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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 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Conformational Panorama and Chirality Controlled Structure–Energy Relationship in a Chiral Carboxylic Acid Dimer

Chirality recognition in dimers of tetrahydro-2-furoic acid (THFA) was studied in a conformer-specific manner using rotational spectroscopy and theoretical approaches. THFA shows a strong preference for the trans- over the cis-COOH configuration. Two drastically different scenarios are possible for the detectable (THFA) 2 : a kinetically preferred dimer bound by feeble interactions between two trans-THFAs or a thermodynamically favored dimer with a double hydrogen-bonded ring structure between two cis subunits. To identify the conformers responsible for the extremely dense rotational spectra observed, it was essential not only to locate several hundred homo/heterochiral (THFA) 2 minima in ab initio calculations but also to evaluate the energetic connectivities among the minima. The study further reveals an interesting chirality dependent structure-energy ordering relationship. A method for enantiomeric excess (ee) determination of THFA is presented using a recently proposed chiral self-tag approach.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Data-Conforming Data-Driven Control: Avoiding Premature Generalizations Beyond Data

Data-driven and adaptive control approaches face the problem of introducing sudden distributional shifts beyond the distribution of data encountered during learning. Therefore, they are prone to invalidating the very assumptions used in their own construction. This is due to the linearity of the underlying system, inherently assumed and formulated in most data-driven control approaches, which may falsely generalize the behavior of the system beyond the behavior experienced in the data. This article seeks to mitigate these problems by enforcing consistency of the newly designed closed-loop systems with data and slowing down any distributional shifts in the joint state-input space. This is achieved through incorporating affine regularization terms and linear matrix inequality constraints to data-driven approaches, resulting in convex semi-definite programs that can be efficiently solved by standard software packages. We discuss the optimality conditions of these programs and then conclude this article with a numerical example that further highlights the problem of premature generalization beyond data and shows the effectiveness of our proposed approaches in enhancing the safety of data-driven control methods.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2024

Microsecond dynamics control the HIV-1 Envelope conformation

The HIV-1 Envelope (Env) glycoprotein facilitates host cell fusion through a complex series of receptor-induced structural changes. Although remarkable progress has been made in understanding the structures of various Env conformations, microsecond timescale dynamics have not been studied experimentally. Here, we used time-resolved, temperature-jump small-angle x-ray scattering to monitor structural rearrangements in an HIV-1 Env SOSIP ectodomain construct with microsecond precision. In two distinct Env variants, we detected a transition that correlated with known Env structure rearrangements with a time constant in the hundreds of microseconds range. A previously unknown structural transition was also observed, which occurred with a time constant below 10 μs, and involved an order-to-disorder transition in the trimer apex. Using this information, we engineered an Env SOSIP construct that locks the trimer in the prefusion closed state by connecting adjacent protomers via disulfides. Our findings show that the microsecond timescale structural dynamics play an essential role in controlling the Env conformation with impacts on vaccine design.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Molecular structures reveal the origin of spectral variation in cryptophyte light harvesting antenna proteins

In addition to their membrane-bound chlorophyll a/c light-harvesting antenna, the cryptophyte algae have evolved a unique phycobiliprotein antenna system located in the thylakoid lumen. The basic unit of this antenna consists of two copies of an αβ protomer where the α and β subunits scaffold different combinations of a limited number of linear tetrapyrrole chromophores. While the β subunit is highly conserved, encoded by a single plastid gene, the nuclear-encoded α subunits have evolved diversified multigene families. It is still unclear how this sequence diversity results in the spectral diversity of the mature proteins. By careful examination of three newly determined crystal structures in comparison with three previously obtained, we show how the α subunit amino acid sequences control chromophore conformations and hence spectral properties even when the chromophores are identical. Previously we have shown that α subunits control the quaternary structure of the mature αβ.αβ complex (either open or closed), however, each species appeared to only harbor a single quaternary form. Here we show that species of the Hemiselmis genus contain expressed α subunit genes that encode both distinct quaternary structures. Finally, we have discovered a common single-copy gene (expressed into protein) consisting of tandem copies of a small α subunit that could potentially scaffold pairs of light harvesting units. Together, our results show how the diversity of the multigene α subunit family produces a range of mature cryptophyte antenna proteins with differing spectral properties, and the potential for minor forms that could contribute to acclimation to varying light regimes.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

