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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 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Isomer of linker for NU-1000 yields a new she -type, catalytic, and hierarchically porous, Zr-based metal–organic framework

The well-known MOF (metal–organic framework) linker tetrakis(p-benzoate)pyrene (TBAPy 4– ) lacks steric hindrance between its benzoates. Changing the 1,3,6,8-siting of benzoates in TBAPy 4– to 4,5,9,10-siting introduces substantial steric hindrance and, in turn, enables the synthesis of a new hierarchically porous, she-type MOF Zr 6 (μ 3 -O)4(μ 3 -OH) 4 (C 6 H 5 COO) 3 (COO) 3 (TBAPy-2) 3/2 (NU-601), where TBAPy-2 4– is the 4,5,9,10 isomer of TBAPy 4– . In conclusion, NU-601 shows high catalytic activity for degradative hydrolysis of a simulant for G-type fluoro-phosphorus nerve agents.

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

Experimental and computational investigation of the bond energy of thorium dicarbonyl cation and theoretical elucidation of its isomerization mechanism to the thermodynamically most stable isomer, thorium oxide ketenylidene cation, OTh + CCO

Collision-induced dissociation (CID) of [Th,2C,2O] + with Xe is performed using a guided ion beam tandem mass spectrometer (GIBMS). The only products observed are ThCO + and Th + by sequential loss of CO ligands. The experimental findings and theoretical calculations support that the structure of [Th,2C,2O] + is the bent homoleptic thorium dicarbonyl cation, Th + (CO) 2 , having quartet spin, which is both thermodynamically and kinetically stable enough in the gas phase to be observed in our GIBMS instrument. Analysis of the kinetic energy-dependent cross sections for this CID reaction yields the first experimental determination of the bond dissociation energy (BDE) of (CO)Th + –CO at 0 K as 1.05 ± 0.09 eV. A theoretical BDE calculated at the CCSD(T) level with cc-pVXZ (X = T and Q) basis sets and a complete basis set (CBS) extrapolation is in very good agreement with the experimental result. Although the doublet spin bent thorium oxide ketenylidene cation, OTh + CCO, is calculated to be the most thermodynamically stable structure, it is not observed in our experiment where [Th,2C,2O] + is formed by association of Th + and CO in a direct current discharge flow tube (DC/FT) ion source. Potential energy profiles of both quartet and doublet spin are constructed to elucidate the isomerization mechanism of Th + (CO) 2 to OTh + CCO. The failure to observe OTh + CCO is attributed to a barrier associated with C–C bond formation, which makes OTh + CCO kinetically inaccessible under our experimental conditions. Furthermore, chemical bonding patterns in low-lying states of linear and bent Th + (CO) 2 and OTh + CCO isomers are also investigated.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2021

Efficient separation of xylene isomers by using a robust calcium-based metal–organic framework through a synergetic thermodynamically and kinetically controlled mechanism

Adsorptive separation of physically and chemically similar molecules and understanding the underlying host–guest interactions at the molecular level are of significant scientific and practical importance. Here we report the development of a novel calcium-based metal–organic framework, formulated as Ca 3 (Htcpp) 2 (H 4 tcpp = 2,3,5,6-tetrakis(4-carboxyphenyl)-pyrazine) featuring microporosity and high stability. This compound shows distinct adsorption behavior toward xylene isomers and is capable of separating them efficiently at an industrially relevant temperature. The selective adsorption is attributed to a synergetic thermodynamic and kinetic effect. Here, the host–guest interactions were probed directly by single-crystal X-ray diffraction analysis and the adsorption affinity was evaluated through computational molecular simulations.

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

57Fe Mössbauer isomer shift of pure iron and iron oxides at high pressure—An experimental and theoretical study

The 57Fe isomer shift (IS) of pure iron has been measured up to 100 GPa using synchrotron Mössbauer spectroscopy in the time domain. Apart from the expected discontinuity due to the α→ε structural and spin transitions, the IS decreases monotonically with increasing pressure. The absolute shifts were reproduced without semi-empirical calibrations by periodic density functional calculations employing extensive localized basis sets with several common density functionals. However, the best numerical agreement is obtained with the B1WC hybrid functional. Extension of the calculations to 350 GPa, a pressure corresponding to the Earth’s inner core, predicted the IS range of 0.00 to -0.85 mm/s, covering the span from Fe(0) to Fe(VI) compounds measured at ambient pressure. The calculations also reproduced the pressure trend from polymorphs of prototypical iron oxide minerals, FeO and Fe2O3. Analysis of the electronic structure shows a strong donation of electrons from oxygen to iron at high pressure. The assignment of formal oxidation to the Fe atom becomes ambiguous under this condition.

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

An efficient LC-MS method for isomer separation and detection of sugars, phosphorylated sugars, and organic acids

Abstract Assessing central carbon metabolism in plants can be challenging due to the dynamic range in pool sizes, with low levels of important phosphorylated sugars relative to more abundant sugars and organic acids. Here, we report a sensitive liquid chromatography–mass spectrometry method for analysing central metabolites on a hybrid column, where both anion-exchange and hydrophilic interaction chromatography (HILIC) ligands are embedded in the stationary phase. The liquid chromatography method was developed for enhanced selectivity of 27 central metabolites in a single run with sensitivity at femtomole levels observed for most phosphorylated sugars. The method resolved phosphorylated hexose, pentose, and triose isomers that are otherwise challenging. Compared with a standard HILIC approach, these metabolites had improved peak areas using our approach due to ion enhancement or low ion suppression in the biological sample matrix. The approach was applied to investigate metabolism in high lipid-producing tobacco leaves that exhibited increased levels of acetyl-CoA, a precursor for oil biosynthesis. The application of the method to isotopologue detection and quantification was considered through evaluating 13C-labeled seeds from Camelina sativa. The method provides a means to analyse intermediates more comprehensively in central metabolism of plant tissues.

