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51. Enhancing Properties of Anionic Poly(ionic liquid)s with 1,2,3-Triazolium Counter Cations

Author: Bhanu P. Mudraboyina, Anatoli Serghei, Eric Drockenmuller, Didier Gigmes, Trang N. T. Phan, and Mona M. Obadia
Subjects: Inorganic Chemistry, chemistry.chemical_compound, Polymers and Plastics, chemistry, Organic Chemistry, Ionic liquid, Inorganic chemistry, Materials Chemistry, Polystyrene, Electrolyte
Abstract: A series of anionic poly(ionic liquid)s with 1,2,3-triazolium counter cations are prepared by cation exchange between tailormade 1,3,4-trialkylated-1,2,3-triazolium iodides and a polystyrene derivative having pendant potassium bis(trifluoromethylsulfonyl)imide groups. The physical and ion-conducting properties of the resulting materials are compared to the parent potassium-containing polyelectrolyte based on
Published: 2022

52. Novel Copper Complexes as Visible Light Photoinitiators for the Synthesis of Interpenetrating Polymer Networks (IPNs)

Author: Mahmoud Rahal, Guillaume Noirbent, Bernadette Graff, Joumana Toufaily, Tayssir Hamieh, Didier Gigmes, Frédéric Dumur, Jacques Lalevée, Institut de Science des Matériaux de Mulhouse (IS2M), Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-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)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Lebanese University [Beirut] (LU), Laboratoire de Matériaux, Catalyse, Environnement et Méthodes Analytiques (MCEMA), MCEMA, and Dumur, Frederic
Subjects: [CHIM.MATE] Chemical Sciences/Material chemistry, CATALYST, CLAISEN-SCHMIDT CONDENSATION, Polymers and Plastics, LED, REDOX PROPERTIES, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, free radical photopolymerization, METAL NANOPARTICLES, TRANSFER RADICAL-ADDITION, EXCITED-STATE DYNAMICS, copper complex, photocomposite, laser write, ADHESIVES, LIGANDS, CHALCONES, PHOTOPOLYMERIZATION
Abstract: International audience; This work is devoted to the study of two copper complexes (Cu) bearing pyridine ligands, which were synthesized, evaluated and tested as new visible light photoinitiators for the free radical photopolymerization (FRP) of acrylates functional groups in thick and thin samples upon light-emitting diodes (LED) at 405 and 455 nm irradiation. These latter wavelengths are considered to be safe to produce polymer materials. The photoinitiation abilities of these organometallic compounds were evaluated in combination with an iodonium (Iod) salt and/or amine (e.g., N-phenylglycine—NPG). Interestingly, high final conversions and high polymerization rates were obtained for both compounds using two and three-component photoinitiating systems (Cu1 (or Cu2)/Iodonium salt (Iod) (0.1%/1% w/w) and Cu1 (or Cu2)/Iod/amine (0.1%/1%/1% w/w/w)). The new proposed copper complexes were also used for direct laser write experiments involving a laser diode at 405 nm, and for the photocomposite synthesis with glass fibers using a UV-conveyor at 395 nm. To explain the obtained polymerization results, different methods and characterization techniques were used: steady-state photolysis, real-time Fourier transform infrared spectroscopy (RT-FTIR), emission spectroscopy and cyclic voltammetry.
Published: 2022
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53. Plasmon-triggered living photopolymerization for elaboration of hybrid polymer/metal nanoparticles

Author: Jacques Lalevée, Olivier Soppera, Renaud Bachelot, Siham Telitel, Céline Fiorini-Debuisschert, Didier Gigmes, Loïc Vidal, Farid Kameche, Dandan Ge, Frédéric Dumur, Sylvie Marguet, Ludovic Douillard, Wajdi Heni, Institut de Science des Matériaux de Mulhouse (IS2M), Centre National de la Recherche Scientifique (CNRS)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Lumière, nanomatériaux et nanotechnologies (L2n), Institut Charles Delaunay (ICD), Université de Technologie de Troyes (UTT)-Centre National de la Recherche Scientifique (CNRS)-Université de Technologie de Troyes (UTT)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Edifices Nanométriques (LEDNA), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Laboratoire d'Electronique et nanoPhotonique Organique (LEPO), Service de physique de l'état condensé (SPEC - UMR3680), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay, Sino-European School of Technology, University of Shanghai [Shanghai], ANR-11-BS08-0016,IMPACT,Photopolymérisation contrôlée par les nitroxydes: Un outil idéal pour la préparation de micropatterns réactivables(2011), ANR-12-BS10-0016,HAPPLE,Nanoemetteurs plasmoniques hybrides anisotropes(2012), ANR-13-NANO-0002,SAMIRé,Sondes Actives pour la MIcroscopie optique en champ proche à très haute Résolution(2013), Palacin, Serge, BLANC - Photopolymérisation contrôlée par les nitroxydes: Un outil idéal pour la préparation de micropatterns réactivables - - IMPACT2011 - ANR-11-BS08-0016 - BLANC - VALID, BLANC - Nanoemetteurs plasmoniques hybrides anisotropes - - HAPPLE2012 - ANR-12-BS10-0016 - BLANC - VALID, Nanotechnologies et nanosystèmes - Sondes Actives pour la MIcroscopie optique en champ proche à très haute Résolution - - SAMIRé2013 - ANR-13-NANO-0002 - P2N - VALID, Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-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)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), 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, [CHIM.MATE] Chemical Sciences/Material chemistry, Materials science, Nanostructure, Atom-transfer radical-polymerization, Mechanical Engineering, Nanotechnology, [CHIM.MATE]Chemical Sciences/Material chemistry, 02 engineering and technology, Polymer, 010402 general chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 01 natural sciences, 0104 chemical sciences, Photopolymer, Polymerization, chemistry, Mechanics of Materials, Surface modification, General Materials Science, Surface plasmon resonance, 0210 nano-technology, Plasmon
Abstract: International audience; Surface plasmon resonance can be used to manipulate light at the nanoscale. It was used here to trigger photopolymerization of an atom transfer radical polymerization (ATRP) molecular system, leading to a thin polymer shell at the surface of the metal nanostructure. The polymerization can be reactivated from the first polymer shell to covalently graft a second monomer layer with precise control over the thickness at the nanometric scale, depending on the photonic parameters. This route can be applied to different nanoobjects and allows an anisotropic surface modification in agreement with the spatial localization of the enhanced electromagnetic field near the nanostructure. This new route opens the door towards the preparation of multifunctional hybrid metal/polymer nanostructures.
Published: 2020
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54. Laser Direct Writing of Arbitrary Complex Polymer Microstructures by Nitroxide-Mediated Photopolymerization

Author: Jean-Pierre Malval, Fabrice Morlet-Savary, Yohann Guillaneuf, Jacques Lalevée, Jason C. Morris, Jean-Louis Clément, Olivier Soppera, Arnaud Spangenberg, Siham Telitel, Didier Gigmes, Institut de Science des Matériaux de Mulhouse (IS2M), Centre National de la Recherche Scientifique (CNRS)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-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)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), ANR-16-CE08-0020,2PhotonInsight,Compréhension de la polymérisation biphotonique utilisée en écriture laser directe via la combinaison de différentes méthodes d'analyse résolues temporellement et spatialement(2016), and Soppera, Olivier
Subjects: Nitroxide mediated radical polymerization, Fabrication, Nanostructure, Materials science, Nanotechnology, 02 engineering and technology, nitroxide-mediated photopolymerization, 010402 general chemistry, 01 natural sciences, General Materials Science, reversible deactivation radical polymerization, surface functionalization, chemistry.chemical_classification, Reversible-deactivation radical polymerization, [CHIM.MATE] Chemical Sciences/Material chemistry, repolymerization, [CHIM.MATE]Chemical Sciences/Material chemistry, Polymer, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Photopolymer, Polymerization, chemistry, Laser direct writing, Proof of concept, polymer micropatterning, 0210 nano-technology, alkoxyamine, oxygen
Abstract: International audience; In this paper, we demonstrate the possibility of generating arbitrary polymer microstructures covalently linked to a first polymer layer by laser direct writing. At the molecular scale, the process relies on nitroxide-mediated photopolymerization (NMP2) triggered by a light-sensitive alkoxyamine. In addition to the proof-of-concept and examples of achievable structures, including multichemistry patterns and 3D structures, this paper aims at investigating the physicochemical phenomena involved under such conditions. In particular, the parameters influencing the repolymerization process are considered, and special attention is paid to the study of the impact of oxygen on the spatial control of the polymerization. Such work opens many possibilities towards the fabrication of on-demand high-resolution (multi)functional polymer micro-and nanostructures.
Published: 2020
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55. Delayed Injection of a Physically Cross-Linked PNIPAAm-g-PEG Hydrogel in Rat Contused Spinal Cord Improves Functional Recovery

Author: Tanguy Marqueste, Thomas Trimaille, Patrick Decherchi, Didier Gigmes, Maxime Bonnet, Olivier Alluin, Institut des Sciences du Mouvement Etienne Jules Marey (ISM), Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU), and Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)
Subjects: General Chemical Engineering, [SDV]Life Sciences [q-bio], Article, Lesion, 03 medical and health sciences, 0302 clinical medicine, Text mining, medicine, Spinal cord injury, QD1-999, ComputingMilieux_MISCELLANEOUS, 030304 developmental biology, PEG Hydrogel, 0303 health sciences, business.industry, General Chemistry, Functional recovery, medicine.disease, Spinal cord, 3. Good health, Chemistry, medicine.anatomical_structure, Anesthesia, medicine.symptom, business, 030217 neurology & neurosurgery
Abstract: Spinal cord injury is a main health issue, leading to multiple functional deficits with major consequences such as motor and sensitive impairment below the lesion. To date, all repair strategies remain ineffective. In line with the experiments showing that implanted hydrogels, immunologically inert biomaterials, from natural or synthetic origins, are promising tools and in order to reduce functional deficits, to increase locomotor recovery, and to reduce spasticity, we injected into the lesion area, 1 week after a severe T10 spinal cord contusion, a thermoresponsive physically cross-linked poly(N-isopropylacrylamide)-poly(ethylene glycol) copolymer hydrogel. The effect of postinjury intensive rehabilitation training was also studied. A group of male Sprague–Dawley rats receiving the hydrogel was enrolled in an 8 week program of physical activity (15 min/day, 5 days/week) in order to verify if the combination of a treadmill step-training and hydrogel could lead to better outcomes. The data obtained were compared to those obtained in animals with a spinal lesion alone receiving a saline injection with or without performing the same program of physical activity. Furthermore, in order to verify the biocompatibility of our designed biomaterial, an inflammatory reaction (interleukin-1β, interleukin-6, and tumor necrosis factor-α) was examined 15 days post-hydrogel injection. Functional recovery (postural and locomotor activities and sensorimotor coordination) was assessed from the day of injection, once a week, for 9 weeks. Finally, 9 weeks postinjection, the spinal reflexivity (rate-dependent depression of the H-reflex) was measured. The results indicate that the hydrogel did not induce an additional inflammation. Furthermore, we observed the same significant locomotor improvements in hydrogel-injected animals as in trained saline-injected animals. However, the combination of hydrogel with exercise did not show higher recovery compared to that evaluated by the two strategies independently. Finally, the H-reflex depression recovery was found to be induced by the hydrogel and, albeit to a lesser degree, exercise. However, no recovery was observed when the two strategies were combined. Our results highlight the effectiveness of our copolymer and its high therapeutic potential to preserve/repair the spinal cord after lesion.
Published: 2020
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56. Mesolytic Versus Homolytic Cleavage in Photochemical Nitroxide-Mediated Polymerization

Author: Didier Gigmes, Jason C. Morris, Yohann Guillaneuf, Jean-Louis Clément, Melinda J. Fule, Nicholas S. Hill, Michelle L. Coote, Australian National University (ANU), Institut de Chimie Radicalaire (ICR), and Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Nitroxide mediated radical polymerization, Polymers and Plastics, Chemistry, Radical, Organic Chemistry, Radical polymerization, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Photochemistry, 01 natural sciences, 0104 chemical sciences, Homolysis, Inorganic Chemistry, Photopolymer, Radical ion, Polymerization, Materials Chemistry, [CHIM]Chemical Sciences, 0210 nano-technology, Bond cleavage
Abstract: International audience; Time-dependent density functional theory calculations have been performed to study the photocleavage reactions of chromophore-functionalized alkoxyamines in nitroxide-mediated photo-polymerization. Two case studies were considered: azaphenalene derivatives and benzophenone-based alkoxyamines. For the azaphenalenes, we show that the expected homolysis pathway is actually inaccessible. Instead, these alkoxyamines exhibit low-lying excited states that exhibit an electronic structure about the nitroxide moiety similar to that of the formally oxidized radical cation. As a result, the cleavage of these alkoxyamines can be described as mesolytic-like, rather than homolytic. As with formally oxidized species, mesolytic cleavage can result in the production of either carbon-centered radicals or carbocations, with only the former resulting in radical polymerization. Here, the cleavage products are found to be dependent on the respective radical/cation stabilities of the monomer units of choice (styrene, ethyl propanoate, and ethyl isobutyrate). In contrast to the azaphenalenes, in the benzophenone-based alkoxyamines, conjugation between the nitroxide and chromophore moieties appears to facilitate homolysis, due to the ideal alignment of singlet and triplet states of different symmetries.
Published: 2020
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57. Light-Induced Thermal Decomposition of Alkoxyamines upon Infrared CO2 Laser: Toward Spatially Controlled Polymerization of Methacrylates in Laser Write Experiments

