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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 271 records · Page 15
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Quantifying Energetic and Entropic Pathways in Molecular Systems

When examining dynamics occurring at nonzero temperatures, both energy and entropy must be taken into account to describe activated barrier crossing events. Furthermore, good reaction coordinates need to be constructed to describe different metastable states and the transition mechanisms between them. Here we use a physics-based machine learning method called state predictive information bottleneck (SPIB) to find nonlinear reaction coordinates for three systems of varying complexity. SPIB is able to correctly predict an entropic bottleneck for an analytical flat-energy double-well system and identify the entropy- and energy-dominated pathways for an analytical four-well system. Lastly, for a simulation of benzoic acid permeation through a lipid bilayer, SPIB is able to discover the entropic and energetic barriers to the permeation process. Given these results, we thus establish that SPIB is a reasonable and robust method for finding the important entropy, energy, and enthalpy barriers in physical systems, which can then be used to enhance the understanding and sampling of different activated mechanisms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Nonane and Hexanol Adsorption in the Lamellar Phase of a Nonionic Surfactant: Molecular Simulations and Comparison to Ideal Adsorbed Solution Theory

Adsorption of n-nonane/1-hexanol (C9/C6OH) mixtures into the lamellar phase formed by a 50/50 w/w triethylene glycol mono-n-decyl ether (C10E3)/water system was studied using configurational-bias Monte Carlo simulations in the osmotic Gibbs ensemble. The interactions were described by the Shinoda–Devane–Klein coarse-grained force field. Prior simulations probing single-component adsorption indicated that C9 molecules preferentially load near the center of the bilayer increasing the bilayer thickness, whereas C6OH molecules are more likely to be found near the interface of the polar and non-polar moieties swelling the bilayer in the lateral dimension. Here, we extend this work to binary C9/C6OH adsorption to probe whether the difference in the spatial preferences may lead to a synergistic effect and enhanced loadings for the mixture. Comparing loading trends and the thermodynamics of binary adsorption to unary adsorption reveals that C9–C9 interactions lead to the largest enhancement, whereas C9–C6OH and C6OH–C6OH interactions are less favorable for this bilayer system. As a result, ideal adsorbed solution theory yields satisfactory predictions of the binary loading.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

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↗
DOE OSTI2025

Side-Chain and Ring-Size Effects on Permeability in Artificial Water Channels

Artificial water channels (AWCs) have emerged as a promising framework for stable water permeation, with water transport rates comparable to aquaporins (3.4–40.3 × 10 8 H 2 O/channel/s). In this study, we probe the influence of ring-size and side-chain length on the water permeability observed within a class of AWCs termed ligand-appended pillar[n]arenes (LAPs) that have an adjustable ring-size (m) and side-chain length (n). Through all-atom molecular dynamics simulations, we calculate the permeability of these channels using the collective diffusion model and find their permeabilities. We characterize the mechanistic influence of pillar[n]arene ring-size and side-chain length on the channel water permeability by analyzing the characteristics of the internal permeating water-wire and the surrounding channel structure. We observe that water permeability decreases as a function of increasing ring-size due to increases in hydrophilic contacts between the permeating water-wire and the oxygen groups on the channel wall. Further, we observe an increase in water permeability as a function of side-chain length due to increased partitioning of the channel terminal groups into the hydrophilic blocks of the surrounding bilayer. For the LAP6 channel, with increase in side-chain length, the distance between terminal groups increases and leads to an increase in pore size, thereby enhancing water permeability. In the case of LAP5, as side-chain length increases, the channel displays a compensatory effect between tilt and bend angle due to the flexible side-chains. Such flexibility leads to higher terminal group partitioning in the hydrophilic blocks of the bilayer and extends the permeating water-wire. Furthermore, this increase in water-wire length and hydrophilic block access overcomes the nonmonotonic pore size trend in pillar[5]arene channels.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Confinement Effects on Furfuryl Alcohol Reactions over Porous Bilayer Silica-Modified Pd(111)

In recent years, hexagonally ordered silica bilayer films have been successfully grown and characterized on metal substrates. To investigate how confinement effects from the silica films can influence catalytic reactions, we studied the reaction of furfuryl alcohol on a Pd(111) surface modified with a ~4 Å thick silica bilayer film [BL-silica/Pd(111)] containing micro- and mesopores. Temperature-programmed desorption (TPD) experiments showed that BL-silica/Pd(111) catalyzed similar reactions to those catalyzed by bare Pd(111); however, the products desorbed at higher temperatures in the presence of the film. In addition, hydrogenation of trapped C3HX fragments at high temperature was detected on BL-silica/Pd(111), which resulted in propane production. Density functional theory calculations indicated that the BL-silica film weakened adsorption of reaction intermediates, including atomic hydrogen, on the Pd surface. The overall effect of the film opens the possibility of selectively hydrogenating multifunctional molecules, with significantly higher selectivity than on the bare Pd(111) surface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Variable Laser Ignition Pathways in Al/Pt Reactive Multilayers across 10 Decades of Pulse Duration

