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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 793 records · Page 44
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Chemoselective Hydrogenation with Supported Organoplatinum(IV) Catalyst on Zn(II)-Modified Silica

For this research, well-defined organoplatinum(IV) sites were grafted on a Zn(II)-modified SiO 2 support via surface organometallic chemistry in toluene at room temperature. Solid-state spectroscopies including XAS, DRIFTS, DRUV–vis, and solid-state (SS) NMR enhanced by dynamic nuclear polarization (DNP), as well as TPR-H 2 and TEM techniques revealed highly dispersed (methylcyclopentadienyl)methylplatinum(IV) sites on the surface ((MeCp)PtMe/Zn/SiO 2 , 1). In addition, computational modeling suggests that the surface reaction of (MeCp)PtMe 3 with Zn(II)-modified SiO 2 support is thermodynamically favorable (ΔG = -12.4 kcal/mol), likely due to the increased acidity of the hydroxyl group, as indicated by NH 3 -TPD and DNP-enhanced 17 O{ 1 H} SSNMR. In situ DRIFTS and XAS hydrogenation experiments reveal the probable formation of a surface Pt(IV)-H upon hydrogenolysis of Pt-Me groups. The heterogenized organoplatinum(IV)-hydride sites catalyze the selective partial hydrogenation of 1,3-butadiene to butenes (up to 95%) and the reduction of nitrobenzene derivatives to anilines (up to 99%) with excellent tolerance of reduction-sensitive functional groups (olefin, carbonyl, nitrile, halogens) under mild reaction conditions.

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

A Crystalline Polyimide Porous Organic Framework for Selective Adsorption of Acetylene over Ethylene

The separation of acetylene from ethylene is a crucial process in the petrochemical industry, as even small acetylene impurities can lead to premature termination of ethylene polymerization. Herein, we present the synthesis of a robust, crystalline naphthalene diimide porous aromatic framework via imidization of linear naphthalene-1,4,5,8-tetracarboxylic dianhydride and triangular tris(4-aminophenyl)amine. The resulting material, PAF-110, exhibits impressive thermal and long-term structural stability, as indicated by thermogravimetric analysis and powder X-ray diffraction characterization. Gas adsorption characterization reveals that PAF-110 has a capacity for acetylene that is more than twice its ethylene capacity at 273 K and 1 bar, and it exhibits a moderate acetylene selectivity of 3.9 at 298 K and 1 bar. Complementary computational investigation of each guest binding in PAF-110 suggests that this affinity and selectivity for acetylene arises from its stronger electrostatic interaction with the carbonyl oxygen atoms of the framework. As a result, to the best of our knowledge, PAF-110 is the first crystalline porous organic material to exhibit selective adsorption of acetylene over ethylene, and its properties may provide insight into the further optimized design of porous organic materials for this key gas separation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Elucidation of Active Sites in Aldol Condensation of Acetone over Single-Facet Dominant Anatase TiO 2 (101) and (001) Catalysts

Aldol condensations of carbonyl compounds for C–C bond formation are a very important class of reactions in organic synthesis and upgrading of biomass-derived feedstocks. However, the atomic level understanding of reaction mechanisms and structure-activity correlation on widely used transition metal oxide catalysts are limited due to the high degree of struc-tural heterogeneity of catalysts such as commercial TiO 2 powders. Here, we provide a deep understanding of the reaction mechanisms, kinetics, and structure–function relationships for vapor phase acetone aldol condensation through the con-trolled synthesis of two catalysts with high surface areas and clean, dominant facets, coupled with detailed characterization and kinetic studies that are further assisted by density functional theory (DFT) calculations. Temperature-dependent diffuse reflectance infrared Fourier transform spectroscopy showed the existence of abundant acetone bonded to surface hydroxyl groups (acetone-O s H) and acetone bonded to Lewis acid sites (acetone-Ti 5c ) on surface of both {101} and {001} facet dom-inant TiO 2 . Intermolecular C–C coupling of enolate intermediate from acetone-Ti 5c and a vicinal acetone-O s H is a kinetically relevant step, which is consistent with kinetic and isotopic studies and DFT calculations. The {001} facet showed a lower apparent activation energy (or higher reactivity) than the {101} facet. This is likely caused by the weaker Lewis acid and Brønsted base strengths of the {001} facet which favors the reprotonation–desorption of the coupled intermediate, making the C–C coupling step more exothermic on the {001} facet and resulting in an earlier transition state with a lower activation barrier. It is also possible that the {001} facet has a smoother surface configuration and less steric hindrance during intermo-lecular C–C bond formation than the {101} facet.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Reactive Landing of Dendrimer Ions onto Activated Self-assembled Monolayer Surfaces

