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Nanocellulose-based membranes have attracted intense attention in bioelectronic devices due to their low cost, flexibility, biocompatibility, degradability, and sustainability. Herein, we demonstrate a flexible ionic diode using a cross-linked bipolar membrane fabricated from positively and negatively charged cellulose nanofibrils (CNFs). The rectified current originates from the asymmetric charge distribution, which can selectively determine the direction of ion transport inside the bipolar membrane. The mechanism of rectification was demonstrated by electrochemical impedance spectroscopy with voltage biases. The rectifying behavior of this kind of ionic diode was studied by using linear sweep voltammetry to obtain current-voltage characteristics and the time dependence of the current. In addition, the performance of cross-linked CNF diodes was investigated while changing parameters such as the thickness of the bipolar membranes, the scanning voltage range, and the scanning rate. A good long-term stability due to the high density cross-linking of the diode was shown in both current-voltage characteristics and the time dependence of current., QC 20240326

QC 20240215

Aqueous organic redox flow battery (AORFB) is a technological route towards the large-scale sustainable energy storage. However, several factors need to be controlled to maintain the AORFB performance. Prevention of posolyte and negolyte cross-contamination in asymmetric AORFBs, one of the main causes of capacity decay, relies on their membranes' ability to prevent migration of the redox-active species between the two electrolytes. The barrier properties are often traded for a reduction in ionic conductivity which is crucial to enable the device operation. Another factor greatly affecting quinone-based AORFBs is the Michael addition reaction (MAR) on the charged posolyte, quinone, which has been identified as a major reason for all-quinone AORFBs performance deterioration. Herein, we investigate deterioration scenarios of an all-quinone AORFB using both experimental and computational methods. The study includes a series of membranes based on sulfonated cellulose nanofibrils and different membrane modifications. The layer-by-layer (LbL) surface modifications, i.e. the incorporation of inorganic materials and the reduction of the pore size of the sulfonated cellulose membranes, were all viable routes to reduce the passive diffusion permeability of membranes which correlated to an increased cycling stability of the battery. The kinetics of MAR on quinone was detected using NMR and its impact on the performance fading was modeled computationally. The localization of MAR close to the membrane, which can be assigned to the surface reactivity, affects the diffusion of MAR reagent and the deterioration dynamics of the present all-quinone AORFB., QC 20240222

Electrocatalysis enables the industrial transition to sustainable production of chemicals using abundant precursors and electricity from renewable sources. De-centralized production of hydrogen peroxide (H2O2) from water and oxygen of air is highly desirable for daily life and industry. We report an effective electrochemical refinery (e-refinery) for H2O2 by means of electrocatalysis-controlled comproportionation reaction (2(H)O + O -> 2(HO)), feeding pure water and oxygen only. Mesoporous nickel (II) oxide (NiO) was used as electrocatalyst for oxygen evolution reaction (OER), producing oxygen at the anode. Conducting polymer poly(3,4-ethylenedioxythiophene): poly(styrene sulfonate) (PEDOT:PSS) drove the oxygen reduction reaction (ORR), forming H2O2 on the cathode. The reactions were evaluated in both half-cell and device configurations. The performance of the H2O2 e-refinery, assembled on anion-exchange solid electrolyte and fed with pure water, was limited by the unbalanced ionic transport. Optimization of the operation conditions allowed a conversion efficiency of 80%., Funding: Swedish Agency for Innovation Systems (Vinnova) [2016-05156]; Swedish Energy Agency [42022-1]; Swedish Research Council [VR 2021-04427, VR 2019-05577, VR 2016-05990]; Centre in Nanoscience and Technology (CeNano, Linkoeping Institute of Technology (LiTH), Linkoeping University, 2020, 2021); Swedish Government Strategic Research Area in Materials Science on Advanced Functional Materials at Linkoeping University (Faculty Grant SFO-Mat-LiU) [2009-00971]; Knut and Alice Wallenberg Foundation (H2O2) [KAW 2018.0058]

