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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 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Two-Dimensional Crystallization of Poly( N -isopropylacrylamide)-Capped Gold Nanoparticles

Surface-sensitive X-ray reflectivity and grazing incidence small-angle X-ray scattering reveal the structure of polymer-capped-gold nanoparticles (AuNPs that are grafted with poly(N-isopropylacrylamide); PNIPAM–AuNPs) as they self-assemble and crystallize at the aqueous suspension/vapor interface. Citrate-stabilized AuNPs (5 and 10 nm in nominal diameter) are ligand-exchanged by 6 kDa PNIPAM-thiol to form corona brushes around the AuNPs that are highly stable and dispersed in aqueous suspensions. Surprisingly, no clear evidence of thermosensitive effect on surface enrichment or self-assembly of the PNIPAM–AuNPs is observed in the 10–35 °C temperature range. However, addition of simple salts (in this case, NaCl) to the suspension induces migration of the PNIPAM–AuNPs to the aqueous surface, and above a threshold salt concentration, two-dimensional crystals are formed. In conclusion, the 10 nm PNIPAM–AuNPs form a highly ordered single layer with in-plane triangular structure, whereas the 5 nm capped NPs form short-range triangular structure that gradually becomes denser as salt concentration increases.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Electronic Properties of Free-Standing Surfactant-Capped Lead Halide Perovskite Nanocrystals Isolated in Vacuo

We report an investigation of lead halide perovskite CH3NH3PbBr3 nanocrystals and associated ligand molecules by combining several different state-of-the-art experimental techniques, including synchrotron radiation-based XPS and VUV PES of free-standing nanocrystals isolated in vacuum. By using this novel approach for perovskite materials, we could directly obtain complete band alignment to vacuum of both CH3NH3PbBr3 nanocrystals and the ligands widely used in their preparation. We discuss the possible influence of the ligand molecules to apparent perovskite properties, and we compare the electronic properties of nanocrystals to those of bulk material. The experimental results were supported by DFT calculations.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Assembling PNIPAM-Capped Gold Nanoparticles in Aqueous Solutions

Employing small-angle X-ray scattering (SAXS), we explore the conditions under which assembly of gold nanoparticles (AuNPs) grafted with the thermosensitive polymer poly(N-isopropylacrylamide) (PNIPAM) emerges. We find that short-range order assembly emerges by combining the addition of electrolytes or polyelectrolytes with raising the temperature of the suspensions above the lower-critical solution temperature (LCST) of PNIPAM. Our results show that the longer the PNIPAM chain is, the better organization in the assembled clusters. Interestingly, without added electrolytes, there is no evidence of AuNPs assembly as a function of temperature, although untethered PNIPAM is known to undergo a coil-to-globule transition above its LCST. This study demonstrates another approach to assembling potential thermosensitive nanostructures for devices by leveraging the unique properties of PNIPAM.

Nayak, Binay P↗
DOE OSTI2016

Structural basis for m7G recognition and 2'-O-methyl discrimination in capped RNAs by the innate immune receptor RIG-I

RNAs with 5'-triphosphate (ppp) are detected in the cytoplasm principally by the innate immune receptor Retinoic Acid Inducible Gene-I (RIG-I), whose activation triggers a Type I IFN response. It is thought that self RNAs like mRNAs are not recognized by RIG-I because 5'ppp is capped by the addition of a 7-methyl guanosine (m7G) (Cap-0) and a 2'-O-methyl (2'-OMe) group to the 5'-end nucleotide ribose (Cap-1). Here we provide structural and mechanistic basis for exact roles of capping and 2'-O-methylation in evading RIG-I recognition. Surprisingly, Cap-0 and 5'ppp double-stranded (ds) RNAs bind to RIG-I with nearly identical K d values and activate RIG-I’s ATPase and cellular signaling response to similar extents. On the other hand, Cap-0 and 5'ppp single-stranded RNAs did not bind RIG-I and are signaling inactive. Three crystal structures of RIG-I complexes with dsRNAs bearing 5'OH, 5'ppp, and Cap-0 show that RIG-I can accommodate the m7G cap in a cavity created through conformational changes in the helicase-motif IVa without perturbing the ppp interactions. In contrast, Cap-1 modifications abrogate RIG-I signaling through a mechanism involving the H830 residue, which we show is crucial for discriminating between Cap-0 and Cap-1 RNAs. Furthermore, m7G capping works synergistically with 2'-O-methylation to weaken RNA affinity by 200-fold and lower ATPase activity. Interestingly, a single H830A mutation restores both high-affinity binding and signaling activity with 2'-O-methylated dsRNAs. Our work provides new structural insights into the mechanisms of host and viral immune evasion from RIG-I, explaining the complexity of cap structures over evolution.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2016

