Increasing plants photosynthetic efficienc y is a major challenge that must be addressed in order to cover the food demands of the growing population in the changing climate. Photosynthes i s is greatly limited at the initial carboxylation reaction, where CO2 is converted to the organic acid 3-PGA, catalyzed by the RuBisCO enzyme. RuBisCO has poor affinity for CO2, but also the CO2 concentration at the RuBisCO site is limited by the diffusion of atmospheric CO2 through the various leaf compartments to the reaction site. Beyond genetic engineer-ing, nanotechnology can offer a materials-based approach for enhancing photosynthesis, and yet, it has mostly been explored for the light-dependent reactions. In this work, we developed polyethyleneimine-based nanoparticl e s for enhancing the carbox-ylation reaction. We demonstrate that the nanoparticles can capture CO2 in the form of bicarbonate and increase the CO2 that reacts with the RuBisCO enzyme, enhancing the 3-PGA production in in vitro assays by 20%. The nanoparticles can be introduced to the plant via leaf infiltration and, because of the functionalization with chitosan oligomers, they do not induce any toxic effect to the plant. In the leaves, the nanoparticles localize in the apoplastic space but also spontaneously reach the chloroplasts where photosynthetic activity takes place. Their CO2 loading-dependent fluorescence verifies that, in vivo, they maintain their abi l i t y to capture CO2 and can be therefore reloaded with atmospheric CO2 while in planta. Our results contribute to the development of a nanomaterials-based CO2-concentrating mechanism in plants t h a t can potentially increase photosynthetic efficiency and overall plants CO2 storage.

Conducting cellulose composites are promising sustainable functional materials that have found application in energy devices, sensing and water purification. Herein, conducting aerogels are fabricated based on nanofibrillated cellulose and poly(3,4-ethylenedioxythiophene) polystyrene sulfonate, using the ice templating technique, and their bulk morphology is characterized with X-ray microtomography. The freezing method (-20 degrees C in a freezer vs liquid nitrogen) does not impact the mean porosity of the aerogels but the liquid-N2 aerogels have smaller pores. The integration of carbon fibers as addressing electrodes prior to freezing results in increased mean porosity and pore size in the liquid-N2 aerogels signifying that the carbon fibers alter the morphology of the aerogels when the freezing is fast. Spatially resolved porosity and pore size distributions also reveal that the liquid-N2 aerogels are more inhomogeneous. Independent of the freezing method, the aerogels have similar electrochemical properties. For aerogels without carbon fibers, freezer-aerogels have higher compression modulus and are less stable under cycling compression fatigue test. This can be explained by higher porosity with larger pores in the center of liquid-N2 aerogels and thinner pore walls. This work demonstrates that micro-CT is a powerful tool for characterizing the morphology of aerogels in a non-destructive and spatially resolved manner. Conducting aerogels based on nanofibrillated cellulose and poly(3,4-ethylenedioxythiophene) polystyrene sulfonate are fabricated with the ice templating technique and their bulk morphology is characterized in a spatially resolved manner with X-ray microtomography. The effect of the freezing temperature and the integration of carbon fibers electrodes prior to freezing on the morphology, mechanical, and electrochemical properties is examined.

Plant vasculature transports molecules that play a crucial role in plant signaling including systemic responses and acclimation to diverse environmental conditions. Targeted controlled delivery of molecules to the vascular tissue can be a biomimetic way to induce long distance responses, providing a new tool for the fundamental studies and engineering of stress-tolerant plants. Here, a flexible organic electronic ion pump, an electrophoretic delivery device, for controlled delivery of phytohormones directly in plant vascular tissue is developed. The c-OEIP is based on polyimide-coated glass capillaries that significantly enhance the mechanical robustness of these microscale devices while being minimally disruptive for the plant. The polyelectrolyte channel is based on low-cost and commercially available precursors that can be photocured with blue light, establishing much cheaper and safer system than the state-of-the-art. To trigger OEIP-induced plant response, the phytohormone abscisic acid (ABA) in the petiole of intact Arabidopsis plants is delivered. ABA is one of the main phytohormones involved in plant stress responses and induces stomata closure under drought conditions to reduce water loss and prevent wilting. The OEIP-mediated ABA delivery triggered fast and long-lasting stomata closure far away from the delivery point demonstrating systemic vascular transport of the delivered ABA, verified delivering deuterium-labeled ABA.

Next-generation implantable computational devices require long-term-stable electronic components capable of operating in, and interacting with, electrolytic surroundings without being damaged. Organic electrochemical transistors (OECTs) emerged as fitting candidates. However, while single devices feature impressive figures of merit, integrated circuits (ICs) immersed in common electrolytes are hard to realize using electrochemical transistors, and there is no clear path forward for optimal top-down circuit design and high-density integration. The simple observation that two OECTs immersed in the same electrolytic medium will inevitably interact hampers their implementation in complex circuitry. The electrolytes ionic conductivity connects all the devices in the liquid, producing unwanted and often unforeseeable dynamics. Minimizing or harnessing this crosstalk has been the focus of very recent studies. Herein, the main challenges, trends, and opportunities for realizing OECT-based circuitry in a liquid environment that could circumnavigate the hard limits of engineering and human physiology, are discussed. The most successful approaches in autonomous bioelectronics and information processing are analyzed. Elaborating on the strategies to circumvent and harness device crosstalk proves that platforms capable of complex computation and even machine learning (ML) can be realized in liquido using mixed ionic-electronic conductors (OMIECs).

