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Glucose-Sensitive Biohybrid Roots for Supercapacitive Bioanodes
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  • Gwennaël Dufil*
    Gwennaël Dufil
    Department of Science and Technology, Laboratory of Organic Electronics, Linköping University, Bredgatan 33, Norrkoping 601 74, Sweden
    *Email: [email protected]
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    Orcidhttps://orcid.org/0000-0001-5213-9002
  • Julie Pham
    Julie Pham
    Universite Paris Cite, ITODYS, CNRS UMR 7086, 15 rue J.-A. de Baïf, Paris, île-de-France F-750 13, France
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  • Chiara Diacci
    Chiara Diacci
    Department of Science and Technology, Laboratory of Organic Electronics, Linköping University, Bredgatan 33, Norrkoping 601 74, Sweden
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  • Yohann Daguerre
    Yohann Daguerre
    Department of Forest Genetics and Plant Physiology, Umeå Plant Science Centre, Linnéus väg 6, Umeå 901 36, Sweden
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  • Daniele Mantione
    Daniele Mantione
    POLYMAT, University of the Basque Country, Avenida Tolosa 72, Donostia-San Sebastian 200 18, Spain
    IKERBASQUE, Basque Foundation for Science, María Díaz de Haro 3, Bilbao 480 13, Spain
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    Orcidhttps://orcid.org/0000-0001-5495-9856
  • Samia Zrig
    Samia Zrig
    Universite Paris Cite, ITODYS, CNRS UMR 7086, 15 rue J.-A. de Baïf, Paris, île-de-France F-750 13, France
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  • Torgny Näsholm
    Torgny Näsholm
    Department of Forest Ecology and Management, Umeå Plant Science Centre, Skogsmarksgränd 17, Umeå 901 87, Sweden
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  • Mary J. Donahue
    Mary J. Donahue
    Department of Science and Technology, Laboratory of Organic Electronics, Linköping University, Bredgatan 33, Norrkoping 601 74, Sweden
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  • Vasileios K. Oikonomou
    Vasileios K. Oikonomou
    Department of Science and Technology, Laboratory of Organic Electronics, Linköping University, Bredgatan 33, Norrkoping 601 74, Sweden
    Department of Science and Technology, Wallenberg Wood Science Center, Linköping University, Bredgatan 33, Norrkoping 601 74, Sweden
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  • Vincent Noël
    Vincent Noël
    Universite Paris Cite, ITODYS, CNRS UMR 7086, 15 rue J.-A. de Baïf, Paris, île-de-France F-750 13, France
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    Orcidhttps://orcid.org/0000-0003-3901-8358
  • Benoit Piro
    Benoit Piro
    Universite Paris Cite, ITODYS, CNRS UMR 7086, 15 rue J.-A. de Baïf, Paris, île-de-France F-750 13, France
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  • Eleni Stavrinidou*
    Eleni Stavrinidou
    Department of Science and Technology, Laboratory of Organic Electronics, Linköping University, Bredgatan 33, Norrkoping 601 74, Sweden
    Department of Forest Genetics and Plant Physiology, Umeå Plant Science Centre, Linnéus väg 6, Umeå 901 36, Sweden
    Department of Science and Technology, Wallenberg Wood Science Center, Linköping University, Bredgatan 33, Norrkoping 601 74, Sweden
    *Email: [email protected]
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    Orcidhttps://orcid.org/0000-0002-9357-776X
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ACS Applied Bio Materials

Cite this: ACS Appl. Bio Mater. 2024, 7, 12, 8632–8641
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https://doi.org/10.1021/acsabm.4c01425
Published December 3, 2024

Copyright © 2024 The Authors. Published by American Chemical Society. This publication is licensed under

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Abstract

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Plants as living organisms, as well as their material–structural components and physiological processes, offer promising elements for developing more sustainable technologies. Previously, we demonstrated that plants could acquire electronic functionality, as their enzymatic activity catalyzes the in vivo polymerization of water-soluble conjugated oligomers. We then leveraged plant-integrated conductors to develop biohybrid energy storage devices and circuits. Here, we extend the concept of plant biohybrids to develop plant-based energy-harvesting devices. We demonstrate plant biohybrids with modified roots that can convert common root exudates, such as glucose, to electricity. To do so, we developed a simple one-step approach to convert living roots to glucose-sensitive electrodes by dipping the root in a solution of the conjugated trimer ETE-S and the enzyme glucose dehydrogenase flavin adenine dinucleotide. The biohybrid device responds to glucose concentrations down to 100 μM while it saturates at 100 mM. The performance of our approach was compared with a classic mediator-based glucose biosensor functionalization method. While the latter method increases the stability of the sensor, it results in less sensitivity and damages the root structure. Finally, we show that glucose oxidation can be combined with the volumetric capacitance of p(ETE-S)-forming devices that generate current in the presence of glucose and store it in the same biohybrid root electrodes. The plant biohybrid devices open a pathway to biologically integrated technology that finds application in low-power devices, for example, sensors for agriculture or the environment.

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Introduction

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Plants are remarkably diverse organisms that are essential for sustaining life in our ecosystem and for the prosperity of the planet. The inherent processes and structures of plants can also be leveraged for technological purposes contributing to the development of more sustainable technologies. (1) Plants are carbon-negative as they capture more carbon dioxide than they emit, and they convert sunlight into chemical energy while releasing oxygen. Furthermore, plants have many other characteristics that were optimized via evolution such as responsiveness and acclimation to their environment, self-repair and regeneration, a plethora of biocatalytic pathways, and hierarchical structures. (2) To enable plant-based technological systems, functional materials or devices are interfaced with plants, forming biohybrids that combine natural and artificial characteristics.
The natural processes of plants have been explored for energy-harvesting. Biofuel cells can convert naturally produced sugars and oxygen to electricity. In most examples, macroscopic electrodes prefunctionalized with enzymes and redox mediators were inserted directly into sugar-rich plant tissues such as the ground tissue of succulent plants or even fruits. (3−7) However, these systems had a limited lifetime due to enzyme degradation and were highly invasive, as the insertion of the electrode creates a large wound in the plant tissues. Plant microbial fuel cells consist of a less invasive energy-harvesting device where electrodes are placed in the rhizosphere area, where roots release chemicals for bacterial symbiosis, to generate electricity. (8) These devices produce enough energy to power small devices but require microbiologists to design an efficient plant/bacteria association and can be applied only with waterlogged plants. (9,10) Apart from their chemical environment, plant movements were also leveraged for energy-harvesting. Biohybrid triboelectric generators produce electricity via the electrification phenomenon when natural and artificial leaves come in contact due to the wind. (11−15) Artificial leaves were simply attached to the plant, rendering this approach noninvasive and these devices long lasting.
Energy storage has also been explored in plant biohybrids. (16−20) We harnessed the plants own biocatalytic machinery to grow charge storage electrodes directly in the rich electrolytic plant tissue and fabricated supercapacitors within the plant structure. (19) Specifically, we found that water-soluble conjugated oligomers polymerize in vivo due to the endogenous peroxidase enzymes of the plants, which are stress regulatory enzymes that tune the cell wall density through the synthesis of biopolymers. (21,22) By distributing trimers via the vasculature or simply by watering the plants, we formed integrated conductors in the vascular tissue of plant cuttings or along the root system of intact plants. The in vivo formed charge storage electrodes had high conductivity and charge storage capacity, enabling seamlessly integrated supercapacitors in living plants. (20)
Other plant biohybrid systems aim at sensing. Most examples of plant sensor devices rely on nanomaterials that are introduced into the plant via leaf infiltration and root uptake. The nanoparticles are designed to interact with targeted analytes and to produce a readable output such as a change in fluorescence. (23) This approach has been used to monitor endogenous biomolecules such as H2O2 or analytes that are present in the soil, for example, nitroaromatic compounds and arsenic. (24−27) In the latter case, the plant collects and concentrates the analyte of interest into the functionalized leaf via its internal microfluidic network, the vascular tissue, which connects the root to the shoot.
Among plant organs, the root system is particularly attractive for building biohybrid systems. Roots are responsible for the uptake of nutrients and minerals required for the plant development but also release primary and secondary metabolites into the soil as exudates. (28) These exudates have a dual function: lubricating the soil to facilitate root navigation and orchestrating the formation of the rhizosphere that includes various symbiotic microorganisms. (29) Exudates also correlate with the physiological status of the plants and their response to various environmental stimuli. Sensors integrated in the root system of the plant can therefore provide valuable information on the dynamic processes related to plant heath and its interaction with the local environment. (30,31)
In this work, we developed biohybrid electrodes based on living plant roots that can convert glucose to current, opening possibilities for sensing and energy-harvesting applications. Leveraging the oxidative environment of the root, we fabricated in a single step a glucose-sensitive root by combining the in vivo polymerization of the conjugated trimer 4-[2-{2,5-bis(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)thiophen-3-yl}ethoxy]butane-1-sulfonate sodium salt (ETE-S) with the simultaneous immobilization of glucose dehydrogenase flavin adenine dinucleotide (GDH-FAD) in the polymer matrix. We then compared this simple approach with a classical one where glucose oxidase is immobilized in a redox hydrogel at the root-electrode surface. (32) Both approaches led to glucose sensitivity with differences in the dynamic range, stability, and effect on the root morphology. Finally, we combined the biocatalytic current generation with the charge storage ability of the p(ETE-S) layer, demonstrating a multifunctional biohybrid root.

Results and Discussion

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The conjugated trimer ETE-S polymerizes on the root epidermis due to the presence of endogenous peroxidase enzymes forming an integrated electroactive layer with conducting and capacitive properties. (21,22) In this study, we aimed to advance the functionality of the biohybrid roots by introducing electrocatalytic activity, specifically glucose sensitivity, via the in vivo polymerization process. We hypothesized that by having a glucose-sensing enzyme within the solution of the ETE-S monomer, the enzyme will be entrapped in the conducting matrix, while the p(ETE-S) layer is formed (Figure 1A). We selected GDH-FAD as it is one of the glucose oxidase enzymes that shows electron transfer without the need for a mediator. (33,34) We therefore simply immersed roots of Phaseolus vulgaris (common bean plant) in a mixture of GDH-FAD and ETE-S for 24 h (Figure 1B).

Figure 1

Figure 1. (A) Schematic representation of the root biofunctionalization method using ETE-S mixed with GDH-FAD. GDH-FAD is entrapped in the p(ETE-S) layer, while it is formed via in vivo polymerization. The biofunctionalized root then acquires glucose sensitivity. (B) The one-step process consists of polymerizing ETE-S in the same medium that contains the GDH-FAD enzyme. The two-step process consists of first polymerizing ETE-S on a root for 24 h and then transferring the root into a GDH-FAD solution for 24 h more. (C) Chronoamperometric curve for glucose detection comparing the one-step process (red, n = 6) with the two-step process (black, n = 3) for a potential of +0.5 V vs Ag/AgCl. (D) Cyclic voltammogram in 10 mM KCl at 5 mV s–1 vs Ag/AgCl of a p(ETE-S) root (dashed black line) and p(ETE-S)/GDH-FAD (one-step process) before (solid black line) and after the addition of 100 mM glucose (red).

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A dark coating was formed on the root surface, indicating the in vivo polymerization of ETE-S into p(ETE-S). (21) The roots were then mounted in a three-electrode setup for evaluating their glucose response by chronoamperometry and cyclic voltammetry (Figure 1C,D). We applied +0.5 V to the root electrode for chronoamperometry, as this potential resulted in a higher generated current without overoxidation of p(ETE-S) over time (Figure S1). The normalized response- eq 1 -showed that the root became glucose-sensitive. The absence of a soluble mediator in the system points out a direct electron transfer between GDH-FAD and p(ETE-S). Microbial GDH-FAD, like the one used in this study, has been shown to support direct electron transfer when the electrode is made of carbon nanotubes or graphene that reach very close proximity with the FAD subunit of the enzyme. (35−37) Additionally, GDH-FAD is oxygen-independent and does not generate H2O2 as a byproduct. (38) Therefore, in the presence of electrolyte and glucose, the current collected by the p(ETE-S) electrode can only come from the enzyme to the conjugated polymer.
Current was generated from 100 μM glucose with a linear normalized response for glucose concentrations between 1 and 100 mM. To verify that the enzyme was entrapped during the polymerization process and not just adsorbed on the polymer surface, we performed control experiments where p(ETE-S) roots were immersed in the enzyme solution after the p(ETE-S) layer formation (Figure 1B). In this case, no response to glucose was observed (Figure 1C). With cyclic voltammetry, we examined how the electrochemical properties of the roots were affected by the GDH-FAD entrapment. p(ETE-S) roots behave as capacitive electrodes in an electrochemical window delimited by the polymer overoxidation and oxygen reduction (Figure 1D). (19,39) We observed that the capacitance is lower for the p(ETE-S)/GDH-FAD roots than for the p(ETE-S) roots possibly due to the presence of the enzyme in the conducting polymer matrix. When glucose was added to the system, an increase in current was observed for roots with enzymes. In the absence of glucose, we do not observe any redox peaks arising from the enzyme cofactor. This observation indicates that electron transfer may not occur via redox reactions. A reported work from Filipiak et al. showed a similar behavior with GDH-FAD on a single graphene sheet while Ishida et al. observed similar results with carbon nanotube electrodes. (34,36) The latter group proposed that direct electron transfer occurs through electron tunneling, which relies on the proximity of the two redox centers, in our case p(ETE-S) and GDH-FAD. (35) We did not investigate the mechanism that drives the enzyme entrapment and interaction with the polymer matrix in this work, but we believe that this would improve the device performance.
We then compared the one-step functionalization process with a classical mediator-based approach that is commonly used in the field of biosensors and biofuel cells. (32,40,41) In this approach, glucose oxidase (GOx) is immobilized within a redox hydrogel: polyvinyl imidazole-osmium 2,2′-bipyridine dichloride (PVI–Os(Bpy)2Cl2) -PVI–Os in the text. In this electrochemical cascade, glucose will be oxidized by GOx, while the osmium redox hydrogel will transfer electrons from the reduced enzyme to the working electrode- the p(ETE-S) root (Figure 2A). The osmium bipyridine complexes are a well-established choice for GOx mediators as they are fast and reversible systems. (32) In addition, osmium redox systems offer a tunable window, around 400 mV vs SCE (170 mV vs Ag/AgCl), which is in the range of the GOx oxidation potential (+100 mV vs Ag/AgCl). (42)

Figure 2

Figure 2. Root biofunctionalization method using a redox hydrogel matrix composed of GOx, and PVI–Os crosslinked with PEGDE and drop-cast on a p(ETE-S) root. (A) Cyclic voltammogram showing the redox activity of 1 mM PVI–Os with an electropolymerized p(ETE-S) on ITO as the working electrode in 0.1 M KCl vs Ag/AgCl at scan rates of 25 mV s–1 (dark red), 10 mV s–1 (red), and 5 mV s–1 (orange). Cascade reaction of glucose oxidation and transport of electrons from the redox mediator to the p(ETE-S) root. (B) Cyclic voltammogram of p(ETE-S) roots (black dotted line), p(ETE-S)/PVI-Os/PEGDGE/GOx before (black) and after the addition of 100 mM glucose (red), in 10 mM KCl electrolyte with a scan rate of 5 mV s–1 vs Ag/AgCl. (C) Chronoamperometry of p(ETE-S) root (black), p(ETE-S)/PVI–Os/PEGDGE root (yellow), p(ETE-S)/GOx/PEGDGE root (red), and p(ETE-S)/PVI–Os/GO/PEGDGE root (brown) with successive additions of glucose. The concentration after each addition is indicated above the arrow. The p(ETE-S) root potential is fixed at +0.5 V vs Ag/AgCl.

