Performance Evaluation of an Oxygen Sensor as a Function of the Samaria Doped Ceria Film Thickness

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

Sanghavi, Rahul P.; Nandasiri, Manjula I.; Kuchibhatla, Satyanarayana V N T

The current demand in the automobile industry is in the control of air-fuel mixture in the combustion engine of automobiles. Oxygen partial pressure can be used as an input parameter for regulating or controlling systems in order to optimize the combustion process. Our goal is to identify and optimize the material system that would potentially function as the active sensing material for such a device that monitors oxygen partial pressure in these systems. We have used thin film samaria doped ceria (SDC) as the sensing material for the sensor operation, exploiting the fact that at high temperatures, oxygen vacancies generatedmore » due to samarium doping act as conducting medium for oxygen ions which hop through the vacancies from one side to the other contributing to an electrical signal. We have recently established that 6 atom % Sm doping in ceria films has optimum conductivity. Based on this observation, we have studied the variation in the overall conductivity of 6 atom % samaria doped ceria thin films as a function of thickness in the range of 50 nm to 300 nm at a fixed bias voltage of 2 volts. A direct proportionality in the increase in the overall conductivity is observed with the increase in sensing film thickness. For a range of oxygen pressure values from 1 mTorr to 100 Torr, a tolerable hysteresis error, good dynamic response and a response time of less than 10 seconds was observed« less

Anisotropic vacancy-mediated phonon mode softening in Sm and Gd doped ceria.

PubMed

Jung, Dong-Hyuk; Lee, Ji-Hwan; Kilic, Mehmet Emin; Soon, Aloysius

2018-04-18

Ceria doped with Sm and Gd (SDC and GDC) has been suggested as a promising candidate for the electrolyte used in solid oxide fuel cells (SOFCs), since it has relatively high oxygen ion conductivity at intermediate temperature. There have been many previous experimental and computational studies to investigate the properties, structure, and effect of vacancies, etc. for SDC and GDC. However, in these previous studies, it is commonly assumed that the interaction between oxygen vacancies is negligible and many focus only on the mono-vacancy system. In addition, the possibility of anisotropic vibrational motion of the oxygen ions around vacancies is often neglected. In this paper, using both first-principle density-functional theory and classical molecular dynamics calculations, we investigate the structural and vibrational properties of the optimized SDC and GDC structures, such as bonding analysis, phonon density-of-state and mean-square-displacement of the oxygen ions. Also, we report the direction-dependent vibrations at the specific frequency of the oxygen ions near the vacancies, activation energies, and diffusion coefficients of SDC and GDC which can extend our understanding of diffusion dynamics in doped ceria-based electrolytes for SOFC applications.

Biogas as a fuel for solid oxide fuel cells and synthesis gas production: effects of ceria-doping and hydrogen sulfide on the performance of nickel-based anode materials.

PubMed

Laycock, Christian J; Staniforth, John Z; Ormerod, R Mark

2011-05-28

Numerous investigations have been carried out into the conversion of biogas into synthesis gas (a mixture of H(2) + CO) over Ni/YSZ anode cermet catalysts. Biogas is a variable mixture of gases consisting predominantly of methane and carbon dioxide (usually in a 2 : 1 ratio, but variable with source), with other constituents including sulfur-containing gases such as hydrogen sulfide, which can cause sulfur poisoning of nickel catalysts. The effect of temperature on carbon deposition and sulfur poisoning of 90 : 10 mol% Ni/YSZ under biogas conversion conditions has been investigated by carrying out a series of catalytic reactions of methane-rich (2 : 1) CH(4)/CO(2) mixtures in the absence and presence of H(2)S over the temperature range 750-1000 °C. The effect of ceria-doping on carbon dioxide reforming, carbon deposition and sulfur tolerance has also been investigated by carrying out a similar series of reactions over ceria-doped Ni/YSZ. Ceria was doped at 5 mol% of the nickel content to give an anode catalyst composition of 85.5 : 4.5 : 10 mol% Ni/CeO(2)/YSZ. Reactions were followed using quadrupolar mass spectrometry (QMS) and the amount of carbon deposition was analysed by subjecting the reacted catalyst samples to a post-reaction temperature programmed oxidation (TPO). On undoped Ni/YSZ, carbon deposition occurred predominantly through thermal decomposition of methane. Ceria-doping significantly suppressed methane decomposition and at high temperatures simultaneously promoted the reverse Boudouard reaction, significantly lowering carbon deposition. Sulfur poisoning of Ni/YSZ occurred in two phases, the first of which caused the most activity loss and was accelerated on increasing the reaction temperature, while the second phase had greater stability and became more favourable with increasing reaction temperature. Adding H(2)S significantly inhibited methane decomposition, resulting in much less carbon deposition. Ceria-doping significantly increased the sulfur

Proton Relaxivity and Magnetic Hyperthermia Evaluation of Gadolinium Doped Nickel Ferrite Nanoparticles as Potential Theranostic Agents.

PubMed

Yadavalli, Tejabhiram; Raja, Paradeep; Ramaswamy, Shivaraman; Chandrasekharan, Gopalakrishnan; Chennakesavulu, Ramasamy

2017-02-01

This paper outlines the preparation of gadolinium doped nickel ferrite nanoparticles as potential magnetic carriers and longitudinal magnetic resonance imaging contrast agents using hydrothermal method with gadolinium concentration varying from 10% to 40%. A concise effect on the crystal structure was observed at 10% and 20% gadolinium doping, while gadolinium oxide was observed to leach at concentrations exceeding 20%. Further, gadolinium doped nickel ferrites were analyzed for their morphological, magnetic, proton relaxation and magnetic hyperthermia heating properties to understand their potential role as magnetic carrier agents. Low temperature and room temperature magnetic studies conducted on the samples showed comparatively high magnetic saturation with low remanent magnetization. Further, relaxometry studies revealed a high relaxation rate of 6.63 s−1 at a concentration of 0.1 mg/mL. Magnetic hyperthermia studies of the samples at a concentration of 1 mg/mL, assessed that the samples attained a temperature of 68 °C in 240 seconds.

Detonation nanodiamond introduced into samarium doped ceria electrolyte improving performance of solid oxide fuel cell

NASA Astrophysics Data System (ADS)

Pei, Kai; Li, Hongdong; Zou, Guangtian; Yu, Richeng; Zhao, Haofei; Shen, Xi; Wang, Liying; Song, Yanpeng; Qiu, Dongchao

2017-02-01

A novel electrolyte materials of introducing detonation nanodiamond (DNDs) into samarium doped ceria (SDC) is reported here. 1%wt. DNDs doping SDC (named SDC/ND) can enlarge the electrotyle grain size and change the valence of partial ceria. DNDs provide the widen channel to accelerate the mobility of oxygen ions in electrolyte. Larger grain size means that oxygen ions move easier in electrolyte, it can also reduce the alternating current (AC) impedance spectra of internal grains. The lower valence of partial Ce provides more oxygen vacancies to enhance mobility rate of oxygen ions. Hence all of them enhance the transportation of oxygen ions in SDC/ND electrolyte and the OCV. Ultimately the power density of SOFC can reach 762 mw cm-2 at 800 °C (twice higher than pure SDC, which is 319 mw cm-2 at 800 °C), and it remains high power density in the intermediate temperature (600-800 °C). It is relatively high for the electrolyte supported (300 μm) cells.

Molten carbonate fuel cell cathode with mixed oxide coating

DOEpatents

Hilmi, Abdelkader; Yuh, Chao-Yi

2013-05-07

A molten carbonate fuel cell cathode having a cathode body and a coating of a mixed oxygen ion conductor materials. The mixed oxygen ion conductor materials are formed from ceria or doped ceria, such as gadolinium doped ceria or yttrium doped ceria. The coating is deposited on the cathode body using a sol-gel process, which utilizes as precursors organometallic compounds, organic and inorganic salts, hydroxides or alkoxides and which uses as the solvent water, organic solvent or a mixture of same.

Calcium-doped ceria/titanate tabular functional nanocomposite by layer-by-layer coating method

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

Liu, Xiang W., E-mail: lxwluck@gmail.co; Devaraju, M.K.; Yin, Shu

2010-07-15

Ca-doped ceria (CDC)/tabular titanate (K{sub 0.8}Li{sub 0.27}Ti{sub 1.73}O{sub 4}, TT) UV-shielding functional nanocomposite with fairly uniform CDC coating layers was prepared through a polyelectrolyte-associated layer-by-layer (LbL) coating method. TT with lepidocrocite-like layered structure was used as the substrate, poly (diallyldimethylammonium chloride) (PDDA) was used as a coupling agent, CDC nanoparticles were used as the main UV-shielding component. CDC/TT nanocomposites with various coating layers of CDC were obtained through a multistep coating process. The phases were studied by X-ray diffraction. The morphology and coating quality were studied by scanning electron microscopy and element mapping of energy dispersive X-ray analysis. The oxidationmore » catalytic activity, UV-shielding ability and using comfort were characterized by Rancimat test, UV-vis spectra and dynamic friction test, respectively. CDC/TT nanocomposites with low oxidation catalytic activity, high UV-shielding ability and good using comfort were finally obtained. - Graphical abstract: Through the control of surface charge of particles calcium-doped ceria/titanate composites with low oxidation catalytic activity, higher UV-shielding ability and excellent comfort was obtained by a facile layer-by-layer coating method.« less

Stability of Gadolinium-Doped Liquid Organic Scintillators

NASA Astrophysics Data System (ADS)

Gromov, M. B.; Kuznetsov, D. S.; Murchenko, A. E.; Novikova, G. Ya.; Obinyakov, B. A.; Oralbaev, A. Yu.; Plakitina, K. V.; Skorokhvatov, M. D.; Sukhotin, S. V.; Chepurnov, A. S.; Etenko, A. V.

2018-03-01

The technology of preparing a linear-alkylbenzene-based gadolinium-doped liquid organic scintillator (Gd-LOS) as a target material in reactor antineutrino detectors has been developed. Results of longterm measurements of the light yield of Gd-LOS in contact with acryl and stainless steel are presented, which confirm the compatibility of Gd-LOS with these materials. The measurements were performed for two otherwise identical LOS detectors only differing in wall materials of the sensitive volume: acryl versus stainless steel. The results of measurements over about one year showed almost the same, relatively small decreases in the light yield of both detectors. It is concluded that both structural materials can be used in detector parts contacting with Gd-doped scintillator. Such a long-term parallel comparative test was carried out for the first time.

Preparation and characterization of Pd doped ceria-ZnO nanocomposite catalyst for methyl tert-butyl ether (MTBE) photodegradation.

PubMed

Seddigi, Zaki S; Bumajdad, Ali; Ansari, Shahid P; Ahmed, Saleh A; Danish, Ekram Y; Yarkandi, Naeema H; Ahmed, Shakeel

2014-01-15

A series of binary oxide catalysts (ceria-ZnO) were prepared and doped with different amounts of palladium in the range of 0.5%-1.5%. The prepared catalysts were characterized by SEM, TEM, XRD and XPS, as well as by N2 sorptiometry study. The XPS results confirmed the structure of the Pd CeO2-x-ZnO. The photocatalytic activity of these catalysts was evaluated for degradation of MTBE in water. These photocatalyst efficiently degrade a 100ppm aqueous solution of MTBE upon UV irradiation for 5h in the presence of 100mg of each of these photocatalysts. The removal of 99.6% of the MTBE was achieved with the ceria-ZnO catalyst doped with 1% Pd. In addition to the Pd loading, the N2 sorptiometry study introduced other factors that might affect the catalytic efficiency is the catalyst average pore sizes. The photoreaction was determined to be a first order reaction. Copyright © 2013 Elsevier B.V. All rights reserved.

Converting ceria polyhedral nanoparticles into single-crystal nanospheres.

PubMed

Feng, Xiangdong; Sayle, Dean C; Wang, Zhong Lin; Paras, M Sharon; Santora, Brian; Sutorik, Anthony C; Sayle, Thi X T; Yang, Yi; Ding, Yong; Wang, Xudong; Her, Yie-Shein

2006-06-09

Ceria nanoparticles are one of the key abrasive materials for chemical-mechanical planarization of advanced integrated circuits. However, ceria nanoparticles synthesized by existing techniques are irregularly faceted, and they scratch the silicon wafers and increase defect concentrations. We developed an approach for large-scale synthesis of single-crystal ceria nanospheres that can reduce the polishing defects by 80% and increase the silica removal rate by 50%, facilitating precise and reliable mass-manufacturing of chips for nanoelectronics. We doped the ceria system with titanium, using flame temperatures that facilitate crystallization of the ceria yet retain the titania in a molten state. In conjunction with molecular dynamics simulation, we show that under these conditions, the inner ceria core evolves in a single-crystal spherical shape without faceting, because throughout the crystallization it is completely encapsulated by a molten 1- to 2-nanometer shell of titania that, in liquid state, minimizes the surface energy. The principle demonstrated here could be applied to other oxide systems.

Thickness effects of yttria-doped ceria interlayers on solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Fan, Zeng; An, Jihwan; Iancu, Andrei; Prinz, Fritz B.

2012-11-01

Determining the optimal thickness range of the interlayed yttria-doped ceria (YDC) films promises to further enhance the performance of solid oxide fuel cells (SOFCs) at low operating temperatures. The YDC interlayers are fabricated by the atomic layer deposition (ALD) method with one super cycle of the YDC deposition consisting of 6 ceria deposition cycles and one yttria deposition cycle. YDC films of various numbers of ALD super cycles, ranging from 2 to 35, are interlayered into bulk fuel cells with a 200 um thick yttria-stabilized zirconia (YSZ) electrolyte. Measurements and analysis of the linear sweep voltammetry of these fuel cells reveal that the performance of the given cells is maximized at 10 super cycles. Auger elemental mapping and X-ray photoelectron spectroscopy (XPS) techniques are employed to determine the film completeness, and they verify 10 super cycles of YDC to be the critical thickness point. This optimal YDC interlayer condition (6Ce1Y × 10 super cycles) is applied to the case of micro fuel cells as well, and the average performance enhancement factor is 1.4 at operating temperatures of 400 and 450 °C. A power density of 1.04 W cm-2 at 500 °C is also achieved with the optimal YDC recipe.

Solid solutions of gadolinium doped zinc oxide nanorods by combined microwave-ultrasonic irradiation assisted crystallization

NASA Astrophysics Data System (ADS)

Kiani, Armin; Dastafkan, Kamran; Obeydavi, Ali; Rahimi, Mohammad

2017-12-01

Nanocrystalline solid solutions consisting of un-doped and gadolinium doped zinc oxide nanorods were fabricated by a modified sol-gel process utilizing combined ultrasonic-microwave irradiations. Polyvinylpyrrolidone, diethylene glycol, and triethylenetetramine respectively as capping, structure directing, and complexing agents were used under ultrasound dynamic aging and microwave heating to obtain crystalline nanorods. Crystalline phase monitoring, lattice parameters and variation, morphology and shape, elemental analysis, functional groups, reducibility, and the oxidation state of emerged species were examined by PXRD, FESEM, TEM, EDX, FTIR, micro Raman, H2-TPR, and EPR techniques. Results have verified that irradiation mechanism of gelation and crystallization reduces the reaction time, augments the crystal quality, and formation of hexagonal close pack structure of Wurtzite morphology. Besides, dissolution of gadolinium within host lattice involves lattice deformation, unit cell distortion, and angular position variation. Structure related shape and growth along with compositional purity were observed through microscopic and spectroscopic surveys. Furthermore, TPR and EPR studies elucidated more detailed behavior upon exposure to the exerted irradiations and subsequent air-annealing including the formed oxidation states and electron trapping centers, presence of gadolinium, zinc, and oxygen disarrays and defects, as well as alteration in the host unit cell via gadolinium addition.

Role of associated defects in oxygen ion conduction and surface exchange reaction for epitaxial samaria-doped ceria thin films as catalytic coatings

DOE PAGES

Yang, Nan; Shi, Yanuo; Schweiger, Sebastian; ...

2016-05-18

Samaria-doped ceria (SDC) thin films are particularly important for energy and electronic applications such as micro-solid oxide fuel cells, electrolysers, sensors and memristors. In this paper we report a comparative study investigating ionic conductivity and surface reactions for well-grown epitaxial SDC films varying the samaria doping concentration. With increasing doping above 20 mol% of samaria, an enhancement in the defect association was observed by Raman spectroscopy. The role of such defect associates on the films` oxygen ion transport and exchange was investigated by electrochemical impedance spectroscopy and electrochemical strain microscopy (ESM). The measurements reveal that the ionic transport has amore » sharp maximum in ionic conductivity and drop in its activation energy down to 0.6 eV for 20 mol% doping. Increasing the doping concentration further up to 40 mol%, raises the activation energy substantially by a factor of two. We ascribe the sluggish transport kinetics to the "bulk" ionic-near ordering in case of the heavily doped epitaxial films. Analysis of the ESM first order reversal curve measurements indicate that these associated defects may have a beneficial role by lowering the activation of the oxygen exchange "surface" reaction for heavily doped 40 mol% of samaria. We reveal in a model experiment through a solid solution series of samaria doped ceria epitaxial films that the occurrence of associate defects in the bulk affects the surface charging state of the films to increase the exchange rates. Lastly, the implication of these findings are the design of coatings with tuned oxygen surface exchange by control of bulk associate clusters for future electro-catalytic applications.« less

On direct internal methane steam reforming kinetics in operating solid oxide fuel cells with nickel-ceria anodes

NASA Astrophysics Data System (ADS)

Thallam Thattai, A.; van Biert, L.; Aravind, P. V.

2017-12-01

Major operating challenges remain to safely operate methane fuelled solid oxide fuel cells due to undesirable temperature gradients across the porous anode and carbon deposition. This article presents an experimental study on methane steam reforming (MSR) global kinetics for single operating SOFCs with Ni-GDC (gadolinium doped ceria) anodes for low steam to carbon (S/C) ratios and moderate current densities. The study points out the hitherto insufficient research on MSR global and intrinsic kinetics for operating SOFCs with complete Ni-ceria anodes. Further, it emphasizes the need to develop readily applicable global kinetic models as a subsequent step from previously reported state-of-art and complex intrinsic models. Two rate expressions of the Power law (PL) and Langmuir-Hinshelwood (LH) type have been compared and based on the analysis, limitations of using previously proposed rate expressions for Ni catalytic beds to study MSR kinetics for complete cermet anodes have been identified. Firstly, it has been shown that methane reforming on metallic (Ni) current collectors may not be always negligible, contrary to literature reports. Both PL and LH kinetic models predict significantly different local MSR reaction rate and species partial pressure distributions along the normalized reactor length, indicating a strong need for further experimental verifications.

The Sulphur Poisoning Behaviour of Gadolinia Doped Ceria Model Systems in Reducing Atmospheres

PubMed Central

Gerstl, Matthias; Nenning, Andreas; Iskandar, Riza; Rojek-Wöckner, Veronika; Bram, Martin; Hutter, Herbert; Opitz, Alexander Karl

2016-01-01

An array of analytical methods including surface area determination by gas adsorption using the Brunauer, Emmett, Teller (BET) method, combustion analysis, XRD, ToF-SIMS, TEM and impedance spectroscopy has been used to investigate the interaction of gadolinia doped ceria (GDC) with hydrogen sulphide containing reducing atmospheres. It is shown that sulphur is incorporated into the GDC bulk and might lead to phase changes. Additionally, high concentrations of silicon are found on the surface of model composite microelectrodes. Based on these data, a model is proposed to explain the multi-facetted electrochemical degradation behaviour encountered during long term electrochemical measurements. While electrochemical bulk properties of GDC stay largely unaffected, the surface polarisation resistance is dramatically changed, due to silicon segregation and reaction with adsorbed sulphur. PMID:28773771

Engineered gadolinium-doped carbon dots for magnetic resonance imaging-guided radiotherapy of tumors.

PubMed

Du, Fengyi; Zhang, Lirong; Zhang, Li; Zhang, Miaomiao; Gong, Aihua; Tan, Youwen; Miao, Jiawen; Gong, Yuhua; Sun, Mingzhong; Ju, Huixiang; Wu, Chaoyang; Zou, Shenqiang

2017-03-01

The effectiveness of radiotherapy can decrease due to inaccurate positioning of machinery and inherent radioresistance of tumors. To address this issue, we present a novel theranostic nanoplatform based on gadolinium-doped carbon dots (Gd-doped CDs) designed specifically for magnetic resonance imaging (MRI)-guided radiotherapy of tumors. The Gd-doped CDs (∼18 nm) with dispersibility in water and stable photoluminescence were synthesized via a one-step hydrothermal approach. After tail vein injection of the Gd-doped CDs, they exhibited a relatively long circulation time (∼6 h), enabled efficient passive tumor targeting. Gd-doped CDs accumulate in the kidney and could be cleared out of the body from bladder. Importantly, they exhibited favorable biocompatibility with excellent performance in longitudinal relaxivity rate (r 1 ) of 6.45 mM -1 S -1 and radiosensitization enhancements. These results show that Gd-doped CDs are excellent T 1 contrast agents and radiosensitizers, possessing great promise for MRI-guided radiotherapy of tumors. Copyright © 2016 Elsevier Ltd. All rights reserved.

High-pressure high-temperature phase diagram of gadolinium studied using a boron-doped heater anvil

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

Montgomery, J. M.; Samudrala, G. K.; Vohra, Y. K.

A boron-doped designer heater anvil is used in conjunction with powder x-ray diffraction to collect structural information on a sample of quasi-hydrostatically loaded gadolinium metal up to pressures above 8 GPa and 600 K. The heater anvil consists of a natural diamond anvil that has been surface modified with a homoepitaxially grown chemical-vapor-deposited layer of conducting boron-doped diamond, and is used as a DC heating element. Internally insulating both diamond anvils with sapphire support seats allows for heating and cooling of the high-pressure area on the order of a few tens of seconds. This device is then used to scan the phasemore » diagram of the sample by oscillating the temperature while continuously increasing the externally applied pressure and collecting in situ time-resolved powder diffraction images. In the pressure-temperature range covered in this experiment, the gadolinium sample is observed in its hcp, αSm, and dhcp phases. Under this temperature cycling, the hcp → αSm transition proceeds in discontinuous steps at points along the expected phase boundary. From these measurements (representing only one hour of synchrotron x-ray collection time), a single-experiment equation of state and phase diagram of each phase of gadolinium is presented for the range of 0–10 GPa and 300–650 K.« less

High-pressure high-temperature phase diagram of gadolinium studied using a boron-doped heater anvil

NASA Astrophysics Data System (ADS)

Montgomery, J. M.; Samudrala, G. K.; Velisavljevic, N.; Vohra, Y. K.

2016-04-01

A boron-doped designer heater anvil is used in conjunction with powder x-ray diffraction to collect structural information on a sample of quasi-hydrostatically loaded gadolinium metal up to pressures above 8 GPa and 600 K. The heater anvil consists of a natural diamond anvil that has been surface modified with a homoepitaxially grown chemical-vapor-deposited layer of conducting boron-doped diamond, and is used as a DC heating element. Internally insulating both diamond anvils with sapphire support seats allows for heating and cooling of the high-pressure area on the order of a few tens of seconds. This device is then used to scan the phase diagram of the sample by oscillating the temperature while continuously increasing the externally applied pressure and collecting in situ time-resolved powder diffraction images. In the pressure-temperature range covered in this experiment, the gadolinium sample is observed in its hcp, αSm, and dhcp phases. Under this temperature cycling, the hcp → αSm transition proceeds in discontinuous steps at points along the expected phase boundary. From these measurements (representing only one hour of synchrotron x-ray collection time), a single-experiment equation of state and phase diagram of each phase of gadolinium is presented for the range of 0-10 GPa and 300-650 K.

Incorporating Rich Mesoporosity into a Ceria-Based Catalyst via Mechanochemistry

DOE PAGES

Zhan, Wangcheng; Yang, Shize; Zhang, Pengfei; ...

2017-08-15

Ceria-based materials possessing mesoporous structures afford higher activity than the corresponding bulk materials in CO oxidation and other catalytic applications, because of the wide pore channel and high surface area. The development of a direct, template-free, and scalable technology for directing porosity inside ceriabased materials is highly welcome. Here in this paper, a family of mesoporous transition-metaldoped ceria catalysts with specific surface areas up to 122 m 2 g -1 is constructed by mechanochemical grinding. No templates, additives, or solvents are needed in this process, while the mechanochemistry-mediated restructuring and the decomposing of the organic group led to plentiful mesopores.more » Interestingly, the copper species are evenly dispersed in the ceria matrix at the atomic scale, as observed in high resolution scanning transmission electron microscopy in high angle annular dark field. The copper-doped ceria materials show good activity in the CO oxidation.« less

Dielectric properties and activation behavior of gadolinium doped nanocrystalline yttrium chromite

NASA Astrophysics Data System (ADS)

Sinha, R.; Basu, S.; Meikap, A. K.

2018-04-01

Gadolinium doped Yttrium Chromite nanoparticles are synthesized following sol-gel method. The formation of the nanoparticles are confirmed by XRD and TEM measurements. Dielectric permittivity and dielectric loss are estimated within the temperature range 298K to 523K and in the frequency range 20 Hz to 1 MHz. Dielectric permittivity follows the power law ɛ'(f) ∝ Tm. It is observed that the temperature exponent m increases with the decreasing frequency. The temperature variation of resistivity shows that the samples have semiconducting behavior. The activation energy is also measured.

Ga and In modified ceria as supports for cobalt-catalyzed Fischer-Tropsch synthesis

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

Gnanamani, Muthu Kumaran; Jacobs, Gary; Shafer, Wilson D.

Ga- and In-modified ceria (Ce 0.8Ga 0.2O 2, Ce 0.8In 0.2O 2) materials were used as supports for cobalt-catalyzed Fischer-Tropsch synthesis (FTS). The addition of Ga to ceria was found to improve CO conversion for cobalt-catalyzed FTS, while the addition of In tended to decrease it. A similar trend was observed with the Ag-promoted cobalt/ceria catalysts. Doping of ceria with Ga or In decreased methane and increased the selectivity to olefins and alcohols for Ag-promoted cobalt/ceria. The sum of the products of olefins and alcohols for various catalysts exhibited a decreasing trend as follows: Ag-Co/Ce-Ga > Ag-Co/Ce-In > Ag-Co/Ce. Resultsmore » of H 2-TPR-XANES showed that adding of Ga or In to ceria increases the fraction of Ce 3+ in the surface shell for both unpromoted and Ag-promoted catalysts in the range of temperature typical of catalyst activation. In conclusion, this partially reduced ceria plays an important role in controlling the product selectivity of cobalt-catalyzed FT synthesis.« less

Ga and In modified ceria as supports for cobalt-catalyzed Fischer-Tropsch synthesis

DOE PAGES

Gnanamani, Muthu Kumaran; Jacobs, Gary; Shafer, Wilson D.; ...

2017-08-24

Ga- and In-modified ceria (Ce 0.8Ga 0.2O 2, Ce 0.8In 0.2O 2) materials were used as supports for cobalt-catalyzed Fischer-Tropsch synthesis (FTS). The addition of Ga to ceria was found to improve CO conversion for cobalt-catalyzed FTS, while the addition of In tended to decrease it. A similar trend was observed with the Ag-promoted cobalt/ceria catalysts. Doping of ceria with Ga or In decreased methane and increased the selectivity to olefins and alcohols for Ag-promoted cobalt/ceria. The sum of the products of olefins and alcohols for various catalysts exhibited a decreasing trend as follows: Ag-Co/Ce-Ga > Ag-Co/Ce-In > Ag-Co/Ce. Resultsmore » of H 2-TPR-XANES showed that adding of Ga or In to ceria increases the fraction of Ce 3+ in the surface shell for both unpromoted and Ag-promoted catalysts in the range of temperature typical of catalyst activation. In conclusion, this partially reduced ceria plays an important role in controlling the product selectivity of cobalt-catalyzed FT synthesis.« less

Synthesis of samarium doped gadolinium oxide nanorods, its spectroscopic and physical properties

NASA Astrophysics Data System (ADS)

Boopathi, G.; Gokul Raj, S.; Ramesh Kumar, G.; Mohan, R.; Mohan, S.

2018-06-01

One-dimensional samarium doped gadolinium oxide [Sm:Gd2O3] nanorods have been synthesized successfully through co-precipitation technique in aqueous solution. The as-synthesized and calcined products were characterized by using powder X-ray diffraction pattern, Fourier transform Raman spectroscopy, thermogravimetric/differential thermal analysis, scanning electron microscopy with energy-dispersive X-ray analysis, transmission electron microscopy, Fourier transform infrared spectroscopy, Ultraviolet-Visible spectrometry, photoluminescence spectrophotometer and X-ray photoelectron spectroscopy techniques. The obtained results are discussed in detailed manner.

A palladium-doped ceria@carbon core-sheath nanowire network: a promising catalyst support for alcohol electrooxidation reactions

NASA Astrophysics Data System (ADS)

Tan, Qiang; Du, Chunyu; Sun, Yongrong; Du, Lei; Yin, Geping; Gao, Yunzhi

2015-08-01

A novel palladium-doped ceria and carbon core-sheath nanowire network (Pd-CeO2@C CSNWN) is synthesized by a template-free and surfactant-free solvothermal process, followed by high temperature carbonization. This hierarchical network serves as a new class of catalyst support to enhance the activity and durability of noble metal catalysts for alcohol oxidation reactions. Its supported Pd nanoparticles, Pd/(Pd-CeO2@C CSNWN), exhibit >9 fold increase in activity toward the ethanol oxidation over the state-of-the-art Pd/C catalyst, which is the highest among the reported Pd systems. Moreover, stability tests show a virtually unchanged activity after 1000 cycles. The high activity is mainly attributed to the superior oxygen-species releasing capability of Pd-doped CeO2 nanowires by accelerating the removal of the poisoning intermediate. The unique interconnected one-dimensional core-sheath structure is revealed to facilitate immobilization of the metal catalysts, leading to the improved durability. This core-sheath nanowire network opens up a new strategy for catalyst performance optimization for next-generation fuel cells.A novel palladium-doped ceria and carbon core-sheath nanowire network (Pd-CeO2@C CSNWN) is synthesized by a template-free and surfactant-free solvothermal process, followed by high temperature carbonization. This hierarchical network serves as a new class of catalyst support to enhance the activity and durability of noble metal catalysts for alcohol oxidation reactions. Its supported Pd nanoparticles, Pd/(Pd-CeO2@C CSNWN), exhibit >9 fold increase in activity toward the ethanol oxidation over the state-of-the-art Pd/C catalyst, which is the highest among the reported Pd systems. Moreover, stability tests show a virtually unchanged activity after 1000 cycles. The high activity is mainly attributed to the superior oxygen-species releasing capability of Pd-doped CeO2 nanowires by accelerating the removal of the poisoning intermediate. The unique

Fe-doping effects on the structural, vibrational, magnetic, and electronic properties of ceria nanoparticles

NASA Astrophysics Data System (ADS)

Aragón, Fermin F. H.; Aquino, Juan C. R.; Ramos, Jesus E.; Coaquira, José A. H.; Gonzalez, Ismael; Macedo, Waldemar A. A.; da Silva, Sebastião W.; Morais, Paulo C.

2017-11-01

In this work, we report on a single-pot synthesis route based on a polymeric precursor method used for successfully producing undoped and iron-doped CeO2 nanoparticles with iron contents up to 10.0 mol. %. The formation of high-crystalline nanoparticles with a cubic fluorite structure is determined for all the studied samples. Meanwhile, the magnetic measurements of the undoped ceria nanoparticles revealed the occurrence of ferromagnetism of bound magnetic polarons of a fraction of Ce3+ at room temperature, and only a paramagnetic behavior of Fe3+ ions was determined for Fe-doped ceria nanoparticles. A monotonous reduction of the effective magnetic moment of the Fe3+ ions was determined. It suggests a change from a high-spin to low-spin state of Fe ions as the Fe content is increased. The 3+ valence state of the iron ions has been confirmed by the Fe K-edge X-ray absorption near-edge structure (XANES) and Mössbauer spectroscopy measurements. X-ray photoelectron spectroscopy data analysis evidenced a coexistence of Ce3+ and Ce4+ ions and a decreasing tendency of the relative fraction of Ce3+ ions in the surface region of the particles as the iron content is increased. Although the coexistence of Ce3+ and Ce4+ is confirmed by results obtained via Ce L3-edge XANES measurements, any clear dependence of the relative relation of Ce3+ ions on the iron content is determined, suggesting a homogeneous distribution of Ce3+ and Ce4+-ions in the whole volume of the particles. Ce L3-edge extended X-ray absorption fine structure revealed that the Ce-O bond distance shows a monotonous decrease as the Fe content is increased, which is in good agreement with the shrinking of the unit cell volume with the iron content determined from XRD data analysis, reinforcing the substitutional solution of Ce and Fe ions in the CeO2 matrix.

Carbonate-mediated Mars-van Krevelen mechanism for CO oxidation on cobalt-doped ceria catalysts: facet-dependence and coordination-dependence.

PubMed

Liu, Bing; Li, Wenping; Song, Weiyu; Liu, Jian

2018-06-13

Carbonate intermediates have been reported to play an active role in CO oxidation over ceria-based catalysts in recent experimental studies. However, the detailed CO oxidation mechanism involving carbonate intermediates over ceria-based catalysts remains obscure. In this work, we carried out systematic density functional theory calculations corrected by on-site Coulomb interactions (DFT+U) to investigate the complete CO oxidation mechanism involving carbonate intermediates over cobalt-doped CeO2 catalysts, aiming to unravel how the carbonate participates in CO oxidation and shed light on the underlying factors that control the carbonate-mediated reaction mechanism. A novel carbonate-mediated Mars-van Krevelen (M-vK) mechanism was proposed, in which the carbonate acts as an active intermediate rather than a spectator and can react with CO to form CO2. This carbonate-mediated M-vK mechanism is facet-dependent because it is predominant on the (110) surface whereas the conventional M-vK mechanism is more favorable on (111) and (100) surfaces. The origin of facet-dependence was discussed by analyzing the geometric and electronic structures. It is found that the negatively charged bent CO2- intermediate formed on the (110) surface plays a critical role in the carbonate-mediated M-vK mechanism, whereas the formation of a neutral linear CO2 intermediate on (111) and (100) surfaces hinders the carbonate-mediated M-vK mechanism. The surface oxygen vacancy hinders the formation of carbonate intermediates, indicating that the carbonate-mediated M-vK mechanism is also vacancy-dependent. The formation of carbonate intermediates on different metal (Ti, V, W, Mo and Re) doped CeO2(110) surfaces was studied and the results indicate that the coordination environment of the dopant species is a key factor that determines the carbonate-mediated M-vK mechanism. This study provides atomic-scale insights into the reaction mechanism involving carbonate intermediates and the structure

High-pressure high-temperature phase diagram of gadolinium studied using a boron-doped heater anvil

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

Montgomery, J. M.; Samudrala, G. K.; Velisavljevic, N.

A boron-doped designer heater anvil is used in conjunction with powder x-ray diffraction to collect structural information on a sample of quasi-hydrostatically loaded gadolinium metal up to pressures above 8 GPa and 600 K. The heater anvil consists of a natural diamond anvil that has been surface modified with a homoepitaxially-grown chemical-vapor-deposited layer of conducting boron-doped diamond, and is used as a DC heating element. Internally insulating both diamond anvils with sapphire support seats allows for heating and cooling of the high pressure area on the order of a few tens of seconds. This device is then used to scanmore » the phase diagram of the sample by oscillating the temperature while continuously increasing the externally applied pressure and collecting in situ time-resolved powder diffraction images. In the pressure-temperature range covered in the experiment the gadolinium sample is observed in its hcp, αSm, and dhcp phases. Under this temperature cycling, the hcp→αSm transition proceeds in discontinuous steps at points along the expected phase boundary. Additionally, the unit cell volumes of each phase deviate from the expected thermal expansion behavior just before each transition is observed from the diffraction data. From these measurements (representing only one hour of synchrotron x-ray collection time), a single-experiment equation of state and phase diagram of each phase of gadolinium is presented for the range of 0 - 10 GPa and 300 - 650 K.« less

High-pressure high-temperature phase diagram of gadolinium studied using a boron-doped heater anvil

DOE PAGES

Montgomery, J. M.; Samudrala, G. K.; Velisavljevic, N.; ...

2016-04-07

A boron-doped designer heater anvil is used in conjunction with powder x-ray diffraction to collect structural information on a sample of quasi-hydrostatically loaded gadolinium metal up to pressures above 8 GPa and 600 K. The heater anvil consists of a natural diamond anvil that has been surface modified with a homoepitaxially-grown chemical-vapor-deposited layer of conducting boron-doped diamond, and is used as a DC heating element. Internally insulating both diamond anvils with sapphire support seats allows for heating and cooling of the high pressure area on the order of a few tens of seconds. This device is then used to scanmore » the phase diagram of the sample by oscillating the temperature while continuously increasing the externally applied pressure and collecting in situ time-resolved powder diffraction images. In the pressure-temperature range covered in the experiment the gadolinium sample is observed in its hcp, αSm, and dhcp phases. Under this temperature cycling, the hcp→αSm transition proceeds in discontinuous steps at points along the expected phase boundary. Additionally, the unit cell volumes of each phase deviate from the expected thermal expansion behavior just before each transition is observed from the diffraction data. From these measurements (representing only one hour of synchrotron x-ray collection time), a single-experiment equation of state and phase diagram of each phase of gadolinium is presented for the range of 0 - 10 GPa and 300 - 650 K.« less

Design and development of a Gadolinium-doped water Cherenkov detector

NASA Astrophysics Data System (ADS)

Poudyal, Nabin

This thesis describes a research and development project for neutron capture and detection in Gadolinium doped water. The Sanford Underground Research Facility (SURF) is exploring rare event physics, such as neutrinoless double beta decay (MAJORANA Project) and dark-matter detection (LUX experiment). The success of these experiments requires a careful study and understanding of background radiation, including flux and energy spectrum. The background radiation from surface contamination, radioactive decays of U-238, Th-232, Rn-222 in the surrounding rocks and muon induced neutrons have a large impact on the success of rare-event physics. The main objective of this R&D project is to measure the neutron flux contributing to ongoing experiments at SURF and suppress it by identification and capture method. For this purpose, we first modeled and designed a detector with Geant4 software. The approximate dimension of the detector is determined. The neutron capture percentage of the detector is estimated using Monte Carlo. The energy response of the detector is simulated. Next, we constructed the experimental detector, an acrylic rectangular tank (60cm x 30cm x 30cm), filled with Gadolinium-doped deionized water. The tank is coated with high efficient reflector and then taped with black electrical tape to make it opaque. The voltage dividers attached to PMTs are covered with mu-metal. Two 5-inch Hamamatsu Photomultiplier tubes were attached on both sides facing the tank to collect the Cherenkov light produced in the water. The detector utilizes the principle of Cherenkov light emission by a charged particle moving through a water at a speed higher than the speed of light in the water, hence it has an inherent energy threshold of Cherenkov photon production. This property reduces the lower energy backgrounds. Event data are obtained using the Data Acquisition hardware, Flash Analog to digital converter, along with Multi Instance Data Acquisition software. Post

Gadolinia-Doped Ceria Cathodes for Electrolysis of CO2

NASA Technical Reports Server (NTRS)

Adler, Stuart B.

2009-01-01

Gadolinia-doped ceria, or GDC, (Gd(0.4)Ce(0.6)O(2-delta), where the value of delta in this material varies, depending on the temperature and oxygen concentration in the atmosphere in which it is being used) has shown promise as a cathode material for high-temperature electrolysis of carbon dioxide in solid oxide electrolysis cells. The polarization resistance of a GDC electrode is significantly less than that of an otherwise equivalent electrode made of any of several other materials that are now in use or under consideration for use as cathodes for reduction of carbon dioxide. In addition, GDC shows no sign of deterioration under typical temperature and gas-mixture operating conditions of a high-temperature electrolyzer. Electrolysis of CO2 is of interest to NASA as a way of generating O2 from the CO2 in the Martian atmosphere. On Earth, a combination of electrolysis of CO2 and electrolysis of H2O might prove useful as a means of generating synthesis gas (syngas) from the exhaust gas of a coal- or natural-gas-fired power plant, thereby reducing the emission of CO2 into the atmosphere. The syngas a mixture of CO and H2 could be used as a raw material in the manufacture, via the Fisher-Tropsch process, of synthetic fuels, lubrication oils, and other hydrocarbon prod

Structure, morphology and reducibility of ceria-doped zirconia

NASA Astrophysics Data System (ADS)

Aribi, Koubra; Soltani, Zohra; Ghelamallah, Madani; Granger, Pascal

2018-03-01

Zr1-xCexOx has been prepared by hydrolysis, in neutral medium, starting from rough ZrO2 and CeO2 materials as simple and cheaper synthesis method compared to sol-gel routes. The oxy-hydroxide precursors thus obtained were calcined under air at 450 °C, 900 °C and 1200 °C. The impact of those thermal treatments on the structure, texture and related redox properties has been investigated. Higher specific surface area than those observed on ceria were observed after calcination at low temperature, i.e., 450 °C. Above that temperature thermal sintering occurs having a detrimental effect on the specific surface area related to crystal growth more accentuated on CeO2. The formation of several Zrsbnd Ce mixed oxide phases formed by incorporation and substitution of Zr in the structure of ceria was characterized. A complete loss of specific surface area is noticeable after calcination at 1200 °C. XRD and SEM analysis revealed the formation of two mixed oxides structure, i.e. Ce2Zr2O7.04 and Ce2Zr2O7 corresponding to different redox behavior evidenced from H2-TPR experiments.

Photoluminescent properties of spider silk coated with Eu-doped nanoceria

NASA Astrophysics Data System (ADS)

Dmitrović, Svetlana; Nikolić, Marko G.; Jelenković, Branislav; Prekajski, Marija; Rabasović, Mihailo; Zarubica, Aleksandra; Branković, Goran; Matović, Branko

2017-02-01

Spider dragline silk was coated with pure as well as Eu-doped ceria nanopowders at the room temperature. The treatment was done by immersion of the spider silk mesh into aqueous solutions of cerium nitrate (Ce(NO3)3) and ammonium hydroxide (NH4OH). Depending on the relationship between Ce3+ ion and ammonium hydroxide concentration, coated fibers exhibited a different thickness. Obtained materials were studied by means of FESEM. It was found that ceria nanoparticles of average size of 3 nm were coated along spider thread. X-ray diffraction (XRD) and selected-area electron diffraction (SAED) confirmed crystal nature of nanoparticle coating of spider silk. By using Williamson-Hall plots, crystallite size and strain were estimated. EDS measurement confirmed the presence of Eu in spider-Eu-doped ceria composite, and according to FTIR analysis, the interaction between CeO2 and spider silk was proposed. The morphology of obtained composite was observed by TEM. The photoluminescence emission spectra of spider silk coated with Eu-doped ceria were measured with two different excitations of 385 and 466 nm. The two-photon excited auto-fluorescence of spider silk coated with Eu-doped ceria was detected using a nonlinear laser scanning microscope. Obtained composite has a potential as a fluorescent labeling material in diverse applications.

Catalytic oxidation of soot on mesoporous ceria-based mixed oxides with cetyltrimethyl ammonium bromide (CTAB)-assisted synthesis.

PubMed

Zhu, Hongjian; Xu, Jing; Yichuan, Yuge; Wang, Zhongpeng; Gao, Yibo; Liu, Wei; Yin, Henan

2017-12-15

Mesoporous ceria and transition metal-doped ceria (M 0.1 Ce 0.9 O 2 (M=Mn, Fe, Co, Cu)) catalysts were synthesized via CTAB-assisted method. The physicochemical properties of the prepared catalysts were characterized by XRD, DLS analysis, SEM, BET, Raman, H 2 -TPR and in situ DRIFT techniques. The catalytic activity tests for soot oxidation were performed under tight contact of soot/catalyst mixtures in the presence of O 2 and NO+O 2 , respectively. The obtained results show that mesoporous ceria-based solid solutions can be formed with large surface areas and small crystallite size. Transition metals doping enhances the oxygen vacancies and improves redox properties of the solids, resulting in the increased NO oxidation capacity and NO x adsorption capacity. The soot oxidation activity in the presence of O 2 is enhanced by doping transition metal, which may be related to their high surface area, increased oxygen vacancies and improved redox properties. The soot combustion is accelerated by the NO 2 -assisted mechanism under NO+O 2 atmosphere, facilitating an intimate contact between the soot and the catalyst. Copyright © 2017 Elsevier Inc. All rights reserved.

A palladium-doped ceria@carbon core-sheath nanowire network: a promising catalyst support for alcohol electrooxidation reactions.

PubMed

Tan, Qiang; Du, Chunyu; Sun, Yongrong; Du, Lei; Yin, Geping; Gao, Yunzhi

2015-08-28

A novel palladium-doped ceria and carbon core-sheath nanowire network (Pd-CeO2@C CSNWN) is synthesized by a template-free and surfactant-free solvothermal process, followed by high temperature carbonization. This hierarchical network serves as a new class of catalyst support to enhance the activity and durability of noble metal catalysts for alcohol oxidation reactions. Its supported Pd nanoparticles, Pd/(Pd-CeO2@C CSNWN), exhibit >9 fold increase in activity toward the ethanol oxidation over the state-of-the-art Pd/C catalyst, which is the highest among the reported Pd systems. Moreover, stability tests show a virtually unchanged activity after 1000 cycles. The high activity is mainly attributed to the superior oxygen-species releasing capability of Pd-doped CeO2 nanowires by accelerating the removal of the poisoning intermediate. The unique interconnected one-dimensional core-sheath structure is revealed to facilitate immobilization of the metal catalysts, leading to the improved durability. This core-sheath nanowire network opens up a new strategy for catalyst performance optimization for next-generation fuel cells.

Aluminum-doped ceria-zirconia solid solutions with enhanced thermal stability and high oxygen storage capacity.

PubMed

Dong, Qiang; Yin, Shu; Guo, Chongshen; Sato, Tsugio

2012-10-01

A facile solvothermal method to synthesize aluminum-doped ceria-zirconia (Ce0.5Zr0.5-xAlxO2-x/2, x = 0.1 to 0.4) solid solutions was carried out using Ce(NH4)2(NO3)6, Zr(NO3)3·2H2O Al(NO3)3·9H2O, and NH4OH as the starting materials at 200°C for 24 h. The obtained solid solutions from the solvothermal reaction were calcined at 1,000°C for 20 h in air atmosphere to evaluate the thermal stability. The synthesized Ce0.5Zr0.3Al0.2O1.9 particle was characterized for the oxygen storage capacity (OSC) in automotive catalysis. For the characterization, X-ray diffraction, transmission electron microscopy, and the Brunauer-Emmet-Teller (BET) technique were employed. The OSC values of all samples were measured at 600°C using thermogravimetric-differential thermal analysis. Ce0.5Zr0.3Al0.2O1.9 solid solutions calcined at 1,000°C for 20 h with a BET surface area of 18 m2 g-1 exhibited a considerably high OSC of 427 μmol-O g-1 and good OSC performance stability. The same synthesis route was employed for the preparation of the CeO2 and Ce0.5Zr0.5O2. The incorporation of aluminum ion in the lattice of ceria-based catalyst greatly enhanced the thermal stability and OSC.

Gadolinium doped ceria interlayers for Solid Oxide Fuel Cells cathodes: Enhanced reactivity with sintering aids (Li, Cu, Zn), and improved densification by infiltration

NASA Astrophysics Data System (ADS)

Nicollet, Clement; Waxin, Jenny; Dupeyron, Thomas; Flura, Aurélien; Heintz, Jean-Marc; Ouweltjes, Jan Pieter; Piccardo, Paolo; Rougier, Aline; Grenier, Jean-Claude; Bassat, Jean-Marc

2017-12-01

This paper reports the study of the densification of 20% Gd doped ceria (Ce0.8Gd0.2O1.9 (GDC)) interlayers in SOFC cathodes through two different routes: the well-known addition of sintering elements, and an innovative densification process by infiltration. First, Li, Cu, and Zn nitrates were added to GDC powders. The effect of these additives on the densification was studied by dilatometry on pellets, and show a large decrease of the sintering temperature from 1330 °C (pure GDC), down to 1080 °C, 950 °C, and 930 °C for Zn, Cu, and Li addition, respectively. However, this promising result does not apply to screen-printed layers, which are more porous than pellets and in which the shrinkage is constrained by the substrate. The second approach consists in preparing a pre-sintered GDC layer, which is subsequently infiltrated with Ce and Gd nitrates and sintered at 1250 °C to increase its density. Such an approach results in highly dense GDC interlayers. Using La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) as electrode, the influence of the interlayers on the cathode performance was studied. The addition of sintering aids dramatically increases the cell resistances, most likely because the additives increase the reactivity between GDC and either Yttria Stabilized Zirconia (YSZ) or LSCF, thus losing the expected benefit related to the decrease of sintering temperatures. The interlayers prepared by infiltration do not induce additional resistances in the cell, which results in power densities of single cells 40-50% higher than those of cells prepared with commercial GDC interlayers, making this approach a valuable alternative to sintering aids.

Nanoparticle Precipitation in Irradiated and Annealed Ceria Doped with Metals for Emulation of Spent Fuels

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

Jiang, Weilin; Conroy, Michele A.; Kruska, Karen

Epsilon alloy precipitates have been observed with varied compositions and sizes in spent nuclear fuels, such as UO2. Presence of the inclusions, along with other oxide precipitates, gas bubbles and irradiation-induced structural defects, can significantly degrade the physical properties of the fuel. To predict fuel performance, a fundamental study of the precipitation processes is needed. This study uses ceria (CeO2) as a surrogate for UO2. Polycrystalline CeO2 films doped with Mo, Ru, Rh, Pd and Re (surrogate for Tc) were grown at 823 K using pulsed laser deposition, irradiated at 673 K with He+ ions, and subsequently annealed at highermore » temperatures. A number of methods, including transmission electron microscopy and atom probe tomography, were applied to characterize the samples. The results indicate that there is a uniform distribution of the doped metals in the as-grown CeO2 film. Pd particles of ~3 nm in size appear near dislocation edges after He+ ion irradiation to ~13 dpa. Thermal annealing at 1073 K in air leads to formation of precipitates with Mo and Pd around grain boundaries. Further annealing at 1373 K produces 70 nm sized precipitates with small grains at cavities.« less

Effect of solid-phase amorphization on the spectral characteristics of europium-doped gadolinium molybdate

NASA Astrophysics Data System (ADS)

Shmurak, S. Z.; Kiselev, A. P.; Kurmasheva, D. M.; Red'Kin, B. S.; Sinitsyn, V. V.

2010-05-01

A method is proposed for detecting spectral characteristics of optically inactive molybdates of rare-earth elements by their doping with rare-earth ions whose luminescence lies in the transparency region of all structural modifications of the sample. Gadolinium molybdate is chosen as the object of investigations, while europium ions are used as an optically active and structurally sensitive admixture. It is shown that after the action of a high pressure under which gadolinium molybdate passes to the amorphous state, the spectral characteristics of Gd1.99Eu0.01(MoO4)3 (GMO:Eu) change radically; namely, considerable line broadening is observed in the luminescence spectra and the luminescence excitation spectra, while the long-wave threshold of optical absorption is shifted considerably (by approximately 1.1 eV) towards lower energies. It is found that by changing the structural state of GMO:Eu by solid-state amorphization followed by annealing, the spectral characteristics of the sample can be purposefully changed. This is extremely important for solving the urgent problem of designing high-efficiency light-emitting diodes producing “white” light.

Transfer hydrogenation over sodium-modified ceria: Enrichment of redox sites active for alcohol dehydrogenation

DOE PAGES

Nelson, Nicholas C.; Boote, Brett W.; Naik, Pranjali; ...

2017-01-17

Ceria (CeO 2) and sodium-modified ceria (Ce-Na) were prepared through combustion synthesis. Palladium was deposited onto the supports (Pd/CeO 2 and Pd/Ce-Na) and their activity for the aqueous-phase transfer hydrogenation of phenol using 2-propanol under liquid flow conditions was studied. Pd/Ce-Na showed a marked increase (6×) in transfer hydrogenation activity over Pd/CeO 2. Material characterization indicated that water-stable sodium species were not doped into the ceria lattice, but rather existed as subsurface carbonates. Modification of ceria by sodium provided more adsorption and redox active sites (i.e. defects) for 2-propanol dehydrogenation. This effect was an intrinsic property of the Ce-Na supportmore » and independent of Pd. The redox sites active for 2-propanol dehydrogenation were thermodynamically equivalent on both supports/catalysts. At high phenol concentrations, the reaction was limited by 2-propanol adsorption. Furthermore, the difference in catalytic activity was attributed to the different numbers of 2-propanol adsorption and redox active sites on each catalyst.« less

Magnetic and magnetothermal studies of pure and doped gadolinium silicide nanoparticles for self-controlled hyperthermia applications

NASA Astrophysics Data System (ADS)

Alnasir, M. Hisham; Awan, M. S.; Manzoor, Sadia

2018-03-01

We report on magnetic and magnetothermal properties of undoped and doped gadolinium silicide (Gd5Si4) nanoparticles with the objective of simultaneously attaining high specific absorption rate (SAR) and low Curie temperature (TC) suitable for self-controlled hyperthermia applications for which TC ∼ 315-320 K. Pellets of doped gadolinium silicide Gd5(Si1-xGex)4 and (Gd1-xRx)5Si4 with R = Ho, Nd and Er and 0 ≤ x ≤ 0.35 were made by arc melting and reduced to nanoparticulate form by surfactant assisted ball milling. Structural and morphological studies were done using X-ray diffraction and scanning electron microscopy respectively. All samples show soft magnetic properties. At low fields there is a ferromagnetic to paramagnetic transition that reduces remanance and coercivity to zero making these materials very attractive for biomedical applications. Zero-field-cooled thermal demagnetization measurements showed that TC of these nanoparticles can be lowered to lie within the limits required for self-controlled hyperthermia by varying the dopant concentration. Specific absorption rates (SAR's) were obtained from magnetothermia measurements made in an ac magnetic field of amplitude 10 Oe and frequency 300 kHz. We have identified samples that have SAR values larger or comparable to those of magnetite and several ferrite nanoparticles, while having Curie temperatures that are low enough for self controlled hyperthermia applications.

Kinetics of CO2 Reduction over Nonstoichiometric Ceria

PubMed Central

2015-01-01

The kinetics of CO2 reduction over nonstoichimetric ceria, CeO2−δ, a material of high potential for thermochemical conversion of sunlight to fuel, has been investigated for a wide range of nonstoichiometries (0.02 ≤ δ ≤ 0.25), temperatures (693 ≤ T ≤ 1273 K), and CO2 concentrations (0.005 ≤ pCO2 ≤ 0.4 atm). Samples were reduced thermally at 1773 K to probe low nonstoichiometries (δ < 0.05) and chemically at lower temperatures in a H2 atmosphere to prevent particle sintering and probe the effect of higher nonstoichiometries (δ < 0.25). For extents greater than δ = 0.2, oxidation rates at a given nonstoichiometry are hindered for the duration of the reaction, presumably because of near-order changes, such as lattice compression, as confirmed via Raman Spectroscopy. Importantly, this behavior is reversible and oxidation rates are not affected at lower δ. Following thermal reduction at very low δ, however, oxidation rates are an order of magnitude slower than those of chemically reduced samples, and rates monotonically increase with the initial nonstoichiometry (up to δ = 0.05). This dependence may be attributed to the formation of stable defect complexes formed between oxygen vacancies and polarons. When the same experiments are performed with 10 mol % Gd3+ doped ceria, in which defect complexes are less prevalent than in pure ceria, this dependence is not observed. PMID:26693270

Ceria Doped Zinc Oxide Nanoflowers Enhanced Luminol-Based Electrochemiluminescence Immunosensor for Amyloid-β Detection.

PubMed

Wang, Jing-Xi; Zhuo, Ying; Zhou, Ying; Wang, Hai-Jun; Yuan, Ruo; Chai, Ya-Qin

2016-05-25

In this work, ceria doped ZnO nanomaterials with flower-structure (Ce:ZONFs) were prepared to construct a luminol-based electrochemiluminescence (ECL) immunosensor for amyloid-β protein (Aβ) detection. Herein, carboxyl groups (-COOH) covered Ce:ZONFs were synthesized by a green method with lysine as reductant. After that, Ce:ZONFs-based ECL nanocomposite was prepared by combining the luminophore of luminol and Ce:ZONFs via amidation and physical absorption. Luminol modified on Ce:ZONFs surface could generate a strong ECL signal under the assistance of reactive oxygen species (ROSs) (such as OH(•) and O2(•-)), which were produced by a catalytic reaction between Ce:ZONFs and H2O2. It was worth noticing that a quick Ce(4+) ↔ Ce(3+) reaction in this doped material could increase the rate of electron transfer to realize the signal amplification. Subsequently, the luminol functionalized Ce:ZONFs (Ce:ZONFs-Lum) were covered by secondary antibody (Ab2) and glucose oxidase (GOD), respectively, to construct a novel Ab2 bioconjugate (Ab2-GOD@Ce:ZONFs-Lum). The wire-structured silver-cysteine complex (AgCys NWs) with a large number of -COOH, which was synthesized by AgNO3 and l-cysteine, was used as substrate of the immunosensor to capture the primary antibody (Ab1). Under the optimal conditions, this proposed ECL immunosensor had exhibited high sensitivity for Aβ detection with a wide linear range from 80 fg/mL to 100 ng/mL and an ultralow detection limit of 52 fg/mL. Meanwhile, this biosensor had good specificity for Aβ, indicating that the provided strategy had a promising potential in the detection of Aβ.

[Optical and spectral parameters in Ce3+ -doped gadolinium gallium aluminum garnet glass-ceramics].

PubMed

Gong, Hua; Zhao, Xin; Yu, Xiao-bo; Setsuhisa, Tanabe; Lin, Hai

2010-01-01

The crystalline phases of Ce3+ -doped gadolinium gallium aluminum garnet (GGAG) glass-ceramics were investigated by X-ray diffraction, and the fluorescence spectra were recorded under the pumping of blue light-emitting diode (LED) using an integrating sphere of 10-inch in diameter, which connected to a CCD detector. The spectral power distribution of the glass-ceramics was obtained from the measured spectra first, and then the quantum yield was derived based on the photon distribution. The quantum yield of Ce3+ emission in GGAG glass-ceramics is 29.2%, meanwhile, the color coordinates and the correlated color temperature (CCT) of combined white light were proved to be x = 0.319, y = 0.349 and 6086 K, respectively. Although the quantum yield is a little smaller than the value in Ce3+ -doped YAG glass-ceramics, the CCT of the combined white light is much smaller than that in the latter. The optical behavior of GGAG glass-ceramics provides new vision for developing comfortable LED lighting devices.

Mechanical characterization of hydroxyapatite, thermoelectric materials and doped ceria

NASA Astrophysics Data System (ADS)

Fan, Xiaofeng

For a variety of applications of brittle ceramic materials, porosity plays a critical role structurally and/or functionally, such as in engineered bone scaffolds, thermoelectric materials and in solid oxide fuel cells. The presence of porosity will affect the mechanical properties, which are essential to the design and application of porous brittle materials. In this study, the mechanical property versus microstructure relations for bioceramics, thermoelectric (TE) materials and solid oxide fuel cells were investigated. For the bioceramic material hydroxyapatite (HA), the Young's modulus was measured using resonant ultrasound spectroscopy (RUS) as a function of (i) porosity and (ii) microcracking damage state. The fracture strength was measured as a function of porosity using biaxial flexure testing, and the distribution of the fracture strength was studied by Weibull analysis. For the natural mineral tetrahedrite based solid solution thermoelectric material (Cu10Zn2As4S13 - Cu 12Sb4S13), the elastic moduli, hardness and fracture toughness were studied as a function of (i) composition and (ii) ball milling time. For ZiNiSn, a thermoelectric half-Heusler compound, the elastic modulus---porosity and hardness---porosity relations were examined. For the solid oxide fuel cell material, gadolina doped ceria (GDC), the elastic moduli including Young's modulus, shear modulus, bulk modulus and Poisson's ratio were measured by RUS as a function of porosity. The hardness was evaluated by Vickers indentation technique as a function of porosity. The results of the mechanical property versus microstructure relations obtained in this study are of great importance for the design and fabrication of reliable components with service life and a safety factor. The Weibull modulus, which is a measure of the scatter in fracture strength, is the gauge of the mechanical reliability. The elastic moduli and Poisson's ratio are needed in analytical or numerical models of the thermal and

Alkali metal and alkali earth metal gadolinium halide scintillators

DOEpatents

Bourret-Courchesne, Edith; Derenzo, Stephen E.; Parms, Shameka; Porter-Chapman, Yetta D.; Wiggins, Latoria K.

2016-08-02

The present invention provides for a composition comprising an inorganic scintillator comprising a gadolinium halide, optionally cerium-doped, having the formula A.sub.nGdX.sub.m:Ce; wherein A is nothing, an alkali metal, such as Li or Na, or an alkali earth metal, such as Ba; X is F, Br, Cl, or I; n is an integer from 1 to 2; m is an integer from 4 to 7; and the molar percent of cerium is 0% to 100%. The gadolinium halides or alkali earth metal gadolinium halides are scintillators and produce a bright luminescence upon irradiation by a suitable radiation.

Rare-Earth Doping and Co-Doping of GaN for Magnetic and Luminescent Applications

DTIC Science & Technology

2010-08-16

The main focus of this project is the study of Gadolinium doped Gallium Nitride. Calculations were carried out to elucidate the origin of the reported...Ga vacancies in the triple negative charge state, which is the most likely charge state in semi-insulating samples, 1. REPORT DATE (DD-MM-YYYY) 4...applications Report Title ABSTRACT The main focus of this project is the study of Gadolinium doped Gallium Nitride. Calculations were carried out to

Band-gap modulation via gallium substitution in cerium doped gadolinium aluminum garnet using a mixed fuel combustion approach

NASA Astrophysics Data System (ADS)

Tyagi, Mohit; Pitale, Shreyas S.; Ghosh, Manoranjan; Shinde, Seema

2014-04-01

Cerium doped Gadolinium garnets (Gd3AlxGa5-xO12 where 0≤x≤5) are synthesized via combustion synthesis using mixture of urea and glycine fuels. A 4h Post annealing at 1400 oC is found to be necessary for pure phase formation. Lattice spacing variation as a result of partial or total Ga substitution at Al site was mapped by X-ray diffraction. Photoluminescence emission of Ce shifts as a consequence of Ga substitution and therefore suggests a local re-adjustment of crystal field around activator site.

Gadolinium-doped water cerenkov-based neutron and high energy gamma-ray detector and radiation portal monitoring system

DOEpatents

Dazeley, Steven A; Svoboda, Robert C; Bernstein, Adam; Bowden, Nathaniel

2013-02-12

A water Cerenkov-based neutron and high energy gamma ray detector and radiation portal monitoring system using water doped with a Gadolinium (Gd)-based compound as the Cerenkov radiator. An optically opaque enclosure is provided surrounding a detection chamber filled with the Cerenkov radiator, and photomultipliers are optically connected to the detect Cerenkov radiation generated by the Cerenkov radiator from incident high energy gamma rays or gamma rays induced by neutron capture on the Gd of incident neutrons from a fission source. The PMT signals are then used to determine time correlations indicative of neutron multiplicity events characteristic of a fission source.

Nanoamplifiers synthesized from gadolinium and gold nanocomposites for magnetic resonance imaging

NASA Astrophysics Data System (ADS)

Tian, Xiumei; Shao, Yuanzhi; He, Haoqiang; Liu, Huan; Shen, Yingying; Huang, Wenlin; Li, Li

2013-03-01

We have synthesized an efficient and highly sensitive nanoamplifier composed of gadolinium-doped silica nanoparticles and gold nanoparticles (AuNPs). Magnetic resonance imaging (MRI) in vitro and in vivo assays revealed enhancement of signal sensitivity, which may be explained by electron transfer between water and gadolinium-doped nanoparticles, apparent in the presence of gold. In vitro and in vivo evaluation demonstrated nanoamplifier incurred minimal cytotoxicity and immunotoxicity, increased stability, and gradual excretion patterns. Tumor targeted properties were preliminarily determined when the nanoamplifier was injected into mouse models of colon cancer liver metastasis. Furthermore, although AuNPs departed from the nanoamplifiers in specific mice tissues, optical and magnetic resonance imaging was efficient, especially in metastatic tumors. These assays validate our nanoamplifier as an effective MRI signal enhancer with sensitive cancer diagnosis potential.We have synthesized an efficient and highly sensitive nanoamplifier composed of gadolinium-doped silica nanoparticles and gold nanoparticles (AuNPs). Magnetic resonance imaging (MRI) in vitro and in vivo assays revealed enhancement of signal sensitivity, which may be explained by electron transfer between water and gadolinium-doped nanoparticles, apparent in the presence of gold. In vitro and in vivo evaluation demonstrated nanoamplifier incurred minimal cytotoxicity and immunotoxicity, increased stability, and gradual excretion patterns. Tumor targeted properties were preliminarily determined when the nanoamplifier was injected into mouse models of colon cancer liver metastasis. Furthermore, although AuNPs departed from the nanoamplifiers in specific mice tissues, optical and magnetic resonance imaging was efficient, especially in metastatic tumors. These assays validate our nanoamplifier as an effective MRI signal enhancer with sensitive cancer diagnosis potential. Electronic supplementary information

Highly transparent cerium doped gadolinium gallium aluminum garnet ceramic prepared with precursors fabricated by ultrasonic enhanced chemical co-precipitation.

PubMed

Zhang, Ji-Yun; Luo, Zhao-Hua; Jiang, Hao-Chuan; Jiang, Jun; Chen, Chun-Hua; Zhang, Jing-Xian; Gui, Zhen-Zhen; Xiao, Na

2017-11-01

Cerium doped gadolinium gallium aluminum garnet (GGAG:Ce) ceramic precursors have been synthesized with an ultrasonic chemical co-precipitation method (UCC) and for comparison with a traditional chemical co-precipitation method (TCC). The effect of ultra-sonication on the morphology of powders and the transmittance of GGAG:Ce ceramics are studied. The results indicate that the UCC method can effectively improve the homogenization and sinterability of GGAG:Ce powders, which contribute to obtain high transparent GGAG ceramic with the highest transmittance of 81%. Copyright © 2017 Elsevier B.V. All rights reserved.

Band-gap modulation via gallium substitution in cerium doped gadolinium aluminum garnet using a mixed fuel combustion approach

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

Tyagi, Mohit; Pitale, Shreyas S.; Ghosh, Manoranjan

2014-04-24

Cerium doped Gadolinium garnets (Gd{sub 3}Al{sub x}Ga{sub 5−x}O{sub 12} where 0≤x≤5) are synthesized via combustion synthesis using mixture of urea and glycine fuels. A 4h Post annealing at 1400 oC is found to be necessary for pure phase formation. Lattice spacing variation as a result of partial or total Ga substitution at Al site was mapped by X-ray diffraction. Photoluminescence emission of Ce shifts as a consequence of Ga substitution and therefore suggests a local re-adjustment of crystal field around activator site.

Luminescence studies of rare earth doped yttrium gadolinium mixed oxide phosphor

NASA Astrophysics Data System (ADS)

Som, S.; Choubey, A.; Sharma, S. K.

2012-09-01

This paper reports the photoluminescence and thermoluminescence properties of gamma ray induced rare earth doped yttrium gadolinium mixed oxide phosphor. The europium (Eu3+) was used as rare earth dopant. The phosphor was prepared by chemical co-precipitation method according to the formula (Y2-x-yGdx) O3: Euy3+ (x=0.5; y=0.05). The photoluminescence emission spectrum of the prepared phosphor shows intense peaks in the red region at 615 nm for 5D0→7F2 transitions and the photoluminescence excitation spectra show a broad band located around 220-270 nm for the emission wavelength fixed at 615 nm. The thermoluminescence studies were carried out after irradiating the phosphor by gamma rays in the dose range from 100 Gy to 1 KGy. In the thermoluminescence glow curves, one single peak was observed at about 300 °C of which the intensity increases linearly in the studied dose range of gamma rays. The glow peak was deconvoluted by GlowFit program and the kinetic parameters associated with the deconvoluted peaks were calculated. The kinetic parameters were also calculated by various glow curve shape and heating rate methods.

Anomalous Hall effect in calcium-doped lanthanum cobaltite and gadolinium

NASA Astrophysics Data System (ADS)

Baily, Scott Alan

The physical origin of the anomalous (proportional to magnetization) Hall effect is not very well understood. While many theories account for a Hall effect proportional to the magnetization of a material, these theories often predict effects significantly smaller than those found in ferromagnetic materials. An even more significant deficiency of the conventional theories is that they predict an anomalous Hall resistivity that is proportional to a power of the resistivity, and in the absence of a metal insulator transition cannot account for the anomalous Hall effect that peaks near TC. Recent models based on a geometric, or Berry, phase have had a great deal of success describing the anomalous Hall effect in double-exchange systems (e.g., lanthanum manganite and chromium dioxide). In gadolinium, as in double-exchange magnets, the exchange interaction is mediated by the conduction electrons and the anomalous Hall effect may therefore resemble that of CrO2 and other metallic double-exchange ferromagnets. Lanthanum cobaltite is similar to manganite in many ways, but a strong double-exchange interaction is not present. Calcium-doped lanthanum cobaltite films were found to have the largest anomalous Hall effect of any ferromagnetic metal. The primary purpose of this study is to gain insight into the origin of the anomalous Hall effect with the hope that these theories can be extended to account for the effect in other materials. The Hall resistivity, magnetoresistance, and magnetization of a Gadolinium single crystal were measured in fields up to 30 T. Cobaltite films were grown via laser ablation and characterized by a variety of techniques. Hall resistivity, magnetoresistance, magnetization, and magnetothermopower of L 1-xCaxCoO3 samples with 0.15 < x < 0.4 were measured in fields up to 7 T. The Gd results suggest that Berry's phase contributes partially to the Hall effect near TC. Berry's phase theories hold promise for explaining the large anomalous Hall effect in

Synthesis and characterization of mesoporous ceria/alumina nanocomposite materials via mixing of the corresponding ceria and alumina gel precursors.

PubMed

Khalil, Kamal M S

2007-03-01

Mesoporous ceria/alumina, CeO(2)/Al(2)O(3), composites containing 10, 20 and 30% (w/w) ceria were prepared by a novel gel mixing method. In the method, ceria gel (formed via hydrolysis of ammonium cerium(IV) nitrate by aqueous ammonium carbonate solution) and alumina gel (formed via controlled hydrolysis of aluminum tri-isopropoxide) were mixed together. The mixed gel was subjected to subsequent drying and calcination for 3 h at 400, 600, 800 and 1000 degrees C. The uncalcined (dried at 110 degrees C) and the calcined composites were investigated by different techniques including TGA, DSC, FTIR, XRD, SEM and nitrogen adsorption/desorption isotherms. Results indicated that composites calcined for 3 h at 800 degrees C mainly kept amorphous alumina structure and gamma-alumina formed only upon calcinations at 1000 degrees C. On the other hand, CeO(2) was found to crystallize in the common ceria, cerinite, phase and it kept this structure over the entire calcination range (400-1000 degrees C). Therefore, high surface areas, stable surface textures, and non-aggregated nano-sized ceria dispersions were obtained. A systematic texture change based on ceria ratio was observed, however in all cases mesoporous composite materials exposing thermally stable texture and structure were obtained. The presented method produces composite ceria/alumina materials that suit different applications in the field of catalysis and membranes technology, and throw some light on physicochemical factors that determine textural morphology and thermal stability of such important composite.

Radioluminescence and optical studies of gadolinium calcium phosphate oxyfluoride glasses doped with Sm3+

NASA Astrophysics Data System (ADS)

Meejitpaisan, P.; Insiripong, S.; Kedkaew, C.; Kim, H. J.; Kaewkhao, J.

2017-08-01

Sm3+-doped gadolinium calcium phosphate oxyfluoride glasses have been synthesized and investigated their optical, photo and radioluminescence properties. The glasses were prepared by melt quenching technique at 1400 °C. The characteristic absorption bands of Sm3+ ions originating from the 6H5/2 ground state and occurring absorbed photon in visible light (VIS) and near-infrared (NIR) region with clearly observed from absorption spectra. From the photoluminescence (PL), the glasses showed the emission at 561 (4G5/2→6H5/2), 598 (4G5/2→6H7/2), 644 (4G5/2→6H9/2) and 705 nm (4G5/2→6H11/2). The radioluminescence (RL), emission spectra were corresponding to those from PL measurements. From RL measurement, the integral scintillation efficiency of developed glass was determined at 43% when compared with BGO crystal.

Methane Oxidation on Pd-Ceria. A DFT Study of the Combustion Mechanism over Pd, PdO and Pd-ceria Sites

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

Mayernick, Adam D.; Janik, Michael J.

2010-12-24

Palladium/ceria exhibits unique catalytic activity for hydrocarbon oxidation; however, the chemical and structural properties of active sites on the palladium–ceria surface are difficult to characterize. Strong interactions between palladium and the ceria support stabilize oxidized Pd δ+ species, which may contribute to the significant activity of Pd/ceria for methane oxidation. We present a density functional theory (DFT + U) investigation into methane oxidation over Pd/ceria and quantify the activity of the Pd xCe 1-xO 2(1 1 1) mixed oxide surface in comparison with the PdO(1 0 0) and Pd(1 1 1) surfaces. The methane activation barrier is lowest over themore » Pd xCe 1-xO 2(1 1 1) surface, even lower than over the Pd(1 1 1) surface or low coordinated stepped or kinked Pd sites. Subsequent reaction steps in complete oxidation, including product desorption and vacancy refilling, are considered to substantiate that methane activation remains the rate-limiting step despite the low barrier over Pd xCe 1-xO 2(1 1 1). The low barrier over the Pd xCe 1-xO 2(1 1 1) surface demonstrates that mixed ceria-noble metal oxides offer the potential for improved hydrocarbon oxidation performance with respect to dispersed noble metal particles on ceria.« less

Composite ceria-coated aerogels and methods of making the same

DOEpatents

Eyring, Edward M; Ernst, Richard D; Turpin, Gregory C; Dunn, Brian C

2013-05-07

Ceria-coated aerogels can include an aerogel support material having a stabilized ceria coating thereon. The ceria coating can be formed by solution or vapor deposition of alcogels or aerogels. Additional catalytic metal species can also be incorporated into the coating to form multi-metallic compounds having improved catalytic activity. Further, the ceria coated aerogels retain high surface areas at elevated temperatures. Thus, improvements in catalytic activity and thermal stability can be achieved using these ceria-coated composite aerogels.

Gadolinium Scandium Gallium Garnet (GSGG) as a Solid-State Laser Host

DTIC Science & Technology

1987-07-01

o*SATI CODSi1.SBEC EM (otne nrvrs fnceayad dniy nb)k ubr ~~~~~~~~ Gadolinium Scandium Gallium Garnet (GSGG)asaSldtteLerHt 17. ABSTRACT 6.SUJCTTEM...certain other garnet materials for replacement. It also addresses the solid-state laser host material Gadolinium Scandium Gal- lium Garnet (GSGG) and its...by neodymium-doped yttrium aluminum garnet (Nd:YAG) or other mate- rials for most applications. In the years after the invention of the ruby laser, in

Characterization of ceria electrolyte in solid oxide fuel cell applications

NASA Astrophysics Data System (ADS)

Milliken, Christopher Edward

The goal of this research effort is to characterize cation doped cerium dioxide for use as an electrolyte material in solid oxide fuel cell applications. A variety of analytical techniques including thermogravimetric analysis, controlled atmosphere dilatometry, and AC/DC electronic measurements on single cells and stacks have been coupled with thermodynamic calculations to evaluate the suitability of several doping schemes. The results of this analysis indicate that doping CeOsb2 with 20% SmOsb{1.5} or codoping with 19% GdOsb{1.5} + 1% PrOsb{1.83} provides the best combination of stability and performance. Under dual atmosphere fuel cell conditions, these dopants do not provide sufficient stabilization energy to prevent the reduction of ceria. A significant oxygen leakage current can be expected, particularly near open circuit conditions. Incorporation of 10% SrO provides similar short-term advantages to the lanthanide doped system but this electrolyte material undergoes an irreversible degradation mechanism that results in cell failure within 1500 hours of test. Under fuel cell conditions, the maximum efficiency of such systems in stacks will be below 40% at 200 mW/cmsp2 when operated on humidified hydrogen fuels. This compares to an expected efficiency of 45-50% at a similar power density for nonmixed conducting electrolyte (e.g., YSZ).

