Fungus mediated synthesis of biomedically important cerium oxide nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Khan, Shadab Ali; Ahmad, Absar, E-mail: a.ahmad@ncl.res.in

2013-10-15

Graphical abstract: - Highlights: • First time biological synthesis of cerium oxide oxide nanoparticles using fungus Humicola sp. • Complete characterization of cerium oxide nanoparticles. • Biosynthesis of naturally protein capped, luminescent and water dispersible CeO{sub 2} nanoparticles. • Biosynthesized CeO{sub 2} nanoparticles can be used for many biomedical applications. - Abstract: Nanomaterials can be synthesized by chemical, physical and the more recently discovered biological routes. The biological routes are advantageous over the chemical and physical ones as unlike these, the biological synthesis protocols occur at ambient conditions, are cheap, non-toxic and eco-friendly. Although purely biological and bioinspired methods formore » the synthesis of nanomaterials are environmentally benign and energy conserving processes, their true potential has not been explored yet and attempts are being made to extend the formation of technologically important nanoparticles using microorganisms like fungi. Though there have been reports on the biosynthesis of oxide nanoparticles by our group in the past, no attempts have been made to employ fungi for the synthesis of nanoparticles of rare earth metals or lanthanides. Here we report for the first time, the bio-inspired synthesis of biomedically important cerium oxide (CeO{sub 2}) nanoparticles using the thermophilic fungus Humicola sp. The fungus Humicola sp. when exposed to aqueous solutions of oxide precursor cerium (III) nitrate hexahydrate (CeN{sub 3}O{sub 9}·6H{sub 2}O) results in the extracellular formation of CeO{sub 2} nanoparticles containing Ce (III) and Ce (IV) mixed oxidation states, confirmed by X-ray Photoemission Spectroscopy (XPS). The formed nanoparticles are naturally capped by proteins secreted by the fungus and thus do not agglomerate, are highly stable, water dispersible and are highly fluorescent as well. The biosynthesized nanoparticles were characterized by UV–vis spectroscopy

Direct growth of cerium oxide nanorods on diverse substrates for superhydrophobicity and corrosion resistance

NASA Astrophysics Data System (ADS)

Cho, Young Jun; Jang, Hanmin; Lee, Kwan-Soo; Kim, Dong Rip

2015-06-01

Superhydrophobic surfaces with anti-corrosion properties have attracted great interest in many industrial fields, particularly to enhance the thermal performance of offshore applications such as heat exchangers, pipelines, power plants, and platform structures. Nanostructures with hydrophobic materials have been widely utilized to realize superhydrophobicity of surfaces, and cerium oxide has been highlighted due to its good corrosion resistive and intrinsically hydrophobic properties. However, few studies of direct growth of cerium oxide nanostructures on diverse substrates have been reported. Herein we report a facile hydrothermal method to directly grow cerium oxide nanorods on diverse substrates, such as aluminum alloy, stainless steel, titanium, and silicon. Diverse substrates with cerium oxide nanorods exhibited superhydrophobicity with no hydrophobic modifiers on their surfaces, and showed good corrosion resistive properties in corrosive medium. We believe our method could pave the way for realization of scalable and sustainable corrosion resistive superhydrophobic surfaces in many industrial fields.

Processing and Characterization of Sol-Gel Cerium Oxide Microspheres

DOE Office of Scientific and Technical Information (OSTI.GOV)

McClure, Zachary D.; Padilla Cintron, Cristina

Of interest to space exploration and power generation, Radioisotope Thermoelectric Generators (RTGs) can provide long-term power to remote electronic systems without the need for refueling or replacement. Plutonium-238 (Pu-238) remains one of the more promising materials for thermoelectric power generation due to its high power density, long half-life, and low gamma emissions. Traditional methods for processing Pu-238 include ball milling irregular precipitated powders before pressing and sintering into a dense pellet. The resulting submicron particulates of Pu-238 quickly accumulate and contaminate glove boxes. An alternative and dust-free method for Pu-238 processing is internal gelation via sol-gel techniques. Sol-gel methodology createsmore » monodisperse and uniform microspheres that can be packed and pressed into a pellet. For this study cerium oxide microspheres were produced as a surrogate to Pu-238. The similar electronic orbitals between cerium and plutonium make cerium an ideal choice for non-radioactive work. Before the microspheres can be sintered and pressed they must be washed to remove the processing oil and any unreacted substituents. An investigation was performed on the washing step to find an appropriate wash solution that reduced waste and flammable risk. Cerium oxide microspheres were processed, washed, and characterized to determine the effectiveness of the new wash solution.« less

Molecular and physiological responses to titanium dioxide and cerium oxide nanoparticles in Arabidopsis

EPA Science Inventory

- Changes in tissue transcriptomes and productivity of Arabidopsis thaliana were investigated during exposure of plants to two widely-used engineered metal oxide nanoparticles, titanium dioxide (nano-titanium) and cerium dioxide (nano-cerium). Microarray analyses confirmed that e...

Analysis of cerium-composite polymer-electrolyte membranes during and after accelerated oxidative-stability test

NASA Astrophysics Data System (ADS)

Shin, Dongwon; Han, Myungseong; Shul, Yong-Gun; Lee, Hyejin; Bae, Byungchan

2018-02-01

The oxidative stability of membranes constructed from a composite of pristine sulfonated poly(arylene ether sulfone) and cerium was investigated by conducting an accelerated oxidative-stability test at the open-circuit voltage (OCV). The membranes were analyzed in situ through OCV and impedance measurements, cyclic voltammetry, and linear-sweep voltammetry to monitor the electrochemical properties during the stability test. Although the high-frequency resistance of a composite membrane was slightly higher than that of a pristine membrane because of the exchange of protons from the sulfonic acid with cerium ions, the composite membrane maintained its potential for much longer than the pristine membrane. The effect of the cerium ions as radical scavengers was confirmed by analyzing the drain water and chemical structure after operation. These post-operation analyses confirmed that cerium ions improved the oxidative stability of the hydrocarbon-based polymer during fuel-cell operation. It is clear that the cerium-based radical scavengers prevented chemical degradation of the polymer membrane as well as the electrode in terms of hydrogen cross-over, polymer-chain scission, and the electrochemical surface area, while they rarely diffused outward from the membrane.

Change of Cu+ species and synergistic effect of copper and cerium during reduction-oxidation treatment for preferential CO oxidation

NASA Astrophysics Data System (ADS)

Zhang, Hao; Zhao, Xiaozhou; Wang, Shuang; Zeng, Shanghong; Su, Haiquan

2018-05-01

The CuO-CeO2@SiO2 catalyst with flower-sphere morphology was prepared by the impregnation method and then experienced the reduction-oxidation treatment at different temperatures. The multi-technique characterization shows that the reduction-oxidation treatment can remodel CuO, improve textural and surface properties and change Cu+ content and synergistic effect of copper and cerium. The importance of this work lies in the fact that the decrease of Cu+ content and synergistic effect of copper and cerium that occurs in the reduction-oxidation process results in the decrease of catalytic activity over the CuO-CeO2@SiO2 catalyst for preferential CO oxidation. The process of reaction in rich-hydrogen streams is equivalent to a reduction procedure which decreases Cu+ content and synergistic effect of copper and cerium.

Electrode electrolyte interlayers containing cerium oxide for electrochemical fuel cells

DOEpatents

Borglum, Brian P.; Bessette, Norman F.

2000-01-01

An electrochemical cell is made having a porous fuel electrode (16) and a porous air electrode (13), with solid oxide electrolyte (15) therebetween, where the air electrode surface opposing the electrolyte has a separate, attached, dense, continuous layer (14) of a material containing cerium oxide, and where electrolyte (16) contacts the continuous oxide layer (14), without contacting the air electrode (13).

Predicting the Effects of Nano-Scale Cerium Additives in Diesel Fuel on Regional-Scale Air Quality

EPA Science Inventory

Diesel vehicles are a major source of air pollutant emissions. Fuel additives containing nanoparticulate cerium (nCe) are currently being used in some diesel vehicles to improve fuel efficiency. These fuel additives also reduce fine particulate matter (PM_2.5) emissio...

Predicting the effects of nanoscale cerium additives in diesel fuel on regional-scale air quality.

PubMed

Erdakos, Garnet B; Bhave, Prakash V; Pouliot, George A; Simon, Heather; Mathur, Rohit

2014-11-04

Diesel vehicles are a major source of air pollutant emissions. Fuel additives containing nanoparticulate cerium (nCe) are currently being used in some diesel vehicles to improve fuel efficiency. These fuel additives also reduce fine particulate matter (PM2.5) emissions and alter the emissions of carbon monoxide (CO), nitrogen oxides (NOx), and hydrocarbon (HC) species, including several hazardous air pollutants (HAPs). To predict their net effect on regional air quality, we review the emissions literature and develop a multipollutant inventory for a hypothetical scenario in which nCe additives are used in all on-road and nonroad diesel vehicles. We apply the Community Multiscale Air Quality (CMAQ) model to a domain covering the eastern U.S. for a summer and a winter period. Model calculations suggest modest decreases of average PM2.5 concentrations and relatively larger decreases in particulate elemental carbon. The nCe additives also have an effect on 8 h maximum ozone in summer. Variable effects on HAPs are predicted. The total U.S. emissions of fine-particulate cerium are estimated to increase 25-fold and result in elevated levels of airborne cerium (up to 22 ng/m3), which might adversely impact human health and the environment.

Heteroaggregation of cerium oxide nanoparticles and nanoparticles of pyrolyzed biomass

USDA-ARS?s Scientific Manuscript database

Heteroaggregation with indigenous particles is an important process controlling the mobility of engineered nanomaterials in the environment. We studied heteroaggregation of cerium oxide nanoparticles (n-CeO2), which are widely used commercially, with nanoparticles of pyrogenic carbonaceous material ...

Multifunctional cerium-based nanomaterials and methods for producing the same

DOEpatents

O'Keefe, Matthew J.; Castano Londono, Carlos E.; Fahrenholtz, William G.

2018-01-09

Embodiments relate to a cerium-containing nano-coating composition, the composition including an amorphous matrix including one or more of cerium oxide, cerium hydroxide, and cerium phosphate; and crystalline regions including one or more of crystalline cerium oxide, crystalline cerium hydroxide, and crystalline cerium phosphate. The diameter of each crystalline region is less than about 50 nanometers.

Environmental geochemistry of cerium: applications and toxicology of cerium oxide nanoparticles.

PubMed

Dahle, Jessica T; Arai, Yuji

2015-01-23

Cerium is the most abundant of rare-earth metals found in the Earth's crust. Several Ce-carbonate, -phosphate, -silicate, and -(hydr)oxide minerals have been historically mined and processed for pharmaceutical uses and industrial applications. Of all Ce minerals, cerium dioxide has received much attention in the global nanotechnology market due to their useful applications for catalysts, fuel cells, and fuel additives. A recent mass flow modeling study predicted that a major source of CeO2 nanoparticles from industrial processing plants (e.g., electronics and optics manufactures) is likely to reach the terrestrial environment such as landfills and soils. The environmental fate of CeO2 nanoparticles is highly dependent on its physcochemical properties in low temperature geochemical environment. Though there are needs in improving the analytical method in detecting/quantifying CeO2 nanoparticles in different environmental media, it is clear that aquatic and terrestrial organisms have been exposed to CeO2 NPs, potentially yielding in negative impact on human and ecosystem health. Interestingly, there has been contradicting reports about the toxicological effects of CeO2 nanoparticles, acting as either an antioxidant or reactive oxygen species production-inducing agent). This poses a challenge in future regulations for the CeO2 nanoparticle application and the risk assessment in the environment.

Method of applying a cerium diffusion coating to a metallic alloy

DOEpatents

Jablonski, Paul D [Salem, OR; Alman, David E [Benton, OR

2009-06-30

A method of applying a cerium diffusion coating to a preferred nickel base alloy substrate has been discovered. A cerium oxide paste containing a halide activator is applied to the polished substrate and then dried. The workpiece is heated in a non-oxidizing atmosphere to diffuse cerium into the substrate. After cooling, any remaining cerium oxide is removed. The resulting cerium diffusion coating on the nickel base substrate demonstrates improved resistance to oxidation. Cerium coated alloys are particularly useful as components in a solid oxide fuel cell (SOFC).

Thermometric titrimetry Studies of the cerium(IV) oxidation of alpha-mercaptocarboxylic acids.

PubMed

Alexander, W A; Mash, C J; McAuley, A

1969-04-01

The cerium(IV) oxidation of thioglycollic, thiolactic and thiomalic acids has been examined by thermometric titration. The titration curves indicate stoichiometries of more than 1 mole of cerium(IV) per mole of alpha-thiol, suggesting possible side-reactions. In the presence of methyl acrylate, however, the expected ratio is observed. The overall heat of each reaction has been derived. Only with a titration method of this kind where allowance can be made for side-reactions can the heats of reaction for these systems be measured.

Environmental Geochemistry of Cerium: Applications and Toxicology of Cerium Oxide Nanoparticles

PubMed Central

Dahle, Jessica T.; Arai, Yuji

2015-01-01

Cerium is the most abundant of rare-earth metals found in the Earth’s crust. Several Ce-carbonate, -phosphate, -silicate, and -(hydr)oxide minerals have been historically mined and processed for pharmaceutical uses and industrial applications. Of all Ce minerals, cerium dioxide has received much attention in the global nanotechnology market due to their useful applications for catalysts, fuel cells, and fuel additives. A recent mass flow modeling study predicted that a major source of CeO2 nanoparticles from industrial processing plants (e.g., electronics and optics manufactures) is likely to reach the terrestrial environment such as landfills and soils. The environmental fate of CeO2 nanoparticles is highly dependent on its physcochemical properties in low temperature geochemical environment. Though there are needs in improving the analytical method in detecting/quantifying CeO2 nanoparticles in different environmental media, it is clear that aquatic and terrestrial organisms have been exposed to CeO2 NPs, potentially yielding in negative impact on human and ecosystem health. Interestingly, there has been contradicting reports about the toxicological effects of CeO2 nanoparticles, acting as either an antioxidant or reactive oxygen species production-inducing agent). This poses a challenge in future regulations for the CeO2 nanoparticle application and the risk assessment in the environment. PMID:25625406

Manganese-cerium oxide catalysts prepared by non-thermal plasma for NO oxidation: Effect of O2 in discharge atmosphere

NASA Astrophysics Data System (ADS)

Liu, Lu; Zheng, Chenghang; Wu, Shenghao; Gao, Xiang; Ni, Mingjiang; Cen, Kefa

2017-09-01

Non-thermal plasma with different O2 concentration in discharge atmosphere was applied to synthesize manganese and cerium mixed-oxides catalysts, which were compared in NO oxidation activity. Discharge atmosphere displayed a crucial influence on the performance of the catalysts prepared by plasma. Relatively low O2 concentration in discharge atmosphere allows synthesizing manganese-cerium oxides catalysts in a moderate environment and therefore is favorable for better physicochemical properties which lead to superior catalytic behavior. The best catalyst was obtained by treatment with 10% O2/N2 plasma and presented over 80% NO conversion in the temperature range of 275-325 °C, whereas catalyst prepared in pure O2 discharge atmosphere had the same activity with a catalyst prepared by calcinations. A correlation between the surface properties of the plasma prepared catalysts and its catalytic activity in NO oxidation is proposed. The amount of the surface adsorbed oxygen has an obvious linear correlation with the amount of Ce3+, the H2 consumption at low temperatures and the catalytic performance. The superior catalytic performance is mainly attributed to the stronger interaction between manganese oxides and ceria, and the formation of poorly crystallized Mn-O-Ce phase in the catalyst which resulted from the slow decomposition of nitrates and organics during plasma treatment. Catalysts prepared in relatively low O2 concentration have large specific surface area and is abundant in Ce3+ species and active oxygen species. The study suggests that plasma treatment with proper discharge gas components is a promising method to prepare effective manganese- cerium oxides catalyst for NO oxidation.

Correlation of the oxidation state of cerium in sol-gel glasses as a function of thermal treatment via optical spectroscopy and XANES studies.

PubMed

Assefa, Zerihun; Haire, R G; Caulder, D L; Shuh, D K

2004-07-01

Sol-gel glass matrices containing lanthanides have numerous technological applications and their formation involves several chemical facets. In the case of cerium, its ability to exist in two different oxidation states or in mixed valence state provides additional complexities for the sol-gel process. The oxidation state of cerium present during different facets of preparation of sol-gel glasses, and also as a function of the starting oxidation state of cerium added, were studied both by optical spectroscopy and X-ray absorption near-edge structures (XANES). The findings acquired by each approach were compared. The primary focus was on the redox chemistries associated with sample preparation, gelation, and thermal treatment. When Ce3+ is introduced into the starting sols, the trivalent state normally prevails in the wet and room temperature-dried gels. Heating in air at >100 degrees C can generate a light yellow coloration with partial oxidation to the tetravalent state. Above 200 degrees C and up to approximately 1000 degrees C, cerium is oxidized to its tetravalent state. In contrast, when tetravalent cerium is introduced into the sol, both the wet and room temperature-dried gels lose the yellow-brown color of the initial ceric ammonium nitrate solution. When the sol-gel is heated to 110 degrees C it turns yellowish as the cerium tends to be re-oxidized. The yellow color is believed to represent the effect of oxidation and oligomerization of the cerium-silanol units in the matrix. The luminescence properties are also affected by these changes, the details of which are reported herein.

Exposure, Health and Ecological Effects Review of Engineered Nanoscale Cerium and Cerium Oxide Associated with its Use as a Fuel Additive

EPA Science Inventory

Advances of nanoscale science have produced nanomaterials with unique physical and chemical properties at commercial levels which are now incorporated into over 1000 products. Nanoscale cerium (di) oxide (CeO(2)) has recently gained a wide range of applications which includes coa...

Preparation of the porous cerium dioxide film by two-step anodization and heat treating method

NASA Astrophysics Data System (ADS)

Liu, Xiaozhen; Zhu, Bolun; Liu, Yuze; Wang, Shanshan; Chen, Jie; Wang, Xiaoyu

2017-12-01

The porous cerium dioxide films were prepared with cerium foils as raw materials by two-step anodization and heat treating method. The anodic cerium oxide films were heat treated in 25∼400°C respectively. The cerium dioxide films were characterized with X-ray diffraction (XRD), Fourier transform infrared (FTIR) techniques, energy-dispersive analyses of X-ray (EDAX) and scanning electron microcopy (SEM), respectively. The anodic cerium oxide film is composed of Ce(OH)3, CeO2 and Ce2O3. When the anodic cerium oxide films were heat treated in 300°C∼400°C for 2h, Ce(OH)3 and Ce2O3 in the anodic cerium oxide films may be converted to CeO2, and the heat treated anodic cerium oxide films are the cerium dioxide films. Water, ethylene glycol and CO2 are adsorbed in the anodic cerium oxide film. The adsorbing water, ethylene glycol and CO2 in the anodic cerium oxide film are removed at 300°C. The cerium dioxide film has strong absorption in the range of 1600∼4000cm-1. The structure of the cerium dioxide film is the porous.

Antioxidant and antigenotoxic properties of CeO2 NPs and cerium sulphate: Studies with Drosophila melanogaster as a promising in vivo model.

PubMed

Alaraby, Mohamed; Hernández, Alba; Annangi, Balasubramanyam; Demir, Esref; Bach, Jordi; Rubio, Laura; Creus, Amadeu; Marcos, Ricard

2015-01-01

Although in vitro approaches are the most used for testing the potential harmful effects of nanomaterials, in vivo studies produce relevant information complementing in vitro data. In this context, we promote the use of Drosophila melanogaster as a suitable in vivo model to characterise the potential risks associated to nanomaterials exposure. The main aim of this study was to evaluate different biological effects associated to cerium oxide nanoparticles (Ce-NPs) and cerium (IV) sulphate exposure. The end-points evaluated were egg-to-adult viability, particles uptake through the intestinal barrier, gene expression and intracellular reactive oxygen species (ROS) production by haemocytes, genotoxicity and antigenotoxicity. Transmission electron microscopy images showed internalisation of Ce-NPs by the intestinal barrier and haemocytes, and significant expression of Hsp genes was detected. In spite of these findings, neither toxicity nor genotoxicity related to both forms of cerium were observed. Interestingly, Ce-NPs significantly reduced the genotoxic effect of potassium dichromate and the intracellular ROS production. No morphological malformations were detected after larvae treatment. This study highlights the importance of D. melanogaster as animal model in the study of the different biological effects caused by nanoparticulated materials, at the time that shows its usefulness to study the role of the intestinal barrier in the transposition of nanomaterials entering via ingestion.

Multicolored redox active upconverter cerium oxide nanoparticle for bio-imaging and therapeutics†

PubMed Central

Babu, Suresh; Cho, Jung-Hyun; Dowding, Janet M.; Heckert, Eric; Komanski, Chris; Das, Soumen; Colon, Jimmie; Baker, Cheryl H.; Bass, Michael; Self, William T.; Seal, Sudipta

2011-01-01

Cytocompatible, co-doped cerium oxide nanoparticles exhibited strong upconversion properties that were found to kill lung cancer cells by inducing apoptosis thereby demonstrating the potential to be used as clinical contrast agents for imaging and as therapeutic agents for treatment of cancer. PMID:20683524

Intergenerational responses of wheat (Triticum aestivum L.) to cerium oxide nanoparticles exposure

EPA Science Inventory

The intergenerational impact of engineered nanomaterials in plants is a key knowledge gap in the literature. A soil microcosm study was performed to assess the effects of multi-generational exposure of wheat (Triticum aestivum L.) to cerium oxide nanoparticles (CeO2-NPs). Seeds f...

The effect of cerium oxide argon-annealed coatings on the high temperature oxidation of a FeCrAl alloy

NASA Astrophysics Data System (ADS)

Nguyen, C. T.; Buscail, H.; Cueff, R.; Issartel, C.; Riffard, F.; Perrier, S.; Poble, O.

2009-09-01

Ceria coatings were applied in order to improve the adherence of alumina scales developed on a model Fe-20Cr-5Al alloy during oxidation at high temperature. These coatings were performed by argon annealing of a ceria sol-gel coating at temperatures ranging between 600 and 1000 °C. The influence of these coatings on the alloy oxidation behaviour was studied at 1100 °C. In situ X-ray diffraction (XRD) was performed to characterize the coating crystallographic nature after annealing and during the oxidation process. The alumina scale morphologies were studied by means of scanning electron microscopy (SEM) coupled with energy dispersive X-ray spectroscopy (EDS). The present work shows that the alumina scale morphology observed on cerium sol-gel coated alloy was very convoluted. On the cerium sol-gel coated alloy, argon annealing results in an increase of the oxidation rate in air, at 1100 °C. The 600 °C argon annealing temperature results in a good alumina scale adherence under thermal cycling conditions at 1100 °C.

Corrosion resistance of flaky aluminum pigment coated with cerium oxides/hydroxides in chloride and acidic electrolytes

NASA Astrophysics Data System (ADS)

Niroumandrad, S.; Rostami, M.; Ramezanzadeh, B.

2015-12-01

The objective of this study was to enhance the corrosion resistance of lamellar aluminum pigment through surface treatment by cerium oxides/hydroxides. The surface composition of the pigments was studied by energy-dispersive spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS). The corrosion resistance of the pigment was evaluated by conventional hydrogen evolution measurements in acidic solution and electrochemical impedance spectroscopy (EIS) in 3.5% NaCl solution. Results showed that the Ce-rich coating composed of Ce2O3 and CeO2 was precipitated on the pigment surface after immersion in the cerium solution. The corrosion resistance of pigment was significantly enhanced after modification with cerium layer.

Polyelectrolyte-mediated assembly of copper-phthalocyanine tetrasulfonate multilayers and the subsequent production of nanoparticulate copper oxide thin films.

PubMed

Chickneyan, Zarui Sara; Briseno, Alejandro L; Shi, Xiangyang; Han, Shubo; Huang, Jiaxing; Zhou, Feimeng

2004-07-01

An approach to producing films of nanometer-sized copper oxide particulates, based on polyelectrolyte-mediated assembly of the precursor, copper(II)phthalocyanine tetrasulfonate (CPTS), is described. Multilayered CPTS and polydiallyldimethylammonium chloride (PDADMAC) were alternately assembled on different planar substrates via the layer-by-layer (LbL) procedure. The growth of CPTS multilayers was monitored by UV-visible spectrometry and quartz crystal microbalance (QCM) measurements. Both the UV-visible spectra and the QCM data showed that a fixed amount of CPTS could be attached to the substrate surface for a given adsorption cycle. Cyclic voltammograms at the CPTS/PDADMAC-covered gold electrode exhibited a decrease in peak currents with the layer number, indicating that the permeability of CPTS multilayers on the electrodes had diminished. When these CPTS multilayered films were calcined at elevated temperatures, uniform thin films composed of nanoparticulate copper oxide could be produced. Ellipsometry showed that the thickness of copper oxide nanoparticulate films could be precisely tailored by varying the thickness of CPTS multilayer films. The morphology and roughness of CPTS multilayer and copper oxide thin films were characterized by atomic force microscopy. X-ray diffraction (XRD) measurements indicated that these thin films contained both CuO and Cu2O nanoparticles. The preparation of such copper oxide thin films with the use of metal complex precursors represents a new route for the synthesis of inorganic oxide films with a controlled thickness.

Cerium anomaly at microscale in fossils.

PubMed

Gueriau, Pierre; Mocuta, Cristian; Bertrand, Loïc

2015-09-01

Patterns in rare earth element (REE) concentrations are essential instruments to assess geochemical processes in Earth and environmental sciences. Excursions in the "cerium anomaly" are widely used to inform on past redox conditions in sediments. This proxy resources to the specificity of cerium to adopt both the +III and +IV oxidation states, while most rare earths are purely trivalent and share very similar reactivity and transport properties. In practical terms, the level of cerium anomaly is established through elemental point quantification and profiling. All these models rely on a supposed homogeneity of the cerium oxidation state within the samples. However, this has never been demonstrated, whereas the cerium concentration can significantly vary within a sample, as shown for fossils, which would vastly complicate interpretation of REE patterns. Here, we report direct micrometric mapping of Ce speciation through synchrotron X-ray absorption spectroscopy and production of local rare earth patterns in paleontological fossil tissues through X-ray fluorescence mapping. The sensitivity of the approach is demonstrated on well-preserved fishes and crustaceans from the Late Cretaceous (ca. 95 million years (Myr) old). The presence of Ce under the +IV form within the fossil tissues is attributed to slightly oxidative local conditions of burial and agrees well with the limited negative cerium anomaly observed in REE patterns. The [Ce(IV)]/[Ce(tot)] ratio appears remarkably stable at the microscale within each fossil and is similar between fossils from the locality. Speciation maps were obtained from an original combination of synchrotron microbeam X-ray fluorescence, absorption spectroscopy, and diffraction, together with light and electron microscopy. This work also highlights the need for more systematic studies of cerium geochemistry at the microscale in paleontological contexts, in particular across fossil histologies.

Tuning Reactivity and Electronic Properties through Ligand Reorganization within a Cerium Heterobimetallic Framework

DOE Office of Scientific and Technical Information (OSTI.GOV)

Robinson, Jerome R.; Gordon, Zachary; Booth, Corwin H.

2014-06-24

Cerium compounds have played vital roles in organic, inorganic, and materials chemistry due to their reversible redox chemistry between trivalent and tetravalent oxidation states. However, attempts to rationally access molecular cerium complexes in both oxidation states have been frustrated by unpredictable reactivity in cerium(III) oxidation chemistry. Such oxidation reactions are limited by steric saturation at the metal ion, which can result in high energy activation barriers for electron transfer. An alternative approach has been realized using a rare earth/alkali metal/1,1'-BINOLate (REMB) heterobimetallic framework, which uses redox-inactive metals within the secondary coordination sphere to control ligand reorganization. The rational syntheses ofmore » functionalized cerium(IV) products and a mechanistic examination of the role of ligand reorganization in cerium(III) oxidation are presented.« less

Phenotypic and genomic responses to titanium dioxide and cerium oxide nanoparticles in Arabidopsis germinants

EPA Science Inventory

The effects of exposure to two nanoparticles (NPs) -titanium dioxide (nano-titania) and cerium oxide (nano-ceria) at 500 mg NPs L-1 on gene expression and growth in Arabidopsis thaliana germinants were studied using microarrays and phenotype studies. After 12 days post treatment,...

Oxidation behaviour and electrical properties of cobalt/cerium oxide composite coatings for solid oxide fuel cell interconnects

NASA Astrophysics Data System (ADS)

Harthøj, Anders; Holt, Tobias; Møller, Per

2015-05-01

This work evaluates the performance of cobalt/cerium oxide (Co/CeO2) composite coatings and pure Co coatings to be used for solid oxide fuel cell (SOFC) interconnects. The coatings are electroplated on the ferritic stainless steels Crofer 22 APU and Crofer 22H. Coated and uncoated samples are exposed in air at 800 °C for 3000 h and oxidation rates are measured and oxide scale microstructures are investigated. Area-specific resistances (ASR) in air at 850 °C of coated and uncoated samples are also measured. A dual layered oxide scale formed on all coated samples. The outer layer consisted of Co, Mn, Fe and Cr oxide and the inner layer consisted of Cr oxide. The CeO2 was present as discrete particles in the outer oxide layer after exposure. The Cr oxide layer thicknesses and oxidations rates were significantly reduced for Co/CeO2 coated samples compared to for Co coated and uncoated samples. The ASR of all Crofer 22H samples increased significantly faster than of Crofer 22 APU samples which was likely due to the presence of SiO2 in the oxide/metal interface of Crofer 22H.

An environmentally compliant cerium-based conversion coating for aluminum protection

NASA Astrophysics Data System (ADS)

Lin, Xuan

Chromate conversion coatings have been extensively used in the aircraft industry for the corrosion protection of aluminum alloys. Unfortunately, hexavalent chromium, which is a primary component in the chromating process, is a confirmed carcinogen. Because of rising remediation and disposal costs caused by increasingly strict regulations, the replacement of the traditional chromate conversion process is becoming a top priority in the metal finishing industry. This research focused on the electrodeposition of cerium-based coatings on 7075-T6 aluminum alloy in an electrolyte containing a cerium salt, an oxidizing agent and an organic solvent. The cerium-rich deposits were characterized by phase composition, oxidation state, coating thickness, surface morphology, deposition mechanism and polarization behavior. Chemical and electrochemical tests were utilized to compare the corrosion resistance between cerium-based coatings and chromate conversion coatings. To characterize and simulate the deposition process, a variety of approaches were utilized to study the oxidation states of cerium in various soluble and precipitated forms as a function of hydrogen peroxide and electrolyte pH. The pH ranges where the oxidation and reduction reactions dominate were determined. Further studies were performed to optimize the corrosion performance of cerium-based coatings and to understand the effects of electrolyte constituents and deposition parameters. The optimum levels for these variables were identified. A patent disclosure on the cerium-based coating process was made to the University of Missouri-Rolla and has now been officially filed with the U.S. Patent Office.

Solar hydrogen production with cerium oxides thermochemical cycle

NASA Astrophysics Data System (ADS)

Binotti, Marco; Di Marcoberardino, Gioele; Biassoni, Mauro; Manzolini, Giampaolo

2017-06-01

This paper discusses the hydrogen production using a solar driven thermochemical cycle. The thermochemical cycle is based on nonstoichiometric cerium oxides redox and the solar concentration system is a solar dish. Detailed optical and redox models were developed to optimize the hydrogen production performance as function of several design parameters (i.e. concentration ratio, reactor pressures and temperatures) The efficiency of the considered technology is compared against two commercially available technologies namely PV + electrolyzer and Dish Stirling + electrolyzer. Results show that solar-to-fuel efficiency of 21.2% can be achieved at design condition assuming a concentration ratio around 5000, reduction and oxidation temperatures of 1500°C and 1275 °C. When moving to annual performance, the annual yield of the considered approach can be as high as 16.7% which is about 43% higher than the best competitive technology. The higher performance implies that higher installation costs around 40% can be accepted for the innovative concept to achieve the same cost of hydrogen.

Cerium oxide nanoparticles protect endothelial cells from apoptosis induced by oxidative stress.

PubMed

Chen, Shizhu; Hou, Yingjian; Cheng, Gong; Zhang, Cuimiao; Wang, Shuxiang; Zhang, Jinchao

2013-07-01

Oxidative stress is well documented to cause injury to endothelial cells (ECs), which in turn trigger cardiovascular diseases. Previous studies revealed that cerium oxide nanoparticles (nanoceria) had antioxidant property, but the protective effect of nanoceria on ROS injury to ECs and cardiovascular diseases has not been reported. In the current study, we investigated the protective effect and underlying mechanisms of nanoceria on oxidative injury to ECs. The cell viability, lactate dehydrogenase release, cellular uptake, intracellular localization and reactive oxygen species (ROS) levels, endocytosis mechanism, cell apoptosis, and mitochondrial membrane potential were performed. The results indicated that nanoceria had no cytotoxicity on ECs but had the ability to prevent injury by H2O2. Nanoceria could be uptaken into ECs through caveolae- and clathrin-mediated endocytosis and distributed throughout the cytoplasma. The internalized nanoceria effectively attenuated ROS overproduction induced by H2O2. Apoptosis was also alleviated greatly by nanoceria pretreatment. These results may be helpful for more rational application of nanoceria in biomedical fields in the future.

Altering properties of cerium oxide thin films by Rh doping

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ševčíková, Klára, E-mail: klarak.sevcikova@seznam.cz; NIMS Beamline Station at SPring-8, National Institute for Materials Science, Sayo, Hyogo 679-5148; Nehasil, Václav, E-mail: nehasil@mbox.troja.mff.cuni.cz

2015-07-15

Highlights: • Thin films of ceria doped by rhodium deposited by RF magnetron sputtering. • Concentration of rhodium has great impact on properties of Rh–CeO{sub x} thin films. • Intensive oxygen migration in films with low concentration of rhodium. • Oxygen migration suppressed in films with high amount of Rh dopants. - Abstract: Ceria containing highly dispersed ions of rhodium is a promising material for catalytic applications. The Rh–CeO{sub x} thin films with different concentrations of rhodium were deposited by RF magnetron sputtering and were studied by soft and hard X-ray photoelectron spectroscopies, Temperature programmed reaction and X-ray powder diffractionmore » techniques. The sputtered films consist of rhodium–cerium mixed oxide where cerium exhibits a mixed valency of Ce{sup 4+} and Ce{sup 3+} and rhodium occurs in two oxidation states, Rh{sup 3+} and Rh{sup n+}. We show that the concentration of rhodium has a great influence on the chemical composition, structure and reducibility of the Rh–CeO{sub x} thin films. The films with low concentrations of rhodium are polycrystalline, while the films with higher amount of Rh dopants are amorphous. The morphology of the films strongly influences the mobility of oxygen in the material. Therefore, varying the concentration of rhodium in Rh–CeO{sub x} thin films leads to preparing materials with different properties.« less

Controlling the physics and chemistry of binary and ternary praseodymium and cerium oxide systems.

PubMed

Niu, Gang; Zoellner, Marvin Hartwig; Schroeder, Thomas; Schaefer, Andreas; Jhang, Jin-Hao; Zielasek, Volkmar; Bäumer, Marcus; Wilkens, Henrik; Wollschläger, Joachim; Olbrich, Reinhard; Lammers, Christian; Reichling, Michael

2015-10-14

Rare earth praseodymium and cerium oxides have attracted intense research interest in the last few decades, due to their intriguing chemical and physical characteristics. An understanding of the correlation between structure and properties, in particular the surface chemistry, is urgently required for their application in microelectronics, catalysis, optics and other fields. Such an understanding is, however, hampered by the complexity of rare earth oxide materials and experimental methods for their characterisation. Here, we report recent progress in studying high-quality, single crystalline, praseodymium and cerium oxide films as well as ternary alloys grown on Si(111) substrates. Using these well-defined systems and based on a systematic multi-technique surface science approach, the corresponding physical and chemical properties, such as the surface structure, the surface morphology, the bulk-surface interaction and the oxygen storage/release capability, are explored in detail. We show that specifically the crystalline structure and the oxygen stoichiometry of the oxide thin films can be well controlled by the film preparation method. This work leads to a comprehensive understanding of the properties of rare earth oxides and highlights the applications of these versatile materials. Furthermore, methanol adsorption studies are performed on binary and ternary rare earth oxide thin films, demonstrating the feasibility of employing such systems for model catalytic studies. Specifically for ceria systems, we find considerable stability against normal environmental conditions so that they can be considered as a "materials bridge" between surface science models and real catalysts.

Inhaled Diesel Emissions Generated with Cerium Oxide Nanoparticle Fuel Additive Induce Adverse Pulmonary and Systemic Effects

EPA Science Inventory

Diesel exhaust (DE) exposure induces adverse cardiopulmonary effects. Cerium oxide nanoparticles added to diesel fuel (DECe) increases fuel burning efficiency but leads to altered emission characteristics and potentially altered health effects. Here, we evaluated whether DECe res...

Surface-charge-dependent cell localization and cytotoxicity of cerium oxide nanoparticles.

PubMed

Asati, Atul; Santra, Santimukul; Kaittanis, Charalambos; Perez, J Manuel

2010-09-28

Cerium oxide nanoparticles (nanoceria) have shown great potential as antioxidant and radioprotective agents for applications in cancer therapy. Recently, various polymer-coated nanoceria preparations have been developed to improve their aqueous solubility and allow for surface functionalization of these nanoparticles. However, the interaction of polymer-coated nanoceria with cells, their uptake mechanism, and subcellular localization are poorly understood. Herein, we engineered polymer-coated cerium oxide nanoparticles with different surface charges (positive, negative, and neutral) and studied their internalization and toxicity in normal and cancer cell lines. The results showed that nanoceria with a positive or neutral charge enters most of the cell lines studied, while nanoceria with a negative charge internalizes mostly in the cancer cell lines. Moreover, upon entry into the cells, nanoceria is localized to different cell compartments (e.g., cytoplasm and lysosomes) depending on the nanoparticle's surface charge. The internalization and subcellular localization of nanoceria plays a key role in the nanoparticles' cytotoxicity profile, exhibiting significant toxicity when they localize in the lysosomes of the cancer cells. In contrast, minimal toxicity is observed when they localize into the cytoplasm or do not enter the cells. Taken together, these results indicate that the differential surface-charge-dependent localization of nanoceria in normal and cancer cells plays a critical role in the nanoparticles' toxicity profile.

Nanoporous cerium oxide thin film for glucose biosensor.

PubMed

Saha, Shibu; Arya, Sunil K; Singh, S P; Sreenivas, K; Malhotra, B D; Gupta, Vinay

2009-03-15

Nanoporous cerium oxide (CeO(2)) thin film deposited onto platinum (Pt) coated glass plate using pulsed laser deposition (PLD) has been utilized for immobilization of glucose oxidase (GOx). Atomic force microscopy studies reveal the formation of nanoporous surface morphology of CeO(2) thin film. Response studies carried out using differential pulsed voltammetry (DPV) and optical measurements show that the GOx/CeO(2)/Pt bio-electrode shows linearity in the range of 25-300 mg/dl of glucose concentration. The low value of Michaelis-Menten constant (1.01 mM) indicates enhanced enzyme affinity of GOx to glucose. The observed results show promising application of the nanoporous CeO(2) thin film for glucose sensing application without any surface functionalization or mediator.

Bioavailability of cerium oxide nanoparticles to Raphanus sativus L. in two soils.

PubMed

Zhang, Weilan; Musante, Craig; White, Jason C; Schwab, Paul; Wang, Qiang; Ebbs, Stephen D; Ma, Xingmao

2017-01-01

Cerium oxide nanoparticles (CeO 2 NP) are a common component of many commercial products. Due to the general concerns over the potential toxicity of engineered nanoparticles (ENPs), the phytotoxicity and in planta accumulation of CeO 2 NPs have been broadly investigated. However, most previous studies were conducted in hydroponic systems and with grain crops. For a few studies performed with soil grown plants, the impact of soil properties on the fate and transport of CeO 2 NPs was generally ignored even though numerous previous studies indicate that soil properties play a critical role in the fate and transport of environmental pollutants. The objectives of this study were to evaluate the soil fractionation and bioavailability of CeO 2 NPs to Raphanus sativus L (radish) in two soil types. Our results showed that the silty loam contained slightly higher exchangeable fraction (F1) of cerium element than did loamy sand soil, but significantly lower reducible (F2) and oxidizable (F3) fractions as CeO 2 NPs concentration increased. CeO 2 NPs associated with silicate minerals or the residue fraction (F4) dominated in both soils. The cerium concentration in radish storage root showed linear correlation with the sum of the first three fractions (r 2  = 0.98 and 0.78 for loamy sand and silty loam respectively). However, the cerium content in radish shoots only exhibited strong correlations with F1 (r 2  = 0.97 and 0.89 for loamy sand and silty loam respectively). Overall, the results demonstrated that soil properties are important factors governing the distribution of CeO 2 NPs in soil and subsequent bioavailability to plants. Copyright © 2015 Elsevier Masson SAS. All rights reserved.

Sulfonated macro-RAFT agents for the surfactant-free synthesis of cerium oxide-based hybrid latexes.

PubMed

Garnier, Jérôme; Warnant, Jérôme; Lacroix-Desmazes, Patrick; Dufils, Pierre-Emmanuel; Vinas, Jérôme; van Herk, Alex

2013-10-01

Three types of amphiphatic macro-RAFT agents were employed as compatibilizers to promote the polymerization reaction at the surface of nanoceria for the synthesis of CeO2-based hybrid latexes. Macro-RAFT copolymers and terpolymers were first synthesized employing various combinations of butyl acrylate as a hydrophobic monomer and acrylic acid (AA) and/or 2-acrylamido-2-methylpropane sulfonic acid (AMPS) as hydrophilic monomers. After characterizing the adsorption of these macro-RAFT agents at the cerium oxide surface by UV-visible spectrometry, emulsion copolymerization reactions of styrene and methyl acrylate were then carried out in the presence of the surface-modified nanoceria. Dynamic Light Scattering and cryo-Transmission Electron Microscopy were employed to confirm the hybrid structure of the final CeO2/polymer latexes, and proved that the presence of acrylic acid units in amphiphatic macro-RAFT agents enabled an efficient formation of hybrid structures, while the presence of AMPS units, when combined with AA units, resulted in a better distribution of cerium oxide nanoclusters between latex particles. Copyright © 2013 Elsevier Inc. All rights reserved.

A novel cerium oxide nanoparticles-based colorimetric sensor using tetramethyl benzidine reagent for antioxidant activity assay.

PubMed

Ozdemir Olgun, F Ayca; Üzer, Ayşem; Ozturk, Birsen Demirata; Apak, Reşat

2018-05-15

Antioxidant activity (AOA) assays using nanotechnology are recently developed utilizing nanoparticles of transition metal oxides, especially nanoceria that can switch between trivalent and tetravalent oxidation states of cerium. Cerium oxide nanoparticles (CeO-NPs) may act as both an oxidant and an antioxidant, depending on the preparation method and particle size. A novel colorimetric sensor for AOA assay is proposed with the use of poly(acrylic acid) sodium salt (PAANa)-coated CeO-NPs. PAANa-coated CeO-NPs oxidized tetramethyl benzidine (TMB), a peroxidase substrate, in a slightly acidic solution at pH 4.0 to a blue charge-transfer complex. Antioxidants decreased the color intensity of the nanoceria suspension, and were indirectly determined by absorbance difference. Detection limits, linearity, additivity and precision were calculated, e.g., quercetin quantification with the proposed assay showed a detection limit of 8.25 × 10 -9 mol L -1 . The trolox equivalent antioxidant capacities of hydrophilic and lipophilic antioxidants were compatible with those of conventional antioxidant assays. Potential interferents such as glucose, citric acid, mannitol, sorbitol and benzoic acid did not adversely affect AOA determination. The developed sensor is more sensitive and selective than similar colorimetric sensors relying on the intrinsic color change of nanoceria. The measurement wavelength is sufficiently red-shifted, preventing possible interferences from plant pigments. Copyright © 2018 Elsevier B.V. All rights reserved.

Cerium-modified doped strontium titanate compositions for solid oxide fuel cell anodes and electrodes for other electrochemical devices

DOEpatents

Marina, Olga A [Richland, WA; Stevenson, Jeffry W [Richland, WA

2010-03-02

The present invention provides novel compositions that find advantageous use in making electrodes for electrochemical cells and electrochemical devices such as solid oxide fuel cells, electrolyzers, sensors, pumps and the like, the compositions comprising cerium-modified doped strontium titanate. The invention also provides novel methods for making and using anode material compositions and solid oxide fuel cells and solid oxide fuel cell assemblies having anodes comprising the compositions.

Cerium-modified doped strontium titanate compositions for solid oxide fuel cell anodes and electrodes for other electrochemical devices

DOEpatents

Marina, Olga A [Richland, WA; Stevenson, Jeffry W [Richland, WA

2010-11-23

The present invention provides novel compositions that find advantageous use in making electrodes for electrochemical cells and electrochemical devices such as solid oxide fuel cells, electrolyzers, sensors, pumps and the like, the compositions comprising cerium-modified doped strontium titanate. The invention also provides novel methods for making and using anode material compositions and solid oxide fuel cells and solid oxide fuel cell assemblies having anodes comprising the compositions.

Coal and tire burning mixtures containing ultrafine and nanoparticulate materials induce oxidative stress and inflammatory activation in macrophages.

PubMed

Gasparotto, Juciano; Somensi, Nauana; Caregnato, Fernanda F; Rabelo, Thallita K; DaBoit, Kátia; Oliveira, Marcos L S; Moreira, José C F; Gelain, Daniel P

2013-10-01

Ultra-fine and nano-particulate materials resulting from mixtures of coal and non-coal fuels combustion for power generation release to the air components with toxic potential. We evaluated toxicological and inflammatory effects at cellular level that could be induced by ultrafine/nanoparticles-containing ashes from burning mixtures of coal and tires from an American power plant. Coal fly ashes (CFA) samples from the combustion of high-S coal and tire-derived fuel, the latter about 2-3% of the total fuel feed, in a 100-MW cyclone utility boiler, were suspended in the cell culture medium of RAW 264.7 macrophages. Cell viability, assessed by MTT reduction, SRB incorporation and contrast-phase microscopy analysis demonstrated that CFA did not induce acute toxicity. However, CFA at 1mg/mL induced an increase of approximately 338% in intracellular TNF-α, while release of this proinflammatory cytokine was increased by 1.6-fold. The expression of the inflammatory mediator CD40 receptor was enhanced by 2-fold, the receptor for advanced glycation endproducts (RAGE) had a 5.7-fold increase and the stress response protein HSP70 was increased nearly 12-fold by CFA at 1mg/mL. Although CFA did not induce cell death, parameters of oxidative stress and reactive species production were found to be altered at several degrees, such as nitrite accumulation (22% increase), DCFH oxidation (3.5-fold increase), catalase (5-fold increase) and superoxide dismutase (35% inhibition) activities, lipoperoxidation (4.2 fold-increase) and sulfhydryl oxidation (40% decrease in free SH groups). The present results suggest that CFA containing ultra-fine and nano-particulate materials from coal and tire combustion may induce sub-chronic cell damage, as they alter inflammatory and oxidative stress parameters at the molecular and cellular levels, but do not induce acute cell death. © 2013.

Antioxidant Cerium Oxide Nanoparticles in Biology and Medicine

PubMed Central

Nelson, Bryant C.; Johnson, Monique E.; Walker, Marlon L.; Riley, Kathryn R.; Sims, Christopher M.

2016-01-01

Previously, catalytic cerium oxide nanoparticles (CNPs, nanoceria, CeO2-x NPs) have been widely utilized for chemical mechanical planarization in the semiconductor industry and for reducing harmful emissions and improving fuel combustion efficiency in the automobile industry. Researchers are now harnessing the catalytic repertoire of CNPs to develop potential new treatment modalities for both oxidative- and nitrosative-stress induced disorders and diseases. In order to reach the point where our experimental understanding of the antioxidant activity of CNPs can be translated into useful therapeutics in the clinic, it is necessary to evaluate the most current evidence that supports CNP antioxidant activity in biological systems. Accordingly, the aims of this review are three-fold: (1) To describe the putative reaction mechanisms and physicochemical surface properties that enable CNPs to both scavenge reactive oxygen species (ROS) and to act as antioxidant enzyme-like mimetics in solution; (2) To provide an overview, with commentary, regarding the most robust design and synthesis pathways for preparing CNPs with catalytic antioxidant activity; (3) To provide the reader with the most up-to-date in vitro and in vivo experimental evidence supporting the ROS-scavenging potential of CNPs in biology and medicine. PMID:27196936

Titanium-doped cerium oxide nanoparticles protect cells from hydrogen peroxide-induced apoptosis

PubMed Central

Clark, Andrea; Zhu, Aiping; Petty, Howard R.

2014-01-01

To develop new nanoparticle materials possessing anti-oxidative capacity with improved physical characteristics, we have studied titanium-doped cerium oxide (CeTiO2) nanoparticles. CeTiO2 nanoparticles had a mode diameter of 15-20 nm. These nanoparticles demonstrated catalase activity, and did not promote the activation of hemolytic or cytolytic pathways in living cells. Using surface plasmon resonance enhanced microscopy, we find that these nanoparticles associate with cells. Transmission electron microscopy studies demonstrated that these nanoparticles accumulate within the vacuolar compartment of cells. Importantly, CeTiO2 nanoparticles decrease hydrogen peroxide-mediated apoptosis of cells as judged by the reduced cleavage of a caspase 3-sensitive label. CeTiO2 nanoparticles may contribute to deflecting tissue damage in a broad spectrum of oxidant-mediated diseases, such as macular degeneration and Alzheimer's disease. PMID:24791147

Nutritional quality assessment of tomato fruits after exposure to uncoated and citric acid coated cerium oxide nanoparticles, bulk cerium oxide, cerium acetate and citric acid.

PubMed

Barrios, Ana Cecilia; Medina-Velo, Illya A; Zuverza-Mena, Nubia; Dominguez, Osvaldo E; Peralta-Videa, Jose R; Gardea-Torresdey, Jorge L

2017-01-01

Little is known about the effects of surface modification on the interaction of nanoparticles (NPs) with plants. Tomato (Solanum lycopersicum L.) plants were cultivated in potting soil amended with bare and citric acid coated nanoceria (nCeO 2, nCeO 2 +CA), cerium acetate (CeAc), bulk cerium oxide (bCeO 2 ) and citric acid (CA) at 0-500 mg kg -1 . Fruits were collected year-round until the harvesting time (210 days). Results showed that nCeO 2 +CA at 62.5, 250 and 500 mg kg -1 reduced dry weight by 54, 57, and 64% and total sugar by 84, 78, and 81%. At 62.5, 125, and 500 mg kg -1 nCeO 2 +CA decreased reducing sugar by 63, 75, and 52%, respectively and at 125 mg kg -1 reduced starch by 78%, compared to control. The bCeO 2 at 250 and 500 mg kg -1 , increased reducing sugar by 67 and 58%. In addition, when compared to controls, nCeO 2 at 500 mg kg -1 reduced B (28%), Fe (78%), Mn (33%), and Ca (59%). At 125 mg kg -1 decreased Al by 24%; while nCeO 2 +CA at 125 and 500 mg kg -1 increased B by 33%. On the other hand, bCeO 2 at 62.5 mg kg -1 increased Ca (267%), but at 250 mg kg -1 reduced Cu (52%), Mn (33%), and Mg (58%). Fruit macromolecules were mainly affected by nCeO 2 +CA, while nutritional elements by nCeO 2 ; however, all Ce treatments altered, in some way, the nutritional quality of tomato fruit. To our knowledge, this is the first study comparing effects of uncoated and coated nanoceria on tomato fruit quality. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

Determination of chemical speciations of cerium in nuclear waste glasses

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gong, Meiling; Li, Hong

1996-12-31

Cerium oxides have been widely used as a surrogate for plutonium in the investigation of the melt and durability behavior of simulated nuclear waste glasses. It is well known that there is a cerous-ceric equilibrium in silicate glasses under normal melting conditions. The position of this equilibrium depends on glass composition, melting temperature, furnace atmosphere, and possibly the total amounts of cerium in glass. The oxidation state of cerium affects total solubility of cerium in glass, solubilities of other components in glass, viscosities and liquidus temperatures of the melts, and the chemical durability of the glasses. A procedure was developedmore » for the determination of the ceric and cerous distribution. The glass was ground to small particles of less than 300 meshes and was dissolved in mixture of HF and H{sub 2}SO{sub 4}. The ceric oxide was graduately reduced to cerous species in the presence of HF acid during the dissolution. To compensate the change of the equilibrium during the dissolution, a calibration curve is made with a mixture of standard solution of ceric sulphate and one gram of glass of the same composition containing no cerium. Boric acid was added to complex the fluoride ions, and the resultant solution was titrated potentiometrically with 0.01 N ferrous ammonium sulphate solution. The corrected ceric concentration was obtained on the calibration curve. The total cerium content in the above solution was analyzed using ICP-AES and the cerous content was the difference between the total Ce and Ce(+4).« less

Adsorption of cadmium on cerium oxide nanoparticles and oyster shells

NASA Astrophysics Data System (ADS)

Ji, Yongbo; Liu, Zhuomiao; Dang, Yonghui; Xu, Lina; Ning, Fangyuan; Xue, Yinhao; Wei, Yongpeng; Dai, Yanhui

2018-03-01

This study investigated the adsorption of cadmium (Cd(II)) by cerium oxide nanoparticles (CeO2 NPs) and oyster shells in seawater. The results showed that the addition of Cd(II) significantly inhibited the agglomeration of CeO2 NPs both in DI water and seawater, increased the positive charges of CeO2 NPs in DI water and neutralized the negative charges of CeO2 NPs in seawater. Additionally, CeO2 NPs could adsorb Cd and the bioavailability of Cd was reduced in the presence of oyster shells. This study demonstrated that the adsorption of metals on shells should not be neglected for the accumulation of metals by shellfish.

Germination and early plant development of ten plant species exposed to titanium dioxide and cerium oxide nanoparticles

EPA Science Inventory

Ten agronomic plant species were exposed to different concentrations of nano titanium dioxide (nTiO2) or nano cerium oxide (nCeO2) (0, 250, 500 and 1000 mg/L) to examine potential effects on germination and early seedling development. We modified a standard test protocol develop...

Cerium Oxide Nanoparticles Decorated Graphene Nanosheets for Selective Detection of Dopamine.

PubMed

Nayak, Pranati; Santhosh, P N; Ramaprabhu, S

2015-07-01

The fabrication of a novel amperometric biosensor based on selective determination of dopamine (DA) using nafion coated cerium oxide nanoparticles (NPs) decorated graphene nanosheets (CeO2-HEG-nafion) as a transducer candidate is reported. Graphene was synthesized by hydrogen exfoliation technique. Decoration of CeO2NPs over graphene nanosheets was done by chemical reduction method. The electrochemical impedance spectroscopy (EIS) study shows the enhanced electron transfer kinetics of the composite compared to HEG modified and bare glassy carbon electrode (GCE). The response of the composite towards dopamine displays a lower oxidation potential of 0.23 V and a high oxidation current. The sensor exhibits linearity from 10 µM to 780 µM with a detection limit of 1 µM. In the presence of nafion, it shows excellent selectivity for coexisting interference species like Ascorbic acid (AA) and Uric acid (UA). The excellent performance of the biosensor can be attributed to large active surface area, enhanced electron transfer kinetics and high catalytic activity of the composite.

Metal-organic chemical vapor deposition of cerium oxide, gallium-indium-oxide, and magnesium oxide thin films: Precursor design, film growth, and film characterization

NASA Astrophysics Data System (ADS)

Edleman, Nikki Lynn

A new class of volatile, low-melting, fluorine-free lanthanide metal-organic chemical vapor deposition (MOCVD) precursors has been developed. The neutral, monomeric cerium, neodymium, gadolinium, and erbium complexes are coordinatively saturated by a versatile, multidentate, ether-functionalized beta-ketoiminate ligand, and complex melting point and volatility characteristics can be tuned by altering the alkyl substituents on the ligand periphery. Direct comparison with lanthanide beta-diketonate complexes reveals that the present precursor class is a superior choice for lanthanide oxide MOCVD. Epitaxial CeO 2 buffer layer films have been grown on (001) YSZ substrates by MOCVD at significantly lower temperatures than previously reported using one of the newly developed cerium precursors. High-quality YBCO films grown on these CeO2 buffer layers by POMBE exhibit very good electrical transport properties. The cerium complex has therefore been explicitly demonstrated to be a stable and volatile precursor and is attractive for low-temperature growth of coated conductor multilayer structures by MOCVD. Gallium-indium-oxide thin films (GaxIn2-xO 3), x = 0.0˜1.1, have been grown by MOCVD using the volatile metal-organic precursors In(dpm)3 and Ga(dpm)3. The films have a homogeneously Ga-substituted, cubic In2O3 microstructure randomly oriented on quartz or heteroepitaxial on (100) YSZ single-crystal substrates. The highest conductivity of the as-grown films is found at x = 0.12. The optical transmission window and absolute transparency of the films rivals or exceeds that of the most transparent conductive oxides known. Reductive annealing results in improved charge transport characteristics with little loss of optical transparency. No significant difference in electrical properties is observed between randomly oriented and heteroepitaxial films, thus arguing that carrier scattering effects at high-angle grain boundaries play a minor role in the film conductivity mechanism

Redox-active cerium oxide nanoparticles protect human dermal fibroblasts from PQ-induced damage.

PubMed

von Montfort, Claudia; Alili, Lirija; Teuber-Hanselmann, Sarah; Brenneisen, Peter

2015-01-01

Recently, it has been published that cerium (Ce) oxide nanoparticles (CNP; nanoceria) are able to downregulate tumor invasion in cancer cell lines. Redox-active CNP exhibit both selective pro-oxidative and antioxidative properties, the first being responsible for impairment of tumor growth and invasion. A non-toxic and even protective effect of CNP in human dermal fibroblasts (HDF) has already been observed. However, the effect on important parameters such as cell death, proliferation and redox state of the cells needs further clarification. Here, we present that nanoceria prevent HDF from reactive oxygen species (ROS)-induced cell death and stimulate proliferation due to the antioxidative property of these particles. Copyright © 2014 The Authors. Published by Elsevier B.V. All rights reserved.

Titanium-doped cerium oxide nanoparticles protect cells from hydrogen peroxide-induced apoptosis

NASA Astrophysics Data System (ADS)

Clark, Andrea; Zhu, Aiping; Petty, Howard R.

2013-12-01

To develop new nanoparticle materials possessing antioxidative capacity with improved physical characteristics, we have studied titanium-doped cerium oxide (CeTiO2) nanoparticles. CeTiO2 nanoparticles had mode diameters in the range of 15-20 nm. These nanoparticles demonstrated catalase activity, and did not promote the activation of hemolytic or cytolytic pathways in living cells. Using surface plasmon resonance-enhanced microscopy, we find that these nanoparticles associate with cells. Transmission electron microscopy studies demonstrated that these nanoparticles accumulate within the vacuolar compartment of cells. Importantly, CeTiO2 nanoparticles decrease hydrogen peroxide-mediated apoptosis of cells as judged by the reduced cleavage of a caspase 3-sensitive label. CeTiO2 nanoparticles may contribute to deflecting tissue damage in a broad spectrum of oxidant-mediated diseases, such as macular degeneration and Alzheimer's disease.

Unusual kinetics of poly(ethylene glycol) oxidation with cerium(IV) ions in sulfuric acid medium and implications for copolymer synthesis.

PubMed

Szymański, Jan K; Temprano-Coleto, Fernando; Pérez-Mercader, Juan

2015-03-14

The cerium(IV)-alcohol couple in an acidic medium is an example of a redox system capable of initiating free radical polymerization. When the alcohol has a polymeric nature, the outcome of such a process is a block copolymer, a member of a class of compounds possessing many useful properties. The most common polymer with a terminal -OH group is poly(ethylene glycol) (PEG); however, the detailed mechanism of its reaction with cerium(IV) remains underexplored. In this paper, we report our findings for this reaction based on spectrophotometric measurements and kinetic modeling. We find that both the reaction order and the net rate constant for the oxidation process depend strongly on the nature of the acidic medium used. In order to account for the experimental observations, we postulate that protonation of PEG decreases its affinity for some of the cerium(IV)-sulfate complexes formed in the system.

Geometry of electromechanically active structures in Gadolinium - doped Cerium oxides

DOE PAGES

Li, Yuanyuan; Kraynis, Olga; Kas, Joshua; ...

2016-05-20

Local distortions from average structure are important in many functional materials, such as electrostrictors or piezoelectrics, and contain clues about their mechanism of work. However, the geometric attributes of these distortions are exceedingly difficult to measure, leading to a gap in knowledge regarding their roles in electromechanical response. This task is particularly challenging in the case of recently reported non-classical electrostriction in Cerium-Gadolinium oxides (CGO), where only a small population of Ce-O bonds that are located near oxygen ion vacancies responds to external electric field. In this study, we used high-energy resolution fluorescence detection (HERFD) technique to collect X-ray absorptionmore » spectra in CGO in situ, with and without an external electric field, coupled with theoretical modeling to characterize three-dimensional geometry of electromechanically active units.« less

Geometry of electromechanically active structures in Gadolinium - doped Cerium oxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Yuanyuan; Zacharowicz, Renee; Frenkel, Anatoly I., E-mail: igor.lubomirsky@weizmann.ac.il, E-mail: anatoly.frenkel@yu.edu

2016-05-15

Local distortions from average structure are important in many functional materials, such as electrostrictors or piezoelectrics, and contain clues about their mechanism of work. However, the geometric attributes of these distortions are exceedingly difficult to measure, leading to a gap in knowledge regarding their roles in electromechanical response. This task is particularly challenging in the case of recently reported non-classical electrostriction in Cerium-Gadolinium oxides (CGO), where only a small population of Ce-O bonds that are located near oxygen ion vacancies responds to external electric field. We used high-energy resolution fluorescence detection (HERFD) technique to collect X-ray absorption spectra in CGOmore » in situ, with and without an external electric field, coupled with theoretical modeling to characterize three-dimensional geometry of electromechanically active units.« less

Bio-sensing applications of cerium oxide nanoparticles: Advantages and disadvantages.

PubMed

Charbgoo, Fahimeh; Ramezani, Mohammad; Darroudi, Majid

2017-10-15

Cerium oxide nanoparticles (CNPs) contain several properties such as catalytic activity, fluorescent quencher and electrochemical, high surface area, and oxygen transfer ability, which have attracted considerable attention in developing high-sensitive biosensors. CNPs can be used as a whole sensor or a part of recognition or transducer element. However, reports have shown that applying these nanoparticles in sensor design could remarkably enhance detection sensitivity. CNP's outstanding properties in biosensors which go from high catalytic activity and surface area to oxygen transfer and fluorescent quenching capabilities are also highlighted. Herein, we discuss the advantages and disadvantages of CNPs-based biosensors that function through various detection modes including colorimetric, electrochemistry, and chemoluminescent regarding the detection of small organic chemicals, metal ions and biomarkers. Copyright © 2017 Elsevier B.V. All rights reserved.

Shifts in oxidation states of cerium oxide nanoparticles detected inside intact hydrated cells and organelles

PubMed Central

Szymanski, Craig J.; Munusamy, Prabhakaran; Mihai, Cosmin; Xie, Yumei; Hu, Dehong; Gilles, Mary K.; Tyliszczak, Tolek; Thevuthasan, Suntharampillai; Baer, Donald R.; Orr, Galya

2015-01-01

Cerium oxide nanoparticles (CNPs) have been shown to induce diverse biological effects, ranging from toxic to beneficial. The beneficial effects have been attributed to the potential antioxidant activity of CNPs via certain redox reactions, depending on their oxidation state or Ce3+/Ce4+ ratio. However, this ratio is strongly dependent on the environment and age of the nanoparticles and it is unclear whether and how the complex intracellular environment impacts this ratio and the possible redox reactions of CNPs. To identify any changes in the oxidation state of CNPs in the intracellular environment and better understand their intracellular reactions, we directly quantified the oxidation states of CNPs outside and inside intact hydrated cells and organelles using correlated scanning transmission x-ray and super resolution fluorescence microscopies. By analyzing hundreds of small CNP aggregates, we detected a shift to a higher Ce3+/Ce4+ ratio in CNPs inside versus outside the cells, indicating a net reduction of CNPs in the intracellular environment. We further found a similar ratio in the cytoplasm and in the lysosomes, indicating that the net reduction occurs earlier in the internalization pathway. Together with oxidative stress and toxicity measurements, our observations identify a net reduction of CNPs in the intracellular environment, which is consistent with their involvement in potentially beneficial oxidation reactions, but also point to interactions that can negatively impact the health of cells. PMID:26056725

Shifts in oxidation states of cerium oxide nanoparticles detected inside intact hydrated cells and organelles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Szymanski, Craig J.; Munusamy, Prabhakaran; Mihai, Cosmin

2015-09-01

Cerium oxide nanoparticles (CNPs) have been shown to induce diverse biological effects, ranging from toxic to beneficial. The beneficial effects have been attributed to the potential antioxidant activity of CNPs via certain redox reactions, depending on their oxidation state or Ce3+/Ce4+ ratio. However, this ratio is strongly dependent on the environment and age of the nanoparticles and it is unclear whether and how the complex intracellular environment impacts this ratio and the possible redox reactions of CNPs. To identify any changes in the oxidation state of CNPs in the intracellular environment and better understand their intracellular reactions, we directly quantifiedmore » the oxidation states of CNPs outside and inside intact hydrated cells and organelles using correlated scanning transmission x-ray and super resolution fluorescence microscopies. By analyzing hundreds of small CNP aggregates, we detected a shift to a higher Ce3+/Ce4+ ratio in CNPs inside versus outside the cells, indicating a net reduction of CNPs in the intracellular environment. We further found a similar ratio in the cytoplasm and in the lysosomes, indicating that the net reduction occurs earlier in the internalization pathway. Together with oxidative stress and toxicity measurements, our observations identify a net reduction of CNPs in the intracellular environment, which is consistent with their involvement in potentially beneficial oxidation reactions, but also point to interactions that can negatively impact the health of cells.« less

The biological effects of subacute inhalation of diesel exhaust following addition of cerium oxide nanoparticles in atherosclerosis-prone mice.

PubMed

Cassee, Flemming R; Campbell, Arezoo; Boere, A John F; McLean, Steven G; Duffin, Rodger; Krystek, Petra; Gosens, Ilse; Miller, Mark R

2012-05-01

Cerium oxide (CeO(2)) nanoparticles improve the burning efficiency of fuel, however, little is known about health impacts of altered emissions from the vehicles. Atherosclerosis-prone apolipoprotein E knockout (ApoE(-/-)) mice were exposed by inhalation to diluted exhaust (1.7 mg/m(3), 20, 60 or 180 min, 5 day/week, for 4 weeks), from an engine using standard diesel fuel (DE) or the same diesel fuel containing 9 ppm cerium oxide nanoparticles (DCeE). Changes in hematological indices, clinical chemistry, atherosclerotic burden, tissue levels of inflammatory cytokines and pathology of the major organs were assessed. Addition of CeO(2) to fuel resulted in a reduction of the number (30%) and surface area (10%) of the particles in the exhaust, whereas the gaseous co-pollutants were increased (6-8%). There was, however, a trend towards an increased size and complexity of the atherosclerotic plaques following DE exposure, which was not evident in the DCeE group. There were no clear signs of altered hematological or pathological changes induced by either treatment. However, levels of proinflammatory cytokines were modulated in a brain region and liver following DCeE exposure. These results imply that addition of CeO(2) nanoparticles to fuel decreases the number of particles in exhaust and may reduce atherosclerotic burden associated with exposure to standard diesel fuel. From the extensive assessment of biological parameters performed, the only concerning effect of cerium addition was a slightly raised level of cytokines in a region of the central nervous system. Overall, the use of cerium as a fuel additive may be a potentially useful way to limit the health effects of vehicle exhaust. However, further testing is required to ensure that such an approach is not associated with a chronic inflammatory response which may eventually cause long-term health effects. Copyright © 2012 Elsevier Inc. All rights reserved.

Atomic layer deposition of cerium oxide for potential use in diesel soot combustion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ivanova, Tatiana V., E-mail: tatiana.ivanova@lut.fi, E-mail: ivanova.tatyana.v@gmail.com; Toivonen, Jenni; Maydannik, Philipp S.

The particulate soot emission from diesel motors has a severe impact on the environment and people's health. The use of catalytic convertors is one of the ways to minimize the emission and decrease the hazard level. In this paper, the activity of cerium oxide for catalytic combustion of diesel soot was studied. Thin films of cerium dioxide were synthesized by atomic layer deposition using tetrakis(2,2,6,6-tetramethyl-3,5-heptanedionato)cerium [Ce(thd){sub 4}] and ozone as precursors. The characteristics of the films were studied as a function of deposition conditions within the reaction temperature range of 180–350 °C. Thickness, crystallinity, elemental composition, and morphology of the CeO{submore » 2} films deposited on Si (100) were characterized by ellipsometry, x-ray diffraction, x-ray photoelectron spectroscopy, atomic force microscopy, and field emission scanning electron microscopy, respectively. The growth rate of CeO{sub 2} was observed to be 0.30 Å/cycle at temperatures up to 250 °C with a slight increase to 0.37 Å/cycle at 300 °C. The effect of CeO{sub 2} films grown on stainless steel foil supports on soot combustion was measured with annealing tests. Based on the analysis of these, in catalytic applications, CeO{sub 2} has been shown to be effective in lowering the soot combustion temperature from 600 °C for the uncoated substrates to 370 °C for the CeO{sub 2} coated ones. It was found that the higher deposition temperatures had a positive effect on the catalyst performance.« less

Switchable Ionic Liquids: An Environmentally Friendly Medium to Synthesise Nanoparticulate Green Rust

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lao, David; Kukkadapu, Ravi; Kovarik, Libor

Under anoxic conditions, a novel nanoparticulate green rust with carbonate (nano GR) was synthesized by addition of methanol to degassed switchable ionic liquid (SWIL) solution comprised of 1-hexanol, diazabicycloundec-7-ene (DBU), CO2 and Fe(C2H3O2)2 (Fe(OAc)2). Variable temperature Mössbauer spectroscopy studies indicated the product to be predominantly GR while TEM-SAED method confirmed it be nanoparticulate in nature. Experiments with and without methanol in the SWIL medium suggest that methanol may be responsible for Fe(II) oxidation to Fe(III) necessary for GR formation. Studies with Ar instead of CO2 trigger gas indicated that CO2 is essential for GR formation. Conditions to generate CO32- anionmore » was most likely provided by basic environment of the medium. The nano GR suspension was very reactive and instantaneously oxidized completely to a reddish-brown precipitate upon exposure to ambient atmosphere. The nature of the oxidized sample is not certain. The oxidized product, however, appears to be a mix of ferric green rust- [GR(CO32-]*; major] and ferrihydrite-like minerals. To our knowledge, this is first report of use of environmentally-friendly SWIL reagents to synthesize very reactive nano GR materials.« less

Nanoparticulate-catalyzed oxygen transfer processes

DOEpatents

Hunt, Andrew T [Atlanta, GA; Breitkopf, Richard C [Dunwoody, GA

2009-12-01

Nanoparticulates of oxygen transfer materials that are oxides of rare earth metals, combinations of rare earth metals, and combinations of transition metals and rare earth metals are used as catalysts in a variety of processes. Unexpectedly large thermal efficiencies are achieved relative to micron sized particulates. Processes that use these catalysts are exemplified in a multistage reactor. The exemplified reactor cracks C6 to C20 hydrocarbons, desulfurizes the hydrocarbon stream and reforms the hydrocarbons in the stream to produce hydrogen. In a first reactor stage the steam and hydrocarbon are passed through particulate mixed rare earth metal oxide to crack larger hydrocarbon molecules. In a second stage, the steam and hydrocarbon are passed through particulate material that desulfurizes the hydrocarbon. In a third stage, the hydrocarbon and steam are passed through a heated, mixed transition metal/rare earth metal oxide to reform the lower hydrocarbons and thereby produce hydrogen. Stages can be alone or combined. Parallel reactors can provide continuous reactant flow. Each of the processes can be carried out individually.

Catalyst support of mixed cerium zirconium titanium oxide, including use and method of making

DOEpatents

Willigan, Rhonda R [Manchester, CT; Vanderspurt, Thomas Henry [Glastonbury, CT; Tulyani, Sonia [Manchester, CT; Radhakrishnan, Rakesh [Vernon, CT; Opalka, Susanne Marie [Glastonbury, CT; Emerson, Sean C [Broad Brook, CT

2011-01-18

A durable catalyst support/catalyst is capable of extended water gas shift operation under conditions of high temperature, pressure, and sulfur levels. The support is a homogeneous, nanocrystalline, mixed metal oxide of at least three metals, the first being cerium, the second being Zr, and/or Hf, and the third importantly being Ti, the three metals comprising at least 80% of the metal constituents of the mixed metal oxide and the Ti being present in a range of 5% to 45% by metals-only atomic percent of the mixed metal oxide. The mixed metal oxide has an average crystallite size less than 6 nm and forms a skeletal structure with pores whose diameters are in the range of 4-9 nm and normally greater than the average crystallite size. The surface area of the skeletal structure per volume of the material of the structure is greater than about 240 m.sup.2/cm.sup.3. The method of making and use are also described.