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Initially, the electrochemical performance of the redox mediator PVI–Os was evaluated on p(ETE-S) films electropolymerized on ITO-coated glass slides. From the cyclic voltammogram, the potential of the osmium redox couple E0 (Os2+/Os3+) was found at 229 mV vs Ag/AgCl, which suggests that the redox polymer can act as a mediator for the glucose oxidase enzyme (Figure 2A). The anodic and cathodic peak currents increase linearly with the square root of the scan rate indicating that the osmium complex is able to freely diffuse to the working electrode even though it is branched on the PVI (Figure S2). (43) Then, to test the electrochemical cascade, GOx and glucose were added to the solution (Figure S3B), and indeed, a catalytic current was generated. As a control, we performed the same experiment without the p(ETE-S) film by having a neat ITO as the working electrode. In that case, we generated a 10 times lower current (Figure S3A). Since the mediator is in solution, the current depends on the diffusion layer around the electrode surface; the p(ETE-S) film increases the surface area of the electrode and therefore the interaction with the mediator.
To develop the biohybrid glucose-sensitive electrodes, we first functionalized the roots of young bean plants with p(ETE-S) to form an integrated conductor and biofunctionalized the conducting roots by casting a matrix containing GOx and PVI–Os crosslinked with poly(ethylene glycol) diglycidyl ether (PEGDGE). The epoxy rings of PEGDGE covalently bind the amine groups at the surface of the enzyme. (32,44) The roots were then mounted in a three-electrode setup for evaluating their glucose sensitivity using cyclic voltammetry and chronoamperometry.
Figure 2B shows the cyclic voltammogram of the p(ETE-S) roots with and without the addition of a glucose-sensing matrix. The biofunctionalized roots were less capacitive than the p(ETE-S) roots. The black solid line peaks at 347 and −41 mV- respectively in the anodic and cathodic currents- signifying that the redox hydrogel can be addressed with the p(ETE-S) root electrode. The peak-to-peak difference (ΔEp), however, was larger than in the case where PVI–Os was in solution, signifying that a higher potential must be applied for the redox reaction to take place; There is a higher resistivity for the electron transferwith the p(ETE-S)-ITO electrode.
When we added glucose to the solution, we observed a high catalytic activity resulting in high current generation. At the same time, the volumetric capacitance of p(ETE-S) was lost, with a visible decrease in the cyclic voltammogram width in the noncatalytic region. This shows that the modified p(ETE-S) root during glucose oxidation no longer acts as a volumetric capacitor but only as a resistor. The capacitance of the electrode recovers slowly during cycling, while the catalytic current decreases (Figure S4).
To assess the response of the biofunctionalized root to glucose, we performed chronoamperometry in solution with an increasing amount of glucose. We observed a linear increase in the current for glucose concentrations ranging from 4 to 14 mM (Figure 2C and Figure S5). To verify that all components of the biofunctionalization matrix were taking part in the reaction, we performed a series of sensing experiments for roots modified with PEGDGE/PVI–Os, PEGDGE/GOx, and PVI–Os/GOx/PEGDGE. No current increase was observed upon glucose addition for nonmodified p(ETE-S) roots- in the absence of GOx- while when p(ETE-S) roots were modified with GOx crosslinked with PEGDGE, we observed a reduction current 10 times lower than the one generated by the oxidation of glucose with p(ETE-S)/PVI–Os/GOx/PEGDGE (Figure 2C). It has been shown that conducting polymers such as PEDOT can favor the reduction of oxygen into hydrogen peroxide but not in potential windows in which we were carrying out the experiments. (45) More experiments should be carried out to elucidate the source of the reduction current.
Next, we investigated the performance and stability of p(ETE-S)/PVI–Os/GOx/PEGDGE and p(ETE-S)/GDH-FAD roots while still being attached to the plant (Figure 3A). To do so, we developed a setup where the biofunctionalized root is placed in an electrochemical cell with 10 mM KCl while the rest of the root system is placed in a sugar-free 1/2 MS MES medium at pH 5.8. The glucose response of the functionalized roots was assessed on the day of the biofunctionalization, after 1 day, and after 1 week. Plants were placed back in the hydroponics growth chamber after each measurement. The biohybrid root was biased at +0.5 V vs Ag/AgCl, and- after the current stabilized- the glucose concentration of the solution was increased stepwise from 100 nM to 1M. In the case of the p(ETE-S)/PVI–Os/GOx/PEGDGE root, we observed a glucose response at 1 mM, saturation at 100 mM, and a decrease at 1 M glucose concentration (Figure 3B). Sensing curves corresponding to the day of functionalization and 1 day after showed similar responses. However, after a week, a decrease in the performance was observed, indicating that the activity of the enzyme was reduced.

Figure 3

Figure 3. Glucose sensing in intact plants. (A) Image of the sensing measurement setup with an intact plant. A 2-week-old plant is placed in a 1/2 MS MES nutrient medium without sugar, while the biofunctionalized root (still attached on the plant) is placed in an electrolytic cell with 10 mM KCl. (B) Normalized response of glucose sensing measurement of a p(ETE-S)/PVI–Os/GOx/PEGDGE root at +0.5 V vs Ag/AgCl. Measurement on day 1 (red), day 2 (blue), and 1 week after biofunctionalization (black). (C) Normalized response of glucose sensing measurement of a p(ETE-S)/GDH-FAD root at +0.5 V vs Ag/AgCl. Measurement on day 1 (red), day 2 (blue), and 1 week after biofunctionalization (black). Standard deviation obtained for N = 6 replicates.

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Figure 3C shows that roots with p(ETE-S)/GDH-FAD produce a 4 times lower normalized response than the p(ETE-S)/PVI–Os/GOx/PEGDGE roots. We speculate that in the first case the electron transfer to the p(ETE-S) electrode is limited as it relies on the physical distance between the enzyme cofactor and the conducting layer. For the p(ETE-S)/PVI–Os/GOx/PEGDGE roots, on the other hand, the redox mediator facilitates the transfer from the enzyme cofactor to the electrode. However, p(ETE-S)/GDH-FAD roots showed a response to glucose starting at 100 μM concentration but decreasing 1 day after the functionalization (Figure 1C). This indicates that the enzyme is either no longer active or present in the vicinity of the p(ETE-S) network of the root. The literature shows that glucose dehydrogenase activity notably decreases under continuous operation at room temperature. (46,47) Despite the difference in performance and stability, SEM micrographs (Figure S6) revealed that in p(ETE-S)/PVI–Os/GOx/PEGDGE roots, the crosslinked matrix altered the root morphology. In contrast, in p(ETE-S)/GDH-FAD, the root structure was preserved. Maintaining the root morphology and function is vital for nutrient uptake and exudation. Root exudation is particularly relevant, as it involves the release of glucose and other sugars in the soil that could be directly oxidized by the biohybrid roots. To evaluate the sugar exudation of the bean plants, we collected exudates from adult plants and quantified their glucose and sucrose concentration using gas chromatography coupled with mass spectrometry (GC–MS; Methods in the Supporting Information). We found that sucrose exudation was 1 order of magnitude higher than that of glucose with respective values of 34.88 and 1.62 nM h–1 per plant (Figure S7). No significant difference in the exudation was found between the control and ETE-S root systems, indicating that ETE-S functionalization does not negatively affect the root exudation of glucose and sucrose, possibly since glucose and sucrose have no electric charge. The biohybrid roots generate notable current when the glucose concentration is higher than 100 μM. This concentration can be reached in 17 min for sucrose and 370 min (6 h) for glucose in 100 μL of growth medium. Therefore, the biohybrid roots can be used for sensing or energy-harvesting using a miniaturized compartment or by enhancing the glucose sensitivity.
So far, we have established that roots modified with glucose oxidase enzymes can catalyze the oxidation of glucose. As the next step, we aimed to combine the biocatalytic current generation with the charge storage ability of the p(ETE-S) layer on the roots. To demonstrate the dual function of the enzyme-modified roots, we performed galvanostatic charge–discharge characterization of a pair of roots in a supercapacitor configuration with or without glucose present in the electrolyte (Figure 4A). We characterized the response of a supercapacitor made with roots modified only with p(ETE-S). As we have shown previously, p(ETE-S) is a mixed ionic/electronic conductor, (19) and p(ETE-S) roots show capacitive charging without the generation of a faradic current. We calculated the capacitance from the linear discharge curves- area with a constant capacitance-for -5 μA applied, -. and the equivalent series resistance (ESR) from the ohmic drop of the discharge curve.

Figure 4

Figure 4. ETE-S/GDH-FAD roots are supercapacitive bioanodes. (A) Schematic representation of the experimental setup for the galvanostatic charge/discharge characterization of two roots functionalized with 1 mM ETE-S + 5 mg mL–1 GDH-FAD. (B) Galvanostatic charge/discharge curve for a ±5 μA applied current for a voltage range of [0, +0.5] V. The electrolyte used here is either 10 mM KCl (black) or 10 mM KCl electrolyte +100 mM glucose (red) for 2 roots functionalized with ETE-S (upper graph) and 2 roots functionalized with ETE-S + GDH-FAD (lower graph).

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The capacitance of the p(ETE-S) supercapacitor was 1.2 mF and decreased to 1.1 mF with the addition of glucose. p(ETE-S)/GDH-FAD roots exhibited lower capacitance values of 1 and 0.80 mF before and after glucose addition, respectively (Figure S8). This correlates with the conductivity recorded with the 4-point probe measurement of p(ETE-S) roots and p(ETE-S)/GDH-FAD roots (49 ± 31 and 2 ± 1 S cm–1, respectively; Figure S9), as the conductivity and capacitance depend on the coupling between electronic and ionic carriers within the conjugated polymer matrix. (48,49)
p(ETE-S)/GDH-FAD roots indicate a larger ESR (34 kΩ) than the p(ETE-S) root supercapacitors (6 kΩ), which confirms the lower conductivity of our modified root; it is harder for the electronic charges to cross the polymer with the embedded enzyme present in the structure.
When we added glucose in the electrolyte, we observed different charging responses with a plateau developing when the voltage became higher than the oxidation potential of the GDH-FAD enzyme. Overall, we can conclude that the biofunctionalized roots demonstrate a dual function that combines both current generation via glucose oxidation and the charge storage capacity with the p(ETE-S) mixed conducting layer.

Conclusions

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In this work, we demonstrate an elegant method to produce in one step an electronic root that converts glucose to current by simply placing a root in a solution with the conjugated trimer ETE-S and the glucose dehydrogenase enzyme (GDH-FAD). The endogenous peroxidase enzymes on the root epidermis catalyze the polymerization of ETE-S to a conducting layer that, at the same time, entraps the enzyme. We show clear glucose oxidation catalyzed by the enzyme and the collection of the electronic charge via the self-organized p(ETE-S) layer on the root epidermis. We then compared the performance of p(ETE-S)/GDH-FAD with p(ETE-S) roots that were functionalized with a redox mediator hydrogel branched with glucose oxidase with PEGDE (PVI–Os/GOx/PEGDGE/p(ETE-S) roots). We found that while in the first case the sensitivity increased by 1 order of magnitude, overall lower currents were generated due to the absence of a mediator and the dependence on direct electron transfer from the enzyme to the electrode. GDH-FAD was also less stable than GOx as we observed a clear drop in sensitivity after 1 day. On the other hand, the PVI–Os/GOx/PEGDGE/p(ETE-S) root morphology was greatly impacted due to the use of a crosslinker in the biofunctionalization process . Osmium complex degradation in nature also poses inherent risks due to the toxicity of osmium oxides. (50) These facts could hinder the implementation of such devices in living plants. Furthermore, we quantified the sugar exudation of our plant model and found that the biohybrid roots can, in principle, be used to sense metabolites from living plants. However, further development would be needed to enhance the sensitivity and stability of the biohybrid roots. Finally, we combined the glucose oxidation catalytic matrix with the inherent volumetric capacitance of the p(ETE-S). We demonstrated that the root p(ETE-S)/GDH-FAD could dually extract the current from a glucose source and store the charge at the conjugated polymer bulk. Such devices could potentially find application in biofuel cells for powering low-energy consumption devices such as environmental sensors or local delivery systems. (51)

Methods

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Cyclic Voltammetry of 1 mM PVI–Os(Bpy)2Cl2 on ETE-S

An ITO-coated glass (Ossila) was placed in an electrochemical cell (BMM EC 15 ML, Redox.me) and used as the working electrode with a Pt wire counter electrode and 3 M KCl-saturated Ag/AgCl as the reference electrode. For the electropolymerization of ETE-S, a 1 mM ETE-S solution in 0.1 M KCl was used and a chronoamperometric deposition was performed (+0.4 V vs Ag/AgCl) for 500 s. After deposition, the cell was rinsed several times and the electrolyte was replaced by 1 mM PVI–Os(Bpy)2Cl2 (Mw = 1150.9 g mol–1) diluted in 0.1 M KCl. The solution was purged for 15 min using N2 gas prior measurements.

