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At least 1,747 records · Page 97
All sourcesNASA NTRSDOE OSTI
DOE OSTI2013

Gas-Phase Synthesis of Singly and Multiply Charged Polyoxovanadate Anions Employing Electrospray Ionization and Collision Induced Dissociation

Electrospray ionization mass spectrometry (ESI-MS) combined with in-source fragmentation and tandem mass spectrometry (MS/MS) experiments were used to generate a wide range of singly and multiply charged vanadium oxide cluster anions including V x O y n– and V x O y Cl n– ions (x = 1–14, y = 2–36, n = 1–3), protonated clusters, and ligand-bound polyoxovanadate anions. The cluster anions were produced by electrospraying a solution of tetradecavanadate, V 14 O 36 Cl(L) 5 (L = Et 4 N + , tetraethylammonium), in acetonitrile. Under mild source conditions, ESI-MS generates a distribution of doubly and triply charged V x O y Cl n– and V x O y Cl(L) (n–1)– clusters predominantly containing 14 vanadium atoms as well as their protonated analogs. Accurate mass measurement using a high-resolution LTQ/Orbitrap mass spectrometer (m/Δm = 60,000 at m/z 410) enabled unambiguous assignment of the elemental composition of the majority of peaks in the ESI-MS spectrum. In addition, high-sensitivity mass spectrometry allowed the charge state of the cluster ions to be assigned based on the separation of the major from the much less abundant minor isotope of vanadium. In-source fragmentation resulted in facile formation of smaller V x O y Cl (1–2)– and V x O y (1–2)– anions. Collision-induced dissociation (CID) experiments enabled systematic study of the gas-phase fragmentation pathways of the cluster anions originating from solution and from in-source CID. Surprisingly simple fragmentation patterns were obtained for all singly and doubly charged V x O y Cl and V x O y species generated through multiple MS/MS experiments. In contrast, cluster anions originating directly from solution produced comparatively complex CID spectra. These results are consistent with the formation of more stable structures of V x O y Cl and V x O y anions through low-energy CID. Finally and furthermore, our results demonstrate that solution-phase synthesis of one precursor cluster anion combined with gas-phase CID is an efficient approach for the top-down synthesis of a wide range of singly and multiply charged gas-phase metal oxide cluster anions for subsequent investigations of structure and reactivity using mass spectrometry and ion spectroscopy techniques.

collision-induced dissociation↗
DOE OSTI2018

Towards the synthesis of modular process intensification systems with safety and operability considerations - application to heat exchanger network

In this paper, we present a systematic framework for the synthesis of safely operable process intensification systems. Herein, intensified designs are automatically generated by using phenomena-based Generalized Modular Representation Framework, while their safety and operability performances are guaranteed by incorporating: (i) flexibility analysis and multiperiod design, (ii) inherent safety analysis utilizing quantitative risk assessment, and (iii) multi-parametric model predictive control strategies developed via the PAROC framework. As an example from a broader set of intensified systems, the proposed framework is applied to heat exchanger network synthesis for thermal intensification, demonstrating its capability on enhancing safety and operability at early design stage.

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

Towards a systematic framework for the synthesis of operable process intensification systems

In this work we present an integrated framework to derive intensified designs with guaranteed safety and operability performance. A step-by-step procedure is described featuring: (i) superstructure-based process synthesis using Generalized Modular Representation Framework, (ii) development of advanced multi-parametric control strategies following the PAROC framework and software platform, and (iii) inherent safety analysis at early design stage utilizing quantitative risk assessment. Here, two case studies with increasing intensification complexity, namely heat exchanger network synthesis and reactive distillation column design, are investigated to demonstrate the capabilities of the proposed framework.

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

Enhanced metal loading in SBA-15-type catalysts facilitated by salt addition. Synthesis, characterization and catalytic epoxide alcoholysis activity of molybdenum incorporated porous silica

We report a novel method to increase the metal loading in SBA-15 silica matrix via direct synthesis. It was demonstrated through the synthesis and characterization of a series of molybdenum containing SBA-15 mesoporous silica catalysts prepared with and without diammonium hydrogen phosphate (DHP) as an additive. Catalysts prepared with DHP show a 2–3 times increase in incorporation of molybdenum in the silica matrix and pore size enlargement. The synthesized catalysts were characterized using nitrogen sorption, X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma–optical emission spectroscopy (ICP–OES). The catalytic activity of catalysts prepared with DHP for alcoholysis of epoxides was superior than the catalyst prepared without DHP. Alcoholysis of epoxides was demonstrated for a range of alcohols and epoxides under ambient conditions in as little as 30 min with high selectivity.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Synthesis and stabilization of small Pt nanoparticles on TiO 2 partially masked by SiO 2

