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Beyond the need to find a non-toxic alternative to DiGlycidyl Ether of Bisphenol-A (DGEBA), the serious subject of non-epichlorohydrin epoxy resins production remains a crucial challenge that must be solved for the next epoxy resin generations. In this context, this study focuses on the valorization of vegetable oils (VOs) into thermoset materials by using (i) epoxidation of the VOs through the “double bonds to epoxy” synthetic route and (ii) synthesis of crosslinked homopolymers by UV or hardener-free thermal curing processes. A thorough identification, selection and physico-chemical characterization of non-edible or non-valuated natural vegetable oils were performed. Selected VOs, characterized by a large range of double bond contents, were then chemically modified into epoxides thanks to an optimized, robust and sustainable method based on the use of acetic acid, hydrogen peroxide and Amberlite® IR-120 at 55 °C in toluene or cyclopentyl methyl ether (CMPE) as a non-hazardous and green alternative solvent. The developed environmentally friendly epoxidation process allows reaching almost complete double bond conversion with an epoxy selectivity above 94% for the 12 studied VOs. Finally, obtained epoxidized vegetable oils (EVOs), characterized by an epoxy index from 2.77 to 6.77 meq. g−1 were cured using either UV or hardener-free thermal curing. Both methods enable the synthesis of 100% biobased EVO thermoset materials whose thermomechanical performances were proved to linearly increase with the EVOs' epoxy content. This paper highlights that tunable thermomechanical performances (Tα from −19 to 50 °C and Tg from −34 to 36 °C) of EVO based thermoset materials can be reached by well selecting the starting VO raw materials.

Oxidative stress, which is one of the main harmful mechanisms of pathologies including is-chemic stroke, contributes to both neurons and endothelial cell damages, leading to vascular lesions. Although many antioxidants have been tested in preclinical studies, no treatment is currently available for stroke patients. Since cerium oxide nanoparticles (CNPs) exhibit remarkable antioxidant capacities, our objective is to develop an innovative coating to enhance CNPs biocompatibility without disrupting their antioxidant capacities or enhance their toxicity. This study reports the synthesis and characterization of functional polymers and their impact on the enzyme-like catalytic activity of CNPs. To study the toxicity and the antioxidant properties of CNPs for stroke and particularly endothelial damages, in vitro studies are conducted on a cerebral endothelial cell line (bEnd.3). Despite their internalization in bEnd.3 cells, coated CNPs are devoid of cytotoxicity. Microscopy studies report an intracellular localization of CNPs, more precisely in endosomes. All CNPs reduces glutamate-induced intracellular production of ROS in endothelial cells but one CNP significantly reduces both the production of mitochondrial super-oxide anion and DNA oxidation. In vivo studies report a lack of toxicity in mice. This study there-fore describes and identifies biocompatible CNPs with interesting antioxidant properties for ischemic stroke and related pathologies., 27 pages 9 figures

The combination of multiple functionalities in a single material is an appealing strategy for the de-velopment of smart materials with unique features. In this work, we present the preparation of thermoresponsive magnetic nanoparticles and their one-dimensional assembly into transient micro-filaments. The material is based on 9.4 nm iron oxide nanoparticles grafted with poly(N-n-propylacrylamide) via multiphosphonic acid anchoring sites. The hybrid nanoparticles present a low critical solution temperature (LCST) transition between 21 {\deg}C and 28 {\deg}C, depending on the pH and the ionic strength. When heated above the LCST in defined conditions, the nanoparticles ag-gregate and respond to an external magnetic field. An intrinsic characteristic of the thermorespon-sive particles is an asymmetric transition between cooling and heating cycles, that was favorably exploited to build one-dimensional permanent microstructures, such as magnetic microfilaments and cilia. In summary, we present the development of a nanoplatform responsive to multiple stimu-li, including temperature, magnetic field, pH and ionic strength and its transformation into magneti-cally active microfilaments that could find potential applications in remotely controlled devices., Comment: 18 pages, 8 figures