A Metal-on-Metal Growth Approach to Metal–Metal Oxide Core–Shell Nanostructures with Plasmonic Properties

Hybrid core–shell nanoparticles integrate the material properties from individual components; however, the synthesis of core–shell nanoparticles with dissimilar materials remains challenging. Herein, we applied a metal-on-metal thin film growth approach to control the conformal deposition of non-precious metal shells on the Cu-based metal cores to form core–shell structures of metal–metal oxide hybrids (M–M'O x , where M = AuCu 3 or Cu, M' = Fe, Mn, and Ni). The deposition kinetics were controlled by a temperature-regulated thermal decomposition of zerovalent transition metal complexes. It is predicted that the conformal deposition can be promoted by keeping the initial deposition temperature close to the thermal decomposition temperature of the zerovalent precursors. The mechanisms of strain reduction and interdiffusion facilitate conformal deposition over island growth in the synthesis with slow reaction kinetics. This study provides insightful guidance to metal-on-metal growth in solution at the nanoscale and thus the seed-mediated approach to hybrid core–shell structures. The optical properties of these metal–metal oxide hybrids were investigated experimentally and interpreted by theoretical simulations. Despite damping effects, the plasmonic properties of these Cu-based core-metal oxide shell structures may have the potential to enable plasmon-enhanced applications.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Amphiphile conformation impacts aggregate morphology and solution structure across multiple lengthscales

Although the self-assembly of amphiphiles is well-studied in aqueous solutions, much less is understood about the fundamental driving forces and structure property relationships in non-polar media. In recent work [Journal of Physical Chemistry B, 2020, 124, 10822.] the authors have studied a series of malonomide-based amphiphiles that are relevant to liquid-liquid extraction. That work demonstrated that aggregation is largely driven by local dipole-dipole interactions between molecules. Here, we build upon this observation to develop a more detailed understanding of how the balance of dipole-dipole interactions (controlled by conformation) and molecular architecture influences the morphology of the aggregates across lengthscales. Using constrained molecular dynamics about key degrees of freedom, we demonstrate that the conformation of N,N-dimethyl,N,N-dioctylhexylethoxy malonamide (DMDOHEMA) and N,N-dimethyl,N,N-dibutyltetradecyl malonamide (DMDBTDMA) has a significant impact upon self-association - where appropriate conformational sampling is essential. To quantify the aggregate morphology, several graph theoretic and persistent homology based properties are determined. The former examines the patterns of intermolecular interactions within clusters, while the latter examines the 3-dimensional spatial distribution. Based upon these analyses, we find that the morphology of aggregates, particularly at higher malonamide concentration, depends on a balance of dipole alignment and alkyl tail sterics. Dipole alignment encourages linear patterns of the intermolecular interactions within aggregates, while the alkyl tail steric interactions between the malonamide result in noticeably less linear aggregates for DMDOHEMA than DMDBTDMA. This is reflected in the spatial distribution, where more holes or voids exist between extractants within the DMDOHEMA that distribute within the solution in more of a "swiss cheese" arrangement as opposed to the more filamentous distribution of DMBDTDMA. This study links conformation and molecular structure to the morphology of amphiphile assemblies, and serves as a basis for ongoing study of multicomponent amphiphile solutions with polar and other solutes, and how these impact aggregation phenomena.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Engineering Structural Transitions in a Multilevel Molecular Switch via Intermolecular Coupling