Controlling metal nanoparticle size and preserving metal dispersion at elevated temperature remain key challenges in designing new supported metal catalysts. Many methods have been proposed to stabilize metal nanoparticles for catalysis, but the use of specialized equipment or metal precursors can limit the application of these methods for scalable production. Here, we demonstrate a synthesis strategy to improve the dispersion and thermal stability of Pt nanoparticles on an oxide support. A thin SiO 2 coat (<2 nm) was deposited on TiO2 through repeated condensation cycles of tetraethyl orthosilicate (TEOS) with or without an organic template on the surface. H 2 PtCl 6 was deposited using wetness impregnation, and the samples were dried, calcined, and reduced. The as-synthesized Pt nanoparticles are 1–2 nm by TEM and maintain dispersion >45% by CO chemisorption even after prolonged heating at 500 °C, whereas Pt nanoparticles on unmodified TiO 2 are less dispersed (~33%) and their dispersion falls further upon prolonged heating. Ethylene hydrogenation demonstrates that the Pt nanoparticles on modified TiO 2 preserve the catalytic activities of Pt on unmodified TiO 2 . The use of wet chemistry-based oxide modification and wetness impregnation makes this strategy a scalable and generalizable synthesis method to prepare other supported metal nanoparticles for catalysis applications.

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

Temperature-induced changes in the synthesis gas composition in a high-temperature H 2 O and CO 2 co-electrolysis system

Solid oxide electrolysis cell (SOEC) is an attractive renewable technology capable of producing synthesis gas (H 2 + CO) from H 2 O and CO 2 . An SOEC consists of a solid oxide electrolyte and two ceramic or metal-ceramic electrodes. H 2 O and CO 2 are electrolyzed at the cathode producing H 2 and CO, releasing O 2- ions, which travel through the electrolyte to the anode side and recombine to produce pure oxygen gas as the byproduct. In the present study, a La 0.7 Sr 0.2 Ni 0.2 Fe 0.8 O 3 cathode was used to co-electrolyze H 2 O and CO 2 at three different operating temperatures- 700 °C, 750 °C and 800 °C. Synthesis gas was produced at all three operating temperatures with 100% Faradaic efficiency. The composition of the syngas, however, was found to be a function of the operating temperature. In general, the H 2 /CO ratio in the syngas decreased with increased temperature. This was partially due to CO 2 electrolysis becoming more favorable compared to H 2 O electrolysis at higher temperatures.

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

Selective Catalytic Reduction of NO by NH 3 with WO 3 -TiO 2 Catalysts: Influence of Catalyst Synthesis Method

A series of supported WO 3 /TiO 2 catalysts was prepared by a new synthesis procedure involving co-precipitation of an aqueous TiO(OH) 2 and (NH 4 ) 10 W 12 O 41 *5H 2 O slurry under controlled pH conditions. The morphological properties, molecular structures, surface acidity and surface chemistry of the supported WO 3 /TiO 2 catalysts were determined with BET, in situ Raman, in situ IR and temperature-programmed surface reaction (TPSR) spectroscopy, respectively. Isotopic 18 O- 16 O exchange demonstrated that tungsten oxide was exclusively present as surface WO x species on the TiO 2 support with mono-oxo W=O coordination. In contrast to previous studies employing impregnation synthesis that found only surface one mono-oxo O=WO 4 site on TiO 2 , the co-precipitation procedure resulted in the formation of two distinct surface WO x species: mono-oxo O=WO 4 (~1010-1017 cm -1 ) on low defect density patches of TiO 2 and a second mono-oxo O=WO 4 (~983-986 cm -1 ) on high defect density patches of TiO 2 . The concentration of the second WO x surface species increases as a function of solution pH. Both surface WOx sites, however, exhibited the same NO/NH 3 SCR reactivity. The co-precipitated WO 3 -TiO 2 catalysts synthesized in alkaline solutions exhibited enhanced performance for the NO/NH 3 SCR reaction that is ascribed to the greater number of surface defects on the resulting TiO2 support. For the co-precipitated catalyst prepared at pH10, surface NH 4 + species on Br nsted acid sites were found to be more reactive than surface NH 3 * species on Lewis acid sites for SCR of NO with NH 3 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

A one-pot synthesis of high-density biofuels through bifunctional mesoporous zeolite-encapsulated Pd catalysts

