Search

Because the combination of π-conjugated polymers with biocompatible synthetic counterparts leads to the development of bio-relevant functional materials, this paper reports a new oligo(2-methyl-2-oxazoline) (OMeOx)-containing thiophene macromonomer, denoted Th-OMeOx . It can be used as a reactive precursor for synthesis of a polymerizable 2,2'-3-OMeOx-substituted bithiophene by Suzuki coupling. Also a grafted polythiophene amphiphile with OMeOx side chains was synthesized by its self-acid-assisted polymerization (SAAP) in bulk. The results showed that Th-OMeOx is not only a reactive intermediate but also a versatile functional material in itself. This is due to the presence of 2-bromo-substituted thiophene and ω-hydroxyl functional end-groups, and due to the multiple functionalities encoded in its structure (photosensitivity, water self-dispersibility, self-assembling capacity). Thus, analysis of its behavior in solvents of different selectivities revealed that Th-OMeOx forms self-assembled structures (micelles or vesicles) by "direct dissolution".Unexpectedly, by exciting the Th-OMeOx micelles formed in water with λ abs of the OMeOx repeating units, the intensity of fluorescence emission varied in a concentration-dependent manner.These self-assembled structures showed excitation-dependent luminescence as well. Attributed to the clusteroluminescence phenomenon due to the aggregation and through space interactions of electron-rich groups in non-conjugated, non-aromatic OMeOx, this behavior certifies that polypeptides mimic the character of Th-OMeOx as a non-conventional intrinsic luminescent material.

Poly(3-alkylthiophene) (PT)-based conjugated polyelectrolytes (CPEs) constitute an important class of responsive polymers with excellent optical properties. The electrostatic interactions between PTs and target analytes trigger complexation and concomitant conformational changes of the PT backbones that produce distinct optical responses. These conformation-induced optical responses of the PTs enable them to be utilized as reporters for detection of various analytes by employing simple UV-vis spectrophotometry or the naked eye. Numerous PTs with unique pendant groups have been synthesized to tailor their interactions with analytes such as nucleotides, ions, surfactants, proteins, and bacterial and viral pathogens. In this perspective, we discuss PT-target analyte complexation for bioanalytical applications and highlight recent advancements in point-of-care and field deployable assays. Subsequently, we highlight a few areas of critical importance for future applications of PTs as reporters, including (i) design and synthesis of specific PTs to advance the understanding of the mechanisms of interaction with target analytes, (ii) using arrays of PTs and linear discriminant analysis for selective and specific detection of target analytes, (iii) translation of conventional homogeneous solution-based assays into heterogeneous membrane-based assay formats, and finally (iv) the potential of using PT as an alternative to conjugated polymer nanoparticles and dots in bioimaging.

Initially developed for classic systems composed of fatty acids and phospholipids, the Langmuir and Langmuir-Blodgett (LB) techniques allow the fabrication of nanometer-scale devices at self-assembly interfaces with high control over the thickness and molecular architecture. Their application in the research and production of new plastic materials has grown considerably over the past few decades due to the efficiency of conjugated polymers (CPs) for the production of light-emitting diodes, flexible displays, solar cells, and other photoelectronic devices. The structuring of polymers at different interfaces is not trivial as this class of macromolecules can undergo through different processes of folding/unfolding, which hinders the formation of stable Langmuir monolayers and, consequently, the production of Langmuir-Blodgett films. With these ideas in mind, the present article aims to review a series of elements related to the formation of stable Langmuir and Langmuir-Blodgett films of CPs, especially those based on poly(phenylene vinylene)s, polyfluorenes, and polythiophenes. This review is divided into two parts where we first discuss the formation of neat CP films, and then the strategies for the formation of stable CP films based on the co-immobilization with fatty acids, other polymers, and enzymes as mixed films., Competing Interests: Declaration of Competing Interest None. Declaration of Competing Interest I hereby declare no conflict of interest for the above cited paper submitted., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Fast and efficient identification of bacterial pathogens in water and biological fluids is an important issue in medical, food safety, and public health concerns that requires low-cost and efficient sensing strategies. Impedimetric sensors are promising tools for monitoring bacteria detection because of their reliability and ease-of-use. We herein report a study on new biointerface-based amphiphilic poly(3-hexylthiophene)- b -poly(3-triethylene-glycol-thiophene), P3HT- b -P3TEGT, for label-free impedimetric detection of Escherichia coli ( E. coli ). This biointerface is fabricated by the self-assembly of P3HT- b -P3TEGT into core-shell nanoparticles, which was further decorated with mannose, leading to an easy-to-use solution-processable nanoparticle material for biosensing. The hydrophilic block P3TEGT promotes antifouling and prevents nonspecific interactions, while improving the ionic and electronic transport properties, thus enhancing the electrochemical-sensing capability in aqueous solution. Self-assembly and micelle formation of P3HT- b -P3TEGT were analyzed by 2D-NMR, Fourier transform infrared, dynamic light scattering, contact angle, and microscopy characterizations. Detection of E. coli was characterized and evaluated using electrochemical impedance spectroscopy and optical and scanning electron microscopy techniques. The sensing layer based on the mannose-functionalized P3HT- b -P3TEGT nanoparticles demonstrates targeting ability toward E. coli pili protein with a detection range from 10 3 to 10 7 cfu/mL, and its selectivity was studied with Gram(+) bacteria. Application to real samples was performed by detection of bacteria in tap and the Nile water. The approach developed here shows that water/alcohol-processable-functionalized conjugated polymer nanoparticles are suitable for use as electrode materials, which have potential application in fabrication of a low-cost, label-free impedimetric biosensor for the detection of bacteria in water.

In this work, a series of eight thiophene-based polymers (exploited as "donors" in bulk heterojunction photovoltaics cells), whose structures were designed to be suitably tuned with the electronic characteristics of the [6,6]-Phenyl C61 butyric acid methyl ester (PCBM), is considered,. The electronic properties of the mono-, di-, trimeric oligomers are reckoned (at the Hartree-Fock and DFT level of the theory) and compared to experimental spectroscopic and electrochemical results. Indeed, electrochemical and spectroscopic results show a systematic difference whose physical nature is assessed and related to the exciton (electron-hole) binding energy ( J e , h ). The critical comparison of the experimental and theoretical band gaps, i.e., the HOMO-LUMO energy difference, suggests that electrochemical and DFT values are the most suited to being used in the design of a polythiophene-based p-n junction for photovoltaics.

The dispersion mechanism of carbon nanotubes (CNTs) in organic solutions of poly(3-alkyl thiophenes, P3ATs) was examined in a study that combines experimental investigation of the dispersion mechanism and molecular theory calculations of the effective intertube potential for polymer wrapped CNTs. The minimal polymer concentration required for dispersion of CNT served as a comparative measure of the efficiency of P3AT derivatives that differ in the length of the alkyl side chains or the regiochemistry of the monomers in three solvents: 1,2 and 1,3 dichlorobenzene and chloroform. While previous studies focused on the adsorption mechanism of P3ATs onto SWNT, we find that the dispersing efficiency depends not only on the stacking of the polymer backbone onto the CNT ("wrapping"), but also on the steric repulsion among the side chains of adsorbed P3ATs. In accordance with the experiments, our calculations indicate that high surface density of polymers with longer side chains and large tube diameter promote the formation of stable dispersions of relatively high loadings of CNTs, at low polymer:CNT ratios., (Copyright © 2015 Elsevier Inc. All rights reserved.)

