Molecular-Potential and Redox Coregulated Cathodic Electrosynthesis toward Ionic Azulene-Based Thin Films for Organic Memristors.

Organic memristors as promising electronic units are attracting significant attention owing to their simplicity of molecular structure design. However, fabricating high-quality organic films via novel synthetic technologies and exploring unprecedented chemical structures to achieve excellent memory performance in organic memristor devices are highly challenging. In this work, we report a cathodic electropolymerization to synthesize an ionic azulene-based memristive film (PPMAz-Py+Br-) under the molecular-potential and redox coregulation. During the cathodic electropolymerization process, electropositive pyridinium salts migrate to the cathode under an electric field, undergo a reduction-coupling deprotonation reaction, and polymerize into a uniform film with a controllable thickness on the electrode surface. The prepared Al/PPMAz-Py+Br-/ITO devices not only exhibit a high ON/OFF ratio of 1.8 × 103, high stability, long memory retention, and endurance under a wide range of voltage scans, but also achieve excellent multilevel storage and history-dependent memristive performance. In addition, the devices can mimic important biosynaptic functions, such as learning/forgetting function, synaptic enhancement/inhibition, paired-pulse facilitation/depression, and spiking-rate-dependent plasticity. The tunable memristive performances are attributed to the capture of free electrons on pyridinium cations, the migration of the aluminum ions (Al3+), and the form of Al conductive filaments under voltage scans.

Ultrasensitive detection of chloramphenicol in water using functionalized polymers with an aluminium organic framework.

Metal-Organic Frameworks (MOFs) are extensively used as electrode material in various sensing applications due to their efficacious porous nature and tunable properties. However, pristine MOFs lack conductive attributes that hinder their wide usage in electrochemical applications. Electropolymerization of several aromatic monomers has been a widely used strategy for preparing conducting electrode materials for various sensing applications in the past decades. Herein, we report a similar approach by employing the electropolymerization method to create a functional polymer layer to enhance the sensitivity of an Aluminium Organic Framework (DUT-4) for the selective detection of Chloramphenicol (CAP) antibiotic in aqueous environment. The combined strategy using the conducting polymer layer with the porous Al MOF provides surpassing electrochemical performance for sensing CAP with regard to the very low detection limit (LOD = 39 nM) and exceptionally high sensitivity (11943 µA mM-1 cm-2). In addition, the fabricated sensor exhibited good selectivity, reproducibility and stability. The developed method was successfully evaluated in various real samples including lake water and river water for CAP detection with good recovery percentages even at lower concentrations.

Ultra-Stable High-Capacity Polythiophene Derivative for Wide-Potential-Window Supercapacitors.

Conducting polymer (CP)-based supercapacitors show great promise for applications in the field of wearable and portable electronics. However, these supercapacitors face persistent challenges, notably low energy density and inadequate stability. In this study, we introduce a polythiophene derivative, designated as poly(EPE), synthesized via the electrochemical polymerization of 8-bis(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-3,3-dimethyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine (EPE). The resulting poly(EPE) polymer exhibits an exemplary 3D porous network-like structure, significantly enhancing its capacitance performance. When employed as the electrode material, the symmetric supercapacitor demonstrates an exceptionally high specific capacitance of 1342 F g-1 at a current density of 4.0 A g-1, along with impressive energy and power densities of 119.3 W h kg-1 and 38.83 kW kg-1, respectively. These capacitance values surpass those of previously reported pristine CP-based supercapacitors. Notably, the supercapacitor showcases outstanding stability, maintaining a retention rate of 92.5% even after 50,000 charge-discharge cycles. These findings underscore the substantial potential of poly(EPE) as an electrode material for the advancement of the supercapacitor technology.

Electrochemical Behavior of Janus Kinase Inhibitor Ruxolitinib at a Taurine-Electropolymerized Carbon Paste Electrode: Insights into Sensing Mechanisms.

Ruxolitinib (RXL) is a Janus kinase inhibitor used for treating intermediate- or high-risk myelofibrosis. This study presents an electrode modified with electrochemically polymerized taurine on a carbon paste electrode via cyclic voltammetry (CV). The surface characterization of the poly(taurine)-CP electrode was evaluated by using electrochemical (electrochemical impedance spectroscopy─EIS, CV), morphological (scanning electron microscope─SEM), and spectroscopic (Fourier-transform infrared spectroscopy─FT-IR) techniques. Under optimized conditions, RXL exhibited good linearity within the 0.01-1.0 µM concentration range, with a limit of detection (LOD) of 0.005 µM. The proposed electrochemical sensor demonstrated excellent selectivity, accuracy, precision, and repeatability. Furthermore, it effectively detected RXL in human urine and pharmaceutical samples.