Author: Jacques Lalevée, Didier Gigmes, Aude-Héloise Bonardi, Frédéric Dumur, Yangyang Xu, Institut de Science des Matériaux de Mulhouse (IS2M), Centre National de la Recherche Scientifique (CNRS)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Département de Photochimie Générale (DPG), Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS), Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-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)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), and Dumur, Frederic
Subjects: Materials science, General Chemical Engineering, 02 engineering and technology, 010402 general chemistry, Photochemistry, Methacrylate, 01 natural sciences, Article, law.invention, chemistry.chemical_compound, law, QD1-999, ComputingMilieux_MISCELLANEOUS, [CHIM.MATE] Chemical Sciences/Material chemistry, Thermal decomposition, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, Photothermal therapy, 021001 nanoscience & nanotechnology, Laser, 0104 chemical sciences, Chemistry, Monomer, Photopolymer, chemistry, Polymerization, Heat generation, 0210 nano-technology
Abstract: Systems combining photopolymerization and thermal polymerization have already been reported in the literature. Upon near-infrared (NIR) light exposure, this principle of polymerization is called photoinduced thermal polymerization or photothermal polymerization. Thanks to an NIR dye used as the light-to-heat convertor (called hereafter a heater), an alkoxyamine (e.g., BlocBuilder-MA) is dissociated upon NIR light irradiation, initiating the free-radical polymerization of methacrylates. In the present paper, a novel approach is presented for the first time to decompose the alkoxyamine through a direct heat generation upon mid-infrared irradiation by a CO2 laser at 10.6 μm. Compared with previous approaches, there is no additional heater used in this work, as the heat is directly generated by laser irradiation on the alkoxyamine/monomer system. The polymerization can be initiated for benchmark methacrylate monomers with spatial controllability, that is, only in the laser-irradiated area, opening the way for laser write or three-dimensional printing applications in the presence of fillers.
Published: 2020
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58. Free‐radical polymerization upon near‐infrared light irradiation, merging photochemical and photothermal initiating methods

Author: Aude Héloïse Bonardi, Guillaume Noirbent, Didier Gigmes, Jacques Lalevée, Fabien Bonardi, Céline Dietlin, Frédéric Dumur, Dumur, Frederic, Institut de Science des Matériaux de Mulhouse (IS2M), Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-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)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Informatique, BioInformatique, Systèmes Complexes (IBISC), Université d'Évry-Val-d'Essonne (UEVE)-Université Paris-Saclay, Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, and Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)
Subjects: [CHIM.POLY] Chemical Sciences/Polymers, Materials science, Polymers and Plastics, Radical polymerization, 02 engineering and technology, Photothermal therapy, 010402 general chemistry, 021001 nanoscience & nanotechnology, Methacrylate, Photochemistry, 01 natural sciences, 0104 chemical sciences, Electron transfer, [CHIM.POLY]Chemical Sciences/Polymers, Photopolymer, Polymerization, Materials Chemistry, Irradiation, Physical and Theoretical Chemistry, Fourier transform infrared spectroscopy, 0210 nano-technology, [SPI.SIGNAL]Engineering Sciences [physics]/Signal and Image processing, [SPI.SIGNAL] Engineering Sciences [physics]/Signal and Image processing
Abstract: International audience; Polymerization of (meth)acrylate resins upon near‐infrared (NIR) light remains a huge challenge. In this study, a new photoinduced method of polymerization of methacrylic monomers is presented, originally merging a photochemical and a photothermal pathway. A four‐component system is proposed comprising an NIR dye combined with an iodonium salt, a phosphine, and a thermal initiator. A selection of dyes is suggested regarding electron transfer properties and/or light‐to‐heat conversion abilities. Several thermal initiators are studied: an alkoxyamine (BlocBuilder MA), an azo derivative, and a peroxide. For the first time, an NIR absorbing dye is used in photopolymerization using both its capacities of light‐to‐heat conversion and its ability to initiate an electron transfer reaction. Three wavelengths of irradiation will be presented here: 785, 940, and 1064 nm. These long wavelengths are challenging because the energy of photons is extremely low but these wavelengths offer significant advantages in term of light penetration (e.g., for the access to composites through photopolymerization processes). The different systems presented here exhibit high and rapid conversions of methacrylate functions. The underlying chemical mechanism will be fully depicted by real‐time Fourier transform infrared spectroscopy and thermal imaging measurements.
Published: 2020
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59. Radical ring-opening polymerization of novel azlactone-functionalized vinyl cyclopropanes

Author: Laurent Fontaine, Sagrario Pascual, Véronique Montembault, Kamel Mabrouk, Didier Gigmes, Trang N. T. Phan, Soioulata Aboudou, hien ho, Marion Rollet, Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Molécules et Matériaux du Mans (IMMM), and Le Mans Université (UM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: chemistry.chemical_classification, Bioconjugation, Polymers and Plastics, 010405 organic chemistry, Chemistry, Organic Chemistry, Bioengineering, Polymer, 010402 general chemistry, 01 natural sciences, Biochemistry, Combinatorial chemistry, Ring-opening polymerization, 0104 chemical sciences, chemistry.chemical_compound, [CHIM.POLY]Chemical Sciences/Polymers, Monomer, Polymerization
Abstract: International audience; Azlactone-functionalized polymers are considered powerful materials for bioconjugation and many other applications. However, the limited number of azlactone monomers available and their multistage syntheses pose major challenges for the preparation of new reactive polymers from these monomers. In this article, we report the synthesis of a new class of azlactone monomers based on vinylcyclopropane (VCP). Furthermore, the (co)polymerization of the azlactone-functionalized VCPs has been successfully demonstrated to provide new azlactone polymers by using free-radical polymerization. The ability of the resulting amine-reactive polymers to be engaged in post-polymerization modifications was demonstrated using dansylcadaverine. These new azlactone-functionalized VCP monomers and polymers are potential candidates for the synthesis of innovative (bio)materials.
Published: 2020
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60. Enantioselective Radical Reactions Using Chiral Catalysts

Author: Shovan Mondal, Frédéric Dumur, Didier Gigmes, Mukund P. Sibi, Michèle P. Bertrand, Malek Nechab, Syamsundar College, Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and North Dakota State University (NDSU)
Subjects: Stereoisomerism, General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, Oxidation-Reduction, Catalysis, ComputingMilieux_MISCELLANEOUS, Hydrogen, Lewis Acids
Abstract: Benefiting from the impressive increase in fundamental knowledge, the last 20 years have shown a continuous burst of new ideas and consequently a plethora of new catalytic methods for enantioselective radical reactions. This review aims to provide a complete survey of progress achieved over this latter period. The first part of this review focuses on the use of chiral organocatalysts, and these include catalysts covalently linked to the substrate and those that interact with the substrate by weaker interactions like hydrogen bonds. The second part of the review is devoted to transition-metal redox catalysis which is organized according to increasing atomic number for the first-row transition metals (Ti, Cr, Fe, Mn, Co, Ni, Cu). Bioinspired manganese- and iron-mediated hydroxylations and oxidations are also discussed. A specific section is dedicated to the reactivity of Ru, Rh, and Ir complexes as Lewis acids with a special focus on complexes chiral at metal. Absorption of photons result in different events such as energy transfer, single-electron transfer, and hydrogen-atom transfer facilitating the formation of radicals. Organocatalysis has been successfully combined with photocatalysts, a reactivity which has opened new pathways enlarging the number of radical precursors available. The merger of photocatalysis with organo- or metalla-photocatalysis has brought novelty and allowed for the discovery of a large number of original transformations. The use of enzyme-catalyzed reactions involving radical intermediates which also largely benefit from visible-light irradiation are included in the review. This review provides a comprehensive inventory of progress in enantioselective radical reactions with a goal of detailing the reaction mechanisms involved in these transformations such that any nonspecialist could find their own creativity to invent yet unknown applications.
Published: 2022
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61. Polyhedral Oligomeric Silsesquioxane-Based Macroanions to Level Up the Li + Transport Number of Electrolytes for Lithium Batteries

Author: Thi Khanh Ly Nguyen, Trang N. T. Phan, Fabrice Cousin, Didier Devaux, Sumit Mehan, Fabio Ziarelli, Stéphane Viel, Didier Gigmes, Priscillia Soudant, Renaud Bouchet, Matériaux Interfaces ELectrochimie (MIEL), Laboratoire d'Electrochimie et de Physico-chimie des Matériaux et des Interfaces (LEPMI), Institut de Chimie du CNRS (INC)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA), Laboratoire de Physico-chimie des Polymères et des Interfaces (LPPI), Fédération INSTITUT DES MATÉRIAUX DE CERGY-PONTOISE (I-MAT), CY Cergy Paris Université (CY)-CY Cergy Paris Université (CY), Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Léon Brillouin (LLB - UMR 12), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), LLB - Matière molle et biophysique (MMB), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), ANR-17-CE05-0032, and ANR-17-CE05-0032,SELPHy,Batterie au Li-métal à électrolyte hybride conducteur uniquement par ions lithium(2017)
Subjects: [CHIM.POLY]Chemical Sciences/Polymers, lithium, General Chemical Engineering, transport, Materials Chemistry, General Chemistry, electrolyte, [CHIM.MATE]Chemical Sciences/Material chemistry, macro-anion, POSS
Abstract: International audience; Increasing lithium transport number in liquid and polymers electrolytes is an important task for higher power performance since it limits the promotion of concentration gradient and the mitigation of dendrite nucleation. One promising route to limit the anion mobility is the design of macro-anions. In this paper, by varying the number of LiTFSI salt and PEG chains attached to POSS nanoparticles, a series of POSS-based macro-anions were synthesized and complexed with tetraglyme (TEG) model solvent to form electrolytes at different concentrations from EO/Li=10 to 25. While a high transport number in between 0.7 to 0.86 was obtained as expected, a significantly lower cationic conductivity was observed compared to TEG-LiTFSI reference electrolyte at the same lithium concentration. The understanding of this behavior is necessary for the design of the next electrolyte generation. Thus, a complete study coupling morphologic (SAXS), thermal (DSC/ATG), conductivity (EIS), and 1H, 7Li, 19F diffusion NMR analyses is provided to establish in a single equation (Equation 11) the relationship between the Li+ ionic transport properties and the size of macro-anion which impacts strongly, beside the transport number, the electrolyte bulk properties, such as the viscosity and the tortuosity induced by the large POSS inorganic cores. In addition, it is shown that the chemical affinity of the organic POSS shell and the solvent pilots the Li+ dissociation rate, and thus the content of free Li+ ion. These results provide a deep insight on the intricacy of the physical properties (Equation 11) that leads to high cationic conductivity which can be a helpful intellectual platform for the target-design of new macro-anions.
Published: 2022
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62. Nitroxide mediated radical polymerization for the preparation of poly(vinyl chloride) grafted poly(acrylate) copolymers

Author: Aurélien Vebr, Magali Dallegre, Laurent Autissier, Charlotte Drappier, Karel Le Jeune, Didier Gigmes, Anthony Kermagoret, Unité Matériaux et Transformations - UMR 8207 (UMET), Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Global Compounds, Centre National de la Recherche Scientifique (CNRS)European Commission, and Aix-Marseille Universite
Subjects: [CHIM.POLY]Chemical Sciences/Polymers, Polymers and Plastics, Organic Chemistry, Bioengineering, Biochemistry
Abstract: International audience; In view to control the thermal properties of PVC without the use of toxic phthalate derivatives, alkoxyamines were grafted onto an azide modified PVC, through copper catalyzed azide-alkyne cycloaddition (CuAAC), to initiate a radical polymerization of acrylate monomers including butyl acrylate (BA) and polyethylglycol acrylate (PEGA) monomers. A series of PVC-g-PBA copolymers having glass various temperature transition (Tg) between 63.5 to-10.5 °C were obtained. The PVC-g-PEGA copolymers presented a semi-crystalline behavior with a Tg of-4 °C and a Tm of 43 °C. This method, combining CuAAC click reaction and radical polymerization, was efficient to covalently link a plasticizing group on PVC. This "grafting from" strategy using alkoxyamine functionalized PVC can be expanded to produce new materials via nitroxide mediated polymerization of various monomers.
Published: 2022
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63. Phosphonate-Functionalized Polycarbonates Synthesis through Ring-Opening Polymerization and Alternative Approaches

Author: Hien The Ho, Nam Hoai Nguyen, Marion Rollet, Trang N. T. Phan, and Didier Gigmes
Subjects: phosphonate-functionalized polycarbonate, Polymers and Plastics, post-modification, ring-opening polymerization (ROP), General Chemistry, “click” chemistry
Abstract: Well-defined phosphonate-functionalized polycarbonate with low dispersity (Ð = 1.22) was synthesized using organocatalyzed ring-opening polymerization (ROP) of novel phosphonate-based cyclic monomers. Copolymerization was also performed to access different structures of phosphonate-containing polycarbonates (PC). Furthermore, phosphonate-functionalized PC was successfully synthesized using a combination of ROP and post-modification reaction.
Published: 2023
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64. Thionolactone as a Resin Additive to Prepare (Bio)degradable 3D Objects via VAT Photopolymerization