Modulating neural activity with electrical or chemical stimulus can be used for fundamental and applied research. Typically, neuronal stimulation is performed with intracellular and extracellular electrodes that deliver brief electrical pulses to neurons. However, alternative wireless methodologies based on functional materials may allow clinical translation of technologies to modulate neuronal function. Here, we show that the organic semiconducting oligomer 4-[2-{2,5-bis(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)thiophen-3-yl}ethoxy]butane-1-sulfonate (ETE-S) induces precise behaviors in the small invertebrate Hydra, which were dissected through pharmacological and electrophysiological approaches. ETE-S-induced behavioral response relies on the presence of head neurons and calcium ions and is prevented by drugs targeting ionotropic channels and muscle contraction. Moreover, ETE-S affects Hydras electrical activity enhancing the contraction burst frequency. The unexpected neuromodulatory function played by this conjugated oligomer on a simple nerve net opens intriguing research possibilities on fundamental chemical and physical phenomena behind organic bioelectronic interfaces for neuromodulation and on alternative methods that could catalyze a wide expansion of this rising technology for clinical applications.

In Arabidopsis thaliana, local wounding and herbivore feeding provoke leaf-to-leaf propagating Ca2+ waves that are dependent on the activity of members of the glutamate receptor-like channels (GLRs). In systemic tissues, GLRs are needed to sustain the synthesis of jasmonic acid (JA) with the subsequent activation of JA dependent signaling response required for the plant acclimation to the perceived stress. Even though the role of GLRs is well established, the mechanism through which they are activated remains unclear. Here, we report that in vivo, the amino-acid-dependent activation of the AtGLR3.3 channel and systemic responses require a functional ligand-binding domain. By combining imaging and genetics, we show that leaf mechanical injury, such as wounds and burns, as well as hypo-osmotic stress in root cells, induces the systemic apoplastic increase of L-glutamate (L-Glu), which is largely independent of AtGLR3.3 that is instead required for systemic cytosolic Ca2+ elevation. Moreover, by using a bioelectronic approach, we show that the local release of minute concentrations of L-Glu in the leaf lamina fails to induce any long-distance Ca2+ waves.

Interfacing electronics with neural tissue is crucial for understanding complex biological functions, but conventional bioelectronics consist of rigid electrodes fundamentally incompatible with living systems. The difference between static solid-state electronics and dynamic biological matter makes seamless integration of the two challenging. To address this incompatibility, we developed a method to dynamically create soft substrate-free conducting materials within the biological environment. We demonstrate in vivo electrode formation in zebrafish and leech models, using endogenous metabolites to trigger enzymatic polymerization of organic precursors within an injectable gel, thereby forming conducting polymer gels with long-range conductivity. This approach can be used to target specific biological substructures and is suitable for nerve stimulation, paving the way for fully integrated, in vivo-fabricated electronics within the nervous system.

Electrical signals in plants are mediators of long-distance signaling and correlate with plant movements and responses to stress. These signals are studied with single surface electrodes that cannot resolve signal propagation and integration, thus impeding their decoding and link to function. Here, we developed a conformable multielectrode array based on organic electronics for large-scale and high-resolution plant electrophysiology. We performed precise spatiotemporal mapping of the action potential (AP) in Venus flytrap and found that the AP actively propagates through the tissue with constant speed and without strong directionality. We also found that spontaneously generated APs can originate from unstimulated hairs and that they correlate with trap movement. Last, we demonstrate that the Venus flytrap circuitry can be activated by cells other than the sensory hairs. Our work reveals key properties of the AP and establishes the capacity of organic bioelectronics for resolving electrical signaling in plants contributing to the mechanistic understanding of long-distance responses in plants.

The porosity of filters is typically fixed; thus, complex purification processes require application of multiple specialized filters. In contrast, smart filters with controllable and tunable properties enable dynamic separation in a single setup. Herein, an electroactive filter with controllable pore size is demonstrated. The electroactive filter is based on a metal mesh coated with a polythiophene polymer with ethylene glycol sidechains (p(g3T2)) that exhibit unprecedented voltage-driven volume changes. By optimizing the polymer coating on the mesh, controllable porosity during electrochemical addressing is achieved. The pores reversibly open and close, with a dynamic range of more than 95%, corresponding to over 30 mu m change of pores widths. Furthermore, the pores widths could be defined by applied potential with a 10 mu m resolution. From among hundreds of pores from different samples, about 90% of the pores could be closed completely, while only less than 1% are inactive. Finally, the electroactive filter is used to control the flow of a dye, highlighting the potential for flow control and smart filtration applications.