Luminescence properties and electronic structure of Ce{sup 3+}-doped gadolinium aluminum garnet

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

Dotsenko, V.P., E-mail: ssclab@ukr.net; Berezovskaya, I.V.; Voloshinovskii, A.S.

2015-04-15

Highlights: • The luminescence properties of Ce{sup 3+} ions in (Y, Gd){sub 3}Al{sub 5}O{sub 12} are analyzed. • The Gd{sup 3+} → Y{sup 3+} substitution leads to increasing of Ce{sup 3+} noncubic crystal field splitting parameter. • The excitation spectra for the Ce{sup 3+} emission in GdAG contain bands at 6.67, 7.75, and 9.76 eV. • These features are due to the Ce{sup 3+}-bound exciton formation and O 2p → Al 3s, 3p transitions. • Contributions from Al atoms to the conduction-band density of states are quite essential. - Abstract: Yttrium-gadolinium aluminum garnets (YGdAG) doped with Ce{sup 3+} ions havemore » been prepared by co-precipitation method. The luminescent properties of Ce{sup 3+} ions in Gd{sub 3(1−x)}Ce{sub 3x}Al{sub 5}O{sub 12} (x = 0.01) have been studied upon excitation in the 2–20 eV region. The substitution of Gd{sup 3+} for Y{sup 3+} in the garnet structure results in broadening the emission band and shifting its maximum towards the longer wavelengths. It was found that in addition to the 4f → 5d excitation bands of Ce{sup 3+} ions, the excitation spectra for the Ce{sup 3+} emission contain bands at 6.67, 7.75, and 9.76 eV. These bands are attributed to the Ce{sup 3+}-bound exciton formation and O 2p → Al 3s, 3p transitions, respectively. Although gadolinium states dominate near the bottom of the conduction band of Gd{sub 3}Al{sub 5}O{sub 12}, contributions from Al{sub tetr} and Al{sub oct} atoms to the conduction-band density of states are evaluated as quite essential.« less

Evaluation of the Effect of Sulfur on the Performance of Nickel/Gadolinium‐Doped Ceria Based Solid Oxide Fuel Cell Anodes

PubMed Central

Yurkiv, Vitaliy; Costa, Rémi; Schiller, Günter; Friedrich, K. Andreas

2016-01-01

Abstract The focus of this study is the measurement and understanding of the sulfur poisoning phenomena of Ni/gadolinium‐doped ceria (CGO) based solid oxide fuel cells (SOFC). Cells with Ni/CGO10 and NiCu5/CGO40 anodes were characterized by using impedance spectroscopy at different temperatures and H2/H2O fuel ratios. The short‐term sulfur poisoning behavior was investigated systematically at temperatures of 800–950 °C, current densities of 0–0.75 A cm−2, and H2S concentrations of 1–20 ppm. A sulfur poisoning mitigation effect was observed at high current loads and temperatures. The poisoning behavior was reversible for short exposure times. It was observed that the sulfur‐affected processes exhibited significantly different relaxation times that depend on the Gd content in the CGO phase. Moreover, it was demonstrated that the capacitance of Ni/CGO10 anodes is strongly dependent on the temperature and gas‐phase composition, which reflects a changing Ce3+/Ce4+ ratio. PMID:27863123

Slurry spin coating of thin film yttria stabilized zirconia/gadolinia doped ceria bi-layer electrolytes for solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Kim, Hyun Joong; Kim, Manjin; Neoh, Ke Chean; Han, Gwon Deok; Bae, Kiho; Shin, Jong Mok; Kim, Gyu-Tae; Shim, Joon Hyung

2016-09-01

Thin ceramic bi-layered membrane comprising yttria-stabilized zirconia (YSZ) and gadolinia-doped ceria (GDC) is fabricated by the cost-effective slurry spin coating technique, and it is evaluated as an electrolyte of solid oxide fuel cells (SOFCs). It is demonstrated that the slurry spin coating method is capable of fabricating porous ceramic films by adjusting the content of ethyl-cellulose binders in the source slurry. The porous GDC layer deposited by spin coating under an optimal condition functions satisfactorily as a cathode-electrolyte interlayer in the test SOFC stack. A 2-μm-thick electrolyte membrane of the spin-coated YSZ/GDC bi-layer is successfully deposited as a dense and stable film directly on a porous NiO-YSZ anode support without any interlayers, and the SOFC produces power output over 200 mW cm-2 at 600 °C, with an open circuit voltage close to 1 V. Electrochemical impedance spectra analysis is conducted to evaluate the performance of the fuel cell components in relation with the microstructure of the spin-coated layers.

Synthesis of gadolinium doped titanium(IV) oxide and their photocatalytic activity to decrease chemical oxygen demand (COD) value of water pollutants

NASA Astrophysics Data System (ADS)

Eddy, Diana Rakhmawaty; Dwiyanti, Dina; Rahayu, Iman; Hastiawan, Iwan; Bahti, Husein H.

2017-05-01

Pesticides are widely used for the control of plant disease. Unfortunately they are highly toxic to terraneous and aquatic life; this is a particular problem in agricultural areas. TiO2 is widely used for pesticide control because of its photocatalytic activity, but it still has inadequacy in its wide band gap. Alternatively, the wide band gap of TiO2 could be narrowed by modification with rare earth element such as gadolinium, so the photocatalytic activity of TiO2could be significantly enhanced. The purpose of this experiment is to synthesize Gd/TiO2 and its application to reduce COD of water pollutants such as carbosulfan pesticide. This experiment is done by doping gadolinium oxide into titanium tetra isopropoxide by sol-gel method. The crystal structure is characterized by using XRD, shown anatase successfully obtained with the smallest crystallite size is 37.655 nm, indicated optimum calcination time is 4 hours. SEM-EDX result shown morphology of crystal is big aggregates. Photocatalytic activity is tested to carbosulfan pesticide, obtained the COD percent decreases up to 87.88%.

UV-shielding property, photocatalytic activity and photocytotoxicity of ceria colloid solutions.

PubMed

Zholobak, N M; Ivanov, V K; Shcherbakov, A B; Shaporev, A S; Polezhaeva, O S; Baranchikov, A Ye; Spivak, N Ya; Tretyakov, Yu D

2011-01-10

UV-shielding property, photocatalytic activity and cytotoxicity (including photocytotoxicity) of citrate-stabilized ceria colloid solutions were studied. It was established that UV-shielding property (namely, the sun protection factor, the critical absorption wavelength and the UVA/UVB-ratio) of ceria nanoparticles are as good as those of titanium dioxide and zinc oxide nanoparticles. It was further demonstrated that ceria nanoparticles possesses substantially lower photocatalytic activity, which additionally decreases upon decrease in ceria particle size. It was found that colloid ceria solutions are non-toxic to mouse fibroblasts (L929) and fibroblast-like cells of African Green monkey (VERO). Moreover, ceria nanoparticles are capable to protect these cells from UV-irradiation-induced damage. It was proposed that nanocrystalline ceria could be used not only as UV-blocking material, but also as prophylactic and even therapeutic compound for sunburns treatment. Copyright © 2010 Elsevier B.V. All rights reserved.

Effect of Dopants and Sintering Method on the Properties of Ceria-Based Electrolytes for IT-SOFCs Applications

NASA Astrophysics Data System (ADS)

Sharma, Payal; Sharma, Chetan; Singh, Kanchan L.; Singh, Anirudh P.

2018-05-01

Doped and co-doped ceria ceramics are used as electrolyte materials in solid oxide fuel cells. In this work, ceria-based oxides, Ce0.90Gd0.06Y0.02M0.02O2-δ (M = Ca, Fe, La, and Sr) were prepared by conventional as well as microwave processing from the precursors prepared by the mixed oxide method. The consolidated calcined powders in pellet form were sintered in microwave energy at 1400°C for 20 min and in an electric furnace of IR radiation at 1400°C for 6 h. The x-ray diffraction analysis confirmed that all the compositions were crystallized into a cubic fluorite structure. Surface morphology of the sintered products was studied using scanning electron microscopy and the microhardness was investigated using the Vickers hardness test. The comparative results analysis shows that the microwave-sintered samples have uniform grain growth, higher density and higher microhardness than the corresponding conventionally sintered products. The microwave-sintered sample of composition Ce0.90Gd0.06Y0.02Sr0.02O2-δ was found to have the highest microhardness among the four compositions due to its high density and smallest grain size.

Pt/Ceria-based Catalysts for Small Alcohol Electrooxidation

NASA Astrophysics Data System (ADS)

Menendez-Mora, Christian L.

High emissions of fossil-based energy sources have led to scientists around the world to develop new alternatives for the future. In this sense, fuel cells are a remarkable and promising energy option with less environmental impact. The most used fuels for this technology are hydrogen and small chain alcohols, which can be oxidized to transform their chemical energy into electrical power. To do this, fuel cells need catalysts that will act as an active surface where the oxidation can take place. The problem with platinum catalysts is its possible CO poisoning with intermediates that are produced before the complete oxidation of alcohol to CO2. Different approaches have been taken to try to resolve this issue. In this case, cerium oxide (ceria) was selected as a co-catalyst to mitigate the effect of CO poisoning of platinum. Ceria is a compound that has the ability to work as an "oxygen tank" and can donate oxygen to carbon monoxide that is strongly adsorbed at platinum surface to produce CO2 (carbon dioxide), regenerating the Pt surface for further alcohol oxidation. Therefore, enhancing the current density as well as the power output of a fuel cell. First, an occlusion deposition technique was used to prepare platinum/ceria composite electrodes and tested them towards small chain alcohol oxidation such as methanol oxidation reaction in acidic and alkaline media. The preliminary results demonstrated that the Pt/ceria electrodes were more efficient towards methanol electrooxidation when compared to Pt electrodes. This enhancement was attributed to the presence of ceria. A second preparation method was selected for the synthesis of ceria/Pt catalysts. In this case, a hydrothermal method was used and the catalysis were studied for the effect of MeOH, EtOH and n-BuOH oxidation. The observed effect was that electrodes made of Pt/Pt:CeO2-x showed better catalytic effect than Pt/ceria and platinum electrodes. Moreover, a comparison between ceria nanorods versus

Deep eutectic-solvothermal synthesis of nanostructured ceria

PubMed Central

Hammond, Oliver S.; Edler, Karen J.; Bowron, Daniel T.; Torrente-Murciano, Laura

2017-01-01

Ceria is a technologically important material with applications in catalysis, emissions control and solid-oxide fuel cells. Nanostructured ceria becomes profoundly more active due to its enhanced surface area to volume ratio, reactive surface oxygen vacancy concentration and superior oxygen storage capacity. Here we report the synthesis of nanostructured ceria using the green Deep Eutectic Solvent reline, which allows morphology and porosity control in one of the less energy-intensive routes reported to date. Using wide Q-range liquid-phase neutron diffraction, we elucidate the mechanism of reaction at a molecular scale at considerably milder conditions than the conventional hydrothermal synthetic routes. The reline solvent plays the role of a latent supramolecular catalyst where the increase in reaction rate from solvent-driven pre-organization of the reactants is most significant. This fundamental understanding of deep eutectic-solvothermal methodology will enable future developments in low-temperature synthesis of nanostructured ceria, facilitating its large-scale manufacturing using green, economic, non-toxic solvents. PMID:28120829

Sulfation of ceria-zirconia model automotive emissions control catalysts

NASA Astrophysics Data System (ADS)

Nelson, Alan Edwin

Cerium-zirconium mixed metal oxides are used in automotive emissions control catalysts to regulate the partial pressure of oxygen near the catalyst surface. The near surface oxygen partial pressure is regulated through transfer of atomic oxygen from the ceria-zirconia solid matrix to the platinum group metals to form metal oxides capable of oxidizing carbon monoxide and unburned hydrocarbons. Although the addition of zirconium in the cubic lattice of ceria increases the oxygen storage capacity and thermal stability of the ceria matrix, the cerium-zirconium oxide system remains particularly susceptible to deactivation from sulfur compounds. While the overall effect of sulfur on these systems is understood (partially irreversible deactivation), the fundamental and molecular interaction of sulfur with ceria-zirconia remains a challenging problem. Ceria-zirconia metal oxide solid solutions have been prepared through co-precipitation with nitrate precursors. The prepared powders were calcined and subsequently formed into planer wafers and characterized for chemical and physical attributes. The prepared samples were subsequently exposed to a sulfur dioxide based environment and characterized with spectroscopic techniques to characterize the extent of sulfation and the nature of surface sulfur species. The extent of sulfation of the model ceria-zirconia systems was characterized with Auger electron spectroscopy (AES) prior to and after treatment in a microreactor. Strong dependencies were observed between the atomic ratio of ceria to zirconia and the extent of sulfation. In addition, the partial pressure of sulfur dioxide during treatments also correlated to the extent of sulfation, while temperature only slightly effected the extent of sulfation. The AES data suggests the gas phase sulfur dioxide preferentially chemisorbs on surface ceria atoms and the extent of sulfation is heavily dependent on sulfur dioxide concentrations and only slightly dependent on catalyst

Impacts of a Nanosized Ceria Additive on Diesel Engine Emissions of Particulate and Gaseous Pollutants

PubMed Central

Zhang, Junfeng; Nazarenko, Yevgen; Zhang, Lin; Calderon, Leonardo; Lee, Ki-Bum; Garfunkel, Eric; Schwander, Stephan; Tetley, Teresa D.; Chung, Kian Fan; Porter, Alexandra E.; Ryan, Mary; Kipen, Howard; Lioy, Paul J.; Mainelis, Gediminas

2014-01-01

Fuel additives incorporating nanosized ceria have been increasingly used in diesel engines as combustion promoters. However, few studies have assessed the impact of these nanotechnology-based additives on pollutant emissions. Here, we systematically compare emission rates of particulate and gaseous pollutants from a single-cylinder, four-cycle diesel engine using fuel mixes containing nanoceria of varying concentrations. The test fuels were made by adding different amounts of a commercial fuel additive Envirox into an ultralow-sulfur diesel fuel at 0 (base fuel), 0.1-, 1-, and 10-fold the manufacturer-recommended concentration of 0.5 mL Envirox per liter of fuel. The addition of Envirox resulted in ceria-concentration-dependent emission reductions of CO2, CO, total particulate mass, formaldehyde, acetaldehyde, acrolein, and several polycyclic aromatic hydrocarbons. These reductions at the manufacturer-recommended doping concentration, however, were accompanied by a substantial increase of certain other air pollutants, specifically the number of ultrafine particles (+32%), NOx (+9.3%), and the particle-phase benzo[a]pyrene toxic equivalence quotient (+35%). Increasing fuel ceria concentrations also led to decreases in the size of emitted particles. Given health concerns related to ultrafine particles and NOx, our findings call for additional studies to further evaluate health risks associated with the use of nanoceria additives in various engines under various operating conditions. PMID:24144266

Relationship Between Particle and Plasma Properties and Coating Characteristics of Samaria-Doped Ceria Prepared by Atmospheric Plasma Spraying for Use in Solid Oxide Fuel Cells

NASA Astrophysics Data System (ADS)

Cuglietta, Mark; Kesler, Olivera

2012-06-01

Samaria-doped ceria (SDC) has become a promising material for the fabrication of high-performance, intermediate-temperature solid oxide fuel cells (SOFCs). In this study, the in-flight characteristics, such as particle velocity and surface temperature, of spray-dried SDC agglomerates were measured and correlated to the resulting microstructures of SDC coatings fabricated using atmospheric plasma spraying, a manufacturing technique with the capability of producing full cells in minutes. Plasmas containing argon, nitrogen and hydrogen led to particle surface temperatures higher than those in plasmas containing only argon and nitrogen. A threshold temperature for the successful deposition of SDC on porous stainless steel substrates was calculated to be 2570 °C. Coating porosity was found to be linked to average particle temperature, suggesting that plasma conditions leading to lower particle temperatures may be most suitable for fabricating porous SOFC electrode layers.

Preparation and properties of plate-like titanate (PLT)/calcia-doped ceria (CDC) composites by sol-gel coating method.

PubMed

Liu, Xiangwen; Liu, Jingxiao; Dong, Xiaoli; Yin, Shu; Sato, Tsugio

2009-08-01

In order to obtain UV-shielding materials with good comfort, higher safety and effective UV-shielding ability, lepidocrocite type plate-like titanate (K(0.8)Li(0.27)Ti(1.73)O(4), donated as: PLT)/calcia-doped ceria (donated as: CDC) composites were synthesized by a sol-gel method. After dissolving Ce(NO(3))(3).6H(2)O and Ca(NO(3))(2).4H(2)O into absolute ethanol at 40 degrees C, glacial acetic acid (HAc) and PLT particles dispersed into absolute ethanol were added. Then, the solution was heated at 60 degrees C to get gel-like substance. This gel was dried in a vacuum oven at 333 K for 5 h, and then, the product was collected and ground in an agate mortar followed by calcination at 1073 K for 2 h to form PLT/CDC composites. By optimization, 20 mass% of CDC was coated by one operation. PLT/CDC composites with higher CDC content were obtained by repeating the coating process. The morphology, catalytic activity for the oxidation of organic material, UV-shielding ability and dynamic friction coefficient of as-obtained PLT/CDC composites were characterized. As a result, broad-spectrum UV-shielding composite materials with good comfort and low oxidation catalytic activity were successfully synthesized.

Zr-doped ceria additives for enhanced PEM fuel cell durability and radical scavenger stability

DOE PAGES

Baker, Andrew M.; Williams, Stefan Thurston DuBard; Mukundan, Rangachary; ...

2017-06-06

Doped ceria compounds demonstrate excellent radical scavenging abilities and are promising additives to improve the chemical durability of polymer electrolyte membrane (PEM) fuel cells. Here in this paper, Ce 0.85Zr 0.15O 2 (CZO) nanoparticles were incorporated into the cathode catalyst layers (CLs) of PEM fuel cells (based on Nafion XL membranes containing 6.0 μg cm -2 ion-exchanged Ce) at loadings of 10 and 55 μg cm -2. When compared to a CZO-free baseline, CZO-containing membrane electrode assemblies (MEAs) demonstrated extended lifetimes during PEM chemical stability accelerated stress tests (ASTs), exhibiting reduced electrochemical gas crossover, open circuit voltage decay, and fluoridemore » emission rates. The MEA with high CZO loading (55 μg cm -2) demonstrated performance losses, which are attributed to Ce poisoning of the PEM and CL ionomer regions, which is supported by X-ray fluorescence (XRF) analysis. In the MEA with the low CZO loading (10 μg cm -2), both the beginning of life (BOL) performance and the performance after 500 hours of ASTs were nearly identical to the BOL performance of the CZO-free baseline MEA. XRF analysis of the MEA with low CZO loading reveals that the BOL PEM Ce concentrations are preserved after 1408 hours of ASTs and that Ce contents in the cathode CL are not significant enough to reduce performance. Therefore, employing a highly effective radical scavenger such as CZO, at a loading of 10 μg cm -2 in the cathode CL, dramatically mitigates degradation effects, which improves MEA chemical durability and minimizes performance losses.« less

Zr-doped ceria additives for enhanced PEM fuel cell durability and radical scavenger stability

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

Baker, Andrew M.; Williams, Stefan Thurston DuBard; Mukundan, Rangachary

Doped ceria compounds demonstrate excellent radical scavenging abilities and are promising additives to improve the chemical durability of polymer electrolyte membrane (PEM) fuel cells. Here in this paper, Ce 0.85Zr 0.15O 2 (CZO) nanoparticles were incorporated into the cathode catalyst layers (CLs) of PEM fuel cells (based on Nafion XL membranes containing 6.0 μg cm -2 ion-exchanged Ce) at loadings of 10 and 55 μg cm -2. When compared to a CZO-free baseline, CZO-containing membrane electrode assemblies (MEAs) demonstrated extended lifetimes during PEM chemical stability accelerated stress tests (ASTs), exhibiting reduced electrochemical gas crossover, open circuit voltage decay, and fluoridemore » emission rates. The MEA with high CZO loading (55 μg cm -2) demonstrated performance losses, which are attributed to Ce poisoning of the PEM and CL ionomer regions, which is supported by X-ray fluorescence (XRF) analysis. In the MEA with the low CZO loading (10 μg cm -2), both the beginning of life (BOL) performance and the performance after 500 hours of ASTs were nearly identical to the BOL performance of the CZO-free baseline MEA. XRF analysis of the MEA with low CZO loading reveals that the BOL PEM Ce concentrations are preserved after 1408 hours of ASTs and that Ce contents in the cathode CL are not significant enough to reduce performance. Therefore, employing a highly effective radical scavenger such as CZO, at a loading of 10 μg cm -2 in the cathode CL, dramatically mitigates degradation effects, which improves MEA chemical durability and minimizes performance losses.« less

Lung deposition and extrapulmonary translocation of nano-ceria after intratracheal instillation

NASA Astrophysics Data System (ADS)

He, Xiao; Zhang, Haifeng; Ma, Yuhui; Bai, Wei; Zhang, Zhiyong; Lu, Kai; Ding, Yayun; Zhao, Yuliang; Chai, Zhifang

2010-07-01

The broad potential applications of manufactured nanomaterials call for urgent assessment of their environmental and biological safety. However, most of the previous work focused on the cell level performance; little was known about the consequences of nanomaterial exposure at the whole-body and organ levels. In the present paper, the radiotracer technique was employed to study the pulmonary deposition and the translocation to secondary target organs after ceria nanoparticles (nano-ceria) were intratracheally instilled into Wistar rats. It was found that 63.9 ± 8.2% of the instilled nano-ceria remained in the lung by 28 d postexposure and the elimination half-life was 103 d. At the end of the test period, only 1/8-1/3 of the daily elimination of nano-ceria from the lung was cleared via the gastrointestinal tract, suggesting that phagocytosis by alveolar macrophages (AMs) with subsequent removal towards the larynx was no longer the predominant route for the elimination of nano-ceria from the lung. The whole-body redistribution of nano-ceria demonstrated that the deposited nano-ceria could penetrate through the alveolar wall into the systemic circulation and accumulate in the extrapulmonary organs. In vitro study suggested that nano-ceria would agglomerate and form sediments in the bronchoalveolar aqueous surrounding while binding to protein would be conducive to the redispersion of nano-ceria. The decrease in the size of agglomerates might enhance the penetration of nano-ceria into the systemic circulation. Our findings suggested that the effect of nanomaterial exposure, even at low concentration, should be assessed because of the potential lung and systemic cumulative toxicity of the nanomaterials.

Multifunctional Gadolinium-Doped Mesoporous TiO2 Nanobeads: Photoluminescence, Enhanced Spin Relaxation, and Reactive Oxygen Species Photogeneration, Beneficial for Cancer Diagnosis and Treatment.

PubMed

Imani, Roghayeh; Dillert, Ralf; Bahnemann, Detlef W; Pazoki, Meysam; Apih, Tomaž; Kononenko, Veno; Repar, Neža; Kralj-Iglič, Veronika; Boschloo, Gerrit; Drobne, Damjana; Edvinsson, Tomas; Iglič, Aleš

2017-05-01

Materials with controllable multifunctional abilities for optical imaging (OI) and magnetic resonant imaging (MRI) that also can be used in photodynamic therapy are very interesting for future applications. Mesoporous TiO 2 sub-micrometer particles are doped with gadolinium to improve photoluminescence functionality and spin relaxation for MRI, with the added benefit of enhanced generation of reactive oxygen species (ROS). The Gd-doped TiO 2 exhibits red emission at 637 nm that is beneficial for OI and significantly improves MRI relaxation times, with a beneficial decrease in spin-lattice and spin-spin relaxation times. Density functional theory calculations show that Gd 3+ ions introduce impurity energy levels inside the bandgap of anatase TiO 2 , and also create dipoles that are beneficial for charge separation and decreased electron-hole recombination in the doped lattice. The Gd-doped TiO 2 nanobeads (NBs) show enhanced ability for ROS monitored via • OH radical photogeneration, in comparison with undoped TiO 2 nanobeads and TiO 2 P25, for Gd-doping up to 10%. Cellular internalization and biocompatibility of TiO 2 @xGd NBs are tested in vitro on MG-63 human osteosarcoma cells, showing full biocompatibility. After photoactivation of the particles, anticancer trace by means of ROS photogeneration is observed just after 3 min irradiation. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Random lasing in Nd{sup 3+} doped potassium gadolinium tungstate crystal powder

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

Moura, André L., E-mail: andre.moura@fis.ufal.br; Departamento de Física, Universidade Federal de Pernambuco, 50670-901 Recife, PE; Fewo, Serge I.

2015-02-28

Random laser (RL) emission in Nd{sup 3+} doped potassium gadolinium tungstate—KGd(WO{sub 4}){sub 2}:Nd{sup 3+}—crystal powder is demonstrated. The powder was excited at 813 nm in resonance with the Nd{sup 3+} transition {sup 4}I{sub 9/2}→{sup 4}F{sub 5/2}. RL emission at 1067 nm due to the {sup 4}F{sub 3/2}→{sup 4}I{sub 11/2} transition was observed and characterized. An intensity threshold dependent on the laser spot area and bandwidth narrowing from ≈2.20 nm to ≈0.40 nm were observed and measured. For a beam spot area of 0.4 mm{sup 2}, a RL threshold of 6.5 mJ/mm{sup 2} (90 MW/cm{sup 2}) was determined. For excitation intensity smaller than the RL threshold, only spontaneousmore » emission from level {sup 4}F{sub 3/2} with decay time in the tens microsecond range was observed, but for excitation above the RL threshold, significant shortening of excited level lifetime, characteristic of a stimulated process was found. The overall characteristics measured show that KGd(WO{sub 4}){sub 2}:Nd{sup 3+} is an efficient material for operation of solid state RLs in the near-infrared.« less

Surface coating of ceria nanostructures for high-temperature oxidation protection

NASA Astrophysics Data System (ADS)

Aadhavan, R.; Bhanuchandar, S.; Babu, K. Suresh

2018-04-01

Stainless steels are used in high-temperature structural applications but suffer from degradation at an elevated temperature of operation due to thermal stress which leads to spallation. Ceria coating over chromium containing alloys induces protective chromia layer formation at alloy/ceria interface thereby preventing oxidative degradation. In the present work, three metals of differing elemental composition, namely, AISI 304, AISI 410, and Inconel 600 were tested for high-temperature stability in the presence and absence of ceria coating. Nanoceria was used as the target to deposit the coating through electron beam physical vapor deposition method. After isothermal oxidation at 1243 K for 24 h, Ceria coated AISI 304 and Inconel 600 exhibited a reduced rate of oxidation by 4 and 1 orders, respectively, in comparison with the base alloy. The formation of spinel structure was found to be lowered in the presence of ceria due to the reduced migration of cations from the alloy.

High-performance field-effect transistors based on gadolinium doped indium oxide nanofibers and their application in logic gate

NASA Astrophysics Data System (ADS)

Wang, Chao; Meng, You; Guo, Zidong; Shin, Byoungchul; Liu, Guoxia; Shan, Fukai

2018-05-01

One-dimensional metal oxide nanofibers have been regarded as promising building blocks for large area low cost electronic devices. As one of the representative metal oxide semiconducting materials, In2O3 based materials have attracted much interest due to their excellent electrical and optical properties. However, most of the field-effect transistors (FETs) based on In2O3 nanofibers usually operate in a depletion mode, which lead to large power consumption and a complicated integrated circuit design. In this report, gadolinium (Gd) doped In2O3 (InGdO) nanofibers were fabricated by electrospinning and applied as channels in the FETs. By optimizing the doping concentration and the nanofiber density, the device performance could be precisely manipulated. It was found that the FETs based on InGdO nanofibers, with a Gd doping concentration of 3% and a nanofiber density of 2.9 μm-1, exhibited the best device performance, including a field-effect mobility (μFE) of 2.83 cm2/V s, an on/off current ratio of ˜4 × 108, a threshold voltage (VTH) of 5.8 V, and a subthreshold swing (SS) of 2.4 V/decade. By employing the high-k ZrOx thin films as the gate dielectrics in the FETs, the μFE, VTH and SS can be further improved to be 17.4 cm2/V s, 0.7 V and 160 mV/decade, respectively. Finally, an inverter based on the InGdO nanofibers/ZrOx FETs was constructed and a gain of ˜11 was achieved.

Fuel cells with doped lanthanum gallate electrolyte

NASA Astrophysics Data System (ADS)

Feng, Man; Goodenough, John B.; Huang, Keqin; Milliken, Christopher

Single cells with doped lanthanum gallate electrolyte material were constructed and tested from 600 to 800°C. Both ceria and the electrolyte material were mixed with NiO powder respectively to form composite anodes. Doped lanthanum cobaltite was used exclusively as the cathode material. While high power density from the solid oxide fuel cells at 800°C was achieved. our results clearly indicate that anode overpotential is the dominant factor in the power loss of the cells. Better anode materials and anode processing methods need to be found to fully utilize the high ionic conductivity of the doped lanthanum galiate and achieve higher power density at 800°C from solid oxide fuel cells.

Surface structure of coherently strained ceria ultrathin films

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

Shi, Yezhou; Stone, Kevin H.; Guan, Zixuan

2016-11-14

Cerium oxide, or ceria, is an important material for solid oxide fuel cells and water splitting devices. Although the ceria surface is active in catalytic and electrochemical reactions, how its catalytic properties are affected by the surface structure under operating conditions is far from understood. We investigate the structure of the coherently strained CeO 2 ultrathin films on yttria-stabilized zirconia (001) single crystals by specular synchrotron x-ray diffraction (XRD) under oxidizing conditions as a first step to study the surface structure in situ. An excellent agreement between the experiment data and the model is achieved by using a “stacks andmore » islands” model that has a two-component roughness. One component is due to the tiny clusters of nanometer scale in lateral dimensions on each terrace, while the other component is due to slightly different CeO 2 thickness that span over hundreds of nanometers on neighboring terraces. We attribute the nonuniform thickness to step depairing during the thin film deposition that is supported by the surface morphology results on the microscopic level. Importantly, our model also shows that the polarity of the ceria surface is removed by a half monolayer surface coverage of oxygen. In conclusion, the successful resolution of the ceria surface structure using in situ specular synchrotron XRD paves the way to study the structural evolution of ceria as a fuel cell electrode under catalytically relevant temperatures and gas pressures.« less

Shaped Ceria Nanocrystals Catalyze Efficient and Selective Para-Hydrogen-Enhanced Polarization.

PubMed

Zhao, Evan W; Zheng, Haibin; Zhou, Ronghui; Hagelin-Weaver, Helena E; Bowers, Clifford R

2015-11-23

Intense para-hydrogen-enhanced NMR signals are observed in the hydrogenation of propene and propyne over ceria nanocubes, nano-octahedra, and nanorods. The well-defined ceria shapes, synthesized by a hydrothermal method, expose different crystalline facets with various oxygen vacancy densities, which are known to play a role in hydrogenation and oxidation catalysis. While the catalytic activity of the hydrogenation of propene over ceria is strongly facet-dependent, the pairwise selectivity is low (2.4% at 375 °C), which is consistent with stepwise H atom transfer, and it is the same for all three nanocrystal shapes. Selective semi-hydrogenation of propyne over ceria nanocubes yields hyperpolarized propene with a similar pairwise selectivity of (2.7% at 300 °C), indicating product formation predominantly by a non-pairwise addition. Ceria is also shown to be an efficient pairwise replacement catalyst for propene. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The reduction and oxidation of ceria: A natural abundance triple oxygen isotope perspective

NASA Astrophysics Data System (ADS)

Hayles, Justin; Bao, Huiming

2015-06-01

Ceria (CeO2) is a heavily studied material in catalytic chemistry for use as an oxygen storage medium, oxygen partial pressure regulator, fuel additive, and for the production of syngas, among other applications. Ceria powders are readily reduced and lose structural oxygen when subjected to low pO2 and/or high temperature conditions. Such dis-stoichiometric ceria can then re-oxidize under higher pO2 and/or lower temperature by incorporating new oxygen into the previously formed oxygen site vacancies. Despite extensive studies on ceria, the mechanisms for oxygen adsorption-desorption, dissociation-association, and diffusion of oxygen species on ceria surface and within the crystal structure are not well known. We predict that a large kinetic oxygen isotope effect should accompany the release and incorporation of ceria oxygen. As the first attempt to determine the existence and the degree of the isotope effect, this study focuses on a set of simple room-temperature re-oxidation experiments that are also relevant to a laboratory procedure using ceria to measure the triple oxygen isotope composition of CO2. Triple-oxygen-isotope labeled ceria powders are heated at 700 °C and cooled under vacuum prior to exposure to air. By combining results from independent experimental sets with different initial oxygen isotope labels and using a combined mass-balance and triangulation approach, we have determined the isotope fractionation factors for both high temperature reduction in vacuum (⩽10-4 mbar) and room temperature re-oxidation in air. Results indicate that there is a 1.5‰ ± 0.8‰ increase in the δ18O value of ceria after being heated in vacuum at 700 °C for 1 h. When the vacuum is broken at room temperature, the previously heated ceria incorporates 3-19% of its final structural oxygen from air, with a δ18O value of 2.1-4.1+7.7 ‰ for the incorporated oxygen. The substantial incorporation of oxygen from air supports that oxygen mobility is high in vacancy

Modifying ceria (111) with a TiO2 nanocluster for enhanced reactivity.

PubMed

Nolan, Michael

2013-11-14

Modification of ceria catalysts is of great interest for oxidation reactions such as oxidative dehydrogenation of alcohols. Improving the reactivity of ceria based catalysts for these reactions means that they can be run at lower temperatures and density functional theory (DFT) simulations of new structures and compositions are proving valuable in the development of these catalysts. In this paper, we have used DFT+U (DFT corrected for on-site Coulomb interactions) to examine the reactivity of a novel modification of ceria, namely, modifying with TiO2, using the example of a Ti2O4 species adsorbed on the ceria (111) surface. The oxygen vacancy formation energy in the Ti2O4-CeO2 system is significantly reduced over the bare ceria surfaces, which together with previous work on ceria-titania indicates that the presence of the interface favours oxygen vacancy formation. The energy gain upon hydrogenation of the catalyst, which is the rate determining step in oxidative dehydrogenation, further points to the improved oxidation power of this catalyst structure.

STRUCTURAL ANALYSIS OF THE COMBUSTION SYNTHESIZED Y3+ DOPED CERIA (Ce0.9Y0.1O1.95)

NASA Astrophysics Data System (ADS)

Jeyanthi, C. Esther; Siddheswaran, R.; Kumar, Pushpendra; Mangalaraja, R. V.; Siva Shankar, V.; Rajarajan, K.

2013-07-01

Y3+ doped CeO2 nanopowders (Ce0.9Y0.1O1.95, abbreviated as YDC) were synthesized by citrate-nitrate-auto combustion process using cerium nitrate hexahydrate, yttrium nitrate hexahydrate and citric acid. The as-synthesized powders were calcined at 700°C and converted into dense bodies followed by sintering at 1200°C. The microstructure of the synthesized powders and sintered bodies were examined by scanning electron microscopy (SEM). The surface morphology of the nanoparticles and clusters were also analysed by transmission electron microscopy (TEM). The particles size of the YDC was found to be in the range from 10 to 30 nm, which is in good agreement with the crystallite size calculated from X-ray peak broadening method. Also, the X-ray diffraction confirmed that the Ce0.9Y0.1O1.95 crystallizes as the cubic fluorite structure of pure ceria. The optical absorption by functional molecules, impurities and oxygen vacancies were analysed by FTIR and Raman spectroscopic studies. From the FTIR spectrum, the absorption peak found at 530 cm-1 is attributed to the vibrations of metal-oxygen bonds. The characteristic Raman peak was found to be 468 cm-1, and the minute absorption of oxygen vacancies were observed in the region 500-640 cm-1.

A Novel Hybrid Axial-Radial Atmospheric Plasma Spraying Technique for the Fabrication of Solid Oxide Fuel Cell Anodes Containing Cu, Co, Ni, and Samaria-Doped Ceria

NASA Astrophysics Data System (ADS)

Cuglietta, Mark; Kuhn, Joel; Kesler, Olivera

2013-06-01

Composite coatings containing Cu, Co, Ni, and samaria-doped ceria (SDC) have been fabricated using a novel hybrid atmospheric plasma spraying technique, in which a multi-component aqueous suspension of CuO, Co3O4, and NiO was injected axially simultaneously with SDC injected radially in a dry powder form. Coatings were characterized for their microstructure, permeability, porosity, and composition over a range of plasma spray conditions. Deposition efficiency of the metal oxides and SDC was also estimated. Depending on the conditions, coatings displayed either layering or high levels of mixing between the SDC and metal phases. The deposition efficiencies of both feedstock types were strongly dependent on the nozzle diameter. Plasma-sprayed metal-supported solid oxide fuel cells utilizing anodes fabricated with this technique demonstrated power densities at 0.7 V as high as 366 and 113 mW/cm2 in humidified hydrogen and methane, respectively, at 800 °C.

Gadolinium toxicity and treatment.

PubMed

Ramalho, Joana; Ramalho, Miguel; Jay, Michael; Burke, Lauren M; Semelka, Richard C

2016-12-01

Gadolinium based contrast agents (GBCAs) play an important role in the diagnostic evaluation of many patients. The safety of these agents has been once again questioned after gadolinium deposits were observed and measured in brain and bone of patients with normal renal function. This retention of gadolinium in the human body has been termed "gadolinium storage condition". The long-term and cumulative effects of retained gadolinium in the brain and elsewhere are not as yet understood. Recently, patients who report that they suffer from chronic symptoms secondary to gadolinium exposure and retention created gadolinium-toxicity on-line support groups. Their self-reported symptoms have recently been published. Bone and joint complaints, and skin changes were two of the most common complaints. This condition has been termed "gadolinium deposition disease". In this review we will address gadolinium toxicity disorders, from acute adverse reactions to GBCAs to gadolinium deposition disease, with special emphasis on the latter, as it is the most recently described and least known. Copyright © 2016 Elsevier Inc. All rights reserved.

Measurement of gamma-ray production from thermal neutron capture on gadolinium for neutrino experiments

NASA Astrophysics Data System (ADS)

Yano, Takatomi; 2012B0025 Collaboration; 2014B0126 Collaboration

2017-02-01

Recently, several scientific applications of gadolinium are found in neutrino physics experiments. Gadolinium-157 is the nucleus, which has the largest thermal neutron capture cross-section among all stable nuclei. Gadolinium-155 also has the large cross-section. These neutron capture reactions provide the gamma-ray cascade with the total energy of about 8 MeV. This reaction is applied for several neutrino experiments, e.g. reactor neutrino experiments and Gd doped large water Cherenkov detector experiments, to recognize inverse-beta-decay reaction. A good Gd(n,γ) simulation model is needed to evaluate the detection efficiency of the neutron capture reaction, i.e. the efficiency of IBD detection. In this presentation, we will report the development and study status of a Gd(n,γ) calculation model and comparison with our experimental data taken at ANNRI/MLF beam line, J-PARC.

Ameliorative role of nano-ceria against amine coated Ag-NP induced toxicity in Labeo rohita

NASA Astrophysics Data System (ADS)

Khan, Muhammad Saleem; Qureshi, Naureen Aziz; Jabeen, Farhat

2018-03-01

Silver nanoparticles (Ag-NPs) and its byproducts can spread pollution in aquatic habitat. Liver and gills are key target for toxicity. Oxidative stress, tissue alterations, and hemotoxicity are assumed to be associated with Ag-NPs in target animals. Cerium oxide nanoparticles (nano-ceria) show antioxidant potential in scavenging the free radicals generated in Ag-NP-induced oxidative stress. We determined ameliorated role of nano-ceria against Ag-NP-induced toxicity in fresh water Labeo rohita (L. rohita). Four groups were used in study including control, nano-ceria, Ag-NPs, and Ag-NPs + nano-ceria. Ag-NPs (30 mg l-1) and nano-ceria (50 µg kg-1) were given through water and prepared feed, respectively. The samples were taken after 28 days. Results demonstrated that pre-treatment of nano-ceria recovered L. rohita from Ag-NP-induced toxicity and oxidative stress. Nano-ceria pre-treatment actively mimics the activity of GST, GSH, CAT, and SOD. Furthermore, Ag-NPs' treatment caused severe inflammation and necrosis in hepatic parenchyma which leaded to congestion of blood in hepatic tissues. Accumulation of a yellow pigment in hepatic tissue was also seen due to necrosis of affected cells. In nano-ceria pre-treatment, there was no congestion in hepatic tissue. Vacuolization of cells and necrosis in some area was recorded in nano-ceria pre-treated group, but the gill and hepatic tissue showed improvement against Ag-NP-induced damage. Nano-ceria pre-treatment also improved hematological parameters in Ag-NP-treated fish. This study concluded that Ag-NP-induced toxicity in treated fish and pre-treatment of nano-ceria show ameliorative role.

Thermally stable single-atom platinum-on-ceria catalysts via atom trapping

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

Jones, John; Xiong, Haifeng; DelaRiva, Andrew

2016-07-08

Catalysts based on single atoms of scarce precious metals can lead to more efficient use through enhanced reactivity and selectivity. However, single atoms on catalyst supports can be mobile and aggregate into nanoparticles when heated at elevated temperatures. High temperatures are detrimental to catalyst performance unless these mobile atoms can be trapped. We used ceria powders having similar surface areas but different exposed surface facets. When mixed with a platinum/ aluminum oxide catalyst and aged in air at 800°C, the platinum transferred to the ceria and was trapped. Polyhedral ceria and nanorods were more effective than ceria cubes at anchoringmore » the platinum. Performing synthesis at high temperatures ensures that only the most stable binding sites are occupied, yielding a sinter-resistant, atomically dispersed catalyst.« less

Adhesion and Atomic Structures of Gold on Ceria Nanostructures:The Role of Surface Structure and Oxidation State of Ceria Supports

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

Lin, Yuyuan; Wu, Zili; Wen, Jianguo

2015-01-01

Recent advances in heterogeneous catalysis have demonstrated that oxides supports with the same material but different shapes can result in metal catalysts with distinct catalytic properties. The shape-dependent catalysis was not well-understood owing to the lack of direct visualization of the atomic structures at metal-oxide interface. Herein, we utilized aberration-corrected electron microscopy and revealed the atomic structures of gold particles deposited on ceria nanocubes and nanorods with {100} or {111} facets exposed. For the ceria nanocube support, gold nanoparticles have extended atom layers at the metal-support interface. In contrast, regular gold nanoparticles and rafts are present on the ceria nanorodmore » support. After hours of water gas shift reaction, the extended gold atom layers and rafts vanish, which is associated with the decrease of the catalytic activities. By understanding the atomic structures of the support surfaces, metal-support interfaces, and morphologies of the gold particles, a direct structure-property relationship is established.« less

Simultaneous NOx and Particulate Matter Removal from Diesel Exhaust by Hierarchical Fe-Doped Ce–Zr Oxide

PubMed Central

2017-01-01

Particulate matter and NOx emissions from diesel exhaust remains one of the most pressing environmental problems. We explore the use of hierarchically ordered mixed Fe–Ce–Zr oxides for the simultaneous capture and oxidation of soot and reduction of NOx by ammonia in a single step. The optimized material can effectively trap the model soot particles in its open macroporous structure and oxidize the soot below 400 °C while completely removing NO in the 285–420 °C range. Surface characterization and DFT calculations emphasize the defective nature of Fe-doped ceria. The isolated Fe ions and associated oxygen vacancies catalyze facile NO reduction to N2. A mechanism for the reduction of NO with NH3 on Fe-doped ceria is proposed involving adsorbed O2. Such adsorbed O2 species will also contribute to the oxidation of soot. PMID:28603656

Space charge induced surface stresses: implications in ceria and other ionic solids.

PubMed

Sheldon, Brian W; Shenoy, Vivek B

2011-05-27

Volume changes associated with point defects in space charge layers can produce strains that substantially alter thermodynamic equilibrium near surfaces in ionic solids. For example, near-surface compressive stresses exceeding -10 GPa are predicted for ceria. The magnitude of this effect is consistent with anomalous lattice parameter increases that occur in ceria nanoparticles. These stresses should significantly alter defect concentrations and key transport properties in a wide range of materials (e.g., ceria electrolytes in fuel cells). © 2011 American Physical Society

Gadolinium diethylenetriaminopentaacetic acid-loaded chitosan microspheres for gadolinium neutron-capture therapy.

PubMed

Saha, Tapan Kumar; Ichikawa, Hideki; Fukumori, Yoshinobu

2006-12-11

In order to provide a suitable device that would contain water-soluble drugs, highly water-soluble gadolinium diethylenetriaminopentaacetic acid-loaded chitosan microspheres (CMS-Gd-DTPA) were prepared by the emulsion method using glutaraldehyde as a cross-linker and Span 80 as a surfactant for gadolinium neutron-capture therapy of cancer. The gadolinium content and the mass median diameter of CMS-Gd-DTPA were estimated. The size and morphology of the CMS-Gd-DTPA were strongly influenced by the initial applied weight ratio of Gd-DTPA:chitosan. FTIR spectra showed that the electrostatic interaction between chitosan and Gd-DTPA accelerated the formation of gadolinium-enriched chitosan microspheres. Sufficient amounts of glutaraldehyde and Span 80 were necessary for producing discrete CMS-Gd-DTPA. The CMS-Gd-DTPA having a mass median diameter 11.7microm and 11.6% of gadolinium could be used in Gd-NCT following intratumoral injection.

Pyrolysis result of polyethylene waste as fuel for solid oxide fuel cell with samarium doped-ceria (SDC)-carbonate as electrolyte

NASA Astrophysics Data System (ADS)

Syahputra, R. J. E.; Rahmawati, F.; Prameswari, A. P.; Saktian, R.

2017-02-01

In this research, the result of pyrolysis on polyethylene was used as fuel for a solid oxide fuel cell (SOFC). The pyrolysis result is a liquid which consists of hydrocarbon chains. According to GC-MS analysis, the hydrocarbons mainly consist of C7 to C20 hydrocarbon chain. Then, the liquid was applied to a single cell of NSDC-L | NSDC | NSDC-L. NSDC is a composite SDC (samarium doped-ceria) with sodium carbonate. Meanwhile, NSDC-L is a composite of NSDC with LiNiCuO (LNC). NSDC and LNC were analyzed by X-ray diffraction to understand their crystal structure. The result shows that presence of carbonate did not change the crystal structure of SDC. SEM EDX analysis for fuel cell before and after being loaded with polyethylene oil to get information of element diffusion to the electrolyte. Meanwhile, the conductivity properties were investigated through impedance measurement. The presence of carbonate even increases the electrical conductivity. The single cell test with the pyrolysis result of polyethylene at 300 - 600 °C, found that the highest power density is at 600 °C with the maximum power density of 0.14 mW/cm2 and open circuit voltage of 0.4 Volt. Elemental analysis at three point spots of single cell NDSC-L |NSDC|NSDC-L found that a migration of ions was occurred during fuel operation at 300 - 600 °C.

Soot Combustion over Nanostructured Ceria with Different Morphologies

PubMed Central

Zhang, Wen; Niu, Xiaoyu; Chen, Liqiang; Yuan, Fulong; Zhu, Yujun

2016-01-01

In this study, nano-structure ceria with three different morphologies (nanorod, nanoparticle and flake) have been prepared by hydrothermal and solvothermal methods. The ceria samples were deeply characterized by XRD, SEM, TEM, H2-TPR, XPS and in-situ DRIFTS, and tested for soot combustion in absence/presence NO atmospheres under loose and tight contact conditions. The prepared ceria samples exhibit excellent catalytic activities, especially, the CeO2 with nanorod (Ce-R) shows the best catalytic activity, for which the peak temperature of soot combustion (Tm) is about 500 and 368 °C in loose and tight contact conditions, respectively. The catalytic activity for Ce-R is higher than that of the reported CeO2 catalysts and reaches a level that of precious metals. The characterization results reveal that the maximal amounts of adsorbed oxygen species on the surface of the nanostructure Ce-R catalyst should be the crucial role to decide the catalytic soot performance. High BET surface area may also be a positive effect on soot oxidation activity under loose contact conditions. PMID:27353143

XPS studies of Mg doped GDC (Ce0.8Gd0.2O2-δ) for IT-SOFC

NASA Astrophysics Data System (ADS)

Tyagi, Deepak; Rao, P. Koteswara; Wani, B. N.

2018-04-01

Fuel Cells have gained much attention as efficient and environment friendly device for both stationary as well as mobile applications. For intermediate temperature SOFC (IT-SOFC), ceria based electrolytes are the most promising one, due to their higher ionic conductivity at relatively lower temperatures. Gd doped ceria is reported to be having the highest ionic conductivity. In the present work, Mg is codoped along with Gd and the electronic structure of the constituents is studied by XPS. XPS confirm that the Cerium is present in +4 oxidation state only which indicates that electronic conduction can be completely avoided.

Adsorption and desorption characteristics of arsenic onto ceria nanoparticles

PubMed Central

2012-01-01

The rapid increase in the use of engineered nanoparticles [ENPs] has resulted in an increasing concern over the potential impacts of ENPs on the environmental and human health. ENPs tend to adsorb a large variety of toxic chemicals when they are emitted into the environment, which may enhance the toxicity of ENPs and/or adsorbed chemicals. The study was aimed to investigate the adsorption and desorption behaviors of arsenic on ceria NPs in aqueous solution using batch technique. Results show that the adsorption behavior of arsenic on ceria NPs was strongly dependent on pH and independent of ionic strength, indicating that the electrostatic effect on the adsorption of these elements was relatively not important compared to surface chemical reactions. The adsorption isotherms fitted very well to both the Langmuir and Freundlich models. The thermodynamic parameters (ΔH0, ΔS0, and ΔG0) for the adsorption of arsenic were determined at three different temperatures of 283, 303, and 323 K. The adsorption reaction was endothermic, and the process of adsorption was favored at high temperature. The desorption data showed that desorption hysteresis occurred at the initial concentration studied. High adsorption capacity of arsenic on ceria NPs suggests that the synergistic effects of ceria NPs and arsenic on the environmental systems may exist when they are released into the environment. PMID:22269298

On the growth mechanisms of polar (100) surfaces of ceria on copper (100)

NASA Astrophysics Data System (ADS)

Hackl, Johanna; Duchoň, Tomáš; Gottlob, Daniel M.; Cramm, Stefan; Veltruská, Kateřina; Matolín, Vladimír; Nemšák, Slavomír; Schneider, Claus M.

2018-05-01

We present a study of temperature dependent growth of nano-sized ceria islands on a Cu (100) substrate. Low-energy electron microscopy, micro-electron diffraction, X-ray absorption spectroscopy, and photoemission electron microscopy are used to determine the morphology, shape, chemical state, and crystal structure of the grown islands. Utilizing real-time observation capabilities, we reveal a three-way interaction between the ceria, substrate, and local oxygen chemical potential. The interaction manifests in the reorientation of terrace boundaries on the Cu (100) substrate, characteristic of the transition between oxidized and metallic surface. The reorientation is initiated at nucleation sites of ceria islands, whose growth direction is influenced by the proximity of the terrace boundaries. The grown ceria islands were identified as fully stoichiometric CeO2 (100) surfaces with a (2 × 2) reconstruction.

Response of gadolinium doped liquid scintillator to charged particles: measurement based on intrinsic U/Th contamination

NASA Astrophysics Data System (ADS)

Du, Q.; Lin, S. T.; He, H. T.; Liu, S. K.; Tang, C. J.; Wang, L.; Wong, H. T.; Xing, H. Y.; Yue, Q.; Zhu, J. J.

2018-04-01

A measurement is reported for the response to charged particles of a liquid scintillator named EJ-335 doped with 0.5% gadolinium by weight. This liquid scintillator was used as the detection medium in a neutron detector. The measurement is based on the in-situ α-particles from the intrinsic Uranium and Thorium contamination in the scintillator. The β–α and the α–α cascade decays from the U/Th decay chains were used to select α-particles. The contamination levels of U/Th were consequently measured to be (5.54±0.15)× 10‑11 g/g, (1.45±0.01)× 10‑10 g/g and (1.07±0.01)× 10‑11 g/g for 232Th, 238U and 235U, respectively, assuming secular equilibrium. The stopping power of α-particles in the liquid scintillator was simulated by the TRIM software. Then the Birks constant, kB, of the scintillator for α-particles was determined to be (7.28±0.23) mg/(cm2ṡMeV) by Birks' formulation. The response for protons is also presented assuming the kB constant is the same as for α-particles.

Ceria-based model catalysts: fundamental studies on the importance of the metal–ceria interface in CO oxidation, the water–gas shift, CO 2 hydrogenation, and methane and alcohol reforming

DOE PAGES

Rodriguez, José A.; Grinter, David C.; Liu, Zongyuan; ...

2017-02-17

Model metal/ceria and ceria/metal catalysts have been shown to be excellent systems for studying fundamental phenomena linked to the operation of technical catalysts. In the last fifteen years, many combinations of well-defined systems involving different kinds of metals and ceria have been prepared and characterized using the modern techniques of surface science. So far most of the catalytic studies have been centered on a few reactions: CO oxidation, the hydrogenation of CO 2, and the production of hydrogen through the water–gas shift reaction and the reforming of methane or alcohols. By using model catalysts it is been possible to examinemore » in detail correlations between the structural, electronic and catalytic properties of ceria–metal interfaces. In situ techniques (X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, infrared spectroscopy, scanning tunneling microscopy) have been combined to study the morphological changes under reaction conditions and investigate the evolution of active phases involved in the cleavage of C–O, C–H and C–C bonds. Several studies with model ceria catalysts have shown the importance of strong metal–support interactions. Generally, a substantial body of knowledge has been acquired and concepts have been developed for a more rational approach to the design of novel technical catalysts containing ceria.« less

Phosphate modified ceria as a Brønsted acidic/redox multifunctional catalyst

DOE PAGES

Nelson, Nicholas C.; Wang, Zhuoran; Naik, Pranjali; ...

2017-01-06

Deposition of trimethylphosphate onto ceria followed by thermal treatment resulted in the formation of surface phosphates with retention of the ceria fluorite structure. The structural and chemical properties of the phosphate-functionalized ceria were studied using 31P solid-state NMR, XPS, zeta titration, ammonia thermal desorption, pyridine adsorption, and model reactions. The introduction of phosphates generated Brønsted acid sites and decreased the number of Lewis acid sites on the surface. The relative amount of Lewis and Brønsted acids can be controlled by the amount of trimethylphosphate used in the synthesis. Upon deposition of Pd, the multifunctional material showed enhanced activity for themore » hydrogenolysis of eugenol and guaiacol compared to Pd on the unmodified ceria support. As a result, this was attributed to the cooperativity between the Lewis acid sites, which activate the substrate for dearomatization, and the redox/Brønsted acid properties, which catalyze hydrogenolysis.« less

Rare-earth doped gadolinia based phosphors for potential multicolor and white light emitting deep UV LEDs.

PubMed

Bedekar, Vinila; Dutta, Dimple P; Mohapatra, M; Godbole, S V; Ghildiyal, R; Tyagi, A K

2009-03-25

Gadolinium oxide host and europium/dysprosium/terbium doped gadolinium oxide nanoparticles were synthesized using the sonochemical technique. Gadolinium oxide nanocrystals were also co-doped with total 2 mol% of Eu(3+)/Dy(3+),Eu(3+)/Tb(3+),Dy(3+)/Tb(3+), and also Eu(3+)/Dy(3+)/Tb(3+) ions, by the same method. The nanoparticles obtained were characterized using powder x-ray diffraction (XRD), transmission electron microscopy (TEM), and selected area electron diffraction (SAED) techniques. The size of the particles ranged from 15 to 30 nm. The triple doped samples showed multicolor emission on single wavelength excitation. The photoluminescence results were correlated with the lifetime data to get an insight into the luminescence and energy transfer processes taking place in the system. On excitation at 247 nm, the novel nanocrystalline Gd(2)O(3):RE (RE = Dy, Tb) phosphor resulted in having very impressive CIE chromaticity coordinates of x = 0.315 and y = 0.316, and a correlated color temperature of 6508 K, which is very close to standard daylight.

Europium-doped gadolinium sulfide nanoparticles as a dual-mode imaging agent for T1-weighted MR and photoluminescence imaging.

PubMed

Jung, Jongjin; Kim, Mi Ae; Cho, Jee-Hyun; Lee, Seung Jae; Yang, Ilseung; Cho, Janggeun; Kim, Seong Keun; Lee, Chulhyun; Park, Joung Kyu

2012-08-01

We present a facile synthesis of europium-doped gadolinium sulfide (GdS:Eu(3+)) opto-magnetic nanoparticles (NPs) via sonochemistry. Their photoluminescence and strong paramagnetic properties enable these NPs to be utilized as an in vitro cell imaging and in vivo T(1)-weighted MR imaging probe. The GdS:Eu(3+) NPs have a prominent longitudinal (r(1)) relaxivity value, which is a critical parameter for T(1)-weighted MR imaging. Here, we showed not only their strong positive contrast effect to blood vessels and organs of mice, but also blood half-life and biodistribution including clearance from organs, in order to assess the GdS:Eu(3+) NPs as a competent nanocrystal-based T(1) contrast agent. We further showed confocal images of breast cancer cells containing GdS:Eu(3+) NPs to evaluate as a photoluminescence probe. Dual-mode imaging capability obtained from the GdS:Eu(3+) NPs will allow target-oriented cellular imaging as well as the resulting disease-specific MR imaging. Copyright © 2012 Elsevier Ltd. All rights reserved.

Samaria-doped Ceria Modified Ni/YSZ Anode for Direct Methane Fuel in Tubular Solid Oxide Fuel Cells by Impregnation Method

NASA Astrophysics Data System (ADS)

Zhang, Long-shan; Gao, Jian-feng; Tian, Rui-fen; Xia, Chang-rong

2009-08-01

A porous NiO/yttria-stabilized zirconia anode substrate for tubular solid oxide fuel cells was prepared by gel casting technique. Nano-scale samaria-doped ceria (SDC) particles were formed onto the anode substrate to modify the anode microstructure by the impregnation of solution of Sm(NO3)3 and Ce(NO3)3. Electrochemical impedance spectroscopy, current-voltage and current-powder curves of the cells were measured using an electrochemical workstation. Scanning electron microcopy was used to observe the microstructure. The results indicate that the stability of the performance of the cell operated on humidified methane can be significantly improved by incorporating the nano-structured SDC particles, compared with the unmodified cell. This verifies that the coated SDC electrodes are very effective in suppressing catalytic carbon formation by blocking methane from approaching the Ni, which is catalytically active towards methane pyrolysis. In addition, it was found that a small amount of deposited carbon is beneficial to the performance of the anode. The cell showed a peak power density of 225 mW/cm2 when it was fed with H2 fuel at 700 °C, but the power density increased to 400 mW/cm2 when the fuel was switched from hydrogen to methane at the same flow rate. Methane conversion achieved about 90%, measured by gas chromatogram with a 10.0 mL/min flow rate of fuel at 700 °C. Although the carbon deposition was not suppressed absolutely, some deposited carbon was beneficial for performance improvement.

Subcellular SIMS imaging of gadolinium isotopes in human glioblastoma cells treated with a gadolinium containing MRI agent

NASA Astrophysics Data System (ADS)

Smith, Duane R.; Lorey, Daniel R.; Chandra, Subhash

2004-06-01

Neutron capture therapy is an experimental binary radiotherapeutic modality for the treatment of brain tumors such as glioblastoma multiforme. Recently, neutron capture therapy with gadolinium-157 has gained attention, and techniques for studying the subcellular distribution of gadolinium-157 are needed. In this preliminary study, we have been able to image the subcellular distribution of gadolinium-157, as well as the other six naturally abundant isotopes of gadolinium, with SIMS ion microscopy. T98G human glioblastoma cells were treated for 24 h with 25 mg/ml of the metal ion complex diethylenetriaminepentaacetic acid Gd(III) dihydrogen salt hydrate (Gd-DTPA). Gd-DTPA is a contrast enhancing agent used for MRI of brain tumors, blood-brain barrier impairment, diseases of the central nervous system, etc. A highly heterogeneous subcellular distribution was observed for gadolinium-157. The nuclei in each cell were distinctly lower in gadolinium-157 than in the cytoplasm. Even within the cytoplasm the gadolinium-157 was heterogeneously distributed. The other six naturally abundant isotopes of gadolinium were imaged from the same cells and exhibited a subcellular distribution consistent with that observed for gadolinium-157. These observations indicate that SIMS ion microscopy may be a viable approach for subcellular studies of gadolinium containing neutron capture therapy drugs and may even play a major role in the development and validation of new gadolinium contrast enhancing agents for diagnostic MRI applications.

High performance of SDC and GDC core shell type composite electrolytes using methane as a fuel for low temperature SOFC

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

Irshad, Muneeb; Siraj, Khurram, E-mail: razahussaini786@gmail.com, E-mail: khurram.uet@gmail.com; Javed, Fayyaz

Nanocomposites Samarium doped Ceria (SDC), Gadolinium doped Ceria (GDC), core shell SDC amorphous Na{sub 2}CO{sub 3} (SDCC) and GDC amorphous Na{sub 2}CO{sub 3} (GDCC) were synthesized using co-precipitation method and then compared to obtain better solid oxide electrolytes materials for low temperature Solid Oxide Fuel Cell (SOFCs). The comparison is done in terms of structure, crystallanity, thermal stability, conductivity and cell performance. In present work, XRD analysis confirmed proper doping of Sm and Gd in both single phase (SDC, GDC) and dual phase core shell (SDCC, GDCC) electrolyte materials. EDX analysis validated the presence of Sm and Gd in bothmore » single and dual phase electrolyte materials; also confirming the presence of amorphous Na{sub 2}CO{sub 3} in SDCC and GDCC. From TGA analysis a steep weight loss is observed in case of SDCC and GDCC when temperature rises above 725 °C while SDC and GDC do not show any loss. The ionic conductivity and cell performance of single phase SDC and GDC nanocomposite were compared with core shell GDC/amorphous Na{sub 2}CO{sub 3} and SDC/ amorphous Na{sub 2}CO{sub 3} nanocomposites using methane fuel. It is observed that dual phase core shell electrolytes materials (SDCC, GDCC) show better performance in low temperature range than their corresponding single phase electrolyte materials (SDC, GDC) with methane fuel.« less

Ceria-based electrospun fibers for renewable fuel production via two-step thermal redox cycles for carbon dioxide splitting.

PubMed

Gibbons, William T; Venstrom, Luke J; De Smith, Robert M; Davidson, Jane H; Jackson, Gregory S

2014-07-21

Zirconium-doped ceria (Ce(1-x)Zr(x)O2) was synthesized through a controlled electrospinning process as a promising approach to cost-effective, sinter-resistant material structures for high-temperature, solar-driven thermochemical redox cycles. To approximate a two-step redox cycle for solar fuel production, fibrous Ce(1-x)Zr(x)O2 with relatively low levels of Zr-doping (0 < x < 0.1) were cycled in an infrared-imaging furnace with high-temperature (up to 1500 °C) partial reduction and lower-temperature (∼800 °C) reoxidation via CO2 splitting to produce CO. Increases in Zr content improve reducibility and sintering resistance, and, for x≤ 0.05, do not significantly slow reoxidation kinetics for CO production. Cycle stability of the fibrous Ce(1-x)Zr(x)O2 (with x = 0.025) was assessed for a range of conditions by measuring rates of O2 release during reduction and CO production during reoxidation and by assessing post-cycling fiber crystallite sizes and surface areas. Sintering increases with reduction temperature but occurs primarily along the fiber axes. Even after 108 redox cycles with reduction at 1400 °C and oxidation with CO2 at 800 °C, the fibers maintain their structure with surface areas of ∼0.3 m(2) g(-1), higher than those observed in the literature for other ceria-based structures operating at similarly high temperature conditions. Total CO production and peak production rate stabilize above 3.0 mL g(-1) and 13.0 mL min(-1) g(-1), respectively. The results show the potential for electrospun oxides as sinter-resistant material structures with adequate surface area to support rapid CO2 splitting in solar thermochemical redox cycles.

Effect of gadolinium dopant on structural, magneto-transport, magnetic and thermo-power of Pr0.8Sr0.2MnO3

NASA Astrophysics Data System (ADS)

Poojary, Thrapthi; Babu, P. D.; Sanil, Tejaswini; Daivajna, Mamatha D.

2018-07-01

In the present investigation structural, magneto-transport, magnetic and thermo-power measurements of Gadolinium (Gd) doped Pr0.8-xGdxSr0.2MnO3 (0, 0.2, 0.25 and 0.3) manganites have been done. All the samples are single phased with orthorhombic structure. Temperature variation of resistance exhibits a high temperature transition occurring at 156 K and a low temperature cusp at around 95 K for pristine sample. With Gd doping resistance behavior shows insulating behavior throughout the whole temperature range. Magneto-Resistance (MR%) increases with Gd doping. A huge increase in thermo-electric power is observed with Gd doping.

Controlled Growth of Ceria Nanoarrays on Anatase Titania Powder: A Bottom-up Physical Picture.

PubMed

Kim, Hyun You; Hybertsen, Mark S; Liu, Ping

2017-01-11

The leading edge of catalysis research motivates physical understanding of the growth of nanoscale oxide structures on different supporting oxide materials that are themselves also nanostructured. This research opens up for consideration a diverse range of facets on the support material, versus the single facet typically involved in wide-area growth of thin films. Here, we study the growth of ceria nanoarchitectures on practical anatase titania powders as a showcase inspired by recent experiments. Density functional theory (DFT)-based methods are employed to characterize and rationalize the broad array of low energy nanostructures that emerge. Using a bottom-up approach, we are able to identify and characterize the underlying mechanisms for the facet-dependent growth of various ceria motifs on anatase titania based on formation energy. These motifs include 0D clusters, 1D chains, 2D plates, and 3D nanoparticles. The ceria growth mode and morphology are determined by the interplay of several factors including the role of the common cation valence, the interface template effect for different facets of the anatase support, enhanced ionic binding for more compact ceria motifs, and the local structural flexibility of oxygen ions in bridging the interface between anatase and ceria structures.

Controlled Growth of Ceria Nanoarrays on Anatase Titania Powder: A Bottom-up Physical Picture

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

Kim, Hyun You; Hybertsen, Mark S.; Liu, Ping

The leading edge of catalysis research motivates physical understanding of the growth of nanoscale oxide structures on different supporting oxide materials that are themselves also nanostructured. This research opens up for consideration a diverse range of facets on the support material, versus the single facet typically involved in wide-area growth of thin films. In this paper, we study the growth of ceria nanoarchitectures on practical anatase titania powders as a showcase inspired by recent experiments. Density functional theory (DFT)-based methods are employed to characterize and rationalize the broad array of low energy nanostructures that emerge. Using a bottom-up approach, wemore » are able to identify and characterize the underlying mechanisms for the facet-dependent growth of various ceria motifs on anatase titania based on formation energy. These motifs include 0D clusters, 1D chains, 2D plates, and 3D nanoparticles. Finally, the ceria growth mode and morphology are determined by the interplay of several factors including the role of the common cation valence, the interface template effect for different facets of the anatase support, enhanced ionic binding for more compact ceria motifs, and the local structural flexibility of oxygen ions in bridging the interface between anatase and ceria structures.« less

Controlled Growth of Ceria Nanoarrays on Anatase Titania Powder: A Bottom-up Physical Picture

DOE PAGES

Kim, Hyun You; Hybertsen, Mark S.; Liu, Ping

2016-12-05

The leading edge of catalysis research motivates physical understanding of the growth of nanoscale oxide structures on different supporting oxide materials that are themselves also nanostructured. This research opens up for consideration a diverse range of facets on the support material, versus the single facet typically involved in wide-area growth of thin films. In this paper, we study the growth of ceria nanoarchitectures on practical anatase titania powders as a showcase inspired by recent experiments. Density functional theory (DFT)-based methods are employed to characterize and rationalize the broad array of low energy nanostructures that emerge. Using a bottom-up approach, wemore » are able to identify and characterize the underlying mechanisms for the facet-dependent growth of various ceria motifs on anatase titania based on formation energy. These motifs include 0D clusters, 1D chains, 2D plates, and 3D nanoparticles. Finally, the ceria growth mode and morphology are determined by the interplay of several factors including the role of the common cation valence, the interface template effect for different facets of the anatase support, enhanced ionic binding for more compact ceria motifs, and the local structural flexibility of oxygen ions in bridging the interface between anatase and ceria structures.« less

Removal of gadolinium by peritoneal dialysis.

PubMed

Murashima, M; Drott, H R; Carlow, D; Shaw, L M; Milone, M; Bachman, M; Tsai, D E; Yang, S-L; Bloom, R D

2008-05-01

An association between gadolinium-containing contrast and the development of nephrogenic systemic fibrosis (NSF) has been increasingly recognized. For patients receiving hemodialysis (HD) who are exposed to gadolinium, the Federal Drug Administration (FDA) recommends HD to remove this contrast agent in order to minimize the risk of NSF. This study examines if gadolinium can be removed by frequent exchanges by peritoneal dialysis (PD). Following administration of 0.1 mmol/kg of gadodiamide to a patient with end-stage renal disease, the serum clearance of this contrast agent by automated PD was examined. 10 and 15 exchanges of PD using an automated cycler were respectively performed during the first and second 24-hour periods after gadolinium exposure. Serum gadolinium levels were measured 1 hour after the gadolinium administration, then at 24 and 48 hours after PD was initiated. 90% of the gadolinium was removed from the circulation in 2 days with a regimen of 10-15 exchanges per day of PD. For patients on chronic maintenance PD who receive gadolinium, our case suggests that a temporary intensive automated PD regimen, aimed at maximizing clearance of this contrast agent immediately after exposure, could be an effective alternative when institution of HD is problematic.

Ceria nanoclusters on graphene/Ru(0001): A new model catalyst system

DOE PAGES

Novotny, Z.; Netzer, F. P.; Dohnalek, Z.

2016-03-22

In this study, the growth of ceria nanoclusters on single-layer graphene on Ru(0001) has been examined, with a view towards fabricating a stable system for model catalysis studies. The surface morphology and cluster distribution as a function of oxide coverage and substrate temperature has been monitored by scanning tunneling microscopy (STM), whereas the chemical composition of the cluster deposits has been determined by Auger electron spectroscopy (AES). The ceria nanoparticles are of the CeO 2(111)-type and are anchored at the intrinsic defects of the graphene surface, resulting in a variation of the cluster densities across the macroscopic sample surface. Themore » ceria clusters on graphene display a remarkable stability against reduction in ultrahigh vacuum up to 900 K, but some sintering of clusters is observed for temperatures > 450 K. The evolution of the cluster size distribution suggests that the sintering proceeds via a Smoluchowski ripening mechanism, i.e. diffusion and aggregation of entire clusters.« less

Dramatic impact of the giant local magnetic fields on spin-dependent recombination processes in gadolinium based garnets

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

Romanov, N. G., E-mail: nikolai.romanov@mail.ioffe.ru; Tolmachev, D. O.; Gurin, A. S.

2015-06-29

A giant magnetic field effect on spin-dependent recombination of the radiation-induced defects has been found in cerium doped gadolinium based garnet crystals and ceramics, promising materials for scintillator applications. A sharp and strong increase in the afterglow intensity stimulated by external magnetic field and an evidence of the magnetic field memory have been discovered. The effect was ascribed to huge Gd-induced internal magnetic fields, which suppress the recombination, and cross-relaxation with Gd{sup 3+} ions leading to reorientation of the spins of the electron and hole centers. Thus, the spin system of radiation-induced defects in gadolinium garnet based scintillator materials wasmore » shown to accumulate significant energy which can be released in external magnetic fields.« less

Survival of Verwey transition in gadolinium-doped ultrasmall magnetite nanoparticles.

PubMed

Yeo, Sunmog; Choi, Hyunkyung; Kim, Chul Sung; Lee, Gyeong Tae; Seo, Jeong Hyun; Cha, Hyung Joon; Park, Jeong Chan

2017-09-28

We have demonstrated that the Verwey transition, which is highly sensitive to impurities, survives in anisotropic Gd-doped magnetite nanoparticles. Transmission electron microscopy analysis shows that the nanoparticles are uniformly distributed. X-ray photoelectron spectroscopy and EDS mapping analysis confirm Gd-doping on the nanoparticles. The Verwey transition of the Gd-doped magnetite nanoparticles is robust and the temperature dependence of the magnetic moment (zero field cooling and field cooling) shows the same behaviour as that of the Verwey transition in bulk magnetite, at a lower transition temperature (∼110 K). In addition, irregularly shaped nanoparticles do not show the Verwey transition whereas square-shaped nanoparticles show the transition. Mössbauer spectral analysis shows that the slope of the magnetic hyperfine field and the electric quadrupole splitting change at the same temperature, meaning that the Verwey transition occurs at ∼110 K. These results would provide new insights into understanding the Verwey transition in nano-sized materials.

Structural, optical and magnetic properties of gadolinium sesquioxide nanobars synthesized via thermal decomposition of gadolinium oxalate

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

Manigandan, R.; Giribabu, K.; Suresh, R.

2013-10-15

Graphical abstract: - Highlights: • The cubic Gd{sub 2}O{sub 3} nanobars are synthesized by decomposition of C{sub 6}H{sub 20}Gd{sub 2}O{sub 22}. • The nanoparticles are rectangular bar shape with high porous surface. • The combination of magnetic and optical properties within a single particle. • The Gd{sub 2}O{sub 3} nanobars have tailorable nanostructure, wide bandgap and are paramagnetic. - Abstract: Gadolinium oxide nanobars were obtained by thermal decomposition of gadolinium oxalate, which was synthesized by the chemical precipitation method along with glycerol. The functional group analysis and formation of gadolinium oxide from gadolinium oxalate were characterized by the Fourier transformmore » infrared spectroscopy and thermo gravimetric analyzer. The crystal structure, average crystallite size, and lattice parameter were analyzed by X-ray diffraction technique. Moreover, Raman shifts, elemental composition and morphology of the gadolinium oxide was widely investigated by the laser Raman microscope, X-ray photoelectron spectroscopy, FE-SEM-EDAX and HR-TEM, respectively. Furthermore, the optical properties like band gap, absorbance measurement of the gadolinium oxide were extensively examined. In addition, the paramagnetic property of gadolinium oxide nanobars was explored by the vibrating sample magnetometer.« less

A method to explore the quantitative interactions between metal and ceria for M/CeO2 catalysts

NASA Astrophysics Data System (ADS)

Zhu, Kong-Jie; Liu, Jie; Yang, Yan-Ju; Xu, Yu-Xing; Teng, Bo-Tao; Wen, Xiao-Dong; Fan, Maohong

2018-03-01

To explore the quantitative relationship of metal interaction with ceria plays a key role in the theoretical design of M/CeO2 catalysts, especially for the new hot topic of atomically dispersed catalysts. A method to quantitatively explore the interactions between metal and ceria is proposed in the present work on the basis of the qualitative analysis of the effects of different factors on metal adsorption at different ceria surfaces by using Ag/CeO2 as a case. Two parameters are firstly presented, Ep which converts the total adsorption energy into the interaction energy per Agsbnd O bond, and θdiff which measures the deviation of Agsbnd Osbnd Ce bond angle from the angle of the sp3 orbital hybridization of O atom. Using the two parameters, the quantitative relationship of the interaction energy between Ag and ceria is established. There is a linear correlation between Ep and dAgsbndO with θdiff. The higher θdiff, the weaker Ep, and the longer Agsbnd O bond. This method is also suitable for other metals (Cu, Ni, Pd, and Rh, etc.) on ceria. It is the first time to establish the quantitative relationship for the interaction between metal and ceria, and sheds light into the theoretical design of M/CeO2 catalysts.