Plant Growth

Phaseolus vulgaris seeds (Impecta Fröhandel) were germinated in peat-based cubes for 5 days (Root riot) in the dark at 23 °C. After germination, plants were transferred to a hydroponic chamber filled with 0.2% vol/tap water commercial nutrient solution (Nelson Garden). Hydroponics chambers were placed for 9 days in a controlled growth greenhouse environment with the following conditions: 23–25 °C, humidity 50–60%, and 12h light/dark cycles with neon lights providing a light intensity of 80–100 mmol m–2 s–1.

Root Biofunctionalization with Glucose Oxidase, PVI–Os(Bpy)2Cl2, and PEGDGE

One root of the plant was isolated and placed in 0.5 mL of a solution of 1 mM ETE-S overnight. The next day, the root was removed, washed several times with DI water, and placed on a parafilm foil with a 20 μL drop of the biofunctionalization medium following the protocol from Taylor et al. (32) and allowed to dry overnight. The biofunctionalization medium consists of 5 μL of 5.6 mg mL–1 PEGDGE (Mn= 500 Da, Sigma-Aldrich), 5 μL of 16 mg mL–1 glucose oxidase from Aspergillus niger (Type X–S 100–250 kU g–1 solid, Sigma-Aldrich), and 10 μL of 20 mg mL–1 PVI–Os(Bpy)2Cl2 (Mw = 1150.9 g mol–1, Paris Diderot University). The next day, the root was washed several times and used directly for the glucose-sensing experiments.

Root Biofunctionalization with GDH-FAD

One root was isolated and placed overnight in 0.5 mL of a solution containing 1 mM ETE-S and 5 mg mL–1 GDH-FAD (500 U mg–1, GLD- 3, BBI solutions). The next day, the root was washed 5 times with DI water before being used for the glucose-sensing experiments.

Biohybrid Root Electrical Contact

We achieved contact with the root using micropositioners with a Au-plated tungsten probe (50 μm tip) from Quarter Research (model XYZ300). Roots were placed on a glass Petri dish with perpendicularly aligned carbon fibers as contact electrodes for the roots. Tungsten probes coated with carbon paste, which improve the smoothness of the tip, were gently positioned on top of the carbon fiber to electrically address them. The probe was brought closer to the carbon fiber with a stereomicroscope to ensure soft contact and avoid going through the root sample.

Glucose Sensing Setup

The 3D printed electrolytic cell (PLA, AA 0.4, scheme available in SI) was placed in a square Petri dish filled with polydimethylsiloxane (PDMS, Sylgard 184, Dow Corning, 10:1) and cured overnight at 50 °C. Kapton tape was used to delimit the PDMS areas. The day after, the plant was attached to a stand and immersed in a 1/2 MS MES medium on the half of the Petri dish without PDMS. The counter/reference electrode was an Ag/AgCl electrode (2.0 × 4 mm, World Precision Instruments). The 1/2 MS MES was prepared from reagents purchased from Sigma-Aldrich. A micronutrient stock of 1 L was prepared with: 4.460 g of MnSO4·4H2O, 1.720 g of ZnSO4·7H2O, 1.240 g of H3BO3, 166 mg of KI, 50 mg of NaMoO4·2H2O, 5 mg of CoCl2·6H2O, and 5 mg of CuSO4·5H2O. A micronutrient stock solution of 1 L was prepared with: 367.08 mg of FeNaEDTA, 3.695 g of MgSO4·7H2O, and 1.7 g of KH2PO4. A 1 L stock solution of CaCl2 was prepared with 4.395 g of CaCl2·2H2O. A 1 L stock solution of KCl was prepared with 7.456g of KCl. To prepare 1 L of 1/2 MS MES, we added:2.5 mL of micronutrient stock, 50 mL of macronutrient stock, 50 mL of CaCl2 solution, 1.5 g of MES, 303 mg of KNO3, and 7 mL of KCl solution. The pH was adjusted to 5.8 before we completed the volume of 1L with Milli-Q water and sterilized the bottle in an autoclave.

Glucose Sensing

To obtain Figure 2C and Figure S5, the glucose sensing was performed as follows: sensing experiments were conducted in a 1 mL drop of 10 mM KCl with the addition of 100 μL of 50 mM d-glucose every 10 min in a 3-electrode setup. After 30 min, a 100 μL drop of d-glucose in 10 mM KCl was added to the initial drop every 10 min. To obtain Figure 3B and C, a serial dilution of d-glucose was performed from a 1 M stock solution to attain a concentration of 100 nM. After placing the root in the glucose sensing setup, the glucose concentration was increased by switching the previous concentration to the next one. Data were acquired using a source meter Keithley (K2600B) with a potential of +0.5 V vs Ag/AgCl applied to the functionalized root and a data recording frequency of 10 Hz. The normalized response was determined using the formula:
NR=(I−I0)I0
(1)

Collection of Sucrose and Glucose Exudate for GC–MS

Plants (Phaseolus vulgaris) were germinated for 4 days before being transferred to a hydroponic system in 1/2 MS MES medium (pH 5.8) + 3 mM KNO3. 20 days after germination, plants are placed in 15 mL of 1 mM ETE-S in 1/2 MS MES medium (pH 5.8) + KNO3 with or without 1 mM ETE-S. Plants were rinsed 24 h later in three consecutives baths of 300 mL of 0.1 mM CaCl2 and then transferred to 20 mL of 0.5 mM CaCl2 to collect the exudate for 24 h. 9 mL was kept in the vials, freeze-dried, and redissolved in 1 mL of DI water for GC–MS.

Galvanostatic Charge–Discharge Curve

Two roots treated with ETE-S or two roots treated with ETE-S/GDH-FAD were placed in parallel. A galvanostatic program created on Lab View was used to control a Keithley source meter (K2600B). A constant current of 5 μA was applied, and the current was then reversed when the accumulated potential reached +0.5 V. Charge and discharge curves were obtained in a 10 mM KCl electrolyte with and without the presence of 100 mM glucose. The capacitance of the root was then extracted from the linear regime of the discharge curve using the following formula:
C=i(t)(dV(t)dt)−1
(2)
where I is the applied current, and dV/dt is the slope obtained from a linear fit of the discharge curve.
The ESR was also extracted from the galvanostatic charge–discharge curve using the following formula:
ESR=ΔV2I
(3)
where I is the applied current and ΔV is the voltage difference measured at the drop of the discharge curve behavior.

Multielectrode Array Fabrication

A conformable multielectrode array (MEA) was fabricated to interface with the biohybrid roots. The array consists of 8 electrodes with dimensions of 450 μm × 200 μm in a 2 × 4 arrangement. The device was fabricated with microfabrication, as described previously. (52) Briefly, the substrate is a 2 μm thick, flexible parylene-C layer that is deposited by chemical vapor deposition (Diener electronic GmbH) on clean glass microscope slides. The glass was cleaned by ultrasonication first in 2% Hellmanex in DI water, followed by acetone and then isopropanol. The conductive interconnects were patterned using a lift-off process with a negative photoresist (AZ nLof 2070), an MA6 Suss mask aligner with an i-line filter, and a developer (AZ 326 MIF). Following patterning of the photoresist, a 5 nm titanium adhesion layer and 80 nm thick gold layer were thermally evaporated onto the substrates, and lift-off was carried out in acetone. The metal interconnects provided the electrode contacts and allowed electrical connection to the back-end contact pads for wiring upon completion. Next, an O2 plasma process was carried out (2 min, 50 W), and a second 1.5 μm thick insulating parylene-C layer was deposited over the metal lines (using an adhesion promoter in the deposition chamber, A-174). The outline shape of the probes was defined using reactive ion etching (RIE, O2/CF4 gases, 150 W) after patterning with a photoresist etch mask (AZ 10XT). The etch mask was removed with an acetone wash followed by an isopropanol rinse. Afterward, the electrode surface and back contact pads were opened using the same RIE etch process with the AZ 10XT photoresist etch mask to define and provide a back-end contact possibility. The etch mask was removed from the substrate using acetone and isopropanol, and finally, the completed probes were removed from the glass substrates using DI to assist the process.

Electropolymerization of ETE-S on Gold to Obtain the Gold Microarray

A MEA was fitted on a Kapton film to rigidify the contact area of the electrode.. Commercial nail polish was applied between the electrodes and contacts- front and back side of the array- to prevent electrolyte leakage to the contacts of the MEA. Next, the MEA was treated with UV/O3 for 2.5 min- 50 W power output and an O2 pressure of 0.6 bar (Plasma cleaner Zepto-W6). The polymerization of ETE-S was achieved using cyclic voltammetry between [−0.5 and +0.5]V vs Ag/AgCl for 8 cycles with a drop of 1 mM ETE-S in 10 mM KCl electrolyte.

4-Point Probe Measurement

The MEA was placed on the roots functionalized with p(ETE-S) and p(ETE-S)/GDH-FAD. A current I between 1 and 10 μA was then delivered between contacts 2 and 8 of the array using a source meter Keithley (K2600B) apparatus. The voltage drop ΔV between the two inner resistances was then recorded and used to calculate the sheet resistance with the following formula:
Rs=πln(2)ΔVI=4.53236ΔVI
(4)

Supporting Information

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsabm.4c01425.

  • Cyclic voltammetry of p(ETE-S) on ITO substrates, reduction/oxidation peaks of Os2+/Os3+ versus (v)1/2, cyclic voltammetry of PVI–Os catalysis on ITO with/without p(ETE-S), cyclic voltammetry of p(ETE-S) capacitance recovery after catalysis, normalized response of p(ETE-S)/PEGDE/Gox/PVI–Os with the addition of glucose, SEM image of the root morphology after enzyme deposition, metabolomics of root exudates, extracted data of charge/discharge curves, and precision of the 4-point probe measurements (PDF)

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Author Information

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  • Corresponding Authors
    • Gwennaël Dufil - Department of Science and Technology, Laboratory of Organic Electronics, Linköping University, Bredgatan 33, Norrkoping 601 74, Sweden;  Orcidhttps://orcid.org/0000-0001-5213-9002;  Email: [email protected]
    • Eleni Stavrinidou - Department of Science and Technology, Laboratory of Organic Electronics, Linköping University, Bredgatan 33, Norrkoping 601 74, Sweden;  Department of Forest Genetics and Plant Physiology, Umeå Plant Science Centre, Linnéus väg 6, Umeå 901 36, Sweden;  Department of Science and Technology, Wallenberg Wood Science Center, Linköping University, Bredgatan 33, Norrkoping 601 74, Sweden;  Orcidhttps://orcid.org/0000-0002-9357-776X;  Email: [email protected]
  • Authors
    • Julie Pham - Universite Paris Cite, ITODYS, CNRS UMR 7086, 15 rue J.-A. de Baïf, Paris, île-de-France F-750 13, France
    • Chiara Diacci - Department of Science and Technology, Laboratory of Organic Electronics, Linköping University, Bredgatan 33, Norrkoping 601 74, Sweden
    • Yohann Daguerre - Department of Forest Genetics and Plant Physiology, Umeå Plant Science Centre, Linnéus väg 6, Umeå 901 36, Sweden
    • Daniele Mantione - POLYMAT, University of the Basque Country, Avenida Tolosa 72, Donostia-San Sebastian 200 18, Spain;  IKERBASQUE, Basque Foundation for Science, María Díaz de Haro 3, Bilbao 480 13, Spain;  Orcidhttps://orcid.org/0000-0001-5495-9856
    • Samia Zrig - Universite Paris Cite, ITODYS, CNRS UMR 7086, 15 rue J.-A. de Baïf, Paris, île-de-France F-750 13, France
    • Torgny Näsholm - Department of Forest Ecology and Management, Umeå Plant Science Centre, Skogsmarksgränd 17, Umeå 901 87, Sweden
    • Mary J. Donahue - Department of Science and Technology, Laboratory of Organic Electronics, Linköping University, Bredgatan 33, Norrkoping 601 74, Sweden
    • Vasileios K. Oikonomou - Department of Science and Technology, Laboratory of Organic Electronics, Linköping University, Bredgatan 33, Norrkoping 601 74, Sweden;  Department of Science and Technology, Wallenberg Wood Science Center, Linköping University, Bredgatan 33, Norrkoping 601 74, Sweden
    • Vincent Noël - Universite Paris Cite, ITODYS, CNRS UMR 7086, 15 rue J.-A. de Baïf, Paris, île-de-France F-750 13, France;  Orcidhttps://orcid.org/0000-0003-3901-8358
    • Benoit Piro - Universite Paris Cite, ITODYS, CNRS UMR 7086, 15 rue J.-A. de Baïf, Paris, île-de-France F-750 13, France
  • Notes
    The authors declare no competing financial interest.

Acknowledgments

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This work was supported by the European Union’s Horizon 2020 research and innovation program under Grant Agreement No. 800926 (FET-OPEN-HyPhOE) by the European Union (ERC-2021-STG, 4DPhytoHybrid, 101042148) and the Swedish Research Council (VR-2017-04910). Additional funding was provided by the Swedish Government Strategic Research Area in Materials Science on Advanced Functional Materials at Linköping University (Faculty Grant SFO-Mat- LiU No. 2009-00971) and the Wallenberg Wood Science Center (KAW 2018.0452). The Swedish Metabolomics Centre, Umeå, Sweden (www.swedishmetabolomicscentre.se), is acknowledged for glucose and sucrose quantification by GC–MS. Figure 1A, Figure 1B, Figure 2A, Figure 3C, and Figure 4A were Created in BioRender. Stavrinidou, E. (2024) https:// BioRender.com/x79z879”.

