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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 1,297 records · Page 72
All sourcesNASA NTRSDOE OSTI
DOE OSTI2013

Endoglucanase Peripheral Loops Facilitate Complexation of Glucan Chains on Cellulose via Adaptive Coupling to the Emergent Substrate Structures

We examine how the catalytic domain of a glycoside hydrolase family 7 endoglucanase catalytic domain (Cel7B CD) facilitates complexation of cellulose chains from a crystal surface. With direct relevance to the science of biofuel production, this problem also represents a model system of biopolymer processing by proteins in Nature. Interactions of Cel7B CD with a cellulose microfibril along different paths of complexation are characterized by mapping the atomistic fluctuations recorded in free-energy simulations onto the parameters of a coarse-grain model. The resulting patterns of protein-biopolymer couplings also uncover the sequence signatures of the enzyme in peeling off glucan chains from the microfibril substrate. We show that the semiopen active site of Cel7B CD exhibits similar barriers and free energies of complexation over two distinct routes; namely, scooping of a chain into the active-site cleft and threading from the chain end into the channel. On the other hand, the complexation energetics strongly depends on the surface packing of the targeted chain and the resulting interaction sites with the enzyme. A revealed principle is that Cel7B CD facilitates cellulose deconstruction via adaptive coupling to the emergent substrate. The flexible, peripheral segments of the protein outside of the active-site cleft are able to accommodate the varying features of cellulose along the simulated paths of complexation. The general strategy of linking physics-based molecular interactions to protein sequence could also be helpful in elucidating how other protein machines process biopolymers.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2023

Irradiation-enhanced Interactions at UO 2 /Al 2 O 3 /Al Interfaces

Combustion synthesis is used to prepare thin UO 2 films on aluminum alloy substrates. This simple preparation method involves electrospraying uranyl nitrate + acetylacetone + 2-methoxyethanol solution on the substrate, followed by a short annealing at 350 or 550 °C. The irradiation of films with a 40 Ar 2+ ion beam (energy of 1.7 MeV and fluences of 7.7 × 10 16 and 1.3 × 10 17 ions/cm 2 ) is conducted to investigate irradiation-induced restructuring processes. High-resolution transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) investigations show that the annealing temperature significantly influences the crystallinity and stability of materials during irradiation. A small amount of Mg in the alloy substrate diffuses into the amorphous Al 2 O 3 interfacial layer between the film and the substrate. Local thermal spikes from the incoming ions facilitate the irradiation-induced mixing of immiscible Al 2 O 3 and UO 2 for the materials prepared at 350 °C. This mass diffusion produces relatively large cavities at the interface. Selective diffusion of a more significant amount of Mg for the materials prepared at 550 °C suppresses the mixing of the Al 2 O 3 interlayer with the film but forms Mg y U 1–y O 2±x solid solutions during irradiation. Local thermal heating triggers the precipitation of a discontinuous crystalline MgO layer close to the film surface. As a result, the enhanced and selective diffusion of Mg into the film makes the materials prepared at 550 °C more robust and mechanically stable than those prepared at 350 °C.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Desorption of Benzene, 1,3,5-Trifluorobenzene, and Hexafluorobenzene from a Graphene Surface: The Effect of Lateral Interactions on the Desorption Kinetics

The desorption of benzene, 1,3,5-trifluorobenzene (TFB), and hexafluorobenzene (HFB) from a graphene covered Pt(111) substrate was investigated using temperature programmed desorption (TPD). All three species have well-resolved monolayer and second layer desorption peaks. The desorption spectra for submonolayer coverages of benzene and hexafluorobenzene are consistent with first-order desorption kinetics. In contrast, the submonolayer TPD spectra for 1,3,5- trifluorobenzene align on a common leading-edge which is indicative of zero-order desorption kinetics. The desorption behavior of the three molecules can be correlated with the strength of the quadrupole moments. Calculations (second-order Møller-Plesset perturbation and density functional theory) show that the potential minimum for coplanar TFB dimers is more than a factor of two greater than that for either benzene or HFB dimers. The calculations support the interpretation that benzene and HFB are less likely to form the two-dimensional islands that are needed for submonolayer zero-order desorption kinetics.

