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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 829 records · Page 46
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

Simple synthetic route to manganese-containing nanowires with the spinel crystal structure

This report describes a new route to synthesize single-crystalline manganese-containing spinel nanowires (NWs) by a two-step hydrothermal and solid-state synthesis. Interestingly, a nanowire or nanorod morphology is maintained during conversion from MnO{sub 2}/MnOOH to CuMn{sub 2}O{sub 4}/Mg{sub 2}MnO{sub 4}, despite the massive structural rearrangement this must involve. Linear sweep voltammetry (LSV) curves of the products give preliminary demonstration that CuMn{sub 2}O{sub 4} NWs are catalytically active towards the oxygen evolution reaction (OER) in alkaline solution, exhibiting five times the magnitude of current density found with pure carbon black. - Highlights: • Synthesis of single-crystalline manganese-containing spinel nanowires. • Binary oxide nanowire converted to ternary oxide wire through solid state reaction. • Approach to structure conversion with shape retention could be generally applicable. • Copper and Manganese display multiple oxidation states with potential for catalysis. • CuMn{sub 2}O{sub 4} nanowires show promise as catalysts for the oxygen evolution reaction.

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

Keggin polyoxometalates based hybrid compounds containing helix/nanocages for colorimetric biosensing

Highlights: • Two new Keggin polyoxometalates (POMs) based hybrid compounds containing helix/nanocages are reported. • Compounds 1 and 2 both exhibit higher peroxidase-like activities and broader applications range than other POMs involved peroxidase-like mimics. • Compounds 1 and 2 both exhibit faster respond time and lower detection limit than other POMs involved peroxidase-like mimics. - Abstract: Two Keggin polyoxometalate (POMs) based hybrid compounds containing helix/nanocages as peroxidase-like mimics have been synthesized and structurally characterized. Single crystal X-ray diffraction analysis reveals that compound 1 exhibits a POM-pillared framework with open nanotube channels (ca. 5.6 × 5.8 Å{sup 2}), in which SiW{sub 12} polyanions are sandwiched between the adjacent Cu-fkz sheets with meso-helix. And an unprecedented twisted octahedral hexamer nanocage (ca. 10 × 10 Å{sup 2}) is observed in compound 2. Compared with the other POMs involved peroxidase-like mimics, both compounds 1 and 2 exhibit higher peroxidase-like catalytic activities, broader applications range, faster respond time and lower detection limit, which maybe attribute to the maximized synergistic effects of SiW{sub 12} clusters, fkz molecules, metal ions and the distinct structure. Based on the facts, compounds 1 and 2 as enzyme mimics might expand their application around physiological pH conditions, and can be used as one kind of effective probe to detect H{sub 2}O{sub 2} in live organism.

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

Tribological properties of self-lubricating NiAl/Mo-based composites containing AgVO{sub 3} nanowires

Silver vanadate (AgVO{sub 3}) nanowires were synthesized by hydrothermal method and self-lubricating NiAl/Mo-AgVO{sub 3} composites were fabricated by powder metallurgy technique. The composition and microstructure of NiAl/Mo-based composites were characterized and the tribological properties were investigated from room temperature to 900 °C. The results showed that NiAl/Mo-based composites were consisted of nanocrystalline B2 ordered NiAl matrix, Al{sub 2}O{sub 3}, Mo{sub 2}C, metallic Ag and vanadium oxide phase. The appearance of metallic Ag and vanadium oxide phase can be attributed to the decomposition of AgVO{sub 3} during sintering. Wear testing results confirmed that NiAl/Mo-based composites have excellent tribological properties over a wide temperature range. For example, the friction coefficient and wear rate of NiAl/Mo-based composites containing AgVO{sub 3} were significantly lower than the composites containing only metallic Mo or AgVO{sub 3} lubricant when the temperature is above 300 °C, which can be attributed to the synergistic lubricating action of metallic Mo and AgVO{sub 3} lubricants. Furthermore, Raman results indicated that the composition on the worn surface of NiAl-based composites was self-adjusted after wear testing at different temperatures. For example, Ag{sub 3}VO{sub 4} and Fe{sub 3}O{sub 4} lubricants were responsible for the improvement of tribological properties at 500 °C, AgVO{sub 3}, Ag{sub 3}VO{sub 4} and molybdate for 700 °C, and AgVO{sub 3} and molybdate for 900 °C of NiAl-based composites with the addition of metallic Mo and AgVO{sub 3}. - Highlights: • NiAl/Mo-AgVO{sub 3} nanocomposites were prepared by mechanical alloying and sintering. • AgVO{sub 3} decomposed to metallic Ag and vanadium oxide during the sintering process. • NiAl/Mo-AgVO{sub 3} exhibited superior tribological properties at a board temperature range. • Phase composition on the worn surface was varied with temperatures. • Self-adjusted action was responsible for the improvement of tribological properties.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Effects of Mg-Al-O-Mn-S inclusion on the nucleation of acicular ferrite in magnesium-containing low-carbon steel

