Search

Your search keyword '"Vincent Ladmiral"' showing total 162 results
Start Over Author "Vincent Ladmiral"
162 results on '"Vincent Ladmiral"'

1. 4-Vinyl Guaiacol: A Key Intermediate for Biobased Polymers

Author

Elena Rigo, Cédric Totée, Vincent Ladmiral, Sylvain Caillol, and Patrick Lacroix-Desmazes

Subjects
biobased, guaiacol, polymers, radical polymerization, Organic chemistry, QD241-441
Abstract

In order to contribute to the shift from petro-based chemistry to biobased chemistry, necessary to minimize the environmental impacts of the chemical industry, 2-methoxy-4-vinylphenol (4-vinyl guaiacol, 4VG) was used to synthesize a platform of biobased monomers. Thus, nine biobased monomers were successfully prepared. The synthesis procedures were investigated through the green metrics calculations in order to quantify the sustainability of our approaches. Their radical homopolymerization in toluene solution initiated by 2,2′-azobis(2-methylpropionitrile) (AIBN) was studied and the effect of residual 4VG as a radical inhibitor on the kinetics of polymerization was also explored. The new homopolymers were characterized by proton nuclear magnetic resonance (1H-NMR) spectroscopy, size exclusion chromatography and thermal analyses (dynamical scanning calorimetry DSC, thermal gravimetric analysis TGA). By varying the length of the alkyl ester or ether group of the 4VG derivatives, homopolymers with Tg ranging from 117 °C down to 5 °C were obtained. These new biobased monomers could be implemented in radical copolymerization as substitutes to petro-based monomers to decrease the carbon footprint of the resulting copolymers for various applications.

Published
2024
Full Text
View/download PDF

2. Photochemical [2+2] Cycloaddition of Biobased Latexes for Composites with Microfibrillated Cellulose

Author

Sara Dalle Vacche, Samantha Molina-Gutierrez, Vincent Ladmiral, Sylvain Caillol, Patrick Lacroix-Desmazes, and Roberta Bongiovanni

Subjects
Chemical engineering, TP155-156, Computer engineering. Computer hardware, TK7885-7895
Abstract

A biobased latex was obtained by copolymerization in emulsion of ethoxy dihydroeugenyl methacrylate (EDMA) and coumarin methacrylate (CMA). Thin films of poly(EDMA-co-CMA) were irradiated with UV light at 365 nm, to promote the [2+2] photocycloaddition reaction of the coumarin moieties. The advancement of the reaction was followed by monitoring the intensity of the UV-Vis absorbance at 320 nm, characteristic of coumarin, after different irradiation times. Complete dimerization of the coumarin moieties could be achieved. A microfibrillated cellulose (MFC) reinforcement was added to the poly(EDMA-co-CMA) latexes to prepare composite materials. The permeability of the composite films to oxygen, before and after crosslinking, was assessed. For the non-crosslinked films, increasing the cellulose content from 5 wt% to 30 wt% decreased the oxygen transmission rate (OTR) by approximately 70%. When 1 wt% CMA moieties were present in the polymer backbone the OTR was approximately 50 % lower with respect to poly(EDMA) composites. A further slight decrease of permeability was observed upon crosslinking of the composite poly(EDMA-co-CMA)/MFC films.

Published
2022
Full Text
View/download PDF

3. Dihydroxyacetone: A User Guide for a Challenging Bio-Based Synthon

Author

Léo Bricotte, Kamel Chougrani, Valérie Alard, Vincent Ladmiral, and Sylvain Caillol

Subjects
bio-based, carbohydrates, DHA, monomer, polymer, glycerol, Organic chemistry, QD241-441
Abstract

1,3-dihydroxyacetone (DHA) is an underrated bio-based synthon, with a broad range of reactivities. It is produced for the revalorization of glycerol, a major side-product of the growing biodiesel industry. The overwhelming majority of DHA produced worldwide is intended for application as a self-tanning agent in cosmetic formulations. This review provides an overview of the discovery, physical and chemical properties of DHA, and of its industrial production routes from glycerol. Microbial fermentation is the only industrial-scaled route but advances in electrooxidation and aerobic oxidation are also reported. This review focuses on the plurality of reactivities of DHA to help chemists interested in bio-based building blocks see the potential of DHA for this application. The handling of DHA is delicate as it can undergo dimerization as well as isomerization reactions in aqueous solutions at room temperature. DHA can also be involved in further side-reactions, yielding original side-products, as well as compounds of interest. If this peculiar reactivity was harnessed, DHA could help address current sustainability challenges encountered in the synthesis of speciality polymers, ranging from biocompatible polymers to innovative polymers with cutting-edge properties and improved biodegradability.

Published
2023
Full Text
View/download PDF

4. Original Fluorinated Non-Isocyanate Polyhydroxyurethanes

Author

Lolwa Haydar, Wassim El Malti, Vincent Ladmiral, Ali Alaaeddine, and Bruno Ameduri

Subjects
aminolysis, cyclocarbonates, fluorinated polymers, polyhydroxyurethanes, SDG3, Organic chemistry, QD241-441
Abstract

New fluorinated polyhydroxyurethanes (FPHUs) with various molar weights were synthesized via the polyaddition reaction of a fluorinated telechelic bis(cyclocarbonate) (bis-CC) with a diamine. The fluorinated bis-CC was initially synthesized by carbonylation of a fluorinated diepoxide, 1,4-bis(2′,3′-epoxypropyl)perfluorobutane, in the presence of LiBr catalyst, in high yield. Then, several reaction conditions were optimized through the model reactions of the fluorinated bis-CC with hexylamine. Subsequently, fluorinated polymers bearing hydroxyurethane moieties (FPHUs) were prepared by reacting the bis-CC with different hexamethylenediamine amounts in bulk at 80 °C and the presence of a catalyst. The chemoselective polymerization reaction yielded three isomers bearing primary and secondary hydroxyl groups in 61–82% yield. The synthesized fluorinated CCs and the corresponding FPHUs were characterized by 1H, 19F, and 13C NMR spectroscopy. They were compared to their hydrogenated homologues synthesized in similar conditions. The gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA) data of the FPHUs revealed a higher molar mass and a slight increase in glass transition and decomposition temperatures compared to those of the PHUs.

Published
2023
Full Text
View/download PDF

5. Thia-Michael Reaction: The Route to Promising Covalent Adaptable Networks

Author

Dimitri Berne, Vincent Ladmiral, Eric Leclerc, and Sylvain Caillol

Subjects
Michael, vitrimers, covalent adaptable network, thia-Michael, Organic chemistry, QD241-441
Abstract

While the Michael addition has been employed for more than 130 years for the synthesis of a vast diversity of compounds, the reversibility of this reaction when heteronucleophiles are involved has been generally less considered. First applied to medicinal chemistry, the reversible character of the hetero-Michael reactions has recently been explored for the synthesis of Covalent Adaptable Networks (CANs), in particular the thia-Michael reaction and more recently the aza-Michael reaction. In these cross-linked networks, exchange reactions take place between two Michael adducts by successive dissociation and association steps. In order to understand and precisely control the exchange in these CANs, it is necessary to get an insight into the critical parameters influencing the Michael addition and the dissociation rates of Michael adducts by reconsidering previous studies on these matters. This review presents the progress in the understanding of the thia-Michael reaction over the years as well as the latest developments and plausible future directions to prepare CANs based on this reaction. The potential of aza-Michael reaction for CANs application is highlighted in a specific section with comparison with thia-Michael-based CANs.

Published
2022
Full Text
View/download PDF

6. Crystal structure of pentacarbonyl(2,2-difluoropropanethioato-κS)manganese(I)

Author

Jean-Claude Daran, Roberto Morales-Cerrada, Christophe Fliedel, Florence Gayet, Vincent Ladmiral, Bruno Ameduri, and Rinaldo Poli

Subjects
crystal structure, Mn(CO)5 derivatives, Mn-S bond, intermolecular contacts, Crystallography, QD901-999
Abstract

The title compound, [Mn{SC(O)CF2CH3}(CO)5], has been isolated as a by-product during the reaction of K[Mn(CO)5] with CH3CF2COCl. It is built up from a difluoromethylpropanethioate bonded to an Mn(CO)5 moiety through the S atom. The Mn atom has an almost perfect octahedral coordination sphere. It is one of the rare examples of compounds containing the (CO)5MnS—C fragment. In the crystal, the methyl group occupies a pocket surrounded by the O atoms of three carbonyl groups of the Mn(CO)5 moiety; however, the H...O distances are rather long. These interactions lead to the formation of layers lying parallel to (101), which enclose R44(15) and R44(16) ring motifs. The CF2 group is disordered over two sets of sites with occupancies of 0.849 (3) and 0.151 (3).

