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As integrated circuits continue to scale toward the atomic limit, bottom-up processes, such as epitaxial growth, have come to feature prominently in their fabrication. At the same time, chemistry has developed highly tunable molecular semiconductors that can perform the functions of ultimately scaled circuit components. Hybrid techniques that integrate programmable structures comprising molecular components into devices however are sorely lacking. Here we demonstrate a wafer-scale process that directs the localization of a conductive polymer, Mw = 20 kg mol-1 polyaniline, from dilute solutions into 50 nm vertical nanogap device architectures using electric-field-driven self-assembly. The resulting metal-polymer-metal junctions were characterized by electron microscopy, Raman spectroscopy and transport measurements demonstrating that our technique is highly selective, assembling conductive polymers only in electrically activated nanogaps. Our results represent a step toward scalable hybrid nanoelectronics that seamlessly integrate established lithographic top-down fabrication with bottom-up synthesized molecular functional circuit components.
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Transparent flexible energy storage devices are limited by the trade-off among flexibility, transparency, and charge storage capability of their electrode materials. Conductive polymers are intrinsically flexible, but limited by small capacitance. Pseudocapacitive MXene provides high capacitance, yet their opaque and brittle nature hinders their flexibility and transparency. Herein, the development of synergistically interacting conductive polymer Ti3C2Tx MXene/PEDOT:PSS composites is reported for transparent flexible all-solid-state supercapacitors, with an outstanding areal capacitance of 3.1 mF cm-2, a high optical transparency of 61.6%, and excellent flexibility and durability. The high capacitance and high transparency of the devices stem from the uniform and thorough blending of PEDOT:PSS and Ti3C2Tx, which is associated with the formation of OâH O H-bonds in the composites. The conductive MXene/polymer composite electrodes demonstrate a rational means to achieve high-capacity, transparent and flexible supercapacitors in an easy and scalable manner.
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In this study, magnetic graphene oxide coated with poly(8-hydroxyquinoline) was successfully synthesized, characterized, and utilized as a novel sorbent for the ultrasonic-assisted dispersive magnetic solid-phase extraction of naproxen and ibuprofen. These analytes served as representative analytes for two nonsteroidal anti-inflammatory drugs in various real samples. Characterization techniques, such as IR, X-ray powder diffraction, field emission scanning electron microscopy, energy-dispersive X-ray-mapping, and Brunauer-Emmett-Teller (BET), were used to confirm the correctness synthesis and preparation of the nanocomposites. Effective parameters on the extraction efficiency were investigated to maximize the analytical performance of the developed method. The dynamic range (1-1000 µg L-1), coefficients of determination (R2 ≥ 0.997), the limits of detection (0.3-1.0 µg L-1), and limit of quantification (1.0-3.0 µg L-1), intra-day and inter-day precisions (3.5%-7.2%) were achieved. The method validation results showed extraction recovery ranging from 80.4% to 96.0% and preconcentration factors ranging from 137 to 140.
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Antiinflamatorios no Esteroideos , Electroforesis Capilar , Grafito , Límite de Detección , Leche Humana , Extracción en Fase Sólida , Aguas Residuales , Grafito/química , Electroforesis Capilar/métodos , Humanos , Antiinflamatorios no Esteroideos/orina , Antiinflamatorios no Esteroideos/análisis , Antiinflamatorios no Esteroideos/aislamiento & purificación , Reproducibilidad de los Resultados , Aguas Residuales/química , Extracción en Fase Sólida/métodos , Leche Humana/química , Modelos Lineales , Nanocompuestos/química , Oxiquinolina/química , Contaminantes Químicos del Agua/análisis , Contaminantes Químicos del Agua/aislamiento & purificación , Nanopartículas de Magnetita/químicaRESUMEN
Conductive polymer hydrogels are vital in strain sensors, yet achieving high resilience and toughness is a challenge. This study employs a prestretch method to engineer a tough conductive polymer hydrogel with sufficient resilience. Initially, a blend film of polyvinylalcohol (PVA) and ethylene-vinyl alcohol copolymer (EVOH) is prepared through solution casting, followed by a swelling process to form a PVA-EVOH hydrogel. This hydrogel, with PVA crystallites as crosslinking points, exhibits high toughness. The hydrogel is then immersed in pyrrole and ferric chloride solutions for in-situ polymerization of polypyrrole (PPy), creating a conductive PPy/PVA-EVOH hydrogel. Finally, a 200% prestretch is applied, breaking short chains within the network, eliminating energy dissipation at low strains. This results in a hydrogel with a 100% elastic deformation range, while maintaining high fracture toughness (1700 J m-2 ). The prestretched PPy/PVA-EVOH hydrogel functions as a strain sensor with low hysteresis, providing consistent strain measurements during loading and unloading. This outperforms the non-prestretched sample, which shows inconsistent responses between stretching and releasing.