Pulsed laser irradiation is used to investigate the local initiation of rapid, self-propagating formation reactions in Al/Pt multilayers. The single pulse direct laser ignition of these 1.6 μm thick freestanding foils was characterized over 10 decades of pulse duration (10 ms to 150 fs). Finite element, reactive heat transport modeling of the near-threshold conditions has identified three distinct ignition pathways. For milli- to microsecond pulses, ignition occurs following sufficient absorption of laser energy to enable diffusion of Al and Pt between layers such that the heat released from the corresponding exothermic reaction overcomes conductive losses outside the laser-irradiated zone. When pulse duration is decreased into the nanosecond regime, heat is concentrated near the surface such that the Al locally melts, and a portion of the top-most bilayers react initially. The favorable kinetics and additional heat enable ignition. Further reducing pulse duration to hundreds of femtoseconds leads to a third ignition pathway. In this work, while much of the energy from these pulses is lost to ablation, the remaining heat beneath the crater can be sufficiently concentrated to drive a transverse self-propagating reaction, wherein the heat released from mixing at each interface occurs under kinetic conditions capable of igniting the subsequent layer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Disconnection-Mediated Transition in Segregation Structures at Twin Boundaries

Twin boundaries play an important role in the thermodynamics, stability, and mechanical properties of nanocrystalline metals. Understanding their structure and chemistry at the atomic scale is key to guide strategies for fabricating nanocrystalline materials with improved properties. In this work, we report an unusual segregation phenomenon at gold-doped platinum twin boundaries, which is arbitrated by the presence of disconnections, a type of interfacial line defect. By using atomistic simulations, we show that disconnections containing a stacking fault can induce an unexpected transition in the interfacial-segregation structure at the atomic scale, from a bilayer, alternating-segregation structure to a trilayer, segregation-only structure. This behavior is found for faulted disconnections of varying step heights and dislocation characters. Supported by a structural analysis and the classical Langmuir–McLean segregation model, we reveal that this phenomenon is driven by a structurally induced drop of the local pressure across the faulted disconnection accompanied by an increase in the segregation volume.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Metastable Metallic Phase of a Bilayer Blue Phosphorene Induced by Interlayer Bonding and Intralayer Charge Redistributions

We have carried out diffusion Monte Carlo calculations for an A 1 B -1 -stacked bilayer blue phosphorene to find that it undergoes a semiconductor-metal transition as the interlayer distance decreases. While the most stable bilayer structure is a semiconducting one with two monolayers coupled through weak van der Waals interaction, the metallic bilayer at a shorter interlayer distance is found to be only metastable. This is in contrast to a recent theoretical prediction based on random phase approximation that the metallic phase would be the most stable bilayer configuration of blue phosphorene. Our analysis of charge density distributions reveals that the metastable metallic phase is induced by interlayer chemical bonding and intralayer charge redistributions. This study enriches our understanding of interlayer binding of a blue phosphorene and contributes to establishment of correct energetic order between its different phases, which will be essential in devising an experimental pathway for a metallic phosphorene.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Nonstereotypical Distribution and Effect of Ergosterol in Lipid Membranes

Ergosterol, found in fungi and some protist membranes, is understudied compared with cholesterol from animal membranes. Generally, ergosterol is assumed to modulate membranes in the same manner as cholesterol, based on their similar chemical structures. Here we reveal some fundamental structural and dynamical differences between them. Neutron diffraction shows that ergosterol is embedded in the lipid bilayer much shallower than cholesterol. Further, ergosterol does not change the membrane thickness as much as cholesterol does, indicating little condensation effect. Neutron spin echo shows that ergosterol can rigidify and soften membranes at different concentrations. The lateral lipid diffusion measured by quasielastic neutron scattering indicates that ergosterol promotes a jump diffusion of the lipid, whereas cholesterol keeps the same continuous lateral diffusion as the pure lipid membrane. Our results point to quite distinct interactions of ergosterol with membranes compared with cholesterol. These insights provide a basic understanding of membranes containing ergosterol with implications for phenomena such as lipid rafts and drug interactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Upconversion on the Micrometer Scale: Impact of Local Heterogeneity

The properties of perovskite/naphtho[2,3-a]pyrene (NaPy) upconversion devices are investigated by a combination of atomic force microscopy and photoluminescence mapping to understand the role of microscopic heterogeneity in the ensemble device properties. The results emphasize strong microscopic inhomogeneity across the perovskite/NaPy upconversion device due to local formation of NaPy microcrystals. NaPy shows emission from three distinct states in the solid state: S 1 ′ emission at 520 nm, excimer emission at 560 nm, and S 1 ″ emission at 620 nm. Clear spatial differences in the emission spectrum under 405 nm excitation are found, highlighting that there is a strong microcrystal-to-microcrystal variation in the optical properties─emphasizing a need for multimodal measurements. Furthermore, our results indicate that microcrystals with strong emission from the strongly coupled low-energy state S 1 ″ (J-dimer) show much higher upconversion intensity than those with dominant emission from the high-energy S 1 ′ state (I-aggregate). Hence, our results suggest that microcrystals with strong emission from the low-energy state S 1 ″ act as isolated hotspots for upconversion.