Published
2019
Full Text
View/download PDF

7. Stimuli-Responsive Thiomorpholine Oxide-Derived Polymers with Tailored Hydrophilicity and Hemocompatible Properties

Author

Laura Vasilica Arsenie, Franziska Hausig, Carolin Kellner, Johannes C. Brendel, Patrick Lacroix-Desmazes, Vincent Ladmiral, and Sylvain Catrouillet

Subjects
pH-responsive polymers, temperature responsive polymers, thiomorpholine oxide, RAFT, cytotoxicity, Organic chemistry, QD241-441
Abstract

Thermo-responsive hydrophilic polymers, including those showing tuneable lower critical solution temperature (LCST), represent a continuous subject of exploration for a variety of applications, but particularly in nanomedicine. Since biological pH changes can inform the organism about the presence of disequilibrium or diseases, the development of dual LCST/pH-responsive hydrophilic polymers with biological potential is an attractive subject in polymer science. Here, we present a novel polymer featuring LCST/pH double responsiveness. The monomer ethylthiomorpholine oxide methacrylate (THOXMA) can be polymerised via the RAFT process to obtain well-defined polymers. Copolymers with hydroxyethyl methacrylate (HEMA) were prepared, which allowed the tuning of the LCST behaviour of the polymers. Both, the LCST behaviour and pH responsiveness of hydrophilic PTHOXMA were tested by following the evolution of particle size by dynamic light scattering (DLS). In weak and strong alkaline conditions, cloud points ranged between 40–60 °C, while in acidic medium no LCST was found due to the protonation of the amine of the THOX moieties. Additional cytotoxicity assays confirmed a high biocompatibility of PTHOXMA and haemolysis and aggregation assays proved that the thiomorpholine oxide-derived polymers did not cause aggregation or lysis of red blood cells. These preliminary results bode well for the use of PTHOXMA as smart material in biological applications.

Published
2022
Full Text
View/download PDF

8. Biobased Composites by Photoinduced Polymerization of Cardanol Methacrylate with Microfibrillated Cellulose

Author

Alessandra Vitale, Samantha Molina-Gutiérrez, W. S. Jennifer Li, Sylvain Caillol, Vincent Ladmiral, Patrick Lacroix-Desmazes, and Sara Dalle Vacche

Subjects
photoinduced polymerization, biobased composites, cardanol methacrylate, microfibrillated cellulose, biobased polymers, Technology, Electrical engineering. Electronics. Nuclear engineering, TK1-9971, Engineering (General). Civil engineering (General), TA1-2040, Microscopy, QH201-278.5, Descriptive and experimental mechanics, QC120-168.85
Abstract

Biobased monomers and green processes are key to producing sustainable materials. Cardanol, an aromatic compound obtained from cashew nut shells, may be conveniently functionalized, e.g., with epoxy or (meth)acrylate groups, to replace petroleum-based monomers. Photoinduced polymerization is recognized as a sustainable process, less energy intensive than thermal curing; however, cardanol-based UV-cured polymers have relatively low thermomechanical properties, making them mostly suitable as reactive diluents or in non-structural applications such as coatings. It is therefore convenient to combine them with biobased reinforcements, such as microfibrillated cellulose (MFC), to obtain composites with good mechanical properties. In this work a cardanol-based methacrylate monomer was photopolymerized in the presence of MFC to yield self-standing, flexible, and relatively transparent films with high thermal stability. The polymerization process was completed within few minutes even in the presence of filler, and the cellulosic filler was not affected by the photopolymerization process.

Published
2022
Full Text
View/download PDF

9. Semi-Fluorinated Di and Triblock Copolymer Nano-Objects Prepared via RAFT Alcoholic Dispersion Polymerization (PISA)

Author

Gregoire Desnos, Adrien Rubio, Chaimaa Gomri, Mathias Gravelle, Vincent Ladmiral, and Mona Semsarilar

Subjects
semi-fluorinated, RAFT, PISA, dispersion polymerization, self-assembly, Organic chemistry, QD241-441
Abstract

A set of well-defined amphiphilic, semi-fluorinated di and triblock copolymers were synthesized via polymerization-induced self-assembly (PISA) under alcoholic dispersion polymerization conditions. This study investigates the influence of the length, nature and position of the solvophobic semi-fluorinated block. A poly(N,N-dimethylaminoethyl methacrylate) was used as the stabilizing block to prepare the di and tri block copolymer nano-objects via reversible addition-fragmentation chain transfer (RAFT) controlled dispersion polymerization at 70 °C in ethanol. Benzylmethacrylate (BzMA) and semi-fluorinated methacrylates and acrylates with 7 (heptafluorobutyl methacrylate (HFBMA)), 13 (heneicosafluorododecyl methacrylate (HCFDDMA)) and 21 (tridecafluorooctyl acrylate (TDFOA)) fluorine atoms were used as monomers for the core-forming blocks. The RAFT polymerization of these semi-fluorinated monomers was monitored by SEC and 1H NMR. The evolution of the self-assembled morphologies was investigated by transmission electron microscopy (TEM). The results demonstrate that the order of the blocks and the number of fluorine atoms influence the microphase segregation of the core-forming blocks and the final morphology of the nano-objects.

Published
2021
Full Text
View/download PDF

10. Evaluation of Self-Assembly Pathways to Control Crystallization-Driven Self-Assembly of a Semicrystalline P(VDF-co-HFP)-b-PEG-b-P(VDF-co-HFP) Triblock Copolymer

Author

Enrique Folgado, Matthias Mayor, Vincent Ladmiral, and Mona Semsarilar

Subjects
PVDF, fluoropolymer, self-assembly, CDSA, Organic chemistry, QD241-441
Abstract

To date, amphiphilic block copolymers (BCPs) containing poly(vinylidene fluoride-co-hexafluoropropene) (P(VDF-co-HFP)) copolymers are rare. At moderate content of HFP, this fluorocopolymer remains semicrystalline and is able to crystallize. Amphiphilic BCPs, containing a P(VDF-co-HFP) segment could, thus be appealing for the preparation of self-assembled block copolymer morphologies through crystallization-driven self-assembly (CDSA) in selective solvents. Here the synthesis, characterization by 1H and 19F NMR spectroscopies, GPC, TGA, DSC, and XRD; and the self-assembly behavior of a P(VDF-co-HFP)-b-PEG-b-P(VDF-co-HFP) triblock copolymer were studied. The well-defined ABA amphiphilic fluorinated triblock copolymer was self-assembled into nano-objects by varying a series of key parameters such as the solvent and the non -solvent, the self-assembly protocols, and the temperature. A large range of morphologies such as spherical, square, rectangular, fiber-like, and platelet structures with sizes ranging from a few nanometers to micrometers was obtained depending on the self-assembly protocols and solvents systems used. The temperature-induced crystallization-driven self-assembly (TI-CDSA) protocol allowed some control over the shape and size of some of the morphologies.

Published
2020
Full Text
View/download PDF

11. Photoinduced Polymerization of Eugenol-Derived Methacrylates

Author

Samantha Molina-Gutiérrez, Sara Dalle Vacche, Alessandra Vitale, Vincent Ladmiral, Sylvain Caillol, Roberta Bongiovanni, and Patrick Lacroix-Desmazes

Subjects
biobased monomer, photoinduced-polymerization, eugenol-derived methacrylate, Organic chemistry, QD241-441
Abstract

Biobased monomers have been used to replace their petroleum counterparts in the synthesis of polymers that are aimed at different applications. However, environmentally friendly polymerization processes are also essential to guarantee greener materials. Thus, photoinduced polymerization, which is low-energy consuming and solvent-free, rises as a suitable option. In this work, eugenol-, isoeugenol-, and dihydroeugenol-derived methacrylates are employed in radical photopolymerization to produce biobased polymers. The polymerization is monitored in the absence and presence of a photoinitiator and under air or protected from air, using Real-Time Fourier Transform Infrared Spectroscopy. The polymerization rate of the methacrylate double bonds was affected by the presence and reactivity of the allyl and propenyl groups in the eugenol- and isoeugenol-derived methacrylates, respectively. These groups are involved in radical addition, degradative chain transfer, and termination reactions, yielding crosslinked polymers. The materials, in the form of films, are characterized by differential scanning calorimetry, thermogravimetric, and contact angle analyses.