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Polímeros , Resiliencia Psicológica , Hidrogeles , Pirroles , Alcohol Polivinílico , Conductividad EléctricaRESUMEN
To resist the plastic deformation of polymer particles during hot press molding, high molecular weights, and moduli are required for composites with segregated structures, thus the prepared composites exhibit poor flexibility. Also, larger particle sizes can bring lower percolation thresholds while the ensuing greater deformation destroys the conductive network. Moreover, segregated composites still face preparation complexities. Herein, a facile method for developing flexible composites with large-size segregated structures is proposed. First, silver-coated polydopamine-modified reduced graphene oxide (Ag@PrGO), as conductive fillers, is prepared by electroless plating. Next, polydimethylsiloxane (PDMS)-coated polyolefin elastomer (POE) beads are put into a bag containing the fillers. After a simple shaking, the fillers are adhered to the POE surface as the cohesive property of cured PDMS. Finally, flexible composites with large-size segregated structures are obtained via hot pressing. Benefiting from the 2D structure of the Ag@PrGO and the ability to slip, the conductive networks possess adaptable deformability. The prepared composites exhibit excellent electrical conductivity (203.55 S cm-1) at filler volume fractions of 3.4 vol%. The EMI shielding effectiveness can reach 70 dB in the X-band at a thickness of 1.9 mm and remains stable after bending and rubbing damage. This work paves the way for constructing large-size segregated structures.
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Elastic polymer-based conductive composites (EPCCs) are of great potential in the field of flexible sensors due to the advantages of designable functionality and thermal and chemical stability. As one of the popular choices for sensor electrodes and sensitive materials, considerable progress in EPCCs used in sensors has been made in recent years. In this review, we introduce the types and the conductive mechanisms of EPCCs. Furthermore, the recent advances in the application of EPCCs to sensors are also summarized. This review will provide guidance for the design and optimization of EPCCs and offer more possibilities for the development and application of flexible sensors.
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Recently, there has been a huge increase in the different ways to manufacture polymer-based sensors. Methods like additive manufacturing, microfluidic preparation, and brush painting are just a few examples of new approaches designed to improve sensor features like self-healing, higher sensitivity, reduced drift over time, and lower hysteresis. That being said, we believe there is still a lot of potential to boost the performance of current sensors by applying modeling, classification, and machine learning techniques. With this approach, final sensor users may benefit from inexpensive computational methods instead of dealing with the already mentioned manufacturing routes. In this study, a total of 96 specimens of two commercial brands of Force Sensing Resistors (FSRs) were characterized under the error metrics of drift and hysteresis; the characterization was performed at multiple input voltages in a tailored test bench. It was found that the output voltage at null force (Vo_null) of a given specimen is inversely correlated with its drift error, and, consequently, it is possible to predict the sensor's performance by performing inexpensive electrical measurements on the sensor before deploying it to the final application. Hysteresis error was also studied in regard to Vo_null readings; nonetheless, a relationship between Vo_null and hysteresis was not found. However, a classification rule base on k-means clustering method was implemented; the clustering allowed us to distinguish in advance between sensors with high and low hysteresis by relying solely on Vo_null readings; the method was successfully implemented on Peratech SP200 sensors, but it could be applied to Interlink FSR402 sensors. With the aim of providing a comprehensive insight of the experimental data, the theoretical foundations of FSRs are also presented and correlated with the introduced modeling/classification techniques.
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The preparation methods and thermal conductivity (TC) of the reported thermal conductive polymers vary significantly. A method to clarify the relationship between TC and influencing factors and to reach consistent conclusions is needed. In this study, we compiled 403 sets of data from the literature. Six typical features and three machine learning (ML) algorithms were selected and optimized. XGBoost algorithm achieved the best prediction of TC of thermal conductive polymer (correlation coefficient with 0.855). To further investigate the influence of the 6 features on the TC of thermal conductive polymer, we conducted the SHapley Additive exPlanations (SHAP) analysis. Based on the above results, pyrrhotite tailings were determined as the filler and the corresponding process parameters were also determined. However, the above model built based on literature was still unsatisfactory. We further optimized XGBoost and built XGBoost-Exp through data from the real experiment. Finally, a small percentage (23%) of real experimental data can significantly improve the prediction power of XGBoost-Exp for unseen data (correlation coefficient with 0.815). To summarize, XGBoost-Exp exhibits exceptional predictive performance for the TC of the unseen data, offering valuable insights into the influence of various features. Meanwhile, this method provides a new perspective for the utilization of hazardous sulfide minerals.