Study of ceria-carbonate nanocomposite electrolytes for low-temperature solid oxide fuel cells.

PubMed

Fan, L; Wang, C; Di, J; Chen, M; Zheng, J; Zhu, B

2012-06-01

Composite and nanocomposite samarium doped ceria-carbonates powders were prepared by solid-state reaction, citric acid-nitrate combustion and modified nanocomposite approaches and used as electrolytes for low temperature solid oxide fuel cells. X-ray Diffraction, Scanning Electron Microscope, low-temperature Nitrogen Adsorption/desorption Experiments, Electrochemical Impedance Spectroscopy and fuel cell performance test were employed in characterization of these materials. All powders are nano-size particles with slight aggregation and carbonates are amorphous in composites. Nanocomposite electrolyte exhibits much lower impedance resistance and higher ionic conductivity than those of the other electrolytes at lower temperature. Fuel cell using the electrolyte prepared by modified nanocomposite approach exhibits the best performance in the whole operation temperature range and achieves a maximum power density of 839 mW cm(-2) at 600 degrees C with H2 as fuel. The excellent physical and electrochemical performances of nanocomposite electrolyte make it a promising candidate for low-temperature solid oxide fuel cells.

Controllable Fabrication and Optical Properties of Uniform Gadolinium Oxysulfate Hollow Spheres

PubMed Central

Chen, Fashen; Chen, Gen; Liu, Tao; Zhang, Ning; Liu, Xiaohe; Luo, Hongmei; Li, Junhui; Chen, Limiao; Ma, Renzhi; Qiu, Guanzhou

2015-01-01

Uniform gadolinium oxysulfate (Gd2O2SO4) hollow spheres were successfully fabricated by calcination of corresponding Gd-organic precursor obtained via a facile hydrothermal process. The Gd2O2SO4 hollow spheres have a mean diameter of approximately 550 nm and shell thickness in the range of 30–70 nm. The sizes and morphologies of as-prepared Gd2O2SO4 hollow spheres could be deliberately controlled by adjusting the experimental parameters. Eu-doped Gd2O2SO4 hollow spheres have also been prepared for the property modification and practical applications. The structure, morphology, and properties of as-prepared products were characterized by XRD, TEM, HRTEM, SEM and fluorescence spectrophotometer. Excited with ultraviolet (UV) pump laser, successful downconversion (DC) could be achieved for Eu-doped Gd2O2SO4 hollow spheres. PMID:26671661

Eco-friendly Synthesis of Ceria Foam via Carboxymethylcellulose Gelation: Application for the Epoxidation of Chalcone

EPA Science Inventory

A simple and innovative process is described for the eco-friendly preparation of ceria foams via the carboxymethylcellulose gelation by Ce4+ cations; heat treatment of the ensuing xerogels produces ceria foams. The influence of the concentration of cerium and of the calcination t...

Hydrodeoxygenation of Guaiacol over Ceria-Zirconia Catalysts.

PubMed

Schimming, Sarah M; LaMont, Onaje D; König, Michael; Rogers, Allyson K; D'Amico, Andrew D; Yung, Matthew M; Sievers, Carsten

2015-06-22

The hydrodeoxygenation of guaiacol is investigated over bulk ceria and ceria-zirconia catalysts with different elemental compositions. The reactions are performed in a flow reactor at 1 atm and 275-400 °C. The primary products are phenol and catechol, whereas cresol and benzene are formed as secondary products. No products with hydrogenated rings are formed. The highest conversion of guaiacol is achieved over a catalyst containing 60 mol % CeO2 and 40 mol % ZrO2 . Pseudo-first-order activation energies of 97-114 kJ mol(-1) are observed over the mixed metal oxide catalysts. None of the catalysts show significant deactivation during 72 h on stream. The important physicochemical properties of the catalysts are characterized by X-ray diffraction (XRD), temperature-programmed reduction, titration of oxygen vacancies, and temperature-programmed desorption of ammonia. On the basis of these experimental results, the reasons for the observed reactivity trends are identified. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Anisotropic chemical strain in cubic ceria due to oxygen-vacancy-induced elastic dipoles.

PubMed

Das, Tridip; Nicholas, Jason D; Sheldon, Brian W; Qi, Yue

2018-06-06

Accurate characterization of chemical strain is required to study a broad range of chemical-mechanical coupling phenomena. One of the most studied mechano-chemically active oxides, nonstoichiometric ceria (CeO2-δ), has only been described by a scalar chemical strain assuming isotropic deformation. However, combined density functional theory (DFT) calculations and elastic dipole tensor theory reveal that both the short-range bond distortions surrounding an oxygen-vacancy and the long-range chemical strain are anisotropic in cubic CeO2-δ. The origin of this anisotropy is the charge disproportionation between the four cerium atoms around each oxygen-vacancy (two become Ce3+ and two become Ce4+) when a neutral oxygen-vacancy is formed. Around the oxygen-vacancy, six of the Ce3+-O bonds elongate, one of the Ce3+-O bond shorten, and all seven of the Ce4+-O bonds shorten. Further, the average and maximum chemical strain values obtained through tensor analysis successfully bound the various experimental data. Lastly, the anisotropic, oxygen-vacancy-elastic-dipole induced chemical strain is polarizable, which provides a physical model for the giant electrostriction recently discovered in doped and non-doped CeO2-δ. Together, this work highlights the need to consider anisotropic tensors when calculating the chemical strain induced by dilute point defects in all materials, regardless of their symmetry.

Pathophysiology of gadolinium-associated systemic fibrosis

PubMed Central

Drel, Viktor; Gorin, Yves

2016-01-01

Systemic fibrosis from gadolinium-based magnetic resonance imaging contrast is a scourge for the afflicted. Although gadolinium-associated systemic fibrosis is a rare condition, the threat of litigation has vastly altered clinical practice. Most theories concerning the etiology of the fibrosis are grounded in case reports rather than experiment. This has led to the widely accepted conjecture that the relative affinity of certain contrast agents for the gadolinium ion inversely correlates with the risk of succumbing to the disease. How gadolinium-containing contrast agents trigger widespread and site-specific systemic fibrosis and how chronicity is maintained are largely unknown. This review highlights experimentally-derived information from our laboratory and others that pertain to our understanding of the pathophysiology of gadolinium-associated systemic fibrosis. PMID:27147669

Investigations of oxidative stress effects and their mechanisms in rat brain after systemic administration of ceria engineered nanomaterials

NASA Astrophysics Data System (ADS)

Hardas, Sarita S.

Advancing applications of engineered nanomaterials (ENM) in various fields create the opportunity for intended (e.g. drug and gene delivery) or unintended (e.g. occupational and environmental) exposure to ENM. However, the knowledge of ENM-toxicity is lagging behind their application development. Understanding the ENM hazard can help us to avoid potential human health problems associated with ENM applications as well as to increase their public acceptance. Ceria (cerium [Ce] oxide) ENM have many current and potential commercial applications. Beyond the traditional use of ceria as an abrasive, the scope of ceria ENM applications now extends into fuel cell manufacturing, diesel fuel additives and for therapeutic intervention as a putative antioxidant. However, the biological effects of ceria ENM exposure have yet to be fully defined. Both pro-and anti-oxidative effects of ceria ENM exposure are repeatedly reported in literature. EPA, NIEHS and OECD organizations have nominated ceria for its toxicological evaluation. All these together gave us the impetus to examine the oxidative stress effects of ceria ENM after systemic administration. Induction of oxidative stress is one of the primary mechanisms of ENM toxicity. Oxidative stress plays an important role in maintaining the redox homeostasis in the biological system. Increased oxidative stress, due to depletion of antioxidant enzymes or molecules and / or due to increased production of reactive oxygen (ROS) or nitrogen (RNS) species may lead to protein oxidation, lipid peroxidation and/or DNA damage. Increased protein oxidation or lipid peroxidation together with antioxidant protein levels and activity can serve as markers of oxidative stress. To investigate the oxidative stress effects and the mechanisms of ceria-ENM toxicity, fully characterized ceria ENM of different sizes (˜ 5nm, 15nm, 30nm, 55nm and nanorods) were systematically injected into rats intravenously in separate experiments. Three brain regions

Plasma sprayed ceria-containing interlayer

DOEpatents

Schmidt, Douglas S.; Folser, George R.

2006-01-10

A plasma sprayed ceria-containing interlayer is provided. The interlayer has particular application in connection with a solid oxide fuel cell used within a power generation system. The fuel cell advantageously comprises an air electrode, a plasma sprayed interlayer disposed on at least a portion of the air electrode, a plasma sprayed electrolyte disposed on at least a portion of the interlayer, and a fuel electrode applied on at least a portion of the electrolyte.

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

First principles study of vibrational dynamics of ceria-titania hybrid clusters

NASA Astrophysics Data System (ADS)

Majid, Abdul; Bibi, Maryam

2017-04-01

Density functional theory based calculations were performed to study vibrational properties of ceria, titania, and ceria-titania hybrid clusters. The findings revealed the dominance of vibrations related to oxygen when compared to those of metallic atoms in the clusters. In case of hybrid cluster, the softening of normal modes related to exterior oxygen atoms in ceria and softening/hardening of high/low frequency modes related to titania dimmers are observed. The results calculated for monomers conform to symmetry predictions according to which three IR and three Raman active modes were detected for TiO2, whereas two IR active and one Raman active modes were observed for CeO2. The comparative analysis indicates that the hybrid cluster CeTiO4 contains simultaneous vibrational fingerprints of the component dimmers. The symmetry, nature of vibrations, IR and Raman activity, intensities, and atomic involvement in different modes of the clusters are described in detail. The study points to engineering of CeTiO4 to tailor its properties for technological visible region applications in photocatalytic and electrochemical devices.

Fabrication of low-temperature solid oxide fuel cells with a nanothin protective layer by atomic layer deposition

PubMed Central

2013-01-01

Anode aluminum oxide-supported thin-film fuel cells having a sub-500-nm-thick bilayered electrolyte comprising a gadolinium-doped ceria (GDC) layer and an yttria-stabilized zirconia (YSZ) layer were fabricated and electrochemically characterized in order to investigate the effect of the YSZ protective layer. The highly dense and thin YSZ layer acted as a blockage against electron and oxygen permeation between the anode and GDC electrolyte. Dense GDC and YSZ thin films were fabricated using radio frequency sputtering and atomic layer deposition techniques, respectively. The resulting bilayered thin-film fuel cell generated a significantly higher open circuit voltage of approximately 1.07 V compared with a thin-film fuel cell with a single-layered GDC electrolyte (approximately 0.3 V). PMID:23342963

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.

Effective Heat and Mass Transport Properties of Anisotropic Porous Ceria for Solar Thermochemical Fuel Generation

PubMed Central

Haussener, Sophia; Steinfeld, Aldo

2012-01-01

High-resolution X-ray computed tomography is employed to obtain the exact 3D geometrical configuration of porous anisotropic ceria applied in solar-driven thermochemical cycles for splitting H2O and CO2. The tomography data are, in turn, used in direct pore-level numerical simulations for determining the morphological and effective heat/mass transport properties of porous ceria, namely: porosity, specific surface area, pore size distribution, extinction coefficient, thermal conductivity, convective heat transfer coefficient, permeability, Dupuit-Forchheimer coefficient, and tortuosity and residence time distributions. Tailored foam designs for enhanced transport properties are examined by means of adjusting morphologies of artificial ceria samples composed of bimodal distributed overlapping transparent spheres in an opaque medium. PMID:28817039

Efficacy of radiosensitizing doped titania nanoparticles under hypoxia and preparation of an embolic microparticle

PubMed Central

Morrison, Rachel A; Rybak-Smith, Malgorzata J; Thompson, James M; Thiebaut, Bénédicte; Hill, Mark A; Townley, Helen E

2017-01-01

The aim of this study was to develop a manufacturing protocol for large-scale production of doped titania radiosensitizing nanoparticles (NPs) to establish their activity under hypoxia and to produce a multimodal radiosensitizing embolic particle for cancer treatment. We have previously shown that radiosensitizing NPs can be synthesized from titania doped with rare earth elements, especially gadolinium. To translate this technology to the clinic, a crucial step is to find a suitable, scalable, high-throughput method. Herein, we have described the use of flame spray pyrolysis (FSP) to generate NPs from titanium and gadolinium precursors to produce titania NPs doped with 5 at% gadolinium. The NPs were fully characterized, and their capacity to act as radiosensitizers was confirmed by clonogenic assays. The integrity of the NPs in vitro was also ascertained due to the potentially adverse effects of free gadolinium in the body. The activity of the NPs was then studied under hypoxia since this is often a barrier to effective radiotherapy. In vitro radiosensitization experiments were performed with both the hypoxia mimetics deferoxamine and cobalt chloride and also under true hypoxia (oxygen concentration of 0.2%). It was shown that the radiosensitizing NPs were able to cause a significant increase in cell death even after irradiation under hypoxic conditions such as those found in tumors. Subsequently, the synthesized NPs were used to modify polystyrene embolization microparticles. The NPs were sintered to the surface of the microparticles by heating at 230°C for 15 minutes. This resulted in a good coverage of the surface and to generate embolization particles that were shown to be radiosensitizing. Such multimodal particles could therefore result in occlusion of the tumor blood vessels in conjunction with localized reactive oxygen species generation, even under hypoxic conditions such as those found in the center of tumors. PMID:28572729

Efficacy of radiosensitizing doped titania nanoparticles under hypoxia and preparation of an embolic microparticle.

PubMed

Morrison, Rachel A; Rybak-Smith, Malgorzata J; Thompson, James M; Thiebaut, Bénédicte; Hill, Mark A; Townley, Helen E

2017-01-01

The aim of this study was to develop a manufacturing protocol for large-scale production of doped titania radiosensitizing nanoparticles (NPs) to establish their activity under hypoxia and to produce a multimodal radiosensitizing embolic particle for cancer treatment. We have previously shown that radiosensitizing NPs can be synthesized from titania doped with rare earth elements, especially gadolinium. To translate this technology to the clinic, a crucial step is to find a suitable, scalable, high-throughput method. Herein, we have described the use of flame spray pyrolysis (FSP) to generate NPs from titanium and gadolinium precursors to produce titania NPs doped with 5 at% gadolinium. The NPs were fully characterized, and their capacity to act as radiosensitizers was confirmed by clonogenic assays. The integrity of the NPs in vitro was also ascertained due to the potentially adverse effects of free gadolinium in the body. The activity of the NPs was then studied under hypoxia since this is often a barrier to effective radiotherapy. In vitro radiosensitization experiments were performed with both the hypoxia mimetics deferoxamine and cobalt chloride and also under true hypoxia (oxygen concentration of 0.2%). It was shown that the radiosensitizing NPs were able to cause a significant increase in cell death even after irradiation under hypoxic conditions such as those found in tumors. Subsequently, the synthesized NPs were used to modify polystyrene embolization microparticles. The NPs were sintered to the surface of the microparticles by heating at 230°C for 15 minutes. This resulted in a good coverage of the surface and to generate embolization particles that were shown to be radiosensitizing. Such multimodal particles could therefore result in occlusion of the tumor blood vessels in conjunction with localized reactive oxygen species generation, even under hypoxic conditions such as those found in the center of tumors.

Use of gadolinium-based magnetic resonance imaging contrast agents and awareness of brain gadolinium deposition among pediatric providers in North America.

PubMed

Mithal, Leena B; Patel, Payal S; Mithal, Divakar; Palac, Hannah L; Rozenfeld, Michael N

2017-05-01

Numerous recent articles have reported brain gadolinium deposition when using linear but not macrocyclic gadolinium-based contrast agents (GBCAs). To determine the current landscape of gadolinium use among pediatric institutions and the knowledge base of radiologists and referring providers with regard to GBCAs and brain gadolinium deposition. We e-mailed voluntary closed surveys to 5,390 physicians in various pediatric professional societies between January 2016 and March 2016. We used chi-square and Fisher exact tests to compare response distributions among specialties. We found that 80% of surveyed pediatric hospitals use macrocyclic contrast agents. In the last year, 58% switched their agent, most commonly to gadoterate meglumine, with the most common reason being brain gadolinium deposition. Furthermore, surveys indicated that 23% of hospitals are considering switching, and, of these, 83% would switch to gadoterate meglumine; the most common reasons were brain gadolinium deposition and safety. Radiologists were more aware of brain gadolinium deposition than non-radiologist physicians (87% vs. 26%; P<0.0001). Radiologists and referring providers expressed similar levels of concern (95% and 89%). Twelve percent of radiologists and 2% of referring providers reported patients asking about brain gadolinium deposition. Radiologists were significantly more comfortable addressing patient inquiries than referring pediatric physicians (48% vs. 6%; P<0.0001). The number of MRIs requested by referring pediatric physicians correlated with their knowledge of brain gadolinium deposition, contrast agent used by their hospital, and comfort discussing brain gadolinium deposition with patients (P<0.0001). Since the discovery of brain gadolinium deposition, many pediatric hospitals have switched to or plan to switch to a more stable macrocyclic MR contrast agent, most commonly gadoterate meglumine. Despite this, there is need for substantial further education of radiologists and

Fast MAS 1H NMR Study of Water Adsorption and Dissociation on the (100) Surface of Ceria Nanocubes: A Fully Hydroxylated, Hydrophobic Ceria Surface

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

Gill, Lance; Beste, Ariana; Chen, Banghao

1H nuclear magnetic resonance (NMR) spectroscopy was used to study hydroxylic surface species on ceria nanocubes, a crystalline, high-surface-area CeO 2 that presents mostly (100) facets. Water adsorption and desorption experiments in combination with fast magic angle spinning (MAS, 20–40 kHz) 1H NMR provide high-resolution 1H spectra that allow the observation of ten resonance bands (water or hydroxyl) on or under the (100) surface. Assignments were made using a combination of adsorption and temperature-programmed desorption, quantitative spin counting, deuterium exchange, spin–lattice (T 1) and spin–spin (T 2) relaxation, and DFT calculations. In air, the (100) surface exists as a fullymore » hydroxylated surface. Water adsorption and dissociation on dry ceria surfaces occur first at oxygen vacancies, but Ce 3+ centers are not required since water dissociation is barrier-less on the fully oxidized surface. Surface $-$OH functionality occurs in two resolved bands representing isolated $-$OH (1 ppm) and hydrogen-bonded $-$OH (9 ppm), the latter being dominant. Deuterium exchange of surface hydroxyls with D 2O does not occur under mild or forcing conditions. Despite large differences in the T 1 of surface hydroxyls and physisorbed water, surface hydroxyl T 1 values are independent of the presence or absence of physisorbed water, demonstrating that the protons within these two functional group pools are not in intimate contact. These observations show that, once hydroxylated, the surface $-$OH functionality preferentially forms hydrogen bonds with surface lattice oxygen, i.e., the hydroxylated (100) surface of ceria is hydrophobic. Near this surface it is energetically more favorable for physisorbed water to hydrogen bond to itself rather than to the surface. DFT calculations support this notion. Impurity Na + remaining in incompletely washed ceria nanocubes increases the surface hydrophilicity. In conclusion, sharp, low-field resonances observed in spectra

Fast MAS 1H NMR Study of Water Adsorption and Dissociation on the (100) Surface of Ceria Nanocubes: A Fully Hydroxylated, Hydrophobic Ceria Surface

DOE PAGES

Gill, Lance; Beste, Ariana; Chen, Banghao; ...

2017-03-22

1H nuclear magnetic resonance (NMR) spectroscopy was used to study hydroxylic surface species on ceria nanocubes, a crystalline, high-surface-area CeO 2 that presents mostly (100) facets. Water adsorption and desorption experiments in combination with fast magic angle spinning (MAS, 20–40 kHz) 1H NMR provide high-resolution 1H spectra that allow the observation of ten resonance bands (water or hydroxyl) on or under the (100) surface. Assignments were made using a combination of adsorption and temperature-programmed desorption, quantitative spin counting, deuterium exchange, spin–lattice (T 1) and spin–spin (T 2) relaxation, and DFT calculations. In air, the (100) surface exists as a fullymore » hydroxylated surface. Water adsorption and dissociation on dry ceria surfaces occur first at oxygen vacancies, but Ce 3+ centers are not required since water dissociation is barrier-less on the fully oxidized surface. Surface $-$OH functionality occurs in two resolved bands representing isolated $-$OH (1 ppm) and hydrogen-bonded $-$OH (9 ppm), the latter being dominant. Deuterium exchange of surface hydroxyls with D 2O does not occur under mild or forcing conditions. Despite large differences in the T 1 of surface hydroxyls and physisorbed water, surface hydroxyl T 1 values are independent of the presence or absence of physisorbed water, demonstrating that the protons within these two functional group pools are not in intimate contact. These observations show that, once hydroxylated, the surface $-$OH functionality preferentially forms hydrogen bonds with surface lattice oxygen, i.e., the hydroxylated (100) surface of ceria is hydrophobic. Near this surface it is energetically more favorable for physisorbed water to hydrogen bond to itself rather than to the surface. DFT calculations support this notion. Impurity Na + remaining in incompletely washed ceria nanocubes increases the surface hydrophilicity. In conclusion, sharp, low-field resonances observed in spectra

Charge distribution and transport properties in reduced ceria phases: A review

NASA Astrophysics Data System (ADS)

Shoko, E.; Smith, M. F.; McKenzie, Ross H.

2011-12-01

The question of the charge distribution in reduced ceria phases (CeO2-x) is important for understanding the microscopic physics of oxygen storage capacity, and the electronic and ionic conductivities in these materials. All these are key properties in the application of these materials in catalysis and electrochemical devices. Several approaches have been applied to study this problem, including ab initio methods. Recently [1], we applied the bond valence model (BVM) to discuss the charge distribution in several different crystallographic phases of reduced ceria. Here, we compare the BVM results to those from atomistic simulations to determine if there is consistency in the predictions of the two approaches. Our analysis shows that the two methods give a consistent picture of the charge distribution around oxygen vacancies in bulk reduced ceria phases. We then review the transport theory applicable to reduced ceria phases, providing useful relationships which enable comparison of experimental results obtained by different techniques. In particular, we compare transport parameters obtained from the observed optical absorption spectrum, α(ω), dc electrical conductivity with those predicted by small polaron theory and the Harrison method. The small polaron energy is comparable to that estimated from α(ω). However, we found a discrepancy between the value of the electron hopping matrix element, t, estimated from the Marcus-Hush formula and that obtained by the Harrison method. Part of this discrepancy could be attributed to the system lying in the crossover region between adiabatic and nonadiabatic whereas our calculations assumed the system to be nonadiabatic. Finally, by considering the relationship between the charge distribution and electronic conductivity, we suggest the possibility of low temperature metallic conductivity for intermediate phases, i.e., x˜0.3. This has not yet been experimentally observed.

White- and blue-light-emitting dysprosium(III) and terbium(III)-doped gadolinium titanate phosphors.

PubMed

Antić, Ž; Kuzman, S; Đorđević, V; Dramićanin, M D; Thundat, T

2017-06-01

Here we report the synthesis and structural, morphological, and photoluminescence analysis of white- and blue-light-emitting Dy 3 + - and Tm 3 + -doped Gd 2 Ti 2 O 7 nanophosphors. Single-phase cubic Gd 2 Ti 2 O 7 nanopowders consist of compact, dense aggregates of nanoparticles with an average size of ~25 nm for Dy 3 + -doped and ~50 nm for Tm 3 + -doped samples. The photoluminescence results indicated that ultraviolet (UV) light excitation of the Dy 3 + -doped sample resulted in direct generation of white light, while a dominant yellow emission was obtained under blue-light excitation. Intense blue light was obtained for Tm 3 + -doped Gd 2 Ti 2 O 7 under UV excitation suggesting that this material could be used as a blue phosphor. Copyright © 2016 John Wiley & Sons, Ltd.

Extended x-ray absorption fine structure spectroscopy and x-ray absorption near edge spectroscopy study of aliovalent doped ceria to correlate local structural changes with oxygen vacancies clustering

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

Shirbhate, S. C.; Acharya, S. A., E-mail: saha275@yahoo.com; Yadav, A. K.

2016-04-04

This study provides atomic scale insight to understand the role of aliovalent dopants on oxygen vacancies clustering and dissociation mechanism in ceria system in order to enhance the performance of oxy-ion conductor. Dopants induced microscale changes in ceria are probed by extended X-ray absorption fine structure spectroscopy, X-ray absorption near edge spectra, and Raman spectroscopy. The results are explored to establish a correlation between atomic level structural changes (coordination number, interatomic spacing) → formation of dimer and trimer type cation-oxygen vacancies defect complex (intrinsic and extrinsic) → dissociation of oxygen vacancies from defect cluster → ionic conductivity temperature. It ismore » a strategic approach to understand key physics of ionic conductivity mechanism in order to reduce operating temperature of electrolytes for intermediate temperature (300–450 °C) electrochemical devices for the first time.« less

Methane oxidation on Pd–Ceria: A DFT study of the mechanism over PdxCe1-xO2, Pd, and PdO

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

Mayernick, Adam D.; Janik, Michael J.

2011-02-14

Palladium/ceria exhibits unique catalytic activity for hydrocarbon oxidation; however, the chemical and structural properties of active sites on the palladium–ceria surface are difficult to characterize. Strong interactions between palladium and the ceria support stabilize oxidized Pdδ+ species, which may contribute to the significant activity of Pd/ceria for methane oxidation. We present a density functional theory (DFT + U) investigation into methane oxidation over Pd/ceria and quantify the activity of the Pd xCe 1-xO 2(1 1 1) mixed oxide surface in comparison with the PdO(1 0 0) and Pd(1 1 1) surfaces. The methane activation barrier is lowest over the Pdmore » xCe 1-xO 2(1 1 1) surface, even lower than over the Pd(1 1 1) surface or low coordinated stepped or kinked Pd sites. Subsequent reaction steps in complete oxidation, including product desorption and vacancy refilling, are considered to substantiate that methane activation remains the rate-limiting step despite the low barrier over Pd xCe 1-xO 2(1 1 1). The low barrier over the Pd xCe 1-xO 2(1 1 1) surface demonstrates that mixed ceria-noble metal oxides offer the potential for improved hydrocarbon oxidation performance with respect to dispersed noble metal particles on ceria.« less

Temperature Dependence Discontinuity in the Stability of Manganese doped Ceria Nanocrystals

DOE PAGES

Wu, Longjia; Dholabhai, Pratik; Uberuaga, Blas P.; ...

2017-01-05

CeO 2 has strong potential for chemical-looping water splitting. It has been shown that manganese doping decreases interface energies of CeO 2, allowing increased stability of high surface areas in this oxygen carrier oxide. The phenomenon is related to the segregation of Mn3+ at interfaces, which causes a measurable decrease in excess energy. Here in the present work, it is shown that, despite the stability of nanocrystals of manganese-doped CeO 2 with relation to undoped CeO 2, the effect is strongly dependent on the oxidation state of manganese, i.e., on the temperature. At temperatures below 800 °C, Mn is inmore » the 3+ valence state, and coarsening is hindered by the reduced interface energetics, showing smaller crystal sizes with increasing Mn content. At temperatures above 800 °C, Mn is reduced to its 2+ valence state, and coarsening is enhanced with increasing Mn content. Atomistic simulations show the segregation of Mn to grain boundaries is relatively insensitive to the charge state of the dopant. However, point defect modeling finds that the reduced state causes a decrease in cation vacancy concentration and an increase in cation interstitials, reducing drag forces for grain boundary mobility and increasing growth rates.« less

Experimental Demonstration of the Thermochemical Reduction of Ceria in a Solar Aerosol Reactor

PubMed Central

2016-01-01

We report on the experimental demonstration of an aerosol solar reactor for the thermal reduction of ceria, as part of a thermochemical redox cycle for splitting H2O and CO2. The concept utilizes a cavity-receiver enclosing an array of alumina tubes, each containing a downward gravity-driven aerosol flow of ceria particles countercurrent to an inert sweep gas flow for intrinsic separation of reduced ceria and oxygen. A 2 kWth lab-scale prototype with a single tube was tested under radiative fluxes approaching 4000 suns, yielding reaction extents of up to 53% of the thermodynamic equilibrium at 1919 K within residence times below 1 s. Upon thermal redox cycling, fresh primary particles of 2.44 μm mean size initially formed large agglomerates of 1000 μm mean size, then sintered into stable particles of 150 μm mean size. The reaction extent was primarily limited by heat transfer for large particles/agglomerates (mean size > 200 μm) and by the gas phase advection of product O2 for smaller particles. PMID:27853339

Experimental Demonstration of the Thermochemical Reduction of Ceria in a Solar Aerosol Reactor.

PubMed

Welte, Michael; Barhoumi, Rafik; Zbinden, Adrian; Scheffe, Jonathan R; Steinfeld, Aldo

2016-10-12

We report on the experimental demonstration of an aerosol solar reactor for the thermal reduction of ceria, as part of a thermochemical redox cycle for splitting H 2 O and CO 2 . The concept utilizes a cavity-receiver enclosing an array of alumina tubes, each containing a downward gravity-driven aerosol flow of ceria particles countercurrent to an inert sweep gas flow for intrinsic separation of reduced ceria and oxygen. A 2 kW th lab-scale prototype with a single tube was tested under radiative fluxes approaching 4000 suns, yielding reaction extents of up to 53% of the thermodynamic equilibrium at 1919 K within residence times below 1 s. Upon thermal redox cycling, fresh primary particles of 2.44 μm mean size initially formed large agglomerates of 1000 μm mean size, then sintered into stable particles of 150 μm mean size. The reaction extent was primarily limited by heat transfer for large particles/agglomerates (mean size > 200 μm) and by the gas phase advection of product O 2 for smaller particles.

Role of ytterbium-erbium co-doped gadolinium molybdate (Gd₂(MoO₄)₃:Yb/Er) nanophosphors in solar cells.

PubMed

Jin, Xiao; Li, Haiyang; Li, Dongyu; Zhang, Qin; Li, Feng; Sun, Weifu; Chen, Zihan; Li, Qinghua

2016-09-05

Insufficient harvest of solar light energy is one of the obstacles for current photovoltaic devices to achieve high performance. Especially, conventional organic/inorganic hybrid solar cells (HSCs) based on PTB7 as p-type semiconductor can only utilize 400-800 nm solar spectrum. One effective strategy to overcome this obstacle is the introduction of up-conversion nanophosphors (NPs), in the virtue of utilizing the near infrared region (NIR) of solar radiation. Up-conversion can convert low-energy photons to high-energy ones through multi-photon processes, by which the solar spectrum is tailored to well match the absorptive domain of the absorber. Herein we incorporate erbium-ytterbium co-doped gadolinium molybdate (Gd₂(MoO₄)₃, GMO), denoted as GMO:Yb/Er, into TiO₂ acceptor film in HSCs to enhance the light harvest. Here Er³⁺ acts as activator while Yb-MoO₄ ^2- is the joint sensitizer. Facts proved that the GMO:Yb/Er single crystal NPs are capable of turning NIR photons to visible photons that can be easily captured by PTB7. Studies on time-resolved photoluminescence demonstrate that electron transfer rate at the interface increases sharply from 0.65 to 1.42 × 10⁹ s^-1. As a result, the photoelectric conversion efficiency of the GMO:Yb/Er doped TiO₂/PTB7 HSCs reach 3.67%, which is increased by around 25% compared to their neat PTB7/TiO₂ counterparts (2.94%). This work may open a hopeful way to take the advantage of those conversional rare-earth ion doped oxides that function in tailoring solar light spectrum for optoelectronic applications.

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

Structural analysis of nickel doped cerium oxide catalysts for fuel reforming in solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Cavendish, Rio

As world energy demands increase, research into more efficient energy production methods has become imperative. Heterogeneous catalysis and nanoscience are used to promote chemical transformations important for energy production. These concepts are important in solid oxide fuel cells (SOFCs) which have attracted attention because of their potential to provide an efficient and environmentally favorable power generation system. The SOFC is also fuel-flexible with the ability to run directly on many fuels other than hydrogen. Internal fuel reforming directly in the anode of the SOFC would greatly reduce the cost and complexity of the device. Methane is the simplest hydrocarbon and a main component in natural gas, making it useful when testing catalysts on the laboratory scale. Nickel (Ni) and gadolinium (Gd) doped ceria (CeO 2) catalysts for potential use in the SOFC anode were synthesized with a spray drying method and tested for catalytic performance using partial oxidation of methane and steam reforming. The relationships between catalytic performance and structure were then investigated using X-ray diffraction, transmission electron microscopy, and environmental transmission electron microscopy. The possibility of solid solutions, segregated phases, and surface layers of Ni were explored. Results for a 10 at.% Ni in CeO2 catalyst reveal a poor catalytic behavior while a 20 at.% Ni in CeO2 catalyst is shown to have superior activity. The inclusion of both 10 at.% Gd and 10 at.% Ni in CeO2 enhances the catalytic performance. Analysis of the presence of Ni in all 3 samples reveals Ni heterogeneity and little evidence for extensive solid solution doping. Ni is found in small domains throughout CeO2 particles. In the 20 at.% Ni sample a segregated, catalytically active NiO phase is observed. Overall, it is found that significant interaction between Ni and CeO2 occurs that could affect the synthesis and functionality of the SOFC anode.

Impact of structure and morphology of nanostructured ceria coating on AISI 304 oxidation kinetics

NASA Astrophysics Data System (ADS)

Aadhavan, R.; Suresh Babu, K.

2017-07-01

Nanostructured ceria-based coatings are shown to be protective against high-temperature oxidation of AISI 304 due to the dynamics of oxidation state and associated defects. However, the processing parameters of deposition have a strong influence in determining the structural and morphological aspects of ceria. The present work focuses on the effect of variation in substrate temperature (50-300 °C) and deposition rate (0.1-50 Å/s) of ceria in electron beam physical vapour evaporation method and correlates the changes in structure and morphology to high-temperature oxidation protection. Unlike deposition rate, substrate temperature exhibited a profound influence on crystallite size (7-18 nm) and oxygen vacancy concentration. Upon isothermal oxidation at 1243 K for 24 h, bare AISI 304 exhibited a linear mass gain with a rate constant of 3.0 ± 0.03 × 10-3 kg2 m-4 s-1 while ceria coating lowered the kinetics by 3-4 orders. Though the thickness of the coating was kept constant at 2 μm, higher deposition rate offered one order lower protection due to the porous nature of the coating. Variation in the substrate temperature modulated the porosity as well as oxygen vacancy concentration and displayed the best protection for coatings deposited at moderate substrate temperature. The present work demonstrates the significance of selecting appropriate processing parameters to obtain the required morphology for efficient high-temperature oxidation protection.

A novel design of anode-supported solid oxide fuel cells with Y 2O 3-doped Bi 2O 3, LaGaO 3 and La-doped CeO 2 trilayer electrolyte

NASA Astrophysics Data System (ADS)

Guo, Weimin; Liu, Jiang

Anode-supported solid oxide fuel cells (SOFCs) with a trilayered yttria-doped bismuth oxide (YDB), strontium- and magnesium-doped lanthanum gallate (LSGM) and lanthanum-doped ceria (LDC) composite electrolyte film are developed. The cell with a YDB (18 μm)/LSGM (19 μm)/LDC (13 μm) composite electrolyte film (designated as cell-A) shows the open-circuit voltages (OCVs) slightly higher than that of a cell with an LSGM (31 μm)/LDC (17 μm) electrolyte film (designated as cell-B) in the operating temperature range of 500-700 °C. The cell-A using Ag-YDB composition as cathode exhibits lower polarization resistance and ohmic resistance than those of a cell-B at 700 °C. The results show that the introduction of YDB to an anode-supported SOFC with a LSGM/LDC composite electrolyte film can effectively block electronic transport through the cell and thus increased the OCVs, and can help the cell to achieve higher power output.

Synthesis and characterization of nanocrystalline Nd{sup 3+}-doped gadolinium scandium aluminum garnet powders by a gel-combustion method

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

Su, Jing, E-mail: zlj007@126.com; Miao, Ju-hong; Xu, Lin-hua

2012-07-15

Graphical abstract: The graph shows the emission spectra (λ{sub ex} = 808 nm) of 1 at.% Nd:GSAG powders sintered at different temperatures for 3 h. Compared with the powder sintered at 900 °C, the PL intensity of the powder sintered at 1000 °C decreased significantly. The changes in the PL intensity should mainly due to the crystallinity and dispersion of the powders. Highlights: ► We synthesized Nd:GSAG nano-powders by gel-combustion method successfully. ► We analyzed the structure and the morphology of the heat-treated products. ► We studied the optical characteristics of Nd:GSAG nano-powders. -- Abstract: Nd{sup 3+}-doped gadolinium scandium aluminummore » garnet (Nd:GSAG) precursor was synthesized by a gel combustion method using metal nitrates and citric acid as raw materials. The structure and morphology of the precursor and the sintered powders were studied by means of X-ray diffraction (XRD), infrared spectroscopy (IR) and transmission electron microscopy (TEM). The results showed that the precursor transformed into pure GSAG polycrystalline phase at about 800 °C, and the powders sintered at 800–1000 °C were well-dispersed with average particle sizes in the range of 30–80 nm. Optical properties of Nd:GSAG nano-powders were characterized by using photoluminescence spectroscopy. The highest photoluminescence intensity was achieved for the powder sintered at 900 °C.« less

Gadolinium Distribution in Cerebrospinal Fluid after Administration of a Gadolinium-based MR Contrast Agent in Humans.

PubMed

Berger, Florian; Kubik-Huch, Rahel A; Niemann, Tilo; Schmid, Hans Ruedi; Poetzsch, Michael; Froehlich, Johannes M; Beer, Jürg H; Thali, Michael J; Kraemer, Thomas

2018-05-08

Purpose To evaluate whether gadolinium penetrates human cerebrospinal fluid (CSF) after MR imaging (MRI) with a gadolinium-based contrast agent (GBCA). Materials and Methods For this retrospective study, the authors analyzed 60 CSF samples from 57 patients (median age, 50 years; range, 3-92 years) who underwent one contrast material-enhanced MRI examination with gadoterate meglumine within 60 days of CSF extraction between January and December 2016. CSF samples from patients who underwent MRI without contrast material administration (n = 22) or those who underwent contrast-enhanced MRI at least 1 year before extraction (n = 2) were analyzed and used as control samples. CSF measurements were performed with inductively coupled plasma mass spectrometry by monitoring the gadolinium 158 isotope. Statistical analyses were performed by using a preliminary Kruskal-Wallis test. Results Higher CSF gadolinium concentrations were detected within the first 8 hours after GBCA administration (mean concentration, 1152 ng/mL ± 734.6). Concentrations were lower between 8 and 48 hours (872 ng/mL ± 586). After 48 hours, gadolinium was almost completely cleared from CSF (121 ng/mL ± 296.3). All but two samples from the 24 control patients (median age, 60.5 years; range, 19-79 years) were negative for the presence of gadolinium. Those samples were from patients who had undergone GBCA-enhanced MRI examination more than a year before CSF extraction (0.1 and 0.2 ng/mL after 1 and 3 years, respectively). The concentrations in patients with chronic renal insufficiency (n = 3), cerebral toxoplasmosis (n = 1), and liver cirrhosis (n = 1) were higher than the mean concentrations. Conclusion Gadoterate meglumine can be detected in human CSF after intravenous administration. © RSNA, 2018.

Giant onsite electronic entropy enhances the performance of ceria for water splitting.

PubMed

Naghavi, S Shahab; Emery, Antoine A; Hansen, Heine A; Zhou, Fei; Ozolins, Vidvuds; Wolverton, Chris

2017-08-18

Previous studies have shown that a large solid-state entropy of reduction increases the thermodynamic efficiency of metal oxides, such as ceria, for two-step thermochemical water splitting cycles. In this context, the configurational entropy arising from oxygen off-stoichiometry in the oxide, has been the focus of most previous work. Here we report a different source of entropy, the onsite electronic configurational entropy, arising from coupling between orbital and spin angular momenta in lanthanide f orbitals. We find that onsite electronic configurational entropy is sizable in all lanthanides, and reaches a maximum value of ≈4.7 k B per oxygen vacancy for Ce 4+ /Ce 3+ reduction. This unique and large positive entropy source in ceria explains its excellent performance for high-temperature catalytic redox reactions such as water splitting. Our calculations also show that terbium dioxide has a high electronic entropy and thus could also be a potential candidate for solar thermochemical reactions.Solid-state entropy of reduction increases the thermodynamic efficiency of ceria for two-step thermochemical water splitting. Here, the authors report a large and different source of entropy, the onsite electronic configurational entropy arising from coupling between orbital and spin angular momenta in f orbitals.

The Role of Dextran Coatings on the Cytotoxicity Properties of Ceria Nanoparticles Toward Bone Cancer Cells

NASA Astrophysics Data System (ADS)

Yazici, Hilal; Alpaslan, Ece; Webster, Thomas J.

2015-04-01

Cerium oxide nanoparticles have demonstrated great potential as antioxidant and radioprotective agents for nanomedicine applications especially for cancer therapy. The surface chemistry of nanoparticles is an important property that has a significant effect on their performance in biological applications including cancer diagnosis, cancer treatment, and bacterial infection. Recently, various nanosized cerium oxide particles with different types of polymer coatings have been developed to improve aqueous solubility and allow for surface functionalization for distinct applications. In this study, the role of ceria nanoparticles coated with dextran on the cytotoxicity properties of bone cancer cells was shown. Specifically, 0.1 M and 0.01 M dextran-coated, <5-nm ceria nanoparticles, were synthesized. The cytotoxicity of 0.1 M and 0.01 M dextran-coated ceria nanoparticles was evaluated against osteosarcoma cells. A change in cell viability was observed when treating osteosarcoma cells with 0.1 M dextran-coated ceria nanoparticles in the 250 -1000 μg/mL concentration range. In contrast, minimal toxicity to bone cancer cells was observed for the 0.01 M dextran coating after 3 days compared with the 0.1 M dextran coating. These results indicated that surface dextran functionalization had a positive impact on the cytotoxicity of cerium oxide nanoparticles against osteosarcoma cells.

Solution-processed gadolinium doped indium-oxide thin-film transistors with oxide passivation

NASA Astrophysics Data System (ADS)

Lee, Seung-Hun; Kim, Taehun; Lee, Jihun; Avis, Christophe; Jang, Jin

2017-03-01

We studied the effect of Gd doping on the structural properties of solution processed, crystalline In2O3 for thin-film transistor (TFT) application. With increasing Gd in In2O3 up to 20%, the material structure changes into amorphous phase, and the oxygen vacancy concentration decreases from 15.4 to 8.4%, and M-OH bonds from 33.5 to 23.7%. The field-effect mobility for the Gd doped In2O3 TFTs decreases and threshold voltage shifts to the positive voltage with increasing Gd concentration. In addition, the stability of the solution processed TFTs can also be improved by increasing Gd concentration. As a result, the optimum Gd concentration is found to be ˜5% in In2O3 and the 5% Gd doped In2O3 TFTs with the Y2O3 passivation layer exhibit the linear mobility of 9.74 cm2/V s, the threshold voltage of -0.27 V, the subthreshold swing of 79 mV/dec., and excellent bias stability.

Gadolinium accumulation in organs of Sprague-Dawley® rats after implantation of a biodegradable magnesium-gadolinium alloy.

PubMed

Myrissa, Anastasia; Braeuer, Simone; Martinelli, Elisabeth; Willumeit-Römer, Regine; Goessler, Walter; Weinberg, Annelie Martina

2017-01-15

Biodegradable magnesium implants are under investigation because of their promising properties as medical devices. For enhancing the mechanical properties and the degradation resistance, rare earth elements are often used as alloying elements. In this study Mg10Gd pins were implanted into Sprague-Dawley® rats. The pin volume loss and a possible accumulation of magnesium and gadolinium in the rats' organs and blood were investigated in a long-term study over 36weeks. The results showed that Mg10Gd is a fast disintegrating material. Already 12weeks after implantation the alloy is fragmented to smaller particles, which can be found within the intramedullary cavity and the cortical bones. They disturbed the bone remodeling until the end of the study. The results concerning the elements' distribution in the animals' bodies were even more striking, since an accumulation of gadolinium could be observed in the investigated organs over the whole time span. The most affected tissue was the spleen, with up to 3240μgGd/kg wet mass, followed by the lung, liver and kidney (up to 1040, 685 and 207μgGd/kg). In the brain, muscle and heart, the gadolinium concentrations were much smaller (less than 20μg/kg), but an accumulation could still be detected. Interestingly, blood serum samples showed no accumulation of magnesium and gadolinium. This is the first time that an accumulation of gadolinium in animal organs was observed after the application of a gadolinium-containing degradable magnesium implant. These findings demonstrate the importance of future investigations concerning the distribution of the constituents of new biodegradable materials in the body, to ensure the patients' safety. In the last years, biodegradable Mg alloys are under investigation due to their promising properties as orthopaedic devices used for bone fracture stabilization. Gadolinium as Rare Earth Element enhances the mechanical properties of Mg-Gd alloys but its toxicity in humans is still questionable

Novel multi-functional europium-doped gadolinium oxide nanoparticle aerosols facilitate the study of deposition in the developing rat lung

NASA Astrophysics Data System (ADS)

Das, Gautom K.; Anderson, Donald S.; Wallis, Chris D.; Carratt, Sarah A.; Kennedy, Ian M.; van Winkle, Laura S.

2016-06-01

Ambient ultrafine particulate matter (UPM), less than 100 nm in size, has been linked to the development and exacerbation of pulmonary diseases. Age differences in susceptibility to UPM may be due to a difference in delivered dose as well as age-dependent differences in lung biology and clearance. In this study, we developed and characterized aerosol exposures to novel metal oxide nanoparticles containing lanthanides to study particle deposition in the developing postnatal rat lung. Neonatal, juvenile and adult rats (1, 3 and 12 weeks old) were nose only exposed to 380 μg m-3 of ~30 nm europium doped gadolinium oxide nanoparticles (Gd2O3:Eu3+) for 1 h. The deposited dose in the nose, extrapulmonary airways and lungs was determined using inductively-coupled plasma mass spectroscopy. The dose of deposited particles was significantly greater in the juvenile rats at 2.22 ng per g body weight compared to 1.47 ng per g and 0.097 ng per g for the adult and neonate rats, respectively. Toxicity was investigated in bronchoalveolar lavage fluid (BALF) by quantifying recovered cell types, and measuring lactate dehydrogenase activity and total protein. The toxicity data suggests that the lanthanide particles were not acutely toxic or inflammatory with no increase in neutrophils or lactate dehydrogenase activity at any age. Juvenile and adult rats had the same mass of deposited NPs per gram of lung tissue, while neonatal rats had significantly less NPs deposited per gram of lung tissue. The current study demonstrates the utility of novel lanthanide-based nanoparticles to study inhaled particle deposition in vivo and has important implications for nanoparticles delivery to the developing lung either as therapies or as a portion of particulate matter air pollution.Ambient ultrafine particulate matter (UPM), less than 100 nm in size, has been linked to the development and exacerbation of pulmonary diseases. Age differences in susceptibility to UPM may be due to a difference in

Characterization of swift heavy ion irradiation damage in ceria

DOE PAGES

Yablinsky, Clarissa A.; Devanathan, Ram; Pakarinen, Janne; ...

2015-03-04

Swift heavy ion induced radiation damage is investigated for ceria (CeO 2), which serves as a UO 2 fuel surrogate. Microstructural changes resulting from an irradiation with 940 MeV gold ions of 42 keV/nm electronic energy loss are investigated by means of electron microscopy accompanied by electron energy loss spectroscopy showing that there exists a small density reduction in the ion track core. While chemical changes in the ion track are not precluded, evidence of them was not observed. Classical molecular dynamics simulations of thermal spikes in CeO 2 with an energy deposition of 12 and 36 keV/nm show damagemore » consisting of isolated point defects at 12 keV/nm, and defect clusters at 36 keV/nm, with no amorphization at either energy. Furthermore, inferences are drawn from modeling about density changes in the ion track and the formation of interstitial loops that shed light on features observed by electron microscopy of swift heavy ion irradiated ceria.« less

Antenna Effect on the Organic Spacer-Modified Eu-Doped Layered Gadolinium Hydroxide for the Detection of Vanadate Ions over a Wide pH Range.

PubMed

Jeong, Heejin; Lee, Byung-Il; Byeon, Song-Ho

2016-05-04

The excitation of the adsorbed vanadate group led to the red emission arising from the efficient energy transfer to Eu-doped layered gadolinium hydroxide (LGdH:Eu). This light-harvesting antenna effect allowed LGdH:Eu to detect selectively a vanadate in aqueous solution at different pHs. Because vanadate exists in various forms by extensive oligomerization and protonation reactions in aqueous solution depending on pH, it is important to detect a vanadate regardless of its form over a wide pH range. In particular, spacer molecules with long alkyl chains greatly facilitated access of a vanadate antenna into the interlayer surface of LGdH:Eu. The concomitant increase in adsorption capacity of LGdH:Eu achieved a strong antenna effect of vanadate on the red emission from Eu(3+). When a suspension containing LGdH:Eu nanosheets (1.0 g/L) was used, the vanadate concentration down to 1 × 10(-5) M could even be visually monitored, and the detection limit based on the (5)D0 → (7)F2 emission intensity could reach 4.5 × 10(-8) M.

Nephrogenic Systemic Fibrosis Manifesting a Decade After Exposure to Gadolinium.

PubMed

Larson, Krista N; Gagnon, Amy L; Darling, Melissa D; Patterson, James W; Cropley, Thomas G

2015-10-01

Nephrogenic systemic fibrosis (NSF) is a fibrosing skin disorder that develops in patients with kidney failure and has been linked to exposure to gadolinium-containing contrast agents. The time between exposure to gadolinium and the initial presentation of NSF is typically weeks to months but has been documented to be as long as 3½ years. We report a case of NSF developing 10 years after exposure to gadolinium. A long-term hemodialysis patient was exposed to gadolinium several times between 1998 and 2004 during magnetic resonance angiography of his abdominal vessels and arteriovenous fistula. In 2014, he was seen at our clinic with new dermal papules and plaques. Biopsy of affected skin showed thickening of collagen, CD34+ spindle cells, and increased mucin in the dermis, supporting the diagnosis of NSF. The clinical history and histopathological features of this case support the diagnosis of NSF 10 years after exposure to gadolinium. Although the use of gadolinium contrast agents in patients with kidney failure has markedly decreased, patients with exposure to gadolinium years to decades previously may manifest the disease.

Temperature and Pressure Sensors Based on Spin-Allowed Broadband Luminescence of Doped Orthorhombic Perovskite Structures

NASA Technical Reports Server (NTRS)

Eldridge, Jeffrey I. (Inventor); Chambers, Matthew D. (Inventor)

2014-01-01

Systems and methods that are capable of measuring pressure or temperature based on luminescence are discussed herein. These systems and methods are based on spin-allowed broadband luminescence of sensors with orthorhombic perovskite structures of rare earth aluminates doped with chromium or similar transition metals, such as chromium-doped gadolinium aluminate. Luminescence from these sensors can be measured to determine at least one of temperature or pressure, based on either the intense luminescence of these sensors, even at high temperatures, or low temperature techniques discussed herein.

Charge transfer and formation of reduced Ce3+ upon adsorption of metal atoms at the ceria (110) surface.

PubMed

Nolan, Michael

2012-04-07

The modification of cerium dioxide with nanoscale metal clusters is intensely researched for catalysis applications, with gold, silver, and copper having been particularly well studied. The interaction of the metal cluster with ceria is driven principally by a localised interaction between a small number of metal atoms (as small as one) and the surface and understanding the fundamentals of the interaction of metal atoms with ceria surfaces is therefore of great interest. Much attention has been focused on the interaction of metals with the (111) surface of ceria, since this is the most stable surface and can be grown as films, which are probed experimentally. However, nanostructures exposing other surfaces such as (110) show high activity for reactions including CO oxidation and require further study; these nanostructures could be modified by deposition of metal atoms or small clusters, but there is no information to date on the atomic level details of metal-ceria interactions involving the (110) surface. This paper presents the results of density functional theory (DFT) corrected for on-site Coulomb interactions (DFT+U) calculations of the adsorption of a number of different metal atoms at an extended ceria (110) surface; the metals are Au, Ag, Cu, Al, Ga, In, La, Ce, V, Cr, and Fe. Upon adsorption all metals are oxidised, transferring electron(s) to the surface, resulting in localised surface distortions. The precise details depend on the identity of the metal atom. Au, Ag, Cu each transfer one electron to the surface, reducing one Ce ion to Ce(3+), while of the trivalent metals, Al and La are fully oxidised, but Ga and In are only partially oxidised. Ce and the transition metals are also partially oxidised, with the number of reduced Ce ions possible in this surface no more than three per adsorbed metal atom. The predicted oxidation states of the adsorbed metal atoms should be testable in experiments on ceria nanostructures modified with metal atoms.

Performance evaluation of Mn and Fe doped SrCo0.9Nb0.1O3-δ cathode for IT-SOFC application

NASA Astrophysics Data System (ADS)

Bele, Lokesh; Lenka, R. K.; Patro, P. K.; Muhmood, L.; Mahata, T.; Sinha, P. K.

2018-02-01

Cathode materials of Mn and Fe doped SrCo0.9Nb0.1O3-δ, are synthesized by solid state route for intermediate temperature fuel cell applications. Phase pure material is obtained after calcining the precursors at 1100 °C. Phase compatibility is observed between this novel cathode material with gadolinia doped ceria (GDC) electrolyte material as reflected in the diffraction pattern. The state of art YSZ electrolyte is not compatible with this cathode material. Average thermal expansion coefficient of the material varies between 17 to 22 X 10-6 K-1 on doping, from room temperature to 800 °C. Increase in thermal expansion coefficient is observed with Mn and Fe doping associated with the loss of oxygen from the crystal. The electrical conductivity of the cathode material decreases with Fe and Mn doping. Mn doped samples show lowest conductivity. From the symmetric cell measurement lower area specific resistance (0.16 Ω-cm2) is obtained for un-doped samples, at 850 °C. From the initial results it can be inferred that Mn/Fe doping improves neither the thermal expansion co-efficient nor the electrochemical activity.

Gadolinium photoionization process

DOEpatents

Paisner, J.A.; Comaskey, B.J.; Haynam, C.A.; Eggert, J.H.

1993-04-13

A method is provided for selective photoionization of the odd-numbered atomic mass gadolinium isotopes 155 and 157. The selective photoionization is accomplished by circular or linear parallel polarized laser beam energy effecting a three-step photoionization pathway.

Gadolinium photoionization process

DOEpatents

Paisner, Jeffrey A.; Comaskey, Brian J.; Haynam, Christopher A.; Eggert, Jon H.

1993-01-01

A method is provided for selective photoionization of the odd-numbered atomic mass gadolinium isotopes 155 and 157. The selective photoionization is accomplished by circular or linear parallel polarized laser beam energy effecting a three-step photoionization pathway.

Synthesis and characterization of rare-earth-doped calcium tungstate nanocrystals

NASA Astrophysics Data System (ADS)

Suneeta, P.; Rajesh, Ch.; Ramana, M. V.

2018-02-01

In this paper, we report synthesis and characterization of rare-earth-ion-doped calcium tungstate (CaWO4) nanocrystals (NCs). Rare-earth ions, such as gadolinium (Gd), neodymium (Nd), praseodymium (Pr), samarium (Sm) and holmium (Ho), were successfully doped in the CaWO4 NCs by changing the synthesis conditions. The adopted synthesis route was found to be fast and eco-friendly. Structural characterizations, such as X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and compositional analysis, were performed using energy dispersive analysis of X-rays (EDAX) on as-synthesized NCs. The results indicate the size of the NCs ranging between 47 to 68nm and incorporation of rare-earth ions in CaWO4 NCs.

Performance of colloidal silica and ceria based slurries on CMP of Si-face 6H-SiC substrates

NASA Astrophysics Data System (ADS)

Chen, Guomei; Ni, Zifeng; Xu, Laijun; Li, Qingzhong; Zhao, Yongwu

2015-12-01

Colloidal silica and ceria based slurries, both using KMnO4 as an oxidizer, for chemical mechanical polishing (CMP) of Si-face (0 0 0 1) 6H-SiC substrate, were investigated to obtain higher material removal rate (MRR) and ultra-smooth surface. The results indicate that there was a significant difference in the CMP performance of 6H-SiC between silica and ceria based slurries. For the ceria based slurries, a higher MRR was obtained, especially in strong acid KMnO4 environment, and the maximum MRR (1089 nm/h) and a smoother surface with an average roughness Ra of 0.11 nm was achieved using slurries containing 2 wt% colloidal ceria, 0.05 M KMnO4 at pH 2. In contrast, due to the attraction between negative charged silica particles and positive charged SiC surface below pH 5, the maximum MRR of silica based slurry was only 185 nm/h with surface roughness Ra of 0.254 nm using slurries containing 6 wt% colloidal silica, 0.05 M KMnO4 at pH 6. The polishing mechanism was discussed based on the zeta potential measurements of the abrasives and the X-ray photoelectron spectroscopy (XPS) analysis of the polished SiC surfaces.

Water–gas shift reaction over gold nanoparticles dispersed on nanostructured CeO x–TiO 2(110) surfaces: Effects of high ceria coverage

DOE PAGES

Grinter, D. C.; Park, J. B.; Agnoli, S.; ...

2016-08-01

We used scanning tunnelling microscopy to study the morphology of an overlayer of ceria in contact with a TiO 2(110) substrate. Two types of domains were observed after ceria deposition. An ordered ceria film covered half of the surface and high-resolution imaging suggested a near-c(6 × 2) relationship to the underlying TiO 2(110)-(1 × 1). For the other half of the surface, it comprised CeO x nanoparticles and reconstructed TiOx supported on TiO 2(110)-(1 × 1). Exposure to a small amount of gold resulted in the formation of isolated gold atoms and small clusters on the ordered ceria film andmore » TiO 2(110)-(1 × 1) areas, which exhibited significant sintering at 500 K and showed strong interaction between the sintered gold clusters and the domain boundaries of the ceria film. The Au/CeO x/TiO 2(110) model system proved to be a good catalyst for the water–gas shift (WGS) exhibiting much higher turnover frequencies (TOFs) than Cu(111) and Pt(111) benchmarks, or the individual Au/TiO 2(110) and Au/CeO 2(111) systems. Finally, for Au/CeO x/TiO 2(110) catalysts, there was a decrease in catalytic activity with increasing ceria coverage that correlates with a reduction in the concentration of Ce 3 + formed during WGS reaction conditions.« less

Water–gas shift reaction over gold nanoparticles dispersed on nanostructured CeO x–TiO 2(110) surfaces: Effects of high ceria coverage

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

Grinter, D. C.; Park, J. B.; Agnoli, S.

We used scanning tunnelling microscopy to study the morphology of an overlayer of ceria in contact with a TiO 2(110) substrate. Two types of domains were observed after ceria deposition. An ordered ceria film covered half of the surface and high-resolution imaging suggested a near-c(6 × 2) relationship to the underlying TiO 2(110)-(1 × 1). For the other half of the surface, it comprised CeO x nanoparticles and reconstructed TiOx supported on TiO 2(110)-(1 × 1). Exposure to a small amount of gold resulted in the formation of isolated gold atoms and small clusters on the ordered ceria film andmore » TiO 2(110)-(1 × 1) areas, which exhibited significant sintering at 500 K and showed strong interaction between the sintered gold clusters and the domain boundaries of the ceria film. The Au/CeO x/TiO 2(110) model system proved to be a good catalyst for the water–gas shift (WGS) exhibiting much higher turnover frequencies (TOFs) than Cu(111) and Pt(111) benchmarks, or the individual Au/TiO 2(110) and Au/CeO 2(111) systems. Finally, for Au/CeO x/TiO 2(110) catalysts, there was a decrease in catalytic activity with increasing ceria coverage that correlates with a reduction in the concentration of Ce 3 + formed during WGS reaction conditions.« less

Catalytic properties of new anode materials for solid oxide fuel cells operated under methane at intermediary temperature

NASA Astrophysics Data System (ADS)

Sauvet, A.-L.; Fouletier, J.

The recent trend in solid oxide fuel cell concerns the use of natural gas as fuel. Steam reforming of methane is a well-established process for producing hydrogen directly at the anode side. In order to develop new anode materials, the catalytic activities of several oxides for the steam reforming of methane were characterized by gas chromatography. We studied the catalytic activity as a function of steam/carbon ratios r. The methane and the steam content were varied between 5 and 30% and between 1.5 and 3.5%, respectively, corresponding to r-values between 0.07 and 0.7. Catalyst (ruthenium and vanadium)-doped lanthanum chromites substituted with strontium, gadolinium-doped ceria (Ce 0.9Gd 0.1O 2) referred as to CeGdO 2, praseodymium oxide, molybdenum oxide and copper oxide were tested. The working temperature was fixed at 850°C, except for 5% ruthenium-doped La 1- xSr xCrO 3 where the temperature was varied between 700 and 850°C. Two types of behavior were observed as a function of the activity of the catalyst. The higher steam reforming efficiency was observed with 5% of ruthenium above 750°C.

Dehydrogenation of methanol to formaldehyde catalyzed by pristine and defective ceria surfaces.

PubMed

Beste, Ariana; Overbury, Steven H

2016-04-21

We have explored the dehydrogenation of methoxy on pristine and defective (111), (100), and (110) ceria surfaces with density functional methods. Methanol conversion is used as a probe reaction to understand structure sensitivity of the oxide catalysis. Differences in reaction selectivity have been observed experimentally as a function of crystallographically exposed faces and degree of reduction. We find that the barrier for carbon-hydrogen cleavage in methoxy is similar for the pristine and defective (111), (100), and (110) surfaces. However, there are large differences in the stability of the surface intermediates on the different surfaces. The variations in experimentally observed product selectivities are a consequence of the interplay between barrier controlled bond cleavage and desorption processes. Subtle differences in activation energies for carbon-hydrogen cleavage on the different crystallographic faces of ceria could not be correlated with structural or electronic descriptors.

Gadolinium-Induced Fibrosis.

PubMed

Todd, Derrick J; Kay, Jonathan

2016-01-01

Gadolinium-based contrast agents (GBCAs), once believed to be safe for patients with renal disease, have been strongly associated with nephrogenic systemic fibrosis (NSF), a severe systemic fibrosing disorder that predominantly afflicts individuals with advanced renal dysfunction. We provide a historical perspective on the appearance and disappearance of NSF, including its initial recognition as a discrete clinical entity, its association with GBCA exposure, and the data supporting a causative relationship between GBCA exposure and NSF. On the basis of this body of evidence, we propose that the name gadolinium-induced fibrosis (GIF) more accurately reflects the totality of knowledge regarding this disease. Use of high-risk GBCAs, such as formulated gadodiamide, should be avoided in patients with renal disease. Restriction of GBCA use in this population has almost completely eradicated new cases of this debilitating condition. Emerging antifibrotic therapies may be useful for patients who suffer from GIF.

Segregation and Migration of the Oxygen Vacancies in the 3 (111) Tilt Grain Boundaries of Ceria

DOE PAGES

Yuan, Fenglin; Liu, Bin; Zhang, Yanwen; ...

2016-03-01

In nanocrystalline materials, defect-grain boundary (GB) interaction plays a key role in determining the structure stability, as well as size-dependent ionic, electronic, magnetic and chemical properties. In this study, we systematically investigated using density functional theory segregation and migration of oxygen vacancies at the Σ3 [110] / (111) grain boundary of ceria. Three oxygen layers near the GB are predicted to be segregation sites for oxygen vacancies. Moreover, the presence of oxygen vacancies stabilizes this tilt GB at a low Fermi level and/or oxygen poor conditions. An atomic strain model was proposed to rationalize layer dependency of the relaxation energymore » for +2 charged oxygen vacancy. The structural origin of large relaxation energies at layers 1 and 2 was determined to be free-volume space that induces ion relaxation towards the GB. Our results not only pave the way for improving the oxygen transport near GBs of ceria, but also provide important insights into engineering the GB structure for better ionic, magnetic and chemical properties of nanocrystalline ceria.« less

Visible-light driven nitrogen-doped petal-morphological ceria nanosheets for water splitting

NASA Astrophysics Data System (ADS)

Qian, Junchao; Zhang, Wenya; Wang, Yaping; Chen, Zhigang; Chen, Feng; Liu, Chengbao; Lu, Xiaowang; Li, Ping; Wang, Kaiyuan; Chen, Ailian

2018-06-01

Water splitting is a promising sustainable technology for solar-to-chemical energy conversion. Herein, we successfully fabricated nitrogen-doped ultrathin CeO2 nanosheets by using field poppy petals as templates, which exhibit an efficiently catalytic activity for water splitting. Abundant oxygen vacancies and substitutional N atoms were experimentally observed in the film due to its unique biomorphic texture. In view of high efficiency and long durability of the as-prepared photocatalyst, this biotemplate method may provide an alternative technique for using biomolecules to assemble 2D nanomaterials.

Gadolinium Chelate Safety in Pregnancy: Barely Detectable Gadolinium Levels in the Juvenile Nonhuman Primate after in Utero Exposure.

PubMed

Prola-Netto, Joao; Woods, Mark; Roberts, Victoria H J; Sullivan, Elinor L; Miller, Christina Ann; Frias, Antonio E; Oh, Karen Y

2018-01-01

Purpose To determine whether gadolinium remains in juvenile nonhuman primate tissue after maternal exposure to intravenous gadoteridol during pregnancy. Materials and Methods Gravid rhesus macaques and their offspring (n = 10) were maintained, as approved by the institutional animal care and utilization committee. They were prospectively studied as part of a pre-existing ongoing research protocol to evaluate the effects of maternal malnutrition on placental and fetal development. On gestational days 85 and 135, they underwent placental magnetic resonance imaging after intravenous gadoteridol administration. Amniocentesis was performed on day 135 prior to administration of the second dose of gadoteridol. After delivery, the offspring were followed for 7 months. Tissue samples from eight different organs and from blood were harvested from each juvenile macaque. Gadolinium levels were measured by using inductively coupled plasma mass spectrometry. Results Gadolinium concentration in the amniotic fluid was 0.028 × 10 -5 %ID/g (percentage injected dose per gram of tissue) 50 days after administration of one gadoteridol dose. Gadolinium was most consistently detected in the femur (mean, 2.5 × 10 -5 %ID/g; range, [0.81-4.1] × 10 -5 %ID/g) and liver (mean, 0.15 × 10 -5 %ID/g; range, [0-0.26] × 10 -5 %ID/g). Levels were undetectable in the remaining sampled tissues, with the exception of one juvenile skin sample (0.07 × 10 -5 %ID/g), one juvenile spleen sample (0.039 × 10 -5 %ID/g), and one juvenile brain (0.095 × 10 -5 %ID/g) and kidney (0.13 × 10 -5 %ID/g) sample. Conclusion The presence of gadoteridol in the amniotic fluid after maternal injection enables confirmation that it crosses the placenta. Extremely low levels of gadolinium are found in juvenile macaque tissues after in utero exposure to two doses of gadoteridol, indicating that a very small amount of gadolinium persists after delivery. © RSNA, 2017.

Greener iodination of arenes using sulphated ceria-zirconia catalysts in polyethylene glycol

EPA Science Inventory

An environmentally benign method for the selective monoiodination of diverse aromatic compounds has been developed using reusable sulphated ceria-zirconia under mild conditions. The protocol provides moderate to good yields of aryl iodides in PEG-200 as a greener solvent. The cat...

Dehydrogenation of methanol to formaldehyde catalyzed by pristine and defective ceria surfaces

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

Beste, Ariana; Overbury, Steven H.

We have explored the dehydrogenation of methoxy on pristine and defective (111), (100), and (110) ceria surfaces with density functional methods. Methanol conversion is used as a probe reaction to understand structure sensitivity of the oxide catalysis. Differences in reaction selectivity have been observed experimentally as a function of crystallographically exposed faces and degree of reduction. We find that the barrier for carbon-hydrogen cleavage in methoxy is similar for the pristine and defective (111), (100), and (110) surfaces. However, there are large differences in the stability of the surface intermediates on the different surfaces. The variations in experimentally observed productmore » selectivities are a consequence of the interplay between barrier controlled bond cleavage and desorption processes. Ultimately, subtle differences in activation energies for carbon-hydrogen cleavage on the different crystallographic faces of ceria could not be correlated with structural or electronic descriptors.« less

Dehydrogenation of methanol to formaldehyde catalyzed by pristine and defective ceria surfaces

DOE PAGES

Beste, Ariana; Overbury, Steven H.

2016-03-09

We have explored the dehydrogenation of methoxy on pristine and defective (111), (100), and (110) ceria surfaces with density functional methods. Methanol conversion is used as a probe reaction to understand structure sensitivity of the oxide catalysis. Differences in reaction selectivity have been observed experimentally as a function of crystallographically exposed faces and degree of reduction. We find that the barrier for carbon-hydrogen cleavage in methoxy is similar for the pristine and defective (111), (100), and (110) surfaces. However, there are large differences in the stability of the surface intermediates on the different surfaces. The variations in experimentally observed productmore » selectivities are a consequence of the interplay between barrier controlled bond cleavage and desorption processes. Ultimately, subtle differences in activation energies for carbon-hydrogen cleavage on the different crystallographic faces of ceria could not be correlated with structural or electronic descriptors.« less

Deactivation of Ceria Supported Palladium through C–C Scission during Transfer Hydrogenation of Phenol with Alcohols

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

Nelson, Nicholas C.; Manzano, J. Sebastián; Slowing, Igor I.

The stability of palladium supported on ceria (Pd/CeO 2) was studied during liquid flow transfer hydrogenation using primary and secondary alcohols as hydrogen donors. For primary alcohols, the ceria support was reduced to cerium hydroxy carbonate within 14 h and was a contributing factor toward catalyst deactivation. For secondary alcohols, cerium hydroxy carbonate was not observed during the same time period and the catalyst was stable upon prolonged reaction. Regeneration through oxidation/reduction does not restore initial activity likely due to irreversible catalyst restructuring. Lastly, a deactivation mechanism involving C–C scission of acyl and carboxylate intermediates is proposed.

Deactivation of Ceria Supported Palladium through C–C Scission during Transfer Hydrogenation of Phenol with Alcohols

DOE PAGES

Nelson, Nicholas C.; Manzano, J. Sebastián; Slowing, Igor I.

2016-11-21

The stability of palladium supported on ceria (Pd/CeO 2) was studied during liquid flow transfer hydrogenation using primary and secondary alcohols as hydrogen donors. For primary alcohols, the ceria support was reduced to cerium hydroxy carbonate within 14 h and was a contributing factor toward catalyst deactivation. For secondary alcohols, cerium hydroxy carbonate was not observed during the same time period and the catalyst was stable upon prolonged reaction. Regeneration through oxidation/reduction does not restore initial activity likely due to irreversible catalyst restructuring. Lastly, a deactivation mechanism involving C–C scission of acyl and carboxylate intermediates is proposed.

Gadolinium-based contrast agent toxicity: a review of known and proposed mechanisms.

PubMed

Rogosnitzky, Moshe; Branch, Stacy

2016-06-01

Gadolinium chelates are widely used as contrast media for magnetic resonance imaging. The approved gadolinium-based contrast agents (GBCAs) have historically been considered safe and well tolerated when used at recommended dosing levels. However, for nearly a decade, an association between GBCA administration and the development of nephrogenic systemic fibrosis (NSF) has been recognized in patients with severe renal impairment. This has led to modifications in clinical practices aimed at reducing the potential and incidence of NSF development. Newer reports have emerged regarding the accumulation of gadolinium in various tissues of patients who do not have renal impairment, including bone, brain, and kidneys. Despite the observations of gadolinium accumulation in tissues regardless of renal function, very limited clinical data regarding the potential for and mechanisms of toxicity is available. This significant gap in knowledge warrants retrospective cohort study efforts, as well as prospective studies that involve gadolinium ion (Gd(3+)) testing in patients exposed to GBCA. This review examines the potential biochemical and molecular basis of gadolinium toxicity, possible clinical significance of gadolinium tissue retention and accumulation, and methods that can limit gadolinium body burden.

Formation of N3(-) during interaction of NO with reduced ceria.

PubMed

Mihaylov, Mihail Y; Ivanova, Elena Z; Aleksandrov, Hristiyan A; St Petkov, Petko; Vayssilov, Georgi N; Hadjiivanov, Konstantin I

2015-04-04

We show that the first stages of interaction between NO and reduced ceria comprise the formation of azides, N3(-), with simultaneous oxidation of Ce(3+) to Ce(4+). This finding imposes revision on some current views of catalytic NO conversion and may contribute to design of new deNOx materials and processes.

Room temperature ferromagnetic gadolinium silicide nanoparticles

DOEpatents

Hadimani, Magundappa Ravi L.; Gupta, Shalabh; Harstad, Shane; Pecharsky, Vitalij; Jiles, David C.

2018-03-06

A particle usable as T₁ and T₂ contrast agents is provided. The particle is a gadolinium silicide (Gd₅Si₄) particle that is ferromagnetic at temperatures up to 290 K and is less than 2 .mu.m in diameter. An MRI contrast agent that includes a plurality of gadolinium silicide (Gd.sub.5Si.sub.4) particles that are less than 1 .mu.m in diameter is also provided. A method for creating gadolinium silicide (Gd₅Si₄) particles is also provided. The method includes the steps of providing a Gd₅Si₄ bulk alloy; grinding the Gd₅Si₄ bulk alloy into a powder; and milling the Gd₅Si₄ bulk alloy powder for a time of approximately 20 minutes or less.

Ceria-Based Anodes for Next Generation Solid Oxide Fuel Cells

NASA Astrophysics Data System (ADS)

Mirfakhraei, Behzad

Mixed ionic and electronic conducting materials (MIECs) have been suggested to represent the next generation of solid oxide fuel cell (SOFC) anodes, primarily due to their significantly enhanced active surface area and their tolerance to fuel components. In this thesis, the main focus has been on determining and tuning the physicochemical and electrochemical properties of ceria-based MIECs in the versatile perovskite or fluorite crystal structures. In one direction, BaZr0.1Ce0.7Y0.1 M0.1O3-delta (M = Fe, Ni, Co and Yb) (BZCY-M) perovskites were synthesized using solid-state or wet citric acid combustion methods and the effect of various transition metal dopants on the sintering behavior, crystal structure, chemical stability under CO2 and H 2S, and electrical conductivity, was investigated. BZCY-Ni, synthesized using the wet combustion method, was the best performing anode, giving a polarization resistance (RP) of 0.4 O.cm2 at 800 °C. Scanning electron microscopy and X-ray diffraction analysis showed that this was due to the exsolution of catalytic Ni nanoparticles onto the oxide surface. Evolving from this promising result, the effect of Mo-doped CeO 2 (nCMO) or Ni nanoparticle infiltration into a porous Gd-doped CeO 2 (GDC) anode (in the fluorite structure) was studied. While 3 wt. % Ni infiltration lowered RP by up to 90 %, giving 0.09 O.cm2 at 800 °C and exhibiting a ca. 5 times higher tolerance towards 10 ppm H2, nCMO infiltration enhanced the H2 stability by ca. 3 times, but had no influence on RP. In parallel work, a first-time study of the Ce3+ and Ce 4+ redox process (pseudocapacitance) within GDC anode materials was carried out using cyclic voltammetry (CV) in wet H2 at high temperatures. It was concluded that, at 500-600 °C, the Ce3+/Ce 4+ reaction is diffusion controlled, probably due to O2- transport limitations in the outer 5-10 layers of the GDC particles, giving a very high capacitance of ca. 70 F/g. Increasing the temperature ultimately

Increased viability of fibroblasts when pretreated with ceria nanoparticles during serum deprivation.

