Organic Mixed Ionic-Electronic Conductors Based on Tunable and Functional Poly(3,4-ethylenedioxythiophene) Copolymers.

Organic mixed ionic-electronic conductors (OMIECs) are being explored in applications such as bioelectronics, biosensors, energy conversion and storage, and optoelectronics. OMIECs are largely composed of conjugated polymers that couple ionic and electronic transport in their structure as well as synthetic flexibility. Despite extensive research, previous studies have mainly focused on either enhancing ion conduction or enabling synthetic modification. This limited the number of OMIECs that excel in both domains. Here, a series of OMIECs based on functionalized poly(3,4-ethylenedioxythiophene) (PEDOT) copolymers that combine efficient ion/electron transport with the versatility of post-functionalization were developed. EDOT monomers bearing sulfonic (EDOTS) and carboxylic acid (EDOTCOOH) groups were electrochemically copolymerized in different ratios on oxygen plasma-treated conductive substrates. The plasma treatment enabled the synthesis of copolymers containing high ratios of EDOTS (up to 68%), otherwise not possible with untreated substrates. This flexibility in synthesis resulted in the fabrication of copolymers with tunable properties in terms of conductivity (2-0.0019 S/cm) and ion/electron transport, for example, as revealed by their volumetric capacitances (122-11 F/cm3). The importance of the organic nature of the OMIECs that are amenable to synthetic modification was also demonstrated. EDOTCOOH was successfully post-functionalized without influencing the ionic and electronic transport of the copolymers. This opens a new way to tailor the properties of the OMIECs to specific applications, especially in the field of bioelectronics.

Mixing Insulating Commodity Polymers with Semiconducting n-type Polymers Enables High-Performance Electrochemical Transistors.

Diluting organic semiconductors with a host insulating polymer is used to increase the electronic mobility in organic electronic devices, such as thin film transistors, while considerably reducing material costs. In contrast to organic electronics, bioelectronic devices such as the organic electrochemical transistor (OECT) rely on both electronic and ionic mobility for efficient operation, making it challenging to integrate hydrophobic polymers as the predominant blend component. This work shows that diluting the n-type conjugated polymer p(N-T) with high molecular weight polystyrene (10 KDa) leads to OECTs with over three times better mobility-volumetric capacitance product (µC*) with respect to the pristine p(N-T) (from 4.3 to 13.4 F V-1 cm-1 s-1) while drastically decreasing the amount of conjugated polymer (six times less). This improvement in µC* is due to a dramatic increase in electronic mobility by two orders of magnitude, from 0.059 to 1.3 cm2 V-1 s-1 for p(N-T):Polystyrene 10 KDa 1:6. Moreover, devices made with this polymer blend show better stability, retaining 77% of the initial drain current after 60 minutes operation in contrast to 12% for pristine p(N-T). These results open a new generation of low-cost organic mixed ionic-electronic conductors where the bulk of the film is made by a commodity polymer.

Cleanroom-Free Direct Laser Micropatterning of Polymers for Organic Electrochemical Transistors in Logic Circuits and Glucose Biosensors.

Organic electrochemical transistors (OECTs) are promising devices for bioelectronics, such as biosensors. However, current cleanroom-based microfabrication of OECTs hinders fast prototyping and widespread adoption of this technology for low-volume, low-cost applications. To address this limitation, a versatile and scalable approach for ultrafast laser microfabrication of OECTs is herein reported, where a femtosecond laser to pattern insulating polymers (such as parylene C or polyimide) is first used, exposing the underlying metal electrodes serving as transistor terminals (source, drain, or gate). After the first patterning step, conducting polymers, such as poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS), or semiconducting polymers, are spin-coated on the device surface. Another femtosecond laser patterning step subsequently defines the active polymer area contributing to the OECT performance by disconnecting the channel and gate from the surrounding spin-coated film. The effective OECT width can be defined with high resolution (down to 2 µm) in less than a second of exposure. Micropatterning the OECT channel area significantly improved the transistor switching performance in the case of PEDOT:PSS-based transistors, speeding up the devices by two orders of magnitude. The utility of this OECT manufacturing approach is demonstrated by fabricating complementary logic (inverters) and glucose biosensors, thereby showing its potential to accelerate OECT research.

2D MXene electrochemical transistors.