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.

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We investigate the possibility of producing biofuel cell electrode materials in vivo by injecting the reagents directly into plant tissues. We first introduce model electroactive substances Fe(CN)(6)(4-) and Ru(NH3)(6)(3+) into a Nicotiana tabacum leaf. In situ electrochemical measurements make it possible to trace the distribution of these substances. As well as mapping the vascular content, electrochemistry can be used to trigger reactions directly inside the plant. The injection of thiophene (T) and ethylenedioxythiophene (E)-based trimers (ETE) anchoring an Os(2,2-bipyridine)(2)(1-(3-aminopropyl)-imidazole)Cl Os-complex followed by the application of anodic polarization triggers a polymerization reaction in the region of the plant vascular system containing the monomer, showing that it is possible to generate electmactive organic macromolecules locally in vivo.

The nervous system poses a grand challenge for integration with modern electronics and the subsequent advances in neurobiology, neuroprosthetics, and therapy which would become possible upon such integration. Due to its extreme complexity, multifaceted signaling pathways, and similar to 1 kHz operating frequency, modern complementary metal oxide semiconductor (CMOS) based electronics appear to be the only technology platform at hand for such integration. However, conventional CMOS-based electronics rely exclusively on electronic signaling and therefore require an additional technology platform to translate electronic signals into the language of neurobiology. Organic electronics are just such a technology platform, capable of converting electronic addressing into a variety of signals matching the endogenous signaling of the nervous system while simultaneously possessing favorable material similarities with nervous tissue. In this review, we introduce a variety of organic material platforms and signaling modalities specifically designed for this role as "translator" , focusing especially on recent implementation in in vivo neuromodulation. We hope that this review serves both as an informational resource and as an encouragement and challenge to the field.

Future brain-machine interfaces, prosthetics, and intelligent soft robotics will require integrating artificial neuromorphic devices with biological systems. Due to their poor biocompatibility, circuit complexity, low energy efficiency, and operating principles fundamentally different from the ion signal modulation of biology, traditional Silicon-based neuromorphic implementations have limited bio-integration potential. Here, we report the first organic electrochemical neurons (OECNs) with ion-modulated spiking, based on all-printed complementary organic electrochemical transistors. We demonstrate facile bio-integration of OECNs with Venus Flytrap (Dionaea muscipula) to induce lobe closure upon input stimuli. The OECNs can also be integrated with all-printed organic electrochemical synapses (OECSs), exhibiting short-term plasticity with paired-pulse facilitation and long-term plasticity with retention >1000 s, facilitating Hebbian learning. These soft and flexible OECNs operate below 0.6 V and respond to multiple stimuli, defining a new vista for localized artificial neuronal systems possible to integrate with bio-signaling systems of plants, invertebrates, and vertebrates. The integration of artificial neuromorphic devices with biological systems plays a fundamental role for future brain-machine interfaces, prosthetics, and intelligent soft robotics. Harikesh et al. demonstrate all-printed organic electrochemical neurons on Venus flytrap that is controlled to open and close.

Life in our planet is highly dependent on plants as they are the primary source of food, regulators of the atmosphere, and providers of a variety of materials. In this work, we review the progress on bioelectronic devices for plants and biohybrid systems based on plants, therefore discussing advancements that view plants either from a biological or a technological perspective, respectively. We give an overview on wearable and implantable bioelectronic devices for monitoring and modulating plant physiology that can be used as tools in basic plant science or find application in agriculture. Furthermore, we discuss plant wearable devices for monitoring a plants microenvironment that will enable optimization of growth conditions. The review then covers plant biohybrid systems where plants are an integral part of devices or are converted to devices upon functionalization with smart materials, including self-organized electronics, plant nanobionics, and energy applications. The review focuses on advancements based on organic electronic and carbon-based materials and discusses opportunities, challenges, as well as future steps.

Leveraging the biocatalytic machinery of living organisms for fabricating functional bioelectronic interfaces, in vivo, defines a new class of micro-biohybrids enabling the seamless integration of technology with living biological systems. Previously, we have demonstrated the in vivo polymerization of conjugated oligomers forming conductors within the structures of plants. Here, we expand this concept by reporting that Hydra, an invertebrate animal, polymerizes the conjugated oligomer ETE-S both within cells that expresses peroxidase activity and within the adhesive material that is secreted to promote underwater surface adhesion. The resulting conjugated polymer forms electronically conducting and electrochemically active μm-sized domains, which are inter-connected resulting in percolative conduction pathways extending beyond 100 μm, that are fully integrated within the Hydra tissue and the secreted mucus. Furthermore, the introduction and in vivo polymerization of ETE-S can be used as a biochemical marker to follow the dynamics of Hydra budding (reproduction) and regeneration. This work paves the way for well-defined self-organized electronics in animal tissue to modulate biological functions and in vivo biofabrication of hybrid functional materials and devices.

