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PEDOT Radical Polymer with Synergetic Redox and Electrical Properties.

ABSTRACT: The development of new redox polymers is being boosted by the increasing interest in the area of energy and health. The development of new polymers is needed to further advance new applications or improve the performance of actual devices such as batteries, supercapacitors, or drug delivery systems. Here we show the synthesis and characterization of a new polymer which combines the present most successful conjugated polymer backbone and the most successful redox active side group, i.e., poly(3,4-ethylenedioxythiophene) (PEDOT), and a nitroxide stable radical. First, a derivative of the 3,4-ethylenedioxythiophene (EDOT) molecule with side nitroxide stable radical group (TEMPO) was synthesized. The electrochemical polymerization of the PEDOT-TEMPO monomer was investigated in detail using cyclic voltammetry, potential step, and constant current methods. Monomer and polymer were characterized by NMR, FTIR, matrix-assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF MS), electron spin resonance (ESR) spectroscopy, elemental analysis, cyclic voltammetry, and four-point probe conductivity. The new PEDOT-TEMPO radical polymer combines the electronic conductivity of the conjugated polythiophene backbone and redox properties of the nitroxide group. As an example of application, this redox active polymer was used as a conductive binder in lithium ion batteries. Good cycling stability with high Coulombic efficiency and increased cyclability at different rates were obtained using this polymer as a replacement of two ingredients: conductive carbon additive and polymeric binders.

SUBMITTER: Casado N

PROVIDER: S-EPMC4727933 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Relation between Morphology and Chiroptical Properties in Chiral Conducting Polymer Films: A Case Study in Chiral PEDOT.

Project description:The electronic properties of conducting polymers are influenced by their micro- and macrostructural orders, which can be tailored by substituent modification. However, while the effect of substituents on conducting polymers is extensively investigated, chiral substituents are far less studied. Furthermore, many chiral conducting polymers have regioirregular structures, which result in polymer films with inferior properties. In this work, we apply electronic circular dichroism (ECD) spectroscopy to study the morphological changes to the chiral polymers under different polymerization conditions. For this purpose, we investigated 3,4-ethylenedioxythiophene (EDOT) derivatives having two stereogenic centers on each monomer and bearing methyl or phenyl side groups (dimethyl-EDOT and diphenyl-EDOT, respectively). Polymerizing the enantiomerically pure monomers produces regioregular and stereoregular dimethyl-PEDOT and diphenyl-PEDOT, respectively. The effect of the electrolyte and solvent on polymer film morphology was studied using scanning electron microscopy (SEM) and ECD, showing a correlation between the polymer's morphology and the chiroptical properties of its films. We found that, for diphenyl-PEDOT, the combination of perchlorate anion electrolyte and acetonitrile solvent resulted in a unique morphology characterized by significant intermolecular interactions. These interactions were clearly observable in the ECD spectra in the form of exciton couplings, whose presence was supported by TD-DFT calculations. A small enantiomeric excess was sufficient to induce very intense ECD signals, demonstrating chiral amplification in electropolymerized films.

| S-EPMC7660938 | biostudies-literature

Consequences of gamma-ray irradiation on structural and electronic properties of PEDOT:PSS polymer in air and vacuum environments.

Project description:In this work, the effects of gamma-ray irradiation (up to 3 kGy) on the structural and electronic properties of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), irradiated in air and vacuum environments are systematically investigated. Raman spectroscopy indicates that there is no significant change in structural conformation of PEDOT:PSS film after gamma-ray irradiation. However, the conductivity of the film decreases as a function of dose in both air and vacuum environments, which can be deduced as a result of defects created in the structure. Hall effect measurements showed higher carrier concentration when the samples are irradiated under vacuum in comparison to the air environment, whereas mobility decreases as a function of dose irrespective of the environment. Furthermore, the electron spin resonance spectra provided evidence of the evolution of polaron population after gamma-ray exposure of 3 kGy, due to the decrease in charge delocalization and molecular ordering of the molecules. This decrease in conductivity and mobility of the PEDOT:PSS films irradiated in air and vacuum environments can be mainly ascribed to the defects and radical formation after gamma-ray exposure, favoring chain scission or cross-linking of the polymers.

| S-EPMC9034154 | biostudies-literature

Synergetic Improvement of Stability and Conductivity of Hybrid Composites formed by PEDOT:PSS and SnO Nanoparticles.

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Superoxide radical anion adduct of 5,5-dimethyl-1-pyrroline N-oxide. 6. Redox properties.

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Exploring the Luminescence, Redox, and Magnetic Properties in a Multivariate Metal-Organic Radical Framework.