Author: Noémie Gil, Constance Thomas, Rana Mhanna, Jessica Mauriello, Romain Maury, Benjamin Leuschel, Jean‐Pierre Malval, Jean‐Louis Clément, Didier Gigmes, Catherine Lefay, Olivier Soppera, Yohann Guillaneuf, Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Science des Matériaux de Mulhouse (IS2M), Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-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)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), ANR-18-CE06-0014,CKAPART,Synthèse de particules dégradables par polymérisation radicalaire en milieu dispersé(2018), ANR-19-CE19-0012,DYNABIO,Capteur Dynamique pour Nano Biomarqueur(2019), Guillaneuf, Yohann, APPEL À PROJETS GÉNÉRIQUE 2018 - Synthèse de particules dégradables par polymérisation radicalaire en milieu dispersé - - CKAPART2018 - ANR-18-CE06-0014 - AAPG2018 - VALID, and Capteur Dynamique pour Nano Biomarqueur - - DYNABIO2019 - ANR-19-CE19-0012 - AAPG2019 - VALID
Subjects: [CHIM.POLY] Chemical Sciences/Polymers, [CHIM.POLY]Chemical Sciences/Polymers, Printing, Three-Dimensional, General Chemistry, General Medicine, Catalysis, Polymerization
Abstract: Three-dimensional (3D) printing and especially VAT photopolymerization leads to cross-linked materials with high thermal, chemical, and mechanical stability. Nevertheless, these properties are incompatible with requirements of degradability and re/upcyclability. We show here that thionolactone and in particular dibenzo[c,e]-oxepane-5-thione (DOT) can be used as an additive (2 wt %) to acrylate-based resins to introduce weak bonds into the network via a radical ring-opening polymerization process. The low amount of additive makes it possible to modify the printability of the resin only slightly, keep its resolution intact, and maintain the mechanical properties of the 3D object. The resin with additive was used in UV microfabrication and two-photon stereolithography setups and commercial 3D printers. The fabricated objects were shown to degrade in basic solvent as well in a homemade compost. The rate of degradation is nonetheless dependent on the size of the object. This feature was used to prepare 3D objects with support structures that could be easily solubilized.
Published: 2021
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65. One-Step Synthesis of Degradable Vinylic Polymer-Based Latexes via Aqueous Radical Emulsion Polymerization

Author: Paul Galanopoulo, Noémie Gil, Didier Gigmes, Catherine Lefay, Yohann Guillaneuf, Maëlle Lages, Julien Nicolas, Muriel Lansalot, Franck D'Agosto, Catalyse, Polymérisation, Procédés et Matériaux (CP2M), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École Supérieure de Chimie Physique Électronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Galien Paris-Saclay (IGPS), Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), and ANR-18-CE06-0014,CKAPART,Synthèse de particules dégradables par polymérisation radicalaire en milieu dispersé(2018)
Subjects: [CHIM.POLY]Chemical Sciences/Polymers, General Chemistry, General Medicine, Catalysis
Abstract: International audience; Aqueous emulsion copolymerizations of dibenzo[c,e]oxepane-5-thione (DOT) were performed with n-butyl acrylate (BA), styrene (S) and a combination of both. In all cases, stable latexes were obtained in less than two hours under conventional conditions; that is in the presence of sodium dodecyl sulfate (SDS) used as surfactant and potassium persulfate (KPS) as initiator. A limited solubility of DOT in BA was observed compared to S, yielding to a more homogeneous integration of DOT units in the PS latex. In both cases, the copolymer could be easily degraded under basic conditions. Emulsion terpolymerization between DOT, BA and S allowed us to produce stable latexes not only composed of degradable chains but also featuring a broad range of glass transition temperatures.
Published: 2021
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66. Thionolactone as Resin Additive to Prepare (bio)degradable 3D Objects via VAT Photopolymerization

Author: Noemie Gil, Constance Thomas, Rana Mhanna, Jessica Mauriello, Romain Maury, Benjamin Leuschel, Jean-Pierre Malval, Jean-Louis Clément, Didier Gigmes, Catherine Lefay, Olivier Soppera, and Yohann Guillaneuf
Abstract: 3D printing and especially VAT photopolymerization leads to cross-linked materials with high thermal, chemical and mechanical properties. Nevertheless, such stability is incompatible with degradability and re/upcyclability. We showed here that thionolactone and especially dibenzo[c,e]-oxepane-5-thione (DOT) could be used as an additive (2 wt%) to acrylate-based resins to introduce weak bonds into the network via a radical ring-opening polymerization process. The low amount of additive allows to only slightly modify the printability of the resin, keep intact its resolution and maintain the mechanical properties of the 3D object. The resin with additive was used in UV microfabrication and 2-photon stereolithography setup and commercial 3D printers. The fabricated objects were shown to degrade in basic solvent as well in a home-made compost. The rate of degradation is nonetheless dependent of the size of the object. This feature was used to prepare 3D objects with support structures that could be easily solubilized.
Published: 2021
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67. Substituent Effects on Photoinitiation Ability of Coumarin-Based Oxime-Ester Photoinitiators for Free Radical Photopolymerization

Author: Nicolas Giacoletto, Didier Gigmes, Guillaume Noirbent, Frédéric Dumur, Bernadette Graff, Fatima Hammoud, Akram Hijazi, Malek Nechab, Jacques Lalevée, Institut de Science des Matériaux de Mulhouse (IS2M), Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-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)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Ecole Doctorale des Sciences et de la Technologie (EDST), Lebanese University [Beirut] (LU), Centre National de la Recherche Scientifique (CNRS)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), and Dumur, Frederic
Subjects: dual initiators, Absorption spectroscopy, Radical, Radical polymerization, Substituent, 02 engineering and technology, 010402 general chemistry, Photochemistry, 01 natural sciences, chemistry.chemical_compound, Materials Chemistry, General Materials Science, Reactivity (chemistry), photoinitiators, visible light, [CHIM.MATE] Chemical Sciences/Material chemistry, coumarins, Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, Chromophore, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Oxime-esters, Photopolymer, Polymerization, 0210 nano-technology
Abstract: International audience; In this paper, a series of coumarin chromophore-based oxime-esters was designed and synthesized as visible light photoinitiators (PIs). Interestingly, upon exposure to irradiation of a LED at 405 nm, the investigated oxime-esters (OXEs) could undergo a direct photocleavage, followed by decarboxylation, generating active free radicals capable to effectively initiate acrylate polymerization. Seven of the 10 investigated OXEs have never been synthesized in the literature. Markedly, the new proposed structures exhibit also thermal initiation ability and can be used as dual photo and thermal initiators. In addition, the oxime-ester system was also paired with an iodonium salt and exhibited a higher efficiency in free radical polymerization (FRP). The chemical mechanisms and the structure/reactivity/efficiency relationships were investigated through different techniques including real-time Fourier Transform Infrared Spectroscopy (RT-FTIR), UV-visible absorption spectroscopy, fluorescence (time-resolved or steady state), cyclic voltammetry as well as molecular modelling calculations. As a proof of their remarkable polymerization performance, the new OXEs were also used at 405 nm for direct laser write applications.
Published: 2021
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68. New Crosslinked Single-Ion Silica-PEO Hybrid Electrolytes

Author: Sébastien Issa, Roselyne Jeanne-Brou, Sumit Mehan, Didier Devaux, Fabrice Cousin, Didier Gigmes, Renaud Bouchet, and Trang N. T. Phan
Subjects: Polymers and Plastics, crosslinked polymers, single-ion hybrid electrolytes, lithium metal batteries, sol–gel polycondensation, electrochemical impedance spectroscopy, General Chemistry
Abstract: New single-ion hybrid electrolytes have been synthetized via an original and simple synthetic approach combining Michael addition, epoxidation, and sol–gel polycondensation. We designed an organic PEO network as a matrix for the lithium transport, mechanically reinforced thanks to crosslinking inorganic (SiO1.5) sites, while highly delocalized anions based on lithium vinyl sulfonyl(trifluoromethane sulfonyl)imide (VSTFSILi) were grafted onto the inorganic sites to produce single-ion hybrid electrolytes (HySI). The influence of the electrolyte composition in terms of the inorganic/organic ratio and the grafted VSTFSILi content on the local structural organization, the thermal, mechanical, and ionic transport properties (ionic conductivity, transference number) are studied by a variety of techniques including SAXS, DSC, rheometry, and electrochemical impedance spectroscopy. SAXS measurements at 25 °C and 60 °C reveal that HySI electrolyte films display locally a spatial phase separation with domains composed of PEO rich phase and silica/VSTFSILi clusters. The size of these clusters increases with the silica and VSTFSILi content. A maximum ionic conductivity of 2.1 × 10−5 S·cm−1 at 80 °C has been obtained with HySI having an EO/Li ratio of 20. The Li+ ion transfer number of HySI electrolytes is high, as expected for a single-ion electrolyte, and comprises between 0.80 and 0.92.
Published: 2022
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69. Switching from Single to Simultaneous Free-Radical and Anionic Polymerization with Enamine-Based Organic Electron Donors

Author: Marion Rollet, Patrice Vanelle, Didier Gigmes, Gabriel Canard, Yuxi Zhao, Laurence Charles, Julie Broggi, Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Aix Marseille Université (AMU), Centre Interdisciplinaire de Nanoscience de Marseille (CINaM), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS), JCJC ANR grant 'iPOD' (17-CE07-000101)Ph.D. fellowships from the China Scholarship Council (CSC)., ANR-17-CE07-0001,iPOD,Conception de donneurs d'électrons organiques polyvalents: Applications en synthèse organique et polymères.(2017), and Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU)
Subjects: Reduction Method, 010405 organic chemistry, Anionic polymerization, [CHIM.ORGA]Chemical Sciences/Organic chemistry, General Medicine, General Chemistry, Electron, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, Photochemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, Enamine, chemistry.chemical_compound, Anionic addition polymerization, Monomer, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Polymerization, Radical polymerization, Organic electron donors, Electron transfer ET, Interpenetrating polymer network
Abstract: International audience; Although most monomers can polymerize through different propagation pathways, polymerization-initiating systems that can switch from one mode to another are rare. In this study, we demonstrate that enamine-based organic electron donors (OEDs) constitute the first systems able to initiate either free-radical or anionic polymerization under simple, mild, and safe conditions. While direct electron-transfer reduction of monomers by OEDs results in the initiation of anionic chaingrowth polymerization, introduction of a competing oxidant with a higher reduction potential than the monomer switches the former anionic propagation to a clean radical-propagation process. The benefit of this dual-mode activator is highlighted in the synthesis of an interpenetrating polymer network through simultaneous initiation of radical and anionic propagation processes.
Published: 2021
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70. Near‐infrared light for polymer re‐shaping and re‐processing applications

Author: Jacques Lalevée, Valentin Launay, Didier Gigmes, Frédéric Dumur, Institut de Science des Matériaux de Mulhouse (IS2M), Centre National de la Recherche Scientifique (CNRS)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-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)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), and Dumur, Frederic
Subjects: Materials science, Polymers and Plastics, 02 engineering and technology, Polyethylene glycol, 010402 general chemistry, 01 natural sciences, chemistry.chemical_compound, Thermal, Materials Chemistry, Irradiation, Physical and Theoretical Chemistry, Diode, chemistry.chemical_classification, [CHIM.MATE] Chemical Sciences/Material chemistry, business.industry, Photothermal effect, Polymer, [CHIM.MATE]Chemical Sciences/Material chemistry, Photothermal therapy, 021001 nanoscience & nanotechnology, 0104 chemical sciences, chemistry, Self-healing hydrogels, Optoelectronics, 0210 nano-technology, business
Abstract: International audience; The shaping and reprocessing of polymers are usually associated with strong energetic costs, strongly limiting their practical usage. In this paper, a new approach is proposed based on a NIR activation of the material in presence of a NIR heater for a highly efficient process upon ecofriendly NIR light emitting diodes irradiation. Markedly, due to this light-triggered process, a spatial control of the shaping/reprocessing behavior can be obtained i.e. only the needed parts are irradiated preventing a heating of all the sample. In this work, different thermoplastics are reshaped or reprocessed due to NIR activation in presence of an organic NIR dye used as heater. As other examples of photothermal treatment upon NIR light, the ondemand dehydration of polyethylene glycol (PEG)-based hydrogels are also provided. All the processes are followed in real time by thermal imaging camera.
Published: 2021
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71. Synthesis, optical and electrochemical properties of a series of push-pull dyes based on the 4,4-bis(4-methoxy phenyl)butadienyl donor

