft]
Abstract: 6 pages; International audience; We report on dispersions of fatty acid-lysine salts in aqueous solutions which are further used to produce foams. The alkyl chain length is varied from dodecyl to stearic. In aqueous solutions, the lysine salt of the dodecyl chain yields an isotropic solution, probably micelles, whereas for longer alkyl chains, vesicles formed but crystallized upon resting at room temperature or when kept at 4 C. Solid stateNMRshowed that in vesicles fatty acids are embedded in a lamellar arrangement passing from a gel to a fluid state upon heating; the transition temperature at which it occurs was determined by DSC. Those results are confirmed by small-angle neutron scattering which also give additional information on the bilayer structure. Incredibly stable foams are obtained using the palmitic acid/Lys salt whereas for other alkyl chain length, poor or no foam is formed. We conclude that the foamability is related to the phase behavior in aqueous solution.
Published: 2010
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37. Dynamic and supramolecular organisation of α-lactalbumin/lysozyme microspheres: A microscopic study

Author: Saïd Bouhallab, Cédric Gaillard, Thomas Croguennec, Michaël Nigen, and Marie-Noelle Madec
Subjects: Morphology (linguistics), apo α-LA, Globular protein, [SDV]Life Sciences [q-bio], Biophysics, Supramolecular chemistry, FITC, 02 engineering and technology, CSLM, Microscopy, Atomic Force, Biochemistry, Microsphere, RBITC, chemistry.chemical_compound, 0404 agricultural biotechnology, Microscopy, Electron, Transmission, assembly mechanism, [SDV.IDA]Life Sciences [q-bio]/Food engineering, LYS, [SPI.GPROC]Engineering Sciences [physics]/Chemical and Process Engineering, lysozyme, Total protein, Lactalbumin, chemistry.chemical_classification, Microscopy, Confocal, Atomic force microscopy, Organic Chemistry, 04 agricultural and veterinary sciences, 021001 nanoscience & nanotechnology, 040401 food science, Crystallography, microspheres, chemistry, SEM, Microscopy, Electron, Scanning, TEM, Muramidase, Lysozyme, Protein Multimerization, AFM, 0210 nano-technology, Apoproteins, α-lactalbumin
Abstract: International audience; Apo α-lactalbumin (apo α-LA) and lysozyme (LYS), two homologous globular proteins have been shown to be able to interact and self-assemble to form microspheres. We report on the organisation and the mechanism of such protein assembly process using a variety of microscopic techniques. We demonstrated that proteins involved into apo α-LA/LYS microspheres exchange with those free in solution. The exchange process takes place from the periphery to the centre of the microspheres. The formed spherical particles observed after fixed incubation time were found to be either individual or aggregated according to the total protein concentration leading to structures with different size and morphology. It appears that protein assembly occurs throughout successive steps of aggregated spherical particles that reorganise into biggest isolated microspheres. Direct microscopic observations over time confirm that microspheres resulted from a reorganisation of aggregated, clustered nanospheres. We propose that the formation of apo α-LA/LYS microspheres follows an "aggregation-reorganisation" mechanism.
Published: 2009
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38. Self assembly of anastomosis-like superstructures in fatty acid/guanidine hydrochloride aqueous dispersions

Author: Cédric Gaillard, Bérénice Houinsou-Houssou, Jean-Paul Douliez, Anne-Laure Fameau, Bruno Novales, Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), Institut National de la Recherche Agronomique (INRA), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)
Subjects: Models, Molecular, Magnetic Resonance Spectroscopy, Hydrochloride, Stereochemistry, Sodium, education, FIBRILLE, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, Microscopy, Atomic Force, 01 natural sciences, Myristic Acid, TUBULES, Phase Transition, DIFFERENTIAL SCANNING CALORIMETRY, MICROSCOPIE ELECTRONIQUE A TRANSMISSION, Biomaterials, chemistry.chemical_compound, Colloid and Surface Chemistry, Microscopy, Electron, Transmission, FIBRILS, Phase (matter), SELF ASSEMBLY, Nanotechnology, Guanidine, ANASTOMOSIS, Superstructure, Calorimetry, Differential Scanning, Fatty Acids, Water, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Nanostructures, Crystallography, Membrane, chemistry, Transmission electron microscopy, TEM, Self-assembly, [CHIM.OTHE]Chemical Sciences/Other, 0210 nano-technology, SOLID STATE NMR
Abstract: International audience; A mixture between 1% sodium myristate and guanidine hydrochloride at a molar ratio of 1 in water forms a gel of membranes below a phase transition of ca. 21Â°C and a viscous limpid and isotropic solution above. As observed by both TEM and AFM, we report the formation of interconnected superstructures in that latter phase. Those assemblies exhibit a size of ca. 4-40nm width and several tens of [mu]m length with unexpected disconnections and reconnections between them having the appearance of an anastomosis-like superstructure.
Published: 2009
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39. Self-Assembling Properties of Well-Defined Poly(ethylene oxide)- b -poly(ethyl acrylate) Diblock Copolymers