We present a theoretical approach for the in silico generation of new polymer structures for the systematic search for new materials with advanced properties. It is based on Bicerano's Regression Model (RM), which uses the structure of the smallest repeating unit (SRU) for fast and adequate prediction of polymer properties. We have developed the programs (a) GenStruc, for generating the new polymer SRUs using the enumeration and Monte Carlo algorithms, and (b) PolyPred, for predicting properties for a given input polymer as well as for multiple structures stored in the database files. The structure database from the original Bicerano publication is used to create databases of backbones and pendant groups. A database of 5,142,153 unique SRUs is generated using the scaffold-based combinatorial method. We show that using only known backbones of the polymer SRU and varying the pendant groups can significantly improve the predicted extreme values of polymer properties. Analysis of the obtained results for the dielectric constant and refractive index shows that the values of the dielectric constant are higher for polyhydrazides than for polyhydroxylamines. The high value predicted for the refractive index of polythiophene and its derivatives is in agreement with the experimental data. [ABSTRACT FROM AUTHOR]

The application of titanium nitride (TiN) as an electrode for electrochemical deposition or characterization requires the removal of an insulating layer from its surface. This process was studied and optimized, and the conditions for the complete removal of this layer through treatment with oxalic acid were formulated. The obtained TiN surfaces were used for the deposition of various conducting and non-conducting polymers. Two different approaches were applied: (i) in situ electrochemical synthesis of the main classes of conducting polymers, including polyaniline, polypyrrole, polythiophene, and selected derivatives thereof, and (ii) electrostatically driven layer-by-layer (LbL) deposition of multilayers of oppositely charged polyelectrolytes. The deposited polymers were characterized by electrochemical methods. The electrochemical properties of the deposited conducting polymers and their deposition on the TiN surface were comparable to those of the metallic electrodes. The films produced via LbL deposition exhibited a pronounced influence of the charge of the last deposited polymer on the redox reaction of ferri/ferrocyanide, validating the charge alteration with each successive polymer layer deposition. The studied deposition technologies can be used for the modification of TiN surfaces required in applications of this material in chemical sensors and other devices. [ABSTRACT FROM AUTHOR]

Activated carbons doped with nitrogen and/or sulfur have been obtained by pyrolysis followed of steam activation of a sulfur containing polymer (polythiophene) and two nitrogen-containing polymers (polyaniline and polypyrrole). These polymers were synthesized by oxidative chemical polymerization in aqueous media of their corresponding monomers. The influence of the steam activation on the textural properties and surface chemistry of the carbons has been evaluated and their catalytic activity has been determined in the hydrogenation reaction of 1-chloro-4-nitrobenzene. The degree of conversion in the reaction depends on the development of adequate porosity in the activated carbon (which is determined by the activation conditions) together with the presence of heteroatoms that act as active catalytic sites, with S showing considerably greater effectiveness than N. A compromise between an acceptable level of doping with sulfur and an adequate porosity is necessary, which has been achieved in a carbon obtained from polythiophene pyrolyzed at 900 °C and steam activated at 800 °C for 4 h, with a specific surface area of 742 m2/g and S content of 1.71 at%. [Display omitted] • N and S containing polymers used as precursors of metal-free doped activated carbons. • S-doped carbons are more active than N-doped carbons in the catalytic hydrogenation of 1-chloro-4-nitrobenzene. • Steam activation at high temperature develops carbon porosity but removes heteroatoms. • Compromise between S-doping and developed porosity is necessary to maximize catalytic performance. • 100 % selectivity in the hydrogenation of the nitro group towards aniline in all cases. [ABSTRACT FROM AUTHOR]

Polythiophene‐based conjugated polyelectrolytes (CPE) are attracting increasing attention as sensor or interface materials in chemistry and biology. While cationic polythiophenes are better understood, limited structural information is available on their anionic counterparts. Limited access to well‐defined polymers has made the study of structure‐property relationships difficult and clear correlations have remained elusive. By combining controlled Kumada catalyst transfer polymerization with a polymer‐analog substitution, regioregular and narrowly distributed poly(6‐(thiophen‐3‐yl)hexane‐1‐sulfonate)s (PTHS) with tailored chain length are prepared. Analysis of their aqueous solution structures by small‐angle neutron scattering (SANS) revealed a cylindrical conformation for all polymers tested, with a length close to the contour length of the polymer chains, while the estimated radii remain too small (<1.5 nm) for extensive π‐stacking of the chains. The latter is particularly interesting as the longest polymer exhibits a concentration‐independent structured absorption typical of crystalline polythiophenes. Increasing the ionic strength of the solution diminishes these features as the Coulomb repulsion between the charged repeat units is shielded, allowing the polymer to adopt a more coiled conformation. The extended π‐conjugation, therefore, appears to be a key parameter for these unique optical features, which are not present in the corresponding cationic polythiophenes. [ABSTRACT FROM AUTHOR]

Polythiophene, as a class of potential electron donor units, is widely used in organic electronics such as transistors. In this work, a novel polymeric material, PDPPTT-FT, was prepared by incorporating the electron acceptor unit into the polythiophene system. The incorporation of the DPP molecule assists in improving the solubility of the material and provides a convenient method for the preparation of field effect transistors via subsequent solution processing. The introduction of fluorine atoms forms a good intramolecular conformational lock, and theoretical calculations show that the structure displays excellent co-planarity and regularity. Grazing incidence wide-angle X-ray (GIWAXS) results indicate that the PDPPTT-FT is highly crystalline, which facilitates carrier migration within and between polymer chains. The hole mobility of this π-conjugated material is as high as 0.30 cm2 V−1 s−1 in organic transistor measurements, demonstrating the great potential of this polymer material in the field of optoelectronics. [ABSTRACT FROM AUTHOR]

Polymerized small molecule acceptors have recently greatly facilitated the development of all‐polymer solar cells (All‐PSCs) with respect to the power conversion efficiencies (PCEs). However, high‐performance and low‐cost polymer donors for All‐PSCs are still lacking, limiting further large‐scale manufacturing of All‐PSCs. Herein, this work designs and synthesizes a new thiophene derivative, FETVT, featuring vinyl‐bridged fluorine and ester‐substituted monothiophene. Incorporation of FETVT into a polymer yields a high‐performance polythiophene derivative PFETVT‐T, which exhibits deep‐lying HOMO level, suitable solution pre‐aggregation ability, finely‐tuned polymer crystallinity, and appropriate thermodynamic miscibility with the polymer acceptor L15. As a result, binary based on PFETVT‐T achieves a record PCE of 11.81% with agood stability, representing a breakthrough for polythiophenes and their derivatives‐based All‐PSCs, which is also significantly higher than that (1.92%) of All‐PSCs based on its isomerized analog. Remarkably, PFETVT‐T achieves an impressive PCE exceeding 16% via the implementation of a ternary blend design. These findings offer a hopeful pathway toward attaining high‐performance, stable, and cost‐effective PSCs. [ABSTRACT FROM AUTHOR]

