Organic Bioelectronic Devices Research Articles

"Clickable" Organic Electrochemical Transistors.

Interfacing the surface of an organic semiconductor with biological elements is a central quest when it comes to the development of efficient organic bioelectronic devices. Here, we present the first example of "clickable" organic electrochemical transistors (OECTs). The synthesis and characterization of an azide-derivatized EDOT monomer (azidomethyl-EDOT, EDOT-N3) are reported, as well as its deposition on Au-interdigitated electrodes through electropolymerization to yield PEDOT-N3-OECTs. The electropolymerization protocol allows for a straightforward and reliable tuning of the characteristics of the OECTs, yielding transistors with lower threshold voltages than PEDOT-based state-of-the-art devices and maximum transconductance voltage values close to 0 V, a key feature for the development of efficient organic bioelectronic devices. Subsequently, the azide moieties are employed to click alkyne-bearing molecules such as redox probes and biorecognition elements. The clicking of an alkyne-modified PEG4-biotin allows for the use of the avidin-biotin interactions to efficiently generate bioconstructs with proteins and enzymes. In addition, a dibenzocyclooctyne-modified thrombin-specific HD22 aptamer is clicked on the PEDOT-N3-OECTs, showing the application of the devices toward the development of organic transistors-based biosensors. Finally, the clicked OECTs preserve their electronic features after the different clicking procedures, demonstrating the stability and robustness of the fabricated transistors.

Benchmarking organic electrochemical transistors for plant electrophysiology.

Plants are able to sense and respond to a myriad of external stimuli, using different signal transduction pathways, including electrical signaling. The ability to monitor plant responses is essential not only for fundamental plant science, but also to gain knowledge on how to interface plants with technology. Still, the field of plant electrophysiology remains rather unexplored when compared to its animal counterpart. Indeed, most studies continue to rely on invasive techniques or on bulky inorganic electrodes that oftentimes are not ideal for stable integration with plant tissues. On the other hand, few studies have proposed novel approaches to monitor plant signals, based on non-invasive conformable electrodes or even organic transistors. Organic electrochemical transistors (OECTs) are particularly promising for electrophysiology as they are inherently amplification devices, they operate at low voltages, can be miniaturized, and be fabricated in flexible and conformable substrates. Thus, in this study, we characterize OECTs as viable tools to measure plant electrical signals, comparing them to the performance of the current standard, Ag/AgCl electrodes. For that, we focused on two widely studied plant signals: the Venus flytrap (VFT) action potentials elicited by mechanical stimulation of its sensitive trigger hairs, and the wound response of Arabidopsis thaliana. We found that OECTs are able to record these signals without distortion and with the same resolution as Ag/AgCl electrodes and that they offer a major advantage in terms of signal noise, which allow them to be used in field conditions. This work establishes these organic bioelectronic devices as non-invasive tools to monitor plant signaling that can provide insight into plant processes in their natural environment.

Functional Infectious Nanoparticle Detector: Finding Viruses by Detecting Their Host Entry Functions Using Organic Bioelectronic Devices.

Emerging viruses will continue to be a threat to human health and wellbeing into the foreseeable future. The COVID-19 pandemic revealed the necessity for rapid viral sensing and inhibitor screening in mitigating viral spread and impact. Here, we present a platform that uses a label-free electronic readout as well as a dual capability of optical (fluorescence) readout to sense the ability of a virus to bind and fuse with a host cell membrane, thereby sensing viral entry. This approach introduces a hitherto unseen level of specificity by distinguishing fusion-competent viruses from fusion-incompetent viruses. The ability to discern between competent and incompetent viruses means that this device could also be used for applications beyond detection, such as screening antiviral compounds for their ability to block virus entry mechanisms. Using optical means, we first demonstrate the ability to recapitulate the entry processes of influenza virus using a biomembrane containing the viral receptor that has been functionalized on a transparent organic bioelectronic device. Next, we detect virus membrane fusion, using the same, label-free devices. Using both reconstituted and native cell membranes as materials to functionalize organic bioelectronic devices, configured as electrodes and transistors, we measure changes in membrane properties when virus fusion is triggered by a pH drop, inducing hemagglutinin to undergo a conformational change that leads to membrane fusion.