Local and long-lasting administration of potent chemotherapeutics is a promising therapeutic intervention to increase the efficiency of chemotherapy of hard-to-treat tumors such as the most lethal brain tumors, glioblastomas (GBM). However, despite high toxicity for GBM cells, potent chemotherapeutics such as gemcitabine (Gem) cannot be widely implemented as they do not efficiently cross the blood brain barrier (BBB). As an alternative method for continuous administration of Gem, we here operate freestanding iontronic pumps - "GemIPs" - equipped with a custom-synthesized ion exchange membrane (IEM) to treat a GBM tumor in an avian embryonic in vivo system. We compare GemIP treatment effects with a topical metronomic treatment and observe that a remarkable growth inhibition was only achieved with steady dosing via GemIPs. Daily topical drug administration (at the maximum dosage that was not lethal for the embryonic host organism) did not decrease tumor sizes, while both treatment regimes caused S-phase cell cycle arrest and apoptosis. We hypothesize that the pharmacodynamic effects generate different intratumoral drug concentration profiles for each technique, which causes this difference in outcome. We created a digital model of the experiment, which proposes a fast decay in the local drug concentration for the topical daily treatment, but a long-lasting high local concentration of Gem close to the tumor area with GemIPs. Continuous chemotherapy with iontronic devices opens new possibilities in cancer treatment: the long-lasting and highly local dosing of clinically available, potent chemotherapeutics to greatly enhance treatment efficiency without systemic side-effects. Significance statement: Iontronic pumps (GemIPs) provide continuous and localized administration of the chemotherapeutic gemcitabine (Gem) for treating glioblastoma in vivo. By generating high and constant drug concentrations near the vascularized growing tumor, GemIPs offer an efficient and less ha, Funding Agencies|PhD program Molecular Medicine (MOLMED) of the Medical University of Graz; PhD program Metabolic and Cardiovascular Disease (DK-MCD) of the Medical University of Graz; Austrian Science Fund (FWF) [TAI 245, W1266, F73 -P09]; Marietta Blau fellowship; European Union's Horizon Europe program via the European Innovation Council under the EIC Pathfinder Open project bioSWITCH [101099963]; Swedish Foundation for Strategic Research; Knut and Alice Wallenberg Foundation [2022.0316]; European Research Council [834677]

Organic electrochemical transistors (OECTs) have emerged as promising candidates for various fields, including bioelectronics, neuromorphic computing, biosensors, and wearable electronics. OECTs operate in aqueous solutions, exhibit high amplification properties, and offer ion-to-electron signal transduction. The OECT channel consists of a conducting polymer, with PEDOT:PSS receiving the most attention to date. While PEDOT:PSS is highly conductive, and benefits from optimized protocols using secondary dopants and detergents, new p-type and n-type polymers are emerging with desirable material properties. Among these, low-oxidation potential oligomers are highly enabling for bioelectronics applications, however the polymers resulting from their polymerization lag far behind in conductivity compared with the established PEDOT:PSS. In this work we show that by careful design of the OECT geometrical characteristics, we can overcome this limitation and achieve devices that are on-par with transistors employing PEDOT:PSS. We demonstrate that the vertical architecture allows for facile electropolymerization of a family of trimers that are polymerized in very low oxidation potentials, without the need for harsh chemicals or secondary dopants. Vertical and planar OECTs are compared using various characterization methods. We show that vOECTs are superior platforms in general and propose that the vertical architecture can be expanded for the realization of OECTs for various applications., Funding agencies: European Research Council (AdG 2018 Magnus Berggren, 834677), the Swedish Research Council (2018-06197), and the Swedish Foundation for Strategic Research (RMX18-0083), the Swedish Research Council (2022-04807, 2023-05459), the Swedish Government Strategic Research Areas in Materials Science on Functional Materials at Linköping University (Faculty Grant SFOMat-LiU No. 2009-00971).