PubMed

Genier, Francielli S; Bizanek, Maximilian; Webster, Thomas J; Roy, Amit K

2018-01-01

Conditions of cellular stress are often the cause of cell death or dysfunction. Sustained cell stress can lead to several health complications, such as extensive inflammatory responses, tumor growth, and necrosis. To prevent disease and protect human tissue during these conditions and to avoid medication side effects, nanomaterials with unique characteristics have been applied to biological systems. This paper introduces the pretreatment in human dermal fibroblasts with cerium oxide nanoparticles during nutritional stress. For this purpose, human dermal fibroblast cells received cell culture media with concentrations of 250 µg/mL and 500 µg/mL of nano-cerium oxide before being exposed to 24, 48, and 72 hours of serum starvation. Contrast images demonstrated higher cell confluence and cell integrity in cells pretreated with ceria nanoparticles compared to untreated cells. It was confirmed by MTS assay after 72 hours of serum starvation that higher cell viability was achieved with ceria nanoparticles. The results demonstrate the potential of cerium oxide nanoparticles as protective agents during cellular starvation.

Giant onsite electronic entropy enhances the performance of ceria for water splitting

DOE PAGES

Naghavi, S. Shahab; Emery, Antoine A.; Hansen, Heine A.; ...

2017-08-18

Previous studies have shown that a large solid-state entropy of reduction increases the thermodynamic efficiency of metal oxides, such as ceria, for two-step thermochemical water splitting cycles. In this context, the configurational entropy arising from oxygen off-stoichiometry in the oxide, has been the focus of most previous work. Here we report a different source of entropy, the onsite electronic configurational entropy, arising from coupling between orbital and spin angular momenta in lanthanide f orbitals. We find that onsite electronic configurational entropy is sizable in all lanthanides, and reaches a maximum value of ≈4.7 k B per oxygen vacancy for Cemore » 4+/Ce 3+ reduction. This unique and large positive entropy source in ceria explains its excellent performance for high-temperature catalytic redox reactions such as water splitting. Our calculations also show that terbium dioxide has a high electronic entropy and thus could also be a potential candidate for solar thermochemical reactions.« less

Ceria-thoria pellet manufacturing in preparation for plutonia-thoria LWR fuel production

NASA Astrophysics Data System (ADS)

Drera, Saleem S.; Björk, Klara Insulander; Sobieska, Matylda

2016-10-01

Thorium dioxide (thoria) has potential to assist in niche roles as fuel for light water reactors (LWRs). One such application for thoria is its use as the fertile component to burn plutonium in a mixed oxide fuel (MOX). Thor Energy and an international consortium are currently irradiating plutonia-thoria (Th-MOX) fuel in an effort to produce data for its licensing basis. During fuel-manufacturing research and development (R&D), surrogate materials were utilized to highlight procedures and build experience. Cerium dioxide (ceria) provides a good surrogate platform to replicate the chemical nature of plutonium dioxide. The project's fuel manufacturing R&D focused on powder metallurgical techniques to ensure manufacturability with the current commercial MOX fuel production infrastructure. The following paper highlights basics of the ceria-thoria fuel production including powder milling, pellet pressing and pellet sintering. Green pellets and sintered pellets were manufactured with average densities of 67.0% and 95.5% that of theoretical density respectively.

Near-Road Modeling and Measurement of Particles Generated by Nanoparticle Diesel Fuel Additive Use

EPA Science Inventory

Cerium oxide (ceria) nanoparticles (n-Ce) are used as a fuel-borne catalyst in diesel engines to reduce particulate emissions, yet the environmental and human health impacts of the ceria-doped diesel exhaust aerosols are not well understood. To bridge the gap between emission mea...

Synthesis and characterization of Gd-doped magnetite nanoparticles

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

Zhang, Honghu; Iowa State Univ., Ames, IA; Malik, Vikash

There has been rising interest in the synthesis of magnetite nanoparticles due to their importance in biomedical and technological applications. Tunable magnetic properties of magnetite nanoparticles to meet specific requirements will greatly expand the spectrum of applications. Tremendous efforts have been devoted to studying and controlling the size, shape and magnetic properties of magnetite nanoparticles. We investigate gadolinium (Gd) doping to influence the growth process as well as magnetic properties of magnetite nanocrystals via a simple co-precipitation method under mild conditions in aqueous media. Gd doping was found to affect the growth process leading to synthesis of controllable particle sizesmore » under the conditions tested (0–10 at% Gd 3+). Typically, undoped and 5 at% Gd-doped magnetite nanoparticles were found to have crystal sizes of about 18 and 44 nm, respectively, supported by X-ray diffraction and transmission electron microscopy. These results showed that Gd-doped nanoparticles retained the magnetite crystal structure, with Gd 3+ randomly incorporated in the crystal lattice, probably in the octahedral sites. The composition of 5 at% Gd-doped magnetite was Fe (3-x)Gd xO 4 (x=0.085±0.002), as determined by inductively coupled plasma mass spectrometry. 5 at% Gd-doped nanoparticles exhibited ferrimagnetic properties with small coercivity (~65 Oe) and slightly decreased magnetization at 260 K in contrast to the undoped, superparamagnetic magnetite nanoparticles. Templation by the bacterial biomineralization protein Mms6 did not appear to affect the growth of the Gd-doped magnetite particles synthesized by this method.« less

Synthesis and characterization of Gd-doped magnetite nanoparticles

DOE PAGES

Zhang, Honghu; Iowa State Univ., Ames, IA; Malik, Vikash; ...

2016-10-04

There has been rising interest in the synthesis of magnetite nanoparticles due to their importance in biomedical and technological applications. Tunable magnetic properties of magnetite nanoparticles to meet specific requirements will greatly expand the spectrum of applications. Tremendous efforts have been devoted to studying and controlling the size, shape and magnetic properties of magnetite nanoparticles. We investigate gadolinium (Gd) doping to influence the growth process as well as magnetic properties of magnetite nanocrystals via a simple co-precipitation method under mild conditions in aqueous media. Gd doping was found to affect the growth process leading to synthesis of controllable particle sizesmore » under the conditions tested (0–10 at% Gd 3+). Typically, undoped and 5 at% Gd-doped magnetite nanoparticles were found to have crystal sizes of about 18 and 44 nm, respectively, supported by X-ray diffraction and transmission electron microscopy. These results showed that Gd-doped nanoparticles retained the magnetite crystal structure, with Gd 3+ randomly incorporated in the crystal lattice, probably in the octahedral sites. The composition of 5 at% Gd-doped magnetite was Fe (3-x)Gd xO 4 (x=0.085±0.002), as determined by inductively coupled plasma mass spectrometry. 5 at% Gd-doped nanoparticles exhibited ferrimagnetic properties with small coercivity (~65 Oe) and slightly decreased magnetization at 260 K in contrast to the undoped, superparamagnetic magnetite nanoparticles. Templation by the bacterial biomineralization protein Mms6 did not appear to affect the growth of the Gd-doped magnetite particles synthesized by this method.« less

Novel multi-functional europium-doped gadolinium oxide nanoparticle aerosols facilitate the study of deposition in the developing rat lung.

PubMed

Das, Gautom K; Anderson, Donald S; Wallis, Chris D; Carratt, Sarah A; Kennedy, Ian M; Van Winkle, Laura S

2016-06-02

Ambient ultrafine particulate matter (UPM), less than 100 nm in size, has been linked to the development and exacerbation of pulmonary diseases. Age differences in susceptibility to UPM may be due to a difference in delivered dose as well as age-dependent differences in lung biology and clearance. In this study, we developed and characterized aerosol exposures to novel metal oxide nanoparticles containing lanthanides to study particle deposition in the developing postnatal rat lung. Neonatal, juvenile and adult rats (1, 3 and 12 weeks old) were nose only exposed to 380 μg m(-3) of ∼30 nm europium doped gadolinium oxide nanoparticles (Gd2O3:Eu(3+)) for 1 h. The deposited dose in the nose, extrapulmonary airways and lungs was determined using inductively-coupled plasma mass spectroscopy. The dose of deposited particles was significantly greater in the juvenile rats at 2.22 ng per g body weight compared to 1.47 ng per g and 0.097 ng per g for the adult and neonate rats, respectively. Toxicity was investigated in bronchoalveolar lavage fluid (BALF) by quantifying recovered cell types, and measuring lactate dehydrogenase activity and total protein. The toxicity data suggests that the lanthanide particles were not acutely toxic or inflammatory with no increase in neutrophils or lactate dehydrogenase activity at any age. Juvenile and adult rats had the same mass of deposited NPs per gram of lung tissue, while neonatal rats had significantly less NPs deposited per gram of lung tissue. The current study demonstrates the utility of novel lanthanide-based nanoparticles to study inhaled particle deposition in vivo and has important implications for nanoparticles delivery to the developing lung either as therapies or as a portion of particulate matter air pollution.

Magnetic resonance characteristics and susceptibility weighted imaging of the brain in gadolinium encephalopathy.

PubMed

Samardzic, Dejan; Thamburaj, Krishnamoorthy

2015-01-01

To report the brain imaging features on magnetic resonance imaging (MRI) in inadvertent intrathecal gadolinium administration. A 67-year-old female with gadolinium encephalopathy from inadvertent high dose intrathecal gadolinium administration during an epidural steroid injection was studied with multisequence 3T MRI. T1-weighted imaging shows pseudo-T2 appearance with diffusion of gadolinium into the brain parenchyma, olivary bodies, and membranous labyrinth. Nulling of cerebrospinal fluid (CSF) signal is absent on fluid attenuation recovery (FLAIR). Susceptibility-weighted imaging (SWI) demonstrates features similar to subarachnoid hemorrhage. CT may demonstrate a pseudo-cerebral edema pattern given the high attenuation characteristics of gadolinium. Intrathecal gadolinium demonstrates characteristic imaging features on MRI of the brain and may mimic subarachnoid hemorrhage on susceptibility-weighted imaging. Identifying high dose gadolinium within the CSF spaces on MRI is essential to avoid diagnostic and therapeutic errors. Copyright © 2013 by the American Society of Neuroimaging.

Ceria based inverse opals for thermochemical fuel production: Quantification and prediction of high temperature behavior

NASA Astrophysics Data System (ADS)

Casillas, Danielle Courtney

Solar energy has the potential to supply more than enough energy to meet humanity's energy demands. Here, a method for thermochemical solar energy storage through fuel production is presented. A porous non-stoichiometric oxide, ceria, undergoes partial thermal reduction and oxidation with concentrated solar energy as a heat source, and water as an oxidant. The resulting yields for hydrogen fuel and oxygen are produced in two discrete steps, while the starting material maintains its original phase. Ordered porosity has been shown superior to random porosity for thermochemical fuel production applications, but stability limits for these structures are currently undefined. Ceria-based inverse opals are currently being investigated to assess the architectural influence on thermochemical hydrogen production. Low tortuosity and continuous interconnected pore network allow for facile gas transport and improved reaction kinetics. Ceria-based ordered materials have recently been shown to increase maximum hydrogen production over non-ordered porous ceria. Thermal stability of ordered porosity was quantified using quantitative image analysis. Fourier analysis was applied to SEM images of the material. The algorithm results in an order parameter gamma that describes the degree of long range order maintained by these structures, where gamma>4 signifies ordered porosity. According to this metric, a minimum zirconium content of 20 atomic percent (at%) is necessary for these architectures to survive aggressive annealing up to 1000°C. Zirconium substituted ceria (ZSC) with Zr loadings in excess of 20at% developed undesired tetragonal phases. Through gamma, we were able to find a balance between the benefit of zirconium additions on structural stability and its negative impact on phase. This work demonstrates the stability of seemingly delicate architectures, and the operational limit for ceria based inverse opals to be 1000°C for 1microm pore size. Inverse opals having sub

Water-gas-shift over metal-free nanocrystalline ceria: An experimental and theoretical study

DOE PAGES

Guild, Curtis J.; Vovchok, Dimitriy; Kriz, David A.; ...

2017-01-23

A tandem experimental and theoretical investigation of a mesoporous ceria catalyst reveals the properties of the metal oxide are conducive for activity typically ascribed to metals, suggesting reduced Ce 3+ and oxygen vacancies are responsible for the inherent bi-functionality of CO oxidation and dissociation of water required for facilitating the production of H 2. The degree of reduction of the ceria, specifically the (1 0 0) face, is found to significantly influence the binding of reagents, suggesting reduced surfaces harbor the necessary reactive sites. The metal-free catalysis of the reaction is significant for catalyst design considerations, and the suite ofmore » in situ analyses provides a comprehensive study of the dynamic nature of the high surface area catalyst system. Finally, this study postulates feasible improvements in catalytic activity may redirect the purpose of the water-gas shift reaction from CO purification to primary hydrogen production.« less

Water-gas-shift over metal-free nanocrystalline ceria: An experimental and theoretical study

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

Guild, Curtis J.; Vovchok, Dimitriy; Kriz, David A.

A tandem experimental and theoretical investigation of a mesoporous ceria catalyst reveals the properties of the metal oxide are conducive for activity typically ascribed to metals, suggesting reduced Ce 3+ and oxygen vacancies are responsible for the inherent bi-functionality of CO oxidation and dissociation of water required for facilitating the production of H 2. The degree of reduction of the ceria, specifically the (1 0 0) face, is found to significantly influence the binding of reagents, suggesting reduced surfaces harbor the necessary reactive sites. The metal-free catalysis of the reaction is significant for catalyst design considerations, and the suite ofmore » in situ analyses provides a comprehensive study of the dynamic nature of the high surface area catalyst system. Finally, this study postulates feasible improvements in catalytic activity may redirect the purpose of the water-gas shift reaction from CO purification to primary hydrogen production.« less

Dynamic formation of single-atom catalytic active sites on ceria-supported gold nanoparticles

PubMed Central

Wang, Yang-Gang; Mei, Donghai; Glezakou, Vassiliki-Alexandra; Li, Jun; Rousseau, Roger

2015-01-01

Catalysis by gold supported on reducible oxides has been extensively studied, yet issues such as the nature of the catalytic site and the role of the reducible support remain fiercely debated topics. Here we present ab initio molecular dynamics simulations of an unprecedented dynamic single-atom catalytic mechanism for the oxidation of carbon monoxide by ceria-supported gold clusters. The reported dynamic single-atom catalytic mechanism results from the ability of the gold cation to strongly couple with the redox properties of the ceria in a synergistic manner, thereby lowering the energy of redox reactions. The gold cation can break away from the gold nanoparticle to catalyse carbon monoxide oxidation, adjacent to the metal/oxide interface and subsequently reintegrate back into the nanoparticle after the reaction is completed. Our study highlights the importance of the dynamic creation of active sites under reaction conditions and their essential role in catalysis. PMID:25735407

Density of Gadolinium Nitrate Solutions for the High Flux Isotope Reactor

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

Taylor, Paul Allen; Lee, Denise L

2009-05-01

In late 1992, the High Flux Isotope Reactor (HFIR) was planning to switch the solution contained in the poison injection tank from cadmium nitrate to gadolinium nitrate. The poison injection system is an emergency system used to shut down the reactor by adding a neutron poison to the cooling water. This system must be able to supply a minimum of 69 pounds of gadolinium to the reactor coolant system in order to guarantee that the reactor would become subcritical. A graph of the density of gadolinium nitrate solutions over a concentration range of 5 to 30 wt% and a temperaturemore » range of 15 to 40{sup o}C was prepared. Routine density measurements of the solution in the poison injection tank are made by HFIR personnel, and an adaptation of the original graph is used to determine the gadolinium nitrate concentration. In late 2008, HFIR personnel decided that the heat tracing that was present on the piping for the poison injection system could be removed without any danger of freezing the solution; however, the gadolinium nitrate solution might get as cold as 5{sup o}C. This was outside the range of the current density-concentration correlation, so the range needed to be expanded. This report supplies a new density-concentration correlation that covers the extended temperature range. The correlation is given in new units, which greatly simplifies the calculation that is required to determine the pounds of gadolinium in the tank solution. The procedure for calculating the amount of gadolinium in the HFIR poison injection system is as follows: (1) Calculate the usable volume in the system; (2) Measure the density of the solution; (3) Calculate the gadolinium concentration using the following equation: Gd(lb/ft{sup 3}) = measured density (g/mL) x 34.681 - 34.785; (4) Calculate the amount of gadolinium in the system using the following equation: Amount of Gd(lb) = Gd concentration (lb/ft{sup 3}) x usable volume (ft{sup 3}). The equation in step 3 is exact for a

Portable Oxygen Generation for Medical Applications.

DTIC Science & Technology

1997-07-01

stabilized zirconia; these include scandia- stabilized zirconia, lanthanum gallate , ceria, and bismuth oxide. Scandia-stabilized zirconia [1] exhibits...uncertainty of using doped ceria is its high thermal expansion coefficient (ceria -13-14 ppm/°C, YSZ -10.5 ppm/°C). Lanthanum gallate (LaGa03) [2-4...the conductivity of lanthanum gallate approximately 2-3 times that of YSZ in the 600- 1000°C temperature range. The enhanced conductivity in lanthanum

Structural and magnetic phase transitions in gadolinium under high pressures and low temperatures

DOE PAGES

Samudrala, Gopi K.; Tsoi, Georgiy M.; Weir, Samuel T.; ...

2014-11-07

High pressure structural transition studies have been carried out on rare earth metal gadolinium in a diamond anvil cell at room temperature to 169 GPa. Gadolinium has been compressed to 38% of its initial volume at this pressure. With increasing pressure, a crystal structure sequence of hcp → Smtype→ dhcp → fcc → dfcc → monoclinic has been observed in our studies on gadolinium. The measured equation of state of gadolinium is presented to 169 GPa at ambient temperature. Magnetic ordering temperature of gadolinium has been studied using designer diamond anvils to a pressure of 25 GP and a temperaturemore » of 10 K. The magnetic ordering temperature has been determined from the four-point electrical resistivity measurements carried out on gadolinium. Furthermore, our experiments show that the magnetic transition temperature decreases with increasing pressure to 19 GPa and then increases when gadolinium is subjected to higher pressures.« less

Structural and magnetic phase transitions in gadolinium under high pressures and low temperatures

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

Samudrala, Gopi K.; Tsoi, Georgiy M.; Weir, Samuel T.

High pressure structural transition studies have been carried out on rare earth metal gadolinium in a diamond anvil cell at room temperature to 169 GPa. Gadolinium has been compressed to 38% of its initial volume at this pressure. With increasing pressure, a crystal structure sequence of hcp → Smtype→ dhcp → fcc → dfcc → monoclinic has been observed in our studies on gadolinium. The measured equation of state of gadolinium is presented to 169 GPa at ambient temperature. Magnetic ordering temperature of gadolinium has been studied using designer diamond anvils to a pressure of 25 GP and a temperaturemore » of 10 K. The magnetic ordering temperature has been determined from the four-point electrical resistivity measurements carried out on gadolinium. Furthermore, our experiments show that the magnetic transition temperature decreases with increasing pressure to 19 GPa and then increases when gadolinium is subjected to higher pressures.« less

Structural and magnetic phase transitions in gadolinium under high pressures and low temperatures

NASA Astrophysics Data System (ADS)

Samudrala, Gopi K.; Tsoi, Georgiy M.; Weir, Samuel T.; Vohra, Yogesh K.

2014-10-01

High pressure structural transition studies have been carried out on rare earth metal gadolinium in a diamond anvil cell at room temperature to 169 GPa. Gadolinium has been compressed to 38% of its initial volume at this pressure. With increasing pressure, a crystal structure sequence of hcp → Sm-type → dhcp → fcc → dfcc → monoclinic has been observed in our studies on gadolinium. The measured equation of state of gadolinium is presented to 169 GPa at ambient temperature. Magnetic ordering temperature of gadolinium has been studied using designer diamond anvils to a pressure of 25 GPa and a temperature of 10 K. The magnetic ordering temperature has been determined from the four-point electrical resistivity measurements carried out on gadolinium. Our experiments show that the magnetic transition temperature decreases with increasing pressure to 19 GPa and then increases when gadolinium is subjected to higher pressures.

Synthesis and evaluation of gadolinium complexes based on PAMAM as MRI contrast agents.

PubMed

Yan, Guo-Ping; Hu, Bin; Liu, Mai-Li; Li, Li-Yun

2005-03-01

Diethylenetriaminepentaacetic acid (DTPA) and pyridoxamine (PM) were incorporated into the amine groups on the surface of ammonia-core poly(amidoamine) dendrimers (PAMAM, Generation 2.0-5.0) to obtain dendritic ligands. These dendritic ligands were reacted with gadolinium chloride to yield the corresponding dendritic gadolinium (Gd) complexes. The dendritic ligands and their gadolinium complexes were characterized by(1)HNMR, IR, UV and elemental analysis. Relaxivity studies showed that the dendritic gadolinium complexes possessed higher relaxation effectiveness compared with the clinically used Gd-DTPA. After administration of the dendritic gadolinium complexes (0.09 mmol kg(-1) ) to rats, magnetic resonance imaging of the liver indicated that the dendritic gadolinium complexes containing pyridoxamine groups enhanced the contrast of the MR images of the liver, provided prolonged intravascular duration and produced highly contrasted visualization of blood vessels.

Water Adsorption and Dissociation on Ceria-Supported Single-Atom Catalysts: A First-Principles DFT+U Investigation.

PubMed

Han, Zhong-Kang; Gao, Yi

2016-02-01

Single-atom catalysts have attracted wide attention owing to their extremely high atom efficiency and activities. In this paper, we applied density functional theory with the inclusion of the on-site Coulomb interaction (DFT+U) to investigate water adsorption and dissociation on clean CeO 2 (111) surfaces and single transition metal atoms (STMAs) adsorbed on the CeO 2 (111) surface. It is found that the most stable water configuration is molecular adsorption on the clean CeO 2 (111) surface and dissociative adsorption on STMA/CeO 2 (111) surfaces, respectively. In addition, our results indicate that the more the electrons that transfer from STMA to the ceria substrate, the stronger the binding energies between the STMA and ceria surfaces. A linear relationship is identified between the water dissociation barriers and the d band centers of STMA, known as the generalized Brønsted-Evans-Polanyi principle. By combining the oxygen spillovers, single-atom dispersion stabilities, and water dissociation barriers, Zn, Cr, and V are identified as potential candidates for the future design of ceria-supported single-atom catalysts for reactions in which the dissociation of water plays an important role, such as the water-gas shift reaction. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Shape-Dependent Activity of Ceria for Hydrogen Electro-Oxidation in Reduced-Temperature Solid Oxide Fuel Cells.

PubMed

Tong, Xiaofeng; Luo, Ting; Meng, Xie; Wu, Hao; Li, Junliang; Liu, Xuejiao; Ji, Xiaona; Wang, Jianqiang; Chen, Chusheng; Zhan, Zhongliang

2015-11-04

Single crystalline ceria nanooctahedra, nanocubes, and nanorods are hydrothermally synthesized, colloidally impregnated into the porous La0.9Sr0.1Ga0.8Mg0.2O3-δ (LSGM) scaffolds, and electrochemically evaluated as the anode catalysts for reduced temperature solid oxide fuel cells (SOFCs). Well-defined surface terminations are confirmed by the high-resolution transmission electron microscopy--(111) for nanooctahedra, (100) for nanocubes, and both (110) and (100) for nanorods. Temperature-programmed reduction in H2 shows the highest reducibility for nanorods, followed sequentially by nanocubes and nanooctahedra. Measurements of the anode polarization resistances and the fuel cell power densities reveal different orders of activity of ceria nanocrystals at high and low temperatures for hydrogen electro-oxidation, i.e., nanorods > nanocubes > nanooctahedra at T ≤ 450 °C and nanooctahedra > nanorods > nanocubes at T ≥ 500 °C. Such shape-dependent activities of these ceria nanocrystals have been correlated to their difference in the local structure distortions and thus in the reducibility. These findings will open up a new strategy for design of advanced catalysts for reduced-temperature SOFCs by elaborately engineering the shape of nanocrystals and thus selectively exposing the crystal facets. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Identification and characterization of gadolinium(III) complexes in biological tissue extracts.

PubMed

Kahakachchi, Chethaka L; Moore, Dennis A

2010-07-01

The gadolinium species present in a rat kidney following intravenous administration of a gadolinium-based magnetic resonance contrast agent (Optimark™, Gadoversetamide injection) to a rat was examined in the present study. The major gadolinium species in the supernatant of the rat kidney tissue extracts was determined by reversed-phase liquid chromatography with online inductively coupled plasma optical emission spectrometry (HPLC-ICP-OES). The identity of the compound was established by liquid chromatography electrospray ionization mass spectrometry (LC-ESI-MS) detection. The principal gadolinium(III) complex in a rat kidney tissue extract was identified as Gd-DTPA-BMEA 24 Hrs and 7 days after a single intravenous injection of Optimark™ (gadoversetamide; Gd-DTPA-BMEA) at a dose of 5 mmol Gd/kg body weight. The study demonstrated for the first time the feasibility of the use of two complementary techniques, HPLC-ICP-OES and HPLC-ESI-MS to study the in vivo behavior of gadolinium-based magnetic resonance contrast media.

Combined Ceria Reduction and Methane Reforming in a Solar-Driven Particle-Transport Reactor.

PubMed

Welte, Michael; Warren, Kent; Scheffe, Jonathan R; Steinfeld, Aldo

2017-09-20

We report on the experimental performance of a solar aerosol reactor for carrying out the combined thermochemical reduction of CeO 2 and reforming of CH 4 using concentrated radiation as the source of process heat. The 2 kW th solar reactor prototype utilizes a cavity receiver enclosing a vertical Al 2 O 3 tube which contains a downward gravity-driven particle flow of ceria particles, either co-current or counter-current to a CH 4 flow. Experimentation under a peak radiative flux of 2264 suns yielded methane conversions up to 89% at 1300 °C for residence times under 1 s. The maximum extent of ceria reduction, given by the nonstoichiometry δ (CeO 2-δ ), was 0.25. The solar-to-fuel energy conversion efficiency reached 12%. The syngas produced had a H 2 :CO molar ratio of 2, and its calorific value was solar-upgraded by 24% over that of the CH 4 reformed.

Combined Ceria Reduction and Methane Reforming in a Solar-Driven Particle-Transport Reactor

PubMed Central

2017-01-01

We report on the experimental performance of a solar aerosol reactor for carrying out the combined thermochemical reduction of CeO2 and reforming of CH4 using concentrated radiation as the source of process heat. The 2 kWth solar reactor prototype utilizes a cavity receiver enclosing a vertical Al2O3 tube which contains a downward gravity-driven particle flow of ceria particles, either co-current or counter-current to a CH4 flow. Experimentation under a peak radiative flux of 2264 suns yielded methane conversions up to 89% at 1300 °C for residence times under 1 s. The maximum extent of ceria reduction, given by the nonstoichiometry δ (CeO2−δ), was 0.25. The solar-to-fuel energy conversion efficiency reached 12%. The syngas produced had a H2:CO molar ratio of 2, and its calorific value was solar-upgraded by 24% over that of the CH4 reformed. PMID:28966440

Gadolinium-enhanced computed tomographic angiography: current status.

PubMed

Rosioreanu, Alex; Alberico, Ronald A; Litwin, Alan; Hon, Man; Grossman, Zachary D; Katz, Douglas S

2005-01-01

This article reviews the research to date, as well as our clinical experience from two institutions, on gadolinium-enhanced computed tomographic angiography (gCTA) for imaging the body. gCTA may be an appropriate examination for the small percentage of patients who would benefit from noninvasive vascular imaging, but who have contraindications to both iodinated contrast and magnetic resonance imaging. gCTA is more expensive than CTA with iodinated contrast, due to the dose of gadolinium administered, and gCTA has limitations compared with CTA with iodinated contrast, in that parenchymal organs are not optimally enhanced at doses of 0.5 mmol/kg or lower. However, in our experience, gCTA has been a very useful problem-solving examination in carefully selected patients. With the advent of 16-64 detector CT, in combination with bolus tracking, we believe that the overall dose of gadolinium needed for diagnostic CTA examinations, while relatively high, can be safely administered.

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

Gadolinium-based magnetic resonance imaging contrast agents in interventional radiology.

PubMed

Atar, Eli

2004-07-01

Gadolinium-based agents are widely used in magnetic resonance imaging as contrast agents. These agents are radio-opaque enough for diagnostic imaging of the vascular tree by using digitally subtracted images as well as for imaging of the biliary system and the urinary tract. The recommended doses for gadolinium do not impair renal function or cause adverse reactions in patients with iodine sensitivity; thus patients with such conditions can safely undergo diagnostic angiography, either by MRI angiography or by catheterization using gadolinium as contrast agent, for diagnostic and therapeutic purposes.

ZnO:Gd nanocrystals for fluorescent applications

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

Divya, N. K., E-mail: divyank90@gmail.com; Pradyumnan, P. P.

2016-05-23

Gadolinium doped ZnO crystals within the solubility limit of gadolinium in ZnO matrix were prepared by solid state reaction technique. The method is relatively less expense and enables the production in large scale. The samples were characterised by X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS), scanning electron microscopy (SEM), UV/Vis diffuse reflectance spectroscopy and photoluminescence techniques. Fluorescent property studies of gadolinium doped ZnO at room temperature show enhanced visible light emission due to the defects and oxygen vacancies produced via doping. This work reports the impact of gadolinium doping in the structural, optical and luminescent properties of ZnO inmore » detail.« less

Ceria nanocubic-ultrasonication assisted dispersive liquid-liquid microextraction coupled with matrix assisted laser desorption/ionization mass spectrometry for pathogenic bacteria analysis.

PubMed

Abdelhamid, Hani Nasser; Bhaisare, Mukesh L; Wu, Hui-Fen

2014-03-01

A new ceria (CeO2) nanocubic modified surfactant is used as the basis of a novel nano-based microextraction technique for highly sensitive detection of pathogenic bacteria (Pseudomonas aeruginosa and Staphylococcus aureus). The technique uses ultrasound enhanced surfactant-assisted dispersive liquid-liquid microextraction (UESA-DLLME) with and without ceria (CeO2) followed by matrix assisted laser desorption/ionization mass spectrometry (MALDI-MS). In order to achieve high separation efficiency, we investigated the influential parameters, including extraction time of ultrasonication, type and volume of the extraction solvent and surfactant. Among various surfactants, the cationic surfactants can selectively offer better extraction efficiency on bacteria analysis than that of the anionic surfactants due to the negative charges of bacteria cell membranes. Extractions of the bacteria lysate from aqueous samples via UESA-DLLME-MALDI-MS were successfully achieved by using cetyltrimethyl ammonium bromide (CTAB, 10.0 µL, 1.0×10(-3) M) as surfactants in chlorobenzene (10.0 µL) and chloroform (10.0 µL) as the optimal extracting solvent for P. aeruginosa and S. aureus, respectively. Ceria nanocubic was synthesized, and functionalized with CTAB (CeO2@CTAB) and then characterized using transmission electron microscopy (TEM) and optical spectroscopy (UV and FTIR). CeO2@CTAB demonstrates high extraction efficiency, improve peaks ionization, and enhance resolution. The prime reasons for these improvements are due to the large surface area of nanoparticles, and its absorption that coincides with the wavelength of MALDI laser (337 nm, N2 laser). CeO2@CTAB-based microextraction offers lowest detectable concentrations tenfold lower than that of without nanoceria. The present approach has been successfully applied to detect pathogenic bacteria at low concentrations of 10(4)-10(5) cfu/mL (without ceria) and at 10(3)-10(4) cfu/mL (with ceria) from bacteria suspensions. Finally, the

Gd-doped BNNTs as T2-weighted MRI contrast agents

NASA Astrophysics Data System (ADS)

Ciofani, Gianni; Boni, Adriano; Calucci, Lucia; Forte, Claudia; Gozzi, Alessandro; Mazzolai, Barbara; Mattoli, Virgilio

2013-08-01

This work describes, for the first time, doping of boron nitride nanotubes (BNNTs) with gadolinium (Gd@BNNTs), a stable functionalization that permits non-invasive BNNT tracking via magnetic resonance imaging (MRI). We report the structure, Gd loading, and relaxometric properties in water suspension at 7 T of Gd@BNNTs, and show the behaviour of these nanostructures as promising T2-weighted contrast agents. Finally, we demonstrate their complete biocompatibility in vitro on human neuroblastoma cells, together with their ability to effectively label and affect contrast in MRI images at 7 T.

Growth Control in Colon Epithelial Cells: Gadolinium Enhances Calcium-Mediated Growth Regulation

PubMed Central

Attili, Durga; Jenkins, Brian; Aslam, Muhammad Nadeem; Dame, Michael K.

2013-01-01

Gadolinium, a member of the lanthanoid family of transition metals, interacts with calcium-binding sites on proteins and other biological molecules. The overall goal of the present investigation was to determine if gadolinium could enhance calcium-induced epithelial cell growth inhibition in the colon. Gadolinium at concentrations as low as 1–5 µM combined with calcium inhibits proliferation of human colonic epithelial cells more effectively than calcium alone. Gadolinium had no detectable effect on calcium-induced differentiation in the same cells based on change in cell morphology, induction of E-cadherin synthesis, and translocation of E-cadherin from the cytosol to the cell surface. When the colon epithelial cells were treated with gadolinium and then exposed to increased calcium concentrations, movement of extracellular calcium into the cell was suppressed. In contrast, gadolinium treatment had no effect on ionomycin-induced release of stored intracellular calcium into the cytoplasm. Whether these in vitro observations can be translated into an approach for reducing abnormal proliferation in the colonic mucosa (including polyp formation) is not known. These results do, however, provide an explanation for our recent findings that a multi-mineral supplement containing all of the naturally occurring lanthanoid metals including gadolinium are more effective than calcium alone in preventing colon polyp formation in mice on a high-fat diet. PMID:23008064

Growth control in colon epithelial cells: gadolinium enhances calcium-mediated growth regulation.

PubMed

Attili, Durga; Jenkins, Brian; Aslam, Muhammad Nadeem; Dame, Michael K; Varani, James

2012-12-01

Gadolinium, a member of the lanthanoid family of transition metals, interacts with calcium-binding sites on proteins and other biological molecules. The overall goal of the present investigation was to determine if gadolinium could enhance calcium-induced epithelial cell growth inhibition in the colon. Gadolinium at concentrations as low as 1-5 μM combined with calcium inhibits proliferation of human colonic epithelial cells more effectively than calcium alone. Gadolinium had no detectable effect on calcium-induced differentiation in the same cells based on change in cell morphology, induction of E-cadherin synthesis, and translocation of E-cadherin from the cytosol to the cell surface. When the colon epithelial cells were treated with gadolinium and then exposed to increased calcium concentrations, movement of extracellular calcium into the cell was suppressed. In contrast, gadolinium treatment had no effect on ionomycin-induced release of stored intracellular calcium into the cytoplasm. Whether these in vitro observations can be translated into an approach for reducing abnormal proliferation in the colonic mucosa (including polyp formation) is not known. These results do, however, provide an explanation for our recent findings that a multi-mineral supplement containing all of the naturally occurring lanthanoid metals including gadolinium are more effective than calcium alone in preventing colon polyp formation in mice on a high-fat diet.

Thermodynamic properties of gadolinium in Ga-Sn and Ga-Zn eutectic based alloys

NASA Astrophysics Data System (ADS)

Maltsev, Dmitry S.; Volkovich, Vladimir A.; Yamshchikov, Leonid F.; Chukin, Andrey V.

2016-09-01

Thermodynamic properties of gadolinium in Ga-Sn and Ga-Zn eutectic based alloys were studied. Temperature dependences of gadolinium activity in the studied alloys were determined at 573-1073 K employing the EMF method. Solubility of gadolinium in the Ga-Sn and Ga-Zn alloys was measured at 462-1073 K using IMCs sedimentation method. Activity coefficients as well as partial and excess thermodynamic functions of gadolinium in the studied alloys were calculated on the basis of the obtained experimental data.

The role of CO 2 as a soft oxidant for dehydrogenation of ethylbenzene to styrene over a high-surface-area ceria catalyst

DOE PAGES

Zhang, Li; Wu, Zili; Nelson, Nicholas; ...

2015-09-22

Catalytic performance and the nature of surface adsorbates were investigated for high-surface-area ceria during ethylbenzene oxidative dehydrogenation (ODH) reaction using CO2 as a soft oxidant. A template assisted method was used to synthesize the high-surface-area ceria. The interactions between ethylbenzene, styrene and CO2 on the surface of ceria and the role of CO2 for the ethylbenzene ODH reaction have been investigated in detail by using activity test, in situ Diffuse Reflectance Infrared and Raman spectroscopy. Not only did CO2 as an oxidant favor the higher yield of styrene, but it also inhibited the deposition of coke during the ethylbenzene ODHmore » reaction. Ethylbenzene ODH reaction over ceria followed a two-step pathway: Ethylbenzene is first dehydrogenated to styrene with H2 formed simultaneously, and then CO2 reacts with H2 via the reverse water gas shift. The styrene produced can easily polymerize to form polystyrene, a key intermediate for coke formation. In the absence of CO2, the polystyrene transforms into graphite-like coke at temperatures above 500 °C, which leads to catalyst deactivation. While in the presence of CO2, the coke deposition can be effectively removed via oxidation with CO2.« less

Ceria-containing uncoated and coated hydroxyapatite-based galantamine nanocomposites for formidable treatment of Alzheimer's disease in ovariectomized albino-rat model.

PubMed

Wahba, Sanaa M R; Darwish, Atef S; Kamal, Sara M

2016-08-01

This paper upraises delivery and therapeutic actions of galantamine drug (GAL) against Alzheimer's disease (AD) in rat brain through attaching GAL to ceria-containing hydroxyapatite (GAL@Ce-HAp) as well ceria-containing carboxymethyl chitosan-coated hydroxyapatite (GAL@Ce-HAp/CMC) nanocomposites. Physicochemical features of such nanocomposites were analyzed by XRD, FT-IR, Raman spectroscopy, UV-vis spectrophotometer, N2-BET, DLS, zeta-potential measurements, SEM, and HR-TEM. Limited interactions were observed in GAL@Ce-HAp with prevailed existence of dispersed negatively charged rod-like particles conjugated with ceria nanodots. On contrary, GAL@Ce-HAp/CMC was well-structured developing aggregates of uncharged tetragonal-shaped particles laden with accession of ceria quantum dots. Such nanocomposites were i.p. injected into ovariectomized AD albino-rats at galantamine dose of 2.5mg/kg/day for one month, then brain tissues were collected for biochemical and histological tests. GAL@Ce-HAp adopted as a promising candidate for AD curativeness, whereas oxidative stress markers were successfully upregulated, degenerated neurons in hippocampal and cerebral tissues were wholly recovered and Aβ-plaques were vanished. Also, optimizable in-vitro release for GAL and nanoceria were displayed from GAL@Ce-HAp, while delayed in-vitro release for those species were developed from GAL@Ce-HAp/CMC. This proof of concept work allow futuristic omnipotency of rod-like hydroxyapatite particles for selective delivery of GAL and nanoceria to AD affected brain areas. Copyright © 2016 Elsevier B.V. All rights reserved.

Gadolinium substitution induced defect restructuring in multiferroic BiFeO3: case study by positron annihilation spectroscopy

NASA Astrophysics Data System (ADS)

Mukherjee, A.; Banerjee, M.; Basu, S.; Nambissan, P. M. G.; Pal, M.

2013-12-01

Positron annihilation spectroscopy (PAS) comprising of the measurements of positron lifetime and coincidence Doppler broadening spectra has been carried out to understand and monitor the evolution of the vacancy-type defects arising from the ionic deficiencies at lattice points of the multiferroic perovskite bismuth ferrite (BiFeO3) doped with 1, 5 and 10 at% gadolinium (Gd3+) ions. Negatively charged defects in the form of Bi3+ monovacancies (V_{Bi}^{3-} ) were present in the undoped nanocrystallites, which strongly trapped positrons. During the successive doping by Gd3+ ions, the positron trapping efficiency decreased while the doped ions combined with the vacancies to form complexes, which became neutral. A fraction of the positrons got annihilated at the crystallite surfaces too, being evident from the very large positron lifetimes obtained and confirming the nano-size-specific characteristics of the samples. Further, the intercrystallite regions provided favourable sites for orthopositronium formation, although in minute concentrations. The dopant ion-complex formation was also depicted clearly by the defect characteristic S-W plot. Also, the large change of electrical resistivity with Gd concentration has been explained nicely by invoking the defect information from the PAS study. The study has demonstrated the usefulness of an excellent method of defect identification in such a novel material system, which is vital information for exploiting them for further technological applications.

Strain Engineering Defect Concentrations in Reduced Ceria for Improved Electro-Catalytic Performance

DTIC Science & Technology

2014-06-30

coupling, curvature relaxation, lanthanum strontium ferrite, ceria. oxygen surface exchange 16. SECURITY CLASSIFICATION OF: 17. LlMITATJON OF a. REPORT...Temperature Lanthanum Strontium Ferrite Oxygen Surface Exchange Coefficient Measurements by Curvature Relaxation. 225th Meeting of the Electrochemical...Manuscripts Received Paper TOTAL: Received Paper TOTAL: 06/30/2014 Received Paper 1.00 Qing Yang, Jason Nicholas. Porous Thick Film Lanthanum Strontium

Are gadolinium-based contrast media nephrotoxic? A renal biopsy study.

PubMed

Akgun, Hulya; Gonlusen, Gulfiliz; Cartwright, Joiner; Suki, Wadi N; Truong, Luan D

2006-09-01

Gadolinium-based contrast media were originally introduced as alternatives to iodinated media for magnetic resonance imaging. Although originally thought to be nonnephrotoxic, gadolinium-based contrast media have recently been reported to be associated with acute renal failure; the mechanism and the underlying renal injury are not completely understood. We report what is, to our knowledge, the first renal biopsy in this context. A 56-year-old patient underwent 2 consecutive vascular imaging procedures in conjunction with gadolinium-based contrast medium administration. A few days later, the patient developed acute renal failure. A renal biopsy showed acute tubular cell injury including patchy tubular cell necrosis, tubular cell degeneration, and marked proliferation of tubular cells, together with mild interstitial edema and interstitial inflammation, but without significant glomerular or vascular changes. During supportive therapy, renal function was partially regained. This case emphasizes the potential nephrotoxicity of gadolinium-based contrast media and suggests that the nephrotoxicity is related to potentially reversible acute tubular cell injury.

Co-Precipitation Synthesis of Gadolinium Aluminum Gallium Oxide (GAGG) via Different Precipitants

NASA Astrophysics Data System (ADS)

Sun, Yan; Yang, Shenghui; Zhang, Ye; Jiang, Jun; Jiang, Haochuan

2014-02-01

In order to obtain a uniform transparent ceramic scintillator, well-dispersed fine starting powders with high-purity, small grain size, spherical morphology and high sinter-ability are necessary. In this study, Ce3+ doped gadolinium aluminum gallium garnet Gd3Al3Ga2O12 (GAGG) powders were synthesized by the co-precipitation method. NH4OH, NH4HCO3 and the mixed solution of NH4OH and NH4HCO3 were used as precipitants, respectively. The precursor composition, phase formation process, microstructure, morphology, particle size distribution and luminescent properties of obtained GAGG powders were measured. The results show that powders prepared using the mixed precipitant exhibit the best microstructural morphology, good sinter-ability and highest luminescent intensity. Pure GAGG polycrystalline powders could be obtained at about 950°C for 1.5 h and the average size of the particles is about 50 nm. The photoluminescence spectrum shows a strong green-yellow emission near 540 nm.

Technical aspects of MRI signal change quantification after gadolinium-based contrast agents' administration.

PubMed

Ramalho, Joana; Ramalho, Miguel; AlObaidy, Mamdoh; Semelka, Richard C

2016-12-01

Over the last 2years several studies have been published regarding gadolinium deposition in brain structures in patients with normal renal function after repeated administrations of gadolinium-based contrast agents (GBCAs). Most of the publications are magnetic resonance imaging (MRI) based retrospective studies, where gadolinium deposition may be indirectly measured by evaluating changes in T1 signal intensity (SI) in brain tissue, particularly in the dentate nucleus (DN) and/or globus pallidi (GP). The direct correlation between T1 signal changes and gadolinium deposition was validated by human pathology studies. However, the variability of the MR equipment and parameters used across different publications, along with the inherent limitations of MRI to assess gadolinium in human tissues should be acknowledged when interpreting those studies. Nevertheless, MRI studies remain essential regarding gadolinium bio-distribution knowledge. The aim of this paper is to overview current knowledge of technical aspects of T1 signal intensity evaluation by MRI and describe confounding factors, with the intention to achieve higher accuracy and maximize reproducibility. Copyright © 2016 Elsevier Inc. All rights reserved.

Cell membrane penetration and mitochondrial targeting by platinum-decorated ceria nanoparticles

NASA Astrophysics Data System (ADS)

Torrano, Adriano A.; Herrmann, Rudolf; Strobel, Claudia; Rennhak, Markus; Engelke, Hanna; Reller, Armin; Hilger, Ingrid; Wixforth, Achim; Bräuchle, Christoph

2016-07-01

In this work we investigate the interaction between endothelial cells and nanoparticles emitted by catalytic converters. Although catalyst-derived particles are recognized as growing burden added to environmental pollution, very little is known about their health impact. We use platinum-decorated ceria nanoparticles as model compounds for the actual emitted particles and focus on their fast uptake and association with mitochondria, the cell's powerhouse. Using live-cell imaging and electron microscopy we clearly show that 46 nm platinum-decorated ceria nanoparticles can rapidly penetrate cell membranes and reach the cytosol. Moreover, if suitably targeted, these particles are able to selectively attach to mitochondria. These results are complemented by cytotoxicity assays, thus providing insights into the biological effects of these particles on cells. Interestingly, no permanent membrane disruption or any other significant adverse effects on cells were observed. The unusual uptake behavior observed for 46 nm nanoparticles was not observed for equivalent but larger 143 nm and 285 nm platinum-decorated particles. Our results demonstrate a remarkable particle size effect in which particles smaller than ~50-100 nm escape the usual endocytic pathway and translocate directly into the cytosol, while particles larger than ~150 nm are internalized by conventional endocytosis. Since the small particles are able to bypass endocytosis they could be explored as drug and gene delivery vehicles. Platinum-decorated nanoparticles are therefore highly interesting in the fields of nanotoxicology and nanomedicine.In this work we investigate the interaction between endothelial cells and nanoparticles emitted by catalytic converters. Although catalyst-derived particles are recognized as growing burden added to environmental pollution, very little is known about their health impact. We use platinum-decorated ceria nanoparticles as model compounds for the actual emitted particles and

Transient heat and mass transfer analysis in a porous ceria structure of a novel solar redox reactor

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

Chandran, RB; Bader, R; Lipinski, W

2015-06-01

Thermal transport processes are numerically analyzed for a porous ceria structure undergoing reduction in a novel redox reactor for solar thermochemical fuel production. The cylindrical reactor cavity is formed by an array of annular reactive elements comprising the porous ceria monolith integrated with gas inlet and outlet channels. Two configurations are considered, with the reactor cavity consisting of 10 and 20 reactive elements, respectively. Temperature dependent boundary heat fluxes are obtained on the irradiated cavity wall by solving for the surface radiative exchange using the net radiation method coupled to the heat and mass transfer model of the reactive element.more » Predicted oxygen production rates are in the range 40-60 mu mol s(-1) for the geometries considered. After an initial rise, the average temperature of the reactive element levels off at 1660 and 1680 K for the two geometries, respectively. For the chosen reduction reaction rate model, oxygen release continues after the temperature has leveled off which indicates that the oxygen release reaction is limited by chemical kinetics and/or mass transfer rather than by the heating rate. For a fixed total mass of ceria, the peak oxygen release rate is doubled for the cavity with 20 reactive elements due to lower local oxygen partial pressure. (C) 2015 Elsevier Masson SAS. All rights reserved.« less

Magnetically recyclable magnetite-ceria (Nanocat-Fe-Ce) nanocatalysts - applications in multicomponent reactions under benign conditions

EPA Science Inventory

A novel magnetite nanoparticle-supported ceria catalyst (Nanocat-Fe-Ce) has been successfully prepared by simple impregnation method and was well characterized by XRD, SIMS, FEG-SEM-EDS, and TEM. The exact nature of Nanocat-Fe-Ce was confirmed by X-ray photoelectron spectroscopy ...

Compensated gadolinium-loaded plastic scintillators for thermal neutron detection (and counting)

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

Dumazert, Jonathan; Coulon, Romain; Bertrand, Guillaume H. V.

2015-07-01

Plastic scintillator loading with gadolinium-rich organometallic complexes shows a high potential for the deployment of efficient and cost-effective neutron detectors. Due to the low-energy photon and electron signature of thermal neutron capture by gadolinium-155 and gadolinium-157, alternative treatment to Pulse Shape Discrimination has to be proposed in order to display a trustable count rate. This paper discloses the principle of a compensation method applied to a two-scintillator system: a detection scintillator interacts with photon radiation and is loaded with gadolinium organometallic compound to become a thermal neutron absorber, while a non-gadolinium loaded compensation scintillator solely interacts with the photon partmore » of the incident radiation. Posterior to the nonlinear smoothing of the counting signals, a hypothesis test determines whether the resulting count rate after photon response compensation falls into statistical fluctuations or provides a robust image of a neutron activity. A laboratory prototype is tested under both photon and neutron irradiations, allowing us to investigate the performance of the overall compensation system in terms of neutron detection, especially with regards to a commercial helium-3 counter. The study reveals satisfactory results in terms of sensitivity and orientates future investigation toward promising axes. (authors)« less

Surface characterization of acidic ceria-zirconia prepared by direct sulfation

NASA Astrophysics Data System (ADS)

Azambre, B.; Zenboury, L.; Weber, J. V.; Burg, P.

2010-05-01

Acidic ceria-zirconia (SCZ) solid acid catalysts with a nominal surface density of ca 2 SO 42-/nm 2 were prepared by a simple route consisting in soaking high specific surface area Ce xZr 1- xO 2 (with x = 0.21 and 0.69) mixed oxides solutions in 0.5 M sulphuric acid. Characterizations by TPD-MS, TP-DRIFTS and FT-Raman revealed that most of surface structures generated by sulfation are stable at least up to 700 °C under inert atmosphere and consist mainly as isolated sulfates located on defects or crystal planes and to a lesser extent as polysulfates. Investigations by pyridine adsorption/desorption have stated that: SCZ possess both strong Brønsted (B) and Lewis (L) acid sites, some of them being presumably superacidic; the B/L site ratio was found to be more dependent on the temperature and hydration degree than on the composition of the ceria-zirconia. By contrast, the reactivity of the parent Ce xZr 1- xO 2 materials towards pyridine is mostly driven by redox properties resulting in the formation of Py-oxide with the participation of Lewis acid sites of moderate strength ( cus Ce x+ and Zr x+ cations). Basicity studies by CO 2 adsorption/desorption reveal that SCZ surfaces are solely acidic whereas the number and strength of Lewis basic sites increases with the Ce content for the parent Ce xZr 1- xO 2 materials.

Nanometer-sized ceria-coated silica-iron oxide for the reagentless microextraction/preconcentration of heavy metals in environmental and biological samples followed by slurry introduction to ICP-OES.

PubMed

Dados, A; Paparizou, E; Eleftheriou, P; Papastephanou, C; Stalikas, C D

2014-04-01

A slurry suspension sampling technique is developed and optimized for the rapid microextraction of heavy metals and analysis using nanometer-sized ceria-coated silica-iron oxide particles and inductively coupled plasma optical emission spectrometry (ICP-OES). Magnetic-silica material is synthesized by a co-precipitation and sol-gel method followed by ceria coating through a precipitation. The large particles are removed using a sedimentation-fractionation procedure and a magnetic homogeneous colloidal suspension of ceria-modified iron oxide-silica is produced for microextraction. The nanometer-sized particles are separated from the sample solution magnetically and analyzed with ICP-OES using a slurry suspension sampling approach. The ceria-modified iron oxide-silica does not contain any organic matter and this probably justifies the absence of matrix effect on plasma atomization capacity, when increased concentrations of slurries are aspirated. The As, Be, Mo, Cr, Cu, Pb, Hg, Sb, Se and V can be preconcentrated by the proposed method at pH 6.0 while Mn, Cd, Co and Ni require a pH ≥ 8.0. Satisfactory values are obtained for the relative standard deviations (2-6%), recoveries (88-102%), enrichment factors (14-19) and regression correlation coefficients as well as detectability, at sub-μg L(-1) levels. The applicability of magnetic ceria for the microextraction of metal ions in combination with the slurry introduction technique using ICP is substantiated by the analysis of environmental water and urine samples. Copyright © 2013 Elsevier B.V. All rights reserved.

Influence of doping on thermal diffusivity of single crystals used in photonics: measurements based on thermal wave methods.

PubMed

Bodzenta, Jerzy; Kaźmierczak-Bałata, Anna; Wokulska, Krystyna B; Kucytowski, Jacek; Łukasiewicz, Tadeusz; Hofman, Władysław

2009-03-01

Three crystals used in solid-state lasers, namely, yttrium aluminum garnet (YAG), yttrium orthovanadate (YVO(4)), and gadolinium calcium oxoborate (GdCOB), were investigated to determine the influence of dopants on their thermal diffusivity. The thermal diffusivity was measured by thermal wave method with a signal detection based on mirage effect. The YAG crystals were doped with Yb or V, the YVO(4) with Nd or Ca and Tm, and the GdCOB crystals contained Nd or Yb. In all cases, the doping caused a decrease in thermal diffusivity. The analysis of complementary measurements of ultrasound velocity changes caused by dopants leads to the conclusion that impurities create phonon scattering centers. This additional scattering reduces the phonon mean free path and accordingly results in the decrease of the thermal diffusivity of the crystal. The influence of doping on lattice parameters was investigated, additionally.

Photosensitizer-Loaded Branched Polyethylenimine-PEGylated Ceria Nanoparticles for Imaging-Guided Synchronous Photochemotherapy.

PubMed

Yang, Zhang-You; Li, Hong; Zeng, Yi-Ping; Hao, Yu-Hui; Liu, Cong; Liu, Jing; Wang, Wei-Dong; Li, Rong

2015-11-04

A multifunctional theranostic platform based on photosensitizer (chlorin e6, Ce6)-loaded branched polyethylenimine-PEGylated ceria nanoparticles (PPCNPs-Ce6) was created for the development of effective cancer treatments involving the use of imaging-guided synchronous photochemotherapy. PPCNPs-Ce6 with high Ce6 photosensitizer loading (Ce6: cerium ∼40 wt %) significantly enhanced the delivery of Ce6 into cells and its accumulation in lysosomes, remarkably improving photodynamic therapeutic (PDT) efficacy levels compared to those in the administration of free Ce6 at ultralow drug doses (∼200 nM). Interestingly, PPCNPs-Ce6 efficiently induced HeLa cell death even at low concentrations (∼10 μM) without the use of laser irradiation and exhibit chemocytotoxicity. Inductively coupled plasma mass spectrometry (ICP-MS) and biology transmission electron microscopy (Bio-TEM) analyses demonstrated that ceria nanoparticles enter cells abundantly and accumulate in lysosomes or large vesicles. We then evaluated the effects of the different materials on lysosomal integrity and function, which revealed that PPCNPs-Ce6 catastrophically impaired lysosomal function compared to results with PPCNPs and Ce6. Studies of apoptosis revealed greater induction of apoptosis by PPCNPs-Ce6 treatment. This multifunctional nanocarrier also exhibited a high degree of solubility and stability in aqueous solutions, suggesting its applicability for extensive biomedical application.

[Rapid imaging in orbito-ocular pathology. Contribution of gadolinium].

PubMed

Pigeau, I; Legeais, J M; D'Hermies, F; Fayet, B; Leport, M; Abenhaim, A; Guinet, C; Levy, C; Renard, G; Vadrot, D

1990-01-01

To evaluate Gradient-Echo Imaging (GEI) in orbito-ocular pathology, 15 volunteers and 34 patients (40 lesions) were examined with GEA T1 and GEA T2 (0.5 T). Results were compared with SE T1 in all cases, with SE T2 in 20 cases and with other imaging modalities (CT). 30 patients were examined before and after injection of gadolinium. Final diagnosis was obtained by surgery or biopsy in 24 cases or by combined results of imaging and clinical findings in 16 cases. Compared with SE, GEA demonstrated a better visualisation of optic nerve, orbital muscles, choroidal-retinal layer, lens capsule and episclera and a better detection of small lesions. It is very helpful for characterisation of lesions containing hemorrhages or paramagnetic components (melanine, gadolinium) or of vascular nature (angioma). Gadolinium was useful for detection of small lesions or characterisation of a few lesions. Thus GEA seems to be an efficient method for the evaluation of orbito-ocular pathology.

Nickel Nanocatalyst Ex-Solution from Ceria-Nickel Oxide Solid Solution for Low Temperature CO Oxidation.

PubMed

Singhania, Amit; Gupta, Shipra Mital

2018-07-01

In this work, in situ growth of Ni nanocatalysts to attach onto the ceria (CeO2) surface through direct Ni ex-solution from the NiO-CeO2 solid solution in a reducing atmosphere at high temperatures with an aim to improve the catalytic activity, and stability for low temperature carbon monoxide (CO) oxidation reaction have been reported. The NiO-CeO2 solid solutions were prepared by solution combustion method, and the results of XRD and RAMAN showed that doping of Ni increases the oxygen vacancies due to charge compensation. Ni is clearly visible in XRD and TEM of Ni ex-solved sample (R-UCe5Ni10) after reduction of NiO-CeO2 (UCe5Ni10) sample by 5% H2/Ar reduction at 1000 °C. TEM analysis revealed a size of 9.2 nm of Ni nanoparticle that is ex-solved on the surface CeO2. This ex-solved sample showed very high catalytic activity (T50 ~ 110 °C), and stability (100 h) for CO oxidation reaction as compared to prepared solid solution samples. This is due to the highly active metallic nano-phase which is ex-solved on the surface of CeO2 and strongly adherent to the support. The apparent activation energy Ni ex-solved sample is found out to be 48.4 kJ mol-1. Thus, the above Ni ex-solved sample shows a practical applicability for the CO reaction.

Distribution and chemical forms of gadolinium in the brain: a review.

PubMed

Kanda, Tomonori; Nakai, Yudai; Hagiwara, Akifumi; Oba, Hiroshi; Toyoda, Keiko; Furui, Shigeru

2017-11-01

In the 3 years since residual gadolinium-based contrast agent (GBCA) in the brain was first reported, much has been learned about its accumulation, including the pathway of GBCA entry into the brain, the brain distribution of GBCA and its excretion. Here we review recent progress in understanding the routes of gadolinium deposition in brain structures.

ROS mediated malignancy cure performance of morphological, optical, and electrically tuned Sn doped CeO2 nanostructures

NASA Astrophysics Data System (ADS)

Abbas, Fazal; Iqbal, Javed; Maqbool, Qaisar; Jan, Tariq; Ullah, Muhammad Obaid; Nawaz, Bushra; Nazar, Mudassar; Naqvi, M. S. Hussain; Ahmad, Ishaq

2017-09-01

To grapple with cancer, implementation of differentially cytotoxic nanomedicines have gained prime attention of the researchers across the globe. Now, ceria (CeO2) at nanoscale has emerged as a cut out therapeutic agent for malignancy treatment. Keeping this in view, we have fabricated SnxCe1-xO2 nanostructures by facile, eco-friendly, and biocompatible hydrothermal method. Structural examinations via XRD and FT-IR spectroscopy have revealed single phase cubic-fluorite morphology while SEM analysis has depicted particle size ranging 30-50nm for pristine and doped nanostructures. UV-Vis spectroscopy investigation explored that Sn doping significantly tuned the band gap (eV) energies of SnxCe1-xO2 nanostructures which set up the base for tremendous cellular reactive oxygen species (ROS) generations involved in cancer cells' death. To observe cytotoxicity, synthesized nanostructures were found selectively more toxic to neuroblastoma cell lines as compared to HEK-293 healthy cells. This study anticipates that SnxCe1-xO2 nanostructures, in future, might be used as nanomedicine for safer cancer therapy.

Feasibility and accuracy of dual-layer spectral detector computed tomography for quantification of gadolinium: a phantom study.

PubMed

van Hamersvelt, Robbert W; Willemink, Martin J; de Jong, Pim A; Milles, Julien; Vlassenbroek, Alain; Schilham, Arnold M R; Leiner, Tim

2017-09-01

The aim of this study was to evaluate the feasibility and accuracy of dual-layer spectral detector CT (SDCT) for the quantification of clinically encountered gadolinium concentrations. The cardiac chamber of an anthropomorphic thoracic phantom was equipped with 14 tubular inserts containing different gadolinium concentrations, ranging from 0 to 26.3 mg/mL (0.0, 0.1, 0.2, 0.4, 0.5, 1.0, 2.0, 3.0, 4.0, 5.1, 10.6, 15.7, 20.7 and 26.3 mg/mL). Images were acquired using a novel 64-detector row SDCT system at 120 and 140 kVp. Acquisitions were repeated five times to assess reproducibility. Regions of interest (ROIs) were drawn on three slices per insert. A spectral plot was extracted for every ROI and mean attenuation profiles were fitted to known attenuation profiles of water and pure gadolinium using in-house-developed software to calculate gadolinium concentrations. At both 120 and 140 kVp, excellent correlations between scan repetitions and true and measured gadolinium concentrations were found (R > 0.99, P < 0.001; ICCs > 0.99, CI 0.99-1.00). Relative mean measurement errors stayed below 10% down to 2.0 mg/mL true gadolinium concentration at 120 kVp and below 5% down to 1.0 mg/mL true gadolinium concentration at 140 kVp. SDCT allows for accurate quantification of gadolinium at both 120 and 140 kVp. Lowest measurement errors were found for 140 kVp acquisitions. • Gadolinium quantification may be useful in patients with contraindication to iodine. • Dual-layer spectral detector CT allows for overall accurate quantification of gadolinium. • Interscan variability of gadolinium quantification using SDCT material decomposition is excellent.

Type of MRI contrast, tissue gadolinium, and fibrosis.

PubMed

Do, Catherine; Barnes, Jeffrey L; Tan, Chunyan; Wagner, Brent

2014-10-01

It has been presupposed that the thermodynamic stability constant (K(therm)) of gadolinium-based MRI chelates relate to the risk of precipitating nephrogenic systemic fibrosis. The present study compared low-K(therm) gadodiamide with high-K(therm) gadoteridol in cultured fibroblasts and rats with uninephrectomies. Gadolinium content was assessed using scanning electron microscopy equipped with energy-dispersive X-ray spectroscopy in paraffin-embedded tissues. In vitro, fibroblasts demonstrated dose-dependent fibronectin generation, transforming growth factor-β production, and expression of activated myofibroblast stress fiber protein α-smooth muscle actin. There were negligible differences with respect to toxicity or proliferation between the two contrast agents. In the rodent model, gadodiamide treatment led to greater skin fibrosis and dermal cellularity than gadoteridol. In the kidney, both contrast agents led to proximal tubule vacuolization and increased fibronectin accumulation. Despite large detectable gadolinium signals in the spleen, skin, muscle, and liver from the gadodiamide-treated group, contrast-induced fibrosis appeared to be limited to the skin and kidney. These findings support the hypothesis that low-K(therm) chelates have a greater propensity to elicit nephrogenic systemic fibrosis and demonstrate that certain tissues are resistant to these effects.

Characteristics of Gadolinium Oxide Nanoparticles Using Terahertz Spectroscopy

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

Lee, Dongkyu; Maeng, Inhee; Son, Joo-Hiuk

2009-04-19

The penetration property of the terahertz electromagnetic (THz) wave is relevant to its use. We used the THz wave spectroscopy system which easily penetrates some materials that do not contain water, e.g., plastic and ceramics. The system has been developed for several purposes, including measuring the properties of semiconductors and bio-materials, and detecting plastic bombs and ceramic knives at airports. It is also used for medical imaging systems, such as magnetic resonance imaging (MRI), at some research institutes. It can show not only the difference in amplitude, but also the difference of the phase of each point of sample. MRImore » technology usually uses contrast agents to enhance the quality of the image. Gadolinium diethylenetriamine pentaacetic acid (Gd-DTPA), made with a heavy metal ion, is commonly used as a clinical MRI contrast agent. Gadolinium oxide (Gd{sub 2}O{sub 3}) nanoparticle is a new contrast agent. It serves to equip the core of each particle with antibodies or ligands. It can freely circulate in blood vessels without amassing in the liver or lungs. This study shows the characteristics of gadolinium oxide nanoparticles to further advance terahertz medical imaging.« less

The impact of thermal treatment conditions on the formation of crystalline structure of Ce-Zr-oxide composite obtained by a modified sol-gel technique

NASA Astrophysics Data System (ADS)

Trusova, E. A.; Khrushcheva, A. A.; Shvorneva, L. I.

2012-02-01

We present the results of the modified sol-gel synthesis of ultrafine ceria-doped zirconia powder for medical ceramics (implants) and catalytic purposes (environmental catalysis and petrochemistry). Special attention has been paid to study the influence of thermal treatment on crystallite size and crystal lattice parameters of zirconia doped by ceria. Zirconyl chloride and cerium nitrate were used as metal sources, and tetraethylammonium hydroxide (TEAH) was used as a sol stabilizer at molar ratio TEAH/Σ (Ce + Zr) equal to 0.5. It was proved that zirconium and cerium practically completely were included in the obtained solid solutions, since their phase compositions fully correspond to initial quantities of cerium and zirconium in reaction mixture. It was shown that average crystallite size of the obtained powders did not exceed 75Å, and the powders were resistant to thermal treatment. It was established that stabilization of the crystal lattice of ZrO2 occurs through formation of a cubic ceria sublattice.

Impact of Dynamic Specimen Shape Evolution on the Atom Probe Tomography Results of Doped Epitaxial Oxide Multilayers: Comparison of Experiment and Simulation

DOE PAGES

Madaan, Nitesh; Bao, Jie; Nandasiri, Manjula I.; ...

2015-08-31

The experimental atom probe tomography results from two different specimen orientations (top-down and side-ways) of a high oxygen ion conducting Samaria-doped-ceria/Scandia-stabilized-zirconia multilayer thin film solid oxide fuel cell electrolyte was correlated with level-set method based field evaporation simulations for the same specimen orientations. This experiment-theory correlation explains the dynamic specimen shape evolution and ion trajectory aberrations that can induce density artifacts in final reconstruction leading to inaccurate estimation of interfacial intermixing. This study highlights the need and importance of correlating experimental results with field evaporation simulations when using atom probe tomography for studying oxide heterostructure interfaces.

Mechanism analysis on finishing of reaction-sintered silicon carbide by combination of water vapor plasma oxidation and ceria slurry polishing

NASA Astrophysics Data System (ADS)

Shen, Xinmin; Tu, Qunzhang; Deng, Hui; Jiang, Guoliang; Yamamura, Kazuya

2015-05-01

Reaction-sintered silicon carbide (RS-SiC), which is considered as a promising mirror material for space telescope systems, requires a high surface property. An ultrasmooth surface with a Ra surface roughness of 0.480 nm was obtained after water vapor plasma oxidation for 90 min followed by ceria slurry polishing for 40 min. The oxidation process of RS-SiC by water vapor plasma was analyzed based on the Deal-Grove model, and the theoretical calculation results are consistent with the measured data obtained by scanning white light interferometer (SWLI), scanning electron microscopy/energy-dispersive x-ray, and atomic force microscope. The polishing process of oxidized RS-SiC by ceria slurry was investigated according to the Preston equation, which would theoretically forecast the evolutions of RS-SiC surfaces along with the increasing of polishing time, and it was experimentally verified by comparing the surface roughnesses obtained by SWLI and the surface morphologies obtained by SEM. The mechanism analysis on the finishing of RS-SiC would be effective for the optimization of water vapor plasma oxidation parameters and ceria slurry polishing parameters, which will promote the application of RS-SiC substrates by improving the surface property obtained by the oxidation-assisted polishing method.

Microstructural Investigation, Raman and Magnetic Studies on Chemically Synthesized Nanocrystalline Ni-Doped Gadolinium Oxide (Gd1.90Ni0.10O3- δ )

NASA Astrophysics Data System (ADS)

Sarkar, B. J.; Mandal, J.; Dalal, M.; Bandyopadhyay, A.; Satpati, B.; Chakrabarti, P. K.

2018-03-01

Nanocrystalline Ni-doped gadolinium oxide (Gd1.90Ni0.10O3- δ , GNO) is synthesized by co-precipitation method. The as-prepared sample is annealed in vacuum at 700°C for 6 h. Analyses of the x-ray diffractogram by Rietveld refinement method, transmission electron microscopy and Raman spectroscopy of GNO recorded at room temperature confirmed the pure crystallographic phase and complete substitution of Ni-ions in Gd2O3 lattice. Magnetization ( M) as a function of temperature ( T) and magnetic field ( H) is measured by a superconducting quantum interference device magnetometer, which suggests the presence of ferromagnetic/antiferromagnetic phases together with a paramagnetic phase. From the M-T curve it can be shown that the ferromagnetic phase dominates over para-/antiferromagnetic phases in the temperature range of 300-100 K, but from 100 K to 50 K, the antiferromagnetic phase dominates over ferro-/paramagnetic phases. Hysteresis loops recorded at different temperatures indicate the presence of weak ferro-/antiferromagnetism, which dominates in the low field region (˜ 4000 Oe), above which magnetization increases linearly. The sharp increase of magnetization in M-T curve observed in the temperature range of 50-5 K confirms the presence of dominating ferromagnetic plus paramagnetic phase over antiferromagnetic part. For the first time a combined formula generated from three-dimensional (3D) spin wave model and Johnston formula is proposed to analyze the coexistence of different magnetic phases in different temperature ranges. Interestingly, the combined formula successfully explains the co-existence of different magnetic phases along with their contribution at different temperatures. The onset of ferromagnetism in Gd1.90Ni0.10O3- δ is explained by oxygen vacancy mediated F-centre exchange (FCE) coupling mechanism.

Quantitative depth profiling of Ce(3+) in Pt/CeO2 by in situ high-energy XPS in a hydrogen atmosphere.

PubMed

Kato, Shunsuke; Ammann, Markus; Huthwelker, Thomas; Paun, Cristina; Lampimäki, Markus; Lee, Ming-Tao; Rothensteiner, Matthäus; van Bokhoven, Jeroen A

2015-02-21

The redox property of ceria is a key factor in the catalytic activity of ceria-based catalysts. The oxidation state of well-defined ceria nanocubes in gas environments was analysed in situ by a novel combination of near-ambient pressure X-ray Photoelectron Spectroscopy (XPS) and high-energy XPS at a synchrotron X-ray source. In situ high-energy XPS is a promising new tool to determine the electronic structure of matter under defined conditions. The aim was to quantitatively determine the degree of cerium reduction in a nano-structured ceria-supported platinum catalyst as a function of the gas environment. To obtain a non-destructive depth profile at near-ambient pressure, in situ high-energy XPS analysis was performed by varying the kinetic energy of photoelectrons from 1 to 5 keV, and, thus, the probing depth. In ceria nanocubes doped with platinum, oxygen vacancies formed only in the uppermost layers of ceria in an atmosphere of 1 mbar hydrogen and 403 K. For pristine ceria nanocubes, no change in the cerium oxidation state in various hydrogen or oxygen atmospheres was observed as a function of probing depth. In the absence of platinum, hydrogen does not dissociate and, thus, does not lead to reduction of ceria.

The dosimetric impact of gadolinium-based contrast media in GBM brain patient plans for a MRI-Linac

NASA Astrophysics Data System (ADS)

Bilal Ahmad, Syed; Paudel, Moti Raj; Sarfehnia, Arman; Kim, Anthony; Pang, Geordi; Ruschin, Mark; Sahgal, Arjun; Keller, Brian M.

2017-08-01

Dosimetric effects of gadolinium based contrast media (Gadovist) were evaluated for the Elekta MRI linear accelerator using the research version of the Monaco treatment planning system (TPS). In order to represent a gadolinium uptake, the contrast was manually assigned to a phantom as well as to the gross tumour volume (GTV) of 6 glioblastoma multiforme (GBM) patients. A preliminary estimate of the dose enhancement, due to gadolinium, was performed using the phantom irradiated with a single beam. A more complicated assessment was performed for the GBM patients using a 7 field IMRT technique. The material table in Monaco was modified in order to identify the presence of a non-biological material. The dose distribution was modelled using GPUMCD (MC algorithm in Monaco) for an unmodified (or default) material table (DMT) as well as for a modified (or custom) material table (CMT) for both the phantom and patients. Various concentrations ranging between 8 and 157 mg ml-1 were used to represent the gadolinium uptake in the patient’s GTV. It was assumed that the gadolinium concentration remained the same for the entire course of radiation treatment. Results showed that at the tissue-Gadovist interface, inside the phantom, dose scored using the DMT was 7% lower compared to that using the CMT for 157 mg ml-1 concentration of gadolinium. Dosimetric differences in the case of the patient study were measured using the DVH parameters. D 50% was higher by 6% when the DMT was used compared to the CMT for dose modelling for a gadolinium concentration of 157 mg ml-1. This difference decreased gradually with decreasing concentration of gadolinium. It was concluded that dosimetric differences can be quantified in Monaco if the tumour-gadolinium concentration is more than 23 mg ml-1. If the gadolinium concentration is lower than 23 mg ml-1, then a correction for the presence of gadolinium may not be necessary in the TPS.

The dosimetric impact of gadolinium-based contrast media in GBM brain patient plans for a MRI-Linac.

PubMed

Ahmad, Syed Bilal; Paudel, Moti Raj; Sarfehnia, Arman; Kim, Anthony; Pang, Geordi; Ruschin, Mark; Sahgal, Arjun; Keller, Brian M

2017-08-01

Dosimetric effects of gadolinium based contrast media (Gadovist) were evaluated for the Elekta MRI linear accelerator using the research version of the Monaco treatment planning system (TPS). In order to represent a gadolinium uptake, the contrast was manually assigned to a phantom as well as to the gross tumour volume (GTV) of 6 glioblastoma multiforme (GBM) patients. A preliminary estimate of the dose enhancement, due to gadolinium, was performed using the phantom irradiated with a single beam. A more complicated assessment was performed for the GBM patients using a 7 field IMRT technique. The material table in Monaco was modified in order to identify the presence of a non-biological material. The dose distribution was modelled using GPUMCD (MC algorithm in Monaco) for an unmodified (or default) material table (DMT) as well as for a modified (or custom) material table (CMT) for both the phantom and patients. Various concentrations ranging between 8 and 157 mg ml -1 were used to represent the gadolinium uptake in the patient's GTV. It was assumed that the gadolinium concentration remained the same for the entire course of radiation treatment. Results showed that at the tissue-Gadovist interface, inside the phantom, dose scored using the DMT was 7% lower compared to that using the CMT for 157 mg ml -1 concentration of gadolinium. Dosimetric differences in the case of the patient study were measured using the DVH parameters. D 50% was higher by 6% when the DMT was used compared to the CMT for dose modelling for a gadolinium concentration of 157 mg ml -1 . This difference decreased gradually with decreasing concentration of gadolinium. It was concluded that dosimetric differences can be quantified in Monaco if the tumour-gadolinium concentration is more than 23 mg ml -1 . If the gadolinium concentration is lower than 23 mg ml -1 , then a correction for the presence of gadolinium may not be necessary in the TPS.

