Additive Blending Effects on PEDOT:PSS Composite Films for Wearable Organic Electrochemical Transistors

Organic electrochemical transistors (OECTs) employing conductive polymers (CPs) have gained remarkable prominence and have undergone extensive advancements in wearable and implantable bioelectronic applications in recent years. Among the diverse arrays of CPs, poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is a common choice for the active-layer channel in p-type OECTs, showing a remarkably high transconductance for the high amplification of signals in biosensing applications. This investigation focuses on the novel engineering of PEDOT:PSS composite materials by seamlessly integrating several additives, namely, dimethyl sulfoxide (DMSO), (3-glycidyloxypropyl)trimethoxysilane (GOPS), and a nonionic fluorosurfactant (NIFS), to fine-tune their electrical conductivity, self-healing capability, and stretchability. To elucidate the intricate influences of the DMSO, GOPS, and NIFS additives on the formation of PEDOT:PSS composite films, theoretical calculations were performed, encompassing the solubility parameters and surface energies of the constituent components of the NIFS, PEDOT, PSS, and PSS-GOPS polymers. Furthermore, we conducted a comprehensive array of material analyses, which reveal the intricacies of the phase separation phenomenon and its interaction with the materials’ characteristics. Our research identified the optimal composition for the PEDOT:PSS composite films, characterized by outstanding self-healing and stretchable capabilities. This composition has proven to be highly effective for constructing an active-layer channel in the form of OECT-based biosensors fabricated onto polydimethylsiloxane substrates for detecting dopamine. Overall, these findings represent significant progress in the application of PEDOT:PSS composite films in wearable bioelectronics and pave the way for the development of state-of-the-art biosensing technologies

Sensitive Detection of Sweat Cortisol Using an Organic Electrochemical Transistor Featuring Nanostructured Poly(3,4-Ethylenedioxythiophene) Derivatives in the Channel Layer

In this study, we examined the influence of functionalized poly­(3,4-ethylenedioxythiophene) (PEDOT) nanostructures decorated on the channel layer of an organic electrochemical transistor (OECT) for the detection of sweat cortisol, an adrenocorticosteroid stress hormone. The OECT device featured a bilayer channel confined by a PEDOT:polystyrenesulfonate (PSS) underlayer and a nanostructure-decorated upper layer engineered from the monomers EDOT-COOH and EDOT-EG3 through template-free electrochemical polymerization. This molecular design allowed antibody conjugation using 1-ethyl-3-(3-dimethylaminopropyl)­carbodiimide/N-hydroxysulfosuccinimide coupling through the carboxylic acid side chain, with EDOT-EG3 known to minimize nonspecific binding of biomolecules. We also engineered an OECT device having a channel area without any nanostructures to gain insight into the effect of the nanostructures on cortisol sensing. Our new nanostructure-embedded OECT device facilitated real-time detection of cortisol at concentrations ranging from 1 fg/mL to 1 μg/mL with a detection limit of 0.0088 fg/mL with good linearity (R2 = 0.9566), in addition to excellent selectivity toward cortisol among other structurally similar interfering compounds and high stability and reproducibility. With its rapid response for the detection of 100 ng/mL cortisol-spiked artificial sweat, this nanostructure-decorated OECT device has potential clinical practicality and utility in wearable sensors for future healthcare applications

Organic Photovoltaics and Bioelectrodes Providing Electrical Stimulation for PC12 Cell Differentiation and Neurite Outgrowth

Current bioelectronic medicines for neurological therapies generally involve treatment with a bioelectronic system comprising a power supply unit and a bioelectrode device. Further integration of wireless and self-powered units is of practical importance for implantable bioelectronics. In this study, we developed biocompatible organic photovoltaics (OPVs) for serving as wireless electrical power supply units that can be operated under illumination with near-infrared (NIR) light, and organic bioelectronic interface (OBEI) electrode devices as neural stimulation electrodes. The OPV/OBEI integrated system is capable to provide electrical stimulation (ES) as a means of enhancing neuron-like PC12 cell differentiation and neurite outgrowth. For the OPV design, we prepared devices incorporating two photoactive material systemsβ-carotene/<i>N</i>,<i>N</i>′-dioctyl-3,4,9,10-perylenedicarboximide (β-carotene/PTCDI-C8) and poly­(3-hexylthiophene)/phenyl-C₆₁-butyric acid methyl ester (P3HT/PCBM)that exhibited open circuit voltages of 0.11 and 0.49 V, respectively, under NIR light LED (NLED) illumination. Then, we connected OBEI devices with different electrode gaps, incorporating biocompatible poly­(hydroxymethylated-3,4-ethylenedioxythiophene), to OPVs to precisely tailor the direct current electric field conditions during the culturing of PC12 cells. This NIR light-driven OPV/OBEI system could be engineered to provide tunable control over the electric field (from 220 to 980 mV mm^–1) to promote 64% enhancement in the neurite length, direct the neurite orientation on chips, or both. The OPV/OBEI integrated systems under NIR illumination appear to function as effective power delivery platforms that should meet the requirements for wirelessly offering medical ES to a portion of the nervous system; they might also be a key technology for the development of next-generation implantable bioelectronics