Published
2020
Full Text
View/download PDF

12. Fluoroalkyl Pentacarbonylmanganese(I) Complexes as Initiators for the Radical (co)Polymerization of Fluoromonomers

Author

Roberto Morales-Cerrada, Vincent Ladmiral, Florence Gayet, Christophe Fliedel, Rinaldo Poli, and Bruno Améduri

Subjects
fluoropolymers, manganese complexes, nuclear magnetic resonance, radicals, organometallic-mediated radical polymerization, vinylidene fluoride, Organic chemistry, QD241-441
Abstract

The use of [Mn(RF)(CO)5] (RF = CF3, CHF2, CH2CF3, COCF2CH3) to initiate the radical polymerization of vinylidene fluoride (F2C=CH2, VDF) and the radical alternating copolymerization of vinyl acetate (CH2=CHOOCCH3, VAc) with tert-butyl 2-(trifluoromethyl)acrylate (MAF-TBE) by generating primary RF• radicals is presented. Three different initiating methods with [Mn(CF3)(CO)5] (thermal at ca. 100 °C, visible light and UV irradiations) are described and compared. Fair (60%) to satisfactory (74%) polyvinylidene fluoride (PVDF) yields were obtained from the visible light and UV activations, respectively. Molar masses of PVDF reaching 53,000 g·mol−1 were produced from the visible light initiation after 4 h. However, the use of [Mn(CHF2)(CO)5] and [Mn(CH2CF3)(CO)5] as radical initiators produced PVDF in a very low yield (0 to 7%) by both thermal and photochemical initiations, while [Mn(COCF2CH3)(CO)5] led to the formation of PVDF in a moderate yield (7% to 23%). Nevertheless, complexes [Mn(CH2CF3)(CO)5] and [Mn(COCHF2)(CO)5] efficiently initiated the alternating VAc/MAF-TBE copolymerization. All synthesized polymers were characterized by 1H and 19F NMR spectroscopy, which proves the formation of the expected PVDF or poly(VAc-alt-MAF-TBE) and showing the chaining defects and the end-groups in the case of PVDF. The kinetics of VDF homopolymerization showed a linear ln[M]0/[M] versus time relationship, but a decrease of molar masses vs. VDF conversion was noted in all cases, which shows the absence of control. These PVDFs were rather thermally stable in air (up to 410 °C), especially for those having the highest molar masses. The melting points ranged from 164 to 175 °C while the degree of crystallinity varied from 44% to 53%.

Published
2020
Full Text
View/download PDF

13. Bis(formylphenolato)cobalt(II)-Mediated Alternating Radical Copolymerization of tert-Butyl 2-Trifluoromethylacrylate with Vinyl Acetate

Author

Sanjib Banerjee, Ekaterina V. Bellan, Florence Gayet, Antoine Debuigne, Christophe Detrembleur, Rinaldo Poli, Bruno Améduri, and Vincent Ladmiral

Subjects
alternating copolymers, cobalt complex, fluoropolymer, organometallic mediated radical polymerization, poly(vinyl acetate), Organic chemistry, QD241-441
Abstract

The organometallic-mediated radical polymerization (OMRP) of vinyl acetate (VAc) and its OMR copolymerization (OMRcoP) with tert-butyl 2-trifluoromethylacrylate (MAF-TBE) mediated by Co(SAL)2 (SAL = 2-formylphenolato or deprotonated salicylaldehyde) produced relatively well-defined PVAc and poly(VAc-alt-MAF-TBE) copolymers at moderate temperature (

Published
2017
Full Text
View/download PDF

15. From vineyards to reshapable materials: α-CF2 activation in 100% resveratrol-based catalyst-free vitrimers

Author

Florian Cuminet, Sébastien Lemouzy, Éric Dantras, Éric Leclerc, Vincent Ladmiral, and Sylvain Caillol

Subjects
Polymers and Plastics, Organic Chemistry, Bioengineering, Biochemistry
Abstract

Vitrimers are a class of polymers bridging resistant crosslinked thermosets and recyclable linear thermoplastics. The material presented here contains 86% bio-based carbon, is catalyst-free, durable and recyclable, and features a high Tg.

Published
2023

16. Utilization of Catechol End-Functionalized PMMA as a Macromolecular Coupling Agent for Ceramic/Fluoropolymer Piezoelectric Composites

Author

Vincent Bouad, Alexandre Fadel, Saj Mohan, Arthur Hamieh, Jean-François Tahon, Joël Lyskawa, Patrice Woisel, Antonio Da Costa, Anthony Ferri, Rachel Desfeux, Freddy Ponchel, Denis Remiens, Vincent Ladmiral, Sophie Barrau, 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 Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), 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), Matériaux et Acoustiques pour MIcro et NAno systèmes intégrés - IEMN (MAMINA - IEMN), INSA Institut National des Sciences Appliquées Hauts-de-France (INSA Hauts-De-France), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut d’Électronique, de Microélectronique et de Nanotechnologie - UMR 8520 (IEMN), Centrale Lille-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université Polytechnique Hauts-de-France (UPHF)-JUNIA (JUNIA), Université catholique de Lille (UCL)-Université catholique de Lille (UCL)-Centrale Lille-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université Polytechnique Hauts-de-France (UPHF)-JUNIA (JUNIA), Université catholique de Lille (UCL)-Université catholique de Lille (UCL), Institut d’Électronique, de Microélectronique et de Nanotechnologie - UMR 8520 (IEMN), UCCS Équipe Couches Minces & Nanomatériaux, Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Funding This work was supported by the French National Research Agency (NanoPiC grant, ANR-16-CE08-0025, and ANR-16-CE08-0025,NanoPiC,Etude du comportement piézoélectrique multi-échelles de composites innovants micro- et nano-structurés(2016)

Subjects
[SPI]Engineering Sciences [physics], Polymers and Plastics, Process Chemistry and Technology, Organic Chemistry, piezoelectric, catechol end-functionalized polymers, composite, fluoropolymers, PMMA, ceramic functionalization
Abstract

International audience; An approach based on the use of a macromolecular coupling agent and the aim to improve the interfacial adhesion between piezoelectric ceramics and piezoelectric polymer matrix in piezoelectric composites is presented. Poly(methyl methacrylate) (PMMA) bearing a catechol moiety was used as a macromolecular coupling agent, as it is known to be miscible to piezoelectric fluoropolymers and catechol groups can strongly bind to a large variety of surfaces. Thus, entanglement between the PMMA chains and the amorphous segments of the fluoropolymer would ensure the desired interfacial adhesion. Well-defined PMMA was synthesized via RAFT polymerization using 2-cyano-2-propyl dodecyl trithiocarbonate as a chain-transfer agent. The PMMA ω-chain end was then functionalized with a catechol group via a one-pot aminolysis/thia-Michael addition procedure using a dopamine acrylamide (DA) derivative as a Michael acceptor. The presence of the catechol moiety at the chain end of PMMA was controlled by 1H NMR and cyclic voltammetry measurements. The resulting PMMA-DA was then grafted onto the surface of a lead-free piezoelectric ceramic film (i.e., a thin film of H2O2-activated (Bi0.5Na0.5)TiO3 (BNT) with a large contact area). The increase of the water contact angle confirmed the efficiency of the grafting. A commercial piezoelectric copolymer P(VDF-co-TrFE) was then spin-coated onto the modified BNT surface to form a bilayer composite. The composite cross section prepared by cryofracture was examined by scanning electron microscopy and revealed that the ceramic/polymer interface of the BNT-PMMA/P(VDF-co-TrFE) bilayer composite exhibits a much better cohesion than its counterpart composite prepared from nonmodified BNT. Moreover, the grazing incidence wide-angle X-ray scattering confirmed that the copolymer crystal structure was not impacted by the presence of the PMMA-DA coupling agent. A strong piezoelectric response was locally detected by piezoresponse force microscopy. This study highlights the potential of PMMA-DA as a macromolecular coupling agent to improve the ceramic/polymer interface in piezoelectric composite materials.

Published
2022

20. Catalyst‐Free Thia‐Michael Addition to alpha‐Trifluoromethylacrylates for 3D Network Synthesis

Author

Dimitri Berne, Sébastien Lemouzy, Pascale Guiffrey, Sylvain Caillol, Vincent Ladmiral, Eric Manoury, Rinaldo Poli, Eric Leclerc, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Laboratoire de chimie de coordination (LCC), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), Institut Universitaire de France (IUF), Ministère de l'Education nationale, de l’Enseignement supérieur et de la Recherche (M.E.N.E.S.R.), and ANR-19-CE06-0014,AFCAN,Réseaux covalents adaptatifs sans additifs(2019)

Subjects
Kinetics, [CHIM.POLY]Chemical Sciences/Polymers, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Michael addition, Organic Chemistry, Fluorine effect, General Chemistry, DFT calculations, Thermosets, Catalysis
Abstract

International audience; Thia-Michael additions (1,4-additions of a thiol to a Michael acceptor) are generally catalyzed by an external Brønsted or Lewis base. A spontaneous (uncatalyzed) Michael addition of thiols to a-trifluoromethyl acrylates is described in this article, as well as its application to the very efficient preparation of a thermoset. A thorough mechanistic investigation, based on an experimental kinetic study and on DFT calculations, is presented for the addition of arene- and alkanethiols to tert-butyl trifluoromethyl acrylate in polar aprotic solvents, unveiling a probable solvent-assisted proton transfer in the rate-determining step and a considerable lowering of the energy barrier induced by the CF3 group.