Spatiotemporal controlled drug delivery minimizes side-effects and enables therapies that require specific dosing patterns. Conjugated polymers (CP) can be used for electrically controlled drug delivery; however so far, most demonstrations were limited to molecules up to 500 Da. Larger molecules could be incorporated only during the CP polymerization and thus limited to a single delivery. This work harnesses the record volume changes of a glycolated polythiophene p(g3T2) for controlled drug delivery. p(g3T2) undergoes reversible volumetric changes of up to 300% during electrochemical doping, forming pores in the nm-size range, resulting in a conducting hydrogel. p(g3T2)-coated 3D carbon sponges enable controlled loading and release of molecules spanning molecular weights of 800-6000 Da, from simple dyes up to the hormone insulin. Molecules are loaded as a combination of electrostatic interactions with the charged polymer backbone and physical entrapment in the porous matrix. Smaller molecules leak out of the polymer while larger ones could not be loaded effectively. Finally, this work shows the temporally patterned release of molecules with molecular weight of 1300 Da and multiple reloading and release cycles without affecting the on/off ratio.

Electrochemical doping of organic mixed ionic-electronic conductors is key for modulating their conductivity, charge storage and volume enabling high performing bioelectronic devices such as recording and stimulating electrodes, transistors-based sensors and actuators. However, electrochemical doping has not been explored to the same extent for modulating the mechanical properties of OMIECs on demand. Here, we report a qualitative and quantitative study on how the mechanical properties of a glycolated polythiophene, p(g3T2), change in situ during electrochemical doping and de-doping. The Young's modulus of p(g3T2) changes from 69 MPa in the dry state to less than 10 MPa in the hydrated state and then further decreases down to 0.4 MPa when electrochemically doped. With electrochemical doping-dedoping the Young's modulus of p(g3T2) changes by more than one order of magnitude reversibly, representing the largest modulation reported for an OMIEC. Furthermore, we show that the electrolyte concentration affects the magnitude of the change, demonstrating that in less concentrated electrolytes more water is driven into the film due to osmosis and therefore the film becomes softer. Finally, we find that the oligo ethylene glycol side chain functionality, specifically the length and asymmetry, affects the extent of modulation. Our findings show that glycolated polythiophenes are promising materials for mechanical actuators with a tunable modulus similar to the range of biological tissues, thus opening a pathway for new mechanostimulation devices. This work investigates the changes in the mechanical properties of glycolated polythiophenes induced by electrochemical addressing and by electrolyte concentration, due to its ability to stabilize water., Funding Agencies|Swedish Foundation for Strategic Research [FFL18-0101]; Swedish Research Council [VR-2020-05045]; Swedish Government Strategic Research Area in Materials Science on Advanced Functional Materials at Linkoeping University [2009-00971]

The quest for eco-friendly materials with anticipated positive impact for sustainability is crucial to achieve the UN sustainable development goals. Classical strategies of composite materials can be applied on novel nanomaterials and green materials. Besides the actual technology and applications also processing and manufacturing methods should be further advanced to make entire technology concepts sustainable. Here, they show an efficient way to combine two low-cost materials, cellulose and zinc oxide (ZnO), to achieve novel functional and "green" materials via paper-making processes. While cellulose is the most abundant and cost-effective organic material extractable from nature. ZnO is cheap and known of its photocatalytic, antibacterial, and UV absorption properties. ZnO nanowires are grown directly onto cellulose fibers in water solutions and then dewatered in a process mimicking existing steps of large-scale papermaking technology. The ZnO NW paper exhibits excellent photo-conducting properties under simulated sunlight with good ON/OFF switching and long-term stability (90 minutes). It also acts as an efficient photocatalyst for hydrogen peroxide (H2O2) generation (5.7 x 10(-9) m s(-1)) with an envision the possibility of using it in buildings to enable large surfaces to spontaneously produce H2O2 at its outer surface. Such technology promise for fast degradation of microorganisms to suppress the spreading of diseases., Funding Agencies|Knut and Alice Wallenberg Foundation; VINNOVA (Digital Cellulose Center); Vetenskapradet [2016-05990]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoeping University [2009-00971]; aForsk Foundation [17-433]