Smith, Ronald S.↗
DOE OSTI2013

Surface-Enhanced Raman Spectroscopy Detection of Ionic Solutes by Surfactant-Mediated Adsorption to a Hydrophobic Surface

Chemical modification of the surfaces of surface-enhanced Raman spectroscopy (SERS)-active metals with thin molecular layers expands the variety of molecular species that can be attracted to the SERS surface from solution. This approach can provide selective detection of new classes of molecules that would not otherwise be detectable through direct interaction with a SERS-active metal. For example, polycyclic aromatic compounds can be attracted from aqueous solution to gold or silver SERS substrates that are modified with alkylsilanes or alkanethiols. While n-alkane monolayers attract hydrophobic solutes to a SERS-active surface, they are not well suited to adsorbing more water-soluble, ionized species from solution. In this work, we address SERS detection of ionic solutes by applying the principles of ion-interaction chromatography, where a charged surfactant is added to solution and adsorbs to an n-alkane-modified, SERS-active surface. The adsorbed charged surfactant serves to attract an ionic solute of opposite charge to the surface, where it can be detected. This concept was tested with a model anionic solute, 3-nitrobenzenesulfonate (NBS – ), with a cationic surfactant, cetylpyridinium (CP + ), that adsorbs to a 1-dodecanethiol (C 12 )-modified silver surface. The interfacial populations of both the surfactant and anionic solute can be determined simultaneously from SERS spectra. The adsorption equilibrium of CP + to the C 12 surface was fit to a Langmuir model, and the effect of supporting electrolyte on its adsorption equilibria was also investigated by SERS. The retention of NBS – at the C 12 surface depends on the concentration of CP + . The binding of NBS – to adsorbed CP + is described by an ion-interaction model that includes competition for the NBS – population due to association with surfactant ions in solution. Furthermore, while the strength of this binding interaction is not as great as the hydrophobic interactions that drive aromatic hydrocarbons to hydrophobic SERS surfaces, SERS detection of analyte ions by this approach could be accomplished at concentrations two orders of magnitude lower compared with Raman detection in free solution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Composite low affinity interactions dictate recognition of the cyclin-dependent kinase inhibitor Sic1 by the SCF[superscript Cdc4] ubiquitin ligase

The ubiquitin ligase SCF{sup Cdc4} (Skp1/Cul1/F-box protein) recognizes its substrate, the cyclin-dependent kinase inhibitor Sic1, in a multisite phosphorylation-dependent manner. Although short diphosphorylated peptides derived from Sic1 can bind to Cdc4 with high affinity, through systematic mutagenesis and quantitative biophysical analysis we show that individually weak, dispersed Sic1 phospho sites engage Cdc4 in a dynamic equilibrium. The affinities of individual phosphoepitopes serve to tune the overall phosphorylation site threshold needed for efficient recognition. Notably, phosphoepitope affinity for Cdc4 is dramatically weakened in the context of full-length Sic1, demonstrating the importance of regional environment on binding interactions. The multisite nature of the Sic1-Cdc4 interaction confers cooperative dependence on kinase activity for Sic1 recognition and ubiquitination under equilibrium reaction conditions. Composite dynamic interactions of low affinity sites may be a general mechanism to establish phosphorylation thresholds in biological responses.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Novel method of recycling perovskite solar cells using iodide solutions

A novel recycling method utilizing aqueous iodide solutions has shown promise at selectively dissolving lead perovskite and preserving the glass substrate of lead perovskite solar cells (PSCs). Perovskite compounds are notorious for degrading upon contact with moisture into lead iodide which can be capitalized upon for recycling. When iodide ions reach a critical concentration in aqueous solutions, the solubility of lead iodide begins to rapidly increase as several complex ions are formed. Iodide solutions selectively interact with the perovskite material which dissolves from the edge inwards, allowing for exfoliation of the back contact and retention of the glass substrate and electron transport layer. PbI 2 solubility studies using KI, HI, and NH 4 I were conducted to determine an effective iodide source to develop a scalable recycling process. Further, retaining the coated glass substrate intact preserves the possibility to manufacture new solar cells from the same materials, by also omitting the use of organic solvents the costs as well as the human and environmental hazards of recycling PSCs can be minimized.