Author: Cédric Gaillard, Sandie Piogé, Sagrario Pascual, Erwan Nicol, Laurent Fontaine, Institut des Molécules et Matériaux du Mans (IMMM), Le Mans Université (UM)-Centre National de la Recherche Scientifique (CNRS), Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), Institut National de la Recherche Agronomique (INRA), and Le Mans Université (UM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: POLYMERISATION RADICALAIRE CONTROLEE, Materials science, Polymers and Plastics, CRYO-TRANSMISSION ELECTRON MICROSCOPY, Dispersity, COPOLYMERE A BLOCS, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Micelle, AGGEGATION NUMBER, MICROSCOPIE ELECTRONIQUE A TRANSMISSION, Inorganic Chemistry, chemistry.chemical_compound, NOMBRE D'AGREGATION, Dynamic light scattering, SELF ASSEMBLY, Polymer chemistry, Materials Chemistry, Copolymer, Static light scattering, FLUORESCENCE, ComputingMilieux_MISCELLANEOUS, POLYETHYLENE OXYDE, Atom-transfer radical-polymerization, Organic Chemistry, ATOM TRANSFER RADICAL POLYMERIZATION, technology, industry, and agriculture, COPOLYMERE AMPHIPHILE, POLYETHYL ACRYLATE, DIBLOCK COPOLYMER, MICELLE, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, TRANSMISSION ELECTRON MICROSCOPY, 0104 chemical sciences, [CHIM.POLY]Chemical Sciences/Polymers, Chemical engineering, chemistry, Polymerization, STATIC LIGHT SCATTERING, Ethyl acrylate, 0210 nano-technology, DYNAMIC LIGHT SCATTERING
Abstract: International audience; Poly(ethylene oxide)-b-poly(ethyl acrylate) amphiphilic diblock copolymers were synthesized by atom transfer radical polymerization (ATRP). The controlled character of the polymerization was confirmed by kinetic studies, evolution of number-average molecular weight and polydispersity index with conversion: Various block copolymers with different PEA/PEO molar ratio were synthesized and their self-assembling properties in aqueous medium were studied by fluorescence measurements, static light scattering (SLS), and dynamic light scattering (DLS). The critical micelle concentrations (CMC) were determined by pyrene fluorescence analysis. The CMC was shown to decrease as the hydrophobic (PEA) block length increases. SLS and DLS allowed the determination of the aggregation numbers (N-agg) and hydrodynamic radii (R-h) of the core-shell micelles formed in water. Both N-agg and R-h exhibit a monotonic increase as a function of the PEA block length. TEM and cryo-TEM micrographs of the ! micelles showed spherical objects with a low polydispersity of sizes. The micelles formed in water are in a thermodynamic equilibrium and the aggregation number of the micelles was shown to vary with the temperature.
Published: 2009
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40. Synthesising gold nanoparticles within bola fatty acid nanosomes