Electrochemical determination of fenitrothion pesticide based on ultrathin manganese oxide nanowires/molybdenum titanium carbide MXene ionic nanocomposite and molecularly imprinting polymer.

A novel molecularly imprinted electrochemical sensor is presented based on one-dimensional ultrathin manganese oxide nanowires/two-dimensional molybdenum titanium carbide MXene (MnO2NWs@Mo2TiC2 MXene) for fenitrothion (FEN) determination. After the synthesis of MnO2NWs@Mo2TiC2 MXene ionic nanocomposite was successfully completed with a facile hydrothermal and the pillaring methods, a new type molecular imprinted electrochemical sensor based on MnO2NWs@Mo2TiC2 MXene was constructed with cyclic voltammetry (CV) polymerization including pyrrole monomer and FEN target molecule. After the characterization studies including spectroscopic, electrochemical and microscopic methods, the analytical applications of the prepared sensor were performed. A linearity of 1.0×10-9-2.0×10-8 mol L-1 was obtained and the values of the quantification limit (LOQ) and the detection limit (LOD) were 1.0×10-9 mol L-1 and 3.0×10-10 mol L-1, respectively. The studies of selectivity, stability and reproducibility of the constructed sensor based on MnO2NWs@Mo2TiC2 nanocomposite and molecularly imprinting polymer (MIP) were carried out in detail. Finally, the developed sensor was applied to white flour samples with the values close to 100%.

A comparative study of electropolymerization and photopolymerization for the determination of molnupiravir and their application in an electrochemical sensor via computationally designed molecularly imprinted polymers.

A comparative analysis of molecularly imprinted polymers based on different synthesis techniques was performed for the recognition of molnupiravir (MOL). The polymerizations were performed with 3-thienyl boronic acid (3-TBA) as a functional monomer by electropolymerization (EP) and with guanine methacrylate (GuaM) as a functional monomer by photopolymerization (PP). Morphological and electrochemical characterizations of the developed sensors were investigated to verify the constructed sensors. Moreover, quantum chemical calculations were used to evaluate changes on the electrode surface at the molecular and electronic levels. The dynamic linear range of both designed sensors under optimized experimental conditions was found to be 7.5 × 10-12-2.5 × 10-10 M and 7.5 × 10-13-2.5 × 10-11 M for EP and PP, respectively. The effect of various interfering agents on MOL peak current was assessed for the selectivity of the study. In the presence of 100 times more interfering agents, the RSD and recovery values were determined. The RSD values of GuaM/MOL@MIP/GCE and poly(Py-co-3-PBA)/MOL@MIP/GCE sensors were found to be 1.99% and 1.72%, respectively. Furthermore, the recovery values of the MIP-based sensors were 98.18-102.69% and 98.05-103.72%, respectively. In addition, the relative selectivity coefficient (k') of the proposed sensor was evaluated, and it exhibited good selectivity for MOL with respect to the NIP sensor. The prepared sensor was successfully applied to determine MOL in commercial serum samples and capsule form. In conclusion, the developed sensors provided excellent reproducibility, repeatability, high sensitivity, and selectivity against the MOL molecule.

Electropolymerized Bipolar Poly(2,3-diaminophenazine) Cathode for High-Performance Aqueous Al-Ion Batteries with An Extended Temperature Range of -20 to 45 °C.

Achieving reversible insertion/extraction in most cathodes for aqueous aluminum ion batteries (AAIBs) is a significant challenge due to the high charge density of Al3+ and strong electrostatic interactions. Organic materials facilitate the hosting of multivalent carriers and rapid ions diffusion through the rearrangement of chemical bonds. Here, a bipolar conjugated poly(2,3-diaminophenazine) (PDAP) on carbon substrates prepared via a straightforward electropolymerization method is introduced as cathode for AAIBs. The integration of n-type and p-type active units endow PDAP with an increased number of sites for ions interaction. The long-range conjugated skeleton enhances electron delocalization and collaborates with carbon to ensure high conductivity. Moreover, the strong intermolecular interactions including π-π interaction and hydrogen bonding significantly enhance its stability. Consequently, the Al//PDAP battery exhibits a large capacity of 338 mAh g-1 with long lifespan and high-rate capability. It consistently demonstrates exceptional electrochemical performances even under extreme conditions with capacities of 155 and 348 mAh g-1 at -20 and 45 °C, respectively. In/ex situ spectroscopy comprehensively elucidates its cation/anion (Al3+ /H3 O+ and ClO4 - ) storage with 3-electron transfer in dual electroactive centers (C═N and -NH-). This study presents a promising strategy for constructing high-performance organic cathode for AAIBs over a wide temperature range.