PEDOT:PSS-Based Bioelectrodes for Multifunctional Drug Release and Electric Cell-Substrate Impedance Sensing

Electric cell-substrate impedance sensing (ECIS) is an innovative approach for the label-free and real-time detection of cell morphology, growth, and apoptosis, thereby playing an essential role as both a viable alternative and valuable complement to conventional biochemical/pharmaceutical analysis in the field of diagnostics. Constant improvements are naturally sought to further improve the effective range and reliability of this technology. In this study, we developed poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) conducting polymer (CP)-based bioelectrodes integrated into homemade ECIS cell-culture chamber slides for the simultaneous drug release and real-time biosensing of cancer cell viability under drug treatment. The CP comprised tailored PEDOT:PSS, poly(ethylene oxide) (PEO), and (3-glycidyloxypropyl)trimethoxysilane (GOPS) capable of encapsulating antitumor chemotherapeutic agents such as doxorubicin (DOX), docetaxel (DTX), and a DOX/DTX combination. This device can reliably monitor impedance signal changes correlated with cell viability on chips generated by cell adhesion onto a predetermined CP-based working electrode while simultaneously exhibiting excellent properties for both drug encapsulation and on-demand release from another CP-based counter electrode under electrical stimulation (ES) operation. Cyclic voltammetry curves and surface profile data of different CP-based coatings (without or with drugs) were used to analyze the changes in charge capacity and thickness, respectively, thereby further revealing the correlation between their drug-releasing performance under ES operation (determined using ultraviolet–visible (UV–vis) spectroscopy). Finally, antitumor drug screening tests (DOX, DTX, and DOX/DTX combination) were performed on MCF-7 and HeLa cells using our developed CP-based ECIS chip system to monitor the impedance signal changes and their related cell viability results

Table_1_Organic Electrochemical Transistors/SERS-Active Hybrid Biosensors Featuring Gold Nanoparticles Immobilized on Thiol-Functionalized PEDOT Films.doc

In this study we immobilized gold nanoparticles (AuNPs) onto thiol-functionalized poly(3,4-ethylenedioxythiophene) (PEDOT) films as bioelectronic interfaces (BEIs) to be integrated into organic electrochemical transistors (OECTs) for effective detection of dopamine (DA) and also as surface-enhanced Raman scattering (SERS)—active substrates for the selective detection of p-cresol (PC) in the presence of multiple interferers. This novel PEDOT-based BEI device platform combined (i) an underlying layer of polystyrenesulfonate-doped PEDOT (PEDOT:PSS), which greatly enhanced the transconductance and sensitivity of OECTs for electrochemical sensing of DA in the presence of other ascorbic acid and uric acid metabolites, as well as amperometric response toward DA with a detection limit (S/N = 3) of 37 nM in the linear range from 50 nM to 100 μM; with (ii) a top interfacial layer of AuNP-immobilized three-dimensional (3D) thiol-functionalized PEDOT, which not only improved the performance of OECTs for detecting DA, due to the signal amplification effect of the AuNPs with high catalytic activity, but also enabled downstream analysis (SERS detection) of PC on the same chip. We demonstrate that PEDOT-based 3D OECT devices decorated with a high-density of AuNPs can display new versatility for the design of next-generation biosensors for point-of-care diagnostics.</p

Morphology Evolution of Spin-Coated Films of Poly(thiophene−phenylene−thiophene) and [6,6]-Phenyl-C₇₁-butyric Acid Methyl Ester by Solvent Effect

This paper describes the influence of the solvent on the morphological evolution and performance of polymer solar cells (PSCs) based on blended films of poly(thiophene−phenylene−thiophene) and [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM). The blends are spin-coated with solvents exhibiting various evaporation rates, including o-dichlorobenzene (DCB), chlorobenzene (CB), chloroform (CF), and tetralin. The changing morphologies of these blended films are monitored using atomic force microscopy (AFM) and transmission electron microscopy (TEM). A solvent having a higher boiling point [1,8-octanedithiol (OT)] is also introduced as an additive to further fine-tune the morphology of the bulk heterojunction (BHJ). We demonstrate herein that the morphology of a blendand, hence, the performance of a BHJ devicecan be manipulated by controlling the rate of solvent evaporation during film formation. The resulted fine-scale phase separation leads to enhanced performance of such organic photovoltaic devices. The highest power efficiency for our PSCs (5.8%, AM 1.5G irradiation (100 mW/cm2)) resulted when we use DCB as the solvent with OT as a processing additive

Improving the Light Trapping Efficiency of Plasmonic Polymer Solar Cells through Photon Management