Author: Cédric Gaillard, Bruno Novales, Jean-Paul Douliez, Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), and Institut National de la Recherche Agronomique (INRA)
Subjects: Carboxylic acid, Palmitic Acid, Metal Nanoparticles, Nanoparticle, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, MICROSCOPIE ELECTRONIQUE A TRANSMISSION, Biomaterials, Palmitic acid, chemistry.chemical_compound, Colloid and Surface Chemistry, Microscopy, Electron, Transmission, SELF ASSEMBLY, Organic chemistry, Dichloromethane, chemistry.chemical_classification, AGENT DE SURFACAGE, NANOSOMES, Fatty acid, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, chemistry, Colloidal gold, Saturated fatty acid, Emulsion, GOLD NANOPARTICLES, FATTY ACID, Spectrophotometry, Ultraviolet, Gold, 0210 nano-technology, [CHIM.OTHE]Chemical Sciences/Other, Nuclear chemistry
Abstract: International audience; We report on the synthesis of gold nanoparticles (AuNP) stabilized by a layer of mercapto and/or hydroxyl bola palmitic acid-tetrabutyl ammonium salts (TBAOH) which form nanosomes in water. Mixing both bola fatty acids in water in various proportions allowed to tune the nanoparticle diameter from 1 to 10 nm using NaBH4 as a reductor. Those nanoparticles could be phase transferred to dichloromethane by adding a more hydrophobic counter-ion than TBAOH, its derivative with octyl chains (TOAOH). Finally, we used those AuNP to formulate emulsions, the stability of which was followed as a function of particle size and time. The emulsions were stable but creamed after several hours. We conclude that bola fatty acid nanosomes are then good candidates to synthesize gold nanoparticles dispersed either in water, organic solvents and emulsions.
Published: 2009
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41. Relation between Chemical Structure and Supramolecular Organization of Synthetic Lignin-Pectin Particles

Author: Bernard Cathala, Marie-Christine Ralet, Cédric Gaillard, Anouck Habrant, Dider Lairez, Fractionnement des AgroRessources et Environnement (FARE), Université de Reims Champagne-Ardenne (URCA)-Institut National de la Recherche Agronomique (INRA), Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), Institut National de la Recherche Agronomique (INRA), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)
Subjects: 0106 biological sciences, Citrus, food.ingredient, Polymers and Plastics, Pectin, Chemical structure, [SDV]Life Sciences [q-bio], Supramolecular chemistry, DHP, Nanoparticle, Bioengineering, 02 engineering and technology, PLANT CELL WALL, 01 natural sciences, Lignin, Biomaterials, chemistry.chemical_compound, LIGNIN-DHP COMPLEX, food, PECTIN, LIGNIFICATION, [SDV.IDA]Life Sciences [q-bio]/Food engineering, Materials Chemistry, Organic chemistry, Molecule, [SPI.GPROC]Engineering Sciences [physics]/Chemical and Process Engineering, Phenols, Particle Size, STRUCTURE SUPRAMOLECULAIRE, ComputingMilieux_MISCELLANEOUS, Molecular Structure, COMPLEXE LIGNINE POLYOSIDE, 021001 nanoscience & nanotechnology, ELECTRON MICROSCOPY, chemistry, [SDE]Environmental Sciences, Pectins, SUPRAMOLECULAR ORGANIZATION, Particle size, LIGHT SCATTERING, 0210 nano-technology, 010606 plant biology & botany
Abstract: International audience
Published: 2009
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42. A Simple Protocol to Stabilize Gold Nanoparticles using Amphiphilic Block Copolymers: Stability Studies and Viable Cellular Uptake