The reactivity of gaseous, amine-terminated polyamidoamine (PAMAM) dendrimer ions with activated self-assembled monolayer (SAM) surfaces terminated with N-hydroxysuccinimidyl ester groups (NHS-SAM) is examined using mass-selected ion deposition combined with in situ infrared reflection absorption spectroscopy (IRRAS). The reaction extent is determined from depletion of the infrared band at 1753 cm-1, corresponding to the stretching vibration of the NHS carbonyl groups following ion deposition. For reaction yields below 10%, NHS band depletion follows a linear dependence on the ion dose. By comparing the kinetics plots obtained for 1,12-dodecanediamine and different generations of dendrimer ions (G0–G3) containing 4, 8, 16, and 32 terminal amino group, we demonstrate that the relative reaction efficiency increases linearly with the number of NH2 groups in the molecule. This finding is rationalized assuming the formation of multiple amide bonds upon collision of higher-generation dendrimers with NHS-SAM. Furthermore, by comparing the NHS band depletion following deposition of [M+4H]4+ ions of the G2 dendrimer at 30, 80, and 120 eV, we demonstrate that the ion’s kinetic energy has no measurable effect on reaction efficiency. Similarly, the ion’s charge state only has a minor effect on the reactive landing efficiency of dendrimer ions. Our results indicate that reactive landing is an efficient approach for highly selective covalent immobilization of complex multifunctional molecules onto organic surfaces terminated with labile functional groups.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2014

Insights into the Structural Changes Occurring upon Photoconversion in the Orange Carotenoid Protein from Broadband Two-Dimensional Electronic Spectroscopy

Carotenoids play an essential role in photoprotection, interacting with other pigments to safely dissipate excess absorbed energy as heat. In cyanobacteria, the short time scale photoprotective mechanisms involve the photoactive orange carotenoid protein (OCP), which binds a single carbonyl carotenoid. Blue-green light induces the photoswitching of OCP from its ground state form (OCPO) to a metastable photoproduct (OCPR). OCPR can bind to the phycobilisome antenna and induce fluorescence quenching. The photoswitching is accompanied by structural and functional changes at the level of the protein and of the bound carotenoid. In this study, we use broadband two-dimensional electronic spectroscopy to look at the differences in excited state dynamics of the carotenoid in the two forms of OCP. Our results provide insight into the origin of the pronounced vibrational lineshape and oscillatory dynamics observed in linear absorption and 2D electronic spectroscopy of OCPO and the large inhomogeneous broadening in OCPR, with consequences for the chemical function of the two forms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Quantitative comparison of organic photovoltaic bulk heterojunction photostability under laser illumination

The photostability of bulk heterojunction organic photovoltaic films containing a polymer donor and a fullerene-derivative acceptor was examined using resonance Raman spectroscopy and controlled laser power densities. The polymer donors were poly(3-hexylthiophene-2,5-diyl) (P3HT), poly[[9-(1-octylnonyl)-9H-carbazole-2,7-diyl]-2,5-thiophenediyl-2,1,3-benzothiadiazole-4,7-diyl-2,5-thiophenediyl] (PCDTBT), or poly({4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl}{3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl}) (PTB7). Four sample preparation methods were studied: (i) thin or (ii) thick films with fast solvent evaporation under nitrogen, (iii) thick films with slow solvent evaporation under nitrogen, and (iv) thin films dried under nitrogen followed by thermal annealing. Polymer order was assessed by monitoring a Raman peak’s full width at half-maximum and location as a function of illumination time and laser power densities from 2.5 × 10 3 to 2.5 × 10 5 W cm –2 . Resonance Raman spectroscopy measurements show that before prolonged illumination, PCDTBT and PTB7 have the same initial order for all preparation conditions, while P3HT order improves with slow solvent drying or thermal annealing. All films exhibited changes to bulk heterojunction structure with 2.5 × 10 5 Wcm –2 laser illumination as measured by resonance Raman spectroscopy, and atomic force microscopy images show evidence of sample heating that affects the polymer over an area greater than the illumination profile. Furthermore, photostability data are important for proper characterization by techniques involving illumination and the development of devices suitable for real-world applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Unimolecular dissociation dynamics of vibrationally activated CH 3 CHOO Criegee intermediates to OH radical products