The mechanism of RNA 5' capping with NAD + , NADH and desphospho-CoA

The chemical nature of the 5' end of RNA is a key determinant of RNA stability, processing, localization and translation efficiency and has been proposed to provide a layer of ‘epitranscriptomic’ gene regulation. Recently it has been shown that some bacterial RNA species carry a 5'-end structure reminiscent of the 5' 7-methylguanylate ‘cap’ in eukaryotic RNA. In particular, RNA species containing a 5'-end nicotinamide adenine dinucleotide (NAD+) or 3'-desphospho-coenzyme A (dpCoA) have been identified in both Gram-negative and Gram-positive bacteria. It has been proposed that NAD+, reduced NAD+ (NADH) and dpCoA caps are added to RNA after transcription initiation, in a manner analogous to the addition of 7-methylguanylate caps. Here we show instead that NAD+, NADH and dpCoA are incorporated into RNA during transcription initiation, by serving as non-canonical initiating nucleotides (NCINs) for de novo transcription initiation by cellular RNA polymerase (RNAP). We further show that both bacterial RNAP and eukaryotic RNAP II incorporate NCIN caps, that promoter DNA sequences at and upstream of the transcription start site determine the efficiency of NCIN capping, that NCIN capping occurs in vivo, and that NCIN capping has functional consequences. We report crystal structures of transcription initiation complexes containing NCIN-capped RNA products. Our results define the mechanism and structural basis of NCIN capping, and suggest that NCIN-mediated ‘ab initio capping’ may occur in all organisms.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Mammalian Nudix proteins cleave nucleotide metabolite caps on RNAs

We recently reported the presence of nicotinamide adenine dinucleotide (NAD)-capped RNAs in mammalian cells and a role for DXO and the Nudix hydrolase Nudt12 in decapping NAD-capped RNAs (deNADding) in cells. Analysis of 5'caps has revealed that in addition to NAD, mammalian RNAs also contain other metabolite caps including flavin adenine dinucleotide (FAD) and dephosphoCoA (dpCoA). In the present study we systematically screened all mammalian Nudix proteins for their potential deNADing, FAD cap decapping (deFADding) and dpCoA cap decapping (deCoAping) activity. We demonstrate that Nudt16 is a novel deNADding enzyme in mammalian cells. Additionally, we identified seven Nudix proteins—Nudt2, Nudt7, Nudt8, Nudt12, Nudt15, Nudt16 and Nudt19, to possess deCoAping activity in vitro. Moreover, our screening revealed that both mammalian Nudt2 and Nudt16 hydrolyze FAD-capped RNAs in vitro with Nudt16 regulating levels of FAD-capped RNAs in cells. All decapping activities identified hydrolyze the metabolite cap substrate within the diphosphate linkage. Crystal structure of human Nudt16 in complex with FAD at 2.7 Å resolution provide molecular insights into the binding and metal-coordinated hydrolysis of FAD by Nudt16. In summary, our study identifies novel cellular deNADding and deFADding enzymes and establishes a foundation for the selective functionality of the Nudix decapping enzymes on non-canonical metabolite caps.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2015

Impact of laser-contaminant interaction on the performance of the protective capping layer of 1w high-reflection mirror coatings

In this paper, high dielectric constant multilayer coatings are commonly used on high-reflection mirrors for high-peak-power laser systems because of their high laser-damage resistance. However, surface contaminants often lead to damage upon laser exposure, thus limiting the mirror’s lifetime and performance. One plausible approach to improve the overall mirror resistance against laser damage, including that induced by laser-contaminant coupling, is to coat the multilayers with a thin protective capping (absentee) layer on top of the multilayer coatings. An understanding of the underlying mechanism by which laser-particle interaction leads to capping layer damage is important for the rational design and selection of capping materials of high-reflection multilayer coatings. In this paper, we examine the responses of two candidate capping layer materials, made of SiO 2 and Al 2 O 3 , over silica-hafnia multilayer coatings. These are exposed to a single oblique shot of a 1053 nm laser beam (fluence ~10 J/cm 2 , pulse length 14 ns), in the presence of Ti particles on the surface. We find that the two capping layers show markedly different responses to the laser-particle interaction. The Al 2 O 3 cap layer exhibits severe damage, with the capping layer becoming completely delaminated at the particle locations. The SiO 2 capping layer, on the other hand, is only mildly modified by a shallow depression. Combining the observations with optical modeling and thermal/mechanical calculations, we argue that a high-temperature thermal field from plasma generated by the laser-particle interaction above a critical fluence is responsible for the surface modification of each capping layer. The great difference in damage behavior is mainly attributed to the large disparity in the thermal expansion coefficient of the two capping materials, with that of Al 2 O 3 layer being about 15 times greater than that of SiO 2 .