In Situ Monitoring of Polaron Localization and Cell Activity with Charge Accumulation Spectroscopy

AbstractLocalization of charge carriers directly affects charge transport and local potential fluctuations and is a critical factor dictating the performance of organic bioelectronic devices. Understanding how the polaron localization at the solid−water interface is influenced by the microscopic structural ordering of the organic semiconducting films can provide complementary information to achieve better control on the electrochemical stability of bioelectronic devices. Here, charge accumulation spectroscopy is utilized to explore the structure‐dependent polaron localization in an electrolyte‐gated organic field‐effect transistor structure. The results reveal that the ordered and closely packed systems exhibit much higher absorption cross‐sections (σp) than disordered and isolated molecules. Therefore, the charge‐induced absorption feature can be utilized to monitor in situ the microscopic morphology variations of organic semiconducting films under electrolyte and trace the entire cell detachment process noninvasively. This study suggests that the spectroscopic signature of polaronic charge carriers, which is highly sensitive to the local environment surrounding the probed chromophores, serves as an effective probe to detect the structure‐dependent charge transport features in organic bioelectronic devices.

Strain-Engineering Induced Anisotropic Crystallite Orientation and Maximized Carrier Mobility for High-Performance Microfiber-Based Organic Bioelectronic Devices.

Despite the importance of carrier mobility, recent research efforts have been mainly focused on the improvement of volumetric capacitance in order to maximize the figure-of-merit, μC* (product of carrier mobility and volumetric capacitance), for high-performance organic electrochemical transistors. Herein, high-performance microfiber-based organic electrochemical transistors with unprecedentedly large μC* using highly ordered crystalline poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) microfibers with very high carrier mobilities are reported. The strain engineering via uniaxial tension is employed in combination with solvent-mediated crystallization in the course of drying coagulated fibers, resulting in the permanent preferential alignment of crystalline PEDOT:PSS domains along the fiber direction, which is verified by atomic force microscopy and transmission wide-angle X-ray scattering. The resultant strain-engineered microfibers exhibit very high carrier mobility (12.9 cm2 V-1 s-1 ) without the trade-off in volumetric capacitance (122Fcm-3 ) and hole density (5.8×1020 cm-3 ). Such advantageous electrical and electrochemical characteristics offer the benchmark parameter of μC* over ≈1500Fcm-1 V-1 s-1 , which is the highest metric ever reported in the literature and can be beneficial for realizing a new class of substrate-free fibrillar and/or textile bioelectronics in the configuration of electrochemical transistors and/or electrochemical ion pumps.

Single‐Material OECT‐Based Flexible Complementary Circuits Featuring Polyaniline in Both Conducting Channels

AbstractThe organic electrochemical transistor (OECT) with a conjugated polymer as the active material is the elementary unit of organic bioelectronic devices. Improved functionalities, such as low power consumption, can be achieved by building complementary circuits featuring two or more OECTs. Complementary circuits commonly combine both p‐ and n‐type transistors to reduce power draw. While p‐type OECTs are readily available, n‐type OECTs are less common mainly due to poor stability of the n‐type active channel material in aqueous electrolyte. Here, a complementary circuit is made using a pair of OECTs having polyaniline (PANI) as the channel material in both transistors. PANI, with a finite electrochemical window accessible at voltages lower than 1 V, exhibits a peak in current versus gate voltage when used as an active channel in an OECT. The current peak has two slopes, one n‐like and one p‐like, which correspond to different electrochemical regimes of the same underlying conjugated polymer. The electrochemistry enables the design of a complementary circuit using only PANI as the channel material. The PANI‐based circuit is shown to have excellent performance with gain of ≈7 and is transferred on a flexible biocompatible chitosan substrate with demonstrated operation in aqueous electrolyte.

Hydrogel‐Enabled Transfer‐Printing of Conducting Polymer Films for Soft Organic Bioelectronics

AbstractThe use of conducting polymers such as poly(3,4‐ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) for the development of soft organic bioelectronic devices, such as organic electrochemical transistors (OECTs), is rapidly increasing. However, directly manipulating conducting polymer thin films on soft substrates remains challenging, which hinders the development of conformable organic bioelectronic devices. A facile transfer‐printing of conducting polymer thin films from conventional rigid substrates to flexible substrates offers an alternative solution. In this work, it is reported that PEDOT:PSS thin films on glass substrates, once mixed with surfactants, can be delaminated with hydrogels and thereafter be transferred to soft substrates without any further treatments. The proposed method allows easy, fast, and reliable transferring of patterned PEDOT:PSS thin films from glass substrates onto various soft substrates, facilitating their application in soft organic bioelectronics. By taking advantage of this method, skin‐attachable tattoo‐OECTs are demonstrated, relevant for conformable, imperceptible, and wearable organic biosensing.