The hydroxyl radical is a vital atmospheric oxidant, and a significant source of its production occurs through alkene ozonolysis. This takes place via a cycloaddition reaction and subsequent fragmentation to form an energized carbonyl oxide (for example, CH 3 CHOO), known as a Criegee intermediate, which can then either react with another atmospheric species or decay and, in doing so, produce the hydroxyl radical. In this work, we examine the dissociation dynamics of a prototypical Criegee intermediate by characterizing the translational and internal energy distributions of the OH radical products, which reflect critical configurations along the reaction pathway. Experimentally, the kinetic energy release to OH products is ascertained through velocity map imaging. Theoretically, quasi-classical trajectories are performed on a new full-dimensional, ab initio potential energy surface. Both experiment and theory show that most of the available energy flows into internal excitation of the vinoxy products. The isotropic angular distribution of OH fragments indicates that dissociation occurs in ≥2 ps, in agreement with theory.

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

Peak growing season gross uptake of carbon in North America is largest in the Midwest USA

Gross primary production (GPP) is a first-order uncertainty in climate predictions. Large-scale CO2 observations can provide information about the carbon cycle, but are not directly useful for GPP. Recently carbonyl sulfide (COS or OCS) has been proposed as a potential tracer for regional and global GPP. Here we present the first regional assessment of GPP using COS. We focus on the North American growing season—a global hotspot for COS air-monitoring and GPP uncertainty. Regional variability in simulated vertical COS concentration gradients was driven by variation in GPP rather than other modelled COS sources and sinks. Consequently we are able to show that growing season GPP in the Midwest USA significantly exceeds that of any other region of North America. These results are inconsistent with some ecosystem models, but are supportive of new ecosystem models from CMIP6. This approach provides valuable insight into the accuracy of various ecosystem land models.

Hilton, Timothy W.↗
DOE OSTI2015

Infrared identification of the Criegee intermediates syn - and anti -CH 3 CHOO, and their distinct conformation-dependent reactivity

The Criegee intermediates are carbonyl oxides that play critical roles in ozonolysis of alkenes in the atmosphere. So far, the mid-infrared spectrum of only the simplest Criegee intermediate CH 2 OO has been reported. Methyl substitution of CH 2 OO produces two conformers of CH 3 CHOO and consequently complicates the infrared spectrum. Here we report the transient infrared spectrum of syn - and anti -CH 3 CHOO, produced from CH 3 CHI + O 2 in a flow reactor, using a step-scan Fourier-transform spectrometer. Guided and supported by high-level full-dimensional quantum calculations, rotational contours of the four observed bands are simulated successfully and provide definitive identification of both conformers. Furthermore, anti -CH 3 CHOO shows a reactivity greater than syn -CH 3 CHOO towards NO/NO 2 ; at the later period of reaction, the spectrum can be simulated with only syn -CH 3 CHOO. Without NO/NO 2 , anti -CH 3 CHOO also decays much faster than syn -CH 3 CHOO. The direct infrared detection of syn - and anti -CH 3 CHOO should prove useful for field measurements and laboratory investigations of the Criegee mechanism.