Highlights: • We redefine the mechanism of AF nucleation from Gibbs free energy of nucleation. • Complex inclusions present a better ability of inducing AF formation due to the Mn-depleted zone. • The lattice misfit and the thermal strain are calculated in this study. - Abstract: The effects of inclusion size and chemical composition on acicular ferrite (AF) nucleation and possible nucleation mechanisms were discussed. With the use of low-carbon structure steel containing 13 ppm Mg, the chemical composition and size of inclusions were quantified by scanning electron microscopy combined with an energy dispersive spectroscopy system. Results showed that the complex inclusions MgO-MnS and MgO-Al{sub 2}O{sub 3}-MnS are the most effective inclusions for inducing AF nucleation in Mg-containing A36, and their probabilities of AF nucleation are 35.8% and 41.4%, respectively. Moreover, the inclusion size in the range of 1–2 μm exhibits the most remarkable ability to induce AF formation. AF nucleates at the interface of MgO and MgO-Al{sub 2}O{sub 3} because of the low lattice misfit with AF. Complex inclusions, such as MgO-MnS and MgO-Al{sub 2}O{sub 3}-MnS, present a better ability of inducing AF formation than that of MnS due to the Mn-depleted zone.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Thermophysical properties of Ni-containing single-phase concentrated solid solution alloys

For this research temperature dependent thermophysical properties, including specific heat capacity, lattice thermal expansion, thermal diffusivity and conductivity, have been systematically studied in Ni and eight Ni-containing single-phase face-centered-cubic concentrated solid solution alloys, at elevated temperatures up to 1273 K. The alloys have similar specific heat values of 0.4–0.5 J·g -1 ·K -1 at room temperature, but their temperature dependence varies greatly due to Curie and K-state transitions. The lattice, electronic, and magnetic contributions to the specific heat have been separated based on first-principles methods in NiCo, NiFe, Ni-20Cr and NiCoFeCr. The alloys have similar thermal expansion behavior, with the exception that NiFe and NiCoFe have much lower thermal expansion coefficient in their ferromagnetic state due to magnetostriction effects. Calculations based on the quasi-harmonic approximation accurately predict the temperature dependent lattice parameter of NiCo and NiFe with < 0.2% error, but underestimated that of Ni-20Cr by 1%, compared to the values determined from neutron diffraction. In addition, all the alloys containing Cr have very similar thermal conductivity, which is much lower than that of Ni and the alloys without Cr, due to the large magnetic disorder.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Thermal cycling-driven microstructural changes of eutectic Al–Si phase change materials in SS304 containers revealed by multi-modal imaging