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Lithium-sulfur batteries (LSBs) are considered a promising candidate for next-generation energy storage devices due to the advantages of high theoretical specific capacity, abundant resources and being environmentally friendly. However, the severe shuttle effect of polysulfides causes the low utilization of active substances and rapid capacity fading, thus seriously limiting their practical application. The introduction of conductive polymer-based interlayers between cathodes and separators is considered to be an effective method to solve this problem because they can largely confine, anchor and convert the soluble polysulfides. In this review, the recent progress of conductive polymer-based interlayers used in LSBs is summarized, including free-standing conductive polymer-based interlayers, conductive polymer-based interlayer modified separators and conductive polymer-based interlayer modified sulfur electrodes. Furthermore, some suggestions on rational design and preparation of conductive polymer-based interlayers are put forward to highlight the future development of LSBs.
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Open-shell conjugated polymers with a high intrinsic conductivity and high-spin ground state hold considerable promise for applications in organic electronics and spintronics. Herein, two novel acceptor-acceptor (A-A) conjugated polymers based on a highly electron-deficient quinoidal benzodifurandione unit have been developed, namely DPP-BFDO-Th and DPP-BFDO. The incorporation of the quinoidal moiety into the polymers backbones enables deeply aligned lower-lying lowest unoccupied molecular orbital (LUMO) levels of below -4.0â eV. Notably, DPP-BFDO exhibits an exceptionally low LUMO (-4.63â eV) and a high-spin ground state characterized by strong diradical characters. Moreover, a self-doping through intermolecular charge-transfer is observed for DPP-BFDO, as evidenced by X-ray photoelectron spectroscopy (XPS) studies. The high carrier concentration in combination with a planar and linear conjugated backbone yields a remarkable electrical conductivity (σ) of 1.04â S cm-1 in the "undoped" native form, ranking among the highest values reported for n-type radical-based conjugated polymers. When employed as an n-type thermoelectric material, DPP-BFDO achieves a power factor of 12.59â µW m-1 K-2. Furthermore, upon n-doping, the σ could be improved to 65.68â S cm-1. This study underscores the great potential of electron-deficient quinoidal units in constructing dopant-free n-type conductive polymers with a high-spin ground state and exceptional intrinsic conductivity.
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Selective separation of nitrate over chloride is crucial for eutrophication mitigation and nitrogen resource recovery but remains a challenge due to their similar ionic radius and the same valence. Herein, a polypyrrole membrane electrode (PME) was fabricated by polymerization of pyrrole (Py) and p-toluenesulfonate (pTS), which was used as a working electrode in redox transistor electrodialysis. The anions in the source solution were first incorporated into the PME at reduction potentials and then released to receiving solution at oxidation potentials. Pulse widths and potentials were optimized to maximize the ion separation performance of PME, resulting in the improvement of NO3-/Cl- separation factor up to 6.93. The ion distributions in various depths of PME indicated that both NO3- and Cl- were incorporated into PME at negative potentials. Then, NO3- was preferentially released from PME at positive potentials, but most Cl- was retained. This was ascribed to the high binding energy between Cl- and PPy/pTS structure, which was 51.4% higher than that between NO3- and PPy/pTS structure. Therefore, the higher transport rate of NO3- in comparison with Cl- was achieved, leading to a high NO3- selectivity over Cl-. This work provides a promising avenue for the selective separation of nitrate over chloride, which may contribute to nitrogen resource recycling and reuse.