14 SOLAR ENERGY↗
DOE OSTI2017

Structural and functional insights into the interaction between the Cas family scaffolding protein p130Cas and the focal adhesion-associated protein paxillin

The Cas family scaffolding protein p130Cas is a Src substrate localized in focal adhesions (FAs) and functions in integrin signaling to promote cell motility, invasion, proliferation, and survival. p130Cas targeting to FAs is essential for its tyrosine phosphorylation and downstream signaling. Although the N-terminal SH3 domain is important for p130Cas localization, it has also been reported that the C-terminal region is involved in p130Cas FA targeting. The C-terminal region of p130Cas or Cas family homology domain (CCHD) has been reported to adopt a structure similar to that of the focal adhesion kinase C-terminal focal adhesion-targeting domain. The mechanism by which the CCHD promotes FA targeting of p130Cas, however, remains unclear. In this study, using a calorimetry approach, we identified the first LD motif (LD1) of the FA-associated protein paxillin as the binding partner of the p130Cas CCHD (in a 1:1 stoichiometry with a Kd ~4.2 μM) and elucidated the structure of the p130Cas CCHD in complex with the paxillin LD1 motif by X-ray crystallography. Of note, a comparison of the CCHD/LD1 complex with a previously solved structure of CCHD in complex with the SH2-containing protein NSP3 revealed that LD1 had almost identical positioning of key hydrophobic and acidic residues relative to NSP3. Because paxillin is one of the key scaffold molecules in FAs, we propose that the interaction between the p130Cas CCHD and the LD1 motif of paxillin plays an important role in p130Cas FA targeting.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Microstructure and magnetic properties of (001) textured L1(0) FePt films on amorphous glass substrate

L1(0) FePt thin films with an island-like morphology and magnetic perpendicular anisotropy were grown at low temperature (300 < T-dep< 375 degrees C) by magnetron sputtering on Hoya glass substrates using a 30-nm thick Cr (2 0 0) underlayer. An MgO buffer layer with a thickness of 2 nm was used to inhibit the diffusion from the Cr underlayer and promote the growth of (0 0 1) oriented L1(0) FePt films by inducing an in-plane lattice distortion. By varying the substrate temperature and the Ar sputter pressure (3.5 < P-Ar< 15 mTorr) during the deposition, the degree of chemical order, the microstructure and the magnetic properties were tuned and the best properties in term of squareness ratio (M-r/M-s similar to 0.95) and coercive field (H-c similar to 14 kOe) were observed for films deposited at T-dep = 350 degrees C and P-Ar= 5 mTorr, due to the appearance of a tensile strain, which favors the perpendicular anisotropy. The analysis of the angular dependence of remanent magnetization curves on the optimized sample suggests that the magnetization reversal is highly incoherent due to the inter-island interactions. Our results provide useful information on the low temperature growth of FePt films with perpendicular anisotropy onto glass substrates, which are relevant for a variety of technological applications, such as magnetic recording and spintronic devices. (C) 2015 Elsevier B.V. All rights reserved.

Speliotis, T↗
DOE OSTI2017

Surface Interactions and Confinement of Methane: A High Pressure Magic Angle Spinning NMR and Computational Chemistry Study

Characterization and modeling of the molecular-level behavior of simple hydrocarbon gases, such as methane, in the presence of both nonporous and nano-porous mineral matrices allows for predictive understanding of important processes in engineered and natural systems. In this study, changes in local electromagnetic environments of the carbon atoms in methane under conditions of high pressure (up to 130 bar) and moderate temperature (up to 346 K) were observed with 13C magic-angle spinning (MAS) NMR spectroscopy while the methane gas was mixed with two model solid substrates: a fumed non-porous, 12 nm particle size silica and a mesoporous silica with 200 nm particle size and 4 nm average pore diameter. Examination of the interactions between methane and the silica systems over temperatures and pressures that include the supercritical regime was allowed by a novel high pressure MAS sample containment system, which provided high resolution spectra collected under in situ conditions. For pure methane, no significant thermal effects were found for the observed 13C chemical shifts at all pressures studied here (28.2 bar, 32.6 bar, 56.4 bar, 65.1 bar, 112.7 bar, and 130.3 bar). However, the 13C chemical shifts of resonances arising from confined methane changed slightly with changes in temperature in mixtures with mesoporous silica. The chemical shift values of 13C nuclides in methane change measurably as a function of pressure both in the pure state and in mixtures with both silica matrices, with a more pronounced shift when meso-porous silica is present. Molecular-level simulations utilizing GCMC, MD and DFT confirm qualitatively that the experimentally measured changes are attributed to interactions of methane with the hydroxylated silica surfaces as well as densification of methane within nanopores and on pore surfaces.