Bio-epoxy resins based on five epoxidized vegetable oils were formulated with an aromatic disulfide crosslinker with diacid functionality, 2,2′-dithiodibenzoic acid (DTBA), to obtain recyclable epoxy thermosets. Flax fibres (FF) and PLA woven were used as bio-based reinforcements for these matrices. Different percentages of reinforcement were tested and the effect of the natural fibres on the matrix's crosslinking reaction was studied by DSC analysis. Then, the obtained materials were analyzed by Differential Scanning Calorimetry (DSC), Thermogravimetric Analysis (TGA), Dynamic Mechanical Analysis (DMA), water absorption and Scanning Electron Microscopy (SEM). The reinforcements improved the thermal and mechanical properties of the neat resins, with tan δ values varying from 91 to 148 °C showing a good compatibility matrix-FF but a reduced one in case of matrix-PLA woven. The dynamic nature of the networks crosslinking allowed the chemical and mechanical recycling of both resins and bio-composites. Moreover, the obtained results show the possibility to recuperate the natural FF filler for the preparation of second-life generation bio-composites.

International audience; The preparation of thermosets based on epoxidized vegetable oils (EVOs) involved a peculiar attention in recent years; however, most of them cannot be recycled once cross-linked. In the present work, epoxy thermosetting resins like-vitrimers with dynamic disulfide covalent bonds were prepared by copolymerizing twelve EVOs with 2,2′-dithiodibenzoic acid, as hardener. Here, we show for the first time the reprocessability, repairability, and recyclability properties of EVOs thermosets. The 3R abilities were evaluated in correlation with the EVO epoxy contents, which influence the final thermo-mechanical properties of the recycled material. The virgin versus recycled materials' comparison was studied by FT-IR, DSC, TGA, and DMA, also comparing their swelling ability and high gel content. The study investigates, in addition, the excellent shape memory properties of the reprocessed EVOs/disulfide materials.

Epoxy resins are widely used in the composite industry due to their dimensional stability, chemical resistance, and thermo-mechanical properties. However, these thermoset resins have important drawbacks. (i) The vast majority of epoxy matrices are based on non-renewable fossil-derived materials, and (ii) the highly cross-linked molecular architecture hinders their reprocessing, repairing, and recycling. In this paper, those two aspects are addressed by combining novel biobased epoxy monomers derived from renewable resources and dynamic crosslinks. Vanillin (lignin) and phloroglucinol (sugar bioconversion) precursors have been used to develop bi- and tri-functional epoxy monomers, diglycidyl ether of vanillyl alcohol (DGEVA) and phloroglucinol triepoxy (PHTE) respectively. Additionally, reversible covalent bonds have been incorporated in the network by using an aromatic disulfide-based diamine hardener. Four epoxy matrices with di erent ratios of epoxy monomers (DGEVA/PHTE wt%: 100/0, 60/40, 40/60, and 0/100) were developed and fully characterized in terms of thermal and mechanical properties. We demonstrate that their performances are comparable to those of commonly used fossil fuel-based epoxy thermosets with additional advanced reprocessing functionalities. This project has received funding from the Bio Based Industries Joint Undertaking under the European Union’s Horizon 2020 research and innovation program under grant agreement No 744311

Cerium oxide nanoparticles have been shown to mimic oxidoreductase enzymes by catalyzing the decomposition of organic substrates and reactive oxygen species. This mimicry can be found in superoxide radicals and hydrogen peroxides, harmful molecules produced in oxidative stress asso-ciated diseases. Despite the fact that nanoparticle functionalization is mandatory in the context of nanomedicine, the influence of polymer coatings on their enzyme-like catalytic activity is poorly understood. In this work, six polymer coated cerium oxide nanoparticles are prepared by associa-tion of 7.8 nm cerium oxide cores with two poly(sodium acrylate) and four poly(ethylene glycol) (PEG) grafted copolymers with different terminal or anchoring end groups, such as phosphonic acids. The superoxide dismutase-, catalase-, peroxidase- and oxidase-like catalytic activities of the coated nanoparticles were systematically studied. It is shown that the polymer coatings do not af-fect the superoxide dismutase-like, impair the catalase-like and oxidase-like and surprisingly im-proves peroxidase-like catalytic activities of cerium oxide nanoparticles. It is also demonstrated that the particles coated with the PEG-grafted copolymers perform better than the poly(acrylic acid) coated ones as oxidoreductase-like enzymes, a result that confirms the benefit of having phosphon-ic acids as anchoring groups at the particle surface., Comment: 23 pages, 8 figures, 3 tables