In-situ surface science studies of the interaction between sulfur dioxide and two-dimensional palladium loaded-cerium/zirconium mixed metal oxide model catalysts

NASA Astrophysics Data System (ADS)

Romano, Esteban Javier

2005-07-01

Cerium and zirconium oxides are important materials in industrial catalysis. Particularly, the great advances attained in the past 30 years in controlling levels of gaseous pollutants released from internal combustion engines can be attributed to the development of catalysts employing these materials. Unfortunately, oxides of sulfur are known threats to the longevity of many catalytic systems by irreversibly interacting with catalytic materials. In this work, polycrystalline cerium-zirconium mixed-metal-oxide (MMO) solid solutions were synthesized. High resolution x-ray photoelectron spectroscopy (XPS) spectral data was collected and examined for revelation of the surface species that form on these metal oxides after in-situ exposures to sulfur dioxide. The model catalysts were exposed to sulfur dioxide using a custom modified in-situ reaction cell and platen heater. The results of this study demonstrate the formation of sulfate and sulfite surface sulfur species. Temperature and compositional dependencies were displayed, with higher temperatures and ceria molar ratios displaying a larger propensity for forming surface sulfur species. In addition to analysis of sulfur photoemission, the photoemission regions of oxygen, zirconium, and cerium were examined for the materials used in this study before and after the aforementioned treatments with sulfur dioxide. The presence of surface hydroxyl groups was observed and metal oxidation state changes were probed to further enhance the understanding of sulfur dioxide adsorption on the synthesized materials. Palladium loaded mixed-metal oxides were synthesized using a unique solid-state methodology to probe the effect of palladium addition on sulfur dioxide adsorption. The addition of palladium to this model system is shown to have a strong effect on the magnitude of adsorption for sulfur dioxide on some material/exposure condition combinations. Ceria/zirconia sulfite and sulfate species are identified on the palladium

Protection from radiation-induced pneumonitis using cerium oxide nanoparticles.

PubMed

Colon, Jimmie; Herrera, Luis; Smith, Joshua; Patil, Swanand; Komanski, Chris; Kupelian, Patrick; Seal, Sudipta; Jenkins, D Wayne; Baker, Cheryl H

2009-06-01

In an effort to combat the harmful effects of radiation exposure, we propose that rare-earth cerium oxide (CeO(2)) nanoparticles (free-radical scavengers) protect normal tissue from radiation-induced damage. Preliminary studies suggest that these nanoparticles may be a therapeutic regenerative nanomedicine that will scavenge reactive oxygen species, which are responsible for radiation-induced cell damage. The effectiveness of CeO(2) nanoparticles in radiation protection in murine models during high-dose radiation exposure is investigated, with the ultimate goal of offering a new approach to radiation protection, using nanotechnology. We show that CeO(2) nanoparticles are well tolerated by live animals, and they prevent the onset of radiation-induced pneumonitis when delivered to live animals exposed to high doses of radiation. In the end, these studies provide a tremendous potential for radioprotection and can lead to significant benefits for the preservation of human health and the quality of life for humans receiving radiation therapy.

Gold-supported cerium-doped NiO x catalysts for water oxidation

DOE PAGES

Ng, Jia Wei Desmond; García-Melchor, Max; Bajdich, Michal; ...

2016-04-29

Here, the development of high-performance catalysts for the oxygen-evolution reaction (OER) is paramount for cost-effective conversion of renewable electricity to fuels and chemicals. Here we report the significant enhancement of the OER activity of electrodeposited NiO x films resulting from the combined effects of using cerium as a dopant and gold as a metal support. This NiCeO x–Au catalyst delivers high OER activity in alkaline media, and is among the most active OER electrocatalysts yet reported. On the basis of experimental observations and theoretical modelling, we ascribe the activity to a combination of electronic, geometric and support effects, where highlymore » active under-coordinated sites at the oxide support interface are modified by the local chemical binding environment and by doping the host Ni oxide with Ce. The NiCeO x–Au catalyst is further demonstrated in a device context by pairing it with a nickel–molybdenum hydrogen evolution catalyst in a water electrolyser, which delivers 50 mA consistently at 1.5 V over 24 h of continuous operation.« less

Cerium oxide-triggered 'one-to-many' catalytic cycling strategy for in situ amplified electronic signal of low-abundance protein.

PubMed

Tang, Juan; Chen, Xian; Zhou, Jun; Li, Qunfang; Chen, Guonan; Tang, Dianping

2013-08-07

Multifunctionalized thionine-modified cerium oxide (Thi-CeO2) nanostructures with redox ability and catalytic activity were designed as the bionanolabels for in situ amplified electronic signal of low-abundance protein (carcinoembryonic antigen, CEA, used as a model) based on a cerium oxide-triggered 'one-to-many' catalytic cycling strategy. Initially, the carried CeO2 nanoparticles autocatalytically hydrolyzed the phosphate ester bond of l-ascorbic acid 2-phosphate (AAP) to produce a new reactant (l-ascorbic acid, AA), then the generated AA was electrochemically oxidized by the assembled thionine on the Thi-CeO2, and the resultant product was then reduced back to AA by the added tris(2-carboxyethy)phosphine (TCEP). The catalytic cycling could be re-triggered by the thionine and TCEP, resulting in amplification of the electrochemical signal. Under the optimized conditions, the electrochemical immunosensor exhibited a wide linear range of 0.1 pg mL(-1) to 80 ng mL(-1) with a low detection limit of 0.08 pg mL(-1) CEA at the 3σblank level. In addition, the methodology was evaluated for the analysis of clinical serum samples, and was in good accordance with values obtained using the commercialized enzyme-linked immunosorbent assay (ELISA) method.

Correlation of Non-proportionality and Scintillation Properties with Cerium Concentration in YAlO 3:Ce

DOE PAGES

Donnald, Samuel B.; Williams, Richard; Melcher, Charles L.; ...

2018-04-19

Cerium doped YAlO3 (YAP:Ce) is an interesting oxide scintillator in that it exhibits a wider range of light yield non-proportionality on a sample-to-sample basis than most other well-known oxide scintillators. In general, most oxide materials, such as BGO and LSO:Ce, are thought to have an intrinsic proportional response that is nearly constant between samples and independent of growth conditions. Since light yield nonproportionality is responsible for degrading the achievable energy resolution of all known scintillators, it is important to understand what contributes to the behavior. In this study, in an attempt to understand if the phenomenon can be affected bymore » growth parameters or by other means, seven samples of YAP:Ce were collected from various sources, and eight samples were grown inhouse using the Czochralski method. Based on optical and scintillation measurement as well as direct measurement of the cerium concentration, it was determined that the light yield proportionality in YAlO3:Ce is strongly related to the cerium concentration. Samples that were found to have a higher relative cerium concentration displayed a more proportional light yield response. In addition, it was determined that samples with a higher cerium concentration also exhibit a faster decay time and an enhanced energy resolution when compared to samples with less cerium. Finally, it was also determined that growth in a reducing atmosphere can effectively suppress a parasitic optical absorption band.« less

Correlation of Non-proportionality and Scintillation Properties with Cerium Concentration in YAlO 3:Ce

DOE Office of Scientific and Technical Information (OSTI.GOV)

Donnald, Samuel B.; Williams, Richard; Melcher, Charles L.

Cerium doped YAlO3 (YAP:Ce) is an interesting oxide scintillator in that it exhibits a wider range of light yield non-proportionality on a sample-to-sample basis than most other well-known oxide scintillators. In general, most oxide materials, such as BGO and LSO:Ce, are thought to have an intrinsic proportional response that is nearly constant between samples and independent of growth conditions. Since light yield nonproportionality is responsible for degrading the achievable energy resolution of all known scintillators, it is important to understand what contributes to the behavior. In this study, in an attempt to understand if the phenomenon can be affected bymore » growth parameters or by other means, seven samples of YAP:Ce were collected from various sources, and eight samples were grown inhouse using the Czochralski method. Based on optical and scintillation measurement as well as direct measurement of the cerium concentration, it was determined that the light yield proportionality in YAlO3:Ce is strongly related to the cerium concentration. Samples that were found to have a higher relative cerium concentration displayed a more proportional light yield response. In addition, it was determined that samples with a higher cerium concentration also exhibit a faster decay time and an enhanced energy resolution when compared to samples with less cerium. Finally, it was also determined that growth in a reducing atmosphere can effectively suppress a parasitic optical absorption band.« less

The biological effects of subacute inhalation of diesel exhaust following addition of cerium oxide nanoparticles in atherosclerosis-prone mice☆

PubMed Central

Cassee, Flemming R.; Campbell, Arezoo; Boere, A. John F.; McLean, Steven G.; Duffin, Rodger; Krystek, Petra; Gosens, Ilse; Miller, Mark R.

2012-01-01

Background Cerium oxide (CeO2) nanoparticles improve the burning efficiency of fuel, however, little is known about health impacts of altered emissions from the vehicles. Methods Atherosclerosis-prone apolipoprotein E knockout (ApoE−/−) mice were exposed by inhalation to diluted exhaust (1.7 mg/m3, 20, 60 or 180 min, 5 day/week, for 4 weeks), from an engine using standard diesel fuel (DE) or the same diesel fuel containing 9 ppm cerium oxide nanoparticles (DCeE). Changes in hematological indices, clinical chemistry, atherosclerotic burden, tissue levels of inflammatory cytokines and pathology of the major organs were assessed. Results Addition of CeO2 to fuel resulted in a reduction of the number (30%) and surface area (10%) of the particles in the exhaust, whereas the gaseous co-pollutants were increased (6–8%). There was, however, a trend towards an increased size and complexity of the atherosclerotic plaques following DE exposure, which was not evident in the DCeE group. There were no clear signs of altered hematological or pathological changes induced by either treatment. However, levels of proinflammatory cytokines were modulated in a brain region and liver following DCeE exposure. Conclusions These results imply that addition of CeO2 nanoparticles to fuel decreases the number of particles in exhaust and may reduce atherosclerotic burden associated with exposure to standard diesel fuel. From the extensive assessment of biological parameters performed, the only concerning effect of cerium addition was a slightly raised level of cytokines in a region of the central nervous system. Overall, the use of cerium as a fuel additive may be a potentially useful way to limit the health effects of vehicle exhaust. However, further testing is required to ensure that such an approach is not associated with a chronic inflammatory response which may eventually cause long-term health effects. PMID:22507957

Catalytic Properties and Biomedical Applications of Cerium Oxide Nanoparticles

PubMed Central

Walkey, Carl; Das, Soumen; Seal, Sudipta; Erlichman, Joseph; Heckman, Karin; Ghibelli, Lina; Traversa, Enrico; McGinnis, James F.; Self, William T.

2014-01-01

Cerium oxide nanoparticles (Nanoceria) have shown promise as catalytic antioxidants in the test tube, cell culture models and animal models of disease. However given the reactivity that is well established at the surface of these nanoparticles, the biological utilization of Nanoceria as a therapeutic still poses many challenges. Moreover the form that these particles take in a biological environment, such as the changes that can occur due to a protein corona, are not well established. This review aims to summarize the existing literature on biological use of Nanoceria, and to raise questions about what further study is needed to apply this interesting catalytic material to biomedical applications. These questions include: 1) How does preparation, exposure dose, route and experimental model influence the reported effects of Nanoceria in animal studies? 2) What are the considerations to develop Nanoceria as a therapeutic agent in regards to these parameters? 3) What biological targets of reactive oxygen species (ROS) and reactive nitrogen species (RNS) are relevant to this targeting, and how do these properties also influence the safety of these nanomaterials? PMID:26207185

Generation of Oxidants From the Reaction of Nanoparticulate Zero-Valent Iron and Oxygen for the use in Contaminant Remediation

NASA Astrophysics Data System (ADS)

Keenan, C. R.; Lee, C.; Sedlak, D. L.

2007-12-01

The reaction of zero-valent iron (ZVI) with oxygen can lead to the formation of oxidants, which may be used to transform recalcitrant contaminants including non-polar organics and certain metals. Nanoparticulate iron might provide a practical mechanism of remediating oxygen-containing groundwater and contaminated soil. To gain insight into the reaction mechanism and to quantify the yield of oxidants, experiments were performed with model organic compounds in the presence of nanoparticulate zero-valent iron and oxygen. At pH values below 5, ZVI nanoparticles were oxidized within 30 minutes with a stoichiometry of approximately two Fe0 oxidized per O2 consumed. Using the oxidation of methanol and ethanol to formaldehyde and acetaldehyde, respectively, we found that less than 2% of the consumed oxygen was converted to reactive oxidants under acidic conditions. The yield of aldehydes increased with pH up to pH 7, with maximum oxidant yields of around 5% relative to the mass of ZVI added. The increase of aldehyde yield with pH was attributable to changes in the processes responsible for oxidant production. At pH values below 5, the corrosion of ZVI by oxygen produces hydrogen peroxide, which subsequently reacts with ferrous iron [Fe(II)] via the Fenton reaction. At higher pH values, the aldehydes are produced when Fe(II), the initial product of ZVI oxidation, reacts with oxygen. The decrease in oxidant yield at pH values above 7 may be attributable to precipitation of Fe(II). The oxidation of benzoic acid and 2-propanol to para-hydroxybenzoic acid and acetone, respectively, followed a very different trend compared to the primary alcohols. In both cases, the highest product yields (approximately 2% with respect to ZVI added) were observed at pH 3. Yields decreased with increasing pH, with no oxidized product detected at neutral pH. These results suggest that two different oxidants may be produced by the system: hydroxyl radical (OH-·) at acidic pH and a more selective

DFT study of the active site of the XoxF-type natural, cerium-dependent methanol dehydrogenase enzyme.

PubMed

Bogart, Justin A; Lewis, Andrew J; Schelter, Eric J

2015-01-19

Rare-earth metal cations have recently been demonstrated to be essential co-factors for the growth of the methanotrophic bacterium Methylacidiphilum fumariolicum SolV. A crystal structure of the rare-earth-dependent methanol dehydrogenase (MDH) includes a cerium cation in the active site. Herein, the Ce-MDH active site has been analyzed through DFT calculations. The results show the stability of the Ce(III)-pyrroloquinoline quinone (PQQ) semiquinone configuration. Calculations on the active oxidized form of this complex indicate a 0.81 eV stabilization of the PQQ(0) LUMO at cerium versus calcium, supporting the observation that the cerium cation in the active site confers a competitive advantage to Methylacidiphilum fumariolicum SolV. Using reported aqueous electrochemical data, a semi-empirical correlation was established based on cerium(IV/III) redox potentials. The correlation allowed estimation of the cerium oxidation potential of +1.35 V versus saturated calomel electrode (SCE) in the active site. The results are expected to guide the design of functional model complexes and alcohol-oxidation catalysts based on lanthanide complexes of biologically relevant quinones. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Virus Removal by Biogenic Cerium

DOE Office of Scientific and Technical Information (OSTI.GOV)

De Gusseme, B.; Du Laing, G; Hennebel, T

2010-01-01

The rare earth element cerium has been known to exert antifungal and antibacterial properties in the oxidation states +III and +IV. This study reports on an innovative strategy for virus removal in drinking water by the combination of Ce(III) on a bacterial carrier matrix. The biogenic cerium (bio-Ce) was produced by addition of aqueous Ce(III) to actively growing cultures of either freshwater manganese-oxidizing bacteria (MOB) Leptothrix discophora or Pseudomonas putida MnB29. X-ray absorption spectroscopy results indicated that Ce remained in its trivalent state on the bacterial surface. The spectra were consistent with Ce(III) ions associated with the phosphoryl groups ofmore » the bacterial cell wall. In disinfection assays using a bacteriophage as model, it was demonstrated that bio-Ce exhibited antiviral properties. A 4.4 log decrease of the phage was observed after 2 h of contact with 50 mg L{sup -1} bio-Ce. Given the fact that virus removal with 50 mg L{sup -1} Ce(III) as CeNO{sub 3} was lower, the presence of the bacterial carrier matrix in bio-Ce significantly enhanced virus removal.« less

Enzyme-free Detection of Hydrogen Peroxide from Cerium Oxide Nanoparticles Immobilized on Poly(4-vinylpyridine) Self-Assembled Monolayers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gaynor, James D.; Karakoti, Ajay S.; Inerbaev, Talgat

2013-05-02

A single layer of oxygen-deficient cerium oxide nanoparticles (CNPs) are immobilized on microscopic glass slide using poly(4-vinylpyridine) (PVP) self-assembled monolayers (SAMs). A specific colorimetric property of CNPs when reacted with hydrogen peroxide allows for the direct, single-step peroxide detection which can be used in medical diagnosis and explosives detection. Multiple PVP-CNP immobilized layers improve sensitivity of detection and the sensor can be regenerated for reuse.

Soft Chemical Fabrication of Iron-Based Thin Film Electrocatalyst for Water Oxidation under Neutral pH and Structure-Activity Tuning by Cerium Incorporation.

PubMed

Saha, Jony; Radhakrishnan, T P

2017-08-29

Design of electrocatalysts for the fundamentally important oxygen evolution reaction can be greatly aided by systematic structure-activity tuning via composition variation. We have explored the iron-cerium system as they are the most abundant transition and rare earth metals, and also due to the mutualistic impact of their size and electronic attributes that can induce critical changes in the structure and electrochemical activity. Submicrometer thick films of a series of Fe(III)-Ce(III) phosphate(oxyhydroxide) (FeCePH) are fabricated using a soft chemical strategy involving surfactant-aided assembly, spin-coating, and mild thermal annealing. FT-IR, Raman, and X-ray photoelectron spectroscopies, chemical analysis, X-ray diffraction, and electron microscopy reveal the systematic structural, electronic, and morphological variation, on tuning the iron-cerium composition. Nitrogen adsorption-desorption studies show the surface area increasing and pore size distribution shrinking with the cerium content, indicating its structure-directing role. The electrocatalysis of water oxidation by FeCePH films on FTO-coated glass is studied in neutral pH conditions. The overpotential and Tafel slope decrease with increasing cerium content, reaching minima at the optimal Fe:Ce ratio of 1:0.5; the turnover frequency shows a corresponding increase and maximum. The trends are explained on the basis of the structural changes in the films, and the coupling of Ce 3+ /Ce 4+ with Fe 3+ /Fe 4+ that leads to active state regeneration. This study presents a rational strategy to tune the efficiency of easily fabricated transition metal-based electrocatalyst thin films through rare earth metal incorporation; it should prove useful in the design of cost-effective catalysts for water oxidation.

Threshold Ionization and Spin-Orbit Coupling of Cerium Monoxide

NASA Astrophysics Data System (ADS)

Cao, Wenjin; Zhang, Yuchen; Wu, Lu; Yang, Dong-Sheng

2017-06-01

Cerium oxides are widely used in heterogeneous catalysis due to their ability to switch between different oxidation states. We report here the mass-analyzed threshold ionization (MATI) spectroscopy of cerium monoxide (CeO) produced by laser ablating a Ce rod in a molecular beam source. The MATI spectrum in the range of 40000-45000 \\wn exhibits several band systems with similar vibrational progressions. The strongest band is at 43015 (5) \\wn, which can be assigned as the adiabatic ionization energy of the neutral species. The spectrum also shows Ce-O stretching frequencies of 817 and 890 \\wn in the neutral and ion states, respectively. By comparing with spin-orbit coupled multireference quasi-degenerate perturbation theory (SO-MCQDPT) calculations, the observed band systems are assigned to transitions from various low-energy spin-orbit levels of the neutral oxide to the two lowest spin-orbit levels of the corresponding ion. The current work will also be compared with previous experimental and computational studies on the neutral species.

Concepts and practices used to develop functional PLGA-based nanoparticulate systems.

PubMed

Sah, Hongkee; Thoma, Laura A; Desu, Hari R; Sah, Edel; Wood, George C

2013-01-01

The functionality of bare polylactide-co-glycolide (PLGA) nanoparticles is limited to drug depot or drug solubilization in their hard cores. They have inherent weaknesses as a drug-delivery system. For instance, when administered intravenously, the nanoparticles undergo rapid clearance from systemic circulation before reaching the site of action. Furthermore, plain PLGA nanoparticles cannot distinguish between different cell types. Recent research shows that surface functionalization of nanoparticles and development of new nanoparticulate dosage forms help overcome these delivery challenges and improve in vivo performance. Immense research efforts have propelled the development of diverse functional PLGA-based nanoparticulate delivery systems. Representative examples include PEGylated micelles/nanoparticles (PEG, polyethylene glycol), polyplexes, polymersomes, core-shell-type lipid-PLGA hybrids, cell-PLGA hybrids, receptor-specific ligand-PLGA conjugates, and theranostics. Each PLGA-based nanoparticulate dosage form has specific features that distinguish it from other nanoparticulate systems. This review focuses on fundamental concepts and practices that are used in the development of various functional nanoparticulate dosage forms. We describe how the attributes of these functional nanoparticulate forms might contribute to achievement of desired therapeutic effects that are not attainable using conventional therapies. Functional PLGA-based nanoparticulate systems are expected to deliver chemotherapeutic, diagnostic, and imaging agents in a highly selective and effective manner.

Concepts and practices used to develop functional PLGA-based nanoparticulate systems

PubMed Central

Sah, Hongkee; Thoma, Laura A; Desu, Hari R; Sah, Edel; Wood, George C

2013-01-01

The functionality of bare polylactide-co-glycolide (PLGA) nanoparticles is limited to drug depot or drug solubilization in their hard cores. They have inherent weaknesses as a drug-delivery system. For instance, when administered intravenously, the nanoparticles undergo rapid clearance from systemic circulation before reaching the site of action. Furthermore, plain PLGA nanoparticles cannot distinguish between different cell types. Recent research shows that surface functionalization of nanoparticles and development of new nanoparticulate dosage forms help overcome these delivery challenges and improve in vivo performance. Immense research efforts have propelled the development of diverse functional PLGA-based nanoparticulate delivery systems. Representative examples include PEGylated micelles/nanoparticles (PEG, polyethylene glycol), polyplexes, polymersomes, core-shell–type lipid-PLGA hybrids, cell-PLGA hybrids, receptor-specific ligand-PLGA conjugates, and theranostics. Each PLGA-based nanoparticulate dosage form has specific features that distinguish it from other nanoparticulate systems. This review focuses on fundamental concepts and practices that are used in the development of various functional nanoparticulate dosage forms. We describe how the attributes of these functional nanoparticulate forms might contribute to achievement of desired therapeutic effects that are not attainable using conventional therapies. Functional PLGA-based nanoparticulate systems are expected to deliver chemotherapeutic, diagnostic, and imaging agents in a highly selective and effective manner. PMID:23459088

Cyclic thermochemical process for producing hydrogen using cerium-titanium compounds

DOEpatents

Bamberger, C.E.

A thermochemical cyclic process for producing hydrogen employs the reaction between ceric oxide and titanium dioxide to form cerium titanate and oxygen. The titanate is treated with an alkali metal hydroxide to give hydrogen, ceric oxide, an alkali metal titanate and water. Alkali metal titanate and water are boiled to give titanium dioxide which, along with ceric oxide, is recycled.

Cyclic thermochemical process for producing hydrogen using cerium-titanium compounds

DOEpatents

Bamberger, Carlos E.

1980-01-01

A thermochemical cyclic process for producing hydrogen employs the reaction between ceric oxide and titanium dioxide to form cerium titanate and oxygen. The titanate is treated with an alkali metal hydroxide to give hydrogen, ceric oxide, an alkali metal titanate and water. Alkali metal titanate and water are boiled to give titanium dioxide which, along with ceric oxide, is recycled.

Thermodynamic properties of gaseous cerium molybdates and tungstates studied by Knudsen effusion mass spectrometry.

PubMed

Shugurov, S M; Panin, A I; Lopatin, S I

2018-06-21

CeO 2 -WO 3 and CeO 2 -MoO 3 catalysts have shown excellent performance in the selective reduction of NO x by ammonia (NH 3 -selective catalytic reduction) over a wide temperature range. Strong interaction between CeO 2 and WO 3 or MoO 3 might be the dominant reason for the high activity of these mixed oxides. Studies of ceria-containing gaseous salts involve considerable experimental difficulties, since the transition of such salts to vapor requires high temperatures. To predict the possibility of the existence of gaseous associates formed by cerium and molybdenum (tungsten) oxides it is important to know their thermodynamic characteristics. Until the present investigation, gaseous cerium oxyacid salts were unknown. Knudsen effusion mass spectrometry was used to determine the partial pressures of vapor species and the equilibrium constants of gas-phase reactions, as well as the formation and atomization enthalpies of gaseous cerium molybdates and tungstates. CeO 2 was evaporated from molybdenum and tungsten effusion cells containing gold metal as a pressure standard. A theoretical study of gaseous cerium gaseous molybdates and tungstates was performed by several quantum chemical methods. In the temperature range 2050-2400 K, CeO, CeO 2 , XO 2 , XO 3 , CeWO 3 , CeXO 4 , CeXO 5 (X = Mo, W) and CeMo 2 O 7 were found to be the main vapor species over the CeO 2 - Mo (W) systems. On the basis of the equilibrium constants of the gaseous reactions, the standard formation enthalpies of gaseous CeWO 3 , CeXO 4 , CeXO 5 (X = Mo, W) and CeMo 2 O 7 at 298 K were determined. Energetically favorable structures of gaseous cerium salts were found and vibrational frequencies were evaluated in the harmonic approximation. The thermal stability of gaseous cerium oxyacid salts was confirmed by high-temperature mass spectrometry. Reaction enthalpies of the gaseous cerium molybdates and tungstates from gaseous cerium, molybdenum and tungsten oxides were evaluated theoretically and the

Arsenic sorption to nanoparticulate mackinawite (FeS): An examination of phosphate competition.

PubMed

Niazi, Nabeel Khan; Burton, Edward D

2016-11-01

Nanoparticulate mackinawite (FeS) can be an important host-phase for arsenic (As) in sulfidic, subsurface environments. Although not previously investigated, phosphate (PO 4 3- ) may compete with As for available sorption sites on FeS, thereby enhancing As mobility in FeS-bearing soils, sediments and groundwater systems. In this study, we examine the effect of PO 4 3- on sorption of arsenate (As(V)) and arsenite (As(III)) to nanoparticulate FeS at pH 6, 7 and 9. Results show that PO 4 3- (at 0.01-1.0 mM P) did not significantly affect sorption of either As(V) or As(III) to nanoparticulate FeS at initial aqueous As concentrations ranging from 0.01 to 1.0 mM. At pH 9 and 7, sorption of both As(III) and As(V) to nanoparticulate FeS was similar, with distribution coefficient (K d ) values spanning 0.76-15 L g -1 (which corresponds to removal of 87-98% of initial aqueous As(III) and As(V) concentrations). Conversely, at pH 6, the sorption of As(III) was characterized by substantially higher K d values (6.3-93.4 L g -1 ) than those for As(V) (K d  = 0.21-0.96 L g -1 ). Arsenic K-edge X-ray absorption near edge structure (XANES) spectroscopy indicated that up to 52% of the added As(V) was reduced to As(III) in As(V) sorption experiments, as well as the formation of minor amounts of an As 2 S 3 -like species. In As(III) sorption experiments, XANES spectroscopy also demonstrated the formation of an As 2 S 3 -like species and the partial oxidation of As(III) to As(V) (despite the strictly O 2 -free experimental conditions). Overall, the XANES data indicate that As sorption to nanoparticulate FeS involves several redox transformations and various sorbed species, which display a complex dependency on pH and As loading but that are not influenced by the co-occurrence of PO 4 3- . This study shows that nanoparticulate FeS can help to immobilize As(III) and As(V) in sulfidic subsurface environments where As co-exists with PO 4 3- . Copyright © 2016 Elsevier Ltd. All

Cerium oxide nanoparticles protect rodent lungs from hypobaric hypoxia-induced oxidative stress and inflammation.

PubMed

Arya, Aditya; Sethy, Niroj Kumar; Singh, Sushil Kumar; Das, Mainak; Bhargava, Kalpana

2013-01-01

Cerium oxide nanoparticles (nanoceria) are effective at quenching reactive oxygen species (ROS) in cell culture and animal models. Although nanoceria reportedly deposit in lungs, their efficacy in conferring lung protection during oxidative stress remains unexplored. Thus, the study evaluated the protective efficacy of nanoceria in rat lung tissue during hypobaric hypoxia. A total of 48 animals were randomly divided into four equal groups (control [C], nanoceria treated [T], hypoxia [H], and nanoceria treated plus hypoxia [T+H]). Animals were injected intraperitoneally with either a dose of 0.5 μg/kg body weight/week of nanoceria (T and T+H groups) or vehicle (C and H groups) for 5 weeks. After the final dose, H and T+H animals were challenged with hypobaric hypoxia, while C and T animals were maintained at normoxia. Lungs were isolated and homogenate was obtained for analysis of ROS, lipid peroxidation, glutathione, protein carbonylation, and 4-hydroxynonenal-adduct formation. Plasma was used for estimating major inflammatory cytokines using enzyme-linked immunosorbent assay. Intact lung tissues were fixed and both transmission electron microscopy and histopathological examinations were carried out separately for detecting internalization of nanoparticles as well as altered lung morphology. Spherical nanoceria of 7-10 nm diameter were synthesized using a microemulsion method, and the lung protective efficacy of the nanoceria evaluated during hypobaric hypoxia. With repeated intraperitoneal injections of low micromole concentration, we successfully localized the nanoceria in rodent lung without any inflammatory response. The lung-deposited nanoceria limited ROS formation, lipid peroxidation, and glutathione oxidation, and prevented oxidative protein modifications like nitration and carbonyl formation during hypobaric hypoxia. We also observed reduced lung inflammation in the nanoceria-injected lungs, supporting the anti-inflammatory properties of nanoceria

One-step synthesis and characterizations of cerium oxide nanoparticles in an ambient temperature via Co-precipitation method

NASA Astrophysics Data System (ADS)

Pujar, Malatesh S.; Hunagund, Shirajahammad M.; Desai, Vani R.; Patil, Shivaprasadgouda; Sidarai, Ashok H.

2018-04-01

We report the simple Co-precipitation method for the synthesis of Cerium oxide (CeO2) nanoparticles (NPs) in an ambient temperature. We have taken the Cerium (III) nitrate hexahydrate (Ce(NO3)3.6H2O) and Sodium hydroxide (NaOH) as the precursors. The obtained NPs were analyzed using the UV-Vis spectrophotometer, Fourier transform infrared spectroscopy (FT-IR) and X-ray diffraction (XRD). The obtained results signify that UV-Vis spectrum exhibited a well-defined absorption peak at 274 nm and the estimated energy gap (Eg) is 4.05 eV. The FT-IR analysis provides the supporting evidence for the presence of bonding of O-H, nitrates, alcohols and O-Ce-O vibrations. The XRD result reveals that the synthesized CeO2 NPs was crystallite with cubic phase structure and the estimated average crystallite size of CeO2 NPs using Scherer's and W-H method was significantly different due to their assumptions. Further, it is purposed to study their photocatalytic biological activities.

Effect of the Cerium Oxide (CeO2) on the Structural and Electrochemical Properties of the LaNi5Ce Metal Hydride Anode

NASA Astrophysics Data System (ADS)

Utami Hapsari, Ade; Zulfia, Anne; Raharjo, Jarot; Agustanhakri

2017-07-01

One of negative electrode, AB5-type alloy electrodes, have been extensively studied and applied in rechargeable Ni-MH batteries due to their excellent electrochemical characteristics. Some researchers have found that addition of rare earth oxides (La, Ce, Pr, Er, Tm, Yb) to AB5-type alloy (MH) electrode improves battery performance significantly. Cerium Oxide (CeO2) is a light rare earth oxide is widely obtained from the processing of tailings in mining activities. During this time, there is still little data for research applications of cerium oxide for electrode materials. In this paper, the effects of adding CeO2 on the performance metal hydride electrode were investigated. In order to study the effects of CeO2 on the performance of anode material, 1%, 2%, and 3% of weight ratio CeO2 was mixed to LaNi5 as an negative electrode. The powder mixtures were mechanically milled at a speed of rpm 240 for 2 hours using ball mill. The powder mixtures were characterized by X-Ray Diffraction (XRD) and Scanning Electron Microscope (SEM). Electrochemical characteristics were measured using electrochemical impedance spectroscopy (EIS). The powder mixing showed the presence of Ce atom substitution into LaNi5 structures that affect the electrochemical properties of the material. The addition of cerium oxide at LaNi5 increase of the value of impedance. However, the addition of the value of impedance at 1% CeO2 is not significant when compared with the addition of 2% and 3% CeO2 that actually make the electrochemical properties of LaNi5 worst. Although the addition of 1% CeO2 also slightly increases the impedance value of LaNi5, but the addition of 1% CeO2 showed increase the corrosion resistance than without the addition of CeO2 and the addition of 2% and 3% CeO2.

Brain suppression of AP-1 by inhaled diesel exhaust and reversal by cerium oxide nanoparticles.

PubMed

Lung, Shyang; Cassee, Flemming R; Gosens, Ilse; Campbell, Arezoo

2014-08-01

One of the uses of cerium oxide nanoparticles (nanoceria, CeO2) is as a diesel fuel additive to improve fuel efficiency. Gene/environment interactions are important determinants in the etiology of age-related disorders. Thus, it is possible that individuals on high-fat diet and genetic predisposition to vascular disease may be more vulnerable to the adverse health effects of particle exposure. The aim of this pilot study was to test the hypothesis that inhalation of diesel exhaust (DE) or diesel exhaust-containing cerium oxide nanoparticles (DCeE) induces stress in the brain of a susceptible animal model. Atherosclerotic prone, apolipoprotein E knockout (ApoE(-/-)) mice fed a high-fat diet, were exposed by inhalation to purified air (control), DE or DCeE. The stress-responsive transcription factor, activator protein-1 (AP-1), was significantly decreased in the cortical and subcortical fraction of the brain after DE exposure. The addition of nanoceria to the diesel fuel reversed this effect. The activation of another stress-related transcription factor (NF-κB) was not inhibited. AP-1 is composed of complexes of the Jun and/or Fos family of proteins. Exposure to DCeE caused c-Jun activation and this may be a mechanism by which addition of nanoceria to the fuel reversed the effect of DE exposure on AP-1 activation. This pilot study demonstrates that exposure to DE does impact the brain and addition of nanoceria may be protective. However, more extensive studies are necessary to determine how DE induced reduction of AP-1 activity and compensation by nanoceria impacts normal function of the brain.

Inhaled Diesel Emissions Generated with Cerium Oxide Nanoparticle Fuel Additive Induce Adverse Pulmonary and Systemic Effects

PubMed Central

Snow, Samantha J.; McGee, John; Miller, Desinia B.; Bass, Virginia; Schladweiler, Mette C.; Thomas, Ronald F.; Krantz, Todd; King, Charly; Ledbetter, Allen D.; Richards, Judy; Weinstein, Jason P.; Conner, Teri; Willis, Robert; Linak, William P.; Nash, David; Wood, Charles E.; Elmore, Susan A.; Morrison, James P.; Johnson, Crystal L.; Gilmour, Matthew Ian; Kodavanti, Urmila P.

2014-01-01

Diesel exhaust (DE) exposure induces adverse cardiopulmonary effects. Cerium oxide nanoparticles added to diesel fuel (DECe) increases fuel burning efficiency but leads to altered emission characteristics and potentially altered health effects. Here, we evaluated whether DECe results in greater adverse pulmonary effects compared with DE. Male Sprague Dawley rats were exposed to filtered air, DE, or DECe for 5 h/day for 2 days. N-acetyl glucosaminidase activity was increased in bronchial alveolar lavage fluid (BALF) of rats exposed to DECe but not DE. There were also marginal but insignificant increases in several other lung injury biomarkers in both exposure groups (DECe > DE for all). To further characterize DECe toxicity, rats in a second study were exposed to filtered air or DECe for 5 h/day for 2 days or 4 weeks. Tissue analysis indicated a concentration- and time-dependent accumulation of lung and liver cerium followed by a delayed clearance. The gas-phase and high concentration of DECe increased lung inflammation at the 2-day time point, indicating that gas-phase components, in addition to particles, contribute to pulmonary toxicity. This effect was reduced at 4 weeks except for a sustained increase in BALF γ-glutamyl transferase activity. Histopathology and transmission electron microscopy revealed increased alveolar septa thickness due to edema and increased numbers of pigmented macrophages after DECe exposure. Collectively, these findings indicate that DECe induces more adverse pulmonary effects on a mass basis than DE. In addition, lung accumulation of cerium, systemic translocation to the liver, and delayed clearance are added concerns to existing health effects of DECe. PMID:25239632

Evaluation of the role of oxidative stress, inflammation and apoptosis in the pulmonary and the hepatic toxicity induced by cerium oxide nanoparticles following intratracheal instillation in male Sprague-Dawley rats

NASA Astrophysics Data System (ADS)

Nalabotu, Siva Krishna

The field of nanotechnology is rapidly progressing with potential applications in the automobile, healthcare, electronics, cosmetics, textiles, information technology, and environmental sectors. Nanomaterials are engineered structures with at least one dimension of 100 nanometers or less. With increased applications of nanotechnology, there are increased chances of exposure to manufactured nanomaterials. Recent reports on the toxicity of engineered nanomaterials have given scientific and regulatory agencies concerns over the safety of nanomaterials. Specifically, the Organization for Economic Co-operation and Development (OECD) has identified fourteen high priority nanomaterials for study. Cerium oxide (CeO2) nanoparticles are one among the high priority group. Recent data suggest that CeO2 nanoparticles may be toxic to lung cell lines in vitro and lung tissues in vivo. Other work has proposed that oxidative stress may play an important role in the toxicity; however, the exact mechanism of the toxicity, has to our knowledge, not been investigated. Similarly, it is not clear whether CeO2 nanoparticles exhibit systemic toxicity. Here, we investigate whether pulmonary exposure to CeO2 nanoparticles is associated with oxidative stress, inflammation and apoptosis in the lungs and liver of adult male Sprague-Dawley rats. Our data suggest that the intratracheal instillation of CeO2 nanoparticles can cause an increased lung weight to body weight ratio. Changes in lung weights were associated with the accumulation of cerium in the lungs, elevations in serum inflammatory markers, an increased Bax to Bcl-2 ratio, elevated caspase-3 protein levels, increased phosphorylation of p38-MAPK and diminished phosphorylation of ERK1/2-MAPK. Our findings from the study evaluating the possible translocation of CeO2 nanoparticles from the lungs to the liver suggest that CeO 2 nanoparticle exposure was associated with increased liver ceria levels, elevations in serum alanine transaminase

Cerium oxide nanoparticle uptake kinetics from the gas-phase into lung cells in vitro is transport limited.

PubMed

Raemy, David O; Limbach, Ludwig K; Rothen-Rutishauser, Barbara; Grass, Robert N; Gehr, Peter; Birbaum, Karin; Brandenberger, Christina; Günther, Detlef; Stark, Wendelin J

2011-04-01

Nowadays, aerosol processes are widely used for the manufacture of nanoparticles (NPs), creating an increased occupational exposure risk of workers, laboratory personnel and scientists to airborne particles. There is evidence that possible adverse effects are linked with the accumulation of NPs in target cells, pointing out the importance of understanding the kinetics of particle internalization. In this context, the uptake kinetics of representative airborne NPs over 30 min and their internalization after 24 h post-exposure were investigated by the use of a recently established exposure system. This system combines the production of aerosolized cerium oxide (CeO(2)) NPs by flame spray synthesis with its simultaneous particle deposition from the gas-phase onto A549 lung cells, cultivated at the air-liquid interface. Particle uptake was quantified by mass spectrometry after several exposure times (0, 5, 10, 20 and 30 min). Over 35% of the deposited mass was found internalized after 10 min exposure, a value that increased to 60% after 30 min exposure. Following an additional 24 h post-incubation, a time span, after which adverse biological effects were observed in previous experiments, over 80% of total CeO(2) could be detected intracellularly. On the ultrastructural level, focal cerium aggregates were present on the apical surface of A549 cells and could also be localized intracellularly in vesicular structures. The uptake behaviour of aerosolized CeO(2) is in line with observations on cerium suspensions, where particle mass transport was identified as the rate-limiting factor for NP internalization. Copyright © 2010 Elsevier B.V. All rights reserved.

Thermoelectric properties of cerium monopnictides

NASA Technical Reports Server (NTRS)

Danielson, L. R.; Alexander, M. N.; Wood, C.; Lockwood, R. A.; Vandersande, J. W.

1987-01-01

Several cerium pnictides have been synthesized from the pure elements and hot pressed into test samples. Measurements of Seebeck coefficients and electrical resistivities were performed on these samples from room temperature to 1000 C. Cerium arsenide and cerium antimonide are n-type; cerium nitride changes from p-type to n-type conduction at 800 C. The materials are semimetals with resistivities below 1 mohm/cm. Cerium arsenide is the most favorable of the pnictides studied for high-temperature thermoelectric energy conversion, with an average power factor of 15 microW/cm K sq from 500 to 1000 C.

Effects of Cerium Oxide Nanoparticles on the Growth of Keratinocytes, Fibroblasts and Vascular Endothelial Cells in Cutaneous Wound Healing

PubMed Central

Chigurupati, Srinivasulu; Mughal, Mohamed R.; Okun, Eitan; Das, Soumen; Kumar, Amit; McCaffery, Michael; Seal, Sudipta; Mattson, Mark P.

2012-01-01

Rapid and effective wound healing requires a coordinated cellular response involving fibroblasts, keratinocytes and vascular endothelial cells (VECs). Impaired wound healing can result in multiple adverse health outcomes and, although antibiotics can forestall infection, treatments that accelerate wound healing are lacking. We now report that topical application of water soluble cerium oxide nanoparticles (Nanoceria) accelerates the healing of full-thickness dermal wounds in mice by a mechanism that involves enhancement of the proliferation and migration of fibroblasts, keratinocytes and VECs. The Nanoceria penetrated into the wound tissue and reduced oxidative damage to cellular membranes and proteins, suggesting a therapeutic potential for topical treatment of wounds with antioxidant nanoparticles. PMID:23266256

PLUTONIUM-CERIUM ALLOY

DOEpatents

Coffinberry, A.S.

1959-01-01

An alloy is presented for use as a reactor fuel. The binary alloy consists essentially of from about 5 to 90 atomic per cent cerium and the balance being plutonium. A complete phase diagram for the cerium--plutonium system is given.

Nanostructured cerium oxide: preparation, characterization, and application in energy and environmental catalysis

DOE PAGES

Tang, Wen-Xiang; Gao, Pu-Xian

2016-11-10

Nanostructured cerium oxide (CeO 2) with outstanding physical and chemical properties has attracted extensive interests over the past few decades in environment and energy-related applications. With controllable synthesis of nanostructured CeO 2, much more features were technologically brought out from defect chemistry to structure-derived effects. This paper highlights recent progress on the synthesis and characterization of nanostructured ceria-based materials as well as the traditional and new applications. Specifically, several typical applications based on the desired ceria nanostructures are focused to showcase the importance of nanostructure-derived effects. Moreover, some challenges and perspectives on the nanostructured ceria are presented, such as defectsmore » controlling and retainment, scale-up fabrication, and monolithic devices. Hopefully, this paper can provide an improved understanding of nanostructured CeO 2 and offer new opportunities to promote the further research and applications in the future.« less

Potential for recovery of cerium contained in automotive catalytic converters

USGS Publications Warehouse

Bleiwas, Donald I.

2013-01-01

Catalytic converters (CATCONs) are required by Federal law to be installed in nearly all gasoline- and diesel-fueled onroad vehicles used in the United States. About 85 percent of the light-duty vehicles and trucks manufactured worldwide are equipped with CATCONs. Portions of the CATCONs (called monoliths) are recycled for their platinum-group metal (PGM) content and for the value of the stainless steel they contain. The cerium contained in the monoliths, however, is disposed of along with the slag produced from the recycling process. Although there is some smelter capacity in the United States to treat the monoliths in order to recover the PGMs, a great percentage of monoliths is exported to Europe and South Africa for recycling, and a lesser amount is exported to Japan. There is presently no commercial-scale capacity in place domestically to recover cerium from the monoliths. Recycling of cerium or cerium compounds from the monoliths could help ensure against possible global supply shortages by increasing the amount that is available in the supply chain as well as the number and geographic distribution of the suppliers. It could also reduce the amount of material that goes into landfills. Also, the additional supply could lower the price of the commodity. This report analyzes how much cerium oxide is contained in CATCONs and how much could be recovered from used CATCONs.

Bioinspired Nanoparticulate Medical Glues for Minimally Invasive Tissue Repair.

PubMed

Lee, Yuhan; Xu, Chenjie; Sebastin, Monisha; Lee, Albert; Holwell, Nathan; Xu, Calvin; Miranda Nieves, David; Mu, Luye; Langer, Robert S; Lin, Charles; Karp, Jeffrey M

2015-11-18

Delivery of tissue glues through small-bore needles or trocars is critical for sealing holes, affixing medical devices, or attaching tissues together during minimally invasive surgeries. Inspired by the granule-packaged glue delivery system of sandcastle worms, a nanoparticulate formulation of a viscous hydrophobic light-activated adhesive based on poly(glycerol sebacate)-acrylate is developed. Negatively charged alginate is used to stabilize the nanoparticulate surface to significantly reduce its viscosity and to maximize injectability through small-bore needles. The nanoparticulate glues can be concentrated to ≈30 w/v% dispersions in water that remain localized following injection. With the trigger of a positively charged polymer (e.g., protamine), the nanoparticulate glues can quickly assemble into a viscous glue that exhibits rheological, mechanical, and adhesive properties resembling the native poly(glycerol sebacate)-acrylate based glues. This platform should be useful to enable the delivery of viscous glues to augment or replace sutures and staples during minimally invasive procedures. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The impact of cerium oxide nanoparticles on the physiology of soybean (Glycine max (L.) Merr.) under different soil moisture conditions.

PubMed

Cao, Zhiming; Rossi, Lorenzo; Stowers, Cheyenne; Zhang, Weilan; Lombardini, Leonardo; Ma, Xingmao

2018-01-01

The ongoing global climate change raises concerns over the decreasing moisture content in agricultural soils. Our research investigated the physiological impact of two types of cerium oxide nanoparticles (CeO 2 NPs) on soybean at different moisture content levels. One CeO 2 NP was positively charged on the surface and the other negatively charged due to the polyvinylpyrrolidone (PVP) coating. The results suggest that the effect of CeO 2 NPs on plant photosynthesis and water use efficiency (WUE) was dependent upon the soil moisture content. Both types of CeO 2 NPs exhibited consistently positive impacts on plant photosynthesis at the moisture content above 70% of field capacity (θ fc ). Similar positive impact of CeO 2 NPs was not observed at 55% θ fc , suggesting that the physiological impact of CeO 2 NPs was dependent upon the soil moisture content. The results also revealed that V Cmax (maximum carboxylation rate) was affected by CeO 2 NPs, indicating that CeO 2 NPs affected the Rubisco activity which governs carbon assimilation in photosynthesis. In conclusion, CeO 2 NPs demonstrated significant impacts on the photosynthesis and WUE of soybeans and such impacts were affected by the soil moisture content. Graphical abstract Soil moisture content affects plant cerium oxide nanoparticle interactions.

Inhaled diesel emissions generated with cerium oxide nanoparticle fuel additive induce adverse pulmonary and systemic effects.

PubMed

Snow, Samantha J; McGee, John; Miller, Desinia B; Bass, Virginia; Schladweiler, Mette C; Thomas, Ronald F; Krantz, Todd; King, Charly; Ledbetter, Allen D; Richards, Judy; Weinstein, Jason P; Conner, Teri; Willis, Robert; Linak, William P; Nash, David; Wood, Charles E; Elmore, Susan A; Morrison, James P; Johnson, Crystal L; Gilmour, Matthew Ian; Kodavanti, Urmila P

2014-12-01

Diesel exhaust (DE) exposure induces adverse cardiopulmonary effects. Cerium oxide nanoparticles added to diesel fuel (DECe) increases fuel burning efficiency but leads to altered emission characteristics and potentially altered health effects. Here, we evaluated whether DECe results in greater adverse pulmonary effects compared with DE. Male Sprague Dawley rats were exposed to filtered air, DE, or DECe for 5 h/day for 2 days. N-acetyl glucosaminidase activity was increased in bronchial alveolar lavage fluid (BALF) of rats exposed to DECe but not DE. There were also marginal but insignificant increases in several other lung injury biomarkers in both exposure groups (DECe > DE for all). To further characterize DECe toxicity, rats in a second study were exposed to filtered air or DECe for 5 h/day for 2 days or 4 weeks. Tissue analysis indicated a concentration- and time-dependent accumulation of lung and liver cerium followed by a delayed clearance. The gas-phase and high concentration of DECe increased lung inflammation at the 2-day time point, indicating that gas-phase components, in addition to particles, contribute to pulmonary toxicity. This effect was reduced at 4 weeks except for a sustained increase in BALF γ-glutamyl transferase activity. Histopathology and transmission electron microscopy revealed increased alveolar septa thickness due to edema and increased numbers of pigmented macrophages after DECe exposure. Collectively, these findings indicate that DECe induces more adverse pulmonary effects on a mass basis than DE. In addition, lung accumulation of cerium, systemic translocation to the liver, and delayed clearance are added concerns to existing health effects of DECe. Published by Oxford University Press on behalf of the Society of Toxicology 2014. This work is written by US Government employees and is in the public domain in the US.

Redox-Sensitive Cerium Oxide Nanoparticles Protect Human Keratinocytes from Oxidative Stress Induced by Glutathione Depletion.

PubMed

Singh, Ragini; Karakoti, Ajay S; Self, William; Seal, Sudipta; Singh, Sanjay

2016-11-22

Cerium oxide nanoparticles (CeNPs) have gathered much attention in the biomedical field due to its unique antioxidant property. It can protect cells and tissues from oxidative stress induced damage due to its autoregenerative redox cycle. Our study explores the antioxidant and antigenotoxic behavior of PEGylated CeNPs toward oxidative insult produced by buthionine sulfoximine (BSO) in human keratinocytes (HaCaT cells). BSO inhibits the γ-glutamylcysteinesynthetase (γ-GCS) enzyme and thus acts as a glutathione (GSH) depleting agent to modulate the cellular redox potential. GSH is a natural ROS scavenger present in the mammalian cells, and its depletion causes generation of reactive oxygen species (ROS). In this study, we challenged HaCaT cells (keratinocytes) with BSO to alter the redox potential within the cell and monitored toxicity, ROS generation, and nuclear fragmentation. We also followed changes in expressions of related proteins and genes. We found that PEGylated CeNPs can protect HaCaT cells from BSO-induced oxidative damage. BSO-exposed cells, preincubated with PEGylated CeNPs, showed better cell survival and significant decrease in the intracellular levels of ROS. We also observed decrease in lactate dehydrogenase (LDH) release and nuclear fragmentation in CeNP-treated cells that were challenged with BSO as compared to treatment with BSO alone. Exposure of HaCaT cells with BSO leads to altered expression of antioxidant genes and proteins, i.e., thioredoxin reductase (TrxR) and peroxiredoxin 6 (Prx6) whereas, in our study, pretreatment of PEGylated CeNPs reduces the need for induction of genes that produce enzymes involved in the defense against oxidative stress. Since, growing evidence argued the involvement of ROS in mediating death of mammalian cells in several ailments, our finding reinforces the use of PEGylated CeNPs as a potent pharmacological agent under the lower cellular GSH/GSSG ratios for the treatment of diseases mediated by free radicals.

Bio-inspired Nanoparticulate Medical Glues for Minimally Invasive Tissue Repair

PubMed Central

Lee, Yuhan; Xu, Chenjie; Sebastin, Monisha; Lee, Albert; Holwell, Nathan; Xu, Calvin; Miranda-Nieves, David; Mu, Luye; Lin, Charles

2015-01-01

Delivery of tissue glues through small-bore needles or trocars is critical for sealing holes, affixing medical devices, or attaching tissues together during minimally invasive surgeries. Inspired by the granule-packaged glue delivery system of sandcastle worms, we have developed a nanoparticulate formulation of a viscous hydrophobic light-activated adhesive based on poly(glycerol sebacate)-acrylate. Negatively charged alginate was used to stabilize the nanoparticulate surface to significantly reduce its viscosity and to maximize injectability through small-bore needles. The nanoparticulate glues can be concentrated to ~30w/v% dispersions in water that remain localized following injection. With the trigger of a positively charged polymer (e.g., protamine), the nanoparticulate glues can quickly assemble into a viscous glue that exhibits rheological, mechanical and adhesive properties resembling the native poly(glycerol sebacate)-acrylate based glues. This platform should be useful to enable the delivery of viscous glues to augment or replace sutures and staples during minimally invasive procedures. PMID:26227833

SOx removal by calcined MgAlFe hydrotalcite-like materials: effect of the chemical composition and the cerium incorporation method.

PubMed

Cantú, Manuel; López-Salinas, Esteban; Valente, Jaime S; Montiel, Ramon

2005-12-15

Sulfur oxides are one of the most hazardous atmospheric pollutants since they contribute directly to acid rain formation. Consequently, stringent environmental regulations limit atmospheric SOx emissions, motivating research on efficient ways to reduce them. To supply an alternative to reduce these emissions in fluid catalytic cracking units, this study discloses efficient SOx reducing materials based on calcined MgAlFe hydrotalcite-like compounds (HT's). Thus, HT materials were synthesized by several methods including cerium addition. The adsorption of SO2 was carried out by contacting the calcined solid with a mixture of SO2 (1%) in air at 650 degrees C. It was demonstrated that the isomorphic incorporation of iron increased its reduction capability which was reflected in higher reduction rates and metal sulfate reduction grade at 550 degrees C. Moreover, when cerium was present in the iron-containing materials the saturation rate was improved, because cerium oxide promotes the oxidation of SO2 to SO3. The way cerium is incorporated influences the SO2 adsorption capacity.

Enhanced chemiluminescence of cerium(IV)-Tween 85 system and the analytical application.

PubMed

Li, Shifeng; Qian, Li; Zhu, Yan; Liu, Manman; Gao, Yinping; Ni, Yonghong

2013-01-01

The oxidation reaction between cerium(IV) and Tween 85 in sulfuric acid medium produced weak chemiluminescence (CL). In this paper, it was found that citrate could strongly enhance the CL of cerium(IV)-Tween 85-polyphenol system. Based on studies of ultraviolet-visible spectra and CL spectra, the CL enhancement mechanism had been proposed. It was surmised that the light emission was from an excited oxygen molecular pair O2((1)Δg)O2((1)∑g(-)). The maximum emission wavelength was about 478 nm. The effects of 17 amino acids and 29 organic compounds on cerium(IV)-Tween 85-citrate CL were investigated by a flow injection procedure. This study showed the present system had a wide application for the determination of these compounds. Copyright © 2012 John Wiley & Sons, Ltd.

Exposure and Health Effects Review of Engineered Nanoscale Cerium and Cerium Dioxide Associated with its Use as a Fuel Additive - NOW IN PRINT IN THE JOURNAL

EPA Science Inventory

Advances of nanoscale science have produced nanomaterials with unique physical and chemical properties at commercial levels that are now incorporated into over 1000 products. Nanoscale cerium (di) oxide (Ce02) has recently gained a wide range of applications which includes coatin...

Comparative cytotoxicity assessments of some manufactured and anthropogenic nanoparticulate materials

NASA Astrophysics Data System (ADS)

Soto, Karla Fabiola

Due to increasing diversity of newly engineered nanoparticles, it is important to consider the hazards of these materials. Very little is known regarding the potential toxicity of relatively new nanomaterials. However, beginning with several historical accounts of nanomaterials applications---chrysotile asbestos and silver---it was assumed that these examples would provide some awareness and guidelines for future nanomaterial and nanotechnology applications, especially health effects. In this study in vitro assays were performed on a murine alveolar macrophage cell line (RAW 264.7), human alveolar macrophage cell line (THB-1), and human epithelial lung cell line (A549) to assess the comparative cytotoxicity of a wide range of manufactured (Ag, TiO2, Fe2O3, Al2O3, ZrO2, black carbon, two different types of multiwall structures and chrysotile asbestos as the toxicity standard) and anthropogenic nanoparticulates. There are several parameters of nanoparticulates that are considered to trigger an inflammatory response (particularly respiratory) or cause toxicity. These parameters include: particle size, shape, specific surface area, transition metals in particulates, and organic compounds. Therefore, a wide variety of manufactured and anthropogenic nanoparticulates having different morphologies, sizes, specific surface area and chemistries as noted were tested. To determine the nanoparticulates' size and morphology, they were characterized by transmission electron microscopy, where it was observed that the commercial multiwall carbon nanotube aggregate had an identical morphology to chrysotile asbestos and combustion-formed carbon nanotubes, i.e.; those that form from natural gas combustion. Light optical microscopy was used to determine cell morphology upon exposure to nanoparticulates as an indication of cell death. Also, the polycyclic aromatic hydrocarbon (PAH) content of the collected nanoparticulates was analyzed and correlated with cytotoxic responses. For

Multifunctional nanoparticulate polyelectrolyte complexes.

PubMed

Hartig, Sean M; Greene, Rachel R; DasGupta, Jayasri; Carlesso, Gianluca; Dikov, Mikhail M; Prokop, Ales; Davidson, Jeffrey M

2007-12-01

Water-soluble, biodegradable, polymeric, polyelectrolyte complex dispersions (PECs) have evolved because of the limitations, in terms of toxicity, of the currently available systems. These aqueous nanoparticulate architectures offer a significant advantage for products that may be used as drug delivery systems in humans. PECs are created by mixing oppositely charged polyions. Their hydrodynamic diameter, surface charge, and polydispersity are highly dependent on concentration, ionic strength, pH, and molecular parameters of the polymers that are used. In particular, the complexation between polyelectrolytes with significantly different molecular weights leads to the formation of water-insoluble aggregates. Several PEC characteristics are favorable for cellular uptake and colloidal stability, including hydrodynamic diameter less than 200 nm, surface charge of >30 mV or <-30 mV, spherical morphology, and polydispersity index (PDI) indicative of a homogeneous distribution. Maintenance of these properties is critical for a successful delivery vehicle. This review focuses on the development and potential applications of PECs as multi-functional, site-specific nanoparticulate drug/gene delivery and imaging devices.

Development and Validation of Spectrofluorimetric Method for Determination of Biotin in Bulk and Pharmaceutical Preparations via its Oxidation with Cerium (IV)

PubMed Central

Walash, M. I.; Rizk, M.; Sheribah, Z. A.; Salim, M. M.

2010-01-01

A simple and sensitive spectrofluorimetric method was developed for the determination of biotin in pure form and in pharmaceutical preparations. The proposed method is based on the oxidation of the drug with cerium (IV) ammonium sulfate in acidic medium. The fluorescence of the produced Cerium (III) was measured at 365 nm after excitation at 255 nm. The different experimental parameters affecting the development and stability of the reaction were carefully studied and optimized. The method is applicable over the concentration range of 30-120 ng/mL with correlation coefficient of 0.9998. The detection limit (LOD) of biotin was 2.41 ng/mL while quantitation limit (LOQ) was 7.29 ng/mL. The proposed procedure was successfully applied for the determination of biotin in pharmaceutical preparations with mean recoveries of 99.55 ± 0.83 and 101.67 ± 1.53 for biotin ampoules and capsules, respectively. The results obtained were in good agreement with those obtained using the official method. PMID:23675202

Nanocasted synthesis of magnetic mesoporous iron cerium bimetal oxides (MMIC) as an efficient heterogeneous Fenton-like catalyst for oxidation of arsenite.

PubMed

Wen, Zhipan; Zhang, Yalei; Dai, Chaomeng; Sun, Zhen

2015-04-28

Magnetic mesoporous iron cerium bimetal oxides (MMIC) with large surface area and pore volume was synthesized via the hard template approach. This obtained MMIC was easily separated from aqueous solution with an external magnetic field and was proposed as a heterogeneous Fenton-like catalyst for oxidation of As(III). The MMIC presented excellent catalytic activity for the oxidation of As(III), achieving almost complete oxidation of 1000ppb As(III) after 60min and complete removal of arsenic species after 180min with reaction conditions of 0.4g/L catalyst, pH of 3.0 and 0.4mM H2O2. Kinetics analysis showed that arsenic removal followed the pseudo-first order, and the pseudo-first-order rate constants increased from 0.0014min(-1) to 0.0548min(-1) as the H2O2 concentration increased from 0.04mM to 0.4mM. On the basis of the effects of XPS analysis and reactive oxidizing species, As(III) in aqueous solution was mainly oxidized by OH radicals, including the surface-bound OHads generated on the MMIC surface which were involved in Fe(2+) and Ce(3+), and free OHfree generation by soluble iron ions which were released from the MMIC into the bulk solution, and the generated As(V) was finally removed by MMIC through adsorption. Copyright © 2015 Elsevier B.V. All rights reserved.

Evaluation of the effect of valence state on cerium oxide nanoparticle toxicity following intratracheal instillation in rats

PubMed Central

Dunnick, Katherine M.; Morris, Anna M.; Badding, Melissa A.; Barger, Mark; Stefaniak, Aleksandr B.; Sabolsky, Edward M.; Leonard, Stephen S.

2016-01-01

Cerium (Ce) is becoming a popular metal for use in electrochemical applications. When in the form of cerium oxide (CeO2), Ce can exist in both 3 + and 4 + valence states, acting as an ideal catalyst. Previous in vitro and in vivo evidence have demonstrated that CeO2 has either anti- or pro-oxidant properties, possibly due to the ability of the nanoparticles to transition between valence states. Therefore, we chose to chemically modify the nanoparticles to shift the valence state toward 3+. During the hydrothermal synthesis process, 10 mol% gadolinium (Gd) and 20 mol% Gd, were substituted into the lattice of the CeO2 nanoparticles forming a perfect solid solution with various A-site valence states. These two Gd-doped CeO2 nanoparticles were compared to pure CeO2 nanoparticles. Preliminary characteristics indicated that doping results in minimal size and zeta potential changes but alters valence state. Following characterization, male Sprague-Dawley rats were exposed to 0.5 or 1.0 mg/kg nanoparticles via a single intratracheal instillation. Animals were sacrificed and bronchoalveolar lavage fluid and various tissues were collected to determine the effect of valence state and oxygen vacancies on toxicity 1-, 7-, or 84-day post-exposure. Results indicate that damage, as measured by elevations in lactate dehydrogenase, occurred within 1-day post-exposure and was sustained 7-day post-exposure, but subsided to control levels 84-day post-exposure. Furthermore, no inflammatory signaling or lipid peroxidation occurred following exposure with any of the nanoparticles. Our results implicate that valence state has a minimal effect on CeO2 nanoparticle toxicity in vivo. PMID:26898289

Nanostructured manganese oxide on silica aerogel: a new catalyst toward water oxidation.

PubMed

Najafpour, Mohammad Mahdi; Salimi, Saeideh; Madadkhani, Sepideh; Hołyńska, Małgorzata; Tomo, Tatsuya; Allakhverdiev, Suleyman I

2016-12-01

Herein we report on the synthesis and characterization of nano-sized Mn oxide/silica aerogel with low density as a good catalyst toward water oxidation. The composite was synthesized by a simple and low-cost hydrothermal procedure. In the next step, we studied the composite in the presence of cerium(IV) ammonium nitrate and photo-produced Ru(bpy) 3 3+ as a water-oxidizing catalyst. The low-density composite is a good Mn-based catalyst with turnover frequencies of ~0.3 and 0.5 (mmol O 2 /(mol Mn·s)) in the presence of Ru(bpy) 3 3+ and cerium(IV) ammonium nitrate, respectively. In addition to the water-oxidizing activities of the composite under different conditions, its self-healing reaction in the presence of cerium(IV) ammonium nitrate was also studied.

PLUTONIUM-CERIUM-COBALT AND PLUTONIUM-CERIUM-NICKEL ALLOYS

DOEpatents

Coffinberry, A.S.

1959-08-25

>New plutonium-base teroary alloys useful as liquid reactor fuels are described. The alloys consist of 10 to 20 atomic percent cobalt with the remainder plutonium and cerium in any desired proportion, with the plutonium not in excess of 88 atomic percent; or, of from 10 to 25 atomic percent nickel (or mixture of nickel and cobalt) with the remainder plutonium and cerium in any desired proportion, with the plutonium not in excess of 86 atomic percent. The stated advantages of these alloys over unalloyed plutonium for reactor fuel use are a lower melting point and a wide range of permissible plutonium dilution.

Cerium oxide nanoparticle elicits oxidative stress, endocrine imbalance and lowers sperm characteristics in testes of balb/c mice.

PubMed

Adebayo, O A; Akinloye, O; Adaramoye, O A

2018-04-01

The toxicity of metallic nanoparticles is a growing concern due to its application in industries and homes. We investigated the toxicity of cerium oxide nanoparticles (CeO 2 NPs) on reproductive system in male balb/c mice. Twenty mice were divided into four groups of five animals each and treated thus: normal saline (control), 100, 200 and 300 μg/kg CeO 2 NPs (i.p.,) thrice in a week for five consecutive weeks. Results showed that CeO 2 NPs significantly reduced the levels of haemoglobin, PCV and RBC count relative to controls. In addition, luteinising and follicle-stimulating hormones (FSH and LH) and prolactin were significantly reduced in the mice. Specifically, CeO 2 NPs at 100 μg/kg decreased testosterone by 23%, while CeO 2 NPs at 200 μg/kg decreased FSH, LH and prolactin by 25%, 26% and 13%, respectively. Testicular malondialdehyde was increased by 103%, 106% and 135% in mice treated with 100, 200 and 300 μg/kg CeO 2 NPs, respectively. CeO 2 NPs caused a significant reduction in activities of antioxidant enzymes and levels of reduced glutathione and total nitric oxide. Moreso, CeO 2 NPs decreased sperm motility and count and increased total sperm abnormality in mice. Histology revealed congestion and degeneration of seminiferous tubules. Overall, CeO 2 NPs induces testicular dysfunction via disruption of antioxidant/oxidant balance and endocrine suppression. © 2017 Blackwell Verlag GmbH.

Untangling the biological effects of cerium oxide nanoparticles: the role of surface valence states

PubMed Central

Pulido-Reyes, Gerardo; Rodea-Palomares, Ismael; Das, Soumen; Sakthivel, Tamil Selvan; Leganes, Francisco; Rosal, Roberto; Seal, Sudipta; Fernández-Piñas, Francisca

2015-01-01

Cerium oxide nanoparticles (nanoceria; CNPs) have been found to have both pro-oxidant and anti-oxidant effects on different cell systems or organisms. In order to untangle the mechanisms which underlie the biological activity of nanoceria, we have studied the effect of five different CNPs on a model relevant aquatic microorganism. Neither shape, concentration, synthesis method, surface charge (ζ-potential), nor nominal size had any influence in the observed biological activity. The main driver of toxicity was found to be the percentage of surface content of Ce3+ sites: CNP1 (58%) and CNP5 (40%) were found to be toxic whereas CNP2 (28%), CNP3 (36%) and CNP4 (26%) were found to be non-toxic. The colloidal stability and redox chemistry of the most and least toxic CNPs, CNP1 and CNP2, respectively, were modified by incubation with iron and phosphate buffers. Blocking surface Ce3+ sites of the most toxic CNP, CNP1, with phosphate treatment reverted toxicity and stimulated growth. Colloidal destabilization with Fe treatment only increased toxicity of CNP1. The results of this study are relevant in the understanding of the main drivers of biological activity of nanoceria and to define global descriptors of engineered nanoparticles (ENPs) bioactivity which may be useful in safer-by-design strategies of nanomaterials. PMID:26489858

Grain size dependence of dielectric relaxation in cerium oxide as high-k layer

PubMed Central

2013-01-01

Cerium oxide (CeO2) thin films used liquid injection atomic layer deposition (ALD) for deposition and ALD procedures were run at substrate temperatures of 150°C, 200°C, 250°C, 300°C, and 350°C, respectively. CeO2 were grown on n-Si(100) wafers. Variations in the grain sizes of the samples are governed by the deposition temperature and have been estimated using Scherrer analysis of the X-ray diffraction patterns. The changing grain size correlates with the changes seen in the Raman spectrum. Strong frequency dispersion is found in the capacitance-voltage measurement. Normalized dielectric constant measurement is quantitatively utilized to characterize the dielectric constant variation. The relationship extracted between grain size and dielectric relaxation for CeO2 suggests that tuning properties for improved frequency dispersion can be achieved by controlling the grain size, hence the strain at the nanoscale dimensions. PMID:23587419

Effects of amorphous silica coating on cerium oxide nanoparticles induced pulmonary responses.

PubMed

Ma, Jane; Mercer, Robert R; Barger, Mark; Schwegler-Berry, Diane; Cohen, Joel M; Demokritou, Philip; Castranova, Vincent

2015-10-01

Recently cerium compounds have been used in a variety of consumer products, including diesel fuel additives, to increase fuel combustion efficiency and decrease diesel soot emissions. However, cerium oxide (CeO2) nanoparticles have been detected in the exhaust, which raises a health concern. Previous studies have shown that exposure of rats to nanoscale CeO2 by intratracheal instillation (IT) induces sustained pulmonary inflammation and fibrosis. In the present study, male Sprague-Dawley rats were exposed to CeO2 or CeO2 coated with a nano layer of amorphous SiO2 (aSiO2/CeO2) by a single IT and sacrificed at various times post-exposure to assess potential protective effects of the aSiO2 coating. The first acellular bronchoalveolar lavage (BAL) fluid and BAL cells were collected and analyzed from all exposed animals. At the low dose (0.15mg/kg), CeO2 but not aSiO2/CeO2 exposure induced inflammation. However, at the higher doses, both particles induced a dose-related inflammation, cytotoxicity, inflammatory cytokines, matrix metalloproteinase (MMP)-9, and tissue inhibitor of MMP at 1day post-exposure. Morphological analysis of lung showed an increased inflammation, surfactant and collagen fibers after CeO2 (high dose at 3.5mg/kg) treatment at 28days post-exposure. aSiO2 coating significantly reduced CeO2-induced inflammatory responses in the airspace and appeared to attenuate phospholipidosis and fibrosis. Energy dispersive X-ray spectroscopy analysis showed Ce and phosphorous (P) in all particle-exposed lungs, whereas Si was only detected in aSiO2/CeO2-exposed lungs up to 3days after exposure, suggesting that aSiO2 dissolved off the CeO2 core, and some of the CeO2 was transformed to CePO4 with time. These results demonstrate that aSiO2 coating reduce CeO2-induced inflammation, phospholipidosis and fibrosis. Published by Elsevier Inc.

Titrimetric and Spectrophotometric Methods for the Assay of Ketotifen Using Cerium(IV) and Two Reagents

PubMed Central

Raghu, Madihalli Srinivas; Basavaiah, Kanakapura; Prashanth, Kudige Nagaraj; Vinay, Kanakapura Basavaiah

2013-01-01

One titrimetric and two spectrophotometric methods are described for the determination of ketotifen fumarate (KTF) in bulk drug and in tablets using cerium(IV) as the oxidimetric agent. In titrimetry (method A), the drug was treated with a measured excess of cerium(IV) in H2SO4 medium and after a standing time of 10 min, the surplus oxidant was determined by back titration with iron(II). The spectrophotometric procedures involve addition of a known excess of cerium(IV) to KTF in acid medium followed by the determination of unreacted oxidant by reacting with either p-dimethyl amino benzaldehyde and measuring the resulting colour at 460 nm (method B) or o-dianisidine and subsequent measurement of the absorbance of coloured product at 470 nm (method C). Titrimetric assay is based on a 1 : 2 reaction stoichiometry between KTF and cerium(IV) and the method is applicable over 2–18 mg range. In spectrophotometry, regression analysis of Beer's law plots showed a good correlation in 0.4–8.0 and 0.4–10.0 g mL−1 KTF ranges for method B and method C, respectively, and the corresponding molar absorptivity coefficients are calculated to be 4.0 × 104 and 3.7 × 104 L mol−1 cm−1. PMID:24324496

Preparation of cerium halide solvate complexes

DOEpatents

Vasudevan, Kalyan V; Smith, Nickolaus A; Gordon, John C; McKigney, Edward A; Muenchaussen, Ross E

2013-08-06

Crystals of a solvated cerium(III) halide solvate complex resulted from a process of forming a paste of a cerium(III) halide in an ionic liquid, adding a solvent to the paste, removing any undissolved solid, and then cooling the liquid phase. Diffusing a solvent vapor into the liquid phase also resulted in crystals of a solvated cerium(III) halide complex.

Cerium Improves Growth of Maize Seedlings via Alleviating Morphological Structure and Oxidative Damages of Leaf under Different Stresses.

PubMed

Hong, Fashui; Qu, Chunxiang; Wang, Ling

2017-10-18

It had been indicated that cerium (Ce) could promote maize growth involving photosynthetic improvement under potassium (K) deficiency, salt stress, and combined stress of K + deficiency and salt stress. However, whether the improved growth is related to leaf morphological structure, oxidative stress in maize leaves is not well understood. The present study showed that K + deficiency, salt stress, and their combined stress inhibited growth of maize seedlings, affecting the formation of appendages of leaf epidermal cells, and stomatal opening, which may be due to increases in H 2 O 2 and malondialdehyde levels, and reductions in Ca 2+ content, ratios of glutathione/oxidized glutathione, ascorbic acid/dehydroascorbic acid, and the activities of superoxide dismutase, catalase, ascorbic acid peroxidase, guaiacol peroxidase, and glutathione reductase in leaves under different stresses. The adverse effects caused by combined stress were higher than those of single stress. Furthermore, our findings demonstrated that adding Ce 3+ could significantly promote seedling growth, and alleviate morphological and structural damage of leaf, decrease oxidative stress and increase antioxidative capacity in maize leaves caused by different stresses.

A fully spray-coated fuel cell membrane electrode assembly using Aquivion ionomer with a graphene oxide/cerium oxide interlayer

NASA Astrophysics Data System (ADS)

Breitwieser, Matthias; Bayer, Thomas; Büchler, Andreas; Zengerle, Roland; Lyth, Stephen M.; Thiele, Simon

2017-05-01

A novel multilayer membrane electrode assembly (MEA) for polymer electrolyte membrane fuel cells (PEMFCs) is fabricated in this work, within a single spray-coating device. For the first time, direct membrane deposition is used to fabricate a PEMFC by spraying the short-side-chain ionomer Aquivion directly onto the gas diffusion electrodes. The fully sprayed MEA, with an Aquivion membrane 10 μm in thickness, achieved a high power density of 1.6 W/cm2 for H2/air operation at 300 kPaabs. This is one of the highest reported values for thin composite membranes operated in H2/air atmosphere. By the means of confocal laser scanning microscopy, individual carbon fibers from the gas diffusion layer are identified to penetrate through the micro porous layer (MPL), likely causing a low electrical cell resistance in the range of 150 Ω cm2 through the thin sprayed membranes. By spraying a 200 nm graphene oxide/cerium oxide (GO/CeO2) interlayer between two layers of Aquivion ionomer, the impact of the electrical short is eliminated and the hydrogen crossover current density is reduced to about 1 mA/cm2. The peak power density of the interlayer-containing MEA drops only by 10% compared to a pure Aquivion membrane of similar thickness.