Conjugated polymers have demonstrated to express chirality, for instance, by strong circular dichroism (CD). However, the shape and intensity of the spectra can be quite different and are very difficult to predict. Molecular irregularity, star‐shapes, and linking polymers have demonstrated to affect the CD, often in a positive way. In this research, we design two different chiral arms, in which the molecular irregularity results in a significantly different CD. Next, the arms are coupled to a linear core in all possible combinations. In this way, we demonstrate that rather small irregularities and linking arms to a central core increases CD, whereas heterogenous combinations result in smaller CD. [ABSTRACT FROM AUTHOR]

Herein, three multifunctional 3',4'-bis(alkyloxy)-2,2':5',2"-terthiophene comprising monomers with different alkyl chains were electrochemically polymerized on an ITO electrode to obtain the polymers; poly(3',4'-dibutoxy-2,2':5',2"-terthiophene) (P1), poly(3',4'-bis(hexyloxy)-2,2':5',2"-terthiophene) (P2), and poly(3',4'-bis(octyloxy)-2,2':5',2"-terthiophene) (P3). Cyclic voltammetry and in situ spectroelectrochemical studies were performed for the polymers to investigate their oxidation potentials, HOMO/LUMO energy levels, band gaps (Egop), optical contrasts (T%), and switching times. All polymers had an optical band gap at around 1.8 and 1.9 eV and revealed different tones of red color in their neutral states and different tones of blue color in their oxidized states with similar electrochromic features. This means that the alteration of the alkyl chain lengths did not affect the band gap and the colors of the resulting polymers significantly. When P1, P2, and P3 were compared in terms of electrochromic contrast and switching studies, P1 had superior optical contrast and switching time values. P1 exhibited 51% optical contrast at 520 nm which is a rare and desired property for π -conjugated conducting polymers in the visible region. P1, P2 and P3 conducting polymer films, which were also used for energy storage applications before, revealed promising electrochromic characters in this study, so these poly(3',4'-bis(alkyloxy)-2,2':5',2"-terthiophene) derivatives can be called as multifunctional next-generation materials. [ABSTRACT FROM AUTHOR]

The novel monomer, 4‐(2‐(4‐(bis(4‐(thiophen‐2‐yl)phenyl)amino)phenyl)‐5‐(thiophen‐2‐yl)thieno[3,2‐b]thiophen‐3‐yl)benzonitrile, is synthesized by applying Suzuki coupling reaction and electropolymerized directly onto indium tin oxide coated glass electrode surface to obtain a conjugated microporous polymer of [Th3CNTT–TPA] (P[Th3CNTT–TPA]). The morphology and structure of the polymer film are characterized by atomic force microscopy, Fourier transform infrared, and UV–visible spectroscopies. Electrochemical properties are studied using cyclic voltammetry, electrochemical impedance spectroscopy, galvanostatic charge–discharge, and chronoamperometric measurements. Its gravimetric capacity and capacitance values are measured to be 65 and 235 F g−1 at a current density of 3 A g−1, respectively. It shows high energy and power densities of 65 and 32.5 kWh kg−1, respectively, and exhibits high coloration efficiency of 513 C−1 cm2 in visible region, switching between yellow and grey colors. Three different electrochromic–supercapacitor devices, that is, one symmetrical (energy storage device (ESD)1) and two asymmetrical, using poly(3,4‐ethylendioxythiophen) (ESD2) and poly(3,4‐propylenedioxypyrrole) (ESD3) as counter electrodes, are fabricated. The asymmetrical device, ESD3, demonstrats better capacity and stability. Regarding the cyclic stability and electrochromic‐energy‐storage properties, P[Th3CNTT–TPA] can be considered as a good candidate for multifunctional applications. [ABSTRACT FROM AUTHOR]

The present work reports the synthesis of water-dispersible polypyrrole (WD-PPy) and polythiophene (WD-PTh) copolymers in different weight ratios and their characterization using experimental and theoretical techniques. The copolymers were spectroscopically characterized using experimental 13C-NMR, FTIR, and UV-visible studies, and theoretical FTIR and UV-visible studies. The theoretical frequency and UV-visible data were computed using Gaussian 09 software with the functional DFT/B3LYP method and 6-31G(d) basis set. For the first time, biophysical interaction studies were carried out using bovine serum albumin (BSA) and human serum albumin (HSA) for these polymers which are not yet reported in the literature. The results showed strong binding of the co-oligomers with BSA/HSA which could be utilized in designing potent inhibitors and biosensors. [ABSTRACT FROM AUTHOR]

The development of the modern society imposes a fast-growing demand for new advanced functional polymer materials. To this aim, one of the most plausible current methodologies is the end-group functionalization of existing conventional polymers. If the end functional group is able to polymerize, this method enables the synthesis of a molecularly complex, grafted architecture that opens the access to a wider range of material properties, as well as tailoring the special functions required for certain applications. In this context, the present paper reports on α-thienyl-ω-hydroxyl-end-groups functionalized oligo-(D,L-lactide) (Th-PDLLA), which was designed to combine the polymerizability and photophysical properties of thiophene with the biocompatibility and biodegradability of poly-(D,L-lactide). Th-PDLLA was synthesized using the path of "functional initiator" in the ring-opening polymerization (ROP) of (D,L)-lactide, assisted by stannous 2-ethyl hexanoate (Sn(oct)2). The results of NMR and FT-IR spectroscopic methods confirmed the Th-PDLLA's expected structure, while the oligomeric nature of Th-PDLLA, as resulting from the calculations based on 1H-NMR data, is supported by the findings from gel permeation chromatography (GPC) and by the results of the thermal analyses. The behavior of Th-PDLLA in different organic solvents, evaluated by UV–vis and fluorescence spectroscopy, but also by dynamic light scattering (DLS), suggested the presence of colloidal supramolecular structures, underlining the nature of the macromonomer Th-PDLLA as an "shape amphiphile". To test its functionality, the ability of Th-PDLLA to work as a building block for the synthesis of molecular composites was demonstrated by photoinduced oxidative homopolymerization in the presence of diphenyliodonium salt (DPI). The occurrence of a polymerization process, with the formation of a thiophene-conjugated oligomeric main chain grafted with oligomeric PDLLA, was proven, in addition to the visual changes, by the results of GPC, 1H-NMR, FT-IR, UV–vis and fluorescence measurements. [ABSTRACT FROM AUTHOR]

In this work, five polythiophene derivatives were synthesized through electrochemical copolymerization of 3,3-bis(bromomethyl)-3,4-dihydro-2 H -thieno[3,4- b ] (Deng et al., 2023; Li et al., 2020) [1,4]dioxepine (ProDOT-Br) and 3,3-dimethyl-3,4-dihydro-2 H -thieno[3,4- b ] (Deng et al., 2023; Li et al., 2020) [1,4]dioxepine (ProDOT-Me) at different mass ratios. DFT results prove that the layer spacing of conjugated blocks was increased from 5.94 Å for PProDOT-Me to 8.89 Å for PProDOT-Br due to the introduction of Br atom into side chain. And, the diverse film morphologies, such as fibre shape, cellular shape, flat shape, etc, were obtained by changing Br content in polymer. Additionally, through optimizing Br content, PBM(1,2) achieved enhanced electrochromic properties relative to two reference polymers [PProDOT-Br and PProDOT-Me], such as high optical contrast (Δ T = 76 %), fast response time (0.5 s), high transparency, and good stability. Finally, the flexible electrochromic device (8 cm × 4 cm) based on PBM(1,2) was constructed, which achieves rapid color change from purple to transparent blue. The results indicate that introducing various contents of Br atom into side chain is an effective strategy for regulating molecular microstructure and optimizing electrochromic properties of conjugated polymers. [Display omitted] • A series of Br modified polythiophene derivatives were prepared by electrochemical method. • Br in side chain could regulate the microstructure of conjugated polymer. • PBM(1,2) achieves high optical contrast (Δ T = 76 %), fast response time (0.5 s), and good stability. [ABSTRACT FROM AUTHOR]