Published
2023

21. Catalyst-Free Epoxy Vitrimers Based on Transesterification Internally Activated by an α–CF3 Group

Author

Dimitri Berne, Florian Cuminet, Sébastien Lemouzy, Christine Joly-Duhamel, Rinaldo Poli, Sylvain Caillol, Eric Leclerc, Vincent Ladmiral, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Laboratoire de chimie de coordination (LCC), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), Institut Universitaire de France (IUF), Ministère de l'Education nationale, de l’Enseignement supérieur et de la Recherche (M.E.N.E.S.R.), and ANR-19-CE06-0014,AFCAN,Réseaux covalents adaptatifs sans additifs(2019)

Subjects
Inorganic Chemistry, Transesterification, Catalysts, Polymers and Plastics, Organic polymers, Organic compounds, Organic Chemistry, Materials Chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Materials
Abstract

International audience; Vitrimers are polymer networks in which associative exchange reactions can take place under specific conditions, thus conferring reprocessability to insoluble materials. Recently, catalyst-free vitrimers have emerged as a new generation of vitrimers able to overcome potential leaching, aging, and sintering issues of catalysts and to ensure the preservation of vitrimer properties after numerous reshaping processes. Here, a catalyst-free epoxy vitrimer featuring α-CF3-substituted ester functions is reported. First, a new tetra-acid precursor was synthesized via a catalyst-free thia-Michael addition. A catalyst-free ring-opening polymerization was then performed on two different diepoxy monomers (DGEBA and BDGE) to obtain polymer networks composed of ester linkages. Curing was evaluated by rheology, differential scanning calorimetry (DSC), and Fourier transform infrared spectroscopy (FTIR) monitoring of the polymerization kinetics. A gel content of over 70% was measured after 24 h in tetrahydrofuran (THF). Finally, the accelerating effect of the α-CF3 group on transesterification reactions was highlighted by stress-relaxation experiments and analyzed computationally on a molecular model system. Reprocessability tests were carried out at 150 °C for 2 h. The mechanical and thermal properties of the reshaped materials were similar to those of the initial ones. This study demonstrates the potential of fluorinated groups as powerful internal activators for transesterification vitrimers.

Published
2022

22. Biobased catalyst-free covalent adaptable networks based on CF3-activated synergistic aza-Michael exchange and transesterification

Author

Dimitri Berne, Baptiste Quienne, Sylvain Caillol, Eric Leclerc, and Vincent Ladmiral

Subjects
Renewable Energy, Sustainability and the Environment, General Materials Science, General Chemistry
Abstract

This study reports the synthesis and characterization of biobased CANs incorporating CF3-activated aza-Michael bonds and ester groups showing remarkable reprocessing abilities and high activation energy.

Published
2022

24. Supramolecular co-assembly of water-soluble nucleobase-containing copolymers: bioinspired synthetic platforms towards new biomimetic materials

Author

Laura Vasilica Arsenie, Mona Semsarilar, Johannes C. Brendel, Patrick Lacroix-Desmazes, Vincent Ladmiral, and Sylvain Catrouillet

Subjects
Polymers and Plastics, Organic Chemistry, Bioengineering, Biochemistry
Abstract

This study presents the development of co-assembled copolymer architectures at physiological pH (pH 7.4) formed via H-bonds between complementary nucleobase-containing copolymers.

Published
2022

26. Catalyst-free transesterification vitrimers: activation via α-difluoroesters

Author

Florian Cuminet, Dimitri Berne, Sébastien Lemouzy, Éric Dantras, Christine Joly-Duhamel, Sylvain Caillol, Éric Leclerc, and Vincent Ladmiral

Subjects
Polymers and Plastics, Organic Chemistry, Bioengineering, Biochemistry
Abstract

Transesterification vitrimers often require high catalyst loadings to prepare 3D networks reprocessable at moderately high temperature.

Published
2022

27. Surface-initiated reversible addition fragmentation chain transfer of fluoromonomers: an efficient tool to improve interfacial adhesion in piezoelectric composites

Author

Vincent Bouad, Kohji Ohno, Ahmed Addad, Adeline Marin, Nicolas Donzel, Sophie Barrau, Joël Lyskawa, Vincent Ladmiral, 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), Department of Material and Life Science, Graduate School of Engineering, Osaka University, Osaka University [Osaka], Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), ANR-16-CE08-0025,NanoPiC,Etude du comportement piézoélectrique multi-échelles de composites innovants micro- et nano-structurés(2016), Université de Lille, CNRS, INRAE, ENSCL, Unité Matériaux et Transformations (UMET) - UMR 8207, and Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier [ICGM ICMMM]

Subjects
[CHIM.POLY]Chemical Sciences/Polymers, Polymers and Plastics, Organic Chemistry, Bioengineering, [CHIM.MATE]Chemical Sciences/Material chemistry, Biochemistry
Abstract

International audience; This article reports the surface-initiated Reversible Addition–Fragmentation chain Transfer polymerization (SI-RAFT) of trifluoroethylene (TrFE) and vinylidene fluoride (VDF) from barium titanate nanoparticles (BTO NPs) for the preparation of piezoelectric composites. A new xanthate chain transfer agent (DOPA-XA) derived from O-ethyl-S-(1-methoxy-carbonyl) ethyldithiocarbonate and integrating a catechol moiety able to efficiently bind onto the BTO NP surface was synthesized, characterized via1H and 13C NMR spectroscopy and employed to mediate SI-RAFT polymerizations. This DOPA-XA was immobilized onto BTO NPs and the grafting efficiency was evaluated by TEM images and XPS measurements while the grafting density (Γ > 0.2 chains per nm2) was calculated using TGA and BET measurements. Poly(trifluoroethylene)- (PTrFE) and poly(vinylidene fluoride-co-trifluoroethylene)- (P(VDF-co-TrFE) functionalized BTO NPs were prepared by SI-RAFT polymerization and characterized by nuclear magnetic resonance (NMR), size exclusion chromatography (SEC), thermogravimetric analysis (TGA), transmission electron macroscopy (TEM) and X-ray photoelectron microscopy (XPS). Interestingly, polymer brushes featuring relatively low dispersities (Đ < 1.5) and high grafting densities (Γ > 0.2 chains per nm2) were obtained. Piezoelectric composite films were then prepared from these fluoropolymer-decorated BTO NPs by incorporation into a P(VDF-co-TrFE) matrix using the solvent casting method. The homogeneity of the NPs dispersion in the copolymer matrix was assessed by SEM and the direct piezoelectric response of the composites was recorded after polarization and compared with composites prepared from non-modified BTO NPs. The measured piezoelectric coefficients (d33) of all the composites were of the same order of magnitude (around −9 pC N−1). Finally, the interface between the NPs and the copolymer matrix was mechanically stressed by stretching. The SEM images of the composite fracture showed, in the case of nongrafted BTO NPs, the presence of cavities close to the NPs associated with a weak interfacial adhesion while, for fluoropolymers grafted BTO NPs, the interface with the copolymer matrix was cohesive. This study leads to innovative composites with a cohesive ceramic/polymer interface for piezoelectric applications.

Published
2022

28. Coordination adaptable networks: zirconium(IV) carboxylates

Author

Meenu Murali, Dimitri Berne, Christine Joly‐Duhamel, Sylvain Caillol, Eric Leclerc, Eric Manoury, Vincent Ladmiral, Rinaldo Poli, Laboratoire de chimie de coordination (LCC), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), and ANR-19-CE06-0014,AFCAN,Réseaux covalents adaptatifs sans additifs(2019)

Subjects
Vitrimer, Organic Chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, General Chemistry, Zirconium, Coordination adaptable network, Rheology, Carboxylate exchange, Catalysis
Abstract

International audience; Vitrimers are 3D “covalent adaptable networks” (CANs) with flow properties thanks to thermally activated associative exchange reactions. The present contribution introduces coordination adaptable networks, or CooANs, that are topologically related to metal-organic frameworks with octahedral Zr 6 clusters as secondary building units in a carboxylic acid-functionalized acrylate-methacrylate copolymer matrix. A series of Zr-CooAN-x materials (x = percent of Zr 6 loading relative to maximum capacity) was synthesized with x = 5, 10, 15, 20, 25, 50 and 100. The mechanical and rheological investigations demonstrate vitrimer-like properties for x up to 50, the crosslink migration being ensured by carboxylate ligand exchange, with relaxation becoming slower as the Zr 6 content is increased. The flow activation energy of Zr-CooAN-10 is 92.9 ± 3.6 kJ mol -1 . Rapid (30 min) hot-press reshaping occurs at temperatures in the 50-100 °C range under a 3-ton pressure and does not significantly alter the material properties.