36 MATERIALS SCIENCE↗
DOE OSTI2023

IACMI Project 4.7: Pultruded Textile Carbon Fiber for Spar Caps (Final Report)

The primary objective of this project was to demonstrate the potential to significantly reduce the cost of wind turbine blades with carbon fiber reinforced polymer (CFRP) structure. Applicability of textile carbon fibers (TCF) were evaluated for use in pultruded spar cap (SC) elements as a path to cost reduction for utility scale wind turbine blades. In earlier work for the Department of Energy (DOE) Wind Energy Technologies Office (WETO), a collaboration of Sandia National Laboratory (SNL), Oak Ridge National Laboratory (ORNL), and Montana State University has demonstrated potential for pultruded TCF to compete with infused fiberglass and commercially available carbon fiber pultruded sections for spar cap construction. In the design cases evaluated, the TCF sections fared well when compared on cost per unit composite stiffness and cost per unit composite compressive strength for those designs [1]. Both stiffness and compressive strength tend to be key factors in the design of blade composite Spar Cap which carry the bulk of the blade structural loads in bending. Spar Cap design tends to distribute largely symmetric tensile and compressive stresses to opposite sides of the spar structure, but since carbon fiber composite compressive strength is typically 20-50% lower than tensile strength, the compressive loading reaches failure levels well before the tensile loading. Stiffness is critical in containing the large tip deflection in high wind loading situations. However, materials and process development were very limited in the earlier study and the work in this project was expanded to make the comparative information more representative of what will be required in order to make further inroads towards implementation. Similar to that study, this project team confirmed that the primary materials of interest for pultruded spar cap elements should be thermoset (TS) resins reinforced by carbon fibers, utilizing as high a percentage of TCF as practical to benchmark cost and performance against commercial carbon fibers. To make the closest comparison possible and eliminate specific test article size, resin selection, and equipment/operational nuance effects, the team planned to pultrude sections with 100% commercially available carbon fiber (Panex 35 carbon fiber from Zoltek) as well as samples utilizing high fractions of TCF. The resin system chosen was based on formulations recommended by large wind industry supplier Hexion and consisted of Hexion resin RSL-4597, curing agent CCA-138, and internal mold release additive 117, along with common kaolin filler ASP400P from BASF. As commonly deployed in spar cap configurations, the team had a mold built to pultrude a rectangular spar cap element of 100mm width and 3mm thickness. The extremely limited number of samples produced for the earlier study were produced with a “generic” epoxy utilized for a variety of applications by the pultruder contracted to produce test articles for demonstration purposes. More importantly, those samples were produced at a fiber fraction only slightly over 50%. Based on feedback from our industrial advisory team for that project and strongly recommended by this project team, the consensus is that it is highly desirable to obtain fiber fractions of 65-68% for significant penetration in wind blade spar cap. Although this requirement has yet to be exhaustively confirmed in readily available information, this was established as a project goal and informally decided we needed to exceed 60% fiber fraction to gain serious industry consideration. Previous TCF pultrusion trials have been challenged by the lack of robust TCF packages, resulting in non-uniform tension across and between tows, as well as excess labor and waste for removal of interleaved paper. The non-uniform tension and associated intermingling of tows in textile acrylic fiber tows and associated difficulties created from broken filaments in carbon fiber conversion inhibit the ordered packing necessary to enhance fiber fraction elevation. (These “cross-overs” are not considered undesirable for textile applications and there is some sense that they might be advantageous for those applications). In addition to work that is ongoing at the acrylic fiber manufacturers to improve their formats, The Institute of Advanced Composites Manufacturing Innovation (IACMI) Project 6.12 (report PA16-0349-6.12-01) [2] has developed and demonstrated a more robust packaging and creeling approach that at least partially addresses these issues, thus improving control of the TCF feed into the pultrusion unit. It was hoped that these and other improvements currently being implemented would allow us to achieve fiber fractions at least approaching these fiber fraction targets. During this project, sections utilizing 100% commercially available carbon fiber reinforcement were produced as a baseline, as well as sections reinforced with about 94% TCF and the balance being commercially available fiber for comparison. The most important finding was that similar to results reported in the earlier WETO-funded project and results from tests of TCF reported at IACMI meetings, this work demonstrated that sections pultruded with TCF in an epoxy resin frequently utilized in actual spar cap production had stiffness and compressive strengths largely comparable to similar sections pultruded with a commercially available carbon fiber also frequently utilized in the wind industry. Although the amount of that data is limited, some of the tensile strength results were actually closer than would have been expected based on fiber strength results provided by the TCF and commercial fiber producers. The actual test data are reported and discussed in detail in Section 5. The pultruded sections dominated by TCF reinforcement were approximately 8-10% lower in fiber fraction than for the sections produced using commercial fiber alone, making direct comparison difficult. The COVID-19 project has provided significant insight into the current state-of-the-art with various TCF product forms. The data obtained in this project will guide the planned improvements at the precursor level, especially in attaining uniform tensioning and payout to facilitate enhanced fiber fractions and overall processability of the TCF composites. The project team is providing guidance to stakeholders concerning the attributes, needs, and potential demand for TCF in wind blade spar caps. Results achieved in this project are consistent with findings in the related work cited [1] and support this guidance and the high potential for this product type. TCF precursor-producing partners continue to express interest in enhancing their product forms and the team looks forward to working with these improved materials as they become available.