Functionalized Organic Thin Film Transistors for Biosensing.

The rise of organic bioelectronics efficiently bridges the gap between semiconductor devices and biological systems, leading to flexible, lightweight, and low-cost organic bioelectronic devices suitable for health or body signal monitoring. The introduction of organic semiconductors in the devices can soften the boundaries between microelectronic systems and dynamically active cells and tissues. Therefore, organic bioelectronics has attracted much attention recently due to the unique properties and promising applications. Organic thin film transistors (OTFTs), owing to their inherent capability of amplifying received signals, have emerged as one of the state-of-the-art biosensing platforms. The advantages of organic semiconductors in terms of synthetic freedom, low temperature solution processing, biocompatibility, and mechanical flexibility render OTFTs ideal transducers for wearable electronics, e-skin, and implantable devices. How to realize highly sensitive, selective, rapid, and efficient signal capture and extraction of biological recognition events is the major challenge in the design of biosensors. OTFTs are prone to converting the presence or change of target analytes into specific electrical signals even in complex biological systems. More importantly, OTFT sensors can be conveniently functionalized with chemical or biological modifications and exhibit substantially improved device sensitivity and selectivity as well as other analytical figure of merits, including calibration range, linearity, and accuracy. However, the stability and reproducibility of the organic devices need to be further improved. In this Account, we first introduce the unique features of OTFTs for bioelectronic applications. Two typical OTFT configurations, including organic electrochemical transistor (OECT) and electrolyte gated organic field effect transistor (EGOFET), are highlighted in their sensing applications mainly due to the operation of the devices in electrolytes and the combination of ionic and electronic charge transports in the devices. These devices are potentiometric transducers with low working voltages (<1 V) and high sensitivity, and are thus suitable for wearable applications with low power consumption. Second, the functionalization strategies on channel materials, electrolytes, and gate electrodes based on various modification methods and sensing mechanisms are discussed in sequence. In an OECT- or EGOFET-based biosensor, the device performance is particularly sensitive to the physical properties of the two interfaces, including channel/electrolyte and gate/electrolyte interfaces. Any change in the potential drop or capacitance of either interface can influence the channel current substantially. Therefore, the functionalization of the interfaces is critical to the sensing performance. In particular, when an electrochemically active material is modified on the interfaces, the reaction of the analyte catalyzed by the modified material can influence the interface potential and lead to a channel current response much stronger than that of a conventional electrochemical measurement. So the biosensors are much more sensitive than typical analytical methods due to the signal amplification of the transistors. Third, the processing techniques including screen printing and inkjet printing and the possibility for mass production are discussed. The applications of organic transistors in wearable electronics and healthcare monitoring systems, especially the fabric OECT-based biosensors for noninvasive detection, are presented. It is expected that the versatile organic transistors will enable various compact, flexible and disposable biosensors compatible with wearable electronics.

Electrical Stimulation by an Organic Transistor Architecture Induces Calcium Signaling in Nonexcitable Brain Cells.

Organic bioelectronics have a huge potential to generate interfaces and devices for the study of brain functions and for the therapy of brain pathologies. In this context, increasing efforts are needed to develop technologies for monitoring and stimulation of nonexcitable brain cells, called astrocytes. Astroglial calcium signaling plays, indeed, a pivotal role in the physiology and pathophysiology of the brain. Here, the use of transparent organic cell stimulating and sensing transistor (O-CST) architecture, fabricated with N,N'-ditridecylperylene-3,4,9,10-tetracarboxylic diimide (P13), to elicit and monitor intracellular calcium concentration ([Ca2+ ]i ) in primary rat neocortical astrocytes is demonstrated. The transparency of O-CST allows performing calcium imaging experiments, showing that extracellular electrical stimulation of astrocytes induces a drastic increase in [Ca2+ ]i . Pharmacological studies indicate that transient receptor potential (TRP) superfamily are critical mediators of the [Ca2+ ]i increase. Experimental and computational analyses show that [Ca2+ ]i response is enabled by the O-CST device architecture. Noteworthy, the extracellular field application induces a slight but significant increase in the cell volume. Collectively, it is shown that the O-CST is capable of selectively evoking astrocytes [Ca2+ ]i , paving the way to the development of organic bioelectronic devices as glial interfaces to excite and control physiology of non-neuronal brain cells.