Conjugated polymers of BTTP and BTTP–CN comprising thiophene and benzothiadiazole substituents were subjected under chemical doping process. The polymers were doped with different Lewis acids such as AlCl3, H3BO3, BF3, Cu(II), Fe(II), HCl and I2. The doped and undoped polymers have been analyzed with the aid of FTIR, UV–Vis, fluorescence spectrometer, electrochemical conductivity and cyclic voltammetry. Upon doping, the absorption maximum of the polymers (403 and 397 nm) were dramatically shifted and emission wavelength of BTTP and BTTP–CN was red shifted due to chemical interaction among dopants. The electrochemical band gap of undoped polymers BTTP and BTTP–CN has been measured as 1.9 and 1.6 eV and conductivity was measured as 3.62 and 1.46 × 10–5 Ω−1 cm−1, respectively. After doping with Lewis acids, band gap was reduced and conductivity was increased. The reactivity of the polymers with AlCl3, BF3, and HCl dopants produced low band gap, high conductivity up to 0.79 eV, 5.98 × 10–5 Ω−1 for BTTP and 1.0 eV, 4.43 × 10–5 Ω−1 for BTTP–CN, respectively. Introduction of dopants to the conjugated polymers opens up the opportunity to increase conjugation, Turn off/on fluorescence and shifting of energy levels in solar cell applications. [ABSTRACT FROM AUTHOR]

Matrix‐assisted laser desorption/ionization mass spectrometry (MALDI MS) requires a matrix, and traditionally small organic matrices (SOMs) carrying acidic or basic functional groups are used. However, the analyte ionization via secondary processes in the gas‐phase seems to be more important than primary processes. For conjugated polymeric matrices, an even more complicated picture emerges due to their apolar and aprotic nature, high molecular weight, and low tendency to desorb. Poly(3‐dodecylthiophene‐2,5‐diyl) (P3DDT), a good matrix for low‐molecular weight (LMW) analytes, does not give matrix‐related peaks in the LMW area. Here, carboxylic acid (COOH) side‐chains are introduced via postpolymerization modification. The polymers are characterized by NMR, FT‐IR, CV, MALDI MS, and, when possible, GPC. The electron withdrawing side‐chains serve three functions; i) raising the ionization potential (IP), ii) improving the absorption maximum, and iii) acting as a source of protons. When measuring basic amines, this results in the occurrence of additional [Analyte + H+]+ signals compared to polymers without acidic groups, where only radical cations [Analyte]+• are detected. Similarly, estradiol and testosterone, compounds with high IPs, are not detected by polythiophenes without acidic groups, while P3DDT‐COOH enables detection as protonated species. [ABSTRACT FROM AUTHOR]

Initially, pristine polymers were used to develop corrosion-resistant coatings. Later, the trend shifted to the use of polymeric nanocomposites in anti-corrosion materials. In this regard, graphene has been identified as an important corrosion-resistant nanomaterial. Consequently, polymer/graphene nanocomposites have been applied for erosion protection applications. Among polymers, conducting polymers (polyaniline, polypyrrole, polythiophene, etc.) and nonconducting polymers (epoxy, poly(methyl methacrylate), etc.) have been used as matrices for anticorrosion graphene nanocomposites. The corrosion-resistant polymer/graphene nanocomposites have found several important applications in biomedical fields such as biocompatible materials, biodegradable materials, bioimplants, tissue engineering, and drug delivery. The biomedical performance of the nanomaterials depends on the graphene dispersion and interaction with the polymers and living systems. Future research on the anti-corrosion polymer/graphene nanocomposite is desirable to perceive further advanced applications in the biomedical arenas. [ABSTRACT FROM AUTHOR]

[Display omitted] • Nanocomposites of MWCNTs/PTh were synthesized via in-situ polymerization method. • These composites were employed as catalyst materials for the counter electrode of DSSCs. • FTIR and XRD analyses conform the interaction of MWCNTs with PTh in composites. • MWCNTs contents in composites affect the efficiency of DSSCs. • DSSC with 30 %MWCNTs/PTh shows the PCE of 1.608%, higher than Pt based cell (1.067%). Platinum is utilized to a significant degree as a catalyst material in the fabrication of dye-sensitized solar cells. However, its utilization is constrained by its high cost, scarcity, requirement for high purity, poor corrosion resistance against liquid electrolytes, and energy-intensive deposition techniques. It is possible to substitute platinum with carbon allotropes or composites built of conductive polymer materials. In this study, in-situ polymerization was used to synthesize nanocomposites of multi-walled carbon nanotubes and polythiophene. X-ray Diffraction, Fourier-Transform Infrared Spectroscopy, and Scanning Electron Microscopy were used to examine the interactions between ingredients and the morphological features of composites, respectively. The results showed that the amount of multi-walled carbon nanotubes in composites affects the effectiveness of solar devices. Compared to cells based on 10% and 60 %MWCNTs/PTh, the efficiency of the cell that was made with 30 %MWCNTs/PTh exhibited a greater level of performance. The results also showed that the MWCNTs/PTh device outperformed Pt-based solar cells in terms of performance. [ABSTRACT FROM AUTHOR]

Aromatic polymers are the first-choice platform for current organic materials due to their distinct optical, electronic, and mechanical properties as well as their biocompatibility. However, bare aromatic polymer backbones tend to strongly aggregate, rendering them essentially insoluble in organic solvent. While the typical solution is to install many solubilizing substituents on the backbones, this often provokes undesired property changes. Herein, we report the synthesis of bare aromatic polymers enabled by a dendrimer support. An initiator arene containing a diterpenoid-based dendrimer undergoes Pd-catalyzed polymerization with monomers bearing no solubilizing substituents to furnish bare aromatic polymers such as polythiophenes and poly(para-phenylene)s. The high solubility of dendrimer-ligated polymers allows not only the unveiling of the properties of unsubstituted π-conjugated backbone, but also mild release of dendrimer-free aromatic polymers and even transfer of aromatic polymers to other materials, such as silica gel and protein, which may accelerate the creation of hybrid materials nowadays challenging to access. Unsubstituted aromatic polymers are materials with multiple potential applications, but their preparation remains challenging. Here, the authors report a dendrimer-enabled synthesis of soluble bare aromatic polymers and explore their properties; these compounds can be further transformed into other materials. [ABSTRACT FROM AUTHOR]