Published
2022

29. Understanding the Reshaping of Fluorinated Polyester Vitrimers by Kinetic and DFT Studies of the Transesterification Reaction

Author

Sébastien Lemouzy, Florian Cuminet, Dimitri Berne, Sylvain Caillol, Vincent Ladmiral, Rinaldo Poli, Eric Leclerc, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Laboratoire de chimie de coordination (LCC), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), Institut Universitaire de France (IUF), Ministère de l'Education nationale, de l’Enseignement supérieur et de la Recherche (M.E.N.E.S.R.), Institut Carnot Chimie Balard Cirimat for funding (CatFreeCAN program), and ANR-19-CE06-0014,AFCAN,Réseaux covalents adaptatifs sans additifs(2019)

Subjects
[CHIM.POLY]Chemical Sciences/Polymers, Covalent adaptable networks, Fluorine effect, Organic Chemistry, Vitrimers, General Chemistry, DFT calculations, Transesterification kinetics, Catalysis
Abstract

International audience; Vitrimers are a third class of polymers gathering the mechanical properties and solvent resistance of 3D thermosets and the reprocessability of thermoplastics. This unique behaviour is due to the triggering of certain covalent exchange reactions that allow the network to rearrange upon application of a stimulus. The constitutive feature of vitrimers is the adoption of a glass-like viscosity during the rearrangement of the network, often due to an associative mechanism for the exchange reaction. Transesterification networks are one of the most studied type of vitrimers that usually require the incorporation of a catalyst, implying the associated drawbacks. Our group recently reported catalyst-free transesterification vitrimers in which the ester functions are particularly reactive thanks to the presence of fluorine atoms in a- or b-position. In the present contribution, we present parallel DFT calculations and an experimental kinetic study on model molecules in order to quantitatively assess the effect of neighbouring fluorinated groups on the transesterification reaction rate.

Published
2022

30. Combination of Cationic and Radical RAFT Polymerizations: A Versatile Route to Well-Defined Poly(ethyl vinyl ether)

Author

Marc, Guerre, Mineto, Uchiyama, Enrique, Folgado, Mona, Semsarilar, Bruno, Améduri, Kotaro, Satoh, Masami, Kamigaito, and Vincent, Ladmiral

Abstract

Poly(vinylidene fluoride)-containing block copolymers are difficult to prepare and still very rare in spite of their potential use in high added value applications. This communication describes in detail the synthesis of unprecedented poly(ethyl vinyl ether)

Published
2022

32. Hemiacetal Ester Exchanges, Study of Reaction Conditions and Mechanistic Pathway

Author

David Boucher, Claire Negrell, Vincent Ladmiral, Nadine Pébère, Nicolas Caussé, Jeppe Madsen, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Danmarks Tekniske Universitet (DTU), Centre interuniversitaire de recherche et d'ingenierie des matériaux (CIRIMAT), Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National Polytechnique (Toulouse) (Toulouse INP), and Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)

Subjects
exchange reaction, Carboxylic acid, Kinetics, 010402 general chemistry, 01 natural sciences, Catalysis, chemistry.chemical_compound, hemiacetal ester, associative, Organic chemistry, Molecule, General Environmental Science, Associative, chemistry.chemical_classification, Reaction conditions, Exchange reaction, 010405 organic chemistry, Associative substitution, Phosphate, 0104 chemical sciences, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, kinetics, General Earth and Planetary Sciences, Hemiacetal, Hemiacetal ester
Abstract

International audience; A range of hemiacetal esters were synthesized by the reaction between carboxylic acids and butyl vinyl ether using n-dodecyl dihydrogen phosphate as catalyst. Specifically, nonanoic, propionic, acrylic, sebacic, and fumaric acids were used as substrates to prepare the corresponding hemiacetal esters. These compounds were used as model molecules to demonstrate the ability of hemiacetal ester functional groups to undergo the exchange reaction in the presence of weak carboxylic acids without any catalyst. Kinetics studies examined the effect of the carboxylic acid concentration on the exchange rate, and revealed that the exchange reaction proceeds through an associative mechanism.

Published
2020

33. Sustainable design of vanillin-based vitrimers using vinylogous urethane chemistry

Author

Stéphanie Engelen, Aleksandra Alicja Wróblewska, Kevin De Bruycker, Resat Aksakal, Vincent Ladmiral, Sylvain Caillol, and Filip E. Du Prez

Subjects
Chemistry, Polymers and Plastics, HIGH-PERFORMANCE, Organic Chemistry, RENEWABLE RESOURCES, Bioengineering, AMINES, EPOXY VITRIMER, Biochemistry, NETWORKS
Abstract

Research on bio-based covalent adaptable networks is popular nowadays in the search for an optimal implementation of thermoset materials and composites in a circular context. Herein, a vanillin derivative is integrated into vitrimers with promising material properties in which the vinylogous urethane associative chemistry has been used as a dynamic covalent chemistry platform. The vanillin derivative, 2-methoxyhydroquinone, is epoxidised and aminated by aqueous ammonia, with the formation of a bi-functional aromatic beta-hydroxy-amine. The straightforward synthesis protocol is high yielding and up-scalable, without the need for any chromatographic purification step. The presented rigid, catalyst-free vitrimers have a high renewable carbon content (up to 86%), glass transition temperatures up to 80 degrees C and show very fast reprocessing and consequently a swift recyclability with relaxation times in the range of seconds by virtue of the applied beta-hydroxy-amine functionality. This research thus provides a sustainable approach for the synthesis of vanillin-based vitrimers and fits in with growing interest for the design of recyclable crosslinked polymer materials.

Published
2022

34. Grafting from Fluoropolymers Using ATRP: What is Missing?

Author

Marc Guerre, Mona Semsarilar, Vincent Ladmiral, Interactions moléculaires et réactivité chimique et photochimique (IMRCP), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées, Institut Européen des membranes (IEM), Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie de Toulouse (ICT), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut Ecologie et Environnement (INEE), Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Fédération de Recherche Fluides, Energie, Réacteurs, Matériaux et Transferts (FERMAT), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), P3R - Polymères de Précision par Procédés Radicalaires (P3R), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie de Toulouse (ICT), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), and Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM)

Subjects
PVDF, Dehydrofluorination, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, Grafting-from strategy, [CHIM.POLY]Chemical Sciences/Polymers, [CHIM]Chemical Sciences, 0210 nano-technology, Fluoropolymers, ComputingMilieux_MISCELLANEOUS
Abstract

International audience; Grafting polymers from fluoropolymer backbones is very advantageous to modify the properties of these often non-functional materials. It is particularly useful in the field of ultrafiltration membranes to tune the hydrophilicity of PVDF membranes and to add other properties such as antifouling for example. One of the main techniques used to effect such grafting is ATRP. A large number of papers are published every year on this topic. However, careful examination of this body of work reveals that the evidence provided to support the covalent bonding of polymer chains on the fluoropolymers are often limited and rather unconvincing. This is of course due to the difficult detection of the rare connecting covalent bonds. Nevertheless, this detection problem is not the only issue. Grafting from fluoropolymers using ATRP relies on the homolytic cleavage of C−F bond, notorious for their high stability and BDE. Moreover, fluoropolymers based on VDF are prone to dehydrofluorination by reaction with bases and nucleophiles, which leads to the formation of unsaturations within the polymer backbone. This reaction is often completely ignored even though ATRP ligands can trigger this elimination. These two very often overlooked reactivity features seriously question the use of ATRP as an efficient grafting technique for fluoropolymers.

Published
2021

35. Plant–environment microscopy tracks interactions of Bacillus subtilis with plant roots across the entire rhizosphere

Author

Ilonka Engelhardt, Timothy S. George, Daniel Patko, Michael P. MacDonald, Tim J. Daniell, Vincent Ladmiral, Bruno Ameduri, Nicola R. Stanley-Wall, Lionel X. Dupuy, Nicola Holden, Yangminghao Liu, Conservation of Natural Resources, NEIKER, 48160 Derio, Spain, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)

Subjects
0303 health sciences, Rhizosphere, Multidisciplinary, biology, Plant roots, 030306 microbiology, Microorganism, Bacillus subtilis, 15. Life on land, biology.organism_classification, Mesocosm, 03 medical and health sciences, Seedling, Botany, Microscopy, [CHIM]Chemical Sciences, Root cap, 030304 developmental biology
Abstract

International audience; Our understanding of plant–microbe interactions in soil is limited by the difficulty of observing processes at the microscopic scale throughout plants’ large volume of influence. Here, we present the development of three-dimensional live microscopy for resolving plant–microbe interactions across the environment of an entire seedling growing in a transparent soil in tailor-made mesocosms, maintaining physical conditions for the culture of both plants and microorganisms. A tailor-made, dual-illumination light sheet system acquired photons scattered from the plant while fluorescence emissions were simultaneously captured from transparent soil particles and labeled microorganisms, allowing the generation of quantitative data on samples ∼3,600 mm 3 in size, with as good as 5 µm resolution at a rate of up to one scan every 30 min. The system tracked the movement of Bacillus subtilis populations in the rhizosphere of lettuce plants in real time, revealing previously unseen patterns of activity. Motile bacteria favored small pore spaces over the surface of soil particles, colonizing the root in a pulsatile manner. Migrations appeared to be directed toward the root cap, the point of “first contact,” before the subsequent colonization of mature epidermis cells. Our findings show that microscopes dedicated to live environmental studies present an invaluable tool to understand plant–microbe interactions.