Author: Cédric Ayela, Cédric Gaillard, Kamil Rahme, Fabienne Gauffre, Bruno Payré, Christophe Mingotaud, Patricia Vicendo, 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 d'analyse et d'architecture des systèmes (LAAS), Université Toulouse - Jean Jaurès (UT2J)-Université Toulouse 1 Capitole (UT1), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées, Laboratoire de l'intégration, du matériau au système (IMS), Université Sciences et Technologies - Bordeaux 1-Institut Polytechnique de Bordeaux-Centre National de la Recherche Scientifique (CNRS), Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), Institut National de la Recherche Agronomique (INRA), Centre de Microscopie Électronique Appliquée à la Biologie (CMEAB), Hôpital de Rangueil, CHU Toulouse [Toulouse]-CHU Toulouse [Toulouse]-Toulouse Réseau Imagerie-Genotoul ( TRI-Genotoul), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), 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), Université Toulouse Capitole (UT Capitole), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université Toulouse - Jean Jaurès (UT2J), Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT), Université Sciences et Technologies - Bordeaux 1 (UB)-Institut Polytechnique de Bordeaux-Centre National de la Recherche Scientifique (CNRS), Toulouse Réseau Imagerie-Genotoul ( TRI-Genotoul), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse 1 Capitole (UT1)-Université Toulouse - Jean Jaurès (UT2J), CHU Toulouse [Toulouse]-CHU Toulouse [Toulouse]-Université Toulouse III - Paul Sabatier (UT3), and Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées
Subjects: Nanoparticle, Metal Nanoparticles, Nanotechnology, 02 engineering and technology, CHO Cells, 010402 general chemistry, 01 natural sciences, Micelle, Catalysis, STABILITE, MICROSCOPIE ELECTRONIQUE A TRANSMISSION, Cricetulus, Microscopy, Electron, Transmission, Cricetinae, Amphiphile, Copolymer, NANOPARTICLES, Animals, CYTOTOXICITY, GOLD, AMPHIPHILES, ComputingMilieux_MISCELLANEOUS, Micelles, COPOLYMERE EN BLOC, chemistry.chemical_classification, Organic Chemistry, NANOTECHNOLOGY, General Chemistry, Polymer, Quartz crystal microbalance, 021001 nanoscience & nanotechnology, 0104 chemical sciences, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Chemical engineering, Ionic strength, Colloidal gold, POLYMERE AMPHIPHILE, POLYMERS, 0210 nano-technology
Abstract: International audience; Di- and triblock non-ionic copolymers based on poly(ethylene oxide) and poly(propylene oxide) were studied for the stabilization of nanoparticles in water at high ionic strength. The effect of the molecular architecture (di- vs. triblock) of these amphiphilic copolymers was investigated by using gold nanoparticles (AuNPs) as probes for colloidal stability. The results demonstrate that both di- and triblock copolymers can provide long term stability, and that in both cases AuNPs are individually embedded within globules of polymers. However, in the case of diblock copolymers, the colloidal stability was related to the formation of micelles, in contrast with the case of triblock copolymers, which were previously shown to provide good stability even at concentrations at which micelles do not form. Quartz crystal microbalance (QCM) experiments showed that the presence of the hydrophobic block in the structure of the polymer is important to ensure quantitative adsorption upon a g! old surface and to limit desorption. We demonstrate that with an appropriate choice of polymer, the polymer/AuNP hybrids can also undergo filtration and freeze-drying without noticeable aggregation, which can be very convenient for further applications. Finally, preliminary studies of the cytotoxicity effect on fibroblast cells show that the polymer/AuNP hybrids were not cytotoxic. TEM micrographs on ultrathin sections of cells after incubation with the colloidal solutions show that the nanoparticles were internalized into the cells, conserving their initial size and shape.
Published: 2009
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43. Ultrastructure of Ulvan: A Polysaccharide from Green Seaweeds

Author: Jean-François Sassi, Cédric Gaillard, Audrey Robic, Yannick Lerat, Marc Lahaye, Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), Institut National de la Recherche Agronomique (INRA), and Centre d'Etude et de Valorisation des Algues (CEVA)
Subjects: Morphology (linguistics), Macromolecular Substances, BIOPOLYMERS, Intrinsic viscosity, Sodium, Chemical structure, Biophysics, chemistry.chemical_element, 02 engineering and technology, Polysaccharide, Biochemistry, MICROSCOPIE ELECTRONIQUE A TRANSMISSION, Biomaterials, Boric acid, 03 medical and health sciences, chemistry.chemical_compound, Ulva, Microscopy, Electron, Transmission, Polysaccharides, [SDV.IDA]Life Sciences [q-bio]/Food engineering, Organic chemistry, Ammonium, [SPI.GPROC]Engineering Sciences [physics]/Chemical and Process Engineering, 030304 developmental biology, chemistry.chemical_classification, 0303 health sciences, Aqueous solution, Molecular Structure, Chemistry, Organic Chemistry, ATOMIC FORCE MICROSCOPY, General Medicine, Hydrogen-Ion Concentration, 021001 nanoscience & nanotechnology, ELECTRON MICROSCOPY, SOLUTIONS PROPERTIES, POLYSACCHARIDE, Chemical engineering, NANOHETEROGENEITY, 0210 nano-technology, Gels
Abstract: Ultrastructural analysis of the gel forming green seaweed sulfated polysaccharide ulvan revealed a spherical-based morphology (10-18 nm diameter) more or less aggregated in aqueous solution. At pH 13 in TBAOH (tetrabutyl ammonium hydroxyde) or NaOH, ulvan formed an open gel-like structure or a continuous film by fusion or coalescence of bead-like structures, while in acidic pH conditions, ulvan appeared as dispersed beads. Low concentrations of sodium chloride, copper or boric acid induced the formation of aggregates. These results highlight the hydrophobic and aggregative behavior of ulvan that are discussed in regard to the peculiar gel formation and the low intrinsic viscosity of the polysaccharide in aqueous solution. (c) 2009 Wiley Periodicals, Inc. Biopolymers 91: 652-664, 2009.This article was originally published online as an accepted preprint. The "Published Online" date corresponds to the preprint version. You can request a copy of the preprint by emailing the Biopolymers editorial office at biopolymers@wiley.com.
Published: 2009
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44. Simultaneous ROMP and ATRP in Aqueous Dispersed Media: a Straightforward Strategy to Prepare Polymer Composite Particles with Original Morphologies