Developing a powerful bifunctional catalyst for tandem reactions is essential to the future carbon neutrality by reducing the energy consumption in chemical industries. Herein, mesoporous zeolite-encapsulated palladium (Pd) nanoparticles (Pd@meso-ZSM-5) synthesized via emulsification-demulsification followed by a dry-gel transformation method were demonstrated to have a remarkable catalytic performance for a one-pot multiple tandem reaction of cyclic ketones (cyclopentanone, cyclohexanone) to bicyclic alkanes (bicyclopentane, bicyclohexane). Compared with supported catalysts (Pd/meso-ZSM-5) and microporous zeolite-encapsulated catalysts (Pd@ZSM-5) with a primary product of monocyclic alkane (cyclopentane, cyclohexane), Pd@meso-ZSM-5 shows much higher catalytic efficiency for the bicyclic alkanes synthesis, which was previously unattainable in the conventional two-step synthesis route. Controlled experiments and detailed characterizations show that mesoporosity provides sufficient space for the generation and diffusion of large molecular intermediates, and the intimate acid-Pd interface promotes the conversion of intermediates. As a result, this work proposes a design strategy for a mesoporous zeolite-encapsulated metal catalyst, which efficiently provides cooperative acid-hydrogenation catalysis.

09 BIOMASS FUELS↗
DOE OSTI2020

Alternative route for electrochemical ammonia synthesis by reduction of nitrate on copper nanosheets

We propose an efficient and clean avenue for ammonia synthesis, via electroreduction of nitrate which could be obtained from industrial wastewater, domestic sewage, sodium nitrate ore, and nitrification of bacteria and electrochemical oxidation of nitrogen, which addresses the water pollution issues and simultaneously upgrades the nitrate to high-value ammonia. At a low overpotential of -0.15 V versus RHE, Cu nanosheets achieved an ammonia formation rate of 390.1 μg mg -1 Cu h -1 and a Faradaic efficiency of 99.7%, attributed to suppression of the HER activity and apparent improvement of the rate of rate-determining step on Cu (111). Such an ammonia formation rate is more than two orders of magnitude higher than electrochemical nitrogen reduction reaction to ammonia. This work not only develops a powerful strategy to the rational design of robust and efficient catalysts by crystal facet engineering, but also provides an alternative route for electrochemical ammonia synthesis by reduction of nitrate.

36 MATERIALS SCIENCE↗
DOE OSTI2016

A new approach of the synthesis of SiO 2 nanowires by using bulk copper foils as catalyst

In this paper, a novel procedure for the growth of SiO 2 nanowires (SiO 2 NWs) directly from polycrystalline copper foils is reported. The single-step synthesis procedure consists of a thermal treatment at 900°C without the need for additional catalysts. As a result, nanowires with an average diameter of 100 nm are synthesized. A systematic study undertaken at different stages of the SiO 2 NWs growth confirmed the generation of nucleation centers on the Cu surface, as well as revealed the existence of an intermediate gaseous SiO species at the synthesis temperature. Lastly, on the basis of these evidences, the vapor-liquid-solid (VLS) route has been proposed as the mechanism responsible for the growth.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Same solution synthesis and self-assembly of porous silica nanoparticles into microspheres

The ability to couple self-assembly to the synthesis of materials in situ is an attractive concept for both basic and applied research. Self-assembly has been demonstrated for dense solid building blocks; however, it remains underdeveloped for porous materials, especially in situ assembly. Herein, we report the one-step synthesis and self-assembly of porous silica nanoparticles into silica microspheres by using polyvinylpyrrolidone-pentanol emulsion droplet system. Furthermore, nanoparticle size can be tuned by modifying the reaction conditions.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Fe-carbide/Fe-oxide-based nanocomposites synthesized as magnetic nanomaterials via laser ablation synthesis in solution (LASiS)

Magnetic nanostructured materials (MNMs) have gained prominence in materials technology developments owing to their potential biomedical applications for hyperthermia cancer treatment, and transplant organ cryopreservation. Herein, we report the facile and cost-effective synthesis of Fe-based composite MNMs, comprising both Fe@Fe 2 O 3 and Fe 3 C@C core-shell nanoparticles (NPs), via Laser Ablation Synthesis in Solution (LASiS) using Fe targets ablated under acetone and toluene. Detailed materials characterizations using electron microscopy-based imaging, diffraction studies, and spectroscopic analyses - including Raman and Mössbauer spectroscopy - relate the structure-composition properties for different Fe-oxide/carbide phases in the aforesaid MNMs to their respective magnetic responses. Specifically, we confirm the presence of ultra-small (2–10 nm) amorphous Fe-oxide NPs, as well as Fe@Fe 2 O 3 core-shell NPs (20–40 nm) in the samples synthesized by ablating Fe under acetone. In contrast, samples synthesized under toluene indicate a higher concentration of Fe 3 C@C core-shell NPs (20–40 nm) with a relatively low concentration of Fe 2 O 3 NPs (2–10 nm). Furthermore, the crystallinity of the metallic phases and carbonaceous shell coatings are systematically increased by carrying out LASiS under heated toluene (up to ~95 °C). Importantly, mössbauer spectroscopy results indicate that the elevation in toluene temperature leads to an increase in the concentrations of Fe 3 C@C NPs from ~40 % to ~53 % (at.).