Combustion-derived nanoparticulate induces the adverse vascular effects of diesel exhaust inhalation

PubMed Central

Mills, Nicholas L.; Miller, Mark R.; Lucking, Andrew J.; Beveridge, Jon; Flint, Laura; Boere, A. John F.; Fokkens, Paul H.; Boon, Nicholas A.; Sandstrom, Thomas; Blomberg, Anders; Duffin, Rodger; Donaldson, Ken; Hadoke, Patrick W.F.; Cassee, Flemming R.; Newby, David E.

2011-01-01

Aim Exposure to road traffic and air pollution may be a trigger of acute myocardial infarction, but the individual pollutants responsible for this effect have not been established. We assess the role of combustion-derived-nanoparticles in mediating the adverse cardiovascular effects of air pollution. Methods and results To determine the in vivo effects of inhalation of diesel exhaust components, 16 healthy volunteers were exposed to (i) dilute diesel exhaust, (ii) pure carbon nanoparticulate, (iii) filtered diesel exhaust, or (iv) filtered air, in a randomized double blind cross-over study. Following each exposure, forearm blood flow was measured during intra-brachial bradykinin, acetylcholine, sodium nitroprusside, and verapamil infusions. Compared with filtered air, inhalation of diesel exhaust increased systolic blood pressure (145 ± 4 vs. 133 ± 3 mmHg, P< 0.05) and attenuated vasodilatation to bradykinin (P= 0.005), acetylcholine (P= 0.008), and sodium nitroprusside (P< 0.001). Exposure to pure carbon nanoparticulate or filtered exhaust had no effect on endothelium-dependent or -independent vasodilatation. To determine the direct vascular effects of nanoparticulate, isolated rat aortic rings (n= 6–9 per group) were assessed in vitro by wire myography and exposed to diesel exhaust particulate, pure carbon nanoparticulate and vehicle. Compared with vehicle, diesel exhaust particulate (but not pure carbon nanoparticulate) attenuated both acetylcholine (P< 0.001) and sodium-nitroprusside (P= 0.019)-induced vasorelaxation. These effects were partially attributable to both soluble and insoluble components of the particulate. Conclusion Combustion-derived nanoparticulate appears to predominately mediate the adverse vascular effects of diesel exhaust inhalation. This provides a rationale for testing environmental health interventions targeted at reducing traffic-derived particulate emissions. PMID:21753226

The use of nanoparticulates to treat breast cancer.

PubMed

Tang, Xiaomeng; Loc, Welley S; Dong, Cheng; Matters, Gail L; Butler, Peter J; Kester, Mark; Meyers, Craig; Jiang, Yixing; Adair, James H

2017-10-01

Breast cancer is a major ongoing public health issue among women in both developing and developed countries. Significant progress has been made to improve the breast cancer treatment in the past decades. However, the current clinical approaches are invasive, of low specificity and can generate severe side effects. As a rapidly developing field, nanotechnology brings promising opportunities to human cancer diagnosis and treatment. The use of nanoparticulate-based platforms overcomes biological barriers and allows prolonged blood circulation time, simultaneous tumor targeting and enhanced accumulation of drugs in tumors. Currently available and clinically applicable innovative nanoparticulate-based systems for breast cancer nanotherapies are discussed in this review.

Nanoparticulate delivery systems for antiviral drugs.

PubMed

Lembo, David; Cavalli, Roberta

2010-01-01

Nanomedicine opens new therapeutic avenues for attacking viral diseases and for improving treatment success rates. Nanoparticulate-based systems might change the release kinetics of antivirals, increase their bioavailability, improve their efficacy, restrict adverse drug side effects and reduce treatment costs. Moreover, they could permit the delivery of antiviral drugs to specific target sites and viral reservoirs in the body. These features are particularly relevant in viral diseases where high drug doses are needed, drugs are expensive and the success of a therapy is associated with a patient's adherence to the administration protocol. This review presents the current status in the emerging area of nanoparticulate delivery systems in antiviral therapy, providing their definition and description, and highlighting some peculiar features. The paper closes with a discussion on the future challenges that must be addressed before the potential of nanotechnology can be translated into safe and effective antiviral formulations for clinical use.

Cerium migration during PEM fuel cell accelerated stress testing

DOE PAGES

Baker, Andrew M.; Mukundan, Rangachary; Borup, Rodney L.; ...

2016-01-01

Cerium is a radical scavenger which improves polymer electrolyte membrane (PEM) fuel cell durability. During operation, however, cerium rapidly migrates in the PEM and into the catalyst layers (CLs). In this work, membrane electrode assemblies (MEAs) were subjected to accelerated stress tests (ASTs) under different humidity conditions. Cerium migration was characterized in the MEAs after ASTs using X-ray fluorescence. During fully humidified operation, water flux from cell inlet to outlet generated in-plane cerium gradients. Conversely, cerium profiles were flat during low humidity operation, where in-plane water flux was negligible, however, migration from the PEM into the CLs was enhanced. Humiditymore » cycling resulted in both in-plane cerium gradients due to water flux during the hydration component of the cycle, and significant migration into the CLs. Fluoride and cerium emissions into effluent cell waters were measured during ASTs and correlated, which signifies that ionomer degradation products serve as possible counter-ions for cerium emissions. Fluoride emission rates were also correlated to final PEM cerium contents, which indicates that PEM degradation and cerium migration are coupled. Lastly, it is proposed that cerium migrates from the PEM due to humidification conditions and degradation, and is subsequently stabilized in the CLs by carbon catalyst supports.« less

Oxidation-state sensitive imaging of cerium dioxide by atomic-resolution low-angle annular dark field scanning transmission electron microscopy.

PubMed

Johnston-Peck, Aaron C; Winterstein, Jonathan P; Roberts, Alan D; DuChene, Joseph S; Qian, Kun; Sweeny, Brendan C; Wei, Wei David; Sharma, Renu; Stach, Eric A; Herzing, Andrew A

2016-03-01

Low-angle annular dark field (LAADF) scanning transmission electron microscopy (STEM) imaging is presented as a method that is sensitive to the oxidation state of cerium ions in CeO2 nanoparticles. This relationship was validated through electron energy loss spectroscopy (EELS), in situ measurements, as well as multislice image simulations. Static displacements caused by the increased ionic radius of Ce(3+) influence the electron channeling process and increase electron scattering to low angles while reducing scatter to high angles. This process manifests itself by reducing the high-angle annular dark field (HAADF) signal intensity while increasing the LAADF signal intensity in close proximity to Ce(3+) ions. This technique can supplement STEM-EELS and in so doing, relax the experimental challenges associated with acquiring oxidation state information at high spatial resolutions. Published by Elsevier B.V.

Effects of calcium and phosphate on uranium(IV) oxidation: Comparison between nanoparticulate uraninite and amorphous UIV-phosphate

NASA Astrophysics Data System (ADS)

Latta, Drew E.; Kemner, Kenneth M.; Mishra, Bhoopesh; Boyanov, Maxim I.

2016-02-01

The mobility of uranium in subsurface environments depends strongly on its redox state, with UIV phases being significantly less soluble than UVI minerals. This study compares the oxidation kinetics and mechanisms of two potential products of UVI reduction in natural systems, a nanoparticulate UO2 phase and an amorphous UIV-Ca-PO4 analog to ningyoite (CaUIV(PO4)2·1-2H2O). The valence of U was tracked by X-ray absorption near-edge spectroscopy (XANES), showing similar oxidation rate constants for UIVO2 and UIV-phosphate in solutions equilibrated with atmospheric O2 and CO2 at pH 7.0 (kobs,UO2 = 0.17 ± 0.075 h-1 vs. kobs,UIVPO4 = 0.30 ± 0.25 h-1). Addition of up to 400 μM Ca and PO4 decreased the oxidation rate constant by an order of magnitude for both UO2 and UIV-phosphate. The intermediates and products of oxidation were tracked by electron microscopy, powder X-ray diffraction (pXRD), and extended X-ray absorption fine-structure spectroscopy (EXAFS). In the absence of Ca or PO4, the product of UO2 oxidation is Na-uranyl oxyhydroxide (under environmentally relevant concentrations of sodium, 15 mM NaClO4 and low carbonate concentration), resulting in low concentrations of dissolved UVI (<2.5 × 10-7 M). Oxidation of UIV-phosphate produced a Na-autunite phase (Na2(UO2)PO4·xH2O), resulting in similarly low dissolved U concentrations (<7.3 × 10-8 M). When Ca and PO4 are present in the solution, the EXAFS data and the solubility of the UVI phase resulting from oxidation of UO2 and UIV-phosphate are consistent with the precipitation of Na-autunite. Bicarbonate extractions and Ca K-edge X-ray absorption spectroscopy of oxidized solids indicate the formation of a Ca-UVI-PO4 layer on the UO2 surface and suggest a passivation layer mechanism for the decreased rate of UO2 oxidation in the presence of Ca and PO4. Interestingly, the extractions were unable to remove all of the oxidized U from partially oxidized UO2 solids, suggesting that oxidized U is distributed between

Cerium(IV)-mediated oxidation of flavonol with relevance to flavonol 2,4-dioxygenase. Direct evidence for spin delocalization in the flavonoxy radical.

PubMed

Kaizer, József; Ganszky, Ildikó; Speier, Gábor; Rockenbauer, Antal; Korecz, László; Giorgi, Michel; Réglier, Marius; Antonczak, Serge

2007-06-01

The cerium(IV)-mediated oxidation of 3-hydroxy-4'-methylflavone (1) proceeds by H-atom abstraction forming the flavonoxy radical (7), and the subsequent combination of its resonance forms leads to the 3-hydroxy-4'-methylflavone dehydro dimer (9). The above system serves as direct evidence for the intermediacy of the flavonoxy radical, its spin delocalization, and also indirect evidence for valence tautomerism as a key step on the substrate activation both in the quercetinase and its biomimic model system.

Nanoparticules d'or: De l'imagerie par resonance magnetique a la radiosensibilisation

NASA Astrophysics Data System (ADS)

Hebert, Etienne M.

Cette thèse approfondit l'étude de nanoparticules d'or de 5 nm de diamètre recouvertes de diamideéthanethioldiethylènetriaminepentacétate de gadolinium (DTDTPA:Gd), un agent de contraste pour l'imagerie par résonance magnétique (IRM). En guise de ciblage passif, la taille des nanoparticules a été contrôlée afin d'utiliser le réseau de néovaisseaux poreux et perméable des tumeurs. De plus les tumeurs ont un drainage lymphatique déficient qui permet aux nanoparticules de demeurer plus longtemps dans le milieu interstitiel de la tumeur. Les expériences ont été effectuées sur des souris Balb/c femelles portant des tumeurs MC7-L1. La concentration de nanoparticules a pu être mesurée à l'IRM in vivo. La concentration maximale se retrouvait à la fin de l'infusion de 10 min. La concentration s'élevait à 0.3 mM dans la tumeur et de 0.12 mM dans le muscle environnant. Les nanoparticules étaient éliminées avec une demi-vie de 22 min pour les tumeurs et de 20 min pour le muscle environnant. Les nanoparticules ont été fonctionnalisées avec le peptide Tat afin de leur conférer des propriétés de ciblage actif La rétention de ces nanoparticules a ainsi été augmentée de 1600 %, passant d'une demi-vie d'élimination de 22 min à 350 min. La survie des souris a été mesurée à l'aide de courbes Kaplan-Meier et d'un modèle mathématique évalue l'efficacité de traitements. Le modèle nous permet, à l'aide de la vitesse de croissance des tumeurs et de l'efficacité des traitements, de calculer la courbe de survie des spécimens. Un effet antagoniste a été observé au lieu de l'effet synergétique attendu entre une infusion de Au@DTDTPA:Gd et l'irradiation aux rayons X. L'absence d'effet synergétique a été attribuée à l'épaisseur du recouvrement de DTDTPA:Gd qui fait écran aux électrons produits par l'or. De plus, le moyen d'ancrage du recouvrement utilise des thiols qui peuvent s'avérer être des capteurs de radicaux. De plus

Potential of using cerium oxide nanoparticles for protecting healthy tissue during accelerated partial breast irradiation (APBI)

PubMed Central

Ouyang, Zi; Mainali, Madan Kumar; Sinha, Neeharika; Strack, Guinevere; Altundal, Yucel; Hao, Yao; Winningham, Thomas Andrew; Sajo, Erno; Celli, Jonathan; Ngwa, Wilfred

2016-01-01

The purpose of this study is to investigate the feasibility of using cerium oxide nanoparticles (CONPs) as radical scavengers during accelerated partial breast irradiation (APBI) to protect normal tissue. We hypothesize that CONPs can be slowly released from the routinely used APBI balloon applicators—via a degradable coating—and protect the normal tissue on the border of the lumpectomy cavity over the duration of APBI. To assess the feasibility of this approach, we analytically calculated the initial concentration of CONPs required to protect normal breast tissue from reactive oxygen species (ROS) and the time required for the particles to diffuse to various distances from the lumpectomy wall. Given that cerium has a high atomic number, we took into account the possible inadvertent dose enhancement that could occur due to the photoelectric interactions with radiotherapy photons. To protect against a typical MammoSite treatment fraction of 3.4 Gy, 5 ng-g−1 of CONPs is required to scavenge hydroxyl radicals and hydrogen peroxide. Using 2 nm sized NPs, with an initial concentration of 1 mg-g−1, we found that 2–10 days of diffusion is required to obtain desired concentrations of CONPs in regions 1–2 cm away from the lumpectomy wall. The resultant dose enhancement factor (DEF) is less than 1.01 under such conditions. Our results predict that CONPs can be employed for radioprotection during APBI using a new design in which balloon applicators are coated with the NPs for sustained/controlled in-situ release from within the lumpectomy cavity. PMID:27053452

Interactions between sub-10-nm iron and cerium oxide nanoparticles and 3T3 fibroblasts: the role of the coating and aggregation state

NASA Astrophysics Data System (ADS)

Safi, M.; Sarrouj, H.; Sandre, O.; Mignet, N.; Berret, J.-F.

2010-04-01

Recent nanotoxicity studies revealed that the physico-chemical characteristics of engineered nanomaterials play an important role in the interactions with living cells. Here, we report on the toxicity and uptake of cerium and iron oxide sub-10-nm nanoparticles by NIH/3T3 mouse fibroblasts. Coating strategies include low-molecular weight ligands (citric acid) and polymers (poly(acrylic acid), MW = 2000 g mol - 1). Electrostatically adsorbed on the surfaces, the organic moieties provide a negatively charged coating in physiological conditions. We find that most particles were biocompatible, as exposed cells remained 100% viable relative to controls. Only the bare and the citrate-coated nanoceria exhibit a slight decrease in mitochondrial activity at very high cerium concentrations (>1 g l - 1). We also observe that the citrate-coated particles are internalized/adsorbed by the cells in large amounts, typically 250 pg/cell after 24 h incubation for iron oxide. In contrast, the polymer-coated particles are taken up at much lower rates (<30 pg/cell). The strong uptake shown by the citrated particles is related to the destabilization of the dispersions in the cell culture medium and their sedimentation down to the cell membranes. In conclusion, we show that the uptake of nanomaterials by living cells depends on the coating of the particles and on its ability to preserve the colloidal nature of the dispersions.

Biomineralization-Inspired Synthesis of Cerium-Doped Carbonaceous Nanoparticles for Highly Hydroxyl Radical Scavenging Activity

NASA Astrophysics Data System (ADS)

Zou, Shenqiang; Zhu, Xiaofang; Zhang, Lirong; Guo, Fan; Zhang, Miaomiao; Tan, Youwen; Gong, Aihua; Fang, Zhengzou; Ju, Huixiang; Wu, Chaoyang; Du, Fengyi

2018-03-01

Cerium oxide nanoparticles recently have received extensive attention in biomedical applications due to their excellent anti-oxidation performance. In this study, a simple, mild, and green approach was developed to synthesize cerium-doped carbonaceous nanoparticles (Ce-doped CNPs) using bio-mineralization of bull serum albumin (BSA) as precursor. The resultant Ce-doped CNPs exhibited uniform and ultrasmall morphology with an average size of 14.7 nm. XPS and FTIR results revealed the presence of hydrophilic group on the surface of Ce-doped CNPs, which resulted in excellent dispersity in water. The CCK-8 assay demonstrated that Ce-doped CNPs possessed favorable biocompatibility and negligible cytotoxicity. Using H2O2-induced reactive oxygen species (ROS) as model, Ce-doped CNPs showed highly hydroxyl radical scavenging capability. Furthermore, flow cytometry and live-dead staining results indicated that Ce-doped CNPs protected cells from H2O2-induced damage in a dose-dependent effect, which provided a direct evidence for anti-oxidative performance. These findings suggest that Ce-doped CNPs as novel ROS scavengers may provide a potential therapeutic prospect in treating diseases associated with oxidative stress.

Protective effects of Curcuma longa against neurobehavioral and neurochemical damage caused by cerium chloride in mice.

PubMed

Kadri, Yamina; Nciri, Riadh; Brahmi, Noura; Saidi, Saber; Harrath, Abdel Halim; Alwasel, Saleh; Aldahmash, Waleed; El Feki, Abdelfatteh; Allagui, Mohamed Salah

2018-05-07

Cerium chloride (CeCl 3 ) is considered an environmental pollutant and a potent neurotoxic agent. Medicinal plants have many bioactive compounds that provide protection against damage caused by such pollutants. Curcuma longa is a bioactive compound-rich plant with very important antioxidant properties. To study the preventive and healing effects of Curcuma longa on cerium-damaged mouse brains, we intraperitoneally injected cerium chloride (CeCl 3 , 20 mg/kg BW) along with Curcuma longa extract, administrated by gavage (100 mg/kg BW), into mice for 60 days. We then examined mouse behavior, brain tissue damage, and brain oxidative stress parameters. Our results revealed a significant modification in the behavior of the CeCl 3 -treated mice. In addition, CeCl 3 induced a significant increment in lipid peroxidation, carbonyl protein (PCO), and advanced oxidation protein product levels, as well as a significant reduction in superoxide dismutase (SOD) and glutathione peroxidase (GPx) activities. Acetylcholinesterase (AChE) activity remarkably increased in the brain of CeCl 3 -treated mice. Histopathological observations confirmed these results. Curcuma longa attenuated CeCl 3 -induced oxidative stress and increased the activities of antioxidant enzymes. It also decreased AChE activity in the CeCl 3 -damaged mouse brain that was confirmed by histopathology. In conclusion, this study suggests that Curcuma longa has a neuroprotective effect against CeCl 3 -induced damage in the brain.

Antioxidative study of Cerium Oxide nanoparticle functionalised PCL-Gelatin electrospun fibers for wound healing application.

PubMed

Rather, Hilal Ahmad; Thakore, Ria; Singh, Ragini; Jhala, Dhwani; Singh, Sanjay; Vasita, Rajesh

2018-06-01

Skin wound healing involves a coordinated cellular response to achieve complete reepithelialisation. Elevated levels of reactive oxygen species (ROS) in the wound environment often pose a hindrance in wound healing resulting in impaired wound healing process. Cerium oxide nanoparticles (CeNPs) have the ability to protect the cells from oxidative damage by actively scavenging the ROS. Furthermore, matrices like nanofibers have also been explored for enhancing wound healing. In the current study CeNP functionalised polycaprolactone (PCL)-gelatin nanofiber (PGNPNF) mesh was fabricated by electrospinning and evaluated for its antioxidative potential. Wide angle XRD analysis of randomly oriented nanofibers revealed ∼2.6 times reduced crystallinity than pristine PCL which aided in rapid degradation of nanofibers and release of CeNP. However, bioactive composite made between nanoparticles and PCL-gelatin maintained the fibrous morphology of PGNPNF upto 14 days. The PGNPNF mesh exhibited a superoxide dismutase (SOD) mimetic activity due to the incorporated CeNPs. The PGNPNF mesh enhanced proliferation of 3T3-L1 cells by ∼48% as confirmed by alamar blue assay and SEM micrographs of cells grown on the nanofibrous mesh. Furthermore, the PGNPNF mesh scavenged ROS, which was measured by relative DCF intensity and fluorescence microscopy; and subsequently increased the viability and proliferation of cells by three folds as it alleviated the oxidative stress. Overall, the results of this study suggest the potential of CeNP functionalised PCL-gelatin nanofibrous mesh for wound healing applications.

Effects of Cerium Oxide Nanoparticles on Sorghum Plant Traits

NASA Astrophysics Data System (ADS)

Mu, L.; Chen, Y.; Darnault, C. J. G.; Rauh, B.; Kresovich, S.; Korte, C.

2015-12-01

Nanotechnology and nanomaterials are considered as the development of the modern science. However, besides with that wide application, nanoparticles arouse to the side effects on the environment and human health. As the catalyst of ceramics and fuel industry, Cerium (IV) oxide nanoparticles (CeO2 NPs) can be found in the environment following their use and life-cycle. Therefore, it is critical to assess the potential effects that CeO2 NPs found in soils may have on plants. In this study, CeO2 NPs were analyzed for the potential influence on the sorghum [Sorghum bicolor (L.) Moench] (Reg. no. 126) (PI 154844) growth and traits. The objectives of this research were to determine whether CeO2 NPs impact the sorghum germination and growth characteristics. The sorghum was grown in the greenhouse located at Biosystems Research Complex, Clemson University under different CeO2 NPs treatments (0mg; 100mg; 500mg; 1000mg CeO2 NPs/Kg soil) and harvested around each month. At the end of the each growing period, above ground vegetative tissue was air-dried, ground to 2mm particle size and compositional traits estimated using near-infrared spectroscopy. Also, the NPK value of the sorghum tissue was tested by Clemson Agriculture Center. After the first harvest, the result showed that the height of above ground biomass under the nanoparticles stress was higher than that of control group. This difference between the control and the nanoparticles treatments was significant (F>F0.05; LSD). Our results also indicated that some of the compositional traits were impacted by the different treatments, including the presence and/or concentrations of the nanoparticles.

Pharmacological potential of cerium oxidenanoparticles

NASA Astrophysics Data System (ADS)

Celardo, Ivana; Pedersen, Jens Z.; Traversa, Enrico; Ghibelli, Lina

2011-04-01

Nanotechnology promises a revolution in pharmacology to improve or create ex novo therapies. Cerium oxidenanoparticles (nanoceria), well-known as catalysts, possess an astonishing pharmacological potential due to their antioxidant properties, deriving from a fraction of Ce3+ ions present in CeO2. These defects, compensated by oxygen vacancies, are enriched at the surface and therefore in nanosized particles. Reactions involving redox cycles between the Ce3+ and Ce4+oxidation states allow nanoceria to react catalytically with superoxide and hydrogen peroxide, mimicking the behavior of two key antioxidant enzymes, superoxide dismutase and catalase, potentially abating all noxious intracellularreactive oxygen species (ROS) via a self-regenerating mechanism. Hence nanoceria, apparently well tolerated by the organism, might fight chronic inflammation and the pathologies associated with oxidative stress, which include cancer and neurodegeneration. Here we review the biological effects of nanoceria as they emerge from in vitro and in vivo studies, considering biocompatibility and the peculiar antioxidant mechanisms.

Comparison of Elemental Mercury Oxidation Across Vanadium and Cerium Based Catalysts in Coal Combustion Flue Gas: Catalytic Performances and Particulate Matter Effects.

PubMed

Wan, Qi; Yao, Qiang; Duan, Lei; Li, Xinghua; Zhang, Lei; Hao, Jiming

2018-03-06

This paper discussed the field test results of mercury oxidation activities over vanadium and cerium based catalysts in both coal-fired circulating fluidized bed boiler (CFBB) and chain grate boiler (CGB) flue gases. The characterizations of the catalysts and effects of flue gas components, specifically the particulate matter (PM) species, were also discussed. The catalytic performance results indicated that both catalysts exhibited mercury oxidation preference in CGB flue gas rather than in CFBB flue gas. Flue gas component studies before and after dust removal equipment implied that the mercury oxidation was well related to PM, together with gaseous components such as NO, SO 2 , and NH 3 . Further investigations demonstrated a negative PM concentration-induced effect on the mercury oxidation activity in the flue gases before the dust removal, which was attributed to the surface coverage by the large amount of PM. In addition, the PM concentrations in the flue gases after the dust removal failed in determining the mercury oxidation efficiency, wherein the presence of different chemical species in PM, such as elemental carbon (EC), organic carbon (OC) and alkali (earth) metals (Na, Mg, K, and Ca) in the flue gases dominated the catalytic oxidation of mercury.

Polyacrylic acid-coated cerium oxide nanoparticles: An oxidase mimic applied for colorimetric assay to organophosphorus pesticides.

PubMed

Zhang, Shi-Xiang; Xue, Shi-Fan; Deng, Jingjing; Zhang, Min; Shi, Guoyue; Zhou, Tianshu

2016-11-15

It is important and urgent to develop reliable and highly sensitive methods that can provide on-site and rapid detection of extensively used organophosphorus pesticides (OPs) for their neurotoxicity. In this study, we developed a novel colorimetric assay for the detection of OPs based on polyacrylic acid-coated cerium oxide nanoparticles (PAA-CeO2) as an oxidase mimic and OPs as inhibitors to suppress the activity of acetylcholinesterase (AChE). Firstly, highly dispersed PAA-CeO2 was prepared in aqueous solution, which could catalyze the oxidation of TMB to produce a color reaction from colorless to blue. And the enzyme of AChE was used to catalyze the substrate of acetylthiocholine (ATCh) to produce thiocholine (TCh). As a thiol-containing compound with reducibility, TCh can decrease the oxidation of TMB catalyzed by PAA-CeO2. Upon incubated with OPs, the enzymatic activity of AChE was inhibited to produce less TCh, resulting in more TMB catalytically oxidized by PAA-CeO2 to show an increasing blue color. The two representative OPs, dichlorvos and methyl-paraoxon, were tested using our proposed assay. The novel assay showed notable color change in a concentration-dependent manner, and as low as 8.62 ppb dichlorvos and 26.73 ppb methyl-paraoxon can be readily detected. Therefore, taking advantage of such oxidase-like activity of PAA-CeO2, our proposed colorimetric assay can potentially be a screening tool for the precise and rapid evaluation of the neurotoxicity of a wealth of OPs. Copyright © 2016 Elsevier B.V. All rights reserved.

Cerium nanoparticle effect on sensitivity of Fricke gel dosimeter: Initial investigation

NASA Astrophysics Data System (ADS)

Ebenezer Suman Babu, S.; Peace Balasingh, S. Timothy; Benedicta Pearlin, R.; Rabi Raja Singh, I.; Ravindran, B. Paul

2017-05-01

Fricke gel dosimeters (FXGs) have been the preferred dosimeters because of its ease in preparation and water and tissue equivalency. Visible changes happen three dimensionally in the dosimeter as the ferrous (Fe2+) ions change into ferric (Fe3+) ions upon irradiation and the measure of this change can be correlated to the dose absorbed. Nanoparticles are promising entities that can improve the sensitivity of the gel dosimeter. Cerium Oxide nanoparticle was investigated for possible enhancement of absorbed dose in the FXG. Various concentrations of the nanoparticle based gel dosimeters were prepared and irradiated for a clinical dose range of 0-3 Gy in a telegamma unit. The optimal concentration of 0.1 mM nanoparticle incorporated in the FXG enhances the radiation sensitivity of the unmodified FXG taken as reference without modifying the background absorbance prior to irradiation. The gel recipe consisted of 5% (wt) gelatin, 50 mM Sulphuric acid, 0.05 mM Xylenol Orange, 0.5 mM Ferrous Ammonium Sulphate and 0.1 mM Cerium (IV) Oxide nanoparticle (< 25 nm particle size) and triple distilled water. The FXGs with nanoparticle showed linear dose response in the dose range tested.

Effects of calcium and phosphate on uranium(IV) oxidation: Comparison between nanoparticulate uraninite and amorphous U IV–phosphate

DOE PAGES

Latta, Drew E.; Kemner, Kenneth M.; Mishra, Bhoopesh; ...

2015-11-17

The mobility of uranium in subsurface environments depends strongly on its redox state, with U IV phases being significantly less soluble than U VI minerals. This study compares the oxidation kinetics and mechanisms of two potential products of U VI reduction in natural systems, a nanoparticulate UO 2 phase and an amorphous U IV–Ca–PO 4 analog to ningyoite (CaU IV(PO 4) 2·1–2H 2O). The valence of U was tracked by X-ray absorption near-edge spectroscopy (XANES), showing similar oxidation rate constants for U IVO 2 and U IV–phosphate in solutions equilibrated with atmospheric O 2 and CO 2 at pH 7.0more » (k obs,UO2 = 0.17 ± 0.075 h -1 vs. k obs,U IV PO4 = 0.30 ± 0.25 h -1). Addition of up to 400 μM Ca and PO 4 decreased the oxidation rate constant by an order of magnitude for both UO 2 and U IV–phosphate. The intermediates and products of oxidation were tracked by electron microscopy, powder X-ray diffraction (pXRD), and extended X-ray absorption fine-structure spectroscopy (EXAFS). In the absence of Ca or PO 4, the product of UO 2 oxidation is Na–uranyl oxyhydroxide (under environmentally relevant concentrations of sodium, 15 mM NaClO 4 and low carbonate concentration), resulting in low concentrations of dissolved U VI (<2.5 × 10 -7 M). Oxidation of U IV–phosphate produced a Na-autunite phase (Na 2(UO 2)PO 4·xH 2O), resulting in similarly low dissolved U concentrations (<7.3 × 10 -8 M). When Ca and PO 4 are present in the solution, the EXAFS data and the solubility of the UVI phase resulting from oxidation of UO 2 and UIV–phosphate are consistent with the precipitation of Na-autunite. Bicarbonate extractions and Ca K-edge X-ray absorption spectroscopy of oxidized solids indicate the formation of a Ca–UVI–PO 4 layer on the UO 2 surface and suggest a passivation layer mechanism for the decreased rate of UO 2 oxidation in the presence of Ca and PO 4. Interestingly, the extractions were unable to remove all of the oxidized U from partially

Cerium oxide nanoparticles promote neurogenesis and abrogate hypoxia-induced memory impairment through AMPK–PKC–CBP signaling cascade

PubMed Central

Arya, Aditya; Gangwar, Anamika; Singh, Sushil Kumar; Roy, Manas; Das, Mainak; Sethy, Niroj Kumar; Bhargava, Kalpana

2016-01-01

Structural and functional integrity of the brain is adversely affected by reduced oxygen saturation, especially during chronic hypoxia exposure and often encountered by altitude travelers or dwellers. Hypoxia-induced generation of reactive nitrogen and oxygen species reportedly affects the cortex and hippocampus regions of the brain, promoting memory impairment and cognitive dysfunction. Cerium oxide nanoparticles (CNPs), also known as nanoceria, switch between +3 and +4 oxidation states and reportedly scavenge superoxide anions, hydrogen peroxide, and peroxynitrite in vivo. In the present study, we evaluated the neuroprotective as well as the cognition-enhancing activities of nanoceria during hypobaric hypoxia. Using polyethylene glycol-coated 3 nm nanoceria (PEG-CNPs), we have demonstrated efficient localization of PEG-CNPs in rodent brain. This resulted in significant reduction of oxidative stress and associated damage during hypoxia exposure. Morris water maze-based memory function tests revealed that PEG-CNPs ameliorated hypoxia-induced memory impairment. Using microscopic, flow cytometric, and histological studies, we also provide evidences that PEG-CNPs augmented hippocampus neuronal survival and promoted neurogenesis. Molecular studies revealed that PEG-CNPs promoted neurogenesis through the 5′-adenine monophosphate-activated protein kinase–protein kinase C–cyclic adenosine monophosphate response element-binding protein binding (AMPK-PKC-CBP) protein pathway. Our present study results suggest that nanoceria can be translated as promising therapeutic molecules for neurodegenerative diseases. PMID:27069362

Investigating effects of nano cerium oxide reinforcement on mechanical properties of composite based on natural rubber

NASA Astrophysics Data System (ADS)

Bao, Le Quoc; Phan, Vu Hoang Giang; Khuyen, Nguyen Quang

2018-04-01

Polymer nanocomposites that based on combination of nanomaterials (such as nanoparticles, nanotubes, nanorods, nanofibers, and nanosheets) and polymeric matrices are receiving great attention in research and application. However, separate and homogenous dispersion rather than aggregates of nanoparticles into matrices meet big difficulty due to large interaction between nanoparticles. The poor dispersion leads to low properties of nanocomposites. In this study, we find out the appropriate method to separately disperse cerium oxides (CeO2) nanoparticles into natural rubber, aiming to increase mechanical properties of natural rubber. The SEM images were used to evaluate the dispersion of nano CeO2 in natural rubber matrix. The mechanical properties of nanocomposites were measured after vulcanization to investigate effects of nano CeO2 amount on prepared composite. The findings exhibited that the addition of CeO2 by dispersion of nano CeO2 in water via ultrasonication before mixing with rubber latex, significantly increase modulus, tear and wear resistance of natural rubber.

Effect of Adding Cerium on Microstructure and Morphology of Ce-Based Inclusions Formed in Low-Carbon Steel

PubMed Central

Adabavazeh, Z.; Hwang, W. S.; Su, Y. H.

2017-01-01

Intra-granular Acicular Ferrite (IAF), as one of the most well-known desirable microstructure of ferrite with a chaotic crystallographic orientation, can not only refine the microstructure and retard the propagation of cleavage crack but also provide excellent combination of strength and toughness in steel. The effect of adding cerium on microstructure and controlling proper cerium-based inclusions in order to improve properties in low-carbon commercial steel (SS400) were investigated. The type of inclusions can be controlled by changing S/O ratio and Ce content. Without Ce modification, MnS is a dominate inclusion. After adding Ce, the stable inclusion phases change from AlCeO3 to Ce2O2S. The optimum amount of cerium, 0.0235 wt.%, lead in proper grain refinement and formation of cerium oxide, oxy-sulfide and sulfide inclusions. Having a high amount of cerium results in increasing the number of inclusions significantly as a result it cannot be effective enough and the inclusions will act like barriers for others. It is found that the inclusions with a size of about 4∼7 μm can serve as heterogeneous nucleation sites for AF formation. Thermodynamic calculations have been applied to predict the inclusion formation in this molten steel as well, which show a good agreement with experimental one. PMID:28485376

Cardioprotective effect of cerium oxide nanoparticles in monocrotaline rat model of pulmonary hypertension: A possible implication of endothelin-1.

PubMed

Nassar, Seham Zakaria; Hassaan, Passainte S; Abdelmonsif, Doaa A; ElAchy, Samar Nabil

2018-05-15

Cerium oxide nanoparticles (CeO 2 NPs) have been recently introduced into the medical field for their antioxidant properties. The ability of CeO 2 NPs alone or in combination with spironolactone (SP) to attenuate monocrotaline (MCT)-induced pulmonary hypertension and associated right ventricular hypertrophy was studied in rats. A special emphasis was given to endothelin-1 pathway. Pulmonary hypertension was induced in albino rats by a single subcutaneous injection of MCT (60 mg/kg). Rats received either single CeO 2 NPs therapy or combined therapy with SP for 2 weeks. CeO 2 NPs improved pulmonary function tests with concomitant decrease in serum endothelin-1 and pulmonary expression of endothelin-1 and its receptor ETAR. Besides, CeO 2 NPs diminished MCT-induced right ventricular hypertrophy and reduced cardiac oxidative stress and apoptosis. CeO 2 NPs could improve pulmonary hypertension and associated right ventricular hypertrophy with no additive value for SP. Besides being an antioxidant, CeO 2 NPs work through endothelin-1 pathway to improve pulmonary hypertension. Copyright © 2018 Elsevier Inc. All rights reserved.

Tuning the Selectivity of Catalytic Carbon Dioxide Hydrogenation over Iridium/Cerium Oxide Catalysts with a Strong Metal-Support Interaction.

PubMed

Li, Siwei; Xu, Yao; Chen, Yifu; Li, Weizhen; Lin, Lili; Li, Mengzhu; Deng, Yuchen; Wang, Xiaoping; Ge, Binghui; Yang, Ce; Yao, Siyu; Xie, Jinglin; Li, Yongwang; Liu, Xi; Ma, Ding

2017-08-28

A one-step ligand-free method based on an adsorption-precipitation process was developed to fabricate iridium/cerium oxide (Ir/CeO 2 ) nanocatalysts. Ir species demonstrated a strong metal-support interaction (SMSI) with the CeO 2 substrate. The chemical state of Ir could be finely tuned by altering the loading of the metal. In the carbon dioxide (CO 2 ) hydrogenation reaction it was shown that the chemical state of Ir species-induced by a SMSI-has a major impact on the reaction selectivity. Direct evidence is provided indicating that a single-site catalyst is not a prerequisite for inhibition of methanation and sole production of carbon monoxide (CO) in CO 2 hydrogenation. Instead, modulation of the chemical state of metal species by a strong metal-support interaction is more important for regulation of the observed selectivity (metallic Ir particles select for methane while partially oxidized Ir species select for CO production). The study provides insight into heterogeneous catalysts at nano, sub-nano, and atomic scales. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Preparation and evaluation of cerium oxide-bovine hydroxyapatite composites for biomedical engineering applications.

PubMed

Gunduz, O; Gode, C; Ahmad, Z; Gökçe, H; Yetmez, M; Kalkandelen, C; Sahin, Y M; Oktar, F N

2014-07-01

The fabrication and characterization of bovine hydroxyapatite (BHA) and cerium oxide (CeO2) composites are presented. CeO2 (at varying concentrations 1, 5 and 10wt%) were added to calcinated BHA powder. The resulting mixtures were shaped into green cylindrical samples by powder pressing (350MPa) followed by sintering in air (1000-1300°C for 4h). Density, Vickers microhardness (HV), compression strength, scanning electron microscopy (SEM) and X-ray diffraction (XRD) studies were performed on the products. The sintering behavior, microstructural characteristics and mechanical properties were evaluated. Differences in the sintering temperature (for 1wt% CeO2 composites) between 1200 and 1300°C, show a 3.3% increase in the microhardness (564 and 582.75HV, respectively). Composites prepared at 1300°C demonstrate the greatest compression strength with comparable results for 5 and 10wt% CeO2 content (106 and 107MPa) which are significantly better than those for 1wt% and those that do not include any CeO2 (90 and below 60MPa, respectively). The results obtained suggest optimal parameters to be used in preparation of BHA and CeO2 composites, while also highlighting the potential of such materials in several biomedical engineering applications. Copyright © 2014 Elsevier Ltd. All rights reserved.

Protection and Sensitization of Human Cells to Proton Radiation by Cerium Oxide Nanoparticles

NASA Astrophysics Data System (ADS)

Carlson, Nathan B.

In radiation therapy for the treatment of cancer, there is demand for novel approaches that will improve tumor cell killing while protecting healthy tissue. One such approach that has shown considerable promise is the application of nanoparticles as radiation sensitizers for tumor cells and as radiation protectants for healthy tissue. In this investigation, cerium oxide nanoparticles (CNPs) obtained from the University of Central Florida's NanoScience Technology Center were studied for their protective effect to charged particle radiation in non-malignant breast cells, and for their sensitizing effect in breast and prostate cancer cell lines. These experiments were conducted at East Carolina University, where human cells were grown in the cell culture facility in the Department of Biology and then irradiated with energetic protons in the Accelerator Laboratory in the Department of Physics. Prior to irradiation, the cells were treated with distinct CNP preparations ranging in concentrations from 10 nanomolar to 10 micromolar, and cell viability was assessed using multiple assays post-irradiation. Radioprotection and radiosensitization were observed for several of the CNP treatments tested. Ultimately, the goal is to find a specific nanoparticle treatment that holds the synergistic effect of enhancing the rate of killing in tumor cells while simultaneously improving the survival of normal cells.

Near-road modeling and measurement of cerium-containing particles generated by nanoparticle diesel fuel additive use

EPA Science Inventory

Cerium oxide nanoparticles (nCe) are used as a fuel-borne catalyst in diesel engines to reduce particulate emissions, yet the environmental and human health impacts of the exhaust particles are not well understood. To bridge the gap between emission measurements and ambient impac...

Synthesis of mesoporous cerium compound for CO2 capture

NASA Astrophysics Data System (ADS)

Liu, Guiqing; Tatsuda, Kou; Yoneyama, Yoshiharu; Tsubaki, Noritatsu

2017-11-01

A mesoporous adsorbent was simply synthesized by adding alkaline substances to cerium(III) nitric hydrate. The surface characteristics of the synthesized cerium compound were determined with BET, XRD and TEM analysis. It was found that although the specific surface areas of the synthesized cerium compounds were among about 120-200m2 per gram (BET area) which were smaller than the common used zeolite 13X (BET area 743 m2/g) and activated carbon (BET area 1079 m2/g), but the cerium compounds had excellent performances for CO2 adsorption as well as the CO2 desorption.

Modeles numeriques de la stimulation optique de neurones assistee par nanoparticules plasmoniques

NASA Astrophysics Data System (ADS)

Le Hir, Nicolas

La stimulation de neurones par laser emerge depuis plusieurs annees comme une alternative aux techniques plus traditionnelles de stimulation artificielle. Contrairement a celles-ci, la stimulation lumineuse ne necessite pas d'interagir directement avec le tissu organique, comme c'est le cas pour une stimulation par electrodes, et ne necessite pas de manipulation genetique comme c'est le cas pour les methodes optogenetiques. Plus recemment, la stimulation lumineuse de neurones assistee par nanoparticules a emerge comme un complement a la stimulation simplement lumineuse. L'utilisation de nanoparticules complementaires permet d'augmenter la precision spatiale du procede et de diminuer la fluence necessaire pour observer le phenomene. Ceci vient des proprietes d'interaction entre les nanoparticules et le faisceau laser, comme par exemple les proprietes d'absorption des nanoparticules. Deux phenomenes princpaux sont observes. Dans certains cas, il s'agit d'une depolarisation de la membrane, ou d'un potentiel d'action. Dans d'autres experiences, un influx de calcium vers l'interieur du neurone est detecte par une augmentation de la fluorescence d'une proteine sensible a la concentration calcique. Certaines stimulations sont globales, c'est a dire qu'une perturbation se propage a l'ensemble du neurone : c'est le cas d'un potentiel d'action. D'autres sont, au contraire, locales et ne se propagent pas a l'ensemble de la cellule. Si une stimulation lumineuse globale est rendue possible par des techniques relativement bien maitrisees a l'heure actuelle, comme l'optogenetique, une stimulation uniquement locale est plus difficile a realiser. Or, il semblerait que les methodes de stimulation lumineuse assistees par nanoparticules puissent, dans certaines conditions, offrir cette possibilite. Cela serait d'une grande aide pour conduire de nouvelles etudes sur le fonctionnement des neurones, en offrant de nouvelles possibilites experimentales en complement des possibilites

Occurrence and behaviour of dissolved, nano-particulate and micro-particulate iron in waste waters and treatment systems: new insights from electrochemical analysis.

PubMed

Matthies, R; Aplin, A C; Horrocks, B R; Mudashiru, L K

2012-04-01

Cyclic-, Differential Pulse- and Steady-state Microdisc Voltammetry (CV, DPV, SMV) techniques have been used to quantify the occurrence and fate of dissolved Fe(ii)/Fe(iii), nano-particulate and micro-particulate iron over a 12 month period in a series of net-acidic and net-alkaline coal mine drainages and passive treatment systems. Total iron in the mine waters is typically 10-100 mg L(-1), with values up to 2100 mg L(-1). Between 30 and 80% of the total iron occurs as solid phase, of which 20 to 80% is nano-particulate. Nano-particulate iron comprises 20 to 70% of the nominally "dissolved" (i.e. <0.45 μm) iron. Since coagulation and sedimentation are the only processes required to remove solid phase iron, these data have important implications for the generation or consumption of acidity during water treatment. In most waters, the majority of truly dissolved iron occurs as Fe(ii) (average 64 ± 22%). Activities of Fe(ii) do not correlate with pH and geochemical modelling shows that no Fe(ii) mineral is supersaturated. Removal of Fe(ii) must proceed via oxidation and hydrolysis. Except in waters with pH < 4.4, activities of Fe(iii) are strongly and negatively correlated with pH. Geochemical modelling suggests that the activity of Fe(iii) is controlled by the solubility of hydrous ferric oxides and oxyhydroxysulfates, supported by scanning and transmission electron microscopic analysis of solids. Nevertheless, the waters are generally supersaturated with respect to ferrihydrite and schwertmannite, and are not at redox equilibrium, indicating the key role of oxidation and hydrolysis kinetics on water treatment. Typically 70-100% of iron is retained in the treatment systems. Oxidation, hydrolysis, precipitation, coagulation and sedimentation occur in all treatment systems and - independent of water chemistry and the type of treatment system - hydroxides and oxyhydroxysulfates are the main iron sinks. The electrochemical data thus reveal the rationale for incomplete

Molecular Dynamics Modeling and Simulation of Diamond Cutting of Cerium.

PubMed

Zhang, Junjie; Zheng, Haibing; Shuai, Maobing; Li, Yao; Yang, Yang; Sun, Tao

2017-12-01

The coupling between structural phase transformations and dislocations induces challenges in understanding the deformation behavior of metallic cerium at the nanoscale. In the present work, we elucidate the underlying mechanism of cerium under ultra-precision diamond cutting by means of molecular dynamics modeling and simulations. The molecular dynamics model of diamond cutting of cerium is established by assigning empirical potentials to describe atomic interactions and evaluating properties of two face-centered cubic cerium phases. Subsequent molecular dynamics simulations reveal that dislocation slip dominates the plastic deformation of cerium under the cutting process. In addition, the analysis based on atomic radial distribution functions demonstrates that there are trivial phase transformations from the γ-Ce to the δ-Ce occurred in both machined surface and formed chip. Following investigations on machining parameter dependence reveal the optimal machining conditions for achieving high quality of machined surface of cerium.

Molecular Dynamics Modeling and Simulation of Diamond Cutting of Cerium

NASA Astrophysics Data System (ADS)

Zhang, Junjie; Zheng, Haibing; Shuai, Maobing; Li, Yao; Yang, Yang; Sun, Tao

2017-07-01

The coupling between structural phase transformations and dislocations induces challenges in understanding the deformation behavior of metallic cerium at the nanoscale. In the present work, we elucidate the underlying mechanism of cerium under ultra-precision diamond cutting by means of molecular dynamics modeling and simulations. The molecular dynamics model of diamond cutting of cerium is established by assigning empirical potentials to describe atomic interactions and evaluating properties of two face-centered cubic cerium phases. Subsequent molecular dynamics simulations reveal that dislocation slip dominates the plastic deformation of cerium under the cutting process. In addition, the analysis based on atomic radial distribution functions demonstrates that there are trivial phase transformations from the γ-Ce to the δ-Ce occurred in both machined surface and formed chip. Following investigations on machining parameter dependence reveal the optimal machining conditions for achieving high quality of machined surface of cerium.

ADSORPTION OF CERIUM VALUES FROM AQUEOUS SOLUTIONS

DOEpatents

Roberts, F.P.

1963-08-13

Cerium can be removed from aqueous nitric acid (2 to 13 M) solutions by passing the latter over a PbO/sub 2/-containing anion exchange resin. The cerium is taken up by the resin, while any lanthanides, yttrium, and strontium present remain in the solution. (AEC)

Shock driven melting and resolidification upon release in cerium

NASA Astrophysics Data System (ADS)

Bolme, Cindy; Bronkhorst, Curt; Brown, Don; Cherne, Frank; Cooley, Jason; Furlanetto, Michael; Gleason, Arianna; Jensen, Brian; Owens, Charles; Ali, Suzanne; Fratanduono, Dayne; Galtier, Eric; Granados, Eduardo; Lee, Hae Ja; Nagler, Bob

2017-06-01

The temperature rise due to increasing entropy during shock compression and the corresponding temperature decrease due to isentropic expansion upon release cause the physics of melting and solidification under dynamic pressure changes to differ fundamentally from the more common liquid-solid transitions governed by thermal diffusion. We investigated laser shock driven melting and resolidification during release in cerium to examine the dynamics of these processes. Cerium was selected as the material of study due to the low pressure at which γ-cerium melts along the principle Hugoniot and due to cerium's anomalous melt boundary at low pressure, which facilitates its transition from liquid to solid during isentropic release. The structural phase of cerium was probed with X-ray diffraction using the LCLS X-ray free electron laser, which provided in situ measurements of the transition dynamics. The experimental results will be presented showing the resolidification occurring over 10s of ns.

Production of Monodisperse Cerium Oxide Microspheres with Diameters near 100 µm by Internal-Gelation Sol-Gel Methods

DOE Office of Scientific and Technical Information (OSTI.GOV)

Katalenich, Jeffrey A.; Kitchen, Brian B.; Pierson, Bruce

Cerium dioxide microspheres with uniform diameters between 65 – 211 µm were fabricated using internal gelation sol-gel methods. Although uniform microspheres are produced for nuclear fuel applications with diameters above 300 µm, sol-gel microspheres with diameters of 50 - 200 µm have historically been made by emulsion techniques and had poor size uniformity [1, 2]. An internal gelation, sol-gel apparatus was designed and constructed to accommodate the production of small, uniform microspheres whereby cerium-containing solutions were dispersed into flowing silicone oil and heated in a gelation column to initiate solidification [3, 4]. Problems with premature feed gelation and microsphere coalescencemore » were overcome by equipment modifications unique among known internal gelation setups. Microspheres were fabricated and sized in batches as a function of dispersing needle diameter and silicone oil flow rate in the two-fluid nozzle in order to determine the range of sizes possible and corresponding degree of monodispersity. Initial experiments with poor size uniformity were linked to microsphere coalescence in the gelation column prior to solidification as well as excessive flow rates for the cerium feed solution. Average diameter standard deviations as low as 2.23% were observed after optimization of flow rates and minimization of coalescence reactions.« less

Production of monodisperse cerium oxide microspheres with diameters near 100 µm by internal-gelation sol–gel methods

DOE Office of Scientific and Technical Information (OSTI.GOV)

Katalenich, Jeffrey A.; Kitchen, Brian B.; Pierson, Bruce D.

Cerium dioxide microspheres with uniform diameters between 65 – 211 µm were fabricated using internal gelation sol-gel methods. Although uniform microspheres are produced for nuclear fuel applications with diameters above 300 µm, sol-gel microspheres with diameters of 50 - 200 µm have historically been made by emulsion techniques and had poor size uniformity [1, 2]. An internal gelation, sol-gel apparatus was designed and constructed to accommodate the production of small, uniform microspheres whereby cerium-containing solutions were dispersed into flowing silicone oil and heated in a gelation column to initiate solidification [3, 4]. Problems with premature feed gelation and microsphere coalescencemore » were overcome by equipment modifications unique among known internal gelation setups. Microspheres were fabricated and sized in batches as a function of dispersing needle diameter and silicone oil flow rate in the two-fluid nozzle in order to determine the range of sizes possible and corresponding degree of monodispersity. Initial experiments with poor size uniformity were linked to microsphere coalescence in the gelation column prior to solidification as well as excessive flow rates for the cerium feed solution. Average diameter standard deviations as low as 2.23% were observed after optimization of flow rates and minimization of coalescence reactions.« less

Anionic Cerium Oxide Nanoparticles Protect Plant Photosynthesis from Abiotic Stress by Scavenging Reactive Oxygen Species.

PubMed

Wu, Honghong; Tito, Nicholas; Giraldo, Juan P

2017-11-28

Plant abiotic stress leads to accumulation of reactive oxygen species (ROS) and a consequent decrease in photosynthetic performance. We demonstrate that a plant nanobionics approach of localizing negatively charged, sub-11 nm, spherical cerium oxide nanoparticles (nanoceria) inside chloroplasts in vivo augments ROS scavenging and photosynthesis of Arabidopsis thaliana plants under excess light (2000 μmol m -2 s -1 , 1.5 h), heat (35 °C, 2.5 h), and dark chilling (4 °C, 5 days). Poly(acrylic acid) nanoceria (PNC) with a hydrodynamic diameter (10.3 nm)-lower than the maximum plant cell wall porosity-and negative ζ-potential (-16.9 mV) exhibit significantly higher colocalization (46%) with chloroplasts in leaf mesophyll cells than aminated nanoceria (ANC) (27%) of similar size (12.6 nm) but positive charge (9.7 mV). Nanoceria are transported into chloroplasts via nonendocytic pathways, influenced by the electrochemical gradient of the plasma membrane potential. PNC with a low Ce 3+ /Ce 4+ ratio (35.0%) reduce leaf ROS levels by 52%, including hydrogen peroxide, superoxide anion, and hydroxyl radicals. For the latter ROS, there is no known plant enzyme scavenger. Plants embedded with these PNC that were exposed to abiotic stress exhibit an increase up to 19% in quantum yield of photosystem II, 67% in carbon assimilation rates, and 61% in Rubisco carboxylation rates relative to plants without nanoparticles. In contrast, PNC with high Ce 3+ /Ce 4+ ratio (60.8%) increase overall leaf ROS levels and do not protect photosynthesis from oxidative damage during abiotic stress. This study demonstrates that anionic, spherical, sub-11 nm PNC with low Ce 3+ /Ce 4+ ratio can act as a tool to study the impact of oxidative stress on plant photosynthesis and to protect plants from abiotic stress.

Optical properties of cerium doped oxyfluoroborate glass.

PubMed

Bahadur, A; Dwivedi, Y; Rai, S B

2013-06-01

Cerium doped oxyfluoroborate glasses have been prepared and its spectroscopic properties have been discussed. It is found that the absorption edge shifts towards the lower energy side for the higher concentration of cerium dopant. Optical band gap for these glasses have been calculated and it is found that the number of non-bridging oxygen increases with cerium content. The emission spectra of these glasses have been recorded using UV laser radiations (266 and 355 nm) and it is observed that these glasses show bright blue emission. On the basis of excitation and emission spectra we have reported the existence of at least two different emission centers of Ce(3+)ions. Copyright © 2013 Elsevier B.V. All rights reserved.

Specific Features of the Response of Cerium to Pulsed Actions

NASA Astrophysics Data System (ADS)

Atroshenko, S. A.; Zubareva, A. N.; Morozov, V. A.; Savenkov, G. G.; Utkin, A. V.

2018-02-01

Experimental studies of cerium at high rates and nanosecond durations of action have been performed. The isomorphic phase transition was studied upon shock compression. The spall strength of cerium has been determined. Cerium demonstrates anomalous compressibility upon dynamic loading. Stress waves dampen under action of a high-current electron beam due to the energy dissipation during fragmentation and twinning.

Corrosion resistance of BIS 2062-grade steel coated with nano-metal-oxide mixtures of iron, cerium, and titanium in the marine environment

NASA Astrophysics Data System (ADS)

Ashraf, P. Muhamed; Anuradha, R.

2018-02-01

BIS 2062-grade carbon steel is extensively used for fishing boat construction. The steel is highly susceptible to corrosion on the hull and welding joints under marine environment. Here, we demonstrate the application of a novel multifunctional nano-metal-oxide mixture comprised of iron, titanium, and cerium as a marine coating to prevent corrosion. The electrochemical performance of nano-metal-oxide mixture coatings, applied over boat-building steel, was evaluated at 3.5% NaCl medium. The nano-mixture surface coatings showed an efficient corrosion resistance with increased polarization resistance of 6043 Ω cm2 and low corrosion current density of 3.53 × 10-6 A cm-2. The electrochemical impedance spectral data exhibited improvement in the polarization resistance of outermost surface and internal layers. The coating responded faster recovery to normal state when subjected to an induced stress over the coating. The nano-material in the coating behaves as a semiconductor; this enhanced electronic activity over the surface of the steel.

Cerium oxide nanozyme modulate the ‘exercise’ redox biology of skeletal muscle

NASA Astrophysics Data System (ADS)

Arya, Aditya; Sethy, Niroj Kumar; Gangwar, Anamika; Bhargava, Neelima; Dubey, Amarish; Roy, Manas; Srivastava, Gaurav; Singh, Sushil Kumar; Das, Mainak; Bhargava, Kalpana

2017-05-01

‘Exercise’ is a double-edged sword for the skeletal muscle. Small amount of ROS generated during mild exercise, is essential for normal force generation; whereas large quantity of ROS generated during intense exercise, may cause contractile dysfunction, resulting in muscle weakness and fatigue. One of the key question in skeletal muscle physiology is ‘could antioxidant therapy improve the skeletal muscle endurance? A question, which has resulted in contradictory experimental findings till this date. This work has addressed this ‘very question’ using a synthetic, inorganic, antioxidant nano-material viz., ‘cerium oxide nanozyme’ (CON). It has been introduced in the rat by intramuscular injection, and the skeletal muscle endurance has been evaluated. Intramuscular injections of CON, concurrent with exercise, enhanced muscle mass, glycogen and ATP content, type I fiber ratio, thus resulting in significantly higher muscle endurance. Electron microscope studies confirmed the presence of CON in the vicinity of muscle mitochondria. There was an increase in the number and size of the muscle mitochondria in the CON treated muscle, following exercise, as compared to the untreated group with only exercised muscle. Quantitative proteomics data and subsequent biological network analysis studies, identified higher levels of oxidative phosphorylation, TCA cycle output and glycolysis in CON supplemented exercised muscle over only exercised muscle. This was further associated with significant increase in the mitochondrial respiratory capacity and muscle contraction, primarily due to higher levels of electron transport chain proteins like NDUFA9, SDHA, ATP5B and ATP5D, which were validated by real-time PCR and western blotting. Along with this, persistence of CON in muscle was evaluated with ICP-MS analysis, which revealed clearance of the particles after 90 d, without exhibiting any inflammation or adverse affects on the health of the experimental animals. Thus a

Effect of Thickness on the Morphology and Corrosion Behavior of Cerium-Based Conversion Coatings on AZ31B Magnesium Alloy

NASA Astrophysics Data System (ADS)

Castano, Carlos E.; Maddela, Surender; O'Keefe, Matthew J.; Wang, Yar-Ming

Cerium-based conversion coatings (CeCCs) were deposited onto AZ31B magnesium alloy substrates using a spontaneous reaction of CeCl3, H2O2 and gelatin in a water-based solution. The coating thickness was adjusted by controlling the immersion time in the deposition solution. Prior to deposition, the AZ31B substrates were treated using an acid pickling in nitric acid and then an alkaline cleaning in sodium metasilicate pentahydrate. After deposition, the coated samples were immersed in a phosphate bath that converted cerium oxide/hydroxide into cerium phosphate. Electrochemical impedance spectroscopy, potentiodynamic polarization and neutral salt spray testing studies indicated that 100 nm thick CeCC had better corrosion performance than 400 nm coatings. Characterization of the CeCCs by transmission electron microscopy (TEM) revealed a three layer structure with different compositions.

Modified cermet fuel electrodes for solid oxide electrochemical cells

DOEpatents

Ruka, Roswell J.; Spengler, Charles J.

1991-01-01

An exterior porous electrode (10), bonded to a solid oxygen ion conducting electrolyte (13) which is in contact with an interior electrode (14), contains coarse metal particles (12) of nickel and/or cobalt, having diameters from 3 micrometers to 35 micrometers, where the coarse particles are coated with a separate, porous, multiphase layer (17) containing fine metal particles of nickel and/or cobalt (18), having diameters from 0.05 micrometers to 1.75 micrometers and conductive oxide (19) selected from cerium oxide, doped cerium oxide, strontium titanate, doped strontium titanate and mixtures thereof.

[Ion chromatography of L-ascorbic acid, sulfite and thiosulfate using their postcolumn reactions with cerium (IV) and fluorescence detection of cerium (III)].

PubMed

Chen, Q; Hu, K; Miura, Y

1999-09-01

An ion chromatographic method was used to separate the species of L-ascorbic acid, sulfite and thiosulfate in their mixtures. This method is based on the separation of each anion in their mixtures by using a separation column, and then on the fluorimetric measurement of cerium (III) formed by a postcolumn reaction of cerium (IV) with the species of L-ascorbic acid, sulfite and thiosulfate in the effluent. The optimal conditions for separating and determining the above three species have been established. By using a 3 mmol/L carbonate eluent, the species of L-ascorbic acid, sulfite and thiosulfate could be eluted at the proper retention times of 1.7, 2.6 and 5.0 min, respectively, and these three anions could be separated completely. The effects of the concentrations of cerium (IV) and sulfuric acid in the postcolumn reaction solution on the chromatographic peak-height were tested in order to obtain the optimal peak-height. It was found that the peak-height at first increases rapidly with an increase in the concentration of cerium (IV) and sulfuric acid respectively up to a certain concertation, then increases slowly. These critical concentrations of cerium (IV) and sulfuric acid also depend on the amount of the analyte injected. Meanwhile the baseline signals of the sepectra increase with an increase in the concentration of cerium (IV). Some concentrations above the critical concentration of sulfuric acid could be selected as the optimal concentration of sulfuric acid, but the concentration of cerium (IV) should be optimized by establishing a compromise between the higher peak-height and the lower baseline signal. The detection limit of this method was found to be 1 mumol/L for thiosulfate when an amount of 100 microL analyte was injected.

Cerium migration during PEM fuel cell assembly and operation

DOE PAGES

Baker, Andrew M.; Torraco, Dennis; Judge, Elizabeth J.; ...

2015-09-14

Cerium migration between PEM fuel cell components is influenced by potential-driven mobility, ionic diffusion, and gradients in water content. These factors were investigated in ex situ experiments and in operating fuel cells. Potential-induced migration was measured ex situ in hydrated window cells. Cerium-containing MEAs were also fabricated and tested under ASTs. MEA disassembly and subsequent XRF analysis were used to observe rapid cerium migration during cell assembly and operation. During MEA hot pressing, humidification, and low RH operation at OCV, ionic diffusion causes uniform migration from the membrane into the catalyst layers. During high RH operation at OCV, in-plane ceriummore » gradients arise due to variations in water content. These gradients may diminish the scavenging efficacy of cerium by reducing its proximity to generated radicals.« less

Trapped in the coordination sphere: Nitrate ion transfer driven by the cerium(III/IV) redox couple

DOE PAGES

Ellis, Ross J.; Bera, Mrinal K.; Reinhart, Benjamin; ...

2016-11-07

Redox-driven ion transfer between phases underpins many biological and technological processes, including industrial separation of ions. Here we investigate the electrochemical transfer of nitrate anions between oil and water phases, driven by the reduction and oxidation of cerium coordination complexes in oil phases. We find that the coordination environment around the cerium cation has a pronounced impact on the overall redox potential, particularly with regard to the number of coordinated nitrate anions. Our results suggest a new fundamental mechanism for tuning ion transfer between phases; by 'trapping' the migrating ion inside the coordination sphere of a redox-active complex. Here, thismore » presents a new route for controlling anion transfer in electrochemically-driven separation applications.« less

Modulation of surface structure and catalytic properties of cerium oxide nanoparticles by thermal and microwave synthesis techniques

NASA Astrophysics Data System (ADS)

He, Jian; Zhou, Lan; Liu, Jie; Yang, Lu; Zou, Ling; Xiang, Junyu; Dong, Shiwu; Yang, Xiaochao

2017-04-01

Cerium oxide nanoparticles (CNPs) have been intensively explored for biomedical applications in recent few years due to the versatile enzyme mimetic activities of the nanoparticles. However, the control of CNPs quality through the optimization of synthesis conditions remains largely unexplored as most of the previous studies only focus on utilizing the catalytic activities of the nanoparticles. In the present study, CNPs with size about 5 nm were synthesized by thermal decomposition method using traditional convective heating and recently developed microwave irradiation as heating source. The quality of CNPs synthesized by the two heating manner was evaluated. The CNPs synthesized by convective heating were slightly smaller than that synthesized by microwave irradiation heating. The cores of the CNPs synthesized by the two heating manner have similar crystal structure. While the surface subtle structures of the CNPs synthesized by two heating manner were different. The CNPs synthesized by microwave irradiation have more surface reactive hot spot than that synthesized by convective heating as the nanoparticles responded more actively to the redox environment variation. This difference resulted in the higher superoxide dismutase (SOD) mimetic activity of CNPs synthesized by microwave irradiation heating than that of the convective heating. Preliminary experiments indicated that the CNPs synthesized by microwave irradiation heating could better protect cells from oxidative stress due to the higher SOD mimetic activity of the nanoparticles.

Nanostructured manganese oxide/carbon nanotubes, graphene and graphene oxide as water-oxidizing composites in artificial photosynthesis.

PubMed

Najafpour, Mohammad Mahdi; Rahimi, Fahime; Fathollahzadeh, Maryam; Haghighi, Behzad; Hołyńska, Małgorzata; Tomo, Tatsuya; Allakhverdiev, Suleyman I

2014-07-28

Herein, we report on nano-sized Mn oxide/carbon nanotubes, graphene and graphene oxide as water-oxidizing compounds in artificial photosynthesis. The composites are synthesized by different and simple procedures and characterized by a number of methods. The water-oxidizing activities of these composites are also considered in the presence of cerium(IV) ammonium nitrate. Some composites are efficient Mn-based catalysts with TOF (mmol O2 per mol Mn per second) ~ 2.6.

Effects of amorphous silica coating on cerium oxide nanoparticles induced pulmonary responses

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ma, Jane, E-mail: jym1@cdc.gov; Mercer, Robert R.; Barger, Mark

2015-10-01

Recently cerium compounds have been used in a variety of consumer products, including diesel fuel additives, to increase fuel combustion efficiency and decrease diesel soot emissions. However, cerium oxide (CeO{sub 2}) nanoparticles have been detected in the exhaust, which raises a health concern. Previous studies have shown that exposure of rats to nanoscale CeO{sub 2} by intratracheal instillation (IT) induces sustained pulmonary inflammation and fibrosis. In the present study, male Sprague–Dawley rats were exposed to CeO{sub 2} or CeO{sub 2} coated with a nano layer of amorphous SiO{sub 2} (aSiO{sub 2}/CeO{sub 2}) by a single IT and sacrificed at variousmore » times post-exposure to assess potential protective effects of the aSiO{sub 2} coating. The first acellular bronchoalveolar lavage (BAL) fluid and BAL cells were collected and analyzed from all exposed animals. At the low dose (0.15 mg/kg), CeO{sub 2} but not aSiO{sub 2}/CeO{sub 2} exposure induced inflammation. However, at the higher doses, both particles induced a dose-related inflammation, cytotoxicity, inflammatory cytokines, matrix metalloproteinase (MMP)-9, and tissue inhibitor of MMP at 1 day post-exposure. Morphological analysis of lung showed an increased inflammation, surfactant and collagen fibers after CeO{sub 2} (high dose at 3.5 mg/kg) treatment at 28 days post-exposure. aSiO{sub 2} coating significantly reduced CeO{sub 2}-induced inflammatory responses in the airspace and appeared to attenuate phospholipidosis and fibrosis. Energy dispersive X-ray spectroscopy analysis showed Ce and phosphorous (P) in all particle-exposed lungs, whereas Si was only detected in aSiO{sub 2}/CeO{sub 2}-exposed lungs up to 3 days after exposure, suggesting that aSiO{sub 2} dissolved off the CeO{sub 2} core, and some of the CeO{sub 2} was transformed to CePO{sub 4} with time. These results demonstrate that aSiO{sub 2} coating reduce CeO{sub 2}-induced inflammation, phospholipidosis and fibrosis. - Highlights

Use of boiled hexamethylenetetramine and urea to increase the porosity of cerium dioxide microspheres formed in the internal gelation process

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hunt, R. D.; Collins, J. L.; Cowell, B. S.

Cerium dioxide (CeO 2) is a commonly used simulant for plutonium dioxide and for plutonium (Pu) in a mixed uranium (U) and Pu oxide [(U, Pu)O 2] in nuclear fuel development. This effort developed CeO 2 microspheres with different porosities and diameters for use in a crush-strength study. The internal gelation technique has produced CeO 2 microspheres with limited initial porosity. When an equal molar solution of urea and hexamethylenetetramine (HMTA) is gently boiling for 1 hr and used in the gelation process, the crystallite size and porosity of mixed U and thorium oxide microspheres and the (U, Pu)O 2more » microspheres increased significantly. In this study with cerium, the combination of ammonium cerium nitrate and 1-h boiled HMTA-urea failed to produce a stable feed broth. However, when the 1-h heated HMTA-urea was combined with unheated HMTA-urea in 1 to 3 volume ratio or the boiling time of the HMTA-urea was reduced to 15-20 min, a stable solution of HMTA, urea, and Ce was formed at 273 K. This new Ce solution produced CeO 2 microspheres with much higher initial porosities. Intermediate porosities were possible when the heated HMTA/urea was aged prior to use.« less

Use of boiled hexamethylenetetramine and urea to increase the porosity of cerium dioxide microspheres formed in the internal gelation process

DOE PAGES

Hunt, R. D.; Collins, J. L.; Cowell, B. S.

2017-05-13

Cerium dioxide (CeO 2) is a commonly used simulant for plutonium dioxide and for plutonium (Pu) in a mixed uranium (U) and Pu oxide [(U, Pu)O 2] in nuclear fuel development. This effort developed CeO 2 microspheres with different porosities and diameters for use in a crush-strength study. The internal gelation technique has produced CeO 2 microspheres with limited initial porosity. When an equal molar solution of urea and hexamethylenetetramine (HMTA) is gently boiling for 1 hr and used in the gelation process, the crystallite size and porosity of mixed U and thorium oxide microspheres and the (U, Pu)O 2more » microspheres increased significantly. In this study with cerium, the combination of ammonium cerium nitrate and 1-h boiled HMTA-urea failed to produce a stable feed broth. However, when the 1-h heated HMTA-urea was combined with unheated HMTA-urea in 1 to 3 volume ratio or the boiling time of the HMTA-urea was reduced to 15-20 min, a stable solution of HMTA, urea, and Ce was formed at 273 K. This new Ce solution produced CeO 2 microspheres with much higher initial porosities. Intermediate porosities were possible when the heated HMTA/urea was aged prior to use.« less

Cellular partitioning of nanoparticulate versus dissolved metals in marine phytoplankton.

PubMed

Bielmyer-Fraser, Gretchen K; Jarvis, Tayler A; Lenihan, Hunter S; Miller, Robert J

2014-11-18

Discharges of metal oxide nanoparticles into aquatic environments are increasing with their use in society, thereby increasing exposure risk for aquatic organisms. Separating the impacts of nanoparticle from dissolved metal pollution is critical for assessing the environmental risks of the rapidly growing nanomaterial industry, especially in terms of ecosystem effects. Metal oxides negatively affect several species of marine phytoplankton, which are responsible for most marine primary production. Whether such toxicity is generally due to nanoparticles or exposure to dissolved metals liberated from particles is uncertain. The type and severity of toxicity depends in part on whether phytoplankton cells take up and accumulate primarily nanoparticles or dissolved metal ions. We compared the responses of the marine diatom, Thalassiosira weissflogii, exposed to ZnO, AgO, and CuO nanoparticles with the responses of T. weissflogii cells exposed to the dissolved metals ZnCl2, AgNO3, and CuCl2 for 7 d. Cellular metal accumulation, metal distribution, and algal population growth were measured to elucidate differences in exposure to the different forms of metal. Concentration-dependent metal accumulation and reduced population growth were observed in T. weissflogii exposed to nanometal oxides, as well as dissolved metals. Significant effects on population growth were observed at the lowest concentrations tested for all metals, with similar toxicity for both dissolved and nanoparticulate metals. Cellular metal distribution, however, markedly differed between T. weissflogii exposed to nanometal oxides versus those exposed to dissolved metals. Metal concentrations were highest in the algal cell wall when cells were exposed to metal oxide nanoparticles, whereas algae exposed to dissolved metals had higher proportions of metal in the organelle and endoplasmic reticulum fractions. These results have implications for marine plankton communities as well as higher trophic levels, since

Solubility of Nanocrystalline Cerium Dioxide: Experimental Data and Thermodynamic Modeling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Plakhova, Tatiana V.; Romanchuk, Anna Yu.; Yakunin, Sergey N.

For this study, ultrafine 5 nm ceria isotropic nanoparticles were prepared using the rapid chemical precipitation approach from cerium(III) nitrate and ammonium hydroxide aqueous solutions. The as-prepared nanoparticles were shown to contain predominantly Ce(IV) species. The solubility of nanocrystalline CeO 2 at several pH values was determined using ICP-MS and radioactive tracer methods. Phase composition of the ceria samples remained unchanged upon partial dissolution, while the shape of the particles changed dramatically, yielding nanorods under neutral pH conditions. According to X-ray absorption spectroscopy investigation of the supernatant, Ce(III) was the main cerium species in solution at pH < 4. Basedmore » on the results obtained, a reductive dissolution model was used for data interpretation. According to this model, the solubility product for ceria nanoparticles was determined to be log K sp = -59.3 ± 0.3 in 0.01 M NaClO 4. Taken together, our results show that the pH dependence of ceria anti- and pro-oxidant activity can be related to the dissolution of CeO 2 in aqueous media.« less

Solubility of Nanocrystalline Cerium Dioxide: Experimental Data and Thermodynamic Modeling

DOE PAGES

Plakhova, Tatiana V.; Romanchuk, Anna Yu.; Yakunin, Sergey N.; ...