Author: Cédric Airaud, Emmanuel Ibarboure, Valérie Héroguez, Cédric Gaillard, Laboratoire de Chimie des Polymères Organiques (LCPO), Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Centre National de la Recherche Scientifique (CNRS), TEAM 1 LCPO, Université de Bordeaux (UB)-Institut Polytechnique de Bordeaux-Centre National de la Recherche Scientifique (CNRS), INRA-Unité BIA Plateforme BIBS-Microscopie, Institut National de la Recherche Agronomique (INRA), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Team 1 LCPO : Polymerization Catalyses & Engineering, and Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)
Subjects: Materials science, Polymers and Plastics, Radical polymerization, 02 engineering and technology, atom-transfer radical polymerization (ATRP), 010402 general chemistry, 01 natural sciences, Living free-radical polymerization, Chain-growth polymerization, microemulsion polymerization, polymer composite particles, Polymer chemistry, Materials Chemistry, Reversible addition−fragmentation chain-transfer polymerization, Organic Chemistry, Chain transfer, 021001 nanoscience & nanotechnology, Condensed Matter Physics, ring-opening metathesis polymerization (ROMP), 0104 chemical sciences, End-group, [CHIM.POLY]Chemical Sciences/Polymers, Chemical engineering, Polymerization, miniemulsion polymerization, Precipitation polymerization, 0210 nano-technology
Abstract: International audience; The simultaneous combination of the ring-opening metathesis polymerization of norbornene and the atom-transfer radical polymerization of methyl methacrylate is used as a convenient tool to prepare polymer composite particles in a single step and using only one catalyst. The current article reviews the use of miniemulsion and microemulsion conditions to reach this aim. The two developed approaches are assessed on chemical and colloidal levels and the prepared composite particles are scrutinized from a morphological point of view.
Published: 2009

45. Pluronics-stabilized gold nanoparticles: investigation of the structure of the polymer-particle hybrid

Author: Kamil Rahme, Cédric Gaillard, Christophe Mingotaud, Julian Oberdisse, Ralf Schweins, Fabienne Gauffre, and Jean-Daniel Marty
Subjects: Materials science, Light, Polymers, Surface Properties, Nanoparticle, Metal Nanoparticles, Nanotechnology, 02 engineering and technology, Poloxamer, 010402 general chemistry, 01 natural sciences, Micelle, Dynamic light scattering, Scattering, Radiation, Physical and Theoretical Chemistry, Particle Size, Micelles, Temperature, Reproducibility of Results, 021001 nanoscience & nanotechnology, Small-angle neutron scattering, Atomic and Molecular Physics, and Optics, 0104 chemical sciences, Molecular Weight, Solutions, Chemical engineering, Colloidal gold, Particle, Particle size, Gold, 0210 nano-technology, Hydrophobic and Hydrophilic Interactions
Abstract: Hybrid gold-polymer nanoparticles are obtained by self-assembly of amphiphilic copolymers (Pluronics) in solutions containing preformed gold nanoparticles (diameter ca. 12 nm). Dynamic light scattering, TEM, cryo-TEM, and small-angle neutron scattering experiments with contrast variation are used to characterize the structure of the gold-polymer particles. Five Pluronics (F127, F68, F88, F108, P84) with different molecular weights and hydrophilic/hydrophobic balances are investigated. Gold nanoparticles are individually embedded within globules of polymer, even under conditions for which Pluronics micelles do not form in solution. The hybrid particles are several tens of nanometers in size (larger than micelles of the corresponding Pluronics), and the size can be tuned by changing the temperature.
Published: 2008

