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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

Synthesis of mixed-valent [alpha]- and [beta]-NaFe[subscript 2]O[subscript 3] polymorphs under controlled partial oxygen pressure

Synthesis of mixed valent compounds, especially when multiple polymorphs exist, requires careful control of the preparation conditions. {alpha}- and {beta}-NaFe{sub 2}O{sub 3} polymorphs were synthesized under controlled partial oxygen pressure (pO{sub 2}). pO{sub 2} regions of stability at 850 C were determined for both phases for the first time. A modified oxygen buffer method was developed for the facile preparation of mixed valent oxides under controlled pO{sub 2}. {beta}-NaFe{sub 2}O{sub 3} is the only known n = 2 member of the AM{sub n}O{sub n+1} (A = alkali metal, M = 3d metal) rock-salt related homolog series with layered cation ordering. The possibility of new members of the homolog series with other 3d metals is considered.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Conversion of Human Steroid 5[beta]-Reductase (AKR1D1) into 3[beta]-Hydroxysteroid Dehydrogenase by Single Point Mutation E120H: Example of Perfect Enzyme Engineering

Human aldo-keto reductase 1D1 (AKR1D1) and AKR1C enzymes are essential for bile acid biosynthesis and steroid hormone metabolism. AKR1D1 catalyzes the 5{beta}-reduction of {Delta}{sup 4}-3-ketosteroids, whereas AKR1C enzymes are hydroxysteroid dehydrogenases (HSDs). These enzymes share high sequence identity and catalyze 4-pro-(R)-hydride transfer from NADPH to an electrophilic carbon but differ in that one residue in the conserved AKR catalytic tetrad, His120 (AKR1D1 numbering), is substituted by a glutamate in AKR1D1. We find that the AKR1D1 E120H mutant abolishes 5{beta}-reductase activity and introduces HSD activity. However, the E120H mutant unexpectedly favors dihydrosteroids with the 5{alpha}-configuration and, unlike most of the AKR1C enzymes, shows a dominant stereochemical preference to act as a 3{beta}-HSD as opposed to a 3{alpha}-HSD. The catalytic efficiency achieved for 3{beta}-HSD activity is higher than that observed for any AKR to date. High resolution crystal structures of the E120H mutant in complex with epiandrosterone, 5{beta}-dihydrotestosterone, and {Delta}{sup 4}-androstene-3,17-dione elucidated the structural basis for this functional change. The glutamate-histidine substitution prevents a 3-ketosteroid from penetrating the active site so that hydride transfer is directed toward the C3 carbonyl group rather than the {Delta}{sup 4}-double bond and confers 3{beta}-HSD activity on the 5{beta}-reductase. Structures indicate that stereospecificity of HSD activity is achieved because the steroid flips over to present its {alpha}-face to the A-face of NADPH. This is in contrast to the AKR1C enzymes, which can invert stereochemistry when the steroid swings across the binding pocket. These studies show how a single point mutation in AKR1D1 can introduce HSD activity with unexpected configurational and stereochemical preference.

59 BASIC BIOLOGICAL SCIENCES↗

The Majorana Demonstrator: A Search for Neutrinoless Double-beta Decay of 76 Ge

Neutrinoless double-beta (0νββ) decay is a hypothesized process where in some even-even nuclei it might be possible for two neutrons to simultaneously decay into two protons and two electrons without emitting neutrinos. This is possible only if neutrinos are Majorana particles, i.e. fermions that are their own antiparticles. Neutrinos being Majorana particles would explicitly violate lepton number conservation, and might play a role in the matter-antimatter asymmetry in the universe. The observation of neutrinoless double-beta decay would also provide complementary information related to neutrino masses. The MAJORANA Collaboration is constructing the MAJORANA DEMONSTRATOR, a 40-kg modular germanium detector array, to search for the 0νββ decay of 76Ge and to demonstrate a background rate at or below 3 counts/(ROI-t-y) in the 4 keV region of interest (ROI) around the 2039 keV Q-value for 76Ge 0νββ decay. In this paper, we discuss the physics of neutrinoless double beta decay and then focus on the MAJORANA DEMONSTRATOR, including its design and approach to achieve ultra-low backgrounds and the status of the experiment.