Author: Frédéric Dumur, Guillaume Noirbent, Corentin Pigot, Didier Gigmes, Thanh-Tuân Bui, Sébastien Péralta, Malek Nechab, Sylvain Duval, Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Physico-chimie des Polymères et des Interfaces (LPPI), Fédération INSTITUT DES MATÉRIAUX DE CERGY-PONTOISE (I-MAT), CY Cergy Paris Université (CY)-CY Cergy Paris Université (CY), Ecole Nationale Supérieure de Chimie de Lille (ENSCL), Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), ANR-17-CE08-0010,DUALITY,Elaboration de réseaux covalents bidimensionnels nanoporeux dirigés par la surface(2017), ANR-17-CE08-0054,VISICAT,Nouveaux Photocatalyseurs Redox pour la Synthèse sous Lumière Visible de Réseaux Polymères Interpénétrés(2017), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU), and Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille
Subjects: chemistry.chemical_classification, Absorption spectroscopy, 010405 organic chemistry, Chemistry, Process Chemistry and Technology, General Chemical Engineering, Solvatochromism, solvatochromism, indanedione, TNF, TCF, [CHIM.MATE]Chemical Sciences/Material chemistry, Electron acceptor, 010402 general chemistry, Photochemistry, Electrochemistry, 01 natural sciences, Push-pull dyes, Michler's aldehyde, 0104 chemical sciences, Solvent, Polarizability, rhodanine, Absorption (chemistry), Cyclic voltammetry
Abstract: International audience; A series of twelve dyes based on the 4,4-bis(4-methoxyphenyl)butadienyl donor and differing by the electron acceptors have been designed and synthesized. The different dyes were characterized by UV-visible absorption spectroscopy as well as cyclic voltammetry. By fine tuning the electron-accepting ability of the fourteen selected acceptors, dyes absorbing between 400 and 650 nm could be obtained with this π-extended donor. To get a deeper insight into the optical properties, solvatochromism was investigated in 23 different solvents and remarkable linear correlations could be obtained using the Taft and Catalan solvatochromism scales. A comparison with four dyes used as reference compounds and differing from the series of twelve dyes by the structure of the electron-donating groups was also established so that the electron releasing ability of the 4,4-bis(4-methoxyphenyl)butadienyl donor could be compared with the reference ones. To prepare these four references compounds, only two electron acceptors previously used for the design of the twelve dyes have been employed. Interestingly, variation of the absorption maxima of the twelve dyes was determined as being more influenced by the polarizability of the solvent rather than by its polarity. To support the experimental results, theoretical calculations were carried out.
Published: 2021
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72. A Cucurbit[8]uril 2:2 Complex with a Negative p K a Shift

Author: Anthony Kermagoret, Olivier Ouari, Roselyne Rosas, Valérie Monnier, Qian Cheng, Hang Yin, Ruibing Wang, Stéphane Viel, Didier Gigmes, Didier Siri, Laurence Charles, David Bardelang, State Key Laboratory of Quality Research in Chinese Medicine Taipa, Macau SAR, (Institute of Chinese Medical Sciences), State Key Laboratory of Quality Research in Chinese Medicine, Institute of Chinese Medical Sciences, University of Macau, Taipa, Macau, China, Spectropôle - Aix Marseille Université (AMU SPEC), Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU), Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Chimie Provence (LCP), Centre National de la Recherche Scientifique (CNRS)-Université de Provence - Aix-Marseille 1-Institut de Chimie du CNRS (INC), Chimie, biologie et radicaux libres - UMR 6517 (CBRL), Université de la Méditerranée - Aix-Marseille 2-Université Paul Cézanne - Aix-Marseille 3-Université de Provence - Aix-Marseille 1-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265 (C2P2), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS), Université de Provence - Aix-Marseille 1-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Université de Lyon-Université de Lyon-École Supérieure de Chimie Physique Électronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Benzimidazole, 010405 organic chemistry, Chemistry, Stereochemistry, Organic Chemistry, Viologen, Protonation, General Chemistry, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, Deprotonation, Cucurbituril, medicine, [CHIM]Chemical Sciences, Imidazole, Molecule, Pyridinium, medicine.drug
Abstract: A viologen derivative carrying a benzimidazole group (V‐P‐I 2+; viologen–phenylene–imidazole V‐P‐I) can be dimerized in water using cucurbit[8]uril (CB[8]) in the form of a 2:2 complex resulting in a negative shift of the guest pKa, by more than 1 pH unit, contrasting with the positive pKa shift usually observed for CB‐based complexes. Whereas 2:2 complex protonation is unclear by NMR, silver cations have been used for probing the accessibility of the imidazole groups of the 2:2 complexes. The protonation capacity of the buried imidazole groups is reduced, suggesting that CB[8] could trigger proton release upon 2:2 complex formation. The addition of CB[8] to a solution containing V‐P‐ I3+ indeed released protons as monitored by pH‐metry and visualized by a coloured indicator. This property was used to induce a host/guest swapping, accompanied by a proton transfer, between V‐P‐I 3+⋅CB[7] and a CB[8] complex of 1‐methyl‐4‐(4‐pyridyl)pyridinium. The origin of this negative pKa shift is proposed to stand in an ideal charge state, and in the position of the two pH‐responsive fragments inside the two CB[8] which, alike residues engulfed in proteins, favour the deprotonated form of the guest molecules. Such proton release triggered by a recognition event is reminiscent of several biological processes and may open new avenues toward bioinspired enzyme mimics catalyzing proton transfer or chemical reactions.
Published: 2019
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73. Redox two-component initiated free radical and cationic polymerizations: Concepts, reactions and applications

Author: Jacques Lalevée, Jean-Pierre Fouassier, Didier Gigmes, Frédéric Dumur, Céline Dietlin, Fabrice Morlet-Savary, Patxi Garra, Institut de Science des Matériaux de Mulhouse (IS2M), Centre National de la Recherche Scientifique (CNRS)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Aix Marseille Université (AMU), Gigmes, Didier, Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-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)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, and Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)
Subjects: chemistry.chemical_classification, Polymers and Plastics, Chemistry, Component (thermodynamics), Organic Chemistry, Cationic polymerization, 02 engineering and technology, Surfaces and Interfaces, Polymer, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Combinatorial chemistry, Redox, 0104 chemical sciences, Polymerization, [CHIM] Chemical Sciences, Oxidizing agent, Materials Chemistry, Ceramics and Composites, [CHIM]Chemical Sciences, 0210 nano-technology
Abstract: WOS:000474332100002; International audience; Redox polymerizations are of huge importance throughout academic and industrial polymer science. Many authors propose the reaction of reducing (Red) and oxidizing (Ox) agents to accelerate/initiate radical or cationic polymerizations. As a result of activation energies typically below 80 kJ/mol, such reactions can occur under mild conditions, e.g., at room temperature, with reduced energy consumptions and robust in applications, such as the fabrication of composites. However, a clear definition of redox polymerization can only be found in reviews dealing with redox free radical polymerizations (FRP) published twenty years ago (or more). Therefore, a fresh and broader update is provided here for more recent work. The concepts involved when the Redand Oxagents (constituting the redox initiating system) are mixed under mild conditions are presented, followed by a discussion of the redox FRP initiating systems in bulk. Initiating systems dealing with the redox cationic polymerization (CP) are reviewed, and parallels between conventional FRP/CP and controlled polymerizations, in which redox systems are used, is provided. Many redox agents are useful in both modes. Finally, dual-cure (redox/photochemical; redox dual FRP/CP) systems is presented and selected applications are reviewed. Altogether, the state of the art for redox two-component polymerizations is provided, along with some perspectives. (C) 2019 Elsevier B.V. All rights reserved.
Published: 2019
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74. Melt radical grafting of diethylmaleate and maleic anhydride onto oligoamide-11 (OA11) and polyamide-11 (PA11) in presence of acyloxyimide derivatives: Toward the compatibilization of PA11/EVOH blends

Author: Didier Gigmes, Mohamed Ihab El Assil, Sébastien Quinebeche, Yohann Guillaneuf, Emmanuel Beyou, Mamy-Daniel Rakotorinina, Didier Siri, Jean-Jacques Flat, Philippe Cassagnau, Anouk Gaudel-Siri, and Marc Baron
Subjects: Materials science, Chemical structure, Maleic anhydride, 02 engineering and technology, Compatibilization, 010402 general chemistry, 021001 nanoscience & nanotechnology, Grafting, 01 natural sciences, 0104 chemical sciences, Autoclave, chemistry.chemical_compound, chemistry, Chemical engineering, Mechanics of Materials, Polyamide, Materials Chemistry, Copolymer, Surface modification, General Materials Science, 0210 nano-technology
Abstract: For the first time, the melt radical grafting of diethylmaleate (DEM) and maleic anhydride (MA) onto oligoamide-11 (OA11) and polyamide-11 (PA11) was performed in presence of new acyloxyimide derivatives in the temperature range 190 °C–250 °C in an autoclave and a mini-extruder, respectively. The DEM grafting degree was studied as a function of reaction temperature, the DEM concentration, the acyloxyimide concentration and its chemical structure. The degree of grafting of DEM was determined by 1H NMR and we obtained a DES (diethylsuccinimate) functionalization degree (FD) as high as 9 mol% onto OA11 when using tBu-NAPI as H-abstractor at 230 °C. However, the transposition of this grafting reaction at a pilot scale did not permit to obtain such a high DES FD while the morphological study of PA11/EVOH blends with the grafted copolymer did not significantly improve the adhesion between the two phases.
Published: 2019
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75. Organische Photosäuren‐ und Photobasenbildner für Polymerisationen: Jüngste Fortschritte und Herausforderungen

Author: Haritz Sardon, Paula K. Kuroishi, Didier Gigmes, Andrew P. Dove, Frédéric Dumur, and Nicolas Zivic
Subjects: Materials science, 02 engineering and technology, General Medicine, 010402 general chemistry, 021001 nanoscience & nanotechnology, 0210 nano-technology, 01 natural sciences, 0104 chemical sciences
Published: 2019
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76. Collision-induced dissociation of stable nitroxides: A combined tandem mass spectrometry and computational study of TEMPO• and SG1•

Author: Vincent Ledentu, Didier Siri, Cathie Marchal, Laurence Charles, Didier Gigmes, and Anouk Gaudel-Siri
Subjects: Nitroxide mediated radical polymerization, Collision-induced dissociation, Chemistry, 010401 analytical chemistry, Protonation, General Medicine, 010402 general chemistry, Photochemistry, Tandem mass spectrometry, Mass spectrometry, 01 natural sciences, 7. Clean energy, Atomic and Molecular Physics, and Optics, Dissociation (chemistry), 0104 chemical sciences, Fragmentation (mass spectrometry), Molecule, Spectroscopy
Abstract: The dissociation behavior of two stable nitroxides, namely 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO•) and N-tert-butyl-1-diethylphosphono-2,2-dimethylpropyl nitroxide (SG1•), subjected as protonated molecules to collisional activation was investigated using a combination of different mass spectrometry experiments and theoretical calculations. Elemental composition of reaction products was derived from accurate mass data measured in high resolution tandem mass spectrometry experiments, primary fragments were distinguished from secondary ions based on both breakdown curves and MS3 data, and H/D exchange experiments were performed to support proposed structures. Postulated fragmentation pathways were then studied in terms of energetic, using the standard B3LYP/6-31G(d) method. While protonation of TEMPO• mainly occurred on the oxygen atom of the nitroxyl function, a series of protomers were found for SG1• with the adducted proton preferentially located onto the P=O group of this phosphorylated species. For both protonated nitroxides, major product ions measured in tandem mass spectrometry arose from reactions occurring at low energy costs via elimination of radical species. Formation of secondary fragments that were detected with low abundance when raising the activation level of both precursor ions could be rationalized with pathways proceeding via high energy transition states.
Published: 2019
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77. Ultraschnelle Synthese multivalenter radikalischer Nanopartikel durch ringöffnende Metathesepolymerisations‐induzierte Selbstorganisation

Author: Carsten Weiss, Vincent Pertici, Guillaume Delaittre, Dao Le, Didier Gigmes, Silvia Diabaté, and Marco Dilger
Subjects: Chemistry, General Medicine
Published: 2019
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78. Ultra‐Fast Synthesis of Multivalent Radical Nanoparticles by Ring‐Opening Metathesis Polymerization‐Induced Self‐Assembly

Author: Dao Le, Vincent Pertici, Didier Gigmes, Carsten Weiss, Silvia Diabaté, Guillaume Delaittre, Marco Dilger, Institute for Chemical Technology and Polymer Chemistry, Karlsruhe Institute of Technology (KIT), Institute of Toxicology and Genetics [Karlsruhe] (ITG), Institut de Chimie Radicalaire (ICR), and Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Biocompatibility, 010405 organic chemistry, technology, industry, and agriculture, Nanoparticle, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, 010402 general chemistry, Metathesis, 01 natural sciences, Combinatorial chemistry, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, Monomer, chemistry, Amphiphile, Copolymer, Ring-opening metathesis polymerisation, Norbornene
Abstract: WOS:000462622700049; International audience; We report the straightforward, time-efficient synthesis of radical core-shell nanoparticles (NPs) by polymerization-induced self-assembly. A nitroxide-containing hydrophilic macromolecular precursor was prepared by ring-opening metathesis copolymerization of norbornenyl derivatives of TEMPO and oligoethylene glycol and was chain-extended insitu with norbornene in ethanolic solution, leading to simultaneous amphiphilic block copolymer formation and self-assembly. Without any intermediate purification from the monomers to the block copolymers, radical NPs with tunable diameters ranging from 10 to 110 nm are obtained within minutes at room temperature. The high activity of the radical NPs as chemoselective and homogeneous, yet readily recyclable catalysts is demonstrated through oxidation of a variety of alcohols and recovery by simple centrifugation. Furthermore, the NPs show biocompatibility and antioxidant activity invitro.
Published: 2019
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79. Lebetin Peptides, A New Class of Potent Platelet Aggregation Inhibitors: Chemical Synthesis, Biological Activity and NMR Spectroscopic Study