In this study, we have explored how light trapping efficiency can be enhanced by using gold nanoparticles (Au NPs) of various sizes and shapes on the front of polymer solar cells (PSCs) with the active layerblends of poly­(3-hexyl thiophene) and [6,6]-phenyl-C₆₁-butyric acid methyl ester. The light-concentrating behavior was enhanced after we had incorporated gold nanospheres or nanorods into the anodic buffer layer [based on poly­(3,4-ethylenedioxythiophene):polystyrenesulfonate] to trigger various localized surface plasmon resonance (LSPR) bands. Comparison of the optical characteristics and the performance of the PSCs prepared with and without Au NPs, and we found that the UV–vis and wavelength-dependent photoluminescent spectral data corroborated with the device performance due to the photon management by considering the light scattering and LSPR effects at the active layer. The presence of Au NPs increased the power conversion efficiency to approximately 4.3% (an enhancement of 24%)

Facile Transfer Method for Fabricating Light-Harvesting Systems for Polymer Solar Cells

In this study, we used a transferring process to fabricate a simple light-harvesting system featuring 2D periodic granular-like electrodes for polymer solar cells (PSCs). This transferring technique, which was based on nanosphere lithography, could be used to fabricate periodic nanostructures on both the photoactive layers and the Al electrodes in the normal PSC device configuration (indium tin oxide glass/PEDOT:PSS/photoactive layer/Al). We investigated the properties of the PSC devices featuring periodic nanostructures in the photoactive layers using reflection UV–vis spectra and in terms of their external quantum efficiency (EQE) and photocurrent–voltage characteristics. In addition, we used numerical simulations to evaluate the electromagnetic field distributions in the devices. The light trapping efficiency in the PSCs featuring periodic nanostructures was enhanced as a result of light scattering and surface plasmon resonance effects. Relative to conventional devices featuring a flat geometry, the power conversion efficiency of a thin (ca. 150 nm) photoactive P3HT/C70 bilayer device increased by 90% when it featured a periodic nanostructure, with up to 20-fold increases in EQE observed at the absorption edge. Furthermore, when we engineered periodic nanostructures into bulk heterojunction devices incorporating a low-bandgap (LBG) photoactive layer (PTPTBT:PC70BM), the photocurrent increased by 20%, suggesting that this facile light-harvesting system is suitable for both thin P3HT and LBG PSC applications in the visible to near-infrared (NIR) region

Biophysical Electrical and Mechanical Stimulations for Promoting Chondrogenesis of Stem Cells on PEDOT:PSS Conductive Polymer Scaffolds

The investigation of the effects of electrical and mechanical stimulations on chondrogenesis in tissue engineering scaffolds is essential for realizing successful cartilage repair and regeneration. The aim of articular cartilage tissue engineering is to enhance the function of damaged or diseased articular cartilage, which has limited regenerative capacity. Studies have shown that electrical stimulation (ES) promotes mesenchymal stem cell (MSC) chondrogenesis, while mechanical stimulation (MS) enhances the chondrogenic differentiation capacity of MSCs. Therefore, understanding the impact of these stimuli on chondrogenesis is crucial for researchers to develop more effective tissue engineering strategies for cartilage repair and regeneration. This study focuses on the preparation of poly­(3,4-ethylenedioxythiophene)-poly­(styrenesulfonate) (PEDOT:PSS) conductive polymer (CP) scaffolds using the freeze-drying method. The scaffolds were fabricated with varying concentrations (0, 1, 3, and 10 wt %) of (3-glycidyloxypropyl) trimethoxysilane (GOPS) as a crosslinker and an additive to tailor the scaffold properties. To gain a comprehensive understanding of the material characteristics and the phase aggregation phenomenon of PEDOT:PSS scaffolds, the researchers performed theoretical calculations of solubility parameters and surface energies of PSS, PSS-GOPS, and PEDOT polymers, as well as conducted material analyses. Additionally, the study investigated the potential of promoting chondrogenic differentiation of human adipose stem cells by applying external ES or MS on a PEDOT:PSS CP scaffold. Compared to the group without stimulation, the group that underwent stimulation exhibited significantly up-regulated expression levels of chondrogenic characteristic genes, such as SOX9 and COL2A1. Moreover, the immunofluorescence staining images exhibited a more vigorous fluorescence intensity of SOX9 and COL II proteins that was consistent with the trend of the gene expression results. In the MS experiment, the strain excitation exerted on the scaffold was simulated and transformed into stress. The simulated stress response showed that the peak gradually decreased with time and approached a constant value, with the negative value of stress representing the generation of tensile stress. This stress response quantification could aid researchers in determining specific MS conditions for various materials in tissue engineering, and the applied stress conditions could be further optimized. Overall, these findings are significant contributions to future research on cartilage repair and biophysical ES/MS in tissue engineering