Gadolinium-enhanced cardiovascular magnetic resonance: administered dose in relationship to United States Food and Drug Administration (FDA) guidelines.

PubMed

Nacif, Marcelo S; Arai, Andrew E; Lima, Joao A C; Bluemke, David A

2012-02-29

Myocardial late gadolinium enhancement was originally validated using higher than label-recommended doses of gadolinium chelate. The objective of this study was to evaluate available evidence for various gadolinium dosing regimens used for CMR. The relationship of gadolinium dose warnings (due to nephrogenic systemic fibrosis) announced in 2008 to gadolinium dosing regimens was also examined. We conducted a meta-analysis of peer reviewed publications from January, 2004 to December, 2010. Major subject search headings (MeSh) terms from the National Library of Medicine's PubMed were: contrast media, gadolinium, heart, magnetic resonance imaging; searches were limited to human studies with abstracts published in English. Case reports, review articles, editorials, MRA related papers and all reports that did not indicate gadolinium type or weight-based dose were excluded. For all included references, full text was available to determine the total administered gadolinium dose on a per kg basis. Average and median dose values were weighted by the number of subjects in each study. 399 publications were identified in PubMed; 233 studies matched the inclusion criteria, encompassing 19,934 patients with mean age 54.2 ± 11.4 (range 9.3 to 76 years). 34 trials were related to perfusion testing and 199 to myocardial late gadolinium enhancement. In 2004, the weighted-median and weighted-mean contrast dose were 0.15 and 0.16 ± 0.06 mmol/kg, respectively. Median contrast doses for 2005-2010 were: 0.2 mmol/kg for all years, respectively. Mean contrast doses for the years 2005-2010 were: 0.19 ± 0.03, 0.18 ± 0.04, 0.18 ± 0.10, 0.18 ± 0.03, 0.18 ± 0.04 and 0.18 ± 0.04 mmol/kg, respectively (p for trend, NS). Gadopentetate dimeglumine was the most frequent gadolinium type [114 (48.9%) studies]. No change in mean gadolinium dose was present before, versus after the Food and Drug Administration (FDA) black box warning (p > 0.05). Three multi-center dose ranging trials have been

Continuous Precipitation of Ceria Nanoparticles from a Continuous Flow Micromixer

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

Tseng, Chih Heng; Paul, Brian; Chang, Chih-hung

2013-01-01

Cerium oxide nanoparticles were continuously precipitated from a solution of cerium(III) nitrate and ammonium hydroxide using a micro-scale T-mixer. Findings show that the method of mixing is important in the ceria precipitation process. In batch mixing and deposition, disintegration and agglomeration dominates the deposited film. In T-mixing and deposition, more uniform nanorod particles are attainable. In addition, it was found that the micromixing approach reduced the exposure of the Ce(OH)3 precipates to oxygen, yielding hydroxide precipates in place of CeO2 precipitates. Advantages of the micro-scale T-mixing approach include shorter mixing times, better control of nanoparticle shape and less agglomeration.

Synthesis and Characterization of Yttria-Stabilized Zirconia Nanoparticles Doped with Ytterbium and Gadolinium: ZrO2 9.5Y2O3 5.6Yb2O3 5.2Gd2O3

NASA Astrophysics Data System (ADS)

Bahamirian, M.; Hadavi, S. M. M.; Rahimipour, M. R.; Farvizi, M.; Keyvani, A.

2018-03-01

Defect cluster thermal barrier coatings (TBCs) are attractive alternatives to Yttria-stabilized zirconia (YSZ) in advanced applications. In this study, YSZ nanoparticles doped with ytterbium and gadolinium (ZrO2 9.5Y2O3 5.6Yb2O3 5.2Gd2O3 (ZGYbY)) were synthesized through a chemical co-precipitation and calcination method, and characterized by in situ high-temperature X-ray diffraction analysis in the temperature range of 25 °C to 1000 °C (HTK-XRD), thermogravimetric analysis, differential thermal analysis, Fourier transform infrared spectroscopy, Raman spectroscopy, and field emission scanning electron microscopy (FE-SEM). Precise cell parameters of t-prime phase and the best zirconia phase for TBC applications were calculated by Cohen's and Rietveld refinement methods. Optimum crystallization temperature of the precursor powder was found to be 1000 °C. Furthermore, FE-SEM results for the calcined ZGYbY powders indicated orderly particles of uniform shape and size with a small tendency toward agglomeration. Average lattice thermal expansion coefficient in the temperature range of 25 °C to 1000 °C was determined to be 31.71 × 10-6 K-1.

Synthesis and Characterization of Yttria-Stabilized Zirconia Nanoparticles Doped with Ytterbium and Gadolinium: ZrO2 9.5Y2O3 5.6Yb2O3 5.2Gd2O3

NASA Astrophysics Data System (ADS)

Bahamirian, M.; Hadavi, S. M. M.; Rahimipour, M. R.; Farvizi, M.; Keyvani, A.

2018-06-01

Defect cluster thermal barrier coatings (TBCs) are attractive alternatives to Yttria-stabilized zirconia (YSZ) in advanced applications. In this study, YSZ nanoparticles doped with ytterbium and gadolinium (ZrO2 9.5Y2O3 5.6Yb2O3 5.2Gd2O3 (ZGYbY)) were synthesized through a chemical co-precipitation and calcination method, and characterized by in situ high-temperature X-ray diffraction analysis in the temperature range of 25 °C to 1000 °C (HTK-XRD), thermogravimetric analysis, differential thermal analysis, Fourier transform infrared spectroscopy, Raman spectroscopy, and field emission scanning electron microscopy (FE-SEM). Precise cell parameters of t-prime phase and the best zirconia phase for TBC applications were calculated by Cohen's and Rietveld refinement methods. Optimum crystallization temperature of the precursor powder was found to be 1000 °C. Furthermore, FE-SEM results for the calcined ZGYbY powders indicated orderly particles of uniform shape and size with a small tendency toward agglomeration. Average lattice thermal expansion coefficient in the temperature range of 25 °C to 1000 °C was determined to be 31.71 × 10-6 K-1.

Method of separating and purifying gadolinium-153

DOEpatents

Bray, Lane A [Richland, WA; Corneillie, Todd M [Davis, CA

2001-01-01

The present invention is an improvement to the method of separating and purifying gadolinium from a mixture of gadolinium and europium having the steps of (a) dissolving the mixture in an acid; (b) reducing europium+3 to europium+2; and (c) precipitating the europium+2 with a sulfate ion in a superstoichiometric amount; wherein the improvement is achieved by using one or more of the following: (i) the acid is an anoic acid; (ii) the reducing is with zinc metal in the absence of a second metal or with an amount of the second metal that is ineffective in the reducing; (iii) adding a group IIA element after step (c) for precipitating the excess sulfate prior to repeating step (c); (iv) the sulfate is a sulfate salt with a monovalent cation; (v) adding cold europium+3 prior to repeating step (c).

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

Dholabhai, Pratik P., E-mail: pratik.dholabhai@asu.ed; Anwar, Shahriar, E-mail: anwar@asu.ed; Adams, James B., E-mail: jim.adams@asu.ed

Kinetic lattice Monte Carlo (KLMC) model is developed for investigating oxygen vacancy diffusion in praseodymium-doped ceria. The current approach uses a database of activation energies for oxygen vacancy migration, calculated using first-principles, for various migration pathways in praseodymium-doped ceria. Since the first-principles calculations revealed significant vacancy-vacancy repulsion, we investigate the importance of that effect by conducting simulations with and without a repulsive interaction. Initially, as dopant concentrations increase, vacancy concentration and thus conductivity increases. However, at higher concentrations, vacancies interfere and repel one another, and dopants trap vacancies, creating a 'traffic jam' that decreases conductivity, which is consistent with themore » experimental findings. The modeled effective activation energy for vacancy migration slightly increased with increasing dopant concentration in qualitative agreement with the experiment. The current methodology comprising a blend of first-principle calculations and KLMC model provides a very powerful fundamental tool for predicting the optimal dopant concentration in ceria related materials. -- graphical abstract: Ionic conductivity in praseodymium doped ceria as a function of dopant concentration calculated using the kinetic lattice Monte Carlo vacancy-repelling model, which predicts the optimal composition for achieving maximum conductivity. Display Omitted Research highlights: {yields} KLMC method calculates the accurate time-dependent diffusion of oxygen vacancies. {yields} KLMC-VR model predicts a dopant concentration of {approx}15-20% to be optimal in PDC. {yields} At higher dopant concentration, vacancies interfere and repel one another, and dopants trap vacancies. {yields} Activation energy for vacancy migration increases as a function of dopant content« less

Synthesis of nanocrystalline Ni/Ce-YSZ powder via a polymerization route

NASA Astrophysics Data System (ADS)

Abolghasemi, Z.; Tamizifar, M.; Arzani, K.; Nemati, A.; Khanfekr, A.; Bolandi, M.

2013-08-01

Pechini process was used for preparation of three kinds of nanocrystalline powders of yttria-stabilized zirconia (YSZ): doped with 1.5 mol% nickel oxide, doped with 15 mol% ceria, and doped with 1.5 mol% nickel oxide plus 15 mol% ceria. Zirconium chloride, yttrium nitrate, cerium nitrate, nickel nitrate, citric acid and ethylene glycol were polymerized at 80 °C to produce a gel. XRD, SEM and TEM analyses were used to investigate the crystalline phases and microstructures of obtained compounds. The results of XRD revealed the formation of nanocrystalline powder at 900 °C. Morphology of the powder calcined at 900 °C, examined with a scanning electron microscope, showed that the presence of nickel and cerium inhibited the grain growth in the system. The average crystallite size of the material doped with nickel oxide (9.33 nm) was bigger than the one doped with cerium oxide (9.29 nm), while the YSZ doping with the two oxides simultaneously promoted the grain growth with crystallite size of 11.37 nm. Yttria-stabilized zirconia powder with a mean crystallite size of 9.997 nm was prepared successfully by this method.

Controlling Heteroepitaxy by Oxygen Chemical Potential: Exclusive Growth of (100) Oriented Ceria Nanostructures on Cu(111)

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

Höcker, Jan; Duchoň, Tomáš; Veltruská, Kateřina

2016-01-06

We present a novel and simple method for the preparation of a well-defined CeO 2(100) model system on Cu(111) based on the adjustment of the Ce/O ratio during growth. The method yields micrometer-sized, several nanometers high, single-phase CeO 2(100) islands with controllable size and surface termination that can be benchmarked against the known (111) nanostructured islands on Cu(111). We also demonstrate the ability to adjust the Ce to O stoichiometry from CeO 2(100) (100% Ce 4+) to c-Ce 2O 3(100) (100% Ce 3+), which can be readily recognized by characteristic surface reconstructions observed by low-energy electron diffraction. Finally, the discoverymore » of the highly stable CeO x(100) phase on a hexagonally close packed metal surface represents an unexpected growth mechanism of ceria on Cu(111), and it provides novel opportunities to prepare more elaborate models, benchmark surface chemical reactivity, and thus gain valuable insights into the redox chemistry of ceria in catalytic processes.« less

Gadolinium: Central Metal of the Lanthanoids

ERIC Educational Resources Information Center

Laing, Michael

2009-01-01

The physical and chemical properties of gadolinium are compared with those of the other lanthanoids. Some properties are intermediate between those of lanthanum and lutetium; some between those of barium and hafnium; and others (unexpectedly) between those of ytterbium and lutetium. Both the remarkably high molar heat capacity of the metal and the…

Gadolinium Use in Spine Pain Management Procedures for Patients with Contrast Allergies: Results in 527 Procedures

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

Safriel, Yair; Ang, Roberto; Ali, Muhammed

2008-03-15

Introduction. To review the safety and efficacy of gadolinium in spine pain management procedures in patients at high risk for a contrast reaction and who are not suitable candidates for the use of standard non-ionic contrast. Methods. We reviewed records over a 61-month period of all image-guided spinal pain management procedures where patients had allergies making them unsuitable candidates for standard non-ionic contrast and where gadolinium was used to confirm needle tip placement prior to injection of medication. Results. Three hundred and four outpatients underwent 527 procedures. A spinal needle was used in all but 41 procedures. Gadolinium was visualizedmore » using portable C-arm fluoroscopy in vivo allowing for confirmation of needle tip location. The gadolinium dose ranged from 0.2 to 10 ml per level. The highest dose received by one patient was 15.83 ml intradiscally during a three-level discogram. Three hundred and one patients were discharged without complication or known delayed complications. One patient had documented intrathecal injection but without sequelae and 2 patients who underwent cervical procedures experienced seizures requiring admission to the intensive care unit. Both the latter patients were discharged without any further complications. Conclusion. Based on our experience we recommend using gadolinium judiciously for needle tip confirmation. We feel more confident using gadolinium in the lumbar spine and in cervical nerve blocks. Gadolinium should probably not be used as an injectate volume expander. The indications for gadolinium use in cervical needle-guided spine procedures are less clear and use of a blunt-tipped needle should be considered.« less

[Gadolinium-based contrast agents for magnetic resonance imaging].

PubMed

Carrasco Muñoz, S; Calles Blanco, C; Marcin, Javier; Fernández Álvarez, C; Lafuente Martínez, J

2014-06-01

Gadolinium-based contrast agents are increasingly being used in magnetic resonance imaging. These agents can improve the contrast in images and provide information about function and metabolism, increasing both sensitivity and specificity. We describe the gadolinium-based contrast agents that have been approved for clinical use, detailing their main characteristics based on their chemical structure, stability, and safety. In general terms, these compounds are safe. Nevertheless, adverse reactions, the possibility of nephrotoxicity from these compounds, and the possibility of developing nephrogenic systemic fibrosis will be covered in this article. Lastly, the article will discuss the current guidelines, recommendations, and contraindications for their clinical use, including the management of pregnant and breast-feeding patients. Copyright © 2014 SERAM. Published by Elsevier Espana. All rights reserved.

Theoretical study of structure and stability of small gadolinium carboxylate complexes in liquid scintillator solvents.

PubMed

Huang, Pin-Wen

2014-09-01

The structural properties of three small gadolinium carboxylate complexes in three liquid scintillator solvents (pseudocumene, linear alkylbenzene, and phenyl xylylethane) were theoretically investigated using density functional theory (B3LYP/LC-RECP) and polarizable continuum model (PCM). The average interaction energy between gadolinium atom and carboxylate ligand (E(int)) and the energy difference of the highest singly occupied molecular orbital and lowest unoccupied molecular orbital (Δ(SL)) were calculated to evaluate and compare the relative stability of these complexes in solvents. The calculation results show that the larger (with a longer alkyl chain) gadolinium carboxylate complex has greater stability than the smaller one, while these gadolinium carboxylates in linear alkylbenzene were found to have greater stability than those in the other two solvents.

Characteristics of Gadolinium Oxide Nanoparticles Using Terahertz Spectroscopy (abstract)

NASA Astrophysics Data System (ADS)

Lee, Dongkyu; Maeng, Inhee; Oh, Seung Jae; Kim, Taekhoon; Cho, Byung Kyu; Lee, Kwangyeol; Son, Joo-Hiuk

2009-04-01

The penetration property of the terahertz electromagnetic (THz) wave is relevant to its use. We used the THz wave spectroscopy system which easily penetrates some materials that do not contain water, e.g., plastic and ceramics. The system has been developed for several purposes, including measuring the properties of semiconductors and bio-materials, and detecting plastic bombs and ceramic knives at airports. It is also used for medical imaging systems, such as magnetic resonance imaging (MRI), at some research institutes. It can show not only the difference in amplitude, but also the difference of the phase of each point of sample. MRI technology usually uses contrast agents to enhance the quality of the image. Gadolinium diethylenetriamine pentaacetic acid (Gd-DTPA), made with a heavy metal ion, is commonly used as a clinical MRI contrast agent. Gadolinium oxide (Gd2O3) nanoparticle is a new contrast agent. It serves to equip the core of each particle with antibodies or ligands. It can freely circulate in blood vessels without amassing in the liver or lungs. This study shows the characteristics of gadolinium oxide nanoparticles to further advance terahertz medical imaging.

Toxicological and pharmacological effects of gadolinium and samarium chlorides

PubMed Central

Haley, T. J.; Raymond, K.; Komesu, N.; Upham, H. C.

1961-01-01

A study has been made of the toxicology and pharmacology of gadolinium and samarium chlorides. The symptoms of acute toxicity following intraperitoneal injection are described. The chronic oral ingestion of both chemicals for 12 weeks produced no effects on growth or the blood picture, and only the male rats receiving gadolinium chloride showed liver damage. The pharmacological responses to both chemicals were mainly depressant on all systems studied, and death was associated with cardiovascular collapse coupled with respiratory paralysis. The greatest damage seen was on abraded skin, where non-healing ulcers were produced by both chemicals, whereas irritation of intact skin and ocular tissues was only transient in nature. PMID:13903826

Single crystal Ce doped scintillator material with garnet structure sensitive to gamma ray and neutron radiation

NASA Astrophysics Data System (ADS)

Solodovnikov, D.; Weber, M. H.; Haven, D. T.; Lynn, K. G.

2012-08-01

A mixed garnet scintillator host material is obtained from the melt—Yttrium Gadolinium Gallium Aluminum Garnet (YGGAG). In addition to the high thermal and chemical stability and radiation hardness found in garnet crystals, it offers sensitivity to neutrons due to the presence of Gd atoms, has lower melting temperature than yttrium aluminum garnet, and similar crystallization behavior suitable for growth of large volume crystals. Crystals of YGGAG doped with Ce of 10×10×10 mm3 have already demonstrated energy resolution of 10% at 662 keV.

Porphyrin-containing polyaspartamide gadolinium complexes as potential magnetic resonance imaging contrast agents.

PubMed

Yan, Guo-Ping; Li, Zhen; Xu, Wei; Zhou, Cheng-Kai; Yang, Lian; Zhang, Qiao; Li, Liang; Liu, Fan; Han, Lin; Ge, Yuan-Xing; Guo, Jun-Fang

2011-04-04

Porphyrin-containing polyaspartamide ligands (APTSPP-PHEA-DTPA) were synthesized by the incorporation of diethylenetriaminepentaacetic acid (DTPA) and 5-(4'-aminophenyl)-10,15,20-tris(4'-sulfonatophenyl) porphyrin, trisodium salt (APTSPP) into poly-α,β-[N-(2-hydroxyethyl)-l-aspartamide] (PHEA). These ligands were further reacted with gadolinium chloride to produce macromolecule-gadolinium complexes (APTSPP-PHEA-DTPA-Gd). Experimental data of (1)H NMR, IR, UV and elemental analysis evidenced the formation of the polyaspartamide ligands and gadolinium complexes. In vitro and in vivo property tests indicated that APTSPP-PHEA-DTPA-Gd possessed noticeably higher relaxation effectiveness, less toxicity to HeLa cells, and significantly higher enhanced signal intensities (SI) of the VX2 carcinoma in rabbits with lower injection dose requirement than that of Gd-DTPA. Moreover, APTSPP-PHEA-DTPA-Gd was found to greatly enhance the contrast of MR images of the VX2 carcinoma, providing prolonged intravascular duration, and distinguished the VX2 carcinoma and normal tissues in rabbits according to MR image signal enhancements. These porphyrin-containing polyaspartamide gadolinium complexes can be used as the candidates of contrast agents for targeted MRI to tumors. Crown Copyright © 2011. Published by Elsevier B.V. All rights reserved.

In-situ Characterization of Cu/CeO 2 Nanocatalysts during CO 2 Hydrogenation: Morphological Effects of Nanostructured Ceria on the Catalytic Activity

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

Lin, Lili; Yao, Siyu; Liu, Zongyuan

Here, a combination of time-resolved X-ray diffraction (TR-XRD), ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) was used to carry out an in-situ characterization of Cu/CeO 2 nanocatalysts during the hydrogenation of CO 2. Morphological effects of the ceria supports on the catalytic performances were investigated by examining the behavior of copper/ceria-nanorods (NR) and nanospheres (NS). At atmospheric pressures, the hydrogenation of CO 2 on the copper-ceria catalysts produced mainly CO through the reverse-water gas shift reaction (RWGS) and a negligible amount of methanol. The Cu/CeO 2-NR catalyst displayed the higher activity, which demonstrates thatmore » the RWGS is a structure sensitive reaction. In-situ TR-XRD and AP-XPS characterization showed significant changes in the chemical state of the catalysts under reaction conditions with the copper being fully reduced and a partial Ce 4+ to Ce 3+ transformation occurring. A more effective CO 2 dissociative activation at high temperature and a preferential formation of active bidentate carbonate and formate intermediates over CeO 2(110) terminations are probably the main reasons for the better performance of the Cu/CeO 2-NR catalyst in the RWGS reaction.« less

In-situ Characterization of Cu/CeO 2 Nanocatalysts during CO 2 Hydrogenation: Morphological Effects of Nanostructured Ceria on the Catalytic Activity

DOE PAGES

Lin, Lili; Yao, Siyu; Liu, Zongyuan; ...

2018-05-28

Here, a combination of time-resolved X-ray diffraction (TR-XRD), ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) was used to carry out an in-situ characterization of Cu/CeO 2 nanocatalysts during the hydrogenation of CO 2. Morphological effects of the ceria supports on the catalytic performances were investigated by examining the behavior of copper/ceria-nanorods (NR) and nanospheres (NS). At atmospheric pressures, the hydrogenation of CO 2 on the copper-ceria catalysts produced mainly CO through the reverse-water gas shift reaction (RWGS) and a negligible amount of methanol. The Cu/CeO 2-NR catalyst displayed the higher activity, which demonstrates thatmore » the RWGS is a structure sensitive reaction. In-situ TR-XRD and AP-XPS characterization showed significant changes in the chemical state of the catalysts under reaction conditions with the copper being fully reduced and a partial Ce 4+ to Ce 3+ transformation occurring. A more effective CO 2 dissociative activation at high temperature and a preferential formation of active bidentate carbonate and formate intermediates over CeO 2(110) terminations are probably the main reasons for the better performance of the Cu/CeO 2-NR catalyst in the RWGS reaction.« less

An open circuit voltage equation enabling separation of cathode and anode polarization resistances of ceria electrolyte based solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Zhang, Yanxiang; Chen, Yu; Yan, Mufu

2017-07-01

The open circuit voltage (OCV) of solid oxide fuel cells is generally overestimated by the Nernst equation and the Wagner equation, due to the polarization losses at electrodes. Considering both the electronic conduction of electrolyte and the electrode polarization losses, we express the OCV as an implicit function of the characteristic oxygen pressure of electrolyte (p* [atm], at which the electronic and ionic conductivities are the same), and the relative polarization resistance of electrodes (rc = Rc/Ri and ra = Ra/Ri, where Ri/c/a [Ωcm2] denotes the ionic resistance of electrolyte, and the polarization resistances of cathode and anode, respectively). This equation approaches to the Wagner equation when the electrodes are highly active (rc and ra → 0), and approaches to the Nernst equation when the electrolyte is a purely ionic conductor (p* → 0). For the fuel cells whose OCV is well below the prediction of the Wagner equation, for example with thin doped ceria electrolyte, it is demonstrated that the combination of OCV and impedance spectroscopy measurements allows the determination of p*, Rc and Ra. This equation can serve as a simple yet powerful tool to study the internal losses in the cell under open circuit condition.

Removal of gadolinium, a neutron poison from the moderator system of nuclear reactors.

PubMed

Rufus, A L; Kumar, Padma S; Jeena, K; Velmurugan, S

2018-01-15

Gadolinium as gadolinium nitrate is used as neutron poison in the moderator system for regulating and controlling the power generation of Pressurized Heavy Water Reactors (PHWR) and proposed to be used in Advanced Heavy Water Reactors (AHWR) owing to its high neutron absorption cross section. Removal of the added gadolinium nitrate (Gd 3+ and NO 3 - ) from the system after its intended use is done using ion exchange resins. In the present investigation, attempts have been made to optimize the ion exchange process for generation of low radioactive waste and maximize utilization of the ion exchange resins by employing different types of resins and different modes of operation. The investigations revealed that use of mixed bed (MB) resin column consisting of Strong Acid Cation (SAC) resin and Strong Base Anion (SBA) resin followed by SAC resin column is efficient in removing the Gd 3+ and NO 3 - from the system besides maintaining the pH of the moderator system in the desirable regime, where gadolinium does not get precipitated as its hydroxide. Copyright © 2017 Elsevier B.V. All rights reserved.

The feasibility of in vivo quantification of bone-gadolinium in humans by prompt gamma neutron activation analysis (PGNAA) following gadolinium-based contrast-enhanced MRI

NASA Astrophysics Data System (ADS)

Mostafaei, F.; McNeill, F. E.; Chettle, D. R.; Noseworthy, M. D.; Prestwich, W. V.

2015-11-01

The feasibility of using a 238Pu/Be-based in vivo prompt γ-ray neutron activation analysis (IVNAA) system, previously successfully used for measurements of muscle, for the detection of gadolinium (Gd) in bone was presented. Gd is extensively used in contrast agents in MR imaging. We present phantom measurement data for the measurement of Gd in the tibia. Gd has seven naturally occurring isotopes, of which two have extremely large neutron capture cross sections; 155Gd (14.8% natural abundance (NA), σ= 60,900 barns) and 157Gd (15.65% NA, σ= 254,000 barns). Our previous work focused on muscle but this only informs about the short term kinetics of Gd. We studied the possibility of measuring bone, as it may be a long term storage site for Gd. A human simulating bone phantom set was developed. The phantoms were doped with seven concentrations of Gd of concentrations 0.0, 25, 50, 75, 100, 120 and 150 ppm. Additional elements important for neutron activation analysis, Na, Cl and Ca, were also included to create an overall elemental composition consistent with Reference Man. The overall conclusion is that the potential application of this Pu-Be-based prompt in vivo NAA for the monitoring of the storage and retention of Gd in bone is not feasible.

Splitting CO2 with a ceria‐based redox cycle in a solar‐driven thermogravimetric analyzer

PubMed Central

Takacs, M.; Ackermann, S.; Bonk, A.; Neises‐von Puttkamer, M.; Haueter, Ph.; Scheffe, J. R.; Vogt, U. F.

2016-01-01

Thermochemical splitting of CO2 via a ceria‐based redox cycle was performed in a solar‐driven thermogravimetric analyzer. Overall reaction rates, including heat and mass transport, were determined under concentrated irradiation mimicking realistic operation of solar reactors. Reticulated porous ceramic (RPC) structures and fibers made of undoped and Zr4+‐doped CeO2, were endothermally reduced under radiative fluxes of 1280 suns in the temperature range 1200–1950 K and subsequently re‐oxidized with CO2 at 950–1400 K. Rapid and uniform heating was observed for 8 ppi ceria RPC with mm‐sized porosity due to its low optical thickness and volumetric radiative absorption, while ceria fibers with μm‐sized porosity performed poorly due to its opacity to incident irradiation. The 10 ppi RPC exhibited higher fuel yield because of its higher sample density. Zr4+‐doped ceria showed increasing reduction extents with dopant concentration but decreasing specific CO yield due to unfavorable oxidation thermodynamics and slower kinetics. © 2016 American Institute of Chemical Engineers AIChE J, 63: 1263–1271, 2017 PMID:28405030

Gadolinium Brain Deposition after Macrocyclic Gadolinium Administration: A Pediatric Case-Control Study.

PubMed

Tibussek, Daniel; Rademacher, Christin; Caspers, Julian; Turowski, Bernd; Schaper, Jörg; Antoch, Gerald; Klee, Dirk

2017-10-01

Purpose To determine whether signal intensity (SI) in T1 sequences as a potential indicator of gadolinium deposition increases after repeated administration of the macrocyclic gadolinium-based contrast agents (GBCAs) gadoteridol and gadoterate meglumine in a pediatric cohort. Materials and Methods This retrospective case-control study of children with brain tumors who underwent nine or more contrast material-enhanced brain magnetic resonance (MR) imaging studies from 2008 to 2015 was approved by the local ethics board. Informed consent was obtained for MR imaging. Twenty-four case patients aged 5-18 years and appropriate control patients with nonpathologic MR neuroimaging findings (and no GBCA administration), matched for age and sex, were inculded. SI was measured on unenhanced T1-weighted MR images for the following five regions of interest (ROIs): the dentate nucleus (DN), pons, substantia nigra (SN), pulvinar thalami, and globus pallidus (GP). Paired t tests were used to compare SI and SI ratios (DN to pons, GP to thalamus) between case patients and control patients. Pearson correlations between relative signal changes and the number of GBCA administrations and total GBCA dose were calculated. Results The mean number of GBCA administrations was 14.2. No significant differences in mean SI for any ROI and no group differences were found when DN-to-pons and GP-to-pulvinar ratios were compared (DN-to-pons ratio in case patients: mean, 1.0083 ± 0.0373 [standard deviation]; DN-to-pons ratio in control patients: mean, 1.0183 ± 0.01917; P = .37; GP-to-pulvinar ratio in case patients: mean, 1.1335 ± 0.04528; and GP-to-pulvinar ratio in control patients: mean, 1.1141 ± 0.07058; P = .29). No correlation was found between the number of GBCA administrations or the total amount of GBCA administered and signal change for any ROI. (Number of GBCA applications: DN: r = -0.254, P = .31; pons: r = -0.097, P = .65; SN: r = -0.194, P = .38; GP: r = -0.175, P = .41; pulvinar: r

Gadolinium Endohedral Metallofullerene-Based MRI Contrast Agents

NASA Astrophysics Data System (ADS)

Bolskar, Robert D.

With the ability to encapsulate and carry the highly paramagnetic Gd3+ ion, gadolinium endohedral metallofullerenes or "gadofullerenes" are being explored as alternatives to the chelate complexes that are currently used for contrast-enhanced magnetic resonance imaging (MRI). Reviewed here are the various water-soluble derivatives of the gadofullerenes Gd@C82, Gd@C60, and Gd3N@C80 that have been investigated as MRI contrast agents. The water proton r1 relaxivities of gadofullerenes can be more than an order of magnitude higher than those of clinically used chelate agents. Gadofullerene relaxivity mechanisms have been studied, and multiple factors are found to contribute to their high relaxivities. In vitro and in vivoT1-weighted MRI tests of gadofullerene derivatives have shown their utility as bright image-enhancing agents. The gadofullerene MRI contrast agents are a promising new and unique style of gadolinium carrier for advanced imaging applications, including cellular and molecular imaging.

High power density solid oxide fuel cells

DOEpatents

Pham, Ai Quoc; Glass, Robert S.

2004-10-12

A method for producing ultra-high power density solid oxide fuel cells (SOFCs). The method involves the formation of a multilayer structure cells wherein a buffer layer of doped-ceria is deposited intermediate a zirconia electrolyte and a cobalt iron based electrode using a colloidal spray deposition (CSD) technique. For example, a cobalt iron based cathode composed of (La,Sr)(Co,Fe)O (LSCF) may be deposited on a zirconia electrolyte via a buffer layer of doped-ceria deposited by the CSD technique. The thus formed SOFC have a power density of 1400 mW/cm.sup.2 at 600.degree. C. and 900 mW/cm.sup.2 at 700.degree. C. which constitutes a 2-3 times increased in power density over conventionally produced SOFCs.

Method of Fabrication of High Power Density Solid Oxide Fuel Cells

DOEpatents

Pham, Ai Quoc; Glass, Robert S.

2008-09-09

A method for producing ultra-high power density solid oxide fuel cells (SOFCs). The method involves the formation of a multilayer structure cells wherein a buffer layer of doped-ceria is deposited intermediate a zirconia electrolyte and a cobalt iron based electrode using a colloidal spray deposition (CSD) technique. For example, a cobalt iron based cathode composed of (La,Sr)(Co,Fe)O(LSCF) may be deposited on a zirconia electrolyte via a buffer layer of doped-ceria deposited by the CSD technique. The thus formed SOFC have a power density of 1400 mW/cm.sup.2 at 600.degree. C. and 900 mW/cm.sup.2 at 700.degree. C. which constitutes a 2-3 times increased in power density over conventionally produced SOFCs.

Gadolinium Deposition in Human Brain Tissues after Contrast-enhanced MR Imaging in Adult Patients without Intracranial Abnormalities.

PubMed

McDonald, Robert J; McDonald, Jennifer S; Kallmes, David F; Jentoft, Mark E; Paolini, Michael A; Murray, David L; Williamson, Eric E; Eckel, Laurence J

2017-11-01

Purpose To determine whether gadolinium deposits in neural tissues of patients with intracranial abnormalities following intravenous gadolinium-based contrast agent (GBCA) exposure might be related to blood-brain barrier integrity by studying adult patients with normal brain pathologic characteristics. Materials and Methods After obtaining antemortem consent and institutional review board approval, the authors compared postmortem neuronal tissue samples from five patients who had undergone four to 18 gadolinium-enhanced magnetic resonance (MR) examinations between 2005 and 2014 (contrast group) with samples from 10 gadolinium-naive patients who had undergone at least one MR examination during their lifetime (control group). All patients in the contrast group had received gadodiamide. Neuronal tissues from the dentate nuclei, pons, globus pallidus, and thalamus were harvested and analyzed with inductively coupled plasma mass spectrometry (ICP-MS), transmission electron microscopy with energy-dispersive x-ray spectroscopy, and light microscopy to quantify, localize, and assess the effects of gadolinium deposition. Results Tissues from the four neuroanatomic regions of gadodiamide-exposed patients contained 0.1-19.4 μg of gadolinium per gram of tissue in a statistically significant dose-dependent relationship (globus pallidus: ρ = 0.90, P = .04). In contradistinction, patients in the control group had undetectable levels of gadolinium with ICP-MS. All patients had normal brain pathologic characteristics at autopsy. Three patients in the contrast group had borderline renal function (estimated glomerular filtration rate <45 mL/min/1.73 m 2 ) and hepatobiliary dysfunction at MR examination. Gadolinium deposition in the contrast group was localized to the capillary endothelium and neuronal interstitium and, in two cases, within the nucleus of the cell. Conclusion Gadolinium deposition in neural tissues after GBCA administration occurs in the absence of intracranial

Tailoring gadolinium-doped ceria-based solid oxide fuel cells to achieve 2 W cm(-2) at 550 °C.

PubMed

Lee, Jin Goo; Park, Jeong Ho; Shul, Yong Gun

2014-06-04

Low-temperature operation is necessary for next-generation solid oxide fuel cells due to the wide variety of their applications. However, significant increases in the fuel cell losses appear in the low-temperature solid oxide fuel cells, which reduce the cell performance. To overcome this problem, here we report Gd0.1Ce0.9O1.95-based low-temperature solid oxide fuel cells with nanocomposite anode functional layers, thin electrolytes and core/shell fibre-structured Ba0.5Sr0.5Co0.8Fe0.2O3-δ-Gd0.1Ce0.9O1.95 cathodes. In particular, the report describes the use of the advanced electrospinning and Pechini process in the preparation of the core/shell-fibre-structured cathodes. The fuel cells show a very high performance of 2 W cm(-2) at 550 °C in hydrogen, and are stable for 300 h even under the high current density of 1 A cm(-2). Hence, the results suggest that stable and high-performance solid oxide fuel cells at low temperatures can be achieved by modifying the microstructures of solid oxide fuel cell components.

Recent progress in advanced optical materials based on gadolinium aluminate garnet (Gd3Al5O12)

PubMed Central

Li, Ji-Guang; Sakka, Yoshio

2015-01-01

This review article summarizes the recent achievements in stabilization of the metastable lattice of gadolinium aluminate garnet (Gd3Al5O12, GAG) and the related developments of advanced optical materials, including down-conversion phosphors, up-conversion phosphors, transparent ceramics, and single crystals. Whenever possible, the materials are compared with their better known YAG and LuAG counterparts to demonstrate the merits of the GAG host. It is shown that novel emission features and significantly improved luminescence can be attained for a number of phosphor systems with the more covalent GAG lattice and the efficient energy transfer from Gd3+ to the activator. Ce3+ doped GAG-based single crystals and transparent ceramics are also shown to simultaneously possess the advantages of high theoretical density, fast scintillation decay, and high light yields, and hold great potential as scintillators for a wide range of applications. The unresolved issues are also pointed out. PMID:27877750

Recent progress in advanced optical materials based on gadolinium aluminate garnet (Gd3Al5O12)

NASA Astrophysics Data System (ADS)

Li, Ji-Guang; Sakka, Yoshio

2015-02-01

This review article summarizes the recent achievements in stabilization of the metastable lattice of gadolinium aluminate garnet (Gd3Al5O12, GAG) and the related developments of advanced optical materials, including down-conversion phosphors, up-conversion phosphors, transparent ceramics, and single crystals. Whenever possible, the materials are compared with their better known YAG and LuAG counterparts to demonstrate the merits of the GAG host. It is shown that novel emission features and significantly improved luminescence can be attained for a number of phosphor systems with the more covalent GAG lattice and the efficient energy transfer from Gd3+ to the activator. Ce3+ doped GAG-based single crystals and transparent ceramics are also shown to simultaneously possess the advantages of high theoretical density, fast scintillation decay, and high light yields, and hold great potential as scintillators for a wide range of applications. The unresolved issues are also pointed out.

Designing Tripodal and Triangular Gadolinium Oxide Nanoplates and Self-Assembled Nanofibrils as Potential Multimodal Bioimaging Probes

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

Paik, T; Gordon, TR; Prantner, AM

2013-03-01

Here, we report the shape-controlled synthesis of tripodal and triangular gadolinium oxide (Gd2O3) nanoplates. In the presence of lithium ions, the shape of the nanocrystals is readily controlled by tailoring reaction parameters such as temperature and time. We observe that the morphology transforms from an initial tripodal shape to a triangular shape with increasing reaction time or elevated temperatures. Highly uniform Gd2O3 nanoplates are self-assembled into nanofibril-like liquid-crystalline superlattices with long-range orientational and positional order. In addition, shape-directed self-assemblies are investigated by tailoring the aspect ratio of the arms of the Gd2O3 nanoplates. Due to a strong paramagnetic response, Gd2O3more » nanocrystals are excellent candidates for MRI contrast agents and also can be doped with rare-earth ions to form nanophosphors, pointing to their potential in multimodal imaging. In this work, we investigate the MR relaxometry at high magnetic fields (9,4 and 14.1 T) and the optical properties including near-IR to visible upconversion luminescence and X-ray excited optical luminescence of doped Gd2O3 nanoplates. The complex shape of Gd2O3 nanoplates, coupled with their magnetic properties and their ability to phosphoresce under NIR or X-ray excitation which penetrate deep into tissue, makes these nanoplates a promising platform for multimodal imaging in biomedical applications.« less

Gadolinium-based nanoparticles to improve the hadrontherapy performances.

PubMed

Porcel, Erika; Tillement, Olivier; Lux, François; Mowat, Pierre; Usami, Noriko; Kobayashi, Katsumi; Furusawa, Yoshiya; Le Sech, Claude; Li, Sha; Lacombe, Sandrine

2014-11-01

Nanomedicine is proposed as a novel strategy to improve the performance of radiotherapy. High-Z nanoparticles are known to enhance the effects of ionizing radiation. Recently, multimodal nanoparticles such as gadolinium-based nanoagents were proposed to amplify the effects of x-rays and g-rays and to improve MRI diagnosis. For tumors sited in sensitive tissues, childhood cases and radioresistant cancers, hadrontherapy is considered superior to x-rays and g-rays. Hadrontherapy, based on fast ion radiation, has the advantage of avoiding damage to the tissues behind the tumor; however, the damage caused in front of the tumor is its major limitation. Here, we demonstrate that multimodal gadolinium-based nanoparticles amplify cell death with fast ions used as radiation. Molecular scale experiments give insights into the mechanisms underlying the amplification of radiation effects. This proof-of-concept opens up novel perspectives for multimodal nanomedicine in hadrontherapy, ultimately reducing negative radiation effects in healthy tissues in front of the tumor. Gadolinium-chelating polysiloxane nanoparticles were previously reported to amplify the anti-tumor effects of x-rays and g-rays and to serve as MRI contrast agents. Fast ion radiation-based hadrontherapy avoids damage to the tissues behind the tumor, with a major limitation of tissue damage in front of the tumor. This study demonstrates a potential role for the above nanoagents in optimizing hadrontherapy with preventive effects in healthy tissue and amplified cell death in the tumor. Copyright © 2014 Elsevier Inc. All rights reserved.

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.

Retention of Gadolinium-Based Contrast Agents in Multiple Sclerosis: Retrospective Analysis of an 18-Year Longitudinal Study.

PubMed

Forslin, Y; Shams, S; Hashim, F; Aspelin, P; Bergendal, G; Martola, J; Fredrikson, S; Kristoffersen-Wiberg, M; Granberg, T

2017-07-01

Gadolinium-based contrast agents have been associated with lasting high T1-weighted signal intensity in the dentate nucleus and globus pallidus, with histopathologically confirmed gadolinium retention. We aimed to longitudinally investigate the relationship of multiple gadolinium-based contrast agent administrations to the Signal Intensity Index in the dentate nucleus and globus pallidus and any associations with cognitive function in multiple sclerosis. The Signal Intensity Index in the dentate nucleus and globus pallidus was retrospectively evaluated on T1-weighted MR imaging in an 18-year longitudinal cohort study of 23 patients with MS receiving multiple gadolinium-based contrast agent administrations and 23 healthy age- and sex-matched controls. Participants also underwent comprehensive neuropsychological testing. Patients with MS had a higher Signal Intensity Index in the dentate nucleus ( P < .001), but not in the globus pallidus ( P = .19), compared with non-gadolinium-based contrast agent-exposed healthy controls by an unpaired t test. Increasing numbers of gadolinium-based contrast agent administrations were associated with an increased Signal Intensity Index in the dentate nucleus (β = 0.45, P < .001) and globus pallidus (β = 0.60, P < .001). This association remained stable with corrections for the age, disease duration, and physical disability for both the dentate nucleus (β = 0.43, P = .001) and globus pallidus (β = 0.58, P < .001). An increased Signal Intensity Index in the dentate nucleus among patients with MS was associated with lower verbal fluency scores, which remained significant after correction for several aspects of disease severity (β = -0.40 P = .013). Our data corroborate previous reports of lasting gadolinium retention in brain tissues. An increased Signal Intensity Index in the dentate nucleus and globus pallidus was associated with lower verbal fluency, which does not prove causality but encourages further studies on cognition

In vivo demonstration of enhanced radiotherapy using rare earth doped titania nanoparticles†

PubMed Central

Townley, Helen E.; Kim, Jeewon; Dobson, Peter J.

2017-01-01

Radiation therapy is often limited by damage to healthy tissue and associated side-effects; restricting radiation to ineffective doses. Preferential incorporation of materials into tumour tissue can enhance the effect of radiation. Titania has precedent for use in photodynamic therapy (PDT), generating reactive oxygen species (ROS) upon photoexcitation, but is limited by the penetration depth of UV light. Optimization of a nanomaterial for interaction with X-rays could be used for deep tumour treatment. As such, titania nanoparticles were doped with gadolinium to optimize the localized energy absorption from a conventional medical X-ray, and further optimized by the addition of other rare earth (RE) elements. These elements were selected due to their large X-ray photon interaction cross-section, and potential for integration into the titania crystal structure. Specific activation of the nanoparticles by X-ray can result in generation of ROS leading to cell death in a tumour-localized manner. We show here that intratumoural injection of RE doped titania nanoparticles can enhance the efficacy of radiotherapy in vivo. PMID:22767269

In vivo demonstration of enhanced radiotherapy using rare earth doped titania nanoparticles.

PubMed

Townley, Helen E; Kim, Jeewon; Dobson, Peter J

2012-08-21

Radiation therapy is often limited by damage to healthy tissue and associated side-effects; restricting radiation to ineffective doses. Preferential incorporation of materials into tumour tissue can enhance the effect of radiation. Titania has precedent for use in photodynamic therapy (PDT), generating reactive oxygen species (ROS) upon photoexcitation, but is limited by the penetration depth of UV light. Optimization of a nanomaterial for interaction with X-rays could be used for deep tumour treatment. As such, titania nanoparticles were doped with gadolinium to optimize the localized energy absorption from a conventional medical X-ray, and further optimized by the addition of other rare earth (RE) elements. These elements were selected due to their large X-ray photon interaction cross-section, and potential for integration into the titania crystal structure. Specific activation of the nanoparticles by X-ray can result in generation of ROS leading to cell death in a tumour-localized manner. We show here that intratumoural injection of RE doped titania nanoparticles can enhance the efficacy of radiotherapy in vivo.

Myocardial late gadolinium enhancement in specific cardiomyopathies by cardiovascular magnetic resonance: a preliminary experience.

PubMed

Silva, Caterina; Moon, James C; Elkington, Andrew G; John, Anna S; Mohiaddin, Raad H; Pennell, Dudley J

2007-12-01

Late gadolinium enhancement cardiovascular magnetic resonance (CMR) can visualize myocardial interstitial abnormalities. The aim of this study was to assess whether regions of abnormal myocardium can also be visualized by late enhancement gadolinium CMR in the specific cardiomyopathies. A retrospective review of all referrals for gadolinium CMR with specific cardiomyopathy over 20 months. Nine patients with different specific cardiomyopathies were identified. Late enhancement was demonstrated in all patients, with a mean signal intensity of 390 +/- 220% compared with normal regions. The distribution pattern of late enhancement was unlike the subendocardial late enhancement related to coronary territories found in myocardial infarction. The affected areas included papillary muscles (sarcoid), the mid-myocardium (Anderson-Fabry disease, glycogen storage disease, myocarditis, Becker muscular dystrophy) and the global sub-endocardium (systemic sclerosis, Loeffler's endocarditis, amyloid, Churg-Strauss). Focal myocardial late gadolinium enhancement is found in the specific cardiomyopathies, and the pattern is distinct from that seen in infarction. Further systematic studies are warranted to assess whether the pattern and extent of late enhancement may aid diagnosis and prognostic assessment.

Pediatric Patients Demonstrate Progressive T1-Weighted Hyperintensity in the Dentate Nucleus following Multiple Doses of Gadolinium-Based Contrast Agent.

PubMed

Roberts, D R; Chatterjee, A R; Yazdani, M; Marebwa, B; Brown, T; Collins, H; Bolles, G; Jenrette, J M; Nietert, P J; Zhu, X

2016-12-01

While there have been recent reports of brain retention of gadolinium following gadolinium-based contrast agent administration in adults, a retrospective series of pediatric patients has not previously been reported, to our knowledge. We investigated the relationship between the number of prior gadolinium-based contrast agent doses and increasing T1 signal in the dentate nucleus on unenhanced T1-weighted MR imaging. We hypothesized that despite differences in pediatric physiology and the smaller gadolinium-based contrast agent doses that pediatric patients are typically administered based on weighted-adjusted dosing, the pediatric brain would also demonstrate dose-dependent increasing T1 signal in the dentate nucleus. We included children with multiple gadolinium-based contrast agent administrations at our institution. A blinded reader placed ROIs within the dentate nucleus and adjacent cerebellar white matter. To eliminate reader bias, we also performed automated ROI delineation of the dentate nucleus, cerebellar white matter, and pons. Dentate-to-cerebellar white matter and dentate-to pons ratios were compared with the number of gadolinium-based contrast agent administrations. During 20 years at our institution, 280 patients received at least 5 gadolinium-based contrast agent doses, with 1 patient receiving 38 doses. Sixteen patients met the inclusion/exclusion criteria for ROI analysis. Blinded reader dentate-to-cerebellar white matter ratios were significantly associated with gadolinium-based contrast agent doses (r s = 0.77, P = .001). The dentate-to-pons ratio and dentate-to-cerebellar white matter ratios based on automated ROI placement were also significantly correlated with gadolinium-based contrast agent doses (t = 4.98, P < .0001 and t = 2.73, P < .02, respectively). In pediatric patients, the number of prior gadolinium-based contrast agent doses is significantly correlated with progressive T1-weighted dentate hyperintensity. Definitive confirmation of

The High Radiosensitizing Efficiency of a Trace of Gadolinium-Based Nanoparticles in Tumors

NASA Astrophysics Data System (ADS)

Dufort, Sandrine; Le Duc, Géraldine; Salomé, Murielle; Bentivegna, Valerie; Sancey, Lucie; Bräuer-Krisch, Elke; Requardt, Herwig; Lux, François; Coll, Jean-Luc; Perriat, Pascal; Roux, Stéphane; Tillement, Olivier

2016-07-01

We recently developed the synthesis of ultrasmall gadolinium-based nanoparticles (GBN), (hydrodynamic diameter <5 nm) characterized by a safe behavior after intravenous injection (renal clearance, preferential accumulation in tumors). Owing to the presence of gadolinium ions, GBN can be used as contrast agents for magnetic resonance imaging (MRI) and as radiosensitizers. The attempt to determine the most opportune delay between the intravenous injection of GBN and the irradiation showed that a very low content of radiosensitizing nanoparticles in the tumor area is sufficient (0.1 μg/g of particles, i.e. 15 ppb of gadolinium) for an important increase of the therapeutic effect of irradiation. Such a promising and unexpected result is assigned to a suited distribution of GBN within the tumor, as revealed by the X-ray fluorescence (XRF) maps.

In vitro radiosensitizing effects of ultrasmall gadolinium based particles on tumour cells.

PubMed

Mowat, P; Mignot, A; Rima, W; Lux, F; Tillement, O; Roulin, C; Dutreix, M; Bechet, D; Huger, S; Humbert, L; Barberi-Heyob, M; Aloy, M T; Armandy, E; Rodriguez-Lafrasse, C; Le Duc, G; Roux, S; Perriat, P

2011-09-01

Since radiotherapy is widely used in cancer treatment, it is essential to develop strategies which lower the irradiation burden while increasing efficacy and become efficient even in radio resistant tumors. Our new strategy is relying on the development of solid hybrid nanoparticles based on rare-earth such as gadolinium. In this paper, we then evidenced that gadolinium-based particles can be designed to enter efficiently into the human glioblastoma cell line U87 in quantities that can be tuned by modifying the incubation conditions. These sub-5 nm particles consist in a core of gadolinium oxide, a shell of polysiloxane and are functionalized by diethylenetriaminepentaacetic acid (DTPA). Although photoelectric effect is maximal in the [10-100 keV] range, such particles were found to possess efficient in-vitro radiosensitizing properties at an energy of 660 keV by using the "single-cell gel electrophoresis comet assay," an assay that measures the number of DNA damage that occurs during irradiation. Even more interesting, the particles have been evidenced by MTT assays to be also efficient radiosensitizers at an energy of 6 MeV for doses comprised between 2 and 8 Gy. The properties of the gadolinium-based particles give promising opening to a particle-assisted radio-therapy by using irradiation systems already installed in the majority of hospitals.

In situ fabrication of high-performance Ni-GDC-nanocube core-shell anode for low-temperature solid-oxide fuel cells

PubMed Central

Yamamoto, Kazuhiro; Qiu, Nan; Ohara, Satoshi

2015-01-01

A core–shell anode consisting of nickel–gadolinium-doped-ceria (Ni–GDC) nanocubes was directly fabricated by a chemical process in a solution containing a nickel source and GDC nanocubes covered with highly reactive {001} facets. The cermet anode effectively generated a Ni metal framework even at 500 °C with the growth of the Ni spheres. Anode fabrication at such a low temperature without any sintering could insert a finely nanostructured layer close to the interface between the electrolyte and the anode. The maximum power density of the attractive anode was 97 mW cm–2, which is higher than that of a conventional NiO–GDC anode prepared by an aerosol process at 55 mW cm–2 and 600 °C, followed by sintering at 1300 °C. Furthermore, the macro- and microstructure of the Ni–GDC-nanocube anode were preserved before and after the power-generation test at 700 °C. Especially, the reactive {001} facets were stabled even after generation test, which served to reduce the activation energy for fuel oxidation successfully. PMID:26615816

Gadolinium-Conjugated Gold Nanoshells for Multimodal Diagnostic Imaging and Photothermal Cancer Therapy

PubMed Central

Coughlin, Andrew J.; Ananta, Jeyarama S.; Deng, Nanfu; Larina, Irina V.; Decuzzi, Paolo

2014-01-01

Multimodal imaging offers the potential to improve diagnosis and enhance the specificity of photothermal cancer therapy. Toward this goal, we have engineered gadolinium-conjugated gold nanoshells and demonstrated that they enhance contrast for magnetic resonance imaging, X-Ray, optical coherence tomography, reflectance confocal microscopy, and two-photon luminescence. Additionally, these particles effectively convert near-infrared light to heat, which can be used to ablate cancer cells. Ultimately, these studies demonstrate the potential of gadolinium-nanoshells for image-guided photothermal ablation. PMID:24115690

Highly CO2-Tolerant Cathode for Intermediate-Temperature Solid Oxide Fuel Cells: Samarium-Doped Ceria-Protected SrCo0.85Ta0.15O3-δ Hybrid.

PubMed

Li, Mengran; Zhou, Wei; Zhu, Zhonghua

2017-01-25

Susceptibility to CO 2 is one of the major challenges for the long-term stability of the alkaline-earth-containing cathodes for intermediate-temperature solid oxide fuel cells. To alleviate the adverse effects from CO 2 , we incorporated samarium-stabilized ceria (SDC) into a SrCo 0.85 Ta 0.15 O 3-δ (SCT15) cathode by either mechanical mixing or a wet impregnation method and evaluated their cathode performance stability in the presence of a gas mixture of 10% CO 2 , 21% O 2 , and 69% N 2 . We observed that the CO 2 tolerance of the hybrid cathode outperforms the pure SCT15 cathode by over 5 times at 550 °C. This significant enhancement is likely attributable to the low CO 2 adsorption and reactivity of the SDC protective layer, which are demonstrated through thermogravimetric analysis, energy-dispersive spectroscopy, and electrical conductivity study.

Gadolinium-hydrogen ion exchange of zirconium phosphate

NASA Technical Reports Server (NTRS)

Liu, D. C.; Power, J. L.

1972-01-01

The Gd(+3)/H(+) ion exchange on a commercial zirconium phosphate ion exchanger was investigated in chloride, sulfate, and phosphate solutions of Gd(+3) at gadolinium concentrations of 0.001 to 1 millimole per cc and in the pH range of 0 to 3.5. Relatively low Gd(+3) capacities, in the range of 0.01 to 0.1 millimole per g of ion exchanger were found at room temperature. A significant difference in Gd(+3) sorption was observed, depending on whether the ion exchanger was converted from initial conditions of greater or lesser Gd(+3) sorption than the specific final conditions. Correlations were found between decrease in Gd(+3) capacity and loss of exchanger phosphate groups due to hydrolysis during washing and between increase in capacity and treatment with H3PO4. Fitting of the experimental data to ideal ion exchange equilibrium expressions indicated that each Gd(+3) ion is sorbed on only one site of the ion exchanger. The selectivity quotient was determined to be 2.5 + or - 0.4 at room temperature on gadolinium desorption in chloride solutions.

The Effect of gadolinium on the ESR response of alanine and ammonium tartrate exposed to thermal neutrons.

PubMed

Marrale, Maurizio; Brai, Maria; Gennaro, Gaetano; Bartolotta, Antonio; D'Oca, Maria Cristina

2008-02-01

Many efforts have been made to develop neutron capture therapy (NCT) for cancer treatment. Among the challenges in using NCT is the characterization of the features of the mixed radiation field and of its components. In this study, we examined the enhancement of the ESR response of pellets of alanine and ammonium tartrate with gadolinium oxide exposed to a thermal neutron beam. In particular, the ESR response of these dosimeters as a function of the gadolinium content inside the dosimeter was analyzed. We found that the addition of gadolinium improves the sensitivity of both alanine and ammonium tartrate. However, the use of gadolinium reduces or abolishes tissue equivalence because of its high atomic number (Z(Gd) = 64). Therefore, it is necessary to find the optimum compromise between the sensitivity to thermal neutrons and the reduction of tissue equivalence. Our analysis showed that a low concentration of gadolinium oxide (of the order of 5% of the total mass of the dosimeter) can enhance the thermal neutron sensitivity more than 13 times with an insignificant reduction of tissue equivalence.

Gadolinium-loaded Plastic Scintillators for Thermal Neutron Detection using Compensation

NASA Astrophysics Data System (ADS)

Dumazert, Jonathan; Coulon, Romain; Hamel, Matthieu; Carrel, Frédérick; Sguerra, Fabien; Normand, Stéphane; Méchin, Laurence; Bertrand, Guillaume H. V.

2016-06-01

Plastic scintillator loading with gadolinium-rich organometallic complexes shows a high potential for the deployment of efficient and cost-effective neutron detectors. Due to the low-energy photon and electron signature of thermal neutron capture by Gd-155 and Gd-157, alternative treatment to pulse-shape discrimination has to be proposed in order to display a count rate. This paper discloses the principle of a compensation method applied to a two-scintillator system: a detection scintillator interacts with photon and fast neutron radiation and is loaded with gadolinium organometallic compound to become a thermal neutron absorber, while a not-gadolinium loaded compensation scintillator solely interacts with the fast neutron and photon part of incident radiation. After the nonlinear smoothing of the counting signals, a hypothesis test determines whether the resulting count rate post-background response compensation falls into statistical fluctuations or provides a robust indication of neutron activity. Laboratory samples are tested under both photon and neutron irradiations, allowing the authors to investigate the performance of the overall detection system in terms of sensitivity and detection limits, especially with regards to a similar-active volume He-3 based commercial counter. The study reveals satisfactory figures of merit in terms of sensitivity and directs future investigation toward promising paths.

Tracing gadolinium-based contrast agents from surface water to drinking water by means of speciation analysis.

PubMed

Birka, Marvin; Wehe, Christoph A; Hachmöller, Oliver; Sperling, Michael; Karst, Uwe

2016-04-01

In recent decades, a significant amount of anthropogenic gadolinium has been released into the environment as a result of the broad application of contrast agents for magnetic resonance imaging (MRI). Since this anthropogenic gadolinium anomaly has also been detected in drinking water, it has become necessary to investigate the possible effect of drinking water purification on these highly polar microcontaminats. Therefore, a novel highly sensitive method for speciation analysis of gadolinium is presented. For that purpose, the hyphenation of hydrophilic interaction liquid chromatography (HILIC) and inductively coupled plasma-mass spectrometry (ICP-MS) was employed. In order to enhance the detection power, sample introduction was carried out by ultrasonic nebulization. In combination with a novel HILIC method using a diol-based stationary phase, it was possible to achieve superior limits of detection for frequently applied gadolinium-based contrast agents below 20pmol/L. With this method, the contrast agents Gd-DTPA, Gd-DOTA and Gd-BT-DO3A were determined in concentrations up to 159pmol/L in samples from several waterworks in a densely populated region of Germany alongside the river Ruhr as well as from a waterworks near a catchment lake. Thereby, the direct impact of anthropogenic gadolinium species being present in the surface water on the amount of anthropogenic gadolinium in drinking water was shown. There was no evidence for the degradation of contrast agents, the release of Gd(3+) or the presence of further Gd species. Copyright © 2016 Elsevier B.V. All rights reserved.

A polymeric fastener can easily functionalize liposome surfaces with gadolinium for enhanced magnetic resonance imaging.

PubMed

Smith, Cartney E; Shkumatov, Artem; Withers, Sarah G; Yang, Binxia; Glockner, James F; Misra, Sanjay; Roy, Edward J; Wong, Chun-Ho; Zimmerman, Steven C; Kong, Hyunjoon

2013-11-26

Common methods of loading magnetic resonance imaging (MRI) contrast agents into nanoparticles often suffer from challenges related to particle formation, complex chemical modification/purification steps, and reduced contrast efficiency. This study presents a simple, yet advanced process to address these issues by loading gadolinium, an MRI contrast agent, exclusively on a liposome surface using a polymeric fastener. The fastener, so named for its ability to physically link the two functional components together, consisted of chitosan substituted with diethylenetriaminepentaacetic acid (DTPA) to chelate gadolinium, as well as octadecyl chains to stabilize the modified chitosan on the liposome surface. The assembly strategy, mimicking the mechanisms by which viruses and proteins naturally anchor to a cell, provided greater T1 relaxivity than liposomes loaded with gadolinium in both the interior and outer leaflet. Gadolinium-coated liposomes were ultimately evaluated in vivo using murine ischemia models to highlight the diagnostic capability of the system. Taken together, this process decouples particle assembly and functionalization and, therefore, has considerable potential to enhance imaging quality while alleviating many of the difficulties associated with multifunctional particle fabrication.

A Polymeric Fastener can Easily Functionalize Liposome Surfaces with Gadolinium for Enhanced Magnetic Resonance Imaging

PubMed Central

Smith, Cartney E.; Shkumatov, Artem; Withers, Sarah G.; Glockner, James F.; Misra, Sanjay; Roy, Edward J.; Wong, Chun-Ho; Zimmerman, Steven C.; Kong, Hyunjoon

2013-01-01

Common methods of loading magnetic resonance imaging (MRI) contrast agents into nanoparticles often suffer from challenges related to particle formation, complex chemical modification/purification steps, and reduced contrast efficiency. This study presents a simple, yet advanced process to address these issues by loading gadolinium, an MRI contrast agent, exclusively on a liposome surface using a polymeric fastener. The fastener, so named for its ability to physically link the two functional components together, consisted of chitosan substituted with diethylenetriaminepentaacetic acid (DTPA) to chelate gadolinium, as well as octadecyl chains to stabilize the modified chitosan on the liposome surface. The assembly strategy, mimicking the mechanisms by which viruses and proteins naturally anchor to a cell, provided greater T1 relaxivity than liposomes loaded with gadolinium in both the interior and outer leaflet. Gadolinium-coated liposomes were ultimately evaluated in vivo using murine ischemia models to highlight the diagnostic capability of the system. Taken together, this process decouples particle assembly and functionalization, and therefore has considerable potential to enhance imaging quality while alleviating many of the difficulties associated with multifunctional particle fabrication. PMID:24083377

Ceria-supported ruthenium nanoparticles as highly active and long-lived catalysts in hydrogen generation from the hydrolysis of ammonia borane.

PubMed

Akbayrak, Serdar; Tonbul, Yalçın; Özkar, Saim

2016-07-05

Ruthenium(0) nanoparticles supported on ceria (Ru(0)/CeO2) were in situ generated from the reduction of ruthenium(iii) ions impregnated on ceria during the hydrolysis of ammonia borane. Ru(0)/CeO2 was isolated from the reaction solution by centrifugation and characterized by ICP-OES, BET, XRD, TEM, SEM-EDS and XPS techniques. All the results reveal that ruthenium(0) nanoparticles were successfully supported on ceria and the resulting Ru(0)/CeO2 is a highly active, reusable and long-lived catalyst for hydrogen generation from the hydrolysis of ammonia borane with a turnover frequency value of 361 min(-1). The reusability tests reveal that Ru(0)/CeO2 is still active in the subsequent runs of hydrolysis of ammonia borane preserving 60% of the initial catalytic activity even after the fifth run. Ru(0)/CeO2 provides a superior catalytic lifetime (TTO = 135 100) in hydrogen generation from the hydrolysis of ammonia borane at 25.0 ± 0.1 °C before deactivation. The work reported here includes the formation kinetics of ruthenium(0) nanoparticles. The rate constants for the slow nucleation and autocatalytic surface growth of ruthenium(0) nanoparticles were obtained using hydrogen evolution as a reporter reaction. An evaluation of rate constants at various temperatures enabled the estimation of activation energies for both the reactions, Ea = 60 ± 7 kJ mol(-1) for the nucleation and Ea = 47 ± 2 kJ mol(-1) for the autocatalytic surface growth of ruthenium(0) nanoparticles, as well as the activation energy of Ea = 51 ± 2 kJ mol(-1) for the catalytic hydrolysis of ammonia borane.

SolarSyngas: Results from a virtual institute developing materials and key components for solar thermochemical fuel production

NASA Astrophysics Data System (ADS)

Roeb, Martin; Steinfeld, Aldo; Borchardt, Günter; Feldmann, Claus; Schmücker, Martin; Sattler, Christian; Pitz-Paal, Robert

2016-05-01

The Helmholtz Virtual Institute (VI) SolarSynGas brings together expertise from solar energy research and materials science to develop metal oxide based redox materials and to integrate them in a suitable way into related process technologies for two-step thermochemical production of hydrogen and carbon monoxide from water and CO2. One of the foci of experimental investigation was exploring the impact of doping on the feasibility of ceria-based materials - mainly by Zr-doping. The results indicate that a certain Zr-content enhances the reducibility and therefore the splitting performance. Increasing the Zr-content to x = 0.15 improved the specific CO2-splitting performance by 50% compared to pure ceria. This finding agrees with theoretical studies attributing the improvements to lattice modification caused by the introduction of Zr4+. Thermogravimetric relaxation experiments and equilibrium oxygen isotope exchange experiments with subsequent depth profiling analysis were carried out on ceria. As a result the reduction reaction of even dense samples of pure ceria with a grain size of about 20 µm is surface reaction controlled. The structure of the derived expression for the apparent activation energy suggests that the chemical surface exchange coefficient should show only a very weak dependence on temperature for ceria doped with lower valence cations. A solar receiver reactor exhibiting a foam-type reticulated porous ceramics made of ceria was tested. It could be shown that applying dual-scale porosity to those foams with mm-size pores for effective radiative heat transfer during reduction and μm-size pores within its struts for enhanced kinetics during oxidation allows enhancing the performance of the reactor significantly. Also a particle process concept applying solid-solid heat recovery from redox particles in a high temperature solar thermochemical process was analysed that uses ceramic spheres as solid heat transfer medium. This concept can be implemented

Structure and chemistry of epitaxial ceria thin films on yttria-stabilized zirconia substrates, studied by high resolution electron microscopy

DOE PAGES

Sinclair, Robert; Lee, Sang Chul; Shi, Yezhou; ...

2017-03-18

Here, we have applied aberration-corrected transmission electron microscopy (TEM) imaging and electron energy loss spectroscopy (EELS) to study the structure and chemistry of epitaxial ceria thin films, grown by pulsed laser deposition onto (001) yttria-stabilized zirconia (YSZ) substrates. There are few observable defects apart from the expected mismatch interfacial dislocations and so the films would be expected to have good potential for applications. Under high electron beam dose rate (above about 6000 e-/Å 2s) domains of an ordered structure appear and these are interpreted as being created by oxygen vacancy ordering. The ordered structure does not appear at lower losemore » rates (ca. 2600 e-/Å 2s) and can be removed by imaging under 1 mbar oxygen gas in an environmental TEM. EELS confirms that there is both oxygen deficiency and the associated increase in Ce 3+ versus Ce 4+ cations in the ordered domains. In situ high resolution TEM recordings show the formation of the ordered domains as well as atomic migration along the ceria thin film (001) surface.« less

Structure and chemistry of epitaxial ceria thin films on yttria-stabilized zirconia substrates, studied by high resolution electron microscopy

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

Sinclair, Robert; Lee, Sang Chul; Shi, Yezhou

Here, we have applied aberration-corrected transmission electron microscopy (TEM) imaging and electron energy loss spectroscopy (EELS) to study the structure and chemistry of epitaxial ceria thin films, grown by pulsed laser deposition onto (001) yttria-stabilized zirconia (YSZ) substrates. There are few observable defects apart from the expected mismatch interfacial dislocations and so the films would be expected to have good potential for applications. Under high electron beam dose rate (above about 6000 e-/Å 2s) domains of an ordered structure appear and these are interpreted as being created by oxygen vacancy ordering. The ordered structure does not appear at lower losemore » rates (ca. 2600 e-/Å 2s) and can be removed by imaging under 1 mbar oxygen gas in an environmental TEM. EELS confirms that there is both oxygen deficiency and the associated increase in Ce 3+ versus Ce 4+ cations in the ordered domains. In situ high resolution TEM recordings show the formation of the ordered domains as well as atomic migration along the ceria thin film (001) surface.« less

Current German Laser and Quantum Optics Research Reviewed at the 50th Annual Meeting of the Physikalische Gesellschaft.

DTIC Science & Technology

1986-04-23

Physics, Munster In the area of generating useable University) studied an interesting de- coherent high-frequency radiation, I vice, a silicon Fabry ...has a substantial crys- tingen) described studies with Cr- plus tal growing capability. One paper from Nd-doped gadolinium -scandium-gallium the Hamburg...institute, read by J. Drube, garnets (GSGG), and also with Cr-doped reported on Xe-flashlamp-pumped Cr:CSA(; % gadolinium -scandium-aluminum garnets

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.

Gadolinium deposition disease: Initial description of a disease that has been around for a while.

PubMed

Semelka, Richard C; Ramalho, Joana; Vakharia, Ami; AlObaidy, Mamdoh; Burke, Lauren M; Jay, Michael; Ramalho, Miguel

2016-12-01

To describe the clinical manifestations of presumed gadolinium toxicity in patients with normal renal function. Participants were recruited from two online gadolinium toxicity support groups. The survey was anonymous and individuals were instructed to respond to the survey only if they had evidence of normal renal function, evidence of gadolinium in their system beyond 30days of this MRI, and no pre-existent clinical symptoms and/or signs of this type. 42 subjects responded to the survey (age: 28-69, mean 49.1±22.4years). The most common findings were: central pain (n=15), peripheral pain (n=26), headache (n=28), and bone pain (n=26). Only subjects with distal leg and arm distribution described skin thickening (n=22). Clouded mentation and headache were the symptoms described as persistent beyond 3months in 29 subjects. Residual disease was present in all patients. Twenty-eight patients described symptoms following administration of one brand of Gadolinium-Based Contrast Agent (GBCA), 21 after a single GBCA administration and 7 after multiple GBCA administrations, including: gadopentetate dimeglumine, n=9; gadodiamide, n=4; gadoversetamide, n=4; gadobenate dimeglumine, n=4; gadobutrol, n=1; gadoteridol, n=2; and unknown, n=4. Gadolinium toxicity appears to arise following GBCA administration, which appears to contain clinical features seen in Nephrogenic Systemic Fibrosis, but also features not observed in that condition. Copyright © 2016 Elsevier Inc. All rights reserved.

Gadolinium-based Contrast Media, Cerebrospinal Fluid and the Glymphatic System: Possible Mechanisms for the Deposition of Gadolinium in the Brain.

PubMed

Taoka, Toshiaki; Naganawa, Shinji

2018-04-10

After Kanda's first report in 2014 on gadolinium (Gd) deposition in brain tissue, a considerable number of studies have investigated the explanation for the observation. Gd deposition in brain tissue after repeated administration of gadolinium-based contrast medium (GBCM) has been histologically proven, and chelate stability has been shown to affect the deposition. However, the mechanism for this deposition has not been fully elucidated. Recently, a hypothesis was introduced that involves the 'glymphatic system', which is a coined word that combines 'gl' for glia cell and 'lymphatic' system. According to this hypothesis, the perivascular space functions as a conduit for cerebrospinal fluid to flow into the brain parenchyma. The perivascular space around the arteries allows cerebrospinal fluid to enter the interstitial space of the brain tissue through water channels controlled by aquaporin 4. The cerebrospinal fluid entering the interstitial space clears waste proteins from the tissue. It then flows into the perivascular space around the vein and is discharged outside the brain. In addition to the hypothesis regarding the glymphatic system, some reports have described that after GBCM administration, some of the GBCM distributes through systemic blood circulation and remains in other compartments including the cerebrospinal fluid. It is thought that the GBCM distributed into the cerebrospinal fluid cavity via the glymphatic system may remain in brain tissue for a longer duration compared to the GBCM in systemic circulation. Glymphatic system may of course act as a clearance system for GBCM from brain tissue. Based on these findings, the mechanism for Gd deposition in the brain will be discussed in this review. The authors speculate that the glymphatic system may be the major contributory factor to the deposition and clearance of gadolinium in brain tissue.

Gadolinium-based Contrast Media, Cerebrospinal Fluid and the Glymphatic System: Possible Mechanisms for the Deposition of Gadolinium in the Brain

PubMed Central

Taoka, Toshiaki; Naganawa, Shinji

2018-01-01

After Kanda’s first report in 2014 on gadolinium (Gd) deposition in brain tissue, a considerable number of studies have investigated the explanation for the observation. Gd deposition in brain tissue after repeated administration of gadolinium-based contrast medium (GBCM) has been histologically proven, and chelate stability has been shown to affect the deposition. However, the mechanism for this deposition has not been fully elucidated. Recently, a hypothesis was introduced that involves the ‘glymphatic system’, which is a coined word that combines ‘gl’ for glia cell and ‘lymphatic’ system. According to this hypothesis, the perivascular space functions as a conduit for cerebrospinal fluid to flow into the brain parenchyma. The perivascular space around the arteries allows cerebrospinal fluid to enter the interstitial space of the brain tissue through water channels controlled by aquaporin 4. The cerebrospinal fluid entering the interstitial space clears waste proteins from the tissue. It then flows into the perivascular space around the vein and is discharged outside the brain. In addition to the hypothesis regarding the glymphatic system, some reports have described that after GBCM administration, some of the GBCM distributes through systemic blood circulation and remains in other compartments including the cerebrospinal fluid. It is thought that the GBCM distributed into the cerebrospinal fluid cavity via the glymphatic system may remain in brain tissue for a longer duration compared to the GBCM in systemic circulation. Glymphatic system may of course act as a clearance system for GBCM from brain tissue. Based on these findings, the mechanism for Gd deposition in the brain will be discussed in this review. The authors speculate that the glymphatic system may be the major contributory factor to the deposition and clearance of gadolinium in brain tissue. PMID:29367513

Improvement of performance in low temperature solid oxide fuel cells operated on ethanol and air mixtures using Cu-ZnO-Al2O3 catalyst layer

NASA Astrophysics Data System (ADS)

Morales, M.; Espiell, F.; Segarra, M.

2015-10-01

Anode-supported single-chamber solid oxide fuel cells with and without Cu-ZnO-Al2O3 catalyst layers deposited on the anode support have been operated on ethanol and air mixtures. The cells consist of gadolinia-doped ceria electrolyte, Ni-doped ceria anode, and La0.6Sr0.4CoO3-δ-doped ceria cathode. Catalyst layers with different Cu-ZnO-Al2O3 ratios are deposited and sintered at several temperatures. Since the performance of single-chamber fuel cells strongly depends on catalytic properties of electrodes for partial oxidation of ethanol, the cells are electrochemically characterized as a function of the temperature, ethanol-air molar ratio and gas flow rate. In addition, catalytic activities of supported anode, catalytic layer-supported anode and cathode for partial oxidation of ethanol are analysed. Afterwards, the effect of composition and sintering temperature of catalyst layer on the cell performance are determined. The results indicate that the cell performance can be significantly enhanced using catalyst layers of 30:35:35 and 40:30:30 wt.% Cu-ZnO-Al2O3 sintered at 1100 °C, achieving power densities above 50 mW cm-2 under 0.45 ethanol-air ratio at temperatures as low as 450 °C. After testing for 15 h, all cells present a gradual loss of power density, without carbon deposition, which is mainly attributed to the partial re-oxidation of Ni at the anode.

Do we need gadolinium-based contrast medium for brain magnetic resonance imaging in children?