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Cloruros , Nitratos , Polímeros/química , Pirroles/química , Aniones , Electrodos , Oxidación-ReducciónRESUMEN
A poly(thiophene acetic acid)/Au/poly(methylene blue) nanostructured interface was electrochemically assembled step-by-step on screen-printed carbon electrodes (SPCE) for label-free detection of p53 protein. The initial electrical conductive properties of the polymeric interface were increased with an additional layer of poly(methylene blue) electropolymerized in the presence of gold nanoparticles. The nano-immunosensing architecture was prepared by covalent immobilization of anti-p53 antibodies as bioreceptors through the poly(thiophene acetic acid) moieties. The nano-immunosensor assembly was extensively characterized by ultraviolet-visible spectrophotometry, dynamic and electrophoretic light scattering, scanning electron microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, atomic force microscopy, cyclic voltammetry, and electrochemical impedance spectroscopy. Under optimal conditions, p53 was specifically and selectively detected by square wave voltammetry in a linear range between 1 and 100 ng mL-1 with a limit of detection of 0.65 ng mL-1. In addition, the electrochemical nano-immunosensor detected p53 in spiked human serum samples and colorectal cancer cell lysates, and the results were validated with a standard spectrophotometric method using a paired samples t test, which did not exhibit significant differences between both methods. The resultant p53 nano-immunosensor is simple to assemble, robust, and has the potential for point-of-care biomarker detection applications.
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Ácido Acético , Nanopartículas del Metal , Humanos , Técnicas Electroquímicas/métodos , Oro/química , Nanopartículas del Metal/química , Azul de Metileno , TiofenosRESUMEN
The hydrophobic/hydrophilic character of some conductive polymer (CP) coatings can be switched in the function of the working conditions of these adaptive materials. We studied the influence of electrical stimuli and intrinsic physical characteristics (nature of the polymerizable core, dopants, the droplet dimension and physical properties, surface roughness, etc.) on the CP wettability. A simulation strategy was developed for determining the contact angle (CA) of a liquid droplet on a CP layer with roughness. The method was tested for new reported CP composites, but with new dopants. The results indicate that the influences on the material wettability are correlated, and in practice, modification of more than one parameter converges to a wanted behavior of the material. E.g., the CP porous film of poly(3-hexylthiophene) (P3HT) + [6,6]-phenyl-C61-butyricacid-methyl-ester (PCBM) changes its wettability at voltages of up to 26 V, but if doping ions are inserted and the roughness geometry is modified, the voltage decreases twice. Our multi-parametrical study points out that the polymer wettability type is driven by the voltage, but this effect is tuned differently by each internal parameter. The thin films' effect and the dopants (in-situ and ex-situ) significantly decrease the actuation voltage. We also illustrated that the wettability type does not change for specific sets of parameters.
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Electrodes based on PEDOT:PSS are gaining increasing importance as conductive electrodes and functional layers in various sensors and biosensors due to their easy processing and biocompatibility. This study investigates PEDOT:PSS/graphene layers deposited via spray coating on flexible PET substrates. The layers are characterized in terms of their morphology, roughness (via AFM and SEM), and electrochemical properties in artificial sweat using electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The layers exhibit dominant capacitive behavior at low frequencies, with cut-off frequencies determined for thicker layers at 1 kHz. The equivalent circuit used to fit the EIS data reveals a resistance of about three orders of magnitude higher inside the layer compared to the charge transfer resistance at the solid/liquid interface. The capacitance values determined from the CV curves range from 54.3 to 122.0 mF m-2. After 500 CV cycles in a potential window of 1 V (from -0.3 to 0.7 V), capacitance retention for most layers is around 94%, with minimal surface changes being observed in the layers. The results suggest practical applications for PEDOT:PSS/graphene layers, both for high-frequency impedance measurements related to the functioning of individual organs and systems, such as impedance electrocardiography, impedance plethysmography, and respiratory monitoring, and as capacitive electrodes in the low-frequency range, realized as layered PEDOT:PSS/graphene conductive structures for biosignal recording.
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With the development of device miniaturization, a flexible and fast preparation method is in demand for achieving microstructures with desired patterns. We develop a novel photoreduction-polymerization method for preparing conductive metal-polymer patterns. Ag/polyaniline (PANI) nanocomposites have been successfully synthesized by maskless optical projection lithography (MOPL) technology, which is based on multiphoton absorption and the localized surface plasmon resonance (LSPR) effect. The individualized design and synthesis of the nanocomposite patterns at the micro-nano scale are flexibly realized on a variety of substrates. The surface-enhanced Raman scattering (SERS) effect of Rhodamine 6G (R6G) is demonstrated on the microstructure of a square maze-shaped Ag/PANI nanocomposite. The electrical conductivity of the as-prepared nanocomposite is obtained. The preparation protocol proposed in this study opens up new avenues for the fabrication of micro-nano devices such as sensors and detectors.
