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Increasing plants photosynthetic efficienc y is a major challenge that must be addressed in order to cover the food demands of the growing population in the changing climate. Photosynthes i s is greatly limited at the initial carboxylation reaction, where CO2 is converted to the organic acid 3-PGA, catalyzed by the RuBisCO enzyme. RuBisCO has poor affinity for CO2, but also the CO2 concentration at the RuBisCO site is limited by the diffusion of atmospheric CO2 through the various leaf compartments to the reaction site. Beyond genetic engineer-ing, nanotechnology can offer a materials-based approach for enhancing photosynthesis, and yet, it has mostly been explored for the light-dependent reactions. In this work, we developed polyethyleneimine-based nanoparticl e s for enhancing the carbox-ylation reaction. We demonstrate that the nanoparticles can capture CO2 in the form of bicarbonate and increase the CO2 that reacts with the RuBisCO enzyme, enhancing the 3-PGA production in in vitro assays by 20%. The nanoparticles can be introduced to the plant via leaf infiltration and, because of the functionalization with chitosan oligomers, they do not induce any toxic effect to the plant. In the leaves, the nanoparticles localize in the apoplastic space but also spontaneously reach the chloroplasts where photosynthetic activity takes place. Their CO2 loading-dependent fluorescence verifies that, in vivo, they maintain their abi l i t y to capture CO2 and can be therefore reloaded with atmospheric CO2 while in planta. Our results contribute to the development of a nanomaterials-based CO2-concentrating mechanism in plants t h a t can potentially increase photosynthetic efficiency and overall plants CO2 storage. Funding Agencies|European Union [800926, 101042148]; Swedish Research Council [VR-2017-04910]; Swedish Government Strategic Research Area in Materials Science on Advanced Functional Materials at Linkoping University [2009-00971]; MCIN/AEI [Ayuda RYC2021-031668-I]

Electrocardiography imaging (ECGi) is a non‐invasive inverse reconstruction procedure which employs body surface potential maps (BSPM) obtained from surface electrode array measurements to improve the spatial resolution and interpretability of conventional electrocardiography (ECG) for the diagnosis of cardiac dysfunction. ECGi currently lacks precision, which has prevented its adoption in clinical setups. The introduction of high‐density electrode arrays could increase ECGi reconstruction accuracy but is not attempted before due to manufacturing and processing limitations. Advances in multiple fields have now enabled the implementation of such arrays which poses questions on optimal array design parameters for ECGi. In this work, a novel conducting polymer electrode manufacturing process on flexible substrates is proposed to achieve high‐density, mm‐sized, conformable, long‐term, and easily attachable electrode arrays for BSPM with parameters optimally selected for ECGi applications. Temporal, spectral, and correlation analysis are performed on a prototype array demonstrating the validity of the chosen parameters and the feasibility of high‐density BSPM, paving the way for ECGi devices fit for clinical application.

Eutectogels are an emerging family of soft ionic materials alternative to ionic liquid gels and organogels, offering fresh perspectives for designing functional dynamic platforms in water-free environments. Herein, the first example of mixed ionic and electronic conducting supramolecular eutectogel composites is reported. A fluorescent glutamic acid-derived low-molecular-weight gelator (LMWG) was found to self-assemble into nanofibrillar networks in deep eutectic solvents (DES)/poly(3,4-ethylenedioxythiophene) (PEDOT): chondroitin sulfate dispersions. These dynamic materials displayed excellent injectability and self-healing properties, high ionic conductivity (up to 10−2 S cm−1), good biocompatibility, and fluorescence imaging ability. This set of features turns the mixed conducting supramolecular eutectogels into promising adaptive materials for bioimaging and electrostimulation applications. This work was supported by Marie Sklodowska-Curie Research and Innovation Staff Exchanges (RISE) under the grant agreement No 823989 “IONBIKE”. The financial support received from CONICET and ANPCyT (Argentina) is also gratefully acknowledged. M. C.-G. thanks Emakiker Grant Program of POLYMAT. L. C. T. is grateful to Fundação para a Ciência e a Tecnologia (FCT/MCTES) in Portugal for her research contract under Scientific Employment Stimulus (2020.01555.CEECIND), and Associate Laboratory for Green Chemistry—LAQV, which is also financed by FCT/MCTES (UIDB/50006/2020 and UIDP/50006/2020). D. M. thanks “Ayuda RYC2021-031668-I financiada por MCIN/AEI/10.13039/501100011033 y por la Unión Europea NextGenerationEU/PRTR”. The authors thank the technical and human support provided by SGIker (UPV/EHU/ERDF, EU).