46. Multiblock copolymer behaviour of alpha-CD/PEO-based polyrotaxanes: towards nano-cylinder self-organization of alpha-CDs

Author: Alain Lapp, Dimitri A. Ivanov, Cédric Gaillard, Cyril Brochon, Pascal Hébraud, Denis V. Anokhin, Georges Hadziioannou, Christophe Travelet, Guy Schlatter, Laboratoire d'Ingenierie des Polymères pour les Hautes Technologies, Centre National de la Recherche Scientifique (CNRS)-Université Louis Pasteur - Strasbourg I, Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université Louis Pasteur - Strasbourg I-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Physico-Chimie des Polymères et des Milieux Dispersés (PPMD), Université Pierre et Marie Curie - Paris 6 (UPMC)-ESPCI ParisTech-Centre National de la Recherche Scientifique (CNRS), 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, Unité de recherche biopolymeres interactions assemblages (BIA), Institut National de la Recherche Agronomique (INRA), Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-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), Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), 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)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)
Subjects: Materials science, INCLUSION COMPLEXES, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, chemistry.chemical_compound, Polymer chemistry, Nano, Cylinder, SCATTERING, chemistry.chemical_classification, Cyclodextrin, Ethylene oxide, Hydrogen bond, Dimethyl sulfoxide, General Chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, CYCLODEXTRIN, 0104 chemical sciences, Solvent, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Chemical engineering, Crystallite, 0210 nano-technology
Abstract: International audience; The present work demonstrates that alpha-cyclodextrin/poly(ethylene oxide) (alpha-CD/PEO)-based polyrotaxanes (PRs) behave as multiblock copolymers. One block type consists of a rod-like tube made of 6 to 7 weakly stacked alpha-CDs threaded along the PEO chain. The other one is made of a naked PEO segment, i.e. the PR part that is not covered by alpha-CDs. This multiblock behaviour induces the self-organization of PRs in concentrated solution in dimethyl sulfoxide ( DMSO) at room temperature leading to the formation of nano-cylinders. These nano-cylinders consist of assemblies of roughly 60 alpha-CD rod-like tubes through hydrogen bonding. Moreover, crystallites of naked PEO segments are formed since PEO is in poor solvent conditions ( DMSO) at room temperature. Furthermore, the formation of alpha-CD nano-cylinders as well as of naked PEO segment crystallites leads to physical gelation of PRs in DMSO.
Published: 2008
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47. Supramolecular organization of heteroxylan-dehydrogenation polymers (synthetic lignin) nanoparticles