Controlling molecular conformations with atomic precision is essential for advancing molecular functional electronics, as well as our understanding of molecular dynamics. While switching between bistable molecular conformers is common in nature, creating systems with multiple, addressable states remains synthetically challenging. Here, we demonstrate a bottom-up strategy in which intermolecular interactions give rise to multilevel functionality within a simple two-molecule assembly. Using low-temperature scanning tunneling microscopy, we show that a pyrrolidine dimer on Cu(100) exhibits six distinct adsorption conformations, exceeding the four expected from two independent bistable units. This unusual complexity arises from the interplay between intermolecular van der Waals attraction and steric repulsion, which reshapes the potential energy landscape and changes a single high-energy transition into a sequential two-step pathway. Each step is driven by low-energy inelastic electron excitations, achieving a switching efficiency an order of magnitude higher than that of the monomer. Here, by tuning the bias voltage and tip–molecule distance, we achieve deterministic control over multiple stable states, establishing a general design principle for on-demand engineering of collective molecular behavior and energy-efficient multilevel molecular devices.

Molecular interactions↗
DOE OSTI2023

Xylan-cellulose core structure of oat water-extractable β-glucan macromolecule: Insight into interactions and organization of the cell wall complex

Water-extractable β-glucan with high molar mass (HM) determines health benefits of oat food. Oat β-glucan was extracted by a standardized in vitro digestion method and co-existing water-extractable polysaccharide (WEP) fraction and its HM-arabinoxylan (HM-AX) subfraction were isolated to identify their highly acid-resistant subunit and investigate molecular interactions between constituent polymers. The WEP and HM-AX samples consisted of arabinoxylans (AXs) (74 and 76 %, respectively), however, cellulose constituted the secondary component (6.6 and 12.8 %, respectively). Multi-detection HPSEC along with specific enzymatic hydrolysis of AXs revealed the presence of the HM-xylan domain (16 and 34 %, respectively) built of numerous single- and multi-component populations with random coil and rod-like conformations, which were embedded in a xylan matrix with spherical conformation and controlled the macromolecular shape. Unlike single-component populations, the multi-component ones were resistant to hydrolytic action of AX-hydrolyzing enzymes and represented the subunits that anchor matrix polysaccharides onto cellulose surface. These results indicate that water-extractable β-glucan macromolecule comprises as integral element a cellulose core with two linking populations, HM-xylan and low molar mass glucomannan, which are surrounded by a feruloylated AX-arabinan-arabinogalactan composite and next laminated by β-glucan matrix. Here, the stiff cellulose-xylan backbone is the basis of HM β-glucan organization, controlled by its cellulose-like segments.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Selective penetration behavior of microgels in superpermeable channels and reservoir matrices

Gel treatment is an effective way to attack excessive water production in many mature oilfields around the world. Selective penetration is desired for successful gel treatments. That is, gel materials should easily penetrate the target zones (i.e., channeling features such as superpermeable channels) without entering/damaging the nontarget zones (i.e., reservoir matrices or oil zones). This study revealed that presence of threshold penetration pressure (ΔP th ) was responsible for selective penetration behavior of tested microgels. The concept of ΔP th was utilized to figure out favorable working conditions for effective gel treatments. Microgel dispersions were injected into superpermeable (super-k) sandpacks (mimicking super-k channels in reservoirs, 60–221 darcies), heterogeneous models with super-k channels (79–230 darcies), and sandstone cores (mimicking reservoir matrices, 50–5000 md). The results demonstrated that a minimum differential driving pressure (i.e., threshold penetration pressure, ΔP th ) was required to push microgel particles to penetrate channels or matrices. The critical penetration behavior was closely related to the particle/pore size ratio. Low ΔP th at smaller particle/pore ratios was beneficial to allow easy penetration of gel materials into the channeling zones. On the contrary, high ΔPth at larger particle/pore ratios was desirable to prevent gel materials from massively invading and damaging the matrices. Instead, the gel particles accumulated at the inlet surface, and a gel cake was gradually formed. The cake further prevented the invasion of the gels. The cake could be removed by chemical breakers to resume the injectivity/productivity of the matrices. Correlations were developed to describe the relationship between ΔP th and particle/pore ratio. A distinct transition was identified at the particle/pore ratio of about 3. This research could help identify the favorable conditions to achieve successful gel treatments. In an effective conformance treatment, the particle/pore ratio in the channel should be sufficiently low to allow easy penetration of gel materials into the channel (e.g., particle/pore ratio<2 in this study). Meanwhile, the particle/pore ratio in the matrix should be large enough to support a high ΔP th and thus prevent massive gel invasion into the matrix. This study advances the current pore scale studies (a single particle passing through a single channel) to Darcy-scale characterization.