The conductivity of organic polymer heterojunction devices relies on the electron dynamics occurring along interfaces between the acceptor and donor moieties. To investigate these dynamics with chemical specificity, spectroscopic techniques are employed to obtain localized snapshots of the electron behavior at selected interfaces. In this study, charge transfer in blends (by weight 10, 50, 90, and 100%) of p-type polymer P(g(4)2T-T) (bithiophene-thiophene) and n-type polymer BBL (poly(benzimidazo-benzo-phenanthroline)) was measured by resonant Auger spectroscopy. Electron spectra emanating from the decay of core-excited states created upon X-ray absorption in the donor polymer P(g(4)2T-T) were measured in the sulfur KL2,3L2,3 Auger kinetic energy region as a function of the excitation energy. By tuning the photon energy across the sulfur K-absorption edge, it is possible to differentiate between decay paths in which the core-excited electron remained on the atom with the core-hole and those where it tunneled away. Analyzing the competing decay modes of these localized and delocalized (charge-transfer) processes facilitated the computation of charge-transfer times as a function of excitation energy using the core-hole clock method. The electron delocalization times derived from the measurements were found to be in the as/fs regime for all polymer blends, with the fastest charge transfer occurring in the sample with an equal amount of donor and acceptor polymer. These findings highlight the significance of core-hole clock spectroscopy as a chemically specific tool for examining the local charge tunneling propensity, which is fundamental to understanding macroscopic conductivity. Additionally, the X-ray absorption spectra near the sulfur K-edge in the P(g(4)2T-T) polymer for different polymer blends were analyzed to compare molecular structure, orientation, and ordering in the polymer heterojunctions. The 50% donor sample exhibited the most pronounced angular dependenc, QC 20240201

The nature of mass transport in plants has recently inspired the development of low-cost and sustainable wood-based electronics. Herein, we report a wood electrochemical transistor (WECT) where all three electrodes are fully made of conductive wood (CW). The CW is prepared using a two-step strategy of wood delignification followed by wood amalgamation with a mixed electron-ion conducting polymer, poly(3,4-ethylenedioxythiophene)–polystyrene sulfonate (PEDOT:PSS). The modified wood has an electrical conductivity of up to 69 Sm−1 induced by the formation of PEDOT:PSS microstructures inside the wood 3D scaffold. CW is then used to fabricate the WECT, which is capable of modulating an electrical current in a porous and thick transistor channel (1 mm) with an on/off ratio of 50. The device shows a good response to gate voltage modulation and exhibits dynamic switching properties similar to those of an organic electrochemical transistor. This wood-based device and the proposed working principle demonstrate the possibility to incorporate active electronic functionality into the wood, suggesting different types of bio-based electronic devices., QC 20230713

Soft vibrotactile devices have the potential to expandthe functionalityof emerging electronic skin technologies. However, those devices oftenlack the necessary overall performance, sensing-actuation feedbackand control, and mechanical compliance for seamless integration onthe skin. Here, we present soft haptic electromagnetic actuators thatconsist of intrinsically stretchable conductors, pressure-sensitiveconductive foams, and soft magnetic composites. To minimize jouleheating, high-performance stretchable composite conductors are developedbased on in situ-grown silver nanoparticles formed within the silverflake framework. The conductors are laser-patterned to form soft anddensely packed coils to further minimize heating. Soft pressure-sensitiveconducting polymer-cellulose foams are developed and integrated totune the resonance frequency and to provide internal resonator amplitudesensing in the resonators. The above components together with a softmagnet are assembled into soft vibrotactile devices providing high-performanceactuation combined with amplitude sensing. We believe that soft hapticdevices will be an essential component in future developments of multifunctionalelectronic skin for future human-computer and human-roboticinterfaces.