Published
2021

36. Plant-environment microscopy tracks interactions of

Author

Yangminghao, Liu, Daniel, Patko, Ilonka, Engelhardt, Timothy S, George, Nicola R, Stanley-Wall, Vincent, Ladmiral, Bruno, Ameduri, Tim J, Daniell, Nicola, Holden, Michael P, MacDonald, and Lionel X, Dupuy

Subjects
Microscopy, Silicon, Temperature, Plant Biology, Equipment Design, Environment, Lettuce, Biological Sciences, Plant Roots, Fluorescence, Soil, Biophysics and Computational Biology, Seedlings, Calibration, Rhizosphere, Physical Sciences, Image Processing, Computer-Assisted, environmental imaging, rhizosphere, Soil Microbiology, Bacillus subtilis, root–microbe interactions
Abstract

Significance The lack of suitable approaches for studying root–microbe interactions, live and in situ, has severely limited our ability to understand the rhizosphere. In this study, we overcome this major limitation with an imaging system that combines transparent soils with cutting edge light sheet microscopy. The study revealed that the root cap is a point of first contact for microbes before establishment and reveals how the pore structure influences the patterns of interactions between the microbe and the plant. With the combined use of light sheet microscopy and transparent soils, we shed light on previously unseen interaction phenomena and accelerate the understanding of how rhizospheres are formed., Our understanding of plant–microbe interactions in soil is limited by the difficulty of observing processes at the microscopic scale throughout plants’ large volume of influence. Here, we present the development of three-dimensional live microscopy for resolving plant–microbe interactions across the environment of an entire seedling growing in a transparent soil in tailor-made mesocosms, maintaining physical conditions for the culture of both plants and microorganisms. A tailor-made, dual-illumination light sheet system acquired photons scattered from the plant while fluorescence emissions were simultaneously captured from transparent soil particles and labeled microorganisms, allowing the generation of quantitative data on samples ∼3,600 mm3 in size, with as good as 5 µm resolution at a rate of up to one scan every 30 min. The system tracked the movement of Bacillus subtilis populations in the rhizosphere of lettuce plants in real time, revealing previously unseen patterns of activity. Motile bacteria favored small pore spaces over the surface of soil particles, colonizing the root in a pulsatile manner. Migrations appeared to be directed toward the root cap, the point of “first contact,” before the subsequent colonization of mature epidermis cells. Our findings show that microscopes dedicated to live environmental studies present an invaluable tool to understand plant–microbe interactions.

Published
2021

37. Thia-Michael Reaction: The Route to Promising Covalent Adaptable Networks

Author

Vincent Ladmiral, Sylvain CAILLOL, Eric Leclerc, and Dimitri BERNE

Subjects
Polymers and Plastics, General Chemistry
Abstract

While the Michael addition has been employed for more than 130 years for the synthesis of a vast diversity of compounds, the reversibility of this reaction when heteronucleophiles are involved has been generally less considered. First applied to medicinal chemistry, the reversible character of the hetero-Michael reactions has recently been explored for the synthesis of Covalent Adaptable Networks (CANs), in particular the thia-Michael reaction and more recently the aza-Michael reaction. In these cross-linked networks, exchange reactions take place between two Michael adducts by successive dissociation and association steps. In order to understand and precisely control the exchange in these CANs, it is necessary to get an insight into the critical parameters influencing the Michael addition and the dissociation rates of Michael adducts by reconsidering previous studies on these matters. This review presents the progress in the understanding of the thia-Michael reaction over the years as well as the latest developments and plausible future directions to prepare CANs based on this reaction. The potential of aza-Michael reaction for CANs application is highlighted in a specific section with comparison with thia-Michael-based CANs.

Published
2022

38. Thermal Degradation of Fluorosilicone Elastomers

Author

Emmanuel Richaud, Leticia Pires, Sébastien Roland, Laurianne Truffault, Lucien Laiarinandrasana, Alice Corfa, Julien Pinaud, Sylvain Caillol, Vincent Ladmiral, and Christophe Beauvais

Subjects
Polymers and Plastics, Organic Chemistry, Materials Chemistry, Condensed Matter Physics
Published
2022

39. Partially acrylated linseed oil UV-cured coating containing a dihemiacetal ester for the corrosion protection of an aluminium alloy

Author

Vincent Ladmiral, Nadine Pébère, Claire Negrell, David Boucher, Nicolas Caussé, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Centre interuniversitaire de recherche et d'ingenierie des matériaux (CIRIMAT), Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC), Centre National de la Recherche Scientifique - CNRS (FRANCE), Ecole Nationale Supérieure de Chimie de Montpellier - ENSCM (FRANCE), Institut National Polytechnique de Toulouse - Toulouse INP (FRANCE), Université Toulouse III - Paul Sabatier - UT3 (FRANCE), and Université de Montpellier (FRANCE)

Subjects
Water uptake, food.ingredient, Materials science, Matériaux, General Chemical Engineering, Self-healing, 02 engineering and technology, Thermal treatment, engineering.material, 010402 general chemistry, 01 natural sciences, Corrosion, [SPI.MAT]Engineering Sciences [physics]/Materials, food, Linseed oil, Coating, Bio-based coating, Materials Chemistry, Aluminium alloy, Glass transition temperature, chemistry.chemical_classification, Barrier properties, Organic Chemistry, Epoxy, Polymer, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Surfaces, Coatings and Films, Dielectric spectroscopy, chemistry, Chemical engineering, visual_art, visual_art.visual_art_medium, engineering, 0210 nano-technology, Electrochemical impedance spectroscopy
Abstract

International audience; The present work focused on the development of a partially bio-based polymer matrix for the corrosion protection of the 3003 aluminium alloy. A dihemiacetal ester (1,10-dibutoxyethyl sebacate (DBES)) was added to the formulation to afford, after an additional thermal treatment, further cross-linking and a repairing effect of the polymer matrix. First, an epoxidized linseed oil was partially acrylated and subsequently copolymerized with (3,4-dihydroxyphenetyl)-acrylamide and N,N-dimethyl acrylamide, with and without DBES under UV irradiation. Under thermal treatment, the DBES released dicarboxylic acid able to react with epoxy functions. The corrosion protection of the resulting coatings (with and without DBES and with and without the thermal treatment) was assessed by electrochemical impedance spectroscopy (EIS). The diagrams were obtained for various immersion times in a 0.5 M NaCl solution. The coatings had good barrier properties, which remained stable throughout the duration of the impedance measurements (two weeks). The addition of the DBES in the formulation, followed by the thermal treatment, resulted in an increase of the barrier properties, a decrease of water uptake and a healing of some small matrix defects. The improvement of the anticorrosion ability of the coating containing the DBES after the thermal treatment was attributed to an additional cross-linking. This work illustrates an original strategy for the development of self-healing bio-based coatings by using temporarily protected functions (here, dihemiacetal ester functions).

Published
2021

40. Polystyrene Hybrid-Vitrimer Based on the Hemiacetal Ester Exchange Reaction

Author

David Boucher, Nadine Pébère, Jeppe Madsen, Qian Huang, Nicolas Caussé, Liyun Yu, Claire Negrell, Vincent Ladmiral, Centre National de la Recherche Scientifique - CNRS (FRANCE), Ecole Nationale Supérieure de Chimie de Montpellier - ENSCM (FRANCE), Institut National Polytechnique de Toulouse - Toulouse INP (FRANCE), Université Toulouse III - Paul Sabatier - UT3 (FRANCE), Technical University of Denmark (DENMARK), Université de Montpellier (FRANCE), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Danmarks Tekniske Universitet (DTU), Wuhan University [China], Centre interuniversitaire de recherche et d'ingenierie des matériaux (CIRIMAT), Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National Polytechnique (Toulouse) (Toulouse INP), and Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)

Subjects
Polymers and Plastics, Carboxylic acid, Butyl acrylate, Dimer, Matériaux, Ether, 010402 general chemistry, 01 natural sciences, Styrene, Inorganic Chemistry, chemistry.chemical_compound, Polymer chemistry, Organic compounds, Materials Chemistry, [CHIM]Chemical Sciences, Nucleic acid structure, Materials, ComputingMilieux_MISCELLANEOUS, chemistry.chemical_classification, 010405 organic chemistry, Copolymers, Organic Chemistry, 0104 chemical sciences, chemistry, Vitrimers, Hemiacetal, Polystyrene, Ethers
Abstract

Vitrimer materials, which are permanently cross-linked but reshapable polymers, are a class of materials of growing interest due to their potential in recycling and sustainable development. More precisely, vitrimers derived from commodity polymers could have a drastic impact on plastic consumption in the upcoming years. Here, the development of a polystyrene-based vitrimer harnessing the recently discovered hemiacetal ester exchange reaction of carboxylic acid is presented. 1,4-Cyclohexanedimethanol divinyl ether was reacted with 4-vinylbenzoic acid (VBA) to form a divinyl species containing two hemiacetal ester functions. This dimer was then copolymerized with styrene, butyl acrylate, and VBA to form a cross-linked material presenting pendent acid groups. This material exhibited three distinct behaviors at different temperature regimes: below 80 °C, despite the exchange reactions able to occur at this temperature, the cross-linked material behaved as a frozen material due to the hydrogen bonding formed by the carboxylic acid pendent groups. Between 80 and 130 °C, the vitrimer behavior was demonstrated by rheological creep experiments. At higher temperatures, the dissociation of the hemiacetal ester groups led to the loss of the covalent cross-linking.