Plant processes, ranging from photosynthesis through production of biomaterials to environmental sensing and adaptation, can be used in technology via integration of functional materials and devices. Previously, plants with integrated organic electronic devices and circuits distributed in their vascular tissue and organs have been demonstrated. To circumvent biological barriers, and thereby access the internal tissue, plant cuttings were used, which resulted in biohybrids with limited lifetime and use. Here, we report intact plants with electronic functionality that continue to grow and develop enabling plant-biohybrid systems that fully maintain their biological processes. The biocatalytic machinery of the plant cell wall was leveraged to seamlessly integrate conductors with mixed ionic-electronic conductivity along the root system of the plants. Cell wall peroxidases catalyzed ETE-S polymerization while the plant tissue served as the template, organizing the polymer in a favorable manner. The conductivity of the resulting p(ETE-S) roots reached the order of 10 S cm(-1) and remained stable over the course of 4 weeks while the roots continued to grow. The p(ETE-S) roots were used to build supercapacitors that outperform previous plant-biohybrid charge storage demonstrations. Plants were not affected by the electronic functionalization but adapted to this new hybrid state by developing a more complex root system. Biohybrid plants with electronic roots pave the way for autonomous systems with potential applications in energy, sensing and robotics.

Electrochemically induced volume changes in organic mixed ionic-electronic conductors (OMIECs) are particularly important for their use in dynamic microfiltration systems, biomedical machinery, and electronic devices. Although significant advances have been made to maximize the dimensional changes that can be accomplished by OMIECs, there is currently limited understanding of how changes in their molecular structures impact their underpinning fundamental processes and their performance in electronic devices. Herein, a series of ethylene glycol functionalized conjugated polymers is synthesized, and their electromechanical properties are evaluated through a combined approach of experimental measurements and molecular dynamics simulations. As demonstrated, alterations in the molecular structure of OMIECs impact numerous processes occurring during their electrochemical swelling, with sidechain length shortening decreasing the number of incorporated water molecules, reducing the generated void volumes and promoting the OMIECs to undergo different phase transitions. Ultimately, the impact of these combined molecular processes is assessed in organic electrochemical transistors, revealing that careful balancing of these phenomena is required to maximize device performance.

Bioelectronic devices that convert biochemical signals to electronic readout enable biosensing with high spatiotemporal resolution. These technologies have been primarily applied in biomedicine while in plants sensing is mainly based on invasive methods that require tissue sampling, hindering in-vivo detection and having poor spatiotemporal resolution. Here, we developed enzymatic biosensors based on organic electrochemical transistors (OECTs) for in-vivo and real-time monitoring of sugar fluctuations in the vascular tissue of trees. The glucose and sucrose OECT-biosensors were implanted into the vascular tissue of trees and were operated through a low-cost portable unit for 48hr. Our work consists a proof-of-concept study where implantable OECT-biosensors not only allow real-time monitoring of metabolites in plants but also reveal new insights into diurnal sugar homeostasis. We anticipate that this work will contribute to establishing bioelectronic technologies as powerful minimally invasive tools in plant science, agriculture and forestry.

Our Emerging Investigator Series features exceptional work by early-career researchers working in the field of materials science.

Polar polythiophenes with oligoethylene glycol side chains are exceedingly soft materials. A low glass transition temperature and low degree of crystallinity prevents their use as a bulk material. The synthesis of a copolymer comprising 1) soft polythiophene blocks with tetraethylene glycol side chains, and 2) hard urethane segments is reported. The molecular design is contrary to that of other semiconductor-insulator copolymers, which typically combine a soft nonconjugated spacer with hard conjugated segments. Copolymerization of polar polythiophenes and urethane segments results in a ductile material that can be used as a free-standing solid. The copolymer displays a storage modulus of 25 MPa at room temperature, elongation at break of 95%, and a reduced degree of swelling due to hydrogen bonding. Both chemical doping and electrochemical oxidation reveal that the introduction of urethane segments does not unduly reduce the hole charge-carrier mobility and ability to take up charge. Further, stable operation is observed when the copolymer is used as the active layer of organic electrochemical transistors.

Conductive polymer PEDOT:Tos (3,4-ethylenedioxythiophene doped with molecular tosylate) gained considerable attention in various devices for bioelectronic applications, such as organic transistors and sensors. Many of these devices function upon oxidation/reduction processes in contact with aqueous electrolytes. So far, theoretical insight into morphological changes, ion injection, and water intake during these processes was rather limited. In the present work, we combined experiments and molecular dynamics simulations to study the water intake, swelling, and exchange of ions in the PEDOT:Tos film during cyclic voltammetry. We showed that the film underwent significant changes in morphology and mass during the redox processes. We observed both experimentally and in simulations that the film lost its mass during reduction, as tosylate and Na were expelled and gained mass during oxidation mainly due to the uptake of anions, i.e., tosylate and Cl. The results were in line with the UV-VIS-NIR absorption measurements and X-ray photoelectron spectroscopy (XPS) measurements, which revealed that during the redox process a portion of Tos was replaced by Cl- as the counterion for PEDOT. Also, the relative mass change between the most oxidized and reduced states was similar to 10 to 14% according to both experiments and simulations. We detected an overall material loss of the film during voltammetry cycles indicating that a portion of the material leaving the film during reduction did not return to the film during the consecutive oxidation. Our combined experimental/simulation study unraveled the underlying molecular processes in the PEDOT:Tos film upon the redox process, providing the essential understanding needed to improve and assess the performance of bioelectronic devices.

