Emerging Ionic Polymers for CO2 Conversion to Cyclic Carbonates: An Overview of Recent Developments

In this mini review, we highlight some key work from the last 2 years where ionic polymers have been used as a catalyst to convert CO2 into cyclic carbonates. Emerging ionic polymers reported for this catalytic application include materials such as poly(ionic liquid)s (PILs), ionic porous organic polymers (iPOPs) or ionic covalent organic frameworks (iCOFs) among others. All these organic materials share in common the ionic moiety cations such as imidazolium, pyridinium, viologen, ammonium, phosphonium, and guanidinium, and anions such as halides, [BF4]-, [PF6]-, and [Tf2N]-. The mechanistic aspects and efficiency of the CO2 conversion reaction and the polymer design including functional groups and porosity are discussed in detail. This review should provide valuable information for researchers to design new polymers for important catalysis applications

New electroactive macromonomers and multi-responsive PEDOT graft copolymers

Poly(3,4-ethylenedioxithiophene) (PEDOT) is the conducting polymer with the biggest prospects in the field of organic electronics due to its high electrical conductivity and transparency as thin films.Marie Curie IF BIKE Project No. 74286

A Na+ conducting hydrogel for protection of organic electrochemical transistors.

Organic electrochemical transistors (OECTs) are being intensively developed for applications in electronics and biological interfacing. These devices rely on ions injected in a polymer film from an aqueous liquid electrolyte for their operation. However, the development of solid or semi-solid electrolytes are needed for future integration of OECTs into flexible, printed or conformable bioelectronic devices. Here, we present a new polyethylene glycol hydrogel with high Na+ conductivity which is particularly suitable for OECTs. This novel hydrogel was synthesized using cost-effective photopolymerization of poly(ethylene glycol)-dimethacrylate and sodium acrylate. Due to the high water content (83% w/w) and the presence of free Na+, the hydrogel showed high ionic conductivity values at room temperature (10-2 S cm-1) as characterized by electrochemical impedance spectroscopy. OECTs made using this hydrogel as a source of ions showed performance that was equivalent to that of OECTs employing a liquid electrolyte. They also showed improved stability, with only a 3% drop in current after 6 h of operation. This hydrogel paves the way for the replacement of liquid electrolytes in high performance OECTs bringing about advantages in terms of device integration and protection

Expanding the Applicability of Poly(Ionic Liquids) in Solid Phase Microextraction: Pyrrolidinium Coatings

Crosslinked pyrrolidinium-based poly(ionic liquids) (Pyrr-PILs) were synthesized through a fast, simple, and solventless photopolymerization scheme, and tested as solid phase microextraction (SPME) sorbents. A series of Pyrr-PILs bearing three different alkyl side chain lengths with two, eight, and fourteen carbons was prepared, characterized, and homogeneously coated on a steel wire by using a very simple procedure. The resulting coatings showed a high thermal stability, with decomposition temperatures above 350 degrees C, excellent film stability, and lifetime of over 100 injections. The performance of these PIL-based SPME fibers was evaluated using a mixture of eleven organic compounds with different molar volumes and chemical functionalities (alcohols, ketones, and monoterpenes). The Pyrr-PIL fibers were obtained as dense film coatings, with 67 mu m thickness, with an overall sorption increase of 90% and 55% as compared to commercial fibers of Polyacrylate (85 mu m) (PA85) and Polydimethylsiloxane (7 mu m) (PDMS7) coatings, respectively. A urine sample doped with the sample mixture was used to study the matrix effect and establish relative recoveries, which ranged from 60.2% to 104.1%.David J. S. Patinha, and Liliana C. Tome are grateful to FCT (Fundacao para a Ciencia e a Tecnologia) for the PhD research grant SFRH/BD/97042/2013 and the Post-Doctoral research grant (SFRH/BPD/101793/2014), respectively. David J. S. Patinha also thanks the financial support from COST-Exil Project 1206. The NMR data was acquired at CERMAX (Centro de Ressonncia Magnetica Antnio Xavier) which is a member of the National NMR network. This work was partially supported by FCT through Research Unit GREEN-it " Bioresources for Sustainability" (UID/Multi/04551/2013) and the Associate Laboratory CICECO Aveiro Institute of materials (UID/CTM/50011/2013)

Ionic Hydrogel for Accelerated Dopamine Delivery via Retrodialysis.