Author: Brigitte Chabbert, Abdellatif Barakat, Bernard Cathala, Cédric Gaillard, Luc Saulnier, Didier Lairez, Fractionnement des AgroRessources et Environnement (FARE), Université de Reims Champagne-Ardenne (URCA)-Institut National de la Recherche Agronomique (INRA), Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), Institut National de la Recherche Agronomique (INRA), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)
Subjects: Polymers and Plastics, Polymers, [SDV]Life Sciences [q-bio], NANOPARTICLE, Supramolecular chemistry, Nanoparticle, Bioengineering, 02 engineering and technology, 010402 general chemistry, Microscopy, Atomic Force, 01 natural sciences, Lignin, Light scattering, Biomaterials, chemistry.chemical_compound, SYNTHETIC LIGNIN, Indentation, Polymer chemistry, [SDV.IDA]Life Sciences [q-bio]/Food engineering, Materials Chemistry, Dehydrogenation, [SPI.GPROC]Engineering Sciences [physics]/Chemical and Process Engineering, chemistry.chemical_classification, Chemistry, technology, industry, and agriculture, ATOMIC FORCE MICROSCOPY, Polymer, 021001 nanoscience & nanotechnology, Fluorescence, HETEROXYLAN, 0104 chemical sciences, Chemical engineering, [SDE]Environmental Sciences, Pyrene, Nanoparticles, SUPRAMOLECULAR ORGANIZATION, Xylans, LIGHT SCATTERING, FLUORESCENT PROBE, Hydrogenation, 0210 nano-technology
Abstract: International audience; The supramolecular organization of particles composed of heteroxylans (HX) and synthetic lignin (dehydrogenation polymer, DHPs) was studied by light scattering (LS), atomic force microscopy (AFM), and fluorescent probes. Results from static and quasi-elastic light scattering indicate a dense core surrounded by a soft corona. Such organization is also supported by AFM images of the particles that display Gaussian height profiles when a low tapping force is applied, whereas the shape of the profile obtained at a higher mechanical solicitation is irregular and sharp due to deformation of the particles resulting from the tip indentation. This suggests a difference in mechanical behavior between the inner and outer parts of the particles. The formation of local chemical heterogeneities was demonstrated by use of two fluorescent polarity probes (pyrene and methyl-amino-pyrene) to be induced by the core−corona organization.
Published: 2008
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48. Convenient synthesis and properties of polypropyleneimine dendrimer-functionalized polymer nanoparticles

Author: Paresh Sanghvi, Caroline Cannizzo, Anne Delgado, Chantal Larpent, Fabrice Gouanvé, Cédric Gaillard, Gérard Bacquet, Université de Versailles Saint-Quentin-en-Yvelines (UVSQ), Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), Institut National de la Recherche Agronomique (INRA), and Rhodia S.A.
Subjects: Materials science, Nanoparticle, 02 engineering and technology, DENDRIMERE, 010402 general chemistry, Microscopy, Atomic Force, Polypropylenes, 01 natural sciences, Nanomaterials, MICROSCOPIE ELECTRONIQUE A TRANSMISSION, Biomaterials, chemistry.chemical_compound, Microscopy, Electron, Transmission, Dendrimer, [SDV.IDA]Life Sciences [q-bio]/Food engineering, NANOPARTICLES, Organic chemistry, General Materials Science, DENDRIMERS, [SPI.GPROC]Engineering Sciences [physics]/Chemical and Process Engineering, NANO-BUILDING BLOCKS, SYNTHESE, chemistry.chemical_classification, Spectroscopy, Near-Infrared, Cationic polymerization, DIFFUSION QUASIELASTIQUE DE LA LUMIERE, General Chemistry, Polymer, 021001 nanoscience & nanotechnology, 0104 chemical sciences, SYNTHETIC METHODS, Azobenzene, chemistry, Polymerization, Chemical engineering, Spectrophotometry, Ultraviolet, Polystyrene, POLYMERS, 0210 nano-technology, Biotechnology
Abstract: International audience; A simple synthesis of polymer core-dendrimer shell nanoparticles (NPs) in the 15-20-nm-diameter range is presented. Amine-terminated polypropyleneimine (PPI) dendrimers DAB-dendri-(NH2)(4) and DAB-dendri-(NH2)(16) (DAB4 and DAB16) are covalently attached to the surface of primary polystyrene-based NPs bearing reactive chlorobenzyl groups produced by microemulsion polymerization in the presence of a cationic surfactant. The grafting readily proceeds under mild conditions and leads to translucent aqueous suspensions of core-shell-type NPs with a high density of peripheral amine groups that have been characterized relative to their size and chemical composition. The dendritic shell acts as a protective ionizable outer layer and provides an improvement of the colloidal stability in neutral and acidic media. The metal-binding capacity of the PPI dendrimers is retained, and spectrophotometric titrations show that the dendrimer-grafted NPs can trap a large number of Cu2+ ions (more than 900 Cu per NP-DAB16). These properties make them potentially valuable templates for the elaboration of hybrid nanomaterials. The reactivity of the external amine groups is used to link covalently azobenzene chromophores (disperse Red 1 residues) through aza-Michael addition in aqueous suspension. This simple method gives access to colored NPs with high dye contents in the outer layer (up to 1000-1500 dye molecules per NP), which indicates that dendrimer-functionalized NPs are valuable building blocks for the construction of multifunctional nanomaterials.
Published: 2008
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49. Assessment of in vitro binding of isolated pectic domains to cellulose by adsorption isotherms, electron microscopy, and X-ray diffraction methods