02 PETROLEUM↗
DOE OSTI2020

Structures of ISCth4 transpososomes reveal the role of asymmetry in copy-out/paste-in DNA transposition

Copy-out/paste-in transposition is a major bacterial DNA mobility pathway. It contributes significantly to the emergence of antibiotic resistance, often by upregulating expression of downstream genes upon integration. Unlike other transposition pathways, it requires both asymmetric and symmetric strand transfer steps. Here, we report the first structural study of a copy-out/paste-in transposase and demonstrate its ability to catalyze all pathway steps in vitro. X-ray structures of ISCth4 transposase, a member of the IS256 family of insertion sequences, bound to DNA substrates corresponding to three sequential steps in the reaction reveal an unusual asymmetric dimeric transpososome. During transposition, an array of N-terminal domains binds a single transposon end while the catalytic domain moves to accommodate the varying substrates. These conformational changes control the path of DNA flanking the transposon end and the generation of DNA-binding sites. Our results explain the asymmetric outcome of the initial strand transfer and show how DNA binding is modulated by the asymmetric transposase to allow the capture of a second transposon end and to integrate a circular intermediate.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Electrostatically assembled open square and checkerboard superlattices

Programmable assembly of nanoparticles into structures other than two-dimensional hexagonal lattices remains challenging. Assembling an open checkerboard or square lattice is harder to achieve compared to a close-packed hexagonal structure. Here, in this study, we introduce a unified, robust approach to assemble nanoparticles into a diverse family of two-dimensional superlattices at the liquid–air interface. Gold nanoparticles are grafted with pH-responsive, water-soluble poly(ethylene glycol) chains terminating in single bondCOOH or -NH 2 end groups, enabling control over interparticle Coloumbic interactions, while the molecular weight of grafted polymer dictates its conformation. This combined control of charges and conformation enables crystallization into checkerboard, simple-square, and body-centered honeycomb superlattices. Furthermore, tuning the pH induces structural transitions between different lattice types. This approach opens new avenues for the fabrication of colloidal superstructures with tailored architectures.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Molecular Alignment of a Meta-Aramid on Carbon Nanotubes by In Situ Interfacial Polymerization

Molecularly organized nanocomposites of polymers and carbon nanotubes (CNTs) have great promise as high-performance materials; in particular, conformal deposition of polymers can control interfacial properties for mechanical load transfer, electrical or thermal transport, or electro/chemical transduction. However, controllability of polymer-CNT interaction remains a challenge with common processing methods that combine CNTs and polymers in melt or in solution, often leading to nonuniform polymer distribution and CNT aggregation. In this work, we demonstrate CNTs within net-shape sheets can be controllably coated with a conformal coating of meta-aramid by simultaneous capillary infiltration and interfacial polymerization. We determine that π-interaction between the polymer and CNTs results in chain alignment parallel to the CNT outer wall. Subsequent nucleation and growth of the precipitated aramid forms a smooth continuous layered sheath around the CNTs. These findings motivate future investigation of mechanical properties of the resulting composites, and adaptation of the in situ polymerization method to other substrates.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2022

Switching charge states in quasi-2D molecular conductors

Abstract 2D molecular entities build next-generation electronic devices, where abundant elements of organic molecules are attractive due to the modern synthetic and stimuli control through chemical, conformational, and electronic modifications in electronics. Despite its promising potential, the insufficient control over charge states and electronic stabilities must be overcome in molecular electronic devices. Here, we show the reversible switching of modulated charge states in an exfoliatable 2D-layered molecular conductor based on bis(ethylenedithio)tetrathiafulvalene molecular dimers. The multiple stimuli application of cooling rate, current, voltage, and laser irradiation in a concurrent manner facilitates the controllable manipulation of charge crystal, glass, liquid, and metal phases. The four orders of magnitude switching of electric resistance are triggered by stimuli-responsive charge distribution among molecular dimers. The tunable charge transport in 2D molecular conductors reveals the kinetic process of charge configurations under stimuli, promising to add electric functions in molecular circuitry.