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    Electronic plants, e-Plants, are an org. 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 manufd. org. electronic devices and circuits in vivo, leveraging the internal structure and physiol. 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 phys. template, whereas the plant's biochem. response mechanism acts as the catalyst for polymn. In addn., the oligomer can cross through the veins and enter the apoplastic space in the leaves. Finally, using the plant's natural architecture we manuf. 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.
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  17. 17
    Liang, J.; Yu, M.; Liu, J.; Yu, Z.; Liang, K.; Wang, D. W. Energy Storing Plant Stem with Cytocompatibility for Supercapacitor Electrode. Adv. Funct. Mater. 2021, 31 (52), 1– 9,  DOI: 10.1002/adfm.202106787
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    Stavrinidou, E.; Gabrielsson, R.; Gomez, E.; Crispin, X.; Nilsson, O.; Simon, D. T.; Berggren, M. Electronic Plants. Sci. Adv. 2015, 1 (10), e1501136  DOI: 10.1126/sciadv.1501136
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    Parker, D.; Daguerre, Y.; Dufil, G.; Mantione, D.; Solano, E.; Cloutet, E.; Hadziioannou, G.; Näsholm, T.; Berggren, M.; Pavlopoulou, E.; Stavrinidou, E. Biohybrid Plants with Electronic Roots via in Vivo Polymerization of Conjugated Oligomers. Materials Horizons 2021, 8 (12), 3295– 3305,  DOI: 10.1039/D1MH01423D
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    Parker, D.; Dar, A. M.; Armada-Moreira, A.; Bernacka Wojcik, I.; Rai, R.; Mantione, D.; Stavrinidou, E. Biohybrid Energy Storage Circuits Based on Electronically Functionalized Plant Roots. ACS Appl. Mater. Interfaces 2024, 16 (45), 61475– 61483,  DOI: 10.1021/acsami.3c16861
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    Dufil, G.; Parker, D.; Gerasimov, J. Y.; Nguyen, T.-Q.; Berggren, M.; Stavrinidou, E. Enzyme-Assisted In Vivo Polymerisation of Conjugated Oligomer Based Conductors. J. Mater. Chem. B 2020, 8 (19), 4221– 4227,  DOI: 10.1039/D0TB00212G
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    21
    Enzyme-assisted in vivo polymerisation of conjugated oligomer based conductors
    Dufil, Gwennael; Parker, Daniela; Gerasimov, Jennifer Y.; Nguyen, Thuc-Quyen; Berggren, Magnus; Stavrinidou, Eleni
    Journal of Materials Chemistry B: Materials for Biology and Medicine (2020), 8 (19), 4221-4227CODEN: JMCBDV; ISSN:2050-7518. (Royal Society of Chemistry)
    Conjugated polymers conduct both electronic and ionic carriers and thus can stimulate and translate biol. 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, the authors recently demonstrated spontaneous in vivo polymn. of the conjugated oligomer ETE-S in the vascular tissue of plants and the formation of conducting wires. The authors elucidate the mechanism of the in vivo polymn. of the ETE-S trimer and demonstrate that ETE-S polymerizes due to an enzymic 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 enzymically polymd. in vivo. By reproducing the reaction in vitro, the authors gain further insight on the polymn. 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 biochem. pathway and integrates within the plant cell wall, forming conductors along the plant structure.
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  22. 22
    Mantione, D.; Istif, E.; Dufil, G.; Vallan, L.; Parker, D.; Brochon, C.; Cloutet, E.; Hadziioannou, G.; Berggren, M.; Stavrinidou, E.; Pavlopoulou, E. Thiophene-Based Trimers for In Vivo Electronic Functionalization of Tissues. ACS Appl. Electron. Mater. 2020, 2 (12), 4065– 4071,  DOI: 10.1021/acsaelm.0c00861
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    22
    Thiophene-Based Trimers for In Vivo Electronic Functionalization of Tissues
    Mantione, Daniele; Istif, Emin; Dufil, Gwennael; Vallan, Lorenzo; Parker, Daniela; Brochon, Cyril; Cloutet, Eric; Hadziioannou, Georges; Berggren, Magnus; Stavrinidou, Eleni; Pavlopoulou, Eleni
    ACS Applied Electronic Materials (2020), 2 (12), 4065-4071CODEN: AAEMBP; ISSN:2637-6113. (American Chemical Society)
    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 polymn. of the conjugated oligomer ETE-S in plants, forming conductors along the plant structure. The EDOT-thiophene-EDOT trimer with a sulfonate side group polymd. due to the native enzymic 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 enzymically in physiol. 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.
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  23. 23
    Zhang, J.; Landry, M. P.; Barone, P. W.; Kim, J. Molecular Recognition Using Corona Phase Complexes Made of Synthetic Polymers Adsorbed on Carbon Nanotubes. Nat. Nanotechnol. 2013, 8, 959– 968,  DOI: 10.1038/nnano.2013.236
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    23
    Molecular recognition using corona phase complexes made of synthetic polymers adsorbed on carbon nanotubes
    Zhang, Jingqing; Landry, Markita P.; Barone, Paul W.; Kim, Jong-Ho; Lin, Shangchao; Ulissi, Zachary W.; Lin, Dahua; Mu, Bin; Boghossian, Ardemis A.; Hilmer, Andrew J.; Rwei, Alina; Hinckley, Allison C.; Kruss, Sebastian; Shandell, Mia A.; Nair, Nitish; Blake, Steven; Sen, Fatih; Sen, Selda; Croy, Robert G.; Li, Deyu; Yum, Kyungsuk; Ahn, Jin-Ho; Jin, Hong; Heller, Daniel A.; Essigmann, John M.; Blankschtein, Daniel; Strano, Michael S.
    Nature Nanotechnology (2013), 8 (12), 959-968CODEN: NNAABX; ISSN:1748-3387. (Nature Publishing Group)
    Understanding mol. recognition is of fundamental importance in applications such as therapeutics, chem. catalysis and sensor design. The most common recognition motifs involve biol. macromols. such as antibodies and aptamers. The key to biorecognition consists of a unique three-dimensional structure formed by a folded and constrained bioheteropolymer that creates a binding pocket, or an interface, able to recognize a specific mol. Here, we show that synthetic heteropolymers, once constrained onto a single-walled carbon nanotube by chem. adsorption, also form a new corona phase that exhibits highly selective recognition for specific mols. To prove the generality of this phenomenon, we report three examples of heteropolymer-nanotube recognition complexes for riboflavin, L-thyroxine and oestradiol. In each case, the recognition was predicted using a two-dimensional thermodn. model of surface interactions in which the dissocn. consts. can be tuned by perturbing the chem. structure of the heteropolymer. Moreover, these complexes can be used as new types of spatiotemporal sensors based on modulation of the carbon nanotube photoemission in the near-IR, as we show by tracking riboflavin diffusion in murine macrophages.
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  24. 24
    Giraldo, J. P.; Landry, M. P.; Faltermeier, S. M.; McNicholas, T. P.; Iverson, N. M.; Boghossian, A. A.; Reuel, N. F.; Hilmer, A. J.; Sen, F.; Brew, J. A.; Strano, M. S. Plant Nanobionics Approach to Augment Photosynthesis and Biochemical Sensing. Nat. Mater. 2014, 13 (4), 400– 408,  DOI: 10.1038/nmat3890
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    24
    Plant nanobionics approach to augment photosynthesis and biochemical sensing
    Giraldo, Juan Pablo; Landry, Markita P.; Faltermeier, Sean M.; McNicholas, Thomas P.; Iverson, Nicole M.; Boghossian, Ardemis A.; Reuel, Nigel F.; Hilmer, Andrew J.; Sen, Fatih; Brew, Jacqueline A.; Strano, Michael S.
    Nature Materials (2014), 13 (4), 400-408CODEN: NMAACR; ISSN:1476-1122. (Nature Publishing Group)
    The interface between plant organelles and non-biol. nanostructures has the potential to impart organelles with new and enhanced functions. Here, we show that single-walled carbon nanotubes (SWNTs) passively transport and irreversibly localize within the lipid envelope of extd. plant chloroplasts, promote over three times higher photosynthetic activity than that of controls, and enhance max. electron transport rates. The SWNT-chloroplast assemblies also enable higher rates of leaf electron transport in vivo through a mechanism consistent with augmented photoabsorption. Concns. of reactive oxygen species inside extd. chloroplasts are significantly suppressed by delivering poly(acrylic acid)-nanoceria or SWNT-nanoceria complexes. Moreover, we show that SWNTs enable near-IR fluorescence monitoring of nitric oxide both ex vivo and in vivo, thus demonstrating that a plant can be augmented to function as a photonic chem. sensor. Nanobionics engineering of plant function may contribute to the development of biomimetic materials for light-harvesting and biochem. detection with regenerative properties and enhanced efficiency.
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  25. 25
    Wong, M. H.; Giraldo, J. P.; Kwak, S. Y.; Koman, V. B.; Sinclair, R.; Lew, T. T. S.; Bisker, G.; Liu, P.; Strano, M. S. Nitroaromatic Detection and Infrared Communication from Wild-Type Plants Using Plant Nanobionics. Nat. Mater. 2017, 16 (2), 264– 272,  DOI: 10.1038/nmat4771
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    25
    Nitroaromatic detection and infrared communication from wild-type plants using plant nanobionics
    Wong, Min Hao; Giraldo, Juan P.; Kwak, Seon-Yeong; Koman, Volodymyr B.; Sinclair, Rosalie; Lew, Tedrick Thomas Salim; Bisker, Gili; Liu, Pingwei; Strano, Michael S.
    Nature Materials (2017), 16 (2), 264-272CODEN: NMAACR; ISSN:1476-1122. (Nature Publishing Group)
    Plant nanobionics aims to embed non-native functions to plants by interfacing them with specifically designed nanoparticles. Here, we demonstrate that living spinach plants (Spinacia oleracea) can be engineered to serve as self-powered pre-concentrators and autosamplers of analytes in ambient groundwater and as IR communication platforms that can send information to a smartphone. The plants employ a pair of near-IR fluorescent nanosensors-single-walled carbon nanotubes (SWCNTs) conjugated to the peptide Bombolitin II to recognize nitroaroms. via IR fluorescent emission, and polyvinyl-alc. functionalized SWCNTs that act as an invariant ref. signal-embedded within the plant leaf mesophyll. As contaminant nitroaroms. are transported up the roots and stem into leaf tissues, they accumulate in the mesophyll, resulting in relative changes in emission intensity. The real-time monitoring of embedded SWCNT sensors also allows residence times in the roots, stems and leaves to be estd., calcd. to be 8.3 min (combined residence times of root and stem) and 1.9 min mm-1 leaf, resp. These results demonstrate the ability of living, wild-type plants to function as chem. monitors of groundwater and communication devices to external electronics at standoff distances.
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  26. 26
    Lew, T. T. S.; Park, M.; Cui, J.; Strano, M. S. Plant Nanobionic Sensors for Arsenic Detection. Adv. Mater. 2021, 33, 2005683  DOI: 10.1002/adma.202005683
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    26
    Plant Nanobionic Sensors for Arsenic Detection
    Lew, Tedrick Thomas Salim; Park, Minkyung; Cui, Jianqiao; Strano, Michael S.
    Advanced Materials (Weinheim, Germany) (2021), 33 (1), 2005683CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)
    Arsenic is a highly toxic heavy-metal pollutant which poses a significant health risk to humans and other ecosystems. In this work, the natural ability of wild-type plants to pre-conc. and ext. arsenic from the belowground environment is exploited to engineer plant nanobionic sensors for real-time arsenic detection. Near-IR fluorescent nanosensors are specifically designed for sensitive and selective detection of arsenite. These optical nanosensors are embedded in plant tissues to non-destructively access and monitor the internal dynamics of arsenic taken up by the plants via the roots. The integration of optical nanosensors with living plants enables the conversion of plants into self-powered autosamplers of arsenic from their environment. Arsenite detection is demonstrated with three different plant species as nanobionic sensors. Based on an exptl. validated kinetic model, the nanobionic sensor could detect 0.6 and 0.2 ppb levels of arsenic after 7 and 14 days resp. by exploiting the natural ability of Pteris cretica ferns to hyperaccumulate and tolerate exceptionally high level of arsenic. The sensor readout could also be interfaced with portable electronics at a standoff distance, potentially enabling applications in environmental monitoring and agronomic research.
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  27. 27
    Lew, T. T. S.; Koman, V. B.; Silmore, K. S.; Seo, J. S.; Gordiichuk, P.; Kwak, S. Y.; Park, M.; Ang, M. C. Y.; Khong, D. T.; Lee, M. A.; Chan-Park, M. B.; Chua, N. H.; Strano, M. S. Real-Time Detection of Wound-Induced H2O2 Signalling Waves in Plants with Optical Nanosensors. Nature Plants 2020, 6 (4), 404– 415,  DOI: 10.1038/s41477-020-0632-4
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    Haller, T.; Stolp, H. Quantitative Estimation of Root Exudation of Maize Plants. Plant and Soil 1985, 86 (2), 207– 216,  DOI: 10.1007/BF02182895
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    Walker, T. S.; Bais, H. P.; Grotewold, E.; Vivanco, J. M. Update on Root Exudation and Rhizosphere Biology. Plant Physiol. 2003, 132, 44– 51,  DOI: 10.1104/pp.102.019661
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    Root exudation and rhizosphere biology
    Walker, Travis S.; Bais, Harsh Pal; Grotewold, Erich; Vivanco, Jorge M.
    Plant Physiology (2003), 132 (1), 44-51CODEN: PLPHAY; ISSN:0032-0889. (American Society of Plant Biologists)
    A review on the recent advancements in root exudation and rhizosphere biol. Several lines of evidence indicate that root exudates in their various forms may regulate plant and microbial communities in the rhizosphere. The vast majority of microbes exhibit incompatible interactions with plants, which could be explained by the const. and diverse secretion of antimicrobial root exudates. An understanding of the biol. of root exudation processes may contribute to devising novel strategies for improving plant fitness and the isolation of novel value-added compds. found in the root exudates.
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    Tiziani, R.; Mimmo, T.; Valentinuzzi, F.; Pii, Y.; Celletti, S.; Cesco, S. Root Handling Affects Carboxylates Exudation and Phosphate Uptake of White Lupin Roots. Frontiers in Plant Science 2020, 11, 584568  DOI: 10.3389/fpls.2020.584568
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    Baetz, U.; Martinoia, E. Root Exudates: The Hidden Part of Plant Defense. Trends in Plant Science 2014, 19 (2), 90– 98,  DOI: 10.1016/j.tplants.2013.11.006
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    Taylor, C.; Katakis, G.; Heller, A.; Rajagopalan, R. Wiring of Glucose Oxidase within a Hydrogel Made with Polyvinyl Imidazole Complexed with (Os-4,4-Dimethyl 2,2’-Bipyridine)Cl+/2+. J. Electroanal. Chem. 1995, 396, 511– 515,  DOI: 10.1016/0022-0728(95)04080-8
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    Lee, I.; Loew, N.; Tsugawa, W.; Lin, C. E.; Probst, D.; La Belle, J. T.; Sode, K. The Electrochemical Behavior of a FAD Dependent Glucose Dehydrogenase with Direct Electron Transfer Subunit by Immobilization on Self-Assembled Monolayers. Bioelectrochemistry 2018, 121, 1– 6,  DOI: 10.1016/j.bioelechem.2017.12.008
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    The electrochemical behavior of a FAD dependent glucose dehydrogenase with direct electron transfer subunit by immobilization on self-assembled monolayers
    Lee, Inyoung; Loew, Noya; Tsugawa, Wakako; Lin, Chi-En; Probst, David; La Belle, Jeffrey T.; Sode, Koji
    Bioelectrochemistry (2018), 121 (), 1-6CODEN: BIOEFK; ISSN:1567-5394. (Elsevier B.V.)
    Continuous glucose monitoring (CGM) is a vital technol. for diabetes patients by providing tight glycemic control. Currently, many com. available CGM sensors use glucose oxidase (GOD) as sensor element, but this enzyme is not able to transfer electrons directly to the electrode without oxygen or an electronic mediator. We previously reported a mutated FAD dependent glucose dehydrogenase complex (FADGDH) capable of direct electron transfer (DET) via an electron transfer subunit without involving oxygen or a mediator. In this study, we investigated the electrochem. response of DET by controlling the immobilization of DET-FADGDH using 3 types of self-assembled monolayers (SAMs) with varying lengths. With the employment of DET-FADGDH and SAM, high current densities were achieved without being affected by interfering substances such as acetaminophen and ascorbic acid. Addnl., the current generated from DET-FADGDH electrodes decreased with increasing length of SAM, suggesting that the DET ability can be affected by the distance between the enzyme and the electrode. These results indicate the feasibility of controlling the immobilization state of the enzymes on the electrode surface.
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    Shida, K. I.; Rihara, K. O.; Uguruma, H. M.; Wasa, H. I.; Iratsuka, A. H.; Suji, K. T.; Ishimoto, T. K. Comparison of Direct and Mediated Electron Transfer in Electrodes with Novel Fungal Flavin Adenine Dinucleotide Glucose Dehydrogenase. Anal. Sci. 2018, 34, 783– 787,  DOI: 10.2116/analsci.17P613
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    Suzuki, A.; Ishida, K.; Muguruma, H.; Iwasa, H.; Tanaka, T.; Hiratsuka, A.; Tsuji, K.; Kishimoto, T. Diameter Dependence of Single-Walled Carbon Nanotubes with Flavin Adenine Dinucleotide Glucose Dehydrogenase for Direct Electron Transfer Bioanodes. Jpn. J. Appl. Phys. 2019, 58, 051015  DOI: 10.7567/1347-4065/ab14fb
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    35
    Diameter dependence of single-walled carbon nanotubes with flavin adenine dinucleotide glucose dehydrogenase for direct electron transfer bioanodes
    Suzuki, Atsuya; Ishida, Kazuya; Muguruma, Hitoshi; Iwasa, Hisanori; Tanaka, Takeshi; Hiratsuka, Atsunori; Tsuji, Katsumi; Kishimoto, Takahide
    Japanese Journal of Applied Physics (2019), 58 (5), 051015CODEN: JJAPB6; ISSN:1347-4065. (IOP Publishing Ltd.)
    The diam. dependence of single-walled carbon nanotubes (SWCNTs) with FAD glucose dehydrogenase (FAD-GDH) for direct electron transfer (DET) type bioanodes is presented for the first time. In order to address the issue, we use SWCNTs having different diams. fabricated by direct-injection pyrolytic synthesis, which can control the diam. in a wide range with the other parameters fixed. Three different diams. of SWCNTs are examd.: av. diam. dm = 1.0, 1.5, and 2.0 nm. In order to achieve DET, a debundled, individual SWCNT has to be placed at the FAD position in the GDH protein pocket. The bioanodes with dm = 1.0 and 1.5 nm SWCNTs show better performance than that with dm = 2.0 nm SWCNTs. The diam. dependence of SWCNTs for bioanode performance is thought to be related to the distance between the SWCNTs and FAD positioned in the reaction center of the GDH protein shell.
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  36. 36
    Filipiak, M. S.; Vetter, D.; Thodkar, K.; Gutiérrez-Sanz, O.; Jönsson-Niedziółka, M.; Tarasov, A. Electron Transfer from FAD-Dependent Glucose Dehydrogenase to Single-Sheet Graphene Electrodes. Electrochim. Acta 2020, 330, 134998  DOI: 10.1016/j.electacta.2019.134998
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    Electron transfer from FAD-dependent glucose dehydrogenase to single-sheet graphene electrodes
    Filipiak, Marcin S.; Vetter, Daniel; Thodkar, Kishan; Gutierrez-Sanz, Oscar; Joensson-Niedziolka, Martin; Tarasov, Alexey
    Electrochimica Acta (2020), 330 (), 134998CODEN: ELCAAV; ISSN:0013-4686. (Elsevier Ltd.)
    Continuous glucose monitoring (CGM) is an emerging technol. that can provide a more complete picture of the diabetes patient's glucose levels. Amperometric blood glucose tests typically require redox mediators to facilitate charge transfer from the enzyme to the electrode, that are not ideal in CGM settings because of their potential toxicity or long-term stability issues. Direct electron transfer (DET) would eliminate this need and has therefore attracted substantial interest. However, most DET-based glucose biosensor studies so far used glucose oxidase (GOx) leading to controversial results because the O dependency may be misinterpreted as DET. Here, the authors overcome this challenge by using an O-insensitive glucose dehydrogenase (GDH). To enable direct electron transfer, the enzyme was immobilized on the surface of high-quality single-layer graphene electrodes via short pyrene linkers (<1 nm). The biosensor strongly responded to glucose even without a redox mediator, implying direct electron transfer. Control measurements on different surfaces further confirm that the response is enzyme-specific. The activity of immobilized enzymes was confirmed by glucose measurements with a conventional ferrocenemethanol mediator as well as relatively unexplored redox mediator - nitrosoaniline. The influence of a most potent interferent in blood, ascorbic acid, was assessed. This is the 1st demonstration of application of single-layer graphene electrode to obtain DET from an O insensitive enzyme (GDH), highlighting the potential of such devices for applications in CGM.
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  37. 37
    Jeon, W.; Kim, H.; Jang, H.; Lee, Y.; Sang, U.; Kim, H.; Choi, Y. A Stable Glucose Sensor with Direct Electron Transfer, Based on Glucose Dehydrogenase and Chitosan Hydro Bonded Multi-Walled Carbon Nanotubes. Biochem. Eng. J. 2022, 187, 108589  DOI: 10.1016/j.bej.2022.108589
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    Tsujimura, S.; Kojima, S.; Kano, K.; Ikeda, T.; Sato, M.; Sanada, H.; Omura, H. Novel FAD-Dependent Glucose Dehydrogenase for a Dioxygen-Insensitive Glucose Biosensor. Biosci., Biotechnol., Biochem. 2006, 70 (3), 654– 659,  DOI: 10.1271/bbb.70.654
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    Gerasimov, J. Y.; Gabrielsson, R.; Forchheimer, R.; Stavrinidou, E.; Simon, D. T.; Berggren, M.; Fabiano, S. An Evolvable Organic Electrochemical Transistor for Neuromorphic Applications. Adv. Sci. 2019, 6 (7), 1801339  DOI: 10.1002/advs.201801339
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    An Evolvable Organic Electrochemical Transistor for Neuromorphic Applications
    Gerasimov Jennifer Y; Gabrielsson Roger; Stavrinidou Eleni; Simon Daniel T; Berggren Magnus; Fabiano Simone; Forchheimer Robert
    Advanced science (Weinheim, Baden-Wurttemberg, Germany) (2019), 6 (7), 1801339 ISSN:2198-3844.
    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.
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  • Abstract