The solid-state field-effect transistor, FET, and its theories were paramount in the discovery and studies of graphene. In the past two decades another transistor based on conducting polymers, called organic electrochemical transistor (ECT), has been developed and largely studied. The main difference between organic ECTs and FETs is the mode and extent of channel doping; while in FETs the channel only has surface doping through dipoles, the mixed ionic-electronic conductivity of the channel material in organic ECTs enables bulk electrochemical doping. As a result, organic ECTs maximize conductance modulation at the expense of speed. To date ECTs have been based on conducting polymers, but here we show that MXenes, a class of 2D materials beyond graphene, enable the realization of electrochemical transistors (ECTs). We show that the formulas for organic ECTs can be applied to these 2D ECTs and used to extract parameters like mobility. These MXene ECTs have high transconductance values but low on-off ratios. We further show that conductance switching data measured using ECT, in combination with other in situ-ex situ electrochemical measurements, is a powerful tool for correlating the change in conductance to that of the redox state, to our knowledge, this is the first report of this important correlation for MXene films. 2D ECTs can draw great inspiration and theoretical tools from the field of organic ECTs and have the potential to considerably extend the capabilities of transistors beyond those of conducting polymer ECTs, with added properties such as extreme heat resistance, tolerance for solvents, and higher conductivity for both electrons and ions than conducting polymers.

Probabilistic cell seeding and non-autofluorescent 3D-printed structures as scalable approach for multi-level co-culture modeling.

To model complex biological tissue in vitro, a specific layout for the position and numbers of each cell type is necessary. Establishing such a layout requires manual cell placement in three dimensions (3D) with micrometric precision, which is complicated and time-consuming. Moreover, 3D printed materials used in compartmentalized microfluidic models are opaque or autofluorescent, hindering parallel optical readout and forcing serial characterization methods, such as patch-clamp probing. To address these limitations, we introduce a multi-level co-culture model realized using a parallel cell seeding strategy of human neurons and astrocytes on 3D structures printed with a commercially available non-autofluorescent resin at micrometer resolution. Using a two-step strategy based on probabilistic cell seeding, we demonstrate a human neuronal monoculture that forms networks on the 3D printed structure and can establish cell-projection contacts with an astrocytic-neuronal co-culture seeded on the glass substrate. The transparent and non-autofluorescent printed platform allows fluorescence-based immunocytochemistry and calcium imaging. This approach provides facile multi-level compartmentalization of different cell types and routes for pre-designed cell projection contacts, instrumental in studying complex tissue, such as the human brain.

Corrigendum to "Probabilistic cell seeding and non-autofluorescent 3D-printed structures as scalable approach for multi-level co-culture modeling" [Mater. Today Bio 21, August 2023, 100706].

[This corrects the article DOI: 10.1016/j.mtbio.2023.100706.].

Current Progress of Interfacing Organic Semiconducting Materials with Bacteria.

Microbial bioelectronics require interfacing microorganisms with electrodes. The resulting abiotic/biotic platforms provide the basis of a range of technologies, including energy conversion and diagnostic assays. Organic semiconductors (OSCs) provide a unique strategy to modulate the interfaces between microbial systems and external electrodes, thereby improving the performance of these incipient technologies. In this review, we explore recent progress in the field on how OSCs, and related materials capable of charge transport, are being used within the context of microbial systems, and more specifically bacteria. We begin by examining the electrochemical communication modes in bacteria and the biological basis for charge transport. Different types of synthetic organic materials that have been designed and synthesized for interfacing and interrogating bacteria are discussed next, followed by the most commonly used characterization techniques for evaluating transport in microbial, synthetic, and hybrid systems. A range of applications is subsequently examined, including biological sensors and energy conversion systems. The review concludes by summarizing what has been accomplished so far and suggests future design approaches for OSC bioelectronics materials and technologies that hybridize characteristic properties of microbial and OSC systems.

A One Step Procedure toward Conductive Suspensions of Liposome-Polyaniline Complexes.

Interaction of conjugated polymers with liposomes is an attractive approach that benefits from both systems' characteristics such as electroactivity and enhanced interaction with cells. Conjugated polymer-liposome complexes have been investigated for bioimaging, drug delivery, and photothermal therapy. Their fabrication has largely been achieved by multistep procedures that require first the synthesis and processing of the conjugated polymer. Here, a new one step fabrication approach is reported based on in situ polymerization of a conjugated monomer precursor around liposomes. Polyaniline (PANI) doped with phytic acid is synthesized via oxidative polymerization in the presence of 1,2-dioleoyl-sn-glycero-3-phosphatidylcholine (DOPC) vesicles to produce a conductive aqueous suspension of Liposome-PANI complexes. PANI interacts with liposomes without disrupting the bilayer as shown using differential scanning calorimetry and fluorescence quenching studies of the hydrophobic Nile red probe. The electronic conductivity of the Liposome-PANI complexes, which stems from the doped PANI accessible on the liposome surface, is confirmed using conductive atomic force microscopy and electrochemical impedance spectroscopy. Further, short-term in vitro cell studies show that the complexes colocalize with the cell membrane without reducing cell proliferation. This study presents a novel fabrication route to conductive suspensions of conjugated polymer-liposome complexes suitable for potential applications at the biointerface.