Aluminum-based Al–Si alloys are widely used as phase change materials (PCMs) in thermal energy storage (TES) systems owing to their high volumetric latent heat and superior thermal conductivity. However, their long-term reliability is limited by degradation processes that remain insufficiently understood. In this work, we employ a multimodal, correlative characterization framework to systematically resolve the degradation behavior of eutectic Al–Si PCMs in contact with SS304 containers under repeated thermal cycling. By integrating high-resolution electron microscopy, three-dimensional X-ray fluorescence (3D XRF) imaging, and differential scanning calorimetry (DSC), we directly link spatially resolved compositional and microstructural evolution to changes in thermophysical properties. The correlative analysis reveals that elemental leaching of Fe, Cr, and Ni from the stainless-steel container into the PCM drives the formation of intermetallic compounds (IMCs) both at the interface and within the bulk PCM, leading to pronounced compositional heterogeneity. These interfacial reactions and diffusion-induced transformations progressively destabilize the Al–Si eutectic, reducing the effective phase-transforming fraction. Consistent with these observations, DSC measurements show a decrease in melting temperature and latent heat of fusion with thermal cycling. These results underscore the critical influence of interfacial reactions and material compatibility on the stability, durability, and overall performance of Al–Si-based TES systems.

25 ENERGY STORAGE↗
DOE OSTI2013

Comparisons of short carbon nanotubes containing conductive additives of cathode for lithium ion batteries

Graphical abstract: - Highlights: • Short carbon nanotubes (SCNT) containing conductive additives were used. • SCNT/graphite powder (GP) mixture is better than SCNT/mesoporous carbon mixture. • SCNT connect many isolated GP particles to form a more valid conductive network. • SCNT absorb some electrolyte solution allowing quick electrochemical reactions. - Abstract: Short carbon nanotubes (SCNT) containing conductive additives, i.e. SCNT/graphite powder (GP) mixture (SCNTGP) and SCNT/mesoporous carbon (MC) mixture (SCNTMC) were employed as conductive additives for LiCoO{sub 2} cathode. GP and MC have similar particle size, but GP has lower specific surface area and higher electronic conductivity. Electrochemical measurements indicate that SCNTGP is more effective in improving the electrochemical performance of LiCoO{sub 2} composite cathode under the same conditions. The reason is described as follows. SCNT connect the isolated GP particles to form a more valid conductive network. In addition, SCNT has a certain specific mesoporous surface area, which can absorb some electrolyte solution and then provide buffer lithium ions for quick electrochemical reactions. Consequently, the combination of these two factors would be responsible to the improvement in the electrochemical performance of the SCNTGP loaded cathode.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Optical properties of transparent glass–ceramics containing lithium–mica nanocrystals: Crystallization effect

Graphical abstract: Optical properties of transparent Li{sub 2}O–MgO–Al{sub 2}O{sub 3}–SiO{sub 2}–F glasses containing lithium–mica nanocrystals are studied and crystallization condition has been evaluated and optimized to produce transparent glass–ceramics. Crystallization temperatures were determined by differential thermal analysis and crystalline phases were identified and quantified by X-ray diffraction. Scanning electron microscopy was used for morphological variations and UV–vis absorption spectroscopy for comparative analysis of transparency. In order to investigate the optical properties of transparent glass–ceramics, optical band gap, Fermi energy level and Urbach energy are calculated. The results of the investigation illustrate that band gap is reduced with increases in crystallization time and temperature. Enhanced orderliness in the arrangement of atoms might be regarded as possible reasons for the above changes. - Highlights: • The optimum temperature and time of crystallization were determined. • Li–mica nanocrystals with size of <30 nm were formed using a two-step heat-treatment. • Optical band gap and Fermi energy of nanocrystalline materials decreased with increasing of crystallization temperature and time. • Urbach band tailing was decreased with increasing of crystallization condition. - Abstract: Optical properties of transparent Li{sub 2}O–MgO–Al{sub 2}O{sub 3}–SiO{sub 2}–F glasses containing lithium–mica nanocrystals were studied. The crystallization condition of these glasses was evaluated and optimized to produce transparent glass–ceramics. Crystallization temperatures were determined by differential thermal analysis and crystalline phases were identified and quantified by X-ray diffraction. Scanning electron microscopy was used to detect morphological changes and UV–vis absorption spectroscopy was used for comparative analysis of transparency. In order to investigate the optical properties of the transparent glass–ceramics, optical band gap, Fermi energy level and Urbach energy were calculated. The results of the investigation illustrate that the band gap is reduced with increases in crystallization time and temperature. Enhanced orderliness in the arrangement of atoms might be regarded as possible reasons for the above changes.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Controllable synthesis and tunable luminescence of glass ceramic containing Mn{sup 2+}:ZnAl{sub 2}O{sub 4} and Pr{sup 3+}:YF{sub 3} nano-crystals