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A preparation method of nanocomposites based on poly (3-octylthiophene-2,5-diyl) (POT) and carbon black (CB) as the transducer of an all-solid potassium ion selective electrode is proposed. POT is used as the dispersant of CB, and the obtained nanocomposites have unique characteristics, including high conductivity, high capacitance and high stability. The potassium ion selective electrode based on POT and CB was characterized by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and chronopotentiometry. The results showed that the detection limit of potassium ions was 10-6.2 M, and the slope was 57.6 ± 0.8 mV/façade. The water layer test and anti-interference test show that the electrode has high hydrophobicity, the static contact angle reaches 139.7° and is not easily affected by light, O2 and CO2.
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The rapid advancement of electronic communication technology has greatly aided human productivity and quality of life, but it has also resulted in significant electromagnetic pollution issues. Traditional metals and alloys are often used for electromagnetic interference (EMI) shielding due to their excellent electrical conductivity. However, they have drawbacks such as being heavy, expensive, and having low corrosion resistance, which limits their application in electromagnetic shielding. Therefore, it is crucial to develop novel EMI shielding materials. Polymers, being highly flexible, corrosion-resistant, and possessing high specific strength, are frequently employed in electromagnetic shielding materials. In this review, we firstly introduce the basic theory of electromagnetic shielding. Then, we outline the processing methods and recent developments of polymer-based electromagnetic shielding composites, including uniform-, foam-, layered-, and segregated structures. Lastly, we present the challenges and prospects for the field, aiming to provide direction and inspiration for the study of polymer-based electromagnetic shielding composite materials.
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Electromagnetic shielding materials are special materials that can effectively absorb and shield electromagnetic waves and protect electronic devices and electronic circuits from interference and damage by electromagnetic radiation. This paper presents the research progress of intrinsically conductive polymer materials and conductive polymer-based composites for electromagnetic shielding as well as an introduction to lightweight polymer composites with multicomponent systems. These materials have excellent electromagnetic interference shielding properties and have the advantages of electromagnetic wave absorption and higher electromagnetic shielding effectiveness compared with conventional electromagnetic shielding materials, but these materials still have their own shortcomings. Finally, the paper also discusses the future opportunities and challenges of intrinsically conductive polymers and composites containing a conductive polymer matrix for electromagnetic shielding applications.
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We report on the synthesis of activated carbon-semi-polycrystalline polyaniline (SPani-AC) composite material using in-situ oxidative polymerization of aniline on the carbon surface in an aqueous HCl medium at an elevated temperature of 60 °C. The electroactive polymeric composite material exhibits a uniformly distributed spindle-shaped morphology in scanning electron microscopy (SEM) and well-defined crystallographic lattices in the high-resolution transmission electron microscopy (TEM) images. The X-ray diffraction (XRD) spectrum reveals sharp peaks characteristic of crystalline polyaniline. The characteristic chemical properties of polyaniline are recorded using laser Raman spectroscopy. The cyclic voltammetry curves exhibit features of surface-redox pseudocapacitance. The specific capacitance calculated for the material is 507 F g-1 at the scan rate of 10 mV s-1. The symmetrical two-electrodes device exhibits a specific capacitance of 45 F g-1 at a current density of 5 A g-1. The capacitive retention calculated was found to be 96% up to 4500 continuous charge-discharge cycles and observed to be gradually declining at the end of 10,000 cycles. On the other hand, Coulombic efficiency was observed to be retained up to 85% until 4500 continuous charge-discharge cycles which declines up to 72% at the end of 10,000 cycles. The article also presents a detailed description of material synthesis, the formation of polyaniline (Pani) chains, and the role of material architecture in the performance as surface redox supercapacitor electrode.
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Compuestos de Anilina , Carbón Orgánico , Microscopía Electrónica de Rastreo , Microscopía Electrónica de Transmisión , Compuestos de Anilina/químicaRESUMEN
Currently, there is very limited information on the electrophoretic behavior of particles at a liquid-liquid interface formed by two conducting liquid solutions. Here, electrophoretic velocities of polystyrene particles at a polyethylene glycol (PEG)-dextran (DEX) interface were investigated in this paper. Experimental results show that the particle at the interface moves in the opposite direction to the applied electric field, with a velocity much lower than that in the PEG-rich phase and a litter larger than that in the DEX-rich phase. Similarly to the movement in Newtonian fluids, the velocity increases linearly with the increase in the applied electric field. Different to particle electrophoresis in Newtonian fluids, the velocities of the particles at the PEG-DEX interface increase linearly with the decrease in particle's diameters, implying a possible size-based particle differentiation at an interface.