Energy storage will be a primordial actor of the ecological transition initiated in the energy and transport sectors. As such, innovative approaches to design high-performance electrode materials are crucial for the development of the next generation of batteries. Herein, a novel dual redox-active and porous polyimide network (MTA-MPT), based on mellitic trianhydride (MTA) and 3,7-diamino-N-methylphenothiazine (MPT) monomers, is proposed for applications in both high energy density lithium batteries and symmetric all-organic batteries. The MTA-MPT porous polyimide was synthesized using a novel environmentally-friendly hydrothermal polymerization method. Rooted in its dual redox proprieties, the MTA-MPT porous polyimide exhibits a high theoretical capacity making it a very attractive cathode material for high energy density battery applications. The cycling performance of this novel electrode material was assessed in both high energy density lithium batteries and light-weight symmetric all-organic batteries, displaying excellent rate capability and long-term cycling stability. N. Goujon acknowledges the funding from the European Union's Horizon 2020 framework programme under the Marie Sklodowska-Curie agreement No. 101028682. M. Lahnsteiner, H. M. Moura, D. A. Cerron-Infantes and M. M. Unterlass acknowledge funding through the Austrian Science Fund's (FWF) START programme under grant no. Y1037-N28. We thank Dr Jerpme Roeser and Prof. Arne Thomas (TU Berlin) for gas sorption measurements.

Ionic liquids and poly(ionic liquid)s act as bulk and/or passivation agents when used as additives in methylammonium-free lead perovskites, leading to devices showing enhanced power conversion efficiencies, reduced hysteresis and improved stability.

The use of plastic waste to develop high added value materials, also known as upcycling, is a useful strategy towards the development of more sustainable materials. More specifically, the use of plastic waste as a feedstock for synthesising new materials for energy storage devices can not only provide a route to upgrading plastic waste but can also help in the search for sustainable materials. This perspective describes recent strategies for the use of plastic waste as a sustainable, cheap and abundant feedstock in the production of new materials for electrochemical energy storage devices such as lithium batteries, sodium batteries and supercapacitors. Two main strategies are described, the development of conducting carbons by combustion of plastic waste and the depolymerization of plastics into new chemicals and materials. In both cases, catalysis has been key to ensuring high efficiency and performance. Future opportunities and challenges are highlighted and hypotheses are made on how the use of plastic waste could enhance the circularity of current energy storage devices. NG acknowledges the funding from the European Union’s Horizon 2020 framework programme under the Marie Skłodowska-Curie agreement No. 101028682. CJ acknowledges the financial support from el Ministerio de ciencia e innovación from the Juan de la Cierva Program (FJC2020-045872-I). The funding from the European Union’s Horizon 2020 framework programme under the Marie Skłodowska-Curie agreement No. 101028975 and Ministerio de ciencia e innovación under PDC2021-121461-I00 project is acknowledged.

Functionalized cyclic carbonates are attractive monomers for the synthesis of innovative polycarbonates or polyurethanes for various applications. Even though their synthesis has been intensively investigated, doing so in a sustainable and efficient manner remains a challenge. Herein, we propose an organocatalytic procedure based on the depolymerization of a commodity polymer, bisphenol A based polycarbonate (BPA-PC). Different carbonate-containing heterocycles are obtained in good to excellent yields employing BPA-PC as a sustainable and inexpensive source of carbonate, including functionalized six-membered cyclic carbonates.

Chemical recycling of plastic waste represents a greener alternative to landfill and incineration, and potentially offers a solution to the environmental consequences of increased plastic waste. Most plastics that are widely used today are designed for durability, hence currently available depolymerisation methods typically require harsh conditions and when applied to blended and mixed plastic feeds generate a mixture of products. Herein, we demonstrate that the energetic differences for the glycolysis of BPA-PC and PET in the presence of a protic ionic salt TBD:MSA catalyst enables the selective and sequential depolymerisation of these two commonly employed polymers. Employing the same procedure, functionalised cyclic carbonates can be obtained from both mixed plastic wastes and industrial polymer blend. This methodology demonstrates that the concept of catalytic depolymerisation offers great potential for selective polymer recycling and also presents plastic waste as a "greener" alternative feedstock for the synthesis of high added value molecules.

International audience; We leverage the attractive properties of a high χ-low N BCP, i.e. poly(styrene)-block-poly(2-fluoro ethyl methylacrylate) (PS-b-P2FEMA) and illustrate its utility for next-generation nano-manufacturing. The synthesis, physical characterization and thin film self-assembly of a series of lamellar and cylindrical PS-b-P2FEMA BCPs is delineated. PS-b-P2FEMA BCPs with total molecular weights ranging from 7 kg mol -1 to 22 kg mol -1 were synthesized using reversible-addition-fragmentation chain-transfer (RAFT) polymerization. Temperature resolved small angle X-ray scattering (SAXS) measurements revealed a large χ value (0.13@ 150°C) for PS-b-P2FEMA. Solvo-thermal vapor annealing of PS-b-P2FEMA films produced highly oriented fingerprint patterns in as short as 60 seconds. Lamellar period sizes ranged from 25.9 nm down to 14.2 nm with feature sizes as small as 7 nm observed. We also demonstrate the integration feasibility of PS-b-P2FEMA BCPs through alumina hardmask formation using sequential infiltration synthesis. The highly favorable characteristics of the P2FEMA based BCPs detailed here provide a versatile material option to the current library of available BCPs for sub-10 nm nanolithography.

RAFT polymerization of N‐vinylimidazole followed pseudo‐first‐order kinetics. Morpholine‐based chain transfer agents for rapid polymerization of vinyl acetate afforded high‐molar‐mass poly(vinyl acetate) (up to 130 kg mol−1).