We synthesized the polythiophene‐based copolymers (poly(3‐thiopheneacetic acid‐co‐3‐dodecylthiophene)s [poly(3TA‐co‐3DT)s]) and homopolymer (poly(3‐dodecylthiophene) [P3DT]) as a polymer host to apply on quasi‐solid‐state electrolytes of dye‐sensitized solar cells (DSSCs). In order to improve their solubility and interface adsorption onto nanoporous TiO2 surface, the poly(3TA‐co‐3DT)s were designed with the chemical structure containing long‐alkyl group and carboxyl group, and the polythiophene‐based homopolymer (P3DT) was synthesized to compare the photovoltaic characteristics according to the presence of the carboxyl group. The quasi‐solid‐state DSSCs using P3DT, poly(3TA‐co‐3DT)‐1, and poly(3TA‐co‐3DT)‐2 have power conversion efficiencies of 2.62%, 2.97%, and 2.90% under photointensity of 100 mW/cm2 at AM1.5, respectively. In particular, the Jsc and power conversion efficiency of DSSC device using poly(3TA‐co‐3DT)‐1 increased up to 16.81 mA/cm2 and 4.45% by the addition of the ionic liquid. [ABSTRACT FROM AUTHOR]

Converting small organic molecules to their lithium salts or polymerization effectively solves the capacity fading caused by the dissolution of small organic molecules in electrolytes. While polymer lithium salts have the characteristics of small molecular lithium salts and polymers and can obtain good cycle stability and rate performance. The 3‐carboxylithium substituted thiophene (3‐TCOOLi) and polymer (P3‐TCOOLi) anode materials for lithium‐ion batteries were synthesized, and their electrochemical properties were compared. Compared with the small‐molecule lithium salt 3‐TCOOLi electrode, the polymer P3‐TCOOLi electrode exhibits superior cycling and rate performance. The P3‐TCOOLi electrode still has a specific capacity of 390 mAh g−1 after 100 cycles at a current density of 50 mA g−1. During the rate charge and discharge process, when the current density increased to 1000 mA g−1, the specific capacity was 305 mAh g−1. It shows that the idea of small molecule lithium salt polymerization is feasible. [ABSTRACT FROM AUTHOR]

In this study, a simple and effective method was presented for the preparation of binder-free conducting polymer/metal oxide binary composite electrode materials. The novel electropolymerizable thiophene monomer, 3-[(2,2′:5′,2′′-terthiophen-3′-yl)]-2-cyanoacrylic acid) (SDOGA), was specifically designed to fabricate homogeneous and chemically stable redox-active composite electrodes for pseudocapacitor applications. Poly(3-[(2,2′:5′,2′′-terthiophen-3′-yl)]-2-cyanoacrylic acid) (PSDOGA) was electrochemically deposited on stainless steel substrates and modified with TiO2 and V2O5 particles via a simple, efficient and low-cost process without any polymeric binder. Cyclic voltammetry (CV), galvanostatic charge/discharge (GCD) and electrochemical impedance spectroscopy (EIS) techniques were used to study the pseudocapacitive properties of PSDOGA/TiO2 and PSDOGA/V2O5 binder-free binary composites in both three-electrode and two-electrode cell configurations. PSDOGA/TiO2 and PSDOGA/V2O5 composites delivered high specific capacitances of 396.4 Fg−1 and 444.5 Fg−1, respectively, at 2.5 mA cm−2 current density in single electrode measurements. Symmetrical supercapacitor devices assembled by using PSDOGA/TiO2 and PSDOGA/V2O5 binder-free binary composite electrodes exhibited satisfactory energy (78 W h kg−1 and 94.8 W h kg−1) and power (700 W kg−1 and 736 W kg−1) densities with good charge/discharge characteristics at a large operating voltage of 1.85 V. Furthermore, symmetric type supercapacitor cells achieved an excellent capacitance retention of 87% and 90% for 12 500 consecutive galvanic charge/discharge cycles at a constant current density of 2.5 mA cm−2. The experimental results revealed that the cooperation between conducting polymer film and metal oxide particles not only greatly enhanced the capacitive performances, but also improved the long-term charge/discharge stability of the redox-active electrode materials. [ABSTRACT FROM AUTHOR]

The two new semiconducting polymers, poly((sexithiophene-5,5'''''-diyl)bis(tridecan-1-one))(PSTTO) and poly((sexithiophene-5,5'''''-diyl)bis(tridecan-1-one)bithiophene) (PSTTOBT), are synthesized and characterized. PSTTO and PSTTOBT have backbone donor and side chain acceptor structure. Compare to poly(3-hexylthiophene), both polymers had deep HOMO levels of 5.15 and 5.14 eV, respectively, due to intramolecular repulsing between the main chain and side chain as well as the introduction of electron withdrawing side chains. In addition, the introduction of bithiophene into the repeating unit of PSTTOBT showed increased long wave absorption and better intermolecular interaction. PSTTO and PSTTOBT based cell showed power conversion efficiencies of 1.1% and 1.6%, respectively. [ABSTRACT FROM AUTHOR]

A novel iron-coordinated conducting polymer is synthesized, followed by the preparation of Fe 3 N nanoparticle-embedded sulfur and nitrogen-doped carbon (Fe 3 N/SNC) nanostructures via a one-step polymer pyrolysis strategy, which can exceptionally catalyze the oxygen reduction reaction (ORR) in both alkaline and acidic media, and the oxidation of catecholamines. To synthesize the metal coordinated polymer, FeCl 3 is used as an oxidant and metal source for the polymerization of 3′,4′-diamino-terthiophene (DAT) to form poly-FeDAT. It is subsequently pyrolyzed at 900 °C to attain the Fe 3 N/SNC catalyst. The Fe 3 N/SNC electrocatalyst exhibit a more positive onset (0.985 V vs RHE), half-wave potentials (0.848 V), a higher limiting current density (5.47 mAcm−2), alcohol resistance and durability than the benchmark Pt/C in 0.1 M KOH, and it is comparable to Pt/C in 0.1 M HClO 4. It also displays exceptional performance for the catalytic oxidation of catecholamines and AP, which results in simultaneous detection of DA and AP in trace amounts (the detection limits were 110 nM and 270 nM (S/N = 3) for each species, respectively). The unique catalytic activity is ascribable to the presence of pyridinic-N, graphitic-N, and Fe–N along with thiophene-S in the carbon, resulting in catalytically enhanced electron transfer from Fe 3 N to N, S doped carbon. [Display omitted] • Fe 3 N NPs embedded S/N doped carbon is synthesized by a facile, one step polymer pyrolysis strategy. • The catalyst possesses extraordinary catalytic activity for oxygen reduction reaction and catecholamines oxidation. • The catalyst can simultaneously detect dopamine (DA) and acetaminophen (AP) in human urine samples. [ABSTRACT FROM AUTHOR]

