RESUMO

Deep Eutectic Solvents (DES) are a new class of ionic conductive compounds attracting significant attention as greener alternatives to costly ionic liquids. Herein, we developed novel mixed ionic-electronic conducting materials by simple mixing of poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT:PSS) and various DES as additives. The DES addition induces the supramolecular assembly and gelification of PEDOT:PSS forming eutectogels triggered by extensive hydrogen bonding and charge stabilization. The eutectogels feature boosts the mixed ionic-electronic conductivity of PEDOT:PSS up to 368 S cm-1, unveiling great potential as flexible bioelectronics. All the PEDOT:PSS/DES gels showed shear-thinning behavior and viscosity values ranging from 100 to 1000 Pa s. The eutectogels show good injectability with almost instantaneous elastic recovery, making them ideal materials for direct ink writing (DIW). As proof of that, PEDOT:PSS/DES (choline chloride:lactic acid) was 3D printed in different patterns, annealed at high temperature, and assembled into adhesive electrodes. This way tattoos-like electrodes, denoted as Eutecta2 were fabricated and placed in vivo on the forearm and the thumb of human volunteers for electromyography measurements. Eutecta2 hexagonal patterns showed excellent conformability, and their signal-to-noise ratio (SNR) was higher than Ag/AgCl commercial electrodes for thumb motion measurements. Furthermore, forearm motion was measured after 14 days with similar values of SNR, demonstrating long-term stability and reusability. All in all, our findings revealed that DES could be used as inexpensive and safe additives to direct the self-assembly of PEDOT:PSS into supramolecular eutectogels inks for flexible bioelectronics.

RESUMO

There is an actual need for developing materials for wound healing applications with anti-inflammatory, antioxidant, or antibacterial properties in order to improve the healing performance. In this work, we report the preparation and characterization of soft and bioactive iongel materials for patches, based on polymeric poly(vinyl alcohol) (PVA) and four ionic liquids containing the cholinium cation and different phenolic acid anions, namely cholinium salicylate ([Ch][Sal]), cholinium gallate ([Ch][Ga]), cholinium vanillate ([Ch][Van]), and cholinium caffeate ([Ch][Caff]). Within the iongels, the phenolic motif in the ionic liquids plays a dual role, acting as a PVA crosslinker and a bioactive compound. The obtained iongels are flexible, elastic, ionic conducting, and thermoreversible materials. Moreover, the iongels demonstrated high biocompatibility, non-hemolytic activity, and non-agglutination in mice blood, which are key-sought material specifications in wound healing applications. All the iongels have shown antibacterial properties, being PVA-[Ch][Sal], the one with higher inhibition halo for Escherichia Coli. The iongels also revealed high values of antioxidant activity due to the presence of the polyphenol, with the PVA-[Ch][Van] iongel having the highest activity. Finally, the iongels show a decrease in NO production in LPS-stimulated macrophages, with the PVA-[Ch][Sal] iongel displaying the best anti-inflammatory activity (>63% at 200 µg/mL).

RESUMO

Natural deep eutectics solvents (NADES), owing to their high solvation capacity and nontoxicity, are actively being sought for many technological applications. Herein, we report a series of novel NADES based on choline chloride and plant-derived polyphenols. Most of the obtained phenolic NADES have a wide liquid range and high thermal stability above 150 °C. Among them, small-sized polyphenols, like pyrogallol, vanillyl alcohol, or gentisic acid, lead to low-viscosity liquids with ionic conductivities in the order of 10-3 S cm-1 at room temperature. Interestingly, polyphenols possess valuable properties as therapeutic agents, antioxidants, adhesives, or redox-active compounds, among others. Thus, we evaluated the potential of these novel NADES for two applications: bioadhesives and corrosion protection. The mixture of choline chloride-vanillyl alcohol (2:3 mol ratio) and gelatin resulted in a highly adhesive viscoelastic liquid (adhesive stress ≈ 135 kPa), affording shear thinning behavior. Furthermore, choline chloride-tannic acid (20:1) showed an extraordinary ability to coordinate iron ions, reaching excellent corrosion inhibitive efficiencies in mild steel protection.

RESUMO

Iongels are soft ionic conducting materials, usually composed of polymer networks swollen with ionic liquids (ILs), which are being investigated for applications ranging from energy to bioelectronics. The employment of iongels in bioelectronic devices such as bioelectrodes or body sensors has been limited by the lack of biocompatibility of the ILs and/or polymer matrices. In this work, we present iongels prepared from solely biocompatible materials: (i) a biobased polymer network containing tannic acid as a cross-linker in a gelatin matrix and (ii) three different biocompatible cholinium carboxylate ionic liquids. The resulting iongels are flexible and elastic with Young's modulus between 11.3 and 28.9 kPa. The morphology of the iongels is based on a dual polymer network system formed by both chemical bonding due to the reaction of the gelatin's amines with the polyphenol units and physical interactions between the tannic acid and the gelatin. These biocompatible iongels presented high ionic conductivity values, from 0.003 and up to 0.015 S·cm-1 at room temperature. Furthermore, they showed excellent performance as a conducting gel in electrodes for electromyography and electrocardiogram recording as well as muscle stimulation.

Assuntos

RESUMO

Iongels have attracted much attention over the years as ion-conducting soft materials for applications in several technologies including stimuli-responsive drug release and flexible (bio)electronics. Nowadays, iongels with additional functionalities such as electronic conductivity, self-healing, thermo-responsiveness, or biocompatibility are actively being searched for high demanding applications. In this work, a simple and rapid synthetic pathway to prepare elastic and thermoreversible iongels is presented. These iongels are prepared by supramolecular crosslinking between polyphenols biomolecules with a hydroxyl-rich biocompatible polymer such as poly(vinyl alcohol) (PVA) in the presence of ionic liquids. Using this strategy, a variety of iongels are obtained by combining different plant-derived polyphenol compounds (PhC) such as gallic acid, pyrogallol, and tannic acid with imidazolium-based ionic liquids, namely 1-ethyl-3-methylimidazolium dicyanamide and 1-ethyl-3-methylimidazolium bromide. A suite of characterization tools is used to study the structural, morphological, mechanical, rheological, and thermal properties of the supramolecular iongels. These iongels can withstand large deformations (40% under compression) with full recovery, revealing reversible transitions from solid to liquid state between 87 and 125 °C. Finally, the polyphenol-based thermoreversible iongels show appropriated properties for their potential application as printable electrolytes for bioelectronics.

Assuntos