International audience; The landscape of block copolymer (BCP) lithographic patterning has evolved significantly from the early days of the first generation BCP material, poly(styrene)-block-poly(methyl methacrylate) (PS-b-PMMA). The low Flory–Huggins interaction parameter (χ) of the workhorse material PS-b-PMMA prevents ultra-low dimensional scaling (

Certainly, the success of polythiophenes is due in the first place to their outstanding electronic properties and superior processability. Nevertheless, there are additional reasons that contribute to arouse the scientific interest around these materials. Among these, the large variety of chemical modifications that is possible to perform on the thiophene ring is a precious aspect. In particular, a turning point was marked by the diffusion of synthetic strategies for the preparation of terthiophenes: the vast richness of approaches today available for the easy customization of these structures allows the finetuning of their chemical, physical, and optical properties. Therefore, terthiophene derivatives have become an extremely versatile class of compounds both for direct application or for the preparation of electronic functional polymers. Moreover, their biocompatibility and ease of functionalization make them appealing for biology and medical research, as it testifies to the blossoming of studies in these fields in which they are involved. It is thus with the willingness to guide the reader through all the possibilities offered by these structures that this review elucidates the synthetic methods and describes the full chemical variety of terthiophenes and their derivatives. In the final part, an in-depth presentation of their numerous bioapplications intends to provide a complete picture of the state of the art. Operational Program Research, Development, and Education Project “MSCAfellow4@MUNI” (No. CZ.02.2.69/0.0/0.0/20_079/0017045) is acknowledged. The European Union is acknowledged for funding this research through Horizon 2020 MSCA-IF-2018 No 838171 (TEXTHIOL).

The discovery of antibiotics was one of the crowning achievements of the 20th century, revolutionizing the treatment of infectious disease. However, widespread improper use of antibiotics has led t...

Carbon nanomaterials are at the forefront of the newest technologies of the third millennium, and together with conductive polymers, represent a vast area of indispensable knowledge for developing the devices of tomorrow. This review focusses on the most recent advances in the field of conductive nanotechnology, which combines the properties of carbon nanomaterials with conjugated polymers. Hybrid materials resulting from the embedding of carbon nanotubes, carbon dots and graphene derivatives are taken into consideration and fully explored, with discussion of the most recent literature. An introduction into the three most widely used conductive polymers and a final section about the most recent biological results obtained using carbon nanotube hybrids will complete this overview of these innovative and beyond belief materials. The European Union is acknowledged for funding this research through Horizon 2020 MSCA-IF-2018 No 838171 (TEXTHIOL). IMDEA Nanociencia acknowledges support from the “Severo Ochoa” Programme for Centres of Excellence in R&D (MINECO, Grant SEV- 2016-0686). European Regional Development fund Project “MSCAfellow4 @ MUNI” supported by MEYS CR (No. CZ.02.2.69/0.0/0.0/20_079/0017045) is acknowledged. N.A. has received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie grant agreement no. 753293, acronym NanoBEAT.

Plant processes, ranging from photosynthesis through production of biomaterials to environmental sensing and adaptation, can be used in technology via integration of functional materials and devices. Previously, plants with integrated organic electronic devices and circuits distributed in their vascular tissue and organs have been demonstrated. To circumvent biological barriers, and thereby access the internal tissue, plant cuttings were used, which resulted in biohybrids with limited lifetime and use. Here, we report intact plants with electronic functionality that continue to grow and develop enabling plant-biohybrid systems that fully maintain their biological processes. The biocatalytic machinery of the plant cell wall was leveraged to seamlessly integrate conductors with mixed ionic-electronic conductivity along the root system of the plants. Cell wall peroxidases catalyzed ETE-S polymerization while the plant tissue served as the template, organizing the polymer in a favorable manner. The conductivity of the resulting p(ETE-S) roots reached the order of 10 S cm(-1) and remained stable over the course of 4 weeks while the roots continued to grow. The p(ETE-S) roots were used to build supercapacitors that outperform previous plant-biohybrid charge storage demonstrations. Plants were not affected by the electronic functionalization but adapted to this new hybrid state by developing a more complex root system. Biohybrid plants with electronic roots pave the way for autonomous systems with potential applications in energy, sensing and robotics. Funding Agencies|European UnionEuropean Commission [800926, 838171]; Swedish Research CouncilSwedish Research CouncilEuropean Commission [VR-2017-04910]; Knut and Alice Wallenberg FoundationKnut & Alice Wallenberg Foundation; Wallenberg Wood Science Center [KAW 2018.0452]; Swedish Government Strategic Research Area in Materials Science on Advanced Functional Materials at Linkoping University [2009-00971]; European Research Council (ERC)European Research Council (ERC)European Commission [834677]