Highlights: • Glass ceramic containing ZnAl{sub 2}O{sub 4} and YF{sub 3} nano-crystals is fabricated. • Mn{sup 2+} and Pr{sup 3+} are selectively incorporated into ZnAl{sub 2}O{sub 4} and YF{sub 3}, respectively. • The luminescence color can be tuned by adjusting the excitation wavelength. - Abstract: Glass ceramic containing spinel ZnAl{sub 2}O{sub 4}:Mn{sup 2+} and orthorhombic YF{sub 3}:Pr{sup 3+} nano-crystals has been successfully prepared by a melt-quenching technique. X-ray diffraction and transmission electron microscopy demonstrated that two nano-phases, i.e. ZnAl{sub 2}O{sub 4} and YF{sub 3}, were homogeneously distributed among the glass matrix. Importantly, the selective incorporation of Pr{sup 3+} ions into the Y{sup 3+} nine-fold coordinated sites of YF{sub 3} and the segregation of Mn{sup 2+} dopants in the Zn{sup 2+} tetrahedral sites of ZnAl{sub 2}O{sub 4} were confirmed based on the excitation/emission spectra and the crystal field calculation. Under blue light excitation, both Pr{sup 3+} and Mn{sup 2+} in the glass ceramic can be simultaneously excited, and emit red and green luminescence, respectively, owing to the suppression of energy transfer between them. The luminescence color of the obtained glass ceramic can be easily tuned by adjusting the excitation wavelength. These results indicate the potential application of the glass ceramic as converting phosphor to generate white-light after coupling with the blue LED chip.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Biogas reforming over Ni catalysts dispersed in different mixed oxides containing Zn2+, Al3+ and Zr4+cations

Highlights: • The oxides mixture containing NiO, ZnO, Al{sub 2}O{sub 3}, NiAl{sub 2}O{sub 4} and ZnAl{sub 2}O{sub 4} was detected. • The results exhibited intermediate interactions between Ni0 and other phases. • Dry reforming of methane was applied to production of synthesis gas. • Deposition of the carbon filamentous on the catalysts surface was observed. - Abstract: The active phase plays an important role in the catalytic activity. However, its applicability is directly associated with other present phases in the mixture. In view of this, we report the performance of Ni catalysts dispersed on mixed oxides containing Zn{sup 2+}, Al{sup 3+} and Zr{sup 4+}cations in biogas reforming. For this purpose, the samples were characterized by X-ray powder diffraction, which showed the formation of a homogeneous mixture of binary (NiO, ZnO, ZrO{sub 2} and Al{sub 2}O{sub 3}) and ternary (NiAl{sub 2}O{sub 4} and ZnAl{sub 2}O{sub 4}) oxides. The temperature-programmed reduction (H{sub 2}-TPR) provided information on the catalyst reduction. The performance of the catalysts was evaluated using two reduction temperatures (650 °C and 750 °C). The reactions were carried out at 750 °C, where the Ni/ZnAlZr catalyst presented the highest CO{sub 2} conversion attributed to the basic sites, which favored the CO{sub 2} adsorption. Otherwise, the Ni/ZnZr catalyst (reduced at 650 °C) showed a high CH{sub 4} conversion. The catalysts were also reduced at 750 °C and a lower conversion of both reactants (CH{sub 4} and CO{sub 2}) was observed. We argued that the agglomeration process during the reduction condition deteriorates the performance of the catalysts reduced at 750 °C.