Oxygen reduction reaction (ORR) is a critical process for several electrocatalytic and photocatalytic devices. Poly(3,4‐ethylenedioxythiophene), PEDOT, is an efficient ORR catalyst, with hydrogen peroxide (H2O2) being the primary reaction product. Although H2O2 is a green fuel for batteries and fuel cells and used as an industrial oxidant, it is toxic for living systems. As such, its production should be limited when PEDOT films are used in bioelectronic devices. In this work, the ORR behavior of a series of electropolymerized PEDOT films is investigated. By varying the counterion (monomeric vs polymeric), including a hydroxyl‐terminated EDOT monomer in the polymer architecture, or adding a conductivity enhancer in the reaction mixture, the authors aim to understand the parameters governing the ORR properties. It is that the polymer's pristine doping level—influenced by counterion type and the presence of the conductivity enhancer—controls the ORR pathway in PEDOT films. High levels of intrinsic doping led to films with H2O2 as the major ORR product. This work suggests strategies for the design of conducting polymers with optimized performance for electrocatalytic applications and minimized production of harmful chemicals for bioelectronic devices. [ABSTRACT FROM AUTHOR]

In view of increasing applications of electro‐conductive polymers in various fields such as electronics, smart textiles, sensors, energy storage, and medical. Researchers & Scientists from all over the world have continuously investigating the intrinsic conductive polymers (CPs) and its doping process to gain appreciable electrical conductivity suitable for particular applications. Its unique features such as superior stability, processability, workability, light weight, corrosion resistant, tailoribility, flexibility, and gaining wide range of electrical conductivity on doping drives CPs as a possible substitute for metals and semiconductors. An effort has been made to bring various aspects of CPs viz. different methods of synthesis, its applications, doping techniques, characterization techniques, and current trends of its utility. This review article clearly specifies about the different techniques available for the synthesis of CPs such as Polyacetylene, Polyaniline, Polypyrrole, Polyphenylene, Polythiophene, Polyphenyl vinylene, and Poly(3,4‐ethylenedioxythiophene) via polymerization using chemical, plasma, electro‐chemical, photo‐chemical, metathesis methods, and so on, and their electrical conductivity values achieved with and without dopants. [ABSTRACT FROM AUTHOR]

The functionalization of carbon nanotubes by polymers necessitates two steps, first their modification by oxidizing them or by covalently attaching small compounds to them, then the growth of the polymer chains from these anchors or their grafting onto them. In order to better control the process and the rate of functionalization, we develop polymers able to covalently react with the carbon nanotubes by their side chains in one step. We describe the synthesis of a copolymer of dodecylthiophene and its analogue bearing an aniline group at the end of the dodecyl side chain. This copolymer can functionalize single-walled carbon nanotubes (SWNTs) non-covalently and disperse more SWNTs than its hexyl analogues. UV-Vis and fluorescence spectroscopies show that in these non-covalent hybrids, the polymer forms p-stacked aggregates on the SWNTs. The noncovalent hybrids can be transformed into covalent ones by diazonium coupling. In these covalent hybrids the polymer is no longer p-stacked. According to Raman spectroscopy, the conformation of the poly(3-hexylthiophene) backbone is more ordered in the non-covalent hybrids than in the covalent ones. [ABSTRACT FROM AUTHOR]

The development of n‐type organic electrochemical transistors (OECTs) lags far behind their p‐type counterparts. In order to address this dilemma, we report here two new fused bithiophene imide dimer (f‐BTI2)‐based n‐type polymers with a branched methyl end‐capped glycol side chain, which exhibit good solubility, low‐lying LUMO energy levels, favorable polymer chain orientation, and efficient ion transport property, thus yielding a remarkable OECT electron mobility (μe) of up to ≈10−2 cm2 V−1 s−1 and volumetric capacitance (C*) as high as 443 F cm−3, simultaneously. As a result, the f‐BTI2TEG‐FT‐based OECTs deliver a record‐high maximum geometry‐normalized transconductance of 4.60 S cm−1 and a maximum μC* product of 15.2 F cm−1 V−1 s−1. The μC* figure of merit is more than one order of magnitude higher than that of the state‐of‐the‐art n‐type OECTs. The emergence of f‐BTI2TEG‐FT brings a new paradigm for developing high‐performance n‐type polymers for low‐power OECT applications. [ABSTRACT FROM AUTHOR]

The photoelectric and optical characteristics of an organic solar cell (OSС) with a hole-transport layer based on a polyaniline complex and a photoactive layer with a bulk heterojunction based on P3HT polythiophene derivative and PC71BM fullerene have been studied. The results of modeling the optical properties of the functional layers and experimental measurements of the OSC characteristics enabled the optimal values of the thickness of the functional layers resulting in the maximum power conversion efficiency of the device to be identified. It has been determined that the hole-transport layer with a thickness of 30–60 nm, while having a transmission of more than 80%, effectively transferred holes to the photoanode from the photoactive layer, in which the exciton generation rate was 5.6–5.9 × 1016 cm–2 s–1. These values of the exciton generation rate at the maximum total light absorption in the device were provided by a photoactive layer with a thickness of 90–100 nm. [ABSTRACT FROM AUTHOR]

The development of semiconductor polymers for electronic applications requires tailored synthetic strategies to obtain materials with tunable electronic properties and morphology to enhance their properties. Towards this goal, here is reported the expedient synthesis of a novel class of thiophene‐based electrochromic polymers, processable in organic solvents and as nanoparticles (NPs) in water. Their characterization and application in flexible solid‐state electrochromic devices (ECDs) are described. All polymers have a repeat unit made of the same linear thienyl–phenyl–thienyl–thienyl fragment. The tuning of the electro‐optical properties is achieved by introducing alkyl or alkoxy substituents in thiophene and/or by the presence of either CHCH or CH2CH2 linkers connecting the repeat units and acting as conjugation modulators. The ECDs display a bright yellow or red/magenta color in the neutral state and dark blue in the oxidized state. Redox potentials, color contrast, switching time, and stability of the devices are reported, and it is demonstrated that the use of NPs films spray‐coated from water instead of cast films from chloroform significantly improves their performance. Density functional theory calculations allow to elucidate the relationship between polymer structure and electrochromic properties and shed light on electronic structure changes upon oxidation, in agreement with spectroelectrochemistry. [ABSTRACT FROM AUTHOR]

Bei der Photokatalyse werden kleine organische Moleküle mithilfe von lichtempfindlichen Materialien, elektromagnetischer Strahlung und Elektronenvermittlern in gewünschte Produkte umgewandelt. Die Substitution von niedermolekularen Reagenzien durch redoxaktive Funktionsmaterialien kann den Nutzen der Photokatalyse über die organische Synthese und Umweltanwendungen hinaus erhöhen. Geleitet von den allgemeinen Prinzipien der Photokatalyse, entwarfen wir in der aktuellen Studie hybride Nanokomposite, die aus n‐Typ halbleitendem Kalium‐Poly(heptazinimid) (K‐PHI) und p‐Typ leitendem Poly(3,4‐ethylendioxythiophen) Polystyrolsulfonat (PEDOT:PSS) als redoxaktivem Substrat bestehen. Die elektrische Leitfähigkeit des hybriden Nanokomposits, das einen optimalen K‐PHI‐Gehalt aufweist, wird reversibel moduliert, indem eine Reihe von externen Stimuli kombiniert werden, die von sichtbarem Licht unter inerten Bedingungen bis hin zu dunklen Bedingungen unter einer O2‐Atmosphäre reichen. Die Verwendung eines leitfähigen Polymers als redoxaktives Substrat ermöglicht die Untersuchung der photokatalytischen Prozesse, die durch halbleitende Photokatalysatoren vermittelt werden, durch Messungen der elektrischen Leitfähigkeit. [ABSTRACT FROM AUTHOR]