International audience; Bisphenol A based epoxy thermosets involve both environmental and health risks. By reacting a vegetal oil-based epoxide with an aromatic diacid containing S-S bonds a thermoset is produced. Herein, reprocessable thermosets were synthesized, the recyclability being designed through a dual mechanism: that of disulfide metathesis and of transesterifications. To assess the feasibility of the reprocessing, a series of ten initiators were tested to probe their effect not only on the crosslinking reaction but also on the recyclability. This study introduces for the first time the key role of the initiator on the material performances and on their reprocessing. A very good reprocessability was obtained for thermosets prepared using as initiator the imidazole. Moreover, the thermosets exhibit complete chemical recyclability in 1N NaOH at 80 °C, after 3 days, without needing additional chemicals. The reprocessed materials have similar performances with the virgin ones, even after 10 cycles of reprocessing.

International audience; In a sustainable development context, epoxidized vegetable oils (EVO) have unlimited and promising future prospects as renewable and environmentally friendly feedstock. The only drawback to their use is their low and non-selective reactivity compared to the aromatic epoxides. Properly, a small optimized amount of "true" initiators can overcome this issue and also beneficially serve in properties such as glass transition, modulus, strength, elongation at break, and chemical resistance. This paper presents efforts to understand and identify the initiator's effect to more accurately predict how to select a good initiator on EVO/dicarboxylic acid systems. A new bio-based reprocessable epoxy resin was prepared from epoxidized linseed oil (ELO) and 2,2′-dithiodibenzoic acid (DTBA). The evolution of the chemical structures and the reactions' mechanisms have been systematically studied by in situ Fourier transform infrared (FT-IR) and nuclear magnetic resonance (NMR) spectroscopies and differential scanning calorimetry (DSC). A screening of 10 initiators was performed for the ELO/DTBA cross-linking reaction. The influence of the initiator's structure, basicity, and nucleophilicity was assessed and ranked in terms of the kinetic response including the epoxy− acid reaction rate and the percentage of functional group consumption. An excellent effect achieved by imidazole as an initiator was demonstrated. An attempt has been proposed to corroborate the experimental values with the results of quantum chemistry calculations.

International audience; For the first time, the effect of reactant structure, stoichiometry and heating rate on the reactivity of epox-idized perilla oil (EPLO) and epoxidized safflower oil (ESFO) with dicarboxylic acids (DCAs) was studied using in situ FT-IR. The epoxy content in the monomer structure was found to affect the copolymeriza-tion system's reactivity, with epoxidized linseed oil (ELO) considered as a reference. In this study we discuss also the influence of the DCA structure on the copolymerization reactivity. Two aromatic diacids, dithiodibenzoic acid (DTBA) and diphenic acid (DPA), were studied and compared in the copolymerization of the 3 EVOs, in the presence of imidazole (IM) initiator. The kinetics of these reactions were followed by in situ FT-IR. The corresponding activation energies were calculated via different kinetic models. These data highlight the higher reactivity of the EPLO monomer and the DTBA hardener.

Bio-inspired materials are commonly used in the development of functional devices. The fabrication of artificial cilia mimicking the biological functions has emerged as a promising strategy for fluid manipulation in miniaturized systems. In this study, we propose a different physicochemical insight for the preparation of magnetic cilia based on the temperature-triggered reversible assembly of coated iron oxide nanoparticles in a bio-compatible template-free approach. The length of the prepared cilia could be tuned between 10 and 100 microns reaching aspect ratios up to 100 in a very dense array of flexible structures with persistence lengths around 8 microns. Magnetic actuation of the cilia revealed robust structures (over several hours of actuation) with a wide range of bending amplitudes resulting from high susceptibility of the filaments. The results demonstrate that the proposed strategy is an efficient and versatile alternative for templated fabrication methods and producing cilia with remarkable characteristics and dimensions within the template-free approaches., Comment: 15 pages 5 figures

International audience; The end-of-life of thermoset materials is a real issue that confronts our society, and the strategy of introducing dynamic reversible bonds can be a sustainable solution to overcome this problem. This study shows an efficient way to produce biobased and recyclable thermosets, for a circular use. To reduce the production costs linked to energy and duration, an improved curing process is proposed by combining aromatic and aliphatic diacid hardeners containing dynamic S−S bonds. The work demonstrates the increased reactivity of epoxidized vegetable oil reacted with the two diacids. The structural evolutions during the exchange reactions that allow the recyclability were followed by Fourier transformed-infrared and nuclear magnetic resonance spectroscopies, high-performance liquid chromatography, and mass spectroscopy. The curing process was studied by differential scanning calorimetry and kinetic study.