Electropolymerization of an EDOT-Quinoxaline Monomer for Green Electrochromic Thin Films and Devices.

In this study, we present a 5,8-bis(3,4-ethylenedioxythiophene)quinoxaline monomer with two 4-(octyloxy)phenyl side chains (EDOTPQ) that can be electropolymerized on ITO glass in standard electrolytes containing lithium salts and propylene carbonate as solvent. The electrochemically deposited PEDOTPQ layers show very good adhesion and homogeneity on ITO. The green-colored polymer thin films exhibit promising electrochromic (EC) properties and are interesting for applications such as adaptive camouflage, as well as smart displays, labels, and sensors. Novel organic-inorganic (hybrid) EC cell configurations were realized with Prussian blue (PB) or titanium-vanadium oxide (TiVOx) as ion storage electrodes, showing a highly reversible and fast color change from green to light yellow.

In-Situ Spontaneous Electropolymerization Enables Robust Hydrogel Electrolyte Interfaces in Aqueous Batteries.

Hydrogels hold great promise as electrolytes for emerging aqueous batteries, for which establishing a robust electrode-hydrogel interface is crucial for mitigating side reactions. Conventional hydrogel electrolytes fabricated by ex situ polymerization through either thermal stimulation or photo exposure cannot ensure complete interfacial contact with electrodes. Herein, we introduce an in situ electropolymerization approach for constructing hydrogel electrolytes. The hydrogel is spontaneously generated during the initial cycling of the battery, eliminating the need of additional initiators for polymerization. The involvement of electrodes during the hydrogel synthesis yields well-bonded and deep infiltrated electrode-electrolyte interfaces. As a case study, we attest that, the in situ-formed polyanionic hydrogel in Zn-MnO2 battery substantially improves the stability and kinetics of both Zn anode and porous MnO2 cathode owing to the robust interfaces. This research provides insight to the function of hydrogel electrolyte interfaces and constitutes a critical advancement in designing highly durable aqueous batteries.

Development of double-layer poly (amino acid) modified electrochemical sensor for sensitive and direct detection of betamethasone in cosmetics.

Screening for illegal use of glucocorticoids (GCs) in cosmetics by electrochemical methods is extremely challenging due to the poor electrochemical activity of GCs. In this study, poly-L-Serine/poly-Taurine modified electrode (P(Tau)/P(L-Ser)/GCE) was prepared for sensitive and direct determination of betamethasone in cosmetics by a simple two-step in situ electropolymerization reaction. The relevant parameters of preparation and electroanalytical conditions were respectively studied, including the concentration of polymerization solution, the number of scanning circles and the scanning rate. The SEM and EDS mapping demonstrated successful preparation of P(Tau)/P(L-Ser)/GCE. The electro-catalytic properties of the obtained electrodes were investigated using cyclic voltammetry and differential pulse voltammetry methods, showing a remarkable improvement of sensitivity for the detection of betamethasone due to the synergic effect of both P(L-Ser) and P(Tau). In addition, we investigated the electrochemical reduction of betamethasone on the surface of modified electrode. It was found that the process was controlled by diffusion effect and involved the transfer of two electrons and two protons. Then the electrochemical sensor method based on P(Tau)/P(L-Ser)/GCE was established and delivered a linear response to betamethasone concentration from 0.5 to 20 µg mL-1 with a limit of detection of 32.2 ng mL-1, with excellent recoveries (98.1%-106.8%) and relative standard deviations (＜4.8%). Furthermore, the established electrochemical sensor method was compared with conventional HPLC method. The results showed that both of them were comparable. Moreover, the established electrochemical sensor method was with the merits of short analysis time, environmentally friendly, low cost and easy to achieve in-site detection.

Advancing amyotrophic lateral sclerosis disease diagnosis: A lab-on-chip electrochemical immunosensor for ultra-sensitive TDP-43 protein detection and monitoring in serum patients'.

