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Results for “electrical properties of membranes”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 19 records

Effects of Normal and Lateral Electric Fields on Membrane Mechanical Properties

As a core component of biological and synthetic membranes, lipid bilayers are key to compartmentalizing chemical processes. Bilayer morphology and mechanical properties are heavily influenced by electric fields such as those caused by biological ion concentration gradients. We present atomistic simulations exploring the effects of electric fields applied normally and laterally to lipid bilayers. We find that normal fields decrease membrane tension, while lateral fields increase it. Free energy perturbation calculations indicate the importance of dipole-dipole interactions to these tension changes, especially for lateral fields. We additionally show that membrane area compressibilities can be related to their cohesive energies, allowing us to estimate changes in membrane bending rigidity under applied fields. We find that normal fields decrease bending rigidity, while lateral fields increase it. Furthermore, these results point to the use of directed electric fields to locally control membrane stiffness, thereby modulating associated cellular processes.

Chemistry↗

Capturing membrane structure and function in lattice Boltzmann models

Here, we develop a mesoscopic approach to model the nonequilibrium behavior of membranes at the cellular scale. Relying on lattice Boltzmann methods, we develop a solution procedure to recover the Nernst-Planck equations and Gauss's law. A general closure rule is developed to describe mass transport across the membrane, which is able to account for protein-mediated diffusion based on a coarse-grained representation. We demonstrate that our model is able to recover the Goldman equation from first principles and show that hyperpolarization occurs when membrane charging dynamics are controlled by multiple relaxation timescales. The approach provides a promising way to characterize non-equilibrium behaviors that arise due to the role of membranes in mediating transport based on realistic three-dimensional cell geometries.

59 BASIC BIOLOGICAL SCIENCES↗

Plasma–liquid interactions in the presence of organic matter—A perspective

As investigations in the biomedical applications of plasma advance, a demand for describing safe and efficacious delivery of plasma is emerging. It is quite clear that not all plasmas are “equal” for all applications. This Perspective discusses limitations of the existing parameters used to define plasma in context of the need for the “right plasma” at the “right dose” for each “disease system.” The validity of results extrapolated from in vitro studies to preclinical and clinical applications is discussed. We make a case for studying the whole system as a single unit, in situ. Furthermore, we argue that while plasma-generated chemical species are the proposed key effectors in biological systems, the contribution of physical effectors (electric fields, surface charging, dielectric properties of target, changes in gap electric fields, etc.) must not be ignored.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

(2 + δ)-dimensional theory of the electromechanics of lipid membranes: Electrostatics

The coupling of electric fields to the mechanics of lipid membranes gives rise to intriguing electromechanical behavior, as, for example, evidenced by the deformation of lipid vesicles in external electric fields. Electromechanical effects are relevant for many biological processes, such as the propagation of action potentials in axons and the activation of mechanically gated ion channels. Currently, a theoretical framework describing the electromechanical behavior of arbitrarily curved and deforming lipid membranes does not exist. Purely mechanical models commonly treat lipid membranes as two-dimensional surfaces, ignoring their finite thickness. While holding analytical and numerical merit, this approach cannot describe the coupling of lipid membranes to electric fields and is thus unsuitable for electromechanical models. In a sequence of articles, we derive an effective surface theory of the electromechanics of lipid membranes, called the (2 + δ)-dimensional theory, which has the advantages of surface descriptions while accounting for finite thickness effects. The present article proposes a generic dimension reduction procedure relying on low-order spectral expansions. This procedure is applied to the electrostatics of lipid membranes to obtain the (2 + δ)-dimensional theory that captures potential differences across and electric fields within lipid membranes. Finally, this model is tested on different geometries relevant for lipid membranes, showing good agreement with the corresponding three-dimensional electrostatics theory.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Molecular Dynamics Studies of Structure and Functions of Water-Membrane Interfaces