Xu, W.↗

Development of Cryogenic Bolometer for 0{nu}{beta}{beta} in {sup 124}Sn

Cryogenic bolometer detectors, with their high resolution spectroscopy capability, are ideal for neutrino mass experiments as well as for search of rare processes like neutrinoless double beta decay (0{nu}{beta}{beta}) and dark matter. A feasibility study for investigation of 0{nu}{beta}{beta} in {sup 124}Sn at the upcoming underground facility of India based Neutrino Observatory (INO) has been initiated. This paper describes endeavors towards cryogenic tin bolometer development.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

The role of estrogen receptor {beta} (ER{beta}) in malignant diseases-A new potential target for antiproliferative drugs in prevention and treatment of cancer

The discovery of ER{beta} in the middle of the 1990s represents a paradigm shift in our understanding of estrogen signaling. It has turned out that estrogen action is not mediated by one receptor, ER{alpha}, but by two balancing factors, ER{alpha} and ER{beta}, which are often antagonistic to one another. Excitingly, ER{beta} has been shown to be widespread in the body and to be involved in a multitude of physiological and pathophysiological events. This has led to a strong interest of the pharmaceutical industry to target ER{beta} by drugs against various diseases. In this review, focus is on the role of ER{beta} in malignant diseases where the anti proliferative activity of ER{beta} gives hope of new therapeutic approaches.

60 APPLIED LIFE SCIENCES↗

Sodium-Beta Alumina Batteries: Status and Challenges

Sodium-beta alumina batteries, have been extensively developed for a few decades and encouraging progress has been achieved so far. The anode is typically molten sodium while the cathode can be molten sulfur (Na-S battery) or solid transition metal halides plus a liquid phase secondary electrolyte (e.g., ZEBRA battery). The electrolyte typically used is a β"-Al2O3 solid membrane. The issues prohibiting broad commercialization of this type of technology are dependent on the materials used, but can be broadly described as relatively high cost, safety (particularly for the Na-S couple), and low power. This paper offers a review on materials and designs for the batteries and discusses the challenges ahead for further technology improvement.

25 ENERGY STORAGE↗

Beneficial effect of 17{beta}-estradiol on hyperglycemia and islet {beta}-cell functions in a streptozotocin-induced diabetic rat model

The modulating effect of estrogen on glucose homeostasis remains a controversial issue at present. In this study, we sought to determine the beneficial effect of 17{beta}-estradiol (E{sub 2}) on hyperglycemia and islet {beta}-cell functions in streptozotocin (STZ)-induced diabetic rats. Male Sprague-Dawley rats were injected i.p. with STZ to induce a relatively mild diabetic condition. The rats were then treated with E{sub 2} orally at 500 {mu}g/kg body weight/day for 15 days to evaluate the modulating effect on hyperglycemia, insulin secretion, and islet {beta}-cell proliferation. E{sub 2} administration for 10 days significantly lowered plasma glucose levels, increased plasma insulin levels, and improved glucose tolerance by attenuating insulin response to oral glucose loading. These beneficial effects of E{sub 2} were accompanied by increases in islet number and volume, rate of islet cell proliferation, and the amount of insulin secreted. The growth-stimulatory effect of E{sub 2} on islet cells was linked to the functions of the estrogen receptor {alpha}. Notably, these protective effects of E{sub 2} on diabetic conditions were basically not observed when the STZ-treated rats had a more severe degree of islet damage and hyperglycemia. Taken together, we conclude that E{sub 2} can promote the regeneration of damaged pancreatic islets by stimulating {beta}-cell proliferation in diabetic rats, and this effect is accompanied by improvements in glucose tolerance and a decrease in plasma glucose levels. These findings suggest that oral administration of E{sub 2} may be beneficial in diabetic patients with an accelerated loss of islet {beta}-cells.

60 APPLIED LIFE SCIENCES↗

Titanium-Beta Zeolites Catalyze the Stereospecific Isomerization of D-Glucose to L-Sorbose via Intramolecular C5-C1 Hydride Shift