Published
2021

41. Solution self-assembly of fluorinated polymers, an overview

Author

Vincent Ladmiral, Gérald Lopez, Mona Semsarilar, Bruno Ameduri, Marc Guerre, Interactions moléculaires et réactivité chimique et photochimique (IMRCP), Institut de Chimie de Toulouse (ICT-FR 2599), Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Recherche pour le Développement (IRD)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM), Institut Européen des membranes (IEM), Université de Montpellier (UM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut Ecologie et Environnement (INEE), Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Fédération de Recherche Fluides, Energie, Réacteurs, Matériaux et Transferts (FERMAT), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), P3R - Polymères de Précision par Procédés Radicalaires (P3R), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie de Toulouse (ICT), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)

Subjects
chemistry.chemical_classification, Materials science, Polymers and Plastics, Organic Chemistry, chemistry.chemical_element, Bioengineering, Nanotechnology, 02 engineering and technology, Polymer, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Biochemistry, Ferroelectricity, 0104 chemical sciences, Electronegativity, Fluorinated monomers, chemistry, Fluorine, Copolymer, Fluorinated Polymers, [CHIM]Chemical Sciences, Self-assembly, 0210 nano-technology
Abstract

Fluoropolymers constitute an attractive family of polymer materials with remarkable properties such as high resistance to chemicals, UV and heat, ferroelectricity and piezoelectricity for semi-crystalline polymers, to name a few. The incorporation of fluorinated moieties in a polymer can confer unique properties. Due to the fluorine atom's high electronegativity and the peculiar interactions of the fluorinated group, such polymers readily self-assemble in solution and often lead to original morphologies endowed with rare properties. Thanks to advances made in organic and polymer chemistry, a large variety of fluorinated monomers and polymers have been used to design fluorinated copolymer architectures. This review gives an overview of the current state of the art of the solution self-assembly of these fluorinated copolymer architectures.

Published
2021

42. Semi-Fluorinated Di and Triblock Copolymer Nano-Objects Prepared via RAFT Alcoholic Dispersion Polymerization (PISA)

Author

Chaimaa Gomri, Gregoire Desnos, Mathias Gravelle, Mona Semsarilar, Vincent Ladmiral, Adrien Rubio, Institut Européen des membranes (IEM), Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Université de Montpellier (UM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)

Subjects
Materials science, Polymers and Plastics, Organic chemistry, 02 engineering and technology, 010402 general chemistry, Methacrylate, 01 natural sciences, Article, chemistry.chemical_compound, QD241-441, Polymer chemistry, Copolymer, [CHIM]Chemical Sciences, semi-fluorinated, RAFT, PISA, dispersion polymerization, self-assembly, Reversible addition−fragmentation chain-transfer polymerization, Dispersion polymerization, Acrylate, Chain transfer, General Chemistry, Raft, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Monomer, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, 0210 nano-technology
Abstract

A set of well-defined amphiphilic, semi-fluorinated di and triblock copolymers were synthesized via polymerization-induced self-assembly (PISA) under alcoholic dispersion polymerization conditions. This study investigates the influence of the length, nature and position of the solvophobic semi-fluorinated block. A poly(N,N-dimethylaminoethyl methacrylate) was used as the stabilizing block to prepare the di and tri block copolymer nano-objects via reversible addition-fragmentation chain transfer (RAFT) controlled dispersion polymerization at 70 °C in ethanol. Benzylmethacrylate (BzMA) and semi-fluorinated methacrylates and acrylates with 7 (heptafluorobutyl methacrylate (HFBMA)), 13 (heneicosafluorododecyl methacrylate (HCFDDMA)) and 21 (tridecafluorooctyl acrylate (TDFOA)) fluorine atoms were used as monomers for the core-forming blocks. The RAFT polymerization of these semi-fluorinated monomers was monitored by SEC and 1H NMR. The evolution of the self-assembled morphologies was investigated by transmission electron microscopy (TEM). The results demonstrate that the order of the blocks and the number of fluorine atoms influence the microphase segregation of the core-forming blocks and the final morphology of the nano-objects.

Published
2021

45. Ferulic acid-based reactive core–shell latex by seeded emulsion polymerization

Author

Patrick Lacroix-Desmazes, Kotaro Satoh, Mona Semsarilar, Masami Kamigaito, Vincent Ladmiral, Claire Negrell, Wing Sze Jennifer Li, Sylvain Caillol, Hisaaki Takeshima, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Department of Molecular Design and Engineering (Graduate School of Engineering, Nagoya University), Institut Européen des membranes (IEM), and Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)

Subjects
chemistry.chemical_classification, Polymers and Plastics, Chemistry, Organic Chemistry, Emulsion polymerization, Bioengineering, 02 engineering and technology, Polymer, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Biochemistry, 0104 chemical sciences, chemistry.chemical_compound, [CHIM.POLY]Chemical Sciences/Polymers, Monomer, Chemical engineering, Emulsion, Particle, Radical initiator, Ammonium persulfate, Particle size, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract

A recently revisited biobased styrenic monomer, acetyl-protected 4-vinylguaiacol (AC4VG), was used for the synthesis of partially biobased, functional core–shell polymers. P(S-co-BA)@PAC4VG and PBA@PAC4VG latex particles with a PAC4VG shell were prepared using a two-step seeded radical emulsion polymerization process. The P(S-co-BA) and PBA seed particles were synthesized first, and the AC4VG monomer was subsequently added as a pre-emulsion over time. The aqueous emulsion polymerizations were carried out at 10 wt% solids at 80 °C using ammonium persulfate as a radical initiator and sodium dodecyl sulfate as a surfactant. These polymerizations resulted in colloidally stable latexes with high monomer conversions (>95%). The resulting particles were 80–90 nm in diameter (intensity-average) and TEM observations revealed core–shell and partially encapsulated particle morphologies. Up to 70% of the acetoxy groups of PAC4VG in the P(S-co-BA)@PAC4VG latex were deprotected under mild basic conditions over 18 hours to produce core–shell polymers decorated with phenolic functions on their surface. This deprotection procedure did not adversely affect the particle size or colloidal stability of the latex. Finally, partially biobased phenolic networks (phenolic resins) were produced from these functional core–shell particles by crosslinking with glyoxal, a naturally-sourced dialdehyde.

Published
2019

46. π-Stacking Interactions of Graphene-Coated Cobalt Magnetic Nanoparticles with Pyrene-Tagged Dendritic Poly(Vinylidene Fluoride)

Author

Vincent Collière, Anne-Marie Caminade, Enrique Folgado, Marc Guerre, Christian Bijani, Kathleen I. Moineau-Chane Ching, Bruno Ameduri, Nidhal Mimouni, Vincent Ladmiral, Armelle Ouali, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), and Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
π-stacking, magnetic nanoparticles, Dendrimers, Materials science, Stacking, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Fluorescence spectroscopy, law.invention, chemistry.chemical_compound, law, Dendrimer, Moiety, Pyrenes, Graphene, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Poly(vinylidenefluoride), [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Chemical engineering, Pyrene, Magnetic nanoparticles, 0210 nano-technology, Cobalt
Abstract

International audience; This study investigates the non-covalent coating of cobalt magnetic nanoparticles (MNPs) involving a graphene surface with pyrene-tagged dendritic poly(vinylidene fluoride) (PVDF). Dendrimers bearing a pyrene moiety were selected to play the role of spacers between the graphene surface of the MNPs and the PVDF chains, the pyrene unit being expected to interact with the surface of the MNPs. The pyrene-tagged dendritic spacer 11 decorated with ten acetylenic units was prepared and fully characterized. Azido-functionalized PVDF chains were then grafted onto each branch of the dendrimer using Huisgen’s [3 + 2] cycloaddition reaction. Next, the association of the resulting pyrene-tagged dendritic PVDF 13 with commercially available Co/C MNPs by π -stacking interactions was studied by fluorescence spectroscopy. Evaluated were the stability of the π -stacking interactions when the temperature increased and the reversibility of the process when the temperature de- creased. Also, hybrid MNPs were prepared from pyrene-tagged dendrimers decorated either with acetylenic functions ( 11 ) or with PVDF branches ( 13 ), and they were characterized by transmission electron microscopy and comparative elemental analysis was carried out with naked MNPs.