A large number of essential cellular processes occur at the interfaces between water and membranes. The selectivity and dynamics of these processes are largely determined by the structural and electrical properties of the water-membrane interface. We investigate these properties by the molecular dynamics method. Over the time scales of the simulations, the membrane undergoes fluctuations described by the capillary wave model. These fluctuations produce occasional thinning defects in the membrane which provide effective pathways for passive transport of ions and small molecules across the membrane. Ions moving through the membrane markedly disrupt its structure and allow for significant water penetration into the membrane interior. Selectivity of transport, with respect to ionic charge, is determined by the interfacial electrostatic potential. Many small molecules. of potential significance in catalysis, bioenergetics and pharmacology, are shown to bind to the interface. The energetics and dynamics of this process will be discussed.

Pohorille, Andrew↗

Curvature Memory in Electrically Stimulated Lipid Membranes

Here, we demonstrate, using non-equilibrium molecular dynamics simulations, that lipid membrane capacitance varies with surface charge accumulation linked to membrane shape and curvature changes. Specifically, we show that lipid membranes exhibit a hysteretic response when exposed to oscillatory electric fields. The electromechanical coupling in these membranes leads to hysteretic buckling, in which the membrane can spontaneously buckle in one of two distinct directions along the electric field, even for the same ionic charge accumulation at the water–membrane interface. In this regard, these binary buckled membrane states suggest potential applications in neuromorphic computing. Their bistable nature, characterized by two distinct and stable configurations, could serve as a foundation for implementing memory storage systems and logic operations. Furthermore, we introduce a circuit model that captures these dynamic effects, offering insights into emergent memory effects in electrically stimulated lipid membranes. Finally, this work presents lipid bilayers as dynamic, adaptable elements and suggests a new platform for exploring energy storage, information processing, and memory encoding at the lipid membrane level.

59 BASIC BIOLOGICAL SCIENCES↗

Thermally driven phase transitions in freestanding low-buckled silicene, germanene, and stanene

Low-buckled silicene, germanene, and stanene are group-IV graphene allotropes. They form a honeycomb lattice out of two interpenetrating (A and B) triangular sublattices that are vertically separated by a small distance Δ z . The atomic numbers Z of silicon, germanium, and tin are larger than that of carbon (Z C = 6), making them the first experimentally viable two-dimensional topological insulators. Those materials have a twice-energy-degenerate atomistic structure characterized by the buckling direction of the B sublattice with respect to the A sublattice [whereby the B atom either protrudes above (Δ z > 0) or below (Δ z < 0) the A atoms], and the consequences of that energy degeneracy on their elastic and electronic properties have not been reported thus far. Here, we uncover ferroelastic, bistable behavior on silicene, which turns into an average planar structure at about 600 K. Furthermore, the creation of electron and hole puddles obfuscates the zero-temperature spin-orbit coupling (SOC)-induced band gaps at temperatures as low as 200 K, which may discard silicene as a viable two-dimensional topological insulator for room-temperature applications. Germanene, on the other hand, never undergoes a low-buckled-to-planar two-dimensional transformation, becoming amorphous at around 675 K instead, and preserving its SOC-induced band gap despite band broadening. Stanene undergoes a transition onto a crystalline three-dimensional structure at about 300 K, preserving its SOC-induced electronic band gap up to that temperature. Unlike what is observed in silicene and germanene, stanene readily develops a higher-coordinated structure with a high degree of structural order. Furthermore, the structural phenomena are shown to have far-reaching consequences for the electronic and vibrational properties of those two-dimensional topological insulators.