Electronic materials that can self-organize in vivo and form functional components along the tissue of interest can result in a seamless integration of the bioelectronic interface. Previously, we presented in vivo polymerization of the conjugated oligomer ETE-S in plants, forming conductors along the plant structure. The EDOT-thiophene-EDOT trimer with a sulfonate side group polymerized due to the native enzymatic activity of the plant and integrated within the plant cell wall. Here, we present the synthesis of three different conjugated trimers based on thiophene and EDOT or purely EDOT trimers that are able to polymerize enzymatically in physiological pH in vitro as well as in vivo along the roots of living plants. We show that by modulating the backbone and the side chain, we can tune the electronic properties of the resulting polymers as well as their localization and penetration within the root. Our work paves the way for the rational design of electronic materials that can self-organize in vivo for spatially controlled electronic functionalization of living tissue., European Union (EU); Horizon 2020; Research and Innovation Program; HyPhOE; MSCA-IF-2018; TEXTHIOL

Eutectogels are a new class of soft ion conductive materials that are attracting attention as an alternative to conventional hydrogels and costly ionic liquid gels to build wearable sensors and bioelectrodes. Herein, the first example of mixed ionic and electronic conductive eutectogels showing high adhesion, flexibility, nonvolatility, and reversible low-temperature gel transition for 3D printing manufacturing is reporting. The eutectogels consist of choline chloride/glycerol deep eutectic solvent, poly(3,4-ethylenedioxythiophene): lignin sulfonate, and gelatin as the biocompatible polymer matrix. These soft materials are flexible and stretchable, show high ionic and electronic conductivities of 7.3 and 8.7 mS cm−1, respectively, and have high adhesion energy. Due to this unique combination of properties, they could be applied as strain sensors to precisely detect physical movements. Furthermore, these soft mixed ionic electronic conductors possess excellent capacity as conformal electrodes to record epidermal physiological signals, such as electrocardiograms and electromyograms, over a long time. M.L.P. and A.G. contributed equally to this work. This work was supported by Marie Sklodowska-Curie Research and Innovation Staff Exchanges (RISE) under the grant agreement No 823989 “IONBIKE.” The financial support received from CONICET and ANPCyT (Argentina) is also gratefully acknowledged. Thanks to the Flexible Electronic Department (FEL) of Ecole des Mines de Saint-Etienne (EMSE) for the combined mechanical/electrical characterization.

The incorporation of organic corrosion inhibitors into waterborne coatings is optimized in this work. Herein, p-coumaric acid (4-hydroxycinnamic acid) is modified by a butyl radical and its effectiveness as an anticorrosive free inhibitor in solution is confirmed by potentiodynamic polarization (PP). The molecule is then successfully incorporated into waterborne polymeric binders by employing different polymerization techniques in dispersed media. Whenever possible, the inhibitor is also blended into the bare latexes to compare the effect of the incorporating method. The anticorrosion performance of the obtained coatings is tested and compared by electrochemical analysis. Promising results are obtained for the coatings produced by semibatch emulsion polymerization even at the low concentration of 1.5 mg of inhibitor g(-1) latex. The intact control coating without inhibitor shows an impedance of up to 10(6) omega and a phase angle of 72 degrees after 1 h of immersion in the corrosive medium, meanwhile the coating with inhibitor shows higher values, 10(6.7) omega and 80 degrees. Active corrosion inhibition is observed in the coating with inhibitor in which a defect has been done, as the impedances drop to 10(3.9) omega after 24 h of immersion in the saline solution while in the control scratched coating it drops to 10(3.6) omega. The authors would like to thank for the financial support received from the Basque Government (IT-999-16), and the Spanish Government (MINECO CTQ -2017-87841-R and MICINN PDC2021-121416-I00).

Poly(3,4-ethylenedioxythiophene) (PEDOT) is the most popular conducting polymer in the emerging field of bioelectronics. Besides its excellent properties and commercial availability, its success is due to the aqueous processability of its anionically stabilized solutions or dispersions. In this work, a water soluble version of PEDOT is shown, which is cationically stabilized. This work reports the chemical oxidative (co)polymerization of EDOT-ammonium derivative leading to PEDOT-N (co)polymers. PEDOT- N shows the typical features of PEDOT such as UV absorbance, bipolaron band, electrical conductivity, electrochemical behavior, and film formation ability. Furthermore, the PEDOT-N films show good biocompatibility in the presence of the human embryonic kidney-293 cell line. The water solu- bility of PEDOT-N and its cationic nature allows its processability in the form of thin films obtained by the layer-by-layer technique or as conducting hydrogels.

A green, efficient and stable solar cell based only on water and safe and cheap elements of the periodic table is proposed in this work, finally consolidating (also from a sustainability viewpoint) the concept of “artificial photosynthesis” studied for decades by the scientific community. The concept of dye-sensitized solar cells is re-proposed here with a metal-free organic dye, an iodine-based electrolyte in a 100% aqueous environment and a new cathode (cationic PEDOT) synthesized for the first time with the aim of inhibiting the repulsion between the anions of redox couples and the PEDOT:PSS matrix commonly used as the counter-electrode. This elegant setup leads to a record efficiency of 7.02%, the highest value ever obtained for a water-based solar cell and, in general, for a photovoltaic device free of both organic solvents and expensive/heavy metals., A new cationic PEDOT derivative inhibits repulsion phenomena within iodine-based electrolytes, boosting the efficiency of aqueous solar cells.

