An official website of the United States government
Abstract In biology, heterosynaptic plasticity maintains homeostasis in synaptic inputs during associative learning and memory, and initiates long-term changes in synaptic strengths that nonspecifically modulate different synapse types. In bioinspired neuromorphic circuits, heterosynaptic plasticity may be used to extend the functionality of two-terminal, biomimetic memristors. In this article, we explore how changes in the pH of droplet interface bilayer aqueous solutions modulate the memristive responses of a lipid bilayer membrane in the pH range 4.97–7.40. Surprisingly, we did not find conclusive evidence for pH-dependent shifts in the voltage thresholds ( V* ) needed for alamethicin ion channel formation in the membrane. However, we did observe a clear modulation in the dynamics of pore formation with pH in time-dependent, pulsed voltage experiments. Moreover, at the same voltage, lowering the pH resulted in higher steady-state currents because of increased numbers of conductive peptide ion channels in the membrane. This was due to increased partitioning of alamethicin monomers into the membrane at pH 4.97, which is below the pKa (~5.3–5.7) of carboxylate groups on the glutamate residues of the peptide, making the monomers more hydrophobic. Neutralization of the negative charges on these residues, under acidic conditions, increased the concentration of peptide monomers in the membrane, shifting the equilibrium concentrations of peptide aggregate assemblies in the membrane to favor greater numbers of larger, increasingly more conductive pores. It also increased the relaxation time constants for pore formation and decay, and enhanced short-term facilitation and depression of the switching characteristics of the device. Modulating these thresholds globally and independently of alamethicin concentration and applied voltage will enable the assembly of neuromorphic computational circuitry with enhanced functionality. Impact statement We describe how to use pH as a modulatory “interneuron” that changes the voltage-dependent memristance of alamethicin ion channels in lipid bilayers by changing the structure and dynamical properties of the bilayer. Having the ability to independently control the threshold levels for pore conduction from voltage or ion channel concentration enables additional levels of programmability in a neuromorphic system. In this article, we note that barriers to conduction from membrane-bound ion channels can be lowered by reducing solution pH, resulting in higher currents, and enhanced short-term learning behavior in the form of paired-pulse facilitation. Tuning threshold values with environmental variables, such as pH, provide additional training and learning algorithms that can be used to elicit complex functionality within spiking neural networks. Graphical abstract
more »
« less
Scalable Manufacturing of Radiation‐Tolerant Potentiometric Electrodes: A Systematic Transition from Laboratory to Semiautomated Fabrication
A “lab‐to‐fab” transition is described that enables the semiautomated production of thin‐film potentiometric pH electrodes, designed for use in sterile single‐use bioreactors. Manual methods of materials deposition and film casting are replaced with spray coating on a moving web and the production of membranes with a programmable dispenser operating at constant rates. These provide a greater degree of control over membrane thickness and a reduction in voltage spread between electrodes, which are evaluated in batches using a multichannel analyzer. γ‐ray ionization of the pH electrodes introduces a predictable voltage drift that follows a log decay function on the day timescale; the voltage decay rate correlates with membrane thickness and can be modeled as a parallel diode–capacitor circuit. Batches of radiation‐sterilized pH electrodes are tested in cell culture media and yield mean pH values within 0.05 units relative to a commercial meter (ground truth) following a single‐point calibration protocol. Quantitative uncertainty analysis attributes more than half of total error to variations caused by ionizing radiation and yields novel insights into strategies for reducing uncertainty.