We demonstrate the fabrication, by exclusive means of inkjet-printing, of capacitive relative humidity sensors on flexible, plastic substrate. These sensors can be successfully used for the measurement of relative-humidity in both air and common soil. We also show that the same technique may be used for the fabrication of the same type of sensors on the surface of the leaves of El AE gnus Ebbingei (silverberry).Our results demonstrate the suitability of leaves as substrate for printed electronics and pave the way to the next generation of sensors to be used in fields such as agriculture and flower farming.

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Conjugated polymers conduct both electronic and ionic carriers and thus can stimulate and translate biological signals when used as active materials in bioelectronic devices. Self- and on-demand organization of the active material directly in the in vivo environment can result in the seamless integration of the bioelectronic interface. Along that line, we recently demonstrated spontaneous in vivo polymerization of the conjugated oligomer ETE-S in the vascular tissue of plants and the formation of conducting wires. In this work, we elucidate the mechanism of the in vivo polymerization of the ETE-S trimer and demonstrate that ETE-S polymerizes due to an enzymatic reaction where the enzyme peroxidase is the catalyst and hydrogen peroxide is the oxidant. ETE-S, therefore, represents the first example of a conducting polymer that is enzymatically polymerized in vivo. By reproducing the reaction in vitro, we gain further insight on the polymerization mechanism and show that hydrogen peroxide is the limiting factor. In plants the ETE-S triggers the catalytic cycle responsible for the lignification process, hacks this biochemical pathway and integrates within the plant cell wall, forming conductors along the plant structure.

Extracellular electron transfer (EET) denotes the process of microbial respiration with electron transfer to extracellular acceptors and has been exploited in a range of microbial electrochemical systems (MESs). To further understand EET and to optimize the performance of MESs, a better understanding of the dynamics at the microscale is needed. However, the real-time monitoring of EET at high spatiotemporal resolution would require sophisticated signal amplification. To amplify local EET signals, a miniaturized bioelectronic device, the so-called organic microbial electrochemical transistor (OMECT), is developed, which includes Shewanella oneidensis MR-1 integrated onto organic electrochemical transistors comprising poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) combined with poly(vinyl alcohol) (PVA). Bacteria are attached to the gate of the transistor by a chronoamperometric method and the successful attachment is confirmed by fluorescence microscopy. Monitoring EET with the OMECT configuration is achieved due to the inherent amplification of the transistor, revealing fast time-responses to lactate. The limits of detection when using microfabricated gates as charge collectors are also investigated. The work is a first step toward understanding and monitoring EET in highly confined spaces via microfabricated organic electronic devices, and it can be of importance to study exoelectrogens in microenvironments, such as those of the human microbiome.

Materials that efficiently transport and couple ionic and electronic charge are key to advancing a host of technological developments for next-generation bioelectronic, optoelectronic and energy storage devices. Here we highlight key progress in the design and study of organic mixed ionic–electronic conductors (OMIECs), a diverse family of soft synthetically tunable mixed conductors. Across applications, the same interrelated fundamental physical processes dictate OMIEC properties and determine device performance. Owing to ionic and electronic interactions and coupled transport properties, OMIECs demand special understanding beyond knowledge derived from the study of organic thin films and membranes meant to support either electronic or ionic processes only. We address seemingly conflicting views and terminology regarding charging processes in these materials, and highlight recent approaches that extend fundamental understanding and contribute to the advancement of materials. Further progress is predicated on multimodal and multi-scale approaches to overcome lingering barriers to OMIEC design and implementation.

Biosensors based on organic electrochemical transistors (OECT) are attractive devices for real-time monitoring of biological processes. The direct coupling between the channel of the OECT and the electrolyte enables intimate interfacing with biological environments at the same time bringing signal amplification and fast sensor response times. So far, these devices are mainly applied to mammalian systems; cells or body fluids for the development of diagnostics and various health status monitoring technology. Yet, no direct detection of biomolecules from cells or organelles is reported. Here, an OECT glucose sensor applied to chloroplasts, which are the plant organelles responsible for the light-to-chemical energy conversion of the photosynthesis, is reported. Real-time monitoring of glucose export from chloroplasts in two distinct metabolic phases is demonstrated and the transfer dynamics with a time resolution of 1 min is quantified, thus reaching monitoring dynamics being an order of magnitude better than conventional methods.