2016-09-12

For this study, ultrafine 5 nm ceria isotropic nanoparticles were prepared using the rapid chemical precipitation approach from cerium(III) nitrate and ammonium hydroxide aqueous solutions. The as-prepared nanoparticles were shown to contain predominantly Ce(IV) species. The solubility of nanocrystalline CeO 2 at several pH values was determined using ICP-MS and radioactive tracer methods. Phase composition of the ceria samples remained unchanged upon partial dissolution, while the shape of the particles changed dramatically, yielding nanorods under neutral pH conditions. According to X-ray absorption spectroscopy investigation of the supernatant, Ce(III) was the main cerium species in solution at pH < 4. Basedmore » on the results obtained, a reductive dissolution model was used for data interpretation. According to this model, the solubility product for ceria nanoparticles was determined to be log K sp = -59.3 ± 0.3 in 0.01 M NaClO 4. Taken together, our results show that the pH dependence of ceria anti- and pro-oxidant activity can be related to the dissolution of CeO 2 in aqueous media.« less

Zinc-doped cerium oxide nanoparticles: Sol-gel synthesis, characterization, and investigation of their in vitro cytotoxicity effects

NASA Astrophysics Data System (ADS)

Akbari, Alireza; Khammar, Mansoureh; Taherzadeh, Danial; Rajabian, Arezoo; Khorsand Zak, Ali; Darroudi, Majid

2017-12-01

Zinc-doped cerium oxide nanoparticles (Zn-doped CeO2-NPs) with Ce1-xZnxO2 composition, where x equals to 0.0, 0.01, 0.03, and 0.05 are synthesized through a green based sol-gel method from nitrate precursors and gelatin at the fixed calcination temperature of 600 °C maintained for 2 h. The powder X-ray diffraction (PXRD) patterns displayed the single-crystalline structure of these particular samples, which seemed to be completely indexed with the cubic fluorite phase. The evolution of crystalline phases in Ce1-xZnxO2 are assured by the observed broadening in PXRD peaks, while the field emission scanning electron microscopy (FE-SEM) images revealed that the spherical-shaped single-crystalline NPs do exist and confirmed the size estimations that were obtained from the Scherrer's equation. A dose dependent toxicity with non-toxic effects of concentrations up to 31.25 μg/ml is illustrated through the In vitro cytotoxicity studies regarding Neuro2A cells.

Ingenierie de nanoparticules plasmoniques robustes pour la generation de bulles par laser en vue d'applications biomedicales

NASA Astrophysics Data System (ADS)

Lachaine, Remi

Les chirurgiens generent des bulles dans le corps humain a l'aide d'irradiation laser depuis plusieurs decennies. Ils utilisent ces bulles comme de petits scalpels, leur permettant de faire des incisions precises et localisees. Une des applications de cet outil chirurgical est la perforation cellulaire. Au lieu d'utiliser une aiguille pour perforer la membrane des cellules, il est possible de focaliser des impulsions laser en surface d'une cellule, formant un plasma au point focal du laser et generant une bulle qui perfore la membrane cellulaire. Toutefois, ce procede est assez lent et la perforation massive de cellules in-vivo n'est pas envisageable. Pour accelerer le processus, il est possible d'utiliser des nanoparticules plasmoniques. Ces dernieres agissent comme des nano-antennes qui permettent de concentrer la lumiere sur une echelle nanometrique. La possibilite d'irradier un grand nombre de nanoparticules simultanement a donne un nouvel elan a la generation de bulle comme outil de perforation cellulaire. L'utilisation de nanoparticules dans un contexte biomedical comporte toutefois certains risques. En particulier, la fragmentation de nanoparticules peut augmenter la toxicite du traitement. Dans un cas ideal, il est preferable d'utiliser des nanoparticules qui ne sont pas endommagees par l'irradiation laser. Cette these a pour but de developper une methode d'ingenierie de nanoparticules robustes permettant la generation efficace de bulles a des fins biomedicales. Il est tout d'abord demontre experimentalement que la formation de plasma est bel et bien le mecanisme physique principal menant a la generation de bulles lors de l'irradiation infrarouge (longueur d'onde de 800 nm) et ultrarapide (temps d'impulsion entre 45 fs et 1 ps) de nanoparticules d'or de 100 nm. Pour realiser cette demonstration, une methode pompe-sonde de detection de bulles d'environ 1 mum a ete elaboree. Cette methode a permis de mettre en evidence une difference de taille de 18% entre

Cerium-doped scintillating fused-silica fibers

NASA Astrophysics Data System (ADS)

Akchurin, N.; Cowden, C.; Damgov, J.; Dragoiu, C.; Dudero, P.; Faulkner, J.; Kunori, S.

2018-04-01

We report on a set of measurements made on (scintillating) cerium-doped fused-silica fibers using high-energy particle beams. These fibers were uniformly embedded in a copper absorber in order to utilize electromagnetic showers as a source of charged particles for generating signals. This new type of cerium-doped fiber potentially offers myriad new applications in calorimeters in high-energy physics, tracking systems, and beam monitoring detectors for future applications. The light yield, pulse shape, attenuation length, and light propagation speeds are given and discussed. Possible future applications are also explored.

Thermal decomposition kinetics of hydrazinium cerium 2,3-Pyrazinedicarboxylate hydrate: a new precursor for CeO2.

PubMed

Premkumar, Thathan; Govindarajan, Subbiah; Coles, Andrew E; Wight, Charles A

2005-04-07

The thermal decomposition kinetics of N(2)H(5)[Ce(pyrazine-2,3-dicarboxylate)(2)(H(2)O)] (Ce-P) have been studied by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), for the first time; TGA analysis reveals an oxidative decomposition process yielding CeO(2) as the final product with an activation energy of approximately 160 kJ mol(-1). This complex may be used as a precursor to fine particle cerium oxides due to its low temperature of decomposition.

Role of epithelial-mesenchymal transition (EMT) and fibroblast function in cerium oxide nanoparticles-induced lung fibrosis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ma, Jane

The emission of cerium oxide nanoparticles (CeO{sub 2}) from diesel engines, using cerium compounds as a catalyst to lower the diesel exhaust particles, is a health concern. We have previously shown that CeO{sub 2} induced pulmonary inflammation and lung fibrosis. The objective of the present study was to investigate the modification of fibroblast function and the role of epithelial-mesenchymal transition (EMT) in CeO{sub 2}-induced fibrosis. Male Sprague-Dawley rats were exposed to CeO{sub 2} (0.15 to 7 mg/kg) by a single intratracheal instillation and sacrificed at various times post-exposure. The results show that at 28 days after CeO{sub 2} (3.5 mg/kg)more » exposure, lung fibrosis was evidenced by increased soluble collagen in bronchoalveolar lavage fluid, elevated hydroxyproline content in lung tissues, and enhanced sirius red staining for collagen in the lung tissue. Lung fibroblasts and alveolar type II (ATII) cells isolated from CeO{sub 2}-exposed rats at 28 days post-exposure demonstrated decreasing proliferation rate when compare to the controls. CeO{sub 2} exposure was cytotoxic and altered cell function as demonstrated by fibroblast apoptosis and aggregation, and ATII cell hypertrophy and hyperplasia with increased surfactant. The presence of stress fibers, expressed as α-smooth muscle actin (SMA), in CeO{sub 2}-exposed fibroblasts and ATII cells was significantly increased compared to the control. Immunohistofluorescence analysis demonstrated co-localization of TGF-β or α-SMA with prosurfactant protein C (SPC)-stained ATII cells. These results demonstrate that CeO{sub 2} exposure affects fibroblast function and induces EMT in ATII cells that play a role in lung fibrosis. These findings suggest potential adverse health effects in response to CeO{sub 2} nanoparticle exposure. - Highlights: • CeO{sub 2} exposure induced lung fibrosis. • CeO{sub 2} were detected in lung tissue, alveolar type II (ATII) cells and fibroblasts. • CeO{sub 2} caused

Divalent fluoride doped cerium fluoride scintillator

DOEpatents

Anderson, David F.; Sparrow, Robert W.

1991-01-01

The use of divalent fluoride dopants in scintillator materials comprising cerium fluoride is disclosed. The preferred divalent fluoride dopants are calcium fluoride, strontium fluoride, and barium fluoride. The preferred amount of divalent fluoride dopant is less than about two percent by weight of the total scintillator. Cerium fluoride scintillator crystals grown with the addition of a divalent fluoride have exhibited better transmissions and higher light outputs than crystals grown without the addition of such dopants. These scintillators are useful in radiation detection and monitoring applications, and are particularly well suited for high-rate applications such as positron emission tomography (PET).

Negative cerium anomalies in manganese (hydr)oxide precipitates due to cerium oxidation in the presence of dissolved siderophores

NASA Astrophysics Data System (ADS)

Kraemer, Dennis; Tepe, Nathalie; Pourret, Olivier; Bau, Michael

2017-01-01

We present experimental results on the sorption behavior of rare earth elements and yttrium (REY) on precipitating manganese (hydr)oxide in the presence of the biogenic siderophore desferrioxamine B (DFOB). In marked contrast to inorganic systems, where preferential adsorption of HREY and depletion of LREY is commonly observed in manganese (hydr)oxide precipitates, sorption of REY in presence of the DFOB siderophore leads to HREY-depleted and LREY-enriched patterns in the precipitates. Moreover, our data indicate that surface oxidation of Ce(III) to Ce(IV) during sorption onto manganese (hydr)oxides and the resulting development of a positive Ce anomaly, which are commonly observed in inorganic experiments, are prevented in the presence of DFOB. Instead, Ce(III) is oxidized to Ce(IV) but associated with the dissolved desferrioxamine B which forms complexes with Ce(IV), that are at least twenty orders of magnitude more stable than those with Ce(III) and REY(III). The overall result is the formation of a positive Ce anomaly in the solution and a negative Ce anomaly in the Mn (hydr)oxides. The distribution of the strictly trivalent REY and Eu(III) between the manganese (hydr)oxide phase and the remaining ambient solution mimics the distribution of published stability constants for complexes of REY(III) with DFOB, i.e. the heavy REY form more stable complexes with the ligand and hence are better shielded from sorption than the LREY. Surface complexation modeling corroborates our experimental results. Negative Ce anomalies in Mn precipitates have been described from biogenic Mn oxides. Our results provide experimental evidence for the development of negative Ce anomalies in abiogenic Mn (hydr)oxide precipitates and show that the presence of the widespread siderophore desferrioxamine B during mineral precipitation results in HREY-depleted Mn (hydr)oxides with negative Ce anomalies.

Antimicrobial cerium ion-chitosan crosslinked alginate biopolymer films: A novel and potential wound dressing.

PubMed

Kaygusuz, Hakan; Torlak, Emrah; Akın-Evingür, Gülşen; Özen, İlhan; von Klitzing, Regine; Erim, F Bedia

2017-12-01

Wound dressings require good antiseptic properties, mechanical strength and, more trustably, natural material ingredients. Antimicrobial properties of cerium ions and chitosan are known and alginate based wound dressings are commercially available. In this study, the advantages of these materials were combined and alginate films were crosslinked with cerium(III) solution and chitosan added cerium(III) solution. Films were characterized by Fourier transform infrared spectroscopy (FTIR), light transmittance, scanning electron microscopy (SEM), swelling experiments, water vapor transmittance tests, and mechanical stretching tests. The antibacterial and physical properties of the films were compared with those of conventional calcium alginate films. Both cerium ion crosslinked and cerium ion-chitosan crosslinked alginate films gained antibacterial activity against Gram-negative (Escherichia coli) and Gram-positive (Staphylococcus aureus) bacteria. Cerium alginate-chitosan films showed high resistance to being deformed elastically. Results show that cerium alginate-chitosan films can be flexible, ultraviolet-protecting, and antibacterial wound dressings. Copyright © 2017 Elsevier B.V. All rights reserved.

Pulmonary toxicity of well-dispersed cerium oxide nanoparticles following intratracheal instillation and inhalation

NASA Astrophysics Data System (ADS)

Morimoto, Yasuo; Izumi, Hiroto; Yoshiura, Yukiko; Tomonaga, Taisuke; Oyabu, Takako; Myojo, Toshihiko; Kawai, Kazuaki; Yatera, Kazuhiro; Shimada, Manabu; Kubo, Masaru; Yamamoto, Kazuhiro; Kitajima, Shinichi; Kuroda, Etsushi; Kawaguchi, Kenji; Sasaki, Takeshi

2015-11-01

We performed inhalation and intratracheal instillation studies of cerium dioxide (CeO2) nanoparticles in order to investigate their pulmonary toxicity, and observed pulmonary inflammation not only in the acute and but also in the chronic phases. In the intratracheal instillation study, F344 rats were exposed to 0.2 mg or 1 mg of CeO2 nanoparticles. Cell analysis and chemokines in bronchoalveolar lavage fluid (BALF) were analyzed from 3 days to 6 months following the instillation. In the inhalation study, rats were exposed to the maximum concentration of inhaled CeO2 nanoparticles (2, 10 mg/m3, respectively) for 4 weeks (6 h/day, 5 days/week). The same endpoints as in the intratracheal instillation study were examined from 3 days to 3 months after the end of the exposure. The intratracheal instillation of CeO2 nanoparticles caused a persistent increase in the total and neutrophil number in BALF and in the concentration of cytokine-induced neutrophil chemoattractant (CINC)-1, CINC-2, chemokine for neutrophil, and heme oxygenase-1 (HO-1), an oxidative stress marker, in BALF during the observation time. The inhalation of CeO2 nanoparticles also induced a persistent influx of neutrophils and expression of CINC-1, CINC-2, and HO-1 in BALF. Pathological features revealed that inflammatory cells, including macrophages and neutrophils, invaded the alveolar space in both studies. Taken together, the CeO2 nanoparticles induced not only acute but also chronic inflammation in the lung, suggesting that CeO2 nanoparticles have a pulmonary toxicity that can lead to irreversible lesions.

Influence of Collector Surface Composition and Water Chemistry on the Deposition of Cerium Dioxide Nanoparticles: QCM-D and Column Experiment Approaches

EPA Science Inventory

The deposition behavior of cerium dioxide (CeO2) nanoparticles (NPs) in dilute NaCl solutions was investigated as a function of collector surface composition, pH, ionic strength, and organic matter (OM). Sensors coated separately with silica, iron oxide, and alumina were applied ...

Dielectrophoretic Isolation and Detection of cfc-DNA Nanoparticulate Biomarkers and Virus from Blood

PubMed Central

Sonnenberg, Avery; Marciniak, Jennifer Y.; McCanna, James; Krishnan, Rajaram; Rassenti, Laura; Kipps, Thomas J.; Heller, Michael J.

2015-01-01

Dielectrophoretic (DEP) microarray devices allow important cellular nanoparticulate biomarkers and virus to be rapidly isolated, concentrated and detected directly from clinical and biological samples. A variety of sub-micron nanoparticulate entities including cell free circulating (cfc) DNA, mitochondria and virus can be isolated into DEP high-field areas on microelectrodes, while blood cells and other micron-size entities become isolated into DEP low-field areas between the microelectrodes. The nanoparticulate entities are held in the DEP high-field areas while cells are washed away along with proteins and other small molecules which are not affected by the DEP electric fields. DEP carried out on 20 µL of whole blood obtained from Chronic Lymphocytic Leukemia (CLL) patients showed a considerable amount of SYBR Green stained DNA fluorescent material concentrated in the DEP high-field regions. Whole blood obtained from healthy individuals showed little or no fluorescent DNA materials in the DEP high-field regions. Fluorescent T7 bacteriophage virus could be isolated directly from blood samples, and fluorescently stained mitochondria could be isolated from biological buffer samples. Using newer DEP microarray devices, high molecular weight (hmw) DNA could be isolated from serum and detected at levels as low as 8–16 ng/mL. PMID:23436471

Study of an ultrasound-based process analytical tool for homogenization of nanoparticulate pharmaceutical vehicles.

PubMed

Cavegn, Martin; Douglas, Ryan; Akkermans, Guy; Kuentz, Martin

2011-08-01

There are currently no adequate process analyzers for nanoparticulate viscosity enhancers. This article aims to evaluate ultrasonic resonator technology as a monitoring tool for homogenization of nanoparticulate gels. Aqueous dispersions of colloidal microcrystalline cellulose (MCC) and a mixture of clay particles with xanthan gum were compared with colloidal silicon dioxide in oil. The processing was conducted using a laboratory-scale homogenizing vessel. The study investigated first the homogenization kinetics of the different systems to focus then on process factors in the case of colloidal MCC. Moreover, rheological properties were analyzed offline to assess the structure of the resulting gels. Results showed the suitability of ultrasound velocimetry to monitor the homogenization process. The obtained data were fitted using a novel heuristic model. It was possible to identify characteristic homogenization times for each formulation. The subsequent study of the process factors demonstrated that ultrasonic process analysis was equally sensitive as offline rheological measurements in detecting subtle manufacturing changes. It can be concluded that the ultrasonic method was able to successfully assess homogenization of nanoparticulate viscosity enhancers. This novel technique can become a vital tool for development and production of pharmaceutical suspensions in the future. Copyright © 2011 Wiley-Liss, Inc.

Effects of cerium oxide nanoparticles on soil enzymatic activities and wheat grass nutrients uptake

NASA Astrophysics Data System (ADS)

Li, Biting; Chen, Yirui; Bai, Lingyun; Jacobson, Astrid; Darnault, Christophe

2015-04-01

The US National Science Foundation estimated that the use of nanomaterials and nanotechnology would reach a global market value of 1 million this year. Concomitant with the wide applications of nanoparticles is an increasing risk of adverse effects to the environment and human health. As a common nanomaterial used as a fuel catalyst and polish material, cerium (IV) oxide nanoparticles (CeO2 NP) were tested for their potential impact on soil health and plant growth. Through exposure by air, water, and solid deposition, nanoparticles may accumulate in soils and impact agricultural systems. The objectives of this research were to determine whether CeO2 NPs affect the growth of wheat grass and selected soil enzyme activities chose as indicators of soil health. Wheat grass was grown in plant boxes containing CeO2 NPs mixed with agricultural soil at different concentrations. Two control groups were included: one consisting of soil with plants but no CeO2 NPs, and one containing only soil, i.e., no NP or wheat plants added. The plants were grown for 10 weeks and harvested every two weeks in a laboratory under sodium growth lights. At the end of the each growing period, two weeks, soils were assayed for phosphatase, β-glucosidase, and urease activities, and NPK values. Spectrophotometer analyses were used to assess enzyme activities, and NPK values were tested by Clemson Agricultural Center. Wheat yields were estimated by shoot and root lengths and weights.

Casting Characteristics of High Cerium Content Aluminum Alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Weiss, D; Rios, O R; Sims, Z C

This paper compares the castability of the near eutectic aluminum-cerium alloy system to the aluminum-silicon and aluminum-copper systems. The alloys are compared based on die filling capability, feeding characteristics and tendency to hot tear in both sand cast and permanent mold applications. The castability ranking of the binary Al–Ce systems is as good as the aluminum-silicon system with some deterioration as additional alloying elements are added. In alloy systems that use cerium in combination with common aluminum alloying elements such as silicon, magnesium and/or copper, the casting characteristics are generally better than the aluminum-copper system. In general, production systems formore » melting, de-gassing and other processing of aluminum-silicon or aluminum-copper alloys can be used without modification for conventional casting of aluminum-cerium alloys.« less

Porous nano-cerium oxide wood chip biochar composites for aqueous levofloxacin removal and sorption mechanism insights.

PubMed

Yi, Shengze; Sun, Yuanyuan; Hu, Xin; Xu, Hongxia; Gao, Bin; Wu, Jichun

2017-01-14

The adsorption removal of levofloxacin (LEV), a widely used fluoroquinolone antibiotic, by using the biochars derived from the pyrolysis of pine wood chip pretreated with cerium trichloride was investigated through batch sorption experiments and multiple characterization techniques. The differences in the basic physicochemical properties between Ce-impregnated biochars and the pristine biochars were confirmed by the analysis of elemental compositions, specific surface areas, energy dispersive spectrometry, X-ray diffraction, and thermo-gravimetry. FT-IR spectra of the pre- and post-sorption biochars confirmed the chemical adsorption for LEV sorption onto the biochars. Large shifts in the binding energy of Ce 3d , O 1s , C 1s , and N 1s regions on the pre- and post-sorption biochars indicated the surface complexation of LEV molecule onto the biochars. The binding species of Ce 4+ and Ce 3+ identified by X-ray photoelectron spectroscopy reflect the role of Ce oxides during sorption. Batch adsorption showed the significant enhancement of adsorption capacity for LEV after the Ce modification. Batch adsorption kinetic data fitted well with the pseudo-second-order model. Both the Langmuir and the Freundlich models reproduced the isotherm data well. Findings from this work indicated that Ce-impregnated biochars can be effective for the removal of aqueous LEV.

Critical indices for reversible gamma-alpha phase transformation in metallic cerium

NASA Astrophysics Data System (ADS)

Soldatova, E. D.; Tkachenko, T. B.

1980-08-01

Critical indices for cerium have been determined within the framework of the pseudobinary solution theory along the phase equilibrium curve, the critical isotherm, and the critical isobar. The results obtained verify the validity of relationships proposed by Rushbrook (1963), Griffiths (1965), and Coopersmith (1968). It is concluded that reversible gamma-alpha transformation in metallic cerium is a critical-type transformation, and cerium has a critical point on the phase diagram similar to the critical point of the liquid-vapor system.

Study of Degradation Kinetics of Parathion Methyl On Mixed Nanocrystalline Titania-Zirconium and Titania-Cerium Oxides

NASA Astrophysics Data System (ADS)

Kuráň, Pavel; Pšenička, Martin; Šťastný, Martin; Benkocká, Monika; Janoš, Pavel

2016-10-01

The unique surface properties of some nanocrystalline metal oxides and their application for removal of various toxic compounds were reported in early 1990s. Recently, a reliable method for the preparation of reactive cerium dioxide sorbent and its application for degradation of the organophosphate pesticides, such as parathion methyl, chlorpyrifos, dichlofenthion, fenchlorphos, and prothiofos, as well as of some chemical warfare agents-nerve gases soman and O-ethyl S-[2-(diisopropylamino) ethyl] methylphosphonothioate (VX) was published. This paper reports on the kinetics study of degradation of parathion methyl as a representative organophosphate on nanocrystalline metal oxides TiO2, ZrO2, CeO2 and their mixtures in different molar ratios of particular elements. The tested sorbents except of CeO2 were prepared by different methods (e.g. sol-gel, precipitation) in cooperation with Institute of Inorganic Chemistry (Rez, Czech Republic). The degradation kinetics of parathion methyl on tested sorbents was followed by HPLC equipped with diode array detector. The basic kinetics parameters (half-lives of parathion methyl degradation, rate constants of degradation product formation) were calculated for each sorbent from Weber-Morris equation of 1st order diffusion kinetic model. The results proved the ability of prepared sorbents to degrade parathion methyl under formation of 4-nitrophenol as the main degradation product. The most efficient sorbents were TiCe (2:8), TiCe (1:1), TiCe (0:1) (50-70 %) followed by TiZr (1:1), TiCe (8:2), TiZr (8:2), TiZr (2:8) (20-30%) and TiO2, ZrO2 (less than 5 %).

Nanoparticulate strategies for effective delivery of poorly soluble therapeutics.

PubMed

Gokce, Evren H; Ozyazici, Mine; Souto, Eliana B

2010-07-01

The pharmacological activity of a drug molecule depends on its ability to dissolve and interact with its biological target, either through dissolution and absorption, or through dissolution and receptor interaction. The low bioavailability that characterizes poorly water-soluble drugs is usually attributed to the dissolution kinetic profile. Novel strategies to effectively deliver these drugs include nanoparticulate approaches that either increase the surface area of the drug or improve the solubility characteristics of the drug. Nanosizing approaches are based on the production of drug nanocrytals dispersed in an aqueous surfactant solution, whereas other possibilities include drug loading in nanoparticles. Promising nanoparticulate approaches include the development of lipid-based nanocarriers to increase drug solubility followed by enhanced bioavailability. To select the best approach there are, however, some critical considerations to take into account, for example the physicochemical properties of the drug, the possibility to scale-up the production process, the toxicological considerations of the use of solvents and cosolvents, the selection of an environmentally sustainable methodology and the development of a more patient-friendly dosage form. This article addresses these relevant questions and provides feasible examples of novel strategies with respect to relevant administration routes.

Synthesis and structural studies on cerium substituted La0.4Ca0.6MnO3 as solid oxide fuel cell electrode material

NASA Astrophysics Data System (ADS)

Singh, Monika; Kumar, Dinesh; Singh, Akhilesh Kumar

2018-04-01

For solid oxide fuel cell electrode material, calcium doped lanthanum manganite La0.4Ca0.6MnO3 (LCMO) and cerium-incorporated on Ca-site with composition La0.40Ca0.55Ce0.05MnO3 (LCCMO) were synthesized using most feasible and efficient glycine-nitrate method. The formation of crystalline single phase was confirmed by x-ray diffraction (XRD). The Rietveld analysis reveals that both systems crystallize into orthorhombic crystal structure with Pnma space group. Additionally, 8 mole % Y2O3 stabilized ZrO2 (8YSZ) solid electrolyte was also synthesized using high energy ball mill to check the reaction with electrode materials. It was found that the substitution of Ce+4 cations in LCMO perovskite suppressed formation of undesired insulating CaZrO3 phase.

Composite solid oxide fuel cell anode based on ceria and strontium titanate

DOEpatents

Marina, Olga A.; Pederson, Larry R.

2008-12-23

An anode and method of making the same wherein the anode consists of two separate phases, one consisting of a doped strontium titanate phase and one consisting of a doped cerium oxide phase. The strontium titanate phase consists of Sr.sub.1-xM.sub.xTiO.sub.3-.delta., where M is either yttrium (Y), scandium (Sc), or lanthanum (La), where "x" may vary typically from about 0.01 to about 0.5, and where .delta. is indicative of some degree of oxygen non-stoichiometry. A small quantity of cerium may also substitute for titanium in the strontium titanate lattice. The cerium oxide consists of N.sub.yCe.sub.1-yO.sub.2-.delta., where N is either niobium (Nb), vanadium (V), antimony (Sb) or tantalum (Ta) and where "y" may vary typically from about 0.001 to about 0.1 and wherein the ratio of Ti in said first phase to the sum of Ce and N in the second phase is between about 0.2 to about 0.75. Small quantities of strontium, yttrium, and/or lanthanum may additionally substitute into the cerium oxide lattice. The combination of these two phases results in better performance than either phase used separately as an anode for solid oxide fuel cell or other electrochemical device.

Effect of nano-sized cerium-zirconium oxide solid solution on far-infrared emission properties of tourmaline powders

NASA Astrophysics Data System (ADS)

Guo, Bin; Yang, Liqing; Hu, Weijie; Li, Wenlong; Wang, Haojing

2015-10-01

Far-infrared functional nanocomposites were prepared by the co-precipitation method using natural tourmaline (XY3Z6Si6O18(BO3)3V3W, where X is Na+, Ca2+, K+, or vacancy; Y is Mg2+, Fe2+, Mn2+, Al3+, Fe3+, Mn3+, Cr3+, Li+, or Ti4+; Z is Al3+, Mg2+, Cr3+, or V3+; V is O2-, OH-; and W is O2-, OH-, or F-) powders, ammonium cerium(IV) nitrate and zirconium(IV) nitrate pentahydrate as raw materials. The reference sample, tourmaline modified with ammonium cerium(IV) nitrate alone was also prepared by a similar precipitation route. The results of Fourier transform infrared spectroscopy show that tourmaline modified with Ce and Zr has a better far-infrared emission property than tourmaline modified with Ce alone. Through characterization by transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS), the mechanism for oxygen evolution during the heat process in the two composite materials was systematically studied. The XPS spectra show that Fe3+ ratio inside tourmaline modified with Ce alone can be raised by doping Zr. Moreover, it is showed that there is a higher Ce3+ ratio inside the tourmaline modified with Ce and Zr than tourmaline modified with Ce alone. In addition, XRD results indicate the formation of CeO2 and Ce1-xZrxO2 crystallites during the heat treatment and further TEM observations show they exist as nanoparticles on the surface of tourmaline powders. Based on these results, we attribute the improved far-infrared emission properties of Ce-Zr doped tourmaline to the enhanced unit cell shrinkage of the tourmaline arisen from much more oxidation of Fe2+ to Fe3+ inside the tourmaline caused by the change in the catalyst redox properties of CeO2 brought about by doping with Zr4+. In all samples, tourmaline modified with 7.14 wt.% Ce and 1.86 wt.% Zr calcined at 800∘C for 5 h has the best far-infrared emission property with the maximum emissivity value of 98%.

Impacts of cerium oxide nanoparticles on bacterial community in activated sludge.

PubMed

Kamika, I; Tekere, M

2017-12-01

Rapidly developing industry raises concerns about the environmental impacts of nanoparticles, but the effects of inorganic nanoparticles on bacterial community in wastewater treatment remain unclear. The present research assessed the impact of cerium oxide nanoparticles (nCeO) on the microbiome of activated sludge system. The results showed that 18,330 over 28,201 reads generated from control samples were assigned to Proteobacteria while 5527 reads (19.6%), 3260 reads (11.567%), and 719 reads (2.55%) were assigned to unclassified_Bacteria, Firmicutes and Actinobacteria, respectively. When stressed with nCeO 2 NPs, a decrease on reads was noted with 53, 48, 27.7 and 24% assigned to Proteobacteria. Gammaproteobacteria (80.57%) was found to be the most predominant Proteobacteria. The impact of nCeO 2 NPs was also observed on pollutants removal as only 1.83 and 35.15% of phosphate and nitrate could be removed in the bioreactor stressed with 40 mg-nCeO 2 -NPs/L. This was confirmed by a drastic reduction of activities for enzymes catalysing denitrification (NaR and NiR) and degradation of polyphosphate (ADK and PPK). ADK appeared to be the most affected enzyme with activity decrease reaching over 90% when stressed with 10 mg-nCeO 2 /L. Furthermore, bacterial diversity was not significantly different whereas their species richness showed significant difference between control and treated samples. A large number of reads from control samples could not be classified down to the lower taxonomic level "genera" suggesting hitherto vast untapped microbial diversity. The denitrification related genera including Trichococcus and Acinetobacter were found to alternatively dominating treated samples highlighting those nCeO 2 NPs could enhance the growth of some bacterial species while inhibiting those of others. Nevertheless, the study indicates that nCeO 2 NPs in wastewater at very high concentrations may have some adverse effects on activated sludge process as they inhibit the

Catalyst for reduction of nitrogen oxides

DOEpatents

Ott, Kevin C.

2010-04-06

A Selective Catalytic Reduction (SCR) catalyst was prepared by slurry coating ZSM-5 zeolite onto a cordierite monolith, then subliming an iron salt onto the zeolite, calcining the monolith, and then dipping the monolith either into an aqueous solution of manganese nitrate and cerium nitrate and then calcining, or by similar treatment with separate solutions of manganese nitrate and cerium nitrate. The supported catalyst containing iron, manganese, and cerium showed 80 percent conversion at 113 degrees Celsius of a feed gas containing nitrogen oxides having 4 parts NO to one part NO.sub.2, about one equivalent ammonia, and excess oxygen; conversion improved to 94 percent at 147 degrees Celsius. N.sub.2O was not detected (detection limit: 0.6 percent N.sub.2O).

Beneficial Effects of Cerium Oxide Nanoparticles in Development of Chondrocyte-Seeded Hydrogel Constructs and Cellular Response to Interleukin Insults

PubMed Central

Ponnurangam, Sathish; O'Connell, Grace D.; Chernyshova, Irina V.; Wood, Katherine; Hung, Clark Tung-Hui

2014-01-01

The harsh inflammatory environment associated with injured and arthritic joints represents a major challenge to articular cartilage repair. In this study, we report the effect of cerium oxide nanoparticles, or nanoceria, in modulating development of engineered cartilage and in combating the deleterious effects of interleukin-1α. Nanoceria was found to be biocompatible with bovine chondrocytes up to a concentration of 1000 μg/mL (60,000 cells/μg of nanoceria), and its presence significantly improved compressive mechanical properties and biochemical composition (i.e., glycosaminoglycans) of engineered cartilage. Raman microspectroscopy revealed that individual chondrocytes with internalized nanoceria have increased concentrations of proline, procollagen, and glycogen as compared with cells without the nanoparticles in their vicinity. The inflammatory response due to physiologically relevant quantities of interluekin-1α (0.5 ng/mL) is partially inhibited by nanoceria. To the best of the authors' knowledge, these results are the first to demonstrate a high potential for nanoceria to improve articular cartilage tissue properties and for their long-term treatment against an inflammatory reaction. PMID:24762195

Beneficial effects of cerium oxide nanoparticles in development of chondrocyte-seeded hydrogel constructs and cellular response to interleukin insults.

PubMed

Ponnurangam, Sathish; O'Connell, Grace D; Chernyshova, Irina V; Wood, Katherine; Hung, Clark Tung-Hui; Somasundaran, Ponisseril

2014-11-01

The harsh inflammatory environment associated with injured and arthritic joints represents a major challenge to articular cartilage repair. In this study, we report the effect of cerium oxide nanoparticles, or nanoceria, in modulating development of engineered cartilage and in combating the deleterious effects of interleukin-1α. Nanoceria was found to be biocompatible with bovine chondrocytes up to a concentration of 1000 μg/mL (60,000 cells/μg of nanoceria), and its presence significantly improved compressive mechanical properties and biochemical composition (i.e., glycosaminoglycans) of engineered cartilage. Raman microspectroscopy revealed that individual chondrocytes with internalized nanoceria have increased concentrations of proline, procollagen, and glycogen as compared with cells without the nanoparticles in their vicinity. The inflammatory response due to physiologically relevant quantities of interluekin-1α (0.5 ng/mL) is partially inhibited by nanoceria. To the best of the authors' knowledge, these results are the first to demonstrate a high potential for nanoceria to improve articular cartilage tissue properties and for their long-term treatment against an inflammatory reaction.

Stabilized tin-oxide-based oxidation/reduction catalysts

NASA Technical Reports Server (NTRS)

Watkins, Anthony Neal (Inventor); Oglesby, Donald M. (Inventor); Gulati, Suresh T. (Inventor); Summers, Jerry C. (Inventor); Schryer, David R. (Inventor); Davis, Patricia P. (Inventor); Leighty, Bradley D. (Inventor); Jordan, Jeffrey D. (Inventor); Schryer, Jacqueline L. (Inventor)

2008-01-01

The invention described herein involves a novel approach to the production of oxidation/reduction catalytic systems. The present invention serves to stabilize the tin oxide reducible metal-oxide coating by co-incorporating at least another metal-oxide species, such as zirconium. In one embodiment, a third metal-oxide species is incorporated, selected from the group consisting of cerium, lanthanum, hafnium, and ruthenium. The incorporation of the additional metal oxide components serves to stabilize the active tin-oxide layer in the catalytic process during high-temperature operation in a reducing environment (e.g., automobile exhaust). Moreover, the additional metal oxides are active components due to their oxygen-retention capabilities. Together, these features provide a mechanism to extend the range of operation of the tin-oxide-based catalyst system for automotive applications, while maintaining the existing advantages.

Preparation of Carbon-Platinum-Ceria and Carbon-Platinum-Cerium catalysts and its application in Polymer Electrolyte Fuel Cell: Hydrogen, Methanol, and Ethanol

NASA Astrophysics Data System (ADS)

Guzman Blas, Rolando Pedro

This thesis is focused on fuel cells using hydrogen, methanol and ethanol as fuel. Also, in the method of preparation of catalytic material for the anode: Supercritical Fluid Deposition (SFD) and impregnation method using ethylenediaminetetraacetic acid (EDTA) as a chelating agent. The first part of the thesis describes the general knowledge about Hydrogen Polymer Exchange Membrane Fuel Cell (HPEMFC),Direct Methanol Fuel Cell (DMFC) and Direct Ethanol Fuel Cell (DEFC), as well as the properties of Cerium and CeO2 (Ceria). The second part of the thesis describes the preparation of catalytic material by Supercritical Fluid Deposition (SFD). SFD was utilized to deposit Pt and ceria simultaneously onto gas diffusion layers. The Pt-ceria catalyst deposited by SFD exhibited higher methanol oxidation activity compared to the platinum catalyst alone. The linear sweep traces of the cathode made for the methanol cross over study indicate that Pt-Ceria/C as the anode catalyst, due to its better activity for methanol, improves the fuel utilization, minimizing the methanol permeation from anode to cathode compartment. The third and fourth parts of the thesis describe the preparation of material catalytic material Carbon-Platinum-Cerium by a simple and cheap impregnation method using EDTA as a chelating agent to form a complex with cerium (III). This preparation method allows the mass production of the material catalysts without additional significant cost. Fuel cell polarization and power curves experiments showed that the Carbon-Platinum-Cerium anode materials exhibited better catalytic activity than the only Vulcan-Pt catalysts for DMFC, DEFC and HPEMFC. In the case of Vulcan-20%Pt-5%w Cerium, this material exhibits better catalytic activity than the Vulcan-20%Pt in DMFC. In the case of Vulcan-40% Pt-doped Cerium, this material exhibits better catalytic activity than the Vulcan-40% Pt in DMFC, DEFC and HPEMFC. Finally, I propose a theory that explains the reason why the

Size determination and quantification of engineered cerium oxide nanoparticles by flow field-flow fractionation coupled to inductively coupled plasma mass spectrometry.

PubMed

Sánchez-García, L; Bolea, E; Laborda, F; Cubel, C; Ferrer, P; Gianolio, D; da Silva, I; Castillo, J R

2016-03-18

Facing the lack of studies on characterization and quantification of cerium oxide nanoparticles (CeO2 NPs), whose consumption and release is greatly increasing, this work proposes a method for their sizing and quantification by Flow Field-flow Fractionation (FFFF) coupled to Inductively Coupled Plasma-Mass Spectrometry (ICP-MS). Two modalities of FFFF (Asymmetric Flow- and Hollow Fiber-Flow Field Flow Fractionation, AF4 and HF5, respectively) are compared, and their advantages and limitations discussed. Experimental conditions (carrier composition, pH, ionic strength, crossflow and carrier flow rates) are studied in detail in terms of NP separation, recovery, and repeatability. Size characterization of CeO2 NPs was addressed by different approaches. In the absence of feasible size standards of CeO2 NPs, suspensions of Ag, Au, and SiO2 NPs of known size were investigated. Ag and Au NPs failed to show a comparable behavior to that of the CeO2 NPs, whereas the use of SiO2 NPs provided size estimations in agreement to those predicted by the theory. The latter approach was thus used for characterizing the size of CeO2 NPs in a commercial suspension. Results were in adequate concordance with those achieved by transmission electron microscopy, X-ray diffraction and dynamic light scattering. The quantification of CeO2 NPs in the commercial suspension by AF4-ICP-MS required the use of a CeO2 NPs standards, since the use of ionic cerium resulted in low recoveries (99 ± 9% vs. 73 ± 7%, respectively). A limit of detection of 0.9 μg L(-1) CeO2 corresponding to a number concentration of 1.8 × 1012 L(-1) for NPs of 5 nm was achieved for an injection volume of 100 μL. Copyright © 2016 Elsevier B.V. All rights reserved.

Enhanced oral bioavailability of fenofibrate using polymeric nanoparticulated systems: physicochemical characterization and in vivo investigation

PubMed Central

Yousaf, Abid Mehmood; Kim, Dong Wuk; Oh, Yu-Kyoung; Yong, Chul Soon; Kim, Jong Oh; Choi, Han-Gon

2015-01-01

Background The intention of this research was to prepare and compare various solubility-enhancing nanoparticulated systems in order to select a nanoparticulated formulation with the most improved oral bioavailability of poorly water-soluble fenofibrate. Methods The most appropriate excipients for different nanoparticulated preparations were selected by determining the drug solubility in 1% (w/v) aqueous solutions of each carrier. The polyvinylpyrrolidone (PVP) nanospheres, hydroxypropyl-β-cyclodextrin (HP-β-CD) nanocorpuscles, and gelatin nanocapsules were formulated as fenofibrate/PVP/sodium lauryl sulfate (SLS), fenofibrate/HP-β-CD, and fenofibrate/gelatin at the optimized weight ratios of 2.5:4.5:1, 1:4, and 1:8, respectively. The three solid-state products were achieved using the solvent-evaporation method through the spray-drying technique. The physicochemical characterization of these nanoparticles was accomplished by powder X-ray diffraction, differential scanning calorimetry, scanning electron microscopy, and Fourier-transform infrared spectroscopy. Their physicochemical properties, aqueous solubility, dissolution rate, and pharmacokinetics in rats were investigated in comparison with the drug powder. Results Among the tested carriers, PVP, HP-β-CD, gelatin, and SLS showed better solubility and were selected as the most appropriate constituents for various nanoparticulated systems. All of the formulations significantly improved the aqueous solubility, dissolution rate, and oral bioavailability of fenofibrate compared to the drug powder. The drug was present in the amorphous form in HP-β-CD nanocorpuscles; however, in other formulations, it existed in the crystalline state with a reduced intensity. The aqueous solubility and dissolution rates of the nanoparticles (after 30 minutes) were not significantly different from one another. Among the nanoparticulated systems tested in this study, the initial dissolution rates (up to 10 minutes) were higher with

Superconductive articles including cerium oxide layer

DOEpatents

Wu, Xin D.; Muenchausen, Ross E.

1993-01-01

A ceramic superconductor comprising a metal oxide substrate, a ceramic high temperature superconductive material, and a intermediate layer of a material having a cubic crystal structure, said layer situated between the substrate and the superconductive material is provided, and a structure for supporting a ceramic superconducting material is provided, said structure comprising a metal oxide substrate, and a layer situated over the surface of the substrate to substantially inhibit interdiffusion between the substrate and a ceramic superconducting material deposited upon said structure.

Using cerium anomaly as an indicator of redox reactions in constructed wetland

NASA Astrophysics Data System (ADS)

Liang, R.

2013-12-01

The study area, Chiayi County located in southern Taiwan, has highly developed livestock. The surface water has very low dissolved oxygen and high NH4. Under the situation, constructed wetland becomes the most effective and economic choice to treat the wastewater in the natural waterways. Hebao Island free surface constructed wetland started to operate in late 2006. It covers an area of 0.28 km2 and is subdivided into 3 major cells, which are sedimentation cell, 1st aeration cell with rooted plants and 2nd aeration cell with float plants. The water depth of cells ranges from 0.6 m to 1.2 m. The total hydraulic retention time is about a half day. In this study, the water samples were sequentially collected along the flow path. The results of hydrochemical analysis show that the untreated inflow water can be characterized with enriched NH4 (11 ppm), sulfate (6 ppm) and arsenic (50 ppb). The removal efficiency of NH4 in the first two cells is <15%. However, the efficiency dramatically increases in the 2nd aeration cell, which is over 90%. Simultaneously, almost all of the hydrochemical properties, including EC, Ca, Mg, As Fe, Mn and other heavy metals, decrease while dissolve oxygen increases close to saturated level and aluminum is almost doubled in the exit of constructed wetland. However, the removal of sulfate and phosphate is very weak. It is worth to note that arsenic is still higher than the permissible limits recommended by WHO (10 ppb). The wetland operation should be tuned to take more arsenic away in the future. As demonstrated in the above, oxidation reaction is the most dominant mechanism to remove pollutants from the wastewater; therefore, dissolved oxygen is traditionally considered as an important indicator to evaluate the operation efficiency of wetland. However, it would need longer time to achieve equilibrium state of redox reaction involving dissolved oxygen due to the slower reaction rate. For example, the input water in this study has fairly high

The Effect of Cerium Oxide Nanoparticle Valence State on Reactive Oxygen Species and Toxicity.

PubMed

Dunnick, Katherine M; Pillai, Rajalekshmi; Pisane, Kelly L; Stefaniak, Aleksandr B; Sabolsky, Edward M; Leonard, Stephen S

2015-07-01

Cerium oxide (CeO2) nanoparticles, which are used in a variety of products including solar cells, gas sensors, and catalysts, are expected to increase in industrial use. This will subsequently lead to additional occupational exposures, making toxicology screenings crucial. Previous toxicology studies have presented conflicting results as to the extent of CeO2 toxicity, which is hypothesized to be due to the ability of Ce to exist in both a +3 and +4 valence state. Thus, to study whether valence state and oxygen vacancy concentration are important in CeO2 toxicity, CeO2 nanoparticles were doped with gadolinium to adjust the cation (Ce, Gd) and anion (O) defect states. The hypothesis that doping would increase toxicity and decrease antioxidant abilities as a result of increased oxygen vacancies and inhibition of +3 to +4 transition was tested. Differences in toxicity and reactivity based on valence state were determined in RLE-6TN rat alveolar epithelial and NR8383 rat alveolar macrophage cells using enhanced dark field microscopy, electron paramagnetic resonance (EPR), and annexin V/propidium iodide cell viability stain. Results from EPR indicated that as doping increased, antioxidant potential decreased. Alternatively, doping had no effect on toxicity at 24 h. The present results imply that as doping increases, thus subsequently increasing the Ce(3+)/Ce(4+) ratio, antioxidant potential decreases, suggesting that differences in reactivity of CeO2 are due to the ability of Ce to transition between the two valence states and the presence of increased oxygen vacancies, rather than dependent on a specific valence state.

Superconductive articles including cerium oxide layer

DOEpatents

Wu, X.D.; Muenchausen, R.E.

1993-11-16

A ceramic superconductor comprising a metal oxide substrate, a ceramic high temperature superconductive material, and a intermediate layer of a material having a cubic crystal structure, said layer situated between the substrate and the superconductive material is provided, and a structure for supporting a ceramic superconducting material is provided, said structure comprising a metal oxide substrate, and a layer situated over the surface of the substrate to substantially inhibit interdiffusion between the substrate and a ceramic superconducting material deposited upon said structure. 7 figures.

Effects of the Physical Characteristics of Cerium Oxide on Plasma-Enhanced Tetraethylorthosiliate Removal Rate of Chemical Mechanical Polishing for Shallow Trench Isolation

NASA Astrophysics Data System (ADS)

Kim, Sang-Kyun; Paik, Ungyu; Oh, Seong-Geun; Park, Yong-Kook; Katoh, Takeo; Park, Jea-Gun

2003-03-01

Ceria powders were synthesized by two different methods, solid-state displacement reaction and wet chemical precipitation, and the influence of the physical characteristics of cerium oxide on the removal rate of plasma-enhanced tetraethylorthosilicate (PETEOS) and chemical vapor deposition (CVD) nitride films in chemical mechanical planarization (CMP) was investigated. The fundamental physicochemical property and electrokinetic behavior of ceria particles in aqueous suspending media were investigated to identify the correlation between the colloidal property of ceria and the CMP performance. The surface potentials of two different ceria particles are found to have different isoelectric point (pHiep) values and differences in physical properties of ceria particles such as porosity and density were found to be the key parameters in CMP of PETEOS films. Ceria powders synthesized by the solid-state displacement reaction method yielded a higher removal rate of PETEOS and higher selectivity than powders synthesized by the wet chemical precipitation method.

Nanoparticulate drug delivery platforms for advancing bone infection therapies

PubMed Central

Uskoković, Vuk; Desai, Tejal A

2015-01-01

Introduction The ongoing surge of resistance of bacterial pathogens to antibiotic therapies and the consistently aging median member of the human race signal an impending increase in the incidence of chronic bone infection. Nanotechnological platforms for local and sustained delivery of therapeutics hold the greatest potential for providing minimally invasive and maximally regenerative therapies for this rare but persistent condition. Areas covered Shortcomings of the clinically available treatment options, including poly(methyl methacrylate) beads and calcium sulfate cements, are discussed and their transcending using calcium-phosphate/polymeric nanoparticulate composites is foreseen. Bone is a composite wherein the weakness of each component alone is compensated for by the strength of its complement and an ideal bone substitute should be fundamentally the same. Expert opinion Discrepancy between in vitro and in vivo bioactivity assessments is highlighted, alongside the inherent imperfectness of the former. Challenges entailing the cross-disciplinary nature of engineering a new generation of drug delivery vehicles are delineated and it is concluded that the future for the nanoparticulate therapeutic carriers belongs to multifunctional, synergistic and theranostic composites capable of simultaneously targeting, monitoring and treating internal organismic disturbances in a smart, feedback fashion and in direct response to the demands of the local environment. PMID:25109804

PLUTONIUM-CERIUM-COPPER ALLOYS

DOEpatents

Coffinberry, A.S.

1959-05-12

A low melting point plutonium alloy useful as fuel is a homogeneous liquid metal fueled nuclear reactor is described. Vessels of tungsten or tantalum are useful to contain the alloy which consists essentially of from 10 to 30 atomic per cent copper and the balance plutonium and cerium. with the plutontum not in excess of 50 atomic per cent.

Cerium; crystal structure and position in the periodic table.

PubMed

Johansson, Börje; Luo, Wei; Li, Sa; Ahuja, Rajeev

2014-09-17

The properties of the cerium metal have intrigued physicists and chemists for many decades. In particular a lot of attention has been directed towards its high pressure behavior, where an isostructural volume collapse (γ phase → α phase) has been observed. Two main models of the electronic aspect of this transformation have been proposed; one where the 4f electron undergoes a change from being localized into an itinerant metallic state, and one where the focus is on the interaction between the 4f electron and the conduction electrons, often referred to as the Kondo volume collapse model. However, over the years it has been repeatedly questioned whether the cerium collapse really is isostructural. Most recently, detailed experiments have been able to remove this worrisome uncertainty. Therefore the isostructural aspect of the α-γ transition has now to be seriously addressed in the theoretical modeling, something which has been very much neglected. A study of this fundamental characteristic of the cerium volume collapse is made in present paper and we show that the localized [rlhar2 ] delocalized 4f electron picture provides an adequate description of this unique behavior. This agreement makes it possible to suggest that an appropriate crossroad position for cerium in The Periodic Table.

Cerium; Crystal Structure and Position in The Periodic Table

PubMed Central

Johansson, Börje; Luo, Wei; Li, Sa; Ahuja, Rajeev

2014-01-01

The properties of the cerium metal have intrigued physicists and chemists for many decades. In particular a lot of attention has been directed towards its high pressure behavior, where an isostructural volume collapse (γ phase → α phase) has been observed. Two main models of the electronic aspect of this transformation have been proposed; one where the 4f electron undergoes a change from being localized into an itinerant metallic state, and one where the focus is on the interaction between the 4f electron and the conduction electrons, often referred to as the Kondo volume collapse model. However, over the years it has been repeatedly questioned whether the cerium collapse really is isostructural. Most recently, detailed experiments have been able to remove this worrisome uncertainty. Therefore the isostructural aspect of the α-γ transition has now to be seriously addressed in the theoretical modeling, something which has been very much neglected. A study of this fundamental characteristic of the cerium volume collapse is made in present paper and we show that the localized ⇌ delocalized 4f electron picture provides an adequate description of this unique behavior. This agreement makes it possible to suggest that an appropriate crossroad position for cerium in The Periodic Table. PMID:25227991

Transport of cerium oxide nanoparticles in saturated silica media: influences of operational parameters and aqueous chemical conditions

NASA Astrophysics Data System (ADS)

Zhang, Zhaohan; Gao, Peng; Qiu, Ye; Liu, Guohong; Feng, Yujie; Wiesner, Mark

2016-10-01

This paper aimed to investigate the influences of operational parameters and aqueous chemical conditions on transport behaviors of cerium oxides nanoparticles (CeO2-NPs) in saturated silica media. Results indicated that increasing rates of attachment efficiency (α) were related with cationic types, and critical deposition concentration (CDC) for divalent cation (Ca2+ and Mg2+) were more than 31-fold of that for monovalent cation (Na+ and K+). Increase or reduction of electrolyte pH could both promote the mobility of CeO2-NPs in glass beads, while influence was more evident at alkaline conditions. α increased linearly with NPs concentrations, while decreased linearly with flow velocity in the column, and effects were related with electrolyte contents. Presence of surfactants could sharply decreased α, and SDS was more effective to facilitate CeO2-NPs transport than Triton X-100. With DOMs concentrations increasing, α firstly kept constant, then sharply declined, and finally reduced very slowly. The influence of DOMs on NPs deposition was in order of SA > HA > TA >  BSA. Overall, this study revealed that aqueous chemical conditions was crucial to NPs transport in porous media, and would provide significant information for our understanding on the fate and transport of nanoparticles in natural environment.

Electrochemical characterization of cerium-based conversion coatings on aluminum alloy 7075-T6

NASA Astrophysics Data System (ADS)

Joshi, Simon

This research used electrochemical techniques to characterize the deposition and corrosion protection behavior of cerium-based conversion coatings on Al 7075-T6. Alkaline activation decreased native oxide impedance (5.9 kO-cm2) by ˜25% promoting deposition of 250--500 nm coatings. Activation in NaOH solutions deposited coatings with large cracks and craters, whereas Na2CO3 activation resulted in uniform coatings, i.e., fewer cracks and almost no craters. Uniformly deposited coatings exhibited better cathodic inhibition and higher impedance (˜200 kO-cm 2) than on NaOH activated substrates (˜100 kO-cm 2). Subsurface crevices, caused by Cl- and H 2O2 in the deposition solution, were found under large cracks and craters. Thus, Na2CO3 activation produced fewer subsurface crevices. To reduce subsurface crevice formation, Ce(NO3) 3 and CeCl3 were used in different ratios. Coatings made using 100% Ce(NO3)3 solutions were ˜60 nm thick without subsurface crevices, but the coatings offered little corrosion protection. Despite formation of subsurface crevices, Cl- was necessary as impedance increased linearly with Cl- concentration in the deposition solution. To characterize the different non-uniform features of the coatings, microelectrochemical testing was performed and it showed three distinct regions: active, intermediate, and passive. Humidity experiments were performed to understand the effect of moisture during salt spray testing and showed an increase in coating impedance by making the exposed substrate oxide more passive. However, this passive oxide could not provide corrosion resistance in a chloride environment. Dissolution studies showed that cerium migration was only possible at pH ≤2. Overall, deposition of uniform 250--500 nm thick outings was essential to make it an effective barrier to Cl - attach and prevent subsurface crevices on Al 7075-T6.

Trivalent cerium coped crystals as tunable laser systems: two bad apples

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hamilton, D.S.

1985-01-01

The 5d-4f transitions of trivalent doped crystals have broad emission bands with large oscillator strengths and near unity quantum efficiency. These characteristics make cerium systems strong candidates for tunable solid state lasers. However, two such cerium crystals will probably never lase. The first is Ce/sup 3 +/:YAG where a strong excited state absorption quenches the lasing transition. Our recent measurements have indicated that the excited state absorption terminates in the YAG conduction band with a peak cross section of 1.0 x 10/sup -17/ cm/sup 2/ at 700 nm. Some of the general features of impurity ion to band spectra aremore » discussed. The second system is Ce/sup 3 +/:CaF/sub 2/ where a uv pump induced photochromic center is produced following excitation of the cerium ions. The initial measurements of cerium related transient absorptions in Ce/sup 3 +/:YLF are also presented.« less

Nickel aluminides and nickel-iron aluminides for use in oxidizing environments

DOEpatents

Liu, Chain T.

1988-03-15

Nickel aluminides and nickel-iron aluminides treated with hafnium or zirconium, boron and cerium to which have been added chromium to significantly improve high temperature ductility, creep resistance and oxidation properties in oxidizing environments.

An Economic Model and Experiments to Understand Aluminum-Cerium Alloy Recycling

NASA Astrophysics Data System (ADS)

Iyer, Ananth V.; Lim, Heejong; Rios, Orlando; Sims, Zachary; Weiss, David

2018-04-01

We provide an economic model to understand the impact of adoption, sorting and pricing of scrap on the recycling of a new aluminum-cerium (AlCe) alloy for use in engine blocks in the automobile industry. The goal of the laboratory portion of this study is to investigate possible effects of cerium contamination on well-established aluminum recycling streams. Our methodology includes three components: (1) focused data gathering from industry supply chain participants, (2) experimental data through laboratory experiments to understand the impact of cerium on existing alloys and (3) an economic model to understand pricing incentives on a recycler's separation of AlCe engine blocks.

Ellipsometric analysis and optical absorption characterization of gallium phosphide nanoparticulate thin film

NASA Astrophysics Data System (ADS)

Zhang, Qi-Xian; Wei, Wen-Sheng; Ruan, Fang-Ping

2011-04-01

Gallium phosphide (GaP) nanoparticulate thin films were easily fabricated by colloidal suspension deposition via GaP nanoparticles dispersed in N,N-dimethylformamide. The microstructure of the film was performed by x-ray diffraction, high resolution transmission electron microscopy and field emission scanning electron microscopy. The film was further investigated by spectroscopic ellipsometry. After the model GaP+void|SiO2 was built and an effective medium approximation was adopted, the values of the refractive index n and the extinction coefficient k were calculated for the energy range of 0.75 eV-4.0 eV using the dispersion formula in DeltaPsi2 software. The absorption coefficient of the film was calculated from its k and its energy gaps were further estimated according to the Tauc equation, which were further verified by its fluorescence spectrum measurement. The structure and optical absorption properties of the nanoparticulate films are promising for their potential applications in hybrid solar cells.

Prophylactic Treatment with Cerium Oxide Nanoparticles Attenuate Hepatic Ischemia Reperfusion Injury in Sprague Dawley Rats.

PubMed

Manne, Nandini D P K; Arvapalli, Ravikumar; Graffeo, Vincent A; Bandarupalli, Venkata V K; Shokuhfar, Tolou; Patel, Sweetu; Rice, Kevin M; Ginjupalli, Gautam Kumar; Blough, Eric R

2017-01-01

Hepatic ischemia reperfusion is one the main causes for graft failure following transplantation. Although, the molecular events that lead to hepatic failure following ischemia reperfusion (IR) are diverse and complex, previous studies have shown that excessive formation of reactive oxygen species (ROS) are responsible for hepatic IR injury. Cerium oxide (CeO2) nanoparticles have been previously shown to act as an anti-oxidant and anti-inflammatory agent. Here, we evaluated the protective effects of CeO2 nanoparticles on hepatic ischemia reperfusion injury. Male Sprague Dawley rats were randomly assigned to one of the four groups: Control, CeO2 nanoparticle only, hepatic ischemia reperfusion (IR) group and hepatic ischemia reperfusion (IR) plus CeO2 nanoparticle group (IR+ CeO2). Partial warm hepatic ischemia was induced in left lateral and median lobes for 1h, followed by 6h of reperfusion. Animals were sacrificed after 6h of reperfusion and blood and tissue samples were collected and processed for various biochemical experiments. Prophylactic treatment with CeO2 nanoparticles (0.5mg/kg i.v (IR+CeO2 group)) 1 hour prior to hepatic ischemia and subsequent reperfusion injury lead to a decrease in serum levels of alanine aminotransaminase and lactate dehydrogenase at 6 hours after reperfusion. These changes were accompanied by significant decrease in hepatocyte necrosis along with reduction in several serum inflammatory markers such as macrophage derived chemokine, macrophage inflammatory protein-2, KC/GRO, myoglobin and plasminogen activator inhibitor-1. However, immunoblotting demonstrated no significant changes in the levels of apoptosis related protein markers such as bax, bcl2 and caspase 3 in IR and IR+ CeO2 groups at 6 hours suggesting necrosis as the main pathway for hepatocyte death. Taken together, these data suggest that CeO2 nanoparticles attenuate IR induced cell death and can be used as a prophylactic agent to prevent hepatic injury associated with graft

Study of cerium diffusion in undoped lithium-6 enriched glass with Rutherford backscattering spectrometry

NASA Astrophysics Data System (ADS)

Zhang, Xiaodong; Moore, Michael E.; Lee, Kyung-Min; Lukosi, Eric D.; Hayward, Jason P.

2016-07-01

Undoped lithium-6 enriched glasses coated with pure cerium (99.9%) with a gold protection layer on top were heated at three different temperatures (500, 550, and 600 °C) for varied durations (1, 2, and 4 h). Diffusion profiles of cerium in such glasses were obtained with the conventional Rutherford backscattering technique. Through fitting the diffusion profiles with the thin-film solution of Fick's second law, diffusion coefficients of cerium with different annealing temperatures and durations were solved. Then, the activation energy of cerium for the diffusion process in the studied glasses was found to be 114 kJ/mol with the Arrhenius equation.

Catalyst and method for reduction of nitrogen oxides

DOEpatents

Ott, Kevin C [Los Alamos, NM

2008-05-27

A Selective Catalytic Reduction (SCR) catalyst was prepared by slurry coating ZSM-5 zeolite onto a cordierite monolith, then subliming an iron salt onto the zeolite, calcining the monolith, and then dipping the monolith either into an aqueous solution of manganese nitrate and cerium nitrate and then calcining, or by similar treatment with separate solutions of manganese nitrate and cerium nitrate. The supported catalyst containing iron, manganese, and cerium showed 80 percent conversion at 113 degrees Celsius of a feed gas containing nitrogen oxides having 4 parts NO to one part NO.sub.2, about one equivalent ammonia, and excess oxygen; conversion improved to 94 percent at 147 degrees Celsius. N.sub.2O was not detected (detection limit: 0.6 percent N.sub.2O).

Catalyst and method for reduction of nitrogen oxides

DOEpatents

Ott, Kevin C [Los Alamos, NM

2008-08-19

A Selective Catalytic Reduction (SCR) catalyst was prepared by slurry coating ZSM-5 zeolite onto a cordierite monolith, then subliming an iron salt onto the zeolite, calcining the monolith, and then dipping the monolith either into an aqueous solution of manganese nitrate and cerium nitrate and then calcining, or by similar treatment with separate solutions of manganese nitrate and cerium nitrate. The supported catalyst containing iron, manganese, and cerium showed 80 percent conversion at 113 degrees Celsius of a feed gas containing nitrogen oxides having 4 parts NO to one part NO.sub.2, about one equivalent ammonia, and excess oxygen; conversion improved to 94 percent at 147 degrees Celsius. N.sub.2O was not detected (detection limit: 0.6 percent N.sub.2O).

Effect of Cerium Oxide on Morphologies and Electrochemical Properties of Ni-W-P Coating on AZ91D Magnesium

NASA Astrophysics Data System (ADS)

Sun, Wan-chang; Xu, Jia-Min; Wang, Yuan; Guo, Fang; Jia, Zong-Wei

2017-12-01

AZ91D magnesium alloy substrate was first pretreated in a phosphoric acid to obtain a phosphate coating, and then, the electroless ternary Ni-W-P coating was deposited using a sulfate nickel bath. The morphologies of the Ni-W-P coating were observed by using scanning electron microscope, the deposition rate of the coating was examined with the method of gravimetric analysis, and the phase analysis was identified by x-ray diffractometer. Electrochemical property was tested by means of an electrochemical analyzer. The results indicated that the addition of an optimum concentration of CeO2 (cerium oxide) particles could evidently improve the deposition rate and the stability of the plating bath. However, it acted as an inhibiting effect as the concentration of CeO2 particles exceeded to 8 mg/L in the sulfate nickel bath. The results also revealed that the morphology of Ni-W-P coating became more smooth, compact and uniform with the increase in the concentrations of CeO2 particles in the bath, but the corrosion resistance decreased due to the precipitation of crystal phases (Ni3P, Ni4W, etc.) after heat treatment.

Corrosion protection properties and interfacial adhesion mechanism of an epoxy/polyamide coating applied on the steel surface decorated with cerium oxide nanofilm: Complementary experimental, molecular dynamics (MD) and first principle quantum mechanics (QM) simulation methods

NASA Astrophysics Data System (ADS)

Bahlakeh, Ghasem; Ramezanzadeh, Bahram; Saeb, Mohammad Reza; Terryn, Herman; Ghaffari, Mehdi

2017-10-01

The effect of cerium oxide treatment on the corrosion protection properties and interfacial interaction of steel/epoxy was studied by electrochemical impedance spectroscopy, (EIS) classical molecular dynamics (MD) and first principle quantum mechanics (QM) simulation methods X-ray photoelectron spectroscopy (XPS) was used to verify the chemical composition of the Ce film deposited on the steel. To probe the role of the curing agent in epoxy adsorption, computations were compared for an epoxy, aminoamide and aminoamide modified epoxy. Moreover, to study the influence of water on interfacial interactions the MD simulations were executed for poly (aminoamide)-cured epoxy resin in contact with the different crystallographic cerium dioxide (ceria, CeO2) surfaces including (100), (110), and (111) in the presence of water molecules. It was found that aminoamide-cured epoxy material was strongly adhered to all types of CeO2 substrates, so that binding to ceria surfaces followed the decreasing order CeO2 (111) > CeO2 (100) > CeO2 (110) in both dry and wet environments. Calculation of interaction energies noticed an enhanced adhesion to metal surface due to aminoamide curing of epoxy resin; where facets (100) and (111) revealed electrostatic and Lewis acid-base interactions, while an additional hydrogen bonding interaction was identified for CeO2 (110). Overall, MD simulations suggested decrement of adhesion to CeO2 in wet environment compared to dry conditions. Additionally, contact angle, pull-off test, cathodic delamination and salt spray analyses were used to confirm the simulation results. The experimental results in line with modeling results revealed that Ce layer deposited on steel enhanced substrate surface free energy, work of adhesion, and interfacial adhesion strength of the epoxy coating. Furthermore, decrement of adhesion of epoxy to CeO2 in presence of water was affirmed by experimental results. EIS results revealed remarkable enhancement of the corrosion

Application of Cerium (IV) as an Oxidimetric Agent for the Determination of Ethionamide in Pharmaceutical Formulations

PubMed Central

2016-01-01

Two simple methods are described for the determination of ethionamide (ETM) in bulk drug and tablets using cerium (IV) sulphate as the oxidimetric agent. In both methods, the sample solution is treated with a measured excess of cerium (IV) solution in H2SO4 medium, and after a fixed standing time, the residual oxidant is determined either by back titration with standard iron (II) solution to a ferroin end point in titrimetry or by reacting with o-dianisidine followed by measurement of the absorbance of the orange-red coloured product at 470 nm in spectrophotometry. In titrimetry, the reaction proceeded with a stoichiometry of 1 : 2 (ETM : Ce (IV)) and the amount of cerium (IV) consumed by ETM was related to the latter's amount, and the method was applicable over 1.0–8.0 mg of drug. In spectrophotometry, Beer's law was obeyed over the concentration range of 0.5–5.0 μg/mL ETM with a molar absorptivity value of 2.66 × 104 L/(mol·cm). The limits of detection (LOD) and quantification (LOQ) calculated according to ICH guidelines were 0.013 and 0.043 μg/mL, respectively. The proposed titrimetric and spectrophotometric methods were found to yield reliable results when applied to bulk drug and tablets analysis, and hence they can be applied in quality control laboratories. PMID:27818836

Mixed oxide nanoparticles and method of making

DOEpatents

Lauf, Robert J.; Phelps, Tommy J.; Zhang, Chuanlun; Roh, Yul

2002-09-03

Methods and apparatus for producing mixed oxide nanoparticulates are disclosed. Selected thermophilic bacteria cultured with suitable reducible metals in the presence of an electron donor may be cultured under conditions that reduce at least one metal to form a doped crystal or mixed oxide composition. The bacteria will form nanoparticles outside the cell, allowing easy recovery. Selection of metals depends on the redox potentials of the reducing agents added to the culture. Typically hydrogen or glucose are used as electron donors.

Incorporation of cerium oxide into hydroxyapatite coating regulates osteogenic activity of mesenchymal stem cell and macrophage polarization.

PubMed

Li, Kai; Shen, Qingyi; Xie, Youtao; You, Mingyu; Huang, Liping; Zheng, Xuebin

2017-02-01

Biomedical coatings for orthopedic implants should facilitate osseointegration and mitigate implant-induced inflammatory reactions. Cerium oxide (CeO 2 ) ceramics possess anti-oxidative properties and can be used to decrease mediators of inflammation, which makes them attractive for biomedical applications. In our work, two kinds of CeO 2 incorporated hydroxyapatite coatings (HA-10Ce and HA-30Ce) were prepared via plasma spraying technique and the effects of CeO 2 addition on the responses of bone mesenchymal stem cells (BMSCs) and RAW264.7 macrophages were investigated. An increase in CeO 2 content in the HA coatings resulted in better osteogenic behaviors of BMSCs in terms of cell proliferation, alkaline phosphatase (ALP) activity and mineralized nodule formation. RT-PCR and western blot analysis suggested that the incorporation of CeO 2 may promote the osteogenic differentiation of BMSCs through the Smad-dependent BMP signaling pathway, which activated Runx2 expression and subsequently enhanced the expression of ALP and OCN. The expression profiles of macrophages cultured on the CeO 2 modified coating revealed a tendency toward a M2 phenotype, because of an upregulation of M2 surface markers (CD163 and CD206), anti-inflammatory cytokines (TNF-α and IL-6) and osteoblastogenesis-related genes (BMP2 and TGF-β1) as well as a downregulation of M1 surface markers (CCR7 and CD11c), proinflammatory cytokines (IL-10 and IL-1ra) and reactive oxygen species production. The results suggested the regulation of BMSCs behaviors and macrophage-mediated responses at the coating's surface were associated with CeO 2 incorporation. The incorporation of CeO 2 in HA coatings can be a valuable strategy to promote osteogenic responses and reduce inflammatory reactions.

Novel borothermal route for the synthesis of lanthanum cerium hexaborides and their field emission properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Menaka; Patra, Rajkumar; Ghosh, Santanu

2012-10-15

The present study describes the development of a simple approach to stabilize polycrystalline lanthanum cerium hexaborides without using any flux and at ambient pressure. The nanostructured lanthanum-cerium borides were synthesized using hydroxide precursors. These precursors (La{sub 1-x}Ce{sub x}(OH){sub 3}, x=0.1, 0.2, 0.3 and 0.5) were synthesized via hydrothermal route in the presence of Tergitol (surfactant, nonylphenol ethoxylate) as a capping agent. The precursors on heating with boron at 1300 Degree-Sign C lead to the formation of nanostructures (cubes, rods and pyramids) of lanthanum cerium hexaboride. We have investigated the field emission behaviour of the hexaboride films fabricated by spin coating.more » It was observed that the pyramidal shaped nanostructures of La{sub 0.5}Ce{sub 0.5}B{sub 6} shows excellent field emission characteristics with high field enhancement factor of 4502. - Graphical abstract: Nanostructured lanthanum cerium hexaboride with efficient field emission have fabricated by low temperature hydroxide precursor mediated route. Highlights: Black-Right-Pointing-Pointer New methodology to prepare lanthanum cerium hexaboride at 1300 Degree-Sign C via borothermal route. Black-Right-Pointing-Pointer Nanostructured lanthanum cerium hexaboride film by spin coating process. Black-Right-Pointing-Pointer Nanopyramids based lanthanum cerium hexaboride shows excellent field emission.« less

Effects of Cerium and Titanium Oxide Nanoparticles in Soil on the Nutrient Composition of Barley (Hordeum vulgare L.) Kernels

PubMed Central

Pošćić, Filip; Mattiello, Alessandro; Fellet, Guido; Miceli, Fabiano; Marchiol, Luca

2016-01-01

The implications of metal nanoparticles (MeNPs) are still unknown for many food crops. The purpose of this study was to evaluate the effects of cerium oxide (nCeO2) and titanium oxide (nTiO2) nanoparticles in soil at 0, 500 and 1000 mg·kg−1 on the nutritional parameters of barley (Hordeum vulgare L.) kernels. Mineral nutrients, amylose, β-glucans, amino acid and crude protein (CP) concentrations were measured in kernels. Whole flour samples were analyzed by ICP-AES/MS, HPLC and Elemental CHNS Analyzer. Results showed that Ce and Ti accumulation under MeNPs treatments did not differ from the control treatment. However, nCeO2 and nTiO2 had an impact on composition and nutritional quality of barley kernels in contrasting ways. Both MeNPs left β-glucans unaffected but reduced amylose content by approximately 21%. Most amino acids and CP increased. Among amino acids, lysine followed by proline saw the largest increase (51% and 37%, respectively). Potassium and S were both negatively impacted by MeNPs, while B was only affected by 500 mg nCeO2·kg−1. On the contrary Zn and Mn concentrations were improved by 500 mg nTiO2·kg−1, and Ca by both nTiO2 treatments. Generally, our findings demonstrated that kernels are negatively affected by nCeO2 while nTiO2 can potentially have beneficial effects. However, both MeNPs have the potential to negatively impact malt and feed production. PMID:27294945

Understanding Interactions between Manganese Oxide and Gold That Lead to Enhanced Activity for Electrocatalytic Water Oxidation

PubMed Central

2015-01-01

To develop active nonprecious metal-based electrocatalysts for the oxygen evolution reaction (OER), a limiting reaction in several emerging renewable energy technologies, a deeper understanding of the activity of the first row transition metal oxides is needed. Previous studies of these catalysts have reported conflicting results on the influence of noble metal supports on the OER activity of the transition metal oxides. Our study aims to clarify the interactions between a transition metal oxide catalyst and its metal support in turning over this reaction. To achieve this goal, we examine a catalytic system comprising nanoparticulate Au, a common electrocatalytic support, and nanoparticulate MnOx, a promising OER catalyst. We conclusively demonstrate that adding Au to MnOx significantly enhances OER activity relative to MnOx in the absence of Au, producing an order of magnitude higher turnover frequency (TOF) than the TOF of the best pure MnOx catalysts reported to date. We also provide evidence that it is a local rather than bulk interaction between Au and MnOx that leads to the observed enhancement in the OER activity. Engineering improvements in nonprecious metal-based catalysts by the addition of Au or other noble metals could still represent a scalable catalyst as even trace amounts of Au are shown to lead a significant enhancement in the OER activity of MnOx. PMID:24661269

Understanding interactions between manganese oxide and gold that lead to enhanced activity for electrocatalytic water oxidation.

PubMed

Gorlin, Yelena; Chung, Chia-Jung; Benck, Jesse D; Nordlund, Dennis; Seitz, Linsey; Weng, Tsu-Chien; Sokaras, Dimosthenis; Clemens, Bruce M; Jaramillo, Thomas F

2014-04-02

To develop active nonprecious metal-based electrocatalysts for the oxygen evolution reaction (OER), a limiting reaction in several emerging renewable energy technologies, a deeper understanding of the activity of the first row transition metal oxides is needed. Previous studies of these catalysts have reported conflicting results on the influence of noble metal supports on the OER activity of the transition metal oxides. Our study aims to clarify the interactions between a transition metal oxide catalyst and its metal support in turning over this reaction. To achieve this goal, we examine a catalytic system comprising nanoparticulate Au, a common electrocatalytic support, and nanoparticulate MnO(x), a promising OER catalyst. We conclusively demonstrate that adding Au to MnO(x) significantly enhances OER activity relative to MnO(x) in the absence of Au, producing an order of magnitude higher turnover frequency (TOF) than the TOF of the best pure MnO(x) catalysts reported to date. We also provide evidence that it is a local rather than bulk interaction between Au and MnO(x) that leads to the observed enhancement in the OER activity. Engineering improvements in nonprecious metal-based catalysts by the addition of Au or other noble metals could still represent a scalable catalyst as even trace amounts of Au are shown to lead a significant enhancement in the OER activity of MnO(x).