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

Atomically precise graphene nanoribbon heterojunctions from a single molecular precursor

The rational bottom-up synthesis of atomically defined graphene nanoribbon (GNR) heterojunctions represents an enabling technology for the design of nanoscale electronic devices. Synthetic strategies used thus far have relied on the random copolymerization of two electronically distinct molecular precursors to yield GNR heterojunctions. In this paper we report the fabrication and electronic characterization of atomically precise GNR heterojunctions prepared through late-stage functionalization of chevron GNRs obtained from a single precursor. Post-growth excitation of fully cyclized GNRs induces cleavage of sacrificial carbonyl groups, resulting in atomically well-defined heterojunctions within a single GNR. The GNR heterojunction structure was characterized using bond-resolved scanning tunnelling microscopy, which enables chemical bond imaging at T = 4.5 K. Scanning tunnelling spectroscopy reveals that band alignment across the heterojunction interface yields a type II heterojunction, in agreement with first-principles calculations. Finally, GNR heterojunction band realignment proceeds over a distance less than 1 nm, leading to extremely large effective fields.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2026

Dynamically tunable membrane metasurfaces for infrared spectroscopy and strong light-matter interactions

Mid-infrared spectroscopy enables biochemical sensing by identifying vibrational molecular fingerprints, but it faces limitations in instrumentation portability and analytical sensitivity. Optical metasurfaces with strong mid-infrared photonic resonances provide an attractive solution towards on-chip spectrometry and sensitive molecular detection, yet their static nature hinders their anticipated impact. Here, we introduce and demonstrate dynamically tunable silicon membrane metasurfaces exhibiting high-Q transmissive resonances in the fingerprint region. By harnessing silicon’s thermo-optical properties, we achieve continuous modulation of coupling-induced transparency (CIT) modes that emerge upon the interference of quasi-bound states in the continuum (q-BICs) and surface lattice modes (SLMs). We measure a spectral tuning rate of 0.06 cm −1 K −1 by continuously sweeping the sharp CIT resonances over a 23.5 cm −1 spectral range across a temperature range of 300–700 K. In the current proof‑of‑concept implementation, the dynamic transmission control enables non-contact chemical analysis of polymer films by detecting characteristic absorption bands of polystyrene (1450 and 1492 cm −1 ) and poly(methyl methacrylate) (1730 cm −1 ) without requiring conventional spectrometers. When analyte molecules fill the metasurface-generated photonic cavities, we demonstrate vibrational strong coupling between the poly(methyl methacrylate)’s carbonyl band and the CIT mode, manifested in a Rabi splitting of ~43 cm −1 . Our results establish a new photonic platform that unites spectral precision, strong field enhancement, and reconfigurability, offering diverse potential for compact mid-infrared spectroscopy, molecular sensing, and programmable polaritonic photonics.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2018

Soil exchange rates of COS and CO18O differ with the diversity of microbial communities and their carbonic anhydrase enzymes

Abstract Differentiating the contributions of photosynthesis and respiration to the global carbon cycle is critical for improving predictive climate models. Carbonic anhydrase (CA) activity in leaves is responsible for the largest biosphere-atmosphere trace gas fluxes of carbonyl sulfide (COS) and the oxygen-18 isotopologue of carbon dioxide (CO18O) that both reflect gross photosynthetic rates. However, CA activity also occurs in soils and will be a source of uncertainty in the use of COS and CO18O as carbon cycle tracers until process-based constraints are improved. In this study, we measured COS and CO18O exchange rates and estimated the corresponding CA activity in soils from a range of biomes and land use types. Soil CA activity was not uniform for COS and CO2, and patterns of divergence were related to microbial community composition and CA gene expression patterns. In some cases, the same microbial taxa and CA classes catalyzed both COS and CO2 reactions in soil, but in other cases the specificity towards the two substrates differed markedly. CA activity for COS was related to fungal taxa and β-D-CA expression, whereas CA activity for CO2 was related to algal and bacterial taxa and α-CA expression. This study integrates gas exchange measurements, enzyme activity models, and characterization of soil taxonomic and genetic diversity to build connections between CA activity and the soil microbiome. Importantly, our results identify kinetic parameters to represent soil CA activity during application of COS and CO18O as carbon cycle tracers.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2019

Harnessing calcineurin-FK506-FKBP12 crystal structures from invasive fungal pathogens to develop antifungal agents