Published
2018

47. Thermal Decomposition of Fluoroalkyl Pentacarbonylmanganese(I) Derivatives by α-Fluorine Elimination

Author

Rinaldo Poli, Roberto Morales-Cerrada, Florence Gayet, Vincent Ladmiral, Christophe Fliedel, Bruno Ameduri, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Institut Universitaire de France (IUF), Ministère de l'Education nationale, de l’Enseignement supérieur et de la Recherche (M.E.N.E.S.R.), Centre National de la Recherche Scientifique (CNRS), ANR-14-CE07-0012,FLUPOL,Meilleurs polymères fluorés par la polymérisation radicalaire par voie organométallique(2014), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, Organic Chemistry, Thermal decomposition, chemistry.chemical_element, Fluorine-19 NMR, Manganese, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, Dissociation (chemistry), 0104 chemical sciences, Homolysis, Inorganic Chemistry, chemistry.chemical_compound, chemistry, Fluorine, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Bond cleavage, Organometallic chemistry
Abstract

International audience; This contribution brings to light the first example of an α-F elimination process in manganese organometallic chemistry. As shown in a recent contribution ( Chem. Eur. J., DOI: 10.1002/chem.201804007) the thermal decomposition of compounds [Mn(RF)(CO)5] (RF = CF3, 1; CHF2, 2; CH2CF3, 3) in C6D6 at 70–100 °C leads primarily to homolytic Mn–RF bond cleavage, followed by RF• trapping in the presence of (Me3Si)3SiH (TTMSS) to yield RF–H. However, the formation of other products was revealed by a detailed 19F NMR investigation. Compounds 1 and 2 also produced significant amounts of (Me3Si)3SiF and of F-poorer organic compounds (namely, CH2F2 and CH3F from 1; CH3F from 2). The extent of this additional process was rather important (67%) for 1 but minor (10%) for 2. In contrast, no traces of either (Me3Si)3SiF or CH3CHF2 were detected during the decomposition of 3. A DFT investigation shows that the process occurs via CO dissociation followed by α-F elimination from [Mn(RF)(CO)4] to yield [cis-MnF(CXF)(CO)4] (X = F for 1, H for 2). The latter can then react with TTMSS via a rate-determining transition state, which is located at a comparable energy to that of the homolytic bond breaking asymptote, to yield (Me3Si)3SiF and [Mn(CXHF)(CO)5] after CO addition. The greater extent of (Me3Si)3SiF formation produced by the H/F exchange in the order 1 > 2 agrees with the stronger Mn–RF bond in the same order. Analysis of the relative barriers for the two competitive processes at 100 °C confirms that the experimentally determined ΔH⧧ for the thermal decompositions of 1, 2, and 3 are close estimates of the Mn–RF bond dissociation energies (BDEs).

Published
2018

48. Preparation of well-defined 2D-lenticular aggregates by self-assembly of PNIPAM- b -PVDF amphiphilic diblock copolymers in solution

Author

Franck Godiard, Enrique Folgado, Matthias Mayor, Vincent Ladmiral, Michel Ramonda, Mona Semsarilar, Didier Cot, Laboratoire de chimie de coordination (LCC), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie de Toulouse (ICT-FR 2599), Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Recherche pour le Développement (IRD)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées, Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Centrale de Technologie en Micro et Nanoélectronique CTM-­LMCP, Université de Montpellier (UM), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM), Institut Européen des membranes (IEM), Université de Montpellier (UM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)

Subjects
chemistry.chemical_classification, Materials science, Molar mass, Polymers and Plastics, Organic Chemistry, Bioengineering, Chain transfer, 02 engineering and technology, Polymer, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Biochemistry, 0104 chemical sciences, chemistry, Chemical engineering, Amphiphile, Copolymer, [CHIM]Chemical Sciences, Lamellar structure, Reversible addition−fragmentation chain-transfer polymerization, Self-assembly, 0210 nano-technology
Abstract

PNIPAM-b-PVDF (poly(N-isopropylacrylamide)-b-poly(vinylidene fluoride)) amphiphilic block copolymers (BCPs) were synthesized via RAFT polymerization from PNIPAM macromolecular chain transfer agents (macro-CTAs). PNIPAM was used as it is one of the few hydrophilic polymers soluble in dimethyl carbonate (DMC) and which can be synthesized using a xanthate CTA with relatively good control. The polymerizations were conducted at 73 °C in DMC using two PNIPAM macro-CTAs of different molar masses and targeting various DPs for the PVDF block. The RAFT polymerization of VDF resulted in relatively well-defined BCPs (Đ ≤ 1.50). These amphiphilic BCPs were able to self-assemble into various morphologies such as spherical, crumpled, lamellar and lenticular 2D aggregates by changing the common solvent or the self-assembly protocol. The size of the aggregates could be controlled by varying the DP of the PVDF block. The polymers were characterized by 1H and 19F NMR, SEC, TGA and DSC, and the assembled structures were studied by TEM, SEM and AFM. The thermosensitive behavior of the 2D lenticular aggregates was also examined.

Published
2021

49. RAFT Polymerisation of Trifluoroethylene: The importance of understanding reverse additions

Author

Rinaldo Poli, Cédric Totée, Vincent Bouad, Jean-Francois Tahon, Vincent Ladmiral, Olinda Gimello, Marc Guerre, Gilles Silly, Sophie Barrau, Bruno Ameduri, 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), Interactions moléculaires et réactivité chimique et photochimique (IMRCP), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut Ecologie et Environnement (INEE), Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Fédération de Recherche Fluides, Energie, Réacteurs, Matériaux et Transferts (FERMAT), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), P3R - Polymères de Précision par Procédés Radicalaires (P3R), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie de Toulouse (ICT), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de chimie de coordination (LCC), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), ANR-16-CE08-0025,NanoPiC,Etude du comportement piézoélectrique multi-échelles de composites innovants micro- et nano-structurés(2016), 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)-Centrale Lille Institut (CLIL), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), and Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, Polymers and Plastics, Organic Chemistry, Kinetics, Bioengineering, 02 engineering and technology, Nuclear magnetic resonance spectroscopy, Raft, Crystal structure, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Biochemistry, 0104 chemical sciences, chemistry.chemical_compound, Monomer, [CHIM.POLY]Chemical Sciences/Polymers, Transfer agent, Chemical engineering, chemistry, Polymerization, 0210 nano-technology
Abstract

International audience; This article is the first report of the RAFT polymerisation of trifluoroethylene (TrFE). Trifluoroethylene is a rare but very important fluoromonomer, as it allows the preparation of materials endowed with unique electroactivity via copolymerisation with vinylidene fluoride (VDF) and other fluoromonomers. RAFT polymerisations carried out using O-ethyl-S-(1-methoxycarbonyl) ethyldithiocarbonate as a chain transfer agent and a thermal initiator were carefully examined. The polymerisation, its kinetics and the chain-end evolution were investigated by GPC, 1H{19F} and 19F{1H} NMR spectroscopy as well as MALDI-TOF mass spectrometry. Similar to the RAFT polymerisation of VDF, irreversible transfer reactions and reverse additions significantly affect the control of the polymerisation as well as the chain-end functionality. However, in contrast to VDF, unusual reverse propagation of TrFE, although limited to a few monomer units, was evidenced thanks to a combined NMR spectroscopy and DFT calculation approach. RAFT polymerisation afforded relatively well-defined PTrFE with a crystalline structure consistent with previous reports.

Published
2021

50. Plant-environment microscopy tracks interactions of Bacillus subtilis with plant roots across the entire rhizosphere

Author

Daniel Patko, Lionel X. Dupuy, Yangminghao Liu, Ilonka Engelhardt, Bruno Ameduri, Nicola Holden, Tim J. Daniell, Timothy S. George, Nicola R. Stanley-Wall, Michael P. MacDonald, and Vincent Ladmiral

Subjects
Colonisation, Rhizosphere, biology, Seedling, Microorganism, Botany, Microscopy, Bacillus subtilis, biology.organism_classification, Root cap, Mesocosm
Abstract

Our understanding of plant-microbe interactions in soil is limited by the difficulty of observing processes at the microscopic scale throughout plants’ large volume of influence. Here, we present the development of 3D live microscopy for resolving plant-microbe interactions across the environment of an entire seedling growing in a transparent soil in tailor-made mesocosms, maintaining physical conditions for the culture of both plants and microorganisms. A tailor made dual-illumination light-sheet system acquired scattering signals from the plant whilst fluorescence signals were captured from transparent soil particles and labelled microorganisms, allowing the generation of quantitative data on samples approximately 3600 mm3 in size with as good as 5 μm resolution at a rate of up to one scan every 30 minutes. The system tracked the movement of Bacillus subtilis populations in the rhizosphere of lettuce plants in real time, revealing previously unseen patterns of activity. Motile bacteria favoured small pore spaces over the surface of soil particles, colonising the root in a pulsatile manner. Migrations appeared to be directed towards the root cap, the point “first contact”, before subsequent colonisation of mature epidermis cells. Our findings show that microscopes dedicated to live environmental studies present an invaluable tool to understand plant-microbe interactions.

Published
2021

Catalog

Books, media, physical & digital resources
See catalog results