Author: Ernest Giralt, Ameur Cherif, Pascal Mansuelle, Naziha Marrakchi, Soumaya Kouidhi, Didier Gigmes, Amor Mosbah, Hervé Darbon, Gaëtan Herbette, Kamel Mabrouk, and Mohamed El Ayeb
Subjects: chemistry.chemical_classification, Gene isoform, 010405 organic chemistry, Bioengineering, Peptide, Biological activity, 01 natural sciences, Biochemistry, Chemical synthesis, 0104 chemical sciences, Analytical Chemistry, chemistry, Drug Discovery, Glycine, Molecular Medicine, Platelet aggregation inhibitor, Platelet, Platelet activation
Abstract: Platelets have a well-established role in atherosclerosis and related diseases. Lebetins from the venom of Vipera lebetina, lacking the RGD sequence, emerged as a new family of platelet aggregation inhibitors. However, the interaction sites and precise mechanism between lebetin and its substrate remain unclear. Here, we successfully synthesized two peptide analogs, which differ only by one glycine residue at the N-terminus: lebetin 2α (sL2α residues) and lebetin 2β (sL2ββ residues) were produced in sufficient quantities for structural and functional studies. NMR structure determination showed that the sL2α peptide adopts a compact ring conformation stabilized by a disulfide bond, from which emerge one loop and two extended regions, the C- and N-termini. Interestingly, two RGD-like motifs were identified in the structure of the peptides, suggesting an anti-platelet aggregation effect of the two isoforms. Indeed, activity was demonstrated on human and rabbit platelet-rich plasma where sL2α and sL2β showed more potent inhibitory effect on platelet aggregation compared to the previously described native lebetin 1. Synthetic lebetin 2 peptides constitute promising candidates for drug design toward chimeric compounds with high anti-platelet and natriuretic effects. These findings contribute to a novel field of research triggering platelet activation and natriuretic action.
Published: 2019
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80. Different NIR dye scaffolds for polymerization reactions under NIR light

Author: Aude Héloïse Bonardi, Jacques Lalevée, Didier Gigmes, Frédéric Dumur, Guillaume Noirbent, Fabrice Bonardi, Jean Pierre Fouassier, Céline Dietlin, Institut de Science des Matériaux de Mulhouse (IS2M), Centre National de la Recherche Scientifique (CNRS)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Département de Photochimie Générale (DPG), Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS), Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-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)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), and Dumur, Frederic
Subjects: Materials science, Polymers and Plastics, Radical polymerization, Bioengineering, 02 engineering and technology, 010402 general chemistry, Methacrylate, Photochemistry, 01 natural sciences, Biochemistry, chemistry.chemical_compound, [CHIM]Chemical Sciences, Cyanine, ComputingMilieux_MISCELLANEOUS, [CHIM.MATE] Chemical Sciences/Material chemistry, Organic Chemistry, Photothermal effect, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Porphyrin, 0104 chemical sciences, Photopolymer, chemistry, Polymerization, 0210 nano-technology, Phosphine
Abstract: WOS:000501007300010; In this article, near-infrared dyes of different structures have been investigated as new photoinitiators/photosensitizers for the free radical polymerization (FRP) of methacrylates upon Near InfraRed (NIR) light exposure using a laser diode @785 nm, @940 nm and @1064 nm. Interestingly, the use of squaraine, squarylium, boron-pyrromethene and porphyrin derivatives as efficient photoinitiators is clearly highlighted. These dyes are used in combination with an iodonium salt and a phosphine. Additionally, a thermal initiator can be added to the resin to take advantage of the photothermal effect, i.e., to the heat release during the polymerization process, so that polymerization kinetics could be greatly improved compared to the pure photochemical mode. These dyes can be proposed as alternatives to the well-established cyanine dyes, more commonly used for the photopolymerization of (meth)acrylates under NIR light.
Published: 2019
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81. 3-Carboxylic Acid and Formyl-Derived Coumarins as Photoinitiators in Photo-Oxidation or Photo-Reduction Processes for Photopolymerization upon Visible Light: Photocomposite Synthesis and 3D Printing Applications

Author: Jacques Lalevée, Joumana Toufaily, Mahmoud Rahal, Tayssir Hamieh, Frédéric Dumur, Didier Gigmes, Bernadette Graff, Guillaume Noirbent, Institut de Science des Matériaux de Mulhouse (IS2M), Centre National de la Recherche Scientifique (CNRS)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Lebanese University [Beirut] (LU), Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Dumur, Frederic, Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-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)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), and ANR-17-CE08-0054,VISICAT,Nouveaux Photocatalyseurs Redox pour la Synthèse sous Lumière Visible de Réseaux Polymères Interpénétrés(2017)
Subjects: Pharmaceutical Science, Lalevée, photocomposites, 02 engineering and technology, Photochemistry, 01 natural sciences, coumarin, Analytical Chemistry, M, chemistry.chemical_compound, DESIGN, direct laser write, Drug Discovery, Noirbent, ComputingMilieux_MISCELLANEOUS, chemistry.chemical_classification, free radical polymerization, DERIVATIVES, LEDS, T, Gigmes, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, J. 3-Carboxylic Acid and Formyl-Derived Coumarins as Photoinitiators in Photo-Oxidation or Photo-Reduction Processes for Photopolymerization upon Visible Light: Photocomposite Synthesis and coumarin, POLYMERIZATION, Photopolymer, Chemistry (miscellaneous), D, Molecular Medicine, Cyclic voltammetry, 0210 nano-technology, Visible spectrum, Carboxylic acid, Radical polymerization, Graff, 010402 general chemistry, Article, lcsh:QD241-441, lcsh:Organic chemistry, G, PHOTOCATALYSTS, Physical and Theoretical Chemistry, Hamieh, [CHIM.MATE] Chemical Sciences/Material chemistry, Acrylate, Rahal, Organic Chemistry, Photodissociation, LED, J, 0104 chemical sciences, B, chemistry, Polymerization, Toufaily, Dumur, F
Abstract: In this paper, nine organic compounds based on the coumarin scaffold and different substituents were synthesized and used as high-performance photoinitiators for free radical photopolymerization (FRP) of meth(acrylate) functions under visible light irradiation using LED at 405 nm. In fact, these compounds showed a very high initiation capacity and very good polymerization profiles (both high rate of polymerization (Rp) and final conversion (FC)) using two and three-component photoinitiating systems based on coum/iodonium salt (0.1%/1% w/w) and coum/iodonium salt/amine (0.1%/1%/1% w/w/w), respectively. To demonstrate the efficiency of the initiation of photopolymerization, several techniques were used to study the photophysical and photochemical properties of coumarins, such as: UV-visible absorption spectroscopy, steady-state photolysis, real-time FTIR, and cyclic voltammetry. On the other hand, these compounds were also tested in direct laser write experiments (3D printing). The synthesis of photocomposites based on glass fiber or carbon fiber using an LED conveyor at 385 nm (0.7 W/cm2) was also examined.
Published: 2021
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82. Guest Exchange by a Partial Energy Ratchet in Water

Author: Xue Yang, Qian Cheng, Anthony Kermagoret, Olivier Ouari, Valérie Monnier, David Bardelang, Hakim Karoui, Ruibing Wang, Laurence Charles, Didier Gigmes, Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), State Key Laboratory of Quality Research in Chinese Medicine, Institute of Chinese Medical Sciences, University of Macau, Taipa, Macau, China, Spectropôle - Aix Marseille Université (AMU SPEC), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS), University of Macau. Grant Numbers: MYRG2017-00010-ICMS, MYRG2019-00059-ICMSNational Science Foundation of China. Grant Number: 21871301, ANR-11-IDEX-0001,Amidex,INITIATIVE D'EXCELLENCE AIX MARSEILLE UNIVERSITE(2011), European Project: 713750,H2020,H2020-MSCA-COFUND-2015,DOC2AMU(2016), and Aix Marseille Univ, CNRS, Centrale Marseille, FSCM, Spectropole, Marseille, France
Subjects: Work (thermodynamics), Chemistry, 010405 organic chemistry, Ratchet, water, Supramolecular chemistry, General Chemistry, General Medicine, Kinetic energy, 010402 general chemistry, 01 natural sciences, Catalysis, Molecular machine, supramolecular chemistry, 0104 chemical sciences, cucurbituril, Cucurbituril, Chemical physics, Self-healing hydrogels, Molecule, [CHIM]Chemical Sciences, host–guest interactions, ratchet
Abstract: International audience; Molecular machines are ubiquitous in nature and function away from equilibrium by consuming fuels to produce appropriate work. Chemists have recently excelled at mimicking the fantastic job performed by natural molecular machines with synthetic systems soluble in organic solvents. In efforts toward analogous systems working in water, we show that guest molecules can be exchanged in the synthetic macrocycle cucurbit[7]uril by involving kinetic traps, and in such a way as modulating energy wells and kinetic barriers using pH, light and redox stimuli. Ditolyl-viologen can also be exchanged using the best kinetic trap and interfaced with alginate thus affording pH-responsive blue, fluorescent hydrogels. With tunable rate and binding constants toward relevant guests, cucurbiturils may become excellent ring molecules for the construction of advanced molecular machines working in water.
Published: 2021
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83. Near-Infrared PhotoInitiating Systems: Photothermal Effect vs. Triplet-Triplet Annihilation -based UpConversion Polymerization

Author: Jacques Lalevée, Didier Gigmes, Aurore Caron, Guillaume Noirbent, Frédéric Dumur, Institut de Science des Matériaux de Mulhouse (IS2M), Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-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)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), ANR-17-CE08-0054,VISICAT,Nouveaux Photocatalyseurs Redox pour la Synthèse sous Lumière Visible de Réseaux Polymères Interpénétrés(2017), Centre National de la Recherche Scientifique (CNRS)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), and Dumur, Frederic
Subjects: Materials science, Free Radicals, Polymers and Plastics, Radical polymerization, Near-Infrared Light, Triplet-Triplet Annihilation, 02 engineering and technology, 010402 general chemistry, Photochemistry, 7. Clean energy, 01 natural sciences, UpConversion, Polymerization, Materials Chemistry, Fourier transform infrared spectroscopy, [CHIM.MATE] Chemical Sciences/Material chemistry, Organic Chemistry, Photothermal effect, Near-infrared spectroscopy, Temperature, [CHIM.MATE]Chemical Sciences/Material chemistry, Photothermal therapy, 021001 nanoscience & nanotechnology, Photon upconversion, 0104 chemical sciences, Photopolymer, 0210 nano-technology
Abstract: International audience; NIR light induced polymerization has attracted more and more attention in the photopolymerization field due to the possibility to use safer and more penetrating wavelengths, reducing the hazardousness. Here, a novel perspective for the Free Radical Polymerization (FRP) of acrylate-based monomers based on Triplet-Triplet Annihilation UpConversion (TTA-UC) is proposed, avoiding the introduction of heavy metals, usually required in the TTA processes. Thermal imaging experiments and Real Time Fourier Transform Infrared (RT-FTIR) spectroscopy have been respectively used to record the temperature during NIR irradiation and measure the reactive function conversion. The competition between the TTA-UC and the NIR photothermal activation was investigated to compare the relative efficiency of both NIR processes. In view of the results obtained by the different methods, the photothermal effect seems to get the hupper hand over the photoactivation of the system.
Published: 2021
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84. Triphenylamine-based aldehydes: Photoinitiators for multiphoton polymerization

Author: Frédéric Dumur, Dimitra Ladika, Areti Mourka, Guillaume Noirbent, David Gray, Didier Gigmes, and Maria Farsari
Subjects: chemistry.chemical_classification, Benzaldehyde, chemistry.chemical_compound, Acrylate, Aniline, Photopolymer, Polymerization, chemistry, Substituent, Organic chemistry, Triphenylamine, Aldehyde
Abstract: Photopolymerization of (meth)acrylate-based formulations has become a widespread method for industry due to the high energy efficiency and low curing times of this technology. Various products from simple coatings to more complex applications such as additive manufacturing technologies are based on this versatile method. Common industrial radical photoinitiators are generally based on aromatic ketones. Benzaldehyde is an organic compound consisting of a benzene ring with a formyl substituent. It is the simplest aromatic aldehyde and one of the most industrially useful; for instance in the preparation of various aniline dyes, perfumes, flavorings, and pharmaceutics. Parallel to this, triphenylamines are extensively used for the design of dyes used for solar energy conversion. In this work, three triphenylamine derivatives bearing formyl groups are as a new substance class of multi-photon lithography photoinitiators. The photophysical properties of the PIs were investigated by UV−Vis abs
Published: 2021
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85. New Multifunctional Benzophenone-based Photoinitiators with High Migration Stability and the Application in 3D Printing