Conjugated polymers exhibit electrically driven volume changes when included in electrochemical devices via the exchange of ions and solvent. So far, this volumetric change is limited to 40% and 100% for reversible and irreversible systems, respectively, thus restricting potential applications of this technology. A conjugated polymer that reversibly expands by about 300% upon addressing, relative to its previous contracted state, while the first irreversible actuation can achieve values ranging from 1000-10 000%, depending on the voltage applied is reported. From experimental and theoretical studies, it is found that this large and reversible volumetric switching is due to reorganization of the polymer during swelling as it transforms between a solid-state phase and a gel, while maintaining percolation for conductivity. The polymer is utilized as an electroactive cladding to reduce the void sizes of a porous carbon filter electrode by 85%.

A series of glycolated polythiophenes for use in organic electrochemical transistors (OECTs) is designed and synthesized, differing in the distribution of their ethylene glycol chains that are tethered to the conjugated backbone. While side chain redistribution does not have a significant impact on the optoelectronic properties of the polymers, this molecular engineering strategy strongly impacts the water uptake achieved in the polymers. By careful optimization of the water uptake in the polymer films, OECTs with unprecedented steady-state performances in terms of [mu C*] and current retentions up to 98% over 700 electrochemical switching cycles are developed.

Energy harvesting from photosynthetic membranes, proteins, or bacteria through bio-photovoltaic or bio-electrochemical approaches has been proposed as a new route to clean energy. A major shortcoming of these and solar cell technologies is the underutilization of solar irradiation wavelengths in the IR region, especially those in the far IR region. Here, a biohybrid energy-harvesting device is demonstrated that exploits IR radiation, via convection and thermoelectric effects, to improve the resulting energy conversion performance. A composite of nanocellulose and the conducting polymer system poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) is used as the anode in biohybrid cells that includes thylakoid membranes (TMs) and redox mediators (RMs) in solution. By irradiating the conducting polymer electrode by an IR light-emitting diode, a sixfold enhancement in the harvested bio-photovoltaic power is achieved, without compromising stability of operation. Investigation of the output currents reveals that IR irradiation generates convective heat transfer in the electrolyte bulk, which enhances the redox reactions of RMs at the anode by suppressing diffusion limitations. In addition, a fast-transient thermoelectric component, originating from the PEDOT:PSS-nanocellulose-electrolyte interphase, further increases the bio-photocurrent. These results pave the way for the development of energy-harvesting biohybrids that make use of heat, via IR absorption, to enhance energy conversion efficiency.

Electronic materials that can self-organize in vivo and form functional components along the tissue of interest can result in a seamless integration of the bioelectronic interface. Previously, we presented in vivo polymerization of the conjugated oligomer ETE-S in plants, forming conductors along the plant structure. The EDOT-thiophene-EDOT trimer with a sulfonate side group polymerized due to the native enzymatic activity of the plant and integrated within the plant cell wall. Here, we present the synthesis of three different conjugated trimers based on thiophene and EDOT or purely EDOT trimers that are able to polymerize enzymatically in physiological pH in vitro as well as in vivo along the roots of living plants. We show that by modulating the backbone and the side chain, we can tune the electronic properties of the resulting polymers as well as their localization and penetration within the root. Our work paves the way for the rational design of electronic materials that can self-organize in vivo for spatially controlled electronic functionalization of living tissue.

Transcranial electrical stimulation is a noninvasive neurostimulation technique with a wide range of therapeutic applications. However, current electrode materials are typically not optimized for this abiotic/biotic interface which requires high charge capacity, operational stability, and conformability. Here, a plant-based composite electrode material based on the combination of aloe vera (AV) hydrogel and a conducting polymer (CP; poly(3,4-ethylenedioxythiophene):polystyrene sulfonate, PEDOT:PSS) is reported. This material system is fabricated into films and provides biocompatibility, conformability, and stability, while offering desirable electrical properties of the PEDOT:PSS. AVCP films are also molded onto the rough surface of the skull leading to a mechanically stable and robust interface. The in vivo efficacy of the AVCP films is verified to function as stimulating and recording electrodes by placing them on the skull of a rat and concomitantly inducing focal seizures and acquiring the evoked neural activity. AVCP films pave the way for high-quality biological interfaces that are broadly applicable and can facilitate advances in closed-loop responsive stimulation devices.

An evolvable organic electrochemical transistor (OECT), operating in the hybrid accumulation-depletion mode is reported, which exhibits short-term and long-term memory functionalities. The transistor channel, formed by an electropolymerized conducting polymer, can be formed, modulated, and obliterated in situ and under operation. Enduring changes in channel conductance, analogous to long-term potentiation and depression, are attained by electropolymerization and electrochemical overoxidation of the channel material, respectively. Transient changes in channel conductance, analogous to short-term potentiation and depression, are accomplished by inducing nonequilibrium doping states within the transistor channel. By manipulating the input signal, the strength of the transistor response to a given stimulus can be modulated within a range that spans several orders of magnitude, producing behavior that is directly comparable to short- and long-term neuroplasticity. The evolvable transistor is further incorporated into a simple circuit that mimics classical conditioning. It is forecasted that OECTs that can be physically and electronically modulated under operation will bring about a new paradigm of machine learning based on evolvable organic electronics.