Spectroscopic Study of Charge Transport at Organic Solid–Water Interface

Charge transport in an organic solid and its coupling with the neighboring aqueous biological environment dictates the performance of many organic bioelectronic devices. Understanding how the transport property at the solid–water interface is influenced by the surface structure characteristics of the organic solid is essential for rational design of organic bioelectronics and chemical sensors. However, in situ probing such structure–property relationships has been difficult due to lack of experimental techniques with sufficient sensitivity to the water-buried interface. Here, we demonstrate a charge accumulation spectroscopy (CAS)-based protocol, exploiting water-gated organic field-effect transistor as the testing platform, to investigate the structure-dependent localization of polaronic charge carriers at the organic semiconductor–liquid interface. Our results reveal that the degree of charge delocalization is reduced drastically when the charge carriers are moved from the bulk semiconductor to the semiconductor–water interface, suggesting the existence of a highly disordered surface layer in contact with water. It is also found that the charge delocalization could be further reduced by intercalation of chloride ions (from salt water) in the semiconductor surface layer. This study suggests that the spectroscopic signatures of polaronic charge carriers could be a sensitive probe to detect the structure-dependent charge localization at organic solid–liquid interfaces.

Molecular Approach to Conjugated Polymers with Biomimetic Properties.

The field of bioelectronics involves the fascinating interplay between biology and human-made electronics. Applications such as tissue engineering, biosensing, drug delivery, and wearable electronics require biomimetic materials that can translate the physiological and chemical processes of biological systems, such as organs, tissues. and cells, into electrical signals and vice versa. However, the difference in the physical nature of soft biological elements and rigid electronic materials calls for new conductive or electroactive materials with added biomimetic properties that can bridge the gap. Soft electronics that utilize organic materials, such as conjugated polymers, can bring many important features to bioelectronics. Among the many advantages of conjugated polymers, the ability to modulate the biocompatibility, solubility, functionality, and mechanical properties through side chain engineering can alleviate the issues of mechanical mismatch and provide better interface between the electronics and biological elements. Additionally, conjugated polymers, being both ionically and electrically conductive through reversible doping processes provide means for direct sensing and stimulation of biological processes in cells, tissues, and organs. In this Account, we focus on our recent progress in molecular engineering of conjugated polymers with tunable biomimetic properties, such as biocompatibility, responsiveness, stretchability, self-healing, and adhesion. Our approach is general and versatile, which is based on functionalization of conjugated polymers with long side chains, commonly polymeric or biomolecules. Applications for such materials are wide-ranging, where we have demonstrated conductive, stimuli-responsive antifouling, and cell adhesive biointerfaces that can respond to external stimuli such as temperature, salt concentration, and redox reactions, the processes that in turn modify and reversibly switch the surface properties. Furthermore, utilizing the advantageous chemical, physical, mechanical and functional properties of the grafts, we progressed into grafting of the long side chains onto conjugated polymers in solution, with the vision of synthesizing solution-processable conjugated graft copolymers with biomimetic functionalities. Examples of the developed materials to date include rubbery and adhesive photoluminescent plastics, biomolecule-functionalized electrospun biosensors, thermally and dually responsive photoluminescent conjugated polymers, and tunable self-healing, adhesive, and stretchable strain sensors, advanced functional biocidal polymers, and filtration membranes. As outlined in these examples, the applications of these biomimetic, conjugated polymers are still in the development stage toward truly printable, organic bioelectronic devices. However, in this Account, we advocate that molecular engineering of conjugated polymers is an attractive approach to a versatile class of organic electronics with both ionic and electrical conductivity as well as mechanical properties required for next-generation bioelectronics.