Huang, Yulong (ORCID:0000000296160134)↗
DOE OSTI2021

Atomic Layer Deposition for Materials-Based H2 Storage: Opportunities and Limitations

The transportation demands in our growing hydrogen (H2) economy requires robust storage systems. The current commercially implemented technology in fuel cell cars relies on the well-established technology of hydrogen gas compressed to 350-700 bar, depending on the application. The compressed gas tanks in use today are bulky and cost intensive. To address this challenge, material-based storage is one of the long-term alternatives considered and constitutes the focus of this talk. Material-based storage is broadly defined as hydrogen bound to solid materials, with its binding strength varying from physisorption to porous materials, such as zeolites and metal organic frameworks, to chemisorption in (complex) metal hydrides. The ultimate targets set by the U.S. Department of Energy for this technology include a system gravimetric capacity of 6.5 wt% and volumetric capacity of 40 g/L at 100 bar, operating temperatures ranging between -40 C and +40 C and adsorption/desorption timescales of < 5 min. Storage in the form of physisorbed or chemisorbed hydrogen has guided the materials research, which metal- organic framework and (complex) metal hydrides being the most promising materials classes. A variety of these materials have met one or more of the targets, but it has remained elusive for a single material system to meet all these stringent requirements. Nano-encapsulation and low-concentration chemical additives have previously been employed separately to overcome such challenges. Functionalization via atomic layer deposition (ALD), however, offers unique characteristics that make it suitable for both, nano-encapsulation and "doping" with low-concentration additives. This deposition technique has sub-monolayer thickness control, is highly conformal in high-surface area materials and is self-limiting, i.e., once the gas-phase precursor reacts with the available surface sites, the surface reactions stop. In this presentation, we will showcase examples where ALD, more generally vapor-phase functionalization, on (complex) metal hydrides and organic frameworks has improved the material properties for H2 storage. In our first study, Al2O3 was deposited on magnesium borohydride, Mg(BH4)2, at room temperature using trimethylaluminum (TMA) and water. From our findings, encouraging initial results were obtained: the H2 desorption temperature was lowered by 60-120 degrees C, the desorbed gravimetric H2 capacity at temperatures < 250 degrees C was doubled, and the desorption kinetics increased by a factor of ~6 compared to uncoated Mg(BH4)2. However, hydrolysis reactions caused by residual surface -OH groups from the ALD water-pulse degraded the sample substantially. Through this study, the use of TMA was observed to be highly reactive with the Mg(BH4)2 surface species, leading to the strategy of exposing the sample only to TMA. The relative mole fraction of the vapor-phase additive can be precisely controlled with the number of TMA pulses and pulse duration. By tuning these parameters, we show in our second study that 10 pulses of TMA at ambient conditions were able to decrease the H2 desorption temperature by ~100 degrees C while retaining <95 % of its H2 capacity. We applied this approach with other additives such as BBr3, TiCl4 and tetrahydrofuran, and demonstrate that this unique approach opens the door to a new class of molecular additives and catalysts which cannot easily be introduced with conventional mechano-chemical or solvent-based techniques for (complex) metal-hydrides. In the case of metal organic frameworks, ALD is a promising technique to functionalize the pores with metal atoms or functional groups able to tune the gas selectivity and binding energy, for which ~15 kJ/mol has been established as the optimal value for H2 storage in sorbent materials. Vapor-phase techniques such as ALD have numerous benefits over other functionalization tools for H2 storage materials opening innumerable opportunities to the field. To exploit these opportunities, the current limitations on room temperature and water-less ALD processes needs to be overcome which will greatly expand the possibilities of encapsulation and incorporation of additives for organic frameworks and (complex) metal hydrides.

atomic layer deposition↗