Author: Hong Chen, Damien Brunel, Jacques Lalevée, Fabrice Morlet-Savary, Guillaume Noirbent, Pu Xiao, Didier Gigmes, Shaohui Liu, Alexandre Mau, Bernadette Graff, Frédéric Dumur, Institut de Science des Matériaux de Mulhouse (IS2M), Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-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)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Australian National University (ANU), ANR-17-CE08-0054,VISICAT,Nouveaux Photocatalyseurs Redox pour la Synthèse sous Lumière Visible de Réseaux Polymères Interpénétrés(2017), Dumur, Frederic, Centre National de la Recherche Scientifique (CNRS)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, and Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)
Subjects: [CHIM.MATE] Chemical Sciences/Material chemistry, Sulfonium, Cationic polymerization, 02 engineering and technology, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, Photochemistry, Hydrogen atom abstraction, 01 natural sciences, 0104 chemical sciences, chemistry.chemical_compound, Photopolymer, chemistry, Polymerization, Materials Chemistry, Benzophenone, Molecule, General Materials Science, 0210 nano-technology, Photoinitiator
Abstract: In this paper, seven new photoinitiators based on the benzophenone scaffold are specifically designed for photopolymerization under mild conditions upon light-emitting diode (LED) irradiation, i.e. four benzophenone-triphenylamine photoinitiators (denoted as BT1–BT4) and three benzophenone-carbazole photoinitiators (denoted as BC1–BC3). Noticeably, these structures have never been reported in the literature except for BT4, so these molecules have been specifically designed for photopolymerization applications. Remarkably, various combinations of chemical groups were investigated in this work to determine the effects of the substitution patterns on their photoinitiation abilities. The formation of benzophenone-triphenylamine and benzophenone-carbazole hybrid structures not only contributes to red-shift of the absorption maxima but also strongly enhances their molar extinction coefficients. The different compounds showed high photoinitiation abilities upon irradiation with an LED@405 nm, and the free radical photopolymerization of acrylates and the cationic polymerization of epoxides could be promoted with high final function conversions (e.g. 77% for the BT3/iodonium salt/amine system in free radical photopolymerization). Remarkably, these new PIs are also able to sensitize sulfonium salts upon irradiation @405 nm. Markedly, because of the benzophenone moiety, a monocomponent Type II PI behavior could be observed, e.g. these compounds could initiate the polymerization alone. Remarkably, benzophenone-triphenylamine compounds BT2, BT3 and BT4 exhibited better hydrogen abstraction abilities as Type II photoinitiators than the benchmark and commercial photoinitiator 2-isopropylthioxanthone in the absence of amines as well as in the presence of amines. Furthermore, the interaction between the photoinitiators and the different additives was investigated by steady state photolysis and fluorescence quenching experiments. The free radical generation in the BT3/amine system was confirmed by the electron spin resonance-spin trapping technique, and the chemical mechanisms related to the polymerization efficiency are discussed. In addition, the migration stability of BT3 was investigated, which was excellent due to its high molecular weight and its trifunctional character. Finally, the three-component photoinitiating system based on BT3 was successfully applied in 3D printing and the 3D patterns showed a good spatial resolution.
Published: 2021
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86. NIR organic dyes as innovative tools for reprocessing/recycling of plastics: Benefits of the photothermal activation in the near-infrared range

Author: Guillaume Noirbent, Aurore Caron, Didier Gigmes, Jacques Lalevée, Valentin Launay, Frédéric Dumur, Institut de Science des Matériaux de Mulhouse (IS2M), Centre National de la Recherche Scientifique (CNRS)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-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)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), and Dumur, Frederic
Subjects: [CHIM.MATE] Chemical Sciences/Material chemistry, Range (particle radiation), Materials science, Nir light, Near-infrared spectroscopy, technology, industry, and agriculture, Nanotechnology, 02 engineering and technology, [CHIM.MATE]Chemical Sciences/Material chemistry, Photothermal therapy, 010402 general chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 01 natural sciences, 0104 chemical sciences, Electronic, Optical and Magnetic Materials, Biomaterials, Electrochemistry, 0210 nano-technology
Abstract: International audience; Photoinduced thermal polymerization upon Near-InfraRed (NIR) light has been recently reported in the literature as an efficient tool for polymer synthesis. In these different studies, a component capable to convert a NIR light into heat (called hereafter heater) was used in combination with a thermal initiator, promoting the Free-Radical Polymerization (FRP) of acrylate monomer. In this work, a completely different approach was developed since polymeric materials containing a very low amount of a stimuli-responsive compound were prepared by using a benchmark UV photoinitiator. As the stimuli-responsive compound, an
Published: 2021
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87. Allyloxy ketones as efficient photoinitiators with high migration stability in free radical polymerization and 3D printing

Author: Guillaume Noirbent, Damien Brunel, Didier Gigmes, Zhaofu Ding, Yangyang Xu, Pu Xiao, Jacques Lalevée, Frédéric Dumur, Bernadette Graff, Institut de Science des Matériaux de Mulhouse (IS2M), Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-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)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Australian National University (ANU), ANR-17-CE08-0054,VISICAT,Nouveaux Photocatalyseurs Redox pour la Synthèse sous Lumière Visible de Réseaux Polymères Interpénétrés(2017), Dumur, Frederic, Centre National de la Recherche Scientifique (CNRS)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, and Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)
Subjects: chemistry.chemical_classification, [CHIM.MATE] Chemical Sciences/Material chemistry, Ketone, Materials science, Process Chemistry and Technology, General Chemical Engineering, Radical polymerization, Cyclohexanone, 02 engineering and technology, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, Photochemistry, 01 natural sciences, 0104 chemical sciences, chemistry.chemical_compound, Monomer, Photopolymer, chemistry, Amine gas treating, Fourier transform infrared spectroscopy, Trimethylolpropane, 0210 nano-technology
Abstract: Five ketone derivatives (ketone-1~ketone-5) never synthesized in the literature and containing the same peripheral 1,3-bis(allyloxy)benzene substituting group but different central cyclohexanone cores were designed and proposed as high-performance photoinitiators for the free radical polymerization of acrylates under mild conditions. In combination with an amine and an iodonium salt (Iod), these ketones could initiate the photopolymerization of di(trimethylolpropane) tetraacrylate (TA), a tetrafunctional acrylates monomer, upon visible LED irradiation at room temperature in both thick films (1.4 mm) and thin films (25 μm) conditions. The distinct photopolymerization profiles of acrylates were studied by real time Fourier transform infrared spectroscopy, which indicated that the ketone-2/amine/Iod system could induce the highest final conversion of acrylates in thick films condition, while ketone-5/amine/Iod system could induce the highest final conversion of acrylates in thin films condition. Photoreactivity of ketone-2 and ketone-5 was systematically investigated by steady state photolysis and fluorescence quenching experiments in the presence of an amine and an iodonium salt, respectively. Moreover, eminent migration stability of ketones in photocured TA was observed. Finally, the ketone-2 and ketone-5-based three-component photoinitiating systems were applied for the laser writing experiments of TA, and macroscopically tridimensional patterns were fabricated with an excellent spatial resolution.
Published: 2021
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88. Bis-Chalcone Derivatives Derived from Natural Products as Near-UV/Visible Light Sensitive Photoinitiators for 3D/4D Printing

Author: Bernadette Graff, Pu Xiao, Didier Gigmes, Hong Chen, Guillaume Noirbent, Damien Brunel, Ke Sun, Jacques Lalevée, Yijun Zhang, Frédéric Dumur, Fabrice Morlet-Savary, Shaohui Liu, Institut de Science des Matériaux de Mulhouse (IS2M), Centre National de la Recherche Scientifique (CNRS)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Australian National University (ANU), Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-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)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Dumur, Frederic, and ANR-17-CE08-0054,VISICAT,Nouveaux Photocatalyseurs Redox pour la Synthèse sous Lumière Visible de Réseaux Polymères Interpénétrés(2017)
Subjects: [CHIM.MATE] Chemical Sciences/Material chemistry, Radical polymerization, Cationic polymerization, 02 engineering and technology, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, Photochemistry, 01 natural sciences, 0104 chemical sciences, chemistry.chemical_compound, Photopolymer, chemistry, Ferrocene, Pyridine, photopolymerization, Materials Chemistry, Alkoxy group, Thiophene, General Materials Science, Amine gas treating, 0210 nano-technology, Reversible shape memory, Bis-chalcones
Abstract: Four series of bis-chalcone compounds based on benzylpiperidinone, tetrahydrothiopyranone, pyridine or biphenyl central parts are designed and synthesized, enabling the development of ten bis-chalcones varying both by the central cores and by the substitution patterns (ortho, meta, para-positions) and the choice of the different groups attached to the peripheral substituents (alkoxy or allyloxy-substituted aromatic rings, thiophene, or ferrocene). In this series of ten bis-chalcones, eight of them were never synthesized before (i.e. only bis-chalcones 8 and 10 were already reported albeit never used as photoinitiators). These different dyes are proposed as new near-UV/visible light sensitive photoinitiators, in combination with an amine and an iodonium salt, to initiate the free radical photopolymerization (FRP) of PEG-diacrylate and the cationic photopolymerization (CP) of EPOX under LED@405 nm and LED@375 nm irradiation conditions. For the photopolymerization of acrylates carried out between thin films in laminate, all the bis-chalcones proposed in this work show higher photoinitiation abilities upon irradiation with a LED at 375 nm than at 405 nm, which is mainly due to their excellent light absorption properties in the near-UV region. Markedly, in contrast with the other two series of bis-chalcone compounds, pyridine-based bis-chalcones prove to be the most efficient photoinitiators, especially the bis-chalcones 5 and 9. Furthermore, all of them can also promote the cationic polymerization of epoxides upon LED irradiation at 375 nm, in the presence of an iodonium salt and an amine. More interestingly, some 3D patterns fabricated through the free radical polymerization of PEG-diacrylate demonstrate reversible swelling properties and shape-memory for access to 4D printing.
Published: 2021
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89. Synthesis, optical and electrochemical properties of a series of push-pull dyes based on the 2-(3-cyano-4,5,5- trimethylfuran-2(5H)-ylidene)malononitrile (TCF) acceptor

Author: Didier Gigmes, Thanh-Tuân Bui, Malek Nechab, Frédéric Dumur, Sébastien Péralta, Corentin Pigot, Guillaume Noirbent, Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Physico-chimie des Polymères et des Interfaces (LPPI), Fédération INSTITUT DES MATÉRIAUX DE CERGY-PONTOISE (I-MAT), CY Cergy Paris Université (CY)-CY Cergy Paris Université (CY), ANR-17-CE08-0010,DUALITY,Elaboration de réseaux covalents bidimensionnels nanoporeux dirigés par la surface(2017), ANR-17-CE08-0054,VISICAT,Nouveaux Photocatalyseurs Redox pour la Synthèse sous Lumière Visible de Réseaux Polymères Interpénétrés(2017), and Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU)
Subjects: Materials science, Polarity (physics), General Chemical Engineering, solvatochromism, Electron donor, 02 engineering and technology, 010402 general chemistry, Electrochemistry, Photochemistry, 01 natural sciences, chemistry.chemical_compound, Claisen-Schmidt condensation, Malononitrile, chemistry.chemical_classification, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Process Chemistry and Technology, Solvatochromism, near infrared absorption, visible absorption, TCF, Chromophore, Electron acceptor, 021001 nanoscience & nanotechnology, Acceptor, Push-pull dyes, 0104 chemical sciences, chemistry, 0210 nano-technology
Abstract: International audience; A series of chromophores was designed and synthesized using 2-(3-cyano-4,5,5-trimethylfuran-2 (5H)-ylidene) malononitrile (TCF) as the electron acceptor and differing from each other by the use of thirteen different electron donors. The different dyes were characterized for their optical and electrochemical properties and theoretical calculations were also carried out to support the experimental results. By changing the electron donor in the thirteen dyes, chromophores absorbing between 430 nm and 700 nm could be synthesized. Solvatochromism of the different dyes was analyzed in 23 solvents of different polarity and a positive solvatochromism was determined for all chromophores using the semi-empirical solvent polarity scales based on the Kamlet-Taft parameters (π *) or the Catalan parameters (SdP and SPP).
Published: 2021
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90. Mechanistic Investigation of ε-Thiono-Caprolactone Radical Polymerization: An Interesting Tool to Insert Weak Bonds into Poly(vinyl esters)

Author: Noémie Gil, Christopher M. Plummer, Pierre-Emmanuel Dufils, Yohann Guillaneuf, D. James Wilson, Catherine Lefay, Didier Gigmes, Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Solvay (France), and ANR-18-CE06-0014,CKAPART,Synthèse de particules dégradables par polymérisation radicalaire en milieu dispersé(2018)
Subjects: chemistry.chemical_classification, polythioester, Acrylate, Polymers and Plastics, 010405 organic chemistry, Chemistry, Process Chemistry and Technology, Organic Chemistry, Radical polymerization, poly(vinyl acetate), Polymer, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, chemistry.chemical_compound, Monomer, [CHIM.POLY]Chemical Sciences/Polymers, Polymerization, thionolactone, Polymer chemistry, Copolymer, Vinyl acetate, Caprolactone, degradable (co)polymers, radical ring-opening polymerization
Abstract: International audience; The incorporation of heteroatoms into the backbone of commodity polymers prepared by radical polymerization is an elegant way to confer (bio)degradability to such materials. This could be achieved via the radical ring-opening polymerization of cyclic monomers. Thionolactones were recently identified as promising comonomers for rROP but only reacting with activated monomers such as acrylate and acrylamide derivatives. Herein, we describe two thionolactone monomers, oxepane-2-thione i.e. εthiono-caprolactone (thCL) and 7-butyloxepane-2-thione, i.e ε-thiono-decalactone (thDL) capable of performing radical ringopening polymerization with less activated monomers such as vinyl acetate (VAc) to produce readily degradable copolymers via the insertion of thioester containing repeating units. A thorough mechanistic investigation was performed to understand the reactivity of the two cyclic monomers. We identified the initiation as the main parameter to perform the polymerization of such thionolactone monomers. In a specific case the poly(ε-thCL) homopolymer was successfully obtained. Concerning the copolymerization with vinyl acetate, a variety of polymerizations with differing feed ratios were performed, and the degradability of the copolymers via aminolysis examined by SEC. To demonstrate the usefulness of thionolactones a variety of block copolymers containing thioester linkages involving N,N-dimethylacrylamide and VAc were also prepared and degraded.
Published: 2021
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91. Click chemistry: an efficient tool to control the functionalization of metallic surfaces with alkyl chains possessing two reactive end groups