PubMed

Dünger, Dennis; Krause, Matthias; Gräfe, Daniel; Merkenschlager, Andreas; Roth, Christian; Sorge, Ina

2018-06-01

Brain imaging is the most common examination in pediatric magnetic resonance imaging (MRI), often combined with the use of a gadolinium-based contrast medium. The application of gadolinium-based contrast medium poses some risk. There is limited evidence of the benefits of contrast medium in pediatric brain imaging. To assess the diagnostic gain of contrast-enhanced sequences in brain MRI when the unenhanced sequences are normal. We retrospectively assessed 6,683 brain MR examinations using contrast medium in children younger than 16 years in the pediatric radiology department of the University Hospital Leipzig to determine whether contrast-enhanced sequences delivered additional, clinically relevant information to pre-contrast sequences. All examinations were executed using a 1.5-T or a 3-T system. In 8 of 3,003 (95% confidence interval 0.12-0.52%) unenhanced normal brain examinations, a relevant additional finding was detected when contrast medium was administered. Contrast enhancement led to a change in diagnosis in only one of these cases. Children with a normal pre-contrast brain MRI rarely benefit from contrast medium application. Comparing these results to the risks and disadvantages of a routine gadolinium application, there is substantiated numerical evidence for avoiding routine administration of gadolinium in a pre-contrast normal MRI examination.

Accumulation of MRI contrast agents in malignant fibrous histiocytoma for gadolinium neutron capture therapy.

PubMed

Fujimoto, T; Ichikawa, H; Akisue, T; Fujita, I; Kishimoto, K; Hara, H; Imabori, M; Kawamitsu, H; Sharma, P; Brown, S C; Moudgil, B M; Fujii, M; Yamamoto, T; Kurosaka, M; Fukumori, Y

2009-07-01

Neutron-capture therapy with gadolinium (Gd-NCT) has therapeutic potential, especially that gadolinium is generally used as a contrast medium in magnetic resonance imaging (MRI). The accumulation of gadolinium in a human sarcoma cell line, malignant fibrosis histiocytoma (MFH) Nara-H, was visualized by the MRI system. The commercially available MRI contrast medium Gd-DTPA (Magnevist, dimeglumine gadopentetate aqueous solution) and the biodegradable and highly gadopentetic acid (Gd-DTPA)-loaded chitosan nanoparticles (Gd-nanoCPs) were prepared as MRI contrast agents. The MFH cells were cultured and collected into three falcon tubes that were set into the 3-tesra MRI system to acquire signal intensities from each pellet by the spin echo method, and the longitudinal relaxation time (T1) was calculated. The amount of Gd in the sample was measured by inductively coupled plasma atomic emission spectrography (ICP-AES). The accumulation of gadolinium in cells treated with Gd-nanoCPs was larger than that in cells treated with Gd-DTPA. In contrast, and compared with the control, Gd-DTPA was more effective than Gd-nanoCPs in reducing T1, suggesting that the larger accumulation exerted the adverse effect of lowering the enhancement of MRI. Further studies are warranted to gain insight into the therapeutic potential of Gd-NCT.

Multispectral Emissions of Lanthanide-Doped Gadolinium Oxide Nanophosphors for Cathodoluminescence and Near-Infrared Upconversion/Downconversion Imaging

PubMed Central

Thi Kim Dung, Doan; Fukushima, Shoichiro; Furukawa, Taichi; Niioka, Hirohiko; Sannomiya, Takumi; Kobayashi, Kaori; Yukawa, Hiroshi; Baba, Yoshinobu; Hashimoto, Mamoru; Miyake, Jun

2016-01-01

Comprehensive imaging of a biological individual can be achieved by utilizing the variation in spatial resolution, the scale of cathodoluminescence (CL), and near-infrared (NIR), as favored by imaging probe Gd2O3 co-doped lanthanide nanophosphors (NPPs). A series of Gd2O3:Ln3+/Yb3+ (Ln3+: Tm3+, Ho3+, Er3+) NPPs with multispectral emission are prepared by the sol-gel method. The NPPs show a wide range of emissions spanning from the visible to the NIR region under 980 nm excitation. The dependence of the upconverting (UC)/downconverting (DC) emission intensity on the dopant ratio is investigated. The optimum ratios of dopants obtained for emissions in the NIR regions at 810 nm, 1200 nm, and 1530 nm are applied to produce nanoparticles by the homogeneous precipitation (HP) method. The nanoparticles produced from the HP method are used to investigate the dual NIR and CL imaging modalities. The results indicate the possibility of using Gd2O3 co-doped Ln3+/Yb3+ (Ln3+: Tm3+, Ho3+, Er3+) in correlation with NIR and CL imaging. The use of Gd2O3 promises an extension of the object dimension to the whole-body level by employing magnetic resonance imaging (MRI). PMID:28335291

Multispectral Emissions of Lanthanide-Doped Gadolinium Oxide Nanophosphors for Cathodoluminescence and Near-Infrared Upconversion/Downconversion Imaging.

PubMed

Thi Kim Dung, Doan; Fukushima, Shoichiro; Furukawa, Taichi; Niioka, Hirohiko; Sannomiya, Takumi; Kobayashi, Kaori; Yukawa, Hiroshi; Baba, Yoshinobu; Hashimoto, Mamoru; Miyake, Jun

2016-09-06

Comprehensive imaging of a biological individual can be achieved by utilizing the variation in spatial resolution, the scale of cathodoluminescence (CL), and near-infrared (NIR), as favored by imaging probe Gd₂O₃ co-doped lanthanide nanophosphors (NPPs). A series of Gd₂O₃:Ln 3+ /Yb 3+ (Ln 3+ : Tm 3+ , Ho 3+ , Er 3+ ) NPPs with multispectral emission are prepared by the sol-gel method. The NPPs show a wide range of emissions spanning from the visible to the NIR region under 980 nm excitation. The dependence of the upconverting (UC)/downconverting (DC) emission intensity on the dopant ratio is investigated. The optimum ratios of dopants obtained for emissions in the NIR regions at 810 nm, 1200 nm, and 1530 nm are applied to produce nanoparticles by the homogeneous precipitation (HP) method. The nanoparticles produced from the HP method are used to investigate the dual NIR and CL imaging modalities. The results indicate the possibility of using Gd₂O₃ co-doped Ln 3+ /Yb 3+ (Ln 3+ : Tm 3+ , Ho 3+ , Er 3+ ) in correlation with NIR and CL imaging. The use of Gd₂O₃ promises an extension of the object dimension to the whole-body level by employing magnetic resonance imaging (MRI).

Critical Questions Regarding Gadolinium Deposition in the Brain and Body After Injections of the Gadolinium-Based Contrast Agents, Safety, and Clinical Recommendations in Consideration of the EMA's Pharmacovigilance and Risk Assessment Committee Recommendation for Suspension of the Marketing Authorizations for 4 Linear Agents.

PubMed

Runge, Val M

2017-06-01

For magnetic resonance, the established class of intravenous contrast media is the gadolinium-based contrast agents. In the 3 decades since initial approval, these have proven in general to be very safe for human administration. However, in 2006, a devastating late adverse reaction to administration of the less stable gadolinium-based contrast agents was identified, nephrogenic systemic fibrosis. The result of actions taken by the European Medicines Agency and the US Food and Drug Administration, stratifying the agents by risk and contraindicating specific agents in severe renal dysfunction, has led to no new cases being identified in North America or Europe. Subsequently, in 2014, long-term deposition in the brain of gadolinium was first shown, after administration of 2 nonionic linear chelates, gadodiamide, and gadopentetate dimeglumine. This has led to an intense focus on the question of in vivo distribution, possible dechelation, and subsequent deposition of gadolinium, together with substantial clarification of the phenomenon as well as stratification of the agents on this basis. This review focuses on 8 critical questions regarding gadolinium deposition in the brain and body, with the answers and discussion therein important for future regulatory decisions and clinical practice. It is now clear that dechelation of gadolinium occurs in vivo with the linear agents and is responsible for this phenomenon, with key experts in the field recommending, except where there is no suitable alternative, a shift in clinical practice from the linear to macrocyclic agents. In addition, on March 10, 2017, the Pharmacovigilance and Risk Assessment Committee of the European Medicines Agency recommended suspension of the marketing authorization for 4 linear gadolinium contrast agents-specifically Omniscan, Optimark, Magnevist, and MultiHance (gadodiamide, gadoversetamide, gadopentetate dimeglumine, and gadobenate dimeglumine)-for intravenous injection. Cited in the report was

Type-II domains in ferroelectric gadolinium molybdate (in German)

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

Bohm, J.; Kuersten, H.D.

Etching (001)-faces of gadolinium molybdate (GMO) reveals new kinds of domains. They are created by a translation, that leaves the spontaneous polarization and the transition parameter invariant. The translation vector is a part of a lattice vector, similar to stacking faults. (auth)

Preparation of Sm-doped ceria (SDC) nanowires and tubes by gas-liquid co-precipitation at room temperature

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

Gu Lina; School of Chemistry and Chemical Engineering, Anhui University, 230039 Hefei; Meng Guangyao

Sm-doped cerium dioxide (SDC) with fcc structure was formed using a gas-liquid chemical co-precipitation process at room temperature. Morphology and structure of the as-prepared samples were characterized using TG, XRD, TEM, HRTEM and SAED techniques. Under our specific experimental conditions, two kinds of 1D nano-structures SDC have been mainly obtained. SDC nanowires are 0.3-1.2 {mu}m in lengths and 5-20 nm in diameters. SDC nanotubes have outer diameters in 10-40 nm with lengths up to 2 {mu}m. The as-prepared SDC shows very strong UV absorption ability and the maximum absorption peak redshifts compared with that of SDC nanoparticles.

Color-Center Production and Formation in Electron-Irradiated Magnesium Aluminate Spinel and Ceria

DOE PAGES

Costantini, Jean-Marc; Lelong, Gerald; Guillaumet, Maxime; ...

2016-06-20

Single crystals of magnesium aluminate spinel (MgAl2O4) with (100) or (110) orientations and cerium dioxide or ceria (CeO2) were irradiated by 1.0-MeV and 2.5-MeV electrons in a high fluence range. Point-defect production was studied by off-line UV-visible optical spectroscopy after irradiation. For spinel, regardless of both crystal orientation and electron energy, two characteristic broad bands centered at photon energies of 5.4 eV and 4.9 eV were assigned to F and F+ centers (neutral and singly-ionized oxygen vacancies), respectively, on the basis of available literature data. No clear differences in colour-centre formation were observed for the two crystal orientations. Using calculationsmore » of displacement cross sections by elastic collisions, these results are consistent with a very large threshold displacement energy (200 eV) for oxygen atoms at RT. A third very broad band centered at 3.7 eV might be attributed either to an oxygen hole center (V-type center) or an F2 dimer center (oxygen di-vacancy). The onset of recovery of these color centers took place at 200°C with almost full bleaching at 600°C. Activation energies (~0.3-0.4 eV) for defect recovery were deduced from the isochronal annealing data by using a first-order kinetics analysis. For ceria, a sub band-gap absorption feature peaked at ~3.1 eV was recorded for 2.5-MeV electron irradiation only. Assuming a ballistic process, we suggest that the latter defect might result from cerium atom displacement on the basis of computed cross sections.« less

Unique properties of ceria nanoparticles supported on metals: novel inverse ceria/copper catalysts for CO oxidation and the water-gas shift reaction.

PubMed

Senanayake, Sanjaya D; Stacchiola, Dario; Rodriguez, Jose A

2013-08-20

Oxides play a central role in important industrial processes, including applications such as the production of renewable energy, remediation of environmental pollutants, and the synthesis of fine chemicals. They were originally used as catalyst supports and were thought to be chemically inert, but now they are used to build catalysts tailored toward improved selectivity and activity in chemical reactions. Many studies have compared the morphological, electronic, and chemical properties of oxide materials with those of unoxidized metals. Researchers know much less about the properties of oxides at the nanoscale, which display distinct behavior from their bulk counterparts. More is known about metal nanoparticles. Inverse-model catalysts, composed of oxide nanoparticles supported on metal or oxide substrates instead of the reverse (oxides supporting metal nanoparticles), are excellent tools for systematically testing the properties of novel catalytic oxide materials. Inverse models are prepared in situ and can be studied with a variety of surface science tools (e.g. scanning tunneling microscopy, X-ray photoemission spectroscopy, ultraviolet photoemission spectroscopy, low-energy electron microscopy) and theoretical tools (e.g. density functional theory). Meanwhile, their catalytic activity can be tested simultaneously in a reactor. This approach makes it possible to identify specific functions or structures that affect catalyst performance or reaction selectivity. Insights gained from these tests help to tailor powder systems, with the primary objective of rational design (experimental and theoretical) of catalysts for specific chemical reactions. This Account describes the properties of inverse catalysts composed of CeOx nanoparticles supported on Cu(111) or CuOx/Cu(111) as determined through the methods described above. Ceria is an important material for redox chemistry because of its interchangeable oxidation states (Ce⁴⁺ and Ce³⁺). Cu(111), meanwhile, is

The Effect of Pressure and Temperature on Separation of Free Gadolinium(III) From Gd-DTPA Complex by Nanofiltration-Complexation Method

NASA Astrophysics Data System (ADS)

Rahayu, Iman; Anggraeni, Anni; Ukun, MSS; Bahti, Husein H.

2017-05-01

Nowdays, the utilization of rare earth elements has been carried out widely in industry and medicine, one of them is gadolinium in Gd-DTPA complex is used as a contrast agent in a magnetic resonance imaging (MRI) diagnostic to increase the visual contrast between normal tissue and diseased. Although the stability of a given complex may be high enough, the complexation step couldnot have been completed, so there is possible to gadolinium(III) in the complex compound. Therefore, the function of that compounds should be dangerous because of the toxicity of gadolinium(III) in human body. So, it is necessarry to separate free gadolinium(III) from Gd-DTPA complex by nanofiltration-complexation. The method of this study is complexing of Gd2O3 with DTPA ligand by reflux and separation of Gd-DTPA complex from gadolinium(III) with a nanofiltration membrane on the variation of pressures(2, 3, 4, 5, 6 bars) and temperature (25, 30, 35, 40 °C) and determined the flux and rejection. The results of this study are the higher of pressures and temperatures, permeation flux are increasing and ion rejections are decreasing and gave the free gadolinium(III) rejection until 86.26%.

Assessment of gadolinium calcium oxoborate (GdCOB) for laser applications

NASA Astrophysics Data System (ADS)

Bajor, A. L.; Kisielewski, J.; Kłos, A.; Kopczyński, K.; Łukasiewicz, T.; Mierczyk, J.; Młyńczak, J.

2011-12-01

Increasing demand for growing high quality laser crystals puts a question about their most important parameters that one should concentrate on to get a desired product which will exhibit best properties in practical use. And by no means, this is a simple question. Apart of the usual lasing properties associated with a special dopant in the host material itself, one needs to consider another two lasing phenomena, namely second (SHG) and higher harmonic generation, and self-frequency doubling (SFD). Not necessarily all of these three can meet altogether in the same host material to yield in its best appearance in every case. We have made a review of basic properties of gadolinium oxoborate GdCa4O(BO3)3 (GdCOB) crystal and came to the conclusion that, currently, as a host material this is probably the best in all of its lasing applications. Although GdCOB has low thermal conductivity, which requires a suitable cooling, on the other hand it has got small thermo-optic coefficients which govern good operation in SHG and SFD experiments. Two inch dia. Nd-doped crystals were grown by the Czochralski technique. Since a large discrepancy in the literature exists on exact values of nonlinear coefficients, one is never sure about this whether theoretically predicted phase-matching angles (PMA) are those that are really optimal. Besides, none has yet measured the values of nonlinear coefficients as a function of doping concentration. Therefore we have not decided to cut numerous differently oriented samples for generation of different wavelengths in SHG and SFD, but rather tried to generate different wavelengths from the same samples. We have also not paid special attention to get highest possible conversion efficiencies. However, we have concentrated our attention on potential use of the core region in laser technique. Unlike in YAG crystals, when the core is by all means a parasitic structure, we discovered that the core region in GdCOB, that majority of investigators are

Biocompatible Polyhydroxyethylaspartamide-based Micelles with Gadolinium for MRI Contrast Agents

PubMed Central

2010-01-01

Biocompatible poly-[N-(2-hydroxyethyl)-d,l-aspartamide]-methoxypoly(ethyleneglycol)-hexadecylamine (PHEA-mPEG-C16) conjugated with 1,4,7,10-tetraazacyclododecan-1,4,7,10-tetraacetic acid-gadolinium (DOTA-Gd) via ethylenediamine (ED) was synthesized as a magnetic resonance imaging (MRI) contrast agent. Amphiphilic PHEA-mPEG-C16-ED-DOTA-Gd forms micelle in aqueous solution. All the synthesized materials were characterized by proton nuclear magnetic resonance (1H NMR). Micelle size and shape were examined by dynamic light scattering (DLS) and atomic force microscopy (AFM). Micelles with PHEA-mPEG-C16-ED-DOTA-Gd showed higher relaxivities than the commercially available gadolinium contrast agent. Moreover, the signal intensity of a rabbit liver was effectively increased after intravenous injection of PHEA-mPEG-C16-ED-DOTA-Gd. PMID:21170410

Biocompatible Polyhydroxyethylaspartamide-based Micelles with Gadolinium for MRI Contrast Agents

NASA Astrophysics Data System (ADS)

Jeong, Sang Young; Kim, Hyo Jeong; Kwak, Byung-Kook; Lee, Ha-Young; Seong, Hasoo; Shin, Byung Cheol; Yuk, Soon Hong; Hwang, Sung-Joo; Cho, Sun Hang

2010-12-01

Biocompatible poly-[ N-(2-hydroxyethyl)- d, l-aspartamide]-methoxypoly(ethyleneglycol)-hexadecylamine (PHEA-mPEG-C16) conjugated with 1,4,7,10-tetraazacyclododecan-1,4,7,10-tetraacetic acid-gadolinium (DOTA-Gd) via ethylenediamine (ED) was synthesized as a magnetic resonance imaging (MRI) contrast agent. Amphiphilic PHEA-mPEG-C16-ED-DOTA-Gd forms micelle in aqueous solution. All the synthesized materials were characterized by proton nuclear magnetic resonance (1H NMR). Micelle size and shape were examined by dynamic light scattering (DLS) and atomic force microscopy (AFM). Micelles with PHEA-mPEG-C16-ED-DOTA-Gd showed higher relaxivities than the commercially available gadolinium contrast agent. Moreover, the signal intensity of a rabbit liver was effectively increased after intravenous injection of PHEA-mPEG-C16-ED-DOTA-Gd.

Electron magnetic resonance investigation of gadolinium diffusion in zircon powders

NASA Astrophysics Data System (ADS)

de Biasi, R. S.; Grillo, M. L. N.

2011-11-01

The electron magnetic resonance (EMR) technique was used to investigate the diffusion of gadolinium in zircon (ZrSiO4) powders. The EMR absorption intensity was measured for several annealing times and three different temperatures of isothermal annealing: 1273, 1323 and 1373 K. The activation energy for diffusion, calculated from the experimental data using a theoretical model based on the Fick equation, was found to be EA=506±5 kJ mol-1. This value is close to the ones for the diffusion of Gd in UO2 and CeO2, but much larger than for the diffusion of gadolinium in a compound with the same crystal structure as zircon, YVO4. This is attributed to a difference in the relative sizes of the ions involved in the diffusion process.

Gadolinium concentration analysis in brain phantom by X-ray fluorescence.

PubMed

Almalki, Musaed; Majid, Samir Abdul; Butler, Philip H; Reinisch, Lou

2010-06-01

We have measured the X-ray fluorescence from gadolinium as a function of concentration and position in tumors of different sizes and shapes in a head phantom. The gadolinium fluorescence was excited with a 36 GBq Am-241 source. The fluorescence signal was detected with a CdTe detector and a multi-channel analyzer. The fluorescence peak was clearly separated from the scattered X-rays. Concentrations of 5.62-78.63 mg/ml of Gd ion were used in 1, 2, and 3 cm diameter spherical tumors and a 2x4 cm oblate spheroid tumor. The data show trends approaching saturation for the highest concentrations, probably due to reabsorption in the tumor. A comparison of X-ray photographic imaging and densitometer measurements to determine concentration is also presented.

Recovery of methamphetamine associated cardiomyopathy predicted by late gadolinium enhanced cardiovascular magnetic resonance.

PubMed

Lopez, Javier E; Yeo, Khung; Caputo, Gary; Buonocore, Michael; Schaefer, Saul

2009-11-11

Methamphetamine is known to cause a cardiomyopathy which may be reversible with appropriate medical therapy and cessation of use. Late gadolinium enhancement cardiovascular magnetic resonance (CMR) has been shown to identify fibrosis in ischemic and non-ischemic cardiomyopathies. We present a case of severe methamphetamine-associated cardiomyopathy in which cardiac function recovered after 6 months. Evaluation by CMR using late gadolinium enhancement was notable for an absence of enhancement, suggesting an absence of irreversible myocyte injury and a good prognosis. CMR may be useful to predict recovery in toxin-associated non-ischemic cardiomyopathies.

Recovery of methamphetamine associated cardiomyopathy predicted by late gadolinium enhanced cardiovascular magnetic resonance

PubMed Central

2009-01-01

Methamphetamine is known to cause a cardiomyopathy which may be reversible with appropriate medical therapy and cessation of use. Late gadolinium enhancement cardiovascular magnetic resonance (CMR) has been shown to identify fibrosis in ischemic and non-ischemic cardiomyopathies. We present a case of severe methamphetamine-associated cardiomyopathy in which cardiac function recovered after 6 months. Evaluation by CMR using late gadolinium enhancement was notable for an absence of enhancement, suggesting an absence of irreversible myocyte injury and a good prognosis. CMR may be useful to predict recovery in toxin-associated non-ischemic cardiomyopathies. PMID:19906310

Acute side effects of three commonly used gadolinium contrast agents in the paediatric population.

PubMed

Neeley, Chris; Moritz, Michael; Brown, Jeffrey J; Zhou, Yihua

2016-07-01

To determine the incidence of acute side effects of three commonly used gadolinium contrast agents in the paediatric population. A retrospective review of medical records was performed to determine the incidence of acute adverse side effects of i.v. gadolinium contrast agents [MultiHance(®) (Bracco Diagnostics Inc., Princeton, NJ), Magnevist(®) (Bayer Healthcare Pharmaceuticals, Wayne, NJ) or Gadavist(®) (Bayer HealthCare Pharmaceuticals)] in paediatric patients. 40 of the 2393 patients who received gadolinium contrast agents experienced acute side effects, representing an incidence of 1.7%. The majority of the acute side effects (in 30 patients) were nausea and vomiting. The incidence was significantly higher in non-sedated patients (2.37% vs 0.7%; p = 0.0018). Furthermore, without sedation, the incidence of both nausea and vomiting was significantly higher in children receiving MultiHance, with a 4.48% incidence of nausea when compared with Magnevist (0.33%, p < 0.0001) and Gadavist (0.28%, p < 0.0001) and a 2.36% incidence of vomiting compared with those for Magnevist (0.50%, p = 0.0054) and Gadavist (0.28%, p = 0.014), whereas no difference was observed between Magnevist and Gadavist within the power of the study. In addition, there was no apparent difference between any of the three contrast agents for the incidence of allergy or other acute side effects detected, given the sample size. The gadolinium contrast agents MultiHance, Magnevist and Gadavist have a low incidence of acute side effects in the paediatric population, a rate that is further reduced in moderately sedated patients. MultiHance demonstrated significantly increased incidence of gastrointestinal symptoms compared with Magnevist and Gadavist. The incidence of acute side effects of three commonly used gadolinium contrast agents was determined in the paediatric population, which can have clinical implications.

Layered gadolinium hydroxides for low-temperature magnetic cooling.

PubMed

Abellán, Gonzalo; Espallargas, Guillermo Mínguez; Lorusso, Giulia; Evangelisti, Marco; Coronado, Eugenio

2015-09-28

Layered gadolinium hydroxides have revealed to be excellent candidates for cryogenic magnetic refrigeration. These materials behave as pure 2D magnetic systems with a Heisenberg-Ising critical crossover, induced by dipolar interactions. This 2D character and the possibility offered by these materials to be delaminated open the possibility of rapid heat dissipation upon substrate deposition.

Gadolinium-148 and other spallation production cross section measurements for accelerator target facilities

NASA Astrophysics Data System (ADS)

Kelley, Karen Corzine

At the Los Alamos Neutron Science Center accelerator complex, protons are accelerated to 800 MeV and directed to two tungsten targets, Target 4 at the Weapons Neutron Research facility and the 1L target at the Lujan Center. The Department of Energy requires hazard classification analyses to be performed on these targets and places limits on certain radionuclide inventories in the targets to avoid characterizing the facilities as "nuclear facilities." Gadolinium-148 is a radionuclide created from the spallation of tungsten. Allowed isotopic inventories are particularly low for this isotope because it is an alpha-particle emitter with a 75-year half-life. The activity level of Gadolinium-148 is low, but it encompasses almost two-thirds of the total dose burden for the two tungsten targets based on present yield estimates. From a hazard classification standpoint, this severely limits the lifetime of these tungsten targets. The cross section is not well-established experimentally and this is the motivation for measuring the Gadolinium-148 production cross section from tungsten. In a series of experiments at the Weapons Neutron Research facility, Gadolinium-148 production was measured for 600- and 800-MeV protons on tungsten, tantalum, and gold. These experiments used 3 mum thin tungsten, tantalum, and gold foils and 10 mum thin aluminum activation foils. In addition, spallation yields were determined for many short-lived and long-lived spallation products with these foils using gamma and alpha spectroscopy and compared with predictions of the Los Alamos National Laboratory codes CEM2k+GEM2 and MCNPX. The cumulative Gadolinium-148 production cross section measured from tantalum, tungsten, and gold for incident 600-MeV protons were 15.2 +/- 4.0, 8.31 +/- 0.92, and 0.591 +/- 0.155, respectively. The average production cross sections measured at 800 MeV were 28.6 +/- 3.5, 19.4 +/- 1.8, and 3.69 +/- 0.50 for tantalum, tungsten, and gold, respectively. These cumulative

Effect of composition and calcination temperature of ceria-zirconia-alumina mixed oxides on catalytic performances of ethanol conversion

NASA Astrophysics Data System (ADS)

Chuklina, S. G.; Maslenkova, S. A.; Pylinina, A. I.; Podzorova, L. I.; Ilyicheva, A. A.

2017-02-01

In the present study, we investigated the effect of preparation method, phase composition and calcination temperature of the (Ce-TZP) - Al2O3 mixed oxides on their structural features and catalytic performance in ethanol conversion. Ceria-zirconia-alumina mixed oxides with different (Ce+Zr)/Al atomic ratios were prepared via sol-gel method. Catalytic activity and selectivity were investigated for ethanol conversion to acetaldehyde, ethylene and diethyl ether.

The network formers role of gadolinium(III) ions in some zinc-borate glass ceramics

NASA Astrophysics Data System (ADS)

Bosca, Maria; Pop, Lidia; Pascuta, Petru

2017-12-01

EPR and magnetic susceptibility measurements were performed on glass ceramics from the (Gd2O3)x.(B2O3)(60-x).(ZnO)40 system, with 0 ≤ x ≤ 15 mol%, in order to determine the role of gadolinium ions on structural and magnetic properties. At low Gd2O3 contents (x ≤ 1 mol%) the EPR spectra show four resonance lines with effective g-values of ˜ 6, 4.8, 2.8 and 2, typical for Gd3+ ions uniformly distributed in the glass and glass ceramic samples. For higher contents of gadolinium ions (x ≥ 3 mol%) the EPR spectra are dominated by a single broad line centered at g ˜ 2, which can be due to the magnetic clusters containing Gd3+ ions. The magnetic susceptibility data show that the gadolinium ions are involved in superexchange interactions in all the investigated glass ceramics, being antiferromagnetically coupled.

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

Nelson, Nicholas C.; Boote, Brett W.; Naik, Pranjali

Ceria (CeO 2) and sodium-modified ceria (Ce-Na) were prepared through combustion synthesis. Palladium was deposited onto the supports (Pd/CeO 2 and Pd/Ce-Na) and their activity for the aqueous-phase transfer hydrogenation of phenol using 2-propanol under liquid flow conditions was studied. Pd/Ce-Na showed a marked increase (6×) in transfer hydrogenation activity over Pd/CeO 2. Material characterization indicated that water-stable sodium species were not doped into the ceria lattice, but rather existed as subsurface carbonates. Modification of ceria by sodium provided more adsorption and redox active sites (i.e. defects) for 2-propanol dehydrogenation. This effect was an intrinsic property of the Ce-Na supportmore » and independent of Pd. The redox sites active for 2-propanol dehydrogenation were thermodynamically equivalent on both supports/catalysts. At high phenol concentrations, the reaction was limited by 2-propanol adsorption. Furthermore, the difference in catalytic activity was attributed to the different numbers of 2-propanol adsorption and redox active sites on each catalyst.« less

Sensitive and transportable gadolinium-core plastic scintillator sphere for neutron detection and counting

NASA Astrophysics Data System (ADS)

Dumazert, Jonathan; Coulon, Romain; Carrel, Frédérick; Corre, Gwenolé; Normand, Stéphane; Méchin, Laurence; Hamel, Matthieu

2016-08-01

Neutron detection forms a critical branch of nuclear-related issues, currently driven by the search for competitive alternative technologies to neutron counters based on the helium-3 isotope. The deployment of plastic scintillators shows a high potential for efficient detectors, safer and more reliable than liquids, more easily scalable and cost-effective than inorganic. In the meantime, natural gadolinium, through its 155 and mostly 157 isotopes, presents an exceptionally high interaction probability with thermal neutrons. This paper introduces a dual system including a metal gadolinium core inserted at the center of a high-scale plastic scintillator sphere. Incident fast neutrons are thermalized by the scintillator shell and then may be captured with a significant probability by gadolinium 155 and 157 nuclei in the core. The deposition of a sufficient fraction of the capture high-energy prompt gamma signature inside the scintillator shell will then allow discrimination from background radiations by energy threshold, and therefore neutron detection. The scaling of the system with the Monte Carlo MCNPX2.7 code was carried out according to a tradeoff between the moderation of incident fast neutrons and the probability of slow neutron capture by a moderate-cost metal gadolinium core. Based on the parameters extracted from simulation, a first laboratory prototype for the assessment of the detection method principle has been synthetized. The robustness and sensitivity of the neutron detection principle are then assessed by counting measurement experiments. Experimental results confirm the potential for a stable, highly sensitive, transportable and cost-efficient neutron detector and orientate future investigation toward promising axes.

T1 relaxivity of core-encapsulated gadolinium liposomal contrast agents--effect of liposome size and internal gadolinium concentration.

PubMed

Ghaghada, Ketan; Hawley, Catherine; Kawaji, Keigo; Annapragada, Ananth; Mukundan, Srinivasan

2008-10-01

Long circulating core-encapsulated gadolinium (CE-Gd) liposomal nanoparticles that have surface conjugated polyethylene glycol are a promising platform technology for use as blood pool T1-based magnetic resonance (MR) contrast agents. The objective of this study was to investigate the effect of liposome size and internal (core) Gd concentration on the T1 relaxivity of CE-Gd liposomes. Twelve different liposomal formulations were synthesized and characterized, resulting in a size (50, 100, 200, and 400 nm) and core Gd-concentration (200, 350, and 500 mM) "matrix" of test samples. Subsequently, CE-Gd liposomes were diluted in deionized water (four diluted samples) and molar T1 relaxivity (r1) measurements were performed at 2- and 7-T MR field strengths. The r1 of CE-Gd liposomes was inversely related to the liposome size. The largest change in r1 was observed between liposomes that were extruded through 50- and 100-nm filter membranes. At both field strengths, the variation in internal gadolinium concentration did not show any significant correlation (alpha < or = 0.05) with r1. The size of CE-Gd liposomal nanoparticles significantly affects the T1 relaxivity. An inverse relation was observed between liposome size and T1 relaxivity. The T1 relaxivity did not change significantly with core Gd concentration over the measured concentration range.

Magnetization reversal and inverted magnetoresistance of exchange-biased spin valves with a gadolinium layer

NASA Astrophysics Data System (ADS)

Milyaev, M.; Naumova, L.; Chernyshova, T.; Proglyado, V.; Kamensky, I.; Krinitsina, T.; Ryabukhina, M.; Ustinov, V.

2017-03-01

FeMn-based spin valves with a gadolinium layer have been fabricated by magnetron sputtering. The magnetoresistive properties of the spin valves have been investigated at temperatures of 80-293 K. Temperature-induced switching between low- and high-resistance magnetic states has been revealed. Realization of the low- or high-resistance states depends on which magnetic moment dominates in the exchange-coupled Gd/CoFe, of Gd or CoFe. It has been shown that the switching temperature depends on the thickness of the gadolinium layer.

Dependence of Non-Prestonian Behavior of Ceria Slurry with Anionic Surfactant on Abrasive Concentration and Size in Shallow Trench Isolation Chemical Mechanical Polishing

NASA Astrophysics Data System (ADS)

Kang, Hyun‑Goo; Kim, Dae‑Hyeong; Katoh, Takeo; Kim, Sung‑Jun; Paik, Ungyu; Park, Jea‑Gun

2006-05-01

The dependencies of the non-Prestonian behavior of ceria slurry with anionic surfactant on the size and concentration of abrasive particles were investigated by performing chemical mechanical polishing (CMP) experiments using blanket wafers. We found that not only the abrasive size but also the abrasive concentration with surfactant addition influences the non-Prestonian behavior. Such behavior is clearly exhibited with small abrasive sizes and a higher concentrations of abrasives with surfactant addition, because the abrasive particles can locally contact the film surface more effectively with applied pressure. We introduce a factor to quantify these relations with the non-Prestonian behavior of a slurry. For ceria slurry, this non-Prestonian factor, βNP, was determined to be almost independent of the abrasive concentration for a larger size and a smaller weight conentration of abrasive particles, but it increased with the surfactant concentration for a smaller size and a higher concentration of abrasives with surfactant addition.

Plastic optical fibre sensor for in-vivo radiation monitoring during brachytherapy

NASA Astrophysics Data System (ADS)

Woulfe, P.; Sullivan, F. J.; Lewis, E.; O'Keeffe, S.

2015-09-01

An optical fibre sensor is presented for applications in real-time in-vivo monitoring of the radiation dose a cancer patient receives during seed implantation in Brachytherapy. The sensor is based on radioluminescence whereby radiation sensitive scintillation material is embedded in the core of a 1mm plastic optical fibre. Three scintillation materials are investigated: thallium-doped caesium iodide (CsI:Tl), terbium-doped gadolinium oxysulphide (Gd2O2S:Tb) and europium-doped lanthanum oxysulphide (La2O2S:Eu). Terbium-doped gadolinium oxysulphide was identified as being the most suitable scintillator and further testing demonstrates its measureable response to different activities of Iodine-125, the radio-active source commonly used in Brachytherapy for treating prostate cancer.

Gadolinium-based nanoparticles for highly efficient T1-weighted magnetic resonance imaging

NASA Astrophysics Data System (ADS)

Lim, Eun-Kyung; Kang, Byunghoon; Choi, Yuna; Jang, Eunji; Han, Seungmin; Lee, Kwangyeol; Suh, Jin-Suck; Haam, Seungjoo; Huh, Yong-Min

2014-06-01

We developed Pyrene-Gadolinium (Py-Gd) nanoparticles as pH-sensitive magnetic resonance imaging (MRI) contrast agents capable of showing a high-Mr signal in cancer-specific environments, such as acidic conditions. Py-Gd nanoparticles were prepared by coating Py-Gd, which is a complex of gadolinium with pyrenyl molecules, with pyrenyl polyethyleneglycol PEG using a nano-emulsion method. These particles show better longitudinal relaxation time (T1) MR signals in acidic conditions than they do in neutral conditions. Furthermore, the particles exhibit biocompatibility and MR contrast effects in both in vitro and in vivo studies. From these results, we confirm that Py-Gd nanoparticles have the potential to be applied for accurate cancer diagnosis and therapy.

Characterization of the reaction products and precipitates at the interface of carbon fiber reinforced magnesium–gadolinium composite

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

Wang, Yaping; Jiang, Longtao, E-mail: longtaojiang@163.com; Chen, Guoqin

2016-03-15

In the present work, carbon fiber reinforced magnesium-gadolinium composite was fabricated by pressure infiltration method. The phase composition, micro-morphology, and crystal structure of reaction products and precipitates at the interface of the composite were investigated. Scanning electron microscopy and energy dispersive spectroscopy analysis revealed the segregation of gadolinium element at the interface between carbon fiber and matrix alloy. It was shown that block-shaped Gd4C5, GdC2 and nano-sized Gd2O3 were formed at the interface during the fabrication process due to the interfacial reaction. Furthermore, magnesium-gadolinium precipitates including needle-like Mg5Gd (or Mg24Gd5) and thin plate-shaped long period stacking-ordered phase, were also observedmore » at the interface and in the matrix near the interface. The interfacial microstructure and bonding mode were influenced by these interfacial products, which were beneficial for the improvement of the interfacial bonding strength. - Highlights: • Gadolinium element segregated on the surface of carbon fibers. • Block-shaped Gd{sub 4}C{sub 5} and GdC{sub 2} were formed at the interface via chemical reaction. • Gadolinium and oxygen reacted at the interface and formed nano-scaled Gd{sub 2}O{sub 3}. • The precipitates formed in the interface were identified to be Mg{sub 5}Gd (or Mg{sub 24}Gd{sub 5}) and plate-shaped long period stacking-ordered phase.« less

Two-stage epitaxial growth of vertically-aligned SnO 2 nano-rods on(001) ceria

DOE PAGES

Solovyov, Vyacheslav F.; Wu, Li-jun; Rupich, Martin W.; ...

2014-09-20

Growth of high-aspect ratio oriented tin oxide, SnO 2, nano-rods is complicated by a limited choice of matching substrates. We show that a (001) cerium oxide, CeO 2, surface uniquely enables epitaxial growth of tin-oxide nano-rods via a two-stage process. First, (100) oriented nano-wires coat the ceria surface by lateral growth, forming a uniaxially-textured SnO 2 deposit. Second, vertical SnO 2nano-rods nucleate on the deposit by homoepitaxy. We demonstrate growth of vertically oriented 1-2 μm long nano-rods with an average diameter of ≈20 nm.

Designed synthesis of multi-functional PEGylated Yb2O3:Gd@SiO2@CeO2 islands core@shell nanostructure.

PubMed

Li, Junqi; Yao, Shuang; Song, Shuyan; Wang, Xiao; Wang, Yinghui; Ding, Xing; Wang, Fan; Zhang, Hongjie

2016-07-28

Nanomaterials that can restrain or reduce the production of excessive reactive oxygen species such as H2O2 to defend and treat against Alzheimer's disease (AD) have attracted much attention. In this paper, we adopt the strategy of layer-by-layer deposition; namely, first synthesizing available gadolinium-doped ytterbia nanoparticles (Yb2O3:Gd NPs) as cores, and then coating them with silica via the classical Stöber method to prevent leakage and act as a carrier for subsequent ceria deposition and PEGylation, and finally obtain the expected core@shell-structured nanocomposite of PEGylated Yb2O3:Gd@SiO2@CeO2 islands. The nanomaterial has proved not only to be a high-performance dual-modal contrast agent for use in MRI and CT, but also to exhibit excellent catalase mimetic activity, which may help the prognosis, diagnosis and treatment of AD in the future. In addition, scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared (FTIR) spectroscopy characterization have revealed the successful design and synthesis of the cores with remarkable size uniformity, with well-distributed CeO2 islands decorated on the surface of SiO2 shells, and tightly immobilized PEG.

Synthesis and luminescent properties of Gd3Ga2Al3O12 phosphors doped with Eu3+ or Ce3+

NASA Astrophysics Data System (ADS)

Oh, M. J.; Kim, H. J.

2016-09-01

Eu3+-or Ce3+-doped gadolinium gallium aluminum garnet (GGAG), Gd3Ga2Al3O12, phosphors are fabricated using solid-state reactions with Gd2O3, Ga2O3, Al2O3, CeO2 and Eu2O3 powders. The Eu3+-or Ce3+-doped Gd3Ga2Al3O12 phosphors are sintered at 1300 °C or 1600 °C for 5 hours by using an electric furnace under normal atmosphere. X-ray diffraction and field-emission scanning electron microscopy studies are carried out in order to analyze the physical properties of these materials, and their luminescence properties are also measured by using UV and X-ray sources. The Eu3+-or Ce3+-doped Gd3Ga2Al3O12 phosphors show higher light yields in comparison to commercial phosphors such as Gd2O2S:Tb (gadox). This indicates that Gd3Ga2Al3O12:Eu3+ phosphors are promising materials for use in X-ray imaging and dose monitoring at proton beamlines.

Simple method for quantification of gadolinium magnetic resonance imaging contrast agents using ESR spectroscopy.

PubMed

Takeshita, Keizo; Kinoshita, Shota; Okazaki, Shoko

2012-01-01

To develop an estimation method of gadolinium magnetic resonance imaging (MRI) contrast agents, the effect of concentration of Gd compounds on the ESR spectrum of nitroxyl radical was examined. A solution of either 4-oxo-2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPONE) or 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPOL) was mixed with a solution of Gd compound and the ESR spectrum was recorded. Increased concentration of gadolinium-diethylenetriamine pentaacetic acid chelate (Gd-DTPA), an MRI contrast agent, increased the peak-to-peak line widths of ESR spectra of the nitroxyl radicals, in accordance with a decrease of their signal heights. A linear relationship was observed between concentration of Gd-DTPA and line width of ESR signal, up to approximately 50 mmol/L Gd-DTPA, with a high correlation coefficient. Response of TEMPONE was 1.4-times higher than that of TEMPOL as evaluated from the slopes of the lines. The response was slightly different among Gd compounds; the slopes of calibration curves for acua[N,N-bis[2-[(carboxymethyl)[(methylcarbamoyl)methyl]amino]ethyl]glycinato(3-)]gadolinium hydrate (Gd-DTPA-BMA) (6.22 μT·L/mmol) and gadolinium-1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid chelate (Gd-DOTA) (6.62 μT·L/mmol) were steeper than the slope for Gd-DTPA (5.45 μT·L/mmol), whereas the slope for gadolinium chloride (4.94 μT·L/mmol) was less steep than that for Gd-DTPA. This method is simple to apply. The results indicate that this method is useful for rough estimation of the concentration of Gd contrast agents if calibration is carried out with each standard compound. It was also found that the plot of the reciprocal square root of signal height against concentrations of contrast agents could be useful for the estimation if a constant volume of sample solution is taken and measured at the same position in the ESR cavity every time.

Nephrogenic systemic fibrosis (NSF): a late adverse reaction to some of the gadolinium based contrast agents

PubMed Central

Marckmann, Peter; Logager, Vibeke B.

2007-01-01

Abstract Until recently it was believed that extracellular gadolinium based contrast agents were safe for both the kidneys and all other organs within the dose range up to 0.3 mmol/kg body weight. However, in 2006, it was demonstrated that some gadolinium based contrast agents may trigger the development of nephrogenic systemic fibrosis, a generalised fibrotic disorder, in renal failure patients. Accordingly, the use of gadodiamide and gadopentate dimeglumine for renal failure patients was banned in Europe in spring 2007. The same two compounds should only be used cautiously in patients with moderate renal dysfunction. The current paper reviews the situation (July 2007) regarding gadolinium based contrast agent and the severe delayed reaction to some of these agents. The fear of nephrogenic systemic fibrosis should not lead to a denial of a well indicated enhanced magnetic resonance imaging examination. PMID:17905680

Measurement of gadolinium retention: current status and review from an applied radiation physics perspective.

PubMed

Gräfe, James L; McNeill, Fiona E

2018-06-28

This article briefly reviews the main measurement techniques for the non-invasive detection of residual gadolinium (Gd) in those exposed to gadolinium-based contrast agents (GBCAs). Approach and Main results: The current status of in vivo Gd measurement is discussed and is put into the context of concerns within the radiology community. The main techniques are based on applied atomic/nuclear medicine utilizing the characteristic atomic and nuclear spectroscopic signature of Gd. The main emission energies are in the 40-200 keV region and require spectroscopic detectors with good energy resolution. The two main techniques, prompt gamma neutron activation analysis and x-ray fluorescence, provide adequate detection limits for in vivo measurement, whilst delivering a low effective radiation dose on the order of a few µSv. Gadolinium is being detected in measureable quantities in people with healthy renal function who have received FDA approved GBCAs. The applied atomic/nuclear medicine techniques discussed in this review will be useful in determining the significance of this retention, and will help on advising future administration protocols.

Influence of xc functional on thermal-elastic properties of Ceria: A DFT-based Debye-Grüneisen model approach

NASA Astrophysics Data System (ADS)

Lee, Ji-Hwan; Tak, Youngjoo; Lee, Taehun; Soon, Aloysius

Ceria (CeO2-x) is widely studied as a choice electrolyte material for intermediate-temperature (~ 800 K) solid oxide fuel cells. At this temperature, maintaining its chemical stability and thermal-mechanical integrity of this oxide are of utmost importance. To understand their thermal-elastic properties, we firstly test the influence of various approximations to the density-functional theory (DFT) xc functionals on specific thermal-elastic properties of both CeO2 and Ce2O3. Namely, we consider the local-density approximation (LDA), the generalized gradient approximation (GGA-PBE) with and without additional Hubbard U as applied to the 4 f electron of Ce, as well as the recently popularized hybrid functional due to Heyd-Scuseria-Ernzehof (HSE06). Next, we then couple this to a volume-dependent Debye-Grüneisen model to determine the thermodynamic quantities of ceria at arbitrary temperatures. We find an explicit description of the strong correlation (e.g. via the DFT + U and hybrid functional approach) is necessary to have a good agreement with experimental values, in contrast to the mean-field treatment in standard xc approximations (such as LDA or GGA-PBE). We acknowledge support from Samsung Research Funding Center of Samsung Electronics (SRFC-MA1501-03).

Revisiting the Pharmacokinetic Profiles of Gadolinium-Based Contrast Agents: Differences in Long-Term Biodistribution and Excretion.

PubMed

Lancelot, Eric

2016-11-01

Gadolinium-based contrast agents (GBCAs) have been used for years for magnetic resonance imaging examinations. Because of their rapid blood clearance, they were considered as very safe products until some of them were shown to induce nephrogenic systemic fibrosis in patients with renal failure and hypersignals on T1-weighted unenhanced brain scans of patients with normal renal function. To date, these adverse effects have been related almost exclusively to the use of low-stability linear agents, which are more prone to release free gadolinium. The aim of the present meta-analysis was to ascertain the existence of a deep compartment for gadolinium storage in the body and to assess whether all the GBCAs present the same toxicokinetic profile. Applying a systematic literature search methodology, all clinical and preclinical studies reporting time-dependent plasma concentrations and renal excretion data of gadolinium were identified and analyzed. Since the individual data were not available, the analysis focused on the average values per groups of subjects or animals, which had received a given GBCA at a given dose. The rate constants of the distribution phase (α), rapid elimination phase (β), and residual excretion phase (γ) of gadolinium were determined in each group from the plasma concentration (Cp) time curves and the relative urinary excretion rate (rER) time curves, taking the 2-hour time point as a reference. Moreover, as bone may represent a reservoir for long-term gadolinium accumulation and slow release into the blood stream, the time curves of the relative concentration in the bone (rCB) of Gd-labeled GBCAs in mice or rats were analyzed taking day 1 concentrations as a reference. The ratio of gadolinium concentrations in the bone marrow (CBM) as compared with the bone (CB) was also calculated. The relative urinary excretion rate (rER) plots revealed a prolonged residual excretion phase of gadolinium in healthy volunteers, consistent with the existence of

Synthesis, photophysical analysis, and in vitro cytotoxicity assessment of the multifunctional (magnetic and luminescent) core@shell nanomaterial based on lanthanide-doped orthovanadates

NASA Astrophysics Data System (ADS)

Szczeszak, Agata; Ekner-Grzyb, Anna; Runowski, Marcin; Mrówczyńska, Lucyna; Grzyb, Tomasz; Lis, Stefan

2015-03-01

Rare earths orthovanadates (REVO4) doped with luminescent lanthanide ions (Ln3+) play an important role as promising light-emitting materials. Gadolinium orthovanadate exhibits strong absorption of ultraviolet radiation and as a matrix doped with Eu3+ ions is well known for its efficient and intense red emission, induced by energy transfer from the VO4 3- groups to Eu3+ ions. In the presented study, Fe3O4@SiO2@GdVO4:Eu3+ 5 % nanomaterial was investigated. The core@shell structures demonstrate attractive properties, such as higher thermal stability, enhanced water solubility, increased optical response, higher luminescence, longer decay times, and magnetic properties. Silica coating may protect nanocrystals from the surrounding environment. Therefore, such silica-covered nanoparticles (NPs) are successfully utilized in biomedical research. Multifunctional magnetic nanophosphors are very interesting due to their potential biomedical applications such as magnetic resonance imaging, hyperthermic treatment, and drug delivery. Therefore, the aim of our study was to investigate photophysical, chemical, and biological properties of multifunctional REVO4 doped with Ln3+. Moreover, the studied NPs did not affect erythrocyte sedimentation rate, cell membrane permeability, and morphology of human red blood cells.

Gadolinium prevents high airway pressure-induced permeability increases in isolated rat lungs.

PubMed

Parker, J C; Ivey, C L; Tucker, J A

1998-04-01

To determine the initial signaling event in the vascular permeability increase after high airway pressure injury, we compared groups of lungs ventilated at different peak inflation pressures (PIPs) with (gadolinium group) and without (control group) infusion of 20 microM gadolinium chloride, an inhibitor of endothelial stretch-activated cation channels. Microvascular permeability was assessed by using the capillary filtration coefficient (Kfc), a measure of capillary hydraulic conductivity. Kfc was measured after ventilation for 30-min periods with 7, 20, and 30 cmH2O PIP with 3 cmH2O positive end-expiratory pressure and with 35 cmH2O PIP with 8 cmH2O positive end-expiratory pressure. In control lungs, Kfc increased significantly to 1.8 and 3.7 times baseline after 30 and 35 cmH2O PIP, respectively. In the gadolinium group, Kfc was unchanged from baseline (0.060 +/- 0.010 ml . min-1 . cmH2O-1 . 100 g-1) after any PIP ventilation period. Pulmonary vascular resistance increased significantly from baseline in both groups before the last Kfc measurement but was not different between groups. These results suggest that microvascular permeability is actively modulated by a cellular response to mechanical injury and that stretch-activated cation channels may initiate this response through increases in intracellular calcium concentration.

Hyperintense Dentate Nuclei on T1-Weighted MRI: Relation to Repeat Gadolinium Administration

PubMed Central

Adin, M.E.; Kleinberg, L.; Vaidya, D.; Zan, E.; Mirbagheri, S.; Yousem, D.M.

2016-01-01

BACKGROUND AND PURPOSE A hyperintense appearance of the dentate nucleus on T1-weighted MR images has been related to various clinical conditions, but the etiology remains indeterminate. We aimed to investigate the possible associations between a hyperintense appearance of the dentate nucleus on T1-weighted MR images in patients exposed to radiation and factors including, but not limited to, the cumulative number of contrast-enhanced MR images, amount of gadolinium administration, dosage of ionizing radiation, and patient demographics. MATERIALS AND METHODS The medical records of 706 consecutive patients who were treated with brain irradiation at The Johns Hopkins Medical Institutions between 1995 and 2010 were blindly reviewed by 2 readers. RESULTS One hundred eighty-four subjects were included for dentate nuclei analysis. Among the 184 subjects who cumulatively underwent 2677 MR imaging studies following intravenous gadolinium administration, 103 patients had hyperintense dentate nuclei on precontrast T1-weighted MR images. The average number of gadolinium-enhanced MR imaging studies performed in the group with normal dentate nuclei was significantly lower than that of the group with hyperintense dentate nuclei. The average follow-up time was 62.5 months. No significant difference was observed between hyperintense and normal dentate nuclei groups in terms of exposed radiation dose, serum creatinine and calcium/phosphate levels, patient demographics, history of chemotherapy, and strength of the scanner. No dentate nuclei abnormalities were found on the corresponding CT scans of patients with hyperintense dentate nuclei (n = 44). No dentate nuclei abnormalities were found in 53 healthy volunteers. CONCLUSIONS Repeat performance of gadolinium-enhanced studies likely contributes to a long-standing hyperintense appearance of dentate nuclei on precontrast T1-weighted-MR images. PMID:26294649

The Gadolinium (Gd3+) and Tin (Sn4+) Co-doped BiFeO3 Nanoparticles as New Solar Light Active Photocatalyst

PubMed Central

Irfan, Syed; Rizwan, Syed; Shen, Yang; Li, Liangliang; Asfandiyar, A; Butt, Sajid; Nan, Ce-Wen

2017-01-01

The process of photocatalysis is appealing to huge interest motivated by the great promise of addressing current energy and environmental issues through converting solar light directly into chemical energy. However, an efficient solar energy harvesting for photocatalysis remains a critical challenge. Here, we reported a new full solar spectrum driven photocatalyst by co-doping of Gd3+ and Sn4+ into A and B-sites of BiFeO3 simultaneously. The co-doping of Gd3+ and Sn4+ played a key role in hampering the recombination of electron-hole pairs and shifted the band-gap of BiFeO3 from 2.10 eV to 2.03 eV. The Brunauer-Emmett-Teller (BET) measurement confirmed that the co-doping of Gd3+ and Sn4+ into BiFeO3 increased the surface area and porosity, and thus the photocatalytic activity of the Bi0.90Gd0.10Fe0.95Sn0.05O3 system was significantly improved. Our work proposed a new photocatalyst that could degrade various organic dyes like Congo red, Methylene blue, and Methyl violet under irradiation with different light wavelengths and gave guidance for designing more efficient photocatalysts. PMID:28195198

The evolution of gadolinium based contrast agents: from single-modality to multi-modality

NASA Astrophysics Data System (ADS)

Zhang, Li; Liu, Ruiqing; Peng, Hui; Li, Penghui; Xu, Zushun; Whittaker, Andrew K.

2016-05-01

Gadolinium-based contrast agents are extensively used as magnetic resonance imaging (MRI) contrast agents due to their outstanding signal enhancement and ease of chemical modification. However, it is increasingly recognized that information obtained from single modal molecular imaging cannot satisfy the higher requirements on the efficiency and accuracy for clinical diagnosis and medical research, due to its limitation and default rooted in single molecular imaging technique itself. To compensate for the deficiencies of single function magnetic resonance imaging contrast agents, the combination of multi-modality imaging has turned to be the research hotpot in recent years. This review presents an overview on the recent developments of the functionalization of gadolinium-based contrast agents, and their application in biomedicine applications.

Two-stage epitaxial growth of vertically-aligned SnO2 nano-rods on (001) ceria

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

Solovyov, VF; Wu, LJ; Rupich, MW

2014-12-15

Growth of high-aspect ratio oriented tin oxide, SnO2, nano-rods is complicated by a limited choice of matching substrates. We show that a (001) cerium oxide, CeO2, surface uniquely enables epitaxial growth of tin-oxide nano-rods via a two-stage process. First, (100) oriented nano-wires coat the ceria surface by lateral growth, forming a uniaxially-textured SnO2 deposit. Second, vertical SnO2 nano-rods nucleate on the deposit by homoepitaxy. We demonstrate growth of vertically oriented 1-2 mu m long nano-rods with an average diameter of approximate to 20 nm. 2014 Elsevier B.V. All rights reserved.

Sub-nA spatially resolved conductivity profiling of surface and interface defects in ceria films

DOE PAGES

Farrow, Tim; Yang, Nan; Doria, Sandra; ...

2015-03-17

Spatial variability of conductivity in ceria is explored using scanning probe microscopy with galvanostatic control. Ionically blocking electrodes are used to probe the conductivity under opposite polarities to reveal possible differences in the defect structure across a thin film of CeO2. Data suggest the existence of a large spatial inhomogeneity that could give rise to constant phase elements during standard electrochemical characterization, potentially affecting the overall conductivity of films on the macroscale. The approach discussed here can also be utilized for other mixed ionic electronic conductor systems including memristors and electroresistors, as well as physical systems such as ferroelectric tunnelingmore » barriers« less

High performance electrodes for reduced temperature solid oxide fuel cells with doped lanthanum gallate electrolyte. I. Ni-SDC cermet anode

NASA Astrophysics Data System (ADS)

Ohara, S.; Maric, R.; Zhang, X.; Mukai, K.; Fukui, T.; Yoshida, H.; Inagaki, T.; Miura, K.

A Ni-samaria-doped ceria (SDC) cermet was selected as the anode material for reduced temperature (800°C) solid oxide fuel cells. The NiO-SDC composite powder, synthesized by spray pyrolysis, was employed as the starting anode powder in this study. The influence of Ni content in Ni-SDC cermets on the electrode performance was investigated in order to create the most suitable microstructures. It was found that anodic polarization was strongly influenced by the Ni content in Ni-SDC cermets. The best results were obtained for anode cermets with Ni content of around 50 vol.%; anodic polarization was about 30 mV at a current density of 300 mA/cm 2. This high performance seems to be attributable to the microstructure, in which Ni grains form a skeleton with well-connected SDC grains finely distributed over the Ni grains surfaces; such microstructure was also conducive to high stability of the anode.

Helium defectoscopy of cerium gadolinium ceramics Ce0.8Gd0.2O1.9 with a submicrocrystalline structure in the impurity disorder region

NASA Astrophysics Data System (ADS)

Koromyslov, A. V.; Zhiganov, A. N.; Kovalenko, M. A.; Kupryazhkin, A. Ya.

2013-12-01

The concentration of impurity anion vacancies formed upon the dissociation of gadolinium-vacancy complexes has been determined using helium defectoscopy of the cerium gadolinium ceramics Ce0.8Gd0.2O1.9 with a submicrocrystalline structure in the temperature range T = 740-1123 K and at saturation pressures ranging from 0.05 to 15 MPa. It has been found that the energy of dissociation of gadoliniumvacancy complexes is E {eff/ D }= 0.26 ± 0.06 eV, and the energy of dissolution of helium in anion vacancies in the impurity disorder region is E P = -0.31 ± 0.09 eV. The proposed mechanism of dissolution has been confirmed by the investigation of the electrical conductivity of the cerium gadolinium ceramics, as well as by the high-speed molecular dynamics simulation of the dissociation of gadolinium-vacancy complexes. It has been assumed that a decrease in the effective dissolution energy in comparison with the results of the previously performed low-temperature investigations is caused by the mutual repulsion of vacancies formed upon the dissociation of gadolinium-vacancy complexes in highly concentrated solutions of gadolinium in CeO2 with increasing temperature.

Vacancy–Vacancy Interaction Induced Oxygen Diffusivity Enhancement in Undoped Nonstoichiometric Ceria

DOE PAGES

Yuan, Fenglin; Zhang, Yanwen; Weber, William J.

2015-05-19

In this paper, molecular dynamics simulations and molecular static calculations have been used to systematically study oxygen vacancy transport in undoped nonstoichiometric ceria. A strong oxygen diffusivity enhancement appears in the vacancy concentration range of 2–4% over the temperature range from 1000 to 2000 K. An Arrhenius ion diffusion mechanism by vacancy hopping along the (100) direction is unambiguously identified, and an increasing trend of both the oxygen migration barrier and the prefactor with increasing vacancy concentration is observed. Within the framework of classical diffusion theory, a weak concentration dependence of the prefactor in oxygen vacancy migration is shown tomore » be crucial for explaining the unusual fast oxygen ion migration in the low concentration range and consequently the appearance of a maximum in oxygen diffusivity. Finally, a representative (100) direction interaction model is constructed to identify long-range vacancy–vacancy interaction as the structural origin of the positive correlation between oxygen migration barrier and vacancy concentration.« less

Size dependent compressibility of nano-ceria: Minimum near 33 nm

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

Rodenbough, Philip P.; Chemistry Department, Columbia University, New York, New York 10027; Song, Junhua

2015-04-20

We report the crystallite-size-dependency of the compressibility of nanoceria under hydrostatic pressure for a wide variety of crystallite diameters and comment on the size-based trends indicating an extremum near 33 nm. Uniform nano-crystals of ceria were synthesized by basic precipitation from cerium (III) nitrate. Size-control was achieved by adjusting mixing time and, for larger particles, a subsequent annealing temperature. The nano-crystals were characterized by transmission electron microscopy and standard ambient x-ray diffraction (XRD). Compressibility, or its reciprocal, bulk modulus, was measured with high-pressure XRD at LBL-ALS, using helium, neon, or argon as the pressure-transmitting medium for all samples. As crystallite sizemore » decreased below 100 nm, the bulk modulus first increased, and then decreased, achieving a maximum near a crystallite diameter of 33 nm. We review earlier work and examine several possible explanations for the peaking of bulk modulus at an intermediate crystallite size.« less

Light deflection in gadolinium molybdate ferroelastic crystals

NASA Astrophysics Data System (ADS)

Staniorowski, Piotr; Bornarel, Jean

2000-02-01

The deflection of a He-Ne light beam by polydomain gadolinium molybdate (GMO) crystals has been studied with respect to incidence angle icons/Journals/Common/alpha" ALT="alpha" ALIGN="TOP"/> i on the sample at room temperature. The A and B deflected beams do not cross each other during the icons/Journals/Common/alpha" ALT="alpha" ALIGN="TOP"/> i variation, in contrast to results and calculations previously published. The model using the Fresnel equation confirms this result. The model presented is more accurate for numerical calculation than that using the Huygens construction.

Studies on Synthesis, Microstructure and Transport Properties of Doped Cerium Oxides

NASA Astrophysics Data System (ADS)

Handal, Hala Talaat Abd El-Samei

Acceptor-doped ceria exhibits mixed ionic electronic conduction in reducing conditions and chemical stability against sulfur poisoning and coking. This thesis's primary goal is to explore new anode materials based on ceria--solid solutions for solid oxide fuel cells (SOFCs). The physicochemical and electrochemical performance of Ce0.9-xY 0.1MnxO2-delta ( x = 0 to 15 mol%) (CYMO) and Ce0.87Y0.1Mn 0.01N0.02O2-delta (N = Mg or Ca) were studied. Among the materials investigated in this study, Ce0.89Y 0.1Mn0.01Mg0.02O2-delta (Mg-CYMO) showed the highest total conductivity of 0.2 S cm-1 at 700°C in H2. An area specific polarization resistance of 0.23 O cm2 was observed for both Mg-CYMO and Ce0.8Y 0.1Mn0.1O2-delta (10CYMO) at 800°C, in wet H2. Chronoamperometric measurement for the symmetrical cell configuration based on 10CYMO electrodes showed stable performance upon exposure to 10 ppm H2S/H2. In a full cell configuration, 10CYMO (anode)/YSZ (electrolyte)/La0.8Sr0.2MnO3 (LSM)-YSZ cathode, polarization resistance of 1.4 O cm2 and power density of 75 mW/cm2 were obtained at 800°C in wet H2. The main challenge of employing proton-conducting electrolytes in SOFC is their poor chemical stability in the presence of steam and hydrocarbon fuels. Another goal of this thesis is to develop a chemically stable proton-conducting electrolyte for SOFCs. The effects of Fe and Co substitution on the electrical and physicochemical properties of BaCe0.9Sm0.1O 3-delta (BCS) were evaluated. Thermogravimetric analysis showed that incorporation of 5 to 10 mol% Fe or Co in BCS did not improve the chemical stability in CO2 at elevated temperatures. The BCSC10 sample sintering at 1400°C showed the highest electrical conductivity of 0.02 S cm -1 at 600°C in air, but it did not show any appreciable proton mobility under humidified atmosphere.

Effect of temperature and rare-earth doping on charge-carrier mobility in indium-monoselenide crystals

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

Abdinov, A. Sh., E-mail: abdinov-axmed@yandex.ru; Babayeva, R. F., E-mail: Babaeva-Rena@yandex.ru; Amirova, S. I.

2013-08-15

In the temperature range T = 77-600 K, the dependence of the charge-carrier mobility ({mu}) on the initial dark resistivity is experimentally investigated at 77 K ({rho}d{sub 0}), as well as on the temperature and the level (N) of rare-earth doping with such elements as gadolinium (Gd), holmium (Ho), and dysprosium (Dy) in n-type indium-monoselenide (InSe) crystals. It is established that the anomalous behavior of the dependences {mu}(T), {mu}({rho}d{sub 0}), and {mu}(N) found from the viewpoint of the theory of charge-carrier mobility in crystalline semiconductors is related, first of all, to partial disorder in indium-monoselenide crystals and can be attributedmore » to the presence of random drift barriers in the free energy bands.« less

Suppression of Rabbit VX‐2 Subcutaneous Tumor Growth by Gadolinium Neutron Capture Therapy

PubMed Central

Tokita, Nobuhiko; Tokuuye, Koichi; Satoh, Michinao; Churei, Hisahiko; Pechoux, Cécile Le; Kobayashi, Tooru; Kanda, Keiji

1993-01-01

VX‐2 tumors growing in hind legs of New Zealand White rabbits (n=4) were exposed to thermal neutrons for 40 min (2.1 × 1012 neutrons cm−2) while one of two hind leg tumors of each rabbit was infused continuously with meglumine gadopentetate through a branch of the left femoral artery. The contralateral (uninfused) tumors served as controls. Although no differential distribution of gadolinium was achieved between the tumor and its adjacent normal tissue, the gadolinium concentration in the infused tumor was approximately 5–6 fold higher than that in the contralateral tumor. Growth of gadolinium‐infused tumors was significantly inhibited compared to that of control tumors (P<0.05) between the 16th and 23rd days after treatment. PMID:8407547

Progressing Toward a Cohesive Pediatric 18F-FDG PET/MR Protocol: Is Administration of Gadolinium Chelates Necessary?

PubMed

Klenk, Christopher; Gawande, Rakhee; Tran, Vy Thao; Leung, Jennifer Trinh; Chi, Kevin; Owen, Daniel; Luna-Fineman, Sandra; Sakamoto, Kathleen M; McMillan, Alex; Quon, Andy; Daldrup-Link, Heike E

2016-01-01

With the increasing availability of integrated PET/MR scanners, the utility and need for MR contrast agents for combined scans is questioned. The purpose of our study was to evaluate whether administration of gadolinium chelates is necessary for evaluation of pediatric tumors on (18)F-FDG PET/MR images. First, in 119 pediatric patients with primary and secondary tumors, we used 14 diagnostic criteria to compare the accuracy of several MR sequences: unenhanced T2-weighted fast spin-echo imaging; unenhanced diffusion-weighted imaging; and-before and after gadolinium chelate contrast enhancement-T1-weighted 3-dimensional spoiled gradient echo LAVA (liver acquisition with volume acquisition) imaging. Next, in a subset of 36 patients who had undergone (18)F-FDG PET within 3 wk of MRI, we fused the PET images with the unenhanced T2-weighted MR images (unenhanced (18)F-FDG PET/MRI) and the enhanced T1-weighted MR images (enhanced (18)F-FDG PET/MRI). Using the McNemar test, we compared the accuracy of the two types of fused images using the 14 diagnostic criteria. We also evaluated the concordance between (18)F-FDG avidity and gadolinium chelate enhancement. The standard of reference was histopathologic results, surgical notes, and follow-up imaging. There was no significant difference in diagnostic accuracy between the unenhanced and enhanced MR images. Accordingly, there was no significant difference in diagnostic accuracy between the unenhanced and enhanced (18)F-FDG PET/MR images. (18)F-FDG avidity and gadolinium chelate enhancement were concordant in 30 of the 36 patients and 106 of their 123 tumors. Gadolinium chelate administration is not necessary for accurate diagnostic characterization of most solid pediatric malignancies on (18)F-FDG PET/MR images, with the possible exception of focal liver lesions. © 2016 by the Society of Nuclear Medicine and Molecular Imaging, Inc.

In vitro comparison of intracranial stent visibility using various concentrations of gadolinium contrast agent under 1.5 T and 3 T MR angiography.

PubMed

Chiang, Chen-Hua; Tseng, Ying-Chi; Chen, Ai-Chi; Huang, Yen-Lin; Chen, David Yen-Ting; Chen, Chi-Jen; Lin, Yen-Kuang; Hsu, Hui-Ling

2017-04-01

MR angiography (MRA) is an increasingly used evaluation method following intracranial stenting. However, the various artifacts created by the stent limit this technique. The purpose of this study was to investigate the effects of various concentrations of gadolinium contrast agent on the visibility and signal characteristics of two stents using the a contrast enhanced MRA technique. Two intracranial stents (Enterprise and Helistent) were placed in polyvinyl chloride tubes as vascular phantoms. They were filled with six different doses of gadolinium contrast agent (1.0, 2.0, 4.0, 6.0, 8.0, and 10.0 mmol/L dimeglumine gadopentetate, respectively) and imaged using 3 T and 1.5 T MR systems. Relative in-stent signal (RIS) was calculated and artificial luminal narrowing (ALN) was obtained using pixel by pixel analysis. The Enterprise stent, performed in both 1.5 T and 3 T MR systems, showed mean RIS values much less than those for the Helistent for all different doses of gadolinium solution. Increased gadolinium concentration resulted in a gradual reduction in RIS values in the Enterprise group. Also, ALN in the Enterprise group showed no or little change with various gadolinium doses. The Enterprise stent demonstrated good luminal visibility regardless of gadolinium concentration. The relative in-stent signals were more predictable in the Enterprise stent with various doses of gadolinium. Therefore, the Enterprise stent has been shown to provide better in-stent visibility compared with the Helistent using various gadolinium doses. Published by the BMJ Publishing Group Limited. For permission to use (where not already granted under a licence) please go to http://www.bmj.com/company/products-services/rights-and-licensing/.

Microfabrication of a gadolinium-derived solid-state sensor for thermal neutrons

PubMed Central

Achyuthan, Komandoor E.; Allen, Matthew; Denton, Michele L. B.; Siegal, Michael P.; Manginell, Ronald P.

2017-01-01

Abstract Neutron sensing is critical in civilian and military applications. Conventional neutron sensors are limited by size, weight, cost, portability and helium supply. Here the microfabrication of gadolinium (Gd) conversion material–based heterojunction diodes for detecting thermal neutrons using electrical signals produced by internal conversion electrons (ICEs) is described. Films with negligible stress were produced at the tensile-compressive crossover point, enabling Gd coatings of any desired thickness by controlling the radiofrequency sputtering power and using the zero-point near p(Ar) of 50 mTorr at 100 W. Post-deposition Gd oxidation–induced spallation was eliminated by growing a residual stress-free 50 nm neodymium-doped aluminum cap layer atop Gd. The resultant coatings were stable for at least 6 years, demonstrating excellent stability and product shelf-life. Depositing Gd directly on the diode surface eliminated the air gap, leading to a 200-fold increase in electron capture efficiency and facilitating monolithic microfabrication. The conversion electron spectrum was dominated by ICEs with energies of 72, 132 and 174 keV. Results are reported for neutron reflection and moderation by polyethylene for enhanced sensitivity, and γ- and X-ray elimination for improved specificity. The optimal Gd thickness was 10.4 μm for a 300 μm-thick partially depleted diode of 300 mm2 active surface area. Fast detection (within 10 min) at a neutron source-to-diode distance of 11.7 cm was achieved with this configuration. All ICE energies along with γ-ray and Kα,β X-rays were modeled to emphasize correlations between experiment and theory. Semi-conductor thermal neutron detectors offer advantages for field-sensing of radioactive neutron sources. PMID:28369631

Study of the Photon Strength Functions for Gadolinium Isotopes with the DANCE Array

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

Dashdorj, D.; Mitchell, G. E.; Baramsai, B.

2009-03-10

The gadolinium isotopes are interesting for reactor applications as well as for medicine and astrophysics. The gadolinium isotopes have some of the largest neutron capture cross sections. As a consequence they are used in the control rod in reactor fuel assembly. From the basic science point of view, there are seven stable isotopes of gadolinium with varying degrees of deformation. Therefore they provide a good testing ground for the study of deformation dependent structure such as the scissors mode. Decay gamma rays following neutron capture on Gd isotopes are detected by the DANCE array, which is located at flight pathmore » 14 at the Lujan Neutron Scattering Center at Los Alamos National Laboratory. The high segmentation and close packing of the detector array enable gamma-ray multiplicity measurements. The calorimetric properties of the DANCE array coupled with the neutron time-of-flight technique enables one to gate on a specific resonance of a specific isotope in the time-of-flight spectrum and obtain the summed energy spectrum for that isotope. The singles gamma-ray spectrum for each multiplicity can be separated by their DANCE cluster multiplicity. Various photon strength function models are used for comparison with experimentally measured DANCE data and provide insight for understanding the statistical decay properties of deformed nuclei.« less

Kinetic characteristics of the luminescence decay for industrial yttrium-gadolinium-aluminium garnet based phosphors

NASA Astrophysics Data System (ADS)

Lisitsyn, V. M.; Stepanov, S. A.; Valiev, D. T.; Vishnyakova, E. A.; Abdullin, H. A.; Marhabaeva, A. A.; Tulegenova, A. T.

2016-02-01

The spectral and decay kinetic characteristics of pulse cathodoluminescence and photoluminescence of phosphors based on yttrium-gadolinium-aluminum garnet were investigated using pulsed optical time resolved spectroscopy.

Geometrically confined ultrasmall gadolinium oxide nanoparticles boost the T1 contrast ability

NASA Astrophysics Data System (ADS)

Ni, Kaiyuan; Zhao, Zhenghuan; Zhang, Zongjun; Zhou, Zijian; Yang, Li; Wang, Lirong; Ai, Hua; Gao, Jinhao

2016-02-01

High-performance magnetic resonance imaging (MRI) contrast agents and novel contrast enhancement strategies are urgently needed for sensitive and accurate diagnosis. Here we report a strategy to construct a new T1 contrast agent based on the Solomon-Bloembergen-Morgan (SBM) theory. We loaded the ultrasmall gadolinium oxide nanoparticles into worm-like interior channels of mesoporous silica nanospheres (Gd2O3@MSN nanocomposites). This unique structure endows the nanocomposites with geometrical confinement, high molecular tumbling time, and a large coordinated number of water molecules, which results in a significant enhancement of the T1 contrast with longitudinal proton relaxivity (r1) as high as 45.08 mM-1 s-1. Such a high r1 value of Gd2O3@MSN, compared to those of ultrasmall Gd2O3 nanoparticles and gadolinium-based clinical contrast agents, is mainly attributed to the strong geometrical confinement effect. This strategy provides new guidance for developing various high-performance T1 contrast agents for sensitive imaging and disease diagnosis.High-performance magnetic resonance imaging (MRI) contrast agents and novel contrast enhancement strategies are urgently needed for sensitive and accurate diagnosis. Here we report a strategy to construct a new T1 contrast agent based on the Solomon-Bloembergen-Morgan (SBM) theory. We loaded the ultrasmall gadolinium oxide nanoparticles into worm-like interior channels of mesoporous silica nanospheres (Gd2O3@MSN nanocomposites). This unique structure endows the nanocomposites with geometrical confinement, high molecular tumbling time, and a large coordinated number of water molecules, which results in a significant enhancement of the T1 contrast with longitudinal proton relaxivity (r1) as high as 45.08 mM-1 s-1. Such a high r1 value of Gd2O3@MSN, compared to those of ultrasmall Gd2O3 nanoparticles and gadolinium-based clinical contrast agents, is mainly attributed to the strong geometrical confinement effect. This strategy

MRI of normal and abnormal duodenum using Half-Fourier Single-Shot RARE and gadolinium-enhanced spoiled gradient echo sequences.