Control over orientation and conformation of surface-immobilized proteins, determining their biological activity, plays a critical role in biointerface engineering. Specific protein state can be achieved with adjusted surface preparation and immobilization conditions through different types of protein-surface and protein-protein interactions, as outlined in this work. Time-of-flight secondary ion mass spectroscopy, combining surface sensitivity with excellent chemical specificity enhanced by multivariate data analysis, is the most suited surface analysis method to provide information about protein state. This work highlights recent applications of the multivariate principal component analysis of TOF-SIMS spectra to trace orientation and conformation changes of various proteins (antibody, bovine serum albumin, and streptavidin) immobilized by adsorption, specific binding, and covalent attachment on different surfaces, including self-assembled monolayers on silicon, solution-deposited polythiophenes, and thermo-responsive polymer brushes. Multivariate TOF-SIMS results correlate well with AFM data and binding assays for antibody-antigen and streptavidin-biotin recognition. Additionally, several novel extensions of the multivariate TOF-SIMS method are discussed. Graphical abstract [ABSTRACT FROM AUTHOR]

Organic polymer semiconductor‐based polymer solar cells (PSCs) are drawing tremendous research interest for their superior electrical, structural, optical, mechanical, and chemical properties. During the last two decades, immense efforts have been made toward the development of PSCs. Generally, poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is used as hole transport layer (HTL) of PSCs to improve hole extraction efficiency, but highly acidic PEDOT:PSS reduces device lifetime by destroying indium tin oxide (ITO) electrodes and active layers. To avoid this, some have attempted to develop inverted structured PSCs with different electron transport layers (ETLs); however, the power conversion efficiency (PCE) of these devices is limited owing to low electron mobility of their ETLs. Therefore, an attempt is made to improve the PCE of an inverted‐structured PSC by using indium gallium zinc oxide (IGZO) with optimized amount of indium (In), gallium (Ga), and zinc (Zn). Inverted PSCs with ZnO or IGZO (having various molar ratios of In, Ga, and Zn) as ETL with the structure ITO/ETL/PTB7:PC71BM/MoO3/Al are constructed. The PCE of the inverted PSC can be increased from 6.22% to 8.72% by using IGZO with an optimized weight ratio of In, Ga, and Zn as an ETL. [ABSTRACT FROM AUTHOR]

Solid-state humidity sensors are generally AC powered as they sense the fluctuations in the dielectric polarization and/or ionic conductance of the water layer formed by Kelvin condensation on the effective surface of their hydrophilic sensing elements. DC-powered, printable, and bendable hygrometers, however, are demanded for battery-driven wearable electronics. Here, we demonstrate that the electronic (as opposed to ionic) conduction in the polymer composite poly(3,4-ethylenedioxythiophene–poly(styrenesulfonate) (PEDOT:PSS) thin films constantly decreases with increasing relative humidity (RH) in the surrounding atmosphere and use this property for the fabrication of a DC-powered solid state hygrometer. PEDOT, the conductive component of this composite, is hydrophobic, and the hydrogen bonding of the airborne H2O to the surface available sulfonic acid groups of the non-conductive component, PSS, is verified as the main cause of sensitivity. This hydrogen bonding deters the doping action involving H+ transfer from the sulfonic acid groups to the thiophene groups on the PEDOT chain and decreases the bulk conductivity of the sensing element. As predicted by this model, the electrical resistance measurements carried out by applying DC and AC electric fields lead to different RH dependences; the former demonstrates the positive RH dependence in the full RH range, while the latter results in strongly nonlinear RH sensitivity crossing zero around RH 60%. Our model assists better understanding of the charge conduction mechanisms in PEDOT:PSS. The described sensing mechanism is anticipated to initiate research on many two-component organic composites for the fabrication of varieties of gas and humidity sensors. [ABSTRACT FROM AUTHOR]

Conducting polymers, polythiophene (PT) and polypyrrole (PPy) were prepared by chemical oxidative polymerization (COP) method. A ternary PPy-PT/TiO2 composite involve the blending of two polymers namely polythiophene and polypyrrole and further, addition of TiO2 nanoparticles in the multipart-polymer. PPy-PT/TiO2 composite exhibits the highest specific capacitance of 271.8 F/g as compared to PT/TiO2 (109.6 F/g) and PPy/TiO2 (80.4 F/g), respectively. Multipart-conducting polymers boost the conductivity of fabricated device, which enhanced specific capacitance of TiO2 based supercapacitor network, due to their improved surface area, that offers large energy storage and additional pseudocapacitance. [ABSTRACT FROM AUTHOR]

Conductive organic polymers are most commonly generated from the oxidation or reduction of conjugated polymers. Although such conjugated polymers are typically viewed as modern materials, the earliest examples of these polymers date back to the early 19th century. The modern era of conjugated polymers began with the first reports of their conductive nature in the early 1960s. However, it was advances in the 1970s that brought particular focus to these materials with the first example of conductivity values in the metallic regime, for which the 2000 Nobel Prize in Chemistry was awarded to Hideki Shirakawa, Alan MacDiarmid, and Alan Heeger. Unfortunately, the historical narrative of these polymers is currently quite muddled in the primary literature, with various inaccuracies commonly propagated. In an effort to present a more accurate account as a resource for the field, the present report will review the first 150 years of the four primary parent polymers-polyaniline, polypyrrole, polyacetylene, and polythiophene, from their early origins in 1834 to their rapid development in the mid-1980s. [ABSTRACT FROM AUTHOR]

Two thiophene backbone-based hole-transporting polymers, namely, poly[(2,2′-bithiophene-5,5′-diyl)-alt-(5,7-bis(2-butyloctyl)-4H,8H-benzo[1,2-c:4,5-c′]dithiophene-4,8-dione-1,3-diyl)] (PT2-BDD) and poly[(3,3′-difluoro-[2,2′-bithiophene]-5,5′-diyl)-alt-(5,7-bis(2-butyloctyl)-4H,8H-benzo[1,2-c:4,5-c′]dithiophene-4,8-dione-1,3-diyl)] (PF2-BDD), were prepared by using electron-withdrawing pendant groups such as ketone and fluorine moieties. They both exhibited a planar backbone with efficient π conjugation, which is suitable for hole transport in organic thin-film transistors (OTFTs). However, the fluorinated one (i.e., PF2-BDD), despite its perfect backbone planarity and strong intra- and intermolecular interactions, could not enhance the OTFT performance; due to its solvent resistance, electron negativity, and random orientation, PF2-BDD showed 10 times lower hole mobility than the non-fluorinated polymer (i.e., PT2-BDD). Nonetheless, the two-dimensional grazing incidence X-ray diffraction and temperature-dependent absorption spectra of the synthesized polymers provided crucial information to understand the relationship between their hole transport behavior and molecular structure. [ABSTRACT FROM AUTHOR]