Author: Mathieu Koudia, Vikas Jangid, Gérard Berginc, David Duché, Chrystelle Lebouin, Anil Kumar Bharwal, Damien Brunel, Jean-Jacques Simon, Didier Gigmes, Thierry Buffeteau, Rose Marie Sauvage, Ludovic Escoubas, Mathieu Abel, Esteban Sanchez Adaime, Frédéric Dumur, Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Matériaux, de Microélectronique et des Nanosciences de Provence (IM2NP), Université de Toulon (UTLN)-Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU), Institut des Sciences Moléculaires (ISM), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Matériaux divisés, interfaces, réactivité, électrochimie (MADIREL), Direction générale de l'armement [Bagneux] (DGA), Thalès Optronique, Aix Marseille Université (AMU)-Université de Toulon (UTLN)-Centre National de la Recherche Scientifique (CNRS), and Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Materials science, General Physics and Astronomy, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Contact angle, chemistry.chemical_compound, XPS, Molecule, Alkyl, surface functionalization, chemistry.chemical_classification, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Surfaces and Interfaces, General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, Combinatorial chemistry, 0104 chemical sciences, Surfaces, Coatings and Films, PM-IRRAS, Ferrocene, chemistry, Click chemistry, Surface modification, Click Chemistry, Azide, Cyclic voltammetry, 0210 nano-technology
Abstract: International audience; Major challenges in the design of devices based on self-assembled monolayers (SAMs) standing in sandwich between two electrodes rely in SAMs of high quality and to simultaneously self-assemble them between two different electrodes, especially in case of Metal-Molecule-Metal junction devices. In this study, we demonstrate the synthesis and the characterization of two ferrocene-based functional molecules with two active thiol/thiol-acetate anchoring groups which could be used to bind with two different electrodes. To control the orientation of the molecules at the surface of the bottom electrode, a Copper catalysed Alkyne Azide Cycloaddition (CuAAC) (click chemistry) approach is applied on ultra-smooth template stripped gold substrates. Self-assembly of the two molecules could be obtained in two consecutive steps enabling us to control the orientation and the regularity of the SAMs. Cyclic voltammetry results shows that the SAMs obtained by mean of the two-step procedure are of high quality with more than 60% of the gold surface covered by molecules. We further investigated the SAMs by PM-IRRAS, XPS, ellipsometry and contact angle measurements to investigate the presence of functional groups, individual elements and succession of the click reaction on surface.
Published: 2021
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92. Dyes with tunable absorption properties from the visible to the near infrared range : 2,4,5,7-tetranitrofluorene (TNF) as a unique electron acceptor

Author: Malek Nechab, Corentin Pigot, Frédéric Dumur, Guillaume Noirbent, Sébastien Péralta, Didier Gigmes, Thanh-Tuân Bui, Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Physico-chimie des Polymères et des Interfaces (LPPI), Fédération INSTITUT DES MATÉRIAUX DE CERGY-PONTOISE (I-MAT), CY Cergy Paris Université (CY)-CY Cergy Paris Université (CY), ANR-17-CE08-0010,DUALITY,Elaboration de réseaux covalents bidimensionnels nanoporeux dirigés par la surface(2017), and ANR-17-CE08-0054,VISICAT,Nouveaux Photocatalyseurs Redox pour la Synthèse sous Lumière Visible de Réseaux Polymères Interpénétrés(2017)
Subjects: Materials science, Absorption spectroscopy, General Chemical Engineering, solvatochromism, TNF, Electron donor, 02 engineering and technology, 010402 general chemistry, Photochemistry, Electrochemistry, 01 natural sciences, chemistry.chemical_compound, chromophore, mechanosynthesis, Absorption (electromagnetic radiation), chemistry.chemical_classification, Range (particle radiation), [CHIM.ORGA]Chemical Sciences/Organic chemistry, Process Chemistry and Technology, Near-infrared spectroscopy, Solvatochromism, near infrared absorption, Electron acceptor, 021001 nanoscience & nanotechnology, Push-pull dyes, 0104 chemical sciences, chemistry, Knoevenagel reaction, tetranitrofluorene, 0210 nano-technology
Abstract: International audience; Fourteen dyes based on 2,4,5,7-tetranitrofluorene (TNF) as the electron acceptor have been designed and prepared in a one-step synthesis. By modifying the electron donor, optical properties of the dyes could be efficiently tuned and an absorption ranging between 450 nm and 700 nm could be determined by UV-visible absorption spectroscopy. To get a deeper insight into the optical properties, solvatochromism of the fourteen dyes has also been examined. For all dyes, a positive solvatochromism was determined using different solvent polarity scales such as the Kamlet-Taft and the Catalan empirical scales. Finally, electrochemical properties were also examined, and a comparison of the electrochemical and optical bandgaps could be established. Theoretical calculations were also performed to characterize the different dyes.
Published: 2021
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93. Total Knee Arthroplasty with a Ti6Al4V/PEEK Prosthesis on an Osteoarthritis Rat Model: Behavioral and Neurophysiological Analysis

Author: Mathieu Lecocq, Didier Gigmes, Patrick Decherchi, Marielle Eyraud, Sandrine Roffino, Jean-Marc Linares, Erick Dousset, Julien Chaves-Jacob, Thelma Coyle, Institut des Sciences du Mouvement Etienne Jules Marey (ISM), Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU), Matériaux divisés, interfaces, réactivité, électrochimie (MADIREL), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Radicalaire (ICR), and Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Male, Polymers, medicine.medical_treatment, [SDV.NEU.NB]Life Sciences [q-bio]/Neurons and Cognition [q-bio.NC]/Neurobiology, Total knee arthroplasty, lcsh:Medicine, Osteoarthritis, Knee Joint, Prosthesis, Polyethylene Glycols, H-Reflex, Weight-Bearing, Random Allocation, Postoperative Complications, 0302 clinical medicine, Peripheral Nerve Injuries, Arthroplasty, Replacement, Knee, lcsh:Science, Gait, Titanium, Multidisciplinary, Rehabilitation, Ketones, Osteoarthritis, Knee, Iodoacetic Acid, Knee Prosthesis, Femoral Nerve, musculoskeletal diseases, medicine.medical_specialty, Neurophysiology, Article, Benzophenones, 03 medical and health sciences, Physical medicine and rehabilitation, Femoral nerve, Alloys, medicine, Animals, Muscle, Skeletal, Bone, [SDV.IB.BIO]Life Sciences [q-bio]/Bioengineering/Biomaterials, Gait Disorders, Neurologic, 030203 arthritis & rheumatology, Afferent Pathways, business.industry, lcsh:R, Recovery of Function, medicine.disease, Arthroplasty, Rats, Disease Models, Animal, lcsh:Q, business, 030217 neurology & neurosurgery
Abstract: Arthroplasty is a surgical procedure to restore the function of the joint of patient suffering from knee osteoarthritis. However, postoperative functional deficits are reported even after a rehabilitation program. In order to determine the origin of functional deficits of patient suffering from knee osteoarthritis and total knee arthroplasty, we developed a rodent model including a chemically-induced-osteoarthritis and designed a knee prosthesis (Ti6Al4V/PEEK) biomechanically and anatomically adapted to rat knee joint. Dynamic Weight-Bearing, gait kinematics, H-reflex from vastus medialis muscle and activities from metabosensitive III and IV afferent fibers in femoral nerve were assessed at 1 and 3 months post-surgery. Results indicate that knee osteoarthritis altered considerably the responses of afferent fibers to their known activators (i.e., lactic acid and potassium chloride) and consequently their ability to modulate the spinal sensorimotor loop, although, paradoxically, motor deficits seemed relatively light. On the contrary, results indicate that, after the total knee arthroplasty, the afferent responses and the sensorimotor function were slightly altered but that motor deficits were more severe. We conclude that neural changes attested by the recovery of the metabosensitive afferent activity and the sensorimotor loop were induced when a total knee replacement was performed and that these changes may disrupt or delay the locomotor recovery.
Published: 2020
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94. Novel Push–Pull Dyes Derived from 1H-cyclopenta[b]naphthalene-1,3(2H)-dione as Versatile Photoinitiators for Photopolymerization and Their Related Applications: 3D Printing and Fabrication of Photocomposites

Author: Didier Gigmes, Pu Xiao, Malek Nechab, Corentin Pigot, Yijun Zhang, Ke Sun, Frédéric Dumur, Shaohui Liu, Jacques Lalevée, Fabrice Morlet-Savary, Bernadette Graff, Damien Brunel, Institut de Science des Matériaux de Mulhouse (IS2M), Centre National de la Recherche Scientifique (CNRS)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Australian National University (ANU), Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-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)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), and ANR-17-CE08-0010,DUALITY,Elaboration de réseaux covalents bidimensionnels nanoporeux dirigés par la surface(2017)
Subjects: Materials science, Tertiary amine, Radical polymerization, naphthalene-1,3-dione, 02 engineering and technology, naphthalene-1, lcsh:Chemical technology, 010402 general chemistry, Photochemistry, 01 natural sciences, Catalysis, lcsh:Chemistry, chemistry.chemical_compound, 3-dione, lcsh:TP1-1185, push-pull dye, Physical and Theoretical Chemistry, chemistry.chemical_classification, free radical polymerization, LED, three-component system, [CHIM.MATE]Chemical Sciences/Material chemistry, 3D printing, Electron acceptor, Chromophore, 021001 nanoscience & nanotechnology, 3. Good health, 0104 chemical sciences, Light intensity, Monomer, Photopolymer, lcsh:QD1-999, chemistry, Polymerization, push–pull dye, 0210 nano-technology
Abstract: A series of eleven push&ndash, pull chromophores with specific structures have been designed for the free radical polymerization of acrylates, but also for the fabrication of photocomposites and 3D-printed structures. New photoinitiating systems comprising the different push&ndash, pull dyes showed excellent photochemical reactivities at 405 nm. Notably, polymerization reactions could be initiated with light-emitting diodes (LEDs) which constitute a unique opportunity to promote the free radical polymerization under mild conditions, i.e., low light intensity (e.g., sunlight) and under air. Photopolymerization is an active research field, and push&ndash, pull dyes have already been investigated for this purpose. Besides, it remains of crucial interest to investigate new reactive structures capable of efficiently initiating photopolymerization reactions. The plausible potential of these structures to act as efficient photoinitiators in vat photopolymerization (or 3D printing) and fabrication of photocomposites prompts us to select eleven new push&ndash, pull dyes to design multi-component photoinitiating systems activable with LEDs emitting at 405 nm. Precisely, a tertiary amine, i.e., ethyl dimethylaminobenzoate (EDB) used as an electron/hydrogen donor and an iodonium salt used as an electron acceptor were selected to behave as powerful co-initiators to construct three-component photoinitiating systems (PISs) with the different push&ndash, pull dyes. Among these new PISs, dye 8 and 9-based PISs could efficiently promote the free radical photopolymerization of acrylates upon exposure to a LED emitting at 405 nm also upon sunlight irradiation, highlighting their huge performance. Photoinitiating abilities could be explained on the basis of steady state photolysis experiments. Fluorescence measurements and electron spin resonance (ESR) spin-trapping experiments were also performed to obtain a deeper insight into the chemical mechanisms supporting the polymerization reaction and determine the way the initiating species, i.e., the radicals, are observed. Finally, two investigated dye-based PISs were applied to the fabrications of photocomposites. Three-dimensional patterns with excellent spatial resolutions were generated by the laser writing technique to identify the effects of photopolymerization of acrylates both in the absence and presence of fillers (silica). Interestingly, comparison between the 3D objects fabricated by the PISs/monomer systems and the PISs/monomer/filler photocomposites indicates that the newly designed photocomposites are suitable for practical applications.
Published: 2020
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95. Novel Bulky Lithium Salts And Their Electrolytes For Safer Solid-state Lithium Metal Battery