PubMed

Marcos, H B; Semelka, R C; Noone, T C; Woosley, J T; Lee, J K

1999-07-01

The objective of this research was two-fold: First, to describe the normal and abnormal MR appearances of the duodenum using combined Half-Fourier Acquisition Single Shot RARE (HASTE) and gadolinium-enhanced standard and fat suppressed spoiled gradient echo (SGE) sequences. The second objective was to assess the ability of these combined sequences to detect and characterize duodenal diseases. MR examinations were performed on fifty consecutive patients with no clinical history of duodenal diseases, who were 1) imaged with HASTE and gadolinium-enhanced standard and fat suppressed SGE sequences and 2) referred to MR examination for reasons other than duodenal diseases, and were reviewed retrospectively to determine the normal MR appearances of the duodenum. A second population of patients with abnormal duodenum who were imaged with the same MR sequences were included in the second part of this study. This population was composed of 20 consecutive patients with subsequently proven duodenal abnormalities, including: malrotation (2), diverticula (4), intussusception (1), sprue (1), polyps (2), neurofibroma (1), lymphoma (1), Zollinger Ellison syndrome (1), metastatic disease (1), Crohn's disease (1), and wall thickening and duodenitis (5). Normal measurements of the duodenum are described. Abnormalities of wall thickness and duodenal masses required combined HASTE and gadolinium-enhanced SGE images to evaluate well. Abnormalities of the bowel lumen (e.g., diverticula and intussusception), and developmental variants (e.g., malrotation), were sufficiently visualized on HASTE images alone. Bowel inflammation was best shown on gadolinium-enhanced fat suppressed SGE images. HASTE and gadolinium-enhanced fat suppressed SGE sequences are complementary techniques for the demonstration of normal and abnormal duodenum. The combined use of both sequences allows evaluation of different aspects of bowel diseases; abnormalities of position, lumen, and contents are well shown on HASTE

Gd, I-doped TiO2 thin films coated on solid waste material: synthesis, characterization, and photocatalytic activity under UV or visible light irradiation

NASA Astrophysics Data System (ADS)

Deng, Siwei; Yu, Jiang; Yang, Chun; Chang, Jiahua; Wang, Yizheng; Wang, Ping; Xie, Shiqian

2017-10-01

In this work, titanium dioxide thin films doped with different concentrations of gadolinium (Gd) and iodine (I) were synthesized using the sol-gel method and successfully coated on solid waste material (made in our lab) by dipping, resulting in the titanium dioxide thin-film-coated material (TiO2M). Then, the doped titanium dioxide thin films were characterized by X-ray diffraction (XRD), SEM, and UV-Vis spectroscopy; the optimum coating cycle was evaluated by removal rates of COD and ammonia nitrogen in raw wastewater and secondary effluent. Moreover, the photocatalytic activity was determined by degradation efficiency of methyl orange. The results showed that TiO2M had desirable reusability and the photocatalytic activity was attractive under ultraviolet light irradiation. Furthermore, it is found that the amount of dopant in TiO2 was a key parameter in increasing the photoactivity. 1% Gd-doped TiO2M exhibited the best photocatalytic activity for the degradation of methyl orange with the removal rate reaching 85.55%. The result was in good agreement with the observed smaller crystallite size and profitable crystal structure (anatase phase). Besides, the TiO2M (0.8% Gd-doped TiO2M, 1% Gd-doped TiO2M, 10% I-doped TiO2M, and 5% I-1% Gd-doped TiO2M) with desirable photocatalytic activity at ultraviolet light irradiation was selected for the visible light photocatalytic experiments with taking methyl orange as the target pollutants. The results showed that all of them exhibited the similar photocatalytic activity after 7 h of sunlight irradiation (around 90% removal effect). In general, this research developed a very effective and environmentally friendly photocatalyst for pollutant degradation.

Applying Amide Proton Transfer MR Imaging to Hybrid Brain PET/MR: Concordance with Gadolinium Enhancement and Added Value to [18F]FDG PET.

PubMed

Sun, Hongzan; Xin, Jun; Zhou, Jinyuan; Lu, Zaiming; Guo, Qiyong

2018-06-01

The purpose of this study is to evaluate the diagnostic concordance and metric correlations of amide proton transfer (APT) imaging with gadolinium-enhanced magnetic resonance imaging (MRI) and 2-deoxy-2-[ 18 F-]fluoro-D-glucose ([ 18 F]FDG) positron emission tomography (PET), using hybrid brain PET/MRI. Twenty-one subjects underwent brain gadolinium-enhanced [ 18 F]FDG PET/MRI prospectively. Imaging accuracy was compared between unenhanced MRI, MRI with enhancement, APT-weighted (APTW) images, and PET based on six diagnostic criteria. Among tumors, the McNemar test was further used for concordance assessment between gadolinium-enhanced imaging, APT imaging, and [ 18 F]FDG PET. As well, the relation of metrics between APT imaging and PET was analyzed by the Pearson correlation analysis. APT imaging and gadolinium-enhanced MRI showed superior and similar diagnostic accuracy. APTW signal intensity and gadolinium enhancement were concordant in 19 tumors (100 %), while high [ 18 F]FDG avidity was shown in only 12 (63.2 %). For the metrics from APT imaging and PET, there was significant correlation for 13 hypermetabolic tumors (P < 0.05) and no correlation for the remaining six [ 18 F]FDG-avid tumors. APT imaging can be used to increase diagnostic accuracy with no need to administer gadolinium chelates. APT imaging may provide an added value to [ 18 F]FDG PET in the evaluation of tumor metabolic activity during brain PET/MR studies.

Highly Sensitive Detection of Glucose by a "Turn-Off-On" Fluorescent Probe Using Gadolinium-Doped Carbon Dots and Carbon Microparticles.

PubMed

Hu, Meixin; Qi, Jianrong; Ruan, Jing; Shen, Guangxia

2018-06-01

Carbon dots, as a potential substitute for semiconductor quantum dots, have drawn great interest in recent years. The preparation of fluorescent carbon dots has been made easy with many significant advances, but the complicated purifying processes, low quantum yield, and blue emission wavelength still limit its wider application in biosensors, biomedicine, and photonic devices. Here we report a strategy to synthesis Gd-doped carbon dots (Gd-Cdots) of super-high quantum yield with a microwave assisted hydrothermal method. The Gd-Cdots, with a diameter of 47∼8 nm, can be purified easily with conventional centrifugal techniques. Carbon microparticles (CMPs) have also been synthesized with a similar procedure. Meanwhile, we demonstrated a novel "turn-off-on" fluorescent biosensor, which has been developed for highly sensitive detection of glucose using Gd-doped carbon dots as probes. The proposed biosensor has exhibited low-cost and non-toxic properties, with high sensitivity and good specificity. In addition, the results in real blood samples further confirmed it as a promising application in diabetes diagnosis.

Experimental and modeling studies of sorption of ceria nanoparticle on microbial biofilms.

PubMed

Jing, Hengye; Mezgebe, Bineyam; Aly Hassan, Ashraf; Sahle-Demessie, Endalkachew; Sorial, George A; Bennett-Stamper, Christina

2014-06-01

This study focuses on the interaction of ceria nanoparticles (CeO2-NPs) with Pseudomonas fluorescens and Mycobacterium smegmatis biofilms. Confocal laser microscopy and transmission electron microscopy determined the distribution of NPs in the complex structures of biofilm at molecular levels. Visual data showed that most of the adsorption takes place on the bacterial cell walls and spores. The interaction of nanoparticles (NPs) with biofilms reached equilibrium after the initial high adsorption rate regardless of biofilm heterogeneity and different nanoparticle concentrations in the bulk liquid. Physical processes may dominate this sorption phenomenon. Pseudo first order sorption kinetics was used to estimate adsorption and desorption rate of CeO2-NPs onto biofilms. When biofilms got exposed to CeO2-NPs, a self-protecting mechanism was observed. Cells moved away from the bulk solution in the biofilm matrix, and portions of biofilm outer layer were detached, hence releasing some CeO2-NPs back to the bulk phase. Published by Elsevier Ltd.

Finite-temperature lattice dynamics and superionic transition in ceria from first principles

NASA Astrophysics Data System (ADS)

Klarbring, Johan; Skorodumova, Natalia V.; Simak, Sergei I.

2018-03-01

Ab initio molecular dynamics (AIMD) in combination with the temperature dependent effective potential (TDEP) method has been used to go beyond the quasiharmonic approximation and study the lattice dynamics in ceria, CeO2, at finite temperature. The results indicate that the previously proposed connection between the B1 u phonon mode turning imaginary and the transition to the superionic phase in fluorite structured materials is an artifact of the failure of the quasiharmonic approximation in describing the lattice dynamics at elevated temperatures. We instead show that, in the TDEP picture, a phonon mode coupling to the Eu mode prevents the B1 u mode from becoming imaginary. We directly observe the superionic transition at high temperatures in our AIMD simulations and find that it is initiated by the formation of oxygen Frenkel pairs (FP). These FP are found to form in a collective process involving simultaneous motion of two oxygen ions.

Polythermal investigation of viscosity of solution of metal carboxylates in VIK-grade mixed carboxylic acids: Yttrium and gadolinium carboxylates

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

Mezhov, E.A.; Samatov, A.V.; Troyanovskii, L.V.

Kinematic viscosities have been measured for solutions of yttrium and gadolinium carboxylates in grade VIK mixed carboxylic acids (MCA). It has been established that the optimal fluidity of these metal carboxylate solutions for application to articles is reached at 333 K. A regression model has been developed to describe the concentration and temperature dependences of the viscosity of yttrium- and gadolinium-containing MCA solutions. 2 refs., 3 tabs.

Single-step synthesis of Er3+ and Yb3+ ions doped molybdate/Gd2O3 core-shell nanoparticles for biomedical imaging

NASA Astrophysics Data System (ADS)

Kamińska, Izabela; Elbaum, Danek; Sikora, Bożena; Kowalik, Przemysław; Mikulski, Jakub; Felcyn, Zofia; Samol, Piotr; Wojciechowski, Tomasz; Minikayev, Roman; Paszkowicz, Wojciech; Zaleszczyk, Wojciech; Szewczyk, Maciej; Konopka, Anna; Gruzeł, Grzegorz; Pawlyta, Mirosława; Donten, Mikołaj; Ciszak, Kamil; Zajdel, Karolina; Frontczak-Baniewicz, Małgorzata; Stępień, Piotr; Łapiński, Mariusz; Wilczyński, Grzegorz; Fronc, Krzysztof

2018-01-01

Nanostructures as color-tunable luminescent markers have become major, promising tools for bioimaging and biosensing. In this paper separated molybdate/Gd2O3 doped rare earth ions (erbium, Er3+ and ytterbium, Yb3+) core-shell nanoparticles (NPs), were fabricated by a one-step homogeneous precipitation process. Emission properties were studied by cathodo- and photoluminescence. Scanning electron and transmission electron microscopes were used to visualize and determine the size and shape of the NPs. Spherical NPs were obtained. Their core-shell structures were confirmed by x-ray diffraction and energy-dispersive x-ray spectroscopy measurements. We postulated that the molybdate rich core is formed due to high segregation coefficient of the Mo ion during the precipitation. The calcination process resulted in crystallization of δ/ξ (core/shell) NP doped Er and Yb ions, where δ—gadolinium molybdates and ξ—molybdates or gadolinium oxide. We confirmed two different upconversion mechanisms. In the presence of molybdenum ions, in the core of the NPs, Yb3+-{{{{MoO}}}4}2- (∣2F7/2, 3T2〉) dimers were formed. As a result of a two 980 nm photon absorption by the dimer, we observed enhanced green luminescence in the upconversion process. However, for the shell formed by the Gd2O3:Er, Yb NPs (without the Mo ions), the typical energy transfer upconversion takes place, which results in red luminescence. We demonstrated that the NPs were transported into cytosol of the HeLa and astrocytes cells by endocytosis. The core-shell NPs are sensitive sensors for the environment prevailing inside (shorter luminescence decay) and outside (longer luminescence decay) of the tested cells. The toxicity of the NPs was examined using MTT assay.

The performance of hafnium and gadolinium self powered neutron detectors in the TREAT reactor

NASA Astrophysics Data System (ADS)

Imel, G. R.; Hart, P. R.

1996-05-01

The use of gadolinium and hafnium self powered neutron detectors in a transient reactor is described in this paper. The detectors were calibrated to the fission rate of U-235 using calibrated fission chambers; the calibration factors were tested in two reactors in steady state and found to be consistent. Calibration of the detectors in transient reactor conditions was done by using uranium wires that were analyzed by radiochemistry techniques to determine total fissions during the transient. This was correlated to the time-integrated current of the detectors during the transient. A temperature correction factor was derived to account for self-shielding effects in the hafnium and gadolinium detectors. The dynamic response of the detectors under transient conditions was studied, and found to be excellent.

Identification of ε-Fe2O3 nano-phase in borate glasses doped with Fe and Gd

NASA Astrophysics Data System (ADS)

Ivanova, O. S.; Ivantsov, R. D.; Edelman, I. S.; Petrakovskaja, E. A.; Velikanov, D. A.; Zubavichus, Y. V.; Zaikovskii, V. I.; Stepanov, S. A.

2016-03-01

A new type of magnetic nanoparticles was revealed in borate glasses co-doped with low contents of iron and gadolinium. Structure and magnetic properties of the particles differ essentially from that of the α-Fe2O3, γ-Fe2O3, or Fe3O4 nanoparticles which were detected earlier in similar glass matrices. Transmission electron microscopy including STEM-HAADF and EDX, synchrotron radiation-based XRD, static magnetic measurements, magnetic circular dichroism, and electron magnetic resonance studies allow referring the nanoparticles to the iron oxide phase-ε-Fe2O3. Analysis of the data set has shown that it is Gd atoms that govern the process of nanoparticles' nucleation and its incorporation into the particles in different proportions can be used to adjust their magnetic and magneto-optical characteristics.

Breakthrough reactions of iodinated and gadolinium contrast media after oral steroid premedication protocol.

PubMed

Jingu, Akiko; Fukuda, Junya; Taketomi-Takahashi, Ayako; Tsushima, Yoshito

2014-10-06

Adverse reactions to iodinated and gadolinium contrast media are an important clinical issue. Although some guidelines have proposed oral steroid premedication protocols to prevent adverse reactions, some patients may have reactions to contrast media in spite of premedication (breakthrough reaction; BTR).The purpose of this study was to assess the frequency, type and severity of BTR when following an oral steroid premedication protocol. All iodinated and gadolinium contrast-enhanced radiologic examinations between August 2011 and February 2013 for which the premedication protocol was applied in our institution were assessed for BTRs. The protocol was applied to a total of 252 examinations (153 patients, ages 15-87 years; 63 males, 90 females). Of these, 152 were for prior acute adverse reactions to contrast media, 85 were for a history of bronchial asthma, and 15 were for other reasons. There were 198 contrast enhanced CTs and 54 contrast enhanced MRIs. There were nine BTR (4.5%) for iodinated contrast media, and only one BTR (1.9%) for gadolinium contrast media: eight were mild and one was moderate. No patient who had a mild index reaction (IR) had a severe BTR. Incidence of BTRs when following the premedication protocol was low. This study by no means proves the efficacy of premedication, but provides some support for following a premedication protocol to improve safety of contrast-enhanced examinations when prior adverse reactions are mild, or when there is a history of asthma.

Breakthrough reactions of iodinated and gadolinium contrast media after oral steroid premedication protocol

PubMed Central

2014-01-01

Background Adverse reactions to iodinated and gadolinium contrast media are an important clinical issue. Although some guidelines have proposed oral steroid premedication protocols to prevent adverse reactions, some patients may have reactions to contrast media in spite of premedication (breakthrough reaction; BTR). The purpose of this study was to assess the frequency, type and severity of BTR when following an oral steroid premedication protocol. Methods All iodinated and gadolinium contrast-enhanced radiologic examinations between August 2011 and February 2013 for which the premedication protocol was applied in our institution were assessed for BTRs. Results The protocol was applied to a total of 252 examinations (153 patients, ages 15–87 years; 63 males, 90 females). Of these, 152 were for prior acute adverse reactions to contrast media, 85 were for a history of bronchial asthma, and 15 were for other reasons. There were 198 contrast enhanced CTs and 54 contrast enhanced MRIs. There were nine BTR (4.5%) for iodinated contrast media, and only one BTR (1.9%) for gadolinium contrast media: eight were mild and one was moderate. No patient who had a mild index reaction (IR) had a severe BTR. Conclusion Incidence of BTRs when following the premedication protocol was low. This study by no means proves the efficacy of premedication, but provides some support for following a premedication protocol to improve safety of contrast-enhanced examinations when prior adverse reactions are mild, or when there is a history of asthma. PMID:25287952

Bimetallic Nickel/Ruthenium Catalysts Synthesized by Atomic Layer Deposition for Low-Temperature Direct Methanol Solid Oxide Fuel Cells.

PubMed

Jeong, Heonjae; Kim, Jun Woo; Park, Joonsuk; An, Jihwan; Lee, Tonghun; Prinz, Fritz B; Shim, Joon Hyung

2016-11-09

Nickel and ruthenium bimetallic catalysts were heterogeneously synthesized via atomic layer deposition (ALD) for use as the anode of direct methanol solid oxide fuel cells (DMSOFCs) operating in a low-temperature range. The presence of highly dispersed ALD Ru islands over a porous Ni mesh was confirmed, and the Ni/ALD Ru anode microstructure was observed. Fuel cell tests were conducted using Ni-only and Ni/ALD Ru anodes with approximately 350 μm thick gadolinium-doped ceria electrolytes and platinum cathodes. The performance of fuel cells was assessed using pure methanol at operating temperatures of 300-400 °C. Micromorphological changes of the anode after cell operation were investigated, and the content of adsorbed carbon on the anode side of the operated samples was measured. The difference in the maximum power density between samples utilizing Ni/ALD Ru and Pt/ALD Ru, the latter being the best catalyst for direct methanol fuel cells, was observed to be less than 7% at 300 °C and 30% at 350 °C. The improved electrochemical activity of the Ni/ALD Ru anode compared to that of the Ni-only anode, along with the reduction of the number of catalytically active sites due to agglomeration of Ni and carbon formation on the Ni surface as compared to Pt, explains this decent performance.

Hydrodeoxygenation of vicinal OH groups over heterogeneous rhenium catalyst promoted by palladium and ceria support.

PubMed

Ota, Nobuhiko; Tamura, Masazumi; Nakagawa, Yoshinao; Okumura, Kazu; Tomishige, Keiichi

2015-02-02

Heterogeneous ReOx-Pd/CeO2 catalyst showed excellent performance for simultaneous hydrodeoxygenation of vicinal OH groups. High yield (>99%), turnover frequency (300 h(-1)), and turnover number (10,000) are achieved in the reaction of 1,4-anhydroerythritol to tetrahydrofuran. This catalyst can be applied to sugar alcohols, and mono-alcohols and diols are obtained in high yields (≥85%) from substrates with even and odd numbers of OH groups, respectively. The high catalytic performance of ReOx-Pd/CeO2 can be assigned to rhenium species with +4 or +5 valence state, and the formation of this species is promoted by H2/Pd and the ceria support. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Developing Cost-Effective Dense Continuous SDC Barrier Layers for SOFCs

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

Nguyen, Hoang Viet P.; Hardy, John S.; Coyle, Christopher A.

Significantly improved performance during electrochemical testing of a cell with a dense continuous pulsed laser deposited (PLD) samarium doped ceria (SDC) layer spurred investigations into the fabrication of dense continuous SDC barrier layers by means of cost-effective deposition using screen printing which is amenable to industrial production of SOFCs. Many approaches to improve the SDC density have been explored including the use of powder with reduced particle sizes, inks with increased solids loading, and doping with sintering aids (1). In terms of sintering aids, dopants like Mo or binary systems of Mo+Cu or Fe+Co greatly enhance SDC sinterability. In fact,more » adding dopants to a screen printed, prefired, porous SDC layer made it possible to achieve a dense continuous barrier layer atop the YSZ electrolyte without sintering above 1200°C. Although the objective of fabricating a dense continuous layer was achieved, additional studies have been initiated to improve the cell performance. Underlying issues with constrained sintering and dopant-enhanced ceria-zirconia solid solubility are also addressed in this paper.« less

Effect of Cu2+ substitution on the structural, magnetic and electrical properties of gadolinium orthoferrite

NASA Astrophysics Data System (ADS)

Sai Vandana, C.; Hemalatha Rudramadevi, B.

2018-04-01

The pure and copper (Cu) substituted Gadolinium orthoferrites, GdFeO3, GdCu0.1Fe0.9O3, GdCu0.2Fe0.8O3 and GdCu0.3Fe0.7O3 were synthesized by conventional solid state method. The structural, morphological, dielectric, magnetic and impedance properties of Cu substituted Gadolinium orthoferrites have been investigated. The crystallographic phase as well as the substitution of Cu2+ ions in the lattice of GdFeO3 is confirmed from the x-ray diffraction patterns. The Fourier transform infrared spectra exhibit two prominent fundamental absorption peaks at ∼417 cm‑1 and 545 cm‑1. These bands are related to inherent stretching vibrations of metals at octahedral and tetrahedral sites respectively. The coercivity (Hc) and saturation magnetization (Ms) of the synthesized samples at different temperatures were determined from the hysteresis plots. Higher coercive values, 598 Oe and 600 Oe were achieved in GdCu0.1Fe0.9O3 ferrites compared to 527 Oe and 360 Oe in pure GdFeO3 at room temperature (300 K) and low temperature (20 k) respectively. Dielectric dispersion has been observed for gadolinium ferrite samples with Maxwell–Wagner type interfacial polarization. The decrease of dielectric constant and dielectric loss tangent with an increase in frequency was observed. The conduction due to charge hopping between localized states was confirmed from AC conductivity measurements. The composition dependent cationic distributions estimated from XRD, magnetic and electrical studies are in good agreement with each other. The achieved results indicate that the substitution of Cu in gadolinium orthoferrite strongly influences the crystal structure, magnetic and electrical properties thereby making them suitable as multiple state memory devices, transducers, electronic field controlled ferromagnetic resonance devices and spintronic devices.

Pathways for Ethanol Dehydrogenation and Dehydration Catalyzed by Ceria (111) and (100) Surfaces

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

Beste, Ariana; Steven Overbury

2015-01-08

We have performed computations to better understand how surface structure affects selectivity in dehydrogenation and dehydration reactions of alcohols. Ethanol reactions on the (111) and (100) ceria surfaces were studied starting from the dominant surface species, ethoxy. We used DFT (PBE+U) to explore reaction pathways leading to ethylene and acetaldehyde and calculated estimates of rate constants employing transition state theory. To assess pathway contributions, we carried out kinetic analysis. Our results show that intermediate and transition state structures are stabilized on the (100) surface compared to the (111) surface. Formation of acetaldehyde over ethylene is kinetically and thermodynamically preferred onmore » both surfaces. Our results are consistent with temperature programmed surface reaction and steady-state experiments, where acetaldehyde was found as the main product and evidence was presented that ethylene formation at higher temperature originates from changes in adsorbate and surface structure.« less

Application of an oscillation-type linear cadmium telluride detector to enhanced gadolinium K-edge computed tomography

NASA Astrophysics Data System (ADS)

Matsukiyo, Hiroshi; Sato, Eiichi; Hagiwara, Osahiko; Abudurexiti, Abulajiang; Osawa, Akihiro; Enomoto, Toshiyuki; Watanabe, Manabu; Nagao, Jiro; Sato, Shigehiro; Ogawa, Akira; Onagawa, Jun

2011-03-01

A linear cadmium telluride (CdTe) detector is useful for carrying out energy-discrimination X-ray imaging, including computed tomography (CT). To perform enhanced gadolinium K-edge CT, we used an oscillation-type linear CdTe detector with an energy resolution of 1.2 keV. CT is performed by repeating the linear scan and the rotation of an object. Penetrating X-ray photons from the object are detected by the CdTe detector, and event signals of X-ray photons are produced using charge-sensitive and shaping amplifiers. Both the photon energy and the energy width are selected using a multichannel analyzer, and the number of photons is counted by a counter card. In energy-discrimination CT, tube voltage and current were 80 kV and 20 μA, respectively, and X-ray intensity was 1.55 μGy/s at 1.0 m from the source at a tube voltage of 80 kV. Demonstration of enhanced gadolinium K-edge X-ray CT was carried out by selecting photons with energies just beyond gadolinium K-edge energy of 50.3 keV.

Deep learning enables reduced gadolinium dose for contrast-enhanced brain MRI.

PubMed

Gong, Enhao; Pauly, John M; Wintermark, Max; Zaharchuk, Greg

2018-02-13

There are concerns over gadolinium deposition from gadolinium-based contrast agents (GBCA) administration. To reduce gadolinium dose in contrast-enhanced brain MRI using a deep learning method. Retrospective, crossover. Sixty patients receiving clinically indicated contrast-enhanced brain MRI. 3D T 1 -weighted inversion-recovery prepped fast-spoiled-gradient-echo (IR-FSPGR) imaging was acquired at both 1.5T and 3T. In 60 brain MRI exams, the IR-FSPGR sequence was obtained under three conditions: precontrast, postcontrast images with 10% low-dose (0.01mmol/kg) and 100% full-dose (0.1 mmol/kg) of gadobenate dimeglumine. We trained a deep learning model using the first 10 cases (with mixed indications) to approximate full-dose images from the precontrast and low-dose images. Synthesized full-dose images were created using the trained model in two test sets: 20 patients with mixed indications and 30 patients with glioma. For both test sets, low-dose, true full-dose, and the synthesized full-dose postcontrast image sets were compared quantitatively using peak-signal-to-noise-ratios (PSNR) and structural-similarity-index (SSIM). For the test set comprised of 20 patients with mixed indications, two neuroradiologists scored blindly and independently for the three postcontrast image sets, evaluating image quality, motion-artifact suppression, and contrast enhancement compared with precontrast images. Results were assessed using paired t-tests and noninferiority tests. The proposed deep learning method yielded significant (n = 50, P < 0.001) improvements over the low-dose images (>5 dB PSNR gains and >11.0% SSIM). Ratings on image quality (n = 20, P = 0.003) and contrast enhancement (n = 20, P < 0.001) were significantly increased. Compared to true full-dose images, the synthesized full-dose images have a slight but not significant reduction in image quality (n = 20, P = 0.083) and contrast enhancement (n = 20, P = 0.068). Slightly

Supported Pd nanoclusters with enhanced hydrogen spillover for NOx removal via H2-SCR: the elimination of "volcano-type" behaviour.

PubMed

Peng, Zhezhe; Li, Zongyuan; Liu, Yun-Quan; Yan, Shuai; Tong, Jianing; Wang, Duo; Ye, Yueyuan; Li, Shuirong

2017-05-30

A rational design of a Pd catalyst with highly dispersed Pd nanoclusters on an Al doped ceria-based oxide for low temperature selective catalytic reduction of NO x by hydrogen with excess O 2 was achieved. The supported Pd nanocluster shows a high hydrogen spillover ability and a NO x conversion of >84% within 100-300 °C.

[Preparation and photocatalytic activity of boron doped CeO2/TiO2 mixed oxides].

PubMed

Tang, Xin-hu; Wei, Chao-hai; Liang, Jie-rong; Wang, Bo-guang

2006-07-01

Boron doped CeO2/TiO2 mixed oxides photocatalysts were prepared by adding boric acid and cerous nitrate during the hydrolyzation of titanium trichloride and tetrabutyl titanate. XRD, UV-Vis DRS and XPS techniques were used to characterize the crystalline structure, light absorbing ability and the chemical state of Boron element in the photocatalyst sample. The photocatalytic activities were evaluated by monitoring the degradation of acid red B under UV irradiation. These results indicate that the wavelengths at adsorbing edge are affected by the content of cerous nitrate and the maximum absorption wavelength is about 481 nm when the mole ratio of Ce/Ti is 1.0. For higher dosage of Cerium, the absorbance edge shifts to blue slightly. The prepared photocatalyst is composed of anatase TiO2 and cubic CeO2 when calcined at 500 degrees C. An increase in the calcination temperature transforms the crystalline structure of the titanium oxides from anatase to rutile, and has no obvious influence on crystalline structure of CeO2 but crystallites growth up. The absorbance edge decreases drastically with the increase of calcination temperature. With a view to the stability of photocatalyst and utilization of sun energy, 500 degrees C of calcination temperature is recommended. The XP spectrum for B1s exhibits that only a few boron ions dope into titania and ceria matrix, others exist in B2O3. The photocatalytic activity increases with increase of cerous nitrate dosage, and decreases drastically due to higher dosage (the mol ratio of Ce/Ti > 0.5). After 10 min UV irradiation, 96% of acid red B is degraded completely over photocatalyst under optimum reaction condition.

Kondo effect and enhanced magnetic properties in gadolinium functionalized carbon nanotube supramolecular complex.

PubMed

Ncube, S; Coleman, C; Strydom, A; Flahaut, E; de Sousa, A; Bhattacharyya, S

2018-05-23

We report on the enhancement of magnetic properties of multiwalled carbon nanotubes (MWNTs) functionalized with a gadolinium based supramolecular complex. By employing a newly developed synthesis technique we find that the functionalization method of the nanocomposite enhances the strength of magnetic interaction leading to a large effective moment of 15.79 µ B and non-superparamagnetic behaviour unlike what has been previously reported. Saturating resistance at low temperatures is fitted with the numerical renormalization group formula verifying the Kondo effect for magnetic impurities on a metallic electron system. Magnetoresistance shows devices fabricated from aligned gadolinium functionalized MWNTs (Gd-Fctn-MWNTs) exhibit spin-valve switching behaviour of up to 8%. This study highlights the possibility of enhancing magnetic interactions in carbon systems through chemical modification, moreover we demonstrate the rich physics that might be useful for developing spin based quantum computing elements based on one-dimensional (1D) channels.

Imaging of cauda equina edema in lumbar canal stenosis by using gadolinium-enhanced MR imaging: experimental constriction injury.

PubMed

Kobayashi, S; Uchida, K; Takeno, K; Baba, H; Suzuki, Y; Hayakawa, K; Yoshizawa, H

2006-02-01

It has been reported that disturbance of blood flow arising from circumferential compression of the cauda equina by surrounding tissue plays a major role in the appearance of neurogenic intermittent claudication (NIC) associated with lumbar spinal canal stenosis (LSCS). We created a model of LSCS to clarify the mechanism of enhancement within the cauda equina on gadolinium-enhanced MR images from patients with LSCS. In 20 dogs, a lumbar laminectomy was performed by applying circumferential constriction to the cauda equina by using a silicon tube, to produce 30% stenosis of the circumferential diameter of the dural tube. After 1 and 3 weeks, gadolinium and Evans blue albumin were injected intravenously at the same time. The sections were used to investigate the status of the blood-nerve barrier function under a fluorescence microscope and we compared gadolinium-enhanced MR images with Evans blue albumin distribution in the nerve. The other sections were used for light and transmission electron microscopic study. In this model, histologic examination showed congestion and dilation in many of the intraradicular veins, as well as inflammatory cell infiltration. The intraradicular edema caused by venous congestion and Wallerian degeneration can also occur at sites that are not subject to mechanical compression. Enhanced MR imaging showed enhancement of the cauda equina at the stenosed region, demonstrating the presence of edema. Gadolinium-enhanced MR imaging may be a useful tool for the diagnosis of microcirculatory disorders of the cauda equina associated with LSCS.

Partial Oxidation of Hydrocarbons in a Segmented Bed Using Oxide-based Catalysts and Oxygen-conducting Supports

NASA Astrophysics Data System (ADS)

Smith, Mark W.

Two objectives for the catalytic reforming of hydrocarbons to produce synthesis gas are investigated herein: (1) the effect of oxygen-conducting supports with partially substituted mixed-metal oxide catalysts, and (2) a segmented bed approach using different catalyst configurations. Excess carbon deposition was the primary cause of catalyst deactivation, and was the focus of the experiments for both objectives. The formation and characterization of deposited carbon was examined after reaction for one of the selected catalysts to determine the quantity and location of the carbon on the catalyst surface leading to deactivation. A nickel-substituted barium hexaaluminate (BNHA), with the formula BaAl 11.6Ni0.4O18.8, and a Rh-substituted lanthanum zirconate pyrochlore (LCZR) with the formula La1.89Ca0.11 Zr1.89Rh0.11, were combined with two different doped ceria supports. These supports were gadolinium-doped ceria (GDC) and zirconium-doped ceria (ZDC). The active catalyst phases were combined with the supports in different ratios using different synthesis techniques. The catalysts were characterized using several different techniques and were tested under partial oxidation (POX) of n-tetradecane (TD), a diesel fuel surrogate. It was found that the presence of GDC and ZDC reduced the formation of carbon for both catalysts; the optimal ratio of catalyst to support was different for the hexaaluminate and the pyrochlore; a loading of 20 wt% of the pyrochlore with ZDC produced the most stable performance in the presence of common fuel contaminants (>50 h); and, the incipient wetness impregnation synthesis method of applying the active catalyst to the support produced more stable product yields than the catalyst prepared by a solid-state mixing technique. Different hexaaluminate and pyrochlore catalysts were used in different configurations in a segmented bed approach. The first strategy was to promote the indirect reforming mechanism by placing a combustion catalyst in the

In vitro study of novel gadolinium-loaded liposomes guided by GBI-10 aptamer for promising tumor targeting and tumor diagnosis by magnetic resonance imaging.

PubMed

Gu, Meng-Jie; Li, Kun-Feng; Zhang, Lan-Xin; Wang, Huan; Liu, Li-Si; Zheng, Zhuo-Zhao; Han, Nan-Yin; Yang, Zhen-Jun; Fan, Tian-Yuan

2015-01-01

Novel gadolinium-loaded liposomes guided by GBI-10 aptamer were developed and evaluated in vitro to enhance magnetic resonance imaging (MRI) diagnosis of tumor. Nontargeted gadolinium-loaded liposomes were achieved by incorporating amphipathic material, Gd (III) [N,N-bis-stearylamidomethyl-N'-amidomethyl] diethylenetriamine tetraacetic acid, into the liposome membrane using lipid film hydration method. GBI-10, as the targeting ligand, was then conjugated onto the liposome surface to get GBI-10-targeted gadolinium-loaded liposomes (GTLs). Both nontargeted gadolinium-loaded liposomes and GTLs displayed good dispersion stability, optimal size, and zeta potential for tumor targeting, as well as favorable imaging properties with enhanced relaxivity compared with a commercial MRI contrast agent (CA), gadopentetate dimeglumine. The use of GBI-10 aptamer in this liposomal system was intended to result in increased accumulation of gadolinium at the periphery of C6 glioma cells, where the targeting extracellular matrix protein tenascin-C is overexpressed. Increased cellular binding of GTLs to C6 cells was confirmed by confocal microscopy, flow cytometry, and MRI, demonstrating the promise of this novel delivery system as a carrier of MRI contrast agent for the diagnosis of tumor. These studies provide a new strategy furthering the development of nanomedicine for both diagnosis and therapy of tumor.

In vitro study of novel gadolinium-loaded liposomes guided by GBI-10 aptamer for promising tumor targeting and tumor diagnosis by magnetic resonance imaging

PubMed Central

Gu, Meng-Jie; Li, Kun-Feng; Zhang, Lan-Xin; Wang, Huan; Liu, Li-Si; Zheng, Zhuo-Zhao; Han, Nan-Yin; Yang, Zhen-Jun; Fan, Tian-Yuan

2015-01-01

Novel gadolinium-loaded liposomes guided by GBI-10 aptamer were developed and evaluated in vitro to enhance magnetic resonance imaging (MRI) diagnosis of tumor. Nontargeted gadolinium-loaded liposomes were achieved by incorporating amphipathic material, Gd (III) [N,N-bis-stearylamidomethyl-N′-amidomethyl] diethylenetriamine tetraacetic acid, into the liposome membrane using lipid film hydration method. GBI-10, as the targeting ligand, was then conjugated onto the liposome surface to get GBI-10-targeted gadolinium-loaded liposomes (GTLs). Both nontargeted gadolinium-loaded liposomes and GTLs displayed good dispersion stability, optimal size, and zeta potential for tumor targeting, as well as favorable imaging properties with enhanced relaxivity compared with a commercial MRI contrast agent (CA), gadopentetate dimeglumine. The use of GBI-10 aptamer in this liposomal system was intended to result in increased accumulation of gadolinium at the periphery of C6 glioma cells, where the targeting extracellular matrix protein tenascin-C is overexpressed. Increased cellular binding of GTLs to C6 cells was confirmed by confocal microscopy, flow cytometry, and MRI, demonstrating the promise of this novel delivery system as a carrier of MRI contrast agent for the diagnosis of tumor. These studies provide a new strategy furthering the development of nanomedicine for both diagnosis and therapy of tumor. PMID:26316749

Impact of Impaired Renal Function on Gadolinium Retention After Administration of Gadolinium-Based Contrast Agents in a Mouse Model.

PubMed

Kartamihardja, A Adhipatria P; Nakajima, Takahito; Kameo, Satomi; Koyama, Hiroshi; Tsushima, Yoshito

2016-10-01

The aim of this study was to investigate the impact of impaired renal function on gadolinium (Gd) retention in various organs after Gd-based contrast agent injection. After local animal care and review committee approval, 23 normal mice and 26 with renal failure were divided into 4 treatment groups (Gd-DTPA-BMA, 5 mmol/kg; Gd-DOTA, 5 mmol/kg; GdCl3, 0.02 mmol/kg; and saline, 250 μL). Each agent was intravenously administered on weekdays for 4 weeks. Samples were collected on days 3 (short-term) and 45 (long-term) after the last injection. Gadolinium concentrations were quantified by inductively coupled plasma-mass spectrometry. Three mice with renal failure and 2 normal mice in the GdCl3 group and 1 mouse with renal failure in the Gd-DTPA-BMA group died. In the Gd-DTPA-BMA group, impaired renal function increased short-term Gd retention in the liver, bone, spleen, skin, and kidney (P < 0.01) but did not affect long-term Gd retention. Gd-DTPA-BMA showed higher Gd retention than Gd-DOTA. Although Gd retention in the Gd-DOTA group was generally low, impaired renal function increased only long-term hepatic Gd retention. Hepatic and splenic Gd retentions were significantly higher than other organs' Gd retention in the GdCl3 group (P < 0.01). Renal function did not affect brain Gd retention, regardless of the Gd compound used. The tendency of Gd retention varied according to the agent, regardless of renal function. Although renal impairment increased short-term Gd retention after Gd-DTPA-BMA administration, long-term Gd retention for Gd-based contrast agents was almost unaffected by renal function, suggesting that the chemical structures of retained Gd may not be consistent and some Gd is slowly eliminated after initially being retained.

Gadolinium-Doped Gallic Acid-Zinc/Aluminium-Layered Double Hydroxide/Gold Theranostic Nanoparticles for a Bimodal Magnetic Resonance Imaging and Drug Delivery System.

PubMed

Sani Usman, Muhammad; Hussein, Mohd Zobir; Fakurazi, Sharida; Masarudin, Mas Jaffri; Ahmad Saad, Fathinul Fikri

2017-08-31

We have developed gadolinium-based theranostic nanoparticles for co-delivery of drug and magnetic resonance imaging (MRI) contrast agent using Zn/Al-layered double hydroxide as the nanocarrier platform, a naturally occurring phenolic compound, gallic acid (GA) as therapeutic agent, and Gd(NO₃)₃ as diagnostic agent. Gold nanoparticles (AuNPs) were grown on the system to support the contrast for MRI imaging. The nanoparticles were characterized using techniques such as Hi-TEM, XRD, ICP-ES. Kinetic release study of the GA from the nanoparticles showed about 70% of GA was released over a period of 72 h. The in vitro cell viability test for the nanoparticles showed relatively low toxicity to human cell lines (3T3) and improved toxicity on cancerous cell lines (HepG2). A preliminary contrast property test of the nanoparticles, tested on a 3 Tesla MRI machine at various concentrations of GAGZAu and water (as a reference) indicates that the nanoparticles have a promising dual diagnostic and therapeutic features to further develop a better future for clinical remedy for cancer treatment.

Gadolinium-Doped Gallic Acid-Zinc/Aluminium-Layered Double Hydroxide/Gold Theranostic Nanoparticles for a Bimodal Magnetic Resonance Imaging and Drug Delivery System

PubMed Central

Sani Usman, Muhammad; Hussein, Mohd Zobir; Fakurazi, Sharida; Ahmad Saad, Fathinul Fikri

2017-01-01

We have developed gadolinium-based theranostic nanoparticles for co-delivery of drug and magnetic resonance imaging (MRI) contrast agent using Zn/Al-layered double hydroxide as the nanocarrier platform, a naturally occurring phenolic compound, gallic acid (GA) as therapeutic agent, and Gd(NO3)3 as diagnostic agent. Gold nanoparticles (AuNPs) were grown on the system to support the contrast for MRI imaging. The nanoparticles were characterized using techniques such as Hi-TEM, XRD, ICP-ES. Kinetic release study of the GA from the nanoparticles showed about 70% of GA was released over a period of 72 h. The in vitro cell viability test for the nanoparticles showed relatively low toxicity to human cell lines (3T3) and improved toxicity on cancerous cell lines (HepG2). A preliminary contrast property test of the nanoparticles, tested on a 3 Tesla MRI machine at various concentrations of GAGZAu and water (as a reference) indicates that the nanoparticles have a promising dual diagnostic and therapeutic features to further develop a better future for clinical remedy for cancer treatment. PMID:28858229

Disparate ultrafast dynamics of itinerant and localized magnetic moments in gadolinium metal

PubMed Central

Frietsch, B.; Bowlan, J.; Carley, R.; Teichmann, M.; Wienholdt, S.; Hinzke, D.; Nowak, U.; Carva, K.; Oppeneer, P. M.; Weinelt, M.

2015-01-01

The Heisenberg–Dirac intra-atomic exchange coupling is responsible for the formation of the atomic spin moment and thus the strongest interaction in magnetism. Therefore, it is generally assumed that intra-atomic exchange leads to a quasi-instantaneous aligning process in the magnetic moment dynamics of spins in separate, on-site atomic orbitals. Following ultrashort optical excitation of gadolinium metal, we concurrently record in photoemission the 4f magnetic linear dichroism and 5d exchange splitting. Their dynamics differ by one order of magnitude, with decay constants of 14 versus 0.8 ps, respectively. Spin dynamics simulations based on an orbital-resolved Heisenberg Hamiltonian combined with first-principles calculations explain the particular dynamics of 5d and 4f spin moments well, and corroborate that the 5d exchange splitting traces closely the 5d spin-moment dynamics. Thus gadolinium shows disparate dynamics of the localized 4f and the itinerant 5d spin moments, demonstrating a breakdown of their intra-atomic exchange alignment on a picosecond timescale. PMID:26355196

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.

K3 Li3 Gd7 (BO3 )9 : A New Gadolinium-Rich Orthoborate for Cryogenic Magnetic Cooling.

PubMed

Xia, Mingjun; Shen, Shipeng; Lu, Jun; Sun, Young; Li, Rukang

2018-03-02

Magnetic cooling technology based on magnetocaloric effect (MCE) has attracted great interest in obtaining extremely low temperatures, for example, for space exploration. Here, we grew a new gadolinium-rich orthoborate K 3 Li 3 Gd 7 (BO 3 ) 9 (1) as a promising cryogenic magnetic coolant. It exhibits a complicated three dimensional framework constructed from BO 3 groups and gadolinium-oxygen chains. The Gd-O chain consists of two types of clusters of Gd 3 O 20 and Gd 3 O 19 interconnection by Gd(4)O 8 polyhydron. Due to its high gadolinium concentration, a large -ΔS m of 56.6 J kg -1  K -1 for 1 was obtained at 2 K and ΔH=7 T, much larger than that of the commercial benchmark Gd 3 Ga 5 O 12 (GGG) crystal (38.4 J kg -1  K -1 ), suggesting it to be an excellent MCE material. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Transient arterial phase respiratory motion-related artifact in MR imaging of the liver: an analysis of four different gadolinium-based contrast agents.

PubMed

Shah, Mansi R; Flusberg, Milana; Paroder, Viktoriya; Rozenblit, Alla M; Chernyak, Victoria

The purpose was to compare hepatic arterial phase (HAP) respiratory motion artifact (RMA) between gadoxetate, gadobutrol, gadopentetate, and gadobenate. Two hundred cases of each gadolinium agent were included. RMA was assigned using 5-point Likert scale (1=no motion, 5=extreme motion) on precontrast and HAP. RMA increase (increase ≥1 on HAP from precontrast) was the outcome in logistic regression. Odds of RMA increase for gadoxetate were 5.5 (P<.001), 3.6 (P=.034), and 9.5 (P<.001) times higher than gadobutrol, gadopentetate, and gadobenate, respectively. Gadolinium volume and dose were not independent predictors of RMA increase. Gadoxetate has increased odds of RMA compared with other gadolinium agents; tight contrast bolus is not a contributor. Copyright © 2016 Elsevier Inc. All rights reserved.

Efficient charge transfer and utilization of near-infrared solar spectrum by ytterbium and thulium codoped gadolinium molybdate (Gd2(MoO4)3:Yb/Tm) nanophosphor in hybrid solar cells.

PubMed

Sun, Weifu; Chen, Zihan; Zhang, Qin; Zhou, Junli; Li, Feng; Jin, Xiao; Li, Dongyu; Li, Qinghua

2016-11-09

In this work, thulium and ytterbium codoped gadolinium molybdate (Gd 2 (MoO 4 ) 3 :Yb/Tm) nanophosphors (NPs) have been synthesized, followed by being incorporated into a photo-catalytic titania (TiO 2 ) nanoparticle layer. In detail, morphology and phase identification of the prepared NPs are first characterized and then the up-conversion of the Gd 2 (MoO 4 ) 3 :Yb/Tm NPs is studied. Electron transfer dynamics after interfacing with bare or NP-doped electron donor TiO 2 and the corresponding photovoltaic performance of solar cells are explored. The results show that Gd 2 (MoO 4 ) 3 :Yb/Tm NPs excited at 976 nm exhibit intense blue (460-498 nm) and weak red (627-669 nm) emissions. The lifetime of electron transfer is shortened from 817 to 316 ps after incorporating NPs and correspondingly the electron transfer rate outstrips by 3 times that of the bare TiO 2 . Consequently, a notable power conversion efficiency of 4.15% is achieved as compared to 3.17% of pure TiO 2 /PTB7. This work demonstrates that the co-doping of robust rare earth ions with different unique functions can widen the harvesting range of the solar spectrum, boost electron transfer rate and eventually strengthen device performance, without complicated interfacial and structural engineering.

Gadolinium-enhanced inner ear magnetic resonance imaging for evaluation of delayed endolymphatic hydrops, including a bilateral case.

PubMed

Fukushima, Munehisa; Oya, Ryohei; Akazawa, Hitoshi; Tsuruta, Yukinori; Inohara, Hidenori

2016-01-01

The data suggests that gadolinium-enhanced inner ear MR imaging is useful for diagnosis of delayed endolymphatic hydrops (DEH) because it is independent of inner ear function, and the size of the affected endolymphatic space is clearly enlarged. This study was performed to semi-quantitatively evaluate the endolymphatic space in patients with all types of DEH using gadolinium-enhanced inner ear magnetic resonance (MR) imaging. Seven patients (age range = 21-77 years; five female, two male) with ipsilateral DEH (n = 5), contralateral DEH (n = 1), and bilateral DEH (n = 1). All patients underwent 3T MR imaging 4 h after intravenous injection of gadolinium. Software was used to determine the size of the endolymphatic space. Pure tone audiometry and caloric testing using an electronystagmogram were carried out. One side of the endolymphatic space was dominantly extended in patients with ipsilateral DEH, and both sides of the space were extended in patients with contralateral and bilateral DEH. In patients with ipsilateral DEH, the volume ratio of endolymph to vestibule was 2.5-4.3-times that in the unaffected ear. The volume ratio of endolymph to vestibule was nearly equal in patients with contralateral and bilateral DEH.

Monte Carlo simulation of energy absorbed in phenolic ESR dosimeters added with gadolinium exposed to thermal, epithermal and fast neutrons

NASA Astrophysics Data System (ADS)

Longo, A.; Collura, G.; Gallo, S.; Bartolotta, A.; Marrale, M.

2017-11-01

In this work analyses of the energy released per unit mass in phenolic compound exposed to neutron beams were performed with the aim of predicting the increase in dose achievable by addition of gadolinium (Gd) inside the pellets. In particular, Monte Carlo (MC) simulations were carried out for IRGANOX® 1076 phenolic compound irradiated with neutron beams with different energy spectra at various depths inside a water phantom. The addition of gadolinium increases sensitivity of phenolic ESR (electron spin resonance) dosimeters to neutrons thanks to the high gadolinium cross section for neutron capture and to the large number of secondary particles (mainly Auger and internal conversion electrons) which are able to release energy inside the sensitive material layers. For small depths in water phantom and low energy neutron spectra the increase in dose due to gadolinium is large (more than a factor 50). The enhancement is smaller in case of epithermal neutron beam, whereas the increase in dose for fast neutrons is less than 50%. In order to have a comparison with other ESR dosimeters the energy released per unit mass in phenolic compound was compared with that calculated in alanine pellets. For thermal neutron beams the energy released in phenolic compound with gadolinium is comparable to that released in alanine for small depths in phantom, whereas it is larger than in alanine for large depths. In case of epithermal and fast neutron beams the energy released in phenolic compound is larger than in alanine samples because the elastic scattering with hydrogen nuclei is more probable for high neutron energies and this phenolic compound is characterized by an higher number of 1H nuclei than alanine. All results here found suggest that these phenolic pellets could be fruitfully used for dosimetric applications in Neutron Capture Therapy.

Optical Properties of Nd Doped Rare Earth Vanadates (Preprint)

DTIC Science & Technology

2010-07-01

Rare earth orthovanadates are being used as substitute for traditional solid state laser hosts such as yttrium aluminium garnet (YAG). While the most...common of these is yttrium orthovanadate, other rare earth vanadates such as lutetium vanadate and gadolinium vanadate are being used for their... gadolinium vanadate are being used for their special properties in certain applications. We report new measurements of the refractive indices and thermo

Role of Pullulan in preparation of ceria nanoparticles and investigation of their biological activities

NASA Astrophysics Data System (ADS)

Khorrami, Mohammad Bagher; Sadeghnia, Hamid Reza; Pasdar, Alireza; Ghayour-Mobarhan, Majid; Riahi-Zanjani, Bamdad; Darroudi, Majid

2018-04-01

Throughout this work, a facile, environmental-friendly, and "green" method is delineated for preparing ceria nanoparticles (CNPs), which utilizes nontoxic and renewable degraded polysaccharide polymer including pullulan as a natural matrix. Pullulan behaves as a suitable stabilizing (capping) agent for CNPs that are effectively formed at various high temperatures, while they are structurally analyzed through different techniques such as TGA/DTG, XRD, FESEM, and FTIR instruments. This procedure was found to be comparable to the ones that were acquired from conventional preparation methods that employ hazardous materials, which confirms this approach to be an exquisite alternative in preparing CNPs through the benefit of bioorganic materials. The in vitro cytotoxicity studies on Neuro2A cells have mentioned nontoxic particles in a range of concentrations (0.97-125 μg/ml) and thus, we reckon that the prepared particular CNPs will have persistent utilization in various fields of biology and medicine.

Renal function, nephrogenic systemic fibrosis and other adverse reactions associated with gadolinium-based contrast media.

PubMed

Canga, Ana; Kislikova, Maria; Martínez-Gálvez, María; Arias, Mercedes; Fraga-Rivas, Patricia; Poyatos, Cecilio; de Francisco, Angel L M

2014-01-01

Nephrogenic systemic fibrosis is a fibrosing disorder that affects patients with impaired renal function and is associated with the administration of gadolinium-based contrast media used in MRI. Despite being in a group of drugs that were considered safe, report about this potentially serious adverse reaction was a turning point in the administration guidelines of these contrast media. There has been an attempt to establish safety parameters to identify patients with risk factors of renal failure. The close pharmacovigilance and strict observation of current regulations, with special attention being paid to the value of glomerular filtration, have reduced the published cases involving the use of gadolinium-based contrast media. In a meeting between radiologists and nephrologists we reviewed the most relevant aspects currently and recommendations for its prevention.

Gadolinium chelate coated gold nanoparticles as contrast agents for both X-ray computed tomography and magnetic resonance imaging.

PubMed

Alric, Christophe; Taleb, Jacqueline; Le Duc, Géraldine; Mandon, Céline; Billotey, Claire; Le Meur-Herland, Alice; Brochard, Thierry; Vocanson, Francis; Janier, Marc; Perriat, Pascal; Roux, Stéphane; Tillement, Olivier

2008-05-07

Functionalized gold nanoparticles were applied as contrast agents for both in vivo X-ray and magnetic resonance imaging. These particles were obtained by encapsulating gold cores within a multilayered organic shell which is composed of gadolinium chelates bound to each other through disulfide bonds. The contrast enhancement in MRI stems from the presence of gadolinium ions which are entrapped in the organic shell, whereas the gold core provides a strong X-ray absorption. This study revealed that these particles suited for dual modality imaging freely circulate in the blood vessels without undesirable accumulation in the lungs, spleen, and liver.

Bioconjugation of luminescent silicon quantum dots to gadolinium ions for bioimaging applications

NASA Astrophysics Data System (ADS)

Erogbogbo, Folarin; Chang, Ching-Wen; May, Jasmine L.; Liu, Liwei; Kumar, Rajiv; Law, Wing-Cheung; Ding, Hong; Yong, Ken Tye; Roy, Indrajit; Sheshadri, Mukund; Swihart, Mark T.; Prasad, Paras N.

2012-08-01

Luminescent imaging agents and MRI contrast agents are desirable components in the rational design of multifunctional nanoconstructs for biological imaging applications. Luminescent biocompatible silicon quantum dots (SiQDs) and gadolinium chelates can be applied for fluorescence microscopy and MRI, respectively. Here, we report the first synthesis of a nanocomplex incorporating SiQDs and gadolinium ions (Gd3+) for biological applications. The nanoconstruct is composed of a PEGylated micelle, with hydrophobic SiQDs in its core, covalently bound to DOTA-chelated Gd3+. Dynamic light scattering reveals a radius of 85 nm for these nanoconstructs, which is consistent with the electron microscopy results depicting radii ranging from 25 to 60 nm. Cellular uptake of the probes verified that they maintain their optical properties within the intracellular environment. The magnetic resonance relaxivity of the nanoconstruct was 2.4 mM-1 s-1 (in terms of Gd3+ concentration), calculated to be around 6000 mM-1 s-1 per nanoconstruct. These desirable optical and relaxivity properties of the newly developed probe open the door for use of SiQDs in future multimodal applications such as tumour imaging.Luminescent imaging agents and MRI contrast agents are desirable components in the rational design of multifunctional nanoconstructs for biological imaging applications. Luminescent biocompatible silicon quantum dots (SiQDs) and gadolinium chelates can be applied for fluorescence microscopy and MRI, respectively. Here, we report the first synthesis of a nanocomplex incorporating SiQDs and gadolinium ions (Gd3+) for biological applications. The nanoconstruct is composed of a PEGylated micelle, with hydrophobic SiQDs in its core, covalently bound to DOTA-chelated Gd3+. Dynamic light scattering reveals a radius of 85 nm for these nanoconstructs, which is consistent with the electron microscopy results depicting radii ranging from 25 to 60 nm. Cellular uptake of the probes verified that they

Removal of gadolinium nitrate from heavy water

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

Wilde, E.W.

2000-03-22

Work was conducted to develop a cost-effective process to purify 181 55-gallon drums containing spent heavy water moderator (D2O) contaminated with high concentrations of gadolinium nitrate, a chemical used as a neutron poison during former nuclear reactor operations at the Savannah River Site (SRS). These drums also contain low level radioactive contamination, including tritium, which complicates treatment options. Presently, the drums of degraded moderator are being stored on site. It was suggested that a process utilizing biological mechanisms could potentially lower the total cost of heavy water purification by allowing the use of smaller equipment with less product loss andmore » a reduction in the quantity of secondary waste materials produced by the current baseline process (ion exchange).« less

Thermal, spectroscopic and laser properties of Nd3+ in gadolinium scandium gallium garnet crystal produced by optical floating zone method

NASA Astrophysics Data System (ADS)

Tian, Li; Wang, Shuxian; Wu, Kui; Wang, Baolin; Yu, Haohai; Zhang, Huaijin; Cai, Huaqiang; Huang, Hui

2013-12-01

A neodymium-doped gadolinium scandium gallium garnet (Nd:GSGG) single crystal with dimensions of Φ 5 × 20 mm2 has been grown by means of optical floating zone (OFZ). X-ray powder diffraction (XRPD) result shows that the as-grown Nd:GSGG crystal possesses a cubic structure with space group Ia3d and a cell parameter of a = 1.2561 nm. Effective elemental segregation coefficients of the Nd:GSGG as-grown crystal were calculated by using X-ray fluorescence (XRF). The thermal properties of the Nd:GSGG crystal were systematically studied by measuring the specific heat, thermal expansion and thermal diffusion coefficient, and the thermal conductivity of this crystal was calculated. The absorption and luminescence spectra of Nd:GSGG were measured at room temperature (RT). By using the Judd-Ofelt (J-O) theory, the theoretical radiative lifetime was calculated and compared with the experimental result. Continuous wave (CW) laser performance was achieved with the Nd:GSGG at the wavelength of 1062 nm when it was pumped by a laser diode (LD). A maximum output power of 0.792 W at 1062 nm was obtained with a slope efficiency of 11.89% under a pump power of 7.36 W, and an optical-optical conversion efficiency of 11.72%.

Studies of MRI relaxivities of gadolinium-labeled dendrons

NASA Astrophysics Data System (ADS)

Pan, Hongmu; Daniel, Marie-Christine

2011-05-01

In cancer detection, imaging techniques have a great importance in early diagnosis. The more sensitive the imaging technique and the earlier the tumor can be detected. Contrast agents have the capability to increase the sensitivity in imaging techniques such as magnetic resonance imaging (MRI). Until now, gadolinium-based contrast agents are mainly used for MRI, and show good enhancement. But improvement is needed for detection of smaller tumors at the earliest stage possible. The dendrons complexed with Gd(DOTA) were synthesized and evaluated as a new MRI contrast agent. The longitudinal and transverse relaxation effects were tested and compared with commercial drug Magnevist, Gd(DTPA).

Characterization of cubic ceria?zirconia powders by X-ray diffraction and vibrational and electronic spectroscopy

NASA Astrophysics Data System (ADS)

Sánchez Escribano, Vicente; Fernández López, Enrique; Panizza, Marta; Resini, Carlo; Gallardo Amores, José Manuel; Busca, Guido

2003-10-01

The X-ray diffraction (XRD) patterns and the Infrared, Raman and UV-visible spectra of CeO 2ZrO 2 powders prepared by co-precipitation are presented. Raman spectra provide evidence for the largely predominant cubic structure of the powders with CeO 2 molar composition higher than 25%. Also skeletal IR spectra allow to distinguish cubic from tetragonal phases which are instead not easily distinguished on the basis of the XRD patterns. All mixed oxides including pure ceria are strong UV absorbers although also absorb in the violet visible region. By carefully selecting their composition and treatment temperature, the onset of the radiation that they cut off can be chosen in the 425-475 nm interval. Although they are likely metastable, the cubic phases are still pure even after heating at 1173 K for 4 h.

Insights into the use of gadolinium and gadolinium/boron-based agents in imaging-guided neutron capture therapy applications.

PubMed

Deagostino, Annamaria; Protti, Nicoletta; Alberti, Diego; Boggio, Paolo; Bortolussi, Silva; Altieri, Saverio; Crich, Simonetta Geninatti

2016-05-01

Gadolinium neutron capture therapy (Gd-NCT) is currently under development as an alternative approach for cancer therapy. All of the clinical experience to date with NCT is done with (10)B, known as boron neutron capture therapy (BNCT), a binary treatment combining neutron irradiation with the delivery of boron-containing compounds to tumors. Currently, the use of Gd for NCT has been getting more attention because of its highest neutron cross-section. Although Gd-NCT was first proposed many years ago, its development has suffered due to lack of appropriate tumor-selective Gd agents. This review aims to highlight the recent advances for the design, synthesis and biological testing of new Gd- and B-Gd-containing compounds with the task of finding the best systems able to improve the NCT clinical outcome.

Effect of Dopants on the Adsorption of Carbon Dioxide on Ceria Surfaces

DOE PAGES

Li, Meijun; Tumuluri, Uma; Wu, Zili; ...

2015-09-25

Here, high-surface-area nanosized CeO 2 and M-doped CeO 2 (M=Cu, La, Zr, and Mg) prepared by a surfactant-templated method were tested for CO 2 adsorption. Cu, La, and Zr are doped into the lattice of CeO 2, whereas Mg is dispersed on the CeO 2 surface. The doping of Cu and La into CeO 2 leads to an increase of the CO 2 adsorption capacity, whereas the doping of Zr has little or no effect. The addition of Mg causes a decrease of the CO 2 adsorption capacity at a low Mg content and a gradual increase at a highermore » content. The CO 2 adsorption capacity follows the sequence Cu-CeO 2>La-CeO 2>Zr-CeO 2≈CeO 2>Mg-CeO 2 at low dopant contents, in line with the relative amount of defect sites in the samples. It is the defect sites on the surface, not in the bulk of CeO 2, modified by the dopants that play the vital role in CO 2 chemisorption. Lastly, the role of surface oxygen vacancies is further supported by an in situ IR spectroscopic study of the surface chemistry during CO 2 adsorption on the doped CeO 2.« less

Quantitative assessment of the rheumatoid synovial microvascular bed by gadolinium-DTPA enhanced magnetic resonance imaging

PubMed Central

Gaffney, K.; Cookson, J.; Blades, S.; Coumbe, A.; Blake, D.

1998-01-01

OBJECTIVE—To examine the relation between rate of synovial membrane enhancement, intra-articular pressure (IAP), and histologically determined synovial vascularity in rheumatoid arthritis, using gadolinium-DTPA enhanced magnetic resonance imaging (MRI).
METHODS—Dynamic gadolinium-DTPA enhanced MRI was performed in 31 patients with knee synovitis (10 patients IAP study, 21 patients vascular morphometry study). Rate of synovial membrane enhancement was quantified by line profile analysis using the image processing package ANALYZE. IAP was measured using an intra-compartmental pressure monitor system. Multiple synovial biopsy specimens were obtained by a blind biopsy technique. Blood vessels were identified immunohistochemically using the endothelial cell marker QBend30 and quantified (blood vessel numerical density and fractional area).
RESULTS—Median blood vessel numerical density and fractional area were 77.5/mm2 (IQR; 69.3-110.7) and 5.6% (IQR; 3.4-8.5) respectively. The rate of synovial membrane enhancement (median 2.74 signal intensity units/s, IQR 2.0-3.8) correlated with both blood vessel numerical density (r = 0.46, p < 0.05) and blood vessel fractional area (r = 0.55, p < 0.02). IAP did not influence the rate of enhancement.
CONCLUSIONS—Gadolinium-DTPA enhanced MRI may prove to be a valuable technique for evaluating drugs that influence angiogenesis.

 Keywords: magnetic resonance imaging; rheumatoid arthritis; synovitis; vascularity PMID:9640130

Hybrid Calcium Phosphate-Polymeric Micelles Incorporating Gadolinium Chelates for Imaging-Guided Gadolinium Neutron Capture Tumor Therapy.

PubMed

Mi, Peng; Dewi, Novriana; Yanagie, Hironobu; Kokuryo, Daisuke; Suzuki, Minoru; Sakurai, Yoshinori; Li, Yanmin; Aoki, Ichio; Ono, Koji; Takahashi, Hiroyuki; Cabral, Horacio; Nishiyama, Nobuhiro; Kataoka, Kazunori

2015-06-23

Gadolinium (Gd) chelates-loaded nanocarriers have high potential for achieving magnetic resonance imaging (MRI)-guided Gd neutron capture therapy (GdNCT) of tumors. Herein, we developed calcium phosphate micelles hybridized with PEG-polyanion block copolymers, and incorporated with the clinical MRI contrast agent Gd-diethylenetriaminepentaacetic acid (Gd-DTPA/CaP). The Gd-DTPA/CaP were nontoxic to cancer cells at the concentration of 100 μM based on Gd-DTPA, while over 50% of the cancer cells were killed by thermal neutron irradiation at this concentration. Moreover, the Gd-DTPA/CaP showed a dramatically increased accumulation of Gd-DTPA in tumors, leading to the selective contrast enhancement of tumor tissues for precise tumor location by MRI. The enhanced tumor-to-blood distribution ratio of Gd-DTPA/CaP resulted in the effective suppression of tumor growth without loss of body weight, indicating the potential of Gd-DTPA/CaP for safe cancer treatment.

Are gadolinium contrast agents suitable for gadolinium neutron capture therapy?

PubMed

De Stasio, Gelsomina; Rajesh, Deepika; Casalbore, Patrizia; Daniels, Matthew J; Erhardt, Robert J; Frazer, Bradley H; Wiese, Lisa M; Richter, Katherine L; Sonderegger, Brandon R; Gilbert, Benjamin; Schaub, Sebastien; Cannara, Rachel J; Crawford, John F; Gilles, Mary K; Tyliszczak, Tolek; Fowler, John F; Larocca, Luigi M; Howard, Steven P; Mercanti, Delio; Mehta, Minesh P; Pallini, Roberto

2005-06-01

Gadolinium neutron capture therapy (GdNCT) is a potential treatment for malignant tumors based on two steps: (1) injection of a tumor-specific (157)Gd compound; (2) tumor irradiation with thermal neutrons. The GdNC reaction can induce cell death provided that Gd is proximate to DNA. Here, we studied the nuclear uptake of Gd by glioblastoma (GBM) tumor cells after treatment with two Gd compounds commonly used for magnetic resonance imaging, to evaluate their potential as GdNCT agents. Using synchrotron X-ray spectromicroscopy, we analyzed the Gd distribution at the subcellular level in: (1) human cultured GBM cells exposed to Gd-DTPA or Gd-DOTA for 0-72 hours; (2) intracerebrally implanted C6 glioma tumors in rats injected with one or two doses of Gd-DOTA, and (3) tumor samples from GBM patients injected with Gd-DTPA. In cell cultures, Gd-DTPA and Gd-DOTA were found in 84% and 56% of the cell nuclei, respectively. In rat tumors, Gd penetrated the nuclei of 47% and 85% of the tumor cells, after single and double injection of Gd-DOTA, respectively. In contrast, in human GBM tumors 6.1% of the cell nuclei contained Gd-DTPA. Efficacy of Gd-DTPA and Gd-DOTA as GdNCT agents is predicted to be low, due to the insufficient number of tumor cell nuclei incorporating Gd. Although multiple administration schedules in vivo might induce Gd penetration into more tumor cell nuclei, a search for new Gd compounds with higher nuclear affinity is warranted before planning GdNCT in animal models or clinical trials.

Gadolinium based contrast agents in current practice: Risks of accumulation and toxicity in patients with normal renal function

PubMed Central

Ranga, Anju; Agarwal, Yatish; Garg, Kanika J

2017-01-01

Despite being decked as the most prized compounds in the nugget box of contrast agents for clinical radiologists, and carrying an indisputable tag of safety of the US Food and Drug Administration for close to three decades, all may not be seemingly well with the family of gadolinium compounds. If the first signs of violations of primum non nocere in relation to gadolinium-based contrast agents (GBCAs) appeared in the millennium year with the first published report of skin fibrosis in patients with compromised renal function, the causal relationship between the development of nephrogenic systemic fibrosis (NSF) and GBCAs, first proposed by two European groups in 2006, further precluded their use in renocompromised patients. The toxicity, pharmacokinetics, and pharmacodynamics of GBCAs, however, has come under hawk-eyed scrutiny with recent reports that gadolinium tends to deposit cumulatively in the brain of patients with normal hepatobiliary function and intact blood–brain barrier. While the jury on the long-term hazard significance of this critical scientific finding is still out, the use of GBCAs must be guided by due clinical diligence, avoidance of repeated doses, and preferring GBCAs with the best safety profiles. PMID:28744073

Reaction of gadolinium chelates with ozone and hydroxyl radicals.

PubMed

Cyris, Maike; Knolle, Wolfgang; Richard, Jessica; Dopp, Elke; von Sonntag, Clemens; Schmidt, Torsten C

2013-09-03

Gadolinium chelates are used in increasing amounts as contrast agents in magnetic resonance imaging, and their fate in wastewater treatment has recently become the focus of research. Oxidative processes, in particular the application of ozone, are currently discussed or even implemented for advanced wastewater treatment. However, reactions of the gadolinium chelates with ozone are not yet characterized. In this study, therefore, rate constants with ozone were determined for the three commonly used chelates Gd-DTPA, Gd-DTPA-BMA, and Gd-BT-DO3A, which were found to be 4.8 ± 0.88, 46 ± 2.5, and 24 ± 1.5 M(-1) s(-1), respectively. These low rate constants indicate that a direct reaction with ozone in wastewater is negligible. However, application of ozone in wastewater leads to substantial yields of (•)OH. Different methods have been applied and compared for determination of k((•)OH+Gd chelate). From rate constants determined by pulse radiolysis experiments (k((•)OH+Gd-DTPA) = 2.6 ± 0.2 × 10(9) M(-1) s(-1), k((•)OH+Gd-DTPA-BMA) = 1.9 ± 0.7 × 10(9) M(-1) s(-1), k((•)OH+Gd-BT-DO3A) = 4.3 ± 0.2 × 10(9) M(-1) s(-1)), it is concluded that a reaction in wastewater via (•)OH radicals is feasible. Toxicity has been tested for educt and product mixtures of both reactions. Cytotoxicity (MTT test) and genotoxicity (micronuclei assay) were not detectable.

Neuroprotective effect of gadolinium: a stretch-activated calcium channel blocker in mouse model of ischemia-reperfusion injury.

PubMed

Gulati, Puja; Muthuraman, Arunachalam; Jaggi, Amteshwar S; Singh, Nirmal

2013-03-01

The present study was designed to investigate the potential of gadolinium, a stretch-activated calcium channel blocker in ischemic reperfusion (I/R)-induced brain injury in mice. Bilateral carotid artery occlusion of 12 min followed by reperfusion for 24 h was given to induce cerebral injury in male Swiss mice. Cerebral infarct size was measured using triphenyltetrazolium chloride staining. Memory was assessed using Morris water maze test and motor incoordination was evaluated using rota-rod, lateral push, and inclined beam walking tests. In addition, total calcium, thiobarbituric acid reactive substance (TBARS), reduced glutathione (GSH), and acetylcholinesterase (AChE) activity were also estimated in brain tissue. I/R injury produced a significant increase in cerebral infarct size. A significant loss of memory along with impairment of motor performance was also noted. Furthermore, I/R injury also produced a significant increase in levels of TBARS, total calcium, AChE activity, and a decrease in GSH levels. Pretreatment of gadolinium significantly attenuated I/R-induced infarct size, behavioral and biochemical changes. On the basis of the present findings, we can suggest that opening of stretch-activated calcium channel may play a critical role in ischemic reperfusion-induced brain injury and that gadolinium has neuroprotective potential in I/R-induced injury.

Analytical Interference in Serum Iron Determination Reveals Iron Versus Gadolinium Transmetallation With Linear Gadolinium-Based Contrast Agents

PubMed Central

Fretellier, Nathalie; Poteau, Nathalie; Factor, Cécile; Mayer, Jean-François; Medina, Christelle; Port, Marc; Idée, Jean-Marc; Corot, Claire

2014-01-01

Objectives The purposes of this study were to evaluate the risk for analytical interference with gadolinium-based contrast agents (GBCAs) for the colorimetric measurement of serum iron (Fe3+) and to investigate the mechanisms involved. Materials and Methods Rat serum was spiked with several concentrations of all molecular categories of GBCAs, ligands, or “free” soluble gadolinium (Gd3+). Serum iron concentration was determined by 2 different colorimetric methods at pH 4.0 (with a Vitros DT60 analyzer or a Cobas Integra 400 analyzer). Secondly, the cause of interference was investigated by (a) adding free soluble Gd3+ or Mn2+ to serum in the presence of gadobenic acid or gadodiamide and (b) electrospray ionization mass spectrometry. Results Spurious decrease in serum Fe3+ concentration was observed with all linear GBCAs (only with the Vitros DT60 technique occurring at pH 4.0) but not with macrocyclic GBCAs or with free soluble Gd3+. Spurious hyposideremia was also observed with the free ligands present in the pharmaceutical solutions of the linear GBCAs gadopentetic acid and gadodiamide (ie, diethylene triamine pentaacetic acid and calcium-diethylene triamine pentaacetic acid bismethylamide, respectively), suggesting the formation of Fe-ligand chelate. Gadobenic acid-induced interference was blocked in a concentration-dependent fashion by adding a free soluble Gd3+ salt. Conversely, Mn2+, which has a lower affinity than Gd3+ and Fe3+ for the ligand of gadobenic acid (ie, benzyloxypropionic diethylenetriamine tetraacetic acid), was less effective (interference was only partially blocked), suggesting an Fe3+ versus Gd3+ transmetallation phenomenon at pH 4.0. Similar results were observed with gadodiamide. Mass spectrometry detected the formation of Fe-ligand with all linear GBCAs tested in the presence of Fe3+ and the disappearance of Fe-ligand after the addition of free soluble Gd3+. No Fe-ligand chelate was found in the case of the macrocyclic GBCA gadoteric

Dispersion characteristic of photoluminescence decay times of phosphor YAG: Ce, Gd

NASA Astrophysics Data System (ADS)

Lisitsyn, V. M.; Ju, Yangyang; Stepanov, S. A.; Soschin, N. M.

2017-05-01

The dispersion of the characteristic decay times of gadolinium co-doped yttrium aluminum garnet doped with cerium phosphors were studied. In the present work, an ultraviolet semiconductor laser (λem=375 nm, τ = 1 ns) was used as excitation source for measuring kinetics characteristics of phosphor groups based on YAG with different content of cerium.

In Situ Spectroscopy and Mechanistic Insights into CO Oxidation on Transition-Metal-Substituted Ceria Nanoparticles

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

Elias, Joseph S.; Stoerzinger, Kelsey A.; Hong, Wesley T.

Herein we investigate the reaction intermediates formed during CO oxidation on copper-substituted ceria nanoparticles (Cu0.1Ce0.9O2–x) by means of in situ spectroscopic techniques and identify an activity descriptor that rationalizes a trend with other metal substitutes (M0.1Ce0.9O2–x, M = Mn, Fe, Co, Ni). In situ X-ray absorption spectroscopy (XAS) performed under catalytic conditions demonstrates that O2– transfer occurs at dispersed copper centers, which are redox active during catalysis. In situ XAS reveals a dramatic reduction at the copper centers that is fully reversible under catalytic conditions, which rationalizes the high catalytic activity of Cu0.1Ce0.9O2–x. Ambient pressure X-ray photoelectron spectroscopy (AP-XPS) andmore » in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) show that CO can be oxidized to CO32– in the absence of O2. We find that CO32– desorbs as CO2 only under oxygen-rich conditions when the oxygen vacancy is filled by the dissociative adsorption of O2. These data, along with kinetic analyses, lend support to a mechanism in which the breaking of copper–oxygen bonds is rate-determining under oxygen-rich conditions, while refilling the resulting oxygen vacancy is rate-determining under oxygen-lean conditions. On the basis of these observations and density functional calculations, we introduce the computed oxygen vacancy formation energy (Evac) as an activity descriptor for substituted ceria materials and demonstrate that Evac successfully rationalizes the trend in the activities of M0.1Ce0.9O2–x catalysts that spans three orders of magnitude. The applicability of Evac as a useful design descriptor is demonstrated by the catalytic performance of the ternary oxide Cu0.1La0.1Ce0.8O2–x, which has an apparent activation energy rivaling those of state-of-the-art Au/TiO2 materials. Thus, we suggest that cost-effective catalysts for CO oxidation can be rationally designed by judicious choice of

Analysis of Blood Gadolinium in an Isotope Geochemist Following Contrast MRI

NASA Astrophysics Data System (ADS)

Wasylenki, L. E.