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    Figure 1

    Figure 1. (A) Schematic representation of the root biofunctionalization method using ETE-S mixed with GDH-FAD. GDH-FAD is entrapped in the p(ETE-S) layer, while it is formed via in vivo polymerization. The biofunctionalized root then acquires glucose sensitivity. (B) The one-step process consists of polymerizing ETE-S in the same medium that contains the GDH-FAD enzyme. The two-step process consists of first polymerizing ETE-S on a root for 24 h and then transferring the root into a GDH-FAD solution for 24 h more. (C) Chronoamperometric curve for glucose detection comparing the one-step process (red, n = 6) with the two-step process (black, n = 3) for a potential of +0.5 V vs Ag/AgCl. (D) Cyclic voltammogram in 10 mM KCl at 5 mV s–1 vs Ag/AgCl of a p(ETE-S) root (dashed black line) and p(ETE-S)/GDH-FAD (one-step process) before (solid black line) and after the addition of 100 mM glucose (red).

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    Figure 2

    Figure 2. Root biofunctionalization method using a redox hydrogel matrix composed of GOx, and PVI–Os crosslinked with PEGDE and drop-cast on a p(ETE-S) root. (A) Cyclic voltammogram showing the redox activity of 1 mM PVI–Os with an electropolymerized p(ETE-S) on ITO as the working electrode in 0.1 M KCl vs Ag/AgCl at scan rates of 25 mV s–1 (dark red), 10 mV s–1 (red), and 5 mV s–1 (orange). Cascade reaction of glucose oxidation and transport of electrons from the redox mediator to the p(ETE-S) root. (B) Cyclic voltammogram of p(ETE-S) roots (black dotted line), p(ETE-S)/PVI-Os/PEGDGE/GOx before (black) and after the addition of 100 mM glucose (red), in 10 mM KCl electrolyte with a scan rate of 5 mV s–1 vs Ag/AgCl. (C) Chronoamperometry of p(ETE-S) root (black), p(ETE-S)/PVI–Os/PEGDGE root (yellow), p(ETE-S)/GOx/PEGDGE root (red), and p(ETE-S)/PVI–Os/GO/PEGDGE root (brown) with successive additions of glucose. The concentration after each addition is indicated above the arrow. The p(ETE-S) root potential is fixed at +0.5 V vs Ag/AgCl.

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    Figure 3

    Figure 3. Glucose sensing in intact plants. (A) Image of the sensing measurement setup with an intact plant. A 2-week-old plant is placed in a 1/2 MS MES nutrient medium without sugar, while the biofunctionalized root (still attached on the plant) is placed in an electrolytic cell with 10 mM KCl. (B) Normalized response of glucose sensing measurement of a p(ETE-S)/PVI–Os/GOx/PEGDGE root at +0.5 V vs Ag/AgCl. Measurement on day 1 (red), day 2 (blue), and 1 week after biofunctionalization (black). (C) Normalized response of glucose sensing measurement of a p(ETE-S)/GDH-FAD root at +0.5 V vs Ag/AgCl. Measurement on day 1 (red), day 2 (blue), and 1 week after biofunctionalization (black). Standard deviation obtained for N = 6 replicates.

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    Figure 4

    Figure 4. ETE-S/GDH-FAD roots are supercapacitive bioanodes. (A) Schematic representation of the experimental setup for the galvanostatic charge/discharge characterization of two roots functionalized with 1 mM ETE-S + 5 mg mL–1 GDH-FAD. (B) Galvanostatic charge/discharge curve for a ±5 μA applied current for a voltage range of [0, +0.5] V. The electrolyte used here is either 10 mM KCl (black) or 10 mM KCl electrolyte +100 mM glucose (red) for 2 roots functionalized with ETE-S (upper graph) and 2 roots functionalized with ETE-S + GDH-FAD (lower graph).