Conducting polymer scaffolds can promote cell growth by electrical stimulation, which is advantageous for some specific type of cells such as neurons, muscle, or cardiac cells. As an additional feature, the measure of their impedance has been demonstrated as a tool to monitor cell growth within the scaffold. In this work, we present innovative conducting polymer porous scaffolds based on poly(3,4-ethylenedioxythiophene) (PEDOT):xanthan gum instead of the well-known PEDOT:polystyrene sulfonate scaffolds. These novel scaffolds combine the conductivity of PEDOT and the mechanical support and biocompatibility provided by a polysaccharide, xanthan gum. For this purpose, first, the oxidative chemical polymerization of 3,4-ethylenedioxythiophene was carried out in the presence of polysaccharides leading to stable PEDOT:xanthan gum aqueous dispersions. Then, by a simple freeze-drying process, porous scaffolds were prepared from these dispersions. Our results indicated that the porosity of the scaffolds and mechanical properties are tuned by the solid content and formulation of the initial PEDOT:polysaccharide dispersion. Scaffolds showed interconnected pore structure with tunable sizes ranging between 10 and 150 μm and Young's moduli between 10 and 45 kPa. These scaffolds successfully support three-dimensional cell cultures of MDCK II eGFP and MDCK II LifeAct epithelial cells, achieving good cell attachment with very high degree of pore coverage. Interestingly, by measuring the impedance of the synthesized PEDOT scaffolds, the growth of the cells could be monitored.

In this work, poly(ionic liquid)–ionic liquid (PIL–IL) composite membranes were prepared using the solvent casting technique. The studied PILs have pyrrolidinium polycation backbone ([Pyr11]+), while the five ILs display either an imidazolium ([C2mim]+) or a pyrrolidinium ([Pyr14]+) based cation. Both the PIL and IL components comprised cyano-functionalized anions ([N(CN)2]–, [C(CN)3]– or [B(CN)4]–), being the anion for each component different from one another. The use of the [NTf2]– anion was also tested for comparison. Several experimental conditions for the solvent casting procedure were tested in order to prepare homogenous and free standing PIL–IL composite membranes. The CO2 and N2 permeation properties (permeability, diffusivity and solubility) were evaluated at a fixed temperature (293 K) and constant trans-membrane pressure differential (100 kPa) using a time-lag apparatus, so that trends regarding the different anions either on the PIL or IL could be obtained and evaluated. From all 42 PIL–IL combinations tested, 21 were suitable membranes (homogeneous and free standing) for gas permeation experiments and 4 of them were on top or surpassed the 2008 Robeson upper bound for CO2/N2 separation. The best performance membranes contain the [C(CN)3]– and [B(CN)4]– anions, enlightening therefore the promise these anions entail for future high performance membranes for post-combustion CO2 separation.

Carboxylic acid functional ethoxythiophene (PRODOT‐COOH) monomer has been synthetized and polymerized chemically and electrochemically. This monomer can be used as intermediate to prepare three additional PRODOT monomers via simple condensation with HATU or DCC and electropolymerized to afford functionalized conductive polymers.

Recent interest in bioelectronics has prompted the exploration of properties of conducting polymer films at the interface with biological milieus. Poly(3,4-ethylenedioxythiophene) doped with poly(styrenesulfonate) (PEDOT:PSS) from a commercially available source has been used as a model system for these studies. Different cross-linking schemes have been used to stabilize films of this material against delamination and redispersion, but the cost is a decrease in the electrical conductivity and/or additional heat treatment. Here we introduce divinylsulfone (DVS) as a new cross-linker for PEDOT:PSS. Thanks to the higher reactiveness of the vinyl groups of DVS, the cross-linking can be performed at room temperature. In addition, DVS does not reduce electronic conductivity of PEDOT:PSS but rather increases it by acting as a secondary dopant. Cell culture studies show that PEDOT:PSS:DVS films are cytocompatible and support neuroregeneration. As an example, we showed that this material improved the transconductance value and stability of an organic electrochemical transistor (OECT) device. These results open the way for the utilization of DVS as an effective cross-linker for PEDOT:PSS in bioelectronics applications.

Conducting polymer hydrogels are attracting much interest in biomedical and energy-storage devices due to their unique electrochemical properties including their ability to conduct both electrons and ions. They suffer, however, from poor stability due to water evaporation, which causes the loss of mechanical and ion conduction properties. Here we show for the first time a conducting polymer gel where the continuous phase is a nonvolatile ionic liquid. The novel conducting iongel is formed by a natural polysaccharide (guar gum), a conductive polymer poly(3,4-ethylenedioxythiophene) (PEDOT), and an ionic liquid (IL) 1-butyl-3-methylimidazolium chloride (BMIMCl). First, an aqueous dispersion of PEDOT:guar gum is synthesized by an oxidative polymerization process of EDOT in the presence of the polysaccharide as stabilizer. The resulting PEDOT:guar gum was isolated as a powder by removing the water via freeze-drying process. In the final step, conducting iongels were prepared by the PEDOT:guar gum mixed with the ionic liquid by a heating-cooling process. The rheological properties show that the material exhibits gel type behavior between 20 and 80 °C. Interestingly, the conducting polymer iongel presents redox properties as well as high ionic conductivities (10