42 ENGINEERING↗
DOE OSTI2017

Using Prescribed Fire to Manage the Fernald On-Site Disposal Facility Vegetated Cap - 17401

The Fernald Preserve is a former uranium processing plant that underwent extensive remediation pursuant to the Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA). It is situated on a 425 ha (1,050 acre) tract of land, approximately 29 km (18 miles) northwest of Cincinnati, Ohio. Remedial activities and subsequent ecological restoration have converted the site from an industrial production facility to an undeveloped park, encompassing a series of wetlands, prairies, and forested communities. The remediation of buildings and soil contamination was completed in 2006, but aquifer remediation is ongoing. Since 2007, the site has been managed by the US Department of Energy (DOE) Office of Legacy Management. Portions of the site are open to the public, with approximately 11 km (7 miles) of walking trails that are open year-round and a visitors center. Site remediation included the construction of an On-Site Disposal Facility (OSDF) for the long-term disposal of contaminated soil and building materials. The OSDF consists of eight disposal cells that encompass approximately 30 hectares (75 acres) on the eastern portion of the Fernald site. Cells are lined and capped, and each has a separate leak detection and leachate collection system. The integrated cap is vegetated with native grasses and forbs. Management of the Fernald Preserve includes the monitoring and maintenance of ecologically restored communities and the vegetated OSDF cap, as required by the site's institutional controls plan. Prescribed burning is recognized as the preferred method for prairie management. Prescribed fire has been used at the Fernald site since 2009 for established prairies in restored areas, but not on the OSDF cap. Stakeholders had reservations regarding the safety of using prescribed fire on the OSDF cap. Because of that, vegetation on the cap was managed as a grassland community. It was mowed, raked, and baled to remove thatch, and promote the continued establishment of native grasses and forbs. Since agricultural use is restricted at the site, the resulting hay bales were kept on property and reused as organic matter and mulch. Over time, more hay bales were being generated in a season than were reused. Therefore in 2015, DOE decided to revisit stakeholder acceptance of prescribed fire on the OSDF cap. Ongoing relationships with local stakeholders allowed for extensive discussions regarding the current management and proposed use of prescribed fire on the OSDF cap. The public was provided information about the planning and implementation of prescribed burns at the site and invited to observe the execution of a successful site burn. This approach led to stakeholder acceptance of DOE's proposal, and vegetation on the caps of cells 4, 5, and 6 was burned in late March 2016. The burn was successful and resulted in several benefits from a land stewardship and cost perspective. This paper details the stakeholder engagement approach and the resulting benefits from the use of prescribed fire on the OSDF cap. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2015

Crystallinity of tellurium capping and epitaxy of ferromagnetic topological insulator films on SrTiO 3

Thin films of topological insulators are often capped with an insulating layer since topological insulators are known to be fragile to degradation. However, capping can hinder the observation of novel transport properties of the surface states. To understand the influence of capping on the surface states, it is crucial to understand the crystal structure and the atomic arrangement at the interfaces. Here, we use x-ray diffraction to establish the crystal structure of magnetic topological insulator Cr-doped (Bi,Sb) 2 Te 3 (CBST) films grown on SrTiO 3 (1 1 1) substrates with and without a Te capping layer. We find that both the film and capping layer are single crystal and that the crystal quality of the film is independent of the presence of the capping layer, but that x-rays cause sublimation of the CBST film, which is prevented by the capping layer. Our findings show that the different transport properties of capped films cannot be attributed to a lower crystal quality but to a more subtle effect such as a different electronic structure at the interface with the capping layer. Our results on the crystal structure and atomic arrangements of the topological heterostructure will enable modelling the electronic structure and design of topological heterostructures.

33 ADVANCED PROPULSION SYSTEMS↗