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      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXkvFWku7o%253D&md5=ce5afeecbe293df2c6278494cf8e7801
    10. 10
      Rabaey, K.; Lissens, G.; Siciliano, S. D.; Verstraete, W. A Microbial Fuel Cell Capable of Converting Glucose to Electricity at High Rate and Efficiency. Biotechnol. Lett. 2003, 25 (18), 1531– 1535,  DOI: 10.1023/A:1025484009367
      There is no corresponding record for this reference.
    11. 11
      Jie, Y.; Jia, X.; Zou, J.; Chen, Y.; Wang, N.; Wang, Z. L.; Cao, X. Natural Leaf Made Triboelectric Nanogenerator for Harvesting Environmental Mechanical Energy. Adv. Energy Mater. 2018, 8 (12), 1– 7,  DOI: 10.1002/aenm.201703133
      There is no corresponding record for this reference.
    12. 12
      Feng, Y.; Zhang, L.; Zheng, Y.; Wang, D.; Zhou, F.; Liu, W. Leaves Based Triboelectric Nanogenerator (TENG) and TENG Tree for Wind Energy Harvesting. Nano Energy 2019, 55, 260– 268,  DOI: 10.1016/j.nanoen.2018.10.075
      12
      Leaves based triboelectric nanogenerator (TENG) and TENG tree for wind energy harvesting
      Feng, Yange; Zhang, Liqiang; Zheng, Youbin; Wang, Daoai; Zhou, Feng; Liu, Weimin
      Nano Energy (2019), 55 (), 260-268CODEN: NEANCA; ISSN:2211-2855. (Elsevier Ltd.)
      Triboelec. nanogenerators based on biodegradable plant leaf and leaf powder is fabricated through a simple and cost effective method. The short-circuit current (Isc) and output voltage (Vo) of fresh leaf can reach 15 μA and 430 V. Dry leaf is grinded into powder to make solve problem of frangibility when contact and make full use of the leaf. Poly-L-Lysine is used to modify leaf powder and enhance the output performance of leaf powder based TENG. After surface modification, the Isc and Vo can reach high as 60 μA and 1000 V, resp., which can easily power a com. elec. watch and 868 LEDs. To extend the drive mode, wind driven TENG (WTENG) based on PLL modified leaf powder is designed for harvesting wind energy and the max. Isc can reach 150 μA under 7 m/s wind speed. The WTENG is designed to power an "EXIT" LED light for exit passageway in windy weather. Furthermore, TENG tree is designed basing on the live leaves and artificial leaves, which have promising potential use in the remote regions, such as in the mountains or islands, for early warning and indicator light.
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    13. 13
      Jiang, J.; Fei, W.; Pu, M.; Chai, Z.; Wu, Z. A Facile Liquid Alloy Wetting Enhancing Strategy on Super-Hydrophobic Lotus Leaves for Plant-Hybrid System Implementation. Advanced Materials Interfaces 2022, 9 (17), 1– 9,  DOI: 10.1002/admi.202200516
      There is no corresponding record for this reference.
    14. 14
      Meder, F.; Thielen, M.; Mondini, A.; Speck, T.; Mazzolai, B. Living Plant-Hybrid Generators for Multidirectional Wind Energy Conversion. Energy Technology 2020, 8 (7), 2000236  DOI: 10.1002/ente.202000236
      There is no corresponding record for this reference.
    15. 15
      Wu, H.; Chen, Z.; Xu, G.; Xu, J.; Wang, Z.; Zi, Y. Fully Biodegradable Water Droplet Energy Harvester Based on Leaves of Living Plants. ACS Appl. Mater. Interfaces 2020, 12 (50), 56060– 56067,  DOI: 10.1021/acsami.0c17601
      15
      Fully Biodegradable Water Droplet Energy Harvester Based on Leaves of Living Plants
      Wu, Hao; Chen, Zefeng; Xu, Guoqiang; Xu, Jianbin; Wang, Zuankai; Zi, Yunlong
      ACS Applied Materials & Interfaces (2020), 12 (50), 56060-56067CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
      Triboelec. nanogenerators (TENGs) have obtained soaring interest due to their capability for environmental energy harvesting. However, as a harvester for green energy, the frequent adoption of the hardly degradable plastic films is not desirable. Here, we report a fully biodegradable TENG (FBD-TENG) that all elements are made from natural substances, and the utilization of plastic materials is avoided. The leaf cuticle and the inside conductive tissue are utilized as the tribo-material and electrode for one part in the FBD-TENG, and water droplets are employed as the counterpart. By using water droplets to bridge the originally disconnected components into a closed-loop elec. system, we successfully collect energy from the droplet impact onto a plant leaf. The electricity generation phenomenon and the working mechanism of the FBD-TENG have been investigated. Five kinds of plants, as well as rain water droplets, are employed to demonstrate the wide availability of the proposed approach. This study provides a strategy to utilize the pervasively presented electrostatic charges in nature in an eco-friendly way.
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    16. 16
      Stavrinidou, E.; Gabrielsson, R.; Nilsson, K. P. R.; Singh, S. K.; Franco-Gonzalez, J. F.; Volkov, A. V.; Jonsson, M. P.; Grimoldi, A.; Elgland, M.; Zozoulenko, I. V.; Simon, D. T.; Berggren, M. In Vivo Polymerization and Manufacturing of Wires and Supercapacitors in Plants. Proc. Natl. Acad. Sci. U. S. A. 2017, 114 (11), 2807– 2812,  DOI: 10.1073/pnas.1616456114
      16
      In vivo polymerization and manufacturing of wires and supercapacitors in plants
      Stavrinidou, Eleni; Gabrielsson, Roger; Nilsson, K. Peter R.; Singh, Sandeep Kumar; Franco-Gonzalez, Juan Felipe; Volkov, Anton V.; Jonsson, Magnus P.; Grimoldi, Andrea; Elgland, Mathias; Zozoulenko, Igor V.; Simon, Daniel T.; Berggren, Magnus
      Proceedings of the National Academy of Sciences of the United States of America (2017), 114 (11), 2807-2812CODEN: PNASA6; ISSN:0027-8424. (National Academy of Sciences)
      Electronic plants, e-Plants, are an org. 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 manufd. org. electronic devices and circuits in vivo, leveraging the internal structure and physiol. 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 phys. template, whereas the plant's biochem. response mechanism acts as the catalyst for polymn. In addn., the oligomer can cross through the veins and enter the apoplastic space in the leaves. Finally, using the plant's natural architecture we manuf. 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.
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    17. 17
      Liang, J.; Yu, M.; Liu, J.; Yu, Z.; Liang, K.; Wang, D. W. Energy Storing Plant Stem with Cytocompatibility for Supercapacitor Electrode. Adv. Funct. Mater. 2021, 31 (52), 1– 9,  DOI: 10.1002/adfm.202106787
      There is no corresponding record for this reference.
    18. 18
      Stavrinidou, E.; Gabrielsson, R.; Gomez, E.; Crispin, X.; Nilsson, O.; Simon, D. T.; Berggren, M. Electronic Plants. Sci. Adv. 2015, 1 (10), e1501136  DOI: 10.1126/sciadv.1501136
      There is no corresponding record for this reference.
    19. 19
      Parker, D.; Daguerre, Y.; Dufil, G.; Mantione, D.; Solano, E.; Cloutet, E.; Hadziioannou, G.; Näsholm, T.; Berggren, M.; Pavlopoulou, E.; Stavrinidou, E. Biohybrid Plants with Electronic Roots via in Vivo Polymerization of Conjugated Oligomers. Materials Horizons 2021, 8 (12), 3295– 3305,  DOI: 10.1039/D1MH01423D
      There is no corresponding record for this reference.
    20. 20
      Parker, D.; Dar, A. M.; Armada-Moreira, A.; Bernacka Wojcik, I.; Rai, R.; Mantione, D.; Stavrinidou, E. Biohybrid Energy Storage Circuits Based on Electronically Functionalized Plant Roots. ACS Appl. Mater. Interfaces 2024, 16 (45), 61475– 61483,  DOI: 10.1021/acsami.3c16861
      There is no corresponding record for this reference.
    21. 21
      Dufil, G.; Parker, D.; Gerasimov, J. Y.; Nguyen, T.-Q.; Berggren, M.; Stavrinidou, E. Enzyme-Assisted In Vivo Polymerisation of Conjugated Oligomer Based Conductors. J. Mater. Chem. B 2020, 8 (19), 4221– 4227,  DOI: 10.1039/D0TB00212G
      21
      Enzyme-assisted in vivo polymerisation of conjugated oligomer based conductors
      Dufil, Gwennael; Parker, Daniela; Gerasimov, Jennifer Y.; Nguyen, Thuc-Quyen; Berggren, Magnus; Stavrinidou, Eleni
      Journal of Materials Chemistry B: Materials for Biology and Medicine (2020), 8 (19), 4221-4227CODEN: JMCBDV; ISSN:2050-7518. (Royal Society of Chemistry)
      Conjugated polymers conduct both electronic and ionic carriers and thus can stimulate and translate biol. 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, the authors recently demonstrated spontaneous in vivo polymn. of the conjugated oligomer ETE-S in the vascular tissue of plants and the formation of conducting wires. The authors elucidate the mechanism of the in vivo polymn. of the ETE-S trimer and demonstrate that ETE-S polymerizes due to an enzymic 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 enzymically polymd. in vivo. By reproducing the reaction in vitro, the authors gain further insight on the polymn. 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 biochem. pathway and integrates within the plant cell wall, forming conductors along the plant structure.
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    22. 22
      Mantione, D.; Istif, E.; Dufil, G.; Vallan, L.; Parker, D.; Brochon, C.; Cloutet, E.; Hadziioannou, G.; Berggren, M.; Stavrinidou, E.; Pavlopoulou, E. Thiophene-Based Trimers for In Vivo Electronic Functionalization of Tissues. ACS Appl. Electron. Mater. 2020, 2 (12), 4065– 4071,  DOI: 10.1021/acsaelm.0c00861
      22
      Thiophene-Based Trimers for In Vivo Electronic Functionalization of Tissues
      Mantione, Daniele; Istif, Emin; Dufil, Gwennael; Vallan, Lorenzo; Parker, Daniela; Brochon, Cyril; Cloutet, Eric; Hadziioannou, Georges; Berggren, Magnus; Stavrinidou, Eleni; Pavlopoulou, Eleni
      ACS Applied Electronic Materials (2020), 2 (12), 4065-4071CODEN: AAEMBP; ISSN:2637-6113. (American Chemical Society)
      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 polymn. of the conjugated oligomer ETE-S in plants, forming conductors along the plant structure. The EDOT-thiophene-EDOT trimer with a sulfonate side group polymd. due to the native enzymic 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 enzymically in physiol. 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.
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    23. 23
      Zhang, J.; Landry, M. P.; Barone, P. W.; Kim, J. Molecular Recognition Using Corona Phase Complexes Made of Synthetic Polymers Adsorbed on Carbon Nanotubes. Nat. Nanotechnol. 2013, 8, 959– 968,  DOI: 10.1038/nnano.2013.236
      23
      Molecular recognition using corona phase complexes made of synthetic polymers adsorbed on carbon nanotubes
      Zhang, Jingqing; Landry, Markita P.; Barone, Paul W.; Kim, Jong-Ho; Lin, Shangchao; Ulissi, Zachary W.; Lin, Dahua; Mu, Bin; Boghossian, Ardemis A.; Hilmer, Andrew J.; Rwei, Alina; Hinckley, Allison C.; Kruss, Sebastian; Shandell, Mia A.; Nair, Nitish; Blake, Steven; Sen, Fatih; Sen, Selda; Croy, Robert G.; Li, Deyu; Yum, Kyungsuk; Ahn, Jin-Ho; Jin, Hong; Heller, Daniel A.; Essigmann, John M.; Blankschtein, Daniel; Strano, Michael S.
      Nature Nanotechnology (2013), 8 (12), 959-968CODEN: NNAABX; ISSN:1748-3387. (Nature Publishing Group)
      Understanding mol. recognition is of fundamental importance in applications such as therapeutics, chem. catalysis and sensor design. The most common recognition motifs involve biol. macromols. such as antibodies and aptamers. The key to biorecognition consists of a unique three-dimensional structure formed by a folded and constrained bioheteropolymer that creates a binding pocket, or an interface, able to recognize a specific mol. Here, we show that synthetic heteropolymers, once constrained onto a single-walled carbon nanotube by chem. adsorption, also form a new corona phase that exhibits highly selective recognition for specific mols. To prove the generality of this phenomenon, we report three examples of heteropolymer-nanotube recognition complexes for riboflavin, L-thyroxine and oestradiol. In each case, the recognition was predicted using a two-dimensional thermodn. model of surface interactions in which the dissocn. consts. can be tuned by perturbing the chem. structure of the heteropolymer. Moreover, these complexes can be used as new types of spatiotemporal sensors based on modulation of the carbon nanotube photoemission in the near-IR, as we show by tracking riboflavin diffusion in murine macrophages.
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    24. 24
      Giraldo, J. P.; Landry, M. P.; Faltermeier, S. M.; McNicholas, T. P.; Iverson, N. M.; Boghossian, A. A.; Reuel, N. F.; Hilmer, A. J.; Sen, F.; Brew, J. A.; Strano, M. S. Plant Nanobionics Approach to Augment Photosynthesis and Biochemical Sensing. Nat. Mater. 2014, 13 (4), 400– 408,  DOI: 10.1038/nmat3890
      24
      Plant nanobionics approach to augment photosynthesis and biochemical sensing
      Giraldo, Juan Pablo; Landry, Markita P.; Faltermeier, Sean M.; McNicholas, Thomas P.; Iverson, Nicole M.; Boghossian, Ardemis A.; Reuel, Nigel F.; Hilmer, Andrew J.; Sen, Fatih; Brew, Jacqueline A.; Strano, Michael S.
      Nature Materials (2014), 13 (4), 400-408CODEN: NMAACR; ISSN:1476-1122. (Nature Publishing Group)
      The interface between plant organelles and non-biol. nanostructures has the potential to impart organelles with new and enhanced functions. Here, we show that single-walled carbon nanotubes (SWNTs) passively transport and irreversibly localize within the lipid envelope of extd. plant chloroplasts, promote over three times higher photosynthetic activity than that of controls, and enhance max. electron transport rates. The SWNT-chloroplast assemblies also enable higher rates of leaf electron transport in vivo through a mechanism consistent with augmented photoabsorption. Concns. of reactive oxygen species inside extd. chloroplasts are significantly suppressed by delivering poly(acrylic acid)-nanoceria or SWNT-nanoceria complexes. Moreover, we show that SWNTs enable near-IR fluorescence monitoring of nitric oxide both ex vivo and in vivo, thus demonstrating that a plant can be augmented to function as a photonic chem. sensor. Nanobionics engineering of plant function may contribute to the development of biomimetic materials for light-harvesting and biochem. detection with regenerative properties and enhanced efficiency.