New polymeric materials such as polymer electrolytes or redox polymers are actively being searched for in order to increase the performance and security of electrochemical energy storage devices such as batteries. Poly(ionic liquid)s are very popular materials in energy nowadays finding applications as ion conducting polymer electrolytes and electrode binders for batteries and supercapacitors. In this work, the incorporation of redox-active counter anions (anthraquinone and nitroxide molecules) into poly(ionic liquid)s has broadened the scope of applications as redox-active materials in different energy storage technologies. Polymers having those known redox-active molecules usually involve challenging synthetic routes and yield insoluble materials very difficult to handle. In this paper, we show that the synthesis of the redox-active poly(ionic liquid)s can be achieved through a straightforward and simple anion exchange reaction. We also show that this new family of redox-active poly(ionic liquid)s can be applied in several electrochemical energy storage technologies such as lithium batteries, as electrocatalysts in fuel cells and metal–air batteries or as electrolytes in organic redox flow batteries.

Magnetic resonance imaging (MRI) is one of the leading imaging modalities because of the combination of convenient non-invasive application, high spatial resolution, and tomographic capability. MRI is not as sensitive as other techniques, and gadolinium (Gd(III)) based contrast agents must be added to increase the spatial resolution. Recent studies demonstrated that Gd(III) based contrast agents are not completely released from the body after treatment, which can cause damage, especially in renal impaired patients such as the nephrogenic systemic fibrosis (NSF) due to the toxicity of free Gd(III). In this context, we synthesize gadolinium-free macromolecular contrast agents, PU-ORCAs (polyurethane based organic contrast agents) containing nitroxides for MRI. Nitroxides are stable, organic, free radicals with a single unpaired electron, showing a potential for MRI applications. First, we successfully synthesize an MRI active novel diol monomer containing a nitroxide. Afterwards we copolymerize the nitroxide containing diol with polyethylene glycol end-capped diol and hexamethylene diisocyanate in the presence of the diazabicyclo[5.4.0]undec-7-ene (DBU) catalyst to prepare the macromolecular polyurethane based contrast agents. The ability of these amphiphilic polyurethanes to self-assemble in water is demonstrated. In addition, we show that PU-ORCAs are able to increase the water proton relaxivity (r1) and (r2), at 1.5 T, up to 0.66 and 0.98 mM−1 s−1 respectively. Phantom studies confirm that in the presence of low PU-ORCA concentrations (3.3 mM) there is a significant contrast enhancement, especially in the T1-imaging modality. In addition, r2/r1 = 1.3 value is close to 1 in human serum.

All-organic batteries are a promising sustainable energy storage technology owing to the wide availability, flexibility, and recyclability of organic/polymeric compounds. The development of all-organic or polymer batteries is still a challenge, as both electrode materials need to be carefully optimized to have a wide difference of redox potential and compatibility with the electrolyte. Herein, dual redox-active polyimides based on phenothiazine and naphthalene tetracarboxylic dianhydride units are presented. After only one optimization step, the electrodes based on these dual redox polymers can be applied simultaneously as anode and cathode in a symmetric all-organic battery. The phenothiazine functional polyimide shows two redox active voltages at around 2.5 and 3.7 V (vs. Li/Li+ ) with high discharge capacities of 160 mAh g-1 . Moreover, the symmetric full battery delivers high power density up to 1542 W kg-1 with stable cyclability for 1000 cycles. This work demonstrates an efficient strategy to develop dual redox active polymer electrodes for next generation all-polymer batteries.

International audience; Polymer acceptors are a class of “non‐fullerene” electron‐transporting materials that can replace [6,6]‐phenyl C61/71 butyric acid (PC61/71BM) in bulk‐heterojunction (BHJ) solar cells. In this contribution is reported the use of N‐acyl‐substituted isoindigo (IID) motifs (IID(CO)) as electron‐deficient units in the design of polymer acceptors for “all‐polymer” BHJ solar cells. While IID motifs are commonly used in the design of polymer donors for efficient BHJ solar cells with the fullerene PC61/71BM acceptors, here it is shown that IID(CO) building units used in conjunction with suitable co‐monomers represent a practical avenue for polymer acceptors with electron affinity values comparable to that of PC61/71BM (i.e., 4.2 eV).

International audience; Herein, we describe the design and synthesis of novel pyridinium containing amide based poly(ionic liquid)s (PAPILs) for CO2 capture and separation. Additionally, a new and unique crystal structure of pyridinium containing diamine monomer [MDAP][TFSI] is also presented. PAPILs reveal potential for CO2/CH4 separation and isosteric heat of adsorption in the physisorption range.