confinement↗
DOE OSTI2014

Detachment of semiflexible polymer chains from a substrate: A molecular dynamics investigation

Using Molecular Dynamics simulations, we study the force-induced detachment of a coarse-grained model polymer chain from an adhesive substrate. One of the chain ends is thereby pulled at constant speed off the attractive substrate and the resulting saw-tooth profile of the measured mean force 〈f〉 vs height D of the end-segment over the plane is analyzed for a broad variety of parameters. It is shown that the observed characteristic oscillations in the 〈f〉-D profile depend on the bending and not on the torsional stiffness of the detached chains. Allowing for the presence of hydrodynamic interactions (HI) in a setup with explicit solvent and dissipative particle dynamics-thermostat, rather than the case of Langevin thermostat, one finds that HI have little effect on the 〈f〉-D profile. Also the change of substrate affinity with respect to the solvent from solvophilic to solvophobic is found to play negligible role in the desorption process. In contrast, a changing ratio ε{sub s}{sup B}/ε{sub s}{sup A} of the binding energies of A- and B-segments in the detachment of an AB-copolymer from adhesive surface strongly changes the 〈f〉-D profile whereby the B-spikes vanish when ε{sub s}{sup B}/ε{sub s}{sup A}<0.15. Eventually, performing an atomistic simulation of (bio)-polymers, we demonstrate that the simulation results, derived from our coarse-grained model, comply favorably with those from the all-atom simulation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Laser-induced transfer of gel microdroplets for cell printing

We study thermal and transport processes involved in the transfer of gel microdroplets under the conditions of laser cell microprinting. The specific features of the interaction of pulsed laser radiation ( λ = 1.064 µm, pulse duration 4 – 200 ns, energy 2 µJ – 1 mJ) with the absorbing gold film deposited on the glass donor substrate are determined. The investigation of the dynamics of transport processes by means of fast optical video recording and optoacoustic methods makes it possible to determine the characteristics of the produced gel jets as functions of the laser operation regimes. The hydrodynamic process of interaction between the laser radiation and the gold coating with the hydrogel layer on it is considered and the temperature in the region of the laser pulse action is estimated. It is shown that in the mechanism of laser-induced transfer a significant role is played by the processes of explosive boiling of water (in gel) and gold. The amount of gold nanoparticles arriving at the acceptor plate in the process of the laser transfer is determined. For the laser pulse duration 8 ns and small energies (less than 10 µJ), the fraction of gold nanoparticles in the gel microdroplets is negligibly small, and their quantity linearly grows with increasing pulse energy. The performed studies offer a base for optimising the processes of laser transfer of gel microdroplets in the rapidly developing technologies of cell microprinting. (interaction of laser radiation with matter. laser plasma)

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
NASA NTRS1991

Low Earth orbital atomic oxygen micrometeoroid, and debris interactions with photovoltaic arrays

Polyimide Kapton solar array blankets can be protected from atomic oxygen in low earth orbit if SiO sub x thin film coatings are applied to their surfaces. The useful lifetime of a blanket protected in this manner strongly depends on the number and size of defects in the protective coatings. Atomic oxygen degradation is dominated by undercutting at defects in protective coatings caused by substrate roughness and processing rather than micrometeoroid or debris impacts. Recent findings from the Long Duration Exposure Facility (LDEF) and ground based studies show that interactions between atomic oxygen and silicones may cause grazing and contamination problems which may lead to solar array degradation.