Project description:Persistent neutral organic radicals are excellent building blocks for the design of functional molecular materials due to their unique electronic, magnetic, and optical properties. Among them, triphenylmethyl radical derivatives have attracted a lot of interest as luminescent doublet emitters. Although neutral organic radicals have been underexplored as linkers for building metal-organic frameworks (MOFs), they hold great potential as organic elements that could introduce additional electronic properties within these frameworks. Herein, we report the synthesis and characterization of a novel multicomponent metal-organic radical framework (PTMTCR@NR-Zn MORF), which is constructed from the combination of luminescent perchlorotriphenylmethyl tricarboxylic acid radical (PTMTCR) and nonemissive nonradical (PTMTCNR) organic linkers and Zn(II) ions. The PTMTCR@NR-Zn MORF structure is layered with microporous one-dimensional channels embedded within these layers. Kelvin probe force microscopy further confirmed the presence of both organic nonradical and radical linkers in the framework. The luminescence properties of the PTMTCR ligand (first studied in solution and in the solid state) were maintained in the radical-containing PTMTCR@NR-Zn MORF at room temperature as fluorescence solid-state quenching is suppressed thanks to the isolation of the luminescent radical linkers. In addition, magnetic and electrochemical properties were introduced to the framework due to the incorporation of the paramagnetic organic radical ligands. This work paves the way for the design of stimuli-responsive hybrid materials with tunable luminescence, electrochemical, and magnetic properties by the proper combination of closed- and open-shell organic linkers within the same framework.

| S-EPMC10870702 | biostudies-literature

Modulation of action potentials using PEDOT:PSS conducting polymer microwires.

Project description:We describe the use of PEDOT:PSS conducting polymer microwires to modulate action potentials in single cells.PedotPSS conducting polymer microwires are electrochemically synthesized with diameters ranging from 860?nm to 4.5??m and conductivities of ~30?S/cm. The length of the microwires is controlled by the spacing of the electrodes used for the electrochemical polymerization. We demonstrate the use of these microwires to control the action potentials of cardiomyocytes, showing that the cellular contractions match the frequency of the applied voltage. Membrane integrity assays confirm that the voltage delivered by the wires does not damage cells. We expect the conducting polymer microwires will be useful as minimally invasive devices to control the electrical properties of cells with high spatial precision.

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Structural, Morphological, Electrical and Electrochemical Properties of PVA: CS-Based Proton-Conducting Polymer Blend Electrolytes.

Project description:Polymer blend electrolytes based on poly(vinyl alcohol):chitosan (PVA:CS) incorporated with various quantities of ammonium iodide were prepared and characterized using a range of electrochemical, structural and microscopic techniques. In the structural analysis, X-ray diffraction (XRD) was used to confirm the buildup of the amorphous phase. To reveal the effect of dopant addition on structural changes, field-emission scanning electron microscope (FESEM) was used. The protrusions of salt aggregates with large quantity were seen at the surface of the formed films at 50 wt.% of the added salt. The nature of the relationship between conductivity and dielectric properties was shown using electrochemical impedance spectroscopy (EIS). The EIS spectra were fitted with electrical equivalent circuits (EECs). It was observed that both dielectric constant and dielectric loss were high in the low-frequency region. For all samples, loss tangent and electric modulus plots were analyzed to become familiar with the relaxation behavior. Linear sweep voltammetry (LSV) and transference number measurement (TNM) were recorded. A relatively high cut-off potential for the polymer electrolyte was obtained at 1.33 V and both values of the transference number for ion (tion) and electronic (telec) showed the ion dominant as charge carrier species. The TNM and LSV measurements indicate the suitability of the samples for energy storage application if their conductivity can be more enhanced.

| S-EPMC7231387 | biostudies-literature

Fabrication of PEDOT:PSS/Ag2Se Nanowires for Polymer-Based Thermoelectric Applications.

Project description:Flexible Ag2Se NW/PEDOT:PSS thermoelectric composite films with different Ag2Se contents (10, 20, 30, 50, 70, and 80 wt.%) are fabricated. The Ag2Se nanowires are first fabricated with solution mixing. After that, Ag2Se NW/PEDOT:PSS composite film was fabricated using a simple drop-casting method. To evaluate the potential applications of the Ag2Se NW/PEDOT:PSS composite, their thermoelectric properties are analyzed according to their Ag2Se contents, and strategies for maximizing the thermoelectric power factor are discussed. The maximum room-temperature power factor of composite film (178.59 μW/m·K2) is obtained with 80 wt.% Ag2Se nanowires. In addition, the composite film shows outstanding durability after 1000 repeat bending cycles. This work provides an important strategy for the fabrication of high-performance flexible thermoelectric composite films, which can be extended to other inorganic/organic composites and will certainly promote their development and thermoelectric applications.

| S-EPMC7764283 | biostudies-literature

Human Bone Marrow Stromal Cells cultured on polymer scaffolds with varied properties

Project description:Microarray analysis was used to evaluate expression differences from a single donor human bone marrow stromal cells (hBMSCs) as a function of varied polymer-based tissue engineering scaffolds. The results revealed that gene expression patterns of hBMSCs grouped according to scaffold. A library of scaffolds prepared from polycaprolactone (PCL) or poly D,L-lactic acid (PDLLA) was sythesized and cultured with hBMSCs for 14 days with RNA extracted from cells on Day 1 and Day 14. Gene expression analysis was performed using BRB ArrayTools. GF = gas foam, SC = spun coat, BNF = big nanofiber, SNF = small nanofiber, FFF = free-form fabricated, TCPS = tissue culture polystyrene, TCPS+OS = tissue culture polystyrene with osteogenic supplements. The 72 arrays data was used previously in the publication: Kumar et al. The determination of stem cell fate by 3D scaffold structures through the control of cell shape, Biomaterials (2011) 32, 9188-9196. A companion data set of 24 arrays was submitted separately to GEO as GSE50744 and will be referenced to Baker et al. Ontology Analysis of Global Gene Expression Differences of Human Bone Marrow Stromal Cells Cultured on 3D Scaffolds or 2D Films

2013-11-01 | E-GEOD-50743 | biostudies-arrayexpress

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