36 MATERIALS SCIENCE↗

Physical insights into biological memory using phospholipid membranes

Electrical signals may propagate along neuronal membranes in the brain, thus enabling communication between nerve cells. In doing so, lipid bilayers, fundamental scaffolds of all cell membranes, deform and restructure in response to such electrical activity. These changes impact the electromechanical properties of the membrane, which then physically store biological memory. This memory can exist either over a short or long period of time. Traditionally, biological memory is defined by the strengthening or weakening of transmissions between individual neurons. In this report we show that electrical stimulation may also alter the properties of the lipid membrane, thus pointing toward a novel mechanism for memory storage. Furthermore, based on the analysis of existing electrophysiological data, we study molecular mechanisms underlying the long-term potentiation in phospholipid membranes. Finally, we examine possible relationships between the memory capacitive properties of lipid membranes, neuronal learning, and memory.

59 BASIC BIOLOGICAL SCIENCES↗

Coupled Interfacial Kinetics and Transport Resistances Govern High-Current Behavior in Bipolar Membranes

Bipolar membranes (BPMs) enable electrochemical systems that operate across large pH gradients; however, high-current operation is often limited by voltage losses whose origins remain difficult to resolve in membrane−electrode assemblies. Here, we combine electrochemical impedance spectroscopy with distribution of relaxation times (EIS–DRT) analysis and operando synchrotron X-ray diffraction to examine interfacial polarization, membrane hydration, and transport in commercial and synthesized BPMs. EIS–DRT isolates the BPM-associated interfacial contribution and shows that the commercial BPM exhibits larger water-dissociation-associated overpotentials than the synthesized BPM. Operando hydration mapping shows that both membranes retain water at the bipolar junction during high-current operation, while anode-adjacent hydration gradients are more pronounced in the commercial membrane. These results indicate that high-current voltage losses are not governed by junction water starvation alone but by coupled interfacial polarization and transport resistances.

36 MATERIALS SCIENCE↗

Electrochemical Activation of Ni–Fe Oxides for the Oxygen Evolution Reaction in Alkaline Media

The oxygen evolution reaction (OER) is essential to many key electrochemical devices, including H 2 O electrolyzers, CO 2 electrolyzers, and metal−air batteries. NiFe oxides have been historically identified as active for the OER, though they have been less studied in their more commercially relevant bulk oxide forms, such as NiFe 2 O 4 . Past works have demonstrated that the initial starting phase of Ni(Fe) precatalysts can influence their activation to the Ni(Fe)OOH active phase, including the rate and degree of conversion, pointing to the necessity of understanding activation protocols and in situ characteristics of catalyst materials at the device level. In this work, we investigate the characteristics of commercially relevant NiFe bulk oxides (NiFe 2 O 4 and a physical mixture of NiO and γ-Fe 2 O 3 ) during multiple activation procedures. Our results demonstrate that significant performance enhancement is observed for these bulk oxides regardless of the Fe incorporation in the initial form (i.e., atomically or macroscopically integrated), leading to significant performance enhancement (up to 30×) over time on stream. We hypothesize that this activation is due to the formation of NiFeOOH active sites on the surface, supported by in situ cyclic voltammetry and Raman spectroscopy results. We further show that not only the starting material but also the method of activation influences the number of Ni(Fe)OOH active sites formed and suggest that these sites can be quantified from the Ni 2+ to Ni 3+ redox transition using cyclic voltammetry. Broadly, this work demonstrates the necessity of in situ characterization of catalyst materials for cell-level design and testing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Pure-Water-Fed Forward-Bias Bipolar Membrane CO 2 Electrolyzer