09 BIOMASS FUELS↗
DOE OSTI2021

Water and salt transport properties of pentiptycene-containing sulfonated polysulfones for desalination membrane applications

A series of pentiptycene-containing disulfonated polysulfone copolymers (PENT-BP) were synthesized via condensation polymerization. Water and salt transport properties (solubility, diffusivity and permeability) were characterized for acid-form membranes (PENT-BP(H)) and compared with triptycene-based sulfonated polysulfones (TRP-BP(H)) and a non-iptycene-containing 4,4'-biphenol-based series (BPS(H)) of polysulfones to investigate the effect of pentiptycene on membrane performance. At comparable water content, the PENT-BP(H) exhibited increased water and salt permeability due to the additional free volume introduced by the pentiptycene units. Enhanced water/salt permeability selectivity of PENT-BP(H) series was also observed due to a significantly higher diffusivity selectivity. At comparable water permeance (P w D ~ 8 X 10 -6 cm 2 /s), the salt rejection of PENT-BP (H) copolymers obtained from dead-end filtration reached 91–93% at 400 psi, higher than that of a corresponding BPS(H) series. This study suggests that incorporation of iptycene moieties into polymer backbone is an effective strategy to enhance desalination membrane performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Strengthening mechanisms for microstructures containing unimodal and bimodal γ' precipitates in ATI 718Plus

Here, the influence of γ' precipitate size distribution on the deformation mechanisms under tensile loading in ATI 718Plus was studied. A set of aging treatments within the temperature range of 720 °C–900 °C was performed on solution-treated samples to obtain various γ' precipitate size distributions. Unimodal and bimodal γ' precipitate size distributions were achieved through single-step and two-step aging sequences, respectively, and such microstructures were tensile tested to failure to assess their yield strength, ultimate tensile strength, and elongation-to-failure. Some of the tensile samples were interrupted after achieving 3–4 % plastic strain, and the deformed microstructures were examined using transmission electron microscopy to investigate the γ' precipitate-dislocation interactions. For the unimodal γ' precipitate size distribution samples with the smaller γ' precipitates (radius ~ 7 nm), dislocations sheared through the precipitates. Both dislocation loops and paired dislocations were observed for the microstructures containing larger γ' precipitates (radius ~ 24 nm). The microstructure containing a bimodal γ' precipitate size distribution, which included average γ' precipitate radii of ~6 nm and ~28 nm, exhibited shearing as the dominant deformation mechanism, and this microstructure exhibited the highest strength values. The experimental observations were rationalized based on the theoretically-calculated critical resolved shear stress values for shearing and looping and a modified model for predicting the yield strength for bimodal microstructures was introduced.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Zinc-based cyclens containing pyridine and cross-bridges: X-ray and DFT structures, Lewis acidity, gas-phase acidity, and p K a values

Herein it is well known that catalytic centers containing the zinc(II) ion can act as both Lewis and Bronsted-Lowry acids. In addition to coordination number, the Zn coordination geometry can also strongly impact the acidity of the active site, no matter what measure of acidity is considered. Herein, we report the first pentacoordinate, zinc-ammonia complex containing a pyridine based tetraazamacrocycle, [(pyclen)Zn(NH 3 )](PF 6 ) 2 , that has applications in Lewis acid catalysis. From this structure, we obtain binding energies and acidities for a series of related pyclen and cross-bridged cyclen type tetraazamacrocycles comprising the pentacoordinate N 4 Zn(II)–OH 2 entity, collectively referred to as [(R-cyclen)Zn–OH 2 ] 2+ . Results from gas- and aqueous-phase density functional theory (M05-2X) and ab initio (MP2) calculations reported herein demonstrate that molecular geometry has a substantial influence on both the Zn–OH x binding strengths and the deprotonation energy of coordinated H 2 O, but not necessarily in a predicable way. While generally more constrained N–Zn–N coordination leads to greater Zn–OH 2 binding energies (Lewis acidities), the corresponding Lewis acidities of the complexes don’t always correlate with the Zn–OH 2 bond lengths nor the (Bronsted) acidity of the coordinated H 2 O. Additionally, the order of the Lewis acid strength of the [(R-cyclen)Zn(II)] complexes changes as the basic –OH 2 ligand is replaced with its –OH counterpart.