Microstructure, texture evolution and magnetic properties of strip-casting non-oriented 6.5 wt.% Si electrical steel doped with cerium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Hao-Ze, E-mail: lhzqq83@163.com; Liu, Hai-Tao; Liu, Zhen-Yu, E-mail: zyliu@mail.neu.edu.cn

A 0.3 mm thick non-oriented 6.5 wt.% Si electrical steel sheet doped with cerium is produced by twin-roll strip casting, hot rolling, warm rolling and annealing. A detailed study of the cerium precipitates in the as-cast strip, microstructure and texture evolution at different processing stages is carried out by electron probe micro-analysis, optical microscopy, X-ray diffraction and electron backscattered diffraction analysis. Grain interior distributing precipitates identified as Ce-oxides, Ce-oxysulfides and Ce-phosphides, and boundary distributing Ce-oxides and Ce-phosphides are observed in the as-cast strip. The initial as-cast strip is characterized by a much finer solidification microstructure and dominated by obvious //ND texture through the strip thickness. After hot and warm rolling, inhomogeneous microstructure containing large amounts of in-grain shear bands is characterized by mixed < 110 >//RD and < 111 >//ND textures. The texture of the annealed sheet with a relatively large average grain size is far more optimized by the domination of the beneficial cube, rotated cube, (001)< 120 > to (001)< 130 > and Goss texture components, and the elimination of the detrimental γ-fiber texture, leading to a superior magnetic induction and improved iron loss. - Highlights: • An Fe–6.5 wt.% Si as-cast strip doped with cerium was produced. • A thin warm rolled sheet with limited edge cracks was obtained. • Microstructure and texture evolution at each stage were investigated. • Strong λ-fiber and Goss recrystallization textures were formed. • The magnetic properties of the annealed sheet were significantly improved.« less

Microwave synthesis of pure and doped cerium (IV) oxide (CeO2) nanoparticles for methylene blue degradation.

PubMed

El Rouby, W M A; Farghali, A A; Hamdedein, A

2016-11-01

Cerium (IV) oxide (CeO 2 ), samarium (Sm) and gadolinium (Gd) doped CeO 2 nanoparticles were prepared using microwave technique. The effect of microwave irradiation time, microwave power and pH of the starting solution on the structure and crystallite size were investigated. The prepared nanoparticles were characterized using X-ray diffraction, FT-Raman spectroscopy, and transmission electron microscope. The photocatalytic activity of the as-prepared CeO 2 , Sm and Gd doped CeO 2 toward degradation of methylene blue (MB) dye was investigated under UV light irradiation. The effect of pH, the amount of catalyst and the dye concentration on the degradation extent were studied. The photocatalytic activity of CeO 2 was kinetically enhanced by trivalent cation (Gd and Sm) doping. The results revealed that Gd doped CeO 2 nanoparticles exhibit the best catalytic degradation activity on MB under UV irradiation. For clarifying the environmental safety of the by products produced from the degradation process, the pathways of MB degradation were followed using liquid chromatography/mass spectroscopy (LC/MS). The total organic carbon content measurements confirmed the results obtained by LC/MS. Compared to the same nanoparticles prepared by another method, it was found that Gd doped CeO 2 prepared by hydrothermal process was able to mineralize MB dye completely under UV light irradiation.

Synthesis of Biocompatible Nanoparticulate Coordination Polymers for Diagnostic and Therapeutic Applications

NASA Astrophysics Data System (ADS)

Kandanapitiye, Murthi S.

The combination of nanotechnology with medicinal chemistry has developed into a burgeoning research area. Nanomaterials (NMs) could be seamlessly interfaced with various facets in biology, biochemistry, medicinal chemistry and environmental chemistry that may not be available to the same material in the bulk scale. This dissertation research has focused on the development of nanoparticulate coordination polymers for diagnostic and therapeutic applications. Modern imaging techniques include X-ray computed tomography (CT), magnetic resonance imaging (MRI), single photon emission computed tomography (SPECT) and positron emission tomography (PET). We have successfully developed several types of nanoparticulate diagnostics and therapeutics that have some potential usefulness in biomedicine. Synthesis and characterization of nanoparticulate based PET (Positron emission tomography)/SPECT (Single photon emission computed tomography) are discussed in chapter 3. In chapter 4, preparation and potential utility of non-gadolinium based MRI contrast agent are reported for T1-weighted application. As far as the solely effectiveness of relaxation is concerned, Gd-based T 1-weighted MRI contrast agents have excellent enhancement of image contrast but they have risks of biological toxicity. Consequently, the search for T 1-weighted CAs with high efficacy and low toxicity has gained attention toward the Mn(II) and Fe(III). Fe(III) is considered to be more toxic to cells because free ferric or ferrous ions can catalyze the production of reactive oxygen species via the Fenton reactions. Paramagnetic chelates of Mn(II) could be employed as T1-weighted CAs. However, it is challenging to design and synthesize highly stable Mn(II) complexes that could maintain the integrity when administered to living system. Chapter 4 describes the synthesis and utility of nanoparticulate Mn analogue of Prussian blue (K2Mn 3[FeII(CN)6]2) as an effective T1 MRI contrast agent for cellular imaging X

Submicron and Nanoparticulate Matter Removal by HEPA-Rated Media Filters and Packed Beds of Granular Materials

NASA Technical Reports Server (NTRS)

Perry, J. L.; Agui, J. H.; Vijayakimar, R

2016-01-01

Contaminants generated aboard crewed spacecraft by diverse sources consist of both gaseous chemical contaminants and particulate matter. Both HEPA media filters and packed beds of granular material, such as activated carbon, which are both commonly employed for cabin atmosphere purification purposes have efficacy for removing nanoparticulate contaminants from the cabin atmosphere. The phenomena associated with particulate matter removal by HEPA media filters and packed beds of granular material are reviewed relative to their efficacy for removing fine (less than 2.5 micrometers) and ultrafine (less than 0.01 micrometers) sized particulate matter. Considerations are discussed for using these methods in an appropriate configuration to provide the most effective performance for a broad range of particle sizes including nanoparticulates.

Effect of support size on the catalytic activity of metal-oxide-doped silica particles in the glycolysis of polyethylene terephthalate.

PubMed

Wi, Rinbok; Imran, Muhammad; Lee, Kyoung G; Yoon, Sun Hong; Cho, Bong Gyoo; Kim, Do Hyun

2011-07-01

Zinc oxide (ZnO) and cerium oxide (CeO2) nanoparticles were deposited on the surface of preformed silica spheres with diameters ranging from 60 to 750 nm. Ultrasonic irradiation was employed to promote the deposition of the metal oxide nanoparticles on the surface of silica. Silica-supported zinc oxide or cerium oxide was used as a catalyst in the glycolysis of polyethylene terephthalate, one of the key processes in the depolymerization of polyethylene terephthalate. The effect of the support size on the catalytic activity was studied in terms of monomer yield, and the monomer concentration was analyzed via high-performance liquid chromatography (HPLC). The morphologies and surface properties of the catalysts were characterized using a scanning electron microscope, a transmission electron microscope, and a BET surface area analyzer, while the monomer was characterized via HPLC and nuclear-magnetic-resonance spectroscopy. Both the zinc oxide and cerium oxide deposited on a smaller support showed better distribution and less aggregation. The high specific surface area of the smaller support catalysts provided a large number of active sites. The highest monomer yield was obtained with a catalyst of 60-nm silica support.

Anomalous absorption of isolated silver nanoparticulate films in visible region of electromagnetic field.

PubMed

Kim, Sang Woo; Hui, Bang Jae; Bae, Dong-Sik

2008-02-01

Anomalous absorption of isolated silver nanoparticulate films with different morphological patterns prepared by the wet colloidal route and followed by thermal treatment were investigated. A polymer embedded silver nanoparticulate film thermally treated at 200 degrees C showed maximum absorbance at approximately 412 nm. The peak position of the surface plasmon band was slightly different but still consistent with theoretical prediction derived by the Mie theory. An isolated nanopariculate film thermally treated at 300 degrees C showed anomalous absorption. Its maximum absorption band was shifted to green regime of 506.9 nm and the bandwidth at half-maximum absorbance of the surface plasmon band was greatly broadened. The plasmon band and its bandwidth were much deviated compared to the theoretical prediction calculated for the silver nanoparticles in the surrounding medium of air and poly(vinyl pyrrolidone) or soda-lime-silica glass. Even though there was no significant growth of silver nanoparticles during thermal treatment at 300 degrees C, the anomalous absorption was observed. The anomalous absorption was not attributed to effects of particle shape and size but to effects of pores induced by development of a great number of pores in the nanoparticulate film. The anomalous absorption greatly decreased with increase in heating temperature from 400 degrees C to 500 degrees C. The extraordinary plasmon damping of the isolated film decreased and the plasmon absorption band was re-shifted to violet regime of 416 nm because of large decrease in size of particles with dramatic change of pore morphology from circular pores with rim to small continuous pores induced by spontaneous formation of new silver nanoparticles.

Probing and tuning the size, morphology, chemistry and structure of nanoscale cerium oxide

NASA Astrophysics Data System (ADS)

Kuchibhatla, Satyanarayana Vnt

Cerium oxide (ceria)-based materials in the nanoscale regime are of significant fundamental and technological interest. Nanoceria in pure and doped forms has current and potential use in solid oxide fuel cells, catalysis, UV-screening, chemical mechanical planarization, oxygen sensors, and bio-medical applications. The characteristic feature of Ce to switch between the +3 and +4 oxidation states renders oxygen buffering capability to ceria. The ease of this transformation was expected to be enhanced in the nanoceria. In most the practical scenarios, it is necessary to have a stable suspension of ceria nanoparticles (CNPs) over longer periods of time. However, the existing literature is confined to short term studies pertaining to synthesis and property evaluation. Having understood the need for a comprehensive understanding of the CNP suspensions, this dissertation is primarily aimed at understanding the behavior of CNPs in various chemical and physical environments. We have synthesized CNPs in the absence of any surfactants at room temperature and studied the aging characteristics. After gaining some understanding about the behavior of this functional oxide, the synthesis environment and aging temperature were varied, and their affects were carefully analyzed using various materials analysis techniques such as high resolution transmission electron microscopy (HRTEM), UV-Visible spectroscopy (UV-Vis), and X-ray photoelectron spectroscopy (XPS). When the CNPs were aged at room temperature in as-synthesized condition, they were observed to spontaneously assemble and evolve as fractal superoctahedral structures. The reasons for this unique polycrystalline morphology were attributed to the symmetry driven assembly of the individual truncated octahedral and octahedral seed of the ceria. HRTEM and Fast Fourier Transform (FFT) analyses were used to explain the agglomeration behavior and evolution of the octahedral morphology. Some of the observations were supported by

Effects of PEG4000 template on sol-gel synthesis of porous cerium titanate photocatalyst

NASA Astrophysics Data System (ADS)

Zhang, Wenjie; Tao, Yingjie; Li, Chuanguo

2018-04-01

Porous cerium titanate was synthesized by sol-gel method, using polyethylene glycol (PEG4000) as template agent. Brannerite structured CeTi2O6 in monoclinic system is the major substance formed in the materials. Formation of CeO2 and rutile TiO2 depends on the amount of PEG4000. The addition of PEG4000 leads to production of fine particles in the samples, but it does not apparently affect the band gap energy. Pore volume of the cerium titanate sample continuously increases with rising PEG4000 amount. The sample obtained using 3.5 g PEG4000 has BET surface area of 16.2 m2/g and pore volume of 0.0232 cm3/g. The addition of PEG4000 can obviously promote photocatalytic activity of cerium titanate, which can be proven by both enhanced production of hydroxyl radical and ofloxacin degradation efficiency. As much as 95.2% of the initial ofloxacin molecules are removed from the solution after 50 min of photocatalytic degradation on the cerium titanate obtained using 3.5 g PEG4000, while only 48.4% ofloxacin is removed on cerium titanate obtained without PEG4000.

Immobilization of simulated radioactive soil waste containing cerium by self-propagating high-temperature synthesis

NASA Astrophysics Data System (ADS)

Mao, Xianhe; Qin, Zhigui; Yuan, Xiaoning; Wang, Chunming; Cai, Xinan; Zhao, Weixia; Zhao, Kang; Yang, Ping; Fan, Xiaoling

2013-11-01

A simulated radioactive soil waste containing cerium as an imitator element has been immobilized by a thermite self-propagating high-temperature synthesis (SHS) process. The compositions, structures, and element leaching rates of products with different cerium contents have been characterized. To investigate the influence of iron on the chemical stability of the immobilized products, leaching tests of samples with different iron contents with different leaching solutions were carried out. The results showed that the imitator element cerium mainly forms the crystalline phases CeAl11O18 and Ce2SiO5. The leaching rate of cerium over a period of 28 days was 10-5-10-6 g/(m2 day). Iron in the reactants, the reaction products, and the environment has no significant effect on the chemical stability of the immobilized SHS products.

Methodology for the effective stabilization of tin-oxide-based oxidation/reduction catalysts

NASA Technical Reports Server (NTRS)

Jordan, Jeffrey D. (Inventor); Schryer, David R. (Inventor); Leighty, Bradley D. (Inventor); Watkins, Anthony N. (Inventor); Summers, Jerry C. (Inventor); Davis, Patricia P. (Inventor); Oglesby, Donald M. (Inventor); Schryer, Jacqueline L. (Inventor); Gulati, Suresh T. (Inventor)

2011-01-01

The invention described herein involves a novel approach to the production of oxidation/reduction catalytic systems. The present invention serves to stabilize the tin oxide reducible metal-oxide coating by co-incorporating at least another metal-oxide species, such as zirconium. In one embodiment, a third metal-oxide species is incorporated, selected from the group consisting of cerium, lanthanum, hafnium, and ruthenium. The incorporation of the additional metal oxide components serves to stabilize the active tin-oxide layer in the catalytic process during high-temperature operation in a reducing environment (e.g., automobile exhaust). Moreover, the additional metal oxides are active components due to their oxygen-retention capabilities. Together, these features provide a mechanism to extend the range of operation of the tin-oxide-based catalyst system for automotive applications, while maintaining the existing advantages.

Mesoporous CeO2 nanoparticles synthesized by an inverse miniemulsion technique and their catalytic properties in methane oxidation

NASA Astrophysics Data System (ADS)

Nabih, Nermeen; Schiller, Renate; Lieberwirth, Ingo; Kockrick, Emanuel; Frind, Robert; Kaskel, Stefan; Weiss, Clemens K.; Landfester, Katharina

2011-04-01

Cerium(IV) oxide nanoparticles were synthesized using an inverse miniemulsion technique with cerium nitrate hexahydrate as precursor. The resulting nanocrystallites are as small as 5 nm with a specific surface area of 158 m2 g - 1 after calcination at 400 °C. With the addition of cetyltrimethylammonium bromide (CTAB) or (poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide)) triblock copolymers (PEO-PPO-PEO) as template in the miniemulsion droplets, the specific surface area can be increased up to 255 m2 g - 1. The miniemulsions were characterized by dynamic light scattering (DLS) and the obtained oxides were examined by x-ray diffraction (XRD), nitrogen sorption (BET and BJH), and transmission electron microscopy (TEM). The catalytic activity of the resulting ceria was investigated for the temperature-programmed oxidation (TPO) of methane.

Oxide modified air electrode surface for high temperature electrochemical cells

DOEpatents

Singh, Prabhakar; Ruka, Roswell J.

1992-01-01

An electrochemical cell is made having a porous cermet electrode (16) and a porous lanthanum manganite electrode (14), with solid oxide electrolyte (15) between them, where the lanthanum manganite surface next to the electrolyte contains a thin discontinuous layer of high surface area cerium oxide and/or praseodymium oxide, preferably as discrete particles (30) in contact with the air electrode and electrolyte.

Corrosion-Activated Chemotherapeutic Function of Nanoparticulate Platinum as a Cisplatin Resistance-Overcoming Prodrug with Limited Autophagy Induction.

PubMed

Cheng, Hsien-Jen; Wu, Te-Haw; Chien, Chih-Te; Tu, Hai-Wei; Cha, Ting-Shan; Lin, Shu-Yi

2016-11-01

Despite nanoparticulate platinum (nano-Pt) has been validated to be acting as a platinum-based prodrug for anticancer therapy, the key factor in controlling its cytotoxicity remains to be clarified. In this study, it is found that the corrosion susceptibility of nano-Pt can be triggered by inducing the oxidization of superficial Pt atoms, which can kill both cisplatin-sensitive/resistance cancer cells. Direct evidence in the oxidization of superficial Pt atoms is validated to observe the formation of platinum oxides by X-ray absorption spectroscopy. The cytotoxicity is originated from the dissolution of nano-Pt followed by the release of highly toxic Pt ions during the corrosion process. Additionally, the limiting autophagy induction by nano-Pt might prevent cancer cells from acquiring autophagy-related drug resistance. With such advantages, the possibility of further autophagy-related drug resistance could be substantially reduced or even eliminated in cancer cells treated with nano-Pt. Moreover, nano-Pt is demonstrated to kill cisplatin-resistant cancer cells not only by inducing apoptosis but also by inducing necrosis for pro-inflammatory/inflammatory responses. Thus, nano-Pt treatment might bring additional therapeutic benefits by regulating immunological responses in tumor microenvironment. These findings support the idea that utilizing nano-Pt for its cytotoxic effects might potentially benefit patients with cisplatin resistance in clinical chemotherapy. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Perovskite catalysts for oxidative coupling

DOEpatents

Campbell, K.D.

1991-06-25

Perovskites of the structure A[sub 2]B[sub 2]C[sub 3]O[sub 10] are useful as catalysts for the oxidative coupling of lower alkane to heavier hydrocarbons. A is alkali metal; B is lanthanide or lanthanum, cerium, neodymium, samarium, praseodymium, gadolinium or dysprosium; and C is titanium.

Perovskite catalysts for oxidative coupling

DOEpatents

Campbell, Kenneth D.

1991-01-01

Perovskites of the structure A.sub.2 B.sub.2 C.sub.3 O.sub.10 are useful as catalysts for the oxidative coupling of lower alkane to heavier hydrocarbons. A is alkali metal; B is lanthanide or lanthanum, cerium, neodymium, samarium, praseodymium, gadolinium or dysprosium; and C is titanium.

Production of cerium dioxide microspheres by an internal gelation sol–gel method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Katalenich, Jeffrey A.

An internal gelation sol-gel technique was used to prepare cerium dioxide microspheres with uniform diameters near 100 µm. In this process, chilled aqueous solutions containing cerium, hexamethylenetetramine (HMTA), and urea are transformed into a solid gel by heat addition and are subsequently washed, dried, and sintered to produce pure cerium dioxide. Cerous nitrate and ceric ammonium nitrate solutions were compared for their usefulness in microsphere production. Gelation experiments were performed with both cerous nitrate and ceric ammonium nitrate to determine desirable concentrations of cerium, HMTA, and urea in feed solutions as well as the necessary quantity of ammonium hydroxide addedmore » to cerium solutions. Analysis of the pH before and after sample gelation was found to provide a quantitative metric for optimal parameter selection along with subjective evaluations of gel qualities. The time necessary for chilled solutions to gel upon inserting into a hot water bath was determined for samples with a variety of parameters and also used to determine desirable formulations for microsphere production. A technique for choosing the optimal mixture of ceric ammonium nitrate, HMTA, and urea was determined using gelation experiments and used to produce microspheres by dispersion of the feed solution into heated silicone oil. Gelled spheres were washed to remove excess reactants and reaction products before being dried and sintered. X-ray diffraction of air-dried microspheres, sintered microspheres, and commercial CeO 2 powders indicated that air-dried and sintered spheres were pure CeO 2.« less

Protection by Thermal and Chemical Activation with Cerium Salts of the Alloy AA2017 in Aqueous Solutions of NaCl

NASA Astrophysics Data System (ADS)

Bethencourt, Manuel; Botana, Francisco Javier; Cano, María José; González-Rovira, Leandro; Marcos, Mariano; Sánchez-Amaya, José María

2012-01-01

A wide variety of anticorrosive treatments for aluminum alloys that can be employed as "green" alternatives to those based on Cr(VI) are currently under development. This article reports a study of the morphological and anticorrosive characteristics of surface layers formed on the Al-Cu alloy AA2017 by immersion treatment in baths of cerium salt, accelerated by increased temperature and the employment of hydrogen peroxide. Scanning electron microscopy (SEM)/X-ray energy dispersive spectroscopy (XEDS) studies of the samples treated have demonstrated the existence of a heterogeneous layer formed by a film of aluminum oxide/hydroxide on the matrix, and a series of dispersed islands of cerium over the cathodic intermetallics. The protective efficacy has been evaluated using electrochemical techniques, linear polarizations (LP) and electrochemical impedance spectroscopy (EIS), and salt spray tests. The results obtained indicate that the layer provided good resistance to corrosion in media with chlorides, and the method gives a considerable reduction of the time required for the immersion treatments.

Synthesis of cerium and nickel doped titanium nanofibers for hydrolysis of sodium borohydride.

PubMed

Tamboli, Ashif H; Gosavi, S W; Terashima, Chiaki; Fujishima, Akira; Pawar, Atul A; Kim, Hern

2018-07-01

A recyclable titanium nanofibers, doped with cerium and nickel doped was successfully synthesized by using sol-gel and electrospinning method for hydrogen generation from alkali free hydrolysis of NaBH 4 . The resultant nanocomposite was characterized to find out the structural and physical-chemical properties by a series of analytical techniques such as FT-IR (Fourier transform infrared spectroscopy), XRD (X-ray diffraction), SEM (scanning electron microscope), EDX (energy-dispersive X-ray spectroscopy),N 2 adsorption-desorption and BET (Brunauer-Emmett-Teller), etc. The results revealed that cerium and nickel nanoparticles were homogeneously distributed on the surface of the TiO 2 nanofibers due to having similar oxidation state and atomic radium of TiO 2 nanofibers with CeO 2 and NiO for the effective immobilization of metal ions. The NiO doped catalyst showed superior catalytic performance towards the hydrolysis reaction of NaBH 4 at room temperature. These catalysts have ability to produce 305 mL of H 2 within the time of 160 min at room temperature. Additionally, reusability test revealed that the catalyst is active even after five runs of hydrolytic reaction, implying the as-prepared NiO doped TiO 2 nanofibers could be considered as a potential candidate catalyst for portable hydrogen fuel system such as PEMFC (proton exchange membrane fuel cells). Copyright © 2018 Elsevier Ltd. All rights reserved.

Controlled Redox Chemistry at Cerium within a Tripodal Nitroxide Ligand Framework

DOE PAGES

Bogart, Justin A.; Lippincott, Connor A.; Carroll, Patrick J.; ...

2015-10-27

Ligand reorganization has been shown to have a profound effect on the outcome of cerium redox chemistry. Through the use of a tethered, tripodal, trianionic nitroxide ligand, [((2-tBuNOH)C 6 H 4 CH 2 ) 3 N] 3- (TriNO x 3- ), controlled redox chemistry at cerium was accomplished, and typically reactive complexes of tetravalent cerium were isolated. These included rare cationic complexes [Ce(TriNO x )thf][BAr F 4 ], in which Ar F =3,5-(CF 3 ) 2 -C 6 H 3 , and [Ce(TriNO x )py][OTf] . A rare complete Ce-halide series, Ce(TriNO x )X, in which X=F - , Clmore » - , Br - , I - , was also synthesized. We explored the solution chemistry of these complexes through detailed solution-phase electrochemistry and 1 H NMR experiments and showed a unique shift in the ratio of species with inner- and outer-sphere anions with size of the anionic X - group. DFT calculations on the series of calculations corroborated the experimental findings. Also, the use of a bulky and strongly donating tethered tripodal nitroxide ligand allowed the controlled redox chemistry at cerium. As a result, rare examples of cationic Ce IV complexes were synthesized and fully characterized. The full Ce-halide series supported by the tripodal ligand framework is also reported (see scheme).« less

Structural, topographical and electrical properties of cerium doped strontium barium niobate (Ce:SBN60) ceramics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Raj, S. Gokul; Mathivanan, V.; Mohan, R.

2016-05-06

Tungsten bronze type cerium doped strontium barium niobate (Ce:SBN - Sr{sub 0.6}B{sub 0.4}Nb{sub 2}O{sub 6}) ceramics were synthesized by solid state process. Cerium was used as dopant to improve its electrical properties. Influence of Ce{sup +} ions on the photoluminescence properties was investigated in detail. The grain size topographical behavior of SBN powders and their associated abnormal grain growth (AGG) were completely analyzed through SEM studies. Finally dielectric, measurement discusses about the broad phase transition observed due to cerium dopant The results were discussed in detail.

Corrosion resistance and durability of superhydrophobic surface formed on magnesium alloy coated with nanostructured cerium oxide film and fluoroalkylsilane molecules in corrosive NaCl aqueous solution.

PubMed

Ishizaki, Takahiro; Masuda, Yoshitake; Sakamoto, Michiru

2011-04-19

The corrosion resistant performance and durability of the superhydrophobic surface on magnesium alloy coated with nanostructured cerium oxide film and fluoroalkylsilane molecules in corrosive NaCl aqueous solution were investigated using electrochemical and contact angle measurements. The durability of the superhydrophobic surface in corrosive 5 wt% NaCl aqueous solution was elucidated. The corrosion resistant performance of the superhydrophobic surface formed on magnesium alloy was estimated by electrochemical impedance spectroscopy (EIS) measurements. The EIS measurements and appropriate equivalent circuit models revealed that the superhydrophobic surface considerably improved the corrosion resistant performance of magnesium alloy AZ31. American Society for Testing and Materials (ASTM) standard D 3359-02 cross cut tape test was performed to investigate the adhesion of the superhydrophobic film to the magnesium alloy surface. The corrosion formation mechanism of the superhydrophobic surface formed on the magnesium alloy was also proposed. © 2011 American Chemical Society

Structural characterization of terrestrial microbial Mn oxides from Pinal Creek, AZ

USGS Publications Warehouse

Bargar, J.R.; Fuller, C.C.; Marcus, M.A.; Brearley, A.J.; Perez De la Rosa, M.; Webb, S.M.; Caldwell, W.A.

2009-01-01

The microbial catalysis of Mn(II) oxidation is believed to be a dominant source of abundant sorption- and redox-active Mn oxides in marine, freshwater, and subsurface aquatic environments. In spite of their importance, environmental oxides of known biogenic origin have generally not been characterized in detail from a structural perspective. Hyporheic zone Mn oxide grain coatings at Pinal Creek, Arizona, a metals-contaminated stream, have been identified as being dominantly microbial in origin and are well studied from bulk chemistry and contaminant hydrology perspectives. This site thus presents an excellent opportunity to study the structures of terrestrial microbial Mn oxides in detail. XRD and EXAFS measurements performed in this study indicate that the hydrated Pinal Creek Mn oxide grain coatings are layer-type Mn oxides with dominantly hexagonal or pseudo-hexagonal layer symmetry. XRD and TEM measurements suggest the oxides to be nanoparticulate plates with average dimensions on the order of 11 nm thick ?? 35 nm diameter, but with individual particles exhibiting thickness as small as a single layer and sheets as wide as 500 nm. The hydrated oxides exhibit a 10-?? basal-plane spacing and turbostratic disorder. EXAFS analyses suggest the oxides contain layer Mn(IV) site vacancy defects, and layer Mn(III) is inferred to be present, as deduced from Jahn-Teller distortion of the local structure. The physical geometry and structural details of the coatings suggest formation within microbial biofilms. The biogenic Mn oxides are stable with respect to transformation into thermodynamically more stable phases over a time scale of at least 5 months. The nanoparticulate layered structural motif, also observed in pure culture laboratory studies, appears to be characteristic of biogenic Mn oxides and may explain the common occurrence of this mineral habit in soils and sediments. ?? 2008 Elsevier Ltd.

Radioprotective cerium oxide nanoparticles: Molecular imaging investigations of conps' pharmacokinetics, efficacy, and mechanisms of action

NASA Astrophysics Data System (ADS)

McDonagh, Philip Reed Wills, III

Cerium oxide nanoparticles (CONPs) are being investigated for several anti-oxidant applications in medicine. One of their most promising applications is as a radioprotective drug, an area of research in need due to the severe side effects from radiation therapy. In this work, the potential of CONPs as a radioprotective drug is examined using four criteria: favorable biodistribution/pharmacokinetics, low toxicity, ability to protect normal tissue from radiation damage, and lack of protection of tumor. The mechanisms of action of CONPs are also studied. Biodistribution was determined in radiolabeled CONPs with surface coatings including citrate, dextran T10-amine (DT10-NH2), dextran T10-polyethylene glycol (DT10-PEG), dextran T10-sulfobetaine (DT10-SB) and poly(acrylic acid) (PAA), and compared to uncoated. 89Zr was incorporated into CONPs for positron emission tomography (PET) imaging and ex vivo tissue analysis in tumor bearing mice. Compared to uncoated [ 89Zr]CONPs, coated [89Zr]CONPs showed improved biodistribution, including significantly enhanced renal clearance of PAA- [89Zr]CONPs. The toxicity of CONPs was evaluated in vitro and in vivo, with low toxicity at therapeutic doses. After clinically mimetic radiation therapy, pre-treatment of mice with coated and uncoated CONPs showed greater than 50% reduction of cell death in normal colon tissue, comparable to the clinically available radioprotective drug amifostine. Tumor control after irradiation of spontaneous colon tumors was unchanged with PAA-CONP pre-treatment, while citrate, DT10-PEG, and uncoated CONP pre-treatment had slightly less tumor control. Xenograft tumors were irradiated after pH normalizing treatment with sodium bicarbonate and PAA-CONP pre-treatment. Treatment of these tumors showed slightly less tumor control than irradiation alone or PAA-CONP plus irradiation, demonstrating that the acidic pH of the tumor microenvironment may be the basis of preventing CONPs' radioprotective properties in

Stabilization of 238Pu-contaminated combustible waste by molten salt oxidation

NASA Astrophysics Data System (ADS)

Stimmel, Jay J.; Remerowski, Mary Lynn; Ramsey, Kevin B.; Heslop, J. Mark

2000-07-01

Surrogate studies were conducted using the molten salt oxidation system at the Naval Surface Warfare Center-Indian Head Division. This system uses a rotary feed system and an alumina molten salt oxidation vessel. The combustible materials were tested individually and together in a homogenized mixture. A slurry containing pyrolyzed cheesecloth ash spiked with cerium oxide, which is used as a surrogate for plutonium, and ethylene glycol were also treated in the molten salt oxidation vessel.

Integrated Heat Switch/Oxide Sorption Compressor

NASA Technical Reports Server (NTRS)

Bard, Steven

1989-01-01

Thermally-driven, nonmechanical compressor uses container filled with compressed praseodymium cerium oxide powder (PrCeOx) to provide high-pressure flow of oxygen gas for driving closed-cycle Joule-Thomson-expansion refrigeration unit. Integrated heat switch/oxide sorption compressor has no moving parts except check valves, which control flow of oxygen gas between compressor and closed-cycle Joule-Thomson refrigeration system. Oxygen expelled from sorbent at high pressure by evacuating heat-switch gap and turning on heater.

Ferroportin mediates the intestinal absorption of iron from a nanoparticulate ferritin core mimetic in mice

PubMed Central

Aslam, Mohamad F.; Frazer, David M.; Faria, Nuno; Bruggraber, Sylvaine F. A.; Wilkins, Sarah J.; Mirciov, Cornel; Powell, Jonathan J.; Anderson, Greg J.; Pereira, Dora I. A.

2014-01-01

The ferritin core is composed of fine nanoparticulate Fe3+ oxohydroxide, and we have developed a synthetic mimetic, nanoparticulate Fe3+ polyoxohydroxide (nanoFe3+). The aim of this study was to determine how dietary iron derived in this fashion is absorbed in the duodenum. Following a 4 wk run-in on an Fe-deficient diet, mice with intestinal-specific disruption of the Fpn-1 gene (Fpn-KO), or littermate wild-type (WT) controls, were supplemented with Fe2+ sulfate (FeSO4), nanoFe3+, or no added Fe for a further 4 wk. A control group was Fe sufficient throughout. Direct intestinal absorption of nanoFe3+ was investigated using isolated duodenal loops. Our data show that FeSO4 and nanoFe3+ are equally bioavailable in WT mice, and at wk 8 the mean ± sem hemoglobin increase was 18 ± 7 g/L in the FeSO4 group and 30 ± 5 g/L in the nanoFe3+ group. Oral iron failed to be utilized by Fpn-KO mice and was retained in enterocytes, irrespective of the iron source. In summary, although nanoFe3+ is taken up directly by the duodenum its homeostasis is under the normal regulatory control of dietary iron absorption, namely via ferroportin-dependent efflux from enterocytes, and thus offers potential as a novel oral iron supplement.—Aslam, M. F., Frazer, D. M., Faria, N., Bruggraber, S. F. A., Wilkins, S. J., Mirciov, C., Powell, J. J., Anderson, G. J., Pereira, D. I. A. Ferroportin mediates the intestinal absorption of iron from a nanoparticulate ferritin core mimetic in mice. PMID:24776745

Composite catalyst for carbon monoxide and hydrocarbon oxidation

DOEpatents

Liu, W.; Flytzani-Stephanopoulos, M.

1996-03-19

A method and composition are disclosed for the complete oxidation of carbon monoxide and/or hydrocarbon compounds. The method involves reacting the carbon monoxide and/or hydrocarbons with an oxidizing agent in the presence of a metal oxide composite catalyst. The catalyst is prepared by combining fluorite-type oxygen ion conductors with active transition metals. The fluorite oxide, selected from the group consisting of cerium oxide, zirconium oxide, thorium oxide, hafnium oxide, and uranium oxide, and may be doped by alkaline earth and rare earth oxides. The transition metals, selected from the group consisting of molybdenum, copper, cobalt, manganese, nickel, and silver, are used as additives. The atomic ratio of transition metal to fluorite oxide is less than one.

Composite catalyst for carbon monoxide and hydrocarbon oxidation

DOEpatents

Liu, Wei; Flytzani-Stephanopoulos, Maria

1996-01-01

A method and composition for the complete oxidation of carbon monoxide and/or hydrocarbon compounds. The method involves reacting the carbon monoxide and/or hydrocarbons with an oxidizing agent in the presence of a metal oxide composite catalyst. The catalyst is prepared by combining fluorite-type oxygen ion conductors with active transition metals. The fluorite oxide, selected from the group consisting of cerium oxide, zirconium oxide, thorium oxide, hafnium oxide, and uranium oxide, and may be doped by alkaline earth and rare earth oxides. The transition metals, selected from the group consisting of molybdnum, copper, cobalt, maganese, nickel, and silver, are used as additives. The atomic ratio of transition metal to fluorite oxide is less than one.

Investigation of americium-241 metal alloys for target applications. [Alloys with cerium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Conner, W.V.

1980-01-01

Several americium-241 metal alloys have been investigated for possible use in the Lawrence Livermore National Laboratory Radiochemical Diagnostic Tracer Program. Alloys investigated have included uranium-americium, aluminum-americium, and cerium-americium. Uranium-americium alloys with the desired properties proved to be difficult to prepare, and work with this alloy was discontinued. Aluminum-americium alloys were much easier to prepare, but the alloy consisted of an aluminum-americium intermetallic compound (AmAl/sub 4/) in an aluminum matrix. This alloy could be cast and formed into shapes, but the low density of aluminum, and other problems; made the alloy unsuitable for the intended application. Americium metal was found tomore » have a high solid solubility in cerium and alloys prepared from these two elements exhibited all of the properties desired for the tracer program application. Cerium-americium alloys containing up to 34 wt % americium have been prepared using both comelting and coreduction techniques. The latter technique involves coreduction of Ce F/sub 4/ and AmF/sub 4/ with calcium metal in a sealed reduction vessel. Casting techniques have been developed for preparing up to eight 0.87 inch (2.2 cm) diameter disks in a single casting, and cerium-americium metal alloy disks containing from 10 to 25 wt % americium-241 have been prepared using these techniques.« less

Pyrazolates advance cerium chemistry: a CeIII/CeIV redox equilibrium with benzoquinone.

PubMed

Werner, Daniel; Deacon, Glen B; Junk, Peter C; Anwander, Reiner

2017-05-16

Two stable cerium(iv) 3,5-dialkylpyrazolate complexes are presented, namely dimeric [Ce(Me 2 pz) 4 ] 2 (Me 2 pz = 3,5-dimethylpyrazolate) and monomeric Ce(tBu 2 pz) 4 (tBu 2 pz = 3,5-di-tert-butylpyrazolate) along with their trivalent counterparts [Ce(Me 2 pz) 3 ] and [Ce(tBu 2 pz) 3 ] 2 . All complexes were obtained from protonolysis reactions employing the silylamide precursors Ce[N(SiHMe 2 ) 2 ] 4 and Ce[N(SiMe 3 ) 2 ] 3 . Treatment of homoleptic Ce IV and Ce III Me 2 pz complexes with 1,4-hydroquinone (H 2 hq) or 1,4-benzoquinone (bq), respectively, ultimately gave the same trimetallic Ce III species via a cerium redox equilibrium. The Ce III complex Ce 3 (Me 2 pz) 5 (pchd) 2 (L) (pchd = 1,4-bis(3,5-dimethylpyrazol-1-yl)cyclohex-2,5-diene-1,4-diolato; L = Me 2 pzH or (thf) 2 ) results from a di-1,4-pyrazolyl attack on pre-coordinated bq. The reduction of bq by [Ce(Me 2 pz) 3 (thf)] 2 , and re-oxidation by the resulting Ce IV species was supported by UV-vis spectroscopic investigations. Comparisons with the redox-innocent complexes [Ln(Me 2 pz) 3 (thf)] 2 (Ln = La and Pr) revealed far less selective reactions with bq, giving hexametallic and octametallic rare-earth metal side products containing 2-Me 2 pz substituted hq ligands.

3D highly oriented nanoparticulate and microparticulate array ofmetal oxide materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vayssieres, Lionel; Guo, Jinghua; Nordgren, Joseph

2006-09-15

Advanced nano and micro particulate thin films of 3d transition and post-transition metal oxides consisting of nanorods and microrods with parallel and perpendicular orientation with respect to the substrate normal, have been successfully grown onto various substrates by heteronucleation, without template and/or surfactant, from the aqueous condensation of solution of metal salts or metal complexes (aqueous chemical growth). Three-dimensional arrays of iron oxide nanorods and zinc oxide nanorods with parallel and perpendicular orientation are presented as well as the oxygen K-edge polarization dependent x-ray absorption spectroscopy (XAS) study of anisotropic perpendicularly oriented microrod array of ZnO performed at synchrotron radiationmore » source facility.« less

Low temperature solid oxide electrolytes (LT-SOE): A review

NASA Astrophysics Data System (ADS)

Singh, B.; Ghosh, S.; Aich, S.; Roy, B.

2017-01-01

Low temperature solid oxide fuel cell (LT-SOFC) can be a source of power for vehicles, online grid, and at the same time reduce system cost, offer high reliability, and fast start-up. A huge amount of research work, as evident from the literature has been conducted for the enhancement of the ionic conductivity of LT electrolytes in the last few years. The basic conduction mechanisms, advantages and disadvantages of different LT oxide ion conducting electrolytes {BIMEVOX systems, bilayer systems including doped cerium oxide/stabilised bismuth oxide and YSZ/DCO}, mixed ion conducting electrolytes {doped cerium oxides/alkali metal carbonate composites}, and proton conducting electrolytes {doped and undoped BaCeO3, BaZrO3, etc.} are discussed here based on the recent research articles. Effect of various material aspects (composition, doping, layer thickness, etc.), fabrication methods (to achieve different microstructures and particle size), design related strategies (interlayer, sintering aid etc.), characterization temperature & environment on the conductivity of the electrolytes and performance of the fuel cells made from these electrolytes are shown in tabular form and discussed. The conductivity of the electrolytes and performance of the corresponding fuel cells are compared. Other applications of the electrolytes are mentioned. A few considerations regarding the future prospects are pointed.

Preparation of olefins from synthesis gas using ruthenium supported on ceric oxide

DOEpatents

Pierantozzi, Ronald

1985-01-01

A catalyst comprising a ruthenium carbonyl compound deposited on a cerium oxide-containing support material provides for the selective synthesis of low molecular weight olefinic hydrocarbons from mixtures of hydrogen and carbon monoxide.

Preparation of olefins from synthesis gas using ruthenium supported on ceric oxide

DOEpatents

Pierantozzi, R.

1985-04-09

A catalyst comprising a ruthenium carbonyl compound deposited on a cerium oxide-containing support material provides for the selective synthesis of low molecular weight olefinic hydrocarbons from mixtures of hydrogen and carbon monoxide.

Catalytic ozonation of dimethyl phthalate over cerium supported on activated carbon.

PubMed

Li, Laisheng; Ye, Weiying; Zhang, Qiuyun; Sun, Fengqiang; Lu, Ping; Li, Xukai

2009-10-15

Cerium supported on activated carbon (Ce/AC), which was prepared by dipping method, was employed to degrade dimethyl phthalate (DMP) in water. The mineral matter present in the activated carbon positively contributes to its activity to enhance DMP ozonation process. A higher dipping Ce(NO(3))(3) concentration and calcination process increase its microporous volume and surface area, and decreases its exterior surface area. The catalytic activity reaches optimal when 0.2% (w/w) cerium is deposited on activated carbon. Ce/AC catalyst was characterized by XRD, SEM and BET. The presence of either activated carbon or Ce/AC catalyst considerably improves their degradation and mineralization in the ozonation of DMP. During the ozonation (50mg/h ozone flow rate) of a 30 mg/L DMP (initial pH 5.0) with the presence of Ce/AC catalyst, TOC removal rate reaches 68% at 60 min oxidation time, 48% using activated carbon as catalyst, only 22% with ozonation alone. The presence of tert-butanol (a well known OH radical scavenger) strongly inhibits DMP degradation by activated carbon or Ce/AC catalytic ozonation. TOC removal rate follows the second-order kinetics model well. In the ozonation of DMP with 50mg/h ozone flow rate, its mineralization rate constant with the presence of Ce/AC catalyst is 2.5 times higher than that of activated carbon, 7.5 times higher than that of O(3) alone. Ce/AC catalyst shows the better catalytic activity and stability based on 780 min sequential reaction in the ozonation of DMP. Ce/AC was a promising catalyst for ozonizing organic pollutants in the aqueous solution.

An investigation of the use of cerium and polyhedral oligomeric silsesquioxanes for the protection of polymeric epoxy compounds in the low Earth orbit environment

NASA Astrophysics Data System (ADS)

Piness, Jessica Miriam

with the epoxy-amine matrix. A sedimented layer of the most incompatible POSS moiety was observed at the bottom of bars at the highest loading level of 5 wt% POSS. It was concluded that POSS could form a sedimented layer in this epoxy during cure. Epoxy amine materials containing POSS derivatives were tested by exposure to atomic oxygen at NASA Glenn Research Center with each POSS derivative present in separate samples at 2.5 wt% loading levels. Mass loss did not decrease against an unfilled control and glassification was not observed, leading to the conclusion that POSS could not be effectively concentrated at a surface to reduce degradation given the methods used. Taking this into account, the study transitioned into seeking ways to integrate highly UV absorbent cerium compounds with POSS. This part of the study is reported in Chapter IV. It was anticipated that POSS with a polar pendant group would interact through intermolecular forces with cerium (IV) oxide and produce a suspension that could be cured at the surface of polymers. However, in every experiment, the cerium (IV) oxide was not dispersed. However, a homogeneous dispersion of a cerium-containing compound was achieved by combining trisilanol phenyl POSS with cerium (III) nitrate hexahydrate. NMR and mass spectrometry showed that the mixture of Cerium nitrate and trisilanol phenyl POSS did not result in the formation of a chemical compound but FTIR studies indicated the presence of hydrogen bonding between the POSS silanols and cerium-associated water. The resulting material was termed "CePOSS". CePOSS was more UV absorbent in the UVc region than POSS or other cerium compounds as measured by solution UV-vis spectroscopy. In addition, CePOSS could be mixed into a POSS-epoxy coating, after pre-blending with poly(ethylene glycol) POSS, to produce films that were essentially opaque in the UV region below a wavelength of about 300 nm, and transparent in the visible region above 300 nm. The discovery of a 'window

Cerium LIII-edge x-ray absorption study of the CexFe4-yCoySb12 skutterudites

NASA Astrophysics Data System (ADS)

Grandjean, Fernande; Long, Gary J.; Cortes, Robert; Morelli, Donald T.; Meisner, Gregory P.

2000-11-01

The cerium LIII-edge x-ray absorption near-edge spectra of the CexFe4-yCoySb12 compounds have been obtained at 295 K and unambiguously indicate that cerium is in the 4f1 electronic ground state for all values of 0.22<=x<=0.98 and 0.0<=y<=3.5. This stable trivalent state of cerium is in agreement with the proposed (CeFe4Sb12)1-α(□Co4Sb12)α, solid solution structure, in which the cerium atoms are always surrounded by twelve antimony first neighbors and six iron second neighbors, the observed magnetic properties of CeFe4Sb12 and Ce0.9Fe3CoSb12, and the electronic structure of CeFe4Sb12 obtained from band-structure calculations.

A chemical-spectrochemical method for the determination of rare earth elements and thorium in cerium minerals

USGS Publications Warehouse

Rose, H.J.; Murata, K.J.; Carron, M.K.

1954-01-01

In a combined chemical-spectrochemical procedure for quantitatively determining rare earth elements in cerium minerals, cerium is determined volumetrically, a total rare earths plus thoria precipitate is separated chemically, the ceria content of the precipitate is raised to 80??0 percent by adding pure ceria, and the resulting mixture is analyzed for lanthanum, praseodymium, neodymium, samarium, gadolinium, yttrium, and thorium spectrochemically by means of the d.c. carbon arc. Spectral lines of singly ionized cerium are used as internal standard lines in the spectrochemical determination which is patterned after Fassel's procedure [1]. Results of testing the method with synthetic mixtures of rare earths and with samples of chemically analyzed cerium minerals show that the coefficient of variation for a quadruplicate determination of any element does not exceed 5??0 (excepting yttrium at concentrations less than 1 percent) and that the method is free of serious systematic error. ?? 1954.

Characterization of rabies pDNA nanoparticulate vaccine in poloxamer 407 gel.

PubMed

Bansal, Amit; Wu, Xianfu; Olson, Victoria; D'Souza, Martin J

2018-07-10

Plasmid DNA (pDNA) vaccines have the potential for protection against a wide range of diseases including rabies but are rapid in degradation and poor in uptake by antigen-presenting cells. To overcome the limitations, we fabricated a pDNA nanoparticulate vaccine. The negatively charged pDNA was adsorbed onto the surface of cationic PLGA (poly (d, l-lactide-co-glycolide))-chitosan nanoparticles and were used as a delivery vehicle. To create a hydrogel for sustainable vaccine release, we dispersed the pDNA nanoparticles in poloxamer 407 gel which is liquid at 4 °C and turns into soft gels at 37 °C, providing ease of administration and preventing burst release of pDNA. Complete immobilization of pDNA to cationic nanoparticles was achieved at a pDNA to nanoparticles ratio (P/N) of 1/50. Cellular uptake of nanoparticles was both time and concentration dependent and followed a saturation kinetics with V max of 11.389 µg/mL h and K m of 139.48 µg/mL. The in vitro release studies showed the nanoparticulate vaccine has a sustained release for up to 24 days. In summary, pDNA PLGA-chitosan nanoparticles were non-cytotoxic, their buffering capacity and cell uptake were enhanced, and sustained the release of pDNA. We expect our pDNA vaccine's potency will be greatly improved in the animal studies. Copyright © 2018 Elsevier B.V. All rights reserved.

Fabrication of mesoporous cerium dioxide films by cathodic electrodeposition.

PubMed

Kim, Young-Soo; Lee, Jin-Kyu; Ahn, Jae-Hoon; Park, Eun-Kyung; Kim, Gil-Pyo; Baeck, Sung-Hyeon

2007-11-01

Mesoporous cerium dioxide (Ceria, CeO2) thin films have been successfully electrodeposited onto ITO-coated glass substrates from an aqueous solution of cerium nitrate using CTAB (Cetyltrimethylammonium Bromide) as a templating agent. The synthesized films underwent detailed characterizations. The crystallinity of synthesized CeO2 film was confirmed by XRD analysis and HR-TEM analysis, and surface morphology was investigated by SEM analysis. The presence of mesoporosity in fabricated films was confirmed by TEM and small angle X-ray analysis. As-synthesized film was observed from XRD analysis and HR-TEM image to have well-crystallized structure of cubic phase CeO2. Transmission electron microscopy and small angle X-ray analysis revealed the presence of uniform mesoporosity with a well-ordered lamellar phase in the CeO2 films electrodeposited with CTAB templating.

Development studies for a novel wet oxidation process

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dhooge, P.M.; Hakim, L.B.

1994-01-01

A catalytic wet oxidation process (DETOX), which uses an acidic iron solution to oxidize organic compounds to carbon dioxide, water, and other simple products, was investigated as a potential method for the treatment of multicomponent hazardous and mixed wastes. The organic compounds picric acid, poly(vinyl chloride), tetrachlorothiophene, pentachloropyridine, Aroclor 1260 (a polychlorinated biphenyl), and hexachlorobenzene were oxidized in 125 ml reaction vessels. The metals arsenic, barium, beryllium, cadmium, cerium (as a surrogate for plutonium), chromium, lead, mercury, neodymium (as a surrogate for uranium), nickel, and vanadium were tested in the DETOX solution. Barium, beryllium, cerium, chromium, mercury, neodymium, nickel, andmore » vanadium were all found to be very soluble (>100 g/l) in the DETOX chloride-based solution. Arsenic, barium, cadmium, and lead solubilities were lower. Lead could be selectively precipitated from the DETOX solution. Chromium(VI) was reduced to relatively non-toxic chromium(III) by the solution. Six soils were contaminated with arsenic, barium, beryllium, chromium, lead, and neodymium oxides at approximately 0.1% by weight, and benzene, trichloroethene, mineral oil, and Aroclor 1260 at approximately 5% by weight total, and 5.g amounts treated with the DETOX solution in unstirred 125. ml reaction bombs. It is felt that soil treatment in a properly designed system is entirely possible despite incomplete oxidation of the less volatile organic materials in these unstirred tests.« less

Laser-induced breakdown spectroscopy of light water reactor simulated used nuclear fuel: Main oxide phase

DOE PAGES

Campbell, Keri R.; Judge, Elizabeth J.; Barefield, James E.; ...

2017-04-22

We show the analysis of light water reactor simulated used nuclear fuel using laser-induced breakdown spectroscopy (LIBS) is explored using a simplified version of the main oxide phase. The main oxide phase consists of the actinides, lanthanides, and zirconium. The purpose of this study is to develop a rapid, quantitative technique for measuring zirconium in a uranium dioxide matrix without the need to dissolve the material. A second set of materials including cerium oxide is also analyzed to determine precision and limit of detection (LOD) using LIBS in a complex matrix. Two types of samples are used in this study:more » binary and ternary oxide pellets. The ternary oxide, (U,Zr,Ce)O 2 pellets used in this study are a simplified version the main oxide phase of used nuclear fuel. The binary oxides, (U,Ce)O 2 and (U,Zr)O 2 are also examined to determine spectral emission lines for Ce and Zr, potential spectral interferences with uranium and baseline LOD values for Ce and Zr in a UO 2 matrix. In the spectral range of 200 to 800 nm, 33 cerium lines and 25 zirconium lines were identified and shown to have linear correlation values (R 2) > 0.97 for both the binary and ternary oxides. The cerium LOD in the (U,Ce)O 2 matrix ranged from 0.34 to 1.08 wt% and 0.94 to 1.22 wt% in (U,Ce,Zr)O 2 for 33 of Ce emission lines. The zirconium limit of detection in the (U,Zr)O 2 matrix ranged from 0.84 to 1.15 wt% and 0.99 to 1.10 wt% in (U,Ce,Zr)O 2 for 25 Zr lines. Finally, the effect of multiple elements in the plasma and the impact on the LOD is discussed.« less

Photovoltaic performance and stability of fullerene/cerium oxide double electron transport layer superior to single one in p-i-n perovskite solar cells

NASA Astrophysics Data System (ADS)

Xing, Zhou; Li, Shu-Hui; Wu, Bao-Shan; Wang, Xin; Wang, Lu-Yao; Wang, Tan; Liu, Hao-Ran; Zhang, Mei-Lin; Yun, Da-Qin; Deng, Lin-Long; Xie, Su-Yuan; Huang, Rong-Bin; Zheng, Lan-Sun

2018-06-01

Interface engineering that involves in the metal cathodes and the electron transport layers (ETLs) facilitates the simultaneous improvement of device performances and stability in perovskite solar cells (PSCs). Herein, low-temperature solution-processed cerium oxide (CeOx) films are prepared by a facile sol-gel method and employed as the interface layers between [6,6]-phenyl-C61-butyric acid methyl ester (PC61BM) and an Ag back contact to form PC61BM/CeOx double ETLs. The introduction of CeOx enables electron extraction to the Ag electrode and protects the underlying perovskite layer and thus improves the device performance and stability of the p-i-n PSCs. The p-i-n PSCs with double PC61BM/CeOx ETLs demonstrate a maximum power conversion efficiency (PCE) of 17.35%, which is superior to those of the devices with either PC61BM or CeOx single ETLs. Moreover, PC61BM/CeOx devices exhibit excellent stability in light soaking, which is mainly due to the chemically stable CeOx interlayer. The results indicate that CeOx is a promising interface modification layer for stable high-efficiency PSCs.

Chemiluminescence from an oxidation reaction of rhodamine B with cerium(IV) in a reversed micellar medium of cetyltrimethylammonium chloride in 1-hexanol-cyclohexane/water.

PubMed

Hasanin, Tamer H A; Tsunemine, Yusuke; Tsukahara, Satoshi; Okamoto, Yasuaki; Fujiwara, Terufumi

2011-01-01

The chemiluminescence (CL) emission, observed when rhodamine B (RB) in 1-hexanol-cyclohexane was mixed with cerium(IV) sulfate in sulfuric acid dispersed in a reversed micellar medium of cetyltrimethylammonium chloride (CTAC) in 1-hexanol-cyclohexane/water, was investigated using a flow-injection system. The CL emission from the oxidation reaction of RB with Ce(IV) was found to be stronger in the CTAC reversed micellar solution compared with an aqueous solution. Bearing on the enhancement effect of the CTAC reverse micelles on the RB-Ce(IV) CL, several studies including stopped-flow, fluorescence and electron spin resonance (ESR) spectrometries were performed. Rapid spectral changes of an intermediate in the RB-Ce(IV) reaction in the aqueous and reversed micellar solutions were successfully observed using a stopped-flow method. The effect of the experimental variables, i.e., oxidant concentration, sulfuric acid concentration, the mole fraction of 1-hexanol, water-to-surfactant molar concentration ratio, flow rate, upon the CL intensity was evaluated. Under the experimental conditions optimized for a flow-injection determination of RB based on the new reversed micellar-mediated CL reaction with Ce(IV), a detection limit of 0.08 µmol dm(-3) RB was achieved, and a linear calibration graph was obtained with a dynamic range from 0.5 to 20 µmol dm(-3). The relative standard deviation (n = 6) obtained at an RB concentration of 3 µmol dm(-3) was 3%.

Rapid detection of cancer related DNA nanoparticulate biomarkers and nanoparticles in whole blood

NASA Astrophysics Data System (ADS)

Heller, Michael J.; Krishnan, Raj; Sonnenberg, Avery

2010-08-01

The ability to rapidly detect cell free circulating (cfc) DNA, cfc-RNA, exosomes and other nanoparticulate disease biomarkers as well as drug delivery nanoparticles directly in blood is a major challenge for nanomedicine. We now show that microarray and new high voltage dielectrophoretic (DEP) devices can be used to rapidly isolate and detect cfc-DNA nanoparticulates and nanoparticles directly from whole blood and other high conductance samples (plasma, serum, urine, etc.). At DEP frequencies of 5kHz-10kHz both fluorescent-stained high molecular weight (hmw) DNA, cfc-DNA and fluorescent nanoparticles separate from the blood and become highly concentrated at specific DEP highfield regions over the microelectrodes, while blood cells move to the DEP low field-regions. The blood cells can then be removed by a simple fluidic wash while the DNA and nanoparticles remain highly concentrated. The hmw-DNA could be detected at a level of <260ng/ml and the nanoparticles at <9.5 x 109 particles/ml, detection levels that are well within the range for viable clinical diagnostics and drug nanoparticle monitoring. Disease specific cfc-DNA materials could also be detected directly in blood from patients with Chronic Lymphocytic Leukemia (CLL) and confirmed by PCR genotyping analysis.

Active radar guides missile to its target: receptor-based targeted treatment of hepatocellular carcinoma by nanoparticulate systems.

PubMed

Yan, Jing-Jun; Liao, Jia-Zhi; Lin, Ju-Sheng; He, Xing-Xing

2015-01-01

Patients with hepatocellular carcinoma (HCC) usually present at advanced stages and do not benefit from surgical resection, so drug therapy should deserve a prominent place in unresectable HCC treatment. But chemotherapy agents, such as doxorubicin, cisplatin, and paclitaxel, frequently encounter important problems such as low specificity and non-selective biodistribution. Recently, the development of nanotechnology led to significant breakthroughs to overcome these problems. Decorating the surfaces of nanoparticulate-based drug carriers with homing devices has demonstrated its potential in concentrating chemotherapy agents specifically to HCC cells. In this paper, we reviewed the current status of active targeting strategies for nanoparticulate systems based on various receptors such as asialoglycoprotein receptor, transferrin receptor, epidermal growth factor receptor, folate receptor, integrin, and CD44, which are abundantly expressed on the surfaces of hepatocytes or liver cancer cells. Furthermore, we pointed out their merits and defects and provided theoretical references for further research.

Apparatus and method for constant flow oxidizing of organic materials

DOEpatents

Surma, Jeffrey E.; Nelson, Norvell; Steward, G. Anthony; Bryan, Garry H.

1999-01-01

The invention is a method and apparatus using high cerium concentration in the anolyte of an electrochemical cell to oxidize organic materials. The method and apparatus further use an ultrasonic mixer to enhance the oxidation rate of the organic material in the electrochemical cell. A reaction vessel provides an advantage of independent reaction temperature control and electrochemical cell temperature control. A separate or independent reaction vessel may be used without an ultrasonic mixer to oxidize gaseous phase organic materials.

[application of the analytical transmission electron microscopy techniques for detection, identification and visualization of localization of nanoparticles of titanium and cerium oxides in mammalian cells].

PubMed

Shebanova, A S; Bogdanov, A G; Ismagulova, T T; Feofanov, A V; Semenyuk, P I; Muronets, V I; Erokhina, M V; Onishchenko, G E; Kirpichnikov, M P; Shaitan, K V

2014-01-01

This work represents the results of the study on applicability of the modern methods of analytical transmission electron microscopy for detection, identification and visualization of localization of nanoparticles of titanium and cerium oxides in A549 cell, human lung adenocarcinoma cell line. A comparative analysis of images of the nanoparticles in the cells obtained in the bright field mode of transmission electron microscopy, under dark-field scanning transmission electron microscopy and high-angle annular dark field scanning transmission electron was performed. For identification of nanoparticles in the cells the analytical techniques, energy-dispersive X-ray spectroscopy and electron energy loss spectroscopy, were compared when used in the mode of obtaining energy spectrum from different particles and element mapping. It was shown that the method for electron tomography is applicable to confirm that nanoparticles are localized in the sample but not coated by contamination. The possibilities and fields of utilizing different techniques for analytical transmission electron microscopy for detection, visualization and identification of nanoparticles in the biological samples are discussed.

Jet formation in cerium metal to examine material strength

DOE PAGES

Jensen, B. J.; Cherne, F. J.; Prime, M. B.; ...

2015-11-18

Examining the evolution of material properties at extreme conditions advances our understanding of numerous high-pressure phenomena from natural events like meteorite impacts to general solid mechanics and fluid flow behavior. Some recent advances in synchrotron diagnostics coupled with dynamic compression platforms have introduced new possibilities for examining in-situ, spatially resolved material response with nanosecond time resolution. In this work, we examined jet formation from a Richtmyer-Meshkov instability in cerium initially shocked into a transient, high-pressure phase, and then released to a low-pressure, higher-temperature state. Cerium's rich phase diagram allows us to study the yield stress following a shock induced solid-solidmore » phase transition. X-ray imaging was used to obtain images of jet formation and evolution with 2–3 μm spatial resolution. And from these images, an analytic method was used to estimate the post-shock yield stress, and these results were compared to continuum calculations that incorporated an experimentally validated equation-of-state (EOS) for cerium coupled with a deviatoric strength model. Reasonable agreement was observed between the calculations and the data illustrating the sensitivity of jet formation on the yield stress values. Finally, the data and analysis shown here provide insight into material strength during dynamic loading which is expected to aid in the development of strength aware multi-phase EOS required to predict the response of matter at extreme conditions.« less

Improvement and analysis of the hydrogen-cerium redox flow cell

NASA Astrophysics Data System (ADS)

Tucker, Michael C.; Weiss, Alexandra; Weber, Adam Z.

2016-09-01

The H2-Ce redox flow cell is optimized using commercially-available cell materials. Cell performance is found to be sensitive to the upper charge cutoff voltage, membrane boiling pretreatment, methanesulfonic-acid concentration, (+) electrode surface area and flow pattern, and operating temperature. Performance is relatively insensitive to membrane thickness, Cerium concentration, and all features of the (-) electrode including hydrogen flow. Cell performance appears to be limited by mass transport and kinetics in the cerium (+) electrode. Maximum discharge power of 895 mW cm-2 was observed at 60 °C; an energy efficiency of 90% was achieved at 50 °C. The H2-Ce cell is promising for energy storage assuming one can optimize Ce reaction kinetics and electrolyte.

Low-temperature abatement of toluene over Mn-Ce oxides catalysts synthesized by a modified hydrothermal approach

NASA Astrophysics Data System (ADS)

Du, Jinpeng; Qu, Zhenping; Dong, Cui; Song, Lixin; Qin, Yuan; Huang, Na

2018-03-01

Mn-Ce oxides catalysts were synthesized by a novel method combining redox-precipitation and hydrothermal approach. The results indicate that the ratio between manganese and cerium plays a crucial role in the formation of catalysts, and the textual properties as well as catalytic activity are remarked affected. Mn0.6Ce0.4O2 possesses a predominant catalytic activity in the oxidation of toluene, over 70% of toluene is converted at 200 °C, and the complete conversion temperature is 210 °C. The formation of Mn-Ce solid solution markedly improves the surface area as well as pore volume of Mn-Ce oxide catalyst, and Mn0.6Ce0.4O2 possesses the largest surface area of 298.5 m2/g. The abundant Ce3+ and Mn3+ on Mn0.6Ce0.4O2 catalyst facilitate the formation of oxygen vacancies, and improve the transfer of oxygen in the catalysts. Meanwhile, it is found that cerium in Mn-Ce oxide plays a key role in the adsorption of toluene, while manganese is proved to be crucial in the oxidation of toluene, the cooperation between manganese and cerium improves the catalytic reaction process. In addition, the reaction process is investigated by in situ DRIFT measurement, and it is found that the adsorbed toluene could be oxidized to benzyl alcohol as temperature rises around 80-120 °C that can be further be oxidized to benzoic acid. Then benzoic acid could be decomposed to formate and/or carbonate species as temperature rises to form CO2 and H2O. In addition, the formed by-product phenol could be further oxidized into CO2 and H2O when the temperature is high enough.

Anomalous elastic properties across the γ to α volume collapse in cerium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lipp, Magnus J.; Jenei, Zs.; Cynn, H.

2017-10-31

The behavior of the f-electrons in the lanthanides and actinides governs important macroscopic properties but their pressure and temperature dependence is not fully explored. Cerium with nominally just one 4f electron offers a case study with its iso-structural volume collapse from the γ-phase to the α-phase ending in a critical point (pC, VC, TC), unique among the elements, whose mechanism remains controversial. Here, we present longitudinal (cL) and transverse sound speeds (cT) versus pressure from higher than room temperature to TC for the first time. While cL experiences a non-linear dip at the volume collapse, cT shows a step-like change.more » This produces very peculiar macroscopic properties: the minimum in the bulk modulus becomes more pronounced, the step-like increase of the shear modulus diminishes and the Poisson’s ratio becomes negative—meaning that cerium becomes auxetic. At the critical point itself cerium lacks any compressive strength but offers resistance to shear.« less

Intergenerational responses of wheat (Triticum aestivum L.) to cerium oxide nanoparticles exposure

DOE PAGES

Rico, Cyren M.; Johnson, Mark G.; Marcus, Matthew A.; ...

2017-02-06

The intergenerational impact of engineered nanomaterials in plants is a major knowledge gap in the literature. A soil microcosm study was performed to assess the effects of multi-generational exposure of wheat (Triticum aestivum L.) to cerium oxide nanoparticles (CeO 2 -NPs). Seeds from plants that were exposed to 0, 125, and 500 mg CeO 2-NPs kg -1 soil (Ce-0, Ce-125 or Ce-500, respectively) in first generation (S1) were cultivated in factorial combinations of Ce-0, Ce-125 or Ce-500 to produce second generation (S2) plants. The factorial combinations for first/second generation treatments in Ce-125 were S1-Ce-0/S2-Ce-0, S1-Ce-0/S2-Ce-125, S1-Ce-125/S2-Ce-0 and S1-Ce-125/S2-Ce-125, and inmore » Ce-500 were S1-Ce-0/S2-Ce-0, S1-Ce-0/S2-Ce-500, S1-Ce-500/S2-Ce-0 and S1-Ce-500/S2-Ce-500. Agronomic, elemental, isotopic, and synchrotron X-ray fluorescence (XRF) and X-ray absorption near-edge spectroscopy (XANES) data were collected on second generation plants. Results showed that plants treated during the first generation only with either Ce-125 or Ce-500 (e.g. S1-Ce-125/S2-Ce-0 or S1-Ce-500/S2-Ce-0) had reduced accumulation of Ce (61 or 50%), Fe (49 or 58%) and Mn (34 or 41%) in roots, and δ 15 N (11 or 8%) in grains compared to the plants not treated in both generations (i.e. S1-Ce-0/S2-Ce-0). Plants treated in both generations with Ce-125 (i.e. S1-Ce-125/S2-Ce-125) produced grains that had lower Mn, Ca, K, Mg and P relative to plants treated in the second generation only (i.e. S1-Ce-0/S2-Ce-125). In addition, synchrotron XRF elemental chemistry maps of soil/plant thin-sections revealed limited transformation of CeO 2-NPs with no evidence of plant uptake or accumulation. The findings demonstrated that first generation exposure of wheat to CeO 2-NPs affects the physiology and nutrient profile of the second generation plants. However, the lack of concentration-dependent responses indicate that complex physiological processes are involved which alter uptake and

Intergenerational responses of wheat (Triticum aestivum L.) to cerium oxide nanoparticles exposure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rico, Cyren M.; Johnson, Mark G.; Marcus, Matthew A.

The intergenerational impact of engineered nanomaterials in plants is a major knowledge gap in the literature. A soil microcosm study was performed to assess the effects of multi-generational exposure of wheat (Triticum aestivum L.) to cerium oxide nanoparticles (CeO 2 -NPs). Seeds from plants that were exposed to 0, 125, and 500 mg CeO 2-NPs kg -1 soil (Ce-0, Ce-125 or Ce-500, respectively) in first generation (S1) were cultivated in factorial combinations of Ce-0, Ce-125 or Ce-500 to produce second generation (S2) plants. The factorial combinations for first/second generation treatments in Ce-125 were S1-Ce-0/S2-Ce-0, S1-Ce-0/S2-Ce-125, S1-Ce-125/S2-Ce-0 and S1-Ce-125/S2-Ce-125, and inmore » Ce-500 were S1-Ce-0/S2-Ce-0, S1-Ce-0/S2-Ce-500, S1-Ce-500/S2-Ce-0 and S1-Ce-500/S2-Ce-500. Agronomic, elemental, isotopic, and synchrotron X-ray fluorescence (XRF) and X-ray absorption near-edge spectroscopy (XANES) data were collected on second generation plants. Results showed that plants treated during the first generation only with either Ce-125 or Ce-500 (e.g. S1-Ce-125/S2-Ce-0 or S1-Ce-500/S2-Ce-0) had reduced accumulation of Ce (61 or 50%), Fe (49 or 58%) and Mn (34 or 41%) in roots, and δ 15 N (11 or 8%) in grains compared to the plants not treated in both generations (i.e. S1-Ce-0/S2-Ce-0). Plants treated in both generations with Ce-125 (i.e. S1-Ce-125/S2-Ce-125) produced grains that had lower Mn, Ca, K, Mg and P relative to plants treated in the second generation only (i.e. S1-Ce-0/S2-Ce-125). In addition, synchrotron XRF elemental chemistry maps of soil/plant thin-sections revealed limited transformation of CeO 2-NPs with no evidence of plant uptake or accumulation. The findings demonstrated that first generation exposure of wheat to CeO 2-NPs affects the physiology and nutrient profile of the second generation plants. However, the lack of concentration-dependent responses indicate that complex physiological processes are involved which alter uptake and

Ruthenium carbonyl catalyst supported on ceric oxide for preparation of olefins from synthesis gas

DOEpatents

Pierantozzi, R.

1985-04-02

A catalyst comprising a ruthenium carbonyl compound deposited on a cerium oxide-containing support material provides for the selective synthesis of low molecular weight olefinic hydrocarbons from mixtures of hydrogen and carbon monoxide.

Ruthenium carbonyl catalyst supported on ceric oxide for preparation of olefins from synthesis gas

DOEpatents

Pierantozzi, Ronald

1985-01-01

A catalyst comprising a ruthenium carbonyl compound deposited on a cerium oxide-containing support material provides for the selective synthesis of low molecular weight olefinic hydrocarbons from mixtures of hydrogen and carbon monoxide.

Effect of Zirconium Oxide and Zinc Oxide Nanoparticles on Physicochemical Properties and Antibiofilm Activity of a Calcium Silicate-Based Material

PubMed Central

Guerreiro-Tanomaru, Juliane Maria; Trindade-Junior, Adinael; Cesar Costa, Bernardo; da Silva, Guilherme Ferreira; Drullis Cifali, Leonardo; Basso Bernardi, Maria Inês

2014-01-01

The aim of the present study was to evaluate the antibiofilm activity against Enterococcus faecalis, compressive strength. and radiopacity of Portland cement (PC) added to zirconium oxide (ZrO2), as radiopacifier, with or without nanoparticulated zinc oxide (ZnO). The following experimental materials were evaluated: PC, PC + ZrO2, PC + ZrO2 + ZnO (5%), and PC + ZrO2 + ZnO (10%). Antibiofilm activity was analyzed by using direct contact test (DCT) on Enterococcus faecalis biofilm, for 5 h or 15 h. The analysis was conducted by using the number of colony-forming units (CFU/mL). The compressive strength was performed in a mechanical testing machine. For the radiopacity tests, the specimens were radiographed together with an aluminium stepwedge. The results were submitted to ANOVA and Tukey tests, with level of significance at 5%. The results showed that all materials presented similar antibiofilm activity (P > 0.05). The addition of nanoparticulated ZnO decreased the compressive strength of PC. All materials presented higher radiopacity than pure PC. It can be concluded that the addition of ZrO2 and ZnO does not interfere with the antibiofilm activity and provides radiopacity to Portland cement. However, the presence of ZnO (5% or 10%) significantly decreased the compressive strength of the materials. PMID:25431798

Facile synthesis of heterostructured cerium oxide/yttrium oxide nanocomposite in UV light induced photocatalytic degradation and catalytic reduction: Synergistic effect of antimicrobial studies.

PubMed

Maria Magdalane, C; Kaviyarasu, K; Judith Vijaya, J; Siddhardha, B; Jeyaraj, B

2017-08-01

Ceria (CeO 2 ) is an exciting alternative noble metal catalyst, because it has ability to release and absorb oxygen in the redox system, and function as an oxygen buffer. In this study, heterostructured catalysts consisting of CeO 2 /Y 2 O 3 nanocomposites were successfully synthesized by hydrothermal method in the presence of sodium hydroxide as a reducing agent from cerium nitrate and yttrium nitrate as a precursor which was then evaluated for its photocatalytic activity in the degradation of Rhodamine B (RhB) synthetic dye. Scanning electron microscopy (SEM) imparts the surface morphology and size of the prepared sample. Elemental compositions and the purity of the nanoparticles are proved by energy dispersive X-ray Spectroscopy (EDX). CeO 2 /Y 2 O 3 nanoparticles were made up of CeO and YO bonds which are confirmed by Fourier transform infrared spectroscopy (FTIR). Synthesis temperature and pressure, during hydrothermal reactions, plays a critical role in controlling the shape, size, oxygen vacancy concentration, and low temperature reducibility in CeO 2 based nanocomposites. The lattice constants and oxygen vacancy concentrations of ceria nanoparticles also depend upon the concentration of hydroxide ion which leads to better morphology at low temperature and pressure. Hydrogenation of p-nitrophenol to p-aminophenol with a reducing agent is conveniently carried out in aqueous medium by using this binary metal oxide catalyst. Further, the photocatalytic performance of the synthesized nanoparticles was monitored by photocatalytic degradation of Rhodamine B synthetic dye under UV light irradiation. To get maximum photocatalytic degradation (PCD) efficiency, we have used H 2 O 2 for the generation of excess reactive oxygen species (ROS). In addition, the antibacterial activity of nanoparticles against bacteria was also examined. The observed antibacterial activity results are comparable with the results obtained using the standard antibiotic. Copyright © 2017

Nano-particulate Aluminium Nitride/Al: An Efficient and Versatile Heterogeneous Catalyst for the Synthesis of Biginelli Scaffolds

NASA Astrophysics Data System (ADS)

Tekale, S. U.; Tekale, A. B.; Kanhe, N. S.; Bhoraskar, S. V.; Pawar, R. P.