Silk protein nanowires patterned using electron beam lithography

Nanofabrication approaches to pattern proteins at the nanoscale are useful in applications ranging from organic bioelectronics to cellular engineering. Specifically, functional materials based on natural polymers offer sustainable and environment-friendly substitutes to synthetic polymers. Silk proteins (fibroin and sericin) have emerged as an important class of biomaterials for next generation applications owing to excellent optical and mechanical properties, inherent biocompatibility, and biodegradability. However, the ability to precisely control their spatial positioning at the nanoscale via high throughput tools continues to remain a challenge. In this study electron beam lithography (EBL) is used to provide nanoscale patterning using methacrylate conjugated silk proteins that are photoreactive ‘photoresists’ materials. Very low energy electron beam radiation can be used to pattern silk proteins at the nanoscale and over large areas, whereby such nanostructure fabrication can be performed without specialized EBL tools. Significantly, using conducting polymers in conjunction with these silk proteins, the formation of protein nanowires down to 100 nm is shown. These wires can be easily degraded using enzymatic degradation. Thus, proteins can be precisely and scalably patterned and doped with conducting polymers and enzymes to form degradable, organic bioelectronic devices.

Redox‐Stability of Alkoxy‐BDT Copolymers and their Use for Organic Bioelectronic Devices

AbstractOrganic semiconductors can be employed as the active layer in accumulation mode organic electrochemical transistors (OECTs), where redox stability in aqueous electrolytes is important for long‐term recordings of biological events. It is observed that alkoxy‐benzo[1,2‐b:4,5‐b′]dithiophene (BDT) copolymers can be extremely unstable when they are oxidized in aqueous solutions. The redox stability of these copolymers can be improved by molecular design of the copolymer where it is observed that the electron rich comonomer 3,3′‐dimethoxy‐2,2′‐bithiophene (MeOT2) lowers the oxidation potential and also stabilizes positive charges through delocalization and resonance effects. For copolymers where the comonomers do not have the same ability to stabilize positive charges, irreversible redox reactions are observed with the formation of quinone structures, being detrimental to performance of the materials in OECTs. Charge distribution along the copolymer from density functional theory calculations is seen to be an important factor in the stability of the charged copolymer. As a result of the stabilizing effect of the comonomer, a highly stable OECT performance is observed with transconductances in the mS range. The analysis of the decomposition pathway also raises questions about the general stability of the alkoxy‐BDT unit, which is heavily used in donor–acceptor copolymers in the field of photovoltaics.

DNA assisted regioregular poly (3, 3‴-didodecylquarterthiophene), rr-PQT-12 fiber: Organic bio-electronic devices

Abstract Present work has focused on the development of bio-organic hybrid materials based on hydrophobic DNA-complex incorporated in polymer and the study of charge transport properties across the junction formed by sandwiching it between conducting electrodes (called hetero-structured vertical diode). The inclusion of hydrophilic DNAs, both natural DNA and synthetic DNA (single strand DNA, ss-DNA and double strand DNA, ds-DNA), in organic semiconducting polymer specially regioregular poly (3, 3‴-didodecylquarterthiophene) (rr-PQT-12), have done in chloroform. Prior to DNAs inclusion, hydrophobic DNA-DDAB complexes have formed by reaction of hydrophilic DNA and didodecyldimethylammonium bromide, DDAB in aqueous solvent. Thereafter, as-mixed solution has been aged for 45 min to obtain fibrils' growth and used for the fabrication of devices. Various parameters including rectification ratio, ideality factor, saturation current, barrier height and device stability have been measured to study the nature of charge transport and effect of DNAs on the performance of devices. The device performance has been observed better with the incorporation of G-C rich DNAs. ds-DNA based devices exhibit improved rectification ratio i.e. two times higher than that of ss-DNA and three times higher than that of rr-PQT-12 with least turn-on voltage (0.56 V) or even low ideality factor (3.02), due to hot carrier injection phenomenon by assembled rr-PQT-12 to nearby nucleotide bases.

Influence of Electrical and Ionic Conductivities of Organic Electronic Ion Pump on Acetylcholine Exchange Performance.