Pure-silica zeolite beta containing Lewis acidic framework Ti 4+ centers (Ti-Beta) is shown to catalyze the isomerization of D-glucose to L-sorbose via an intramolecular C5–C1 hydride shift. Glucose–sorbose isomerization occurs in parallel to glucose–fructose isomerization on Ti-Beta in both water and methanol solvents, with fructose formed as the predominant product in water and sorbose as the predominant product in methanol (at 373 K) at initial times and over the course of >10 turnovers. Isotopic tracer studies demonstrate that 13 C and D labels placed respectively at the C1 and C2 positions of glucose are retained respectively at the C6 and C5 positions of sorbose, consistent with its formation via an intramolecular C5–C1 hydride shift isomerization mechanism. This direct Lewis acid-mediated pathway for glucose–sorbose isomerization appears to be unprecedented among heterogeneous or biological catalysts and sharply contrasts indirect base-mediated glucose–sorbose isomerization via 3,4-enediol intermediates or via retro-aldol fragmentation and recombination of sugar fragments. Measured first-order glucose–sorbose isomerization rate constants (per total Ti; 373 K) for Ti-Beta in methanol are similar for glucose and glucose deuterated at the C2 position (within a factor of ~1.1), but are a factor of ~2.3 lower for glucose deuterated at each carbon position, leading to H/D kinetic isotope effects expected for kinetically relevant intramolecular C5–C1 hydride shift steps. Optical rotation measurements show that isomerization of D-(+)-glucose (92% enantiomeric purity) with Ti-Beta in water (373 K) led to the formation of L-(-)-sorbose (73% enantiomeric purity) and D-(-)-fructose (87% enantiomeric purity) as the predominant stereoisomers, indicating that stereochemistry is preserved at carbon centers not directly involved in intramolecular C5–C1 or C2–C1 hydride shift steps, respectively. This new Lewis acid-mediated rearrangement of glucose to sorbose does not appear to have a metalloenzyme analog.

bio-inspired, hydrogen and fuel cells↗

Novel Insights Into The Mode of Inhibition of Class A SHV-1 Beta-Lactamases Revealed by Boronic Acid Transition State Inhibitors

Boronic acid transition state inhibitors (BATSIs) are potent class A and C {beta}-lactamase inactivators and are of particular interest due to their reversible nature mimicking the transition state. Here, we present structural and kinetic data describing the inhibition of the SHV-1 {beta}-lactamase, a clinically important enzyme found in Klebsiella pneumoniae, by BATSI compounds possessing the R1 side chains of ceftazidime and cefoperazone and designed variants of the latter, compounds 1 and 2. The ceftazidime and cefoperazone BATSI compounds inhibit the SHV-1 {beta}-lactamase with micromolar affinity that is considerably weaker than their inhibition of other {beta}-lactamases. The solved crystal structures of these two BATSIs in complex with SHV-1 reveal a possible reason for SHV-1's relative resistance to inhibition, as the BATSIs adopt a deacylation transition state conformation compared to the usual acylation transition state conformation when complexed to other {beta}-lactamases. Active-site comparison suggests that these conformational differences might be attributed to a subtle shift of residue A237 in SHV-1. The ceftazidime BATSI structure revealed that the carboxyl-dimethyl moiety is positioned in SHV-1's carboxyl binding pocket. In contrast, the cefoperazone BATSI has its R1 group pointing away from the active site such that its phenol moiety moves residue Y105 from the active site via end-on stacking interactions. To work toward improving the affinity of the cefoperazone BATSI, we synthesized two variants in which either one or two extra carbons were added to the phenol linker. Both variants yielded improved affinity against SHV-1, possibly as a consequence of releasing the strain of its interaction with the unusual Y105 conformation.

59 BASIC BIOLOGICAL SCIENCES↗

CUPID-0: the first array of enriched scintillating bolometers for 0$\nu \beta \beta$ decay investigations

The CUPID-0 detector hosted at the Laboratori Nazionali del Gran Sasso, Italy, is the first large array of enriched scintillating cryogenic detectors for the investigation of 82 Se neutrinoless double-beta decay (0$\nu \beta \beta$). CUPID0 aims at measuring a background index in the region of interest (RoI) for 0$\nu \beta \beta$ at the level of 10 -3 counts/(keV kg years), the lowest value ever measured using cryogenic detectors. CUPID-0 operates an array of Zn 82 Se scintillating bolometers coupled with bolometric light detectors, with a state of the art technology for background suppression and thorough protocols and procedures for the detector preparation and construction. In this paper, the different phases of the detector design and construction will be presented, from the material selection (for the absorber production) to the new and innovative detector structure. The successful construction of the detector lead to promising preliminary detector performance which is discussed here.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Searches for double beta decay of Xe 134 with EXO-200