Coupling renewable electricity to reduce carbon dioxide (CO 2 ) electrochemically into carbon feedstocks offers a promising pathway to produce chemical fuels sustainably. While there has been success in developing materials and theory for CO 2 reduction, the widespread deployment of CO 2 electrolyzers has been hindered by challenges in the reactor design and operational stability due to CO 2 crossover and (bi)carbonate salt precipitation. Herein, we design asymmetrical bipolar membranes assembled into a zero-gap CO 2 electrolyzer fed with pure water, solving both challenges. By investigating and optimizing the anion-exchangelayer thickness, cathode differential pressure, and cell temperature, the forward-bias bipolar membrane CO 2 electrolyzer achieves a CO faradic efficiency over 80% with a partial current density over 200 mA cm –2 at less than 3.0 V with negligible CO 2 crossover. In addition, this electrolyzer achieves 0.61 and 2.1 mV h –1 decay rates at 150 and 300 mA cm –2 for 200 and 100 h, respectively. Postmortem analysis indicates that the deterioration of catalyst/polymer– electrolyte interfaces resulted from catalyst structural change, and ionomer degradation at reductive potential shows the decay mechanism. Furthermore, all these results point to the future research direction and show a promising pathway to deploy CO 2 electrolyzers at scale for industrial applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Heterogeneous Integration of Freestanding Bilayer Oxide Membrane for Multiferroicity

Transition metal oxides exhibit a plethora of electrical and magnetic properties described by their order parameters. In particular, ferroic orderings offer access to a rich spectrum of fundamental physics phenomena, in addition to a range of technological applications. The heterogeneous integration of ferroelectric and ferromagnetic materials is a fruitful way to design multiferroic oxides. The realization of freestanding heterogeneous membranes of multiferroic oxides is highly desirable. In this study, epitaxial BaTiO 3 /La 0.7 Sr 0.3 MnO 3 freestanding bilayer membranes are fabricated using pulsed laser epitaxy. The membrane displays ferroelectricity and ferromagnetism above room temperature accompanying the finite magnetoelectric coupling constant. Further, this study reveals that a freestanding heterostructure can be used to manipulate the structural and emergent properties of the membrane. In the absence of the strain caused by the substrate, the change in orbital occupancy of the magnetic layer leads to the reorientation of the magnetic easy-axis, that is, perpendicular magnetic anisotropy. These results of designing multiferroic oxide membranes open new avenues to integrate such flexible membranes for electronic applications.

36 MATERIALS SCIENCE↗

How Low Can You Go? Nanoscale Membranes for Efficient Water Electrolysis

Motivated by the need to lower the cost of hydrogen (H 2 ) production by water electrolysis, significant research efforts are focused on making proton (H + ) exchange membrane (PEM) water electrolyzers more efficient and capable of operating at higher current densities. These aims can be met by making H + -conducting membranes thinner, which has the effect of lowering ohmic drops across the membrane that represent the largest efficiency loss at high current densities (>2 A cm –2 ). However, decreasing membrane thickness below 50 μm is not trivial due to trade-offs between membrane resistance, H 2 crossover (safety), membrane degradation, and manufacturing throughput. Furthermore, descriptions of key processes, limitations, and trade-offs that arise in thin membranes are provided that can be used to guide the design of ultrathin (i.e., submicron thick), low-resistance membrane materials that have the potential to transform the field of clean H 2 production.

08 HYDROGEN↗

Semiconductor Thermal and Electrical Properties Decoupled by Localized Phonon Resonances

Abstract Thermoelectric materials convert heat into electricity through thermally driven charge transport in solids or vice versa for cooling. To compete with conventional energy‐conversion technologies, a thermoelectric material must possess the properties of both an electrical conductor and a thermal insulator. However, these properties are normally mutually exclusive because of the interconnection between scattering mechanisms for charge carriers and phonons. Recent theoretical investigations on sub‐device scales have revealed that nanopillars attached to a membrane exhibit a multitude of local phonon resonances, spanning the full spectrum, that couple with the heat‐carrying phonons in the membrane and cause a reduction in the in‐plane thermal conductivity, with no expected change in the electrical properties because the nanopillars are outside the pathway of voltage generation and charge transport. Here this effect is demonstrated experimentally for the first time by investigating device‐scale suspended silicon membranes with GaN nanopillars grown on the surface. The nanopillars cause up to 21% reduction in the thermal conductivity while the power factor remains unaffected, thus demonstrating an unprecedented decoupling in the semiconductor's thermoelectric properties. The measured thermal conductivity behavior for coalesced nanopillars and corresponding lattice‐dynamics calculations provide evidence that the reductions are mechanistically tied to the phonon resonances. This finding paves the way for high‐efficiency solid‐state energy recovery and cooling.