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

Polybenzimidazole based random copolymers containing hexafluoroisopropylidene functional groups for gas separations at elevated temperatures

Polybenzimidazoles (PBIs) are attractive membrane materials for H 2 /CO 2 separation at hydrocarbon fuel derived synthesis gas operating conditions due to their exceptional physicochemical stability and promising permselectivity character. PBI molecular structure modification is a viable approach to disrupt chain packing altering the free-volume architecture which results in improved gas transport characteristics. This work is focused on the synthesis and characterization of novel PBI random copolymers for application as elevated temperature H 2 /CO 2 membranes. The co-polymerization route is expected to result in tailorable permeability and selectivity by combining the high H 2 permeability aspect of the highly disrupted loosely packed hexafluoroisopropylidene diphenyl group containing PBI segments (6F-PBI) with the highly selective tightly packed phenylene group containing PBI segments (m-PBI). 6F/m-PBI copolymers with varying 6F-PBI and m-PBI ratios having high inherent viscosity were synthesized. The structure and ratio of the 6F- and m-PBI fractions were confirmed using FTIR and NMR spectroscopic techniques. The measured gas transport properties of copolymer thin films cast in controlled environment were measured as a function of the operating conditions. Lastly, the H 2 permeability increased while H 2 /CO 2 selectivity decreased as the 6F-PBI copolymer fraction was increased.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Solidification behavior and cracking mechanisms of Ru-containing BCC-B2 superalloys

Many precipitation-strengthened alloys are highly susceptible to cracking during additive manufacturing (AM), which often requires compositional adjustments to mitigate. Recently, it has been demonstrated that refractory BCC alloys can be precipitation strengthened with ordered Ru-containing B2 precipitates to temperatures exceeding 1200 °C. This motivates a study of the potential fabricability of quaternary and quinary refractory BCC-B2 alloys by AM using single track laser experiments. Alloys with greater than 9 at.% Ru exhibit crack formation upon cooling. Solidification cracking was observed in all Zr-containing alloys, which can be mitigated by substituting Hf. Furthermore, this cracking is attributed to the strong partitioning of Zr during solidification, as revealed by characterization of alloy solidus, liquidus, and partition coefficients. Hf 5 Ru 4 -Nb 63 V 28 is identified as a promising BCC-B2 composition with a high B2 solvus (>1300 °C) and solidus (1695 °C) along with a high resistance to cracking.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Brønsted acid-base reactions with anhydrous sulfamates as a pathway to [SO 3 N] 3- -containing compounds: Preparation of Li 3 SO 3 N

Li 3 SO 3 N has been prepared by the mechanochemical reaction between lithium sulfamate (LiSO 3 NH 2 ) and lithium amide or lithium hydride. This is the first example of an anhydrous compound containing the rare [SO 3 N] 3- polyanion. Li 3 SO 3 N adopts the low-temperature Pmn21β structure of isoelectronic Li 3 PO 4 . Structural refinement from neutron powder diffraction data supports disordering of nitrogen over two of the three anion sites, although a fully disordered model cannot be conclusively refuted. While the compound is a poor ionic conductor, it is electrochemically stable to at least 5 V vs. Li + /Li 0 . This simple mechanochemical pathway should be suitable for preparing a host of other alkali-rich nitrogen-containing polyanionic compounds.