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    25. 25
      Wong, M. H.; Giraldo, J. P.; Kwak, S. Y.; Koman, V. B.; Sinclair, R.; Lew, T. T. S.; Bisker, G.; Liu, P.; Strano, M. S. Nitroaromatic Detection and Infrared Communication from Wild-Type Plants Using Plant Nanobionics. Nat. Mater. 2017, 16 (2), 264– 272,  DOI: 10.1038/nmat4771
      25
      Nitroaromatic detection and infrared communication from wild-type plants using plant nanobionics
      Wong, Min Hao; Giraldo, Juan P.; Kwak, Seon-Yeong; Koman, Volodymyr B.; Sinclair, Rosalie; Lew, Tedrick Thomas Salim; Bisker, Gili; Liu, Pingwei; Strano, Michael S.
      Nature Materials (2017), 16 (2), 264-272CODEN: NMAACR; ISSN:1476-1122. (Nature Publishing Group)
      Plant nanobionics aims to embed non-native functions to plants by interfacing them with specifically designed nanoparticles. Here, we demonstrate that living spinach plants (Spinacia oleracea) can be engineered to serve as self-powered pre-concentrators and autosamplers of analytes in ambient groundwater and as IR communication platforms that can send information to a smartphone. The plants employ a pair of near-IR fluorescent nanosensors-single-walled carbon nanotubes (SWCNTs) conjugated to the peptide Bombolitin II to recognize nitroaroms. via IR fluorescent emission, and polyvinyl-alc. functionalized SWCNTs that act as an invariant ref. signal-embedded within the plant leaf mesophyll. As contaminant nitroaroms. are transported up the roots and stem into leaf tissues, they accumulate in the mesophyll, resulting in relative changes in emission intensity. The real-time monitoring of embedded SWCNT sensors also allows residence times in the roots, stems and leaves to be estd., calcd. to be 8.3 min (combined residence times of root and stem) and 1.9 min mm-1 leaf, resp. These results demonstrate the ability of living, wild-type plants to function as chem. monitors of groundwater and communication devices to external electronics at standoff distances.
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    26. 26
      Lew, T. T. S.; Park, M.; Cui, J.; Strano, M. S. Plant Nanobionic Sensors for Arsenic Detection. Adv. Mater. 2021, 33, 2005683  DOI: 10.1002/adma.202005683
      26
      Plant Nanobionic Sensors for Arsenic Detection
      Lew, Tedrick Thomas Salim; Park, Minkyung; Cui, Jianqiao; Strano, Michael S.
      Advanced Materials (Weinheim, Germany) (2021), 33 (1), 2005683CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)
      Arsenic is a highly toxic heavy-metal pollutant which poses a significant health risk to humans and other ecosystems. In this work, the natural ability of wild-type plants to pre-conc. and ext. arsenic from the belowground environment is exploited to engineer plant nanobionic sensors for real-time arsenic detection. Near-IR fluorescent nanosensors are specifically designed for sensitive and selective detection of arsenite. These optical nanosensors are embedded in plant tissues to non-destructively access and monitor the internal dynamics of arsenic taken up by the plants via the roots. The integration of optical nanosensors with living plants enables the conversion of plants into self-powered autosamplers of arsenic from their environment. Arsenite detection is demonstrated with three different plant species as nanobionic sensors. Based on an exptl. validated kinetic model, the nanobionic sensor could detect 0.6 and 0.2 ppb levels of arsenic after 7 and 14 days resp. by exploiting the natural ability of Pteris cretica ferns to hyperaccumulate and tolerate exceptionally high level of arsenic. The sensor readout could also be interfaced with portable electronics at a standoff distance, potentially enabling applications in environmental monitoring and agronomic research.
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    27. 27
      Lew, T. T. S.; Koman, V. B.; Silmore, K. S.; Seo, J. S.; Gordiichuk, P.; Kwak, S. Y.; Park, M.; Ang, M. C. Y.; Khong, D. T.; Lee, M. A.; Chan-Park, M. B.; Chua, N. H.; Strano, M. S. Real-Time Detection of Wound-Induced H2O2 Signalling Waves in Plants with Optical Nanosensors. Nature Plants 2020, 6 (4), 404– 415,  DOI: 10.1038/s41477-020-0632-4
      There is no corresponding record for this reference.
    28. 28
      Haller, T.; Stolp, H. Quantitative Estimation of Root Exudation of Maize Plants. Plant and Soil 1985, 86 (2), 207– 216,  DOI: 10.1007/BF02182895
      There is no corresponding record for this reference.
    29. 29
      Walker, T. S.; Bais, H. P.; Grotewold, E.; Vivanco, J. M. Update on Root Exudation and Rhizosphere Biology. Plant Physiol. 2003, 132, 44– 51,  DOI: 10.1104/pp.102.019661
      29
      Root exudation and rhizosphere biology
      Walker, Travis S.; Bais, Harsh Pal; Grotewold, Erich; Vivanco, Jorge M.
      Plant Physiology (2003), 132 (1), 44-51CODEN: PLPHAY; ISSN:0032-0889. (American Society of Plant Biologists)
      A review on the recent advancements in root exudation and rhizosphere biol. Several lines of evidence indicate that root exudates in their various forms may regulate plant and microbial communities in the rhizosphere. The vast majority of microbes exhibit incompatible interactions with plants, which could be explained by the const. and diverse secretion of antimicrobial root exudates. An understanding of the biol. of root exudation processes may contribute to devising novel strategies for improving plant fitness and the isolation of novel value-added compds. found in the root exudates.
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    30. 30
      Tiziani, R.; Mimmo, T.; Valentinuzzi, F.; Pii, Y.; Celletti, S.; Cesco, S. Root Handling Affects Carboxylates Exudation and Phosphate Uptake of White Lupin Roots. Frontiers in Plant Science 2020, 11, 584568  DOI: 10.3389/fpls.2020.584568
      There is no corresponding record for this reference.
    31. 31
      Baetz, U.; Martinoia, E. Root Exudates: The Hidden Part of Plant Defense. Trends in Plant Science 2014, 19 (2), 90– 98,  DOI: 10.1016/j.tplants.2013.11.006
      There is no corresponding record for this reference.
    32. 32
      Taylor, C.; Katakis, G.; Heller, A.; Rajagopalan, R. Wiring of Glucose Oxidase within a Hydrogel Made with Polyvinyl Imidazole Complexed with (Os-4,4-Dimethyl 2,2’-Bipyridine)Cl+/2+. J. Electroanal. Chem. 1995, 396, 511– 515,  DOI: 10.1016/0022-0728(95)04080-8
      There is no corresponding record for this reference.
    33. 33
      Lee, I.; Loew, N.; Tsugawa, W.; Lin, C. E.; Probst, D.; La Belle, J. T.; Sode, K. The Electrochemical Behavior of a FAD Dependent Glucose Dehydrogenase with Direct Electron Transfer Subunit by Immobilization on Self-Assembled Monolayers. Bioelectrochemistry 2018, 121, 1– 6,  DOI: 10.1016/j.bioelechem.2017.12.008
      33
      The electrochemical behavior of a FAD dependent glucose dehydrogenase with direct electron transfer subunit by immobilization on self-assembled monolayers
      Lee, Inyoung; Loew, Noya; Tsugawa, Wakako; Lin, Chi-En; Probst, David; La Belle, Jeffrey T.; Sode, Koji
      Bioelectrochemistry (2018), 121 (), 1-6CODEN: BIOEFK; ISSN:1567-5394. (Elsevier B.V.)
      Continuous glucose monitoring (CGM) is a vital technol. for diabetes patients by providing tight glycemic control. Currently, many com. available CGM sensors use glucose oxidase (GOD) as sensor element, but this enzyme is not able to transfer electrons directly to the electrode without oxygen or an electronic mediator. We previously reported a mutated FAD dependent glucose dehydrogenase complex (FADGDH) capable of direct electron transfer (DET) via an electron transfer subunit without involving oxygen or a mediator. In this study, we investigated the electrochem. response of DET by controlling the immobilization of DET-FADGDH using 3 types of self-assembled monolayers (SAMs) with varying lengths. With the employment of DET-FADGDH and SAM, high current densities were achieved without being affected by interfering substances such as acetaminophen and ascorbic acid. Addnl., the current generated from DET-FADGDH electrodes decreased with increasing length of SAM, suggesting that the DET ability can be affected by the distance between the enzyme and the electrode. These results indicate the feasibility of controlling the immobilization state of the enzymes on the electrode surface.
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    34. 34
      Shida, K. I.; Rihara, K. O.; Uguruma, H. M.; Wasa, H. I.; Iratsuka, A. H.; Suji, K. T.; Ishimoto, T. K. Comparison of Direct and Mediated Electron Transfer in Electrodes with Novel Fungal Flavin Adenine Dinucleotide Glucose Dehydrogenase. Anal. Sci. 2018, 34, 783– 787,  DOI: 10.2116/analsci.17P613
      There is no corresponding record for this reference.
    35. 35
      Suzuki, A.; Ishida, K.; Muguruma, H.; Iwasa, H.; Tanaka, T.; Hiratsuka, A.; Tsuji, K.; Kishimoto, T. Diameter Dependence of Single-Walled Carbon Nanotubes with Flavin Adenine Dinucleotide Glucose Dehydrogenase for Direct Electron Transfer Bioanodes. Jpn. J. Appl. Phys. 2019, 58, 051015  DOI: 10.7567/1347-4065/ab14fb
      35
      Diameter dependence of single-walled carbon nanotubes with flavin adenine dinucleotide glucose dehydrogenase for direct electron transfer bioanodes
      Suzuki, Atsuya; Ishida, Kazuya; Muguruma, Hitoshi; Iwasa, Hisanori; Tanaka, Takeshi; Hiratsuka, Atsunori; Tsuji, Katsumi; Kishimoto, Takahide
      Japanese Journal of Applied Physics (2019), 58 (5), 051015CODEN: JJAPB6; ISSN:1347-4065. (IOP Publishing Ltd.)
      The diam. dependence of single-walled carbon nanotubes (SWCNTs) with FAD glucose dehydrogenase (FAD-GDH) for direct electron transfer (DET) type bioanodes is presented for the first time. In order to address the issue, we use SWCNTs having different diams. fabricated by direct-injection pyrolytic synthesis, which can control the diam. in a wide range with the other parameters fixed. Three different diams. of SWCNTs are examd.: av. diam. dm = 1.0, 1.5, and 2.0 nm. In order to achieve DET, a debundled, individual SWCNT has to be placed at the FAD position in the GDH protein pocket. The bioanodes with dm = 1.0 and 1.5 nm SWCNTs show better performance than that with dm = 2.0 nm SWCNTs. The diam. dependence of SWCNTs for bioanode performance is thought to be related to the distance between the SWCNTs and FAD positioned in the reaction center of the GDH protein shell.
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    36. 36
      Filipiak, M. S.; Vetter, D.; Thodkar, K.; Gutiérrez-Sanz, O.; Jönsson-Niedziółka, M.; Tarasov, A. Electron Transfer from FAD-Dependent Glucose Dehydrogenase to Single-Sheet Graphene Electrodes. Electrochim. Acta 2020, 330, 134998  DOI: 10.1016/j.electacta.2019.134998
      36
      Electron transfer from FAD-dependent glucose dehydrogenase to single-sheet graphene electrodes
      Filipiak, Marcin S.; Vetter, Daniel; Thodkar, Kishan; Gutierrez-Sanz, Oscar; Joensson-Niedziolka, Martin; Tarasov, Alexey
      Electrochimica Acta (2020), 330 (), 134998CODEN: ELCAAV; ISSN:0013-4686. (Elsevier Ltd.)
      Continuous glucose monitoring (CGM) is an emerging technol. that can provide a more complete picture of the diabetes patient's glucose levels. Amperometric blood glucose tests typically require redox mediators to facilitate charge transfer from the enzyme to the electrode, that are not ideal in CGM settings because of their potential toxicity or long-term stability issues. Direct electron transfer (DET) would eliminate this need and has therefore attracted substantial interest. However, most DET-based glucose biosensor studies so far used glucose oxidase (GOx) leading to controversial results because the O dependency may be misinterpreted as DET. Here, the authors overcome this challenge by using an O-insensitive glucose dehydrogenase (GDH). To enable direct electron transfer, the enzyme was immobilized on the surface of high-quality single-layer graphene electrodes via short pyrene linkers (<1 nm). The biosensor strongly responded to glucose even without a redox mediator, implying direct electron transfer. Control measurements on different surfaces further confirm that the response is enzyme-specific. The activity of immobilized enzymes was confirmed by glucose measurements with a conventional ferrocenemethanol mediator as well as relatively unexplored redox mediator - nitrosoaniline. The influence of a most potent interferent in blood, ascorbic acid, was assessed. This is the 1st demonstration of application of single-layer graphene electrode to obtain DET from an O insensitive enzyme (GDH), highlighting the potential of such devices for applications in CGM.
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    37. 37
      Jeon, W.; Kim, H.; Jang, H.; Lee, Y.; Sang, U.; Kim, H.; Choi, Y. A Stable Glucose Sensor with Direct Electron Transfer, Based on Glucose Dehydrogenase and Chitosan Hydro Bonded Multi-Walled Carbon Nanotubes. Biochem. Eng. J. 2022, 187, 108589  DOI: 10.1016/j.bej.2022.108589
      There is no corresponding record for this reference.
    38. 38
      Tsujimura, S.; Kojima, S.; Kano, K.; Ikeda, T.; Sato, M.; Sanada, H.; Omura, H. Novel FAD-Dependent Glucose Dehydrogenase for a Dioxygen-Insensitive Glucose Biosensor. Biosci., Biotechnol., Biochem. 2006, 70 (3), 654– 659,  DOI: 10.1271/bbb.70.654
      There is no corresponding record for this reference.
    39. 39
      Gerasimov, J. Y.; Gabrielsson, R.; Forchheimer, R.; Stavrinidou, E.; Simon, D. T.; Berggren, M.; Fabiano, S. An Evolvable Organic Electrochemical Transistor for Neuromorphic Applications. Adv. Sci. 2019, 6 (7), 1801339  DOI: 10.1002/advs.201801339
      39
      An Evolvable Organic Electrochemical Transistor for Neuromorphic Applications
      Gerasimov Jennifer Y; Gabrielsson Roger; Stavrinidou Eleni; Simon Daniel T; Berggren Magnus; Fabiano Simone; Forchheimer Robert
      Advanced science (Weinheim, Baden-Wurttemberg, Germany) (2019), 6 (7), 1801339 ISSN:2198-3844.
      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.
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    40. 40