Conjugated Polymers for Assessing and Controlling Biological Functions.

The field of organic bioelectronics is advancing rapidly in the development of materials and devices to precisely monitor and control biological signals. Electronics and biology can interact on multiple levels: organs, complex tissues, cells, cell membranes, proteins, and even small molecules. Compared to traditional electronic materials such as metals and inorganic semiconductors, conjugated polymers (CPs) have several key advantages for biological interactions: tunable physiochemical properties, adjustable form factors, and mixed conductivity (ionic and electronic). Herein, the use of CPs in five biologically oriented research topics, electrophysiology, tissue engineering, drug release, biosensing, and molecular bioelectronics, is discussed. In electrophysiology, implantable devices with CP coating or CP-only electrodes are showing improvements in signal performance and tissue interfaces. CP-based scaffolds supply highly favorable static or even dynamic interfaces for tissue engineering. CPs also enable delivery of drugs through a variety of mechanisms and form factors. For biosensing, CPs offer new possibilities to incorporate biological sensing elements in a conducting matrix. Molecular bioelectronics is today used to incorporate (opto)electronic functions in living tissue. Under each topic, the limits of the utility of CPs are discussed and, overall, the major challenges toward implementation of CPs and their devices to real-world applications are highlighted.

Di- and Tetrairon(III) µ-Oxido Complexes of an N3S-Donor Ligand: Catalyst Precursors for Alkene Oxidations.

The new di- and tetranuclear Fe(III) µ-oxido complexes [Fe4(µ-O)4(PTEBIA)4](CF3SO3)4(CH3CN)2] (1a), [Fe2(µ-O)Cl2(PTEBIA)2](CF3SO3)2 (1b), and [Fe2(µ-O)(HCOO)2(PTEBIA)2](ClO4)2 (MeOH) (2) were prepared from the sulfur-containing ligand (2-((2,4-dimethylphenyl)thio)-N,N-bis ((1-methyl-benzimidazol-2-yl)methyl)ethanamine (PTEBIA). The tetrairon complex 1a features four µ-oxido bridges, while in dinuclear 1b, the sulfur moiety of the ligand occupies one of the six coordination sites of each Fe(III) ion with a long Fe-S distance of 2.814(6) Å. In 2, two Fe(III) centers are bridged by one oxido and two formate units, the latter likely formed by methanol oxidation. Complexes 1a and 1b show broad sulfur-to-iron charge transfer bands around 400-430 nm at room temperature, consistent with mononuclear structures featuring Fe-S interactions. In contrast, acetonitrile solutions of 2 display a sulfur-to-iron charge transfer band only at low temperature (228 K) upon addition of H2O2/CH3COOH, with an absorption maximum at 410 nm. Homogeneous oxidative catalytic activity was observed for 1a and 1b using H2O2 as oxidant, but with low product selectivity. High valent iron-oxo intermediates could not be detected by UV-vis spectroscopy or ESI mass spectrometry. Rather, evidence suggest preferential ligand oxidation, in line with the relatively low selectivity and catalytic activity observed in the reactions.

Active Materials for Organic Electrochemical Transistors.

The organic electrochemical transistor (OECT) is a device capable of simultaneously controlling the flow of electronic and ionic currents. This unique feature renders the OECT the perfect technology to interface man-made electronics, where signals are conveyed by electrons, with the world of the living, where information exchange relies on chemical signals. The function of the OECT is controlled by the properties of its core component, an organic conductor. Its chemical structure and interactions with electrolyte molecules at the nanoscale play a key role in regulating OECT operation and performance. Herein, the latest research progress in the design of active materials for OECTs is reviewed. Particular focus is given on the conducting polymers whose properties lead to advances in understanding the OECT working mechanism and improving the interface with biological systems for bioelectronics. The methods and device models that are developed to elucidate key relations between the structure of conducting polymer films and OECT function are discussed. Finally, the requirements of OECT design for in vivo applications are briefly outlined. The outcomes represent an important step toward the integration of organic electronic components with biological systems to record and modulate their functions.

Highly Stable Conjugated Polyelectrolytes for Water-Based Hybrid Mode Electrochemical Transistors.