Even though the hydrosilylation reaction has been the method of choice to produce organosilicon compounds for 70 years, improving its selectivity still remains a current challenge. In this work, a comprehensive study of the influence of experimental parameters on hydrosilylation side reactions was undertaken by applying a fractional factorial design of experiments. The study was conducted for polyethylene glycol (PEG, 1000 g mol−1) terminated allyl ether, which is commonly employed as a reactive functional group toward hydrosilylation. In addition, the resulting silane-functionalized PEG happens to be a molecule of interest in various domains such as the biomedical, cosmetic or food industry thanks to its properties in accordance with these sectors' requirements. This methodology enables highlighting an optimized combination of experimental parameters as well as a cause–effect relationship between the different side reactions, leading to a better control of the hydrosilylation reaction.

This paper reports the synthesis of epoxy functionalized bio-renewable monomers that can be applied in cationic photopolymerization. The cationic UV-curing process was efficient giving rise to crosslinked coatings with a wide range of thermo-mechanical properties. The final properties were analysed based on the monomer chemical structure.

Whether it is for imparting anti-corrosion, anti-fogging or stable optical properties, hydrophobic coatings have been at the center of numerous research studies these last few decades. While surface perfluorination and surface roughening have been thoroughly studied, few studies discuss the introduction of fluoroalkylsilanes (FASs) directly into sol–gel networks in order to obtain water-repellent silica films. The latter method, referred to as co-condensation, is yet easier to perform (one-pot and mild conditions) and in accordance with industrial standards. However, so far its implementation to achieve maximum surface hydrophobicity has not been well-controlled and the influence of such FAS molecules trapped in the sol–gel network on the mechanical properties has not been investigated. In this work, how the co-condensation method affects the distribution of the fluorinated additives in the sol–gel network is studied by obtaining a precise XPS profile of the FASs within the material. The water-repellent, optical and mechanical properties of such coatings were evaluated. From these results, the one-step co-condensation method was proved to exhibit similar properties to a classic multi-step surface silanization. Moreover, by getting a better understanding of the mechanisms involved during the film formation, it is henceforth possible to accurately control the concentration of FASs needed to optimize the water-repellency. Besides, it was demonstrated that these results were not impacted by the chemical structure of the FASs, thus highlighting various alternative synthesis strategies of interest. Based on these conclusions, the co-condensation is, for the first time, demonstrated to be a method of choice to prepare water-repellent sol–gel coatings, presenting the significant advantage compared to classic silanization to allow an accurate adjustment of the FAS concentration in order to achieve maximum hydrophobicity.

SPECIFIC POLYMERS is a SME acting as R&D service provider in the field of functional monomers, polymers and materials with high specificity. In more than 12 years, SP has developed the synthesis of more than 1000 functional building blocks, monomers and polymers and is now working with more than 400 customers and partners in more than 30 countries worldwide in all field of applications such as surface finishing (glass, metal, metal oxides, nanoparticles, plastics), aeronautic, automotive, pharmaceutical industry, cosmetic, electronic, optic, energy (fuel cells, solar cells or lithium batteries). Since 2013, SP is developing innovative materials for electronic devices. As for example, SP is involved in PiezoMAT European Project and develops UV-crosslinkable thin layer polymeric materials for the encapsulation of ZnO nanowires (NWs) in multi-NWs pressure based fingerprint sensors.

To estimate the potential of ZnO nanostructures for force sensing applications, arrays of single nanowires and arrays of nanowire bundles have been fabricated by wet chemical growth method. The piezoelectrical and electrical properties of the single nanowires have been investigated by atomic force microscopy based techniques. The piezoelectric constant d(33) = 15 pm/V has been determined from vibration analyses. The electrical response in the range up to 400 fA upon applying force between 40 nN and 1 mu N has been recorded. The nanowire bundles were studied by electro-mechanical macro probing technique within the force range 1 - 10 mN, where a reproducible response in pA range has been measured.