The global increase in population aging has led to a rise in neurodegenerative diseases (NDs), posing significant challenges to public health. Developing selective and specific biomarkers for early diagnosis and drug development is crucial addressing the growing burden of NDs. In this context, the RNA-binding protein TDP-43 has emerged as a promising biomarker for amyotrophic lateral sclerosis (ALS), frontotemporal lobar degeneration (FTLD), and TDP-43-associated proteinopathies. However, existing detection methods suffer from limitations such as cost, complexity, and operator dependence. Here, we present a novel electrochemical biosensor integrated into a lab-on-chip (LoC) platform to detect TDP-43. The sensor utilizes electrosynthesized polypyrrole derivatives with carboxylic groups for transducer functionalization, enabling targeted immobilization of TDP-43 antibodies. Differential pulsed voltammetry (DPV) is used for the indirect detection and quantification of TDP-43. The chip exhibits rapid response, good reproducibility, a linear detection range, and sensitivity from 0.01 ng/mL to 25 ng/mL of TDP-43 protein concentration with a LOD = 10 pg/mL. Furthermore, successful TDP-43 detection in complex matrices like serum of ALS patients and healthy individuals demonstrates its potential as a point-of-care diagnostic device. This electrochemical biosensor integrated into a chip offers good sensitivity, rapid response, and robust performance, providing a promising avenue for advancing neurodegenerative disease diagnostics and therapeutic development.

Single-Component Electroactive Polymer Architectures for Non-Enzymatic Glucose Sensing.

Organic mixed ionic-electronic conductors (OMIECs) have emerged as promising materials for biological sensing, owing to their electrochemical activity, stability in an aqueous environment, and biocompatibility. Yet, OMIEC-based sensors rely predominantly on the use of composite matrices to enable stimuli-responsive functionality, which can exhibit issues with intercomponent interfacing. In this study, an approach is presented for non-enzymatic glucose detection by harnessing a newly synthesized functionalized monomer, EDOT-PBA. This monomer integrates electrically conducting and receptor moieties within a single organic component, obviating the need for complex composite preparation. By engineering the conditions for electrodeposition, two distinct polymer film architectures are developed: pristine PEDOT-PBA and molecularly imprinted PEDOT-PBA. Both architectures demonstrated proficient glucose binding and signal transduction capabilities. Notably, the molecularly imprinted polymer (MIP) architecture demonstrated faster stabilization upon glucose uptake while it also enabled a lower limit of detection, lower standard deviation, and a broader linear range in the sensor output signal compared to its non-imprinted counterpart. This material design not only provides a robust and efficient platform for glucose detection but also offers a blueprint for developing selective sensors for a diverse array of target molecules, by tuning the receptor units correspondingly.

A Solar Evaporator Based on Polypyrrole Coated 3D Carbon Nanotube Materials for Efficient Solar-Driven Vapor Generation.

Highly porous light absorbers are fabricated based on polypyrrole (PPy)-coated carbon nanotube (CNT). Carbon nanotube sponge (CNTS) or carbon nanotube array (CNTA) with three-dimensional (3D) network structure is the framework of porous light absorbers. Both PPy@CNTS and PPy@CNTA composites exhibit excellent light absorption of the full solar spectrum. The CNTS and CNTA with porous structures have extremely large effective surface area for light absorption and for water evaporation that has great practical benefit to the solar-driven vapor generation. The PPy layer on CNT sidewalls significantly improves the hydrophilicity of porous CNTS and CNTA. The good wettability of water on CNT sidewalls makes water transport in porous CNT materials highly efficient. The PPy@CNTS and PPy@CNTA light absorbers achieve high water evaporation rates of 3.35 and 3.41 kg m-2 h-1 , respectively, under 1-sun radiation. The orientation of nano channels in CNTA-based light absorbers also plays an important role in the solar-driven vapor generation. The water transport and vapor escape are more efficient in CNTA-based light absorbers as compared to the CNTS-based light absorbers due to the relatively short path for the water transport and the vapor escape in CNTA-based light absorbers.

Electropolymerization of Preferred-Oriented Conjugated Microporous Polymer Films for Enhanced Fluorescent Sensing.

High-quality conjugated microporous polymer (CMP) films with orientation and controlled structure are extremely desired for applications. Here, we report the effective construction of CMP 3D composite films (pZn/PTPCz) with a controlled porosity structure and preferred orientation using the template-assisted electropolymerization (EP) approach for the first time. The structure of pZn/PTPCz composite thin films and nitrophenol sensing performance were thoroughly studied. When compared to the control CMP film made on flat indium tin oxide (ITO) substrates, the as-prepared pZn/PTPCz composite films showed significantly enhanced fluorescent intensity and much better sensing performance for the model explosive. This was attributed to the metal-enhanced fluorescence (MEF) of porous nanostructured zinc (pZn) and the additional macroporosity of the pZn/PTPCz composite films. This work provides a feasible approach for creating oriented 3D CMP-based thin films for advanced applications.