Crystals↗
DOE OSTI2020

Understanding the Structure and Dynamics of Complex Biomembrane Interactions by Neutron Scattering Techniques

The membrane is one of the key structural materials of biology at the cellular level. Composed predominantly of a bilayer of lipids with embedded and bound proteins, it defines the boundaries of the cell and many organelles essential to life and therefore is involved in almost all biological processes. Membrane-specific interactions, such as drug binding to a membrane receptor or the interactions of an antimicrobial compound with the lipid matrix of a pathogen membrane, are of interest across the scientific disciplines. Herein we present a review, aimed at nonexperts, of the major neutron scattering techniques used in membrane studies: small-angle neutron scattering, neutron membrane diffraction, neutron reflectometry, quasielastic neutron scattering, and neutron spin echo. Neutron scattering techniques are well suited to studying biological membranes. The nondestructive nature of cold neutrons means that samples can be measured for long periods without fear of beam damage from ultraviolet, electron, or X-ray radiation, and neutron beams are highly penetrating, thus offering flexibility in samples and sample environments. Most important is the strong difference in neutron scattering lengths between the two most abundant forms of hydrogen, protium and deuterium. Changing the relative amounts of protium/deuterium in a sample allows the production of a series of neutron scattering data sets, enabling the observation of differing components within complex membrane architectures. This approach can be as simple as using the naturally occurring neutron contrast between different biomolecules to study components in a complex by changing the solution H 2 O/D 2 O ratio or as complex as selectively labeling individual components with hydrogen isotopes. This review presents an overview of each experimental technique with the neutron instrument configuration, related sample preparation and sample environment, and data analysis, highlighted by a special emphasis on using prominent neutron contrast to understand structure and dynamics. This review gives researchers a practical introduction to the often enigmatic suite of neutron beamlines, thereby lowering the barrier to taking advantage of these large-facility techniques to achieve new understandings of membranes and their interactions with other molecules.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Functionalized Polymersomes from a Polyisoprene-Activated Polyacrylamide Precursor

Self-assembled polymer nanoparticles have tremendous potential in biomedical and environmental applications. For all applications, tailored polymer chemistries are critical. In this study, we demonstrate a precursor approach in which an activated, organic solvent-soluble block polymer precursor is modified through mild postpolymerization modifications to access new polymer structures. We synthesized and characterized poly(isoprene)-block-poly(di-Boc acrylamide) diblock polymers. This activated-acrylamide-based polymer was then reacted with amines or reductants in the absence of catalysts to yield the hydrophilic blocks polyacrylamide, poly(hydroxypropylene), and poly(N-ethyl acrylamide). The resulting amphiphilic block polymers self-assembled in water to form polymersomes, as confirmed by cryo-electron microscopy and confocal microscopy. The approach also enables simple functionalization with specialized ligands, which we demonstrated by tagging polymers with an amino-fluorophore and imaging by confocal microscopy. Here, we expect that the methodologies established in this study will open doors to new and useful solution nanostructures with surface chemistries that can be optimized for various applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Defect Repair of Polyelectrolyte Bilayers Using SDS: The Action of Micelles Versus Monomers

Defects within single, double, and triple polyelectrolyte bilayers derived from poly(sodium 4-styrenesulfonate) (PSS) and poly(diallyldimethyammonium chloride) (PDDA) have been repaired using aqueous solutions of sodium dodecyl sulfate (SDS), as evidenced by a reduction in their permeability and an increase in their permeation selectivity. In contrast to the use of monomer solutions of SDS, which were moderately effective in repairing only double and triple bilayers, micellar solutions proved highly effective for all three assemblies. Here, evidence for intact micelles or micellar fragments being deposited on the surface of single bilayers of PSS/PDDA has been obtained from a combination of atomic force microscopy, X-ray photoelectron spectroscopy, ellipsometry, and contact angle measurements. Observed CO 2 permeances of ca. 200 GPU and CO 2 /N 2 selectivities of ca. 30 for SDS-repaired, single bilayers of PSS/PDDA suggest that further development of such assemblies could have the practical potential for the separation of CO 2 from N 2 in the flue gas.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Raman Microscopy Investigation of GLP-1 Peptide Association with Supported Phospholipid Bilayers