Solid‐state polymer supercapacitors (SSP‐SCs) have vast potential for future development due to their compact, safe, environment‐friendly, and facile designing. Thus, prevalent researches have been explored in this area. In this article, poly(3,4‐ethylenedioxythiophene) (PEDOT) SSP‐SCs were assembled by using poly(3,4‐ethylenedioxythiophene)/carbon paper (PEDOT/CP) as electrodes and polyvinyl alcohol/sulfuric acid/potassium iodide (PVA/H2SO4/KI) as the gel polymer electrolyte. The effect of KI content on the electrochemical performance of the SC was studied by cyclic voltammetry, galvanostatic charge–discharge measurements (GCD), and electrochemical impedance spectroscopy. The results indicated that the PEDOT SSP‐SC has excellent electrochemical properties when KI doping amount was 60 wt %. The introduction of KI increased the specific capacitance due to the improved ionic conductivity and additional pseudocapacitance reaction at the electrode–electrolyte interface. The PEDOT SSP‐SC showed high energy and power densities of 451.32 Wh kg−1 and 13.29 kW kg−1, respectively, as well as a specific capacitance of 352.59 F g−1 for a discharge current of 1 mA cm−2. In addition, after 1000 GCD cycles, the PVA/H2SO4/KI‐based PEDOT SSP‐SC showed capacitance retention of 74.08%. Therefore, the SC exhibits outstanding energy and power density and good cycle stability and has great potential to be used in high‐energy density equipment. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020, 137, 48723. [ABSTRACT FROM AUTHOR]

A novel iodine vapour promoted polymerization method of 2,5-dibromo-3,4-ethylenedioxythiophene, and 2,5-diiodo-3,4-ethylenedioxythiophene and their derivatives at room temperature without using any solvent has been developed. The resulting polymers are conducting and electroactive in nature. After dedoping, the neutral polymers were analyzed in terms of their elemental composition, and the soluble polymers were characterized by 1H NMR and gel permeation chromatography analysis. A systematic study of the cyclic voltammetry, UV-vis absorption and spectroelectrochemistry of these polymers obtained by iodine vapour polymerization has been reported and they have been compared with previously reported solid state polymerization and electrochemically obtained polymers where applicable. [ABSTRACT FROM AUTHOR]

We have measured transient drain current in millisecond range for some poly(thiophene) transistors with different channel length. Under fixed gate bias and with source grounded, a voltage pulse is applied periodically to the drain and the current waveform is recorded. The drain current of a 50 μm channel device is almost proportional to the drain bias at 0.2 ms after the drain bias application. As the time progresses, the transient output curve starts to show a sign of saturation at a large drain bias. For a shorter-channel device, this initial resistorlike characteristic is less apparent. Two mechanisms are considered to account for this behavior. First, we analyze contribution from the channel charges that exist in excess of the steady-state distribution. Although the linear dependency on the drain bias is correctly predicted, its time dependence underestimates the observed drain current. This suggests that the number of mobile carriers in the channel is more than those balancing the gate potential during the early stage. Second, we consider relaxation of this excess current. Its decay is well fit by a stretched exponential function. Using an empirical expression for the data at a certain low drain bias, transient drain current at other drain biases is calculated. The resultant output curves more or less reproduce the measurement. [ABSTRACT FROM AUTHOR]

We report on high crystalline thin films of liquid-crystalline polythiophene derivative, poly(2,5-bis(3-hexadecylthiophene-2-yl)thieno[3,2-b]thiophene) (PB16TTT) that exhibit terrace structures and molecular steps of its polymer chains by annealing in its liquid-crystalline phase. The crystallinity of the PB16TTT polymer films formed on SiO2 gate insulating layers with smooth self-assembled monolayer was improved by changing the octyltrichlorosilane treatment time for the SiO2, which led to reproducible high field-effect mobilities of the polymer thin-film transistors up to 0.44 cm2/V s. High stability of the transistor for repeated stressing in ambient air was also demonstrated. [ABSTRACT FROM AUTHOR]

• New strategy to disrupt planarity and obtain available color. • pQ3TQ exhibited magenta-to-transmissive with excellent EC performances. • Novel ECS bifunctional materials were prepared. • pQ3TQ has large area capacitance for 2.47 mF·cm−2. • Completing the CMY palette through electropolymerization. Developing electropolymerized magenta-to-transmissive electrochromic polymers is crucial in completing the CMY color palette. In this paper, three pure donor-type monomers (E3TE, Q3TQ and pro3Tpro) with various degrees of twisting blocks as peripheral electropolymerization units (EDOT/Prodot-Me 2 /proDot) and terthiophene (3T) as the central nucleus have been synthesized. Moreover, the corresponding polymers (pE3TE, pQ3TQ) were prepared via electropolymerization successfully. The electrochemical and electrochromic properties of both polymers were systematically investigated. Introducing the 3, 4-propylenedioxythiophene into 3T yields pQ3TQ with heightened degrees of twisting along the polymer backbone, slightly increasing the onsets of oxidation and blue-shifting the absorption precisely. The neutral polymer colors were fine-tunable from purple to magenta while maintaining transmissive oxidized states from pE3TE to pQ3TQ. The pQ3TQ has low oxidation potential (less than 1 V (E vs Ag/AgCl)), fast-switching time (0.63 s/0.29 s at 531 nm), reasonable optical contrast (31.9 % at 531 nm), good optical memory, excellent coloring efficiency (479.9 cm2/C), robust cycle stability (600 cycles) and large area specific capacitance (2.47 mF/cm2). This work provides a novel strategy to precisely disrupt planarity to obtain available color adjustment of electropolymerized polymer films and also provides an electrochromic-supercapacitor bifunctional material. [ABSTRACT FROM AUTHOR]

In conjugated polymers the optical excitation energy transfer is usually described as Förster-type hopping between so-called spectroscopic units. In the simplest approach using the point-dipole approximation the transfer rate is calculated based on the interaction between the transition dipoles of two spectroscopic units. In the present work we compare this approach with three others: The line-dipole approximation, the Coulomb integral between the transition densities, and a quantum-chemical calculation of the interacting dimer as entity. The latter two approaches are based on the semiempirical method ZINDO. The line-dipole approximation is an attractive compromise between computational effort and precision for calculations of the excitonic coupling in extended conjugated polymers. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Triplet energies from a family of polythiophenes in which effective conjugation length is controlled by steric torsion have been measured for the isolated polymer chain regime, i.e., benzene solution. Triplet states are stabilized by some 0.6 eV as effective conjugation length increases up to ca. 6 repeat units, then saturation occurs. This triplet stabilization must occur by electron delocalization and implies that singlet states are stabilized as conjugation length increases by a combination of electron and exciton delocalization. [ABSTRACT FROM AUTHOR]

Membrane technologies that do not rely on heat for industrial gas separation would lower global energy cost. While polymeric, inorganic, and mixed‐matrix separation membranes have been rapidly developed, the bottleneck is balancing the processability, selectivity, and permeability. Reported here is a softness adjustment of rigid networks (SARs) strategy to produce flexible, stand‐alone, and molecular‐sieving membranes by electropolymerization. Here, 14 membranes were rationally designed and synthesized and their gas separation ability and mechanical performance were studied. The separation performance of the membranes for H2/CO2, H2/N2, and H2/CH4 can exceed the Robeson upper bound, among which, H2/CO2 separation selectivity reaches 50 with 626 Barrer of H2 permeability. The long‐term and chemical stability tests demonstrate their potential for industrial applications. This simple, scalable, and cost‐effective strategy holds promise for the design other polymers for key energy‐intensive separations. [ABSTRACT FROM AUTHOR]