more »
« less
- Award ID(s):
- 2204206
- PAR ID:
- 10640135
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Engineering Materials
- Volume:
- 27
- Issue:
- 12
- ISSN:
- 1438-1656
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Abstract Arrays of flexible polymer piezoelectric film cantilevers that mimic grass or leaves is a prospective idea for harvesting wind energy in urban areas, where the use of traditional technologies is problematic due to low wind velocities. Conversion of this idea into an economically attractive technology depends on various factors including the shape and dimensions of individual films to maximize generated power and to minimize associated costs of production, operation, and maintenance. The latter requirement can be satisfied with rectangular films undergoing flutter in ambient air. Flexible piezoelectric films that displace due to low forces and can convert mechanical energy into electrical energy are ideal for this application. The goal of the presented study is to determine the key dimensions of the piezoelectric film to enhance generated power within the wind range characteristic for urban areas from 1.3 to 7.6 m/s. For this purpose, experiments were conducted in a wind tunnel using piezoelectric polymer films of polyvinylidine fluoride with the length, width, and thickness varying in the ranges of 32–150, 16–22, and 40–64 μm, respectively. Voltage and power outputs for individual samples were measured at wind speeds ranging from 0.5 to 16.5 m/s. Results demonstrated that a single film could produce up to 0.74 nW and that the optimal film dimensions are 63 mm × 22 mm × 40 μm (from considered samples) for the wind energy harvesting in urban areas. Further improvement in power production can be expected when using films with reduced thickness, low elastic modulus, and increased length, and by assembling films in arrays.more » « less
-
null (Ed.)Organic electrosynthesis is emerging as a cost-effective and environmental-friendly chemical production strategy by utilizing renewable electricity. Paired electrolysis cogenerates valuable chemicals at both electrodes can optimize the energy efficiency and economic feasibility. We report pairing hydrogenation and oxidation of 5-(hydroxymethyl)furfural (HMF) or furfural to desired chemicals at a single electrolysis cell. Electrocatalytic hydrogenation of HMF to 2,5-bis(hydroxymethyl)furan (BHMF) and furfural to furfural alcohol (FA) with high selectivity of >90% can be operated at near-neutral pH on Ag-based and Pb-based catalysts, respectively. In addition, oxidizing HMF to 2,5-furandicarboxylic acid (FDCA) and furfural to furoic acid can both be realized at TEMPO mediated process by using carbon-based catalysts or at Ni-based catalyst in an alkaline medium. Taken together, HMF or furfural can be performed in a single electrolysis cell with a minimized cell voltage only around 1.6 V. Products selectivity and faradaic efficiency are highly related to the reaction conditions, including potential or current density, architectures of the reactor, type of catalysts. By optimizing the single flow reactor, a three-electrode system, two-electrode membrane assembly architecture, and pH-symmetric and pH-asymmetric structure can be designed to reduce the capital expense, minimize required energy, and simplify processing steps. Finally, a complete electrons economy can be achieved by pairing two electrochemical reactions, and the overall charge efficiency can attain over 170% without any crossover issue detected. As a result, the continuous cogeneration of high value-added BHMF or FA and FDCA or furoic acid can be performed in a single electrolyzer.more » « less
-
Low-cost polyamide thin-film composite membranes are being explored as alternatives to expensive cation exchange membranes for seawater electrolysis. However, chloride transport from seawater to the anode chamber must be reduced to minimize production of chlorine gas. A double-polyamide membrane composite structure was created that reduced chloride transport. Adding five polyamide layers on the back of a conventional polyamide composite membrane reduced chloride ion transport by 53% and did not increase the applied voltage. Decelerated chloride permeation was attributed to enhanced electrostatic and steric repulsion created by the new polyamide layer. Charge was balanced through increased sodium ion transport (52%) from the anolyte to the catholyte rather than a change in water ion transport. As a result, the Nernstian loss arising from the pH difference between the anolyte and catholyte remained relatively constant during electrolysis despite membrane modifications. This lack of a change in pH showed that transport of proton and hydroxide during electrolysis was independent of salt ion transport. Therefore, only sodium ion transport could compensate for the reduction of chloride flux to maintain the set current. Overall, these results prove the feasibility of using double-polyamide structure to control chloride permeation during seawater electrolysis without sacrificing energy consumption.more » « less
-
Planar magnesium diboride Josephson junctions are fabricated using focused helium ion beam irradiation. A single track of ion irradiation with a 30 kV He+ beam with nominal beam diameter < 0.5 nm is used to create a normal-metal barrier on a MgB2 film deposited by hybrid physical-chemical vapor deposition. Josephson coupling is observed below the critical temperature of the electrodes for a He+ doses between 8x1015/cm2 to 4x1016/cm2. Analysis of the temperature dependence of the normal resistance and critical voltage of the junctions shows highly uniform barriers with nearly ideal resistively-shunted junction behavior for higher-dose junctions, while nonequilibrium effects dominate the properties of lower-dose junctions over most of the temperature range. These results demonstrate that focused helium ion beam irradiation can produce high-quality proximity-coupled MgB2 Josephson junctions with tailorable properties, promising for use in superconducting devices and circuits.more » « less