Seamless integration between biological systems and electrical components is essential for enabling a twinned biochemical–electrical recording and therapy approach to understand and combat neurological disorders. Employing bioelectronic systems made up of conjugated polymers, which have an innate ability to transport both electronic and ionic charges, provides the possibility of such integration. In particular, translating enzymatically polymerized conductive wires, recently demonstrated in plants and simple organism systems, into mammalian models, is of particular interest for the development of next-generation devices that can monitor and modulate neural signals. As a first step toward achieving this goal, enzyme-mediated polymerization of two thiophene-based monomers is demonstrated on a synthetic lipid bilayer supported on a Au surface. Microgravimetric studies of conducting films polymerized in situ provide insights into their interactions with a lipid bilayer model that mimics the cell membrane. Moreover, the resulting electrical and viscoelastic properties of these self-organizing conducting polymers suggest their potential as materials to form the basis for novel approaches to in vivo neural therapeutics., Funding: Swedish Foundation for Strategic Research [RMX18-0083]; Swedish Research Council [201806197]; European Research Council [834677 e-NeuroPharma ERC-2018-ADG]

The interfacial energetics are known to play a crucial role in organic diodes, transistors, and sensors. Designing the metal-organic interface has been a tool to optimize the performance of organic (opto)electronic devices, but this is not reported for organic thermoelectrics. In this work, it is demonstrated that the electrical power of organic thermoelectric generators (OTEGs) is also strongly dependent on the metal-organic interfacial energetics. Without changing the thermoelectric figure of merit (ZT) of polythiophene-based conducting polymers, the generated power of an OTEG can vary by three orders of magnitude simply by tuning the work function of the metal contact to reach above 1000 mu W cm(-2). The effective Seebeck coefficient (S-eff) of a metal/polymer/metal single leg OTEG includes an interfacial contribution (V-inter/Delta T) in addition to the intrinsic bulk Seebeck coefficient of the polythiophenes, such that S-eff = S + V-inter/Delta T varies from 22.7 mu V K-1 [9.4 mu V K-1] with Al to 50.5 mu V K-1 [26.3 mu V K-1] with Pt for poly(3,4-ethylenedioxythiophene):p-toluenesulfonate [poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate)]. Spectroscopic techniques are used to reveal a redox interfacial reaction affecting locally the doping level of the polymer at the vicinity of the metal-organic interface and conclude that the energetics at the metal-polymer interface provides a new strategy to enhance the performance of OTEGs., Funding Agencies|Knut and Alice Wallenberg Foundation; EU [ESR 955837_HORATES]; Swedish Research Council [2016-06146, 2016-03979]; Forsk [18-313]; Academy of Finland Postdoctoral Researcher [340103]; EU H2020 Marie Sklodowska-Curie [101022777]; Swedish Foundation for Strategic Research (SiOS); Swedish Government Strategic Research Area in Materials Science on Advanced Functional Materials at Linkoeping University [2009-00971]

Lignin, obtained as a waste product in huge quantities from the large-scale cellulose processing industries, holds a great potential to be used as sustainable electrode material for large-scale electroactive energy storage systems. The fixed number of redox-active phenolic groups present within the lignin structure limits the electrochemical performance and the total energy storage capacity of the lignin-based electrodes. Herein, the way to enhance the charge storage capacity of lignin by incorporating additional small catechol molecules into the lignin structure is demonstrated. The catechol derivatives are covalently attached to the lignin via aromatic electrophilic substitution reaction. The increased phenolic groups in all functionalized lignin derivatives notably increase the values of capacitance compared to pristine lignin. Further, solvent fractionation of lignin followed by functionalization using catechol boosts three times the charge capacity of lignin electrode. Herein, a scalable, cost-effective method to enhance the electrochemical performance of lignin electrodes via incorporation of small redox active moieties into the lignin structure is demonstrated. Solvent fractionation of lignin followed by functionalization using catechol increases the charge storage capacity of the lignin-carbon composite electrode by a factor of 3 reaching record high charge capacity above 100 mAh g-1., Funding Agencies|Knut and Alice Wallenberg Foundation [KAW 2020-0174]; Wallenberg Wood Science Center; Swedish Energy Agency [P52023-1]; Forsk Foundation [22-134]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoeping University [2009-00971]