Spann, Bryan T.↗

Characterizing Hydrated Polymers via Dielectric Relaxation Spectroscopy: Connecting Relative Permittivity, State of Water, and Salt Transport Properties of Sulfonated Polysulfones

Sulfonated polysulfone is a promising membrane material for separation and energy generation processes that rely on membranes to control the rates of small-molecule (e.g., water and ions) transport. The interactions among water molecules, ions, and the sulfonate groups in these polymers play a key role in controlling these rates of transport, but much remains unknown about these fundamental interactions in sulfonated polymers. In this study, we used dielectric relaxation spectroscopy to characterize water molecule dynamics in sulfonated polysulfone and Nafion. We found that the charged sulfonate groups contribute to a restriction of water molecule dynamics (i.e., a reduction in the characteristic time scale of dipolar motions) in a manner that is governed by the concentration and nature (i.e., conjugate base strength) of the sulfonate group. Additionally, we develop strategies to use these data to aid in modeling ion transport in sulfonated polysulfone. These results may be useful to guide engineering strategies for polymeric membranes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ultrathin electron and proton-conducting membranes for nanoscale integrated artificial photosystems

Reducing the thickness of separation membranes without compromising their selectivity and robustness is the most effective way of maximizing the areal conductivity. This is especially important for the integration of visible light-driven water oxidation and carbon dioxide (or proton) reduction into a complete artificial photosystem on the shortest possible length scale – the nanoscale – because of the efficiency advantages over macroscale photosystems. In addition to their excellent separation property, ultrathin membranes of 10 nm thickness or less need to exhibit sufficient electrical and proton conductivity in order for the photocatalytic rates to keep up with the photon flux at maximum solar intensity. Furher, two materials, graphene and amorphous silica with embedded molecular wires, have emerged as promising ultrathin membranes for the development of nanoscale integrated solar-fuel systems. Moreover, electrically conducting metal–organic or covalent–organic frameworks can be used to fabricate high surface area-supports that enable the use of molecular catalysts and/or light absorbers at an adequate areal density for nanoscale integration with graphene membranes. Following an overview of the electron and proton conductivity of these ultrathin materials and recent examples of photoelectrocatalytic applications that take advantage of some but not all the properties that constitute a complete functional membrane, the status and future opportunities for complete nanoscale integrated photosystems featuring an ultrathin membrane are discussed.

59 BASIC BIOLOGICAL SCIENCES↗

The delayed rectifier, IKI, is the major conductance in type I vestibular hair cells across vestibular end organs

Hair cells were dissociated from the semicircular canal, utricle, lagena and saccule of white king pigeons. Type I hair cells were identified morphologically based on the ratios of neck width to cuticular plate width (NPR < 0.72) as well as neck width to cell body width (NBR < 0.64). The perforated patch variant of the whole-cell recording technique was used to measure electrical properties from type I hair cells. In voltage-clamp, the membrane properties of all identified type I cells were dominated by a predominantly outward potassium current, previously characterized in semicircular canal as IKI. Zero-current potential, activation, deactivation, slope conductance, pharmacologic and steady-state properties of the complex currents were not statistically different between type I hair cells of different vestibular end organs. The voltage dependence causes a significant proportion of this conductance to be active about the cell's zero-current potential. The first report of the whole-cell activation kinetics of the conductance is presented, showing a voltage dependence that could be best fit by an equation for a single exponential. Results presented here are the first data from pigeon dissociated type I hair cells from utricle, saccule and lagena suggesting that the basolateral conductances of a morphologically identified population of type I hair cells are conserved between functionally different vestibular end organs; the major conductance being a delayed rectifier characterized previously in semicircular canal hair cells as IKI.

NASA Discipline Number 40-99↗