Plant Sciences↗
DOE OSTI2025

Reduction in Nuclear Size and Quadrupole Deformation of High-Spin Isomers of 127,129 In

We employed laser spectroscopy of atomic transitions to measure the nuclear charge radii and electromagnetic properties of the high-spin isomeric states in neutron-rich indium isotopes (𝑍 =49) near the closed proton and neutron shells at 𝑍 = 50 and 𝑁 = 82. Our data reveal a reduction in the nuclear charge radius and intrinsic quadrupole moment when protons and neutrons are fully aligned in 129 In ⁢(𝑁 = 80), to form the high spin isomer. Such a reduction is not observed in 127 In ⁢(𝑁 = 78), where more complex configurations can be formed by the existence of four neutron holes. These observations are not consistently described by nuclear theory.

high spin states↗
DOE OSTI2025

Astrophysical significance of the isomer 119⁢𝑚 Ag demonstrated through a direct mass measurement

Here, the abundance of elements heavier than iron produced via the astrophysical rapid-neutron-capture process depends sensitively on the atomic mass of the involved nuclei as well as the behavior of a few special types of nuclear isomers called “astromers.” High-precision mass measurements of 119 Cd and 119 Ag and their respective isomeric states have been performed with the phase-imaging ion cyclotron resonance (PI-ICR) method with a precision of 𝛿⁢𝑚/𝑚 ≈ 10 −8 using the Canadian Penning trap. The ground-state mass excess, as well as the excitation energy, agrees with recent Penning trap measurements from JYFLTRAP. Network calculations using these new measurements have revealed that, contrary to previous expectations, 119⁢𝑚 Ag behaves as an astromer, which significantly affects the population of 119 Ag .

Rivero, F. [University of Notre Dame, IN (United S↗
DOE OSTI2023

Data for MALDI-MS Screening of Microbial Colonies With Isomer Resolution to Select Fatty Acid Desaturase Variants

Creating controlled lipid unsaturation locations in oleochemicals can be a key to many bioengineered products. However, evaluating the effects of modifications to the acyl-ACP desaturase on lipid unsaturation is not currently amenable to high-throughput assays, limiting the scale of redesign efforts to <200 variants. Here, we report a rapid mass spectrometry (MS) assay for profiling the positions of double bonds on membrane lipids produced by Escherichia coli colonies after treatment with ozone gas. By MS measurement of the ozonolysis products of Δ6 and Δ8 isomers of membrane lipids from colonies expressing recombinant Thunbergia alata desaturase, we screened a randomly mutagenized library of the desaturase gene at 5 s per sample. Two variants with altered regiospecificity were isolated, indicated by an increase in 16:1 Δ8 proportion. We also demonstrated the ability of these desaturase variants to influence the membrane composition and fatty acid distribution of E. coli strains deficient in the native acyl-ACP desaturase gene, fabA. Finally, we used the fabA deficient chassis to concomitantly express a non-native acyl-ACP desaturase and a medium-chain thioesterase from Umbellularia californica, demonstrating production of only saturated free fatty acids.

Conversion↗
DOE OSTI2023

Catalytic Transformation of Positional Nitrophenol Isomers on Highly Active Ag/Linde‐Type A4 Zeolite: A Comparative Analysis

Abstract The catalytic transformation of ortho‐( o‐ NP), meta‐( m‐ NP) and para‐nitrophenols ( p‐ NP) by Ag nanoparticles (Ag‐NPs) stabilised on zeolite A4 (ZA4) is presented for the first time. The catalysts are prepared by microwave‐assisted synthesis (Ag/ZA4‐MW) or ion exchange (Ag/ZA4‐IE). The results indicate that the nitrophenol reduction rate depends on the molecule structure and the presence of low‐coordinated metallic Ag‐NPs (∼2 nm and sub nanometric species). Meanwhile, the reactivity tendency depends on the synthesis methodology ( m‐ NP> p‐ NP> o‐ NP and o‐ NP> m‐ NP> p‐ NP for Ag/ZA4‐MW and Ag/ZA4‐IE, respectively). The turnover frequency (TOF) values estimated for nitrophenols reduction are superior for Ag/ZA4‐MW catalyst by several orders of magnitude compared with those obtained for Ag/ZA4‐IE catalyst. In addition, the catalyst exhibits remarkable catalytic stability for the reduction of p‐ NP even after the fifth consecutive catalytic run. The presently prepared catalysts are characterised by superior catalytic activity for the reduction of nitroaromatic compounds than similar Ag‐based materials reported in the literature.

Horta‐Fraijo, Patricia↗
DOE OSTI2020

Branching ratio and γ -ray emission probabilities in the decay of the J π = 13 / 2 + isomer in 197Hg

Gamma rays following the decay of the 197 g Hg and 197 m Hg radionuclides were measured using chemically-purified sources and a planar HPGe detector. In the case of 197 m Hg, precise values of 94.68 (9)% and 5.32 (9)% were confirmed for the IT and EC branches, respectively, the latter discovered to differ significantly from previously published data. The half-lives of 197 g Hg and 197 m Hg were also measured as 64.81 (24) h and 23.82 (4) h.

197𝑔Hg↗