Electronic control of biological processes with bioelectronic devices holds promise for sophisticated regulation of physiology, for gaining fundamental understanding of biological systems, providing new therapeutic solutions, and digitally mediating adaptations of organisms to external factors. The organic electronic ion pump (OEIP) provides a unique means for electronically-controlled, flow-free delivery of ions, and biomolecules at cellular scale. Here, a miniaturized OEIP device based on glass capillary fibers (c-OEIP) is implanted in a biological organism. The capillary form factor at the sub-100 mu m scale of the device enables it to be implanted in soft tissue, while its hyperbranched polyelectrolyte channel and addressing protocol allows efficient delivery of a large aromatic molecule. In the first example of an implantable bioelectronic device in plants, the c-OEIP readily penetrates the leaf of an intact tobacco plant with no significant wound response (evaluated up to 24 h) and effectively delivers the hormone abscisic acid (ABA) into the leaf apoplast. OEIP-mediated delivery of ABA, the phytohormone that regulates plants tolerance to stress, induces closure of stomata, the microscopic pores in leafs epidermis that play a vital role in photosynthesis and transpiration. Efficient and localized ABA delivery reveals previously unreported kinetics of ABA-induced signal propagation.

The coupling between charge accumulation in a conjugated polymer and the ionic charge compensation, provided from an electrolyte, defines the mode of operation in a vast array of different organic electrochemical devices. The most explored mixed organic ion-electron conductor, serving as the active electrode in these devices, is poly(3,4-ethyelenedioxythiophene) doped with polystyrelensulfonate (PEDOT:PSS). In this progress report, scientists of the Laboratory of Organic Electronics at Linkoping University review some of the achievements derived over the last two decades in the field of organic electrochemical devices, in particular including PEDOT:PSS as the active material. The recently established understanding of the volumetric capacitance and the mixed ion-electron charge transport properties of PEDOT are described along with examples of various devices and phenomena utilizing this ion-electron coupling, such as the organic electrochemical transistor, ionic-electronic thermodiffusion, electrochromic devices, surface switches, and more. One of the pioneers in this exciting research field is Prof. Olle Inganas and the authors of this progress report wish to celebrate and acknowledge all the fantastic achievements and inspiration accomplished by Prof. Inganas all since 1981.

Microbial electrochemical systems provide an environmentally-friendly means of energy conversion between chemical and electrical forms, with applications in wastewater treatment, bioelectronics, and biosensing. However, a major challenge to further development, miniaturization, and deployment of bioelectronics and biosensors is the limited thickness of biofilms, necessitating large anodes to achieve sufficient signal-to-noise ratios. Here we demonstrate a method for embedding an electroactive bacterium, Shewanella oneidensis MR-1, inside a conductive three-dimensional poly(3,4-ethylenedioxy thiophene): poly(styrenesulfonate) (PEDOT:PSS) matrix electropolymerized on a carbon felt substrate, which we call a multilayer conductive bacterial-composite film (MCBF). By mixing the bacteria with the PEDOT:PSS precursor in a flow-through method, we maintain over 90% viability of S. oneidensis during encapsulation. Microscopic analysis of the MCBFs reveal a tightly interleaved structure of bacteria and conductive PEDOT:PSS up to 80 mu m thick. Electrochemical experiments indicate S. oneidensis in MCBFs can perform both direct and riboflavin-mediated electron transfer to PEDOT:PSS. When used in bioelectrochemical reactors, the MCBFs produce 20 times more steady-state current than native biofilms grown on unmodified carbon felt. This versatile approach to control the thickness of bacterial composite films and increase their current output has immediate applications in microbial electrochemical systems, including field-deployable environmental sensing and direct integration of microorganisms into miniaturized organic electronics.

Conjugated polymers have been increasingly considered for the design of conductive materials in the field of regenerative medicine. However, optimal scaffold properties addressing the complexity of the desired tissue still need to be developed. The focus of this study lies in the development and evaluation of a conductive scaffold for bone tissue engineering. In this study PEDOT:PSS scaffolds were designed and evaluated in vitro using MC3T3-E1 osteogenic precursor cells, and the cells were assessed for distinct differentiation stages and the expression of an osteogenic phenotype. Ice-templated PEDOT:PSS scaffolds presented high pore interconnectivity with a median pore diameter of 53.6 +/- 5.9 mu m and a total pore surface area of 7.72 +/- 1.7 m(2).g(-1). The electrical conductivity, based on I-V curves, was measured to be 140 mu S.cm(-1) with a reduced, but stable conductivity of 6.1 mu S.cm(-1) after 28 days in cell culture media. MC3T3-E1 gene expression levels of ALPL, COL1A1 and RUNX2 were significantly enhanced after 4 weeks, in line with increased extracellular matrix mineralisation, and osteocalcin deposition. These results demonstrate that a porous material, based purely on PEDOT:PSS, is suitable as a scaffold for bone tissue engineering and thus represents a promising candidate for regenerative medicine. Statement of Significance Tissue engineering approaches have been increasingly considered for the repair of non-union fractions, craniofacial reconstruction or large bone defect replacements. The design of complex biomaterials and successful engineering of 3-dimensional tissue constructs is of paramount importance to meet this clinical need. Conductive scaffolds, based on conjugated polymers, present interesting candidates to address the piezoelectric properties of bone tissue and to induce enhanced osteogenesis upon implantation. However, conductive scaffolds have not been investigated in vitro in great measure. To this end, we have developed a highly porous, electrically conductive scaffold based on PEDOT:PSS, and provide evidence that this purely synthetic material is a promising candidate for bone tissue engineering. (C) 2017 Acta Materialia Inc. Published by Elsevier Ltd.