Calcineurin is important for fungal virulence and a potential antifungal target, but compounds targeting calcineurin, such as FK506, are immunosuppressive. Here we report the crystal structures of calcineurin catalytic (CnA) and regulatory (CnB) subunits complexed with FK506 and the FK506-binding protein (FKBP12) from human fungal pathogens (Aspergillus fumigatus, Candida albicans, Cryptococcus neoformans and Coccidioides immitis). Fungal calcineurin complexes are similar to the mammalian complex, but comparison of fungal and human FKBP12 (hFKBP12) reveals conformational differences in the 40s and 80s loops. NMR analysis, molecular dynamic simulations, and mutations of the A. fumigatus CnA/CnB-FK506-FKBP12-complex identify a Phe88 residue, not conserved in hFKBP12, as critical for binding and inhibition of fungal calcineurin. These differences enable us to develop a less immunosuppressive FK506 analog, APX879, with an acetohydrazine substitution of the C22-carbonyl of FK506. APX879 exhibits reduced immunosuppressive activity and retains broad-spectrum antifungal activity and efficacy in a murine model of invasive fungal infection.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2019

Dopant-tuned stabilization of intermediates promotes electrosynthesis of valuable C3 products

The upgrading of CO 2 /CO feedstocks to higher-value chemicals via energy-efficient electrochemical processes enables carbon utilization and renewable energy storage. Substantial progress has been made to improve performance at the cathodic side; whereas less progress has been made on improving anodic electro-oxidation reactions to generate value. Here we report the efficient electroproduction of value-added multi-carbon dimethyl carbonate (DMC) from CO and methanol via oxidative carbonylation. We find that, compared to pure palladium controls, boron-doped palladium (Pd-B) tunes the binding strength of intermediates along this reaction pathway and favors DMC formation. We implement this doping strategy and report the selective electrosynthesis of DMC experimentally. We achieve a DMC Faradaic efficiency of 83 ± 5%, fully a 3x increase in performance compared to the corresponding pure Pd electrocatalyst.

42 ENGINEERING↗
DOE OSTI2019

Mechanically rigid supramolecular assemblies formed from an Fmoc-guanine conjugated peptide nucleic acid

The variety and complexity of DNA-based structures make them attractive candidates for nanotechnology, yet insufficient stability and mechanical rigidity, compared to polyamide-based molecules, limit their application. Here, we combine the advantages of polyamide materials and the structural patterns inspired by nucleic-acids to generate a mechanically rigid fluorenylmethyloxycarbonyl (Fmoc)-guanine peptide nucleic acid (PNA) conjugate with diverse morphology and photoluminescent properties. The assembly possesses a unique atomic structure, with each guanine head of one molecule hydrogen bonded to the Fmoc carbonyl tail of another molecule, generating a non-planar cyclic quartet arrangement. This structure exhibits an average stiffness of 69.6 ± 6.8 N m –1 and Young’s modulus of 17.8 ± 2.5 GPa, higher than any previously reported nucleic acid derived structure. This data suggests that the unique cation-free “basket” formed by the Fmoc-G-PNA conjugate can serve as an attractive component for the design of new materials based on PNA self-assembly for nanotechnology applications.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

High-performance light-driven heterogeneous CO 2 catalysis with near-unity selectivity on metal phosphides

Akin to single-site homogeneous catalysis, a long sought-after goal is to achieve reaction site precision in heterogeneous catalysis for chemical control over patterns of activity, selectivity and stability. Herein, we report on metal phosphides as a class of material capable of realizing these attributes and unlock their potential in solar-driven CO 2 hydrogenation. Selected as an archetype, Ni 12 P 5 affords a structure based upon highly dispersed nickel nanoclusters integrated into a phosphorus lattice that harvest light intensely across the entire solar spectral range. Motivated by its panchromatic absorption and unique linearly bonded nickel-carbonyl-dominated reaction route, Ni 12 P 5 is found to be a photothermal catalyst for the reverse water gas shift reaction, offering a CO production rate of 960 ± 12 mmol g cat –1 h –1 , near 100% selectivity and long-term stability. Successful extension of this idea to Co2P analogs implies that metal phosphide materials are poised as a universal platform for high-rate and highly selective photothermal CO 2 catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