The organic electronic ion pump (OEIP) is an on-demand electrophoretic drug delivery device, that via electronic to ionic signal conversion enables drug delivery without additional pressure or volume changes. The fundamental component of OEIPs is their polyelectrolyte membranes which are shaped into ionic channels that conduct and deliver ionic drugs, with high spatiotemporal resolution. The patterning of these membranes is essential in OEIP devices and is typically achieved using laborious micro processing techniques. Here, we report the development of an inkjet printable formulation of polyelectrolyte, based on a custom anionically functionalized hyperbranched polyglycerol (i-AHPG). This polyelectrolyte ink greatly simplifies the fabrication process, and is used in the production of free standing, OEIPs on flexible polyimide substrates. Both i-AHPG and the OEIP devices are characterized, exhibiting favorable iontronic characteristics of charge selectivity and ability to transport aromatic compounds. Further, the applicability of these technologies is demonstrated by transport and delivery of the pharmaceutical compound bupivacaine to dorsal root ganglion cells with high spatial precision and effective nerve-blocking, highlighting the applicability of these technologies for biomedical scenarios., Funding: Swedish Foundation for Strategic Research; Knut and Alice Wallenberg Foundation; Swedish Research Council; European Research Council [834677]; Swedish Government Strategic Research Area in Materials Science on Advanced Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009-00971]; Vinnova

Despite a range of available pain therapies, most patients report so-called “breakthrough pain.” Coupled with global issues like opioid abuse, there is a clear need for advanced therapies and technologies for safe and effective pain management. Here the authors demonstrate a candidate for such an advanced therapy: precise and fluid-flow-free electrophoretic delivery via organic electronic ion pumps (OEIPs) of the commonly used anesthetic drug bupivacaine. Bupivacaine is delivered to dorsal root ganglion (DRG) neurons in vitro. DRG neurons are a good proxy for pain studies as they are responsible for relaying ascending sensory signals from nociceptors (pain receptors) in the peripheral nervous system to the central nervous system. Capillary based OEIPs are used due to their probe-like and free-standing form factor, ideal for interfacing with cells. By delivering bupivacaine with the OEIP and recording dose versus response (Ca2+ imaging), it is observed that only cells close to the OEIP outlet (≤75 µm) are affected (“anaesthetized”) and at concentrations up to 10s of thousands of times lower than with bulk/bolus delivery. These results demonstrate the first effective OEIP deliveryof a clinically approved and widely used analgesic pharmaceutical, and thus are a major translational milestone for this technology., Funding agencies: This work was supported by the Swedish Foundation for Strategic Research, the Knut and Alice Wallenberg Foundation, the Swedish Research Council, the European Research Council (AdG 2018 Magnus Berggren, 834677 and CoG 2019 Camilla Svensson, 866075), and Vinnova. Additional support 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).

Internet-of-Everything (IoE) is defined as networked connections of things, people, data, and processes. IoE nodes, preferably shaped as printed flexible systems, serve as the frontier outpost of the Internet and comprise devices to record and regulate states and functions. To power distributed IoE nodes in an ecofriendly manner, a technology to scavenge energy from ambience and self-powered devices is developed. For this, piezoelectricity is regarded as a key property; however, the current technology typically based on polyvinylidene difluoride (PVDF) copolymers is expensive and produced via toxic protocols. We report piezoelectric characteristics of electrochemically poled cellulose nanofiber (CNF) thin films processed from water dispersions. Poling these films under humid conditions causes breaking and reorientation of CNF segments, which results in enhanced crystal alignment rendering the resulting material piezoelectric. Generators based on poled CNF show similar piezoelectric voltage and coefficient, here measured as d(33) = 46 pm V-1, to devices including PVDF copolymer layers of similar thickness. Our findings promise low-cost and printable ecofriendly piezoelectric-powered IoE nodes., Funding Agencies|Knut and Alice Wallenberg Foundation; Swedish Research Council [2016-06146, 2018- 04037, 2009-00971]; NCD- SWEET beamline of ALBA synchrotron in Barcelona, Spain; [VR 2016-05990]