Author: Didier Devaux, Renaud Bouchet, Fannie Alloin, Thi Khanh Ly Nguyen, Didier Gigmes, Clémence Yver, Trang N. T. Phan, Matériaux Interfaces ELectrochimie (MIEL), Laboratoire d'Electrochimie et de Physico-chimie des Matériaux et des Interfaces (LEPMI), Institut de Chimie du CNRS (INC)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA), Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Nguyen, Thi Khanh Ly
Subjects: Battery (electricity), [CHIM.MATE] Chemical Sciences/Material chemistry, Materials science, chemistry, SAFER, Inorganic chemistry, Solid-state, chemistry.chemical_element, Lithium, Electrolyte, [CHIM.MATE]Chemical Sciences/Material chemistry, Lithium metal, ComputingMilieux_MISCELLANEOUS
Abstract: In recent years, Lithium metal batteries (LMBs) have gained great interests thanks to their high capacity that can respond to the continuous increasing need for energy storage and device. The design and development of new solid-state electrolytes e.g. polymer based ones (SPEs) then became crucial towards intrinsically safer LMBs. A successful electrolyte candidate needs to fulfill several requirements such as high transference number (tLi +) and a compromise between two antagonist properties: conductivity and mechanical properties. Most researches focused on the synthesis of single-ion conducting electrolytes as a strategy to overcome these difficulties1,2. However, these materials often require complicated and delicate chemistry and their conductivity often remains low (σ < 10-5 S/cm at 60°C). An alternative promising route that received much less attention is the development of bulky Lithium salts with macroanion. The bulky anion reduces ion paring and salts aggregation and present negligible mobility compared to Lithium cation resulting in higher transference number3. In this work, we present a new macroanion based on Polyhedral Oligomeric Silsesquioxane (POSS) grafted with either polyethylene oxide oligomers (PEG) and/or Lithium sulfonyl (trifluoromethanesulfonyl) imide (LiTFSI) denoted as POSS-LiTFSI-PEG or POSS-LiTFSI respectively. Thus, SPE has been prepared with a reference high molecular weight polyethylene oxide at different OE/Li ratio from 10 to 25. This new concept of bulky multi-anion based on TFSI moieties allows a complete salt dissociation, an enhancement of the mechanical properties thanks to the presence of the inorganic POSS multi anions that play the role of nano fillers, and finally, a strong increase of the Li+ transference number (tLi+>0,55), which opens many perspectives. The cycling performance obtained in both Lithium symmetric cells and LMBs prototypes will be also presented. References (1) Bouchet, R.; Maria, S.; Meziane, R.; Aboulaich, A.; Lienafa, L.; Bonnet, J.-P. P.; Phan, T. N. T.; Bertin, D.; Gigmes, D.; Devaux, D.; et al. Single-Ion BAB Triblock Copolymers as Highly Efficient Electrolytes for Lithium-Metal Batteries. Nat. Mater. 2013, 12 (5), 452–457. (2) Zhang, H.; Li, C.; Piszcz, M.; Coya, E.; Rojo, T.; Rodriguez-Martinez, L. M.; Armand, M.; Zhou, Z. Single Lithium-Ion Conducting Solid Polymer Electrolytes: Advances and Perspectives. Chem. Soc. Rev. 2017, 46 (3), 797–815. (3) Chinnam, P. R.; Wunder, S. L. Polyoctahedral Silsesquioxane-Nanoparticle Electrolytes for Lithium Batteries: POSS-Lithium Salts and POSS-PEGs. Chem. Mater. 2011, 23 (23), 5111–5121. Figure 1
Published: 2020

96. Novel ketone derivatives based photoinitiating systems for free radical polymerization under mild conditions and 3D printing

Author: Guillaume Noirbent, Bernadette Graff, Didier Gigmes, Jacques Lalevée, Yangyang Xu, Frédéric Dumur, Zhaofu Ding, Damien Brunel, Pu Xiao, Institut de Science des Matériaux de Mulhouse (IS2M), Centre National de la Recherche Scientifique (CNRS)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Australian National University (ANU), Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-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)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Dumur, Frederic, and ANR-17-CE08-0054,VISICAT,Nouveaux Photocatalyseurs Redox pour la Synthèse sous Lumière Visible de Réseaux Polymères Interpénétrés(2017)
Subjects: chemistry.chemical_classification, Acrylate, [CHIM.MATE] Chemical Sciences/Material chemistry, Ketone, Materials science, Polymers and Plastics, Organic Chemistry, Radical polymerization, Bioengineering, 02 engineering and technology, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, Photochemistry, 01 natural sciences, Biochemistry, 0104 chemical sciences, chemistry.chemical_compound, Photopolymer, chemistry, Photosensitivity, Polymerization, Amine gas treating, Trimethylolpropane, 0210 nano-technology
Abstract: Photopolymerization of acrylates under mild conditions is promising not only for academic research but also for industrial applications. However, it still remains a huge challenge to develop effective photoinitiators or photoinitiating systems for the free radical polymerization of acrylates under visible light-emitting diode (LED) irradiation. In this work, twelve novel ketone derivatives containing either tertiary amines or anthracenes as peripheral substituting groups (noted as Ami-1–Ami-6 and Anth-1–Anth-6) were elaborately synthesized and proposed for the polymerization of di(trimethylolpropane) tetraacrylate (TA), a tetrafunctional polyether acrylate, under both thin and thick film conditions under LED@405 nm irradiation. Remarkably, eight of the selected ketones (Ami-2, Ami-6, Anth-1–Anth-6) had never been synthesized before. In combination with an amine and/or an iodonium salt (Iod), these ketones could form distinct photoinitiating systems, among which the Ami-2/amine/Iod system could lead to the highest final conversion of acrylates under the thick film (∼1.4 mm) conditions while the Ami-6/amine/Iod system could induce the highest final conversion of acrylates under the thin film (∼25 μm) conditions. The photosensitivity of Ami-2 and Ami-6 was systematically investigated by steady state photolysis and fluorescence quenching experiments. Finally, the photocuring 3D printing technique was applied to TA, and both Ami-2- and Ami-6-based photoinitiating systems could be used to fabricate macroscopic 3D patterns with excellent spatial resolution.
Published: 2020
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97. Polyesters by a Radical Pathway: Rationalization of the Cyclic Ketene Acetal Efficiency

Author: Didier Siri, Catherine Lefay, Yohann Guillaneuf, Christopher M. Plummer, Didier Gigmes, Noémie Gil, Antoine Tardy, Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and ANR-18-CE06-0014,CKAPART,Synthèse de particules dégradables par polymérisation radicalaire en milieu dispersé(2018)
Subjects: 010405 organic chemistry, Radical polymerization, Acetal, Ketene, General Chemistry, General Medicine, 010402 general chemistry, Combinatorial chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, Polyester, chemistry.chemical_compound, Monomer, chemistry, Polymerization, Copolymer, [CHIM]Chemical Sciences, Major complication, ComputingMilieux_MISCELLANEOUS
Abstract: Radical ring-opening polymerization (rROP) of cyclic ketene acetals (CKAs) combines the advantages of both ring-opening polymerization and radical polymerization thereby allowing the robust production of polyesters coupled with the mild polymerization conditions of a radical process. rROP was recently rejuvenated by the possibility to copolymerize CKAs with classic vinyl monomers leading to the insertion of cleavable functionality into a vinyl-based copolymer backbone and thus imparting (bio)degradability. Such materials are suitable for a large scope of applications, particularly within the biomedical field. The competition between the ring-opening and ring-retaining propagation routes is a major complication in the development of efficient CKA monomers, ultimately leading to the use of only four monomers that are known to completely ring-open under all experimental conditions. In this article we investigate the radical ring-opening polymerization of model CKA monomers and demonstrate by the combination of DFT calculations and kinetic modeling using PREDICI software that we are now able to predict in silico the ring-opening ability of CKA monomers.
Published: 2020
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98. Rectifying antennas for energy harvesting from the microwaves to visible light: A review

Author: Clément A. Reynaud, Gérard Berginc, David Duché, Chrystelle Lebouin, Jörg Ackermann, Jean-Jacques Simon, Christian A. Nijhuis, Olivier Margeat, Didier Gigmes, Ludovic Escoubas, Frédéric Dumur, Vikas Jangid, Estéban Sanchez-Adaime, Damien Brunel, Institut des Matériaux, de Microélectronique et des Nanosciences de Provence (IM2NP), Université de Toulon (UTLN)-Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU), Centre Interdisciplinaire de Nanoscience de Marseille (CINaM), Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU), Matériaux divisés, interfaces, réactivité, électrochimie (MADIREL), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Radicalaire (ICR), Thales LAS France, Department of Chemical and Biomolecular Engineering, National University of Singapore, National University of Singapore (NUS), Aix Marseille Université (AMU)-Université de Toulon (UTLN)-Centre National de la Recherche Scientifique (CNRS), and Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Rectenna, Fabrication, Terahertz radiation, Infrared, Computer science, 02 engineering and technology, 7. Clean energy, 01 natural sciences, law.invention, 010309 optics, Rectifier, law, 0103 physical sciences, Rectifying antenna, Electrical and Electronic Engineering, Statistical and Nonlinear Physics, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Engineering physics, Atomic and Molecular Physics, and Optics, Electronic, Optical and Magnetic Materials, Plasmonics, Antenna (radio), Photolithography, Molecular Electronics, 0210 nano-technology, Energy harvesting
Abstract: Rectifying antennas are often prensented as a potentiel technological breakthrough for energy harvesting. First theorized in the 1970’s, the downsizing of an antenna coupled with a rectifier has become technologically achievable with the progresses of fabrication techniques such as electron beam or photolithography. However, reaching infrared or visible region of the electromagnetic spectra still entails challenges on the integration of a rectifier operating in the terahertz range. New bottom up approaches are likely to bring a promising solution to this issue. To improve our understanding of the key points of rectifying antennas’ design for the infrared and visible light, and the challenges of device fabrication, this work reviews the progresses of this technology, going back from the first historical RF energy harvesting systems and covering the most innovative trends to this date.
Published: 2020
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99. Selective Bond Cleavage in Informational Poly(Alkoxyamine Phosphodiester)s

Author: Jean-Louis Clément, Didier Gigmes, Gianni Cavallo, Laurence Charles, Jean-François Lutz, Institut Charles Sadron (ICS), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Lutz, Jean-François, Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), and ANR-16-CE29-0004,00111001,Synthèse et séquençage de macromolécules contenant de l'information(2016)
Subjects: Nitroxide mediated radical polymerization, [CHIM.POLY] Chemical Sciences/Polymers, Polymers and Plastics, Polymers, Electrospray ionization, 02 engineering and technology, 010402 general chemistry, Tandem mass spectrometry, 01 natural sciences, Dissociation (chemistry), Fragmentation (mass spectrometry), Polymer chemistry, Materials Chemistry, Amines, Bond cleavage, chemistry.chemical_classification, Molecular Structure, Chemistry, Organic Chemistry, Polymer, 021001 nanoscience & nanotechnology, Organophosphates, 0104 chemical sciences, [CHIM.POLY]Chemical Sciences/Polymers, Phosphodiester bond, 0210 nano-technology
Abstract: International audience; The collision-induced dissociation (CID) of sequence-defined poly(alkoxyamine phosphodiester)s was studied by electrospray ionization mass spectrometry. These informational polymers were synthesized using three different nitroxide building blocks, namely proxyl-, SG1-and TEMPO-derivatives. For a polymer containing TEMPO-and SG1based main chain alkoxyamines, it was found that both types of alkoxyamines break in CID tandem mass spectrometry (MS/MS). However, SG1-sites are preferentially cleaved and this predominance can be increased by reducing collision energy, even though selective bond fragmentation was not observed. On the other hand, for a polymer containing proxyl-and SG1alkoxyamines, selective bond cleavage was observed at all studied collision energies. The SG1alkoxyamines can be first cleaved in MS/MS conditions and secondly the proxyl-alkoxyamines in pseudo-MS 3 conditions. These results open up interesting new avenues for the design of readable, erasable or programmable informational polymers.
Published: 2020
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100. New push-pull dyes based on 2-(3-oxo-2,3-dihydro-1H-cyclopenta[b]naphthalen-1-ylidene)malononitrile: An amine-directed synthesis

Author: Sébastien Péralta, Guillaume Noirbent, Sylvain Duval, Frédéric Dumur, Pierre-Henri Aubert, Thanh-Tuan Bui, Malek Nechab, Corentin Pigot, Didier Gigmes, Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Physico-chimie des Polymères et des Interfaces (LPPI), Fédération INSTITUT DES MATÉRIAUX DE CERGY-PONTOISE (I-MAT), Université de Cergy Pontoise (UCP), Université Paris-Seine-Université Paris-Seine-Université de Cergy Pontoise (UCP), Université Paris-Seine-Université Paris-Seine, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), ANR-17-CE08-0010,DUALITY,Elaboration de réseaux covalents bidimensionnels nanoporeux dirigés par la surface(2017), ANR-17-CE08-0054,VISICAT,Nouveaux Photocatalyseurs Redox pour la Synthèse sous Lumière Visible de Réseaux Polymères Interpénétrés(2017), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU), and CY Cergy Paris Université (CY)-CY Cergy Paris Université (CY)
Subjects: chemistry.chemical_classification, Process Chemistry and Technology, General Chemical Engineering, Aromatization, 02 engineering and technology, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Aldehyde, Medicinal chemistry, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Nucleophile, [CHIM]Chemical Sciences, Knoevenagel condensation, Amine gas treating, Piperidine, 0210 nano-technology, Derivative (chemistry), ComputingMilieux_MISCELLANEOUS, Malononitrile
Abstract: International audience; A series of twelve dyes have been designed using 2-(3-oxo-2,3-dihydro-1H-cyclopenta[b]naphthalen-1-yli-dene)malononitrile as the electron acceptor. While using piperidine as a classical base for the Knoevenagel reaction , a nucleophilic attack of the amine on the formed push-pull chromophore occurred, producing an azaflu-orenone derivative. By varying the amine, a series of azafluorenones could be obtained. By using an aldehyde of extended conjugation, a spontaneous aromatization following the cyclization reaction could also be demonstrated. The optical, electrochemical properties of the different dyes were examined. Theoretical calculations were also carried out to support the experimental results.
Published: 2020
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