2011-12-01

Nano-particulate aluminium nitride/Al (7:1) is reported as a new heterogeneous solid acid catalyst for the synthesis of 3, 4-dihydroxypyrimidi-2-(1H)-ones and their sulphur analogues using the Biginelli reaction. This method involves short reaction time, easy separation, high yields and purity of products.

Method of electrode fabrication for solid oxide electrochemical cells

DOEpatents

Jensen, R.R.

1990-11-20

A process for fabricating cermet electrodes for solid oxide electrochemical cells by sintering is disclosed. First, a porous metal electrode is fabricated on a solid oxide cell, such as a fuel cell by, for example, sintering, and is then infiltrated with a high volume fraction stabilized zirconia suspension. A second sintering step is used to sinter the infiltrated zirconia to a high density in order to more securely attach the electrode to the solid oxide electrolyte of the cell. High performance fuel electrodes can be obtained with this process. Further electrode performance enhancement may be achieved if stabilized zirconia doped with cerium oxide, chromium oxide, titanium oxide, and/or praseodymium oxide for electronic conduction is used. 5 figs.

Method of electrode fabrication for solid oxide electrochemical cells

DOEpatents

Jensen, Russell R.

1990-01-01

A process for fabricating cermet electrodes for solid oxide electrochemical cells by sintering is disclosed. First, a porous metal electrode is fabricated on a solid oxide cell, such as a fuel cell by, for example, sintering, and is then infiltrated with a high volume fraction stabilized zirconia suspension. A second sintering step is used to sinter the infiltrated zirconia to a high density in order to more securely attach the electrode to the solid oxide electrolyte of the cell. High performance fuel electrodes can be obtained with this process. Further electrode performance enhancement may be achieved if stabilized zirconia doped with cerium oxide, chromium oxide, titanium oxide, and/or praseodymium oxide for electronic conduction is used.

Improvement and analysis of the hydrogen-cerium redox flow cell

DOE PAGES

Tucker, Michael C.; Weiss, Alexandra; Weber, Adam Z.

2016-08-03

In this paper, the H 2-Ce redox flow cell is optimized using commercially-available cell materials. Cell performance is found to be sensitive to the upper charge cutoff voltage, membrane boiling pretreatment, methanesulfonic-acid concentration, (+) electrode surface area and flow pattern, and operating temperature. Performance is relatively insensitive to membrane thickness, Cerium concentration, and all features of the (-) electrode including hydrogen flow. Cell performance appears to be limited by mass transport and kinetics in the cerium (+) electrode. Maximum discharge power of 895 mW cm -2 was observed at 60 °C; an energy efficiency of 90% was achieved at 50more » °C. Finally, the H 2-Ce cell is promising for energy storage assuming one can optimize Ce reaction kinetics and electrolyte.« less

Neuropathic Pain and Lung Delivery of Nanoparticulate Drugs: An Emerging Novel Therapeutic Strategy.

PubMed

Islam, Nazrul; Abbas, Muzaffar; Rahman, Shafiqur

2017-01-01

Neuropathic pain is a chronic neurological disorder affecting millions of people around the world. The currently available pharmacologic agents for the treatment of neuropathic pain have limited efficacy and are associated with dose related unwanted adverse effects. Due to the limited access of drug molecules across blood-brain barrier, a small percentage of drug that is administered systematically, reaches the central nervous system in active form. These therapeutic agents also require daily treatment regimen that is inconvenient and potentially impact patient compliance. Application of nanoparticulate drugs for enhanced delivery system has been explored extensively in the last decades. Pulmonary delivery of nanomedicines for the management of various diseases has become an emerging treatment strategy that ensures the targeted delivery of drugs both for systemic and local effects with low dose and limited adverse effects. To the best of our knowledge, there are no inhaled drug products available on market for the treatment of neuropathic pain. The advantages of delivering therapeutics into deep lungs include non-invasive drug delivery, higher bioavailability with low dose, lower systemic toxicity, and potentially greater blood-brain barrier penetration. This review discusses and highlights the important issues on the application of emerging nanoparticulate lung delivery of drugs for the effective treatment of neuropathic pain. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Low-lying energy spectrum of the cerium dimer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nikolaev, A. V.; Skobeltsyn Institute of Nuclear Physics, Moscow State University, Vorob'evy Gory 1/2, 119991, Moscow

2011-07-15

The electronic structure of Ce{sub 2} is studied in a valence bond model with two 4f electrons localized at two cerium sites. It is shown that the low-lying energy spectrum of the simplest cerium chemical bond is determined by peculiarities of the occupied 4f states. The model allows for an analytical solution, which is discussed along with the numerical analysis. The energy spectrum is a result of the interplay between the 4f valence bond exchange, the 4f Coulomb repulsion, and the spin-orbit coupling. The calculated ground state is the even {Omega}={Lambda}={Sigma}=0 level, the lowest excitations situated at {approx}30 K aremore » the odd {Omega}={Lambda}={Sigma}=0 state and the {sup 3}6{sub 5} doublet ({Omega}={+-}5,{Lambda}={+-}6,{Sigma}={+-}1). The calculated magnetic susceptibility displays different behavior at high and low temperatures. In the absence of the spin-orbit coupling the ground state is the {sup 3}{Sigma}{sub g}{sup -} triplet. The results are compared with other many-electron calculations and experimental data.« less

Fabrication and characterization of cerium-doped barium titanate inverse opal by sol-gel method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jin Yi; Zhu Yihua; Yang Xiaoling

Cerium-doped barium titanate inverted opal was synthesized from barium acetate contained cerous acetate and tetrabutyl titanate in the interstitial spaces of a polystyrene (PS) opal. This procedure involves infiltration of precursors into the interstices of the PS opal template followed by hydrolytic polycondensation of the precursors to amorphous barium titanate and removal of the PS opal by calcination. The morphologies of opal and inverse opal were characterized by scanning electron microscope (SEM). The pores were characterized by mercury intrusion porosimetry (MIP). X-ray photoelectron spectroscopy (XPS) investigation showed the doping structure of cerium, barium and titanium. And powder X-ray diffraction allowsmore » one to observe the influence of doping degree on the grain size. The lattice parameters, crystal size and lattice strain were calculated by the Rietveld refinement method. The synthesis of cerium-doped barium titanate inverted opals provides an opportunity to electrically and optically engineer the photonic band structure and the possibility of developing tunable three-dimensional photonic crystal devices. - Graphical abstract: Cerium-doped barium titanate inverted opal was synthesized from barium acetate acid contained cerous acetate and tetrabutyl titanate in the interstitial spaces of a PS opal, which involves infiltration of precursors into the interstices of the PS opal template and removal of the PS opal by calcination.« less

A mixed acid based vanadium-cerium redox flow battery with a zero-gap serpentine architecture

NASA Astrophysics Data System (ADS)

Leung, P. K.; Mohamed, M. R.; Shah, A. A.; Xu, Q.; Conde-Duran, M. B.

2015-01-01

This paper presents the performance of a vanadium-cerium redox flow battery using conventional and zero-gap serpentine architectures. Mixed-acid solutions based on methanesulfonate-sulfate anions (molar ratio 3:1) are used to enhance the solubilities of the vanadium (>2.0 mol dm-3) and cerium species (>0.8 mol dm-3), thus achieving an energy density (c.a. 28 Wh dm-3) comparable to that of conventional all-vanadium redox flow batteries (20-30 Wh dm-3). Electrochemical studies, including cyclic voltammetry and galvanostatic cycling, show that both vanadium and cerium active species are suitable for energy storage applications in these electrolytes. To take advantage of the high open-circuit voltage (1.78 V), improved mass transport and reduced internal resistance are facilitated by the use of zero-gap flow field architecture, which yields a power density output of the battery of up to 370 mW cm-2 at a state-of-charge of 50%. In a charge-discharge cycle at 200 mA cm-2, the vanadium-cerium redox flow battery with the zero-gap architecture is observed to discharge at a cell voltage of c.a. 1.35 V with a coulombic efficiency of up to 78%.

High Temperature Oxidation and Electrochemical Studies Related to Hot Corrosion

DTIC Science & Technology

1992-05-01

sulfidation. In sulfidation, NaCI reacts with sulfur found in the fuel to form Na2SO4. The sodium sulfate reacts with the protective oxide scale resulting...fluxing or acid -base reaction model. In sufidation, 4 Bornstein explains that the oxide scales are insoluble in stoichiometric sodium sulfate , but due to...oxygen partial pressures an electron hopping mechanism dominates. Reduced cerium ions and Ce3+- oxygen vacancy associates generate these conducting

Biogenic unmodified gold nanoparticles for selective and quantitative detection of cerium using UV-vis spectroscopy and photon correlation spectroscopy (DLS).

PubMed

Priyadarshini, E; Pradhan, N; Panda, P K; Mishra, B K

2015-06-15

The ability of self-functionalized biogenic GNPs towards highly selective colorimetric detection of rare earth element cerium is being reported for the first time. GNPs underwent rapid aggregation on addition of cerium indicated by red shift of SPR peak followed by complete precipitation. Hereby, this concept of co-ordination of cerium ions onto the GNP surface has been utilized for detection of cerium. The remarkable capacity of GNPs to sensitively detect Ce without proves beneficial compared to previous reports of colorimetric sensing. MDL was 15 and 35 ppm by DLS and UV-vis spectroscopy respectively, suggesting DLS to be highly sensitive and a practical alternative in ultrasensitive detection studies. The sensing system showed a good linear fit favouring feasible detection of cerium in range of 2-50 ppm. Similar studies further showed the superior selectivity of biogenic GNPs compared to chemically synthesized counterparts. The sensing system favours on-site analysis as it overcomes need of complex instrumentation, lengthy protocols and surface modification of GNP. Copyright © 2015 Elsevier B.V. All rights reserved.

Eucalyptus tolerance mechanisms to lanthanum and cerium: subcellular distribution, antioxidant system and thiol pools.

PubMed

Shen, Yichang; Zhang, Shirong; Li, Sen; Xu, Xiaoxun; Jia, Yongxia; Gong, Guoshu

2014-12-01

Guanglin 9 (Eucalyptus grandis × Eucalyptus urophlla) and Eucalyptus grandis 5 are two eucalyptus species which have been found to grow normally in soils contaminated with lanthanum and cerium, but the tolerance mechanisms are not clear yet. In this study, a pot experiment was conducted to investigate the tolerance mechanisms of the eucalyptus to lanthanum and cerium. Cell walls stored 45.40-63.44% of the metals under lanthanum or cerium stress. Peroxidase and catalase activities enhanced with increasing soil La or Ce concentrations up to 200 mg kg(-1), while there were no obvious changes in glutathione and ascorbate concentrations. Non-protein thiols concentrations increased with increasing treatment levels up to 200 mg kg(-1), and then decreased. Phytochelatins concentrations continued to increase under La or Ce stress. Therefore, the two eucalyptus species are La and Ce tolerant plants, and the tolerance mechanisms include cell wall deposition, antioxidant system response, and thiol compound synthesis. Copyright © 2014 Elsevier Ltd. All rights reserved.

Effect of ultrasound treatment on the morpho-structural and luminescent characteristics of cerium doped yttrium silicate phosphors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Muresan, L.E., E-mail: laura_muresan2003@yahoo.com; Cadis, A.I.; Perhaita, I.

Highlights: • Y{sub 2}SiO{sub 5}:Ce is prepared by gel combustion in ultrasound conditions (US). • Morpho-structural characteristics are revealed based on FTIR, SEM, XRD, BET. • Incorporation of Ce{sup 3+} in X1/X2 type centers depends on preparative conditions. • US treatment increases the luminescent performances up to 151%. - Abstract: Cerium activated yttrium silicate (Y{sub 2}SiO{sub 5}:Ce) phosphors were prepared by gel-combustion, using yttrium–cerium nitrate as oxidizer, aspartic acid as fuel and TEOS as source of silicon. Two modalities for samples preparation were approached namely: the classical gel-combustion and sonication gel-combustion. The ultrasound treatment during the gelling stage has amore » positive effect on the structural and luminescent characteristics of the final product. Therefore, a well crystallized single X2–Y{sub 2}SiO{sub 5} phase phosphor was obtained at 1200 °C. Based on FT-IR and XRD investigations, conversion of X1 to X2–Y{sub 2}SiO{sub 5} phases is observed as the firing temperature is varied (1100 °C, 1200 °C, 1300 °C 1400 °C). The ultrasound treatment leads to smaller particle size and enhances the luminescent performances up to 151% in comparison with samples prepared by classical way.« less

Ultrastructural Interactions and Genotoxicity Assay of Cerium Dioxide Nanoparticles on Mouse Oocytes

PubMed Central

Courbiere, Blandine; Auffan, Mélanie; Rollais, Raphaël; Tassistro, Virginie; Bonnefoy, Aurélie; Botta, Alain; Rose, Jérôme; Orsière, Thierry; Perrin, Jeanne

2013-01-01

Cerium dioxide nanoparticles (CeO2 ENPs) are on the priority list of nanomaterials requiring evaluation. We performed in vitro assays on mature mouse oocytes incubated with CeO2 ENPs to study (1) physicochemical biotransformation of ENPs in culture medium; (2) ultrastructural interactions with follicular cells and oocytes using Transmission Electron Microscopy (TEM); (3) genotoxicity of CeO2 ENPs on follicular cells and oocytes using a comet assay. DNA damage was quantified as Olive Tail Moment. We show that ENPs aggregated, but their crystal structure remained stable in culture medium. TEM showed endocytosis of CeO2 ENP aggregates in follicular cells. In oocytes, CeO2 ENP aggregates were only observed around the zona pellucida (ZP). The comet assay revealed significant DNA damage in follicular cells. In oocytes, the comet assay showed a dose-related increase in DNA damage and a significant increase only at the highest concentrations. DNA damage decreased significantly both in follicular cells and in oocytes when an anti-oxidant agent was added in the culture medium. We hypothesise that at low concentrations of CeO2 ENPs oocytes could be protected against indirect oxidative stress due to a double defence system composed of follicular cells and ZP. PMID:24185910

METHOD OF SEPARATING TETRAVALENT PLUTONIUM VALUES FROM CERIUM SUB-GROUP RARE EARTH VALUES

DOEpatents

Duffield, R.B.; Stoughton, R.W.

1959-02-01

A method is presented for separating plutonium from the cerium sub-group of rare earths when both are present in an aqueous solution. The method consists in adding an excess of alkali metal carbonate to the solution, which causes the formation of a soluble plutonium carbonate precipitate and at the same time forms an insoluble cerium-group rare earth carbonate. The pH value must be adjusted to bctween 5.5 and 7.5, and prior to the precipitation step the plutonium must be reduced to the tetravalent state since only tetravalent plutonium will form the soluble carbonate complex.

Design and in vivo evaluation of solid lipid nanoparticulate systems of Olanzapine for acute phase schizophrenia treatment: Investigations on antipsychotic potential and adverse effects.

PubMed

Joseph, Emil; Reddi, Satish; Rinwa, Vibhu; Balwani, Garima; Saha, Ranendra

2017-06-15

The present paper discusses the design, characterization and in vivo evaluation of glyceryl monostearate nanoparticles of Olanzapine, an atypical antipsychotic drug for acute schizophrenia treatment, during which hospitalization is mandatory and adverse effects are at its peak. The solid lipid nanoparticulate system was obtained by emulsification-ultra sonication technique wherein three factors such as solid lipid content, concentration of surfactant and drug: solid lipid ratio were selected at three different levels in order to study their influence on significant characteristic responses such as particle size, encapsulation efficiency and drug content. A Box Behnken design with 17 runs involving whole factors at three levels was employed for the study. The optimized formulation was further coated with Polysorbate 80 in order to enhance its brain targeting potential through endocytosis transport process via blood brain barrier. The designed formulations were pre-clinically tested successfully in Wistar rat model for in vivo antipsychotic efficacy (apomorphine induced psychosis) and adverse effects (weight gain study for 28days). The results obtained indicated that solid lipid nanoparticles had very narrow size distribution (151.29±3.36nm) with very high encapsulation efficiency (74.51±1.75%). Morphological studies by SEM have shown that solid lipid nanoparticles were spherical in shape with smooth surface. Olanzapine-loaded nanoparticles prepared from solid lipid, extended the release of drug for 48h, as found by the in vitro release studies. The formulations also exhibited high redispersibility after freeze-drying and stability study results demonstrated good stability, with no significant change for a period of 6months. In vivo evaluation and adverse effects studies of Olanzapine-loaded nanoparticulate systems in animal model have demonstrated an improved therapeutic efficacy than pure Olanzapine. The antipsychotic effect of drug loaded nanoparticulate systems

A TEM analysis of nanoparticulates in a Polar ice core

DOE Office of Scientific and Technical Information (OSTI.GOV)

Esquivel, E.V.; Murr, L.E

2004-03-15

This paper explores the prospect for analyzing nanoparticulates in age-dated ice cores representing times in antiquity to establish a historical reference for atmospheric particulate regimes. Analytical transmission electron microscope (TEM) techniques were utilized to observe representative ice-melt water drops dried down on carbon/formvar or similar coated grids. A 10,000-year-old Greenland ice core was melted, and representative water drops were transferred to coated grids in a clean room environment. Essentially, all particulates observed were aggregates and either crystalline or complex mixtures of nanocrystals. Especially notable was the observation of carbon nanotubes and related fullerene-like nanocrystal forms. These observations are similar withmore » some aspects of contemporary airborne particulates including carbon nanotubes and complex nanocrystal aggregates.« less

Magmatic oxygen fugacity estimated using zircon-melt partitioning of cerium

NASA Astrophysics Data System (ADS)

Smythe, Duane J.; Brenan, James M.

2016-11-01

Using a newly-calibrated relation for cerium redox equilibria in silicate melts (Smythe and Brenan, 2015), and an internally-consistent model for zircon-melt partitioning of Ce, we provide a method to estimate the prevailing redox conditions during crystallization of zircon-saturated magmas. With this approach, oxygen fugacities were calculated for samples from the Bishop tuff (USA), Toba tuff (Indonesia) and the Nain plutonic suite (Canada), which typically agree with independent estimates within one log unit or better. With the success of reproducing the fO2 of well-constrained igneous systems, we have applied our Ce-in-zircon oxygen barometer to estimating the redox state of Earth's earliest magmas. Using the composition of the Jack Hills Hadean zircons, combined with estimates of their parental magma composition, we determined the fO2 during zircon crystallization to be between FMQ -1.0 to +2.5 (where FMQ is the fayalite-magnetite-quartz buffer). Of the parental magmas considered, Archean tonalite-trondhjemite-granodiorite (TTG) compositions yield zircon-melt partitioning most similar to well-constrained modern suites (e.g., Sano et al., 2002). Although broadly consistent with previous redox estimates from the Jack Hills zircons, our results provide a more precise determination of fO2, narrowing the range for Hadean parental magmas by more than 8 orders of magnitude. Results suggest that relatively oxidized magmatic source regions, similar in oxidation state to that of 3.5 Ga komatiite suites, existed by ∼4.4 Ga.

Nanoparticulate mackinawite formation; a stopped and continuous flow XANES and EXAFS investigation

NASA Astrophysics Data System (ADS)

Butler, I. B.; Bell, A. M.; Charnock, J. M.; Rickard, D.; Vaughan, D. J.; Oldroyd, A.

2009-12-01

The sequestration of sulfur and iron within sedimentary iron sulfides, and ultimately as pyrite, is a major sink in global biogeochemical cycles of those elements and has impacts on global carbon and oxygen cycles. The formation of the metastable black iron (II) monosulfide mackinawite is a key process because mackinawite forms in aqueous solutions where the Fe(II) and S(-II) IAP exceeds mackinawite’s Ksp. Mackinawite is the first formed iron sulfide phase, a consequence of Ostwald’s step rule and is a reactant phase during the formation of thermodynamically stable sedimentary iron sulfide minerals such as pyrite. The reaction of dissolved Fe(II) and sulfide is extremely fast and reactions in the environmentally significant near-neutral pH range tend to completion in <1 second. We have combined stopped and continuous flow techniques with X-ray absorption spectroscopy to evaluate the products of the fast precipitation kinetics of mackinawite over millisecond timescales. EXAFS spectra and data collected during flow experiments were compared with those from a well characterised freeze-dried nanoparticulate mackinawite standard and with published data. Published work has used Rietveld crystal structure refinement to determine bond distances of 2.2558 and 2.5976Å for Fe-S and Fe-Fe respectively. In our experiments Fe K edge XANES is consistent with tetrahedrally coordinated Fe in the precipitated sulfide phase. EXAFS data show that local Fe-S and Fe-Fe coordination and interatomic distances (Fe-S = 2.24Å; Fe-Fe = 2.57Å) are consistent with those determined for the standard mackinawite and published data. The coordination and spacing are developed in the precipitated phase after <10ms reaction at pH5, and considerably faster in experiments at near neutral to alkaline pH. No evidence for phases structurally intermediate between hexaqua Fe(II) and precipitated mackinawite was observed. Aqueous FeS° cluster complexes previously identified as intermediates during

Structure and corrosion behavior of sputter deposited cerium oxide based coatings with various thickness on Al 2024-T3 alloy substrates

NASA Astrophysics Data System (ADS)

Liu, Yuanyuan; Huang, Jiamu; Claypool, James B.; Castano, Carlos E.; O'Keefe, Matthew J.

2015-11-01

Cerium oxide based coatings from ∼100 to ∼1400 nm in thickness were deposited onto Al 2024-T3 alloy substrates by magnetron sputtering of a 99.99% pure CeO2 target. The crystallite size of CeO2 coatings increased from 15 nm to 46 nm as the coating thickness increased from ∼100 nm to ∼1400 nm. The inhomogeneous lattice strain increased from 0.36% to 0.91% for the ∼100 nm to ∼900 nm thick coatings and slightly decreased to 0.89% for the ∼1400 nm thick coating. The highest adhesion strength to Al alloy substrates was for the ∼210 nm thick coating, due to a continuous film coverage and low internal stress. Electrochemical measurements indicated that sputter deposited crystalline CeO2 coatings acted as physical barriers that provide good cathodic inhibition for Al alloys in saline solution. The ∼900 nm thick CeO2 coated sample had the best corrosion performance that increased the corrosion resistance by two orders magnitude and lowered the cathodic current density 30 times compared to bare Al 2024-T3 substrates. The reduced defects and exposed surface, along with suppressed charge mobility, likely accounts for the improved corrosion performance as coating thickness increased from ∼100 nm to ∼900 nm. The corrosion performance decreased for ∼1400 nm thick coatings due in part to an increase in coating defects and porosity along with a decrease in adhesion strength.

Humic Substances-dependent Aggregation and Transport of Cerium Oxide Nanoparticles in Porous Media at Different pHs and Ionic Strengths

NASA Astrophysics Data System (ADS)

Mu, L.; Jacobson, A. R.; Darnault, C. J. G.

2015-12-01

Cerium oxide nanoparticles (CeO2 NPs) are commonly used in several fields and industries, such as chemical and pharmaceutical, due to both their physical and chemical properties. For example, they are employed in the manufacturing of catalysts, as fuel additives, and as polishing agents. The release and exposure to CeO2 NPs can occur during their fabrication, application, and waste disposal, as well as through their life-cycle and accidents. Therefore, the assessment of the dynamic nature of CeO2 NPs stability and mobilty in the environment is of paramount importance to establish the environmental and public health risks associated with their inevitable release in the environment. Humic substances are a key element of soils and have been revealed to possibly affect the fate and transport of nanoparticles in soils. Consequently, our present research aims at investigating the influence that different pHs, monovalent and divalent cations, Suwannee River humic acid, and Suwanee River fulvic acid have on the aggregation, transport, and deposition of CeO2 NPs. Batch studies performed with different concentrations of humic and fulvic acids associated with a wide spectrum of pHs and ionic strengths were examined. Key variables from these batch studies were then examined to simulate experimental conditions commonly encountered in the soil-water system to conduct column transport experiments in order to establish the fate and transport of CeO2 NPs in saturated porous media, which is a critical phase in characterizing the behavior of CeO2 NPs in subsurface environmental systems.

Silica coating influences the corona and biokinetics of cerium oxide nanoparticles.

PubMed

Konduru, Nagarjun V; Jimenez, Renato J; Swami, Archana; Friend, Sherri; Castranova, Vincent; Demokritou, Philip; Brain, Joseph D; Molina, Ramon M

2015-10-12

The physicochemical properties of nanoparticles (NPs) influence their biological outcomes. We assessed the effects of an amorphous silica coating on the pharmacokinetics and pulmonary effects of CeO2 NPs following intratracheal (IT) instillation, gavage and intravenous injection in rats. Uncoated and silica-coated CeO2 NPs were generated by flame spray pyrolysis and later neutron-activated. These radioactive NPs were IT-instilled, gavaged, or intravenously (IV) injected in rats. Animals were analyzed over 28 days post-IT, 7 days post-gavage and 2 days post-injection. Our data indicate that silica coating caused more but transient lung inflammation compared to uncoated CeO2. The transient inflammation of silica-coated CeO2 was accompanied by its enhanced clearance. Then, from 7 to 28 days, clearance was similar although significantly more (141)Ce from silica-coated (35%) was cleared than from uncoated (19%) (141)CeO2 in 28 days. The protein coronas of the two NPs were significantly different when they were incubated with alveolar lining fluid. Despite more rapid clearance from the lungs, the extrapulmonary (141)Ce from silica-coated (141)CeO2 was still minimal (<1%) although lower than from uncoated (141)CeO2 NPs. Post-gavage, nearly 100% of both NPs were excreted in the feces consistent with very low gut absorption. Both IV-injected (141)CeO2 NP types were primarily retained in the liver and spleen. The silica coating significantly altered the plasma protein corona composition and enhanced retention of (141)Ce in other organs except the liver. We conclude that silica coating of nanoceria alters the biodistribution of cerium likely due to modifications in protein corona formation after IT and IV administration.

Calcium manganese(IV) oxides: biomimetic and efficient catalysts for water oxidation.

PubMed

Najafpour, Mohammad Mahdi; Pashaei, Babak; Nayeri, Sara

2012-04-28

CaMnO(3) and Ca(2)Mn(3)O(8) were synthesized and characterized by SEM, XRD, FTIR and BET. Both oxides showed oxygen evolution activity in the presence of oxone, cerium(IV) ammonium nitrate and H(2)O(2). Oxygen evolution from water during irradiation with visible light (λ > 400 nm) was also observed upon adding these manganese oxides to an aqueous solution containing tris(2,2'-bipyridyl) ruthenium(II), as photosensitizer, and chloro pentaammine cobalt(III) chloride, as electron acceptor, in an acetate buffer. The amounts of dissolved manganese and calcium from CaMnO(3) and Ca(2)Mn(3)O(8) in the oxygen evolving reactions were reported and compared with other (calcium) manganese oxides. Proposed mechanisms of oxygen evolution and proposed roles for the calcium ions are also considered. This journal is © The Royal Society of Chemistry 2012

Catalytic wet air oxidation of aniline with nanocasted Mn-Ce-oxide catalyst.

PubMed

Levi, R; Milman, M; Landau, M V; Brenner, A; Herskowitz, M

2008-07-15

The catalytic wet air oxidation of aqueous solution containing 1000 ppm aniline was conducted in a trickle-bed reactor packed with a novel nanocasted Mn-Ce-oxide catalyst (surface area of 300 m2/g) prepared using SBA-15 silica as a hard template. A range of liquid hourly space velocities (5-20 h(-1)) and temperatures (110-140 degrees C) at 10 bar of oxygen were tested. The experiments were conducted to provide the intrinsic performance of the catalysts. Complete aniline conversion, 90% TOC conversion, and 80% nitrogen mineralization were achieved at 140 degrees C and 5 h(-1). Blank experiments yielded relatively low homogeneous aniline (<35%) and negligible TOC conversions. Fast deactivation of the catalysts was experienced due to leaching caused by complexation with aniline. Acidification of the solution with HCI (molar HCI to aniline ratio of 1.2) was necessary to avoid colloidization and leaching of the nanoparticulate catalyst components. The catalyst displayed stable performance for over 200 h on stream.

Stabilization of miniemulsion droplets by cerium oxide nanoparticles: a step toward the elaboration of armored composite latexes.

PubMed

Zgheib, Nancy; Putaux, Jean-Luc; Thill, Antoine; D'Agosto, Franck; Lansalot, Muriel; Bourgeat-Lami, Elodie

2012-04-10

Stable methyl methacrylate (MMA) miniemulsions were successfully prepared using for the first time cerium oxide (CeO(2)) nanoparticles as solid stabilizers in the absence of any molecular surfactant. The interaction between MMA droplets and CeO(2) nanoparticles was induced by the use of methacrylic acid (MAA) as a comonomer. Both MAA and CeO(2) contents played a key role on the diameter and the stability of the droplets formed during the emulsification step. Cryo-transmission electron microscopy (TEM) images of the suspensions formed with 35 wt % of CeO(2) showed the presence of polydisperse 50-150 nm spherical droplets. More surprisingly, some nonspherical (likely discoidal) objects that could be the result of the sonication step were also observed. The subsequent polymerization of these Pickering miniemulsion droplets led to the formation of composite PMMA latex particles armored with CeO(2). In all cases, the conversion was limited to ca. 85%, concomitant with a loss of stability of the latex for CeO(2) contents lower than 35 wt %. This stability issues were likely related to the screening of the cationic charges present on CeO(2) nanoparticles upon polymerization. TEM images showed mostly spherical particles with a diameter ranging from 100 to 400 nm and homogeneously covered with CeO(2). Besides, for particles typically larger than 200 nm, a buckled morphology was observed supporting the presence of residual monomer at the end of the polymerization and consistent with the limited conversion. The versatility of these systems was further demonstrated using 35 wt % of CeO(2) and replacing MMA by n-butyl acrylate (BA) either alone or in combination with MMA. Stable monomer emulsions were always obtained, with the droplet size increasing with the hydrophobicity of the oil phase, pointing out the key influence of the wettability of the solid stabilizer. The polymerization of Pickering miniemulsion stabilized by CeO(2) nanoparticles proved to be an efficient strategy

Connexin 43 expression of foreign body giant cells after implantation of nanoparticulate hydroxyapatite.

PubMed

Herde, Katja; Hartmann, Sonja; Brehm, Ralph; Kilian, Olaf; Heiss, Christian; Hild, Anne; Alt, Volker; Bergmann, Martin; Schnettler, Reinhard; Wenisch, Sabine

2007-11-01

In bone a role of connexin 43 has been implicated with the fusion of mononuclear precursors of the monocyte/macrophage lineage into multinucleated cells. In order to investigate the putative role of connexin 43 in formation of bone osteoclast-like foreign body giant cells which are formed in response to implantation of biomaterials, nanoparticulate hydroxyapatite had been implanted into defects of minipig femura. After 20 days the defect areas were harvested and connexin 43 expression and synthesis were investigated by using immunohistochemistry, Western Blot, and in situ hybridization within macrophages and osteoclast-like foreign body giant cells. Morphological analysis of gap junctions is performed ultrastructurally. As shown on protein and mRNA level numerous connexin 43 positive macrophages and foreign body giant cells (FBGC) were localized within the granulation tissue and along the surfaces of the implanted hydroxyapatite (HA). Besides, the formation of FBGC by fusion of macrophages could be shown ultrastructurally. Connexin 43 labeling observed on the protein and mRNA level could be attributed to gap junctions identified ultrastructurally between macrophages, between FBGC, and between FBGC and macrophages. Annular gap junctions in the cytoplasm of FBGC pointed to degradation of the channels, and the ubiquination that had occurred in the course of degradation was confirmed by Western blot analysis. All in all, the presently observed pattern of connexin 43 labeling refers to an functional role of gap junctional communication in the formation of osteoclast-like foreign body giant cells formed in response to implantation of the nanoparticulate HA.

Deconstruction of lignocellulosic biomass with hydrated cerium (III) chloride in water and ethanol

DOE PAGES

Akalin, Mehmet K.; Das, Parthapratim; Alper, Koray; ...

2017-08-08

Lignocellulosic biomass was decomposed to produce crude bio-oil in water and ethanol using hydrated cerium (III) chloride as a catalyst. Use of the catalyst affected not only the yield of crude bio-oil but also the composition of bio-crude for both water and ethanol. The catalyst had a detrimental effect on the crude bio-oil yields obtained from water processing for all runs. However, in ethanol, use of the catalyst improved the crude bio-oil yields in all tested runs. The solid residue yields decreased with the catalyst use in the runs with water but increased in all studies with ethanol, except thosemore » with the shortest tested residence time of 10 min. The highest crude bio-oil yield of 48.2 wt% was obtained at 300 °C using 5 mmol of hydrated cerium (III) chloride at a residence time of 90 min in ethanol. The heating values of the crude bio-oils increased with the catalyst use for both water and ethanol processing. In conclusion, the highest heating value of 33.3 MJ kg –1 was obtained with hydrated cerium (III) chloride at 300 °C and a residence time of 120 min.« less

Deconstruction of lignocellulosic biomass with hydrated cerium (III) chloride in water and ethanol

DOE Office of Scientific and Technical Information (OSTI.GOV)

Akalin, Mehmet K.; Das, Parthapratim; Alper, Koray

Lignocellulosic biomass was decomposed to produce crude bio-oil in water and ethanol using hydrated cerium (III) chloride as a catalyst. Use of the catalyst affected not only the yield of crude bio-oil but also the composition of bio-crude for both water and ethanol. The catalyst had a detrimental effect on the crude bio-oil yields obtained from water processing for all runs. However, in ethanol, use of the catalyst improved the crude bio-oil yields in all tested runs. The solid residue yields decreased with the catalyst use in the runs with water but increased in all studies with ethanol, except thosemore » with the shortest tested residence time of 10 min. The highest crude bio-oil yield of 48.2 wt% was obtained at 300 °C using 5 mmol of hydrated cerium (III) chloride at a residence time of 90 min in ethanol. The heating values of the crude bio-oils increased with the catalyst use for both water and ethanol processing. In conclusion, the highest heating value of 33.3 MJ kg –1 was obtained with hydrated cerium (III) chloride at 300 °C and a residence time of 120 min.« less

Different effect of hydrogelation on anti-fouling and circulation properties of dextran–iron oxide nanoparticles

PubMed Central

Karmali, Priya Prakash; Chao, Ying; Park, Ji-Ho (Joe); Sailor, Michael J.; Ruoslahti, Erkki; Esener, Sadik C.; Simberg, Dmitri

2012-01-01

Premature recognition and clearance of nanoparticulate imaging and therapeutic agents by macrophages in the tissues can dramatically reduce both the nanoparticle half-life and delivery to the diseased tissue. Grafting nanoparticles with hydrogels prevents nanoparticulate recognition by liver and spleen macrophages and greatly prolongs circulation times in vivo. Understanding the mechanisms by which hydrogels achieve this “stealth” effect has implications for the design of long-circulating nanoparticles. Thus, the role of plasma protein absorption in the hydrogel effect is not yet understood. Short-circulating dextran-coated iron oxide nanoparticles could be converted into stealth hydrogel nanoparticles by crosslinking with 1-chloro-2,3-epoxypropane. We show that hydrogelation did not affect the size, shape and zeta potential, but completely prevented the recognition and clearance by liver macrophages in vivo. Hydrogelation decreased the number of hydroxyl groups on the nanoparticle surface and reduced the binding of the anti-dextran antibody. At the same time, hydrogelation did not reduce the absorption of cationic proteins on the nanoparticle surface. Specifically, there was no effect on the binding of kininogen, histidine-rich glycoprotein, and protamine sulfate to the anionic nanoparticle surface. In addition, hydrogelation did not prevent activation of plasma kallikrein on the metal oxide surface. These data suggest that: (a) a stealth hydrogel coating does not mask charge interactions with iron oxide surface and (b) the total blockade of plasma protein absorption is not required for maintaining iron oxide nanoparticles’ long-circulating stealth properties. These data illustrate a novel, clinically promising property of long-circulating stealth nanoparticles. PMID:22243419

Nanoparticulation improves bioavailability of Erlotinib.

PubMed

Yang, Kyung Mi; Shin, In Chul; Park, Joo Won; Kim, Kab-Sig; Kim, Dae Kyong; Park, Kyungmoon; Kim, Kunhong

2017-09-01

Nanoparticulation using fat and supercritical fluid (NUFS TM ) is a drug delivery platform technology enabling efficient and effective formulation of poorly soluble drugs. We performed experiments to examine whether NUFS™ could improve poor bioavailability and reduce fed-fasted bioavailability variances of erlotinib (Ert). NUFS-Ert was prepared using NUFS™ technology; its physical properties were characterized, and drug release was measured. Furthermore, in vitro and in vivo efficacy tests and pharmacokinetic analysis were performed. NUFS-Ert nanoparticles had an average size of 250 nm and were stable for 2 months at 40 °C, 4 °C, and room temperature. The dissolution rate of NUFS-Ert increased in bio-relevant dissolution media. NUFS-Ert was more potent in inhibiting EGF signaling and in suppressing the proliferation of A549, a human non-small cell lung cancer cell line. Furthermore, A549 xenografts in BALB/c nude mice treated with NUFS-Ert regressed more efficiently than those in the mice treated with vehicle or Tarceva ® . In addition, experimental lung metastasis was more efficiently inhibited by NUFS-Ert than by Tarceva ® . The relative bioavailability of NUFS-Ert compared with that of Tarceva ® was 550% and the ratio of the area under the concentration-time curve (AUC) of fed state to the AUC of fasted state was 1.8 for NUFS-Ert and 5.8 for Tarceva ® . NUFS-Ert could improve poor bioavailability and reduce fed-fasted bioavailability variances of Ert. NUFS-Ert was more efficacious than Tarceva ® .

TU-H-CAMPUS-TeP2-05: Selective Protection of Normal Tissue by Cerium Oxide Nanoparticles During Radiation Therapy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ouyang, Z; Ngwa, W; Brigham and Women’s Hospital, Dana-Farber Cancer Institute and Harvard Medical School, Boston, MA

2016-06-15

Purpose: Cerium oxide nanoparticles (CONPs) have unique pH dependent properties such that they act as a radical modulator. These properties may be used in radiation therapy (RT) to protect normal tissue. This work investigates the selective radioprotection of CONPs in-vitro and potential for in-situ delivery of CONPs in prostate cancer RT. Methods: i) Normal human umbilical vein endothelial cells (HUVEC) and human prostate cancer cells (PC-3) were treated with 0 or 2 ng/mL CONPs (NP size: 5 nm). 2 Gy of 100 kVp radiation was delivered to the cells 4 hours after the CONP treatment. Cell viability was checked 48more » hours later using MTS assays. ii) A prostate tumor was modeled as a 2-cm diameter sphere. CONPs were proposed to be loaded in a hollow radiotherapy fiducial marker. The concentration profile for the CONPs within the tumor was modeled with a previously validated diffusion equation employed in other studies for nanoparticles 10 nm or less. Results: i) Without radiation, cell viability was above 90% when treated with 2 ng/mL CONPs for both HUVEC and PC-3. After irradiation, a slightly higher viability was observed in HUVEC with CONPs than the ones without CONPs, and this effect was not observed in PC-3. ii) Based on the calculations, 2 ng/mL of CONPs could be delivered to normal cells by diffusion with a 1 µg/mL initial concentration within two weeks. Conclusion: We conclude that CONPs can provide selective radioprotection. The delivery of needed concentrations of CONPs is feasible via in-situ release from radiotherapy biomaterials (e.g. fiducials) loaded with the CONPs.« less

Cerium oxide nanoparticles alter the salt stress tolerance of Brassica napus L. by modifying the formation of root apoplastic barriers.

PubMed

Rossi, Lorenzo; Zhang, Weilan; Ma, Xingmao

2017-10-01

Rapidly growing global population adds significant strains on the fresh water resources. Consequently, saline water is increasingly tapped for crop irrigation. Meanwhile, rapid advancement of nanotechnology is introducing more and more engineered nanoparticles into the environment and in agricultural soils. While some negative effects of ENPs on plant health at very high concentrations have been reported, more beneficial effects of ENPs at relatively low concentrations are increasingly noticed, opening doors for potential applications of nanotechnology in agriculture. In particular, we found that cerium oxide nanoparticles (CeO 2 NPs) improved plant photosynthesis in salt stressed plants. Due to the close connections between salt stress tolerance and the root anatomical structures, we postulated that CeO 2 NPs could modify plant root anatomy and improve plant salt stress tolerance. This study aimed at testing the hypothesis with Brassica napus in the presence of CeO 2 NPs (0, 500 mg kg -1 dry sand) and/or NaCl (0, 50 mM) in a growth chamber. Free hand sections of fresh roots were taken every seven days for three weeks and the suberin lamellae development was examined under a fluorescence microscope. The results confirmed the hypothesis that CeO 2 NPs modified the formation of the apoplastic barriers in Brassica roots. In salt stressed plants, CeO 2 NPs shortened the root apoplastic barriers which allowed more Na + transport to shoots and less accumulation of Na + in plant roots. The altered Na + fluxes and transport led to better physiological performance of Brassica and may lead to new applications of nanotechnology in agriculture. Copyright © 2017 Elsevier Ltd. All rights reserved.

Evidence that Soil Properties and Organic Coating Drive the Phytoavailability of Cerium Oxide Nanoparticles.

PubMed

Layet, Clément; Auffan, Mélanie; Santaella, Catherine; Chevassus-Rosset, Claire; Montes, Mélanie; Ortet, Philippe; Barakat, Mohamed; Collin, Blanche; Legros, Samuel; Bravin, Matthieu N; Angeletti, Bernard; Kieffer, Isabelle; Proux, Olivier; Hazemann, Jean-Louis; Doelsch, Emmanuel

2017-09-05

The ISO-standardized RHIZOtest is used here for the first time to decipher how plant species, soil properties, and physical-chemical properties of the nanoparticles and their transformation regulate the phytoavailability of nanoparticles. Two plants, tomato and fescue, were exposed to two soils with contrasted properties: a sandy soil poor in organic matter and a clay soil rich in organic matter, both contaminated with 1, 15, and 50 mg·kg -1 of dissolved Ce 2 (SO 4 ) 3 , bare and citrate-coated CeO 2 nanoparticles. All the results demonstrate that two antagonistic soil properties controlled Ce uptake. The clay fraction enhanced the retention of the CeO 2 nanoparticles and hence reduced Ce uptake, whereas the organic matter content enhanced Ce uptake. Moreover, in the soil poor in organic matter, the organic citrate coating significantly enhanced the phytoavailability of the cerium by forming smaller aggregates thereby facilitating the transport of nanoparticles to the roots. By getting rid of the dissimilarities between the root systems of the different plants and the normalizing the surfaces exposed to nanoparticles, the RHIZOtest demonstrated that the species of plant did not drive the phytoavailability, and provided evidence for soil-plant transfers at concentrations lower than those usually cited in the literature and closer to predicted environmental concentrations.

Mediated electrochemical oxidation (MEO) process: a study on nonylphenol ethoxylates (NPE) oxidation in batch mode using cerium (IV) oxidant

NASA Astrophysics Data System (ADS)

Setiyanto, H.; Adyatmika, I. M.; Syaifullah, M. M.; Zulfikar, M. A.; Buchari

2018-05-01

Nonylphenol ethoxylate (NPE-10) is one type of non-ionic surfactants from the class of alkylphenol ethoxylate (APE). This compound is already tightened their use in European Union countries. However, these surfactants are still used widely in Indonesia because the price is relatively cheap. Consequently, these compounds can accumulate in aquatic environments. NPE-10 can disrupt aquatic ecosystems. This study aimed to describe the electro-oxidation process of NPE-10 based on the parameters of a potential difference, concentration of NPE-10, concentration of Ce (III), and oxidation time. The result of oxidation NPE-10 was measured by the amount of current generated from voltammetry technique. Studies of cyclic voltammetry using carbon paste electrodes illustrates the potential value of the oxidation of Ce (III) / Ce (IV) of 1.25 V and the reduction potential value of Ce (IV) / Ce (III) of 1.192 V. NPE-10 are electroactive irreversible because it only provides the potential value of oxidation at 1.44 V. Percent of total degradation of 84.96% was obtained at electro-oxidation of 500 ppm NPE-10 by the addition of 0.015 M Ce (III) for 90 minutes at 0.2 M H2SO4and the use of potential of 6 V.

Nanoparticulate NaA zeolite composites for MRI: Effect of iron oxide content on image contrast

NASA Astrophysics Data System (ADS)

Gharehaghaji, Nahideh; Divband, Baharak; Zareei, Loghman

2018-06-01

In the current study, Fe3O4/NaA nanocomposites with various amounts of Fe3O4 (3.4, 6.8 & 10.2 wt%) were synthesized and characterized to study the effect of nano iron oxide content on the magnetic resonance (MR) image contrast. The cell viability of the nanocomposites was investigated by MTT assay method. T2 values as well as r2 relaxivities were determined with a 1.5 T MRI scanner. The results of the MTT assay confirmed the nanocomposites cytocompatibility up to 6.8% of the iron oxide content. Although the magnetization saturations and susceptibility values of the nanocomposites were increased as a function of the iron oxide content, their relaxivity was decreased from 921.78 mM-1 s-1 for the nanocomposite with the lowest iron oxide content to 380.16 mM-1 s-1 for the highest one. Therefore, Fe3O4/NaA nanocomposite with 3.4% iron oxide content led to the best MR image contrast. Nano iron oxide content and dispersion in the nanocomposites structure have important role in the nanocomposite r2 relaxivity and the MR image contrast. Aggregation of the iron oxide nanoparticles is a limiting factor in using of the high iron oxide content nanocomposites.

Blue light emission from trivalent cerium doped in sol-gel silica glass

NASA Astrophysics Data System (ADS)

Tokumitsu, Seika; Murakami, Yukon; Oda, Hisaya; Kawabe, Yutaka

2017-02-01

Rare earths in glass matrices are promising for active optical devices as amplifiers and lasers. Emission originating from d-f transitions in sol-gel glass has not been studied very often, while those based on f-f transitions were widely utilized. However, d-f emission in rare earths is very important because of their strong oscillator strength and broad emission widths suitable for the application to scintillators and solid-state lasers. Co-doping of aluminum in sol-gel synthesis was known to be effective for the emission enhancement of trivalent terbium and europium. Recently, we applied aluminum co-doping to cerium and europium systems in sol-gel glass to succeed in the observation of strong blue light emission originating from d-f transitions. Glass samples were prepared with conventional sol-gel process where tetramethylorthosilicate was hydrolyzed in the mixture of water, ethanol and dimethylformamide with nitric acid catalyst. After adding cerium nitrate and aluminum nitrate, the solution experienced drying followed by calcination at 1,050°C under air environment. When molar ratio of cerium to silicon was adjusted at 0.1% and Al concentration was varied in 0.1 2.0%, transparent glass products showed bright and broad blue photoluminescence under UV illumination. The fluorescence lifetimes were found to be about 50 90 ns, indicating that the emission was due to d-f transitions. Considering the simplicity of the process, blue phosphors based on sol-gel glass will be very promising for future applications.

Nanoparticulated docetaxel exerts enhanced anticancer efficacy and overcomes existing limitations of traditional drugs.

PubMed

Choi, Jinhyang; Ko, Eunjung; Chung, Hye-Kyung; Lee, Jae Hee; Ju, Eun Jin; Lim, Hyun Kyung; Park, Intae; Kim, Kab-Sig; Lee, Joo-Hwan; Son, Woo-Chan; Lee, Jung Shin; Jung, Joohee; Jeong, Seong-Yun; Song, Si Yeol; Choi, Eun Kyung

2015-01-01

Nanoparticulation of insoluble drugs improves dissolution rate, resulting in increased bioavailability that leads to increased stability, better efficacy, and reduced toxicity of drugs. Docetaxel (DTX), under the trade name Taxotere™, is one of the representative anticancer chemotherapeutic agents of this era. However, this highly lipophilic and insoluble drug has many adverse effects. Our novel and widely applicable nanoparticulation using fat and supercritical fluid (NUFS™) technology enabled successful nanoscale particulation of DTX (Nufs-DTX). Nufs-DTX showed enhanced dissolution rate and increased aqueous stability in water. After confirming the preserved mechanism of action of DTX, which targets microtubules, we showed that Nufs-DTX exhibited similar effects in proliferation and clonogenic assays using A549 cells. Interestingly, we observed that Nufs-DTX had a greater in vivo tumor growth delay effect on an A549 xenograft model than Taxotere™, which was in agreement with the improved drug accumulation in tumors according to the biodistribution result, and was caused by the enhanced permeability and retention (EPR) effect. Although both Nufs-DTX and Taxotere™ showed negative results for our administration dose in the hematologic toxicity test, Nufs-DTX showed much less toxicity than Taxotere™ in edema, paralysis, and paw-withdrawal latency on a hot plate analysis that are regarded as indicators of fluid retention, peripheral neuropathy, and thermal threshold, respectively, for toxicological tests. In summary, compared with Taxotere™, Nufs-DTX, which was generated by our new platform technology using lipid, supercritical fluid, and carbon dioxide (CO2), maintained its biochemical properties as a cytotoxic agent and had better tumor targeting ability, better in vivo therapeutic effect, and less toxicity, thereby overcoming the current hurdles of traditional drugs.

Electrohydrodynamic atomization: A two-decade effort to produce and process micro-/nanoparticulate materials

PubMed Central

Xie, Jingwei; Jiang, Jiang; Davoodi, Pooya; Srinivasan, M. P.; Wang, Chi-Hwa

2014-01-01

Electrohydrodynamic atomization (EHDA), also called electrospray technique, has been studied for more than one century. However, since 1990s it has begun to be used to produce and process micro-/nanostructured materials. Owing to the simplicity and flexibility in EHDA experimental setup, it has been successfully employed to generate particulate materials with controllable compositions, structures, sizes, morphologies, and shapes. EHDA has also been used to deposit micro- and nanoparticulate materials on surfaces in a well-controlled manner. All these attributes make EHDA a fascinating tool for preparing and assembling a wide range of micro- and nanostructured materials which have been exploited for use in pharmaceutics, food, and healthcare to name a few. Our goal is to review this field, which allows scientists and engineers to learn about the EHDA technique and how it might be used to create, process, and assemble micro-/nanoparticulate materials with unique and intriguing properties. We begin with a brief introduction to the mechanism and setup of EHDA technique. We then discuss issues critical to successful application of EHDA technique, including control of composition, size, shape, morphology, structure of particulate materials and their assembly. We also illustrate a few of the many potential applications of particulate materials, especially in the area of drug delivery and regenerative medicine. Next, we review the simulation and modeling of Taylor cone-jet formation for a single and co-axial nozzle. The mathematical modeling of particle transport and deposition is presented to provide a deeper understanding of the effective parameters in the preparation, collection and pattering processes. We conclude this article with a discussion on perspectives and future possibilities in this field. PMID:25684778

Aerosol Physics Considerations for Using Cerium Oxide CeO 2 as a Surrogate for Plutonium Oxide PuO 2 in Airborne Release Fraction Measurements for Storage Container Investigations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moore, Murray E.; Tao, Yong

Cerium oxide (CeO2) dust is recommended as a surrogate for plutonium oxide (PuO2) in airborne release fraction experiments. The total range of applicable particle sizes for PuO2 extends from 0.0032 μm (the diameter of a single PuO2 molecule) to 10 μm (the defined upper boundary for respirable particles). For particulates with a physical particle diameter of 1.0 μm, the corresponding aerodynamic diameters for CeO2 and PuO2 are 2.7 μm and 3.4 μm, respectively. Cascade impactor air samplers are capable of measuring the size distributions of CeO2 or PuO2 particulates. In this document, the aerodynamic diameters for CeO2 and PuO2 weremore » calculated for seven different physical diameters (0.0032, 0.02, 0.11, 0.27, 1.0, 3.2, and 10 μm). For cascade impactor measurements, CeO2 and PuO2 particulates with the same physical diameter would be collected onto the same or adjacent collection substrates. The difference between the aerodynamic diameter of CeO2 and PuO2 particles (that have the same physical diameter) is 39% of the resolution of a twelve-stage MSP Inc. 125 cascade impactor, and 34% for an eight-stage Andersen impactor. An approach is given to calculate the committed effective dose (CED) coefficient for PuO2 aerosol particles, compared to a corresponding aerodynamic diameter of CeO2 particles. With this approach, use of CeO2 as a surrogate for PuO2 material would follow a direct conversion based on a molar equivalent. In addition to the analytical information developed for this document, several US national labs have published articles about the use of CeO2 as a PuO2 surrogate. Different physical and chemical aspects were considered by these investigators, including thermal properties, ceramic formulations, cold pressing, sintering, molecular reactions, and mass loss in high temperature gas flows. All of those US national lab studies recommended the use of CeO2 as a surrogate material for PuO2.« less

Use of a nanoparticulate carboxymethyl cellulose film containing sinigrin as an antimicrobial precursor to kill Escherichia coli O157:H7 on fresh beef.

PubMed

Herzallah, S; Holley, R

2015-08-01

Nanocomposite carboxymethyl cellulose films containing sinigrin (SNG) were prepared by stirring 2% (w/v) carboxymethyl cellulose (CMC) and 2% (w/v) glycerol (as a plasticizer) in distilled water with or without SNG (an antimicrobial precursor) as a 99% pure reagent (pSNG) or as a crude extract (cSNG). These films plus normal CMC film with or without SNG were tested on Escherichia coli O157:H7- inoculated beef for antimicrobial activity. Beef pieces measuring 6 × 5 × 2 cm(3) (L × W × H) were dipped in an E. coli O157:H7 broth suspension containing >8 log10 CFU ml(-1) and were drained for 3 min over a sterile cloth. They were wrapped in CMC or NCMC films, placed in a high oxygen barrier film (Deli *1), vacuum-packaged and stored at 8°C for 5, 8, 12 and 18 days. The CMC and NCMC films without SNG were not antimicrobial against E. coli O157:H7; however, NCMC and CMC films with SNG were highly antimicrobial. After 5 days at 8°C, E. coli O157:H7 was reduced more than 4 log10 by the NCMC•pSNG film and this reduction remained almost the same until 18 days at 8°C when E. coli O157:H7 was reduced >5 log10  CFU g(-1) meat. Transparent nanoparticulate carboxymethyl cellulose (CMC) films containing sinigrin (SNG), an antimicrobial precursor, controlled surface contamination of packaged fresh beef by the pathogen Escherichia coli O157:H7 when stored at 8°C. Films with nanoparticulation that carried pure SNG or the naturally occurring SNG in Oriental mustard were significantly more antimicrobial than similar films without nanoparticulation. As films without sinigrin were not antimicrobial, the combinations studied showed that nanoparticulation of the packaging film enhanced delivery of the antimicrobial incorporated within the film. © 2015 The Society for Applied Microbiology.

Rate-programming of nano-particulate delivery systems for smart bioactive scaffolds in tissue engineering.

PubMed

Izadifar, Mohammad; Haddadi, Azita; Chen, Xiongbiao; Kelly, Michael E

2015-01-09

Development of smart bioactive scaffolds is of importance in tissue engineering, where cell proliferation, differentiation and migration within scaffolds can be regulated by the interactions between cells and scaffold through the use of growth factors (GFs) and extra cellular matrix peptides. One challenge in this area is to spatiotemporally control the dose, sequence and profile of release of GFs so as to regulate cellular fates during tissue regeneration. This challenge would be addressed by rate-programming of nano-particulate delivery systems, where the release of GFs via polymeric nanoparticles is controlled by means of the methods of, such as externally-controlled and physicochemically/architecturally-modulated so as to mimic the profile of physiological GFs. Identifying and understanding such factors as the desired release profiles, mechanisms of release, physicochemical characteristics of polymeric nanoparticles, and externally-triggering stimuli are essential for designing and optimizing such delivery systems. This review surveys the recent studies on the desired release profiles of GFs in various tissue engineering applications, elucidates the major release mechanisms and critical factors affecting release profiles, and overviews the role played by the mathematical models for optimizing nano-particulate delivery systems. Potentials of stimuli responsive nanoparticles for spatiotemporal control of GF release are also presented, along with the recent advances in strategies for spatiotemporal control of GF delivery within tissue engineered scaffolds. The recommendation for the future studies to overcome challenges for developing sophisticated particulate delivery systems in tissue engineering is discussed prior to the presentation of conclusions drawn from this paper.

Tungsten carbide-cobalt as a nanoparticulate reference positive control in in vitro genotoxicity assays.

PubMed

Moche, Hélène; Chevalier, Dany; Barois, Nicolas; Lorge, Elisabeth; Claude, Nancy; Nesslany, Fabrice

2014-01-01

With the increasing human exposure to nanoparticles (NP), the evaluation of their genotoxic potential is of significant importance. However, relevance for NP of the routinely used in vitro genotoxicity assays is often questioned, and a nanoparticulate reference positive control would therefore constitute an important step to a better testing of NP, ensuring that test systems are really appropriate. In this study, we investigated the possibility of using tungsten carbide-cobalt (WC-Co) NP as reference positive control in in vitro genotoxicity assays, including 2 regulatory assays, the mouse lymphoma assay and the micronucleus assay, and in the Comet assay, recommended for the toxicological evaluation of nanomedicines by the French Agency of Human Health Products (Afssaps). Through these assays, we were able to study different genetic endpoints in 2 cell types commonly used in regulatory genotoxicity assays: the L5178Y mouse lymphoma cell line and primary cultures of human lymphocytes. Our results showed that the use of WC-Co NP as positive control in in vitro genotoxicity assays was conceivable, but that different parameters have to be considered, such as cell type and treatment schedule. L5178Y mouse lymphoma cells did not provide satisfactory results in the 3 performed tests. However, human lymphocytes were more sensitive to genotoxic effects induced by WC-Co NP, particularly after a 24-h treatment in the in vitro micronucleus assay and after a 4-h treatment in the in vitro Comet assay. Under such conditions, WC-Co could be used as a nanoparticulate reference positive control in these assays.

Cerium chloride stimulated controlled conversion of B-to-Z DNA in self-assembled nanostructures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bhanjadeo, Madhabi M.; Academy of Scientific & Innovative Research; Nayak, Ashok K.

DNA adopts different conformation not only because of novel base pairs but also while interacting with inorganic or organic compounds. Self-assembled branched DNA (bDNA) structures or DNA origami that change conformation in response to environmental cues hold great promises in sensing and actuation at the nanoscale. Recently, the B-Z transition in DNA is being explored to design various nanomechanical devices. In this communication we have demonstrated that Cerium chloride binds to the phosphate backbone of self-assembled bDNA structure and induce B-to-Z transition at physiological concentration. The mechanism of controlled conversion from right-handed to left-handed has been assayed by various dyemore » binding studies using CD and fluorescence spectroscopy. Three different bDNA structures have been identified to display B-Z transition. This approach provides a rapid and reversible means to change bDNA conformation, which can be used for dynamic and progressive control at the nanoscale. - Highlights: • Cerium-induced B-to-Z DNA transition in self-assembled nanostructures. • Lower melting temperature of Z-DNA than B-DNA confirmed by CD spectroscopy. • Binding mechanism of cerium chloride is explained using fluorescence spectroscopy. • Right-handed to left-handed DNA conformation is also noticed in modified bDNA structure.« less

Attachment of nanoparticulate drug-release systems on poly(ε-caprolactone) nanofibers via a graftpolymer as interlayer.

PubMed

de Cassan, Dominik; Sydow, Steffen; Schmidt, Nadeschda; Behrens, Peter; Roger, Yvonne; Hoffmann, Andrea; Hoheisel, Anna Lena; Glasmacher, Birgit; Hänsch, Robert; Menzel, Henning

2018-03-01

Electrospun poly(ε-caprolactone) (PCL) fiber mats are modified using a chitosan grafted with PCL (CS-g-PCL), to improve the biological performance and to enable further modifications. The graft copolymer is immobilized by the crystallization of the PCL grafts on the PCL fiber surface as binding mechanism. In this way, the surface of the fibers is covered with chitosan bearing cationic amino groups, which allow adsorption of oppositely charged nanoparticulate drug-delivery systems. The modification of the fiber mats and the attachment of the drug delivery systems are easy and scalable dip processes. The process is also versatile; it is possible to attach different polymeric and inorganic nanoparticulate drug-release systems of cationic or anionic nature. The modifications are verified using scanning electron microscopy (SEM) and confocal laser scanning microscopy (CLSM). As proof of principle, the release of ciprofloxacin from silica nanoparticles attached to the modified fiber mats is shown; however, the method is also suited for other biologically active substances including growth factors. The initial cellular attachment and proliferation as well as vitality of the cells is improved by the modification with CS-g-PCL and is further influenced by the type of the drug delivery system attached. Hence, this method can be used to transfer PCL fiber mats into bioactive implants for in-situ tissue engineering applications. Copyright © 2018 Elsevier B.V. All rights reserved.

Microstructure and electrochemical behavior of cerium conversion coating modified with silane agent on magnesium substrates

NASA Astrophysics Data System (ADS)

Lei, Li; Shi, Jing; Wang, Xin; Liu, Dan; Xu, Haigang

2016-07-01

The cerium conversion coating with and without different concentrations of silane agent bis-(γ-triethoxysilylpropyl)-tetrasulfide (BTESPT) modification is obtained on magnesium alloys. Detailed properties of the coatings and the role of BTESPT as an additive are studied and followed with careful discussion. The coating morphology, wettability, chemical composition and corrosion resistance are characterized by scanning electronic microscope (SEM), water contact-angle, X-ray photoelectron spectroscopy (XPS), potentiodynamic measurements and electrochemical impedance spectroscopy (EIS). The electrochemical behavior of the coatings is investigated using EIS. The results indicate that the coating morphology and composition can be controlled by changing silane concentration. The combination of cerium ions and silane molecules could promote the formation of more homogenous and higher hydrophobic coating. The coating turns to be more compact and the adhesive strength between the coating and the magnesium substrate are strongly improved with the formation of Sisbnd Osbnd Si and Sisbnd Osbnd M chemical bonds. The optimum corrosion resistance of the coating in the corrosive media is obtained by 25 ml L-1 BTESPT modification. This whole study implies that the cerium conversion coating modified with certain silane agent deserves cautiousness before its application for corrosion resistance.

Mixed cerium-platinum oxides: Electronic structure of [CeO]Pt{sub n} (n = 1, 2) and [CeO{sub 2}]Pt complex anions and neutrals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ray, Manisha; Kafader, Jared O.; Topolski, Josey E.

The electronic structures of several small Ce–Pt oxide complexes were explored using a combination of anion photoelectron (PE) spectroscopy and density functional theory calculations. Pt and Pt{sub 2} both accept electron density from CeO diatomic molecules, in which the cerium atom is in a lower-than-bulk oxidation state (+2 versus bulk +4). Neutral [CeO]Pt and [CeO]Pt{sub 2} complexes are therefore ionic, with electronic structures described qualitatively as [CeO{sup +2}]Pt{sup −2} and [CeO{sup +}]Pt{sub 2}{sup −}, respectively. The associated anions are described qualitatively as [CeO{sup +}]Pt{sup −2} and [CeO{sup +}]Pt{sub 2}{sup −2}, respectively. In both neutrals and anions, the most stable molecularmore » structures determined by calculations feature a distinct CeO moiety, with the positively charged Ce center pointing toward the electron rich Pt or Pt{sub 2} moiety. Spectral simulations based on calculated spectroscopic parameters are in fair agreement with the spectra, validating the computationally determined structures. In contrast, when Pt is coupled with CeO{sub 2}, which has no Ce-localized electrons that can readily be donated to Pt, the anion is described as [CeO{sub 2}]Pt{sup −}. The molecular structure predicted computationally suggests that it is governed by charge-dipole interactions. The neutral [CeO{sub 2}]Pt complex lacks charge-dipole stabilizing interactions, and is predicted to be structurally very different from the anion, featuring a single Pt–O–Ce bridge bond. The PE spectra of several of the complexes exhibit evidence of photodissociation with Pt{sup −} daughter ion formation. The electronic structures of these complexes are related to local interactions in Pt-ceria catalyst-support systems.« less

Combustion-Generated Nanoparticulates in the El Paso, TX, USA / Juarez, Mexico Metroplex: Their Comparative Characterization and Potential for Adverse Health Effects

PubMed Central

Murr, L. E.; Soto, K. F.; Garza, K. M.; Guerrero, P. A.; Martinez, F.; Esquivel, E. V.; Ramirez, D. A.; Shi, Y.; Bang, J. J.; Venzor, J.

2006-01-01

In this paper we report on the collection of fine (PM1) and ultrafine (PM0.1), or nanoparticulate, carbonaceous materials using thermophoretic precipitation onto silicon monoxide/formvar-coated 3 mm grids which were examined in the transmission electron microscope (TEM). We characterize and compare diesel particulate matter (DPM), tire particulate matter (TPM), wood burning particulate matter, and other soot (or black carbons (BC)) along with carbon nanotube and related fullerene nanoparticle aggregates in the outdoor air, as well as carbon nanotube aggregates in the indoor air; and with reference to specific gas combustion sources. These TEM investigations include detailed microstructural and microdiffraction observations and comparisons as they relate to the aggregate morphologies as well as their component (primary) nanoparticles. We have also conducted both clinical surveys regarding asthma incidence and the use of gas cooking stoves as well as random surveys by zip code throughout the city of El Paso. In addition, we report on short term (2 day) and longer term (2 week) in vitro assays for black carbon and a commercial multiwall carbon nanotube aggregate sample using a murine macrophage cell line, which demonstrate significant cytotoxicity; comparable to a chrysotile asbestos nanoparticulate reference. The multi-wall carbon nanotube aggregate material is identical to those collected in the indoor and outdoor air, and may serve as a surrogate. Taken together with the plethora of toxic responses reported for DPM, these findings prompt concerns for airborne carbonaceous nanoparticulates in general. The implications of these preliminary findings and their potential health effects, as well as directions for related studies addressing these complex issues, will also be examined. PMID:16823077

Long range ordered alloys modified by addition of niobium and cerium

DOEpatents

Liu, C.T.

1984-08-22

Long range ordered alloys are described having the nominal composition (Fe,Ni,Co)/sub 3/ (V,M) where M is a ductility enhancing metal selected from the group Ti, Zr, Hf with additions of small amounts of cerium and niobium to dramatically enhance the creep properties of the resulting alloys.

Long range ordered alloys modified by addition of niobium and cerium

DOEpatents

Liu, Chain T.

1987-01-01

Long range ordered alloys are described having the nominal composition (Fe,Ni,Co).sub.3 (V,M) where M is a ductility enhancing metal selected from the group Ti, Zr, Hf with additions of small amounts of cerium and niobium to drammatically enhance the creep properties of the resulting alloys.

Evaluation of in vitro cytotoxicity, biocompatibility, and changes in the expression of apoptosis regulatory proteins induced by cerium oxide nanocrystals

NASA Astrophysics Data System (ADS)

Khan, Shahanavaj; Ansari, Anees A.; Rolfo, Christian; Coelho, Andreia; Abdulla, Maha; Al-Khayal, Khayal; Ahmad, Rehan

2017-12-01

Cerium oxide nanocrystals (CeO2-NCs) exhibit superoxide dismutase and catalase mimetic activities. Based on these catalytic activities, CeO2-NCs have been suggested to have the potential to treat various diseases. The crystalline size of these materials is an important factor that influences the performance of CeO2-NCs. Previous reports have shown that several metal-based nanocrystals, including CeO2-NCs, can induce cytotoxicity in cancer cells. However, the underlying mechanisms have remained unclear. To characterize the anticancer activities of CeO2-NCs, several assays related to the mechanism of cytotoxicity and induction of apoptosis has been performed. Here, we have carried out a systematic study to characterize CeO2-NCs phase purity (X-ray diffraction), morphology (electron microscopy), and optical features (optical absorption, Raman scattering, and photoluminescence) to better establish their potential as anticancer drugs. Our study revealed anticancer effects of CeO2-NCs in HT29 and SW620 colorectal cancer cell lines with half-maximal inhibitory concentration (IC50) values of 2.26 and 121.18 μg ml-1, respectively. Reductions in cell viability indicated the cytotoxic potential of CeO2-NCs in HT29 cells based on inverted and florescence microscopy assessments. The mechanism of cytotoxicity confirmed by estimating possible changes in the expression levels of Bcl2, BclxL, Bax, PARP, cytochrome c, and β-actin (control) proteins in HT29 cells. Down-regulation of Bcl2 and BclxL and up-regulation of Bax, PARP, and cytochrome c proteins suggested the significant involvement of CeO2-NCs exposure in the induction of apoptosis. Furthermore, biocompatibility assay showed minimum effect of CeO2-NCs on human red blood cells.

Characterization of the corrosion protection mechanism of cerium-based conversion coatings on high strength aluminum alloys

NASA Astrophysics Data System (ADS)

Pinc, William Ross

The aim of the work presented in this dissertation is to investigate the corrosion protection mechanism of cerium-based conversion coatings (CeCCs) used in the corrosion protection of high strength aluminum alloys. The corrosion resistance of CeCCs involves two general mechanisms; barrier and active. The barrier protection mechanism was influenced by processing parameters, specifically surface preparation, post-treatment, and the use of gelatin. Post-treatment and the addition of gelatin to the coating solution resulted in fewer cracks and transformation of the coating to CePO4, which increased the corrosion resistance by improving the barrier aspect of CeCCs. CeCCs were found to best act as barriers when crack size was limited and CePO4 was present in the coating. CeCCs were found to protect areas of the substrate that were exposed in the coating, indicating that the coatings were more than simple barriers. CeCCs contained large cracks, underneath which subsurface crevices were connected to the surface by the cracks. Despite the observation that no cerium was present in crevices, coatings with crevices exhibited significant corrosion protection. The impedance of post-treated coatings with crevices increased during salt spray exposure. The increase in impedance was associated with the formation of protective oxides / hydroxides; however, crevice-free coatings also exhibited active protection leading to the conclusion that the formation of interfacial layers between the CeCC and the substrate also contributed to the active protection. Based on the overall results of the study, the optimal corrosion protection of CeCCs occurred when processing conditions produced coatings with morphologies and compositions that facilitated both the barrier and active protection mechanisms.

Metal Oxide Nanoparticles: The Importance of Size, Shape, Chemical Composition, and Valence State in Determining Toxicity

NASA Astrophysics Data System (ADS)

Dunnick, Katherine

, cerium oxide nanoparticles were chemically modified using a process known as doping, to alter their valence state. The size and shape of the cerium oxide nanoparticles remained constant. Overall, results indicated that cerium oxide was not toxic in both RLE-6TN and NR8383 pulmonary rat cells, however, chemically modifying the valence state of the nanomaterial did affect the antioxidant potential. To determine if this trend was measureable in vivo, rats were exposed to various cerium oxide nanoparticles via intratracheal instillation and damage, changes in pulmonary cell differentials, and phagocytic cell activity were assessed. Results implicate that chemically modifying the nanoparticles had an effect on the overall damage induced by the material but did not dramatically affect inflammatory potential or phagocytic cell activity. Overall the data from these studies imply that size, shape, chemical composition, and valence state of nanomaterials can be manipulated to alter their toxicity.

Diversity of Mn oxides produced by Mn(II)-oxidizing fungi

DOE Office of Scientific and Technical Information (OSTI.GOV)

Santelli, Cara M.; Webb, Samuel M.; Dohnalkova, Alice

Manganese (Mn) oxides are environmentally abundant, highly reactive mineral phases that mediate the biogeochemical cycling of nutrients, contaminants, carbon, and numerous other elements. Despite the belief that microorganisms (specifically bacteria and fungi) are responsible for the majority of Mn oxide formation in the environment, the impact of microbial species, physiology, and growth stage on Mn oxide formation is largely unresolved. Here, we couple microscopic and spectroscopic techniques to characterize the Mn oxides produced by four different species of Mn(II)-oxidizing Ascomycete fungi (Plectosphaerella cucumerina strain DS2psM2a2, Pyrenochaeta sp. DS3sAY3a, Stagonospora sp. SRC1lsM3a, and Acremonium strictum strain DS1bioAY4a) isolated from acid minemore » drainage treatment systems in central Pennsylvania. The site of Mn oxide formation varies greatly among the fungi, including deposition on hyphal surfaces, at the base of reproductive structures (e.g., fruiting bodies), and on envisaged extracellular polymers adjacent to the cell. The primary product of Mn(II) oxidation for all species growing under the same chemical and physical conditions is a nanoparticulate, poorly-crystalline hexagonal birnessite-like phase resembling synthetic d-MnO2. The phylogeny and growth conditions (planktonic versus surface-attached) of the fungi, however, impact the conversion of the initial phyllomanganate to more ordered phases, such as todorokite (A. strictum strain DS1bioAY4a) and triclinic birnessite (Stagonospora sp. SRC1lsM3a). Our findings reveal that the species of Mn(II)-oxidizing fungi impacts the size, morphology, and structure of Mn biooxides, which will likely translate to large differences in the reactivity of the Mn oxide phases.« less

Application of x-ray nano-particulate markers for the visualization of intermediate layers and interfaces using scanning electron microscopy

NASA Astrophysics Data System (ADS)

Bessudnova, Nadezda O.; Bilenko, David I.; Zakharevich, Andrey M.

2012-03-01

In this study the methodology of biological sample preparation for dental research using SEM/EDX has been elaborated. (1)The original cutting equipment supplied with 3D user-controlled sample fixation and an adjustable cooling system has been designed and evaluated. (2) A new approach to the root dentine drying procedure has been developed to preserve structure peculiarities of root dentine. (3) A novel adhesive system with embedded X-Ray nanoparticulate markers has been designed. (4)The technique allowing for visualization of bonding resins, interfaces and intermediate layers between tooth hard tissues and restorative materials of endodontically treated teeth using the X-ray nano-particulate markers has been developed and approved. These methods and approaches were used to compare the objective depth of penetration of adhesive systems of different generations in root dentine. It has been shown that the depth of penetration in dentine is less for adhesive systems of generation VI in comparison with bonding resins of generation V, which is in agreement with theoretical evidence. The depth of penetration depends on the correlation between the direction of dentinal tubules, bonding resin delivery and gravity.