Local drug delivery directly to the source of a given pathology using retrodialysis is a promising approach to treating otherwise untreatable diseases. As the primary material component in retrodialysis, the semipermeable membrane represents a critical point for innovation. This work presents a new ionic hydrogel based on polyethylene glycol and acrylate with dopamine counterions. The ionic hydrogel membrane is shown to be a promising material for controlled diffusive delivery of dopamine. The ionic nature of the membrane accelerates uptake of cationic species compared to a nonionic membrane of otherwise similar composition. It is demonstrated that the increased uptake of cations can be exploited to confer an accelerated transport of cationic species between reservoirs as is desired in retrodialysis applications. This effect is shown to enable nearly 10-fold increases in drug delivery rates from low concentration solutions. The processability of the membrane is found to allow for integration with microfabricated devices which will in turn accelerate adaptation into both existing and emerging device modalities. It is anticipated that a similar materials design approach may be broadly applied to a variety of cationic and anionic compounds for drug delivery applications ranging from neurological disorders to cancer

3D Printable Conducting and Biocompatible PEDOT-graft-PLA Copolymers by Direct Ink Writing

Tailor-made polymers are needed to fully exploit the possibilities of additive manufacturing, constructing complex, and functional devices in areas such as bioelectronics. In this paper, the synthesis of a conducting and biocompatible graft copolymer which can be 3D printed using direct melting extrusion methods is shown. For this purpose, graft copolymers composed by conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) and a biocompatible polymer polylactide (PLA) are designed. The PEDOT-g-PLA copolymers are synthesized by chemical oxidative polymerization between 3,4-ethylenedioxythiophene and PLA macromonomers. PEDOT-g-PLA copolymers with different compositions are obtained and fully characterized. The rheological characterization indicates that copolymers containing below 20 wt% of PEDOT show the right complex viscosity values suitable for direct ink writing (DIW). The 3D printing tests using the DIW methodology allows printing different parts with different shapes with high resolution (200\ua0\ub5m). The conductive and biocompatible printed patterns of PEDOT-g-PLA show excellent cell growth and maturation of neonatal cardiac myocytes cocultured with fibroblasts

Hybrid biopolymer electrodes for lithium- and sodium-ion batteries in organic electrolytes

The use of earth abundant and renewable materials is encouraging for the future development of environmentally clean, safe and affordable electrodes for lithium- and sodium-ion batteries. Biohybrid electrodes based on lignin and several conducting polymers have been studied mainly for supercapacitor applications. Here, we show that biohybrid electrodes containing natural lignin and a PEDOT conjugated polymer serve as electroactive materials for lithium- and sodium-ion batteries using liquid organic electrolytes. A reversible discharge capacity of 74 mA h g−1, at C/20 (4 mA g−1) rate, was achieved in the voltage range between 1 V and 4.5 V, with peak values of up to 159 mA h g−1. These properties make the natural lignin–PEDOT hybrid material a suitable organic positive electrode for Li- and Na-ion batteries

Biobased supramolecular ionic networks with optimized crystallinity and mechanical properties as promising dynamic materials for eutectogels design

Ionic supramolecular networks are attractive materials for technological applications with unique properties such as ionic conductivity, stimuli-responsiveness, recyclability, and self-healing. Herein, new semicrystalline supramolecular ionic networks are designed from fully biobased building blocks such as tartaric acid, phytic acid, sebacic acid, and a fatty dimer diamine (Priamine™ 1071). The combination of tartaric acid with Priamine™ 1071 results in a crystalline and brittle polymer, but its molecular regularity can be controlled by incorporating sebacic acid or phytic acid, affording tough materials with appropriate mechanical properties (elastic moduli ranging 19–42 MPa). Furthermore, the ionic polymers show network-to-liquid phase transitions between 75 and 127 °C, and in the liquid state, they were found to be miscible with a lithium-based deep eutectic solvent, yielding flexible and conductive eutectogels. Altogether, these dynamic networks could open new prospects for developing fully green soft ionic materials from their combination with other innovative and low-cost eutectic mixtures.Open Access funding provided by the University of Basque Country. The financial support received from CONICET and ANPCyT (PICT 2018-01032) (Argentina) is gratefully acknowledged

Conducting Polymer‐Ionic Liquid Electrode Arrays for High‐Density Surface Electromyography

Abstract: Surface electromyography (EMG) is used as a medical diagnostic and to control prosthetic limbs. Electrode arrays that provide large‐area, high density recordings have the potential to yield significant improvements in both fronts, but the need remains largely unfulfilled. Here, digital fabrication techniques are used to make scalable electrode arrays that capture EMG signals with mm spatial resolution. Using electrodes made of poly(3,4‐ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) composites with the biocompatible ionic liquid (IL) cholinium lactate, the arrays enable high quality spatiotemporal recordings from the forearm of volunteers. These recordings allow to identify the motions of the index, little, and middle fingers, and to directly visualize the propagation of polarization/depolarization waves in the underlying muscles. This work paves the way for scalable fabrication of cutaneous electrophysiology arrays for personalized medicine and highly articulate prostheses