Searches for double beta decay of 134 Xe were performed with EXO-200, a single-phase liquid xenon detector designed to search for neutrinoless double beta decay of 136 Xe. Using an exposure of 29.6 kg ∙ yr , the lower limits of T$2νββ\atop{1/2}$ > 8.7 × 10 20 yr and T$0νββ\atop{1/2}$ > 1.1 × 10 23 yr at 90% confidence level were derived, with corresponding half-life sensitivities of 1.2 × 10 21 yr and 1.9 × 10 23 yr . In conclusion, these limits exceed those in the literature for 134 Xe , improving by factors of nearly 10 5 and 2 for the two antineutrino and neutrinoless modes, respectively.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Short-baseline electron neutrino disappearance, tritium beta decay, and neutrinoless double-beta decay

We consider the interpretation of the MiniBooNE low-energy anomaly and the gallium radioactive source experiments anomaly in terms of short-baseline electron neutrino disappearance in the framework of 3+1 four-neutrino mixing schemes. The separate fits of MiniBooNE and gallium data are highly compatible, with close best-fit values of the effective oscillation parameters {Delta}m{sup 2} and sin{sup 2}2{theta}. The combined fit gives {Delta}m{sup 2}(greater-or-similar sign)0.1 eV{sup 2} and 0.11(less-or-similar sign)sin{sup 2}2{theta}(less-or-similar sign)0.48 at 2{sigma}. We consider also the data of the Bugey and Chooz reactor antineutrino oscillation experiments and the limits on the effective electron antineutrino mass in {beta} decay obtained in the Mainz and Troitsk tritium experiments. The fit of the data of these experiments limits the value of sin{sup 2}2{theta} below 0.10 at 2{sigma}. Considering the tension between the neutrino MiniBooNE and gallium data and the antineutrino reactor and tritium data as a statistical fluctuation, we perform a combined fit which gives {Delta}m{sup 2}{approx_equal}2 eV and 0.01(less-or-similar sign)sin{sup 2}2{theta}(less-or-similar sign)0.13 at 2{sigma}. Assuming a hierarchy of masses m{sub 1}, m{sub 2}, m{sub 3}<<m{sub 4}, the predicted contributions of m{sub 4} to the effective neutrino masses in {beta} decay and neutrinoless double-{beta} decay are, respectively, between about 0.06 and 0.49 and between about 0.003 and 0.07 eV at 2{sigma}. We also consider the possibility of reconciling the tension between the neutrino MiniBooNE and gallium data and the antineutrino reactor and tritium data with different mixings in the neutrino and antineutrino sectors. We find a 2.6{sigma} indication of a mixing angle asymmetry.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

NH3-SCR on Cu, Fe and Cu+Fe exchanged Beta and SSZ-13 catalysts: hydrothermal aging and propylene poisoning effects

Cu, Fe and Cu+Fe ion exchanged Beta and SSZ-13 catalysts were prepared by solution ion exchange using commercial NH4/Beta, and NH4/SSZ-13 that was prepared in-house. To study hydrothermal aging effects, Beta supported catalysts were aged hydrothermally at 700 C and SSZ-13 supported catalysts were aged at 750 C. In order to reveal the effects of Fe addition in the co-exchanged catalysts, these catalysts were characterized by means of powder X-ray diffraction (XRD), N2 adsorption-desorption, electron paramagnetic resonance (EPR), 27Al-nuclear magnetic resonance (27Al-NMR) and propylene coking followed with temperature programmed reaction (TPR), and further tested with standard NH3-SCR with and without the presence of propylene. Collectively, the catalyst characterizations and reaction testing indicated minor beneficial effects of Fe addition in Cu,Fe/Beta, where NH3-SCR activity, N2 selectivity and hydrothermal stability were all slightly improved. In contrast, Fe addition did not show apparent beneficial effects in low-temperature SCR for the Cu,Fe/SSZ-13 case. At elevated reaction temperatures, however, the presence of Fe indeed considerably improved NO conversion and N2 selectivity for the hydrothermally aged Cu,Fe/SSZ-13 catalyst in the presence of propylene. The authors from Pacific Northwest National Laboratory (PNNL) gratefully acknowledge the US Department of Energy (DOE), Energy Efficiency and Renewable Energy, Vehicle Technologies Office for the support of this work. The research described in this paper was performed in the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at PNNL. PNNL is operated for the US DOE by Battelle. The authors from East China University of Science and Technology acknowledge support from National Basic Research Program of China (2013CB933200), National Natural Science Foundation of China (21577035, 21577034), Commission of Science and Technology of Shanghai Municipality (15DZ1205305) and 111 Project (B08021). Aiyong Wang also gratefully acknowledges the China Scholarship Council for a Joint-Training Scholarship Program with PNNL.

Wang, Aiyong↗