The supporting information is attached. Aliphatic polycarbonates have emerged as promising polymer electrolytes due to their combination of moderate ionic conductivity and high lithium transference numbers. However, the mechanical properties of the aliphatic polycarbonates polymer electrolytes are usually weak due to the low molecular weight achieved and plasticization effect of the added lithium salt. In this article, we present a copolymer having poly(ethylene oxide) segments linked by carbonate groups with cross-linkable methacrylic pendant groups. Once the polymer and the lithium salt were mixed, the poly(ethylene oxide carbonate) was cross-linked by UV light producing a free standing solid polymer electrolyte (SPE). Different SPE formulations were designed by varying the LiTFSI concentration within the polymer matrix showing the highest ionic conductivity of 1.3·10−3 S cm−1 and a lithium transference number of 0.59 at 70 °C. 7Li solid-state NMR experiments were used to correlate the lithium cation environment and dynamics with ionic conductivity. At the same temperature the electrochemical stability window was analyzed, and a reasonable value of 4.9 V was achieved. The study was complemented by mechanical and thermal stability measurements. Finally, the optimized UV-cross-linked poly(ethylene oxide carbonate) was tested as electrolyte in lithium metal symmetric cell at 70 °C, showing low over-potential values and a stable solid electrolyte interphase layer. We are grateful to the financial support of the European Research Council by Starting Grant Innovative Polymers for Energy Storage (iPes) 306250 and the Basque Government through ETORTEK Energigune 2013 and IT 999-16. Leire Meabe thanks Spanish Ministry of Education, Culture and Sport for the predoctoral FPU fellowship received to carry out this work. The authors would like to thank the European Commission for their financial support through the project SUSPOL-EJD 642671 and the Gobierno Vasco/Eusko Jaurlaritza (IT 999-16). The authors thank for technical and human support provided by SGIker of UPV/EHU for the NMR facilities of Gipuzkoa campus.

International audience; Two steps synthesis of EDOT (3,4-ethylenedioxythiophene) derivate bearing a carboxylic acid group (carboxyl-EDOT) is presented. This reactive monomer has been copolymerized with EDOT to afford PEDOT copolymers. Thanks to the most common additives usually added to the PEDOT:PSS dispersion, ethylene glycol and 4-Dodecylbenzenesulfonic acid (DBSA), the carboxylic acid has been used to crosslink the material via esterification reactions. This result offers the possibility to produce a polymer network without adding any crosslinking agent. Furthermore, the short synthetic pathway of carboxyl-EDOT offers the possibility to incorporate new functionality either in EDOT monomer or in PEDOT materials with a reasonable chemical effort and background.

Chemical recycling of plastic wastes represents a greener alternative to landfill and incineration, and potentially offers a solution to the environmental consequences of increased plastic waste. Most plastics that are widely used today are designed for durability, hence currently available depolymerization methods typically require harsh conditions and when applied to blended and mixed plastic feeds generate a mixture of products. Herein, the selective depolymerization of bisphenol A polycarbonate (BPA-PC) mediated by a thermally stable dual organocatalyst is performed to create bisphenol A and a range of added-value cyclic carbonate monomers. Moreover, we demonstrate that the energetic differences in the catalytic glycolysis enables not only the selective and sequential depolymerization of BPA-PC and PET (which cannot be separated based on their density) but more importantly from technical grade BPA-PC/PET blends. This methodology both presents waste BPA-PC as a ‘greener’ alternative for the synthesis of small molecule carbonates and demonstrates the concept that catalytic depolymerization offers great potential for selective plastic recycling.

Glycopolymers, synthetic sugar-containing macromolecules, are attracting ever-increasing interest from the chemistry community. Glycidyl methacrylate (GMA) is an important building block for the synthesis of sugar based methacrylate monomers and polymers. Normally, glycidyl methacrylate shows some advantages such as reactivity against nucleophiles or milder synthetic conditions such as other reactive methacrylate monomers. However, condensation reactions of glycidyl methacrylate with for instance protected galactose monomer leads to a mixture of two products due to a strong competition between the two possible pathways: epoxide ring opening or transesterification. In this paper, we propose two alternative routes to synthesize regiospecific galactose-based methacrylate monomers using the epoxy-ring opening reaction. In the first alternative route, the protected galactose is first oxidized to the acid in order to make it more reactive against the epoxide of GMA. In the second route, the protected sugar was first treated with epichlorohydrin followed by the epoxy ring opening reaction with methacrylic acid, to create an identical analogue of the ring-opening product of GMA. These two monomers were polymerized using conventional radical polymerization and were compared to the previously known galactose-methacrylate one. The new polymers show similar thermal stability but lower glass transition temperature (Tg) with respect to the known galactose methacrylate polymer.

Racemic 4-oxocyclopent-2-en-1-yl acetate was used in a short synthesis of nucleoside analogues with pyrimidine and purine heterobases. The protocol is based on a typical nucleophilic substitution process. Uracil, thymine, 6-chloropurine, and some adenines gave the expected 4-heterosubstituted products along with the isomeric 2-heterosubstituted compounds as minor components. Samples of selected products were evaluated for their antiviral activity in a primary screening against a variety of viruses belonging to different classes. One of the compounds was found to be highly active against human papilloma virus (HPV).

Reduction of anthropogenic CO2 emissions and CO2 separation from post-combustion flue gases are among the imperative issues in the spotlight at present. Hence, it is highly desirable to develop efficient adsorbents for mitigating climate change with possible energy savings. Here, we report the design of a facile one pot catalyst-free synthetic protocol for the generation of three different nitrogen rich nanoporous amide networks (NANs) based on tetraphenyladamantane. Besides the porous architecture, CO2 capturing potential and high thermal stability, these NANs possess notable CO2/N2 selectivity with reasonable retention while increasing the temperature from 273 K to 298 K. The quantum chemical calculations also suggest that CO2 interacts mainly in the region of polar amide groups (–CONH–) present in NANs and this interaction is much stronger than that with N2 thus leading to better selectivity and affirming them as promising contenders for efficient gas separation.