Banks, Bruce A.↗
DOE OSTI2011

Preparation and Characterization of Ultrathin Stainless Steel Films

We report on the preparation of polycrystalline austenitic 310 ({sup 57}Fe{sub 0.55}Cr{sub 0.25}Ni{sub 0.20}) stainless steel (SS) thin films on Si substrates and the characterization of their residual magnetism via {sup 57}Fe conversion-electron Moessbauer spectroscopy (CEMS). The films were structurally characterized at room temperature by X-ray diffraction (XRD). The virgin films were found to be structurally disordered. Subsequent annealing at moderate temperatures in ultrahigh vacuum produces the ordered martensitic and austenitic SS phases. Further annealing at higher temperatures (up to temperatures where long-range diffusion into the substrate is still weak) transforms the films into the austenitic phase with no trace of a magnetic hyperfine interaction. However, when a 2 nm thick SS thin film is embedded between two carbon layers, the as prepared disordered SS film does not transform to the martensitic or austenitic SS phase irrespective of the annealing temperature, probably because the interdiffusion with C prohibits the formation of these phases.

36 MATERIALS SCIENCE↗
DOE OSTI2019

External strain-enhanced cysteine enantiomeric separation ability on alloyed stepped surfaces

Using density functional theory with an accurate treatment of van der Waals interactions, we investigate the enantioselective recognition and separation of chiral molecules on stepped metal surfaces. Our calculations demonstrate that the separation ability of metal substrates can be significantly enhanced by surface decoration and external strain. For example, applying 2% tensile strain to the Ag-alloyed Au(532) surface leads to a dramatic increase (by 89%) in cysteine enantioselectivity as compared to that of pristine Au(532). Analysis on the computed binding energies shows that the interaction energy is the predominant factor that affects the separation efficiency in strongly bound systems. Furthermore our study presents a new strategy to modify the enantioselectivity of stepped metal surfaces and paves the way for exploring high efficiency chiral separation technology in pharmaceutical industry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Using MbtH-Like Proteins to Alter the Substrate Profile of a Nonribosomal Peptide Adenylation Enzyme

MbtH-like proteins (MLPs) are required for soluble expression and/or optimal activity of some adenylation (A) domains of nonribosomal peptide synthetases (NRPSs). Since A domains can interact with noncognate MLP partners, we investigated how the function of an A domain, TioK, involved in the biosynthesis of the bisintercalator thiocoraline, is altered by noncognate MLPs. Measuring TioK activity with 12 different MLPs from a variety of bacterial species using a radiometric assay suggested that the A domain substrate promiscuity could be altered by foreign MLPs. Kinetic studies and bioinformatics analysis indicated that MLPs’ functions are not as simple as previously thought.

antibiotics, synthethic biology, non-ribosomal pep↗
DOE OSTI2020

Mechanistic insights explain the transforming potential of the T507K substitution in the protein-tyrosine phosphatase SHP2

The protein-tyrosine phosphatase SHP2 is an allosteric enzyme critical for cellular events downstream of growth factor receptors. Mutations in the SHP2 gene have been linked to many different types of human diseases, including developmental disorders, leukemia, and solid tumors. Unlike most SHP2-activating mutations, the T507K substitution in SHP2 is unique in that it exhibits oncogenic Ras-like transforming activity. However, the biochemical basis of how the SHP2/T507K variant elicits transformation remains unclear. By combining kinetic and biophysical methods, X-ray crystallography, and molecular modeling, as well as using cell biology approaches, in this work we uncovered that the T507K substitution alters both SHP2 substrate specificity and its allosteric regulatory mechanism. We found that although SHP2/T507K exists in the closed, autoinhibited conformation similar to the WT enzyme, the interactions between its N-SH2 and protein-tyrosine phosphatase domains are weakened such that SHP2/T507K possesses a higher affinity for the scaffolding protein Grb2-associated binding protein 1 (Gab1). We also discovered that the T507K substitution alters the structure of the SHP2 active site, resulting in a change in SHP2 substrate preference for Sprouty1, a known negative regulator of Ras signaling and a potential tumor suppressor. Our results suggest that SHP2/T507K's shift in substrate specificity coupled with its preferential association of SHP2/T507K with Gab1 enable the mutant SHP2 to more efficiently dephosphorylate Sprouty1 at pTyr-53. This dephosphorylation hyperactivates Ras signaling, which is likely responsible for SHP2/T507K's Ras-like transforming activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