We report on the synthesis, characterization, stability and pharmacokinetics of novel iron based contrast agents for magnetic resonance imaging (MRI). Statistical copolymers combining multiple phosphonic acid groups and poly(ethylene glycol) (PEG) were synthesized and used as coating agents for 10 nm iron oxide nanocrystals. In vitro, protein corona and stability assays show that phosphonic acid PEG copolymers outperform all other coating types examined, including low molecular weight anionic ligands and polymers. In vivo, the particle pharmacokinetics is investigated by monitoring the MRI signal intensity from mouse liver, spleen and arteries as a function of the time, between one minute and seven days after injection. Iron oxide particles coated with multi-phosphonic acid PEG polymers are shown to have a blood circulation lifetime of 250 minutes, i.e. 10 to 50 times greater than that of recently published PEGylated probes and benchmarks. The clearance from the liver takes in average 2 to 3 days and is independent of the core size, coating and particle stability. By comparing identical core particles with different coatings, we are able to determine the optimum conditions for stealth MRI probes., Comment: 19 pages 8 figures, RSC Advances, 2016

When disperse in biological fluids, engineered nanoparticles are selectively coated with proteins, resulting in the formation of a protein corona. It is suggested that the protein corona is critical in regulating the conditions of entry into the cytoplasm of living cells. Recent reports describe this phenomenon as ubiquitous and independent of the nature of the particle. For nanomedicine applications however, there is a need to design advanced and cost-effective coatings that are resistant to protein adsorption and that increase the biodistribution in vivo. In this study, phosphonic acid poly(ethylene glycol) copolymers were synthesized and used to coat iron oxide particles. The copolymer composition was optimized to provide simple and scalable protocols as well as long-term stability in culture media. It is shown that polymers with multiple phosphonic acid functionalities and PEG chains outperform other types of coating, including ligands, polyelectrolytes and carboxylic acid functionalized PEG. PEGylated particles exhibit moreover exceptional low cellular uptake, of the order of 100 femtograms of iron per cell. The present approach demonstrates that the surface chemistry of engineered particles is a key parameter in the interactions with cells. It also opens up new avenues for the efficient functionalization of inorganic surfaces., 21 page, 7 figures,Biomacromolecules 2014

In this paper, original thermosensitive copolymers bearing phosphonic acid groups, namely the poly(N-n-propylacrylamide-stat-2-(methacryloyloxy)methylphosphonic acid) (P(NnPAAm-stat-hMAPC1)) were synthesized, and their sorption properties for three divalent cations (Ni(2+), Ca(2+), Cd(2+)) and one trivalent cation (Al(3+)) have been investigated. The sorption experiments were performed with increasing relative amount of cationic pollution compared to the amount of sorption sites (C(n+)/P ratio) in mono and multi-component solutions to investigate the sorption mechanisms. C(n+)/P proved to strongly affect the sorption capacity and high capacities were obtained for all cations at highest C(n+)/P ratios, reaching one mole of C(sorbed)(n+) per phosphonated moiety. For divalent cations, sorption mechanisms were likely to be described by electrostatic interactions only, whereas for aluminum trivalent cation the sorption not only resulted from electrostatic interactions but also from the formation of coordination binding. The selectivity of the phosphonic acid moieties for aluminum cations was demonstrated, highlighting the interest of P(NnPAAm-stat-(h)MAPC1) for their use for the treatment of metallic pollution from wastewater.

International audience; In this work, new thermosensitive copolymers bearing phosphonated groups were synthesized and used to remove metal pollution. Sorption properties are brought by hydrolysed (dimethoxyphosphoryl)methyl 2-methylacrylate (hMAPC1) monomer. N-n-propylacrylamide (NnPAAm) led to the thermoresponsive properties of the copolymers. Low Lower Critical Solution Temperature (LCST) values were observed, ranging between 20 °C and 25 °C depending on the molar ratio of each monomer in the copolymer. Sorption properties of these copolymers toward nickel ions were evaluated for increasing temperatures (10 to 40 °C), Ni ions concentrations of 20 mg.L-1 and pH values between 3 and 7. Best results were observed for temperatures just lower than the LCST (20 °C), when the copolymer was fully soluble in water solution. For temperature higher than the LCST, phosphonic diacid groups accessibility was considerably reduced by the precipitation of the thermosensitive part of the copolymer leading to lower sorption properties. In these conditions, the highest Ni removal by the copolymer was observed for pH = 7, when there was almost no competition between the sorption of H+ and Ni2+ ions on the phosphonic acid groups. These optimal conditions enabled to remove about 70% of the Nickel in the synthetic effluent.