By using an easy and effective method of depositing conjugated polymers (PEDOT:PSS) on flexible substrates, a new design for organic bioelectronic devices has been developed. The purpose was to build up a system that mimics the motion of neurotransmitters in the synaptic cleft by obtaining an electrical to chemical signal transport. Fourier transform infrared (FTIR) spectroscopy and Raman measurements have demonstrated that electrochemical overoxidation region which separates the pristine PEDOT:PSS electrodes and allows ionic conduction has been achieved successfully. The influence of both electrical and ionic conductivities on organic electronic ion pump (OEIP) performances has been studied. The ultimate goal was to achieve the highest equilibrium current density at the lowest applied voltage via enhancing the electrical conductivity of PEDOT:PSS and ionic conductivity of electrochemically overoxidized region. The highest equilibrium current density, which corresponds to 4.81 × 1017 number of ions of acetylcholine was about 41 μA cm−2 observed for the OEIP with the electrical conductivities of 54 S cm−1. This was a threshold electrical conductivity beyond which the OEIP performances were not changed much. Once Nafion™ has been applied for enhancing the ionic conductivity, the equilibrium current density increased about ten times and reached up to 408 μA cm−2. Therefore, it has been demonstrated that the OEIP performance mainly scales with the ionic conductivity. A straightforward method of producing organic bioelectronics is proposed here may provide a clue for their effortless mass production in the near future.

Organic Bioelectronic Tools for Biomedical Applications

Organic bioelectronics forms the basis of conductive polymer tools with great potential for application in biomedical science and medicine. It is a rapidly growing field of both academic and industrial interest since conductive polymers bridge the gap between electronics and biology by being electronically and ionically conductive. This feature can be employed in numerous ways by choosing the right polyelectrolyte system and tuning its properties towards the intended application. This review highlights how active organic bioelectronic surfaces can be used to control cell attachment and release as well as to trigger cell signaling by means of electrical, chemical or mechanical actuation. Furthermore, we report on the unique properties of conductive polymers that make them outstanding materials for labeled or label-free biosensors. Techniques for electronically controlled ion transport in organic bioelectronic devices are introduced, and examples are provided to illustrate their use in self-regulated medical devices. Organic bioelectronics have great potential to become a primary platform in future bioelectronics. We therefore introduce current applications that will aid in the development of advanced in vitro systems for biomedical science and of automated systems for applications in neuroscience, cell biology and infection biology. Considering this broad spectrum of applications, organic bioelectronics could lead to timely detection of disease, and facilitate the use of remote and personalized medicine. As such, organic bioelectronics might contribute to efficient healthcare and reduced hospitalization times for patients.

(Invited) Conducting Polymer Transistors Making Use of Activated Carbon Gate Electrodes

The characteristics of the gate electrode have significant effects on the behaviour of organic electrochemical transistors (OECTs), which are intensively investigated for applications in the booming field of organic bioelectronics. In this work, high specific surface area activated carbon (AC) was used as gate electrode material in OECTs based on the conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) doped with poly(styrene sulfonate) (PSS).1 We found that the high specific capacitance of the AC gate electrodes leads to high drain-source current modulation in OECTs. Cyclic voltammetry studies, where PEDOT:PSS is used as the working electrode (WE) and AC is used as the reference electrode (RE) and counter electrode (CE), show that high double-layer capacitance and absence of Faradaic processes permit the development of stable OECTs where the channel potential is uniquely determined by the applied gate bias. The intrinsic quasi-reference characteristics of AC electrodes make unnecessary the presence of an additional reference electrode to monitor the OECT channel potential. The ease of process of AC electrodes for in plane, flexible device architectures constitutes a step forward in the search of new electrode materials for OECTs to be used in iontronics, printed electronics, bio analytical sensing, and other organic bioelectronic devices.

(Invited) Thin Films of Eumelanin Pigment: Charge Carrier Transport, Ion Storage, and Interaction with Metal Electrodes