36 MATERIALS SCIENCE↗
DOE OSTI2013

UAP56 is an important mediator of Angiotensin II/platelet derived growth factor induced vascular smooth muscle cell DNA synthesis and proliferation

Highlights: ► Knockdown of UAP56 inhibits Angiotensin II/PDGF induced vascular smooth muscle cell proliferation. ► UAP56 is a positive regulator of E2F transcriptional activation. ► UAP56 is present in the vessel wall of low flow carotid arteries. -- Abstract: Angiotensin (Ang) II and platelet-derived growth factor (PDGF) are important mediators of pathologic vascular smooth muscle cell (VSMC) proliferation. Identifying downstream mediators of Ang II and PDGF signaling may provide insights for therapies to improve vascular proliferative diseases. We have previously demonstrated that breakpoint cluster region (Bcr) is an important mediator of Ang II/PDGF signaling in VSMC. We have recently reported that the DExD/H box protein UAP56 is an interacting partner of Bcr in regulating VSMC DNA synthesis. We hypothesized that UAP56 itself is an important regulator of VSMC proliferation. In this report we demonstrate that knockdown of UAP56 inhibits Ang II/PDGF induced VSMC DNA synthesis and proliferation, and inhibits E2F transcriptional activity. In addition, we demonstrate that UAP56 is present in the vessel wall of low-flow carotid arteries. These findings suggest that UAP56 is a regulator of VSMC proliferation and identify UAP56 as a target for preventing vascular proliferative disease.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2013

The mitochondrial fatty acid synthesis (mtFASII) pathway is capable of mediating nuclear-mitochondrial cross talk through the PPAR system of transcriptional activation

Highlights: •The function of the mitochondria fatty acid synthesis pathway is partially unknown. •Overexpression of the pathway causes transcriptional activation through PPARs. •Knock down of the pathway attenuates that activation. •The last enzyme in the pathway regulates its own transcription. •Products of the mtFASII pathway are able to drive nuclear transcription. -- Abstract: Mammalian cells contain two fatty acid synthesis pathways, the cytosolic FASI pathway, and the mitochondrial FASII pathway. The selection behind the conservation of the mitochondrial pathway is not completely understood, given the presence of the cytosolic FAS pathway. In this study, we show through heterologous gene reporter systems and PCR-based arrays that overexpression of MECR, the last step in the mtFASII pathway, causes modulation of gene expression through the PPAR pathway. Electromobility shift assays (EMSAs) demonstrate that overexpression of MECR causes increased binding of PPARs to DNA, while cell fractionation and imaging studies show that MECR remains localized to the mitochondria. Interestingly, knock down of the mtFASII pathway lessens the effect of MECR on this transcriptional modulation. Our data are most consistent with MECR-mediated transcriptional activation through products of the mtFASII pathway, although we cannot rule out MECR acting as a coactivator. Further investigation into the physiological relevance of this communication will be necessary to better understand some of the phenotypic consequences of deficits in this pathway observed in animal models and human disease.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2016

The protein inhibitor of nNOS (PIN/DLC1/LC8) binding does not inhibit the NADPH-dependent heme reduction in nNOS, a key step in NO synthesis

