Electric double-layer (EDL) gating using a custom-synthesized polyester single-ion conductor (PE400-Li) is demonstrated on two-dimensional (2D) crystals for the first time. The electronic properties of graphene and MoTe2 field-effect transistors (FETs) gated with the single-ion conductor are directly compared to a poly(ethylene oxide) dual-ion conductor (PEO:CsClO4). The anions in the single-ion conductor are covalently bound to the backbone of the polymer, leaving only the cations free to form an EDL at the negative electrode and a corresponding cationic depletion layer at the positive electrode. Because the cations are mobile in both the single- and dual-ion conductors, a similar enhancement of the n-branch is observed in both graphene and MoTe2. Specifically, the single-ion conductor decreases the subthreshold swing in the n-branch of the bare MoTe2 FET from 5000 to 250 mV/dec and increases the current density and on/off ratio by two orders of magnitude. However, the single-ion conductor suppressed the p-branch in both the graphene and the MoTe2 FETs, and finite element modeling of ion transport shows that this result is unique to single-ion conductor gating in combination with an asymmetric gate/channel geometry. Both the experiments and modeling suggest that single-ion conductor-gated FETs can achieve sheet densities up to 1014 cm–2, which corresponds to a charge density that would theoretically be sufficient to induce several percent strain in monolayer 2D crystals and potentially induce a semiconductor-to-metal phase transition in MoTe2.
Electrofuels processes are potentially promising platforms for biochemical production from CO using renewable energy. When coupled to solar panels, this approach could avoid the inefficiencies of photosynthesis and there is no competition with food agriculture. In addition, these systems could potentially be used to store intermittent or stranded electricity generated from other renewable sources. Here we develop reactor configurations for continuous electrofuels processes to convert electricity and CO to isobutyric acid (IBA) using genetically modified (GM) chemolithoautotrophic Acidithiobacillus ferrooxidans. These cells oxidize ferrous iron which can be electrochemically reduced. During two weeks of cultivation on ferrous iron, stable cell growth and continuous IBA production from CO were achieved in a process where media was circulated between electrochemical and biochemical rectors. An alternative process with an additional electrochemical cell for accelerated ferrous production was developed, and this system achieved an almost three-fold increase in steady state cell densities, and an almost 4-fold increase in the ferrous iron oxidation rate. Combined, this led to an almost 8-fold increase in the steady state volumetric productivity of IBA up to 0.063±0.012mg/L/h, without a decline in energy efficiency from previous work. Continued development of reactor configurations which can increase the delivery of energy to the genetically modified cells will be required to increase product titers and volumetric productivities.
Gangliosides, glycolipids that are abundant in the plasma membrane outer leaflet, play an integral role in cellular recognition, adhesion, and infection by interacting with different endogenous molecules, viruses, and toxins. Model membrane systems, such as ganglioside-enriched supported lipid bilayers (SLBs), present a useful tool for sensing, characterizing, and quantifying such interactions. In this work, we report the formation of ganglioside GM1-rich SLBs on conducting polymer electrodes using a solvent-assisted lipid bilayer assembly method to investigate changes in membrane electrical properties upon binding of the B subunit of cholera toxin. The sensing capabilities of our platform were investigated by varying both the receptor and the toxin concentrations in the system as well as using a complex sample (milk contaminated with the toxin) and monitoring the changes in the electrical properties of the membrane. Our work highlights the potential of such conducting polymer-supported biomembrane-based platforms for detecting the toxins within a complex environment, studying ganglioside-specific biomolecular interactions with toxins and screening inhibitory molecules to prevent these interactions.
Silver nanofilament formation dynamics are reported for an ionic liquid (IL)-filled solid polymer electrolyte prepared by a direct-write process using a conductive atomic force microscope (C-AFM). Filaments are electrochemically formed at hundreds of xy locations on a ≈40 nm thick polymer electrolyte, polyethylene glycol diacrylate (PEGDA)/[BMIM]PF 6 . Although the formation time generally decreases with increasing bias from 0.7 to 3.0 V, an unexpected non-monotonic maximum is observed ≈2.0 V. At voltages approaching this region of inverted kinetics, IL electric double layers (EDLs) become detectable; thus, the increased nanofilament formation time can be attributed to electric field screening, which hinders silver electromigration and deposition. Scanning electron microscopy confirms that nanofilaments formed in this inverted region have significantly more lateral and diffuse features. Timedependent formation currents reveal two types of nanofilament growth dynamics: abrupt, where the resistance decreases sharply over as little as a few ms, and gradual where it decreases more slowly over hundreds of ms. Whether the resistance change is abrupt or gradual depends on the extent to which the EDL screens the electric field. Tuning the formation time and growth dynamics using an IL opens the range of accessible resistance states, which is useful for neuromorphic applications.
Materials with reconfigurable optical properties are candidates for applications such as optical cloaking and wearable sensors. One approach to fabricate these materials is to use external fields to form and dissolve nanoscale conductive channels in well-defined locations within a polymer. In this study, conductive atomic force microscopy is used to electrochemically form and dissolve nanoscale conductive filaments at spatially distinct points in a polyethylene glycol diacrylate (PEGDA)-based electrolyte blended with varying amounts of ionic liquid (IL) and silver salt. The fastest filament formation and dissolution times are detected in a PEGDA/IL composite that has the largest modulus (several GPa) and the highest polymer crystal fraction. This is unexpected because filament formation and dissolution events are controlled by ion transport, which is typically faster within amorphous regions where polymer mobility is high. Filament kinetics in primarily amorphous and crystalline regions are measured, and two different mechanisms are observed. The formation time distributions show a power-law dependence in the crystalline regions, attributable to hopping-based ion transport, while amorphous regions show a normal distribution. The results indicate that the timescale of filament formation/dissolution is determined by local structure, and suggest that structure could be used to tune the optical properties of the film.
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