Porous Electropolymerized Films of Ruthenium Complex: Photoelectrochemical Properties and Photoelectrocatalytic Synthesis of Hydrogen Peroxide.

The photoelectrochemical cells (PECs) performing high-efficiency conversions of solar energy into both electricity and high value-added chemicals are highly desirable but rather challenging. Herein, we demonstrate that a PEC using the oxidatively electropolymerized film of a heteroleptic Ru(II) complex of [Ru(bpy)(L)2](PF6)2Ru1 {bpy and L stand for 2,2'-bipyridine and 1-phenyl-2-(4-vinylphenyl)-1H-imidazo[4,5-f][1,10]phenanthroline respectively}, polyRu1, as a working electrode performed both efficient in situ synthesis of hydrogen peroxide and photocurrent generation/switching. Specifically, when biased at -0.4 V vs. saturated calomel electrode and illuminated with 100 mW·cm-2 white light, the PEC showed a significant cathodic photocurrent density of 9.64 µA·cm-2. Furthermore, an increase in the concentrations of quinhydrone in the electrolyte solution enabled the photocurrent polarity to switch from cathodic to anodic, and the anodic photocurrent density reached as high as 11.4 µA·cm-2. Interestingly, in this single-compartment PEC, the hydrogen peroxide yield reached 2.63 µmol·cm-2 in the neutral electrolyte solution. This study will serve as a guide for the design of high-efficiency metal-complex-based molecular systems performing photoelectric conversion/switching and photoelectrochemical oxygen reduction to hydrogen peroxide.

Electrochemically Synthesized MIP Sensors: Applications in Healthcare Diagnostics.

Early-stage detection and diagnosis of diseases is essential to the prompt commencement of treatment regimens, curbing the spread of the disease, and improving human health. Thus, the accurate detection of disease biomarkers through the development of robust, sensitive, and selective diagnostic tools has remained cutting-edge scientific research for decades. Due to their merits of being selective, stable, simple, and having a low preparation cost, molecularly imprinted polymers (MIPs) are increasingly becoming artificial substitutes for natural receptors in the design of state-of-the-art sensing devices. While there are different MIP preparation approaches, electrochemical synthesis presents a unique and outstanding method for chemical sensing applications, allowing the direct formation of the polymer on the transducer as well as simplicity in tuning the film properties, thus accelerating the trend in the design of commercial MIP-based sensors. This review evaluates recent achievements in the applications of electrosynthesized MIP sensors for clinical analysis of disease biomarkers, identifying major trends and highlighting interesting perspectives on the realization of commercial MIP-endowed testing devices for rapid determination of prevailing diseases.

Searching High-Potential Dihydroxynaphthalene Cathode for Rocking-Chair All-Organic Aqueous Proton Batteries.

The lack of acid-proof high-potential cathode largely limits the development and competitiveness of proton batteries. Herein, the authors systematically investigated six dihydroxynaphthalenes (DHNs) and found that 2,6-DHN delivered the best cathode performance in proton battery with the highest redox potential (0.84 V, vs SHE) and a specific capacity of 91.6 mAh g-1 at 1 A g-1 . In situ solid-state electropolymerization of DHNs is responsible for the voltage and capacity fading of DHNs, and 2,6-DHN's excellent electrochemical performance is derived from its high polymerization energy barrier. By compounding with rGO, the 2,6-DHN/rGO electrode can maintain a specific capacity of 89 mAh g-1 even after 12 000 cycles at 5 A g-1 . When it is paired with the 2,6-dihydroxyanthraquinone (DHAQ) anode, the assembled rocking-chair all-organic proton battery exhibited a high cell voltage of 0.85 V, and excellent energy/power densities (70.8 Wh kg-1 /850 W kg-1 ). This study showcases a new-type high-potential proton-containing organic cathode and paves the way for constructing a high-voltage rocking-chair proton battery. Also, in situ solid-state electropolymerization will inspire the further study of phenol-based small-molecule electrodes.

Electrodeposited Poly(5-Amino-2-Naphthalenesulfonic Acid-co-o-Aminophenol) as the Electrode Material for Flexible Supercapacitor.