Hydrophobic, self-doped conjugated polyelectrolytes (CPEs) are introduced as highly stable active materials for organic electrochemical transistors (OECTs). The hydrophobicity of CPEs renders films very stable in aqueous solutions. The devices operate at gate voltages around zero and show no signs of degradation when operated for 104 cycles under ambient conditions. These properties make the produced OECTs ideal devices for applications in bioelectronics.

Water oxidation catalyzed by molecular di- and nonanuclear Fe complexes: importance of a proper ligand framework.

The synthesis of two molecular iron complexes, a dinuclear iron(iii,iii) complex and a nonanuclear iron complex, based on the dinucleating ligand 2,2'-(2-hydroxy-5-methyl-1,3-phenylene)bis(1H-benzo[d]imidazole-4-carboxylic acid) is described. The two iron complexes were found to drive the oxidation of water by the one-electron oxidant [Ru(bpy)3](3+).

Electronic polymers in lipid membranes.

Electrical interfaces between biological cells and man-made electrical devices exist in many forms, but it remains a challenge to bridge the different mechanical and chemical environments of electronic conductors (metals, semiconductors) and biosystems. Here we demonstrate soft electrical interfaces, by integrating the metallic polymer PEDOT-S into lipid membranes. By preparing complexes between alkyl-ammonium salts and PEDOT-S we were able to integrate PEDOT-S into both liposomes and in lipid bilayers on solid surfaces. This is a step towards efficient electronic conduction within lipid membranes. We also demonstrate that the PEDOT-S@alkyl-ammonium:lipid hybrid structures created in this work affect ion channels in the membrane of Xenopus oocytes, which shows the possibility to access and control cell membrane structures with conductive polyelectrolytes.

Structural, spectroscopic, and electrochemical properties of tri- and tetradentate N3 and N3S copper complexes with mixed benzimidazole/thioether donors.

Cupric and cuprous complexes of bis(2-methylbenzimidazolyl)(2-methylthiophene)amine (L(1)), bis(2-methylbenzimidazolyl)benzylamine (L(2)), bis(2-methylbenzimidazolyl)(2,4-dimethylphenylthioethyl)amine (L(3)), bis(1-methyl-2-methylbenzimidazolyl)benzylamine (Me(2)L(2)), and bis(1-methyl-2-methylbenzimidazolyl)(2,4-dimethylphenylthioethyl)amine (Me(2)L(3)) have been spectroscopically, structurally, and electrochemically characterised. The thioether-containing ligands L(3) and Me(2)L(3) give rise to complexes with Cu-S bonds in solution and in the solid state, as evidenced by UV-vis spectroscopy and X-ray crystallography. The Cu(2+) complexes [L(1)CuCl(2)] (1), [L(2)CuCl(2)] (2) and [Me(2)L(3)CuCl]ClO(4) (3(Me,ClO4)) are monomeric in solution according to ESI mass spectrometry data, as well as in the solid state. Their Cu(+) analogues [L(1)Cu]ClO(4), [L(2)Cu]ClO(4), [L(3)Cu]ClO(4) (4-6), [BOC(2)L(1)Cu(NCCH(3))]ClO(4) (4(BOC)), [Me(2)L(2)Cu(NCCH(3))(2)]PF(6) (5(Me)) and [Me(2)L(3)Cu](2)(ClO(4))(2) (6(Me)) are also monomeric in acetonitrile solution, as confirmed crystallographically for 4(BOC) and 5(Me). In contrast, 6(Me) is dimeric in the solid state, with the thioether group of one of the ligands bound to a symmetry-related Cu(+) ion. Cyclic voltammetry studies revealed that the bis(2-methylbenzimidazolyl)amine-Cu(2+)/Cu(+) systems possess half-wave potentials in the range -0.16 to -0.08 V (referenced to the ferrocenium-ferrocene couple); these values are nearly 0.23 V less negative than those reported for related bis(picolyl)amine-derived ligands. Based on these observations, the N(3) or N(3)S donor set of the benzimidazole-derived ligands is analogous to previously reported chelating systems, but the electronic environment they provide is unique, and may have relevance to histidine and methionine-containing metalloenzymes. This is also reflected in the reactivity of [Me(2)L(2)Cu(NCCH(3))(2)](+) (5(Me)) and [Me(2)L(3)Cu](+) (6(Me)) towards dioxygen, which results in the production of the superoxide anion in both cases. The thioether-bound Cu(+) centre in 6(Me) appears to be more selective in the generation of O(2)˙(-) than 5(Me), lending evidence to the hypothesis of the modulating properties of thioether ligands in Cu-O(2) reactions.