Manipulating the Rate-Limiting Step in Water Oxidation Catalysis by Ruthenium Bipyridine–Dicarboxylate Complexes

DOE PAGES

Shaffer, David W.; Xie, Yan; Szalda, David J.; ...

2016-11-01

In order to gain a deeper mechanistic understanding of water oxidation by [(bda)Ru(L) 2] catalysts (bdaH 2 = [2,2'-bipyridine]-6,6'-dicarboxylic acid; L = pyridine-type ligand), a series of modified catalysts with one and two trifluoromethyl groups in the 4 position of the bda 2– ligand was synthesized and studied using stopped-flow kinetics. The additional $-$CF 3 groups increased the oxidation potentials for the catalysts and enhanced the rate of electrocatalytic water oxidation at low pH. Stopped-flow measurements of cerium(IV)-driven water oxidation at pH 1 revealed two distinct kinetic regimes depending on catalyst concentration. At relatively high catalyst concentration (ca. ≥10 –4more » M), the rate-determining step (RDS) was a proton-coupled oxidation of the catalyst by cerium(IV) with direct kinetic isotope effects (KIE > 1). At low catalyst concentration (ca. ≤10 –6 M), the RDS was a bimolecular step with k H/k D ≈ 0.8. The results support a catalytic mechanism involving coupling of two catalyst molecules. The rate constants for both RDSs were determined for all six catalysts studied. The presence of $-$CF 3 groups had inverse effects on the two steps, with the oxidation step being fastest for the unsubstituted complexes and the bimolecular step being faster for the most electron-deficient complexes. Finally, though the axial ligands studied here did not significantly affect the oxidation potentials of the catalysts, the nature of the ligand was found to be important not only in the bimolecular step but also in facilitating electron transfer from the metal center to the sacrificial oxidant.« less

Oriented conductive oxide electrodes on SiO2/Si and glass

DOEpatents

Jia, Quanxi; Arendt, Paul N.

2001-01-01

A thin film structure is provided including a silicon substrate with a layer of silicon dioxide on a surface thereof, and a layer of cubic oxide material deposited upon the layer of silicon dioxide by ion-beam-assisted-deposition, said layer of cubic oxide material characterized as biaxially oriented. Preferably, the cubic oxide material is yttria-stabilized zirconia. Additional thin layers of biaxially oriented ruthenium oxide or lanthanum strontium cobalt oxide are deposited upon the layer of yttria-stabilized zirconia. An intermediate layer of cerium oxide is employed between the yttria-stabilized zirconia layer and the lanthanum strontium cobalt oxide layer. Also, a layer of barium strontium titanium oxide can be upon the layer of biaxially oriented ruthenium oxide or lanthanum strontium cobalt oxide. Also, a method of forming such thin film structures, including a low temperature deposition of a layer of a biaxially oriented cubic oxide material upon the silicon dioxide surface of a silicon dioxide/silicon substrate is provided.

Adsorption kinetics of NO on ordered mesoporous carbon (OMC) and cerium-containing OMC (Ce-OMC)

NASA Astrophysics Data System (ADS)

Chen, Jinghuan; Cao, Feifei; Chen, Songze; Ni, Mingjiang; Gao, Xiang; Cen, Kefa

2014-10-01

Ordered mesoporous carbon (OMC) and cerium-containing OMC (Ce-OMC) were prepared using evaporation-induced self-assembly (EISA) method and used to adsorb NO. N2 sorption, X-ray diffraction (XRD) and transmission electron microscopy (TEM) were used to confirm their structures. The results showed that the ordered and uniform structures were successfully synthesized and with the introduction of cerium pore properties were not significantly changed. The NO adsorption capacity of OMC was two times larger than that of activated carbon (AC). With the introduction of cerium both the adsorption capacity and the adsorption rate were improved. The effects of residence time and oxygen concentration on NO adsorption were also investigated. Oxygen played an important role in the NO adsorption (especially in the form of chemisorption) and residence time had small influence on the NO adsorption capacity. The NO adsorption kinetics was analyzed using pseudo-first-order, pseudo-second-order, Elovich equation and intraparticle diffusion models. The results indicated that the NO adsorption process can be divided into rapid adsorption period, slow adsorption period, and equilibrium adsorption period. The pseudo-second-order model was the most suitable model for NO adsorption on OMC and Ce-OMC. The rate controlling step was the intraparticle diffusion together with the adsorption reaction.

Cerium Binding Activity of Pectins Isolated from the Seagrasses Zostera marina and Phyllospadix iwatensis

PubMed Central

Khotimchenko, Yuri; Khozhaenko, Elena; Kovalev, Valeri; Khotimchenko, Maxim

2012-01-01

Cerium binding activity of three different water soluble pectin compounds of different origin was studied in a batch sorption system. The Langmuir, Freundlich and BET sorption models were adopted to describe the binding reactions between metal ions and pectin molecules. The Langmuir model provided the best fit. Within the pH range from 4.0 to 6.0, the largest amount of the cerium ions was bound by pectin isolated from the seagrass Phylospadix iwatensis in comparison to pectin extracted from the seagrass Zostera marina and pectin obtained from citrus peel (commercial grade). The Langmuir constants were also highest for the pectin samples isolated from the seagrass P. iwatensis. The results obtained from this study suggest that pectin is a prospective source for the development of radioisotope-removing pharmaceuticals. PMID:22690146

Experimental Investigation of Performance and emission characteristics of Various Nano Particles with Bio-Diesel blend on Di Diesel Engine

NASA Astrophysics Data System (ADS)

Karthik, N.; Goldwin Xavier, X.; Rajasekar, R.; Ganesh Bairavan, P.; Dhanseelan, S.

2017-05-01

Present study provides the effect of Zinc Oxide (ZnO) and Cerium Oxide (CeO2) nanoparticles additives on the Performance and emission uniqueness of Jatropha. Jatropha blended fuel is prepared by the emulsification technique with assist of mechanical agitator. Nano particles (Zinc Oxide (ZnO)) and Cerium Oxide (CeO2)) mixed with Jatropha blended fuel in mass fraction (100 ppm) with assist of an ultrasonicator. Experiments were conducted in single cylinder constant speed direct injection diesel engine for various test fuels. Performance results revealed that Brake Thermal Efficiency (BTE) of Jatropha blended Cerium Oxide (B20CE) is 3% and 11% higher than Jatropha blended zinc oxide (B20ZO) and Jatropha blended fuel (B20) and 4% lower than diesel fuel (D100) at full load conditions. Emission result shows that HC and CO emissions of Jatropha blended Cerium Oxide (B20CE) are (6%, 22%, 11% and 6%, 15%, 12%) less compared with Jatropha blended Zinc Oxide (B20ZO), diesel (D100) and Jatropha blended fuel (B20) at full load conditions. NOx emissions of Jatropha blended Cerium Oxide is 1 % higher than diesel fuel (D100) and 2% and 5% lower than Jatropha blended Zinc Oxide, and jatropha blended fuel.

Development of High Temperature Superconducting Josephson Junction Device Technology

DTIC Science & Technology

1998-07-09

neodymium gallate , cerium oxide-buffered sapphire, and lanthanum aluminate, are not ideal for an in situ thallium cuprate junction technology. Moreover...determined that the standard HTS substrates, neodymium gallate , cerium oxide-buffered sapphire, and lanthanum aluminate, are not ideal for an in situ...2.2.1. Deposition Uniformity 10 2.2.2. Radiative Element 12 2.3. SUBSTRATES 13 2.3.1. Neodymium gallate 14 2.3.2. Cerium Oxide-Buffered Sapphire 16

Oxide strengthened molybdenum-rhenium alloy

DOEpatents

Bianco, Robert; Buckman, Jr., R. William

2000-01-01

Provided is a method of making an ODS molybdenum-rhenium alloy which includes the steps of: (a) forming a slurry containing molybdenum oxide and a metal salt dispersed in an aqueous medium, the metal salt being selected from nitrates or acetates of lanthanum, cerium or thorium; (b) heating the slurry in the presence of hydrogen to form a molybdenum powder comprising molybdenum and an oxide of the metal salt; (c) mixing rhenium powder with the molybdenum powder to form a molybdenum-rhenium powder; (d) pressing the molybdenum-rhenium powder to form a molybdenum-rhenium compact; (e) sintering the molybdenum-rhenium compact in hydrogen or under a vacuum to form a molybdenum-rhenium ingot; and (f) compacting the molybdenum-rhenium ingot to reduce the cross-sectional area of the molybdenum-rhenium ingot and form a molybdenum-rhenium alloy containing said metal oxide. The present invention also provides an ODS molybdenum-rhenium alloy made by the method. A preferred Mo--Re-ODS alloy contains 7-14 weight % rhenium and 2-4 volume % lanthanum oxide.

Properties of Cerium Hydroxides from Matrix Infrared Spectra and Electronic Structure Calculations.

PubMed

Fang, Zongtang; Thanthiriwatte, K Sahan; Dixon, David A; Andrews, Lester; Wang, Xuefeng

2016-02-15

Reactions of laser ablated cerium atoms with hydrogen peroxide or hydrogen and oxygen mixtures diluted in argon and condensed at 4 K produced the Ce(OH)3 and Ce(OH)2 molecules and Ce(OH)2(+) cation as major products. Additional minor products were identified as the Ce(OH)4, HCeO, and OCeOH molecules. These new species were identified from their matrix infrared spectra with D2O2, D2, and (18)O2 isotopic substitution and correlating observed frequencies with values calculated by density functional theory. We find that the amounts of Ce(OH)3 and of the Ce(OH)2(+) cation increase on UV (λ > 220 nm) photolysis, while Ce(OH)2, Ce(OH)4, and HCeO are photosensitive. The observed major species for Ce are in the +III or +II oxidation state, and the minor product, Ce(OH)4, is in the +IV oxidation state. The calculations for the vibrational frequencies with the B3LYP functional agree well with the experiment. The NBO analysis shows significant backbonding to the metal 4f and 5d orbitals for the closed shell species. Most open shell species have the excess spin in the 4f with paired spin in the 5d due to backbonding. The heats of formation of the observed species were derived from the available data from experiment and the calculated reaction energies. The major products in this study are different from similar reactions for Th where the tetrahydroxide was the major species.

Nano-crystalline thin and nano-particulate thick TiO{sub 2} layer: Cost effective sequential deposition and study on dye sensitized solar cell characteristics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Das, P.; Sengupta, D.; CSIR-Central Mechanical Engineering Research Institute, Academy of Scientific and Innovative Research

Highlights: • Thin TiO{sub 2} layer is deposited on conducting substrate using sol–gel based dip coating. • TiO{sub 2} nano-particles are synthesized using hydrothermal route. • Thick TiO{sub 2} particulate layer is deposited on prepared thin layer. • Dye sensitized solar cells are made using thin and thick layer based photo-anode. • Introduction of thin layer in particulate photo-anode improves the cell efficiency. - Abstract: A compact thin TiO{sub 2} passivation layer is introduced between the mesoporous TiO{sub 2} nano-particulate layer and the conducting glass substrate to prepare photo-anode for dye-sensitized solar cell (DSSC). In order to understand the effectmore » of passivation layer, other two DSSCs are also developed separately using TiO{sub 2} nano-particulate and compact thin film based photo-anodes. Nano-particles are prepared using hydrothermal synthesis route and the compact passivation layer is prepared by simply dip coating the precursor sol prepared through wet chemical route. The TiO{sub 2} compact layer and the nano-particles are characterised in terms of their micro-structural features and phase formation behavior. It is found that introduction of a compact TiO{sub 2} layer in between the mesoporous TiO{sub 2} nano-particulate layer and the conducting substrate improves the solar to electric conversion efficiency of the fabricated cell. The dense thin passivation layer is supposed to enhance the photo-excited electron transfer and prevent the recombination of photo-excited electrons.« less

Effect of oxidizer to fuel molar ratio on particle size and DC conductivity of CeO{sub 2} nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Harish, B. M.; Rajeeva, M. P.; Naveen, C. S.

2016-05-06

Cerium oxide nanoparticles were synthesized by solution combustion method with varying the oxidizer (cerium nitrate hexa hydrate) to fuel (Glycine) molar ratio. The prepared samples were characterized by UV-visible spectrometer, X-ray diffractometer (XRD), Scanning electron microscope (SEM) and Energy dispersive X-Ray analysis (EDAX). XRD pattern reveals the formation of cubic fluorite structure of CeO{sub 2}. It was observed that finest crystallites were found at extreme fuel-deficient condition and it is good enough to produce favorable powder characteristics. The average crystallite size was found to be 14.46 nm to 21.57 nm. The temperature dependent dc conductivity was carried out using Keithleymore » source meter between the temperature range from 300 K to 573 K. From this study it was found that the conductivity increases with increase of temperature due to semiconducting behavior of CeO{sub 2} and it decreases with particle size due to increase in the energy band gap.« less

Fuel electrode containing pre-sintered nickel/zirconia for a solid oxide fuel cell

DOEpatents

Ruka, Roswell J.; Vora, Shailesh D.

2001-01-01

A fuel cell structure (2) is provided, having a pre-sintered nickel-zirconia fuel electrode (6) and an air electrode (4), with a ceramic electrolyte (5) disposed between the electrodes, where the pre-sintered fuel electrode (6) contains particles selected from the group consisting of nickel oxide, cobalt and cerium dioxide particles and mixtures thereof, and titanium dioxide particles, within a matrix of yttria-stabilized zirconia and spaced-apart filamentary nickel strings having a chain structure, and where the fuel electrode can be sintered to provide an active solid oxide fuel cell.

Redox conditions in the Late Cretaceous Chalk Sea: the possible use of cerium anomalies as palaeoredox indicators in the Cenomanian and Turonian Chalk of England

NASA Astrophysics Data System (ADS)

Jeans, Christopher V.; Wray, David S.; Williams, C. Terry

2015-09-01

The cerium anomalies preserved in the Chalk have been investigated as possible palaeoredox indicators of the Late Cretaceous Sea and its sediment. This has been based upon over a hundred new rare earth element analyses of selected samples and grain size fractions from the Chalk. Particular attention has been given to the methodology of differentiating between the cerium anomalies preserved in the bioclastic calcite and those in carbonate-fluorapatite preserved in the acetic acid insoluble residues of chalks. Variations in the cerium anomaly of different particle size fractions of uncemented chalks suggest that fractionation of rare earth elements between the Chalk's seawater and the various organisms that contributed skeletal material to the bioclastic calcite of the Chalk may have occurred. Post-depositional processes of calcite cementation and late diagenetic sulphidisation have had no apparent effect on the cerium anomaly of the acetic acid insoluble residues. The cerium anomalies associated with the acetic acid insoluble residues from (1) an alternating sequence of chalks and marls from Ballard Cliff (Dorset, UK) typical of Milankovitch cyclicity show a marked diagenetic pattern, whereas those from (2) non-volcanic and volcanic marls display a pattern that is best explained by the variations in the availability of phosphorus and the timing of argillisation of volcanic glass during diagenesis. The general conclusion is drawn that the cerium anomalies preserved in the Chalk can provide an insight into the changing palaeoredox conditions in the Late Cretaceous Sea as well as in the pore fluids of its sediments.

[Na5(THF)10Ce(mnt)4]infinity: a honeycomb network polymer that yields homoleptic cerium(III) tetrakis(dithiolene) complexes in donor solvents.

PubMed

Weis, Eric M; Barnes, Charles L; Duval, Paul B

2006-12-11

The first example of a lanthanide tetrakis(dithiolene) complex, [Na5(THF)10Ce(mnt)4] (1) (mnt = 1,2-maleonitrile-1,2-dithiolate), has been synthesized and characterized by X-ray crystallography and spectroscopic methods. In the solid state, 1 exists as a 2-D corrugated honeycomb network polymer in which the monomeric units comprising the trigonal nodes are knitted together by interlocking dative Na-N bonds extended from nitrile groups of bifunctional mnt ligands coordinated through the sulfur atoms to adjacent cerium centers. Individual honeycomb sheets are separated by 14.8 A. Compound 1 dissolves in donor solvents such as THF and acetonitrile to give soluble [Ce(mnt)4]5- units that exhibit spectroscopic features (i.e., NMR, luminescence, UV-vis) that are consistent with the 4f1 Ce(III) ion. In the first examination of the redox chemistry of a lanthanide dithiolene complex, cyclic voltammetry measurements conducted on 1 reveal a single irreversible oxidation wave that is likely attributable to ligand-centered oxidation.

International strategic minerals inventory summary report; rare-earth oxides

USGS Publications Warehouse

Jackson, W.D.; Christiansen, Grey

1993-01-01

Bastnaesite, monazite, and xenotime are currently the most important rare-earth minerals. Bastnaesite occurs as a primary mineral in carbonatites. Monazite and xenotime also can be found in primary deposits but are recovered principally from heavy-mineral placers that are mined for titanium or tin. Each of these minerals has a different composition of the 15 rare-earth elements. World resources of economically exploitable rare-earth oxides (REO) are estimated at 93.4 million metric tons in place, composed of 93 percent in primary deposits and 7 percent in placers. The average mineral composition is 83 percent bastnaesite, 13 percent monazite, and 4 percent of 10 other minerals. Annual global production is about 67,000 metric tons of which 41 percent is from placers and 59 percent is from primary deposits; mining methods consist of open pits (94 percent) and dredging (6 percent). This output could be doubled if the operations that do not currently recover rare earths would do so. Resources are more than sufficient to meet the demand for the predictable future. About 52 percent of the world's REO resources are located in China. Ranking of other countries is as follows: Namibia (22 percent), the United States (15 percent), Australia (6 percent), and India (3 percent); the remainder is in several other countries. Conversely, 38 percent of the production is in China, 33 percent in the United States, 12 percent in Australia, and 5 percent each in Malaysia and India. Several other countries, including Brazil, Canada, South Africa, Sri Lanka, and Thailand, make up the remainder. Markets for rare earths are mainly in the metallurgical, magnet, ceramic, electronic, chemical, and optical industries. Rare earths improve the physical and rolling properties of iron and steel and add corrosion resistance and strength to structural members at high temperatures. Samarium and neodymium are used in lightweight, powerful magnets for electric motors. Cerium and yttrium increase the

Composites of Polymer Hydrogels and Nanoparticulate Systems for Biomedical and Pharmaceutical Applications

PubMed Central

Zhao, Fuli; Yao, Dan; Guo, Ruiwei; Deng, Liandong; Dong, Anjie; Zhang, Jianhua

2015-01-01

Due to their unique structures and properties, three-dimensional hydrogels and nanostructured particles have been widely studied and shown a very high potential for medical, therapeutic and diagnostic applications. However, hydrogels and nanoparticulate systems have respective disadvantages that limit their widespread applications. Recently, the incorporation of nanostructured fillers into hydrogels has been developed as an innovative means for the creation of novel materials with diverse functionality in order to meet new challenges. In this review, the fundamentals of hydrogels and nanoparticles (NPs) were briefly discussed, and then we comprehensively summarized recent advances in the design, synthesis, functionalization and application of nanocomposite hydrogels with enhanced mechanical, biological and physicochemical properties. Moreover, the current challenges and future opportunities for the use of these promising materials in the biomedical sector, especially the nanocomposite hydrogels produced from hydrogels and polymeric NPs, are discussed. PMID:28347111

Leishmaniasis: focus on the design of nanoparticulate vaccine delivery systems.

PubMed

Doroud, Delaram; Rafati, Sima

2012-01-01

Although mass vaccination of the entire population of an endemic area would be the most cost-effective tool to diminish Leishmania burden, an effective vaccine is not yet commercially available. Practically, vaccines have failed to achieve the required level of protection, possibly owing to the lack of an appropriate adjuvant and/or delivery system. Therefore, there is still an imperative demand for an improved, safe and efficient delivery system to enhance the immunogenicity of available vaccine candidates. Nanoparticles are proficient in boosting the quality and magnitude of immune responses in a predictable fashion. Herein, we discuss how nanoparticulate vaccine delivery systems can be used to induce appropriate immune responses against leishmaniasis by controlling physicochemical properties of the vaccine. Stability, production reproducibility, low cost per dose and low risk-benefit ratios are desirable characteristics of an ideal vaccine formulation and solid lipid nanoparticles may serve as one of the most promising practical strategies to help to achieve such a leishmanial vaccine, at least in canine species in the developing world.

Photochemical water oxidation by crystalline polymorphs of manganese oxides: structural requirements for catalysis.

PubMed

Robinson, David M; Go, Yong Bok; Mui, Michelle; Gardner, Graeme; Zhang, Zhijuan; Mastrogiovanni, Daniel; Garfunkel, Eric; Li, Jing; Greenblatt, Martha; Dismukes, G Charles

2013-03-06

Manganese oxides occur naturally as minerals in at least 30 different crystal structures, providing a rigorous test system to explore the significance of atomic positions on the catalytic efficiency of water oxidation. In this study, we chose to systematically compare eight synthetic oxide structures containing Mn(III) and Mn(IV) only, with particular emphasis on the five known structural polymorphs of MnO2. We have adapted literature synthesis methods to obtain pure polymorphs and validated their homogeneity and crystallinity by powder X-ray diffraction and both transmission and scanning electron microscopies. Measurement of water oxidation rate by oxygen evolution in aqueous solution was conducted with dispersed nanoparticulate manganese oxides and a standard ruthenium dye photo-oxidant system. No Ru was absorbed on the catalyst surface as observed by XPS and EDX. The post reaction atomic structure was completely preserved with no amorphization, as observed by HRTEM. Catalytic activities, normalized to surface area (BET), decrease in the series Mn2O3 > Mn3O4 ≫ λ-MnO2, where the latter is derived from spinel LiMn2O4 following partial Li(+) removal. No catalytic activity is observed from LiMn2O4 and four of the MnO2 polymorphs, in contrast to some literature reports with polydispersed manganese oxides and electro-deposited films. Catalytic activity within the eight examined Mn oxides was found exclusively for (distorted) cubic phases, Mn2O3 (bixbyite), Mn3O4 (hausmannite), and λ-MnO2 (spinel), all containing Mn(III) possessing longer Mn-O bonds between edge-sharing MnO6 octahedra. Electronically degenerate Mn(III) has antibonding electronic configuration e(g)(1) which imparts lattice distortions due to the Jahn-Teller effect that are hypothesized to contribute to structural flexibility important for catalytic turnover in water oxidation at the surface.

The tortoise versus the hare - Possible advantages of microparticulate zerovalent iron (mZVI) over nanoparticulate zerovalent iron (nZVI) in aerobic degradation of contaminants.

PubMed

Ma, Jinxing; He, Di; Collins, Richard N; He, Chuanshu; Waite, T David

2016-11-15

A comparative study of the ability of microparticulate zerovalent iron (mZVI) and nanoparticulate zerovalent iron (nZVI) to oxidize a target compound (in this study, 14 C-labelled formate) under aerobic conditions has been conducted with specific consideration given to differences in reaction mechanisms. Results of Fe K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy showed that mZVI underwent a slow transformation to ferrihydrite while nZVI, in contrast, rapidly transformed into lepidocrocite. The behavior of mZVI (compared to nZVI) could be attributed to either (i) a lower reactivity with oxygen and/or water, (ii) surface passivation by ferrihydrite resulting in reduced electron conductivity, and/or (iii) the relatively low concentration of Fe(II) which, in the case of nZVI, catalyzed the transformation of ferrihydrite to lepidocrocite. The influence of these structural transformations on contaminant removal was profound with the ferrihydrite that formed on mZVI inducing rapid adsorption of formate and moderating reactions of mZVI with oxygen and/or water. Although surface passivation of mZVI was significant, the effectiveness of the ensuing heterogeneous redox reactions in the mZVI/O 2 system, as characterized by the molar ratio of oxidized formate to consumed Fe(0) (i.e., 13.7 ± 0.8 μM/M), was comparable to that for nZVI (16.5 ± 1.4 μM/M). The results of this study highlight the potential of mZVI for the oxidative degradation of target organics in preference to nZVI despite its lower intrinsic reactivity though some means (either natural or engineered) of inducing continual depassivation of the iron oxyhydroxide-coated mZVI would be required in order to maintain ongoing oxidant production. Copyright © 2016 Elsevier Ltd. All rights reserved.

Direct hydrothermal growth of GDC nanorods for low temperature solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Hong, Soonwook; Lee, Dohaeng; Yang, Hwichul; Kim, Young-Beom

2018-06-01

We report a novel synthesis technique of gadolinia-doped ceria (GDC) nano-rod (NRs) via direct hydrothermal process to enhance performance of low temperature solid oxide fuel cell by increasing active reaction area and ionic conductivity at interface between cathode and electrolyte. The cerium nitrate hexahydrate, gadolinium nitrate hexahydrate and urea were used to synthesis GDC NRs for growth on diverse substrate. The directly grown GDC NRs on substrate had a width from 819 to 490 nm and height about 2200 nm with a varied urea concentration. Under the optimized urea concentration of 40 mMol, we confirmed that GDC NRs able to fully cover the substrate by enlarging active reaction area. To maximize ionic conductivity of GDC NRs, we synthesis varied GDC NRs with different ratio of gadolinium and cerium precursor. Electrochemical analysis revealed a significant enhanced performance of fuel cells applying synthesized GDC NRs with a ratio of 2:8 gadolinium and cerium precursor by reducing polarization resistance, which was chiefly attributed to the enlarged active reaction area and enhanced ionic conductivity of GDC NRs. This method of direct hydrothermal growth of GDC NRs enhancing fuel cell performance was considered to apply other types of catalyzing application using nano-structure such as gas sensing and electrolysis fields.

High-pressure synthesis and characterization of the first cerium fluoride borate CeB{sub 2}O{sub 4}F

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hinteregger, Ernst; Wurst, Klaus; Tribus, Martina

2013-08-15

CeB{sub 2}O{sub 4}F is the first cerium fluoride borate, which is exclusively built up of one-dimensional, infinite chains of condensed trigonal-planar [BO{sub 3}]{sup 3−} groups. This new cerium fluoride borate was synthesized under high-pressure/high-temperature conditions of 0.9 GPa and 1450 °C in a Walker-type multianvil apparatus. The compound crystallizes in the orthorhombic space group Pbca (No. 61) with eight formula units and the lattice parameters a=821.63(5), b=1257.50(9), c=726.71(6) pm, V=750.84(9) Å{sup 3}, R{sub 1}=0.0698, and wR{sub 2}=0.0682 (all data). The structure exhibits a 9+1 coordinated cerium ion, one three-fold coordinated fluoride ion and a one-dimensional chain of [BO{sub 3}]{sup 3−}more » groups. Furthermore, IR spectroscopy, Electron Micro Probe Analysis and temperature-dependent X-ray powder diffraction measurements were performed. - Graphical abstract: A new rare-earth fluoride borate CeB{sub 2}O{sub 4}F could be synthesized under high-pressure/high-temperature conditions of 0.9 °GPa and 1450 °Cin a Walker-type multianvil apparatus. The crystal structure represents a new structure type in the class of rare-earth fluoride borates. The structure exhibits a 9+1 coordinated cerium ion, one three-fold coordinated fluoride ion and a one-dimensional chain of [BO{sub 3}]{sup 3−} groups. A closer view on the ac-plane shows an interesting wave-like modulation of the borate chains. Highlights: • CeB{sub 2}O{sub 4}F is the first fluoride borate exclusively built up of one-dimensional, infinite chains of condensed trigonal-planar [BO{sub 3}]{sup 3−} groups. • CeB{sub 2}O{sub 4}F is the first cerium fluoride borate. • High-pressure conditions were necessary to synthesize CeB{sub 2}O{sub 4}F.« less

Chemoselective phototransformation of C-H bonds on a polymer surface through a photoinduced cerium recycling redox reaction.

PubMed

Huang, Zhenhua; Wu, Zhengfang; Yang, Peng; Yang, Wantai

2014-09-01

It is generally accepted that Ce(4+) is unable to directly oxidize unreactive alkyl C-H bonds without the assistance of adjacent polar groups. Herein, we demonstrate in our newly developed confined photochemical reaction system that this recognized issue may be challenged. As we found, when a thin layer of a CeCl(3)/HCl aqueous solution was applied to a polymeric substrate and the substrate subjected to UV irradiation, Ce(3+) was first photooxidized to form Ce(4+) in the presence of H(+), and the in situ formed Ce(4+) then performs an oxidation reaction on the C-H bonds of the polymer surface to form surface-carbon radicals for radical graft polymerization reactions and functional-group transformations, while reducing to Ce(3+) and releasing H(+) in the process. This photoinduced cerium recycling redox (PCRR) reaction behaved as a biomimetic system in an artificial recycling reaction, leading to a sustainable chemical modification strategy for directly transforming alkyl C-H bonds on polymer surfaces into small-molecule groups and polymer brushes. This method is expected to provide a green and economical tool for industrial applications of polymer-surface modification. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Biogenic manganese oxide nanoparticle formation by a multimeric multicopper oxidase Mnx

DOE Office of Scientific and Technical Information (OSTI.GOV)

Romano, Christine A.; Zhou, Mowei; Song, Yang

Bacteria that produce Mn oxides are extraordinarily skilled engineers of nanomaterials that contribute significantly to global biogeochemical cycles. Their enzyme-based reaction mechanisms may be genetically tailored for environmental remediation applications or bioenergy production. However, significant challenges exist for structural characterization of the enzymes responsible for biomineralization. The active Mn oxidase, Mnx, in Bacillus sp. PL-12 is a complex composed of a multicopper oxidase (MCO), MnxG, and two accessory proteins MnxE and MnxF. MnxG shares sequence similarity with other, structurally characterized MCOs. However, MnxE and MnxF have no similarity to any characterized proteins. The ~200 kDa complex has been recalcitrant tomore » crystallization, so its structure is unknown. In this study, native mass spectrometry defines the subunit topology and copper binding of the Mnx complex, while high resolution electron microscopy visualizes the protein and nascent Mn oxide minerals. These data provide critical structural information for conceptualizing how Mnx produces nanoparticulate Mn oxides.« less

Kinetic and catalytic analysis of mesoporous metal oxides on the oxidation of Rhodamine B

NASA Astrophysics Data System (ADS)

Xaba, Morena S.; Noh, Ji-Hyang; Mokgadi, Keabetswe; Meijboom, Reinout

2018-05-01

In this study, we demonstrate the synthesis and catalytic activity of different mesoporous transition metal oxides, silica (SiO2), copper oxide (CuO), chromium oxide (Cr2O3), iron oxide (Fe2O3) cobalt oxide (Co3O4), cerium oxide (CeO2) and nickel oxide (NiO), on the oxidation of a pollutant dye, Rhodamine B (RhB). These metal oxides were synthesized by inverse micelle formation method and characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), adsorption-desorption isotherms (BET) and H2-temperature programmed reduction (TPR). UV-vis spectrophotometry was used to monitor the time-resolved absorbance of RhB at λmax = 554 nm. Mesoporous copper oxide was calcined at different final heating temperatures of 250, 350, 450 and 550 °C, and each mesoporous copper oxide catalyst showed unique physical properties and catalytic behavior. Mesoporous CuO-550 with the smallest characteristic path length δ, proved to be the catalyst of choice for the oxidation of RhB in aqueous media. We observed that the oxidation of RhB in aqueous media is dependent on the crystallite size and characteristic path length of the mesoporous metal oxide. The Langmuir-Hinshelwood model was used to fit the experimental data and to prove that the reaction occurs on the surface of the mesoporous CuO. The thermodynamic parameters, EA, ΔH#, ΔS# and ΔG# were calculated and catalyst recycling and reusability were demonstrated.

Methane Activation Mediated by a Series of Cerium-Vanadium Bimetallic Oxide Cluster Cations: Tuning Reactivity by Doping.

PubMed

Ma, Jia-Bi; Meng, Jing-Heng; He, Sheng-Gui

2016-04-18

The reactions of cerium-vanadium cluster cations Cex Vy Oz (+) with CH4 are investigated by time-of-flight mass spectrometry and density functional theory calculations. (CeO2 )m (V2 O5 )n (+) clusters (m=1,2, n=1-5; m=3, n=1-4) with dimensions up to nanosize can abstract one hydrogen atom from CH4 . The theoretical study indicates that there are two types of active species in (CeO2 )m (V2 O5 )n (+) , V[(Ot )2 ](.) and [(Ob )2 CeOt ](.) (Ot and Ob represent terminal and bridging oxygen atoms, respectively); the former is less reactive than the latter. The experimentally observed size-dependent reactivities can be rationalized by considering the different active species and mechanisms. Interestingly, the reactivity of the (CeO2 )m (V2 O5 )n (+) clusters falls between those of (CeO2 )2-4 (+) and (V2 O5 )1-5 (+) in terms of C-H bond activation, thus the nature of the active species and the cluster reactivity can be effectively tuned by doping. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Flow injection chemiluminescent determination of tetracycline using a tris(2,2'-bipyridine)ruthenium(II)-cerium(IV) sulphate system.

PubMed

Guo, Liangqia; Xie, Zenghong; Lin, Xucong; Liu, Xiaohua; Zhang, Weilin; Chen, Guonan

2004-01-01

A flow-injection chemiluminescence method for the determination of tetracycline was developed. The method is based on an enhancement by tetracycline of the chemiluminescence light emission of tris(2,2'-bipyridine)ruthenium(II). In sulphuric acid medium, the chemiluminescence is generated by the continuous oxidation of tris(2,2'-bipyridine)ruthenium(II) by cerium (IV) sulphate. The light-emission intensity is greatly enhanced in the presence of tetracycline. Under the optimum conditions, the calibration curve is linear over the range 3.75 x 10(-8) g/mL-1.5 x 10(-5) g/mL for tetracycline with the linear equation: deltaINT = 205.898 x C - 20.442 (R2 = 0.9974). The detection limit is 3.27 x 10(-8) g/mL. The proposed method was also successfully used to determine tetracycline in pharmaceutical formulation (mean recovery of tetracycline, 100.7%). Copyright 2004 John Wiley & Sons, Ltd.

Metal/metal oxide doped oxide catalysts having high deNOx selectivity for lean NOx exhaust aftertreatment systems

DOEpatents

Park, Paul W.

2004-03-16

A lean NOx catalyst and method of preparing the same is disclosed. The lean NOx catalyst includes a ceramic substrate, an oxide support material, preferably .gamma.-alumina, deposited on the substrate and a metal promoter or dopant introduced into the oxide support material. The metal promoters or dopants are selected from the group consisting of indium, gallium, tin, silver, germanium, gold, nickel, cobalt, copper, iron, manganese, molybdenum, chromium, cerium, vanadium, oxides thereof, and combinations thereof. The .gamma.-alumina preferably has a pore volume of from about 0.5 to about 2.0 cc/g; a surface area of between about 80 to 350 m.sup.2 /g; an average pore size diameter of between about 3 to 30 nm; and an impurity level of less than or equal to 0.2 weight percent. In a preferred embodiment the .gamma.-alumina is prepared by a sol-gel method, with the metal doping of the .gamma.-alumina preferably accomplished using an incipient wetness impregnation technique.

Ceria nanoparticles vis-à-vis cerium nitrate as corrosion inhibitors for silica-alumina hybrid sol-gel coating

NASA Astrophysics Data System (ADS)

Lakshmi, R. V.; Aruna, S. T.; Sampath, S.

2017-01-01

The present work provides a comparative study on the corrosion protection efficiency of defect free sol-gel hybrid coating containing ceria nanoparticles and cerium nitrate ions as corrosion inhibitors. Less explored organically modified alumina-silica hybrid sol-gel coatings are synthesized from 3-glycidoxypropyltrimethoxysilane and aluminium-tri-sec-butoxide. The microemulsion derived nanoparticles and the hybrid coatings are characterized and compared with coatings containing cerium nitrate. Corrosion inhibiting capability is assessed using electrochemical impedance spectroscopy. Scanning Kelvin probe measurements are also conducted on the coatings for identifying the apparent corrosion prone regions. Detailed X-ray photoelectron spectroscopy (XPS) analysis is carried out to comprehend the bonding and corrosion protection rendered by the hybrid coatings.

Experimental determination of water activity for binary aqueous cerium(III) ionic solutions: application to an assessment of the predictive capability of the binding mean spherical approximation model.

PubMed

Ruas, Alexandre; Simonin, Jean-Pierre; Turq, Pierre; Moisy, Philippe

2005-12-08

This work is aimed at a description of the thermodynamic properties of actinide salt solutions at high concentration. The predictive capability of the binding mean spherical approximation (BIMSA) theory to describe the thermodynamic properties of electrolytes is assessed in the case of aqueous solutions of lanthanide(III) nitrate and chloride salts. Osmotic coefficients of cerium(III) nitrate and chloride were calculated from other lanthanide(III) salts properties. In parallel, concentrated binary solutions of cerium nitrate were prepared in order to measure experimentally its water activity and density as a function of concentration, at 25 degrees C. Water activities of several binary solutions of cerium chloride were also measured to check existing data on this salt. Then, the properties of cerium chloride and cerium nitrate solutions were compared within the BIMSA model. Osmotic coefficient values for promethium nitrate and promethium chloride given by this theory are proposed. Finally, water activity measurements were made to examine the fact that the ternary system Ce(NO3)3/HNO3/H2O and the quaternary system Ce(NO3)3/HNO3/N2H5NO3/H2O may be regarded as "simple solutions" (in the sense of Zdanovskii and Mikulin).

Optical, Structural, and Thermal Properties of Cerium-Doped Zinc Borophosphate Glasses.

PubMed

Choi, Su-Yeon; Ryu, Bong-Ki

2015-11-01

In this study, we verify the relationship between the optical properties and structure of cerium-doped zinc borophosphate glasses that have concurrence of non-bridging oxygen (NBO) and bridging oxygen (BO), Ce3+ and Ce4+, and BO3 structure and BO4 structure. We prepared cerium-doped zinc borophosphate glass with various compositions, given by xCeO2-(100-x)[50ZnO-10B2O3 -40P2O5] (x = 1 mol% to 6 mol%), and analyzed their optical band energy, glass transition temperature, crystallization temperature, density, and molar volume. Some of the techniques used for analysis were Fourier transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS). In the investigated glasses, the optical band gap energy decreased from 3.28 eV to 1.73 eV. From these results, we can deduce the changes when transitions occur from BO to NBO, from Ce3+ to Ce4+, and from the BO3 structure to the BO4 structure with increasing CeO2 content using FT-IR and XPS analysis. We also verified the changes in structural and physical properties from quantitative properties such as glass transition temperature, crystallization temperature, density, and molar volume.

Nitric oxide nanoparticles

PubMed Central

Schairer, David O.; Martinez, Luis R.; Blecher, Karin; Chouake, Jason S.; Nacharaju, Parimala; Gialanella, Philip; Friedman, Joel M.; Nosanchuk, Joshua D.; Friedman, Adam J.

2012-01-01

Nitric oxide (NO) is a critical component of host defense against invading pathogens; however, its therapeutic utility is limited due to a lack of practical delivery systems. Recently, a NO-releasing nanoparticulate platform (NO-np) was shown to have in vitro broad-spectrum antimicrobial activity and in vivo pre-clinical efficacy in a dermal abscess model. To extend these findings, both topical (TP) and intralesional (IL) NO-np administration was evaluated in a MRSA intramuscular murine abscess model and compared with vancomycin. All treatment arms accelerated abscess clearance clinically, histologically, and by microbiological assays on both days 4 and 7 following infection. However, abscesses treated with NO-np via either route demonstrated a more substantial, statistically significant decrease in bacterial survival based on colony forming unit assays and histologically revealed less inflammatory cell infiltration and preserved muscular architecture. These data suggest that the NO-np may be an effective addition to our armament for deep soft tissue infections. PMID:22286699

Photoluminescence from trivalent-cerium-doped silica glass prepared by sol-gel method with aluminum co-dopant

NASA Astrophysics Data System (ADS)

Tokumitsu, Seika; Murakami, Yukon; Oda, Hisaya; Kawabe, Yutaka

2018-01-01

Trivalent cerium is an important luminescent center giving light emission in short wavelength region depending on host materials. Sol-gel formed silica glass is an ideal matrix due to its high transparency, robustness, and low-temperature processability, but the emission from cerium in silica matrix is often mixed up with that from defects in the matrix, making it difficult to obtain well-determined characteristics. Bright emission from Ce ions peaking at about 400 nm was observed in sol-gel silica glasses synthesized with aluminum co-dopant. From luminescence decay time, the origin was confirmed to be d-f transition in trivalent Ce. From dependence of emission characteristics and UV absorbance on aluminum concentration, it was found that the co-dopant plays an important role to convert the optically inactive tetravalent ions to emissive trivalent state.

High performance Aurivillius phase sodium-potassium bismuth titanate lead-free piezoelectric ceramics with lithium and cerium modification

NASA Astrophysics Data System (ADS)

Wang, Chun-Ming; Wang, Jin-Feng

2006-11-01

The piezoelectric properties of the lithium and cerium modified A-site vacancies sodium-potassium bismuth titanate (NKBT) lead-free piezoceramics are investigated. The piezoelectric activity of NKBT ceramics is significantly improved by the modification of lithium and cerium. The Curie temperature TC, piezoelectric coefficient d33, and mechanical quality factor Qm for the NKBT ceramics modified with 0.10mol% (LiCe) are found to be 660°C, 25pC/N, and 3135, respectively. The Curie temperature gradually decreases from 675to650°C with the increase of (LiCe) modification. The dielectric spectroscopy shows that all the samples possess stable piezoelectric properties, demonstrating that the (LiCe) modified NKBT-based ceramics are the promising candidates for high temperature applications.

Chemical analysis of extracting transition metal oxides from polymetallic ore by sulphate process

NASA Astrophysics Data System (ADS)

Enkh-Uyanga, Otgon-Uul; Munkhtsetseg, Baatar; Urangoo, Urtnasan; Tserendulam, Enkhtur; Agiimaa, Davaadorj

2017-06-01

In this research work we attempt to improve the purity of polymetallic ores in Mongolia whilst developing practical applications of its refinement processes and this paper presents the results of chemical research of extracting transition metal titanium oxides, ferrous oxide and rare earth oxides from polymetallic ore. Thereby, chemical and mineral analysis of polymetallic ore is carried out basis of responses to the support process at various degrees of water whereas transition metal sulphates solubility differ. As a result of sulphate and resulphurization process we have extracted anatase with 62.5 percent titanium dioxide and brookite mineral with 89.6 percent of titanium dioxide as well as mineral with 83.8 percent of ferrous oxide hematite and rare earth oxides with 57.6 percent of cerium oxide. These oxides are identified under various conditions in the thermal processing. The morphology structure and chemical content compound of the mineral has been verified as a result of the XRF, XRD, SEM-EDX analysis.

Nanoparticulate, sub-micron and micron sized particles emanating from hydrothermal vents

NASA Astrophysics Data System (ADS)

Luther, G. W., III; Gartman, A.; Findlay, A.; Yucel, M.; Chan, C. S. Y.

2015-12-01

Recent data from Geotraces cruises over the MAR and SEPR indicate dissolved and particulate Fe enrichment in waters 1000 and 4000 km from their vent sources, respectively. Deep-sea hydrothermal vents and the waters in the reactive mixing zone above vent orifices have been suggested to be an important source of fine material that can pass through normal filters (0.2 and 0.4 μm). In this work, nanoparticles are defined operationally as that which can pass through a 0.2 μm filter. We investigated two vent sites (Lau Basin and the MAR). Chimneys from both vent sites have fluids that can be sulfide rich or metal rich. We also present chemical and physical chemical data (SEM-EDS, TEM, XRD, EELS) showing some of the materials found in these (nano)particulate phases including pyrite, metal sulfides, silicate and aluminosilicate material. Enrichment of Mg and K in the latter suggest that reverse weathering may occur in the waters within 1-2 meters of the vent orifice where vent waters mix with cold oxygenated bottom waters.

Single-Nanoparticle Photoelectrochemistry at a Nanoparticulate TiO2 -Filmed Ultramicroelectrode.

PubMed

Peng, Yue-Yi; Ma, Hui; Ma, Wei; Long, Yi-Tao; Tian, He

2018-03-26

An ultrasensitive photoelectrochemical method for achieving real-time detection of single nanoparticle collision events is presented. Using a micrometer-thick nanoparticulate TiO 2 -filmed Au ultra-microelectrode (TiO 2 @Au UME), a sub-millisecond photocurrent transient was observed for an individual N719-tagged TiO 2 (N719@TiO 2 ) nanoparticle and is due to the instantaneous collision process. Owing to a trap-limited electron diffusion process as the rate-limiting step, a random three-dimensional diffusion model was developed to simulate electron transport dynamics in TiO 2 film. The combination of theoretical simulation and high-resolution photocurrent measurement allow electron-transfer information of a single N719@TiO 2 nanoparticle to be quantified at single-molecule accuracy and the electron diffusivity and the electron-collection efficiency of TiO 2 @Au UME to be estimated. This method provides a test for studies of photoinduced electron transfer at the single-nanoparticle level. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electric dipole transitions for four-times ionized cerium (Ce V)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Usta, Betül Karaçoban, E-mail: bkaracoban@sakarya.edu.tr; Akgün, Elif, E-mail: elif.akgun@ogr.sakarya.edu.tr; Alparslan, Büşra, E-mail: busra.alparslan1@ogr.sakarya.edu.tr

2016-03-25

We have calculated the transition parameters, such as wavelengths, oscillator strengths, and transition probabilities (or rates), for the electric dipole (E1) transitions in four-times ionized cerium (Ce V, Z = 58) by using the multiconfiguration Hartree-Fock method within the framework of Breit-Pauli (MCHF+BP) relativistic corrections and the relativistic Hartree-Fock (HFR) method. The obtained results have been compared with other works available in literature. A discussion of these calculations for Ce V in this study has also been in view of the MCHF+BP and HFR methods.

Nano-sized Mn3O4 and β-MnOOH from the decomposition of β-cyclodextrin-Mn: 2. The water-oxidizing activities.

PubMed

Najafpour, Mohammad Mahdi; Mostafalu, Ramin; Hołyńska, Małgorzata; Ebrahimi, Foad; Kaboudin, Babak

2015-11-01

Nano-sized Mn oxides contain Mn3O4, β-MnOOH and Mn2O3 have been prepared by a previously reported method using thermal decomposition of β-cyclodextrin-Mn complexes. In the next step, the water-oxidizing activities of these Mn oxides using cerium(IV) ammonium nitrate as a chemical oxidant are studied. The turnover frequencies for β-MnO(OH) and Mn3O4 are 0.24 and 0.01-0.17 (mmol O2/mol Mns), respectively. Subsequently, water-oxidizing activities of these compounds are compared to the other previously reported Mn oxides. Important factors affecting water oxidation by these Mn oxides are also discussed. Copyright © 2015 Elsevier B.V. All rights reserved.

Oxidative Stress, Inflammation, and DNA Damage Responses Elicited by Silver, Titanium Dioxide, and Cerium Oxide Nanomaterials

EPA Science Inventory

Previous literature on the biological effects of engineered nanomaterials has focused largely on oxidative stress and inflammation endpoints without further investigating potential pathways. Here we examine time-sensitive biological response pathways affected by engineered nanoma...

Absence of systemic toxicity in mouse model towards BaTiO3 nanoparticulate based eluate treatment.

PubMed

Dubey, Ashutosh Kumar; Thrivikraman, Greeshma; Basu, Bikramjit

2015-02-01

One of the existing issues in implant failure of orthopedic biomaterials is the toxicity induced by the fine particles released during long term use in vivo, leading to acute inflammatory response. In developing a new class of piezobiocomposite to mimic the integrated electrical and mechanical properties of bone, bone-mimicking physical properties as well as in vitro cytocompatibility properties have been achieved with spark plasma sintered hydroxyapatite (HA)-barium titanate (BaTiO3) composites. However, the presence of BaTiO3 remains a concern towards the potential toxicity effect. To address this issue, present work reports the first result to conclusively confirm the non-toxic effect of HA-BaTiO3 piezobiocomposite nanoparticulates, in vivo. Twenty BALB/c mice were intra-articularly injected at their right knee joints with different concentrations of HA-BaTiO3 composite of up to 25 mg/ml. The histopathological examination confirmed the absence of any trace of injected particles or any sign of inflammatory reaction in the vital organs, such as heart, spleen, kidney and liver at 7 days post-exposure period. Rather, the injected nanoparticulates were found to be agglomerated in the vicinity of the knee joint, surrounded by macrophages. Importantly, the absence of any systemic toxicity response in any of the vital organs in the treated mouse model, other than a mild local response at the site of delivery, was recorded. The serum biochemical analyses using proinflammatory cytokines (TNF-α and IL-1β) also complimented to the non-immunogenic response to injected particulates. Altogether, the absence of any inflammatory/adverse reaction will open up myriad of opportunities for BaTiO3 based piezoelectric implantable devices in biomedical applications.

Method of preparing doped oxide catalysts for lean NOx exhaust

DOEpatents

Park, Paul W.

2004-03-09

The lean NOx catalyst includes a substrate, an oxide support material, preferably .gamma.-alumina deposited on the substrate and a metal or metal oxide promoter or dopant introduced into the oxide support material. The metal promoters or dopants are selected from the group consisting of indium, gallium, tin, silver, germanium, gold, nickel, cobalt, copper, iron, manganese, molybdenum, chromium cerium, and vanadium, and oxides thereof, and any combinations thereof. The .gamma.-alumina preferably has a pore volume of from about 0.5 to about 2.0 cc/g; a surface area of between 80 and 350 m.sup.2 /g; an average pore size diameter of between about 3 to 30 nm; and an impurity level of less than or equal to about 0.2 weight percent. In a preferred embodiment the .gamma.-alumina is prepared by a sol-gel method, with the metal doping of the .gamma.-alumina preferably accomplished using an incipient wetness impregnation technique.

Modeling of the steam hydrolysis in a two-step process for hydrogen production by solar concentrated energy

NASA Astrophysics Data System (ADS)

Valle-Hernández, Julio; Romero-Paredes, Hernando; Pacheco-Reyes, Alejandro

2017-06-01

In this paper the simulation of the steam hydrolysis for hydrogen production through the decomposition of cerium oxide is presented. The thermochemical cycle for hydrogen production consists of the endothermic reduction of CeO2 to lower-valence cerium oxide, at high temperature, where concentrated solar energy is used as a source of heat; and of the subsequent steam hydrolysis of the resulting cerium oxide to produce hydrogen. The modeling of endothermic reduction step was presented at the Solar Paces 2015. This work shows the modeling of the exothermic step; the hydrolysis of the cerium oxide (III) to form H2 and the corresponding initial cerium oxide made at lower temperature inside the solar reactor. For this model, three sections of the pipe where the reaction occurs were considered; the steam water inlet, the porous medium and the hydrogen outlet produced. The mathematical model describes the fluid mechanics; mass and energy transfer occurring therein inside the tungsten pipe. Thermochemical process model was simulated in CFD. The results show a temperature distribution in the solar reaction pipe and allow obtaining the fluid dynamics and the heat transfer within the pipe. This work is part of the project "Solar Fuels and Industrial Processes" from the Mexican Center for Innovation in Solar Energy (CEMIE-Sol).

Effects of the addition of nanoparticulate calcium carbonate on setting time, dimensional change, compressive strength, solubility and pH of MTA.

PubMed

Bernardi, A; Bortoluzzi, E A; Felippe, W T; Felippe, M C S; Wan, W S; Teixeira, C S

2017-01-01

To evaluate nanoparticulate calcium carbonate (NPCC) using transmission electron microscopy and the effects of NPCC addition to MTA in regard to the setting time, dimensional change, compressive strength, solubility and pH. The experimental groups were G1 (MTA), G2 (MTA with 5% NPCC) and G3 (MTA with 10% NPCC). The tests followed ISO and ADA standards. The specimens in the dimensional change and compressive strength tests were measured immediately after setting, after 24 h and after 30 days. In the solubility test, rings filled with cement were weighed after setting and after 30 days. The pH was measured after 24 h and 30 days. The data were analysed with the ANOVA, Tukey's and Kruskal-Wallis tests (α = 5%). The setting time was reduced (P < 0.05) in samples from G2 and G3 compared to G1. After 24 h, the dimensional change was similar amongst the groups, and after 30 days, G2 was associated with less alteration than G1 and G3. There was a difference in the compressive strength (P < 0.001) after 24 h and 30 days (G1 > G2 > G3). The solubility test revealed a difference amongst the groups when the specimens were hydrated: G2 > G1 > G3 and dehydrated: G3 > G2 > G1. The pH of the groups was similar at 24 h with higher values in each group after 30 days (P < 0.05), and G2 and G3 had similar mean pH values but both were higher than G1. Nanoparticulate calcium carbonate had a cubic morphology with few impurities. The addition of nanoparticulate calcium carbonate to MTA accelerated the setting time, decreased compressive strength and, after 30 days, resulted in lower dimensional change (G2), higher solubility and a higher pH. © 2015 International Endodontic Journal. Published by John Wiley & Sons Ltd.

Synergistic properties of graphitic carbon nitride/cerium molybdate nanocomposites for enhanced photocatalytic activity

NASA Astrophysics Data System (ADS)

Bhargava, V. S.; Singh, Gajendar; Sharma, Manu

2018-05-01

A polymeric semiconductor (g-C3N4), based nanocomposites have been achieved much attention due to its excellent thermal, chemical stability and suitable band positions for water splitting. g-C3N4 based nanocomposites show good performance in the field of photocatalysis, sensors, Li-ion batteries, supercapacitors and water purification technology. In this work, a series of novel g-C3N4/CeM nano composites were synthesized using a facile one-step ultra-sonication method. X-ray diffraction (XRD) pattern confirms the formation of g-C3N4 and cerium molybdate. The photocatalytic activity of nanocomposites indicated the substantial degradation of Methylene Blue (MB) dye up to 97% over the surface of g-C3N4/CeM under visible light illumination. All the g-C3N4/CeM composites possess higher photocatalytic activity than pure cerium molybdate. The proposed mechanism demonstrated that the different weight ratios of photocatalyst were most likely attributed to a synergistic effect between g-C3N4 and CeM. This approach is very simple, cost effective, and free from any surfactant that makes it valuable catalyst for various future applications.

Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium-sulfur battery design

NASA Astrophysics Data System (ADS)

Tao, Xinyong; Wang, Jianguo; Liu, Chong; Wang, Haotian; Yao, Hongbin; Zheng, Guangyuan; Seh, Zhi Wei; Cai, Qiuxia; Li, Weiyang; Zhou, Guangmin; Zu, Chenxi; Cui, Yi

2016-04-01

Lithium-sulfur batteries have attracted attention due to their six-fold specific energy compared with conventional lithium-ion batteries. Dissolution of lithium polysulfides, volume expansion of sulfur and uncontrollable deposition of lithium sulfide are three of the main challenges for this technology. State-of-the-art sulfur cathodes based on metal-oxide nanostructures can suppress the shuttle-effect and enable controlled lithium sulfide deposition. However, a clear mechanistic understanding and corresponding selection criteria for the oxides are still lacking. Herein, various nonconductive metal-oxide nanoparticle-decorated carbon flakes are synthesized via a facile biotemplating method. The cathodes based on magnesium oxide, cerium oxide and lanthanum oxide show enhanced cycling performance. Adsorption experiments and theoretical calculations reveal that polysulfide capture by the oxides is via monolayered chemisorption. Moreover, we show that better surface diffusion leads to higher deposition efficiency of sulfide species on electrodes. Hence, oxide selection is proposed to balance optimization between sulfide-adsorption and diffusion on the oxides.

Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium-sulfur battery design.

PubMed

Tao, Xinyong; Wang, Jianguo; Liu, Chong; Wang, Haotian; Yao, Hongbin; Zheng, Guangyuan; Seh, Zhi Wei; Cai, Qiuxia; Li, Weiyang; Zhou, Guangmin; Zu, Chenxi; Cui, Yi

2016-04-05

Lithium-sulfur batteries have attracted attention due to their six-fold specific energy compared with conventional lithium-ion batteries. Dissolution of lithium polysulfides, volume expansion of sulfur and uncontrollable deposition of lithium sulfide are three of the main challenges for this technology. State-of-the-art sulfur cathodes based on metal-oxide nanostructures can suppress the shuttle-effect and enable controlled lithium sulfide deposition. However, a clear mechanistic understanding and corresponding selection criteria for the oxides are still lacking. Herein, various nonconductive metal-oxide nanoparticle-decorated carbon flakes are synthesized via a facile biotemplating method. The cathodes based on magnesium oxide, cerium oxide and lanthanum oxide show enhanced cycling performance. Adsorption experiments and theoretical calculations reveal that polysulfide capture by the oxides is via monolayered chemisorption. Moreover, we show that better surface diffusion leads to higher deposition efficiency of sulfide species on electrodes. Hence, oxide selection is proposed to balance optimization between sulfide-adsorption and diffusion on the oxides.

Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium–sulfur battery design

DOE PAGES

Tao, Xinyong; Wang, Jianguo; Liu, Chong; ...

2016-04-05

Lithium–sulfur batteries have attracted attention due to their six-fold specific energy compared with conventional lithium-ion batteries. Dissolution of lithium polysulfides, volume expansion of sulfur and uncontrollable deposition of lithium sulfide are three of the main challenges for this technology. State-of-the-art sulfur cathodes based on metal-oxide nanostructures can suppress the shuttle-effect and enable controlled lithium sulfide deposition. However, a clear mechanistic understanding and corresponding selection criteria for the oxides are still lacking. Herein, various nonconductive metal-oxide nanoparticle-decorated carbon flakes are synthesized via a facile biotemplating method. The cathodes based on magnesium oxide, cerium oxide and lanthanum oxide show enhanced cycling performance.more » Adsorption experiments and theoretical calculations reveal that polysulfide capture by the oxides is via monolayered chemisorption. Moreover, we show that better surface diffusion leads to higher deposition efficiency of sulfide species on electrodes. Lastly, oxide selection is proposed to balance optimization between sulfide-adsorption and diffusion on the oxides.« less

Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium–sulfur battery design

PubMed Central

Tao, Xinyong; Wang, Jianguo; Liu, Chong; Wang, Haotian; Yao, Hongbin; Zheng, Guangyuan; Seh, Zhi Wei; Cai, Qiuxia; Li, Weiyang; Zhou, Guangmin; Zu, Chenxi; Cui, Yi

2016-01-01

Lithium–sulfur batteries have attracted attention due to their six-fold specific energy compared with conventional lithium-ion batteries. Dissolution of lithium polysulfides, volume expansion of sulfur and uncontrollable deposition of lithium sulfide are three of the main challenges for this technology. State-of-the-art sulfur cathodes based on metal-oxide nanostructures can suppress the shuttle-effect and enable controlled lithium sulfide deposition. However, a clear mechanistic understanding and corresponding selection criteria for the oxides are still lacking. Herein, various nonconductive metal-oxide nanoparticle-decorated carbon flakes are synthesized via a facile biotemplating method. The cathodes based on magnesium oxide, cerium oxide and lanthanum oxide show enhanced cycling performance. Adsorption experiments and theoretical calculations reveal that polysulfide capture by the oxides is via monolayered chemisorption. Moreover, we show that better surface diffusion leads to higher deposition efficiency of sulfide species on electrodes. Hence, oxide selection is proposed to balance optimization between sulfide-adsorption and diffusion on the oxides. PMID:27046216

Development and characterization of polymeric nanoparticulate delivery system for hydrophillic drug: Gemcitabine

NASA Astrophysics Data System (ADS)

Khurana, Jatin

Gemcitabine is a nucleoside analogue, used in various carcinomas such as non small cell lung cancer, pancreatic cancer, ovarian cancer and breast cancer. The major setbacks to the conventional therapy with gemcitabine include its short half-life and highly hydrophilic nature. The objectives of this investigation were to develop and evaluate the physiochemical properties, drug loading and entrapment efficiency, in vitro release, cytotoxicity, and cellular uptake of polymeric nano-particulate formulations containing gemcitabine hydrochloride. The study also entailed development and validation of a high performance liquid chromatography (HPLC) method for the analysis of gemcitabine hydrochloride. A reverse phase HPLC method using a C18 Luna column was developed and validated. Alginate and Poly lactide co glycolide/Poly-epsilon-caprolactone (PLGA:PCL 80:20) nanoparticles were prepared by multiple emulsion-solvent evaporation methodology. An aqueous solution of low viscosity alginate containing gemcitabine was emulsified into 10% solution of dioctyl-sulfosuccinate in dichloro methane (DCM) by sonication. The primary emulsion was then emulsified in 0.5% (w/v) aqueous solution of polyvinyl alcohol (PVA). Calcium chloride solution (60% w/v) was used to cause cross linking of the polymer. For PLGA:PCL system, the polymer mix was dissolved in dichloromethane (DCM) and an aqueous gemcitabine (with and without sodium chloride) was emulsified under ultrasonic conditions (12-watts; 1-min). This primary emulsion was further emulsified in 2% (w/v) PVA under ultrasonic conditions (24-watts; 3-min) to prepare a multiple-emulsion (w/o/w). In both cases DCM, the organic solvent was evaporated (20- hours, magnetic-stirrer) prior to ultracentrifugation (10000-rpm for PLGA:PCL; 25000-rpm for alginate). The pellet obtained was washed thrice with de-ionized water to remove PVA and any free drug and re-centrifuged. The particles were re-suspended in de-ionized water and then lyophilized to

Mixed valency and site-preference chemistry for cerium and its compounds: A predictive density-functional theory study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alam, Aftab; Johnson, Duane D.

Cerium and its technologically relevant compounds are examples of anomalous mixed valency, originating from two competing oxidation states—itinerant Ce4+ and localized Ce3+. Under applied stress, anomalous transitions are observed but not well understood. Here we treat mixed valency as an “alloy” problem involving two valences with competing and numerous site-occupancy configurations. We use density-functional theory with Hubbard U (i.e., DFT+U) to evaluate the effective valence and predict properties, including controlling the valence by pseudoternary alloying. For Ce and its compounds, such as (Ce,La)2(Fe,Co)14B permanent magnets, we find a stable mixed-valent α state near the spectroscopic value of νs=3.53. Ce valencymore » in compounds depends on its steric volume and local chemistry. For La doping, Ce valency shifts towards γ-like Ce3+, as expected from steric volume; for Co doping, valency depends on local Ce-site chemistry and steric volume. Our approach captures the key origins of anomalous valency and site-preference chemistry in complex compounds.« less

IRIS TOXICOLOGICAL REVIEW AND SUMMARY ...

EPA Pesticide Factsheets

Cerium is a member of the lanthanoid series of rare earth metals. It is also the most abundant and most reactive of the rare earth metals. Cerium oxidizes at room temperature and forms a variety of salt compounds including oxides, hydroxides, sulfates and chlorides. Cerium is used in a variety of ways and is present in many products. For example, cerium is used as a catalyst in emission control systems for gasoline engines, and most recently, as a fuel borne catalyst for diesel engines. In addition, cerium is found in carbon arc lamps, the polishing of lens and mirrors, high temperature ceramics, and the printing and lithographic industries. Cerium is released to the environment as salt compounds from the various uses listed above. This assessment will present reference values for the noncancer effects (RfD and RfC), where supported by the available data, and a cancer evaluation of cerium and cerium compounds. The assessment will be subject to internal review and external peer review along with Agency review. The final product will reflect the Agency's opinion on the toxicity of Cerium and cerium compounds. The U.S. EPA is conducting a new health assessment of cerium (stable) and compounds that will appear on the Agency's online database, the Integrated Risk Information System (IRIS). IRIS is an EPA database containing Agency scientific positions on potential adverse human health effects that may result from chronic (or lifetime) exposure to chemicals i

Cerium and zinc: Dual-doped LiMn 2O 4 spinels as cathode material for use in lithium rechargeable batteries

NASA Astrophysics Data System (ADS)

Thirunakaran, R.; Sivashanmugam, A.; Gopukumar, S.; Rajalakshmi, R.

Pristine spinel lithium manganese oxide (LiMn 2O 4) and zinc- and cerium-doped lithium manganese oxide [LiZn xCe yMn 2- x- yO 4 (x = 0.01-0.10; y = 0.10-0.01)] are synthesized for the first time via the sol-gel route using p-amino benzoic acid as a chelating agent to obtain micron-sized particles and enhanced electrochemical performance. The sol-gel route offers shorter heating time, better homogeneity and control over stoichiometry. The resulting spinel product is characterized through various methods such as thermogravimetic and differential thermal analysis (TG/DTA), Fourier-transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDAX) and electrochemical galvanostatic cycling studies. Charge-discharge studies of LiMn 2O 4 samples heated at 850 °C exhibit a discharge capacity of 122 mAh g -1 and a corresponding 99% coulombic efficiency in the 1st cycle. The discharge capacity and cycling performance of LiZn 0.01Ce 0.01Mn 1.98O 4 is found to be superior (124 mAh g -1), with a low capacity fade (0.1 mAh g -1 cycle -1) over the investigated 10 cycles.

Destruction of organic pollutants by cerium(IV) MEO process: a study on the influence of process conditions for EDTA mineralization.

PubMed

Balaji, Subramanian; Chung, Sang Joon; Matheswaran, Manickam; Vasilivich, Kokovkin Vasily; Moon, Il Shik

2008-02-11

The mediated electrochemical oxidation (MEO) process with cerium(IV) and nitric acid as the oxidizing medium was employed for the destruction of various model organic pollutants in continuous organic feeding mode. A near complete destruction was observed for all the organics studied. The effects of various experimental conditions were evaluated with respect to EDTA mineralization. The key parameters varied in the process were concentration of EDTA (67-268 mM), temperature (70, 80 and 95 degrees C), concentrations of Ce(IV) (0.7, 0.8 and 0.95 M), nitric acid (2, 3 and 4M) and duration of organic addition (30 and 120 min). Under the experimental conditions of 80 degrees C and 0.95 M Ce(IV) in 3 M nitric acid, nearly 90% destruction was achieved based on CO(2) production and 95% based on TOC analyses for all the organic compounds studied. The in situ regeneration of mediator ion by the electrochemical cell was found to be good during the organic destruction within the range of experimental conditions studied. In the case of long term organic feeding (120 min) the destruction was calculated after the CO(2) evolution attained the steady state and under this condition the destruction efficiency was found to be 85% based on CO(2) evolution.

Modeling of a CeO2 thermochemistry reduction process for hydrogen production by solar concentrated energy

NASA Astrophysics Data System (ADS)

Valle-Hernández, Julio; Romero-Paredes, Hernando; Arancibia-Bulnes, Camilo A.; Villafan-Vidales, Heidi I.; Espinosa-Paredes, Gilberto

2016-05-01

In this paper the simulation of the thermal reduction for hydrogen production through the decomposition of cerium oxide is presented. The thermochemical cycle for hydrogen production consists of the endothermic reduction of CeO2 at high temperature, where concentrated solar energy is used as a source of heat; and of the subsequent steam hydrolysis of the resulting cerium oxide to produce hydrogen. For the thermochemical process, a solar reactor prototype is proposed; consisting of a cubic receptacle made of graphite fiber thermally insulated. Inside the reactor a pyramidal arrangement with nine tungsten pipes is housed. The pyramidal arrangement is made respect to the focal point where the reflected energy is concentrated. The solar energy is concentrated through the solar furnace of high radiative flux. The endothermic step is the reduction of the cerium oxide to lower-valence cerium oxide, at very high temperature. The exothermic step is the hydrolysis of the cerium oxide (III) to form H2 and the corresponding initial cerium oxide made at lower temperature inside the solar reactor. For the modeling, three sections of the pipe where the reaction occurs were considered; the carrier gas inlet, the porous medium and the reaction products outlet. The mathematical model describes the fluid mechanics; mass and energy transfer occurring therein inside the tungsten pipe. Thermochemical process model was simulated in CFD. The results show a temperature distribution in the solar reaction pipe and allow obtaining the fluid dynamics and the heat transfer within the pipe. This work is part of the project "Solar Fuels and Industrial Processes" from the Mexican Center for Innovation in Solar Energy (CEMIE-Sol).

Determination of thorium and of rare earth elements in cerium earth minerals and ores

USGS Publications Warehouse

Carron, M.K.; Skinner, D.L.; Stevens, R.E.

1955-01-01

The conventional oxalate method for precipitating thorium and the rare earth elements in acid solution exhibits definite solubilities of these elements. The present work was undertaken to establish conditions overcoming these solubilities and to find optimum conditions for precipitating thorium and the rare earth elements as hydroxides and sebacates. The investigations resulted in a reliable procedure applicable to samples in which the cerium group elements predominate. The oxalate precipitations are made from homogeneous solution at pH 2 by adding a prepared solution of anhydrous oxalic acid in methanol instead of the more expensive crystalline methyl oxalate. Calcium is added as a carrier. Quantitative precipitation of thorium and the rare earth elements is ascertained by further small additions of calcium to the supernatant liquid, until the added calcium precipitates as oxalate within 2 minutes. Calcium is removed by precipitating the hydroxides of thorium and rare earths at room temperature by adding ammonium hydroxide to pH > 10. Thorium is separated as the sebacate at pH 2.5, and the rare earths are precipitated with ammonium sebacate at pH 9. Maximum errors for combined weights of thorium and rare earth oxides on synthetic mixtures are ??0.6 mg. Maximum error for separated thoria is ??0.5 mg.

Investigation of a new pH-responsive nanoparticulate pore former for controlled release enteric coating with improved processability and stability.

PubMed

Chen, Kuan; Chang, Hao Han R; Shalviri, Alireza; Li, Jason; Lugtu-Pe, Jamie Anne; Kane, Anil; Wu, Xiao Yu

2017-11-01

Water-soluble polymers are often used as pore formers to tailor permeability of film-forming hydrophobic polymers on coated dosage forms. However, their addition to a coating formulation could significantly increase the viscosity thus making the coating process difficult. Moreover, the dissolution of pore formers after oral administration could compromise film integrity resulting in undesirable, inconsistent release profiles. Therefore, a non-leaching, pH-responsive nanoparticulate pore former is proposed herein to preserve film integrity and maintain pH-dependent permeability. Poly(methacrylic acid)-polysorbate 80-grafted-starch terpolymer nanoparticles (TPNs) were incorporated within an ethylcellulose (EC) film (TPN-EC) by casting or spray coating. TPNs at 10%wt (pore former level) only increased viscosity of EC coating suspension slightly while conventional pore formers increased the viscosity by 490-11,700%. Negligible leaching of TPNs led to superior mechanical properties of TPN-EC films compared to Eudragit® L-EC films. As pH increased from 1.2 to 6.8, TPN-EC films with 10% pore former level exhibited an 8-fold higher diltiazem permeability compared to Eudragit® L-EC films. The pH-dependent drug release kinetics of diltiazem HCl beads coated with TPN-EC films was tunable by adjusting the pore former level. These results suggest that the TPNs are promising pH-sensitive nanoparticulate pore formers in EC-coated dosage forms. Copyright © 2017 Elsevier B.V. All rights reserved.

An artificial photosynthesis anode electrode composed of a nanoparticulate photocatalyst film in a visible light responsive GaN-ZnO solid solution system

NASA Astrophysics Data System (ADS)

Imanaka, Yoshihiko; Anazawa, Toshihisa; Manabe, Toshio; Amada, Hideyuki; Ido, Sachio; Kumasaka, Fumiaki; Awaji, Naoki; Sánchez-Santolino, Gabriel; Ishikawa, Ryo; Ikuhara, Yuichi

2016-10-01

The artificial photosynthesis technology known as the Honda-Fujishima effect, which produces oxygen and hydrogen or organic energy from sunlight, water, and carbon dioxide, is an effective energy and environmental technology. The key component for the higher efficiency of this reaction system is the anode electrode, generally composed of a photocatalyst formed on a glass substrate from electrically conductive fluorine-doped tin oxide (FTO). To obtain a highly efficient electrode, a dense film composed of a nanoparticulate visible light responsive photocatalyst that usually has a complicated multi-element composition needs to be deposited and adhered onto the FTO. In this study, we discovered a method for controlling the electronic structure of a film by controlling the aerosol-type nanoparticle deposition (NPD) condition and thereby forming films of materials with a band gap smaller than that of the prepared raw material powder, and we succeeded in extracting a higher current from the anode electrode. As a result, we confirmed that a current approximately 100 times larger than those produced by conventional processes could be obtained using the same material. This effect can be expected not only from the materials discussed (GaN-ZnO) in this paper but also from any photocatalyst, particularly materials of solid solution compositions.

An artificial photosynthesis anode electrode composed of a nanoparticulate photocatalyst film in a visible light responsive GaN-ZnO solid solution system

PubMed Central

Imanaka, Yoshihiko; Anazawa, Toshihisa; Manabe, Toshio; Amada, Hideyuki; Ido, Sachio; Kumasaka, Fumiaki; Awaji, Naoki; Sánchez-Santolino, Gabriel; Ishikawa, Ryo; Ikuhara, Yuichi

2016-01-01

The artificial photosynthesis technology known as the Honda-Fujishima effect, which produces oxygen and hydrogen or organic energy from sunlight, water, and carbon dioxide, is an effective energy and environmental technology. The key component for the higher efficiency of this reaction system is the anode electrode, generally composed of a photocatalyst formed on a glass substrate from electrically conductive fluorine-doped tin oxide (FTO). To obtain a highly efficient electrode, a dense film composed of a nanoparticulate visible light responsive photocatalyst that usually has a complicated multi-element composition needs to be deposited and adhered onto the FTO. In this study, we discovered a method for controlling the electronic structure of a film by controlling the aerosol-type nanoparticle deposition (NPD) condition and thereby forming films of materials with a band gap smaller than that of the prepared raw material powder, and we succeeded in extracting a higher current from the anode electrode. As a result, we confirmed that a current approximately 100 times larger than those produced by conventional processes could be obtained using the same material. This effect can be expected not only from the materials discussed (GaN-ZnO) in this paper but also from any photocatalyst, particularly materials of solid solution compositions. PMID:27759108

Synthesis and characterization of nanoparticulate MnS within the pores of mesoporous silica

NASA Astrophysics Data System (ADS)

Barry, Louse; Copley, Mark; Holmes, Justin D.; Otway, David J.; Kazakova, Olga; Morris, Michael A.