Electronic plants, e-Plants, are an organic bioelectronic platform that allows electronic interfacing with plants. Recently we have demonstrated plants with augmented electronic functionality. Using the vascular system and organs of a plant, we manufactured organic electronic devices and circuits in vivo, leveraging the internal structure and physiology of the plant as the template, and an integral part of the devices. However, this electronic functionality was only achieved in localized regions, whereas new electronic materials that could be distributed to every part of the plant would provide versatility in device and circuit fabrication and create possibilities for new device concepts. Here we report the synthesis of such a conjugated oligomer that can be distributed and form longer oligomers and polymer in every part of the xylem vascular tissue of a Rosa floribunda cutting, forming long-range conducting wires. The plant’s structure acts as a physical template, whereas the plant’s biochemical response mechanism acts as the catalyst for polymerization. In addition, the oligomer can cross through the veins and enter the apoplastic space in the leaves. Finally, using the plant’s natural architecture we manufacture supercapacitors along the stem. Our results are preludes to autonomous energy systems integrated within plants and distribute interconnected sensor-actuator systems for plant control and optimization

A recently synthesized self-doped conducting oligomer, salt of bis[3,4-ethylenedioxythiophene]3thiophene butyric acid, ETE-S, is a novel promising material for green energy applications. Recently, it has been demonstrated that it can polymerize in vivo, in plant systems, leading to a formation of long-range conducting wires, charge storage and supercapacitive behaviour of living plants. Here we investigate the morphology of ETE-S combining the experimental characterisation using Grazing Incidence Wide Angle X-ray Scattering (GIWAXS) and atomistic molecular dynamics (MD) simulations. The GIWAXS measurements reveal a formation of small crystallites consisting of π–π stacked oligomers (with the staking distance 3.5 Å) that are further organized in h00 lamellae. These experimental results are confirmed by MD calculations, where we calculated the X-ray diffraction pattern and the radial distribution function for the distance between ETE-S chains. Our MD simulations also demonstrate the formation of the percolative paths for charge carriers that extend throughout the whole structure, despite the fact that the oligomers are short (6–9 rings) and crystallites are thin along the π–π stacking direction, consisting of only two or three π–π stacked oligomers. The existence of the percolative paths explains the previously observed high conductivity in in vivo polymerized ETE-S. We also explored the geometrical conformation of ETE-S oligomers and the bending of their aliphatic chains as a function of the oligomer lengths.

A recently developed water-soluble self-doped sodium salt of bis[3,4-ethylenedioxythiophene] 3thiophene butyric acid (ETE-S) is electropolymerized and characterized by means of spectroelectrochemistry, electron paramagnetic resonance spectroscopy, and cyclic voltammetry, combined with the density functional theory (DFT) and time-dependent DFT calculations. The focus of the studies is to underline the nature of the charge carriers when the electrochemically polymerized ETE-S films undergo a reversible transition from reduced to electrically conductive oxidized states. Spectroelectrochemistry shows clear distinctions between absorption features from reduced and charged species. In the reduced state, the absorption spectrum of ETE-S electropolymerized film shows a peak that is attributed to HOMO. LUMO transition. As the oxidation level increases, this peak diminishes and the absorption of the film is dominated by spinless bipolaronic states with some admixture of polaronic states possessing a magnetic momentum. For fully oxidized samples, the bipolaronic states fully dominate, and the features in the absorption spectra are related to the drastic changes of the band structure, exhibiting a strong decrease of the band gap when a polymeric film undergoes oxidation.

The roots, stems, leaves, and vascular circuitry of higher plants are responsible for conveying the chemical signals that regulate growth and functions. From a certain perspective, these features are analogous to the contacts, interconnections, devices, and wires of discrete and integrated electronic circuits. Although many attempts have been made to augment plant function with electroactive materials, plants’ “circuitry” has never been directlymerged with electronics. We report analog and digital organic electronic circuits and devices manufactured in living plants. The four key components of a circuit have been achieved using the xylem, leaves, veins, and signals of the plant as the template and integral part of the circuit elements and functions. With integrated and distributed electronics in plants, one can envisage a range of applications including precision recording and regulation of physiology, energy harvesting from photosynthesis, and alternatives to genetic modification for plant optimization.