The neuronal nitric oxide synthase (nNOS) is an essential enzyme involved in the synthesis of nitric oxide (NO), a potent neurotransmitter. Although previous studies have indicated that the dynein light chain 1 (DLC1) binding to nNOS could inhibit the NO synthesis, the claim is challenged by contradicting reports. Thus, the mechanism of nNOS regulation remained unclear. nNOS has a heme-bearing, Cytochrome P450 core, and the functional enzyme is a dimer. The electron flow from NADPH to Flavin, and finally to the heme of the paired nNOS subunit within a dimer, is facilitated upon calmodulin (CaM) binding. Here, we show that DLC1 binding to nNOS-CaM complex does not affect the electron transport from the reductase to the oxygenase domain. Therefore, it cannot inhibit the rate of NADPH-dependent heme reduction in nNOS, which results in L-Arginine oxidation. Also, the NO release activity does not decrease with increasing DLC1 concentration in the reaction mix, which further confirmed that DLC1 does not inhibit nNOS activity. These findings suggest that the DLC1 binding may have other implications for the nNOS function in the cell. - Highlights: • The effect of interaction of nNOS with DLC1 has been debatable with contradicting reports in literature. • Purified DLC1 has no effect on electron transport between reductase and oxygenase domain of purified nNOS-CaM. • The NO release activity of nNOS was not altered by DLC1, supporting that DLC1 does not inhibit the enzyme. • These findings suggest that the DLC1 binding may have other implications for the nNOS function in the cell.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2018

Hypothesis: Hypoxia induces de novo synthesis of NeuGc gangliosides in humans through CMAH domain substitute

Highlights: • In humans, the key enzyme for NeuGc synthesis, CMAH, is non-functional. • The presence of NeuGc gangliosides in human cancer cells represents an enigma. • We tested the effect of hypoxia by stable isotope labeling in cell culture (SILAC). • Subunit B of respiratory complex II (SDHB) was found upregulated. • Could CMAH be substituted by SDHB, another [Fe{sub 2}S{sub 2}]-containing domain? Immunotherapy is a growing field in cancer research. A privileged tumor-associated antigen that has received much attention is N-glycolyl (NeuGc) GM3. This ganglioside is present in several types of cancer, but is almost undetectable in human healthy tissues. However, its non-hydroxylated variant, NeuAc GM3, is abundant in all mammals. Due to a deletion in the human gene encoding the key enzyme for synthesis of NeuGc, humans, in contrast to other mammals, cannot synthesize NeuGc GM3. Therefore the presence of this ganglioside in human cancer cells represents an enigma. It has been shown that hypoxic conditions trigger the expression of NeuGc gangliosides, which not only serve as attractive targets for cancer therapy, but also as diagnostic and prognostic tumor marker. Here, we confirm hypoxia-induced expression of the NeuGc GM3 ganglioside also in HeLa cells and reveal several candidate proteins, in particular GM3 synthase and subunit B of respiratory complex II (SDHB), that may be involved in the generation of NeuGc GM3 by SILAC-based proteome analysis. These findings have the potential to significantly advance our understanding of how this enigmatic tumor-associated antigen is produced in humans, and also suggest a possible mechanism of action of anti-tumor antibodies that recognize hypoxia markers, such as 14F7.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2018

GhUMC1, a blue copper-binding protein, regulates lignin synthesis and cotton immune response

Highlights: • Knock-down of GhUMC1 attenuates the cotton immune response. • GhUMC1 has a spatio-temporal regulation in cotton disease resistance. • GhUMC1 acts upstream of lignin synthesis and is involved in cell wall remodeling. Verticillium wilt caused by the soil-borne fungus Verticillium dahliae is a serious problem for the sustainable production of cotton. The mechanism of cotton resistance to V. dahliae is unclear, which makes it is difficult to improve cotton resistance breeding. In this study, we characterized an umecyanin-like gene GhUMC1 in cotton, which is homologous to the AtBCB gene in Arabidopsis. It is predominantly expressed in roots and responds to pathogen infection. Knock-down of GhUMC1 increases plant susceptibility to V. dahliae. Expression levels of genes in the JA and SA signaling pathways in roots were down-regulated in GhUMC1-silenced plants. The transcripts of lignin synthesis genes, such as C4H, HCT, CCoAOMT and CAD, were also decreased in GhUMC1 knock-down seedlings, as was lignin content. Interestingly, knock-down of the GhUMC1 also decreased the contents of H{sub 2}0{sub 2} compared with the control. Our results suggest that GhUMC1 is involved in cotton resistance to V. dahliae by the regulation of the JA signaling pathway and lignin metabolism.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2013

Discovery and gram-scale synthesis of BMS-593214, a potent, selective FVIIa inhibitor

A 6-amidinotetrahydroquinoline screening hit was driven to a structurally novel, potent, and selective FVIIa inhibitor through a combination of library synthesis and rational design. An efficient gram-scale synthesis of the active enantiomer BMS-593214 was developed, which required significant optimization of the key Povarov annulation. Importantly, BMS-593214 showed antithrombotic efficacy in a rabbit arterial thrombosis model. A crystal structure of BMS-593214 bound to FVIIa highlights key contacts with Asp 189, Lys 192, and the S2 pocket.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