The ubiquitous natural pigment eumelanin is widely studied for its photoprotective, thermoregulating, free-radical scavenging, and anti-oxidant functions in the human body. Recently, eumelanin received increased attention for potential applications in organic bioelectronics due to its unique set of physicochemical properties including strong broad-band UV-Vis absorption, metal chelation properties, and potentially mixed electronic-ionic conduction in a hydrated state [1,2]. To further explore the use of eumelanin in organic bioelectronic devices, the properties of eumelanin thin films interfaced with device components such as metal electrodes need to be investigated in presence of water and ionic species. A good understanding of the interaction of eumelanin with different metal electrodes is also essential to study the intrinsic charge transport properties of eumelanin films, which are still largely undiscovered. We characterized eumelanin films grown on substrates patterned with gold, platinum, and palladium hydride electrodes using hydration-dependent transient electrical current and atomic force microscopy measurements. We discovered an electrochemical interaction among metal-chelating catechol groups of hydrated eumelanin, Cl- traces in the eumelanin material and Au electrodes, assumed to be electrochemically stable in previously published works on the electrical properties of eumelanin. This interaction leads to the growth of highly conductive Au-eumelanin dendrites between the electrodes, ultimately leading to sudden resistive changes of the sample. This phenomenon suggests new possibilities for biocompatible memory devices and has to be taken into account when integrating eumelanin-like materials in electronic devices [3]. Electrical characterization of eumelanin films interfaced with ion-blocking Pt and proton-transparent electrodes [4] complemented by cyclic voltammetry and impedance spectroscopy measurements give new insights into the charge transport properties of eumelanin films. Our results indicate the presence of protonic currents in eumelanin thin films, increasing with sample hydration, and cannot exclude the presence of electronic currents. These results support recently published data obtained by spectroscopic measurements on eumelanin pellets [2] and underline the attractiveness of eumelanin films for applications at the interface of electronics and biology. [1] M. D’Ischia et al., Angew. Chem. Int. Edit. 48, 3914 (2009). [2] A. B. Mostert et al., Proc. Natl. Acad. Sci. 109, 8943 (2012). [3] J. Wünsche et al., Adv. Funct. Mater. 23, 5569 (2013). [4] C. Zhong, Y. Deng, A. F. Roudsari, A. Kapetanovic, M. P. Anantram, M. Rolandi, Nat. Commun. 2, 476 (2011).

Flexible Organic Electronics in Biology: Materials and Devices.

At the convergence of organic electronics and biology, organic bioelectronics attracts great scientific interest. The potential applications of organic semiconductors to reversibly transmit biological signals or stimulate biological tissues inspires many research groups to explore the use of organic electronics in biological systems. Considering the surfaces of movable living tissues being arbitrarily curved at physiological environments, the flexibility of organic bioelectronic devices is of paramount importance in enabling stable and reliable performances by improving the contact and interaction of the devices with biological systems. Significant advances in flexible organic bio-electronics have been achieved in the areas of flexible organic thin film transistors (OTFTs), polymer electrodes, smart textiles, organic electrochemical ion pumps (OEIPs), ion bipolar junction transistors (IBJTs) and chemiresistors. This review will firstly discuss the materials used in flexible organic bioelectronics, which is followed by an overview on various types of flexible organic bioelectronic devices. The versatility of flexible organic bioelectronics promises a bright future for this emerging area.

Electrically tunable organic bioelectronics for spatial and temporal manipulation of neuron-like pheochromocytoma (PC-12) cells

BackgroundOrganic bioelectronic devices consisting of alternating poly(3,4-ethylenedioxythiophene) (PEDOT) and reduced graphite oxide (rGO) striped microelectrode arrays were fabricated by lithography technology. It has been demonstrated that the organic bioelectronic devices can be used to spatially and temporally manipulate the location and proliferation of the neuron-like pheochromocytoma cells (PC-12 cells). MethodsBy coating an electrically labile contact repulsion layer of poly(l-lysine-graft-ethylene glycol) (PLL-g-PEG) on the PEDOT electrode, the location and polarity of the PC-12 cells were confined to the rGO electrodes. ResultsThe outgrowth of spatially confined bipolar neurites was found to align along the direction of the 20μm wide electrode. The location of the PC-12 cells can also be manipulated temporally by applying electrical stimulation during the neurite differentiation of PC-12 cells, allowing the PC-12 cells to cross over the boundary between the PEDOT and the rGO regions and construct neurite networks in an unconfined manner where the contact repulsive coating of PLL-g-PEG was removed. ConclusionsThis adsorption and desorption of the PLL-g-PEG without and with electrical stimulation can be attributed to the tunable surface properties of the PEDOT microelectrodes, whose surface charge can switch from being negative to positive under electrical stimulation. General significanceThe electrically tunable organic bioelectronics reported here could potentially be applied to tissue engineering related to the development and regeneration of mammalian nervous systems. The spatial and temporal control in this device would also be used to study the synapse junctions of neuron–neuron contacts in both time and space domains. This article is part of a Special Issue entitled Organic Bioelectronics — Novel Applications in Biomedicine.