Kurzman, Joshua A.↗
DOE OSTI2013

Hypoxia inducible factor-1 (HIF-1)–flavin containing monooxygenase-2 (FMO-2) signaling acts in silver nanoparticles and silver ion toxicity in the nematode, Caenorhabditis elegans

In the present study, nanotoxicity mechanism associated with silver nanoparticles (AgNPs) exposure was investigated on the nematode, Caenorhabditis elegans focusing on the hypoxia response pathway. In order to test whether AgNPs-induced hypoxia inducible factor-1 (HIF-1) activation was due to hypoxia or to oxidative stress, depletion of dissolved oxygen (DO) in the test media and a rescue effect using an antioxidant were investigated, respectively. The results suggested that oxidative stress was involved in activation of the HIF-1 pathway. We then investigated the toxicological implications of HIF-1 activation by examining the HIF-1 mediated transcriptional response. Of the genes tested, increased expression of the flavin containing monooxygenase-2 (FMO-2) gene was found to be the most significant as induced by AgNPs exposure. We found that AgNPs exposure induced FMO-2 activation in a HIF-1 and p38 MAPK PMK-1 dependent manner, and oxidative stress was involved in it. We conducted all experiments to include comparison of AgNPs and AgNO{sub 3} in order to evaluate whether any observed toxicity was due to dissolution or particle specific. The AgNPs and AgNO{sub 3} did not produce any qualitative differences in terms of exerting toxicity in the pathways observed in this study, however, considering equal amount of silver mass, in every endpoint tested the AgNPs were found to be more toxic than AgNO{sub 3}. These results suggest that Ag nanotoxicity is dependent not only on dissolution of Ag ion but also on particle specific effects and HIF-1–FMO-2 pathway seems to be involved in it. - Highlights: • HIF-1 signaling was investigated in C. elegans exposed to AgNPs and AgNO{sub 3}. • HIF-1 and PMK-1 were needed for AgNPs- and AgNO{sub 3}-induced fmo-2 gene expression. • PMK-1–HIF-1–FMO-2 pathway was dependent on oxidative stress. • AgNPs and AgNO{sub 3} did not produce any qualitative differences in HIF-1 signaling. • AgNPs were more toxic than an equal amount of silver mass contained in AgNO{sub 3}.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2015

Environmentally persistent free radical-containing particulate matter competitively inhibits metabolism by cytochrome P450 1A2

Combustion processes generate different types of particulate matter (PM) that can have deleterious effects on the pulmonary and cardiovascular systems. Environmentally persistent free radicals (EPFRs) represent a type of particulate matter that is generated after combustion of environmental wastes in the presence of redox-active metals and aromatic hydrocarbons. Cytochromes P450 (P450/CYP) are membrane-bound enzymes that are essential for the phase I metabolism of most lipophilic xenobiotics. The EPFR formed by chemisorption of 2-monochlorophenol to silica containing 5% copper oxide (MCP230) has been shown to generally inhibit the activities of different forms of P450s without affecting those of cytochrome P450 reductase and heme oxygenase-1. The mechanism of inhibition of rat liver microsomal CYP2D2 and purified rabbit CYP2B4 by MCP230 has been shown previously to be noncompetitive with respect to substrate. In this study, MCP230 was shown to competitively inhibit metabolism of 7-benzyl-4-trifluoromethylcoumarin and 7-ethoxyresorufin by the purified, reconstituted rabbit CYP1A2. MCP230 is at least 5- and 50-fold more potent as an inhibitor of CYP1A2 than silica containing 5% copper oxide and silica, respectively. Thus, even though PM generally inhibit multiple forms of P450, PM interacts differently with the forms of P450 resulting in different mechanisms of inhibition. P450s function as oligomeric complexes within the membrane. We also determined the mechanism by which PM inhibited metabolism by the mixed CYP1A2–CYP2B4 complex and found that the mechanism was purely competitive suggesting that the CYP2B4 is dramatically inhibited when bound to CYP1A2. - Highlights: • Combustion of organic pollutants generates long-lived particulate radicals (EPFRs). • Particulate matter (PM) competitively inhibited CYP1A2 activity. • EPFRs were much more potent CYP1A2 inhibitors than other types of PM. • PM interacts differently with different forms of P450. • PM competitively inhibited metabolism by the mixed CYP1A2–CYP2B4 complex.

60 APPLIED LIFE SCIENCES↗