      Mano, N.; Heller, A. A Miniature Membrane-Less Biofuel Cell Operating at + 0.60 V under Physiological Conditions. ACS Div. Fuel Chem. 2005, 50 (2), 584– 585,  DOI: 10.1149/1.1592519
      There is no corresponding record for this reference.
    41. 41
      Wilson, R.; Turner, A. P. F. Glucose Oxidase: An Ideal Enzyme. Biosens. Bioelectron. 1992, 7 (3), 165– 185,  DOI: 10.1016/0956-5663(92)87013-F
      41
      Glucose oxidase: an ideal enzyme
      Wilson, R.; Turner, A. P. F.
      Biosensors & Bioelectronics (1992), 7 (3), 165-85CODEN: BBIOE4; ISSN:0956-5663.
      A review with 168 refs. The properties of glucose oxidase (I) are described in relation to the widespread use of this enzyme in biosensors. The shortcomings of other enzymes that oxidize glucose are indicated. Isolation of and early work on I are briefly summarized. The sources and the phys. characteristics of I are listed. The structure of I and how it relates to the immobilization and stability of the enzyme is described along with other factors that influence stability. The role of FAD and attempts to use it in immobilization of the enzyme are described. Inhibitors of the enzyme are listed, and substrates of the enzyme and the reaction mechanism are discussed in detail. The role of electron acceptors in amperometric biosensors is described, and alternatives to their use are highlighted. Other uses of I are described and the properties of the enzyme are summarized with ref. to a com. successful biosensor.
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    42. 42
      Vogt, S.; Schneider, M.; Schäfer-Eberwein, H.; Nöll, G. Determination of the pH Dependent Redox Potential of Glucose Oxidase by Spectroelectrochemistry. Anal. Chem. 2014, 86 (15), 7530– 7535,  DOI: 10.1021/ac501289x
      There is no corresponding record for this reference.
    43. 43
      Elgrishi, N.; Rountree, K. J.; McCarthy, B. D.; Rountree, E. S.; Eisenhart, T. T.; Dempsey, J. L. A Practical Beginner’s Guide to Cyclic Voltammetry. J. Chem. Educ. 2018, 95 (2), 197– 206,  DOI: 10.1021/acs.jchemed.7b00361
      43
      A Practical Beginner's Guide to Cyclic Voltammetry
      Elgrishi, Noemie; Rountree, Kelley J.; McCarthy, Brian D.; Rountree, Eric S.; Eisenhart, Thomas T.; Dempsey, Jillian L.
      Journal of Chemical Education (2018), 95 (2), 197-206CODEN: JCEDA8; ISSN:0021-9584. (American Chemical Society and Division of Chemical Education, Inc.)
      Despite the growing popularity of cyclic voltammetry, many students do not receive formalized training in this technique as part of their coursework. Confronted with self-instruction, students can be left wondering where to start. Here, a short introduction to cyclic voltammetry is provided to help the reader with data acquisition and interpretation. Tips and common pitfalls are provided, and the reader is encouraged to apply what is learned in short, simple training modules provided in the Supporting Information. Armed with the basics, the motivated aspiring electrochemist will find existing resources more accessible and will progress much faster in the understanding of cyclic voltammetry.
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    44. 44
      Rasmussen, M.; Ritzmann, R. E.; Lee, I.; Pollack, A. J.; Scherson, D. An Implantable Biofuel Cell for a Live Insect. J. Am. Chem. Soc. 2012, 134 (3), 1458– 1460,  DOI: 10.1021/ja210794c
      44
      An implantable biofuel cell for a live insect
      Rasmussen, Michelle; Ritzmann, Roy E.; Lee, Irene; Pollack, Alan J.; Scherson, Daniel
      Journal of the American Chemical Society (2012), 134 (3), 1458-1460CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      A biofuel cell incorporating a bienzymic trehalase/glucose oxidase trehalose anode and a bilirubin oxidase dioxygen cathode using Os complexes grafted to a polymeric backbone as electron relays was designed and constructed. The specific power densities of the biofuel cell implanted in a female Blabera discoidalis through incisions into its abdomen yielded max. values of ∼55 μW/cm2 at 0.2 V that decreased by only ∼5% after ∼2.5 h of operation.
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    45. 45
      Mitraka, E.; Gryszel, M.; Vagin, M.; Jafari, M. J.; Singh, A.; Warczak, M.; Mitrakas, M.; Berggren, M.; Ederth, T.; Zozoulenko, I.; Crispin, X.; Głowacki, E. D. Electrocatalytic Production of Hydrogen Peroxide with Poly(3,4-Ethylenedioxythiophene) Electrodes. Advanced Sustainable Systems 2019, 3 (2), 1– 6,  DOI: 10.1002/adsu.201800110
      There is no corresponding record for this reference.
    46. 46
      Masakari, Y.; Hara, C.; Nakazawa, H.; Ichiyanagi, A.; Umetsu, M. Comparison of the Stability of Mucor-Derived Flavin Adenine Dinucleotide-Dependent Glucose Dehydrogenase and Glucose Oxidase. J. Biosci. Bioeng. 2022, 134 (4), 307– 310,  DOI: 10.1016/j.jbiosc.2022.06.017
      There is no corresponding record for this reference.
    47. 47
      Zafar, M. N.; Beden, N.; Leech, D.; Sygmund, C.; Ludwig, R.; Gorton, L. Characterization of Different FAD-Dependent Glucose Dehydrogenases for Possible Use in Glucose-Based Biosensors and Biofuel Cells. Anal. Bioanal. Chem. 2012, 402 (6), 2069– 2077,  DOI: 10.1007/s00216-011-5650-7
      47
      Characterization of different FAD-dependent glucose dehydrogenases for possible use in glucose-based biosensors and biofuel cells
      Zafar, Muhammad Nadeem; Beden, Najat; Leech, Donal; Sygmund, Christoph; Ludwig, Roland; Gorton, Lo
      Analytical and Bioanalytical Chemistry (2012), 402 (6), 2069-2077CODEN: ABCNBP; ISSN:1618-2642. (Springer)
      In this study, different FAD-dependent glucose dehydrogenases (FADGDHs) were characterized electrochem. after "wiring" them with an osmium redox polymer [Os(4,4'-dimethyl-2,2'-bipyridine)2(PVI)10Cl]+ on graphite electrodes. One tested FADGDH was that recently discovered in Glomerella cingulata (GcGDH), another was the recombinant form expressed in Pichia pastoris (rGcGDH), and the third was a com. available glycosylated enzyme from Aspergillus sp. (AspGDH). The performance of the Os-polymer "wired" GDHs on graphite electrodes was tested with glucose as the substrate. Optimal operational conditions and anal. characteristics like sensitivity, linear ranges and c.d. of the different FADGDHs were detd. The performance of all three types of FADGDHs was studied at physiol. conditions (pH 7.4). The current densities measured at a 20 mM glucose concn. were 494±17, 370±24, and 389±19 μA cm-2 for GcGDH, rGcGDH, and AspGDH, resp. The sensitivities towards glucose were 2.16, 1.90, and 1.42 μA mM-1 for GcGDH, rGcGDH, and AspGDH, resp. Addnl., deglycosylated rGcGDH (dgrGcGDH) was investigated to see whether the reduced glycosylation would have an effect, e.g., a higher c.d., which was indeed found. GcGDH/Os-polymer modified electrodes were also used and investigated for their selectivity for a no. of different sugars.
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    48. 48
      Rudge, A.; Davey, J.; Raistrick, I.; Gottesfeld, S.; Ferraris, J. P. Conducting Polymers as Active Materials in Electrochemical Capacitors. J. Power Sources 1994, 47 (1), 89– 107,  DOI: 10.1016/0378-7753(94)80053-7
      48
      Conducting polymers as active materials in electrochemical capacitors
      Rudge, Andy; Davey, John; Raistrick, Ian; Gottesfeld, Shimshon; Ferraris, John P.
      Journal of Power Sources (1994), 47 (1-2), 89-107CODEN: JPSODZ; ISSN:0378-7753.
      Electronically conducting polymers represent an interesting class of materials for use in electrochem. capacitors thanks to the combination of high capacitive energy d. and low materials cost. Three generalized types of electrochem. capacitors can be constructed using conducting polymers as active material, and in the 3rd of these, which uses conducting polymers that can be both n- and p-doped, energy densities of up to 39 Wh per kg of active material on both electrodes were demonstrated. This energy d. is obtained using poly-3-(4-fluorophenyl)thiophene (PFPT) in an electrolyte of 1M tetramethylammonium trifluoromethanesulfonate (TMATFMS) in acetonitrile. This unique system exhibits reversible n- and p-doping to high charge d. in relatively thick films of the active polymer and a cell voltage exceeding 3 V in the fully charged state. Impedance data for both n- and p-doped PFPT suggest that high power densities can be obtained in electrochem. capacitors based on this active conducting polymer.
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    49. 49
      Inal, S.; Rivnay, J.; Suiu, A.-O.; Malliaras, G. G.; McCulloch, I. Conjugated Polymers in Bioelectronics. Acc. Chem. Res. 2018, 51 (6), 1368– 1376,  DOI: 10.1021/acs.accounts.7b00624
      49
      Conjugated Polymers in Bioelectronics
      Inal, Sahika; Rivnay, Jonathan; Suiu, Andreea-Otilia; Malliaras, George G.; McCulloch, Iain
      Accounts of Chemical Research (2018), 51 (6), 1368-1376CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)
      A review. The emerging field of org. bioelectronics bridges the electronic world of org.-semiconductor-based devices with the soft, predominantly ionic world of biol. This crosstalk can occur in both directions. For example, a biochem. reaction may change the doping state of an org. material, generating an electronic readout. Conversely, an electronic signal from a device may stimulate a biol. event. Cutting-edge research in this field results in the development of a broad variety of meaningful applications, from biosensors and drug delivery systems to health monitoring devices and brain-machine interfaces. Conjugated polymers share similarities in chem. "nature" with biol. mols. and can be engineered on various forms, including hydrogels that have Young's moduli similar to those of soft tissues and are ionically conducting. The structure of org. materials can be tuned through synthetic chem., and their biol. properties can be controlled using a variety of functionalization strategies. Finally, org. electronic materials can be integrated with a variety of mech. supports, giving rise to devices with form factors that enable integration with biol. systems. While these developments are innovative and promising, it is important to note that the field is still in its infancy, with many unknowns and immense scope for exploration and highly collaborative research. The first part of this Account details the unique properties that render conjugated polymers excellent biointerfacing materials. The authors then offer an overview of the most common conjugated polymers that have been used as active layers in various org. bioelectronics devices, highlighting the importance of developing new materials. These materials are the most popular ethylenedioxythiophene derivs. as well as conjugated polyelectrolytes and ion-free org. semiconductors functionalized for the biol. interface. The authors then discuss several applications and operation principles of state-of-the-art bioelectronics devices. These devices include electrodes applied to sense/trigger electrophysiol. activity of cells as well as electrolyte-gated field-effect and electrochem. transistors used for sensing of biochem. markers. Another prime application example of conjugated polymers is cell actuators. External modulation of the redox state of the underlying conjugated polymer films controls the adhesion behavior and viability of cells. These smart surfaces can be also designed as three-dimensional architectures because of the processability of conjugated polymers. As such, cell-loaded scaffolds based on electroactive polymers enable integrated sensing or stimulation within the engineered tissue itself. A last application example is org. neuromorphic devices, an alternative computing architecture that takes inspiration from biol. and, in particular, from the way the brain works. Leveraging ion redistribution inside a conjugated polymer upon application of an elec. field and its coupling with electronic charges, conjugated polymers can be engineered to act as artificial neurons or synapses with complex, history-dependent behavior. The authors conclude this Account by highlighting main factors that need to be considered for the design of a conjugated polymer for applications in bioelectronics-although there can be various figures of merit given the broad range of applications, as emphasized in this Account.
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    50. 50
      Pelclova, D. Osmium. In Handbook on the Toxicology of Metals; Elsevier, 2022; pp 639– 647.
      There is no corresponding record for this reference.
    51. 51
      Bernacka-Wojcik, I.; Talide, L.; Abdel Aziz, I.; Simura, J.; Oikonomou, V. K.; Rossi, S.; Mohammadi, M.; Dar, A. M.; Seitanidou, M.; Berggren, M.; Simon, D. T.; Tybrandt, K.; Jonsson, M. P.; Ljung, K.; Niittylä, T.; Stavrinidou, E. Flexible Organic Electronic Ion Pump for Flow-Free Phytohormone Delivery into Vasculature of Intact Plants. Advanced Science 2023, 10 (14), 1– 11,  DOI: 10.1002/advs.202206409
      There is no corresponding record for this reference.
    52. 52
      Donahue, M. J.; Kaszas, A.; Turi, G. F.; Rózsa, B.; Slézia, A.; Vanzetta, I.; Katona, G.; Bernard, C.; Malliaras, G. G.; Williamson, A. Multimodal Characterization of Neural Networks Using Highly Transparent Electrode Arrays. eNeuro 2018, 5 (6), ENEURO.0187-18.2018  DOI: 10.1523/ENEURO.0187-18.2018
      There is no corresponding record for this reference.

  • Supporting Information

    Supporting Information

    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsabm.4c01425.

    • Cyclic voltammetry of p(ETE-S) on ITO substrates, reduction/oxidation peaks of Os2+/Os3+ versus (v)1/2, cyclic voltammetry of PVI–Os catalysis on ITO with/without p(ETE-S), cyclic voltammetry of p(ETE-S) capacitance recovery after catalysis, normalized response of p(ETE-S)/PEGDE/Gox/PVI–Os with the addition of glucose, SEM image of the root morphology after enzyme deposition, metabolomics of root exudates, extracted data of charge/discharge curves, and precision of the 4-point probe measurements (PDF)


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