A fast and simple synthetic route towards a new family of poly(ionic liquids) based on aromatic crosslinked poly(azomethine-pyridinium) salts is described. These new polymers were prepared in one step from new diamine methyl pyridinium salts and isopthaldehyde, in 30 min under microwave irradiation. By this method, poly(azomethine-pyridinium) containing chloride (Cl), bis(trifluoromethylsulfonyl)imide (TFSI) and hexaflorophosphate (PF6) as counter-anions were synthetized. This new pyridinium poly(ionic liquid)s were obtained as insoluble powders showing high thermal stability. The poly(azomethine-pyridinium)s were tested as heterogeneous catalysts in the cycloaddition of CO2 to epichlorohydrin to obtain chloropropylene carbonate. The polymers containing chloride anion shows high content of catalytically active sites and the best performance of the series, with 100% selectivity towards the chloropropylene carbonate in a reaction without solvent at 3 bar of CO2, 100 °C and low catalyst loading (0.5 mol%). Spanish Government, MINECO (Projects MAT2014-52085-C2-2-P and MAT2017-82288-C2-2-P, MAT2017-83373-R)

There is a great interest in incorporating catechol moieties into polymers in a controlled manner due to their interesting properties, such as the promotion of adhesion, redox activity or bioactivity. One possibility is to incorporate the catechol as end-group in a polymer chain using a functional initiator by means of controlled polymerization strategies. Nevertheless, the instability of catechol moieties under oxygen and basic pH requires tedious protection and deprotection steps to perform the polymerization in a controlled fashion. In the present work, we explore the organocatalyzed synthesis of catechol end-functional, semi-telechelic polylactide (PLLA) using non-protected dopamine, catechol molecule containing a primary amine, as initiator. NMR and SEC-IR results showed that in the presence of a weak organic base such as triethylamine, the ring-opening polymerization (ROP) of lactide takes place in a controlled manner without need of protecting the cathechol units. To further confirm the end-group fidelity the catechol containing PLLA was characterized by Cyclic Voltammetry and MALDI-TOF confirming the absence of side reaction during the polymerization. In order to exploit the potential of catechol moieties, catechol end-group of PLLA was oxidized to quinone and further reacted with aliphatic amines. In addition, we also confirmed the ability of catechol functionalized PLLA to reduce metal ions to metal nanoparticles to obtain well distributed silver nanoparticles. It is expected that this new route of preparing catechol-PLLA polymers without protection will increase the accessibility of catechol containing biodegradable polymers by ROP. This work was supported by Basque Government (GV/EJ) Department of Education (IT-927-16), The European Commission support through the project SUSPOL-EJD 64267 and the Gobierno Vasco/Eusko Jaurlaritza (IT 999-16 and IT-618-13). Haritz Sardon gratefully acknowledges financial support from MINECO through project SUSPOL and FDI 16507. Christophe Detrembleur thanks the "Fonds de la Recherche Scientifique" (FRS-FNRS) and the Belgian Science Policy in the frame of the Interuniversity Attraction Poles Program (P7/05)-Functional Supramolecular Systems (FS2) for financial supports. Christophe Detrembleur is Research Director by the FRS-FNRS. Nerea Sadaba is thankful for the predoctoral fellowship to POLYMAT Fundazioa-Basque Center for Macromolecular Design and Engineering.

Poly(3,4-ethylenedioxythiophene)s are the conducting polymers (CP) with the biggest prospects in the field of bioelectronics due to their combination of characteristics (conductivity, stability, transparency and biocompatibility). The gold standard material is the commercially available poly(3,4-ethylenedioxythiophene): poly(styrene sulfonate) (PEDOT:PSS). However, in order to well connect the two fields of biology and electronics, PEDOT: PSS presents some limitations associated with its low (bio) functionality. In this review, we provide an insight into the synthesis and applications of innovative poly(ethylenedioxythiophene)-type materials for bioelectronics. First, we present a detailed analysis of the different synthetic routes to (bio) functional dioxythiophene monomer/polymer derivatives. Second, we focus on the preparation of PEDOT dispersions using different biopolymers and biomolecules as dopants and stabilizers. To finish, we review the applications of innovative PEDOT-type materials such as biocompatible conducting polymer layers, conducting hydrogels, biosensors, selective detachment of cells, scaffolds for tissue engineering, electrodes for electrophysiology, implantable electrodes, stimulation of neuronal cells or pan-bio electronics. The work was supported by EU through the projects FP7-PEOPLE-2012-ITN 316832-OLIMPIA and FP7-PEOPLE-2013-ITN 607896-OrgBio. Ana Sanchez-Sanchez is thankful for the Postdoctoral Funding for Doctoral Research Staff Improvement Grant from the Basque Government. David Mecerreyes thanks Becas de Practicas en el Extranjero "Global Training".