In order to remove metal ions from wastewaters, thermosensitive copolymers bearing sorption properties toward metal cations were prepared by free radical copolymerization between the N- n -propylacrylamide (N n PAAm) and the (dimethoxyphosphoryl)methyl 2-methylacrylate (MAPC1), followed by a hydrolysis of the phosphonated esters into phosphonic diacid groups ( h MAPC1). The thermosensitivity and the sorption abilities of the resulting poly(N n PAAm- stat - h MAPC1) copolymers were studied. Lower Critical Solution Temperatures (LCST) of these copolymers ranged from 22 °C to 26 °C, depending on the molar ratio of phosphonated monomers and were lower than those obtained with usual poly(N- iso propylacrylamide)-based polymers. The influence of both the temperature and the pH on the sorption properties of the copolymers was evaluated for Ni 2+ cations. The most interesting results were obtained for temperatures around the LCST, i.e. when the proximity of the complexing groups favored the sorption of metallic cations. Concerning the pH effect, the maximum sorption capacity was obtained at pH 7, i.e. in the absence of competition between the sorption of H + and Ni 2+ ions on the phosphonic acid groups. The influence of the molar ratio of metal ions and phosphonate moieties was also studied and different sorption mechanisms were proposed.

International audience; The present contribution reports on the synthesis and controlled polymerization of a novel acrylamide monomer containing phosphonated moieties, namely diethyl-2-(acrylamido)ethylphosphonate. This monomer appears to be of great interest due to the phosphonated moieties, which can lead to a wide range of applications, associated with the chemical stability of the acrylamide compared to more common (meth)acrylate monomers. Reversible Addition-Fragmentation Transfer (RAFT) polymerization of this monomer was investigated using two different trithiocarbonate chain transfer agents, and it allowed the synthesis of poly(diethyl-2-(acrylamido)ethylphosphonate) with controlled molecular weight and low dispersity. Additionally, a diblock copolymer was successfully prepared by a similar RAFT procedure using thermosensitive poly(N-n-propylacrylamide) as a macro-chain transfer agent. A combination of both stimuli-responsive and phosphonated ester or phosphonic diacid (after hydrolysis) containing blocks appears valuable for drug delivery or water treatment, for instance.

International audience; This Review is focused on the growing interest brought to phosphorus-containing organic materials for applications in the biomedical field, mainly because of their properties such as biocompatibility, hemocompatibility, and protein adsorption resistance. It mainly describes relevant works achieved on these materials for various applications: dentistry, regenerative medicine, and drug delivery. Special attention was given to 2-methacryloyloxyethyl phosphorylcholine (MPC) monomer as the latter appeared of great importance because of its biomimetic structure due to the presence of the phospholipid group on its structure. As a result, much research effort is currently concentrated on the development of phosphorylcholine- containing (co)polymers that represent a promising class of materials.

International audience; This work reports for the first time the copolymerization studies of 11 newly synthesized epoxidized vegetable oils (EVOs) that reacted with a disulfide-based aromatic dicarboxylic acid (DCA) to produce thermoset materials with recyclability properties. These new EVOs’ reactivity and properties were compared with those of the two commercial references: epoxidized linseed oil (ELO) and epoxidized soybean oil (ESO). The structure–reactivity correlation is proposed by differential scanning calorimetry (DSC) analysis, corroborating the epoxy content of EVO monomers, the initiator effect, the copolymerization reaction enthalpy, and the temperature range. The thermomechanical properties of the obtained thermosets were evaluated and discussed in correlation with the structure and reactivity of monomers by dynamic mechanical analysis (DMA), tensile testing, and thermogravimetric analysis (TGA). It has been found that the higher the EVO functionality, the higher is the reactivity, cross-linking density, and final performances, with tan δ values ranging from 34 to 111 °C. This study investigates the chemical recycling and the solvent resistance of these vitrimer-like materials that have a high bio-based carbon content, from 58 to 79%, with potential application in coating or composite materials in the automotive sector