A wide range of important biological processes occur at phospholipid membranes including cell signaling, where a peptide or small molecule targets a membrane-localized receptor protein. In this work, we report the adaptation of confocal-Raman microscopy to quantify populations of unlabeled glucagon-like peptide-1 (GLP-1), a membrane-active 30-residue incretin peptide, in supported phospholipid bilayers deposited on the interior surfaces of wide-pore porous silica particles. Quantification of lipid bilayer-associated peptide is achieved by measuring the Raman scattering intensity of the peptide relative to that of the supported-lipid bilayer, which serves as an internal standard. The dependence of the bilayer-associated GLP-1 population on the solution-concentration of GLP-1 produces an isotherm used to determine the equilibrium constant for peptide-bilayer association and the maximum peptide surface coverage. The maximum coverage of GLP-1 in the lipid bilayer was found to be only 1/5th of a full monolayer based on its hydrodynamic radius. The saturation coverage, therefore, is not limited by the size of GLP-1 but by the ability of the bilayer to accommodate the peptide at high concentrations within the bilayer. Raman spectra show that GLP-1 association with the supported bilayer is accompanied by structural changes consistent with the intercalation of the peptide into bilayer, where the observed increase in acyl-chain order would increase the lipid density and provide free volume needed to accommodate the peptide. Furthermore, these results were compared with previous measurements of the association of fluorescently-labeled GLP-1 with a planar-supported bilayer; the unlabeled peptide exhibits a 3-fold greater affinity for the lipid-bilayer on the porous-silica support suggesting that the fluorescent label alters GLP-1 lipid-bilayer association.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Binding of Cholera Toxin B-Subunit to a Ganglioside GM1-Functionalized PEG-Tethered Lipid Membrane

We report neutron reflectometry (NR) studies of polyethylene glycol (PEG)-tethered model lipid membranes at the solid–liquid interface and of cholera toxin’s B-subunit (CTxB) binding to tethered membranes containing ganglioside GM1 receptors. First, tethered polymer brushes were formed by grafting silane-functionalized PEG lipopolymers to quartz from solution. Subsequent deposition of lipids by Langmuir–Blodgett/Langmuir–Schaefer (LB/LS) resulted in a tethered bilayer structure separated from the solid support by a hydrated PEG layer. NR revealed that the tethers formed a highly hydrated polymer brush, uniformly separating the bilayer from the underlying solid substrate. Further, the lipid bilayer did not significantly perturb the brush’s conformation relative to a free brush. Biological functionality of the tethered bilayers was verified by interacting CTxB, with ganglioside GM1 receptors incorporated into the bilayer. The surface coverage of CTxB bound to the lipid membrane, θ CTB = 0.58 ± 0.08, was consistent with the coverage predicted for random sequential absorption, and toxin binding did not impact the membrane conformation.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Inter-Leaflet Phospholipid Exchange Impacts the Ligand Density Available for Protein Binding at Supported Lipid Bilayers

Phospholipid bilayers formed at solid-liquid interfaces have garnered interest as mimics of cell-membranes to model association reactions of proteins with lipid-bilayer-tethered ligands. Despite the importance of understanding how ligand density in a lipid bilayer impacts the protein-ligand association response, relating the ligand-modified lipid fraction to the absolute density of solution-accessible ligands in a lipid bilayer remains a challenge in interfacial quantitative analysis. In this work, confocal-Raman microscopy is employed to quantify the association of anti-biotin IgG with a small fraction of biotinylated lipids dispersed in either gel-phase or liquid-crystalline supported lipid bilayers, deposited on the interior surfaces of wide-pore silica surfaces. We examine the question whether inter-leaflet lipid translocation contributes to the population of solution-accessible biotin ligands on the distal leaflet of a supported lipid bilayer by comparing their protein accumulation response with ligands dispersed in lipid monolayers on nitrile-derivatized silica surfaces. The binding of antibody to biotin ligands dispersed in gel-phase bilayers exhibited an equivalent biotin-coverage response as the accumulation of IgG onto gel-phase monolayers, indicating that gel-phase bilayer symmetry was preserved. This result contrasts with the ~60% greater anti-biotin capture observed at fluid-phase bilayers compared to fluid-phase monolayers prepared at equivalent biotin fractions. This enhanced protein capture is attributed to biotin-capped lipids being transferred from the surface-associated proximal leaflet of the bilayer to the solution-exposed distal leaflet by the inter-leaflet exchange or lipid flip-flop, a facile process in fluid-phase supported lipid bilayers. Here, the results suggest caution in interpreting the results of quantitative studies of protein binding to lipid-tethered ligands dispersed in fluid-phase phospholipid bilayers.

36 MATERIALS SCIENCE↗