2007-12-01

Mesoporous silica was loaded with nanoparticulate MnS via a simple post-synthesis treatment. The mesoporous material that still contained surfactant was passivated to prevent MnS formation at the surface. The surfactant was extracted and a novel manganese ethylxanthate was used to impregnate the pore network. This precursor thermally decomposes to yield MnS particles that are smaller or equal to the pore size. The particles exhibit all three common polymorphs. The passivation treatment is most effective at lower loadings because at the highest loadings (SiO 2:MnS molar ratio of 6:1) large particles (>50 nm) form at the exterior of the mesoporous particles. The integrity of the mesoporous network is maintained through the preparation and high order is maintained. The MnS particles exhibit unexpected ferromagnetism at low temperatures. Strong luminescence of these samples is observed and this suggests that they may have a range of important application areas.

Relative contributions of copper oxide nanoparticles and dissolved copper to Cu uptake kinetics of Gulf killifish (Fundulus grandis) embryos

USGS Publications Warehouse

Jiang, Chuanjia; Castellon, Benjamin T.; Matson, Cole W.; Aiken, George R.; Hsu-Kim, Heileen

2017-01-01

The toxicity of soluble metal-based nanomaterials may be due to the uptake of metals in both dissolved and nanoparticulate forms, but the relative contributions of these different forms to overall metal uptake rates under environmental conditions are not quantitatively defined. Here, we investigated the linkage between the dissolution rates of copper(II) oxide (CuO) nanoparticles (NPs) and their bioavailability to Gulf killifish (Fundulus grandis) embryos, with the aim of quantitatively delineating the relative contributions of nanoparticulate and dissolved species for Cu uptake. Gulf killifish embryos were exposed to dissolved Cu and CuO NP mixtures comprising a range of pH values (6.3–7.5) and three types of natural organic matter (NOM) isolates at various concentrations (0.1–10 mg-C L–1), resulting in a wide range of CuO NP dissolution rates that subsequently influenced Cu uptake. First-order dissolution rate constants of CuO NPs increased with increasing NOM concentration and for NOM isolates with higher aromaticity, as indicated by specific ultraviolet absorbance (SUVA), while Cu uptake rate constants of both dissolved Cu and CuO NP decreased with NOM concentration and aromaticity. As a result, the relative contribution of dissolved Cu and nanoparticulate CuO species for the overall Cu uptake rate was insensitive to NOM type or concentration but largely determined by the percentage of CuO that dissolved. These findings highlight SUVA and aromaticity as key NOM properties affecting the dissolution kinetics and bioavailability of soluble metal-based nanomaterials in organic-rich waters. These properties could be used in the incorporation of dissolution kinetics into predictive models for environmental risks of nanomaterials.

PURIFICATION OF PLUTONIUM USING A CERIUM PRECIPITATE AS A CARRIER FOR FISSION PRODUCTS

DOEpatents

Faris, B.F.; Olson, C.M.

1961-07-01

Bismuth phosphate carrier precipitation processes are described for the separation of plutonium from fission products wherein in at least one step bismuth phosphate is precipitated in the presence of hexavalent plutonium thereby carrying a portion of the fission products from soluble plu tonium values. In this step, a cerium phosphate precipitate is formed in conjunction with the bismuth phosphate precipitate, thereby increasing the amount of fission products removed from solution.

Observations on the microvasculature of bone defects filled with biodegradable nanoparticulate hydroxyapatite.

PubMed

Kilian, Olaf; Wenisch, Sabine; Karnati, Srikanth; Baumgart-Vogt, Eveline; Hild, Anne; Fuhrmann, Rosemarie; Jonuleit, Tarja; Dingeldein, Elvira; Schnettler, Reinhard; Franke, Ralf-Peter

2008-01-01

The microvascularization of metaphyseal bone defects filled with nanoparticulate, biodegradable hydroxyapatite biomaterial with and without platelet factors enrichment was investigated in a minipig model. Results from morphological analysis and PECAM-1 immunohistochemistry showed the formation of new blood vessels into the bone defects by sprouting and intussusception of pre-existing ones. However, no significant differences were observed in the microvascularization of the different biomaterials applied (pure versus platelet factors-enriched hydroxyapatite), concerning the number of vessels and their morphological structure at day 20 after operation. The appearance of VEGFR-2 positive endothelial progenitor cells in the connective tissue between hydroxyapatite particles was also found to be independent from platelet factors enrichment of the hydroxyapatite bone substitute. In both groups formation of lymphatic vessels was detected with a podoplanin antibody. No differences were noted between HA/PLF- and HA/PLF+ implants with respect to the podoplanin expression level, the staining pattern or number of lymphatic vessels. In conclusion, the present study demonstrates different mechanisms of blood and lymphatic vessel formation in hydroxyapatite implants in minipigs.

Ab initio MCHF structural calculations of Mg-like cerium

NASA Astrophysics Data System (ADS)

Wajid, Abdul; Jabeen, S.; Husain, Abid

2018-05-01

Energy levels and emission line wavelengths of high-Z materials are useful for impurity diagnostics in the next generation fusion devices. For this here we have calculated E1, M2 transitions, oscillator strengths, and transition probabilities for transitions among the terms belonging to the 2p63s2, 2p63s3p, 2p63p2 and 2p63s3d for the Magnesium like cerium (Ce XLVII) using the GRASP2K package based on the fully relativistic multi-configuration Dirac-Fock method. The electron correlation effects, Breit interaction and quantum electrodynamics effects to the atomic state wave functions and the corresponding energies have been taken into account.

Distribution and size fractionation of elemental sulfur in aqueous environments: The Chesapeake Bay and Mid-Atlantic Ridge

NASA Astrophysics Data System (ADS)

Findlay, Alyssa J.; Gartman, Amy; MacDonald, Daniel J.; Hanson, Thomas E.; Shaw, Timothy J.; Luther, George W.

2014-10-01

Elemental sulfur is an important intermediate of sulfide oxidation and may be produced via abiotic and biotic pathways. In this study the concentration and size fractionation of elemental sulfur were measured in two different sulfidic marine environments: the Chesapeake Bay and buoyant hydrothermal vent plumes along the Mid-Atlantic Ridge. Nanoparticulate sulfur (<0.2 μm) was found to comprise up to 90% of the total elemental sulfur in anoxic deep waters of the Chesapeake Bay. These data were compared with previous studies of elemental sulfur, and represent one of the few reports of nanoparticulate elemental sulfur in the environment. Additionally, a strain of phototrophic sulfide oxidizing bacteria isolated from the Chesapeake Bay was shown to produce elemental sulfur as a product of sulfide oxidation. Elemental sulfur concentrations are also presented from buoyant hydrothermal vent plumes located along the Mid-Atlantic Ridge. In the Mid-Atlantic Ridge plume, S0 concentrations up to 33 μM were measured in the first meter of rising plumes at three different vent sites, and nanoparticulate S0 was up to 44% of total elemental sulfur present.

Polymorphic Transitions in Cerium-Substituted Zirconolite (CaZrTi 2O 7)

DOE PAGES

Clark, Braeden M.; Sundaram, S. K.; Misture, Scott T.

2017-07-19

Compounds with the formulae CaZr 1–xCe xTi 2O 7 with x = 0.1–0.5 were synthesized by solid state reaction. Cerium was used as a surrogate for actinide elements. A transition from the 2M polymorph to the 4M polymorph (expanded unit cell due to cation ordering) in zirconolite was observed with increasing cerium content. The presence of both tri- and tetravalent Ce, contrary to formulation, was confirmed using X-ray absorption near edge spectroscopy, suggesting substitution on both Ca and Zr sites. Sintering was carried out via spark plasma sintering, during which the perovskite phase (Ca 0.4Ce 0.4TiO 3) was stabilized duemore » to the reducing conditions of this technique. Scanning electron microscopy and energy dispersive spectrometry revealed that the 2M polymorph was dilute in Ce content in comparison to the 4M-zirconolite. High temperature X-ray diffraction was used to detail the kinetics of perovskite to zirconolite transition. It was found that CaCeTi 2O 7 (cubic pyrochlore) formed as an intermediate phase during the transition. Lastly, our results show that a transition from 2M- to 4M-zirconolite occurs with increasing Ce content and can be controlled by adjusting the P O2 and the heat treatment temperature.« less

Polymorphic Transitions in Cerium-Substituted Zirconolite (CaZrTi 2O 7)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Clark, Braeden M.; Sundaram, S. K.; Misture, Scott T.

Compounds with the formulae CaZr 1–xCe xTi 2O 7 with x = 0.1–0.5 were synthesized by solid state reaction. Cerium was used as a surrogate for actinide elements. A transition from the 2M polymorph to the 4M polymorph (expanded unit cell due to cation ordering) in zirconolite was observed with increasing cerium content. The presence of both tri- and tetravalent Ce, contrary to formulation, was confirmed using X-ray absorption near edge spectroscopy, suggesting substitution on both Ca and Zr sites. Sintering was carried out via spark plasma sintering, during which the perovskite phase (Ca 0.4Ce 0.4TiO 3) was stabilized duemore » to the reducing conditions of this technique. Scanning electron microscopy and energy dispersive spectrometry revealed that the 2M polymorph was dilute in Ce content in comparison to the 4M-zirconolite. High temperature X-ray diffraction was used to detail the kinetics of perovskite to zirconolite transition. It was found that CaCeTi 2O 7 (cubic pyrochlore) formed as an intermediate phase during the transition. Lastly, our results show that a transition from 2M- to 4M-zirconolite occurs with increasing Ce content and can be controlled by adjusting the P O2 and the heat treatment temperature.« less

Effect of oxidizing adulterants on human urinary steroid profiles.

PubMed

Kuzhiumparambil, Unnikrishnan; Fu, Shanlin

2013-02-01

Steroid profiling is the most versatile and informative technique adapted by doping control laboratories for detection of steroid abuse. The absolute concentrations and ratios of endogenous steroids including testosterone, epitestosterone, androsterone, etiocholanolone, 5α-androstane-3α,17β-diol and 5β-androstane-3α,17β-diol constitute the significant characteristics of a steroid profile. In the present study we report the influence of various oxidizing adulterants on the steroid profile of human urine. Gas chromatography-mass spectrometry analysis was carried out to develop the steroid profile of human male and female urine. Oxidants potassium nitrite, sodium hypochlorite, potassium permanganate, cerium ammonium nitrate, sodium metaperiodate, pyridinium chlorochromate, potassium dichromate and potassium perchlorate were reacted with urine at various concentrations and conditions and the effect of these oxidants on the steroid profile were analyzed. Most of the oxidizing chemicals led to significant changes in endogenous steroid profile parameters which were considered stable under normal conditions. These oxidizing chemicals can cause serious problems regarding the interpretation of steroid profiles and have the potential to act as masking agents that can complicate or prevent the detection of the steroid abuse. Copyright © 2012 Elsevier Inc. All rights reserved.

Elastic Properties across the y→α Volume Collapse in Cerium versus Pressure and Temperature

DOE PAGES

Lipp, M. J.; Jenei, Zs.; Cynn, H.; ...

2017-10-31

Here, the longitudinal and transverse sound speeds, c L and c T, of polycrystalline cerium were measured isothermally vs pressure up to the critical temperature across the iso-structural γ-α volume collapse (VC) phase transition. We deduce values for the adiabatic bulk modulus BS, the shear modulus G = ρc T 2, the Poisson’s ratio ν and the Debye temperature, θ D(p). We find that the elastic constant C 12 is solely responsible for the decrease of B S with pressure towards the VC at RT. With increasing temperature, the lattice contribution ΔS vib(γ→α) to the total entropy change across themore » VC decreases more rapidly to zero than the total entropy itself suggesting that another mechanism, possibly disorder, assists in stabilizing the γ-phase entropically against the α-phase. Also, with increasing temperature, the Poisson’s ratio becomes negative near the VC transition, meaning that cerium metal takes on auxetic characteristics over a small pressure range. At the critical point the Poisson’s ratio ought to be -1, since the isothermal bulk modulus vanishes and the shear modulus remains nonzero.« less

Elastic Properties across the y→α Volume Collapse in Cerium versus Pressure and Temperature

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lipp, M. J.; Jenei, Zs.; Cynn, H.

Here, the longitudinal and transverse sound speeds, c L and c T, of polycrystalline cerium were measured isothermally vs pressure up to the critical temperature across the iso-structural γ-α volume collapse (VC) phase transition. We deduce values for the adiabatic bulk modulus BS, the shear modulus G = ρc T 2, the Poisson’s ratio ν and the Debye temperature, θ D(p). We find that the elastic constant C 12 is solely responsible for the decrease of B S with pressure towards the VC at RT. With increasing temperature, the lattice contribution ΔS vib(γ→α) to the total entropy change across themore » VC decreases more rapidly to zero than the total entropy itself suggesting that another mechanism, possibly disorder, assists in stabilizing the γ-phase entropically against the α-phase. Also, with increasing temperature, the Poisson’s ratio becomes negative near the VC transition, meaning that cerium metal takes on auxetic characteristics over a small pressure range. At the critical point the Poisson’s ratio ought to be -1, since the isothermal bulk modulus vanishes and the shear modulus remains nonzero.« less

Alkali metal hafnium oxide scintillators

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bourret-Courchesne, Edith; Derenzo, Stephen E.; Taylor, Scott Edward

The present invention provides for a composition comprising an inorganic scintillator comprising an alkali metal hafnate, optionally cerium-doped, having the formula A 2HfO 3:Ce; wherein A is an alkali metal having a valence of 1, such as Li or Na; and the molar percent of cerium is 0% to 100%. The alkali metal hafnate are scintillators and produce a bright luminescence upon irradiation by a suitable radiation.

Effect of the conditions of REM microalloying of steel on the corrosion activity of nonmetallic inclusions

NASA Astrophysics Data System (ADS)

Movenko, D. A.; Kotel'nikov, G. I.; Pavlov, A. V.; Bytsenko, O. A.

2015-11-01

Experimental heats of low-alloy steel are performed under various conditions of rare-earth metal microalloying and aluminum and calcium deoxidation. Electron-probe microanalysis of nonmetallic inclusions and a metallographic investigation of a metal are used to show that, when interacting with water, nonmetallic cerium oxide inclusions do not form hydrates and, correspondingly, are not aggressive. When aluminum, calcium, and cerium additions are sequentially introduced into a melt, a continuous cerium oxide shell forms on calcium aluminates, protects corrosive nonmetallic inclusions against interaction with water, and weakens local metal corrosion.

Effect of Cerium Doped on the Poly(3-(Trimethoxysilyl)propyl methacrylate) Characteristic as Corrosion Protection Material of Carbon Steel

NASA Astrophysics Data System (ADS)

Rochmah, D. N.; Syakir, N.; Susilawati, T.; Suryaningsih, S.; Fitrilawati

2017-05-01

The hybrid polymer precursor was synthesized from monomer of 3-(trimethoxysilyl) propyl methacrylate (TMSPMA) using sol-gel method and doped with inhibitor of Cerium Nitrate Hexahydrate with a concentration of 0.2%. The synthesized material was coated on a carbon steel surface by solution casting technique and followed by a photopolymerisation process. Corrosion tests were performed by using Electrochemical Impedance Spectroscopy (EIS) in 3.5% NaCl at the critical temperature of 75°C. Result of EIS data and their fitting analysis using an equivalent circuit model shows that a coating of poly(TMSPMA)-Cerium on the surface of carbon steel form a layer of protection and caused increasing of impedance value significantly. The impedance is higher compared to the carbon steel that coated with poly(TMSPMA) only.

A systematic review on the efficiency of cerium-impregnated activated carbons for the removal of gas-phase, elemental mercury from flue gas.

PubMed

Sowlat, Mohammad Hossein; Kakavandi, Babak; Lotfi, Saeedeh; Yunesian, Masud; Abdollahi, Mohammad; Rezaei Kalantary, Roshanak

2017-05-01

In the present systematic review, we aimed to collect and analyze all the relevant evidence on the efficiency of cerium-impregnated versus virgin-activated carbons (ACs) for the removal of gas-phase elemental mercury (Hg 0 ) from the flue gas of coal-fired power plants and to assess the effect of different calcination and operational parameters on their efficiency. A total of eight relevant papers (out of 1193 hits produced by the search) met the eligibility criteria and were included in the study. Results indicated that the Hg 0 adsorption capacity of cerium-impregnated ACs is significantly higher than that of virgin ACs, depending highly on the impregnation and operational parameters. It was noticed that although cerium-impregnated ACs possessed smaller surface areas and pore volumes, their Hg 0 removal efficiencies were still higher than their virgin counterparts. An increased Hg 0 removal efficiency was in general found by increasing the operational adsorption temperature as high as 150-170 °C. Studies also indicated that NO, SO 2 , and HCl have promoting impacts on the Hg 0 removal efficiency of Ce-impregnated ACs, while H 2 O has an inhibitory effect.

Iridium-Doped Ruthenium Oxide Catalyst for Oxygen Evolution

NASA Technical Reports Server (NTRS)

Valdez, Thomas I.; Narayan, Sri R.; Billings, Keith J.

2011-01-01

NASA requires a durable and efficient catalyst for the electrolysis of water in a polymer-electrolyte-membrane (PEM) cell. Ruthenium oxide in a slightly reduced form is known to be a very efficient catalyst for the anodic oxidation of water to oxygen, but it degrades rapidly, reducing efficiency. To combat this tendency of ruthenium oxide to change oxidation states, it is combined with iridium, which has a tendency to stabilize ruthenium oxide at oxygen evolution potentials. The novel oxygen evolution catalyst was fabricated under flowing argon in order to allow the iridium to preferentially react with oxygen from the ruthenium oxide, and not oxygen from the environment. Nanoparticulate iridium black and anhydrous ruthenium oxide are weighed out and mixed to 5 18 atomic percent. They are then heat treated at 300 C under flowing argon (in order to create an inert environment) for a minimum of 14 hours. This temperature was chosen because it is approximately the creep temperature of ruthenium oxide, and is below the sintering temperature of both materials. In general, the temperature should always be below the sintering temperature of both materials. The iridium- doped ruthenium oxide catalyst is then fabricated into a PEM-based membrane- electrode assembly (MEA), and then mounted into test cells. The result is an electrolyzer system that can sustain electrolysis at twice the current density, and at the same efficiency as commercial catalysts in the range of 100-200 mA/sq cm. At 200 mA/sq cm, this new system operates at an efficiency of 85 percent, which is 2 percent greater than commercially available catalysts. Testing has shown that this material is as stable as commercially available oxygen evolution catalysts. This means that this new catalyst can be used to regenerate fuel cell systems in space, and as a hydrogen generator on Earth.

Microstructures and Nanostructures for Environmental Carbon Nanotubes and Nanoparticulate Soots

PubMed Central

Murr, L. E.

2008-01-01

This paper examines the microstructures and nanostructures for natural (mined) chrysotile asbestos nanotubes (Mg3 Si2O5 (OH)4) in comparison with commercial multiwall carbon nanotubes (MWCNTs), utilizing scanning and transmission electron microscopy (SEM and TEM). Black carbon (BC) and a variety of specific soot particulate (aggregate) microstructures and nanostructures are also examined comparatively by SEM and TEM. A range of MWCNTs collected in the environment (both indoor and outdoor) are also examined and shown to be similar to some commercial MWCNTs but to exhibit a diversity of microstructures and nanostructures, including aggregation with other multiconcentric fullerenic nanoparticles. MWCNTs formed in the environment nucleate from special hemispherical graphene “caps” and there is evidence for preferential or energetically favorable chiralities, tube growth, and closing. The multiconcentric graphene tubes (∼5 to 50 nm diameter) differentiate themselves from multiconcentric fullerenic nanoparticles and especially turbostratic BC and carbonaceous soot nanospherules (∼8 to 80 nm diameter) because the latter are composed of curved graphene fragments intermixed or intercalated with polycyclic aromatic hydrocarbon (PAH) isomers of varying molecular weights and mass concentrations; depending upon combustion conditions and sources. The functionalizing of these nanostructures and photoxidation and related photothermal phenomena, as these may influence the cytotoxicities of these nanoparticulate aggregates, will also be discussed in the context of nanostructures and nanostructure phenomena, and implications for respiratory health. PMID:19151426

Coated silicon comprising material for protection against environmental corrosion

NASA Technical Reports Server (NTRS)

Hazel, Brian Thomas (Inventor)

2009-01-01

In accordance with an embodiment of the invention, an article is disclosed. The article comprises a gas turbine engine component substrate comprising a silicon material; and an environmental barrier coating overlying the substrate, wherein the environmental barrier coating comprises cerium oxide, and the cerium oxide reduces formation of silicate glass on the substrate upon exposure to corrodant sulfates.

Synthesis & characterization of Bi7.38Ce0.62O12.3 and its optical and electrocatalytic property

NASA Astrophysics Data System (ADS)

Padmanaban, A.; Dhanasekaran, T.; Kumar, S. Praveen; Gnanamoorthy, G.; Stephen, A.; Narayanan, V.

2017-05-01

Bismuth cerium oxide was synthesized by thermal decomposition method. The material was characterized by X-ray diffraction technique, DRS UV-Vis, Raman spectral methods and FE-SEM. The electrocatalytic sensing activity of bismuth cerium oxide modified GCE toward 4-nitrophenol exhibits better activity than the bare GCE. The modified electrode shows higher anodic current response with lower potential.

Protective interlayer for high temperature solid electrolyte electrochemical cells

DOEpatents

Singh, P.; Vasilow, T.R.; Richards, V.L.

1996-05-14

The invention is comprised of an electrically conducting doped or admixed cerium oxide composition with niobium oxide and/or tantalum oxide for electrochemical devices, characterized by the general formula: Nb{sub x}Ta{sub y}Ce{sub 1{minus}x{minus}y}O{sub 2} where x is about 0.0 to 0.05, y is about 0.0 to 0.05, and x+y is about 0.02 to 0.05, and where x is preferably about 0.02 to 0.05 and y is 0, and a method of making the same is also described. This novel composition is particularly applicable in forming a protective interlayer of a high temperature, solid electrolyte electrochemical cell, characterized by a first electrode; an electrically conductive interlayer of niobium and/or tantalum doped cerium oxide deposited over at least a first portion of the first electrode; an interconnect deposited over the interlayer; a solid electrolyte deposited over a second portion of the first electrode, the first portion being discontinuous from the second portion; and, a second electrode deposited over the solid electrolyte. The interlayer is characterized as being porous and selected from the group consisting of niobium doped cerium oxide, tantalum doped cerium oxide, and niobium and tantalum doped cerium oxide or admixtures of the same. The first electrode, an air electrode, is a porous layer of doped lanthanum manganite, the solid electrolyte layer is a dense yttria stabilized zirconium oxide, the interconnect layer is a dense, doped lanthanum chromite, and the second electrode, a fuel electrode, is a porous layer of nickel-zirconium oxide cermet. The electrochemical cell can take on a plurality of shapes such as annular, planar, etc. and can be connected to a plurality of electrochemical cells in series and/or in parallel to generate electrical energy. 5 figs.

Protective interlayer for high temperature solid electrolyte electrochemical cells

DOEpatents

Singh, Prabhakar; Vasilow, Theodore R.; Richards, Von L.

1996-01-01

The invention comprises of an electrically conducting doped or admixed cerium oxide composition with niobium oxide and/or tantalum oxide for electrochemical devices, characterized by the general formula: Nb.sub.x Ta.sub.y Ce.sub.1-x-y O.sub.2 where x is about 0.0 to 0.05, y is about 0.0 to 0.05, and x+y is about 0.02 to 0.05, and where x is preferably about 0.02 to 0.05 and y is 0, and a method of making the same. This novel composition is particularly applicable in forming a protective interlayer of a high temperature, solid electrolyte electrochemical cell (10), characterized by a first electrode (12); an electrically conductive interlayer (14) of niobium and/or tantalum doped cerium oxide deposited over at least a first portion (R) of the first electrode; an interconnect (16) deposited over the interlayer; a solid electrolyte (18) deposited over a second portion of the first electrode, the first portion being discontinuous from the second portion; and, a second electrode (20) deposited over the solid electrolyte. The interlayer (14) is characterized as being porous and selected from the group consisting of niobium doped cerium oxide, tantalum doped cerium oxide, and niobium and tantalum doped cerium oxide or admixtures of the same. The first electrode (12), an air electrode, is a porous layer of doped lanthanum manganite, the solid electrolyte layer (18) is a dense yttria stabilized zirconium oxide, the interconnect layer (16) is a dense, doped lanthanum chromite, and the second electrode (20), a fuel electrode, is a porous layer of nickel-zirconium oxide cermet. The electrochemical cell (10) can take on a plurality of shapes such as annular, planar, etc. and can be connected to a plurality of electrochemical cells in series and/or in parallel to generate electrical energy.

Zebrafish as an early stage screening tool to study the systemic circulation of nanoparticulate drug delivery systems in vivo.

PubMed

Sieber, Sandro; Grossen, Philip; Detampel, Pascal; Siegfried, Salome; Witzigmann, Dominik; Huwyler, Jörg

2017-10-28

Nanomedicines have gained much attention for the delivery of small molecules or nucleic acids as treatment options for many diseases. However, the transfer from experimental systems to in vivo applications remains a challenge since it is difficult to assess their circulation behavior in the body at an early stage of drug discovery. Thus, innovative and improved concepts are urgently needed to overcome this issue and to close the gap between empiric nanoparticle design, in vitro assessment, and first in vivo experiments using rodent animal models. This study was focused on the zebrafish as a vertebrate screening model to assess the circulation in blood and extravasation behavior of nanoparticulate drug delivery systems in vivo. To validate this novel approach, monodisperse preparations of fluorescently labeled liposomes with similar size and zeta potential were injected into transgenic zebrafish lines expressing green fluorescent protein in their vasculature. Phosphatidylcholine-based lipids differed by fatty acid chain length and saturation. Circulation behavior and vascular distribution pattern were evaluated qualitatively and semi-quantitatively using image analysis. Liposomes composed of lipids with lower transition temperature (<28°C) as well as PEGylated liposomes showed longer circulation times and extravasation. In contrast, liposomes composed of lipids with transition temperatures>28°C bound to venous parts of the vasculature. This circulation patterns in the zebrafish model did correlate with published and experimental pharmacokinetic data from mice and rats. Our findings indicate that the zebrafish model is a useful vertebrate screening tool for nanoparticulate drug delivery systems to predict their in vivo circulation behavior with respect to systemic circulation time and exposure. Copyright © 2017 Elsevier B.V. All rights reserved.

Nanoparticulate carbon black in cigarette smoke induces DNA cleavage and Th17-mediated emphysema.

PubMed

You, Ran; Lu, Wen; Shan, Ming; Berlin, Jacob M; Samuel, Errol Lg; Marcano, Daniela C; Sun, Zhengzong; Sikkema, William Ka; Yuan, Xiaoyi; Song, Lizhen; Hendrix, Amanda Y; Tour, James M; Corry, David B; Kheradmand, Farrah

2015-10-05

Chronic inhalation of cigarette smoke is the major cause of sterile inflammation and pulmonary emphysema. The effect of carbon black (CB), a universal constituent of smoke derived from the incomplete combustion of organic material, in smokers and non-smokers is less known. In this study, we show that insoluble nanoparticulate carbon black (nCB) accumulates in human myeloid dendritic cells (mDCs) from emphysematous lung and in CD11c(+) lung antigen presenting cells (APC) of mice exposed to smoke. Likewise, nCB intranasal administration induced emphysema in mouse lungs. Delivered by smoking or intranasally, nCB persisted indefinitely in mouse lung, activated lung APCs, and promoted T helper 17 cell differentiation through double-stranded DNA break (DSB) and ASC-mediated inflammasome assembly in phagocytes. Increasing the polarity or size of CB mitigated many adverse effects. Thus, nCB causes sterile inflammation, DSB, and emphysema and explains adverse health outcomes seen in smokers while implicating the dangers of nCB exposure in non-smokers.

Ice sheets as a significant source of highly reactive nanoparticulate iron to the oceans.

PubMed

Hawkings, Jon R; Wadham, Jemma L; Tranter, Martyn; Raiswell, Rob; Benning, Liane G; Statham, Peter J; Tedstone, Andrew; Nienow, Peter; Lee, Katherine; Telling, Jon

2014-05-21

The Greenland and Antarctic Ice Sheets cover ~ 10% of global land surface, but are rarely considered as active components of the global iron cycle. The ocean waters around both ice sheets harbour highly productive coastal ecosystems, many of which are iron limited. Measurements of iron concentrations in subglacial runoff from a large Greenland Ice Sheet catchment reveal the potential for globally significant export of labile iron fractions to the near-coastal euphotic zone. We estimate that the flux of bioavailable iron associated with glacial runoff is 0.40-2.54 Tg per year in Greenland and 0.06-0.17 Tg per year in Antarctica. Iron fluxes are dominated by a highly reactive and potentially bioavailable nanoparticulate suspended sediment fraction, similar to that identified in Antarctic icebergs. Estimates of labile iron fluxes in meltwater are comparable with aeolian dust fluxes to the oceans surrounding Greenland and Antarctica, and are similarly expected to increase in a warming climate with enhanced melting.

Synthesis and characterization of cerium- and gallium-containing borate bioactive glass scaffolds for bone tissue engineering.

PubMed

Deliormanlı, Aylin M

2015-02-01

Bioactive glasses are widely used in biomedical applications due to their ability to bond to bone and even to soft tissues. In this study, borate based (13-93B3) bioactive glass powders containing up to 5 wt% Ce2O3 and Ga2O3 were prepared by the melt quench technique. Cerium (Ce+3) and gallium (Ga+3) were chosen because of their low toxicity associated with bacteriostatic properties. Bioactive glass scaffolds were fabricated using the polymer foam replication method. In vitro degradation and bioactivity of the scaffolds were evaluated in SBF under static conditions. Results revealed that the cerium- and gallium-containing borate glasses have much lower degradation rates compared to the bare borate glass 13-93B3. In spite of the increased chemical durability, substituted glasses exhibited a good in vitro bioactive response except when the Ce2O3 content was 5 wt%. Taking into account the high in vitro hydroxyapatite forming ability, borate glass scaffolds containing Ce+3 and Ga+3 therapeutic ions are promising candidates for bone tissue engineering applications.

Cerium Addition Improved the Dry Sliding Wear Resistance of Surface Welding AZ91 Alloy

PubMed Central

Zhao, Zhihao; Zhu, Qingfeng; Wang, Gaosong; Tao, Kai

2018-01-01

In this study, the effects of cerium (Ce) addition on the friction and wear properties of surface welding AZ91 magnesium alloys were evaluated by pin-on-disk dry sliding friction and wear tests at normal temperature. The results show that both the friction coefficient and wear rate of surfacing magnesium alloys decreased with the decrease in load and increase in sliding speed. The surfacing AZ91 alloy with 1.5% Ce had the lowest friction coefficient and wear rate. The alloy without Ce had the worst wear resistance, mainly because it contained a lot of irregularly shaped and coarse β-Mg17Al12 phases. During friction, the β phase readily caused stress concentration and thus formed cracks at the interface between β phase and α-Mg matrix. The addition of Ce reduced the size and amount of Mg17Al12, while generating Al4Ce phase with a higher thermal stability. The Al-Ce phase could hinder the grain-boundary sliding and migration and reduced the degree of plastic deformation of subsurface metal. Scanning electron microscopy observation showed that the surfacing AZ91 alloy with 1.5% Ce had a total of four types of wear mechanism: abrasion, oxidation, and severe plastic deformation were the primary mechanisms; delamination was the secondary mechanism. PMID:29415492

Preclinical Evaluation to Specifically Target Ovarian Cancer with Folic Acid-Conjugated Nanoceria

DTIC Science & Technology

2014-08-01

cancer . Our experimental nanoparticle is Nanoceria (NCe), a cerium oxide nanoparticle . Nanotechnology -based tools and techniques are rapidly... cancer we proposed the present work, where we are integrating the field of nanotechnology with ovarian cancer cell’s unique property of...overexpressing folic acid receptor alpha (FR-a) to specifically target ovarian cancer . A cerium oxide nanoparticle , called Nanoceria (NCe), that has the ability

Low-temperature carbon monoxide oxidation over zirconia-supported CuO-CeO2 catalysts: Effect of zirconia support properties

NASA Astrophysics Data System (ADS)

Moretti, Elisa; Molina, Antonia Infantes; Sponchia, Gabriele; Talon, Aldo; Frattini, Romana; Rodriguez-Castellon, Enrique; Storaro, Loretta

2017-05-01

A study was conducted to investigate the effect of the preparation route of ZrO2 in CuO-CeO2/ZrO2 catalysts for the oxidation of carbon monoxide at low temperature (COX). Four ZrO2 supports were synthetized via either type sol-gel methodology or precipitation. The final Cu-Ce-Zr oxide catalysts were prepared by incipient wetness co-impregnation with copper and cerium solutions (with a loading of 6 wt% of CuO and 20 wt% of CeO2). The catalyst crystalline phases, texture and active species reducibility were determined by XRD, N2 physisorption at -196 °C and H2-TPR, respectively; meanwhile the surface composition and copper-cerium electronic states were studied by XPS. The catalytic activity was evaluated in the oxidation of CO to CO2, in the 40-215 °C temperature range. Catalytic results evidenced that the samples prepared by a sol-gel methodology showed, after the impregnation, a severe decrease of specific surface area and pore volume attributable to a wide degree of pore blockage caused by the presence of metal oxide particles and a collapse of the structure partially burying the active sites. A simple co-impregnation of a zirconia support, obtained through facile and fast precipitation, provided instead a catalyst with very good redox properties and high dispersion of the active phases, which completely oxidizes CO in the range 115-215 °C with T50 of 65 °C. This higher observed activity was ascribed to the formation of a larger fraction of highly dispersed and easily reducible Cu species and ceria nanocrystallites, mainly present as Ce(IV), with an average size of 5 nm.

Characteristics of environmental correlations between iron (oxyhydr)oxide nanoparticles and microbial activity

NASA Astrophysics Data System (ADS)

Tamura, T.; Kyono, A.; Muratani, M.

2014-12-01

Nanoparticulate iron oxides and oxyhydroxides with large surface area and high chemical reactivity cause the immobilization of heavy metals and the provision of essential nutrients to organisms. Environmental correlations between microbial activity and nanomorphology of iron (oxyhydr)oxides are significantly important for earth surface processes. In this study, we characterize iron (oxyhydr)oxide nanoparticles and microorganisms in natural lake sediments and describe their association observed between particle nanostructures and microbial species. About 40 cm depth of boring core sample was collected from Lake Kasumigaura, Lake Ushiku, Kokai River and Lake Tega, Japan. To distinguish both iron nanoparticles and growing bacterial colonies with depths, boring core samples were divided into three to five pieces. Particle morphologies, size, aggregation states, mineral species, and microorganisms were observed by transmission electron microscopy (TEM), X-ray diffraction (XRD), and rRNA gene sequences. Redox potential and pH of the lake sediments were also measured. The core sample from top is mainly composed of quartz of coarse-grained materials, while that from bottom is of ferrihydrite of fine grained materials. The authors will show the results of experiments and discuss the interrelation between iron nanoparticles and microorganisms.

Enhanced oxygen reduction activity and solid oxide fuel cell performance with a nanoparticles-loaded cathode.

PubMed

Zhang, Xiaomin; Liu, Li; Zhao, Zhe; Tu, Baofeng; Ou, Dingrong; Cui, Daan; Wei, Xuming; Chen, Xiaobo; Cheng, Mojie

2015-03-11

Reluctant oxygen-reduction-reaction (ORR) activity has been a long-standing challenge limiting cell performance for solid oxide fuel cells (SOFCs) in both centralized and distributed power applications. We report here that this challenge has been tackled with coloading of (La,Sr)MnO3 (LSM) and Y2O3 stabilized zirconia (YSZ) nanoparticles within a porous YSZ framework. This design dramatically improves ORR activity, enhances fuel cell output (200-300% power improvement), and enables superior stability (no observed degradation within 500 h of operation) from 600 to 800 °C. The improved performance is attributed to the intimate contacts between nanoparticulate YSZ and LSM particles in the three-phase boundaries in the cathode.

Pyrochlore-rich titanate ceramics for the immobilization of plutonium: redox effects on phase equilibria in cerium- and thorium- substituted analogs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ryerson, F J; Ebbinghaus, B

2000-05-25

Three compositions representing plutonium-free analogs of a proposed Ca-Ti-Gd-Hf-U-PU oxide ceramic for the immobilization of plutonium were equilibrated at 1 atm, 1350 C over a range of oxygen fugacities between air and that equivalent to the iron-wuestite buffer. The cerium analog replaces Pu on a mole-per-mole basic with Ce; the thorium analog replaces Pu with Th. A third material has 10 wt% Al{sub 2}O{sub 3} added to the cerium analog to encourage the formation of a Hf-analog of, CaHfTi{sub 2}O{sub 7}, zirconolite, which is referred to as hafnolite. The predominant phase produced in each formulation under all conditions is pyrochlore,more » A{sub 2}T{sub 2}O{sub 7}, where the T site is filled by Ti, and Ca, the lanthanides, Hf, U and Pu are accommodated on the A-site. Other lanthanide and uranium-bearing phases encountered include brannerite (UTi{sub 2}O{sub 6}), hafnolite (CaHfTi{sub 2}O{sub 7}), perovskite (CaTiO{sub 3}) and a calcium-lanthanide aluminotitanate with nominal stoichiometry (Ca,Ln)Ti{sub 2}Al{sub 9}O{sub 19}, where Ln is a lanthanide. The phase compositions show progressive shifts with decreasing oxygen fugacity. All of the phases observed have previously been identified in titanate-based high-level radioactive waste ceramics and demonstrate the flexibility of these ceramics to variations in processing parameters. The main variation is an increase in the uranium concentrations of pyrochlore and brannerite which must be accommodated by variations in modal abundance. Pyrochlore compositions are consistent with existing spectroscopic data suggesting that uranium is predominantly pentavalent in samples synthesized in air. A simple model based on ideal stoichiometry suggests the U{sup +4}/{Sigma}U varies linearly with log fO{sub 2} and that all of the uranium is quadravalent at the iron-wuestite buffer.« less

Nanoparticulate STING agonists are potent lymph node–targeted vaccine adjuvants

PubMed Central

Hanson, Melissa C.; Crespo, Monica P.; Abraham, Wuhbet; Moynihan, Kelly D.; Szeto, Gregory L.; Chen, Stephanie H.; Melo, Mariane B.; Mueller, Stefanie; Irvine, Darrell J.

2015-01-01

Cyclic dinucleotides (CDNs) are agonists of stimulator of IFN genes (STING) and have potential as vaccine adjuvants. However, cyclic di-GMP (cdGMP) injected s.c. shows minimal uptake into lymphatics/draining lymph nodes (dLNs) and instead is rapidly distributed to the bloodstream, leading to systemic inflammation. Here, we encapsulated cdGMP within PEGylated lipid nanoparticles (NP-cdGMP) to redirect this adjuvant to dLNs. Compared with unformulated CDNs, encapsulation blocked systemic dissemination and markedly enhanced dLN accumulation in murine models. Delivery of NP-cdGMP increased CD8+ T cell responses primed by peptide vaccines and enhanced therapeutic antitumor immunity. A combination of a poorly immunogenic liposomal HIV gp41 peptide antigen and NP-cdGMP robustly induced type I IFN in dLNs, induced a greater expansion of vaccine-specific CD4+ T cells, and greatly increased germinal center B cell differentiation in dLNs compared with a combination of liposomal HIV gp41 and soluble CDN. Further, NP-cdGMP promoted durable antibody titers that were substantially higher than those promoted by the well-studied TLR agonist monophosphoryl lipid A and comparable to a much larger dose of unformulated cdGMP, without the systemic toxicity of the latter. These results demonstrate that nanoparticulate delivery safely targets CDNs to the dLNs and enhances the efficacy of this adjuvant. Moreover, this approach can be broadly applied to other small-molecule immunomodulators of interest for vaccines and immunotherapy. PMID:25938786

Nanoparticulate STING agonists are potent lymph node-targeted vaccine adjuvants.

PubMed

Hanson, Melissa C; Crespo, Monica P; Abraham, Wuhbet; Moynihan, Kelly D; Szeto, Gregory L; Chen, Stephanie H; Melo, Mariane B; Mueller, Stefanie; Irvine, Darrell J

2015-06-01

Cyclic dinucleotides (CDNs) are agonists of stimulator of IFN genes (STING) and have potential as vaccine adjuvants. However, cyclic di-GMP (cdGMP) injected s.c. shows minimal uptake into lymphatics/draining lymph nodes (dLNs) and instead is rapidly distributed to the bloodstream, leading to systemic inflammation. Here, we encapsulated cdGMP within PEGylated lipid nanoparticles (NP-cdGMP) to redirect this adjuvant to dLNs. Compared with unformulated CDNs, encapsulation blocked systemic dissemination and markedly enhanced dLN accumulation in murine models. Delivery of NP-cdGMP increased CD8+ T cell responses primed by peptide vaccines and enhanced therapeutic antitumor immunity. A combination of a poorly immunogenic liposomal HIV gp41 peptide antigen and NP-cdGMP robustly induced type I IFN in dLNs, induced a greater expansion of vaccine-specific CD4+ T cells, and greatly increased germinal center B cell differentiation in dLNs compared with a combination of liposomal HIV gp41 and soluble CDN. Further, NP-cdGMP promoted durable antibody titers that were substantially higher than those promoted by the well-studied TLR agonist monophosphoryl lipid A and comparable to a much larger dose of unformulated cdGMP, without the systemic toxicity of the latter. These results demonstrate that nanoparticulate delivery safely targets CDNs to the dLNs and enhances the efficacy of this adjuvant. Moreover, this approach can be broadly applied to other small-molecule immunomodulators of interest for vaccines and immunotherapy.

Assigning the Cerium Oxidation State for CH2CeF2 and OCeF2 Based on Multireference Wave Function Analysis.

PubMed

Mooßen, Oliver; Dolg, Michael

2016-06-09

The geometric and electronic structure of the recently experimentally studied molecules ZCeF2 (Z = CH2, O) was investigated by density functional theory (DFT) and wave function-based ab initio methods. Special attention was paid to the Ce-Z metal-ligand bonding, especially to the nature of the interaction between the Ce 4f and the Z 2p orbitals and the possible multiconfigurational character arising from it, as well as to the assignment of an oxidation state of Ce reflecting the electronic structure. Complete active space self-consistent field (CASSCF) calculations were performed, followed by orbital rotations in the active orbital space. The methylene compound CH2CeF2 has an open-shell singlet ground state, which is characterized by a two-configurational wave function in the basis of the strongly mixed natural CASSCF orbitals. The system can also be described in a very compact way by the dominant Ce 4f(1) C 2p(1) configuration, if nearly pure Ce 4f and C 2p orbitals are used. In the basis of these localized orbitals, the molecule is almost monoconfigurational and should be best described as a Ce(III) system. The singlet ground state of the oxygen OCeF2 complex is of closed-shell character when a monoconfigurational wave function with very strongly mixed Ce 4f and O 2p CASSCF natural orbitals is used for the description. The transformation to orbitals localized on the cerium and oxygen atoms leads to a multiconfigurational wave function and reveals characteristics of a mixed valent Ce(IV)/Ce(III) compound. Additionally, the interactions of the localized active orbitals were analyzed by evaluating the expectation values of the charge fluctuation operator and the local spin operator. The Ce 4f and C 2p orbital interaction of the CH2CeF2 compound is weakly covalent and resembles the interaction of the H 1s orbitals in a stretched hydrogen dimer. In contrast, the interaction of the localized active orbitals for OCeF2 shows ionic character. Calculated vibrational Ce

Hydroxamic acid interactions with solvated cerium hydroxides in the flotation of monazite and bastnäsite-Experiments and DFT study

NASA Astrophysics Data System (ADS)

Sarvaramini, A.; Azizi, D.; Larachi, F.

2016-11-01

Density functional theory (DFT) simulations and experiments were performed to clarify the interaction mechanisms between hydroxamic acid collectors and cerium hydroxides during the flotation of bastnäsite and monazite minerals. These minerals showed considerable floatability at moderately alkaline pH which was related to the adsorption of hydroxamic acids on their surfaces as confirmed by vibrational spectroscopic and zeta potential measurements. DFT simulations showed that at moderately alkaline pH, the interactions between solvated Ce(OH)2+ and Ce(OH)2+ and heptyl-hydroxamic acid (HHA) anions resulted in the formation of, respectively, [Ce(OH)(HHA)x(H2O)y]2-x (x[y = ] = 1[6],2[3],3[1]) and [Ce(OH)2(HHA)x(H2O)y]1-x (x[y = ] = 1[5],2[1],3[0]) complexes. The collector anions were found to interact directly through formation of two covalent bonds between their two polar-head oxygen atoms and cerium in the hydroxide complexes. However, formation of such new bonds resulted in breakage of a few covalent/electrostatic bonds between cerium and water molecules initially present in the first hydration shell of the rare-earth metal cation. Building up in the electric double layer of the semi-soluble minerals, these complexes, and by extension, those from other rare-earth elements belonging to monazite and bastnäsite, are speculated to play a role in the interactions between rare-earth minerals and hydroxamic acid collectors.

Pressure induced phase transition and elastic properties of cerium mono-nitride (CeN)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yaduvanshi, Namrata, E-mail: namrata-yaduvanshi@yahoo.com; Singh, Sadhna

2016-05-23

In the present paper, we have investigated the high-pressure structural phase transition and elastic properties of cerium mono-nitride. We studied theoretically the structural properties of this compound (CeN) by using the improved interaction potential model (IIPM) approach. This compound exhibits first order crystallographic phase transition from NaCl (B{sub 1}) to tetragonal (BCT) phase at 37 GPa. The phase transition pressures and associated volume collapse obtained from present potential model (IIPM) show a good agreement with available theoretical data.

Difference of EGCg adhesion on cell surface between Staphylococcus aureus and Escherichia coli visualized by electron microscopy after novel indirect staining with cerium chloride.

PubMed

Nakayama, Motokazu; Shigemune, Naofumi; Tsugukuni, Takashi; Tokuda, Hajime; Miyamoto, Takahisa

2011-07-01

We developed a novel method using indirect staining with cerium chloride for visualization of the catechin derivative epigallocatechin gallate (EGCg) on the surface of particles, i.e., polystyrene beads and bacterial cells, by electron microscopy. The staining method is based on the fact that in an alkaline environment, EGCg produces hydrogen peroxide, and then hydrogen peroxide reacts with cerium, resulting in a cerium hydroperoxide precipitate. This precipitate subsequently reacts with EGCg to produce larger deposits. The amount of precipitate is proportional to the amount of EGCg. Highly EGCg-sensitive Staphylococcus aureus and EGCg-resistant Escherichia coli were treated with EGCg under various pH conditions. Transmission electron microscopy observation showed that the amount of deposits on S. aureus increased with an increase in EGCg concentration. After treating bacterial cells with 0.5mg/mL EGCg (pH 6.0), attachment of EGCg was significantly lower to E. coli than to S. aureus. This is the first report that shows differences in affinity of EGCg to the cell surfaces of Gram-positive and -negative bacteria by electron microscopy. Copyright © 2011 Elsevier B.V. All rights reserved.

Key process parameters to modify the porosity of cerium dioxide microspheres formed in the internal gelation process

DOE PAGES

Hunt, Rodney Dale; Collins, Jack Lee; Reif, Tyler J.; ...

2017-08-04

Recently, an internal gelation study demonstrated that the use of heated urea and hexamethylenetetramine can have a pronounced impact on the porosity and sintering characteristics of cerium dioxide (CeO 2) microspheres. This effort has identified process variables that can significantly change the initial porosity of the CeO 2 microspheres with slight modifications. A relatively small difference in the sample preparation of cerium ammonium nitrate and ammonium hydroxide solution had a large reproducible impact on the porosity and slow pour density of the produced microspheres. Increases in the gelation temperature as small as 0.5 K also produced a noticeable increase inmore » the slow pour density. If the gelation temperature was increased too high, the use of the heated hexamethylenetetramine and urea was no longer observed to be effective in increasing the porosity of the CeO 2 microspheres. In conclusion, the final process variable was the amount of dispersing agent, Span™ 80, which can increase the slow pour density and produce significantly smaller microspheres.« less

Key process parameters to modify the porosity of cerium dioxide microspheres formed in the internal gelation process

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hunt, Rodney Dale; Collins, Jack Lee; Reif, Tyler J.

Recently, an internal gelation study demonstrated that the use of heated urea and hexamethylenetetramine can have a pronounced impact on the porosity and sintering characteristics of cerium dioxide (CeO 2) microspheres. This effort has identified process variables that can significantly change the initial porosity of the CeO 2 microspheres with slight modifications. A relatively small difference in the sample preparation of cerium ammonium nitrate and ammonium hydroxide solution had a large reproducible impact on the porosity and slow pour density of the produced microspheres. Increases in the gelation temperature as small as 0.5 K also produced a noticeable increase inmore » the slow pour density. If the gelation temperature was increased too high, the use of the heated hexamethylenetetramine and urea was no longer observed to be effective in increasing the porosity of the CeO 2 microspheres. In conclusion, the final process variable was the amount of dispersing agent, Span™ 80, which can increase the slow pour density and produce significantly smaller microspheres.« less

Predictive tests to evaluate oxidative potential of engineered nanomaterials

NASA Astrophysics Data System (ADS)

Ghiazza, Mara; Carella, Emanuele; Oliaro-Bosso, Simonetta; Corazzari, Ingrid; Viola, Franca; Fenoglio, Ivana

2013-04-01

Oxidative stress constitutes one of the principal injury mechanisms through which particulate toxicants (asbestos, crystalline silica, hard metals) and engineered nanomaterials can induce adverse health effects. ROS may be generated indirectly by activated cells and/or directly at the surface of the material. The occurrence of these processes depends upon the type of material. Many authors have recently demonstrated that metal oxides and carbon-based nanoparticles may influence (increasing or decreasing) the generation of oxygen radicals in a cell environment. Metal oxide, such as iron oxides, crystalline silica, and titanium dioxide are able to generate free radicals via different mechanisms causing an imbalance within oxidant species. The increase of ROS species may lead to inflammatory responses and in some cases to the development of cancer. On the other hand carbon-based nanomaterials, such as fullerene, carbon nanotubes, carbon black as well as cerium dioxide are able to scavenge the free radicals generated acting as antioxidant. The high numbers of new-engineered nanomaterials, which are introduced in the market, are exponentially increasing. Therefore the definition of toxicological strategies is urgently needed. The development of acellular screening tests will make possible the reduction of the number of in vitro and in vivo tests to be performed. An integrated protocol that may be used to predict the oxidant/antioxidant potential of engineered nanoparticles will be here presented.

Highly efficient Cu-decorated iron oxide nanocatalyst for low pressure CO 2 conversion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Halder, Avik; Kilianová, Martina; Yang, Bing

We report a nanoparticulate iron oxide based catalyst for CO2 conversion with high efficiency at low pressures and on the effect of the presence of copper on the catalyst's restructuring and its catalytic performance. In situ X-ray scattering reveals the restructuring of the catalyst at the nanometer scale. In situ X-ray absorption near edge structure (XANES) shows the evolution of the composition and oxidation state of the iron and copper components under reaction conditions along with the promotional effect of copper on the chemical transformation of the iron component. X-ray diffraction (XRD), XANES and Raman spectroscopy proved that the startingmore » nano catalyst is composed of iron oxides differing in chemical nature (alpha-Fe2O3, Fe3O4, FeO(OH)) and dimensionality, while the catalyst after CO2 conversion was identified as a mixture of alpha-Fe, Fe3C, and traces of Fe5C2. The significant increase of the rate CO2 is turned over in the presence of copper nanoparticles indicates that Cu nanoparticles activate hydrogen, which after spilling over to the neighbouring iron sites, facilitate a more efficient conversion of carbon dioxide.« less

Enhanced Formation of Oxidants from Bimetallic Nickel-Iron Nanoparticles in the Presence of Oxygen

PubMed Central

Lee, Changha; Sedlak, David L.

2009-01-01

Nanoparticulate zero-valent iron (nZVI) rapidly reacts with oxygen to produce strong oxidants, capable of transforming organic contaminants in water. However, the low yield of oxidants with respect to the iron added normally limits the application of this system. Bimetallic nickel-iron nanoparticles (nNi-Fe; i.e., Ni-Fe alloy and Ni-coated Fe nanoparticles) exhibited enhanced yields of oxidants compared to nZVI. nNi-Fe (Ni-Fe alloy nanoparticles with [Ni]/[Fe] = 0.28 and Ni-coated Fe nanoparticles with [Ni]/[Fe] = 0.035) produced approximately 40% and 85% higher yields of formaldehyde from the oxidation of methanol relative to nZVI at pH 4 and 7, respectively. Ni-coated Fe nanoparticles showed a higher efficiency for oxidant production relative to Ni-Fe alloy nanoparticles based on Ni content. Addition of Ni did not enhance the oxidation of 2-propanol or benzoic acid, indicating that Ni addition did not enhance hydroxyl radical formation. The enhancement in oxidant yield was observed over a pH range of 4 – 9. The enhanced production of oxidant by nNi-Fe appears to be attributable to two factors. First, the nNi-Fe surface is less reactive toward hydrogen peroxide (H2O2) than the nZVI surface, which favors the reaction of H2O2 with dissolved Fe(II) (the Fenton reaction). Second, the nNi-Fe surface promotes oxidant production from the oxidation of ferrous ion by oxygen at neutral pH values. PMID:19068843

Self-assembled Lyotropic Liquid Crystalline Phase Behavior of Monoolein-Capric Acid-Phospholipid Nanoparticulate Systems.

PubMed

Zhai, Jiali; Tran, Nhiem; Sarkar, Sampa; Fong, Celesta; Mulet, Xavier; Drummond, Calum J

2017-03-14

We report here the lyotropic liquid crystalline phase behavior of two lipid nanoparticulate systems containing mixtures of monoolein, capric acid, and saturated diacyl phosphatidylcholines dispersed by the Pluronic F127 block copolymer. Synchrotron small-angle X-ray scattering (SAXS) was used to screen the phase behavior of a library of lipid nanoparticles in a high-throughput manner. It was found that adding capric acid and phosphatidylcholines had opposing effects on the spontaneous membrane curvature of the monoolein lipid layer and hence the internal mesophase of the final nanoparticles. By varying the relative concentration of the three lipid components, we were able to establish a library of nanoparticles with a wide range of mesophases including at least the inverse bicontinuous primitive and double diamond cubic phases, the inverse hexagonal phase, the fluid lamellar phase, and possibly other phases. Furthermore, the in vitro cytotoxicity assay showed that the endogenous phospholipid-containing nanoparticles were less toxic to cultured cell lines compared to monoolein-based counterparts, improving the potential of the nonlamellar lipid nanoparticles for biomedical applications.

Nanoparticulate carbon black in cigarette smoke induces DNA cleavage and Th17-mediated emphysema

PubMed Central

You, Ran; Lu, Wen; Shan, Ming; Berlin, Jacob M; Samuel, Errol LG; Marcano, Daniela C; Sun, Zhengzong; Sikkema, William KA; Yuan, Xiaoyi; Song, Lizhen; Hendrix, Amanda Y; Tour, James M; Corry, David B; Kheradmand, Farrah

2015-01-01

Chronic inhalation of cigarette smoke is the major cause of sterile inflammation and pulmonary emphysema. The effect of carbon black (CB), a universal constituent of smoke derived from the incomplete combustion of organic material, in smokers and non-smokers is less known. In this study, we show that insoluble nanoparticulate carbon black (nCB) accumulates in human myeloid dendritic cells (mDCs) from emphysematous lung and in CD11c+ lung antigen presenting cells (APC) of mice exposed to smoke. Likewise, nCB intranasal administration induced emphysema in mouse lungs. Delivered by smoking or intranasally, nCB persisted indefinitely in mouse lung, activated lung APCs, and promoted T helper 17 cell differentiation through double-stranded DNA break (DSB) and ASC-mediated inflammasome assembly in phagocytes. Increasing the polarity or size of CB mitigated many adverse effects. Thus, nCB causes sterile inflammation, DSB, and emphysema and explains adverse health outcomes seen in smokers while implicating the dangers of nCB exposure in non-smokers. DOI: http://dx.doi.org/10.7554/eLife.09623.001 PMID:26437452

Influence of the physico-chemical properties of CeO 2-ZrO 2 mixed oxides on the catalytic oxidation of NO to NO 2

NASA Astrophysics Data System (ADS)

Atribak, Idriss; Guillén-Hurtado, Noelia; Bueno-López, Agustín; García-García, Avelina

2010-10-01

Commercial and home-made Ce-Zr catalysts prepared by co-precipitation were characterised by XRD, Raman spectroscopy, N 2 adsorption at -196 °C and XPS, and were tested for NO oxidation to NO 2. Among the different physico-chemical properties characterised, the surface composition seems to be the most relevant one in order to explain the NO oxidation capacity of these Ce-Zr catalysts. As a general trend, Ce-Zr catalysts with a cerium-rich surface, that is, high XPS-measured Ce/Zr atomic surface ratios, are more active than those with a Zr-enriched surface. The decrease in catalytic activity of the Ce-Zr mixed oxided upon calcinations at 800 °C with regard to 500 °C is mainly attributed to the decrease in Ce/Zr surface ratio, that is, to the surface segregation of Zr. The phase composition (cubic or t'' for Ce-rich compositions) seems not to be a direct effect on the catalytic activity for NO oxidation in the range of compositions tested. However, the formation of a proper solid solution prevents important surface segregation of Zr upon calcinations at high temperature. The effect of the BET surface area in the catalytic activity for NO oxidation of Ce-Zr mixed oxides is minor in comparison with the effect of the Ce/Zr surface ratio.

Dynamique de nanobulles et nanoplasmas generes autour de nanoparticules plasmoniques irradiees par des impulsions ultracourtes

NASA Astrophysics Data System (ADS)

Dagallier, Adrien

L'emergence des lasers a impulsion ultrabreves et des nanotechnologies a revolutionne notre perception et notre maniere d'interagir avec l'infiniment petit. Les gigantesques intensites generees par ces impulsions plus courtes que les temps de relaxation ou de diffusion du milieu irradie induisent de nombreux phenomenes non-lineaires, du doublement de frequence a l'ablation, dans des volumes de dimension caracteristique de l'ordre de la longueur d'onde du laser. En biologie et en medecine, ces phenomenes sont utilises a des fins d'imagerie multiphotonique ou pour detruire des tissus vivants. L'introduction de nanoparticules plasmoniques, qui concentrent le champ electromagnetique incident dans des regions de dimensions nanometriques, jusqu'a une fraction de la longueur d'onde, amplifie les phenomenes non-lineaires tout en offrant un controle beaucoup plus precis de la deposition d'energie, ouvrant la voie a la detection de molecules individuelles en solution et a la nanochirurgie. La nanochirurgie repose principalement sur la formation d'une bulle de vapeur a proximite d'une membrane cellulaire. Cette bulle de vapeur perce la membrane de maniere irreversible,entrainant la cellule a sa mort, ou la perturbe temporairement, ce qui permet d'envisager de faire penetrer dans la cellule des medicaments ou des brins d'ADN pour de la therapie genique. C'est principalement la taille de la bulle qui va decider de l'issue de l'irradiation laser. Il est donc necessaire de controler finement les parametres du laser et la geometrie de la nanoparticule afin d'atteindre l'objectif fixe. Le moyen le plus direct a l'heure actuelle de valider un ensemble de conditions experimentales est de realiser l'experience en laboratoire,ce qui est long et couteux. Les modeles de dynamique de bulle existants ne prennent pas en compte les parametres de l'irradiation et ajustent souvent leurs conditions initiales a partir de leurs mesures experimentales, ce qui limite la portee du modele au cas pour

Gamma ray induced decomposition of double nitrates of lanthanum and cerium with some mono and bivalent cations in solid state

NASA Astrophysics Data System (ADS)

Kulkarni, S. P.; Garg, A. N.

Gamma ray induced decomposition of two series of double nitrates; 2M INO 3⋯Ln(NO 3) 3⋯ x H 2O (where MI = NH+4, Na+, K+, Rb+, Cs+; LnIII = La3+, Ce3+ and x = 2 or 4) and 3M II(NO 3) 2·2Ln III(NO 3) 3⋯24H 2O (where MII = Mg2+, Co2+, Zn2+; LnIII = La3+, Ce3+) has been studied in solid state over a wide absorbed dose range at room temperature. G(NO -2) values have been found to depend on the absorbed dose and the nature of cation in both the series of double salts. Radiation sensitivity of lanthanum double nitrates with monovalent cations at an absorbed dose of 158 kGy follows the order NH +4 < Rb + ≅ Cs + < Na + < K + and those of cerium NH +4 < Rb + cerium salts are in the range 0.62-0.91 in the order Zn 2+ ≅ Co 2+ < Mg 2+. In fact double nitrates of cerium with Zn 2+ and Co 2+ exhibit almost similar G(NO -2) values over the dose range 5-640 kGy. X-ray powder diffraction patterns of the irradiated Mg-La double salt indicate the possibility of structural phase transformation at certain doses.

Effect of variable cerium concentration on photoluminescence behaviour in ZrO2 phosphor synthesized by combustion synthesis method

NASA Astrophysics Data System (ADS)

Dubey, Vikas; Kaur, Jagjeet

2016-05-01

Present paper reports synthesis and characterization of trivalent cerium (Ce3+) doped zirconium dioxide (ZrO2) phosphors. Effect of variable concentration of cerium on photoluminescence (PL) is studied. Samples were prepared by combustion synthesis technique which is suitable for less time taking techniques also for large scale production for phosphors. Starting material used for sample preparation are Zr(NO3)3 and Ce(NO3)3 and urea used as a fuel. All prepared phosphor with variable concentration of Ce3+ (0.1 to 2mol%) was studied by photoluminescence analysis it is found that the excitation spectra of prepared phosphor shows broad excitation centred at 390nm. The excitation spectra with variable concentration of Ce3+ show strong peaks at 447nm. Spectrophotometric determinations of peaks are evaluated by Commission Internationale de I'Eclairage technique. Using this phosphor, the desired CIE values including emissions throughout the violet (390 nm) and blue (427 nm) of the spectra were achieved. Efficient blue light emitting diodes were fabricated using Ce3+ doped phosphor based on near ultraviolet (NUV) excited LED lights.

Activation cross-section measurement of proton induced reactions on cerium

NASA Astrophysics Data System (ADS)

Tárkányi, F.; Hermanne, A.; Ditrói, F.; Takács, S.; Spahn, I.; Spellerberg, S.

2017-12-01

In the framework of a systematic study of proton induced nuclear reactions on lanthanides we have measured the excitation functions on natural cerium for the production of 142,139,138m,137Pr, 141,139,137m,137g,135Ce and 133La up to 65 MeV proton energy using the activation method with stacked-foil irradiation technique and high-resolution γ-ray spectrometry. The cross-sections of the investigated reactions were compared with the data retrieved from the TENDL-2014 and TENDL-2015 libraries, based on the latest version of the TALYS code system. No earlier experimental data were found in the literature. The measured cross-section data are important for further improvement of nuclear reaction models and for practical applications in nuclear medicine, other labeling and activation studies.

High performance aluminum–cerium alloys for high-temperature applications

DOE PAGES

Sims, Zachary C.; Rios, Orlando R.; Weiss, David; ...

2017-08-01

Light-weight high-temperature alloys are important to the transportation industry where weight, cost, and operating temperature are major factors in the design of energy efficient vehicles. Aluminum alloys fill this gap economically but lack high-temperature mechanical performance. Alloying aluminum with cerium creates a highly castable alloy, compatible with traditional aluminum alloy additions, that exhibits dramatically improved high-temperature performance. These compositions display a room temperature ultimate tensile strength of 400 MPa and yield strength of 320 MPa, with 80% mechanical property retention at 240 °C. A mechanism is identified that addresses the mechanical property stability of the Al-alloys to at least 300more » °C and their microstructural stability to above 500 °C which may enable applications without the need for heat treatment. Lastly, neutron diffraction under load provides insight into the unusual mechanisms driving the mechanical strength.« less

Oxidative Alteration of Ferrous Smectites and Implications for the Redox Evolution of Early Mars

NASA Astrophysics Data System (ADS)

Chemtob, Steven M.; Nickerson, Ryan D.; Morris, Richard V.; Agresti, David G.; Catalano, Jeffrey G.

2017-12-01

Surface conditions on early Mars were likely anoxic, similar to early Earth, but the timing of the evolution to oxic conditions characteristic of contemporary Mars is unresolved. Ferrous trioctahedral smectites are the thermodynamically predicted products of anoxic basalt weathering, but orbital analyses of Noachian-aged terrains find primarily Fe3+-bearing clay minerals. Rover-based detection of Fe2+-bearing trioctahedral smectites at Gale Crater suggests that ferrous smectites are the unoxidized progenitors of orbitally detected ferric smectites. To assess this pathway, we conducted ambient-temperature oxidative alteration experiments on four synthetic ferrous smectites having molar Fe/(Mg + Fe) from 1.00 to 0.33. Smectite suspension in air-saturated solutions produced incomplete oxidation (24-38% Fe3+/ΣFe). Additional smectite oxidation occurred upon reexposure to air-saturated solutions after anoxic hydrothermal recrystallization, which accelerated cation and charge redistribution in the octahedral sheet. Oxidation was accompanied by contraction of the octahedral sheet (d(060) decreased from 1.53-1.56 Å to 1.52 Å), consistent with a shift toward dioctahedral structure. Ferrous smectite oxidation by aqueous hydrogen peroxide solutions resulted in nearly complete Fe2+ oxidation but also led to partial Fe3+ ejection from the structure, producing nanoparticulate hematite. Reflectance spectra of oxidized smectites were characterized by (Fe3+,Mg)2-OH bands at 2.28-2.30 μm, consistent with oxidative formation of dioctahedral nontronite. Accordingly, ferrous smectites are plausible precursors to observed ferric smectites on Mars, and their presence in late-Noachian sedimentary units suggests that anoxic conditions may have persisted on Mars beyond the Noachian.

Long term effects of cerium dioxide nanoparticles on the nitrogen removal, micro-environment and community dynamics of a sequencing batch biofilm reactor.

PubMed

Xu, Yi; Wang, Chao; Hou, Jun; Wang, Peifang; Miao, Lingzhan; You, Guoxiang; Lv, Bowen; Yang, Yangyang; Zhang, Fei

2017-12-01

The influences of cerium dioxide nanoparticles (CeO 2 NPs) on nitrogen removal in biofilm were investigated. Prolonged exposure (75d) to 0.1mg/L CeO 2 NPs caused no inhibitory effects on nitrogen removal, while continuous addition of 10mg/L CeO 2 NPs decreased the treatment efficiency to 53%. With the progressive concentration of CeO 2 NPs addition, the removal efficiency could nearly stabilize at 67% even with the continues spike of 10mg/L. The micro-profiles of dissolved oxygen, pH, and oxidation reduction potential suggested the developed protection mechanisms of microbes to progressive CeO 2 NPs exposure led to the less influence of microenvironment, denitrification bacteria and enzyme activity than those with continuous ones. Furthermore, high throughput sequencing illustrated the drastic shifted communities with gradual CeO 2 NPs spiking was responsible for the adaption and protective mechanisms. The present study demonstrated the acclimated microbial community was able to survive CeO 2 NPs addition more readily than those non-acclimated. Copyright © 2017 Elsevier Ltd. All rights reserved.

Nanoparticulate zinc oxide as a coating material for orthopedic and dental implants.

PubMed

Memarzadeh, Kaveh; Sharili, Amir S; Huang, Jie; Rawlinson, Simon C F; Allaker, Robert P

2015-03-01

Orthopedic and dental implants are prone to infection. In this study, we describe a novel system using zinc oxide nanoparticles (nZnO) as a coating material to inhibit bacterial adhesion and promote osteoblast growth. Electrohydrodynamic atomisation (EHDA) was employed to deposit mixtures of nZnO and nanohydroxyapatite (nHA) onto the surface of glass substrates. Nano-coated substrates were exposed to Staphylococcus aureus suspended in buffered saline or bovine serum to determine antimicrobial activity. Our results indicate that 100% nZnO and 75% nZnO/25% nHA composite-coated substrates have significant antimicrobial activity. Furthermore, osteoblast function was explored by exposing cells to nZnO. UMR-106 cells exposed to nZnO supernatants showed minimal toxicity. Similarly, MG-63 cells cultured on nZnO substrates did not show release of TNF-α and IL-6 cytokines. These results were reinforced by both proliferation and differentiation studies which revealed that a substrate coated with exclusively nZnO is more efficient than composite surface coatings. Finally, electron and light microscopy, together with immunofluorescence staining, revealed that all cell types tested, including human mesenchymal cell (hMSC), were able to maintain normal cell morphology when adhered onto the surface of the nano-coated substrates. Collectively, these findings indicate that nZnO can, on its own, provide an optimal coating for future bone implants that are both antimicrobial and biocompatible. © 2014 Wiley Periodicals, Inc.

Development and characterization of nanoparticulate formulation of a water soluble prodrug of dexamethasone by HIP complexation.

PubMed

Gaudana, Ripal; Parenky, Ashwin; Vaishya, Ravi; Samanta, Swapan K; Mitra, Ashim K

2011-01-01

The objective of this study was to develop and characterize a nanoparticulate-based sustained release formulation of a water soluble dipeptide prodrug of dexamethasone, valine-valine-dexamethasone (VVD). Being hydrophilic in nature, it readily leaches out in the external aqueous medium and hence partitions poorly into the polymeric matrix resulting in minimal entrapment in nanoparticles. Hence, hydrophobic ion pairing (HIP) complexation of the prodrug was employed with dextran sulphate as a complexing polymer. A novel, solid in oil in water emulsion method was employed to encapsulate the prodrug in HIP complex form in poly(lactic-co-glycolic acid) matrix. Nanoparticles were characterized with respect to size, zeta potential, crystallinity of entrapped drug and surface morphology. A significant enhancement in the entrapment of the prodrug in nanoparticles was achieved. Finally, a simple yet novel method was developed which can also be applicable to encapsulate other charged hydrophilic molecules, such as peptides and proteins.

Development and characterization of nanoparticulate formulation of a water soluble prodrug of dexamethasone by HIP complexation

PubMed Central

Gaudana, Ripal; Parenky, Ashwin; Vaishya, Ravi; Samanta, Swapan K.; Mitra, Ashim K.

2015-01-01

The objective of this study was to develop and characterize a nanoparticulate-based sustained release formulation of a water soluble dipeptide prodrug of dexamethasone, valine–valine-dexamethasone (VVD). Being hydrophilic in nature, it readily leaches out in the external aqueous medium and hence partitions poorly into the polymeric matrix resulting in minimal entrapment in nanoparticles. Hence, hydrophobic ion pairing (HIP) complexation of the prodrug was employed with dextran sulphate as a complexing polymer. A novel, solid in oil in water emulsion method was employed to encapsulate the prodrug in HIP complex form in poly(lactic-co-glycolic acid) matrix. Nanoparticles were characterized with respect to size, zeta potential, crystallinity of entrapped drug and surface morphology. A significant enhancement in the entrapment of the prodrug in nanoparticles was achieved. Finally, a simple yet novel method was developed which can also be applicable to encapsulate other charged hydrophilic molecules, such as peptides and proteins. PMID:20939702

β Coronae Bolealis: Lithium and Cerium Contribution to the Blend at 6708 Å

NASA Astrophysics Data System (ADS)

Drake, N. A.; Hubrig, S.; Polosukhina, N. S.; de La Reza, R.

2006-06-01

We analyze the Li I 6708 Å spectral region of the chemically peculiar Ap star βCrB using high resolution, high signal-to-noise spectra obtained at different rotation phases. Our study shows that the Ce II line at 6708.099 Å is a main contributor to the spectral feature at 6708 Å. This fact explains the observed red shift of the Li I doublet of about 0.2 Å found by Hack et al. (1997). We derive the values of lithium and cerium abundances for different rotation phases and show that βCrB has ``cosmic'' Li abundance.

Role of cerium oxide nanoparticle-induced autophagy as a safeguard to exogenous H2O2-mediated DNA damage in tobacco BY-2 cells.

PubMed

Sadhu, Abhishek; Ghosh, Ilika; Moriyasu, Yuji; Mukherjee, Anita; Bandyopadhyay, Maumita

2018-04-13

The effect of cerium oxide nanoparticle (CeNP) in plants has elicited substantial controversy. While some investigators have reported that CeNP possesses antioxidant properties, others observed CeNP to induce reactive oxygen species (ROS). In spite of considerable research carried out on the effects of CeNP in metazoans, fundamental studies that can unveil its intracellular consequences linking ROS production, autophagy and DNA damage are lacking in plants. To elucidate the impact of CeNP within plant cells, tobacco BY-2 cells were treated with 10, 50 and 250 µg ml-1 CeNP (Ce10, Ce50 and Ce250), for 24 h. Results demonstrated concentration-dependent accumulation of Ca2+ and ROS at all CeNP treatment sets. However, significant DNA damage and alteration in antioxidant defence systems were noted prominently at Ce50 and Ce250. Moreover, Ce50 and Ce250 induced DNA damage, analysed by comet assay and DNA diffusion experiments, complied with the concomitant increase in ROS. Furthermore, to evaluate the antioxidant property of CeNP, treated cells were washed after 24 h (to minimise CeNP interference) and challenged with H2O2 for 3 h. Ce10 did not induce genotoxicity and H2O2 exposure to Ce10-treated cells showed lesser DNA breakage than cells treated with H2O2 only. Interestingly, Ce10 provided better protection over N-acetyl-L-cysteine against exogenous H2O2 in BY-2 cells. CeNP exposure to transgenic BY-2 cells expressing GFP-Atg8 fusion protein exhibited formation of autophagosomes at Ce10. Application of vacuolar protease inhibitor E-64c and fluorescent basic dye acridine orange, further demonstrated accumulation of particulate matters in the vacuole and occurrence of acidic compartments, the autophagolysosomes, respectively. BY-2 cells co-treated with CeNP and autophagy inhibitor 3-methyladenine exhibited increased DNA damage in Ce10 and cell death at all assessed treatment sets. Thus, current results substantiate an alternative autophagy-mediated, antioxidant and

Cadmium sulfide quantum dots induce oxidative stress and behavioral impairments in the marine clam Scrobicularia plana.