2011-12-01

Normal brain tissue does not have blood flowing throughout it; instead oxygen diffuses across a blood-brain barrier in order to oxygenate brain cells. Brain tumors, however, do grow blood supplies, so an abnormal distribution of blood in the brain is a key indicator of abnormal cell growth. But how is the distribution of blood in inside the brain observed? The lanthanide ion gadolinium(III) has unpaired 5f-shell electrons and is thus paramagnetic. As such, the presence of Gd causes the nuclei of nearby atoms to relax more quickly when excited to high-energy spin states by pulses of radio-frequency energy than they would without Gd nearby. The signal in magnetic resonance imaging correlates with this nuclear spin relaxation time, so gadolinium's presence in certain body tissues makes those tissues appear as bright areas on MRI images. Gadolinium is therefore commonly injected intravenously just prior to MRI imaging, so that the distribution of blood in and around the brain can be mapped. Gadolinium as a free ion is toxic, so it is injected in a relatively inert form, often as gadoversetamide, in which Gd is tightly bound in nine-fold coordination with N, C, and O. This compound is removed from the blood by the kidneys at a rate that is fast compared to the rate of breakdown of this compound in the blood, thus preventing release of toxic Gd in the bloodstream. But how quickly can the kidneys of an isotope geochemist remove Gd from blood? In this experiment, a single isotope geochemist's wristwatch was synchronized with that of the MRI technician and then left in a dressing room with all other magnetically susceptible objects until after the MRI. The time of intravenous injection of gadoversetamide into the isotopist was recorded by the technician and later transmitted verbally to the isotopist. Following the MRI session, blood samples were collected by self-fingerprick, in a Class 100 trace metal clean lab, from 47 to 281 minutes after intravenous injection. For each

Ultrasmall lanthanide-doped nanoparticles as multimodal platforms

NASA Astrophysics Data System (ADS)

Yust, Brian G.; Pedraza, Francisco J.; Sardar, Dhiraj K.

2014-03-01

Recently, there has been a great amount of interest in nanoparticles which are able to provide a platform with high contrast for multiple imaging modalities in order to advance the tools available to biomedical researchers and physicians. However, many nanoparticles do not have ideal properties to provide high contrast in different imaging modes. In order to address this, ultrasmall lanthanide doped oxide and fluoride nanoparticles with strong NIR to NIR upconversion fluorescence and a strong magnetic response for magnetic resonance imaging (MRI) have been developed. Specifically, these nanoparticles incorporate gadolinium, dysprosium, or a combination of both into the nano-crystalline host to achieve the magnetic properties. Thulium, erbium, and neodymium codopants provide the strong NIR absorption and emission lines that allow for deeper tissue imaging since near infrared light is not strongly absorbed or scattered by most tissues within this region. This also leads to better image quality and lower necessary excitation intensities. As a part of the one pot synthesis, these nanoparticles are coated with peg, pmao, or d-glucuronic acid to make them water soluble, biocompatible, and bioconjugable due to the available carboxyl or amine groups. Here, the synthesis, morphological characterization, magnetic response, NIR emission, and the quantum yield will be discussed. Cytotoxicity tested through cell viability at varying concentrations of nanoparticles in growth media will also be discussed.

Rare Earth Laser Engineering Program. Part II.

DTIC Science & Technology

YTTRIUM ALUMINUM GARNET , NEAR INFRARED RADIATION, CONCENTRATION(CHEMISTRY), YTTRIUM COMPOUNDS, ALUMINUM COMPOUNDS, OXIDES, RELAXATION, RATES...VANADATES, DOPING, LANTHANUM, ERBIUM, HOLMIUM, GADOLINIUM COMPOUNDS, GARNET , TRANSPORT PROPERTIES, OSCILLATORS, LANTHANUM COMPOUNDS, FLUORIDES.

Direct Single-Enzyme Biomineralization of Catalytically Active Ceria and Ceria–Zirconia Nanocrystals

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

Curran, Christopher D.; Lu, Li; Jia, Yue

Biomineralization is an intriguing approach to the synthesis of functional inorganic materials for energy applications whereby biological systems are engineered to mineralize inorganic materials and control their structure over multiple length scales under mild reaction conditions. Herein we demonstrate a single-enzyme-mediated biomineralization route to synthesize crystalline, catalytically active, quantum-confined ceria (CeO2–x) and ceria–zirconia (Ce1–yZryO2–x) nanocrystals for application as environmental catalysts. In contrast to typical anthropogenic synthesis routes, the crystalline oxide nanoparticles are formed at room temperature from an otherwise inert aqueous solution without the addition of a precipitant or additional reactant. An engineered form of silicatein, rCeSi, as a singlemore » enzyme not only catalyzes the direct biomineralization of the nanocrystalline oxides but also serves as a templating agent to control their morphological structure. The biomineralized nanocrystals of less than 3 nm in diameter are catalytically active toward carbon monoxide oxidation following an oxidative annealing step to remove carbonaceous residue. The introduction of zirconia into the nanocrystals leads to an increase in Ce(III) concentration, associated catalytic activity, and the thermal stability of the nanocrystals.« less

Nonlinear Impedance Analysis of La 0.4Sr 0.6Co 0.2Fe 0.8O 3-δ Thin Film Oxygen Electrodes

DOE PAGES

Geary, Tim C.; Lee, Dongkyu; Shao-Horn, Yang; ...

2016-07-23

Here, linear and nonlinear electrochemical impedance spectroscopy (EIS, NLEIS) were used to study 20 nm thin film La 0.6Sr 0.4Co 0.2Fe 0.8O 3-δ (LSCF-6428) electrodes at 600°C in oxygen environments. LSCF films were epitaxially deposited on single crystal yttria-stabilized zirconia (YSZ) with a 5 nm gadolinium-doped ceria (GDC) protective interlayer. Impedance measurements reveal an oxygen storage capacity similar to independent thermogravimetry measurements on semi-porous pellets. However, the impedance data fail to obey a homogeneous semiconductor point-defect model. Two consistent scenarios were considered: a homogeneous film with non-ideal thermodynamics (constrained by thermogravimetry measurements), or an inhomogeneous film (constrained by a semiconductormore » point-defect model with a Sr maldistribution). The latter interpretation suggests that gradients in Sr composition would have to extend beyond the space-charge region of the gas-electrode interface. While there is growing evidence supporting an equilibrium Sr segregation at the LSCF surface monolayer, a long-range, non-equilibrium Sr stratification caused by electrode processing conditions offers a possible explanation for the large volume of highly reducible LSCF. Additionally, all thin films exhibited fluctuations in both linear and nonlinear impedance over the hundred-hour measurement period. This behavior is inconsistent with changes solely in the surface rate coefficient and possibly caused by variations in the surface thermodynamics over exposure time.« less

The Anti-Doping Movement.

PubMed

Willick, Stuart E; Miller, Geoffrey D; Eichner, Daniel

2016-03-01

Historical reports of doping in sports date as far back as the ancient Greek Olympic Games. The anti-doping community considers doping in sports to be cheating and a violation of the spirit of sport. During the past century, there has been an increasing awareness of the extent of doping in sports and the health risks of doping. In response, the anti-doping movement has endeavored to educate athletes and others about the health risks of doping and promote a level playing field. Doping control is now undertaken in most countries around the world and at most elite sports competitions. As athletes have found new ways to dope, however, the anti-doping community has endeavored to strengthen its educational and deterrence efforts. It is incumbent upon sports medicine professionals to understand the health risks of doping and all doping control processes. Copyright © 2016 American Academy of Physical Medicine and Rehabilitation. Published by Elsevier Inc. All rights reserved.

Doped Organic Transistors.

PubMed

Lüssem, Björn; Keum, Chang-Min; Kasemann, Daniel; Naab, Ben; Bao, Zhenan; Leo, Karl

2016-11-23

Organic field-effect transistors hold the promise of enabling low-cost and flexible electronics. Following its success in organic optoelectronics, the organic doping technology is also used increasingly in organic field-effect transistors. Doping not only increases device performance, but it also provides a way to fine-control the transistor behavior, to develop new transistor concepts, and even improve the stability of organic transistors. This Review summarizes the latest progress made in the understanding of the doping technology and its application to organic transistors. It presents the most successful doping models and an overview of the wide variety of materials used as dopants. Further, the influence of doping on charge transport in the most relevant polycrystalline organic semiconductors is reviewed, and a concise overview on the influence of doping on transistor behavior and performance is given. In particular, recent progress in the understanding of contact doping and channel doping is summarized.

Gadolinium enhanced cardiovascular magnetic resonance in Anderson-Fabry disease. Evidence for a disease specific abnormality of the myocardial interstitium.

PubMed

Moon, James C C; Sachdev, Bhavesh; Elkington, Andrew G; McKenna, William J; Mehta, Atul; Pennell, Dudley J; Leed, Philip J; Elliott, Perry M

2003-12-01

Anderson-Fabry Disease (AFD), an X-linked disorder of sphingolipid metabolism, is a cause of idiopathic left ventricular hypertrophy but the mechanism of hypertrophy is poorly understood. Gadolinium enhanced cardiovascular magnetic resonance can detect focal myocardial fibrosis. We hypothesised that hyperenhancement would be present in AFD. Eighteen males (mean 43+/-14 years) and eight female heterozygotes (mean 48+/-12 years) with AFD underwent cine and late gadolinium cardiovascular magnetic resonance. Nine male (50%) had myocardial hyperenhancement ranging from 3.4% to 20.6% (mean 7.7+/-5.7%) of total myocardium; in males, percentage hyperenhancement related to LV mass index (r=0.78, P=0.0002) but not to ejection fraction or left ventricular volumes. Lesser hyperenhancement was also found in four (50%) heterozygous females (mean 4.6%). In 12 (92%) patients with abnormal gadolinium uptake, hyperenhancement occurred in the basal infero-lateral wall where, unlike myocardial infarction, it was not sub-endocardial. In two male patients with severe LVH (left ventricular hypertrophy) and systolic impairment there was additional hyperenhancement in other myocardial segments. These observations suggests that myocardial fibrosis occurs in AFD and may contribute to the hypertrophy and the natural history of the disease.

Electrical and Structural Substrate of Arrhythmogenic Right Ventricular Cardiomyopathy Determined Using Noninvasive Electrocardiographic Imaging and Late Gadolinium Magnetic Resonance Imaging.

PubMed

Andrews, Christopher M; Srinivasan, Neil T; Rosmini, Stefania; Bulluck, Heerajnarain; Orini, Michele; Jenkins, Sharon; Pantazis, Antonis; McKenna, William J; Moon, James C; Lambiase, Pier D; Rudy, Yoram

2017-07-01

Arrhythmogenic right ventricular cardiomyopathy (ARVC) is a significant cause of sudden cardiac death in the young. Improved noninvasive assessment of ARVC and better understanding of the disease substrate are important for improving patient outcomes. We studied 20 genotyped ARVC patients with a broad spectrum of disease using electrocardiographic imaging (a method for noninvasive cardiac electrophysiology mapping) and advanced late gadolinium enhancement cardiac magnetic resonance scar imaging. Compared with 20 healthy controls, ARVC patients had longer ventricular activation duration (median, 52 versus 42 ms; P =0.007) and prolonged mean epicardial activation-recovery intervals (a surrogate for local action potential duration; median, 275 versus 241 ms; P =0.014). In these patients, we observed abnormal and varied epicardial activation breakthrough locations and regions of nonuniform conduction and fractionated electrograms. Nonuniform conduction and fractionated electrograms were present in the early concealed phase of ARVC. Electrophysiological abnormalities colocalized with late gadolinium enhancement scar, indicating a relationship with structural disease. Premature ventricular contractions were common in ARVC patients with variable initiation sites in both ventricles. Premature ventricular contraction rate increased with exercise, and within anatomic segments, it correlated with prolonged repolarization, electric markers of scar, and late gadolinium enhancement (all P <0.001). Electrocardiographic imaging reveals electrophysiological substrate properties that differ in ARVC patients compared with healthy controls. A novel mechanistic finding is the presence of repolarization abnormalities in regions where ventricular ectopy originates. The results suggest a potential role for electrocardiographic imaging and late gadolinium enhancement in early diagnosis and noninvasive follow-up of ARVC patients. © 2017 American Heart Association, Inc.

Switching of the polarization of ferroelectric-ferroelastic gadolinium molybdate in a magnetic field

NASA Astrophysics Data System (ADS)

Yakushkin, E. D.

2017-10-01

A change in the character of the electric switching of polydomain ferroelectric-ferroelastic gadolinium molybdate in an external magnetic field has been detected. This change has been attributed to a magnetically stimulated increase in the pinning of domain walls. Under certain conditions, the loop of switchable polarization is degenerated into an ellipse characteristic of a linear insulator with leakage current.

Cerium reduction at the interface between ceria and yttria-stabilised zirconia and implications for interfacial oxygen non-stoichiometry

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

Song, Kepeng; Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Wenhua Road 72, 110016 Shenyang; Schmid, Herbert

2014-03-01

Epitaxial CeO{sub 2} films with different thickness were grown on Y{sub 2}O{sub 3} stabilised Zirconia substrates. Reduction of cerium ions at the interface between CeO{sub 2} films and yttria stabilised zirconia substrates is demonstrated using aberration-corrected scanning transmission electron microscopy combined with electron energy-loss spectroscopy. It is revealed that most of the Ce ions were reduced from Ce{sup 4+} to Ce{sup 3+} at the interface region with a decay of several nanometers. Several possibilities of charge compensations are discussed. Irrespective of the details, such local non-stoichiometries are crucial not only for understanding charge transport in such hetero-structures but also formore » understanding ceria catalytic properties.« less

Neurosarcoidosis--demonstration of meningeal disease by gadolinium enhanced magnetic resonance imaging.

PubMed Central

Khaw, K T; Manji, H; Britton, J; Schon, F

1991-01-01

Arriving at a firm diagnosis of neurosarcoidosis continues to pose serious problems, particularly when evidence of granulomatous disease outside the nervous system is lacking. The commonest mode of presentation of neurosarcoidosis is with cranial nerve palsies. Two cases of presumed neurosarcoidosis with cranial nerve palsies showed clear evidence of focal meningeal disease on gadolinium-DTPA enhanced MRI brain scans. Although not specific for sarcoidosis, this technique may be very useful in aiding the diagnosis in suspected cases. Images PMID:1880510

Implicit versus explicit attitude to doping: Which better predicts athletes' vigilance towards unintentional doping?

PubMed

Chan, Derwin King Chung; Keatley, David A; Tang, Tracy C W; Dimmock, James A; Hagger, Martin S

2018-03-01

This preliminary study examined whether implicit doping attitude, explicit doping attitude, or both, predicted athletes' vigilance towards unintentional doping. A cross-sectional correlational design. Australian athletes (N=143;M age =18.13, SD=4.63) completed measures of implicit doping attitude (brief single-category implicit association test), explicit doping attitude (Performance Enhancement Attitude Scale), avoidance of unintentional doping (Self-Reported Treatment Adherence Scale), and behavioural vigilance task of unintentional doping (reading the ingredients of an unfamiliar food product). Positive implicit doping attitude and explicit doping attitude were negatively related to athletes' likelihood of reading the ingredients table of an unfamiliar food product, and positively related to athletes' vigilance towards unintentional doping. Neither attitude measures predicted avoidance of unintentional doping. Overall, the magnitude of associations by implicit doping attitude appeared to be stronger than that of explicit doping attitude. Athletes with positive implicit and explicit doping attitudes were less likely to read the ingredients table of an unknown food product, but were more likely to be aware of the possible presence of banned substances in a certain food product. Implicit doping attitude appeared to explain athletes' behavioural response to the avoidance of unintentional doping beyond variance explained by explicit doping attitude. Copyright © 2017 Sports Medicine Australia. Published by Elsevier Ltd. All rights reserved.

Gadolinium-modulated 19F signals from Perfluorocarbon Nanoparticles as a New Strategy for Molecular Imaging

PubMed Central

Neubauer, Anne M.; Myerson, Jacob; Caruthers, Shelton D.; Hockett, Franklin D.; Winter, Patrick M.; Chen, Junjie; Gaffney, Patrick J.; Robertson, J. David; Lanza, Gregory M.; Wickline, Samuel A.

2008-01-01

Recent advances in the design of fluorinated nanoparticles for magnetic resonance molecular imaging have enabled specific detection of 19F nuclei, providing unique and quantifiable spectral signatures. However, a pressing need for signal enhancement exists because the total 19F in imaging voxels is often limited. By directly incorporating a relaxation agent (gadolinium) into the lipid monolayer that surrounds the perfluorocarbon, a marked augmentation of the 19F signal from 200nm nanoparticles was achieved. This design increases the magnetic relaxation rate of the 19F nuclei 4-fold at 1.5 T and effects a 125% increase in signal, an effect which is maintained when they are targeted to human plasma clots. By varying the surface concentration of gadolinium, the relaxation effect can be quantitatively modulated to tailor particle properties. This novel strategy dramatically improves the sensitivity and range of 19F MRI/MRS and forms the basis for designing contrast agents capable of sensing their surface chemistry. PMID:18956457

Current Status of Doping in Japan Based on Japan Anti-Doping Disciplinary Panels of the Japan Anti-Doping Agency (JADA): A Suggestion on Anti-Doping Activities by Pharmacists in Japan.

PubMed

Imanishi, Takashi; Kawabata, Takayoshi; Takayama, Akira

2017-01-01

In 2009, the Japan Anti-Doping Agency (JADA) established the "Sports Pharmacist Accreditation Program" to prevent doping in sports. Since then, anti-doping activities in Japan have been attracting attention. In this study, we investigated research about the current status of doping from 2007 to 2014 in Japan to make anti-doping activities more concrete, and we also discussed future anti-doping activities by pharmacists. In Japan, bodybuilding was the sporting event with the highest number and rate of doping from 2007 to 2014. Many of the positive doping cases were detected for class S1 (anabolic agents), S5 (diuretics and masking agents), and S6 (stimulants). Within class S1, supplements were the main cause of positive doping. Within class S5, medicines prescribed by medical doctors were the main cause of positive doping. Within class S6, non-prescription medicines (e.g., OTC) were the main cause of positive doping. When we looked at the global statistics on doping, many of the positive doping cases were detected for class S1. On comparing the Japanese statistics with the global statistics, the rate of positive doping caused by class S1 was significantly lower, but that caused by classes S5 and S6 was significantly higher in Japan than in the world. In conclusion, pharmacists in Japan should pay attention to class S1, S5, and S6 prohibited substances and to the sport events of bodybuilding. Based on this study, sports pharmacists as well as common pharmacists should suggest new anti-doping activities to prevent doping in the future.

Right ventricular stress-induced perfusion defects and late gadolinium enhancement in coronary artery disease.

PubMed

Milks, Michael Wesley; Upadhya, Bharathi; Hall, Michael E; Vasu, Sujethra; Hundley, William Gregory; Stacey, Richard Brandon

2015-01-01

The assessment of right ventricular (RV) perfusion defects has remained challenging during vasodilator stress perfusion with cardiovascular magnetic resonance (CMR). The significance of RV signal abnormalities during vasodilator stress perfusion and late gadolinium-enhanced CMR is yet uncertain. Among 61 individuals who underwent adenosine CMR stress testing before cardiac catheterization, we assessed the severity of coronary artery stenoses, mortality, the presence of stress and rest perfusion defects, as well as the presence of late gadolinium enhancement (LGE). Right ventricular stress-induced perfusion defects were positively associated with left anterior descending artery and proximal right coronary artery stenoses but were negatively associated with left circumflex artery stenoses. The presence of RVLGE was associated with mortality, but 77% of those with RVLGE also had left ventricular LGE. Proximal right coronary artery and left anterior descending artery stenoses are positively associated, whereas left circumflex artery stenoses are negatively associated with RV stress-induced perfusion defects. Right ventricular LGE was associated with mortality, but further study is needed to determine whether this is independent of left ventricular LGE.

Graphene oxide-gadolinium (III) oxide nanoparticle composite: a novel MR contrast agent with high longitudinal and transverse relaxivity

NASA Astrophysics Data System (ADS)

Venkatesha, N.; Poojar, Pavan; Geethanath, Sairam; Srivastava, Chandan

2014-12-01

Production of bio-compatible contrast agent materials to enhance the sensitivity of the magnetic resonance imaging (MRI) technique is a highly active area in MRI related research. This work illustrates the potential of a new material: graphene oxide-gadolinium (III) oxide nanoparticle (GO-Gd2O3) composite in yielding both transverse (16.3 mM-1 s-1) and longitudinal relaxivity (40 mM-1 s-1) values which are significantly higher than the proton relaxivity values achieved using the gadolinium based contrast agents currently used in MRI. Such high proton relaxivity values can facilitate low dosage of GO-Gd2O3 composite for obtaining both T1 and T2 weighted high signal-to-noise ratio images in MRI.

A comparison of the COG and MCNP codes in computational neutron capture therapy modeling, Part II: gadolinium neutron capture therapy models and therapeutic effects.

PubMed

Wangerin, K; Culbertson, C N; Jevremovic, T

2005-08-01

The goal of this study was to evaluate the COG Monte Carlo radiation transport code, developed and tested by Lawrence Livermore National Laboratory, for gadolinium neutron capture therapy (GdNCT) related modeling. The validity of COG NCT model has been established for this model, and here the calculation was extended to analyze the effect of various gadolinium concentrations on dose distribution and cell-kill effect of the GdNCT modality and to determine the optimum therapeutic conditions for treating brain cancers. The computational results were compared with the widely used MCNP code. The differences between the COG and MCNP predictions were generally small and suggest that the COG code can be applied to similar research problems in NCT. Results for this study also showed that a concentration of 100 ppm gadolinium in the tumor was most beneficial when using an epithermal neutron beam.

Gadolinium chloride as a contrast agent for imaging wood composite components by magnetic resonance

Treesearch

Thomas L. Eberhardt; Chi-Leung So; Andrea Protti; Po-Wah So

2009-01-01

Although paramagnetic contrast agents have an established track record in medical uses of magnetic resonance imaging (MRI), only recently has a contrast agent been used for enhancing MRI images of solid wood specimens. Expanding on this concept, wood veneers were treated with a gadolinium-based contrast agent and used in a model system comprising three-ply plywood...

Nannochloropsis algae pyrolysis with ceria-based catalysts for production of high-quality bio-oils.

PubMed

Aysu, Tevfik; Sanna, Aimaro

2015-10-01

Pyrolysis of Nannochloropsis was carried out in a fixed-bed reactor with newly prepared ceria based catalysts. The effects of pyrolysis parameters such as temperature and catalysts on product yields were investigated. The amount of bio-char, bio-oil and gas products, as well as the compositions of the resulting bio-oils was determined. The results showed that both temperature and catalyst had significant effects on conversion of Nannochloropsis into solid, liquid and gas products. The highest bio-oil yield (23.28 wt%) and deoxygenation effect was obtained in the presence of Ni-Ce/Al2O3 as catalyst at 500°C. Ni-Ce/Al2O3 was able to retain 59% of the alga starting energy in the bio-oil, compared to only 41% in absence of catalyst. Lower content of acids and oxygen in the bio-oil, higher aliphatics (62%), combined with HHV show promise for production of high-quality bio-oil from Nannochloropsis via Ni-Ce/Al2O3 catalytic pyrolysis. Copyright © 2015 Elsevier Ltd. All rights reserved.

Use of gadolinium chloride as a contrast agent for imaging spruce knots by magnetic resonance

Treesearch

Thomas L. Eberhardt; Chi-Leung So; Amy H. Herlihy; Po-Wah So

2006-01-01

Treatments of knot-containing spruce wood blocks with a paramagnetic salt, gadolinium (III) chloride, in combination with solvent pretreatments, were evaluated as strategies to enhance the visualization of wood features by magnetic resonance imaging (MRI). Initial experiments with clear wood and excised knot samples showed differences in moisture uptake after...

Highly concentrated, stable nitrogen-doped graphene for supercapacitors: Simultaneous doping and reduction

NASA Astrophysics Data System (ADS)

Jiang, Baojiang; Tian, Chungui; Wang, Lei; Sun, Li; Chen, Chen; Nong, Xiaozhen; Qiao, Yingjie; Fu, Honggang

2012-02-01

In this work, we developed a concentrated ammonia-assisted hydrothermal method to obtain N-doped graphene sheets by simultaneous N-doping and reduction of graphene oxide (GO) sheets. The effects of hydrothermal temperature on the surface chemistry and the structure of N-doped graphene sheets were also investigated. X-ray photoelectron spectroscopy (XPS) study of N-doped graphene reveals that the highest doping level of 7.2% N is achieved at 180 °C for 12 h. N binding configurations of sample consist of pyridine N, quaternary N, and pyridine-N oxides. N doping is accompanied by the reduction of GO with decreases in oxygen levels from 34.8% in GO down to 8.5% in that of N-doped graphene. Meanwhile, the sample exhibits excellent N-doped thermal stability. Electrical measurements demonstrate that products have higher capacitive performance than that of pure graphene, the maximum specific capacitance of 144.6 F/g can be obtained which ascribe the pseudocapacitive effect from the N-doping. The samples also show excellent long-term cycle stability of capacitive performance.

[Interdisciplinary strategies versus doping].

PubMed

Vitzthum, Karin; Mache, Stefanie; Quarcoo, David; Groneberg, David A; Schöffel, Norman

2010-06-01

Doping is a phenomenon which in the past years through the various incidences in professional cycling has come more and more into the focus of the public interest. Whilst in the young past the problems were to define the term "doping" exactly, today's problem is to prevent adolescents and children of doping. This shall be achieved by carrying out controls and serious sanctions for doping violations. Scientific research proved that doping usage can be avoided by broad specific prevention measures. In general, the earlier the athletes dope the higher the risk to become addicted later on in life to other legal or illegal drugs. The aim of this review is to analyse the prevalence of doping regarding youth-, competitive-, high performance and recreational sports and to examine further aspects of doping abuse, risks of addiction, the legal situation, current strategies in the fight against doping and to enhance chances of further doping prevention opportunities. By means of this data an all-embracing view should be given over the current situation, problems and prospects in German-speaking countries.

Materials system for intermediate temperature solid oxide fuel cells based on doped lanthanum-gallate electrolyte

NASA Astrophysics Data System (ADS)

Gong, Wenquan

2005-07-01

The objective of this work was to identify a materials system for intermediate temperature solid oxide fuel cells (IT-SOFCs). Towards this goal, alternating current complex impedance spectroscopy was employed as a tool to study electrode polarization effects in symmetrical cells employing strontium and magnesium doped lanthanum gallate (LSGM) electrolyte. Several cathode materials were investigated including strontium doped lanthanum manganite (LSM), Strontium and iron doped lanthanum cobaltate (LSCF), LSM-LSGM, and LSCF-LSGM composites. Investigated Anode materials included nickel-gadolinium or lanthanum doped cerium oxide (Ni-GDC, or Ni-LDC) composites. The ohmic and the polarization resistances of the symmetrical cells were obtained as a function of temperature, time, thickness, and the composition of the electrodes. Based on these studies, the single phase LSM electrode had the highest polarization resistance among the cathode materials. The mixed-conducting LSCF electrode had polarization resistance orders of magnitude lower than that of the LSM-LSGM composite electrodes. Although incorporating LSGM in the LSCF electrode did not reduce the cell polarization resistance significantly, it could reduce the thermal expansion coefficient mismatch between the LSCF electrodes and LSGM electrolyte. Moreover, the polarization resistance of the LSCF electrode decreased asymptotically as the electrode thickness was increased thus suggesting that the electrode thickness needed not be thicker than this asymptotic limit. On the anode side of the IT-SOFC, Ni reacted with LSGM electrolyte, and lanthanum diffusion occurred from the LSGM electrolyte to the GDC barrier layer, which was between the LSGM electrolyte and the Ni-composite anode. However, LDC served as an effective barrier layer. Ni-LDC (70 v% Ni) anode had the largest polarization resistance, while all other anode materials, i.e. Ni-LDC (50 v% Ni), Ni-GDC (70 v% NO, and Ni-GDC (50 v% Ni), had similar polarization

Conversion of Methane into Methanol and Ethanol over Nickel Oxide on Ceria-Zirconia Catalysts in a Single Reactor

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

Okolie, Chukwuemeka; Belhseine, Yasmeen F.; Lyu, Yimeng

Direct conversion of methane into alcohols is a promising technology for converting stranded methane reserves into liquids that can be transported in pipelines and upgraded to value-added chemicals. We demonstrate that a catalyst consisting of small nickel oxide clusters supported on ceria-zirconia (NiO/CZ) can selectively oxidize methane to methanol and ethanol in a single, steady-state process at 723 K using O2 as an abundantly available oxidant. The presence of steam is required to obtain alcohols rather than CO2 as the product of catalytic combustion. The unusual activity of this catalyst is attributed to the synergy between the small Lewis acidicmore » NiO clusters and the redox-active CZ support, which also stabilizes the small NiO clusters.« less

Conversion of Methane to Methanol and Ethanol over Nickel Oxide on Ceria-Zirconia Catalysts in a Single Reactor

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

Okolie, Chukwuemeka; Belhseine, Yasmeen F.; Lyu, Yimeng

Here, the conversion of methane into alcohols under moderate reaction conditions is a promising technology for converting stranded methane reserves into liquids that can be transported in pipelines and upgraded to value-added chemicals. We demonstrate that a catalyst consisting of small nickel oxide clusters supported on ceria-zirconia (NiO/CZ) can convert methane to methanol and ethanol in a single, steady-state process at 723 K using O 2 as an abundantly available oxidant. The presence of steam is required to obtain alcohols rather than CO 2 as the product of catalytic combustion. The unusual activity of this catalyst is attributed to themore » synergy between the small Lewis acidic NiO clusters and the redox-active CZ support, which also stabilizes the small NiO clusters.« less

Conversion of Methane to Methanol and Ethanol over Nickel Oxide on Ceria-Zirconia Catalysts in a Single Reactor

DOE PAGES

Okolie, Chukwuemeka; Belhseine, Yasmeen F.; Lyu, Yimeng; ...

2017-08-08

Here, the conversion of methane into alcohols under moderate reaction conditions is a promising technology for converting stranded methane reserves into liquids that can be transported in pipelines and upgraded to value-added chemicals. We demonstrate that a catalyst consisting of small nickel oxide clusters supported on ceria-zirconia (NiO/CZ) can convert methane to methanol and ethanol in a single, steady-state process at 723 K using O 2 as an abundantly available oxidant. The presence of steam is required to obtain alcohols rather than CO 2 as the product of catalytic combustion. The unusual activity of this catalyst is attributed to themore » synergy between the small Lewis acidic NiO clusters and the redox-active CZ support, which also stabilizes the small NiO clusters.« less

Strategies for the preparation of bifunctional gadolinium(III) chelators

PubMed Central

Frullano, Luca; Caravan, Peter

2012-01-01

The development of gadolinium chelators that can be easily and readily linked to various substrates is of primary importance for the development high relaxation efficiency and/or targeted magnetic resonance imaging (MRI) contrast agents. Over the last 25 years a large number of bifunctional chelators have been prepared. For the most part, these compounds are based on ligands that are already used in clinically approved contrast agents. More recently, new bifunctional chelators have been reported based on complexes that show a more potent relaxation effect, faster complexation kinetics and in some cases simpler synthetic procedures. This review provides an overview of the synthetic strategies used for the preparation of bifunctional chelators for MRI applications. PMID:22375102

SWI enhances vein detection using gadolinium in multiple sclerosis

PubMed Central

Mazzoni, Lorenzo N; Moretti, Marco; Grammatico, Matteo; Chiti, Stefano; Massacesi, Luca

2015-01-01

Susceptibility weighted imaging (SWI) combined with the FLAIR sequence provides the ability to depict in vivo the perivenous location of inflammatory demyelinating lesions – one of the most specific pathologic features of multiple sclerosis (MS). In addition, in MS white matter (WM) lesions, gadolinium-based contrast media (CM) can increase vein signal loss on SWI. This report focuses on two cases of WM inflammatory lesions enhancing on SWI images after CM injection. In these lesions in fact the CM increased the contrast between the parenchyma and the central vein allowing as well, in one of the two cases, the detection of a vein not visible on the same SWI sequence acquired before CM injection. PMID:25815209

The structural response of gadolinium phosphate to pressure

DOE PAGES

Heffernan, Karina M.; Ross, Nancy L.; Spencer, Elinor C.; ...

2016-06-16

In this study, accurate elastic constants for gadolinium phosphate (GdPO 4) have been measured by single-crystal high-pressure diffraction methods. The bulk modulus of GdPO 4 determined under hydrostatic conditions, 128.1(8) GPa (K'=5.8(2)), is markedly different from that obtained with GdPO 4 under non-hydrostatic conditions (160(2) GPa), which indicates the importance of shear stresses on the elastic response of this phosphate. Finally, high pressure Raman and diffraction analysis indicate that the PO 4 tetrahedra behave as rigid units in response to pressure and that contraction of the GdPO 4 structure is facilitated by bending/twisting of the Gd–O–P links that result inmore » increased distortion in the GdO 9 polyhedra.« less

Preparation of 152Gd targets from a small quantity of gadolinium oxide in a pyrochemical reaction

NASA Astrophysics Data System (ADS)

Lipski, A. R.

1995-02-01

A simple method utilizing small amounts (< 5 mg) of isotopically enriched material for the production of gadolinium targets is discussed. An electrostatically focused e-gun is used in the procedure in which 152Gd 2O 3 powder undergoes reduction-distillation and deposition onto an Fe foil.

High Relaxivity Gadolinium Hydroxypyridonate-Viral Capsid Conjugates: Nano-sized MRI Contrast Agents

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

Meux, Susan C.; Datta, Ankona; Hooker, Jacob M.

2007-08-29

High relaxivity macromolecular contrast agents based on the conjugation of gadolinium chelates to the interior and exterior surfaces of MS2 viral capsids are assessed. The proton nuclear magnetic relaxation dispersion (NMRD) profiles of the conjugates show up to a five-fold increase in relaxivity, leading to a peak relaxivity (per Gd{sup 3+} ion) of 41.6 mM{sup -1}s{sup -1} at 30 MHz for the internally modified capsids. Modification of the exterior was achieved through conjugation to flexible lysines, while internal modification was accomplished by conjugation to relatively rigid tyrosines. Higher relaxivities were obtained for the internally modified capsids, showing that (1) theremore » is facile diffusion of water to the interior of capsids and (2) the rigidity of the linker attaching the complex to the macromolecule is important for obtaining high relaxivity enhancements. The viral capsid conjugated gadolinium hydroxypyridonate complexes appear to possess two inner-sphere water molecules (q = 2) and the NMRD fittings highlight the differences in the local motion for the internal ({tau}{sub RI} = 440 ps) and external ({tau}{sub RI} = 310 ps) conjugates. These results indicate that there are significant advantages of using the internal surface of the capsids for contrast agent attachment, leaving the exterior surface available for the installation of tissue targeting groups.« less

Practical Doping Principles

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

Zunger, A.

2003-05-01

'Theoretical investigations of doping of several wide-gap materials suggest a number of rather general, practical"doping principles" that may help guide experimental strategies of overcoming doping bottlenecks. This paper will be published as a journal article in the future.

Corrosion resistance of 0Kh18N10T steel in gadolinium nitrate solutions in the liquid regulation of the reactivity of nuclear reactors

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

Ganzha, V.D.; Konoplev, K.A.; Mashchetov, V.P.

1986-03-01

This study was carried out in connection with the preparation of the design for the PIK research reactor. The corrosion resistance of 0Kh18N10T steel in gadolinium nitrate solutions was tested in laboratory, ampule, and loop corrosion tests. At all stages of the tests, the authors investigated the effect produced on the corrosion processes by factors related to the technology of preparation of the equipment (mechanical working of the surfaces, welding, sensitizing, annealing, stressed state of the material, cracks, etc.). Ampule tests were conducted in order to determine the effect produced by reactor radiation and shutdown regimes on the corrosion resistancemore » of the steel. Special ampules made of 0Kh18N10T steel were filled with gadolinium nitrate solutions of various concentrations, sealed, and irradiated for a long period in the core of the VVR-M reactor at a temperature of 20-50 degrees C. The results of the tests are shown. The investigations showed that the corrosion of 0Kh18N10T steel in solutions of gadolinium nitrate is uniform, regardless of the state of the surface, the concentration of gadolinium nitrate, the duration of the tests, the action of the reactor radiation under static and dynamic conditions, and the presence of mechanical stresses.« less

A novel cryogenic magnetic refrigerant metal-organic framework based on 1D gadolinium(III) chain

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

Tang, Qun; Li, Peng-Fei; Zou, Zhi-Ming, E-mail: 2014005@glut.edu.cn

2017-02-15

A metal-organic framework (MOF) based on gadolinium ion (Gd{sup 3+}) and tricarboxylate ligand, [Gd(BTPCA)(H{sub 2}O)]·2DMF·3H{sub 2}O (Gd-BTPCA) (H{sub 3}BTPCA =1,1′,1′-(benzene-1,3,5-triyl)tripiperidine-4-carboxylic acid; DMF=dimethylformamide), was synthesized and structurally characterized. The adjacent Gd{sup 3+} ions are intraconnected by the carboxylate groups of the BTPCA{sup 3-} ligands to form a 1D Gd{sup 3+} ion chain. The 1D Gd{sup 3+} ion chains are interconnected by the BTPCA{sup 3-} ligands, giving rise to a 3D framework with 1D open channel. The magnetic studies indicate that Gd-BTPCA exhibits weak ferromagnetic interactions, and acts as a cryogenic magnetic refrigerant having the magnetic entropy change (−ΔS{sub m}) of 20.40more » J kg{sup −1} K{sup −1} for ΔH =7 T at 3 K. - Graphical abstract: A 1D gadolinium(III) chains-based metal-organic framework performed ferromagnetic coupling on the magnetic property. Magnetic investigation reveals that Gd-BTPCA exhibits the entropy change (−ΔS{sub m}) of 20.40 J kg{sup −1} K{sup −1} for ΔH =7 T at 3 K. - Highlights: • The MOF based on gadolinium ion and tricarboxylate ligand was synthesized. • This MOF is connected with 1D Gd{sup 3+} ions chain and the carboxylate groups of BTPCA{sup 3-} ligands. • The magnetic studies indicate that the MOF exhibits the weak ferromagnetic interactions. • Magnetic investigation reveals that the MOF exhibits the high entropy change.« less

Influence of acquired obesity on coronary vessel wall late gadolinium enhancement in discordant monozygote twins.

PubMed

Makowski, Marcus R; Jansen, Christian H P; Ebersberger, Ullrich; Schaeffter, Tobias; Razavi, Reza; Mangino, Massimo; Spector, Tim D; Botnar, Rene M; Greil, Gerald F

2017-11-01

The aim of this study was to investigate the impact of BMI on late gadolinium enhancement (LGE) of the coronary artery wall in identical monozygous twins discordant for BMI. Coronary LGE represents a useful parameter for the detection and quantification of atherosclerotic coronary vessel wall disease. Thirteen monozygote female twin pairs (n = 26) with significantly different BMIs (>1.6 kg/m2) were recruited out of >10,000 twin pairs (TwinsUK Registry). A coronary 3D-T2prep-TFE MR angiogram and 3D-IR-TFE vessel wall scan were performed prior to and following the administration of 0.2 mmol/kg of Gd-DTPA on a 1.5 T MR scanner. The number of enhancing coronary segments and contrast to noise ratios (CNRs) of the coronary wall were quantified. An increase in BMI was associated with an increased number of enhancing coronary segments (5.3 ± 1.5 vs. 3.5 ± 1.6, p < 0.0001) and increased coronary wall enhancement (6.1 ± 1.1 vs. 4.8 ± 0.9, p = 0.0027) compared to matched twins with lower BMI. This study in monozygous twins indicates that acquired factors predisposing to obesity, including lifestyle and environmental factors, result in increased LGE of the coronary arteries, potentially reflecting an increase in coronary atherosclerosis in this female study population. • BMI-discordant twins allow the investigation of the influence of lifestyle factors independent from genetic confounders. • Only thirteen obesity-discordant twins were identified underlining the strong genetic component of BMI. • In female twins, a BMI increase is associated with increased coronary late gadolinium enhancement. • Increased late gadolinium enhancement in the coronary vessel wall potentially reflects increased atherosclerosis.

Fabrication and in vitro characterization of gadolinium-based nanoclusters for simultaneous drug delivery and radiation enhancement

NASA Astrophysics Data System (ADS)

Yoo, Shannon S.; Guo, Linghong; Sun, Xuejun; Shaw, Andrew R.; Yuan, Zhipeng; Löbenberg, Raimar; Roa, Wilson H.

2016-09-01

We report the synthesis of a gadolinium hydroxide (Gd(OH)3) nanorod based doxorubicin (Dox) delivery system that can enhance both magnetic resonance imaging contrast and radiation sensitivity. A simple and cost effective wet-chemical method was utilized in the presence of manganese (Mn) ions and Dox to produce the Gd(OH)3:Mn·Dox nanocluster structure. The Gd(OH)3:Mn·Dox nanocluster was composed of Mn-doped Gd(OH)3 nanorods arranged in parallel with Dox as a linker molecule between the adjacent nanorods. No other studies have utilized Dox as both the linker and therapeutic molecule in a nanostructure to date. The Gd(OH)3 nanorod is reported to have no significant cellular or in vivo toxicity, which makes it an ideal base material for this biomedical application. The Gd(OH)3:Mn·Dox nanocluster exhibited paramagnetic behavior and was stable in a colloidal solution. The nanocluster also enabled high Dox loading capacity and specifically released Dox in a sustained and pH-dependent manner. The positively charged Gd(OH)3:Mn·Dox nanoclusters were readily internalized into MDA-MB-231 breast cancer cells via endocytosis, which resulted in intracellular release of Dox. The released Dox in cells was effective in conferring cytotoxicity and inhibiting proliferation of cancer cells. Furthermore, a synergistic anticancer effect could be observed with radiation treatment. Overall, the Gd(OH)3:Mn·Dox nanocluster drug delivery system described herein may have potential utility in clinics as a multifunctional theranostic nanoparticle with combined benefits in both diagnosis and therapy in the management of cancer.

Investigation of suspected Guillain-Barre syndrome in childhood: what is the role for gadolinium enhanced magnetic resonance imaging of the spine?

PubMed

Smith, Nicholas; Pereira, John; Grattan-Smith, Padraic

2014-10-01

To review the role of gadolinium-enhanced magnetic resonance imaging of the spine in the diagnosis of paediatric Guillain-Barre syndrome and compare it with nerve conduction studies and cerebrospinal fluid analysis. A retrospective review of investigations undertaken in children admitted to our institution with acute Guillain-Barre syndrome over a 10-year period was performed. Seven of eight children (88%) displayed post-gadolinium nerve root enhancement consistent with Guillain-Barre syndrome. This compared with supportive nerve conduction studies in 21/24 children (88%) and cerebrospinal fluid protein analysis consistent with the diagnosis in 16/20 children (80%). Nerve conduction studies are the recognised 'gold standard' technique for confirming a clinical diagnosis of Guillain-Barre syndrome. In this study, a high positive rate was demonstrated. While more experience is necessary, this study and the literature support gadolinium enhanced magnetic resonance imaging of the spine as a valuable, although not necessarily superior, investigation in the diagnosis of Guillain-Barre syndrome. It may be of particular benefit when specialist neurophysiology expertise is unavailable. © 2010 The Authors. Journal compilation © 2010 Paediatrics and Child Health Division (Royal Australasian College of Physicians).

Clinical application of a gadolinium-based capsule as an MRI contrast agent in slow transit constipation diagnostics.

PubMed

Zhi, M; Zhou, Z; Chen, H; Xiong, F; Huang, J; He, H; Zhang, M; Su, M; Gao, X; Hu, P

2017-06-01

As a traditional method for the assessment of colon dynamics, radio-opaque markers (ROMs) are limited in clinical use because of their ionizing radiation. We compared the accuracy and applicability of gadolinium-based capsules with ROMs in the measurement of colon dynamics in healthy controls and slow transit constipation (STC) patients. Seven patients with STC and nine healthy controls under a normal diet orally consumed ROMs and gadolinium-based capsules simultaneously. All subjects underwent X-ray and magnetic resonance imaging (MRI). Healthy control images were acquired at 12, 24, and 48 h, and STC patient images were acquired at 24, 48, and 72 h. The scores based on the position of the labeling capsules and ROMs in the colon and the colon transit times (CTTs) in the two groups were compared. The CTTs obtained via the ROMs were 34.7±17.4 and 67.3±6.5 h in the healthy controls and STC patients, respectively (P<.05). The CTTs obtained via MRI were 30.9±15.9 and 74.1±7.2 h in the healthy controls and STC patients, respectively (P<.05). The CTTs of the STC patients were significantly longer than the healthy controls. The correlation (r s ) between the scores based on the position of the labeling capsule and ROMs in the healthy group and the STC patients was .880 (P<.05) and .889 (P<.05), respectively. As a MRI contrast label, gadolinium-based capsules exhibit results comparable to ROMs in colon motility measurements. © 2017 John Wiley & Sons Ltd.

Evaluation of Novel 64Cu-Labeled Theranostic Gadolinium-Based Nanoprobes in HepG2 Tumor-Bearing Nude Mice

NASA Astrophysics Data System (ADS)

Hu, Pengcheng; Cheng, Dengfeng; Huang, Tao; Banizs, Anna B.; Xiao, Jie; Liu, Guobing; Chen, Quan; Wang, Yuenan; He, Jiang; Shi, Hongcheng

2017-09-01

Radiation therapy of liver cancer is limited by low tolerance of the liver to radiation. Radiosensitizers can effectively reduce the required radiation dose. AGuIX nanoparticles are small, multifunctional gadolinium-based nanoparticles that can carry radioisotopes or fluorescent markers for single-photon emission computed tomography (SPECT), positron emission tomography (PET), fluorescence imaging, and even multimodality imaging. In addition, due to the high atomic number of gadolinium, it can also serve as a tumor radiation sensitizer. It is critical to define the biodistribution and pharmacokinetics of these gadolinium-based nanoparticles to quantitate the magnitude and duration of their retention within the tumor microenvironment during radiotherapy. Therefore, in this study, we successfully labeled AGuIX with 64Cu through the convenient built-in chelator. The biodistribution studies indicated that the radiotracer 64Cu-AGuIX accumulates to high levels in the HepG2 xenograft of nude mice, suggesting that it would be a potential theranostic nanoprobe for image-guided radiotherapy in HCC. We also used a transmission electron microscope to confirm AGuIX uptake in the HepG2 cells. In radiation therapy studies, a decrease in 18F-FDG uptake was observed in the xenografts of the nude mice irradiated with AGuIX, which was injected 1 h before. These results provide proof-of-concept that AGuIX can be used as a theranostic radiosensitizer for PET imaging to guide radiotherapy for liver cancer.

Evaluation of Novel 64Cu-Labeled Theranostic Gadolinium-Based Nanoprobes in HepG2 Tumor-Bearing Nude Mice.

PubMed

Hu, Pengcheng; Cheng, Dengfeng; Huang, Tao; Banizs, Anna B; Xiao, Jie; Liu, Guobing; Chen, Quan; Wang, Yuenan; He, Jiang; Shi, Hongcheng

2017-09-06

Radiation therapy of liver cancer is limited by low tolerance of the liver to radiation. Radiosensitizers can effectively reduce the required radiation dose. AGuIX nanoparticles are small, multifunctional gadolinium-based nanoparticles that can carry radioisotopes or fluorescent markers for single-photon emission computed tomography (SPECT), positron emission tomography (PET), fluorescence imaging, and even multimodality imaging. In addition, due to the high atomic number of gadolinium, it can also serve as a tumor radiation sensitizer. It is critical to define the biodistribution and pharmacokinetics of these gadolinium-based nanoparticles to quantitate the magnitude and duration of their retention within the tumor microenvironment during radiotherapy. Therefore, in this study, we successfully labeled AGuIX with 64 Cu through the convenient built-in chelator. The biodistribution studies indicated that the radiotracer 64 Cu-AGuIX accumulates to high levels in the HepG2 xenograft of nude mice, suggesting that it would be a potential theranostic nanoprobe for image-guided radiotherapy in HCC. We also used a transmission electron microscope to confirm AGuIX uptake in the HepG2 cells. In radiation therapy studies, a decrease in 18 F-FDG uptake was observed in the xenografts of the nude mice irradiated with AGuIX, which was injected 1 h before. These results provide proof-of-concept that AGuIX can be used as a theranostic radiosensitizer for PET imaging to guide radiotherapy for liver cancer.

Relaxivity enhancement of aquated Tris(β-diketonate)gadolinium(III) chelates by confinement within ultrashort single-walled carbon nanotubes.

PubMed

Law, Justin J; Guven, Adem; Wilson, Lon J

2014-01-01

Ultrashort single-walled carbon nanotubes loaded with gadolinium ions (gadonanotubes) have been previously shown to exhibit extremely high T1 -weighted relaxivities (>100 mm(-1) s(-1) ). To further examine the effect of nanoconfinement on the relaxivity of gadolinium-based contrast agents for magnetic resonance imaging, a series of ultrashort single-walled carbon nanotube (US-tube) materials internally loaded with gadolinium chelates have been prepared and studied. US-tubes were loaded with Gd(acac)3  · 2H2 O, Gd(hfac)3  · 2H2 O, and Gd(thd)3 (acac = acetylacetone, hfac = hexafluoroacetylacetone, thd = tetramethylheptanedione). The longitudinal relaxivities of the prepared materials determined at 25°C in a 1.5 T field were 103 mm(-1) s(-1) for Gd(acac)3  · 2H2 O@US-tubes, 105 mm(-1) s(-1) for Gd(hfac)3  · 2H2 O@US-tubes and 26 mm(-1) s(-1) for Gd(thd)3 @US-tubes. Compared with the relaxivities obtained for the unloaded chelates (<10 mm(-1) s(-1) ) as well as accounting for the T1 reduction observed for the empty US-tubes, the boost in relaxivity for chelate-loaded US-tubes is attributed to confinement within the nanotube and depends on the number of coordinated water molecules. Copyright © 2014 John Wiley & Sons, Ltd.

Thermophysical Property Measurements of Liquid Gadolinium by Containerless Methods

NASA Astrophysics Data System (ADS)

Ishikawa, T.; Okada, J. T.; Paradis, P.-F.; Watanabe, Y.

2010-02-01

Thermophysical properties of liquid gadolinium were measured using non-contact diagnostic techniques with an electrostatic levitator. Over the 1585 K to 1920 K temperature range, the density can be expressed as ρ( T) = 7.41 × 103 - 0.46 ( T - T m) (kg · m-3) where T m = 1585 K, yielding a volume expansion coefficient of 6.2 × 10-5 K-1. In addition, the surface tension data can be fitted as γ( T) = 8.22 × 102 - 0.097( T - T m)(10-3 N · m-1) over the 1613 K to 1803 K span and the viscosity as η( T) = 1.7exp[1.4 × 104/( RT)](10-3 Pa · s) over the same temperature range.

Complex imaging features of accidental cerebral intraventricular gadolinium administration.

PubMed

Nayak, Nita B; Huang, Jimmy C; Hathout, Gasser M; Shaba, Wisam; El-Saden, Suzie M

2013-05-01

Gadolinium diethylenetriamine pentaacetic acid (Gd-DTPA) is a contrast agent commonly used for enhancing MRI. In this paper, the authors report on 2 cases of postoperative inadvertent administration of Gd-DTPA directly into a ventriculostomy tubing side port that was mistaken for intravenous tubing. Both cases demonstrated a low signal on MRI throughout the ventricular system and dependent portions of the subarachnoid spaces, which was originally believed to be CSF with areas of T1 shortening in the nondependent portions of the subarachnoid spaces, and misinterpreted as basal leptomeningeal enhancement and meningitis. The authors propose that the appearance of profound T1 hypointensity within the ventricles and diffuse susceptibility artifact along the ependyma is pathognomonic of intraventricular Gd-DTPA and should be recognized.

Doped graphene supercapacitors.

PubMed

Kumar, Nanjundan Ashok; Baek, Jong-Beom

2015-12-11

Heteroatom-doped graphitic frameworks have received great attention in energy research, since doping endows graphitic structures with a wide spectrum of properties, especially critical for electrochemical supercapacitors, which tend to complement or compete with the current lithium-ion battery technology/devices. This article reviews the latest developments in the chemical modification/doping strategies of graphene and highlights the versatility of such heteroatom-doped graphitic structures. Their role as supercapacitor electrodes is discussed in detail. This review is specifically focused on the concept of material synthesis, techniques for electrode fabrication and metrics of performance, predominantly covering the last four years. Challenges and insights into the future research and perspectives on the development of novel electrode architectures for electrochemical supercapacitors based on doped graphene are also discussed.

Doped graphene supercapacitors

NASA Astrophysics Data System (ADS)

Ashok Kumar, Nanjundan; Baek, Jong-Beom

2015-12-01

Heteroatom-doped graphitic frameworks have received great attention in energy research, since doping endows graphitic structures with a wide spectrum of properties, especially critical for electrochemical supercapacitors, which tend to complement or compete with the current lithium-ion battery technology/devices. This article reviews the latest developments in the chemical modification/doping strategies of graphene and highlights the versatility of such heteroatom-doped graphitic structures. Their role as supercapacitor electrodes is discussed in detail. This review is specifically focused on the concept of material synthesis, techniques for electrode fabrication and metrics of performance, predominantly covering the last four years. Challenges and insights into the future research and perspectives on the development of novel electrode architectures for electrochemical supercapacitors based on doped graphene are also discussed.

Magnetic resonance imaging with gadolinium arthrography to assess acetabular cartilage delamination.

PubMed

Zaragoza, Edward; Lattanzio, Pierre-Jean; Beaule, Paul E

2009-01-01

Recent reports have demonstrated magnetic resonance imaging (MRI) as a promising technique in detecting articular cartilage lesions of the hip joint. The purpose of our study was to evaluate the diagnostic performance of MRI with gadolinium arthrography in detecting acetabular cartilage delamination in patients with pre-arthritic hip pain. 46 patients (48 hips) underwent surgical dislocation of the hip. Mean age was 38.8 (range 17-56). There were 26 males and 20 females. All patients had Magnetic Resonance Imaging with gadolinium arthrography (MRA) before undergoing open hip surgery where the acetabular cartilage was inspected. Acetabular cartilage delamination on MRA was seen on sagittal images as a linear intra-articular filling defect of low signal intensity >1mm in thickness on T1 weighted images and surrounded by contrast. On MRA all hips had a labral tear confirmed at surgery. At surgery 30 hips had evidence of acetabular cartilage delamination, 4 hips had ulceration and 14 had no articular cartilage damage. The majority of labral tears and cartilage damage were located in the antero-superior quadrant. The sensitivity and specificity of MRA detection of cartilage delamination confirmed at surgery were 97% and 84%, respectively. The positive and negative predictive values of the MRA finding were 90% and 94%, respectively. The presence of the acetabular cartilage delamination represents an early stage of articular cartilage degeneration. When evaluating a young adult with hip pain, labral tears in association with cartilage delamination should be considered. MRA represents an effective diagnostic tool.

In situ trapping of As, Sb and Se hydrides on nanometer-sized ceria-coated iron oxide-silica and slurry suspension introduction to ICP-OES.

PubMed

Dados, A; Kartsiouli, E; Chatzimitakos, Th; Papastephanou, C; Stalikas, C D

2014-12-01

A procedure is developed for the analysis of sub-μg L(-1) levels of arsenic, antimony and selenium after preconcentration of their hydrides. The study highlights the capability of an aqueous suspension of a nanometer-sized magnetic ceria, in the presence of iodide, to function as a sorbent for the in situ trapping and preconcentration of the hydrides of certain metalloids. After extraction, the material is magnetically separated from the trapping solution and analyzed. A slurry suspension sampling approach with inductively coupled plasma-optical emission spectrometry (ICP-OES) is employed for measurements, as the quantitative elution of the adsorbed metalloids is not feasible. The whole analytical procedure consists of five steps: (i) pre-reduction of As, Sb and Se, (ii) generation of the hydrides AsH3, SbH3 and SeH2, (iii) in situ collection in the trapping suspension of magnetic ceria, (iv) isolation of the particles by applying a magnetic field, and (v) measurement of As, Sb and Se concentrations using ICP-OES. Under the established experimental conditions, the efficiency of trapping accounted for 94 ± 2%, 89 ± 2% and 98 ± 3% for As, Sb and Se, respectively, signifying the effective implementation of the overall procedure. The applicability of the procedure has been demonstrated by analyzing tap and lake water and a reference material (soft drinking water). The obtained analytical figures of merit were satisfactory for the analysis of the above metalloids in natural waters by ICP-OES. Copyright © 2014 Elsevier B.V. All rights reserved.

A simple gold plate electrode modified with Gd-doped TiO₂ nanoparticles used for determination of trace nitrite in cured food.

PubMed

Zhang, M-L; Cao, Z; He, J-L; Xue, L; Zhou, Y; Long, S; Deng, T; Zhang, L

2012-01-01

A simple gold plate electrode (GPE) based on a gadolinium-doped titanium dioxide (Gd/TiO₂) ultrathin film was successfully constructed by using a surface sol-gel technique, and used for the detection of trace amounts of nitrite in cured foods. The Gd/TiO₂ nanoparticles were synthesised and characterised via scanning electron microscopy (SEM) and X-ray diffraction (XRD), indicating that the Gd-doped TiO₂ formed an anatase phase through roasting at 450°C, generating actively interstitial oxygen at the interface of the surface of TiO₂ lattice surrounded by Gd³⁺. The electro-catalytic effect for oxidation of nitrite on the modified electrode was investigated by cyclic voltammetry in 0.10 mol l⁻¹ sulfuric acid media solution, showing that the modified electrode exhibited excellent response performance to nitrite with good reproducibility, selectivity and stability. The catalytic peak current was found to be linear with nitrite concentrations in the range of 8.0 × 10⁻⁷ to 4.0 × 10⁻⁴) mol l⁻¹, with a detection limit of 5.0 × 10⁻⁷ mol l⁻¹ (S/N = 3). The modified electrode could be used for the determination of nitrite in the cured sausage samples with a satisfactory recovery in the range of 95.5-104%, showing its promising application for food safety monitoring.

Physical, structural and luminescence investigation of Eu3+-doped lithium-gadolinium bismuth-borate glasses for LEDs

NASA Astrophysics Data System (ADS)

Zaman, F.; Rooh, G.; Srisittipokakun, N.; Wongdeeying, C.; Kim, H. J.; Kaewkhao, J.

2018-06-01

The aim of the current report is to fabricate Eu3+-doped glasses with the chemical composition of 50Li2O-15Gd2O3-5Bi2O3-(30-x)B2O3-xEu2O3 (where x = 0.5, 1.0, 1.5, 2.0 and 2.5 mol%), with the help of conventional melt quenching technique. The fabricated glasses have been studied with help of physical, structural and luminescence properties for application of LEDs. The structural properties were investigated by XRD and FTIR spectra. Physical properties have been measured. Direct and indirect optical energy band gap (Eg) have been calculated and found to be increasing with Eu2O3 concentration. Luminescence spectra have been observed from photo and radioluminescence spectra and found in good agreement with each other, however the concentration quenching was not determined for the samples. The high-covalence and asymmetric nature was confirmed from Photoluminescence emission and RL emission transition as well as from the higher values of luminescence intensity ratio. The JO parameters have been found for the better performance of lasing materials. The lifetime's data have been found to be decreasing from 1.64 to 1.50 ms, which is the confirmation of energy transfer in Eu3+ ions through cross relaxations. From the calculated properties it has been suggested that the present glass samples might be good for red-light emitting devices.

Liver acquisition with acceleration volume acquisition gadolinium-enhanced magnetic resonance combined with T2 sequences in the diagnosis of local recurrence of rectal cancer.

PubMed

Cao, Wuteng; Li, Fangqian; Gong, Jiaying; Liu, Dechao; Deng, Yanhong; Kang, Liang; Zhou, Zhiyang

2016-11-22

To investigate the efficacy of liver acquisition with acceleration volume acquisition (LAVA) gadolinium-enhanced magnetic resonance (MR) sequences and to assess its added accuracy in diagnosing local recurrence (LR) of rectal cancer with conventional T2-weighted fast spin echo (FSE) sequences. Pelvic MRI, including T2-weighted FSE sequences, gadolinium-enhanced sequences of LAVA and T1-weighted FSE with fat suppression, was performed on 225 patients with postoperative rectal cancer. Two readers evaluated the presence of LR according to "T2" (T2 sequences only), "T2 + LAVA-Gad" (LAVA and T2 imaging), and "T2 + T1-fs-Gad" (T1 fat suppression-enhanced sequence with T2 images). To evaluate diagnostic efficiency, imaging quality with LAVA and T1-fs-Gad by subjective scores and the signal intensity (SI) ratio. In the result, the SI ratio of LAVA was significantly higher than that of T1-fs-Gad (p = 0.0001). The diagnostic efficiency of "T2 + LAVA-Gad" was better than that of "T2 + T1-fs-Gad" (p = 0.0016 for Reader 1, p = 0.0001 for Reader 2) and T2 imaging only (p = 0.0001 for Reader 1; p = 0.0001 for Reader 2). Therefore, LAVA gadolinium-enhanced MR increases the accuracy of diagnosis of LR from rectal cancer and could replace conventional T1 gadolinium-enhanced sequences in the postoperative pelvic follow-up of rectal cancer.

Gadolinium Enhanced MR Coronary Vessel Wall Imaging at 3.0 Tesla.

PubMed

Kelle, Sebastian; Schlendorf, Kelly; Hirsch, Glenn A; Gerstenblith, Gary; Fleck, Eckart; Weiss, Robert G; Stuber, Matthias

2010-10-11

Purpose. We evaluated the influence of the time between low-dose gadolinium (Gd) contrast administration and coronary vessel wall enhancement (LGE) detected by 3T magnetic resonance imaging (MRI) in healthy subjects and patients with coronary artery disease (CAD). Materials and Methods. Four healthy subjects (4 men, mean age 29 ± 3 years and eleven CAD patients (6 women, mean age 61 ± 10 years) were studied on a commercial 3.0 Tesla (T) whole-body MR imaging system (Achieva 3.0 T; Philips, Best, The Netherlands). T1-weighted inversion-recovery coronary magnetic resonance imaging (MRI) was repeated up to 75 minutes after administration of low-dose Gadolinium (Gd) (0.1 mmol/kg Gd-DTPA). Results. LGE was seen in none of the healthy subjects, however in all of the CAD patients. In CAD patients, fifty-six of 62 (90.3%) segments showed LGE of the coronary artery vessel wall at time-interval 1 after contrast. At time-interval 2, 34 of 42 (81.0%) and at time-interval 3, 29 of 39 evaluable segments (74.4%) were enhanced. Conclusion. In this work, we demonstrate LGE of the coronary artery vessel wall using 3.0 T MRI after a single, low-dose Gd contrast injection in CAD patients but not in healthy subjects. In the majority of the evaluated coronary segments in CAD patients, LGE of the coronary vessel wall was already detectable 30-45 minutes after administration of the contrast agent.

Effects of gadolinium-based MRI contrast agents on liver tissue.

PubMed

Mercantepe, Tolga; Tümkaya, Levent; Çeliker, Fatma Beyazal; Topal Suzan, Zehra; Çinar, Seda; Akyildiz, Kerimali; Mercantepe, Filiz; Yilmaz, Adnan

2018-04-01

MRI with contrast is often used clinically. However, recent studies have reported a high accumulation of gadolinium-based contrast agents (GBCAs) in kidney, liver, and spleen tissues in several mouse models. To compare the effects on liver tissue of gadolinium-based MRI contrast agents in the light of biochemical and histopathological evaluation. Institutional Review Board (IRB)-approved controlled longitudinal study. In all, 32 male Sprague-Dawley rats were divided into a healthy control group subjected to no procedure (Group 1), a sham group (Group 2), a gadodiamide group (Group 3), and a gadoteric acid group (Group 4). Not applicable. Liver tissues removed at the end of the fifth week and evaluated pathologically (scored Knodell's histological activity index [HAI] method by two histopathologists) immunohistochemical (caspase-3 and biochemical tests (AST, ALT, TAS, TOS, and OSI method by Erel et al) were obtained. Differences between groups were analyzed using the nonparametric Kruskal-Wallis test followed by the Tamhane test, and one-way analysis of variance (ANOVA) followed by Turkey's HSD test. An increase was observed in histological activity scores in sections from rats administered gadodiamide and gadoteric acid, and in caspase-3, AST and ALT values (P < 0.05). In contrast, we determined no change in TOS (P = 0.568 and P = 0.094, respectively), TAS (P = 0.151 and P = 0.055, respectively), or OSI (P = 0.949 and P = 0.494, respectively) values. These data suggest that gadodiamide and gadoteric acid trigger hepatocellular necrosis and apoptosis by causing damage in hepatocytes, although no change occurs in total antioxidant and antioxidant capacity. 1 Technical Efficacy: Stage 4 J. Magn. Reson. Imaging 2018. © 2018 International Society for Magnetic Resonance in Medicine.

The impact of steam and current density on carbon formation from biomass gasification tar on Ni/YSZ, and Ni/CGO solid oxide fuel cell anodes

NASA Astrophysics Data System (ADS)

Mermelstein, Joshua; Millan, Marcos; Brandon, Nigel

The combination of solid oxide fuel cells (SOFCs) and biomass gasification has the potential to become an attractive technology for the production of clean renewable energy. However the impact of tars, formed during biomass gasification, on the performance and durability of SOFC anodes has not been well established experimentally. This paper reports an experimental study on the mitigation of carbon formation arising from the exposure of the commonly used Ni/YSZ (yttria stabilized zirconia) and Ni/CGO (gadolinium-doped ceria) SOFC anodes to biomass gasification tars. Carbon formation and cell degradation was reduced through means of steam reforming of the tar over the nickel anode, and partial oxidation of benzene model tar via the transport of oxygen ions to the anode while operating the fuel cell under load. Thermodynamic calculations suggest that a threshold current density of 365 mA cm -2 was required to suppress carbon formation in dry conditions, which was consistent with the results of experiments conducted in this study. The importance of both anode microstructure and composition towards carbon deposition was seen in the comparison of Ni/YSZ and Ni/CGO anodes exposed to the biomass gasification tar. Under steam concentrations greater than the thermodynamic threshold for carbon deposition, Ni/YSZ anodes still exhibited cell degradation, as shown by increased polarization resistances, and carbon formation was seen using SEM imaging. Ni/CGO anodes were found to be more resilient to carbon formation than Ni/YSZ anodes, and displayed increased performance after each subsequent exposure to tar, likely due to continued reforming of condensed tar on the anode.

Bi-atrial fibrosis detected using three-dimensional late gadolinium enhancement magnetic resonance imaging in a patient with cardiac sarcoidosis.

PubMed

Spence, Stewart; Pena, Elena; Thornhill, Rebecca E; Nery, Pablo B; Birnie, David H

2018-05-01

Presented is the case of a 62-year old male with a history of sarcoidosis and sinus node dysfunction, who underwent late gadolinium enhancement magnetic resonance imaging, which demonstrated left ventricular hyperenhancement and bi-atrial fibrosis.

Reversible and Precisely Controllable p/n-Type Doping of MoTe2 Transistors through Electrothermal Doping.

PubMed

Chang, Yuan-Ming; Yang, Shih-Hsien; Lin, Che-Yi; Chen, Chang-Hung; Lien, Chen-Hsin; Jian, Wen-Bin; Ueno, Keiji; Suen, Yuen-Wuu; Tsukagoshi, Kazuhito; Lin, Yen-Fu

2018-03-01

Precisely controllable and reversible p/n-type electronic doping of molybdenum ditelluride (MoTe 2 ) transistors is achieved by electrothermal doping (E-doping) processes. E-doping includes electrothermal annealing induced by an electric field in a vacuum chamber, which results in electron (n-type) doping and exposure to air, which induces hole (p-type) doping. The doping arises from the interaction between oxygen molecules or water vapor and defects of tellurium at the MoTe 2 surface, and allows the accurate manipulation of p/n-type electrical doping of MoTe 2 transistors. Because no dopant or special gas is used in the E-doping processes of MoTe 2 , E-doping is a simple and efficient method. Moreover, through exact manipulation of p/n-type doping of MoTe 2 transistors, quasi-complementary metal oxide semiconductor adaptive logic circuits, such as an inverter, not or gate, and not and gate, are successfully fabricated. The simple method, E-doping, adopted in obtaining p/n-type doping of MoTe 2 transistors undoubtedly has provided an approach to create the electronic devices with desired performance. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Statistical error in simulations of Poisson processes: Example of diffusion in solids

NASA Astrophysics Data System (ADS)

Nilsson, Johan O.; Leetmaa, Mikael; Vekilova, Olga Yu.; Simak, Sergei I.; Skorodumova, Natalia V.

2016-08-01

Simulations of diffusion in solids often produce poor statistics of diffusion events. We present an analytical expression for the statistical error in ion conductivity obtained in such simulations. The error expression is not restricted to any computational method in particular, but valid in the context of simulation of Poisson processes in general. This analytical error expression is verified numerically for the case of Gd-doped ceria by running a large number of kinetic Monte Carlo calculations.

Evaluating the potential of chelation therapy to prevent and treat gadolinium deposition from MRI contrast agents

DOE PAGES

Rees, Julian A.; Deblonde, Gauthier J. -P.; An, Dahlia D.; ...

2018-03-13

Several MRI contrast agent clinical formulations are now known to leave deposits of the heavy metal gadolinium in the brain, bones, and other organs of patients. This persistent biological accumulation of gadolinium has been recently recognized as a deleterious outcome in patients administered Gd-based contrast agents (GBCAs) for MRI, prompting the European Medicines Agency to recommend discontinuing the use of over half of the GBCAs currently approved for clinical applications. Here, to address this problem, we find that the orally-available metal decorporation agent 3,4,3-LI(1,2-HOPO) demonstrates superior efficacy at chelating and removing Gd from the body compared to diethylenetriaminepentaacetic acid, amore » ligand commonly used in the United States in the GBCA Gadopentetate (Magnevist). Using the radiotracer 153Gd to obtain precise biodistribution data, the results herein, supported by speciation simulations, suggest that the prophylactic or post-hoc therapeutic use of 3,4,3-LI(1,2-HOPO) may provide a means to mitigate Gd retention in patients requiring contrast-enhanced MRI.« less

Evaluating the potential of chelation therapy to prevent and treat gadolinium deposition from MRI contrast agents

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

Rees, Julian A.; Deblonde, Gauthier J. -P.; An, Dahlia D.

Several MRI contrast agent clinical formulations are now known to leave deposits of the heavy metal gadolinium in the brain, bones, and other organs of patients. This persistent biological accumulation of gadolinium has been recently recognized as a deleterious outcome in patients administered Gd-based contrast agents (GBCAs) for MRI, prompting the European Medicines Agency to recommend discontinuing the use of over half of the GBCAs currently approved for clinical applications. Here, to address this problem, we find that the orally-available metal decorporation agent 3,4,3-LI(1,2-HOPO) demonstrates superior efficacy at chelating and removing Gd from the body compared to diethylenetriaminepentaacetic acid, amore » ligand commonly used in the United States in the GBCA Gadopentetate (Magnevist). Using the radiotracer 153Gd to obtain precise biodistribution data, the results herein, supported by speciation simulations, suggest that the prophylactic or post-hoc therapeutic use of 3,4,3-LI(1,2-HOPO) may provide a means to mitigate Gd retention in patients requiring contrast-enhanced MRI.« less

[Combined use of contrast media containing iodine and gadolinium for imaging and intervention : A hitherto widely ignored topic in radiological practice].

PubMed

Golder, W

2012-02-01

The synchronous use of chemically different contrast media in the same body compartment is a challenge for the radiologist, whether it is scheduled or unexpected. However, to inject contrast media containing iodine and gadolinium at the same time can be a prerequisite for the examination of several organs or organ systems. Unlike other topics of contrast-enhanced imaging procedures, the difficulties encountered with double contrast injections have been widely ignored in the literature. In the absence of reliable data from experimental and clinical studies the radiologist is dependent on case reports, information provided by the contrast media manufacturers, personal communications, mostly scanty personal experiences and a skilful time management, in order to overcome the situation. Only the combination of X-ray, computed tomography and magnetic resonance arthrography can be performed without another thought. However, the more or less synchronous vascular application of contrast media containing iodine and gadolinium requires vigilance. The more seriously ill the patient is, the more caution is advised even if the decision on the combined administration has to be reached urgently. The following overview gives a description of the properties of contrast media containing iodine and gadolinium as far as interactions following simultaneous administration are concerned. Subsequently, the clinically relevant situations and constellations are outlined and analyzed.

Rapid colorimetric sensing of gadolinium by EGCG-derived AgNPs: the development of a nanohybrid bioimaging probe.

PubMed

Singh, Rohit Kumar; Mishra, Sourav; Jena, Satyapriya; Panigrahi, Bijayananda; Das, Bhaskar; Jayabalan, Rasu; Parhi, Pankaj Kumar; Mandal, Dindyal

2018-04-17

Polyphenol functionalized silver nanoparticles (AgNPs) have been developed and demonstrated as colorimetric sensors for the selective detection of gadolinium. The newly obtained AgNP-Gd3+ conjugates exhibit high aqueous dispersibility and excitation dependent fluorescence emission. The conjugates offer multicolor bioimaging potential owing to their excellent luminescence properties.

A first principles kinetic Monte Carlo investigation of the adsorption and mobility of gadolinium on the (100) surface of tungsten

NASA Astrophysics Data System (ADS)

Samin, Adib J.; Zhang, Jinsuo

2017-05-01

An accurate characterization of lanthanide adsorption and mobility on tungsten surfaces is important for pyroprocessing. In the present study, the adsorption and diffusion of gadolinium on the (100) surface of tungsten was investigated. It was found that the hollow sites were the most energetically favorable for the adsorption. It was further observed that a magnetic moment was induced following the adsorption of gadolinium on the tungsten surface and that the system with adsorbed hollow sites had the largest magnetization. A pathway for the surface diffusion of gadolinium was determined to occur by hopping between the nearest neighbor hollow sites via the bridge site and the activation energy for the hop was calculated to be 0.75 eV. The surface diffusion process was further assessed using two distinct kinetic Monte Carlo models; one that accounted for lateral adsorbate interactions up to the second nearest neighbor and one that did not account for such interatomic interactions in the adlayer. When the lateral interactions were included in the simulations, the diffusivity was observed to have a strong dependence on coverage (for the coverage values being studied). The effects of lateral interactions were further observed in a one-dimensional simulation of the diffusion equation where the asymmetry in the surface coverage profile upon its approach to a steady state distribution was clear in comparison with the simulations which did not account for those interactions.

Doping droops.

PubMed

Chaturvedi, Aditi; Chaturvedi, Harish; Kalra, Juhi; Kalra, Sudhanshu

2007-01-01

Drug abuse is a major concern in the athletic world. The misconception among athletes and their coaches is that when an athlete breaks a record it is due to some "magic ingredient" and not because of training, hard work, mental attitude and championship performance. The personal motivation to win in competitive sports has been intensified by national, political, professional and economic incentives. Under this increased pressure athletes have turned to finding this "magic ingredient". Athlete turns to mechanical (exercise, massage), nutritional (vitamins, minerals), pharmacological (medicines) or gene therapies to have an edge over other players. The World Anti-Doping Agency (WADA) has already asked scientists to help find ways to prevent gene therapy from becoming the newest form of doping. The safety of the life of athletes is compromised with all forms of doping techniques, be it a side effect of a drug or a new technique of gene doping.