Copolymers of 5-amino-2-naphthalenesulfonic acid (ANS) and o-aminophenol (oAP) are electropolymerized on carbon cloth substrate from aqueous solutions, and the electropolymerization process is investigated using electrochemical quartz-crystal microbalance. The surface of the copolymer (PANS-co-oAP) appears rough and is capable to store charge as the battery-type electrode in 1 m H2 SO4 (102.9 mAh g-1 at 1 A g-1 ) or in 1 m ZnSO4 (79.75 mAh g-1 at 1 A g-1 ) aqueous solutions. Compared with PANS and PoAP, the high specific capacity of the PANS-co-oAP is originated from the increased number of electrochemically active sites and increased diffusion rates of ions. Evidence of amino/imino and hydroxyl/carbonyl groups redox processes and cation insertion and extraction are given by ex situ X-ray photoelectron spectroscopy. When used as the electrode material in the flexible solid-state supercapacitors, the specific capacitance is at 37.9 F g-1 which does not significantly alter with the bending angle. The flexible solid-state supercapacitor shows a specific energy of 5.4 Wh kg-1 and a power density of 250.3 W kg-1 at 0.5 A g-1 , and a high capacitance retention (88.2%) after 3000 cycles at 5 A g-1 is achieved.

Polymeric nanocomposite electrode for enhanced electrochemical detection of α-lipoic acid: Application in neuroinflammation prevention and clinical analysis.

Using poly (vanillin-co-chitosan)/functionalized MWCNTs/GCE (PV-CS/f-MWCNTs/GCE) as a polymeric nanocomposite modified electrode, the present investigation has been conducted on the electrochemical detection of α-lipoic acid (α-LA) to prevent the activation of microglia inflammation of the nervous system. The manufacture of modified polymeric nanocomposite electrodes was carried out using the established electropolymerization process. Field emission scanning electron microscopy (FE-SEM) and X-ray diffraction (XRD) analyses of structure revealed that the electropolymerization of poly (vanillin-co-chitosan) on the surface of the f-MWCNTs modified electrode was successful. Vanillin-co-chitosan electropolymerization on f-MWCNTs as electroactive sheets can enhance the signal for α-LA electrochemical sensors, according to research on the electrochemical characteristics utilizing cyclic voltammetry (CV) and differential pulse voltammetry (DPV) methodologies. The PV-CS/f-MWCNTs/GCE demonstrated that it had a sensitivity of 0.04664 µA/µM, a detection limit of 0.012 µM, and an excellent response, linear range, and wide linear range to α-LA from 0 to 3000 µM. The results of the application of PV-CS/f-MWCNTs/GCE for determining the concentration of α-LA in a prepared real sample of human serum by DPV and human lipoic acid ELISA Kit analyses via standard addition method illustrated the substantial conformity between the findings of both assays. The results of the DPV analyses resulted in acceptable recovery values (97.60%-99.10%) and appropriate values of the Relative Standard Deviation (RSD) (3.58%-5.07%), which demonstrated the great applicability and accuracy of the results of PV-CS/f-MWCNTs/GCE for determining α-LA concentration in biological fluids and pharmaceutical specimens.

Exploring the optimal electropolymerization strategy for the preparation of solid-phase microextraction fibers using pyrrole-dopamine copolymers.

In-situ electropolymerization of conductive polymers on the surface of stainless-steel substrates is a well-established but promising procedure for the preparation of solid-phase microextraction (SPME) tools. Herein, different electrochemical methods including constant potential (CP), constant potential pulse (CPP), and cyclic voltammetry (CV) were utilized to fabricate SPME fibers by in-situ electropolymerization of pyrrole-dopamine copolymers (PPY/PDA) on the surface of stainless-steel fibers. The coated fibers were characterized and applied for the direct-immersion SPME (DI-SPME) sampling of ultra-trace amounts of plant hormones including abscisic acid (ABA), gibberellic acid (GA3), and indole acetic acid (IAA) in fruit juices, followed by HPLC-UV determination. The results showed that CV electropolymerization is significantly more efficient than the two other methods. The coatings created by the CV method were satisfactorily uniform, adhesive, and durable and exhibited higher extraction performance compared to the CP and CPP procedures. The important experimental variables of the proposed DI-SPME-HPLC method were evaluated and optimized using response surface methodology with a Box-Behnken design. The developed method showed wide-range linearities, spanning from 0.05 to 20µg mL-1 for GA3, and 0.02 to 20µg mL-1 for ABA and IAA. The limits of detection were obtained 0.01µg mL-1 for GA3, and 0.005µg mL-1 for ABA and IAA. The fiber was successfully employed for the simultaneous DI-SPME-HPLC analysis of plant hormones in fruit juice samples.