Author: Catherine Garnier, Jean-François Thibault, Agata Zykwinska, Bruno Pontoire, Cédric Gaillard, Alain Buléon, Marie-Christine Ralet, Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), and Institut National de la Recherche Agronomique (INRA)
Subjects: 0106 biological sciences, Morphology (linguistics), POLYSACCHARIDES PARIETAUX, Polymers and Plastics, Bioengineering, 02 engineering and technology, IN VITRO BINDING, 01 natural sciences, law.invention, Biomaterials, Cell wall, Diffusion, chemistry.chemical_compound, Adsorption, Microscopy, Electron, Transmission, X-Ray Diffraction, law, Cell Wall, Polysaccharides, Polymer chemistry, [SDV.IDA]Life Sciences [q-bio]/Food engineering, Materials Chemistry, Side chain, Scattering, Radiation, [SPI.GPROC]Engineering Sciences [physics]/Chemical and Process Engineering, Cellulose, Glucans, X-Rays, Hydrogen Bonding, 021001 nanoscience & nanotechnology, Xyloglucan, Microscopy, Electron, chemistry, DIFFRACTION DES RAYONS X, CELLULOSE, Pectins, Microfibril, Electron microscope, 0210 nano-technology, PECTIC DOMAIN, 010606 plant biology & botany, Hydrogen
Abstract: International audience; Isolated pectic domains representative of the pectic backbone and the neutral sugar side chains were tested for their ability to interact with cellulose in comparison to the well-known binding of xyloglucan. Pectic side chains displayed a significant in vitro binding capacity to cellulose, whereas pectic backbone domains exhibited only slight adsorption to cellulose microfibrils. To support the binding results, electron microscopy and X-ray diffraction were applied. Celluloses from bacteria and sugar beet cell walls were used as substrates for the precipitation of isolated pectic domains or xyloglucan by acetone vapor diffusion. Pectic side chains grew attached to the cellulose surfaces, whereas pectic backbone domains were observed separately from cellulose microfibrils. Xyloglucan seeded with cellulose provoked a decrease of microfibrils entanglement, but no clear cross-links between neighboring microfibrils were observed. These results led to the elucidation of the pectic! domains responsible for binding with cellulose microfibrils.
Published: 2007
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50. Novel Lipid System Forming Hollow Microtubes at High Yields and Concentration

Author: Frédéric Nallet, Jean-Paul Douliez, Laurence Navailles, Cédric Gaillard, Unité de recherche biopolymeres interactions assemblages (BIA), Institut National de la Recherche Agronomique (INRA), Centre de recherches Paul Pascal (CRPP), Centre National de la Recherche Scientifique (CNRS), Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), and Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Supramolecular chemistry, Salt (chemistry), 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Chemical synthesis, chemistry.chemical_compound, Ethanolamine, hollow microtubes, Electrochemistry, Organic chemistry, General Materials Science, Tube (fluid conveyance), Spectroscopy, chemistry.chemical_classification, Chemistry, Bilayer, Surfaces and Interfaces, lipid systems, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Chemical engineering, Self-assembly, 0210 nano-technology, Layer (electronics), [PHYS.COND.CM-SCM]Physics [physics]/Condensed Matter [cond-mat]/Soft Condensed Matter [cond-mat.soft]
Abstract: There is considerable interest in constructing supramolecular hollow tube architectures based on amphiphilic molecules. This can be achieved by using relatively expensive synthetic lipids. Herein, we report on the facile preparation of self-assembled microtubes from a novel low-cost lipid mixture that does not require a previous chemical synthesis step and consists of the ethanolamine salt of 12-hydroxy-stearic acid in water. Tubes of more than 10 microm in length spontaneously form upon cooling from an isotropic solution. They exhibit inner and outer diameters of 400 and 600 nm, respectively, and their walls consist of concentric stacked bilayers of fatty acid salts, each separated by a layer of water.
Published: 2006
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